EQUATION OF STATE

(EOS)

PAB1033 RESERVOIR ROCK & FLUID
PROPERTIES
Acknowledgement:
Prof. Adrian Todd of Heriot Watt University
Lesson Learning Outcome
At the end of the session, students should be
able to:
Explain the governing laws of gas behaviour
Relate volume to pressure and temperature
using EOS

Introduction
A gas is a homogenous fluid that has low density
and viscosity. It has no definite volume but fills
completely the vessel in which it is placed in.
Gas behavior is very much different from liquid
behavior.For eg, gas is much affected by pressure
changes than liquid.
The system behaviour of gases is vital to
petroleum engineers and the law governing their
behaviour should be understood.
For simple gases these laws are straightforward
but the behaviour of actual hydrocarbon gases
particularly at the conditions occurring in the
reservoir are most complicated.
Ideal Gases
Assumptions
Volume of molecules are insignificant with
respect to the total volume of the gas.
There are no attractive or repulsive forces
between molecules or molecules and
container walls.
No internal energy loss when molecules
collide.
Ideal Gases
Boyles Law
1
V
P
o
or
PV cons tant =
T is constant
P = pressure, V = volume, T = temperature
Ideal Gases
Charles Law
V T o
or
V
cons tan t
T
=
P is constant
Pressure and temperature in both laws are in
absolute units
Absolute Units
Temperature
Kelvin K =
o
C + 273
Rankin
o
R =
o
F + 460
Pressure
Psia (lb/in
2
) = psi(lb/in
2
) + 14.7
Psia (lb/in
2
) = psf(lb/ft
2
) x 1/144
Ideal Gas Law
The Ideal Equation of State
Combining Boyles Law and Charles
Law gives an equation relating P,T & V
PV
cons tan t
T
=
Constant is termed R when quantity of gas is one mole
R is termed Universal Gas Constant
Universal Gas Constant
o
cu.ft.psia
R 10.73
l b.mol. R
=
o
cu.ft.psia
R 10.73
l b.mol. R
=
psfta
For n mole the equation becomes: PV = nRT
T = absolute temperature K or R
K = 273 + C and R = 460 + F
To find the volume occupied by a quantity of gas
when the conditions of temperature and pressure
are changed from state 1 to state 2
n = PV/ RT is a constant so that

The Equation of State For An Ideal
Gas
2
2 2
1
1 1
T
V P
T
V P
=
The Density Of An Ideal Gas
Since density is defined as the weight per unit
volume, the ideal gas law can be used to calculate
densities




RT
P MW
=
P
RT
V =
g = mass/ volume = m/V
Where g is the gas density
For 1 mole , m = MW (where MW = Molecular weight)

P
RT m
=
P
RT MW
=

Standard Conditions
Oil and gas occur under a whole range of
temperatures and pressures
Convenient to express volumes at a reference
condition.
Common practice to relate volumes to surface /
standard conditions (SC). 14.7 psia and 60
o
F

res res SC SC
res SC
P V P V
T T
=
res - reservoir conditions
SC - standard conditions
This equation assumes ideal behavior. This is
NOT the case for real reservoir gases
Mixture Of Ideal Gases
Petroleum engineering is concerned not with single
component gases but mixtures of a number of gases
Laws established over early years governing ideal
gas mixtures include:

Daltons Law

Amagats Law

Mixtures of Ideal Gases
Daltons Law of Partial Pressures
Total pressure is the sum of the partial pressures
A B C D
P P P P P ......... = + + + +
Therefore
A B C
RT RT RT
P n n n .....
V V V
= + + +
i.e.
j
RT
P n
V
=

Therefore
j j
j
P n
y
P n
= =
y
j
=mole fraction of j
th
component
Example of Daltons Law
Calculate the partial pressure exerted by methane
in the following gas when the gas is at a pressure
of 750 psia. Assume that the gas is a mixture of
ideal gases.

Component Composition
mole fraction
Methane 0.85
Ethane 0.10
Propane 0.05
Total 1.00
Solution
Determine the partial pressure of methane;

Partial Pres = Mole frac * Pres of Mixture
= (0.85)* 750 psia
= 638 psia
Amagats Law
States that the volume occupied by an ideal gas mixture
is equal to the sum of the volumes that the pure
components would occupy at the same temperature and
pressure.
Law of additive volumes.
A B C
V V V V .... = + + +
A B C
RT RT RT
V n n n ...
P P P
= + + +
i.e.
j
RT
V n
P
=

j j
j
V n
y
V n
= =
For ideal gas, volume fraction is equal to mole fraction
Apparent Molecular Weight
A mixture does not have a molecular weight.
It behaves as though it has a molecular
weight.
Called Apparent Molecular Weight, AMW
j j
AMW y MW =

MWj is the molecular weight of component j.

Example of Apparent MW
Dry air is a gas mixture consisting essentially of
nitrogen oxygen and small amounts of other gases.
Compute the apparent MW of air given its
approximate composition as below :
Component Composition
mole fraction
Nitrogen 0.78
Oxygen 0.21
Argon 0.01
Total 1.00
Solution Apparent MW ( M
a
)


M
a
= E (Mole Fraction * MW)
= (0.78 *28) + (0.21*32) + (0.01*40)
=28.96 lb/lb mole

Component MW of pure
gas
Composition
mole fraction
Nitrogen 28 0.78
Oxygen 32 0.21
Argon 40 0.01
Total 1.00
Specific Gravity of a Gas
The specific gravity of a gas is the ratio of the density of
the gas relative to that of dry air at the same conditions.
g
g
air

Assuming that the gas and air are ideal

g
g
air
air
M P
M
RT
M P
M
RT

g
=
Mg = AMW of mixture, Mair = AMW of air
=
Behaviour of Real Gases
At high pressures and temperatures the volume of
molecules are no longer negligible and attractive
forces are significant.
The ideal gas law is not too applicable to light
hydrocarbons and their associated fluids and it is
necessary to use a more refined equation.
There are two general methods of correcting the ideal
gas law equation:
By using a correction factor in the equation,
PV = znRT
By using another equation- of- state
Compressibility Factor For
Natural Gases
The correction factor z which is a function of the gas
composition, pressure and temperature is used to modify
the ideal gas law to: PV = znRT
The factor z is known as the compressibility factor and
the equation is known as the compressibility equation- of-
state or the compressibility equation
The compressibility factor is not a constant but varies with
changes in gas composition, temperature and pressure
and must be determine experimentally
Compressibility factor
To compare states, the equation now takes the form
res res SC SC
res res SC SC
P V P V
z T z T
=
Z is an expression of the actual volume to what the
ideal volume would be. i.e.
To
Z = V actual / V ideal
Compressibility factor
@ low pressure
V
actual
< V
ideal
@ high pressure
V
actual
> V
ideal
Gas acts like ideal gas
Law of Corresponding States
Law of corresponding states shows that the properties of pure
liquids and gases have the same value at the same reduced
temperature, Tr and reduced pressure, Pr.
r
c
T
T
T
= and
r
c
P
P
P
=


Tc and Pc are the critical temperature and critical pressure.

Presented as a function of T
r
(R) and P
r
(psia).
Methane
Ethane
Propane
Law of Corresponding States as
Applied to Mixtures
The law of corresponding states does not apply to
hydrocarbon reservoir fluids.
The law has been modified to be used for mixtures by
defining parameters

Pseudo critical temperature, Tpc
Pseudo critical pressure, Ppc
PC j cj
T y T =

and
PC j cj
P y P =

Tcj and Pcj are the critical temperatures and

pressures of component j.
Pseudo critical temperature, Tpc
and Pseudo critical pressure, Ppc .
These pseudo critical temperatures and pressures
are not the same as the real critical temperature and
pressure.
By definition they must lie between the extreme
values of the pure components making up the
mixture.
Gas A B C D Ppc Tpc
Component Mol. Wt Mol. Frac. Pc-psi Tc-
o
R
Methane 16.04 0.921 667 344 614.3 316.8
Ethane 30.07 0.059 708 550 41.8 32.5
Propane 44.09 0.02 616 666 12.3 13.3
Total 1 668.4 362.6
Pseudo critical pressure = 668 psia
Pseudo critical temperature = 363
o
R
PC j cj
T y T =

PC j cj
P y P =

Compressibility Factors for Natural

Gases
These are presented as a function of pseudoreduced
pressure, Ppr and pseudoreduced temperature, Tpr.
PR
PC
T
T
T
=
and
PR
PC
P
P
P
=
Compressibility
Factors for Natural
Gases (Standing &
Katz)
Ppc = 668 psia
Tpc = 362
o
R
Example:
Find z value for natural gas
at 3500 psia and 150
o
F
Ppr = 5.24 and Tpr = 1.68
z = 0.88
PR
PC
T
T
T
=
PR
PC
P
P
P
=
In many cases, composition of a natural gas is NOT AVAILABLE!
How to obtain pseudocritical properties i.e Tpc, Ppc ?
Use Standing Correlation
based on specific gravity of the gas (more easily
measured)

Standing Correlation for natural gas system
2
5 . 12 325 168
g g
Tpc + =
2
5 . 37 0 . 15 677
g g
Ppc + =
Standing Correlation for condensate gas system
2
5 . 71 332 187
g g
Tpc + =
2
1 . 11 7 . 51 706
g g
Ppc + =
Pseudocritical
Properties for
Natural Gases

Resource: McCain textbook pg. 119
Equation Of State
One of the difficulties of the compressibility
equation:
PV = ZnRT

To describe the behaviour of gases is that the
compressibility factor is not constant and
therefore mathematical manipulations cannot be
made directly but must be carried out through
graphical or numerical techniques

Rather than use this modified equation of real
gases
Impact of Nonhydrocarbons on Z
value
H
2
S and CO
2
have significant impact on z.
Wichert & Aziz have developed equation to enable
correction.
'
pc pc
T T = c
and
( )
'
pc pc
'
pc
pc H2S H2S
P T
P
T y 1 y
=
+ c
c obtained from Wichert & Aziz paper
Impact of Nonhydrocarbons on Z value
Resource: McCain textbook pg. 122
Many of the real gas equation of states have been
worked to calculate z for use in the above equation,
example
Van de Waals Equation (1873)
This most basic EOS, which correct for the volume of
the molecules and attractive and collision forces using
empirical constraints a and b, accurate only at low
pressure
(P + a/ V) (V b) = RT
Benedict- Webb- Rubin Equation (BWR), 1940
Redlich- Kwong Equation (1949)
P = [RT/ V b] - [ a(T) / V(V+ b)]
Where a and b are functions of temperature
Soave, Redlich Kwong equation
Peng Robinson Equation of State (1975)
P = RT/ V b - ac / [V (V + b) + b(V b)]
ac = 0.457235RT/ PC and b = 0.0778RTC / PC

Equation Of State
The Coefficient of Isothermal
Compressibility of Gas
A measure of the relative volume change of a
fluid or solid as a response to a pressure (or
mean stress) change.
Provides Instantaneous change of volume with P
at constant T
( )
T
g
P
V
V
T P C
(

c
c
=
1
,
Also with molar volume
and specific volume
Gas Compressibility
Volume changes of gas
Example
Viscosity of Gases
Viscosity is a measure of resistance to
flow.
Units: centipoise - gm./100 sec.cm.
Termed: dynamic viscoisty.
Divide by density.
Termed kinematic viscosity
Units: centistoke -cm
2
/100sec
Viscosity of Gases
Gas viscosity reduces as pressure decreases
At low pressures, increase in temperature increases viscosity.
At high pressures, increase in temperature decreases
viscosity.
Viscosity
of Gases
At low pressures
viscosity can be
obtained from
correlations.
Viscosity of pure
components at 1 atmos.
Viscosity of Gases
At low pressures viscosity can be obtained
from correlations.
Viscosity of
gases (MW)
at
atmospheric
pressure.
Viscosity of Gases
Carr presented a method to determine viscosity at higher
pressure and temperature.
Uses pseudo reduced temperature and pseudo reduced
pressure.
Viscosity Ratio
/
atm

Viscosity of Mixtures
A formulae which can be used for
mixtures
j j j
mix
j j
y M
y M

Other equations of state, EOS

The z factor is used to modify the ideal
EOS for real gas application.
PV=znRT
Rather than use this correction factor
other equations have been developed.
An irony is that many of these advanced
equations are used to generate z for
use in the PV=znRT equation.
Van der Waal EOS, 1873
( )
2
a
P V b RT
V
| |
+ =
|
\ .
Two corrective terms used to overcome limiting
assumptions of ideal gas equation.
Internal pressure or cohesion term a/V
2
.
Co-volume term b. Represents volume
occupied by one mole at infinite pressure.
Can also be written as
3 2
RT a ab
V b V V 0
P P P
| | | |
+ + =
| |
\ . \ .
Termed cubic equations of state
Van de Waal EOS
When written to solve for z becomes
( )
3 2
Z Z 1 B ZA AB 0 + + =
where
( )
2
aP
A
RT
=
and
bP
B
RT
=
Values for a and b are positive constants
for particular fluids.
Benedict-Webb-Rubin EOS,BWR-
1940
Van de Waals equation not able to represent
gas properties over wide range of T&P.
BWR equation developed for light HCs and
found application for thermodynamic
properties of natural gases
Constants which need to be determined by experiment
For mixtures mixing rules required.
o
o o
2
2 3 6 3 2 2 2
C
B RT A
RT bRt a a c
T
P 1 exp
V V V V V T V V

o
| | | |
= + + + + +
| |
\ . \ .
o o o
B , A , C , a, b, c, , and o
Redlich-Kwong EOS, 1949
Numerous equations with increasing
number of constants for specific pure
components.
More recently a move to cubic EOS.
( )
1/ 2
RT a
P
V b T V V b
=
+
The term a and b are functions of temperature
At the critical point
2 2
c c
c c
R T RT
a 0.42748 and b 0.08664
P P
= =
Soave,Redlich-Kwong EOS , SRK, 1972
Soave modified RK equation and
replaced a/T
0.5
term with a temperature
dependant term a
T
.
a
T
=a
c
o
( )
c
a RT
P
V b V V b
o
=
+
o is a non dimensionless temperature dependent term.
Value of 1 at critical temperature
o is from
( )
2
r
1 m 1 T
(
o = +

where
2
m 0.480 1.574 0.176 = + e e
e is the Pitzer
accentric factor from
tables
Peng Robinson EOS , PR,
1975
Peng and Robinson modified the
attractive term.
Predictions of liquid density are
improved.
( ) ( )
c
a RT
P
V b V V b b V b
o
=
( + +

2 2
c
c
c
R T
a 0.457235
P
=
and
c
c
RT
b 0.0778
P
=
o is the same as for the SRK equation, except w function is
different.
2
m 0.37464 1.54226 0.26992 = + e e
Widely Used EOS
SRK and PR equations are widely used
in the industry.
Used in simulation software to predict
behaviour in reservoirs, wells and
processing.
There are other EOS.
Reluctance to change because of
investment in associated parameters.
Application to Mixtures
With mixtures mixing rules required to
combine data from pure components.
For both SRK and PR equation
j j
j
b y b =
and ( )
i j i j ij
i j
a y y a a 1 k =

k
ij
are termed binary interaction coefficients.
They have NO physical property significance.
Each equation has its own binary interaction coefficients.