oelicS a Order} ~ Exferimentally cbserved CeO DLk: ofl cincentrations of Yeactants i, the ote equation A+8 ies, e Rate> @ [ad tel? order = a+% f molecules imvolved each ‘step (ox) Rate determina ting Step Whe (or wh Yote % fadependent -tont~at ba dA = ~Rdt of tr), Chy- fw}, = ~ &t (n] = [s),- Rt dla) = ala dt {a) Slope: -R Unt of Rate Constant R to Lal, evo order eaction is ~ mmol 7! sec! ct x Half - Wife Time $7 the time % which the onterbration of reactant becomes milf fs Glled half Vie Fime ieee (LA) pe Noo WI = fa], REY, a In Zero Order reaction, hat life fe dfrectly Proportional to ‘ardfal Concentration of reactant -% — Ehomple of gore Order Reabfons © trverse of Haber's Process 25 gy —? “ot Mo ¢) O photochemical reactionsx Fisst order Reactions: The steaction ota which Yate ‘6 Vnearly | dependent on the Concentration of only one veg Ctonb A ass) too [a], : 9 tet La) . —d (a) _ ere) ght | ne) ~dlAl. Kat ta} + He gm) - -k) dt ta ta) do Loertad, > ~ Ke (os) é tk tin fect order veaction , Unit oF aa ‘« ny W 8. set! By dnt, Slope= 7 ik @ Jol)Te Cte ree Oder Yeacttons. Ate ee Lu ee fm, g rah) el, [p), - Re Jn Wo = In fa, k th tn [a- sng = An to), = Kt os = kth Walt Ife o¢ fest order veattton cloes not depend On Initio Conceribration of Ye attant mele for fist -Onle veaclion’s Fadto- active decays 2 aes 4 NO gst ay Se cond Order Reachion’- a> dt]. (alt Rate = at. 5 = oll) Sher tay Z| die) _ en tea ie—Sr- | [aJ a) ons na Tr) fay, * KE Or {A}. I+ kt [A], DOC MCGtel constants td] Second Order Yeottion #5 “ i Mol Tk Sec \ wb) Slope=k ia, | & 2D EKomple of Second oder teattion’- No, + Co — > Not (a tt % ‘dependent of tntentrtin of (o K aor eee (eee is), leds at tt, [ohx Eber “Tepete = 0) Sole) 4. ax fate = RE at ae cy =k [6dls) dH (ax) (ls) atdx a en (Be)-») (GI) Muldigly and divide with [é),- fo], x elie = es INS & ((e)- 4) (ia a 7 J kat x alse ler) ans In (Por® 4 (e),- (6), |; Me ie [ Exarnple > Alkaline hydrolysis of (Hz 600 (gHe toh + Cols OH (t,-) ®] | (fa- 0) (Hy Coo(gHs + oH? > Hs ffote = K [ 04, coos] [oue) * Pseudo Btcck Ovder__reottton $~ A+ B —> Produtt od 18) (a [él _ df] —dl6) date = Sai : x gt ot Wee “tod thigh) “Te 28), then, Yobe = a =k fe Le) = k [alwhere , R >K (8), TH looks Whe First ovder veaction. Hence SUM Feud fest order reattion. & 77 Beudo first order Yeaction, one of the Yeactont's Concentration 9% Very high Ad hydrolysis of ester > Hydrolysis er 4 Suter e Se x General form of th order eat bion § oxi Se (#, Cr) F c Rate = ~ale os a te)A bat |ife Lime foc general order Roane lulet wits Au, tat: Led, ) mt = | a “Bae ds key, i ay (o-)K 2A+ 3G——> P Rote. 2D 4 wlower wrt 4 ie Ss order wWvet- B * Povollel Reactions sees, OS h 4—>8 a es {nde Lele, (l= Lle=0 tok (ot, tad 1 = _ -600) © \yo) + Ye LA) = Rate = ris rE t i dts) ~ fy rhx) dt — Tas (el 5 bier he) fed = freUl 1605 Rate ale) ate a = ¥,(0) ole) ~On+ ap: iki Le Me)t = (Ktky)¢ a= fy tnd, © 2) ie a : ee Jalal leh je [ et Vue Similarly for Ce] Karel) = Hy [a) dt fo tet |. ae KH te) = td, Ky Ko + Production Ratio? Rattc of loncentrations of products at gme tt" (2) . Ky Production Yat'o = ay ba * It % constant ie Time independent 0 Ra (e) (onc T 0) (a) f=Consecutive Reaction ; R Ke 4 —=> aGaaG Pau. © Abe, Ll, ° ie pttet Ca) [e) tc) > ex chlorination of Methane Uy. Oe ¢ ho > a any CHy nd Cla, cd aCe Hy Up ee chal, ap hy Rate = a ery, le) {fe} ih tt aol” oht (aye [8).€ wow, de}, x, (0) - tole dt ht 40) mate) > * [o}, ¢ ee Integrating factor 5 é Hat Maultiely both sides wb @ = (i #Hy) t Be E + [81 ae maH Ac (6),4 \3 [." ‘a] = = 1 (0), ‘ gt a dt (el=9, to tae * [6], ee ht ] Ko- R* oO © Cc) = fo), - Ce) - te] one) 3 ele a] S toy cha Ccl> En),= Kile Ky Ke Home Tasks 5 time TE © M>k2 plot the graeh Qualvtatively (5) hy > hy K, ke ~dow that eae [aJ, Vaal , ys hy -K ky ty[ir Me est) Mpaky kK a# Reversible Gx) Opposing teactions 2 k, A =e iy At to fe), ta, ce 6), (equi vie) ee ate ta) Ce) At Squillbviem Founord wate = eachword role k, (eJeq * [ey Nhe (Jer K, er qittbrine Gnstnt (M)> Dey thermadynarnits kK Kinetics aTAd,, = y Kirk, = (iohema) ce = @) ‘s O% ® Woe Get = (K+ 4.) (E99- (ley) ag +189). ate kk, ha [e)- [ea 0 4 ee paste fla} . -Q+K.1)¢ le Caey : i } = (hth jt ta I= it oe [oly ) &* Series Reversible Fo 6 After 52s AY thes te With k, Reaction 3- i ~ 1° order Me De ee Se 1 Rate 2H). Ae (a) Reth_y [de 4-< ee = Ky foya Kak [e] Koki dla) aa a pers | Pe area cal, &- th dt : igett, Vox Ky fo Valid eventhorgh Kk, < bth.) looks ke fest ovder veattin 9 C Pegs Rytty Th pew# Chetn “Reacdton e Ee c Hot By —> ouey From experimental observation, FLV] _ K [on] [ony \4m [rer] "= Constante ter] = Proposed Mechan‘sen: Ol ee x, Smee Gr, > 5 () Rogagations- gi 4H M2, hers th K, ; {48% —> HBr + Fetordatiny f+ hav its Hy + Br °, con = . , \ RMS aSEON ss oy .gy eaet, Bry From Proposed = ™meChan’sm, & (we) = k, Cex) Ded + HsLHi) [ea)—%,[4) [asy] Pe > 2K fen ]- Hofer) [m)+ Hs LH I[82) + Ky [al[ne) -Aieec[ed” —>®© 2p) = [60H I- 3 LiL) Hy ee | sig Steady State Approximation . oti) [ei] =o & ernie pe ee At Sheady state approx fmation , add 8 & O= Ler, ] - Hs Ler)” ti. (Sa) od2 ee E vied) Bae 646 } 9} Qe 0 ; Gr] Ce] | i re yedo laimamysgxa mor! Gard m+ = Oh oe —=y 0+ O [eel teakiao) =m Be gf iene)? 8) migpiFint 3 degltion Beeson, veto l6], tad (a0), se. Ks Li ee (iors ER te 2909 = mort (oi) (ol) eb. b tla) yj [05)oe t 4 eae (s),.. in ® bi d with a ta) we get ty NI fay Palais.) Sol > Hy {ere} + ky Ler) 655 ee _ Meth) ier) + Hs 14) 18%) * Ky Ltd [werd 84 puttin cH) & fer) Y Ye qe) + ha (fe) C20 © y there he 2p ray pe aly Ks ks Heme Tash s- Os depletion mechaniste ¥ Phase veactions vote Unimeleculor reaction Uniroelecular reactie Experimentally , mang qae are fo\low'og ferst order Exh ee Rate=~ [eqelo- prorane] Sroackion Co-ordinatesEenthogh we require — atleast 2 .. < re molecules Ry ‘ iL i, Snow Zoe these reactions undergo tirst order veactions. Proposed a Unimolecular teachion mechanism overall I neo tor di, ata B, Seb: ; et ae kia] | Mec hentsm'- K * oo Aas ea at, 6 mos f+ 9 Ki faege > Ree - al - x, [o*) 9 4 hich *— not eg lst a Bier phen su kali] &'[a*d[o) - Le") Under Steady Feu Approximation , d uy ae) ie Ko fo* [a*) = —— ky + Ka fal Now, — general Vor pons ip Ka to]* pe y expression 1S Rate = dle) _ at Ket ko £9) we have bachwote decomposition ab hgh pressure ~\ bav , neocon vate °S Yreater than Yeattion Yate Ka! Lat] 0) > 7 Ko Lat)ie {aj >> Ky ! 5 Bs agg F ted Sots also experimentally Nev? fred that at low Pressure , bachword wile 7s less the detompos* Sha YOte wa tnt d Lo) << Ko La* Ke [od g< Ke Benes f9u0l Rate = Kalal® bo undego od order at low pressure : as ° dok re 5100 toke - general exp’ a Ky \), de} = g (A) a‘ Le. ccpi Eo Temperature dependence of “R's Ts Wen Sas, alice, @-ordinates > Equations AS RT as % a c g. seston Loo Ks lmole Beebe: peo BO- Be ll PS: A % early ome che a : Be x cniewless 4 order) W | By iy (Ob emol \s (for binoole culov) equrre?* Catalysis catalyst change the reaction Pathwoy *e- alternative Poth «=o with = less activation energy which Promotes dhe reaction faster: ete K-low “(qren T) bac 5 Pec —- BAigh (geen T) Prelit Ona = — Michael’ Menton epechan?sm Gin == ES lt Eso ere, rxe Ke LES Jp wequired fo Very lowi Wo (TOES, W089, area ks © | ro),, EI) k, [5 ]+ (K+ 2) Rate - a Ce) eek 1LCI613) at ks) + (414¥) vy. 8], Ke LL) 2 t initial Ts) + Keo reece oe zee vijon EDS 7 eae when [5] < Me tele [8 yaa =) W when ToleHe, ve Karle Doe j From = above equation, we have ee fH. ok, feb S$Ken | ky LE), i Lene weaver - Burk plot fal, tain vole of ie ; + of erdyme (ameun’ Producté Chemistry Tetons Ht 25% the — Specifte tate constant for the hydrolysis of ethyl acetate by NOH ts 6.36 Ittmoig!mta!. Starting with [ease] and [ester] of oot molel tlre What proportion of ester wht! be hydrolysed in lomins 7 He 6:36 Jit [mol min It % Seond order reaction {e,- Usd. = oor rool€5,] libre Cz, C00 CMe + Nao —9 CHacof fol. (eI, fox '-* Rate: k [ele] A> 0-02 mol /i;4Fi x me NOC, Uno) MAG! Ne ded that | on doubling Concentration of both Yeactants, the rate increases g- fold. But on doubling | the concentration of Morita alswesisub rate only doubles: what *S overall order. » Lnot Clp > Nock an Cj Mates SE = Coo)" oe ]® > Leal? Cet)” => 1@) ep fs fer Qin, grs [ano)* [2ce] tPF no” Cole)” —>@® gr el # ov = [no] ys) eee nin), —” © O-8 ut kee] @:0 «2. #3 [e-9 ¥ the rate of deco mposttion of a gas uns F205 %q Some unit when 5% had reacted ond 2 yes Sle tO ad untt when 20% | ad undergene decomposition calculate the order Rate at tel ad % order of veaction « Foca [ore co) | | a gas ~ hk [09s (61) 6) Siys kK (o8 0a)” —>0BE esc, the half ttle perfod fy the decomposition of Moe % Sah and % \ndependent of Mmrtigl Pressure of Neds - Galculote (a) the Spetfic vate Constant : e) time Yequived to qo to 9% Gompeti tion Liles S- Hh Given, veattion % O Frat order ei. 0-693 kK