Physical Properties of Gas

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

2 Chapter 2
2.1 PHYSICAL PROPERTIES OF GAS
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.

The primary difference between a gas reservoir and an oil reservoir is the
difference in composition in which the hydrocarbon material occurs at the original
reservoir P and T:
• Oil reservoirs are usually a mixture in which heavier hydrocarbon
components (normally liquid at atmospheric temperature and pressure)
comprise the major fraction of the fluid.
• Gas reservoirs are a mixture in which the dominant constituents are lighter
components.
• Understanding how properties of oil and gas change with pressure and
temperature is undoubtedly the key to reservoir engineering and
production.

A PHASE IS DEFINED AS ANY homogeneous part of a system that is physically


distinct and separated from other parts of the system by definite boundaries.
• For example, ice, liquid water, and water vapor constitute three separate
phases of the pure substance H2O, because each is homogeneous and
physically distinct from the others; moreover, each is clearly defined by the
boundaries existing between them.
• Whether a substance exists in a solid, liquid, or gas phase is determined by
the temperature and pressure acting on the substance. It is known that ice
(solid phase) can be changed to water (liquid phase) by increasing its
temperature and, by further increasing the temperature, water changes to
steam (vapor phase). This change in phases is termed phase behavior.
• Hydrocarbon systems found in petroleum reservoirs are known to display
multiphase behavior over wide ranges of pressures and temperatures. The
most important phases that occur in petroleum reservoirs are a liquid phase,
such as crude oils or condensates, and a gas phase, such as natural gases.
• The conditions under which these phases exist are a matter of considerable
practical importance. The experimental or the mathematical determinations

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
of these conditions are conveniently expressed in different types of
diagrams, commonly called phase diagrams.

2.2 SOLUTION OR DISSOLVED GAS RESERVOIR


• Consider (as an example) a reservoir initially at pi= 3000 psia and Ti = 125 °F,
represented by point 1i on Fig. 1
• Because point 1i is in the single-phase region above the bubble point line and
Ti<TC the HYDROCARBON MIXTURE is in the liquid phase, i .e. an oil reservoir.
• This type of reservoir is referred to by several names: bubble point, dissolved
gas, undersaturated oil, depletion, solution gas drive, expansion, and internal
gas drive reservoir.
• As the pressure declines in the reservoir (due to oil production) at a
constant T, the bubble point will be reached (in Fig. 1 at point S where p =
2550 psia).
• Bubble point pressure pb (or saturation pressure) refers to the highest
pressure at which the first gas bubble comes out of solution from the oil and
exists as free gas in the reservoir.
• Below this pressure, a free gas phase will appear. Eventually the free gas
evolved begins to flow to the wellbore in ever-increasing quantities.
Conversely, the oil flows in ever-decreasing quantities.
2.2.1 GAS CAP
• If the same HYDROCARBON MIXTURE in the above discussion occurred (for
instance) at pi = 2000 psia and Ti = 215 °F, as shown in Fig. 1 (point 2), it
would be an oil reservoir with a gas cap, or gas cap reservoir.
• The slightest reduction in pressure causes liberation of gas from oil (because
pipb) making this a saturated oil reservoir. Hence, anytime pipb, we can
conclude that the reservoir has an initial gas cap.
2.2.2 GAS CONDENSATE
• Most known gas-condensate reservoirs are in the range of 3000-6000 psia
and 200-400 °F. They exist primarily as vapor phase (gas not liquid). Fig. 1.1
is a typical phase diagram of a gas condensate or “retrograde gas” reservoir
(PpcPcricon).
• Gas-condensate reservoirs may be approximately defined as those which
produced liquid with gravity above 45 oAPI at gas-oil ratios in the range of
5000 to 1000,000 scf /bbl. A gas condensate reservoir typically contains:
➢ methane (as the major component),
➢ intermediate components: propane, butane, pentane and hexane, and small
fraction of heavy components: heptane and heavier
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
• Consider a reservoir at, for instance, pi = 3300 psia and Ti = 230 °F, shown as
point 3i in Fig. 1.

Figure 1: Pressure-Temperature phase diagram of reservoir fluid (P.133)

• Since point 3i is outside the two-phase envelope and pi > Pc and Tcric> Ti > Tc,
this reservoir exists initially in the gaseous state, and is referred to as a gas
condensate reservoir (Tcricon is the cricondentherm or the maximum
temperature of the two-phase envelope).
• As production begins from the reservoir and pressure declines, no change in
the state of the reservoir fluid occurs until the dew point pressure is reached
(in this example, at 2700 psia, point D).
• As the reservoir pressure drops with production and the dew point line is
crossed, a liquid condenses out of the reservoir fluid.
✓ At the surface, this is normally indicated by the fact that the gas
produced has a lower liquid content and the producing GOR rises.
• This condensation is NOT a normal phenomenon. Normally (or theoretically)
one expects vaporization to occur with decreasing pressure. It is for this

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
reason that this abnormal behavior is commonly referred to as “retrograde”
condensation.

Figure 1.1
• At the molecular level, retrograde condensation results from the fact that the
attraction between light and heavy hydrocarbon components decreases as
the pressure drops and the lighter molecules become separated. As the
attraction between the heavier molecules becomes dominant, they coalesce
and form a liquid, as shown in Fig. 2.2B.

2.2.3 WET GAS RESERVOIR


Fig. 1.2 shows the phase diagram of a typical wet gas.
• Consider a reservoir initially at 350 °F and 3600 psia, represented by point
4i in Fig.1.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
• Since this point is outside the two-phase envelope and pi>Pc the reservoir
fluid is at no point the isothermal depletion line (path 4i – 4a 100% gas. Also,
since Ti>Tcricon is crossed.
• Therefore, the fluid in the RESERVOIR never changes composition; it is
always in the gaseous state.
• During production, the reservoir fluid leaves the reservoir and enters the
wellbore and then the separators along line 4i - 4S.
• Point 4S is at surface T and p conditions and is inside the two-phase
envelope. This accounts for the recovery of condensate liquid in the
separator.

Figure 1.2
2.2.4 DRY GAS RESERVOIR
• Fig. 1.3 is the phase diagram of a typical dry gas reservoir.
• If the phase diagram is such that point (Fig.2.2), i.e. separator conditions of P
and T lies outside the two-phase envelope and in the single-phase (gas)
region, then only gas will be produced at the surface.
• No liquid will be formed in the reservoir or at the surface, during isothermal
production, and the gas is called “dry gas” reservoir.
• It contains very little (if any) heavy hydrocarbons. This is true because at
high pressure the molecules composing the mixture are close together, and
attractive forces of the light for the heavier components are so high that the
heavier components are carried into the gas phase.
• A dry gas is composed principally of methane with only minor amounts of
ethane, propane and butane.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Figure 1.3

2.3 EQUATIONS OF STATE OR GAS LAWS


2.3.1 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 (SPE uses 100 kPa)
T = 60°F = 520°R = 288.72°K (SPE uses 288° K)

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. An ideal gas
is defined as one in which: (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.

2.3.1.1 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

V ∝ 1/P or PV = constant
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
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

V∝𝑇 or V/T = constant


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 600F and 14.7 psia occupies a volume of 379.4 cu-ft. One mole of a
material is the quantity of that material whose mass, in the system of units
selected, is numerically equal to the molecular weight. This means that one mole of
any ideal gas, that is, 2.73 x 1026 molecules of any gas, will occupy the same volume
at a given pressure and temperature.

2.3.1.2 The Ideal Gas Law (Equation of State)


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 p1 and temperature T1, and imagine the
following process, through which the gas reaches volume V2 at pressure p2 and
temperature T2:
Step 1
(V1 at p1 mT1 ) → (V at p2 mT1 )
T1 = constant
Step 2
(V at p2 mT1 ) → (V2 at p2 mT2 )
p2 = constant

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
𝑝1 𝑉1 = 𝑝2 𝑉 or 𝑉 = 𝑝1 𝑉1 /𝑝2 (1)
where V represents the volume at pressure p2 and temperature TI. 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

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
𝑉/𝑇1 = 𝑉2 /𝑇2 or 𝑉 = 𝑉2 𝑇1 /𝑇2 (2)
Elimination of volume V between Eq. 1 and 2 gives:

𝑝1 𝑉1 /𝑝2 = 𝑉2 𝑇1 /𝑇2
𝑝1 𝑉1 𝑝2 𝑉2
= (3)
𝑇1 𝑇2
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,
𝑝V𝑚
=𝑅
T
Where V𝑚 is the volume of one molecular weight of the gas at p and T.
In order to show that R is the same for any gas, Avogadro's Law is invoked. In
symbolic form, this law states:
V𝑀𝐴 = V𝑀𝐵
where V𝑀𝐴 represents the volume of one molecular weight of gas A. and
V𝑀𝐵 represents the volume of one molecular weight of gas B, both at pressure, p,
and temperature T this implies that
pVMA /T = R A or VMA = R A T/p
and
pVMB /T = R B or VMB = R B T/p
where R A represents the gas constant for gas A and R B represents the gas constant
for gas B. The Combination of the above equations reveals that
RBT RAT
= 𝑜𝑟 RA = RB
p p
Thus, the constant R is the same for all ideal gases and is referred to as the
universal gas constant. Therefore, the equation of state for one molecular weight of
any ideal gas is
pVM = RT (4)
For n moles of ideal gas this equation becomes
𝑝𝑉 = 𝑛RT (5)
where V is the total volumes of n moles of gas at temperature, T, and the pressure,
p. Since m is the mass of gas divided by the molecular weight M, the equation can
be written as
𝑚
𝑝𝑉 = ( )RT
𝑀
or, since m/V is the gas density,
𝑝 = (ρ/M)RT (6)
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

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
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 tbs 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 degree Rankin, and moles
in pound moles. Avogadro's law states that 1 lb-mole of any ideal gas occupies
379.4 cu ft at 60°F and 14.7 psia. Therefore,

R = pV/nT = (14.7 psia)(379.4 cu ft)/(lb − mole)(520 R)


= 10.73 psia cu ft/lb-mole R
Table 1 gives numerical values of R for various systems of units.

Example 1: A quantity of gas at P1 = 50 psig has a volume V1 = 1000 cuft. If the gas
is compressed to P2 = 100 psig, what volume (V2) would it occupy, assuming the
temperature is kept constant and Psc = 14.73 psia?
Solution:
Using Eq. 1 (Boyle’s law), we have:
V2 = 1000x(50+14.73)7(100+14.73) = 564.19 cuft

Example 2:
(a) A given mass of gas has a volume of 500 cuft when the temperature is 50 °F and
the pressure is 10 psig. If P remains constant and T is changed to 100 °F, what will
be the volume of the gas?
(b) What would be the new P of this gas if V remains constant and T is increased
from 50 °F to 100 °F?
Solution:
(a) Using Eq. 2 (Charles’ law) we have:
V2= 500 x (100 + 460)/(50 + 460) = 549.02 cuft
(b) Using Eq. 2. (Charles’ law) we have:
P2 = (10 + 14.73)x(100 + 460)/(50 + 460) = 27.15 psia

Example 3: How many SCF of an ideal gas are required to fill a 100 cuft tank to a
pressure of 40 psig when the temperature of the gas in the tank is 90 °F?
Solution:
𝑝1 𝑉1 𝑝 𝑉 𝑝 𝑉𝑇
Using Eq. 3, we have: = 22 𝑉2 = 1 1 2
𝑇 𝑇 1 2 𝑝 𝑇 2 1
Where: T1=90 + 460 = 550 °R
T2 = TX = 60 +460 = 520 °R

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
P1 = 14.73+ 40 = 54.73 psia
P2 = Psc = 14.73 psia
V1= 100 cuft
Substituting these values into Eq. 3 a gives V2 = 351 SCF

EXAMPLE 4: Repeat Example 3 using the ideal gas law, Eq. (5)
Solution:
Since one pound-mole (lb-mole) of an ideal gas occupies 378.6 SCF, the gas volume
(in SCF) needed to fill a 100 cuft tank is:
VSC = 378.6 n (Substitute this term into Eq.5)
gives Vsc = 378.6 (PV / RT)
= 378.6 (54.73x100 / 10.732x550)
= 378.6x0.927 = 351 scf

EXAMPLE 5: Calculate the contents of a 500 fi3 tank of ethane at 100 psia and 100
°F in: moles, pounds, molecules, and SCF
Solution
• Assuming ideal gas behavior:
Moles =(100x500)/(10.73x560)=8.32
Pounds= 8.32x30.07=250.2
Molecules=8.32x2.733x1026 = 22.738x1026
SCF=8.32x379.4=3157
• Alternate solution using the ideal gas law:
VSC = nRT/p=(8.32x10.73x520/14.7)=3158 SCF

Example 6: Calculate the mass of methane gas contained at 1000 psia and 68°F in
a cylinder with volume of 3.20 cu ft. Assume that methane is an ideal gas.

Solution
𝑚 𝑝𝑀𝑉
𝑝𝑉 = ( )RT ➔ 𝑚 =
𝑀 RT
m = (1000 psia)(16.0 lbm/lb-mole)(3.20 ft3)/{(10.73 psi/ft3/lb-mole 0R)(528°R )}
m = 9.0 lbm

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Table 2 Numerical values of R for various systems of units

2.3.1.3 Ideal Mixtures


The previous treatment of the behavior of gases applied only to single component
gases.
As the gas engineer 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 Pressure.
The partial exerted by each component of the gas mixture can he 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:
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑝𝐴 = 𝑛𝐴 ( ) 𝑝𝐵 = 𝑛𝐵 ( ) 𝑝𝐶 = 𝑛𝐶 ( )
𝑉 𝑉 𝑉
According to Dalton' s Law, the total pressure is the sum of the partial pressures
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

𝑝 = 𝑝𝐴 + 𝑝𝐵 + 𝑝𝐶
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑝 = 𝑛𝐴 ( ) + 𝑛𝐵 ( ) + 𝑛𝐶 ( )
𝑉 𝑉 𝑉
𝑅𝑇 𝑅𝑇
𝑝 = ( ) ∑ 𝑛𝑗 = ( ) 𝑛
𝑉 𝑉
It follows that the ratio of the partial pressure of component j, pj, to the total
pressure of the mixture p is
𝑝𝑗 /𝑝 = 𝑛𝑗 /Σ𝑛𝑗 = 𝑛𝑗 /𝑛 = 𝑦𝑗 (7)
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: 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 containing nA
moles of component A, nB moles of component B, and so on, can be calculated
using the ideal gas law
(nA )RT (nB )RT (nC )RT
𝑉𝐴 = , V𝐵 = , 𝑉𝐶 =
p p p
Thus, according to Amagat law the total volume is
𝑉 = 𝑉𝐴 + V𝐵 + 𝑉𝐶
(nA )RT (nB )RT (nC )RT RT RT
V= + + → V= =
p p p p ∑ 𝑛𝑗 p(n)
It follows that the ratio of the partial volume of component j on the total volume of
the mixture is

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
𝑉𝑗 /𝑉 = (𝑛𝑗 )(𝑅𝑇/𝑝)/(𝑛)(𝑅𝑇/𝑝) = 𝑛𝑗 /𝑛 = 𝑦𝑗 (8)

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
𝑀𝑎 = Σ𝑦𝑗 𝑀𝑗 (9)

Example 7: Dry air is a gas mixture consisting essentially of nitrogen, oxygen, and
small amounts of other gases. Compute the apparent molecular weight of air given
its approximate composition. The molecular weight of each component may be
found in Table 2.

Component Mole fraction (yj)


Nitrogen 0.78
Oxygen 0.21
Argon 0.01

Solution
Ma = yN2 MN2 + yO2 MO2 + yA MA
Ma = (0.78)(28.01) + (0.21)(32) + (0.01)(39.94)
= 28.97
A value of 29.0 is usually considered sufficiently accurate for engineering
calculations.

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,
𝛾g = 𝜌g /𝜌air (10)
Assuming that the behavior of both the gas and air may be represented by the ideal
gas law, specific gravity may be given as
𝛾g = (Mg p/RT)/(Mair /RT) = Mg /Mair = Mg /29 (11)
where Ma is the apparent molecular weight of the gas mixture.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Example 8: Calculate the gravity of a natural gas of the following composition.
Component Mole fraction( vi)
Methane 0.85
Ethane 0.09
Propane 0.04
n-Butanc 0.02
1,00
Solution;
Component Mole fraction Molecular weigh yi*Mi
C, 0.85 16.0 13.6
C2 0.09 30.1 2.71
C3 0.04 44.1 1.76
n -C4 0.02 58.1 1.16
1.0 Ma=19.23
Mg 19.23
𝛾g = = = 0.66
Mair 29
2.3.2 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,
𝑍 = 𝑉actual /𝑉ideal or 𝑉actual = zVideal
The equation of state is
PVideal = nRT or pVactual /z = nRT
Therefore, the equation of state for any gas becomes
pV = 𝑧nRT (12)
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 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

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
would indicate that ideal gas behavior does in fact occur. Compressibility factors
for several hydrocarbon gases are given in Figures 2, 3, and 4.

Figure 1: Typical plot of the compressibility' factor as a function of pressure at constant temperature.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Figur.1 Compressibility factors for methane.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Figure.2 Compressibility factors for ethane.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Figure.4:Compressibility factors for propane.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Figure.5:Compressibility factors for pure hydrocarbon gase as a Function of reduced pressure and
temperature.

2.3.3 Real Gas Mixtures


Compressibility charts are available for most of the single component light
hydrocarbon gases, but in practice a single component gas is rarely encountered.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
In order to get z factors for natural 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 similar substances. This means that all pure gases have the same
z factor at the same values of reduced temperature and pressure, where the
reduced values are defined as
Tr = T/Tc , Pr = P/Pc
Where Tc and pc are the critical temperature and pressure for the gas, respectively.
The values must be in absolute units.

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 engineers deal with are composed of molecules of the same class of
organic compounds known as paraffin hydrocarbons. The law of corresponding
states has been extended to cover mixture of gases that are closely related
chemically. Since it is somewhat difficult to obtain the critical point for
multicomponent mixtures, the quantities of pseudo-critical temperature and
pseudo-critical pressure have been conceived. These quantities are defined as

𝑇𝑝𝑐 = ∑ 𝑦𝑗 𝑇𝑐𝑗 𝑃𝑝𝑐 = ∑ 𝑦𝑗 𝑃cj (13)


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. It must be understood, however, that these pseudo-critical properties were
devised simply for use in correlating compressibility factors and in no way relate
to the actual critical properties of the gas mixture.

Example 9: Calculate the pseudo-critical temperature and pseudo-critical pressure


of the following natural gas mixture. Use the critical constants given in Table (2).
Solution:

Critical Critical
Mole
Component Temperature Pressure
Fraction
(R) (Psi)
yj Tcj yj Tcj pcj yj pcj
C1 0.85 343.1 291.6 667.8 567.6
C2 0.09 549.8 49.5 707.8 63.7
C3 0.04 665.7 26.6 616.3 24.7
n-C4 0.02 765.3 15.3 550.7 11.0
1.0 Tpc=383 R ppc=667 Psi
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

The compressibility factors for natural gases have been correlated using pseudo-
critical properties and are presented in Figures 6, 7, and 8. Compressibility factors
are a function of composition as well as temperature and pressure. It has been
pointed out that the components of most natural gases are hydrocarbons of the
same family, and therefore a correlation of this type is possible.
If the volume fraction is given at conditions other than standard, the volume
fraction must be converted to a mole fraction basis, taking into account the
deviation from ideal behavior. The following example illustrates this procedure.

Example 10: A gas has the following composition measured at 2500 psia and
300°F Calculate the composition in mole fraction. The volume percent at these
conditions are:
C1 = 67%, C2 = 30%, C3 = 1%, C02 = 2%.
Solution:
To convert from volume to moles, assume 100 ft3 as a basis. Then use
n = pV/zRT = 2500 V/(10.73)(760)(z) = 0.3062V/z
Component Vi(ft3)
Tr pr z V/z nj nj/n
C1 67 2.22 3.72 0.963 69.6 21.3 0.595
C2 30 1.4 3.53 0.708 42.5 13 0.363
C3 1 1.14 4.06 0.585 1.8 0.55 0.015
CO2 2 1.3 2.32 0.658 3.2 0.48 0.027
100 38.83 1

In most cases the composition of the 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 9 can be used to
estimate the pseudo-critical properties. The properties can also be calculated
using the following equations.
Tpc = 170.5 + 307.3𝛾g (14)
ppc = 709.6 − 58.7𝛾g (15)
For condensate fluids:
Tpc = 187 + 330𝛾g + 71.5𝛾g 2

ppc = 706 − 51.7𝛾g + 11.1𝛾g 2


Example 10: Dry air is a mixture of nitrogen, oxygen, and small amount of other
inert gases as given in the following table:
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
( a) Calculate its apparent molecular weight and density of air
( b) Calculate the pseudo critical temperature and pressure. (H.W)
Component mole fract. M
Nitrogen 0.78 28.01
Oxygen 0.21 32
Argon 0.01 39.94
Total=1.0
Solution:
(a) The apparent molecular mass of air is obtained from Eqs. 9 to11.:
𝑀𝑎 = Σ𝑦𝑗 𝑀𝑗 = (yM)nitrogen + (yM)oxygen + (yM)argon
Mair = (0.78)(28.01) + (0.21)(32.00) + (0.01)(39.94)
= 28.97 Ib/lb-mole or 28.97 kg/kg-mole
• For all practical purposes, Mair = 29 is used for calculating specific gravity of
gases.
• The density of air at standard conditions of P and T is obtained from Eq.:
ρ = M p / R T = [28.97x14.73] / [10.732x(60+460) ]
Pair = 0.07646 Ib/cuft

2.3.4 FACTOR Z FROM VOLUME CHANGE


Step 1. Some quantity of gas (n moles) is charged into a cylinder maintained at the
same temperature T throughout the experiment.
Step 2. Measure the initial volume of gas at an atmospheric pressure of 14.7 psia,
V0 .
Step 3. Apply the real gas law at the atmospheric pressure (Z = 1): 14.7xV0=nRT
Step 4. Vary the volume of the gas in the cylinder by moving the piston in the
cylinder and read the pressure p and the corresponding volume V. The
corresponding equation for each pair of p, V will be pV=ZnRT.
Step 5. Divide the two equations for each pair p, V to the initial one and find
Z=(pV)/(14.7xV0). Therefore, by varying p and measuring V, the isothermal Z(p)
function can be readily obtained.

2.3.5 FACTOR Z FROM SPECIFIC GRAVITY AND DENSITY OF GAS


Knowing the gas composition, the specific gravity and density of any gas is
determined as follows:
Step 1 - Calculate the apparent molecular weight (MJ of the hydrocarbon
components from Eq. 9:
𝑀𝑎 = ∑ 𝑦𝑖 𝑀𝑗 (16)
where
𝑦𝑖 = mole fraction of component I in gaseous state
pci = pseudo critical pressure of component i
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Tci = pseudo critical temperature of component i
Step 2 - Calculate the specific gravity of gas from following Eq.:
Ma
𝛾g =
29
Step 3 - The density of gas is obtained from Eq. 2.2.13
𝜌g = 𝜌air 𝛾g
Step 4 - Calculate z from the gas law
m pMa
𝜌g = =
V zRT

• The specific gravity of gas is useful in determining (in addition of gas density) the
gas pseudo-critical pressure and temperature from Fig. 2.4 (or correlations such as
Equation in section 2.3.6.2).

2.3.6 FACTOR Z FOR DRY SWEET GAS


For our purpose a dry sweet gas is defined as a gas reservoir in which:
• The C7+ fraction is negligible, and
• The mole fraction of C02, H2S, N2 and H2O are negligible
As stated earlier, the principle of corresponding states suggests that:
• pure gases have the same z-factor at the same values Ppr and Tpr
• mixtures of similar gases can also be correlated with Ppr and Tpr
Where the pseudo-reduced temperature and pressure are defined as:
P 𝑇
ppr = , 𝑇𝑝𝑟 = (17)
Ppc 𝑇𝑝𝑐
All charts and correlations for determining the z- factor require Ppr and Tpr values.
This section discusses methods for calculating the pseudocritical pressure and
temperature of a gas mixture:
2.3.6.1 Gas Composition is Known
A - Ppc, Tpc and z from Graphs
If the gas does not contain significant non-hydrocarbon components and 𝛾g is
known from lab. data, then
Step 1 - Determine Ppc and Tpc from Fig. 2.4
Step 2 - Calculate Ppr and Tpr from Eq 17:
P 𝑇
ppr = , 𝑇𝑝𝑟 =
Ppc 𝑇𝑝𝑐
Step 3 - Obtain the gas deviation factor z from the Standing-Katz Chart, Fig. 6, or
one of several correlations (section 2.4).

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

B - Ppc and Tpc from Gas Composition


Step 1 - Obtain the critical pressures (Pc) and temperatures (Tc) of the
components of the gas mixture from Table 2.5
Step 2 - Determine the pseudo-critical pressure (Ppc) and temperature (Tpc), and
𝑇𝑝𝑐 = Σ𝑦𝑗 𝑇𝑐𝑗 𝑝𝑝𝑐 = Σyj 𝑝cj

Step 3 - Calculate the pseudoreduced pressure (Ppr) and temperature (Tpr)


P 𝑇
ppr = 𝑇𝑝𝑟 =
Ppc 𝑇𝑝𝑐
Step 4 - The factor z is then determined either from the Standing-Katz chart or one
of several correlations in the next section (i.e. 2.4).

EXAMPLE 11: Problem: Given the gas mixture whose composition is shown in the
following table
(a) Calculate the specific gravity of this gas mixture
(b) Calculate the density of this gas mixture at 1000 psia and 150 °F, treating it as
(i) Ideal gas, and
(ii) Real gas
Component Mole fraction, yi
Methane (C1) 0.8
Ethane (C2) 0.12
Propane(C3) 0.06
n-Butane(C4) 0.02

Solution
(a) Specific gravity of gas mixture:
First calculate the apparent molecular weight (Ma) of the gas mixture

The apparent molecular weight of the gas mixture is 20.249


• Specific gravity of gas mixture
Ma
𝛾g = = 20.249 / 29 = 0.698
Mair=29
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
(b) Density of gas mixture, 1000 psia and 150 °F:
m pM
𝜌g = = a
V zRT
(i) If the gas mixture is treated as an ideal gas, i.e. z = 1, the gas density is:
1000 × 20.249
𝜌g = = 3.095lb/ft 3
1 × 10.732 × (460 + 150)
(ii) In order to correct the gas density for non-ideal behavior, the gas deviation
factor, z, is needed and is calculated as follows:

• Thus, the pseudo-critical temperature and pressure are:


Tpc = 395.6 °R, ppc= 665.87 psia
• The pseudo-reduced temperature and pressure are:
Tpr = (460 + 150) / 395.6 = 1.54, ppr = (1000) / (665.87) = 1.502
• From the Standing-Katz chart (Fig. 6) the gas deviation factor is: z = 0.89
• The gas density of this (real) gas is:
1000 × 20.249
𝜌g = = 3.477lb/ft 3
0.89 × 10.732 × (460 + 150)
• Comparing the two values of the density of gas, we find that the assumption of
ideal gas leads to an (unacceptable) error of:
3.477 − 3.095
error = = 11%
3.477

2.3.6.2 Gas composition is NOT known


Step 1 - Determine experimentally the specific gravity of gas
Step 2 - Knowing the gas gravity use Table 2.2, Fig. 2.4 or the following Sutton
correlations (for dry gas) to calculate Ppc [psia] and Tpc [°R]:
ppc = 756.8 − 131.0𝛾g − 3.6𝛾g2
Tpc = 169.2 + 349.5𝛾g − 74.0𝛾g2
Where: Tpc, Ppc, and yg are the pseudo-critical T and P, and specific gas gravity
(air=l) of the hydrocarbon components

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• 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 𝛾g in the above correlation is the
separator gas gravity or the gravity of the well stream fluid
• These equations are valid only if the total impurity content is 7% or less.

For California dry gas reservoirs (~ similar to Algeria gases), these equations
become:
ppc = 677 + 15𝛾g − 37.5𝛾g2 (20)
Tpc = 168 + 325𝛾g − 12.5𝛾g2 (21)
For condensate gases, the following correlations should be used:
ppc = 706 − 51.7𝛾g − 11.1𝛾g2
Tpc = 187 + 330𝛾g − 71.5𝛾g2
Step 3- Calculate the pseudo-reduced temperature and pressure
Step 4- Determine the z-factor using the Standing-Katz chart or one of the
correlations in Section 2.4

2.3.7 Z FACTOR OF DRY SOUR GAS


• Fig. 6 is a correlation of the Z-factor as a function of pseudo-reduced temperature
(Tpr) and pseudo-reduced pressure (Ppr) Fig. 6 is generated for sweet natural gases
and corrected for those containing H2S, N2 and C02.
• If the gas contains more than 15 % of non-hydrocarbon components (yCO2>12%,
yN2>3%, and/or any H2S), Ppc and Tpc of the TOTAL gas mixture (i.e. hydrocarbon
components plus impurities) and the gas deviation factor z are calculated as
follows:
Step 1:- Calculate the total mole fraction of non-hydrocarbon components,
including water vapor (yH2O):
yT =yCO2 + yH2S + yN2 + yH20 (30)
Step 2:- Calculate the specific gravity correction factor:
𝛾wcor = 1.1767yH2S + 1.5196yCO2 + 0.9672yN2 + 0.622yH2O (31)
Step 3:- Calculate the specific gas gravity of the hydrocarbon components:
𝛾 −𝛾
𝛾gh = w wcor (32)
1−yT
where: 𝛾w = specific gas gravity of the well-stream fluid; if a separator is used then
𝛾w is the separator gas gravity
Step 4:- Calculate and of the hydrocarbon mixture (only) using Sutton’s
correlations (Eqs. 20 and 21):

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
2
ppch = 756.8 + 131𝛾gh − 3.6𝛾gh (33)
2
Tpch = 169.2 + 349.5𝛾gh − 74𝛾gh
Step 5: - Calculate the pseudo-critical pressure and temperature of the ENTIRE gas
mixture (including contaminants):
𝑃𝑝𝑐 = (1 − 𝑦𝑇 )𝑃𝑝𝑐ℎ + (1306𝑦𝐻2𝑆 + 1071𝑦𝐶𝑂2 + 493𝑦𝑁2 + 3200𝑦𝐻2𝑂 )
(34)
𝑇𝑝𝑐 = (1 − 𝑦𝑇 )𝑇𝑝𝑐ℎ + (672.4𝑦𝐻2𝑆 + 547.6𝑦𝐶𝑂2 + 227𝑦𝑁2 + 1165𝑦𝐻2𝑂 )
Where the constants are actually the critical pressures and temperatures of the
corresponding contaminants (e. g., 1306 and 672.4 are respectively the critical
pressure and temperature of H2S, etc . )
Step 6: - Adjust the pseudo-critical properties for H2S and C02 by the Wichert and
Aziz factor 𝜀3 , which can be obtained from Fig.2.5, or from the following
expression:
𝜀3 = 120(𝑦𝑐+ℎ0.9 1.6
− 𝑦𝑐+ℎ ) + 15(𝑦ℎ0.5 − 𝑦ℎ4 ) (35)
Step 7: - Calculate the adjusted (for C02 and H2S) pseudo-critical values

Tpc = 𝑇𝑝𝑐 − 𝜀3 (36)
ppc T′pc
p′pc = (37)
Tpc +yH2 S (1−yH2 S )𝜀3
where:
ppc = pseudo-critical pressure of the entire gas mixture, psia (from step 5)
Tpc = pseudo-critical temperature of the entire gas mixture, °R (from step 5)

Eqs. 35 through 37 yield z factors within 5% of experimental value of z (at


temperatures and pressures of up to 300° F and 7000 psia, respectively) and for:
yC02 ≤ 55% and yH2S ≤ 75%
• These correlations assume that the Z-factor values are not greatly affected by the
presence of nitrogen.
Step 8: - Assuming yN2 and yH2O are negligible, i.e. yN2+yH2O<5% (if they are not go
to Step 9) calculate the adjusted pseudo-reduced pressure and temperature from
the following expressions, then determine the z-factor, either from the Standing-
Katz chart or one of the correlations for z (see next section)
𝑇 P
𝑇𝑝𝑟 = ′ Ppr = ′ (38)
Tpc Ppc
Step 9:- If yN2 and yH2O are NOT negligible Tpc
and Ppc

(in step 7) and P’pr and T’pr

(in step 8) must further be adjusted for nitrogen and water vapor content:
(a) The adjusted (for all 4 contaminants) pseudo- critical properties are:

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Tpc ′ −(227yN2 +1165yH2O )
Tpc ′′ = )
− (246yN2 − 400yH2O )
1−(y +y
N2 H2O
(39)
′′ Ppc′ −(493yN2 +3200yH2O )
Ppc = − (162yN2 − 1270yH2O )
1−(yN2 +yH2O )
(b) The adjusted (for all 4 contaminants) pseudo-reduced properties are:
𝑇 P
𝑇𝑝𝑟 = ′′ Ppr = ′′ (40)
Tpc Ppc
(c) The gas deviation factor is then calculated either from the Standing-Katz
chart or from one of the correlations in the next section.
• The z-factor values calculated as described above are about as accurate as can be
measured in the laboratory. This is true even for wet gases and retrograde gases
with specific gravity as high as 1.6.

EXAMPLE 12: The composition of a sour gas mixture at 1623 psia (11.2 kPa) and
100°F (37.8°C) is shown in the following table.

(a) Use the Wichert and Aziz adjustment factor method and the Standing and Katz
chart to calculate the gas deviation factor of this mixture. Compare with the lab.
measured value of Z = 0.822.
(b) Determine the specific gravity and density of this sour gas mixture

Solution:
(a) The gas deviation factor z is determined as follows:
Step 1 - Obtain the critical temperature and critical pressure values of the
constituents from Table 2.5
Step 2 - Calculate the pseudo-critical properties for the mixture using
𝑝𝑝𝑐 = Σyj 𝑝cj = 748.3 𝑝𝑠𝑖𝑎, 𝑇𝑝𝑐 = Σ𝑦𝑗 𝑇𝑐𝑗 = 384.5 0R

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Step 3 - From Fig. 2.5, read the critical adjustment factor: 𝜀3 = 20 0R

• Eq. 35 gives a similar value for 𝑦ℎ = 7.35% and 𝑦𝐶+ℎ = 7.44 + 7.35 = 14.79%
0.9
𝜀3 = 120(𝑦𝑐+ℎ 1.6
− 𝑦𝑐+ℎ ) + 15(𝑦ℎ0.5 − 𝑦ℎ4 ) = 19.91 0R
Step 4 - The adjusted pseudo-critical pressure and temperature are obtained from
Eqs. 36 & 37

Tpc = 𝑇𝑝𝑐 − 𝜀3 = 384.5 − 20 = 364.5 0R
ppc T′pc 748.3×364.5
p′pc = = = 678.7 psia
Tpc +yH2 S (1−yH2 S )𝜀3 384.5+0.0735(1−0.0735)(20)
Step 5 - The pseudo-reduced pressure and temperature are:
𝑇 560 P 1623
𝑇𝑝𝑟 = ′ = = 1.54 Ppr = ′ = = 2.39
Tpc 364.5 Ppc 678.7
Step 6 - Obtain the gas deviation factor z from the Standing Katz chart, i .e. Fig.2.3
z= 0.82. Thus, the calculated value of z is in good agreement with the lab. measured
value (0.8211).
(b) The specific gravity and density of this sour gas is obtained as follows:
1 . The apparent molecular weight (MJ of this sour gas mixture is calculated
from:
Ma = ∑i yi Mi =20.3

Where the mole fractions (y ) and molecular weights Mt of the gas components are
respectively shown in the Table E (above) and Table 2.5.
M 20.03
2. The specific gravity of this sour gas is calculated from: 𝛾g = a = = 0.69
29 29
3. The density of this gas at reservoir pressure of 1623 psia and temperature of
pM 1623×20.03
100 ° F (z = 0.82) is obtained from: 𝜌g = a = = 6.6lb/cuft
zRT 0.82×10.732×(460+100)

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Figure 2.4: Pseudo-critical properties of natural gases.Ppc - Tpc

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Figure.6: Compressibility factors for natural gases

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Figure.7: Generalized plot of compressibility factors at low reduced pressures

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Figure.8: Compressibility factors for gases near atmospheric pressure.

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2.3.8 COMPRESSIBILITY OF NATURAL GASES


Knowledge of the variability of fluid compressibility with pressure and
temperature is essential in performing many reservoir engineering calculations.
For a liquid phase, the compressibility is small and usually assumed to be constant.
For a gas phase, the compressibility is neither small nor constant.
By definition, the isothermal gas compressibility is the change in volume per unit
volume for a unit change in pressure at constant temperature or, in equation form:
1 ∂𝑉
𝐶𝑔 = − ( ) (41)
𝑉 ∂𝑃 𝑇
Where: Cg = isothermal gas compressibility, 1/psi, V= Volume of one mole of the
gas.
From the real gas law equation, the volume of gas can be expressed as:
𝑧
𝑉 = 𝑛𝑅𝑇 (42)
𝑝
Differentiating V with respect to pressure and substituting into Eq. 41 yields:
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
1 1 ∂𝑧
𝐶𝑔 = − ( ) (43)
𝑃 𝑧 ∂𝑃
Where dz/dp is the slope of a straight-line tangent to the z vs p curve at a point
where pressure is p.
• For an ideal gas, i.e. z=l, Eq. 2.6.3 becomes:
1
𝐶𝑔 = (psia-1) (44)
𝑃

From the definition of pseudo-reduced pressure the pressure is:


P = PprPpc Substitution of this expression into Eq. 43
1 1 1 ∂z
cg = [p − z (∂p )] (45)
ppc pr pr
Moving Ppc to the left hand side of the equation, and calling the product the
pseudoreduced compressibility cr:
cr=cgPpc (46)
Therefore, the pseudo-reduced compressibility for any gas mixtures can be
expressed as:

1 1 ∂z
cr = − ( ) (47)
ppr z ∂p pr
This relationship was used to develop charts in which crTr is plotted as a function
of Tr and Pr on a loglog graph (Figures 2.8a and 2.8b).
Note, in these figures: Tr = Tpr and Pr = Ppr

These figures are used to determine the gas compressibility cg as follows:


Step 1: Calculate the pseudo-critical P and T from Eqs. 13 (if the gas composition is
known), i.e.
𝑇𝑝𝑐 = Σ𝑦𝑗 𝑇𝑐𝑗 𝑝𝑝𝑐 = Σyj 𝑝cj
If gas composition is unknown, then use Equation in section 2.3.6.2 (Gas
composition is NOT known).
Step 2: Calculate the pseudo-reduced P and T from:
𝑇 P
𝑇𝑝𝑟 = ppr =
𝑇𝑝𝑐 Ppc
Step 3: Determine the value of crTr from Fig 2.8a or 2.8b
Step 4: Calculate the compressibility of gas from Eq. 23:
𝑐
𝑐𝑔 = 𝑟 (48)
𝑃𝑝𝑐
EXAMPLE 13: What is the gas compressibility of the sweet gas mixture in
EXAMPLE 11
Solution:
• The pseudo-critical and pseudo-reduced pressure and temperature values in
EXAMPLE 11 are:

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Tpc = 395.6 °R, Ppc= 665.87 psia, Tpr = 1.54, Ppr = 1.502 @ p = 1000 psia
• From Fig. 2.8b the product crTr at Pr = 1.5 and Tr = 1.54 is approximately:
crTr = 1.14
• The pseudo-reduced compressibility value is:
cr = Tr / 1.14 = 1.54 / 1.14 = 1.35
• The compressibility of the sweet gas mixture in EXAMPLE 11 is obtained
from Eq. 48:
𝑐𝑟 1.35
𝑐𝑔 = = = 2.027 × 10−3 psia
𝑃𝑝𝑐 665.87
• Note: If the gas mixture had been assumed to be an ideal gas, cg is:
1 1
𝑐𝑔 = = = 1.0 × 10−3 𝑝𝑠𝑖𝑎−1
𝑃 1000
which is only half of the correct value of cg. This approximation should always be
avoided.

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2.3.9 GAS FORMATION VOLUME FACTOR


The gas formation volume factor is used to relate the volume of gas, as measured
at reservoir conditions, to the volume of the gas as measured at standard
conditions, i.e., 60°F and 14.7 psia. This gas property is then defined as the actual
volume occupied by a certain amount of gas at a specified pressure and
temperature, divided by the volume occupied by the same amount of gas at
standard conditions. In an equation form, the relationship is expressed as

Bg = Vp,T / Vsc
Where:
Bg = gas formation volume factor, ft3/scf,
Vp,T = volume of gas at pressure p and temperature, T, ft3
Vsc =volume of gas at standard conditions, scf
Applying the real gas equation-of-state, and substituting for the volume V, gives:
𝑧𝑛𝑅𝑇
𝑝 psc zT
𝐵𝑔 = =
𝑧sc 𝑛𝑅𝑇sc Tsc p
𝑝sc
Where:
Zsc = z-factor at standard conditions = 1.0
Psc, Tsc = standard pressure and temperature, Assuming that the standard
conditions are represented by Psc =14.7 psia and Tsc= 520, the above expression
can be reduced to the following relationship:
zT
𝐵𝑔 = 0.02827 (49)
p
Where:
zT
Bg = gas formation volume factor, ft3/scf. 𝐵𝑔 = 0.00504 (bbl/scf)
p
z = gas compressibility factor
T = temperature, °R
Equation 49 can be expressed in term of the gas density ρg if combined with
1 pM
following Equation 𝜌g = = a
v zRT
Ma Ma
To give Bg = 0.02827 = 0.002635 ; (ft 3 /scf)
R𝜌g 𝜌g
Where:
𝜌g = gas density, lb/ft3
Ma = apparent molecular weight of gas
The reciprocal of the gas formation volume factor is called the gas expansion
factor and is designated by the symbol Eg, or:

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
p
Eg = 35.37 3
, (scf/ft ) (50)
zT
𝐵𝑔𝑖
%Recovery = 100 × (1 − ) (51)
𝐵𝑔𝑎
Where:
Bgi = gas formation volume factor at initial reservoir pressure, Pi
Bga = gas formation volume factor at abandonment reservoir pressure, Pa

Example 14 At initial reservoir pressure of 2500 psia and temperature of 180 °F,
the gas deviation factor z = 0.85.
(a) Calculate the gas formation volume factor
( b) How many SCF of this gas are contained in the reservoir with gas pore volume
of 109 cuft?
Solution:
(a) Using Eq. 49, the gas FVF is
zT 0.85x(180 + 460)
𝐵𝑔 = 0.02827 = 0.02827 = 0.00616 (Scf/ft3)
p 2500

(b) The initial gas in place is:


Vr 109
𝐼𝐺𝐼𝑃 = = = 162.388 × 109 scf
Bgi 0.00616
(c ) In SI units, Bgi is calculated from Eq.:
ZT 0.3495 × 0.85 × 355.55
Bgi = 0.3495 = = 6.128 × 10−3 (m3 /scm3 )
pi 17237.5
where temperature and pressure are converted to SI units as follows:
T (in °K ) = 0.5555 [T (in °F) + 460 ] = 0.5555 [ 1 8 0 + 460] = 355.55

2.3.10 VISCOSITY OF GASES


Viscosity is a measure of the resistance to flow exerted by a fluid.
• At high reservoir pressures (Fig. 10 ), gas viscosity increases as the reservoir
pressure increases, and decreases with increasing temperature.
• At low pressure (p<1000 psi) as shown in Fig. 11, gas viscosity increases with
increasing temperature (T>200°F).
• 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.
METHOD 1
• The NGSMA chart, Fig. 12, is one of the simplest graphs for determining gas
viscosity. This figure gives gas viscosity as a function of reservoir gas gravity, p and
T.

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
• Its use is illustrated by the arrows: For a 0.7 gravity gas at reservoir p and T of
750 psia and 220 °F, respectively, the gas viscosity is 0.0158 cp.

Fig. 10

Fig. 11
METHOD 2
Carr-Kobayashi-Burrow (CKB) developed one of the most common equations for
determining viscosity of gas mixtures.
• It requires knowledge of the gas composition and of the viscosity of each
component at atmospheric pressure and reservoir temperature
• The CKB equation for viscosity of a gas mixture at atmospheric P and reservoir

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
1/2
∑[𝜇gi yi (Mi )]
T is: 𝜇ga = 1/2 (52)
∑[yi (Mi )]

Fig. 12
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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Where, 𝜇ga =Viscosity of the gas mixture at 1 atm, 𝜇gi = Viscosity of the component
i (Fig. 13), 𝑀𝑖 = Molecular mass of component I, yi = Mole fraction of component i
• If the gas composition is not known, Fig. 14 may be used to estimate the gas
viscosity at atmospheric pressure and reservoir temperature, where the apparent
molecular weight of the gas mixture is obtained from: M= 29γg
The following procedure is recommended for determining gas viscosity
(from the CKB equation) at reservoir conditions of P and T:

(A) Sweet Gas


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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Step 1:- Determine the pseudo-critical pressure (Ppc) and pseudo-critical
temperature (Tpc).
Step 2:- Determine the pseudo-reduced pressure (Ppr) and pseudo-reduced
temperature (Tpr).
Step 3:- Determine the viscosity of the gas mixture at atmospheric and reservoir T,
𝜇ga , using either Eq . 52 (or Fig. 14 knowing M)
Step 4:- Obtain the ratio 𝜇g / 𝜇ga from Figures 2.18.
Step 5:- Calculate the gas viscosity at reservoir P and T from:
𝜇g = [𝜇g /𝜇ga ] × 𝜇ga

EXAMPLE .15: Calculate the viscosity of the gas described in EXAMPLE 11

Solution:
Since the gas only contains hydrocarbon components, the procedure for sweet gas
is applicable.
Step 1 - From EXAMPLE 11:
Tpc = 395.6 °R, Ppc= 665.87 psia, Tpr = 1.54, Ppr = 1.502 @ p = 1000 psia
Step 2 - From EXAMPLE 11:
Tpr = 1.54, Ppr = 1.502
Step 3 - From EXAMPLE 11, the apparent molecular weight of the gas mixture is
20.249. Using Fig. 14 the viscosity of the gas mixture at atmospheric pressure and
reservoir T= 150 °F is: 𝜇ga = 0.0122 cp
Step 4 - Obtain the ratio 𝜇g /𝜇ga : 𝜇g /𝜇ga = 3.7 2
Step 5 - Calculate the gas viscosity at reservoir P = 1000 psia and T = 150 from
𝜇g = [𝜇g /𝜇ga ] × 𝜇ga = 3.72 x 0.0122 = 0.0454 cp

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Fig. 13

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

Fig. 14

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.

(B) Sour gas


• The inserts in Fig. 14 are corrections for the presence of carbon dioxide (C02),
hydrogen sulfide (H2S) and nitrogen (N2) and for 4 gas gravity values: 0.6, 1, 1.5,
and 2.
• The effect of each of the non-hydrocarbon gases is to increase the viscosity of the
gas mixture.
• The corrections are (reasonably) accurate only if the mole fractions of C0 2, H2S
and N2 are less than 15%. If the mole fractions are higher than 15% and up to 25%,
corrections (less accurate) are still possible by linearly extrapolating the lines in
the inserts. The procedure for calculating the viscosity of a sour gas at
reservoir P and T is:
Step l: - Determine the pseudo-critical pressure (Ppc) and pseudo-critical
temperature (Tpc) of the total gas mixture
Step 2: - The pseudo-critical properties are adjusted with a factor 𝜀3 , using Eqs.
35-37: Tpc

and p′pc
Step 3: - Determine the adjusted pseudo-reduced pressure (Ppr) and pseudo-
reduced temperature (Tpr) from:
𝑇 P
𝑇𝑝𝑟 = ′ Ppr = ′
Tpc Ppc
Step 4: - Determine the (uncorrected) viscosity of the gas mixture at atmospheric
and reservoir T, 𝜇gau , using either Eq. 52 (or Fig. 2.11 knowing M)
Step 5: - Knowing the gas gravity 𝛾𝑔 and the mole fractions of the non-
hydrocarbon components i.e. yCO2 , yH2 , and yN2 obtain the viscosity correction
factors from, the vertical axis of the inserts in Fig. 14:
𝜇corCO 2 , 𝜇cor H2𝑆 , 𝑎𝑛𝑑 𝜇cor 𝑁2
Step 6: - Calculate the total viscosity correction factor for non-hydrocarbon
components:
𝜇corNH = 𝜇corCO 2 + 𝜇cor H2𝑆 + 𝜇cor 𝑁2
Step 7: - Calculate the corrected viscosity of the gas mixture at atmospheric and
reservoir
𝜇ga = 𝜇corNH + 𝜇gau
Step 8: - Using the adjusted pseudo-reduced pressure (P’pr) and pseudo-reduced
temperature (T’pr) from step 3, determine the ratio 𝜇g /𝜇ga from Figure 2.18

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Pet. Eng. Dept.- College of Engineering Gas Technology, 4th Stage Usama Alameedy, Ph.D.
Step 9 - Calculate the gas viscosity at reservoir P and T from the following
Equation:
𝜇g
𝜇g = ( ) × 𝜇g
𝜇ga
EXAMPLE 16 Calculate the viscosity of the gas described in EXAMPLE 12
Solution:
Since the gas contains non-hydrocarbon components, the procedure for sour gas is
applicable:
Step 1 - From EXAMPLE 12:
𝑝𝑝𝑐 = Σyj 𝑝cj = 748.3 𝑝𝑠𝑖𝑎, 𝑇𝑝𝑐 = Σ𝑦𝑗 𝑇𝑐𝑗 = 384.5 0R
Step 2 - From EXAMPLE 12, the adjusted values are:

Tpc = 𝑇𝑝𝑐 − 𝜀3 = 384.5 − 20 = 364.5 0R
ppc T′pc 748.3×364.5
p′pc = = = 678.7 psia
Tpc +yH2 S (1−yH2 S )𝜀3 384.5+0.0735(1−0.0735)(20)
Step 3 - From EXAMPLE 12:
𝑇 560 P 1623
𝑇𝑝𝑟 = = = 1.54 Ppr = = = 2.39
T′pc 364.5 P′pc 678.7
Step 4 - From EXAMPLE 12, Ma = 20.03. Using Fig. 14 the (uncorrected) viscosity
of the gas mixture at atmospheric pressure and reservoir T = 100 ° F is:
𝜇ga = 0.0108 cp
Step 5 - From EXAMPLE 12, 𝛾 = 0.69 The viscosity correction factors from the
vertical axis of the inserts in Fig. 14:
yCO2 = 7.44% 𝜇corCO2 = 0.0004
yH2S = 7.35% 𝜇corH2S = 0.00015
yN2 = 0.81% 𝜇corN2 = 0.00008
Step 6 - Calculate the total viscosity correction factor for non-hydrocarbon
components from :
𝜇corNH = 𝜇corCO 2 + 𝜇cor H2𝑆 + 𝜇cor 𝑁2
= 0.0004 + 0.00015 + 0.00008 = 0.00063 cp
Step 7 - Calculate the corrected viscosity of the gas mixture at atmospheric and
reservoir T, 𝜇ga from : 𝜇ga = 𝜇corNH + 𝜇gau = 0.0108 + 0.00063 = 0.01143 cp
Step 8 - Using the adjusted values ofPpr and Tprfrom step 3 (Ppr= 2.39, Tpr= 1.54),
obtain the ratio 𝜇g /𝜇ga : 𝜇g /𝜇ga =1.32
Step 9 - Calculate the gas viscosity at reservoir P = 1623 psia and T - 100 °F from:
𝜇g
𝜇g = ( ) × 𝜇g = 1.32 x 0.01143 = 0.0151 cp
𝜇ga

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