1! ZL NI oS ‘ Enz qi3e tea 7 aaa Enz ree = i | ene E)aice 37 eo “ves “ipo a ~~ : ee : ai i 4 | >| 7 Chemical Kinetics | a ii eu t- . 8 oe ; e @ «ECddddddddddddddddddddddddu : CHEMICAL KINETICS - 7 Rate of Reaction: "The rateof change in concentration ofreactant or product with respect to time.” Change in Concentration time mol/lit Rate A‘ Product Rate « [AJ; Rate=K{A]; k=Rate constant or Velocity constant Specific Rate Constanf(k): When [A] i taken 1 molar then Rate Constants known as specific Rate Constant, oa For Reactant: t,> t, but x, oC+aD 3 t=0 ab 0-0 Rate of disiegration of éactait = Rate of formation of product TA) _ = af] 1 ofc] _ 1 af) bo dtc dtd at erie ireieiirear sample: 28+ B—5L0+!D :pae=—3 HA] Example > 7 fp eee 2 dt vor ra oie Una SD” [moW/lit}” Example: n= 0, = [ROW soot tne n ——— = mol! / lit? time"*= time: : oe 5 vot n = mol" lit time? n mor*? fit?®? time? time time noe nocerensee Mesa andor oe #8910400 b; Rate~k{A}![B}* Oider of Reaction 1 +m : 720. a ar mao a a ensamnace](CE sssstes 02 wan, sie Sarai Near IFT, New DeIN-16, Ph: 011-2685 ants womamemoe | “Molecutarity: Iti the su of stoichiomeiri coeficients of reactant al king patina reaction, « Order of reaction: Sum of powers raised upon the concentration of reactant in a given rate law expression, : Molecutarity Onder of reaction : “6 ‘Abvaysa positive Can be any eal number : imeger +1,+2>0 « This isthe theoretical concept Experimental concept < Do not change with temperature and pressure (Can change with temperature and pressure « v 1. Indetermining order of a complex reaction ofreaction. 2, Order of cone. ofreactant is taken into account if t varies with rate of reaction. 3.1fin any reaction njore than 2 (whose molecularty is> 3) only slow step contributes in order eactants.are present and any one of them is taken ito excess than the rate of S ‘eaetion willnot Vary wr. the excess concentration containing reacant. Soils presence in rate bw expres, sion is kept as constant and its order isnot taken into count in the overall order of react - Rate=K[AT* [B]'[CY; Order ofreactionw.s1.A=m; Order of reaction wat. B Order ofreaction wart. C= ¢ Overall order of raction=m +/+ /; mA mB +1C-—> Product; molecularity= m+n +7 “ Irate = K(APIBP[CY a IF Bis in excess then overall order of Rez m+ 3 h as //Feeudo Order Reaction: Those reaction which appears to be ni order (w.. rate law expression) but are har found to be different from n* order, called Pseudo order reaction, v Example: Hydrolysis of ester: = s é i acid Hyo—C—0-67H, + 11,0 Molecularity: Onder of rene =2 tion ~ 1 as water is taken into excess Example: For the reaction, 2N,O,~ Rate of decomposition is expressed as i “~ HyC—C~—OH + CHjOH 4NO; +0, a so afy,0, NO, 10, G Neu kIN.0] @ a Jex,to.) Gp 12.4 1N,04) ¢] ‘Then which of followings correct 2% (hyn k— DK=Ajmk, A= 2=3k, —(4)None E q _1 dlN.0,]. 1 glno,) “alo, 4 er re _& 1 _d[N,0,}]_1fa[No,]]_ alo.) G : 4 Mf a fa rg 2k, N,0,J=-Lk,[x,0. = Aamo, 24 2 3 4 q rect answers i¢ : cm q For NET JRF/GATE &ITJAM Exams C2) Fo Soa teaee as ey &¢ e(GAS To aun tase oe Kinetics of Zero Order Reaction [New Dethi-16: Ph 11-26881008, 26861009 werneareerendcavourcom "In this case rate depends on the zero power of reactant concentration, Or In thor words, rate is intependent ofthe concentration ofreactant. A—>P y A t=0 a 0 . @-») x (audy] fie fp — hax) 0 Gx (kis constant) x mk, z = ysmx Expression for Half Life Time(t,,): The lime period in which halFof the reactant is consumed A ->P ~ = a= AKU) yom x a m= 2k, Institute For NET-JRF/GATE & HIT-JAM a eeSr Nee Ne D6, P= 1-268, 20) wuncrenndeenon | Kinetics of First “order of reaction Inthis type ofreaction, rate depends on the first power of reactant concentration. (2) (where C,= concentration of A kita time t) Exponentially 6 |\,. decrensing ‘raph Graph for I order reaction: ‘a 2303 ven(4) foe covey # 1(ans) Yam X ws ’ FAK n een Te 19 ew 6 Pog = L- oaEdd do dd DES EDI III IIA II I I I Dd SD (Geese. 0 Hawi de Sous nent ee Dem A — Product t=0 a “o t=t (acx) x ay i “at a Rate at any time twill be =A] fay a - ak, ._ aiSiaNRL iasuees xa(a-x) _ a TH (a-x) eta a tn? 3B 9(_2 tt ee y= mix i, "0 (3% 7 os 2.303, : to AE, Llobet (a-x)] logy (x Fie eesarerericit Institute For NET JRF/GATE & I[Geese os aia sen ForHalf Life Fime: © i i i From the above expression, itis clear that halflife ime does not depend on the initial concentration in rst order s reaction. Therefore, the graph showing the variation of, vs'a! willbe "| ne z — § Exampie: In a first order reaction 50% ofa substance decompose in 5 min, than how long will take to & decompose 87.5% and 99.9%. S 2.303 100 = los = x( i00— ] 2 . ‘ ti 2 saat - = i) = é S : S = 2 tye 15min & = 2.303 Bing => bay Hog1000 i > tne S 2 tn Gi a (i) isdivided by (iii) S S « 2 => yy” 50min & Institute For NETJRF/GATE & HT-JAM Exams[| GPSs225. 0, man mamnathinbancn 012681008 2861069 vocoder | Teample: In decorhposionofN,0,, iti found ha ater 30 min otalpresareofsysem 350 mm of Hy é afer complete Decomposition, it was found 450 mm of Hg then caklaterate coms, . Soln, At 2N20, —> 4N0,+0, oR oo =30min P,-2x ax or (Rx) 2x x2 P.-x42x 1 x2=350 P.+ 3x2 = 350 0 Aflercompletion of reaction 2N20, —> ANDO, + 0, ° 2 Re For complete Decomposition > 0+2P +P2=450 = 450 a 59208 s0mmn, ne Ve Pecmok fraction Pi value put into‘equation () 180+ 3x/2~ 350; 3x/2= 1705 3x=340; x~340/3 Fo 8—| 5] 30 80) sag |= 4) Sore : EE EEE AS RO A AS WD |caer ‘i Kinetics of Second Order Reaction (ar IT, New Deb-16, Ph: O11-268S1008, 26861009 wwwceaccerendesvourcom ‘Those reactions in which rate depends on the second power of reactant concentration. Case 1:When both reactants are same. 2A —> Product t=0 a 0 t=t (ax) xSta ire bah 16 ht 260082081009 wrneencnencom | — ha | ge on c=ta —o Fxample; How many ctor, for2*order reaction does it ifler from, [Relation between and tJ L y= a3, Kxa(a-0.75a) "ka , ! “ase-U: When.both reactants are diferent - A+ B —~ Product 130) ca ob ° tat @=x)b=9) = dx ; Pte (a=n) (6-%) is : ae es o ; la S : In[b(a-x)fa(b-x)} Putting the value of =a, Slope=k,(a-b) : > at ' 1=A(b~a) +B (aa) - (b-a) . Now puttingx=b. I=B@-+Ab—b) > > dx = k, fae [omy Setisenle ae] eK |: Saale]2 [ Sees iio: sare a Sarh neath new hvac ro env auasioon aatdloe) “wwucsnooarounen Fa Kinetics.of Third"order reaction . 7 ‘When all reactants are same be Product t=0 a o tt @-x) x 3 sa ai ian i il ii ih ah a gh ae gi. a tha th fh at eee al€ y ra > gre cok 2a ‘Putting the value of Cin equation (i) mi t) =x? 42ax hte , aes [2 xe Institute For I -JRF/GATE & IT-JAM Exams “ca 3 meea H.O.: 284/11, Jit Sarai, Near, New Detbi-16, Phi Kinetics of n'* order reaction 26451008, 26861009 www carcerendenourcom nA —> Product wo 7” [Te Hes sal ak xt For halflife time: =, x*al2 eal + weal [asta les Reactions of frictional order: 1. Rate constant: ee < hall ife value for factional order reaction is invercely proportional to the od under-ootof ths inal concentration Relation between half-life period and temperature: ‘Herekationship between ty, and'T forareactn can be obtained with the help of Arrhenius equation k=Ac Taking ‘log’ to the base ‘e”. E, na =O) Institute For NET-JRF/GATE & NT-JAM Exams=a] [ Sees oii Br Nev ola a Co auinsSeloib wooloconca Now, for one component system ie., > nA—sproducts > ‘he half if period isielated to its initial concentration by the equation (2) except n= I ie. ., _ ne {Capek ~@ Ifthe reaction is of pseudo-order, the half-life is always defined with respect to the concentration. ‘of species present insmell amounts. “Taking “en ofequation (2) oo énty = en] —~ mi a © ‘Combining equations (1) and (3), we get - ooysa s a (A) (6) Equation 5) shows that the insease oftemprsture decreases the ali period. ‘The plot off ty versus T'isa straight line and the slope is equalto E, /R Ins Intercept ~ na? Ifat two temperatures‘, from equation (5) ans (ty), then bs lecreases with increase of temperature, CECT CTE_PTTC_VrI_tec_Es?t ae(Ges wos mani Sarai Near tT, New Det 16, Ph: 01-26851008, 26861009 wwwsareerindcavouteom - SUMMARY OF RATE LAWS OF VARIOUS ORDER 1. Zero order reaction A—P Rater=k rateconsant fe wa felon Hatt Lite fy = Se O, yet, SEIS ID DES DA First order reaction: A——3p; Rate r=K[A] 1 x-le ue Notethat t,, isindependent of initial concentration Graphs: = First onder gaseous reactions Bet ay 2N,0,—>4N0,+ 0, (Tota pressure) Ital pressure, P ey , Aller time ax xi Pvax/2=P, Institute For NEY-JRF/GATE & IT JAM Exame APP SG PES OP GF atSAE 0.2 anata Sara, Near, New Deh, Ph: DI-26RS1008, 26861009, wo.careerendeatourcom ‘And rate constant : : Or, Similarly other gaseous reactions in which total pressure is measured are treated for kinetics of I" order reactions. Second order reaction: Case-I: When both reactants are same. 2A—»Ps Rate r= k[AT on Graphs: és | Slope =k at Tha | ik: = = Case-1I: When both reactants are different. A + B—>P Att ab Attime' —a-x box (8) Second order with different enefficients of reactants AvB—>P Aso ab Attime't! a-x b-3x 1, baa) ib) "alo ae Institute For NET-JRF/GATE & IIT-JAM Exams 149 & bee 4 =o! care ‘ aan 4 q 4 y 7 iEddd ddd dd ddd ddd Idd CET (@) Second order reaction with autocatalysis AP nate e=KLAJP). concentrations of Aand Pat time t are a-x and b+ x respectively. Thenk (rate constant) ~ 1 aloes) | 7 ese)” bax) (6) Third Order reaction: ee a 3A—9P; Rate=k[APs Kay] nae Reaction 2A+B—>P ; Rate=k[Af |B] bk : 5 bla—2x)_ (20~a)(2x) on Eokle-297 (b—v) 5] oe Day a (0) n* order reaction: ASP; Rate = k[AT: Or, 1), *C, = constant > 2 order Or, 4s = constant => 1 order ce| GSE iroisbeani sa sn Heart New Den, Ph 01126451008 861007 worncareeendeavourcom | Study of fast equilibrium reaciton via perturbation relaxation method Relaxation time for different kind of reversible reaction: ‘The idea ofa relaxation method fsto disturb an existing equilibrium and watch how it decay back to equilib- rium. You can disturb the equilibrium by a sudden small change in temperature (called the T:jump method), or ‘by a sudden small increase'n pressure (called the p-jump method), or in some other way. You can follow the progress of the reaction a treturns to equilibrium electronically by measuring the change in some property ike clectrical conductivity or spectroscopic absorption, or te. Relaxation time for different kind of reversible reaction: Definition of relaxation ‘time: For a reversible reaction it is the time when the deviation of reacant from equilibrium ‘after a short span of time becomes We times of the initial deviation ofthe réatort fomequiltiimnic, Ax=.A.x, o ala}_afB] Rate of reaction a tine t, — (cof reactional tine, === i) Product “> Initial quantity xisa fixed amount or it sconstant for time ‘Ax, ~ Initial deviation of reactant from the equilibriam Ax™= Deviation ofreactan from the equilibrium aller a short span of tine At equilibrium, rom equation () rate of reaction is: ax, Be 2 (4) “Ks 0) And x= 3x, fax) _ ab a Substract equation (i rom ( Institute For NETURF/GATE&ITJAMExams C16]Oddd ddd dd dddddddddddddddddd ry Deh 6, 012685100, 26861009 www caeerenenvourcom OO) cea Hach, tos) k(, a, (x,-%) (+k )Oe-x) oy MO) (4) Hf sha ‘Now integrating equation (iy [6,1 far: we -( (ky +k Jat For relaxation timet=tand when tea, one mare (hither Ine th yar > le(k, +k) é A Bo ete '¢ t-0 a, 6, 6 tet (a-x) (bx) x t= 8) (box) x Rate eqtin wie dx FMA) K(%) Atequilibrium @ Fea hls x Mbp, )-Ke (5) > ‘Equation (i) —equation (ii) dx -dx, Gt ar Bs e—X)(by =) —K (JK, (25x, )bp—¥,) 4K (2) Sadak bhace hit “ha kotha skin, ka? +h, am on tO ba thagn tkbar, “hhactka?-ka? sheath, a IaH) Ky (X=) +, (2? x2) -K ee) i B= (s-a)fekay—kiby Krk, (x) te For NET-JRF/GATE & GD1 4 Fs “x )fhiaethibs tka] ky (es: x een ). SEE - (=n [kine ib, +h)ky(8-,)] Ix=x, X+x,=2K, Ax[ (kya) thy, +k.,)~K,2x, ] (i AS M24) an) w (an 2A = Product t=0 a 0 Lt (ay-2x) x tat, “(a5-2%,) x, a, = (aj ~2n,) x Rate law equation, =k, (0=2x)' kx 0 aut ay, : Atequilibsium, Peake 2x.) kx, Equation (i) = Fem 2x)" -k.x~(ks(0=2s,)° -(K0,) BE ak (0-20) =k, (a-2x,)' kx, dAx [a #4x? ~4ox] -k yx—k,[ a? +e, hax, Jk x, GR tk! ag? Ake Akan, KK, ™ = 4k, (x? =x,2)~4ka(x—x,)-k.,(X-X,) BES ak (ea) (ata) akan nk aa) 8} 4 —rYEVIVIVIVG. AVIVtIITdd4 eh Ci) \ ;NI, Sia Sari, NeoPM, Nest Dethc16, Phe SUES, 266109 menareendevourcom M8 fk (ax, aka kJ =x )PAk Gtx.) Aa K., ] => (x-x,)=ax i thy (,)-aka~K, Jat; in ax =[4k, (4 x,)-dka-k, Jere ie t ] Ift=O:dx= Ax; C= in dx; Indx~In dx, = ~1[4ka~4k, (x + x,)+k,] tne ai (a- Germ ok J] wax, oo hee) Aka 4k, (x+%,)+K ,), where Ax = dan, T= +k, (2%) 4k] avy Xo Ye (xox) (yg +x) (etx) (yo+x,) ot X) (Ye +X) m0) Atcquikim =K, (3,24) (x5 +,) (ys om,) @ Equation ()- (ji). Se Be (ayn) haley Nye) Ky (o~ x.) #8. (no #X,)(v548,) ue = (hits Kar) ky (rapt kax tay Hx?) -k, (ay x) HR (spi, tayy tx) rn Fite FX Raa RAK A, Kx hay ddd ddd ddd dda did gd vd ddddd TZ PRY TKK. EK KG HK? a POKER GRAY, KP HK XK, OX +R YS AR? Gir” tA kava kage RYE TR HR? : Ax ae en a a Os ee en MO nA okabsrr rer es, ))}, 2 ( SKID HG (x6 Hy HE. 58] Le GddddK,(a)—9/2) ke i 0 FS i Atequilibrium, —°= k, (a,x /2)-k x, (ii) Equation) K, (a —9/2)-K x? Ky (a5 x.) PK? 10% oka, Ek kat -hay Berka? a 2 2 M5 nf rn Gors)| (x-x,)= Ax and x 1x, =2x,5 ME) hn 999995. Rana 99999999999999994 Institute For NET-JRF/GATE @& NT-JAM Exams men 49444 4Vdd d dd Fb bbl Idd db IIb dh tI ISI DISD BEAM da Sarai, Nese, New Delhin6, Ph: O3-36851008, 2686100) wwwcarerendeavourcom KINETICS OF CONSECUTIVE REACTION a A—*>B—55¢ ‘Those reaction ni which one armoré than one intermediate steps are formed in which some steps are slow and some are fast The steps which ae slow are only taken into count in termination ofrate Law expression: In consecutive reactions each stepshas its own velocity constant (rate constant). : Example: KS,0, + HPO, + H,0—> I1,PO, + H,S0, + K,S0, 1" step: K,S,0,+2HI 1 4H,S0,+K,SO, +1, (fast) 2 step: HyPO;Hy!H,0 —2911,PO, 4281 (slow). Example: Decomposition of H,0,; 2H,0, —>2H,0+0, YQ, 2 >H,0+0; O10 0, Example: Thermal decomposition ofacetone: ° i cH, -C-cH,—5.cH, =c-0+CH, cH, OB stoH,+60 Example: Saponificaionofethyl succinate ° i cr, b-ocat, ~ 4) oH + NaOEt (Siow) Cre ¢— 0c CHy-E—0Cae 8 é ? ky Gthe-6-ona See = + NAOB (fast) cH~¢—oNa W 8 le (429 seo bg one 5 1 ae t=0 a ° 0 ~G ke Clin etn ye es) a Rate of decomposition of Ais given as oA a)SABRE 110i ai te ark Neri New Dana Pa 2685108, 26861009 rowcarecrndeavourcom From equation (i : nx k,t—Ina = Or -InX=kt > a This shows that decomposition ofA follows I* order decay ie. exponential decay. . From above expression its clear that conversion ofA into B follows fst order kinetic since itsexponential —/ decaying expression. ft TEVIVEVTIVION Integral rate law for B: Rate of deformation of B is Above expression i first ord Iw8solution is y= Ik, >>k, For first order of reaction: 99d Ie 69312 (td, ? For maximum value of y: “eee @ q. Segbigbaet Hue] Be Monet ne] Ferman, f= + Formaxima, 2 Yd 30-8] 4 9 eis ncreasing, But con, ofB initially increases and goes upto a maximum level and then decreases that is be ly there isa formation of B and when a certain amount of Bi formed it stants disintegrating ond the formation of C at that pascal time ‘rand C is continuously increasing as time passes in a very short spam of ime interval concentration of snes less slopy nd then cenfinvous increment in concentrationof C takes place. ove it isclear that concentitaion of reactant is a function of time. Institute For NET-JRF/GATE & IIT-JAM Exams € 23) Edd ddd ddd ddd dd dd ddd ddddddddNew DEG, Fr 126851008, 26841009 somenrrintaveercom |] + ‘Kinetics of reversible reaction/opposing reactions The reactigns in which the producis of cherhical change react together to form the original reactants, are called reversible reaction. ‘i ‘The kinetics of reversible reaction is studied in four ways. 1, First order opposed by first order: initial cone.(t = 0) a ii ‘cone. at time t a-x x a=x, % : 4 a ‘ ‘i e+) ee . = % ‘a = o o : — S k, and k, are the velocity constans of forward and backward reaction, Net rate of formation of B at time *t” & Ae ans)- bx ay “Atequi rion, =0.& x=x, (a—x,)-kix, a : From equation (1) and (2) ax Bak (a- ah a at Onintgrating equation (3). f i “Sy xo ens, x) a Iniiallywhent=0, x= 0 = —tn(x,-0)= 248x040 C==tx, Putting value of °C” in equation (4) mins, -xJ= Bats, tnx, -n)= 2 (SI Institute For NET-JRF/GATE &Odd dd ddd ddd dd ddd ddd EET III SII SBE 1.0.5 29 nso Nea tN DG FO 2651008, 268600) wemarrendesoatoom |] “Tusk, can be measured. From equation (2) ak-x, ky =k, X35 %. (kK, +k.) =ak, : . (4%) o From equation (5) and (6), we get ' a Now theequlrism constant ofreactinisgven, K= [2] = + TA] - (a-x,)- Ka-K 5 x, (I4K)=Ka = (8) ree es ee Or xX,= =) illgo to completion onlyif K>> 1 ive. or k>>k; Example: (i) Conversion of Ammonium thiocyanato to urea NH,CNO=3=CO(NH,), (i) Mutarotation af «—D ghiose into - D—elucose @—D glucose 2 B-D- glucose First order forward reaction opposed by second order hackward reaction: ATES BHC Initial Cone.(=0) “a 80 Cone. at time” Equilibrium Cone. Net rate of reaction, ' ox Oak, (a=) Kx a) ox Aowittrm = =0, & ian xox, O=k,(a—x,)-k.x? e -® institute For NETJRF/GATE @ TIT-JAM Examses (Ge tho tasers nant ev boa viv ne aaloon ernctrerndemrcons |“ ge ‘Therefore, equation (1) becomes, Paes k i i S Boa a-n)- :.@) . at = Integrating equation (3) under the condition that at t=0,x=0 sy x, ax, + | e Xs py] Be ia=x,) [ a, | aan a = ‘Thus k, & k, canbe obtained from equation (2) andl (4) 4 = eg. () PC ==2PCI, +c, s (iy CH,COOC, H, + 1,0 ='CH,COOH4 C.H,0H > (ii) Both forward and backward reactions are ofsecond order: c a AGB =H CHD : Initial cone. (t=0) a oo ‘Cone. at time 1 aX ax, xe > Equilibrium cone. aea-x, x x sf Net rate of reaction € = (ax) (1), > S = At equity & 3 dt ad 7 7 e on f@aBD 2 cS From equation(1) and (2) _ et x ‘ obey | ~0) fe Integrating equation (3) under the condition that tt = 0, x=0, we get 3 c k= Fe py] Blam?) 40%, " 2at(a-%,) a(x,—x) mo} c from equation (2) and (3) k, and k, can be caleulated. S & & _ institute For NPT IRF/GATE a HTJAN Exams C26) 7 » & Le |ESSSSSSSSE'’S=SIS (Cseee ican ; Example: H, +1, = 2m i NGAMIT, New Deibii6, Ph 011-26851008, 26861009 orerwecareerendeavour.con (8 CH,COOC,H, + NaOH CH,COONa + C.HOH Second order forward réaction is opposed by frst order backward reaction; AsB gkac Initial cone. (t=0) aa 0 Cone. at time ax ax x Equilibrium cone. BK AK x, Netrateof forward reaction dx. dt K(x)’ ha w a 2 ‘at equitibrium, 2X = 02k (a-x.' kx, oe uae ; ekG=xy ee -Q) fomequation (and) 2 Boel BOY, @) we [pee | ‘hus from equation 2) and (4), and, ean be culated, Peample: GN, +311, —==2NH, @ (® CH.OH+CH,coon—= cH, coc OCH, +H,0[ GER 0: isa Soak Near New Deas e112AS108, 20D wvanrenenacwonrrow KINETICS OF PARALLEL OR CONCURRENT REACTIONS ‘Those reactions which proceed through more than one ways are known as parallel or concurrent reactions. on k Nop on a. o-Nitro phenoh, oH + HNo,; — Phenol Lk. P-Nitro phenol No, ky : . [> GH, + HO” Main product ky CH\CH,-OH > CH.CHO + Hy Ethanol ib, LS CH,0CHy Side product ono ky Benzyl chloride Toners ie o-chloro Toluene Lt A paral equation A a t=t (ax) Rate of formation of B=k, (ax); Rate of formation of C= k, (ax) Rate ofdecomposition of A= Rate of formationof B+ Rate of formation of C “a MAMOANIMNINTTINTITTIITITIIT TTI, ‘ coSSSVESEGOSE MLO 28/01, Sarai NearIT, New Dli16, Ph: 01126881008, 26861009 wwwncarecrendvovenrcom | Mak (a-x) sf ae ee ne s x) : «i dy de Putting the value of a and { inequation() s(a-x)+k,(a-x) => Fa(ky rk )(0-x) On integrating thisunder suitable limit gives, 2303 ktky ‘Example: In arparallel reaction reactant goes into the product into 2 different modes. If resultant of the rate constant in this reaction found to be 6.4 * 107 sec and ratio of them is 4 then find the rate constant: k 1k, = 64% 107 see? ~() (2) Solving equation (1) and (2), gives 64x10? =1.28%10"s" order of the both product proceeding in parallel reaction is.1. then ratio of the rate of formation dy Ki _ ky (a=x) at ofBand c= gear k, (a-x) a ‘Ratio is concentration Independent ic. the ratio of formation ofboth the prod of product, Forder of reaction is follow m* order in both ways. isindependent onconeziration Wegscheider’s test for side reactions: According to this test the ratio of amounts ofsubstances formed in two side reactions is independent oftime, provided the order of two side reactions be same, This test will not be applicable iforder of two side sections ‘snot the same. Case]: When order of ea ‘h side reaction is‘n': PS a APS OS OF OF OP AD OS OS SL ey : « Ss ©GAS22= no. War ia Sarai, Nea ‘Amount whent=0 a Amount attimet > > ey) : (New Delhi 16, Ph’: 011-26851008, 26861009 “www.carcérehdeavourcom “Amount of B’at any stage = Rate of formation of B_ Ki(@-x)" _ ky _ Amount of Cat same stage Rate of formation of k,(a—x)" ky ‘Since z isindependent of time, therefore Wegscheider’s test is valid, Case H: When order of both side reactions are different: ‘i fs. ‘Order =m A , Ke Order= a © Amount whent =0 a Amount at ¢ ax Amount of B at any stage _ Rate of formation of B_k,(a—x)" . k, [e-0"] Amount of C at same stage Rate of formation of k,(a—x)" " k, aa ‘But (a-x) depends on time, hence j."(@~)"" isnot independent af time. Ke ‘Therefore, wegscheider’s test fails in such cases ay TIITTITVITITAITI TTT DIT IT TT eyIEE EEEEIIITDTDES' = OO (= SS ee Serv Near, New eib 18, PX 61-2085108, 26861009 wurncncenengsns com} SUMMARY OFSOME ‘COMPLEX REACTIONS. OF VARIOUS. ORDERS Parallel reactions: ‘The rate equation for Ais A talon tal-th tel] "hs the disappearance ofA will be frst order reaction and wecan write : [Als[ahe af 7 ‘The rate equation for B is ae), [A]=K [A] Os Pacem o> BEAL aot] Concentation FB) Concentration of Ce Sinitaty teeth [eto] Opposing or Reversible Reaction: (Case: (I) First order opposed by i order Initiateanc. a 0 Attimet a-x x At equiibvion a—x, x, Net rate offormation of B at time ‘tis Bek (an) =) SS « Acai = 0andx x, Thus, k, (a—x,)=k, x, k,(a=x,) c[k BOI] ue Substituting the value of k,n the equation(1) gives, dx a TE & WT-JAM Exams ee NaS‘Case (I): first order reaction opposed by second order reaction ASE B+ Initiale a0 Altime't? a-x x Atequilibrium- a—x, x, x, Net rate ofreaction <=, (a—x)-| TUr?tITggase BS ype lara) x We get, ket (a x,) S i@-x) "alx.—x) - > Case (IM): second order opposed by 2 order a A+Bee=c+D a i = Initisteone a0 : Attime't! a-x x x e At Equilibrium ax, x, x, a = i Baig(ex) ke? = mn Bh BE Oe ek ee ee Re Consider a first order consecutivereaction A 4» B—-» C Because each step of this mechanism is an elementary reactionthe rate knws for each species A, B and C are @ Ai) (i) ° When 1=0,C, |IIIS IIIS Idd I ISI ISS oS wot « « Eases 6, Soln: 2A, Sha Sarai, Nea Nev Dis6 Po 00-2851008 26861009 worwcarendenourcom | Equation (Dis first order differential equation and ean be solved as usual : z Equation (iis als first order differential equation andis given by 2 +Py=Q whose solution is, [Remember that in consecutive reaction A—>B—+¢ a GG, +C, (At all times) Example: Example ofconsecutive reaction for the reaction P& Qs 5 Giventhat [P],=1.0M, k, = 1507s" R nre 0.5966 M and 0.0355 M respectively i (2) 500 see (6) 750 see (©) 1000 see (@) 15000 see 1105" the time at which the concentration of Q and IGATE: 2004 Since, [PL= [P}+[o]+[R] PPE PPL - { [2}+ [2 =1.0~f.5966+.0353}- 0.3679 Now for concentration of P PPI=IPL ©" 5 0.3679 = ces in 03679-11073 n (0.3679) Since, == 3679 ; 1 4 1x10? aM Eams C3)[Gees Tb Sa se sae ecu new bang ra atesiois lasiioy woweananaemas ‘oriationin concentrations of consecutive fist orderresetion when = 7,0 44 (i) ky >> ky (il) k, << ky ia} -& Cone Cone} \ B] | ~ Ay Sas or Chain reaciton: is defined as series of'suecessive elementary processes in which active intermediate species sre-consumed and regenerated bere the proshicts are obtained. It cosists of following steps. ()Chaininitiation i) Chain propagation (ii) Chain transier G6) Chain inhibition (9) Chain termination. Cin easton ‘Steady-stateappruximation:The assuinptions involved in the steady-state approximation is that concentra- “ tion of reactive intermediate can be assumed to be constant. If the reactiveintermedite, ther [€,}=constant [ci] dt ‘This approximation is applied only for short-lived species a Kineties of chain reactions: g Let achain easton, inwhich Ais reactant, Ris active chaincairier, Pisthe product and’." isthe mumber. = of chain carier produced by the carir in the propagation step 1. Chain nit ition: AR 2. Chain propagation: R+A—*=>P 4 aR 3. Chain termination: R > Destruction d[R} The rate of formation of chain carrier, a =k [A]+k, (a=I)[R][A]~k, [R] Although S.S.A. isnot applicable on R but in orderto know the steady state and explosion limit, $8.4. can be applied Accordingto steady-state treatment to R. e _aN. "eos =k (a- IR ]LA} +4, [R]=0 € : a]. : WAT ky 7 Institute For NET-JRF/GATE & HT-JAM Exains aOagGdadAagagaagqggagegepeaereraggage@gteqgdeaewrinlear Gass alae 1, New Delli-16, Ph 011-26851008, 26861009" wwrw.carcerendeavourcom ‘The termination (destruction) 6f chain carriers ma mokeulesin gas phase. Wk, ty be due to cblision withthe walls of vessels, or with other locity constant for wall reaction and k, = Velocity constant fer gas phase reaction ‘Then, k=k, +k, k, [A] k,(-a)[A}+k, +k, ay ‘The rate of overall reaction is given by step 2 Sky [RIA] ax kk [Ay "atk, (I-a)[ApHE +k, ‘sdefined as the number of cycles that an active intermediate specie formation step and termination step. putting value of [R}, we get Chain lenga between can participate in “Rate of overall reaction kk [AT aon au ate of initiation reaction” k, [A](k, (I-a)[A]+k, +k) kK [l-a][A}ek, +k, Analysis of équation (1): Chain length=. ky[A] _ Rate of formation of Ky Rete of destruction of Such reactions are called non-branched o¥ stalionary chain reactions. ase: When o=1, them, [R} Case II: Explosion limits, when > 1, such rcactionsare called branched or non-stationary chain reac: ‘ons. The chain carrier destruction rate, I. , depends on the diffusion ofRto the walls and israpid at low pressure. When at a particular pressure Rate of destruction of R on walls = Rate of formation of R hen, no explosion occurs. This gives first explosion limit (stho resareineeses the dition of R to wall decreates hence K, deoretses while nreses If Pressure increases conned to sucha stage tht (k, +k,) eourterbaances k, (I«)[A] ie k, +h, +k, (I-@)[A]=0, then [R ‘his gives second explosion limit, above this pressure, reac sure (explosion) limit is due to thermal effects tion proceeds with finite speed. The third pres- Explosion Tet exten & etal paessure > Sta ale aise Teron 0), Institute For NET-JRF/GATE & It Edi I GG CCC CCC CISC IOI DEI ISI IESoln, Soln, (] ews Wo tiv ae a ss als th sonido, 26861009 womcarerendeavourcom Example: Suggesta probable mechanism forthe following oxidation reduction nag, soliton, a Hg? +01 —o2Hg? 411" Which is consistent with rate Law ¥[He,”] [71] teen Hl? —= He + He (fst) Hg4 TI" —sHg” +11" (slow) [He”] ne] ; . -£ [Her] rate =k Hg}; rate kf }ex,, bE] te=k (Hg) % rate P71") XT > «K. Med eae: € Example: At any time t the rate of change in the no. of decaying nucleous is times he no. of nuclei # Present, where % is decay.constant then the time at which 2/3rd of the originally: present nuclei would have decay, ven aN 78 = tat 2 Cronin 5 JR T InNJN =x In3=t5 a CATV OTT I TTA III as