Ex.2 The oxidation of iodide ion by peroxy disulphate Jon is described by the equatios 3+ S,0," +1, +250," (ay BEET o 5+ 10> me fora parce time interval, what isthe vaiue of ~ I forthe same time interval ? (b) What is the average rate of formation of SO, ‘during that time interval ? Ex.2_In the following reaction 2H,0, -+ 2H,0 + 0, rate of formation of 0, is 36 g min, (A) What is rate of formation of H,0 ? {B) What is rate of disappearance of H,O, ? Ex.3 The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is 2Br +H,0, + 2H* -+ Br, + 2H,0 ‘Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric equation buts rate = k(H,0,) (H")] [Br] (2) If the concentration of HO, is"Ihcreased by a factor of 3, by what factor is the rate‘of consumiption of Br ions increased ? (bd) If, under certain conditions, the rate of consumption of Br ions ts 7.2.x 10° mole dm” s"', whats the rate of consumption ot hydrogen peroxide ? What is the rate of production of bromine (c) What is the effect on the rate constant k of increasing the concentration of bromide ions ? (0) If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect on the rate of change on change on the concentration of Br? What would be the effect on the rate constant k ? Ex.4 For a reaction 2P + Q-+5 ; following data were collected. Calculate the overall order of the reaction. ‘Also find out the reaction rate constant. P(mole/L) Q(mole/L) Rate 2. 6x 107 1x10? 0.012 2 6x107 = 2x10? 0.024 3. 2x10? 1.5107 0.0024 4 4x107 1.5 «107 0.0096 Ex.5A 22.4 litre flask contains 0.76 mm of ozone at 259C, Calculate (i) the concentration of oxygen atom needed so that the reaction 0 + 0, -+ 20, having rate constant equal to 1.5 x 10° litre mot" sec can proceed with a rate of 0.15 mol litre" sec (il) the rate of formativon of oxygen under this condi- tion, Ex.6 The rate of a reaction A + B + products is studied to give following data. Wedel Alin mot | total immetA | rate QrollUmin) on an ‘aos cc en coo en 1 ‘a0e8 Ts the rate Taw ? What Is the half-life of Ain the reaction Ex.7 For the'reaction : Ag+ Boe C+ ABSC the rate = K(AJ[BP with k = 2.0 x 10M? st, Calculate the initial rate of the reaction when [A] = 0.1 M, [8] = 0.2 M and [C] = 0.8 M. If the rate of Teverse reaction is negligible then calculate the rate of reaction after [A] is reduced to 0.06 M. Ex.8 A&B are two different chemical species ‘undergoing 1* order decomposition with haiflives equal to.0.231 8 0.3465 sec respectively. Ifthe initial conc. of An borane te 32 atte Hae theree half lives of ‘A’. Ex9A + B+C Time T . vs vs Volume of reagent Reagent reacts with all A, Band C and have 'n' factors, in the ratio of 1 : 2: 3 with the reagent. Find k. Ex.10 Inversion of sucrose is studied by measuring angle of rotation at any time t. C,.H,,0,, (sucrose) + H,0 —+ C,H,,0, (glucose) +°GH,0, (fructose) Ik is found that are (r,- Fan) = a and (r,~ Fc) = (2= x) where Ff, Bnd Fp are the angle of rotation at the start, at the time t and at the end of the respec tively, From the following values calculate the rate constant and time at which solution is optically inac- tive. Time/ min. 00 © 46.0 o Rotation of Glucose 8 Fructose 24.1 100 10.7 Ex.11 The first order reaction :sucrose —»Glu- cose + Fructose takes place at 308° K in 0.5 NHCI. At time zero the initial total rotation of the mixture Is 32.4, After 10 minutes the total rotation is 28.8. If the rotation of sucrose per mole is 85°, that of glu- ‘cose of the glucose is 74* and fructose is -86.04°. Calculate half life of the reaction. x.42 At room temperature (20°C) milk turns sour in about 65 hours. In a refrigerator at 3°C milk can be stored three times as long before its sours. Estimate (a) Activation energy of the reaction that causes: the souring of milk, (b) How long should it take milk to ‘sour at 40°C. Ex.13 When the catalyst is removed from a reaction at SOO*K the rate decreases upto 4 times and act ton energy Is increased by 20%. Find the ratio of velocity constants at temperature 320°K and 300% Inthe absence of catalyst. Assume activation energy is independent to temperature. COMPREHENSION For a reaction, itveffective rate constant k’ is given where k,, kj, ky, k, are rate pve 22(H constants for different steps of the reaction Ex.14 The effective activation energy is @) 8 °6,-6,+36,-26, (6) &-B, +6, -B, +B, (c) & #6, +6, -6,-&, (0) *B, +6, -6,- 6 ‘Ex.15 The effective frequency factor wy a-(2)(% a= AA HARA r-(B)(m)" Ex.16 Which one is correct ? we aha * op) Fa Bt “VE ] b) 2 tA o | 6. 6, aS a] AA : 15 [Fa t+ +B wot teifoee[ SS! (d) none of these. Ex.17 A certain organic compound A decomposes by two parallel first order mechanism 8 PQ, tik lat 1S and k, #13 108s Calculate the concentration ratio off .tovA, if an ex- periment is started with only And allowed to run for ‘one hour. 8 hy bo 2x38 Fora parallel first order reaction “ c » . where k, = he and k, 10: 100, coca f, Shane BE = Ex.19 An organic compound A de composes following two parallel first order mechanisms : ky 8 ky » : Me hy ti c Calculate the concentration ratio of C to A after one hour from the start of the reaction, assuming only A was present in beginning. 1 79 and k, = ahr, £x.20.The reaction a is ~ Cr(en), (OH), SES trans - Crfen), (OHY; {first order is both directions, At 25°C the equilibrium,‘constant is 0.16 and the rate constant k, is 3.3 10 “5-1 Inan experiment starting with the pure cis form, hhow long would it take for half the equilibrium amount fof the trans isomer to be formed ? Ex.21 Two reactions (i) A -+ products (Ii) B + products, follow first order kinetics. The rate of the reaction (I) s doubled when the temperature is raised from 300 K to 310 K. The half life for this reaction at 310 K is 30 minutes. At the same temperature B ‘decomposes twice as fast as A. If the energy of activation for the reaction (ii) is half that of reaction (), calculate the rate constant of the reaction 300K. Ex.22 For a reaction A, + B, -+ 2A8, evaluate the ‘energy of activation from the following data: Tink) $0) og, ‘500 3.0 200 2.0 2x10 Sx10> Ex.23 A reaction proceeds five times more'at 60°C as it does at 30°C. Estimate energy of activation. x.24 For the reaction A es 8, AE for the reaction is -33.040 mobn’Calculate : (2) equilibrium constant K. for the reaction at 300 K (b) If and E, are in the ratio 20 : 31, calculate E, E, ‘at 300 K. Assuming pre-exponential factor same for forward and backward reactions. Ex.25 A first order reaction A -+ 8 requires activation ‘energy of 70 kJ mol"', When a 20% solution of A was, kept at 25°C for 20 minute, 25% decomposition took place. What will be the percent decomposition in the ‘Same time in a 30% solution maintained at 40°C? As- ‘sume that activation energy remains constant in this, range of temperature. Ex.26 At 380°C, the half life period for the first order ‘decomposition of H,0, is 360 min. The energy of actl- vation of the reaction is 200 k} mol". Calculate the time required for 75% decomposition at 450°C. Ex.27 The energy of activation for a reaction is 100 Kd mot", Presence of a catalyst lowers the energy of activation by 75%. What will be effect on rate of reaction at 20°C; other things being equal? €x.28 (2) The reaction A proceeds in parallel chan- . nels cS [though the A + C branch is thermody- namically fore favorable than the branch A.» B, the product B may dominate in quantity over C. Why may this be so? () In the above problem, suppose the hall life val- ues for the two branches are 60 minutes and 90 min- utes, what Is the overall half-life value? Ex.29 Deduce rate law expressions for the conver sion of H, and I, to HI at 400°C corresponding to each of the following mechanisms’? (a) H, + I, » 2HI (one step), (o) 20 214 Hy +/2HI (slow) 22P 1+, 1M, TH, +1 241 (slow) (2) Can the observed rate law expression rate = K{H,J[1 distinguish among these mechanisms ? (@) If it is known that ultraviolet light causes the ‘reaction of H, and I, to proceed at 200° C with the ‘same rate law expression, which of these mechanisms becomes most improbable ? Are any of these mecha- isms proved ? Ex.30 Hydrolysis of methyl acetate in aqueous ‘olution has been studied by titrating the liberated acetic acid against sodium hydroxide. The concen- tration of the ester at different times is given below. min o 306090 C/mal 0.8500 0.8004 0.7538 0.7096 What is the value of k’ in this quation if Rate = k’ [CHsCOOCH)][H20)EXERCISE - 1 OBJECTIVE PROBLEMS (JEE MAIN) 11, The rate of a reaction Is expressed in different ways as follows : (AAC), 140). 144) a8) a 3a 8a ‘The reaction is: (A) 4448-420 +30 (C)A+B4C40 (8) B+ 30-+4A+ 20 (0)B+D4A4C 2.The rate constant for the forward reaction A(g) =P 28(9) is 1.5 x 10 s at 100 K, IF 10% moles of A and 100 moles of B are present in 2 10 litre \vessel at equilibrium then rate constant forthe backward Feaction at this temperature is (A) 1.50 x 10* Limos"! (B) 1.5 x 10 L mol s* (C)1.5 x 10" L mot? s* (0) 1.5 x 10" ‘3. Reaction A + B-+C + D follow’s following rate law : rate = K(Ay"?[B}"?. Starting with initial conc. of 1 M of A and B each, what is the time taken for concen- tration of A of become 0.25 M. Given: k = 2.303 x 10° sec. (A) 300 sec (8) 60sec (C) 900 sec (D) none of these ‘4. Consider the following first order competing reac tions : XA ASB and yetscid if 50% of the reaction of K was completed when 96% of the reaction of ¥ was completed, the ratio of their fea} rate constants ($2) 1 (A) 4.06 (B)O.21S (C)1.2 (D) 4.65 Units of rate constant for fst and zero order reactions in terms of molarity (M) are respectively. (A) sec, M sec (8) sec, M (C) M sec, sec (D) M, sec 6. For the reaction A + 8 + C; starting with different initial concentration of A and B, initial rate of reaction ‘were determined graphically in four experiments. 390. one) [re wa 310" 187 ange 1810 so a Rate law for reaction from above data is (Ayr = KIAPTB? (8)r= KAPIB] (C)r= k (Altar (D) r= K{AI(8] 7. For a reaction pA + qB -> products, the rate law ‘expression is r = k[A}{B]>, then : (A) (p +a) < (1 +m) (8)(p+q)> (+m) (C) (p + a) may or may not be equal to (I + m) (0) (p+q)=(1+m) 1B. In the reaction : A + 2B -+ 3C + D, which of the following expression does not describe changes in the ‘conc. of various species as a function of time : (A) {-d{C}/at) = {3/20{8)/dt) (8) {30[D)/at} = {aICVoty (C) {3d[BY/dt} = {-24[C)/at) () {2d[B1/ae} = {d[A}/ae} 9. For the reaction, 2NO(g) + 2H,(9) -+N,(g) + 2H,0 (g) the rate expression can be written in the following ways : {4{N, Vat) = k(NO}H,] (N50) /dt ) = KINOILH,) ; (-d{NOV/sty= KyFENOILH,]; (404, dt) = k",[NO}[H, }. The relationship between k, k,, k’, and k7 is ‘10. Atcertain temperature, the halflife period in the thermal decomposition of a gaseous substance as fol- lows : (mmHg) 500-280 (nmin) 235980 Find the order of reaction (Given log (23.5) = 1.37 ; log (95) = 1.97] (AL (B)2 (25 — (0)3 41, A first order reaction is 50% completed in 20 ‘minutes at 27°C and in 5 min at 47°C. The energy of activation of the reaction is (A) 43.85 kl/mol (C) 11.97 ka/mol (8) 55.14 ka/mol (0) 6.65 ki/mot 12. For the first order reaction A + B + C, carried ut at 27°C if 3.8 x 10% of the reactant mol- ecules exists in the activated state, the E, (a vation energy) of the reaction is (A) 12 ki/mole (8) 831.4 kymole (C)100 Ki/mote (0) 88.57/mole 13. The rate constant, the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are 3.0 x 105", 104.4 kJ mot" and 6.0 x 10s" respectively. The value of the rate constant at T > is (A) 2.0 x 10s" (8) 6.0 x 10s" (C)infinity (0) 6x 10% 5"14, The following mechanism has been proposed for the exothermic catalyzed complex reaction. Ate BMS TAB 4, AB+I UP +A If k, is much smaller than k,. The most sultable qualitative plot of potential energy (RE.) versus reaction coordinate for the above reaction. BAT ahr ner Peet rae © Pus Racoon cosa Reacron ooo Ike abel AvP PE. “ © Reactor coord 15. Choose the correct set of identifications. te Reacion cooranale Re a @ (A) 36 for, for: E, for Fre es'ES errors vB" ests (8) for aE for, for aE ESS+ESECS+ES ES EP forS +P (©) E,for —E, for SE sn AE for ESSEPEP+E +P forS+P EP+E+P (0) E,for —_ E, for E, for NE va E 5-65 ES -+EPEP +E+P forS +P {E) AE for aE, AE for —_E, for E+S+ES forS—P EP+E+P EP +E+P 16. Consider ages + heat, If activation energy {for forward reaction is 100 ki/mole then activation energy for backward reaction and heat of reaction is (A) 100, 200 (8) 80, 20 (C) 120, 220 (D) 140, 40 17. Ina reaction, the thershold energy Is equal to : (A) Activation energy + normal energy of reactants, (8) Activation energy ~ normal energy of reactants (C) Activation energy (0) Normal energy of reactants. 18, The first order rate constant k is related to tem- perature as log k = 15.0 ~ (108/T), Which of the fol~ towing pair of value is correct ? (A) A= 10! and E = 1.9 x 10" KI (8) A= 10 and € = 40K) (C)A= 10" andE = 40K) (0) A= 10 and E = 1.9% 10" 419, When a graph between log K and 1/T is drawn 9 straight line Is obtained. The temperature at which line cuts y-axis and x: (A) 0, £/2.303 Rog A (©)0, 1694 (8) =, E/(RIN A) (0) None of these 20, The rate constant, the activation energy and the frequency factor of a chemical reaction at 25°C are 3.0 x 107, 104.4 K) mot and 6.0 x 10 5" respectively. ‘The vaiue of the rate constant as T -» » is (A) 2.0 x 10s" (B) 6.0 x 10' (C)infinity (0) 3.6 x 10s 21, The rate data for the net reaction at 25°C for the reaction X + 2Y +32 are given below : Ded Ya gms Feared for [2] t0 Increase by 0.005 mol pertitre. 0.01. 0.01. 72sec 0.02 / 0.005)" 36sec 0.02 0.01 "18 sec ‘The intial rate (as given by Z) is (A) First order in both X and Y (8) Second order in X and first order in Y (C) First order in X and second order in ¥ (0) None of the above 22, The rate of production of NH, in N, + 3H, -» 2NH, 1s 3.4 kg mint, The rate of consumption of His : (A) 5.1 kg min” (B) 0.01 kg sec* (C) 0.6 kg hr? (0) None of these 23. Fora given reaction of first order it takes 20 min. for the conc. to drop from 1.0 M to 0.60 M. The time required for the conc. to drop from 0.60 M to 0.36 M will be = (A) more than 20 min (8)20min (C) less than 30 min (0) cannot tell. 24, For a first order reaction, the concentration of reactant (A)is independent of time (B) varies linearty with time (C) varies exponentially with time (D) None 25, Graph between conc. of the product and time of the reaction A -+ B is of the type. Hence graph be- ween “2 ag time ibe of they:beaayey) (a) Felayey © 26, Mathematical representation fort, life for first ‘order reaction is over is given by : (A) t= [(2.303)/(K)] og 4 (B) ty, = [(2.303/(k)} fog 3 (C) t= [(2.303)/(K)] 1og(4/3) (O)t,,. = ((2.303/(K)]l09(3/4) 27. For a reaction A -+ Products, the conc. of reac tant C,, aC,, 2°C,, 8°C, after time interval 0, tt. jere 'a" is constant. Then (A) reaction is of 1 st order and K = (1/t) In a (B) reaction is of 2nd order and K = (1/tC;)(1 (C) reaction is of 1st order and =\(1/t) In(1/a) (0) reaction is of zero order and k = {(1.- a))Cyt ace 2s, Ne —> C1 + Np Half-life is independent of conc. of A. Affer 10 minutes volume NN, gas is 10L and after complete reaction 50 L. Hence rate constant in min : (A) (2.303/10)|og 5 (B) (2.303/10) log 1.25 (C) (2.303/10) log 2 (0) (2.303/10) log 4 29. Areaction 2A +8 _* , C + Dis first order with respect to A and 2nd order with respect to B. Initial conc. (t = 0) of Ais C, while Bis 2C,. If att = 30 minutes the conc. of € is C4 then rate at t = 30 minutes is : TOK ig) 270K 2470 5) 49KC} wees of os 130._In acidic medium the rate of reaction between (6r0,)- and Br ions is given by the expression, - {6(Br, Yak) = K(BrO, Be JTH"}°1t means : (A) Rate constant of overall reaction is 4 sec* (@) Rate of reaction is Independent ofthe conc. of aid (C) The change in pH of the solution will not affect the rate (©) Doubling the cone. of H' lons will increase the reaction rate by 4 times. ya ‘34. The decomposition of a gaseous substance (A) to yield gaseous products (8), (C) follows first order kinetics. If initially only (A) is present and 10 minutes after the start of the reaction the pressure of (A) is 200 mm Hg and that of over all mixture is 300mm Hg, then the rate constant for 2A» B + 3Cis (A) (1/600) In 1.25 sec" (B) (2.303/10) log 1.5 min (C) G0) In 1.25 sec* (D) None of these 32, For a certain reaction of order ‘n’ the time for half change t,,'s given by t,, = [(2 - s2)/k] x C,?, where K Is rate constant and C, 1s the initial concen- tration. The valve of nis : (Ay. (B)2 (oo (O05 '33._Two first order reaction have halflife in the ratio 3: 2. Calculate the ratio of time intervals t, : t. The time t, and t, are the time period for 25%" and 75% completion’for the first and second reaction respectively = (A031 1 (B) 0.420: 1 (0.27351 (D) 0.11971 34, A reaction proceeds in three stages, The first stage is a slow second, order reaction, the second stage is fast and of first order, the third stage is fast ‘and is a third order reaction. The overall order of the reaction is : (A) First order (B) Second order (C)hird order (0) Zero order. ‘35. A reaction of the type A + 2B + C+D occurs by following mechanism ‘A+ B-+X rapid equlibrium X+C+Y Slow Y +840 Fast ‘What is the order of the reaction : (ay (8)2 (D) Non determinable 36. Following mechanism has been proposed for are- actions, 2A+B+D+E; (3 A+B4C#D.....(Slow) ; A+ CE vsseen ‘The rate law expression for the reaction is : (Ayr= KAP. (8)r= K(APIB] (OR= KAP (0)r = Kia) (8) Lo 37. For the reaction H, + 1, == 2ML. The rate law expression is : (A) (41/2) ofHIV/at) = bk, (4,) () (8) [(+1/2) afti/ae] = ¢k, (FNP 7, (4,100) (C) [(+1/2) ofeirar) = k, tH, C0) ~ ce) (0) (41/2) afHay/at] = k, k, EH,50)38. A subtance undergoes first order decomposition. ‘The decomposition follows two parallel first order re- actions as : and K, = 1.26 x 10“ sect; K, = 3.8 x 10 Sec, The percentage distribution of Band C are (A) 80% Band 20% C_(B) 76.83% B and 23.17% C (C) 90% Band 10% C_(D) 60% B and 40% C B—43C. k,=2%10" sect and k, = 3x10+I/mol-sec. {[B]/dt} equal to: (A) k, (A) - ,(B]—(B) , [AP = k, [8] (C)k TA)- (BP (0) KAP - k, [CP 41, For the reaction : A+ 2B <=> AB, ; the rate of forward reactions = 1 1O{AI9) = 1 10148). The rate contents fr forward ond backward ren meee (aT 0 ms, 1 10sec (i x tose’ io ume (C) 1 = 10' ? ms", 1 x 10* sect (O) 1 x 10° Lev! s"', 1 x 10° sec 42, At the point of intersection of the two curves ‘shown for the reaction il i A> 7B time —> the concentration of Bis given by : cay Ae (oy Ae, =, to Me oon (0) 43. For a hypothetical reaction aA + b8 -+ Product, the rate law is : rate = K[A]'[B)’. then : (A) (@ +b) = (x+y) (B) (2 +b) < (x + y) (C) (a+b) >(x+y) (D) Any of these 44, For the reaction : 2NO + Br, => 2NOBr; the mechanism is given in two steps : (1) No + Br, E88t= Noer, (2) NOBr, + NO_#=, 2NOBr. ‘The rate expression for the reaction is: (A)r= KINOFIBr,] (8)r= K(NOI(Br,] (C)r = KINO}EF (©) = K{NOBe,) 45, For a gaseous reaction, the rate is expressed in 0 ° ac terms of G In place of SF or Cr, where C is con- centration, nis number of moles and 'P’ is pressure of reactant. The three are related as : arial lal ©) eel" vier] ois} 46. For a chemical reaction : A -»Product, the rate of disappearance of Ais given by : nin S, Soa, SA alow €, the order of reaction and rate constoms are respectively: (0) None of these LR EK, (OME (OU, Ge 47. For a reversible reaction, A+ 8 =>C+D; 4H = ~ Akcal. If energy of activation for the forward reaction is B kcal, the energy of activation for back- ward reaction in kcal is (A)-A+B(B)A+B (C)A-B (D)-A-8 48, The reaction A (g) —+ B(g) + 2C (g) Is a first ‘order reaction with rate constant 3465 x 10-6 5". ‘Starting with 0.1 mole of A in 2 litre vessel, find the ‘concentration of A after 200 sec., when the reaction is allowed to take place at constant pressure and temperature. (A)0.05M (8)0.025M (0) None of these (c)0.0125M 48. How much faster would a reaction proceed at 25°C than at 0°C if the activation energy Is 2 cal : (A) 2 times (B) 16 times (C)11 times (0) Almost at same speed ‘SO. The temperature coefficient of reaction 1 ‘and reaction IT Is 3. Both have same speed at 25° ‘and show I order kinetics. The ratio of rates of reac- tions of these two at 75°C is : (7.6 (B)5.6 — (C)6.6 2 (0)8.6EXER Single correct 41. The reaction CH, ~ CH, ~ NO, + OH" + CH, ~ CH - NO, + H,0 obeys the rate law for pseudo first order kinetics in the presence of a large excess of hydrox- Ide lon. If 1% of nitro ethane undergoes reaction in half a minute when the reactant concentration is 0.002 M, What is the pseudo first order rate constant 7 (A)0.02 min (B)0.05 mire (€)0.01 min (0) 0.04 mire 2. Decomposition of H,0, is a first order reaction. A solution of H,0, lebelled as "16.8 V" was left open. Due to this, some H,0, decomposed. To determine the new volume strength after 2.303 hours, 20 mL of this solution was diluted to 100 mL. 25 mL of this diluted solution was titrated against 37.5 mL of 0.02 MKMnO, solution under acidic conditions [Given : STP is 1 atm and 273 K] Calculate the rate constant (in he) for decomposition of H,0,. (06 (B05 (Cc) 0.4 (D)0.8 3. The reaction A —“"» Byobeys the'rate law for pseudo first order Kinetics in the presenet of a large excess of hydroxide'ion. If 90% of A undergoes reac- tion in haifa minute when the reactant concentration is 0.002 M, What is the pseudo first order rate con- stant in mint (A) 4.61 (B)2.61 (C) 3.61 (D) 5.61 4.A—“—+B, qt 10min 3xA——_4 € Both reaction have same rate constant and each oc- curring following first order kinetics. Choose the correct option for second reaction. (A)t,, = 10/3 min (B)t,, = 30min (C)t2 = 10min (0) Bdka insumicient 5. The gas phase decomposition (in closed con- tainer) 2A, + 4B, +C,, Follaws the first order rate law. At a given tempera- ture specific reaction rate is 7.5 x 10° 5"!. The initial pressure of A is 0,1 atm. Calculate the time of OBJECTIVE PROBLEMS (JEE ADVANCED) jecomposntion ie total pressure comes 0.15 atm. (log 1.4925 = 0.1739). (A) 66.6 sec (8) 22.24 sec (C) 53-4 sec (0) None of these 6. Which graph represents zero order reaction (Ata) + 8(9)) 48) c wl ®* T T ‘ ue «cy (0) Tb, Tn 7211 decomposition’reaction A (g)—+ B (9) follows firstorder kinetics then the graph of rate of formation (R),oF B against time twill be. Ry Ry (a) I (8) / a q Ry © |\ OLD a a ‘8. For the first order decomposition of SO,Cl,(9), $0,C1,(9) -> SO0,(g) + C,(9) a graph of log (a, ~ x) vs t is shown in figure. What Is the rate constant (sect)? Time tmin) + 2468 0 1" (ayo. (oz, Wass ie, (0) 1.15 x 10°9. The variation of concentration of A with time in two experiments starting with two different initial concentration of A Is given in the following graph. The reaction is represented as A(aq)—» B(aq). What is the rate of reaction (M/min) when concentration of A in aqueous solution was 1.8 M? tmgmn)-+ (A) 0.08 mint “(B) 0.036 M mint (C)0.13M mie! (D) 1M mint 10, SO, gasis entering the environment at a constant rate of 6.93 * 10°¢ gm/L/day due to the emission of polluting gases from thermal power plant, but at the same time it Is decomposing & following first order kinetics with halflife of 100 days. Based on above information select the true statement(s). (A) Concentration of SO, in Kota is 1.25 x 40-5 M (Assume SO, present in air reaches:stendy state) (8) If 107 L of air is passed through't'L pure water (assuming allSOs to be dissolved init) & resulting solution is titrated against 1N NaOH solution, 15 mlis required to reach end point. (C) An industry is manufacturing H,S0, at the rate of 980 kg per day with the use of SO, in air it should Use 8 x 10° Litre air /day. (0) If SO, emission is stopped then after 1000 days Its concentrations will reduce to = 1.2 x10" M. 114, For the reaction A» B, the rate law expression —MA) ‘sae Aly, then (A) The integerated rate expression is k = IN = k [A}?2. If initial concentration of [A] is (B) The graph of VA Vs t will be (C) The half ite period t= Ab (D) The time taken for 75% completion of reaction 12. Consider the reaction, eB ee rs ie tC ‘A, Band Call are optically active compound . If optical rotation per unit concentration of A, B and C are 60°, select write statement(s). (A) Solution will be optically active and dextro after very long time (8) Solution will be optically active and levo after very long time (C) Halt life of reaction is 15min (O) After 759% conversion of Winto B and C angle of rotation of solution will be 36°. (REASONING TYPE Directions : Read the following questions and choose (A) If both the statements are true and state- ‘ment-2 Is the correct explanation of satement-1. (B) If both the statements are true and state- ment-2 Is not the correct explanation o satement-1. (C) If statement-1 is True and statement-2 is False. (0) If statement-1 is False and statement-2 is True. Assertion & Reasoning type questions 13, Statement-1 : A fractional order reaction ‘must be a complex reaction. ‘Statement-2 : Fractional order of RDS equals to AA) (8)(B)_—(C)(C)_— (0) (0) 14, Statemant-1 : The time of completion of reactions of type A» product (order <1) may be determined. Statement-2 : Reactions with order Lare either too slow or too fast and hence the time of ‘completion can not be determined, A) (8B) (C(C)——(DY(D)15. Statement-1 : Temperature coefficient of an ‘one step reaction may be negative. Statement-2 : The rate of reaction having negative order with respect to a reactant decreases with the increase in concentration of the reactant. MA GB) (C—O) (0) 16. Statement-1: The overall rate of a reversible reaction may decrease with the increase in temperature. Statement-2 : When the activation energy of forward reaction is less than that of backward reaction, then the increase in the rate of backward reaction is more than that of forward reaction on increasing the temperature. (ay (A) (B)(B) (CDEC) 17. Statement-1 : _ In a reversible endothermic reaction, E,,, of forward reaction Is higher than that ‘of backward reaction ‘Statement-2 : The threshold energy of forward reaction is more than that of backward reaction YA) (B)(B) (D(C) (0) (O) 18, Statement-1 : A catalyst provides an alternative path to the reaction in which conversion of reactants into products takes place quickly Statement-2 : The catalyst forms. an activated: complex of lower potential energy, with the reactants by which more number of molecules are able to cross the barrier per unit of time, AA) (BB) (VC) 19, Statement-1 : Rate of a chemical reaction in- creases as the temperature is increased, Statement-2 : As the temperature is increased frac- tion of molecules occupying E, or more increases. (AY (8)(B)—(C)(C)_—(0)(0) (0) (0) (0) (0) 20. Statement-1 : For the bimolecular reaction to react, reactant must collide with each other. Statement-2 : Bond breaking and formation occurs during the collision. (AA) B)B) (CVC) (0) (0) 24, Statement-1 : Catalyst does not change the SH value of the reaction. ‘Statemant-2 : Catalyst are generally added in very ‘small quantities and not stoichiometrically. (aya) (8B) (C)(C)_ (DY (0) 22. Ozone decomposes according to the equation 20,(g) -» 30,(g) Mechanism of the reaction is Step I: 0,9) == 0,(9)+ O(9) (fast) Step Il: 0,(g) + O(g) —_, 20,(9) (slow) Which of the following is correct ? (A) for step I, molecularity is 2 (B) for step Il, molecularity is 1 (C) step Il is rate determining step (D) Rate law expression for the overall reaction is ~£10,1-M0,710,"" 23. Consider the following case of competing 1st order reactions ‘After the start of the reaction at t = 0, with only P, concentration of Qs equal to R at all times. The time in which all, » the three P. Bhn concentration will be equal Is given by caye a Peace (ay 1 Se too (Ot tome? (0) t= BP og.92 24, Asubstance undergoes first order decomposition. ‘The decomposition follows two parallel first order reactions as ky ky21.26 * 10-45 re ky=3.8 = 10-591 a The % distribution of B and C is respectively. (8) 23.17%C (0) 76.83%C “(Wy 76.83%8 (C) 23.17% 25, Which of the following concepts are correct (A) Iffor, A+B aH = +qcal then for, B +A aH = ~qcal (8) If for, A == B equilibrium constant = K then for, B <= A equilibrium constant = (C) If for, A -+ B rate constant = k then for, B+ rate constant » k (0) If for, A+ B energy of activation = E then for, B+ A energy of activation = - E26, The basic theory behind Arrhenious equation is that (A) the activation energy and pre exponential factor are always temperature independent. (B) the number of effective collisions is proportional tothe number of molecules above a certain threshold energy. (C) as the temperature increases, 50 does the number of molecules with energies exceeding threshold energy. (0) rate constant is a function of temperature. 27. Which of the following statements are correct about half life period ? (A) Itis proportional ta initial concentration for a zero order reaction. (8) Average life = 1.44 times half life for a first order reaction. (C) Time of 75% reaction is thrice of half life period in second order reaction. (0) 99.9% reaction which is first order, takes place in 100 ‘minutes ifthe rate constant of the reaction is 0.0693 mir: 28, For a reaction : 2A + 28 -+ products, the rate law expression is r = k[A}? [B]. Which of the following is/are correct? (A) The reaction is first order wart. B (8) The reaction is of second order wart: A (C) The reaction Is of third order, overall {D) Slowest step of the reaction is givenas A+ Bs» AB 2% 6 8 ® foe E> of. Me Me os 0 o Which of the following statements are correct ? (A) Itis 5, 1 if (1) oF (U1) is formed. (8) It ts S,1 If equimolar mixture of (1) and (11) is formed. (C) It is §,2 if (1) or (II) is formed. {D) It is $,2 if (11) is formed. ‘30. Rate constant k varies with temperature by equation log, k(min) = 5 ~ 22°. we can conclude (A) pre exponential factor Ais 10° (8) E, is 2000 k cal (C)E, is 9.212 k cal (0) pre exponential factor Ais 5 31. Areaction is catalysed by H" jon. In presence of HA, rate constant is 2 x 10° min-! and in presence ‘of HB rate constant is 1 x 10°? min. HA and HB being strong acids, we may conclude that (A) HB is stronger acid than HA (B) HAis stronger acid than HB. (C) relative strength HA and H8 is 2. (D) HAs weaker than HB and relative strength is 0.5. 32. The potential energy diagram for a reaction R -+ Pis given below Which of the following is true 7 (A) E, (forward) = y (B) E, (backward) = 2 (e=x+y (0) aH, =% 33. An organic compound A decomposes by following {wo parallel first order mechanisms : Select the correct statement(s) (A) If three moles of are completely decomposed then 2 moles of B and 1 mole of C will be formed. (8) If three moles of A are completely decomposed then 1 moles of B and 2 mole of C will be formed. (C) hall life for the decomposition of Ais 20 min (O) half life for the decomposition of B Is 0.33 min 34, Half life for which ofthe following varies with initial concentration (A,] (A) zero order (C) second order 35._In which of the following, E, for backward ‘reoction is greater than E, for forward reaction ? (A) a—EecS2t ob aH = —10kcal ) (C) Ect 4b aH = +10kcal (8) first order (0) third order a Eft yb AH = -20kcal (0) a ExO8 oy aH = -20kcat COMPREHENSION - 1 ‘Oxidation of metals is generally a slow electrochemi- al reaction involving many steps. These steps in- volve electron transfer reactions. A particular type of oxidation involve overall first order kinetics with re- ‘spect to fraction of unoxidised metal (1 ~ f) surface thickness relative to maximum thickness (T) of oxidised surface, when metal surface is exposed to air for con- siderable period of time.of oxide film at time 't' & T = thickness of oxide film at t=» A graph of In (1 ~ f) vs tis shown in the adjacent figure. |36. The time taken for thickness to grow 50% of Tis (A) 23.1 hrs (B) 46.2 hrs (C) 100 hrs (D) 92.4 hrs (37. The exponential variation of 'f with t(hrs) is given by (A) [1-0-9 (8) 74 (C) ewe (0) gz Initially only 2 moles of A are present. ‘38. The total number of moles of A, B AC atthe end (of 50% reaction are’ (ay (8)3 os 39. Number of moles of B are 2 (1 (C)0.666 (0)0.333 (0) None COMPREHENSION -3 The rate of a reaction increases significantly with in- crease in temperature. Generally, rates of reaction are doubled for every 10° rise in temperature. Temperature coefficient gives us an idea about the cchonge in rate of a reaction for every 10° ‘change in temperature. __ Rate constant of (T= 107°C Temperature coefficient # = rae ‘Arrhenious gave an equation which describes rate con- stant k as a function of temperature is k = A*"*? where k is a rate constant ‘A's frequency factor or pre exponential factor E, Is activation energy Tis temperature in kelvin and Ris universal gas constant Equation when expressed in logarithmic form becomes 40, Fora reaction E, = 0 and k = 3.2 « 1 5 at 325K. The value of k at 335 K would be (A)3.2 x 16s (B) 6.4 x 10's (C) 12.8 x 10's (D) 25.6 x 10s 441. For which ofthe following reactions k,,./ky., Would bemaximum ? (A) P+Q +R: E, = 10k) (C) AsB +CiE, -10.5ks (8) E+F-+0.E, =21k (D) L+M ONE, = Ska 442. Activation energies of two reaction are E, and E, with E, > E,, If the temperature of the reacting sys" tems is increased from T, to T, (k’ are rate constants at higher temperature). KK KG Oi Once Kok 2 Oi > 43. For the reactions, following’data is given a «i= 10m (=20%) 4 gap, (= 2000 5D | te = 10" emp {=00) Temperature at which = ks (A) 434.22 K (B) 1000 K (C) 2000 K (D) 868.44 K COMPREHENSION - 4 The rate and mechanism of chemical reactions are studied In chemical kinetics. The elementary reac- tions are single step reactions having no mechanism, ‘The order of reaction and molecularity are same for elementary reactions, The rate of forward reaction aA + DB-+cC + dD Is given as j= 1 HAI ._ 1 618). 1 d1C). 1 (0) Maen ea ea mee K{A}{B}. In case of reversible reactions net rate ex- pression can be written as : rate = K,[A}[8)* - K,{CH{O}. At equilibrium, rate = 0. The constants K, XK), Ky, are rate constants of respective reaction. In ‘2e of reactions governed by two or more steps re- ‘actions mechanism, the rate is given by the solwest, step of mechanism, 44, The rate of formation of SO, in the following re- action : 250, + 0, -+ 250, is 10'g sec, The rate of disappearance of ©, will be : (A) 5g sec (C) 209 sec rate +| $} (8) 100 g sec (0) 2g sec45. For the reaction : aA + BB; oft -nfS)-t onen: (A)3.98 (B) 2.18 (C) 1.48 (o)o 446. Fora reaction, 2ND, +N, + 30, ; OO 2 kino; MH - K,tno,) a a Tal -K,90,), then : (AK, =, =k, (8) 3K, = 6K, = 2K, (C)K, = 2k, = k, (0) K, = K, = 2K, COMPREHENSION - 5 ee The rate ofa reaction (S*) varies with nature, ps ‘cal state and concentration of reactants, tempera- ture, exposure to light and catalyst, whereas rate constant (K) varies with temperature and catalyst, only. The rate constant K is given a5 K. Ag" where Als Arrhenius parameter or pre-exponential fac tor and E, is energy of activation. The minimum en= ergy required for a reaction is called threshold energy {and the additional energy required by reactant mol~ ‘ecules to attain threshold energy level is calledien= ergy of activation. 47. For a reaction, A+B; if 425» ne 4og,,K(sec:!) 4 > K, the,Arrhenius pa- rameter and energy of activation forthe reaction are (A) 10 sec, 239.34) (B)14,57.6 kcal (C) 10 sect, 23.93k) —(D) 10° sec, 5.76 kcal 48. At what conditions exponential factor is 1 for a reaction : (A) Infinite temperature (B) Free radical combination (C)E,=0 (0) Al of these 49. For an endothermic reaction, which one is true if 4H is heat of reaction and E, ls energy of activation : (A)E,> aH (BE, <3H (C)E, za ()E=0 (MATCH THE FOLLOWING 50. Match the column Column column -11 (A) First order reaction _(P) Rate constant increases on increasing the concentration (Q) Half life depends on the initial concentration (8) Second order reaction (C) Zero order reaction _(R) Reaction must be complex (O) Fractional (+ ve) (S) Half life decreases on order reaction Increasing the temperature (1) The plot of concentration of reactant verses time wall bearectanguar hyperbola ‘51. Consider the following energy diagram for the re~ action. A+B, <> 208 t 50 tok 39) 1 Fopen tomar Column I Column Ir A) ECO) (P) 101g mal" ) Ee) (Q)404e) mort ah, (R) 304) mot 9 g (5) 504: mot* 52. For the reaction of type A(g) —» 28(9) (Column contains four entries and column- IIT contains four entries. Entry of column-I are to be matched with ONLY ONE ENTRY of ume Colum x (A) 49) |, 4 for first order (8) {A} vst for Rat order (©) [B] vs t for first order ©) [Alyse forzeroorder @) \ ‘s) / Column-I and column-IT. Entry of column-1 are ta be matched with ONE ENTRIES of column-II and vice versa.Column 1 (Graphs reaction A-» Products) ole \ @ }|\ o Column Ir (Co-ordinates) (P) in [A] (y-axis), t (x-axis) (order = 1) (Q) ty (y-anis), [Ay] (x-axis) (order = 1) (R) Ffy-axis), (x-dx0s) (order > 0) (S) + (yraxis),t (s-axds) (order = 0) (Ty (y-axis), [Ag] Graxis) (order > 1) t (W)—_jqj (rams), tans) (order = 2) ()e(y-axis), (A] (x-axis) (order = 1) ROGER TPS 54, The complex [CO(NH,),F] according to the equation. [CONH, WET? + HzO [CO(NH, )6(H201)"- 0 The rate of the reaction = rate const. x, [complex]? x [H']*. The reaction Is acid. catalysed |.e. [H*] does not change during the reaction. Thus rate = k[Complex]* where k’ (H'), calculate given the following data at 25°C. reacts with water [Complex]M [HJM Tye on 0.01 1 oz 0.02 Os 55. An optically active compaund A upon acid catalysed hydrolysis yield two optically active com- Pound 8 and C by pseudo first order kinetics. The ‘observed rotation of the mixture after 20 min was 5° ‘optical rotation per mole of A, B & C are 60°, 40° & — 80°. Calculate half life of the reaction. 56. Consider the following first order decomposition : V. ay ” 1 Here, “t" corresponds to the time at which (2) of reactant Is decomposed. The value of *n" Is 57. For 2 1* order reaction (gaseous) (cont. V, T) aA-—+(b-1)B+ C (with b >a) the pressure of the : system cress by 502-1} in tinea 10min Shenson recta entre paca 58. The rate of decomposition of NH,(g) at 10 atm (on platinum surface is zero order. What Is rate of formation (in M min") of H,(g), if rate constant of reaction 2NH, .,-»N, (9)+3H, (9) is 2.0 M min"? 59. SA—sProduct In above reaction, half-life period is directly proportional to initial concentration of reactant. The initial rate of reaction is 400 mol lit! min" Calculate the half-life period (in sec) when initial concentration of reactant is 200 mol lit"). 60. In an elementary reaction’A(p) +28(9)—+ C(o) the intial pressure of Aand B are P,=0.40 atm and Py '=0.60 atm respectively. After time T, if pressure of Cis observed'0.1 atm, then find the value of sfintial rate ot reaction) ‘ilrate of reaction after time t) 61. Carbon monoxide reacts with O, to form CO, : 2C0(g)+0,(6) —» 200, (g) information ‘on this reaction ‘s_giveninthetable [CO] mot/t| [0] mel 0.02 0.02 0.0 oz (Rate of reaction (mol/L rin) 4x10" 1.610" 0,04 219 Vora ere vate Yara rate conSiot Tor We rencion In proper related unit ? 62. Half-life for the zero order reaction, A(g)-»8(g)+C(g) and half-life for the first order reaction X(g)—+ Y(g)+Z(9) is equal. If completion time for the zero order reaction is 13.86 ‘min, then calculate the rate ‘constant (in he *) for the reaction X(g)-»¥(9)+Z(9)- 63. For any acid catalysed reaction, 4,5, Half-life period is independent of concentration of A at given pH. At same concentration of A half-life time is 10 min at pH=2 and half-life time is 100 min at pH=3. Ifthe rate law expression of reaction is F=k{A}'{H']y then calculate the value of (x+y), 64, For a reaction, A g=aB equilibrium constant is 1,66 and 166 hr. Calculate the time (in hours) when concentration of Bis 80% of its equilibrium concentration. (Given : In 25=3.20)EXERCISE Qi For the reaction NH, +N, + 3H, ‘a curve is plotted between [NH,] is time as shown Time (sec) Calculate (a) rate of disappearance between Sto 10 sec {b) rate of disappearance between 10 to 20 sec (2 For the reaction 3810" +03 + 28" in an alka- line aquesous solution, the value of the second order (in Bro) rate constant at 80°C in the rate law for 0") was found to be 0.056 L mol's". What is the rate of constant when the rate law is written for Q.3 Dinitropentaoxide détomposes as follows : N0,(0) »2NO\(9) + 20,10 Given that =8423! 49,051 BOE 4,051 SCA) - 4,05) What isthe relation between fy, k, and k,? Q-4 The reaction 2A + B + C-+D + Eis found to be first order in A second order in B and zero order in C. (i) Give the rate law for the reaction in the form of differential equation. (li) What is the effect in rate of increasing concen- trations of A, B, and C two times ? Q5 For the elementary reaction 2A + B, -» 2AB. Cal- culate how much the rate of reaction will change if the volume of the vessel is reduced to one third of its, ‘original volume? 1nd oxygen reacts at higher tempera- ANH,(9) + 50,(g) + 4NO(9) + 6H,0(9) SUBJECTIVE PROBLEMS (JEE ADVANCED) In an experiment, the concentration of NO increases by 1.08 x 10+ mol litre-' in 3 seconds. Calculate. (i) rate of reaction. (il) rate of disappearance of ammoni (iil) rate of formation of water. Q.7 Inthe following reaction 2H,0, -+ 2H,0 + O, rate of formation of O, is 3.6 M min, (2) What is rate of formation of H,0 7 (b) What is rate of disappearance of H,0, ? Q.8 The reaction A(g) + 2B(9) -» C(g) + D (9) is an elementary process. In an experiment, the initial par- tial pressure of A & Bare P, = 0.6.and P, = 0.8.atm, if P, = 0.2 atm then calculate the ratio of rate of reac- ton relative to initial rate. Q9 In the following reaction, rate constant is 1.2 x 107 Ms"A +.B, What Is concentration of B after 10 and 20 min., if we start with 10M of A. Q.40 |For thé following data for the reaction ‘A+ products. Calculate the value of k. Time (min.) TA) 0.0 010M 1.0 0.09m 2.0 0.08 Q.11 The rate constant for a zero order reaction is 2x 107 mol L" sec’, if the concentration of the reactant after 25 sec Is 0.25 M, calculate the initial concentration. Q12_Adrop of solution (volume 0.10 mi) contains 6 x 10 mole of H’, if the rate constant of disappear- ance of H" is 1 x 10” mole litre’ sec. How long would it take for H" in drop to disappear ? Q.43. Acertain substance A is mixed with an equimo- lar quantity of substance B. At the end of an hour Ais 75% reacted. Calculate the time when A is 10% unreacted. (Given : order of reaction is zero) Q.14 A first order reaction is 75% completed in 72 min. How long time will It take for (1) 50% completion (ii) 87.5% completion 2.15 _A first order reaction is 20% complete in 10 min, Calculate (1) the specific rate constant, (ii) thetime taken for the reactions to go to 75% completion. Q.16 Show that in case of unimolecutar reaction, the time required for 99.996 of the reaction of take place in ‘ten times that required for half ofthe reaction. Q.17 A first order reaction has a rate constant is 1.5 x 10° Sec", How long will .0 9 of this reactant take to reduce to 1.25 g. Q.18 A crug is known to be ineffective after It has decomposed 30%. The original concentration of 3 sample was 500 units/ml. When analyzed 20 months later, the concentration was found to be 420 units/ mi. Assuming that decomposition is of I order, what will be the expiry time of the drug? Q.19 A virl preperation wes inactivated in a chemi cal bath. The inactivation process was found to be first order in virus concentration. At the beginning of the experiment 2.0% of the virus was found to be. Inactivated per minute. Evaluate k for inactivation pro- Q.20 Consider the reaction : A-+B + C. Initial con- centration of As 1 M. 20 minutes time I required for completion of 20% reaction. +H than cs late half ite (t,) of reaction, Q.21 The reaction $0,Clfg) =1'80,(9) +'CH(g) is a frst order gos reaction with kim 2.3 % 107 sec" at 320°C. What % of SO,Cl, is decomposed on heating this gas,for 90 min, ORDER OF REACTION & RATE LAW Q.22 At 800°C the rate of reaction 2NO +H, +N, +H,0 CChanges with the concentration of NO and H, are twolmm twin 2°01 nat secs ® 1$x1+ 4xtor aa ios MeSEiee S2iGs 331g: (W) 3.0 x 102 x 107 8x 10" (2) What is the order of this reaction ? (b) What is the rate equation for the reaction ? (€) What is the rate when [H,] = 1.5 « 107 Mand (NO} = 1.1.x 107M > Q.23 The data below are for the reaction if NO and Cl, toform NOCI at 295 K Concentration of [6] Concentrstion of WO Initi ace (Par) 0.05 00s 1x10 ous 0.05 3x 107 0.05 15 3x 109 (2) What is the order w.rt NO and Gy, inthe reaction. () Write the rate expression {(c) Calculate the rate constant (d) Determine the reaction rate when concentration Of Cl, and NO are 0.2 M & 0.4 M respectively. 24 _The catalytic decomposition of W,0 by gold at So0e cand at an inl pressure of 20brt 30% comples in $3 minutes te 3M coptete 100 Sar woe {Whats the order ofthe reaction 7 (ji) Calculate the velocity constant. {i} wow mucho 0 wl Secomposen 100 min. t the same temperdlre but at ital pressure of scone Q.25_ The following data are for the reaction A+ B = products : Conc.A Conc. 8 Initial Rate my on (molt s+) on 0.1 4.0 10" oz 02 1.6 x 10 os ot 2.0% 107 05) os Lox 107 ())What isithe order with respect to A and B for the ‘reaction ? {i Caleulate the rate constant. (ill Determine the reaction rate when the concentra- tions of A and B are 0.2 M and 0.35M, respectively. 926 The pressure of a gas decomposing at the sur- face of a solid catalyst has been measured diferent times and the results are given below t(sec) 0 100 200 300 Pr. (Pascal)4 x 10°3.5x 10? 3x10 2.5% 10? Determine the order of reaction, its rate constant. Q.27_Thehalf life period of decomposition of a com- ound is 50 minutes. If the initial concentration is halved, the half life period is reduced to 25 minutes, What Is the order of reaction ? Q.28 At 600°C, acetone (CH,COCH,) decomposes to ketene (CH, = C= 0) and vangus hydrocarbons. Given the initial rate data inthe table (2) Whatis the order ? (©) weite rate faw {€) Calculate rate constant (@) Calculate the rate of decomposition when the tone concentration is 1.8% 10° M Experiment Initial (CH,COCH,] Rate Ms" 1 6.0 x 107M S.2x 10" 2 9.0 x 109M 7.8 x 10+ 3 1.8 «107M, ?Q.29 The half life period of a first order reaction Is ‘50 min. In what time will it go to 90% completion ? Q.30 A first order reaction has k = 1.5 x 10+ per second at 200°C. If the reaction is allowed to run for 10 brs., what percentage of the initial concentration would have changed into the product ? What is the half life of this reaction ? Q.31 Show that in case of a first order reaction, the time required for 93.75% of the reaction to take place is four times that required for half of the reaction. Q.32_ The half time of the first order decomposition of nitramide is 2.1 hour at 15°C. NH,NO,(aq.) -» N,O(g) + H,0() If 6.2.9 of NH,NO, is allowed to decompose, calculate (i) time taker for'NH,NO, to decompose 99%, and (i) Volume of dry N,O produced at this point, measured at 1 atm & 273 K. Q.33._Affask contains a mixture of compounds A and 8. Both compounds decompose by first-order kinet- lcs. The half-lives are 54.0 min for A and 18.0 min. for 8. Ifthe concentartions of A and 8 are equal intially, how long will it take for the concentration of A to be. four times that of B? Q.34 Two substances A (t,, = S mins) and B (t, 15 mins) follow first order kinetics are'taken in way that initially [A] =-4{B]. Calculate the time after which the eoncentration of bath the substance will be equal. (CONCENTRATION REPLACED BY OTHER QUANTI: ‘TKESIN FIRST ORDER INTEGRATED RATE LAW Qs Tn this case we have A+B+c Time t = Total pressure ofA+B+C P,P, Find k. Q.36 A+B+C Time t = Total pressure of (B+C) P,P, Find k. a7 A +B+c of Volumestreagent _V, The Teagent roc with, B and é. Find k. Q.3B_A +28 +3C Time t * Volume ofreagent —_v, Reagent reacts with all A, B and O39 S+G+F Time t * Rotation of Glucose & Fructose r, f Find k. 40 At 27°C it was observed during a reaction of hhydrogenation that the pressure of hydrogen gas de- creases from 2 atmosphere to 1.1 atmosphere in 7: minutes, Calculate the rate of reaction (in M sec” and rate of reaction in terms of pressure. Q.41 At 100° C the gaseous reaction A+ 28 + C was observed to be of first order. On starting with pure A it is found that at the end of 10 minutes the total pressure of system is 176 mm. Hg and after a ong time 270 mm Hg. From these data find (a) initial pressure of A (b) the pressure of A at the end of 10 minutes (c) the specific rate of reaction and (4) the halflife period of the reaction ? 42 The reaction ASH(G)u» ASCs) + FHh{6) was followed at constant volume’at 310°C by measuring the gas pressure at intervals Show from the following figures that reaction is of first order. Time (in hs) 0 s 7.5 10 “Total pressure(inmm) 758 827856 (882 Q43_ The decomposition of N,O, according to the equation 2N,0, (g) -+4 NO, (9) + 0, (g) is a first order reaction. After’30 min, from start of decomposition in a dosed vessel the total pressure developed in found tobe 284.5 mm Hg. On complete decomposition, the toal pressure is 584.5 mm Hg. Calculate the rate con- stant of the reaction. Q44 The thermal decomposition of dimethyl ether {a5 measured by finding the increase in pressure of the reaction. (CH,), O(9) + CH,(9) + H,(9) + CO (9) ‘At 500® Cis as follows = Time (sec.) 3001195355 Pre. increase (mmHg) 9 250 467 619 the initial pressure of ether was 312 mm Hg. Write the rate equation for this reaction and determine the rate constant of reaction. Q.45__From the following data show that decomposi- ton of H,0, in aqueous solution is first order. Time (in'minutes) ° 10 20 Volume (in c.c. of KMnO,) 22.8 13.3 8.25Q.46 Adefinite volume of H,0, under going sponta- neous decomposition required 22.8 cc. of standard permanganate solution for titration. After 10 and 20 minutes respectively the volumes of permanganate required were 13.8 and 8.25 c.c. (2) Find order of reaction. How many the result be explained ? (b) Calculate the time required for the decomposition tobe half completed. (©) Calculate the fraction of H,0, decomposed after 25 minutes. Q.47 The following data were obtained in experi ment on inversion of cane sugar. Time(minutes)O 60 120 180360 = Angle of $13.1 4116 +10.2 49.0 +587 -3.8 rotation (degree) ‘Show that the reaction Is of first order. After what time would you expect a zero reading in polarimeter ? Q.48_ Inthe hydrolysis of propyl acetate in the pres- ence of dilute hydrochloric acid in dilute aqueous so- lution the following data were recorded : Time from start in minutes 60. 350 Percentage of ester decomposed 18.17 69.12, alain the ie in whe ba he str was decor Q.49_ Hydrogen peroxide solution was stored in a mild steel vessel. It was found, however, that the hydro- {gen peroxide decompased on the walls of the vessel (@ first order reaction). An experiment with 100 ml of solution gave 10.31 ml oxygen (corrected to 1 atm & 273 K) after 5:1 days under similar storage condi tions. Find how long the peroxide can be stored be- fore the loss of 20.00 mi oxygen occurs (per 100 mi ‘solution) if complete decomposition of the sample to H,O, gave 46.34 mi oxygen. Q.50 The reaction given below, rate constant for disappearance of Ais 7.48 x 10" secc', Calculate the time required for the total pressure in a system con- taining A at an initial pressure of 0.1 atm to rise to 0.145 atm and also find the total pressure after 100 sec. 2A (g) + 4B(g) + C (a) PARALLEL AMD SEOUEYTIAL REACTION St Forareaction X__, calelate value of ra- me tio, tty at any given instant t. a a qs2 ky sche ky rh = 1:10, Caleu= Wc ci tc ater one aro the Sat othe action Assuming only A was present in the beginning. Q.53_ Asubstance undergoes first order decomposi- Sen. The decompesiton fellows we paral fat or ae der reactions as 4: bk, = 1.26 « 10 sect De and = 3.6 «104 2 atelate the catrbation of BAC. Q.54 Fora reaction A+ B+ Ct,, for A&B are 4 ‘and 2 minutes respectively. How much time would be required for the Bto reach maximum concentration. ‘TEMPERATURE DEPENDENCE OF RATE Q55 For the two parallel reactions a4 4g and ‘A—1.C, Show'that the activation energy E' for the disappearance of/A Is given in terms of activation energies Ej and E, for the two paths by eke tke yoke (ACTIVATION ENERGY) Q.56 The energy of activation of a first order reac- ton is 104.5 ki mole” and pre-exponential factor (A) is 'S x 10° sect, At what temperature, will the reaction have a half life of 1 minute ? Q.57 The specific rate constant for a reaction in- ‘creases by a factor of 4, if the temperature is changed from 27°C to 47°C. Find the activation energy for the reaction. Q.58_ The energy of activation and specific rate con- stant for a first order reaction at 25°C are 100 ki/ mole and 3.46 x 10” sec' respectively. Determine the temperature at which half life of the reaction is 2 hours. Q59 A first order reaction is 50% complete in 30 ‘minutes at 27°C and in 10 minutes at 47°C. Calculate the (2) rate constant for the reaction at 27°C & 47° C and (b) energy of activation for the reaction. Q.60 A catalyst lowers the activation energy for a certain reaction from 75 k) to 25 k) mol". What will be the effect on the rate of reaction at 25°C, after things being equal.Q.61 Given that the temperature coefficient for the ‘saponification of ethyl acetate by NaOH is 1.75. Cal- culate activation energy for the saponification of ethyl acetate. Q.62_The rate constants of a reaction at 500 K and 700 K are 0.02 s" and 0.07 5", respectively. Calcu- late the values of E, and A at 500K. (MECHANISM Of REACTION Q.63 The reaction 2NO + Br, -+ 2NOB,, is supposed to follow the following mechanism tas (nO + 6, 8s nowr, (W)NoBr, + NO 8M, 2NOBr Suggest the rate of law expression. .64 For the reaction 2H, + 2NO +N, + 2H,0, the fallowing mechanism has been suggested : 2NO <= N,0, equilibrium constant K, (fast) NO, + H, NO + H,0(slow) N.O+H, —% , N, +H,0 (fest) Establish the rate law for given reaction. Q.65 Reaction between NO and O, to form NO, is, 2NO + 0, + 2NO, follows the following mechanism’ Ke NO + NO <= NO» (mn rapid equidtium) 1 N,0, + 0, —%_, 2NO, (slow) ‘Show that the rate of reaction is given by 4/aNOd)) yl 4[ POH) .xeoFi0;1 La 66, Forthe mechanism A+ BEC: C40 (2) Derive the rate law using the steady-state ap- proximation to eliminate the concentration of C. (5) “Assuming that ky < < k, express the pre-expo- nena factor Aad forthe apparent econ oder fate constant in terms of Ay A, and A, and EE and E,, for the three steps. 67. The reaction of formation of phosgene from CO and Cl, CO + Cl, -»COCI, ‘The proposed mechanism (1), SE 241 (fast equim) "a (rsco coe CO (fast equilbeium) Gil) COC + C1, “2, CO, + CI (slow) ‘Show that the above mechanism leads to the follow- Ing rate taw AECL) Kicoyc,)? where wy Koki 68, The approach to the following equilibrium was observed kinetically from both directions : PGi” + H,0 <> PuH,0,65] + Cat 25°C, it was found that = 3 pat) = 13.9 x 10° sec] roe) - [2.4 « 10° > Lmot! sec] x (PUH,O}G,) [Cr] What is the value of equilibrium constant for the complexation of the fourth Cl by P(t)? 69. Asolution of Ais mixed with an equal volume of » solution of B containing the same number of moles, ‘and the reaction A + B = C occurs. At the end of 1h, Als 75% reacted. How much of A will be left unreacted ‘at the end of 2 h if the reaction is (2) first order in A and zero order in 8; (b) first order in both A and B ; and (c) zero order in both A and B ? 70. The decomposition of a compound P, at tempera- ture T according to the equation Big) AQ ig) + Rig) +S, is the first order reaction. Af- iter 30 minutres from the start of decomposition in a dosed vessel, the total pressure developed is found fRer a long period of time the to be 617 mm Hg. Calculate the total pressure of the vessel after 75 mintute, if vol- Lume of liquid S is supposed to be negligible. Also calaulate the time fraction tye. Given : Vapour pressure of S(/) at temperature T = 32.5mmHg 71. A certain reactant 8 is getting converted to Be" in solution, The rate constant of this reaction is measured by titrating a volume of the solution with reducing reagent which only reacts with B’ and 8” In this process, It converts B” to 2" and B=" to BP, ALE = 0, the volume of the reagent consumed is 25 ml and at t = 10 min, the volume used up is 32 ml, Calculate the rate constant of the con- version of Br* to gin) assuming it to be a first order reaction. 72. A metal slowly forms an oxide film which com= pletely protects the metal when the film thickness is 3.956 thousand ths of an inch. Ifthe film thickness is, 1.281 thou. in 6 weeks, how much longer will it be before it is 2.481 thou? The rate of film formation follows first order kinetics.73, Avessel contains dimethyl ether at a pressure of 0.4 atm. Dimethyl ether decomposes as CHLOCH,(g) -+ CHA(Q) + CO(Q) + H,(g). The rate constant of decomposition is 4.78 x 10° min, Calculate the ratio of initial rate of diffusion to rate of diffusion after 4.5 hours of initiation of decomposition. Assume the composition of gas present and composition of 928 diffusing tobe same. 74, For the following first order gaseous reaction co ++ 28(9) wo-f CI a The initial pressure in a container of capacity Viitres. is 1 atm. Pressure at time t= 10 sec is 1.4 atm and after infinite time it becomes 1.5 atmosphere. Find the rate constant k, and k, for the appropriate reac tions. 75. The gaseous reaction : n,A(Q) -+ n,8(g) is first order with respect to A. It is studied at 8 constant Dressure, with a, as the initial amount of A.Show that ‘the volume of system at the concentration of A at ‘time ''t’ are given by the expressions. vee IAL = 1A,Lever -I Qi For the reaction ¥ + 1 <== 2A the true relationship is - [AIEEE-2002] aH ath én we (ey St = - a, - Me 2a) a t Q.2 Achemical reaction (2A) + [28] + {C]— Bestek toons the rate equation : r= {A] [OP the Order of reaction is ~ [ateee-2002] (0) (ayo (1 (2 (0)3 Q.3 The unit of rate constant of first & second order reaction is respectively - [ATEEE-2002] (A) time, mol (B) mole itr, timer? {C) mole, litre, time-t, time-! (0) sect, trent Q-4 In the equation = bog Co - | , the. Sven aediog Cisse tasseerso3) (A)astraight line (B)a parabola, (C)a hyperbola (0) none 5 Considet following two reactions Stal pe rode = 2 Ia e+ most > - 2 = 4 10 Gs nt a are nee ety L+) and time (sec!) as ~ [AIBEE-2002) (A) sect, M sec-? (8) M sec,M sect (C) sect, M-! sec-! (0) M secm!, sec“! Q.6 H, 925 is adsorbed on the metal surface like tungsten, This follows........... OFder reaction — [AIEEE-2002) (A) Third (8) Second (©) Zero (0) First Q.7 Incespect of the equation k = Ae-€+*7 in chemical Kinetics, which one ofthe following statement is correct? [ATEEE-2003) (A) Ey is energy of activation (B) Ris Rydberg’s constant (C) kis equilisaum constant (©) Ais adsorption factor JEE MAIN (Q.8 For the reaction system: 2NO(g) + 03(9) —» $N0,(9) volume is suddenly reduced to half ts value by increasing the pressure on it. If the reaction is of first order with respect to O, and second order with Fepect to NO, the rate of reaction will ~[ATEEE-2003] (A) Increase to eight times of its initial value (B) Increase to four times of its initial value (C) Decrease to one-fourth of its initial value (©) Decrease to one-eighth ofits init @.9 The rate law for a reaction between substances and Bis given by Rate = k [A}* [B]™ On doubling the concentration of ‘and halving the concentration of B, the ratio of the ‘new rate to the earlier rate of the reaction will be as— [AIEEE-2003) 1 (A) (mm) (B) 2 (CY) eq (0) (m¥N) Q.20_ Ina first order reaction, the concentration of the reactant, .decreases from 0.8 M to 0.4 M in 15 minutes, The time taken for the concentration to change from 0.1Mto0.025 Mis- [AIBEE-2004] (A)30 minutes (B) 15 minutes. (©) 2.5 minutes (0) 60 minutes @QA1_The rate equation for the reaction 2A + B-»C 1S found to be : rate = k [A] [8] . The correct Statement in relation to this reaction is that the [ATEEE-2004) (A) unit of k must be s"* (8) tia 1s 2 constant (C) rake of formation of C is twice the rate of disappearance of A (0) value of k Is independent of the initial Concentrations of A and 8 Q-12 Consider an endothermic reaction X —+ Y with the activation energies E, and E, for the backard and forward reactions, ively. in general [AIEEE-2005) (AE, > & (8) E, < Ey {C) there Is no definite relation between E, and E, (0) E, = E; Q.13 Areaction involing two different reactants can never be - [AIEEE-2005) (A) first order reaction (B) unimolecular reaction (C) bimolecular reaction (0) second order reactionQ.14 1, can be taken as the time taken for the concentration of a reactant to drop to of its initial value. Ifthe rate constant fora frst order reaction Is K, t, can be written as ~ [ATEEE-2005) (a 0.29% (8) 0.10/K (C)0.75%K (0) 0.69% Q.25 A reaction was found to be second order with respect to the concentration of carbon monoxide. If the concentration of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will [ATEEE 2006} (A) triple (B) increase by a factor of 4 (C) double (D) remain unchanged Q.16 Rate of reaction can be expressed by Arrhenius equation as k = Ae€/RT, In this equation, E represents [ATEEE 2006) (A) the energy below which colliding molecules will ot react (B) the total energy of the reacting molecule at a temperature, T (C) the fraction of molecules with energy greater than the activation energy of the reaction (0) the energy above which all the colliding molectles will react Q.17 The following mechanism has been proposed for the reaction.of NO with Br, to form NOBr : NO(Q) + Br (9) we NOBS, (of NOBr, (a) NO a). »2 Node (5) If the second step is the rate determining step, the order of the reaction with respect to NO (9) is = [AIEEE 2006) (Ayo (8)3 (c)2 (0)1 Q.18 The energies of activation for forward and reverse reactions for A, +B, 2AB are 180 kK) mol-} and 200 ki mol~! respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse) reactions by 100 k} mol"!. ‘The enthalpy change of the reaction (A, + B, + 2AB) in the presence of catalyst. will Gin kd mol) = (AIEEE 2007] (A) 300 (8) 120 (C) 280 (0) 20 Q.19 Consider the reaction, 2A + B -+ Products. When concentration of B alone was doubled, the half-life of B did not change. When’ the concentration of A alone was doubled, the rate increased by two times. The unit of rate constant for this Feaction is- [AIEEE 2007) (A) Lm (8) no unit (C) mol L~4s- (D) s=3 Q.20. Fora reaction A+ 28, rate of disappearance Of A’ related to the rate of appearance of '8' by the [TATERE 2008) oA a4 (0) - Q.21. The half life period of a first order chemical reaction is 6.93 minutes. The time required for the ‘completion of 98% of the chemical reaction will be (log 2 = 0.301) [AIgee 2009} (A) 23.03 minutes (B) 46.06 minutes (C) 460.6 minutes (D) 230.3 minutes Q.22 The time for half life period of a certain reaction ‘A+ products is 1 hour. When the initial concentration of the reactant ‘A, is 2.0 mol Lt, how much time does. it take for its concentration to come from 0.50 to 0.25 mol Lift is a zero order reaction 2 (A) 4h (8) 0.5 (C) 0.256 (D) 1h Q.23 The rate of a chemical reaction doubles for every 10°C rise of temperature. Ifthe temperature Israised bby.508C, the raté ofthe reaction increases by about TATEEE 2011] {AY24 times (B) 32 times (C) 64 times (0) 10 times Q.24 For a first order (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 Ais 0.01 M, Is : [AIEEE 2012] (A) 3.47 x 10-5 M/min (B) 1.73 x 10-4 M/min (C)1.73 x 10-5 M/min (0) 3.47 x 10-4 M/min Q.25 The rate of a reaction doubles when its tem- erature changes from 300 K to 310K. Activation energy of such a reaction will be: (R = 8.314 JK"! mot" and log 2 = 0.301) (A) 58.510 mol" (HIT Mains 2013) (8) 60.510 mol (©) 53.61 mot (0) 48.613 motC teve—u QBJECTIVE 2 The rte constant forthe reaction 280,440, + 0, 1s 3.010% sec" tne rates 2.4 10? mol tre sec", then the concentration of NO, (in mol litre") Is {pense 3000) (AL.4 —(B)1.2 —— (C)0.004 (0)0.8 3.1 Lis the intensity of absorbed light and Cis the concentration of AB for the photochemical process AB + hv > ABS, the rate of formation of AB* is Girectly proportional to [pee ScR 2001] we (at (or (ya 4. Consider the chemical reaction, N,(a) + 3H,(9) > 2NH,(g). The rate ofthis reaction can be expressed in term of time derivative of concentration of N,(9), H,(9) oF NH,(g). Identity the correct relationship amongst the rate expressions. (DEE SCR 2002) == Pal. Soh), 1H) (ayrates- “ge "3 a 2 at 2) 36a) (2M) (8) Rate = - Sal = 2a) . 24a = Ma, 1H, jl (cyrate = Sal. 3 a (0) Rate = Sul . Fal. ae S.In a first order reaction the concentration of reactant decreases trom 800 mol/dm’ to 50 mol/dm* in 2 x 10* sec. The rate constant of reaction in sec is: [DEESCR 2003) (A)2 x 10" (8) 3.45 x 10 (©)1.3486 x10" (D) 2x 10" 6. The reaction, X » Product follows first order kinetics. In 40 minutes the concentration of X changes. from 0.1 M to 0.025 M. Then the rate of reaction when concentration of X is 0.01M [JEESCR 2004] (A)1.73 x 10*M mine! (B) 3.47 x 105M min (€)3.47 x 10*M mint (D) 1.73 x 10*M min JEE ADVANCED ] 7. Which of the following statement is incorrect about order of reaction ? [DEE 2005] (A) Order of reaction is determined experimentally (8) It Is the sum of power af concentration terms in the rate law expression (C) It does not necessarily depend on stoichiometric. coefficients. (0) Order of the reaction can not have fractional value. 8. Consider a reaction aG + bH -+ Products. When concentration of both the reactants G and H is Coubled, the rate increases by eight times. However, when concentration of G is doubled keeping the concentration of H fixed, the rate is doubled. The overall order of the reaction is [EE 2006) ao (8)1 (2 (0)3 9.Under the same feaction conditions, initial concentration of 1.386 mol.dm-? of a substance becomes half in-40 seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio (F5) sor the rate"constans fr frst order (,) and 2e10 order (k,) ofthe reactions is (JE 2008) (A) 0.5 mol dm (8) 1.0 mol dm? (C) 1.5 mol dm? (D) 2.0 mol! dm? 10. Fora first order reaction A» P, the temperature (7) dependent rate constant (k) was found to follow the equation fog k = - (2000) 1/T + 6.0. The pr exponential factor A and the activation energy respectively, are (A) 1.0 x 10%" and 9.2 kd mot! (B) 6.0 5" and 16.640 mot! {C) 1.0 x 10*S+! and 16.6 1) mot-* (0) 1.0 x 10" and 38.3 kJ mol [Dee 2009) 11, Plots showing the variation of the rate constant (K) with temperature (T) are given below. The plot that follows Arrhenius equation is (Dez 2010) ! ! ) a© T= 12. For the first order reaction 2N20s(9) -+ 4NO-{g) + 0,19) (A) The concentration of the reactant decreases ex onentially with time. (B) The half-life of the reaction decreases with in- ‘creasing temperature. (C) The half-life of the reaction depends on the initiat concentration of the reactant. (D) the reaction proceeds to 99.6% completion in eight half-life duration. cmv 14, Ahydrogenation reaction is carried out at S00 K. If the same reaction is carried out in the presence of 2 catalyst at the same rate, the temperature required is-400 K. Calculate the activation energy of the'reaction ifthe catalyst lowers the activation barrier by 20 kJ) mot. (RE 2000) 15. ‘The rate of frstorder reaction is 0.04 mole litre s"* at 10 minutes and 0.03 mol litre’' s-* at 20 minutes fter initiation. Find the half life of the reaction. [DEE 2001) 16. 2X(g) + 3¥(9) + 2Z(9) Time (in Min) ° 100 200 Partial pressure of X 800400 200 (in mm of Hg) ‘Assuming ideal gas condition. Calculate (A) Order of reaction (8) Rate constant (C) Time taken for 75% completion of reaction (0) Total pressure when P,= 700mm. [J8E 2008] 17. The concentration of R in the reaction R-» P was ‘measured as a function of time and the following data is obtained: [rime] 1.0 | a7 | o4o | oro | Luminy [oo | aos [ ow | or | (DEE 2010) The order of the reaction is 18. An organic compound undergoes first-order decomposition. The time taken for its decomposition to 1/8 and 1/10 of its initial concentration are tyyy and ty1. respectively. What is the value of pat +10? (take 1og,,2 = 0.3) am 19. Inthe reaction, P+Q——_»R+5) the time taken for 75% reaction of P is twice the time taken for 50% reaction of B, The concentration of Q varies with reaction time as shown in figure. the overall order of the reaction is. (a2 (8)3 [Dee 2013) [alo] i} Time (yo (1[ Answer-Key ] Exercise-I rz o¢ a oo 10. D . 2c 3. OO aA 16. 0 ww 19. 8 20. 8 2B mc 2. 0c 3s. c 8 30. 0 OD 320 ue. 8B 3. moc 3a. 8 wc ac a0 aan “8 ac #_D SoA Exercise-II 7 ¢ aoc aa 10. AD 11, 480 12 AD 13. ¢ mac 45. D 16. A 7c wa 1. 6 mA 2. 8 2 cD 2. AB 2. AB 25. AC 26. A.B,C,D\ 27, ABCD ms. ABC 29. BD 30 AC 31. BC 32, ABD. 33. BC 3 ACD 3S. AB 38 a7 A wa mC wk a8 ac 43, 8 “> aA “6. 8 ann 48. 0 ak 50. A-S, B-QST, C-QRS, D-QRS SL ASR, B5Q C4P DS. 52 ASS, BYR C+B DQ SX ASP B+QS CORT DV INTEGER TYPE BA 2 55. 20 56. 5 57. 10 5a. 6 50.3 oo 3 61.5 62 6 6. 2 6 Exercise-III 2. (a) 0.04M/sec (b) 0.02 2 (a) 0.019 mol L* 5, (b) 0.037 mol Ls" 3 kak, = 4k, 4) & = KIA (BP, (i rate increases by 8 times 5. rate Increase by 27 times 6 Cr ENO). 9.10 mot titre see, (i!) 36 x 10 mol tre" sec, (ill) 54 x 10 mol litre sec! 7 (2)7.2mol ttre min, (1) 7.2 mol tre mins BE 9 (i)7.2M, (i) 10M 10, K=O.01Mmin* 44, 0.75M A, 6 x 10 sec 12h a 14, (1) 36 min, (i!) 108 min. 48, (1) 0.0223 min, (ii) 62.17 min 17, 924,362 sec. 18, expiry time = 41 months 19, 3.3% 10s" 20. 62.13 min 21, 11.2% 22, (2) Third order, (b) r= k [NO}*(H,], (c) 8.85 x 10M sec"! 23, (a) order wrt NO = 2 and wnt Cl, = 1, (b)r = K [NO] [Cl,], (e) K = BL? mot? s+ (d) rate = 0.256 mole L' s* 24, (() first order (i) k = 1.308 x 107 min (il) 73% 25. (i) rate = [AN[B); (W) k= 4 107 Mts; (i) rate = 2.8 x 109 Ms26, (i) Zero order, (1) k= $F 27, Zero order 2B. (a) n= 1, (b) $ = K(CH,COCH,], (€) 8.67 x 10 5", (4) 1.56 x 107M s+ 29. 166.6 min 30. 5.26%, 4.62 « 10° sec 32. (i) t = 13.96 hes, (11) 2.2176 litre 33. Stmin 34. 15min =p _Ps ~tm—Pa_ ~!m— 3s ape) Mee 3 ay-w) 1, _4V: 1 =tn “Ms _ hi 3a Kein ag, Keim 40. 8.12 x 10 Ms", 0.012 atm mint =") 41, (2) 90mm, (b) 47 mm, (c) 6.49 x 10” per minutes, (4) 10.677 min. 42. First order 43. k, = 2.605 x 107 min? 44 (i) = KI(CH,),0}, 0.000428 sec* 45. First order 46. (2) first order, (b) 13.75 minutes, (c) 0.716 47. 966min ‘48. 206.9 min 49, 11.45 days 50, 0.180 atm, 47.69 sec. 1 [C110 SR ay OY 53.77.7,223 Sate Amin 56. 349.1k 57, 55.3340 mole 58, 306k 59. (a) 2.31 x 10° mint, 6.93 x 107 mim, (b) 43.85 1) mole 60, rate of reaction increases 5.81 x 10 times 61. 10.272 kcal mot 621.585 63, r=KINO}(Br,) 64, r= K(NOP[H,}, where K =k, x K, kg (A A 66) Oe (bE, =E,,°6, -€, aon. 68. 53.04 68. (9) 6.25; (b) 14,37) (C) 0% «70, P, = 379.55 mmHg, ty, = 399.96 min 74, 0.0207 min! 72, 15.13 week » | 73. 0.26:1 74, 0.0805 Exercise-IV 1 2 o 5 6 C mo & 1A 12, AD 13. 3.435 x 107 M/min 24, 10010mol-! 15. t,, = 24.14 min 17. 16. (8) 1 (B)6.93 x 10min (C) 200 min (0)950 mm 1s 009,Solt Sol2 CHEMICAL KINETICS [ EXeRcIsE I SINGLE CORRECT (OBJECTIVE QUESTIONS) ] 8 B+sD=20+40 . AG) = 2819) Kent Sa tote Aleg™, RR IAL = KBP On solving: = 1.5 10-" 8 AsB + C+D k= 2303 « 10° sec" 2208, 1 ‘09 925 2.303.100 * 2303«10 28 = 10°» (0.605) = 600 sec D t. 2303 59100. 230852 « 2 SP ot t 322 2303, k= BP 2iogs = 2300.2. omne P ee re A sec, Msec* 8 From the above data, itis clear that on doubling the concentration of B, the rate is doubled hence or- der vert. Bist Simitary, Order wii. A= 2 = rate = KAP) Sol 7 C Bol 8 A+ qB -+ Products = KANBE (p+ q) may or may not be equal to 1+ m) (ordet may or may not be equal to stoichiometiic coet- ficient for a complex reacton, . Ae2B +30 4D _4A)__ 148) _ 1c) _ 0} a 2a 3a Solo SoL10 D ‘Soltt 2NO + 2H, +N, s2HO {BO 1 hd} Pa 2a a ‘Multiplying eq” (1) by 2 gives: AND}, _ Ha) , 2aNa} _ AH20 a a a” at Putting the vakve on the given questions KG YNOIHa] - KINOIM2] = 2K (NONH,) = KINOI,) Sky K) 2K, #K wa(Z! tay (ah (oy Wah a2 35/500)" 350 GPRS toh = (1092 = y= 20-min at 300 K U3, =Smin at 320K 0.693 hat ee ‘Aa300R #20 7 ea i er Ry -35! nae 0-3]‘Onsotving, Ea =55303.12J = 553K Bol. 12. A-Bec 7 ent 3 fa 2.303l09(3.8*10") Ea= 100 KJimol 801.13 D Attemperature = = Rate constant = Anthenious constant Sol. 14 AB Fit UBM, ABSI_1 ASP ‘Since K, <<<, *mostimp. peack wil be higher PE. ‘Onty one option because E,=E, + AH.O. reaction SOL ITA In a reaction, the threshold energy is equalto: ‘Activation energy + Normal energy of reactants. Soh 18 A wis 198 log k= 15-108 E249" 10 Ks Sol.198 1 ‘69 «| \ wT When tine cuts axe eos fete) When lect X-axis fa a beg as 5 Sol. 208 Kea=tos! Eas 104.4 Ksimol A=6* 10" Value of rate constant at T = * willbe equal to frequency factor ie. A= 6» 10" x" Sol. 21 B 1 Rate a Since, ‘Rate becomes four times by doubling the concen ation of A > Order wet Ais? ‘No, ‘by doubling the concentration of B, the rate becomes double = Orderwact Bist.Sot 22 8 Sol. 28 B Ph-N,Cl_N/Gu, Ph-cleN, Hal fe is independent of concentration = reactions of frst order Ph—N,Cl>PACI+N, to OOF oo ag 12300 Ax ox ok 1 Kgmin® tee o AOA xa 10 $ot23 8 Aa50 Prete) 2.303, Ao ka eae 50 20 1 2303, 10 og: 303 0:60 2 1 036 . Since, Rate constant wil be equal 303 . So (00 (1.25) mer" soize D A + 8 — \c * to Ge, oo te30 a! 2 x eS snr soronWee,-26h « B tei=20,- 0 = Me Thy) von [S]) > Re AE 3 soi30 D #01). yoo seree? Dopion ia comect. seiat D woes x so BO a bp! = 200 colt) = 2p + p'# 3p" = 300 , * 2p" = 300 @)ke ton 2e soit 8 Zi" 200 1 k = tomas 1, ke sai pe ty 19 = None it comect fh S0l32 D OF ek * 100 a 2 tot fC Solo A = t,aC,* 2A = B +3C Io 3 6, (where nate order of reaction ) : St-n=t22n=05 2c 4, 30 Sol33 A 144 Solse D Sols? ¢ 3 ae TAP KBHC 3 BE 3, (AP = 9 BHCY nl) from2*reacton oc . “2a (Mr « = Sesaner m sols B _.% Slowest steps rale determining sep. From ay ) = SK IAP 3K IBICT ~ 2K {CY Avzeec +0 AB, XiRapiey 0 sais c wt Ao @ 2A, B KL, 3K, 22% 10% 0c", K,=3. 10 Lmobsec Yo {0 Faw) a) From the unit of rate consiant fo the given 8- Rate = KDXIC] a) quental reactions, itis cler tha frst reaction is of ‘Since Xisnotin the orginal action, hence thas frat order the second reaction is of second order. tobe alimnsted once, rate law fa given a8 1 Rate = K\(A}-KJ8)* from eq? (1}.K, = Tae) =P = K (ANB) solaic Putting this vaiue in ear (4), m/sec = (K,][M/L}? Rate = KK AIBIC) (K\] = UM sec Rate = 1c (AIBC) MU sec" = (,)IM/L] > Order=3 IK) = sec 2A+B+D+E solazc A+B 40+ (Slow) A 48 A+ E Fast) ar) <> Rate = KIAIB} Arx ne {As sowest step is rate determing step me Ane x= Ao x aol Hs “ $3 rani, on‘Solas 0 ‘Complex reaction order of reaction depends on rate determining step (RDS) x Y y are not related to a & b. Solaac All the reactins = k{No][NOBe,} Rate of reaction expression do not contain chtermediate r= k{NO}(Br,) 2NO + Br, + 2NOBr t Ea (Backward) = A+B solasc A+B + 2c Axx Ronen Se vm ae an yer ? 0.05 fay= 2S ~ 0.0125 Sol49D wnfte 2[ 85st) 1 geile Solsoa Ria = 28h Rag = RYpF Sols, 20 mt 2% 10011 —p 25rd whan out H,0, + KMnO, > n=? n=5 {et normality of h,O, = N Nx25 = 37.5 x 0.03% 5 N=0.15. [15 = 20x" N=0.75 Initial normals = “O° = 3 K=log4 = 0.602 A,- 2k tae +e 0.15 Aeor inc.syx 22 at tesnane [ORRECT (OBJECTIVE QUESTIONS)] Sol7 4B -4A a at = Ayke™ logt x) = loga, ~ ktloge 2 Kloge = 75 Into _ 2.303 ss = 0.46 Solo A 9. Soh10 ABD tq = 100 days entry = sour Qo 60° ~(x,) + 429(x, segs) #2000 eit xe "2 = 120° -168%,SoLi3c Order = reaction ‘complex reaction. Soliac eg. Zero order reaction completion time can be determind for order > 1 time can be ‘determined SolisD fa>0 order -% Ke" fap ‘SOL16 A Awe A IAN) Tekt + Kt SL7A Ea, > Fact sH>O Solas A Solio Sol20A Sol218 Catalyst forms an alternative path for reactant to convert into product thus decreasing activation energy. Setz2 ¢D 20,(9) et 30,19) ‘Slowest stepis rate determing stop rate = K(O,IO} ......(1) Since, [0] is natin the cxiginal reaction hence i has tobe ehminated. From frat sep {0,10} Kil03) Ke 10s) == 10a AQ) Putting the value of (O] in the eq. (1) 103) mie = KK (Oy}iQ3) Rate = K(O,P{0,"" ‘S0l25 ‘Since [0] = [Rall the times, pho a a4 Lt yc K, = 1.26 10% sec? ky = 98% 10% coc" K, = ic 100 = WBE (Gj 100" 78.83% k, = he ato = MC ig Sy 100 23.17% ABC Energy of actvation can never be negative (Option (0) is incorrect.Sol26 BCD COnty ans wall be given ABCD (A)Forzero order reacton =o hn* 3 = yg. 85 (inital concentration ) (8) Forfirst order reaction Average Me™ 1.44 «hall te (C) For tr¢ order reaction 1 ya" Rtg (Co™ intial concentration) ae Also Kt = wf 2 8, "KG Kee a & + Gol4 Co -Sety2 Ste dehy 2.303 45100 ons as 0a yo 100 min ABC Rate = KIAFIB) > ralewst B= 1 Overall order of the reaction = 2+ 1 = 3 for a complex reaction the rate determing step Is ‘determined expenmentally. Solz9 BO {In SN! reaction, formation of carbocation takes place whichis planer. = equimolar misdure of (1) and (il) wil be formed in cate of SN’, In SN? reaction Nuclaophile will attack from the opposite to leaving group = Product I!) wil be formed in case of SN? reaction. Sol3t Ac lesyKimin 09K *)o9 A 2503RT log A=55A= 105 E, 2000 ft. 2303RT 7 E, = 2000 « 2.303 « 8.314 cal E, = 9.212 Keal Bc aA 8 Rate = KIH"HA) Rate = KTAy Hi has greater value for HA = [H*] has tobe large = for that acid has be stronger = [HA] is strangers that HE, ‘Also Relative strength = 2 ABD From figure iis clear that E,{forward) = y E (teckward) =Z ates ex ABC From the given data, W's clear that (A) keeping [8] constant, After doubling the concen- ‘ration of [A] makes the rate of reaction four times. = reaction s of order twow.r1.A. (6) Simtarty order wrt B= 1 (C) Rate = APB) Bx 104 =K «(25 104} «3.0% 10% 3K = 267 +108 mot? st (D) order = 2+ 1=3Sols ACD ya 0f (A) z0r0 (C) second (0) third order varies with ‘concentration. AB (AVA _Ea-Sobcat aH 10KCal Ea (backward) = 60KCal yA _Ea-sOhea AH = — 20KCad Ea (backward) = 80KCat (C)A _f2-S0ieal_, BAM = +10KCal Ea (backward) = 40KCal (O)A 2-80 8 aH= + 20KCal 2 f=1-04 Putting the value of kin romeqr{t) fete ° 2 Es aly c y 2ax-yst aetyet zo, 41 KIA) Meas! oP Beeston, enn =) =I BBY conf) Solving (1) and (2) No. of Moles of 8 = 2. 2208 =0.668 8040 A E log k= logieA- SagteT, When E, = 0, k= 32 *10° aides not depend on T Sol4t B Wen E, = fe. max, Kao ioe WOU be maxhoe Menge t2 27ers 3h, * 6k, =2, (oy mutipying wih 6) ‘S0LA7 A AaB wooke = 1282104.) e {ook = loga. 2.303RT ry ted TS Soles D g, 125-104 fe. 280, + 0,-+280, 2303RT T = Ee2suK Solas D Exponential tacior = 0 when T= = Free radical combination, Energy of acivation + Threshold energy = | Souda Foran endothermic reaction sotse te =e if temperature increases. k increases ': decreases. A-S B-Qs, c-5.Q 0-Q.Rs, theonttical question Sol51 AR,B-O.C-,D-S From the figure itis clear that. A, +B; == 208 (A) Eat = 40 Kstnol {C) ales = 10 KJimolAss ~ A+P.B+0S8, C+RT D-V Sotsa The reacton iso! fist order as can be seen from the given ata ‘Aso, Rate = K(H\Comples Weave s=1 and tig @ HTP trom give data (yah 1 1K qq vend 1 = 058 Kooap 2) 09" (1) ea. (2) 20min 60 (a—x) +40 x- 80x" 5 60a 100x=5 30- 100x= 'No. of moles of Ais becoming hai after 20min ty 20minKn Krre 3,1, =203K,T, #276 K Beh TT « (w)2s0ste 2 « aeze &, (2 F Uiasz76 E, = 10453.95 cal = 10.454 Keal « (o)Auo.2.903169 £2 « This time, E, = 10.454 K cal, T, = 313K, T; = 203K Ka _ 10454210? 313-293 2.303109 K, 2 3-293 x Ky omen? ak "Ka ty ket * ime ‘Also. i juice is not spod upto 64 he at 20°C it wil not spall upto 192 hr at 20°C. ‘Sentarty'we canhave seen th 2205he K, Ke Behe Ky a2 For the change, A-+B 20% solution of Adecompotes 25% in 20 minutes at 25. Letamount of solute undergoing decay ‘amt of solute let (2 x) ater 20 minutes 20 = 70( 75) a5 = 144+ 10° ier? al Ka 2303100 KS = Kug__ 701000] 31 208 2.303109 Goj4q ~ 8314 (3134296 Kyg = 5.58 10? mi? ‘The reaction if carsied out by 30% solution shows the left amount (ax) = min 20 min 2303 Keep “WS ax 2303 558% 107 = 28 30 "0m m= 9.63 ‘% decompositon = [(a mya] * 100 += ((30-9.83 y30) « 100 = 672% neo AL ders ero tek = 4000 TAL, AL = kt aA. 200 1.2 Na Be” Tag ~ 4M g 700 0c = 18800. A+2B 4c =P, Py =KO4 x06? osno4y 1 k10.4x0.6" 0.36 ©” k-05-04" “0.12 “3Sols 200+0,-+260, 4x10*= K (0.02) (0.027 1.6*10*=K (0.04) (0.02P 1.610" “aor 4°? a=2 ‘8x10 = K (0.02)(0.04" 1a 2lz) oe 4104 #K (0.02) « 0.02 =k A810" 2610) 980 10°K tn (AL aed TAL A), #2 aya 2K, 13.86 Paka IAP KA) 0.693, Ko K. #00683 =k = (0.01) 0.693 Ko K._,= 0.00693 = k (0.001) 6930 BP 10-17 yet xeyetere2 =100 Sotes k= 1.66 Ki 0.168 0.166 tte 0.166—1__ SUBJECTIVE QUESTIONS 7 +0 02 Sota (a) AAA) . 04-08) . 92 004 > SME) a sense -ANH4y) | 402-04) 02 _ a 2-04) 02 «492 ti PEON. 6x NON ga uso Sot B05"), 9058 rep soir a) SHO 228) eae age72 at 3 7 at => TARO], =-ABO;1 , AB] oy EPH ara Er at” Bar 5 sous A +m ceo > k= 0000 PRizo 0808 a oo iso, BCL. 2 o0sei@o7 Mferreaction 06-x 08-2 x x = K=0037 “0.2 gots —ANOs) , ANOz] _ 240)) eV a Tae et Wehave Ry =k ALIBP = k 06 « (0.87 KIN,O4] = ZKANLOI = 2k, Mal PavsINBok 04s 47 Raat 1 Rs Ky = J Moe ky * sete ae ns on x Bold 0) Ge MIANBP = 7, ® neem ee . wyet2 102" 10% 60872M (WH) ry = KI2AN2B} = 6r, y= 1.2 = 10°? = 20 * 60 = 14.4.M (Not possible) [B) att = 20 min = 10M ‘Sols 1, = KAP (B,) Sol10 Tne [A] Fy = RISAP (38) 00 010 1 : hig }xro01 upon reccing 3 10 © 0.09 = 0.02 = 77 (AF 1B) = 27r, 20 008 mt Hence thee zero order reaction. Now x oot=kx1 k=001Soltt t=0 tet xekt x= Ze 102" 25 = 0.50 Now, a- x= 0.25 =025+0.50#0.75M Soltek wehme x= (intial conctofH*) atthe m1 gates 107 sts A > 8 ‘aherreacton (1-0.75) = O75=k=k= 60 = 08 ke "60 when x09 09 t= 2806012 hour Soir yg 72min = 2 hal roe 1y938 me iq? Shall ves 3.6% 3= 1.8 min 80118 (= 2.20%! = 223 mir 2.303, 1 (2303 joq100 | min = 62.11 see. ot ($a jones Solt6 Solt7 Bolts ‘Sot9 2303, 1 soize k= 2S bog ste $93 « 62.23 min 2.303 |, _100 Sota *= 90.60 !°9700-% "22 * 10% = KEI $0L22 [2] keeping conc” of H const, when INO] is doubled. the rates 4 bmes. keeping INO] constant, when [H,]!s doubled therale is doubled rate = k [NOP [H,} order of reaction = 3 fb] rate = K [NOF [H,) = 44104 (157 «107» 45107 {e] rate = K(NO} [M,] = 0.85% 109 M sect = « BoL23 [a] order wit. NO=2 order wrt. y= [by rate = K (NOP ICL] 1510", seats lel k= aayyoosy = OL more {6 rate = [C1] INOF = 0.256 Sot2e ky = SP eo013 0.893 5 1 a= tag 200.013 0) ASK, =k, the reaction is of the first order © = 0.013 mie? i) 7%sus ceerer | 4 104k (0.177 [0.1 24109 =k (0.5 (0.17 @ Equation 2¥(1) sor" = met so, 2 «107 =k (0.5"(0.1" 8 19107 =k OS" OS! “ Equation (49(3) sr = nat @ Rate = K [A] (8) (H) Rate = 4 » 1072 (0.2) = (0.35) 228010 Met Soler 0 100-200-300 DP) OS * 10> 1103 1.5 «10? SP) gsxt0 08=10 05% 10 a 220 kconatnn)=5 Pa) pemacten a rot siz treed tava Atematvay (sh loot) P= 1 fog(a,),=Toola,), Sol.28 Rate = KIA" Rate K (6* 1027 = 5.2104 KOH P= 78x05 B67 x 103 et (©) > Rate 8.67 109 «1.8 «10-9 156 «105 Me a a «ay Sol3t sctazt, = 2999 0689 6) t= 228g 9 13900 @ —_NH.NO, —+ N, 049) + H,00) No. of moles. 0.1(1-0.98) 0.088 0.099 ORT, 0.090+0.082.273 ‘Volume of H,0= 9 =2210L, Sol33Time =A} [8] 70 a t= 84 a t= 84minSots4Time [A 8 Pro = in —M_ (@y-Ve) Sol3e Am) mx t=0 8 oo tet anx & 3x ts© 0 a Now, Vyp (a—x) + 2x6 3x V,¥ (aan) 0 Aso, Vyu5a @ From atm equsten SV, u (Se + 20x) @) From equation (2) and (3) 5V,-V, 20x My dy, B yy we ay YY ws any BBS MM (13-2) Re* 0a2. 78-607300 sez ie!Solat As mec to Py o 0 tet Pp-P oP OP tez 0 2, Py Gren 3P,* 270 mm Hg (a) P= 90mm Hg Also, Py + 2P = 176 mm Hg = 176-00 = P=43mmHg Po) Py-P=90-43= 47 mmHg fel k= 2209 log 9 = 0.0640 min-* fh t= 2892 10.677min S042 P,=758 at 5 Py~ x,08/2827 > x,2138 = Pp-xj=758~ 138 = 620 ‘at 10 P-2,¢3/2=882 + 1°248 Pex 510 my _ 758 -5 = from 0105 = 5 = @20 from 510 10 Po-%1 , 620 Poom, 510 ration is same first order S0LA3 2N,0,—+ 4NO, because of 7N,0y Ly Aa eon?) PyaBe dan» Peed 0 2,py2 » St Py+e=284.5 equation (1) Fo ase45 1727338 +9016 2 because reactant 2N,O, Solas —(CH,), O16) —+ CHAIG) + Hy(9) + COV) t=o 312 o 0 0 Pressure att=3008 0312p pp Gren 312+ 2P #3126 96 E r iiss "9 5rz=na5 2428104 AB kek hy the reactions of Mord Rate = K{(CH,) O} wd k= 420 = 10+ sect2.303, (13.138) We eo lit 303,50 (13.1438) too Bip eo ass 2.303, (13.1+3.8) ‘s* “a0 0 (9-38) kg = 2,308 jog (13.1+3.8 360 °9(5.87+3.8) As, kak» ky» ky, Coleulate ky ‘The reaction is of order Atzero reading , = 0 2.303, 18:3+38 Keg" Sp (09 (3.8) ond >t 866min 2.303, 100 = "eg 109 700 18:77) 2.3034, 100 *2* "350 199 700=69.12) fea to 8 ° tet ax 3 tee 0 : . 2 xp volume of O, berated at ime t ‘By volume of ©, liberated at time = 303, 46.4 = te A 00 (46 34-20) = 1145 days, Sol50 —2Ng)—»4Bg)* Cia) ts0 01 °° Pp tet ot-x om cen are Boas = vs00s nso, =MAl «748 * 10914) 01 Toney Wohave, = 2808 748 + 10 = 2203 jog 0 1247.60 second Aso, 7.484 10-92 2303 jog 04 Solst a” FP fy goes] Pe govern] kok, ,-4,) _AatAle (t (AK TTARe™ 10 jg = 10-4)BASS Eqy)— Fxg) = DH E yg) = 77-72 = 8 kJ mot sea nt SOLS logk =logA~ aaha*y 0.693 gage 10% sect k= 2683 Ae 5 2 10 cee E,= 106.5% 109s mot! Ky = 346 * 10° sec! | 100-10? | 1 wenevton es» Sgr a T#306K Sot50 10 K, pe O88 099 Ky * Kine 282 Ky (oilog i” 208 > E,= 43.05 KU mot SOLEOK, = agrE.h/RT Ky aah ih k, Ka VT 4 Ma ea En RT ghd esate tot oe, Solas SoL6t log Kgs * 2300R 206 308 Kage Kar #175, R= 2 Calorie moh" Ke* a “+E, = 10.257 K eal mort 380+ 273+ 683k Teme 01608 = 2S Ea = 200 « 10°J mot’ caluste 2.303 = 2308 jog 100 19704 mines Sol632NO + Br, —+ 2NOBr 1 NO + br, lait» Nowe, K NOB, = ky INO} [Br]rate = ky yg INOF 18] gq INOP [Be] SoL64 rate =k, IN,03)H,] wa ot! = INO} = k, [NOP rate = yk (MOF H,) Sol6S rate = k; 1031 N,03) we NOp nor W,0) = {mor rate = 110 Nor NO.) = BO -nmorioy Sotee ase 64D, dc) SO = KNB) - KCI - Kc} Asteody site Sl «9 KYAIB) = (= K, +K3) go) K Neo, Ma "KCI" “Gg + Ka) i Neo, Ky ES an 06, 27K) AdAy griEas-£o, £4, 0A -% Comparing LHS &RHS AWAY asp ond Ea = Ea, + Ea- Ea, ol) “The amt lef afer 2 he (no. oft," 4) 24) «cage KA? for order as tAly = [Blya ote tke 700-78 * 100 ait 4.38. 25 100 ~ 100 100 ox 20 25.7% traction = 14.3% (©) For zero order, (Al gine ae a, Se emntian Sole - Spe] 2k, prot - kure,ora,rte1 Kg forgven reactions jet SoL70 2%) > 40g) + Rig) + 5) 20 Py 0 0 (328 PP (mm Hg) Pe tesomPpP eS aS Pe tee 0 a, § 25 com 27+ os2s-6i7 = B vous oase Pp Ea bP Poms Fa Pye TF a37 325 =7845 aPs338 PP = 200 2.30%joq_P2 30 Ke =293.8 + 113.264 325 = 379.55 mm Hg Sol7t Br Brees intial a 0 20+ 8" »Bre tete-ge Se+ Bo" Bm" Let normality of reducing agent be N thus at t=O, ax2=N«2S 2a =25N at tetann). 260.55 32N x= 7N303, to vGo- 0 Ke 3.956 2.303, kee 956-1267) 3 weeks Sol73 CH, -O-CH,(g) +CH,(g)+ CO(g) + H,(9) t=0 04 ° ° ° Mer Od-x x x 04-x= 0.110 x=04~0.110 =0.290 = Olt 46 + 0.29029, 28402042 S0t74 Total pressure at = 10 sec, Tago 86K , 2A y_g-6 ok, )0) Ky+Ke te IAb lteter * Keke Neo, t= = 2 Ke [ee akan ts yok Ky Kyoky “15> Kony 12S Ka > Krk 798 Aso, erteonar Ka eI Lg 11K 3 KK 10 9 8g 315-059 X>10= 04 = (Ky) "10 = In (02) (0.2) akon Mg 016 * K,= 05 «0.16 = 0.0805 nA B ar) arae xeajt- om)SS Varo. of moles So. ay - x4 x uv. Yo te ag ~ ag(t- 0K - 1) .——___4— a cae] ete -1- (ape ete] Also, ts 2 = Notte10 timer, mole. litre. ina* a straight ine M sec’, sec! c Zoro A E, is energy of activation A Increase to eight tmes of ts initial value % 215 minutes number of half lifes = 2 (for change of 0.1 100.025) i230 minutes n 12 1 % 7. 3 value of kis independent ofthe initial concentrations of AandB DH =, ~ Ey ForDH = postive E Unear variation of ‘conc. with time suggest that itis zero order reaction wrt Ot Time tye ® Mbp, > Mordeswrt Hence rate law expression c= KIPY [Oy over allorder= 101