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Petroleum Fluid Properties

CHAPTER 1
FUNDAMENTALS OF PETROLEUM CHEMISTRY
1-1

INTRODUCTION

Petroleum reservoir fluids are naturally occurring mixtures of hydrocarbons that exist in
the reservoir at elevated temperatures and pressures. Reservoir fluids vary widely in
chemical composition and - depending on location and origin of the reservoir - have
entirely different physical and chemical properties.
Reservoir fluids are found in gaseous state as natural gas, in liquid state as petroleum or
crude oil, or in solid state such as bitumen or tars. Generally, crude oil at reservoir
conditions contains varying amounts of lighter hydrocarbons which would be gaseous at
atmospheric pressure and temperature and it usually contains long chain and heavy
hydrocarbons such as waxes, resins and asphaltenes. Its appearance varies from yellow
liquid to a dark, often a black coloured, highly viscous material, the variety obviously
being a function of composition.
The exact origin of petroleum deposits is not fundamentally certain, but it is generally
considered to be derived from the remains of organic organisms such as plant, animal, and
marine life (kerogen).

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CHEMICAL COMPOSITION OF HYDROCARBON RESERVOIR FLUIDS

The composition of hydrocarbon reservoir fluids consist mainly of hydrocarbons with a

small percentage of organic and inorganic non-hydrocarbon compounds.
Hydrocarbons are molecules consisting of carbon and hydrogen atoms. The complexity of
hydrocarbon mixtures results from the extremely large number of unique hydrocarbon
molecules. These molecules have traditionally been characterised by the total number of
carbon atoms within each molecule. Hydrocarbons are divided into two main classes:
aliphatics and aromatics. Aliphatic hydrocarbons are further divided into alkanes (or
paraffins); unsaturated hydrocarbons (olefins) such as the alkenes and alkynes; and
The general formula and nature of the chemical
cyclic aliphatics (naphthenes).
structures are shown in Figure 1.
In addition to hydrocarbons, the non-hydrocarbons such as nitrogen (N2), carbon dioxide
(CO2) and hydrogen sulphide (H2S) are found in petroleum fluids. Finally petroleum
fluids may also contain hydrogen (H2), helium (He), and traces of metals such as Sodium
(Na), Potassium (K).
Crude oils can be classified according to the type of the hydrocarbons which make up their
composition. This grouping (Paraffinic, Naphthenic, and Aromatic) is commonly referred to
as the PNA distribution (characterising the percentage of each grouping in the crude).

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Petroleum Fluid Properties

Hydrocarbons

Aromatics
(Arenes)

Aliphatics

Paraffinics

Alkanes

Naphthenics

Olefinics

Alkenes

Alkynes

Cyclic Aliphatics

Isoparaffins

Normal

C H
n

2n+2

-CH-CH2
2

C H
n

2n

-CH -- CH-

C H
n

C H

2n-2

-C -- C-

CH2
CH

C H

2n

CH2

CH2

CH2
CH

Figure 1: Petroleum Hydrocarbon Classifications

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ALKANE OR PARAFFINIC HYDROCARBONS

The first group in the aliphatic hydrocarbons is the alkanes (or paraffins). Alkanes are the
largest constituent of crude oil and are characterised by relative chemical inertness. They
consist of chain hydrocarbon segments with a single (-C-C-) (Carbon-Carbon) bond. The
molecules may be un-branched, ie: normal hydrocarbon, or branched iso-paraffins.
The general formula for the paraffin hydrocarbon series is CnH2n+2 where n varies from 1 to
1,000. Methane (CH4) is the simplest paraffin and it is the most common constituent of
petroleum reservoir fluids. It is gaseous at room conditions. Pentane (C5H12) to
Pentadecane (C15H32) are liquids; these being the main constituents of gasoline and other
fuel fractions. The higher members of paraffin (n>15) are waxy solids at room conditions.
Table 1 gives some basic physical properties of the more common hydrocarbons of the
paraffin series. The properties of the n-alkanes show a relatively smooth trend with
increasing chain length. This is illustrated for several important properties in Figure 2.
Chemical formulae alone, however, do not represent the actual structure of the molecules.
Isomers are substances of the same composition that have different molecular structure
and therefore different chemical and physical properties. The larger the alkane molecule,
the greater the number of structural arrangements. For example, methane through
propane have no structural isomers, butane has two, pentane has three, hexane has eight
while n-decane has 75 and C30 has an estimated three billion possible isomers. Since
most naturally occurring hydrocarbon system contains some C30, and in many cases even
higher carbon numbers, the complexity of petroleum fluids becomes apparent. For
comparison, Table 2 presents the physical properties of the four isomers of Hexane.

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Petroleum Fluid Properties

Component

Formula

Mol Wt
(g mole-1)

Density
(g cm-3)

Normal
Boiling
Point (C)

Melting
Point
(C)

Paraffins
Methane
Ethane
Propane
iso-Butane
n-Butane
iso-Pentane
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Nonanes
n-Decane
n-Undecane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane

CH4
C2H6
C3H8
C4H10
C4H10
C5H12
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32

16.0
30.1
44.1
58.1
58.1
72.2
72.2
86.2
100.2
114.2
128.3
142.3
147.0
161.0
175.0
190.0
206.0

0.2997
0.3558
0.5065
0.5623
0.5834
0.6238
0.6305
0.6632
0.6874
0.7061
0.7212
0.7334
0.7890
0.8000
0.8110
0.8220
0.8320

-161.5
-88.6
-42.1
-11.8
-0.5
27.8
36.1
49.3
98.4
125.7
150.8
165.8
187.2
208.3
227.2
246.4
266.1

-182.5
-182.8
-187.6
-159.6
-138.4
-159.9
-129.7
-95.3
-90.5
-56.8
-53.5
-29.6
-25.6
-9.6
-5.4
5.9
9.9

Napthenes
neo-Pentane
M-C-Pentane
Cyclohexane
M-C-Hexane

C5H12
C6H12
C6H12
C7H12

72.2
84.2
84.2
98.2

0.5968
0.7533
0.7827
0.7740

9.5
71.8
80.7
100.9

-16.6
-142.5
6.6
-126.6

80.1
110.6
136.2
139.1
144.4
165.8

5.5
-95.0
-95.0
-47.8
-25.2
-25.3

Aromatics
Benzene
C6H6
78.1
0.8820
Toluene
C7H8
92.1
0.8734
EthylBenzene
C8H10
106.2
0.8735
M-Xylene
C8H10
106.2
0.8671
O-Xylene
C8H10
106.2
0.8840
T-M-Benzene
C9H12
120.2
0.8797
Table 1: Physical Properties of Some Hydrocarbons

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Petroleum Fluid Properties

200

T / oC

0.75

100

0.70

boiling point

Density
(g cm -3)

density

0.65

melting point

-100

0.60

-200

0.55
1

10

11

12

Carbon Number
Figure 2: Some Properties of the n-Alkanes Homologous Series.
Boiling
Point
(oF)

Melting
Point
(oF)

Specific
Gravity
60o/60o

n-hexane

155.7

-139.6

0.664

3-methylpentane

145.9

-180.4

0.669

2-methylpentane
(isohexane)

140.5

-244.6

0.658

2,3-dimethylbutane

136.4

-199.4

0.666

2,2-dimethylbutane

121.5

-147.8

0.654

Isomer

Table 2: Physical Properties of Hexane Isomers

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ALKENES AND ALKYNES

These groups are also classed unsaturated hydrocarbons (or olefins) and have double or
triple bonds between carbon atoms, ie: Alkenes (-C=C-); Alkynes (-CC-). They have the
potential to combine with more hydrogen or other elements and are therefore termed
unsaturated. Hence they are generally not found in crude oil except in refined products
(as a by-product of cracking).

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Petroleum Fluid Properties

1-2-3

CYCLIC ALIPHATICS

These components, sometimes called cyclo-paraffins (or naphthenes), are identified by

having single (-C-C-) bonds but the carbon chain is closed and is saturated. The general
formula for these rings is CnH2n and - being very stable components - are important
constituents of crude oil. Their chemical properties are similar to those of the paraffins.
The most common naphthenic compounds found in natural petroleum are shown in Table
3.
Boiling
Point
(oF)

Melting
Point
(oF)

Cyclopropane

-27

-197

Cyclobutane

55

-122

Cyclopentane

121

-137

0.750

Cyclohexane

177

44

0.783

Cycloheptane

244

10

0.810

Cyclooctane

300

57

0.830

Methylcyclopentane

161

-224

0.754

cis-1,2-dimethylcyclopentane

320

-80

0.772

trans-1.2-dimethylcyclopentane

198

-184

0.750

Methylcyclohexane

214

-196

0.774

Cyclopentene

115

-135

0.774

1,2-cyclopentadiene

108

-121

0.798

Cyclohexene

181

-155

0.810

1,3-cyclohexadiene

177

-144

0.840

1,4-cyclohexadiene

189

-56

0.847

Name

Specific
Gravity
()

Table 3: Some Physical Properties of Cyclic Aliphatic Hydrocarbons

1-2-4

AROMATICS

The aromatic series have one or more ring structures with aromatic double bonds similar
to Benzene (C6H6). These hydrocarbons are unsaturated closed rings with a strong
aromatic odour.
Naphthalene (C10H8), anthracene (C14H10) and other polycyclic
compounds are all commonly found in natural crude oil. Some of the simpler aromatic
constituents of crude oil are illustrated in Figure 3.

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Petroleum Fluid Properties

BENZENE

NAPTHALENE

ANTHRACENE

Figure 3: Some Examples of Petroleum Aromatic Compounds

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SULPHUR COMPOUNDS

The most common sulphur compounds found in crude oil Systems are Hydrogen
Sulphide and Mercaptans (in the range of 0.04 - 5 wt% ) as well as free sulphur itself. The
natural gas and crude systems which contain sulphur compounds are called 'sour' whilst
those without sulphur compounds are sometimes called 'sweet'.
Hydrogen sulphide
Hydrogen sulphide (H2S) is a colourless gas with a boiling point of -59.5 oC and an
extremely unpleasant odour. Hydrogen sulphide is highly poisonous and its presence is
detrimental to the petroleum refiner since sulphur deteriorates (poisons) the metallic
catalysts used in the refining process. It is usually removed from natural gas by
absorption with Ethanolamines. However, some natural gases with high concentration of
H2S are used in the production of sulphur as a by-product.
Mercaptans
The mercaptans or thiols have the general formula R-S-H in which R represents any
organic group such as alkyl or cyclic aliphatics, ie:
H - S - CH3
Methanethiol

R' - S - H
Thiophenyl
where: R' = Benzene ring

In general the mercaptans have a more disagreeable odour than hydrogen sulphide and
must be processed and removed from crude during the refining process.

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Petroleum Fluid Properties

Alkyl Sulphides
The alkyl sulphides or thio ethers have the general formula of (R-S-R). Their distinctive
odours are not as disagreeable as H2S or mercaptans, but they cause much the same
problems.
CH2=CH-CH2-S-CH2-CH=CH2

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Alkyl sulphide

OTHER COMPONENTS CONTAINING NON-HYDROCARBONS

Compounds incorporating nitrogen and oxygen are also found in limited amounts in
crude oil. Organic acids contain oxygen (up to 0.5 wt% ) while nitrogen occurs (up to 0.1
wt% ) in the form of bases and neutral nitrogen compounds (Figure 4).

PYRIDINE

PYROLLES
H

CARBAZOLES

QUINOLENES
H

Figure 4: Typical Nitrogen Compounds found in Crude Oil

Free elemental nitrogen can also occur in petroleum, however free oxygen does not due to
oxidative reactions.

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WATER, ELECTROLYTES AND METALS

Water, inorganic salts (eg: Magnesium Chloride (MgCl2), Calcium Chloride (CaCl2), Sodium
Chloride (NaCl)) in aqueous solution and metals such as Copper (Cu), Zinc (Zn),Iron (Fe),
and Vanadium (Va) are also found in crude oil in small quantities. Many of these salts
need to be removed before refining as some generate Hydrochloric Acid (HCl) when heated
with water.

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Petroleum Fluid Properties

1-3

ANALYSIS OF RESERVOIR FLUIDS

Since the number of compounds in a crude oil are virtually innumerable, no crude oil has
been separated into all of its individual components. The compositional analysis of
reservoir fluids is usually reported by paraffin fractions (groups of components falling into
the boiling ranges - see Reservoir Fluid Analysis) which is sufficient for most applications.
In general, all isomers are reported individually up to n-pentane, but above n-pentane
they are lumped together as groups designated C6, C7, .... Cn+ where n+ is everything above
a specified carbon number n. Examples of field compositions for Natural Gas, Separator
gas and oil, and gas condensates for the North Sea are shown in Table 5.
Crude oils can also be classified chemically according to the structure of the larger
molecules in the mixture. As already mentioned, classification may be expressed by
Paraffinic, Naphthenic, Aromatic, and Asphaltic.
Paraffinic oils yield very fine lubricating oils and also paraffin wax from the distillation
residuum, while Asphaltic oils produce heavier fractions which are used for pitch, roofing,
and paving asphalt.
More generally, oil may be classified according to :
i)

The American Petroleum Institute (API) gravity number (see Chapter 3)

ii)

The general Refractive Index (range for oils is 1.39 to 1.49)

iii)

Fluorescence of oil measured under UV light.

API GRAVITY No.

RANGE

COLOUR

2 - 10

Non-Fluorescent(Dull)

10 - 18

Yellow-Brown to Gold

18 - 45

Gold to Pale Yellow

45 - Above

Blue- White to White

Table 4

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Petroleum Fluid Properties

Component

Gas

Gas
Condensate

Volatile
Oil

Black
Oil

N2

0.30

0.71

1.67

0.67

CO2

1.10

8.65

2.18

2.11

C1

90.00

70.86

60.51

34.93

C2

4.90

8.53

7.52

7.00

C3

1.90

4.95

4.74

7.82

C4 (i+n)

1.10

2.00

4.12

5.48

C5 (i+n)

0.40

0.81

2.97

3.80

C6 (i+n)

6+ : 0.30

0.46

1.99

3.04

C7

0.61

2.45

4.39

C8

0.71

2.41

4.71

C9

0.39

1.69

3.21

C10

0.28

1.42

1.79

C11

0.20

1.02

1.72

C12

0.15

12+ : 5.31

1.74

C13

0.11

1.74

C14

0.10

1.35

C15

0.07

1.34

C16

0.05

1.06

C17

17+ : 0.37

1.02

C18

1.00

C19

0.90

C20
Total:

20+ : 9.18
100.00

100.00

100.00

100.00

Table 5: Typical Compositions of Fluids

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