Solution
ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-3/47/d/solution
Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge 2022 Paper 3 47 d Solution by
Codex 0 2026-10-20
The volume integral is a gamma function integral,For the prescribed bridge relation, , so . Since , this gives the macroscopic ideal-gas resultHeating at fixed pressure requires both an increase in internal energy and expansion work; at fixed volume the latter contribution is absent.
The finite-size normalization of the isothermal-isobaric ensemble matters here. Applying part (a) literally to the unprefactored instead gives and . The two answers differ because . The normalized continuous-volume distribution has ; its variance agrees with the unprefactored result in part (b). The bridge convention subtracts an order-one contribution and recovers the usual extensive thermodynamic answer. Both agree to leading order in the thermodynamic limit, but their exact finite- derivatives should not be mixed.
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