Titrimetric microdetermination of silver, lead and cadmium with thioglycollic acid and of mercury(II) with 2-mercaptopropanoic acid

A simple and rapid titrimetric method is described for the microdetermination of Ag(+), Cd(2+) and Pb(2+), based on their formation of mercaptides with a measured excess of 2-mercaptopropanoic acid, and similar determination of Hg(2+) with thioglycollic acid. Univalent and bivalent metal ions release one and two thiol protons respectively, which along with the carboxyl protons of the thiol reagent are titrated with standard alkali. The difference from the blank titration gives the increase in acidity which is a function of the metal-ion concentration. The proposed procedure is applicable to samples containing 0.025-0.25 mmole of these ions, the average deviation being in the range 0.2-0.5%.     

Determination of cysteine, 3-mercaptopropionic, and mercaptosuccinic acid with neutral hexacyanoferrate(III)

Two procedures are proposed for the determination of -SH groups. In both a known amount of hexacyanoferrate(III) is added to the sample and the excess is then determined. In one procedure an excess of ascorbic acid is added and the excess of that is titrated with iodine. In the other, the excess is determined by direct titration with ascorbic acid. Both procedures avoid errors resulting from side-reactions of iodine which takes place if the excess of hexacyariofcrrate(III) is reacted with potassium iodide.     

Determination of sulphur functions with iodoso-compounds

Iodoso derivatives, e.g., m- and p-chlorophenyl, m- and p-methylphenyl and p-nitrophenyl-iodosoacetates and o-diacetoxyiodobenzoate, have been thoroughly investigated as oxidants and are proposed as analytical reagents for the determination of thiols, thioureas, isothiocyanates, organic sulphides, disulphides, xanthates, dithiocarbamates, amines and alcohols in aqueous and non-aqueous (acetic acid, acetonitrile, dimethylformamide) media. The error of the determination of thiols is 0.2% thioureas 0.5%, organic sulphides and disulphides 0.4%, isothiocyanates 0.4%, dithiocarbamates 0.4%, and xanthates 0.5%. All the methods are precise to 0.2-0.5%. It is also shown that the properties of the o-derivatives differ markedly from those of the m- and p-derivatives. The o-derivatives contain a 1-substituted 1,2-benzoiodoxilin-3-one ring system. The stability of this system is apparently associated with the size of the five-membered ring; other compounds in which iodine is apparently part of larger rings are less stable. o-Diacetoxyiodobenzoate appears to be the best analytical reagent of the iodoso series. The m- and p-iodosobenzoates are found unsuitable for quantitative oxidation of cysteine.