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18 Nov 2019
Anomalous Arrhenius. (Modified from Silbey 18.30) For the generic single-step reaction, below, draw an Arrhenius plot (In(k) vs 1/T). Is the reaction faster at high temperatures or low temperatures? A + B rightarrow AB Now consider the reaction B+C+D rightarrow E which is comprised of the two steps shown below where all reactions are first order for all species. The first step is a rapid equilibrium between B, C and BC, with equilibrium constant K = [BC]/([B][C]). B+C rightwards harpoon over leftwards harpoon BC BC + D rightarrow E Show that the dependence of the overall reaction rate on temperature is given by the equation below, where delta H degree is the enthalpy change for the first step and E _a, is the activation barrier for the second step. k = A exp [- (E _a + delta h bar degree)/RT] Under what condition does the rate constant, above, have the opposite temperature dependence to that shown in part a)?
Anomalous Arrhenius. (Modified from Silbey 18.30) For the generic single-step reaction, below, draw an Arrhenius plot (In(k) vs 1/T). Is the reaction faster at high temperatures or low temperatures? A + B rightarrow AB Now consider the reaction B+C+D rightarrow E which is comprised of the two steps shown below where all reactions are first order for all species. The first step is a rapid equilibrium between B, C and BC, with equilibrium constant K = [BC]/([B][C]). B+C rightwards harpoon over leftwards harpoon BC BC + D rightarrow E Show that the dependence of the overall reaction rate on temperature is given by the equation below, where delta H degree is the enthalpy change for the first step and E _a, is the activation barrier for the second step. k = A exp [- (E _a + delta h bar degree)/RT] Under what condition does the rate constant, above, have the opposite temperature dependence to that shown in part a)?
Lelia LubowitzLv2
6 May 2019