Compressibility For Non Ideal Gases
Compressibility For Non Ideal Gases
Compressibility For Non Ideal Gases
Working with
Non-Ideal Gases
Here are two proven methods for
predicting gas compressibility factors.
(1)
(2)
The compressibility factor can be viewed as that which corrects for the non-ideality of the gas. Thus, a gas for which Z
= 0.90 will occupy only 90% of the volume occupied by an
ideal gas at the same temperature and pressure. The values
of Z range from about 0.2 to a little over 1.0 for pressures
and temperatures of up to 10 times the critical values. Z itself is a complex function of the reduced temperature Tr, reduced pressure Pr and one or more other parameters, such
as the critical compressibility factor, Zc, or acentric factor,
. No simple analytical equations have yet been offered to
express this complex relationship.
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available in standard handbooks (2). Thermodynamic tables for many common compounds often include PVT data
in addition to enthalpy data. When such data exist, Z can
be determined by direct substitution of the tabulated values
into Eq. 2. Product brochures may also provide a good
source of PVT data for specific gases or vapors. The following example illustrates how Z can be determined from
tabulated thermodynamic data.
Example 1. A relief valve must be sized to relieve saturated ammonia at 317.2 psia and 127.4F. Thermodynamic
data for ammonia indicate that the specific volume, v, of
ammonia vapors at 307.8 psia (20.94 atm) and 125F
(324.8 K) is 0.973 ft3/lb. The molecular weight, MW, of ammonia is 17.03 lb/lbmol. Calculate Z at relieving conditions.
Solution. The tabulated values are close to the relieving
conditions, so the calculated value of Z will be applicable
for the relieving conditions. Z is obtained by substituting
the PVT data into Eq. 2 and using R = 1.314 atm-ft3/lbmolK and MW = 17.03 lb/lbmol. Z = (20.94 0.973
17.03)/(1 1.314 324.8) = 0.813.
Fluids Handling
(3)
(4)
(5)
(6)
(7)
h = b/V = b*P/Z
(8)
Nomenclature
a = constant in Redlich-Kwong equation of state
a*2 = term defined in Eq. 5
b = constant in Redlich-Kwong equation of state
b* = term defined in Eq. 5
h = term defined in Eq. 5
MW = molecular weight of gas, lb/lbmol
n = moles, lbmol
P = pressure, atm
Pc = critical pressure, atm
Pr = reduced pressure, P/Pc, dimensionless
R = universal gas constant = 1.314 atm-ft3/lbmol-K
T = operating temperature, K
Tc = critical temperature, K
Tr = reduced temperature, T/Tc, dimensionless
V = volume, ft3
w = weight, lb
x = mole fraction of gas component in mixture
Z = compressibility factor, dimensionless
Zav = average compressibility factor as defined in Eq. 9, dimensionless
Zc = critical compressibility factor, dimensionless
v = specific volume, ft3/lb
= acentric factor
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(9)
Comparing methods
The table lists Z factors estimated by the two methods reviewed in this article and compares these values with experimental Z factors (where available) at the same T and P. The
conditions selected are somewhat arbitrary, but generally reflect conditions encountered in the chemical industries.
The analysis reveals that the two methods predict Z factors that are in good agreement with each other and with the
Critical Data
Reduced Values
Case Compound
Molecular
Weight T, K
P, atm V, ft3/lb
Tc, K
Pc, atm
Tr
Pr
Actual
Z Factors
Compressibility Factors
Compressibility Redlich-Kwong
Charts
Equation
1
2
3
4
5
6
7
8
9
10
11
Acetic acid
60.05
Acetone
58.08
Ammonia
17.03
Boron trifluoride
67.80
Bromine
159.82
n-Butane
58.12
1-Butene
56.10
CFC-114
170.92
Carbon dioxide
44.01
Carbon monoxide 28.01
Chlorine
70.91
533.15
463.15
324.80
293.00
380.00
388.80
522.00
344.10
323.00
300.00
299.80
21.27
22.47
20.94
103.04
3.96
20.41
40.82
7.46
59.21
100.00
7.93
NA
NA
0.9730
0.0258
0.7640
0.2761
0.2460
0.2934
0.1183
0.1398
0.6357
594.80
509.10
405.70
260.90
584.00
425.20
419.60
418.90
304.20
133.00
417.00
57.10
47.00
111.32
49.20
101.65
37.50
39.70
32.20
72.90
34.50
76.10
0.896
0.910
0.801
1.123
0.651
0.914
1.244
0.821
1.062
2.256
0.719
0.373
0.478
0.188
2.094
0.039
0.544
1.028
0.232
0.812
2.899
0.104
NA
NA
0.8130
0.4682
0.9684
0.6411
0.8213
0.8274
0.7263
0.9934
0.9074
Z
% Error
0.80
NA
0.75
NA
0.84
3.3
0.45 3.9
0.94 2.9
0.66
3.0
0.82 0.2
0.82 0.9
0.72 0.9
0.99 0.3
0.88 3.0
Z
% Error
0.795
NA
0.734
NA
0.866
6.5
0.464 0.9
0.955 1.4
0.687
7.2
0.808 1.6
0.843
1.9
0.722 0.6
0.980 1.3
0.903 0.5
12
13
14
15
16
17
18
19
20
21
22
Ethanol
Hydrogen
Methane
Methanol
Methyl chloride
Nitrogen
Oxygen
n-Octane
Sulfur dioxide
Toluene
Water
427.15
300.00
300.00
487.15
349.80
300.00
300.00
563.15
366.30
553.15
502.40
6.80
100.00
100.00
39.25
19.31
98.70
98.70
21.34
23.61
24.07
27.21
1.6630
2.0802
0.2101
0.3691
0.3613
0.1433
0.1191
NA
0.2460
NA
11610
516.35
33.20
190.70
513.20
416.30
126.20
154.80
569.00
430.70
592.00
647.00
63.00
12.96
45.50
78.50
65.90
33.50
50.10
24.50
77.70
41.60
218.30
0.827
9.036
1.573
0.949
0.840
2.377
1.938
0.990
0.850
0.934
0.777
0.108
7.716
2.198
0.500
0.293
2.946
1.970
0.871
0.304
0.579
0.125
0.9282
1.0607
0.8549
0.7251
0.7664
1.0050
0.9543
NA
0.7730
NA
0.8618
0.92
1.05
0.86
0.73
0.78
0.99
0.95
0.55
0.80
0.68
0.87
0.934
1.063
0.855
0.762
0.808
0.990
0.947
0.551
0.807
0.690
0.907
46.07
2.01
16.04
32.04
50.49
28.01
32.00
114.23
64.06
92.13
18.01
0.9
1.0
0.6
0.7
1.8
1.5
0.4
NA
3.5
NA
0.9
0.6
0.2
0.0
5.1
5.4
1.5
0.8
NA
4.4
NA
5.2
* Compounds for which the specific volume was not readily available in standard references are marked with NA. For these compounds, the actual Z value could not be calculated.
Literature Cited
1. Reid, R. and T. Sherwood, The Properties of Gases and Liquids
Their Estimation and Correlation, 2nd Ed., McGraw-Hill Co.,
New York (1966).
2. Perry, R. (Editor), Chemical Engineers Handbook, 5th Ed., McGraw-Hill Book Co., New York.
3. Nelson, L. and E. Obert, Trans. ASME, 76, p. 1057 (1954) as cited
in Ref. 1.
4. Nelson, L. and E. Obert, How to Use the New Generalized Compressibility Charts, Chem. Eng., 61, (7) pp. 203208 (July 1954).
5. Redlich, O. and J. Kwong, On the Thermodynamics of Solutions, Chem. Rev., 44, pp. 233244 (1949).
The generalized compressibility charts are based on experimental data for 30 gases. Typical deviations are reportedly 12%, but some gases such as methane, water and fluoromethane display deviations of up to 4% in different regions
of the charts. The Redlich-Kwong equation is a well-established method to model PVT relationships, but information
on its accuracy was not readily available to the author. It reportedly yields Z factors that are in good agreement with experimental values over a wide range of conditions, and is particularly recommended for high-pressure conditions. However, this equation is not accurate at or near critical conditions.
Program available
A Microsoft Excel-based template is available to calculate the compressibility factor using the Redlich-Kwong
equation of state. Readers who are interested in obtaining
the template should contact the author via e-mail. CEP
JIMMY PERESS is director of Tritech Consulting Engineers, Inc. (Jamaica, NY;
Phone: (718) 454-3920; E-mail: [email protected]). He has over 30 years
of experience in process engineering, process troubleshooting, software
development and regulatory compliance (emission inventories and air
permitting). Prior to starting his consulting practice in 1983, Peress was a
process development manager and a senior consultant for Chem Systems,
Inc. (Tarrytown, NY). He earned a BS in chemical engineering from the Israel
Institute of Technology and an MS in chemical engineering from the City
Univ. of New York. He is a professional engineer registered in New York, New
Jersey and Delaware, holds seven U.S. patents and is a member of AIChE.
CEP
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