Pyrolysis of thio- and isothio-cyanates. Part III. Pyrolysis of s-butyl isothiocyanate

Abstract

The gas phase decomposition of s-butyl isothiocyanate has been investigated in the temperature range 273—325 °C by use of a conventional static system. The calculated first-order rate constants are independent of the initial pressure within the experimental limits 47—350 mmHg and were fitted to the least-squares Arrhenius equation (i). k₁/s^–1= 10^{12·46 ± 0·25} exp [(–41,333 ± 645)/RT](i) The results are interpreted in terms of an homogeneous, unimolecular mechanism. The geometry and polar character of the transition state for isothiocyanate decomposition is discussed.