Q.Identify the correct statement : (A) Molecularity of a reaction is an experimental quantity. (B) For complex reactions molecularity has no meaning. (C) Molecularity of a reaction can be zero or even a fraction. (D) Molecularity more than three is very common in chemical reactions.
Molecularity is a theoretical concept tied to the elementary step, not an experimental quantity; it is always a positive integer (1, 2, or 3) and has no meaning for complex reactions. The correct statement is (B).
The Concept: What Molecularity Really Means
Molecularity is one of those terms that sounds like it should be complicated, but it’s actually very simple — provided you remember one crucial thing: molecularity only applies to an elementary step, never to the overall reaction.
An elementary step is a single collision or a single molecular event. If two molecules collide and react in one step, that step is bimolecular (molecularity = 2). If one molecule breaks apart on its own, it’s unimolecular (molecularity = 1). That’s it. There is no such thing as a termolecular step involving four or five molecules simultaneously — the probability of that many particles colliding at the exact same instant is astronomically small. So molecularity is always a small positive integer: 1, 2, or rarely 3.
Now contrast this with order of reaction, which is an experimental quantity. Order can be zero, fractional, or even negative — it comes from the rate law you determine in the lab. Molecularity is a theoretical label for a step, not something you measure.
Let’s examine each option carefully.
Step-by-Step Analysis
1. Option (A): “Molecularity of a reaction is an experimental quantity.”
This is false. You cannot measure molecularity by doing an experiment. You can measure the rate and find the order, but molecularity is deduced from the mechanism — it’s a theoretical count of how many molecules participate in an elementary step. For example, if you propose that happens in one step, you assign it a molecularity of 2; you don’t “find” it experimentally.
2. Option (B): “For complex reactions molecularity has no meaning.”
This is true. A complex reaction proceeds through multiple elementary steps. The overall reaction has no single molecularity — each step has its own. Asking “what is the molecularity of the overall reaction?” is like asking “what is the age of a family?” — it doesn’t apply. Molecularity is defined only for an elementary step.
3. Option (C): “Molecularity of a reaction can be zero or even a fraction.”
False. Molecularity is the number of molecules (or atoms, ions) that collide in an elementary step. You cannot have a fraction of a molecule colliding, nor can you have zero molecules — a reaction with zero molecules is a contradiction. Zero and fractional values belong to order, not molecularity.
A common mistake is to confuse molecularity with order. Remember: order can be 0, 1, 2, fractional, or negative; molecularity is always a positive integer (1, 2, or 3).
4. Option (D): “Molecularity more than three is very common in chemical reactions.”
False. Molecularity greater than 3 is extremely rare because the chance of four or more particles meeting simultaneously is negligible. In practice, reactions with apparent higher molecularity actually occur via a sequence of bimolecular steps.
The correct statement is (B) — for complex reactions, molecularity has no meaning.
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