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Q.

The rate of a reaction : A+B⟶A + B \longrightarrow product is given below as a function of different initial concentrations of A and B.

Experiment[A]/mol L−1L^{-1}[B]/mol L−1L^{-1}Initial Rate/mol L−1L^{-1} min−1min^{-1}
10·010·015×10−35 \times 10^{-3}
20·020·011×10−21 \times 10^{-2}
30·010·025×10−35 \times 10^{-3}

Calculate the order of the reaction with respect to A and B. Determine the rate constant of the reaction.

CBSECBSE Class XII Board 2025Subjective· 3mImportance★★★★★
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The reaction is zero order in B and first order in A (overall order = 1). The rate constant is 0.5 min−10.5 \ \text{min}^{-1}.

Why this approach works

The rate law for a reaction A+B→productA + B \to \text{product} has the general form:

Rate=k[A]m[B]n\text{Rate} = k[A]^m[B]^n

where mm and nn are the orders with respect to A and B. To find mm and nn, we compare experiments where only one concentration changes while the other stays constant. This isolates the effect of that single reactant.

The key insight: if doubling [A] doubles the rate, the order in A is 1. If doubling [A] quadruples the rate, the order is 2. If changing [B] does nothing to the rate, the order in B is 0.


Step-by-step solution

1. Find the order with respect to B (nn)

Compare experiments 1 and 3 — here [A] is constant at 0.01 mol L−10.01 \ \text{mol L}^{-1}, while [B] doubles from 0.010.01 to 0.02 mol L−10.02 \ \text{mol L}^{-1}.

  • Experiment 1: Rate = 5×10−3 mol L−1min−15 \times 10^{-3} \ \text{mol L}^{-1} \text{min}^{-1}
  • Experiment 3: Rate = 5×10−3 mol L−1min−15 \times 10^{-3} \ \text{mol L}^{-1} \text{min}^{-1}

The rate is identical. Doubling [B] produces no change in rate.

Rate3Rate1=5×10−35×10−3=1=(0.020.01)n=2n\frac{\text{Rate}_3}{\text{Rate}_1} = \frac{5 \times 10^{-3}}{5 \times 10^{-3}} = 1 = \left( \frac{0.02}{0.01} \right)^n = 2^n

Since 2n=12^n = 1, we get n=0n = 0.

Watch out

A common mistake is to assume the order in B is 1 just because B appears in the reaction equation. The data clearly shows B has no effect on the rate — the order is zero, not one.

2. Find the order with respect to A (mm)

Compare experiments 1 and 2 — here [B] is constant at 0.01 mol L−10.01 \ \text{mol L}^{-1}, while [A] doubles from 0.010.01 to 0.02 mol L−10.02 \ \text{mol L}^{-1}.

  • Experiment 1: Rate = 5×10−3 mol L−1min−15 \times 10^{-3} \ \text{mol L}^{-1} \text{min}^{-1}
  • Experiment 2: Rate = 1×10−2 mol L−1min−11 \times 10^{-2} \ \text{mol L}^{-1} \text{min}^{-1}

The rate doubles when [A] doubles.

Rate2Rate1=1×10−25×10−3=2=(0.020.01)m=2m\frac{\text{Rate}_2}{\text{Rate}_1} = \frac{1 \times 10^{-2}}{5 \times 10^{-3}} = 2 = \left( \frac{0.02}{0.01} \right)^m = 2^m

Since 2m=22^m = 2, we get m=1m = 1. …

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