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/c/solution

Away from singular regimes, assume enthalpy and heat capacity at constant pressure are extensive: and , with nonzero intensive . The enthalpy fluctuation formula then gives
Absolute fluctuations grow as , while the mean grows as . In the thermodynamic limit, enthalpy per particle therefore concentrates around its mean; it is relative, rather than absolute, fluctuations that vanish. This is the usual relative fluctuations of an extensive observable scaling. It assumes ordinary extensive heat capacity and a nonzero mean with a stated energy reference; a critical divergence or an artificially zero mean requires separate analysis.

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