Chapter 12_ Chemical Kinetics 283 Exercises Section 12.1 1. At40°C H,0,(aq) will decompose according tothe following reaction: 2H,0,(ag) ~ 2H,0() + Og) ‘The following data were collected for the concentration of H,O, at various times, timests LOU) 0 1.000 2.16 * 10° 0.500 43210! 0.250 % Calculate the average rate of decomposition of H,O, between 0 and 2.16 = 10" s, Use this rate to calculate the rate of production of O.(g) 'b. What are these rates for the time period 2.16 x 10's to 4.32 x 1085? 2. Given the following hypothetical equation and data fA ~ 9B +3C -ALA}It = 0.156 moVLs +A[BY/t = 0.026 mol/L s +A(CHt = 0.078 molt s find the coefficients fand g. Section 12. 3. Use the given data for the hypothetical reaction: 2A +B ~ products to determine the rate law and to evaluate the rate constant at 30°C. Reaction# = [A] {B]__[nital rate (mol/L. 1 Or on 3x10" zZ ol 03 3x 107 3 02 03 6x 107 4. Derive the rate law expression and calculate the rate constant for the reaction: A+B +3C ~ products given the following data for 15°C. Reaction# = [A] {B]_ {C} Initial rate (mol/L s) 1 04 01 On 6.0* 10" 2 04 02 01 6.0« 10 3 04 03 02 12% 107 4 nee az ou 5. Indicate the overall order of reaction for each of the following rate laws. = KINO,)[F,] = KOPIH] b « (H,JCL]* nae284 Chapter 12_Chemical Kinetics 6. The following hypothetical reaction was performed: A+ 2B+C+ 4D — products Determine the rate law and calculate the rate constant forthe following data collected at 20 Reaction # #1 8 « Dl Initial rate (mol/L. s) 1 025 030 0.60 O15, 7.20 107 2 075 030 060 015 217 «104 3 025 030. 020 0.15 7.20 «10° 4 0.75 030 0.60 0.45 6.51 «10 5 075 044 0.60 os 4.67» 10" Section 12. 7. The decomposition of H,0,(ag) into H,O(!) and O.(g) is first order, From the data in Problem 1, determine the rate constant and the half-life. 8. _ Using the answer from the previous problem, calculate the concentration of HO, remaining after 8 hours if the initial concentration was 5.0 M. 9. Determine the rate constant (k) and t, forthe data pertaining to the decomposition of phosphine (PH,) 4PH,(g) * P(g) + 6H,O() Reaction # PH] —-Rate(moVi.s 1 0.18 24® 10" 2 0.54 7.210? 3 1.08 14107 10. Using the data and answers from the previous problem, calculate the amount of PH, remaining after 2 ‘minutes, ifthe initial concentration of phosphine is 1.00 M. How mueh time would be needed for 90% of the phosphine to decompose? 11, _ Data for the decomposition of compound AB to give A and B is given below. Determine the rate expression, the rate constant, and t,, fora I M solution Reaction # 1B] Rate (moVL s) 1 02 3.210" 2 04 12.8% 10" 3 06 28.8 «107 12, The rate law for the following second-order reaction at 10°C can be written as 2NOBK(g) > 2NO(g) + Brig) [NOBr], where k = 0.80 Limol s Determine t, when [NOBr], ~ 0.650 M. b. Calculate [NOBr] at t= 5.80 10” s if [(NOBr], ~ 0.650 M. ©. If fNOBr], = 1.00 M, how long would it take for $0% NOBr to react? rate 13. Using the information in the previous problem, calculate [NOBr], if it took 4.31 s for 75% to react,Chapter 12_Chemical Kinetics 285 14. Theketone acid, (CH,COOH),CO, undergoes first-order decomposition in aqueous solutionto yield acetone and carbon dioxide: (CH,COOH),CO + (CH,),CO +2C0, 8, Write the expression rate forthe reaction. ». The rate constant, k, has been determined experimentally as $48 ~ 107, Calculate t, a 60°C ¢. The rate constant at O*C has been determined as 2.46 » 10", Calculate t, at this temperature 15. The decomposition of NOCI is a second-order reaction with k~ 4.0 * 10 Limol s, Given an inital concentration of 0.50 M, what isthe half-life? How much is left after 1 * 10"? Whats the half-life for an initial concentration of 0.25 M? 16, TBr(g) decomposes to form L(g) and Br,(g). A plot of 1/[Br]v. time gave a straight line. Write the general rate law for the reaction, 17, The rate law for the reaction: 2NOK) + Cig) > 2NOCKE) is R= KINO}{Cl]. If an experiment was performed in which the partial pressure of NO(g) initially was 0.1 atmand the initial partial pressure of Cl,(g) was 10 atm, what experimental data would give a straight line plot? 18. Forthe reaction A+B ~ C the following data were obtained + Inexperiment J, with 0.10 M as the initial concentrations for both A and B, the observed formation of Cis 1.0 10" Mimi, + Ineexperiment I, A and B are, respectively, 0.10 M and 0,30 M. The initial rate is 9.0 » 10° Mimi, + Inexperiment II, with the initial concentrations ofboth A and B at 0.30 M, the inital rte of formation i82.7 «10? Mimin. a, Write the rate law for the reaction. Calculate the value of the specific rate constant © Ifthe initial concentrations of both A and B are 0.40 M, what is the intial rate of formation of C? Section 12.6 19. Write the rate laws forthe following proposed mechanisms for the decomposition of IBr to I, and Br a IBr(g) ~ Iie) + Brig) (ast) IBr(g) + Brig) ~ Iie) + Br(g) low) 1g) * Wa) > 1s) (fast) b, IBi(g) > 1) + Brig) (low) Ug) + IBr(g) = Ig) + Brig) (fast) Brg) + Brig) > Brg) (fast) © IBx(g) + IBi(g) * 1.Br(@) + Br(@) (fast) LBr(g) ~ Brig) + L(g) (slow) Br(g) + Br(g) ~ Brg) (ast) 4. IBr(g) + IBr(g) > 12) + Brig) (one step) 20. Which of the following mechanisms are consistent with the observed rate law, R = (HOI 10,07), for the reaction HO, + 31 + 2H" > 24,0 + 1,286 Chapter 12_Chemical Kinetics fany are mot, write a rate equation that is consistent with the mechanism. a HO'+T + HI+ HO (fast) 1,0, + HI ~ H,O + HOI (slow) HOI + HO"+1 + 2H,0 +1, (fast) 7 r+h7y (fast) b, 1,0" + H,0, > H,0," + H,0 (ast) HO," + Fr 7 H,0 + HOD (slow) HOI + HO" + > 2H,0 +1, (ast) epee (fast) © HO, +I + 1,0 + On (slow) HO" +1 ~ HO + HI (fast) HO" + OF + HI ~ 28,0 +1, (fast) try (fast) “21. Write the rate law for the following predicted mechanism for the production of nitrogen dioxide (NO,) NO + 0, * NO, (fast) NO, + NO + 2NO; (slow) 22, Which of the following rate laws is consistent with the proposed mechanism for the reaction: 3C10" + ClO” + 2c1 ClO" + ClO + Clos + Cr (slow CIO + ClO” + CIO” + CI Cast) a. R=K{CIOJ[CIO,) b. R=KICIO'? c R=K{CIOF{CIO,) a RK{ClOF Section 12.7 23. The activation energy for the decomposition of H(g) to H,(g) and I,(g) is 186 kJ/mol, The rate constant at 555 K is 3.52 * 10°’ Limol s. What is the rate constant at 645 K? 24. The rate constant for the decomposition of acetone to carbonic acid was determined to be 6.42 « 10° Limo s at 10°C and 2.03 « 10° at 78°C. Calculate the activation energy. 25, The rate constant for the reaction: Cally 2H, at 325°C is 6.1 10°" 5", At 525°C, the rate constant is 3.16 = 10s". Calculate the activation energy. 26, The rate of a reaction increases 2.21 times as the temperature changes from 70°C to 80°C. Calculate the activation energy. 27. ‘The activation energy for the hypothetical reaction 2A + B ~ Cis 8.9 x 10* Jémol. If the original rate ofthe reaction is tripled ata temperature of 325 K, at what temperature did the reaction begin?7 28. 29, 31 Chapter 12 Chemical Kinetios 287 Multiple Choice Questions The rate of decomposition of ammonia to hydrogen gas and nitrogen gas, 2NH\(g) + Nig) + 3H.(@) is expressed as ~A[NHL,V/ t. Express the rate of reaction in terms of a{H,)/At A. Rate=23 A[HJAt B. Rate=A[Hilor C. Rate=3A(HJAt D. Rate=2 A(H,VAt Given the following information, calculate the average rate, A[SO,/At,, between 10 and 40 minutes for the production of SO;. 280, (g) 7 28042) + Og) [s0,] (SO,) {0;] 0.124 09 ci) 10.0 0.092 0.03: 0.01 20.0 0.068 0.056 0.028 30.0 0.050 0.074 0.037 40.0 0.037 0.087 0.044 50.0 0.028 0.096 0.048 AL 1.810% M/min BL 15% 10Mimin C. 3.0% 10% M/min — D, 3.210 M/min Given the following information, calculate the average rate, A[O,}/At , between 20 and 40 minutes for the production of O;, 280; (g) ~ 2SO,(g) + O.(g) (nin) {80 {803 ©, 00 0.28 00 00 109 0.092 0032 001 200 0.068 0.086 0.028 300 0.080 ors 0.037 400 0037 0.087 0.088 500 0.028 0.096 0.088 A. 8.0% 107 Mimin —-B, 1.6% 10? M/min C. 6.7% 10 Mimin D. 8.0 10 M/min Given the following information, calculate the average rate, - A[NH,)/At, between 10 and 30 minutes for the production of NH,, 2NH,(g) ~ Nig) + 3H,(2) (min) {NH,} {H,) 00 1.00 00 00 100 0.083, 0.034 oul 200 0.063 0.044 0.024 30.0 0.045 0.053 0.036 40.0 0.033 0.059 0.044 50.0 0.025 0.063 0.049 A. 80%10%Mimin — B. 1L9*10"Mimin C. 1.5% 10?Mimin D, 2.3 x 10" Mimin288 32 33 34. 35. 36. 37 Chapter 12__ Chemical Kinetics Based on the following equation, which one ofthe following compounds would you expect to undergo the ‘most change in concentration in a certain amount of time? INH (g) — Nfs) + 31K) A. Nitrogen B. Ammonia ©. Hydrogen D._ None of the molecules For the following reaction under circumstances where the reverse reaction can be neglected, the reaction rate will depend on which ofthe options below? AIC (g) + PH(g) + CLAIPE(@) A. AlCl, B. AICI, and PH, C. PH, D. CLAIPH, For the following rate law: RekIxP What is the order on X? a) B 4 co D3 Based on the following data, determine the rate law of this reaction: 80, (g)+ Clg) + SOCI, + C1018) Experiment [s0,] oy Initial rate (Mis) 1 0.400 0.400 0.2918 2 0.400 0200 0.0730 5) 0.400 0.800 1.1674 4 0.200 0.800 0.5837 A, R=K{SO,] B. R=k{SO,J{Ch] C. R=K{Cl,) D. R=K[SO,} {CLF Based on the following data, determine the rate constant for the reaction: $0,(g)+ Clg) + SOCl, +€1,0%8) Experiment [S0,] {C1 1) Initial rate (M/s) 1 0.400 0.400 0.2918 2 0.400 0.200 0.0730 3 0.400 0.800 1.1674 4 0.200 0.800 0.5837 AL 182 B. 9.12 Cc. 456 D. 0.0351 Based on the following data, determine the overall order of this reaction 2PO(g)+ Clg) > 2POCK(g) Experiment Poly (Cl) Initial rate (Mis) 1 0.20 0.20 0.40 2 0.20 0.40 0.80 3 0.60 020 32 4 0.60 0.60 96 a3 B2 © 52 D4Chapter 12_ Chemical Kinetics 289 38 39. 40. 41 42 4B 4s. 46. 47. Fill in the missing data item in this table: Experiment AB) (M) icv, . Initial rate (ne) t 1.00 0.500 Zz 2 1.00 0.730 2 3 2.00 0.750 3.002 4 1.00 0.250 0.5002 A. 1.002 B. 1.50Z c. 2.002 D. L75Z Jn @ zero-order rate expression, what units must the specific rate constant possess? ACU Bin c MA D. uMx+ The rate of decomposition of a substance is first order. If k = 2.46 = 10° s", what concentration of this substance remains after 2 minutes, knowing that (Substance), = 0.550 M? A. 0.409M B. 0.547M ©. 0553M D. 0739M A particular drug can be sold until 20% of the original drug has undergone change. Knowing that k= 1.25 x 10"/day and the change is frst order, how long, in days, will take before the drug ean no longer be sold? AL I7days B. 18 days C. 18hours D. 35 hours A gas phase reaction in which substance A reacts with substance B to produce AB, is found to be second orderon A. Knowing that k= 0.0368 M"! x hr, and that [A], = 2.25M, what percent of A remains after 177 hours of reaction? A. 3.31% B. 85.6% C. 144% D. 639% The decomposition of N;O gas obeys zero-order kinetics. Given a rate constant = 2.46 * 10 M’s and [N,O].2 = 0.155 M, calculate [N,O}, AL 0445M B. 0.450M Cc. 0550M D. 0.225M The decomposition of N,O gas obeys zero-order kinetics. Given a rate constant = 2.46 » 107 -M/s and [N,0], = 0.450 M, calculate (N,O] atthe end of 0.0445 hours. A, 0.0558 M B. 0221M ©. 0.225M D. 0.450M To determine whether data from different experiments correspond to a zero-order rate expression, a plot of ‘what variables will yield a straight line? A. (X]vs. 1 B. [X]vs.t C. WX}vs.t D. [xy A specific reaction is known to have a first-order rate expression. If ~ 1.52 « 10°Y/min, what the half life in minutes, of this reaction? A912 B. 667 B38 D. 456 ‘The following is a proposed mechanism for this reaction: Hyg) +Br(g) + 2HBrg) Br, + light > 2Br 2Br~ 2H, ~ 2HBr+ 2H HBr, + HBr+Br H+HBr > H,+Br Br+Br ~ Br, In this proposed mechanism, which steps are bimolecular’ Aa B. bode © all D. bed290 48, 49, 31 92 53, 54, 55 Chapter 12_Chemicai Kinetics The following is a proposed mechanism for this reaction: HL@)+ Bulg) > 2HBrg) Bry light ~* 2Br 2Br+2H, ~ 2HBr+2H H+ Br, > HBr+ Br H+HBr > H,+Br Br Br -* In this proposed mechanism, which step consists only of intermediates as reactants? Ae Boa CG od Db For a reaction to take place, the molecules that are reacting: A. Must have more energy than the produets 1B. Must have less energy than the products C. Must be able to reach the activation energy D. Must be in considerable numbers Which of the following is not a factor determining the energy of activation according to the Arthenius equation? ‘A. Orientation of molecules C. Frequency factor B. Temperature D. None ofthese choices Caleulate E, when k, =2.00 and k, = 10.0, T, = 318 K and T, = 371 K. A, 9.03 B. 300K) C. 850k D. 313 Calculate T, when E, = 30,0 kJ, T, = 285K, k, = 3.00, and ky = 15.0. AL 327K B. 253K C 158K D. 253K Ina “reaction progress” graph, reacting molecules are most unstable at A. Their initial position CC. Right after they collide B. When they are about to collide D. Atthe transition state A catalyst: A. Is consumed during a reaction, while effectively increasing the number of reacting molecules that can reach the energy of activation Changes an endothermic reaction into an exothermic reaction Increases the energy of the products Provides an altemate pathway tothe reaction, effectively lowering E, pow In which ofthe following examples isa heterogenous catalyst NOT used? Hydrogenation of fats Oxidation of sulfur dioxide Devomposition of ozone Catalytic converters of automobile exhaust systems poeChapter 12__Chemical Kinetics 291 Answers to Exercises 1. a, Average rate of decomposition of H,O; = 2.31 » 10° mol/L s Rate of production of O, = 1.16 * 10 mol/L. s b. Average rate of decomposition of H,O, = 1.16 « 10" moVL s Rate of production of 0, = 5.79 = 10 mol/L 3. RekiAKk=03s 4. R=K{APIC]: k= 0.38 Liimol? s 6 ReK{AIBPID], =2.14* 10 L''mol! s 7. k=3.21* 10%S%; y= 216 « 10's 8 20M 9. KALI RIO? Q.=538 10. (PH,]=0.21M; 177s =2 min. $7 see 11, R=KABF; k= 0.080 Limol s; t.,= 125s 12, a t= 192s b. [NOB] = 0.648 M c tn 128s 13, PNOBr], = 0.87 M 14. a. R=-K{(CH,COOH),CO} b.ty,= 12.64 seconds © ty, "281 * 10* seconds 15, tya(0.50M)=5.0* 10" s; [NOCH q ,=0.17 My tha(0.25 M) = 1% 108s 16, R=KUBrF 17, UNO} vs. pseudo-second order) 18, a ReATIBE k=0.1 Limos: © R= 0.064 mol/Ls 19, a R=K{IBY c. R= KIB b R=kilBr) 4 RekiBH 20, a and b; fore the rate Law would be R = KH,0,}(V) 21, R= KINO}{O) Get)292 Chapter 12_Chemical Kinetics 23. 9.76 « 10 Limol s 24. 98.0 kiimol 25, 2.61 * 10° Himol =261 ki/mol 26. 79.9 Kiimol 27. 315K 280A 2A 30. D 3B 32. 0c a3. B) 34D D 36.0 37. -D 38. OB 39. C 40. 4B 2. Dd B. 2B iA 45.8 46. D 7. 2B 48 A 9c 50. D 5B 520A 3D 4D 55. C “y