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The Thermal Decomposition of Ethyl Mercaptan and Ethyl Sulphide

1933; American Institute of Physics; Volume: 1; Issue: 1 Linguagem: Inglês

10.1063/1.1749223

1520-9032

Nelson R. Trenner, H. Austin Taylor,

Molecular Junctions and Nanostructures

The thermal decompositions of ethyl mercaptan and ethyl sulphide have been studied by a static method and shown to proceed homogeneously in glass vessels which have become poisoned by products of reaction. The rate curves of both exhibit an induction period shown to be due to a reaction between ethyl and hydrogen sulphides yielding what appears to be a dimercaptan. The subsequent decomposition of this intermediate is unimolecular but complicated by a reverse reaction. The energies of activation of formation and decomposition of the intermediate are each about 40,000 calories, the rate of formation being slightly greater than the rate of decomposition at temperatures around 400°C. The unimolecular rate falls off below 150 mm which would correspond with six squared terms involved in the activation. No foreign gas has been found to maintain the rate. The existence of a complex equilibrium detracts somewhat from the certainty of interpretation of data and mechanism. A critique of similar recent work substantiates the conclusions here drawn though differing from previous interpretations.