Unit 2: CH02 Syllabus Node

Kinetics, Collision Theory & Catalysis

Collision theory, activation energy, Maxwell-Boltzmann energy distribution changes with temperature, and catalysed reaction pathways.

1. Collision Theory and Activation Energy

For a chemical reaction to occur between reacting particles, they must satisfy two essential conditions:

  1. Particles must collide with kinetic energy equal to or greater than the activation energy (\(E \ge E_a\)).
  2. Particles must collide with the correct steric orientation.
Activation Energy (\(E_a\))

The minimum kinetic energy required for colliding reactant particles to result in a successful reaction.

2. The Maxwell-Boltzmann Distribution

In any gas or liquid sample, molecular speeds vary across a broad spectrum due to random collisions. The energy distribution is described by the Maxwell-Boltzmann curve:

Maxwell-Boltzmann Distribution with Temperature and Catalysts Molecular Kinetic Energy (E) Fraction of Molecules T1 (Lower Temp) T2 > T1 (Higher Temp) E_a (Uncatalysed) E_cat (Catalysed) Area = molecules with E >= Ea

Mathematical Characteristics

  • Starts at the origin \((0,0)\): No molecules have zero kinetic energy.
  • Peak of the curve: Corresponds to the most probable energy (\(E_{mp}\)).
  • Mean energy: Located slightly to the right of the peak because of the extended high-energy tail.
  • Asymptotic tail: The curve never touches the x-axis at high energy because there is no theoretical upper limit to molecular velocity.
  • Area under the curve: Represents the total number of particles in the sample.

3. The Effect of Temperature on Reaction Rate

When the temperature of a reaction mixture increases from \(T_1\) to \(T_2\):

  • Molecules gain kinetic energy and move faster.
  • The distribution curve flattens and broadens; the peak shifts to the right and downwards.
  • The total area under the curve remains identical (total particle count is constant).
  • The fraction of molecules possessing energy equal to or greater than the activation energy (\(E \ge E_a\)) increases significantly (shaded area expands dramatically).
  • Consequently, the frequency of successful collisions increases markedly, producing a sharp rise in reaction rate.

4. Catalysts and Reaction Pathways

Catalyst

A substance that increases the rate of a chemical reaction without undergoing permanent chemical change or being consumed.

Mechanism of Action

A catalyst provides an alternative reaction pathway with a lower activation energy (\(E_{cat} < E_a\)).

On the Maxwell-Boltzmann distribution, the threshold line shifts to the left from \(E_a\) to \(E_{cat}\). A much larger proportion of colliding particles now possess sufficient energy to react successfully upon collision.

5. Practice Questions

Practice Problem (3 Marks)
Use collision theory and the Maxwell-Boltzmann distribution to explain why a modest 10 K rise in temperature can cause a reaction rate to approximately double, even though collision frequency increases by only a few percent.

Mark Scheme:

  • At higher temperature, average kinetic energy increases, shifting the Maxwell-Boltzmann distribution peak right and down. (1 mark)
  • A much larger fraction of particles possess kinetic energy equal to or greater than the activation energy (\(E \ge E_a\)). (1 mark)
  • Therefore, the frequency of successful collisions increases significantly, far outweighing the small increase in total collision rate. (1 mark)