The progress of a reaction in the aqueous phase was monitored by the absorbance of a reactant ‘various times: ‘Timels 0 54 171-390-720 10101190 Absorbance 1.67 151 1.24 0847 0478 0301 0.216 Determine the order of the reaction and the rate constant. ‘The absorbance of a reactant is proportional to its concentration. The following plot shows. absorbance as a function of time for the reactant. 1s 16 i “4 | 12 10 208 2 06 os 02 00, © 100 200 300 400 500 600 700 800 900 1000 1100 1200 Time/s2 According to the plot, the absorbance decreases from 1.4 10 0.70 as t goes from 100 s to 505 s. ‘That is, the half-life is 405 s when the absorbance is 1.4, The absorbance decreases from 0.70 10 0.35, over the period + equals 50S s to 910 s. That is, the half-life is 405 s when the absorbance is 0.70. Since the half-life is independent of reactant concentration, this is a first order reaction. ‘Let [C} and [Cl be the concentrations of the reactant at time ¢ and at the beginning of the reactior respectively; and let A and Aq be the absorbance of the reactant at time ¢ and at the beginning of the reaction, respectively. Since this isa first-order reaction, [C] = [Cle* 1 Ao, iG, "4,7 Alot of In (A/Ag) vs t will give a straight line with a slope of —k. Tims 0 #0 D090 in(A/A,) 00000 ~0.1007 0.2977 0.6789 1251-1713 —2045 ‘The equation of the li 1.71 x 10-*x — 6.94 x 10°. Therefore, k = 1.71 x 10? isy= 00 02 a4 06 08 <0 2 ‘9 100 200 300 400 500 600 700 800 900 1000 1100 1200 Time/s ‘Cyclobutane decomposes to ethytene according tothe equation CyHy(e) + 2C,H,(@) Determine the order of the reaction and the rate constant based on the following pressures, which ‘were recorded when the reaction was carried out at 430°C in a constant-volume vessel: Timels Poy, /mmg 0 400 2000 316 4000 248 6000 196 8000 155 10000 12At constant temperature and volume, the pressure of cyclobutane is proportional to its ‘concentration. A plotof In P vs¢ shows a straight line with an equation of Y= —1.19 x 10° + 5.99. Thus, the reaction is first ordet. ‘The slope of the line is —k. In other words, k = 1.19 x 10-4s-!, . 55 a &s52 fs 48 : 46, ‘© 1000 2000 3000 4000 000 6000 7000 8000 9000 10000 Time/s the half-life of a compound if 75% of a given sample of the compound decomposes in ‘min? Assume first-order kinetics. ‘The rate constant is first calculated. [Al ia «* = In (1 ~ 0.75) = 2.31 x 10°? min=! ‘The half-life is7 12,137 The decomposition of N,O to N, and O, isa first-order reaction. At’730°C, the half-life ofthe ‘eaction is 3.58 x 10° min. If the initial pressure of N,O is 2.10 atm at 730°C, calculate the total {gas pressure after one half-life. Assume thatthe volume remains constant. ‘The reaction is N,0() — Ny(@) + 30,0) After one half-life, the pressure of N,O becomes 1.05 atm. Since an equal amount, 1.05 atm, of N,O reacts, 1.05 atm of N, and 1.05 atm/2 = 0.525 atm of O, are produced. Therefore, the total as pressure is P= Pyot Py, + Po, = 1.05 atm + 1.05 atm + 0.525 atm = 2.63 atm IF the first half-life of a zero-order reaction is 200 s, what will be the duration of the next fe? Since the first hal ‘The next half-if& Consider the following nuclear decay i j Seu Zn 8B 12.8 br | ‘ip Starting with one mole of “Cu, calculate the number of grams of “Zn formed after 25.6 hours. “Two half-lives would have elapsed after 25.6 hours. After the frst half-life, 1/2 mole of 'Cu ‘would remain. After the second half-life, 1/4 mol of “Cu would remain. Thus, a total of 3/4 mole of “Cu decays to form 3/4 mole of “Zn, The mass of “Zn produced is = G mel) (63.93 gmol"!) = 47.95 8eee following data were collected forthe reaction between hydrogen and nitric oxide at S °C: 2HH,(g) + 2NO(g) ~> 2H,O(6) + Ny(6) Experiment [H,VM (NOYM Initial ratefs~? 1 0010 0028 24x 10-6 2 0.0050 0,025 1.2.x 10-6 3 0.010 0.0125 0.60 x 10% (@) What is the rate law for the reaction? (b) Calculate the rate constant for the reaction, (©) Suggest a plausible reaction mechanism that is consistent with the rate law. (Hint: Assume that the oxygen atom is the intermediate.) (d) More careful studies of the reaction show that the rate law over a wide range of concentrations of reactants should be te = UNOPCH,) 1+) ‘What happens to the rate law at very high and very low hydrogen concentrations? (a) Comparing Experiment 1 and Experiment 2, the concentration of NO is constant and the | concentration of H, has decreased by one-half. The initial rate has also decreased by one-half. ‘Therefore, the initial rate is directly proportional to the concentration ‘of H,. That is, the reaction is first order in H. Comparing Experiment | and Experiment 3, the concentration of H, is constant and the ‘concentration of NO has decreased by one-half. The initial rate has decreased by one-fourth, ‘Therefore, the initial rate is proportional to the squared concentration of NO. That i, the reaction is second order in NO. ‘Therefore, the rate law is Rate INOPTH,) (b) Using Experiment 1 to calculate the rate constant, Rate, 24x 10-°Ms"! ee NOPE ~ Go2sm* oom ~ °°" () The rate law suggests that the slow step in the reaction mechanism will probably involve one H, molecule and two NO molecules. Additionally the hint suggests that the O atom is an intermediate, A plausible mechanism is, ! H,+2NO—+N,+H,0+0 ——slowstep +H, > HO fast step (@) At very high hydrogen concentrations, k, [H,] >> 1. Therefore, the rate law becomes _ AINOP EG) _ wen Em NT At very low hydrogen concentrations, ky (H,] < I. Therefore, the rate law becomes rate = k (NOP(H,]‘The rate law for the decomposition of ozone to molecular oxygen 20,() + 30,(@) israte= kT - The mechanism proposed for this process is 4 0, #0+0, a 040, 20, Derive the rate law from these elementary steps. Clearly state the assumptions you use in the derivation. Explain why the rate decreases with increasing Q, concentration. “The first step involves forward and reverse reactions that are much faster than the second step. The rates of the reaction in the first step are given by Forward rate = k,[03] = k_[0]0,] Assume that these two processes rapidly reach a state of dynamic equilibrium in which the rates of the forward and reverse reactions are equal: Reverse rat {04} = k_,[O](0;) Solving for [0], ‘The rate for the second step gives the rate of reaction, kaka (0,P" _ {050° Ky [0,] ~~ (0,] ‘The rate law shows that higher concentrations of O, will decrease the reaction rate. This is due to the reverse reaction inthe first step of the mechanism. If more O, molecules are present, they wi serve to scavenge free O atoms and thus slow the disappearance of O,, {04} : =p flO Rate = hfO103] = hag 1101s @ In recent years, ozone in the stratosphere has been depleted at an alarmingly fast rate by f wofluorocarbons (CFCs). A CFC molecule such as CFCI, is first decomposed by UV radiation: CFCI, —> CFCI, +CI ‘The chlorine radical then reacts with ozone as follows: C1+0, + ClO+0, Cl0+O > Cl+0, (@) Write the overall reaction for the last two steps. (b) What are the roles of C1 and C10? (c) Why is the fluorine radical not important in this mechanism? (@) One suggestion for reducing the concentration of chlorine radicals is to add hydrocarbons such as ethane (C,H,) tothe stratosphere. How will this approach work? (e) Draw potential energy versus reaction progress diagrams for the ‘uncatalyzed and catalyzed (by Cl) destruction of ozone: O, + O -> 20). Use the thermodynamic data in Appendix B to determine whether the reaction is exothermic or endothermic. (@) The sum of the following reactions +0, + cl0+0, co+0— ci+0, 0,+0— 20, (b) Clis a catalyst; C10 is an intermediate. (©) The C-F bond is stronger than the C-Cl bond. Thus, Cl is formed more easily than F (@) Ethane will remove the CI atom: CH, + Cl — C,H, + HCI© 2 uncatalyzed 2 E : 5 | 040, a & 2, Reaction progress catalyzed Cl+0+0, Potential Energy C10+0,+0 C1+20, Reaction Progress ‘The reaction is exothermic./pver a range of about 3° from normal body temperatre the metabolic rate, M,, i given My = Myy(11)*7, where Mg is the normal rate and AT is the change in T. Discuss this equation in terms ofa possible molecular interpretation, Source: “Eco-Chem,”J. A. Campbell, J Chem, Educ. 52,327 (1975)] es Converting to kelvin, and using the Arthenius equation, ne ._ Fe (F i ) My RAT ~ 310K, Since the temperature range is so small, f(T) = 4 — sro may be expanded in a Taylor series shout Ty = 310K. Keeping only the frsinon2eo tem results in (7) ~ —8F, whee AT = 310K - 7. Thus, . be pay" Which i ofthe observed form, providing an implicit factor of 1K is incorporated into the argument of the exponential function andthe A7 is interpreted asa unitless number. Specifically, it must be true that 1 In Lt = 0.0953, RT (1K™) (8.314 1K"! mot) (310 Ky? (0.0953) .6 x 10° mol! ‘This activation energy is consistent witha single rate determining step controlling the metabolic tate within this temperature range, etterial hydrolysis of fish muscle is twice as great at 2.2°C as at —1.1°C. if lue for this reaction. Is there any relation to the problem of storing fish for food? | | [Source: “Eco-Chem,” J. A. Campbell, J. Chem, Educ. 52, 390 (1975).] | Using the Arrhenius equation, with temperatures converted to the kelvin scale, | L 1 8.3143K™' mol™ (aaax ~ 21 z) I E, 2, = 1.3 x 10° Jmol! (Note that there is a math error in the solution given in the reference that makes the answer there too large by a factor of 3.37.) Nevertheless, this is a relatively large E,, and temperature will have a large effect on reaction rate, Thus, refrigeration is an essential, effective method of preserving fish and preventing spoilage. Note thatthe rate of bacterial hydrolysis at room temperature (298 K) is "74 times greater than the rate at 275.4 K. The rate constants for the first-order decomposition of an organic compound in solution are TReasured at several temperatures: Hs! 492x107 0.0216 0.0950 0.326 1.15 re 50 53545 Determine graphically the pre-exponential factor and the energy of activation for the reaction. Since E, | Ink=mnA~ 3 : A plotof ink vs 1/T gives a slope of —E,/R and an intercept of In A. The following data are used for the plot: WHT 3.595 3.470 3.353 3.253.143 | Ink/s) -5314 3835-2354 —1.121 0.140 1 ° i ry a2 z3 4 s Sn 32 33 34 35 36 Wo K/T ‘The equation for the line that best fits these points is y = ~1.207 x 10*x + 38.06. Therefore, .00 x 10 Jmol~! = ($1.207 x 104 K“') (8.314 K™! mol™!)ee 12.33) The rate at which tree crickets chirp is 2.0 x 10” per minute at 27°C but only 39.6 per minute /-C., From these data, calculate the “activation energy” for the chirping process. (Hint: The ratio of rates is equal to the ratio of rate constants.) Find the chirping rate at 15°C. First find the “activation energy” forthe chirping process. k nds eee i, RAT, n 20% 10? min7! E, Ae 39.6min —— 8.314SK~' mol! \300.2K — 278.2K, 5.11 x 104 Jmol"? E, = 5.111 x 108 Jmol [Now use one of the known rates and E, to find the chirping rate at 15°C (288.2 K). mB 4 (£-) Rae, ~~ M7, 7 5.111 x 10¢ Jmol 1 be 1 8.314) K"! mol” 288.2K 278.2 K, Rate, = 85.2 min“!1/3 (2H ne ‘equilibrium between dissolved CO, and carbonic acid can be represented by kn H+ HOS HCO fa 4a] bs sa] ke CO; + 20 Show that ED +49) 160,1~ (45 +2) arr ymco51 where K = [H*] [HCO; /[H,CO,]. From the equilibrium, (Co, ie 202)) = kys{H*HCO§ ] ~ kyylCO,) + bos CO) — fyglC0,) ‘Since HO is present in a great quantity, the effectively constant concentration, {HO}, is, incorporated into the constants ky, and ky.. Rearranging the expression gives ace Da — (iy eg) [C0,) + hf IHCO5] + £(H,C0,) 1244.1) Since H* and HCO; are in equilibrium with H,CO,, let (HCO; 1H,CO,) 1H,C0,) = erecon (12442) K= Substitute Eq, 12.44.2 into Eq, 12.44.1, (co, 05) SHCOA) a — y+ hg) [C04] + Kg TICO5) + fy EMBO == (bt fa) (C03 (hy + 4B) erramicozy (Co, ~AIGOSD 5 by by) [C04] — (« 9B) wa COs)74 (spe ‘certain elevated temperature, ammonia decomposes on the surface of tungsten metal as. fows: NH, — 3N, + FH, ‘The kinetic data are expressed as the variation ofthe half-life with the initial pressure of NHy: Pho 264 130 59 16 tals 456 228 102-60 (@) Determine the order of the reaction. (b) How does the order depend on the initial pressure? (©) How does the mechanism of the reaction vary with pressure? (@) The half-life of a reaction and the initial concentration are related by 1 fagt tae ‘where C is a constant. Taking the common logarithm of both sides of the equation, logt,2 = log C — (n — 1) log Aly ‘Since pressure is proportional to concentration at constant temperature, the above equation can also be written as tog typ = log C’ — (n ~ 1)log P A plot of log t, 2 vs log P gives a slope of n — 1. The data used for the plot are log(P/tor) 2.42 2114 1.97 1.20 ogtyn/8) 2.659 2358 2.009 1.78 There are clearly two types of behavior exhibited in the graph. At pressures above 50 torr the graph appears to be a straight line, and fitting to these three points results in a best fit line with an ‘equation of y = 1.00x + 0.24, Thus, 1 = —(n ~ 1), orm =O, and the reaction is zero-order. Although the data are limited, it is clear that there is a change in slope below 50 torr, indicating a change in reaction order. It does appear thatthe limiting slope as pressure approaches zero is itself zero. Thus, 0 = ~(n ~ 1), orn = 1, and the limiting behavior is that of a first-order reactionIS 10 12 14 16 18 20 22 24 26 og (P / torr) (@) As discovered in part (a), the reaction is first order at low pressures and zero order at pressures. above 50 tort. (© The mechanism is actually the same at all pressures considered. At low pressures, the fraction, of the tungsten surface covered is proportional to the pressure of NH,, so the rate of decomposition ‘will have a first order dependence on ammonia pressure. As discussed in Problem 12.16, however, at increased pressures, all the catalytic sites are occupied by, in this case, NH, molecules and the rate becomes independent of the ammonia pressure and zero order in NH.Ci bromination of acetone is acid-catalyzed: CH,COCH, + Br, © CH,COCH,Br+H* + Br "The rate of disappearance of bromine was measured for several different concentrations of acetone, bromine, and H* ions at a certain temperature: Rate of leappear [CH,COCH,VM (BeyyM UNM ance of Br Ms a) 030 0.050 0.080 5.7 10" @ 030 0.10 0.050 5.7 x 10° ® 030 0050 On 12x10 ® 0.40 008002 3.x 10 o 0.40 0.050 0.050 7.6 10-5 (a) What is the rate law for the reaction? (b) Determine the rate constant. (c) The following ‘mechanism has been proposed for the reaction: on HCCC, + HO (fast equim) c ae oem —e eins mo | Hota + HOt ‘Show that the rate law deduced from the mechanism is consistent with that shown in (a). (2) Comparing Experiment (1) and Experiment (5), the concentrations of Br, and H* are constant and the concentration of CH,COCH, has increased 1.33 times, The rate has also increased 1.33 times. Therefore, the rate is directly proportional to the concentration of CH,COCH. That is, the reaction is first order in CH,COCH,. ‘Comparing Experiment (1) and Experiment (2), the concentrations of CH,COCH, and H* are constant and the concentration of Br, has increased 2.0 times but the rate has not changed. ‘Therefore, the rate is independent of the concentration of Br,. That is, the reaction is zeroth order in Bry. (Comparing Experiment (1) and Experiment (3), the concentrations of CH,COCH, and Br, are ‘constant and the concentration of H* has increased 2.0 times. The rate has increased 2.1 times. ‘Therofore, the rate is directly proportional to the concentration of H*. That is the reaction is first order in Ht. ‘Therefore, the rate law is Rate = k{CH,COCH,]H*](7 (b) The rate constant can be calculated using data from any experiment. Using Exp. 1, Rate = 5.7 x 107 Ms“! = & (0.30 M) (0.050 M) k= 38x 10 ats! (©) Since step 2 is the slow step, Rate = k,[CH, COHCHY} J(H,0] (1254.1) ‘The intermediate, CH,COHCH] can be written in terms of the reactants using the first fast equilibrium step. Forward rate of step 1 4k, [CH,COCH, 104,0*] = [CH,COHCH} 11H, 0} Reverse rate of step 1 ._ (CH, COHCH J(H,0} Av tcH,cocH,IH,0°) (12.54.2) Et Substituting Eq, 12.54.2 into Eq, 12.54.1, the rate law becomes Rate = A cH,coce, 1,0") = Pucacocar) which has the same form as that shown in (a).a Gat seme (C,,H,20,;). commonly called table sugar, undergoes hydrolysis (reaction with er) to produce fructose (C,H,,0,) and glucose (C,H,,0,): Cr + HO —> Celi. fructose slucose ‘This reaction has particular significance in the candy industry. First, fructose is sweeter than sucrose. Second, a mixture of fructose and glucose, called invert sugar, does not crystallize, so candy made with this combination is chewier and not brittle as crystalline sucrose is. Sucrose is dextrorotatory (+) whereas the mixture of glucose and fructose resulting from inversion in Ievorotatory (—). Thus, a decrease in the concentration of sucrose will be accompanied by & proportional decrease in the optical rotation. (a) From the following kinetic data, show that the reaction is fist order and determine the rate constant. time/min ° 720° 180-70 ey ‘optical rotation (a) +2408" 421.40" 417.79 415.01" -10.73° (b) Explain why the rate law does not include [H,O] even though water isa reactant (a) The total change in rotation (from ¢ = 0 to # = 00), given by (ay — a,), will be proportional to the decrease in concentration of sucrose by that time. Therefore, the concentration of sucrose remaining at time t will be proportional to (9 ~ 0) ~ (aa) If the reaction is first order, thentf. A plot of [tn (a, ~ «,,) / (&% — a,,)] ¥S t should give a straight line with a slope of —k. The plot uses the following data: time/nin 0 120 0 2710 In(a,~a)/(%—a2) 0 8015x107 -020181 -0.30186 0.0 0s 0.10 -oas 020 In (= 0) ay 0.) 030 10 15 20 25 30 Time / min ‘The plot indeed results in a line described by y = —1.112 x 10-*x + 1.5 x 10~*, Therefore, the rate constant is 1.11 x 107? mi (B) The rate law does not include (H,O] because water is present in very high concentration (ca. ‘55.5 M) and this is a pseudo first-order reaction, Eee eee eee eeeeeee EEE206 12.59 ) Thallium) is oxidized by cerium(1V) in solution as follows: Tit +20e —> TH + 2Ce%* ‘The elementary steps, in the presence of Mn({I), are Cett + Mn?* —> Ce + Mn? Cet + Mn?* —> Co + Mntt Tit + Mn+ —> TI + Mn (@) Identify the catalyst, intermediates, and the rate-determining step if the rate law is rate = k[(Ce'*] {Mn**}, (b) Explain why the reaction is slow without the catalyst. (¢) Classify the type of catalysis (homogeneous or heterogeneous). (@) The catalyst is Mn*. It participates in the reaction but is regenerated at the end, The intermediates are Mn** and Mn‘*. ‘The first step is the rate-determining step because the rate depends on the concentrations of the reactants for that step. (b) Without the catalyst, the reaction would be a termolecular one involving 3 cations (TI* and two Ce**), The reaction would be slow. (©) The catalyst is @ homogeneous catalyst because it has the same phase (aqueous) as the reactants. Ganon ‘certain conditions the gas-phase decomposition of ozone is found to be second order in ‘and inhibited by molecular oxygen. Apply the steady-state approximation to the following ‘mechanisti to show that the rate law is consistent with the experimental observations: p 0, +0,+0 0+0, 20, ‘State any assumption made in the derivation. ‘The rate of decomposition of O, is a Hea = k,[0,] —&_[0,}[0] + k,[0]f0,} = k,[05} + (kq{03] — #_,[0,]) [0] (2.60.1) Apply the steady state approximation to O: £101 = 4,(0,)-4.,10,10] - {01105} =0 [ol= k,[0,) = Dota (12.602)2! Substitute Eq. 12.60.2 into Eq. 12.60.1: 4105) _ a 4,{0,] ~ TG = AilOa] + (F104 — kL0,]) E10.) 5101 = HikeslOsMOg}+ KtO3F , _KybelO,F* ___ ky. 1051104) TROD RIO EG10,) 4105] K(0,)+ 2,105) = blo? (12.603) &_[0,] + k,[05} Ifthe rate of the second step is assumed to be much slower than the rate of the reverse reaction for the first step, then k,[OMO5] « k_,{0,][0] 4104) « k_,10,) Equation 12.60.3 becomes 410g] _ 2kvkylOsP? dr k {0,1 ‘Since the rate for the reaction 20, -» 30, is —1{!%%! the rate law predicted by this mechanism is 4104) _ HbIOF a ~ &,10,7 Rate = which is consistent with experimental observations. 12461) The rte constants forthe reaction I nealtteec, 5 yo=feao —— Cr a have been measured at several temperatures: Wu's! 0.138 163 7.2 368 81 re 1553 2083 2465 2958 330.8 Calculate the values of the pre-exponential factor, E,, AS", and AH* for the reaction. Use $16 Kas the mean temperature for your calculation. (Data taken from G. B. Kistiakowsky and J. R. Lacher, J. Am. Chem. Soc. 58, 123 (1936),] Since ke Aen ERT E, Ink=InAoe A plot of Ink vs 1/T gives a straight line with a slope of ~E,/R and an interoept of In A. 1 KT 23337 2.0768 1.9242 1.7575 1.6556 Ink/M-!.s}) 8.8883 6.4192 -4.934 -3,3023 -2.513 2 3 a4 is = r4 ay 8 9 16 17° «1B 19-2022 10 K/T ‘The best fit ine has a formula of y = —9499x + 13.31. Therefore, .897 x 10° mol! (-9499 K) (8.314 TK mol”) 90 x 108 Jmol" A= el! = 6.032 x 10° Mo = 6.03 x 105 M's! For this gas-phase, bimolecular reaction, (see Equation 12.43) aT ast ye Anew tr (in ta as =8( mer 2 = (83143! mot”) [> (1M) (6.626 x 10-** Js) (6.032 x 10° M-! s = 155K" mor AH‘ = £,-2RT = 7.897 x 10" Smol~! — 2 (8.314 JK~! mol") (516 K) = 7.04 x 10S mol