Chemical kinedies C reaction > Rate o _> Robe is omen in eoncentnalion overt o diene. period aos wWherk 5 D means “ahangt | CL] means enolare ntact: 4 represents time. & Average rate reales % ay Tashan taneous rate > Types of measured ci) Tailial rate Avera nate > of 4ae rteachanl ort concentnation of any ao The change in unit dime over oo definite produc pert any of the time jnterval. aw7P ot = 4. 7h: or > (R], ~ CAs or- (rl, ~ (Pd, > Average robe of the ceatlion ating dime interval Dt > Crow) a [G2 aRole of change in conanination of o reactant on & product al a pardiculare dime. instant during the. course of a reaction = is edlad indantanzous rate of reeacion. A — 8 Wy The instantaneous tale reaachion in Aenms of change 0 , toncenination of -~—rteachant A at time, eat => Bie (=88, - - 38 avo \ ot ~ a + Tn denms of produc 8, the trslontanzous cote of = raction » stim AB = 88 ar70 8 at tangent do cunve at anu pont se Ae > The slope of ine inclontongous ala ot hat dime. Rate law 7 mr A 4 2b =» 3699 pote = -slAl 2 - at Se > The cate of daensace of B of ASsue? 0,40, == 2N0 i de = - A = Rade in tereros of reactants [me] - xu [ 02) fale in terms of producls = 2d [m0] considering she sto chiomalry of v-revaction 5 the rale of reaction can of rea clion 7 Eactone hat affect cate ————— ae when dwo chemicals react » cHeie molecules have to collide wit = each —otisre. with sufficient energy Lore the reaaction to dake. place. theory > : che: molecules tao Aempanalurce , mans ‘Tn erceasin move Dade. of reactants > ssa — kinetic Gh Concentration Ce = Moree rtsnctants means — morte. collision if enough onary is pre send , Speeds uw achvalion the rewaction by Meigering ho Anargies »of ao solid reactant 2 ~sonlact , do be in dv) Surface area Passa Lor evaclonts Mong area Buller seg) (Bread - and teeaclanis ore products ~ CO Prascurce of garenus (earns eee bangla er Jnereared no. of collisions. reales vail tf studing _nsaetion : maisduree will rove - Pasdicls how quicly a reaction qo -iKe2 equilbrium edale, 7 By - eontrollin: he affecting faclons » We can proceed sta saction at optimum rtqle. Te rele te foremulale the mechanienr of reaction. Rade equation oe rate lag = of meachion crate with > Tells us aloud = he dipendence athe concentration of the reacting components - > can only be foremulaled on He baeie of euperiman al dola. =a EN Ben ie beorsing with tha cloichiomel nic equation .‘pale Rale law fore any reaction cannol be predicled be merely lookin at +e balaneed chemical hao eclically bul mus} be delermined equation iQ, expecinen tally . Low of mass achion ~ Se ee erm a oy The, rate of ah, “ureters reaction Ca reaction Q ahol preeceeds Ahreough on one drrancition " edale ore one =n echanis tic step) 4s prioperelional to: the product eno locules. of *A2 concentrations of Hae participaling Rale law — aoe the ale of a — homogenous - reaction of te reactants is pro portional 4o tthe — preeducl of Ae eoncandnalions Talked 40 some power. 3 Thus, fon a general Agiclon 1 aA OB TT. C+ dO aoe « LAI* CI" 9 Bale = CAT" cel? ok Athe prcoportional conelons kacwn as rate constant ore specific role ore piel constant. ~ Har a specific value at a given dlom perradures .Oredore ofa avoaclion 7 eagles herein — Th sum of =e powers of concen dreation deems («4 @) Yn the rate equation is known as the overall —ortdare of — reaction. — K,B are calkd he partial orders with reen peed lo reaclanis Q@and B respectively. Ly ce ondere’ Of a cpnaction . hae generally a value of O° 40 3. ‘ 5 oredere can have also fractional value . eat decomposition of acetaldehyde - cHgchO chy +00 le ( oye vale = [cH ,CH0 ] onde = Fy om 1-6 Ordre 8 Ai ffenant fore sdoichiomedntic. aoe (ficient dederemined eupecinentally and nezds to be for on ondere rezaction A ——> product Rate = kLA]” ke Rate 2 Rale x A conc. 1 cal” Cal° tiew —— Ceone.)” > |k = Gn “1 + Liens wha ,m = ortdere of reaction.liatasslleelig of a _ reaction ~ 5 Gwimnteal reactions may be clactified into two Ayres = Slementar reaction ! raackon which eccurs In single sep. > _Gomplen_sepastion | reaction whieh occurs tn dwo ore more steps, Moveeutonily of an tlanandan reaction aa =o The eaolecalentl of an elementary, reaction is difingd as the mo. of — reeactant roolecules involved in a rteaclion. 5 Zero Orcdere reaction 7 eS ee 2NH, —> Nat 3H Role = K[NReI° 5 Firteh Ortdere tea lion 7 aS a aid 4,0, — Me +02 4 Rata: K LH20r] — pn | mostly radioactive and decomposition reaciions come undere first oredere eegaction. > Pseudo fire) ovdere rteaction See eye mE (seems 40 be second artelert) CHecd0CzHs + He Tame che cool} + Cah OH Bale does nol depend upon CH.0].(ences of 0) ts needed, hale: K [eWoC00CsHe | — Tero Order = ee Aa — P AO a 0 Ask, Can) ” Rate & Ca-a)° [fore zero ortdare reaction | > 8H x Can)” > sr AG *) » oe 2k (aa)? ek at » dusk at On Tolegrating » We a 2 > ke we 4Asky (a) ”w au ek Caen)! at On tabling, » We | S5 Becond Orders Halt - Life of a scenolion = zero ortdert reaction + dy 2 Wey i 1693 Fiach ortdert. reaction ¢ 4y, = ° 643 1, Becond ortdere reaction ! ty, = Ix | ) | Reaction — | Oredae Until of reale conelant i P ha | zen | 0 mol Lt 4 ot got a eden. Se eel, 2 calle | | s (ero U*) L a — ler. ~ oredare, 1 |) melt 7 [Ts Gut vt) fo 7 Second ortdere 2 mot Lo 1 am Lacbeenved vale laws Gore some reactions } ae ote Examples of fabs gee ce &) 3N0 \) — 2.0 cH) + N02 (9) rale = & [no] (na order in NO 3 Und ortdere overall ) & 2 w0.t) Bla) — 2M0aF 7) role =k (MOT Fe] (as) orden ip MO 5 Js) ovedne m Fe 1 Ded ovedn auvll) ay 2N01(4) — 2N0 (q) + 0. (4) role = k Laoa]’ (and ordere io N01 3 Und oredere overall ) G) HhD2 (aq) 4 317 (aq) 4 2H? (aq) — 220 (® 4 ToC 4) wale = wed ICI J (re ord in H202 ana Ainel onder in IT” 5 zero ondere io wt 4 ad oredere. overall)gieady stale approximation » stale app rronina tion and | quiliberiam sug _> Read of cornplee reactions. je He study oy For Findin rate of complex reeaclions ateady sdale approximations and equilibreium concep! is applied. 9 Tf ‘I? is InJeremediale at steady states rate of change of concentration of — intermediales is constont, formation of inlartediale = consumplion [11 +0 at 3 —Theree arco foure “ype of complen reactions ! re 5 slow slep and rtale conlnalling elep finst shop OND, + Fe > 2NOF Step 7 NOL4 Fe —“ 5 nok + F Ke Shep N02 + FF mJ ANO,F Q. show that ale of reaction is ~.twoy] = 2m LNOoITA] tins Boplying sloady slate approx. to F 5 a trl 20 = ky [no:] [ Fo] Rabe of — forernation = kL LAoILFd Rate of consumplion =S Role of formation = Rale of consumption > ks Eno l ad -ee Lvottr] = > KM CNOTL Fe] = he {wo.] (FI xs [FY Ma 4 [Fi * —— Rale of “disappeareance af 0, = Role of Step 1 + Rate of Shep 2 - Awd - i Cw JC Fe] 4 me teo.JLFR] “ —— dp From eq” (i) and ui , Ano] eer Cno, IDF] + ka [w0.1( Ley = 2, (woe LAT Ka Hence» proved. Tye a7 d finsk step in GW second step —? slow step equilibrium ; ano 4 Hy ——? M0 athO slop Tt ayo ee NaOe ° ke a “step Tt pd, 4 Hy 70 4 WO (sow) Q. Find rate. TIntenmsdiale is Noe. So\0 > relying eles stale Approwimalion ds Mbp2-[n,0,1 +0 at 7- % [n.d] [HJ =0 p we (noy? = Ka COT ME >. two) = Key M027 a, ON.0. 70h > ws [0OT” = [Ar0.1 (ks tet) 9g (M027 = ks Lol" ka eC] —— node = Ma LO TL Ae] = be CPT fs C0)” Kear 9 Ka (He J Case te if ky >> k, CHL] Rale > kike Ld] (HI = eC M07 CHL Ky ke Ka ke Koy cae 2: if kk CHL] ky Role = Ki BONO)" Let. &, Leo]? i One Tee 3: More than wo elancantany stops with one slow clep. cO + ¢@, — + coce, Step T2 ck, => ga = = Ske E- cov co SH code ~* kenshe 8 cpl sd, “+ coh, +¢t ~* Catow) Q. shoo rat 4 [coce, 7 =x Leo] {ce]™ Ants? “There are 2 inlerenadiales ; CL ond COC. tata aquibbrium concapt , Sept LCT = ky £00)" (ca 4" a ka —— & Step 2? From Step 2, w CCLICCO] = x, coca] Cooce] = me ee]Lcol key Pealing. wom OH), Vy [cored = % |ptou | [01 kK. L es Ker From sep 3 5 Rate = kg LC coce][ce, ] eal OL re y > Role = ks Me ts Coal] * Ceo}cetsx, gate = kK CCOTLCOT” 2 —__— 5 = klcoj(cl,1* a [cocd,] = at (Heve / proved Tyre 47 2.0, ——> 1N0, + O2 a. shew at A £04] ekLM0g] 5 Ketek t kas De \y 3 0 Shep U7 M05 = No, + NOs Ke Shep 22 0g + NO, 7 NO4 ND. 402 ( slouo) be, andy Step 3.3. N05 + NP Toleenediales ate NO and Na. Ans. 2 Replying leads slale approuimations to NOs, -$ [nol = 0 > Ks LT LA] = ks C627 C00 J y [wel > M ENO] b : Armand steady slale qppremimalions 46 NOs 5 ki LAOed = ky LNOLTONOLT 4%. Cm0gIT NO] +s lv0sI CVO] s Kilo,06] = [nsf x, Ch01 tka Lhe] + kel yor} 2 kk LNs (* Lol ft I )> thy {,0.] “os k& fad.) 4 2 tea f wy [06] [Wis] {i ) ky CAO] + De Lv, J CNT (est tay = —10 [nos J " y Rate of Me reaction » A [9,] = ki LOT [ 0.7 w aes 15) Paling w in Uh), We gets za Rade ay to > Uni0sd jy tword » fk CN0.] Ky 42k = & Cn05] Wonco , proved (Hence, peeved) Factions, evita Oa et — =? © Bond soy W&) Solvation eneray © trysical shale (a) Polarily piheyo concentration 2 Be Bard on rate law eupression yt, Oredere of eaCBAls _ Tampercalurce > eS — Tompercal urte coefficient = Se = a Tiis fe alio of wale constant which differ by 10°. Lt kz = male conclanl at any Jemperal uce. Tr. Temperalure — coeffici ky + 90 ir Gerorally > Kapp. 2 behwoen 2p 3 bee rale toe kiag 2-3 Himes Maxwellion curves eee ee a gS+ Fraction of molocules which ocd ~ fe Ethesshoid ) Leics she produc. —) Collision 's moree effective when kE il inerteared. = Only Hore Lnaslion af moleculas having ener equal oe greater. shan -Hreeshold eRe cawe ef lechive collisions ot with jnereace in dempeal urea. 1 KE jperteacos Catalyst tmcromse ore clecreeare he ale of moaclion b roviding an —allarenale path. Providing ? “Theories of reales of reaction = ae QW Collision taeorr oy Tee oF unimrolewla, eteacions ort. Lindemann — dire toa Vreore & Wd Activalad complex in — uw) Collision -teony 4 eae — Given “4 Arrhenius and v'anl Holl. —+ Collision ik essential belweon ruraclan| molecules Io LoAie ie. product. —> Even Hough collision {reequaney is very high, allcollisions to ool a" product. > Eeclive collision 4s requiend a) nana reequircamant , }.0., Wreethold onary ) Propere — ortienlalion of 4B2 —molecales « = athrervaltealys , [res 2 fP z= collision Freequaney, perc uni) volume =| ee" eee wi where , 6 = collision v2. w= 4olal no. perc unit We ovecagh £2 frartion of moloceles Vea eneraly fran ~hreethold ena . Ex, _ ew} Bolzmann factore pec uid tiore . tare) erce of acl nq molecules volume velocity i equal do ore moreCase I Collision behvaen similare prolaeules ore parclicles Cae L = Collision between | leg pale (8) 2 2£ 0 322 Eo? :F “a 7 = - Eq, > ne won , [ar ae aro rE aot n TT. a | R22 [zen | Case TL - Collision belweon different molecules gre_parelicles (A and) 4 Tolal ao. of collitions perc ee = A= to" (rn 4% YF r— 22 wr (99 + om) 9% v2 Subleeaeling collyion due to A-A and B-B ie . 2 ie Benn Eo (ng +6) % | ee ay no? B a Je = re Fixe ngng VY [ Cosy)’ -ab b= 2ab | v= (sat [. “an. 2 On +5 | ae ae fe eter a Qt | reduced Massfale R Case 12 oa Se, > 2fP - 2 ={(0 (ists Ths tig, = (2 (S482) m % BRT Jee 2 2uM _| LCi (Bids )onref EEE et ta i dem parcalurce ~ se affect of collision freaeuzo ? Considering iw zm & AGL Explanation fore RAZ 3 RaIT 5 foe, « [212 = 018 Raoo 300 faclore, Care 2 2 Considening Boltzmann faclore A & Bollemann R -£o/R +310 210 » Eq = 100kT7 aa > 2» = -Ea/R > 300 R= 8.314 > Rar = 3.6 Rav ~ Bollemann faclore is reesponrible fore significant Mike in rata. ~ \ Rala is allecled by BileeFann sfaclore.Covet of selualan Sangy 3 omy =o seas. Theaeshold enanay barerion. ==>) © Reaction progres Eq > aclivalion onary. As pert sallsiora ase 4) Aheoree aloays exists enarcgy Lareie? ere beloewn —eraclonls and producls. Rerne honius we * boqyk in, Ke poeelar 1 values incicoates exponentially with +e Weve in “tom peau A — pre enponenial faclore.1 Graphical evaluation s me cea lrg k , 2.303R aT faz —-m x 2.308R us B ecba/ RT 3 Ink = Un A - Ea aT ke le - £4 = 3 "Q' a8 2.303 RT 3 ke rea. 4+ Lon A , My 2.303RT 4 —— - cy ptesembler Ae taal 1Y amt4c. > Yon kK 3 mut -Ea 5 c2beq A 3 8 ’ 2.303RT 4 Yr is 0 straight ine. Tt has Q. “The plot of @nk We ~1.2% 10%. Calculale aelivalion oneray slope of Foc, We know » Unk = On A - Sp RT oo lo A + (2) RT oy Shope = a © 94 x10 ~1.2 710" Pp Ea = Bay > fas 49% 10" Tnal teal Motrod 5 ak Tr 5 dn ky es A ~ el ay Tr 5 On kee Rn Q — 2a am gb aa ea”) feo, O53 We gt!» In k= Unk, = a[na] Ty Te Q. A retaclion proceeds a \ner fatlare al 879°C ae i Aoee al 24°C, Find activation onary « Ast Tae (24 4 243) k = 300K Tre (9% 4273) k=. 310K Ma = Ska Riz 1.98 fog | Ki) . £4 Tr - Ty 4 a 2.3030, | ) ely 9 a io 2.3038 310 «306> Sq = by 3% 2.303% 1.98 x 30% 310 > Sq = 20.233 Keal g. @ fimsh oreden reanclion 16 SO%e complete in 28 minules. at 29°¢ and in & minules al 34%, omen” sl, Case T > (x), = 2S minules ty = (a3 4 273)k = 300k ky > 0-693 0.693 1 i), {3 2:685 wi cae UT 7 — (uy), = 5 minules 2 (gre 243) k= 310k log f ke) 2 22 Be] ‘4 (+) 2.2038 We 25 y Peae (2) ° : aa «] yore 4 Eq = fade ® 4% 2.303 %1-4B% 300731 Calculade activalion 3) Eq = 29,644 keal.Ae Al 300°C , ee olf -life of @ Sires| oredere reraclion js 880 minules . AdTualion oer = $00 kT [rool caleulale Sime foe 10% complttion of ruaction al 400°C - Sol" age a0 KT | mol, case T+ ob ES. Ts GdO4 273) k = SIBK (Ay), = 380 minvles w= (* 0.693, 380 Cae = Tae (4004 243)K = 693k Yo = 2-303 Lo Wo = qe 300-40 gy b= 2805, tears (a) also, Bo ‘we ) . _éa Te Ti Hw} ~ 2.3038 | th. Kxx 380’) , $00 £3000 _ 100 | 0-693 7.503 + 8.344 64346493 | D Qo foes 0.643 > Max 350 ~ 22,38 0.693> he (97.98 x 0648 asO 2 0.04 min” d | pdt = 2.303 + > £2 54-54 min js 20% complele in 30 minules, Q. A fire} ortder reeaclion Sime daken fore 25% completion caleulate reale constant and of reaction. sols Case L +, 2, 4, = 40 minules k> 2803 2.903 9, 100 aL “a ( 700 =20 = 2-303 fo 100. Due Bsr begun ( 202) vy ke 2-303 bog o£) 2(0.011 42) min’! 2 0.022 ara we 0.011 min”! ke ro ) toys (a) J 00m «3p tgs (38) ) a 2.303 ed 0.6 al > VV = 638.018 minOQ. for 9 Weel oredere reoaetion + half ile is 16 min. How euch dime 1s reequined bre ASS completion of reachion, ° . Sols, ty = 1S min. ks 0.693 s 0.693 min? Ay 15 ke 2308, fos eo ) 100-48 > 2.608. 2805 tog ( 200)) > t= 2.303 #18, bog “1 0-643 y Le BO wir. \"s for comlolion a a fore completion ] ASH neation of 50% of reeaclion Q- Tr a second onder reaction ,inilicl coneantralion is 0.2 cpl | idea. Reaclion is 30% complole rtale constant and half-Iife. in SO minules. cateulale a= 0:2 nol 29% of a > HK OD = BLK. 108” 10 SO 4= 50 min,3 — kz SO «0-2 (6.2 - 2 500 a 3) — =X = 0.04 30 (0-14) *SO - . os ed ee ee > F oon oot ? dy, > 12S mine Q, 1 Re aclivalion energy of a reaction is 20-4 1 [eal Calculate the “reaction of = molacale. 400°C , Which to fore Ae product: hove enough ener Gq 2 80.9 KT (mel, = 80.9 +10" T/rol. $.2 Tse (404 278)K= 673K Re 8.314 Ba/RT 5, ~ BA WA ainyoaa 14.45 g e = §3,02 x10{ore a reeaction when He Q, Coleulale activation enaray 5 eealied freoro 360k Je role it doubled = han Hemp 310k. st R=? T; = 300k T= 340k QkKyek 9 Kee? Ky As per Arrchenius equalon, tale = 7a 300 - 310 | ¢ 2:305R 300% 310 ) tos (2) = a8 ( ae 7.303% 0-314 | 300 % 318 0.301 » 2,303 x 8.314 x D0 x 310 0.804 4 2905 pi” OE tee ) Fa = 4 4, Be = 53548 T | rol 4 Fa = 53.6 KT [molconsocuve reonclions recaction which preocands freom reaaclanis CR) to pro ducls (P) in {wo ore enon slaps. Considers a simple consecutive Gree! oredere. ccoaclion. a —“w 9 7 —*— P o oO t20 9% 2 bet % 8 wThe reale of consump tion of eceaclant > pode 2 kh he at so a) Be aretiog <1Ro variables and integrating withia limils , 4 “| - “fat K & 0 y bo (4) = ket aks t x = @ 4 eae kit a =O a ; ? ——> aq Gi) Now ala of — foremalion of — inlecemediale Ii 5 Sy 2 kx -k “ d— of a.rng, ha value of ‘,” {evr eq” Ws ye (eet) my ksh d ky = wae” 7 Bey mating Gott do bath ahdus. woe gel ky -¥s ) 4 fad “ayn 27 Bee 1) 7 ye Cys) + a cot ) 2 > = Cy a ) > kyiae Tregyetting bol® sida, we alls at g ? [ ay. el he [ a) at ip” cme (hi - &) (ms ~ Tolegral ion constant ) Pat. Fore are 3 t26 ¥ To & “SO Raa ea Ke ka Ke L “Wh a: e™ & tra ( wo) aia Ma Kr a-havat :@ eka fhe -kot _ > 4 fu — [ ; Kab e = we ra oe | tin) girls _ :] } A 2 kid ao aX. ky-ks Freom conser yalion of mass 5 > nauning * and 4 fror9 ef” kad z= A-ae ka -Kx ——~ or dv) ae ety 2 Be a-wny. (i) and wy we gel » -ka [et — em kis da - = [ntl Al gate ed]Case LT kb oka* kr kp ye he eo Hence, ky and eo con be negieded. ze aA _ -kpt x) [° tae Bat ) Kat Ffex a Coeme) og ae | My Case TL ~ akit ty woos te a8 ek ge ach Hence, ky and eK can be negated Ky z 2 = [( 2k, e" )-0| Vo.catentnalion of Hrys Graph 7 / ( i 2 phils as a) a ? P Ai a conconteatet R dime R = reeaclant Tt — olecnediale P —+ Product. ive. czaclions fy? fron concaculive eaclions [ okt -kit | oo Me12 a Q, The half-lile of Pk je 306hnr, TY undecgoee decoy fo daughter clerent jar of halt Nile 60.5 mins. Caleulale Re dime al which dovghlen elomend elif have manimure aehivily Sol Ky ke ph —t > @: —* > Po 2 Na, ® 0.68 = 1-089 10 0.6x60 3 w= 0693 2 1.45% 10 60.5 3 Seg ge be(te) = 22 tof Be man Va My tis: 30.361 1.084 = 224 min. QP? (ty, = 3.08 min) decays dog, re (dy, 2 2.68 min) by at, G-ervillere. In an ening A - rays. While Pe is a experiment slanting with 4 gare alom fo”? sdiieio much dime would be required fore the nucle? of pb?” Ip rteath nak coneeniralion.o97 ky =_ 0-693. 9 258 3 nr 7 68 ks = 0:643 _ 09,22% 3.05 4 0.258 doe 2 — 2 dof) = (3 ) to | ie kik te ) aa 0.224 > 0.128 ~ 4,124 mins 0.031 arailel reaction ~, [ajoe Produel and side Creoduct) i ed morte -+han ont _. Reactions in Which _ meactanls ~ reach in ao yy eding differant sels of products. Two reaction 4 Se db Ma joc —___——> Produces Pf, diy) Side reaction —~ Produces Ps. ks —— Pa ge — 4 L_____» Ps Ke — Role of — foremalion eof Mmajere produc! 1 Fra =A Chm] = kLRI + Role of foremation of _ side product 5 Pee CPJ , te fed of — Atvappennance. of R, wCR1 + CRI -(kr 4) (RI ~ Overall , cate “ae CAT = y ACed = dadWin aes bla x) —k,% subsilulin aha value of Ky from a” ci)» Ag = Sloe) tee Coma ab He > 9H 2 ky 0% — Kune — Kan + Ky HM at = Soe q au ya (me -2) Sea = dl Xe. i =— SiewSeparation ho variables of ea (ii) and in tegeating stern whine fimils a &£20 4 x20 ak dime st 5 me * 3 2 | “_ = [oss dt 5) me a 5 “yk 3 Be [»-*3] : wax dt ° Ke ba) 9 Lb (n-x) -fr me) = Bet % 3, Qn % — On Cve-%) = Krak > Oy [_¥e ]) . wal ay & = Me fn / ab Ue -h a citi Substituting value of y fara “f Gi) in op > k = a He a = ath fa). G5)> ky = (a-%e) Lo [ ue at He-U oo) From dil) ond dy, Adding both He oqualions, kee Ka = fe to[ | +, 3-% to] We ] He-K at ‘he -% a > wa ke = ie {aes Ke -% a ppm is aimilaw’ to apie of weale equation oto! ) Le a ging with Lied order aale «k= 180 comparing : Su Hence , eoverceible ruaclion can be Ireodead as single Geeel oder @ Vy » reaction , Where Ks KyThoowies of Roles al oachin ane Se RO ae & Collision thoore Gy Undemann’s dime oa acre or “Thaoery of unimnolzculax reaction Activated complex story g did —> Se Vndinonn’s tne lag Heo» — Drawkads of Collision “Theory > > Collision theory fails to explain “he mreehanisen of unimoleculan — reeacdions. > Th uni-eoleculan reactions follow fits! orden. réxndhon yf wingics - However. rom — collition *aory perspechive > wo soleculgs muck collide , hence 1 should be of 2nd orederc- — Thus, cbllision theory falls 40 explain how birnole cular raactions give Lieek oredee — coaclion. = Lowering of prearsune — convartds dl orden untaveloculan. reaction into 2nd orcdereLindemann’s “Time Lag Theory > Easemanns Ay Moleculs get activaled — thaough collisions . Activated complex — decorapose-s do form the product. > T€ dime Sag every “ dowege. » deachivalion takes place. > Te Home log “is Qess , Accom posifion ‘takes place A+ A — 7 A+ AF At aA —h 2A (Deactivation) at __* > Bre ( decompocilion). Ponlging steady elo}e approwimalion to At > ate") 2° wale of Coremation = rate of consumption > x cad” = & LAvI(Al + x (AY > wLal = («Cal 4x.) CA*] > cat] = kcal’ Kw, CA] 2X3 Role = kglO4] > Pale = kee CAI” k. CA) +s, fase Ls ky LA] > ks Rafa = ale ata) Oy pe dary aad A)Cae 2-7 Ke D kA] : Rale = emt 4 CO) (2nd ort dere vn. a) De G8) Activated Complex stzony_/ Transiton stale sony 9 — (Absolule Reaction Rale “Theor fo > WHR the approach of acting molecules owarde eqch other. There is conlinuous change iq’ inden = moleulan — ditlance and nat ener 3 On reaching mquilibsium veacling rolecylas ge deans ferred ‘into anergy rich aclivaled complon (ac). > Aclivaled — complex ie In equilibrium with the rteaclans. — Achvoled complex must possess an unslable vibrational degree of — frevedom, Activaled — complom decomposes to Lorem { produc, 4 Aclhivation enema is the extra entre, +hol mucl be supplied do reaaeclant te form vachivaled complar. eatiestaliecly 2 A+B —+ Product ts ei A+ == [npl” + Product ee sa > (ral® -y* calce] fRale = cna] * x Fraquanes of deeomposilion of aclivaled , complex,0; -feequancy = P = Eve Ee hv we m |9 92 Eve n pote = k* COIL 8] » ¥T KE j k= Bodt_mann constant | p fale = k* CaT(e] x aT universal gac Nh fatter Moye Number a, Rale = k, Co C8] Bu (A R Op Ca ed h > & = ke aT nh From Van'b Hoff — reachion Gsothorem , DG= -RT Oo K os Fore ockivaled shale , na® = -RT Qo k*™ > Un k* = -an* 4 TAS™ A ee RT 2 an w*® = -on* + TAS* aT * en P/ Ry ps® a Fe tl ‘Mee k* RT OR -on*/er —as*/ 2e b «et R ar oh - atCompanicion of transition slale aon and callision Heer > ae A ————— | to collision “Heong » fale 2fP = 2 ce. e aga wi dreanihiDo alate nang + | gear e -HP/ AT , ante Oey R oar _— Nh -Fa -Ga/RT > oat / oos"/R dae -« e ? i 2 eR ar | (ps Owiastation faclor). — Substance @hidh allens =tAe male of rezaclion, howeverc Wis aecoverted al tha end of He reeaclion without i a ge Fg ute Choraclerio lies of calalycis ~ ~7~—_eoOO Small oreouel enough fo calalyse unlimiled rtocelions. = Equilionivm we reached ver fal,ol calalyst eon be changed by adding fomsign 2 actly substance. Promo bere. + wy — Treneases elficieney of calalysl eg" Ne4 Be > 2NNs : Wa oH, FEM anils [Mo ix HKe, promoter J Poison 7 > Pecreeqres 2 (Licieney of catalys! . Fe . 2nWo 7 08, N24 3he ule Nica ORs Fe-™S , ong [HS “Re poison |] Supe pee a ae a of eteaclion. > Relards the reale > Lan HO, —alucewel_, H.0 4 % Or. A. pillaxentiale poicon and -ve catalyc) with proper, enample. C sm portent Queslion) ~ Produce! of 442 reaction it a calalyel. ~ wgs Acid hydrol ysic of eslerechy coOtiHs + 420 e CH COOH + Ca0H Cell - ealaly y When +4e rteaclants and calalyct are in same p lace ao 442802 tq) + O(g) Nolg) _, 2803 (4). 5 Wrin +82 reoaclants and calalys! are in dif Coreant phare: Welg) 4 aHe CQ) els ~tiad a4). 2a,theories of Calalysis ~ ee — Mochanisn® : ooo — calalys) provides an alteremale. path wilh much Less adiivalion — anare au: + vithoul catalyst voi th calalyst Pp Reaclion = This theory Is helpful in explaining , homogenous calalysis. Tolacmediale compound formalion Hanory ~ aie f ~ Steps 2 — catalyst reacts with — prime reeaclant 40 form an \olerceediale « —» Trheoodiole compound sreoacis with the otha resactant to Loren produc, Lslowes! and rale dalansitning, elop J]. pechesgelicdlg fie gy =e) pg a at SS ae Koaca B 2 ABS (dow) . Talexmadiale is AC , ayhsing, steady clale appromimalion do AC -A_ (acl =0. at “wv, Caltc] = kCacl + k, Cac] [a] y wal tc] = Cecd Cas kote] } ¢ Gel 7, bm wake [oJ ef eh Role = xs Cac] C8] > stsl to C9) £6 Kia kg 68] (2 fron ot) f > ity SSID k& + ka C8] Case T ~ k, >> kg C81 3 Pale = bk ks carceite] | Xa = k Cal tal C¢cI (* ke Wks Ma cae E> xs C8 >> hb 3 fale = A Cl Ce? ; =k, Cal Cc) MK Cor¥ qs bolt caces , eale depends upon eontaniixcalion of calolysl. Eocample_7 2.80, (q) + Orla) cxetp _, 280s Ca) _Sieps 2N0 40, —— 2N0z 2N0, + S02 —— 7 S09 + 2N0 Limilalions of —Tatercms diate compound pan = _~_-~-~--~ORervowvwm"="nm—=—~™ = 9 Thad ails tv explain th Helenogenous catalyse . a of catalyst» Jn Gb deerease ore Inemeare in ethtcten.sy presence of forenign substance . Ddeorcption “Theory ~ — = = Reaclin moleules are allowed 4o reacl in presence of catalyst. These gpk diffused on the surface of colalys. > Reaclants gt adeortbad om the sueface of cata lyst through = Van dee Waal’s Fereces + — > Basorled eactant molecules get Lnanstenned inte belied. rich complex. 4 Activalad complex decomposes to form tha product.+ 04 8B Adsonplion | Caenctants) Gately’) — L 4 = Le + AB desorption rey, “Craedel) 4 | 4 Gectelyel) (Complex) | Mathemalically » fale = dx x fraction of suretace of ca Yelyel hich is ~~ 6 ae aceupied « x a O03 34 = 20 ab at — aight © =XiP 5 P= Preesuce | isotenm ) dake hy = coetficienk of adsorption Advantages - > Smallse Is the pardicle eize more \s He sure face aren , hence more ficge, valenees — roc valencies ane occupied » Poiton — Ubich = pecdniele the eactant,a alecetifal siles een in ereacks promoters — oceypies which Leads 40 more free dolenntéss michales Mentex — Mechanisn> ee E4+S ae Es ry —th > Produet (£8 forems produc! J angry btehag elale approximation to ES > 4 otes] +0 ces] x, CEILS] = &, Fesd a¥, CEST felts] , fiest Keo fesy =< metertsy , fests) ka ake aa Z moka Kt [ vers michales conel. | afesd = Le] [sJ ken w 1, [eo] = Tolal enzyme conantralion tel = fee eng test = Ceo] - led - (Ceol fed Now, [es] = Cel [st Keoj{eed = CEJ 4 cells} . [ed [; 3 be | ken [el + fe] sey] . [ele ko CEs J xo A LS] Rele- wo CES] =% Tels) » gle = fs] ih tFo1 —=— % Yon km+ LSJ \k, CET (sd Km 4 [8] ——) +) |fale = cact 7 km (8) cae Role = Ya TeotCs3 4 Ordre ic J wal. aubslrale, ken Care 23 (S$) >> ken Care 22. tole = Fr CEOTLST » ky CE] 3 Onden te D worl subclnele. csi Evaluation of Michaeles constant Ee rw (Bol = Les] Role = &, CEST ye ki [es] Orn Sine = k, [Edka + [S41 vs Meas] g = bos Eel — % ; $ kn + [8] as 1 s kn 4 eT Loz ke a Tman (SI Sinay LS slope =km q , 4 hs Intercept = 1 Cran Vesy => Ken > Slope Intercept