Interpretation paradoxes in unimolecular heterolysis kinetics |
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Authors: | G F Dvorko |
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Institution: | 1.Kiev Polytechnic Institute,Kiev,Ukraine |
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Abstract: | The rate constant of the first-order rate equation w = kRX] that is derived from the variation of the reaction product concentration or determined by the verdazyl method characterizes
the lifetime of the transition state or that of the solvent-separated ion pair rather than the heterolysis rate. The diffusion
rate constant is equal to the dissociation rate constant of the contact ion pair and to the reverse of the lifetime of the
solvent-separated ion pair: k
D ≈ k = 1/τ ≈ 1010 s−1. |
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Keywords: | |
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