Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-4/66/c/iv/solution

For B, is consistent with bond fission and release/reorganization of electrostricted solvent on reaching a fragmentation transition state. The ordinary methoxy ester has , consistent with associative hydroxide addition and the compact, strongly solvated developing tetrahedral species.
The opposite signs corroborate distinct mechanisms. Since both values include solvation and any pre-equilibria, they should not be interpreted merely as geometric volumes of isolated molecules.

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