Homework solution to Advanced Thermodynamics #8

8.1-1
S
U U ,V V , N 
S 
U U ,V V , N 2S 
U ,V , N  for stability
S S
S 
U U ,V V , N S 
U ,V , N 
 U   V

UV 
VU

1
2 S  2 S  2 S  2 

 
 

U 
2
2
 

 U V 
 V ...

2 
 U
2
U
2  V  V  

SUU 
U 2SUV UV SVV 
V 0
2 2

2
multiplied by SUU , then SUU U 2SUU SUV UV SUU SVV 
2
V 0
2


SUU U SUV V SUU SVV SUV
2 2
 
V 0  2

SUV
If we take U V SUU SVV SUV
2
0
SUU

8.2-1
d 2Y
(a) If Y X ,n
2
n n 1 X n 2 0 for n 0 or n 1
dX
(b-e) Case c is convex in P and therefore unstable.
Case b,d and e are nominally stable, but we must still check the “
fluting condition”(8.6).
We can do this directly or alternatively we can “
rotate coordinates”(i.e., make a Legendre
transformation) and again check only primary curvatures.
1 A 2 N 5
For case (b), we easily find U  , which is concave in S,V and N.
4 SV 3
So it is unstable.
1 C 2S 4
For case (d), we easily find U  , which is convex in all three variables.
4 VN 2

(It is of interest to check that it also satisfies the condition U SS U VV U SV

2
0 .)

Hence case (d) is stable.

3U U U
For case (e), we find U SS  2 , U VV 2 2 , U SV 3
4S V SV
2
15 U 
and U SS U VV U 2
SV    0 . So it is unstable.
2 SV 

In summary, only case (d) is stable.

8.2-3
For global stability
G T T , P P  G 
T T , P P 
2G 
T , P 0
Expanding to second order in T and P
1
2

G GT T G P P  GTT 
T 2GTP TP G PP 
2

P  G GT T G P P
2

1
2

 GTT T 2GTP TP G PP 
2
P  2G 0
2

GTT 
T 2GTP TP G PP 
P 0 for all T and P
2 2

Taking P = 0, GTT 0
Taking T = 0, G PP 0
T
Let X  , and dividing by P
P
GTT X 2 2GTP X G PP 0


GTT X GTP GTT G PP GTP
2 2
0

Take the minimum: GTT X GTP 0  GTT G PP GTP

2
0

8.3-2
3 U V 5 N
S  NR ln NR ln  NR ln
2 U0 V0 2 N0
3 NR NR 5 R
S UU  2 0 , SVV  2 0 , SUV 0 , S NN  0
2U V 2N

SUU SVV SUV

2
0 , SUU S NN SUN
2
0 , SVV S NN S VN
2
0 .