Related Formula
From the Arrhenius equation, rate constants vary exponentially with temperature:
k = A · e-Eₐ / RT$$k = A \cdot e^{-E_a / RT}$$
When rate constants combine multiplicatively or via roots, their corresponding activation energies combine linearly.
Core Logic
Given the overall rate constant expression:
k = ((k₁ · k₃)/(k₂))1/2$$k = \left(\frac{k_1 \cdot k_3}{k_2}\right)^{1/2}$$
Substitute the Arrhenius expression (kᵢ = Aᵢ · e^-Eₐᵢ/RT$k_i = A_i \cdot e^{-E_{ai}/RT}$) for each rate constant:
A · e-Eₐ/RT = [ (A₁ · e^-Eₐ₁/RT) · (A₃ · e^-Eₐ₃/RT)A₂ · e^-Eₐ₂/RT]1/2$$A \cdot e^{-E_a/RT} = \left[\frac{(A_1 \cdot e^{-E_{a1}/RT}) \cdot (A_3 \cdot e^{-E_{a3}/RT})}{A_2 \cdot e^{-E_{a2}/RT}}\right]^{1/2}$$
Equating the exponential terms yields the linear relationship for the overall activation energy (Eₐ$E_a$):
(Eₐ)/(RT) = (1)/(2) ( Eₐ₁RT + Eₐ₃RT - Eₐ₂RT)$$\frac{E_a}{RT} = \frac{1}{2} \left(\frac{E_{a1}}{RT} + \frac{E_{a3}}{RT} - \frac{E_{a2}}{RT}\right)$$
Eₐ = Eₐ₁ + Eₐ₃ - Eₐ₂2$$E_a = \frac{E_{a1} + E_{a3} - E_{a2}}{2}$$
Substitute the given activation energy values (Eₐ₁ = 60, Eₐ₂ = 30, Eₐ₃ = 10 kJ/mol$E_{a1} = 60, E_{a2} = 30, E_{a3} = 10\text{ kJ/mol}$):
Eₐ = (60 + 10 - 30)/(2) = (40)/(2) = 20 kJ mol⁻¹$$E_a = \frac{60 + 10 - 30}{2} = \frac{40}{2} = 20\text{ kJ mol}^{-1}$$
The overall activation energy is 20 kJ/mol$20\text{ kJ/mol}$.
Pattern Recognition
Shortcut: Convert the rate constant algebraic expression directly into an activation energy formula by swapping k$k$ for Eₐ$E_a$, turning multiplications into additions, divisions into subtractions, and powers into multipliers. Here, k = (k₁ k₃ / k₂)1/2$k = (k_1 k_3 / k_2)^{1/2}$ translates directly to Eₐ = (1)/(2)(Eₐ₁ + Eₐ₃ - Eₐ₂)$E_a = \frac{1}{2}(E_{a1} + E_{a3} - E_{a2})$.
Chapter Mix
Class 12 Chemistry: Chemical Kinetics