A R Vasudeva Murthy
Articles written in Proceedings – Section A
Volume 34 Issue 5 November 1951 pp 283-298
Certain sulphides, in presence of a small amount of moisture were found to catalyse the reaction between hydrogen sulphide and sulphur dioxide. The kinetics of this reaction was studied in a closed system, using an all-glass, gas circulation pump.
The partial pressure of water in the reacting system was maintained constant with the aid of a hygrostat [mixture of a hydrated salt and its anhydrous form (or lower hydrate)]. The higher the partial pressure of water, the greater was the velocity of reaction, for a given catalyst.
Of the sulphides employed, cobalt thiomolybdate was found to be the best catalyst. Cobalt sulphide and molybdenum sulphide were less efficient. Next in order of efficiency, was silver sulphide.
Boron trifluoride and anhydrous aluminium chloride were found to have no catalytic effect on the union between hydrogen sulphide and sulphur dioxide.
The mechanism of the reaction could be explained on the basis of the formation of thiosulphurous acid, as the primary product.
Volume 35 Issue 1 January 1952 pp 7-13
When hydrogen sulphide is oxidised by chloramine-T, the sulphide may yield sulphur, or sulphate, or both the products. The relative proportion of the two products of oxidation depends on the pH, of the solution and on the presence of certain catalysts. At low pH, sulphate is produced in relatively high amounts, while at higher pH values, sulphur formation is greater. Presence of molybdate increases sulphate yield, while tungstate on the other hand, diminishes it. It is suggested that the primary product of oxidation of hydrogen sulphide is dihydrogen sulphoxide (H2SO) which, being analogous to hydrogen peroxide and hydrogen persulphide, is likely to be more stable at low pH values. The sulphoxide undergoes two simultaneous reactions, (
Volume 35 Issue 2 February 1952 pp 69-71
Potentials of the chloramine-T—sulphonamide system have been found to be real redox potentials. With an increase in pH, the oxidation potential decreases. Depending on the pH of the solution, the oxidation of hydrogen sulphide by chloramine-T yields varying proportions of sulphur and sulphate. Reagents like osmic acid, sodium tungstate and sodium molybdate are also found to affect the ratio of sulphur to sulphate, formed by the oxidation of hydrogen sulphide.
A complete explanation for the observed results cannot be based on the effect of pH on the redox potential, as these reagents do not alter the potential. The specific effect of these reagents is probably due to their influence on dihydrogen sulphoxide, the primary product of oxidation of hydrogen sulphide.
Volume 35 Issue 2 February 1952 pp 99-101
Volume 36 Issue 5 November 1952 pp 388-401
Volume 36 Issue 6 December 1952 pp 425-439
Volume 36 Issue 6 December 1952 pp 537-543
1. Hydrogen sulphide and sulphur dioxide react in carbon tetrachloride (kept at — 16° C.), in presence of moisture, to give a yellow solution which contains disulphur monoxide—the anhydride of the hypothetical thiosulphurous acid. For the formation of the oxide, sulphur dioxide has to be in large excess.
2. The chemical behaviour of disulphur monoxide in the yellow solution was identical with that of the oxide obtained by the combustion of sulphur, under oxygen at low pressure.
3. A spectrophotometric study showed identical behaviour of disulphur monoxide in the two solutions.
Volume 37 Issue 1 January 1953 pp 11-16
Volume 37 Issue 1 January 1953 pp 17-22
Volume 37 Issue 1 January 1953 pp 23-28
Volume 51 Issue 5 May 1960 pp 270-279
1. Anhydrous aluminium chloride reacts with phosphorus oxychloride to give a complex with a composition AlCl3.2 POCl3 which can be prepared in the form of a free flowing powder.
2. The phosphorus oxychloride-aluminium chloride complex in nitrobenzene dissociates into AlCl3.POCl3 and POCl3 as indicated by the cryoscopic measurements.
3. The solution of the complex in nitrobenzene has a higher specific conductivity than the corresponding electrical conductivities of individual components. Similar higher electrical conductance is observed when the two components are mixed in nitrobenzene in different proportions.
4.When a solution of anhydrous aluminium chloride in nitrobenzene is titrated conductometrically against a solution of phosphorus oxychloride in nitrobenzene, a limiting value in the conductivity is reached at point corresponding to the molecular composition, the components in the ratio of 1:2 AlCl3: POCl3 in solution.
5. The absorption maxima of the complex in nitrobenzene solution differ from the absorption maximum of the individual components.
Volume 55 Issue 3 March 1962 pp 168-173
Elemental sulphur dissolved in organic solvents (such as chloroform, carbon tetrachloride and benzene) reacts rapidly and quantitatively, with aqueous alkali at room temperature, when this immiscible liquid mixture is homogenized by the addition of ethyl alcohol. The products of reaction under these experimental conditions are sulphide, thiosulphate and a small quantity of sulphite. A mechanism involving the intermediate formation and decomposition of dihydrogen sulphoxide, HSOH, is suggested for the reaction.
Volume 56 Issue 3 September 1962 pp 130-140
The hydrolytic reactions of esters and amides of thiosulphurous acid are investigated in a homogeneous medium. The esters are hydrolysed by alkali to give sulphide, sulphite and thiosulphate whereas the amides are resistant towards alkali. Both the esters and amides are hydrolysed by acids giving hydrogen sulphide, sulphur dioxide, polythionates and elemental sulphur. The hydrolysis of these esters and amides in presence of sulphurous acid and thiosulphuric acid gives tetrathionate and hexathionate, respectively.
Volume 59 Issue 4 April 1964 pp 263-267
When the products of reaction between elemental sulphur and copper oxide at elevated temperature in vacuum are bubbled through chilled inert organic solvents like carbontetrachloride, orange-yellow solutions were obtained indicating the presence of lower oxide of sulphur. This lower oxide has been found to be disulphur monoxide as shown by three different types of reactions; (1) Mercury decomposition, (2) Reaction with hydrogen iodide and hydrolytic reaction in an alkaline homogeneous medium.