Analysis of flow dynamics in a new, very low pressure reactor. Application to the reaction: Cl + CH4⇌ HCl + CH3

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Abstract
A new, improved variant of the very low pressure reactor (VLPR) system with interchangeable discharge orifices was used for studying the compatibility of the chemical and physical processes occurring simultaneously. It is shown that the ratio of calculated and effective escape rate constants is a complex function of the reactor cell geometry for reactions of non‐spherical symmetry.The test reaction of atomic chlorine with methane proved to be a pure chemical process free of side reactions and was used to calibrate the system. The measured rate constant is k1 = (0.993 ± 0.013) × 10‐13 cm3/molec‐s at 25°C. A new procedure is outlined for measuring the equilibrium constant by changing the concentrations of all three components resulting in a remarkable accuracy of K1 = 1.406 ± 0.034 for the test reaction at 25°C.