Lecture8 - Rate constants for bimolecular reactions in...

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1 Physical Chemistry Lecture 8 Reactions in solution and relaxation methods in fast kinetics The cage effect In solution, solvent is a major factor in kinetics Limited proximity of reactants Molecules must diffuse into reaction zone 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  B A B A eff B A B A r r D D L k B A r r D D L v ) ( 4 ] ][ [ ) ( 4 Products B A Rate constants for bimolecular 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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This note was uploaded on 02/02/2012 for the course CHEM 419 taught by Professor Staff during the Fall '10 term at University of Delaware.

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Lecture8 - Rate constants for bimolecular reactions in...

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