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T
v
P
s
v
s
Note:
1. The decrease in Helmholtz function of a
system sets an upper limit to the work done in
any process between two equilibrium states at
the same temperature during which the system
exchanges heat only with a single reservoir at
this temperature. Since the decrease in the
Helmholtz potential represents the potential to
do work by the system, it is also a
thermodynamic potential.
2. The decrease in Gibbs function of a system
sets an upper limit to the work, exclusive of
pdv work in any process between two states at
the same temperature and pressure, provided the
system exchanges heat only with a single
reservoir at this temperature and that the
surroundings are at a constant pressure equal to
that in the end states of the pressure.
N=
Maxwells relations:
v
T
P
P
T
v
P
[From equation du Tds Pdv ]
s v
v
Mnemonic Diagram
The
differential
expressions
for
the
thermodynamic potentials and Maxwell relations
can be remembered conveniently in terms of a
thermodynamic Mnemonic diagram.
The diagram consists of a square with two
diagonal arrows pointing upwards and the
thermodynamic potentials in alphabetical order
clockwise on the sides as shown in figure. The
du = (sign)Tds + (sign)Pdv
du = +Tds - Pdv
To write the Maxwell relations we need to
concentrate on the direction of the arrows and
the natural variables only.
If both the arrows pointing in the same direction,
there is no need to change the sign, otherwise
the equation should carry a negative sign.
du Cv dT
ds
Cv
1 u
dT
T
T v
P dv
v T
Using thrid Maxwell's relation,
s P
1 u
v T T v T v
From this we obtain
u
P
v T T
P
v
T v v
R
u
T
P PP 0
v
v T
Cv
P
ds
dT
dv
T
T v
Similarly it can be shown using Fourth
Maxwells relation that
ds
CP
v
dT
dP
T
T P
CP Cv
(P / T )v
dP
dT
dv
T (v / T ) P
u / T P
T (v / T ) P T v
1 v
v P T
T v v P P
or ,
1
T
(v / T ) P
P
T v
P T
Therefore,
C P Cv
T v / P P
v / P T
Reciprocal relation:
x
1
y z y
x z
Cyclic relation:
x y z
y z z x x
1
y
x, y
is defined as
p
,
r
x, y
x, y
p
,
r
p, r
x
p
y
p
x
r
x . y x . y
y
p r r p
r
x, y p , r x , y
p, r s , t s, t
x, y x
(ii )
p
,
r
y z
(i )
(iii)[ x, y ] [ y, x]
(iv)[ x, x] 0
If f ( x, y, z ) 0, then we can write z=z(x,y) and
z
z
dx
dy
x y
y x
dz
[ z, y ]
[ z, x]
dz
dx
dy
[ x, y ]
[ y, x]
or
[ x, y ]dz [ y, z ]dx [ z, x]dy 0
Divide the above relation throughout by db
holding a constant to obtain,
[ z , y ]
z
b a [ x, y ]
or ,
[ z , x] y
[ y , x] b
a
[ z , a ] [ z , y ] [ x, a ] [ z , x ] [ y , a ]
[ x, y ][ z, a] [ y, z ][ x, a] [ z, x][ y, a] 0
where a is a dummy variable.
If dz=Mdx+Ndy then [z,a]=M[x,a]+N[y,a]
Where a is a dummy variable.
Applying above properties of Jacobian to
thermodynamic variables,
[T , s ] [ P, v ]
1 [v, P ]
;
v [T , P ]
1 [ v, T ]
k
;
v [T , P ]
[ P, v ]
/k
;
[T , v]
[ s, P ]
Cp T
;
[T , P ]
[ s, v ]
Cv T
[T , v]
Methodology
1.
2.
[h, x] T [ s, x] v[ P, x];
[a, x] s[T , x] P[v, x ];
[ g , x] s[T , x] v[ P, x]
3.
4.
ds
dT
p
dP
T
[ s, P ]
[ s, T ]
dT
dP
[T , P ]
[ p, T ]
1 [v, P ]
v [T , P ]
T [ s, P ]
[T , P ]
Hence,
ds
Cp
dT vdP
T
s
s
dT
T v
v
ds
dv
T
Or,
ds
[ s, v]
[ s, T ]
dT
dv
[T , v ]
[ v, T ]
T [ s, v]
[T , v ]
we obtain,
ds
Cv
[ v, P ]
dT
dv
T
[ v, T ]
[v , T ]
we obtain,
ds
Cv
dT dv
T
dv
dh
dT
p
[ h, P ]
[ h, T ]
dT
dP
[T , P ]
[ P, T ]
dP
T
dh
T [ s, T ]
T [ s, P ]
dT
v dP
[T , P ]
[ P, T ]
[ s, P ]
[T , P ]
and [T,s]=[P,v]
we get,
[ P, v ]
dh CpdT v T
dP
[ P, T ]
Cp T (s / T ) p T [ s, P ] [v, T ]
[ s, P ] [T , v ]
.
Cv
T (s / T )v
[T , P ] T [ s, v ] [ s, v] [T , P ]
s P
or
Joule-Thomson Coefficient
The Joule-Thomson coefficient is defined as:
JT
or , JT
[T , h] [ h, T ]
[ P , h ] [ h, P ]
the
[h,P]=T[s,P]+v[P,P]=T[s,P]
[h,T]=T[s,T]+v[P,T]
we get:
JT
T [ s, T ] v[ P, T ]
T [ s, P ]
T [v, P ] v[ P, T ]
Cp[T , P ]
1
1
(Tv v)
v(T 1)
Cp
Cp