Modeling the isotope effect in Walden inversion reactions

Israel Schechter

doi:10.1016/0009-2614(91)87150-A

Modeling the isotope effect in Walden inversion reactions

Israel Schechter^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH₃T and CH₂TF from the reaction T + CH₃F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

Original language	English
Pages (from-to)	260-264
Number of pages	5
Journal	Chemical Physics Letters
Volume	180
Issue number	3
DOIs	https://doi.org/10.1016/0009-2614(91)87150-A
State	Published - 17 May 1991
Externally published	Yes

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title = "Modeling the isotope effect in Walden inversion reactions",

abstract = "A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH3T and CH2TF from the reaction T + CH3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.",

author = "Israel Schechter",

note = "Funding Information: I thank Professor B. Katz for raising the subject, providing the recent experimental data [ 11, and for useful discussions and help in preparation of the model. I also thank Professor R.D. Levine for suggesting the application of the model to reactions of hot atoms with methane and for stimulating discussions. The Fritz Haber Research Center is supported by Minerva Gesellschaft ftir die Forschung, mbH, Munich, Germany.",

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doi = "10.1016/0009-2614(91)87150-A",

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N1 - Funding Information: I thank Professor B. Katz for raising the subject, providing the recent experimental data [ 11, and for useful discussions and help in preparation of the model. I also thank Professor R.D. Levine for suggesting the application of the model to reactions of hot atoms with methane and for stimulating discussions. The Fritz Haber Research Center is supported by Minerva Gesellschaft ftir die Forschung, mbH, Munich, Germany.

PY - 1991/5/17

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N2 - A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH3T and CH2TF from the reaction T + CH3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

AB - A simple model to explain the isotope effect in the Walden exchange reaction is suggested. It is developed in the spirit of the line-of-centers models, and considers a hard-sphere collision that transfers energy from the relative translation to the desired vibrational mode, as well as geometrical properties and steric requirements. This model reproduces the recently measured cross sections for the reactions of hydrogen with isotopic silanes and older measurements of the substitution reactions of tritium atoms with isotopic methanes. Unlike previously given explanations, this model explains the effect of the attacking atom as well as of the other participating atoms. The model provides also qualitative explanation of the measured relative yields and thresholds of CH3T and CH2TF from the reaction T + CH3F. Predictions for isotope effects and cross sections of some unmeasured reactions are given.

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DO - 10.1016/0009-2614(91)87150-A

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SN - 0009-2614

VL - 180

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 3

ER -

Modeling the isotope effect in Walden inversion reactions

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