1. Consider a system that may be unoccupied with energy zero, or occupied by one particle in either of two states, one of energy zero and one of energy \(\varepsilon\). Find the Gibbs sum for this system is in terms of the activity \(\lambda\equiv e^{\beta\mu}\). Note that the system can hold a maximum of one particle.

2. Solve for the thermal average occupancy of the system in terms of \(\lambda\).

3. Show that the thermal average occupancy of the state at energy \(\varepsilon\) is \begin{align} \langle N(\varepsilon)\rangle = \frac{\lambda e^{-\frac{\varepsilon}{kT}}}{\mathcal{Z}} \end{align}

4. Find an expression for the thermal average energy of the system.

5. Allow the possibility that the orbitals at \(0\) and at \(\varepsilon\) may each be occupied each by one particle at the same time; Show that \begin{align} \mathcal{Z} &= 1 + \lambda + \lambda e^{-\frac{\varepsilon}{kT}} + \lambda^2 e^{-\frac{\varepsilon}{kT}} \\ &= (1+\lambda)\left(1+e^{-\frac{\varepsilon}{kT}}\right) \end{align} Because \(\mathcal{Z}\) can be factored as shown, we have in effect two independent systems.

These lecture notes for the first week of https://paradigms.oregonstate.edu/courses/ph441 include a couple of small group activities in which students work with the Gibbs formulation of the entropy.

These notes from the fifth week of https://paradigms.oregonstate.edu/courses/ph441 cover the grand canonical ensemble. They include several small group activities.

Consider two noninteracting systems \(A\) and \(B\). We can either treat these systems as separate, or as a single combined system \(AB\). We can enumerate all states of the combined by enumerating all states of each separate system. The probability of the combined state \((i_A,j_B)\) is given by \(P_{ij}^{AB} = P_i^AP_j^B\). In other words, the probabilities combine in the same way as two dice rolls would, or the probabilities of any other uncorrelated events.

1. Show that the entropy of the combined system \(S_{AB}\) is the sum of entropies of the two separate systems considered individually, i.e. \(S_{AB} = S_A+S_B\). This means that entropy is extensive. Use the Gibbs entropy for this computation. You need make no approximation in solving this problem.
2. Show that if you have \(N\) identical non-interacting systems, their total entropy is \(NS_1\) where \(S_1\) is the entropy of a single system.

Note

In real materials, we treat properties as being extensive even when there are interactions in the system. In this case, extensivity is a property of large systems, in which surface effects may be neglected.

In each of the following sums, shift the index \(n\rightarrow n+2\). Don't forget to shift the limits of the sum as well. Then write out all of the terms in the sum (if the sum has a finite number of terms) or the first five terms in the sum (if the sum has an infinite number of terms) and convince yourself that the two different expressions for each sum are the same:

1. \begin{equation} \sum_{n=0}^3 n \end{equation}
2. \begin{equation} \sum_{n=1}^5 e^{in\phi} \end{equation}
3. \begin{equation} \sum_{n=0}^{\infty} a_n n(n-1)z^{n-2} \end{equation}

The Gibbs free energy, \(G\), is given by \begin{align*} G = U + pV - TS. \end{align*}

1. Find the total differential of \(G\). As always, show your work.
2. Interpret the coefficients of the total differential \(dG\) in order to find a derivative expression for the entropy \(S\).
3. From the total differential \(dG\), obtain a different thermodynamic derivative that is equal to \[ \left(\frac{\partial {S}}{\partial {p}}\right)_{T} \]

None

Many students do not know what it means to add two functions graphically. Students are shown graphs of two simple functions and asked to sketch the sum.

Students learn about the geometric meaning of the amplitude and period parameters in the sine function. They also practice sketching the sum of two functions by hand.