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The bimolecular reaction: C 2 H 5  + Cl 2  4 → C 2 H 5 Cl + Cl is studied in the very low pressure reactor (VLPR) system at 298K starting with Cl/C 2 H 6 /Cl 2  mixtures. Mass conservation is found to be 97 ± 3% for the overall chemical change in the system. From the C 2 H 5 Cl product formation kinetics, k 4 =(1.05±0.05)·10 -12 cm 3 /(molecule-s) is derived. Two independent estimates of the A factor gives A 4 =1.3 ·10 -12 cm 3 /(molecule-s). These parameters yield a positive activation energy of 0.13 kcal/mol in contrast with recently reported negative activation energy values. Some side reactions of small extent are initiated by H atom contamination in the system. The measurement of CH 3 Cl product formed from CH 3 +Cl 2  11 →CH 3 Cl+Cl gives k 11 =(3.4±0.3) · 10 -12 cm 3 /(molecule-s) with an estimated A factor of A 11 =5.0×10 -12 cm 3 /(molecules). The source of CH 3  radicals is the side reaction H+C 2 H 5 →2CH 3 .

zeitschrift für physikalische chemie

Detailed Kinetic Investigation of the C 2 H 5 +Cl 2  Reaction and Analysis of the Reaction of CH 3 +Cl 2  Initiated by H-Atom Contamination at 298K and at Millitorr Pressures