The selectivity of the hydrogenation of linseed oil
We have invest igated the se lec t iv i ty of the hydrogenat ion of l inseed oil, which is a mix tu re of t r i g l y c e r ides of fatty acids of different degrees of unsaturat ion linolenic, l inoleic, and ole ic and sa tura ted fatty acids . Depending on the conditions of hydrogenat ing oils and fats , the p roce s s may go according to the following scheme , given in the l i t e r a tu re [1]:
Some additional notes on the kinetics and theory of fatty oil hydrogenation
Summary1.Equations are given for estimating from the composition of oil samples the relative reaction rates of the different unsaturated fatty acids in an oil subjected to catalytic hydrogenation.2.Application of the equations to data from the hydrogenation of cottonseed oil reveals that the ratio of reaction rates, linoleic acid to oleic acid, varies from about 4 to 1 in very non-selective to about 50 to 1 in very selective hydrogenation. Re-examination of analytical data on two series of linseed oils hydrogenated selectively and non-selectively showed the following relative reaction rates for oleic, isolinoleic (9: 10, 15: 16 octadecadienoic), linoleic, and linolenic acids, respectively: non-selective, 1, 2.5, 7.5, 12.5; selective, 1, 3.85, 31, 77. In the non-selective hydrogenation of the oil, 24% of the linolenic acid reacting went to linoleic acid, 65% to isolinoleic acid, and 11% directly to oleic acid. In the selective reaction the corresponding figures were none to linoleic acid, 54% to isolinoleic acid, and 46% to oleic acid. The behavior of soybean oil hydrogenated selectively was quite similar to that of linseed oil.3.The results are discussed in relation to the theory of catalytic hydrogenation. They indicate that the solution of hydrogen in the oil and the adsorption of unsaturated oil on the catalyst are the two steps which are controlling with respect to the reaction rate. It is suggested that the hydrogen pressure, the degree of hydrogen dispersion through the oil, the catalyst concentration, and the temperature all affect the selectivity of the reaction through their influence on the concentration of hydrogen in the reaction zone, with selectivity being favored by a low concentration.
The Illinois Legislature
It further provides that the county must have voted "for license" at the last general election on that subject. Also, that the petition, together with all names and addresses on it, must first be published in at least two issues of some newspaper published in the town where the petition was circulated, for at least ten days before the petition is acted upon. Any officer authorized to issue licenses violating the provisions of this act is liable to a fine of from $500 to $1000 and imprisonment in the county jail for from two to twelve months. The act does not repeal any local laws forbidding the sale of liquor, but is cumulative to all anti-liquor laws now in force. The final section is: "This Act being necessary for the public peace, health, and safety, shall take effect and be in force from and after December 31, 1913." The postponement of the time for going into effect was made io order not to interfere with licenses already issued and to give the liquor dealers time to adjust themselves to the provisions of the act. But the liquor people denied that the emergency clause could be attached to an act the operation of which was postponed nearly a year. They called attention to the omission of the word "immediate," and declared that the postponement was in itself sufficient evidence that it was not necessary for the "immmediate preservation of the public health, peace and safety." A petition for reference was circulated and the necessary number of signatures was secured. The attorney-general was first asked for his opinion as to whether the act was subject to the referendum. That officer stated that he could find no precedent for such a case. Basing his decision on reason and common sense he declared the act not subject to the referendum. The circuit court was then asked for a write of mandamus against the secretary of state to compel him to submit the act, but the court refused to grant it, saying that the attachment of the emergency clause was evidence that the legislature intended to prevent its submission. At this writing the question is pending on appeal before the supreme court.