THERMODYNAMICS 2

Engr. Orley G. Fadriquel

LESSON 5
REAL GAS
In Thermodynamics 1, we have discussed ideal gas, gas laws and the
thermodynamic properties of different substances. Unfortunately, most substances do
not act as ideal gas. Unlike ideal gas, we cannot find tables and charts of the basic
properties of real gas.
For most applications, such a detailed analysis is unnecessary, and the ideal gas
approximation can be used with reasonable accuracy. Real-gas models have to be
used near condensation point of gases, near critical point, at very high pressures, and in
several other less usual cases.
Equations of State
In physics and thermodynamics, an equation of state is a relation between state
variables. More specifically, an equation of state is a thermodynamic equation
describing the state of matter under a given set of physical conditions. It is a constitutive
equation which provides a mathematical relationship between two or more state
functions associated with the matter, such as its temperature, pressure, volume, or
internal energy. Equations of state are useful in describing the properties of fluids,
mixtures of fluids, solids, and even the interior of stars.
The most prominent use of an equation of state is to predict the state of gases
and liquids. One of the simplest equations of state for this purpose is the ideal gas law,
which is roughly accurate for gases at low pressures and moderate temperatures.
However, this equation becomes increasingly inaccurate at higher pressures and lower
temperatures, and fails to predict condensation from a gas to a liquid. Therefore, a
number of much more accurate equations of state 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.
COMPRESSIBILITY FACTOR
Ideal gas equation of state for ideal gas is very convenient to use in
thermodynamic calculations. This equation is good approximation at low density.
However, if the density goes high, is the equation of state for ideal gas still applicable?
At what range of density will the ideal gas equation be accurate?
As discussed in the previous lessons, looking at the T-s diagram, it can be seen
that as the state becomes further removed from the saturation region, the gas behavior
becomes closer for the ideal-gas model.
A more quantitative study of the of the question of the ideal-gas approximation
Can be conducted by introducing the compressibility factor, Z,

or

Van der Waals equation of state

The van der Waals equation is an equation of state for a fluid composed of
particles that have a non-zero size and a pairwise attractive inter-particle force (such as
the van der Waals force.) It was derived by Johannes Diderik van der Waals in 1873,
based on a modification of the ideal gas law, who received the Nobel prize in 1910 for
"his work on the equation of state for gases and liquids". The equation approximates the
behavior of real fluids, taking into account the nonzero size of molecules and the
attraction between them. His new formula revolutionized the study of equations of state,
and was most famously continued via the RedlichKwong equation of state.

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Engr. Orley G. Fadriquel

Van der Waals model

Real gases are often modeled by taking into account their molar weight and
molar volume.
a
(p + 2 ) (Vm b) = RT
Vm
where P is the pressure, T is the temperature, R the ideal gas constant, and Vm
the molar volume. The constant b is intended to correct for the volume occupied by the
molecules, and the term a/v 2 is a correction that accounts for the intermolecular forces
of attraction. The terms a and b are parameters that are determined empirically for each
gas, but are sometimes estimated from their critical temperature (Tc) and critical
pressure (Pc) using these relations:
27R2 Tc2
a=
64Pc
RTc
b=
8Pc
The compressibility factor at the critical point for the van der Waals equation is

3
=
= 8

RedlichKwong equation of state

The RedlichKwong equation of state is an equation that is derived from the
van der Waals equation. It is generally more accurate than the van der Waals equation
and often more accurate than some equation with more than two parameters, but not
used as frequently because the increased difficulty in its derivatives and overall use. It
was formulated by Otto Redlich and J. N. S. Kwong in 1949. The equation is
P=

RT
a

Vm b T Vm (Vm + b)

where:
P is the gas pressure
R is the gas constant,
T is temperature,
Vm is the molar volume (V/n),
a is a constant that corrects for attractive potential of molecules, and
b is a constant that corrects for volume.
The constants are different depending on which gas is being analyzed. The
constants can be calculated from the critical point data of the gas.
a=

5
2 2
0.4275R Tc

Pc
0.08664RTc
b=
Pc

where:
Tc is the temperature at the critical point, and
Pc is the pressure at the critical point.
The RedlichKwong equation is adequate for calculation of gas phase properties
when the ratio of the pressure to the critical pressure (reduced pressure) is less than
about one-half of the ratio of the temperature to the critical temperature (reduced
temperature):
p
T
<
pc 2Tc
Berthelot and modified Berthelot model
The Berthelot Equation is very rarely used,

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

RT
a

V b TV2
but the modified version is somewhat more accurate
P=

P=

RT
9PTc (1 6Tc2 )
(1 +
)
V
128Pc T
T2

Clausius model
The Clausius equation is a very simple three-parameter equation used to model gases.
a
) (Vm b)
RT = (P +
T(Vm + c)2
where
Vc RTc
a=
4Pc
3RTc
b=
Vc
8Pc
27R2 R3c
c=
64Pc
Beattie-Bridgeman Model
The Beattie-Bridgeman equation
Rc 2
RBc 3 RBbcd4
)
(BbRT
)d +
d
+
+
Aa

T2
T2
T2
where d is the molal density and a, b, c, A, and B are empirical parameters.
P = RTd + (BRT A

Benedict-Webb-Rubin Model
Instead of the ideal-gas model to represent gas behaviour, or even the
generalized compressibility chart, which is approximate, it is desirable to have an
equation of state that accurately represents P-v-T behaviour for a particular gas over
the entire superheated vapour region. Such an equation is necessarily more
complicated and consequently more difficult to use. Many such equations have been
proposed and used to correlate the observed behaviour of gases and to illustrate one
equation, the Benedict-Webb-Rubin equation of state.
The BWR equation, sometimes referred to as the BWRS equation
1
P = RTd + d2 (RT(B + b) (A + ad ad4 ) 2 [C cd(1 + d2 )exp(d2 )])
T
where d is the molal density and where a, b, c, A, B, C, , and are empirical
constants.
DIETERICI Equation
Pv b e

a
RTv

RT

where :
2
2

a 4 R Tc

e 2 Pc

RT c
b

e
P
c

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

PROBLEM SOLVING EXERCISES:

1) Use the BERTHELOT Equation and the fuel is propane, C3H8

P 2 v b RT
Tv

where
3
2

a 27 R Tc

64 Pc

b c
3

3 Pc v c Tc

Problem:
a) Show the expressions for the constants a and b.
b) Compute the approximate values of the constants a and b for the fuel stated.
Solution:
a) Derive the formula:
a

P 2 v b RT
Tv

a
Let m =
T
m

P 2 v b RT
v

Differentiate p with respect to v,

m

p 2
v

p 2
v

2m

(1) v b p' 3 0 ; 1st derivative

v

2m 2mb

p' v b 2 3 0 ; sin ce p' 0

v
v

m
2m 2mb

p 2 0 v b 2 3 0
v
v
v

m 2mb
p 2 3 0
equation 1
v
v

Getting the 2nd derative of p with respect to v,

m
2m

p 2 v b p' 3 0 ;
v
v

m
2m 2mb

p 2 p' v b 2 3 0 ;
v
v
v

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

m
m 2mb

p 2 p' v b 2 3 0
v
v
v

p' p' p' ' v b 2m3 6mb

0
v
v4
2m 6mb
2p' p' ' v b 3 4 0 ; sin ce p' 0 and p" 0
v
v
m 6mb
4 0
v3
v
4
v (2m)
b
v 3 (6m)
b

v
3

vc
3

From equation1, substitute b,

m 2mb
p 2 3 0
v
v
v
2m
m
3 0
p 2
v
v3
m 2m
p 2 3 0
v
3v
m
p 2 0
3v
a
m 3v 2 p ; m
T
a
3v 2 p
T
a 3v 2pT

a 3v c p c Tc
2

b) Berthelot Equation, using Propane fuel,

From Table Item B18,
Tc = 6660R = 370 0K
Pc = 42.1 atm = 4,265.78 kPa
kN m
R = 8.31
kg mole 0K
kg
M =44.09
kg mole

kN m
8.31
R
kN m
kg mole 0K

0.18846
R=
kg
M
kg 0K
44.09
kg mole
Formula:

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THERMODYNAMICS 2
3
2

a 27 R Tc

64 Pc

Engr. Orley G. Fadriquel

3 Pc v c Tc

b c
3

and

kN m
0
27 0.18846
3
370 K
2
0
kg K
27R Tc

a
=
kN
64Pc

64 4,265.78 2
m

a = 177.92

Vc2 =

kN m 4 0 K
kg

a
3 p c Tc

kN m 4 0 K
kg
Vc2 =
kN

3 4265.78 2 370 0K
m

177.92

Vc2 = 3.7576 x 10 -3

Vc = 6.13 x 10-3

b=

Vc

m6
kg

m3
kg

6.13x 10 3

m3
kg

b = 2.043 x 10-3 m3/kg

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

2) Use the DIETERICI Equation and the fuel is benzene, C6H6

Problem:
a) Show the expressions for the constants a and b.
b) Compute the approximate values of the constants a and b for the fuel stated.
Solution:
a) Derive the formula
a
RTv

Pv b e
and show

2
2

a 4 R Tc

e 2 Pc

RT
b 2 c

e Pc

Pv be

a
RTv

RT

a
RT

RT ; let m =

pv b e
m
v

m
v

RT
m
v

pve pbe RT (Differentiate )

m
m
mv m mv mv

m
v
p ve 2 e (1) ve p' pbe 2 e v p' b 0
v
v

m
v

m
v

m
v

m
v

mpe
pbme

p e p' ve
p' b e v 0 (multiply both sides by v 2 )
v
v2

m
v

m
v

m
v

m
v

m
v

mvpe pv e p' v e pbme p' v be 0

m

p' v 3 e v p' v 2be v mvpe v pbme v pv 2e v

m

p' v 2 (e v )( v b) pe v (mv mb v 2 )
p' v 2 ( v b) p(mv mb v 2 ) ; ( first derivative )
sin ce p' 0
thus,
0 p(mv mb v 2 )

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equation 1

THERMODYNAMICS 2

Engr. Orley G. Fadriquel

Obtaining sec ond derivative

p' v 2 ( v b) p(mv mb v 2 )
p' v 3 p' v 2b) p(mv mb v 2 )

p' (3v 2 ) v 3 (p" ) p' b(2v ) v 2 p" b pm 2v (mv mb v 2 )

3p' v v (p" ) 2p' bv v p" b pm 2v (mv mb v 2 )p'
sin ce
p' 0 and p" 0
0 pm 2v
0 pm 2pv
pm 2pv
a
m 2v ;
sin ce
m
RT
a
2v
RT
2

a 2vRT
From equation 1
mv mb v2 = 0

and m =

a
RT

a
a
(v )
bv2 0
RT
RT
av
ab
v2
; a 2vRT
RT
RT
(2vRT )v
(2vRT )b
v2
RT
RT
2
2
2v v 2vb
v 2 2vb

2v 2v
b

v
2

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

From the equation;

Pv b e

a
RTv

sin ce b

RT

v
and a 2vRT
2

P v e
2

pv 2
e RT
2
2RT
v 2
pe
thus,
a 2vRT

2 vRT
RTv

RT

2RT
2(2RT)(RT)
v pe 2
a
also
b

2
2
pe 2

4R 2 T 2
RT
and b
2
pe
pe 2

b) DIETERICI Equation and the fuel is benzene, C6H6

From Table Item B18,
Tc = 10110R = 561.667 0K
Pc = 47.7 atm = 4,833.2 kPa
kN m
R = 8.31
kg mole 0K
kg
M =78.05364
kg mole

kN m
8.31
R
kN m
kg mole 0K

0.1065
R=
kg
M
kg 0K
78.05364
kg mole

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

Formula:
2
2

a 4 R Tc

e 2 Pc

kN m

561.6670 K
4 0.1065
0

kg K

a
kN

e 2 4,833.2

kN m 4
a 0.400768
kg 2

and

RT
b 2 c

e Pc

kn m
0
0.1065 0 561.667 K
kg K
b

kN

e 2 4,833.2

m2

b 1.675x10 3

m3
kg

3) Use the CLAUSIUS Equation and the fuel is heptane, C7H16

a
P
v b RT
2
T( v c )

where
3
2

a 27 R Tc

64 Pc

RTc
b v

4Pc

Problem:
a) Show the expressions for the constants a and b.
b) Compute the approximate values of the constants a and b for the fuel stated.
Solution:
a) Derive the formula:

a
P
v b RT
2
T
(
v

c
)

a
Let m =
T

m
P
v b RT
( v c ) 2

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THERMODYNAMICS 2

Engr. Orley G. Fadriquel

Differentiate p with respect to v,

m
2m
p
(1) v b p'
0 ; multiplyin g both sides by ( v c )3
2
3
(v c )
(v c )

p ( v c )3 m v c ( v b) p' ( v c )3 2m 0 ; sin ce p' 0

p ( v c )3 m v c ( v b) 0 ;
Obtaining the sec ond derivative of

Equation 1

p ( v c )3 m v c ( v b) p' ( v c )3 2m 0 ;
3p(v+c)2(1) + (v+c)3 p + m(1) +(v-b)[p(3)(v+c)2(1) + (v+c)3 p] + [p(v+c)3-m]
3p(v+c)2 + (v+c)3 p + m +(v-b)[p(3)(v+c)2(1) + (v+c)3 p] + [p(v+c)3-m]

3p(v+c)2 + m 2m = 0
3p(v+c)2 m = 0
m
Equation 2
(v+c)2 =
3p
From equation 1
p ( v c ) 3 m v c ( v b) 0 ;

sin ce ( v c )

m
3p

p ( v c )( v c ) 2 m v c 2m ( v b) 0
1

m m 2
m 2

m
2m ( v b) 0
p
3p 3p
3p
3

m2

m2

3(3p)

1
2

(3p)

1
2

2mb 2mv

2mv 2mb 0

(m)m
3(3p)

4m

2b 2v

1
2

1
2

(m)m
(3p)

1
2

1
2
1

3(3p) 2
b v

1
2

4 m 2

or 2b 2v
3 3p

2
( v c ) Equation 3
3

From the Original equation:

m
P
v b RT;
( v c ) 2

P a v b RT

3pT

[p 3p] ( v b) RT
4pb 4pv RT

4p
4p
4p
bv

(v c )2

; 4p( v b) RT;

m
a
a

; and m
3p 3pT
T

4pv 4pb RT

RT
4p

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