Slide 1 of 23

Real Gases

1
2 Real Gases.nb

Slide 2 of 23

Real Gases
Gases deviate from ideal behavior at low temperatures and high pressures.

The assumptions for ideal behavior are

Spherical Molecules Hhard elastic spheresL.

Non-interacting spheres.

Point particles Hzero volumeL.

The kinetic theory of gases shows that the form of the ideal
gas equation is correct. Non-ideal behavior indicates that
adjustments must be made to predict real gas behavior.

There are hundreds of different corrections to the ideal gas law.

2
 Slide 3 of 23

Real Gases Van der Waals' Equation

At low temperatures and high pressures, the assumptions do not hold.

The Van der Waals' equation attempts to correct for the failure of the
assumptions by adding an attractive term and a volume correction term.

The gas law.

PV=RT
becomes

a
HP + LHV - bL = R T
V2
The constants, a and b are different for each gas.
a
is the attractive term. It adds to pressure because the pressure
V2
would have to be higher to produce the volume.

b is the volume correction, which subtracts from the volume term

because the space available is reduced by the volume of the molecules
|

3
4 Real Gases.nb

Slide 4 of 23

Real Gases Van der Waals' Equation

For pressure in atmospheres, volume in liters, temperature in K, and
Liter atm
R = 0.08205 ,
mole K
a and b are shown for several gases
a b
2
Gas atm liter liter
CH4 2.253 0.04278
C2 H6 5.489 0.0638
C2 H4 4.471 0.05714
C2 H2 4.39 0.05136
CO2 3.592 0.04267

For one mole of CO2 at 273 K and 300 atm the volumes
given by each equation are

PV=RT
V = 0.0747 liter

a
HP + LH V - bL = R T
V2
V = 0.0599 liter

The difference is about 20%.

|

4
 Slide 5 of 23

Real Gases Van der Waals' Equation

Adding moles to the Van der Waals' Equation yields

n2 a
HP + LHV - n bL = n R T
V2
This equationis not well suited for engineering calculations.
There is no simple solution for V.
It also does not include a correction for
non-spherical molecules.

A simple modification of the ideal gas equation coupled with

the magic of dimensionless numbers and reduced variables
can be used to predict gas behavior in most situations.
|

5
6 Real Gases.nb

Slide 6 of 23

Real Gases Compressibility Factor

A generalization of the ideal gas law is given by

PV=znRT

In this equation, z is the compressibility factor or z-factor.

The value of z can range from less than one to greater than one.
A z-factor value of one yields ideal gas behavior.

Solving the equation for z yields

PV
z= Note: z is dimensionless.
nRT
Using experimental PVT data, charts of the z-factor versus
pressure may be generated.

Just like the Van der Waals' constants, there would be a

different chart for each gas.
|

6
 Slide 7 of 23

Real Gases Compressibility Factor

The z-factor pressure curve is similar to the plot shown below.

1.1

1.0

0.9
PV
RT

0.8
z=

0.7

0.6

0.5

0 2 4 6 8
Pressure

7
8 Real Gases.nb

Slide 8 of 23

Real Gases z-Factor Chart for Methane

$Aborted
|

8
 Slide 9 of 23

Real Gases Reduced Temperature and Pressure

Because each gas would have to have a z-factor chart, a method
had to be found to develop a single master chart.

It was discovered that by scaling the temperature and pressure

all of the curves would converge to a single line for each
scaled temperature.

Scaling is accomplished by dividing the temperature and pressure

by the critical values of temperature HTcL and pressure HPcL.
The resulting numbers are called the reduced temperature HTrL
and pressure HPrL.

Reduced Temperature and Pressure

T
Temperature HTrL = Tc

P
Pressure HPrL = Pc

9
10 Real Gases.nb

Slide 10 of 23

Real Gases Critical Values for Selected Gases

Because each gas would have to have a z-factor chart, a method
had to be found to develop a single master chart.

Plotting z on the y-axis and reduced pressure on the x-axis

results in a series of lines for each reduced pressure.

Component MWtCritical Temperature Critical

Pressure
F R psia
Methane CH4 16.04 -116 344 673
Ethane C2 H6 30.07 89 549 712
Propane C3 H8 44.09 206 666 617
n - Butane C4 H10 58.12 306 766 551
i - Butane C4 H10 58.12 272 732 544
n - Pentane C5 H12 72.15 386 846 485
i - Pentane C5 H12 72.15 370 830 483
n - Hexane C6 H14 86.17 454 914 435
n - Heptane C7 H16 100.2 512 972 397
n - Octane C8 H18 114.22 564 1024 362
Carbon Dioxide CO2 44.01 88 548 1073
Nitrogen N2 28.02 -233 227 492
Hydrogen Sulfide H2 S 34.08 213 673 1306

10
 Slide 11 of 23

Real Gases Reduced Temperature and Pressure

z-Factor Chart

11
12 Real Gases.nb

Slide 12 of 23

Real Gases
Example

Calculate the volume of 10 lb of ethane at 145F and 3000 psia.

First calculate the reduced temperature and pressure.

Tr = 605 R = 1.10603
547 R
3000 psia
Pr = = 4.45765
673 psia
Look up the z-factor 0.60
Solving
P V =z n R T for V V = z n R T
P
10 lbm lbmole
Calculate the number of moles n = = 0.333 lbmole
30 lbm
Substituting 0.433 ft3

12
 Slide 13 of 23

Real Gases Pseudo-Critical Temperature and

Pressure
Oilfield gases are rarely pure single component sytems.
Typically, they are composed of a mixture of
methane, ethane, and higher aliphatic hydrocarbons.

A mixture will not have the same critical pressure

and temperature as a pure component system.

Pseudo- reduced temperature and pressure must be used.

Care must be taken when working with gas mixtures

that contain gases other than hydrocarbons.

The pseudo-reduced T and P are calculated by

finding a pseudo-critical T and P for the mixture and
using these to calculate a pseudo-reduced T and P.

Ppr= yiPci and Tpr = yiTci

yi is the mole fraction of component i and

Pci is the critical pressure of component i
Tci is the critical temperature of component i
|

13
14 Real Gases.nb

Slide 14 of 23

Real Gases Pseudo-Critical Pressure Calculation

Example
Example: Find the pseudo-critical pressure for the following mixture.
Component of moles
Methane 2
Ethane 1
Propane 0.5

Solution

First find the mole fractions

ni
yi=
ni

y1 = 2 mole = 0.57
3.5 mole
y2 = 1 mole = 0.29
3.5 mole
y3 = 0.5 mole = 0.14
3.5 mole
Next sum yiPc
Ppc = 0.57 673 + 0.29 712 + 0.14 617
Ppc = 676.47

14
 Slide 15 of 23

Real Gases Approximating Pseudo-Critical

Properties
What do you do when you don't know the mole fractions?

There are several ways to estimate the pseudo-critical

properties from different physical properties.

If the gas gravity is known, the following charts can be used.

700 550

650 500
Ppc

600 Tpc 450

550 400

500 350
0.6 0.8 1.0 1.2 1.4 1.6 1.8 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Gas Specific Gravity Gas Specific Gravity

The equations for the curves are

Ppc = 760.198- 138.715 x

Tpc = 172.848+ 342.183 x - 70.8458 x2

15
16 Real Gases.nb

Slide 16 of 23

Real Gases Pseudo-Critical Properties of Gases

With non-Hydrocarbon Components
Non-hydrocarbon components in natural gas,
specifically CO2 and H2S, make it necessary to
apply a correction to the pseudo-critical properties.

The correction factor is termed e.

The correction is applied as follows

T'pc = Tpc- e

and

Ppc T'pc
P'pc =
Tpc + yHS H1 - yHS L e

16
 Slide 17 of 23

Real Gases Pseudo-Critical Properties of Gases

With non-Hydrocarbon Components
e is obtained from the following plot

17
18 Real Gases.nb

Slide 18 of 23

Real Gases Pseudo-Critical Properties of Gases

With non-Hydrocarbon Components
Rather than use the previous plot the value of e
can be calculated by

T'pc = Tpc- e

and

Ppc T'pc
P'pc =
Tpc + yHS H1 - yHS L e

e = 120HA0.9- A1.6L + 15 Hy0.5 4.0

HS - yHS L

where

A = yHS + yCO2

18
 Slide 19 of 23

Real Gases Calculation of Compressibility Factor

(z-Factor)
There are a number of different empirical correlations
that can be used to calculate the z-Factor. Each has
a range of reduced T and P over which they provide
decent estimates. The simplest is the Papay correlation.
It provides an average error of 4.8%, but it is easy to use

Ppr Ppr
z=1- H0.36748758 - 0.04188423 H LL
Tpr Tpr

Using Ppr = 1.375 and Tpr = 1.433 the Papay correlation produces
a value of the z-Factor of 0.686 which is low by about 20 %.

19
20 Real Gases.nb

Slide 20 of 23

Real Gases Calculation of Compressibility Factor

(z-Factor)
There are other methods that produce far better estimates
of the z-Factor, but they are implicit equations that
must be solved on a computer or high-level calculator.

The method of Hall and Yarborough is a good example.

In the equations below, Y is the reduced gas density.

0.06125 Ppr 1 2
Tpr -1.2 1 - 1
Tpr
z= e
Y
Solve the following to obtain Y
2
-1.2 1 - 1 2 3 4
-0.06125 Ppr 1 e + Y + Y + Y3 - Y
Tpr
Tpr H1 - YL
- H14.76 1 - 9.76 H 1 2
L + 4.58 H 1 L3L Y2
Tpr Tpr Tpr
2.18 + 2.82 1
+ H90.7 H 1 L - 242.2 H 1 L2 + 42.4 H 1 L3LY Tpr
=0
Tpr Tpr Tpr

In order to solve the above equations, some sort of a root

finding routing must be used. In Excel, Goal Seek will find
the answer quickly.
|

20
 Slide 21 of 23

Real Gases Calculation of Compressibility Factor

(z-Factor)
Using the same Ppr and Tpr as was used for the Papay
method, we get z = 0.844, which is as good as the value
can be read from the compressibility chart.

There is another method attribuitable to Dranchuk and

Abu-Kassem that produces almost identical results Hz = 0.845L.

The Hall Yarborough method should not be used for Tpr< 1

and the Dranchuk Abu-Kassem method is restricted to
0.2 b Ppr < 30 and 1 b Tpr b 3.0.

In reality, values of Tpr near one can cause numerical errors.

21
22 Real Gases.nb

Slide 22 of 23

Real Gases Compressibility of Natural Gas

For most liquids, compressibility is small, but
for gases it is not. Compressibility for a gas is defined as
Cg= - 1 H V LT
V p

Given that V = z n R T , the partial

P

derivative above becomes H V LT = n R TH 1 H z LT- Z2 L

P P P P
Substituting into the equation for Cg yields

Cg = 1 - 1 H z LT
p z P

For an ideal gas, z = 1 and H z LT = 0 so

P

Cg = 1 , which is a first approximation to Cg for real gases.

P
Replacing P with PprPpc yields

Cg = 1 - 1H z LT
Ppr Ppc z IPpr PpcM

Multiplying by Ppc and defining Cr = Cg Ppc yields

Cr = 1 - 1 H z LTpr
Ppr z IPprM

The partial derivative term is simply the slope of

the curve on the compressibility graph at constant Tpr.

22
 Slide 23 of 23

Summary
The ideal gas law holds for gases over a narrow range of conditions.
While there are many equations that can be used to
describe non-ideal behavior, for engineering purposes the
compressibility factor method HP V = z n R TL is adequate.
Reduction of the temperature and pressure by dividing by the
critical T and P values allow the use of a universal z-factor chart.
|

23