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Question: The time elapsed between \( 33\;% \) and \( 67\;% \) completion of a first order reaction is \( 30\;...

The time elapsed between 33  33\;% and 67  67\;% completion of a first order reaction is 30  minutes30\;minutes . What is the time needed for 25  25\;% completion?
(A) 15.5  min15.5\;min
(B) 12.5  min12.5\;min
(C) 18.5  min18.5\;min
(D) 16.5  min16.5\;min

Explanation

Solution

Hint : The completion of the reaction represents the change in the concentration of the compound. If we take a reference initial concentration, we can find the change in the concentration and the concentration after some time interval. From the obtained date the rate constant can be calculated. Using rate constant, time required to reach a concentration can be calculated.
Rate constant k=2.303tlogR0Rtk=\dfrac{2.303}{t}\log \dfrac{{{R}_{0}}}{{{R}_{t}}}

Complete Step By Step Answer:
First of all, to simplify the given condition, we can take the initial concentration of the compound as R0=100  MR_0=100\;M .
Now, as per the given data, when the reaction gets 33  33\;% completed, we can say the concentration reduces by 33  M33\;M . Hence, the final concentration after time interval t1t_1 is Rt1=100M33M=67MR_{t1}=100M-33M=67M
From the equation of the rate constant for the first condition,
k=2.303t1logR0Rt1k=\dfrac{2.303}{{{t}_{1}}}\log \dfrac{{{R}_{0}}}{{{R}_{t1}}}
Substituting the obtained values, and making time intervals the subject of the equation.
t1=2.303klog10067{{t}_{1}}=\dfrac{2.303}{k}\log \dfrac{100}{67} …… (1)(1)
Similarly when the reaction gets 67  67\;% completed, we understand that the concentration has reduced by 67  M67\;M . Hence, the final concentration after time interval t2t_2 is Rt2=100M67M=33MR_{t2}=100M-67M=33M
From the equation of the rate constant for the second condition,
k=2.303t2logR0Rt2k=\dfrac{2.303}{{{t}_{2}}}\log \dfrac{{{R}_{0}}}{{{R}_{t2}}}
Substituting the obtained values, and making time intervals the subject of the equation.
t2=2.303klog10033{{t}_{2}}=\dfrac{2.303}{k}\log \dfrac{100}{33} …… (2)(2)
Now, we are given that the difference between the given time intervals is 30  min30\;min .
t2t1=30min\therefore {{t}_{2}}-{{t}_{1}}=30\min
Substituting the values from the equation (1)(1) and (2)(2)
2.303klog100332.303klog10067=30\therefore \dfrac{2.303}{k}\log \dfrac{100}{33}-\dfrac{2.303}{k}\log \dfrac{100}{67}=30
1.11k0.40k=30\therefore \dfrac{1.11}{k}-\dfrac{0.40}{k}=30
Rearranging the equation to find the value of rate constant
k=1.110.4030\therefore k=\dfrac{1.11-0.40}{30}
k=0.0236min1\therefore k=0.0236{{\min }^{-1}}
Now, we are required to find the time interval required for 25  25\;% completion i.e. for the concentration to reduce by 25  M25\;M . Hence, the time required for the final concentration to be Rt=10025=75MR_t=100-25=75M can be obtained as
t=2.303klogR0Rt\therefore t=\dfrac{2.303}{k}\log \dfrac{{{R}_{0}}}{{{R}_{t}}}
Substituting the given values,
t=2.3030.0236log10075\therefore t=\dfrac{2.303}{0.0236}\log \dfrac{100}{75}
t12.5min\therefore t\approx 12.5\min
Hence, the correct answer is Option (B)(B) .

Note :
The point to note is that, here we are given the change or say reduction in the concentration of the compound. For finding the rate constant, we need the concentration of the remaining compound after a particular time interval. Hence, we should remember to take the difference of the initial (reference) concentration and the change in the concentration, to get the final concentration after a time interval.