ENM200 Subsurface

Reservoir Engineering: Fluid Properties

Compressibility of Gases
Dr Ted Mason

Robert Gordon University

Ideal Gas Law

pV = nRT
where
p
V
T
n
R

(1)

pressure (absolute)
volume
temperature (absolute)
number of moles of gas
gas constant for 1 mole
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Ideal Gases
Values of R in the common unit systems are:
pressure volume temperature

kN/m2

m3

8.314 kJ/kmol K

atm

cm3

82.06 cm3 atm/mol K

psia

ft3

10.73 psia ft3/lb mol R

lb/ft2

ft3

1545 ft lb/lb mol R

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Ideal Gases
Volumes occupied by 1 mole of an ideal
gas under the standard conditions of 0C
and 1 atm (1.0133bar) are:
Molar unit:

Volume at 0C and 1 atm:

1 mol (i.e. g-mol)

22.41 litres

1 kmol

22.41 m3

1 lb-mol

359.0 ft3
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Ideal Gases
1 mole of a substance is the quantity of

substance having a mass equal to the molar

mass in grams.
In the SI system of units the kmol i.e. kilomole,
having a mass equal to the molar mass in kg
is used. In Imperial units the lb-mol, having a
mass equal to the molar mass in lb, is used.
To avoid any risk of confusion the mole is
sometimes written g-mol to emphasise that it is
based on the gram as the mass unit.
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Ideal Gases
As an approximate rule, the ideal gas law will
give results within 1% for:

The diatomic gases such as air, oxygen, nitrogen,

hydrogen under conditions where the volume of 1
kmol is greater than 5m3;
The more complex gases such as carbon dioxide,
ammonia and lighter hydrocarbons under conditions
where the volume of 1 kmol is greater than 20m3.

The ideal gas law is the simplest example of an

equation of state (or EOS) - that is, a
relationship between the pressure, volume and
temperature for a given quantity of gas.

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Real Gases

For real gases, we define a compressibility

factor, z (also called the gas deviation
factor), which indicates the extent of
deviation from ideal behaviour by writing

pV = znRT

(2)

Or alternatively

pV
z=
nRT
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(3)
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Real Gases
For ideal gas behaviour z = 1.0. For all gases z approaches
unity when the pressure is low, as seen from Fig. 1 which
gives plots of z versus p at constant temperature for several
gases. Fig. 2 gives curves of z versus p for methane.
2.0
z

N2
CH4

H2

-70C
20C

2.0
z

200C

NH3
1.0

1.0
0C

00

400

800

1200
Pressure (atm)

Fig 1. Plots of z vs. p at constant T

METHANE

00

Fig 2.

400

800

1200
Pressure (atm)

Plots of z vs. p for methane at

several temperatures
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Real Gases
If we have a series of curves such as those in Fig. 2 for
the gas we are dealing with, we can obtain the value of z
for the required conditions of temperature and pressure
and so calculate V. The gas density, , can then be found
from:

m nM
=
=
V
V
where

(4)

m = mass of gas; and

M = relative molar mass (molecular weight).

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Real Gases
Charts similar to Fig. 2. are available for methane

and for natural gas of various specific gravities.

However, such charts are not generally available
for gas mixtures, and then it is necessary to make
use of an important principle based on a
suggestion of van der Waals (in 1873) now usually
called the Principle of Corresponding States.
In order to make use of this principle it is necessary
to know the critical properties of the gas
concerned. Consider a typical pressure-volume
diagram for a pure fluid, as shown in Fig. 3.
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Fig 3. Pressure-Volume
Diagram for a Pure Substance
Pressure
Critical
Point
Critical
Isotherm

LIQUID
LIQUID
+
VAPOUR

GAS

(TWO-PHASE
REGION)

Isotherms
VAPOUR

Saturated Liquid Line

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Saturated
Vapour Line

Temperature
Increasing

Volume
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Critical Properties
The critical point lies at the maximum of the
saturation line, and the isotherm passing through
this point (corresponding to the critical
temperature, TC) has zero slope there.
The co-ordinates of the critical point on the p-V
diagram are the critical pressure, pC, and the
critical volume, VC (Since the volume depends on
the quantity of fluid concerned, VC is normally
given for 1 mole of fluid).

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Reduced Properties
At the critical point the liquid and the vapour have identical

properties. At temperatures above the critical temperature,

a pure gas cannot be liquefied by the application of
pressure, however great.
The reduced properties of the fluid are defined as follows:
p
pc

Reduced pressure

pR =

Reduced volume

V
VR =
Vc

(6)

Reduced temperature

T
TR =
Tc

(7)

(5)

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Principle of Corresponding States

The Principle of Corresponding States proposes that the

equation of state expressed in terms of reduced properties

is the same for all gases and gas mixtures.
Experimental data on the properties of gases shows that
the principle of corresponding states describes quite
closely the actual behaviour of most gases and gas
mixtures over a wide range of conditions. A sensitive test
is the value of zC, the compressibility factor at the critical
point:

p C VC
zC =
RTC

(8)

(n = 1, since VC is taken for 1 mole of fluid)

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Principle of Corresponding States

If the principle of corresponding states is valid,

zC should have the same value for all gases. In

practice, it is found that most gases have zC
values in the range 0.26 to 0.29, although a few
have exceptionally low values (e.g. 0.200 for
acetic acid) or exceptionally high values (e.g.
0.480 for nitrogen dioxide).
The principle of corresponding states can be
expressed mathematically in the form:-

VR = f (p R , TR )

(9)
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Compressibility Chart
If both sides are multiplied by pR / TR, it follows that:

z
= g (p R , TR )
zC

(10)

i.e. the ratio z/zC should be the same function of pR and TR for all
fluids, according to the principle of corresponding states. If we choose
a suitable mean value for zC, this means that a single chart of z versus
pR with TR as a parameter will predict z with reasonable accuracy for a
large number of gases and gas mixtures.

Such a chart was first published by Standing and Katz (1941), and is
referred to as the generalised compressibility chart. This is a twoparameter chart i.e. it gives z in terms of two parameters, pR and TR,
assuming that the average value zC = 0.27 applies to all gases.
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Compressibility
Chart
In using the generalised

compressibility chart, note

that accuracy falls off at
conditions in the
neighbourhood of the
critical point and at very
high pressures.
Also note that corrections
must be applied to the
chart for
(a) mixtures containing
significant amounts of
hydrogen sulphide and/or
carbon dioxide, and
(b) mixtures containing
significant amounts of
hydrogen or helium.
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Kays Rules for Mixtures

The generalised compressibility chart may be used to obtain z

for mixtures of gases provided that the pseudo-reduced

properties of the mixture are used.
Various methods are available for calculating these, but the
simplest and most widely adopted method is given by Kays
rules, which state that for a mixture of gases consisting of
components 1, 2, 3 etc. the pseudo-critical pressure pC' and the
pseudo-critical temperature Tc' are given by:
pc = y1pc1+ y2pc2+ y3pc3 +
Kays rules
Tc = y1Tc1+ y2Tc2+ y3Tc3 +
where:
pC1, pC2 etc. are the critical pressures of the pure components 1, 2
etc.;
TC1, TC2 etc. are the critical temperatures of the pure components 1,
2 etc.; and
y1, y2 etc. are the mole fractions of 1, 2 etc. in the mixture.
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Pseudo Reduced Properties

These pseudo-critical properties are then used to calculate the

pseudo-reduced pressure pR' and the pseudo-reduced temperature

TR' for the mixture:-

p
pR '=
pc '

(11)

T
TR ' =
Tc '

(12)

where p, T are respectively the pressure and temperature of the gas

mixture.
The pseudo-reduced properties pR' and TR' are then used with the
generalised compressibility chart to find z for the mixture in exactly
the same way as pR and TR are used for a pure gas.
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Gas Specific Gravity

Note that Kays rules cannot be used to predict the true

critical properties for the mixture, since they break down

at conditions in the neighbourhood of the critical point.
However, these rules give acceptable accuracy when
used with the generalised compressibility chart to
determine z values for gas mixtures.
Kays rules are the simplest example of the mixing rules
which are necessary when dealing with gas mixtures e.g.
when using EOS methods.
For natural gases, simplified charts are available giving
compressibility factors for gases of various specific
gravities. The specific gravity is defined as:

density of natural gas

specific gravity =
density of air at the same temperature and pressure
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Gas Specific Gravity

Since the specific gravity is nearly always quoted for pressures close to
atmospheric, we may assume ideal gas behaviour, and therefore:-

specific gravity =

molar mass
28.96

(13)

since the molar mass (or molecular weight) of air is 28.96.

For pure methane, the molar mass is 16.04, corresponding to a specific
gravity of 0.554. As the content of higher hydrocarbons in the gas
increases, the specific gravity increases correspondingly.
The GPSA Engineering Data Book gives charts showing the
compressibility factors for natural gases with specific gravities of 0.55,
0.60, 0.65, etc. which are useful if detailed composition data is not
available.
These charts should not be used if it is known that substantial amounts
of non-hydrocarbons (e.g. nitrogen, hydrogen sulphide, carbon dioxide)
are present.
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Limitations of the Method

The Standing and Katz chart does not cover reduced pressures

above the value of 15.0; the more recent chart of Nelson and
Obert (1954) goes up to reduced pressure values of 40. When
using these charts for natural gases a correction (e.g. that of
Wichert and Aziz) must be applied if acid gases (carbon dioxide
and/or hydrogen sulphide) are present to the extent of more than
5% by volume.
The Wichert and Aziz correction method is as follows, if :
A = sum of mole fractions of carbon dioxide and hydrogen
sulphide in the mixture
B = mole fraction of hydrogen sulphide in the mixture.

Then , the correction factor to be used in correcting the pseudo-critical

temperature and pressure values for the mixture is given by:

= 120 (A 0.9 A1.6 ) + 15 (B0.5 B 4.0 )

(14)
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Correction for Acid Gases

Note that is given by the above equation in R.

(Equation 14 for is also given in the form of a chart.)

The corrected pseudo-critical temperature and pressure
values, TC'', pC'' are then given by:

T=
C"

TC '

p c ' Tc "
pc "=
Tc ' + B(1 B)

(15)

(16)

where TC' and pC' are the uncorrected pseudo-critical

temperature and pressure values calculated for the
mixture (including the carbon dioxide and hydrogen
sulphide) in the standard manner using Kays rules.
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Correction for Acid Gases

The corrected pseudo-critical values obtained
are then used to calculate the pseudo-reduced
parameters and the z value obtained from the
Standing and Katz chart in the normal way.
In pipeline engineering calculations the
supercompressibility factor, FPV, is frequently
used. This is related to z as follows:

z=

(F )

(17)

PV

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Example
Analysis of a gas sample gave the following
composition data:Component

Vol %

methane
ethane
propane
isobutane
n-butane

72.5
12.1
8.9
4.0
2.5

Calculate:
a) the density of this gas under the reservoir
conditions of 7900psia and 217F,
b) the specific gravity of the gas.
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Solution
a) Obtain pc' and Tc' (using Kays rules) and
the average molar mass, Mav:Component

yi

pci (psia)

Tci (F)

Mi

C1

0.725

666.4

-116.7

16.04

C2

0.121

706.5

89.9

30.07

C3

0.089

616.0

206.1

44.10

iC4

0.040

527.9

274.5

58.12

nC4

0.025

550.6

305.6

58.12

yipci = pc' = 658.3psia

yiTci = Tc' = -36.8 + 460 = 423.2R
Then pR' = 7900 = 12.0
658.3

TR' =
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217 + 460
423.2

= 1.60
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From chart, z = 1.265 for reservoir conditions.

Also yiMi = 22.97 = mean molar mass, Mav
Now
pV = znRT
p
n
Therefore
= moles/unit vol = zRT
V

7900
lb mol/ft 3
1.265 10.73 (217 + 460)

= 0.860 lb-mol/ft3

= 0.860 22.97 lb/ft3

= 19.7 lb/ft3
Therefore density at reservoir conditions
= 19.7 lb/ft3
Then

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Solution
s.g. = 22.97 = 0.793
28.96

b)

Therefore

specific gravity of gas = 0.793

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