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Kinetic isotope effects in the reactions of bromine atoms with CH4 and CD4

✍ Scribed by Toshitsugu Yokota; Richard B. Timmons

Publisher: John Wiley and Sons
Year: 1970
Tongue: English
Weight: 462 KB
Volume: 2
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550020407

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✦ Synopsis

The competitive reactions of Br atoms with CH, and CD, were studied over the temperature range of 562' to 637°K. Over this temperature interval, the kinetic isotope effect, k,/k,, varied from 3.05 to 2.47 for the reactions Br + CH, -% HBr + CH,

The rate constant ratio k,/k, , expressed in Arrhenius form, was found to equal (1.10 f 0.05) exp (1030 f 6 0 / R T ) . A comparison is presented between the experimental result and the result obtained theoretically from absolute rate theory using the London-Eyring-Polanyi-Sato (LEPS) method of constructing the potential energy surface of the reaction.

The agreement between theory and experiment is very poor, and this is believed to arise from the highly unsymmetrical nature of the potential energy surface involved in these reactions. A comparison is also presented between the k,/k, values obtained in the Br + CH,-CD, experiments and the available data on the corresponding C1 + CH,-CD, reactions.

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