Past exam of the mathematics course of the University of Cambridge 2015 ii Paper 3 33C b ii Solution Created 2026-09-24 Updated 2026-10-06
Combining with the preceding Gibbs free-energy Maxwell relation givesSetting and solving for yields the Joule-Thomson coefficientWhen , a negative pressure change produces cooling.
Past exam of the mathematics course of the University of Cambridge 2020 ii Paper 2 36A Solution Created 2026-09-24 Updated 2026-09-29
For a simple system of fixed composition, the first law of thermodynamics andgiveThusEquality of mixed derivatives gives the Gibbs free-energy Maxwell relation
The heat capacity at constant volume and heat capacity at constant pressure areRegarding as a function of and differentiating along a constant-pressure curve givesThe Maxwell relation from the Helmholtz free energy isTherefore the difference between constant-pressure and constant-volume heat capacities is
Along the liquid-gas phase coexistence curve, the molar Gibbs free energies agree. Differentiating along the curve givesHence the Clausius-Clapeyron relation iswhere is the molar latent heat.
If and the gas is ideal, then , soFor constant , integration yieldswhere is constant over the range in which the approximations apply.
Past exam of the quantum condensed matter course of the University of Cambridge 2004 Section B B7 a Solution Created 2026-10-18 Updated 2026-10-20
This is the Joule-Thomson coefficient, , describing a temperature change during an isenthalpic pressure change. Here is enthalpy, is the heat capacity at constant pressure, and is volume, all for the same chosen amount of substance. Starting with and using the Gibbs free-energy Maxwell relation givesSetting provesIn a steady insulated throttle or porous plug, negligible kinetic- and potential-energy changes make the upstream and downstream enthalpies equal. A positive coefficient gives cooling on a pressure decrease; a negative one gives warming. For an ideal gas, at fixed , so the coefficient is zero. Real-gas interactions permit cooling and an inversion curve, making the effect useful in gas refrigeration and liquefaction.
The measurement of the Joule-Thomson effect with a porous plug compares pressures and thermometers on the two sides of an insulated flow restriction. Suppressing external heat exchange and separating the readings from high-speed jets are part of making the enthalpy argument applicable; an arbitrary adiabatic expansion need not be isenthalpic.