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Physics Department
8.044 Statistical Physics I Spring Term 2013
Solutions to Problem Set #6
We need to find (∂T /∂P )∆Q=0 . To do this we will use in sequence the first law, the energy
derivative given in the statement of the problem, and the chain rule for partial derivatives.
/Q = dU − d/W = dU + P dV
d
∂U ∂U
= dT + + P dV = 0
∂T V ∂V T
| {z } | {z }
CV A
∂V
∂P −1 ∂T P αT
A = T = T = T =
∂T V ∂T ∂V ∂V κT
−
∂V P ∂P T ∂P T
αT
0 = CV dT + dV
κT
αT
0 = CV dT +
κT
(αV0 dT − κT V0 dP )
α 2 T V0
� ∂P �
αT V0 dP = CV + dT
κT
∆T αT
∂V T
= 2
∆P CV α T
+
V0 κT
1
Problem 2: Energy of a Film
a) The best approach to take here is to find a general expression for CA and then show that
its derivative with respect to A is zero.
d/Q
CA ≡
dT A
∂S
= T by the second law
∂T A
∂CA ∂ 2S
= T
∂A T ∂A∂T
∂ ∂S
= T interchanging order of the derivatives
∂T ∂A T A
We use a Maxwell relation to find (∂S/∂A)T . Note that S and S are different variables. I
would normally construct a magic square to find the equivalent derivatives, but for clarity I
will go through the more fundamental route here.
dE = T dS + S dA
dF = dE − d(T S) = −S dT + S dA
Substitute this result into the expression for the derivative of the heat capacity.
∂CA ∂ Nk
=T =0
∂A T ∂T A − b A
This shows that the heat capacity at constant area does not depend on the area: CA (T, A) =
CA (T ).
2
b) Now we find the exact differential for the energy and integrate up.
dE = T dS + S dA
∂S ∂S
= T dT + T + S dA
∂T A ∂A T
| {z } | {z }
CA (T ) N kT
− +S =0
A−b
∂E
⇒ =0
∂A T
E(T, A) = E(T )
Z T
= CA (T 0 ) dT 0 + E(T = 0)
0
dE = T dS − P dV
∂S ∂S
= T dT + T − P dV
∂T V ∂V T
| {z }
CV
dF = dE − d(T S) = −S dT − P dV
∂S ∂P
⇒ − =−
∂V T ∂T V
∂P 3/2 2 ∂S
= (5/2)aT + 3bT =
∂T V ∂V T
∂S
T −P = (5/2)aT 5/2 + 3bT 3 − aT 5/2 − bT 3 − cV −2
∂V T
3
b) Use the fact that the energy is a state function which requires that the cross derivatives
must be equal.
∂ ∂E ∂ ∂E
=
∂V ∂T V T ∂T ∂V T V
⇒ d = (15/4)a, e = 6b
⇒ F 0 = −cV −2 , F = cV −1 + KE
4
Integrate with respect to T first.
⇒ G 0 (V ) = 0, G(V ) = KS
Problem 4: Paramagnet
d/Q
CM ≡
dT M
∂S
= T by the second law
∂T M
∂CM ∂ 2S
= T
∂M T ∂M ∂T
∂ ∂S
= T interchanging order of the derivatives
∂T ∂M T M
A M
M= H ⇒ H= (T − T0 )
T − T0 A
We use a Maxwell relation to find (∂S/∂M )T .
dE = T dS + H dM
dF = dE − d(T S) = −S dT + H dM
5
Substitute this result into the expression for the derivative of the heat capacity.
∂CM ∂ M
=T − =0
∂M T ∂T A M
This shows that the heat capacity at constant magnetization does not depend on the mag-
netization: CM (T, M ) = CM (T ).
b)
dE = T dS + H dM
∂S ∂S
= T dT + T +H dM
∂T M ∂M T
| {z } | {z }
CM (T ) −M T /A + H = −M T0 /A
M T0
= − from dE
A
M 2 T0
⇒ f (M ) = − + KE
2A
Z T
M 2 T0
E(T, M ) = CM (T 0 ) dT 0 − + KE
0 2A
c)
∂S ∂S
dS = dT + dM
∂T M ∂M T
| {z } | {z }
CM (T )/T −M/A from a)
Z T
CM (T 0 ) 0
S(T, M ) = dT + g(M )
0 T0
6
∂S
= g 0 (M ) from above
∂M T
M
= − from dS
A
M2
⇒ g(M ) = − + KS
2A
Z T
CM (T 0 ) 0 M 2
S(T, M ) = dT − + KS
0 T0 2A
7
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