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Theoretical Pressure-Volume Isotherms Based on Different


Equations of State
Banda, Marybeth Hope T.
Abstract: Real gases only obey the Ideal Gas Law at low pressures and at high
temperatures. As a result, modifications of the Ideal Gas Law were developed and these are
called Equations of State. This experiment aims to describe the isotherms of different
equations of state for Neon; differentiate them from each other at the critical temperature;
and to differentiate the equations of state from the ideal gas equation at the critical
temperature. Results show that different equations of state have different forms of their
corresponding isotherms and may be accurate only at a specific volume, pressure, or
temperature range. Different equations of state may or may not be accurate near or at the
critical temperature. Further, different equations of state show considerable deviations from
ideality to describe effectively the real behaviour of a gas, in this case, of neon.
Introduction
A system is said to be at equilibrium when
its properties is independent of time and
there is no heat flowing through the
system. The state of the system is then
defined entirely by state variables.
Examples of these variables are volume,
temperature, and pressure. When a
sufficient number of state variables are
specified, all of the other properties of the
system are fixed (1). When the amount of
the pure substance is held constant, one of
these variables can be calculated when the
other two is known.
The simplest equation that defines the
unknown variable as a function of the
known variables is the ideal gas law.
However, real gases only obey this
equation at low pressures and at high
temperatures.
Consequently,
other
equations of stateas they are called
have been developed to account for these
variations.
The ideal gas law is derived from Boyles
Law, Charles Law, Amontons Law, and
Avogadros Law. Boyles Law states that
pressure is inversely proportional to volume
at constant temperature and amount of
gas:

1
V

P=

k
V

Charles Law states that volume is directly


proportional to temperature at fixed
pressure and amount of gas:

V T

V =kT

Avogadros law states that volume is


directly proportional to the amount of gas
at constant temperature and pressure:

V n

V =kn
Combining these four laws gives:

PV =nkT
PV =nRT
Where R is the universal gas constant.
Experimental results show deviations of the
behaviour of gases from this equation. It
was observed that real gases only obey the
ideal gas equation at high temperatures
and at low pressures.
At high temperatures, the gas molecules
overcome the intermolecular forces of
attraction due to the relatively high kinetic

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energy possessed by the molecules. At low
pressures, the gas molecules are less
hindered and are able to spread further and
thereby
overcoming
the
forces
of
interaction between molecules.
In 1873, a correction to the ideal gas law
was introduced to account for the volume
and
intermolecular
forces
between
molecules (2). This correction is referred to
as the van der Waals equation:

p+

an2
( V nb )=nRT
V2

Where a and b are van der Waals constants


for a particular gas. The constant a
represents the correction due to pressure
and is affected by the interactions between
gas molecules. The constant b represents
the correction due to volume and b is
affected by the size of the gas molecules.
The van der Waals equation predicts the
behaviour of a real gas based on physical
phenomena.
An equation of
Clapeyron-Clausius
Berthelot Equation:

p+

state derived from


Equation (3) is the

8 p 2c V 3c
( V m b ) =RT
R

Another equation of state is the RedlichKwong Equation. It is a two-parameter


equation and is more accurate than the van
der Waals equation of state (4):

P=

RT
a

V mb T V m ( V m+ b )

Another equation of state considered in this


experiment is the equation of state
developed by Peng and Robinson. It was
found to be useful for liquids and gases:

P=

RT
a

V mb V m ( V m+ b ) +b (V mb)

The deviation of a gas from ideality can be


expressed by the compressibility factor, Z:

Z=

PVm
RT

Where P is the pressure of the system, Vm is


the molar volume, R is the universal gas
constant, and T is the temperature of the
system.
When the Z of a gas at a given pressure,
temperature, and volume, is equal to one,
the gas behaves ideally. When Z is greater
than one, the non-ideal behaviour of the
gas is due to repulsive forces. When Z is
lesser than one, the non-ideal behaviour is
due to the attraction between molecules.
The critical volume, temperature, and
pressure of neon is 0.0390927L/mol,
44.40K, and 27.56 bar, respectively.
The objectives of this experiment are to
describe
the
isotherms
of different
equations of state for Neon; differentiate
them from each other at the critical
temperature; and to differentiate the
equations of state from the ideal gas
equation at the critical temperature.
Experimental Methods
This experiment focuses on the plotting of
the isotherms of neon based on different
equations of state and is made possible
with the use of a personal computer that is
installed with Microsoft Excel.
The critical constants of methane and neon
were looked up in literature. From these
values, the different coefficients required
by the different equations of state were
calculated. These coefficients, along with
the critical constants, were used to
calculate the pressure of methane at
different molar volumes around the critical
volume and at different temperatures
around the critical temperature. These
calculated values of pressure were then
plotted against molar volume.
Results and Discussion

3
The objectives of this experiment are to
describe
the
isotherms
of different
equations of state; differentiate them from
each other at the critical temperature; and
to differentiate the equations of state from
the ideal gas equation at the critical
temperature.
Figure 1 shows the Ideal Gas Equation
Isotherms of neon. The pressure was
calculated using (E.1).
As shown on Figure 1, the pressure
decreases as the volume increases. When
the volume is further increased, the
isotherms converge and are asymptotic
with respect to zero pressure.

15.00
150.0

25.00

35.00

Pressure (bar) 100.0


44.40
55.00
50.0

70.00

80.00

90.00

0.0
0.02

220.00
170.00
1.00 120.0015.00
P (bar)

25.00

35.00

44.40

70.00
20.00

0.02 0.04 0.06 0.08 0.10 0.12 0.14


-30.00
55.00
70.00
80.00
90.00
-80.00
-130.00
Volume (L/mol)

Figure 2. van der Waals Isotherm for Neon

200.0
1.00

270.00

0.07

0.12

0.17

Volume (L/mol)

Figure 1. Ideal Gas Isotherm of Neon


In the van der Waals isotherm of Neon,
however, the pressure of the gas becomes
negative as the volume is decreased for
systems at 25.00, 15.00, and 1.00 K; while
for systems at 35.00K and above, the
pressure increases as the volume is
decreased. Still, as the volume is increased,
the isotherms converge and approach zero
pressure.

For the Berthelot Equation of state, the


same thing also happens: the pressure is
negative for systems at 1.00, 15.00, and
25.00 K. The difference between Berthelot
and van der Waals Equation of state is that
for systems at 1.00 K, a considerable dip in
the value of pressure is observed as the
volume is decreased compared with
systems at 15.00 K and at 25.00 K.
The Berthelot Isotherm values of pressure
were calculated using (E.3).
150.0
100.0
1.00

15.00

25.00

35.00

50.0
Pressure (bar)
44.40

The van der Waals Isotherm values for


pressure were calculated using (E.2).

0.0
0.00 0.10 0.20 0.30 0.40 0.50
55.00
70.00
80.00
-50.0
-100.0

90.00
-150.0
Volume (L/mol)

Figure 3. Berthelot Equation Isotherm of

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Neon
Almost the same Isotherms are observed
for Redlich-Kwong Equation of State as
those of the Berthelot Equation of State.
The only alteration is that the pressure of a
system at 35.00 K now becomes negative
as the volume is decreased. A considerable
dip in the value of pressure is still observed
for the isotherm at 1.00 K.
The Redlich-Kwong Isotherm value
pressure was calculated using (E.4).

for

300.0

All isotherms of the different equations of


state converge and approach zero pressure
as the volume is increased.
At 44.4 K, the critical temperature of Neon,
the Redlich-Kwong and the Peng-Robinson
Equation of State has the same isotherm.
The Berthelot Isotherm is almost the same
as the Ideal Gas Isotherm but with a less
steep slope than the Ideal Gas isotherm.
The van der Waals Isotherm also has the
same linear shape as the Ideal Gas
Isotherm but possess a much less steep
slope than the Berthelot Isotherm.

200.0
100.0
1.00
15.00
0.0
0.02
Pressure (bar)
-100.0

120
25.00
0.07

35.00
0.12

100

44.40
0.17
IGL

-200.0
55.00

70.00
-300.0

Pressure (bar)
80.00

PREoS

M olar Volume (L/mol)

The Peng-Robinson Isotherm of Neon is


almost the same as the Redlich-Kwong
Isotherms. The only difference is that no
considerable dip in the pressure of the
isotherm at 1.00 K is observed as the
volume is decreased.
The Peng-Robinson Isotherm values for
pressure were calculated using (E.5).
300.0

Pressure (bar)
44.40

25.00

35.00

0.0
0.03 0.05 0.07 0.09 0.11
55.00
70.00
80.00
-100.0
-200.0

90.00

RKEoS

20
0
0.00000 0.20000 0.40000 0.60000

Figure 4. Redlich-Kwong Equation Isotherm of Neon

200.0
15.00
100.0

BEoS

40

90.00

-400.0

1.00

80
VdW
60

-300.0
Volume (L/mol)

Figure 5. Peng-Robinson Isotherm for Neon

Volume (L/mol)

Figure 6. Different Isotherms at Critical Temperature (44.4


Among the different Equations of State,
Peng-Robinson and Redlich-Kwong Equation
of State has the greatest deviation from
ideality at the critical temperature. The
next Equation of State that showed the
greatest deviation from ideality is the van
der Waals equation of state followed by
Berthelot Equation of State.

1.1
1.0
0.9
0.8
IGL
0.7

VdW

BEoS

RKEoS

Z 0.6
0.5
0.4
PREoS
0.3
0.2
0.0 0.1 0.1 0.2 0.2 0.3 0.3 0.4 0.4 0.5 0.5

pressure, or temperature range. Different


equations of state may or may not be
accurate
near
or
at
the
critical
temperature. Different equations of state
show considerable deviations from ideality
to describe effectively the real behaviour of
a gas, in this case, of neon.
For future conduct of the experiment, the
author recommends that the newer
versions of the different equations of state
be compared; a wider range of volume be
used; the P-V-T graphs for different
equations of state be plotted and
compared; and that the calculated data be
compared with experimental data.

Molar Volume (L/mol)


References
Figure 7. Deviation from Ideality at the Critical Temperature
Conclusion and Recommendations
This experiment aimed to describe the
isotherms of different equations of state;
differentiate them from each other at the
critical temperature; and to differentiate
the equations of state from the ideal gas
equation at the critical temperature.
Due to empirical data that showed that real
gases only follow the Ideal Gas Law at high
temperatures and at low pressures,
different equations of state were developed
to account for these deviations. Different
equations of state have different forms of
their corresponding isotherms and may be
accurate only at a specific volume,

1. Silbey, Robert J., Alberty, Robert A. and


Bawendi, Moungi G. Physical Chemistry. 4th.
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2. Ball, David W. Physical Chemistry. Pacific Grove,
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3. Overview Berthelot Equation. [Online] Oxford
University Press, 2014. [Cited: January 7, 2015.]
http://oxfordindex.oup.com/view/10.1093/oi/authority.
20110803095501662.
4. Young, David. Equations of State. [Online]
Cytoclonal Pharmaceutics Inc. [Cited: January 7,
2015.]
http://www.ccl.net/cca/documents/dyoung/topicsorig/eq_state.html.