quiz3soln - CHEMISTRY 444.11 QUIZ 3 Spring 2008(08S NAME...

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(10 points) Consider the following reaction mechanism: A + A k 2 A * + A A * + A k 2 A + A A + M k 2 ' A * + M A * + M k 2 ' A + M A * k 1 B + C a. Write an expression for the rate of reaction in terms of the concentration of the activated complex A*. d [ B ] dt = k 1 [ A * ] b. Applying an appropriate approximation, determine the reaction rate in terms of the various rate constants, the concentration of A, and the concentration of M. d [ A * ] dt = k 2 [ A ] 2 k 2 [ A ][ A * ] + k 2 ' [ A ][ M ] k 2 ' [ A * ][ M ] k 1 [ A * ] Apply steady state approximation d [ A * ] dt 0 [ A * ] = k 2 [ A ] 2 + k 2 ' [ A ][ M ] k 1 + k 2 [ A ] + k 2 ' [ M ] Rate = d [ B ] dt = k 1 [ A * ] = k 1 k 2 [ A ] 2 + k 2 ' [ A ][ M ] k 1 + k 2 [ A ] + k 2 ' [ M ] If [M]=0, we have the Lindemann mechanism. c. What is the effective rate in the limit of very large concentrations of M? CHEMISTRY 444.11
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quiz3soln - CHEMISTRY 444.11 QUIZ 3 Spring 2008(08S NAME...

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