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Unformatted text preview: A] = k−1[ B ] k2 [ B ] = k−2 [C ] k3 [C ] = k−3[ A]
and multiplying all these together, we also find k1k2 k3 = 1 , k−1k−2 k−3
implying that the six rate constants are not independent of one another and that one of them can be expressed in terms of the other five. II. The Boltzmann distribution. Consider a molecule that can have different energies, ε1 , ε 2 , ε 3 ,... . Let us denote the molecule with energy ε i Ai. Assuming that interconversion between Ai and Aj is described by 1st order kinetics, we have: [Ai]/[Aj] = exp[
µi0/RT]/ exp[
µj0/RT] This relationship is valid for ANY i and j. This suggests [A]i = W exp[
µi0/RT] where W is a constant. Recalling that µ = U − TS + PV , [Ai] = W exp(−U i0 / RT ) exp( Si0 / R)...
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This note was uploaded on 04/24/2011 for the course CH 52635 taught by Professor Makarov during the Spring '11 term at University of Texas at Austin.
 Spring '11
 Makarov

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