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112271

3701662

On the Synthesis of Leucic Acid

396

398

Proceedings of the Royal Society of London

Edward Frankland

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0082

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112271

10.1098/rspl.1862.0082

http://www.jstor.org/stable/112271

Chemistry 2

Fluid Dynamics

Chemistry

III . " On the Synthesis of Leucic Acid . " By Dr. EDWARD FRANKLAND , F.R.S. Received December 26 , 1862 . When oxalic ether is mixed with more than its own weight of zincethyl , the temperature of the mixture slowly rises , and soon considerable quantities of gas begin to be evolved , unless the heat be moderated by plunging the vessel , in which the reaction takes place , into cold water . The gas consists of equal volumes of ethylene and hydride of ethyl ; and as it is the product of a secondary decomposition , its evolution should be avoided as much as possible in the manner just indicated . The final application of a gentle heat completes the reaction . The mixture generally continues fluid , but it becomes of a light strawcolour , and of an oily consistency . On being heated to 130 ? C. in a retort , no distillate passes over . If , after cooling , its own volume of water be very gradually added to it , torrents of hydride of ethyl , derived from excess of zincethyl , are evolved . By subsequent distillation in a water-bath , weak alcohol containing an ethereal oil in solution passes over ; and a further quantity of the oil may be obtained by adding water to the residue in the retort , and continuing the distillation upon a sand-bath . The ethereal oil was precipitated from the alcoholic distillate by the addition of water , and was added to that which floated upon the surface of the aqueous distillate . It was then dried over chloride of calcium , and rectified . A very large proportion of the liquid distilled between 174 ? and 176 ? C. , and was collected apart . Numerous analyses of this liquid agree closely with the formula* C H6 03 . The liquid is in fact the ethylic ether of an acid possessing the same composition as the leucic acid obtained by Strecker* in acting on leucin by nitrous acid . Upon the oxalic acid type its formula may be thus expressed : ( C2 H5 I C2 HR C0,0 1 HO C2 H5 0 . Leucic ether cannot be directly derived from the action of zincethyl upon oxalic ether , but it is produced when water is added to the result of that reaction . There can scarcely be a doubt that the body first formed is zincoleucic ether , rC , H , 02 115 C2 H , C2( 0 ! ZnO . C , H O. I have not succeeded in isolating this body ; but , on the assumption of its production , the action of zincethyl upon oxalic ether may be thus formulated : Co 1 C2H , Z CHO+Zn O ZnO C2HO 1C 5 2ZnO r2C2 Zn 110 CH . 5 Zincethyl . H6 Ethylate of Oxalic ether . ----zinc . Zincoleucic ether . In contact with water zincoleucic ether is decomposed with the formation of leuci c ether and hydratend oide of zinc : c2 0 +H } O=C+Z } O. , ZnO ... ... ..| . H , Zincoleucic ether . Leucic ether . Leucic ether is a colourless , transparent , and somewhat oily liquid , possessing a peculiar and penetrating ethereal odour and a sharp taste . It is insoluble in water , but readily soluble in alcohol or ether . Its specific gravity is '9613 at 18 ? '7 C. ; it boils at 175 ? C. , and distils unchanged . A determination of the density of its vapour gave the number 5 241 : the above formula , corresponding to 2 vols . of vapour* , requires the number 5'528 . When leucic ether is treated with solution of hydrate of baryta , it gradually dissolves even in the cold ; on heating the solution in a water-bath , a liquid having the properties of alcohol distils off ; and on separating the excess of baryta by carbonic acid and filtration , the solution yields , on evaporation , a crystallizable baryta-salt which , after drying at 100 ? C. , gives on analysis numbers closely corresponding with the formula of leucate of baryta : C2H C2 0 HO KBaO . Leucate of potash is similarly produced when leucic ether is treated with an aqueous solution of caustic potash . It separates as a semisolid soap upon the surface of the potash solution , if the latter be concentrated . All the salts of this acid appear to be soluble in water . Leucic acid in solution is obtained when dilute sulphuric acid is added to leucate of baryta ; the acid has a sour taste , reddens litmus strongly , and is readily soluble both in water and alcohol . It can be boiled with water without decomposition , and traces only of the acid distil off with the water . So far as I have studied its properties , leucic acid thus obtained appears to be identical with that derived from leucin ; but it will be necessary to establish this identity by a more rigorous comparison of the two acids . The production of leucic acid from oxalic acid , as just described , obviously affords an insight into the molecular constitution of the class of organic acids of which lactic acid is the representative ; I refrain , however , from offering any opinion upon a point which has already given rise to so many hypotheses , until I have completed the study of this reaction , and extended it to other homologous bodies .

112272

3701662

On the Artificial Production of Fibrin from Albumen

399

407

Proceedings of the Royal Society of London

Alfred Hutchison Smee

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0083

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112272

10.1098/rspl.1862.0083

http://www.jstor.org/stable/112272

Chemistry 2

Physiology

Chemistry

IV . " On the Artificial Production of Fibrin from Albumen . " By ALFRED HUTCHISON SMEE , Junior , Student of St. Bartholomew 's Hospital . Communicated by W. S. SAVORY , Esq. Received January 15 , 1863 . The condition in which fibrin exists in the blood and other fluids , and the deviation in quantity and quality in certain cases of disease from that of normal blood , has been to physiologists a subject of great interest . From the close resemblance of fibrin to albumen , I was induced to undertake a series of experiments , which appear to me to have some value in determining the conditions under which fibrin is derived from albumen , and which have resulted in the discovery of the general principle by which the direct conversion of albumen into fibrin may be effected . On referring to Lehmann 's ' Chemistry , ' in which the analyses of albumen and fibrin are quoted , it will be observed , on comparing them , that the difference appears to be the substitution of 1'5 part of oxygen per 100 for a similar amount of carbon , hydrogen , nitrogen , sulphur , phosphorus conjoined . The following are the analyses quoted -Albumen . Fibrin . 53-5 Carbon ... 52'7 7'0 Hydrogen ... . 69 15'5 Nitrogen ... . 15'4 1'6 Sulphur ... . . 12 0'4 Phosphorus ... . 0'3 22-0 Oxygen. . 23'5 100'0 100'0 The analyses made by Scherer give comparatively the same results . From these analyses I was induced to make some experiments to endeavour to convert albumen into fibrin by the direct addition of oxygen gas , by which I anticipated that not only might the oxygen be imparted to the albumen , but also that the other elements might be oxidized and carried off . In my first experiments I used blood from which the fibrin had been carefully whipped during the period of its coagulation , so that the serum might contain as many blood-cells as possible , upon the supposition that the cells would afford a large amount of surface to the action of the gas . The serum , after being whipped , was permitted to stand for twenty-four hours , that any fibrin which it might contain , and which had not coagulated during the process of whipping , might do so . The apparatus used in all cases will be easily understood by referring to the annexed diagram . It consists , first , of a copper flask containing black oxide of manganese , from which the oxygen was slowly given off by the action of heat . The gas was conveyed thence by tubes into a wash-bottle , B ( containing a dilute solution of potass ) , for the absorption of impurities . From the bottle B the gas passed into the flask C , which contained the defibrinated blood . This flask was placed in a vessel ( D ) containing water at a temperature varying between 95 ? and 100 ? Fahr. ; and I had no difficulty in preserving that heat continuously by a small gas-flame placed under a sand-bath . After the gas had escaped from the blood , I generally passed it through a second portion of defibrinated blood contained in another vessel ( E ) . For all these experiments pig 's blood was invariably chosen , on account of its richness in blood-cells . My apparatus being ready , and oxygen being slowly given off , the whipped blood , from which every particle of fibrin had been previously removed , was introduced into the flask C. The blood employed was arterial , and not venous . At first the bright scarlet colour of the blood increased somewhat , but after twelve hours the bright scarlet began to assume more the colour of venous blood : the cells at the same time began to shrivel . From this time the blood began rapidly to grow darker and darker , when , after thirty-six hours , it was almost black* . Virchow has shown that , by acting on the haematin contained in the blood-cells by acetic acid , and subsequently boiling it , a substance is formed to which he gives the name of hamine , which he considers to be a product in an intermediate stage between heematin and pigment . The black substance formed by oxidation may probably be found to be analogous to , if not identical with , Virchow 's haemin . I found in this blood , at the end of thirty-six hours , small masses , which had , under the microscope , the appearance of fibrin . A small portion of the same blood as that used in the experiment was set aside till the completion of the experiment , when it was examined , but no fibrin was found . Likewise in the glass E , although the gas was passed through it without heat , no fibrin was found , proving that temperature had also an effect on the production of fibrin . This experiment was repeated many times : in all cases the blood assumed the black colour , but I did not invariably find fibrin . The appearance of fibrin in some cases , and the non-appearance in many others , seemed at first sight to be inexplicable , though I shall be able to demonstrate , in a later portion of this paper , that the result may be explained upon the hypothesis that the alkaline salts were in relative excess in those cases where the fibrin did not appear . In my next series of experiments , the white of an egg was added to about 4 oz. of the defibrinated blood . The egg-albumen at first had a tendency to separate and float at the top of the blood-serum , although well agitated together . In these cases the blood assumed the same dark colour as when it was subjected to experiment alone , though it did not appear until after the serum and egg-albumen had completely coalesced , which took place about ten hours after the subjection to temperatures between 95 ? and 100 ? Fahr. , and the action of oxygen gas . At the end of thirty-six hours , the time when the experiment was stopped , masses of substances were found float* Crawford , about fifty years back , found that , after immersing animals in hot water , no difference could be discerned between arterial and venous blood . ing , and also adhering to the bottom and sides of the vessel . These clots were in sufficient quantity to be collected and washed in the filter to free them from blood-cells and other impurities . The washed portion , under the microscope , had the distinct appearance of fibrin . In cases where the albumen had not sufficient time to be mingled with the blood , little or no fibrin was formed . The time occupied for its absorption varied from about ten to twenty hours . In the experiments which I conducted with albumen alone , I experienced at first some difficulty in obtaining the albumen perfectly pure , on account of the presence of chalazm and other foreign matter . To obviate this difficulty , I found that , by adding one drop of glacial acetic acid to every white of egg employed , and then by well beating up the albumen , I obtained , on subsequent filtration , a clear solution which gave to litmus-paper a slightly acid reaction . On placing this transparent albumen in the ordinary apparatus , I found , after the passage of oxygen gas for four hours at the temperature before stated , that fibrin began to be formed . I found that , by placing coils of platinum wire in the albumen whilst undergoing oxidation , the formation of fibrin was not only greatly facilitated , but its subsequent separation from the rest of the albumen was accomplished with greater ease , as the fibrin hung in threads upon the platinum wire . When platinized platinum was used , the formation of fibrin , as might have been expected , was slightly improved . Fibrin produced artificially in these experiments , and especially that formed on platinum wire , had a beautiful and regular arrangement , mostly being deposited in parallel lines . The fibrin likewise was whiter , and had a more delicate consistence than the common fibrin in blood . I next tried the effect of adding a small quantity of a strong solution of ammonia to the albumen , which had naturally a slightly alkaline reaction ; and then it was subjected to the influence of a current of oxygen in the same manner as in the preceding experiments . I found that fibrin was formed to a much smaller extent than when acid albumen was employed . The ammonia in all cases appears to be driven off to some extent by the oxygen , but was never entirely removed . The fibrin in this case formed on the surface of the liquid , and did not appear to be dissolved as the experiment was progressing . It is worthy of particular observation , that fibrin was formed in the liquid which still contained ammonia in appreciable quantity . My father suggested to me that it would be desirable to try the effect of the decomposition of water by electricity on albumen , as by that process the effect of hydrogen and oxygen in a nascent state is presented to different parts of the same fluid . For the purposes of this experiment I employed four cells ( of the test-tube form ) of Smee 's battery , in which the negative pole consisted of a platinized platinum wire . This battery generated a continuous , but feeble , current of electricity ; and the smallest perceptible bubbles were evolved from the platinized platinum wire when in operation for the experiment . The albumen was placed in the decomposition trough , where a very large positive pole was employed , but a smaller negative one , and the temperature was maintained as in former experiments . After the passage of the electric current for some time , the positive pole of the decomposition cell was coated with a hard gelatinous mass , which , being immersed in water at 90 ? Fahr. for a few hours , unravelled itself into long fibres , which had , under the microscope , the appearance of fibrin . On the negative pole , however , a frothy deposit alone was formed ; but great care must be taken to stop the experiment before the products of the two poles grow together , to which they have a great tendency . The moment this takes place the albumen begins to coagulate , and in a very short time the whole becomes converted into an almost semisolid mass . The fibrin is not so perfect when made by this method , and is much more difficult to form than when made from neutral or slightly acid albumen by the ordinary process of oxidation . In my experiments with egg-albumen to which a solution of potass had been added before it was subjected to the action of oxygen , the temperature ranging between 95 ? and 110 ? Fahr. , no fibrin was found when the experiment was stopped . In one case oxygen was passed through a solution of potass and albumen for three days and nights , and yet not the slightest trace of fibrin was found . The albumen became of a dark red hue , but two days after the experiment ceased it resumed its normal colour . A few transparent hard substances were found , insoluble in water and weak acids which had separated from the albumen . A few other small white substances were noticed , which had all the appearance of carbonate of lime , and which were soluble in acid . Albumen was then mixed with gastric juice , and kept at the normal temperature of the body for the space of twelve hours , to produce artificial digestion , when it was subjected to experiment . I should here state that the gastric juice was procured from a dog , which had a fistulous opening made into its stomach by Professor Savory . All symptoms of inflammation and irritation had fully ceased ; the dog , in fact , was in perfect health , and beginning to get fat , when the gastric juice was procured ; so that the latter must be considered as healthy gastric juice . From the dog large quantities of gastric juice were obtainable ; and I have to tender my best thanks to Professor Savory for his great kindness in placing whatever I required at my disposal . After the albumen had been digested for twelve hours and filtered , that the solution might be perfectly clear , it was subjected to the action of oxygen for a few hours , when fibrin was formed , though not in so large an amount as in albumen to which one drop of the glacial acetic acid had been added . The filaments of the fibrin , however , were of a more delicate constitution . From a consideration of the above results , I thought that fibrin might be formed from the albumen which , after digestion with gastric juice , had passed through a membrane made of the parchment paper of Messrs. De la Rue and Gains . In some experiments* to which I had been led from a study of Professor Graham 's elegant researches on dialysis , and which I had formerly been conducting , on the passage of various fluids through membranes , it was observed that albumen , after digestion with gastric juice , dialysed to a certain extent . Three ounces of albumen were digested for the space of twelve hours , at the temperature of the body . It was then placed on the dialyser : it should be remarked that gastric juice does not coagulate the albumen during its conversion into albuminose . The digested albumen was kept for ten hours on the dialyser at the temperature of 98 ? to 110 ? Fahr. The water ( one and a half pint ) into which the digested albumen had passed was concentrated at a temperature of not more than 80 ? Fahr. ; and the concentrated solution being afterwards oxidized , I found that fibrin was formed , notwithstanding the changes it had undergone by digestion , which had rendered it capable of dialysis . During the process of passing oxygen into albumen , I found that carbonic acid was evolved . This was ascertained by passing the oxygen , after it had escaped from the albumen , through limewater . I also found that phosphoric acid was evolved , by subjecting the effluent oxygen to the molybdate-of-ammonia test . Carbonic acid and phosphoric acid were also found when blood-serum was used , by the same tests as those employed when egg-albumen was the material used for experiment . In some cases common air was driven through albumen in the place of oxygen , at a temperature between 95 ? and 110 ? Fahr. , and then I found the formation of fibrin differed but little from the quantity produced when oxygen alone was used . To ascertain whether the formation of fibrin was due really to oxygen alone , I tried hydrogen gas in the place of oxygen or common air , and at the same temperature . When hydrogen was passed into blood-cells sulphur was evolved . This was detected by passing the hydrogen , after it had traversed the serum , into a solution of leadsalt , and also by suspending over the serum strips of lead paper , when they soon became blackened by the sulphur . When egg-albumen was employed instead of the blood-serum , sulphur was again detected . Fibrin was not formed by the action of hydrogen on blood-serum or egg-albumen , although in some cases the hydrogen was passed continuously for forty-eight hours through the fluids . The action of carbonic acid gas on egg-albumen under the same condition of temperature produces no fibrin , but sulphur was again detected by suspending strips of lead paper over the albumen , which in a few hours became tinged . The same result was obtained when defibrinated blood was used ; but in this case , in addition to the sulphur , a minute trace of phosphoric acid was found . Not the slightest trace of fibrin was detected . I conceived , from the result of my experiments on the oxidation of albumen , that , if oxygen was passed into milk , fibrin might be formed , from the fact that the analyses of albumen of egg , and the casein which the milk contains , differ little from each other , and because the analysis of the milk of an animal , a few days before and after parturition , shows that albumen is found in the place of casein . On subjecting , however , milk to experiment , no fibrin was found after the lapse of twenty-four hours . This may be due to either of two causes : first , the casein in the milk may not be in a fit state for undergoing the change before it has been acted on by the various digestive secretions , or , secondly , because in the dilute and fluid state in which it occurs in milk it does not offer sufficient resistance to the passage of the bubbles of oxygen to retain the gas sufficiently long for each bubble to have time to produce an effect . In all my experiments I have found ( other conditions being equal ) the slower the bubbles passed through the liquid material , and the more viscid the fluid was , the greater was the amount of fibrin produced . This may possibly in some degree account for the non-formation of fibrin when oxygen was passed through milk . I tried the effect of oxygen upon fresh grape-juice , but was unable to form any fibrin from it . Further experiments are required upon various vegetable juices . I next experimented upon the oxidation of gluten , which was obtained from wheat-flour by the ordinary method . This was digested in gastric juice for twelve hours , and then filtered . After the clear liquid had been subjected to oxidation for some hours , small threads of a substance were formed . When a portion of this was placed under the microscope , no difference could be detected between it and ordinary fibrin . From these experiments , it seems to me that the following conclusions may be drawn : First , that fibrin is produced by the direct action of oxygen on albumen . Secondly , that the alkalies and alkaline salts prevent the appearance of fibrin when albumen is acted upon by oxygen . Thirdly , that the formation of fibrin from albumen is accompanied by the evolution of sulphur , phosphorus , and carbonic acid . Fourthly , That a temperature ranging between 980 and 110 ? Fahr. promotes the artificial formation of fibrin . Fifthly , that the greatest amount of fibrin appears when the albumen is neutral or slightly acid . Sixthly , that the viscidity of the material employed promotes the formation of fibrin . Seventhly , that albumen , artificially digested in gastric juice , produces fibrin by its subsequent oxidation , even after dialysis . Eighthly , that gluten dissolved in gastric juice , and then oxidized at the ordinary temperature , yields fibrin . The formation of fibrin in the human body , and its relation to albumen , has long been a vexed question . I venture to put forward these experiments in connexion with this important and interesting inquiry .

112273

3701662

Note on the Spectrum of Thallium

407

410

Proceedings of the Royal Society of London

William Allen Miller

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0084

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112273

10.1098/rspl.1862.0084

http://www.jstor.org/stable/112273

Atomic Physics

Chemistry 2

Atomic Physics

V. " Note on the Spectrum of Thallium . ' By Professor WILLIAM ALLEN MILLER , M.D. , LL. D. , Treasurer and V.P.R.S. Received January 15 , 1863 . My friend Mr. Crookes , the discoverer of the new metal thallium* , having kindly put into my hands a small quantity of the metal , which he believes to be chemically pure , I have been enabled to make some experiments upon its spectrum , the results of which may not be without interest to the members of the Royal Society . Thallium , as is well known , when examined in the usual way by the spectroscope , yields a spectrum of remarkable simplicity , furnishing a single intense green line , the occurrence of which , as is familiar to chemists , led Mr. Crookes to the discovery of the metal , and suggested to him the name by which it is known . In order to try the effect of a progressively increasing temperature upon the spectrum furnished by the metal and its compounds , the following experiments were made . Portions of metallic thallium , as well as of an alloy formed by fusing a bead of thallium upon the end of a platinum wire , and portions of the sulphate of the metal were introduced successively , first , into the flame of burning hydrogen , and then into the oxyhydrogen jet , and were in each case viewed by the spectroscope . As the temperature increased in intensity , the brilliancy of the thallium green line increased also , but no new lines made their appearance . Two pieces of stout thallium wire were then arranged as electrodes to the secondary wire of an induction coil . A continuous torrent of sparks was maintained without melting the wires or producing very rapid oxidation , or volatilization of the metal ; the light , however , was much whiter than its ordinary monochromatic character would have led us to expect . Mr. Crookes , who was with me during the experiments , projected the image of the points by means of a lens upon a distant white screen , when it was at once obvious that the extremities of the spark were of a fine green colour , whilst the flickering luminous arc , which filled up the interval , due chiefly top ignited air , was much whiter . On viewing the sparks from the induction-coil by the spectroscope , several new lines , independently of well-marked air-lines , made their appearance . These lines were distinguished from air-lines by the peculiar character which distinguishes most metallic lines , viz. the much greater intensity of their extremities than of their central portions . Besides the usual intense line in the green , five others were particularly observable : first , a very faint one in the orange ; next , two of nearly equal intensity in the green , more refrangible than TlM , with a third much fainter , these three lines in the green being nearly equidistant ; whilst , 5th , in the blue was a bright well-defined line all these were strong at each extremity and evanescent in the central portions . The induction-spark of thallium was then observed when produced in a current of hydrogen gas . The air-lines disappeared , the peculiar lines of hydrogen were very manifest , particularly the line in the red and one of the lines in the blue ; whilst the new thallium lines were preserved , with the exception of the feeblest , though all were reduced in intensity . Finally , a photographic impression of the thallium spectrum upon collodion was obtained by the method which I have described in a paper communicated to the Royal Society in June last . An impression extending to about division 154 of the scale then adopted was obtained . This spectrum contains several very characteristic groups of lines ; it recalls the features of the spectra of cadmium and zinc , and less strongly that of lead . Measuring by the scale already adopted in my former paper , it is found that there are two strong groups of lines at about 103 and 106 . At 116 , 121 , and 126 are three groups the first two less intense than the third , which is of about the same strength as the earliest two . Several feebler pairs of dots follow , and the spectrum terminates rather abruptly with four nearly equidistant groups , commencing respectively at 136 , 141 , 145 , and 151 . The first of these groups is very strongly marked , the others are fainter , but of nearly equal intensity . The remarkable way in which a spectrum at low temperatures so simple becomes increased in complexity , both in the visible and in the extra-visible portions , is of high interest considered in relation to the physical cause of these phenomena ; and it is not without interest in a chemical sense , from its bearing upon the view supported by Dumas , that thallium belongs to the alkaline group . Potassium and sodium exhibit no new lines in the induction-spark , merely a diffuse light filling up the air-lines , and lithium but a single strong group at about 124 . This physical character , added to the more purely chemical ones of the insolubility of the sulphide , the chromate , the iodide , the sparing solubility of the chloride , the phosphate , the oxalate , the ferrocyanide , the occurrence of a powerfully basic oxide , and of a higher feebly acid oxide , may therefore assist in showing the resemblance of thallium to silver or to lead , which latter metal in density , colour , softness , and external appearance it so closely simulates . It would be easy to point out other particulars in which the properties of thallium are in strong contrast with those of the alkali metals . The chemical energy of these metals , lithium , sodium , potassium , rubidium , and caesium , increases in the order mentioned , which is that of their equivalents . Thallium , with a higher equivalent than any of these , shows a greatly diminished chemical activity . The metal is readily reduced by zinc from its solutions . Its oxide , instead of being like that of all the alkalies , excessively deliquescent , is permanent in air , and forms a closely adhering coat like that which is produced upon the surface of zinc or lead , protecting the metal beneath from further change . In many points the chemical reactions of thallium resemble those of silver , to which metal it is also further approximated by the circumstance that the atomic heat of the metal , like that of silver , is double that of the series to which lead belongs . Although therefore in other physical properties thallium differs greatly from silver , it seems to be more closely allied to that metal than to any other

112274

3701662

Researches on Some of the Artificial Colouring Matters.--No. I. On the Composition of the Blue Derivatives of the Tertiary Monamines Derived from Cinchonine

410

418

Proceedings of the Royal Society of London

A. W. Hofmann

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0085

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112274

10.1098/rspl.1862.0085

http://www.jstor.org/stable/112274

Chemistry 2

Biography

Chemistry

I. " Researches on some of the Artificial Colouring Matters . No. I. On the Composition of the Blue Derivatives of the Tertiary Monamines derived from Cinchonine . " By A. W. HOFMANN , LL. D. , F.R.S. Received December 18 , 1862 . The chemical visitors of the International Exhibition will not easily forget the magnificent collection of products displayed in the French court by M. Menier of Paris . Among these compounds , equally remarkable for their variety and beauty , the large crystals of cyanine , rivalling in splendour and purity Mr. Nicholson 's acetate of rosaniline , have attracted general attention . M. Menier , who has produced this new dye on a very large scale , has most liberally placed at my disposal some of the finest of these crystals for examination , hoping that their more minute investigation might perhaps lead to a method of giving solidity to this new colour , which in brilliancy and purity of tint is second to none of the several blues lately derived from coal-tar . The composition of cyanine and its mode of formation having hitherto remained unknown , I have gladly availed myself of this opportunity of performing some experiments with this interesting compound . I am sorry to say that , in a practical point of view , these experiments have failed entirely ; but my studies have led me to some observations on this substance which , as a contribution to the history of cyanine , deserve to be recorded , and which I beg leave to communicate to the Royal Society . The discovery of the blue compounds from chinoline and its homologues dates as far back as 1856 . In that year Mr. G. Williams engaged in a renewed examination of the base extracted by Rung from coal-tar and obtained by Gerhardt from the alkaloids of the cinchona bark , the identity in composition of which I had established in one of my earlier researches . Among the numerous compounds of these bases most carefully examined by Mr. G. Williams on this occasion , were also their methylated and ethylated derivatives , one of which , the iodide of methyl-leucolylammonium , I had discovered when studying the action of iodide of methyl upon ammonia and its analogues . It was in preparing this compound from the chinoline obtained by the distillation of cinchonine , and in separating the ammonium-base corresponding to the iodide by means of oxide of silver , that Mr. Williams first observed the splendid coloration which has led him to the discovery of the new dye now commercially known under the name of cyanine . Precisely similar phenomena were subsequently ( in 1857 ) observed by M. von Babo , who produced them by treating chinoline with the sulphates of methyl and ethyl , and described the coloured substances thus obtained as methylirisine and ethylirisine . Mr. Williams was inclined to attribute the formation of the blue compounds , in which he recognized distinctly basic properties , to a process of oxidation ; M. von Babo represents his methyland ethylirisine , although with very great reserve , by the formulae C11HNO , and CliNG Cll H14 2 02 and C13 H18 N2 02 . No attempt has since been made to establish the composition of these singular compounds by a more minute examination . In fact several years elapsed without any further notice being taken of them , until the development of the aniline industry revived the memory of these remarkable colour phenomena , which have since attracted the general attention of dyers and printers . Mr. G. Williams showed that , among the several coloured compounds produced by the action of iodides of alcohol radicals upon chinoline bases , the one obtained by means of iodide of amyl is particularly rich in tinctorial power ; he has given a very interesting account of this new dye , and accurately described the mode of manufacture of this body , which , under the name of cyanine , soon became an article of commerce . Unfortunately the tint produced by cyanine is less fast than beautifil , and the hopes entertained of the industrial future of the new compound has not been realized ; nevertheless the importance attached by dyers to Mr. Williams 's discovery is well marked by the fact of a gold medal , together with a prize of 10,000 francs , having been proposed for the discovery of a means of rendering stable the beautiful colours dyed by cyanine . The crystals submitted to me for examination by M. Menier were distinct prisms , sufficiently well formed for crystallographical determinations . They are at present in the hands of Quintino Sella . Their substance possesses a beautiful green metallic lustre with a golden tint , by which , as well as by crystalline form , they are readily distinguished from acetate of rosaniline , which they in other respects much resemble . The crystals are insoluble in anhydrous ether , difficultly soluble in water , but dissolve readily in alcohol . The solution has a magnificent blue colour , with a coppery iridescence on its surface . Addition of acids destroys this colour . Ammonia and the fixed caustic alkalies leave the colour apparently untouched ; but it is now produced by a finely divided deep-blue precipitate suspended in the liquid , which may be filtered off , the filtrate separated from it being colourless . The green crystals were found to be the iodide of a peculiar basic compound . The iodine is rather firmly held in this compound ; but it may be precipitated from the alcoholic solution by oxide of silver , and . exchanged for bromine or chlorine by treatment of this solution with bromide or chloride of silver , when the bromide or chloride corresponding to the iodide are produced . The analysis of the crystals gave results indicating unequivocally the formula C3o H39 N , I , which received a close confirmation by the examination of a fine platinum-salt crystallizing in rhombic tablets , which is obtained by precipitating the chloride corresponding to the iodide , strongly acidulated with hydrochloric acid , by dichloride of platinum . Nevertheless slight discrepancies between the theoretical values of the formula and the results obtained led me to assume the existence in the crystals of a compound containing less carbon and hydrogen , indeed of a homologous iodide , C,2 , H , ,3 N2 . This hypothesis , not countenanced at first by the remarkable constancy which the composition of the iodide presented even after three or four crystallizations , was fully confirmed when the chloride was submitted to a systematic partial precipitation by dichloride of platinum . After several repetitions of the process , the partially precipitated platinum-salt being decomposed by sulphuretted hydrogen and the chlorides again partially precipitated , two platinum-salts were obtained , one of which , the less soluble one , proved to be the pure platinum-salt corresponding to the iodide with 30 equivalents of carbon , whilst the other one was sufficiently pure to show that it belonged in reality to the homologous iodide with 2 equivalents of carbon less . The amount of the iodide C28 1H3 N2 I , which contaminated ( if the term may be applied to so beautiful a substance ) the iodide C30 H39 N2 1 , is , however , so small that its presence did not materially influence the analytical results obtained in the further examination of the compound . The explanation of the formation of the iodide presents no difficulty ; this substance obviously derives from lepidine , C1 , H N , whilst only the slight admixture is due to the presence , in the original bases submitted to the action of iodide of amyl , of a small quantity of chinoline , C9 17N . In fact Mr. Williams , in describing the preparation of his dye , distinctly states that the chinoline by no means requires to be pure for the purpose . M. Menier has moreover kindly furnished me with a considerable quantity of the crude material from which the green crystals are obtained . This proved to be a mixture of several bases , in which the presence of lepidine and chinoline was traced without the slightest difficulty , by the analyses of platinum-salts . In the genesis of the new iodide two different phases have to be distinguished , viz. , 1 , the transformation of lepidine into iodide of amyllepidyl-ammonium , C , o H9 N+ Cs H , l I= C0 H2 N I ; Lepidine . Iodide of amyl . Iodide of amyl-lepidyl-ammonium , the condensation under the influence of potash of two molecules of the compound into one molecule of a higher order , 2(C15120 N I ) +K O=C30 H39 N2 I+KI+H2 O Iodide of amyl-lepidyl-ammonium . New iodide . It became indispensable to verify these reactions by the analysis of additional compounds . The green crystals dissolve with facility in boiling dilute hydriodic acid ; the colourless solution deposits on cooling yellow needles of remarkable beauty , the analysis of which has furnished the values of the formula C30 H4 N I2-= C30 H39 N2 I , H I. 'These crystals are isomeric with iodide of amyl-lepidyl-ammonium , from which , however , they are distinguished by all their properties They dissolve in cold water without decomposition , but on addition of alcohol they immediately assume a blue coloration , the original monacid compound being reproduced . The same change takes place at 100 ? ; so that in preparing the compound for analysis it was necessary to dry it in vacuo . In the facility with which the diacid compounds are converted into the monacid salts , this substance resembles rosaniline , which , as I have pointed out in a recent paper , forms likewise colourless acid salts of little stability . The green iodide dissolves with equal facility in hydrochloric and hydrobromic acid , yielding perfectly colourless solutions , and giving rise to the formation of well-crystallized compounds , which contain , in addition to iodine , respectively bromine and chlorine . On submitting the green iodide in alcoholic solution to the action of chloride of silver , the whole of the iodine is separated in the form of iodide of silver , a blue solution being obtained from which the monacid chloride crystallizes , on slow evaporation , in green metallustrous sharply-defined prisms of surpassing beauty . This salt was found to contain Dissolved in hydrochloric acid , tis salt furnished a dicid compound Dissolved in hydrochloric acid , this salt furnished a diacid compound which , on evaporation in vacuo , separates in long straw-coloured needles . The highly deliquescent character of this substance has hitherto prevented me from analysing it ; but if there was the slightest doubt of this compound having the composition Ca0 Ho N , Cl2=C30 H39 N , CI , H C1 , it would be dispelled by the analysis of a fine-yellow difficultly solu . ble platinum-salt crystallizing in small well-defined rhombic plates , which falls directly on addition of dichloride of platinum to the alcoholic solution of the diacid chloride , containing a considerable amount of hydrochloric acid , and which , by analysis , was found to be represented by the formula C30 H4o N2 Cl , 2 Pt Cl2 . The gold-salt is obtained by precipitating the solution of the acid chloride with trichloride of gold , when a yellow , scarcely crystalline precipitate is formed , which , dried in vacuo , contains C30 HI0 N2 C12 , 2Au C13 . I have , moreover , prepared the monacid bromide , which forms beautiful metal-lustrous prisms easily crystallizable ; the diacid nitrate as a crystalline network , on evaporating a solution of the base in nitric acid in vacuo ; and , lastly , the acid sulpliate , which crystallizes in white , well-formed rhombic tables , very soluble in water , but insoluble in alcohol , by which it is not decomposed like the other diacid compounds . I have refrained from multiplying the analytical evidences by the minute examination of these salts , because I was happy enough to observe a reaction which supported the interpretation of the results of analysis in an unequivocal manner . Remembering the simple scission which I had formerly accomplished by exposing the iodide of tetrethylammonium to the action of heat , when the compound splits into iodide of ethyl and triethylamine , I was induced to submit the green iodide to distillation . The green crystals rapidly fuse into a blue liquid , the surface of which presents a peculiar coppery lustre . On raising the temperature , decomposition takes place , and in the receiver is condensed a mixture of lepidine and iodide of amyl , the reunion of which to iodide of amyl-lepidyl-ammonium may be prevented by collecting them in hydrochloric acid ; at the same time a gas is evolved , burning with a brilliant flame and readily absorbed by bromine , and which could easily be condensed by passing it through a serpentine surrounded with ice . I was thus enabled to collect enough of the volatile hydrocarbon to determine its boiling-point , which proved it to be pure amylene . If the heat be carefully regulated , the amount of charcoal remaining in the retort is comparatively small . The interpretation of the phenomena observed is given in the following equation : C30 H39 N2 I= 2C1 H9 N+ C5 H , l I+C Hlo Green iodide . Lepidine . Iodide of Amylene . amyl . Here , again , I have had an opportunity of proving the presence in the crystals of a small quantity of the homologous chinoline compound ; for on submitting , after separating the iodide of 'amyl , the hydrochlorate of the volatilized base to distillation with potassa , and collecting apart the first quantity of the basic liquid which came over with the vapour of water , this substance proved by the platinum determination to be chiefly chinoline , while the portion of the base distilling last proved by the same mode of analysis to be pure lepidine . The results obtained in these experiments furnish new illustrations of the tendency to molecular accumulation by which the ammonias and their derivatives are distinguished . Only a few weeks ago I had the honour of submitting to the Royal Society a short account of this class , which is obtained as a secondary product in the manufacture of aniline . The coloured derivatives of the bases of the chinoline series present in their composition considerable analogy with paraniline . Aniline series . C6 H7 N C6 H7N , HC1 Aniline . Chloride . C6 HN C6 HN1 HC1 C6 H7 N1 HC1 C6 , H , N C06H7N C6H,7N HC1 Paraniline . Monacid chloride . Diacid chloride . Lepidine series . C,5 H19 N2H,0 C51 H9 N , HC1 Hydrated oxide of amylChloride . lepidyl-ammonium . C15 H , , NH2 01 ? C1511 N1 C1 C15 H19 N HC1 C15 H19 NH20 C15 H19 N C15 H19N HC1 Free blue base . Green iodide , monacid . Yellow iodide , diacid . I have written the formulae of the coloured compounds so as to bring out their analogy with the paraniline salts-in fact , so as to characterize them as para-compounds of the amyl-lepidyl-ammonium salts , but I am far from attributing to these formulae any other value . In fact the molecular construction of this new class of compounds remains to be established by further experiments . The theory which ( in 1852 ) satisfactorily represented the constitution of the nitrogen bases then examined , requires an expansion to include the tinctorial ammonias added to our knowledge during the last decade . The time for the enunciation of this amplified theory has not yet arrived . Here only a few experiments may still be mentioned , which were made with the oxide corresponding with the salts described . The action of oxide of silver upon the iodide dissolved in alcohol liberates the base , which , on evaporation of the alcohol , separates as an indistinctly crystalline deep-blue mass , moderately soluble in water , less soluble in anhydrous ether , easily soluble in alcohol . Ether precipitates the base from its alcoholic solution ; I have not examined it . Submitted to distillation , the free oxide gives rise to an oily base , which I naturally expected to be lepidine ; but the experiments which I have hitherto made with this substance appear to negative this assumption . I have undertaken a more minute examination of the compound , because , if it be different , its study will probably throw some light upon the still uncertain constitution of the tertiary bases of the chinoline series , which I have frequently attempted to decipher . It remained now only for me to examine the mode of formation of the remarkable compound the nature of which I have endeavoured to clear up . With this view I have studied the action of iodide of methyl and amyl upon chinoline and lepidine , large quantities of which were kindly placed at my disposal by my friend Mr. David Howard . The products obtained in this reaction I have not submitted to a minute examination , having satisfied myself that their principal phases are well illustrated by the equations which I have given for the formation of the substances produced by the action of iodide of amyl upon lepidine . Nor have I followed out in detail the complicated secondary changes , and more especially the generation of the red colouring matter which is abundantly formed in these reactions . I have nothing to add to the perfect description of these phenomena by the distinguished discoverer of this pigment . In conclusion I may be allowed to express my best thanks to M. Menier : without the magnificent crystals furnished by his ateliers , I could not have even attempted to clear up this question . Though proud of her office as guide of industry , science acknowledges without blushing that there are territories on which she cannot advance without leaning on the strong arm of her powerful companion . Joint labours of this kind cannot fail to seal the pledge of alliance between industry and science .

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3701662

On Some New Compounds Obtained by Nitrogen-Substitution, and New Alcohols Derived Therefrom

418

420

Proceedings of the Royal Society of London

Peter Griess

fla

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http://dx.doi.org/10.1098/rspl.1862.0086

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http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112275

10.1098/rspl.1862.0086

http://www.jstor.org/stable/112275

Chemistry 2

Astronomy

Chemistry

II . " On some new Compounds obtained by Nitrogen-substitution , and new Alcohols derived therefrom . " By PETER GRIESS , Esq. Communicated by Dr. HOFMANN . Received December 18 , 1862 . In the beginning of this year ( 1862 ) I pointed out* that diazoamidobenzol , when submitted to the action of nitric acid containing nitrous acid in solltion , is transformed into a new compound according to the equation CI2 H11 N3- , 2H NO +H NO3=2(C6 H1 N2 , 1 NO3 ) +2 H , 0 . Diazo-amidobenzol . New compound . I have now found that this remarkable compound , the nitrate of diazobenzol , can be much more easily produced by the action of nitrous acid upon nitrate of aniline , C6 H7 N , H NO + N , =C,6 H4 , , N,0 +2H2 O. Nitrate of aniline . Nitrate of diazobenzol . This process has furnished me a considerable number of similarly conconstituted nitrogen-substituted derivatives , not only of monacid monamines , but also of diamines ; and it is to some of the bodies generated by means of the latter that I beg leave to call the attention of the Royal Society . If a current of nitrous acid be passed into a cold solution of the nitrate of benzidine , a base which , by the researches of P. W. Hofmann , has been characterized as a well-defined diacid diamine , a new compound is produced , crystallizing from water in white needles , explosive like fulminate of mercury , the composition of which was established by the analysis of a platinum-salt containing C12 HE N , , 2HCl , 2PtC2 , . The formation of this new substance is illustrated by the following equation : C12 112 N2+ 2H NO3 +2H N2 =C1 H6 N , 2II NO3 +4H 0 . , _L___ , ? JtJ Nitrate of benzidine . New compound . Of subordinate interest themselves , these substances deserve to be noticed on account of the numerous and often peculiar bodies arising from their decomposition . Thus the tetrazo-compoundjust described , when boiled with water , splits according to the equation C12 H , N4 , 2H NO3+2H20= C12 H O , + 2N4+2H NO , . Nitrate of tetrazo-compound , New substance . The new non-nitrogenous substance thus obtained crystallizes in small sublimable plates . Both formula and properties characterize it as a compound standing , like phenol , upon the boundary line between acids and alcohols : it furnishes a very extensive series of derivatives , which may be generally represented by the formula 2Phenyl-body 2H -I new compound , IHere I will only mention the chloride corresponding to the new alcohol ( acid ) . It crystallizes in white volatile plates , which may be readily prepared by heating the above-mentioned platinum-salt with carbonate of sodium . The reaction takes place at 100 ? . C12 H N4 , 2H C1 , 2 PtCl C=012 H C12 + 2PtCIl +4 N. In conclusion , I may be allowed to state that nitrate of naphthylamin likewise yields an azo-compound . This compound , Co1 N HNH N O , when submitted to the action of boiling water , undergoes a transformation analogous to that of nitrate of diazobenzol , C , H , N2 HNO3 + H2 0=C6 0+ 2N+ H NO3 , Nitrate of diazobenzol . Phenol . Clo H6 N2 H NO + H20= C H8 0+ 2N+ H NO , . Nitrate of diazonaphthol . New compound . I have not yet analysed this new compound ; but both mode of formation and properties ( it crystallizes in white very fusible needles , possessing the odour of creosote ) leave no doubt that it is the alcohol of the naphthaline series which has so long eluded the researches of chemists .

112276

3701662

On the Differential Equations of Dynamics. A Sequel to a Paper on Simultaneous Differential Equations. [Abstract]

420

424

Proceedings of the Royal Society of London

George Boole

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6.0.4

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http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112276

http://www.jstor.org/stable/112276

Formulae

Biography

Mathematics

III . " On the Differential Equations of Dynamics . A sequel to a Paper on Simultaneous Differential Equations . " By GEORGE BOOLE , F.R.S. , Professor of Mathematics in Queen 's College , Cork . Received December 22 , 1862 . ( Abstract . ) Jacobi in a posthumous memoir* , which has only this year appeared , has developed two remarkable methods ( agreeing in their general character , but differing in details ) of solving non-linear partial differential equations of the first order , and has applied them in connexion with that theory of the differential equations of dynamics which was established by Sir W. R. Hamilton in the 'Philosophical Transactions ' for 1834-35 . The knowledge , indeed , that the solution of the equation of a dynamical problem is involved in the discovery of a single central function , defined by a single partial differential equation of the first order , does not appear to have been hitherto ( perhaps it will never be ) very fruitful in practical results . But in the order of those speculative truths which enable us to perceive unity where it was unperceived before , its place is a high and enduring one . Given a system of dynamical equations , it is possible , as Jacobi had shown , to construct a partial differential equation such that from any complete primitive of that equation , i. e. from any solution of it involving a number of constants equal to the number of the independent variables , all the integrals of the dynamical equation can be deduced by processes of differentiation . Hitherto , however , the discovery of the complete primitive of a partial differential equation has been supposed to require a previous knowledge of the integrals of a certain auxiliary system of ordinary differential equations ; and in the case under consideration that auxiliary system consisted of the dynamical equations themselves . Jacobi 's new methods do not require the preliminary integration of the auxiliary system . They require , instead of this , the solution of certain systems of simultaneous linear partial differential equations . To this object , therefore , the method developed in my recent paper on " Simultaneous Differential Equations " ( Philosophical Transactions for 1862 ) might be applied . But the systems of equations in question are of a peculiar form . They admit , in consequence of this , of a peculiar analysis . And Jacobi 's methods of solving them are in fact different from mine , though connected with it by remarkable relations . He does indeed refer to the general problem of the solution of simultaneous partial differential equations , and this in language which does not even suppose the condition of linearity . He says , " Non ego hic immorabor queestioni generali quando et quomodo duabus compluribusve sequationibus differentialibus partialibus una eademque functione satisfieri possit , sed ad casum propositum investigationem restringam . Quippe quo preeclaris uti licet artificiis ad integrationem expediendam commodis . " But he does not , as far as I have been able to discover , discuss any systems of equations more general than those which arise in the immediate problem before him . It is only very lately that I have come to understand the nature of the relation between the general method of solving simultaneous partial differential equations , published in my recent memoir , and the particular methods of Jacobi . But in arriving at this knowledge I have been led to perceive how , by a combination of my own method with one of those of Jacobi , the problem may be solved in a new and perhaps better , certainly a remarkable way . This new way forms the subject of the present paper* . Before proceeding to explain it , it will be necessary to describe Jacobi 's methods , to refer to my own already published , and to point out the nature of the connexion between them . The system of linear partial differential equations being given , and it being required to find a simultaneous solution of them , Jacobi , according to his first method , transforms these equations by a change of variables ; he directs that an integral of the first equation be found ; he shows that , in virtue of the form of the equations and the relation which connects the first and second of them , other integrals of the first equation may be derived by mere processes of differentiation from the integral already found ; and he shows how , by means of such integrals of the first equation , a common integral of the first and second equations of the system may be found . This common integral is a function of the known integral and certain variables , and its form is obtained by the solution of a differential equation between two variables-a differential equation which is in general non-linear , and of an order equal to the total number of integrals previously found . An integral of the first two equations of the given system having been obtained , Jacobi shows that by a second process of derivation , followed by the solution of a second differential equation , an integral which will satisfy simultaneously the first three equations of the system may be found ; and thus he proceeds by alternate processes of derivation and integration till an integral satisfying all the equations of the given system together is obtained . In these alternations , it is the function of the processes of derivation to give new integrals of the equations already satisfied ; it is the function of the processes of integration to determine the functional forms by which the remaining equations may in their turn be satisfied . Jacobi 's second method does not require a preliminary transformation of the equations ; but the process of derivation , by which from an integral of the first equation other integrals are derived by virtue of the relation connecting the first and second equations , is carried further than in his first method . It is indeed carried on until no new integrals arise . The difference of result is , that the common integral of the first and second partial differential equations is determined as a function solely of the integrals known , and not as a mixed function of integrals and variables . But its form is determined , as before , by the solution of a differential equation . All the subsequent processes of derivation and integration are of a similar nature . On the other hand , the method of my former paper applied to the same problem leads , by a certain process of derivation , to a system of ordinary differential equations equal in number to the number of possible integrals , and , without being individually exact , susceptible of combination into exact differential equations . The integration of these would give all the common integrals of the given system . All these methods possess , with reference to the requirements of the actual case , a superfluous generality . A single common integral of the system is all that is required . Now the chief result to be established in this paper is the following . If , with Jacobi , according to his second method , we suppose one integral of the untransformed first partial differential equation to be found , if by means of this we construct according to a certain type a new partial differential equation , if to the system thus increased we apply the process of my former paper , continually deriving new partial differential equations until , no more arising , the system is complete , then , under a certain condition hereafter to be explained , a common integral of all the equations of the complete system , and therefore of the original system which is contained in it , may be found by the integration of a single differential equation susceptible of being made integrable by means of a factor . But if the condition referred to is not satisfied , a new integral of the first partial differential equation must be found and the process repeated , with the certainty that sooner or later it will succeed . As soon , then , as the condition is satisfied , a solution not , as by Jacobi 's methods , first of two of the partial differential equations of the given system , then of three , and so on , but of all at once , is obtained ; and this solution is obtained , not as in my former process , by the solution of a system of equations reducible to the exact differential form , but by that of a single differential equation reducible to that form . The condition in question is grounded on the theoretical connexion which exists between the process of derivation of partial differential equations involved in my former method , and the process of derivation of integrals involved in Jacobi 's methods . In the actual problem , and in virtue of the peculiar form of the partial differential equation given , these two processes are coordinate . If each be carried to its utmost extent , then to each new partial differential equation arising from the one will correspond a new integral ( of the first partial differential equation ) arising from the other . The theory now to be developed is founded upon the inquiry whether it is possible to satisfy the completed system of partial differential equations by a function of the completed system of the Jacobian integrals , i. e. to determine a common integral of the completed series of equations as a function of the completed series of integrals of the first equation . The reader is reminded that by the completed series of integrals is meant , not all the integrals of the first partial differential equations that exist , but all that arise from a certain root integral by a certain process of derivation , together with the root integral itself . Now the answer here to be established to this inquiry is the following . The first of the partial differential equations necessarily will , and others may , be satisfied by the proposed function irrespectively of its form . If the number of equations of the completed system which is not thus satisfied is odd ( this is the condition in question ) , the form of the function which will satisfy all is determinable by the solution of a single differential equation of the first order , capable of being made integrable by means of a factor . Although the direct subject of this paper is the solution of partial differential equations of the first order , I wish it rather to be received as a slight contribution to that theory of the dynamical equations which was first published in the Philosophical Transactions , and which sug , gested to Jacobi the line of investigation which I here only seek to pursue a little further ,

112277

3701662

On the Absorption of Gases by Charcoal.--No. I. [Abstract]

424

426

Proceedings of the Royal Society of London

Angus Smith

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6.0.4

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http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112277

http://www.jstor.org/stable/112277

Thermodynamics

Fluid Dynamics

Thermodynamics

" On the Absorption of Gases by Charcoal.-No . I. " By Dr. R. ANGUS SMITH , F.R.S. Received December 27 , 1862 . ( Abstract . ) The following is a summary of the author 's observations:1 . Charcoal absorbs oxygen co as to separate it from common air , or from its mixtures with hydrogen and nitrogen , at common temperatures . 2 . Charcoal continues the absorption of oxygen for at least a month , although the chief amount is absorbed in a few hours , sometimes in a few seconds , according to the quality of the charcoal . 3 . It does not absorb hydrogen , nitrogen , or carbonic acid for the same period . 4 . Although the amount absorbed is somewhat in the relation of the condensibility of the gases by pressure , this is not the only quality regulating the absorption , of oxygen at least . 5 . When it is sought to remove the oxygen from charcoal by warmth , carbonic acid is formed , even at the temperature of boiling water , and slowly even at lower temperatures . 6 . Charcoals differ extremely in absorbing power , and in the capacity of uniting with oxygen , animal charcoal possessing the latter property in a greater degree than wood-charcoal . 7 . Nitrogen and hydrogen , when absorbed by charcoal , diffuse into the atmosphere of another gas with such force as to depress the mercury three-quarters of an inch . 8 . Water expels mercury from the pores of charcoal by an instantaneous action . 9 . The action of porous bodies is not indiscriminate but elective . Theoretical Considerations . 1 . The elective nature of porous bodies may be closely allied to three properties:a . The condensibility of the gases . b. The attraction and perhaps inclination to combine . c. The capacity of combination . 2 . In either case the attraction which results in condensation of the gas is exercised at distances greater than the distances of atoms or molecules in combination . 3 . The gases in porous bodies lie in strata , the outside and more distant being less attracted than the atoms nearer the solid body . 4 . We cannot separate chemical from physical attraction ; but attraction may exist without its ultimate result ( combination ) , which is distinctly chemical . 5 . It is exceedingly probable that as physical attraction moves onwards to chemical combination , it produces the phenomena which have been attributed to so-called masses . Chemical affinity is supposed to involve an attraction which is purely chemical ; we have no proof of any such attraction as a separate power , we have only a proof of the combination . Attraction may exist without the capacity of combining chemically , or , in other words , without chemical affinity . Chemical affinity ( a very inappropriate term ) is only known by combination ; the previous attraction has never yet been shown to be of two kinds ; and it seems more in accordance with Nature to diminish than to increase the number of original powers .

112278

3701662

On the Embryogeny of Comatula rosacea (Linck). [Abstract]

426

428

Proceedings of the Royal Society of London

Wyville Thomson

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6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112278

http://www.jstor.org/stable/112278

Paleontology

Biology 3

Paleontology

" On the Embryogeny of Comatula rosacea ( Linck ) . " By Professor WYVILLE THOMSON , LL. D. , F.R.S , E. , M.R.I.A. , F.G.S. &c. Communicated by Professor HUXLEY . Received December 29 , 1862 . ( Abstract . ) After briefly abstracting Dr. W. Busch 's description of the early stages in the growth of the young of Comatula , the author details his own observations , carried on during the last four years , on the development and subsequent changes of the larva . After complete segmentation of the yelk , a more consistent nucleus appears within the mulberry mass still contained within the vitelline membrane . The external more transparent flocculent portion of the yelk liquefies and is absorbed into this nucleus , which gradually assumes the form of the embryo larva , a granular cylinder contracted at either end and girded with four transverse bands of cilia . This cylinder increases in size till it nearly fills the vitelline sac , gradually increasing in transparency , and ultimately consisting of delicately vacuolated sarcode , the external surface transparent and studded with pyriform oil-cells , the inner portion semifluid and slightly granular . The vitelline membrane now gives way , and , usually shortly after the escape of the larva into the water , the third ciliated band from the anterior extremity arches forwards at one point ; and in the space thus left between it and the fourth band , a large pyriform depression indi cates the position of the larval mouth . At the same time a small round aperture , merely separated from the posterior margin of the mouth by the last ciliated band , becomes connected with the mouth by a short loop-like canal passing under the band , and fulfils the function of an excreting-orifice . A tuft of long cilia , which have a peculiar undulatory motion , is developed at the posterior extremity of the body . The larva now increases rapidly in size , assuming somewhat the form of a kidney bean , the mouth answering in position to the hilum . It swims freely in the water , with a swinging semirotatory motion , by means of its ciliated bands and posterior tuft of cilia . Shortly after the larva has attained its definite independent form , ten minute calcareous spicula make their appearance , imbedded within the external sarcode-layer of the expanded anterior portion of the larva . The ten spicula are arranged in two transverse rings of five , the spicula of the anterior row symmetrically superposed on those of the posterior . By the extension of calcareous network , these spicula rapidly expand into ten plates , which at length form a trellis enclosing a dodecahedral space , open above and below , within the anterior portion of the zooid . Simultaneously with the appearance of these plates , a series of from seven to ten calcareous rings form a chain passing from the base of the posterior row of plates backwards , curving slightly to the left of the larval mouth , and ending by abutting against the centre of a large cribriform plate , which is rapidly developed close to the posterior extremity of the larva . Delicate sheaves of anastomosing calcareous trabeculae shortly arise within these rings , and the series declares itself as the jointed stem of the pentacrinoid stage , the basal and first interradial plates of the calyx being represented by the already formed casket of calcareous network . The skeleton of the Crinoid is thus completely mapped out within the body of the larva , while the latter still retains its independent form and special organs . Within the plates of the calyx of the nascent Crinoid two hemispherical or reniform masses may now be detected , -one superior , of a yellowish , subsequently of a chocolate colour ; the other inferior , colourless and transparent . The lower hemisphere indicates the permanent alimentary canal of the Crinoid , with its glandular follicle ; the upper mass originates the central ring of the ambulacral system , with its craca passing to the arms . The body of the Crinoid is , how ever , at this stage entirely closed in by a dome of sarcode , forming the anterior extremity of the larva . After swimming about freely for a time , averaging from eight hours to a week , and increasing rapidly in size till it has attained a lengh of from 1 to 2 millims. , the larva becomes sluggish , and its form is distorted by the growing Crinoid . The mouth and alimentary canal of the larva disappear , and the external sarcode-layer subsides round the calcareous framework of the included embryo , forming for it a transparent perisom . The stem now lengthens by additions of trabeculm to the ends of the joints . The posterior extremity dilates into a disk of attachment . The anterior extremity becomes expanded , then slightly cupped ; the lip of the cup is divided into five crescentic lobes corresponding to the plates of the upper ring ; and finally five delicate tubes , ceca from the ambulacral circular canal , are protruded from the centre of the cup , the rudiments of the arms of the Pentacrinoid . At some stage during the progress of these later changes the embryo adheres , and at length becomes firmly cemented to some permanent point of attachment . The author states his views as to the morphological and physiological relations of the larval zooid . He believes that all the peculiar independently organized zooids developed from the whole or from a part of the segmented yelk in the Echinoderms , and which form no stage in the development of the perfect form of the species , must be regarded as assimilative extensions of sarcode , analogous in function to the embryonic absorbent appendages in the higher animals . For such an organism the term " pseudembryo " is proposed . In the Echinoderm subkingdom , although constructed apparently upon a common plan , these pseudembryos present considerable range of organization , from a somewhat complex zooid provided with elaborate natatory fringes , with a system of vessels which are ultimately connected with the ambulacral vascular system of the embryo , with a well-developed digestive tract , and in some instances with special nervous ganglia , to a simple layer of absorbent and irritable ' sarcode which invests the nascent embryo . The pseudembryo of Comatula holds an intermediate position . It resembles very closely in external form and in subsequent metamorphosis the " pupa stage ? ' of the Holothuridse , the great distinction between them being that in the Holothuridee the pupa has already passed through the more active " Auricularian " stage , while the analogous form in Comatula has been developed directly from the egg .

112279

3701662

On Some Compounds and Derivatives of Glyoxylic Acid. [Abstract]

429

430

Proceedings of the Royal Society of London

Henry Debus

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112279

http://www.jstor.org/stable/112279

Chemistry 2

Biography

Chemistry

I. " On some Compounds and Derivatives of Glyoxylic Acid . " By HENRY DEBUS , Ph. D. , F.R.S. Received December 31 , 1862 . ( Abstract . ) Glyoxylic acid contains one atom of oxygen less than oxalic acid , and may be considered as glycolic acid minus two atoms of hydrogen . It therefore bears to these two acids the same relation that oil of bitter almonds does to benzoic acid and benzylic alcohol . On another occasion* it has been shown to possess other properties in common with hydride of benzoyl . Dilute nitric acid , for instance , oxidizes glyoxylic acid to oxalic acid , and hydrate of potash converts it into glycolic acid and oxalic acid . The same reagents produce with oil of bitter almonds benzoic acid , benzoate of potash , and benzylic alcohol . C,2203 + HNO3 = C , H2 04 +H NO , , Glyoxylic acid . Oxalic acid . C7H60 + HNO = C7H602 + HNO , , Hydride of Benzoic acid . benzoyl . 2C2 , H203 +3KHO = C2 , H3KO+C , K,0 , 4 2H,0 , Glycolate of Oxalate of potash . potash . 2(C7 H60 ) + KHO = C7H , KO , +C I-O . Hydride of Benzoate of Benzylic benzoyl . potash . alcohol . In the memoir of which this is an abstract certain properties of glyoxylic acid are described which still more intimately connect this body with the class of the aldehydes , so as to leave no doubt as to its position in the system of organic substances . Glyoxylates and sulphites have a strong tendency to combine . Glyoxylic acid expels one-half only of the sulphurous acid from a given quantity of sulphite of soda , and forms the substance represented by the formula Na HS3+ C , H Na O3 ; an excess of sulphurous acid , on the other hand , expels one-half of the acid in glyoxylate of lime , producing Ca HS 03 + C , H Ca 0 , . These salts crystallize well and are very stable . Sulphuretted hydrogen and glyoxylate of lime exchange sulphur and oxygen , water and a new compound , C , 2 Ca 5 } +31H30 , being the result . The sulphur acid in the latter salt seems to bear to glyoxylic acid a relation similar to that in which triacetic acid stands to acetic acid . Glyoxylic acid itself is decomposed by sulphuretted hydrogen , a new crystallizable acid being produced . Ammonia forms definite compounds with glyoxylates . The following of them were investigated:--two bodies formed from NH , and glyoxylate of lime , 3(C H Ca O ) , 2N H , , and 3 ( C , H Ca 3 ) , 2N H , + H[ 0 , one silver and one lead compound . These derivatives are very unstable , but the products of their decomposition could not be obtained in a pure state . Hydrogen in statu nascendi combines with glyoxylic acid and converts it into glycolic acid , C,2H,03 + H , = C , H,40 Glycolic acid . This transformation was brought about by dissolving zinc in dilute glyoxylic acid . Glycolic acid , glyoxylic acid , and oxalic acid therefore possess , as regards composition and some other essential properties , the same connexion as ethylic alcohol , acetic aldehyde , and acetic acid . The differences between the two series arise from the greater number of oxygen-atoms in the molecules of the first three bodies .

112280

3701662

On the Telescopic Appearance of the Planet Mars

431

437

Proceedings of the Royal Society of London

John Phillips

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0091

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112280

10.1098/rspl.1862.0091

http://www.jstor.org/stable/112280

Astronomy

Optics

Astronomy

II . " On the Telescopic Appearance of the Planet Mars . " By JOHN PHILLIPS , M.A. , LL. D. , F.R.S , F.G.S. , Professor of Geology in the University of Oxford . Received February 5 , 1863 . Notwithstanding the descriptions and drawings of Mars , for which we are indebted to eminent observers* , there remains much uncertainty as to the permanent boundaries of the bright and shady parts of the planet , to which respectively , on a first view , we attach , perhaps too readily , the idea of land and seas . The extremely variable aspects under which this planet appears in its excentric orbit , the axis being inclined more than 30 ? to the ecliptic , the different regions very unequally presented to incident light , and very unequally influenced by vicissitudes of heat and cold , may account for much of the uncertainty . Other difficulties arise when the work of different instruments is compared ; for it is established that reflectors will on the whole give the best results for colour , while achromatics of fine quality discover more of detail than instruments of less perfect definition . The author having devoted some evenings between the 27th of September and 13th of December 1862 to the examination of Mars with a 6-inch achromatic by Cooke , equatorially mounted , and moved by clockwork , at Oxford , presented to the Society some results of these observations combined with others , also made with achromatics , by Mr. Grove , Mr. Main , and Mr. Lockyer . These various observations , made entirely without concert , were rendered comparable by a calculated reduction of each to the longitude on Mars corresponding to the epoch of each , according to one standard . [ Tables of these reductions were given in the paper . ] The sketches were then arranged on sheets in the order of the computed longitudes ; and , in addition , two globes were exhibited , on one of which the main results of the author 's observations were drawn , the data for the other being supplied by Mr. Lockyer 's sketches . He was also aided in the explanations by large drawings made with reflectors by Mr. De la Rue and Mr. Nasmyth . From the author 's sketches , three , representing opposite hemispheres , and one intermediate quadrature , have been selected for engraving , -one central to the assumed meridian of 0 ? or 360 ? , the others to the meridians of 90 ? and 180 ? nearly . See figs. 1 , 2 , 3 . Fig. 1.-Mars as seen on the 27th of September and on several other occasions till the 13th of December . ( Longitude 0 ? . ) On considering the surface of the planet , either as seen in the telescope , or delineated on paper , we feel in some doubt as to the meaning of what we see . Are the bright parts ( often seen of a red tint ) land , the darker parts ( often appearing of a greenish grey ) water ? or , as in the moon , are the reflecting powers of different parts of a dry surface very unequal ? Is there any considerable change in the aspect of the masses or boundaries between one epoch and another , so as to indicate atmospheric vicissitudes like those on Jupiter and our own planet ? Taking the latter question first , the author found , on the experience of his observations during 74 days , that no material change took place in the main and prominent features about the longitude which he marks 0 ? . Not that after this considerable interval the appearances remained exactly as at first : that was not , and could not be Fig. 2.-The appearance of Mars at longitude 90 ? , with long oblique ridges south of the great boundary , and nearly or quite running into the northern land , here less broad than in fig. 3 : seen November 11th . Fig. 3.-The llemisphere of Mars , opposite to fig. 1 : seen October 15th and 16th . With a specially dark band expected to be the case , after the planet had increased his distance from the earth to nearly double that when the observations began . Adding to his own the experience of Mr. Lockyer , whose observations began 35 days earlier , this inference , of permanence in the main boundaries of lights and shades , is extended to above 100 revolutions of Mars ; and on comparison of these with the earlier sketches of Madler , Herschel , Jacobs , and De la Rue , the conclusion appears to embrace the whole series of more than thirty years . The author regards as one of the main features very firmly defined in the late opposition , the broad white or rather reddish band which from about 65 ? of north latitude ( the north pole being invisible in these observations ) spreads up into large bright cloudlike prominences toward and beyond the equator , and retires into one principal and several smaller bays toward the pole . From this bright space , which in many parts is sharply defined , a broad dusky tint spreads toward the south , partially relieved by half-lighted expansions with shades of various depths between . The south pole itself is surrounded ( excentrically as it appears ) by a bright white mass , obviously glittering in the telescope . This is believed to be snow ; and the effect of its whiteness is increased in most parts of its circumference by the contrast of a dark ring round it , which expands here and there into broader spaces . Thus a great part of the northern area appeared in the late opposition bright , and often reddish , as if it were land , while a great part of the southern area was of the grey hue which is considered to indicate water , but relieved by various tracts of a tint more or less approaching to that of the brighter spaces of the northern hemisphere . The principal boundary of light and shade , for the most part very well defined , ran obliquely across the equator of Mars , so as to reach latitudes from 20 ? to 30 ? north and south of that line . This may perhaps be understood by the drawings selected for illustration , especially if compared with an orthographic projection of the latitudes* . ( Still better by means of the globes which accompanied the communication , constructed by the author , one from his own sketches , the other from those of Mr. Lockyer . ) Allowing the white spaces to be land , which reflects light as the moon in opposition , it seems a natural supposition that the shady spaces should be called sea ; and this may be supported by the obvious requirement of water somewhere on Mars , to agree with the alternate gathering and melting of the snow round the poles . Still , every observer remarks no small resemblance of some of these shady tracts with particular parts of the unequally tinted grey surfaces of the moon . A positive proof of ocean on the disk of Mars would be afforded by the star-like image of the sun reflected from the quiet surface* , or the more diffused light thrown back from the waves ; but nothing of this sort has been placed on record , nor is there such a variation in the appearance of these spaces from the centre toward the edges as to give any special reason for thinking them occupied by water . Atmospheric vicissitudes , however , appear to be recognized in the somewhat variable aspect of many portions of the grey spaces ; for these , thougli not much changed in the situation of the masses of light or shade , are sufficiently inconstant in.their shapes and details to suggest the idea of a vaporous envelope , brooding over and about some parts more than others , and variable from one epoch to another . The drawings of Mr. Lockyer supply the best evidence of these variations ; for Professor Phillips , except on a few occasions , confined his attention chiefly to the stronger and apparently more settled boundaries of light and shade . The tints on the body of Mars were observed by each of the gentlemen named , but with different results . To Mr. Nasmyth , with a large reflector , the 'land ' appeared of a decidedly red tint , the 'water ' green . The 'land ' appeared red in some parts , but bright and almost silvery in other parts , to Professor Phillips , looking through his achromatic , which also showed the ' water ' of a grey or greenish tint . No redness appeared in Mr. Lockyer 's instrument , which , like many others of excellent quality for astronomical research , is intentionally C over-corrected . ' Mr. Nasmyth saw the snow-patch on the south pole so distinctly bordered , as to give him the impression of its having a cliffboundary . The south snow-patch did not appear to him to agree with the south pole of the planet , but , on the contrary , to be considerably excentric to it ; and he supposed this to be due to the relative distribution of land and water , influencing the position of the centre of greatest cold . Only a faint glimmering of the snowy surfaces round the north pole was seen by any observer . On the whole , the author of this paper concluded that , over a permanent basis of bright and dusky tracts on the surface of Mars , a variable envelope gathers and fluctuates , partially modifying the aspect of the fundamental features , and even in some cases disguising them under new lights and shades , which present no constancy , -a thin vaporous atmosphere probably resting on a surface of land , snow , and water . Addendum . Since the reading of the paper the author has been enabled , by the kindness of the Earl of Rosse , to examine a series of sketches of Mars during the late opposition , from the great telescopes at Birr . These drawings , six in number , were made on July 22 , Sept. 14 , Sept. 16 , Oct. 6 , Oct. 29 , and Nov. 6 . They confirm in a remarkable manner the conclusions already presented by the author , and suggest some interesting questions for further observation and study . On the 22nd of July the southern snow was a large patch , meeting the limb by its diametral line . It must then have had a radius of 500 miles at least : in the later observations it was reduced to less than half this measure . One of the drawings nearly corresponds to longitude 180 ? on the author 's scale , and represents the specially dark short band which distinguishes that aspect of the planet ( fig. 3 ) . Two correspond nearly to fig. 1 , and contain the remarkable deep angular bay which extends so far towards the north pole . In these and the re maining three drawings , general resemblances and special differences appear on comparison with the sketches of Prof. Phillips and Mr. Lockyer . The differences affect principally the grey southern parts , and are remarkable enough to justify serious doubts whether any of our drawings of those parts are much to be trusted as representing permanent physical boundaries . Nor should this be thought surprising ; owing to the high inclination of the axis of Mars to the plane of his orbit , the regions round each pole are presented alternately to the sun through periods somewhat less than our whole year . The effect is seen in the vast outspread of snows round the cold pole , and the contraction of those white sheets to a small glittering ellipse round the warm pole . The enormous transfer of moisture from one hemisphere to the other while the snows are melting round one pole and growing round the other must generate over a great part of the planet heavy storms and great breadths of fluctuating clouds , which would not , as on the quickly rotating mass of Jupiter , gather into equatorial bands , but be more under the influence of prominent land and irregular tracts of ocean .

112281

3701662

On Thallium. [Abstract]

437

440

Proceedings of the Royal Society of London

William Crookes

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112281

http://www.jstor.org/stable/112281

Chemistry 2

Chemistry 1

Chemistry

" On Thallium . " By WILLIAM CROOKES , Esq. Communicated by Professor STOKES , Sec. R.S. Received February 5 , 1863 . ( Abstract . ) After discussing the occurrence and distribution of the new metal in different parts of the globe , the author proceeds to describe the method adopted by him for extracting it from its ore . Thalliferous pyrites is distilled at a bright red heat , in quantities of about 1 cwt . at a time , in cast-iron retorts . The resulting sulphur , varying from 13 to 17 per cent. of the pyrites taken , is then dissolved in aqueous caustic soda , which leaves the sulphide of thallium as an insoluble black precipitate ; this is filtered off , dissolved in acids , and the thallium precipitated in the form of iodide . This is then converted into sulphate , and the metal reduced from the solution by electrolysis . It is obtained in the coherent form by fusion under cyanide of potassium . The physical characteristics of thallium are then described . In appearance it most resembles tin and cadmium , but has a distinct colour of its own ; it has a brilliant metallic lustre , and is susceptible of taking a very high polish ; it oxidizes in the air with almost the rapidity of an alkaline metal , but when coated with oxide , the metal may be freely handled and exposed to the air with scarcely any further change . An oxidized surface applied to the tongue is very biting and caustic , and has a sweetish metallic taste . It is the softest known metal admitting of free exposure to the atmosphere , being scratched by soft lead with the greatest ease . It makes a dark blue mark upon paper , rapidly turning yellow , which in the course of a few hours nearly fades out , but can be restored with sulphide of ammonium . It has little tenacity , is very malleable , and may be readily pressed into wire . The specific gravity of thallium varies from 11881 to 11'91 , and it is probably capable of still greater condensation . When freshly prepared , thallium wire is perfectly amorphous , but when kept in water it gradually assumes a superficial crystalline appearance : this effect is immediately produced when thallium in wire , ingot , or plate , tarnished or clean , is boiled in water . Its melting-point is 550 ? F. , being between bismuth and lead , and the metal does not become pasty before undergoing complete fusion . Two pieces of clean metal weld together by pressure in the cold . It begins to volatilize at a red heat , and boils below a white heat ; it may be distilled in a current of hydrogen . It is a pretty good conductor of heat and electricity , and stands electro-chemically very near cadmium . It is strongly diamagnetic , ranking in this respect near bismuth . The alloys which thallium forms with different metals are next described . Further details are given respecting the spectrum of thallium : the characteristic green line is perfectly single under a very high magnifving power and after refraction through nine heavy glass prisms ; and no new lines make their appearance at the temperature of the oxyhydrogen blowpipe , -although , with the electric spark , Dr. Miller has shown that several new lines come into existence . The delicacy of the optical test for thallium is roughly estimated , the 5oIo 00oth of a grain being easily perceptible . The atomic weight of thallium is given as 203 , being the mean of five experiments . The author states , however , that this is not to be regarded as a final result . The chemical properties of thallium are next described . It does not decompose water even at the boiling-point , but remains bright under this liquid . The superficial tarnish is a powerful base soluble in water , and reacting like an alkaline solution . Melted in the air , thallium forms a readily fusible oxide , its behaviour resembling that of lead . The formation of thallic acid and the properties of some of the thallates are described . Sulphate , nitrate , the chlorides , sulphide , iodide , and other salts of thallium are described in detail . The metal may be quantitatively determined by precipitation , either as protochloride , iodide , or platinochloride . The position of thallium amongst elementary bodies is then discussed . Although one or two of its properties show a resemblance to the alkaline metals , the author does not agree with continental chemists in classing it with this group , -numerous facts proving that its true position is by the side of mercury , lead , or silver . The ready dehydration of its basic oxide ; the insolubility of its sulphide , iodide , chloride , bromide , chromate , phosphate , sulphocyanide , and ferrocyanide ; its great atomic weight ; its ready reduction by zinc to the metallic state ; its power of forming a strongly acid oxide ; and , according to Dr. Miller , the complexity of its photographic spectrum , -all prove that thallium cannot consistently be classed anywhere but amongst the heavy metals , mercury , silver , lead , &c. No weight is attached to M. Dumas 's argument in favour of thallium being related to potassium and sodium because its equivalent is rather near a figure obtained by adding twice the atomic weight of one metal to four times the atomic weight of the other . The author shows that , by similar processes of addition , multiplication , or subtraction , it is not difficult to prove that thallium is related to any desired group of elements . The author gives full analytical notes on thallium , showing where it would occur in the ordinary course of analysis , and detailing accurate methods of separating it from every metal with which it can be accompanied .

112282

3701662

On the Effect of Temperature on the Secretion of Urea, as Observed on a Voyage to China, and at Hong Kong. [Abstract]

440

441

Proceedings of the Royal Society of London

Emil Becher

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112282

http://www.jstor.org/stable/112282

Biography

Meteorology

Biography

I. " On the Effect of Temperature on the Secretion of Urea , as observed on a Voyage to China , and at Hong Kong . " By EMIL BECHER , M.D. , Assistant-Surgeon , Army Medical Staff . Communicated by Dr. EDMUND A. PARKS . Received January 20 , 1863 . ( Abstract . ) With a view to extend our knowledge of the physiological effects of temperature , with especial regard to the influence of tropical heat on the healthy system , Dr. Becher , with the liberal assistance of the Director-General , Army Medical Department , took advantage of a voyage to China ( round the Cape of Good Hope ) in 1857 , and a short residence at Hong Kong , in order to determine on himself the influence of the extreme variations of temperature incidental to that voyage , on the quantity of urine , urea , and chloride of sodium excreted during each twenty-four hours . During a period of 163 days ( 100 days at sea , 63 days at Hong Kong during the change of monsoon ) , Dr. Becher collected the daily quantity of urine , and determined the amount of urea and NaCl by the volumetric method ( solutions of nitrate of mercury ) , and registered meteorological observations as accurately as circumstances would permit , observing all the time as constant a mode of living ( with regard to food , exercise , &c. ) as was practicable without undue restriction . The whole of the observations , divided into the two periods indicated , are fully detailed in Tables , and graphically represented in Diagrams . The results show a most remarkable relation between air-temperature and daily quantity of urea and NaCl , viz. a constant increase with the rising of temperature from 50 ? -70 ? , and an equally constant falling off with the further rise of temperature from 70 ? -90 ? . The physiological limit of the tropical zone , as marked by the sudden decrease in the quantity of urinary water , is constantly fixed at 76 ? . Appended is an extract from a manuscript of Dr. Forbes Watson , containing a series of observations on the daily quantity of urine and the amount of solids therein excreted by a number of healthy soldiers in various temperatures during a voyage to India in 1850 . These observations were made by Dr. Forbes Watson , who most kindly consented to their being added here , as far as they serve to illustrate the influence of temperature under otherwise constant conditions . They are tabulated and graphically represented as much as possible on the same plan as those of Dr. Becher , and in their results show the most satisfactory harmony with the latter .

112283

3701662

On Clinant Geometry, as a Means of Expressing the General Relations of Points in a Plane, Realizing Imaginaries, Reconciling Ordinary Algebra with Plane Geometry, and Extending the Theories of Anharmonic Ratios. [Abstract]

442

443

Proceedings of the Royal Society of London

Alexander J. Ellis

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112283

http://www.jstor.org/stable/112283

Formulae

Fluid Dynamics

Mathematics

II . " On Clinant Geometry , as a means of expressing the General Relations of Points in a Plane , realizing Imaginaries , reconciling Ordinary Algebra with Plane Geometry , and extending the Theories of Anharmonic Ratios . " By ALEXANDER J. ELLIS , B.A. , F.C.P.S. Communicated by ARTHUR CAYLEY , Esq. Received January 28 , 1863 . ( Abstract . ) The serious difficulties presented by " imaginaries " in plane geometry arise from treating the " principle of signs " as a matter of convention , and not as a particular case of a general operation , here termed a clinant , which consists in altering the length of a line in a given ratio , and rotating it through a given angle . As the calculus of clinants furnishes a geometrical representation for every algebraical result , imaginaries disappear , and there is no longer any apparent disagreement between analysis and geometry . Many theories , as , for example , those of anharmonic ratios , hitherto only established for points on a straight line , are also easily extended by means of clinants to embrace any points upon a plane . The object of the present paper is to establish and illustrate these facts . For this purpose it is divided into three distinct but closely connected parts . Part I. shows that clinants obey the same laws of calculation as ordinary algebraical expressions , and explains their notation and geometrical construction . This is illustrated by the solution of the problem of the determinate section generalized , and by a geometrical explanation of " imaginary " trigonometrical functions , applied to the discovery of the " imaginary " double rays in an homography . Part II . establishes the theory of stigmatics . An index point , supposed to move from any origin into every point on a plane , is accompanied by one or more satellite points , termed stigmata , the relative position of the stigmata and index at any time being dependent on the relative position of the index and origin , according to some assigned law . The locus of the stigmata , corresponding to each path of the index , forms a stigmatic curve . The aggregate of these curves constitutes a stigmatic , which therefore consists of points conjugated with each other according to a characteristic law , ulti mately expressible by an equation between the clinant of the line connecting the index with the origin and the clinant of the line connecting the stigma and the index . By elimination between two such equations , the common stigmata ( systigmata ) of two stigmatics , and by the condition of equal roots their coalescent systigmata , or homostigmata , may be determined . These systigmata and homostigmata include , as particular cases , the points of " real " and " imaginary " intersection and contact of algebraical curves . These generalities are illustrated by a consideration of the general stigmatic straight line and the central stigmatic circle . The stigmatic straight line consists of stigmatic curves similar to the paths of the index , and their systigmata are the " double points " of similar figures . The stigmata of a stigmatic circle are always harmonically conjugated with the extremities of its axis ( with which they always lie either on the same straight line , or the circumference of the same circle ) , and hence form an " involution " of points on a plane . The construction of the systigmata and homostigmata of a stigmatic straight line , and stigmatic circle , furnishes a complete geometrical explanation and realization of the " imaginary intersections " of straight lines , with " real " and " imaginary " circles , " imaginary tangents " to such circles , and their polars and radical axes and common chords . Part III . contains an extension of the theories of anharmonic ratios from points on straight lines to any points in a plane , and explains and constructs the homography and involution of.such systems of points , with their double points , &c. Constant reference is made throughout this part to M. Chasles 's 'Geometrie Superieure , ' to show how his fundamental theories may be interpreted as conclusions in clinant geometry , to explain all cases of " imaginaries , " and to establish the fact that " real " and " imaginary " points are only two very particular cases of the general theory of conjugated points . The whole memoir forms an introduction to a new and practical geometrical calculus , including and interpreting all analytical investigations on plane geometry .

112284

3701662

Note on the Lines in the Spectra of Some of the Fixed Stars

444

445

Proceedings of the Royal Society of London

William Huggins|William Allen Miller

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6.0.4

http://dx.doi.org/10.1098/rspl.1862.0095

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112284

10.1098/rspl.1862.0095

http://www.jstor.org/stable/112284

Astronomy

Atomic Physics

Astronomy

III . " Note on the Lines in the Spectra of some of the Fixed Stars . " By WILLIAM HUGGINS , Esq. , F.R.A.S. , and WILLIAM ALLEN MILLER , M.D. , LL. D. , Treasurer and V.P.R.S. Received February 19 , 1863 . The recent detailed examination of the solar spectrum , and the remarkable observations of Kirchhoff upon the connexion of the dark lines of Fraunhofer with the bright lines of artificial flames , having imparted new interest to the investigation of spectra , it has appeared to the authors of the present note that the Royal Society may not consider a brief account of their recent inquiry upon the spectra of some of the self-luminous bodies of the heavens unworthy of attention , although the investigation is as yet far from complete . After devoting considerable time to the construction of apparatus suitable to this delicate branch of inquiry , they have at length succeeded in contriving an arrangement which has enabled them to view the lines in the stellar spectra in much greater detail than has been figured or described by any previous observer . The 'U 7-L1 LAL r1 apparatus also permits of the immediate comparison of the stellar spectra with those of terrestrial flames . The accompanying drawing " X x ; u I > §§ ? Ii 1 % -f j " y ? '1'0 1|\1 r iminA , 1-l 11 111 shows with considerable accuracy the principal lines which the authors have seen in Sirius , Betelgeux , and Aldebaran , and their position relatively to the chief solar lines . Without at present describing in detail , as they propose to do when the experiments are completed , the arrangements of the special apparatus employed , it may be sufficient to state that it is attached to an achromatic telescope of 10 feet focal length , mounted in the observatory of Mr. Huggins at Upper Tulse Hill . The object-glass , which has an aperture of 8 inches , is a very fine one by Alvan Clark of Cambridge , U.S. ; the equatorial mounting is by Cooke of York , and the telescope is carried very smoothly by a clock motion . It may further be stated that the position in the stellar spectra corresponding to that of Fraunhofer 's line D , from which the others are measured , has been obtained by coincidence with a sodium line , the position of which in the apparatus was compared directly with the line D in the solar spectrum . The lines in the drawings against which a mark is placed have been measured . Addendum.-Since the foregoing Note was presented to the Royal Society , the authors have learned that a paper on the same subject , accompanied by diagrams of the spectra of the Moon , Jupiter , Mars , and several of the fixed stars , by Mr. L. M. Rutherfilrd , has appeared in the January Number of the ' American Journal of Science ' for the current year . The method of observing finally employed by Mr. Rutherfurd much resembles that adopted by the authors of this Note . They therefore desire to add that , during the past twelvemonth , they have examined the spectra of the Moon , Jupiter , and Mars , as well as of between thirty and forty stars , including those of Arcturus , Castor , a Lyrae , Capella , and Procyon , some of the principal lines of which they have measured approximatively . They have also observed 3 and y Andromede , a , ,3 , e and r Pegasi , Rigel , j Orionis , 3 Aurigae , Pollux , y Geminorum , a , y and e Cygni , a Trianguli , e , and n Ursae Majoris , a , / 3 , y , e and j Cassiopeiee , and some others.-[Feb . 21 , 1863 . ]

112285

3701662

On Skew Surfaces, Otherwise Scrolls. [Abstract]

446

448

Proceedings of the Royal Society of London

A. Cayley

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112285

http://www.jstor.org/stable/112285

Formulae

Headmatter

Mathematics

I. " On Skew Surfaces , otherwise Scrolls . " By A. CAYLEY , F.R.S. Received February 3 , 1863 . ( Abstract . ) It may be convenient to mention at the outset that in the paper " On the Theory of Skew Surfaces , " Camb . and Dubl . Math. Journ. vol. vi . pp. 171-173 ( 1852 ) , I pointed out that upon any skew surface of the order n there is a singular ( or nodal ) curve meeting each generating line in ( n-2 ) points , and that the class of the circumscribed cone , or what is the same thing , the class of the surface , is equal to the order n of the surface . In the paper " On a Class of Ruled Surfaces , " Camb . and Dubl . Math. Journ. vol. viii . pp. 45,46 , ( 1853 ) , Dr. Salmon considered the surface generated by a line which meets three curves of the orders m , n , p respectively : such surface is there shown to be of the order =2mnp ; and it is noticed that there are upon it a certain number of double right lines ( nodal generators ) ; to determine the number of these , it is necessary to consider the skew surface generated by a line meeting a given right line and a given curve of the order m twice ; and the order of such surface is found to be =--m(m-1)h , where h is the number of apparent double points of the curve . The theory is somewhat further developed in Dr. Salmon 's memoir " On the Degree of a Surface reciprocal to a given one , " Trans. R. Irish Acad. vol. xxiii . pp. 461-488 ( read 1855 ) , where certain minor limits are given for the orders of the nodal curves on the skew surface generated by a line meeting a given right line and two curves of the orders m and n respectively , and on that generated by a line meeting a given right line and a curve of the order m twice . And in the same memoir the author considers the skew surface generated by a line , the equations whereof are ( a,..3t , l)m=O ( al,..]t , l)n=0 , where a,. . al,. . are any linear functions of the coordinates , and t is an arbitrary parameter . And the same theories are reproduced in the Treatise on the Analytic Geometry of three Dimensions , " Dubl . 1862 . I will also , though it is less closely connected with the subject of the present memoir , refer to a paper by M. Chasles , " Description des Courbes a double Courbure de tous les ordres sir les surfaces reglees du troisieme et du quatrieme ordre , " Comptes Rendus , t. liii . ( 1861 , 2 ' Sem . ) , pp. 884-889 . 2K The present memoir ( in the composition of which I have been assisted by a correspondence with Dr. Salmon ) contains a further development of the theory of the skew surfaces generated by a line which meets a given curve or curves : viz. I consider , -lst , the surface generated by a line which meets each of three given curves of the orders m , n , p respectively ; 2nd , the surface generated by a line which meets a given curve of the order m twice , and a given curve of the order n once ; 3rd , the surface which meets a given curve of the order m three times ; or , as it is very convenient to express it , I consider the skew surfaces , or say the " scrolls , " S(m , n , p ) , S(m2 , n ) , S(m3 ) . The chief results are embodied in the Table given after this introduction , at the commencement of the memoir . It is to be noticed that I attend throughout to the general theory , not considering otherwise than incidentally the effect of any singularity in the system of the given curves , or in the given curves separately : the memoir contains , however , some remarks as to what are the singularities material to a complete theory ; and in particular as regards the surface S(m3 ) . I am thus led to mention an entirely new kind of singularity of a curve in space-viz . , such a curve has in general a determinate number of " lines through four points " ( lines which meet the curve in four points ) ; it may happen that of the lines through three points , which can be drawn through any point whatever of the curve , a certain number will unite together and form a line through four ( or more ) points , the number of the lines through four points ( or through a greater number of points ) so becoming infinite .

112286

3701662

Researches on the Refraction, Dispersion, and Sensitiveness of Liquids. [Abstract]

448

453

Proceedings of the Royal Society of London

J. H. Gladstone|T. P. Dale

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112286

http://www.jstor.org/stable/112286

Chemistry 2

Optics

Chemistry

II . " Researches on the Refraction , Dispersion , and Sensitiveness of Liquids . " By J. H. GLADSTONE , Ph. D. , F.R.S. , and the Rev. T. P. DALE , M.A. , F.R.A.S. Received February 5 , 1863 . ( Abstract . ) This communication contains the results of some inquiries which were started by the authors in a previous paper " On the Influence of Temperature on the Refraction of Light " * . The same apparatus had been employed , but some modifications were introduced in the method of observation , which are described ; and the amount of probable error from different sources was determined . The liquids experimented on were either prepared or purified in Dr. Gladstone 's laboratory , or were specimens reputed to be pure , and lent for the purpose of this inquiry by Prof. Hofmann , Prof. Williamson , Prof. Frankland , Drs. Warren De la Rue and Hugo Muller , Mr. Buckton , Dr. Odling , Mr. A. H. Church , Mr. C. Greville Williams , and Mr. Piesse . The data are collected in two long tables forming two appendices : the first containing the refractive indices of the lines A , D , and H , of 78 specimens at two or three different temperatures ; the second , the refractive indices of all the more important lines for 61 of these liquids , and 10 others at the temperature of the room when the observations were made . Five points were investigated , and the following are the results arrived at with respect to each point . I. The relation between the change of refraction ( sensitiveness ) and the change of volume by heat.-The uniform testimony of about 90 different liquids examined was that both refraction and dispersion diminish as the temperature increases . The following Table will suffice as an example , showing as it does that the different rays are more sensitive in the order of their refrangibility : Refractive Indices . Liquid . Temp. A. B. D. E. F. G. H. Bisulphide of 1 11 ? C. 16142 1-6207 1-6333 1-6465 1-6584 16836 1-7090 Carbon ... . . 36 ? -5 1-5945 1-6004 1-6120 1-6248 1'6362 1-6600 1-6827 Difference ... ... 0-0197 0-0203 0-0213 0-0217 0-0222 0-0236 0-0263 , This change of refraction by heat was compared with the known or ascertained change of volume in bisulphide of carbon , water , methylic , ethylic , and amylic alcohols , ether , acetone , acetic acid , formic , acetic , and butyric ethers , methylic and ethylic iodides , salicylate of methyl , bromoform , benzole , xylole , cumole , nitrobenzole , hydrate of phenyl , the rectified oils of turpentine and Portugal and eugenic acid , and in every case it was found that the refractive index minus unity , multiplied by the volume , gave very nearly a constant at different temperatures . Now every refractive index contains at least two coefficients : the one of refraction , which is represented by the theoretical limit of the spectrum ; the other of dispersion , for which the difference between the refractive indices of H and A may be taken as the exponent . The refractive index , minus unity ( ~1 ) , is termed by the authors the " refractive energy " of the substance , and this multiplied by the volume ( , t--1 ) , or divided by the density , is termed the " specific refractive energy . " It was not found as a rule that the theoretical limit of the spectrum gave more truly a constant than the line A ; but the difference is within experimental errors . The empirical law was therefore expressed as follows:-The refractive energy of a liquid varies directly with its density under the influence of change of temperature , or , in other words , the specific refractive energy of a liquid is a constant not affected by temperature . Yet the influence of dispersion renders this not absolutely accurate in the observed numbers , for the change of dispersion does not follow the same law , the spectrum contracting in some cases much more , and in other cases much less rapidly than the volume increases ; indeed no relation is as yet discoverable between the change of dispersion and that of density . II . The refraction and dispersion of mixtures of liquids.-This question has engaged the attention of several experimenters , only one of whom , however , M. Hoek , has offered a solution . His formula depends on '2-1 . Yet most of the results recorded were equally well explained on the supposition that the specific refractive energy of a mixture is the mean of the specific refractive energies of its components . It was clearly desirable to test this in some cases where the refractive indices of the liquids mixed were very wide apart . Fortunately , bisulphide of carbon and ether , substances almost at the opposite limits of the scale , were found to mix without condensation ; and another good experiment was obtained with aniline and alcohol , on mixing which , however , some diminution of volume occurs . In both these cases the experimental numbers were slightly below those deduced from the mean of the specific refractive energies , the discrepancy being beyond the limits of probable error ; yet no other formula could be devised which would give a nearer approximation to the indices actually observed . III . The refSraction , disper sion , and sensitiveness of different members of homologous series.--Many such series were examined , and the results are tabulated , the refractive index of A and the length of the spectrum or dispersion being reduced , if necessary , to 20 ? C. , and the sensitiveness being taken for the 10 degrees rising above 20 ? C. ; the specific refractive energy , dispersion , and sensitiveness also form part of the Tables . Methylic , ethylic , amylic , and caprylic alcohols are the first series examined , and it is found that on ascending the series the refraction increases ; the dispersion does so still more rapidly , while the sensitiveness remains nearly the same . Other homologous series of the same group , such as the iodides , compound ethers , or mercury compounds , were also examined , and they all agree in exhibiting a progressive change in refraction and dispersion with the advancing members of the series ; but in which direction and to what extent depend on the other substances with which the compound radical is combined . Yet , if we regard not the actual indices , but these , minus unity , divided by the density , a pretty regular increase is found to take place as the series advance . The following Tables exhibit this : SSpecific Refractive Energy . Radical . I|iI l| Methyl ... ... C2 H3 *4105 -2359 3905 ... 389 . 1707 3727 Ethyl . C4 H5 4482 -2614 '4127 '3905 -4127 4402 '3502 ' 2112 -3876 Propyl ... ... C ... . 4333 Butyl ... ... . C ... 4402 | Amyl ... . . CO Hl '4895 *3213 4492 -4432 '4527 -4724 '4306 CEnanthyl ... C14 H15 ... '4750 ... ... ... ... ... 5499 Capryl ... . C H7 '5096 ... ... ... ... ... ... ... 5522 Laurostearyl C1 H ... ... 4890 Specific Dispersion . Ether of Mercury Stannic Radical . Alcohol . Iodide . Acid . Acetate . Cd Comp Hydride . Acid . Compd . Compd . Methyl ... ... ... ... 163 209 168 ... 140 256 Ethyl ... ... ... ... 190 218 174 174 170 268 Propyl ... ... ... ... ... ... . . 191 Butyl ... ... ... ... ... . 191 Amyl ... ... ... ... . . 212 224 198 198 ( Enanthyl ... ... ... ... ... ... . . 241 Capryl ... ... ... ... ... ... ... . . 237 Other groups of homologous bodies were also examined . Benzole , toluole , xylole , cumole , and cymole gave nearly the same numbers , and no regular progression . Pyridine , picoline , lutidine , and collidine showed an augmentation of the specific refractive energy , but a diminution of the specific dispersion with the advancing series . Chinoline and lepidine ( which proved to be the most refractive organic liquid known ) showed an increase of each of the optical properties by the addition of C2 HI . Thus the influence of the added increment on the rays of light differs in different groups , just as it does in respect to the boiling-point . IV . The refraction , dispersion , and sensitiveness of isomeric liquids.-Several of the liquids , isomeric with the different members of the benzole series , were examined ; some proved to be identical in all optical properties ; others sensibly the same in actual refraction and dispersion , though slightly different in density ; some again identical in density , but differing in optical properties ; while other isomeric bodies differed slightly in each of these respects . Several hydrocarbons of the type C20 H16 , from essential oils , seemed to be identical in actual refraction , notwithstanding slight differences of their density . In dispersion , too , there were some variations ; but not in sensitiveness . Other hydrocarbons , however , of the same ultimate composition , but differing considerably in physical properties , differed also optically . Compound ethers , as valerianic ether and acetate of amyl , which contain the same number of carbon , hydrogen , and oxygen elements , though differently arranged , are optically identical , as was partially shown by Delffs some years ago . Aniline and picoline , each empirically C , H7 N , are totally different . The conclusion arrived at is that isomeric bodies are sometimes widely different in these optical properties ; but that in many cases , especially where there is close chemical relationship , there is identity also in this respect . V. The effect of chemical substitution.-By observing the amount of change in the optical properties which results from a replacement of one element by another , the chemical type remaining the same , it seemed possible to arrive at a knowledge of the influence of the individual elements on the rays of light transmitted by them . Of the immense number of data required for the perfecting of such an inquiry , the following are afforded by the experiments already made . The replacement of hydrogen by a compound radical , aniline-amylaniline ; and water , alcohol , ether ( according to Williamson 's theory ) . Of hydrogen by oxygen-alcohol , acetic acid ; ether , acetic ether ; and carvene , carvole , eugenic acid . Of hydrogen by peroxide of nitrogen-benzole , nitrobenzole , dinitrobenzole ( in solution ) ; glycerine , nitroglycerine ; and amylic alcohol , nitrate of amyl . Of hydrogen by chlorine-benzole , chlorobenzole , terchlorobenzole ; and the substitution of chlorine by bromine-terchloride of phosphorus , terbromide of phosphorus ; chloroform , bromoform ; and bichloride of chlor-ethylene , bibromide of chlor-ethylene , bibromide of brom-ethylene . When hydrogen is replaced by some other body , there is generally an increase of the actual refraction and dispersion ; but this is due to the increased weight , hydrogen having a very low actual , but a very high specific influence on the rays of light . In each of the five instances of two substitution-products , as , for instance , cllorobenzole and trichlorobenzole , the lower one always retains in its optical properties an intermediate position between the original substance and the higher product . These experiments on substitution sufficed to show , as the examination of isomeric bodies had done , that the special influence exerted on the rays of light by the elements of a compound is greatly dependent on the manner of their combination . The following is given as a generalization approximately , if not absolutely true:-Every liquid has a specific refractive energy composed of the specific refractive energies of its component elements , modified by the manner of combination , and which is unaffected by change of temperature , and this refractive energy accompanies it when mixed with other liquids .

112287

3701662

On the Change of Form Assumed by Wrought Iron and other Metals When Heated and Then Cooled by Partial Immersion in Water

453

472

Proceedings of the Royal Society of London

H. Clerk

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0098

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112287

10.1098/rspl.1862.0098

http://www.jstor.org/stable/112287

Measurement

Chemistry 1

Measurement

III . " On the Change of Form assumed by Wrought Iron and other Metals when Heated and then Cooled by partial immersion in Water . " By Lieut.-Col. H. CLERK , R.A. , F.R.S. Received February 9 , 1863 . Origin of the Experiments.-A short time ago , when about to shoe a wheel with a hoop-tire , to which it was necessary to give a bevel of about xths of an inch , one of the workmen employed suggested that the bevel could be given by heating the tire red-hot and 1863 . ] 453 then immersing it one-half its depth in cold water . This was tried , and found to answer perfectly , that portion of the tire which was out of the water being reduced in diameter . The tire was 3 inches wide , inch thick , and 4 ' 2 " in diameter . As this result was curious and not generally known , I considered it desirable to institute some further experiments in order to try how far , by successive heatings and coolings , this change of form could be augmented , and also whether the same effect could be produced on other metals than wrought iron . Mode of carrying out the Experiments.-The experiments were made on cylinders of wrought iron of different dimensions , both hollow and solid ; immersed , some to one-half of their depth , others to two-thirds ; also on similar cylinders of cast iron , steel , zinc , tin , and gun-metal . The specimens experimented on were all accurately turned in a lathe to the required dimensions , which were carefully noted ; they were then heated to a red heat in a wood-furnace used for heating the tires of wheels . As soon as they had acquired the proper heat , they were taken out and immersed in water to one-half or two-thirds of their depth ( as stated in the experiment ) . The temperature of the water ranged from 60 ? to 70 ? Fahr. The specimens were allowed to remain in the water about two minutes , in which time the portion in the air had lost all redness , and that in the water had become sufficiently cool to handle . These alternate heatings and coolings were repeated till the metal showed signs of cracking or giving way . The dimensions were noted after every five heatings . The circumferences were measured in preference to the diameters , as the true circular form was liable to alter . General Results.-It will be seen by an inspection of the figures that the general effect is a maximum contraction of the metal about one inch above the water-line ; and that this is the same whether the metal be immersed one-half or two-thirds of its depth , or whether it be nine , six , or three inches deep . With wrought iron the heatings and coolings could be repeated from fifteen to twenty times before the metal showed any signs of separation ; but with cast iron after the fifth heating the metal was cracked , and the hollow cylinder separated all round just below the water-line after the second heating . 454 Cast steel stood twenty heatings , but was very much cracked all over its surface . As respects the change of form of cast iron and steel , the result was similar to that in wrought iron , but not nearly so large in amount . The cast iron did not return to its original dimensions , but the smallest diameter was about one inch above the water-line . Tin showed no change of form , there being apparently no intermediate state between the melting-point and absolute solidity . Brass , gun-metal , and zinc showed the effect slightly ; but instead of a contraction just above the water-line , there was an expansion or bulging . The effect on wrought iron is best seen in the solid cylinder ( figs. 9 and 10 ) , where the displacement of particles just above the water-line appears to be compensated by the bulgings at the two extremities . The specimens of wrought iron were submitted by Mr. Abel ( Chemist to the War Department ) to chemical analysis , and he informs me that he found nothing noteworthy in the composition of the metal ; nor was there any appreciable difference in the specific gravity of the metal taken from different parts of the specimen . It appears therefore to be simply a movement of the particles whilst the metal is in a soft or semifluid state . The following is an account of the experiments , which were carried out under the superintendence of Mr. Butter , Draughtsman of the Royal Carriage Department , to whom also I am indebted for the accompanying diagrams . The exact dimensions of each specimen before and after heating are given in a tabulated form at the end of the paper , to facilitate comparison . In figs. 22 and 23 the changes in form of the 9 " cylinders ( one immersed one-half , the other two-thirds its depth ) are shown in section after every five heatings ( half the full size ) . Experiment . 1-A 4 ft. 2 in . hoop-tire of 3 inches breadth and 3ths inch in thickness ( fig. 1 ) was heated and cooled by being immersed to half its depth in cold water five times , by which the effect shown in fig. 2 was produced . 1863 . ] 455 Fig. 1 . ~ ~~~~ ~-_~Fig . 2 . One-eighteenth of full size . The upper edge , or that cooled in air , had contracted 8 inches , or -2Ith its entire length , and slightly increased in thickness ; while the lower edge , cooled in water , had expanded '875 inch , making a difference between the two circumferences of 8'875 inches . The breadth remained unaltered ( 3 inches ) , and kept perfectly straight . Fig. 3 . 1_i I , : ! ? : ' : _Li / L Vlll i ili Irilul liiiii ll , ll ! - , liN ! tuutttilt 2h ! tlttiillikikil KI Section showing the amount of contraction . One-half the full size . The dotted lines show the original form . The quality of the iron was afterwards tested by pieces taken from the upper and lower edges , and also from the centre ; the fibrous -cEZR ----I=---1 ; 17-=1=-I ---- , - ; 2 ? = ? r== ; ; ; :__,.-_L-Ig---- ; -----'- ; ;:LrT ? Sjc--------456 -------=- ... . EIi condition had remained unchanged , the specific gravity had not altered appreciably , and there appeared to be no deterioration in any part of it . Experiment 2.-Two hollow cylinders of wrought iron , 12 inches diameter and I inch thick each , and respectively 9 inches and 6 inches deep , were heated to redness , and cooled by half-immersion in cold water twenty times ; for effects see figs. 4 and 5 . Fig. 4 . Fig. 5 . One-eighth of full size . The 9-inch cylinder did not alter on the upper edge , cooled in air ; but the lower edge , cooled in water , contracted *6 inch , and the circumference , at about one inch above the water-line , was reduced 5*5 inches ; the internal surface had increased in depth '35 inch . The small cylinder diminished it could not be welded , and was therefore riveted , of the same external dimensions as the 9-inch one of the foregoing experiment , was heated to redness and cooled by half-immersion ten times , in order to test the effect when the thickness of the metal was reduced as much as possible . The upper and lower edges were not altered materially , while the greatest contraction took place on the water-line , instead of 1 inch above it as in the last experiment , and amounted to 3'5 inches . The depth measured on the curve had increased 15 inch ( see fig. 6 ) . Fig. 6 . One-eighth of full size . Experiment 4.--Two wrought-iron cylinders , exactly similar to those used in experiment 2 , were heated and cooled by being immersed to two-thirds their depth in water twenty times . The upper edge of the large cylinder was reduced 2 ' 1 inches , and the lower edge '9 inch ; it contracted 5'9 inches at about an inch above Fig. 7 . Fig. 8 . ] ! IT IPi T ! tI r-w , I WWL One-eighthl of full size . the water-line , and the inside surface had increased in depth '35 inch ( see fig. 7 ) . The upper edge of the small cylinder was reduced in circumference 3'6 inches and the lower edge '65 inch , while the greatest contraction at about one inch above the water-line was 4'6 inches ; and the internal surface had increased *15 inch in height ( see fig. 8 ) . Experiment 5.-A solid cylinder of wrought iron , 3 inches in diameter and 6 inches deep , was heated and cooled by being immersed half its depth in water fifteen times . The greatest contraction took place a little above the water-line and on the lower edge , being in each case '45 inch ; the upper edge was reduced only ? 1 inch . Fig. 9 . I I , if ---1 iiI ' II i/ / I I/ / One-half of full size . The dotted lines indicate the original form . A swell of metal took place on the two ends , but was greatest on the bottom , or that cooled in water , being '15 inch in height . The fibre of the iron opened at the fifteenth cooling ( see fig. 9 ) . Experiment 6.-A wrought-iron cylinder exactly similar to the last was cooled by being immersed to two-thirds its depth fifteen times . The greatest contraction , amounting to *4 inch , took place a little above the water-line ; the upper edge was -05 inch smaller , and the lower edge '35 inch , while the swellings on the ends were nearly the same as in the last experiment ( see fig. 10 ) . Fig. 10 . One-half of full size . The dotted lines indicate the original form . The separation of the fibre took place at the fifteenth cooling . Experiment 7.-Two flat pieces of wrought iron , each 12 inches long , 6 inches deep , and -5 inch thick , were heated and cooled twenty times , one being immersed to half , and the other to two-thirds its depth in water . That immersed one-half had contracted or become indented on the ends fully '3 inch ; the other had similar indentations , but to only 460 one-half the amount . They were both turned up into the form of an arc , had thickened on their upper edges , and increased 1 inch in thickness where the contractions on the ends took place ( see figs. 11 and 12 ) . Fig. 1 . ML . _ _--Fig . 12 . h ' One-fourth of full size . Experiment 8.-Two hollow wrought-iron cylinders , 9 inches deep and 12 inches in diameter , were heated and cooled , one by simple exposure to air ( fifteen times ) , and the other by total immersion in water ( ten times ) No alteration occurred in the form of either* . Experiment 9.-A solid cast-steel cylinder , of the same dimensions as that used in Experiment 5 , was heated and cooled by half-immersion twenty times . The effect obtained was similar to that produced upon the solid wrought-iron cylinders , but the breaking up of the structure was different ( see fig. 13 ) . The greatest contraction was slightly above the Fig. 13 . W , L Fig. 14 . ( Top offig . 13 . ) Fig. 15 . ( Bottom of fig. 13 . ) - ... One-half of full size . The dotted lines indicate the original figure . water-line , and amounted to *38 inch ; the bulgings on the ends were *075 inch , being much less than on the wrought-iron cylinders . point it weighed 50 lbs. 1'125 oz. , or 2'625 ozs . heavier than it was at the commencement ; from the tenth to the fifteenth heating the accumulated scales peeled off , and the weight was gradually reduced to that stated above . That which was cooled in water weighed 50 lbs. 12'5 ozs . before the experiment , and 48 lbs. 14'5 ozs . at its conclusion , giving a loss of 1 lb. 14 ozs . , which was due to the action of the water peeling off the scale each time the cylinder was cooled . 46 Experiment 10.-A hollow brass cylinder , 6 inches long , 2 inches in diameter , and lg-th of an inch thick , was heated to redness and cooled by half-immersion thirty-four times . The effect produced was the opposite to that which took place with the iron cylinders , being an expansion instead of a contraction at the water-line , the amount of which was * 75 inch , and it was also expanded on the lower edge ? 1 inch ( see fig. 16 ) . Fig. 16 . One-half of full size . The dotted line indicates the original figure . Experiment 11.-A hollow gun-metal cylinder was heated to redness and cooled twenty times by half-immersion . The thickness of metal being greater than in the last experiment , the effect at the water-line was much less , but the lower edge had expanded ? 1 inch . It began to crack all over at the last cooling . Experiment 12.-A hollow tin cylinder was heated in linseed-oil which was brought to a temperature of 400 ? Fahr. ; it was cooled by half-immersion in water five times . 2 The form was not altered in the least , though the heat was raised in the last instance to the melting-point , as shown by the lower part of the cylinder beginning to melt . Experiment 13.-A hollow zinc cylinder was heated and cooled by half-immersion fifty times . It was heated in a wood furnace , the degree of heat to which it was brought being regulated by the melting of a piece of tin which was conveyed at the same time with it into the furnace . Several experiments with pieces of tin and zinc had been previously made , by means of which it was ascertained that in the same temperature tin melted in two-sevenths of the time requisite to melt zinc ; hence when the zinc cylinder and piece of tin were placed in the furnace together , the time occupied by the tin in reaching its melting-point was carefully noted , and the cylinder was left in the furnace as long again as the time thus observed ; by this means it was brought very nearly to its melting-point without incurring any danger of its actually melting . The last five times , however , it was allowed to remain a little longer in the flame ; and the melting upon the top was retarded the last four times by placing a piece of iron upon it , which conducted heat from that part , allowing it to remain half a minute longer in the furnace . The effect obtained was the same as that produced upon the brass cylinder ( Exp. 10 ) , or the opposite of what took place with iron ; an Fig. 17 . 464 [ March 5 , ( expansion of * 175 inch occurred upon the water-line , and of 115 inch upon the lower edge . Experiment 14.-The hollow wrought-iron cylinder was heated to redness and cooled by half-immersion on its side , instead of on its end as in other experiments , twenty times . The effect was a very complicated one ( see figs. 17 , 18 , and 19 ) ; the dotted lines show the original form . Fig. 18 . ( Side view of fig. 17 . ) *-E , ~~~~~~~~~~~~~~~~~~~~~~~~~ Fig. 19 . ( Front view of fig. 17 . ) The three figures are one-sixth of full size . 1863 . ] 465 II I ? i -2i Experiment 15.-A solid wrought-iron cylinder was heated to redness and cooled by half-immersion on its side twenty times . The effect was of a similar nature to that of the last experiment ( see figs. 20 and 21 ) . Fig. 200 Fig. 21 . One-half of full size . The dotted line indicates original figure . Experiment 16.-A hollow cast-iron cylinder , the dimensions of which were the same as those of the deep cylinder of Experiment 14 , was heated to redness and cooled twice by half-immersion . At the second cooling it fractured nearly all round , about an inch below the water-line . It expanded all over , but the expansion was least about an inch above the water-line , i. e. it did not contract to its original dimensions . Experiment 17.-A solid cast-iron cylinder , 3 inches in diameter and 6 inches deep , was heated and cooled five times by half-immersion . At the fifth cooling it cracked across the bottom ; it also expanded 466 [ March 5 , throughout , and the expansion was least a little above the water-line , i. e. it did not contract to its original dimensions . The subjoined figures ( half the full size ) show the changes produced on the 9-inch cylinders after every five heatings . ( Experiments 2 and 4 . ) Fig. 22 . Fig. 23 . 12 " Cylinder , 9 " high , 1 " thick . 12 " Cylinder , 9 " high , 1 " thick . Vide fig. 4 . Cooled by '-immersion . Vide fig. 7 . Cooled by I-immersion . No. 1 . External surface , original form . No. 1 . External surface , original form . 2 . , , , , after 5 coolings . 2 . , , , , after 5 coolings . 3 . , , , , 10 , , 3 . , , , , , , 10 4 . , , , , , , 15 , , 4 . , , , , , , 15 , , 5 . , , , ,,3 20 , , 5 . , , , , , 20 p --I--- ' -- " ' -----'- ; -`--- ` Tabulated Statement of the Results of the Experiments . Dimensions , in inches . ? 11 ? a 1 ? ?ii Form of article , &c. X| ' 1a . Wrought 5 Hoop-tire for a 4 ' 2 " wheel:iron . External circumf . of upper edge ... 155*5 147'5 8*0 do . do . lower edge ... 155'5 156'375 +0'875 Bevel of face ... ... ... ... ... ... ... . 90 ? ? 69 ? ? 21 2b . Wrought 20 '12 " cylinder , 9 " deep and t " thick : iron . Internal circumf . of upper edge ... 37'6 37'6 0'0 do . do . contraction..i 37'6 32-1 --55 do . do . lower edge ... 37'6 37'0 -0'6 Depth , perpendicular ... ... ... ... ... 90 8-8 -0'2 do . on curve , external ... ... ... 9'0 9'15 +0'15 , ^ do . do . do . internal ... ... ... 90 935 +0'35 2e . Wrought 20 12 " cylinder , 6 " deep and d " thick : iron . Internal circumf . of upper edge ... 37'6 36'9 --070 do . do . contraction ... 37'6 32*35 --5-25 do . do . lower edge ... 37'6 37-9 +0'30 Depth , perpendicular ... ... ... ... ... 6'0 5'7 --030 do . on curve , external ... ... ... 6'0 6'05 +0 05 do do internal ... ... ... 66 30 6 030 +030 3d . Wrought 10 . 12 " cylinder , " derep , thin sheet:iron . External circumf . of upper edge ... 38*40 38*40 0-00 ~ ; -~ " do . do . contraction ... 38-40 34'90 -3'50 do . do . lower edge ... 38 40 38'45 +0-05 Depth , on curve ... ... ... ... ... ... . 9 00 9-15 +0-15 4e . Wrought 20 . 12"cylinder,9"deepand'"thick:iron . External circumf . of upper edge ... 40-90 38*80 --210 do . ' do . contraction ... 40-90 35'00 -5'90 do . do . lower edge ... 40'90 40'00 --090 Depth , perpendicular ... ... ... ... ... 9'00 8'80 --020 do . on curve , external ... ... ... 9'00 9'00 000 do . do . internal ... ... 9. . 900 935 +0'35 4f . Wrought 20 12'cylinder , 6"deep and ' " thick:iron . External circumf . of upperedge ... 40'8 '37-2 -3-6 do . do . contraction ... 40*8 36*2 -4'6 ; ~~ : do . do . lower edge ... 40'8 40*15 --065 Depth , perpendicular ... ... ... ... ... 6'0 6'0 00 - ; do . on curve , external ... ... ... 6-0 6'05 +0-05 do . do . internal ... ... ... 6-0 6'15 +0'15 5g . Wrought 15 1 3 " cylinder , 6 " deep , solid:iron . Circumference , upper edge ... ... ' 9'4 9'3 --01 do . contraction ... ... 9'4 8 95 -0'45 do . lower edge ... . . 94 8S95 -0'45 Bulge on upper end ... ... ... . 0 00 004 -004 f. erdo . lower end ... ... ... ... ... 000 0*15 +-015 a For remarks see end of Table , p. 470 . 468 [ March 5 , TABLE ( continued ) . Dimensions , in inches . *S C. o0 o 6h . Wrought 15 2 3 " cylinder , 6 " deep , solid:iron . Circumference , upper end ... ... ... 9'40 9'35 -0*05 do . contraction ... ... ... 9'40 9'00 --040 do . lower edge ... ... ... 9'40 9-05 -0-35 Bulge on upper end ... ... ... ... ... 0'00 0 05 +0'05 do . lower end ... ... ... ... ... 0'00 0-20 +0'20 7i . Wrought 20 Flat piece , 12 " x6 " X:iron . Length on curve , upper edge ... 12'00 10'75 -1*25 do do lower edge ... 12'00 12'10 -+010 Breadth , ends ... ... ... ... ... ... ... . . 6'00 5'75 -0-25 do . centre ... ... ... ... ... ... . 6-00 6-00 0.00 Upper edge , out of straight ... ... 000 0060 +0-60 Indentation on ends ... ... ... ... ... 000 0'30 +0'30 7k . Wrought 20 4 Flat piece , 12 " x 6 " X " : iron . Length on curve , upper edge ... ... 1200 11'10 -0'90 do . do . lower edge ... ... 1200 12*20 +0-20 Breadth , ends ... ... ... ... ... ... . 6-00 5-87 --013 do . centre ... ... ... ... ... ... ... 6-00 5.95 -0'05 Upper edge , out of straight ... ... 0'00 0'50 +0.50 Indentation on ends ... ... ... ... . 0'00 0'15 +0'15 8 . Wrought 15 0 12 " cylinder , 9 " deep , " thick } N. iron . 10 total do . do . do . 9m . Cast 20 4 3 " cylinder , 6 " deep , solid:steel . Circumference , upper edge ... ... 9 03 8'93 -0'10 do . contraction ... ... 9'03 8-65 -0'38 do . lower edge ... ... 9'03 8'93 -0 ' 10 Depth , perpendicular ... ... ... ... ... . 600 6-10 +0'10 10 " . Brass . 34 4 2 " cylinder , 6 " deep , -1 " thick : External circumf . of upper edge ... 6-175 6-175 0-000 do . do expansion ... 6 ' 175 6'350 +0-175 do . do . lower edge ... . 6'175 6'270 +-0095 11 ? . Gun20 4 3 " cylinder , 6 " deep , - " thick:metal . External circumf . of upper edge ... 9*25 9'24 -0'01 do . do . on water-line ... 9'25 9'26 +0'01 do . do . of lower edge. . 9'25 9'38 +0-13 12 . Tin , 51 2 " cylinder , 5 " deep , 4 " thick ... ... No effect . 13 . Zinc . 50 3 " cylinder , 6 " deep , 4 " thick : External circumf . of upper edge ... 9 525 9 575 +-0050 do . do . expansion ... 9-525 9700 -+0175 do . do . lower edge ... 9'525 9630 +0-105 ! et , predclr . , ... ... '0 61 01 TABLE ( continued ) . Dimensions , in inches . ? g j id Form of article , &c. 99 14P . Wrought 20 2 12 " cylinder , 9 " deep , 2 " thick:iron . on External circumference of edges. . 40 65 39-86 --0-79 its do . do . centre. . 40-65 41,05 +-040 side . Depth on curve , part cooledin air . 9 00 9 00 0 00 do . do . water-line . 9'00 8-25 --075 do . do . in water ... 9-00 8-80 -0-20 Swellofside , 1 " below W.L. ( ata , b ) 0'00 1'00 +1'00 Hollowofside , 4"above do . ( ate , d ) 0-00 0'40 +0-40 Longest ex. diam. 1 " below W. L. 12-94 14-275 +1-335 Shortest do . at rt . angles to W.L. 12-94 12-00 -0-94 Indentation of edges a little above water-line at e ... ... ... 000 0'45 +45 15q . Wrought 20 l 3 " cylinder , 5a " deep , solid:iron . on External circumference of edges. . 9-4 9'2 --0'2 its do do . centre . 9-4 9-475 -+0075 side . Depth along part cooled in air ... 5-375 5-150 -0-225 do . do . on W.L. 5-375 5-100 --0275 do . do . in water . 5-375 5-225 --0'150 Longest diam. at rt . angles to W.L. 3-000 3-100 +0-100 Shortest do . parallel with W.L. 3'000 2760 -0 240 and a little below it ... ... ... 16 . Cast 21 12 " cylinder , 9 " deep , } " thick:iron . External circumf . of upper edge ... 40'90 41'05 +-015 do . do . least expansion 40'90 40-95 +0-05 do . do . of lower edge40-90 41-15 +0'25 17 . Cast 53 3 " solid cylinder , 6 " deep:iron . External circumf . of upper edge ... 9-4 9'55 +0-15 do . do . least expansion 9'4 9-50 +0'10 do . do . of lower edge ... 9-4 9-55 +0-15 Remarks . a The width was unaltered , and the thickness of the upper edge slightly increased . Figs. 1 and 2 . b Fig. 4 . c Fig. 5 . d Fig. 6 . C Fig. 7 . f Fig. 8 . g The fibre opened at the fifteenth cooling . Fig. 9 . h The fibre opened at the fifteenth cooling after having exhibited a slight crack for two or three previous coolings . Fig. 10 . i The thickness of the metal at the indentation on ends increased -1 " . Fig. 11 . k The thickness of the metal at the indentation on ends increased similarly to the last . Fig. 12 . l Cooled in air 15 times . Cooled in water 10 times . m The ends became slightly rounded . Fig. 13 . n At the last cooling the lower end of the cylinder began to crumble away in the water . Fig. 16 . o The expansion of the lower end may probably be due to the cracking of the metal , which was greatest at that part . P Figs. 17 , 18 , 19 . There was an increased thickness of metal at e , q Figs. 20 , 21 . 470 [ March 5 , [ The cause of the curious phenomenon described by Colonel Clerk in the preceding paper seems to be indicated by some of the figures , especially those relating to hollow cylinders of wrought iron , which are very instructive . Imagine such a cylinder divided into two parts by a horizontal plane at the water-line , and in this state immersed after heating . The under part , being in contact with water , would rapidly cool and contract , while the upper part would cool but slowly . Consequently by the time the under part had pretty well cooled , the upper part would be left jutting out ; but when both parts had cooled , their diameters would again agree . Now in the actual experiment this independent motion of the two parts is impossible , on account of the continuity of the metal ; the under part tends to pull in the upper , and the upper to pull out the under . In this contest the cooler metal , being the stronger , prevails , and so the upper part gets pulled in , a little above the water-line , while still hot . But it has still to contract on cooling ; and this it will do to the full extent due to its temperature , except in so far as it may be prevented by its connexion with the rest . Hence , on the whole , the effect of this cause is to leave a permanent contraction a little above the water-line ; and it is easy to see that the contraction must be so much nearer to the waterline as the thickness of the metal is less , the other dimensions of the hollow cylinder and the nature of the metal being given . When the hollow cylinder is very short , so as to be reduced to a mere hoop , the same cause operates ; but there is not room for more than a general inclination of the surface , leaving the hoop bevelled . But there is another cause of deformation at work , the operation of which is well seen in figs. 2 and 3 . Imagine a mass of metal heated so as to be slightly plastic , and then rapidly cooled over a large part of its surface . In cooling , the skin at the same time contracts and becomes stronger , and thereby tends to squeeze out its contents . This accounts for the bulging of the ends of the solid cylinders of wrought iron and the rents seen in their cylindrical surface . The skin at the bottom is of course as strong as at the sides in the part below the water-line ; but a surface which resists . extension far more than bending has far less power to resist pressure of the nature of a fluid pressure when plane than when convex . The effect of the cause first explained is also manifest in these cylinders , although it is less marked than in the case of the hollow cylinders , as might have been expected . The tendency of the cooled skin of a heated metallic mass to squeeze out its contents appears to be what gives rise to the bulging seen near the water-line in the hollow cylinder of brass . Wrought iron , being highly tenacious even at a comparatively high temperature , resists with great force the sliding motion of the particles which must take place in order that the tendency of the cooled skin to squeeze out its contents may take effect ; but brass , approaching in its hotter parts more nearly to the state of a molten mass , exhibits the effect more strongly . It seems probable that even in the case of brass a very thin hollow cylinder would exhibit a contraction just above the water-line . Should there be a metal or alloy which about the temperatures with which we have to deal was stronger hot than cold , the effect of the cause first referred to would be to produce an expansion a little below the water-line.--G . G. S. ]

112288

3701662

On the Influence of Temperature on the Electric Conducting Power of Thallium and Iron. [Abstract]

472

475

Proceedings of the Royal Society of London

A. Matthiessen|C. Vogt

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112288

http://www.jstor.org/stable/112288

Electricity

Chemistry 2

Electricity

I. " On the Influence of Temperature on the Electric Conducting Power of Thallium and Iron . " By A. MATTHIESSEN , F.R.S. , and C. VOGT , Ph. D. Received February 12 , 1863 . ( Abstract . ) Thallium.-The experiments detailed in this paper were made with specimens of thallium lent to us by Mr. Crookes and Professor Lamy of Lille . The values obtained for the conducting power , together with the formulae for the correction of the conducting power for temperature of the different specimens , were : For Mr. Crookes 's metal , 1st wire . 2nd wire at 0 ? . X= 9-3640037936t + 000008467t ' ; 9 169 . For M. Lamy 's first specimen , 2nd wire at 0 ? . 3rd wire . X=9'419--0-039520t+ 0-00009656t2 ; 9-082 ; 9-223 . Second specimen , 2nd wire at 0 ? . X =9'054-0-034697t+0-00006554t2 ; 9-22.6 ; or as mean of all the determinations , some of which are not given here , X=9 1630-036894t+ 0-00008104t2 . The conducting power of thallium therefore decreases between 0 ? and 100§ 31-420 per cent. , which is a larger percentage decrement than that obtained for many other pure metals , namely 29'307 per cent.* Iron.-The specimens of iron experimented were , with two exceptions , lent us by Dr. Percy . In the following Table we give the results obtained with them:(1 . ) Electrotype iron , deposited from solution of pure sulphate of iron . The strips were very thin and porous ; we could not therefore obtain concordant values for the conducting power , but we were able to determine the percentage decrement in the conducting power between 0 ? and 100 ? . We have , for the above reason , taken the first observed conducting power equal 100 . X100-0-51182t+0-0012915t2 , corresponding to a percentage decrement'of 38'262 per cent. ( 2 . ) No. 1 , annealed and cooled in hydrogen . X= 100-0-51894t+0 0013415t2 , corresponding to a percentage decrement of 38*479 per cent. ( 3 . ) Electrotype iron , a strip cut from the same foil as No. 1 . X= 100--051355t 0-0013221t2 , corresponding to a percentage decrement of 38'134 per cent. ( 4 . ) No. 3 , annealed in air . X= 100050895t + 00002735t2 , corresponding to a percentage decrement of 38 160 per cent. ( 5 . ) This , as well as Nos. 6 , 7 , 8 , were specimens of iron which have been analysed . They were all hard drawn . X= 15719 --0074370t+0000 1763t2 , corresponding to a percentage decrement of 36'070 per cent. ( 6 . ) X= 15'672--0074045t+ 0'0001761t2 , corresponding to a percentage decrement of 36'010 per cent. ( 7 . ) X= 14'2690'064133t + 00001456t2 , corresponding to a percentage decrement of 34'742 per cent. ( 8 . ) X= 12-342-0-055894t+0'0001379t2 , corresponding to a percentage decrement of 34 ' 117 per cent. ( 9 . ) Strip of iron , heated in a current of hydrogen at a red heat for two hours . This , as well as Nos. 10 , 11 , 12 , were hardened . X= 14'673-0-067999t+0 0001597t2 , corresponding to a percentage decrement of 35'459 per cent. ( 10 . ) As No. 9 , heated for three hours under sugar charcoal in a current of hydrogen ; the carbon taken up was 0'99 per cent.\= 10-6540'044560t + 000009 789t2 , corresponding to a percentage decrement of 32'637 per cent. ( 11 . ) As No. 9 , heated for four hours under sugar charcoal in a current of hydrogen ; the carbon taken up was 0'933 per cent. X=9'925-0'040097t + 000009168t2 , corresponding to a percentage decrement of 31'163 per cent. ( 12 . ) As No. 9 , heated for three hours under sugar charcoal in a current of hydrogen ; the carbon taken up was 1'06 per cent. X= 9-457 0037573t + 0'00008642t2 , corresponding to a percentage decrement of 30'592 per cent. ( 13 . ) Thin music wire , melted with one quarter of its weight of peroxide of iron under a flux of plate glass . X=13-381 -0'056829t+0'0001230t2 , corresponding to a percentage decrement of 33'278 per cent. ( 14 . ) A piece of narrow watch-spring . X=8-565 -0029099t+0'00005383t2 , corresponding to a percentage decrement of 27*689 per cent. ( 15 . ) Commercial iron wire . X= 13'7720058970t 0-0001 242t2 , corresponding to a percentage decrement of 33'801 per cent. From the results obtained , it is obvious that the higher the conducting power the higher the percentage decrement in the conducting power between 0 ? and 100 ? . This has been proved to be the case with about 100 alloys with which we have experimented . We have also found that we may deduce the conducting power of a pure metal from an impure one when the impurity does not reduce the conducting power more than , say , 10 to 20 per cent. According to our experiments , the percentage decrement in the conducting power of an impure metal between 0 ? and 100 ? varies in the same ratio as the conducting power of the impure metal at 100 ? , compared with that of the pure metal at 100 ? . Thus , from specimens Nos. 5 , 6 , 7 , 9 , 13 , and 15 , the conducting power of pure iron was found to be at 0 ? = 16'725 . In conclusion , we give the values found for specimens of cobalt and nickel wire lent to us by Professor Wohler . They were as follows : Cobalt wire . X= 12-9300-035521t+0-00004887t2 , corresponding to a percentage decrement of 23'692 per cent. Nickel wire . X= 12-222-0-040787t+0-000 7088t2 , corresponding to a percentage decrement of 27'573 per cent. Although these metals were said to be chemically pure , the results obtained seem to indicate that they are not so , having probably taken up some impurities in the process of fusion . The following Table of the conducting powers of pure metals shows the place which the metals treated of in this paper take in the series . Conducting power at 0 ? . Silver ( hard drawn ) ... ... ... ... 100-00 Copper ( hard drawn ) ... ... . . 99.95 Gold ( hard drawn ) ... ... ... ... 77-96 Zinc ... ... ... ... ... ... . 2902 Cadmium ... ... ... ... ... ... . . 23 72 Cobalt* ... ... ... ... ... ... . . 17-22 Iron* ( hard drawn ) ... ... ... . . 1681 Nickel * ... ... ... ... ... . 13-11 Tin ... ... ... ... ... ... ... ... 12-36 Thallium ... ... ... ... . 9'16 Lead ... ... ... ... ... ... ... 8-32 Arsenic ... ... ... ... ... ... 4*76 Antimony ... ... ... ... ... ... 4-62 Bismuth ... ... . . 1-245

112289

3701662

On the Amyloid Substance of the Liver, and Its Ultimate Destination in the Animal Economy. [Abstract]

476

480

Proceedings of the Royal Society of London

Robert McDonnell

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112289

http://www.jstor.org/stable/112289

Physiology

Biology 3

Physiology

II . " On the Amyloid Substance of the Liver , and its ultimate destination in the Animal Economy . " By ROBERT MCDONNELL , M.D. Communicated by WILLIAM BOWMAN , Esq. Received February 13 , 1863 . ( Abstract . ) After briefly referring to the discovery of the amyloid substance of the liver , and the earlier history of the subject , the author examines the facts which have induced Dr. Pavy to conclude that this substance is not normally transformed into sugar during life . The author being led , after a careful repetition of Dr. Pavy 's experiments , to concur in his views , asks , If then the amyloid substance of the liver be not converted into sugar , what becomes of it ? what is its normal destination in the animal economy ? It is the object of the memoir to attempt to answer this question , which , it must be admitted , is one of the greatest delicacy ; nevertheless there appears on the whole to be evidence that the amyloid substance met with in the liver is on its way upwards towards the more exalted or complex immediate animal principles ; that , in fact , the process of healthy assimilation tends , if the expression may be used , to promote it from the rank of ternary ( hydrocarbonous ) to that of quaternary ( azotized ) compounds ; and that its conversion into sugar is to be looked upon as a deviation from this progressive course-a dissimilative instead of an assimilative process . In order to establish this view it became necessary1st . To investigate the chemical and physiological relations of the amyloid substance , not only of the liver , but of other organs and tissues , and to test the very interesting results , which are for the most part due to M. Charles Rouget . 2ndly . To compare the portal and hepatic blood with each other , and with arterial and venous blood derived from other sources ; and 3rdly . To consider the relations to each other of the different functions performed by the liver . For if it be true , as Lehmann , Brown-Sequard , and others have asserted , that the fibrine and much of the albumen of the portal blood vanishes in the liver , and that at the same time that it destroys these azotized compounds it forms its non-azotized amyloid substance , and excretes bile containing so little nitrogen that it need hardly be taken into account , are we not , from the consideration of these functions , led to infer that the nitrogen which leaves the liver by no other outlet may go forth in the hepatic blood in union with the amyloid substance thus changed into a new azotized principle ; -that thus the liver is a great bloodmaking organ , in which there is constantly going on a reconstruction of certain ingredients of the blood ; that in it the fibrine , &c. , which has done its work , is disintegrated , the hydrocarbons of the bile abstracted , and the nitrogen combined with the amyloid substance , which , instead of being normally changed into sugar , emerges from the liver a constituent principle of the protoplasma , from the bosom of which ( to use the words of Bernard with reference to the foetal tissues ) organic evolution is to be accomplished ? Of the existence of the Amyloid Substance of Bernard in the Placenta and other Organs and Tissues . The cells of the placenta contain , during the earlier stages of embryonic life , animal dextrine , having characters identical with those of the amyloid substance of the liver ; its presence may be readily demonstrated under the microscope . Bernard has discovered it in the placentae of rabbits , guinea-pigs , &c. He also made the very interesting observation that the multiple placentulae of the ruminants do not contain any amyloid substance , but that in this class of animals this substance is found in certain cells of the amnion . The presence , however , in the amnion or the placenta , of epithelial cells containing amyloid substance , is a fact quite secondary to the general fact that this substance enters largely into the constitution of most of the tissues of the embryo . Its existence does not indicate a new function of an organ doing temporarily the duty of the liver , but it indicates a new fact with regard to the development of certain structures and a new property of tissue . During embryonic life a great part of the foetal tissues are found to be so impregnated with amyloid substance , that it appears to be the formative material from which these tissues are evolved ; and , in fact , it would seem to be related to their growth and development , as starch is to the growth and development of the tissues of vegetables . In the skin of the chick in ovo , and of the foetuses of rabbits , cats , guinea-pigs , sheep , oxen , pigs , it is readily demonstrated ; it is seen by the addition of acidulated tincture of iodine , and is most abundant at the points where the aggregation of epithelial cells shows that the feathers and hairs are about being developed . The horny structures contain it plentifully ; in the bill , the hoof , and the claws it exists in large proportion . From the hoof of a foetal calf of about four months enough may be obtained , by the alcoholic solution of potash , for chemical examination and fermentation . The muscular tissues of the foetus are full of it ; from 20 to 50 per cent. can be extracted from the muscles of foetal calves of from three to seven months by the aid of the alcoholic solution of potash . Having arrived , by a repetition of Dr. Pavy 's ingenious experiments , at the conclusion that the amyloid substance of the liver is not normally changed into glucose , and finding on examination the accuracy of the facts concerning the physiological relations of the amyloid substance to the foetal and other tissues , discovered by M. Charles Rouget , and investigated by Bernard himself , the question presents itself , May it not be that the liver does for the adult what divers tissues do during the development of the foetus ? May not this great organ form , with the help of the amyloid substance secreted in its cells , a nitrogenous compound , just as the muscles of the foetus convert the amyloid substance contained in them into the highly nitrogenous material of muscular tissue ? May not , in fact , the amyloid substance of the liver be the basis of an azotized protoplasma forming a constituent of the blood of the adult animal , as the amyloid substance of muscle is the basis of the material from which the evolution of muscular tissue is accomplished ? Even a superficial consideration of the functions performed by the liver leads one to answer these questions in the affirmative . For if it be true that the blood which enters the liver is rich in fibrine and albumen , and that these materials are so completely changed within this organ that little or none of them leave it by the hepatic vessels , what becomes of them ? It is true their hydrocarbonous constituents may be thrown out as bile . But what of the nitrogen contained in them ? If it does not escape by the bile-ducts , it has no other mode of exit save by the hepatic vessels . The author conceives it to be reunited with the hydrocarbonous amyloid substance , and to leave the liver as a newly-formed proteic compound , partly perhaps as globuline , and partly as material , in its reactions resembling caseine in some respects , in others albuminose , and which is fully described in the memoir . These considerations lead to the necessity of investigating the several distinct functions of the liver:1st . As to its action on the fibrine and albumen of the blood . 2nd . As to the constitution of healthy bile ( so far as its azotized elements are concerned ) . 3rd . As to the relative composition and characters of the blood which enters and of that which leaves the liver . The author adds his testimony to that of Lehmann and BrownSequard as regards the fibrine-destroying function of the liver ; he attempts to show that , in proportion to the amount of fibrine which disappears in the liver , the quantity of nitrogen eliminated in the form of bile is very small indeed , but that the blood in passing through the liver becomes greatly enriched in colourless corpuscles , and that it contains more abundantly than other blood an azotized compound , resembling what has been described by some authors as blood-caseine . This material , although resembling , is not identical with caseine ; it can be obtained from the serum of blood abstracted by a peculiarly contrived instrument ( a drawing of which accompanies the paper ) from the vena cava , close to the mouths of the hepatic veins . Whatever may be its precise chemical composition and characteristics , whether it is to be regarded as a form of albumen , or albumen-peptone ( albuminose ) , or caseine , it is enough to state , that during active digestion the blood which leaves the liver contains a proteic compound , that it is richer in this compound than arterial blood , and that this latter is richer in it than ordinary venous blood , or than that of the portal vein . At the same time the blood of the hepatic veins contains a far larger quantity of colourless blood-corpuscles than the portal blood . A microscopic examination of these kinds of blood shows that the colourless corpuscles are from five to ten times more numerous in the former than in the latter . Physiologists are so familiar with this fact , as well as with the chief peculiarities of the colourless corpuscles of hepatic blood , that it is unnecessary to dwell upon the circumstances which have induced some of the most distinguished among them to regard as the most important function of the liver , the formation , or at least the rejuvenescence , of the blood-corpuscles . Dr. Carpenter conceives that the appearance of the colourless corpuscles of the blood may be regarded as a phenomenon analogous to the development of cells in the albumen of seeds in the vegetable kingdom . He also supposes that these cells aid in the conversion of crude alimentary matters into proximate principles . Additional support is given to each supposition by the notion that these colourless cells stand in close relationship to the material formed in the liver , so closely resembling dextrine of vegetable origin . It is true that there is nothing novel in the view that the liver is a great blood-forming organ , or rather that it is an organ in which certain components of the blood are disintegrated , while from some of the matter so disintegrated a constant reconstruction of the blood is going forward ; yet it is certain that , not long since , physiologists would have been unwilling to admit that materials constituted as the colourless blood-cells or caseine could be formed within the liver from a substance resembling starch taking to itself nitrogen derived , as one may say , from the retrogressive metamorphosis of tissue . It is very improbable that , looking to the liver alone , such a conclusion would have been arrived at . The consideration , however , of the physiological relations of the amyloid substance ( of Bernard ) , as regards the development of the azotized tissues of the foetus , - the fact that it is , so far as they are concerned , a protoplasma , which , by taking to itself nitrogen , terminates in the evolution of fully-formed nitrogenous tissues , -prepares one to consider the idea that the liver evolves its proteic compounds during adult life by a somewhat similar process . To M. Charles Rouget we unquestionably owe the observation of the fundamental facts which lead to the foregoing conclusions ; yet the author hopes that the recapitulation of facts in this communication will be found worthy of the consideration of physiologists ; for he conceives that not only is the view of the subject which he has ventured to adopt in harmony with a great number of hitherto unexplained circumstances , but that it gives a solution more satisfactory than any yet given of certain pathological phenomena which it would be out of place to speak of here .

112290

3701662

Supplement to a Paper on the Differential Equations of Dynamics. [Abstract]

481

481

Proceedings of the Royal Society of London

George Boole

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112290

http://www.jstor.org/stable/112290

Formulae

Biography

Mathematics

III . Supplement to a Paper " On the Differential Equations of Dynamics . " By Professor GEORGE BOOLE , F.R.S. Received February 9 , 1863 . ( Abstract . ) It is shown in the general paper that if an integral of any one equation of the peculiar system of ( partial differential ) equations there discussed be found , then if a certain numerical result of subsequent and always possible operations prove odd , an integral of the entire system can be found by the solution of a single differential equation of the first order . It is shown in the paper now sent that , when the above numerical result is even * , we can reduce the original system of partial differential equations into a new system , fewer in number by unity at least , and of the same general character , so as to admit of a repetition of the same procedure . Thus the common integral sought will finally be given either by the solution of a single differential equation of the first order , or by finding one integral of the single partial differential equation , which , in the most unfavourable case conceivable , will remain at last .

112291

3701662

On Peculiar Appearances Exhibited by Blood-Corpuscles under the Influence of Solutions of Magenta and Tannin

481

491

Proceedings of the Royal Society of London

William Roberts

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0102

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112291

10.1098/rspl.1862.0102

http://www.jstor.org/stable/112291

Biology 3

Biology 2

Biology

1 . " { On Peculiar Appearances exhibited by Blood-corpuscles under the influence of Solutions of Magenta and Tannin . " By WILLIAM ROBERTS , M.D. , Physician to the Manchester Royal Infirmary . Communicated by Dr. SHARPIEY , Sec. R.S. Received February 18 , 1863 . The object of the following paper is to give an account of certain observations which seem to indicate that the cell-wall of the vertebrate blood-disk does not possess the simplicity of structure usually attributed to it . It is well known that the blood-corpuscles , when floating in their own serum , or after having been treated with acetic acid or water , * Also when odd , but then not required . appear to be furnished with perfectly plain envelopes , composed of a simple homogeneous membrane , without distinction of parts . But , as will appear from the observations here to be related , when the blood is treated with a solution of magenta ( nitrate of rosanilin ) or with a dilute solution of tannin , the corpuscles present changes which seem irreconcilable with such a supposition . Attention is first asked to the effects of -magenta . When a speck of human blood was placed on a glass slide and mixed with a drop of a watery soluition of magenta* , the following changes were observed . The blood-disks speedily lost their natural opacity and yellow colour ; they became perfectly transparent , and assumed a faint rose colour ; they also expanded sensibly , and lost their biconcave figure . In addition , a dark-red speck made its appearance on some portion of their periphery . The pale corpuscles took the colour much more strongly than the red ; and their nuclei were displayed with great clearness , dyed of a magnificent carbuncle-red . Many of the nuclei were seen in the process of division , more or less advanced ; and in some cells the partition had resulted in the production of two , three , or even four distinct secondary nuclei . These appearances were first observed in freshly-drawn blood from the finger . Subsequently blood from the horse , pig , ox , sheep , deer , camel , cat , rabbit , and kangaroo was examined in like manner . The effect on the red corpuscles ( to which all the observations hereinafter recorded are exclusively confined ) was in each instance the same as in human blood . The nucleated blood-disks of the oviparous classes , when treated similarly , yielded analogous results . The coloured colntents were forthwith discharged ; the central nucleus came fully into view , and assumed a deep-red colour ; the corpuscles expanded , they lost something of their oval form , and approached nearly , or sometimes quite , to a circular outline . Lastly , there appeared on the periphery a dark-red macula , of a character and position resembling that seen on the mammalian blood-disk . Such a macula was detected in the fowl , in the frog , and in the dace and minnow , Owing , however , to the large quanltity of molecular matter floating in the serum , and which was coloured by the magenta , difficulties were found in preparing specimens which carried conviction that the macula in question was not an adhering granule . It was also found that it required a nice adjustment of the relative quantities of the solution and of the blood to bring , it out . It was only when the right proportions were hit , and especially when the disks were made to roll over in the field of the microscope , that the existence of a coloured particle organically connected with the cell-wall could be satisfactorily made out . The best specimens were prepared from human blood drawn in the fasting condition , and from the blood of a kitten two days old . From well-prepared specimens of human blood the following particulars were gathered ( see fig. 1):-Nearly every disk possessed the parietal macula ; it could be distinctly recognized in nine-tenths of them ; and in several of those in which it was not at first visible , it came into view as the corpuscles revolved in the field . The macula was clearly situated in the cell-wall , and not in the interior of the corpuscle . Usually it appeared as if imbedded or set in the rim of the disk , like the jewel in a diamond ring ; but sometimes it occupied various positions on the flat surfaces , and when so placed , the spot was difficult or impossible to detect . It commonly presented a thickly lenticular shape ; sometimes it was square , and occasionally in appearance vesicular ( fig. 1 , A , a ) . In some instances , and especially in long-kept specimens , the particle was seen to stand out on the outline of the disk like an excrescence . Fig. 1 . A6 ' lbld B.olslotetd ihm et A. Humanl blood . B. Fowl 's blood treated with magenta . Still more rarely , instead of a spot , a thick red line ran round the circumference for a quarter or a third of its extent ( fig. 1 , A , 6 ) . As a rule it was extremely minute , covering generally not more than a twentieth or thirtieth of the circumference ; but there was a considerable variation in its magnitude and distinctness . Very rarely two specks could be seen ; but the occurrence of adhering granules rendered the verification of this point extremely difficult . This description applies , so far as the iniquiry has yet been prosecuted , to the mammalian blood-disk generally , making allowances for differences in size . In the camel the macula occupied indifferently any part of the oval outline . Among the oviparous classes , the blood of the fowl , frog , dace , and minnow has been most fully examined ( see fig. 1 , B ) ; but the blood of the sparrow , duck , goose , and turkey was also searched , as weli as that of the newt and carp . In all of these a tinted particle appeared , more or less constantly , in the cell-wall , when the corpuscles were treated with magenta * The presence of a central nucleus in these classes caused the macula to be invisible more frequently than in mammalia , inasmuch as it suffered eclipse when situated over or under the central nucleus . In the fowl , dace , and minnow it was fouLnd easy to bring out the parietal macula ; in the fish two spots were not unfrequiently seen . The macula was situated indifferently on any part of the periphery ; and sometimes it projected from the surface . When happily prepared the specimens were even beautiful . The central nucleus was dyed of the finest red ; and on the delicate outline of the cell-wall hung the red parietal macula , offering a not altogether fanciful resemblance to the astronomical figures representing the moon coursing in its orbit round the earth . At this stage of the inquiry it was conceived that an improved demonstration might be obtained by fixing the dye with a mordant , and then subjecting the corpuscles to a lavatory process , so as to get rid of the floating granules which so much interfered with the view . For this purpose a solution of tannin ( which is one of the mordants for magenta used in the arts ) was employed ; and some advantage was found therein . When a solution of tannin , of 3 grains to the ounce of water , was added to blood that had already been dyed with magenta , it was found that the parietal maculae had their colour intensified , and that they became more conspicuous objects . The investigation was , however , not pushed any further in this direction , for it was found that tannin alone produced an even more remarkable effect than magenta . To this effect I now desire to draw particular attention . When a solution of tannin , of the strength of 3 grains to the ounce , was applied to human blood , or to that of the horse , ox , sheep , pig , or cat , the blood immediately became turbid ; and when a drop was placed under the microscope the corpuscles were found greatly changed , as represented in fig. 2 . Fig. 2 . Human blood after the action of tannin . a. Double pullulation . b , b. Hooded modification . c. Outline of the cell seen continuously through the pullulation . d. Bursting of the pullulations independently of destruction of the cell . Each corpuscle appeared to have thrown out a bright , highly refractive bud or projection on its surface . The projections were usually about a fourth part of the size of the corpuscle on which they were fixed ; but they varied considerably . Some were only minutebright specks in the cell-wall ; others were half or even twothirds as large as the corpuscle itself . Very rarely ( in mammalian blood ) two such projections were seen ; and as rarely a corpuscle was devoid of any . The projections were commonly round or dome-shaped , bordered with a deeply refractive outline . Frequently a minute , apparently vesicular body could be seen within this outline , and then the projection presented a curiously hooded aspect ( fig. 2 , 6 , b ) . In a urinary deposit from a lad twelve years of age , containing pus and blood , nearly every blood-disk presented the hooded appearance after the addition of tannin . The blood of the fowl , turkey , duck , and goose showed exactly analogous phenomena with the same reagent ( see fig. 3 ) . Fig. 3 . Blood of fowl after the action of tannin . The projection had sometimes the hooded character with a vesicular body within ; sometimes the projection offered no such distinction of parts . It was situated indifferently on any part of the periphery . In all the birds examined a second projection was as rare as in mammalia . Of fish , the dace , minnow , and carp were examined . T'he tanninsolution produced a similar effect to that seen in the fowl-with this difference , that a large number of corpuscles had two projections instead of one . In the carp double and single projections occurred in about equal proportions ; in the minnow double projections were all but universal . The second projection was situated sometimes at the opposite pole of the disk , sometimes in near proximity to its fellow , or at any point between . Very rarely , a third projection was seen in the dace . In the blood of the frog there was a strong tendency to the indefinite mnultiplication of the projections ; two , three , four , and even five would rise in succession on the surface of the disk . It appeared , too , not unfrequently as if the entire outer membrane of the cell was detached from the parts beneath and raised into eight or ten unequal elevations , giving the outline of the disk an irregularly crenate appearance * . The formation of these singular projections , or pullulations , on the blood-disks could be watched without difficulty by placing a drop of the tannin-solution benieath the covering glass , and permitting a little blood to insinuate itself into the solution inder the microscope . As the blood flowed in and mingled with the tannin , the corpuscles were observed gradually to enlarge , and then sudldenly , without previous warning , to shoot out the projection . As a rule , it does not appear to grow afterwards . The phenomenon was finely seen in the defibrinated blood of the fowl after it had been allowed to sink through a column of syrnp ( sp. gr. 1025 ) in a test-tube . Fowl 's blood washed in this way was mixed , in a little glass , with about five times its volume of the tannin-solution , and a drop immediately put under the microscope . The disks first enlarge and become rounded , and the central nucleus comes into view . In thirty or forty seconds the pullulation begins ; and each corpuscle , with instantaneous rapidity and without previous sign , throws out its bud . The disk itself suffers not the least disturbance during this act ; it preserves its symmetry unchanged , as if it had no concern , beyond that of proximity , with the sudden apparition on its surface . No visible rupture of the cell-wall took place . The circular out . line of the latter could sometimes be distinctly followed through the projection ( fig. 2 , c ) ; and as the altered corpuscles revolved in the field of the microscope , the projection appeared to be organically connected with it , but to form no part of its cavity . In the human blood-disks the application of acetic acid , soon after the tannin , caused , on two occasions , the pullulations gradually to subside , and finally to disappear , and then the disk resumed its original circular outline . I failed to produce this " redux " effect in the fowl ; and did not always succeed with human blood , probably because the change produced by the tannin had gone too far . The modification noted under the term " hooded " appearance depends , I believe , upon secondary conditions of concentration and quantity of the tannin-solution in comparison to the blood . When the hooded condition has been watched in the act of occurrence , it was noticed that the outer hood was shot out first , and instantly after this the highly refractive vesicular body made its appearance within . The contents of the hood ( excluding the vesicular body ) appeared usually to refract the light like the body of the cell , or even less strongly ; sometimes , however , more strongly . The effect of tannin did not cease with the production of the elevations just described . At first the cells and their projections preserved their elasticity ; but after a while ( a few minutes , or several hours , according to the proportions used ) the corpuscles and their projections became solid , and they could be cracked by pressure under the microscope like starch-granules . More slowly the same destruction overtook the corpuscles spontaneously ; and this significanit fact was observed in the course of it:-sometimes the cell ruptured before the projection , the latter persisting as a bright granule amid or near the debris ; sometimes , on the other hand ( in the horse ) , the projection broke up before the disk to which it was attached . In this latter case , the hood ( if there were any ) broke up first into a scattered nebula of granular appearance , and then the nucleolus-like body withini burst into three or four bright fragments ( fig. 2 , d ) . This train of events seemed to remove all doubt as to the complete isolation of the projection from the cavity of the disk . Last of all , the disk itself began to crack ; in a few days all my specimens were thus destroyed . In addition to magenta and tannin the following substalnces were tried , but they did not produce phenomena in the least analogous with the foregoing:-gallic acid , ferrocyanide of potassium , santonine , sulphate of magnesia , alcohol and water , solutions of carbolic acid , of atropine , morphia , iodine , sugar , gum , glycerine , and infusion of coffee . A solution of picric acid produced the appearance of a parietal particle like that brought out by magenta , except that it was not coloured . An exactly similar appearance was on one occasion observed in blood-corpuscles in the urine of a patient with acute Bright 's disease . When magenta was applied after the process of pullulation had taken place , the projections were found to take the dye strongly , and especially the vesicular body within the hood . By this proceeding beautiful and remarkable objects for microscopical examination were obtained . In the fowl , dace , and minnow the projection was tinted earlier than the central nucleus-probably from its more ready access to the pigment . The explanation of these appearances presents great difficulties , and in the present state of the inquiry can only be offered provisionally . The effect of the magenta-solution is not merely to tint , and so render visible a very minute body . In watching the effect of magenta , the first thing observed is that the natural yellowish colour of the disk is discharged , and that a faint rose tint is assumed in its stead . The disks at the same time lose their biconcave shape . The parietal macula is rather " brought out " than revealed , and the action of the solution is , to a very great extent , of a simply osmotic character . The action of the tannin-solution is likewise in the main of a similar nature , but modified in some very peculiar manner . Its first operation is to cause the corpuscle to enlarge byimbibition , and this goes on progressively until at length the cell is destroyed . If the solution be strong , this destruction supervenes at once . The tannin also unites with the cell-contents and coagulates them , imparting to the corpuscle , finally , a solid consistence . The conditions of the imbibition are disturbed by the previous application of magenta ; for no pullulation , or at most only traces , occurs when the corpuscles are treated first with magenta and then with tannin . The bearing of these observations on the current views respecting the structLLre of the vertebrate blood-disk is important . They seem to warrant the inferences drawni in the two following paragraphs : 1 . The exact identity of the appearances produced in the blooddisks of the ovipara with those observed in the mammalian corpuscles lenids strong support to the view that these corpuscles are homologous as wholes ; and that the mammalian blood-disk is not the homologue of the nucleus of the coloured corpuscle of the ovipara , as was conceived by Mr. Wharton Jones . 2 . The observations likewise lead to the belief that the envelope of the vertebrate blood-disk is a duplicate membrane ; in other words , that within the outer covering there exists an interior vesicle which encloses the coloured contents , and , in the ovipara , the nucleus . Dr. Ilensen* of Kiel had already in 1861 convinced himself , from wholly different observations , that the blood-corpuscles of the frog possess such a structure . On this view the blood-corpuscle is anatomically analogous to a vegetable cell , and the inner vesicle corresponds to the primordial utriele . The present observations indicate , by direct proof , a duplication at only one or , at most , two points in the blood-disks of mamimals and birds . Nevertheless certain appearanices , occasionally observed , favour the notion of a complete duplication ( fig. 1 , 6 ) . The aclmission of this hypothesis , however , scarcely removes the difficulties sufficiently to permit a tenable explanation to be offered of the appearanees described in this paper . Yet , as it may prove suggestive to some other inquirer , I will not suppress what appears to me the explanationi least open to objections . It might be conceived that the cells enlarged by imbibition , until at length the less distensible inmner membranie gave way , and permitted an extravasation of a portion of the cell-contents betweeni it and the outer membrane , its own continuity being in the meanwhile instantaneously restored by cohesion of the ruptured borders-t . In this way a microscopic drop of the cell-cointents would be lodged between the outer and inner membrane , and completely severed from the general cell-cavity . The peculiar modification spoken of as the " hooded " appearance might be due to imbibition of fluid between this microscopic drop and the outer envelope . The chief difficulties in the way of this explanation arise out of the differences of nature which appear to exist between the projection and the general cell-contents of which it is supposed to be a detached portion . The projection refracts light much more highly than thie cell-contents ; it also is deeply dyed by magenta , whereas the cellcontents are only very feebly so . In conclusion , it may be added that important advantages may be expected from the use of magenita in histological researches . Its inert chemical character , its prodigious tinting power , and its solubility in water eminently fit it for such a purpose . It will probably prove of especial use in bringing into sight objects which otherwise evade the visual organs from their absolute colourlessness and transparency , and from the equality of their refraction with the medium in which they exist .

112292

3701662

On Quinidine, and Some Double Tartrates of the Organic Bases

491

501

Proceedings of the Royal Society of London

John Stenhouse

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0103

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112292

10.1098/rspl.1862.0103

http://www.jstor.org/stable/112292

Chemistry 2

Agriculture

Chemistry

II . " On Quinidine , and some Double Tartrates of the Organic Bases . " By JOIIN STENHOUSE3 , LL. D. , F.R.S. Received February 23 , 1863 . Quinidine , as is well known , was first observed by Henry and Delondre , and likewise by Sertuerner , in what is called the " quinidine " of commerce , which consists chiefly of a mixture of quinidine , quinine , and resinous matters obtained from the mother-liquors of the suilpbate-of-quinine manufacture . Van Heijningen , however , was the first person who succeeded in separating quinidine , which he called ( 3-quinine , from this mixture and in obtaining it in a pure and crystalline state . He likewise ascertained that quinidine was isomeric with quinine . Its action on polarized light was studied by Pasteur , who observed that its solution in absolute alcohol produces deviation to thie right , while a similar solution of quinine produces rotation to the left ( Buchardat ) . As comparatively few of the salts of quinidine have hitherto been analysed , and those chiefly by Van Ileijningen , I was iniduced to prepare a few more of them , and likewise to examine the action of iodide of ethyl upon the alkaloid itself . I am indebted for the quinidine which I employed for this purpose to Mr. John Elliott Howard of Stratford . It was perfectly white , and consisted of large , well-defined crystals . Before using it , however , I recrystallized it out of alcohol . The quinidine gave a green colour with chlorinewater and ammonia , and the solutions of its salts all exhibited a fluorescent power almost equal to that of quiniine . A solution of its sulphate likewise yielded Hierapath 's so-called sulphate of iodoquinidine , crystallizing in long quadrilateral prisms possessing a deep garnet-red colour and the other well-known characters of that salt . *343 gramme of pure quinidine , dried at 1000C . , gave *9315 gramme carbonic acid and '238 gramme water . This corresponds to 74 04 per cent. of carbon and 7'71 per cent. of hydrogen . The formula C4L H24 N2 04 requires 74-08 and 7-4 per cent. Quinidine Platinum-salt , C401124 N2 04 , 21 Cl + Pt C1 , . -On the addition of bichloride of platinum to a solution of hydrochlorate of quinidine , an immediate precipitate takes place if the solution be cold and concentrated ; but if dilute or hot solutions be employed , it only crystallizes out after some time . It is very insoluble both in cold and in hot water , but crystallizes from boiling dilute hydrochloric acid in brilliant but irregularly-formed crystals , which decomposed when heated to about 2000 C. , evolving a peculiar aromatic odour somewhat resembling that of hawthorn..485 gramme of this salt , when dried at 150 ? C. , on ignition gave *1995 gramme of metallic platinum . This corresponds to 26f66 per cent. The formtula C40 24 N2 04 , 21 Cl + 2Pt Cl , requires 26 81 per cent. Both quinidine and its platinum-salt were first analysed many years ago by Baron Liebig ; but as he employed amorphous quinoidine for this purpose , Gerhardt supposes that he operated on a mixture of the three isomeric alkaloids , quinidine , quiniicine , and quinine . Quinidine Gold-salt , C40 2 , N , 0 , , 21 C1+ 2Au Cl,.-The goldsalt is prepared by dissolving quinidine in hydrochloric acid and adding excess of terchloride of gold , when it falls as a bright yellow powder . This salt appears to be decomposed by boiling with water , turning brown and apparently fusin , . It is therefore necessary to precipitate it in the cold . Well washed and dried in vacuo , oln heatino to 1000 it lost about -5 per cent. , probably hygroscopic water ; when further heated to 1150 , it fuised , turned browni , and began to decom . pose . '3575 gramme of gold-salt dried at 100 ? gave *14 gramme of metallic gold . This is equivalent to 39 15 per ceint . The formula o04 02 04 , 211 C+2Au C13 requires 39'2 per cent. Nihtrate-of-Silver Salt of Quinidinie , 0C4 , 12 , N 04 , Ag NO , . This was prepared by adding , nitrate-of-silver solution to any alcoholic solution of quinidine ; the mixture becamne semisolid from precipitation of the above salt in the form of minute n-eedles . These were thrown on a filter and thoroughly washed with cold water , in which they are scarcely at all soluble . The compound was then recrystallized from hot water slightly acidulated with nitric acid ; after filtration it separates , on cooling , in beautiful silky needles , which , on being freed from the mother-liquor and dried between bibulous paper , htave almost the lustre of metallic silver , such as is produced on igniting its organic salts . It partially decomposes every time it is recrystallized , but much more so when spirit is substituted for water , the solution becoming black from reduced silver . *40 1tgramme of the salt , dried at 100 ? , gave 115 chloride of silver , corresponding to '08656 gramme of metallic silver . This gives 21'59 per cent. According to the formula 020 " 24 N2 04 , Ag NO6 , theory requires 21 86 per cent. Mercuro-hydrochlorate of Quinidcine , C40H124 N204 , 21-1Cl+ Hg Cl. -On mixing solutions of hydrochlorate of quinidine and chloride of mercury , the above salt is precipitated as a white powder . It is slightly soluble in cold water , much more so in hot , especially when acidulated with hydrochloric acid ; but it cannot be conveniently crystallized from this menstruum , as it sometimes separates in resinous masses . By far the best solvent from which to crystallize is boiling alcohol , in which it is readily soltuble , separating in nacreous scales as the solution cools . It fuses at 100G under water , but not when dry . '626 gramme of the above salt , dried at 1000 , yields *507 chloride of silver , which gives of chlorine 20'04 per cent. The formula C40 1124 N2 04 21101 + Hg Cl requires 20'00 per cent. Zinco-hydr-ocklorate of Quinidine , C01H24 , N20,4 21 HC1+2ZaC1 . A moderately strong solution of chloride of zinc , containing a slight excess of hydrchloric acid , is poured into an alcoholic solution of quinidine , when the double salt precipitates as a granular powder . It is very slightly soluble either in hot or in cold water , but dissolves readily in dilute hydrochloric acid and in spirit of 50 per cent. , from which latter it crystallizes in a form very similar to that variety of carbonate of lime known as " dog-tooth " spar . The specimen analysed was crystallized from dilute hydrochloric acid and dried at l00 ? . -447 gramme gave *4825 gramme chloride of silver , equal to 1193 of chlorine . This corresponds to 267 per cent. of chlorine . The formula C40 1124N 2 04 211 Cl+2Zn Cl requires 26X65 per cent. Basic Chloride-of-Zinc Salt , C41124N2 04 , HCI+ZnC1.-The neutral salt described above appears to lose a portion of its hydrochloric acid and chloride of zinc after repeated crystallizations . A solution of the salt so treated deposits , upon slow evaporation , crystals of considerable size , consisting of hexagonal plates and 'prisms . After drying at 1000 , these were sul)mitted to analysis ; the zinc and quilnidine were precipitated together by carbonate of soda , and asfter washing well with water , the quinidine was removed by boiling alcohol ; the residuary oxide of zinc was them again washed with water , and ignited in the usual way..7335 gramme of the salt yielded *0680 grarnme of oxide of ' zinc , equivalent to *05456 of metallic zinc , or 7-44 per cent. The formula C 40 -1 N2 04 , 2H C1 +2 Zn Cl requires 12 2 per cent. The formula C40 H121 N2 O , , E Cl + Zn Cl requires 7-58 per cent. Oxalate of Quinidine , C040 1-2 . N2 01 I-I C2 OV 11O.-The oxalate of quinidine is formed by exactly nieutralizing oxalic acid by quinidine . It consists of very small brittle crystals , which are almost insoluble in cold , but comparatively soluble in hot water , from which it crystallizes again on cooling . After being purified by two recrystallizations and dried at 1000 , it was submitted to analysis . -206 gramme gave -502 carbonic acid and *133 water ; this corresponds to 66 45 per cent. of carbon and 7-17 of hydrogen . The formula C40 1124 N204,0 1020 04+110 requires 66-67 per cenit . carbon and 6-88 per cent. hydrogen . This is evidently , therefore , the neutral oxalate , and differs wholly in appearance and properties from the acid oxalate , C00 H , 2 04 , 120408 + 2Aq , obtained by Van Ileijningen . Picrate of Quinidine.-Quinidine dissolves in a boiling and not too concentrated solution of picr'ic acid ; but it separates on cooling , not in crystals , but as a resinouis mass . When dissolved in hot alcobol , it is deposited by evaporation of the solution in resinous nodules , thus very closely resemlbling , the corresponding salt of quiiiiine . Action of Iodide of Ethyl on Quinidine.-Iodide of ethyl attacks quinidine very readily , so that if the two substances ( the former being in excess ) be heated together in a flask furnished with a perforated cork and lonw tube to condense the iodide of ethyl , combination quickly ensues , and in half an hour the reaction is complete . Water is then added and the excess of iodide distilled off , the residue dissolved in diluite alcohol , filtered , and allowed to crystallize . On cooling , the solution becomes semnisolid , from separation of the iodide of ethyl-quinidine in the form of long silky needles . These are well washed with cold water , in which they are almost insoluble , and then recrystallized from boiling dilute spirit , washed , dried at l00 ? , and submitted to anialysis . -5600 gramme yielded -2735 gramme iodide of silver , equivalent . to -1478 of iodide , or 26 39 per cent. The formula 410 2JN20 4}J requires 26-46 per cent. of iodine . Platinum-salt of Ethyl-quinidine , Co II N 0 ? I C1 } 2Pt C12 . 4 IL 2 t24 11c On treating the foregoing iodide with chloride of silver the chlorine replaces the iodinie , tand we obtain chloride of ethyl-quinidine in solution and iodide of silver . The latter is separated by filtration , and the solutioni , niow free from iodine , is precipitated by the addition of bichloride of platinum . The platinum-salt separates as a paleyellow powder , almost insoluble either in hot or in cold water , and but sparingly soluble in boiling dilute hydrochloric acid , from which it separates almost completely on cooling . The specimen analysed was simply washed with water and dried at 100( . *537 gramme gave 137 metallic platinum , corresponding to 25 61 per cent. 2N The formula C 11H N 04C4 H11c0 2 Pt C12 requires 25'86 per cent. Hydrated Oxide of Ethyl-quinidine . On treating the iodide of ethyl-quinidine with oxide of silver in slight excess , a solution of the hydrated oxide is obtained . It is very bitter to the taste , readily attracting carbonic acid from the air , and is of course highly alkaline to test-paper . On evaporation it does not crvstallize . Action of Iodlide of E thyl on Ilydrcated Oxide of Etthyl-quinidine . -When iodide of ethyl and a strong solution of hydrated oxide of ethyl-quinidine are made to react upon each other in a sealed tube at the temperature of 100 ? , a mass of crystals are produced after digestion for about an hour . These were extracted from the tube , washed with a little water , dried between folds of filtering-paper , and recrystallized from dilute alcohol . On analysis , they proved to be nothing more than reproduced iodide of ethyl-quinidine . *4435 gramme gives 2165 of iodide of silver , correspolnding to *117 of iodine , or 26-38 per cent. The formula C4 215 2"4 } I requires 26A46 per cent. From these experiments it appears that quinidine contains no replaceable hydrogen , and in this respect it agrees with quilline and cinchonine , the alkaloids with which it is associated . Double Tartrate of Quinidine and Antimony , C40 121N2 04 11 C IH 0 SbO , 8 '0 120 When an excess of quinidine in powder is added to a cold saturated solution of tartar-emetic , and heat applied so soon as the mixture begins to boil , the quinidine pretty rapidly dissolves , whilst at the same time a quantity of oxide of antimony is precipitated . The solution is filtered whilst boiling , and on cooling the double tartrate of quiniidine and antimony is deposited in very lonig fine silky nleedles , often more than an inch in length . Any excess of quinidine which has been employed , together with the oxide of antimony which has been precipitated , remains upon the filter . The double tartrate is but slightly soluble in cold water , but dissolves easily in hot , from which it may readily be crystallized . It is also very soluble in boiling spirit of wine , from which it is deposited , almost completely on cooling , in tufts of slender needles . The douible tartrate of quilnidine and antimony was very carefuilly examined for potassa by precipitating the antimoniy by means of suiphuretted hydrogen ; it then left lno perceptible residue on ignition , and a drop of bichloride of platinum gave no precipitate . It therefore could not contain potassa . Analysis.-Dried in vacuo over sulphuric acid , it retains , appareitly uncombined , from 5 to 1 per cent. of water , which it loses at the temperature of 1000 . The salt dried in vacuo gave the following results I. 0 3850 gramme gave 6750 gramme carbonic acid and 1780 gramme water . II . 2375 gramme gave 4175 gramme carbonic acid and 1270 gramme water . III . *5380 gramme gave *1398 gramme of antimolnious acid , Sb 04 . The compounds , after two recrystallizations and drying at 1000 , gave the following results : IV . *5815 gramme gave 1P0100 gramme carbonic acid and 2550 gramme water . V. '5110 gramme gave *893 gramme carbonic acid and -224 gramme water . VI . *7195 gramme substance gave *1949 gramme tersulphide of antimony . This was dried in vacuo and contained 1P3 per cent. of water ; therefore 17195 gramme is equal to *7101 dried at 1000 . Theory . -I . I. II . IV . V. C48 = 288 . 47-28 47-8 47-94 47-36 47-66 H29 = 29 . 4176 513 5 94 4-87 4-87 N2= 28. . 4596 ? o0 8 144..2363 Sb = 120-3 19-74 2053 1961 609-3 100-006 In order to ascertain that the residue upon the filter , in addition to undissolved quinidine , contained precipitated teroxide of antimony , it was washed with hot alcohol and dissolved in strong hydrochloric acid . This solution gave the characteristic reactions of anti . money with water and sulphuretted hydrogen . The mother-liquor , which was quite neutral to test-paper , and from which as much as possible of the quinidine-salt had been separated by concentrationi , was treated by sulphuretted hydrogen to separate the antimony , and was tested for potassa and for tartaric acid , both of which it was found to contain . The reaction may therefore be represented by the following equation:2 Sb ? 2 }C II4 012+ 040 " -121 N2 04+'l0 C40 , H21 N2 0411 c1 ? K c142 ? b. Sb 0 , C8ifI012 + 84 8 24 12 +b 03In order to colnfirm this view of the comiiposition of the salt , some acid tartrate of quinidine was prepared by taking a solution of tartaric acid , dividing it equally into two portions , nieutralizing the one with quinidine , and then adding the other . This solution was then boiled for some hours with excess of freshly-precipitated oxide of antimony , filtered , and allowed to cool , when the same beautiful salt made its appearanice , idelntical in all its properties with the compounld formed by boiling tartar-emetic with quinidine . It will be obvious from these results that tartar-emetic , when boiled with quinidine , undergoes a somewhat sinigular and unexpected decomposition , neutral tartrate of potassa and the double tartrate of quinidine and antimony being , formed , while one-half of the antimony of the original salt is precipitated as oxide . From this and the subsequently to be described double tartrates , the tersulphide of antimony which is precipitated has a light yellow or pale orange colour , and , after being lolng washed with boiling water , still contains some of the base , probably in the state of a salt . This portion of the alkaloid may , however , be abstracted from the tersulphide of anltimony by digesting it with hot alcohol . In order to confirm the fact that the compound contained quinidine and not -an altered base , as it may be observed from the analyses given above that the carbon in the double tartrates is somewhat too high , the antimony was removed from a portion of the salt by means of sulphuretted hydrogen , the base precipitated by amnmonia , well washed with water , and crystallized out of spirit ; it was them obtained with the usual crystalline form assumed by quinidilne , viz. 4-sided prisms , and gave the characteristic reactioni with chlorine-water and ammonia . A platinum-salt also was prepared in the usual way , which , recrystallized from dilute hydrochloric acid , gave the following analytical result : *411 gramme gave *1075 gramme metallic platinum ; this corresponds to 26 16 per cent. C E24 N O , 2H C1 +2 Pt Cl requires 26-81 per cent. The Tartrate of St2ychnine and Antimony , GII1NO H ~CH 0 42 22 24 Sb02 8 It 212 was likewise prepared by adding strychlline to a boiling solution of tartar-emetic . The same solution of the alkaloid and precipitation of oxide of antimony were observed as in the case of quitnidine . Oa cooling , the double tartrate was deposited in very brittle needles , much less soluble in water than the corresponding quinidine-salt . It occasionally crystallizes in leafy plates . The following results were obtained in the analysis of the salt dried at 100 ? :I . *3365 gramme gave *6005 gramme carbonic acid and 133 gramme water . II . *6000 gramme gave *148 gramme Sb 04 . III . 5495 gramme gave *1375 gramme Sb 0 , . Theory . ---I~~ . It . MI . c0o = 300..48 44 48*7 127 = 27. . 4-36 4-39 N2 = 28. . 4-52 018 = 144. . 23 26 Sb = 120(3. . 19'42 19-47 19'76 100 00 This corresponds with the formula C42 1-122N2 04 11 ~CH 0 Sb ? ? 84 12 ' Some of this salt was also decomposed by sulphuretted hydrogen and treated in the manner described in the case of the quinidine . It was then obtained in quadrilateral prisms with pyramidal summits , and gave the usual reactions with sulphuric acid and bichromate of potassa . A platinum-salt of the recovered alkaloid was also prepared and analysed . Dried at 1000 , -630 gramme gave *1150 grainme of mietallic platinum . This is equivalent to 18 26 per cenit . The formula C 42 1122 N204 , 11 1 , Pt Cl12 requires 18527 per cent. Taritrate of Brucine and Antimony , 04 , lla N2081 }C WA 0 Sb02 j84 12 ' The salt was prepared in a precisely similar manner . It formed short and excessively brittle crystals . Analysis seems to assign to this salt the same conistitution as those containing quiniidine and strychnine , as may be seen by the following results : I. *284 gramme brucine compoulnd gave 5000 gramme carbonic acid and *1 185 gramme water . 1I . *4845 gramme yielded These numbers corresponid to the formula C48 H 22N SbO22 C40 17 NO8 H cno SbO 08 81 12 ' Theory . , ~~ ~ ~~1 . Ir . C48 3 288. . 46'43 46 46 1-122 = 22. . 354 31676 N= 14..2-2 . Sb = 120 3. . 19'39 -l985 022 =1 76. . 28'37 620'3 99'98 It is very remarkable that corresponiding crystalline double tartrates are not obtained by boiling tartar-emetic with many of the other organic bases . The following have been tried , but unsuccessfully : Quinine . Aniline . Cincholiine . Theimie . Cinchonidine . Piperine . Furfurilie .

112293

3701662

Researches into the Chemical Constitution of Narcotine, and of Its Products of Decomposition.--Part I. [Abstract]

501

505

Proceedings of the Royal Society of London

A. Matthiessen|George Carey Foster

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112293

http://www.jstor.org/stable/112293

Chemistry 2

Optics

Chemistry

I. " Researches into the Chemical Constitution of Narcotine , and of its Products of Decomposition."-Part I. By A. MATTHIESSEN , F.R.S. , and GEORGE CAREY FOSTER , B.A. Received February 26 , 1863 . ( Abstract . ) An abstract of a considerable portioni of this paper has already appeared in the form of a preliminary notice* of the first results obtained . The most important additional facts now communicated are the following : The anialysis of five additional specimens of narcotine has confirmed the accuracy of the formula 22 H23 NO7 , which the authors adopted for this base in their previous notice . The mean results of all their analyses ( ten determinations of carbon and hydrogen and four determinations of nitrogen ) give for the composition of narcotine , Carbon ... ... ... ... ... 63-78 Hydrogen . 576 Nitrogen ... ... .- . 3-32 Oxygen.27'14 100-00 The formula 22 H23 NO ' corresponds to Carbon ... ... ... ... . . 63 92 Hydrog , en ... ... ... ... . 557 Nitrogen ... ... ... ... 3.39 Oxygen.27 12 100-00 The authors had previously stated that mneconin , opianic acid , and hemipinic acid were all decomposed by boiling concentrated hydriodic acid , with evolution of iodide of methyl. . They now find that hydrochloric acid acts similarly on these bodies , evolving with each of them chloride of methyl . They suggest the name hypoyallic acid for the acid 0 11 O , formed by the action of hydriodic acid on hemipinic acid* , in order to recall the fact of its containing one atom of oxygen less than gallic acid , C ' H16 O5 . They obtained the same product by the prolonged action of hydrochloric acid on hemipinic acid ; but by a shorter action an intermediate product was obtained , which , according to a single analysis , appears to contain H8 H8 0 Calculated . Found . -C ... ... ... . 96 ... 57'14.5665 H8 8 ... ... . . 4-76 ... ... . . 517 4 ... 64 ... 3810 ... . . 8180_4 ... ... . . 68 . 10000 This substance is an acid of much greater stability than bypogallic acid ; it crystallizes in long , thin , transparent prisms , which are anhydrous , and are almost insoluble in cold water , slightly soluble in boiling water , but dissolve more readily in alcohol and ether . At X Proc. Roy . Soc. vol. ; i. p. 58 . about 200 ? C. this acid sublimes unchanged , and it may be heated to 245 ' without melting or becoming coloured ; it dissolves in strong sulphuric acid , and is precipitated urnaltered on addition of water . It gives no coloration with sesquichloride of iron ; with nitrate of silver it gives a white precipitate which slowly blackens on boiling . Its formation from hemipinic acid may be expressed by the equation C"O110 0I1 C+=E0O2++C GE13 Cl+C8 118 0 ' . Hemipinic acid . This substance has the composition of methyl-hypogallic acid ; but its great stability , as compared with hypogallic acid , makes it appear improbable that such is its true constitution . Nascent hydrogeni evolved from sodium-amalgam and water , or from zinc and dilute sulphuric acid , converts opianic acid into rneconin , C"O 1-0 " ( } ' + 1_12 C"10 11 " '+ 112 0 Opianic acid . Mecoriin . Hemipinic acid is unaltered by nascent hydrogen . Aqueous hydrochloric acid decomposes cotarnine at 140 ? C. into chloride of methyl , and a substance which the authors call hydrochlorate of cotarnamic acid and represent by the formula " J1 Hl3 NO ; , HCl , supposing it to be formed according to the following equation : 12,113 NO3 + 11 ' 0+2 IICl=C " l13 NO ' IIC1 + CH3 Cl. Cotarnirie . Hydrochlorate of cotarnamic acid . The formula proposed does not agree perfectly with the results of several anialyses , which are accordant among themselves , and is given as provisional only . Calculated . Found rw ~~~~~(meanl ) . C " . 132 ... . 1 50'87 ... . 49-98 H".14 ... . 540 ... . 5.70 N 14 ... . 5 40 571i 0 ' 64 ... . 24-65 ... . 24-61 Cl ... 35 ... . 13 68 ... . 1 4300 Cll 11NO1,3C4 ... . 259 5 ... . 100 00 ... . 100 00 This body crystallizes in small silky nieedles of a pale yellow colour ; it is partially decomposed , losing hydrochloric acid , when dissolved in pure water , but dissolves unchanged in water containing a trace of free hydrochloric acid . Alkalies , or alkaline carbonates or sul . phites , throw down from the aqueous or acid solution an oran , gecoloured granular precipitate ( cotarnamic acid ? ) free from hydrochloric acid ; this precipitate dissolves in excess of alkali , giving a solution which quickly becomes dark brown by exposure to air ; with hydrochloric acid , it regenerates the originial crystalline compound ; it dissolves slightly in water , with a bright oraiige colour that is visible even in very dilute solutions . The slightly acidulated solution of the hydrochlorate is pale yellow when pure , but acquires a deep . green colour in the air . A few drops of uitric acid added to a hot solution cause it to appear of an opake crimson colour by reflected light , though the liquLid is still transpareint when examined by transmitted light . Nitrate of silver added in quantity more than sufficient to precipitate the chlorine is quickly reduced . The compound acquires a fine crimson colour when evaporated nearly to dryness on the water-bath , with a slight excess of dilute sulphuric acid . Hydriodic and diluted sulphuric acids decompose cotarnine at a high temperature in the same way as hydrochloric acid . The products so formed have not been isolated , but were converted into hydrochlorate of cotarnamic acid . The authors conclucde by offering some suggestions towards the interpretation of the results they have obtained . Only the most important points discussed by them will be briefly indicated here . They suppose that when opianic acid is converted into meconin by the action of nascent hydrogen , or into meconin and hemipinic acid by the action of potash * , a substance containing C " II " 0 ' may possibly be the immediate product of the reaction , and that this body-bearing the same relation to mieconin that glycol , C ' IF ' 02 , does to oxide of ethylene , C E4 0 , or maninite , C. 1I O ' , to mannitan , C'1 -may give rise to meconin by subsequent loss of the elements of water . Making this supposition , the two reactions in question may be represented by the equations ( 1),. . 10uClo 45 + I2 =cl " O12 0 Opianic acid . IHypothetical hydrate of meconin . ( 2 ) 2 ( C " 1I10 0 ' ) +H0= C"O H12 0 ' + Co 1100 o6 Opianic acid . Hypothetical Hemipinic hydrate of meconin . acid . Thus viewed , both transformations appear strictly analooous to the known transformations of oil of bitter almonds and many other substanices ; e. g. , ( 1 ) . 7 H. C 10 , +1 -2 _ 407 I9 0 ( Friedel ) Oil of bitter Benzylic almonds . alcohol . ( 2). . 2(C7 1160 ) + 112 o0 C HI 0+ ? C EIs 02 ( Cannizzaro ) Oil of bitter Benzylic Benzoic almonds . alcohol . acid . and may be regarded as supporting the views of Berthelot , who has suggested that opianic acid ought to be classed as an aldehyde rather than as a true acid . With regard to the constitution of hemipinic acid , the authors suppose that it may be a dimethylized derivative of a bibasic but tetratomic acid , c8 IF 06 ( analogous to tartaric acid , Co 116 06 ) , the two atoms of methyl occupying the places of the two atoms of hydrogen , which , though outside the radical , are incapable of being replaced by metals : hemipinic acid would thus be comparable to Wurtz 's ethyllactic acid , the body at one time described by Butlerow as valerolactic acid . An analogy is further pointed out between the derivatives of malic acid and the substances obtained from cotarnine . This alnalogy becomes apparent on comparing the two following series of formulae Cotarnic acid el . l H12 C0 ' 11 O ' Malic acid . ( ? ) Cotarnamic } . f1 H13 NO ' C " HI NO4 Aspartic acid . lIydrochlorate ~ ' ldohoaeo of cotarnamic } C " HI " NO'6 . CI1 C 11HN4 . HCi { Hydrochlorate of acid ... ... .{ aspartic acid . Cotarnine , or f Malanile , or phemethyl-cotarC 0 " I11 ( CH-3 ) NO3 C 114 ( 06 1 ) NO ' nyl-malimide nimide ... . J The authors initend to colntinue their experiments .

112294

3701662

Postscript to a Paper Read January 15, 1863, on the Formation of Fibrin from Albumen

505

507

Proceedings of the Royal Society of London

Alfred Hutchison Smee Jun.

fla

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112294

http://www.jstor.org/stable/112294

Chemistry 2

Physiology

Chemistry

II . Postscript to a Paper read January 15 , 1863 , " On the Formation of Fibrin from Albumen . " By ALFRED HUTCHISON SMEE , Jun. Communicated by ALFRED SMEE , Esq. , F.R.S. Received March 2 , 1863 . Since the paper was read before the Royal Society the following additional facts have been elicited . Fibrin was obtained from 1863 . ] 505 serum when subjected to oxygen gas , when acetic acid was added to it , although another portion of the same serum had refused to yield it without that addition . In this experiment the acetic acid should be added until the serum is either neutral , or produces a slightly acid reaction on test-paper . Care must be taken in these experiments to prevent the temperature rising too high , for a coagulation then takes place . If blood-cells be present in the serum , the addition of acetic acid attacks the cells in preference to the alkalies of the serum ; and on subsequent exposure to a temperature of 100 ? F. during the period it is under the influence of oxygen , the whole is transformed into a semisolid mass . It is a curious fact that serum which has been placed on a dialyser for the removal of the salts by Graham 's method was not improved in its power of producing fibrin , over serum which had not been submitted to that treatment previous to its oxidation . On the other hand , albumen purified from salts by Graham 's method , and then subjected to the influence of oxygen , yielded the largest amount of fibrin . By this method it is most probable that I should have been able to have transformed the whole of the albumen into fibrin , had not an accident unfortunately brought the experiment to a termination . Nevertheless , although the experiment was not continued long , half the albumen was changed into fibrin . When experimenting upon albumen nearly free from alkalies and alkaline salts , great care must be taken to keep the temperature as low as possible . I found that a temperature between 80 ? and 90 ? F. was the best , for above 98 ? the albumen had a very great tendency to coagulate . WThen albumen was placed in a tube which contained about an equal bulk of oxygen , and in which a platinized platinum wire had been inserted extending the whole length of the tube , to facilitate the action of the oxygen on the albumen , and which tube was subsequently sealed and placed in a water-bath of 98 ? F. , no fibrin made its appearance even after the lapse of 36 hours , but in its place a small quantity of an amorphous material subsided to the bottom of the tube . When , however , a tube of similar size was filled with albumen having free access to the air , and then placed on the same water-bath for an equal length of time , on the surface of the albumen which this tube contained small masses of 506 fibrin were formed , which had an appearance identical with that of blood-fibrin under the microscope , giving a conclusive proof to my mind that , during the formation of fibrin by the action of oxygen on albumen , a volatile constituent is formed and carried off by the excess of oxygen which passes into the albumen in solution . The following are the chief physical and chemical properties of the fibrin artificially formed by the action of oxygen on albumen : It has a lighter specific gravity than albumen , being always found floating on the surface of the albumen , provided it is free and not entangled or attached to the side of the vessel or platinized platinum wire that has been inserted in the albuminous solution . It has a fibrinated appearance under the microscope , and is capable of being teased out into filaments in the same manner as bloodfibrin . Acetic acid completely dissolves it after some time . Soda and potash cause it to swell up and dissolve . Concentrated solution of ammonia , after the lapse of some hours , causes the fibrin to swell up in a gelatinous mass , similar to that which occurs when blood-fibrin is submitted to the same reagent . A hot or cold solution of nitrate of potash does not dissolve it when it is digested in that menstruum for some hours . With Millon 's test it becomes of a brick-red colour . With nitric acid a bright yellow colour became visible . Fibrin heated with hydrochloric acid gave a blue colour , and subsequently dissolved , giving a blue tint to the liquid . An acid solution of acetate of lead caused both blood-fibrin and fibrin artificially prepared to swell up and become translucent after digestion for a certain period .

112295

3701662

On Diffusion of Vapours: A Means of Distinguishing between Apparent and Real Vapour-Densities of Chemical Compounds

507

511

Proceedings of the Royal Society of London

J. A. Wanklyn|J. Robinson

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0106

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112295

10.1098/rspl.1862.0106

http://www.jstor.org/stable/112295

Chemistry 2

Thermodynamics

Chemistry

III . " On Diffusion of Vapours : a means of distinguishing between apparent and real Vapour-densities of Chemical Compounds . " By J. A. WANKLYN and J. ROBINSON , Esq. Communicated by Dr. FRANKLAND . Received March 10 , 1863 . The density of the vapour given off when a chemical compound is heated is not necessarily the vapour-density of that chemical com pound ; sometimes it is only the mean density of the products of decomposition . Some of the best-known substances , such as hydrated sulphurous acid , ammoniacal salts , and pentachloride of phosphorus , suffer decomposition when they are vaporized , and thus have an apparent vapour-density , which is in reality nothing more than the mean density of the products of their decomposition . We recognize such cases-in which the apparent is not the real vapour-density-by making a diffusion-analysis of the vapours . This method of solving questions of the kind was proposed by one of us two years ago* . In carrying it out practically , it was resolved from the first not to diffuse through a porous diaphragm , but to recur to Graham 's original method , namely , to let our vapours diffuse through a simple aperture or through a short tube . Independently of the experimental difficulties attending the use of a porous diaphragm at high temperatures , there is a fatal objection to it , founded upon the inconclusiveness of the results obtained in such a way . Our resolve to avoid porous substances was not by any means shaken by Pebal 's memoirt on the diffusion of chloride-of-ammonium vapour through asbestos ; for what is more likely than that a finely-divided silicate ( a salt of an acid of indefinite capacity of saturation ) should decompose ammoniacal salts at elevated temperatures ? The apparatus used in our experiments is of the sinplest kind . It is represented in the drawing , and consists of two glass flasks , the necks of which do not fit air-tight : the narrow tube proceeding from the upper one is fused to the flask . The lower flask is for the reception of the vapour to be operated upon ; the upper flask is for the atmosphere into which the vapour is to be diffused . The atmoPlayfair and Wanklyn on Vapour-densities , Transactions of Roy . Soc. of Edinburgh , 1861 , vol. xxii . part 3 . p. 458 . In this paper it was proposed to extend to vapours what had previously been applied to gases . One of the earliest , perhaps the earliest example of a precise diffusion-analysis of a gas was given by Frankland in his research upon the isolation of ethyl ( see Quart . Journ. Chem. Soc. vol. ii . p. 285 , 1850 ) . After describing his diffusion-apparatus and its use in the case of ethyl , Frankland proceeds , " This method might in almost every case be employed with advantage to determine whether or not any specimen of gas be simple or mixed . " t Ann. de Ohim . et de Phys. January 1863 . sphere of dry air , or other suitable gas , is kept constantly renewed by the transmission of a slow stream of gas , which enters the upper fbntodI bb / r flask by the narrow tube above , and passes out by the space between the two necks , which , as we have said , do not fit air-tight . When in use , the whole apparatus is kept at a temperature above the condensing-point of the vapour by means of an air-bath . After a diffusion has gone on for a sufficient length of time the apparatus is allowed to cool , and the contents of the lower flask are analysed , by which means it is seen whether diffusion has effected any alteration in the composition of the vapour . We have used a lower flask of about 500 cubic centimetres capacity , with a mouth 10 millimetres in diameter ; the capacity of the upper flask was 100 cubic centimetres . The first substance taken for experiment was sulphuric acid , which is converted at high temperatures into vapour of sulphuric anhydride and vapour of water . Inasmuch as vapour of water is lighter than vapour of sulphuric anhydride , the former should diffuse more rapidly than the latter . Accordingly , the residue after diffusion should be richer in sulphuric anhydride than the acid before diffusion . In one experiment we took an acid composed of 95 Mono-hydrated sulphuric acid . 5 Water . 100 1863 . ] 509 2o After diffusion for an hour at about 520 ? C. , the residue was composed of 60 Mono-hydrated sulphuric acid . 40 Sulphuric anhydride . 100 In another experiment we took an acid containing 99 Mono-hydrate . 1 Water . 100 and after diffusion for a shorter time at 445 ? C. found the residue to consist of 75 Mono-hydrateo 25 Anhydride . 100 In both cases the residues after diffusion fumed strongly on exposure to the air , and consisted partly of crystals and partly of liquid . The substance next submitted to diffusion was pentachloride of phosphorus , which is decomposed by heat into terchloride and free chlorine . The pentachloride which we used gave no reaction with iodide of potassium and starch , and therefore contained no free chlorine ; it gave no precipitate with corrosive sublimate , and therefore contained no terchloride of phosphorus . An analysis of it gave Percentage of chlorine=846 7 The formula requires ... 85 13.In one experiment we diffused into carbonic acid gas* for threequarters of an hour at about 300 ? C. , and afterwards dissolved the contents of the lower flask in water , and precipitated with corrosive sublimate , with the addition of a little hydrochloric acid . '0175 gramme of calomel was obtained . In another experiment ( also into carbonic acid ) the time of diffusion was two hours , temperature 300 ? C. , quantity of calomel obtained '0285 gramme . These two results leave no doubt as to the existence of terchloride of phosphorus in the residue after diffusion ; for the reduction of corrosive sublimate to calomel cannot be otherwise explained . Moreover , the presence of free chlorine in the diffused gases was shown by the reaction with iodide of potassium and starch . We are continuing this research , and hope to lay before the Society the results of an examination of the most prominent cases of so-called abnormal vapour-density .

112296

3701662

On a Simple Formula and Practical Rule for Calculating Heights Barometrically without Logarithms

511

517

Proceedings of the Royal Society of London

Alexander J. Ellis

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0107

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112296

10.1098/rspl.1862.0107

http://www.jstor.org/stable/112296

Formulae

Astronomy

Mathematics

IV . " On a Simple Formula and Practical Rule for calculating Heights baronietrically without Logarithms . " By ALEXANDER J. ELLIS , B.A. , F.C.P.S. Commnunicated by Dr. NEIL ARNOTT , F.R.S. Received February 23 , 1863 . The following formula and table for calculating heights barometrically without logarithms will be found to give the same results as Laplace 's formula up to 30,000 feet , andc the table can be readily extended if required . Let L degrees be the mean latitude of the two stations , I =2 6257cos2L , G=1+0 0026257cos2L , R=20888629 , the number of feet in the earth 's radius . At the lower station . H feet , its height above the sea , H"t=12 H R , B units of any kind , height of barometer , uncorrected , Bt.1 1 % 5 ) 3 3 . $p3 3 , corrected , A-deg . Fahr. , A ' deg. Cent. , A"l deg. Reaum . , temperature of air , M , , 7}Mr , , I , Mit , , , , P , , of mercury . Jt the upper 8tation . It , It " , 6 , bs6a ) a , a " M , m , m " in the same sense . Then h-H1= [ 52400 B-b + e-2-35 . ( M-m ) ] 836 +A a B+6~~~~~~0 + 001 . ( h-Hi ) l+h"-H " , . X O. ( a ) where M-mk=0 , when B , 6=B ' , b6 , and 2 35 ( M-m)=4.23 . ( Ml-mr)=5'29 . ( M1'-m"l ) 836+A+a-500+A'+a ' 400+A"f+a"t 900 500 400 The numbers c , 1 , hft , Hlf are to be taken from the table on the next page , as will appear by the following examples . 2o Ex. 1 . Height of Mont Blanc above Geneva from the observations of MM . Bravais and Martins , August 29th , 1844 . Af 193 B 729-65 mm. M ' 18 6H 1335-33 af7-6 b 424 05 min4-2 L 46 500 0 B+b 1153170 22 81 O09 511-7 B-Z 305 60 x4 23 x 142 p 96-4 q 13 305-6x52400 + 1153 7 141l181 x 511 7 . 500 =13880'0 =14448 5 272-9 c for 1300 10 8 A " for 15000 1 61-6 diff. for 880 12 diff. for 800 ' 103 6 -p P9 -H " for 150l , E 141181 18-7 -q h-H=14459 0 difference of level . Result by Laplace 's formula 14459-4 . Table of Corrections . Feet . c Diff. for h " + Diff. for LLI 100 feet . H"l100 feet . _+ 11000 030 06 0 05 0 ? 0 ? 00 900 2265 2000 + 0-3 0-20 0-20 0-2 5 85 2-61 3000 2-3 0 -41 0-43 0-02 10 80 2-49 4000 6-4 0 72 0477 0 04 15 75 2229 5000 13-6 72 P2 0-04 20 70 2-03 6000 2434 0854 1 72 0056 21 69 iP97 7000 39-8 2-07 2-35 0'07 22 68 1-91 8000 60 5 2768 3-06 0-08 23 67 1P84 9000 87-3 3-35 3-88 0 09 24 66 1-77 10000 120-8 4-16 4.79 0 10 25 65 1P70 11000 162 45 04 5 79 0 11 26 64 1-63 12000 212-8 6-01 6-89 0-12 27 63 1-56 13000 272 9 707 0'13 28 62 1-48 14000 343-6 8-27 9 38 0 14 29 61 1340 15000 426-3 8 55 10 77 0.14 30 60 1-33 16000 521-8 9-55 12-26 0 16 31 59 1-24 17000 631-6 10-98 13-84 0-16 32 58 1-16 80 ? 00 675566 1240 15 51 0'17 33 57 1P08 19000 8997 1 14635 17-28 0 18 34 56 0.99 20000 1059-6 16-05 19-15 0219 35 55 0.91 21000 1239-9 20123 21 11 0 21 36 54 0-82 22000 1442-2 223 23-17 0-21 37 53 0173 23000 1667-8 22556 23133 0-22 38 52 0-64 24000 1919-2 25714 27-58 0'23 39 51 0 55 25000 2198-8 27396 29792 0 24 40 50 0 46 26000 2508-8 31400 32-36 0 24 41 49 0 37 27000 2852 3 37-96 34'90 0n26 42 48 0-27 28000 3231 9 41399 37-53 0-27 43 47 0.18 29000 3651*8 41-99 40-26 0-28 44 46 0 09 30000 4115-4 4636 4309 45 45 000 ... ... .409.45 45.00 Ex. 2 ' . Rush 's balloon ascent , September 10th , 1838 ( see Meteorological Papers by Admiral FitzRoy , No. 9 , p. 19 ) . A 60 Bt 30 496 in . E0a5 bf 10-830 L 52 836 B ' ? + ' 41b326 1 0-64 901 B'--6 ' 19 666 x 27 q 17-3 19 666x52400 ? * 41-326 27116x901 . 900 =24935-8 =27146 1 2198'8 c for 25000 34'9 kf for 27000 1814 diff.for-65 03 diff. for 100 27116-0 1821-q h-11=27164-0 Laplace 's formula gives the same result . As the British highlands do not exceed 5000 feet in altitude , and lie near the parallel of 561 north latitude , the corrections will nearly destroy each other . The following simple rule will therefore suffice for calculating all British heights : " Multiply the difference of the barometers by 524 , and divide the product by the sum of the barometers , retaining three decimal places . Multiply this quotient by the sum of the temperatures of the air increased by 836 , and divide the product by 9 , keeping one decimal place . For aneroid and corrected mercurial barometers , the quotient is the height in English feet . For uncorrected barometers , subtract 21 times the difference of the temperatures of the mercury . " Ex. 3 . Height of Ben Lomond ( see Col. Sir H. James 's Instructions for taking Meteorological Observations , App. ) . A 59-0 B 29'890 in . M 60'8 a 47-8 6 26'656 m 49 3 836'0 B+b 56 546 M-m I1F5 942'8 B-b 3'234 x 22 28'7 3'234 x 524 *.56'546 x 942'8 *-9-28'7=3110'5=h-H . The height by Laplace 's formula is 3110 8 , by levelling 3115'8 . The accuracy of the presenit formula is only initended to be tested by Laplace 's , and it will be wrong to at least the same extent . Very good results may also be obtained by neglecting 11 " , which is always very small , and transposing the terms h1 ' and -2 35 ( M-m ) ; thus h-I=(52400O j+c +h " ) 8369+A+a +001 . ( h-H)-2:(M-m ) , where 2is writteil for 2335 to compensate for omitting to multiply the latter by ( 836 ? A+ a ) +900 . This approximate form gives rise to the following practical rule for determining heights under 10,000 feet , embodying so much of the Table of corrections as is necessary for that purpose . " , Multiply the difference of the barometers by 52400 , and divide by the sum of the barometers . If the number of clear thousands in the quotient be 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 1 0 , add 0 , 0 5 , 2 7 , 7 2 , 14-8 , 26-1 , 42 2 , 63,6 , 91P2 , 125-6 and 0-2 , 0 5 , 0)8 , 1 1 , 16 , 2-1 , 2'9 , 31 for every additional hundred . Then multiply the result by the sum of the temperatures of the air increased by 836 , and divide the product by 900 . To this quotient add for lat ... . 0 , 10 , 20 , 30 , 32 , 34 , 36 , 38 , 40 , 42 , 44 , ,subtract for lat. 90 , 80 , 70 , 60 , 58 , 56 , 54 , 52 , 50 , 48 , 46 the numbers ... . 2-6 , 2 5 , 2 0 , 1P3 , 1P2 , 1 0 , 0 8 , 0 6 , 0 5 , 0 3 , 01 for every clear thousand it contains . For alneroid and corrected mercurial barometers this result is the height in English feet . For uncorrected mercurial barometers , subitract 2-a times the difference of the temperatures of the mercury . " The barometers may be expressed in any units . If the temperatures are expressed in degrees Centigrade , use. . 500 , 500 , 412 . degrees Reaumur , use ... ... . . 400 , 400 , 52 , in place of. . 836 , 900 , 212 , which are only suited for degrees Fahrenheit . The rule and the other numbers remain unaltered , and the result is in English feet . " Ex. 4 . Height of Guanaxuato in Mexico . A 77 5B 30-046 M 77a L 21 a 70 36 23-660 m 70 31 2-0 836-0 B+b 53-706 M-m 7-2 x 6-8 983-8 B-b 6-386 21 q 13-6 p 18-0 6 386 X 52400 '53'706 6260 5x 9838 +900 =623017 =6842 5 26 & 1 for 6000 136 q 317 diff. for 230 181 0-p 6260 5 h-H=6838 1 Result by Laplace 's formula 6838 2 . These results are obtained by transforming Laplace 's formula as , follows . The original expression in the Me'c . Cel . vol. iv . p. 293 , reduced to English measures and the present notation , is h-H=60158-71.(1+0-002845 cos 2L ) . 836 + A+ ) F ! h-HIVI _ Ii II x jI + og+o ) ( log log ) ? j+I.0868589jJ which Deleros has transformed ( in 'Annuaire Meteorologique de la France ' for 1849 ) to the equivalent of h-H= 60158171 x [ log B-log Z-0 0000389278 . ( M-m ) ] x 836+A+a xGx Il h-H+52251 1* 900 it + Rj The last factor may be split into the two ( 1+ 52251 ) * ( 1+hi ) without sensible error . Then , since 60158'71 x ( I+ 251)=60309l19 and 60309-19 x 0'0000389278=2-34770 , if we put h-il for the product of the three first factors on the right-hand side in ( c ) , we find h-H= [ 60309 19 . ( log B-log b)-2 34770 . ( M-m ) ] . 836+A+a h2 ~~~~900 d+ hoH X 26257 cos 2L+ RH-il ' Putting 2-35 for 2-34770 , and 1 , h " , II " for their values , this form ( d ) will be identical with ( a ) , provided that 60309 19 . ( log B-log 6 ) = 52400 . B-6+e Now putting B-b=yB , we have B-b yIy1 y2+ 1 y3+ 1 y4 +* * ) Z B-6 . y+y -y B+6 2-y 2 log B-log 6=log1 ( =.+ 1y2+ 1y3+ 1y4+ 4 )=(d ) where it is the modulus of the tabular logarithms , and 12 8 always a colnvergent series as y is always a proper fraction , and small when y is small , as it is for moderate heights . Hence 6030919 . ( logB-log 6)=6030919 x 2pu , -b +60309 19.pd =52384B+ +c ' . The constant 52384 has been changed to 52400 to facilitate calculation and to divide the correction for the first two thousand feet , and c ' has consequently been altered to c , the tabular values of which were calculated as follows . Put =52400Bb=52400 . 2Y B+62 whence 2x 52400+x.(f ) Then ( e ) becomes x+c=60309 19.(logB-logb)=-60309 19log(I-y ) . ( g ) Make x successively = 1000 , 2000 , &c. up to 30,000 , and find the corresponding values of y from ( f ) and c from ( g ) . As the differences in the values of c are not uniform , slight errors may arise from neglecting second differences in interpolation , but they can scarcely even affect the result by a single unit , and may therefore be safely disregarded . Laplace 's formula itself cannot be depended on within much larger limits . The Table of corrections and tranlsformation of Laplace 's formula here given allow of the following simplification in the logarithmic calculation of h-H . Let log n= log [ log B-log 6-0 00004 . ( M-m ) ] +I18261420+log(836 ? A+a ) =log [ log B-log 6-0000007 . ( M ' -m/ n ) ] + ? 2 0814145+log(.500+AAf a ' ) =log [ log B -log 6-0O00009 . ( M"f imn ) ] +0 1783245 + log ( 400 + A"f + a " ) , then h-I-I=n+ *001 . nl+h"/ -H"l , where 1 8261420+log900=2-0814145+log,500 =21783245 + log 400= 47 7803845 =log 60309-19 . This form requires less previous preparation , avoids the logarithms of numbers near to unity as 1+ 00 A 1 ) , and allows of the use of foreign data to obtain the result in English feet , so that it only becomes necessary to reduce the height of the lower station to EDglish measures .

112297

3701662

Bessel's Hypsometric Tables, as Corrected by Plantamour, Reduced to English Measures and Recalculated

517

517

Proceedings of the Royal Society of London

Alexander J. Ellis

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0108

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112297

10.1098/rspl.1862.0108

http://www.jstor.org/stable/112297

Biography

Tables

Biography

V. " Bessel 's Hypsometric Tables , as corrected by Plantamour , reduced to English Measures and recalculated . " By ALEXANDER J. ELLIS , Esq. Communicated by Dr. NEIL ARNOTT . Received February 23 , 1863 . These Tables , with the preliminary explanations respecting their correction and reduction , have been , by direction of the Council , cornmunicated to Admiral FitzRoy for insertion in the " Meteorological Papers published by Authority of the Board of Trade , " and will appear in the twelfth Number of the series .

112298

3701662

On Ozone. [Abstract]

517

523

Proceedings of the Royal Society of London

E. J. Lowe

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112298

http://www.jstor.org/stable/112298

Chemistry 2

Chemistry 1

Chemistry

1 . " On Ozone . " By E. J. Lows , Esq. , F.R.A.S. , F.L.S. Communicated by Sir J. F. W. HErSCHEL , Bart. Received March 16 , 1863 . ( Abstract . ) This paper consists of two parts , viz. -1 . On the precautions necessary in ozone observation , and on certain corrections requisite before the actual amount can be determinedo 2 . The discovery of dry ozone powders as a substitute for the ordinary tests ; an investigation into the ozone paper tests of M. Schinbein and Dr. Moffat , the determination of a proper formula for the tests , with an account of various observations and experiments made on the subjecte PART I : At the last Meeting of the British Association I read a paper on the precautions and corrections requisite in order that a more perfect knowledge of ozone might be obtained . These precautions comprise uniformity of observation , each observer using the same box and the same tests , suspended at the same height , and as nearly as possible placed under the same circumstances . The corrections necessary are --lst , For the velocity of the air ; 2nd , for the height of the barometer ; 3rd , for temperature ; 4th , for the hygrometrical state of the air ; 5.th , for elevation above the ground . 1 . Velocity of the Air.-The greater the speed the more ozone will be apparent , and this seems to be owing more to the increased velocity of the air than to a greater proportion of ozone . 2 . Height of the Barometer.-It is found that during the last four years , With the barometer at 281 inches the amount of ozone was 5*7 , g.3 29 , , 9 , , 3.5 30 , , , ) , , 301 , 0*4 A law as regards ozone and pressure is clearly apparent ; but as the barometer falls for wind , the excess at low pressures is no doubt partly due to the increased velocity of the air . There is more ozone with the wind between W.S.W. and S.S.E. than when between N.N.W. and E.N.E. , and the barometer is half an inch lower with S.W. winds than with N.E. winds . 3 . Temperature.-Temperatures between 30 ? and 40 ? will give less ozone than when between 40 ? and 50 ? , and the latter less than when between 50 ? and 60 ? . The same holds good when the ozone box is artificially warmed . This does not extend to very high temperatures , because the great dryness of hot weather is against the action of ozone on the tests . 4 . 2'oisture.-Increase of moisture up to a certain point is favourable to the colouring of the tests , beyond which it operates unfavourably ; for when the air is completely saturated with moisture , the effect of ozone is at its minimum . 5 . Altitude.-The higher the test is hung the darker will be the colour obtained . The difference is as 4 to 6 between 4 feet and 35 feet above the ground . There are yet several other circumstances to be mentioned : I. Hour of the Day.-The difference between the ozone readings at night and in the daytime areIn June and July an excess at night of 01 In August and September , , 0'4 In October and November , , 05 In December and January , , 08 In February and March , , 07 In April and May , , 07 the average excess of the summer months being only one-half of that which occurs in winter , 2 . Direction of the Wind.-There is most ozone with the wind between S. and S.W. , and least when between N. and N.E. 3 . Protection of the test from light.-It is absolutely requisite that the test should be in a dark box ; and no box has been found to answer so well as that constructed by myself , and known as Cs Lowe 's Ozone box , " an account of which has been furnished to the Royal Society* and to the British Association . This box , if freely exposed , and made to veer with the wind , so as always to present the opening to the direct current , is everything that could be desired . The foregoing observations will be sufficient to show that precautions are requisite in these records , and that certain corrections are necessary before we can declare whether ozone is present in a certain fixed amount , or whether it changes from hour to hour . These corrections have yet to be found out ; those for the height of the barometer and the force and direction of the wind will be considerable . PART II . The ozone tests heretofore used have appeared to me to be unsatisfactory , and , on close examination , I found them to be faulty in many respects . The paper used had a glaze upon it , which prevented the solution from penetrating it ; substances , moreover , ha d been used in its manufacture which acted injuriously on the tests . Again , the starch of commerce was found to be impure ; it is manufactured with lime , sulphuric acid , and chlorine , substances fatal to these tests . The iodide of potassium was also impure ; and there has been a want of uniformity in the proportions of starch and iodide of potassium employed by different observers . Having found out that the starch of commerce was impure , I procured a jar of wheat-starch in the wet state before any chemicals had been used . This was steeped in distilled water , which was changed every two days until quite sweet to the taste , and , although by a long process , a chemically pure starch was thus obtained . Sir John Herschel suggested trying other vegetable starches ; I therefore made starch from rice , potato , sago , and wheat . I obtained chemically pure iodide of potassium from Mr. Squire of Oxford Street , who forwarded me two samples made expressly for these experiments , the one prepared with water , the other crystallized several times from alcohol . On the recommendation of Dr. R. D. Thomson , 15 grains of prepared chalk have been added to each ounce of air-dried starch to prevent it from becoming sour from any moisture that might be contained in it ; subsequent observations have proved that this is absolutely requisite for uniformity of effect , as the intensity of action depends upon the amount of water contained in the starch , which is apparent from the following experiment : Tests made with air-dried starcha . Without further drying became coloured in 5 minutes . F3 . After further drying by fire-heat for 1 minute became coloured in 7 minuteso y. After further drying by fire-heat for 3 minutes became coloured in 9 minutes . B. After further drying by fire-heat for 10 minutes became coloured in 13 minutes . e. After further drying by fire.heat for 30 minutes became coloured in 20 minutes . r. With chalk added became coloured in 20 minutes . With regard to the calico or paper used for the tests , both stained when impure . However , Mr. Joseph Sidebotham of the Strine Works prepared for me some chemically pure calico , and I was also enabled to procure a very porous chemically pure paper , both of which answer perfectly . Having succeeded with the-ozone slip tests , I tried as a first experiment a mixture of 10 parts of starch to 1 of iodide of potassium as a " dry-powder test ; " this , when well mixed in a mortar , was bottled ready for use . A small portion was placed in the open air , and ten minutes ' exposure showed that powder tests were an undoubted success , being more sensitive than the test slips . My next determination was what strength would colour quickest , and accordingly a number of strengths were prepared , varying in the proportions from 1 of iodide of potassium and 1 of starch up to I of iodide of potassium and 30 of starch , the starch used being made from wheat . From these experiments it was found that the proportion of 1 of iodide of potassium to 5 of starch was invariably the darkest , the degree of darkness diminishing in either direction when other strengths were used ; thus 1 of iodide of potassium to 4 of starch , or 1 to 5 ? , were neither so dark as with a strength of 1 to 5 . On repeating these experiments with potato-starch , the proportion that coloured soonest was 1 to 2 } ; and this second series of experiments proved that with each starch a special formula is requisite . My next experiments were with the view of ascertaining the effect of various acids and chemical substances on the ozone powder tests . For this purpose I procured a number of cups for solutions , and small pill-boxes to hold the powder tests , and these were placed together under separate bell-glasses . The result was that the following coloured the powder tests very rapidly:-Hydrochloric acid , nitric acid , nitrous acid , chloride of lime , phosphorus , iodine ( in scales ) iodine ( dissolved in alcohol ) , carbonate of iron on which sulphuric acid was poured , carbonate of iron on which glacial acetic acid was poured , limestone on which sulphuric acid was poured , limestone on which glacial acetic acid was poured , matches lighted under the bell-glasses . The following did not colour the tests:-Sulphuric acid , glacial acetic acid , carbonate of lime , carbonate of iron , ammonia , matches not lighted . The substances used in the manufacture of ordinary starch of commerce gave the following : Chloride of lime coloured the tests instantaneously . Sulphuric acid did not colour the tests . Lime did not colour the tests . Lime and sulphuric acid mixed coloured the tests rapidly . There are advantages in the powders over the ordinary tests . They are more sensitive , and therefore more rapidly acted upon ; they retain their maximum colour , not afterwards fading , as with the tests of Schinbein and Moffat . ( However , my calico and porous-paper tests are not nearly so liable to fade , owing to the solution penetrating into the fabric used , instead of being merely a surface-covering . ) There is also a more important advantage still to be mentioned from the use of powders . By the aid of powder tests we shall ascertain what colours the tests ; in the experiments it was found that a different colour was imparted to the powder , and that the colour penetrated deeper with some substances and acids than with others , so that differences of effect took place , from which the different materials used might be recognized . Thus:1 . Iodine , although coloured a brown-black , was merely a surface colouring , below the powder remained colourless . 2 . Phosphorus , bluish black on the surface only , below almost colourless . 3 . Chloride of lime , deep brown on the surface only , the powder below slightly yellow . 4 . IHydrochloric acid , grey-pink on the surface only , the powder beneath orange . 5 . Nitric acid , dark-red brown extending slightly into the powder , beneath that colourless . 6 . Carbonate of iron with glacial acetic acid , yellowish brown to the thickness of cardboard , below that buff . 7 . Limestone with sulphuric acid , pale brown to the thickness of cardboard , beneath . slightly coloured . 8 . Carbonate of iron with sulphuric acid , black to the depth of a quarter of an inch . 9 . Nitrous acid , dark brown more than the eighth of an inch deep , beneath yellowish brown . 10 . Nitric acid mixed with exposed ozone powder , blue-black to the sixth of an inch deep , below that reddish brown . 1 . Nitric acid mixed with unexposed ozone powder , blue-black to the sixth of an inch deep , below that reddish brown . These experiments may require some modification , yet they point out the fact that striking differences are apparent , differences which must open up a new method of investigating ozone . Not only have the tests hitherto used been made without due regard to the pureness of the chemicals and fitness of the material used , but the paper box in which they have been kept is not sufficient for their perfect preservation ; a dark , dry , air-tight box is essential and this should not be opened in a room where there is iodine , chlorine , nitric acid , phosphorus , hydrochloric acid , or other chemicals likely to be injurious to the tests . I am now manufacturing the tests , which will be distributed by Messrs. Negretti and Zambra , and I have constructed a proper box in which in future they will be sent .

112299

3701662

On the Equations of Rotation of a Solid Body about a Fixed Point. [Abstract]

523

524

Proceedings of the Royal Society of London

William Spottiswoode

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112299

http://www.jstor.org/stable/112299

Formulae

Fluid Dynamics

Mathematics

II . " On1 the Equations of Rotation of a Solid Body about a fixed Point . " By WILLIAM SPOTTISwooDE , M.A. , F.R.S. Received March 21 , 1863 , ( Abstract . ) In treating the equations of rotation of a solid body about a fixed point , it is usual to employ the principal axes of the body as the moving system of coordinates . Cases , however , occur in which it is advisable to employ other systems ; and the object of the present paper is to develope the fundamental formule of transformation and integration for any system . The integrals found areP-=:a l_ O cos am ( , / ( S+ ) ^O co . sin am ( 7k'-(S+O)h t+f ) ; = / S2)H0 am ( , --/ C1 k_-(s + )h t +f ) where 0 , 01 , 02 are the roots of the cubic ( S +0)3S(S+0)2+S(S+0)-v=0 , V being the determinant of the system A , B , C , -F , --G , -H , S the sum of A , B , C , and S that of the corresponding inverse quantities . Moreover P1 , q1 , r1 are linear functions of p , q , r ( the components of rotation about the axes for which A , B , C , &c. are calculated ) , the coefficients of which are determined in the paper itself .

112300

3701662

On the Fossil Human Jawbone Recently Discovered in the Gravel near Abbeville

524

529

Proceedings of the Royal Society of London

William B. Carpenter

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0111

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112300

10.1098/rspl.1862.0111

http://www.jstor.org/stable/112300

Geography

Headmatter

Geography

III . " On the Fossil Human Jawbone recently discovered in the Gravel near Abbeville , " in a Letter to the President , by W. B. CARPENTER , M.D. , V.P.R.S. Received April 16 , 1863 . University of London , Burlington House , W. April 16 , 1863 . DEAR MR. PRESIDENT , -I esteem it a privilege to have it in my power to communicate , through you , to the Royal Society some particulars of the important discovery just made by M. Boucher de Perthes , of a human maxilla in one of the gravel-beds near Abbeville also yielding the now well-known flint implements . Having been informed of this discovery a few days since , whilst staying in Paris , I became additionally desirous of carrying out my previous intention of stopping at Abbeville on my way homewards ; and accordingly , after a short visit to Amiens , -which gave me the opportunity of disinterring for myself a small but well-characterized flint implement from the gravel-pit of St. Acheul , -I proceeded on the afternoon of Monday last to Abbeville , where I was received with the greatest kindness and attention by M. Boucher de Perthes . The history of his discovery is given in the following extract from the local journal 'L'Abbevillois , ' by which it will be seen that the specimen in question was removed by M. Boucher de Perthes himself from the bed in which the first indications of it had been found by the workman employed in that part of the excavation:"A la fin de mars dernier , le terrassier Halatre , travaillant a cette career , vint lui apporter avec un silex taille un petit fragment d'os qu'il y avait egalement recueilli . Ayant debarrasse ce fragment du sable qui le couvrait , M. de Perthes aper9ut un dent fort endomtnagee , mais qu'il n'en reconnut pas moins pour un molaire humaine . " II suivit immediatement Halatre a Moulin-Quignon , v4rifia la place d'oW venait la hachette et la dent , s'assura que cette place etait net de tout infiltration ou introduction secondaire et fit continuer la fouille . " Elle no produisit ce jour-la aucun resultat nouveau . " Convaincu que quelqu'autre debris du corps d'ou provenait cette molaire devait se trouver la , M. Boucher de Perthes recom . manda aux terrassiers de no rien derarger de ce qu'ils pourraient remarquer pendant son absence , mais de le prevenir sans retard . En effet , le 28 mars le terrassier Vasseur vint lui dire que quelque chose ressemblant a un os paraissait dans le bane . " Rendu sir les lieux , M. de Perthes trouve le terrain comme l'avait dit Vasseur . L'extremite de l'os enferme dans sa gangue se montrait d'environ deux centimetres . " Voulant l'avoir entier , M. de Perthes fit , a l'aide d'une pioche , degager les alentours et , a sa grande satisfaction , il put le retirer du bane sans le rompre . " I1 no s'etait pas trompe dans ses previsions . La dent avait annonce la tate , et dans le morceau qu'il venait d'extraire , il reconnut un machoire humaine.-Un grand problem etait resolu . " A quelques centimetres de ce fossile humain , le premier peut-etre dont la position geologique eut ete aussi nettement constatee , car , par un autre circonstance heureuse , les temoins ici no manquaient pas , etait un hache en silex egalement engagee dans le bane , d'oi , sir l'invitation de M. Boucher de Perthes , M. Oswald Dimpre , jeune archeologue et dessinateur habile bien connu des savants qui ont visit Abbeville , l'enleva mais non sans s'aider aussi de la pioche . " Un chose qui frappa tous les spectateurs , ce fut la parfaite identite de patine ou de couleur de cette machoire , des silex taille 's et des cailloux roules , avec le bane qui les contenait , couleur brune , presque noire , contrastant singulierement avec la teinte jaune ou grise des banes superienrs et la craie blanch sir laquelle elle repose . " Mesure prise de chacune des couches superieures , la machoire fossile etait ainsi que les hachettes a4 metres 52 centimetres * de la superficie et tout pres de la craie . " Ce bane de Moulin-Quignon , place ' sir le plateau qui domnine la vallee , se trouve a 30 metres au-dessus du niveau de la Somme et de la mer. " The particulars I have now to communicate as the result of my own personal examination should , I think , most completely satisfy any unprejudiced person that , on the one hand , the specimen cannot have been a " plant " contrived by the workman , and , on the other , that it could not have found its way into the bed in which it was discovered by any disturbing agency subsequent to the original deposition of that bed * . When M. Boucher de Perthes had the kindness to place in my hands this precious fragment-which consists of the right half of the lower jaw , containing three teeth-I was immediately struck with its almost black colour , its solidity , and its weight : all these peculiarities ( which are in marked contrast to the characters of the bones ordinarily found in these gravel-pits ) being obviously due to one and the same cause , viz. metallic ( ferruginous ? ) infiltration . The ordinary flints , and the flint implements obtained from the same deposit , several of which are in the museum of M. de Perthes , are all of them characterized by a like depth of ferruginous tint , which is not seen in any of those taken from any other part of the same pit , or from any other gravel-pit yet opened in the neighbourhood of Abbeville . As to the anatomical characters of this jaw , I should not wish , without a more careful comparative examination of the specimen than I had the opportunity of making , to give any decided opinion ; but my impression is that they differ very decidedly from those of the same bone in any race at present inhabiting Western Europe . I was struck with the thickness of the bone , the great breadth of the ascending ramus , but especially with the extraordinary breadth and depth of the groove between the ramus and alveolar border , in which I could almost lay my little finger . The jaw would appear to be that of a person advanced in life ; and the tooth originally found , which very probably belonged to the other half of the same jaw , seemed to me to have been " endommagee " by caries during life rather than by subsequent violence . 9 , < Fig. 1 . M. Boucher de Perthes had the kindness to give me the accompanying sketch of the specimen ; and I can testify to the accuracy of its representation of the general form of the bone . On Tuesday morning I repaired , in company with M. Boucher de Perthes , to the gravel-pit of Moulin-Quignon ; in which he showed me , as nearly as he could , the situation in which this most interesting relic had been found . Unfortunately there had occurred , a few days previously to my visit , a slip of the overlying strata , by the debris of which the exact spot was covered ; but a part of the same deposit was visible at a horizontal distance of a yard or two , so that I could indubitably verify its position and its general characters . This deposit , distinguished from every other by the extreme depth of its ferruginous tint ( which corresponds exactly to that of the bone ) , lies at the very bottom of the pit , in immediate contact with the subjacent chalk , as shown in the accompanying representation of the section ( also kindly given to me by M. Boucher de Perthes ) , to the general accuracy of which I can bear the most explicit testimony . I myself took away from this deposit some specimens of the small rounded flints which it contains , and which will serve to show you this peculiar tint . Fig. 2.-Section of the Strata in the Gravel-pit of Moulin-Quignon , near Abbeville . --------_ t. in . 1 . Vegetable mould ... ... ... ... ... I0 2 . Undisturbed subsoil , consist~q3~~~ ing of grey sand with broken flints ... ... ... ... ... ... ... ... ... ... 2 3 / ----^- < ~ 5/ ~ . ? ./ 3 . Yellowish argillaceous sand , with large flints but little - ... ... ... .::- : ... ... .:__- : =l rolled , resting on a layer of -:- ... ... ... ... .--.------::-grey sand ... ... ... ... ... ... ... ... 50 ------4 . Yellow ferruginous sand , containing smaller and more rolled flints , and divided by a second layer of less yellow sand ... ... ... ... ... ... ... ... ... ... 57 5 . Argillaceous sand of a deep brown or almost black hue , sticking to the hand and staining it , containing small I~- ; -~-~=----=L----_ _ _flints more rolled than those -_ ___ of the upper strata.-N.B . The white spaces left in this layer mark the position of the jaw and of the flint hatchet found in contiguity with it . 18 15 6 ... ... . 6 . Chalk . These facts must be admitted , I think , to exclude any possibilitY of doubt as to the truly fossil character of this bone . Its peculiar condition could not have been produced by any artificial means at present known , and most assuredly indicates that it must have been long buried in the deposit from which its metallic impregnation has been derived * . That it could not have found its way into that deposit in any other mode than by original imbedding , may be fairly concluded from the entire absence of the least indication of disturbance in the superjacent strata , which are most regularly superposed ( as seen in the accompanying section ) to a depth of more than 15 feet . This complete regularity of superposition in the strata of the gravel-pits of Moulin-Quignon has , I understand , been already verified by numerous experienced geologists , whose testimony upon such a point is of far higher value than mine ; but it is so obvious that I cannot imagine the least doubt to remain in the mind of any intelligent observer who may visit the locality and examine its condition for himself , of the jaw having been imbedded in the lowest stratum before the deposition of the superincumbent layers . I have further to point out , that as the gravel-bed of MoulinQuignon is about 100 feet above the present level of the river , it corresponds in position with the upper gravel of St. Acheul , not with the lower gravel of Menchecourt . If , therefore , we accept the conclusions of Mr. Prestwich as to the relative ages of these gravels , this human jaw was buried in the very oldest portion of the earliest of these fluviatile deposits , and therefore dates back to the very remotest period at which we have at present any evidence of the existence of Man . Believe me , dear Mr. President , Yours faithfully , WILLIAM B. CARPENTER .

112301

3701662

On the Diurnal Inequalities of Terrestrial Magnetism, as Deduced from Observations Made at the Royal Observatory, Greenwich, from 1841 to 1857. [Abstract]

529

532

Proceedings of the Royal Society of London

George Biddell Airy

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112301

http://www.jstor.org/stable/112301

Meteorology

Tables

Meteorology

I. " On the Diurnal Inequalities of Terrestrial Magnetism , as deduced from observations made at the Royal Observatory , Greenwich , from 1841 to 1857 . " By GEORGE BIDDELL AIRY , F.R.S. , Astronomer Royal . Received April 8 , 1863 . ( Abstract . ) The author describes this paper as one of the class which gives the epitomized results of long series of voluminous observations and laborious calculations , of which the fundamental details have been 1863 . ] 529 printed in works specially devoted to these subjects . It exhibits in curves the diurnal inequalities of terrestrial magnetism , as obtained by the use of instruments essentially the same , through the whole period of seventeen years , during the last ten years of which the magnetic indications have been automatically recorded by photographic self-registration , on a system which has been continued to the present time , and is still to be continued . From the last months of 1840 to the end of 1847 , the observations were made by eye , every two hours . From the beginning of 1848 , for the declination and horizontal force magnetometers , and from the beginning of 1849 , for the vertical force magnetometer , the magnetic indications are recorded by Mr. Brooke 's photographic apparatus . In preparing the reductions of the magnetic records from 1848 to 1857 ( which are printed in the " Results of Magnetical and Meteorological Observations for 1859 , " bound in the volume of 'Greenwich Observations , ' 1859 , and also issued separately ) , the days of unusual magnetic disturbance had been separated from the rest , and the reductions applied to the mass so diminished . For unity of plan , it appeared expedient to follow the same course for the reductions from 1841 to 1847 . In consequence of this , the numbers which are used here differ in some cases by small quantities from those printed in the ' Greenwich Magnetical Observations from 1841 to 1847 . ' The numbers in the reductions from 1848 to 1857 are adopted without change . The author remarks that , taking the number of omitted days as a rough measure of the amount of magnetic disturbance , there is no appearance of decennial cycle in their recurrence , and no distinct relation to the magnitude of diurnal changes . The author then proceeds to the description of the curves . The first four sheets contain the curves in which the horizontal abscissa represents the declination at each hour as compared with the mean for the twenty-four hours and the vertical ordinate represents the horizontal force at each hour as compared with the mean for the twenty-four hours . On the different sheets the days are differently grouped , thus:-On sheet I. all the observations at each nominal hour throughout the year are combined ; this sheet contains the separate curves for 1841 , 1842 , 1843 , 1844 , 1845 , 1846 , 1847 . On sheet II . similar curves are formed for 1848 , 1849 , 1850 , 1851 , 530 1852 , 1853 , 1854 , 1855 , 1856 , 1857 . On sheet III . all the observations at each nominal hour through all the months January from 1841 to 1847 are combined to form the January curve ; all those through the months February to form the February curve , and so on . On sheet IV . similar month-curves are formed from the period 1848 to 1857 . It is remarked that the origin of coordinates necessarily represents the mean declination and mean horizontal force in each month . The author then points out that the means for each month are themselves subject to an annual inequality , which can be ascertained with little difficulty . The values of these inequalities are exhibited , for declination and horizontal force , separately for the period 18411847 and for the period 1848-1857 ; those in the first period far exceed in magnitude those in the second ( as holds also with regard to all the diurnal inequalities ) . If we wished to exhibit the hourly state of magnetism , as referred to the mean state given by the supposition of uniform secular change of normal magnetism , we ought to apply these quantities with sign changed , to the origin of coordinates in each curve , in order to form a new origin of coordinates . For the year-curves , the numbers destroy each other , and no new origin of coordinates is produced ; for the month-curves , however , they shift the origin materially . The author does not perceive that any facility for theoretical reference or other advantage is gained by this step . On examining the year-curves , it is seen that from 1841 to 1848 their magnitude very slowly increases , with a small change of form , but from 1848 to 1857 their magnitude very rapidly diminishes , with a great change of form . Some great cosmical change seems to have come upon the earth , particularly affecting terrestrial magnetism . On comparing these year-curves with the month-curves , especially with those for the period 1848-1857 , it appears that the change of the year-curves from 1848 to 1857 nearly resembles that of the month-curves from summer to winter ; and the author points out as a possible step to a physical explanation of the change from 1848 to 1857 , that the magnetic action of the sun upon the earth 's southern hemisphere may have remained nearly unaltered , while that on the northern hemisphere may have undergone a great diminution . The author then alludes to the curves representing the hourly 1863 . ] 531 state of vertical force , as referred to the mean on each day . The force is here represented by a simple ordinate . The grouping is made by years and by months in the same manner as for the curves already mentioned . The month-curves of the two periods ( 18411847 and 1848-1857 ) differ , in the magnitude and change of magnitude of the ordinates , and in the place and change of place of node . The year-curves of the two periods have some very remarkable differences . From 1847 to 1849 the magnitude of the ordinates increases sensibly ; from 1849 to 1850 still more ; it then remains nearly stationary . In 1846 the descending node is at 11h nearly ; in 1847 it is at 9h nearly ; in 1849 at 7h nearly ; in 1850 at 5h ; in 1851 at 4h ; and there it continues with little alteration . It is important to observe that , though the instrument was changed in 1848 , the change in the place of the node did not then occur suddenly ; it had begun with the old instrument , and continued to advance gradually for several years with the new instrument . The author states that he had verified the correctness of the node in the first period from other observations , but he had not succeeded in finding observations corresponding in date with those of the latter period . The paper is followed by eight sheets of curves , as follows : I. Diurnal Curves of combination of Declination and Horizontal Force . ( 1 ) Mean of all the days in each year ( separately ) , 1841-1847 . ( 2 ) Mean of all the days in each year ( separately ) , 1848-1857 . ( 3 ) Mean of all the days in the aggregate of the same nominal months ( separately ) through the period 1841-1847 . ( 4 ) Mean of all the days in the aggregate of the same nominal months ( separately ) through the period 1848-1857 . II . Diurnal Curves of Vertical Force . ( 5 ) Mean of all the days in each year ( separately ) , 1841-1847 . ( 6 ) Mean of all the days in each year ( separately ) , 1849-1857 . ( 7 ) Mean of all the days in the aggregate of the same nominal months ( separately ) through the period 1841-1847 . ( 8 ) Mean of all the days in the aggregate of the same nominal months ( separately ) through the period 1849-1857 . 53

112302

3701662

On the Direct Transformation of Iodide of Allyle into Iodide of Propyle

533

534

Proceedings of the Royal Society of London

Maxwell Simpson

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0113

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112302

10.1098/rspl.1862.0113

http://www.jstor.org/stable/112302

Chemistry 2

Thermodynamics

Chemistry

II . " On the direct Transformation of Iodide of Allyle into Iodide of Propyle . " By MAXWELL SIMRPSON , M.B. , F.R.S. Received April 7 , 1863 . Iodide of allyle , as is well known , combines directly with two equivalents of metallic mercury , a well-defined crystalline compound being formed . Would it be possible to make the same body combine with two equivalents of hydrogen , and thus to open a direct passage from the allylic to the propylic series of compounds ? Indirectly this transformation has been already effected by M. Berthelot through the intervention of propylene gas . In order to determine the above point , I submitted iodide of allyle to the action of hydriodic acid gas . On passing this gas into the iodide , the latter became strongly heated and black from the liberation of a large quantity of iodine . As soon as the gas was observed to pass unabsorbed through the liquid , the latter was allowed to cool , and filtered through asbestos . It was then decolorized by agitation with a dilute solution of caustic potash , dried over chloride of calcium , and distilled . Almost the entire quantity passed over between 90 ? and 95 ? Cent. The portion distilling between 92 ? and 94 ? Cent. I collected apart and analysed . The numbers obtained correspond with the composition of iodide of propyle , as will be seen from the following table : Theory . Per cent. Experiment . C ... . 36 21-18 21 29 ... ... . 7 4'11 4-16 I ... ... . . 127 74-71 170 100-00 The specific gravity of the iodide is 1 73 at zero . In order to satisfy myself that the body I had in my hands was really an ether of propylic alcohol , I endeavoured to prepare that alcohol from it . This I succeeded in doing in the following manner:-About 60 grammes of the iodide were added to an equivalent of oxalate of silver contained in a flask surrounded by water . The mixture became strongly heated from the violence of the reaction , and the decomposition was soon complete . It was then digested with ether . On submitting the ethereal solution to distillation , I observed that , as soon as the ether had passed over , the thermometer rose rapidly to 186 ? , and that the entire liquid , previously dissolved in the ether , distilled over between that temperature and 197 ? Cent. This was no doubt oxalate of propyle . On heating this body in a retort with solid caustic potash , I obtained a volatile distillate . This I then dried over chloride of calcium , and in order to secure its complete dehydration , treated it with a small piece of sodium . On re-distilling , I found that the entire liquid passed over between 83 ? and 88 ? Cent. The portion distilling between 85 ? and 88 ? gave on analysis results corresponding with the formula of propylic alcohol , as will be seen on inspecting the following table : Theory . Per cent. Experiment . C6 ... ... . . 36 60'00 59'21 IH ... ... . . 8 13-33 13-47 O0 ... ... . . 16 26*67 60 100'00 By treating this body with iodine and phosphorus , I succeeded in regenerating iodide of propyle . This is a very ready method of preparing propylic alcohol when a large quantity is not required .

112303

3701662

On the Distillation of Mixtures: A Contribution to the Theory of Fractional Distillation

534

535

Proceedings of the Royal Society of London

J. A. Wanklyn

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0114

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112303

10.1098/rspl.1862.0114

http://www.jstor.org/stable/112303

Chemistry 2

Thermodynamics

Chemistry

III . " On the Distillation of Mixtures : a Contribution to the Theory of Fractional Distillation . " By J. A. WANKLYN , Esq. Communicated by Dr. FRANKLAND . Received April 17 , 1863 . There are many points in the boiling of mixtures which are obscure . The tension of the vapours at the temperature whereat the mixture boils , and the proportions in which the constituents of the mixture are present , are not the only factors which determine the relative rates at which the constituents distil . There have , for instance , to be taken into account the adhesion of the liquids to one another , and the vapour-densities of these liquids . On the present occasion I have to call attention to the influence of this latter element , which influence seems to have been lost sight of by most of those who have applied themselves to this subject . Leaving out of account for a moment the influence of adhesion , and simplifying the influence of the proportion in which the ingredients are present by taking equal weights of two liquids of different boiling-points , we may set down the rates at which these ingredients will distil as determined by the tensions of the liquids and the densities of the vapours . In the first instant of time the quantity of each ingredient which distils will be found by multiplying its tension at the boiling-point of the mixture by its vapour-density . It thus appears that the liquid with the highest tension will not of necessity distil the quickest , for what the other liquids want in tension they may make up by the greater density of the vapours which they give off . And so when we mix a more volatile with a less volatile liquid and proceed to distil the mixture , we shall now and then find that the less volatile liquid distils faster than the more volatile one . I will here bring forward an experiment to illustrate this point . Vapour-density . Methyl-alcohol boils at 66 ? C ... ... ... 1 107 Iodide of ethyl boils at 72 ? C ... ... ... 5-397 I took 18 grammes of methyl-alcohol and 17 grammes of iodide of ethyl , mixed them , and distilled off rather more than one-third of the mixture . The distillate consisted of 6'0 grammes methyl-alcohol , 8§ 7 grammes iodide of ethyl , 14'7 which shows that in this case the less volatile constituent had boiled the faster , the less volatile iodide of ethyl having a very much higher vapour-density than methyl-alcohol . It will be obvious that when the vapour-densities and tensions are inversely proportional , the mixture must distil over unchanged . This influence of vapour-density goes a great way to explain why homologous bodies are so difficult of separation by means of fractional distillation . The more complex the formula the higher the boiling-point , but also the higher the vapour-density , and therefore the greater the value of the vapour . Why oils , &c. distil so readily in steam is also explained ; for aqueous vapour is one of the lightest , while oily vapours are generally heavy .

112304

3701662

On the Arrangement of the Muscular Fibres of the Ventricular Portion of the Vertebrate Heart; with Physiological Remarks

536

536

Proceedings of the Royal Society of London

James Pettigrew

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0115

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112304

10.1098/rspl.1862.0115

http://www.jstor.org/stable/112304

Biography

Neurology

Biography

IV . " On the Arrangement of the Muscular Fibres of the Ventricular Portion of the Vertebrate Heart ; with Physiological Remarks . " By JAMES PETTIGREW , M.D. Communicated by Professor GOODSIR . Received March 26 , 1863 . This paper is a revised version of a previous one , having the same title , which was communicated to the Society on the 22nd of November , 1859 , and formed the substance of the Croonian Lecture delivered by the author on the 19th of April , 1860 . The author has now inclucded the results of his researches on the structure of the ventricular portion of the heart in fishes , reptiles , and birds .

112305

3701662

On Spectrum Analysis; with a Description of a Large Spectroscope Having Nine Prisms, and Achromatic Telescopes of Two-Feet Focal Power. [Abstract]

536

538

Proceedings of the Royal Society of London

John P. Gassiot

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112305

http://www.jstor.org/stable/112305

Optics

Biography

Optics

I. " On Spectrum Analysis ; with a Description of a large Spectroscope having nine Prisms , andAchromatic Telescopes of two-feet focal power . " By JOIIN P. GAssIOr , F.R.S. Received April 21 , 1863 . ( Abstract . ) The author , after briefly alluding to the discoveries of Fox Talbot , Wheatstone , Foucault , Kirchhoff , and Bunsen , and the importance of spectrum analysis , states that among the numerous spectroscopes which were exhibited in the International Exhibition of 1862 , there was one which had been specially constructed by Messrs. Spencer , Browning , and Co. , philosophical instrument makers in London , which at the time excited considerable attention . This spectroscope had two prisms , with a magnifying power of 40 , its definition being remarkably clear . The skill evinced by Mr. Browning in the construction of this instrument induced the author to have one made in which still better effects might be produced , by multiplying the number of prisms and increasing the magnifying power , with the necessary precaution to avoid as much as possible loss of light . After a few preliminary trials , it was finally arranged to use nine prisms , which is the number that can be applied with this instrument , although the arrangements are such as to allow the whole or any less number to be used with the utmost facility . Verniers and micrometer screws are attached to the knife-edges of the slit through which the light to be observed is admitted to the collimator and to the telescope , also to the large circle of the instrument ; these enable the observer to note the exact position of the lines observed in the spectrum from whatever source it is obtained , and thus enable him to repeat and verify previous results with the utmost exactitude . When two small prisms , one refracting and the other reflecting , are fixed outside the knife-edge slit , spectra obtained from three separate sources can be simultaneously examined ; and an illuminated micrometer scale enables the observer to note the precise relative position of the lines in the three spectra without reference to or reading off from the verniers . By this arrangement a most interesting spectacle may be obtained , showing in the uppermost portion of the field of view the spectrum of thallium , strontium , or lithium , ignited in the flame of a Bunsen 's gas-burner ; in the centre of the field the spectrum of the same substance in the oxyhydrogen blowpipe , and at the bottom one in the voltaic arc ; each successive spectrum there exhibits an increased number of lines . With this spectroscope the author has ascertained that the green line of thallium , so celebrated for its integrity , and hitherto believed . to coincide with one of the lines in the spectrum of baryta , does not so coincide ; for by employing the nine prisms with a power of 80 on the telescope , the thallium line is clearly seen to occupy a dark space in the baryta spectrum , close by the side of the bright line with which it was supposed to coincide . A range of prisms is adapted to the telescope , the highest of which , when used in conjunction with the amplifying lens , gives a power of 110 with good definition . The author states that the results already obtained by this instrument have been so satisfactory as to leave him no cause to regret the time that has been devoted to , or the expense that has been incurred in the construction of this truly beautiful apparatus . A full description of the instrument is introduced , with several diagrams showing the construction and adaptation of the different parts of the apparatus , and two drawings , one showing the general appearance of the instrument when prepared for observation , and the other representing it as seen when viewed from above .

112306

3701662

The Bakerian Lecture: On the Direct Correlation of Mechanical and Chemical Forces

538

550

Proceedings of the Royal Society of London

Henry Clifton Sorby

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0117

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112306

10.1098/rspl.1862.0117

http://www.jstor.org/stable/112306

Chemistry 2

Thermodynamics

Chemistry

II . THE BAKERIAN LECTURE.- " On the Direct Correlation of Mechanical and Chemical Forces . " By HENRY CLIFTON SORBY , F.R.S. Received April 29 , 1863 . Perhaps it may be thought somewhat strange that a geologist should undertake such a subject as the correlation of forces ; but the very fact of my being a geologist has led to the investigations of which I now purpose to give a short preliminary account . In studying general chemical and physical geology , and especially in examining the microscopical structure of rocks , I have for a number of years been greatly perplexed with a class of facts which pointed both to a mechanical and to a chemical origin . At first I attributed them either to a mechanical or a chemical action , or to the two combined ; but in most cases no satisfactory explanation could be given . At length , however , facts turned up which altogether precluded any supposition not involving direct correlation ; for they most clearly indicated that mechanical force had been resolved into chemical action in the same way as , under other circumstances , it may be resolved into heat , electricity , or any other modification of force , as so ably described by Grove in his work ' On the Correlation of Physical Forces . ' The effect of pressure on the solubility of salts has already been made the subject of speculation and experiment * , and a considerable number of facts have been described , showing that pressure will more or less influence such chemical actions as are accompanied by an evolution of gas , so that it may cause a compound to be permanent which otherwise would be'decomposed* ; but the results were for the most part so indefinite and unconnected , or of such a character , that Mr. Grove does not allude to the direct production of chemical action from mechanical force . That this is , however , extremely probable will be evident to all who have considered the manner in which the various physical forces are correlated ; for if mechanical force can be produced by chemical action , why should not the converse be true ? In this paper I shall endeavour to show that such is really the fact , and that in some cases the mechanical equivalent of the chemical force may be determined . In order to obtain the necessary great pressure , I have made use of a modification of the method employed by Bunsen ; but instead of filling the tubes at the ordinary temperature of the atmosphere and then gently heating them for several hours , I in the first instance filled them at a temperature 10 ? or 20 ? C. lower , so that when finally sealed up they contained considerably more liquid than they could hold without pressure at the ordinary temperature of the atmosphere at the time being ; and thus , by its tendency to expand , this liquid and anything enclosed in the tube were subjected to a very great pressure . By keeping the tubes in various parts of the house , according as the weather varied , I have been able to maintain for several weeks or even months a pressure of , for instance , about 100 atmospheres , as measured by means of a capillary-tube pressure-gauge enclosed within the larger tube . Since in all cases I had a second tube which from first to last was treated precisely like the other , pressure excepted , I have been able to determine the effect produced by the pressure with very considerable accuracy-at all events so as to leave no doubt whatever about the general facts . At the same time I wish it to be understood that the results described below must be looked upon only as approximations to the truth . I will first call attention to the well-known influence of pressure on the fusing-point of various substances , since it is a connecting link between well-established facts and those I am about to describe . Bunsen* and IHopkins t have shown that substances which expand when fused have their point of fusion raised by mechanical pressure ; that is to say , since mechanical force must be overcome in melting , the tendency to melt must be increased by heat before that opposition can be overcome ; and the pressure required to keep them solid at any temperature above their natural point of fusion may be looked upon as the mechanical representative of the force with which they tend to fuse at that temperature . Professor VW . Thomson has shown that , on the contrary , water , which expands in freezing , has its point of fusion lowered by pressure ; that is to say , since mechanical force must be overcome in crystallizing , crystallization will not take place under increased pressure unless the force of crystalline polarity be increased by reducing the temperature . Thus , calculating from his experiments and from the known latent heat of ice , and assuming that no heat is gained or lost by contact with external objects , if we had 1 part of ice and 100 of water at 0 ? C. , and then applied a pressure of 103 atmospheres , the ice would , as it were , dissolve in the water , the whole would become liquid , and the temperature be reduced to -'792 ? C. ; or , in other terms , at that temperature the tendency to crystallize is exactly counterbalanced by that pressure . Now I find that similar principles hold true with respect to the solubility of salts in water . If , when they dissolve , the total bulk increases , pressure reduces their solubility ; whereas if the bulk decreases , pressure makes them more soluble ; in other words , solution or crystallization is impeded by pressure according as mechanical force must be overcome in dissolving or in crystallizing . Various authors have written on the volume with which salts enter into solution ? ; but since the subject before us requires a different class of facts to be taken into account , I shall base my conclusions on my own experiments . The volume with which salts exist when in solution , assuming that of the water to remain unchanged , varies greatly in the case of different salts , and also according to the amount in solution and the temperature . Thus , taking sal-ammoniac as an example , when there are 3 per cent. in solution the volume is as if it expanded 3'40 per cent. on dissolving ; whereas when 25'55 per cent. are in solution , the expansion is 11'36 per cent. ; and when nearly concentrated at about 13 ? C. , an additional quantity expands on dissolving 15 78 per cent. In by far the greater number of cases , however , there is a contraction on dissolving , and the amount gradually diminishes for each additional quantity entering into solution , so that the mean result is very different from what occurs when the solution is dilute or nearly saturated . It is this contraction or expansion when a small additional quantity is dissolved in a nearly concentrated solution that must be taken into account in the following calculations . In determining the influence of pressure on the solution of salts , I found it requisite to adopt somewhat different methods according to the peculiarities of the salts . In some cases I sealed up in a saturated solution portions of the salt in clean , solid crystals , and determined the effect due to pressure from their loss in weight ; whereas in other cases I sealed up solutions containilg more salt than could be dissolved at the temperature at which the experirients were made , and determined the effect of pressure from the difference in the weight of the crystals deposited ; being of course careful to make allowance for any difference in the amount of solution in the tube with pressure and in that without , and to avoid any error that might be produced by a different temperature . In all cases I have had a tube with pressure and another without , treated from first to last in precisely the same manner , and kept at exactly the same temperature , so that pressure was the only difference ; and usually the effect was so well marked that there was no doubt about the result . In the case of chloride of sodium , solution goes on so slowly , and the . mechanical equivalent of the force of crystallization is so great , that if pressure had been applied for only a few hours one might have concluded , with Bunsen , that pressure has no influence on solubility ; but , by maintaining it for a week or more , there was no difficulty whatever in perceiving that a solution which was quite saturated without pressure , dissolved more under a pressure of about 100 atmospheres . The solubility of a salt in water appears to me to result from a kind of affinity which decreases in force as the amount of salt in solution increases . This affinity is opposed by the crystalline polarity of the salt ; and when the two forces are equal , the solution is exactly saturated . As is well known , a change in temperature alters this equilibrium ; and , according to my experiments , mechanical pressure relatively increases one or other of these opposing forces , according to the mechanical relations of the salt in dissolving . At all events in the case of chloride of sodium the extra quantity dissolved under pressure varies directly with it for such pressures as glass tubes will resist , in the same manner as , according to Thomson 's experiments , the fusing-point of ice is reduced . Thus I found that for a pressure of 491 atmospheres the extra solubility was 176 per cent. , and for 121 atmospheres '431 , which are almost exactly in the same ratio . Hence , if S be the amount soluble without pressure , under a pressure of p atmospheres the solubility at the same temperature would be S +ps , where the values of S and s are independent , and vary for different temperatures and different salts . Future experiments may perhaps show that this conclusion should be modified ; but yet it will be well to adopt it provisionally , in order to compare together the mechanical relations of different salts which otherwise would not be so intelligible . According to Michel and Krafft* and to Schifft , sal-ammoniac is the only salt known for certain to occupy more space in solution than when crystallized . Hence under pressure mechanical force must be overcome in dissolving , and experiment shows that , on this account , the relative force of crystalline polarity is increased and the solubility decreased . This is the reverse of what results from an elevation of the temperature , so that the effect cannot be due to heat generated by the pressure , but must be the direct consequent of pressure . Calculating from an experiment where the pressure was 164 atmospheres , which gave a decreased solubility of 1'045 per cent. of the whole salt in solution , a pressure of 100 atmospheres would cause '637 per cent. less to be dissolved than is soluble at 20 ? C. without pressure , and the pressure requisite to reduce the solubility to the extent of 1 per cent. would be 157 atmospheres . Expressing this fact in other words , we may say that a pressure of 157 atmospheres is the mechanical force with which the salt tends to dissolve in a solution containing 1 per cent. less than can dissolve at the same temperature without pressure , because the two forces exactly counterbalance one another . In a still more dilute solution the force would of course be still greater , in accordance with the fact of a greater pressure being necessary to prevent the salt from being dissolved . Supposing then that we had a solution a trifle more dilute than that just named , and in such indefinitely large quantity that a cubic inch of the salt could dissolve in it and yet produce no sensible change in its strength , so that from first to last it might be considered to dissolve under a pressure of 157 atmospheres , and also supposing that it was rigidly enclosed on all sides but one , so that the whole expansion must take place in one direction over an area of one square inch , since on dissolving there is an increase in bulk from 100 to 115'78 , the solution of this cubic inch would , as it were , raise 2355 lbs. through the space of 1578 inch . This is mechanically the same as 371k lbs. raised 1 foot , or , the specific gravity of the salt being 1*53 , the same as 171 times the weight of the salt itself raised 1 metre . Since it involves no arbitrary unit but the metre , I shall adopt the last expression as the measure of the total amount of mechanical work done by the solution of salts which expand in dissolving , and which may conversely be looked upon as the measure of the mechanical force rendered latent and , as it were , expended in the act of crystallization when crystals are deposited . The value of this mechanical equivalent of course varies with the strength of the solution , as already remarked . In the case of salts which occupy less space when dissolved than when solid , pressure , like the increased temperature , causes them to be more soluble ; mechanical force is lost when they dissolve , and is , as it were , expended in giving rise to solution . When water thus containing more of a salt than could otherwise be dissolved at the same temperature is just saturated under any given pressure , the amount of pressure represents the force of crystalline polarity tending to cause the salt to be deposited in a crystalline form , but which is exactly counterbalanced by that pressure . I will not give the details for each salt , but subjoin a Table of the results at which I have arrived for such as illustrate particular points of interest , the calculations being all made 1863 . ] 543 in accordance with the principles already described . I also give them in the case of water , calculated from Thomson 's experiments , assuming that , when ice melts and mixes with water , it may be looked upon as dissolving in it ; and , as will be seen , the mechanical force thus deduced is of the same general order of magnitude as that generated by the crystallization of salts . I. II . IV . V. 1 . Chloride of Sodium ... . 1357 97 '407 -419 157 2 . Sulphate of Copper ... . 4-83 60 1 910 3-183 7 3 . Ferridcyanide of Potassium ... ... ... ... . . 2-51 86 -288.335 42 4 . Sulphate of Potash ... . 3121 63 1 840 2-914 42 5 . Ferrocyanide of Potassium ... ... ... ... . . 8'90 66 1-640 2-485 20 6 . Water ... ... ... ... . . 893 ... . 991 106 Nos. 2 and 5 are calculated as hydrated crystals . Column I. gives the expansion of each salt in crystallizing from a nearly saturated solution in water , the volume in a crystalline state being taken at 100 . Column II . gives the actual pressure in atmospheres in the experiment . Column I11 . gives the increased solubility due to the pressure given in column II . , the total amount of salt dissolved without pressure being taken at 100 . Column IV . gives the increase in solubility that would be produced by a pressure of 100 atmospheres , as calculated in accordance with the principles already described , the same unit being taken as in column III . Column V. gives the value of the mechanical work that could be done , or , so to speak , the amount of mechanical force set free when the various substances crystallized from a solution containing 1 per cent. more than would be dissolved without pressure , as measured by the number of times its own weight which any unit of the various salts could raise to the height of 1 metre in the act of crystallization . Conversely , it is the amount of mechanical force which becomes latent in the act of solution ; and in the case of a still more supersaturated solution it would be greater , and vice versed , in accordance with the fact of the increased solubility varying with the pressure . 544 On comparing together the various salts , it will be seen that their properties vary very considerably . Thus , under the same pressure , the extra quantity of sulphate of copper dissolved in nearly ten times that of ferridcyanide of potassium . The mechanical equivalents also vary even more , being ( for chloride of sodium ) about 22times as great as for sulphate of copper . On the contrary , the mechanical equivalents of ferridcyanide of potassium and sulphate of potash are the same ; but , under equal pressures , the extra quantity of the latter dissolved in nearly nine times as great , owing to the difference in the amount of expansion in crystallizing . This latter is , however , nearly the same for water and ferrocyanide of potassium , whilst , under the same pressure , the extra quantity of that salt dissolved is 21times that of ice , in consequence of the much greater mechanical equivalent of the ice . It appears to me that we may provisionally conclude that the increased solubility due to pressure varies directly with the change of volume , and inversely with the mechanical equivalent of the force of crystalline polarity , so that , if S be the total amount of salt which dissolves without pressure , c be some function of the change in volume in dissolving , and m some function of the mechanical equivalent of the force of crystalline polarity , the solubility , at the same temperature , under a pressure of p atmospheres would be S+ o-c . If the salt be one that expands on dissolvin ing , c of course is negative , and therefore under pressure the solubility becomes S-_p-'c ; that is to say , it is diminished , as proved by experiments with sal.ammoniac . If no change in volume took place , we may , I think , also conclude that pressure would not in any way increase or decrease the solubility of a salt . Moreover , since , when a solution is just saturated , the force with which the salt tends to crystallize is equal to that with which it tends to dissolve , their mechanical equivalents must be equal and opposite . Hence we may perhaps conclude that , other circumstances being the same , the mechanical equivalent of a salt like chloride of sodium , which so readily attracts moisture , would be greater than that of one like sulphate of copper , which so readily loses even its water of crystallization ; and thus also the relative influence of equal amounts of 1863 . ] 545 pressure would be very different , as is confirmed by experiment in the case of these and some other salts . The facts I have described , therefore , show that there is a direct correlation between mechanical force and the forces of crystallization and solution . According to some chemists , the latter is an instance of real combination ; but , whatever views be entertained respecting its nature , we cannot , I think , deny that the force represents some modification of chemical affinity , or is at all events most closely allied to it . In comparison with some kinds of affinity , it may indeed be , and probably is , weak ; but yet , as I have shown , it sometimes has a very considerable mechanical equivalent , even when nearly counterbalanced by an opposite force ; and since such pressures as glass tubes will resist have no very great influence on what we may perhaps consider a weak affinity , we cannot expect that any pressure at our command would have much influence on strong affinities . I have , however , succeeded in obtaining some results which apparently show that pressure influences undoubtedly chemical changes taking place slowly , and therefore probably due to weak , or nearly counterbalanced , affinities . The method adopted in this part of the inquiry was to seal up some solid substance in a solution which gives rise to a slow double decomposition , taking great care to have in the tube with pressure , and in that without , pieces cut so as to be of the same size and form , and a solution of the same character , so that , with the exception of pressure , all the conditions were the same . Possibly I may be so fortunate as to discover some case where the affinity is so weak that pressure may determine whether it go forward or not , of which fact the structure of metamorphic rocks furnishes examples ; but hitherto I have only been able to prove that pressure modifies the rate at which chemical action takes place . This branch of the inquiry is , however , beset with many difficulties , for the change in volume produced by double decomposition is small , and its determination involves several complicated questions . The volume of the solids is easily determined ; but that of the salts in solution is not the same when other salts are present as when they are dissolved in pure water , and varies much according to the strength of the solution and the nature of the salts ; and many points are still so obscure , that I shall only give two cases by way of example . 546 When a portion of Witherite is enclosed in a tube with a strong solution of protochloride of iron , there is a slow decomposition into chloride of barium , which is dissolved , and carbonate of iron , which remains firmly attached to the Witherite , and would ultimately give rise to an excellent pseudomorph . The best conclusion at which I have been able to arrive is , that there is in this change an increase in volume equal to about 10'7 per cent. of the Witherite altered , so that , under pressure , mechanical force must be overcome . In an experiment where everything went on in a very satisfactory manner , the pressure was maintained for three months at from 80 to 100 atmospheres , and for one month was under 80 atmospheres , so that , on an average , it was about 80 atmospheres ; and I found that the amount of chemical change was 21*7 per cent. less than when , all other circumstances having been the same , there had been no pressure ; thus clearly showing that pressure had , as it were , diminished the force of chemical affinity . If then one cubic inch had been altered under this pressure , it would have overcome a mechanical force equal to that required to raise 1200 lbs. through the space of *107 inch , which is equivalent to raising twenty-one times its own weight to the height of 1 metre ; and under the same circumstances 1'278 cubic inch would have been altered when no such mechanical force had to be overcome . Supposing then that in both cases the total energy at work was the same , but in one was altogether expended in producing a chemical result , and in the other in producing partly a chemical and partly a mechanical effect , we may say that the force which gives rise to the purely chemical change , taking place at a particular rate , is equal to that which gives rise to this chemical effect , taking place at *783 of that rate , and to a mechanical effect equal to the force required to raise in the same space of time 34'87 times the weight of the Witherite altered to the height of 1 metre . Supposing also that the power of chemical force varies as the rate at which it gives rise to a chemical change , in the same manner as the power of a mechanical force varies as the velocity of motion imparted by it , we may perhaps conclude that this mechanical force is equal to -217 of the chemical force , and that the whole energy of the chemical action under the conditions of the experiment was equal to the mechanical power required to raise in the same period of time 160 times the weight of the Witherite altered to 1863 . ] 547 the height of 1 metre . If these principles are correct , a pressure of more than 370 atmospheres would have entirely counterbalanced the force of chemical affinity , since to produce any chemical change it would then have had to overcome a greater force than it possessed . This is so great a pressure that I fear it will be difficult to prove the deduction by experiment ; and until some such case can be found , capable of being verified , these calculations must be considered as little more than suggestions , which future investigations may confirm or disprove . When calcite is sealed up in a mixed and rather strong solution of chloride of sodium and sulphate of copper , slow double decomposition gives rise to malachite , sulphate of lime , and carbonic acid ; and though this case is extremely complicated , and it is very difficult to determine what would be the change in volume , yet , so far as I am able to make out , until the solution becomes saturated with sulphate of lime , there is a decrease in volume equal to about 8 per cent. of that of the calcite altered , so that , under pressure , mechanical force is the very reverse of being opposed to the chemical change . Three experiments , all indicating the same fact , and in which , on an average , the pressure was about 90 atmospheres for two weeks , show that , as a mean of the whole , the amount of chemical change was 17 per cent. more with the pressure than without ; thus proving that pressure had , as it were , increased the force of chemical affinity . Calculating according to the principles described above , we may conclude that a pressure of 530 atmospheres would have caused the action to take place at double the rate , and that therefore the chemical action is equivalent to the expenditure of that amount of mechanical force , being thus generated by it . Arguing then in a manner similar to that already described , but modified to suit the different conditions , if there be a contraction equal to 8 per cent. of the bulk of the calcite , there must be a loss of mechanical force capable of raising 28 times the weight of the calcite altered to the height of 1 metre , in the time required for the chemical change ; which amount of mechanical energy , as it were , becomes latent , and is transformed into chemical action , and would again exhibit itself as a mechanical force if , by any means , the chemical affinities could be inverted and everything restored to its original state . In a like manner , other experiments indicate that in some cases 548 pressure causes a slower , and in others a quicker chemical action , whilst in others it has scarcely any influence whatever ; and though , for reasons already explained , I say it with some hesitation , yet , bearing in mind what is already known respecting the action of pressure on hydrate of chlorine , hydrated hydrosulphuric acid , and other substances described by the various authors referred to in the notes , I think the facts I have described make it very probable that further research will show that pressure weakens or strengthens chemical affinity according as it acts against or in favour of the change in volume ; as if chemical action were directly convertible into mechanical force , or mechanical force into chemical action , in definite equivalents , according to well-defined general laws , without its being necessary that they should be connected by means of heat or electricity . On the present occasion I shall not attempt to consider the various geological and mineralogical facts which appear to me to admit of the application of the principles I have described , for many of them are peculiarities in structure of which neither myself nor any one else has ever given a description , and would therefore demand a preliminary notice . However , I may say that it appears to me that a number of facts connected with metamorphic rocks and the phenomena of slaty cleavage , which , to me at all events , have hitherto been inexplicable , are readily explained if mechanical force be directly correlated to chemical action , and if in some cases the direction in which crystals are formed be more or less related to pressure , in some such way as there is a connexion between their structure and magnetic force , as shown by the experiments of Plucker , Faraday , Tyndall , and many other observers . We may also , I think , explain the origin of the impressions on the limestone pebbles in the " Nagelflue " in Switzerland , about which so much has been written in Germany and France , without a satisfactory reason having been discovered ; and the same explanation accounts for the mutual penetration of the fragments of which some limestones are formed , apd for the banded structure of some which possess slaty cleavage . The curious teeth-like projections with which one bed of limestone sometimes enters into another , also to a certain extent indicate a chemical action depending on mechanical force ; and probably the same may be said of some of the peculiarities of slickensides and mineral veins . It is also possible that a pressure of several hundred atmospheres may facilitate some of the chemical changes involved in the transformation of water and carbonic acid into the organic compounds met with in animals and plants of low organization found at great depths in the ocean , and thus to a certain extent compensate for diminished light . I , however , most willingly admit that very much remains to be learnt before we can say to what extent the principles I have described are applicable ; and yet , at the same time , cannot but think that henceforth they must be taken into account in many departments of chemical and physical geology , and will readily explain a number of facts which otherwise would be very obscure .

112307

3701662

On the Physiological Properties of Nitrobenzole and Aniline

550

559

Proceedings of the Royal Society of London

Henry Letheby

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0118

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112307

10.1098/rspl.1862.0118

http://www.jstor.org/stable/112307

Biology 2

Chemistry 2

Biology

I. " On the Physiological Properties of Nitrobenzole and Aniline . " By HENRY LETHEBY , M.B. , F.L.S. , &c. , Professor of Chemistry , and late Professor of Toxicology in the Medical College of the London Hospital . Communicated by Dr. SHARPEY , Sec. R.S. Received April 23 , 1863 . It is on record that Thrasyas , the father of Botany , was so skilled in the preparation of drugs , that he knew how to compound a poison which would remain for days in the living body without manifesting its action , and would at last kill by a lingering illness . Theophrastus speaks of this poison , and says its force could be so modified as to occasion death in two , three , or six months , or even at the end of a year or two years . The writings of Plutarch , Tacitus , Quintilian , and Livy are full of instances of what seem to be this kind of slow and occult poisoning . In fact , until recently there has been a common belief among the unlearned that a skilful poisoner could so apportion the dose and combinations of certain subtle agents that he could destroy the life of his victim with certainty , and at the same time measure his allotted moments with the nicest precision , and defy the utmost skill of the physician and the chemist . Even so late as the 16th century this belief was shared by the learned of the medical profession ; for we are told , in Sprat 's ' History of the Royal Society , ' that among other questions which were drawn up by the earlier Fellows to be submitted to the Chinese and Indians was , " ' Whether the Indians can so prepare that stupefying herb , Datura , that they make it lie several days , months , years , according as they will have it , in a man 's body without doing him any hurt , and at the end kill him without missing half an hour 's time ? " Modern toxicologists have long since discarded these notions , and have set them down to the vague fears and exaggerated fancies of the ancients , rather than to the sober contemplation of facts . But the account which I am about to give of the physiological properties of nitrobenzole will show that there is one substance , at least , which realizes to a great extent the extraordinary opinions of the ancients . This compound may be given today , and yet , if the dose be not too large , it shall not manifest its action until tomorrow , or the day after , and shall then destroy life by a lingering illness , which shall not only defy the skill of the physician , but shall also baffle the researches of the medical jurist . These facts are so remarkable , that they would be hardly credited if they were not susceptible of the proof of demonstration . They are likewise the more interesting and important from the circumstance that nitrobenzole is now a common article of commerce , and is accessible to everyone . In every manufactory where nitrobenzole and aniline are prepared on a large scale , the peculiar narcotic effects of these poisons are often observed . The vapours escaping into the atmosphere are breathed by the workmen , and cause distressing headache and a heavy , sleepy sensation . For the most part these effects are not serious , but are quickly relieved by fresh air and a mild stimulant , as a glass of brandy and water . Now and then , however , the workmen , from carelessness in their habits , expose themselves to the action of comparatively large quantities of these poisons , and then the effects are most dangerous . Two fatal cases of poisoning by nitrobenzole have been referred to me by the coroner for investigation during the last two years , and in both instances they were the results of careless manipulation . In one case a man , forty-three years of age , spilt a quantity of the liquid over the front of his clothes , and he went about for several hours in an atmosphere saturated with the poison . In the other a boy , aged seventeen years , received a little of the liquid into his mouth while sucking at a siphon . The effects were nearly the same in both cases , notwithstanding that in one the poison was inhaled , and in the other it was swallowed . For some time there was no feeling of discomfort beyond that of drowsiness ; gradually , however , the face became flushed , the expression stupid , and the gait unsteady the sufferers had the appearance of persons who had been drinking . Little by little this stupor increased , until it passed into profound coma , and in this condition they died . The progress of each case was much the same as that of slow intoxication , excepting that the mind was perfectly clear until the coming on of the fatal coma . This was sudden , like a fit of apoplexy ; and from that moment there was no return of consciousness or of bodily powerthe sufferer lay as if in a deep sleep , and died without a struggle . The duration of each case was nearly the same ; about four hours elapsed frcm the time of taking or inhaling the poison to the setting in of the coma , and the coma lasted for about five hours . After death there were no appearances of convulsion , but rather of narcotism and apoplexy . The face was flushed ; the lips were livid ; the superficial vessels of the body , especially about the throat and arms , were gorged with blood ; the dependent parts were turgid ; the blood was everywhere black and fluid ; the lungs were somewhat congested ; the cavities of the heart were full ; the liver was of a purple colour , and the gall-bladder distended with bile ; the brain and its membranes were turgid , and in the case of the man there was much bloody serosity in the ventricles . Analysis discovered the existence of nitrobenzole in the brain and stomach , and also of aniline . These effects were so remarkable , that I determined to examine them still further by experiments on domestic animals . Dogs and cats were submitted to the action of from thirty to sixty drops of nitrobenzole which had been well washed with dilute sulphuric acid and water to free it from every trace of aniline . The poison was generally administered by pouring it into the mouths of the animals , but sometimes it was given by means of an oesophagus-tube . When the nitrobenzole had come into contact with the mouth , it always caused discomfort , as if from unpleasant taste , and there was profuse salivation . Its local action on the stomach , however , was never very great , for there was rarely any vomiting until the setting in of nervou symptoms , and this seemed to be due to sympathy rather than to any local irritation of the stomach . Two classes of effects were clearly observed : there was either the rapid coma which characterized the operation of the poison on the human subject , or there was a slow setting in of paralysis and coma , after a long period of inaction . 'When the effects were speedily fatal , the animal was soon seized with giddiness and an inability to walk . The weakness of the limbs first appeared in the hind extremities , and was manifested by a difficulty in standing ; but very soon it extended to the fore legs , and then to the head and neck . There was complete loss of voluntary power . The animal lay upon its side , with its head drawn a little back , and with its limbs in constant motion , as if in the act of walking or running . The muscles of the back were occasionally fixed in spasm , and every now and then the animal would have a sort of epileptic fit . It would look distressed , would howl as if in pain , and would struggle violently . After this it would seem exhausted , and would lie powerless . The pupils were widely dilated , the action of the heart was tumultuous and irregular , and the breathing was somewhat difficult . For some time , however , the animal retained its consciousness , for it would look up , and wag its tail when spoken to ; but suddenly , and often at the close of a fit , it would become comatose the eye would remain open , but the conjunctiva would be insensible to touch , and the movements of the limbs would nearly cease ; the breathing would be slow and somewhat stertorous , and the animal would appear as if s it were in a deep sleep . This condition would last until it diedthe time of death varying from twenty-five minutes to twelve hours after the administration of the poison . When the action of the poison was slower , there was often no visible effect for hours or days . At first there was always a little discomfort from the taste of the poison , but this soon subsided , and then for a day or more the animal appeared to be in perfect health . It would go about as usual , would be quite lively in its movements , would eat its food heartily , and in fact would seem to be in no way affected by the poison . Suddenly , however , it would look distressed , it would have an attack of vomiting , and it would tumble over in an epileptic fit . When this had subsided , it was generally found that the animal was weak , or even quite paralysed in its hind extremities ; and after two or three of such attacks , the loss of voluntary power would extend to the fore limbs . The animal would lie upon its side perfectly helpless ; and then the progress of the case was much the same as that already described , except that it was considerably slower . Consciousness , for example , would be retained for days after the animal was paralysed , and , although it was quite unable to stand , it would take food and drink when they were put into its mouth . The condition in which it lay was most distressing : the look was anxious and full of fear ; the limbs were in constant motion ; and every now and then there would be a violent struggle , as if the animal was in a fit , or was making fruitless efforts to rise . This would last for days , and then there would be either a gradual restoration of voluntary power with complete recovery , or death from exhaustion . The time that elapsed from the administration of the poison to the coming on of the first symptoms , namely the epileptic fit , varied from nineteen hours to seventy-two-in most cases it was about two days ; and the time of death was from four to nine days . The post-mortem appearances were nearly the same in all cases , whether the death was quick or slow . The vessels of the brain and its membranes were extremely turgid ; the cavities of the heart were full of blood ; the lungs were but slightly congested ; the liver was of a deep purple tint , and the gall-bladder distended with bile ; the stomach was natural , without sign of local irritation ; and the blood all over the body was black and uncoagulated . Whenever the progress of the case had been quick , and death had taken place within twenty-four hours , the odour of the nitrobenzole was clearly perceptible in the stomach , the brain , and the lungs ; and there was always unmistakeable evidence of the existence of aniline in the organs of the body . In the slower cases the odour of the poison had often entirely disappeared ; but generally there were distinct traces of aniline in the brain and urine , and sometimes in the stomach and liver ; occasionally , however , no poison was found . It has appeared to . me that the facts which are here elucidated are very remarkable ; for they not only indicate a rare circumstance in toxicology , namely , that a poison may be retained in the system for many days without showing its effects , but also that the poison may be changed into an entirely different substance . The importance of these facts cannot be overrated ; they are alike interesting to the chemist , the physiologist , and the medical jurist ; for , without dwelling on a very possible occurrence-namely , the criminal administration of this poison , with the knowledge that the effects would be delayed , that the symptoms would correspond to those of natural disease , that the progress of the case would be lingering , and that there would be either no discovery of poison in the body , or the discovery of a thing different from that administered-it will be manifest that the study of these facts by the medical jurist is of public importance . To the physiologist they are also interesting , insomuch as they indicate a reducing power in the animal body by the conversion of nitrobenzole into aniline . I have endeavoured to ascertain whether this is due to a living or a dead process . In the first place , I find that dead and decomposing organic matter will effect the change alluded to ; for when nitrobenzole is placed in the dead stomach , or is kept in contact with putrid flesh for several hours , there is a partial reduction of it into aniline . This may be the source of the poison found in the dead body ; but , on the other hand , there is a great similarity in the physiological effects of nitrobenzole and those of aniline . When aniline is given to dogs and cats in doses of from twenty to sixty drops , it causes rapid loss of voluntary power . The animal staggers in its gait , looks perplexed , and falls upon its side powerless . Its head is drawn back , the pupils are widely dilated , there are slight twitchings or pasms of the muscles , the breathing is difficult , the action of the heart is tumultuous , and the animal quickly passes into a state of coma . From this it never recovers , but remains upon its side as if in a deep sleep , and so dies in from half an hour to thirty-two hours . The post-mortem appearances are much the same as the last : the brain and its membranes are turgid , the cavities of the heart are nearly full of blood , the lungs are but slightly congested , and the blood all over the body is black and uncoagulated . In every case the poison was easily discovered in the brain , the stomach , and the liver . While however , there seems to be a probable conversion of nitrobenzole into aniline in the living animal body by a process of reduction , there is also undoubtedly a change of an opposite character going on upon the surface of the body , whereby the salts of aniline are oxidized and converted into mauve or magenta purple . Some remarkable facts illustrative of this have been brought under my own notice , and have been the subject of clinical observation . In the month of June 1861 , a boy aged 16 was brought into the London Hospital in a semi-comatose condition . He had been scrubbing out the inside of an aniline vat , and while so doing he breathed an atmosphere charged with the vapour of the alkali , and became insensible . He did not suffer pain or discomfort , but was suddenly seized with giddiness and insensibility . When he was brought to the hospital he looked like a person in the last stage of intoxication : the face and surface of the body were cold , the pulse was slow and almost imperceptible , the action of the heart was feeble , and the breathing was heavy and laborious . After rallying a little , he complained of pain in his head and giddiness . It was then noticed that the face had a purple hue , and that the lips and lining membrane of the mouth and the nails had the same purple tint . The next day , although the narcotic effects of the poison had passed away , he was still remarkably blue , like a patient in the last stage of cholera . In the early part of last year , sulphate of aniline was given in rather large doses to patients in the London Hospital affected with chorea . The doses ranged from a quarter of a grain to seven grains . They were frequently administered , so that large quantities of the salt were taken in a very short time . In one case as much as 406 grains were given in the course of a few days . No very remarkable effects followed beyond this-that after a few doses had been taken , and the system had become , as it were , saturated with the salt , the face became of a leaden blue colour , the lips and gums looked as if the patients had been eating black currants , and the nails also acquired a purple hue . The colour faded a little before the time came for the administration of another dose , but soon after taking it it appeared again ; and this was the subject of constant observation . Dr. Fraser and Dr. Davies have recorded the results of their experience in five cases * , from which it would seem that , although the free alkali is a powerful poison , the sulphate of it has but little action upon the animal body . The general conclusions which appear to me to be warranted by these investigations are:1st . That nitrobenzole and aniline in its free state are powerful narcotic poisons . 2nd . That they exert but little action , as local irritants , on the stomach and bowels . 3rd . That although the effects may be quick , and the fatal termination of them rapid , yet nitrobenzole may remain in the system for a long time without manifesting its action . 4th , That the salts of aniline are not nearly so poisonous as the free alkali . 5th . That in rapid cases of fatal poisoning , both the poisons are readily discovered in the dead body . 6th . That in slow cases the poisons may be entirely changed or eliminated , and therefore not recognizable . 7th . That both of the poisons appear to be changed in the body by processes of oxidation and reduction , nitrobenzole being changed into aniline , and aniline and its salts into mauve cr magenta . In an appendix t are given notes of the two cases of fatal poisoning by nitrobenzole referred to in the paper , and a detailed account of twelve experiments on animals with nitrobenzole , and three with aniline ; also the process employed for the recognition of aniline and nitrobenzole in the dead body , as follows:1st . The matters to be analysed were bruised in a mortar with a little water , and very slightly acidulated with.dilute sulphuric acid , 2nd . They were then submitted to distillation in a glass retort the distilled products being saved in three or four separate portions by changing the receiver at different stages of the process . In this way the presence of nitrobenzole was discovered . 3rd . The residue in the retort , when reduced to a pulpy mass by the distillation , was treated with strong spirit of wine and filtered . 4th . The filtered alcoholic solution which contained the aniline was treated with a slight excess of subacetate of lead , and again filtered . In this way gum , dextrine , &c. were removed . 5th . The filtered solution was treated with a slight excess of a saturated solution of sulphate of soda in water . In this manner the excess of lead was precipitated as a sulphate . 6th . The clear solution was then made very alkaline with caustic potash , and distilled to dryness from an oil-bath . The aniline , together with ammonia from the animal matters , was found in the clear , colourless , distilled spirit . 7th . This was neutralized , or rather made acid , with a slight excess of dilute sulphuric acid , and evaporated nearly to dryness in a white porcelain dish . If necessary , the spirit was saved by distillation . 8th . The residue was of a pinkish colour if aniline was present , and occasionally there were little streaks of blue around the edges of the white porcelain dish . If the quantity of the saline residue was not more than a grain or so , it was at once tested by dissolving it in a few drops , or even in a single drop , of dilute sulphuric acid ( 1 to 1 ) . A small portion of it was then placed upon a strip of bright platinum ; and the platinum having been conneeted with the positive pole of a single cell of a Grove 's battery , the liquid was touched with the negative pole : in a few secon ds , if aniline was present , the liquid would acquire a bronze , a blue , or a pink colour ; the kind of colour being dependent on the am ount of aniline present-bronze being the result of much aniline , and pink of a very little . In this way at least the -iooth part of a grain of aniline was easily recognized . To another portion of the acid liquid placed upon a white porcelain plate , a little peroxide of lead or red prussiate of potash was added , and a blue or purple reaction followed . This test is not so delicate as the last , for it fails when the amount of aniline is less than the T-:ith of a grain . Other tests may be resorted to if necessary , as when the quantity 558 of aniline is large . Thus peroxide of manganese or bichromate of potash may be used in the same way as the red prussiate of potash in the last experiment ; but these tests will not answer with less than the -^)th of a grain of aniline . Lastly , a drop of a solution of chloride of lime may be added to the acid liquid , and if the quantity of aniline exceeds the To-oth part of a grain it will cause a purple reaction . 9th . If the quantity of saline residue from the last operation is large , and there is reason to believe that much ammonia is present , this alkali must be got rid of , for it greatly interferes with the success of the colour-experiments . The residue , therefore , is made moist with water , and rubbed down with about twice its bulk of neutral carbonate of soda . It is then exposed to the air for a short time until the odour of ammonia has passed away . It is then treated with strong alcohol , filtered , acidulated with dilute sulphuric acid , and again evaporated . The aniline is now fit for the colour-experiments . There are no fallacies to these experiments ; for although , as I have elsewhere shown , strychnia will give nearly the same colourreactions , yet in the first place this alkali is not volatile like aniline , and will not therefore distil over as the latter does ; and in the next place , while the best effects , in respect of colour , are developed with dilute acid and aniline , strychnia requires the concentrated acid . These differences are sufficient to prevent any embarrassment as regards the two alkaloids .

112308

3701662

On the Immunity Enjoyed by the Stomach from Being Digested by Its Own Secretion during Life. [Abstract]

559

561

Proceedings of the Royal Society of London

Frederick W. Pavy

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112308

http://www.jstor.org/stable/112308

Biology 2

Physiology

Biology

II . " On the Immunity enjoyed by the Stomach from being digested by its own Secretion during Life . " By FREDERICK W. PAVY , M.D. Communicated by Dr. SHARPEY , Sec. R.S. Received April 29 , 1863 . ( Abstract . ) The author stated that the opposition which his view on the above subject received the evening of its announcement , in his former communication read January 8 , 1863 , had induced him to perform a series of additional experiments . As from these experiments some important confirmatory evidence was supplied , he deemed it desirable to present a further communication to the Society on the subject . He had again denuded the stomach of a patch of mucous mem1863 . ] 559 bran , and in one experiment had allowed the animal to live for ten days . It had fed in an ordinary manner every day , and when killed , reparation was found in an advanced stage towards completion , the walls opposite the denuded part having been considerably thickened by new matter that had been thrown out . Upon much further extended observation the author found that the standard he had taken from the rabbit , as regarded the postmortem action of the contents of the stomach upon the organ itself , was not just in its application to the dog . Actual experiment on the dog had shown that upon the animal being killed at a period of full digestion , and its temperature being afterwards maintained about the degree belonging to life , the effect at the end of five and six hours only amounted to more or less digestion of the mucous membrane . In the rabbit , under similar circumstances , the effect had gone on to perforation , on account , apparently , of the stronger acidity of the gastric contents . In reality , then , the effect of arresting the circulation through the stomach during life , about coincided in both rabbit and dog with what occurred , other circumstances being equal , after death . As a counterpart to the experiments originally mentioned , where dilute non-corrosive acids had been introduced into the stomach of the dog , and the flow of blood through the organ afterwards arrested , an operation that was followed by comparatively rapid perforation , the author had used the same acids , in the same quantities , and similarly diluted , but the circulation was allowed to remain free , and now the stomach resisted digestive attack . Ligatures had of course been applied to secure the retention of the acid liquid introduced . A mode of experimenting suggested by Dr. Sharpey had been undertaken . After an incision through the anterior wall of the stomach , a portion of the posterior wall had been drawn forward , and a ligature placed tightly around it , so as thus to arrest the circulation through a limited portion of the organ 's parietes . It was found that this constricted mass underwent digestion like a morsel of food . An experiment had been performed bearing on the explanation that had been given to account for the attack upon the living frog 's legs and rabbit 's ear by digestion whilst the stomach remained protected . Three drachms of muriatic acid , diluted to three ounces with water , were introduced into the stomach of a dog , and the end of the oesophagus and the pylorus ligatured , without including the vessels , so that the circulation through the organ was left free . In one hour and forty minutes death took place , and on the parts being examined immediately , perforation , with extensive digestion of the interior of the stomach throughout , was found . The author considered that the question of result was clearly shown to resolve itself into one dependent on degree of power possessed by the acid contents of the stomach on the one hand , as against the alkaline circulation on the other . With a certain amount of acid only in the stomach , the circulation can afford the required protection ; whilst with a larger amount the influence of the acid prevails , and digestive solution of the organ is the result . Allow , now , the contents of the stomach to remain the same , and vary the degree of vascularity in the parts submitted to the digestive influence . We have simply here a converse arrangement of the circumstances ; and the position is represented by the situation of the stomach as compared with that of the frog 's legs and rabbit 's ear .

112309

3701662

On a Question of Compound Arrangement

561

563

Proceedings of the Royal Society of London

J. J. Sylvester

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0120

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112309

10.1098/rspl.1862.0120

http://www.jstor.org/stable/112309

Formulae

Tables

Mathematics

III . " On a Question of Compound Arrangement . " By J. J. SYLVESTER , M.A. , F.R.S. , Professor of Mathematics in the Royal Military Academy , Woolwich . Received April 27 , 1863 . My successful but as yet unpublished researches into the Theory of Double Determinants have involved the consideration of the following curious case of arrangements . There are given m+ n1 counters of n distinct colours just capable of being packed into mn urns . The question refers to the distribution of the counters among the urns , subject to the condition that it shall not be possible to form a closed circuit of double colours between any number of the urns chosen arbitrarily , ex. gr. we must allow no distribution of counters in which one urn contains blue and yellow , a second yellow and red , a third red and green , and a fourth green and blue , because here blue , yellow , red , and green would form a closed circuit . This condition , it is evident , excludes the same combination of colours from existing in any two of the urns , and also the repetition of any one colour in the same urn . Any distribution of counters obeying this condition may be called an excyclic distribution . I annex two propositions , one qualitative , the other quantitative , referring to such distributions . Qualitative Theorem . In any excyclic distribution between m urns of m +n-1 counters of n different colours , any set of counters selected at will must befewer in number than the number of distinct colours which they contain added to the number of urnsfrom which they are drawn . Before going on to enunciate the second proposition I must premise one or two simple definitions . The capacity of an urn means the number of counters it will contain , the frequency of a colour the number of counters of that colour , so that the sum of all the capacities and the sum of all the frequencies must be each equal to the number of the counters . Again , by the diminished capacity of any urn or diminished frequency of any colour , I mean such capacity or frequency respectively diminished by unity . Finally , by thepolynomial function of any set of numbers a , b , ... I , I mean the coefficient of xa . yb ... z. in the expansion of ( x+y+ ... )a+b+ ... +l . I can now enunciate the following Quantitative Theorem . The number of modes of excyclic distribution between m urns of m+n1 counters of n different colours is equal to the product of the polynomial function of the diminished frequencies of all the several colours multiplied by the polynomial function of the diminished capacities of all the several urns . Observation . A double determinant means the resultant of a system of ( m +n 1 ) homogeneous equations each containing mn terms , and linear in respect to each of two systems of m and n variables taken separately , but of the second order in respect to the variables of these two systems taken rn(m + n--i ) collectively . Any such resultant is of the degree -r(m1 ) ( --1 ) 7r(m1.)7r(n-1\ in respect of the given coefficients , and may be represented by an ordinary determinant of the ( m + n-)th order , every one of whose terms corresponds to a particular system of capacities of the in urns and of repetitions of the n colours in the question above treated . The total number of such systems or terms will be 7r(m+n-2 ) )2 7r(m1)7r(nl ) ' Every term in this determinant will itself be a sum of simple determinants of the ( mnl)th order , corresponding ( each to each ) with the totality of the excylcic distributions of ( mn+n--1 ) counters in respect of the particular systems of m capacities and n frequencies appertaining to that term ; so that the number of simple determinants whose sum constitutes a term in the grand total determinant is always the product of two polynomial coefficients . In the particular case , where one of the systems contains only two variables , one of these polynomial coefficients becomes unity , and the other sinks down to a binomial coefficient . The only instance of a double determinant which is believed to have been considered up to the present moment is that given by Mr. Cayley in the 'Cambridge and Dublin Mathematical Journal , ' vol. ix . 1854 , for the case of m= 2 , n= 2 .

112310

3701662

On a Theorem Relating to Polar Umbrae

563

565

Proceedings of the Royal Society of London

J. J. Sylvester

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0121

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112310

10.1098/rspl.1862.0121

http://www.jstor.org/stable/112310

Formulae

Neurology

Mathematics

IV . " On a Theorem relating to Polar Umbrae . " By J. J. SYLVESTER , M.A. , F.R.S. Received April 27 , 1863 . By polar umbree I mean such as obey in the strictest manner the polar law of sign , so that not only any two appositions or products of such umbrae derivable from one another by an interchange of two of their elements are to be considered each as the negative of the other , but also any such apposition or product becomes zero if the same element is found in it more than once . Thus Sir W. Hamilton 's i , j , k are not polar umbrae , because although ijk= -jik kij , &c. , ii , j , kk , instead of being nulls , are in the Calculus of Quaternions taken as unities* . Let us now define any set arranged either in line or column of such umbral quantities to be multiplied by a corresponding set of actual quantities when each term of the one set is multiplied by the corresponding one of the other , and the sum taken of the products so obtained as in the ordinary case of the multiplication of the lines or columns of two determinants inter se . Thus , ex. yr . ( a , b , cix , y , z ) , as also ( bsI/ is to mean the same product , viz. ax+ by +cz . Again , imagine a rectangular ( square or oblong ) matrix of polar umbre , and that each line thereof is multiplied by the same line of actual quantities , the product of the products so obtained I call a Factorial of the Matrix . I also call the product similarly obtained when the columns of the matrix are substituted for the lines , a Factorial of the same , but distinguish between the two by giving to one the name of a Transverse , the second of a Longitudinal Factorial of the matrix . We are now in a position to enunciate the following remarkable theorem : The product of any longitudinal by any transverse factorial of the same polar umbral matrix is identically zero . Ex. yr . Let of be a matrix of polar umbrae , but x , y , z and also 4 , n actual quantities . Then ( ax + b , cz ) ( dx + ey +fz ) is a transverse factorial , ( a +d/ ) ( b +en ) ( c +fT ) a longitudinal factorial of the above matrix , and by the theorem their product should be zero . This is easily verified . The two factorials expanded are respectively adx2 + bey2 + cfz + ( ae+ bd)xy + ( bf+ ce)yz+ ( af+ dc)zx , abcS3 + ( abf+ aec + dbc ) , ri + ( dec+ dbf+ aef)W2 + defr3 ; in their product the coefficient of x2T3 ==aboad=O , zxy3 =abcae + abebd= O , t242 " = abfad+ aecad+ dbcad= 0 , wyT2 = abfae + abfbd+ aecae + aecbd+ dbcae + dbcdb = aecbddbeae= aeebdaecbd= 0 , and so for all the other terms . This is the fundamental theorem by aid of which I obtain the resultant of a lineo-linear system of equations in its most perfect form . It is easy to obtain two different solutions , each of them unsymmetrical in respect of the data of the question ; the conversion and fusion of each of these into one and the same determinant , symmetrical in all its relations to the data , is effected instantaneously by a process derived from the above theorem . In that particular application of it , the umbre involved each represent columns of actual quantities in number equal to the number of places in the width and length of the umbral matrix to which they belong , so that each coefficient in the product of a lateral by a longitudinal factorial represents an ordinary determinant made up of these columns , from which it is evident that the polar law of sign and nullity necessary for the truth of the theorem are satisfied in the case supposed .

112311

3701662

Notes, Principally on Thermo-Electric Currents of the Ritterian Species. [Abstract]

565

566

Proceedings of the Royal Society of London

C. K. Akin

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112311

http://www.jstor.org/stable/112311

Electricity

Fluid Dynamics

Electricity

V. " Notes , principally on Thermo-electric Currents of the Ritterian Species . " By C. K. AKIN , Esq. Communicated by Professor STOKES , Sec. R.S. Received March 26 , 1863 . ( Abstract . ) The electromotive force of a thermo-electric couple is a function of the nature of the metals of which it is composed , and of the temperatures of the junctions . It is expressed in this paper by [ Ex y]T where x and y are names of metals , and T and t are temperatures . In this notation Becquerel 's two laws become a , b]t , =[a , 6-[a , b ] ; ... . ( I. ) and ( a , c)T= [ a , ]T+ [ , c]T ... ... ( II . ) From ( I. ) we learn that the electromotive force of a couple may be expressed as the difference of two quantities which are functions of the temperature and of the nature of the circuit , or [ , Y]O=[ , y]T--[l Y ] ... . . ( II . ) From ( II . ) we learn that any number of metals with their ends at the same temperature may be introduced without effect , or [ a , b]t+[b , c]t=[a , C]t ... . . ( IV . ) This equation will always be true if [ L Y ] t= [ t[y ] ... ... . ( V. ) whence we may write ( III . ) [ Iy t[X ? ]t[y]t[T + [ y3 T ; or , in other words , the electromotive force of a couple may be considered as the difference of the electromotive force of two metals , each of which is found by subtracting its tension at the higher temperature from that of the lower one . Everything therefore depends on a knowledge of the value of what may be called the electric tension of each metal at the various temperatures . This for every metal is a function of temperature , and may be called , in the language of the paper , a function of the nature ( or name ) of the metal and the temperature . ( The nature of the metal may be altered otherwise than chemically . ) If the temperature of the metal vary in any way throughout its length , then if it be homogeneous , the electromotive force will depend only on the temperatures of its extremities . In a circuit of one metal , the author considers that at the junction of the ends there may be a real discontinuity of temperature while there is a continuity of electric current . He regards the explanation of the effect by the stratum of air between the unequally heated ends to be unsatisfactory . Mercury , as is known , will not produce thermo-curyents in this way . The author considers that the texture , &c. , as well as the chemical nature of the substance , influences the value of the thermo-electric function . He also shows the possibility of the thermo-electric inversions first discovered by Professor Cumming .

112312

3701662

On the Nature of the Sun's Magnetic Action upon the Earth. [Abstract]

567

567

Proceedings of the Royal Society of London

Charles Chambers

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112312

http://www.jstor.org/stable/112312

Meteorology

Fluid Dynamics

Meteorology

I. " On the Nature of the Sun 's Magnetic Action upon the Earth . " By CHARLES CHAMBERS , Esq. Communicated by the President . Received April 30 , 1863 . ( Abstract . ) If the sun were a magnet of sufficient power to exert a sensible attraction upon a small magnet at the distance of the earth , it would have a real influence on the earth by inducing magnetism in its soft iron , and an apparent one due to the direct action of the sun upon the magnets used for measuring the earth 's variations of force . As the earth rotates upon its axis , producing a varying relation , as to position , of the place of observation with respect to the sun , a diurnal variation will thus be produced in the forces which act upon the magnetometers , which variation is shown to follow the simple law x= A sin ( h + a ) , x being the deviation of the magnet from its normal position , h the hour-angle of the sun ( and for a single day ) , Aa constant coefficient , and aa constant angle . A comparison of this result with the laws of the observed diurnal variations shows that direct and inducing action of the sun is not the sole cause of the variations . An endeavour is then made to prove that if any part of the observed diurnal variations is due to this cause , it is small in comparison with that produced by other forces in operation . This is done by separating from the observed variations the part of them which obeys the law x'=B sin ( h+ / ) , and comparing the variations in the values of B and p from month to month with those of A and a , when it is seen that the former obey a law which has but little similarity to the law of variation of the latter .

112313

3701662

Numerical Elements of Indian Meteorology.--Series I. [Abstract]

567

568

Proceedings of the Royal Society of London

Hermann de Schlagintweit

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112313

http://www.jstor.org/stable/112313

Meteorology

Biography

Meteorology

II . " Numerical Elements of Indian Meteorology."-Series I. By Dr. HERMANN DE SCHLAGINTWEIT , Corr. Memb. of the Academies of Sciences of Munich , Madrid , Lisbon , &c. Communicated by the President . Received May 4 , 1863 . ( Abstract . ) In this paper the author communicates Plates il which the iso2s thermal lines are represented between the latitudes of 5 ? N. and 36 ? W. , and longitudes of 78 ? E. and 98 ? E. of Greenwich . 1st , of the mean temperature of the year ; 2nd , of the cool season , viz. December , January , and February ; 3rd , of the hot season , viz. March , April , and May ; 4th , of the rainy season , viz. June , July , and August ; 5th , of the autumn , viz. September , October , and November . The memoir which accompanies the Plates contains a statement of the data on which the isothermal lines are founded . These are : 1 . Meteorological researches made by the author and his brothers at various stations in India and the Indian Archipelago during the years 1854-1858 . 2 . The original manuscripts in thirty-nine folio volumes of meteorological observations made by various observers under the authority of the Indian Government at 207 stations in British India . In regard to the observations referred to under this head , the author considers that he possesses a special qualification for using them advantageously by having himself visited most of the stations , examined the instruments , and acquainted himself with the circumstances of their employment . The 207 stations are divided into ten geographical groups , as follows1 . Eastern India : 1 , Assam ; 2 , Kharsia Hills ... ... ... . 12 2 . Bengal and Bahar , and Delta of the Ganges and Brahmaputra ... ... ... ... ... ... ... ... ... ... ... ... . . 36 3 . Hindostan , the upper Gangetic plain ... ... ... ... ... . 27 4 . Panjab , including the stations west of the Indus ... ... 24 5 . Western India : Rajvara , Guzrat , Kach , Sindh ... ... . . 10 6 . Central India : Berar , Orissa , MAlva , Bandelkhand ... . 15 7 . 1 , Southern India : hilly districts , Dekhan and Maissur ; 2 , Nilgiris ... ... ... ... ... ... ... ... ... . 29 8 . Southern India , coasts : Konhan , Malabar , Karnatik. . 24 9 . Ceylon 10 . Indo-Chinese Peninsula , Archipelago , and China ... . 20 Each group has its appropriate processes of reduction , which are severally discussed .

112314

3701662

On the Structure of the So-Called Apolar, Unipolar, and Bipolar Nerve-Cells of the Frog. [Abstract]

569

574

Proceedings of the Royal Society of London

Lionel Beale

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112314

http://www.jstor.org/stable/112314

Biology 3

Neurology

Biology

III . " On the Structure of the so-called Apolar , Unipolar , and Bipolar Nerve-cells of the Frog . " By LIONEL BEALE , M.B. , F.R.S. , F.R.C.P. , Professor of Physiology and of General and Morbid Anatomy in King 's College , London , and Physician to King 's College Hospital . Received May 7 , 1863 . ( Abstract . ) The author adverts to the opinion generally received with regard to the existence of apolar , unipolar , bipolar , and multipolar nervecells , and observes that if cells having such very different relations to the nerve-fibres they are supposed to influence , as apolar , unipolar , and multipolar cells , 4o actually exist , as many different kinds of action must be admitted . For it is hardly likely that a nerve-cell unconnected with any fibre can affect the fibres at a distance from it in the same way as a cell acts upon fibres which are in structural continuity with it . Neither is it probable that a cell with but one fibre proceeding from it can constitute an organ which acts upon the same principle as the cell from which two or more fibres proceed . If no fibre , or but one fibre proceeds from certain cells , the formation of complete:nervous circuits , at least in these instances , is impossible ; and if it be admitted that circuits do not exist in every case , a strong argument is advanced against the existence of such complete circuits as a necessary or fundamental condition of a complete nervous apparatus . But if it can be shown , on the other hand , as the author maintains is the case , that all the supposed apolar and unipolar cells have at least two fibres proceeding from them , the fact must be accepted in favour of the view that such complete circuits may exist , while the fact that the fibres connected with many cells have been seen to proceed in opposite directions some distance after leaving the cell , is a very strong argument in favour of such general inference , and at the same time an explanation of many arrangements which are observed constantly in connexion with nerve-fibres in various tissues . Many observers have described apolar and unipolar cells in ganglia in different parts of the frog . The author , on the other hand , has failed to discover any apolar or unipolar cells in this or in any other animal , and considers that the apparent absence of fibres , and the presence of one fibre only in connexion with a cell , result from the defective modes of preparation generally employed . He maintains that every nerve-cell , central or peripheral , has at least two fibres proceeding from it* . In many cases he has demonstrated that these fibres pursue opposite directions , and he considers that such an arrangement is general , and therefore necessary . The author considers himself justified in drawing the following conclusions from observations he has made during the last three years . 1st . That in all cases nerve-fibres are in bodily connexion with the cell or cells which influence them , and this from the earliest period of their formation . 2nd . That there are no apolar cells , and no unipolar cells , in any part of any nervous system . 3rd . That every nerve-cell , central or peripheral , has at least two fibres in connexion with it . Though the present inquiry is limited to the structure of the particular cells connected with the ganglia in different parts of the frog , the author has studied the 'arrangement of nerve-cells and nervefirbes in nervous centres , as well as at their peripheral distribution , in many different animals . 1 . General description of the ganglion-cells connected with the sympathetic and other nerves of the frog . The general form of these cells is oval or spherical ; but the most perfectly formed ganglion-cell is more or less pearor balloon-shaped in its general outline , and by its narrow extremity is continuous with nerve-fibres which may be followed into trunks . The figure represents a well-formed ganglion-cell from a ganglion close to one of the large lumbar nerves of the little green tree-frog ( Hyla arborea ) . The substance of the cell consists of a more or less granular material , which by the slow action of acetic acid becomes decomposed , oil-globules being gradually set free . Near the fundus or rounded end is seen the very large circular nucleus with its nucleolus . In some of these cells , at about the central part or a little higher , are a number of oval nuclei , some of which are in connexion with fibres . The matter of which the mass of the cell consists gradually diminishes in diameter , and contracts so as to form a fibre , in which a nucleus is often seen . At the circumference of the cell , about its middle , the material seems gradually to assume the form of fibres , which contain numerous nuclei , and these pass around So-called " unipolar " nerve-cell , with , 1st , a straight , and 2nd , a spiral fibre emanating from it . The fibres continuous with these are seen to pursue opposite directions . Magnified 700 linear . L LL ... . l 1000th of an inch X 700 . 1000 ' the first fibre in a spiral manner . Thus in the fully formed cell a fibre comes from the centre of the cell ( straightfibre ) , and one or more fibres ( spiral fibres ) proceed from its surface . These points are represented in the figure* . 2 . On the formation of ganglion-cells in the fully formed frog . This subject is arranged under the three following heads , but as it would not be intelligible without figures , it will not be given in abstract . The development of these cells and many other structures may be studied in the fully formed animal as well as in the embryo . a. Ganglion-cells developed from a nucleated granular mass like that which forms the early condition of all tissues . b. Ganglion-cells formed by the division or splitting up of a mass like a single ganglion-cell . c. Ganglion-cells formed by changes occurring in what appears to be the nucleus of a nerve-fibre . 3 . Further changes in the ganglion-cell after its formation . Under this head the movement of the cell from the point where its growth commenced is described . It is shown that the two fibres , which at first seem to come from opposite extremities of the cell , lie parallel to each other . They increase in length , and subsequently one is seen to be twisted round the other , as shown in the figure . Sometimes the fibres below the point where the spiral arrangement exists run parallel for a long distance , but at length pursue opposite directions . The author considers that the formation of the ganglioncell commenced at the point where the fibres diverge , and that subsequently the cell moved away , the parallel fibres , which at length become straight and spiral , being gradually formed or drawn out as it were from the cell . 4 . Of the spiralfibre of the fully formed ganglion-cell . The spiral fibre or fibres can be shown to be continuous with the material of which the body of the cell is composed , as well as the straight fibre , but the former are connected with its surface , while the latter proceeds from the deeper and more central part of its substance . There are many nuclei in connexion with the spiral fibre , and several nuclei of the same character imbedded in the substance of the mass of which the cell is composed . These latter nuclei seem to be connected with an earlier condition of the matter which becomes , when more condensed , spiral fibre . A great difference is observed with regard to the extent of the spiral fibre in cells of different ages . In the youngest cells the fibres near the cell are both parallel to each other , but as the cell grows one is seen to be coiled round the other ; and the number of coils increases as the cell advances in age , while the matter of which the fundus of the cell is composed gradually becomes less-apparently in consequence of undergoing conversion into fibres . Nuclei are found in the course of the straight fibre , as well as in connexion with the spiral fibre . Nuclei have been demonstrated in connexion with the dark-bordered fibres near their origin and near their distribution in all tissues . Next follows a discussion " on the essential nature of the changes occurring during the formation of all nerve-cells , and on the formation of spiral fibres , " but this is not adapted for an abstract . The term " nucleus " is only employed in a general sense . The author believes that the " nucleus , " nucleolus , " and centres within the latter ( " nucleoluli " ) merely represent centres of different ages . He considers that the matter of the nucleus becomes gradually transformed into the formed matter around it , and generally , that these bodies are merely centres which arise in pre-existing centres . He maintains that from the outer formed matter connected with the fibres new nerve-cells could not be produced , while he holds that from the nuclei , nucleoli , and contained centres , entirely new and complete cells could be evolved . So he considers that the difference in the properties and powers of the formed matter on the one hand , and the nuclei and nucleoli on the other , depends upon these two kinds of matter having arrived at different stages of existence . That which is formed cannot form new formed matter , nor appropriate nutrient material ; but the living germinal matter of the nucleus can be resolved into formed matter , and it can appropriate inanimate pabulum , and confer upon it the same wonderful ( vital ) powers which it possesses itself , and which were communicated to it from preexisting germinal matter . 7 . Of the fibres in the nerve-trunks continuous with the straight and spiral fibres of the ganglion-cells . The conclusions upon this important question are as follows:1st . That in some instances very fine fibres , not more than the J-6- , th of an English inch in diameter , are alone continuous with both straight and spiral fibres of the ganglion-cell . 2nd . That a dark-bordered fibre may be traced to the ganglioncell as the straightfibre , while the spiral fibres are continued on as very fine fibres . 3rd . That the spiral fibres may be continued onwards as a darkbordered fibre which may even be wider , at least for some distance , than the fibre continued from the straight fibre . 4th . That both straight and spiral fibres may be continuous with dark-bordered fibres . It is therefore quite certain that the spiral fibre is not connective tissue , although the author considers it probable that many German observers may adopt this view until they have an opportunity of seeing the fibres themselves . 8 . Of the ganglion-cells of the heart . The author 's conclusions are quite opposed to those of Kolliker , who states that all the cells are unipolar , and that the fibre always passes in a peripheral direction , also that the transcurrent fibres of the vagus have no connexion with these cells . The author , on the contrary , affirms that the cells have at least two fibres comingfrom them , that some of the fibres pass towards the heart , and others towards the brain . He regards it as very probable that many at least of these ganglion-cells are connected with fibres of the vagus . Kolliker has also stated ( 1860 ) that many apolar cells could be seen in the heart , ganglia , and in the bladder . The author has been able to demonstrate fibres in connexion with so many cells which appeared devoid of fibres , that he considers himself justified in denying the existence of apolar and unipolar cells altogether . Next follow some observations on " the ganglion-cells and nerves of arteries ; " " on the connexion of the ganglion-cells with each other ; " and the paper concludes with a description of the so-called " capsule " of the ganglion-cell , and a discussion on the nature and formation of the connective tissue and its corpuscles in the immediate neighbourhood of nerve-fibres . The paper is illustrated with forty-seven drawings of the specimens , magnified from 700 to 1700 linear ; and the author states that many of the specimens will probably retain the appearances he has copied for several months . All the preparations have been made in the same manner . An outline of the process has been already given in the author 's previous communications , but the author is aware that it may be some time before the correctness of his conclusions is generally admitted , in consequence of the difficulty of preparing demonstrative specimens .

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On the Belts of Jupiter, in a Note Addressed to the Secretary

575

575

Proceedings of the Royal Society of London

John Phillips

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Optics

Astronomy

Optics

IV . " On the Belts of Jupiter , " in a Note addressed to the Secretary . By JOHN PHILLIPS , M.A. , LL. D. , Professor of Geology , Oxford . Received May 5 , 1863 . Oxford , 4th May , 1863 . DEAR SIR , -The favourable position of Jupiter for scrutiny of his physical features may perhaps have already brought to the Royal Society some notice of the aspect of his belts . Whether that be so or not , I think you will readily excuse the desire I feel to lay before the Society a sketch from my equatorial , which shows the colours of several celestial objects more distinctly than I am accustomed to hear is the case with some other instruments of the achromatic class . The sketch shows the usual equatorial bands* , or rather bands nearly in the usual latitudes north and south of the equator . These , to the eyes of my friends and to mine , appear not dark grey , or greyish brown , or brown , but nearly of the colour of some ochraceous sands , or the yellower parts of what is called " red " deal . Several friends to whom I have shown the planet have immediately exclaimed , " how red the bands are ; " " never saw them so red before . " The bands far from the equator are not reddened , but of a grey tint a little warmed . The space between the equatorial bands , sometimes described as yellow , appears rather bright white and silverymuch the brightest part of the surface . The outer borders of the equatorial bands are not parallel , the inner borders much unequal ; in one part the two bands are connected across . Not the faintest trace of such a tint as that conspicuous in these bands appears on any part of the moon ; but it is pretty nearly the tint of the supposed " land " of Mars . In fact , it was suggested to my mind that these coloured extra-equatorial belts were land , seen between white clouds , of which the brightest band was on the equator . JOHN PHILLIPS , M.A. , LL. D. , F.R.S. , Professor of Geology , Oxford .

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Notes of Researches on the Polyammonias, No. XXIII.--Hydrazobenzol, a New Compound Isomeric with Benzidine

576

578

Proceedings of the Royal Society of London

A. W. Hofmann

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Chemistry 2

Geography

Chemistry

V. " Notes of Researches on the Polyammonias , No. XXIII . Hydrazobenzol , a new Compound isomeric with Benzidine . " By A. W. HOFMANN , LL. D. , F.R.S. , &c. Received May 7 , 1863 . The discovery , among the secondary products of the manufacture of aniline , ofxenylamine , the probable connexion of which with benzidine ( xenylene-diamine ) I have already had an opportunity of pointing out* , has induced me to submit the latter compound to some experiments . In preparing benzidine by the process originally pointed out by Zinint , viz. by treatment of azobenzol with sulphide of ammonium , I was led to the observation of some phenomena which appear to have escaped the attention of those who have hitherto studied this substance . It is generally supposed that the action of reducing agents upon azobenzol produces directly benzidine . C12 Hlo 2+ I2- , = C1 H12 N2 . Y Azobenzol . Benzidine . Such , however , is not the case . The well-defined base designated by the latter name is only a secondary product ; the first compound which is generated in this process being a neutral or feebly basic body , differing in all its properties from benzidine , with which , however , it is isomeric , and into which it may be converted by simple treatment with strong mineral acids . On passing a current of sulphuretted hydrogen into a solution of azobenzol in alcoholic ammonia , the yellowish-red liquid is rapidly decolorized , and yields on addition of water a crystalline precipitate of a peculiar camphor-like smell . This substance contains a minute quantity of the sulphur which separates , the bulk of which , however , remains dissolved as polysulphide of ammonium ; it is easily purified by two or three crystallizations from very dilute alcohol . Submitted to combustion , the compound thus obtained yields numbers which coincide with those furnished by the analysis of benzidine . The properties in which the new substance , for which I propose the name hydrazobenzol , differs from benzidine are the following : Hydrazobenzol crystallizes from alcohol , and more especially from benzol ( in which it is somewhat less soluble ) , in well-developed white plates , benzidine being always deposited from these solvents in welldefined needles ; and whilst the latter is freely soluble in boiling water , from which it separates on cooling in the form of a crystalline mass of nacreous lustre , the former is so sparingly soluble in water that it is impossible to recrystallize it from that solvent . The fusingpoint of hydrazobenzol is 131 ? C. , that of benzidine being 1180 C. The basic properties of benzidine are well defined ; it dissolves even in the weakest acids , such as acetic acid , in which hydrazobenzol is nearly insoluble . Stronger acids , such as hydrochloric and sulphuric acids , more especially on application of heat , dissolve hydrazobenzol ; but the solution thus obtained contains no longer the unchanged body ; the addition of alkali , fixed or volatile , produces a precipitate which now possesses all the properties of benzidine . These characters are sufficient to individualize hydrazobenzol . There is , however , another property which marks its difference from benzidine in even a more conspicuous manner . Benzidine when submitted to a high temperature distils ; a certain portion is decomposed in this process , but the larger quantity is volatilized without decomposition . On heating hydrazobenzol considerably above its fusingpoint , a powerful reaction ensues , the heat evolved being sufficient to carry over nearly the whole amount of substance in the form of a deep red oil , from which , on cooling , crystals of azobenzol are deposited . On addition of an acid the oil yields a further quantity of this substance , and the acid solution is then found to contain abundance of aniline . The reaction which occurs is simple enough . 2C12 12 N2 = C12 Hlo N2 + 2C6 H7 N. Hydrazobenzol . Azobenzol . Aniline . I had hoped that among the products of the reaction paraniline ( C12 H1S 4N=2 C H7 N ) might be met with ; in this hope I have been disappointed . The reproduction of azobenzol from hydrazobenzol may be accomplished in a variety of other ways . Nitrous acid , chlorine , bromine , iodine , chromate and permanganate of potassium , and nitrate of silver produce this effect in a most easy manner ; in these processes the loosely adherent hydrogen is simply eliminated , no aniline being formed as a secondary product . Even when moistened with alcohol and exposed to the action of the atmosphere , hydrazobenzol is gradually reconverted into azobenzol . It deserves to be noticed that some of the chemists who have been engaged in the examination of benzidine must have occasionally worked with hydrazobenzol . Mr. Noble* , who many years ago prepared benzidine in my laboratory , especially remarks that the substance obtained by him is reconverted into azobenzol by the action of nitrous acid . I have satisfied myself that benzidine thus treated yields no trace of azobenzol . From the experiments described , it is obvious that in the formation of benzidine from azobenzol two distinct phases have to be distinguished : in the first phase the molecule of azobenzol assimilates a molecule of hydrogen , but this hydrogen remains in a very feeble state of combination , being eliminated again by a great variety of agents . It is only under the influence of acids that the hydrogen molecule becomes incorporated in the system , if I may use this expression , and fixed benzidine , a substance of great stability , is formed . Whatever view may be taken regarding the nature of azobenzol , the constitution of which it must be admitted is utterly unknown , the intermediate substance has to be viewed as its hydrogen compound , and it is this consideration which induced me to propose the name hydrazobenzol .

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3701662

Note on the Composition of Aniline-Blue

578

579

Proceedings of the Royal Society of London

A. W. Hofmann

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Chemistry 2

Tables

Chemistry

VI . " Note on the Composition of Aniline-Blue . " By A. W. HOFMANN , LL. D. , F.R.S. , &c. Reeeived May 21 , 1863 . The prosecution of my researches on the aniline colours has led me to a result of great simplicity , which I hasten to lay before the Royal Society . Aniline-blue is triphenylic rosaniline . Aniline-red , Rosaniline ... ... ..C20 CH 9 N3 , 12 0 . Aniline-blue , Triphenylic Rosaniline. . C20 116 N,3 H2 0 ( C6 H , )3The commercial article is a salt of the base , the hydrochlorate for example , the composition of which corresponds to the monatomic hydrochlorate of rosaniline . * Chem. Soc. Quart . Journ. vol. viii . p. 292 . Hydrochlorate of Rosaniline ... ... C2O H20 N3 C1 . Hydrochlorate of Triphenylic Rosaniline . 20 H13 C 3 . Details of these experiments I hope to lay before the Society at an early meeting .

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3701662

On the Calculus of Symbols.--Third Memoir. [Abstract]

579

579

Proceedings of the Royal Society of London

W. H. L. Russell

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Formulae

Biography

Mathematics

VII . " On the Calculus of Symbols."-Third Memoir . By W. H. L. RUSSELL , Esq. , A.B. Communicated by A. CAYLEY , F.R.S. Received May 15 , 1863 . ( Abstract . ) In my second Memoir " On the Calculus of Symbols , " I worked out the general case of multiplication according to one of the two systems of combination of non-commutative symbols previously given . In the present paper I propose to investigate the general case of multiplication according to the other system . I commence with the Binomial Theorem , to which the second system gives rise . In my previous researches I obtained the general term of the binomial theorem when the symbols combine according to the first system by equating symbolical coefficients ; here , on the other hand , I consider the nature of the combinations which arise from the symbolical multiplication , and obtain the general term by summation . I next proceed to the multiplication of binomial factors . Here the general term is obtained by considering the alteration of weight undergone by certain symbols in the process of multiplication . The multinomial theorem according to the second system is next considered and its general term calculated . I conclude the memoir with some applications of the calculus of symbols to successive differentiation . This paper completes the investigation of symbolical multiplication and division according to the two systems of combination , the general case of division having been worked out by Mr. Spottiswoode in a very beautiful memoir recently published in the Philosophical Transactions .

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3701662

Anniversary Meeting

580

580

Proceedings of the Royal Society of London

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Biography

Physiology

Biography

580 [ June 11 , June 4 , 1863 . The Annual Meeting for the Election of Fellows was held this day . Major-General SABINE , President , in the Chair . The Statutes relating to the Election of Fellows having been read , Mr. John Bishop and Mr. John Iogg were , with the consent of the Society , nominated Scrutators to assist the Secretaries in examining the lists . The votes of the Fellows present having been collected , the following gentlemen were declared duly elected into the Society-Edward William Cooke , Esq. , A.R.A. William Crookes , Esq. James Fergusson , Esq. Frederick Field , Esq. Rev. Robert Harley . John Russell Hind , Esq. Charles Watkins Merrifield , Esq. Professor Daniel Oliver . Frederick William Pavy , M.D. William Pengelly , Esq. Henry Enfield Roscoe , B.A. Rev. George Salmon , D.D. Samuel James Augustus Salter , M.B. Rev. Arthur Penrhyn Stanley , D.D. Colonel Frederick M. Eardley Wilmot , R.A. June 11 , 1863 . Dr. W. B. CARPENTER , Vice-President , in the Chair . Charles Watkins Merrifield , Esq. ; Professor Daniel Oliver ; Frederick W. Pavy , M.D. ; Samuel James Augustus Salter , M.B. ; and Col. Frederick M. Eardley Wilmot , R.A. , were admitted into the Society . The CROONIAN LECTURE was delivered by Professor JOSEPH LISTER , F.R.S. , " On the Coagulation of the Blood , " as follows : The subject on which I have the honour to address you this evening , is one which lies at the foundation both of Physiology and Pathology , and , on account of its great importance , has engaged the

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The Croonian Lecture: On the Coagulation of the Blood

580

611

Proceedings of the Royal Society of London

Joseph Lister

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Biology 2

Physiology

Biology

" On the Coagulation of the Blood , " as follows : The subject on which I have the honour to address you this evening , is one which lies at the foundation both of Physiology and Pathology , and , on account of its great importance , has engaged the best energies of many very able men , among whom may be mentioned , for example , such distinguished Fellows of this Society as John Hunter and lewson ; so that it might well seem presumptuous in me to hope to communicate anything new regarding it , were it jot that the constant progress of Physiology and the allied sciences is ever opening up fresh paths for inquiry , and ever affording fresh facilities for pursuing them . Indeed , my difficulty , on the present occasion , does not depend so much on the lack of materials as on the complicated relationis of the subject , which make me almost despair of being able , in the short time that can be devoted to a lecture , to give , in anything like an intelligible form , even an adequate selection of the facts at my disposal . It may , in the first place , be worth while , more especially for the sake of any present who may not be physiologists , to mention very briefly some well-known general facts respecting the constitution of the blood . The blood , if examined by the microscope within the vessels of a living animal , is seen to consist of a liquid and numerous small particles suspended in it . The liquid is termed the " liquor sanguinis , " the particles the " blood-corpuscles . " Of these corpuscles a few are colourless , and are named the " coloulrless " or " white corpuscles . " The great majority are coloured and cause the red appearance of the blood , and hence are called the " red corpuscles . " Soon after blood has been shed from the body , it passes from the fluid into the solid form . This depends upon the development in the blood of a solid material termed " fibrin , " so called from its fibrous nature , consisting , as examined by the naked eye , of tenacious fibres , arid having the same character also under the microscope . These fibres form a complicated network among the blood-corpuscles , and from their tenacity are the cause of the firmness of the clot . Soon after the process of solidification or coagulation is complete , the fibrin exhibits a disposition to shrink , and squeezes out from among the corpuscles entangled in its meshes a strawcoloured fluid termed the serum , very rich in albumen , in fact very similar in chemical composition to the fibrin , which , in its turn , may be said to be idelntical chemically with the material of muscular fibre . The question before uls , therefore , is , What is the cause of the development of this solid material , the fibrin ? The subject may be looked at in two aspects , -first , as to the essential nature of the process of coagulation ; and secondly , as to the cause of its occurrence when the blood is removed from the body . With regard to the first point , the essential niature of the process of coagulation , different views have been entertained . John Hunter was of opinion that the coagulation of the blood , the solidification of the fibrin , was an act of life-analogous , in some respects , to the contractioni of muscular fibre . This , on the other hand , was made very unlikely by the observation of his contemporary , Mr. lewson , that blood may be kept in the fluid state by the addition of various neutral salts , but retains the faculty of coagulating when water is added to the mixture . Mr. Gulliver , on one occasion , kept blood fluid , by means of nitre , for upwards of a year , but found that it still coagulated on the addition of water . It seems exceedingly improbable that any part of the human body should retain its vital properties after being thus pickled for more than a year . But here I would wish to make an explanation of the use of this term " vital properties . " When employing it , I do not wish to commit myself to any particular theory of the nature of life , or even to the belief that the actionls of living bodies are not all conducted in obedienice to physical and chemical laws . But it appears that every component tissue of the human body has its own life , its own health , just as we ourselves have ; and as the actions of living men will ever retain their interest whatever views be entertained of the nature of life , so must the actions of the living tissues ever continue to be essential objects of study to the physiologist and pathologist . When , therefore , I use the term " vital properties , " I mean simply properties peculiar to the tissues as components of the healthy living body . Turning now to the other aspect of the subject of coagulation the cause of the occurrence of that process on the escape of the blood from the living body we find that here again various theories have been held , which may be divided into mechianical , chemical , and vital . The mechanical theory was , that mere rest of the blood was sufficient to cause coagulation . I say this was the theory ; but I believe it will be found to be still taught by many , that the cause of the coagulation of the blood in an artery which has been tied is its stagnation in the vicinity of the ligature . As to the chemical theories they have been various . Onie very natural view was , that exposure to the air was the essential cause of coagulation . Mr. Hewson believed that this was , at all events , an importaint element in the causes of the phenomenon ; and many eminelt physiologists and pathologists have held the same view , except that , instead of the air as a whole , the oxygen of the air has been supposed to be the important element . Sir Charles Scudamore considered that coagulation was greatly promoted by the escape of carbonic acid ; and more recently the evolution of ammonia has beeni regarded as the essential cause of the change . According to the ammonia theory , due to Dr. Richardson of this city , the fluidity of the blood within the body depends on a certain amount of free ammonia holding the fibrin in solution , and the coagulation of the blood when withdrawn from the vessels is the result of the escape of the volatile alkali . Then , as to vital theories . These have been held by many physiologists , amo-ng whom may be mentioned Sir Astley Cooper and Mr. Thackrah , who , from experiments which they performed , were led to the inference that the living vessels exert an active influence upon the blood , by which coagualation is prevented ; and Mr. Thackrah wenit so far as to attribute this action of the vessels to nervous influence . The view that the blood is kept fluid by the operation of its natural receptacles has been advocated more recently by Briicke of Vienna , whose essay will be found iu the 'British and Foreign Medical Review ' for 1857 . Br'icke performed his experiments on turtles and frogs , in which animals the blood remains fluid in the heart for days after death ; and I feel bound to say that some of the facts which he has brought forward seem to me quite sufficient to show that the ammonia theory , whatever amounit of truth it may contain , cannot be the whole truth , and cannot explain the flutidity of the blood within the body . For example , Brileke found that , having shed blood from the heart of a living turtle into a basin , and transferred , with a syringe , a portion of that blood into the empty heart of another turtle just killed , the blood thus transferred into the empty heart remained fluid for hours ; whereas that which was left in the basin coagulated in a few minutes . Hle also found that blood continued fluid in the heart of a turltle long afteir the injection of air into the heart through a veini till the cavities of the organ contained a foamny mixture of blood and air . Yet it by no means follows that the vital theory and the ammonia theory are necessarily altogether inconsistent . It might be true for anything we could tell , a priori , that the coagulation of the blood , when shed from the body , might depend on the evolution of a certain amount of ammonia , previously holding the fibrin in solution , and yet it might , at the same time , be true that the cause of the ammonia remaining in the blood in the healthy vessels might be an action of the living vessels retaining it there . It might be that an action of the living vessels might chain down the ammonia and prevent it from escaping , whereas , when shed from the body , it would be free to escape . This notion was , I confess , at one time entertained by myself ; and one of my earliest experiments was performed with a view to the corroboration of the ammonia theory as applied to blood outside the body . It seemed to me desirable that further evidence should be afforded of the effect of mere occlusion from air in maintaining the blood fluid . If the ammonia theory were true , then if blood could be shed directly from a living vessel into an air-tight receptacle composed of ordinary matter it ought to remain fluid . For this purpose , I made the following experiment:-I tied into the jugular vein , V , ( fig. 1 ) of Fig. 1 . v a sheep a long vulcanized india-rubber tube , T , adapted by means of short pieces of glass tule at its extremities , both ends being connected with the vessel so that the current of blood might be permitted to flow through the tube , and then continue its natural course . When it had been ascertained that the blood was circulating freely through the tube , which could be readily done by placing the finger on the cardiac aspect of the vein , which was then made to swell if the circulation was proceeding through the tube , pieces of string well-waxed were tied at intervals of about 2 inches round the tube , which was thus converted into a number of air-tight receptacles containing blood , which certainly had no opportunity for the escape of ammonia . The tube was then removed , and I found , in accordance with the view which I was then disposed to entertain , that the blood , instead of coagulating completely in a few minutes as it would have done if shed into a cup , remained partially fluid in these receptacles after the lapse of three hours . But I have since found that if the experiment be repeated in the same way as regards its earlier stages , and if , after a few of the strings have been tied on , the tube be cut across , the blood which is in the part of the tube in the vicinity of the air , just like that which is in the air-tight receptacles , remains fluid in part for two or three hours . In short , that my precautions in ensuring that these receptacles should be air-tight were , in so far as they applied to that object , utterly unnecessary . I mention this partly as an illustration of the deceptions to which one is liable in this inquiry , and partly because the experiment thus modified seems to tell as clearly against the ammonia theory as the original one seemed to tell in favour of it . Those receptacles which had been formed by the application of ligatures before the tube was opened afforded certainly no opportunity for the escape of ammonia , and yet in them the blood coagulated as quickly as in those which had communication with the air-implying that facility for the evolution of ammonia does not in itself affect the process of coagulation at all . How then , it may be said , is the persistent fluidity of the blood under these circumstances to be explained ? That will become more obvious than I can make it at present in the sequel ; but in the mean time I may observe that there are probably two explanations : one is , the coolness of the tube , and the other , far more important , that the blood , in slipping through this cylindrical tube , had had little opportunity of being influenced by its walls . The portion of the blood that came first in contact with the walls of the tube had coagulated ; and it is to be observed that I never found , in these experiments , the blood altogether fluid , even after a comparatively short time : there has always been a certain amouLnt of coagulation , and only a certain amount of fluidity . A layer of blood having thus coagulated upon the internal surface of the tube , the fresh blood which continued to flow through it , was not brought into contact with the walls of the tube at all , but with their lining of coagulated blood . It has been long known that if blood is stirred with a rod , the process of coagulation is promoted . It seemed desirable to ascertaini distinctly whether the cause of this was the contact of the foreign solid , or the opportunity givenl for the escape of ammonia ; for it is quite true that , in the ordinary process of stirring blood , more or less air is mixed with it . For the purpose of determining this I devised a somewhat complicated experiment , which , however , it may be worth while to mention . I made an apparatus ( fig. 2 ) of two portions of glass tube , A and B , connected in a vertical position by means of vulcanized india-rubber , I , the lower portion of the glass tube being also connected by indiarubber , It , with a wooden handle , which handle , H , was provided with an upright piece of wire , from which spokes pro.ected in different directions , so -Fig . 2. . --g 7A ~~~_VS S $M_4 ; c a ] 12 , that they would , when moved , act as a churn on any blood contained in the lower portion of tube . When the lower piece of tube was fixed by means of a vice , V , the flexibility of the india-rubber permitted the churn to be rotated so as to expose the blood to its influence . This having been arranged , I first poured in strong liquor ammonice , so as to get rid of any slight acidity which the constituents of the apparatus might be conceived to possess , and then , having poured out the ammonia , filled up the apparatus with water , and boiled the whole in a large glass test-tube till all bubbles of air , in any portion of it , were expelled . Having then tied into a branch of the carotid artery , C , of a calf a bent tube of small diameter , as represented , and having permitted the blood to flow till it escaped at the orifice of the tube , I compressed the artery and passed the tube down through the water to the bottom of the apparatus , and then let the blood flow again , which had the effect of displacing all the water ; and when the blood appeared at the top of the apparatus , the tube was withdrawn , when two effectual clamps , Cl , Cl , were placed on the vulcanized india-rubber connecting A and B ; the india-rubber was then divided between the clamps , and we had the state of things represented at the right-hand side of the diagram . The upper portion of the apparatus , the orifice of which was exposed to the air , was set aside and left undisturbed . Having ascertained that the lower portion had been effectually sealed by the clamp , and thus prevented from any opportunity of escape of ammonia , I subjected it to the action of the churn for a certain number of minutes . It so happened that the blood of that calf was very slow in coagulating . I knew this from previous experiments on the animal , and therefore continued the action of the churn for a considerable time , viz. thirty-seven minutes . I then found the wire enveloped in a mass of clot ; and examination of the fluid residue with a needle indicated that the fibrin had been all withdrawn from the blood on which the churn had acted . I did not now examine the other portion of the apparatus , which had been set aside ; but at the end of an hour and a quarter , when more than double the time had elapsed , I investigated this , and found the blood in it , for the most part , still fluid and coagulable . Thus the blood in the churn , which , from the time it left the artery , had nio opportunity of parting with its ammonia , coagulated much more rapidly than that in an open vessel . The difference between the two was , that the lower portion of the blood had been freely exposed to the influence of the foreign solid , whereas the other had only been subjected to the action of the wall of the tube . The same principle may be illustrated by an exceedingly simple experiment which I performed only this very day . Receiving blood from the throat of a bullock into two similar wide-mouthed bottles , I immediately stirred one of them with a clean ivory rod for 10 seconds very gently , so as to avoid the introduction of any air , and then left both undisturbed . At the end of a certain nuinber of minutes I found that , while the blood which had not been disturbed could be poured out as a fluid , with the exception of a thin layer of clot on the surface , and an incrustation on the interior of the vessel , the blood in the other vessel , which had been stirred for so brief a period , was already a solid mass . I have only lately been aware of the great influence exerted upon the blood by exposure for a very short time to a foreign solid , and I feel that many of my own experiments , and many performed by others , have been vitiated for want of this knowledge . Take , for example , the effect of a vacuum , which was observed by Sir Charles Scudamore to promote coagulation . This has been considered by Dr. Richardson as aln illustration of his theory , the vacuum being supposed to ac.t by favouring the escape of ammonia . I have lately inquired into this subject , and I feel no doubt whatever that the greater rapidity of coagulation in a vacuium depends simply on the greater disturbance of the fluid . I made the following experiment : I filled three bottles , such as these , from the throat of a bullock , placed one of them under the small bell jar of an air-pump in good order and exhausted it , leaving the other two unldisturbed . The blood happened to be slow in coagulating ; and at the end of about forty minutes , in the vessels where the blood bad been undisturbed , there was only a slight film of coagulum on the surface , whereas the blood under the vacuum was found on examination to have a very thick crust of clot upon it . But during the process of exhaustion the blood had bubbled very much . Indeed , any exhaustion of blood recently drawn which is su-fficient to cause the evolution of its gases induces great bubbling ; so that the pump cannot be used freely , for fear of the froth overflowing . To this disturbance , involving the exposure of successive portions of blood in the bubbles to the sides of the vessel , I was inclined to attribute the more rapid coagulation ; but in order to prove the point , I stirred for a few seconds the blood in one of the vessels hitherto undisturbed . After eight minutes I emptied the three vessels . I found that that blood which had not been disturbed at all , either by the vacuum or by the rod , was still almost entirely fluid , only showing a thin crust upon the glass and on the surface exposed to the air . The blood which had been subjected to the vacuum had a thick crust of clot on the surface , and the sides of the glass were also thickly encrusted , but it still contained a considerable quantity of fluid that could be poured out from its interior . But that blood which had been stirred for only a few seconds was a solid mass throughout . In other words , gentle stirring of the blood for a few seconds bad much greater effect in producing coagulation than the protracted and efficient exhaustion which was continued for upwards of 40 minutes , which was a considerable time after all evolution of gas , as indicated by bubbles , had ceased . Other experiments precisely similar in their effect were performed . I therefore feel no hesitation in stating that the effects of a vacuum , regarding which , indeed , the statements of different experimenters have hitherto beenl conflicting , afford no evidence in favour of the ammonia theory . There is another point of very great interest in the history of the coagulation of the blood , which has been supposed to give support to the ammonia theory ; and that is , the effect of temperature . It has been long known that blood coagulates more rapidly at a high than at a low temperature , and , indeed , a little above the freezing-point remains entirely fluid . This seemed beautifully in harmony with the ammonia theory , as heat would naturally promote , and cold retard the evolution of the alkali , and a depression of temperature to near the freezing-point might be reasonably supposed to prevent its escape altogether . Indeed Dr. Richardson mentions as a fact , that ammonia artificially mixed with blood ceases to be given off under such circumstances . Though thinking it n)ot unlikely that this was the true explanlation of the influence of temperature on coagulation , I thought it worth while to subject the matter to experiment . For that purpose I kept the blood of a horse fluid by means of a freezing-mixture , and afterwards by ice-cold water ; and when the corpuscles had subsided from the upper part of the blood , I cautiously added to the liquor sanguinis extremely dilute ice-cold acetic acid till it was of distinctly acid reaction , the liquor sanguinis being of a colour that permitted the delicate application of test-paper , which is impossible with red blood . By this means any free ammonia which the fluid might have contained must have been neutralized ; yet so long as it was kept in the cold it continued fluiid , but when brought into a warm room , coagulated just as a specimen which had not been acidulated . Thus , when there could be no free anmmonia in the liquor sanguinis at all , it was still affected as usual by temperature . This experiment may not be satisfactory to all minds , though I confess it appears so to me ; and as this is a point of very great interest , I have sought in another way for evidence regarding it . First , however , I will mention an experiment which will not at once appear to bear on the question of temperature . I drew out a fine glass tube in such a way as to produce a fusiform receptacle continued longitudinally each way into a tube of almost capillary fineness for about two inches , which again expanded at the end , as represented in fig. 3 . Having squeezed out a drop of blood from iny finger , I sucked up a portion into the tube till the receptacle A and its capillary extensions were filled . I then broke off the expanded ends , and placed the little tube thus filled , B , in a bath of the strongest liquor ammonia- . Here certainly the blood was in circumstances in which it could not lose ammonia , but where any change in its amount must be by wav of inierease , and yet I found , on openiig the receptacle by Fig. 3 . A.= snapping it across after a scratch with a file , that instead of remaining longer fluid than in a watch-glass , the blood in it , being more in contact with the glass , was always more quickly coagulated , while coagulation was still more rapid in the capillary tube , where the blood was still more exposed to the influence of the foreign solid the greater proximity to the liquor ammonim having no influence upon it . It may perhaps be argued that the drop of blood employed being , a small drop , and this small drop having been drawn up by suction into the tube , it might have parted with its ammonia before it got into the tube ; but then ( and now comes the bearing of the experiment on the effect of temperature ) I found , if I placed a similar tube filled in the same way in a vessel of snow , so as not to freeze it but to keep it icecold , the blood in it remained fluid as long as I chose to keep it there . Now if all the ammonia had left the blood before it was introduced into the tube , cold ought , according to the ammonia theory , to have had no effect in retarding its coagulation ; for , according to that theory , cold operates by retaining the ammonia . On the other hand , if we take the other alternative and suppose that any ammornia which the blood might have contained was still in these tubes , the former experiment proves clearly that the retention of ammonia has no effect in producing fluidity-no effect in preventing coagulation ; and if the retenition of ammonia has no effect in preventing coagulation , then cold certainly cannot prevent coagulation by retaining the ammonia , because , even if retained , it would not influence the result . In whatever way we look at them , therefore , these simple experimenits prove conclusively that cold maintains the fluidity of the blood in some manner unconnected with any influence it may exert upon ammonia . Then , again , I varied the experiment in this way . I placed such little tubes of blood in baths of liquor ammonie at different temperatures . By careful management , guarding against the volatilization of ammonia and consequent reduction of temperature , I succeeded in employing satisfactorily a bath of liquor ammoniae at 1000 F. , the blood being in the bath within a few seconds of its leaving the vessels of my finger , and I found that the high temperature , though uncder such circumstanices it could not possibly dissipate any ammonia from the blood , vet accelerated its coagulation in precisely the same way as when it was applied to blood in watch-glasses exposed to the air . It is clear , then , that the promotion of the solidification of fibrin by heat is as independent of the evolution of ammonia as the coagulation of albumen under the same agency . Indeed it seems probable that the two cases are analogous , except that a higher temperature is required in the one than in the other . When fine tubes containing blood were placed in liquor ammoniae , the alkali acted only upon those parts which were close to the ends of the tubes ; a very small portioni was rendered brownL by it , and beyond that a little was kept permanently fluid , but the chief length of the blood in the tube was uinaffected . Having thus ascertained that ammonia travels so slowly along tubes of this capillary fineness , I thought T might have an opportunity of giving the ammonia theory a fair test by tying such a tube as has been above described into the jugular vein of a rabbit and filling it directly from the vessel , and then ascertaining whether there was any evidence of retardation of coagulation in the blood thus imprisoned . But I could discover no such evidence , although I soug , ht for it in confirmation of a view I then held . To this , however , there is one special exception to be made , viz. in the case of asphyxia . I found that if two suich tubes were filled from the same blood-vessel of a creature , one under normal circumstances , and the other after asphyxia had been induced , there was a most remarkable difference between the rates of coagulation of the blood in the two tubes , the asphyxial blood coagulating very much more slowly than the ordinary blood ; but when the asphyxial blood was shed into a watch-glass and air was blown through it , it coagulated rapidly , showing that in the state of asphyxia there must be some volatile element in the blood which has an effect in retarding coagulation . Supposing at first that this volatile element must be ammonia , I hoped to be able by chemical means to find evidence of its accumulation in asphyxia , and thus add a fact of great interest to physiology . Imitating experiments previously made by Dr. Richardson , I passed air successively through blood and through hydrochloric acid , and then estitnated the amount of ammonia acquired by the latter by means of oichloride of platinum . In order to prevent the possibility of the loss of any ammonia , I directed blood from the carotid artery of a calf fairly into a Woulfe 's bottle by means of a vulcaniized india-rubber tube tied into the vessel , and then drew a certain volume of air through it by means of an aspirating jar , the experiment being performed first before , and then during asphyxia . The same procedure was adopted with a second calf , the animal being in each case under chloroform , which does not interfere with the development during asphyxia of the peculiarity in the blood above alluded to ; but I could not find satisfactory evidence of accumulation of ammonia ; and without going further into the question at present , I may say that it seems much more probable that the effect is due to carbonic acid , which is known to have a retardinxg influence on coagulation , and which probably accumulates greatly in asphyxial blood . But in justice to the author of the ammonia theory , and to myself , too , who at one time expressed a qualified belief in it , it is but fair to say that this theory is extremely plausible . It has been well shown by Dr. Richardson that ammonia is a substance well fitted to keep the blood fluid if it be present in a sufficient quantity . An experiment of my own illustrates very well the same point . I drew out a tube about a quarter of an inch in calibre ( fig. 4 ) , so that while for two inches at one end it retained its original width , the rest ( some ten inches ) was pretty narrow , though far from having the capillary fineness of those before described . Into the thick part I initroduced a drop of strong liquor ammonie , A , and then securely corked that end of the tube , C. The object of this was that there should be a strong ammoniacal atmosphere in the narrow part of the tube . I then opened a branch of a vein , V , in the neck of a sheep , introduced the narrow end of the tube into the vessel , and pushing it in so that its Fig. 4 . __ , V CA _______ ~~~~~~~ la C7 orifice should be in the currenit of the main trunik of the vein , tied it in securely . I then remnoved the cork and made pressure on the vein at the cardiac side , causing the vessel to swell and blood to pass into the fine part of the tube ; and before the blood had reached the part of the glass moistened by the ammonia , I put in the cork again and withdrew the tube . In a short time , on introducing a hook of fine wire into the extremity of the tube , I found the blood already coagulated ; but on filing off a small portion of the tube , I found the blood there fluid . The portion of blood thus exposed soon coagulated , when , a second small piece of the tube being removed by the file , fluid blood was again disclosed , which again soon coagulated ; and this proceeding was repeated with the same results time after time , till , near the thick part of the tube , the ammoniia in the blood was so strong as to prevent coagulation altogether . This experimenit illustrates how fitted the ammonia is to maintain the fluidity of blood , and also how apt it is , when present in the blood , to fie speedily off from it , leaving it unimpaired in its coagulating properties ; and it must be confessed that the end of the tube sealed with a small clot resembled most deceptively the extremity of a divided artery similarly closed . But although the experiment seems in so far to favour the ammonia theory , it will tell differelntly when I mention the object with which it was performed . It appeared to me that , if the cause of the fluidity of the blood was free ammonia , then , if I provided an ammloniacal atmosphere in the tube , and introdlced blood by pressure directly from the veini into this ammoniiacal atmosphere , this blood , lying between the stronig ammoniacal atmosphere on the one side and the ammonia naturally present in the blood withiin the vein on the other side , ought to remaini fluid ; and if it did remain fluid , this would tend to co.nfirm , the ammonia theory by making it appear that the volatile material was the same at both ends of the tube . But , to my disappointment , I iinvariably found that if I ( Iiew away the tube after a few minutes only had elapsed , there was already a clot in its extremity ; in other words , the amnmoniia had diffused from the end of the tutbe inito the blood within the vein as iito a non-ammoniacal atmosphere . This experiment alone , if duly considered , would , I think , suffice to show that the blood does not containi enouigh ammonia to aceouIlnt for its fluidity . Otne more experiment , however , may be adduced . with the same object . I mounted a short but wide glass tube , open at both ends ( T , fig. 5 ) , ulpon the enid of a piece of strong wire , W , and connected with the latter a coil of fine silver wire , S , so that it hung freely in the tube . I then opened the carotid artery of a horse , and through the wound instantly thrust in the apparatus so far that I was sure the tube lay in the common carotid , which in veterinary language means the enormous trunk common to both sides of the neck of the animal . The tube beinio open at both ends , and slightly funnelshaped at that end which was directed towards the heart , had thus a full current of arterial blood streaming through it . Having ascertained how long the arterial blood took to show the first appearance of coagulation in a watchglass , I very soon after removed the apparatus , and , on taking out the coil of silver wire , found that it was already crusted over with coagulunm . Yet here assuredly there had been no opportunity for the escape of ammonia . From this experiment it is obvious that there is a very great difference between ordinary solid matter and the living vessels in their relation to the blood . But the same conclusion may be drawn much more simply from experiments which I had the opportunity of performing after making an observation which it seems strange should have been left for me to make , and which , I may say , was made by myself purely accidentally ; and this is , that the blood of mammalia , although it coagulates soon after death in the heart and the principal arterial and venous trunks , remains fluid for an indefinite period in the small vessels . If , therefore , a ligature be tied round the foot of a living sheep a little below the joint which is divided by the butcher , the foot being removed and taken home with the blood retained in the veins by the ligatiure , we have a ready opportunity of investigating the suibject of coagulation , and of making observations as satisfactory as they are simple . Here are two feet provided in the way I have alluded to . A superficial vein in each Fig. S. w foot has been exposed . The veins I see have contracted very much sinice I reflected the skin from them before our meeting ; and I may remark that such contraction , dependent on muscular action , may occur days after amputation , indicating the persistence of vital properties in the veins . Now as I cut across this vein , blood flows out , fluid but coagulable . Into the vein of this other foot has been introduced a piece of fine silver wire , and when I slit up the vein you will see the effect it has produced . Exactly as far as the silver wire extends , so far is there a clot in this vessel . Now this experiment , very simple as it is , is of itself sufficient to prove the vital theory in the sense that the living vessels differ entirely from ordinary solids in their relation to the blood . It is perfectly clear that by introducing a clean piece of silver wire ( and platinum or glass or any other substance chemically inert would have had the same effect ) I do not add any chemical material or facilitate the escape of any , and yet coagulation occurs round about the foreign solid . Again , if a blood-vessel be injured at any part , coagulation will occur at the seat of injury . As a good illustration of this , and also as bearing upon the ammonia theory , I may mention the following experiment . Having squeezed the blood out of a limited portion of one of the veins of a sheep 's foot , and prevented its return by appropriate means , I treated the empty portion with caustic ammonia , the neighbouring parts of the vein being , protected from the irritating vapour by lint steeped in olive oil . After the smell of ammonia had passed off , I let the blood flow back again and left it undisturbed for a while , when I found on examination a cylindrieal clot in the part that had been treated with ammoniia , while in the adjacent parts of the same vessel the blood remained fluid . I repeated this experiment several times and always with the same result . Where the ammonia had aeted there was a clot . The chemical agent used here was one which , so long as any of it remained , would keep the blood fluid ; yet its ultimate effect was to induce coagulation , the vital properties of the vein having been destroyed by it . If a needle or a piece of silver wire is introduced for a short time into one of the veins of the sheep 's foot , it is found on withdrawal to be covered over with a very thin crust of fibrin , whereas the wall of the vessel itself is never found to have fibrili or coagulum adhering to it unless it has been injured . Now this seems to imply that the ordinary solid is the active agent with reference to coag-ulation-that it is not that the blood is maintained fluid by any action of the living vessels , but that it is induced to coagulate by an attractive agency on the part of the foreign solid . We see at any rate that the foreign solid has an attraction for fibrin which the wall of the vessel has not . And yet I own I was at first inclined to think that the bloodvessels must in some way actively prevent coagulation . There were two considerations that led to this view . One was , that the blood remained fluid in the small vessels after death , but coagulated in the large . Now why should that be ? It seemed only susceptible of explanation from there being some connexion between the size of the vessel and the circumstance of coagulation . It looked as if in the small veins the action of the wall of the vessel was able to control the blood and keep it fluid , but that the large mass in the principal trunks could not be so kept under control . The other circumstance was , the rapid coagulation of a large quantity of blood shed into a basin . Why should this occur unless there was some spontaneouis tendency in the blood to coagulate ? It seemed scarcely credible that it was the result of contact with the surface of the basin . Both these notions , however , have since been swept away . In the first place , I have observed recently that it is by no means only in small vessels that the blood remains fluid after death . If blood be retainied within the jugular vein of a horse or ox by the application of ligatures , either before or after the animal has been struck with the poleaxe , it will often continue fluid , but coagulable , in that vessel , which is upwards of an inch in diameter , for twenty-four or even forty-eight hours after it has been removed from the body . I say often , but not always . The jugular vein seems to be in that intermediate condition , between the heart and the small vessels , in which it is uncertain whether it will retain its vital properties for many hours , or will lose them in the course of one hour or so . Unfortunately for my present purpose , it happens that in this juigular veini , removed from an ox six hours ago , coagulation has already commenced , as I can ascertain by squeezing the vessel between my fingers . But now that I lay open the vessel , you observe that the chief mass of its contained blood is still fluid , and we shall at all events have an opportunity of seeing , that what is now fluid will in a short tinme be coagulated . It is an interesting , VOoL . X-II 2 u circumstance with reference to the question which we are now considering , that the coagulation always begins in contact with the vein , indicatinDg that it is not the wall of the vessel that keeps the blood fluid , but that , on the contrary , the wall of the vessel , when deprived of vital properties , makes the blood coagulate . The observation of the persistent fluLidity of the blood in these large vessels furnished the opportunity of making a very satisfactory experiment , which I hoped to have exhibited before the Society ; but as there was some clot in the vein , I did not think fit to run the risk of failure . The experiment is performed in the following way . A piece of steel wire is wound spirally round one of the veins in its turgid condition , and with a needle and thread the coats of the vessel are stitched here and there to the wire , care being taken to avoid puncturing the lining membrane , and thus the vessel is converted into a rigid cup . Two such cups being prepared , and the lining membrane of the vein being everted at the orifice of each so as to avoid contact of the blood with any injured tissue , I found that , after pouring blood to and fro through the air in a small stream from one venous receptacle into the other half a dozen times , and closing the orifice of the receptacle to prevent drying , the blood was still more or less completely fluid after the lapse of eight or ten hours . On the other hand , if a fine sewing , -needle is pushed through the wall of an unopened vessel so that its end may lie in the blood , it is found on examination , after a certain time has elapsed , that the needle is surrounded with an encrusting clot . It is scarcely necessary to point out how entirely the ammonia theory and the oxygen theory , as well as that of rest , fail to account for facts like these . While the blood may remain fluid for forty-eight hiouirs in the jugular vein of a horse or an ox , it coagulates soon after death in the heart of very small animals , such as mice ; so that it is obvious that the continuance of fluidity in small vessels is not due to their small size . It is a very curious question , What is the cause of the blood remaining so much longer fluid in some vessels than in others ? I belies-e that we must accept it simply as anl ultimate fact , that just as the braini loses its vital properties earlier than the ganglia of the heart , so the heart and principal vascular trunks lose theirs sooller than the smaller vessels of the viscera , or than more superficial vessels , be they large or small . We can see a final cause for this , so to speak . So long as the heart is acting , circulation will be sure to go on in the heart and principal trunks ; whereas , on the contrary , the more superficial parts are l able to temporary causes of stagnationi , and occasionally to what amoiunts to practical severance form vascular and nervous connexion with the rest of the body ; and it is , so to speak , of great impoirtance that the blood should not coagulate so speedilv in the vessels of a limb thus circumstanced as it does in the heart after it has ceased to beat . Were it not for this provision , the surgeon would be unable to apply a touirniquet without fear of coagoilation occurring in the vessels of the limb . As any illustration of the importance of a knowledge of these facts , I may mention a case that once occurred in my own practice . I was asked by a surgeon in a couytry district to amputate an arm which he despaired of The brachial artery had been wounded , as well as veins and nerves , and at last , being foiled with the hemorrhage , he wound a long bandage round the limb at the seat of the wound as tightly as he possibly could . It had been in this condition with the bandage thus applied for fortyeight hours when I reached the patient ; and the limib had all the appearance of being dead . It was perfectly cold , and any colour which it had was of a livid tint . But having been lately engaged in some of the experiments which I have been describing , and havin-g thus become much impressed with the persistent vitality of the tissues and the concomitant fluidity of the blood , I determined to give the limb a chance by tying the brachial artery . Before I left the patient 's house hie had already a pulse at the wrist , and I afterwards had the satisfactitn of hearing that the arm had proved a useful onie . One of the two arguments in favour of activity Cen the part of the vessels as a cause of the fluidity of the blood having been completely disposed of , let us now consider the other , viz. the rapid coagulation of blood shed into a basin , appearing at first sight to imply a spontaneous tendency of the blood to coagulate , such as would have to be counteracted by the vessels . This also has proved fallacious . In the first place it appears that the coagulation , after all , does not go on in a basini so suddenly as one would at first sight suippose , but always commences in contact with the foieign solid . Wheni blood has beenl shed into a glass jar , if , on the first appearance of a film at the surface , you introduce a mounted needle curved at the end be2 u tween the blood and the side of the glass and make a slight rotatory movement of the handle , you see through the glass the point of the needle detaching a layer of clot whatever part you may examine . The process of coagulation having thus commenced in contact with the surface of the vessel into which the blood is shed , may under favourable circumstances be ascertained to travel inwards , like advancing crvstallization , towards the centre of the mass . It appears , however , that this extension of the coagulating process would not take place had not the blood been prepared for the change by contact , during the process of shedding , with the injured orifice of the blood-vessel and with the surface of the receptacle . I have only very recently become acquainted with the remarkable subtlety of the influence exerted upon blood by ordinary solids . I was lorng since struck with the fact , that if I introduced the point of an ordinary sewing-needle through the wall of a vein in a sheep 's foot and left it for twelve hours undisturbed , the clot was still confined to a crust round the point of the needle , implying that coagulum has only a very limited power of extension . I thought , therefore , that by proper management it might be possible to keep blood fluid in a vessel of ordinary solid matter lined with clot . But various attempts made with this object failed entirely , till I lately adopted the following expedient . Having opened the distal end of an ox 's jugular vein containing blood and held in the vertical position , taking care to avoid contact of any of the blood with the wounded edge of the vessel , I slipped steadily down into it a cylindrical tube of thin glass , somewhat smaller in diameter than the vein , open at both ends , and with the lower edge ground smooth in order that it might pass readily over the lining membrane , and so disturb the blood as little as possible by its introduction , and influence only the circumferential parts of its contents . The tube was then kept pressed down vertically upon the bottom of the vein by a weight , in a room as free as possible from vibration , and I found on examining it at the end of twelve hours that the clot was a tubular one , consisting of a crust about one-eighth of an inch thick next the glass and the part exposed to the air , but containing in its interior fluid and rapidly coagulable blood . In another such experiment , continued for twenty-fours , though the crust of clot was thicker , the central part still furnished coagulable blood . But it may pernaps be argued by those who say that the bloodvessels are active in maintaining fluidity , that the small portion of the vein covering the end of the tube was acting upon the blood , which certainly was fluid where in contact with it , the clot being in the form of a tube open at the lower end . To guard against such an objection I made the following experiment:-I extended a tube like that above described by means of thin sheet gutta percha , G(fig . 6a ) , contriving that the internal surface of the gutta percha should be perfectly continuous with that of the glass tube as represented in section in fig. 6 6 . The lower part of the gutta-percha tissue was strengthened by a ring of soft flexible wire such as is used by veterinary surgeons for sutures , and the wire W was also extended upwards to the top of the glass so as to maintain the rigidity of the gutta-percha portion during its introduction into a vein , but at the same time , from its softness , permit the gutta-percha part to be bent at a right angle after it had been introduced , and so close the orifice of the glass tube with ordinary solid matter . In fig. 6c the tube is represented pressed down by a weight in a vein V , with blood B in the glass portion , while the gutta-percha part closes it below . At the same time I performed a comparative experiment , to which I would invite particular attention , although I am sorry at this late hour to occupy the attention of the Society so long . I tied a thin piece of guttapercha tissue over the lower end of a similar glass tube , and simply Fig. 6 . a 6 . c.d Q ' poured blood into it from the jugular veini of an ox . I wished to compare the condition of blood which had been simply poured into a tube , with blood which had been introduced without any disturbance of its central parts . But in order to make the experiment a fair one , as it might be said that the blood poured from the vein had been more exposed to the air than that into which the tube was slipped , I proceeded in the following way -I obtained a long vein containling plenty of blood , and having first filled the second tube , with the guittapercha bottom ( fig. 6 d ) , by simply pouring blood into it from the vein , I cut off a portion of the veini which had been thus emptied , and having tied one end and everted the lining merTibrane of the other enid , and having also everted the lining membrane of the orifice of the remaindcer of the vessel which was full , I poured the blood from the full portion through the air into the em pty part . In doing this I had difficulty in gettintg blood eniongh , and it passed through the air in slow drops , and that only when the vein was squeezed by my warm hand . At last , having introduLced sufficient for the pwrpose , I slipped down the compound tube arid bent its gutta-perca portion , as represenited in fig. 6 c , and left both tubes for a while und , is , turbed , At the end of three hours aid a half I found that the blood which had been simply poured in was a mass of clot , and fluid squeezed from it yielded no threads of fibrini , coagulation being complete . Eow long it had beenl so I do not know . I did not exaniine the other blood until seven hours and three quarters bad expired . aY1d them found that , just as in the cases where a simple glass tuibe was introduced , the clot was tubular , and the chief part of the blood was still fluid in its interior , the ornly differeniee being that in this ecase the clot formed a complete capsule , being continued over the guitta percha instead of being deficient below , as it was when the vein closed the end of the tube . Now if we consider the two parts of this comparative experiment , we see that thie receptacles in which the blood was ultimately contained were precisely similar in the two cases , viz. glass tubes closed below with gutta perchla ; and that the blood which was simply poured into the tube was much less exposed to the air than the other , and aso was not subjected , like it , to elevation of temperature , a circumstance which promaotes coagulationi ; but yet this blood becamne completely coag , ulated ill a comparatively short time , whereas the other after a much long , er time was coagulated only in a layer in contact with the foreign solid . But in the latter case the blood had been so introduiced as to avoid direct action of ordinary matter on any but the circumferential parts of it ; whereas in the former , though poured quickly , it had run down the side of the glass , auid as a consequence of this almost momentary contact with the foreign solid , the central parts , like the circumferential , underwent the process of coagulation . i Jysterious as this subtle agency of ordinary solids must appear , its occurrence is thus matter of experimental demonstration , and by it the coagulation of blood shed into a basin is accounted for ; while it is also shown conclusively from this experiment that the blood , as it exists within the vessels , has no spontaneous tendenlcy to coagulate , and therefore that the notion of any action on the part of the bloodvessels to prevent coagulation is entirely out of the question . The peculiarity of the living vessels consists not in any such action upon the blood , but in the circumstanice , remarkable indeed as it is , that their lining membrane , when in a state of health , is entirely negative in its relation to coagulation , and fails to cause that molecular disturbance or , if we may so speak , catalytic action which is produced upoul the blood by all ordinary matter . I afterwards found that the simplest method of maintaining blood fluid in a vessel composed entirely of ordinary matter was to employ a glass tube similar to those above described , except that its upper end was closed by a cork perfortated by a narrow tube terminating in a piece of vulcanized inidia-rubber tubing that could be closed by a clamnp . This tube was slipped down inito a vein till the blood , havinSg , filled it completely , showed itself at the orifice of the india-rubber tubing , to which the clamp was then applied . The whole apparatus was now quickly inverted , and the vein was drawn off from over the mouth of the tube , which was then covered with gutta-percha tissue to prevent evaporation . After the inverted tube had been kept unidisturbed in the vertical position for nineteen hours and three quarters , coagulable blood was obtained from the interior of the clot . Ve have seen that a clot has but very slight tendency to induce coagulation in its vicinity unless the blood has been acted on by an ordiniary solid ; and it is probable that with perfectly healthy blood it would be unable to produce such an effect at all . This appears to me to be very interesting physiologically , but especially so with reference to pathology . I must not go now fully into the circumstances that lead me to it ; but I may express the opinion I have formed , that clot must be regarded as living tissue in its relation to the blood . It is no doubt a very peculiar form of tissue , in this respect , that it is soft , easily lacerable , and easily impaired in its vital properties . If disturbed , as in an aneurism , it will readily be brought into that condition which leads to the deposition of more clot ; but if undisturbed , it not only fails to induce further coagulation , but seems to undergo spontaneous organizationl . I have seen a clot in the right side of the heart , and extending into the pulmonary artery and its bralnches , unconnected withi the lining membrane of auricle or ventricle or with the pulmonary artery except at one small spot where it had a slight adhesion , developed into perfect fibrous tissue by virtue , it would appear , of its own inherent properties . Another observation which I once made , and which then completely puzzled me , now seems capable of explanation . In laying open the blood-vessels of a dead body , I observed in maniy of the veins a delicate white lace-like tissue which evidently must have been formed from a clot . This I now believe to have had the same relation to the coagulum as the flimsy cellular tissue of old adhesions has to lymph . It may not be altogether superfluous to mention some other facts illustrative of the active influence of ordinary matter in promoting coagulationl , and the negative charac er of the lining membrane of the vessels . I find that a needle introduced into one of the veins of the foot of a sheep for a much shorter time than is necessary to produce the first appearance of the actual deposit of fibrill upon it , leads after a while to coagulationi where the needle had lain-in other words , that a foreigni solid , by a short period of action on the blood , brings about a change that results in coagulation , though the blood still lies in the living vessels . I have also ascertained that after blood has been made to coagulate in a particular vessel by introducing a needle into it , if the coaguliim as well as needle is removed , and more fluid blood is allowed to pass in , this blood remains fluid for an incdefinite period , showing that the nleedIle had not impaired the properties of the vessel by its presence ; so that the previous coagulation must be attributed not to any loss of power in the vein , but simply to the action of the foreign solid . In seeking for an analogy to this remarkable effect of ordinary solids upon the blood , we are naturally led to the beautiful observations of Professor Graham , lately published in the Philosophical Transactions . He has there shown what insignificant causes are often sufficient to induce a change from the fluid or soluble to the " cpectous , " or insoluble condition of " colloidal " forms of matter . Indeed Mr. Graham has himself alluided to the coagulation of fibrin as being probably an example of such a transition . There is , however , another remarkable circumstance that must be takeni into consideration , of which I myself have been only recently aware , and which may be new to several Fellows of the Society ; and that is , that in spite of the iinfluence of an ordinary solid the liquor sanguinis is not capable of coagulating per se . It was observed many years ago by my colleague , Professor Andrew Buchanan , of Glasgow , that the fluid of a hydrocele , generally regarded as mrlere serum , coagulated firmly if a little coagulum of blood diffused in water was added to it-an effect which he was disposed to attribute to the agency of the white corpuscles* . I repeated Dr. Andrew Buchanan 's observations last year , and satisfied myself first that the diffused clot did not act simiply by providing solid particles to serve as starting-points for the coagulating process . I tried various different materials in a finely divided state , and found that nonie of them , except blood , produced the slightest effect . But I found that if a mixture of serum and red corpuscles from a clot was added to some of this hydrocele-fluid , it was soon converted into a firm solid mass . If a small quantity of the serum and corpuscles was diropped into the fluid and allowed to subside without stirring , coagulation rapidly took place in those parts where the red corpuiscles lay , while other parts of the fluid remained for a long tinme uncoagulated . This seemed to indicate that the red corpuscles had a special virtue in inducing the chanige . I confess , however , that till very lately I was inclined to suppose that in the hydrocele-fluid the fibrin must be in some peculiar spurious form . We know that the buffy coat of the horse 's blood coagulates in a glass without addition of clot , and we know that lymph coagulates ; so that I did not doubt Proccedirmis of the Glasgow Philosophical Society , Fehruary 19 , 1845 . that liquor sanguinis would always undergo the chantge when influenced by ordiniary matter . But an observation which I made not many days ago , shows that this was a mistake . I obtained the jugular vein of a horse , and having kept it for a while in a vertical position till I could see through its transparent coats that the red corpuscles had fallen from the upper part , I removed all bloody tissue from that part of the vein , and punctured it so as to let out the Flequor sarnguiinis iinto a glass . Finding after eighteen minutes that the liquid had not begun to coagulate , I added a drop of serurn and corpuscles to a portion of it , and within seven minutes there was a clot wherever the corpuscles lay , whereas the rest of the fluid was still very imperfectly coaguilated after another half hour had elapsed . That the liquor sanguinis to which no addition had been made coagulated at all , was sufficiently explained by microscopic investigation , which showed not only abundanit white corpuseles , but also several isolated red ones that had not subsided . This observation was made three hours after the death of the horse , but I obtained essentially similar results on repeating the experiment in another horse an hour after death ; so that there can be no doubt whatever that the fibrin was in the same condition as it is in the blood-vessels of a living animal . The observation appears also particularly satisfactory on this account , that the liquor sanguinis was not separated from the corpuscles by any process of transudation through the walls of the blood-vessels , which might be conceived to involve retention of some constituent of the liquid , which , though in solution , might be unable to pass through their pores , but simply by the subsidence of the corpuscles , which must have left all the materials of the liquor sanguinis behinld them . Hence it is proved beyorid question that if the liquor sanguinis could be separated completely from the blood-corpuscles , it would resemble the fluid of hydrocele in being incapable of coagulation when shed into a cup . Now this struck me as a very satisfactory and beautiful truth , inasmuch as it clears away all the old mystery of the distinction between inflammatory exudations and dropsical effusionis . Dropsical efiusions , exhibiting little disposition to coagulate , have been supposed to consist almost excluisively of serum , and the exudation of the entire liquor saniguinis has been regarded as the special characteristic of inflammation ; and very unsatisfactory theories have been put forward by ingenious pathologists to account for this difference . But it now appears that a dropsical effusion , like that of hydrocele , is undistinguishable from pure liquor sanguinis . Various dropsical effusions have been lately investigated with reference to their coagulability on the addition of blood-corpuscles , by Dr. Schmidt of Dorpat , who finds that while they differ from one another in the amount of water they contain ( just as is the case with serum filtered artificially through animal membranes under different degrees of pressure ) , yet they are all but universally coagulable . Schmidt has also carried the investigation further . He has found that by chemical means be can extract from the red corpuscles a soluble material which , when added to these exudations , leads to coagulation . In other words , he shows that the corpuscles do not act as living cells , but by virtue of a chemical material which they contain , which can be used in the state of solution , free from any solid particles whatever . He found also that the aqueous humour made a dropsical effusion coagulaW , and that the same effect was proda:ced by a material extracted from the non-vascular part of the cornea . 1-lence he regards the blood-corpuscles as only resembling other forms of tissue in possessing this property . These observations are e:xtremely interesting , if trustworthy ; and that they are so , I do not at all doubt ; but having only read Schmidt 's papers within the last day or two , I have not yet had opportunity of verifying , ' his statements* . It remains to be ascertained what share the material derived from the corpuscles has in the composition of the fibrin . Schmidt inclines to the opinion that the fibrin is probably composed , in about equal proportions , of a substance fuirriished by them and one present in the liquor sanguinis . If this be true , the action of an ordinary solid in determining the union of the components of the fibrini may be compared to the operation of spongy platinum in promnoting the combination of oxygen and hydrogen . It may be asked , How comes it that when the blood of a horse is shed into a cup , the buffy layer coagulates as rapidly , or nearly so , as the lower parts rich in corpuscles ? This is indeed a question well worthy of careful study . We know that the liquor sanguinis left by the subsidence of the red corpuscles within a healthy vein is incapable of coagulating when shed , except in a slow manner , which is accounted for by the corpuscles that remain behind in it . Hence it appears that when the blood as a whole is shed into a glass , the agency of the ordinary solid leads the corpuscles to communiicate to the liquor sanguinis , before they subside , a material or at least an influence which confers upon it a disposition to coagulate , though it still remains fluid for some time after they have left it . Just as we have seen that a very short time of action of the ordinary solid upon the blood as a whole is sufficient to give rise to coagulationi , so we now see that , provided an ordinary solid be in operation , the presence of the corpuscles for but a little while is enough to make the liquor sanguiniis spontaneously coagulable , though not immediately solidified . We shall see , before concluding , an illustration of the importance of this fact to pathology . It remains to be added , that serous membranes resemble the lining melnbrane of the blood-vessels in their relations to the blood , as is implied by John Hunter 's observation that blood , which had lain for several days in a hydrocele , coagulated when let out . The same thing is well illustrated in a frog prepared like this which I now exhibit . About four hours ago , a knife having been passed between the brain and cord to deprive the creature of voluntarv mnotion in the limbs and trunk , the peritoneal cavity was laid open in the middle line , and its edges being kept raised and drawn aside by pins , I seized the apex of the ventricle of the heart with forceps and removed it with scissors . Inl a short time the whole of the animal 's blood was in the peritoneum , and it may be seen that it is still fluid in spite of this long-continued exposure . When I first performed the experiment three years and a half ago , the weather being cool ( about 45 ? Fahr. ) and a piece of damp lint being kept suspended above the frog to prevent evaporationi and access of dust , I found that the blood remained fluid in the peritoneal cavity for four days , except a thin film on the surface , and a crust of clot on the wounded part of the heart ; but a piece of clean glass placed in the blood in the peritoneum became speedily coated with coagulum . Here , it will be observed , not merely the liquor sanguinis , but the corpuscles also were present in the serous cavity , yet no coagulation took place in contact with its walls . I think it probable , though not yet proved , that all living tissues have these properties with reference to the blood . We know that the interstices of the cellular tissue contain coagulable fluid , and I have seen anasarcous liquid coagulate after emission ; but this indeed may possibly have been merely liquor sanguinis , coagulating in consequence of slight admixture of blood-corpuiscles from the wounds made in obtaining it . Looking now at the principal results which we have arrived at , it must , in the first place , be admitted that the ammonia theory is to be discarded as entirely fallacious . The fact that this theory is exceedingly plausible , and has been supported by many ingenious arguments and experiments , is of course no reason why we should retain it if unsound . On the contrary , the more specious it is the more necessary is it that it should be effectually cleared away ; for it mystifies the subject of coagulation most seriously ; and I may save , for my own part , that it has cost me an amount of experimental labour of which the illustrations brought forward this evening convey but little idea . Still these have been , I trust , sufficient to show that the coagulation of the blood is in no degree connected with the evolution of ammonia , any more than with the influence of oxygen or of rest . The real cause of the coagulation of the blood , when shed from the body , is the influence exerted upon it by ordinary matter , the contact of which for a very brief period effects a change in the blood , inducing a mutual reaction between its solid and fluid constituerts , in which the corpuscles impart to the liquor sanguinis a disposition to coagulate . This reaction is probably simply chemical in its nature ; yet its product , the fibrin , when mixed with blood-corpuscles in the form of an undisturbed coagulum , resembles healthy living tissues in being incapable of that catalytic action upon the blood which is effected by all ordinary solids , and also by the tissues themselves when deprived of their vital properties . These principles have , of course , very extensive applications to the study of disease ; but I must content myself with alluding very brieflv to inflammationi , the most important of all pathological conditions , If we inquire what is the great peculiarity of inflamed parts in relation to the blood as exam:rined by the naked eye , we see that it consists in a tenclency to induce coagulation in their vicinity-implying , according to the conielusions just stated , that the affected tissues have lost for the time being their vital properties , and coimport themselves like ordinary solids . Ths , when an artery or vein is inflamed , coagulation occurs upon its interior , in spite of the current of blood , precisely as would take place if it hadl been artificially deprived of its vital properties . On one occasion I simulated the characteristic adherent clot of Phlebitis by treating the jugular vein of a living sheep with caustic ammonia , and then allowing the circulation to go on through the vessel for a while , when , on slitting it up , I found its lining membralne studded with grains of pink fibrin which could be detached only by scraping firmly with the edge of a knife . Agaill , comparing an inflammatory exudation into the pericar(lium or into the initerstices of the cellular tissue with dropsical effusions into the same situations , we are struck with the fact that , while the liquor sanguinis effused in dropsy remains fluid , the inflammatory product coagulates . Now we know that in intense inflammation the capillaries are choked more or less with accumulated blood-corpuscles , which must cause great increase in the pressure of the blood upon their walls ; and froDI what we know of the effect of venous obstruction in causing dropsical effusion of liquor sanguinis through increased pressure , we are sure that we have in the iulflammatory state the physical conditions for a similar transudation of fluid through the walls of the capillaries . And the inatural interpretation of the difference in the two cases as regards coagulationi seems to be , that whereas in dropsy the fluid is forced through the pores of healthy vessels , in iinflammation the capillary parietes hbave lost their healthy condition , and act like ordinary matter ; so that the liquor sanguinis , having been subjected , immediately before effusion , to the combined influence of the injured tissue and the blood-corpuscles , has acquired a disposition to coagulate , juis like the buffy coat of horses ' blood shed into a glass , or like the frog 's liquor sanguinis filtered by Miiller from its corpuscles , the injured vessels acting uponl the blood like the filter . This view of the condition of intensely inflamed parts is exactly that to which I was led some years ago by a microscopic investigation , the results of which were detailed in a paper* that received the honour of a place in the Philosophical Transactions . It was there shown , as I thinik I may veniture to say , that the tissues generally are capable of being reduced under the action of irrita ts to a state quite distinct from death , but in which they are nevertheless temporarilyr deprived of all vital power , and that inflammatory congestion is due to the blood-corpuscles acquiring adhesiveness sueh as they lIave outside the body , in consequence of the irritated tissues acting towards them like ordinary solids . I cannot avoid expressing my satisfaction that this inquiry inito the coagullation of the blood has furnished indepeildent confirmation of my previous conclusions regarding the nature of inflammation .

112321

3701662

On the Molecular Mobility of Gases. [Abstract]

611

623

Proceedings of the Royal Society of London

Thomas Graham

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112321

http://www.jstor.org/stable/112321

Thermodynamics

Fluid Dynamics

Thermodynamics

I. " On the Molecular Mobility of Gases . " By TIol-MAs GRAHAM , F.R.S. , Mastelr of the Mint . Received May 7 , 1863 . ( Abstract ) . The molecular mobility of gases is here considered in reference chiefly to the passage of gases , under pressure , through a thin porous plate or septum , and to the partial separation of mixed gases which can be effected , as will be shown , by such means . The investigation * " On the Early Stages of Inflammation , " Phil. Trans. for 1858 . 1863 . ] 611 arose out of a renewed and somewhat protracted inquiry regarding the diffusion of gases ( depending upon the same molecular mobility ) , and has afforded certain new results which may prove to be of interest in a theoretical as well as in a practical point of view . In the diffusiometer , as first constructed , a plain cylindrical glass tube , rather less than an inch in diameter and about ten inches in length , was simply closed at one end by a porous plate of plaster of paris , about one-third of an inch in thickness , and thus converted into a gas receiver* . A superior material for the porous plate is now found in the artificially compressed graphite of Mr. Brockedon , of the quality used for making writing-pencils . This material is sold in London in small cubic masses about 2 inches square . A cube may easily be cut into slices of a millimetre or two in thickness by means of a saw of steel spring . By rubbing the surface of the slice without wetting it upon a flat sand-stone , the thickness may be further reduced to about one-half of a millimetre . A circular disk of this graphite , which is like a wafer in thickness but possesses considerable tenacity , is attached by resinous cement to one end of the glass tube above described , so as to close it and form a diffusiometer , The tube is filled with hydrogen gas over a mercurial trough , the porosity of the graphite plate being counteracted for the time by covering it tightly with a thin sheet of gutta percha . On afterwards removing the latter , gaseous diffusion immediately takes place through the pores of the graphite . The whole hydrogen will leave the tube in forty minutes or an hour , and is replaced by a much smaller proportion of atmospheric air ( about one fourth ) , as is to be expected from the law of the diffusion of gases . During the process , the mercury will rise in the tube , if allowed , forming a column of several inches in height-a fact which illustrates strikingly the intensity of the force with which the interpenetration of different gases is effected . The native or mineral graphite is of a lamellar structure , and appears to have little or no porosity . It cannot be substituted for the artificial graphite as a diffusion-septum . Unglazed earthenware comes next in value to graphite for this purpose . The pores of artificial graphite appear to be really so minute , that a gas in mass cannot penetrate the plate at all . It seems to be molecules only which can pass ; and these may be supposed to pass wholly unimpeded by friction , for the smallest pores that can be imagined to exist in the graphite must be tunnels in magnitude to the ultimate atoms of a gaseous body . The sole motive agency appears to be that intestine movement of molecules which is now generally recognized as an essential property of the gaseous condition of matter . According to the physical hypothesis now generally received ' , a gas is represented as consisting of solid and perfectly elastic spherical particles or atoms , which move in all directions , and are animated with different degrees of velocity in different gases . Confined in a vessel , the moving particles are constantly impinging against its sides and occasionally against each other , and such collisions take place without any loss of motion , owing to the perfect elasticity of the particles . Now if the containing vessel be porous , like a diffusiometer , then gas is projected through the open channels , by the atomic motion described , and escapes . Simultaneously the external air or gas , whatever it may be , is carried inwards in the same manner , and takes the place of the gas which leaves the vessel . To the same atomic or molecular movement is due the elastic force , with the power to resist compression , possessed by gases . The molecular movement is accelerated by heat and retarded by cold , the tension of the gas being increased in the first instance and diminished in the second . Even when the same gas is present both within and without the vessel , and is therefore in contact with both sides of the porous plate , the movement is sustained without abatement-molecules continuing to enter and leave in equal number , although nothing of the kind is indicated by change of volume or otherwise . If the gases in communication be different but possess sensibly the same specific gravity and molecular velocity , as nitrogen and carbonic oxide do , an interchange of molecules also takes place without any change in volume . With gases opposed of unequal density and molecular velocity , the amount of penetration ceases of course to be equal in both directions . * D. Bernoulli , J. Herapath , Joule , KrInig , Clausius , Clerk Maxwell , and Cazin . The merit of reviving this hypothesis and first applying it to the facts of gaseous diffusion , is fairly due to Mr. Herapath . See 'Mathematical Physics , ' in two volumes , by John Herapath , Esq. ( 1847 ) . These observations are preliminary to the consideration of the passage through a graphite plate , in one direction only , of gas under pressure , or under the influence of its own elastic force . It is to be supposed that a vacuum is maintained on one side of the porous septum , and that air or some other gas , under a constant pressure , is in contact with the other side . Now a gas may pass into a vacuum in three different modes , or in two modes besides that immediately before us . 1 . The gas may enter the vacuum by passing through a minute aperture in a thin plate , such as a puncture in platinum foil made by a fine steel point . The rate of passage of different gases is then regulated by their specific gravities , according to a pneumatic law which was deduced by Professor John Robison from Torricelli 's well-known theorem of the velocity of efflux of fluids . A gas rushes into a vacuum with the velocity which a heavy body would acquire by falling from the height of an atmosphere composed of the gas in question , and supposed to be of uniform density throughout . The height of the uniform atmosphere will be inversely as the specific gravity of the gas , the atmosphere of hydrogen , for instance , sixteen times higher than that of oxygen . But as the velocity acquired by a heavy body in falling is not directly as the height , but as the square root of the height , the rate of flow of different gases into a vacuum will be inversely as the square root of their respective densities . The velocity of oxygen being 1 , that of hydrogen will be 4 , the square root of 16 . This law has been experimentally verified* . The times of the effusion of gases , as I have spoken of it , are similar to those of the law of molecular diffusion ; but it is important to observe that the phenomena of effusion and diffusion are distinct and essentially different in their nature . The effusion movement affects masses of gas , the diffusion movement affects molecules ; and a gas is usually carried by the former kind of impulse with avelocity many thousand times greater than by the latter . The effusion velocity of air is the same as the velocity of sound . 2 . If the aperture of efflux be in a plate of increased thickness , and so becomes a tube , the effusion-rates of gases are disturbed . The rates of flow of different gases , however , assume again a constant ratio to each other when the capillary tube is considerably elongated , when the length exceeds , the diameter at least 4000 times . These new proportions of efflux are the rates of the " Capillary Transpiration of Gases " * . The rates were found to be the same in a capillary tube composed of copper as they are in a tube of glass , and appear to be independent of the material of the capillary . A film of gas no doubt adheres to the inner surface of the tube , and the friction is really that of gas upon gas , and is consequently unaffected by the nature of the tube-substance . The rates of transpiration are not governed by specific gravity , and are indeed singularly unlike the rates of effusion . The transpiration-velocity of oxygen being 1 , that of chlorine is 1'5 , that of hydrogen 2'26 , of ether vapour at low temperatures the same or nearly the same number as hydrogen , of nitrogen and carbonic oxide half the velocity of hydrogen , of olefiant gas , ammonia , and cyanogen 2 ( double or nearly double that of oxygen ) , of carbonic acid 13 76 , and of the gas of marshes 1'815 . In the same gas the transpirability of equal volumes increases with density , whether occasioned by cold or pressure . The transpiration-ratios of gases appear to be in constant relation with no other known property of the same gases , and they form a class of phenomena remarkably isolated from all else at present known of gases . There is one property of transpiration immediately bearing upon the penetration of the graphite plate by gases . The capillary offers to the passage of gas a resistance analogous to that of friction , proportional to the surface , and consequently increasing as the tube or tubes are multiplied in number and diminished in diameter , with the area of discharge preserved constant . The resistance to the passage of a liquid through a capillary was observed by Poiseuille to be nearly as the fourth power of the diameter of the tube . In gases the resistance also rapidly increases ; but in what ratio , has not been observed . The consequence , however , is certain , that as the diameter of the capillaries may be diminished beyond any assignable limit , so the flow may be retarded indefinitely , and caused at last to become too small to be sensible . We may therefore have a mass of capillaries of which the passages form a large aggregate , but which are individually too small to permit a sensible flow of gas under pressure . A porous solid mass may possess the same reduced penetrability as the congeries of capillary tubes . Indeed the state of porosity described appears to be more or less closely approached by all loosely aggregated mineral masses , such as lime plaster , stucco , chalk , baked clay , non-crystalline earthy powders like hydrate of lime or magnesia compacted by pressure , and in the highest degree perhaps by artificial graphite . 3 . A plate of artificial graphite , although it appears to be practically impenetrable to gas by either of the two modes of passage previously described , is readily penetrated by the agency of the molecular or diffusive movement of gases . This appears on comparing the time required for the passage of equal volumes of different gases under a constant ptessure . Of the following three gases , oxygen , hydrogen , and carbonic acid , the time required for the passage of an equal volume of each through a capillary glass tube , in similar circumstances as to pressure and temperature , was formerly observed to be as follows : Time of capillary transpiration . Oxygen ... ... ... ... . 1 Carbonic acid ... ... ... 0'72 Hydrogen ... ... ... ... . . 044 Through a plate of graphite , of half a millimetre in thickness , the same gases were now observed to pass , under a constant pressure of a column of mercury of 100 millimetres in height , in times which are as follows : Time of molecular Square root of density passage . ( oxygen 1 ) . Oxygen ... ... ... 1 ... . 1 Iydrogen ... ... ... . 0-2472 ... . 0-2502 Carbonic acid ... ... . . 11886 ... . 11760 It appears then that the times of passage through the graphite plate have no relation to the capillary transpiration-times of the same gases first quoted above . The new times in question , however , show a close relation to the square roots of the densities of the respective gases , as is seen in the last Table ; and so far they agree with theoretical times of difusion usually ascribed to the same gases . The experiments were varied by causing the gases to pass into a Torricellian vacuum , and consequently under the full pressure of the 616 atmosphere . The times of penetration of equal volumes of gases were nowTimes . V/ Density , Oxygen ... ... ... . . 1 ... . 1 Air.0 ... ... ... ... 9501 ... . 09507 Carbonic acid ... ... 1-1860 ... . 1P1760 Hydrogen ... ... ... 0-2505 ... . 0-2502 This penetration of the graphite plate by gases appears to be entirely due to their own proper molecular motion , quite unaided by transpiration . It seems to offer the simplest possible exhibition of the molecular or diffusive movement . This pure result is to be ascribed to the wonderfully fine porosity of the graphite . The interstitial spaces , or channels , appear to be sufficiently small to extinguish transpiration , or the passage of masses , entirely . The graphite becomes a molecular sieve , allowing molecules only to pass through . With a plate of stucco , the penetration of gases under pressure is very rapid , and the volumes of air and hydrogen passing in equal times are as 1 to 2'891 , which is a number for hydrogen intermediate between its transpiration-volume 2'04 and diffusion-volume 3 8 , showing that the passage through stucco is a mixed result . With a plate of biscuitware , 2-2 millimetres in thickness , the volume of hydrogen rose to 3'754 ( air= 1 ) , approaching closely to 3'8 , the molecular ratio . The rate of passage of a gas through graphite appeared also to be closely proportional to the pressure . Further , hydrogen was found to penetrate through a graphite plate into a vacuum , with sensibly the same absolute velocity as it diffused into air , establishing the important fact that the impelling force is the same in both movements . The molecular mobility may therefore be spoken of as the diffusive movement of gases ; the passage of gas through a porous plate into vacuum , as diffusion in one direction or single diffusion ; and ordinary diffusion , or the passage of two gases in opposite directions , as double , compound , or reciprocal diffusion . Atmolysis.-A partial separation of mixed gases and vapours of unequal diffusibility can be effected by allowing the mixture to permeate through a graphite plate into a vacuum , as was to be expected from the preceding views . As this method of analysis has a practical character and admits of wide application , it may be convenient to 1863 . ] 617 distinguish it by a peculiar name . The amount of the separation is in proportion to the pressure , and attains its maximum when the gases pass into a nearly perfect vacuum . A variety of experiments were made on this subject , of which perhaps the most interesting were those upon the concentration of the oxygen in atmospheric air . When a portion of air confined in a jar is allowed to penetrate into a vacuum through graphite or unglazed earthenware , the nitrogen should pass more rapidly than the oxygen in the proportion of 1'0668 to 1 , and the proportion of oxygen be proportionally increased in the air left behind in the jar . The increase in the oxygen actually observed when the air in the jar was reduced from 1 volume To 0'5 volume , was 0'48 per cent. 0-25 , , , , 0'98 0-125 , 1-54 0-0625 , , , 2-02 Or , the oxygen increased from 21 to 23'02 per cent. in the last sixteenth part of air left behind in the jar . The most remarkable effects of separation are produced by means of the tu6e atmolyser . This is simply a narrow tube of unglazed earthenware , such as a tobacco-pipe stem two feet in length , which is placedwithin a shorter tube of glass and secured in its position by corks , so as to appear like a Liebig 's condenser . The glass tube is placed in communication with an air-pump , and the annular space between the two tubes is maintained as nearly vacuous as possible . Air or any other mixed gas is then allowed to flow in a stream along the clay tube , and collected as it issues . The gas so atmolysed is of course reduced in volume , much gas penetrating through the pores of the clay tube into the air-pump vacuum ; and the slower the gas is collected the greater the proportional loss . In the gas collected , the denser constituent of the mixture is thus concentrated in an arithmetical ratio , while the volume of the gas is reduced in a geometrical ratio . In one experiment the proportion of oxygen in the air after traversing the atmolyser was increased to 24-5 per cent. , or 16'7 upon 100 oxygen originally present in the air . With gases differing so much in density and diffusibility as oxygen and hydrogen , the separation is of course much more considerable . The explosive mixture of two volumes of hydrogen and one volume of oxygen , gave oxygen containing only 93 per cent. of hydrogen , in which a taper burned without explosion ; and with equal volumes of oxygen and hydrogen , the proportion of the latter was easily reduced from 50 to 5 per cent. Interdifusion of Gases-double diffusion.-The diffusiometer was much improved in construction by Prof. Bunsen , from the application of a lever arrangement to raise and depress the tube in the mercurial trough . But the mass of stucco forming the porous plate in his instrumeht was too voluminous , in my opinion , and , from being dried by heat , had probably detached itself from the walls of the glass tube . The result obtained of 3 4for hydrogen , air being 1 , is , I understand , no longer insisted upon by that illustrious physicist . It is indeed curious that my old experiments generally rather exceeded than fell short of the theoretical number for hydrogen , 9=7997 . With stucco as the material , the cavities in the porous plate form about one-fourth of its bulk , and affect sensibly the ratio in question , according as they are or are not included in the capacity of the instrument . Beginning the diffusion always with these cavities filled with hydrogen , the numbers now obtained with a stucco plate of 12 millims. in thickness , dried without heat , were 3 783 , 3'8 , and 3'739 when the volume of the cavities of stucco is added to the air and hydrogen , and 3'931 , 3'949 , and 3*883 when such addition is not made to these volumes . The graphite plate , on the other hand , being thin , and the volume of its pores too minute to require to be taken into account , its action is not attended with the same uncertainty . With a graphite plate of 2 millims. in thickness , the number for hydrogen into air was 3'876 , and of hydrogen into oxygen 4'124 , instead of 4 . With a graphite plate of 1 millim. in thickness , hydrogen gave 3'993 to air I. With a graphite plate of 0'5 millim. in thickness , the proportional number for hydrogen to air rose to 3*984 , 4*068 , and 4'067 . A similar departure from the theoretical number was observed when hydrogen was diffused into oxygen or carbonic acid , instead of air . All these experiments were made over mercury and with dried gases . It appears that the numbers are most in accordance with theory when the graphite plate is thick , and the diffusion slow in consequence . If the diffusion be very rapid , as it is with the thin plates , something like a current is possibly formed in the channels of the graphite , 1863 . ] 619 taking the direction of the hydrogen and carrying back in mass a little air , or the slower gas , whatever it may be . I cannot account otherwise for the slight predominance which the lighter and faster gas appears always to acquire in diffusing through the porous septum . Speculative ideas respecting the constitution of matter . It is conceivable that the various kinds of matter , now recognized as different elementary substances , may possess one and the same ultimate or atomic molecule existing in different conditions of movement . The essential unity of matter is an hypothesis in harmony with the equal action of gravity upon all bodies . We know the anxiety with which this point was investigated by Newton , and the care he took to ascertain that every kind of substance , " metals , stones , woods , grain , salts , animal substances , &c. , " are similarly accelerated in falling , and are therefore equally heavy . In the condition of gas , matter is deprived of numerous and vary . ing properties with which it appears invested when in the form of a liquid or solid . The gas exhibits only a few grand and simple features . These again may all be dependent upon atomic and molecular mobility . Let us imagine one kind of substance only to exist , ponderable matter ; and further , that matter is divisible into ultimate atoms , uniform in size and weight . We shall have one substance and a common atom . With the atom at rest the uniformity of matter would be perfect . But the atom possesses always more or less motion , due , it must be assumed , to a primordial impulse . This motion gives rise to volume . The more rapid the movement the greater the space occupied by the atom , somewhat as the orbit of a planet widens with the degree of projectile velocity . Matter is thus made to differ only in being lighter or denser matter . The specific motion of an atom being inalienable , light matter is no longer convertible into heavy matter . In short , matter of different density forms different substances-different inconvertible elements as they have been considered . What has already been said is not meant to apply to the gaseous volumes which we have occasion to measure and practically deal with , but to a lower order of molecules or atoms . The combining atoms hitherto spoken of are therefore not the molecules of which the movement is sensibly affected by heat , with gaseous expansion as 620 [ June 18 , the result . The gaseous molecule must itself be viewed as composed of a group or system of the preceding inferior atoms , following as a unit laws similar to those which regulate its constituent atoms . We have indeed carried one step backward and applied to the lower order of atoms ideas suggested by the gaseous molecule , as views derived from the solar system are extended to the subordinate system of a planet and its satellites . The advance of science may further require an indefinite repetition of such steps of molecular division . The gaseous molecule is then a reproduction of the inferior atom on a higher scale . The molecule or system is reached which is affected by heat , the diffusive molecule , of which the movement is the subject of observation and measurement . The diffusive molecules are also to be supposed uniform in weight , but to vary in velocity of movement , in correspondence with their constituent atoms . Accordingly the molecular volumes of different elementary substances have the same relation to each other as the subordinate atomic volumes of the same substances . But further , these more and less mobile or light and heavy forms of matter have a singular relation connected with equality of volume . Equal volumes of two of them can coalesce together , unite their movement , and form a new atomic group , retaining the whole , the half , or some simple proportion of the original movement and consequent volume . This is chemical combination . It is directly an affair of volume , and only indirectly connected with weight . Combining weights are different , because the densities , atomic and molecular , are different . The volume of combination is uniform , but the fluids measured vary in density . This fixed combining measure the metron of simple substances-weighs 1 for hydrogen , 16 for oxygen , and so on with the other " elements . " To the preceding statements respecting atomic and molecular mobility , it remains to be added that the hypothesis admits of another expression . As in the theory of light we have the alternative hypotheses of emission and undulation , so in molecular mobility the motion may be assumed to reside either in separate atoms and molecules , or in a fluid medium caused to undulate . A special rate of vibration or pulsation originally imparted to a portion of the fluid medium enlivens that portion of matter with an individual existence , and constitutes it a distinct substance or element . 621 With respect to the different states of gas , liquid , and solid , it may be observed that there is no real incompatibility with each other in these physical conditions . They are often found together in the same substance . The liquid and the solid conditions supervene upon the gaseous condition rather than supersede it . Gay-Lussac made the remarkable observation that the vapours emitted by ice and water , both at 0 ? C. , are of exactly equal tension . The passage from the liquid to the solid state is not made apparent in the volatility of water . The liquid and solid conditions do not appear as the extinction or suppression of the gaseous condition , but something superadded to that condition . The three conditions ( or constitutions ) probably always coexist in every liquid or solid substance , but one predominates over the others . In the general properties of matter we have , indeed , to include still further ( 1 ) the remarkable loss of elasticity in vapours under great pressure , which is distinguished by Mr. Faraday as the Caignard-Latour state , after the name of its discoverer , and is now undergoing an investigation by Dr. Andrews , which may be expected to throw much light upon its nature ; ( 2 ) the colloidal condition or constitution , which intervenes between the liquid and crystalline states , extending into both and affecting probably all kinds of solid and liquid matter in a greater or less degree . The predominance of a certain physical state in a substance appears to be a distinction of a kind with those distinctions recognized in natural history as being produced by unequal development . Liquefaction or solidification may therefore not involve the suppression of either the atomic or the molecular movement , but only the restriction of its range . The hypothesis of atomic movement has been elsewhere assumed , irrespective of the gaseous condition , and is applied by Dr. Williamson to the elucidation of a remarkable class of chemical reactions which have their seat in a mixed liquid . Lastly , molecular or diffusive mobility has an obvious bearing upon the communication of heat to gases by contact with liquid or solid surfaces . The impact of the gaseous molecule , upon a surface possessing a different temperature , appears to be the condition for the transference of heat , or the heat movement , from one to the other . The more rapid the molecular movement of the gas the more frequent the contact , with consequent communication of heat . Hence , probably , the great cooling power of hydrogen gas as compared with air 62 or oxygen . The gases named have the same specific heat for equal volumes ; but a hot object placed in hydrogen is really touched 3'8 times more frequently than it would be if placed in air , and 4 times more frequently than it would be if placed in an atmosphere of oxygen gas . Dalton had already ascribed this peculiarity of hydrogen to the high " mobility " of that gas . The same molecular property of hydrogen recommends the application of that gas in the air-engine , where the object is to alternately heat and cool a confined volume of gas with rapidity .

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Results of the Magnetic Observations at the Kew Observatory, from 1858 to 1862 Inclusive. --No. I. [Abstract]

623

625

Proceedings of the Royal Society of London

Edward Sabine

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6.0.4

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http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112322

http://www.jstor.org/stable/112322

Meteorology

Tables

Meteorology

II . " Results of the Magnetic Observations at the Kew Observatory , from 1858 to 1862 inclusive."-No . I. By MajorGeneral EDWARD SABINE , P.R.S. Received May 2 ] , 1863 . ( Abstract . ) The first three sections of this paper are occupied by a discussion of the Laws of the Disturbances of the Magnetic Declination at Kew , derived from the photographic records of the Kew Observatory between January 1 , 1858 , and December 31 , 1862 . In the first section a synoptical table is given , showing the direction and amount of the easterly and of the westerly deflections of the declination magnet at 24 equidistant epochs on each of 95 days of principal disturbance occurring in the years 1858 to 1862 inclusive . The deflections are measured from the normals of the same month and hour , computed from the undisturbed positions at the same epochs on the 1825 days comprised in the five years since the commencement of the photographic records . The phenomenal laws of the disturbances on the 95 days are then investigated , and are compared with the corresponding laws derived from a far larger number of observations in the same years , taken out by the well-known process employed by the author in the reduction of the observations of the colonial magnetic observatories . The result is shown to be that , so far as the laws of the disturbances are concerned , the two processes furnish mutual confirmation the laws being approximately the same whether they are derived from the whole body of the hourly positions , or from that portion only which includes 95 days ( or on an average 19 days in each year ) which were specially affected by disturbance , -but that , for the purpose of eliminating the effects of the disturbances in the 623 s1863 . ] subsequent investigation of the secular , periodical , and other minor magnetic variations , the process of elimination introduced by the author and employed by him for several years past in the reduction of the colonial observations has the advantage of separating from the whole body of the observations a far greater portion of the disturbing influence than would be gained by the simple omission of the observations on the 95 days . The laws of the disturbance-diurnal variation , thus found to be approximately the same whether obtained from the narrower or from the wider basis of investigation , are then stated , and are compared with the results of similar investigations recorded in the author 's previous publications the points of accordance or of difference being severally discussed in the third section . The fourth section contains Tables of the " Diurnal Inequality , " and of the " Solar-diurnal Variation " at Kew , showing the mean values at each hour and in each month . The " Diurnal Inequality " is explained as consisting of two principal constituents , viz. the " Disturbance-diurnal Variation , " and the " Solar-diurnal Variation . " It is obtained for each month by taking the differences between the mean positions of the magnet at each of the 24 hours , in the month , and the mean position in the month itself ( viz. the mean of all the days and all the hours)-no omission whatsoever being made of disturbed observations . The " Solar-diurnal Variation " is obtained by a similar process , after the separation and omission of all the observations which differed by a certain small and constant value from the normals of the same month and hour . By this process the effects of the " Casual and Transitory changes " are in a very great degree eliminated , and a very close approximation is obtained to the systematic diurnal action of the sun upon the direction of the horizontal magnet , apart from the effects of disturbances . The solar-diurnal variation thus obtained at Kew is compared with results similarly obtained at six other stations , viz. three stations in the interior of the two great northern continents , one equatorial station , and two stations in the middle latitudes of the southern hemisphere-thus generalizing upon a very extensive scale the action of the sun in producing the phenomena under notice . The fifth section is occupied by a similar generalization of the facts which have placed in evidence the existence of a semiannual inequality 624 [ June 18 , in the solar-diurnal variation , having its epochs coincident , or very nearly so , with the sun 's passage of the equator , and dependent consequently on the earth 's position in its orbit . The sun 's action in producing this semiannual inequality is shown to be characteristically different from that which is manifested in the solar-diurnal variation itself , pointing apparently to a difference in the mode of the sun 's action in the two cases . The sixth section contains a tabular view of the " ' Lunar-diurnal Variation " at Kew , in each of the five years during which the photographic record has been maintained there ; this is followed by a comparison with similar results at other stations on the globe , and a statement of the principal points of agreement or of difference which are shown thereby .

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3701662

Results of the Magnetic Observations at the Kew Observatory, from 1858 to 1862 Inclusive. --No. II. [Abstract]

625

630

Proceedings of the Royal Society of London

Edward Sabine

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112323

http://www.jstor.org/stable/112323

Meteorology

Tables

Meteorology

III . " Results of the Magnetic Observations at the Kew Observatory , from 1858 to 1862 inclusive."--No . II . By MajorGeneral EDWARD SABINE , P.R.S. Received June 18 , 1863 . ( Abstract . ) This paper is a continuation of the preceding one . It consists of two sections , the seventh and eighth . In the seventh section the author discusses the secular change and annual variation of the declination ; and in the eighth section , the annual variation or semiannual inequality of the inclination and of the horizontal and total magnetic force . Seventh Section.-The positions of the horizontal magnet at 24 equidistant epochs in the day , tabulated from the photograms of the Kew declinometer , with the omission of the disturbed observations , as described in the former paper , are grouped in weekly means , forming 52 mean values , corresponding to the number of weeks in the year . A Table is given of these weekly values , comprehending , in five columns , the five years from January 1858 to December 1862 inclusive , and from these a sixth column is formed , representing the mean declination in each of the 52 weeks of a mean or typical year , corresponding in this instance to the year 1860 . The mean declination obtained from all the weekly results in the five years , and corresponding to its middle epoch July 1 , 1860 , is 21§ 39 ' 18"f1 ; and from a comparison of the mean declinations corresponding to July 1 in the 1863 . ] 625 columns which severally present the weekly values in the years from 1858 to 6182 inclusive , the mean value of the secular change corresponding to the period comprised in the Table is deduced . A proportional part of the secular change is then applied with its appropriate sign to each of the weekly values in the mean or typical year . These should all correspond with the mean declination of the whole Table ( viz. 21§ 39 ' 18 " -1 ) , or should exhibit only such small and unsystematic differences as might reasonably be ascribed to casual errors . The final column of the Table contains these differences , in which it is at once seen that they divide themselves into two distinct categories , distinguished by the sign in the semiannual period from March 21 to Sept. 21 , and by the + sign from Sept. 21 to March 21 . Hence the author infers the existence of a variation in the declination at Kew having an annual period , and consisting of a semiannual inequality with epochs coincident , or nearly so , with the sun 's passage of the equator the magnet being deflected towards the east when the sun is north , and towards the west when he is south of the equator . The amount of the semiannual inequality , as shown by the Table , averages 28"'95 in the weeks from March 21 to Sept. 21 , and 29"'9 in those from September to March . The whole amount of the annual variation at Kew is therefore 58"'85 . The result thus obtained from the observations at Kew is compared with the result of an investigation of the corresponding phenomena at Hobarton in the southern hemisphere , obtained from hourly observatious of the declination during five years , commencing in October 1843 , and terminating in September 1848 . The observations themselves are published in the 2nd and 3rd volumes of the Hobarton Observations , and are treated , for the purposes of this paper , precisely in the same way as those of the Kew Observatory , forming a table strictly analogous to the one , previously described , at Kew . The final column of the Hobarton Table exhibits the differences , in each of the 52 weeks of the typical year , from the mean declination derived from the whole of the observations in the five years . The + and signs in this column attest in as striking a manner as do those at Kew , the existence at Hobarton of a semiannual inequality of which the epochs coincide , or very nearly so , with the sun 's passage of the equator : the direction of the deflection is the same as at Kew , viz. , of the north end of the magnet 626 [ June 18 , 1863 . ] towards the east when the sun is north of the equator , and to the west when he is south of the equator . The amount of the deflection in the first-named semiannual period is , on the average , 19"'1 in each week ; and in the opposite semiannual period 19 " ; making together an annual variation of 38 " ' 1 . The author then refers to the result of a similar investigation of the phenomena at St. Helena in the equatorial zone , the particulars of which have been already published in the 2nd volume of the St. Helena Observations . The result , derived from eight years of observation , of which five years were hourly , evidences at that station also the existence of a semiannual inequality with epochs coinciding , or nearly so , with the equinoxes the deflections being also in the same directions as those at Kew and Hobarton , viz. , to the east when the sun is north , and to the west when he is south , of the equator . The amount of the annual variation thus produced is less at St. Helena than at either Kew or Iobarton the semiannual difference being about 7 ' ? , and the annual variation 14 " . The author remarks that the difference in the amount of deflection at the three stations may , in part at least , be occasioned by the difference in amount of the antagonistic force of the earth 's magnetism , tending to retain the magnet in its mean position in opposition to all disturbing causes . The antagonistic force , viz. the horizontal component of the earth 's magnetic force , is approximately 5'6 ( in British units ) at St. Helena , 4*5 at Hobarton , and 3'8 at Kew . In a note appended subsequently to the delivery of this paper , viz. on June 19 , 1863 , the author refers to a similar investigation of the phenomena at the Cape of Good Hope , published in 1851 , in the 1st volume of the magnetical observations at that station . The volume contains the fortnightly means of the declination from July 1842 to July 1846 , corrected for secular change , and collected in Table III . , page v , of that volume . The differences of the declination in each fortnight , so corrected , from the mean declination of the whole period , are shown in its final column . The mean of the thirteen fortnights ( in the four years ) between March 26 and Sept. 23 , is 0'4 more easterly , and of the thirteen fortnights between September 24 and March 25 , 0'4 more westerly than the mean value-showing an annual variation of 0'8 ( or 48 " ) , or a semiannual inequality averaging 24 " to the east in the thirteen fortnights from March 26 627 to Sept. 23 , and 24 " to the west in the thirteen fortnights from Sept. 24 to March 25 . This is in accordance with the conclusions at all the other stations at which the phenomena have been subjected to a suitable investigation . The antagonistic horizontal component of the earth 's magnetism is approximately 4'5 . Eighth Section . In the eighth section the author examines the evidence which the monthly determinations of the dip and of the horizontal component of the magnetic force at Kew afford of the existence of a semiannual inequality in the absolute values of the dip and of the total magnetic force . The results of the monthly determinations from April 1857 to March 1863 are exhibited in two Tables , one appropriated to the dip , and the other to the horizontal force . The whole series of the determinations of the horizontal force were made with the same unifilar magnetometer and the same collimator magnet throughout , and also by the same observer , Mr. Chambers , one of the assistants at the Kew Observatory . In the monthly determinations of the dip from April 1857 to September 1860 , twelve different circles , and their twenty-four needles were occasionally employed , the mean of all the observations in each month being taken as the mean result in that month . There were also several observers in this part of the series , chiefly four . In the months from October 1860 to March 1863 , one circle with its two needles were the sole instruments , and Mr. Chambers the sole observer . The probable error of a single monthly determination of the dip in the first part of the series , when several instruments and several observers were employed , is stated to be + 01"69 ; and in the second part of the series , obtained by a single circle and the same observer throughout , the probable error is + 0 ' 75 ; whence it is inferred that the greater number of partial results which contributed to produce the monthly mean in the earlier period more than counterbalanced the diversities which might have been occasioned by the peculiarities of the different observers and of the different instruments . The probable error of a single monthly determination of the dip , after the application of the corrections for secular change and annual variation , is stated to be + 0'.71 , and of a single monthly determination of the horizontal force derived from the 72 monthly determinations + '0024 . The results of the monthly determinations at Kew , as bearing 628 upon the question of annual variation , may be briefly stated as follows:-1st . The dip is subject to an annual variation , which , on the average of the six years , amounts to 1'35 ; consisting of a semiannual inequality with epochs coinciding , or very nearly so , with the equinoxes ; the mean dip being on the average 0'"65 lower than its annual mean value in the six months from April to September , and 0'`7 higher than its annual mean value in the six months from October to March . 2nd . That the horizontal force is subject to a semiannual inequality having the same epochs-being on the average *0013 higher than its annual mean in each of the six months from April to September , and '0013 lower than its annual mean in each of the months from October to March . 3rd . That , combining the results of the dip and horizontal force , the total terrestrial magnetic force is expressed in British units by 10'3002 as its mean value in the months from April to September , and by 10'30347 in the months from October to March , -there being thus a difference of 00327 , by which the intensity of the magnetic force of the earth is greater in the months when the sun is south of the equator than in the months when he is north of the equator . This conclusion is compared with the results obtained in a corresponding manner from the published observations of the Hobarton Observatory , viz. , with the monthly determinations of the horizontal force in the five years from January 1846 to December 1850 inclusive , and with those of the dip in the ten years from January 1841 to December 1850 inclusive . From these data the conclusions are drawn , 1st , that at Hobarton the dip is subject to an annual variation amounting to 1'18 , consisting of a semiannual inequality with epochs coinciding or nearly so with the equinoxes the ( south ) dip being on the average 0'"59 less in the months from April to September , and 0'"59 greater in the months from October to March than the mean annual value ; and 2nd , that the horizontal force is subject to a similar semiannual inequality , being '0007 less than its mean value in the months from April to September , and '0005 greater in the months from October to March ; and combining these two results , that the total force at Hobarton is expressed in British units by 13-56882 in the months from October to March , and by 13'55195 in the months from April to September : the difference , ? 01687 , expresses the measure of the greater intensity of the earth 's magnetic force when the sun is south than when he is north of the equator . The author concludes this section of his investigations by drawing the attention of the Royal Society to this concurrent evidence , from the observations of three observatories situated in parts of the globe so distant from each other , of a semiannual inequality having such strong features of resemblance in both hemispheres , and remarks that it seems difficult to assign such effects to any other than to a cosmical cause . The " inequalities " may in themselves seem to be small ; but judged of scientifically , i. e. in the proportions they bear to their respective probable errors , they are large .

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Experiments, Made at Watford, on the Vibrations Occasioned by Railway Trains Passing through a Tunnel. [Abstract]

630

633

Proceedings of the Royal Society of London

James South

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6.0.4

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http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112324

http://www.jstor.org/stable/112324

Biography

Astronomy

Biography

IV . " Experiments , made at Watford , on the Vibrations occasioned by Railway Trains passing through a Tunnel . " By Sir JAMES SOUTH , LL. D. , F.R.S. , Member of the Board of Visitors of the Royal Observatory , Greenwich . Received June 17 , 1863 . ( Abstract . ) These experiments were made in consequence of an attempt in 1846 to run a line of railway through Greenwich Park , in what seemed to several competent judges a dangerous proximity to the Royal Observatory . It was abandoned , but ( as Sir James South was informed ) only for a time ; and he thought it right to make some examination of the probable effects of such a vicinity , especially as to the power of a tunnel in deadening the vibrations . The Watford tunnel was chosen as the observing station , being , on the high authority of the late Mr. Warburton , in ground very analogous to that on which the Royal Observatory stands ; and every facility for making observations was afforded by the late Earl of Essex , through whose park and preserves this tunnel passes . As the chief inconvenience to be feared from the proposed railway was the disturbance of the observations by reflexion in mercury , it seemed best to take a series of these under circumstances as nearly as possible resembling those which might be expected at Greenwich . An Observatory was therefore erected , in which a large and powerful [ June 18 , 630 transit-instrument was mounted , with all the attention to stability that could be given in a first-class Observatory ; and it had sufficient azimuthal motion to enable the observer to follow the Pole-star in its whole course ; so that night or day ( if clear ) , he could have the reflected image of the star in the mercurial vessel , ready to testify against the tremors caused by any train . The distance of the vessel from the nearest part of the tunnel was 302 yards , that proposed for Greenwich belng 286 yards . The length of the tunnel is 1812 yards ; its southern or London end is 643 yards from where the mercury was placed , its northern or Tring end 1281 yards ; and about 64 feet of chalk and gravel lie above the brickwork of its crown . The author 's preparations were not complete till December 1846 , and then a continuance of cloudy weather interfered with observation till January the 11th , 1847 , when and on the following nights he obtained results so decisive that he felt it his duty to communicate them at once to the then First Lord of the Admiralty , the late Lord Auckland , who was so satisfied with them , that in a letter to Sir James , dated " Admiralty , Jan. 26 , 1847 , " he recorded the impression they had made on his mind in the following words:-- " They would be quite conclusive if the question of carrying a tunnel through Greenwich Park were again to be agitated . " Sir James , however , continued the work to the end of March . With the ordinary disturbance to which an Observatory is liable ( as wind , carriages , or persons moving near it ) , the reflected image of a star breaks up into a line of stars , perpendicular to the longest side of the mercury-vessel . With increased agitation , another line of stars perpendicular to the first appears , making a cross . With still more the cross becomes a series of parallel lines of stars ; still more makes the images oscillate ; and at last all becomes a confused mass of nebulous light . The first of these ( the line ) is not injurious to onec lass of observations ; but the others are , and therefore the second ( the cross ) was taken as a measure of the beginning and end of injurious disturbance . Signal shots were fired when a train passed the southern entrance of the tunnel , and a shaft 1162 yards from it . Hence the train 's velocity was obtained , and thence its position at any given time . Upwards of 230 observations are given in detail , and their most important results are shown in a Table , which contains the date , the 22 1863 . ] 631 distances at which the cross of stars begins and ceases to be visible , those at which the series of parallel lines is seen , the velocity in miles per hour , the weight of each engine , and also the length and weight of each train ( when it could be identified ) . This Table proves that in all cases but one ( which in fact is scarcely an exception ) there is sufficient vibration to excite the cross at 670 yards , and that in 24 per cent. of the number it is seen beyond 1000 , its maximum being 1176 . At the southern end such distances reach far beyond the tunnel , while at the north they fall within it . From comparing them in the two cases , the author infers that the train 's agitation extends laterally as far when it is in the tunnel as when in the open cutting . The amount of disturbance does not depend solely on the velocity and weight of the train , but also on other circumstances , of which prolonged action and length of train are the chief . In one instance , with only a velocity of 11'4 miles , the cross was seen at 1110 yards-a proof that no regulation of the speed in passing an Observatory at a distance of 300 or 400 yards would be of any avail . The system of parallel lines is only seen between lines making angles of 450 with the perpendicular to the rails , that is , at distances under 427 yards ; it scarcely ever is produced unless the cross be visible beyond 1000 yards . These forms are also produced by the reports of cannon of twelve ounces calibre , at distances from 300 to 3000 yards ; in the last case there is but a faint trace of the cross . In all , the appearance is momentary , not lasting in any case more than a second and a half . They are not produced by the roar of a two-pound rocket fired 82 feet from the mercury , though very loud . When the cannon were fired in the tunnel , where the perpendicular meets it , two sets of tremors were seen-one , he believes , propagated through the ground , the other through the air about a second later , the sound escaping probably through the shafts . Attempts were made to substantiate or refute this hypothesis ; but the difficulties of rapidly shifting and unshifting the coverings prepared for the purpose were such as to compel him to relinquish them . These observations were reduced in 184 7 ; but conceiving all danger to the Royal Observatory was past , the author did not think it necessary then to proceed with them . As , however , no Observatory 63 can now be considered secure from railway injury , he wishes to make them public , in hopes that they may be useful , not only to practical astronomy , but to some other departments of science .

112325

3701662

Preliminary Notice of an Examination of Rubia munjista, the East-Indian Madder, or Munjeet of Commerce

633

639

Proceedings of the Royal Society of London

John Stenhouse

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0136

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112325

10.1098/rspl.1862.0136

http://www.jstor.org/stable/112325

Chemistry 2

Biography

Chemistry

V. " Preliminary Notice of an Examination of Hubia munjista , the East-Indian Madder , or Munjeet of Commerce . " By JOHN STEN-IOUSE , LL. D. , F.R.S. Received June 18 , 1863 . It is rather remarkable that while few vegetable substances have been so frequently and carefully examined by some of the most eminent chemists than the root of the Rubia tinctorum , or ordinary madder , the Rubia munjista , or munjeet , which is so extensivel ) cultivated in India and employed as a dye-stuff , has been , comparatively speaking , very much overlooked , never having been subjected , apparently , to anything but a very cursory examination . Professor Rung , at the close of his very elaborate memoir upon madder , published in 1835 , details a few experiments which he made upon the tinctorial power of munjeet , the constituents of which he regarded as very similar to those of ordinary madder . Professor Rung stated that munjeet contains twice as much available colouring matter as the best Avignon madder . This result was so unexpected that the Prussian Society for the Encouragement of Manufactures , to whom Professor Runge 's memoir was originally addressed , referred the matter to three eminent German dyers , Messrs. Dannenberger , B6hm , and Nobiling . These gentlemen reported , as the result of numerous carefully conducted experiments , that , so far from munjeet being richer in colouring matter than ordinary madder , it contained only half the quantity . This conclusion has been abundantly confirmed by the experience of my friend Mr. John Thom , of Birkacre , near Chorley , one of the most skilful of the Lancashire printers . From some incidental notices of munjeet in Persoz and similar writers , and a few experiments which I made some years ago , I was led to suspect that the colouring matters in -munjeet , though similar , are by no means identical with those of ordinary madder , and that probably the alizarine or purpurine of madder would be found to be replaced by some corresponding colouring principle . This hypothesis I have found to be essentially correct ; for the colouring matter of munjeet , instead of consisting of a mixture of alizarine and purpurine , contains 1863 . ] 633 no alizarine at all , but purpurine and a beautiful orange colouring matter crystallizing in golden scales , to which I purpose giving the name of " munjistine . " Munjistine exists in munjeet in considerable quantity , and can therefore be easily obtained . The colouring matter of munjeet may be extracted in various ways ; that which I have found most suitable is as follows:-each pound of munjeet in fine powder is boiled for four or five hours with two pounds of sulphate of alumina and about sixteen of water . The whole of the colouring matter is not extracted by a single treatment with sulphate of alumina ; the operation must be repeated therefore two or three times . The red liquid thus obtained is strained through cloth filters while still very hot , and the clear liquor acidulated with hydrochloric acid . It soon begins to deposit a bright red precipitate , the quantity of which increases on standing , which it should be allowed to do for about twelve hours . This precipitate is collected on cloth filters and washed with cold water till the greater portion of the acid is removed . It is then dried , reduced to fine powder , and digested in a suitable extracting apparatus with boiling bisulphide of carbon , which dissolves out the crystallizable colouring principles of the munjeet , and leaves a considerable quantity of dark-coloured resinous matter . The excess of the bisulphide of carbon having been removed by distillation , the bright red extract , consisting chiefly of a mixture of munjistine and purpurine , is treated repeatedly with moderate quantities of boiling water and filtered . The munjistine dissolves , forming a clear yellow liquid , while almost the whole of the purpurine remains on the filter . When this solution is acidulated with hydrochloric or sulphuric acid , the munjistine precipitates in large yellow flocks . These are collected on a filter and washed slightly with cold water . The precipitate is then dried by pressure , and dissolved in boiling spirit of wine slightly acidulated with hydrochloric acid to remove any adhering alumina . As the munjistine does not subside from cold alcoholic solutions , even when they are largely diluted with water , about three-fourths of the spirit are drawn off by distillation , when the munjistine is deposited in large yellow scales . By two or three crystallizations out of spirit in the way just described the munjistine is rendered perfectly pure . I have likewise succeeded in extracting munjistine directly from munjeet by boiling it with water , filtering the solution , which has a dark brownish-red colour , and then acidulating with hydrochloric [ June 18 , 634 acid . The precipitate which falls is collected on a filter , washed , dried , and treated with boiling spirit of wine , which leaves a large quantity of pectine undissolved . The munjistine which dissolves in the alcohol is obtained in a pure state by repeated crystallizations in the way already indicated . The first process which I have described is , however , by far the best . The colouring matter of munjeet can likewise be extracted with boiling solutions of alum ; but I find sulphate of alumina greatly preferable , as the alum , by its tendency to crystallize , very much impedes the filtration of the liquids . I likewise attempted to employ Professor E. Kopp 's process with sulphurous acid , which gives such excellent results with ordinary madder , but I found it wholly inapplicable to munjeet . Munjistine , prepared by the processes described , when crystallized out of alcohol , forms golden-yellow plates of great brilliancy . It is but moderately soluble in cold , but dissolves pretty readily in boiling water , forming a bright yellow solution , from which it is deposited in flocks when the liquid cools . Saturated solutions almost gelatinize . It dissolves to some extent in cold , but more readily in boiling spirit of wine , and is not precipitated by the addition of water . It dissolves in carbonate of soda with a bright red colour . In ammonia it forms a red solution with a slight tinge of brown : caustic soda produces with it a rich crimson colour . Both its aqueous and alcoholic solutions , when boiled with alumina , form beautiful flakes of a bright orange colour , almost the whole of the munjistine being withdrawn from solution . These flakes are soluble in a large excess of caustic soda , with a fine crimson colour . Munjistine dyes cloth mordanted with alumina a bright orange . With iron mordant it yields a brownish-purple colour , and with Turkey-red mordant a pleasing deep orange . These colours are moderately permanent , and bear the application of bran and soap tolerably well . The munjistine sensibly modifies the colours produced by munjeet , giving the reds a shade of scarlet , as has been long observed . Commercial nitric acid dissolves munjistine with a yellow colour , but does not appear to decompose it even on boiling . Fuming nitric acid ( 1'5 ) dissolves munjistine in the cold , and on application of heat decomposes it , no oxalic acid being produced . It readily dissolves in cold sulphuric acid with a bright orange colour ; and the solution may be heated nearly to boiling without blackening or 635 1863 . ] giving off sulphurous acid ; it is reprecipitated by water in yellow flocks apparently unaltered . When bromine water is added to a strong aqueous solution of munjistine , a pale-coloured flocculent precipitate is immediately produced ; this , when collected on a filter , washed and dissolved in hot spirit , furnishes minute tufts of crystals , evidently a substitution product . I may remark , in passing , that when alizarine is treated with bromine water in a similar way , it also forms a substitution product crystallizing in needles . I am at present engaged in the examination of both these compounds . When munjistine is strongly heated on platinum foil , it readily inflames and leaves no residue ; when it is carefully heated in a tube , it fuses , and crystallizes again on cooling . It sublimes more readily than either purpurine or alizarine , forming golden scales which consist apparently of unaltered munjistine , as they give the characteristic rich crimson coloration with caustic alkalies . Baryta water produces a yellow precipitate with munjistine . Acetate of lead throws down a bright crimson precipitate , both in its aqueous and alcoholic solutions . I expect , from this and the bromine substitution compound , very shortly to ascertain the atomic weight of this body ; in the mean time I submit the results of its ultimate analysis . I. '314 grm. of munjistine yielded *732 grm. of carbonic acid and '106 grm. of water . II . *228 grm. munjistine yielded *535 grm. carbonic acid and ? 0765 grm. water. . IH . C per cent. 63'6 64-0 H , , 3-77 3-73 O , , 32-63 32-27 100-00 100'00 The munjistine operated upon in each case was prepared at different times ; moreover No. 1 was burnt with oxide of copper , No. 2 with chromate of lead . Munjistine in some of its properties bears considerable resemblance to Runge 's madder-orange , the " rubiacine " of Dr. Schunck : it is , however , essentially different from rubiacine , both in several of its properties , such as its solubility in water and alcohol , &c. , and in the amount of its carbon-rubiacine , according to Dr. Schunck 's analysis , 636 containing 67'01 per cent. of that element , while munjistine contains only 64 . The spectra afforded by solutions of the two substances , as may be seen from the following extract from a letter received from Professor Stokes , are decidedly different . " The two substances are perfectly distinguished by the very different colour of their solution in carbonate of soda , when a small quantity only of substance is used . The solution of munjistine is red inclining to pinkish orange , that of rubiacine a claret-red . The tints are totally different , and indicate a different mode of absorption . Both present a single minimum in the spectrum ; but while that of rubiacine extends from about D to F , that of munjistine extends from a good way beyond D to some way beyond F. The beginning and end of the band in each case is not very definite , and varies of course with the strength of the solution ; but by comparing the substances with different strengths of solution , there can be no doubt of the radical difference in the position of the band of absorption . In this way it is easy to convince oneself that the difference of colour is not to be explained by the possible admixture of some small imn purity present in one or other specimen . With caustic potash munjistine gives as nearly as possible the same colour as rubiacine , agreeing with the colour of rubiacine in carbonate of soda . 'There appears to be a slight difference in the spectrum of the munjistine and rubiacine solutions , but not enough to rely on ; so that the substances are not to be distinguished by their solutions in caustic alkalies . " A second perfectly valid distinction is , however , afforded by the different colour of the fluorescent light of the ethereal solutions . The solid substances themselves and their ethereal solutions are fluorescent to a considerable degree ; but the tint of the fluorescent light of the ethereal solution of rubiacine is orange-yellow , while that of the ethereal solution of munjistine is yellow inclining to green . The examination in a pure spectrum shows that the difference is not due to the admixture of a small impurity , itself yielding a fluorescent solution ; but the tints may be readily contrasted by daylight , almost without apparatus , by the method I have described in a paper 'On the existence of a second crystallizable fluorescent substance in the bark of the horse-chestnut ' ( Quart . Journal Chem. Soc. vol. ii . p. 20 ) . I consider either of the two points of difference I 1863 . ] 637 have mentioned sufficient by itself to establish the non-identity of munjistine and rubiacine " " . The purpurine which I succeeded in extracting from munjeet and in purifying from munjistine in the way already described , formed beautiful dark crimson needles , having all the usual properties of that substance . When examined by Professor Stokes , they gave the very characteristic spectra of purpurine . *3285 grm. of purpurine gave '8005 grm. carbonic acid and ? 1050 grm. water . Analysis . Theory . Found . Debus ( mean ) . C ... ... . . 6667 66-46 66-40 ... ... . . 3-70 3-55 3'86 ... ... . . 2963 29'99 29-74 100-00 100-00 100-00 From the results above detailed there can therefore be no doubt that the colouring matter of munjeet , as already stated , consists of purpurine and munjistine . I cannot conclude this preliminary notice without acknowledging the essential services I have received from Professor Stokes , who kindly submitted the different products obtained by me to optical examination . Though it is plain that a substance optically pure , that is , containing no impurities affecting the spectrum , may still be far from being chemically so , yet the spectroscope is extremely useful in indicating admixtures of kindred substances of very similar properties , having a great affinity for each other , and therefore not readily separable . I feel certain therefore that if Professor Stokes would draw up a short treatise embodying his extensive and accurate observations on the spectra of the colouring matters and similar substances , he would confer a great boon on the cultivators of organic chemistry . PosTscRIPT.-Received July 18 , 1863 . Since the preceding paper was communicated to the Royal Society I have been enabled to examine the action of nitric acid on munjis* I may mention that the rubiacine which Professor Stokes examined was prepared by Dr. Schunck himself . [ June 18 , 638 time much more fully . When munjistine is digested with moderately strong nitric acid , as already stated , copious fumes are given off , the munjistine gradually dissolving and forming a colourless solution . When this is evaporated to dryness on the water-bath , a white crystalline mass is obtained , consisting almost entirely of phthalic acid contaminated with a small quantity only of oxalic acid . The oxalic acid may be easily removed by washing the mass with a little cold water and then pressing between folds of bibulous paper , or by neutralizing the mixture of the two acids with lime and then treating with boiling water , which dissolves the phthalate of lime . The acid freed from oxalic acid by either of these methods presents all the usual reactions of phthalic acid . One of the most convenient ways of purifying it consists in subliming it repeatedly in a Mohr 's apparatus , when the anhydrous acid is obtained in beautifully white iridescent four-sided prisms , frequently several inches in length . ? 3745 grin . of the crystals of the anhydride , burnt with chromate of lead , gave *891 grm. carbonic acid and *095 grm. of water . Theory . Expt. Marignac . Laurent . C1 ... ..96 64-86 64-89 64-88 64-70 11 ... 4 2-70 2-81 2-71 2-38 06 ... .48 32-44 32-30 32-41 32-92 From this result it is evident that the acid chiefly produced by the action of nitric acid upon munjistine is phthalic acid , which , as is well known , may also be procured from alizarine and purpurine . This reaction , therefore , indicates a very close relationship between these three substances , the only true colouring principles of madder with which we are at present acquainted .

112326

3701662

Notes of Researches on the Poly-Ammonias.--No. XXIV. On Isomeric Diamines

639

645

Proceedings of the Royal Society of London

A. W. Hofmann

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0137

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112326

10.1098/rspl.1862.0137

http://www.jstor.org/stable/112326

Chemistry 2

Astronomy

Chemistry

VI . " Notes of Researches on the Poly-Ammonias.-No . XXIV . On Isomeric Diainines . " ByA . W. HOrMANN , LL. D. , F.R.S. Received May 26 , 1863 . In a former paper* I have described phenylene-diamine , an aromatic diamine which is formed by the action of powerful reducing agents upon dinitrobenzol . Phenylene-diamine , the last product of this reaction , is preceded by the formation of an intermediate compound , nitraniline , a substance discovered many years ago by Dr. Muspratt and myself , C6 116 C H4NO 64 NO2 C6 NHi2 NO,2 N , NH2 , . Benzol . Dinitrobenzol . Nitraniline . Phenylene-diamine . Nitraniline , as might have been expected , was found to be readily convertible into phenylene-diamine . By the researches of M. Arppet , chemists have become acquainted with a second nitraniline , which is obtained by the action of fuming nitric acid upon phenyl-pyrotartramide and subsequent treatment of the nitro-compound with potassa . This substance , which , as I afterwards found , may be more readily prepared by a similar treatment of other less difficultly obtainable phenylamides , such as phenylacetamide or phenyl-succinamide , is isomeric with ordinary nitraniline , but differs from the latter compound both in its physical and chemical properties , so as to leave no doubt regarding the individuality of the two compounds , which have accordingly been distinguished as alpha-nitraniline and beta-nitraniline . This singular isomerism , which has been traced also in other phenyl-derivatives , remains unexplainedl . Whilst engaged with the examination of phenylenedic.time , the idea naturally suggested itself , to ascertain whether beta-nitraniline , when submitted to reducing agents , would yield a body isomeric but differing from the phenylene-diamine obtained from dinitrobenzol and alpha-nitraniline . Beta-nitraniline is readily reduced by a mixture of iron and acetic * Chem. Soc. AMem . vol. iii . p. 112 . t Chem. Soc. Journ. vol. viii . p. 175 . + Among the various attempts I have made to decipher this isomerism , I may mention the treatment of the two nitranilines with the iodides of methyl and ethyl . But these substances are not acted upon by the reagents in question , and I take this opportunity of correcting an error which has crept into my paper on the molecular constitution of the volatile organic bases ( Phil. Trans. 1850 , vol. i. p. 93 ) . In this paper I state that the action of iodide of ethyl on nitraniline gives rise to the formation of hydriodate of ethyl-nitraniline . This statement is based upon a single platinum determination . The platinum-salt of nitraniline contains 28'66 per cent. of platinum , that of ethyl-nitraniline 26-53 per cent. Analysis had furnished me 26'23 per cent. I have since satisfied myself that the salt was the imperfectly purified platinum-salt of nitraniline . 640 [ June 18 , acid . The basic compound which distils over has the same compo . sition as phenylene-diamine , viz. C6 H8 N2 , and presents in its properties many analogies with this substance , but it is far from being identical with it . The two diatomic bases obviously are related to each other in the same manner as the two nitranilines from which they are derived , and I propose therefore to distinguish them as alpha-phenylene-diamine and beta-phenylene-diamine . Beta-phenylene-diamine differs from alpha-phenylene-diamine by its superior crystallizing power : whilst the latter for days and often for weeks remains liquid , the former immediately , when separated from one of its salts by an alkali , solidifies into a beautifully crystalline mass . The fusing-point of alpha-phenylene-diamine is 63 ? ( corr . ) , that of betaphenylene-diamine is 140 ? ( corr . ) ; the former boils at 287 ? ( corr . ) , the latter at 267 ? ( corr . ) . Beta-phenylene-diamine is remarkable for the facility with which it sublimes even at temperatures below its boiling-point . The experiment succeeds particularly well in a current of hydrogen gas , when the base is obtained in splendid crystalline plates resembling pyrogallic acid . The salts of beta-phenylene-diamine , although they are more soluble than the corresponding alpha-phenylene-diamine salts , are distinguished by the same superior crystallizing power . They are all remarkable for the facility with which they yield beautiful and mostly well-formed crystals . I have examined only two of these salts somewhat more minutely . Hydrochlorate of Beta-phenylene-diamine.-This salt crystallizes in large prisms , which are at present in the hands of M. Quintino Sella . Extremely soluble in water , difficultly soluble in hydrochloric acid , it contains C H8 N2 , 2I-C1 . Hydrobromate of beta-phenylene-diamine resembles in every respect the hydrochlorate . The crystals , which were found to have the formula C6 II8 N2 , 2 IBr , are apt to assume a reddish tint when left in contact with the air . Platinum-salt.-Light-yellow plates extremely soluble in water and readily decomposed by heat . Composition : C6 8 N2 , , 2 HC1 , 2 Pt C1 . s1863 . ] 641 The sulphate and nitrate are easily crystallizable salts , somewhat less soluble in water than the hydrochlorate . Beta-phenylene-diamine and its salts are remarkable for the facility with which they are converted into violetand blue-coloured compounds under the influence of oxidizing agents such as chlorine , bromine , chromic acid , ferric and platinic chloride , &c. Both alphaand beta-phenylenediamine are readily attacked by the iodides of the alcohol radicals ; and a means was thus afforded of ascertaining whether both substances exhibit the same degree of substitution . Since only the last products of substitution presented any interest , I have submitted the two bases to methylation . This experiment showed that both alphaand beta-phenylene-diamine are capable of absorbing six equivalents of methyl to produce ammonium compounds of perfect substitution , and that both bases must therefore be represented by the formula C6 Hl4 -I2 > N2 . In the case of both bases , alternate treatment with iodide of methyl and oxide of silver or distillation with soda , thrice repeated , leads to the formation of a well-crystallized iodide of the formula C H~ NI =-(Co 11 ) N 0121222 =2 L(C I'i ) }N ] IJ2 Whether prepared from alphaor from beta-phenylene-diamine , this salt crystallizes in plates extremely soluble in water , less so in alcohol . I have found no other difference except that the betaphenylene-compound is more soluble than the derivative of the alpha-base . Whilst studying the methylated derivatives of the two bases , I have , of course , repeatedly obtained the lower , still volatile bases , which on this occasion were submitted to a few experiments . The compound C 1H6 N2 ( C6 Hl ) } N , procured from beta-phenylene-diamine , when submitted to the action of iodide of methyl , was found to produce , in the first place , a rather difficultly soluble iodide , Cn0 Hin N2 I ( C I-I)4 N , CH3 I2 ( C I1)4J 2 ' 3 before it was converted into the final product C( H2 N I= ( C H4 ) N2 , 2CH I ( C61 4)l N2 I 2112,21 ( c 113)4 N,11 CL( 113 ) 6 ) The pentamethylated iodide , when treated with hydriodic acid instead of iodide of methyl , furnished the di-iodide of pentamethylphenylenediammonium , ( HI 114 ) ' C11 H20 N2 I2= [ ( C I , ) , H3 N2 12 The two phenylene-diamines are thus seen not only to be isomeric , but to have actually the same degree of substitution , as far as the latter may be rendered transparent by the action of iodide of methyl . Under these circumstances I was pleased to observe some additional phenomena which removed every doubt regarding their individuality . On mixing a solution of beta-phenylene-diamine in sulphuric acid with peroxide of manganese , the odour of kinone becomes at once perceptible , and on heating the mixture , kinone distils overthe residuary liquid containing the sulphates of manganese and ammonium , C , H,1 N+ 2H2 , S04 M+ Mn2 S0 , = 4 ( H4 N)2 SO , . Beta-phenyKinone . lene-diamine . The reaction proceeds with such ease that a few milligrammes of the diamine , when submitted to this treatment in the test-tube , yield a distinct crystalline sublimate of kinone , readily recognizable by its many salient properties . Alpha-phenylene-diamine , when similarly treated , evolves a faint odour of kinone , but does not yield crystals of this substance . The elegant and easy formation of kinone in this reaction presents some interest , inasmuch as the process appears to be of general application , and will probably lead to the preparation of the higher homologues of kinone . I have observed the formation of beta-phenylene-diamine in two additional reactions , which , in conclusion , I beg leave to mention . In the hopes of obtaining the triamine of the phenyl-series ( C HT , ) " ' " C6 It N=H N , It3 1863 . ] 643 I submitted dinitrophenylamine , [ C6 H3 ( NO2)2 ] C6 H1N304O H SN , HJ to distillation with iron and acetic acid , but , instead of the compound which I endeavoured to procure , I invariably obtained beta-phenylenediamine and ammonia , CH 9N3 + H2 = C6 H , N , + HN . Phenylic triaBeta-phenylenemine . diamnine . Again , dinitrazobenzol , C , H , N , O=C N(NO , , when submitted to the action of powerful reducing agents , yields likewise beta-phenylene-diamine CH12 1 N4 04 , +8H2=4H20+2C,6 HN2 . Dinitrazobenzol . Beta-phenylenediamine . I-ere also beta-phenylene-diamine is the final product of the , reaction , the formation of which is preceded by that of another base , the diphenine of Messrs. Gerhardt and Laurent . Diphenine , according to these chemists , is C12 H N , , a formula chiefly supported by the unequivocal presence of C12 in the molecule of azobenzol , C , 1 HI N2 , whence it derives . The facility , however , with which diphenine under the influence of nascent hydrogen , by treatment with sulphuric acid and zinc , for instance , is converted into beta-phenylene-diamine renders it probable that the molecule of diphenine is C H116 N , when the two bases become related to each other as kinone and hydrokinone , Kinone ... ... C6 , 02 Diphenine ... ... ... . N2 H-Iydrokinone. . CG HI 02 Beta-phenylene-diamine C6 HI N2 . I have hitherto vainly tried to transform kinone into diphenine or beta-phenylene-diamine ; but it deserves to be noticed that M. Woskresensky , by treating kinone with ammonia , has obtained a green * Woskresensky , Journ. Pract . Chem. vol. xxxiv . p. 251 . 644 [ June 18 , beautifully crystalline mass , kinonamide , C6 H5 NO , which stands midway between kinone and diphenine , C6 H4 02+H , N=C , H5 NO+H2 O. Kinone . Kinonamide . Another similar step of transformation would lead to diphenine , C6 H5 NO+H3 N=C6 I , N2+H2 O. Kinonamide . Diphenine . The preparation of azobenzol in large quantity , its transformation into dinitrazobenzol , and , lastly , the conversion by means of sulphide of potassium of the nitro-compound into diphenine , present so little difficulty , that treatment of diphenine with nascent hydrogen affords the easiest and simplest means of procuring beta-phenylene-diamine in appreciable quantity .

112327

3701662

Contributions towards the History of the Colouring Matters Derived from Aniline

645

647

Proceedings of the Royal Society of London

A. W. Hofmann

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0138

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112327

10.1098/rspl.1862.0138

http://www.jstor.org/stable/112327

Chemistry 2

Biography

Chemistry

VII . " Contributions towards the History of the Colouring Matters derived from Aniline . " By A. W. HOFMANN , LL. D. , F.R.S. Received June 2 , 1863 . In a short paper recently submitted to the Royal Society , I pointed out the existence of two aromatic diamines , both represented by the formula ( C , H4 ) " C , HN = H2 N , and closely resembling each other , but differing in some of their fundamental characters to such an extent that I did not hesitate to assert their individuality , and to distinguish them as alpha-phenylene-diamine and beta-phenylene-diamine . The existence of two closely allied bodies among the diatomic derivatives of the phenyl-series very naturally suggested the idea of searching for two similarly related monatomic bases of the same group , and accordingly I undertook during the last week a careful comparison of specimens of aniline prepared by different processes . This comparative study is still incomplete , but I beg leave to record even now an observation which appears to merit the attention of chemists . I have , in the first place , examined aniline obtained by distillation of isatin ( indigo ) with hydrate of potassium . The base prepared in this manner boils at 182 ? , and possesses the general characters attributed to aniline . But neither by treatment with mercuric or stannic chloride nor with arsenic acid is this substance converted into aniline-red . Aniline derived from benzol was next submitted to examination . The benzol employed for the preparation of the base was partly obtained by the distillation of benzoic acid with lime , partly by the fractional distillation of coal-tar naphtha , and the ultimate solidification of the product , boiling between 80 ? and 83 ? . Both varieties of benzol were treated with fuming nitric acid , and the nitro-compound thus obtained converted into aniline by means of iron and acetic acid . The base prepared from benzoic benzol boils at 182 ? . Like indigo-derived aniline , it refuses to yield the red colour by treatment with the agents previously mentioned . Aniline obtained from coal-tar benzol , as might have been expected , likewise boils at 182 ? , and neither mercuric nor stannic chloride nor arsenic acid converts this substance into aniline-red . When I communicated these observations to my friend Mr. E. C. Nicholson , I found that in this case , as in so many others , practice is far in advance of theory . The facts which I have mentioned had been long known to this distinguished manufacturer , who in reply to my note transmitted to me a gallon of absolutely pure aniline boiling at 182 ? , prepared from coal-tar benzol , and perfectly incapable of yielding aniline-red . During the last few months I have had occasion to examine a great variety of commercial specimens of aniline , more especially samples which had been kindly supplied to me by Messrs. Simpson , Maule , and Nicholson , of London , and by Messrs. Renard Brothers and Franc , of Lyons . All these specimens furnished , by the ordinary processes , very notable quantities of aniline-red , but they also invariably boiled at a higher temperature , exhibiting in fact boiling-points varying between 182 ? and 220 ? . It is thus obvious that commercial aniline contains a base different from normal aniline , the cooperation of which is indispensable for the production of aniline-red . Is this base an isomeric variety of aniline , an aniline holding to the normal aniline a relation somewhat similar to that whicn obtains between alphaand beta-phenylene-diamine ? It is well known * Phil. Mag. S. 4 . vol. xiii . p. 415 ( June 1857 ) . that Mr. Church has separated from coal-tar naphtha a hydrocarbon isomeric with benzol , parabenzol , which boils at 97 ? '5 . This substance is readily converted into a nitro-compound , and ultimately into the corresponding base . Is it the base thus formed which gives rise to the formation of aniline-red ? Or is it not more probable that commercial aniline contains another base analogous or homologous with aniline which is involved in the generation of the red ? These are questions equally interesting for theory and practice , and the solution of which will probably throw considerable light upon the still enigmatical genesis of rosaniline .

112328

3701662

Contributions towards the History of the Colouring Matters Derived from Coal-Tar

647

648

Proceedings of the Royal Society of London

A. W. Hofmann

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0139

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112328

10.1098/rspl.1862.0139

http://www.jstor.org/stable/112328

Chemistry 2

Biography

Chemistry

VIII . " Contributions towards the History of the Colouring Matters derived from Coal-tar . " By A. W. HOFMANN , LL. D. , F.R.S. Received June 9 , 1863 . In a previous Note I have shown that the red colouring matter cannot be obtained from normal aniline by the action of the agents usually employed for the preparation of this colour on a large scale . This observation naturally induced me to seek for the constituent in the commercial aniline which gives rise to the formation of aniline-red . I have already remarked that the commercial product which is best suited for the manufacture of the red colour , boils at a temperature appreciably higher than the boiling-point of normal aniline . The idea presented itself of submitting this substance to a fractional distillation , or else of effecting a methodical separation of the hydrocarbons which constitute the starting-point for the manufacture of the bases ; but , as is well known , these processes are difficult and tedious , and there is little chance of success unless the operation be performed on a very large scale . In the hope of accelerating the inquiry , I examined the action of mercuric and stannic chlorides upon the homologues of aniline , of which I fortunately possessed some pure specimens . The contiguous term toluidine was the first to fix my attention . The presence of this base in commercial aniline could not be doubted , since the benzol employed in the manufacture of this substance almost invariably boils at temperatures between 80 ? and 100 ? , or even higher . Indeed Mr. Nicholson having convinced himself that pure aniline is not 2z2 647 available for the preparation of rosaniline , was at one time disposed to consider toluidine the true source of the so-called aniline-red . But toluidine the purity of which was established by combustion when submitted under the most varied circumstances to the action of the agents already mentioned , does not produce a trace of colouring matter . The subject , which thus appeared to become more and more obscure , was elucidated by a happy experiment . A mnixture of pure aniline and pure toluidine , when heated with mercuric chloride , stannic chloride , or with arsenic acid , instantaneously produced a magnificent red of most intense tinctorial power . This experiment appears to show that the red belongs to both the phenic and toluic series . I have not as yet pursued my researches further in the new field opelled by this experiment . In conclusion I may be allowed to state that by transforming into oxalate commercial aniline , and especially a specimen of aniline which was furnished to me by Mr. Nicholson as particularly well adapted for the preparation of the red , I have been enabled to obtain considerable quantities of toluidine in a state of perfect purity . Having thus at my disposal the necessary material , I hope soon to acquire further experimental data for the explanation of the formation of rosaniline .

112329

3701662

On the Measurement of the Chemical Brightness of Various Portions of the Sun's Disc

648

650

Proceedings of the Royal Society of London

Henry Enfield Roscoe

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0140

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112329

10.1098/rspl.1862.0140

http://www.jstor.org/stable/112329

Optics

Astronomy

Optics

IX . " On the Measurement of the Chemical Brightness of various portions of the Sun 's Disc . " By HENRY ENFIELD RoscoE , B.A. , F.R.S. Received June 12 , 1863 . The author has applied the method of measurement of the chemical action of sunlight , which Professor Bunsen and he described in a memoir presented to the Royal Society in November last* , to the measurement of the chemical brightness of various portions of the solar disc ; and although the observations which have as yet been made are only preliminary , yet he thinks that the results obtained are of sufficient interest to warrant his bringing them before the Society . Secchi has shownt that the calorific radiation of the centre of the sun 's disc is nearly double that from its borders , and that the equatorial regions are somewhat hotter than the polar , whilst observers have long noticed a great difference in luminosity between the centre and edge of the disc . For the purpose of obtaining a measurement of the relative chemical brightness of various portions of the solar disc , the image of the sun , of about 4 inches in diameter , obtained by a3 -inch refractor* , was allowed to fall into a camera placed on the instrument , upon a sheet of standard photographic paper prepared according to the method described in the above-mentioned research . The peculiar property of this standard paper is that it can always be prepared of one and the same degree of sensitiveness , and is perfectly homogeneous . The exposure lasted for from 30 to 120 seconds , the sun 's motion being carefully followed by a tangent-screw . After exposure , the shade of tint at several points on the picture was determined by comparison with a graduated photographic strip insolated in the pendulum-photometer , and the chemical intensities corresponding to these shades obtained by reference to the Table given in the memoir above cited . The following numbers give the chemical brightness , thus obtained , at various points on the sun 's disc on May 9th , 1863 . From these numbers it is seen that the intensity of ' the chemically active rays at the centre is from three to five times as great as that at the edge of the disc , the chemical rays thus showing a wider variation than the calorific rays exhibited as determined by Secchi . This is doubtless owing to the relatively greater absorption effected by the solar atmosphere on the more refrangible chemical rays . Chemical Brightness of Sun 's Disc on May 9 , 1863 . 1 . At centre of 2 . At 150 from edge of Sun 's 3 . At edge of Sun 's Dis Sun 's Disc . Disc . N. Pole . Equator . S. Pole . N. Pole . Equator . S. Pole . No. 1 . 100'0 38-8 48-4 58-1 18-7 30'2 28-2 No. 2 . 100-0 52-8 ... ... 56-6 305 ... ... 410 Hence it is likewise seen that on May 9th the chemical brightness of the south polar regions was considerably greater than that of the north polar regions , whilst about the equator the brightness was between that of the poles . Inr order to show that the sensitive paper , when exposed to ordinary sunlight , becomes homogeneously tinted , the author appends the readings , taken in the way described , from various portions of a piece of the standard paper used for the sun-pictures exposed for some seconds to direct sunlight . Reading . Deviation from mean . Portion No. 1. . 101-4 ... . +0-93 , , 2. . 1007 ... . +0-23 3. . 98-5 ... . -1-97 4 . 101-6 ... . +113 , , 5 . , 99.9 ... . -0-57 , 6 . 100-7 ... . +0-23 Mean. . 100-47 The sun-pictures obtained on the sensitive paper must possess only a slight tint , otherwise the differences in shade cannot be accurately observed ; they then exhibit a peculiar coarse mottled appearance , which is not due to imperfections in the paper or the lenses , nor to the action of the earth 's atmosphere . Perhaps these irregular dark and light patches are owing to clouds in the solar atmosphere , and they may have an intimate connexion with the well-known phenomenon of the red prominences . Mr. Baxendell and the author propose to carry out , according to this method , a regular series of observations of the variation of the relative amounts of brightness on the sun 's disc , and they hope before long to be able to present the Society with some further details .

112330

3701662

On the Contractility of Healthy and Paralysed Muscles as Tested by Electricity

650

651

Proceedings of the Royal Society of London

Harry Lobb

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0141

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112330

10.1098/rspl.1862.0141

http://www.jstor.org/stable/112330

Nervous System

Electricity

Nervous System

X. " On the Contractility of Healthy and Paralysed Muscles as tested by Electricity . " By HARRY LOBB , Esq. Communicated by JOHN SIMrON , Esq. Received April 30 , 1863 . If a moist conductor from the positive pole of the finer wire of an electro-magnetic battery* be placed upon the skin covering the origin of a healthy muscle , and the moist conductor from the negative pole , upon its belly , and a current of moderate intensity be allowed to pass , the muscle will contract tonically as long as the current passes ; and if it be increased in intensity , cramp will eventually be induced . The positive pole may be placed upon almost any part of the body to produce this effect ; only as it is removed further from the muscle to be acted on , the intensity of the current must be progressively increased . A healthy muscle contracts with more vigour if the current be direct-that is to say , the positive pole towards the centre , the negative pole towards the periphery . If a muscle paralysed from recent injury to the brain be acted upon in the same way , it will be found to contract more vigorously than a healthy one under the same intensity of current . If an extensor muscle paralysed and wasted , the result of poisoning by lead , be treated in the same way , no contraction can be induced even with the highest power of the apparatus ; the unparalysed flexors will alone contract . If a muscle paralysed and wasted from loss of nutrition , as in those local paralyses which are the sequelae of fever , the exanthemata , convulsions , irritation during teething , &c. , be acted on in the same way , no contraction can be induced ; if the current is increased in intensity , the healthy or antagonistic muscles contract . In these two latter instances-after treatment by the continuous galvanic current , when circulation has been re-established , and the paralysed muscles are better nourished-if the current be reversed , the positive pole placed on the insertion of the muscle , and the negative pole on the belly , and if the current is not too strong , faint contraction takes place , gradually increasing until the muscle is sufficiently restored to contract under the direct stimulus . A singular fact in connexion with these paralysed and wasted muscles is , that they will contract at the will of the patient , for some time , before they will do so to the stimulus of the current ; but the paralysed muscles are not safe from a relapse until they contract vigorously to the ordinary direct electrical stimulus . At a certain stage of improvement , when the paralysed muscle will neither contract to the will nor to the electro-magnetic current , it will do so to the combinationD of the two . 1863.1 651

112331

3701662

On the Influence of Temperature on the Electric Conducting-Power of Alloys. [Abstract]

652

654

Proceedings of the Royal Society of London

A. Matthiessen|C. Vogt

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112331

http://www.jstor.org/stable/112331

Tables

Measurement

Tables

XI . ( " On the Influence of Temperature on the Electric Conducting-Power of Alloys . " By A. MATTHIESSEN , F.R.S. , and C. VOGT , Ph. D. Received June 11 , 1863 . ( Abstract . ) The subject of this paper has been divided into four parts , viz.:I . Experiments on the influence of temperature on the electric conducting-power of alloys composed of two metals . II . Experiments on the influence of temperature on the electric conducting-power of some alloys composed of three metals . III . On a method by which the conducting-power of a pure metal may be deduced from that of the impure one . IV . Miscellaneous and general remarks . In the first part , after having given the numerical results , we proceed to explain the law which regulates this property . It is as follows : The observed percentage decrement in the conducting-power of an alloy between 0 ? and 1000 C. is to that calculated between 0 ? and 100 ? C. as the observed conducting-power at 100 ? C. is to that calculated at 100 ? C. Or in symbols , Po : Pc : : X 10 : X1X ' , where Po and Pc represent the observed and calculated percentage decrements in the conducting-power of the alloy between 0 ? and 100 ? C. ; and X100o and X'l00o its observed and calculated conductingpower at 100 ? C. , Pc is equal in nearly all cases to 29'307 * , the exceptions being only in the instances of thallium and iron alloyst . The above law holds good for most of the alloys belonging to the first and third groups , as well as for a part of those belonging to the second group T. Now , if the above proportion , Po : Pc : : X10o:X'..(1 ) P=:00X ... ... ( 1 ) be converted into terms of resistance , the following formula is obtained , 2= loopo-r0oo= 100 ? -o * . **** ( 2 ) where r100o0 ro 2100r ' and r'0O represent the observed and calculated resistances at 0 ? and 100 ? C. The formula , however , expresses the fact that the absolute dijference between 0 ? and 100 ? C. in the resistance of an alloy is equal to the absolute diff'erence between 00 and 100 ? in the calculated resistance of the alloy . Formula 2 may also be written r100§ 100 ? = ? 0o ' which , if correct , leads to the expression r ' : o r0o ; that is , the absolute deference between the observed and calculated resistances of an alloy at any temperature equals the absolute difference between the observed and calculated resistances at 0 ? C. ; or , in other words , r - ? r= a constant ... ... . ( 3 ) After giving various examples to show the correctness of the above , we prove that from the expression rtr'= a constant ( 3 ) we may deduce the formula for the correction of resistance or conducting-power for temperature of an alloy as soon as we know its composition and its resistance at any temperature ; for , as r'10 r ' 0 , and r ' , may be calculated with the help of the formula given for the correction of conducting-power for temperature for most of the pure metals , if the constant rt-r't be determined , then r100 = rt2100 + constant , rt =r't constant , 0o =r00 + constant ; and from these terms the formula for the correction of resistance or conducting-power for temperature may be calculated , which in most cases will be found very near the truth . In the second part we show by a few experiments that most alloys of three metals will probably be governed by the same law with respect to the influence of temperature on their conducting-power as alloys of two metals . In the third part we deduce iP ' : : M mool.(4 ) P 100P 100te od ad cd ( where P and P ' represent the observed and calculated percentage decrements in the conducting-power of impure and pure metals between 0 ? and 100 ? C. , M1 and ' 10M their conducting-powers at 100 ? C. ; P ' is for most metals 29-307 ) from Po : Pc : : X : X ' ... ( 1 ) 10 0o ... .1 For when we consider the last two terms of the proportion , and bear in mind that a trace of another metal has very little or no effect upon X'100o ( when it represents the conducting-power of an alloy consisting of one metal with only a trace of another metal ) , while it alters X10o to a very marked extent , it is evident that X'100o may be replaced by M1i00o We verify this by comparing the conducting-power of a pure metal directly determined , with the conducting-power of the same metal deduced from a determination of the conducting-power of its alloy with small quantities of other metals . It is a curious fact , that the deduced values from experiments upon hard-drawn wires are in reality the conducting-powers of the annealed ire e of te pure metal . After having thus verified the method , we have not hesitated to employ it in the determination of the conducting-power of certain metals which have not yet been experimented upon in a state of purity . In the fourth part we point out , first , that the percentage decrement in the conducting-power of alloys between 0 ? and 100 ? is never greater than that of the pure metals composing them ; secondly , that the conducting-power of alloys decreases with an increase of temperature ( some bismuth alloys form an exception to this law ) ; thirdly , that in some cases the percentage composition of an alloy may be deduced from its conducting-power , with the aid of the percentage decrement in its conducting-power ; fourthly , the method which we have used for determining the class to which the metals belong in respect to the conducting-power of their alloys ; and fifthly , that the results which we have obtained and described in this memoir fully bear out the views put forward in a former one on the chemical nature of alloys .

112332

3701662

On the Peroxides of the Radicals of the Organic Acids. [Abstract]

655

658

Proceedings of the Royal Society of London

B. C. Brodie

abs

6.0.4

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112332

http://www.jstor.org/stable/112332

Chemistry 2

Tables

Chemistry

XII . " On the Peroxides of the Radicals of the Organic Acids . " By Sir B. C. BRODIE , Bart. , Professor of Chemistry in the University of Oxford . Received June 18 , 1863 . ( Abstract . ) In a former notice published in the 'Proceedings of the Royal Society ' ( vol. ix . p. 361 ) , an announcement was made of the discovery of a new group of organic combinations , the peroxides of the radicals of the organic acids-bodies which in the systems of the combinations of these radicals occupy the same relative position as is held by the peroxides of hydrogen , barium , or manganese in the systems of the combinations of those elements . An account was given of the mode of preparation and properties of two members of this group , the peroxides of benzoyl and of acetyl , C,1 H1o 0 and C4 H6 04 . The present paper contains an extension of this inquiry . In it is given an account of several other peroxides of monatomic radicals , the peroxides of nitro-benzoyl , of cumenyl , of butyl , and of valeryl , and also an inquiry into the action of the peroxide of barium on the bibasic anhydrides . The nitro-benzoic peroxide is formed by the action of fuming nitric acid on the peroxide of benzoyl . It stands to peroxide of benzoyl in the same relation as anhydrous nitro-benzoic acid stands to anhydrous benzoic acid , and may be regarded as derived from that peroxide by the substitution in it of two atoms of peroxide of nitrogen for two of hydrogen . The formula of the substance is C,4 Hg ( NO2)2 0 . Calculated . Found . C14 ... ... . . 168 ... ... . . 50-60 ... ... . . 5060 I , ... ... . . 8 ... ... . . 2-41 ... ... . . 2-58 N ... ... . . 28 ... ... . . 8-43 ... ... . . 849 08 ... ... . . 128 ... ... . . 38-56 ... ... . 38-33 332 100-00 100-00 The peroxide of cumenyl is procured by a process strictly analogous to that by which the peroxide of benzoyl is formed ; it has the constitution C20 I22 04 . The peroxides of butyl and valeryl are prepared by the action of hydrated peroxide of barium on the anhydrous acid . It is only necessary to mix in a mortar equivalent quantities of the two sub1863.J 655 [ June 18 , stances . The peroxide is separated by solution in ether from the water in which it is dissolved and suspended . These substances are dense oily fluids , exploding slightly when heated , but not so readily decomposible as the peroxide of acetyl . The analysis of the peroxide of butyl , dried by chloride of calcium , gave results corresponding with the formula C8 HE1 O0 . Calculated . Found . C8 ... ... . . 96 ... ... . . 55-17 ... ... . . 55-11 1H , ... ... . . 14 ... ... . 8-05 ... ... . . 8-28 0 ... 64 ... ... . . 36-78 ... ... . . 3661 174 100-00 100-00 The analysis of the peroxide of valeryl gave results corresponding with the formula CIo HI1 04 . Calculated . Found . C , , ... ... . . 120 ... ... . . 59-40 ... ... . . 59-39 H , , ... ... . . 18 ... ... . . 8-91 ... ... . . 9-17 0 ... ... . . 64 ... ... . . 31-69 ... ... . . 31-44 202 100-00 100-00 The mode of formation of these peroxides is given in the equation 2R , O0+Ba , 02=2Ba RO+R2 02 . These substances are decomposed as well as formed by the action of the alkaline peroxide , according to the equation R2 02+ Ba202 =2 BaRO 1+0 , , giving a striking example of those consecutive actions referred to in a former paper as the cause of certain catalytic decompositions . The action of the bibasic anhydrides on the alkaline peroxides is of special interest . When anhydrous succinic acid , lactide , or anhydrous camphoric acid is mixed with an equivalent of hydrated peroxide of barium , a solution is obtained possessing the most powerful oxidizing properties , which bleaches indigo , evolves chlorine with hydrochloric acid , and oxidizes the protosalts of iron and manganese , but which does not discolour permanganic acid , or give with chromic acid the blue colour formed by peroxide of hydrogen . When boiled , the solutions evolve oxygen , and afterwards contain a salt of the acid employed-in the case of succinic acid , giving a crystalline precipitate of succinate of 656 1863 . ] barium , and in the case of camphoric acid , giving with acetate of lead a precipitate of camphorate of lead . These solutions are in a state of continual decomposition . Only in one instance , that of camphoric acid , was it found possible to analyse the substance , and that only by indirect processes . The oxygen contained in the organic peroxide was estimated in a measured portion of the solution by means of a standard solution of iodine ; the camphoric acid formed on boiling was determined by precipitation with acetate of lead in another measured portion ; and in a third portion the barium was estimated as sulphate . The results of these determinations are given below , the camphoric acid being assumed as correct . They lead to the conclusion that the solution contains the elements of one equivalent of anhydrous camphoric acid , one of oxygen , and one of baryta . Atomic weight . Calculated ratio . Found . C,0 1 03 ... ... . . 182 ... ... . . 25-12 ... ... . . 25-12 0 ... ... . . 16 ... ... 220 ... ... . . 207 Ba2O ... ... . . 153 ... ... . . 2112 ... ... . . 21-51 the reaction being C , , Hi , 0 , + Ba2 , 0-Co HE , , 0O Ba , . That the substance formed is to be regarded as the baryta salt of the peroxide of camphoryl , and not as the camphorate of the peroxide of barium , is proved by the reactions of the solution , which does not give peroxide of hydrogen when decomposed by acids , or a precipitate of the hydrated peroxide of barium when heated with a solution of baryta . The organic peroxides constitute a new and peculiar group of chemical substances characterized by reactions never hitherto found in any compound of carbon , and which materially extend our views of the possible properties of the so-called organic combinations , and of their analogies to inorganic substances . They are the organic representatives of chlorine in the same sense as the oxides of the compound ammoniums are the representatives of potash , and in a yet closer sense than ether and alcohol resemble the oxide and its hydrate , or than ethyl or marsh-gas are analogous to hydrogen . This analogy is of a profound character , not consisting merely in the analogy of symbolic form , but in the absolute identity of reactions . 657 The admitted analogies of the peroxide of chlorine have as it were their maximum in the organic peroxide . Not only is chlorine represented in the peroxide , but hydrocloric acid is represented in the organic acid , and a series of parallel equations may readily be constructed , showing the identical character of the reactions of the two classes of substances . Both bleach a solution of indigo , oxidize the protosalts of iron and manganese , decompose water under the influence of sunlight , and evolve oxygen with an alkaline peroxide , forming the salt of the corresponding acid .

112333

3701662

Explorations in Spitzbergen, Undertaken by the Swedish Expedition in 1861, with the View of Ascertaining the Practicability of the Measurement of an Arc of the Meridian

658

662

Proceedings of the Royal Society of London

Otto Torell

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0144

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112333

10.1098/rspl.1862.0144

http://www.jstor.org/stable/112333

Biography

Geography

Biography

XIII . " Explorations in Spitzbergen , undertaken by the Swedish Expedition in 1861 , with the view of ascertaining the practicability of the measurement of an Arc of the Meridian . " By Dr. OTTO TORELL , Professor of Zoology in the University of Lund . Communicated by the President . Received June 2nd , 1863 . In the year 1858 I made a voyage to Spitzbergen , in company with two other naturalists , in order to investigate the Natural History of that country . I was thereby induced to study the history of the various Arctic expeditions that had gone out from England . In Beechey 's and Barrow 's works I saw mentioned a suggestion which attracted my attention in a high degree . A letter is there given from Captain Edward Sabine to Mr. Davies Gilbert , in which the writer , on his return from his celebrated Pendulum Expedition , proposes to explore Spitzbergen , with the view of ascertaining whether the measurement of an arc of the meridian could be carried out there* . An arc from Ross Islet to Hope Island would comprise nearly 4- ? of latitude-equivalent to an arc of 9 ? in the mean latitude of France , and of 7 ? in the mean latitude of Great Britain . The difficulties opposed by climate and ground were not considered by Captain Sabine to be so great as not to be surmounted ; and he offered , in company with another officer and a sergeant of Artillery , to show either the feasibility or , once for all , the impossibility of the undertaking . A special advantage is pointed out by Spitzbergen being divided into two nearly equal parts from north to south , thus very materially facilitating communications between the different angular points . Admiral Beechey says that Captain Sabine 's plan was placed before the Royal Society in 1825 by Sir John Herschel , taken into consideration in the autumn of the same year , and warmly supported by Mr. Davies Gilbert , Sir I-Humphry Davy , the then President , and by other members of the Royal Society . The reasons why it was not carried out are not mentioned ; but Sir John Herschel leaves us to infer that Captain Sabine was called upon to display his powers in another scientific undertaking of a more arduous though not less important kind . This explanation appeared to be natural , and thus the whole matter was shelved for many years . The plan in question seemed to me so simple and practical , and at the same time so useful in a scientific point of view , that I could not help espousing it with a very warm interest . In the year 1860 , the Swedish government and Diet , as well as Prince Oscar , granted funds for a new scientific expedition to Spitzbergen . Being placed at the head of this undertaking , in which a rather large number of scientific men were willing to take part , I did not fail to call the attention of the Academy of Sciences to the plan proposed by General Sabine in 1825 . The Academy were alive to its importance ; and their two astronomical members , Professor Selander and Assessor Lindhagen , who had themselves taken part in the Swedish-Norwegian triangulation , considered that the explorations ought to be carried out , and for that purpose they issued the requisite directions to two of the participators in the expedition , Messrs. Duner and Chydenius . To them it was confided to investigate whether suitable angular points could be found from the islands north of Spitzbergen to Hope Island in the South , either along the western coast of Spitzbergen or through iHinloopen Strait and Weide Jans Water , which nearly divide Spitzbergen into two from north to south . One went on board the ship which , according to the plan , was to explore the north of Spitzbergen and Hinloopen Strait , and the other on board the other ship which was to explore the west of Spitzbergen and Weide Jans Water . At the end of May 186 1 the two vessels reached Amsterdam Island , in nearly 80 ? latitude ; and at the commencement of June they passed Verlegen Hook , and anchored in Treurenburg Bay , whence Parry , in 1827 , made his celebrated attempt to reach the North Pole . But the polar ice immediately afterwards pressed against the coast , and imprisoned both vessels more than a month in Treurenburg Bay . The pack was so close that no boat excursions of any extent could be made . The explorations for survey were a good deal impeded by this circumstance ; for the investigation of the western coast of Spitzbergen could not be commenced until a much later period than intended . The survey of Weide Jans Water could not be carried into effect , owing to drift ice , adverse winds , and calms . Mr. Duner , to whom this undertaking was allotted , as well as the investigation of the practicability of the survey along the western coast of Spitzbergen , came to the conclusion that no impediments existed for carrying out the triangulation from Ross Islet to Amsterdam Island , but that the mountains surrounding Magdalena Bay are so steep and difficult or impossible of access , that the continuation of the survey southwards must be considered , if not absolutely impossible , at least so difficult and entailing such heavy expense , that its execution along that coast will probably never be carried into effect . Mr. Chydenius , who was to explore the northern portion of the arc , presumed to be measurable from Ross Islet to Hope Island , was more fortunate in his work . During sundry boat excursions and ascensions of many mountains from the northernmost part of Spitzbergen to the termination of Hinloopen Strait , he succeeded in completely solving the problem as to that part of Spitzbergen , comprising nearly the half of the arc to be measured . The survey was carried out courageously and energetically under circumstances of frequent difficulty , as well in the drift ice as in crossing the glaciers of the interior . The accompanying Ymap makes a detailed description unnecessary , and I therefore confine myself to stating that all the lines of the sights in the network marked with continuous lines are , with one single exception , observed , and that Mr. Chydenius has had opportunities of convincing himself that though not all the lines of the sights in the network marked with dotted lines are observed , yet nothing prevents the angular points connected by them from being seen one from the other . The triangles connected by continuous lines of the sights are nine in number . Their angles are computed by Mr. Chydenius in an accompanying Table . All the angular points are selected on moderately high and accessible mountains , situated close to , or not very far from the coasts , and the distances between them are not greater than will admit of the signals being easily seen . Mr. Chydenius found the ground , as well in Low Island as to the west of Treurenburg , to be favourable for measuring a base . As the survey , so far as carried out , proves that , for executing the measurement of an arc of the meridian , no impediments exist which may not be overcome by courage and perseverance , there remains the question whether the part not yet explored may be expected to be equally favourable ; the reply to this cannot , of course , be fully given until a similar survey has been made of the still unknown portion ; there are , however , means of partially judging of the prospects of success . Mr. Chydenius considers himself almost justified in stating with certainty that the mountains marked X and X on the map will be found to be visible from Weide Jans Water . He is inclined to think that the easiest communication may be made through Lomme Bay . The distance from I-inloopen Strait to Weide Jans Water cannot be great . According to statements which , however , we were unable to verify , there is said to be a strait connecting these two sheets of water , and a vessel is reported to have sailed through it . Mr. Lamont is also of opinion that Weide Jans Water is open to the north . This , if found to be true , would tend greatly to facilitate the work . It is also probable that the network can be drawn from the Waigat Islands at the southern embouchure of Hinloopen Strait to the Walter Thymen Bay , through the latter to Weide Jans Water , and further to Hope Island . There still remains the question as to the facilities that the land on the two sides of Weide Jans Water may afford for the survey . Those walrus-hunters whom I have interrogated regarding that part of the country , are unanimous in their opinion as to the mountains on the western side being similar to those on the west coast , that is to say , as inaccessible as possible . But the country to the east of the said Water is described as a tableland , in which accessible mountains may be found in several places . There are therefore well-founded reasons for thinking that the whole arc will be found measurable if the survey is continued . Mr. Chydenius has offered to furnish the remaining part of the exploration . The Swedish Academy of Sciences consider the completion of the survey so important , that they have petitioned Government to supply funds for carrying it into effect during the present or next year . There is every probability that the money will be granted , and , if the result turn out as expected , that necessary steps will be taken for executing the measurement of the arc itself . The Swedish Government has , at the instance of the Academy of Sciences , already furnished means for preliminary investigations in reference to another gecdetic enterprise , namely , for the Swedish share of the proposed large middle-European triangulation from Palermo to Trondhjem , and have asked the Estates for money for executing the measurement . Should , then , the survey in Spitzbergen also be carried out , an important contribution will be made , not only to ascertain the compression of the globe in the vicinity of the North Pole , but also for the much-sought-after knowledge of the real form of the earth on different portions of its surface ; and the undertaking will to a certain degree complete the results both of the projected middle-European triangulation and of the Russo-Scandinavian already effected . If the triangulation in question be executed , it will not be the only result arising from several years ' scientific labours in Spitzbergen . It is superfluous here to allude to many investigations of importance which may be made ; it is sufficient to keep in mind the situation of Northern Spitzbergen , distant scarcely 10 ? of latitude from the North Pole . There are well-founded reasons for thinking that the execution of the measurement in question may be looked forward to . And if we seek for the origin of the whole matter , we can trace it in Captain Sabine 's well-planned and lucidly explained project , which he submitted to the examination of the Royal Society in 1825 .

112334

3701662

On the Magnetic Disturbance Which Took Place on the 14th of December 1862

663

668

Proceedings of the Royal Society of London

Balfour Stewart

fla

6.0.4

http://dx.doi.org/10.1098/rspl.1862.0145

proceedings

http://corpora.clarin-d.uni-saarland.de/surprisal/6.0.3/?id=112334

10.1098/rspl.1862.0145

http://www.jstor.org/stable/112334