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NCERT Exemplar · Q59

Q.Match the statements given in Column I and Column II.
Column I:

(i) Catalyst alters the rate of reaction
(ii) Molecularity
(iii) Second half life of first order reaction
(iv) e−Ea/RTe^{-E_a/RT}
(v) Energetically favourable reactions are sometimes slow
(vi) Area under the Maxwell Boltzmann curve is constant
Column II:
(a) cannot be fraction or zero
(b) proper orientation is not there always
(c) by lowering the activation energy
(d) is same as the first
(e) total probability is one
(f) refers to the fraction of molecules with energy equal to or greater than activation energy
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This question tests your conceptual grasp of chemical kinetics — each statement in Column I must be matched with its correct explanation in Column II. The key is to understand why each match holds, not just memorise pairings.

Let's go through each statement one by one, building the reasoning from first principles.

1. (i) Catalyst alters the rate of reaction → (c) by lowering the activation energy

A catalyst provides an alternative reaction pathway with a lower activation energy (EaE_a). This means a larger fraction of molecules have enough energy to cross the barrier at the same temperature. The catalyst itself is not consumed — it simply changes the route. The rate increases because more molecules can react per unit time.

Watch out

A catalyst does not change the equilibrium constant or the enthalpy change of the reaction — it only speeds up both forward and backward reactions equally.

2. (ii) Molecularity → (a) cannot be fraction or zero

Molecularity is the number of molecules (or atoms) that collide in an elementary step. It is always a positive integer: 1 (unimolecular), 2 (bimolecular), or rarely 3 (termolecular). It can never be zero (no reaction without at least one molecule) or a fraction (you can't have half a molecule colliding). This is a fundamental definition — molecularity is a theoretical concept, not an experimentally determined number like order.

Tip

Don't confuse molecularity (always integer, for elementary steps) with order of reaction (can be fractional, zero, or even negative, determined experimentally).

3. (iii) Second half life of first order reaction → (d) is same as the first

For a first order reaction, the half-life (t1/2t_{1/2}) is independent of the initial concentration:

t1/2=ln⁡2kt_{1/2} = \frac{\ln 2}{k}

Since kk is constant at a given temperature, every successive half-life is identical. The second half-life equals the first, the third equals the second, and so on. This is a unique property of first order kinetics — no other order has constant half-lives.

For a first order reaction: t1/2=0.693kt_{1/2} = \frac{0.693}{k} — constant regardless of concentration.

4. (iv) e−Ea/RTe^{-E_a/RT} → (f) refers to the fraction of molecules with energy equal to or greater than activation energy

This expression comes directly from the Arrhenius equation:

k=Ae−Ea/RTk = A e^{-E_a/RT}

The exponential term e−Ea/RTe^{-E_a/RT} represents the fraction of molecules that have energy ≥Ea\geq E_a at temperature TT. It is derived from the Maxwell-Boltzmann distribution — only molecules in the high-energy tail of the distribution can overcome the activation barrier.

5. (v) Energetically favourable reactions are sometimes slow → (b) proper orientation is not there always …

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