o,* - farst reactions Relaxotion Theo Reloxation metheds are wed to’ s 3 They iwdve measuring the veloxatio time or & reaction Reloxation time un the dime. that it taker Ff to coves a certam fraction of its poth ower d equi: bem. Tr a veloxction methed the yenetion is Piret allan to attan eqs biven This ea ers recthem ciishr bed! oj Clite suclelenlyy mereasing ‘the temperchre, Pressure or pr) eo that the ~eactiim is ne longer utibium: The speed with which the system in some w at Approaches its nero wiliboum is then Pollewedl, ee ust Spevral aetectin Heehnigues, ond prom om omalysss oP the behaviewy , vate censtonts com be determined . Let us consider the goles, Yeartion . = impl e vreversible ph o> % the ~xeochms m beth direction ove a the Lost oveler “The ky (Q.-%) — ka du. atAt uilibaum . : S #50 a Since cit equilihiun eae Ne Rae ‘sig Pa : uShere ~ yale ef bawkuskrrel wear” | Le = Concentration of x at 2g iti bse let AX = X= Xe = deviation from qu Libium Rate of Chenge of Ax with vespect te time os Alx-%e) 5 t at > dav 2 de - k,(a,-x) — kin at it 2 dee 2 Skaslkw— Kar at = kya, —haaka)% one = kas — Cerrka) (Ax+xe) (= So) But Krom equi baum (see eo) ky (Qe—%Xe) = hn Xe. > haae 2 kyte + kite | D> Oe = (erate ky) Xe & Kk, DS daw @ (kath) re — Kitks) (arere ) at = (kak) [ «- sur) \ dar sid dt* y- Thus the previous ey Shows thot Arn varies wrth time inthe some manner at Jdo€S the Concenkdr, oF — ima first oder veaction beer egration of the bexed eqn t d oe a [& +k)dy ‘Avy 8 lr @we . (ky + kat => ee { The reloxation *e lhe 3, Lbnum composition Epponentiol new ea um comp * seg eas iisiees, eee ini allay ” at equiti baum ator tempaaky, T, 16 subjecteal too gudden chomge cf tempers ae T. Gehen tok He te Ta eee oe Uren eT, ee uthew (Ax. ae: ae then fan] al Be Cy + ka) eal s gi l her Ae 47. veloyation time, the velaxation time is the dime at which the obstance Som eopaids rium ss 1 of the initied chis tance@* The Arwhenius Law The ~wote constomts of most reactrona mereose with TS Temperature The wate of change of reaction vot] Constants Leith temperature is qiver by the Arrhenius equation. The vavaton of the equilibrues conch with tempera, Obey the following low , dln Re uh 5 ee ee qu Lileruams Lenttanr pr2 oA fy expressed terms Ls O Cf concentrations , AE = Energy, Change. Consider the ellesse) veacteon A+8 <= crh Eq udbre, the «ates of the eppesingy veacko pia eau 4 at k, (AT (@] = ki fed (eo) Where k, ancl ki ore Seemd order vate ints, the atvve ~«evessible yeacto Now di ae oe ge CU, : kay {er (8) © Comper nay eqn. D onst @ we get Aint eda ki RAE “aT aT eee eS) votion G) com be lands Lows at aa RE noo fe aSa a m n iy t de Ciara and dl» Kea See Ea ee ar (eae udhere Ea eas Expedwentally it was found that I’ ean be set Ul +o 2ere, the vote constont .*, bei velotect ts the temperature by om euation of the foo aeons Significomce of Tntegratior comtant IS 0 | ink aT A non-zero value of T would mean that the tempersbne dependences of tthe wotes in the Po-rwscerat ond Yeverse chyections ove affected oe Some commen facter- The Sesult thot TL ie. achelly zero mokes it possible Lor ome to assume that the reaction path from A+B to C+d may be divided inte two parts se forword and the baekword reaction. Energet vit con he daid EEE BoRicen the wiMol onsl the epmel stetes there is an intermediate gtate that has energy Ee, greater thon that of A+8. ey Ey iain F Final state Ae c+b Snital State ‘aa te!Thus it com be sugqestedl that the reaction bet Seen" A omd B ic cletermmeal solely by +the difference between the enegy of A+B on thot of the Tahemediat: State. Karnike Note s— the reaction yate for the reaction betwor Aomd B is NO way velated to what ocuns after the imtermedtiate stale has been ~eached. Srmilosly the vate of the ~severse weaction is Se Combrolled Bs the ny eae Totegroting eqn. @ on the previow page Eas -E +tmsl | provided E is RT temperature inclependedt ve a eeler s ‘ 4 Whew Ais a const. Known oO the & ency factor foe Eat le the veachon. The factor eu 38 the Boltzmann expression’ Fox the fraction of systems eat energy in excess of the value E, such that it con be identified wrth the Fraction of the yeactant moleules Cunderges collision at a given instant) that ore activated complexes A Complete under stemeting of the Pacters determining the vate covctant of areaction [os foonn Awhenius lacs yaw olves * ie ee of the actvatin ere oma the Freq bene fas ; The ene factors were takied by the Kinete pera olUsion, im shech the molewles ove trenteal ay hore dies” Bg Oonernie Sy absolute reaction robs Ue eee of asatel wiechon c¢-® + The Kinet ae et Collistons Comsides +0 jelenteal qaseeuy moleules A’ that- undergo a chemical reachow to give product The vate of the abwe veacton in meleutlorenite + e -E/eT uw oi Zane i molewle co! ay ugh ee oan = number of collision $ per second Beben wo molecules of A in lee of a Application of simple Kmete theery to this problem leads to the reault thot the total number of collisions per second of all of the Sy? molester that axe conteineal im lee fan is = Zn b Gorden hi Shere ale ‘chetance Tbetwees centres f spherés when the collision ecurs cf = the Average velouty By kinetic Leo, z. [oe wT! m = mass of each molente Kk = Boltzmam constant of eoek moleule Where Te Temperatuve an the Knelte th the molerles ove @nedera weiiee eee aosTh ise 2 collisten Fregmencs a oases gjiven by Zan = 4 Pat are [ae ™ - axt od Cer The correnpendina, expression fox the feanpwenes ran fox weact om A+8—=3P thew A cmd! Bl ore Unlike venstantomelanle 2 master mg and mp with concentob us Gt of moleudes Per ec) of Ms, ond Ne srespectivelys - 4 ts Zen = Mnecne | oe ap oF mam where dla - sum of the ~so0ki i 2 das ic Known oa the collision cnnss- seth The weoetim vate peth aw ave Ps WoS-B ke eee 2 7 ae = pane dag | SrkeT mats Lata LET mame “8 cam be also gard te be the number of moleute, collidine per gered ond having a jot Sern E im excess of the meom energy - Se Hing the concerti tions of the moleules te tat We can ate i a kic deo | SukT ey mame ' ushew bk’. Phang = Veate const few the Yeachon in, moleutas uni ’ Yee GE eeMuttplying, kL’ with Avergadro’s ne. (N) we get 2 2 y k - Ndbpe fen mate ecg Vet cemol sec mame Comparing the above equation with Arrhemus equaticn , Le op ely We get : : ¢ Frequenuy factor = Az Ndpa i. T mena The above theon, work well fer reaction senvolvin atoms in wmest cares. However the ave deviations ™ predic the vate umstonts ae) the above Simple collision theery - To account Pose deviatreng Prev the above mentimed Simple collision thee it has been postulatect that the number of effective Collisions be less thom that by the kmetse theey Wen This 1% becouse foc Yeacthon to take place acmticalVerientation of the molewe on colli sie ™ay be necessary. k 2 Pee ) k- Pre) Whee Pp. pecban ets or steac factor Now let us to explam the a veversi ble wiction wing the Collision theory , Consider the eqp.. ‘ee i 208ha Pier rue Ty. wkd gr tyes SN The 20) 0 Librium constont Kis eal -€,[et = ene: —E4|RT 2 Roeec oe oe eo fies Cold clans “Ur eatatnenain seca tls YES Sre ay daa we have rere thus (e,-E let rae oO R, Now %- acer asia —aH/RT ==) where AG, AS and AH are the “ncrenres tm een energy , entropy ond heot content Centhalpys . we have Compornsy eon. ® and © akove Ae €,-E4 a Ee eny econer ond aslk eo. Py otic of the stevie factors Le of fosysomreh omrel bark word yeottioThis implie that it os mot sufficient to cotrelate Pe Yo probabi lily Ffochys vith the jerdbabilily that certain seackin Groups come Aogether on collisio . Ty fact the “P Aoctors showd be interpreted im tems ef entrepy “The eq usihibrium const. for a reach A+B= C+D is K 2 eater Petiveted hte X* =e fet 4 a ate * Also Aat Keb Final state fe a ct a ee assist QT Schemahe Pree-ene pone The above eqn com be sph os Fallow s lnk, = -aGh = leas RT ond lak, = =e, eat QT Her the AG? the mevene 2m free energy Shen'm geome) from the wibal state to the achvated statel x*); AG. cs NOT Aneltémersy change that ecturs after the, attainment of X. Similar i true for the bonlewerral Yeackon. Tre above eqs for ky ancl ky can be wnlten ay how hy ef eerWhere V isa conehoot (3) 4 Now we com also ute or AG’. At—tas® We com w*rte the vate constant as ¥ ES ks v ep (4 2H") r The above equation is seen a the correct form Sine iw this equation “the votio of the vate contionts For the Zexword omd reverse yeartions doe invelve Or evtopy brik a heat kenny Carat . LK « ka = eHP Aci se erp PWT AHT Unated oor Na ‘yenslro ky RT ‘SS is ttle etHlerEquidibrium _ ane Rate of veaction — ee ste a Chemical Reaction toc ee FTE a eee! Direction amd extent of Rate of the reaction Chemicol Chomge (k) (Retoted to egpalsbinmygerst) ‘ k depends on the K. doe mot depend Concentrotios of the on the concentroher Comatizaents yeactemts but depends en temperahoe amd alse temperaive. ie ts not im ony simple woy yelated to the vate che» chemical reaction - However, Aneve esis a close selatranship between wiibsa the “theosy of rates’ anol the “theeny of ey Became , moleustes undersien seadim pass threngh Ee states vod, a aVaved approximation com be reaqordecl as im wilubaury wrth the sm pleules Soha eoenrol “Ss ntes he concentratios of- activated meoleule com there fore be calulated b. ordinos libaan theoruuse thot if the probability the clecompesiti on of activated moleules is known the Yate of yeaction com be Calulated. :A pretude towards under standing, the ‘theory gor Absolute Reaction Rotes : Consider the follosng yeaah of +b@== ’ moles ae ond d'meole The porkition function F’ ys defines! er armoleuile as Pe gtr where €; =the energy with vespett te the Zevo-print enemy (hases enewgy ond) Fox a gen anergy Jew U’ ao moleule - i 2 the tmumber of stole comespordin te 3 that one at (degene vou of ther en Ne ve) = Boltzmann Constant T = teabsolute Lempe ratureushere “The €, is the sum of all states, i.e, electronic, tromslabines, Sou tondly oreteanale The above mentimed energy types Ore independent of eath other to a gerd Ppt xi mother 6; (et Bs Tee Thas from above equations, Big z gee ere 3p: ne ay eth ae" ad o> Ff fth ushere £. ie ite ome fe owe seporote porkition Pumehons each ye oo +o one type of meray At orclines temperatures the ener of excted Clectronic’ Jevels of on otom or male vs usual very high te kmoke ang sign ficoml Fume contribebn tousex en. Se Be a meghyy coms clereal as unity, The portites function fox per umit volume for othe foctors con be aus by f, - arm TY pes fp an? (en? nace) tore eT aiid -rofes Wh, Uing a ta m= mass of the molewle A,BandC = Moments of ynevtia about any three rut ually Perpendiailoy axes.hz plomk? const. @* T. Temperature les Beltemoann constant men =f V, = Vibrotional ESBIEYS PAPS The expression —- needs 42 modification if the moleule has cevtam pe of sgmmetey Fox ey fsx O Ramey AsO Rin dd: amoleiutes f° 35 f,- Bu? TT — Shee Le moment of meds Te , es The above eqn. & further cbvaled ae ge a > Poy a homonuclescr molewe - For a moleae Comprseal of “N) ottoms , the total ees A Peealom = 2N No. of tronslatonel freestom aS NI 4 yotatenal treed om ae (Ror non limeocr moleute ) voy , “ = 9: Ge eee ~moleute ) No. 4 Vibrational Reectom = BN-6 (foe sea ~molente yt o ” = BN-S (fey aes) mol The ees of Absolute veortion rates A+ Bec+D Under eguilibsum conditns the activated complex Soll alee De ten hbnen UNth the seodents ond. products a Free ene sas daograns Ate c4dSHS patient: of theory of absolute veocten vetes edhen the veactonts and prectucs ove not atequilibrien, with each ether the activetecl complexes are ot eq sil bron with Lhe reactants For the mentioned teaction [x*] {A} Ce + eae Rays trades const fie Ba UShere “F’ dlenotes the opprprate pow bition SANs Eyes Aifferonce between the 2ero-pointeme / per mele of the actvated complex ond thot of the ~reackants - This energy is the amount of evexg yy that the veactonts must acquire at 0K before they com reaction. : It is +the enerqy of actvation at OK. Sea Oe a leT For the above considered reaction , The atom PB and & will hove 3Np_ and3Ng no- of paxttion functions, udthere Na omal Mg ave the no 4 alkoms unless, yeatton . The actvoateol complex oil! have 3(Wa+ Ne) no- of Pov btiew pune tions ; The total vibyational modes ovailable fer Aone B atoms ave ang-6 omol SNe- 6 ~veapectivela, Jon. nen linewr ae leculas and Shs Ss endl ives ¥ Breoy molewle .The vibyrotrenal modes available fer x* is Baesiee dox dem rom-lineoy and 3(Wp+Ne)-5 for Linear molenle . One of the Vibrotonel mede of KF hosa ols f ferent Choracter thon the vest, Since’ is Cowreaponds to a vey boxe [nose Vibration Ushich allovas the X* +o ae inte the preclucts ¢ and p: Fox this portudar loose vibration te pe fy af = qo Swe ot ds Bassler Peed. ee lky. Now with one vibratim gee , the % achvedeol Complex will have S(Ng¢Ne)-F ne. of vi broths modes. We dénote the porbtron foacki ow for this moleule f atkvatedt complex With me Jess vibyotimel moder a oe el 7 BT AY) ae (Al (2) eee Sole te: SIA) ceakt Fae ee Fa Fe VD is the frequency of dlecomposihm of th X* Now vi{x* | s freq, of dle compen: tion of the avtvateal ior. % Cencen tration ef x = rate of reaction & O's (C80 i slEe recta hori stont—or From the previous 24m v enabT- Re ea fay fs) Lo TERR Date lconste sod kT ecelel oo ete _Appheations ef the thdarg ‘of -Absotite “Restim Rates Reaction between atoms A +8 —= A8 ator atom molewle Dceordlng be the theows > B dloms OP and B first come toge he ackveted complec Fer anolivictual acoms, there to Porm at of degrees af vibrational modes 23k Gene “eoey ope Bg For x ar of deeqres yibrotond mode & Bic % Ga ae = B(vertle) -5 os ae cae) = 342-S Fer chiatomse wmode ea Bub since em x* decomposes te one Jess vibvatiod mode produc +t hoCy Xt has zero degrees of vibrotrenn! fresdom Ba Compseo of oma tromslatrmal ond vetation m odes Ge te eo [an Grate) RT)” gn? LRT gage ciiet Oaie TP dye = distemce between the centers of the odses in the achvated complex then ay = dine meme mats. Since the inclivicluol atoms have only tronslhios degrees of focodem fea wma kT rise ond Pe Qrm6ekKT Saree b The ote const. & for format on of a X care griaby ke kt & pee ier he Gate Hi on “see So The above eqn. he gement vith the vate- const. cateulated on Ses a ow a nerE Vhis eement jhowever, hot seen Fe Pow yveactims Inve lui na, exreleule cReaction between moleusles For melemlas, the Calculate of pewtitton fimetion Be Gieres yates staalvect “Coq ahi PUrpase Approx rahi. Ore made . Fox calulbos sf for meleules , the conbibutiens a eval tronslationglsclatientand vibrotional degrees of Greealom ave unitlen as f., Pa and fy and the tetal portitin fonction © is given by & v 2 £ fa ee Where +, ¥ ond v ove the numbers of the ge degrees of Keedom Conbsbuting. for the veackon between tise oloms mewtionedl i the previcus page, * 2 32 Fate 5 Fa: fe avd Fadi fe > ee knee Oey Fa Fa = e Seas kr fe eee ; i > h Wt ts artedel eae—"| Now let us consider the Yeactim involving tomplex mole! h=e = oe Tee Complex mnor-biney 7 Ohetintes A and & are complex mon-Lmcow molecules Heve, Contesing Ny omd Ng atoms yespee Lively ers Stet 5. 2 3(NatNe) —F One less degree. 3 —» Note of Vibvetional freedom one) eee eels es | The yete constont there face ali ffers Prom thet abtained wm the atemic cose by he factor of HVS. Ae | 3 A The collisim theory thot treate'the moleule as hava Spheres in all cares, g 6 therefeve hos am ener Tee a Since f, is usually of the oxdey of unity, Udheveas fe may s from pee ibs feos a Complex moleule, the xotro Le is Wit. W™ go that By te ts ip to to”,J Reactions behseen Complex molexuiles therefore be expeoted to process! Vey muh slowly than Coutidlates onthe basis d collision they E@e)> Same reactions proceed to final wroducts through « Sewer one or many intermediate steps,i-e, thre 3 J if Contes aXe eleme tony seactons Consider a consezutive Unmoleulor reaction belee A SBS ete ee The yate of unimolecular reach Ate dorm Tis ihe = eae 0 The intermediate is formed from A but decay to P 4 Salina Gait. = (8) - 8 ® Po a z ki) Let the imiol come. at A be Go Ancol ® from oy O ome selvingy oe (A) we have ke fA}. ac ——© Substituting eqn @ ww» eqn C) ara solving for(Z) toe haveAlso, Gi = Ai ere) ee CG wleat Fes ea ee eke The conentotion ef the intermectiate Te rises toe maximum, ond then falls to 2ere. The concentration of P vises from wero torwerls Ae - Suppose that bu d> ky 5 then ushenever on I molewte 1s formed A decays ropidly sate. Ps Because _g- Ket xe etet and ths kk, @ kp Theve fore eqr-@) aeducen “to (Pat =< t pot us G) Tw ao © we see thot the formotion of Products is Solel dependent om the vote umak at. whieh the eats CES as formed fom A Thos , despite being a Sener tro Conse cute teaches the final Prockuct eemation is dependent on oly ‘Ore Slew OF the ~rate ef ome step. This step iswe the cluwat ctep in the multiple step veachion Roe % S a) ; is Called the ‘Rate ecco step A rote determmi step may alse stem from the Loo Concentration of a ee eM ancl need not csxvespend. te the step with highest actyation barrier The ste state DrImat ion Tt ts aon apperxmeteon made For Convement eypessin of compbatest multi-step seactions The < state a Proximatbon assumes that, oftes imitial vee intermediate (IT) concentrates trom zero, the rates ef Chemge of concentratbing Of al wsaation mtermestaste < eves L.gibly small afr) = O at For ~eactown ee ee SN i AOI. kee at AO). ek in) pa = ky(0 - kf Pe pligiag erect shate apps medion & 467 _ 5 alt -> kee). bfx)oye (f=) 9) AP) 2 kf). vk. @} at kg => di). kf) alt Nets oH gny ila, ent t 2c ie oaks ade “dt ia [fe ene | Pre - eq urtibnia A + Bieta oP A pre equilibsiaon omses When the wate of formation of the termediates and ws de hack into veactents are. mush faster than ie wake Hop farmation of ooduile Thus, preag vil: bium ensts fer kass>k, and WR NOT Per ky be kes 1a) Sie (A 1{e> lra). yt dt - kb KiAICE) Side). at kaks fa} [8 ) =o ea