CPT — Chemical Kinetics Chemical Kinetics 2.303 8. 2303 jog 4 - 2303 19616 =4,60« 1025 ail 60s In such cases, the molecules do not collide in proper orientation. Rate ofreaction ()=k[N;Og]=6.2* 10°51 15molL? =93 x 10% mol Ls 1=93 x 105 mol ts! In the vapour state, the molecules of bromine have more kinetic energy than in the liquid state. Therefore, collisions with the molecules of other reactants in the vapour state ‘willbe faster than inthe liquid state. Moreover, inthe vapour state, the surface area available forthe chemical reaction is ‘more as compared tothe liquid state, Hence, bromine in the ‘vapour state reacts at a faster rate compared with the liquid state. ‘As Ey > Ej, this means that the reaction is exothermic in nature, Rate law is derived from slow step as &~£,1No,][NO G7 BAINOsIINO] [NOs] From(i) k= 3" or [NOs]= {NO} [05] [NO}fO] * Substituting value of [NO] in the above rate law, we get a ae = ky xkINOFIO. a el lol Itisrate law. The order of reaction is2+1=3 Caleulation of the rate constant (K) for the reaction a= 100;x=75; (a—x)~ 100-75 =25 ;1=32 minutes 2303, 100 %. G2min) “25 2303 2,303 0.6021 = ga c 2205x 0.6021, G2min °° 32min) = 0.0433 min"! Calculation of halflife period (1,2) _ 0.693 ha= 2.689 min (0.0433 min’ Calculation of concentration after 1h (60 min). 2303 [Alo Jog Ao + IAL [Alp kt_ 45x10 min“!<60min eS ee a taineem= 11775 ETA), | 2303 2.303 [4b {bo — anilog0.11723= 1.3105 [Ayre [Alp (k= 7310-1310 Caleulationofrte after Ih (60 min. Rate after 60 min =K[A],=4.5 « 10-3 min“ x 0.763 M =3.4335 «103 Mmin! or Lets be te order wrt lp and ybe the order w.NO. Rate=HC,}"[NOP From experments(I) and 2) 1,2 104=k[0.010} (0.0107 i) 10.8 x 10=K[0.010}* [0.0307 ii) Dividing () andi). weget IM 0.763M or3?=3ory=2 oy From experiments (2) and (3) 108 10-4=« (0.010) [0.030 i) 21.6 10-4= k 0.020} [0.030 wold) Dividing (ii) and (iv), we get 1 = or2%=2! ors 2 9 Rate equation for the reaction is a a Using Arthenius equation in the following form and substituting the values, we get {C},] [NOP E hy eigen tpn a ar RT 1 Inf Inh = Zo ~Eay) or log? = —1__ 95.24 mo!—50.14K} mol) ee, 2303RT z oF log = —1_ 25.1010 mol") 2.303RT(CHEMISTRY-12 25.10%1000 J mol 2.303*8.314JKImol! x298K or top 251049 er ox Antings 40=251886 i Trerate of eaction will grow by 25118.86 times in presence of catalyst Calculation of time for the decomposition of 99% of NHNO,, 10. i) Rate constam ) = 28 4a 0.693 =i Qin) 3 For the first order reaction, t = 220) __ 2303 33h 2303.2 0.33) Calculation of volume of NO evolved at $.P. (6.2g) x99 100 ie * (100-99) hr =13.96 br Mass of NH;NO, decomposed 6.1382. No. of moles of NHNO, decomposed (6.1388) (62gmol') ‘No. of moles of N,O formed ‘Volume of N,O evolved tS. 099 mol, 099 mot 099% 22400 mL. 217 6mL. 11. According to Arrhenius equation, 0 iE eee t-aataly Iofky =2;7, =295 K; T= 305K; 31434 mo! Soe er) © 2303x(8314 JK mol log? ae 305K @ E, 00 ie ee = 2.303% (8.314Jmol') 295x305 03010 x 2.303 x 8.314 x 295 x 305 10 (mot) =51855.19J mol 51,855 mot oR (ANP (_ concentration of B is tripled, the rate of reaction becomes 9 times 9 (i) Te concentrations of 14’ and 'B' both are doubled, the rate of reaction becomes 8 times. Rate constant is equal to rate of reaction when molar concentration of reactant is unity, Reaction rate = k [NOP [05] Since the volume of the vessel is reduced to one third (1/3) of the original volume, the concentration of the reactants per unit volume will become thrice. Rate with respect to NO will become nine times, Rate with respect to 0, will become thrice. Overall reaction rate will increase to 27 times. There will no change in the order ofthe reaction. (a) For the uncatalysed reaction, represented by upper curve’ Energy of the reactants (E, Energy of the products (E, ‘Change in intemal energy (AE) = = 100-110=—10kS mol Energy of activation forthe forward reaction E,(Q=E°-E,=140-110=30k3 mot! Energy of activation for the reserve reaction E,(b)=E°-E, = 140—100=40 kJ mol (6) For the catalysed reaction, represented by lower curve, E,(h=E°-E,=120-110=10kI mol! E,(6)=F°—E,= 120-100 =20 ki mot! ‘There will no effect on the extent of the reaction because the activation energies for the forward backward reactions have decreased equally. © ‘OR Reaction path Enerey of 2 ~—eg~| without a Eneryof f | Cais rath with cualst Pot Products ‘Rercton cordate fest featalyst on activation crery When 20% of the original matter reacts, 80 4 TAl=7oglAlo oF {Alo Using the equation of first order and substituting, the values, we get 2303, [4h t (4 A oe Lh 1 $Uh 303, r logs “Hoe is oes heed]10 © k= aS x [0.6990-0.6021] ox bx 23B oop = 0206 1 or &=0,0148 min! = 1.4810 min ‘When 10% of the matter remains unreacted 10 [A]= pple (0% has reacted) 2.303 [Al sft gb i009 “bo 2303 = hog 148x107? min? 2.303 = 288 11556 148x107 min © CPT —Chemical Kinetics Amount left after 15 minutes Stale Amount lefl after 20% of reactant has reacted 4 0 = 14h - 5% jo lAl0 20-4 16 = AS a = Fb ‘Again using first order equation and substituting the values, we get 4 03, lle lon Bua Stay eS 148x107 min 4 2303 9.0969 1.48x10