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Consider a large system of Nindistinguishable, noninteracting molecules (perhaps an ideal gas or a dilute solution). Find an expression for the Helmholtz free energy of this system, in terms of Z1, the partition function for a single molecule. (Use Stirling's approximation to eliminate the N!.) Then use your result to find the chemical potential, again in terms ofZ1.

Short Answer

Expert verified

F=-NkTlnZ1N+1

μ=-kTlnZ1N

Step by step solution

01

Step1. Given information

The partition functionZ for a system of Nindistinguishable, noninteracting molecules is given by

role="math" localid="1647058886923" Z=1N!Z1N...........................(1)

02

Step 2. Calculation for Helmholtz free energy

The formula to calculate the Helmholtz free energy of the system is given by

F=-kTlnZ.............(2)

Substitute the value for Zfrom equation (1) into equation (2) and simplify to obtain the free energy.

role="math" localid="1647059254929" F=-kTln1N!Z1N=-kTNlnZ1-lnZ!=-kTNlnZ1-NlnN+N=-NkTlnZ1N+1...................(3)

03

Step 3. Calculation for chemical potential

The formula to calculate the chemical potential of the system is given by

μ=∂F∂NT,V......................(4)

Substitute the value of the free energy from equation (3) into equation (4) and simplify to obtain the chemical potential of the system.

role="math" localid="1647059391759" μ=∂-NkTlnZ1N+1∂N=-kTlnZ1N+1-NkT∂∂N-lnN=-kTlnZ1N

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Most popular questions from this chapter

Apply the result of Problem 6.18 to obtain a formula for the standard deviation of the energy of a system of N identical harmonic oscillators (such as in an Einstein solid), in the high-temperature limit. Divide by the average energy to obtain a measure of the fractional fluctuation in energy. Evaluate this fraction numerically for N = 1, 104, and 1020. Discuss the results briefly.

Verify from Maxwell speed distribution that the most likely speed of a molecule is2kTm.

In this section we computed the single-particle translational partition function,Ztr, by summing over all definite-energy wave functions. An alternative approach, however, is to sum over all position and momentum vectors, as we did in Section 2.5. Because position and momentum are continuous variables, the sums are really integrals, and we need to slip a factor of 1h3to get a unitless number that actually counts the independent wavefunctions. Thus we might guess the formula

role="math" localid="1647147005946" Ztr=1h3∫d3rd3pe-EtrkT

where the single integral sign actually represents six integrals, three over the position components and three over the momentum components. The region of integration includes all momentum vectors, but only those position vectors that lie within a box of volume V. By evaluating the integrals explicitly, show that this expression yields the same result for the translational partition function as that obtained in the text.

In the numerical example in the text, I calculated only the ratio of the probabilities of a hydrogen atom being in two different states. At such a low temperature the absolute probability of being in a first excited state is essentially the same as the relative probability compared to the ground state. Proving this rigorously, however, is a bit problematic, because a hydrogen atom has infinitely many states.

(a) Estimate the partition function for a hydrogen atom at 5800 K, by adding the Boltzmann factors for all the states shown explicitly in Figure 6.2. (For simplicity you may wish to take the ground state energy to be zero, and shift the other energies according!y.)

(b) Show that if all bound states are included in the sum, then the partition function of a hydrogen atom is infinite, at any nonzero temperature. (See Appendix A for the full energy level structure of a hydrogen atom.)

(c) When a hydrogen atom is in energy level n, the approximate radius of the electron wavefunction is a0n2, where ao is the Bohr radius, about 5 x 10-11 m. Going back to equation 6.3, argue that the PdV term is Tot negligible for the very high-n states, and therefore that the result of part (a), not that of part (b), gives the physically relevant partition function for this problem. Discuss.

Suppose you have 10 atoms of weberium: 4 with energy 0 eV, 3 with energy 1 eV, 2 with energy 4 eV, and 1 with energy 6 eV.

(a) Compute the average energy of all your atoms, by adding up all their energies and dividing by 10.

(b) Compute the probability that one of your atoms chosen at random would have energy E, for each of the four values of E that occur.

(c) Compute the average energy again, using the formulaE¯=∑sE(s)P(s)

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