2.II.34D

Statistical Physics
Part II, 2007

Derive the Maxwell relation

(Sp)T=(VT)p\left(\frac{\partial S}{\partial p}\right)_{T}=-\left(\frac{\partial V}{\partial T}\right)_{p}

The diagram below illustrates the Joule-Thomson throttling process for a porous barrier. A gas of volume V1V_{1}, initially on the left-hand side of a thermally insulated pipe, is forced by a piston to go through the barrier using constant pressure p1p_{1}. As a result the gas flows to the right-hand side, resisted by a piston which applies a constant pressure p2p_{2} (with p2<p1p_{2}<p_{1} ). Eventually all of the gas occupies a volume V2V_{2} on the right-hand side. Show that this process conserves enthalpy.

The Joule-Thomson coefficient μJT\mu_{\mathrm{JT}} is the change in temperature with respect to a change in pressure during a process that conserves enthalpy HH. Express the JouleThomson coefficient, μJT(Tp)H\mu_{\mathrm{JT}} \equiv\left(\frac{\partial T}{\partial p}\right)_{H}, in terms of T,VT, V, the heat capacity at constant pressure CpC_{p}, and the volume coefficient of expansion α1V(VT)p\alpha \equiv \frac{1}{V}\left(\frac{\partial V}{\partial T}\right)_{p}.

What is μJT\mu_{\mathrm{JT}} for an ideal gas?

If one wishes to use the Joule-Thomson process to cool a real (non-ideal) gas, what must the sign\operatorname{sign} of μJT\mu_{\mathrm{JT}} be?