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Q.Define order of reaction. Predict the order of reaction in the given graphs, where [R]0[R]_0 is the initial concentration of reactant and t1/2t_{1/2} is half-life:

(a) A plot of t1/2t_{1/2} (y-axis) vs [R]0[R]_0 (x-axis) that is a horizontal straight line — t1/2t_{1/2} is independent of [R]0[R]_0.
(b) A plot of t1/2t_{1/2} (y-axis) vs [R]0[R]_0 (x-axis) that is a straight line passing through the origin with a positive slope — t1/2t_{1/2} is directly proportional to [R]0[R]_0.
CBSECBSE Class XII Board 2019Subjective· 2mImportance★★★★★
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The half-life method distinguishes reaction orders by how t1/2t_{1/2} depends on initial concentration. A horizontal line (constant t1/2t_{1/2}) means first order; a line through the origin (t1/2∝[R]0t_{1/2} \propto [R]_0) means zero order.

What is order of reaction?

The order of a reaction is the sum of the exponents to which concentration terms are raised in the rate law. For a single reactant RR decomposing as R→productsR \to \text{products}, the rate law is:

Rate=k[R]n\text{Rate} = k[R]^n

where nn is the order. The order tells you how the rate responds when you change concentration — and that directly controls how the half-life behaves.

Why half-life reveals the order

Half-life (t1/2t_{1/2}) is the time taken for the concentration of a reactant to fall to half its initial value. For a reaction of order nn (with n≠1n \neq 1), the general relation between t1/2t_{1/2} and initial concentration [R]0[R]_0 is:

t1/2∝1[R]0 n−1t_{1/2} \propto \frac{1}{[R]_0^{\,n-1}}

For n=1n=1, this formula breaks down (division by zero) because the half-life becomes independent of concentration — a special case.

Let’s see what this means for each graph.


Graph (a): t1/2t_{1/2} is constant — horizontal line

  1. A horizontal line means t1/2t_{1/2} does not change when [R]0[R]_0 changes.

    So t1/2∝[R]0 0t_{1/2} \propto [R]_0^{\,0}.

  2. From the general relation t1/2∝[R]0 1−nt_{1/2} \propto [R]_0^{\,1-n}, we set the exponent equal to zero:

1−n=0⇒n=11 - n = 0 \quad \Rightarrow \quad n = 1

  1. This is the first-order case. For a first-order reaction, the half-life is given by:

t1/2=ln⁡2kt_{1/2} = \frac{\ln 2}{k}

which contains no concentration term — it’s a constant for a given temperature.

Tip

First-order half-life is the only one that doesn’t depend on how much reactant you start with. That’s why radioactive decay (always first order) has a fixed half-life regardless of the sample size.


Graph (b): t1/2t_{1/2} is directly proportional to [R]0[R]_0 — straight line through origin

  1. A straight line through the origin means t1/2∝[R]0 1t_{1/2} \propto [R]_0^{\,1}.

    So the exponent of [R]0[R]_0 is +1+1.

  2. Again using t1/2∝[R]0 1−nt_{1/2} \propto [R]_0^{\,1-n}, we set: …

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