2.

Equation of state

2.1 Ideal gas

The "state" of a thermodynamic system can be expressed in terms of its system
properties by an equation in the form:
f (P, V, T, m ) = 0

is called the equation of state of the system

Here only V is an extensive property. If we use the intensive (specific) form of this
property, that is
v=

V
m

or

v=

V
,
n

where n is the number of moles of particles in the system

Then the equation of state becomes:

f (P, v, T ) = 0

This is not dependent on the quantity of the material inside the system.
From experiment, if v and P are measured for fixed values of T , the following graphs can
be plotted:

From these graphs, it is observed that

Pv
P0 8.3143 103 J kmole-1 K-1
T

The value
Pv
= R or
T

for all temperatures and types of gas

R = 8.3143 103 J kmole-1 K-1 is called the Universal Gas Constant

Pv = RT

or

PV = nRT

is the Equation of State for Ideal Gas

2.2 Graphical representation of the equation of state : P-v-T surface

(i)

With fixed T

(ii)

P
= constant
T

Pv = constant
(Boyle's Law)

(iii) With P fixed,

With fixed v

v
= constant
T

(Charles' Law)

3-D graph :

P-v-T surface for ideal gas

v/T = constant

Pv = constant

P/T = constant

2.3 Real gas

If the equation of state is not obeyed, that is
Pv
R
T

the gas is said to be a real gas

The general form of the equation of state of a real gas is :

Pv = A +

B C
+
+ ...........
v v2

where

A = RT

B
C

+
+
.........
Pv = RT 1 +

RTv RTv 2

The factor

B
C

+
+
.........
z = 1 +

RTv RTv 2

is called the Departure Coefficient

B = RTb a , C = RTb2 ............. and so on

If we take

Hence ,

RTb a RTb 2
Pv = RT +
+ 2 + ............
v
v
2
a

b
b
= RT + RT + RT + ........
v
v
v

= RT 1
v

a
v

b b2
= 1 + + 2 + .........
v v

where

1
v

v a
Pv = RT

v b v

P=

Finally,

P + 2 (v b ) = RT
v

van der Waals equation

RT
a
2
vb v

A gas that obeys this equation of state is called the van der Waals gas
In this model of "real gas", the effect of the intermolecular forces and the volume
occupied by the molecules themselves have been taken into consideration.

P+ 2
v

Volume occupied by the molecules themselves

(v b)

Intermolecular forces

Substance
He
H2
O2
CO2
H2O

a
(J m kilomole-2)
3.44 103
24.8 103
138 103
366 103
580 103

b
(m kilomole-1)
0.0234
0.0266
0.0318
0.0429
0.0319

Hg

292 103

0.0055

P-v curves

P-v-T surfaces

2.4 Real substances : P-v-T surfaces

3 possible phases :

solid, liquid, gas (vapor gas at equilibrium with its liquid)

(Reading : Section 2.5, pp 30-40)

2.5 Thermodynamic systems other than P-v-T system (examples)

(a) A metal wire under tension

+ (T To )
L = Lo 1 +
YA

Thermodynamic properties:

(Y : Young's modulus; : coeff. of linear expansion)

tension
length
temperature

,
L,
T

(b) Paramagnetic material

M = Cc

H
T

- Curie's law

Thermodynamic properties:

(Cc : Curie constant)

magnetic field intensity
magnetic moment
temperature

H
M
T

2.6 Partial derivatives

Process 1 2, 4 3 : isobaric
Process 1 4, 2 3 : isothermal
For isobaric process,
volume changes by vp
when temperature changes by Tp
while P is not changed
Taking limit of Tp 0 for

v p
T p

, i.e.

v p

v
=

T p 0 T p
T p
- Partial derivative of v with respect to T
lim

is the tangent at point 1

 v
If v is given as a function of P and T,
can be obtained
T P

Example :

For ideal gas, Pv = RT

R
v
=

T P P

To calculate the change in the volume caused by the change in temperature dTP during
the isobaric process,
v
dv P =
dTP
T P

The quantity

1 v
=

v T P

For ideal gas,

is the coefficient of volume expansion, or expansivity

1R
P R 1
=
=
v P RT P T

For finite temperature change, TP , the average value of expansivity is

1 v P
v1 TP

Using the similar argument by referring to the v-P curve for the isothermal process,
Tangent at each point on the curve:

v
dvT =
dPT
P T

and

1 v
=

v P T

1 vT
v1 PT

P T

- isothermal compressibility
P

- mean compressibility

when the pressure is increased isothermally by PT

 X
X
dX =
dY +
dZ
Y Z
Z Y

In general, we can write for X = f (Y, Z )

and hence,

v
v
dv =
dT +
dP = vdT vdP
T P
P T

or

dv
= dT dP
v

Note that

: expansivity is expressed in unit of ( K-1 )

and

: compressibility is expressed in unit of ( m2 N-1 )

The values of these quantities can be measured experimentally for a material.

Integrate the experssion for dv,

which gives

vo

To

Po

dv = v v o = vdT vdP

v = v o + v o(T To ) v o ( P Po ) = v o [1 + (T To ) ( P Po )]

Example : copper

2.7 Critical constants of a van der Waals gas

For a van der Waals gas,

At the critical point,

=0
v T

P=

RT
a
2
vb v

and

2P

v 2 = 0

Hence,

RTc
2a
P
+
=0

=
2
3
v T
vc
(v c b)

and

2P
2 RTc
6a
=

=0
3
4
v 2
v
b
v
(

)
T

c
c

Solving these equations gives :

v c = 3b , Tc =

8a
27 Rb

and

Pc =

a
27b 2

which are the system parameters at the critical point.

Hence by measuring these values experimentally, the values of a and b for the real gas can be
obtained.
v
From the first equation,
b= c
3
RTc
b=
From the second and third equations,
8 Pc
Pc v c 3
This implies that at the critical point of a van der Waals gas,
= = 0.375
RTc 8
Experimentally, this is found to be not true van der Waals gas model is not accurate!

2.8 Relations between partial derivatives

Volume differential :

V
V
dV =
dT +
dP

T
P

Pressure differential :

P
P
dP =
dV
dT +
V T
T V

Combine these two equations,

V P
V P
V
1

=
+
dV

dT

P
V
P
T
T
T
T
T
V
P

This equation should be obeyed by 2 nearby equilibrium states.

Consider the case when dT = 0 but dV 0, we obtain:

V P

= 0 , that is
1
P
V

1
V

=
P T P

V T

Similarly, we can obtain for the case of dT 0 while dV = 0

V P
V

+
=0
P T T V T P

Hence

V P T

= 1

P T T V V P

In general, if

f ( X, Y, Z ) = 0 , the we can write

1
X

=
Y Z Y

X Z
X Y Z
= 1

Y Z Z X X Y

2.9 Exact differentials

Taking

state 1 : (P1 V1 T1 )
state 2 : (P1 V2 T2 )
state 3 : (P3 V3 T2 )
state 4 : (P3 V4 T1 )

For process 1 3, it can take 3 paths :

first path : 1 3
second path : 1 2 3
third path : 1 4 3

For path 1, it involves all three parameters P V T are varied together cannot be used !

Path 2,

process 1 2 is isobaric ( P = constant)

process 2 3 is isothermal ( T = constant)

Change in volume after these processes (volume differential) :

V
V
dV1 2 3 =
dT +
dP
T P1
P T2
Similarly, for path 3,

If we assume

dV1-2-3 = dV1-4-3

Then, we can write

Hence,

V
V
dV1 4 3 =
dT
dP +
T
P

P3

T1
the volume differential is an exact differential

V
V
V
V

dT +
dP +
dP =
dT

T
P
P
T

P1

T1

T2

P3

V
V

T P3 T P1
dP

V
V

P
P

T2
T1

dT

Take limit that dP 0 and dT 0 ,

lim

dP 0

lim

dT 0

This gives

V
V

T P3 T P1

V
2V
=
=

P
T
P T PT

dP
V
V

P T2 P T1
dT

V
2V
=
=

T
P
T P TP

2V
2V
=
P T T P

This means that the second partial derivatives of V is independent of the order of
differentiation.
The differential of V is then said to be an exact differential.
The differentials of all thermodynamic properties of a system are exact. In other words, a
quantity whose differential is not exact is not a thermodynamic property.