P-V-T behavior of Fluids

P-V-T behavior of Pure Fluids

• Thermodynamic state of pure fluid is described in terms of two independent state variables

• Concept of Critical temperature

and pressure.
• TC = 647.3 K, PC = 220.5 bar
• Highest possible temperature at
which vapor and liquid phases
can exist in equilibrium.
Phase diagram is a plot of temperature at which each phase of a pure substance is
most stable.

• Concept of Triple point

• T = 273.16 K, P = 6.1 x 10-3 bar
 Liquefaction of Gases
• Gases can be converted into liquids by compression at suitable
temperatures.
• Reducing the temperature is the second method
• Liquefaction of gas take place when intermolecular forces of
attraction increase to an extent that gas molecules combine
together to form liquid state.
What happens when pressure is increased
and temperature is reduced for gas
• Pressure is increased, volume of gas decreases
• Decrease in volume of gas brings gas molecules together and space between
them is reduced.
• When temperature reduces average kinetic energy of molecules also decreases
• Force of attraction between the molecules increases as they are moving at low
speed because of high pressure and low temperature.
• Thus a gas is converted into liquid
 Concept of Critical Temperature and Pressure
• Gases can be converted into liquids by compression at suitable
temperatures.
• However as temperature increases it becomes difficult to liquify them
– kinetic energy of gas molecules increases
• Critical temperature – temperature at and above which vapour of
substance cannot be liquified, no matter how large the pressure is.
substance critical temperature (oC)
NH3 132
O2 -119
CO2 31.2
H2O 374

substance critical pressure (atm)

NH3 111.5
O2 49.7
CO2 73.0
H2O 217.7
Critical pressure – Pressure required to liquify a gas at its critical temperature
• Vapor can be condensed by compression at constant temperature / cooling at constant
pressure
• Gas can be condensed only by reduction of temperature at constant pressure – Temperature
has to be brought down below Critical temperature to get it condensed.
Equation of State and Ideal Gas
• The relations between thermodynamic properties such as temperature,
pressure, and volume of a single homogenous fluid is called equation of
state.
• Many mathematical relations have been proposed to represent the PVT
behavior
𝒇 ( 𝑷 , 𝑽 , 𝑻 )=𝟎
• Equation is called as equation of state.
• Most simplest equation or form of equation of state is available for
perfect/ideal gases.
• Derived from kinetic theories and P-V-T behavior of fluids
• Van de Waals equation is a modification to ideal gas equation

• Ideal gas is one

a) Size of the molecule is small as compared to the distance between them.
b) Volume occupied by the molecules is negligible as compared to the total
volume of the gas
c) Intermolecular force of attraction is negligible
• Thermodynamic Characteristics of Ideal gas is one for which following
properties are applicable
1. For one mole of ideal gas equation of state is given by
𝑷𝑽 = 𝑹𝑻 𝑹=𝑼𝒏𝒊𝒗𝒆𝒓𝒔𝒂𝒍 𝑮𝒂𝒔 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
2. Internal energy of ideal gas is dependent only on temperature. It is independent
of pressure and volume

[ ] [ ]
𝝏𝑼
𝝏𝑽 𝑻
=
𝝏𝑼
𝝏𝑷 𝑻
=𝟎

3. Joule Thomson coefficient is Zero for an Ideal Gas.

𝝁=
[ ]
𝝏𝑻
𝝏𝑷 𝑯
=𝟎

Joule Thomson coefficient is signified as the change in temperature resulting from

expansion of gas between two constant pressures under adiabatic conditions with
no work exchange with surroundings.
𝒅𝑯 =𝒅𝑸 − 𝒅𝑾
Equations of State for Real Gas
• Ideal Gas law is inadequate for explaining thermodynamic behavior of real
gases.
• This can be viewed as an approximation to describe the behavior of real
gases at atmospheric pressures or limiting behavior of gases at low
pressures
• Many mathematical relations have been proposed to represent the PVT
behavior
• Three roots for this equation
• Largest volume is vapor volume
• Smallest is liquid volume
• P – saturated pressure, smallest and largest
𝑓 𝑜𝑟 1𝑚𝑜𝑙𝑜𝑓 𝐼𝑑𝑒𝑎𝑙 𝐺𝑎𝑠 roots correspond to volume of saturated vapour
and liquid.
Perfect gas equation fails to explain the P-V-T behaviour of real gases as
• Volume occupied by the molecules of a real gas and the forces of interaction between
them are not negligible as in an ideal gas.
• van der Waals equation takes into account these two features of a real gas by
incorporating certain correction factors
Correction term for Pressure and volume
• consider the forces of attraction on a molecule hitting the wall of the container
• When the molecule hits the wall it experiences a net attractive force towards the
surrounding molecules, thereby, reducing the pressure that would have been exerted by the
molecule on the wall in the absence of intermolecular attraction.
• attractive force is directly related to the number of molecules per unit volume and the
frequency of molecular collision - the net attractive force is proportional to 1/V 2
• centres of two identical molecules are at a distance equal to the molecular diameter at the
instant of collision, molecular separation at collision cannot be smaller than this distance
• Since each molecule is surrounded by a forbidden volume that cannot be penetrated by
another molecule, the effective volume of the gas will be less than the actual volume

Van der Waals Equation of State

𝑓 𝑜𝑟 1𝑚𝑜𝑙𝑜𝑓 𝐼𝑑𝑒𝑎𝑙3𝐺𝑎𝑠 𝑓 𝑜𝑟 𝑛𝑚𝑜𝑙𝑒𝑠

𝑚
𝑉 − 𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒( )
𝑘𝑚𝑜𝑙
[ 𝒏𝟐 𝒂
]
𝑷 + 𝟐 [ 𝑽 −𝒏𝒃 ] =𝑹𝑻
𝑽
 𝑓 𝑜𝑟 𝑛𝑚𝑜𝑙𝑒𝑠

[ ]
𝟐
𝒏 𝒂
𝑷 + 𝟐 [ 𝑽 −𝒏𝒃 ] =𝑹𝑻
𝑽

𝑓 𝑜𝑟 1 𝑚𝑜𝑙𝑒

[ ]
𝜕𝑃
[ ]
2
𝜕 𝑃
=0 =0
𝜕𝑉 𝑇 𝜕𝑉
2
𝑇
 𝑭𝒓𝒐𝒎 𝒆𝒒𝒏 ¿𝟐
2 𝑅 𝑇𝐶 6𝑎
3
= 4
𝑅𝑇 𝑎 (𝑉 𝐶 − 𝑏) 𝑉𝐶
𝑃= − 2
𝑉 −𝑏 𝑉

[ ]
𝜕𝑃
𝜕𝑉 𝑇
=−
𝑅𝑇
2
( 𝑉 −𝑏 ) 𝑉
+
2𝑎
3
=0
𝑭𝒓𝒐𝒎 𝒆𝒒𝒏 ¿𝟏
2𝑎 𝑅𝑇𝐶

[ ]
2
𝜕 𝑃 2 𝑅𝑇 6𝑎 =
2
= 3
− 4
=0 𝑉 𝐶3 ( 𝑉 𝐶 −𝑏 )2
𝜕𝑉 𝑇 ( 𝑉 − 𝑏) 𝑉
𝑺𝒖𝒃𝒔𝒕𝒊𝒕𝒖𝒕𝒊𝒏𝒈𝒊𝒏 𝒆𝒒𝒏¿𝟑
2 𝑅 𝑇𝐶 3 𝑅 𝑇𝐶
=
(𝑉 𝐶 − 𝑏) (𝑉 𝐶 − 𝑏)
2
𝑉 𝐶 ( 𝑉 𝐶 − 𝑏 )2
𝑅𝑇𝐶 2𝑎
− + =0 𝒆𝒒𝒏 ¿ 𝟏
( 𝑉 𝐶 − 𝑏)
2
𝑉 𝐶3 2 3
=
(𝑉 𝐶 − 𝑏) 𝑉 𝐶
2 𝑉 𝐶 =3 𝑉 𝐶 − 3 𝑏 𝑽 𝑪 =𝟑 𝒃
 𝑹𝟖 𝒂 𝒂
𝑭𝒓𝒐𝒎 𝒆𝒒𝒏 ¿𝟏 𝑷 𝑪= −
𝟐𝟕 𝑹𝒃(𝟑 𝒃− 𝒃) 𝟗 𝒃 𝟐
2𝑎 𝑅𝑇𝐶
=
𝑉 𝐶3 ( 𝑉 𝐶 −𝑏 )2 𝟖𝒂 𝒂
𝑷 𝑪= −
𝟐𝟕 𝒃 ×𝟐 𝒃 𝟗 𝒃𝟐

𝟒𝒂 𝒂
𝑷 𝑪= 𝟐
− 𝟐
𝑅𝑇𝐶 2𝑎 𝟐𝟕 𝒃 𝟗 𝒃
2
= 3
( 3 𝑏 −𝑏 ) (3 𝑏) 𝒂
𝑷 𝑪= 𝟐
𝑅 𝑇𝐶 𝟐𝟕 𝒃
2𝑎
=
4 𝑏2 27 𝑏 3 𝑽 𝑪 =𝟑 𝒃
𝑅 𝑇𝐶 2 𝑎 𝟖𝒂
= 𝑻 𝑪=
4 27𝑏 𝟐𝟕 𝑹 𝒃
𝟖𝒂
𝑻 𝑪= 𝑅𝑇 𝑎
𝟐𝟕 𝑹 𝒃 𝑃= −
𝑉 −𝑏 𝑉 2
𝑹𝑻𝑪 𝒂
𝑷 𝑪= −
𝑽 𝑪 − 𝒃 𝑽 𝑪𝟐 𝒚 =𝒎𝒙 + 𝒄
 𝑅𝑇𝐶 𝑎 1
𝑃 𝐶= −
𝑉 𝐶− 𝑏 𝑉 𝐶 2
𝑽 𝑪 =𝟑 𝒃 𝑃 𝐶=
8𝑏
[ 4 𝑅 𝑇 𝐶 −3 𝑅 𝑇 𝐶 ]

𝑅 𝑇𝐶 𝑎 𝑅𝑇𝐶 𝑅 𝑇𝐶
¿ − 𝑃 𝐶= 𝑏=
3 𝑏 −𝑏 9 𝑏2 8𝑏 8 𝑃𝐶
𝑅𝑇𝐶 𝑎 27 𝑅 𝑻 𝑪 𝑅 𝑇 𝐶
¿ − 𝑎 27 𝑅 𝑻 𝑪
2𝑏 2 = 𝑎=
9𝑏 𝑏 8 8 8 𝑃𝐶

[ ]
2 2
1 𝑅 𝑇𝐶 𝑎 27 𝑅 𝑻 𝑪 𝑅 𝑇𝐶
𝑃 𝐶= − 𝑎= 𝑏=
𝑏 2 9𝑏 64 𝑃 𝐶 8 𝑃𝐶
𝟖𝒂
𝑻 𝑪=
𝟐𝟕 𝑹 𝒃
𝑎 27 𝑅 𝑻 𝑪
=
𝑏 8

𝑃 𝐶=
𝑏[
1 𝑅 𝑇 𝐶 27 𝑅 𝑻 𝑪
2
−
9 ×8 ]
Principle of Corresponding States
• Pressure expressed in terms of critical parameters result in principle of
corresponding states.

𝑓 𝑜𝑟 1𝑚𝑜𝑙𝑜𝑓 𝑅𝑒𝑎𝑙 𝐺𝑎𝑠

3
𝑚
𝑉 − 𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒( )
𝑘𝑚𝑜𝑙
• Ratio of pressure, temperature and volume of gas to the corresponding
critical values of gas is called as reduced properties.
𝑷 𝑽 𝑻
𝑷 𝒓= 𝑽 𝒓=
𝑽𝑪
𝑻𝒓= 𝑷 =𝑷 𝒓 𝑷 𝑪𝑽 =𝑽 𝒓 𝑽 𝑪 𝑻 =𝑻 𝒓 𝑻 𝑪
𝑷𝑪 𝑻𝑪
• Substituting the values of P,V,T in the Van der Waals Equation

¿
𝒂
𝑷 𝑪= 𝟐
𝟐𝟕 𝒃
𝑽 𝑪 =𝟑 𝒃

[ 𝒂 𝑷𝒓
𝟐
+
𝒂
𝟐
𝟐𝟕 𝒃 𝟗 𝒃 𝑽 𝒓
2 [
]𝟑 𝒃𝑽 𝒓 −𝒃 =
𝟖 𝒂𝑹 𝑻 𝒓
] 𝟐𝟕 𝑹𝒃 𝑻 𝑪=
𝟖𝒂
𝟐𝟕 𝑹 𝒃
 • If two or more gases have same
𝒂𝒃 𝑷 𝒓
+
[
𝟏
𝒃 𝟐𝟕 𝟗 𝑽 𝒓
𝟐 2 [
𝟑 𝑽 𝒓 −
]
𝟏 =
𝟖 𝒂𝑻𝒓
] 𝟐𝟕 𝒃
reduced pressure and
temperature, then they will have
the same reduced volume.

[ ]
𝑷𝒓 𝟏 𝟖𝑻𝒓 • At a given reduced pressure and
+
𝟐𝟕 𝟗 𝑽 𝒓 2
[ 𝒓 ] 𝟐𝟕
𝟑 𝑽 −𝟏 = temperature fluids will have
same reduced volume.

𝑀𝑢𝑙𝑡𝑖𝑝𝑙𝑦𝑖𝑛𝑔 𝑏𝑜𝑡h 𝑠𝑖𝑑𝑒𝑠 𝑤𝑖𝑡h 27 𝒇 ( 𝑷 𝒓 ,𝑽 𝒓 , 𝑻 𝒓 ) =𝟎

[ 𝟐𝟕 𝑷 𝒓
𝟐𝟕
+
𝟐𝟕
𝟗𝑽 𝒓
2 [
]
𝟑 𝑽 𝒓 −𝟏 ] =
𝟐𝟕 ×𝟖 𝑻 𝒓
𝟐𝟕

𝑤𝑒 𝑔𝑒𝑡
[ 𝑷𝒓 +
𝟑
𝑽𝒓 ]
2 [
𝟑 𝑽 𝒓 − 𝟏 ] =𝟖 𝑻 𝒓

• This equation is called reduced equation

of state.
• Independent of ‘R’ and Van der waals
constant ‘a’ and ‘b’.
• Doesn’t refer to any specific substance
For one mole of ideal gas equation of state is given by

𝑷𝑽 = 𝑹𝑻
Real gas obeys ideal gas law only at low pressures and high temperatures

The deviation of real gas from ideal behavior is expressed in terms of

compressibility factor.
• Non ideality of a gas is expressed by Compressibility factor which is given
by 𝑷𝑽
𝒁=
𝑹𝑻
𝒁=
𝑽 𝑨𝒄𝒕𝒖𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒈𝒂𝒔
𝑹𝑻 ¿
( ) 𝑽𝒐𝒍𝒖𝒎𝒆 𝒑𝒓𝒆𝒅𝒊𝒄𝒕𝒆𝒅 𝒃𝒚 𝒊𝒅𝒆𝒂𝒍 𝒈𝒂𝒔 𝒍𝒂𝒘
𝑷
For ideal gas Z is unity, under all conditions of temperature and pressure

For real gas Z is greater or less than unity

The compressibility factor for a perfect gas has a value of unity at all conditions
For real gas behaves ideally as pressure is reduced, compressibility factor of
real gas approaches unity as pressure is reduced. lim 𝒁=𝟏
𝑷 →𝟎
 𝑷 𝑽 𝑻
𝑷 𝒓= 𝑽 𝒓 = 𝑻 =
𝑷𝑪 𝑽𝑪 𝒓 𝑻𝑪

Methane – TC = 191 K PC = 46 bar

T = 382 K and P = 69 bar
Nitrogen – TC = 126 K PC = 34 bar
T = 252 K and P = 51 bar
𝒁=𝒇 ( 𝑷 ¿ ¿𝒓 ,𝑻 𝒓 )¿

Principle of Corresponding States

All gases when compared at same reduced temperature and reduced pressure,
have approximately same compressibility factor and all deviate from ideal
behavior to the same extent.
• Critical properties is used as a basis for comparison of properties
• Reduced properties are obtained by dividing actual variables by
corresponding critical constants
• Any two gases having same reduced properties will deivate from
corresponding critical properties to the same extent.
• Compressibility factor any single component is a function of two properties
reduced temperature and pressure
Generalized Compressibility Charts

𝒁=𝒇 ( 𝑷 ¿ ¿𝒓 ,𝑻 𝒓 )¿

• Generalized compressibility charts is constructed on the principle of

corresponding states
• Best means of expressing deviation from ideal behaviour
• Alternate for EOS – Compressibility factor can be estimated – deivation of
5%
Virial Equation
Compressibility factor is expressed here as a power series in reciprocal
volumes or pressures
𝑷𝑽 𝑩 𝑪 𝑫
𝒁= =𝟏+ + 𝟐 + 𝟑 +…………….
𝑹𝑻 𝑽 𝑽 𝑽

𝑷𝑽 ′ ′ 𝟐 ′ 𝟑
𝒁= =𝟏+ 𝑩 𝑷 + 𝑪 𝑷 + 𝑫 𝑷 +… … .
𝑹𝑻
• For a given gas these coefficients are functions of temperature only.
• Find its application at low to moderate pressures, truncated after second
term, without much error.
• Strongly correlated through kinetic theory – sound theoretical basis – free
from assumptions.
• Virial coefficients can be given physical interpretations.

B, B’ – Second virial coefficient takes into account the deviation from ideal
behavior resulting from molecular interactions between two molecules
C, C’ – Third virial coefficient takes into account the deviation from ideal
behavior resulting from molecular interactions between three molecules.
 Redlich Kwong Equation Peng – Robinson Equation
𝑅𝑇 𝑎𝛼
𝑅𝑇 𝑎 𝑃= −
𝑃= − 0.5 𝑉 −𝑏 𝑉 ( 𝑉 + 𝑏 ) +𝑏 (𝑉 − 𝑏)
𝑉 −𝑏 𝑇 𝑉 (𝑉 +𝑏)
2 2 .5
0.4278 𝑅 𝑻 𝑪 0.0867 𝑅 𝑇 𝐶
𝑎= 𝑏= Berthelot Equation
𝑃𝐶 𝑃𝐶
𝑅𝑇 𝑎
𝑃= −
Redlich Kwong Soave Equation 𝑉 −𝑏 𝑇𝑉 2

𝑅𝑇 𝑎′ (𝑇 )
𝑃= −
𝑉 −𝑏 𝑉 (𝑉 +𝑏)
′
𝑎 ( 𝑇 )=𝑎 𝛼