Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2024/paper-2/a7/c/iv/solution

The negative activation volume means the transition state occupies less partial molar volume than the two separated reactants. Pressure therefore favours reaching it and increases the forward rate, consistent with a compact associative cycloaddition in which new bonds begin to form.
The magnitude, about , is molecular in scale. It includes packing and solvent reorganization as well as intrinsic bond-length changes, so it should not be interpreted as a simple geometric volume carved out of two rigid molecular surfaces.

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