Thermodynamics – Internal Energy According to the Van der Waals Equation

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I am trying to derive the internal energy of a gas which obeys the van der Waals equation.

I have however encountered some problems. I calculate the integral of $dU$ from $V=0,T=0$ to $V=V, T=\infty$ to $V=V,T=T$.

I can calculate the work:

$$\left(p+\left(\frac{a}{n}\right)^2\right)(V-nb)=nRT \implies p=\frac{nRT}{V-nb}-\frac{an^2}{V^2}$$

For the second part of the path $V$ is constant so $W=0$.

$$W=-\int\limits_\infty^V p\textrm dV=\int\limits_V^\infty \frac{nRT}{V-nb}-\frac{an^2}{V^2} \textrm dV\\=nRT\ln(V-nb)|_V^\infty+\frac{an^2}{V}|_V^\infty\\=
\infty-\infty +\frac{an^2}{\infty}-\frac{an^2}{V}=-\frac{an^2}{V}$$

I know I haven't been mathematically rigorous but that is not really important to me at the moment. I think this is right.

I can't however think of how i should calculate the heat involved in following this path.

Any help on how to do this is appreciated.

EDIT: I see now that the work I calculated is wrong as well as $$nRT\ln(V-nb)|_V^\infty\neq\infty-\infty$$

Best Answer

You and Lubos are integrating the expression $dU = -pdV$ for a constant composition system, but this expression is only valid for constant entropy $S$. During integration you maintain $T$ constant, but the latter is not equivalent to $S$ constant.

If you chose a representation $(T,V)$ then

$$dU = \left( \frac{\partial U}{\partial T}\right)_V dT + \left( \frac{\partial U}{\partial V}\right)_T dV$$

and you can integrate for the special case of constant $T$, but then $({\partial U}/{\partial V})_T$ is not $(-p)$, as you assumed above. The value of this partial derivative can be obtained from the Helmholtz equation $({\partial U}/{\partial V})_T = T^2 [{\partial}/{\partial T} (p/T)]_V$. Integration gives

$$U(T,V,N) = U_0(T,V_0,N) + \int_{V_0}^V T^2 \left( \frac{\partial}{\partial T} \frac{p}{T} \right)_V dV$$

Noting that when the volume tends to infinity the real gas approaches an ideal gas, which implies that $U\to U_\mathrm{ideal}$, we can chose $V_0\to\infty$ to fix the integratino constant $U_0$

$$U(T,V,N) = U_\mathrm{ideal}(T,N) + \int_{\infty}^V T^2 \left( \frac{\partial}{\partial T} \frac{p}{T} \right)_V dV$$

Substituting the van der Waals equation of state

$$\frac{p}{T} = \frac{NR}{V-Nb} - \frac{a}{T} \frac{N^2}{V^2}$$

and working out yields the internal energy of the van der Waals gas

$$U(T,V,N) = U_\mathrm{ideal}(T,N) - \frac{aN^2}{V} $$

The energy of the ideal gas is given by the well-known form $U_\mathrm{ideal} = N C_V T$ with $C_V$ the heat capacity for ideal gas, e.g. $3R/2$ for monoatomic gas. Now you can understand why the appearance of the heat capacity for an ideal gas is not anything wrong, as you commented above.

Notice also that when $V\to\infty$ the internal energy of the van der Waals gas reduces to the internal energy of an ideal gas, which does not depend on volume. This is the correct result.

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