Lecture8 - Physical Chemistry Lecture 8 Reactions in...

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Physical Chemistry Lecture 8 Reactions in solution and relaxation methods in fast kinetics
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The cage effect In solution, solvent is a major factor in kinetics Limited proximity of reactants Molecules must diffuse into reaction zone
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Diffusion control Limiting behavior EVERY molecule entering the cage reacts Diffusive motions control the time it takes to enter the cage Simple bimolecular reaction with diffusion control Typical size of diffusion- controlled rate constant k eff 4 10 9 dm 3 mol -1 s -1 AB B A eff AB B A d D D L k B A d D D L v ) ( 4 ] ][ [ ) ( 4 Products B A
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reactions in solution Reaction k (298 K)/ (dm 3 mol -1 s -1 ) H + + HS - H 2 S 7.5 10 10 H + + CH 3 OH CH 3 OH 2 + 1 10 8 OH - + HCO 3 - CO 3 2- + H 2 O 6 10 9 OH - + CH 3 OH CH 3 O - + H 2 O 3 10 6 OH - + p-C 6 H 4 (COOC 2 H 5 ) 2 p-C 2 H 5 OOCC 6 H 4 COO - + H 2 O 5.4 10 -2 hemoglobin 3 O 2 + O 2 hemoglobin 4 O 2 2 10 7 From W. C. Gardiner, Jr.,
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Lecture8 - Physical Chemistry Lecture 8 Reactions in...

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