Notes prepared by Prof.

Devaraj K

Ideal Gas and Mixture of Gases

Terms and Definitions
Ideal Gas
A substance is said to be an ideal gas if it satisfies the following equations:
pV = mRT

and

u = f (T )

Where p is the pressure exerted by the substance, V is the total volume of the substance, m is the
mass of the substance, T is the absolute temperature in Kelvin, u is the specific internal energy and R
is the Gas constant.
All the real gases almost satisfy the above equation over wide range of pressure and temperature, with
conditions that these gases cannot be treated as ideal gases.

Mole of a Gas
Mole of a gas is numerically equal to its molecular weight. If n is the total number of moles, m is the
mass and M is the molecular weight, then nM=m.

Avogadros Hypothesis
Avogadros law states that equal volumes of all gases measured at the same pressure and temperature
contain the same number of moles.
If two gases a and b are considered, then according to this law if Va = Vb , Ta = Tb & pa = pb then
na = nb . Mathematically, for gas A, it is written as
pa Va = ma Ra Ta = na Ma Ra Ta
pa V a
na =
Ma Ra Ta
Similarly for gas b, we have
pb Vb = mb Rb Tb = nb Mb Rb Tb
pb Vb
nb =
Mb Rb Tb
where R
is called the universal gas constant and its value has been determined
Also Ma Ra = Mb Rb = R,
as 8.3143 kJ/kg-mol K. So the ideal gas equation can be rewritten as,

pV = mRT = nM RT = nRT

Specific heats and its relation

Specific heat at constant volume (Cv )
The general definition of Cv is given by Cv = (

u
du
)v . For an ideal gas u = f (T ), therefore Cv =
.
t
dT

Specific heat at constant pressure (Cp )

The general definition of Cp is given by Cp = (

h
dh
)p . For an ideal gas h = f (T ), therefore Cp =
.
t
dT
1

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Relation between specific heats for an ideal gas

For an ideal gas, specific enthalpy is given
h = u + pv
h = u + RT

pv = RT

Differentiating with respect to T, we get

dh
du
=
+R
dT
dT
Cp = Cv + R
Cp Cv = R
Dividing equation (1) by Cv , and denoting the ratio of

(1)

Cp
as , we have
Cv

R
Cv
R
Cv =
( 1)
1=

(2)

Dividing equation (1) by Cp ,

1
R
=

Cp
R
Cp =
( 1)
1

(3)

Expressions for changes in Internal Energy, Enthalpy and Entropy of an Ideal Gas
Change in Internal Energy
If an ideal gas of mass m changes its state from 1 to 2, then the change in internal energy is given by,
Z 2
U2 U1 = m(u2 u1 ) = m
du
1
Z T2
U2 U1 = m
Cv dT
T1

The above equation can be integrated if the value of Cv is constant for a perfect gas, to get
U2 U1 = mCv (T2 T1 )

(4)

Change in Enthalpy
If an ideal gas of mass m changes its state from 1 to 2, then the change in enthalpy is given by,
Z 2
H2 H1 = m(h2 h1 ) = m
dh
1
Z T2
H2 H1 = m
Cp dT
T1

The above equation can be integrated if the value of Cp is constant for a perfect gas, to get
H2 H1 = mCp (T2 T1 )
2

(5)
Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Change in Entropy
If an ideal gas of mass m changes its state from 1 to 2, with properties of p1 , V1 , T1 to p2 , V2 , T2 , then the
change in entropy is given by
Z 2
ds
S2 S1 = m(s2 s1 ) = m
1
Z 2
du + pdv
T ds = du + pdv and T ds = dh vdp from entropy relations
S2 S1 = m
T
1
Z 2
dT
dv
p
R
{Cv
S2 S1 = m
+R } =
T
v
T
v
1
v2
T2
+ R ln }
S2 S1 = m{Cv ln
T1
v1
We can obtain the similar expression by using the other relation T ds = dh vdp, to get
T2
p2
R ln }
T1
p1

S2 S1 = m{Cp ln

Expression for Work and Heat Transfer for a perfect gas undergoing quasi-static processes
Constant Temperature process
For a constant temperature process T=constant or pV = constant. For an ideal gas pV=mRT. Therefore,
the displacement work is given by,
Z 2
(Wd )12 =
pdV
1
Z 2
p1 V1
dV
(Wd )12 =
V
1
V2
(Wd )12 = p1 V1 ln( )
V1
From First law of Thermodynamics, we have Q12 = W12 + (U2 U1 ) If the work interaction is considered only to be of displacement type, the W12 = (Wd )12 . For an isothermal process U2 = U1 as the
temperature remains constant.
Q12 = W12 = p1 V1 ln(

V2
V2
) = mRT1 ln( )
V1
V1

(6)

Polytropic process pv n = C
For this process the displacement work is given by
Z 2
(Wd )12 =
pdV
1
Z 2
p1 V1 n
(Wd )12 =
(
) dV
V
1
Z 2
n
(Wd )12 = (p1 V1 )
V n dV
1

(Wd )12 = (p1 V1 )n

(V2 )1n (V1 )1n

1n

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

p1 V 1 p2 V 2
n1
(T1 T2 )
= mR
n1

(Wd )12 =
(Wd )12

If the work interaction is considered only to be of displacement type, the W12 = (Wd )12 . From First law
of Thermodynamics, we have Q12 = W12 + (U2 U1 ). Therefore,
Q12 = mR

(T1 T2 )
+ mCv (T2 T1 )
n1

(7)

Reversible adiabatic or Isentropic process

To show pv = constant
For the reversible adiabatic process the entropy remains constant. Therefore the TdS equation can be
written as,
du + pdv = 0 dS = 0 for isentropic process
RT
RT
dv = 0 du = Cv dT & p =
Cv dT +
v
v
Divide through out by Cv T , we get
R dv
dT
+
=0
T
Cv v
Integrating the above equation, we have
R

ln T + ln(v) Cv = Constant
R

(T v) Cv = Constant
(T v)1 = Constant
For an ideal gas pv = RT or T =

R
=1
Cv

(8)

pv
. Substituting for T in the equation (8), we get
R
pv
( )(1) = constant
R
pv = constant

Workdone expression
For reversible adiabatic proces with pv = C, the displacement work is given by,
Z 2
(Wd )12 =
pdV
1
Z 2
p1 V1
) dV
(Wd )12 =
(
V
1
Z 2

(Wd )12 = (p1 V1 )

V dV
1

(V2 )1 (V1 )1
1
p1 V1 p2 V2
=
1
(T1 T2 )
= mR
1

(Wd )12 = (p1 V1 )

(Wd )12
(Wd )12

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Mixture of Ideal Gases

For thermodynamic analysis of systems involving individual gases and its mixture is assumed to be behave
as perfect gas.

Partial pressure of mixture of gases

Partial pressure of a gas in a mixture is defined as the pressure exerted by individual gas when it alsone
occupies mixture volume as mixture temperature.
Consider the mixture of two gases a and b. If V is the volume of mixture gas and its temperature
be T.
.
Partial pressure of gas, a is given by pa V = ma Ra T = na RT

Partial pressure of gas, b is given by pb V = mb Rb T = nb RT

Partial Volume of mixture of gases

Partial volume of the mixture of gases is defined as the volume occupied by individual gas when evaluated
at mixture pressure and its temperature.
Consider the mixture of two gases a and b. If V is the volume of mixture gas and its temperature
be T.
.
Partial volume of gas, a is given by pVa = ma Ra T = na RT

Partial volume of gas, b is given by pVb = mb Rb T = nb RT

Mass fraction(y)
Mass fraction is defined as the ratio of mass of individual gas to the mass of the mixture.
Consider mixture of two gases, a and b,
ma
ma
=
Mass fraction of gas a ya =
m
ma + mb
mb
mb
Mass fraction of gas b yb =
=
m
ma + mb
Also,
m = ma + mb
ma mb
1=
+
m
m
1 = ya + yb

Mole Fraction (x)

Mole fraction is defined as the ratio of number of mole of the individual gas to the number of moles of
mixture.
Consider mixture of two gases, a and b,
na
na
=
Mole fraction of gas a xa =
n
na + nb
nb
nb
Mass fraction of gas b xb =
=
n
na + nb
Also,
n = na + nb
na nb
1=
+
n
n
1 = xa + xb

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Daltons law of partial pressures

It states that total pressure exerted by the mixture of gases is equal to the sum of partial pressure of
individual gases.
Consider the mixture of two gases a and b,
. Such that na = pa V .
For gas a, according to the partial pressure concept pa V = na RT

RT
p
V
b
. Such that nb =
For gas b, from the partial pressure concept pb V = nb RT
.
RT
, such that n = pV .
Now, for the mixture of gas a and b, pV = nRT

RT
We know for a mixture,
n = na + nb
pV
pa V
pb V
= +

RT
RT
RT
p = pa + pb

Amagats law of partial volumes

According to this law the total volume occupied by the mixture of gases is equal to the sum of partial
volumes of individual gases.
Consider the mixture of two gases a and b,
. Such that na = pVa .
For gas a, according to the partial volume concept pVa = na RT

RT
pV
b
. Such that nb =
For gas b, from the partial volume concept pVb = nb RT
.
RT
, such that n = pV .
Now, for the mixture of gas a and b, pV = nRT

RT
We know for a mixture,
n = na + nb
pV
pVa pVb
= +

RT
RT
RT
V = Va + Vb

Relation between partial pressures and mole fraction

From the perfect gas equation for the gas mixture, we have

pV = nRT

(9)

pa V = na RT

(10)

Partial pressure for gas a is given by,

Dividing equation (10) by (17), we get

pa
na
=
= xa
p
n
Partial pressure for gas b is given by,

pb V = nb RT

(11)

Dividing equation (11) by (17), we get

pb
nb
=
= xb
p
n
6

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Relation between partial volume and mole fraction

Partial volume for gas a is given by,

pVa = na RT

(12)

Dividing equation (12) by (17), we get

na
Va
=
= xa
V
n
Partial volume for gas b is given by,

pVb = nb RT

(13)

Dividing equation (13) by (17), we get

Vb
nb
=
= xb
V
n

Gas Constant (R), Molecular weight (M) for the mixture in

terms of mass fraction
For gas a, we have
pa V = ma Ra T

(14)

pb V = mb Rb T

(15)

V (pa + pb ) = (ma Ra + mb Rb )T

(16)

For gas b, we have

Adding equation (14) and (15), we get

For the gas mixture, pV = mRT. Also, from daltons law

p = pa + pb

(17)

Substituting for pa + pb from (16) in (17), we get

(ma Ra + mb Rb )
V
mRT = (ma Ra + mb Rb )T
ma
mb
R=
Ra +
Rb
m
m
R = ya Ra + yb Rb

p=

Molecular weight of the mixture is given by M =

(18)

R
R
. Therefore M =
.
R
ya Ra + yb Rb

Gas Constant (R), Molecular weight of the mixture in terms of Mole fractions
The mass of the mixture of gases a and b is given by, m = ma + mb . Therefore
nM = na Ma + nb Mb
na
nb
M = Ma + Mb
n
n
M = xa Ma + xb Mb
From the Molecular weight relation, R =

(19)

R
R
. So R =
.
M
xa Ma + xb Mb
7

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Gibbs law
This law states that the internal energy, enthalpy, entropy of mixture of gases is equal to the sum of
internal energies, enthalpies and entropies of the individual gases respectively, when evaluated at mixture
pressue p and its temperature T.
Consider the mixture of two gas, a and b, From Gibbs law
U = Ua + Ub
H = Ha + Hb
S = Sa + Sb

Specific Heats of Mixture of Gases

Specific heat at constant volume
Consider a mixture of two gases a and b. From the Gibbs law we have
U = Ua + Ub
mu = ma ua + mb ub
mCv T = ma Cva T + mb Cvb T
mb
ma
Cva +
Cvb
Cv =
m
m
Cv = ya Cva + yb Cvb

(20)

Specific heat at constant pressure

Consider a mixture of two gases a and b. From the Gibbs law we have
H = Ha + Hb
mh = ma uha + mb hb
mCp T = ma Cpa T + mb Cpb T
ma
mb
Cp =
Cpa +
Cpb
m
m
Cp = ya Cpa + yb Cpb

(21)

Real Gases
The ideal gas equation pv = RT can be derived analytically using the kinetic theory of gases by making
the following assumptions:
1. A finite volume of gas contains large number of molecules.
2. The collision of molecules with one another and with the walls of the container are perfectly elastic.
3. The molecules are separated by large distances compared to their own dimensions.
4. The molecules do not exert forces on one another except when they collide.
As long as the above assumptions are valid the behaviour of a real gas approaches closely that of an ideal
gas.
The ideal gas equation of state is very simple, but its range of applicability is limited. It has been
observed through experiments that at relatively low pressures and temperatures most of the real gases
obey Boyles and Charles laws quite closely. Most of the gases behaviour is considerably different at
elevated pressures and low temperatures. The gases that deviate from ideal gas behaviou r and which
8

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

doesnot obey the ideal gas equation of state is known as Real Gases. The equation of state for real gases
is obtained by suitably modifying the ideal gas equation. Two important equation of state for real gases
are:
1. Vander Waals Equation of state
2. Compressibility factor

Van Der Waals Equation of state

In 1873, Van Der Waal proposed an equation of state that composed of two assumptions made in obtaining
ideal gas equation. Namely
1. Intermolecular forces of attraction are negligible
2. Volume of molecules themselves are negligible in comparison to the volume occupied by the gas.
According to Van Der Waal, the assumptions hold good at low pressure and high temperature in
which molecules are closed packed and offer the forces of attraction. Also at this high pressure the gas
a
molecules posses finite volume and hence cannot be neglected, then the term 2 was introduced to include
v
intermolecular force and b for volume occupied by molecule, then the Van Der Waal equatioin can be
written of the form
(p +

a
)(v b) = RT
v2

(22)

)(
v b) = RT
v2

(23)

where,
p = pressure exerted in (N/m2 )
v = specific volume (m3 /kg)
R = Gas constant (J/kg-K)
T = Temperature (K)
Van Der Waal equation can also be written as
(p +
where,
p = pressure exerted in (N/m2 )
v = molecular specific volume (m3 /kg mol)
= Universal Gas constant = 8314 (J/kg-mol)
R
T = Temperature (K)

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Evaluation of constants of Van Der Waals equation

The determination of the constants a,b & R in the Van Der Waal equation is based on the fact that the
critical isotherm on a p-V diagram has horizontal inflexion point at the critical point. Therefore, the first
and second derivative of p with respect to v should be zero, such that
2p
p
( )T =Tc = 0 and ( 2 )T =Tc = 0
v
v
From the Van Der Waals equation (22), we can write as,
a
(p + 2 )(v b) = RT
v
a
RT
(p + 2 ) =
v
(v b)
RT
a
p=
2
(v b) v
At critical point,
a
RTc
2
(24)
pc =
(vc b) vc
Differentiating the equation (24) w.r.t to vc
pc
RTc
2a
(
)=
+ 3
2
vc
(vc b)
vc
2a
RTc
+ 3 =0
2
(vc b)
vc
2a
RTc
= 3
2
(vc b)
vc

(25)

(26)

Differentiating the equation (25) w.r.t to vc

2 pc
2RTc
6a
)=
4
2
3
vc
(vc b)
vc
2RTc
6a
+ 4 =0
3
(vc b)
vc
6a
2RTc
=
(vc b)3
vc4
4a
6a
RTc
2a
vc3 = 4

=
(vc b)
vc
(vc b)2
vc3
2vc
=3
(vc b)
2vc = 3vc 3b
vc
b=
3
Substituting the value of b in (26), we get
RTc
2a
vc 2 = v 3
c
(vc )
3
RTc
2a
= 3
2vc 2
vc
(
)
3
9RTc
2a
= 3
2
4vc
vc
8a
R=
9Tc vc
(

10

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Substituting the value of b and R in the Van Der Waals equation at cri2tical point
a
8a
vc
)
=
Tc
)(v

c
vc2
3
9Tc vc
a 2vc
8a
(pc + 2 )(
)=
vc 3
9vc
3
a
8a

pc + 2 =
vc
9vc 2vc
2
pc vc + a
4a
= 2
2
vc
3vc
2
a = 3pc vc
(pc +

Compressibility factor (z)

Gases deviate from ideal gas behaviour significantly at saturation region and critical point, this deviation
can be accurately accounted by the introduction of correction factor called compressibility factor(z).
The factor which expresses the extent of deviation of gas from the ideal gas is known as compressibility
factor (z). Such that
pv
RT
vactual
z=
videal
z=

z = 1, for ideal gas

z < 1 and z > 1 for real gases

Reduced Properties
Gases behave differently at given pressure and temperature, but they behave similarly when normalized
with respect to their critical properties. Hence reduced properties are the dimensionless properties which
are obtained by taking the ratio of properties of gas to its critical properties. The reduced properties are:
Reduced Pressure (PR )
It is the ratio of existing pressure to the critical pressure of the substance
PR =

p
pc

Reduced Volume (VR )

It is the ratio of existing volume to the critical volume of the substance
VR =

v
vc

Reduced Temperature (TR )

It is the ratio of existing temperature to the critical temperature of the substance
TR =

11

T
Tc

Basic Thermodynamics

Notes prepared by Prof. Devaraj K

Law of corresponding states

The relation among reduced properties PR , VR &TR is known as law of corresponding states. The law is
stated as if any 2 gases have same values of reduced properties such as pressure and temperature, then
they will have same values of reduced vlume. VR is a function of PR &TR . i.e., VR = f (PR , TR ).
The law can also be stated as the compressibility factor for all gases is a function of reduced pressure
and reduced temperature. z = f (PR , TR ).

Generalized Compressibility chart

Figure 1: Compressibility factors Vs reduced pressure for real gas

The law of corresponding state-permit to prepare compressibility chart based on reduced properties. The
generalized compressibility chart is plotted with compressibilty factor (z) Vs reduced pressure (PR ) for
various values of TR . This data can be used for any gas and gives best results for the region away from
critical point for all the gases. From the chart the following observation can be made,
At very low pressures (PR << 1) the gases behave as ideal gas regardless of the temperature, since
z 1.
At high temperatures (TR > 2) the gases approaches ideal gas behaviour with good accuracy regardless of the pressure except when (PR >> 1) .
At critical points, the gas deviates from ideal gas approach.
12

Basic Thermodynamics