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NCERT Class XII Chemistry
Chapter - Chemical Kinetics
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Question : 11 of 39
Marks: +1, -0
The following results have been obtained during the kinetic studies of the reaction :
2A + B → C + D
 Experiment  [A]/ mol L1^{-1}  [B]/ mol L1^{-1}  Initial rate of formation ofD/ mol L1^{-1} min1^{-1}
 I  0.1  0.1  6. 0 × 103^{-3}
 II  0.3  0.2  7.2. × 102^{-2}
 III  0.3  0.4  2.88 × 101^{-1}
 IV  0.4  0.1  2.40 × 102^{-2}
Determine the rate law and the rate constant for the reaction.
Solution:  
Suppose order with respect to A is m and with respect to B is n.Then the rate law will be
Rate =k[A]m[B]n=k[A]^{m}[B]^{n}
Substituting the value of experiments I to IV, we get
Expt. I: Rate =6.0×103=k(0.1)m(0.1)n              =6.0 \times 10^{-3}=k(0.1)^{m}(0.1)^{n}\;\;\;\;\;\;\;...(i)
Expt. II: Rate =7.2×102=k(0.3)m(0.2)n            =7.2 \times 10^{-2}=k(0.3)^{m}(0.2)^{n}\;\;\;\;\;\;...(ii)
Expt. III: Rate =2.88×101=k(0.3)m(0.4)n      =2.88 \times 10^{-1}=k(0.3)^{m}(0.4)^{n}\;\;\;...(iii)
Expt. IV: Rate =2.4×102=k(0.4)m(0.1)n        =2.4 \times 10^{-2}=k(0.4)^{m}(0.1)^{n}\;\;\;\;...(iv)
Comparing equation (i) and equation (iv)
  (Rate)I(Rate)IV=6.0×1032.4×102\therefore\; \frac{(\text{Rate})_{I}}{(\text{Rate})_{IV}} = \frac{6.0 \times 10^{-3}}{2.4 \times 10^{-2}} =k(0.1)m(0.1)nk(0.4)m(0.1)n= \frac{k(0.1)^{m}(0.1)^{n}}{k(0.4)^{m}(0.1)^{n}}
or, 14=(0.1)m(0.4)m=(14)m      m=1\frac{1}{4} = \frac{(0.1)^{m}}{(0.4)^{m}} = \left(\frac{1}{4}\right)^{m} \;\;\;\therefore m=1
Comparing equation(ii) and equation (iii)
(Rate)II(Rate)III=7.2×1022.88×101\frac{(\text{Rate})_{II}}{(\text{Rate})_{III}} = \frac{7.2 \times 10^{-2}}{2.88 \times 10^{-1}} =k(0.3)m(0.2)nk(0.3)m(0.4)n= \frac{k(0.3)^{m}(0.2)^{n}}{k(0.3)^{m}(0.4)^{n}}
or, (12)2=(0.2)n(0.4)n=(12)n      n=2\left(\frac{1}{2}\right)^{2} = \frac{(0.2)^{n}}{(0.4)^{n}} = \left(\frac{1}{2}\right)^{n} \;\;\;\therefore n=2
Rate law expression is : Rate =k[A][B]2k[A][B]^{2}.
The rate constant can be calculated from the given data of any experimentusing expression:
          k=Rate[A][B]2\;\;\;\;\;k = \frac{\text{Rate}}{[A][B]^{2}}
From Expt. I, k=6.0×1030.1×(0.1)2=6.0k = \frac{6.0 \times 10^{-3}}{0.1 \times (0.1)^{2}} = 6.0
  \therefore\;Rate constant k=6.0mol2L2min1k = 6.0 \, \mathrm{mol}^{-2} \, \mathrm{L}^{2} \, \mathrm{min}^{-1}
Unit of k,k=Rate[A][B]2k, k = \frac{\text{Rate}}{[A][B]^{2}}
=molL1min1(molL1)(molL1)2= \frac{\mathrm{mol} \, \mathrm{L}^{-1} \, \mathrm{min}^{-1}}{(\mathrm{mol} \, \mathrm{L}^{-1})(\mathrm{mol} \, \mathrm{L}^{-1})^{2}}
=mol2L2min1= \mathrm{mol}^{-2} \, \mathrm{L}^{2} \, \mathrm{min}^{-1}
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