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Q.

Following carbocation undergoes either methyl shift with rate constant (K2) (or) hydride shift with rate constant (K1) from same carbon at 300K. Both elementary reactions follow Arrhenius equation and have same pre-exponential factor

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*labeled carbon represents radioactive carbon from which methyl or hydride shift occurs
If  K1=116K2, then find ( a – b) in units of K. cal/mol
where ‘a’ and ‘b’ represent energy of activation (k. cal/mol) for formation of

  Question Image and  Question Image from given cation respectively. 

R=2  calmol1K1loge2=0.70

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answer is -1.68.

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Detailed Solution

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K1K2=116 Ea1Ea2=4RTln2=168k.cal/mol 

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