MSc Petroleum Engineering

School of Engineering

Oil PVT Properties

(Compositional Calculation Approach)

Contact hours:11
Credit unit:33
Staff contact info:
roozbeh.rafati@abdn.ac.uk

Lecturer Name, PhD Page 1 www.abdn.ac.uk

Vapor Pressure

Consider a closed evacuated container that has been partially

filled with a pure component in the liquid state. The molecules
of the liquid are in constant motion with different velocities.

When one of these molecules reaches the liquid surface, it may

possess sufficient kinetic energy to overcome the attractive
forces in the liquid and pass into the vapor spaces above. As
the number of molecules in the vapor phase increases, the rate vapor
vapor
of return to the liquid phase also increases. A state of
equilibrium is eventually reached when the number of
molecules leaving and returning is equal. liquid
liquid

The molecules in the vapor phase obviously exert a pressure on

the wall of the container and this pressure is defined as the
vapor pressure, Pv.

Lecturer Name, PhD Page 2 www.abdn.ac.uk

Lecturer Name, PhD
Vapor pressure from Cox Chart

Page 3

• P < system is entirely in vapor phase

• P < system is entirely in liquid phase
• P < vapor and liquid coexist in equilibrium
Figure 7. Cox Chart

www.abdn.ac.uk
Vapor pressure from Lee and Kesler method (1975)

¿
where
6.09648 6
𝐴=5.92714 − − 1.2886 ln(𝑇 𝑟 )+ 0.16934 ( 𝑇 𝑟 )
𝑇𝑟
15.6875 6
𝐵=15.2518 − −13.4721 ln (𝑇 𝑟 )+0.4357 ( 𝑇 𝑟 )
𝑇𝑟
The acentric factor is said to be a measure of
the non-sphericity (centricity) of molecules.
where pv = vapor pressure, psi
pc = critical pressure, psi
Tr = reduced temperature (T / Tc)
T = system temperature, °R
Tc = critical temperature, °R
𝜔= 3 ¿ ¿
ω = acentric factor
where T = Acentric factor
pc = Critical pressure, Psia
Tc = Critical temperature,
Tb = Normal boiling point,

Lecturer Name, PhD Page 4 www.abdn.ac.uk

Escaping Tendency at Equilibrium Condition:
Escaping tendency of each phase when they are at equilibrium is called fugacity. For an ideal gas, fugacity is equal
to its pressure, and the fugacity of each component is equal to its partial pressure. Fugacity has pressure units.

= fugacity = universal gas constant

𝑉 = volume
𝑑( 𝐼𝑛 𝑓 )= 𝑑𝑝
𝑅𝑇 = temperature
= pressure

At equilibrium, the fugacity of the liquid must equal the fugacity of the gas:

𝑓 𝑔= 𝑓 𝐿

The vapour pressure is simply the pressure, for which the fugacity of the liquid equals the fugacity of the gas.

Equation of States (EOS) can be used to calculate the vapour pressure of the pure components
Van Der Waals Equations of State:
Van der Waals improved the ideal gas equation by considering the intermolecular attractive and
repulsive forces, and introduced his well-known equation of state in 1873.

( 𝑃+
𝑎
𝑣2 )
( 𝑣 − 𝑏 ) = 𝑅𝑇

where a/v2 and b represent the attractive and repulsive terms, respectively, and v is the molar volume.
The above equation in terms of volume or compressibility factor takes a cubic form as:
follows:
𝑧𝑅𝑇
𝑣=
𝑝

(
𝑣 3 − 𝑏+
𝑅𝑇
𝑃 ) ( )
𝑣2 +
𝑎
𝑃
𝑣−
𝑎𝑏
𝑃
=0 𝐴=
𝑎𝑃
( 𝑅𝑇 )
2
3 2
𝑍 − ( 1+ 𝐵 ) 𝑍 + 𝐴𝑍 − 𝐴𝐵=0

𝑏𝑃
𝐵=
𝑅𝑇

For a pure compound at T<Tc, the equation may give three real roots for volume (or Z) at any pressure:
• The highest value corresponds to that of vapour
• The lowest value, corresponds to that of liquid
• The middle value, is of no physical significance https://www.youtube.com/watch?v=9_epJ4vUsNI&t=197s
Peng-Robinson Equation of State:

[ 𝑃+
𝑎𝑇
]
𝑉 𝑀 ( 𝑉 𝑀 + 𝑏 ) +𝑏 ( 𝑉 𝑀 − 𝑏 )
( 𝑉 𝑀 −𝑏 )= 𝑅𝑇
𝑎=0. 45724
𝑅 𝑇𝑐
𝑝𝑐
2 2

can be arranged into cubic form, 𝑅𝑇𝑐

𝑏=0.07780
𝑝𝑐

Substitution of
𝑧𝑅𝑇
𝑉 𝑀= 𝑎𝑇 𝑝
𝑝 𝐴= 2 2
𝑅 𝑇
into the Peng-Robinson equation of state gives
𝑏𝑝
𝐵=
𝑅𝑇
𝑧 3 − (1 − 𝐵 ) 𝑧 2+ ( 𝐴 − 2 𝐵 − 3 𝐵2 ) 𝑧 − ( 𝐴𝐵 − 𝐵2 − 𝐵3 ) =0
𝑎 𝑇 =𝑎 𝑐 𝛼
𝑅2 𝑇 2𝑐
𝑎 𝑐 =0.45724
𝑝𝑐
1
𝛼 1/ 2
=1+ ( 0.37464+ 1.54226 𝜔 − 0.26992 𝜔 ) (1 −𝑇 )
2 2
𝑟

each pure substance has a different value of acentric factor, w

Roots of Peng-Robinson Equation of State:

Three values of z-factor cause the equation to equal zero. These three "roots“ are all real when pressure and
temperature are on the vapor pressure line-that is, when liquid and gas are present. One real root and two complex
roots exist when the temperature is above the critical temperature.

The largest root is the z-factor of the equilibrium gas and the smallest is the z-factor of the equilibrium liquid.

[ ( )
]
1

( )
𝑓𝑔 𝑧 𝑔 + 2 +1 𝐵
2
𝐴
Largest root : 𝐼𝑛 = 𝑧 𝑔 − 1− 𝐼𝑛 ( 𝑧 𝑔 − 𝐵 ) − 1.5 𝐼𝑛
−(2 − 1) 𝐵
𝑝 2 𝐵 1
𝑧𝑔 2

[ ( )
]
1

( )
𝑓𝐿 𝑧 𝐿+ 2 + 1 𝐵
2
Smallest root: 𝐴
𝐼𝑛 = 𝑧 𝐿 − 1 − 𝐼𝑛 ( 𝑧 𝐿 − 𝐵 ) − 1.5 𝐼𝑛
−(2 −1) 𝐵
𝑝 2 𝐵 1
𝑧𝐿 2

8
Example: Calculate the vapour pressure of iso-butane at 190°F. Use the Peng-Robinson:
Solution
First, calculate those coefficients which are not pressure dependent
𝑇 190+ 459.67
𝑇 𝑟= = =0.88495
𝑇 𝑐 274.46+ 459.67

𝑅𝑇𝑐 10.732 ∗734.13

𝑏=Ω 𝑏 = ( 0.07780 ) =1.1611
𝑝𝑐 527.9

𝑅𝑇𝑐 ( 10.732 )2 (734.13 )2

𝑎𝑐 = Ω𝑎 =0.45724 =53,765
𝑝𝑐 527.9
1

𝛼=1.0787 𝑤h𝑒𝑟𝑒 𝜔=0.1852 𝛼 1/ 2

=1+ ( 0.37464+ 1.54226 𝜔 − 0.26992 𝜔 ) (1 −𝑇 )
2 2
𝑟

𝑎 𝑇 =𝑎 𝑐 𝛼=53,765 ∗1.0787=57,995

Second, by trial and error, find a pressure which causes the fugacity of the liquid calculated with the following
equations to equal the fugacity of the gas calculated with the same equations. Only the last calculation with a final
trial value of p-228.79 psia will be shown.

𝑎𝑇 𝑝 57,995∗ 228.79 𝑏𝑝 1.1611 ∗ 228.79

𝐴= = =0.27295 𝐵= = =0.038101
( 𝑅𝑇 )
2 2
10.732 ∗ 649.67
2 𝑅𝑇 10.732∗ 649.67
9
The three roots which solve

𝑧 3 − (1 − 𝐵 ) 𝑧 2+ ( 𝐴 − 2 𝐵 − 3 𝐵2 ) 𝑧 − ( 𝐴𝐵 − 𝐵2 − 𝐵3 ) =0

Are 0.067258, 0.18678 and 0.70786.

𝑧 𝐿 =0.067258∧𝑧 𝑔 =0.70786

Then

[ ( )
]
1

( )
𝑓𝑔 𝑧 𝑔 + 2 +1 𝐵2
𝐴
𝐼𝑛 = 𝑧 𝑔 − 1− 𝐼𝑛 ( 𝑧 𝑔 − 𝐵 ) − 1.5 𝐼𝑛
𝑓 𝑔 =176.79 𝑝𝑠𝑖𝑎
−(2 − 1) 𝐵
𝑝 2 𝐵 1
𝑧𝑔 2

and =

[ +( 2 )
]
1
𝑓 𝐿 =176.79 𝑝𝑠𝑖𝑎
( )
𝑓𝐿 𝑧𝐿 +1 𝐵
2
𝐴
𝐼𝑛 = 𝑧 𝐿 − 1 − 𝐼𝑛 ( 𝑧 𝐿 − 𝐵 ) − 1.5 𝐼𝑛
−(2 −1) 𝐵
𝑝 2 𝐵 1
𝑧𝐿 2

10
= thus the trial value of p, 228.79 psia, is the vapor pressure of iso-butane at 190°F. Notice that the molar volumes
can be calculated easily.

𝑧 𝑔 𝑅𝑇 (0.70786) (10.732)( 649.67) cu ft

𝑉 𝑀𝑔 = = =21.57
𝑝 ( 228.79) lb mole

𝑧 𝐿 𝑅𝑇 (0.067258)(10.732)(649.67) cu ft
𝑉 𝑀𝐿 = = =2.050
𝑝 (228.79) lb mole

Compare results with experimental data

Calculated Experimental
Vapor pressure, psia 228.8 228.3
Saturated liquid molar volume, cu ft/lb mole 2.05 2.035
Saturated vapor Molar volume, mole cu ft/lb 21.57 21.68
Liquid z-factor 0.0673 0.0666
Gas z-factor 0.7078 0.7101
11
PVT Calculation of Mixtures using the Equation of State:

Mixtures
The situation with regard to mixtures is somewhat more difficult to visualize. However, equilibrium is attained when the
chemical potential of each component in the liquid equals the chemical potential of that component in the gas.
For mixtures we need to use another useful term which is called fugacity coefficient to calculate fluid properties
using the equation of state. Fugacity coefficient for each component of a mixture is defined as the ratio of fugacity to
partial pressure.
𝑓 𝑗
Fugacity Coefficient 𝜙 𝑗=
𝑦 𝑖𝑝

where fLi = fgi at equilibrium

𝑓 𝐿𝑗
𝜙 𝐿𝑗 𝑥 𝑗 𝑝 𝑦 𝑗
𝐾 𝑗= = =
𝜙𝑔𝑗 𝑓 𝑔𝑗 𝑥𝑗
𝑦 𝑗𝑝

12
 Vapour Pressure Calculation for Mixtures using Peng-Robinson EOS:
1
𝑅 𝑇 𝑐𝑗
𝑎 𝑇 =∑ ∑ 𝑦 𝑖 𝑦 𝑗 ( 𝑎𝑇𝑖 𝑎𝑇𝑗 ) (1− 𝛿𝑖𝑗 )
2
𝑏 𝑗=0.07780

[ ]
𝑅𝑇 𝑎𝑇 𝑖 𝑗 𝑝 𝑐𝑗
𝑝= −
𝑉 𝑀 −𝑏 𝑉 𝑀 ( 𝑉 𝑀 +𝑏 ) +𝑏 ( 𝑉 𝑀 −𝑏 ) 𝑎 𝑇𝑗 =𝑎𝑐𝑗 𝛼 𝑗
𝑏=∑ 𝑦 𝑗 𝑏 𝑗 𝑅 𝑇 𝑐𝑗
2 2

𝑗
𝑎 𝑐𝑗 =0.45724
𝑝 𝑐𝑗
where subscripts i and j refer to components
1
𝛼 1/ 2
𝑗 =1+ ( 0.37464 +1.54226 𝜔 𝑗 − 0.26992 𝜔 ) (1 − 𝑇 ) 2
𝑗
2
𝑟𝑗

Binary interaction coefficients =0

As before, the Peng-Robinson equation can be written as:

𝛿𝑖 𝑗 =𝛿 𝑗 𝑖
Binary interaction coefficients can be extracted from
𝑧 − (1 − 𝐵 ) 𝑧 2+ ( 𝐴 − 2 𝐵 − 3 𝐵2 ) 𝑧 − ( 𝐴𝐵 − 𝐵2 − 𝐵3 ) =0
3
the experiments. If the values are known, you can
insert them into equation. If not, consider 0.
where
𝑎𝑇 𝑝
𝐴=
𝑅2𝑇 2

𝑏𝑝
𝐵=
𝑅𝑇 13
 𝑏𝑗

[ ]
𝐵 ′ 𝑗=
𝑧 + (2 )
1

𝐴
2
+1 𝐵 𝑏
𝐼𝑛 𝜙 𝑗 =− 𝐼𝑛 ( 𝑧 − 𝐵 ) + ( 𝑧 − 1 ) 𝐵′ 𝑗 − ( 𝐴′ 𝑗 − 𝐵′ 𝑗 ) 𝐼𝑛
𝑧 − (2 −1) 𝐵
1.5
2 𝐵

[ ]
1
2 1
1
𝐴′ 𝑗 = 2 𝑎1/𝑇𝑗2 ∑ 𝑦 𝑖 𝑎𝑇𝑖
2
(1− 𝛿𝑖𝑗 )
𝑓 𝐿𝑗 =𝑥 𝑗 𝑝 𝜙 𝐿𝑗 𝑎𝑇 𝑙

𝑓 𝑔𝑗 = 𝑦 𝑗 𝑝 𝜙 𝑔𝑗
If less than 10-3 then the equilibrium is achieved
𝜖 𝑗 = 𝑓 𝐿𝑗 − 𝑓 𝑔𝑗

𝑓 𝑔𝑗 = 𝑓 𝐿𝑗

We can also use equilibrium constant method:

𝑓 𝐿𝑗
𝜙 𝑥 𝑝 𝑦 𝐶 2
𝐾 𝑗 = 𝐿𝑗 = 𝑗 = 𝑗 (𝐾 𝑗 − 𝐾 𝑗 )
𝑇
where KCj are the K-factors just calculated and the
𝜙𝑔𝑗 𝑓 𝑔𝑗 𝑥𝑗 𝜖 𝑗= 𝑇 𝐶
𝑦 𝑗𝑝 𝐾𝑗𝐾𝑗 KTj are the trial values of K-factors.
𝜙 𝐿𝑗
𝐾 𝑗=
𝜙𝑔𝑗
14
Example:

Calculate the compositions of the gas and liquid when the mixture with composition given below is brought to
equilibrium at 160 ⁰F and 1000 psia. Use the Peng-Robinson equation of state. Use binary interaction
coefficients of 0.02 for methane-n-butane, 0.04 for methane-n-decane, and 0.0 for n-butane-n-decane.

Component Composition,
mole fraction
Methane 0.5301
n-Butane 0.1055
n-Decane 0.3644
1

15
Solution:
First, calculate the coefficients of the components of the mixture
1
𝛼 1/ 2
𝑗 =1+ ( 0.37464 +1.54226 𝜔 𝑗 − 0.26992 𝜔 ) (1 − 𝑇 )
2
𝑗
2
𝑟𝑗
2 2
𝑅 𝑇 𝑐𝑗
𝑎 𝑐𝑗 =0.45724
𝑝 𝑐𝑗
𝑎 𝑇𝑗 =𝑎𝑐𝑗 𝛼 𝑗
𝑅 𝑇 𝑐𝑗
𝑏 𝑗=0.07780
𝑝 𝑐𝑗
Component R psia
C1 343 666.4 0.0104 0.7481 9297 6956 0.4297
n-C4 765.3 550.6 0.1995 1.1394 56017 63827 1.1604
n-C10 1111.7 305.2 0.4898 1.6139 213240 344149 3.0411

16
Second, select trial values of K-factors and calculate trial compositions of equilibrium gas and liquid. Only the
final trial, with K-factors as given below is shown.
𝑧𝑗
∑ 𝑥 𝑗 =∑ 1+𝑛 (𝐾 −1)
𝑗 𝑗 𝑔 𝑗

This calculation requires trial and error, only the final trial with n g=0.4015 is shown.

Component Kj zj xj yj
C1 3.992 0.5301 0.2408 0.9613
n-C4 0.2413 0.1055 0.1517 0.0366
n-C10 0.0034 0.3644 0.6075 0.0021
1 1 1

Third, calculate the composition dependent coefficients necessary for z-factor calculations for both
liquid and gas.

𝑏=∑ 𝑦 𝑗 𝑏 𝑗
1
𝑎 𝑇 =∑ ∑ 𝑦 𝑖 𝑦 𝑗 ( 𝑎𝑇𝑖 𝑎𝑇𝑗 ) (1− 𝛿𝑖𝑗 )
2
Phase b A B
𝑖 𝑗 𝑗 Liquid 171,446 2.127 3.8766 0.31983
Gas 8,177 0.4619 0.1849 0.06945
𝑎𝑇 𝑝 𝑏𝑝
𝐴= 𝐵=
𝑅2𝑇 2 𝑅𝑇 17
Fourth, calculate z-factors of liquid and gas:

𝑧 3 − (1 − 𝐵 ) 𝑧 2+ ( 𝐴 − 2 𝐵 − 3 𝐵2 ) 𝑧 − ( 𝐴𝐵 − 𝐵2 − 𝐵3 ) =0

𝑧 𝐿 =0.3922 𝑎𝑛𝑑 𝑧 𝑔 =0.9051

Fifth, calculate the composition dependent coefficients necessary for calculating fugacity coefficients for
both liquid and gas

[ ]
1
1 𝑏𝑗
𝐴′ 𝑗 = 2 𝑎1/𝑇𝑗2 ∑ 𝑦 𝑖 𝑎𝑇𝑖
2
(1− 𝛿𝑖𝑗 ) 𝐵 ′ 𝑗=
𝑎𝑇 𝑙
𝑏

Liquid Gas
Component
C1 0.38893 0.20204 1.844 0.93042
n-C4 1.22127 0.54559 5.5014 2.51253
n-C10 2.83309 1.42979 12.5445 6.58435

18
Sixt, calculate the fugacity coefficients of the components of liquid and gas.

[ ( )
]
1
2
𝐴 𝑧 + 2 +1 𝐵
′
𝐼𝑛 𝜙 𝑗 =− 𝐼𝑛 ( 𝑧 − 𝐵 ) + ( 𝑧 − 1 ) 𝐵 𝑗 − ( 𝐴′ 𝑗 − 𝐵′ 𝑗 ) 𝐼𝑛
𝑧 − (2 −1) 𝐵
1.5
2 𝐵 1
2

Component
C1 3.67552 0.92065
n-C4 0.12878 0.53373
n-C10 0.000699 0.206

Seventh, calculate the K-factors of the components and the error functions.
2
𝜙 𝐿𝑗 ( 𝐾 𝑇𝑗 − 𝐾 𝐶𝑗 )
𝐾 𝑗= 𝜖 𝑗=
𝜙𝑔𝑗 𝑇
𝐾𝑗𝐾𝑗
𝐶

Component
C1 3.992 0
n-C4 0.2413 0
n-C10 0.0034 0
0

19
The sum of the error functions is less than a tolerance of 0.001, so the set of trial values of K-factors was correct and
the calculated values of liquid and gas compositions are correct. Compare results with experimental data.
Calculated Experimental
Component
C1 0.2408 0.9613 0.242 0.963
n-C4 0.1517 0.0366 0.152 0.036
n-C10 0.6075 0.0021 0.606 0.0021
1 1 1 1.0011

Also, the molar volumes and densities can be calculated

𝑝𝑀
𝑧𝑅𝑇 𝜌=
𝑧𝑅𝑇
𝑉 𝑀=
𝑝

Z Ma
Phase fraction cuft/lbmole lb/lbmole lb/cuft
Liquid 0.3922 2.61 99.12 38
Gas 0.9051 6.02 17.84 2.96

20
Equilibrium Ratio:

Equilibrium Ratio for Ideal Gases

In a multicomponent system, the equilibrium ratio of a given component is defined as the ratio of the mole fraction of
the component in the gas phase, to the mole fraction of the component in the liquid phase .
𝑦𝑖
𝐾 𝑖=
𝑥𝑖
Raoult’s and Dalton’s laws:
pi = x i p vi
where pi = partial pressure of a component i, psia
x i 𝜌 vi = y i p
pvi = vapor pressure of component i, psia
xi = mole fraction of component i in the liquid phase y i 𝑝 vi
= =Ki
xi 𝑝
Dalton’s law:

where p = total system pressure, psia.

Equilibrium Ratio for Ideal Gases (2)

𝑛=𝑛 𝐿 +𝑛𝑉 𝑧 𝑖 𝑛=𝑥𝑖 𝑛 𝐿 + 𝑦 𝑖 𝑛𝑉 𝑥𝑖 𝑛 𝐿 + 𝑦 𝑖 𝑛𝑉 =𝑧 𝑖 𝑥𝑖 𝑛 𝐿 + ( 𝑥𝑖 𝐾 𝑖 ) 𝑛𝑉 = 𝑧 𝑖

𝑧𝑖
𝑛 𝐿 +𝑛 𝑉 =1 𝑦 𝑖 𝑝 𝑣𝑖
= =𝐾 𝑖
𝑥𝑖 =
𝑛 𝐿 +𝑛𝑉 𝐾 𝑖
𝑥𝑖 𝑝 𝑧𝑖 𝐾 𝑖
𝑦 𝑖= =𝑥 𝑖 𝐾 𝑖
𝑛 𝐿 +𝑛 𝑉 𝐾 𝑖

𝑧𝑖
∑ 𝑥𝑖 =1∑ 𝑥𝑖 =∑ =1 𝑧𝑖 𝐾 𝑖 𝑧𝑖
𝑖 𝑛 𝐿 + 𝑛𝑉 𝐾 𝑖
𝑖 𝑖
∑ 𝑛 +𝑛 𝐾 − ∑ 𝑛 +𝑛 𝐾 =0
∑ 𝑦 𝑖 =1 𝑧 𝑖 𝐾𝑖
∑ 𝑦 𝑖 =∑ 𝑛 +𝑛 𝐾 =1
𝑖 𝐿 𝑉 𝑖 𝑖 𝐿 𝑉 𝑖
𝑖

∑ ¿¿¿ 𝑓 (𝑛 𝑉 )=∑ ¿ ¿ ¿
𝑖 𝑖 𝐿 𝑉 𝑖

𝑖 𝑖
= mole fraction of component in the entire hydrocarbon mixture
n = total number of moles of the hydrocarbon mixture, lb-mol
= total number of moles in the liquid phase
= total number of moles in the vapor (gas) phase
FLASH CALCULATIONS
Flash calculations are an integral part of all reservoir and process engineering calculations. They are
required whenever it is desirable to know the amounts (in moles) of hydrocarbon liquid and gas coexisting
in a reservoir or a vessel at a given pressure and temperature. These calculations are also performed to
determine the composition of the existing hydrocarbon phases.

• Moles of the gas phase nv

• Moles of the liquid phase nL
• Composition of the liquid phase xi
• Composition of the gas phase yi
Flash calculation steps:

Step 1. Calculation of nv using the Newton-Raphson iteration

n V = A /( A − B )
Assume any arbitrary value of nv between 0 and 1,
e.g., nv = 0.5. A good assumed value may be 𝐴=∑ [ 𝑧 𝑖 ( 𝐾 𝑖 − 1 ) ]
calculated from the following relationship, providing 𝑖

𝐵=∑ [ 𝑧 𝑖 ( 𝐾 𝑖 − 1 ) / 𝐾 𝑖 ]
that the values of the equilibrium ratios are accurate:

𝑖
Evaluate the function f(nv) as given by following Equation using the assumed

𝑓 (𝑛 𝑉 )=∑ ¿ ¿ ¿
value of nv.

𝑖
If the absolute value of the function f(nv) is smaller than a preset tolerance, e.g.,
, then the assumed value of nv is the desired solution.
If the absolute value of f(nv) is greater than the preset tolerance, then a new
value of nv is calculated from the following expression:

[ ]
2
with: 𝑧 𝑖 ( 𝐾 𝑖 −1 )
𝑓 ′=− ∑ 2
𝑖 [ 𝑛𝑉 ( 𝐾 𝑖 −1)+1 ]
Step 2. Calculation of nL: Calculate the number of moles of the liquid phase from
Equation
𝑛 𝐿 =1− 𝑛𝑉
Step 3. Calculation of xi: Calculate the composition of the liquid phase by applying
Equation
𝑧𝑖
𝑥𝑖 =
𝑛 𝐿 +𝑛𝑉 𝐾 𝑖
Step 4. Calculation of yi: Determine the composition of the gas phase from
Equation

𝑧𝑖 𝐾 𝑖
𝑦 𝑖= =𝑥 𝑖 𝐾 𝑖
𝑛 𝐿 +𝑛 𝑉 𝐾 𝑖
Example

A hydrocarbon mixture with the following overall composition is flashed in a

separator at 50 psia and 100°F.
Component
C3 0.20
i-C4 0.10
n-C4 0.10
i-C5 0.20
n-C5 0.20
C6 0.20

Assuming an ideal solution behavior, perform flash calculations and find the
fraction of each component in bot vapor and liquid phases.
Solution

Step 1. Determine the vapor pressure for the Cox chart and calculate the equilibrium
ratios Component at 100 =/50
C3 0.20 190 3.80
i-C4 0.10 72.2 1.444
n-C4 0.10 51.6 1.032
i-C5 0.20 20.44 0.4088
n-C5 0.20 15.57 0.3144
C6 0.20 4.956 0.09912
Step 2. Find nv using the Newton-Raphson method
Iteration nv f(nv)
0 0.08196579 3.073 E-02
1 0.1079687 8.894 E-04
2 0.1086363 7.60 E-07
3 0.1086368 1.49 E-08
4 0.1086368 0
Step 3. Solve for nL:

𝑛 𝐿 =1− 𝑛𝑉
𝑛 𝐿 =1− 0.10866368=0.8913631

Step 4. Solve for xi and yi:

=/
Component (0.8914+0.1086 =
)
C3 0.20 3.80 0.1534 0.5829
i-C4 0.10 1.444 0.0954 0.1378
n-C4 0.10 1.032 0.0997 0.1029
i-C5 0.20 0.4088 0.2137 0.0874
n-C5 0.20 0.3114 0.2162 0.0673
C6 0.20 0.09912 0.2216 0.0220
EQUILIBRIUM RATIOS FOR REAL SOLUTIONS

The equilibrium ratios, which indicate the partitioning of each component between
the liquid phase and gas phase proved to be inadequate because of the basic
assumptions behind Equation:

• The vapor phase is an ideal gas as described by Dalton’s law

• The liquid phase is an ideal solution as described by Raoult’s law

The above combination of assumptions is unrealistic and results in inaccurate

predictions of equilibrium ratios at high pressures.

¿
Calculation of the equilibrium ratios for real solutions

• Wilson’s correlation
• Standing’s correlation
Wilson’s Correlation for estimating K values of the real mixture of
hydrocarbon

Wilson (1968) proposed a simplified thermodynamic expression for estimating K

values. The proposed expression has the following form:

𝐾 𝑖=
𝑝 𝑐𝑖
𝑝 [
exp 5.37(1+ 𝜔𝑖 ) 1−(𝑇 𝑐𝑖
𝑇 )]
where pci = critical pressure of component i, psia
p = system pressure, psia
Tci = critical temperature of component i, °R
T = system temperature, °R
ωi = acentric factor of component i
Standing Correlation for estimating K values of the real mixture of hydrocarbon

at pressures of less than 1,000 psia and temperatures below 200°F.

log ( 𝐾 𝑖 𝑝)=𝑎+ 𝑐 𝐹 𝑖
1 𝑎+𝑐 𝐹
→ 𝐾 𝑖 = 10 𝑖

¿
𝐹 𝑖= ¿ ¿
where Fi = component characterization factor
Tbi = normal boiling point of component i, °R
Example

A hydrocarbon mixture with the following composition is flashed at 1000 psia

and 150°F.
Component
0.009
0.003
0.535
0.115
0.088
0.023
0.023
0.015
0.015
0.015
0.159

If the molecular weight and specific gravity of C7+ are 150.0 and 0.78,
respectively, calculate the equilibrium ratios using Wilson’s correlation
 Solution

Step 1. Calculate the critical pressure, critical temperature, and acentric factor of C7+
by using the characterization method of Riazi and Daubert

𝜃=𝑎 ( 𝑀 )𝑏 𝛾𝑐 exp [ 𝑑(𝑀 )+𝑒𝛾 + 𝑓 (𝑀)𝛾 ]

a b c d e f
, 544.4 0.2998 1.0555 -1.3478 -0.61641 0.0
, psia 4.5203 -0.9063 1.6015 -1.8078 -0.3084 0.0
, ft3/lb 1.206 0.20378 -1.3036 -2.657 0.5287 2.6012
, 6.77857 0.401673 -1.58262 3.77409 2.984036 -4.25288

𝜔= 3 ¿ ¿
𝑇 𝑐 =1139.4 ° 𝑅 , 𝑝𝑐 =320.3 𝑝𝑠𝑖𝑎 , 𝜔=0.5067
Step 2. Apply Wilson’s Equation

𝐾 𝑖=
𝑝 𝑐𝑖
𝑝 [ (
exp 5.37 ( 1+ 𝜔𝑖 ) 1 −
𝑇 𝑐𝑖
𝑇 )]
Component psia psia
0.009 547.9 0.225 2.0923
0.003 227.6 0.040 16.343
0.535 343.37 0.0104 7.155
0.115 343.37 0.0986 1.236
0.088 666.01 0.1542 0.349
0.023 734.98 0.1848 0.144
0.023 765.65 0.2010 0.106
0.015 829.1 0.2223 0.046
0.015 845.7 0.2539 0.036
0.015 913.7 0.3007 0.013
0.159 1139.4 0.5069 0.00029
Equilibrium ratios can also be used to calculate the following parameters:

• Dew-Point Pressure
• Bubble-Point Pressure
Dew-Point Pressure
The dew-point pressure pd of a hydrocarbon system is defined as the pressure at which
an infinitesimal quantity of liquid is in equilibrium with a large quantity of gas.

𝑛 𝐿 =0
where zi = total composition of the system under
𝑛𝑉 =1 𝑧𝑖 consideration.
∑
[ ]
𝑧𝑖
∑ 𝑥 𝑖 =∑ 𝑛 +𝑛 𝐾 =1 𝑖 𝐾𝑖 ∑
𝑧𝑖
=1
𝑖 𝑖 𝐿 𝑉 𝑖 𝑖 𝑝 𝑐𝑖
𝑝𝑑 [
exp 5.37 ( 1+ 𝜔𝑖 ) 1 −
𝑇 (
𝑇 𝑐𝑖
)]
Wilson’s equation Solving for pd yields:
𝑝 𝑐𝑖
[ (
exp 5.37 ( 1+𝜔 𝑖 ) 1−
𝑇 𝑐𝑖
)] 𝑝𝑑=
1

[ ]
𝑝 𝑇 𝑧𝑖
∑
𝑖

[ (
𝑝 𝑐𝑖 exp 5.37 ( 1+ 𝜔 𝑖 ) 1−
𝑇 𝑐𝑖
𝑇 )]
Bubble point pressure calculation
At the bubble-point, pb, the hydrocarbon system is essentially liquid, except for an
infinitesimal amount of vapor. For a total of 1 lb-mol of the hydrocarbon mixture,
the following conditions are applied at the bubble point pressure:

𝑛 𝐿 =1
∑ 𝑧 𝑖 𝐾 𝑖 =1
𝑖

[ ( )]
𝑛𝑉 =0 𝑇 𝑐𝑖

[ )]
𝑝 𝑏 =∑ (𝑧𝑖 𝑝 𝑐𝑖 exp 5.37 ( 1+𝜔𝑖 ) 1 − )
𝑝 𝑐𝑖
( 𝑇
𝑥𝑖 = 𝑧 𝑖
∑ (𝑧 𝑖 𝑝𝑏
exp 5.37 ( 1+𝜔𝑖 ) 1 − 𝑐𝑖 ) =1
𝑇
𝑖 𝑇
𝑖

Wilson’s equation
List of References (Harvard format):

• McCain, W., 1990, Properties of Petroleum Fluids, Elsevier

• Danesh, A., 1998, PVT and Phase Behaviour Of Petroleum Reservoir Fluids
• Ahmed, T., 2013. Equations of state and PVT analysis. Elsevier.
• Ahmed, T., 2006. Reservoir engineering handbook. Gulf Professional Publishing.

Lecturer Name, PhD Page 39 www.abdn.ac.uk