Kinehics ancl Reaction Mechanisms (A2) «Many reockons occur ih a humber of steps. This iS coh fhe vRation mechanisin, + These steps foke plow ot Its own rote omol heme its own vate constant, ©The cvecadd wate of 0 mult’ step process Lepencls On the slowsat sty °The slowsst step is known as the rate, determibing step. « inuustigetion of he. rate eqnedion givin om fda of the stepa fnardescl iho yrnction - «A reoctont thet appears th the chapmical epaatton may have no effet on ranetion vote oA substince which is not a reactont in the chemiced squation Com offet reochich rote. Erxatple | * Reaction batween lodihs and pro pans : CHyCochkh + 1, ——> CH;CocH,I +H2 © The rote equction > rate = k[CHscoots](H"] °C] im the rode equation because reaction 13 Cadediyeol by acid ° [1,] nat in the rate eyuation baconae the reoction has nove thanohe step ancl he slouat step clorent jhvctue Pockue . ° The ate datuemening step mut therefore thuelue prapamere ;Venifycng possibke reaction mechaniting + Kinetic. deta com only shia that a propotact raedtion mechanism is possible , © The reaction machoniitn iS net clechrescl fom the kitake data. ° Example | © Vorious machanising Neve leon propose for the rxn crscocu, +1, Hs cucocitet tHI © OR proposed Imechanisin e faa a fi i Cy bem, +Ht et cmd cy, tou low en + CHy-b—chy 22> cHy-dacth +H ton on fast 2 - cty-e zen, + Te > ely-C- ovr +I 40H e Clh-C~cwmt +1 ft cls-€-cg 1 + HI © The rote equation Fon thas reaction 1s vate = k(CHyCOCH ICH] © From the riechanisin, the rate determing step (slow step) doss net [huclue ether propanshe OF hydeogen jone cliveetly. a. + However, the intermoobote cu,b-cny / derivect fom substances (prpanont ancl beg chrogen fone) which react together to Form it. So beth [escorts] one (H7] eppter in The rade 2pucttion. No+NO, +0, No +n, Mt. 2W0. © Njote that Pwo molecules of MaDe heed fe have, vaacttdl for subsequent staps ty be complied o The rate opvation tells us that the decomposition of thal vithtad ie leans off ricbogen(V) oxide is the rate -detrriing shp The; fits in with The proposeal brchonstsin ho paggeed that the decomposition of Nabe to Forin NOs mol N03 is the slow step. “The sohsequst steps are Wy merch fratnn hy comparison enol do het Mnflasnce The ovrllrode.Exsreise, Ar, oxcdified solution of hyolrogm piroxich reacts with Poole fone. HOaleqy + 2H +21 ey > 2HOu, Ley The vecte eguection fer this r2edtion Is : vote = (H.0.)077] The mechanism below hee barn pro poseat fur this raection - Hoo, +17 ten __,, Hs0 + LO” Ht+ Io” ft, H10 HrorHt+~ S43, +o Explain why thes Inschanrsin TS Comaatent with the vate egnredToh - Wg buty Tha rete equection shunse Hut the vote defects shp- Tnvoturcl Hed, and [~rors. The hybrogen jons do nat opprer jh the rate equation hacanse thay ace imolurd in fast steps Which tudes place offre the rats —dtrrmencng step (slow stp). So the prspossd nachonsily 15 const bef with tha vote equation.Predicting the orden of 0 revction Pom riscton echow i © Lf the jrtrrinadiotes pracent ih the rate dedertihibg Step Cov substenees which react together ty form the prberinsaliadn,) ore Montified, Hum we con predict the orden of reaction Pom a given reection mach ancsin. ° Ex. 2 The vtetion of propanone with bromehe jn okkabrre solutr'on , CH3COCH, + Br, +OH—> CAC ocr Ry tho +Br © The veaction mechansin hon glow ged. wdd-by 40H et > H-c~c-C: +Hso 44 no ° fast oY ~ ptt ea, snl BL, +r a's 4 ©The slow step 78 the vate beter mning step. © The slow step inarelvact one moles ofe Propomore Onel om Ayolrexidle Ton ; So Phage hee Sptetea appren i the rade. oguection. © The reaction is first ovelin with rispact to pimppancte ond first oveby With reapset to yet rice ono, © The overall ovilin fev fhe reaction if Seeovel Oven © The vate agvetion, rate =l{cHcoc LOH] © Bromine dots not appron inthe rate equotion sikee it pokes pact in 0 feat Shep offer vote determiscny shp.Tha hydrolysis of hologemoalkanca . * Heloatteonss (RX) are Mycholysrel by agrees huychror tele Fone s Rx + OH@y) ———7 ROH +X ° There eve tur possible machamisms 1) if yuen rate eqnohon > rate = k [Rx][OH] Mechars'sim | (hydalysis of Panel 2° heloakanto) « One Step reaction + requcres both species to col itle + ode fs affrctect by both reactor © secon arcler overadld . Exo meg le ene OH” —— CtlgC2 OH +B yo spate = kLCH;CAK-Bx) LOH] © The reaction is First orolen with respect to both, the organic Compound amel the hyebroniile (ola, + Both of Thue mmet be talecing port ih the, Slow step ofthe rreestion ©The readkion buat happen by a Straightfr vant collision betivan Hom« @ CHs~CH,~ Br —CHsoH HBr” 30H eT he carbon atom which is hit by the hydbroxitle ion has a slight positive charge on it ancl the bromine ofdin a light negative obs becouse Cs the bfferenc in they, ehacheinegodi vities , cfs the hycbroxite ih epproaches, the bromine is pushacl offin obe Shcoth action, st oh ) Liry Ry —> pay (1) Rf+0H > RPA > is ee) foo ip iYyclven foncla racdecig / red} deterfinans Atep. ° vate Spine lay on RXI/+2) if given rote 2qucchion : rote =kCRx] Mechanism 2 (hysholysis of 8 °haleatkanse) o-fo steps reactions: (i) RX —> REEK™ (ii) R*-+0H —> RoH . Step ti Ps Slower as it ihuctven benel braake anck thse will be the vate diteeimining step. + rate depends only on [RX] «© firsh orcler overall . Example. -(CHs)3C -Br + OH” ——s[CIts)sC—OH FB * rede = K[ICHs),C-Br] + The reaction is First ovclen with raped to Pha organic compound , owl zAre ov cle with raapret do the hy chraxttle fone. + The concentration of tha tyelwxida iene psn’ affocting the overell rote of the veootion . = The hydroxide Jono mut be todecng pact im a loter faat step. « Incr enaiha the conemtrdion of the hageleoxitle ion will speed up te fat stop, but will pot have a hoticeabls effete the overall rats of reaction, + The reaction vote 1S governest boy the sprcel of the slow step -chs I 6 vt oAS cis “Br SDs cinco + Br ch, ony CHs CHs } - Pot 1 cbr sy eee CHy-C-0H ch Hy «| this cose where the slow stop of the reaction is the first step , the vate epuadion tlle yrm what js Peng part in that Slow step Mo lech Tha rusrdosr of Inde Wired porticles of the reacting Specita toking pact ih the rate deteriniinng step to veoction. e4- B+ 2B —> C+D ro lech on hy is3- ot A and two Bis Avent fo collie A —>28 paglaclanty is | = only one Ais involved,