CHAPTER 3

PROPERTIES OF PURE
SUBSTANCES

Equation Of States (EOS)

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EQUATION OF STATES (EOS)
An Equation of State (EOS) is an equation that relates
the pressure, temperature, and the molar volume
(PVT) of a substance.

Types of EOS
i. Ideal Gas (gas)
ii. Virial EOS (gas)
iii. Van der Waals EOS (gas & liquid)
Cubic EOS
iv. Redlich-Kwong EOS (gas & liquid)
Ideal Gas EOS
The simplest and best-known equation of state for
substances in the gas phase is the ideal-gas equation of
state. This equation predicts the P-v-T behavior of a
gas quite accurately within some properly selected
region.
Ideal gas equation of state

For IDEAL gases, Z=1

The Ideal Gas EOS;

~
PV
Z 1
RT
Equation for Process Calculations Involving Ideal Gases

For ideal gas in any closed-system process;(dQ dW) or (dQ + dW) = dU = CvdT

i. Constant Volume Process (Q = U = Cv dT)

ii. Constant Pressure process (Q = H = Cp dT)

iii. Isothermal Process ( H = U = 0)

Q = W or Q = -W = RT ln V2/ V1 = RT ln P1/P2

iv. Adiabatic Process (dQ = 0)

(T2/T1) = (V1/V2) R/Cv TV -1 = Const.
(T2/T1) = (P2/P1) R/Cp TP(1- )/ = Const.
(P2/P1) = (V1/V2) Cp/Cv PV = Const.
W = Cv T = R T / - 1 = R(T2 T1)/ - 1 = (P2V2 P1V1) / - 1
T1 and V2 usually unknown;
W = RT1/ - 1[(P2 /P1) ( -1)/ - 1] = P1V1/ - 1[(P2 /P1) ( -1)/ - 1]

v. Polytropic Process (PV = Const.)

(T2/T1) = (V1/V2) R/Cv TV -1 = Const.
(T2/T1) = (P2/P1) R/Cp TP(1- )/ = Const.
W=[RT1/ - 1][(P2 /P1) ( -1)/ - 1]
Q= (( ) RT1) / (( 1) ( -1)) ((P2 /P1) ( -1)/ 1)
 P(V)^Cp/Cv = P(V)^Cp/Cv
(P/P) = (V/V)^Cp/Cv
[(mRT/V)*(V/mRT)] = (V/V)^Cp/Cv
(TV/TV) = (V/V)^Cp/Cv
(T/T) = (V/V)^Cp/Cv * (V/V)^-1
= (V/V)^[(Cv+R)/Cv - 1]
= (V/V)^[1 - 1 + R/Cv]
(T/T) = (V/V)^ R/Cv

not isobaric, cant transform into enthalpy

mass, m can be cancelled, as it is fixed in closed-system

Adiabatic, 0
(T/T) = (V/V)^ R/Cv = Cp/Cv Cp = Cv
= Cv/Cv + R/Cv
= [(mRT/P)*(P/mRT)]^ R/Cv
= 1 + R/Cv
= (TP/TP)^R/Cv = (T/T)^R/Cv * (P/P)^R/Cv
R = (-1)Cv
(T/T)^(1+ R/Cv) = (P/P)^R/Cv
(T/T)^(Cv/Cv+ R/Cv) = (P/P)^R/Cv
(T/T)^(Cp/Cv) = (P/P)^R/Cv
(T/T) = (P/P)^[(R/Cv)*(Cv/Cp)] (T/T) = (P/P)^ (-1)Cv/Cv
(T/T) = (P/P)^ R/Cp = (P/P)^ (-1)/
T(P)^-(-1)/ = T(P)^-(-1)/
T(P)^(1-)/ = constant
Example; 3.2 (J.M Smith Book)
1 mol of air is compressed from an initial state of 1 bar and 25oC
to a final state of 5 bar and 25oC by three different
mechanically reversible processes in a closed s 25oC system;

a. Heating at constant volume followed by cooling at constant

pressure
b. Isothermal compression
c. Adiabatic compression followed by cooling at constant
volume

Assume air to be an ideal gas with Cv = (5/2)R and Cp = (7/2)R. For

each process, Calculate;

i. The work required

ii. The heat transferred
iii. The changes in internal energy
iv. The changes in enthalpy
v. Show the processes on a Pv diagram
 Solution
a) Heating at constant volume followed by cooling at constant pressure

From Ideal gas law, find v1 and v3, v1 = v2 = 0.02479 m3/mol & v3 =0.004958m3/mol
 b) Isothermal compression

c) Adiabatic compression followed by cooling at constant volume

v- Show the processes on a Pv diagram
Example; 3.3 (J.M Smith Book)
An ideal gas undergoes the following sequence of
mechanically reversible processes in a closed system

a. From initial state of 1 bar and 70oC it is

compressed adiabatically to 150oC
b. It is then cooled to 70oC at constant pressure
c. Finally, it is expanded isothermally to its original
state

i. Calculate W, Q, U, H for each of the three

processes and for the entire cycle.
ii. Show the processes on a Pv diagram.

Given Cv = (3/2)R and Cp = (5/2)R.

Solution
i- Calculate W, Q, U, H for each of the three processes and
for the entire cycle.
Given
R = 8.314 J/mol.K cp = (3/2)R = 20.785 J/mol.K
cv = (5/2)R = 12.471 J/mol.K
Take 1 mole as basis

a) For ideal gas undergoing adiabatic compression, Q = 0

Pressure P2 is found from

b) Cooled to 70oC at constant pressure

c) For ideal gases undergoing an isothermal process,

For the entire cycle

Q = 0-1663+1495 = -168J
W = 998 + 665 1495 = 168J
U = 998-998+ 0 = 0
H = 1663-1663 +0 = 0
ii- Show the processes on a Pv diagram.
Virial EOS
For real gases, 0<Z<1 ; Z>1

Under saturated condition, Virial EOS can be used to

determine the molar volume of vapor phase ONLY

The Virial EOS is based on the Ideal Gas EOS;

~
PV
Z 1
RT
Two Forms of the Virial Equation
compressibility factor

Virial
expansions

(more accurate if P but < )

B, C and so on are the Virial Coefficients

Virial coefficients are function of T only

Example; 3.8 (J.M Smith)

Reported values for the virial coefficients of isopropanol

vapor at 200 C are:
B = -388 cm3mol-1 C = -26000 cm6mol-2

Calculate V and Z for isopropanol vapor at 200 C and

10 bar by:
a) The ideal-gas equation
b) Virial equation in terms of P truncated to 2 terms.
c) Virial equation in terms of V truncated to 3 terms.
Given
T = 200 + 273.15 = 473.15K
P = 10 bar = 10000 kPa
B = -388 cm3mol-1
C = -26000 cm6mol-2

a) The Ideal gas equation

V = Videal = RT/P where Z = 1 for ideal gas

Videal =[ 1 (83.14cm3 bar. mol-1 .K-1) (473.15 K) ]/ (10 bar)

Videal = 3934 cm3/mol

Z = PV/RT = 1 for ideal gas

(b) Virial equation in terms of P truncated to 2 terms.
~
PV BP
1
RT RT

~ RT BP
V [1 ]
P RT
~ RT
V B
P
~ (83.1483.14cm3 bar / mol.K)(473.15 K )
V ( 388cm3 / mol )
10 bar
~
V 3546cm3 / mol

PV (10bar )(3546cm3 / mol )

Z 0.901
RT (83.14cm3 bar / mol.K)(473.15 K )
(c) Virial equation in terms of V truncated to 3 terms.
~
PV B C
Z 1 ~ ~2
RT V V

~ RT B C
V 1 ~ ~2
P V V

Facilitate iteration.; where i iteration number &

~ ~ ~
when i 0 , Vi V0 Videal

(83.14)(473.15) 388 26000

Vi 1 1 ~ ~2
10 Vi Vi
 (83.14)(473.15) 388 26000
Vi 1 1 ~ ~2
10 Vi Vi
(83.14)(473.15) 388 26000 ~ ~
1st iteration ; i 0; V0 1 1 ~ ~2 where V0 Videal 3934 cm3/mol
10 V0 V0
V1 3539 cm3/mol
(83.14)(473.15) 388 26000 ~
2nd iteration ; i 1; V1 1 1 ~ ~2 where V1 3539cm3/mol
10 V1 V1
V2 3495cm3/mol
(83.14)(473.15) 388 26000 ~
3rd iteration ; i 2; V2 1 1 ~ ~2 where V2 3495cm3/mol
10 V2 V2
V3 3489 cm3/mol
(83.14)(473.15) 388 26000 ~
4th iteration ; i 3; V3 1 1 ~ ~2 where V3 3489cm3/mol
10 V3 V3
V4 3488 cm3/mol
(83.14)(473.15) 388 26000 ~
5th iteration ; i 4; V4 1 1 ~ ~2 where V4 3488cm3/mol
10 V4 V4
V5 3488 cm3/mol
~ ~ ~ ~ ~ ~
V5 V4 0 or V5 V4 stop iteration; Final V V5 3488 cm3/mol

PV (10)(3488)
Z 0.8867
RT (83.14)(473.15)
Cubic Equations of State (EOS)

In order to represent both liquid and vapor

behavior, an EOS must be valid for a wide range
of Temperatures and Pressures

Cubic EOS = Polynomial equations that are

cubic in molar volume
The van der Waals EOS - 1 st cubic EOS

isotherm

saturation pressure

saturated liquid
saturated vapor

25
where a & b are (+ve) substance dependent constant
27 2 1
= ; = and; = Critical Temperature
64 8 Appendix B
Table B.1
= Critical pressure

Used to determine the molar volume of both saturated vapor and

saturated liquid phases at given T and P

a
The term is Van der Waals forces which account for the attractive
V2
forces between molecules
Table B.1 : Characteristic Properties of Pure Species
Redlich-Kwong (pg 94)
Modification of Van der Waals equation
It incorporates the temperature dependence of Van der Waal's
forces

Where;
( )2 2
= ;b = Tc & Pc Appendix B, Table B.1

Parameters , ( ), are given in table 3.1

Theorem of corresponding state Acentric
factor

Shows that compressibility factors Z for

different fluids exhibit similar behavior

Reduced temperature Tr & reduced pressure Pr

T P
Tr , Pr
Tc Pc

Definition of acentric factor ,

1.0 log Prsat Tr 0.7
Vapor & Vapor-like roots of the generic cubic
EOS
Apply for vapor substance
Involve iterations with initial value of Z = 1

= +
+ (+)

Related parameters available in Table 3.1 (pg 98)

Liquid & Liquid-like roots of the generic cubic
EOS
Apply for liquid substance

Involve iterations with initial value of Z =

+
= + + + ( )

=

Related parameters available in Table 3.1 (pg. 98)
Example 3.9[J.M Smith pg 98]

Given that the vapor pressure of n-butane at 350 K is 9.4573

bar, find the molar volumes of :

(a) Saturated-vapor n-butane

(b) Saturated-liquid n-butane at these conditions

as given by the Redlich/Kwong equation.

Generalized Correlation For Gases

Techniques to find the Z:

1. Pitzer Correlation for the compressibility

chart/data
2. Pitzer Correlation for the second virial
coefficient
3. Pitzer Correlation for the third virial
coefficient
1) Pitzer Correlation for the Compressibility chart/data

Generalized compressibility factor :

0 1
Z Z Z
Z 0 , Z 1 can be found in Appendix E, Table E1- E4
/Compressibility Chart
can be found in Appendix B, table B1
The compressibility chart Appendix B ; Table B1

Thermodynamics for Chemical Engineers EP205, L4

Appendix E ; Table E1 E4
2) Pitzer Correlation for the Second Virial Coefficient

Recall the Second virial equation:

~
PV BP Pr
Z 1 1 B
RT RT Tr

where

B B 0
B 1

0 0.422 1 0.172
B 0.083 1.6
, B 0.139
Tr Tr4.2
3) Pitzer Correlation for the Third Virial Coefficient

Recall the third virial equation:

2
~
PV B C 1 Pr
B Pr
C
Z 1 ~ ~
RT V V2 Tr Z Tr Z

where C C0 C1

0 0.02432 0.00313
C 0.01407 10.5
,
Tr Tr

1 0.05539 0.00242
C 0.02676
Tr2.7 Tr10.5
Example 3.10[J.M Smith]

Determine the molar volume of n-butane at 510K and 25 bar by

each of the following.

a) The ideal gas equation

b) The generalized compressibility Factor
c) The generalized compressibility factor-Pitzer correlation
d) Pitzer Correlation for second virial coefficient
e) Pitzer Correlation for third virial coefficient

Take, R = 83.14 cm3bar.mol-1K-1

 Class Activity
1. Calculate the compressibility factor and molar volume for methanol at
500 K and 10 bar by using the following equations;
i. Ideal Gas
ii. Van der Waals
iii. Redlich-Kwong

2. Analyze the molar volume of vapor of ethane at 55 oC, 8 bar using Van der
Waals equation.

3. Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the
molar volumes of (a) Saturated-vapor n-butane (b) Saturated-liquid n-
butane at these conditions as given by the van der Waals(vdW) and Peng
Robinson (PR).

4. Analyze the molar volume of n-pentane in cm3/g at 237 oC and 25 bar, using
the generalized Pitzer correlation for third virial coefficient method.
 END

THANK YOU..

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