Cathodic stripping voltammetric determination at a hanging mercury drop electrode of the environmental heavy metal precipitant trimercapto-s-triazine (TMT).
Trimercapto-s-triazine (TMT) is available commercially for precipitating heavy metals in effluents prior to discharge and for recovering silver and copper. The TMT content of an effluent for discharge is normally monitored down to about 2 ppm by means of its UV absorption at 285 nm. Indirect cathodic-stripping voltammetric methods of determining TMT at sub-ppb levels in standard solutions are reported here. These methods might prove suitable for the determination of TMT in effluent at levels lower than is currently possible. TMT can be accumulated and determined indirectly at pH 9.0 as its mercury salt down to sub-ppb levels. Accumulation is made at 0 V and the mercury TMT reduction peak is at -0.47 V. Alternatively, by adding nickel(II), TMT can be determined optimally at pH 7.8, using the catalytic nickel peak at -0.73 V and accumulating between -0.10 and -0.60 V: at this pH the HgTMT peak at -0.47 V is small. At slightly higher pH (pH 8.6) the nickel TMT complex can be accumulated directly at -0.40 V, but at this pH, however, a slightly increased sensitivity can be achieved by accumulating TMT as its mercury salt, at -0.1 V in the presence of nickel(II), the nickel TMT complex being formed during the potential sweep on the release of the TMT when the mercury salt is reduced. Unlike many other thiols TMT is not accumulated as its copper(I) salt on addition of copper(II) to the solution.
Cathodic Stripping Voltammetry of Sulphur-Containing Amino Acids and Peptides in the Presence of Nickel Ion. Catalytic and Inhibiting Effects
Abstract The paper reviews recent studies on the effect of addition of Ni(II) in the cathodic stripping voltammetry of the following compounds: cysteine, penicillamine, cystine, glutathione (either reduced or oxidised) and N-acetylcysteine. With the exception of N-acetylcysteine, the above compounds give a cathodic stripping peak at -0.6 V (vs. Ag/AgCl, 3 M KCl electrode) which is due to the catalytic reduction of nickel ion. Even in the case of the disulphides the actual catalyst is the thiol produced by the cleavage of the -S-S- bond during the accumulation step. The catalytic peak enables the detection of the analyte with a better selectivity than is obtained with the stripping peak due to the reduction of mercury thiolates. In addition, Ni(II) suppresses the mercury thiolate peak of ligands such as cysteine or penicillamine, but does not modify the behaviour of thiols with low complexing properties (such as N-acetylcysteine). Consequently, compounds such as cysteine and its N-acyl derivatives can be d...
Determination of iodide with 1,3-dibromo-5,5-dimethylhydantoin (DBH) in comparison with the ICl-method. Analytical methods of pharmacopeias with DBH in respect to environmental and economical concern. Part 3.
USP 1995 (The United States Pharmacopeia, 23rd Edit., (1995), potassium iodide p. 1265, sodium iodide p. 1424), PH. EUR. 1997 (European Pharmacopoeia, third ed., Council of Europe, Strasbourg, (1997), potassium iodide p. 1367, sodium iodide p. 1493) and JAP 1996 (The Japanes Pharmacopoeia, 13th ed. (1996), potassium iodide p. 578, sodium iodide p. 630) determine iodide with the ICl-method (J. Am. Chem. Soc. 25 (1903) 756-761; Z. Anorg. Chem. 36 (1903) 76-83; Fresenius Z. Anal. Chem. 106 (1936) 12-23; Arzneibuch-Kommentar, Wissenschaftliche Erläuterungen zum Europäischen Arzneibuch, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, Govi-Verlag - Pharmazeutischer Verlag GmbH, Eschborn, 12th suppl. (1999), K10 p. 2), using chloroform, which is toxic and hazardous to environment. Without the application of chlorinated hydrocarbons USP 2000 (The United State Pharmacopeia, 24th ed. (2000), potassium iodide p. 1368, sodium iodide p. 1535) and Brit 1999 (British Pharmacopoeia London, (1999), Appendix VIII C, p. A162) titrate iodide with the redox indicator amaranth. A titration with potentiometric indication giving two end-points at the step of I(2) and [ICl(2)](-) is described. Due to the high concentration of hydrochloric acid required for the ICl-method, the determination with DBH (1,3-dibromo-5,5-dimethylhydantoin; 1,3-dibromo-5,5-dimethyl-2,4-imidazolidinedione) can be recommended and is performed easily. Similarly, the iodide content of gallamine triethiodide may be analyzed with DBH by application of a visual two-phase titration in water and ethyl acetate or with potentiometric indication in a mixture of 2-propanol and water. During the removal of the excess of DBH 4-bromo-triethylgallamine (2,2',2"-[1-bromo-benzene-2,3,4-triyltris(oxy)]N,N,N-triethylethanium) is formed.