Chapter 1

The nature of Petroleum

Petroleum
Petra Rock

November 28, 2018

Oleum Oil

The nature of Petroleum

• Naturally occurring complex mixture of hydrocarbons which
may be liquid, gas or solid depending upon its unique
composition and pressure and temperature at which it is
confined.

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Chemical Composition
Principal hydrocarbon series found in petroleum are

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1. Paraffins (CnH2n+2)

The nature of Petroleum

• Saturated hydrocarbons or alkanes or isomers
• Chemically stable, straight or branched chains
• More volatile (low boiling point)
• Methane, Ethane Propane, n-Butane, iso-Butane

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2. Cycloparaffins (CnH2n)
• napthenes, Ring structure

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• Cyclopropane (C3H6), Cyclobutane ((C4H8)

The nature of Petroleum

3. Aromatics (CnH2n-6)
• Benzene series
• Chemically active, ring structure

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In addition to hydrocarbons, may contain

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impurities like

Carbon dioxide

The nature of Petroleum

Hydrogen sulfide
Nitrogen compounds

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 Gasoline
Kerosene
Diesel Fuels
Refinery

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Oil Lube Oils
Fuel Oils
Wax
Well

The nature of Petroleum

NG (methane)
Gas
Plant LPG (Propane &
Butane)
Natural Gasoline
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Base Classification
1. Paraffin base: Major component is paraffin ,

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complete distillation leave solid residue of wax.

The nature of Petroleum

2. Asphalt base: Major component napthenes,
complete distillation leave solid residue of
asphalt.

3. Mixed base: Falls in middle of two categories.

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Properties of Liquid Petroleum
1. API Gravity

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It is measure of oil’s density and is related to

The nature of Petroleum

specific gravity as follows:
141.5
𝐴𝑃𝐼 𝐺𝑟𝑎𝑣𝑖𝑡𝑦 𝑑𝑒𝑔𝑟𝑒𝑒𝑠 = − 131.5
𝑆𝑝. 𝐺𝑟.

Less denser oil, high API Gravity, more valuable.

API Gravity of 10o is equivalent to a specific gravity 8
of 1
2. Bubble point Pressure, pb
Pressure at which first gas bubble is liberated from
the reservoir oil upon isothermal pressure

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reduction at the reservoir temperature.

3. Oil Formation volume factor, FVF, Bo, RB/STB

The nature of Petroleum

Ratio of the reservoir volume occupied per volume
of tank oil (oil reduced to standard conditions –
14.7 psi and 60oF),
Always greater than 1.0
Bo increase as the pressure decreased from pi to
pb, due to liquid expansion. 9
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4. Solution gas-oil ratio, Rs, SCF/STB
Number of standard cubic feet of gas dissolved per barrel of
tank oil.

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The nature of Petroleum
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 5. Oil Viscosity, µo, Centipoise

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 Flash Vaporization

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Gaseous Petroleum (NG)
Natural gas is produced from

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1. From wells where dominant product is oil (oil
wells)

The nature of Petroleum

2. From wells where gas itself is principal product
(gas wells).
3. As gas from condensate wells. Condensate
wells produce from reservoirs in which the
hydrocarbons (gas and liquid) originally existed
as a single fluid (or phase).
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1. Wet gas: Natural gas if it contains appreciable
natural gasoline contents.
2. GPM: Natural gasoline content of a gas expressed

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in gallons per thousand standard cubic feet
(MCF). Gases having GPM of 1 to 2 are wet while
gas with a GPM of 0.2 is considered as dry gas.

The nature of Petroleum

3. Sour gas: Natural gas containing hydrogen sulfide.
4. Sweet gas: Natural gas with no hydrogen sulfide.
5. Gas gravity: Ratio of density of gas to density of
air at standard conditions.
6. Standard conditions: 14.7 psia and 60oF.
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The Ideal Gas
As a starting point in the study of equation of state
of real gases, we will consider hypothetical gas
known as ideal gas. An ideal gas has these
properties:

• The volume occupied by the molecules is

EQUATIONS OF STATE
insignificant with respect to the volume occupied
by the gas.
• There are no attractive or repulsive forces
between the molecules or between the molecules
and the walls of the container.
• All collisions of molecules are perfectly elastic,
that is, there is no loss of internal energy upon 17
collision.
Boyle’s Law
• Boyle experimentally observed that the volume of an
ideal gas is inversely proportional to pressure for a given
mass of gas when its temperature is maintained
constant.

EQUATIONS OF STATE
• Mathematically:

V ~ 1  PV  Cons tan t
P

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Charles’s Law
• Charles experimentally observed that the volume of an
ideal gas is directly proportional to temperature for a
given mass of gas when its pressure is maintained
constant.

EQUATIONS OF STATE
• Mathematically:

V ~ T V  Cons tan t
T

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Avogadro’s Law
• Avogadro’s law states that, under the same conditions of
temperature and pressure, equal volumes of all ideal
gases contain the same number of molecules. This is
equivalent to the statement that at a given temperature

EQUATIONS OF STATE
and pressure one molecular weight of any ideal gas
occupies the same volume as one molecular weight of
any other ideal gas.
• There are 2.73 E +26 molecules per pound mole of
ideal gas.

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The Equation of State for an Ideal Gas

• The equations of Boyle, Charles, & Avogadro can be combined to

give an equation of state for an ideal gas.
• We must imagine a two – step process in order to combine Boyle’s
equation with Charles’s equation to describe the behavior of an
ideal gas when both temperature & pressure are changed. We start
with a given mass of gas with a volume V1 at pressure P1 and

EQUATIONS OF STATE
temperature T1 and end with a volume of V2 at pressure P2 and
temperature T2. The first step is a change in pressure from P1 to P2
while temperature is kept constant. This cause volume to change
from V1 to V. in the second step, the pressure is maintained constant
at a value of P2. Temperature is changed from a value of T1 to T2,
causing volume to change from V to V2.
• In first step we have Boyle’s equation:

P1V1
P1V1  P2V  V  .......... .(1)
P2 21
• For second step we have Charles’s equation, therefore

V2 V2T1
V  V  .......... ..................( 2)
T1 T2 T2
• Elimination of volume V between equation (1) & (2) we have

P1V1 V2T1 P1V1 P2V2

  

EQUATIONS OF STATE
.......... .........( 3)
P2 T2 T1 T2

• Thus for a given mass of gas, PV/ T is constant. We will denote this
constant by a symbol “R” when quantity of gas is equal to one molecular
weight.
PVM  R..................( 4)
T 22
 • At this point we do not know if R is same for all ideal gases. So we need
to consider Avogadro’s law, that is,

VMA  VMB
• which are volumes of one molecular weight of gases A & B respectively.
Therefore we may write:

PVMA  R  V  RAT , PVMB  R  V  RBT ...(5)

EQUATIONS OF STATE
T A MA P T B MB P
• Where RA & RB represents the gas constant for gas A & B. from equation
(5) we may write:

R AT  R B T  R A  RB .......... .........( 6)
P P 23
• Thus the constant R is the same for all ideal gases and is called the
“Universal Gas Constant”. Thus for any ideal gas we have

PVM  RT .......... .......( 7)

• Where VM is the volume of one molecular weight of the gas, the molar
volume. For “n” moles of ideal gas this equation becomes

PV  nRT.......... .......(8)

EQUATIONS OF STATE
• Where V is the volume of n moles of gas at temperature T and pressure
P. Since “n” is the mass of gas divided by the molecular weight,
therefore we have:

m RT
PV  RT .......... .Or .......... ........ PV  ........( 9)
M M
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• Where m is the mass and V is the volume of one unit of
mass, the specific volume. This equation is known as
“General Gas Law” or “Ideal Gas Law” or the “Perfect Gas
Law”. We will call it as equation of state of an ideal gas or
the ideal gas equation. This equation has limited practical
value since no known gas behaves as an ideal gas, however,
the equation describe the behavior of most real gases at
low pressure. The value of R depends upon the units used

EQUATIONS OF STATE
to express the variables.
Density of an Ideal Gas
• Since density is defined as the mass of gas per unit volume,
an equation of state can be used to calculate the density of
a gas at various temperatures and pressures. From
equation (9) we have:
m PM
g   .......... .......(10) 25
V RT
Specific Gravity of a Gas
• On the assumption that the behavior of both the gas and
air may be represented by the ideal gas equation,
specific gravity may be given as:
PM g

EQUATIONS OF STATE
g RT Mg Mg
g     .........( 27)
 air PM air M air 29
RT
• Where Mg and Mair are the molecular weight of the gas
and air respectively. If the gas is mixture then this
equation can be written as: 26
 Ma Ma
g   .....( 28)
M air 29

• Where Ma is the apparent molecular weight of the gas

mixture. Note that this equation is strictly true only if
both gas and air act like ideal gases.
Behavior of Real Gases

EQUATIONS OF STATE
• Researchers have proposed hundreds of equations of
state for real gases. We will consider first the
compressibility equation of state. This equation of
state is the one used most commonly in the
petroleum industry. This equation have some
limitations; therefore we will examine later several
other equations of state which are used to a lesser
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extent by petroleum engineers.
The Compressibility Equation of State
• To write an equation of state for a real gas is to insert a
correction factor into the ideal gas equation. This results
in:

EQUATIONS OF STATE
• Where the correction factor, Z, is known as
compressibility factor, gas deviation factor, or Z – factor.
Sometimes the reciprocal of compressibility factor is
called super – compressibility.
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• The Z – factor is the ratio of the volume actually
occupied by a gas at given pressure and
temperature to the volume of gas would occupy
at the same temperature and pressure if it
behaved like ideal gas.

EQUATIONS OF STATE
• The Z – factor depends upon the changes in gas
composition, temperature, and pressure.
• At very low pressure the molecules are relatively
far apart, and the conditions of ideal gas behavior
are most likely to be met and Z – factor 29
approaches to 1. 0.
• At moderate pressures, the molecules are closed
enough to exert some attractions between
molecules. This attraction causes the actual

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volume to be somewhat less then the volume
predicted by the ideal gas equation, that is, the Z
– factor will be less than 1. 0.

The nature of Petroleum

• At higher pressures the molecules are forced
close together, the repulsive forces come into
play, the actual volume is greater than the ideal
volume, and Z – factor is greater than 1. 0.
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The Law of Corresponding States
• Reduced temperature and reduced pressure are defined as:
T P
Tr  and Pr 
Tc Pc

EQUATIONS OF STATE
• The law of corresponding states says that “all pure gases
have the same Z – factor at the same values of reduced
pressure and reduced temperature. Some of the deviation
between lines at constant reduced temperatures may be
due to experimental error and some due to inexactness of
the theory. Data for pure hydrocarbon gases such as of
methane, ethane and propane have been put on reduced
basis and are given in Figure.
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EQUATIONS OF STATE 33
• The law of corresponding states is more accurate if the
gases have similar molecular characteristics. Fortunately
most of the gases the petroleum engineer deals with are

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same class of organic compounds.

The nature of Petroleum

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compressibility factor, gas deviation factor (Z)
• To find Z – factor, we may use

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1. Known composition
a) Single Hydrocarbon component
b) Multi Hydrocarbons mixture

The nature of Petroleum

c) Multi Hydrocarbons along with Non-
hydrocarbons mixture

2. Known Specific gravity

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Example:
Determine compressibility factor of ethane at 918 psia and

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117oF.

The nature of Petroleum

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 EQUATIONS OF STATE
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 EQUATIONS OF STATE
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 EQUATIONS OF STATE
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EQUATIONS OF STATE 48
EQUATIONS OF STATE 49
EQUATIONS OF STATE 50
EQUATIONS OF STATE 51
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Reference Book
The Properties of Petroleum Fluids, 2nd Edition,

November 28, 2018

William D. McCain, Jr,
PennWell Publishing Company, ISBN: 978-087814335-1.

The nature of Petroleum

Chapter 3

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 End of Chapter 01

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