The Formation of Sulfur from Hydrogen Sulfide and Sulfur Dioxide. A Contribution to the Vulcanization Process of Peachey

In the reduction of sulfur dioxide by hydrogen sulfide, the course of the reaction depends wholly upon whether water is present or the gases are dry. With water present, there is a ready separation of sulfur, even at room temperature, according to the general reaction: SO2+2H2S→3S+2H2O, though accompanied by more complicated reactions involving the formation of polythionic acids. On the contrary at room temperature the dried gases do not react, and only at elevated temperatures do they give rise to sulfur and water vapor, in which case because the reaction is exothermic the equilibrium is displaced more and more toward the original sulfur dioxide and hydrogen sulfide. Conversely then, the formation of free sulfur is favored by lowering the temperature. The heat of activation of the reaction is however so great, even at room temperature, that the rate of the reaction is imperceptibly small, and accordingly no reaction is observable. In the presence of rubber, on the other hand, conditions are extremely favorable for activation, because the rubber hydrocarbon plays the part of an acceptor of the liberated sulfur and is vulcanized by it, as Peachey and Skipsey were able to show in their well-known work. The question then arises whether, in this form of vulcanization, the water which is already present or which is formed plays a decisive role in starting and continuing the reaction (in which case the formation of polythionic acids might also play a part), or whether the essential reaction takes place between the two gases in the dry state, in which case the reaction progresses in a much more unrestrained way than in the absence of substances which activate the reaction. In view of this, two series of experiments were planned with the object of obtaining a better insight into the reaction. In one series the rate of the reaction with both gases in the dry state was studied by some trial measurements only; in the other series the part played by moisture in vulcanization by the Peachey process and in the vulcanization of rubber swollen in benzene was investigated.