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Q3.10:

In a reaction between \(A\) and \(B\), the initial rate of reaction (\(r_{0}\)) was measured for different initial concentrations of \(A\) and \(B\) as given below: 

What is the order of the reaction with respect to \(A\) and \(B\)?

Solution :

Step 1: Establishing the Rate Law Expression

The general rate law for a reaction involving reactants $A$ and $B$ is expressed as:
$r = k [A]^x [B]^y$
Where $k$ is the rate constant, $x$ is the order with respect to $A$, and $y$ is the order with respect to $B$. [Per the Law of Mass Action and Rate Law definition].

Step 2: Analysis of Experimental Data

Based on the provided data table:

Experiment $[A] \text{ (mol L}^{-1})$ $[B] \text{ (mol L}^{-1})$ Initial Rate $(r_0) \text{ (mol L}^{-1} \text{s}^{-1})$
1 $0.20$ $0.30$ $5.07 \times 10^{-5}$
2 $0.20$ $0.10$ $5.07 \times 10^{-5}$
3 $0.40$ $0.05$ $1.43 \times 10^{-4}$
4 $0.30$ $0.20$ $7.3 \times 10^{-5}$

Step 3: Determining Order ($y$) with respect to $B$

Compare Experiment 1 and 2 where $[A]$ remains constant ($0.20 \text{ M}$):
$\frac{r_1}{r_2} = \frac{k [0.20]^x [0.30]^y}{k [0.20]^x [0.10]^y}$
$\frac{5.07 \times 10^{-5}}{5.07 \times 10^{-5}} = \left( \frac{0.30}{0.10} \right)^y$
$1 = (3)^y$
Since any non-zero number raised to the power of $0$ is $1$, therefore $y = 0$. [Mathematical Axiom of Exponents].

Step 4: Determining Order ($x$) with respect to $A$

Using the value of $y = 0$, the rate law simplifies to $r = k [A]^x$. We use Experiments 1 and 3:
$\frac{r_3}{r_1} = \frac{k [0.40]^x [0.05]^0}{k [0.20]^x [0.30]^0}$
$\frac{1.43 \times 10^{-4}}{5.07 \times 10^{-5}} = \left( \frac{0.40}{0.20} \right)^x$
$2.82 \approx (2)^x$
Rounding the experimental data observation, $2^x \approx 2.82$. Applying logarithms:
$x \ln(2) = \ln(2.82)$
$x = \frac{1.0367}{0.693} \approx 1.5$

Visual Representation of Reaction Order

Concentration [A] Rate Order (x) ≈ 1.5

Final Solution: The order of reaction with respect to $A$ is $1.5$ and the order of reaction with respect to $B$ is $0$. The overall order of the reaction is $1.5 + 0 = 1.5$.


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