Equation of State (EOS)

 an equation of state (EOS) is

– a thermodynamic equation
– relating state variables --- describe the state of matter under
a given set of physical conditions, such as pressure, volume,
temperature (PVT) etc.,
 Use: correlate densities of gases and liquids to
temperatures and pressures.

 Simplest form of EOS is … ideal gas law

 Valid at low pressures and moderate temperatures
 inaccurate at higher pressures and lower temperatures

 Therefore, a number of more EOS have been developed for gases

and liquids.
 At present, there is no single equation of state that accurately
predicts the properties of all substances under all conditions.
 Assumptions of Ideal-Gas Equation
 Molecular interactions between the individual gas
molecules are negligible  pressure exerted due of
attractive forces are negligible compared to the total
pressure of the system.

 The volume occupied by the individual gas molecules are

negligible compared to the total volume of the system.

 The density of the gaseous system is minimum for ideally

behaving gases.

 At low pressures and high temperatures, the density of a

gas decreases and therefore the gas behaves like an ideal-
gas at low densities.
 Ideal Gas Law
 Boyles law …….At constant temperature….𝑉 𝛼 1Τ𝑃
 Charles law …….At constant pressure….𝑉 𝛼 T

 Combining both….. P𝑉 𝛼 T
 …..PV = RT
 R = universal gas constant…..8.314 J/mol K

 For n number of moles….

 …..PV = n RT

 ….P υ = RT………………….υ = V/n = is the molar

volume…..
[Example] 140 kg of nitrogen at a pressure 4.052 × 105 Pa is stored
in a cylinder of volume 30 m3. It is desired to keep the gas
temperature below 25°C. Does the cylinder need cooling if nitrogen
behaves like an ideal gas.
 Implied Property Relations for an Ideal Gas
Isochoric (or isometric) process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 & 𝑑𝑊 = 𝑃𝑑𝑉 = 0 & 𝑑𝑄 = 𝐶𝑉 𝑑𝑇
𝑑𝑈
_ 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 _ 𝐶𝑉 =
Isobaric process: 𝑑𝑇
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 & 𝑑𝑊 = 𝑃𝑑𝑉 = 𝑑(𝑃𝑉) & 𝑑𝑄 = 𝐶𝑃 𝑑𝑇
_ 𝑑𝑈 = 𝐶𝑃 𝑑𝑇 − 𝑑(𝑃𝑉) _ 𝑑𝑈 + 𝑑(𝑃𝑉) = 𝐶𝑃 𝑑𝑇 _ 𝑑𝐻 = 𝐶𝑃 𝑑𝑇
𝑑𝐻
_ 𝐶𝑃 =
Enthalpy: 𝑑𝑇
𝐻 = 𝑈 + 𝑃𝑉 For 1 mole of ideal gas: _ 𝐻 = 𝑈 + 𝑅𝑇

_ 𝑑𝐻 = 𝑑𝑈 + 𝑅𝑑𝑇 % by dT 𝑑𝐻 = 𝑑𝑈 + 𝑅 _ 𝐶 = 𝐶 + 𝑅
𝑃 𝑉
𝑑𝑇 𝑑𝑇
𝐶𝑃 −𝐶𝑉 = 𝑅
Isothermal process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 & 𝑑𝑈 = 0 _ 𝑑𝑄 = 𝑑𝑊 = න 𝑃𝑑𝑉

For 1 mole of ideal gas:

𝑅𝑇 𝑑𝑉
_ 𝑑𝑄 = 𝑑𝑊 = න 𝑑𝑉 = 𝑅𝑇 න
𝑉 𝑉
𝑉2
𝑄 = 𝑊 = 𝑅𝑇 𝑙𝑛
𝑉1

For an ideal gas at constant temperature:

𝑉2 𝑃1 𝑃1
𝑃1 𝑉1 = 𝑃2 𝑉2 _ = _ 𝑄 = 𝑊 = 𝑅𝑇 𝑙𝑛
𝑉1 𝑃2 𝑃2
Adiabatic process:
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 & 𝑑𝑄 = 0 _ 𝑑𝑈 = − 𝑑𝑊 = − 𝑃𝑑𝑉
& 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝐶𝑉 𝑑𝑇 = − 𝑃𝑑𝑉

For 1 mole of ideal gas: _ 𝐶𝑉 𝑑𝑇 = − 𝑅𝑇 𝑑𝑉

𝑉

𝑑𝑇 𝑅 𝑑𝑉 𝑑𝑇 𝐶𝑃 −𝐶𝑉 𝑑𝑉
_‫׬‬ =− ‫𝑉 ׬‬ _‫׬‬ =− ‫𝑉 ׬‬ 𝐶𝑃 −𝐶𝑉 = 𝑅
𝑇 𝐶𝑉 𝑇 𝐶𝑉

𝑑𝑇 𝐶𝑉 𝐶𝑃 𝑑𝑉 𝐶𝑃 𝑑𝑇 𝑑𝑉
_න = − න 𝛾= _න = (1 − 𝛾) න
𝑇 𝐶𝑉 𝐶𝑉 𝑉 𝐶𝑉 𝑇 𝑉
𝛾−1 𝛾−1
𝑇2 𝑉1 𝑇2 𝑃2 𝛾
_ = _ =
𝑇1 𝑉2 𝑇1 𝑃1
_ 𝑃1 𝑉1 𝛾 = 𝑃2 𝑉2 𝛾 =P𝑉 𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Adiabatic process:
𝑑𝑈 = −𝑑𝑊 & 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
Work done: 𝑑𝑊 = − 𝐶𝑉 𝑑𝑇
𝐶𝑃 −𝐶𝑉 = 𝑅
𝑅
_ 𝑊 = 𝐶𝑉 (𝑇1 − 𝑇2 ) & 𝐶𝑉 = 𝐶𝑃
𝛾−1 𝛾=
𝐶𝑉
𝑅𝑇1 − 𝑅𝑇2 𝑃1 𝑉1 − 𝑃2 𝑉2
_ 𝑊= _ 𝑊=
𝛾−1 𝛾−1
1
𝑃1 𝑉1 𝑃2 𝑉2 𝑃1 𝑉1 𝑃2 𝑃1 𝛾
_ 𝑊= 1− _ 𝑊= 1−
𝛾−1 𝑃1 𝑉1 𝛾−1 𝑃1 𝑃2
γ−1
𝑃1 𝑉1 𝑃2 𝛾
_ 𝑊= 1−
𝛾−1 𝑃1
Polytropic process:
𝑃𝑉 𝑛 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 where, n is a constant.
 Polytropic process:
𝑃1 𝑉1 𝑛 = 𝑃2 𝑉2 𝑛 =𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Workdone:
𝑛−1
𝑅𝑇1 − 𝑅𝑇2 𝑃1 𝑉1 𝑃2 𝑛
𝑊= & 𝑊= 1−
𝑛−1 𝑛−1 𝑃1

𝑅 𝑅
𝐶𝑣 = & ∆𝑈 = 𝐶𝑣 𝑇2 − 𝑇1 _ ∆𝑈 = 𝑇 − 𝑇1
𝛾−1 𝛾−1 2

Heat Transfer: ∆𝑈 = 𝑄 − 𝑊 _ 𝑄 = ∆𝑈 + 𝑊

𝑅 𝑅
Q= 𝑇2 − 𝑇1 + 𝑇1 − 𝑇2
𝛾−1 𝑛−1
𝛾−𝑛 𝑅 𝛾−𝑛
Q= × 𝑇1 − 𝑇2 _ Q = (𝛾 − 1) × 𝑊
(𝛾 − 1) 𝑛 − 1
[Example] An ideal gas is undergoing a series of three operations:
The gas is heated at constant volume from 300 K and 1 bar to a
pressure of 2 bar. It is expanded in a reversible adiabatic process
of 1 bar. It is cooled at constant pressure of 1 bar to 300 K.
Determine the heat and work effects for each step. Assume CP =
29.3 kJ/kmol K.
[Example] Calculate the change in internal energy, change in enthalpy,
work done, and the heat supplied in the following processes:
(a) An ideal gas is expanded from 5 bar to 4 bar isothermally at 600 K.
(b) An ideal gas contained in a vessel of 0.1 m3 capacity is initially at 1
bar and 298 K. It is heated at constant volume to 400 K.
(Assume that CP = 30 J/mol K.).
[Example] Twenty kilograms of air is compressed from 1 bar, 300 K
to 5 bar in a single stage compressor. The process is polytropic with
n = 1.25. The specific heat of air at constant pressure in kJ/kmol K
is:
𝐶𝑃 = 27.4528 + 6.1839 × 10−3 𝑇 − 8.9932 × 10−7 𝑇 2
Determine:
(i) The work done by the compressor per cycle and
(ii) The amount of heat transferred to the surroundings
[Example] Methane is stored in a tank of volume 5.7 × 10−2 m3 at a
pressure of 15 bar and 294 K. The tank valve is partially opened
allowing the gas to flow to a gas holder, where pressure is held
constant at 1.15 bar. Determine the mass of methane removed when
the pressure in the tank dropped to 5 bar under the following
conditions :
(i) If the process occurred slowly so that the temperature was
constant.
(ii) If the process occurred so rapidly that the heat transferred
was negligible. Assume ideal gas behavior and take γ = 1.4.
[Example] A steam boiler of volume 2.3 m3 initially contained 1.7 m3
liquid water in equilibrium with 0.6 m3 of vapour at 100 kPa. The
boiler is heated keeping the inlet and discharge valves closed. The
relief valve is set to lift when the pressure in the boiler reaches
5500 kPa. Determine the amount of heat supplied to the contents in
the boiler before the relief valve lifts.
 Limitations of Ideal-Gas Equation of State

 Many familiar gases such as Air, Nitrogen, Oxygen etc

and heavier gases such as Carbon Dioxide CAN be
treated as Ideal-Gas with negligible error (often less
than 1%).
 Dense gases such as Water Vapour in Steam Power
Plants and Refrigerant Vapour in Refrigerators should
NOT be treated as Ideal-Gas. Instead, the Property
Tables should be used.
 EOS for real gases….

• van der Waals equation

• Redlich – Kwong equation (RK equation)
• Soave – Redlich – Kwong equation (SRK equation)
• Peng – Robinson equation (PR equation)
• Benedict – Webb- Rubin equation (BWR equation)
• Virial equation
 van der Waals equation
• Correction factors for Pressure and volume occupied by gas
molecule was introduced in the ideal gas law
• The correction factors are ‘a’ and ‘b’
• a = correction term for pressure to account for the
intermolecular forces of attraction
• b = correction term for volume to account for the volume of the
molecules

 a  RT a
 P  2  V  b   RT P  2
V b V
 V 

27 R 2Tc2 RTc
a 4
.....Nm /mol 2 b ......m 3 / mol
64 Pc 8 Pc
 Derivation of van der Waals constants a & b

(1)

In PV diagram

(1)== (2)

(3)
Derivation of van der Waals constants a & b

(2)= (4)

(5)

(Eqn.3 divided by Eqn.5)

Sub. B value in Eqn.3

Sub. a & b values in Eqn.1 @ critical condition
[Example] One kilomol CO2 occupies a volume of 0.381 m3 at 313 K.
Compare the pressures given by
a) Ideal gas equation
b) van der Waals equation
Take van der Waals equation constants a = 0.365 Nm4/mol2 and b =
4.28 x 10 −5 m3/mol.
 Calculation of molar volumes of vapor
and liquid using van der Waals equation

RT
 a   Vi 1  b 
 P  2 
V  b   RT  a 
 V   P  2 
 Vi 

V  b   RT
• Iterative procedure is used to find
 a 
P 2  the volume
 V 
• Iteration is stopped when Vi+1 ≈ Vi

V  b
RT • For initial / first iteration……i = 0
 a  • If vapor….vo = RT/P
P 2  • If liquid….vo = b
 V 
[Example] Calculate the volume occupied by 1 mol of saturated n-
octane vapor at 427.85 K at a saturation pressure of 0.215 MPa by
van der Waals equation.
Take van der Waals equation constants a = 3.789 Nm4/mol2 and b =
2.37 x 10 –4 m3/mol.
Repeat the calculations for saturated n-octane liquid.
 Redlich – Kwong Equation
• The Redlich – Kwong is a two-parameter equation of state
widely used in engineering calculations.

 a  RT a
 P  T 0.5V (V  b)  V  b   RT P  0 .5
  V  b T V (V  b)

R 2Tc2.5 0.0867 RTc

a  0.4278 .....Nm 4 K 0.5 /mol 2 b ......m 3 / mol
Pc
Pc
[Example] Using the Redlich-Kwong equation calculate the molal
volumes of saturated liquid and saturated vapor of methyl chloride
at 333 K. The saturation pressure of methyl chloride at 333 K is
13.76 bar. The critical temperature and pressure are 416.3 K and
66.8 bar respectively.
[Example] Determine the molar volume of gaseous methane at 300 K
and 600 bar by the following methods:
a) Using ideal gas equation
b) Using VDW equation…given that a = 0.2285 Nm4/mol2 and b =
4.27 x 10 –5 m3/mol.
c) Using RK equation given that Tc =191.1 K and Pc = 46.4 bar.
 The Compressibility Factor, Z
 The ideal-gas equation is very simple and thus very convenient to use.
 But, gases deviate from ideal-gas behavior significantly at states near
the saturation region and the critical point.
 This deviation from ideal-gas behavior at a given temperature and
pressure can accurately accounted by a correction factor called as
compressibility factor, Z.
• It is defined as Z = PV/RT.

• It is the ratio of the volume of a real gas at a set of specified

temperature and pressure to the volume occupied by the gas at the
same temperature and pressure if it
were an ideal gas. Z
V V
 actual
RT Videal
P

• The compressibility factor of an ideal gas is unity at all conditions.

• Since a real gas behaves ideally as pressure is reduced, the
compressibility factor of a real gas approaches unity as the pressure is
reduced to zero.
 The Compressibility Factor, Z
 For an ideal gas, Z = 1 and
the curve of Z vs P is a
straight horizontal line.
 The shape of the curve for a
real gas depends on the
nature of the gas.
 however, since a real gas
behaves ideally as pressure
is reduced, Z = 1 as the P
0
 At the other conditions, the
Z may be < 1 or > 1 depending
on the temperature and
pressure of the gas.
 Principle of Corresponding States
 Gases behave differently at a given temperature and
pressure, but they behave very much the same at
temperatures and pressures normalized with respect to
their critical temperatures and pressures.
 Thisprinciple states that all gases when compared at
the same reduced temperature and the reduced
pressure, have approximately the same compressibility
factor and all deviate from the ideal behavior to the
same extent.
(law of two parameter state)
 The normalization is done as
 Reducedpressure, Pr = P / Pc and Reduced
temperature, Tr = T/Tc
 Principle of Corresponding States
Z factor for all gases is approximately the same at
the same reduced pressure and temperature.
 This is called the principle of corresponding states.
Methane Nitrogen
Tc (K) 191 126
Pc (bar) 46 34
 Methane @ 382 K & 69 bar and Nitrogen @ 252 K & 51
bar will be having the same compressibility factor
because both have same Tr and Pr.
 Pr = P / Pc = 1.5 & Tr = T/Tc = 2
 Thus the principle of corresponding state enables one to
coordinate the properties of a range of gases to a single
diagram such as the generalized compressibility chart.
 Generalized Compressibility Charts
 The generalized compressibility
chart is constructed based on
the principle of corresponding
states.
 Z = f (Tr, Pr)
 Also known as two parameter
compressibility factor method.
 Based on experimental P-V-T
data on 30 gases, Nelson & Obert
prepared these charts which give
the Z with an average deviation
of < than 5% from the
experitmetnal values.
 When precise equation of state is
not available, these charts
provide a convenient method for
the evaluation of compressibility
factor.
[Example] A 6 m3 tank contains 25 kmol of a gas at 275 bar and 882
K. Determine the critical temperature of the gas using generalized
compressibility factor method. Given that the critical pressure is 50
bar.
[Example] Determine the specific volume of superheated water
vapor (Tc: 647.3 K; Pc: 221.2 bar) at 10 MPa and 400°C, using
(a) the ideal-gas equation,
(b) the generalized compressibility chart and compare with the
actual value 4.759x10– 4 m3/mol.
(c) Also determine the error involved in both cases.
[Example] Using Nelson – Obert chart, estimate the volume occupied
by 1 kg water vapor at 17 bar and 500 K; given the critical pressure
and temp of water as 221.2 bar and 647.3 K. Compare the result
with the volume calculated using the ideal gas equation.
 To calculate the pressure using
Compressibility chart…..
• First calculate the Tr
• Calculate the value of Z as a function of Pr
Z = PV/RT =PcPr V/RT
…Z = (constant) Pr
….Y = m X form…..

• Refer the compressibility chart and locate this slope

and join the with the origin and extend the line till
intersects the Tr value…..and read the Z value & Pr

• From Z value….calculate the value of P.

[Example] Using the Nelson-Obert chart calculate the
pressure developed by 4 kg oxygen contained in a vessel
of volume 0.03 m3 at 250 K. The critical constants of
oxygen are 154.6 K & 50.5 bar.
 Virial equation of state
 From the experiments, PV for a gas or vapour along an
isotherm is almost constant and it equal to RT, as the
pressure tend to zero or volume tend to infinity.
 The virial equation of state, proposed by Kammerlingh
Onnes for real gases, wherein the compressibility
factor, Z is expressed in terms of power series in 1/V
or P.
PV B C D
Z  1   2  3  .........
RT V V V

PV
Z   
 1  B P  C P  D P  .........
2 3

RT
 B,C,D and B’, C’, D’ are virial coefficients
 Virial equation of state
 The more the number of virial coefficients used in the
equation the better is the prediction of gas molar
volume.
 The truncated form of virial equations are ….

PV B C
Z  1  2 units of B...m 3 / mol
RT V V

PV
Z  1  BP  C ' P 2 2
units of B'...m / N
RT
[Example] Using the virial equation of state, calculate the
molar volume of methanol vapor at 500 K and 10 bar. The virial
coefficients are, B = –2.19 x 10 – 4 m3/mol; C = –1.73 x 10 – 8
m6/mol2.
[Example] Calculate the molar volume and compressibility
factor of isopropanol vapor at 473 K and 10 bar. Assume that
the isopropanol follows the virial equation of state. The virial
coefficients are, B = –3.88 x 10 – 4 m3/mol; C = –2.6 x 10 – 8
m6/mol2.
 Other Cubic Equations of State
Soave/Redlich/Kwong Equation:

RT a
P 
V  b V (V  b)

R 2Tc2.5 0.0867 RTc

a  0.4278 4 0.5 2 b ......m 3 / mol
Pc .....Nm K /mol Pc

𝛼 = [1 + 0.48 + 1.57 𝜔 − 0.176 𝜔2 (1 − 𝑇𝑟 )]2

.... is the ascentric factor
 Other Cubic Equations of State
Peng/Robinson Equation:
RT a
P  2
V  b V  2bV  b

0.0778 RTc
a  0.45724
R 2Tc2.5
4 0.5 2 b ......m 3 / mol
Pc .....Nm K /mol Pc

𝛼 = [1 + 0.37464 + 1.542 𝜔 − 0.26992 𝜔2 (1 − 𝑇𝑟 )]2

.... is the ascentric factor
 Other Cubic Equations of State
Benedict / Webb / Rubin equation (BWR equation):

where A0, B0, C0, a, b, c, α and γ are constants.

 Equation Application
Ideal-gas Pr < 0.05, Tr >1.5
or, P < 2 atm, T > 25 oC
Van der Waals Only for vapor.
Lower pressure.
Viral Equation Only for vapor.
(C = D =…0) Tr > 0.436 Pr +0.6
Redlich/Kwong Only for vapor.
Lower pressure.
Soave/Redlich/Kwong Saturated vapor and saturated liquid.
Higher pressure.
Peng Robingson Saturated vapor and saturated liquid.
Higher pressure.
Standard to hydrocarbon industry.
Benedict /Webb/Rubin petroleum and natural gas industries -
Light hydrocarbons and their mixtures