CHEMISTRY 573

SPRING SEMESTER 2012 CHEMICAL KINETICS AND TRANSPORT

REVISED HOMEWORK # 2

February 1, 2012

(1) (a) Starting from the solution to Problem 1.9 in Steinfeld, Chapter 1, p 21, Obtain the corresponding integrated forms of the rate expression for the following three cases: (i) [B]0 >> [A]0 and [C]0 >> [A]0 , (ii) [C]0 >> [A]0 and [C]0 >> [B]0 , (iii)[A]0 = [B]0 = [C]0. As discussed in class, the solution to part (iii) of problem 1(a) is obtained in two steps. In the first reduction step shown in class via the lHopital relation, and using the simpler lower-case notation with a0 = [A]0 , b0 = [B]0 , and c0 = [C]0, we proceeded to set c0 = a0 and obtained the following integrated rate equation: (a0 b0)2 t = ln (b0 /b) ln (a0 /a) + (a0 b0)(1/a0 1/a) (1) The second reduction step for part (iii) of problem 1(a) is again done by the use of the lHopital relation by setting b0 = a0. so as to obtain the simple third-order integrated rate equation: 1/a2 1/a02 = 2 t da/dt = db/dt = a2b Now consider the rate law for the reaction 2A + B P, d[A]/dt = d[B]/dt = k3 [A]2[B] (4) Since we have already obtained the integrated rate equation (1) as the solution to the rate eqn. (3), we can exploit this result since a comparison of eqns, (3) and (4) reveals a close similarity. Thus make appropriate substitutions in eqn. (1) in order to obtain the integrated rate eqn. corresponding to the rate eqn. (4). The answer should agree with eqn. (1-57) on p.11 of Steinfeld. (2) Again starting from the solution to Problem 1.9 in Steinfeld, Chapter 1, p 21, obtain the integrated rate expression for the corresponding non-stoichiometric third-order reaction (A)A + (B)B + (C)C Products where the rate in terms of the three reactants should be defined in the usual way and is set equal to k3 [A][B][C]. Use the strategy discussed in class where one modifies the rate expression so as to make use of the integrated rate expression for the simple case of A = B = C = 1. This procedure avoids the need to carry out a cumbersome integration for the non-stoichiometric case. 1 (3) (2) (b) The integrated rate equation (1) shown above corresponds to the rate law: This follows since we modified the rate eqn. in Problem 1.9 by setting c0 = a0. and c = a.

(3) The selection of C&EN articles provided on Olefin Metathesis: Nobel Nod, The Early Days, & Big-Deal Reaction illustrates the typical complexity but also in this case a particularly beautiful and industrially important overall reaction (recall our introductory discussion). This is a chain reaction with initiation and propagation steps. The reactive intermediate that acts as the chain carrier in the reaction is a metal carbene of the form MY, where Y can be A, B, C, or D. Please read the article carefully (a fuller version is available online) and answer the following questions: (a) With the help of the mechanism shown on the first page of the Dec 23, 2002 article on The Early Days (p 5 counting from the front), list all the propagating species that can take part in the reaction. (b) List all the different olefin products that can be formed in the metathesis of the AB and CD starting olefins present in equal concentrations. What would be the statistical distribution if we were to assume that all of the possible overall metathesis reactions can be considered to be of neutral ergonicity (i.e., rG = 0)? (c) (i) The article mentions a high turnover number for a new Grubbs-type catalyst. The turnover number represents the number of molecules that react for each catalyst molecule that becomes inactivated in the process. How could this inactivation occur? (ii) Also of great importance in respect of the kinetics is the turnover frequency which represents the number of molecules that react at each catalyst molecule per second. Use an assumed turnover frequency of 5 x 104 s1 to calculate the rate constant for bimolecular propagation, assuming (i) that the initation step proceeds to completion, (ii) that the different propagating reactions all occur with the same rate constant, and (iii) that the total olefin concentration ( [olefin]) is ~10 M. (d) If we were again to assume that the two olefin reactants AB and CD have the same free energies of formation as all of the possible olefin products such that all of the possible overall reactions can be considered to be of neutral ergonicity (i.e., rG = 0), would the reaction still occur, and if so, what in this case would constitute the driving force for the metathesis reaction?