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Q.What is meant by Half life? Prove that half life period of first order reaction does not depend on its initial concentration. OR Derive expression for rate constant of First order reaction.

Madhya Pradesh MpbseMP Board Higher Secondary 2020Subjective· 4mImportance★★★★★
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The half-life of a first-order reaction, derived from its integrated rate law, comes out as t½ = 0.693/k — a constant depending only on k, with no dependence on the starting concentration.

Half-life (t½):

The half-life of a reaction is the time required for the concentration of a reactant to fall to exactly half its initial value.

Proof that half-life of a first-order reaction is independent of initial concentration:

The integrated rate law for a first-order reaction A → products is:

k=2.303tlog⁡[A]0[A]k = \frac{2.303}{t}\log\frac{[A]_0}{[A]}

At t=t1/2t=t_{1/2}, [A]=[A]02[A]=\dfrac{[A]_0}{2}. Substituting:

k=2.303t1/2log⁡[A]0[A]0/2=2.303t1/2log⁡2k = \frac{2.303}{t_{1/2}}\log\frac{[A]_0}{[A]_0/2} = \frac{2.303}{t_{1/2}}\log 2

Since log⁡2=0.301\log 2 = 0.301:

k=2.303×0.301t1/2=0.693t1/2k = \frac{2.303\times0.301}{t_{1/2}} = \frac{0.693}{t_{1/2}}

Rearranging:

t1/2=0.693kt_{1/2} = \frac{0.693}{k}

This final expression contains only k — [A]0[A]_0 has cancelled out completely. So the half-life of a first-order reaction is a constant, independent of the starting concentration.

OR

Derivation of rate constant expression for a first-order reaction:

For A → products, first order:

−d[A]dt=k[A]-\frac{d[A]}{dt} = k[A]

…

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