Problem_set_2

Problem_set_2 - Problem set 2, Chem. 127/227 fall quarter...

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1 Problem set 2 , Chem. 127/227 – fall quarter 2007 1. The Arrhenius function corresponding to the radical cyclization of the 5-hexenyl radical 1 is given by 9.3 – 5.0/ θ 1 2 (a) What is the Arrhenius activation energy for the process? (b) What is the value of the so-called pre-exponential factor? (c) What is the rate constant at 80 °C, one of the more commonly used temperatures for 5-exo,trig cyclizations? 2. Examine the transformations shown below. In one instance, the entropy of activation is +4.5 eu while in the other case, it’s –17 eu. (a) Match the reaction with the appropriate entropy of activation. (b) Which reaction will benefit the most in terms of reducing the activation barrier for the transformation by virtue of the activation entropy? Explain. (c) By how many kcal/mol will the entropy factor change the free energy of activation in each instance? Assume a temperature of 25 °C. (d) Formulate electron-pushing mechanisms to illustrate each transformation.
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Problem_set_2 - Problem set 2, Chem. 127/227 fall quarter...

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