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26 views17 pages

ch16 K

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Abdullah Altwirqi
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lou} Chapter 1G: Chemical Kinetics Theemodynamas iS Wed to predict whiRn a réaction will procesd under speoyfied conditons — but it cammet be wed fo predict how foot the reaction, uiill go or by what mechanism it will proceed. Example: 2 HUGE + MelOH),c) > Mg Ch ag + 2HO(t) AG--97kT yagi! CGamand) + Q2@ —> COQ. @) AG = -3% kT v. Sow Chemical kinetics is the study of teilts of chemcal reackono (ie. chfeamumnda how foot reachono 90) ond the mechanisms by which. they occur. Lets consider cohat thio means : rate: change in he amesntation. of product or reactant per wnat time. Ht is abunys a positive number. The veactanit over time duappears and The product apaano. Consider. a 1- skp reaction : AB (00% 100% + Néi: fe A> 3B, emeorchation Ret, = — $B = +38, ° O “Tink, . = AA _ -(Ag-A)) role of reaction == PAE = tf, ral oles oti for any tme uneral — sinee At=tyt, Belpre 4B B- Bi . 2 SB = Se oto! produckin At tet, wi at Bick For most purposes we ova untrested unth the unvttal vette of reactions \o-2 which is the rede ot t=O when Re reaction just begins As Yume progresses, we see the raft of reaction slow doum (slope of Line > 0) How do ieacchono occur? They occur vis the rtachon mechanism : the pothuay (or series of skeps) by which the reachon poceeds. The reachin rele is dependent on the reli of midundual skps - ao we shall see. The ret of reachon depen on 4 factors : G) the nostune of tHe reactomts (2) the coooshotion of reacumts @ Lmprodure (4) cotolyeco (1) Nodure of Reactant + chemical achuity + €q Somme meds are more ache than ctv in achwity Kis) > No(s) > Lie) + physical stoi (size of partclr, phour , oft.) (od & Substance trot is fonely ground reacks -poter than the samme, Substance. in chunks due 40 the much greater Surface onea, exposed fr reaction in ‘the poudered sample . (b). reachons “thot occur behueen diaodlued tone in Solution ane truck more rapid thom betwen solids or gases, sunta in the former cose, no bond read to be broken. 2) Concrtrothon of Reactants In ol, an the comcemhation of reactants unotare ‘the probal of collisions increase ve the probability of rachens occurring invuases. Ib-3 For o simple one stp reaching A> B+ QC — (dectmposrtion reaction) . 3C Experiment CATinikio LBJinitioh Thiol rie of fomotion, of C \ 0.10M 010M 2.0 x10-# M-st 2 0.30M ©0.0M 6.0% 104 Ms! 3 0.10M 0.30M 2.0*10% Ms! 4 0.20M O40M HOriot Ms! We know that the rate law expression will be: rol =k CAM (B)” By obsenvotion, we dentfy pains of experiments uhere coeanbrotios of reoctonts ave allithe same, except for one, We look fo see. what affect o change in te emesnhation hae on the unital rile of reaction. Aside: Consider Rota = k (Al” my + if x20 (aeoadn %A): Rote=kLAT? Rete = omotont k Sif x= 1 frst owt 4% A) + Rowe k(al’ Rete < Cal nif x22 (seemd odin %A) + Rede =k (a Rete @ CAT Experiment 1+ 3: (A is coolant = O.10M on [8] imuwaaes by o factor of al earn but the reli of reaction does NOT change =(B] dow not offect the rate + order of reackim O% (wih reapect to) B sys 0 Experiments 243: (Vis cmotant = 0.30M , (Al durant by factor of 3 vole of reachion dacraaces by a. factor of 3S ~ rote @ (AT, orden of veackim %% A =| (fast oder) The outtll, odin im. is (+0) 1 Rota law exprustion: Roti= k{al'(81° = k (Al lo-S Exempla: What is the rete law eypussion fr the following reaction. given. the dota. below ? aA+ Be AC > 3D+H2E Inatiol, Rats of Experiment [A Jinhad (BYinctioh [C]nukal Formation of D U 0.20 M 0.10M O.10M 2x10 M/min a 0.20M 030M ——-0.20M 1B 10% M fin 3 0.40M 010M 0.30M Q« 10% M min 4 ©.10M 0. 60M OHOM 3.¥ 10 M/min “he rot low expression, will have the form: Role = k (AN*C8]# Lc]? Now we mast Jook ot the data 40 derive the valuw of x,y,2. Experumonts 1¥3: LAT, £6] onconotant , (CJ mereoaes by a. factor of 3 c 93) rote does NOT chamge se reaction is 26r0 mdr Wr fo Cand we cam ignore thas dada Experiments [+2 CAL is crmtant , [81 mows by ofactor of 3 role ncwases by o factor fl A (= Ee) we pole & (B1* | reach vo seemd ander Y% B There ove. no exprrimonts here CA] vonito and (BJ remame covstont, So we will howe to evabuote the der of the reachm %% A mathermatcolly Lets we Exp +4 where (AT vorien and writ doum the rite law expressions with, the voluao plugged in, and Solve, Q equothns with A umbnouns > x amd k by dividing one equation by “the ctr. | Reta = k CAI" (e]* [er Expt 4 3oxi0= (01) (o@* Note: Pat the evpinment with Expt 2 1.8* 10% = k @)* (0.3)* the larger rot. on top - the Wuumbers Work out eason that way. Ib-6 (24) (a ae «by xed S reach is frst orden 4% A The voile law expremion is Rote = K[ATLBI* overall oder io 142.23 Example: Using the above rete law expression, if the cmeantation of A were halved cmd the comeentration of B were tripled during a reachin, Labs would! happen to the rete ? Assume the uitial ancmctiakma of A and B were both | M, Thovefore Rott = k (AI(BI? = kK(IY =k Afr the chomge inthe reaction, Reb = k (GP = tk oe the rote of Ye reachon wold demi. nersous bey 0 face of w Spoke Rete Crotant , k Conteh MoM Mae Reachon raft oluays has units of QoS, im = , The wnids of k thewfre depend on the overall ander of the reachn ( Rote: k (AT, Overall Order of Reaction | Unita of k Example ° Met" Rot = k \ e Rate ~ k(AT 2 Mitt Rat = k (AT 3 Matt Rate k (AT? In some examples, umits of kk one omitid - but you ntad to knno thom . To daleamine voluafi kim am example, use the dota. from amy expurimencts inthot example, plug ito the rote lao exprasion and solve hk fot Example : Recall the second example fu which wedbirinimed tte rite ~ law exprassion # Rote = k (ATLBI* Using Expt 1 xid“#h> k (0.20 H)(0.1I0 M)* k = OL M* min! Now we cam write the complite rote, law expressim.: Rate = 0.1 Minin (ALLGT Mamy ture we wish to Know the concorchation ofa reactant that would remain. aftr a specfiad time, or how long it would “phe for Some amount of he reactants fo be uved up. This kads ua 4o the concepts of Holf-life ond the. Integrated Rote, Equation, Cf fut fast order ee ee ed The half-life of o reactant. a the time, required ‘foe holf of the reactant to be consumed in the reaction Oe HELE Oo enw ito AD sen, tae (Menai *) L1 FA CAs has rac ° ty aes, Bxty Naty For reactiono that are fost ordn, 4% A and frat nden overall & vodlioodwe keay) Rate= ABS 88D ~ (a7 shee (Ale + ant ot ce of temaining at time,t Fife ee — (Ale oot (Ale (Ah ee fA}. * i = vehi cnvlont Al (Ale = kt are LA. _ kt [on Bk - akt er log tah * 3303 | or 'og"(ay = 4303 Team lo-8 Nota: “ log is exponent” logo y= x > 10% = y base 10 Inygox @ e=y base € = 2783-1 exompla: 109, 100= 2 lo*= 100 At time taty, CAle > 2LAT. by daftnihin, Five plug this into the previous equation (the one that Tike), we howe Atm, . -kte log “fay. * 2303" ~ 0.30) > Example : Cyclopropane decompores to propene by first order lunetics, joe Cha— cH, > CH3CH= CHa ty = 0.0755 (a) coleulote tte rite cmotamt k : 0-693 0.693 . = tp * O.0ts © 42 5" (©) How much eof a 3.0 9 Sormpla, remains aftr 0.20 s? Ay. pike log Re ~ 4303 Ar -42s'x 0.208 log 3o * 3303 Ay log Bo * 70.799 Take the mverse log of both sides (on colton: inv log or At Bo * 0.159 Ae? 04 9 lo-4 (©) How long does ct take (im seemnds) to have only 0.010 g remaimeng of a. BO q sample ? Ag, akt oq” Ae * “2.303 0.010 - 92st xt loq” 3.0 * ~g.303 2.010 24a stxt simply tae log of 3ot -2A8= 3303 t= Obs @) Wheat fraction of the sample has been converted fo propene aftr Os? Ae, x=kt Ae. . log Ay * @303 whew Ae , the fiction tat emaina! As _ -42s'x0.50s ond (I> Re is the fraction thot hav reacied. log Ae 2.303 A tog a, 7 720 A - Ne = 0.0] 2 0.01 (or 1%) is He fraction. of cycloprapame remaining 0.99 Gr 9%) i the faction thot hao reacted. “Tico theoriss axe wed +b explain why catain {Sors ofed reaction ret, Le Collision Theory of Reaction Ratio (used fa |I- step reactions) premise: in order fro reaction fo occur, the atoms, mokuules or imo @) must collide (come umto comtact) (6) must have om effective collision ie + reaching specia must have o minunum energy which uth be shamsforad undo breaking old beds ane! making rew ono, * veacting specio must have proper orienatvn Consider “the qa phase reach: CO + H,0 -* CO, + Ha 4 Grn = 538.6 oe ran is spoxbmeous Ib-10 C20 + H-O -» Q=C=0 + H-H H What kind of 'a collision do we need to get bond formation. ? ANS. The O atom in HO must come into contact with tle C atom in CO Effective collision Cproviding he ersgy of Unpoct is great enough) TL Troasthin Stata Theory : Premise: ina [-slep reaction, the reactants are fiwt converted into o high. entngy unermadiot shite, called a hansitin state, befre forming products. Consider Xy +Va >= 2X + go transition Gr-excited) stot, -++++ reprrsent Postal . Ea fawaad io te actvaduin mare ed 5, we ee ones aX rears Reaction Coordinate BHY > Wa + Va reactants Xy ond Ye have to poems achvatin enungy, Ea, in oer fo react \f Xy and Yo de react, He change wn udewnal, Ys AE ne i “ Ex-E, <0 | = there is a veke of energy. fivite above reactim Ka, Ya + XY aw gasea, thn AE = 4H and the reachm is exotwumic. AE- 4H- Pay = AH: ner oO Ie-1 Reaction, Mechomusins and thea Rete -Low Expiession, Most reactions cccun im 0. seras of skips called “the wechanitm. ofa. eachin. “These steps ore thought 1 be promaniliy G) unimolecular deamposttion steps eg A>BrC (2) bimolecular collisions * eg AtB3c * trimolecudar collisims between 3 (or mow) species are rare. sunce tb is vey vmproboble “thot 3 (or moy.) spreimo will be ok the some place ot exacity tte some time to collide, ond react: se We do not cmsider them. + the SLOWEST skp dekrmines the rit of the overoll reactim. lt to collad “e*tata-delermining cep” and it: is tHe slep with the - tughst octivosim. enangy (Fig. le: 12. p. b40). _ Polenkol Ereqy Diagram fa B-step reaction; te 2M step wu the rede dulewminirg skp (hao hghut Ea.) The experimentally. derived reti-law expussion a Roti = k fay*C8l” is used to postulate. 0. mechomicm (6 fertactim, The values of x and y — 210 relosed -fo “the coefficionts of the veactonts in the SLOWEST skp, influenced im some comes by eorler steps. “When the. slew slop ino machanitm. is “Re faut slop, the oxder of. reaskim Ye 40.0 Pantinlar reactant (the expment) unsiechin the number maleculas of thot reactant ‘thot oppear ao reactants in thet slew, ate-determining skp. ere ave fit, epuuitim skpa prior (lmfire) to “the slow step, the siluation is more complicated se. oD To~id, “To deleumine. if a propoted mechaniim is the correct one fra reaction, ot Loot Q criteria. mugt be met: 0) the sum of al the skps must be the some ao the overall reachon, when like trams ara cuncelled, @) tHe rite law exprassion of the mechamism. muot moh the tua, exprrimentally-derwed roti. law expression. rion. CI) self explamortory ion @) (a) if the shw , ole-deeuminig Skp 1s the fout sep, hen the rummter of tomes cock reactant appens aoa reackint is the, exponent in the rots. lawexpussim. : Rati = k [each reocant] mmisct tee Hropae. Exompla: Consider the hypothetical, reaction, 2A+B+C — AC + AB Woith the exprrimentally -durwed red. law expression + Roti = k [AS(RTCCI the rete law exprossion Yell uo thot one moleate each of A, Band C ore involved in defermiming “the raiti of the reaction, Possible mechamigm 1: SkepeD A+A>A, (slow) Stp@ Ag+ B—->AB+A (fost) Sep © A+C> Ac (fat) overll QA+B+C—> AC+AB Nate: Ag is called an intr medic; ‘cb io both produced amd consumed in he reactions, Io-13 Titerpretodion of Ais mechamisn: Sep] two atoms of A collide fogetnr with enough energy fo produce L moleae of Ar : Sep@D that molecule. of Ay (onynlermediate, remember) collides with, an atom of B +o produce a molculeof AB and an atom of A. Sep@) the tom of A “hen collides with an atom of C; a chemical, bond is Grmed behaton Acnd C and Voids: a molecule of AC. The. overall reaction is the sum of the reactant and produds ~ afta Cressing out fhe forma So, could Mechaniim 4. be 0 possible machaniim $i “his teachin ? © critiion 1s met — Fe cueroll reachms makh a + the refi law expansirnr , tho, fa this machamim i Reta = kLAT Mechamism 1 camnot be the Correct mechani. im Q(b) If tha slow step is preceeded by fiat, epuildriam skps, ten ue. have he fling stiatim Possible, Mechoniam 2: (for our same hypotfetical reactiom) Sep At Be AB (foot equilibrium) @ AB+C > ABC (Slow) ABC is ucturedits, Skp@ _ABC* A —> AC+AB (fost) overt 2A.+B+C > AC+AB sc crtedon 1 is met: Oveulll reaction ogress with reaction undir shudly + criti 2: usung The. slow step, the vote law exproarion is : Rok = k (aaj(cl lo- ExRA Exomple: 2 Ny0e —> 4NO, + O, Rete = k (Ng051 Ressible mechanism: @O — NgO¢ —> NO,+ NOs (slow) ®@ —NgOs + NOg-> Nady +NOs Chat) @ NOx + Moy? ANON (GA) ® _NOy + NO> ANC +O, Chai) overall = ANOS > 4N0, + Or Recall the slower rhe step, the higher is the achuatim enuay fo that skp. “possible. potential energy diagram. (Assuming *fequoney fickn, A, ia covatanc)) ~ 2 co re UM eay AE fi reaction reachon coordinate. Is the followeng a potential mechanism 7 Step @ Nads > NO + 20x (Slows) @ NOs +NzO > 2NO, + Or+Na (fast) @ Ne 420, -» 2NO, (fost) overcth 2 N05 = 4N0,+ Or Ans. You nught think So; step@® contain V melecute of MpO5 and it is the slow reaction. However skp@® is a jimolecular reaction tbh is not Mikely this is NOT a hhkaly mechonigm (tacky). \o-H i | : i But _AG is net a ractowt; it io formed im Sep and consumed im Sep @ | Fs epuamtactinn | (eq. Skp@ in Mechaniem 2.) we can write Lpedut tIfpodut 2] ote epuiibrium constant, = enchant ICeadtontay eke; Sunelifad, for Stp@: A+ B= AB K= Teor > (ag) ~ Kfaltel ear Substtuding unto he radi. law expression: Rote = k CABI[C] we have, Rati = k (K(ASCBT) (cl = k’ (AIL@ILC] _ whe k’= ke Ko Tenfe thin mechanigm. May be correct. 5 pai mee. __the ueamestiots ABC, inthe laboratory, “Tuo fan, we hove. stadiad -wo-filors fat. contet te eit of Ye actin: > @ hadune of reactants 1 @) concahotion of reactants. »Now we url oddroc (2) Effect of fonpuosure. chan geo on reachon vats — (Cramp: 49, 53) “Consider “te Aske roctin: A+ BC + Rete = k [allB] 8 pasa pil ry dogiom: ft | 6. fr Grund rin ae a Evay” ce) Reaction Coordinate As the Jompercdura imcwases, mor and mow ractant moleenles have te reeeusary caugy, Ea (theactwottn enugy) to react and frm product motreulia upm colliicms Ea does not chamge witk the tmperaturo; it only chamges if mechanism changes Ios | Archerito developed tHe mathematica, relatiosship behuenn, emptrature, rai. covataas, K. (which dees depend nT) and #eactivehim energy , Ee (whieh dea NOT depend on T). Ee k= Ae r where. k Spofic wit. crolnat . a AY flopuuncy -fictor- reloled Tt, BPN, eT PD, kt ott ( nahue of rac . . @) no. + effectiventas _ Taking nabural log of both sidee, __ of collisims S Ea actwolin enagy Inks [nA - RE R_ BIN T/mat K_ . — Tr obsetute T (0) @ of T: “leq k= e log A” = 78 RT. ee loq-ke = log = S358 Oth 7 @ fon ©, Pane Ea lon - log Fl - -lPsaR, 7 2305 R7, #-2)- S(S2)P : Tile log ka- log k= Ee log “ky = Bast Te “Eromnplas lahat. inthe activakam eneagy “te actin: NOG)» Nat + Oni) 2 . voy ot 300°C (S73 K) _— how. k= 2.6510" _kye alxl0’s' ot 330°C (603K) 603-573 amos log. Bez ot s= = PRCT 3d TaRaK (Gass 543 ly 81 = TE (nd) = 200% 10° T/mad or QO0. kT/nek fo-lo (A) Effct of Cotadaysto Cotalysts ane substamces that sped up reaction roti unthout being comnoumed. They Cam appear ‘in. am equation + A+B + caubalyst > C+ catalyst, ov may oly appear over the anow —o>, Mest cotalysts appear to finctim. by Somehow lowering the actwahm enoigy of the cugiral reaction by providing am abtanate reachon pathway. Gee Fig loriS pets), © Eb SS) Tt e BP kT tote t 1 t if wd Potencol Eareverse Potro Eneray spe Eorgy Reaction. Coordinate Reaction Condinate UNCATALY2ED CATALY ZED There are two categories of catalyst : a) homogeneous 2 the catalyst exist in same phase av reactants example + strong acids g 2 Cis €-0-CH,CH ap + yO AS CHyEOH cagy + CHyCHOH Cog) ethyl acetate acetic acid ethanol (2) heterogeneous + the catalyst exists in adiffeunt phase than reactants Ht is Uowallly a Solid - which lowers the actuation enceg by providing a suafice upon which. the reactoa cam occun. evamgle: 2H, @) + Oa EAHOM) *G=-47V RT this teactm. doeo not go appreciably at roam temperature but inthe presence of PE which is forely divided , He reaction is exploswut.

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