Activities
Problem
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.
- 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.
- 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.
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.
Problem
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.
Solve for the thermal average occupancy of the system in terms of \(\lambda\).
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}
Find an expression for the thermal average energy of the system.
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.
Problem
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).
Compute the entropy.
Work out the heat capacity at constant pressure \(C_p\).
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).
- Compute the internal energy \(U\).
Problem
The Gibbs free energy, \(G\), is given by \begin{align*} G = U + pV - TS. \end{align*}
- Find the total differential of \(G\). As always, show your work.
- Interpret the coefficients of the total differential \(dG\) in order to find a derivative expression for the entropy \(S\).
- From the total differential \(dG\), obtain a different thermodynamic derivative that is equal to \[ \left(\frac{\partial {S}}{\partial {p}}\right)_{T} \]
In this entire problem, keep results to first order in the van der Waals correction terms \(a\) and $b.
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}
Show that the energy is \begin{align} U &= \frac32 NkT - \frac{N^2a}{V} \end{align}
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}
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 \(\frac1{V^{\frac23}}\).
Find an expression for the entropy of a Fermi electron gas in the region \(kT\ll \varepsilon_F\). Notice that \(S\rightarrow 0\) as \(T\rightarrow 0\).
Problem
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.
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.
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.
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).
Problem
Suppose \(g(U) = CU^{3N/2}\), where \(C\) is a constant and \(N\) is the number of particles.
Show that \(U=\frac32 N k_BT\).
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.
The goal of this problem is to show that once we have maximized the entropy and found the microstate probabilities in terms of a Lagrange multiplier \(\beta\), we can prove that \(\beta=\frac1{kT}\) based on the statistical definitions of energy and entropy and the thermodynamic definition of temperature embodied in the thermodynamic identity.
The internal energy and entropy are each defined as a weighted average over microstates: \begin{align} U &= \sum_i E_i P_i & S &= -k_B\sum_i P_i \ln P_i \end{align}: We saw in clase that the probability of each microstate can be given in terms of a Lagrange multiplier \(\beta\) as \begin{align} P_i &= \frac{e^{-\beta E_i}}{Z} & Z &= \sum_i e^{-\beta E_i} \end{align} Put these probabilities into the above weighted averages in order to relate \(U\) and \(S\) to \(\beta\). Then make use of the thermodynamic identity \begin{align} dU = TdS - pdV \end{align} to show that \(\beta = \frac1{kT}\).
This short lecture introduces the ideas required for Ice Calorimetry Lab or Microwave oven Ice Calorimetry Lab.
These lecture notes for the second week of https://paradigms.oregonstate.edu/courses/ph441 involve relating entropy and temperature in the microcanonical ensemble, using a paramagnet as an example. These notes include a few small group activities.
Students are placed into small groups and asked to create an experimental setup they can use to measure the partial derivative they are given, in which entropy changes.
This lecture introduces the idea of entropy, including the relationship between entropy and multiplicity as well as the relationship between changes in entropy and heat.
Problem
Consider a three-state system with energies \((-\epsilon,0,\epsilon)\).
- At infinite temperature, what are the probabilities of the three states being occupied? What is the internal energy \(U\)? What is the entropy \(S\)?
- At very low temperature, what are the three probabilities?
- What are the three probabilities at zero temperature? What is the internal energy \(U\)? What is the entropy \(S\)?
- What happens to the probabilities if you allow the temperature to be negative?
Problem
A 100W light bulb is left burning inside a Carnot refridgerator that draws 100W. Can the refridgerator cool below room temperature?
Problem
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).
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 \(T_C\)).
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?
Does the work done on the two isentropic stages cancel each other, as for the ideal gas?
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.
Show that for a reversible heat pump the energy required per unit of heat delivered inside the building is given by the Carnot efficiency: \begin{align} \frac{W}{Q_H} &= \eta_C = \frac{T_H-T_C}{T_H} \end{align} What happens if the heat pump is not reversible?
Assume that the electricity consumed by a reversible heat pump must itself be generated by a Carnot engine operating between the even hotter temperature \(T_{HH}\) and the cold (outdoors) temperature \(T_C\). What is the ratio \(\frac{Q_{HH}}{Q_H}\) of the heat consumed at \(T_{HH}\) (i.e. fuel burned) to the heat delivered at \(T_H\) (in the house we want to heat)? Give numerical values for \(T_{HH}=600\text{K}\); \(T_{H}=300\text{K}\); \(T_{C}=270\text{K}\).
Draw an energy-entropy flow diagram for the combination heat engine-heat pump, similar to Figures 8.1, 8.2 and 8.4 in the text (or the equivalent but sloppier) figures in the course notes. However, in this case we will involve no external work at all, only energy and entropy flows at three temperatures, since the work done is all generated from heat.
Problem
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.
Find an expression for the energy \(U\) of the gas.
Find an expression for the entropy \(\sigma\). The temperature is \(kT\).
Problem
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.
How much heat (in joules) is added to the gas in each of these two processes?
What is the temperature at the end of the second process?
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?
Problem
- Solve for the heat capacity of a vacuum, given the above, and assuming that photons represent all the energy present in vacuum.
- Compare the heat capacity of vacuum at room temperature with the heat capacity of an equal volume of water.
Problem
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.
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 \(\varepsilon\).
From the free energy, find expressions for the internal energy \(U\) and entropy \(S\) of the system.
Plot the entropy versus \(T\). Explain its asymptotic behavior as the temperature becomes high.
Plot the \(S(T)\) versus \(U(T)\). Explain the maximum value of the energy \(U\).
Problem
Find the entropy of a set of \(N\) oscillators of frequency \(\omega\) as a function of the total quantum number \(n\). Use the multiplicity function: \begin{equation} g(N,n) = \frac{(N+n-1)!}{n!(N-1)!} \end{equation} and assume that \(N\gg 1\). This means you can make the Sitrling approximation that \(\log N! \approx N\log N - N\). It also means that \(N-1 \approx N\).
Let \(U\) denote the total energy \(n\hbar\omega\) of the oscillators. Express the entropy as \(S(U,N)\). Show that the total energy at temperature \(T\) is \begin{equation} U = \frac{N\hbar\omega}{e^{\frac{\hbar\omega}{kT}}-1} \end{equation} This is the Planck result found the hard way. We will get to the easy way soon, and you will never again need to work with a multiplicity function like this.
The goal of this problem is to show that once we have maximized the entropy and found the microstate probabilities in terms of a Lagrange multiplier \(\beta\), we can prove that \(\beta=\frac1{kT}\) based on the statistical definitions of energy and entropy and the thermodynamic definition of temperature embodied in the thermodynamic identity.
The internal energy and entropy are each defined as a weighted average over microstates: \begin{align} U &= \sum_i E_i P_i & S &= -k_B\sum_i P_i \ln P_i \end{align} We saw in clase that the probability of each microstate can be given in terms of a Lagrange multiplier \(\beta\) as \begin{align} P_i &= \frac{e^{-\beta E_i}}{Z} & Z &= \sum_i e^{-\beta E_i} \end{align} Put these probabilities into the above weighted averages in order to relate \(U\) and \(S\) to \(\beta\). Then make use of the thermodynamic identity \begin{align} dU = TdS - pdV \end{align} to show that \(\beta = \frac1{kT}\).
In this remote-friendly activity, students use a microwave oven (and optionally a thermometer) to measure the latent heat of melting for water (and optionally the heat capacity). From these they compute changes in entropy. See also Ice Calorimetry Lab.
Problem
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 m^{23} and the volume of the big bottle is 0.01 m^{3}. 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 \(U=\frac32 Nk_BT\).
How many molecules of gas does the large bottle contain? What is the final temperature of the gas?
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).
- Discuss your results.
These lecture notes covering week 8 of https://paradigms.oregonstate.edu/courses/ph441 include a small group activity in which students derive the Carnot efficiency.
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.
This very quick lecture reviews the content taught in https://paradigms.oregonstate.edu/courses/ph423, and is the first content in https://paradigms.oregonstate.edu/courses/ph441.
Students generate a list of properties a glass of water might have. The class then discusses and categorizes those properties.
Students will determine the change in entropy (positive, negative, or none) for both the system and surroundings in three different cases. This is followed by an active whole-class discussion about where the entropy comes from during an irreversible process.
The students will set up a Styrofoam cup with heating element and a thermometer in it. They will measure the temperature as a function of time, and thus the energy transferred from the power supply, from which they compute changes in entropy.