Course Module

Fluid Properties, Equilibrium and Equations of

State

Single-Component
Dry Gas
CHEN 402
Module 3

MacPhail School of Energy Revised: January 2012

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Single-Component Dry Gas
Rationale
Why is it important for you to learn this material?
Gas, especially dry gas, is an important contributor to sales in the petroleum
industry. Unfortunately, gas volume is strongly dependent on pressure and
temperature (that is, gas is very compressible). This module is the first step in
calculating gas behaviour – the single-component gas.

Learning Outcome
When you complete this module you will be able to ….
Calculate the volume of a single-component dry gas at any temperature and
pressure, including standard temperature and pressure. Calculate the changes in
single-component gas volumes due to changes in temperature and pressure.

Learning Objectives
Here is what you will be able to do when you complete each objective.
1. Calculate volumes of a single-component dry gas given pressure and
temperature based on the Ideal Gas Law.

2. Use the Real Gas Law and the Gas Compressibility Factor to calculate the
relationship between pressure, volume and temperature (PVT) of a single-
component dry gas.

3. Calculate the gas density, specific gravity (relative density), Gas Formation
Volume Factor and the Expansion Factor of a single-component dry gas.

Prerequisite
CHEN 402 Modules 1 (Unit Conversions in the Petroleum Industry) and 2 (Phase
Diagrams, Reservoir Hydrocarbons and Reservoir Types) and knowledge of
Excel.

Performance Evaluation
To show you have mastered the material, here is what you will be asked to do.
Calculate the volume of a single-component dry gas at almost any temperature
and pressure (subject to the appropriate equations) and how that volume will
change with changes in pressure and temperature.
1
 OBJECTIVE ONE
When you complete this objective you will be able to…
Calculate volumes of a single-component dry gas given pressure and temperature
based on the Ideal Gas Law.

Learning Activity
Complete each of the Learning Activities listed below.
1. Read the Learning Material.

2. Complete Exercise One.

Learning Material
INTRODUCTION

The behaviour of reservoir fluids is vitally important to the reservoir engineer, for
both deciding how to produce the reservoir and predicting future production. We
will use an Equation of State (EOS) to predict the relationship between the
pressure, temperature and volume (PVT) of the material.

We will start with perhaps the simplest material, dry gas (composition does not
change between reservoir and surface). Here, the isothermal production
temperature will be always greater than the critical point temperature (CP) for a
pure substance (see Figure 1) and greater than the cricondentherm (CT) for a
multi-component mixture (see Figure 2). Make it even simpler; consider only a
single-component dry gas.

Dry Gas Bubble Point Line

Dry Gas
CP
Solid CP
Liquid
Liquid

100% CT
TRIPLE Liquid
Pressure
Pressure

80%
POINT
Gas 60%
Vapour
Pressure 40%
Line Surface/Separator 20%
0% Gas Surface/Separator
Dew Point Line
Temperature
Temperature
Figure 1 Figure 2
Single Component Multi-Component

2
Ideal Gas Law

Definition

We will start with the simplest mathematical way to predict volume from pressure
and temperature: the Ideal Gas Equation of State.

n RT
V
P
Where:
P is ABSOLUTE Pressure (kPaa, psia)
V is Volume (m3, ft3)
T is ABSOLUTE Temperature (K, oR)
n is the number of moles (gmole, kgmole, lbmole)
R is the GAS CONSTANT (value depends on units)

 kPaa.m3 
R  0.008314472  
 gmole.K 
 MPaa.m3 
 0.008314472  
 kgmole.K 
 kPaa.m3 
 8.314472  
 kgmole.K 
 psia.ft 3 
 10.7316  o 
 lbmole. R 

Recall that absolute pressure starts at zero pressure (not atmospheric) and is
indicated with an ‘a’ after the unit and that absolute temperature starts at absolute
zero and is given in degrees Kelvin or Rankine.

The units on the moles are a measure of the mass unit used. The number of the
molar mass (or molecular weight) of the substance remains constant. However,
the mass units can change. The molar mass (also called the molecular weight) of
methane (CH4) is 16.042. A gram-mole (gmole) of methane has 16.042 grams of
methane. A kilogram-mole (kgmole) has 16.042 kilograms of methane. A pound-
mole (lbmole) has 16.042 pounds-mass of methane.

Standard Conditions:

Imperial: 14.65 psia, 60oF

Metric: 101.325 kPaa, 15oC
3
 Ideal Gas Law Example: Find the volume of 12 kgmoles of gas at 70oC and
5,000 kPaa.

nRT
V
P
 kPaa.m3 
12  kgmole  8.314472    70  273.15   K 
  kgmole.K 
5000  kPaa 
 6.85  m3 

Naturally, the Ideal Gas Law can be rewritten to calculate pressure, temperature,
and number of moles as well as volume:

nRT PV PV
P , T , and n 
V nR RT

The Problem

The problem with the Ideal Gas Law is that it does not work, especially at higher
pressures. Basically, it predicts that volume will decrease right down to zero as
pressure increases. This cannot happen; gas molecules have volumes. Thus, the
next step is to include a correction factor to force the equation to fit the
experimental PVT (Pressure-Volume-Temperature) data. This requires the Real
Gas Law, which is discussed in the next objective.

4
Exercise One
1. Find the volume of 57.3 kgmoles of gas at 42.7oC and 15,473 kPaa.

2. Find the pressure of 106.3 lbmoles of gas at 93.6oF in 124.7 ft3.

3. Find the temperature of 448.9 gmoles of gas at 4.198 MPaa in 0.348 m3.

5
 OBJECTIVE TWO
When you complete this objective you will be able to…
Use the Real Gas Law and the Gas Compressibility Factor to calculate the
relationship between pressure, volume and temperature (PVT) of a single-
component dry gas.

Learning Activity
Complete each of the Learning Activities listed below.

1. Read the Learning Material.

2. Complete Exercise Two.

Learning Material
DEFINITION

Define a correction factor, Z, the Gas Compressibility Factor (also called the
Gas Deviation Factor):

ACTUAL Volume of n moles at a fixed T and P

Z
IDEAL Volume of n moles at the same fixed T and P

Z is dimensionless. Therefore, setting V to be the ACTUAL volume of the gas:

n RT  Z 
V
P

This is the Real Gas Law.

Note: PV/TZ is a constant for a fixed amount of gas.

The problem is now to estimate the factor, Z. Fortunately, luck is on our side.

6
Reduced Temperature and Pressure
Assume that we are dealing with a single pure component gas (e.g., methane).
This gas will have a critical point and a critical temperature, Tci, and a critical
pressure, Pci (see Table 1 for these critical values).
Table 1
Physical Properties of Some Natural Gas Components

Gross
Critical Critical
Molar Heating
Name Formula Pressure, Temperature,
Mass Value
Pci (kPaa) Tci (oK)
(MJ/m3)
Nitrogen N2 28.013 3,399.1 126.27 na
Oxygen O2 32.000 5,035.8 154.35 na
Water H2O 18.000 22,058.5 647.20 na
Carbon Dioxide CO2 44.01 7,384.3 304.22 na
Hydrogen Sulphide H2S 34.076 9,004.6 373.55 23.769
Helium He 4.003 229.0 5.30 na
Methane CH4 16.042 4,604.3 190.59 37.676
Ethane C2H6 30.07 4,880.1 305.43 66.004
Propane C3H8 44.097 4,249.2 369.83 93.936
Iso-Butane iC4H10 58.124 3,648.0 408.15 121.374
Normal Butane nC4H10 58.124 3,796.9 425.19 121.726
Iso-Pentane iC5H12 72.151 3,381.2 460.44 149.272
Normal Pentane nC5H12 72.151 3,368.8 469.66 149.613
Hexane C6H14 86.178 3,012.3 507.44 177.474
Heptane+ C7H16+ 114.232 2,486.2 568.84 233.207

Note: Gross heating value requires all combustion products to be adjusted to

101.325 kPaa and 15°C and to be dry. That is, all the water vapour must
be condensed.
The subscript i means that we are dealing with a pure component.
Calculate the Reduced Temperature, Tr, and the Reduced Pressure, Pr, for this
single-component gas at the actual temperature and pressure, T and P:
T (Absolute)
Tr 
Tci (Absolute)

Note: The temperatures are in absolute degrees (K or oR).

Pr  P
(Absolute)
Pci (Absolute)

Note: The pressures are absolute, not gauge.

7
 Law of Corresponding States

The Law of Corresponding States says that all pure gases (only one component)
have the same Z at the same reduced conditions. This is a bit of an approximation.
For example, it implies that all substances have the same Z value at the critical
point (about 0.27); unfortunately, this is not quite true (see Table 2).

Table 2
Z at the Critical Point

Name Formula Z at Critical Point

Nitrogen N2 0.2917
Oxygen O2 0.2880
Water H2O 0.2294
Carbon Dioxide CO2 0.2744

Hydrogen Sulphide H2S 0.2843

Methane CH4 0.2862

Ethane C2H6 0.2793
Propane C3H8 0.2763
Iso-Butane iC4H10 0.2824
Normal Butane nC4H10 0.2739
Iso-Pentane iC5H12 0.2701
Normal Pentane nC5H12 0.2701
Hexane C6H14 0.2959

However, we will accept this approximation. Therefore:

Z only depends on Tr and Pr

There are charts for estimating Z from the reduced temperature and pressure. An
example appears on the next page (Figure 3). (Ignore the prefix “pseudo” for now
– we will discuss this later.)

Note: This graph was generated from an equation for Z and is simplified for ease
of use in this course. In the work world, you may use a more detailed chart
that might give slightly different Z values.

Note: These charts are really only valid for temperatures equal to or greater than
the critical temperature (however, they can apply for temperatures less
than Tci as long as the material is a gas and not a liquid – we have not
shown this part of the charts).

8
Note: Z can also be applied to a liquid as well as a gas – more on this situation
later.

1.10
1.05 T pr = 2.25
1.00
0.95
0.90
0.85
Gas Compressibility Factor, Z

0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45 Pseudoreduced
Temperature, T pr
0.40 from 1.05 to 2.25
0.35 in steps of 0.05

0.30
0.25 T pr = 1.05
0.20
7.5
8.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0

Pseudoreduced Pressure, P pr

Figure 3
Gas Compressibility Factor

We won’t use this chart in this course – it is too complicated. However, notice
three things:

1) Z at low pressure is virtually 1; therefore Z at standard conditions is 1.

2) Z decreases as pressure rises, then increases.
3) Z can be both less than one and greater than one.

9
 Gas Compressibility Add-in in Excel
There are many equations for calculating Z. One of the simplest (and yet still
reasonably accurate) was created by Brill and Beggs and modified by Standing
(Table 3). This is the equation used to calculate Z in your Excel Add-in:
CH_Gas_Compress_Z.
Note: 1  Tr  2.6 and Pr  0 for this Add-in.

Real Gas Volume Example: Given the following data, please find the gas volume
at the supplied pressure and temperature.
Table 3
Real Gas Volume Example Data

n (gmoles) = 5,000 Critical Pressure (kPaa) = 4,651.6

o
T ( C) = 35 Critical Temperature (K) = 242.97
3
P (kPaa) = 8,000 R (kPaa.m /gmole.K) = 0.008314472

First, find the reduced pressure and temperature (remember that temperature is in
absolute degrees and that pressure is also in absolute).

Pr 
8000  kPaa 
 1.72 and Tr 
 35  273.15  K   1.268
4651.6  kPaa  242.97  K 

Therefore, from the simplified chart on the next page (Figure 4): Z  0.71
Thus, the volume calculation is straightforward (recall that both temperature and
pressure are in absolute units).

  kPaa.m3  
5000  gmole  0.008314472     35  273.15   K  0.71
nRTZ   gmole.K 
V 
P 
8000 kPaa 
 1.14 m 3

10
 1.000
0.975
0.950
0.925
0.900
0.875
0.850
0.825 Reduced
Temperature,
Gas Compressibility Facor, Z

0.800
Tr = 1.3
0.775
0.750
0.725
0.700
0.675
0.650
0.625 Reduced
Temperature,
0.600 Tr = 1.2 Calculated
Z
0.575
0.550
0.525
0.500
0.475
0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

2.75

3.00

Reduced Pressure, Pr
Figure 4
Gas Compressibility Factor

11
 New Volumes from the Real Gas Law

The petroleum industry uses volume rather than mass for the various fluids.
However, volume depends on pressure, temperature and composition (for gases
especially, but also for liquids). Thus, we need to calculate new gas volumes for
different pressures and temperatures.

Let some gas go from condition 1 to condition 2, as shown in Figure 5, perhaps

transferring between tanks.

Volume = V2
Volume = V1
Pressure = P2
Pressure = P1
Temperature = T2
Temperature = T1
# of moles = n2 = n1 + (or -) n
# of moles = n1 Add (or Remove) n moles

Condition (1) Condition (2)

Figure 5
Changing Gas Volumes

Each condition has a pressure, temperature and gas volume. To make it more
interesting, add some gas (or subtract some gas) as it moves; thus, there is a
different number of moles of gas in each condition. The question is: if we know
the gas volume at condition 1, what is the gas volume at condition 2? The Real
Gas Law for the two conditions, 1 and 2, gives:

n1 RT1Z1 n2 RT2 Z 2
V1  and V2 
P1 P2

If we divide the second volume by the first and rewrite, we get:

 P  n   T  Z 
V2  V1  1  2   2  2 
 P2  n1   T1  Z1 

Suppose we know everything at condition 1 (volume, temperature, and pressure –

thus Z1). We want to find the new volume of this gas at a different temperature
and pressure; that is, condition 2. Since we know the new temperature and
pressure, we can calculate the new Z, Z2.

12
We could even change the composition of the gas between the two conditions. As
long as we can calculate the two values of Z, this method works. We will discuss
this problem in a later module.

Volume Change Example: A known mass of methane occupies 103 m3 at a

temperature of 65oC and a pressure of 4.5 MPaa. Call this condition 1. This mass
of gas goes into a new tank at a temperature of 35oC and a pressure of 10.5 MPaa
(no extra mass added or subtracted). This is condition 2. What is the volume of
this tank?

Methane has a critical pressure of 4,604.3 kPaa and a critical temperature of

190.59 K. Calculation (or a Z graph) gives a gas compressibility factor, Z1, of
0.954 for the original condition and Z2 = 0.853 for the new condition.

Given these, the new volume is:

 P   n   T  Z 
V2  V1  1   2   2  2 
 P2   n1   T1  Z1 
 4.5  MPaa    Constant # of moles   35  273.15  K    0.853 
 103  m3      
 10.5  MPaa    Constant # of moles   65  273.15  K    0.959 
 35.99 m 3 

We could calculate the number of moles, but since that number cancels, why
bother?

Recall that both pressure and temperature must be absolute.

New Pressures or Temperatures from Iteration

Recall that the Real Gas Law for the gas at two conditions (1 and 2) gives (after
some algebra):

 V2   P1   T2   n2  Z 2 
 V    P   T   n  Z 
 1   2   1   1  1 

Suppose we know the pressure, temperature, number of moles and volume at

condition 1. Since we know the gas and the pressure and temperature, we also
know the Z at condition 1. Now, if we know the temperature, number of moles,
and volume at condition 2, we want to calculate the pressure at condition 2.
Conversely, we might want to know the temperature at condition 2 if we know the
new pressure, number of moles and volume. That is:

 V 1   T 2   n2   Z 2   V 2   P 2   n1   Z 1 
P 2  P1         or T 2  T1        
 V 2   T 1   n1   Z 1   V 1   P1   n 2   Z 2 

13
 Problem: If we want to calculate P2 (or T2) we need to know Z2. Unfortunately, Z2
depends on P2 and T2. Thus, we need to know the right answer before we start.

How to solve this? The answer is a very powerful solution tool called iteration.
In this process, we first guess a value for the final answer (here, Z2). We then use
this Z2 to calculate a value for P2 (or T2). Then we use this new value (note: use
both the new pressure and the new temperature) to find a new Z2. Then use the
new Z2 to find an even newer P2 (or T2). Then another Z2, another P2 (or T2), and
so on. We end the process when the difference between two successively
calculated P2’s (or T2’s) is so small that it makes no practical difference which
value of P2 (or T2) we pick.

The value of the initial guess (here, of Z2) is always open to discussion. One
common starting point is to use the already known value (here, Z1) to begin the
process. Another common starting point is Z2 = 1.

The ending is also always open to dispute. How little difference between one
calculated value and the next cycle’s calculated value is small enough? That is a
question you have to decide.

The downside is that this iteration process can be very slow, require a lot of
iterations and is usually best done by a computer. There is also no guarantee that
the iterations will converge to a single answer, especially if the system is very
nonlinear (such as Z vs. pressure and temperature).

Iteration Example: Take 1 m3 of CH4 at 4 MPaa and –73.3oC. Compress this gas
to a new volume of 0.2 m3 and a new temperature of -65oC. No gas is added or
removed. What is the new pressure?

The critical temperature and pressure for methane are 190.59 oK and 4.6043
MPaa. Thus, the constant reduced temperature is (273.15-73.03)/190.59 = 1.0486.
The initial reduced pressure is 4/4.6043 = 0.8688. Therefore, from a chart or
calculation, the initial Z is approximately 0.6585.

Since the number of moles of gas has not changed, we do not need to calculate it.
However, it will help in this example by showing how the new volume gets closer
to the correct value as the process continues.

PV
n 1 1
RT1Z1
4  MPaa 1 m3 

 MPaa.m3 
0.008314472    73.3  273.15   K   0.6585 
 kgmole.K 
 3.655  kgmole 

14
The equation we use to calculate the new pressure is:

 V 1   T 2   n2   Z 2 
P 2  MPaa   P1        
 V 2   T 1   n1   Z 1 
 1 m3     65.0  273.15   K    3.655  kgmoles    Z 2 
 4  MPaa   3    
 0.2  m     73.3  273.15   K    3.655  kgmoles    0.6585 
 31.6316 Z 2  MPaa 

Start with Z2 = Z1 and calculate a new P2. Then use this to find a new Z2 (use the
new P2 and the final temperature, -65oC, NOT the original temperature), which
we use to find a newer P2 and so on. Note that P1, Z1, T1, T2 and the volumes and
moles DO NOT change between iteration steps. The pressure (and Z) usually
changes less and less with each iteration as the number of iterations increases (the
“final” answer is approximately 13.65 MPaa). Where you decide to stop is up to
you. The first few steps are shown below.

Although not required, calculate the volume at each iteration using the new
pressure and the Z value that created that new pressure from:

nRTZ
V
P
Table 4
Iteration Steps

Iteration New P (New P - Calculated

Old Z New Z
Number (MPaa) Old P) Volume (m3)
1 0.6585 20.8306 0.6114 na 0.1857
2 0.6114 19.3400 0.5741 -1.4907 0.1878
3 0.5741 18.1612 0.5446 -1.1788 0.1897
4 0.5446 17.2280 0.5213 -0.9331 0.1914
5 0.5213 16.4887 0.5027 -0.7394 0.1929

The following four graphs (next two pages) help show what is happening. The
upper left graph (Figure 6) shows the new pressure vs. the iteration number.
Notice that it changes quickly until it settles down to pressures near the final value
after 30 iterations, 13.6461 MPaa. (Note: This is not the final answer – we can
never get to the final answer.)

The upper right graph (Figure 7) displays the change in pressure (defined as the
pressure at the iteration number minus the pressure at the previous iteration
number). The change gets smaller quite quickly.

However, the change does not reach zero. The lower left graph (Figure 8) is the
absolute value of the pressure changes (done to eliminate the negative values so
that we can use a log scale). The change gets smaller, but still does not disappear.
15
 Where you stop it is your choice. The lower right graph (Figure 9) is a plot of the
calculated volume at each iteration (calculated using the new pressure AND the
new temperature). Again, you can see that it approaches the correct value (0.2
m3), but never quite reaches it. It is a good idea to calculate the volume using the
pressure and temperature when you stop calculating just to ensure that your
answer is reasonable.

20 0.1

0.0

19 -0.1

-0.2

-0.3
18
-0.4

-0.5

Change in New Pressure (MPa)

17
-0.6
New Pressure (MPaa)

-0.7
P = (P)i - (P)i-1
16 -0.8 where i = Iteration Number
-0.9

-1.0
15
-1.1

-1.2
14
-1.3

-1.4

13 -1.5
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Iteration Number Iteration Number

Figure 6 Figure 7
Iteration Example: Iteration Example:
New Pressure vs. Iteration Number Δ Pressure vs. Iteration Number

16
 10 0.201

0.200
P = (P)i - (P)i-1
where i = Iteration Number 0.199

0.198

1 0.197
Absolute Value of the Change in New Pressure (MPaa)

0.196

0.195

0.194

Calculated Volume (m3)

0.1 0.193

0.192

0.191

0.190

0.01 0.189

0.188

0.187

0.186

0.001 0.185
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Iteration Number Iteration Number

Figure 8 Figure 9
Iteration Example: Iteration Example:
ABS (Δ Pressure) vs. Iteration Number Calculated Volume vs. Iteration Number

Note: Since Z is not monotonic (Z decreases with increasing pressure but then
increases) it is quite possible that the iteration won’t work. In this case, absolute
value of the change in pressure or temperature with get larger and the iteration
will basically explode. The solution is to try another starting value for Z – either
larger or smaller. Eventually, the iteration should work.

17
 Exercise Two
1. Given the following data, please find the gas volume at the supplied pressure
and temperature using the Real Gas Law and the simplified Z chart on the next
page (Figure 10).

n (kgmoles) = 12,500 Critical Pressure (kPaa) = 4,651.6

T (oC) = 135 Critical Temperature (K) = 242.97
P (kPaa) = 45,500 R (kPaa.m3/kgmole.K) = 8.314472

2. A known mass of methane occupies 34.76 m3 at a temperature of 23.6oC and a

pressure of 24,423 kPaa. This mass of gas goes into a new vessel at a
temperature of 89.33oC and a pressure of 35.89 MPaa. What is the volume of
this vessel? Hint: Remember absolute temperatures and use the simplified Z
chart on the second following page (Figure 11).

3. Given the following data (constant number of moles or mass of gas), calculate
the first three iteration steps (new pressures and Z’s). If you are having
trouble calculating the values, check the first two steps in the answers. Use
the simplified Z chart on the third following page (Figure 12). Remember that
this Z is for the new temperature. If you do this in Excel, try calculating the
final pressure.

Initial Pressure (MPaa) = 25

o
Initial Temp. ( C) = 65
3
Initial Volume (m ) = 75
o
Final Temp. ( C) = 105
3
Final Volume (m ) = 50
Critical Pressure (MPaa) = 4.6043
o
Critical Temperature ( K) = 190.59

18
 1.113

1.112

1.111

1.110

1.109
Gas Compressibility Factor, Z

1.108

1.107

1.106

1.105

1.104

1.103

1.102

1.101

1.100

1.099
350 360 370 380 390 400 410 420 430 440 450
Temperature (K)
Figure 10
Gas Compressibility Factor for Exercise 2, Question 1

19
 1.05

1.00

T = 89.33 oC
Gas Compressibility Factor, Z

0.95

0.90

T = 23.6 oC

0.85

0.80
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37
Pressure (MPaa)

Figure 11
Gas Compressibility Factor for Exercise 2, Question 2

20
 1.40

1.35 Calculated at
Final Temperature

1.30

1.25
Gas Compressibility Factor, Z

1.20

1.15

1.10

1.05

1.00

0.95

0.90
11.0
11.5
10.0
10.5

12.0
12.5
13.0
13.5
14.0
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5

Reduced Pressure, Pr

Figure 12
Gas Compressibility Factor for Exercise 2, Question 3

21
 OBJECTIVE THREE
When you complete this objective you will be able to…
Calculate the gas density, specific gravity (relative density), Gas Formation
Volume Factor and the Expansion Factor of a single-component dry gas.

Learning Activity
Complete each of the Learning Activities listed below.
1. Read the Learning Material.

2. Complete Exercise Three.

Learning Material
GAS DENSITY

Density is mass/volume. For a gas, this is the number of moles in a volume

multiplied by the molecular weight (molar mass), all divided by that volume, or:

mass n  MW 
g  
Volume V

Here, MW is the molecular weight of the gas (mass/mole or the molar mass). At
an absolute temperature and pressure T and P:

n P

V ZT R

P  MW 
Thus, the gas density is: g 
ZT R

Hint: The units of density are mass/volume, so watch the units in this equation.

Gas Density Example: What is the density of methane at -50oC and 7,000 kPaa?
The critical temperature and pressure for methane are 190.59 K and 4,604.3 kPaa.
The molecular weight (molar mass) is 16.042 kg/kgmole. R is 8.314472
kPaa.m3/kgmole.K. Remember that both temperature and pressure are in absolute
units.

Get absolute temperature: T   50  273.15   223.15  K 

22
 T  50  273.15   K 
Reduced temperature: Tr    1.1708
Tci 190.59  K 

P 7000  kPaa 
Reduced pressure: Pr    1.5203
Pci 4604.3  kPaa 

Therefore, the Z value from a chart (or the add-in) is:

Z = 0.6272

Thus, the gas density is:

 kg 
7000  kPaa 16.042  
P  MW   kgmole 
g  
ZT R  kPaa.m3 
0.6272  223.15  K  8.314472  
 kgmole.K 
 kg 
 96.5  3 
m 

Gas Specific Gravity (Relative Density)

However, the petroleum industry rarely uses the gas density. The preferred
variable is the gas specific gravity.

The specific gravity of a liquid is the density of the liquid divided by the density
of water. Similarly, the specific gravity of a gas is the density of the gas divided
by the density of air at the same conditions!

The molecular weight of air is 28.97 kg/kgmole. So, the gas specific gravity, γg,
is calculated from:

 P MWg 
 
 g  Z g T R   Z air   MWg   Z air   MWg 
g      
 air  P MWair   Z g   MWair   Z g   28.97 
 
 Z air T R 

MWg is the molecular weight (molar mass) of the gas.

However, this is too complicated for general use, so engineers make the
approximation Zg = Zair. Thus, the specific gravity of gas is:

23
 MWg
g 
28.97

Since molar mass (molecular weight) does not change with pressure or
temperature, the specific gravity of any particular gas is constant.

The gas specific gravity is sometimes called the relative density, G. However,
using G will lead to confusion when discussing gas production from a reservoir.

Gas Specific Gravity Example: Find the specific gravity of hydrogen sulphide
(H2S).

The molecular weight (molar mass) of H2S is 34.076 (here the units do not
matter). Therefore, the specific gravity of hydrogen sulphide is:

MWH 2 S
 
g H S
2

28.97

34.076
28.97
 1.176

Gas Formation Volume Factor

Definition

Reservoir dry gas is under high pressure and temperature. As we produce the gas
to surface, the volume we have to handle will certainly change due to changes in
pressure and temperature. However, how much volume will we have to handle?

Also, if we want to compare the amount of gas in two or more reservoirs that will
have different pressures and temperatures, how do we do it?

The usual way to handle gas volumes is to convert the actual volume to the
volume at Standard Temperature and Pressure (STP). Comparison is then
simple. However, to make this conversion easier, engineers had to invent a VERY
important parameter, the Gas Formation Volume Factor, Bg. For a fixed mass
of gas, this is:

Gas Volume at Reservoir Conditions

Bg 
Gas Volume at Standard Temperature & Pressure

24
We know the volume of a fixed mass of gas at any condition, V, and at standard
conditions, VSTP:

ZT   Z STP TSTP 

V  n R  and VSTP  n R  
 P   PSTP 

V  Z  T   PSTP 
Therefore: Bg     
VSTP  Z STP   TSTP  P 

However, ZSTP is virtually 1 (the reduced pressure is almost zero), so:

 T   PSTP 
Bg  Z    P 
 TSTP 

Note: T, TSTP, P and PSTP are absolute!

Often the only reason to calculate Z is to calculate Bg.

The Excel Add-in function for the Gas Formation Volume Factor is
Ch_Gas_FVF_Bg.

The physical meaning of Bg is quite simple. It is the final volume 1 cubic metre
of gas at standard conditions achieves as it moves to the actual temperature and
pressure. Basically, it is the behaviour of the gas as it goes from the standard
condition to some other condition.

As shown in Figure 13, Bg falls dramatically as pressure rises (the major effect).
However, Bg rises with increasing temperature.

Notice that Bg can be larger than one if the temperature is high and the pressure is
low. That happens very rarely, but it can happen.

25
 10

Gas is Methane (CH4)

Gas Formation Volume Factor, Bg (rm3/sm3) 0.1

T = 100 oC (373.15 oK)

T = 50 oC
0.01

T = 15 oC

0.001
0 5,000 10,000 15,000 20,000 25,000
Absolute Pressure, P (kPaa)

Figure 13
Gas Formation Volume Factor vs. Temperature and Pressure

Units of the Gas Formation Volume Factor

As Z is dimensionless, Bg is dimensionless (and thus is the same number in either

imperial or metric units). However, it is useful practice to add units for use in later
calculations (defined as reservoir volume/standard volume).

Reservoir volume does NOT only mean a volume in a reservoir. It is

shorthand for a volume at ANY temperature and pressure.

In metric, Bg has the units of reservoir m3/standard m3 (or rm3/sm3, or just

m3/sm3). In imperial, the units are reservoir ft3/standard ft3 (or rft3/sft3, or just
ft3/sft3, or ft3/SCF). In either case, the units cancel (Bg is dimensionless), but we
will keep them for easier calculation; doing so reduces the chance of error.

26
New Volumes from Gas FVF

Calculating new volumes using the gas formation volume factor, Bg, is quite
simple. The definition of Bg is:

 T   PSTP   rm 
3
Bg  Z    P   sm3 
 TSTP 

Condition 1 has P1, T1 (hence Z1) and V1. Condition 2 has P2 and T2 (hence Z2).
There is the same amount of gas at each condition. The situation is shown in
Figure 14.

Volume = V2
Volume = V1
Pressure = P2
Pressure = P1
Temperature = T2
Temperature = T1
# of moles = n
# of moles = n

Condition (1) Condition (2)

Figure 14
Volume Changes with the Gas Formation Volume Factor

The two values of Bg are:

 T   PSTP   rm @ 1   T   PSTP   rm @ 2 
3 3

B 
g 1  Z1  1  P  sm3  and
   B 
g 2  Z2  2  P  sm3 
  
 TSTP  1   TSTP  2 

Dividing one by the other and simplifying gives:

B 
g 2  rm3 @ 2   P1   T2   Z 2 
 3      
B g 1  rm @ 1   P2   T1   Z1 

Therefore, the volume at condition 2 is just the volume at condition 1 multiplied

by this Bg ratio:

V2  V1
B 
g 2  P  T  Z 
 V1  1  2  2 
B 
g 1  P2  T1  Z1 

This is exactly the same as calculating a new volume directly from the Real Gas
Law.
27
 What happens if the amount of gas changes as well? Condition 1 has n1 moles of
gas and Condition 2 has n2 moles.

Rewrite the Gas Formation Volume Factor equation as:

TZ  PSTP 
Bg 
P  TSTP 

TZ V
The Real Gas Law gives: 
P nR

 T 
Therefore: V   nBg   R STP 
 PSTP 

Substitute the values for Conditions 1 and 2, divide V2 by V1, cancel the constants
(R, TSTP, and PSTP), and:

 n2  Bg  
V2  V1  2

 n1  Bg 1 

Note: The gas doesn’t have to have a constant composition; the Bg (and Z) values
will take care of that (as will be shown later).

Gas Expansion Factor

Quite often we want to know how much the gas expands in volume as it rises
from the reservoir to the surface (assuming, of course, that surface is at STP).
Thus, define the Gas Expansion Factor, Eg, of a constant mass of gas as:

1
Gas Expansion Factor  Eg 
Bg

The expansion factor is standard volume/reservoir volume (e.g., sm3/rm3).

The physical meaning of the expansion factor is simple. It is the volume 1 cubic
metre of gas at some actual temperature and pressure achieves as it moves to
standard conditions.

The gas expansion factor rises as the reservoir pressure rises, but falls as the
temperature increases. This is shown by Figure 15.

28
 300

275 Gas is Methane (CH4)

250

225
50 oC
200
Gas Expansion Factor, Eg = 1/Bg (sm3/rm3)

175 T = 15 oC

150

125

100
T = 100 oC (373.15 oK)
75

50

25

0
0 5,000 10,000 15,000 20,000 25,000
Absolute Pressure, P (kPaa)

Figure 15
Gas Expansion Factor vs. Temperature and Pressure

29
 Gas Formation Volume Factor and Expansion Factor Example 1: Given
methane at the following conditions, please find the gas formation volume factor
and the expansion factor.

Pressure (kPaa) = 6,000 Critical Pressure (kPaa) = 4,604.3

o
Temperature ( C) = 25 Critical Temperature (K) = 190.59

The first step is to find the Z at the given pressure and temperature. This needs the
reduced pressure and temperature, or:

Pr 
6000
 1.3031 and Tr 
 25  273.15  1.5644
4604.3 190.59

A quick look at the Z chart (or the computer) gives Z = 0.897. Since TSTP = 15oC
and PSTP = 101.325 kPaa, the gas formation volume factor is simple to calculate
(recall that both pressure and temperature are in absolute units):

 T   PSTP   25  273.15   101.325  rm3

Bg  Z     0.897     0.01567
 TSTP  P   15  273.15   6000  sm3

Therefore, the expansion factor is:

1 1 sm3
Eg    63.81 3
Bg 0.01567 rm

That is, the gas volume increases by 63.81 times from “reservoir” conditions to
STP.

Gas Formation Volume Factor and Expansion Factor Example 2: Move a

constant mass of C3H8 from one tank (150 rm3, 125oC, and 27,000 kPaa) to a
second tank (175oC and 13,000 kPaa). What is the required volume of the second
tank?

The critical pressure and temperature of propane are 4,249.2 kPaa and 369.83 K.
Calculating the reduced pressure and temperature in each tank gives these Z
values.

Tank 1 Tank 2

Z 0.817 0.526

Now calculate the gas formation volume factors for each tank. As an example,
find Bg for tank 1, (Bg)1.

30
  T  P   125  273.15  K    101.325  kPaa  
B   Z1  1   STP   0.817   
 15  273.15  K    27000  kPaa  
g
 TSTP   P1 
1

 rm3 
 4.24 x103  3 
 sm 

Recall that Canadian standard temperature and pressure are 15oC and 101.325
kPaa.

Thus, the gas formation volume factors in each tank are:

Tank 1 Tank 2
-3
Bg 4.24x10 6.38x10-3

Now calculate the volume of the second tank.

3  rm 
3

V2  V1
 Bg 2  150  rm3  6.38 x10  sm3 
 Bg 1  rm3 
4.24x103  3 
 sm 
 225.8 rm 3 

Gas Formation Volume Factor and Expansion Factor Example 3: Move some
C2H6 from one tank (170 rm3, 135oC, and 22,000 kPaa) to a second tank (185oC
and 17,000 kPaa) and add 400 kgmoles of C2H6 to this second tank. What is the
required volume of the second tank?

The problem here is a little more complex as we do not know the amount of gas in
the first tank. However, we can quickly calculate the values of Z and Bg in each
tank before we do anything else.

The critical pressure and temperature of ethane are 4,880.1 kPaa and 305.43 K.
Calculating the reduced pressure and temperature in each tank gives these Z and
Bg values from the chart (or add-in).

Tank 1 Tank 2

Z 0.7048 0.7693

Bg 4.598x10-3 7.290x10-3

The number of kgmoles of gas in the first tank comes from the Real Gas Law:

31
 PV 22000  kPaa  170  rm3 
n1  1 1

RT1Z1  kPaa.m3 
8.314472   135  273.15  K  0.7048
 kgmole.K 
 1563.7  kgmoles 

Therefore:

n2 = n1 + 400 [kgmoles] = (1,563.7 + 400) [kgmoles] = 1,963.7 [kgmoles]

So the volume of the second tank is:

   rm3   
 n2  Bg    1963.7  kgmoles  0.007290  sm3   
V2  V1  2
  170  rm3    
 n1  Bg 1     rm   
3

1563.7  kgmoles   0.004598  3   

   sm   
 338.5 rm 3 

32
Exercise Three
1. What are the two densities of methane in the following table? Use the
simplified Z chart on the next page (Figure 16).

T (oC) P (kPaa)
40 130
-30 10,000

2. Find the specific gravity of the two gas densities in Exercise 1. Notice what
changes and what does not change.

3. What are the gas formation volume factor and the expansion factor of methane
at 50°C and 5 MPaa? (Z = 0.938)

4. What are the gas formation volume factor and the expansion factor of C2H6 at
120°C and 12 MPaa? (Z = 0.641)

5. Move (very carefully) a constant mass of H2S from one tank (375.6 rm3,
226°C and 37,525 kPaa) to a second tank (126°C and 17,045 kPaa). What is
the required volume of the second tank? Find the Z factors from the simplified
chart on the second following page (Figure 17).

33
 1.05

1.00

P = 130 kPaa
0.95

0.90
Gas Compressibility Factor, Z

0.85

0.80

P = 10,000 kPaa

0.75

0.70

0.65

0.60

0.55
-40 -30 -20 -10 0 10 20 30 40 50
Temperature (oC)

Figure 16
Gas Compressibility Factor for Exercise 3, Question 1

34
 0.80

0.75

0.70

0.65 P = 37,525 kPaa

Gas Compressibility Factor, Z

0.60

0.55

0.50
P = 17,045 kPaa
0.45

0.40

0.35

0.30

0.25
1.05 1.10 1.15 1.20 1.25 1.30 1.35
Reduced Temperature, Tr

Figure 17
Gas Compressibility Factor for Exercise 3, Question 5

35
 Exercise One Answers
1. 9.725 m3

2. 5,061.5 psia

3. 349.4 K (76.3oC)

Exercise Two Answers

1.
Reduced Pressure = 9.782 Z= 1.099
3
Reduced Temperature = 1.680 Volume (m ) = 1,024.9

2. Z1 = 0.833, Z2 = 1.014, V2 = 35.17 m3

3. P 2  46.70415 Z 2 , Final Pressure = 62.28 MPaa

Iteration Old P New P

Old Z New Z
Number (MPaa) (MPaa)

1 25 0.89791 41.93590 1.08793

2 41.93590 1.08793 50.81074 1.18941
3 50.81074 1.18941 55.55050 1.24775

36
Exercise Three Answers
1.
T (oC) P (kPaa) Z  g (kg/m3)
40 130 0.998 0.802
-30 10,000 0.657 120.8

2.
T (°C) P (kPaa) Z  g (kg/m3) g
40 130 0.998 0.802 0.554
-30 10,000 0.657 120.8 0.554

3. Z = 0.938, Bg = 0.02131 rm3/sm3, Eg = 46.93 sm3/rm3

4. Z = 0.641, Bg = 0.007383 rm3/sm3, Eg = 135.5 sm3/rm3

5.
Tank 1 Tank 2
Z 0.681 0.286
-3
Bg 3.19x10 2.35x10-3

V2 = 277.3 rm3

37
 Module Self-Test
Directions:

 Answer the following questions.

 Compare your answers to the enclosed answer key.
 If you disagree with any of the answers, review learning activities and/or check with your
instructor.
 If no problems arise, continue on to the next objective or next examination.

1. You are designing a plant to process i-butane. The gas will be moved between
two tanks (called “first tank” and “second tank”). Some gas will be removed
as it moves from the first tank to the second tank. The design details are given
below. Unfortunately, the temperature in the second tank is not available –
you will have to calculate it.

Please fill in the blank tables below and on the next page. You will have to do
an iteration to find the temperature in the second tank – the first two steps are
included to help you. Suggestion: use the Excel Add-in to find the gas
compressibility factor. Although you are only asked for a few steps of the
iteration, you might take it further in Excel to get a reasonable final answer.
Warning: the temperature will rise and fall between steps – that is expected.

First Tank Temperature (oC) = 225

First Tank Pressure (kPaa) = 10,575

3
First Tank Volume (rm ) = 1,541
Second Tank Pressure (kPaa) = 5,445
3
Second Tank Volume (rm ) = 5,140

Amount of Removed Gas (kgmoles) = 1,300

Gas Molar Mass

Gas Specific Gravity, g
Gas Critical Pressure, Pci (kPaa)
Gas Critical Temperature, Tci (K)
Z Value in the First Tank
Amount of Gas in First Tank, kgmoles
Amount of Gas in Second Tank, kgmoles
Final Estimate of Second Tank Temperature (oC)

38
 (New - Old) T2
Step # Old T2 (oC) Old Z2 New T2 (oC) new Z2
(oC)
1 225.000 0.5247 761.794 0.9910 536.794
2 761.794 0.9910 274.786 0.7944 -487.008
3
4
5

Note: T2 and Z2 are the estimated temperature and gas compressibility factor in
the second tank. The starting assumption is that they are equal to the
values in the first tank.

2. You have been asked to decide which of two reservoirs (Big Gas and Little
Hope) has more gas volume. The details about each reservoir are listed below.
Hints: How do you compare volumes, recall how Excel handles powers of
ten, use the Excel Add-in, and the blank answer tables may help you decide
which reservoir has more gas.

Big Gas Little Hope

Gas = CH4 Gas = C2H6
Temperature (oF) = 172 Temperature (oC) = 56
Pressure (psia) = 5,994 Pressure (kPaa) = 35,619
Gas Volume (rft3) = 1.16E+09 Gas Volume (rm3) = 3.48E+07

Big Gas Little Hope

γg γg
Z Z
Bg Bg
Eg Eg
Gas Volume (sm3) Gas Volume (sm3)

39
 3. Your employer, Drain‘em Dry Oil, owns a field producing 100% methane.
Given the following reservoir temperature and pressure and daily produced
volume at surface (defined as standard temperature and pressure), please
calculate the gas volume in the reservoir. Hints: Use the Excel Add-in and the
answer table.

Reservoir Temperature (oC) = 85

Reservoir Pressure (MPaa) = 13.59
3
Production Rate (sm /day) = 3,460,000

Z
Bg
Production Rate (rm3/day)

4. Drain‘em Dry Oil owns a plant using 100% C2H6. Given the following plant
temperature and pressure and number of moles of gas, please calculate the
volume in the plant and at standard conditions. Hints: Find Z and Bg from the
Excel Add-in and the answer table may help guide your calculation.

You will need to use Excel in this course, including calculation, plots and the
Add-in. Thus, please plot Z and Bg at the plant temperature from a pressure of
100 kPaa to 30,000 kPaa in steps of 100 kPaa (use the Excel Add-in and an
Excel Scatterplot with a smoothed line but no point markers and a pressure
scale from 0 to 30,000 – do not use the lineplot; it will not work). Hint: Use a
log scale for Bg to make it easier to see what is happening.

Yet more work. Please plot Z and Bg at the plant pressure from a temperature
of 40oC to 140oC in steps of 1oC (again use the Excel Scatterplot). You won’t
need a log scale for Bg here.

Plant Temperature (oC) = 165

Plant Pressure (kPaa) = 25,798
Number of kgmoles = 7,548

Z=
γg
Gas Volume (rm3)
Bg
Eg
Gas Volume (sm3)

40
Self-Test Answers
1.
Gas Molar Mass 58.124
Gas Specific Gravity, g 2.006
Gas Critical Pressure, Pci (kPaa) 3,648.0
Gas Critical Temperature, Tci (K) 408.15
Z Value in the First Tank 0.5247
Amount of Gas in First Tank, kgmoles 7,499.3
Amount of Gas in Second Tank, kgmoles 6,199.3
o
Final Estimate of Second Tank Temperature ( C) 350

Step # Old T2 (oC) Old Z2 New T2 (oC) New Z2 (New - Old) T2 (oC)
1 225.000 0.5247 761.794 0.9910 536.794
2 761.794 0.9910 274.786 0.7944 -487.008
3 274.786 0.7944 410.346 0.9108 135.561
4 410.346 0.9108 323.029 0.8484 -87.318
5 323.029 0.8484 366.895 0.8838 43.866

2. Little Hope has more gas. Since gas volume is so sensitive to pressure and
temperature, you have to convert reservoir volumes to standard volumes. The
answer tables follow.

Big Gas Little Hope

γg 0.554 γg 1.038
Z 1.0634 Z 0.9281
Bg 3.175E-03 Bg 3.016E-03
Eg 314.94 Eg 331.57
3 3
Gas Volume (sm ) 1.035E+10 Gas Volume (sm ) 1.154E+10

3.
Z 0.9144
Bg 8.474E-03

Production Rate (rm3/day) 29,320

41
 4.
Z= 0.7920
γg 1.038
3
Gas Volume (rm ) 844.21
Bg 4.730E-03
Eg 211.41
3
Gas Volume (sm ) 178,471

Z vs. Pressure Bg vs. Pressure

Z vs. Temperature Bg vs. Temperature

42
References
Bloomer, O. T., Gami, D. C., & Parent, J. K. (1953). Physical-Chemical
Properties of Methane-Ethane Mixtures. Research Bulletin 22, Institute of Gas
Technology, Chicago.

43
 Glossary
Gas Compressibility Factor, Z - A dimensionless factor introduced in the real
gas law to give the correct volume at any temperature or pressure. Theoretically,
it only depends on reduced temperature and pressure. However, in spite of its
name, it can also apply to liquids.

Gas Constant, R - A number (a proportional constant) used in both the ideal and
real gas laws. This number depends on the units in the equation.

Gas Density,  - The mass of a gas divided by its volume. The gas density
changes with temperature and pressure.

Gas Expansion Factor, Eg - The volume of a mass of gas at standard conditions

(STP) divided by the volume of the same mass of gas at a temperature and
pressure. This dimensionless factor depends on Z and changes with pressure and
temperature. It is 1 divided by the gas formation volume factor and is used to
convert gas volumes to standard conditions.

Gas Formation Volume Factor, Bg - The volume of a mass of gas at a

temperature and pressure divided by the volume of the same mass of gas at
standard conditions (STP). This dimensionless factor depends on Z and changes
with pressure and temperature.

Gas Specific Gravity (Relative Density), g - The molar mass (molecular

weight) of a gas divided by the molar mass of air (28.97). The gas specific gravity
is independent of pressure and temperature.

Critical Point - The temperature and pressure at which the gas and the liquid
have the same properties.

Critical Point Pressure for a Single Substance, Pci - The pressure at the critical
point (there is only one critical pressure for each single material).

Critical Point Temperature for a Single Substance, Tci - The temperature at the
critical point (there is only one critical temperature for each single material).

Dry Gas - Gas that remains as gas (does not condense) in any of the appropriate
temperatures and pressures (including standard).

Equation of State (EOS) - A mathematical relationship between the pressure,

temperature and volume (PVT) of a material.

Ideal Gas Law - The relationship between pressure, temperature and volume
(PVT) for an ideal gas – a gas for which the volume is always proportional to
temperature and always inversely proportional to pressure.
44
Law of Corresponding States - The observation that all single-component gases
have the same gas compressibility factor value, Z, at the same reduced conditions.
It is only a useful approximation.

Molar Mass (Molecular Weight) - A number indicating the mass of 1 mole of

material. This number is the same no matter what units are used.

Real Gas Law - The actual relationship between pressure, temperature and
volume (PVT) for a real gas – a gas for which the volume is only roughly
proportional to temperature and only roughly inversely proportional to pressure.

Reduced Pressure, Pr - The actual pressure divided by the single-component

critical pressure (both in absolute units).

Reduced Temperature, Tr - The actual temperature divided by the single-

component critical temperature (both in absolute units).

Single-Component Gas - A gas with only one chemical component (one type of
atom or one type of molecule).

Standard Temperature and Pressure (STP) -The temperature and pressure at

which all volumes of gas are compared. In Canada, STP is 15oC and 101.325
kPaa.

45
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