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Derive equation 6.92 and 6.93 for the entropy and chemical potential of an ideal gas.

Short Answer

Expert verified

S=NklnVNvQ+52-∂Fint∂T

μ=-kTlnVZintNvQ

Step by step solution

01

Step 1. Given information

The Helmholtz free energy for an ideal gas is given by

F=-NkTlnV-lnN-lnvQ+1+Fint.........................(1)

Here, V,N,vQ,Fintare the volume, number of molecules, quantum volume and the internal free energy of the ideal gas.

The quantum volume is given by

vQ=h22Ï€mkT32........................(2)

02

Step2. Calculation for the entropy of the gas

Take logarithm from both sides of equation (2).

lnvQ=lnh22Ï€mkT32=-32lnT+32lnh22Ï€mk32...........................(3)

The formula calculate the entropyS of the gas is given by

S=-∂F∂TV,N................................(4)

Substitute the value of the free energy from equation (1) into equation (4) and simplify to obtain the required entropy.

localid="1647062285813" S=-∂∂T-NkTlnV-lnN-lnvQ+1+Fint=NklnVNvQ+1+NkT32T-∂Fint∂T=NklnVNvQ+52-∂Fint∂T

03

Step 3. Calculation for chemical potential

The internal free energy of the gas is given by

Fint=-NkTlnZint............................(5)

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

μ=-∂F∂NT,V.............................(6)

Substitute the value of the free energy from equation (1) into equation (6) and simplify to obtain the required chemical potential.

μ=∂∂N-NkTlnV-lnN-lnvQ+1+Fint=∂∂N-NkTlnV-lnN-lnvQ+1-NkTlnZint[fromequation(5)]=-kTlnVNvQ+1+NkT1N-kTlnZint=-kTlnVNvQ-kTlnZint=-kTlnVZintNvQ

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Most popular questions from this chapter

Consider a classical "degree of freedom" that is linear rather than quadratic E=cqfor some constant c. (As example would be the kinetic energy of a highly relativistic particle in one dimension, written in terms of its momentum.) Repeat derivation of the equipartition theorem for this system, and show that the average energy isrole="math" localid="1646903677918" E-=kT.

This problem concerns a collection of N identical harmonic oscillators (perhaps an Einstein solid or the internal vibrations of gas molecules) at temperature T. As in Section 2.2, the allowed energies of each oscillator are 0, hf, 2hf, and so on. (

a) Prove by long division that

11-x=1+x+x2+x3+⋯

For what values of x does this series have a finite sum?

(b) Evaluate the partition function for a single harmonic oscillator. Use the result of part (a) to simplify your answer as much as possible.

(c) Use formula 6.25 to find an expression for the average energy of a single oscillator at temperature T. Simplify your answer as much as possible.

(d) What is the total energy of the system of N oscillators at temperature T? Your result should agree with what you found in Problem 3.25.

(e) If you haven't already done so in Problem 3.25, compute the heat capacity of this system and check t hat it has the expected limits as T→0 and T→∞.

A lithium nucleus has four independent spin orientations, conventionally labeled by the quantum number m = -3/2, -1/2, 1/2, 3/2. In a magnetic field B, the energies of these four states are E = mμB, where μ the constant is 1.03 x 10-7 eV/T. In the Purcell-Pound experiment described in Section 3.3, the maximum magnetic field strength was 0.63 T and the temperature was 300 K. Calculate the probability of a lithium nucleus being in each of its four spin states under these conditions. Then show that, if the field is suddenly reversed, the probabilities of the four states obey the Boltzmann distribution for T =-300 K.

A particle near earth's surface traveling faster than about 11km/shas enough kinetic energy to completely escape from the earth, despite earth's gravitational pull. Molecules in the upper atmosphere that are moving faster than this will therefore escape if they do not suffer any collisions on the way out.

(a) The temperature of earth's upper atmosphere is actually quite high, around 1000K.Calculate the probability of a nitrogen molecule at this temperature moving faster than 11km/s, and comment on the result.

(b) Repeat the calculation for a hydrogen molecule (H2)and for a helium atom, and discuss the implications.

(c) Escape speed from the moon's surface is only about 2.4km/s. Explain why the moon has no atmosphere.

In the low-temperature limit (kT<<∈), each term in the rotational partition function is much smaller than the one before. Since the first term is independent of T, cut off the sum after the second term and compute the average energy and the heat capacity in this approximation. Keep only the largest T-dependent term at each stage of the calculation. Is your result consistent with the third law of thermodynamics? Sketch the behavior of the heat capacity at all temperature, interpolating between the high-temperature and low- temperature expressions.

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