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Thermodynamic relations

Gibbs Function and Helmoltz Function


Gibbs equation is
du = Tds - Pdv
The enthalpy h can be differentiated,
dh = du + pdv + vdP
Combining the two results in
dh = Tds + vdP
The coefficients T and v are partial derivative of
h(s,P),
h

T
v

Since v > 0, an isentropic increase in pressure


will result in an increase in enthalpy.

We introduce Helmholtz function


a = u Ts
Combine Gibbs equation with the differential of
a,
da = -Pdv sdT
The coefficient P and s are the partial
derivatives of f(v,T), so
a

P
s

Similarly, using the Gibbs function


g = h Ts
dg = vdP sdT
Consequently,
g

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.

The maximum work is done when the process is


isothermal isobaric. Gibbs function is also called
Chemical Potential.
Some important property relations
dz(x,y) = Mdx + Ndy
where, M =

N=

Mathematically, we would say that dz is an exact


differential, which simply means that z is a
continuous function of the two independent
variables x and y. Since the order in which a
second partial derivative is taken is unimportant,
it follows that,
M

Maxwells relations:

v
T

P
P

T
v

P

[From equation du Tds Pdv ]
s v
v

[From equation dh Tds vdP]


s P
s

[From equation da Pdv sdT ]


T

[From equation dg vdP sdT ]


T

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

natural variables associated with each potential


are placed in the corners.

Diagonal arrows indicate the coefficients


associated with the natural variables in the
differential expression of the potential. The sign
of the coefficient depends on whether the arrow
is pointing towards (- ve) or away from the
natural variable (+ ve).
For example,
du = (sign)(coeff.) ds + (sign)(coeff.) dv

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.

The internal energy


u = u(T,v)
For a simple compressible substance,
u
dv
v T

du Cv dT
ds

Cv
1 u
dT

T
T v

P dv

Taking entropy as a function of temperature and


volume,
Cv
s

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

This important equation expresses the


dependence of the internal energy on the volume
at fixed temperature solely in terms of
measurable T, P and v. This is helpful in
construction of tables for u in terms of measured
T, P and v.

For a perfect gas,


Pv = RT
R
P

T v v
R
u

T
P PP 0

v
v T

This implies that, for a perfect gas, internal


energy is independent of density and depends
only on 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

Using the above two equations and solving for


dP,

CP Cv
(P / T )v
dP
dT
dv
T (v / T ) P
u / T P

Considering P as a function of T and v, we see


that
CP Cv
P

T (v / T ) P T v

Two thermodynamic properties can be defined at


this stage,
1 v

v T P

1 v

v P T

is called the isobaric compressibility and is


called the isothermal compressibility.
From calculus, it can be shown that,
P T v



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

Since v / P T is always negative for all stable


substances, CP is always greater that Cv

Important mathematical relations


f(x, y, z) = 0
Chain rule:
x
x

y z a z

Reciprocal relation:
x
1


y z y

x z
Cyclic relation:
x y z

y z z x x

1
y

Jacobian Methods in Thermodynamics


Jacobian

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

Jacobians obey the followings properties:

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

In Jacobian notation this can be written as,

[ 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 ]

[b, a] [ x, y ] [b, a] [ y, x] [b, a]


Multiply throughout by [x,y][b,a] and rearrange
to obtain

[ 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,

du Tds Pdv;[u , x] T [ s, x] P[v, x]


dh Tds Vdp;[h, x] T [ s, x] v[ P, x ]
da sdT Pdv;[a, x ] s[T , x ] P[v, x]
dg sdT vdP;[ g , x ] s[T , x] v[ P, x ]
where x is dummy variable.

In Jacobian Notation, the Maxwell relations are


given by,

[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.

Express the required partial derivative in


terms of Jacobian
If the Jacobian contain the thermodynamic
potentials, u, h, a and g they may be
eliminated by substituting the following
relations:

[u, x] T [ s, x] P[v, x];

[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.

If the Jacobian contain entropy it can be


eliminated by making use of Maxwell
relation [T,s]=[P,v] or in terms of definitions
of Cp and Cv
The resulting expression contains the
measurable properties P, v, T, Cp, Cv, and
k.

Thermodynamic Relations Involving Entropy


(a) Entropy as a function of T and P:Consider s= s (T,P)
Then the differential in change in the entropy,
s

ds

dT
p

dP
T

Expressing the partial differentials in the


Jacobian notation,
ds

[ s, P ]
[ s, T ]
dT
dP
[T , P ]
[ p, T ]

Eliminating the Jacobians containing entropy in


terms of the Maxwell relations,
[T,s]=[P,v]
and the specific heat, Cp
Cp
[ P, v ]
ds
dT
dP
we obtain,
T
[ P, T ]
Earlier we got,

1 [v, P ]
v [T , P ]

T [ s, P ]
[T , P ]

Hence,

ds

Cp
dT vdP
T

Tds CpdT vTdP

(b) Entropy as a function of T and v:Consider s=s(T,v)


Then,

s
s
dT

T v
v

ds

dv
T

Or,
ds

[ s, v]
[ s, T ]
dT
dv
[T , v ]
[ v, T ]

Eliminating the Jacobians containing entropy


using the definition for Cv,
Cv

T [ s, v]
[T , v ]

and the Maxwell relation,


[T,s]=[P,v]

we obtain,
ds

Cv
[ v, P ]
dT
dv
T
[ v, T ]

Next, eliminating the Jacobian containing P,v


and T using the relation,
[v , P ]

[v , T ]

we obtain,

ds

or, Tds CvdT

Cv

dT dv
T

dv

Thermodynamic relations involving Enthalpy


and Internal energy
Let, h=h(T,P)
Then,
dh

dh

dT
p

[ h, P ]
[ h, T ]
dT
dP
[T , P ]
[ P, T ]

dP
T

Eliminating the Jacobians containing enthalpy


by using the relations:
[h,P]=T[s,P]+v[P,P]=T[s,P]
[h,T]=T[s,T]+v[P,T]
we obtain,

dh

T [ s, T ]

T [ s, P ]
dT
v dP
[T , P ]
[ P, T ]

next, eliminating the Jacobians containing s by


making use of the relations:
Cp T

[ s, P ]
[T , P ]

and [T,s]=[P,v]
we get,

[ P, v ]
dh CpdT v T
dP
[ P, T ]

Finally we can eliminate the Jacobian containing


P, v, T ,
dh CpdT (v Tv )dP

Specific Heat relations


Consider the ratio of specific heats Cp and Cv:

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

That is on a P-v diagram the slope of a


reversible adiabatic process is equal to times
the slope of a reversible isothermal process.

Joule-Thomson Coefficient
The Joule-Thomson coefficient is defined as:

JT

or , JT

[T , h] [ h, T ]

[ P , h ] [ h, P ]

Eliminating the Jacobians containing


potential h by making use of the relations:

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 ]

Eliminating the Jacobians containing entropy,


JT

T [v, P ] v[ P, T ]
Cp[T , P ]

The Jacobian containing P, v, T can be


eliminated to obtain:
JT

1
1
(Tv v)
v(T 1)
Cp
Cp