21 Withovt experimental data we cannot avewer this question, “Me order of reactuin need wot matel. the ctorcnometyy, ames efter doesidt 263 Why choold the way you wie the cbiichomety affect the vake, of reaction? The vate expession remams unchanged. as 2 —% =- 25 tRe ee esos 5 er T= 4 =the 278) We are quer 72 42 amAr sue Cerny? Balancing dimensiems we find R= 266 C@iny ar)! a) \y For an ideal ges eV= RT or eG RT thos ~ as = 2.6664 ~ bewmes ~ oe = 3.66 8T) ~ Cr = [266 (atmy' te Jar Ct 8 ee es new rate constant = fa! oa 15 i Ce \ _ Gate\Qa4e) 64 ony _ =! “I where f'= 306 Geis (eigen C4oa"ke) = 120 (lr) "Con J or 249 From Eq, BS we write Eyl - 1b ise oe ous _ 300 000 (de Sel) =e oF \te 78 ) Se34965 3.4602 3.384 3.36% Ge 33220 58 — 3420 sh DalSpeed) “+ E= (5420) (8-314) = 45062 ae S45 kT 50 “Lk Sane bas ase () 242 22-0 3390 eT aay 3394 aS ~43 262 3.340 1% 2H3 3.364 18 Bhi 3.yoo 90 227 3.382 8H In(Rate) “ slope = - “= -3392 E = (3392) (8-314) #s = 2820) 3 334 336 333 340 = 28.2 kT/mo)C QNT Guess that - tq EQS Ce” 3 fa fe = Where ave % unkuowusek,a ard b ee But we have 2 aquotuis a oS Sb 48 5O= ks! ---a> - 32 = kayrGu” AB =k(S)* GH? -- Dyinde Gd by & ges Gel a] oe Divide > bys gues b= 4s pee R= SAS Regia and b mds gives Ko | . and tet us Fct dts At Be aes rake expression, 2,\4a) Consider the mechamsy MA ZEE wee, Fir reactant A: -tya ki (AT - Q[ATI(AT -----t st state Fir mhemadate : re © ki (AT kafa"](4] - feLat] fo tte fom ohn far]s WO LaT Hy, -—-) Replacing (i) WG) soas to elmmate the unmeasurable AY awes "4 ~ r og = fbolal lees OO And when ky(A | ds ae ab fA] --. or fast oder rx gq a ) Now at low enough Cy we may reach condshons where $,(A }«k,. In such a situation” €q, (i) will reduce to m= RLAT? = or 24 order kinetics Hence lower Cy more and move, This mechanism predicts thet Q pomt wil be reached where the reaction order will shat vising from vne, and wil approach and eventual become two. 4 by22 223 cs Hy Po, +H > X* 4 Ht Hypothese: fe - where X* is an unstable intermediate. X* +O = HgPOs Then as in the xample, pq 19, we write, “aro, = Rb" Lox] = 4, [HsPon | tree Lone Ve = [iat |[H]-4,014 -& be'TLod + by [Hse06] £0 hes Gye mao] rhaleo] 4, [4°] + Fy Lond oo Aesommg chy =0 (and we are cartaialy free to do this ence this is ov model, our brainchild ), replacwig wy in diy then ques = bike [hgeoy']LH*] Loe] © 4 be] elo] Now when bloxl>4fHt] te high ovidiser concentration, £4. ques ey HeP Os, Yaaro, = PiltsPon [LH] ~~ = === On the other hand when ta[H*] >, [Ox] -— ine, tow a Ea.ti) quves a) ae ae fis [igpog] foe] oo ” Sys (Ww) & (v1 fib the endence hone the hypothesized model pin M-M assume that the vevese Teerctions of GD approach YK — RHE @ + equrldoriom quickly , of Ate aK --® eX ok ® tot, ee) K AE @ B-H assume thet quickly Mac =O ®foc MM For B-4 (continued), ore Fom ® eo Cao bax © roe 6 From ©) ie ky X= AF 7 +0 =k AE-(atksX% Elum ate i with i. X= fb AEX) Lee or AE X= Varke, © Eq@ »@ gues tes bs AES : Kates: > a er eo 2) his wealiel the Melaet’s vesult 2 coustauh Cy By careful analysis of careful exgenments Chance, J Gia, Chem, 151 S52 C1442 favors the Brggs— Haldane mechaniom, hater endence removers. His choice, Thus we end vp today with the s0 caked Mehaetis~ Merten equattian’ which it m fact the BH modFication of te M-M equatwin