By Henry Eyring (Eds.)

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1) where C * is the concentration of activated complexes in a length along t h e reaction coordinate of ό* = Η(2πτη^Τ)w h i c h would be in e q u i librium with reactants, while Cb* represents the analogous quantity for activated complexes in equilibrium with p r o d u c t s . H e r e κ is the t r a n s mission coefficient (for the detailed discussion of t h e physical significance f 1/2 9 1. Theory of R e a c t i o n Rates i n C o n d e n s e d P h a s e s 23 of κ, see L i n etaL, 1971), a n d m* denotes t h e mass of t h e activated c o m plex i n motion t h r o u g h t h e distance δ* atop the potential energy barrier.

41) or E q . 43) 1/2 where β = (ε Ι2ε^Τ)(8πΝ β άΙ1000ε^Τ) . T h e effect of ionic strength on reactions between ions can be seen by substituting E q . 43) into E q . 44) B I n particular, for second-order reactions, a = 1, b = 1, a n d E q . 44) reduces to log k = log k ° + 2βζ ζ t t Α Β y/J. 51. A somewhat more precise form of E q . 45) for ions of finite size is log k = log * ° + 2βζ ζ [\ίμΊ(\ t r Α + v7)] Β (4-46) by using E q . 35), a/r == \/~μ , a n d repeating the foregoing derivation. F r o m E q .

T h i s is d e m onstrated in T a b l e V I by some b o n d cleavage reactions ( L e N o b l e , 1967). Volume changes of the solvent due to the reaction are also included in A V*. I n the process of ionization, there is a charge separation in the activated complex that is not present in t h e parent molecule. T h e presence of a charge induces a contraction of the solvent called electrostriction, so that the volume of activation should be negative. Typical magnitudes are —10 to —20 c m m o l e ( L e N o b l e , 1967).

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