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Thermodynamics: A complete undergraduate course

Andrew M. Steane

Chapter 25

Continuous phase transitions - all with Video Answers

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Chapter Questions

Problem 1

Ehrenfest's equations
(i) Show that, for a second-order transition in a $p V$ system, not only are the chemical potentials equal, but so are the volume and entropy per particle.
(ii) Let $v$ be the volume per particle. Using $d v_1=d v_2$ for a small change along the phase boundary, obtain
$$
\frac{\mathrm{d} p}{\mathrm{~d} T}=\frac{\beta_2-\beta_1}{\kappa_2-\kappa_1}=\frac{\Delta \beta}{\Delta \kappa}
$$
(iii) Treating the entropy per particle, obtain
$$
\frac{\mathrm{d} p}{\mathrm{~d} T}=-\frac{1}{v T} \frac{c_{p 2}-c_{p 1}}{\beta_2-\beta_1}=\frac{\Delta C_p}{V T \Delta \beta} .
$$
These are called Ehrenfest's equations. They apply to second-order phase transitions as long as the quantities involved are all well behaved. (Since for many continuous phase transitions some or all of the response functions diverge, these equations are less useful in practice than the Clausius-Clapeyron equation. However the corresponding results for magnetic properties are useful in the study of superconductivity.)

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Problem 2

Obtain the critical exponent $\beta$ for the van der Waals model, as follows. To find the liquid-vapour density difference we need to find the locations of the points $A$ and $B$ indicated in the Maxwell construction shown on Figure 15.6. Let the two volumes be $V_A$ and $V_B$, then since they are at the same pressure on the same isotherm, we may write
$$
p=\frac{8 T}{3 V_A-1}-\frac{3}{V_A^2}=\frac{8 T}{3 V_B-1}-\frac{3}{V_B^2} .
$$
Solve this equation for $T$, to obtain
$$
T=\frac{\left(3 V_A-1\right)\left(3 V_B-1\right)}{8 V_A^2 V_B^2}\left(V_B+V_A\right)
$$
At the critical point we have $V_A=V_B=1$ and then the equation gives $T=1$ as expected. In general we would need the full Maxwell construction to find $V_A$ and $V_B$, but now argue that near the critical point the two volumes must fall equally either side of 1 , i.e. $V_A=1-x$ and $V_B=1+x$ for some $x$ (this can also be shown by expanding the equation of state to third order in powers of $V-1$ and looking at the limit when $T \rightarrow 1$ ). Expand the equation for small $x$ and thus find $T \sim 1-x^2 / 4$, which implies $\left(V_v-V_l\right) \propto\left(T-T_c\right)^{1 / 2}$. Obtain the density difference, and hence the exponent $\beta$ in equation (25.9).

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Problem 3

Obtain equation (25.25).

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