Ideal and Re Sol

We have reviewed PVT behaviour of
pure components. Let’s now, talk

about equation of state
Equations of state are one of the most common thermodynamic models that are
utilized by chemical engineers.
Copyright Dr. Nayef M. Alsaifi, 2013

All rights reserved 2
Equations of state
 Equation of state is a relation between temperature, pressure and molar volume.
𝑓 𝑃, 𝑇, 𝑉 = 0
 Equation of state can be:

 explicit in pressure: 𝑃 = 𝑓(𝑇, 𝑉)
 explicit in volume 𝑉 = 𝑓(𝑇, 𝑃)
 The pressure-explicit form is more common. Almost all used equations of state are
explicit in pressure.

Ideal gas
 The simplest equation of state is the ideal gas law:
𝑃𝑉 = 𝑅𝑇
 Not applicable for real gas; particularly at high pressure and low temperature.
 Assumption made in deriving the ideal gas equation of state:

 Molecules have negligible size
 Intermolecular forces are zero among molecules

Ideal gas
𝑅𝑇 3.1
Ideal gas law 𝑉=
𝑃
Example Evaluate the validity of the ideal gas law

(Volume occupied by a gas)
P= 0.194 atm P= 1.31 atm P= 19.13 atm P= 40.6 atm

methane T= 95 K T= 115 K T= 160 K T= 186 K
Exp. molar volume

(cm3/mol)
3.97E+04 6.92E+003 5.16E2 1.84E2
Cal. molar volume

(cm3/mol)
4.02E+004 7.20E+003 6.86E2 3.76E2
% error 1.2 % 4.1 % 33 % 104 %
 Ideal gas law is not applicable at high pressure.

 As a rule of thumb, use ideal gas only if pressure is ≈< 1 atm
Virial equation of state
 It was proposed by Kamerlingh Onnes in 1901.

 It has two different forms:
 The first form is a power series expansion in reciprocal volumes

(pressure-explicit form):
𝑅𝑇 𝐵 𝐶 𝐷
𝑃= 1+ + 2+ 3+ … 3.2
𝑉 𝑉 𝑉 𝑉
where B, C, D are called second virial coefficient, third virial coefficient

and fourth virial coefficient; respectively.
 The second form is a power series expansion in pressures

(volume-explicit form):
𝑅𝑇 3.3
𝑉= 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃 3 + …
𝑃
where 𝐵′ , 𝐶 ′ , and 𝐷′ are called second virial coefficient, third virial coefficient
and fourth virial coefficients; respectively.

 The virial coefficients in equation 3.2 ( i.e. B, C, D ) and equation 3.3 (i.e. 𝐵′ , 𝐶 ′ , 𝐷′ )
are related as follows:
′
𝐵 𝐶 − 𝐵2 𝐷 − 3𝐵𝐶 + 2𝐵 3
𝐵 = ′
𝐶 = ′
𝐷 =
𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3
 If the above relations are substituted into equation 3.3, the equation is given in terms
of B, C, D, etc. :
𝑅𝑇 𝐵 𝐶 − 𝐵2 2 𝐷 − 3𝐵𝐶 + 2𝐵3 3
𝑉= 1+ 𝑃+( )𝑃 + ( )𝑃 + … 3.4
𝑃 𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3

 The first form (pressure-explicit form)
𝑅𝑇 𝐵 𝐶 𝐷
𝑃= 1+ + 2+ 3+ … 3.2
𝑉 𝑉 𝑉 𝑉
 Truncated after two terms
𝑅𝑇 𝐵 𝐶
𝑃= 1+ + 2
𝑉 𝑉 𝑉
 Truncated after one term
𝑅𝑇 𝐵
𝑃= 1+
𝑉 𝑉

 The second form (volume-explicit form)
𝑅𝑇 𝐵 𝐶 − 𝐵2 2 𝐷 − 3𝐵𝐶 + 2𝐵3 3
𝑉= 1+ 𝑃+( )𝑃 + ( )𝑃 + … 3.4
𝑃 𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3
 Truncated after two terms

𝑅𝑇 𝐵 𝐶 − 𝐵2 2
𝑉= 1+ 𝑃+( )𝑃
𝑃 𝑅𝑇 𝑅𝑇 2
 Truncated after one term
𝑅𝑇 𝐵
𝑉= 1+ 𝑃
𝑃 𝑅𝑇
9
Virial coefficients
 To use the virial equation of state, one needs to have the virial coefficients.
 Virial coefficients are function of temperature only.
 For many substances, B is available.
 For many substances, C is not known.

 Higher coefficients (D,E,..etc. ) are very difficult to obtain.
 Due to the lack of availability of C and higher virial coefficients (C, D, etc.),
we usually truncate the virial equations to:
𝑅𝑇 𝐵
 The first form 𝑃= 1+
𝑉 𝑉
 The second form

𝑅𝑇 𝐵
𝑉= 1+ 𝑃
𝑃 𝑅𝑇
𝑅𝑇 𝐵
Methane 𝑉= 1+ 𝑃
𝑃 𝑅𝑇
Example Evaluate the validity of virial equation of state

(Volume occupied by a gas)
P= 0.194 atm P= 1.31 atm P= 19.13 atm P= 40.6 atm

T= 95 K T= 115 K T= 160 K T= 186 K
Second virial
-446.6325 -322.3972 -161.9940 -120.3444
coefficient (B)
(cm3/mol)
Exp. molar volume

(cm3/mol)
3.97E+04 6.92E+003 5.16E2 1.84E2
Cal. molar volume

(cm3/mol)
3.97e+004 6.88E+003 5.24E2 2.56E2
% error 0.0 % 0.58 % 1.55% 39%

All rights reserved
Equation of state
Recall: The ideal gas law
PV=RT
 Ideal gas assumptions
 Molecules are point masses (negligible size)
 No forces acting between molecules
 Applicable only at low pressure

Evaluation of Ideal gas assumptions
 Molecules have NON-NEGLIGIBLE size
 Ideal gas says that all molecules (methane, ethane, n-decane, n-octanol,
etc.) have negligible sizes
 In reality, we know that these are not true. Molecules occupy space.
we also know that molecules have different sizes. For example, the size of
ethane is bigger than that of methane.
 There are intermolecular forces acting among molecules
Think of evidence for

the existence of inter-
molecular forces

Clausius equation of state
 Clausius modified the ideal gas by considering the size of molecules.
 Clausius noticed that since molecules have sizes, the available volume for
molecular motion (free volume) is not V but (V-b) where b is a measure of the
volume occupied by the gas molecules:
𝑉 → (𝑉 − 𝑏)
Shaded region is the free volume
available for molecular motion
 Therefore, Clausius equation of state is given by:
𝑃 𝑉 − 𝑏 = 𝑅𝑇
or
𝑅𝑇
𝑃=
𝑉−𝑏
What would happen if attractive forces are considered?
 Which case do you think has a higher pressure Case I or Case II?
barometer
Case I Case II
No attractive forces With attractive forces

 In the presence of attractive forces, pressure reduction is expected to happen.
Modification to the ideal gas law
 In 1873, van der waals made two modifications

to the ideal gas law:
 Molecules have definite sizes
 Molecules have intermolecular forces
Real pressure = repulsive pressure + attractive pressure

van der waals
1837-1923
𝑅𝑇
𝑃= - 𝑃 attractive
𝑉−𝑏
The attractive pressure makes a pressure reduction

(therefore negative sign is used)

Modification to the ideal gas law
 Van der waals assumed that the attractive is proportional to

1
𝜌2 (or 2 ):
𝑉
1
𝑃 attractive 𝛼 𝑉2
𝑎
or 𝑃 attractive = 𝑉2
where a is a constant. This constant is a measure of the

attraction between the molecules. van der waals
1837-1923
 Therefore, the van der waals equation of state is given by:
𝑅𝑇 𝑎
𝑃= −
𝑉− 𝑏 𝑉2
 a is related to the measurement of the attractive forces

 b is related to the size of the molecules 17
Determination of a and b from critical constants
 a and b could be estimated by taking the advantage form the critical isotherm
( the red one in the figure)
D
isotherms
B C T > Tc Critical point
T = Tc
Pressure (P)
 Mathematically, at point C,
the derivative of P with respect
to density equals to zero:
𝑑𝑃
=0 T < Tc M
𝑑𝜌
GAS Co-existence region
 Moreover, point C is an inflection LIQUID
point. Therefore, the second Y Z
derivative of pressure with respect to
density equals to zero: X
𝑑2𝑃
=0
𝑑𝜌2 density 18
Determination of a and b from critical constants
 In terms of molar volume, the derivatives are given by:

𝑑𝑃 𝑑2𝑃
=0 (1) =0 (2)
𝑑𝑉 𝑑𝑉 2
 Estimation the derivatives for van der waals equation of state:
 At the critical point, T=Tc, P=Pc and V=Vc. Apply (1) and (2), the following equations
result: 𝑅𝑇𝑐 𝑎 𝑅𝑇𝑐 2𝑎 2𝑅𝑇𝑐 6𝑎
𝑃𝑐 = − 2 0 =− + 0 = + −
(𝑉𝑐 − 𝑏) 𝑉𝑐 𝑉𝑐 − 𝑏 2 𝑉𝑐 3 𝑉𝑐 − 𝑏 3 𝑉𝑐 4
 Three equations with three unknowns (Tc, Pc, Vc). Solve the three equations simultaneously:
 From the above three equations, it could be shown that:
27 𝑅2 𝑇𝑐2 1 𝑅 𝑇𝑐
𝑎= 𝑏=
64 𝑃𝑐 8 𝑃𝑐
19
van der waals equation of state is cubic in volume
 Van der waals equation of state

𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
 The equation can be re-written in an alternative form:
 Make a common denominator for the right hand side:
𝑉 2𝑅 𝑇 − 𝑎 𝑉 − 𝑏
𝑃=
𝑉2 𝑉 − 𝑏
 Multiply the denominator to the other side and re-arrange the terms:
𝑃𝑉 3 − 𝑃𝑏 + 𝑅𝑇 𝑉 2 + 𝑎𝑉 − 𝑎𝑏 = 0
 van der waals equation of state is cubic in volume.
 Many equations have been proposed as a modification to van der waals

equation of state. In general, they are called cubic equations of state.

Cubic equations of state
 widely used in industrial applications.
 Represent the PVT behavior of both liquids and vapors
 No volume explicit form
 Need iterative solution for V
 The most common cubic equations of state:
 Redlich-Kwong (1949)
 Soave-Redlich-Kwong (1949)
 Peng-Robinson (1976)
 All cubic equations of state can be written in the following form:

𝑉 3 + 𝑓1 𝑇, 𝑃, 𝑐 𝑉 2 + 𝑓2 𝑇, 𝑃, 𝑐 𝑉 + 𝑓3 𝑇, 𝑃, 𝑐 = 0
c is adjustable parameters
Cubic equations of state
 van der waals…………..... 𝑅𝑇 𝑎

𝑃= − 2
𝑉−𝑏 𝑉
𝑅𝑇 𝑎/ 𝑇
 Redlich-Kwong…………… 𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
𝑅𝑇 𝑎𝛼(𝑇)
 Soave-Redlich-Kwong….. 𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
𝑅𝑇 𝑎𝛼(𝑇)
 Peng-Robinson…………… 𝑃= −
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)

Solution of cubic equations of state
 The solution of the cubic equations of state have THREE ROOTS in volume for a
given temperature and pressure:
 T > Tc
 one positive real root (the molar volume of supercritical fluid)
 Two roots containing negative or imaginary number (not physical)
 T = Tc,
 three equal real values are obtained (the critical molar volume)
 T < Tc
 the highest positive real root represents the molar volume of the vapor state
 The lowest positive real root represents the molar volume of the liquid state
 The third real root has no physical meaning

Solution of cubic equations of state

van der waals equation of state
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
27 𝑅2 𝑇𝑐2 1 𝑅 𝑇𝑐
𝑎= 𝑏=
64 𝑃𝑐 8 𝑃𝑐
 Vapor & Vapor-like roots

𝑅𝑇
 Initial guess 𝑉=
𝑃
𝑅𝑇 𝑎 (𝑉 − 𝑏)
𝑉= +𝑏−
𝑃 𝑃 𝑉2
 Liquid & liquid-like roots
 Initial guess 𝑉=𝑏
𝑅𝑇 + 𝑏𝑃 − 𝑉𝑃
𝑉=𝑏+ 𝑉2
All rights reserved
𝑎 25
Redlich-Kwong equation of state
𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
0.42748𝑅2 𝑇𝑐2.5 0.08664𝑅 𝑇𝑐

𝑎= 𝑏=
𝑃𝑐 𝑇 1/2 𝑃𝑐

𝑅𝑇
𝑃
𝑅𝑇 𝑎 (𝑉 − 𝑏)
𝑉= +𝑏−
𝑃 𝑃𝑉 𝑉 +𝑏
𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏)
Copyright Dr. Nayef M. Alsaifi, 2013 𝑎
Soave-Redlich-Kwong equation of state
𝑅𝑇 𝑎
𝑃= −
𝑉−𝑏 𝑉 𝑉+𝑏
0.42748𝛼(𝑇)𝑅2 𝑇𝑐2 0.08664𝑅 𝑇𝑐

𝑎= 𝑏=
𝑃𝑐 𝑃𝑐
1/2
𝛼 𝑇 = 1 + 𝜅 1 − 𝑇𝑟 𝜅 = 0.48 + 1.574𝜔 − 0.176𝜔2

𝑅𝑇
𝑃
𝑅𝑇 𝑎(𝑇) (𝑉 − 𝑏)
𝑉= +𝑏−
𝑃 𝑃 𝑉 𝑉+𝑏
Copyright Dr. Nayef M. Alsaifi, 2013 𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏)
All rights reserved 𝑎(𝑇) 27
Peng-Robinson equation of state
𝑅𝑇 𝑎
𝑃= −
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)
0.45724𝛼(𝑇)𝑅2 𝑇𝑐2 0.07780𝑅 𝑇𝑐

𝑎= 𝑏=
𝑃𝑐 𝑃𝑐
2
𝛼 𝑇 = 1 + 𝜅 1 − 𝑇𝑟 𝜅 = 0.37464 + 1.54226𝜔 − 0.26992𝜔2

𝑅𝑇
𝑃
𝑅𝑇 𝑎(𝑇) 𝑉−𝑏
𝑉= +𝑏−
𝑃 𝑃 𝑉 + (1 − 2)𝑏 𝑉 + (1 + 2)𝑏
Copyright Dr. Nayef M. Alsaifi, 2013 𝑉 = 𝑏 + 𝑉 + (1 − 2)𝑏 (𝑉 + (1 + 2)𝑏)
All rights reserved 𝑎(𝑇) 28
Example
 Calculate the molar volume s of saturated vapor and saturated liquid of n-octane
at 0.215 MPa and 427.85 K assuming that the fluid follows the Redlich-Kwong
equation of state. The critical constants of n-octane are Tc=569.4 K and Pc=24.97 bar.
 First Step: Calculate a & b

0.42748𝑅 2 𝑇𝑐2.5 0.08664𝑅 𝑇𝑐
𝑎= 1/2 = 4.4260 m6 Pa mol-2 𝑏= =1.6426e-004 m3/mol
𝑃𝑐 𝑇 𝑃𝑐
 Vapor root
𝑅𝑇
 Initial guess 𝑉= = 0.0155 m3/mol
𝑃
𝑅𝑇 𝑎 𝑉−𝑏
 First iteration 𝑉= +𝑏− = 0.0155 m3/mol
𝑃 𝑃𝑉 𝑉 +𝑏
 Liquid root

= 1.6426e-004 m3/mol
 First iteration 𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏) = 2.0763e-004 m3/mol
𝑎
𝑅𝑇 + 𝑏𝑃 − 𝑉𝑃 = 2.0763e-004 m3/mol
 Second iteration 𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏)
𝑎 29

Ideal and Re Sol

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We have reviewed PVT behaviour of

pure components. Let’s now, talk

Copyright Dr. Nayef M. Alsaifi, 2013

 Equation of state is a relation between temperature, pressure and molar volume.

 Equation of state can be:

 explicit in volume 𝑉 = 𝑓(𝑇, 𝑃)

Copyright Dr. Nayef M. Alsaifi, 2013

 The simplest equation of state is the ideal gas law:

 Assumption made in deriving the ideal gas equation of state:

Copyright Dr. Nayef M. Alsaifi, 2013

Example Evaluate the validity of the ideal gas law

P= 0.194 atm P= 1.31 atm P= 19.13 atm P= 40.6 atm

Exp. molar volume

Cal. molar volume

% error 1.2 % 4.1 % 33 % 104 %

 Ideal gas law is not applicable at high pressure.

 It was proposed by Kamerlingh Onnes in 1901.

 The first form is a power series expansion in reciprocal volumes

where B, C, D are called second virial coefficient, third virial coefficient

 The second form is a power series expansion in pressures

Copyright Dr. Nayef M. Alsaifi, 2013

Copyright Dr. Nayef M. Alsaifi, 2013

 The first form (pressure-explicit form)

 Truncated after two terms

 Truncated after one term

Copyright Dr. Nayef M. Alsaifi, 2013

 The second form (volume-explicit form)

 Truncated after two terms

 Truncated after one term

 For many substances, B is available.

 For many substances, C is not known.

 The second form

Example Evaluate the validity of virial equation of state

P= 0.194 atm P= 1.31 atm P= 19.13 atm P= 40.6 atm

Exp. molar volume

Cal. molar volume

% error 0.0 % 0.58 % 1.55% 39%

Copyright Dr. Nayef M. Alsaifi, 2013

Recall: The ideal gas law

 Ideal gas assumptions

 Molecules are point masses (negligible size)

 No forces acting between molecules

 Applicable only at low pressure

Copyright Dr. Nayef M. Alsaifi, 2013

 Molecules have NON-NEGLIGIBLE size

 There are intermolecular forces acting among molecules

Think of evidence for

Copyright Dr. Nayef M. Alsaifi, 2013

 Clausius modified the ideal gas by considering the size of molecules.

No attractive forces With attractive forces

 In 1873, van der waals made two modifications

 Molecules have definite sizes

 Molecules have intermolecular forces

Real pressure = repulsive pressure + attractive pressure

The attractive pressure makes a pressure reduction

Copyright Dr. Nayef M. Alsaifi, 2013

 Van der waals assumed that the attractive is proportional to

where a is a constant. This constant is a measure of the

 Therefore, the van der waals equation of state is given by:

 a is related to the measurement of the attractive forces

 In terms of molar volume, the derivatives are given by:

 From the above three equations, it could be shown that:

 Van der waals equation of state