Interpretation of the Transition‐State Parameter for Adiabatic Electron‐Transfer Reactions

1967 ◽  
Vol 47 (9) ◽  
pp. 3247-3248 ◽  
Author(s):  
R. Harris ◽  
W. D. Weir
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
State Parameter ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Adiabatic Electron Transfer

Quantum theory of inner sphere electron transfer reactions

1970 ◽  
Vol 23 (7) ◽  
pp. 1287 ◽  
Author(s):  
PP Schmidt
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Bond Formation ◽  
Transfer Reactions ◽  
Reaction Sequence ◽  
Electron Transfer Reactions ◽  
Bond Forming ◽  
Inner Sphere ◽  
Franck Condon ◽  
Activated Complex

This paper reports a theory of inner sphere electron transfer reactions for which, in addition to the electron transfer, there is bond formation and/or destruction. We assume that steps in the reaction sequence which involve bond synthesis take place in intermediate activated complex states. The problem of inner sphere electron transfer is large and complicated. The theory described applies to one aspect of the problem, namely, the dynamics of simultaneous electron transfer and bond break in the transition state complex. However, we assume the intermediate complex exists in steady state equilibrium with the reactants. The theory developed in this paper reveals features important in the unimolecular decay of the transition state. In particular, the importance of the Franck-Condon restrictions on bond forming and breaking steps is demonstrated.

scholarly journals Nonenzymatic NADH-Dependent Reduction of Keggin-Type 12-Tungstocobaltate(III) in Aqueous Medium

2011 ◽  
Vol 8 (3) ◽  
pp. 1152-1157
Author(s):  
Prabla Kumari ◽  
Alaka Das ◽  
Dillip Kumar Baral ◽  
A. K. Pattanaik ◽  
P. Mohanty
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Aqueous Medium ◽  
Transfer Reaction ◽  
Activation Parameters ◽  
Electron Transfer Reaction ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
First Order ◽  
Kinetics Of

The kinetics of the electron transfer reaction of NADH with 12-tungstocobaltate(III) has been studied over the range 5.07 ≤ 104[NADH] ≤ 15.22 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 20 ≤ t ≤ 35oC in aqueous medium. The electron transfer reaction showed first-order dependence each in [NADH]Tand [12-tungstocobaltate(III)]T. The products of the reaction were found to be NAD+and 12-tungstocobaltate(II). The activation parameters ΔH#(kJ mol-1) and ΔS#(JK-1mol-1) of the electron transfer reactions were found to be 64.4±1.8 and -48.86±6.0. Negative value of ΔS#is an indicative of an ordered transition state for the electron transfer reaction.

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