Chapter 4 Chemical Kinetics and Nuclear Chemistry Answer the following Questions 4. The gaseous reaction ¥A(g)*>y,8(9) is first order with respect to A. It is studied at a constant pressure with ‘ax’ 2s the initial amount of A. The volume of the system at time "t'is given by the expression, V = Vo (2-e*) Whore Vp is the volumo of the system at t = 0. Assume ideal behaviour for gases thon value of { “2 | Ww is 2. Reactant A dissociates into different products in concurrent reactions as given below Reaction |: nA 1 Reaction I: n,A —2-+C Reaction Ill : A —2-»D IF all reactions are elementary then total rate of disappearance of Ais —aAl at KAT! + 2k, [AJ + 3kyfAy* The value of a, +, +n, +x is 3. Consider the reaction 2Br + H,0, + 2H’ Br, + 2H, Mechanism Step-l : Br +H,0, +H’ —2>HOBr + H,0 Step-ll : HOBr+ H’ + Br —29Br, +H,0 ‘The value of ky and k, are 10° mol L? sec~* and 10 mor? L? sec respectively Ifthe rate of formation of Br, (in mol L~' sec") when concentration of 81°, HzO, and H" is 0.1 M each isa x 10° Then the Value of a + bs (use steady state approximation) [Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-4762345510 Chemical Kinetics and Nuclear Cherristry (Levelt) 4, The extent of a reaction is defined as where n? and n are the number of moles of reactant or ¥, product(species i) present al the commencement of the reaction (t = 0) and at any time t respecively vis the stoichiometric coefficient of the species ‘i in the balanced equation. For the calculation of the extent of reaction, the stoichiometric coefficient is considered to be positive for product and negative for reactant. ‘The extent of the reaction is the same for all reactants and. products. For the reaction N,(g) + 3H,(g) > 2NH(g). When 0.3 mol of Np and 0.8 mol Hy are taken intially After certain time 0.2 mol of Hy was found in reaction mixture . If the extent of reaction at this instant is x then the value of 10x is 5. Ammonia decomposes on tungsten wire at 1000 K as given below NH3(0) > 5% (6) * SH) ‘The following results were obtained in a constant volume system P (torr) ]310 | 321] 332 | 354] 376 tysec) [o | 100 200 | 400 | 600 ‘The Rate constant of reaction is Z tor s*’ then 100Z - 2X ~ ¥ (to nearest integer) 6 2X(g) > 3¥(g) + 2Z(g) Time(in min.) 0 [700] 200 Partial pressure of X [inmmof Hg] | 600 | 400] 200 Assuming ideal gas condition, calculate () Orderof reaction (i) Rate constant (ii) Time taken for 75% completion of reaction (W)_ Total pressure when P, = 700 mm of Hg 7. Achasahalflfe of22,0years with respectto radioactive decay. The decay folowstwo paralel paths, one leading to22Th and the other to °F. The percentage yield of 22°Th ie 29%. What are the decay constant(A) for each of the separate paths? ‘8 Rate constant for the decomposition of ethylene oxide into CH, and CO may be described by the equation oak 606") = 10.4 ~ 125210" (i) What is the energy of activation of this reaction in kJ mot'? (i) What is the value of k at 670 K in s"? 9. A hydrogenation reaction is carried out at 00 K. If the same reaction is cartied out in the presence of a catalyst at the same rate, the temperature required 's 400 K. Calculate the activation energy of the reaction, if the catalyst lowers the activation barrier by 20 kJ/mol. ‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-47623458(Levelt) Chemical Kinetics and Nuclear Chemistry 41 10. Acounter rate meter is used to measure the activity of a radioactive sample. At a certain instant, the count rate was recorded as 475 counts per minute. Five minutes later, the count rate recorded was 270 counts per minute. Calculate the decay constant znd half Ife period of the sample, 11. Ifor ihe fist order reaction, rate constant varies with temperaiure according to the graph given below. At27°C, 1.5 * 10 percent of the reactant molecules are able to crossover the potential barrier. At 52°C, the slope of this graph is equal to 0.2 K~'s~1. Calculate the value of rate constant at 52°C, assuming that activation eneray does not change in this temperature range. Rate constant Temperature (t) 12, At380°C, the haf life period for the first order decomposition of H,0, is 360 minutes. The energy of activation of the reaction is 200 kd mol’. Calculate the time required for 75% decomposition at 450°C. a 13, Temperature coettiaent Hj °S° of areaction s 1.82. Calculate tne energy of activation in kcal mo 14. The following data were obtained for a given reaction at 300 K Reaction Energy of activation {ksi (1) Uncatalysed 76 @) Catalysed 57 By what factor the rate of catalysed reaction is increased? 15. Consider the hypothetical reaction A + 2B — Product Table given below gives the kinetics for the above reaction at 27°C. Exp. Nod iy] (mbie) (me 1 0.01 | 0.01 | 693% 10° 2 | 002 | 001 }1386% 10% 3, 0.02 | 0.02 | 13.86% 10° Which of the following is correct statement? (Arrhenius factor 02 ¢) (1) Rate of reaction becomes 1.73 x 10° Ms" after 200 s, i inital concentration of A is 0.01 M (@) Rate of reaction becomes 1.73 x 10°° MS“ afler 100 §, finial concentration of A is 0.01 Mt @) Activation energy ofthe reaction is 7.46 kulmot at 27°C (4) After § minutes, rate is 1/16 times of bial rate if intial concentration of Ais 0.01 M ‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tawer, 8, Pusa Road, New Delhi-110005 Ph.011-4762346612 Chemical Kinetics and Nuclear Cherristry (Levelt) 16. Consider the reaction A+B oP Initialy 0.2 M of A and 0.1 M of B are present and concentration of 8 becomes half of initial concentration i 100 seconds, then the rate consiant K Is [In(0.67) = ~0.405] (1) 405 » 10? Me (2) 2.85% 10? M's @) 14 102 tet (4) 3.76% 107 wrist Paragraph for Q. Nos. 17 to 19 Rate of reaction is determined by differential rate equation but this method is not convenient to determine the instantaneous rate. It is difficult to measure rate and order of reaction from differential rate equation. So integrated rate law is used and integrated rate law is different for the reactions of different order. Consider the reaction, nA —> product 1 Graph (I) between 3 and time is given 3 Time (minute) —> Graph | [wnere A, > Concentration at time t, K > Rate constant] 17. inital rate of reaction 's x and rate of reaction after 1000 second is y then 5 is a2 (2) 02 @ 3 (4 18. Which is the most appropriate graph of ty Versus [A], for reaction given in Q.1T? t te ) @ L___, L___, awl tal t t te he ) @ wl ‘wl ‘Aakash Educational Services Limited - Regd. Ofice : Aakash Tower, 8, Pusa Road, New Delhi-110005 Pr.017-47623458(Levelt) Chemical Kinetics and Nuclear Chemistry 13 19. ty, of reaction given in Q.17 is (1) 1000 s (2) 100s (3) 2000s (4) 200s 22. Te reaction) in which poston emission or K-apture tke place () Za 53 Mg 2 kK 8a @ fo—}'e ) Bos 87 Ba gaa ‘Aakash Educational Services Limited - Regd. Ofice = Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623466