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Chemistry · Glossary

What is Kinetic and thermodynamic control?

Also known as: kinetic control · thermodynamic control

Definition 9.17 University Chemistry — Year 1 · Chapter 9 — Reaction Mechanisms: Elementary Steps and Approximations

When a reactant can give two products by competing paths, the reaction is under kinetic control if the product proportions are fixed by the rates of formation (the product of lower barrier dominates), and under thermodynamic control if the paths are reversible and the system reaches equilibrium (the more stable product dominates).

Examples

Example 9.18 (Choosing the product)

A reactant gives B over a barrier of 50 kJ/mol50\,\mathrm{kJ}/\mathrm{mol} (ΔE=−10 kJ/mol\Delta E = -10\,\mathrm{kJ}/\mathrm{mol}) and C over a barrier of 70 kJ/mol70\,\mathrm{kJ}/\mathrm{mol} (ΔE=−40 kJ/mol\Delta E = -40\,\mathrm{kJ}/\mathrm{mol}). At 300 K300\,\mathrm{K} and short times, with equal pre-exponential factors, B forms exp⁡(20000/(8.314×300))≈3000\exp(20000/(8.314 \times 300)) \approx 3000 times faster than C: kinetic control gives B. At high temperature and long times, B returns over its small reverse barrier, C does not, and the system ends as C: thermodynamic control.

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