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 \[ \left(\frac{\partial {S}}{\partial {p}}\right)_{T} \]

Consider a system which has an internal energy \(U\) defined by: \begin{align} U &= \gamma V^\alpha S^\beta \end{align} where \(\alpha\), \(\beta\) and \(\gamma\) are constants. The internal energy is an extensive quantity. What constraint does this place on the values \(\alpha\) and \(\beta\) may have?

You are given the following Gibbs free energy: \begin{equation*} G=-k T N \ln \left(\frac{a T^{5 / 2}}{p}\right) \end{equation*} where \(a\) is a constant (whose dimensions make the argument of the logarithm dimensionless).

1. Compute the entropy.

2. Work out the heat capacity at constant pressure \(C_p\).

3. Find the connection among \(V\), \(p\), \(N\), and \(T\), which is called the equation of state (Hint: find the volume as a partial derivative of the Gibbs free energy).

4. Compute the internal energy \(U\).

Find the differential of each of the following expressions; zap each of the following with \(d\):

1. \[f=3x-5z^2+2xy\]

2. \[g=\frac{c^{1/2}b}{a^2}\]

3. \[h=\sin^2(\omega t)\]

4. \[j=a^x\]

5. \[k=5 \tan\left(\ln{\left(\frac{V_1}{V_2}\right)}\right)\]

The internal energy is of any ideal gas can be written as \begin{align} U &= U(T,N) \end{align} meaning that the internal energy depends only on the number of particles and the temperature, but not the volume.^*

The ideal gas law \begin{align} pV &= Nk_BT \end{align} defines the relationship between \(p\), \(V\) and \(T\). You may take the number of molecules \(N\) to be constant. Consider the free adiabatic expansion of an ideal gas to twice its volume. “Free expansion” means that no work is done, but also that the process is also neither quasistatic nor reversible.

1. What is the change in entropy of the gas? How do you know this?

2. What is the change in temperature of the gas?

The internal energy of helium gas at temperature \(T\) is to a very good approximation given by \begin{align} U &= \frac32 Nk_BT \end{align}

Consider a very irreversible process in which 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. What is the change in temperature when this process is complete? How much of the helium will remain in the small bottle?

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 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.

The isothermal compressibility is defined as \begin{equation} K_{T}=-\frac{1}{V} \left(\frac{\partial V}{\partial p}\right)_{T} \end{equation} \(K_T\) is be found by measuring the fractional change in volume when the the pressure is slightly changed with the temperature held constant. In contrast, the adiabatic compressibility is defined as \begin{equation} K_{S}=-\frac{1}{V} \left(\frac{\partial V}{\partial p}\right)_{S} \end{equation} and is measured by making a slight change in pressure without allowing for any heat transfer. This is the compressibility, for instance, that would directly affect the speed of sound. Show that \begin{equation} \frac{K_{T}}{K_{S}} = \frac{C_{p}}{C_{V}} \end{equation} Where the heat capacities at constant pressure and volume are given by \begin{align} C_{p} &= T \left(\frac{\partial S}{\partial T}\right)_{p} \\ C_{V} &= T \left(\frac{\partial S}{\partial T}\right)_{V} \end{align}

Consider the diagram of \(T\) vs \(V\) for several different constant values of \(p\).

1. Translate this diagram to a \(p\) vs \(V\) w/ constant \(T\) graph, including the point \(A\). Complete your graph by hand and make a fairly accurate sketch by printing out the attached grid or in some other way making nice square axes with appropriate tick marks.

   

2. Are the lines that you drew straight or curved? What feature of the \(TV\) graph would have to change to change this result?

3. Sketch the line of constant temperature that passes through the point \(A\).

4. What are the values of all the thermodynamic variables associated with the point A?

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.

Nuclei of a particular isotope species contained in a crystal have spin \(I=1\), and thus, \(m = \{+1,0,-1\}\). The interaction between the nuclear quadrupole moment and the gradient of the crystalline electric field produces a situation where the nucleus has the same energy, \(E=\varepsilon\), in the state \(m=+1\) and the state \(m=-1\), compared with an energy \(E=0\) in the state \(m=0\), i.e. each nucleus can be in one of 3 states, two of which have energy \(E=\varepsilon\) and one has energy \(E=0\).

1. Find the Helmholtz free energy \(F = U-TS\) for a crystal containing \(N\) nuclei which do not interact with each other.

2. Find an expression for the entropy as a function of temperature for this system. (Hint: use results of part a.)

3. Indicate what your results predict for the entropy at the extremes of very high temperature and very low temperature.

It has been proposed to use the thermal gradient of the ocean to drive a heat engine. Suppose that at a certain location the water temperature is \(22^\circ\)C at the ocean surface and \(4^{o}\)C at the ocean floor.

1. What is the maximum possible efficiency of an engine operating between these two temperatures?

2. If the engine is to produce 1 GW of electrical power, what minimum volume of water must be processed every second? Note that the specific heat capacity of water \(c_p = 4.2\) Jg\(^{-1}\)K\(^{-1}\) and the density of water is 1 g cm\(^{-3}\), and both are roughly constant over this temperature range.

Consider a hanging rectangular rubber sheet. We will consider there to be two ways to get energy into or out of this sheet: you can either stretch it vertically or horizontally. The distance of vertical stretch we will call \(y\), and the distance of horizontal stretch we will call \(x\).

If I pull the bottom down by a small distance \(\Delta y\), with no horizontal force, what is the resulting change in width \(\Delta x\)? Express your answer in terms of partial derivatives of the potential energy \(U(x,y)\).

The spring constant \(k\) for a one-dimensional spring is defined by: \[F=k(x-x_0).\] Discuss briefly whether each of the variables in this equation is extensive or intensive.

A 100W light bulb is left burning inside a Carnot refridgerator that draws 100W. Can the refridgerator cool below room temperature?

1. Find an expression for the free energy as a function of \(T\) of a system with two states, one at energy 0 and one at energy \(\varepsilon\).

2. From the free energy, find expressions for the internal energy \(U\) and entropy \(S\) of the system.

3. Plot the entropy versus \(T\). Explain its asymptotic behavior as the temperature becomes high.

4. Plot the \(S(T)\) versus \(U(T)\). Explain the maximum value of the energy \(U\).