# 17.5: Pressure can be Expressed in Terms of the Canonical Partition Function

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Pressure can also be derived from the canonical partition function. The average pressure is the sum of the probability times the pressure:

$\langle P \rangle = \sum_i{P_i(N,V,T)P_i(N,V)} \nonumber$

The pressure of a macroscopic system is:

$P(N,V) = -\left(\dfrac{\partial E_i}{\partial V}\right)_N \nonumber$

So we can write the average pressure as:

$\begin{split} \langle P \rangle &= \sum_i{P_i(N,V,\beta)\left(-\dfrac{\partial E_i}{\partial V}\right)_N} \\ &= \sum_i{\left(-\dfrac{\partial E_i}{\partial V}\right)_N\dfrac{e^{-E_i(N,V)/kT}}{Q(N,V,T)}} \end{split} \nonumber$

In a few steps we can show that the temperature can be expressed in terms of the partition function:

$Q(N,V,T) = \sum_i{e^{-E_i(N,V)/kT}} \nonumber$

Writing in terms of $$\beta$$ instead of temperature:

$Q(N,V,\beta) = \sum_i{e^{-\beta E_i(N,V)}} \nonumber$

The derivative of the partition function with respect to volume is:

$\left(\dfrac{\partial Q}{\partial V}\right)_{N,\beta} = -\beta \sum_i{\left(\dfrac{\partial E_i}{\partial V}\right)_{N}e^{-\beta E_i(N,V)}} \nonumber$

The average pressure can then be written as:

$\langle P \rangle = \dfrac{kT}{Q(N,V,\beta}\left(\dfrac{\partial Q}{\partial V}\right)_{N,\beta} \nonumber$

Which shows that the pressure can be expressed solely terms of the partition function:

$\langle P \rangle = kT\left(\dfrac{\partial \ln{Q}}{\partial V}\right)_{N,\beta} \nonumber$

We can use this result to derive the ideal gas law. For $$N$$ particles of an ideal gas:

$Q(N,V,\beta) = \dfrac{[q(V,\beta)]^N}{N!} \nonumber$

where:

$q(V,\beta) = \left(\dfrac{2\pi m}{h^2\beta}\right)^{3/2}V \nonumber$

is the translational partition function. The utility of expressing the pressure as a logarithm is clear from the fact that we can write:

$\begin{split} \ln{Q} &= N\ln{q}-\ln{N!} \\ &= -\dfrac{3N}{2}\ln{\left(\dfrac{2\pi m}{h^2\beta}\right)}+N\ln{V}-\ln{N!} \end{split} \nonumber$

We have used the property of logarithms that $$\ln{(AB)} = \ln{(A)} + \ln{(B)}$$ and $$\ln{(X^Y)} = Y\ln{(X)}$$. Only one term in the ln $$Q$$ depends on $$V$$. Taking the derivative of $$N\ln{V}$$ with respect to $$V$$ gives:

$\left(\dfrac{\partial \ln{Q}}{\partial V}\right)_{N,\beta} = \dfrac{N}{V} \nonumber$

Substituting this into the above equation for the pressure gives:

$P = \dfrac{NkT}{V} \nonumber$

which is the ideal gas law. Recall that $$Nk = nR$$ where $$N$$ is the number of molecules and $$n$$ is the number of moles. $$R$$ is the universal gas constant (8.314 J/mol-K) which is nothing more than $$k$$ multiplied by Avagadro’s number. $$N_Ak = R$$ converts the constant from a "per molecule" to a "per mole" basis.

## Gas Compressed by a Piston Figure 17.5.1 : Illustration of a thought experiment in which a system is compressed via a piston pushed into the system along the positive $$z$$ axis.

Let us consider a simple thought experiment, which is illustrated in the figure above: A system of $$N$$ particles is compressed by a piston pushing in the positive $$z$$ direction. Since this is a classical thought experiment, we think in terms of forces. The piston exerts a constant force of magnitude $$F$$ on the system. The direction of the force is purely in the positive $$z$$ direction, so that we can write the force vector $$\bf{F}$$ as $$\bf{F} = \begin{pmatrix} 0, 0, F \end{pmatrix}$$. At equilibrium (the piston is not moving), the system exerts an equal and opposite force on the piston of the form $$\begin{pmatrix} 0, 0, -F \end{pmatrix}$$. If the energy of the system is $$E$$, then the force exerted by the system on the piston will be given by the negative change in $$E$$ with respect to $$z$$:

$-F = -\dfrac{dE}{dz} \label{Eq3.29}$

or:

$F = \dfrac{dE}{dz} \label{Eq3.30}$

The force exerted by the system on the piston is manifest as an observable pressure $$P$$ equal to the force $$F$$ divided by the area $$A$$ of the piston, $$P=F/A$$. Given this, the observed pressure is just:

$P = \dfrac{dE}{Adz} \label{Eq3.31}$

Since the volume decreases when the system is compressed, we see that $$Adz = -dV$$. Hence, we can write the pressure as $$P = -dE/dV$$.

Of course, the relation $$P = -dE/dV$$ is a thermodynamic one, but we need a function of $$x$$ that we can average over the ensemble. The most natural choice is:

$p(x) = -\dfrac{d \mathcal{E} (x)}{dV} \label{Eq3.32}$

so that $$P = \langle p(x) \rangle$$. Setting up the average, we obtain:

\begin{align} P &= -\dfrac{C_N}{Q(N, V, T)} \int \dfrac{\partial \mathcal{E}}{\partial V} e^{-\beta \mathcal{E} (x)} \\ &= \dfrac{C_N}{Q(N, V, T)} \dfrac{1}{\beta} \int \dfrac{\partial}{\partial V} e^{-\beta \mathcal{E} (x)} \\ &= \dfrac{kT}{Q(N, V, T} \dfrac{\partial}{\partial V} C_N \int e^{-\beta \mathcal{E} (x)} \\ &= kT \left( \dfrac{\partial \: \text{ln} \: Q(N, V, T)}{\partial V} \right) \end{align} \label{Eq3.33}

## Ideal Gas in the Canonical Ensemble

Recall that the mechanical energy for an ideal gas is:

$\mathcal{E} (x) = \sum_{i=1}^N \dfrac{\textbf{p}_i^2}{2m} \label{Eq3.36}$

where all particles are identical and have mass $$m$$. Thus, the expression for the canonical partition function $$Q(N, V, T)$$ is:

$Q(N, V, T) = \dfrac{1}{N!h^{3N}} \int dx \: e^{-\beta \sum_{i=1}^N \textbf{p}_i^2/2m} \nonumber$

Note that this can be expressed as:

$Q(N, V, T) = \dfrac{1}{N!h^{3N}}V^N \left[ \int dp \: e^{-\beta p^2/2m} \right]^{3N} \nonumber$

Evaluating the Gaussian integral gives us the final result immediately:

$Q(N, V, T) = \dfrac{1}{N!} \left[ \dfrac{V}{h^3} \left( \dfrac{2 \pi m}{\beta} \right)^{3/2} \right]^N \nonumber$

The expressions for the energy:

$E = -\dfrac{\partial}{\partial \beta} \: \text{ln} \: Q(N, V, T) \nonumber$

which gives:

$E = \dfrac{3}{2}NkT = \dfrac{3}{2}nRT \label{Eq3.37}$

and pressure:

$P = kT \left( \dfrac{\partial \: \text{ln} \: Q(N, V, T)}{\partial V} \right) \nonumber$

giving:

$P = \dfrac{NkT}{V} = \dfrac{nRT}{V} \label{Eq3.38}$

which is the ideal gas law.

17.5: Pressure can be Expressed in Terms of the Canonical Partition Function is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Stefan Franzen, Mark Tuckerman, Jerry LaRue, & Jerry LaRue.