Gas Properties II

PETE 444

Sept. 13
 Gas Properties II

• The Z-Factor for mixtures

• Pseudo-Critical Values
• Calculation methods
– Z-Factor
– Gas Viscosity

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 What Happened in Gas Props I?
• “ Ideal ” gas law begins to unravel at higher
pressures, lower temperatures
• Andrews: continuity of liquid, gas states; defines
critical point of a substance
• van der Waals: new equation of state to replace
ideal gas law; corresponding states concept based
on reduced pressure, temperature
• Amagat and others start to quantify the deviation
of a gas from ideal behavior
• Z-factor is defined

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 The Z-Factor and Gas Mixtures
Experiments had affirmed
the law of corresponding
states for pure components.
However, applying the
same to a mixture was not
so successful.
For example, published
density data for a 60% C1-C3 mixture
methane - 40% propane pr calculated from true pc
Tr = 1.07, based on true Tc
mixture at 55°C was used
to calculate z-factor; it was
then plotted as a function of
Tr, pr, where these reduced
values were determined
using the true critical point Conclusion: true critical point values cannot be
of the mixture. used to calculate z-factor of mixtures.
Brown, Souders and Smith in Industrial and Engineering Chemistry V24 N5, 1932.
C1-C3 data from Sage, in Industrial and Engineering Chemistry, 1934.
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 The Z-Factor and Gas Mixtures
• With known gas composition
– Kay (1936)
• With gas specific gravity only
– Standing and Katz (1941)
– Sutton (1985) and (2005)
– Wichert-Aziz correction for sour gases (1971)

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 W.B. Kay (1936)

• Assumed principle of corresponding states would

somehow apply to these complex mixtures

• Realized that actual critical point of mixtures

cannot be used to calculate Tr, pr for z-factor
determination

• Need pseudo-critical properties Tpc, Ppc

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 Kay’s Method
Kay observed that the critical values for pure components
exhibited a definite trend when plotted against molecular weight,
concluding that…

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 Kay’s Method
Kay’s mixing rule can be expressed as follows:
k Tpc is pseudocritical temperature of mixture
Tpc = å y j Tcj ppc is pseudocritical pressure of mixture
j=1
yj is mole fraction of component j
k
p pc = å y j pcj
Tcj is real critical temperature of component j

j=1 pcj is real critical pressure of component j

k is number of components in mixture

Kay, Ind. Eng. Chem., Vol. 28 No. 9, 1014-1019, Sept. 1936 8

 Example Problem 3.1
Use Kay ’ s method to obtain the pseudo-critical
properties of the 60% methane - 40% propane mixture.

Component Mole Tc, K Pc, kPa

fraction, yi
Methane 0.6 190.6 4599
Propane 0.4 369.8 4240

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 Kay’s Method

k
rg Ma Ma
Ma = å y j M j gg = = =
j=1
rair M air 28.965

NOTE: Not considered accurate for gas specific gravity > 0.75
GPSA Data Handbook, 11th Edition, SI 10
 Example: Actual vs. Pseudo CP
Binary Mixture
CH4: Tc=190.6K
Pc=4599 kPa real mixture Tc, pc

C2H6: Tc=305.4K
Pc=4880 kPa
calculated Tpc, ppc
Tpc= 0.7x190.6 + 0.3x305.4
= 225°K

ppc= 0.7x4599 + 0.3x4880

= 4683 kPa

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 Example: Actual vs. Pseudo CP
Multi-Component Mixture
PSEUDOCRITICAL PT

CH4 (mole frac = 0.8511)

Tc=190.6K
Pc=4599 kPaa

C2H6 (mole frac = 0.1007)

Tc=305.4K
Pc=4880 kPaa

C3H8 (mole frac = 0.0482)

Tc=369.8K
Pc=4240 kPaa

CALCULATED
Tpc=210.8K
ppc=4566 kPaa
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 Standing & Katz (1941)
• Laboratory work with 16 gas samples
• Specific gravity range 0.66 to 1.07
• Extended pressure range of previous work on gas
to establish their landmark super-compressibility
(z-factor) chart
• Their chart is still considered the standard to
match with EOS methods
• Also observed that pseudocritical properties are
roughly a function of gas gravity
– “Gases containing over 2 or 3 per cent of nitrogen or
high concentrations of ethane, propane, and butanes
deviate from the given curves.”
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To determine z-factor:
- obtain Tpr, ppr by Kay’s or correlation
- lookup z on Standing & Katz’ chart.
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 Example Problem 3.2
Use Kay’s method and Standing & Katz’s chart to find
the z-factor of the 60% methane - 40% propane mixture
at 333.15 K and 5 MPa.

Component Mole Tc, K Pc, kPa

fraction, yi
Methane 0.6 190.6 4599
Propane 0.4 369.8 4240

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Pseudoproperties by Sutton (1985)

• Challenged Kay’s method for high MW

gases
• Analyzed 634 gas compositions from
reports
• Presented new (non-linear) correlation for
Tpc, ppc as a function of specific gravity
• Appropriate for light natural gases and gas
condensates

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 Pseudoproperties by Sutton (1985)

Original correlation in English units:

ppc (psia) = 756.8 - 131.0 g - 3.6 g2
Tpc (°R) = 169.2 + 349.5 g - 74 g2

SI version:
ppc (kPa) = 5218.1 - 903.2 g - 24.8 g2
Tpc (°K) = 94 + 194.2g - 41.1 g2

Sutton: “Compressibility Factors for High Molecular-Weight Natural Gases,” SPE Paper 14265, 1985. 17
Sutton Data for Tpc

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Comparison of Pseudocritical Pressure Correlations

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 Example Problem 3.3
Use Sutton’s correlation and Standing & Katz’s chart to
find the z-factor of the 60% methane - 40% propane
mixture at 333.15 K and 5 MPa.

Component Mole Mw (g/mol)

fraction, yi
Methane 0.6 16.04
Propane 0.4 30.07

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 Sutton (Sour Gas)
• Expanded his original dataset to 2264
samples, and sets out the following
procedure:
• Obtain gas gravity γg, and non-hydrocarbon
(sour gas) mole fractions (if available)
• Calculate specific gravity of the
hydrocarbon portion of the gas from:
g g -1.5195yCO - 0.9672yN -1.1765yH S NOTE!
gg = 2 2 2
y is mole fraction
HC
1- yCO2 - yH 2S - yN2 g is specific gravity

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 Sutton (Sour Gas)
• Then, calculate pseudocritical values of the
hydrocarbon component from:
p pc , HC  5218.1  903.2 g HC  24.8 g2HC [kPa]
Tpc , HC  94  194.2 g HC  41.1 g2HC [K]

• Obtain the mole fraction of hydrocarbon in

the mixture:
yHC =1- yH2S - yCO2 - yN2

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 Sutton (Sour Gas)
• Next, determine the intermediate critical
properties with:
pcM  yHC p pc , HC  7382 yCO2  3399 y N2  9005 yH 2 S [kPaa ]
TcM  yHCTpc , HC  304.2 yCO2  126.3 y N2  373.6 yH 2 S [ K ]

• Finally, adjust for acid gases using the

Wichert-Aziz correction
A = yH2S+yCO2
B = yH2S
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 Sutton (Sour Gas)
• Determine the correction factor ε:
  120  A0.9  A1.6   15  B 0.5  B 4 

• Calculate the corrected pseudo-critical

parameters
Tpc  TcM  5 / 9[K]
Ppc  PcM Tpc / TcM  B 1  B  5 / 9   [kPaa]

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 Example Problem 3.4
Example
With Wichert and Aziz’s method, calculate the corrected
pseudocritical values of an acid gas correction given:
TcM = 202.79 K, PcM =4630.9 kPaa and %N2=0.55,
%CO2=1.37

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Example Problem 3.1 (Solution)
Use Kay’s method to obtain the 60% methane - 40% propane
mixture.

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Example Problem 3.2 (Solution)
Based on the Example Solution 3.1, the Tpc and Ppc are
262.18 K and 4455.4 kPa, respectively. Thus, the reduced
pseudo temperature and pressure are,
T 333.15K
Tpr    1.27
Tpc 262.28K
P 5000kPa
Ppr    1.12
Ppc 4455.4kPa
From the Standing & Katz’s chart, z-factor is 0.82.

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Example Problem 3.3 (Solution)
First, get the molecular weight of gas mixtures,

M gas   i yi M i
  0.6 16.04+0.4  44.10  g/mol
 27.26g/mol
The gas specific gravity is
M gas 27.26g/mol
g    0.94
M air 29g/mol

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Example Problem 3.3 (Solution)
From Sutton’s correlation,
Ppc (kPa)  5218.1  903.2 g  24.8  g 2

 
 5218.1  903.2  0.94  24.8  0.942 kPa
 4347.18kPa
Tpc (K)  94  194.2 g  41.1 g 2

 94  194.2  0.94  41.1 0.942 K
 240.23K

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Example Problem 3.3 (Solution)
The reduced pseudo properties are,

P 5000kPa
Ppr    1.15
Ppc 4347.18kPa
T 333.15K
Tpr    1.39
Tpc 240.23K

From the Standing & Katz’s chart, z-factor is 0.86.

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 Example Problem 3.4 (Solution)
Example
With Wichert and Aziz’s method, calculate the corrected pseudocritical
values of an acid gas correction given: TcM = 202.79 K, PcM =4630.9 kPaa
and %N2=0.55, %CO2=1.37

1. Calculate:
A = yH2S+yCO2 = 0.0137 (y is mole fraction of gas)
B = yH2S = 0

2. Determine the correction factor, , from:

 =120(A0.9-A1.6)+15(B0.5-B4) = 120(0.01370.9-0.01371.6)+15(00.5-04) =2.4
OR from the Chart (read about 2.5)

3. Calculate corrected pseudo-critical parameters:

Tpc=TcM- 5/9 = 202.79-5 x 2.4/9 = 201.5 (deg K)
Ppc=PcMTpc/[TcM + B(1- B) (5/9)]
= 4630.9 x 201.5/[202.79+0] = 4600.5 (kPa)
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Class Exercise (from Sutton’s paper)

kPaa 7398
K 304.2
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