Chapter two

Gas Properties
The ability to calculate the performance of a gas
producing system, including the reservoir and the
piping system, requires knowledge of many gas
properties at various, pressures and temperatures.
If the natural gas is in contact with liquids, such as
condensate or water, the effect of the liquids on gas
properties must be evaluated.
This presentation presents the best and most
widely used methods to perform the necessary
calculations. Some of the information presented will
be used only in reservoir calculations and some will
be used only in the piping system design.

IDEAL GASES

The understanding of the behavior of gases with

respect to pressure and temperature changes is
made clearer by first considering the behavior of
gases at conditions near standard conditions of
pressure and temperature; that is:
p = 14.7 psia = 101.325 kPa
T = 60F = 520R = 288.72K
At these conditions the gas is said to behave
ideally, and most of the early work with gases was
conducted at conditions approaching these
conditions.

Characteristics of ideal gas

(1) the volume occupied by the molecules is small
compared to the total gas volume;
(2) all molecular collisions are elastic; and
(3) there are no attractive or repulsive forces
among the molecules.
The basis for describing ideal gas behavior comes
from the combination of some of the so called gas
laws proposed by early experimenters.

Early Gas Laws

Boyle's Law. Boyle observed experimentally that
the volume of an ideal gas is inversely proportional
to the pressure for a given weight or mass of gas
when temperature is constant. This may be
expressed as:

Charles' Law. While working with gases at low

pressures, Charles observed that the volume
occupied by a fixed mass of gas is directly
proportional to its absolute temperature, or

 Avogadro's Law. Avogadro's Law states that under

the same conditions of temperature and pressure,
equal volumes of all ideal gases contain the same
number of molecules.
This is equivalent to the statement that at a given
temperature and pressure one molecular weight of
any ideal gas occupies the same volume as one
molecular weight of another ideal gas.
It has been shown that there are 2.73 x 1026
molecules/lb-mole of ideal gas and that one
molecular weight in pounds of any ideal gas at 60F
and 14.7 psia occupies a volume of 379.4 cu ft.

The Ideal Gas Law

The three gas laws described previously can be
combined to express a relationship among
pressure, volume, and temperature, called the
ideal gas law.
In order to combine Charles' Law and Boyle's Law
to describe the behavior of an ideal gas when both
temperature and pressure are changed, assume a
given mass of gas whose volume is V1 at pressure
pl and temperature Ti, and imagine the following
process through which the gas reaches volume V2
at pressure p2 and temperature T2:

 In the first step the pressure is changed from a

value of p1 to a value of p2 while temperature is
held constant. This causes the volume to change
from V1 to V. In Step 2, the pressure is maintained
constant at a value of p2, and the temperature is
changed from a value of T1 to a value of T2.
The change in volume of the gas during the first
step may be described through the use of Boyle's
Law since the quantity of gas and the temperature
are held constant. Thus

 where V represents the volume at pressure p2

and temperature T1. Charles' Law applies to the
change in the volume of gas during the second
step since the pressure and the quantity of gas
are maintained constant; therefore
Elimination of volume, V, between the two
equations :

Or

 Thus for a given quantity of gas, pV/T = a

constant. The constant is designated with the
symbol R when the quantity of gas is equal to
one molecular weight. That is,
where VM is the volume of one molecular
weight of the gas at p and T.
Therefore, the equation of state for one
molecular weight of any ideal gas is

 For n moles of ideal gas this equation becomes

where V is the total volume of n moles of gas at
temperature, T, and pressure, p. Since n is the
mass of gas divided by the molecular weight, the
equation can be written as
or, since m/V is the gas density,

 This expression is known by various names such as

the ideal gas law, the general gas law, or the perfect
gas law. This equation has limited practical value
since no known gas behaves as an ideal gas;
however, the equation does describe the behavior of
most real gases at low pressure and gives a basis for
developing equations of state which more adequately
describe the behavior of real gases at elevated
pressures.
The numerical value of the constant R depends on
the units used to express temperature, pressure, and
volume. As an example, suppose that pressure is
expressed in psia, volume in cubic feet, temperature
in degrees Ran-kin, and moles in pound moles.
Avogadro's Law states that 1 lb-mole of any ideal gas
occupies 379.4 cu ft at 60F and 14.7 psia. Therefore,

= 10.73 psia cu ft/lbmole R

Table 2-1 gives numerical values of R for various

systems of units.

Ideal Gas Mixtures

The previous treatment of the behavior of gases ap
plies only to single component gases. As the gas engi
neer rarely works with pure gases, the behavior of a
multi-component mixture of gases must be treated.
This requires the introduction of two additional ideal
gas laws.
Dalton's Law:
Dalton's Law states that each gas in a mixture of
gases exerts a pressure equal to that which it would
exert if it occupied the same volume as the total
mixture. This pressure is called the partial pressure.
The total pressure is the sum of the partial pressures.
This law is valid only when the mixture and each
component of the mixture obey the ideal gas law. It is
sometimes called the Law of Additive Pressures.

 partial pressure exerted by each component of the

gas mixture can be calculated using the ideal gas
law. Consider a mixture containing nA moles of
component A, nB moles of component B and nc
moles of component C. The partial pressure
exerted by each component of the gas mixture
may be determined with the ideal gas equation:
According to Dalton's Law, the total pressure is the
sum of the partial pressures

 It follows that the ratio of the partial pressure of

component j, pj, to the total pressure of the
mixture p is:

where yj is defined as the mole fraction of the jth

component in the gas mixture. Therefore, the
partial pressure of a component of a gas mixture is
the product of its mole fraction times the total
pressure.

 Amagat's Law:

Amagat's Law states that the total volume of a

gaseous mixture is the sum of the volumes that each
component would occupy at the given pressure and
temperature. The volumes occupied by the individual
components are known as partial volumes. This law is
correct only if the mixture and each of the
components obey the ideal gas law.
The partial volume occupied by each component of a
gas mixture consisting of nA moles of component A, nB
moles of component B, and so on, can be calculated
using the ideal gas law.

Thus, according to Amagat, the total volume is:

It follows that the ratio of the partial volume of

component j to the total volume of the mixture is:

This implies that for an ideal gas the volume fraction

is equal to the mole fraction.

Apparent Molecular Weight

Since a gas mixture is composed of molecules of

various sizes, it is not strictly correct to say that a
gas mixture has a molecular weight. However, a gas
mixture behaves as if it were a pure gas with a
definite molecular weight. This molecular weight is
known as an apparent molecular weight and is
defined as:

 The specific gravity of a gas is defined as the ratio of

the density of the gas to the density of dry air taken
at standard conditions of temperature and pressure.
Symbolically,

Assuming that the behavior of both the gas and air

may be represented by the ideal gas law, specific
gravity may be given as

 where Mair is the apparent molecular weight of air. If the

gas is a mixture, this equation becomes:

where Ma is the apparent molecular weight of the gas

mixture.
Example 2-4:
Calculate the gravity of a natural gas of the following
composition.

REAL GASES
Several assumptions were made in formulating
the equation of state for ideal gases. Since these
assumptions are not correct for gases at pressures
and temperatures that deviate from ideal or
standard conditions, corrections must be made to
account for the deviation from ideal behavior.
The most widely used correction method in the
petroleum industry is the gas compressibility
factor, more commonly called the Z-factor. It is
defined as the ratio of the actual volume occupied
by a mass of gas at some pressure and
temperature to the volume the gas would occupy
if it behaved ideally. That is,

 Therefore, the equation of state for any gas becomes

where, for an ideal gas, Z = 1.
The compressibility factor varies with changes in gas
composition, temperature, and pressure. It must be
determined experimentally. The results of experimental
determinations of compressibility factors are normally
given graphically and usually take the form shown in
Figure 2-1. The shape of the curve is consistent with
present knowledge of the behavior of gases; at very low
pressure the molecules are relatively far apart and the
conditions of ideal gas behavior are more likely to be
met. At low pressure the compressibility factor
approaches a value of 1.0, which would indicate that
ideal gas behavior does in fact occur.

Real Gas Mixtures

Compressibility factor charts are available for most
of the single component light hydrocarbon gases,
but in practice a single component gas is rarely
encountered. In order to get Z-factors for natural
gas mixtures, the law of corresponding states is
used. This law states that the ratio of the value of
any intensive property to the value of that property
at the critical state is related to the ratios of the
prevailing absolute temperature and pressure to the
critical temperature and pressure by the same
function for all similar substances. This means that
all pure gases have the same Z-factor at the same
values of reduced pressure and temperature, where
the reduced values are defined as

Fig. 2-2. Compressibility factors for methane.

Courtesy Gas Processors Suppliers Association.

Fig. 2-3. Compressibility factors for ethane.

Courtesy Gas Processors Suppliers Association.

Fig. 2-4. Compressibility factors for propane.

Courtesy Gas Processors Suppliers Association

Real Gas Mixtures

where Tc and pc are the critical temperature and

pressure for the gas, respectively. The values
must be in absolute units.
Example 2-6:
Calculate the density of ethane at 900 psia
and 110F. The critical properties, from
Table 2-2, are Tc = 550R, pc = 708 psia, M
= 30.1 Ibm/lb-mole.

Real Gas Mixtures

Assuming ideal behavior, the value calculated would be p

= 13.03 (.34) = 4.43 lbm/ft3.
It has been shown that the Law of Corresponding States
works better for gases of similar molecular characteristics.
This is fortunate since most of the gases that the petroleum
engineer deals with are composed of molecules of the
same class of organic compounds known as paraffin
hydrocarbons.

Real Gas Mixtures

The law of corresponding states has been extended

to cover mixtures of gases that are closely related
chemically. Since it is somewhat difficult to obtain
the critical point for multi-component mixtures,
the quantities of pseudo critical temperature and
pseudo critical pressure have been conceived.
These quantities are defined as
These pseudo critical quantities are used for
mixtures of gases in exactly the same manner as
the actual critical temperatures and critical
pressures are used for pure gases.

Real Gas Mixtures

Example 2-7:
Calculate the pseudo critical temperature and
pseudo critical pressure of the following natural
gas mixture. Use the critical constants given in
Table 2-2.

The compressibility factors for natural gases have been

correlated using pseudo critical properties and are pre
sented in Figures 2-6, 2-7, and 2-8.

Fig. 2-6. Compressibility factors for natural

gases. Courtesy Gas Processors Suppliers Association.

Fig. 2-7. Generalized plot of compressibility

factors at low reduced pressures. Courtesy Gas Processors
Suppliers Association.

Fig. 2-8. Compressibility factors for gases near

atmospheric pressure. Courtesy Gas Processors Suppliers
Association.

In some cases the composition of a gas will be given in weight or

mass percent rather than mole percent. In this event, the
composition must be first converted to mole fraction or
percent before the mixture properties can be calculated. The
following example illustrates this conversion.
Example 2-9:
A gas mixture consists of 50% d, 30% C2, and 20% C3 by
weight. Calculate the apparent molecular weight and specific
gravity of this mixture.

 In most cases the composition of a natural gas will be known

and the apparent molecular weight and critical properties can
be calculated as previously described. Occasionally, however,
only the gas gravity will be known. Also, it is very easy to
measure the gas gravity in the field. If the composition is
unknown, or if accuracy requirements do not justify the longer
calculations, Figure 2-9 can be used to estimate the pseudo
critical properties. The properties can also be calculated using
the following equations:

Fig. 2-9. Pseudo critical properties of natural

gases. Courtesy Gas Processors Suppliers Association.

Compressibility of Natural Gas

Gas compressibility is defined as:

Because the gas law of real gas gives:

viscosity

GAS FORMATION VOLUME FACTOR

Reservoir engineering and pipeline flow calculations require the
volumes at in situ conditions of pressure and temperature, and
there fore a convenient conversion factor from standard
conditions to in situ conditions is needed. This conversion factor
is called the gas formation volume factor and is defined as the
actual volume occupied by the gas at some pressure and
temperature divided by the volume that the gas would occupy at
standard conditions. That is,

CORRECTION FOR NONHYDROCARBON

IMPURITIES
Natural gases frequently contain materials other than
hydrocarbons, such as nitrogen (N2), carbon dioxide (C02), and
hydrogen sulfide (H2S). The presence of these impurities
affects the value obtained from the Z-factor chart.
A procedure for adjusting the critical properties of the gas was
proposed by Wichert and Aziz2 in 1970. The adjusted critical
properties are then used in calculating the reduced properties,
and the Z-factor is then obtained from Figure 2-6.
The procedure for obtaining the Z-factor for sour
gases is:
1-Determine ppc and Tpc for the gas using the gas
composition or Figure 2-9 and
2-Calculate the adjusted critical properties.

3. Calculate, the reduced properties using the corrected critical

properties.
4. Find Z from Figure 2-6 or using the correlation given in the
Appendix.

 Example:
A gas containing 2.87% C02 and 23.27% H2S has a critical
pressure of 822 psia and a critical temperature of 465R. Find
the gas compressibility factor, Z, for p = 1000 psia, T= 100F.
Solution:
B = 0.2327 A = 0.0287 + 0.2327 = 0.2614
= 120 [(0.2614) 0.9 - (0.2614)1.6] + 15 [(0.2327)0.5
- (0.2327)4]
= 29 oF

OTHER EQUATIONS OF STATE

One of the limitations in the use of the compressibility equation
to describe the behavior of gases is that the compressibility
factor is not constant, and therefore mathematical
manipulations cannot be made directly but must be
accomplished through graphical or numerical techniques.
Many equations of state have been proposed for
describing gas behavior and many modifications
and improvements have been made. Only two of
the most commonly used equations will be
described. These will be used later in the
calculation of phase behavior.

Benedict-Webb-Rubin Equation (BWR)

An earlier equation presented by Beattie and
Bridgeman3 was modified and resulted in an
equation with eight empirical constants.

The parameters Bo, Ao, Co, a, b, c, a, and are constants for

pure compounds and are functions of composition for mixtures.
The constants for pure compounds are given in Table 2-3.
These constants may be combined for use with mixtures of
gases according to the following mixture rules.

Redlich-Kwong Equation
(RK):
The Redlich-Kwong Equation4 involves only two empirical
constants as opposed to the eight required in the BWR equation.
The original RK equation is

To simplify the calculations with the RK equation, especially for

application to mixtures, other constants have been defined as

The Dehydration and

Sweetening of Natural Gas
Natural gas destined for the pipeline market must meet certain
requirements of water-vapor content and hydrogen sulfide content.
The water content is normally reduced to about 6 to 8 lb of water
per MMcf of gas. The hydrogen sulfide content of sour gases is
reduced to 0.1 to 0.25 grain per 100 cu ft to make them "sweet."
Processes are available for treating gases to prepare them for the
pipeline market and for eventual domestic or commercial
consumption.

DEHYDRATION OF NATURAL GAS

The dehydration of natural gas is the removal of the
water that is associated with natural gases in vapor
form. The natural gas industry has recognized that
dehydration is necessary to ensure smooth operation
of gas-transmission lines.

 Dehydration prevents the formation of gas hydrates

and reduces corrosion. Unless gases are dehydrated,
liquid water may condense in the pipelines and
accumulate at low points along the line, reducing the
flow capacity of the line. Several methods have been
developed to dehydrate gases on an industrial scale.
Familiarity with all the methods is necessary in
selecting the best and most economical method to
solve a given drying problem.
The methods of dehydration in current usage are
Adsorption
Absorption
Direct cooling
Compression followed by cooling
Chemical reaction

 Absorption
Adsorbents such as alumina, silica gel, and bauxite comprise the
desiceants used in adsorption processes. The absorption processes most
frequently used employ di- and triethylene glycol as desiceants. The last
three methods have minor usage and will be discussed briefly.
Dehydration by Cooling
The saturated-water content of natural gas decreases with increased
pressure or decreased temperature (Fig. 5-8). Thus, hot gases saturated
with water vapor may be partially dehydrated by direct cooling. Gases
subjected to compression are normally "after-cooled," and this cooling
may well remove water from the gas. Unless the cooling process reduces
the temperature to the lowest value that the gas will encounter at the
prevailing pressure, cooling does not prevent further condensation of
water.
The use of Joule-Thomson or expansion cooling in wellhead separators to
dehydrate natural gas is discussed in Chap. 13.