THE KINETICS OF COMPLEX REACTIONS 477 ‘That is, the rate is a maximum when [A] = 2{P], which occurs at Ag—x=2Po+2x, or x= 4(Ao—2Po); y= $1 —2p). Substituting this condition into the integrated rate law gives 1 1 I Ao(Aa + Podkinas = (4) (3a —2p) +n x) I+p or} (Ao + Po)?ktmax = 5 In2p d{P © ae MAIPY. de qt h4o— Pot)? =P Pol f dae a= ee ee fo Ag —2)(Po +x? Integrate by partial fractions (as in part (4) 1 a 1 \ 1 1 1 ee (x vm) L {(as3) +(aan) [ne acealfe 1 1 1 1 Po+x Ao -(s3%) (e-maz)* (oem) [n( Po )+m()]] jf i x 1 (Po+xAo = (aan) (raza) * (erm) "(rracas) | Therefore, with y = —*— and p = 72 erefore, with y= —— and p = 72, > Tal P= Ao y I (Ag + Po)kt = a ae es Aono em +(ap)m( ‘The rate is maximum when = 2K(AIP] (@) +k (®) rr = 2KAJIPlvp — APP vp = A[PJQLA] — [Pvp = 0. 7a That is, at [A] = 3[P]. (On substitution of this condition into the integrated rate law, we find 2-p 1 2 AalAc Po)ktewax = | ————— — = ag? (gata) (a) "3 or (Ao + Po)?ktimax =23.19 P23.21 23.23 478 STUDENT'S SOLUTIONS MANUAL. A>2R I. A+R>R4B kp R+R>R. he ao ; IR] _ 2 Gp = LS RIAMRI] “ZF = 21 — 2st? = 0. 12 ‘The latter implies that [R] = (i) sand so ks y" Al B] _ _ rye) P= ntl = (2) 1a {Al dt k; ‘Therefore, only the combination =; may be determined if the reaction attains a steady state k; 5) COMMENT. Ifthe reaction can be monitored at short enough times so that termination is negligible compared to initiation, then [R] ~ 2it and 481 = kgtt [A]. So monitoring B sheds light on just kz. AENEOS — 1 — kalCHCOd5]ICO] fa ICHCO)sIIMI-+ KelCH{CO)gM] = 0 [steady state, _ 1+ kafCr(CO)sM] Henes, (COs = Teor peat d[Cr(CO)5M) MEKCONSM — ta {CH(CO}s|IM] — ks CH{CO)ML Substituting for [Cr(CO)s] from above, AICK(CO)sM] _ ks/IM] ~ kekalCr(CO)sMICO} a RICO} + ksIM1 —fICHCO)sMI kaka[CO] "S=) BICOL+ kM and we have taken k3/{M] << koka[Cr(CO)sMI[CO]. Therefore, ell s{M] Fy” keks{CO} and a graph of 1/f against [M] should be a straight line. Solutions to applications (a) The mechanism considered is,THE KINETICS OF COMPLEX REACTIONS 479 ‘We apply the steady-state approximation to ((ES)]. d{ES) ” Jt TES! = sg (E11S] ~ A065) — 4 (CES)] + KLENIPL = 0. Substituting [E] = [Elo — [(ES)] we obtain a (LElo — (CES) )[S] — k,{(ES)] — ku{(ES)] + &((E]o — (CES))[P] = 0. (-kalS] = ky — ky — KG[PDIES)] + KalE ofS] — AG{EJoLP] = 0. _ WEP, (S] + (K,/ka) LElolP, fia: {cesy) = AAfEIISI + KEIo(PL _ TEloLS1+ (Ky/ke) [ElofP [r= K 18), KalS] + ky + ky + AIP] Kit + 1S] + (Ki /Aa) (PT fa TE ofS] + (j,/Ka) [ElolP] Ku + (81+ (k/4a) [PI] TElolS] + (Kj, /ka) [Elo P] x [ IElo = Ky + {S] + (kj/ka) [PL _ Ay [TET0IS1-+ (4 /ha) [Elo(P I] — AG IE]oIP IR. 7 Kyu + (S] + (kj/ka) (PI : Then, AOI — a(S) — KIPIIE] = —KIPI Substituting for Kyq in the numerator and rearranging UP} _ AxfEloIS}-+ (K/h) [ElolP] [- a om dt KM +18) + (K/ka) [P] dr (b) For large concentrations of substrate, stich that [S] >> Ky and (S] >> [P], which is the same as for the unmodified mechanism. For [S] >> Ky, but [S] © (P] ty IS] = &/k)IP] ky a = AelElo SIF O/kDIP] k ie a(P] ‘Kk (Elo[P] —K(Elo[P] For [S] + 0, = = 20 _| all eae tee Kathe + KP] | Kp + [Pl ¥ where kp = che Ky23,25 480 STUDENT'S SOLUTIONS MANUAL COMMENT. The negative sign in the expression for d[P|/dt for the case [S] — 0 is to be interpreted to ean that the mechanism in this case is the reverse of the mechanism for the case [P] + 0. The roles of P and S are interchanged. Question. Can you demonstrate the last staternent in the comment above? (a) 7 [ATP}/(umol dm~) 0.60 080 14 20 3.0 v/(umoldm=3s~') 0.81 0.97 1.30 147 1.69 v/[ATP]/ s! 135 1.21 0929 0.735 0.563 Yenax 1+ KwlSlo Taking the inverse and multiplying by Vmax. We find that v Ym = V+ KM eer Thus, v 7 v= Vmax — Km = (Eadie—Hofstee plot) or | ——~ Miso P {Slo (b) The regression slope and intercept of the Eadie-Hofstee data plot of v against »/[Slo gives —Km and Vmax. respectively. Alternatively, the regression slope and intercept of an altemative form of the Eadie-Hofstee data plot of v/[S]o against v gives —1/Ky, and vmax/Km, respectively. The slope and intercept of the latter plot can be used in the calculation of Ky and Vinax- (© We draw up the following table, which includes data rows required for a Eadie-Hofstee plot (v against v/[S]o). The linear regression fit is found for the plot as seen in Fig. 23.4. "| and Kw 1.10 pmol dm~3 _ 1s % 12 = y=-1.1015«+ 2.3031 | £ as 20.998 = WSs23.27 THE KINETICS OF COMPLEX REACTIONS 481 When using reaction rates v, the Lineweaver-Burk plot without inhibition [23.22] has the form: Ky 1 +) Vinax ) [Slo where the intercept and slope are simple functions of van and Ky. When using reaction rates relative to a specific, non-inhibited rate (vze1 = V/Vreferene). the Lineweaver-Burk plot without inhibition has the same basic form: 1 1 Kw 1 a + 2a Yet Vmaxrel \Ymax,ret / [Slo The linear regression fit of the non-inhibited Lineweaver-Burk data plot is = 0.797 + (2.17). W . R= 0.980. Yrel [CBGP]o/10-? mol dm~> Jintercept = 1/0.797 Consequently, Yinaxset 25 and Ky = slope vmaxset = (2.17 x 10-? mol dm~) x (1.25) = 2.71 x 10-? mol dm~, ‘The Lineweaver-Burk plot with inhibition has the basic form ak \ 1 + = Yrel Ymax,rel. \¥max,ret / [Slo ‘The linear regression fit of the Lineweaver-Burk data plot for phenylbutyrate ion inhibition is ————____, =0.972. [CBGP]o/10~? mol dm~* 1.02 + (6.01) Therefore, a’ = intercept * Vmaxret = 1.02 x 1.25 = 1.28 and a = slope X Vmnaxset/Ko = (6.01 x 10-? mol dm~) x (1.25)/(2.71 x 10°? mol dm~3) = 2.77. Since both a > 1 and a’ ~ 1 (see Section 23.6(c)), we conclude that phenylbutyrate ion is a competitive inhibitor of carboxypeptidase. ‘The linear regression fit of the Lineweaver-Burk data plot for benzoate ion inhibition is, L {CBGP]o/10-? mol dm 75 + (3.01) Therefore. a’ = intercept x Vinaxret = 3.75 x 1.25 = 4.69 and @ = slope x Vinas.ca/KM = 3.01 x 10 mol dm) x (1.25)/(2.71 x 10-? mol dm~3) = 1.39. Since both a ~ 1 anda’ > 1, we conclude that benzoate ion is an [ uncompetitive | inhibitor of carboxypeptidase.P23.29 © P23.31 23.33 482 STUDENT'S SOLUTIONS MANUAL _ te _ = oo % 6 r= 2338], RE + RP Er= [23.37] Equating these two expressions for Er and solving for R gives RE at RE+Ro ty eR RE 1 (t/t0)" RYe 1 6 (rote es «a(R Ro. =e) = (t/%9) = @/70) We 1/t9 = 10 ps/10* ps = 0.010 and R= 5.6 nm (:"H0t0 =[260m Hypothesis: The 1270 nm emission band is the emission of the first excited state of On(a' As) as it returns to the O2 ground state (7, ). The singlet oxygen is produced by porphyrin photosensitization pS P4380) > P02. 30 porphyrin Test of hypothesis: tis well known that the dioxygen state a! A+ is 0,977 eV (1270 nm) above the ground state. If the hypothesis is correct the emission intensity should be proportional to both the concentration of dissolved oxygen and to the intensity of the porphyrin absorption, (@ ky =6.2 x 10™cm® molecule ky = 8.0 x 10° cm} molecule” ‘The concentration of atomic oxygen will be very, very small making a binary collision between atomic oxygen extremely unlikely. In fact, the reaction O+0+M—O2+M v=ks[OPIM] is ternary which makes it even less likely. Rate terms in ks may be safely omitted from consideration, (b) For all practical purposes d{Oz]/dt = 0 because very little dioxygen reacts to form either atomic ‘oxygen or ozone. Using ‘molecules per cm", or simply cm}, as the concentration unit, we find that Nap _ Na(10Torr) [021 = FF ROOK) = 3.239 x 10!7 molecules cm’ d[O} OT = 2102] —fafOM102P + #al0a1 ~ ksfOHOs}, = a3 — ay[O] + a3[O3] — a4[O][Os}, dl oi = kx{OM Oz}? ~ kafOs] — ks[O1O5} = a2[O} — a3[03] — agO][O3],THE KINETICS OF COMPLEX REACTIONS 483 where a, = 2k\{O2] = 6.478 x 10° 5! cm a = kx{On]* = 65.0368"', ky =0.016s"', a 4 = ky = 8.0 x 107 cm? (©) We break the time period in two. The early period encompasses the first 0.05 s with the initial conditions [Oo = [O3}o = 0. The second period covers the remainder of the 4 hours with the initial conditions provided by the [Oloos s = [O3loos s values of the early period. Numerical integration of the coupled differential equations yields the concentrations of Figs 23.5(a), (b), and (c).. Early period 2 T T T 4 f (031 5|§ 15 ql a alg J Ele! = {fo} os o 1 1 1 1 0 a01 002 008 004 Time/s Figure 23.5a During the early period (¢ < 0.05 s) UV radiation causes the formation of a small amount of atomic oxygen (less than 10* molecules cm™*). A steady-state is approached in which a near balance is established between production of atomic oxygen by dioxygen dissociation and usage of atomic ‘oxygen to produce ozone. There is, however, a 100-fold growth in the atomic oxygen concentration over the next 4 h so it is not a perfectly steady state. After 4 h of photochemistry the percentage ozone is 0.0123%. ~ 0.123% 4 13 omno3 Percentage ore ~ (; = ) 100 3.24 x 107 car Ozone production does not require low pressure in the Chapman model. Changing the oxy- gen pressure to 100 Torr gives 0.025% ozone after 4h but the increased collision rate reduces atomic oxygen to 1/5'th the value at 10 Torr. However, a pressure increase may require the inclusion in the mechanism of the step 0; +M —> O + Oz +M. This would reduce ozone production,484 STUDENT'S SOLUTIONS MANUAL Atomic oxygen 10 Concentration 10%atoms em a L am L L 1 L L 0 as 1 15 2 25 3 35 4 Times Figure 23.5b Crone 8 T T T ok 5 sl 3 gest ie §|- 2 aL L ! 1 L L L 1 as 1 1s zi 25 3 35 4 Timesh Figure 23.5¢23.35 THE KINETICS OF COMPLEX REACTIONS 485 In this solution the notation differs slightly from that in the problem. ky to ks are replaced by ky t0 ka, respectively, with ki, replaced by k_g. kr is replaced by ke (Ke does not figure in the solution). @) 2NO+N20+O — ka _ initiation O+NO+02+N_ ky propagation N+NO-N2+0 ke propagation 20+M-—>02+M kg termination O2+M-— > 204M _ kg _ initiation {NO} ) me —2ka[NOP = hy [O}LNO} — kel NI[NO}. ‘To determine the steady-state concentration of N, [N]ss, Write the rate expression for d[N}/dr and set it equal to zero. [N AU — ifO1NO] ~ kINIssINOI = 0. ki INIss = 72101 Substitution of {N]sg into the expression for d{NO}/dr indicates that, under steady-state conditions for [NJ vp = ve and {NO} dt —2ka[NO}? — 2k,{O][NO} IN] steady-state conditions: If the propagation step is much more rapid than initiation, the last term predominates {NO} dr —2k[O}[NO] IN] is in steady-state and initiation is very slow: Tf oxygen atoms and molecules are in equilibrium 20+M0,4+M, Substitution into the previous rate expression yields {NO} ene ~ ~m» (5) {02}!(NO} IN] is in steady-state; initiation is very slow; atomic and molecular oxygen are in equilibrium.486 STUDENT'S SOLUTIONS MANUAL (© Since k x e~*/*? where E, is the activation energy. we may write the individual rate constants in the form kj o e~®/T where the subscript ‘a’ has been dropped and ‘i’ represents the ith elementary step with activation energy Ej. Substitution of such expressions in the last equation of part (b) yields q -E-a/RT GINO] |. 6 6/RT (: vt a Sar) [02]'?[NO} Ey _g- (17218 )foo1"?1No}. axel We conclude that the effective activation energy, Ey eff. is given by Eaett = Ep + 3E-a+ (d) Using the estimate that activation energy is approximately equal fo the bond energies that must be broken Enet © B(NO) + $B(O2) — $B(0) = 630.57 kJ mol™! + 5(498.36 kJ mot!) ~ 3(0) * 879.75 kJ mol”! where this is the unimolecular bond-breakage estimate of activation energies. The previous estimate of Ey eff may be much too high because the activation energy of step (b) is probably being greatly overestimated. A more realistic estimate of Ei, would be that difference between the energies of the NO bond that must be broken and the Oz bond that is formed. Then, Eq.et © {B(NO) — B(O2)} + $B(0) + BONO) ~ $B(O2) * 630.57 kJ mol! — 4 (498.36 kJ mol~') =| 381.39 kJ mol7! The energy of the activated complex of step (b) is the difference between bond-breakage and bond- formation energies. It is interesting to compare these estimates with the value based upon E; values that have been determined by experiment Egest = (161 kJ mol!) + $(493 kJ mol!) — $(14 kJ mol!) = 401K) mol! This value is based upon experimental activation energies for the elementary steps.THE KINETICS OF COMPLEX REACTIONS 487 (e) We now eliminate the assumption of ©/O2 equilibrium and assume that both [N] and [O] are at steady-state value. From part (b), [Nss] = kp[O]ss/Ke- fo} dt Kq{NOF — ky[O}ss[NO] + ko[Olss{NO] — 2kalOTggIMI + 2k—alO2][M] = 0. ka{NO]? — 2kalOIRg[MI + 2k_afO21[M] = 0. = kal NOP? ~ ky[Olss + kel] + KefN]ssINO} — 2kglOls(MI + 2k-.41O2]M] = 0. At very low values of [Os] the last term is negligible so that kee Ve 101s ~ (58) INO}. Substitution of the expression for [N]gs and [O]gs into the expression for dfNO} / dr (top of part (b)) gives {NO} a 2 0] —2kg[NOP? — ky[Olss{NO] — ke (see) [NO] = —2kq|NOJ? — 2kplO]ss{NO] z eS ‘a NOF - (585) {NO} kh \'2 If propagation is much more rapid than initiation so that ky ( a =) > ka. this expression a becomes [NO] _ a (©) NO+02-+0+NO2 ke initiation {NO} an —2ka[NOP — ky{O]NO} — ke{N][NO] — ke[ NO][O>} if the conversion has proceeded to the extent that [O2] has become significant and k,[NO}[O3] >> 2kafNOP. {NO} ca —ky{O][NO] — kefNI[NO] — ke[NO][O2]. Applying the steady-state approximation to both [N] and [O] gives [Nlss = kpO]gs/Ke and fo} Gy 7 FAINOF? — kofOlssINO} + kefN]gsENO] ~ 2ke[OKsIMI + 2k alO7M] +ke[O2]|NO] =0 and — kp[O}ssINO) + ke[N]ss[NO] = 0488 STUDENT'S SOLUTIONS MANUAL ‘Thus 2kalORg(M] — 2k—a[O2]fM] — ke[O>][NO] = 0. At high concentrations of O2 species *M’ is likely to be O2 and ka[O]2,[NO] > ky[Olss{NO}. The value of kg is so small that it can be neglected. 2kg[Olgs(M] © kelO2][NO]. k ze 1: 1/2. Olss = = [O2]'?[NO]'?. [Olss (ata) [02}'?[NO}| Substitution of [N]ss and {O]sg into the expression for d[NO] / dt gives {NO} one = —Kp[Olss — kb[O]ss[NO] — ke[N]ss[NO] — ke[NO][O2] = —2ky[Olss[NO] — ke[NO][O2] ~ ar, ( y" 10 1"? [NOP — ke{NONOz]. = (sag)! Pin terms of the formation of an activated complex. In the formulation of the theory, it is assumed that the activated complex and the reactants are in equilibrium, and the concentration of activated complex is calculated in terms of an equilibrium constant, which in tun is calculated from the partition functions of the reactants and a postulated form of the activated complex. It is further supposed that one normal mode of the activated complex, the one corresponding to displacement along the reaction coordinate, has a very low force constant and displacement along this normal mode leads to products provided that the complex enters a certain configuration of its atoms, which is known as the transition state. The derivation of the equilibrium constant from the partition functions leads to eqn 24.51 and in turn to eqn 24.53, the Eyring equation. See Section 24.4 for a more complete discussion of a complicated subject. Infrared chemiluminescence. Chemical reactions may yield products in excited states. The emission of radiation as the molecules decay to lower energy states is called chemiluminescence. If the emission is from vibrationally excited states, then it is infrared chemiluminescence. The vibrationally excited product molecule in the example of Figure 24.13 in the text is CO. By studying the intensities of the infrared emission spectrum, the populations of the vibrational states in the product CO may be determined and this information allows us to determine the relative rates of formation of CO in these excited states. ‘Mutti-photon ionization (MPI). Multi-photon absorption is the absorption of two or more photons by the molecule in its transition to a higher electronic state, The frequencies of the photons satisfy the condition AE=hu thy+- which is similar to the frequency condition for one-photon absorption. However, multi-photon selection rules are different from one-photon selection rules. Therefore, multi-photon processes allow examination of energy states that otherwise could not be reached. In multi-photon ionization, the second or third24.7 E24.1(b) 490 STUDENT'S SOLUTIONS MANUAL. photon takes the molecule into the energy continuum above its highest lying energy state. This technique is especially useful for the study of weakly fluorescing molecules. Resonant multi-photon ionization (REMPI). This is a variant of MPI described above, in which one or more photons promote a molecule to an electronically excited state and then additional photons generate ions from the excited state. The power of this method in the study of chemical reactions is its selectivity. Ina chemically reacting system, individual reactants and products can be chosen by tuning the frequency of the laser generating the radiation to the electronic absorption band of specific molecules. Reaction product imaging. In this technique, product ions are accelerated by an electric field toward a phosphorescent screen and the light emitted from the screen is imaged by a charge-coupled device. The nificance of this experiment to the study of chemical reactions is that it allows for a detailed analysis of the angular distribution of products. Femtosecond spectroscopy. See Section 24.9 for a more detailed discussion. Until recently, because of their exceedingly short lifetimes, there have been no direct observations of the activated complexes postulated to exist in the transition state of chemical reactions. But. after the development of femtosecond pulsed lasers, species resembling activated complexes can now be studied spectroscopically. Transitions to and from the activated complex have been observed and such experiments have greatly extended our knowledge of the dynamics of chemical reactions. ‘The Rb atom must hit the I side of CHsT in order to produce RbI + CH. The orientation of CHI can be controlled by exciting rotations about the CI axis with linearly polarized light; the optimal orientation aims the I side of CHI at the direction of approach of the beam of Rb atoms. Two possible alignments of the reactant beams are shown in Fig. 24.1. In the top depiction, the beams are antiparallel, thereby maximizing the likelihood of collision and the volume within which collision can occur (but also putting ‘each beam source in the path of the other beam). In the lower depiction, the beam paths are at right angles, thereby minimizing the region in which the beams collide, but facilitating the study of that well-defined m volume by a *probe* laser at right angles to both beams. Ha > <—— ® <—— ® HCI Figure 24.1 Solutions to exercises The collision frequency is, 226 @)p 2 8rT\"? aq Cheteg = md? = nr? and (@) = (Sr)MOLECULAR REACTION DYNAMICS 491 = ("= 16pNar2x'/2 aM) ~~ RTM _ 16 x (100 x 10* Pay x (6.022 x 1074 mol~!) x (180 x L0-!? m)? x (77)!/? . 1(8.31453 K~!mol~!) x (298 K) x (28.01 x 10-3 kg mol~")]!/2 6.64 x 10° s7! (6.64 x 10° s~!) x (100 x 10° Pa) © OKT ~ 2(1.381 x 10-23) K-!) x (298K) = [8.07 x 104 m~ Raising the temperature at constant volume means raising the pressure in proportion to the temperature Zan VT so the percent increase in z and Zaq due to a 10 K increase in temperature is [1.6 percent | same as Exercise 24.1(a). E24.2(b) The appropriate fraction is given by root) The values in question are @ @ f=exp = 15x 10°F mort __ 4x1073| (8.3145SK~' mol") x (300K). mol!) x (300K) — =15 x 10° Imo! ii) f= 0:10 Ose se (ae 'mol~') x (800K) ® 0 f= ==1S0/10-I mola TI x10 i) f=en Tx P (831455 K~! mol") x (00K), Gi) f=ex p= SOT MET 1.6 x107!0 = exp ———* ST _) _fiex PY 31451K mol) x (800K) E24.3(b) A straightforward approach would be to compute f = exp(—Ea/RT) at the new temperature and compare it to that at the old temperature. An approximate approach would be to note that changes from So = exp (—Eg/RT) tof = exp(—Eq/RT(1 +), where x is the fractional increase in the temperature. If x is small, the exponent changes from —E,/RT to approximately (~E,/RT)(1 — x) and f changes from exp (—Ea/RT) to exp (—Eq(1 — x)/RT) = exp (—Eq/RT) [exp (—Ea/RT)] * = fof *- Thus the new Boltzmann factor is the old one times a factor of fi:*. The factor of increase is @) f= 24 x 10-3)-1730 — [72] i) fo* = (0.10) = [1.03492 STUDENT'S SOLUTIONS MANUAL. (BY) fo = (7-7 x 10-77) 19900 = [7.4 Gi) fo * = (16 x 10-19)-10/800 E24.4(b) The reaction rate is given by 8kpT\'? = PoE)” Na expt-Fa/RTIDalIB 0, in the absence of any estimate of the reaction probability P, the rate constant is 8kaT\'?, k=o(——) Naexp(—E,/RT) mK = [0.30 x (10- m)?} 8(1.381 x 10-25 K-!) x (450K) \"” 373.9300) x (1,66 x 10-2 kgu) “4 om - 6022 10 ato otal Catan ) (8.3145 5K! mol!) x (450K) = 1.71 x 107 m* mol! 1.7 x 10! dm? mot~! s~! £24.5(b) The rate constant is ka = 400 R*DNa where D is the sum of two diffusion constants. So Ka = 4(0.50 x 10- m) x (2 x 4.2 x 10-° m2 s") x (6.022 x 10° mol!) =|3.2 x 10m? mol"! 5“! In more common units, this is kg =|3.2 x 10! dm? mol! s~! £24.66) (a) A diffusion-controlled rate constant in decylbenzene is SRT _ 8 x (8.3145JK7! mol!) x (298K) _ ka 1.97 10° m3 mol! s~! hy 3x B36 x 103 kgm!) (b) In concentrated sulfuric acid BRT _ 8 x (8.3145IK7! mol!) x (298K = = BX C3MSTRT mol) X C9BK) _ 94 105m? mol-!s! ka 3n 3x (27 x 10-3kgm's-!) 24.7(b) The diffusion-controlled rate constant is SRT _ 8 x (8.3145JK7! mol”!) x (298K) “Fy 3x @60lx103kgm is) 1.10 x 107 m3 mol~! s~!E24.8(b) E24.9(6) MOLECULAR REACTION DYNAMICS 493 In more common units, ky =| 1.10 x 10!°dm? mol! s~! ‘The recombination reaction has a rate of v= kafAIB] with A] = [B] so the half-life is given by F 1 I 12 = sc!) x (1.8 x 10-3 mol dm KIAlo (1.10 x 10! dm? mot ‘The reactive cross-section 0° is related to the collision cross-section & by o* =Po so P=o*/o The collision cross-section o is related to effective molecular diameters by o=nd so d=(o/n)'? 2 Now ons = dhy = [$a + dey] = (oh + off?) Hele role) a) 8.7 x 10-7 © ¥[@0.88)17 + (0.40)") x 10-9 me 141 x10" ‘The diffusion-controlled rate constant is 8RT 8 x (8.31453 K ! mol!) x (293K) — 5.12 x 10° m* mol! s~! 3n 3x (1.27 x 10? kgm! s—!) In more common units, kg = 5.12 x 10°dm3 mol ‘The recombination reaction has a rate of = kg{A][B] = (5.12 x 10° dm? mot | s 1.54 x 108 mol dav ") x (0.200 moldm~4) x (0.150 moldm~3) E24.10(b) The enthalpy of activation for a reaction in solution is ATH = Ey — RY = (83145IK~'! mot!) x (6134K) — (8.3145 K-! mol!) x (298K) = 4.892 x 10° Jmol! = [48.52 mol]494 STUDENT'S SOLUTIONS MANUAL. ‘The entropy of activation is ais =R(in§ -1) whee HET B hp® pa (381 x 10 IK™) x (8.3145 K"! mol!) x (298K)? (6.626 x 10-¥4Js) x (1.00 x 105 Pa) = 1.54 x 10! m¥ mol! s~ 2 dm? mot! w0 15 = 314955 > (hn Ei Wy acini oal (1000 dm} m_ ) x (1.54 x 10! m3 mol! s-!) —32.2)K7! mol! COMMENT. In this connection, the enthalpy of activation is often referred to as “energy” of activation. £24.11(b) The Gibbs energy of activation is related to the rate constant by -a'G kRT? ka J r = #G = —rTIin ha = Bex ( ) where B AtG = -RTIn ky = (6.45 x 10 dm? mot! ye (09375 K) (298K) — 9.47 x 10% dm} mol = 947m mol"! s“! Using the value of B computed in Exercise 27.13(b), we obtain Tino ae 4G = —(8.3145 x 10-3 KI KK! mot!) x (298K) x In ( 247m mols _ 1.54 x 101! m3 mol at A KRT? a(n -2) where B = ——— B (1.381 x 10-9 JK“!) x (8.3145. K7! mol!) x [(55 + 273) KP (6.626 x 10-¥ Js) x (1.00 x 105 Pa) = 1.86 x 10! m* mot! s“! ‘The rate constant is —E, Ea n=see(sB) 1 a=nee(&) a eT 49.6 x 103 Jmol! A= (0.23 m3 mot”! 5!) x exp | ——— (8.3145 K~' mol!) x (328K) 1.8 x 107 m' mols“MOLECULAR REACTION DYNAMICS 495 ea and Ats = (8.31455K-! mot!) x (in +8 *10 mimor Ss) _ 5 1.86 x 10! m3 mol 's~! =|-931K7! mol! E24.13(b) The entropy of activation for a bimolecular reaction in the gas phase is RT? aison(wf-2) ween = 2 For the collision of structureless particles, the rate constant is ‘8kT\'? =A tn=m (2) “cern (=222) so the prefactor is ser? rt \\? a=m(22) o=ann( 22) ° mH aM where we have used the fact that jr = 4m for identical particles and k/m = R/M. So (8.3145 JK! mot~!) x (500K) 1B = x (0.68 x 10-'® m?) at x (78 x 10-3 kg mol!) A=4 x (6.022 x 10% mol!) x ( = 2.13 x 10®m* mot! s~! _ (1.381 x 10-3 JK~!) x (8.3145 K-! mol!) x (500K)? ~ 626 x 10-¥ Js) x (1.00 x 10° Pa) 1 = 4.33 x 10!! m3 mol 2.13 x 108 m3 mol and A'S = (8.31453K~! mol!) x { In 4.33 x 10! m mol 80.0JK—! mol! £24.14(b) (a) The entropy of activation for a unimolecular gas-phase reaction is A ats =8 (ng - 1) where B = 1.54 x 10'! m* mols“! [See Exercise 24.14(a)] so AtS = (8.3145) K~! mol!) zt 2.3 x 10'3 dm} mol! i (1000 dm? m=3) x (1.54 x 10! m3 mols J (b) The enthalpy of activation is ATH = E, — RT = 30.0 x 10° Jmol! — (8.31453 K~! mol!) x (298K) =215 x 10° Jmol"! =[275ki mol!