Past exam of the chemistry A course of the University of Cambridge 2024 Paper 2 A7 a i Solution 2026-10-20
In transition state theory, is the dimensionless equilibrium-like constant for forming the activated complex from the reactants under the chosen standard-state convention. It is not the equilibrium constant for forming the stable product.
is the standard activation free energy, the standard activation enthalpy, and the standard activation entropy. Each is the activated-complex quantity minus the corresponding sum for the reactants, with the unstable reaction-coordinate motion treated by the transition-state flux construction.
is the standard concentration, conventionally for the rate units used here. Its inverse converts the attempt frequency into the units of a bimolecular rate constant. The stated Eyring equation assumes unit transmission coefficient.
Past exam of the chemistry A course of the University of Cambridge 2024 Paper 2 A7 b iii Solution 2026-10-20
The activation enthalpy is obtained from the slope across the measured interval. The activation entropy comes from the intercept at , far outside that interval, so a small slope uncertainty can produce a much larger uncertainty in the extrapolated intercept. Slope and intercept errors are consequently strongly correlated.
The entropy is also sensitive to the assumed prefactor and standard concentration, whereas a constant multiplicative calibration error shifts the intercept without changing the slope. This explains why its inferred precision is often poorer. Since enthalpy and entropy have different units, a claim about which absolute numerical uncertainty is larger requires a stated comparison convention.
Past exam of the chemistry A course of the University of Cambridge 2024 Paper 2 A7 b ii Solution 2026-10-20
The large negative activation entropy is consistent with a strongly organized bimolecular cycloaddition. Two separately translating and rotating molecules must approach with a restricted orientation to form a compact ring-forming transition state. Losing relative positional and orientational freedom lowers entropy.
Past exam of the chemistry A course of the University of Cambridge 2024 Paper 2 A7 b i Solution 2026-10-20
The slope is K, so the activation enthalpy isFor , using in gives the numerical prefactor . The intercept therefore yieldsThe large logarithm must be subtracted; identifying with the activation entropy would omit the transition-state attempt-frequency factor. Changing rate units without changing the standard-concentration prefactor consistently would also give a spurious entropy.
The positive is compatible with fragmentation/desolvation in the elimination route. A simple rate-limiting association of hydroxide with a neutral ester would usually have a less favorable activation entropy.
The measured activation parameters belong to the overall second-order rate constant: the acid-base pre-equilibrium and solvent reorganization contribute as well. Consequently positive activation entropy supports the fragmentation interpretation together with the leaving-group slope, but does not by itself prove a particular elementary transition structure.