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

Boyle’s Law

1
V or PV  cons tan t
P

T is constant

P = pressure, V = volume, T = temperature

Ideal Gases

Charles’ Law

V
VT or  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
 Avogadro’s 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 Boyle’s 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

cu.ft.psia
R  10.73
l b.mol.o R

psfta
The Ideal Equation of State
For n moles equation becomes

PV = nRT

A useful equation to compare conditions at two

conditions 1 & 2

PV P1V1 P2 V2
n= therefore 
RT 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 res - reservoir conditions

 SC - standard conditions
Tres TSC
This equation assumes ideal behaviour. This
is NOT the case for real reservoir gases
Mixtures of Ideal Gases

Petroleum gases are mixtures of gases - Dalton’s Law
and Amagat’s Law
Dalton’s 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
V
 nB
V
 nC
V
 ..... i.e. P 
V
 nj

Therefore Pj nj
  yj
P n
yj =mole fraction of jth component
 Amagat’s 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 RT
V  nA
P
 nB
P
 nC
P
 ... i.e. V 
P
 nj

Vj nj
  yj
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

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
g 
air
Assuming that the gas and air are ideal
Mg P
RT Mg Mg
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 P
Tr  and Pr 
Tc 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
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
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 A B C D Ppc Tpc
Component Mol. WghtMol. Frac. Pc-psi Tc-oR
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 = 668.4 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.

T P
TPR  and PPR 
TPC PPC
 Compressibility
Factors for
Natural Gases
(Standing & Katz)

From previous exercise

Ppc=668psia and Tpc =362 oR
Z value for this mixture at
3500psia and 150oF

Ppr = 5.24 and Tpr = 1.68

Z=0.88
Pseudocritical Properties for Natural
Gases

Can be calculated
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
Gases

Standard volumes are used to describe quanitities
of 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

Bg - rb free gas / SCF gas

Units:
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
VR PSC TR z R Z at standard
Bg   conditions = 1.0
VSC PR TSC zSC
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 znRT z nRT
Bg  VR  V  SC SC
VSC P
SC
PSC

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 j Mj
y j 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  a  ab
V b
3
V  V   0
 P  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 2

where A
aP
and bP
B
 RT 
2
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 HC’s and found
application for thermodynamic properties of natural
gases
Co
Bo RT  A o 
P
RT
 T 2  bRt  a  a  c 1    exp    
   2 
V V2 V3 V 6 V 3T 2  V 2   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

 
2
 is from   1  m 1  Tr 
 
 is the Pitzer
where m  0.480  1.574  0.1762 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 RTc
a c  0.457235 and b  0.0778
Pc Pc

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

different.

m  0.37464  1.54226  0.269922

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 and a   yi y j a i a j  1  k ij 
j i j

kij are termed binary interaction coefficients.

They have NO physical property significance.

Each equation has its own binary interaction coefficients.