Reaction Kerutics (A2) Metreda -for Following Pha com se of @ raection. 2 In odie to Pind out hew the rate of reaction changes with Hint wa hard do soltet a cuideble mmetted to follers the progress of avecction ©The method will wasn ether Ho rote of dicpprarance of & ranctont, er the rete of eppsecence: of 5 pede Ke oo Some methods ave as ftlew f. doclcha cheork reactions ©The. reaction is the oxidation of feclicte ions by Ay thoegen proiicte Umoler acich cohtitieh. HaOaeq+ 2Tiagy + 2Hlayy—> Tategy +24Dy, © fodine als raacts with Soceuim Hivslfets selection © Te the reection mixture Cinclading ths Storch selcion), @ very small fixed asmewd of sodium Harerlfate scludion ales added. © The thie wkfate tora will react withthe Pochice that 1's inctially preducact, arch so The iorking woull affect the starch, anol do rot shaw anny blue ode, © Heweuer, whinthet sinal abwsunt of sock thireubfecte hos bean vord up strane 'S nothin te stop tha rest let of Folie produced Bom raactiy with the starch. The wixtere then Gee+ The experiment com be plana to lok ot the, affict of chonyng the hyctrogim pore niche Coneautrdion , ov the jodie (oh concentration, oF The hychragen 10h concentrection each tins, and mut kup offer teeters constort . 2+ Recetion betwen bivmocthens onol Sodio heb xile © CHGCH, Br + OH” ——> CH3CH.0H + Br” © During the Uurse of the reaction, both bromoethang amc cockium Ayolra rite will get uasel up + Tha exprcéinend com be stortedk by mining equak votuine of bromorthane amck Sockitimn hyctronice ( beth of Seine conertation) . © At ragulontine inter vols clenitg He vraction, a pipette. was vard to choke. Sodnphes © The samples ave quenched by eutdling 0 bmn Volume Cohosin fo be an axctes) of stomcterel Hef. eThedt will wor wep otk the seckium hyclrox ide in the. imcxtere fo that the reaction stops « © Now titede Has proubtitty solition with stoner Sedliiin hydre xide. sctidtton, to fencl out quent ca Hes daffour in the wcrtere . tol eo That Lets Cotertachion t quenhty Hel vsecb “Pp, which is Pra seams a2 qasbty of sob Ig ole xi Ae nwt have, been prtomt in He ompral rrection nixhre . © This sett of Fechni que 5 known oa a bok titre’oh3. Colerine © Ih anny recetion Iwelling a cxtevrect substonce Cetther resctiig ov being prodmcat), & colorimeter iS Uaed to follow the courte of the reaction . tae ig sensitive ee ce. oncl neler. OTe coleun of the light cam be chansid by sebcting a porhicule- colounsel Pitre. The cdivr 1S chosen sothet if is the Pra pucny of light which i508 sre by the. = T 7 © Exomple raachion bit wun proporrons onel joins ih the présence of on acl catalyst CH Coch, +1, —H*—> CH: Coc, I + Ht*+17 © The solution of iodiue ih pyopamona storks uff brown, an than frcls thrngh orange to yellow thon to Urtowrlies ao the Todehe ws useck up + © A cederiimetnr cam measure the amernt of light lohech (3 obsorbad a it passes Horonph ox sebetion— Pacordsd aa the cbsorbanee of the solation , 2 Duvitg the exprimnd, dake the vsncling of absorbance. from fhe moter at 1 jade yale) amet then compared agant calibration curve fo convert Phose voluas into concert ong. Ta egy +2 HQ, 4) pressure bar ogurtinsnt — CCCHs), TZ) ——> C(CH),= CHayg, + Hig, ©. Kg SS Mithod V8. Direct Measurement Matte cl Direct mauuremut method de mit requcre the removed of samples from the reacting maxtire The vecction js determnnecl ot vagelon iidecvels With ot cbisterbihg the reaction net, ©. Sampling Method Tavite potrchad comtata: nation ds Tha rroction be rtre 0 Sampling mathe invelied mary stepa omcl potmbally eredt mere Enron «Rate Eqyrotone ©The rade equation mathematically Linke te the concondraion of reoctonts = can only be foond by deing achuel txpininats, not by locking at the chamecal +guation. © ES the chamcad equetion t A +284 X —> C+D © Arote equation: vote = k(A][B]™ where i nits rote : rate freation conc. (met dee’) tite ke trate constont —— deperol onthe rate sagaction L] ¢ tchentration mot Lin? © Intecpratation . The above rate equotien explaine thet the vote of reaction is! © Preportioncl to the cone of reactrat A cll [A] -will able vate © proportioned te He sputre of the onc B Hanae cnet properkicined te ths cone of X alfa [k]~ he = i‘ effet om rete,+ Example 1. — power of cone of reacterts rut fellow sfrichivinetric 21 ep + S2 Oy egy 9 Tey + 280,°%, rote = kIT] [S.0,°] (ec (rT Ls0e * Example 2.- may inet inclacle al (or any) peactents in Chetnetak equrcction wnilten . (C1a)3C- Clog + OH Wag) — (Cha), C-0 Hog, F Clog rete = kk [CcHs),c-CiJ (nde = [OW] nat opptow inthe vate eqeation) ° Example 3. - Mag include Substomces thet are not reactants ih the hebuitad eguortion 2Niy — > Now) vote = KIN]*[N,] Chote = thengh Ma is a product i the. chatatal &guchion)Order of reaction * [ndevidbaol orien — Tha power to whith & Cohten drotion is raised in the rete 2quoction . © Quscall oreo — The sum of all the jadi orctere inthe vote equechion « eeg. inthe vote eyechon, rete = k(AI(B]* © the order with weapet to Ais] (Ist ovelen’) © the ovclen with reapect rh Bis 2 (andl evel) othe ourall order is 3 (Bveb ovden Gemoralising the findings ° By cathy expeaineds inyelithy a reaction betwen A omot B, It was Foumel fh the vate of the beacon Was related t the cohemtretions of A onl B ih the way 2 ontenet remchion 7 wiirahane A orden of reaction 7 with vaspect to B h pote = KCAL [Be contin 7 q an i rt dia? rede. ih rote constat concendretion of A motcton #s ih tmertedac > © The readion is inth ovdir with rupet to A © The ranebion is hth order with viapatte B © The evirol oncter of the veection is the sum(m+h) © Values «ovis eed not be whole numbers The most Likely ovddin of rection Gre O, Lord. Bud other yaluts eee possible, for axample +63.«orders Cam be Zero if the rate iS unaffected by how puch Substance 1s preset « [sported neha The rete equction is derivect Aroha axpan maastl evithace not by tom an equation 7 Specie inthe shichiomebe equecion somet mea arewl ih the rete 2question = Substances tuck 1h The stoi ioteby 2quch®” Com Apres in the vate eqvedtion . © Rete equcctions for some reections : etic & Ye rete epoch | | Hap +Z2g9 —> 2HTy) if ksh] 2 NO) + COgy + Ontgy —2 NO aig) +COD19) r= k {vo} 2Hoyy) + 2Ny —> 2PbLy -+Nougr = kU Ive) Be Opi +88) by thi BBraty T3IOuy F=Kle-cIls- Example The racetion 2A4+B+C —72D4E rede equchon is > vate = kKLAJLB]~ Whet ove the indi vrdienl orders ancl evar! eviler fem the above veadion® The rrodion is Ist order with rupact tA. The vanction is 2nel onde with riopect t B The reaction iS Zio ove with rupet to C . The overoth order of He reedion is 3 -The vote comstot 2 The pede constact 1s Constant fer a givin recction ondy if ath the changing 1s the concentrstion of the rradets and the othon trots (4g bempacttine, woe of Cotrlyst ef) remains unchangact . © The vate constont varies for a vraction , Mf there 1s chengig in dhe tempacrters, of the reaction, octet & cetelyst , oy howe the coblyst Unds of Rete Constents + The units of the rete constowt clupancl om thy order ofthe reaction P Gn example of O first order rection ig (CHs), CB +04" —> H,) CCH 48-7 © Exprmudelly , the rete equetion is rote =k -[(C4s),C-8.] © Feamamging tha pede aqrcction _ lrete LCHs)2¢-Br] © Hence the unit of k= Urttef rete uncts of ([CH),C-Br] = molding ?st bro bin? =s7 The unt of the rate constent for all Ist orc vaection Fis 7h,© Second ordar reactions HCooNa + CH OH © Expreiinsnctally , the vate equcdion is rete = k.[Heooct ]LNaoH} © hamrranging He rate 2quetion Se cete K = TycooctsIEN=0H] - © Hence the units of K = a (Gas of coincentrations )* raot bin 3S ney oomtide aet S Tha units of the vecte constaut of Ul Seeoirl evetr reetiong are dimntmet 1S, © Thard oder renctiona An exemple. of 0 there ovcler reoehion #8 2NO+CH, ——? 2NMOCH © Ex periimiectally (the vote eynction is vate = k-[AC]* £04] © Hence the vv’ = eh ete rate, i al Lea orere ef concentrocions)” — metalnn igo! vst? hin dim? mt *57t o The umts for the rate constant of alt thirel ovder veactions are dinGinel 7S,Example | CHs-CH=CH, + Br, ——?CHs~CHBr ~CHa By The vote equotton for the above reachon is rate = k (CHs— CH=CH] [Ry] The rate constont, kis 80: 0du Smo 's7! @) Whet is The evelyn of the vecetion 2 6) Whot 1s the rote of rection When the concndrechions Of propene omcl bromine ore both 0-02 melcliw?? Air siser a) The oveler = br = 2, b) The vate = 30.0% 0-02 x0.02 = 0.0/2 mmddn 1s Example 2 2Hig —> Hey +1, The rate equctisn for the renction (8 rate = &.(HI]” AE G29 K onc at a concnfrotion of 200ml din”) te rote of decomposition of. bey thr2g on (ootscle = 24 X foSmncetnc?s"| a) Cokeakate the rete canctat k Por the vacction oC 69K, Give the uncts b) Caletate He Aaimber of hiydro gen jockidle he beebe Phot dacompore por Seon ih |din? eG gesera Inyclro gen, Roebtle at C29K Cat cortentetin 2-20 mutotin”?) , Chrvogacho consent = 6.0% 1078 mat J Risen : a) ka cate hetsetion = 2.onto® 26.0 %10 Hinind "67 D toe teers Se ete b) From the rete of reeetion, 20 Ale Fol of HI is decomposing ih Vda avery Steenol + Hines the hatebrnef molantis decomposing in [dint eviry seennel = 2HOK(e TK EO 1023 HGR ® 10%? ime ba kerodlince order of a reaction by imal retes onc Lnttiok concentrections “Example BrOs Ge) + Brig, teMloy 9 3Brgop +3H>Ou, Fete apprritmints Wire Const owt te inet ther the rete of the above reection depends onthe concnbahons Of BrOs”, Be ond HY. Tha rasalds tore sumimon'seol in The folly. teble « fcxpeninent [805] [Br] | [HJ [lke rote recon xy 2 r ! | 2 [2x] ¥ z 2r pec et ey] ea % x _|2y |2z gr 2) How dow the rete of remction depend on the concentrations of the veactants in The chemuited CquotionZ 6) whet is the rete epuction tor the reaction 7 ©) bihat isthe orden of the reection? Ad) What avetee uncts of the vate congtont 7Answers a) Comparing aypirinds (and 2¢ when lBrOs] is Aowhled, the rate is dowblad Hince rate o€ [BOF] Comparing sxpustnacts | ancl 33 Wh [Br] is dubbed, the rote 18 dowbbed . Hence rate sc [8/7] Comporig experimunts 3 and &; lohan [H"] is dewbld, the vate is Ihertasadl by afector of & Hence vate ve [H*]* b) The vats eguetion, rate =k [Bros ][8-J (u]* c) The ovder of reoction = 1+/-+2 24 _Unsteo rte (units concnchtions) ” 2 eae (rt dw 3)* = dmd ma? 87 9) The units of the rote constort, kCalculation of a rote constant wiihg jatil rate © In the prestnee of Aytragen Bis, hyctrojen prronicle, Hiro, reacts with fodkide fora te forin water enol jodine Hoe Gq) t Tay trey) —> 2400+ 1 ey, © The rate equetion is? vate=kKLO.)[T] ©The progress of the reaction com he fotlewsd imacouring the initio’ vate of Todkinadivimetion , Th tebh shows reaction rates chtrined uschy varius jnchal concentrations of tach racctmct . Expt [bomen Tt? [4 Tone? |Intitraschesatyrttio | as ea 0.0200 [0-cloo | O.c/on | 3.50% lo 2 | 0.0300 [o.oioo |O.0100 | 5:80 x 10% 3_| c.00s [o.0200 | O.0200 | 75 x 10% © Using the dete from eyprinaet |, cobeaboting thy rete comstent aa Showh below Shp li bode = kCH.023 (1 ] Shp2? pp 2 rate : ii (40,I[T] Shp 3: Sebshdote the vole = 88 HIT8 Ly Ze x Jot mol Md S” < * (o02)(0-01) Note > [Ht] is ighersel, because (H1) Mt oppton 1% the rote eqroton. (The reaction IS Ze ovele with aspect to CH]& (4) Caleulete a rot Sate from h i, For a first-order reaction, ha-life is relatect te the rote constant by the expression: z = 2693 - leg ie % | | ) Ey, : the halflife y unit 2 secon Revonte the expression : | 0.693 | k Exampli For the first-order reachon cyclopiopane te proptne, its hoffe is 17.0 min. by, = !Tomin = 17.0 x60 second ' :Exercise G. Use the cheta fom Aypacimoats 2 and @ ik the table of privicus example to calcrtote the vote oomstant for the Following reoetion | Hey + Whey tH > 2Hsbyr + Tofagy The rete cqnetion for Hus rtoction i: rote = kCM03[1] Ansisees K (expuriment 2) = 0: 017 Tole mel ™ fe Cepentmost 3) = 0017S are b- Use the formula 4-22 to caborkate a vole for the rote constout of a raection which is first order ancl Aas a hall-Afe of 480s. CAnswer k= bbq xto 384) C. A fist-ordsy veaction has avate constont of 9-63 x0 SS". Cohcalate @ vrolus for the Alf -Wfs of Hus reocton (Arsure ty = 72005 )Yrapha re peocion agachat contntrettin of reactant reaction rete paetdin tas! , Second ovels~ / rete=k (R]* First ode rote =k(R] 2, Concentration off vanctoch, ERY / mot din? °Grephe show Changes th the Comsndretion of O Veneto alfed the vincten vate of Ztre-, first Oncl teeorcl— ove reactions . Zar orden renction © 2§- DAH ag eS Nays + BHagy «from expt, rote = KINM]° ° Greph rote of reaction agent concen hoction of pamctent ~ a honzorded shoight (ite ° the rection vole dow mt Chonge With Conunbetion, erote =k.stumde reechion , 625. ZNO $44 2May, tO) «froin experiment, rate = k [M20] ' Gr pete =k) « The plot of resctio rate against cohteatmndion of Peactent — an thekined sdeight dine. getog theorgh the, origin © The wate is directly proportioned to the Conantedon of N20, © Debby phe cmanbation of M0 doubles Hes, rate of reaction. a * G rad = Sreond — oven heaton Sie ane eg. NOx F CO%, ofroin ayprmed, rate = k [NO]? © The plot of reaction rete egainet ranctont Conumtredioh — An upwardly curved [Vas - © The vecction rate js cdinnctty proportioned to the sytere of the contentretion of NOr6). © The concentration of M24) devbles, the vote efy reaction jhevoases forurfolel « 2 ot | mbdwt, rate =h(I)*= Ik of 2 molda?, rete =kK(2)*= 4k. + plotting rate vs, [NOL] * gcves a shecght [ine > NO + COru)Exerecse Draw sketch graphs of reaction rate agacnat. Concentration of the renctaut unlerlehect for cach of the following reactions a) Nw + CO, + nig) —> NOt +COs4) For which tha vate xqnrcchion (6: rate = k[wo]* §) 2Hq M4 > Harr + Toy) Pew which the rate equation 1s rate=k Note: the cotelyst hFlusn coo the onclen here — the odin is rot the same do for He Uncately seul ram, ©) (CHs) CCI #OH” ——9 CH) ,CoH #017 for which the rate eyustion ts vate = k[Cctts)3CC]capha reactont concentration Agaciat Hine « shew the chanyts th the vohuntrodion of a rsoctawt ad differ red Pilees ds renction proceed . Conungration of rental ERI / melding Zere ord first orden Second ovclen Pathe Is 8 Con dlishnguish betien 3eo-, first ane Sterol —cv clin rochiong Zero Orplen + the graph is ciacencling staight bine © the vate of reaction is the slope (gradiot) of the Be © the reaction pro teres ot phe Lame rate (courtet ate) whatever the contenpadion of The reactort Eivst Order © deckthes th @ Shetbow curve Szcenol Orch the Curva 8 much deeper than (sh oveler ren + cleo appsces to have 0 relat 'vely longr tect” ce it devel off.wlife (f) Defintion : 1s the fire teten for the concentration of avecctant fo fal do half of its omgrncd value Evampte : resction cycleprepone —> propete Cegeleprop ans] /mkdin A L.cyote prpana] mtd Half ife/man 4,00 f 2:00 ioe 2.60 fo /.00 34.3-17-0=|7.3} 100 0-80 (510-343-167 Tine/iin © A constant helf-life trdecates a First-order Fn. > In the first order reoctron, the half-life is in dep rmclont of He ongined conuntrotion of venctant .5 a oe ane ty (it) tort) tylist) *hlend) turtist) tyQrl tn Filme. time time ehas successive Aate-lives which cheereoars with tine © First-order racction chin & half -life which /s constant. © Second evel reaction o hes succespve helf-[ives whith inerense 6/Ih time. © Kighre evden Por 0 pow talon reacted will alse Show succesive half-lives which jnortate with thes.Example Bon3imachazgonium Chhenile, Cos N2C/ decomposes of rom temp erotics. ‘ Cos NaCl egy + Hoy, —> Cos CHegy + Niaig) + Helos, &- Disembe how this reaction can be motored. b. Ussing Hh acta In tha rtedle , plot a graph of- concentration of Co Hs Na Cl agacnat Hie Tike [5 \[CcHsNaci]/1or mek clm 3 ° 58 200 400 Goo Boo [tooo [1200 | 1400 feo | o3 ©: From your graph Find the valus of toe Successive half - Ives d- Uae the volues of these Aalf —Ii'veato deduce the orden of the reaction .Ansusers - 4) By measuring the volume of Hibegengas giv ef with-tine using 2 ges Sytiys - 1 Geatenscil/1tmetde* 6.0) a) 40} SoS. : 20} Torti Ps ! t ects, 0 rp © Bed bor bce Foo 1000 12e0 Ihe Leow bol ©) From (CcHsN, C1] = 58x10 SmAdin? to [CoHeNs C1) =2.4K10* mat? , Ist Ty =4608 “+ Fem [Cette NaCi] = 2.1416" Sretdag tte [CeHsAlsci}= bs x0 mal ct?» 2nd Ty, = 4408 J) Ty, (ist) more ov dew the same oa Tj,( 2nd), therefore the reaction 28 first avder. 24sing concentration-tine grep hte calobate inciod rote Ht Bry + HCoorhey > 28K) 12Hey +r, © The course of reaction coh be folleted colon ied cathy by mmansuring the intensity of the. ved-hrowh bromine of sudable time intrrvels, “By plotting a celibraction curve of known bromine. Concentrations gaint coleriindtin reecknga, the Concentretions of bromine fromm the colon meten rencbings com be deduced et. vorous tine inpurvols , * Results of Peection betwern bromihe oncl metho cerel Tima /s | EBriJ/metetn > © O-0100 30 0.0090 Go 0-008) qo | o.0073 | 120 0.0066 _ | 180 0.0063 [240 | 0-004y | [360 | e-co28 fe _| 0: 6620 as O0013© The. concentrations CBr] polls? * Shier 4 ieee eae ee Ta? dias © The conuntrotion of bicimne [85] Fede cluning the cose of the reaction . © reattion rate. = — rate c& change of bromine catcen tection - —Al&) de. © hegetive Sigh Used because the bromine 18 being Usedl up, © [hn order to obteih the vention rote ot ema geen time, draw @ fomgint to the Curve at Had pockerle, Hime ancl Imeatens its grec ent . © prodient of a = frat intial rete (at time =O) . grodiont b = Quirage peaction vate for 2o7, completion © gradient of © = average rection vate. for A completron .Kinetics ond Reaction Mechancsma (AZ) © Many reoiohe occur jh Q humber of: steps. This IS coh fhe reotion mechanisin, = These steps toke plo at fs own vote anol hone its own rote constont, © The over rote of & pul’ step protuss depencls On the slowut Step ©The slowst stip is known a0 the rate determing step. © iAUAahy gortion of the. rode eauotion Gives an idee of the shepa frvelvrcl ih Q yrecttoh . « A reoctont thet apprors th the chapmicad @puation nay have ho effet Oh Feoton rote. oA substince which is nota reactent ih the Choims'tol 2tuotion Can offect reaction rete , Example | *Reachion between lodias ancl Propane : CH3Coch + 1, ——» CH3CockK,T +H1 © The rate Lenretion > rete = k[CH; coc] (H7] °(H7] in the rete equedion becouse reaction 18 Cettlyeol loy vec °[1,] net ih the rate equation baconee the reoctivn hoo move thamore stip ancl Ae slowut step lori ihvotue, Poche . © The rote determining step rust therefore huelve propasuore ae ace. !Ven fying possibhe reaction mechaniting © Kinetic deta com only shins thot O proposack beection mechanism 7S possible . ° The reaction machoniin iS hot checlreagl fom the kink date, a Ena maple / © Various machanisme Neve bron pr poset fo the ren CHacocd; +1, > cHscoclal tH & Ohe proposed Ins choni'sin ¢ , Feat w a CHy-C-cH, THY SE CH -c cH, “pe slow ot + CHs-C—CH, ———? CHy—c=Chy +H a : val a cH,-C=ch, +12 ? CH -C~ owt + T oH ° Ch-C~cnt + 7 fat. Cis-E-Ct FHI o The rate equation Poy Has renction 1s rate = k(CH;COCHS ICH] © Frm the miechanisin, the rate determining step (slow st ep) dose not ” invelve erther propanchs or ee joe civectty . a © However, the intermactote cys-6—cy 8 dortveol ae substances ( proponent enol hy chrsgen Fons) which raat hogefher io Porm It. So beth [cHscocts] one (H*] appton in the vate 2eustion. 2H.0u, they, The rece equation fur this reection is rate = CH.0.) (te) The machanisin bilow has bsem pro poseel fur thiy vaodidn. eoeeeene slow. Hot LO" H*++ Io” ft __, H10 Hot #t+ > St 3, +HL0 Explacn why tes Inschaursin TS Cohststent with tha vote agured ton : Arata The. rete equrection Shuws tet the vote decberiectcieg stp» Involved HO2 and Tiong. The hy srogen jonas do hot pron jh the rote quation bypeanee, ore juntushin faut steps abch tobe place offer the rote dle ry mahtng step (slow stp). So the proposed mach on'sin is cons ®tenf wit, tha vate 2erat}on ,Predicting tha orden of 0 reoction Pro im raection bechan' iy © [f the intermediotes prroott Ih The rote detertnibiteg Step Cov substonees which reoct together ty frrin the Prferimaolente ) arg Identified, Han We Con predict the oder of veechon froma given reaction mechancsin, i Error ple > The reaction of propanone with bromine jn otkabre colaton , CH3COCH; + Br, +OH —> CHsC OCH, By t/ho+Br © The headion mechanism . Hoo ait a ° 4 wd oey ie pamistesrs H-C~c-C2” +h aac 4 © Past Oo 4 7 ease > wt & 6-8 +Br 4 # 4 4 © The shas step is the vate —b.cter mibing step. © The slow step imrolued ohe wrolecuke of proporone Orel on hag olore x fle, Ton ) So omy these twe Speieca apprer ih the rate equation, ° The reaction is fst ovelen with rispet to propancre ond first oveler with ra to hyclrw nice Pono, © The wvtrall over fur fhe reaction Ff S2eovel Ov-chey. © The rade. 2gvedioy rate =h[CHscocHts LOH] © Bromine does not appran jn the vate eget on sikeg i} -fokea part in a fast step offer rede determining stp. sThe hydrolysis of halegamocthanes . e Holo Unonss (RX) are Aajobroly seal by Oquenca huyobror iets Tons: : Rx + OH ———7 ROH + x7 ° There ave two possible machenisms « 1) if given rate equation vate = k [Rx][OH] Mechenism | Chgderlys's € 1 anof 2° holoakanse) « One Step retin . requcrss both Specisa thy col litle + vote is affrctect by both reacdont 2 Steondl orcler overald . Ero he a - ClCH, By +07 — CH3CH20H tbr spate = KOCHsCH-B) LOH] © The renection is first orcle~ with respect to both The ovganic computncl andl the hyobror ite ora. » Both of Thise barat be todecng joort th Fhe Slow step of Hh vaection , * The praction must happon by a Straighthy wont collision betwen Hon .Pa o~ cma ———> CH3-CHaxoH} +:Br 20H" oThe | adom which is het by the beg bron jtle fon has a slight positive charge on ifand the bromine otvm a slight nag of Vue Oba he cauee oN The bifference in thei chachoiegodt vities , ° As the hej cbrore ithe jon oppronchss, the bromine Ts pushed offin ole Shisoth acon |* 2) if given rate equation : rate =kURx] E Mechanisin 2 (hydwlysis of 8 *hetoatkansa) efwo steps peactiona > wo RK —> Rt-#X™ (li) R*+0H ——> ROH ° Shep (1) Ts Slower ao it ihvolven bonol breaking anc thas will be the vate detartniing step . © pot, dep encle omy oh ERX & first oreler overall « Example : « (CHs)3C -Bx + OH” ——>(Chts)sC-OH FB * rade = k[CH:)sC-Br] «The reaction is first oveler w ith raaped to the og anit compouncl ; omel Zhe ordler with Ytopect to the hag obra fle lone, © The contentrotion of tha tylwxitla iene isn'E affocting the over rote of the veotion , The hyclrox ice Fone puet be todechg pact ih a loti fort step. o Ihevsasihg the con centred of the hag cbror idle f0n wilt 5 pred up toe frat stap , hut will pot have a Notice obs, on the overall rata of reaction , The readion vote iS Quverneol lay Phe. Sprocl of the slow step -low Gite Ba SEP ci C+ 2 Br dng i CHs~C~Br cH, hs CAs Cho ee) Meeet Chy-C 0} chk Hy ely this case where the show stop of-the raaction is the first step, the vote eguadion tells you whet js teeing part in thaf slow step. Mo leek a : The numbs, ae jraividirsd explo of He raocting spacitatekihg pact ih the rate determing step of a yeodtton, ea. A+ 2B —7 C+D molelaity is 3- One Ar ancl two B's heed to colbrte A —>28 molrelacty a only one AS thuotued.Cotedysis (Az) ; Catalysts (positive cordyst) increose the rote of Ahamicd reaction, fi clo the by providleng on olterhroAtve prt Por the veaction with lower oct yorion orsroy there are Pwo mary cloana : , ‘) Horo genrewe carkedy cis i) Heleog ensona cattelys is . Homog ens.eus cotedy sis . Coctodlyct ancl reactants ace ih the Same phase, © reaction precede Prrough cn jhtsrmecliate Species with lower basegy . ° often involves changer in on ietion Matrlotyn of the johns hued vel fh cotely sis. - Ex ong be 2 hydro gen Vom cotelyse thy Aagdedysis of eter, CHa COOGHe gy + HhOy, HW CH Coothy + CoHeoHey * reoctwds ancl cotedy of ane a jn the Same phase (agrees phade) 5 2 Example : Smalt amounts of jodide jong cotrdyse the decomposition Of Aychrogen paroxicle, * [n the. cotolysack rroction , jodcde jona, Tj are first onideseot to iodoteti) ions, 10" The 1D” ious than veot with Further molecules of hydlro gen prroxidle ancl ove reduced back to Fodktke Fong .H2Osy + Tag ——> Hs0y) + Tova, Haw, ty + IO%y ——> How + Tep #0, © The overcll 2 guration AL 2H Daeg, aaa 20, + Osu, © lone of dtronsifton Cements ore often grok catody sts becouse € their ability ty chonge onicletion Wuinh on, Wyo Example 2 Tha jockihe~prroxodisulfats reaction. * Parone disulfate (on, SOs” onitise ioobitle jone to Tockue . This reotion 13 Vary slow. S 20g" (eg) F 2 Ley —_ 250 + Treg, ° Beth peroxodisulfate ond fodide Moho have Oo negative Aaras . < [rr ovder fo callie ond react, Phase fons heecl considrralle energy to Overcome the repdar'oh farceg when Like chovges Opp roach 2ocd then, * Fa ity toro cockolyse Has ranction. The cately sis Thuotven 2 reeox reacts ha. - ° Reaction | 2 reduction of Leitiong to Fe Vous byl Foust Qty +2 2Feep + Tey * Reaction 2. + onitatione Fe /one beck fo by Se 2Foy t Sabep 7 2Fatag + 2 Pye,* [nr both reoctiong | encl 2, positively chergse ion joke react With hag ohvely chargre ions. © Sihee fore with opposite chaeg en Gre attracted to cack other, those reaching ove more Likely to eeu than direct rection betworn SO,* enol Tjous. 2 The reaction js Costoly eaot by Peep ond (PPS abo catalysed by Fevty- eltis ods bt fo the, reais 2 to OCiun first Fotlowael by preodtion | . B Ensryy profile diagram Fr cottelly secb omek uncectolyad reodtiong ? ewig |sofer™ lat | reachonl |reaeton2 4 pat \ | pee ket_[eore" S um codraly sacl reacton catelysed yrodion cach of He steps has a lower activation energy (Ea enol Ea.) than the sihgls reaction wither A codtdyst « 2S04+T, Progvare of reocten | © The codalyecl reaction Aas 2 yg prake became itis atuo~ stage peaction. o Lh dle, for ths codedysis forrark, the sdancarol elo trode potectiote fon the reactions in voting the cotalyst inst le bet ween the ebectoels potmtials inwot vhs the Piro reoetouts .© Tha electrode potodtial ceagrann Pow the coctalisi's of the weaction SoOp> 49 T° —9 250,74 I, EW +20] —— — — $2097 + 2e° SA ZSHPE™ at - ie zt 4077) — — ee s04 ~~ —~— J, +20 21 ©The wae of ebectocle poteetials in this way 6 p Y Predicts thot the cortly sis iS possible , Ht cloeg hot Give eng inforinafion obout the vote of reoction. Exa.teple > Nitogen on iden and oxidation of SO, © S02 Js Produced when fossil Puels conteutncteg Silt are burht. ; © Ih S02 2acapeo inte the otmwsphore i+ condnhifes to oerd rach, © One of He steps 1h the formation of aciel vain is the oxtdetion of So, to S05 SOrgy + Ye0x19) —> Sig) ° Nitrogen (iv) oxide prasent in the ot mosphoee con Cododyse. the oxidation of S02. S025) tNOay ——P SF Ong) + NAG) rrr © The riche ganl tv) oxide js vafor mel by ranction with cddmea phere on ygen«Exerevse a) Which of the pairs of Substomces () AOU) below might codelyst the reaction > S208 ey + 2Tey ——> 280, + Tagg, Explain oor onsen 0 NP top /Nissy Es -0.r5V (i) Maio [Wings pra 414d Gi) Cepfay Eta 4 ev (iv) “ey/ Coley Ev =40/6V b) Duserthe in perma of onidadion ruibsr change, which Speeres ave being oxidésed Gril which are being reobaced jn these eguatrona : () S0.q 44 Ost ——> SO, °3 +NOqgy Gi) NOB) + 40 x49, —> VPr19 Answers ° Q) stoncarct slectroce potetiod S20, /S0,27 EPs F2-01V (Pron dete bookbt ) t2/t7 EP = 40.54V Both Gir Mn2* [in ord Wii) Co YC™ might cotlyse the ven These ave the paivs whith have ET values between these of the S20, $0,>° onl L7/ Ta pois - b © cridetion bo Change = —~2 radiation — S$ Ong, + NOs (4) ——> SOayq + NO, HOT OD te OT ee {__ensaetion a oxidehion no ch 2 7 exited chenge = 2 ai) [radiction iat Noy + 4Os%) 7 NOxg, +2 © +2 -2 |___onichech’on | + SKidchion ne Chimge = +2Hetrogeniony ely . codtely st ts ina dffer ont phase to ths. reactors o Of fen tavodues gasecue parole chs renting at the Surface, of a solid catalyst. © Action tukeo ploce at active sifes on the surface of a seted (2-9. a mote ) © Gases ore adserbed onfotte Surface ond Form weak bonds with meted atoma. ° Catalysis works jh three stages : 2 Adsoption ~ formodion of bo nde with the mated may use some of the ebechona from bonds within Fla ga roo lecadin thon weaken thage bonds ancl nokecng a subsequont reason Base , + 2- Reaction — ad Sovped gosea mag bo Add on the sinface of Ha mato ih goat the vig ht Onededion for & Veaction Fo otter. This th Grceaey the Chances of Porrourah be colksrona fokeng place . «3. ovption — tha products ore flan veleaganel from the wetive sitea. eferogenesus dsorp-tien — te bon the Sufix ee Adserk — 40 boncl fo the surface Of & Substance, esorpton . Ph sock — to move ight into The Substance - Clike & spo: bsorh. ey nage absorbs fe]=[z]Example: Iron cotelyses the Haber proces Nagit326, 2 2/456) conch fiom: Temp rrocine S00 eC Prassire—lOo atin _ Cotelyse— bron an works by allouring hydrogen ancl Gem molacls to come close tegethe on the Surferce of the fron, Thay ee hay ee o The five steps th Hho hiteogenacus Cockulys is > o |. Diffusion ~ rahe gan 6% ono hey cero.g om gaa ffs tothe Surfers of the iton . °2. Adsorption — the reoctout molecules ave chal adsorbed orto the surface of the iden. The bord formed between the reactort moleules anol the jh Gre 2 = strony sncugh te wroken The covelint boncla within the nihogen anc hydrogen we lecukes So the atome can react with each other . ~ weak emengh to break ancl allow tha products to feaye the surfoee - 3. Renefion—the adsorbed hidog in ancl hy olreg en Ae ee on tha surface of the ‘rondo forin Alyn melke . . 4, Desorption ~the bonds betisgan the Olnroine CL of the iron weaken and are au broken. © f. Dikfuston — amore dffrsea On any ‘fio bs the surface of the fron.o A possible mechanism For code sis in fhe Hoben pp rocisa, uc# NS Dickieersin ner ee Surface of the Tron. 2) adsorption tf iL ih how bonds avin BoA 4 3) resection (in severed steps) Lt 4 He 4) desorption oe i . . wry P 5) diffusion aatouy Brom Surface. a F—_LExample: Cortodestic. removal of inrtog rn owicles in He exhaust goase Brom Stor bgiiee . Codadytic converters holp to cohvert harm fil nitro gen oxtdes ancl carbon mohor/de preaint th the Anhourt 4 oaea from Car ergs to harmless fosea. © Tha. “hehag comb’ stractune insicle the codlytic converter comtuchs Small beacks cootect with pladimum ; pollodum or rhediubr , These, act an hatero geneous cotely sts . © Possible steps Th the codulydic protas Are - adsorption & ritrogen oxen and carbon ime oxide onto the catelyst surface. - weoksnilg of the covaleat bonds within the mitogen oritles and carbon morwr ide. —forimation of new horde betwam » v adjacent nitrogen odo ma to forin hithrog on Imo leentes V carbon mehexide and oxy gen atoms to form carbon oliexitle . = desorption of pihogen pao lecdea ond cordon a ##&#@ #3 « ii of ths, catedystEyes a} Decenbe in govrel fering what 's braant bey desorption . b) Nicked acts ag a cotalyst for the hagolrogenaction of oUeonws, For example 2 CH=CH, +H, YO CH;-CH; Suggest hove rickel cotrlyces tis reaction by refering to the proceso of adsorption, heaetion oh tha met surface anol desorption cy In codnlytic converters, rheckium Codey §20 the pooluetion of pidrogen(tt) oxide, NO to nibegen. Drow dvegram to gg sat: 1) Aow NO 7s aclourbscl onto the Surface of the rhodium muted , G1) how ra'hro gin is formed , foAnswes . a) fon is the veleostng of product from the surface of a cortege 6) Adsorption — The ethens anc hychogen molecule, Ore adsorbsd onto the surface, of the withel . Ty this Precis, lytete bons ove forineol between the ethene ond the surfan of tha nickel ancl betiveon He hujdlro gen and the Surface of the nickel . Reoction — The bonce between the hyolrigen tous Are wiakensd and the TT bowel of fhe etheng (8 alae wealronrd. Aclsorhect Pagobrog ta oto mg close to the aoclsorbect ethene then rract dW forin ethane . the othe of Desorptich — The bores betwen fae Con ths sterdce of the nickel weaken ancl the ethane Mots awoy Prin tha Sbyface of the costeliy st. C) 0) bende weekendng Nand © 6 adserbact 8 " bh a ——> @hoo (1) bonds Porn between i ae t desorphon O Nw i g NEN © 7 7 TTTTTT RA SucfaceThe strength of odserpion is riticad # i adsorption — + feo weak A) [erin Tv er vtoo chong) Ut Tt It fe ihicmdprned™ re . . reaHon , juatrigit (wife) Lvl | Cochdysis of gaseous reactions Com feat to on Tnertase ih rete jn Severed waygo— © ohk speciea js adsorbact onto the Surfoes anel iS more Ackoly to undlor Go a collistey. ° Ohe species js held ih a fausuroble position fora reaction fo occur, ° adsorptich ontothe surface allows bende to breok and frag mints peoet quicker , © two reactonts are adsorbeot oberg s ide och other give & grsetin concntation » Formed of using catelyst — to moxituse its capacity , e Used ina Final civil Povin = jhereases the Surface req = provides more collision Siteg © mounted ih a support haeckiula — marin ses Surface arta and reduces cots.