UNIT – IV

IDEAL AND REAL GASES,

THERMODYNAMIC
RELATIONS
 IDEAL GAS
• An ideal gas is an imaginary substance that
obeys the relation pV = RT or pv = RT
• So, the equation of state is also known as ideal
gas equation.
• A factor introduced to account the deviation of
the ideal gas behavior known as
compressibility factor.
 REAL GASES
• At high pressure, the gases start from ideal gas
behaviour. So, the deviation should be
accounted.
• For accounting this deviation, a factor called
compressibility is introduced.
• So, the state equation for real gases is given by
pv = ZRT
Where, Z – Compressibility factor
The compressibility factor, Z
The compressibility factor can also be expressed
as Z

For ideal gases, Z= 1. but, for real gases, Z is

greater than or less than unity.
 PROPERTIES OF IDEAL GAS
• Obeys the equation of state at all pressures and
temperatures is known as ideal gas.
• The volume may remain constant or pressure
may remain constant.
• But the minimum possible temperature is zero
kelvin.
IDEAL GAS AND REAL GAS COMPARISON
S.no Ideal gas Real gas
The behavior of ideal The behavior of real gases
1
gases is simple. is Complex
Only air is considered as All gases air is considered
2
ideal gas as real gas
The pressure of ideal gas The pressure of real gas is
3
is more Less
4 It follows pv=nRT It follows pv = zRT
Collision of ideal gas Collision of ideal gas
5
particles is elastic particles is non-elastic
No energy involved Collision of particles in
6 during collision of real gas has attracting
particles in ideal gas energy.
Ideal gas has no definite Real gas has definite
7
volume volume.
8 Ideal gas has no mass Real gas has mass.
 EQUATION OF STATE FOR IDEAL
GAS
The ideal as is an substance which obeys the law
of pv = T.
• where:
• P is the pressure of the gas
• V is the volume of the gas
• is universal gas constant = 8.314kJ/kgmole

• T is the temperature of the gas

 EQUATION OF STATE FOR IDEAL
GAS
1. Boyle’s Law
2. Charle’s Law
3. Joules Law
4. Regnault’s Law
5. Avogadro’s Law
6. Characteristics Gas Equation
 BOYLE’S LAW
• Boyles law states that the volume of given
mass of a gas varies inversely with its absolute
pressure.
v α 1/p or pv = constant
The ideal gas at state 1 can be written as p 1v1 = C
At state 2, p2v2 = C
p1v1 = p2v2
 CHARLE’S LAW
Charle’s law state that the volume of given mass
of a gas varies directly with its absolute
temperature when the pressure remains constant
vαT

• At state point 1,

• At state point 2,
Therefore,

So,
 JOULES LAW
• Internal energy of given quantity of a gas
depends only on the temperature
 REGNAULT’S LAW
• It states that the specific heats Cp and Cv of a
gas do not change with the change of
temperature and pressure.
• In other words Cp and Cv are constant.
AVOGADRO’S LAW
Properties of real gas
EQUATION OF STATE FOR
REAL GAS
 EQUATION OF STATE FOR REAL
GAS
• Vander Waal’s Equation
• BEATTIE-BRIDGEMAN EQUATION OF
STATE
• BENEDICT-WEBB-RUBIN EQUATION OF
STATE
• VIRIAL EQUATION OF STATE
 Vander Waal’s Equation
• The equation of state for real gas is given by,

• For ideal gas, the constant a and b are zero.

• If molar volume is considered in the analysis,
the equation of state becomes

Where, - molar volume

- Universal gas constant
 BEATTIE-BRIDGEMAN EQUATION
OF STATE
• This equation is based on five experimentally
determined constraints in the form of,

where

• The beattie-bridgeman equation is known to

be reasonably accurate for densities values up
to 0.8 . Where is the density of the
substance of critical point.
BENEDICT-WEBB-RUBIN EQUATION
OF STATE
VIRIAL EQUATION OF STATE
• Virial or virtual expansions are only applicable
to gases of low and medium densities.
• The equation of state is given by
P

• The coefficient of , , are virial coefficients

 COMPRESSIBILITY FACTOR
• The perfect gas equation is given by,

• But for real gas, a correction factor has to be

introduced in the perfect gas equation to
account the deviation of the real gas from
perfect gas equation.
• This factor is known as compressibility factor
(Z) and is defined by
• The equation of state for real gas at any state
becomes
pv = ZRT
• Similarly, the equation of state for the real gas
at critical point becomes,
pcvc = ZcRTc
COMPRESSIBILITY CHART
GENERALIZED COMPRESSIBILITY
CHART
 Thermodynamic relations
• Maxwell relations
• Tds Equations
• Difference and ratio of heat capacities
• Energy equation
• Joule-Thomson Coefficient
• Clausius Clapeyron equation
• Phase Change Processes.
JOULE THOMSON CO-EFFICIENT
• Joule thomson effect is an efficient way of
cooling gases.
• In this, a gas is made to undergo a continuous
throttling process.
• A constant pressure is maintained at one side
of a porous plug and a constant low pressure at
the other side.
• The apparatus is thermally insulated, so there
is no heat loss.
• Joule thomson coefficient is defined as the
change in temperature with change in pressure
by keeping the enthalpy constant.
 THROTTLING PROCESS
• It is defined as the fluid expansion through a
minute orifice.
• During the throttling process, both pressure
and velocity are reduced.
• But there is no heat transfer and no work is
done on the system.
JOULE – THOMSON EXPERIMENT

 The internal energy of an ideal gas and an

incompressible substance is a function of
temperature only, u = u(T)
 Initially, one tank contains high pressure and the
other tank was evacuated.
 When the thermal equilibrium attains, the valve
is opened to allow air pass from one tank to the
other tank until the pressures are equalized.
 There is no temperature change, because there is
no heat transfer. The tanks are insulated.
 Then there is no change in pressure and volume
due to no work done.
 It is proved that the internal energy is a function
of temperature only and not a function of
pressure or volume
 The figure shows the arrangement of porous
plug at the center.
 In this experiment, a stream of gas at a
pressure p1 and temperature T1 is
continuously allowed to flow through a porous
plug.
 The gas comes out from the other side of the
porous plug at a pressure p2 and temperature
T2.
 The whole apparatus is insulated. Therefore
there is no heat transfer takes place.
Q=0
 The system does not exchange work with the
surrounding.
W=0
 From steady flow energy equation,
 C1
2
  C2
2

h1   Z1 g   Q  h2   Z2 g   W
 2   2 

C1 = C2; Z1 = Z2; Q = 0; W = 0
 So the equation become
h1 = h 2
 It state that the enthalpy is constant for throttling
process.
 The results from this experiment can be plotted
as a constant enthalpy curve on T-p plane.
 The slope of a constant enthalpy is known as
joule – thomson coefficient.

 For real gas μ may be either positive or negative

depending upon the thermodynamic state of gas.
p-T Diagram
Case (i):
There is always a pressure drop in throttling
process. So, pressure and temperature change are
negative. Therefore, μ is positive. This process
produce cooling effect

Case (ii) :
There is always a pressure drop in throttling
process. So, pressure change are negative and
temperature change are positive. Therefore, μ is
negative. This process produce heating effect
Case (iii):
When μ is zero, the temperature remain
constant with throttling process. The temperature
at which μ = 0 is called throttling process.