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Lecture 26 - Chem 338 Lecture 26 Reactions in Solution 1...

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Chem 338 0 / ( ) ( / ) ( ) ( / ) E kT A B rate A B Q k T kT h E e d E kT Q Q κ γ γ γ = Chem 338 Lecture 26 Reactions in Solution 1. Liquid Structure a. Molecular dynamics and radial distribution functions, g ( r ) b. Polarity and solvation c. Cage effect d. Diffusion limit: k rate = k chem k diff / ( k chem + k diff ) e. Viscosity: k diff 8RT / 3 η H 2 O @ 25ºC , k diff 0.7 x 10 10 dm 3 mol –1 sec –1 2. Solution Transition State Theory a. Absolute rates b. Ionic strength c. Volume of activation ( ) ( ) 1 2 10 / log rate sol A B rate gas K T Z Z I K T
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Chem 338 Radial distribution function, g ( r ) , 2 1 1 4 ( ) dN g r N dr r π
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Chem 338 2 2 2 1 n R R i j k = + + Crystals have precise periodic structures n R n /R 1 N(R n ) 1 1 6 2 2 12 3 3 8 4 4 6 5 5 24 2 1 4 ( ) dN r g r N dr π
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Chem 338 Radial distribution function of a Solid Zero-Point Vibrations
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Chem 338 Radial distribution function of a gas
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Chem 338 Radial distribution function of a Liquid
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Chem 338 b. Polarity and solvation
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Chem 338 Differential solvation
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Chem 338 Nonpolar
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Chem 338 Ionic
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Chem 338 Ionic
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Chem 338 Solvent cage effect
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Chem 338 Encounters
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Chem 338 d. Diffusion limit: k rate = k chem k diff / ( k chem + k diff )
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Chem 338 Diffusion Limited Reaction Rates
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