Determination of hydrogen sulphide

According to Skopintsev et al. (1959), only a few percent of the total sulphide content originates in organic sulphur compounds. 

Hydrogen sulphide is a poisonous gas that readily dissolves in water. No higher life forms can survive in water containing hydrogen sulphide, and such areas are therefore transformed into oceanic deserts. Hydrogen sulphide in a water sample is detected easily by its characteristic smell, even at extremely low concentrations. 

In water hydrogen sulphide is ionized in seawater (pH 7-8) it occurs mainly as HS ions  

In an acidic medium, dissolved oxygen will rapidly oxidize hydrogen sulphide to elemental sulphur, but in neutral solutions, including seawater, it is slowly oxidized to sulphate (see Section 6.1)  

Water containing hydrogen sulphide has a negative redox potential and therefore is a reducing medium. 

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Zielinski, E. Use of argon ionisation detector with <3Ni source for chromatographic determination of hydrogen sulphide, sulfur dioxide and carbon oxy-sulfide. Chem. Anal. 14, 521 (1969). - Z. Anal. Chem. 254, 378 (1971). 

A.V. Bulatov, D.K. Goldvirt, L.N. Moskvin, A.L. Moskvin, E.A. Vaskova, Stepwise injection photometric determination of hydrogen sulphide in natural gas, J. Flow Injection Anal 23 (2006) 102. 

A method for determining sulphur in organic compounds was elaborated by Okuno et al. [109], It is based on catalytic destructive hydrogenation of the sample and chromatographic determination of hydrogen sulphide. The detection limit is 10 %. The method can be further developed to determine trace amounts of sulphurous compounds in petroleum at levels down to 10" % [109]. 

Note. The simultaneous determination of hydrogen sulphide may be made from the difference in the total height of the waves obtained before and after addition of cadmium nitrate. 

We recommend spectrophotometric determination of hydrogen sulphide, but other methods will be mentioned as well (see Sections 5.3.3 and 5.3.4). 

The determination of hydrogen sulphide as methylene blue (3,7-bis(dimethylamino)phe-nothiazine-5-onium chloride) was introduced by Fischer (1883) and has been used for seawater in many investigations. Cline (1969) has closely reviewed and tested the methylene blue method and has suggested several improvements. 

The procedure is illustrated by determination of the concentration of hydrogen sulphide water. 

Bunsen 5 showed that the passage of a rapid stream of hydrogen sulphide through a hot solution of an alkali arsenate acidified with hydrochloric acid produced a precipitate of arsenic pentasulphide, and that this was a satisfactory method of determining arsenic quantitatively. These results were confirmed by McCay,6 and led to more systematic investigation of the subject,7 the result of which showed that the conditions favourable for the formation of arsenic pentasulphide, when hydrogen sulphide acts on aqueous arsenic acid or acid solutions of arsenates, are (a) a considerable excess of hydrochloric acid present, (b) a rapid passage of the gas, and (c) a comparatively low temperature—the liquid should be warm, as precipitation is extremely slow in the cold. Under these conditions arsenic pentasulphide alone is formed ... 

Jones, C. N. Gas chromatographic determination of hydrogen, oxygen, carbon monoxide, carbon dioxide, hydrogen sulphide, ammonia, water and C] to C saturated hydrocarbons in refinery gases. Anal. Chem. 39, 1858 (1967). 

In addition to his work on titrimetry, Gay-Lussac made important contributions in other areas of analytical chemistry. He studied the reactions of hydrogen sulphide in different media, thus laying the foundations for the classification of metals into different analytical groups, and in conjunction with Thenard, he developed the first truly practicable method for the determination of carbon and hydrogen in organic compounds.54... 

For ions of initial structure (CH3CH2CH=SH)+ and (CH3CH=SCH3)+, average deuterium isotope effects, i, for metastable ion decompositions effecting loss of hydrogen sulphide of 2.3 and 1.8, respectively, were determined [136]. 

Properties.—Thiophosphoryl chloride is a transparent colourless liquid which fumes in the air and smells of hydrogen sulphide. The formula has been established by analysis and vapour density determination. The density of the liquid is 1-66820 at 0° C. and 1-45.599 at the normal boiling-point, 125-12° C.8 The coefficient of expansion between these temperatures is given by8... 

The quantity of dissolved Mn(II) in natural waters depends on the solubility of hydroxide, carbonate and sulphide. In most natural waters the equilibrium concentration of dissolved manganese is determined by the MnC03 solubility. The production of Mn(OH)2 is considered only in a stronger alkaline medium. In the presence of hydrogen sulphide and its ionic forms the Mn(II) solubility in alkaline media is limited by the MnS solubility and the equilibrium concentrations are the lowest under these conditions. 

Yields of hydrogen and sulphur have been determined in the rare-gas-sensitized radiolysis of hydrogen sulphide. The rate of formation of S2 from shock-heated H2S has been measured by means of the u.v. absorption technique in the temperature range 2380—3000 K. A mechanism for the formation of S2 was proposed and the influence of impurities on its rate of formation studied. The behaviour of an aqueous solution of H2S when submitted to ultrasonic irradiation has been investigated. The formation of molecular hydrogen and the appearance of colloidal sulphur was observed the former was explained by a mechanism involving direct dissociation of H2S, which is probably concurrent with oxidation of the U2S. ... 

Many azo derivatives may be determined by titration with titanous chloride, TiCls. The commercial chloride is boiled briskly with an equal volume of concentrated hydrochloric acid to remove traces of hydrogen sulphide, and then diluted to twenty limes its original volume with water free from oxygen. In the absence of air its... 

Another method for determination of the nickel area is based on chemisorption of hydrogen sulphide [389], Hydrogen sulphide is the stable sulphur compound at conditions for tubular reforming. It is the most severe poison for the reaction (refer to Section 5.4). The adsorption of hydrogen sulphide on nickel is rapid even below room temperature [376] [381]. At temperatures of industrial interest hydrogen sulphide is chemisorbed dissociatively on nickel. 

The method, in which a fivefold excess of hydrogen sulphide does not interfere, was used for the analysis of the atmosphere, exhalations, and wastes in the fibre industry. In an analogous way carbon oxysulphide can be determined. 

On the other hand the determination of aromatic sulphides and thiophene derivatives, after oxidation to the sulphones with hydrogen peroxide< >, appears to be very promising. 

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