MCQMediumJEE 2025Order & Molecularity

JEE Chemistry 2025 Question with Solution

The reaction A2+B22AB\text{A}_2 + \text{B}_2 \to 2\text{AB} follows the mechanism:

A2k1A+(fast)A+B2k2AB+(slow)A+BAB (fast)\text{A}_2 \xrightarrow{k_1} \text{A} + \text{A} \ (\text{fast}) \quad \text{A} + \text{B}_2 \xrightarrow{k_2} \text{AB} + \text{B} \ (\text{slow}) \quad \text{A} + \text{B} \to \text{AB} \ (\text{fast})

The overall order of the reaction is:

  • A

    33

  • B

    1.51.5

  • C

    2.52.5

  • D

    22

Answer

Correct answer:B

Step-by-step solution

Standard Method

Given: The mechanism is

A2k1A+A\text{A}_2 \xrightarrow{k_1} \text{A} + \text{A}

(fast)

A+B2k2AB+B\text{A} + \text{B}_2 \xrightarrow{k_2} \text{AB} + \text{B}

(slow, rate-determining step)

A+BAB\text{A} + \text{B} \to \text{AB}

(fast)

Find: The overall order of the reaction.

The slow step controls the rate, so

Rate=k2[A][B2]\text{Rate} = k_2[\text{A}][\text{B}_2]

Here [A][\text{A}] is an intermediate, so express it in terms of stable reactants. From the fast step, as given in the solution,

[A]=K10.5[A2]0.5[\text{A}] = K_1^{0.5}[\text{A}_2]^{0.5}

Substituting into the rate law,

Rate=k2(K10.5[A2]0.5)[B2]\text{Rate} = k_2\left(K_1^{0.5}[\text{A}_2]^{0.5}\right)[\text{B}_2] Rate=k[A2]0.5[B2]\text{Rate} = k'[\text{A}_2]^{0.5}[\text{B}_2]

Therefore, the overall order is

0.5+1=1.50.5 + 1 = 1.5

Hence, the overall order of the reaction is 1.51.5. The correct option is B.

Detailed Working

Given:

A2+B22AB\text{A}_2 + \text{B}_2 \rightarrow 2\text{AB}

Mechanism:

  1. A2k12A\text{A}_2 \xrightarrow{k_1} 2\text{A} (fast)
  2. A+B2k2AB+B\text{A} + \text{B}_2 \xrightarrow{k_2} \text{AB} + \text{B} (slow)
  3. A+Bk3AB\text{A} + \text{B} \xrightarrow{k_3} \text{AB} (fast)

Find: The overall order.

The second step is the rate-determining step, so

Rate=k2[A][B2]\text{Rate} = k_2[\text{A}][\text{B}_2]

Using the steady-state treatment shown in the solution for intermediate A\text{A}:

2k1[A2]=k2[A][B2]+k3[A][B]2k_1[\text{A}_2] = k_2[\text{A}][\text{B}_2] + k_3[\text{A}][\text{B}] [A]=2k1[A2]k2[B2]+k3[B][\text{A}] = \frac{2k_1[\text{A}_2]}{k_2[\text{B}_2] + k_3[\text{B}]}

The solution further states that

[B][B2]1/2[\text{B}] \propto [\text{B}_2]^{1/2}

so the effective dependence on [B2][\text{B}_2] becomes [B2]1/2[\text{B}_2]^{1/2}. Hence the overall rate law is approximately

Rate[A2]1[B2]1/2\text{Rate} \propto [\text{A}_2]^1[\text{B}_2]^{1/2}

Therefore, the overall order is

1+12=1.51 + \frac{1}{2} = 1.5

So, the overall order of the reaction is 1.51.5.

Common mistakes

  • Using only the molecularity of the overall reaction and concluding the order is 22. This is wrong because order is determined from the rate law, not from the balanced overall equation. Use the slow step and elimination of intermediates instead.

  • Writing the rate law directly as Rate=k[A2][B2]\text{Rate} = k[\text{A}_2][\text{B}_2]. This is wrong because A2\text{A}_2 does not appear directly in the slow step. First write the slow-step rate law in terms of the intermediate and then substitute for [A][\text{A}].

  • Ignoring that A\text{A} is an intermediate and treating its concentration as an independent reactant concentration. This gives an incomplete rate law. Express [A][\text{A}] through the fast equilibrium or approximation provided in the mechanism.

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