Heriot-Watt University

DEPARTMENT OF PETROLEUM ENGINEERING

Behaviour of Gases
Adrian C Todd

Introduction

A gas is a homogeneous fluid

No definite volume

Completely fills the vessel in which it is contained

Behaviour vital to petroleum engineers

Simple gas laws straightforward

Hydrocarbon gases at reservoir conditions are

more 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

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

Avogadros Law

Under the same conditions of temperature and pressure

equal volumes of all ideal gases contain the same number
of molecules.
That is; one molecular weight of any ideal gas occupies the
same volume as the molecular weight of another ideal gas.
2.73 x 1026 molecules/lb.mole of ideal gas
1 lb.mole of any ideal gas at 60oF and 14.7 psia. occupies
379.4 cu.ft.
1 gm.mole at 0oC and atmos. pressure occupies 22.4 litres

lb.mole

One lb.mol of methane CH4 = 16 lb.

One kg.mole of methane CH4 = 16 kg.

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

The Ideal Equation of State

For n moles equation becomes

PV = nRT
A useful equation to compare conditions at two
conditions 1 & 2

PV
n=
RT

therefore

P1V1 P2 V2

T1
T2

Density of an Ideal Gas

m
g weight / volume
V
g is the gas density
For 1 mole m = MW

MW= molecular weight

RT
V
P

MW.P
g
RT

Standard Conditions

Oil and gas occur under a whole range of

temperatures and pressures
Convenient to express volumes at a reference
condition.
Common practise 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 behaviour. This

is NOT the case for real reservoir gases

Mixtures of Ideal Gases

Petroleum gases are mixtures of gases - Daltons Law

and Amagats Law

Daltons Law of Partial Pressures

Total pressure is the sum of the partial pressures

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

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

V
V
V
V
Therefore

Pj
P

nj
n

yj

yj =mole fraction of jth component

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.
AMW for air = 28.97

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 Mg
RT
g

M air P M air 29
RT
Mg = AMW of mixture, Mair = AMW of air

Behaviour of Real Gases

Equations so far for ideal gases

At high pressures and temperatures the volume of molecules are no
longer negligible

and attractive forces are significant.

Ideal gas law is therefore NOT applicable to light hydrocarbons.

Necessary to use more refined equation.

Two general methods.

Using a correction factor in equation PV=nRT

By using another equation of state

Correction Factor for Natural Gases

A correction factor z , a function of gas

composition, pressure and temperature is
used to modify ideal equation.
z is the compressibility factor

PV znRT
Equation known as the
compressibility equation of state.
Z is not the compressibility

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

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.
The compressibility factor follows this law.
Presented as a function of Tr, and Pr.

Law of Corresponding States as

The
law of corresponding
Applied
to Mixtures 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
and
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.

Gas
Component
Methane
Ethane
Propane
Total

A
B
C
D
Ppc
Tpc
Mol. WghtMol. Frac. Pc-psi
Tc-oR
16.04
0.921
667
344
614.3
316.8
30.07
0.059
708
550
41.8
32.5
44.09
0.02
616
666
12.3
13.3
1
668.4
362.6

Pseudo critical pressure = 668.4 psia

Pseudo critical temperature = 362.6 oR

Real Critical Pressures and Temperatures

These are not

average values
based on mole
fractions.
Averaged on
weight fraction
basis would give a
more real value.

Critical pressure much greater

than critical points of pure
components.
Particularly when methane is
involved.

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
From previous exercise
Ppc=668psia
Tpc =362
Naturaland
Gases
& Katz)
Z (Standing
value for this
mixture at
3500psia and 150oF
Ppr = 5.24 and Tpr = 1.68
Z=0.88

Pseudocritical Properties for Natural

Can be calculated
Gases

from basic
composition.

If data not available

can use correlations.
Do not use
composition to
calculate gravity and
hence Ppc & Tpc.

Standard Conditions for Real Reservoir

Standard volumes are used to describe quanitities of
Gases

gas in the industry.

Standard cubic feet

Standard cubic metre.

Determined at standard temperature and pressure.

60oF(15.6oC) & 14.7psia (1 atmos)

It is useful to consider a mass of gas in terms of

standard volumes.

Gas Formation Volume Factor

We need a conversion factor to convert

volumes in the reservoir to those at surface
( standard) conditions.

Termed Formation Volume Factors.

Gases, Gas Formation Volume Factor, Bg.

Is the ratio of the volume occupied at reservoir

conditions to the volume of the same mass
occupied at standard conditions.

volume occupied at reservoir temperature and pressure

Bg
volume occupied at STP

Gas Formation Volume Factor

Definition
Gas Formation Volume Factor is the volume
in barrels (cubic metres) that one standard
cubic foot (standard cubic metre) of gas
willoccupy as free gas in the reservoir at the
prevailing reservoir pressure and
temperature.

Gas Formation Volume Factor

Units:

Bg - rb free gas / SCF gas

Bg - rm3 free gas / SCM gas

Gas Formation Volume Factor

Using equation of state

PV znRT

Pres Vres PSC VSC

and
z res Tres zSC TSC

PSC TR z R
VR
Bg

VSC PR TSC zSC

Z at standard
conditions = 1.0

Reciprocal of Bg often used to reduce risk of misplacing

decimal point as Bg is less than 0.01

1
volume at surface

E
Bg volume in formation
E is referred to as Expansion Factor

Gas Formation Volume Factor

VR
z
nRT
znRT
SC
SC
Bg
V

VR
SC
VSC
PSC
P
Z at standard conditions = 1.0
Therefore

T PSC cu.ft
Bg z
TSC P scf
Since Tsc=520 oR and Psc= 14.7 psia for most cases

zT res.bbl
Bg 0.00504
P scf

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

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
atmos

Viscosity of Mixtures

A formulae which can be used for mixtures

mix

y
j

Mj
Mj

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
2
V b V
P

ab
a
V 0
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

a c
RT
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.
a c
RT
P

V b V V b b V b
R 2Tc2
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.