CHEMISTRY 112 School of Pharmacy University of California, San Francisco Question Set III: Answers 1.

The rate of a reaction with a high activation energy is affected more by a given temperature change than one with a low activation energy. This can be predicted by the equation ln (kT2/kT1) = (Ea/R){(T2 -T1 )/T1 T2 }. The smaller the size of Ea for given values of T1 and T2 , the smaller the ratio (kT2/kT1); this implies that k is affected by most by a given temperature change if the corresponding activation energy is large. In the extreme case when Ea = 0, raising the temperature has no effect k and, therefore, no effect on the rate of the corresponding reaction. 2. It provides an alternate pathway with a lower !G; the reaction can proceed at an enhanced rate over this pathway, as compared to the uncatalyzed pathway. Note that, in actuality, the uncatalyzed reaction still proceeds in competition with reaction via the catalyzed pathway; however the contribution of the uncatalyzed pathway to the amount of product formed is often very small, as compared to that formed via the catalyzed pathway. 3. In general, the slowest step in the reaction sequence leading from reactants to products will have a higher activation energy than the steps preceding it. However, a more accurate statement would be that the rate constant for the slowest step in the forward direction for a reaction sequence has a higher free energy of activation than the steps preceding it. 4. The important factor to consider in kinetics is the free energy of activation, not the free energy of reaction. Reactions that have a very negative free energy of reaction can be very slow if a step with a large positive free energy of activation lies on the pathway leading to products. Problem Set III: Solutions 1. At 25C and pH = 5, t1/2 = 500 min and kapp = 1.4 x 10-3, while at the same temperature and pH = 4, t1/2 = 50 min and kapp = 1.4 x 10-2. Since the half life for inversion of sucrose is constant at a given pH, it must be first order in sucrose or a = 1. Since increasing the hydrogen ion concentration by a factor of 10 decreases the half life by a factor of 10, the rate law must contain [H+] in the numerator. The apparent rate law at a particular pH can be written as d[sucrose]/dt = kapp[sucrose] = k[H+]b [sucrose]. However, since we have two values of kapp (at pH 4 and pH 5), we have two equations in two unknowns (k and b). Thus we can write 1.4 x 10-3 = k(10-5)b and 1.4 x 10-2 = k(10-4)b . Dividing the first by the second, we obtain 10 = (10-4/10-5)b = (10)b . Thus b = 1. Now, if we desired, we could calculate the true rate

100

Pt - Peq

10 0 5000 10000 15000 time (sec)

constant for the reaction (e.g. a rate constant that has no concentration dependence).

2. This data can be shown to represent a reversible first order reaction by plotting the data in an appropriate manner. The equation describing the data for such cases is ln{(Pt - Peq)/(P0 Peq)} = -{(k1 + k-1)t} or, alternatively, ln (Pt - Peq) = -{(k1 + k-1)t} + ln (P0 - Peq). This predicts that plotting of (Pt - Peq) vs. time on semi-log paper should yield a straight line. (We can take the percentage P of a product to be proportional to the concentration.) Evaluating the slope, we find it to be -7.52 x 10-5. From this value, we find (k1 + k-1) to be 7.52 x 10-5 sec-1. Using the relation Keq = [trans]eq/[cis]eq = k1 /k-1, we can calculate that Keq = 83/17 = 4.88. Therefore k1 = 4.88 k-1. Substituting for k1 in the expression for k1 + k-1 and solving for k-1, we find that k-1 = 1.28 x 10-5 sec-1. Then returning to k1 = 4.88 k-1, we find k1 = 6.23 x 10-5 sec-1. 3. There are two possible approaches to this problem. In the first, we plot the data and use the resulting graph to estimate the rate constant at -3 10C (283 K). We then use this rate constant, as -3.5 done below, to calculate how far the reaction proceeds in a given length of time. In the second log k -4 approach, we evaluate the activation energy and Arrhenius constant and then calculate the required -4.5 rate constant. Here, we use the first approach, the -5 graph from plotting the data given in the problem being shown above. The 1/T value at 283 K is -5.5 3.54 x 10-3. This corresponds to a rate constant of 3.31 x 10-6 sec-1. Now, the volume of gas -6 collected is 200 ml. We can calculate the number 3 3.1 3.2 3.3 3.4 3.5 3.6 of moles collected from n = PV/RT = (1 atm)(0.2 l)/(0.082 l atm K-1 mole-1)(283 K) = 3 -1 10 x 1/T, K 0.00863 moles. Now we can use the first order rate equation in its integrated form to calculate how long it will take to form this number of moles of gas. Rearranging the equation log{[A]0 /[A]} = kt/2.3, we obtain t = (2.3 log{[A]0 /[A]})/k. Substituting in, we obtain t = 2.3 {log (0.1)/(0.09137)}/3.31 x 10-6 = 27294 sec.= 454.9 min. = 7.58 hrs. 4. This problem involves plotting the total rate constant k as a function of [H+ ] and determining the slope and intercept of the resulting straight line. The resulting graph is shown below. From the intercept, we find k0 = 1.22 x 10-4 min-1 and, from the slope, we calculate kH+ = 3.45 x 10-3 liter mole-1 min-1. 2.75 -2.5

2.5 2.25 104 x k 2

1.75 1.5 1.25 1 0 0.01 0.02 0.03 0.04 0.05 [HClO4 ], M

5. (a) Since the reaction is first order in antibiotic, we can write [A] = [A]0 e- kt. For a 170 pound man the rate constant at 98.6F = 37C is 3.0 x 10-7 sec-1 lb-1 x W = 3.0 x 10-7 sec-1 lb-1 (170 lb) or k3 7 = 5.1 x 10-5 sec. The value of [A]0 is 500 mg/170 lb and [A] = 170 mg/170 lb. We calculate t from the rearranged first order integrated rate law as t = (2.3/k) log[A]0 /[A] = (2.3/5.1 x 10-5 sec-1) x log{(500 mg /170lb) /(170 mg/170 lb)} or the time required is 21.1 x 103 sec = 5.86 hours. (b) At 102.2F = 39C, the rate constant is 4.0 x 10-7 W sec-1 lb-1. For a 170 lb. man, the rate constant is 6.8 x 10-5 sec-1. As above, we find that t = 15.8 x 103 sec = 4.4 hours. (c) We have only two data points. However, we can make an estimate by use of the relation log (kT2/kT1) = -Ea/2.3R(1/T2 - 1/T1 ). Then log (6.8 x 10-5/5.1 x 10-5) = 0.125 = -{Ea/2.3(1.987)} x {(1/312) - (1/310)} = 4.5 x 10-6 Ea. Solving for Ea, we find its value to be 27.63 kcal or 115.6 kJ. 6. Since radioactive decay is a first order process and cpm is directly proportional to concentration, we can write ln {(cpm)a/(cpm)0 } = -kta, where ta is the age of the wood. Now k is equal to 0.693/t1/2; thus the right hand side of the equation becomes -0.693ta/t1/2 = -0.693ta/5760 years. Since the left hand side of the equation is given by ln (7.04/12.5), we can solve for ta and find it to be 4771 years. 7. Using the equation log (k/T) = log 2 x 101 0 + !S /2.3R - {!H /2.3R}x (1/T), we can plot log (k/T) vs. 1/T and obtain !H from the slope; then !S can be evaluated by picking a point on the graph and calculating the intercept. The resulting graph is shown below. From this graph, we calculate m = -2.15 x 103 and, thus !H = -2.3 Rm = 9.820 kcal = 41.086 kJ, while !S = -42.15 cal/deg = -176.4 J/deg. At 298 K, !G = 22.42 kcal/mole = 93.81 kJ/mole and K = 3.59 x 10-17.

10 107 x (k/T) 1 3.3 3.4 3.5 3.6 3.7 103 x (1/T)

8. We can write k1 = 2 x 101 0Te(!S1 /R)e-!H1 /RT and k2 = 2 x 101 0Te!S2 e-!H2 /RT . Taking the ratio k1 /k2 , we obtain k1 /k2 = e{(!S1 - !S2 )/R}e-(!H1 - !H2 )/RT. However, !H1 - !H2 = 0 and hence e-(!H1 - !H2 )/RT = e0 = 1. Then k1 /k2 = e(10 cal/deg mole)/1.987 cal deg mole = e5.03 or k1 /k2 = 153.3. Problem Set III: Old Exam Problem Solutions 1. (a) By mass balance, [A]0 = [A] + [B] + [C] + [D] at any time. Thus [A]0 = 0.2 M + 0.3 M + 0.4 M + 0.5 M = 1.4 M. (b) Since for parallel 1st order reactions at any time we can write k1 /k2 = [B]/[C], we find that k1 /k2 = 0.2 M/0.3 M = 0.67. (c) First we calculate k1 + k2 + k3 = k. To do this, we use the expression ln [A]/[A]0 = -kt = ln (0.5/1.4) = -k(60 min) or 1.03 = - k(60 min) or k = 0.0171 min-1. Then we use the fact that k3 /k2 = 0.4 M/0.3 M = 1.33. Thus we can write k = 0.67 k2 + k2 + 1.33 k2 = 3k2 = 0.0171 min-1. Therefore k2 = 0.0057 min-1. Since k3 = 1.33 k2 , we find that k3 = 0.0076 min-1. (d) We can use the equation ln [A] = ln [A]0 kt to do this calculation. Substituting in numerical values, we obtain ln [A] = ln 1.4 0.0171 min-1(120 min) = 0.337 2.05 = -1.713. Then [A] = .180 M. 2. (a) The data for reaction(2) can be represented by the equation ln (k/T) = ln 2x1010 + ! S /R !H /RT. This equation has the form of y = b + mx, where y = ln(k/T), b = ln 2x1010 + ! S /R, x = 1/T and m = - !H /R. Using data from the plot, the value of !H /R can be evaluated from the slope of the corresponding plot of k/T vs. 1/T. We find that m = -6159.1 and !H2 = -mR = 51.2 kJ. Now, picking the data point corresponding to x = 0.00215 and y = ln 300 = 5.7, we can calculate b from the relation b = y mx = 5.7 {(-6159.1)(.00215)} = 5.7 + 13.24 = 18.94. 10 Now, using the relation b = 18.94 = ln 2x10 + ! S /R = 23.72 + ! S 2 2 /R, we find that !S2 /R = - 4.78 or !S2 = - 39.7 J/K. 10 !S /R -!H /RT (b) Recall that k = 2x10 Te e . Now,taking the ratio k2 /k1 , we obtain k2 /k1 = 0.5 = a -b/T e e , where a = (!S2 -!S1 )/R and b = (!H2 -!H1 )/R. Then ln k2 /k1 = ln 0.5 = -0.693 =

(!S2 -!S1 )/R - (!H2 -!H1 )/RT = 5.9/R 8703/RT = 0.71 1047/T. Rearranging, we obtain 1.40T = 1047 or T = 748 K. (c) !G1 = !H1 - T! S = (42470 310(-45.6))J = 56.60 kJ ; ln K = ! G /RT = - 56660/8.314(310) 1 1 = - 21.9; thus K = 3.08x10-10. (d) At any time we can write [A] + [B] + [C] = [A]0 ; the fraction of the total material in the reaction mixture is then given by [B]/[A]0 = {k1 /(k1 + k2 )}{1-e-(k1 + k2)t}. Now, using the Eyring transition state equation k = 2x101 0Te!S /Re-!H /RT, we can calculate the values of k1 and k2 at 408 K. Substituting in for T (408 K) and the enthalpies and entropies of activation corresponding to k1 and k2 , we calculate that k1 = 1.71x105 and k2 = 1.91x104 . Adding these two terms together, we find that k1 + k2 = 1.90x105 . Then, we can write that [B]/[A]0 = (1.71x105 /1.90x105 ){1-e-1900000} = 0.90 after 10 min.