CHEMICAL KINETICS Chapter 16 a knowledge of the rate, or time dependence, of chemical change is of critical importance for the successful syn. thesis of new materials and for the utilization of the energy generated by a reaction. During the past century it has become clear that all macroscopic chemical processes consist of many elementary chemical reactions that are themselves simply a series of encounters between atomic or molecular species .. to understand the time-dependence . chemical kineticists have .. focussed on sorting out all of the elementary chemical reactions involved in a macro- Scopic chemical process and determining their respective rates. ‘Yuan T. Lee, Nobel Prize in Chemistry, 1986 ATOMS, MOLECULES, AND IONS MUST COLLIDE IN ORDER TO REACT Rates of Chemical Reactions factors that affect rate rate expressed in terms of reaction stoichiometry TEX I.) Consider the combustion of hydrogen gas: 2h(e) + On(@) > 2H,0(2) Ifhydrogen is burning atthe rate of 0.85 mol s, what isthe rate of consumption of oxygen? ‘What isthe rate of formation of water vapor? ) The reaction 2NO(g) + Ch(g) > 2NOCKg) is carried out in a closed vessel. If the partial pressure of NO is decreasing atthe rate of 23 mm Hg mi is the rate of change of the total pressure of the vessel? what how rate measured: average, instantaneous, FIG I - Disappearance of Reactant FIG IT-- Appearance of Product CaHia(g) + Oa(e) > CaH4O(2) + O,(@) NOx(g) + CO(g) > NO) + COX) ~ Ge 7 ABE ea me E urns Rave | “SN {bon A : savcotmaute'| Cie tL ve “9Rate Laws - Effect of Concentration on Rate (a way to categorize reactions) examples rate law (from experiment!) Hy@) + (@) > 2H) r= RMI} 2NO(g) + Ox() + 2 NOK) r= KINO;}[03] 2N,0,(8) > 4NOg(g) + Ox(8) 1 = KIN2O3] H,POx(ag) + OH™(ag) -> HPO}(aq) + H;(g) r= k{H;PO3)(0H 7? iE rt A(Ha|{Brg}°? Hyg) + Brig) > 2 HBr(e) ” = Gale FET order rate constant determination (see Rate Laws on website for mathematical description) al rate method: EX 2. Consider the gas-phase reaction between nitric oxide and bromine at 273°C. 2NO(g) + Br(g) + 2NOBr(2) “The following data forthe initial rate of appearance of NOBr were obtained Experiment {NO} [Br] Initial Rate 1 010M 020M 24Ms? 2 025 0.20 150 3 0.10 0.50 60 4 035 0.50 735 4) Determine the rate law ») Calculate the average value of the rate constant from the four datasets. ©) How is the rate of appearance of NOBr related to the rate of disappearance of Br,? 4) Whats the rate of disappearance of Bra when {NO} = 0.075 M and (Br] = 0.25 M? FIG III - Rate Law from Linear Regression on Initial Rate vs Concentration Data NH{(aq) +NO3(aq) —> No(g) +2 #200) Experiment Initial NH? ¥C°%L initia NO,” Ans Lobserved Initial “Savy Number Concentration (M) “Concentration (M)___Rate (Ms) 1 010-4605 0200-1609 = Saxio? — AB 2 0.0200 3.912 0.200 « wos x 107 713,94 3 oto ~3.ak 0.200 0 5x10? 713.05 4 0.0600 -2'813 0.200 . maxi0? — 16H 5 0200-1609 gp2 -3.202 108x107 — 13.48 6 020 0 ous 3.209 alex? -— TAOS 7 020 0 00608 2.803 324x107 - IAG 8 om 00808-2516 waaxig? 3S ye & Cong)" Quoc! tacks + cdr DHT + y Sv T005°7Integrated Rate Laws (Dependence of Concentration on Time) 1. first-order reaction FIG IV - Plot of a First-Order Reaction N,0s(g) -> 2.NO2(g) + 1/2 Ox(8) Time) sop Be ans integrated rate 1 i 3 z halflife 0 TeI0 ax 10 ax 108 Time(s) EX, The first-order rate constant forthe decomposition of NO; Ni0s(@) > 2NO4(g) + 1/2.Ox(8) at 70°C is 6. 82x 10° s“!, Suppose we start with 0.0250 mol of NzOx(g) in 2.0L. a) How many moles of N,Os will remain after 2,5 min? b) How many minutes will it take for the quantity of NOs to drop to 0.010 mol? ©) What is the half-life of NOs at 70°C?FIG V - Plots of a Second-Order Reaction 2. second-order reaction NOg(g) > NO(g) + 1/2 Ox(e) integrated rate & 89 100 200 300 half-life 1/[NO3) TEX 4, At300°C the rate constant forthe second order reaction NOx) > NO(g) + 1/2.0x(8) is 0.543 Mts“ Ifthe initial concentration of NO in a closed vessel is 0.0500 M, what is the concentration remaining after 0.500 br? 3. zero-order reaction integrated rateFIG VI - A Reaction Plotted as Various Orders 2.NO,(g) > 2 NO(g) + Ox(a) ow, - ror) Tad: Tale Too Se tade deta, Rat ob Tas TA3~ tet an ° one i ae Tao, - a a,* kt Se tt Toog tlm 0.01 0.0038 0.0066 0.0048 0.0088 F els ° ee 1G VII - A Comparison of Different Rate Laws For a general chemical reaction: aA > products where a denotes the stoichiometric coefficient. The rate law, integrated rate law, half-life, and form of concentration data giving a linear plot are summarized for various orders the reaction could follow. In the table k= ak where & isthe rate constant and a the stoichiometric coefficient. Onder Ratelaw | Integrated Half-life, ty Linear plot 0 (A= (Alfa aan (adver 1 InfA] = InfA]p — ket = InAvst or [A] = [Aloe “ imal T 2 amt a c t oe iar “ag Te o ad (eyrahdeilaeds | eerste alleen 4, fractional livesHow Do Chemical Reactions Occur? Explain Effect of Temperature on Rate collision model - kinetic theory interpretation: to react molecules need 1. to collide 2. to be properly oriented 3. to have a minimum translational Kinetic energy or activation energy (minimum collision energy reactants need inorder to form products) FIG IX - Pressure vs Time for Methyl Isocyanate Rearrangement CH N=C(g) > CHiC=N¢g) pet = Pree HNC BEBE FIG VIII - Collision of Cl with NOCI 1) NOCK(g) + no reaction cues CION(g) > Ch(g) + NO(e) oe «DO ao &@ oe Po aa 0 Reneneo FIG X - Reaction Coordinate for Methyl Isocyanate Rearrangement CH;NeC(g) > CH;C=N(g) where energy comes from: FIG XI - Maxwell-Boltzmann Distribution of Molecular Speeds sensors See eanare | FIG XII - Maxwell-Boltzmann Distribution of Molecular Kinetic Energies a CEC Lower temperature . Higher tomporature energy reared Molecular sped ns)kinetic theory rate model for elementary reaction: B + C > products - to react molecules need 1. to collide 2. to be properly oriented 3. to have a minimum kinetic energy, Ey then the rate, r becomes r = (total # of col jons) x (fraction oriented) x (fraction with E, [B] [C] (size) (speed) (fraction oriented) e™*!*? = k(B)[C] = Ae**" [B][C] Arrhenius equation EX'S, The rate constant for the first-order isomerization of cyclopropane, CjHg, to propene is 6.7% 10 sat 500°C. What is its value at 300°C? A = 1.6% 10" s"!, E, = 272 ki/mol EX 6. Solve for k(300) for the preceding example only using k(S00) = 6.7 x 10 ot se the vale forthe pre-exponential factor. A) |How Do Chemical Reactions Occur? Explain Effect of Concentration on Rate (Reaction Mechanisms) elementary steps molecularity principle of detailed balance rate-determining step reaction coordinate example Gas phase reaction of chlorine with chloroform is described by the stoichiometric equation Ch(g) + CHCI(g) > HCI(g) + CChi(g) A proposed mechanism for the reaction is Ch <=> 21 fast Iy/k Cl+CHCh + HCl+CCh slow CCh + Cl + CCh faut ky working with reaction mechanisms: sequence of elementary steps given steps sum to overall reaction (stoichiometric equation) Kg(Eas)s ke(Eae) foreach step know rate law for each step from molecularity overall rate law found if needed, rate-determining step approximation used prior rapid equilibria used to determine concentration of species not in overall stoichiometry intermediates, catalyst, inhibitors identified rate law compared with experiment, Kexp identified with rate constants and equilibrium constants of individual steps9. Reaction Mechanisms, Reaction Coordinates, and Activation Energy, E, 1. CH:NC(g) > CH3CN(g) EX 7. In this isomerization of methyl isonitrle to acetonitrile the rate was experimentally observed to obey the rate law r = keyglCHsNCI- {@) Show thatthe following mechanism is consistent with the rate law and ident Key. | proposed mechanism: CHNC(g) > CHANG) E@) TCR) | b) From the data in the table deduce the activation energy E, and the frequency factor An the Arthenius equation. Be sure to check the corelation coefficient on your calculator. 252x105 462.9 825x105 472.1 [630% 10% 503.5 [36x 107 524.4 [cc = -0,9997, 158 ki/mol, 1.82 10" s"!] TL. O5(g) + NO(g) > O2(g) + NOz(g) Fig 16.17, prob. 16.68) EX 8. For this reaction of the nitric oxide depletion of ozone in the upper atmosphere the rate was experimentally abserved to obey the rate law 1 = kaxglNONOs} 12) Show that the following mechanism is consistent with the rate law and identify Kx, proposed mechanism: Ox(g) + NOCg) > On(g) + NOx(g) kos) 700) >) From the data in the table deduce the activation energy E, and the frequency factor —— Ain the Arrhenius equation [ec =-0,9970, 11.9 ki/mol, 1.55 x 10! Ms] 1.08% 10? 195 | 2.9510? 230 | 542% 10? 260 |c) If AH? = -198.8 kJ/mol for the reaction what is E, for the reverse reaction? (210.8 ki/mol] 12.0% 10? 298 355% 10" 369 IIL. NOz(g) + CO(g) > NOCg) + CO,(g) (sample prob. 16.3, section 16.7, prob. 16.71) EX 9, The experimental rate law below 500 K is 7 = kagINOSF- 3) Show that the following mechanism is consistent with the rate law and identify Kay. NO, + NO; > NOs + NO slow ky NO, + CO + NO; + CO, fast ky ) What is the function of NO3? ¢) Determine A/H® forthe reaction from the following data co co; NO. NO, AH?(d/mol) -110.5 393.5 9037 33.84-10- IV. 2NO(g) + Ox(g) + 2.NO3(g) (Table and sample prob. 16.2, section 16.7, prob.16.64) EX 10. For this important smog reaction the experimental rate law is r = kexgl NOT [02]. '@) Show that the following mechanism is consistent withthe rate law and identify Kap Proposed mechanism: NO +NO <=> N,0y fast klk N,0; +0; > 2NO; slow ky 'b) What is the function of N,O2? ©) Activation energies are: 82(r,), 205 (r-.) , and 82 (r2) ki/mol, Ifthe Arhenius frequency factors are all approximately the same what happens to the overall rate as the temperature is increased? [r decreases with T V. 2Ce*(ag) + TI*(ag) > 2Ce*(ag) + TH*(aq) EX 11. The experimental rate law is r = keg(Ce*(Ag" ITT!" ICe™'1, 4) Show that the following mechanism is consistent with the rate law and identify Kea proposed mechanism: Cott Agh <> Ce + Apt fast klk TY + Ag > TP + Age slow I Tht + Ce TI + ce fast ky 'b) What is the function of Ag"?ie VI (aq) + ClO“(aq)_ > = TO™(ag) + CI(ag) (prob.16.62) [EK o. For his acon a alaie slaion i xperinenal ails r= I TGOT HOR ‘@) Show that the following mechanism is consistent with the rate law and identify kexp proposed mechanism: ClO” + H,0 <=> HOC! + OH fast klk r+ HOCI*— HOI + cr slow ky OW + HOI <=> IO + H,0 fast kefks 'b) What is the function of OF"? VIL. Hy(g) + In(g) > 2 HI(g) (sample prob. 16.3 follow-up prob., prob. 16.81) EX 13. The following two mechanisms have been proposed for this reaction. Show that they give the proper stoichiometry, determine the rate law they predict, give the function of all species, state the molecularity of each _step, and comment on each mechanistn. ‘mechanism I ‘mechanism II hh <> 21 fast kyle h <> 21 fast klk Hy +21 > 2HI slow ky Hy +1 <> Hy fast lofk HI +1 > 2HI slow ky-12- VII. O5(g) + O(g) > 202(g) (sample prob. 16.9, section 16.8, prob. 16.68) EX 14, Depletion of the ozone layer is believed to be caused by chlorine-catalyzed O decomposition. For the | uncatalyzed reaction Ey = 19 ki/mol. For the following mechanism, Ei =2.1 and Eyp. = 0.4 Ki/mol. ‘Proposed mechanism: Cl+0; > ClO +0; clo+0 + +0; 12) What is AH® for the reaction? £390 ki/mot} bb) What is £,,, forthe uncatalyzed reaction? [409 Kimo!) ©) Which step in the above mechanism is faster? 48) IEAH? for the first reaction is -165 kY/mol, sketch the energy profile for the reaction | AH (ki/mol) 1423 121.7 2475 IX. Reaction Coordinate for a Reaction A > B (prob. 16.67) TEX 15. Based on the following reaction profile Energy Reaction pathway a) What are the intermediates formed in the reaction? +b) How many transition states ae there? Identify them. ©) How many activated complexes ate there? Identify them, 4) Which step is the fastest? ) Which step is the slowest? 1) Is the reaction A_—> _B exothermic or endothermic?