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Experiment Report on the different Pressure-Volume Isotherms

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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

proportional to temperature at fixed

pressure and amount of gas:

V T

V =kT

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

2

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

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+

Equation (3) is the

8 p 2c V 3c

( V m b ) =RT

R

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 )

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)

expressed by the compressibility factor, Z:

Z=

PVm

RT

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

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

-30.00

55.00

70.00

80.00

90.00

-80.00

-130.00

Volume (L/mol)

200.0

1.00

270.00

0.07

0.12

0.17

Volume (L/mol)

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.

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

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)

4

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

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

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

200.0

15.00

100.0

BEoS

40

90.00

-400.0

1.00

80

VdW

60

-300.0

Volume (L/mol)

Volume (L/mol)

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

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.

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,

Bawendi, Moungi G. Physical Chemistry. 4th.

Massachusetts : John Wiley & Sons, Inc., 2005.

2. Ball, David W. Physical Chemistry. Pacific Grove,

CA 93950 : Brooks/ColeThomson Learning, 2003.

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.

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