In our week on radiation, we saw that the Helmholtz free energy of a box of radiation at temperature \(T\) is \begin{align} F &= -8\pi \frac{V(kT)^4}{h^3c^3}\frac{\pi^4}{45} \end{align} From this we also found the internal energy and entropy \begin{align} U &= 24\pi \frac{(kT)^4}{h^3c^3}\frac{\pi^4}{45} V \\ S &= 32\pi kV\left(\frac{kT}{hc}\right)^3 \frac{\pi^4}{45} \end{align} Given these results, let us consider a Carnot engine that uses an empty metalic piston (i.e. a photon gas).

1. Given \(T_H\) and \(T_C\), as well as \(V_1\) and \(V_2\) (the two volumes at \(T_H\)), determine \(V_3\) and \(V_4\) (the two volumes at \(T_C\)).

2. What is the heat \(Q_H\) taken up and the work done by the gas during the first isothermal expansion? Are they equal to each other, as for the ideal gas?

3. Does the work done on the two isentropic stages cancel each other, as for the ideal gas?

4. Calculate the total work done by the gas during one cycle. Compare it with the heat taken up at \(T_H\) and show that the energy conversion efficiency is the Carnot efficiency.

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?

(modified from K&K 4.6) We discussed in class that \begin{align} p &= -\left(\frac{\partial F}{\partial V}\right)_T \end{align} Use this relationship to show that

1. \begin{align} p &= -\sum_j \langle n_j\rangle\hbar \left(\frac{d\omega_j}{dV}\right), \end{align} where \(\langle n_j\rangle\) is the number of photons in the mode \(j\);

2. Solve for the relationship between pressure and internal energy.

Task: Draw a right triangle. Put a circle around the right angle, that is, the angle that is \(\frac\pi2\) radians.

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Consider the finite line with a uniform charge density from class.

1. Write an integral expression for the electric field at any point in space due to the finite line. In addition to your usual physics sense-making, you must include a clearly labeled figure and discuss what happens to the direction of the unit vectors as you integrate.Consider the finite line with a uniform charge density from class.
2. Perform the integral to find the \(z\)-component of the electric field. In addition to your usual physics sense-making, you must compare your result to the gradient of the electric potential we found in class. (If you want to challenge yourself, do the \(s\)-component as well!)

Suppose that a system of \(N\) atoms of type \(A\) is placed in diffusive contact with a system of \(N\) atoms of type \(B\) at the same temperature and volume.

1. Show that after diffusive equilibrium is reached the total entropy is increased by \(2Nk\ln 2\). The entropy increase \(2Nk\ln 2\) is known as the entropy of mixing.

2. If the atoms are identical (\(A=B\)), show that there is no increase in entropy when diffusive contact is established. The difference has been called the Gibbs paradox.

3. Since the Helmholtz free energy is lower for the mixed \(AB\) than for the separated \(A\) and \(B\), it should be possible to extract work from the mixing process. Construct a process that could extract work as the two gasses are mixed at fixed temperature. You will probably need to use walls that are permeable to one gas but not the other.

Note

This course has not yet covered work, but it was covered in Energy and Entropy, so you may need to stretch your memory to finish part (c).

This question is about the lab we did in class: Ice Calorimetry Lab.

1. Plot your data I Plot the temperature versus total energy added to the system (which you can call \(Q\)). To do this, you will need to integrate the power. Discuss this curve and any interesting features you notice on it.
2. Plot your data II Plot the heat capacity versus temperature. This will be a bit trickier. You can find the heat capacity from the previous plot by looking at the slope. \begin{align} C_p &= \left(\frac{\partial Q}{\partial T}\right)_p \end{align} This is what is called the heat capacity, which is the amount of energy needed to change the temperature by a given amount. The \(p\) subscript means that your measurement was made at constant pressure. This heat capacity is actually the total heat capacity of everything you put in the calorimeter, which includes the resistor and thermometer.
3. Specific heat From your plot of \(C_p(T)\), work out the heat capacity per unit mass of water. You may assume the effect of the resistor and thermometer are negligible. How does your answer compare with the prediction of the Dulong-Petit law?
4. Latent heat of fusion What did the temperature do while the ice was melting? How much energy was required to melt the ice in your calorimeter? How much energy was required per unit mass? per molecule?
5. Entropy of fusion The change in entropy is easy to measure for a reversible isothermal process (such as the slow melting of ice), it is just \begin{align} \Delta S &= \frac{Q}{T} \end{align} where \(Q\) is the energy thermally added to the system and \(T\) is the temperature in Kelvin. What is was change in the entropy of the ice you melted? What was the change in entropy per molecule? What was the change in entropy per molecule divided by Boltzmann's constant?
6. Entropy for a temperature change Choose two temperatures that your water reached (after the ice melted), and find the change in the entropy of your water. This change is given by \begin{align} \Delta S &= \int \frac{{\mathit{\unicode{273}}} Q}{T} \\ &= \int_{t_i}^{t_f} \frac{P(t)}{T(t)}dt \end{align} where \(P(t)\) is the heater power as a function of time and \(T(t)\) is the temperature, also as a function of time.

Consider a system of fixed volume in thermal contact with a resevoir. Show that the mean square fluctuations in the energy of the system is \begin{equation} \left<\left(\varepsilon-\langle\varepsilon\rangle\right)^2\right> = k_BT^2\left(\frac{\partial U}{\partial T}\right)_{V} \end{equation} Here \(U\) is the conventional symbol for \(\langle\varepsilon\rangle\). Hint: Use the partition function \(Z\) to relate \(\left(\frac{\partial U}{\partial T}\right)_V\) to the mean square fluctuation. Also, multiply out the term \((\cdots)^2\).

Consider the bottle in a bottle problem in a previous problem set, summarized here.

A small bottle of helium is placed inside a large bottle, which otherwise contains vacuum. The inner bottle contains a slow leak, so that the helium leaks into the outer bottle. The inner bottle contains one tenth the volume of the outer bottle, which is insulated.

The volume of the small bottle is 0.001 m²³ and the volume of the big bottle is 0.01 m³. The initial state of the gas in the small bottle was \(p=106\) Pa and its temperature \(T=300\) K. Approximate the helium gas as an ideal gas of equations of state \(pV=Nk_BT\) and \(U=\frac32 Nk_BT\).

1. How many molecules of gas does the large bottle contain? What is the final temperature of the gas?

2. Compute the integral \(\int \frac{{\mathit{\unicode{273}}} Q}{T}\) and the change of entropy \(\Delta S\) between the initial state (gas in the small bottle) and the final state (gas leaked in the big bottle).

3. Discuss your results.