Mea He ML CEN ed ee Se > Multiple Choice Questions (MCQs) 1. The decomposition of dimethyl ether is a fractional order reaction. The rate of reaction is given by rate = Apeqigcoctig)™”. If the pressure is measured in bar and time in minutes, then what are the units of rate and rate constant respectively? (a) bar min“, bar? min’ (b) bar min~, bar“! min-* (©) bar-Y? min~, bar? min’ (@) bar min”, bar"? min 2. The rate of a gaseous reaction is given by the expression k[APB)’. The volume of the reaction vessel is reduced to one half of the initial volume. What will be the reaction rate as compared to 1 the original rate a? (a) 4a ) ta 3 2 (©) 2a (a) 82a 3. Fora reaction P + Q-» 2R +S. Which of the following statements is incorrect? (a) Rate of disappearance of P = Rate of appearance of S Rate of disappearance of Q = 2 x Rate of appearance of R Rate of disappearance of P = disappearance of Q Rate of disappearance of Q = 1x Rate of appearance of R 2 4, Which of the following statements for order of reaction is not correct? (a) Order can be determined experimentally. (b) Order of reaction is equal to the sum of powers of concentration terms in rate law expression. Order cannot be fractional. Order is not affected by stoichiometric coefficient of the reactants. () ©) Rate of @ ©) @ 5. The halflife of the reaction X — Y, following first order kineties, when the initial concentration of A is 0.01 mol L-! and initial rate is 0.00352 mol Lt min“ will be (a) 19.69 min (b) 1.969 min (©) 7.75 min () 77.5 min 6. The reaction 2X->¥ + Z would be zero order reaction when (a) rate remains unchanged at any concentration of Yand Z rate of reaction doubles if concentration of Y is doubled. rate of reaction remains same at any concentration of X rate of reaction is directly proportional to square of concentration of X. (b) © @ 7. The rate constant of a first order reaction is 15x 10 s"!, How long will 5.0 g of this reactant, take to reduce to 3.0 g? (a) 34.07 5 (b) 7.575 (©) 10.105 (@) bs 8. The decomposition of a substance follows first order kineties. If its concentration is reduced to 1/8 of its initial value in 12 minutes, the rate constant of the decomposition system ta) (2241042) min-* () (2221068) min co ( 9. Which of the following statements is not correct? (a) For a zero order reaction, ty is proportional to initial concentration, 1 Lies) ae ca (rns) 1 eh. where n is order (b) Fora reaction typ =—4,, of the reaction. 0 semtenatsane o—Chemical Kinetics (c) The unit of rate constant for a reaction is mol!~" L"~! s“! where n is order of the reaction. (a) The unit of rate of reaction changes with order of reaction. 10. Consider the reaction, 2N,O; —> 4NO, + 03, In the reaction NO, is being formed at the rate of 0.0125 mol L- s, What is the rate of reaction at this time? (a) 0.0018 mol L's (b) 0.0081 mol L“ s (©) 0.0041 mol Ls (@) 0.050 mol L“* s** 11. Consider the reaction P + Q. The concentration of both the reactants and the products varies exponentially with time. Which of the following figures correctly describes the change in concentration of reactants and prodocia with timst P my ) A * : (a) — ) = 5 i 4 é vy = Time : i lo A i to) (a) é v1 @ 12. The number of molecules of the reactants taking part in a single step of the reaction is indicative of (a) order of a reaction (b) molecularity of a reaction (c) fast step of the mechanism of a reaction (a) half-life of the reaction 13, For a reversible reaction, A +B <== C+D, the graph for rate of reaction with time is given below. o Rate —> o Ta ‘Mark the terms (p), (g) and (7). ry) (a) (p) - rate of backward reaction, (9) - rate of forward reaction, (r) - equilibrium (b) (p) - rate of forward reaction, (q) - rate of backward reaction, (r) - equilibrium (©) (p) - concentration of products, (q) - concentration of reactants, (r) - rate of reaction (4) (p) - instantaneous rate of reaction, (q) - variation of rate, (r)- average rate of reaction 14, For the reaction, 2Nj0; —> 4NO, + Op, the rate of reaction can be expressed in terms of time and concentration by the expression: N,05)__1AlNOp) _ 1.4104) dt 4 dt 2 dt © rane 2A AMON A 15. Inareaction 21> H, + Ip, the concentration of HI decreases from 0.5 mol L~" to 0.4 mol L*! in 10 minutes. What is the rate of reaction during this interval? (a) 5x 10% M min (©) 5x10? M min (b) 2.5 x 10-° M min? (4) 2.5 x 107 M min 16. The unit of rate and rate constant are same for a (a) zero order reaction (b) first order reaction (©) second order reaction (@) third order reaction. 17. In pseudo unimolecular reactions, (a) both the reactants are present in low concentration (b) both the reactants are present in same concentration (©) one of the reactants is present in excess (a) one of the reactants is non-reactive 18. For a reaction RP, the concentration of a reactant changes from 0.05 M to 0.04 M in 30 minutes. What will be the average rate of reaction in minutes? (a) 4x 104M min (b) 8 x 10“ M min (©) 8.3% 10M min (4) 2.2.x 10 M min 0 semtenatsane o—19. For a general reaction X—> Y, the plot of cone. of X us time is given in the figure. What is the order of the reaction and what are the units of rate Cone. of —> Tim —> constant? (a) Zero, mol L's“? (b) First, mol L-! s! © First, (a) Zero, L mol s 20. Which of the following is an example of a fractional order reaction? (a) NH,NO, + N, + 2H,0 (b) NO + 03> NO, + 0, (©) 2NO + Br, > 2NOBr (@) CH,CHO > CH, + CO 21. The value of rate of a pseudo first order reaction depends upon (a) the concentration of both the reactants present in the reaction (b) the concentration of the reactant present in small amount (©) the concentration of the reactant present in excess (d) the value of AH of the reaction. 22. The rate law for a reaction, A+B~C + Dis given by the expression (Al, ‘The rate of reaction will be (a) doubled on doubling the concentration of B (b) halved on reducing the concentration of A to half (©) decreased on increasing the temperature of the reaction unaffected by any change in concentration or temperature. @ 23. Nitrogen dioxide (NO,) dissociates into nitric oxide (NO) and oxygen (O.) as follows: 2NO, > 2NO + 0, If the rate of decrease of concentration of NO, is 6.0 x 10°? mol L“! “1, what will be the rate of increase of concentration of 0,2 (a) 3x 107? mol L-! st (b) 6 x 10-1? mol Lt st (©) 1x 107 mol Lt st (a) 1.5 x 107? mol L757 24. For the reaction ANH, +50,—> 4NO+6H,0, if the rate of disappearance of NHg is 3.6 x 10°? mol L“! s“!, what is the rate of formation of H,0? (a) 5.4% 10° mol Lt s (b) 3.6 x 10° mol L=! 51 (e) 4x 10+ mol L-! s+ (@) 0.6 x 10 mol Lt 25. The rate constant for the reaction, 2N,05 ~ 4NO, + O, is 2x 10% 5". If rate of reaction is 1.4 x 10-° mol L™ s!, what will be the concentration of NO, in mol L7!? (a) 08 ) 0.7 © 12 @1 26. When a chemical reaction takes place, during the course of the reaction the rate of reaction (a) keeps on inereasing with time (b) remains constant with time (©) keeps on decreasing with time (@) shows irregular trend with time. 27. (@) For a unimolecular reaction, the order and molecularity of the slowest step are equal to one molecularity of the reaction can be zero, one or two ) (©) more than one reacting species are involved in one step molecularity of the reaction can be determined only experimentally. 28. Ina reaction 2X ~ Y, the concentration of X decreases from 3.0 molesilitre to 2.0 molesfitre in 5 minutes. The rato of reaction is (a) 0.1 mol L*! min“ (b) 5 mol L mi (©) mol L“! min — (d) 0.5 mol L™ mis 29. The chemical reaction, 20, -> 80, proceeds as @ 03 = 0, + [0] [0] + 0, 20, ‘The rate law expression will be (a) Rate = [O][03] _(b) Rate = A[O,]*[0,)7 (c) Rate = k{O,]” (d) Rate = k{0,](0} 30. Radioactive disintegration is an example of (a) zero order reaction (b) first order reaction (c) second order reaction (d) third order reaction. (fast) (slow) 31. In a first ordor reaction the concentration of reactant decreases from 400 mol L-! to 25 mol L"" in 200 seconds. The rate constant for the reaction isChemical Kinetics (b) 2x 10s? (@) 3.4.x 10 (a) 1.01386 s** (©) 1.886 x 107? s 32. What will be the rate equation for the reaction 2X + YZ, if the order of the reaction is zero? HIXIY] —(b) Rate =k RIXIIY] (a) Rate = RIXIEZ 33. The following data were obtained during the first order thermal decomposition of SO,Cly at a constant volume. 80,Claig)* SOx) + Clary Experiment Time/s"! Total pressure/atm 1 o 05 2 100 06 What is the rate of reaction when total pressure is 0.65 atm? (a) 0.35 atm s+ (b) 2.235 x 10 atm st (©) 7.8 10+ atm st (@) 1.85 x 10+ atm = 34, A first order reaction is 20% complete in 10 minutes. What is the specific rate constant for the reaction? a) 0.0970 min? b) 0.009 mint (©) 0.0228 mint (@) 2.223 mint 35. In a pseudo first order hydrolysis of ester in water, the following results were obtained t o | 80 | 60 | 9 Ester/molL" | 0.55 | 0.31 | 0.17 | 0.085 What will be the average rate of reaction between the time interval 30 to 60 seconds? (a) 1.91 10% st (b) 4.67 x 10°? mol L (©) 1.98x 10 st (d) 2.07 x 107 st 36. Two plots are shown below between concentration and time ¢, Which of the given orders are shown by the graphs respectively? (a) Zero order and first order (b) First order and first order 29 (©) First order and zero order (d) None of these 37. For the reaction Nj + SH, > 2NH,, how are the rate of reaction expressions inter-related (Hy) |, diNHg), aa idly) 141NHg | 38. The expression to calculate time required for completion of zero order reaction is (b) t= (RI [Rol _ (Rl R) @ 39. For the reaction 2NH, ~ Ny + 3H,, if, NH] aONg] - ar = hy (NHg], “G2 = kyl NH], dU} _ wa 7 hs UNH] then the relation between k,, ky and ky is, (a) ky = hy = hy (b) hy = Sky = 2kg (©) 15k, = Bky= hy (4) 2ky = hy = Bk 40. The decomposition of dinitrogen pentoxide (N,05) follows first order rate law. What will be the rate constant from the given data? At t= 800s, [N,O5] = 1.45 mol L At t = 1600s, [N05] = 0.88 mol Lt (a) 8.1210 s (b) 6.24 x 10-4 st (© 284x104st (a) 8.14x 10-45 41. The overall rate of a reaction is governed by (a) the rate of fastest intermediate step (b) the sum total of the rates of all intermediate steps (©) theaverage ofthe rates of all the intermediate steps (d) the rate of slowest intermediate step. 42. Rate of reaction isthe change in concentration of any one of the reactants or products per unit time. 0 semtenatsane o—For a hypothetical reaction, A —> B AA_ AB] dt dt Ina reaction, A+2B—>3C +2D, the concentration of A decreases from 0.5 moV/L. to 0.35 moV/L in 15 seconds. Then a student Ajinkya calculated following rates : 1. Rate of formation of C is 0.03 mol/L-s. IL. Rate of formation of D is 0.025 mol/L-s. IIL. Rate of disappearance of B is 0.02 mol/L-s. Which is/are incorrect statement(s)? (a) Lonly (b) Tonly (©) 1 & UI both (@) T& IT both 43. For a first order reaction, [A] = [A]ge* concentration of reactant decreases exponentially with time. and typ Rate of reaction = — 693 k This relation shows that half-life is independent of concentration and ty, decreases with the increase of temperature For first order reaction, 2N20 54g) —> 4NO zp) + Onip) ‘The reaction proceeds to 99.6% completion in (a) 2 half lives (b) 6 half lives (©) 8 half lives (@) 5 half lives 44, A student of class-12, Jayesh did few experiments for the reaction, 2N 105i) —> 2Nz0 4g) + Ong) and he plotted time against total pressure 0.580 0.520. 6.508 P, 0.510: 512 08: 0100 200 = SD Case Based MCQs Case 1: Read the following and answer the questions from 47 to 51 given below. The half-life of a reaction is the time required for the concentration of reactant to decrease by half, 1 ie. [Al =f (Ay =314] For first order reaction, ty = 693 he If this reaction follows first order kinetics, value of rate constant R is (a) 5.96 x10%s* — (b) 4.98x 104s? (co) 4.13 x 10-9 st (d) 5.85 x 10 s? 45, Priyanshi after learning chemical kinetics chapter in class, she made notes for zero order and first order reactions as given below: [Differential] Integral | Stra-| Half Units Rate [Rate law| ight | Life | IV] law tm | Line | trv m plot am ‘Zero | atri Bt = (Rg | Inf] [TRV lorder | “Ge =1R) | vst iFirst Jace) TRi= | (Ry [in2e | ot lorder [gp ER tye | vst But the made few mistakes. Identify the wrong, listed equations. (a) OnlyLand It (b) Only Tand I (© Only IV (@) Wand IV 46, For the reaction, A+B —>C following data has been observed From the following data for thereaction between A and B. initial rate Ba] tan | mh | mote et at or ee me 300K | 320K T_ [2.6 x 10] 3.0 x 10 [5.0 x 10|2.0 x 10 1 [5.0x10|6.0x10%|40x109| — TH [1.0x10-/6.0x10]16x102] — ‘The incorrect option about this reaction is (a) the order of reaction with respect to A is 2 (b) the order of reaction with respect to B is 1 (©) the rate constant for the given reaction is 2.67 x 10° mol? L? st (@) none of these. thismeanst,pisindependent of initial concentration. Figure shows that typical variation of concentration of reactant exhibiting first order kinetics. It may be noted that though the major \Concertration —> [Namber fal le —>Chemical Kinetics portion of the first order kinetics may be over in a finite time, but the reaction will never cease as the concentration of reactant will be zero only at infinite time. 47. A first order reaction has a rate constant k = 3.01 x 10-* /s. How long it will take to decompose half of the reactant? (a) 2.303 s (b) 23.03 s (©) 230.35 (a) 2308 5 48, The rate constant for a first order reaction is 7.0x 10+ s* If initial concentration of reactant is 0.080 M, what is the half life of reaction? (a) 990s (b) 79.28 (c) 12875 s (d) 10.10 x 10~ s 49. For the half-life period of a first order reaction, which one of the following statements is generally false? (a) It is independent of initial concentration. (b) It is dependent on rate of the reaction. (c) At ty, the concentration of the reactant is reduced by half. () None of these. 50. The rate of a first order reaction is 0.04 mol L's“ at 10 minutes and 0.08 mol L~!s- at 20 minutes after initiation. The half-life of the reaction is (a) 4.408 min (b) 44.086 min (c) 24.086 min (4) 2.408 min 51. The plot of typ vs initial concentration [Alp for a first order reaction is given by 1 t («fa ) a> 7S 1 SN 1 (eo) ha (a) 4] [Alb [Al Case II : Read the following and answer the questions from 52 to 55 given below. For a first order reaction, A — Products, 2303, a = log“, where a is the initial concentration of A and (a-x) is the concentration of A after time t. & is rate constant. Its value is constant at constant temperature for a ke 31 reaction. The time in which half of the reactant is consumed is called halflife period. Half-life period of a first order reaction is constant. Its value is independent of initial concentration or any other external conditions In the following questions (Q. No. 52-55), a statement of assertion followed by a statement of reason is given. Choose the correct answer out of the following choices on the basis of the above passage. (a) Assertion and reason both are correct statements and reason is correct explanation for assertion. Assertion and reason both are correct statements but reason is not correct explanation for assertion. Assertion is correct statement but reason is wrong statement. Assertion is wrong statement but reason is correct statement. 52. Assertion : Rate of reaction doubles when concentration of reactant is doubled if t is a first order reaction. Reason : Rate constant also doubles 53. Assertion : For the first order reaction, (by © @ half-life period is expressed as ty; Reason : The half-life time of a first order reaction is not always constant and it depends upon the initial concentration of reactants. 54, Assertion : For a first order reaction, the concentration of the reactant decreases exponentially with time. Reason : Rate of reaction at any time depends upon the concentration of the reactant at that time. 55. Assertion : Half-life period for a first order reaction is independent of initial concentration of the reactant. Reason : For a first order reaction, ty. where & is rate constant, Case III : Read the following and answer the questions from 56 to 59 given below. Number of molecules which must collide simultaneously to give product is called molecularity. It is equal to sum of coefficients of reactants present in stoichiometric chemical equation. For reaction, mA + myB — Product 0 semtenatsane o—‘Molecularity = [m, + my] In complex reaction each step has its own molecularity which is equal to the sum of coefficients of reactants present in a particular step. Molecularity is a theoretical property. Its value is any whole number. Number of concentration terms on which rate of reaction depends is called order of reaction or sum of powers of concentration terms present in the rate equation is called order of reaction. Ifrate equation of reaction is : Rate =k-Cj! «Cp? Then order of reaction = my + ma. In simple reaction, order and molecularity are same. In complex reaction, order of slowest step is the order of over all reaction. This step is known as rate determining step. Order is an experimental property. Its value may be zero, fractional or negative. 56. The rate of reaction, A + 2B — products, is MA) cane dt If B is present in large excess, the order of the reaction is (a) zero (©) second givenby the following equatio1 (b) first (@) third. 57. The molecularity of the reaction : 6FeSO, + 3H,S0, + KCIO, > KCl + 8Fe(S0,), + 3H,0 is (@) 6 ) 3 © 10 @7 58. Which of the following statements is false in the following? (a) Order of a reaction may be even zero. (b) Molecularity of a reaction is always a whole number. Molecularity and order always have same values for a reaction. Order of a reaction depends upon the mechanism of the reaction. ‘Therateofthe reaction, A +B +C— products, SALA CN. ‘The order of the reaction is 1 1 @, OF © @ 59, is given by r: 1 13 (c) 7 (a) 2 Case IV : Read the following and answer the questions from 60 to 64 given below. For the reaction : 2NOy + Clog) > 2NOChg), the following data were collected. All the measurements were taken at 263 K. = psec a tia (M) (M) (M/min) 1, 0.15 0.15 0.60 3. 0.30 0.15 2.40 4. 0.25 0.25 2 60. The molecularity of the reaction is @ i ae @3 @a4 61. The expression for rate law is (a) r=R(NOMCl,] ——(b) r= AINOFICI,] (©) r=AINOJCl? (a) r= AINOFICI]? 62. The overall order of the reaction is (a) 2 &) 0 © @ 3 63. The value of rate constant is (a) 150.32 M7 min? (b) 200.08 M7! min ©) 177.77 M? mind): 155.75 Mt min 64. The initial rate of disappearance of Cly in experiment 4 is (a) 1.75 M min (b) 3.23 M min (©) 2.25 M min (4) 2.77 M min Case V : Read the following and answer the questions from 65 to 69 given below. Areaction is said to be of the first order if the rate of the reaction depends upon one concentration term only. For a first order reaction of the type A= Products, the rate of the reaction is given as : rate = KA]. The differential rate law is given as : a = -h[A]. The integrated rate law is : in 141. iA ~kt, where [A] is the concentration of reactant left at time t and [Al is the initial concentration of the reactant, is the rate constant. 65. The unit of rate constant for a first order reaction is (a) st (© Lmor" (b) mol L715” (@) L? mor"Chemical Kinetics 66. Half-life period of a first order reaction is 10 min, Starting with initial concentration 12 M, the rate after 20 min is (a) 0.693 x 3 M min“? (b) 0.0693 x 4 M min? (c) 0.0693 M min! (4) 0.0693 x3 M min“ 67. 50% of a first order reaction is complete in 28 minutes. Calculate the time required to complete 90% of the reaction. (a) 70.4 minutes (b) 76.4 minutes (©) 38.7 minutes (4) 35.2 minutes 33 68. For a first order reaction, (A) products, the concentration of A changes from 0.1 M to 0.025 M in 40 minutes. The rate of reaction when the concentration of A is 0.01 M, is (a) 8.47 10 M/min (b) 8.47 x 10 M/min (©) 1.7310 M/min (d) 1.73 x 10° M/min 69. The halflife period of a 18t order reaction is 60 minutes. What percentage will be left over after 240 minutes? (a) 6.25% (©) 5% (b) 4.25% (@) 6% > Assertion & Reasoning Based MCQs For question numbers 70-80, a statement of assertion followed by a statement of reason is given. Choose the correct answer out of the following choices. (@) Assertion and reason both are correct statements and reason is corect explanation for assertion. (0) Assertion and reason both are correct statements but reason isnot correct explanation for assertion. (6) Assertion is correct statement but reason is wrong statement. (a) Assertion is wrong statement but reason is correct statement. 70. Assertion : The rate of the reaction is the rate of change of concentration of a reactant or a product. Reason : Rate of reaction remains constant during the complete reaction. 71. Assertion : The rate law equation can be found only by experiment. Reason : It can be written from stoichiometric ‘equation. 72. Assertion : The order of the reaction CH,COOC;H, + HzO + CHyCOOH + C,H,OH 1 Reason : The molecularity of this reaction is 2. 73. Assertion : For the reaction, 2N05 > 4NO, + 02, Rate = k(N,O5] Reason : Rate of decomposition of NOs is determined by slow step. 74, Assertion : Half-life period of a reaction of first order is independent of initial concentration. Reason : The time taken for completion of 75% of a first order reaction is equivalent to two half lives. 75. Assertion : Chemical kinetics deals with the rate of reaction, the factors affecting the rate of the reaction and the mechanism by which the reaction proceeds. Reason : Nature of reactants, concentration of reactants, products and catalyst affect the rate of reaction. 76. Assertion : Formation of HIis a bimolecular reaction. Reason : Two molecules of reactants are involved in this reaction. 77. Assertion : Hydrolysis of cane sugar is a pseudo first order reaction. Reason : Water is present in large excess during hydrolysis, 78. Assertion : Rate of reaction can be expressed as rate of change in partial pressure of the gaseous reactants or products. Reason : Partial pressure of a gas is equal to its concentration. 79. Assertion : The decomposition of NH on finely divided platinum surface is first order when the concentration is low, however at higher concentration, the reaction becomes zero order. Reason : In first order reaction, the rate of reaction is proportional to the first power of the concentration of the reactant. 80. Assertion : Instantaneous rate of reaction is equal to dv/dt. Reason : It is the rate of reaction at any particular instant of time. 0 semtenatsaneChemical Kinetics 35 > Short Answer Type Questions (SA-II) 21. What do you understand by the ‘order of a reaction’? Identify the reaction order from each of the following units of reaction rate constant (i) 1? mol s Gi) L mors 22, For a chemical reaction 4) R — P, the variation in the ~~ concentration, In {R] vs. time (s) "1 plot is given as aS (i) Prodict the order of the reaction (ii) What is the slope of the curve? ii) Write the unit of the rate constant for this reaction, 23. For a reaction, the rate law is Rate = & [A][B]"”. Can this reaction be an elementary reaction? 24. A reaction is first order in A and second order in B (i) Write differential rate equation. (ii) How is rate affected when concentration of Bis tripled? (iii) How is rate affected when concentration of both A and B is doubled? (iv) What is molecularity of a reaction? 25. In a pseudo first order hyrolysis of ester in water, the following results are obtained : tinseconds | 0 | 30 | 60 | 90 [Ester]M 0.55 | 0.31 | 0.17 | 0.085 (i) Calculate the average rate of reaction between the time interval 30 to 60 seconds. (ii) Calculate the pseudo first order rate constant for the hydrolysis of ester. 26, The rate of decomposition of ammonia is found to depend upon the concentration of NH d@{NHy]__&(NHy] dt ~ 1+ ky(NHy] What will be the order of reaction when (i) concentration of NH, is very high? (ii) concentration of NH, is very low? according to the equation — 27. Acertain reaction takes 5 minutes for initial concentration 0.5 mol L~" ta become 0.25 mol L-! and another 5 minutes to becomes 0.125 mol L". What is the order and specific rate constant of the reaction? 28. Following data are obtained for the reaction N,0, > 2N0, + 10, tls 0 300 600 INO), me) Lt | 26x10? | 08x10) 04x 107 (a) Show that it follows first order reaction. (b) Calculate the half-life. (Given : log 2 = 0.3010, log = 0.6021) 29. A first order reaction takes 160 minutes time for 20% completion. Calculate time required for half completion of reaction. 30. Hydrogen peroxide, Hj0,,) decomposes to HO, and Oy.., in a reaction that is first order in H,0, and has a rate constant k = 1.06% 10 min (@) How long will it take for 15% of a sample of H,0, to decompose? ii) How long will it take for 85% of the sample to decompose? 31. When inversion of sucrose is studied at pH=5, the half-life period is always found to be 500 minutes irrespective of any initial concentration but when it is studied at pH = 6, the half-life period is found to be 50 minutes. Derive the rate law expression for the inversion of sucrose. 32. What will be the rate of decomposition of N,0; and rate of formation of NO, and 0, when [N,O5] = 0.40M for the reaction 2N,0, ~> 4NO, + 02. The rate constant for this reaction is 8.1 x 10 min~*, 33. The following data were obtained during the first order thermal decomposition of SO,Cly at a constant volume 805Clyip) —> SOpig) + Clay, Experiment |Time/s| Total pressure/atm 1 0 04 2 100 07 Calculate the rate constant. (Given : log 4 = 0.6021, log 2 = 0.3010) 0 semtenatsane OeSTEMS sy > Very Short Answer Type Questions (VSA) 1. Distinguish between molecularity and order of a reaction 2. Define the half-life poriod of reaction (t 3. For a reaction R —> P, half-life (ty) is, observed to be independent of the initial concentration of reactants. What is the order of reaction? 4, Ifhalf-life period of a first order reaction is, x and 3/4" life period of the same reaction is y, how are x and y related to each other? 5. Draw a graph between concentration and time for a zero order reaction. > Short Answer Type Questions (SA-I) 11. Forareaction A +B ~ P, the rate law is given by, r = RIA)”? (BP What is the order of this reaction? 12. For a chemical reaction R > P, the variation in the concentration LR] vs. time (t) plot is given as tl (Predict the order of the reaction.‘ Gi) What is the slope of the curve? 13. For a reaction = ‘alkaline media 2H,0. 2H,0+ 0. the proposed mechanism is as given below : (1) H,0, +> —+H,0+ 10° (slow) (2) H,0, +10” —+H,0 +I" +0, (fast) (i) Write rate law for the reaction. (ii) Write the overall order of reaction. ii) Out of steps (1) and (2), which one is rate determining step? 14, For a first order reaction, the time taken to reduce initial concentration by a factor of V/4 is 10 minutes. What will be the time required to reduce initial concentration by a factor of it 6. Express the rate of the following reaction in terms of the formation of ammonia. Naw) + 8Hajg) — 2NHagy 7. Ifthe rate constant of reaction isk = 3 x 104s", then identify the order of the reaction, 8, For the reaction 3H») + Nog) > 2NHsigy ~All, how are the rate of reaction —“!2 expression (NHI e and “N75! interrelated? 9, Define elementary step in a reac 10. Distinguish between ‘rate expression’ and ‘rate constant’ of a reaction. 15. For a first order reaction, show that time required for 99% completion is twice the time required for the completion of 90% of reaction. 16, What is meant by rate of reaction? Differentiate between average rate and instantaneous rate of reaction. 17. For a reaction A + B —> P, the rate is given by Rate = K(AI[B?? (i) How is the rate of reaction affected if the concentration of B is doubled? (ii) What is the overall order of reaction if A is present in large excess? 18. The thermal decomposition of HCO,H is a first order reaction with a rate constant of 2.4x 10s"! at a certain temperature. Calculate how long will it take for three-fourth of initial quantity of HCO,H to decompose. (log 0.25 = - 0.6021) 19. For a reaction : 2NHgp) "> Naw) + 3Hayg) 5 Rate =k (i) Write the order and molecularity of this reaction. (ii) Write the unit of &. 20. For the reaction, 2NzOs49)—> 4NO nig) + Orig), the rate of formation of NOz,)is 2.8 x 10 M st Calculate the rate of disappearance of NzOpig)34, From the data given below, calculate order 35. For the first order thermal decomposition reaction, the following data were obtained : CoH Cly —> CoH yg + HChy of reaction. SNo. | (AID | [BI0 | Rate Ms) i 10 0.20 0.10 a 2.0 0.20 0.20 3. 2.0 0.40 0.80 Time/see Total pressure/atm 0 0.30 300 0.50 Calculate the rate constant. (Given : log 2 = 0.01, log 3 = 0.4771, log 4 = 0.6021) S Long Answer Type Questions (LA). 36. Calculate the order of the reaction and the rate constant for the decomposition of NO; at 80°C from the following rate data. SNo.| Rate of | Concentration of reaction N,0, (Mol L* hr“) (Mol L*) a 0.10 0.34 0.20 0.68 0.40 1.36 37. The half-life period of a first order reaction is 30 minutes. Calculate the specific reaction rate of the reaction. What fraction of the reactant reaction, as the concentration of water remains constant. Gi) Calculate the average rate of reaction between the time interval 30 to 60 seconds. (Given : log 2 = 0.8010, log 4 = 0.6021) 39, For a homogeneous gas phase reaction Aig > By) + Cg) + Digy the pressure of the reaction mixture increases by 40% in 20 minute. Calculate rate constant of a reaction. 40. The following results have been obtained during the kinetic studies of the reactio 24+B—>C+D [Experiment] [A] | (B] | Initial rate of remains after 70 minutes? No. formation of D 38. For the hydrolysis of methyl acetate in 1.0.1 M[o.1M|60x10°M min? | aqueous solution, the following results were 2. (0.3 M [0.2 M|7.2 x 10"? M min? obtained : 3. [08 M[0.4M/2.88 x 107M min tis o | 30 | 60 4. [0.4 M[0.1M[2.40 x 10? M min [CH,COOCH,Vmol L | 0.60 | 0.30 | 0.15] Calculate the rate of formation of D when (i) Show that it follows pseudo first order [A] = 0.5 mol L™ and [B] = 0.2 mol L*, CEM 1. (b): In terms of pressure, Rate = MPa scocis)*? Units of rate = bar min" rate Units of rate constant = a Persons) bet ar mi bah 2. (d): Rate = KAP [BP =a When volume is reduced to one half then conc. of reactants will be doubled. Rate = {2A}? [2B}? = 32 KAD? (6? = 322 3. (b): Rate of disappearance of a=} x rate of appearance of 4, (6) : Order of reaction can be zero, fractional or negative.Chemical Kinetics 5. (6): SeMXl_ Fora fis order eacton) 0.00352 =k x 0.01 => k= 0.352 0.693 _ 0.693 0352 6. (c): Rate of ero order reaction independent ofthe concentration of reactants. 3 (5-24.07 m3 7. (a): =e Aart k (for ist order) hn 969 min 2303, ae 8. (by: k= 2g) 220 1 =(22oge) i" 2 ye C2 9. (a): The unit of rate of reaction is mol I~ not change with order. GINO, at 11. (b)+In a reaction P -> , concentration of reactant decreases as concentration of product increases duting the course of a reaction. 12. (b): The number of molecules of the reactants taking part in a single step ofthe reaction tells about molecuarity of the reaction 13. (b): Rate of forward reaction decreases and rate of backward reaction increases with passage of time. At equilibrium both the rates become equal. 14, (b): For 2N,0; > 4NO, + Op, the rate of reaction can be expressed as 1,0.) It does 10. (b): Rate =: x00125=0.0081 mols 1.41NO,] _ a0, 2 16. (a): For a zer0 order reaction, rate = KAI? = k Units = mol t=! 5 17. (c) : When one of the reactants is in excess the reaction behaves as a first order reaction. lal __((Al.—(Ah) at oh 18. (€) : Average rate (0.04 = 20 3 35104 Mine! 0 30 ox 19. (a): For a zero order reaction, rate = Units of k = mol L's 37 20. (d): CH,CHO > CH, + CO Rate = K{CH,CHOP? 21. (b): If one of the reactant is present in excess, the reaction becomes independent of the concentration of that reactant hence it becomes pseudo frst order reaction Thus, rate of pseudo fist order reaction depends upon the concentration of the reactant present in small amount, 22. (b): The rate of reaction depends upon concentration of only A. 23. (a): For the reaction, 2NO, > 2NO + 0, 1lNO,] _ 1 aINO} _a0,) 2d 2d at N04) = 40°" mol’ a 107"? mol Es” OL 310°? molt! 24, (a); LAAN. , LalHeO aa 6 ot OL 8 3.6107 = 54107 mol 5 25. (b): Rate = KIN,Os) (frst order as unit of rate constant iss) 26. (c) : Rate of reaction = conc. of reactants As the reaction proceeds, concentration of the reactants decreases hence the rate also keeps on decreasing with time 27. (a): For a unimolecular reaction, both order and molecularity are one in rate determining step. 1AIX]__ 12-3) Sear 28. (a): R AT TOA 8) 9.1 mol mir (2): Rate= == =O mol 29, (b):0; =E= 0) + [0] (fast) [0] +0, 2 20, (slow) Rate of reaction is determined by slow step hence, Rate = f,[0]I03] [0] is unstable intermediate so substitute the value of [0] in above equation Rate of forward reaction = ky[03] Rate of backward reaction = k_[0,]/0] At equirium, Rate of forward reaction = Rate of backward reaction 4,103] = K_,10,110] seminar Oe(oy= His E02] Ho) Host Rate = kz] "2" [05] ; Rate = «(Rica on (021 30, (b): Radioactive disintegration is an example of fist order reaction 2303), (Me *Palat) 31. (@): For fis order reaction, 2303),6(_a_) 2303, = 2303, t bos, "200" (SS) = 22.204 = 0.013865" =1 386x107 5 32, (b): Rate = AXP IM? or rate =k 33. (): $;Cl, > 50, + Cly Initial pressure m% 0 0 Pressure at time! p—p pp Let inital pressure pce Ry Pressure at time (, P,=Po-P +P +P =P +p Pressure of reactants at time f,—p = 20) ~Py= R 22a os ) 2505-06 2303 100 SF I091.25 Pressure of $0,Cl, at time so, = 2p P,= 2 x 0.50 ~ 0.65 atm = 0.35 atm Rate at that time = kx Psoscy = (2.2318 x 10°) x (0.35) = 7.8 x 10 atm s-! k=0. 20aIog'2 -0.2303{1-0.9030) 0.2303 x 0.0970 = 0.0223 min 35. (b): Average rate during the time interval 30-60, (017-039 b-h 60-30 30° = 4.67 107? mol L” Rate 36. (a):Linear plots are obtained in the graph of A,¥S t for zero order reaction and In a ~ x vs for first order reaction 37. (a): For the reaction N, + 3H, —> 2NH, Loe, , Lents] 3 ot 2 at 38. (a): (Al =[Rly-Ht For completion of reaction [A] = [Ro ort 39. (c): 2NH, —> N, + 3H, Rate =—1 SINHs] _ Ip] _ 1 dlHa} 2 a a3 at 1 1 2D AIINHg] = kalNHg] = = g[NHg] 15k, = 3k; = hy . 2303 | loglAl 40. (b): k tA) 2303 1.45_2303 20 16 Tié00-200)"% 088 ~ goo *92"6? 24x 104s 41. (d): The slowest step is rate determining step. AC]_1d[D]_-d[A]__ 1018) 42. (b) = — i 3dt 2 at at 2 dt HATA] __ (0095-05) 0.15 |p osm. 1 5 6 ‘0.01mol/L-s =. 0.02mo/L-s AAl3x001=009maliL-s 40) ssaoiatoas 43. (c) : For 99.6% completion, Let a= 100 x=996 a-x=04 2.303, 10 k=—log— =| thos 109 04 250 fasey= 228 iog250 0.693 Ai) fy From equation (i) & (i)Chemical Kinetics tose =23% 96% = D695 44, (b): The following data were obtained during the first order thermal decomposition of N,Osiq at constant volume 2N,0sig) —> 2N2Oqg) + O29) x24 xty2=8ty2 SNNo. Timels Total Pressure/(atm) 1 0 Os 2 100 osi2 Let the pressure of NOsq) decrease by 2x atm. As two moles of N,0; decompose to give two moles of N,Oye) and one mole of 0, (g), the pressure of Nyy increases by 2x atm and that of Oi increases by x atm 04g Dug + Ong Star 1=0 05am Gat” Oaim atime (05-29)am deat xatm Pr = Przos + Phyo * Pop (0.522) + 2x+ x=05+x P,- 0.5 Phos = 0-5 ~ 2x 5 ~ 2 (p05) = 1.5 ~ 2p, Att = 100s; p= 0.512 atm Phos = 15 — 2 x 0.512 = 0.476 atm We know that, 2.908), 05atm 100 P o47éatm x 00216=4.98 10+ s"* 45, (A): For 2210 order reaction, {Al vs tis a straight line plot and hal life ty, fo For first order reaction In [A vst gives straight line pit and half ile = 12 k 46. (€) + () Rate law can be written as follows: Rate = KIAP [8]? From experiments | land li (Rate), = 12.5 x 10-4P [3.0 x 10°57 = 5.0 x 10.) (Rate), = kI5.0 x 10-4 [6.0 x 10-5]? = 4.0 x 10 fi) (Rate), = K[1.0 x 10-9 [6.0 x 10°5]9 = 1.6 x 10°? i) Dividing equation (ii) by equation (i, (Rate), _ (1.0107)? _ 1.6107? at), 0x10) 40x10 or Pah or P=Piep=2 39 Dividing equation (i) by equation (i), (Ratel, _ (50x10)? (60%10°9)4 _ 40107 (ate), 25x10 P BOxI0)7 50x or P.29=8 of 2.2=8 or 27 = 8/2? of 27=2! or g= ‘Thus the rate equation is Rete = KAI? [B] Order of reaction with respect to A = 2 Order of reaction with respect to B= 1 (i) Rate constant (A) at 300 K : From experiment 1, we have Rate = k(2.5 x 10)? (3.0 x 10°) or 50x 10 mol" = K(2.5 x 10-* mol “(3.0 x 10° mol L~ 5.0104 molk"')? (2.510? B.0x11 =267%108 moll? 47. (@) :For a first order reaction 0.693 ha k= 3.01x 10351 48, (a): Half life (,) of a frst order reaction is given as tpn OS® 50593 999, k “Tox10 49. (b): Fora frst order reaction typ = 2622 therefore fy. depends solely on k. 50. (c): Let the concentrations of the reactant after 10-min and 20 min be C, and C; respectively, Rate after 10 min = 0.04 x 60 mol L“Imin! =k.C, and rate after 20 min = 0.03 x 60 mol L°'mi ©, _ 04x60 _ 4 c,” 003x608 Let the reaction stars after 10 minutes 2303), 2303), 4 sO = 23849 4 0.087% So saa 8g onUETe 0.6932 _ 0.6932 k 02878 51. (b) : Fora first order reactions, fy). = HIAI9 = k. Thus fy. is independent of initial concentration. Hence plat off ¥S lg will be a horizontal line 14.086 min seminar Oe52. (6) + For fist order reaction, Rate, = KA] According to question, a] = [24,] c+ Ratey =A(2Aj] => Rate, = 2 Rate, Foraiven reaction, rate constants constant and independent of the concentration of reactant. 52 (9 fora fester ein ba? a-x 2303, a a) 2303 44.4 2303 ty 2a tg 9 Therefore halite period ta 22 og2 Thus ty is independent of initial concentration of reactant for first order reaction. 54, (b): For a first order reaction, [A] = [Ae A) According to eq. (i), concentration of reactant decreases exponentially 55. (a) : Forafirstorder reaction, t, isinversely proportional ‘tok, it does not depend on the initial concentration of the reactant. 56. (b) : From the expression dA) at when B is present in large excess, rate will be independent upon the change in cone. of B, therefore order of reaction will be one 57. (c): The total numberof reactant molecules participating ina chemical reaction is known as its molecularity, hence the molecularity =6 +3 + 1 = 10. 58. (€) : Molecularty may or may not be equal to the order of a reaction KAGE 59. (A): Order of action =24 442 S4443_ 13 2 2 60. (€) 2NOy, + Clyy > 2NOChy, Molecularity = 3 61. (b): Let the rate of this reaction, r= K[NOJ"ICI,)" 0.60 _ k(0.15)"(0.15)" then 4 = 060 _ RO1SI"0.15)" a (0.157°(0307 5 or $G) 3 Pay 1 a Hence, expression for rate law is r=KINOP [cl,)' 62. (4): As the order wrt. NO is 2 and order wrt. Cly is 1, hence the overall order is 3 63. (c) : Substituting the values of experiment 1 in rate law expression (0.60 M min-" = 4(0.15 M)? (0.15 M)" 0.60Mmin~" 0.0225%0.15 M? 64. (d) 171M? min" 177.7 M™ min“™ x (0.25 MY? (0.25 M) 271M mit 65. (a) : Unit of rate constant for a reaction of n™ order = (conc) time™" Fora first order reaction, n= 1 12M —46M—25 3M, itl oe, 10 min 0.693 10693 min AS fy is 10 min, after 20 minutes the concentration will be3 M Hence, Rate = 0.0693 x 3 M mit 67. (b) fy = 23 minutes 0.633 693 tye ke = k ta For 90% completion, 2303, (_a t oc (4): al Jit t= 76.4 minutes Bea 100 ) =" q693 900-90 303, 168. (a): For the fist order reaction, =e a= 01M, 2-x= 0.025 M, t= 40 min 0.1 _ 2303 F P= 2303 04 = 0.0347 mi 025 4p 084 = 90847 min (Al > product Thus, rate = KA] rate ~ 0.0347 > 0.01 M min! = 3.47 x 10-4 M min! 0693 0.693, 0.693 69. (2) hy = 2593, 9693 _ 5 _, 0693 _, @)hn= =F ta 60 = 0.01155 min 303, (4) tae Let the initial amount (a) be 100, “(Z)Chemical Kinetics 0.0115Smin-' x240min 2303 1.204 = log 100 —Iog (a -») 1.204 = 2 - log (@-x) log (a ~2) = 2~ 1.204 = 0.796 (a-1) = 6.25% 70. (c) : Rate of reaction does nat remain constant during the complete reaction because rate depends upon the concentration of reactants which decreases with time 71. (€): The rate law equation cannot be written from stoichiometric equation, 72. (b): During hydrolysis of ester, water is always present in high concentration, thus there is very little change in its concentration and it practically remains constant. Thus, the oder of reaction is 1 (pseudo fist order reaction). 73. (a): Rate of any reaction is equal to the rate of its slowest step and here rate of given reaction = KIN,Os] because the slowest step has only NO; molecule involved. 74, (b) 75. (b) 76. (a): A bimolecular reaction may involve combination of two molecules or exchange of atoms or groups of atoms between the two reactant molecules 77. (a): Hydrolysis of cane sugar is pseudo first order reaction, Since, water is always in excess, rate of reaction does not depend appreciably on its concentration, thus it is an example of pseudo unimolecular reactions. 78. (c) : Fora gaseous reaction at constant I, concentration is directly proportional to the partial pressure ofthe species. Thus, the rate of reaction can be expressed in terms of partial pressure for gaseous reactants or products 79, (b):In a heterogeneous system, the reactant is absorbed on the surface of a solid catalyst. The fraction of the surface of the catalyst covered by the reactant is proportional to its concentration at low values and the rate of reaction is fist order. However at higher concentration, the surface of catalyst is fully covered and the reaction rate becomes independent of concentration and it becomes zero order reaction 80. (b): Instantaneous rate of a reaction is equal to smal change in concentration (dt) during a small interval of time (di) at that particular instant of time divided by the time interval. a ae 1 Order of a reaction 7. [itis the sum of powers] 1 of the concentration] ofthe reactants in the| rate law expression Molecularity of a reaction tis the number of reacting species (atoms, ions or| molecules) taking part in an Jelementary reaction which] must colide simultaneously inorder to bring about a chemical reaction, Iti ahways a whole number 2, it can be zero or even| a fraction. Generally, in a complex reaction the order of reaction is equal to the molecularty ofthe slowest step. 2. The time taken for half ofthe reaction to complete, ie, the time in which the concentration of a reactant is reduced to half ofits original value is called half-life period of the reaction when (a = Al 3. Half-life of frst order reaction is independent of the initial concentration of reactants typ = 0588 n= A. For fst order reaction, k= 9593 = 9698 cee For 2 thie period, a-x=a poe aa 01693 _ 2308 45), 0693 _ 0.6932 xy x y 5. 5 5 z 0 Tine —> 6. Nagy + 3Hyy) —> 2NHyg) Hay] __1 Ha] _ 1 aN} ad 3 dt 2 ot seminar Oe7. First order reaction has s“! as the unit of the rate constant Jaf] _ , 1¢1NH) & ya 2 a 9. Elementary step : Each step of a complex reaction is called an elementary step. 10. Rate expression is 2 way of expressing rate of reaction iin terms of concentration of reactants, €.g., for a general reaction, a + BB —> oC + aD Rate = KA)* [B)” Rate constant (A) is equal to the rate of reaction when molar concentration of reactant is unity. Its units depends upon the order of reaction. 11. Rate law, r= Al"? [BP Order of reaction is sum of the powers of concentration terms, 5 1 Order of reaction =< +2= der of reacion = 5-+2—=5 12. (i) The reaction is of zero order. (i) Slope of the curve = 13. (i) Rate = KiH,0,]I"] (il) Overall order of reaction is 2. (ii) Step (1) being the slow steps the rate determining step of the reaction 14. Let initial concentration (a) = 1 then, final concentration (a— x) = 1/4 2303), 1 ty = 23 og hg = 9G A) 2303, 1 Similar, tyyg = 22? log J milan, tng = hog Tae Ai) Dividing equation (i by () $06 1015 ag 10x 12 20 10 ~ Tags (16 = "0% pGqp5 = 20 mites 15, For fst order reaction, t= 2303 jag Rol TAL For 99% completion of reaction 1 fgg [Aly = 1, UF) = (1 ~ 0.99) = 0. 2303), 1 2303) 4922. ty > log — = log 10? = oll) 09 pea 8 For 90% completion of reaction t= fygo, [Fl = 1, [Fl = (1-0.9) = 0.1 = 107 2303), 1 _ 2303 303 ty90 = 23 lag 1, = 2308 fag 9 = 2308 J ogo = log 5 = tog 1-= «iy Comparing equations (i) and (i), foap = 2 boop 16. Change in concentration i.e. either (decrease in concentration of reactant or increase in concentration of product) per unit time is called rate of reaction, ac b-h At The ratio of change of concentration of reactants to the time consumed in that change is called average rate of reaction. Ak -G at oh The rate of reaction at a particular instant (time) is called instantaneous rate of reaction Rate of reaction = ly = fs d, = small change in concentration d= small time interval 17. (i) From the rate law equation, order of reaction wart. B is 2. Hence, if concentration of Bis doubled, rate will become four times. (ii) If Ais present in large excess, rate of reaction will be independent of concentration of and hence, order of teaction will be 2. 2.303 pq lp eal 18. For a frst order reaction, Given k= 2.4 x 107 st Al iA = (Alo, lAl= "Pt Substituting these values in the equation, we get 2303 24x10 t=57715= 578s 19. (i) The decomposition of gaseous ammonia on a hot platinum surface is a zero order reaction at high pressure. in this reaction, platinum metal acts as a catalyst. At igh pressure, the metal surface gts saturated with gas molecules. So, a further change in eaction conditions is unable to alter the amount of ammonia on the surface ofthe catalyst making fate of the reaction independent of its concentration. However, two molecules of ammonia react to give products thus, the molecularity is two, (id. For a zero order reaction, unit of rate constant is mol 2303 esas tae NO) 20. Given, 8x10-3Ms"t ‘According to rate law expression,Chemical Kinetics ~dIN,O5] _1 at 21. Order of a reaction : It is the sum of the power of reactant in the rate law expression. (C1 mols! ~ era order reaction ws First order reaction 22. () The reaction is of 1 order. (i) For frst order reaction InlAl = -kt+ In [Alp comparing eqn. y= mx x+. we get a straight line with slope to Ini (ii) Unit of rate constant for frst order reaction 28x10 = 14x10 Ms ~k and intercept equal molt"! 4 1 stmt 23. For an elementary reaction, order should be equal to moleculaity and further molecularity should be integral. For the given reaction, order of reaction = 1 + 1/2 = 3/2. Since molecularity cannot be fractional, therefore, for the given reaction, order is not equal to molecularity. Hence given reaction cannot be an elementary reaction. 24. (i) Differential rate equation of reaction is (al'\6)? = Kialla? (i) When conc. of Bis tripled, it means conc. of B becomes Bx B) New ate of reaction, 2 =1AlB87 = SMAIIBP = 9 (*) ie, the rate of reaction will become 9 times. (ii) When conc. of Ais doubled and that of Bis also doubled, then conc. of A becomes [2A] and that of B becomes [2B]. K(2A)|28P = 8k [4llBl? Now rate of reaction, = ‘e, the rate of reaction will become 8 times. () Molecularty of a reaction is the number of reacting particles which collide simultaneously to bring about the chemical change. itis a theoretical concept. 25. () Average rate of reaction between the time interval 30 to 60 seconds is 43 ~f0.17-031]_0.14 60-30 30 = 4.67 x 1073 s [Taking only difference] 303, (Flo Gi) k= SP toa et Att=305, 2303) 055 _ 2.303 logo 0,249 =1.91% 10" 508g aT 7 9p NOMI HII 107%5 Att= 605, 2303), 00.55 _ 2303 7 yong gy = ay x 0.5089=1 9610 Att= 905 2303, 0.55 90 90.085 2303 21 £203 0.8109 =2.07x 10s 90 Average value of k 1.9110"? +1.96 310-2 42.07%10-? < 98107 26. The given rate law equation can be written as INH] _ ky dt TINA +h ()_ FINK] is very high, 1/INH] becomes negligible at og adh jie, rate becomes independent of concentration. Hence, itis of zero order. (id HF INH] is is very small, 1/INH,] will be very large (2>k), so that A can be neglected in comparison to INH] _ ky [NH]. He - = kyINH Ing Hence <= Fr] MINS) Thus, reaction is of Ist order. 27. The given data is Sai San 0.5moll-| = 50,25molt~'="" 40,125molL- Half life period is independent of initial concentration of the reactant, hence reaction is of fist order. For first order reaction 28. (a) The formula of rate constant for fist order reaction is 2.303 gly 1 (Al seminar Oe2) ol 2223 pg UEXIO™ IMAI 3,979 g 3005 °9(0.8%107) mal E 12) molt Simian, fy =2203 pg (1.6210 mal 600s *(0.4x10"4) mol F 3x 107 Unit and magnitude of rate constant shows the given reaction is of first order. (6) The formula for half-life for frst order reaction is 0.693 t= ay 7301.30 mek 23x10 s 29. Given: [Fg = 1, [9] = 0.80, t= 160 min ha For first order reaction, 39107? min" 0.693 — 0883 = 498 min 139x107 [Alo Al {Alp _ 100 = 1.06 x 10° mine?, [Alo = 100 Given k= 1.06 10° min", TGP = ge 2303 __jgg 100 06x10? min 85 2303, : Fp 2leg10—log85Imin 303 1303 0.0706 Tog 2X1-1.9294] = TE t= 153.39 min = 153.4 min i) 1-3 mint Alo _ 100 = 1.06 x 10° mint, [la _ 100 (i) Given k= 1.06 x 10° mi, Th 2303 100 _ 2303 DextO Fmt Is = pg !20g10—log1SImin [ata 230308239 1909 mi gg 2X11 ATEN = BORSA min = 1790 min 31. AtpH = 5, as half-life period is found to be independent of initial concentration of sucrose, this means with respect to sucrose, itis @ reaction of fst ordey, ie, Rate = KSucrose |f mis the order with respect to H* ion, ty eLH*]'™, Le, 500 <= (10°5)'"" [pH = 5 means [H*] = 10M] .() and 50 c= (10°4)'=" [pH = 6 means [H"] = 10°] Ai Dividing (i) by (i), 10 = (10)'-" ie. 1-n=1 orn=0, ie, order with respect to H* ion = 0. Hence, overall rate law is Rate = k [Sucrose] [H*)>. 32. The given reaction is 2N,O, > 4NO, + 0, Unit of rate constant suggests that rate of reaction is first order. Hence, rate of reaction = KIN,O) = 3.1 x 10 min x 0.40 M = 1.24 10 M min Rate of reaction, Ny] __, 10} at at EES = 1.24 x 10-4 Main! x2 2.48 x 10-4 M min? INO] 1.24104 M min 4.96 «10 M min Similarly M02) 4.24 10-4 Mii? a 33. The given reaction is S0,Clyg —> S04) Clog areo oda o ° Autimet (04 shatm Total pressure at time t will be Pa (04-4 x4 x= 04 4X x = (P,-0.4) Pressure of $0,Cl, at time twill be Proje = 04 - = 0.4 -(P,- 0.8) = 08-P, At time t= 100 s, P,= 0.7 atm Pro,cl, = 0.8 ~0.7 = 0.1 atm According to first order kinetic equation p= 2203 qq Psoscoteon #1 Poca recon) 224) 100 0.1 34. Let rate of reaction r= KA)*1B)" From the data 3x10? 10 M s-! = K1.0 M)? (0.20 M)® 0} 20M st = H2.0.M)# (0.20 M? i) = 0.80 Ms“! = 2.0 M)#(0.40 M)? (iy Dividing eqn. () by (i) A 0.10Ms"! _ k(.0M)%(0.20 M)? fh 0.20Ms? K(2.0M)# (0.20 Mm)Chemical Kinetics or, 3-(ff a= "2 2 Dividing egn. (i) by eqn. (i) 0.20 Ms" _ (2.0)*(0.20)% 5 0.80Ms"" (2.0)#(0.40)° Hence, order of reaction = 1 + 2=3 35. The given reaction is GHC —> Ghat Hg srtine t= 0 030 am Attine ¢=300se¢ 030-1 rook Total pressure = 0.30-x+x+x=0.50 or 030+ x= 0.50 x= 0,50~ 0.30 = 0.20 Initial pressure, Py = 0.30 atm Pressure of C,H,Cl after 300 sec, P,=0.30-0.20 = 0.10 atm Using formula for first order reaction, re(3) 2303, (030 300 2 (G50) 2302, 2309x0477 300 =~ 300 66 x 107 sec"! 36. () Letra of eaction AN! = KNyOs|" = 0.10 mol Lo" he! = 34 mol ty" = 0.20 mal "he"! = kx (0.68 mol CY" f= 0.40 mol Une! = kx (1.36 mol ')® A 0.10mol thr! _ (0.34 mol E")" % 0.20molL "hr! (0.68 moll-")” “Hl (i) Rate = KIN,O5) 0.10 mol I" hr" = kx 0.34 mol Lt ipa or j= QO MOLL HT or = 2.9 x 10" he! 0.34 mol 37, For a frst order reaction 016932 _0.6932_9.993tmin-! “hn 30 Suppose the reaction is A —> Products t=0 a 0 min (a—X) x 2303, (_a 1 0.0231= 27 eq( 2.) wal a ) 0.023170 _ 9994 a-x) 2303 38. (i) For a first order reaction, 2.303), (Ale t [4] When t= 30s 2:303,,,(0.60 )_2:303 1 2203,,(00) 23%, o30y = 002s When t= 60s 2303, (0.60 )_ 2.303, 1 Fo9( 22) Gy %0.602= 0.0231 5 As the value of kis constant at different time intervals, the reaction is frst order w.ct. ester when [H,0] is constant. Hence, itis pseudo first order reaction. GC, _~{0.15-0,30) ht 60-30 2B 5x10? mol t's" 39. The given reaction is a ya (i) Average rate =. tial presure $ o G Aer 20min, " x x Total pressure = P,— x4 x4 x4 x= P+ Ok 40 xP, Py +P, x a Pra de= Pere x Bake opiate Po 5 Now, 1A (Rl=P,-x=P,-% =087, 2303, (Rl Using formula, k= 222 ig 2303, Pe 1, k= 2393 iog,. 20min" O8R, 2303 pe 2303 «0.0969 OM Ty ini99 125 20 min k= 1.115 10? min seminar Oe40. Suppose order with respect to Ais m and with respect (pate), 7.2107 10 Bis n, Then the rate law will be Rate = KATE)" Substituting the value of experiments 1 to 4, we get Expt. 1: Rate = 6.0 x 10% = k(0.1)" (0.1)" Expt. 2: Rate = 7.2 x 10°? = k(0.3)" (0.2)" Expt. 3 : Rate = 2.88 x 10"! = k(0.3)" (0.4) Expt. 4: Rate = 2.4 x 10% = k(0.4)" (0.1)".. ‘Comparing equation (i) and equation (iv), (Rate), _ 6.010? _ K(0.1/"(0.1!" (Rate)y 24x 1 «(0.4)"(0.1)" a ov 4 04" 4 m1 ‘Comparing equation (i) and equation (il) Ai) iv) (0.3) (0.2)" (Rate) 288 x10-" K(0.3)"(0.4)” ty 02" (1 2 ee (J (oar Gy Ai) Rate law expression is : Rate = MAILB|? ‘The rate constant can be calculated from the given data of any experiment using expression er 3 From expt. 1, k= S2=10T gg 01x (0.9 Rate constant k = 6.0 mol? ? min™! Unitot k Kalle? =6.0905]l0.2° =6x5x4x 103 =1.2 x 107! mol min ©OO oa