Activities
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 \(U\).
A one-dimensional harmonic oscillator has an infinite series of equally spaced energy states, with \(\varepsilon_n = n\hbar\omega\), where \(n\) is an integer \(\ge 0\), and \(\omega\) is the classical frequency of the oscillator. We have chosen the zero of energy at the state \(n=0\) which we can get away with here, but is not actually the zero of energy! To find the true energy we would have to add a \(\frac12\hbar\omega\) for each oscillator.
Show that for a harmonic oscillator the free energy is \begin{equation} F = k_BT\log\left(1 - e^{-\frac{\hbar\omega}{k_BT}}\right) \end{equation} Note that at high temperatures such that \(k_BT\gg\hbar\omega\) we may expand the argument of the logarithm to obtain \(F\approx k_BT\log\left(\frac{\hbar\omega}{kT}\right)\).
From the free energy above, show that the entropy is \begin{equation} \frac{S}{k_B} = \frac{\frac{\hbar\omega}{kT}}{e^{\frac{\hbar\omega}{kT}}-1} - \log\left(1-e^{-\frac{\hbar\omega}{kT}}\right) \end{equation}
This entropy is shown in the nearby figure, as well as the heat capacity.
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 \[ \left(\frac{\partial {S}}{\partial {p}}\right)_{T} \]
Problem
As discussed in class, we can consider a black body as a large box with a small hole in it. If we treat the large box a metal cube with side length \(L\) and metal walls, the frequency of each normal mode will be given by: \begin{align} \omega_{n_xn_yn_z} &= \frac{\pi c}{L}\sqrt{n_x^2 + n_y^2 + n_z^2} \end{align} where each of \(n_x\), \(n_y\), and \(n_z\) will have positive integer values. This simply comes from the fact that a half wavelength must fit in the box. There is an additional quantum number for polarization, which has two possible values, but does not affect the frequency. Note that in this problem I'm using different boundary conditions from what I use in class. It is worth learning to work with either set of quantum numbers. Each normal mode is a harmonic oscillator, with energy eigenstates \(E_n = n\hbar\omega\) where we will not include the zero-point energy \(\frac12\hbar\omega\), since that energy cannot be extracted from the box. (See the Casimir effect for an example where the zero point energy of photon modes does have an effect.)
- Note
- This is a slight approximation, as the boundary conditions for light are a bit more complicated. However, for large \(n\) values this gives the correct result.
Show that the free energy is given by \begin{align} F &= 8\pi \frac{V(kT)^4}{h^3c^3} \int_0^\infty \ln\left(1-e^{-\xi}\right)\xi^2d\xi \\ &= -\frac{8\pi^5}{45} \frac{V(kT)^4}{h^3c^3} \\ &= -\frac{\pi^2}{45} \frac{V(kT)^4}{\hbar^3c^3} \end{align} provided the box is big enough that \(\frac{\hbar c}{LkT}\ll 1\). Note that you may end up with a slightly different dimensionless integral that numerically evaluates to the same result, which would be fine. I also do not expect you to solve this definite integral analytically, a numerical confirmation is fine. However, you must manipulate your integral until it is dimensionless and has all the dimensionful quantities removed from it!
Show that the entropy of this box full of photons at temperature \(T\) is \begin{align} S &= \frac{32\pi^5}{45} k V \left(\frac{kT}{hc}\right)^3 \\ &= \frac{4\pi^2}{45} k V \left(\frac{kT}{\hbar c}\right)^3 \end{align}
Show that the internal energy of this box full of photons at temperature \(T\) is \begin{align} \frac{U}{V} &= \frac{8\pi^5}{15}\frac{(kT)^4}{h^3c^3} \\ &= \frac{\pi^2}{15}\frac{(kT)^4}{\hbar^3c^3} \end{align}
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.
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.
Problem
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.
What is the change in entropy of the gas? How do you know this?
- What is the change in temperature of the 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 \(\beta = \frac1{kT}\).
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.
Problem
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 \((\cdots)^2\).
This short lecture introduces the ideas required for Ice Calorimetry Lab or Microwave oven Ice Calorimetry Lab.
A student is invited to “act out” motion corresponding to a plot of effective potential vs. distance. The student plays the role of the “Earth” while the instructor plays the “Sun”.
Students calculate probabilities for a particle on a ring using three different notations: Dirac bra-ket, matrix, and wave function. After calculating the angular momentum and energy measurement probabilities, students compare their calculation methods for notation.
A short lecture introducing the idea that most of the energy loss when driving is going into the kinetic energy of the air.
Students consider the change in internal energy during three different processes involving a container of water vapor on a stove. Using the 1st Law of Thermodynamics, students reason about how the internal energy would change and then compare this prediction with data from NIST presented as a contour plot.
Students examine a plastic “surface” graph of the gravitational potential energy of an Earth-satellite system to explore the properties of gravitational potential energy for a spherically symmetric system.
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 \(\beta = \frac1{kT}\).
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
Find the equilibrium value at temperature \(T\) of the fractional magnetization \begin{equation} \frac{\mu_{tot}}{Nm} \equiv \frac{2\langle s\rangle}{N} \end{equation} of a system of \(N\) spins each of magnetic moment \(m\) in a magnetic field \(B\). The spin excess is \(2s\). The energy of this system is given by \begin{align} U &= -\mu_{tot}B \end{align} where \(\mu_{tot}\) is the total magnetization. Take the entropy as the logarithm of the multiplicity \(g(N,s)\) as given in (1.35 in the text): \begin{equation} S(s) \approx k_B\log g(N,0) - k_B\frac{2s^2}{N} \end{equation} for \(|s|\ll N\), where \(s\) is the spin excess, which is related to the magnetization by \(\mu_{tot} = 2sm\). Hint: Show that in this approximation \begin{equation} S(U) = S_0 - k_B\frac{U^2}{2m^2B^2N}, \end{equation} with \(S_0=k_B\log g(N,0)\). Further, show that \(\frac1{kT} = -\frac{U}{m^2B^2N}\), where \(U\) denotes \(\langle U\rangle\), the thermal average energy.
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.
Students sketch the temperature-dependent heat capacity of molecular nitrogen. They apply the equipartition theorem and compute the temperatures at which degrees of freedom “freeze out.”
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.
This lecture is one step in motivating the form of the Planck distribution.
Groups are asked to analyze the following standard problem:
Two identical lumps of clay of (rest) mass m collide head on, with each moving at 3/5 the speed of light. What is the mass of the resulting lump of clay?
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?
Problem
A diesel engine requires no spark plug. Rather, the air in the cylinder is compressed so highly that the fuel ignites spontaneously when sprayed into the cylinder.
In this problem, you may treat air as an ideal gas, which satisfies the equation \(pV = Nk_BT\). You may also use the property of an ideal gas that the internal energy depends only on the temperature \(T\), i.e. the internal energy does not change for an isothermal process. For air at the relevant range of temperatures the heat capacity at fixed volume is given by \(C_V=\frac52Nk_B\), which means the internal energy is given by \(U=\frac52Nk_BT\).
Note: in this problem you are expected to use only the equations given and fundamental physics laws. Looking up the formula in a textbook is not considered a solution at this level.
If the air is initially at room temperature (taken as \(20^{o}C\)) and is then compressed adiabatically to \(\frac1{15}\) of the original volume, what final temperature is attained (before fuel injection)?
- By what factor does the pressure increase?
Problem
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?
In this course, two of the primary examples we will be using are the potential due to gravity and the potential due to an electric charge. Both of these forces vary like \(\frac{1}{r}\), so they will have many, many similarities. Most of the calculations we do for the one case will be true for the other. But there are some extremely important differences:
- Find the value of the electrostatic potential energy of a system consisting of a hydrogen nucleus and an electron separated by the Bohr radius. Find the value of the gravitational potential energy of the same two particles at the same radius. Use the same system of units in both cases. Compare and the contrast the two answers.
- Find the value of the electrostatic potential due to the nucleus of a hydrogen atom at the Bohr radius. Find the gravitational potential due to the nucleus at the same radius. Use the same system of units in both cases. Compare and contrast the two answers.
- Briefly discuss at least one other fundamental difference between electromagnetic and gravitational systems. Hint: Why are we bound to the earth gravitationally, but not electromagnetically?
(Messy algebra) Convince yourself that the expressions for kinetic energy in original and center of mass coordinates are equivalent. The same for angular momentum.
Consider a system of two particles of mass \(m_1\) and \(m_2\).
- Show that the total kinetic energy of the system is the same as that of two “fictitious” particles: one of mass \(M=m_1+m_2\) moving with the velocity of the center of mass and one of mass \(\mu\) (the reduced mass) moving with the velocity of the relative position.
- Show that the total angular momentum of the system can similarly be decomposed into the angular momenta of these two fictitious particles.
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?
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 examine a plastic "surface" graph of the gravitational potential energy of a Earth-satellite system to make connections between gravitational force and gravitational potential energy.
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.
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.
Show that the total energy of the ground state of the gas is \begin{align} U_0 &= \frac34 N\varepsilon_F \end{align}
Consider a white dwarf of mass \(M\) and radius \(R\). The dwarf consists of ionized hydrogen, thus a bunch of free electrons and protons, each of which are fermions. Let the electrons be degenerate but nonrelativistic; the protons are nondegenerate.
Show that the order of magnitude of the gravitational self-energy is \(-\frac{GM^2}{R}\), where \(G\) is the gravitational constant. (If the mass density is constant within the sphere of radius \(R\), the exact potential energy is \(-\frac53\frac{GM^2}{R}\)).
Show that the order of magnitude of the kinetic energy of the electrons in the ground state is \begin{align} \frac{\hbar^2N^{\frac53}}{mR^2} \approx \frac{\hbar^2M^{\frac53}}{mM_H^{\frac53}R^2} \end{align} where \(m\) is the mass of an electron and \(M_H\) is the mas of a proton.
Show that if the gravitational and kinetic energies are of the same order of magnitude (as required by the virial theorem of mechanics), \(M^{\frac13}R \approx 10^{20} \text{g}^{\frac13}\text{cm}\).
If the mass is equal to that of the Sun (\(2\times 10^{33}g\)), what is the density of the white dwarf?
It is believed that pulsars are stars composed of a cold degenerate gas of neutrons (i.e. neutron stars). Show that for a neutron star \(M^{\frac13}R \approx 10^{17}\text{g}^{\frac13}\text{cm}\). What is the value of the radius for a neutron star with a mass equal to that of the Sun? Express the result in \(\text{km}\).
Students use a completeness relations to write hydrogen atoms states in the energy and position bases.
In this activity students work out energy level transitions in hydrogen that lead to visible light.
Students implement a finite-difference approximation for the kinetic energy operator as a matrix, and then use numpy
to solve for eigenvalues and eigenstates, which they visualize.
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.
Students work out heat and work for rectangular paths on \(pV\) and \(TS\) plots. This gives with computing heat and work, applying the First Law, and recognizing that internal energy is a state function, which cannot change after a cyclic process.
Students observe the motion of a puck tethered to the center of the airtable. Then they plot the potential energy for the puck on their small whiteboards. A class discussion follows based on what students have written on their whiteboards.
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}
This lab gives students a chance to take data on the first day of class (or later, but I prefer to do it the first day of class). It provides an immediate context for thermodynamics, and also gives them a chance to experimentally measure a change in entropy. Students are required to measure the energy required to melt ice and raise the temperature of water, and measure the change in entropy by integrating the heat capacity.
In this activity, students apply the Stefan-Boltzmann equation and the principle of energy balance in steady state to find the steady state temperature of a black object in near-Earth orbit.
In this activity students combine energy conservation with the relationship between the de Broglie wavelength and momentum to find the wavelength of atoms that have been dropped a given distance.
Students count the quadratic degrees of freedom of a few toy molecules to predict their internal energy at temperature \(T\).
In this introduction to heat capacity, students determine a derivative that indicates how much the internal energy changes as the temperature changes when volume is held constant.
Students consider how changing the volume of a system changes the internal energy of the system. Students use plastic graph models to explore these functions.
The instructor gives a brief lecture about time dependence of energy eigenstates (e.g. McIntyre, 3.1). Notes for the students are attached.