Compressibility factor

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The compressibility factor (Z), also known as the compression factor, is the ratio of the molar
volume of a gas to the molar volume of an ideal gas at the same temperature and pressure. It is a
useful thermodynamic property for modifying the ideal gas law to account for the real gas
behavior.[1] In general, deviation from ideal behavior becomes more significant the closer a gas is
to a phase change, the lower the temperature or the larger the pressure. Compressibility factor
values are usually obtained by calculation from equations of state (EOS), such as the virial
equation which take compound specific empirical constants as input. For a gas that is a mixture
of two or more pure gases (air or natural gas, for example), a gas composition is required before
compressibility can be calculated.
Alternatively, the compressibility factor for specific gases can be read from generalized
compressibility charts[1] that plot as a function of pressure at constant temperature.

Contents

1 Definition and physical significance

2 Generalized compressibility factor graphs for pure gases

3 Theoretical models

4 Experimental values
o 4.1 Compressibility of air

5 See also

6 References

7 External links

Definition and physical significance

The compressibility factor is defined as

where
is the molar volume,
is the molar volume of the
corresponding ideal gas, is the pressure, is the temperature, and is the gas constant. For
engineering applications, it is frequently expressed as

where is the density of the gas and

the molar mass.

is the specific gas constant,[2]

being

For an ideal gas the compressibility factor is

per definition. In many real world
applications requirements for accuracy demand that deviations from ideal gas behaviour, i.e., real
gas behaviour, is taken into account. The value of generally increases with pressure and
decreases with temperature. At high pressures molecules are colliding more often. This allows
repulsive forces between molecules to have a noticeable effect, making the molar volume of the
real gas ( ) greater than the molar volume of the corresponding ideal gas (
), which causes to exceed one.[3] When pressures are lower, the
molecules are free to move. In this case attractive forces dominate, making
. The closer
the gas is to its critical point or its boiling point, the more deviates from the ideal case.

Generalized compressibility factor graphs for pure gases

Generalized compressibility factor diagram.

The unique relationship between the compressibility factor and the reduced temperature, , and
the reduced pressure,
, was first recognized by Johannes Diderik van der Waals in 1873 and is
known as the two-parameter principle of corresponding states. The principle of corresponding

states expresses the generalization that the properties of a gas which are dependent on
intermolecular forces are related to the critical properties of the gas in a universal way. That
provides a most important basis for developing correlations of molecular properties.
As for the compressibility of gases, the principle of corresponding states indicates that any pure
gas at the same reduced temperature, , and reduced pressure,
, should have the same
compressibility factor.
The reduced temperature and pressure are defined by

and
Here and
are known as the critical temperature and critical pressure of a gas. They are
characteristics of each specific gas with being the temperature above which it is not possible
to liquify a given gas and
is the minimum pressure required to liquify a given gas at its critical
temperature. Together they define the critical point of a fluid above which distinct liquid and gas
phases of a given fluid do not exist.
The pressure-volume-temperature (PVT) data for real gases varies from one pure gas to another.
However, when the compressibility factors of various single-component gases are graphed
versus pressure along with temperature isotherms many of the graphs exhibit similar isotherm
shapes.
In order to obtain a generalized graph that can be used for many different gases, the reduced
pressure and temperature,
and , are used to normalize the compressibility factor data.
Figure 2 is an example of a generalized compressibility factor graph derived from hundreds of
experimental PVT data points of 10 pure gases, namely methane, ethane, ethylene, propane, nbutane, i-pentane, n-hexane, nitrogen, carbon dioxide and steam.
There are more detailed generalized compressibility factor graphs based on as many as 25 or
more different pure gases, such as the Nelson-Obert graphs. Such graphs are said to have an
accuracy within 1-2 percent for values greater than 0.6 and within 4-6 percent for values of
0.3-0.6.
The generalized compressibility factor graphs may be considerably in error for strongly polar
gases which are gases for which the centers of positive and negative charge do not coincide. In
such cases the estimate for may be in error by as much as 15-20 percent.
The quantum gases hydrogen, helium, and neon do not conform to the corresponding-states
behavior and the reduced pressure and temperature for those three gases should be redefined in
the following manner to improve the accuracy of predicting their compressibility factors when
using the generalized graphs:

and
where the temperatures are in kelvin and the pressures are in atmospheres. [4]

Theoretical models
The virial equation is especially useful to describe the causes of non-ideality at a molecular level
(very few gases are mono-atomic) as it is derived directly from statistical mechanics:

Where the coefficients in the numerator are known as virial coefficients and are functions of
temperature.
The virial coefficients account for interactions between successively larger groups of molecules.
For example, accounts for interactions between pairs, for interactions between three gas
molecules, and so on. Because interactions between large numbers of molecules are rare, the
virial equation is usually truncated after the third term.[5]
The Real gas article features more theoretical methods to compute compressibility factors

Experimental values
It is extremely difficult to generalize at what pressures or temperatures the deviation from the
ideal gas becomes important. As a rule of thumb, the ideal gas law is reasonably accurate up to a
pressure of about 2 atm, and even higher for small non-associating molecules. For example
methyl chloride, a highly polar molecule and therefore with significant intermolecular forces, the
experimental value for the compressibility factor is
at a pressure of 10 atm and
temperature of 100 C.[6] For air (small non-polar molecules) at approximately the same
conditions, the compressibility factor is only
(see table below for 10 bars, 400 K).

Compressibility of air
Normal air comprises in crude numbers 80 percent nitrogen N2 and 20 percent oxygen O2. Both
molecules are small and non-polar (and therefore non-associating). We can therefore expect that
the behaviour of air within broad temperature and pressure ranges can be approximated as an
ideal gas with reasonable accuracy. Experimental values for the compressibility factor confirm
this.

Z for air as function of pressure 1-500 bar


75-200 K isotherms

250-1000 K isotherms
Compressibility factor for air (experimental values)
Pressure, bar (absolute)
Temp
,K

1
5
0.005 0.026
75
2
0
0.025
80
0
0.976 0.023
90
4
6
0.979 0.887
100
7
2
0.988 0.937
120
0
3
0.992 0.961
140
7
4
0.995 0.974
160
1
8
0.996 0.983
180
7
2
0.997 0.988
200
8
6
250 0.999 0.995

10
0.051
9
0.049
9
0.045
3
0.045
3
0.886
0
0.920
5
0.948
9
0.966
0
0.976
7
0.991

20
0.103
6
0.099
5
0.094
0
0.090
0
0.673
0
0.829
7
0.895
4
0.931
4
0.953
9
0.982

40
0.206
3
0.198
1
0.186
6
0.178
2
0.177
8
0.585
6
0.780
3
0.862
5
0.910
0
0.967

60
0.308
2
0.295
8
0.278
1
0.263
5
0.255
7
0.331
3
0.660
3
0.797
7
0.870
1
0.954

80
0.409
4
0.392
7
0.368
6
0.349
8
0.337
1
0.373
7
0.569
6
0.743
2
0.837
4
0.946

100
0.509
9
0.488
7
0.468
1
0.433
7
0.413
2
0.434
0
0.548
9
0.708
4
0.814
2
0.941

150
0.758
1
0.725
8
0.677
9
0.638
6
0.596
4
0.590
9
0.634
0
0.718
0
0.806
1
0.945

200
1.012
5
0.958
8
0.892
9
0.837
7
0.772
0
0.769
9
0.756
4
0.798
6
0.854
9
0.971

250

300

400

500

1.193
1
1.109
8
1.039
5
0.953
0
0.911
4
0.884
0
0.900
0
0.931
1
1.015

1.413
9
1.311
0
1.222
7
1.107
6
1.039
3
1.010
5
1.006
8
1.018
5
1.070

1.716
1
1.593
7
1.509
1
1.320
2
1.258
5
1.223
2
1.205
4
1.199

2.110
5
1.953
6
1.736
6
1.590
3
1.497
0
1.436
1
1.394
4
1.339

300
350
400
450
500
600
800
1000

2
0.999
9
1.000
0
1.000
2
1.000
3
1.000
3
1.000
4
1.000
4
1.000
4

7
0.998
7
1.000
2
1.001
2
1.001
6
1.002
0
1.002
2
1.002
0
1.001
8

1
0.997
4
1.000
4
1.002
5
1.003
4
1.003
4
1.003
9
1.003
8
1.003
7

2
0.995
0
1.001
4
1.004
6
1.006
3
1.007
4
1.008
1
1.007
7
1.006
8

1
0.991
7
1.003
8
1.010
0
1.013
3
1.015
1
1.016
4
1.015
7
1.014
2

9
0.990
1
1.007
5
1.015
9
1.021
0
1.023
4
1.025
3
1.024
0
1.021
5

3
0.990
3
1.012
1
1.022
9
1.028
7
1.032
3
1.034
0
1.032
1
1.029
0

1
0.993
0
1.018
3
1.031
2
1.037
4
1.041
0
1.043
4
1.040
8
1.036
5

0
1.007
4
1.037
7
1.053
3
1.061
4
1.065
0
1.067
8
1.062
1
1.055
6

3
1.032
6
1.063
5
1.079
5
1.091
3
1.091
3
1.092
0
1.084
4
1.074
4

2
1.066
9
1.094
7
1.108
7
1.118
3
1.118
3
1.117
2
1.106
1
1.094
8

2
1.108
9
1.130
3
1.141
1
1.146
3
1.146
3
1.142
7
1.128
3
1.113
1

0
1.207
3
1.211
6
1.211
7
1.209
0
1.205
1
1.194
7
1.172
0
1.151
5

2
1.316
3
1.301
5
1.289
0
1.277
8
1.266
7
1.247
5
1.215
0
1.188
9

Source: Perry's chemical engineers' handbook (6ed ed.). MCGraw-Hill. 1984. ISBN 0-07049479-7. (table 3-162). values are calculated from values of pressure, volume (or density),
and temperature in Vassernan, Kazavchinskii, and Rabinovich, "Thermophysical Properties of
Air and Air Components;' Moscow, Nauka, 1966, and NBS-NSF Trans. TT 70-50095, 1971: and
Vassernan and Rabinovich, "Thermophysical Properties of Liquid Air and Its Component,
"Moscow, 1968, and NBS-NSF Trans. 69-55092, 1970.

See also

Real gas

Theorem of corresponding states

Principle of corresponding states

Van der Waals equation

Fugacity

References
1.

^ a b Properties of Natural Gases. Includes a chart of compressibility factors versus

reduced pressure and reduced temperature (on last page of the PDF document)

2.

^ Zucker, Robert D. and Biblarz, Oscar (2002). Fundamentals of Gas Dynamics

(2nd ed.). Wiley Books. ISBN 0-471-05967-6. page 327

3.

^ McQuarrie, Donald A. and Simon, John D. (1999). Molecular Thermodynamics.

University Science Books. ISBN 1-891389-05-X. page 55

4.

^ Y.V.C. Rao (1997). Chemical Engineering Thermodynamics. Universities Press

(India). ISBN ISBN 81-7371-048-1.

5.

^ Smith, J.M. et al. (2005). Introduction to Chemical Engineering

Thermodynamics (Seventh Edition ed.). McGraw Hill. ISBN 0-07-310445-0. page73

6.

^ Perry's chemical engineers' handbook (6ed ed.). MCGraw-Hill. 1984. ISBN 007-049479-7. page 3-268

External links

Compressibility factor (gases) A Citizendium article.

Real Gases includes a discussion of compressibility factors.

EnggCyclopedia's compressibility factor calculator based critical properties

EnggCyclopedia's compressibility factor calculator for natural gas

Categories:

Chemical engineering

Gas laws

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