Physical properties I

Chapter 23
• Compressibility factor (z)
• Pseudo critical properties of gas
• Pseudo reduced properties of gas
• Apparent molecular weight
• Specific gravity
• Density
• Viscosity
1. Compressibility factor (𝒛)
The Compressibility Equation of State
The best way of writing an equation of state for a real gas is to insert a correction factor (𝑧) into the ideal gas
equation.
𝑃𝑉 = 𝑧𝑛𝑅𝑇

𝑚
𝑃𝑉 = 𝑧 𝑅𝑇
𝑀𝑤𝑡
𝑚
𝑃𝑀𝑤𝑡 = 𝑧 𝑅𝑇
𝑉

𝑃𝑀𝑤𝑡 = 𝑧𝜌𝑔𝑅𝑇

𝑃𝑀𝑤𝑡
𝜌𝑔 =
𝑧𝑅𝑇
where 𝑧 = compressibility factor

𝑉𝑎𝑐𝑡𝑢𝑎𝑙
𝑧=
𝑉𝑖𝑑𝑒𝑎𝑙

The z-factor is the ratio of the volume actually occupied by a gas at given pressure and temperature to the volume
the gas would occupy at the same pressure and temperature if it behaved like an ideal gas.(standard condition)
Z-factor: effect of pressure
Behavior of Real Gases

Experiments show that ideal gas behavior does in fact occur at very low pressures.
At moderate pressures, the molecules are close enough to exert some attraction between molecules. This
attraction causes the actual volume to be somewhat less than the volume predicted by the ideal gas
equation, that is, the z-factor will be less than 1.0.
At higher pressures the molecules are forced close together, repulsive forces come into play, the actual volume
is greater than ideal volume, and z-factor is greater than 1.0.
The z-factor varies with changes in :
- gas composition,
- temperature,
- pressure.
It must be determined experimentally. The results of experimental determinations of z-factors usually take the
form charts.
Pseudo critical properties of natural gas:

The Law of Corresponding States has been extended to cover mixtures of gases which are closely
related.
Pseudo critical temperature and pseudo critical pressure have been invented.
These quantities are defined as Kay's mixture rules:

𝑃𝑝𝑐 = ෍ 𝑦𝑗 𝑃𝑐𝑗
𝑗

𝑇𝑝𝑐 = ෍ 𝑦𝑗 𝑇𝑐𝑗
𝑗

Apparent molecular weight of the gas:

MWavg = σ𝑗 𝑦𝑗 𝑀𝑊𝑐𝑗
Pseudo reduced properties of gas:

The realization that this is true for nearly all real gases led to the development of the Law of
Corresponding States and the definition of the terms reduced temperature and reduced pressure.
Reduced temperature and reduced pressure are defined as:
𝑃
𝑃𝑟 =
𝑃𝑐

𝑇
𝑇𝑟 =
𝑇𝑐
Similar behavior of Real Gases

The Law of Corresponding States says that all pure gases have the same z-factor at the same values of
reduced pressure and reduced temperature.
Z factor for methane, propane, n-pentane, and n-hexane( from the handbook of natural gas engineering)
Using charts developed by Standing and
Katz (1942) to determine z- factor
Pseudo critical properties correlations
Effect of non hydrocarbon components

Natural gases commonly contain:

hydrogen sulfide, carbon dioxide, and nitrogen.
The presence of nitrogen does not greatly affect the z-factor obtained by methods previously described; z-factor
increases by about 1% for each 5% of nitrogen in the gas.
The presence of hydrogen sulfide and carbon dioxide causes large errors in compressibility factors obtained by
the methods previously discussed.
The remedy to this problem is to adjust the pseudo critical properties to account for the unusual behavior of these
acid gases. The equations used for this adjustment are:

𝑇′𝑝𝑐 = 𝑇𝑝𝑐 + 𝜀
′
′
𝑃𝑝𝑐 𝑇𝑝𝑐
𝑃𝑝𝑐 =
𝑇𝑝𝑐 + 𝑦𝐻2𝑆 1 − 𝑦𝐻2𝑆 𝜀

Where 𝑇′𝑝𝑐 and 𝑃′𝑝𝑐 are used to calculate 𝑇𝑝𝑟 and 𝑃𝑝𝑟 for acid gases. The pseudo critical temperature adjustment
factor (𝜀) is obtained from the Figure .
The corrections can be made using correlations such as the Wichert-Aziz (1972)* correction expressed as
follows:
𝐴 = 𝑦𝐻2𝑆 + 𝑦𝐶𝑂2 , 𝐵 = 𝑦𝐻2𝑆

𝜀3 = 120 𝐴0.9 − 𝐴1.6 + 15 𝐵0.5 − 𝐵4.0

′ = 𝑇 −𝜀
𝑇𝑝𝑐 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑇𝑝𝑐
𝑝𝑐 3

𝑃 𝑇 ′
′ = 𝑝𝑐 𝑝𝑐
𝑃𝑝𝑐 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑃𝑝𝑐
𝑇𝑝𝑐 + 𝐵 1 − 𝐵 𝜀3
When the composition of a natural gas is unknown, the specific gravity can be inserted into the
following correlation to determine the pseudo critical properties of the gas.

𝑃𝑝𝑐 = 709.604 − 58.718𝛾𝑔

𝑇𝑝𝑐 = 170.491 + 307.344𝛾𝑔

H2S<3%, N22<5%, inorganic component in total<7%

Correlations with impurity corrections for mixture pseudo critical are also available (Ahmed 1989):

𝑃𝑝𝑐 = 678 − 50 𝛾𝑔 − 0.5 − 206.7𝑦𝑁2 + 440𝑦𝐶𝑂2 + 606.7𝑦𝐻2𝑆

𝑇𝑝𝑐 = 326 + 315.7 𝛾𝑔 − 0.5 − 240𝑦𝑁2 − 83.3𝑦𝐶𝑂2 + 133.3𝑦𝐻2𝑆

Quick
method:

Pseudo
critical
properties
when
composition
is unknown
Quick method

Compressibility of
natural gas factor for
different molecular
weight
Example 1:
Calculate the compressibility factor (at 600 R and 500 psia) for the natural gas with the composition
shown in the table using charts developed by Standing and Katz (1941).

Component mol fra

C1 0.85

C2 0.139

C3 0.005

i-C4 0.002

n-C4 0.002

i-C5 0.001

n-C5 0.001

1
Component mol fra Mwt yi*Mwt TC, R yi*Tc Pc, psia yi*Pc

C1 0.85 16.04 13.634 343.34 291.839 667 566.95

C2 0.139 30.07 4.17973 549.92 76.4389 706.6 98.217

C3 0.005 44.096 0.22048 665.92 3.3296 615.5 3.0775

i-C4 0.002 58.122 0.11624 734.41 1.46882 527.9 1.0558

n-C4 0.002 58.122 0.11624 765.55 1.5311 550.9 1.1018

i-C5 0.001 72.149 0.07215 829 0.829 490.4 0.4904

n-C5 0.001 72.149 0.07215 845.8 0.8458 488.8 0.4888

Total 1 Mwtmix 18.411 Tc, mix 376.282 Pc, mix 671.38

Tr=T/Tc Pr=P/Pc z =0.95

1.5945 0.7447
𝑃𝑝𝑐 = 709.604 − 58.718𝛾𝑔

𝑇𝑝𝑐 = 170.491 + 307.344𝛾𝑔

Pc, equation 672.3262 Pc, mix 671.38

Tc, equation 365.612 Tc, mix 376.282

Pr 0.743687 Pr 0.7447

1.5945
Tr 1.641084 Tr

z =0.95
Z Z
Calculate the compressibility factor (at 600 R and 500 psia) for the natural gas with the composition
shown in the table.

Component mol fra

N2 0.0052
CO2 0.1
H2S 0.05
C1 0.75
C2 0.08
C3 0.01
i-C4 0.001
n-C4 0.001
i-C5 0.001
n-C5 0.001
n-C6 0.0008
 𝐴 = 𝑦𝐻2𝑆 + 𝑦𝐶𝑂2 , 𝐵 = 𝑦𝐻2𝑆

𝜀3 = 120 𝐴0.9 − 𝐴1.6 + 15 𝐵0.5 − 𝐵4.0

′
𝑇𝑝𝑐 = 𝑇𝑝𝑐 − 𝜀3 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑇𝑝𝑐

𝑃 𝑇 ′
′ 𝑝𝑐 𝑝𝑐
𝑃𝑝𝑐 = 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑃𝑝𝑐
𝑇𝑝𝑐 + 𝐵 1 − 𝐵 𝜀3
Component mol fra MWT yi*MWT TC, R yi*Tc Pc, psia yi*Pc
N2 0.0052 28.02 0.145704 227.47 1.182844 492.5 2.561
CO2 0.1 44.01 4.401 547.76 54.776 1070 107
H2S 0.05 34.08 1.704 672.81 33.6405 1306.5 65.325
C1 0.75 16.04 12.03 343.34 257.505 667 500.25
C2 0.08 30.07 2.4056 549.92 43.9936 706.6 56.528
C3 0.01 44.096 0.44096 665.92 6.6592 615.5 6.155
i-C4 0.001 58.122 0.058122 734.41 0.73441 527.9 0.5279
n-C4 0.001 58.122 0.058122 765.55 0.76555 550.9 0.5509
i-C5 0.001 72.149 0.072149 829 0.829 490.4 0.4904
n-C5 0.001 72.149 0.072149 845.8 0.8458 488.8 0.4888
n-C6 0.0008 86.175 0.06894 913.8 0.73104 436.9 0.34952
Mwtmix 21.45675 Tc, mix 401.66294 Pc, mix 740.2265
SpGr=21.4675/28.9625
=0.74
Using Wichert Aziz (1972)

A= 0.150 𝐴 = 𝑦𝐻2𝑆 + 𝑦𝐶𝑂2 , 𝐵 = 𝑦𝐻2𝑆

B= 0.050 𝜀3 = 120 𝐴0.9 − 𝐴1.6 + 15 𝐵0.5 − 𝐵4.0

′
e= 19.35 𝑇𝑝𝑐 = 𝑇𝑝𝑐 − 𝜀3 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑇𝑝𝑐
′
′
𝑃𝑝𝑐 𝑇𝑝𝑐
Tcorrected = 382.3 𝑃𝑝𝑐 = 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑒𝑑 𝑃𝑝𝑐
𝑇𝑝𝑐 + 𝐵 1 − 𝐵 𝜀3
Pcorrected = 703.0

Tr_dash = 1.569

Pr_dash = 0.711 z= 0.94 From the figure

Example2: calculate Z factor for natural gas with specific gravity of 1.26 for use at 256oF and
602.5 Psia .
From figure:
Tc=492R
Pc=587Psia
Tr=716/492=1.46
Pr=602.5/587=10.26
From figure :
Z=1.154
Calculate Z for gas at 2500 psia and 180 F
z–factor using EOS:
Soave-Redlich and Kwond EOS: well at Tr > 1

𝑅𝑇 𝑎∝
𝑃= −
𝑣−𝑏 𝑣 𝑣−𝑏

0.42748𝑅2 𝑇𝑐2
𝑎=
𝑃𝑐

0.08664𝑅𝑇𝑐
𝑏=
𝑃𝑐
2
∝= 1 + 𝑚 1 − 𝑇𝑟
𝑚 = 0.48 + 1.574𝜔 − 0.177𝜔2
𝑇𝑟 = reduced temperature, 𝑇/𝑇𝑐
𝜔 = acentric factor of the substance
𝑇 = system temperature, 𝑜𝑅
𝑃 = system pressure, 𝑝𝑠𝑖𝑎
 𝑅𝑇 2 𝑎 ∝ 𝑏𝑅𝑇 𝑎∝𝑏
𝑣3 − 𝑣 + − 2
−𝑏 𝑣− =0
𝑃 𝑃 𝑃 𝑃

𝑧 3 − 𝑧 2 + 𝐴 − 𝐵 − 𝐵2 𝑧 − 𝐴𝐵 = 0
Where:

𝑎∝ 𝑏𝑃
𝐴= & 𝐵=
𝑅𝑇 2 𝑅𝑇
Density:

𝑃𝑀𝑤𝑡
• 𝜌𝑔 =
𝑧𝑅𝑇
𝑀.𝑊𝑇 𝑀.𝑊𝑇
• 𝛾𝑔 = =
𝑀.𝑤𝑡 𝑎𝑖𝑟 29

𝑃(29𝛾𝑔 ) 2.7𝑃𝛾𝑔
• 𝜌𝑔 = = where T: R
𝑧(10.732)𝑇 𝑧𝑇
• P: psia
𝜌𝑔 : lbm/ft3
Specific gravity:
Specific gravity: ratio of average molecular weight of natural gas to the air
𝑀. 𝑊𝑇
𝛾𝑔 =
28.97
MWavg = σ𝑗 𝑦𝑗 𝑀𝑊𝑐𝑗

When the air is 79%N2 and 21%O2

𝑛𝑖
𝑦𝑗 =
𝑛𝑡
Pi=𝑦𝑗 Pt
Gas specific gravity 𝑀. 𝑊𝑇

Review 𝛾𝑔 =
28.97

Apparent molecular weight MWavg = σ𝑗 𝑦𝑗 𝑀𝑊𝑐𝑗

Gas pseudo critical pressure and 𝑃𝑝𝑐 = ෍ 𝑦𝑗 𝑃𝑐𝑗

temperature 𝑗

𝑇𝑝𝑐 = ෍ 𝑦𝑗 𝑇𝑐𝑗
𝑗

𝑃𝑝𝑐 = 709.604 − 58.718𝛾𝑔 As function of specific gravity when:

H2S<3%, N22<5%, inorganic component in total<7%
𝑇𝑝𝑐 = 170.491 + 307.344𝛾𝑔 Guo and Ghalambur (2005)

With impurities such as N2, H2S, CO2

𝑃𝑝𝑐 = 678 − 50 𝛾𝑔 − 0.5 − 206.7𝑦𝑁2 + 440𝑦𝐶𝑂2 + 606.7𝑦𝐻2𝑆 (Ahmed 1989)
𝑇𝑝𝑐 = 326 + 315.7 𝛾𝑔 − 0.5 − 240𝑦𝑁2 − 83.3𝑦𝐶𝑂2 + 133.3𝑦𝐻2𝑆

𝑇′𝑝𝑐 = 𝑇𝑝𝑐 + 𝜀 Corrected pseudo critical pressure and temperature if

′
impurities are exist
𝑃𝑝𝑐 𝑇𝑝𝑐
′
𝑃𝑝𝑐 = (Wichert and Aziz)
𝑇𝑝𝑐 + 𝑦𝐻2𝑆 1 − 𝑦𝐻2𝑆 𝜀
𝐴 = 𝑦𝐻2𝑆 + 𝑦𝐶𝑂2 , 𝐵 = 𝑦𝐻2𝑆

𝜀3 = 120 𝐴0.9 − 𝐴1.6 + 15 𝐵0.5 − 𝐵4.0

Viscosity:
Gas viscosity is a measure of the resistance to flow exerted by the gas. Dynamic viscosity (μg) in
centipoises (cp) is usually used in the natural engineering. [1 cp = 6.72 e-4 lbm/(ft-sec)]

Kinematic viscosity (𝜈𝑔 ) is related to the dynamic viscosity through density (𝜌𝑔 ).

𝜇𝑔
𝑣𝑔 =
𝜌𝑔
If gas composition and viscosities of gas components are known, the mixing rule can be used for
determining the viscosity of the gas mixture: ( sweet gas, at 1 atm)

σ 𝜇𝑔𝑖 𝑦𝑖 𝑀𝑤𝑡𝑖
𝜇𝑔 =
σ 𝑦𝑖 𝑀𝑤𝑡𝑖
Viscosity of pure gases at
atmospheric pressure.
Example: calculate the viscosity of gas mixture at 200oF and 1 atm.

Comp Mole frac

C1 0.85 σ 𝜇𝑔𝑖 𝑦𝑖 𝑀𝑤𝑡𝑖
𝜇𝑔 =
C2 0.09 σ 𝑦𝑖 𝑀𝑤𝑡𝑖
C3 0.04
C4 0.02

• Solution :
comp mole frac Mwt 𝜇𝑔i yi(Mwt)^0.5 𝜇𝑔i*yi(Mwt)^0.5
C1 0.85 16.04 0.013 3.40424735 0.044255216
C2 0.09 30.07 0.0112 0.49352508 0.005527481
C3 0.04 44.1 0.0098 0.26563132 0.002603187
C4 0.02 58.12 0.0091 0.15247295 0.001387504
sum 4.31587669 0.053773387

𝜇𝑔 0.012459cp
 •

• Viscosity correlations:
The gas viscosity correlation of Carr, Kobayashi, and Burrows (1954)* involves a two-step
procedure:
The gas viscosity at temperature and atmospheric pressure is estimated first from gas-specific
gravity and inorganic compound content.
The atmospheric value is then adjusted to pressure conditions by means of a correction factor on the
basis of reduced temperature and pressure state of the gas.
The atmospheric pressure viscosity (𝜇1) can be expressed as: (1 atm)

𝜇1 = 𝜇1𝐻𝐶 + 𝜇1𝑁2 + 𝜇1𝐶𝑂2 + 𝜇1𝐻2𝑆

𝜇1𝐻𝐶 = 8.188 × 10−3 − 6.15 × 10−3𝑙𝑜𝑔 𝛾𝑔 + 1.709 × 10−5 − 2.062 × 10−6𝛾𝑔 𝑇

𝜇1𝑁2 = 9.59 × 10−3 + 8.48 × 10−3𝑙𝑜𝑔 𝛾𝑔 𝑦𝑁2

𝜇1𝐶𝑂2 = 6.24 × 10−3 + 9.08 × 10−3𝑙𝑜𝑔 𝛾𝑔 𝑦𝐶𝑂2

𝜇1𝐻2𝑆 = 3.73 × 10−3 + 8.49 × 10−3 𝑙𝑜𝑔 𝛾𝑔 𝑦𝐻2 𝑆

 Dempsey (1965)** developed the following relation:

𝜇𝑔
𝜇𝑟 = 𝑙𝑛 𝑇
𝜇1 𝑝𝑟
2 + 𝑎 𝑃3 + 𝑇
= 𝑎0 + 𝑎1 𝑃𝑝𝑟 + 𝑎2 𝑃𝑝𝑟 2 3 2 2 3
3 𝑝𝑟 𝑝𝑟 𝑎4 + 𝑎5 𝑃𝑝𝑟 + 𝑎6 𝑃𝑝𝑟 + 𝑎7 𝑃𝑝𝑟 + 𝑇𝑝𝑟 𝑎8 + 𝑎9 𝑃𝑝𝑟 + 𝑎10 𝑃𝑝𝑟 + 𝑎11 𝑃𝑝𝑟

3 2 3
+ 𝑇𝑝𝑟 𝑎12 + 𝑎13 𝑃𝑝𝑟 + 𝑎14 𝑃𝑝𝑟 + 𝑎15 𝑃𝑝𝑟

Thus, once the value of ( 𝜇𝑟 ) is determined from the right-hand side of this equation, gas viscosity at elevated
pressure can be readily calculated using the following relation:

𝜇1 𝜇
𝜇𝑔 = 𝑒 𝑟
𝑇𝑝𝑟
Gas viscosity at atmospheric pressure:
1. By knowing the gravity or average
molecular weight, the viscosity of gas
can be determine from figure.
2. By applying the correction of
containing of sour gases such as carbon
dioxide, hydrogen sulfide, and nitrogen.

Where:
𝜇1: viscosity of gas at 1 atm
Gas viscosity at high pressure

Where:
𝜇1: viscosity of gas at 1 atm
𝜇g: viscosity of gas at given pressure
Example: calculate the viscosity of gas mixture at 200oF and 1 atm.

Comp Mole frac

C1 0.85 σ 𝜇𝑔𝑖 𝑦𝑖 𝑀𝑤𝑡𝑖
𝜇𝑔 =
C2 0.09 σ 𝑦𝑖 𝑀𝑤𝑡𝑖
C3 0.04
C4 0.02

• Solution :
comp mole frac Mwt yi*Mwt
C1 0.85 16.04 13.634
C2 0.09 30.07 2.7063
C3 0.04 44.1 1.764
C4 0.02 58.12 1.1624
sum 19.2667

𝜇𝑔 =0.0124
%N2=1.3 mole
%Co2=1.64mole
%H2S=18.41mole
 Example:
A 0.65 specific gravity natural gas contains 10% nitrogen, 8% carbon dioxide, and 2% hydrogen sulfide. Estimate viscosity of
the gas at 10,000 psia and 180 °F.

Calculated Parameter Values:

Pseudocritical pressure: 697.164 psia 𝑃𝑝𝑐 = 678 − 50 𝛾𝑔 − 0.5 − 206.7𝑦𝑁2 + 440𝑦𝐶𝑂2 + 606.7𝑦𝐻2𝑆

Pseudocritical temperature: 345.357 R 𝑇𝑝𝑐 = 326 + 315.7 𝛾𝑔 − 0.5 − 240𝑦𝑁2 − 83.3𝑦𝐶𝑂2 + 133.3𝑦𝐻2𝑆

𝜇1𝐻𝐶 = 8.188 × 10−3 − 6.15 × 10−3𝑙𝑜𝑔 𝛾𝑔 + 1.709 × 10−5 − 2.062 × 10−6𝛾𝑔 𝑇

Uncorrected gas viscosity at 14.7 psia: 0.01217 cp
𝜇1𝑁2 = 9.59 × 10−3 + 8.48 × 10−3𝑙𝑜𝑔 𝛾𝑔 𝑦𝑁2
N2 correction for gas viscosity at 14.7 psia: 0.0008 cp
𝜇1𝐶𝑂2 = 6.24 × 10−3 + 9.08 × 10−3𝑙𝑜𝑔 𝛾𝑔 𝑦𝐶𝑂2
CO2 correction for gas viscosity at 14.7 psia: 0.00036 cp
𝜇1𝐻2𝑆 = 3.73 × 10−3 + 8.49 × 10−3 𝑙𝑜𝑔 𝛾𝑔 𝑦𝐻2 𝑆
H2S correction for gas viscosity at 14.7 psia: 4.3E-05 cp
Corrected gas viscosity at 14.7 psia (m1): 0.01338 cp 𝜇1 = 𝜇1𝐻𝐶 + 𝜇1𝑁2 + 𝜇1𝐶𝑂2 + 𝜇1𝐻2𝑆
Pseudo-reduced pressure: 14.34
Pseudo-reduced temperature: 1.85
ln (mg/m1*Tpr) 1.60227
Gas viscosity: 0.03584 cp
Lee Gonzalez and Eakin method:
Thermal Conductivity:

Thermal conductivity for natural gas mixtures at elevated pressure depends on temperature;

pressure and composition which can be calculated from an atmospheric value and a pressure

correction. Figs. 23-31 through 23-36 present low pressure thermal conductivity data for gases
Example
Find the thermal conductivity of a natural gas at 700 𝑝𝑠𝑖𝑎 and 300 °𝐹 with properties 𝑀𝑤𝑡 = 25, 𝑇𝑐 = 440 °𝑅 and 𝑃𝑐 =
660 𝑝𝑠𝑖𝑎.

𝐹𝑖𝑔( 23.31) @ 300𝐹: 𝑘𝐴 = 0.0248 𝐵𝑡𝑢/[(ℎ𝑟 𝑓𝑡 2 °𝐹)/𝑓𝑡]

𝑇𝑟 = (300 + 459.67)/440 = 1.73
𝑃𝑟 = 700/660 = 1.06
𝐹𝑟𝑜𝑚 𝐹𝑖𝑔. 23 − 32:
𝑘/𝑘𝐴 = 1.15
𝑘 = (1.15) (0.0248) = 0.0285 𝐵𝑡𝑢/[(ℎ𝑟 𝑓𝑡 2 °𝐹)/𝑓𝑡]