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Physics Department

8.044 Statistical Physics I Spring Term 2013

Solutions to Problem Set #5

a)

3N/2

N 4πemE

Φ = V

3N

S(N, V, T ) = k ln Φ

n o

= k ln V N [2πemkT ]3N/2

= N k ln V + (3/2)N k ln[2πemkT ]

| {z }

6 λN k ln V

=

N1 kT N2 kT

P = = .

V1 V2

Now make use of the definition of α.

N1 kT N2 kT

=

αV (1 − α)V

1−α

N2 = N1

α

N1 N1 N1

= 1−α =α=

N1 + N2 (1 + α )N1 N

N2 N2 N2

= α =1−α=

N1 + N2 ( 1−α + 1)N2 N

1

Since the mixing takes place isothermally (because for ideal gases there is no interaction

between the molecules), the T term in our expression for S of each gas does not change.

∆S1 = N1 k ln V − N1 k ln αV

= N1 k ln(1/α) = N kα ln(1/α)

α ln(1/α) + (1 − α) ln(1/1 − α)

∆S1 + ∆S2 = N k[|{z} >0

| {z } | {z } | {z }

+ + + +

This result is correct if the two gases are different. What should we expect when the gases

are the same? ∆E = 0 since the internal energy of an ideal gas does not depend on the

volume, E(T, V ) = E(T ), and the initial and final temperatures are equal. ∆W = 0 since

no work is necessary to slide the partition in and out (there is no opposing force in the

absence of friction). Using these two results in the first law, ∆E = ∆W + ∆Q, tells us that

∆Q = 0. If the process is reversible ∆S = ∆Q/T and it follows that ∆S = 0. This is

not consistent with the detailed calculation above which indicated a positive ∆S, but which

nowhere required that the two gases be different.

c)

VN

Φ = [2πemkT ]3N/2

N!

S(N, V, T ) = N k ln V − N k ln N + kN}

| {z +(3/2)N k ln[2πemkT ]

neglect compared to

previous term

2

We can summarize the results for the volume-dependent part of the entropies when the

mixing involves only one gas by constructing a table.

with partition without partition

= N k[α ln αV + (1 − α) ln(1 − α)V ]

= N k[α ln α + (1 − α) ln(1 − α) + ln V ] 6= N k ln V

| {z }

+

αV (1−α)V

new S αN k ln αN + (1 − α) ln (1−α)N

= N k[α ln(V /N ) + (1 − α) ln(V /N )]

= N k ln(V /N ) = N k ln(V /N )

3

MIT OpenCourseWare

http://ocw.mit.edu

Spring 2013

For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.

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