Lecture 24

Lecture 24 - Chem 338 Lecture 24 Catalysis 1. Unimolecular...

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Chem 338 C h em 3 3 8 L e c t u r e 2 4 Catalysis 1. Unimolecular reactions a. Lindemann mechanism: R + B* R* + B P + B b. RRKM theory: R* P 2. Chain Reactions a. Initiation b. Propagation (inhibition) c. Termination 3. Catalysis a. Lower Δ G b. New mechanism 4. Enzyme kinetics a. Michaelis - Menton Mechanism b. Fits to data
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Chem 338
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Chem 338
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Chem 338
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Chem 338 B.S.
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Chem 338 The rate of a multistep reaction is ALWAYS determined ENTIRELY by the transition state with the highest Gibbs free energy. E a,1 E a,-1 E a,2 E a,1 + E a,2 - E a,-1 () ( ) ( ) 12 1 1 1 2 2 2 1 1 1 ‡‡ 2 - BB B RR R R B B R qV kT AA A hh h q V h Ah h k T h q V == =
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Chem 338 The rate of a multistep reaction is ALWAYS determined ENTIRELY by the transition state with the HIGHEST GIBBS FREE ENERGY . E a,1 + E a,2 - E a,-1 ( ) () 2 21 1 / B RB obs R qV kT E Ek T k h e −− =
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Chem 338
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Chem 338 2. Chain Reactions
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Chem 338 Steady State 32 1 2 [HBr] [H][Br ] d k dt =
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Chem 338 H 2 > HBr >> Br 2
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Chem 338 Steady State Steady State
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Chem 338 32 1 2 [HBr] [H][Br ] d k dt =
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Chem 338 3. Catalysis a. Lower Δ G b. New mechanism
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Chem 338 4. Enzyme kinetics
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Chem 338 Δ 5 -ketosteroid isomerase
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Chem 338 Δ 5 Δ 4 -androstene-3,17-dione
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Chem 338 Reaction Path -5 5 0 Energy (kcal/mol)
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This note was uploaded on 06/28/2010 for the course CHEM 338 taught by Professor Petersson during the Spring '10 term at Wesleyan.

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Lecture 24 - Chem 338 Lecture 24 Catalysis 1. Unimolecular...

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