Reservoir Engineering

CGE566
Gas Behavior
March 2012

Lesson Learning Outcome

At the end of the session, students should be able to:
1.
2.

Explain the laws governing gas behavior

Relate Volume-Pressure-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 example, 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
between each other and the container walls.

Ideal Gases
Boyles Law
1
V
P

or

PV cons tan t

T is constant
P = pressure, V = volume, T = temperature

Ideal Gases
Charles Law

VT

or

V
cons tan t
T

P is constant
Pressure and temperature in both laws are in
absolute units

Absolute Units
Temperature
Kelvin K = oC + 273
Rankin oR = oF + 460

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

cu.ft.psia
R 10.73
l b.mol.o R

R 10.73

psfta

cu.ft.psia
l b.mol.o R

Equation of State For An Ideal Gas

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

P1V1 P2V2

T1
T2

The Density Of An Ideal Gas

Since density is defined as the mass per unit volume, the
ideal gas law can be used to calculate densities

RT
V
P

= mass/ volume = m/V

Where g is the gas density

For 1 mole , m = MW (where MW = Molecular weight)

MW P

RT

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 conditions.
14.7 psia and 60oF

Pres Vres PSC VSC

Tres
TSC

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

P PA PB PC PD .........
Therefore

RT
RT
RT
RT
P nA
nB
nC
..... i.e. P
nj

V
V
V
V
Therefore

Pj
P

nj
n

yj

yj =mole fraction of jth 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
Total

0.05
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.

V VA VB VC ....
RT
RT
RT
V nA
nB
nC
...
P
P
P

Vj
V

nj
n

RT
nj

i.e. V
P

yj

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

AMW y jMWj
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
Oxygen

0.78
0.21

Argon
Total

0.01
1.00

Solution Apparent MW ( Ma )
Component

MW of pure
gas

Composition
mole fraction

Nitrogen

28

0.78

Oxygen

32

0.21

Argon
Total

40

0.01
1.00

Ma = (Mole Fraction * MW)

= (0.78 *28) + (0.21*32) + (0.01*40)
=28.96 lb/lb mole

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
air

Assuming that the gas and air are ideal

Mg P
Mg
RT

g
MairP
Mair
RT
Mg = AMW of mixture, Mair = AMW of air

EQUATIONS OF STATE OR GAS LAWS

1) IDEAL GAS EQUATION OF STATE (EOS)
) An EOS seeks to describe specific PVT relationships of fluids
mathematically.
) There are hundreds of these equations ranging from those for
a specific pure compound to of multi component mixtures.
) The normal starting point for any discussion of the properties
of gases is the ideal gas equation of state, or ideal gas law.

 This equation is a combination of several

fundamental gas laws: Boyle's law, Charles
law and Avogadro's law.

Avogadro's law
Under the same conditions of P and T, equal V of ideal gases contain
the same number (n) of molecules.
As a result of this law:
There are 2.733xl026 molecules in one pound-mole of any gas.
One pound-mole of an ideal gas occupies 378.6 cuft at standard
pressure and
temperature.
Note that Standard temperature and pressure vary from country to
country, but
the most common values used are:
Tsc = 60 OF, Psc = 14.73 psia

 Although none of the hydrocarbon gases

behaves as ideal gas at reservoir conditions,
the behavior of most gases at low pressure
condition (close to atmospheric pressure) is
represented reasonably well by the ideal
gas law:

Example 1

Example 2

 At very low pressures, many gases exhibit

ideal behavior and the ideal gas law is valid.
At higher pressures, such as those found in
gas reservoirs, the ideal gas is not valid.
Many attempts have been made to modify the
ideal gas law so that it can be used to describe
real gases over a wide range ofP and T.
The van der Waals equation and the
Benedict-Webb-Rubin equation are examples
of such equations.
PV = ZnRT

 The z-factor, which is also referred to as the "gas

deviation factor", is the ratio of the volume of
real gas to the volume that would be occupied if
the gas behaved as an ideal gas under the same
conditions of P and T.
This factor varies with P, T, and composition, and
should be (preferably) determined
experimentally or from charts and/or empirical
correlations.

Van der Waals' Equation

Vander Waals added terms to the ideal-gas law in an
attempt to take into account forces between molecules as
well as volume of the molecules themselves.

 where V M is the molar volume and a and b are

constants characteristic of the gas.
The term b is a constant to correct for the volume
occupied by the molecules themselves.
The term V M is a correction factor to account for
the attraction between molecules as a
function of the average distance between them
(which is related to the molar volume).

How to use Vans equations

When an EOS such as the van der Waals
equation is applied to mixtures, either special
constants for a and b must be developed for each
mixture
or constants for each gas in the mixture must be
included in the equation along with adjustments
for the interaction between unlike gases.
The latter is the more common approach.

The Peng-Robinson EOS

where a and b are constants characteristic of

the fluid, aCT) is a functional relationship,
and V M is the molar volume. It is available
from the Gas Processors Suppliers Assn.
(GPSA).

The Peng-Robinson EOS

where a and b are constants characteristic of

the fluid, aCT) is a functional relationship,
and V M is the molar volume. It is available
from the Gas Processors Suppliers Assn.
(GPSA).

Equation Of State
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

SPECIFIC GRAVITY AND DENSITY OF

GAS
The density of gas is obtained by experimentally measuring
the specific gravity of the gas, and then using the following
relationship.

g = air
Since density is defmed as mass of gas per unit volume (mIV), the
real gas equation of state can also be used to calculate the z-factor:

GAS DEVIATION FACTOR

 With change in composition, the important engineering

properties of gases vary over awide range. Properties of
gases such as gas deviation factor (z), density (p ),
compressibility (c) and viscosity are important for:

calculating gas in place and well flow rates,

simulating the gas volume changes
analyzing reservoir pressure behavior, and
design of hydrocarbon-handling systems

THEOREM OF CORRESPONDING
STATES
"If the pressure relative to the critical pressure
and the temperature relative to the critical
temperature are the same for two different
substances, then the substances are in
corresponding states and any other property,
like the density relative to the critical
density, will be the same for both
substances"

 The principle of corresponding states has been

useful in correlating the properties of gases.
This principle was developed because
observers noticed that the behavior of pure
gases was qualitatively similar when compared
(on p-V plots, for instance) even though the
quantitative values of P and V were very
dissimilar.

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

Pres Vres PSC VSC

To
z res Tres zSC TSC
Z is an expression of the actual volume to what the
ideal volume would be. i.e.
Z = V actual / V ideal

Compressibility factor
Gas acts like ideal gas

@ low pressure
Vactual

< V ideal

@ high pressure
Vactual

> V ideal

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.

T
Tr
Tc

and

P
Pr
Pc

Tc and Pc are the critical temperature and critical pressure.

Presented as a function of Tr (R) and Pr (psia).

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

TPC y jTcj

and

PPC y jPcj

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.

PPC y jPcj

TPC y jTcj

Pseudo critical pressure = 668 psia

Pseudo critical temperature = 363 oR

Compressibility Factors for Natural

Gases

These are presented as a function of pseudoreduced

pressure, Ppr and pseudoreduced temperature, Tpr.

TPR

TPC

and

PPR

PPC

Compressibility
Factors for Natural
Gases (Standing &
Katz)
Example:
Find z value for natural gas
at 3500 psia and 150oF
Ppc = 668 psia
Tpc = 362 oR
Ppr = 5.24 and Tpr = 1.68
z = 0.88

Z Factor FROM SPECIFIC GRAVITY

AND DENSITY OF GAS
Step 1 - Calculate the apparent molecular weight
(MJ of the hydrocarbon components

Example 3

Solution

Z factor FOR DRY SWEET GAS

The C7+ fraction is negligible, and
The mole fraction of CO2, H2S, N2 and H20 are
negligible As stated earlier, the principle of
corresponding states suggests that:
pure gases have the same z-factor at the same values
P pr and T pr
mixtures of similar gases can also be correlated with
P pr and T pr

 Where the pseudo-reduced temperature and pressure are

defined as:

1 : Known gas composition

Method A : Ppc, Tpc and Z graph

Method B : Ppc, Tpc and Composition relationships

Step 4 : following equation could be used

2.Unknown gas composition

Range of application
If the gas is dry (I.e. no condensate is
formed) and contains less than 12% C02,
less than 3% N2, and no H2S, then Y g in
the above correlation is the separator gas
gravity or the gravity of the well stream
fluid

Z FACTOR OF DRY SOUR

GAS (FYI)
Standing graph was developed for impuriy < 15 %.

If the gas contains more than 15% of non hydrocarbon

components (yC02>12%, yN2>3%, and/or any H2S),
Ppc and Tpc of the TOTAL gas mixture (I.e.
hydrocarboncomponents plus impurities) and the gas
deviation factor z are calculated as follows:

 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

Tpc 168 325 g 12.5 g2

Ppc 677 15.0 g 37.5 g2
Standing Correlation for condensate gas system

Tpc 187 332 g 71.5

2
g

Ppc 706 51.7 g 11.1 g2

Question 1

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
H2S and CO2 have significant impact on z.
Wichert & Aziz have developed equation to enable
correction.

T Tpc
'
pc

and

Ppc'

Ppc Tpc'

Tpc y H2S 1 y H2S

obtained from Wichert & Aziz paper

Impact of Nonhydrocarbons on Z value

Resource: McCain textbook pg. 122

VISCOUSITY OF GASES
g

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 -cm2/100sec

Definition: Viscosity is a measure of the resistance to flow exerted by a fluid.

At high reservoir pressures, gas viscosity increases as the reservoir

pressure increases, and decreases with increasing temperature.
At low pressure (p<1000 psi) as shown in Fig. 2.10, gas viscosity
increases with increasing temperature >200F.
Measuring gas viscosities at reservoir conditions of pressure and
temperature is a difficult procedure. Correlations based on gas gravity
are commonly used in place of actual laboratory measurements.

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

mix

y
j

Mj
Mj

Viscosity of Gases
Standing Correlations

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Viscosity of Gases

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Viscosity of Gases

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Steps for determining viscosity

CKB for sour gas

Calculating Viscosity at reservoir P and T

Example 7
Calculate the viscosity of the gas at P=1000
psi and T=150 F with following properties:

Solution

Viscosity of Gases
Dempsey Correlation

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Viscosity of Gases

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Viscosity of Gases

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Viscosity of Gases

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Viscosity of Gases

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Viscosity of Gases

Note:

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Viscosity of Gases

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Viscosity of Gases

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Viscosity of Gases

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COMPRESSIBILITY OF
NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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COMPRESSIBILITY OF NATURAL GASES

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Z=0.78

Figure 2-1.
Standing and Katz
compressibility
factors chart
Page 39
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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 de Waal EOS, 1873

a
P 2 V b RT
V

Two corrective terms used to overcome limiting

assumptions of ideal gas equation.
Internal pressure or cohesion term a/V2.
Co-volume term b. Represents volume
occupied by one mole at infinite pressure.
Can also be written as

RT

V b V 2
P

ab
a
0
V
P
P

Termed cubic equations of state

Van de Waal EOS

When written to solve for z becomes

Z Z 1 B ZA AB 0
3

where

aP

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
RT
P

Bo RT A o
V2

Co

T 2 bRt a a c 1 exp

3
6
3 2
2
2
V
V
VT
V
V

Bo , A o , Co , a, b, c, , and
Constants which need to be determined by experiment
For mixtures mixing rules required.

Redlich-Kwong EOS, 1949

Numerous equations with increasing
number of constants for specific pure
components.
More recently a move to cubic EOS.
RT
a
P
1/ 2
V b T V V b

The term a and b are functions of temperature

At the critical point
R 2 Tc2
RT
a 0.42748
and b 0.08664 c
Pc
Pc

Soave,Redlich-Kwong EOS , SRK, 1972

Soave modified RK equation and replaced
a/T0.5 term with a temperature dependant
term aT.
aT =ac

RT
a c
P

V b V V b

is a non dimensionless temperature dependent term.

Value of 1 at critical temperature
is from

1 m 1 Tr

where m 0.480 1.574 0.1762

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.
RT
a c
P

V b V V b b V b
R 2 Tc2
a c 0.457235
Pc

and

RTc
b 0.0778
Pc

is the same as for the SRK equation, except w function is

different.

m 0.37464 1.54226 0.269922

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

b y jb j
j

and

a yi y j a i a j 1 k ij
i

kij are termed binary interaction coefficients.

They have NO physical property significance.
Each equation has its own binary interaction coefficients.