These notes from week 6 of https://paradigms.oregonstate.edu/courses/ph441 cover the ideal gas from a grand canonical standpoint starting with the solutions to a particle in a three-dimensional box. They include a number of small group activities.

Consider one mole of an ideal monatomic gas at 300K and 1 atm. First, let the gas expand isothermally and reversibly to twice the initial volume; second, let this be followed by an isentropic expansion from twice to four times the original volume.

1. How much heat (in joules) is added to the gas in each of these two processes?

2. What is the temperature at the end of the second process?

3. Suppose the first process is replaced by an irreversible expansion into a vacuum, to a total volume twice the initial volume. What is the increase of entropy in the irreversible expansion, in J/K?

1. Find the chemical potential of an ideal monatomic gas in two dimensions, with \(N\) atoms confined to a square of area \(A=L^2\). The spin is zero.

2. Find an expression for the energy \(U\) of the gas.

3. Find an expression for the entropy \(\sigma\). The temperature is \(kT\).

Students consider whether the thermo surfaces reflect the properties of an ideal gas.

These lecture notes from week 7 of https://paradigms.oregonstate.edu/courses/ph441 apply the grand canonical ensemble to fermion and bosons ideal gasses. They include a few small group activities.

Consider an ideal gas of \(N\) particles, each of mass \(M\), confined to a one-dimensional line of length \(L\). The particles have spin zero (so you can ignore spin) and do not interact with one another. Find the entropy at temperature \(T\). You may assume that the temperature is high enough that \(k_B T\) is much greater than the ground state energy of one particle.

Students struggle with understanding that entropy can be created. It's an extensive quantity, and is the only one that isn't normally conserved, so that makes it pretty weird. We (professors) don't always realize how very weird this is, and students don't have the vocabulary to explain it to us, and are often afraid to try.

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Suppose \(g(U) = CU^{3N/2}\), where \(C\) is a constant and \(N\) is the number of particles.

1. Show that \(U=\frac32 N k_BT\).

2. Show that \(\left(\frac{\partial^2S}{\partial U^2}\right)_N\) is negative. This form of \(g(U)\) actually applies to a monatomic ideal gas.

These notes, from the third week of https://paradigms.oregonstate.edu/courses/ph441 cover the canonical ensemble and Helmholtz free energy. They include a number of small group activities.

For electrons with an energy \(\varepsilon\gg mc^2\), where \(m\) is the mass of the electron, the energy is given by \(\varepsilon\approx pc\) where \(p\) is the momentum. For electrons in a cube of volume \(V=L^3\) the momentum takes the same values as for a non-relativistic particle in a box.

1. Show that in this extreme relativistic limit the Fermi energy of a gas of \(N\) electrons is given by \begin{align} \varepsilon_F &= \hbar\pi c\left(\frac{3n}{\pi}\right)^{\frac13} \end{align} where \(n\equiv \frac{N}{V}\) is the number density.

2. Show that the total energy of the ground state of the gas is \begin{align} U_0 &= \frac34 N\varepsilon_F \end{align}

1. Show that a Fermi electron gas in the ground state exerts a pressure \begin{align} p = \frac{\left(3\pi^2\right)^{\frac23}}{5} \frac{\hbar^2}{m}\left(\frac{N}{V}\right)^{\frac53} \end{align} In a uniform decrease of the volume of a cube every orbital has its energy raised: The energy of each orbital is proportional to \(\frac1{L^2}\) or to \(\frac1{V^{\frac23}}\).

2. Find an expression for the entropy of a Fermi electron gas in the region \(kT\ll \varepsilon_F\). Notice that \(S\rightarrow 0\) as \(T\rightarrow 0\).

(K&K 7.11) Show for a single orbital of a fermion system that \begin{align} \left<(\Delta N)^2\right> = \left<N\right>(1+\left<N\right>) \end{align} if \(\left<N\right>\) is the average number of fermions in that orbital. Notice that the fluctuation vanishes for orbitals with energies far enough from the chemical potential \(\mu\) so that \(\left<N\right>=1\) or \(\left<N\right>=0\).

In this entire problem, keep results to first order in the van der Waals correction terms \(a\) and $b.

1. Show that the entropy of the van der Waals gas is \begin{align} S &= Nk\left\{\ln\left(\frac{n_Q(V-Nb)}{N}\right)+\frac52\right\} \end{align}

2. Show that the energy is \begin{align} U &= \frac32 NkT - \frac{N^2a}{V} \end{align}

3. Show that the enthalpy \(H\equiv U+pV\) is \begin{align} H(T,V) &= \frac52NkT + \frac{N^2bkT}{V} - 2\frac{N^2a}{V} \\ H(T,p) &= \frac52NkT + Nbp - \frac{2Nap}{kT} \end{align}

Consider one particle confined to a cube of side \(L\); the concentration in effect is \(n=L^{-3}\). Find the kinetic energy of the particle when in the ground state. There will be a value of the concentration for which this zero-point quantum kinetic energy is equal to the temperature \(kT\). (At this concentration the occupancy of the lowest orbital is of the order of unity; the lowest orbital always has a higher occupancy than any other orbital.) Show that the concentration \(n_0\) thus defined is equal to the quantum concentration \(n_Q\) defined by (63): \begin{equation} n_Q \equiv \left(\frac{MkT}{2\pi\hbar^2}\right)^{\frac32} \end{equation} within a factor of the order of unity.

Consider a column of atoms each of mass \(M\) at temperature \(T\) in a uniform gravitational field \(g\). Find the thermal average potential energy per atom. The thermal average kinetic energy is independent of height. Find the total heat capacity per atom. The total heat capacity is the sum of contributions from the kinetic energy and from the potential energy. Take the zero of the gravitational energy at the bottom \(h=0\) of the column. Integrate from \(h=0\) to \(h=\infty\). You may assume the gas is ideal.