The Unimolecular Decomposition of Gaseous Chloropicrin

The decomposition of gaseous chloropicrin has been investigated in the temperature range 138 to 170°C at pressures from 6 to 20 cm. The reaction is homogeneous and unimolecular, the rate constants being expressed by the equation $${\text{k=4.90×10}}^{15}{e}^{\text{−37670/RT}}\hspace{0.17em}\sec {.}^{\text{−1}}.$$ The products of the reaction are phosgene, nitrosyl chloride, nitric oxide, and chlorine, as represented stoichiometrically by the equation $$\begin{array}{c}{\mathrm{CCl}}_3{\mathrm{NO}}_2={\mathrm{COCl}}_2+\mathrm{NOCl}\\ \mathrm{\downarrow \; \uparrow \hspace{0.17em}\hspace{0.17em}}\\ \mathrm{NO}+\frac{1}{2}{\mathrm{Cl}}_2.\end{array}$$ There is, however, evidence to show that at least part of the nitric oxide and chlorine are formed otherwise than by the decomposition of nitrosyl chloride.