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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

will result in an increase in enthalpy.

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

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.

isothermal isobaric. Gibbs function is also called

Chemical Potential.

Some important property relations

dz(x,y) = Mdx + Ndy

where, M =

N=

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

s P

s

T

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

are placed in the corners.

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.

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

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

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.

Pv = RT

R

P

T v v

R

u

T

P PP 0

v

v T

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

dP,

CP Cv

(P / T )v

dP

dT

dv

T (v / T ) P

u / T P

that

CP Cv

P

T (v / T ) P T v

this stage,

1 v

v T P

1 v

v P T

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

substances, CP is always greater that Cv

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

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 ]

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,

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.

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.

terms of Jacobian

If the Jacobian contain the thermodynamic

potentials, u, h, a and g they may be

eliminated by substituting the following

relations:

[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.

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.

(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

Jacobian notation,

ds

[ s, P ]

[ s, T ]

dT

dP

[T , P ]

[ p, T ]

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

Then,

s

s

dT

T v

v

ds

dv

T

Or,

ds

[ s, v]

[ s, T ]

dT

dv

[T , v ]

[ v, T ]

using the definition for Cv,

Cv

T [ s, v]

[T , v ]

[T,s]=[P,v]

we obtain,

ds

Cv

[ v, P ]

dT

dv

T

[ v, T ]

and T using the relation,

[v , P ]

[v , T ]

we obtain,

ds

Cv

dT dv

T

dv

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

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 ]

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 ]

P, v, T ,

dh CpdT (v Tv )dP

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

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 ]

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 ]

JT

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

Cp[T , P ]

eliminated to obtain:

JT

1

1

(Tv v)

v(T 1)

Cp

Cp

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