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(a) Show that the specific heat at constant volume (CV ) is a function of T only.
Remember the
S
CV = T T V
.
CV
V
= 0.
T
So:
CV S 2S S
V
= V
T T V
=T V T
=T T V
T T V T
Using
F F 2F 2F
F (T, V ) = S dT p dV = dT + dV and =
T V V T V T T V
S p
V T
= T V
2p
CV
V
=T (T )2 V
T
Using
RT a
p= V b
V2
CV
V
=0
T
1
(b) Is the results still true if the fluid obeys the Dieterici equation of state?
No, for the Dieterici equation of state, we find that:
2p
1
(T )2 V
= 1
R2 V 2 T 3 (V b)
e RT V 6= 0.
(c) Find the entropy S(T, V ) for the van der Waals fluid.
Remember that we can write:
S S 1 p
dS = T V
dT + V
dV = C
T V
dT + T
dV
T V
Using:
p R
T
= V b
1 R
dS = C
T V
dT + V b
dV
S= CV T1 dT + R ln(V b)
R
S = CV ln T + R ln(V b) + constants
2
2. Simple paramagnet
For N particles:
Using G = kB T ln ZN :
This means that a = N kB and b = kB
.
(b) Find the expression of the magnetization M and the magnetic enthalpy H = G + T S
in terms of Hext and T. Verify that H = M Hext .
z N .
M =
To find
z , we use:
Hext Hext
e kB T e kB T
z (s) P (s) = P P , where P =
P
z = Z
= H
2 cosh k ext
and
s B T
Hext Hext
e kB T e kB T
P = Z
= H
2 cosh k ext
.
T B
Hext Hext
z = H
2 cosh k ext
e kB T
e kB T
= tanh H ext
kB T
.
B T
So,
3
The entropy S is given by:
G
S= T V
G N Hext
S= T V
= N k ln 2 cosh muH ext
kB T
T
tanh muH ext
kB T
Using H = G + T S:
H = N KB T ln 2 cosh muH ext
kB T
+ N KB T ln 2 cosh muH ext
kB T
T N H
T
ext
tanh muH ext
kB T
H = M Hext
(c) Show that the expression of the entropy S obeys the Planck formulation of the third
principle.
G N Hext
S= T V
= N k ln 2 cosh muH ext
kB T
T
tanh muH ext
kB T
The third principle states that the specific heat will go to 0 for T approaching 0K.
we can use:
S
CV = T T
S N 2 Hext
2
T T = 1
kB T muHext
cosh2 kB T
1
Since cosh x for large x, and CV is proportional to coshx
, the third principle is fulfilled.
4
(d) Is the expression of the isotheral susceptibility T in terms of Hext and T consistent
with the postulates of thermodynamics?
N 2
M 1
T = Hext T
= kB T Hext
cosh2 kB T
Hext Hext
For kB T
1, cosh kB T
1, which means that in the limit of high temperatures:
N 2
T = kB T
Curies Law.
Hext Hext
In the limit of low temperature, kB T
, cosh kB T
, so that:
lim T = 0
T 0
5
3. Degenerate Fermi Gas
(a) For the low temperature limit (i.e. T = 0K), find the Fermi energy EF and the total
energy U0 of all electrons in the conduction band (per unit volume). Express your answer in
eV.
R
N= g()f () d.
0
Rf Rf Rf 3/2 3/2
1 2m 1 2m 2 3/2
N= g()f () d = g() d = 2 2 h2
1/2 d = 2 2 h2
3 f
0 0 0
h2
3/2
f = 2m
(3 2 N )
f = 1.1 1018 J 7 eV
Rf 3/2 Rf 3/2
1 2m 2 1 2m 5/2
U0 = g() d = 2 2 h2
3/2 /, d = 5 2 2 h2
f
0 0
2
U0 = 5
N f
(b) Calculate the energy interval that is occupied by the electrons that participate in the
current flow at room temperature (i.e. T = 300K).The occupancy at non-zero temperature
is given by:
1
n
() = f
+1
e kB T
1
0.9 = 1 f
+1
e kB T
1 = f kB T ln 9
6
1
0.1 = 2 f
+1
e kB T
2 = f + kB T ln 9
= 0.11 eV
(c) Using your answers to part (b), find the fraction of current carrying electrons N1 over
N1
the total number of electrons in the conduction band Ntotal (i.e. Ntotal
).
First, find the number of current carrying electrons N1 in the energy window f 2
,
using = 0.11 eV and f = 7 eV :
f +
2
R
N1 = n
()g() d
f
2
For a small energy window, we can assume that g() is independent of energy (i.e. g(f
2
) = 32 Nf , and n (f
varies linearly with energy, i.e. n 2
) = 12 4kB T (using only the
linear term in the series expansion of the Fermi-Dirac distribution).
f +
2
2
3N R 1
3N 1
()g() d
R
N1 = n 2f 2 4kB T
d = 2f 2
f
2
2
N1
So, the fraction of charges contributing to the current N
is now given by:
N1 3N 3
N
= 3N f
= 4f
N1
N
= 0.012
This means that only 1.2% of all the electrons in the conduction band contribute to the
current in Cu at 300K.
7
4. The Ideal Gas
(a) Determine the kind of compression that took place here. Explain!
This is an adiabatic compression with Q = 0.
(b) Find the temperature T2 and the volume V2 in terms of V1 , p2 and T1 after the thermo-
dynamic equilibrium has been reached.
U = Q pdV
CV (T2 T1 ) = p2 (V2 V1 )
N kB T2
Now use p2 V2 = N kB T2 V2 = p2
:
T2 = CpV2 N kB T2
p2
V1 + T1
T2 = p2 V1 +C
Cp
V T1
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(c) Find the final values of the temperature Tf and volume Vf in terms of p1 , V2 , and T2
after the thermodynamic equilibrium is reached again.
N kB Tf
Tf = CV T2C+p
p
1 V2
and Vf = p1
CV (T2 T1 ) + p2 (V2 V1 ) = 0
CV (Tf T2 ) + p1 (V1 V2 ) = 0
CV (Tf T1 ) + p2 (V2 V1 ) + p1 (Vf V2 ) = 0
using pV = N kB T
(pV ) = pV + V p = N kB T
Using CV T + pV = 0:
pV
pV + V p = N kB CV
CP pV + CV V p = 0
CP p2 (V2 V1 ) + CV V2 (p2 p1 ) = 0
CP p1 (Vf V2 ) + CV Vf (pf p2 ) = 0
p2 (V2 V1 ) + p1 (Vf V2 ) = CCVP [V2 (p1 p2 ) + Vf (p2 pf )]
Using pf = p1 and Vf = V1 , we can plug this into the equation above and find:
Tf T1 = CV
(CP )2
(p1 p2 )2 V2
P2
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This result shows that the temperature difference Tf T1 will always be positive, as required
by the thermodynamic principles. Also, it appears that the temperature difference is only a
2nd -order correction term, which will become very small for P 0.
10
5. Einstein Solid
(a) For the most probable macrostate, determine the number of units of heat energy in each
of the two systems. Explain your approach.
!
q+N 1 (q+N 1)!
= = q!(N 1)!
q
and
total = A B
qA A qB B total
8 165 12 6188 1.021 106
7 120 13 8568 1.028 106
6 84 14 11628 0.98 106
(b) Determine the probability of finding the system in the most probable macrostate.
To determine the probability of a macrostate, we need to calculate:
A B
P = total
using
! !
q + Ntotal 1 20 + 10 1
total = = = 10.02 107
q 20
A B
P = total
= 0.1
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