Entropy of mixing

  • Entropy Equilibrium Sackur-Tetrode
    • assignment Radiation in an empty box

      assignment Homework

      Radiation in an empty box
      Thermal physics Radiation Free energy Thermal and Statistical Physics 2020

      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.

      1. 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!

      2. 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}

      3. 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}

    • assignment Ideal gas calculations

      assignment Homework

      Ideal gas calculations
      Ideal gas Entropy Sackur-Tetrode Thermal and Statistical Physics 2020

      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?

    • assignment Active transport

      assignment Homework

      Active transport
      Active transport Concentration Chemical potential Thermal and Statistical Physics 2020

      The concentration of potassium \(\text{K}^+\) ions in the internal sap of a plant cell (for example, a fresh water alga) may exceed by a factor of \(10^4\) the concentration of \(\text{K}^+\) ions in the pond water in which the cell is growing. The chemical potential of the \(\text{K}^+\) ions is higher in the sap because their concentration \(n\) is higher there. Estimate the difference in chemical potential at \(300\text{K}\) and show that it is equivalent to a voltage of \(0.24\text{V}\) across the cell wall. Take \(\mu\) as for an ideal gas. Because the values of the chemical potential are different, the ions in the cell and in the pond are not in diffusive equilibrium. The plant cell membrane is highly impermeable to the passive leakage of ions through it. Important questions in cell physics include these: How is the high concentration of ions built up within the cell? How is metabolic energy applied to energize the active ion transport?

      David adds
      You might wonder why it is even remotely plausible to consider the ions in solution as an ideal gas. The key idea here is that the ideal gas entropy incorporates the entropy due to position dependence, and thus due to concentration. Since concentration is what differs between the cell and the pond, the ideal gas entropy describes this pretty effectively. In contrast to the concentration dependence, the temperature-dependence of the ideal gas chemical potential will not be so great.

    • keyboard Sinusoidal basis set

      keyboard Computational Activity

      120 min.

      Sinusoidal basis set
      Computational Physics Lab II 2022 (2 years)

      inner product wave function quantum mechanics particle in a box

      Students compute inner products to expand a wave function in a sinusoidal basis set. This activity introduces the inner product for wave functions, and the idea of approximating a wave function using a finite set of basis functions.
    • face Energy and Entropy review

      face Lecture

      5 min.

      Energy and Entropy review
      Thermal and Statistical Physics 2020 (3 years)

      thermodynamics statistical mechanics

      This very quick lecture reviews the content taught in Energy and Entropy, and is the first content in Thermal and Statistical Physics.
    • assignment Spin Fermi Estimate

      assignment Homework

      Spin Fermi Estimate
      Quantum Fundamentals 2022 The following two problems ask you to make Fermi estimates. In a good Fermi estimate, you start from basic scientific facts you already know or quantities that you can reasonably estimate based on your life experiences and then reason your way to estimate a quantity that you would not be able guess. You may look up useful conversion factors or constants. Use words, pictures, and equations to explain your reasoning:
      1. Imagine that you send a pea-sized bead of silver through a Stern-Gerlach device oriented to measure the z-component of intrinsic spin. Estimate the total z-component of the intrinsic spin of the ball you would measure in the HIGHLY improbable case that every atom is spin up.
      2. Protons, neutrons, and electrons are all spin-1/2 particles. Give a (very crude) order of magnitude estimate of the number of these particles in your body.
    • face Fermi and Bose gases

      face Lecture

      120 min.

      Fermi and Bose gases
      Thermal and Statistical Physics 2020

      Fermi level fermion boson Bose gas Bose-Einstein condensate ideal gas statistical mechanics phase transition

      These lecture notes from week 7 of Thermal and Statistical Physics apply the grand canonical ensemble to fermion and bosons ideal gasses. They include a few small group activities.
    • face Entropy and Temperature

      face Lecture

      120 min.

      Entropy and Temperature
      Thermal and Statistical Physics 2020

      paramagnet entropy temperature statistical mechanics

      These lecture notes for the second week of Thermal and Statistical Physics involve relating entropy and temperature in the microcanonical ensemble, using a paramagnet as an example. These notes include a few small group activities.
    • group Ideal Gas Model

      group Small Group Activity

      30 min.

      Ideal Gas Model

      Ideal Gas surfaces thermo

      Students should be familiar with the basic definitions of pressure, volume, temperature, and internal energy.
    • group Expectation Values for a Particle on a Ring

      group Small Group Activity

      30 min.

      Expectation Values for a Particle on a Ring
      Central Forces 2022 (2 years)

      central forces quantum mechanics eigenstates eigenvalues hermitian operators quantum measurements degeneracy expectation values time dependence

      Quantum Ring Sequence

      Students calculate the expectation value of energy and angular momentum as a function of time for an initial state for a particle on a ring. This state is a linear combination of energy/angular momentum eigenstates written in bra-ket notation.
  • Thermal and Statistical Physics 2020

    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).