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Q.For the following question, two statements are given – one labelled as Assertion (A) and the other labelled as Reason (R). Select the correct answer from the codes (A), (B), (C) and (D) as given below. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true. Assertion (A) : Order of reaction and molecularity are always same for complex reactions. Reason (R) : Order is determined experimentally and molecularity is applicable only for elementary reactions.

CBSECBSE Class XII Board 2024MCQ· 1mImportance★★★★★
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The assertion is false because for complex reactions, order and molecularity are not always the same — order is experimental and can be fractional, while molecularity is a theoretical integer defined only for elementary steps. The reason is true. Hence the correct choice is (D).


Concept and Intuition

This question tests a fundamental distinction in chemical kinetics: the difference between order and molecularity. Many students mix them up because both involve counting molecules, but they come from completely different worlds.

Order is an experimental number — you run a reaction, measure how the rate changes with concentration, and deduce the exponent. It can be 0, 1, 2, or even a fraction like 1.5. It tells you nothing about the actual mechanism; it just describes the observed rate law.

Molecularity is a theoretical concept — it applies only to an elementary reaction (a single step that happens exactly as written). It is always a positive integer (1, 2, or rarely 3) because it counts how many molecules must collide simultaneously in that step. For a complex reaction (one with multiple elementary steps), molecularity is meaningless for the overall reaction — you can only talk about the molecularity of each individual step.

The assertion claims they are "always same" for complex reactions. That cannot be true: a complex reaction has no single molecularity, and its order (determined experimentally) often differs from the molecularity of any one step.


Step-by-Step Reasoning

  1. Understand the Assertion (A):

    "Order of reaction and molecularity are always same for complex reactions."

    A complex reaction proceeds through two or more elementary steps. The overall order is found by experiment — it could be 1, 2, 1.5, or even zero. Molecularity, however, is defined only for an elementary step. Since a complex reaction has multiple steps, it does not have a single molecularity. Therefore, comparing "order" (a single number) with "molecularity" (which doesn't exist for the overall reaction) is meaningless. Even if you tried to compare, they are rarely equal — for example, the complex reaction 2NO+O2→2NO22NO + O_2 \rightarrow 2NO_2 has an experimental order of 2 (not 3), while no elementary step has molecularity 3. So the assertion is false.

  2. Understand the Reason (R):

    "Order is determined experimentally and molecularity is applicable only for elementary reactions." …

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