Crude Oil and Products Properties

Source of Oil
• Composition of crude oil and Theories of oil source.
• Petroleum (also called crude oil) is a naturally mixture of hydrocarbons,
generally in the liquid state, that may also include compounds of sulfur,
nitrogen, oxygen, and metals and other elements. Inorganic sediment and water
may also be present. Thus, for the purposes of this text, a petroleum product is
any product that is manufactured during petroleum refining and, as a
consequence, petrochemical products are not included in this definition.

• It consists of hydrocarbons of various molecular weights and other 

organic compounds. The name petroleum covers both naturally occurring
unprocessed crude oil and products that are made up of refined crude oil. A 
fossil fuel, petroleum is formed when large quantities of dead organisms,
usually zooplankton and algae, are buried underneath sedimentary rock and
subjected to intense heat and pressure.
More direct chemical information is often desirable and can be supplied by
means of the correlation index (CI). The correlation index is useful in
evaluating individual fractions from crude oils. The CI values are not
quantitative, but the lower the CI value, the greater the concentrations of
paraffin hydrocarbons in the fraction; and the higher the CI value, the greater
the concentrations of naphthenes and aromatics.
 • CI =[ 87552/TB]+ 473.7G – 456.8
 
• Where:
• G is the specific gravity and TB is the average boiling point of the petroleum fraction as
determined by the standard distillation method (ASTM D-86, ASTM D-1160).
•  
• ‫٭‬Another derived number, the UOP (characterization factor, is also a widely used
method for defining petroleum; the Characterization Factor is derived from the formula:
Kw = TB1/3/ G
• Where:
• TB is the average boiling point in degrees Rankine (°F + 460) and G is the specific
gravity (60°/60°F).
 

• The Watson characterization factor :KW ~15 for highly paraffinic compounds , KW <10

for highly aromatic materials and KW vary from 10.5 to 12.9. For a highly naphthenic

crude it is 10.5 to 12.9 for a paraffinic base crude.

 Composition of Crude Oil

Petroleum includes only crude oil, but in common usage it

includes all liquid, gaseous, and solid hydrocarbons. Under
surface pressure and temperature conditions, lighter hydrocarbons 
methane, ethane, propane and butane occur as gases, while 
pentane and heavier ones are in the form of liquids or solids.
However, in an underground oil reservoir  the proportions of gas,
liquid, and solid depend on subsurface conditions and on the 
phase diagram of the petroleum mixture.
An oil well produces predominantly crude oil, with some natural
gas dissolved in it. Because the pressure is lower at the surface
than underground, some of the gas will come out of solution and
be recovered (or burned) as associated gas or solution gas.
• A gas well produces predominantly natural gas. However, because the
underground temperature and pressure are higher than at the surface, the gas
may contain heavier hydrocarbons such as pentane, hexane, and heptanes in
the gaseous state. At surface conditions these will condense out of the gas to
form natural gas condensate, often shortened to condensate. Condensate
resembles gasoline in appearance and is similar in composition to some 
volatile light crude oils.

• The proportion of light hydrocarbons in the petroleum mixture varies greatly

among different oil fields, ranging from as much as 97 percent by weight in
the lighter oils to as little as 50 percent in the heavier oils and bitumen’s.

• The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various 

aromatic hydrocarbons, while the other organic compounds contain nitrogen
, oxygen and sulfur, and trace amounts of metals such as iron, nickel, copper
and vanadium. Many oil reservoirs contain live bacteria.
 The exact molecular composition varies widely from formation to
formation but the proportions of chemical elements vary over
fairly narrow limits as follows:
 Table (2) Composition by weight

Element Percent range

Hydrocarbon Average Range

Carbon 83 to 85%

Alkanes (paraffin’s) 30% 15 to 60%

Hydrogen 10 to 14%

Nitrogen 0.1 to 2% Naphthenes 49% 30 to 60%

Oxygen 0.05 to 1.5%

Aromatics 15% 3 to 30%

Sulfur 0.05 to 6.0%

Asphaltic 6% remainder

Metals < 0.1%

• Any theory regarding the origin of petroleum must explain two
sets of observations, one geological and the other chemical.

Geological observations are that major accumulations:

• Occur in sedimentary rocks.
• Are characteristic of un metamorphosed marine (shallow, deep water)
and continental sediments.
• Occur in porous material totally encapsulated from other porous
material.
 
Chemical observations are:
• crude oil (even numbered carbon chains) differs from recent
hydrocarbons (odd numbered carbon chains) formed in shallow
environments, and crude has over 50% light hydrocarbons while light
hydrocarbons are rare or absent in the recent variety.
•Inorganic theory: of the origin of the petroleum states that hydrogen and
carbon came together under great temperature and pressure, far below the
earth’s surface and formed oil and gas.  The oil and gas then seeped through
porous rock to deposit in various natural underground traps.
•Organic theory:  is the one most widely accepted.  According to organic
theory, the oil and gas are formed from remains of prehistoric plants and
animals.  Remains of plants have been transformed to coal and animals’ to oil
and gas.  These remains were settled in to seas and lands along with sands and
slits, mud and other minerals.  As the rocks and slit settled, layer upon layer
piled into rivers, along coastlines and on the sea bottom. Geological shifts
resulted in some of these layers being buried deep in the earth.

Over the time, the layers of the organic material were compressed under the
weight of the sediment above them.  The increase in pressure and temperature
changed the mud, sand, slit in to rock and organic matter in petroleum.
Liquid petroleum flowed upward through porous rock until it became
trapped and could flow no further forming the oil and gas that we
explore for at present as shown in figure (4).

But the chemistry of the hydrocarbons found in the end product (oil,
and gas) differs somewhat from those we find in living thing. Thus
changes, transformation, take place between the deposition of the
organic remains and the creation of petroleum oil and gas:
• Petroleum end product = ([Raw material + Accumulations
+Transformation + Migration] = Geological time).
• The complication is that Petroleum is complex mixtures of many
hydrocarbons occurring in homologous series with no two Petroleum
exactly alike in composition. This is probably due to variations in
primary source materials and subsequent processes during formation
such as catalysis, polymerization, pressure and temperature changes.
Although the components of petroleum unite to form complex mixtures.
Petroleum Assay
Density
The density, or more precisely, the volumetric mass density, of a
substance is its mass per unit volume. The symbol most often used for
density is ρ, although the Latin letter D can also be used.
Mathematically, density is defined as mass divided by volume:
 ρ = m / V
Where ρ is the density, m is the mass, and V is the volume.
• In some cases (for instance, in the United States oil and gas industry), density is
loosely defined as its weight per unit volume, although this is scientifically inaccurate
– this quantity is more specifically called specific weight.

• To simplify comparisons of density across different systems of units, it is sometimes

replaced by the dimensionless quantity "relative density" or "specific gravity", i.e. the
ratio of the density of the material to that of a standard material, usually water. Thus a
relative density less than one means that the substance floats in water.

• The density of a material varies with temperature and pressure. This variation is
typically small for solids and liquids but much greater for gases. Increasing the
pressure on an object decreases the volume of the object and thus increases its
density. Increasing the temperature of a substance (with a few exceptions) decreases
its density by increasing its volume. In most materials, heating the bottom of fluid
results in convection of the heat from the bottom to the top, due to the decrease in the
density of the heated fluid. This causes it to rise relative to more dense unheated
material.
 Measurements of Density
1. Homogeneous materials
The density at all points of a homogeneous object equals its total mass
 divided by its total volume. The mass is normally measured with a 
scale or balance; the volume may be measured directly (from the
geometry of the object) or by the displacement of a fluid. To
determine the density of a liquid or a gas, a hydrometer, adasymeter or
a Coriolis flow meter may be used, respectively.
2. Heterogeneous materials
If the body is not homogeneous, then its density varies between
different regions of the object. In that case the density around any
given location is determined by calculating the density of a small
volume around that location. In the limit of an infinitesimal volume
the density of an inhomogeneous object at a point becomes: ρ ( r→) =
dm/dV, where dV is an elementary volume at position r. The mass of
the body then can be expressed as:
3. Non-compact materials
• In practice, bulk materials such as sugar, sand, or snow contain
voids. Many materials exist in nature as flakes, pellets, or
granules. Voids are regions which contain something other than the
considered material. Commonly the void is air, but it could also be
vacuum, liquid, solid, or a different gas or gaseous mixture.

• The bulk volume of a material—inclusive of the void fraction—is

often obtained by a simple measurement (e.g. with a calibrated
measuring cup) or geometrically from known dimensions. Mass
divided by bulk volume determines bulk density. This is not the
same thing as volumetric mass density. To determine volumetric
mass density, one must first discount the volume of the void
fraction.
 API gravity
• The American Petroleum Institute gravity, or API gravity, is a measure
of how heavy or light a petroleum liquid is compared to water: API
gravity is thus an inverse measure of a petroleum liquid's density relative
to that of water (also known as specific gravity). It is used to compare
densities of petroleum liquids. Although mathematically, API gravity is a
dimensionless quantity, see the formula below, it is referred to as being
in 'degrees'. API gravity is gradated in degrees on a 
hydrometer instrument. API gravity values of most petroleum liquids fall
between 10 and 70 degrees.
• The formula to calculate API gravity from Specific Gravity (SG) is:

• In the oil industry, quantities of crude oil are often measured in metric 
tons. One can calculate the approximate number of barrels per metric ton
for a given crude oil based on its API gravity:
Classifications or grades
Generally speaking, oil with API gravity between 40 and 45°
commands the highest prices. Above 45°, the molecular chains
become shorter and less valuable to refineries. Crude oil is classified
as light, medium, or heavy according to its measured API gravity.
•Light crude oil has an API gravity higher than 31.1° (i.e., less than
870 kg/m3)
•Medium oil has an API gravity between 22.3 and 31.1° (i.e., 870 to
920 kg/m3)
•Heavy crude oil has an API gravity below 22.3° (i.e., 920 to
1000 kg/m3)
•Extra heavy oil has an API gravity below 10.0° (i.e., greater than
1000 kg/m3)
• However, not all parties use the same grading. The 
United States Geological Survey uses slightly different ranges. Crude
oil with API gravity less than 10° is referred to as extra heavy oil or 
bitumen. Bitumen derived from oil sands deposits in Alberta, Canada,
has an API gravity of around 8°. It can be diluted with lighter
hydrocarbons to produce diluted bitumen, which has an API gravity of
less than 22.3°, or further "upgraded" to an API gravity of 31 to 33° as 
synthetic crude.
 
Viscosity
The viscosity of a fluid is a measure of its resistance to gradual
deformation by shear stress or tensile stress.  For liquids, it
corresponds to the informal concept of "thickness".
Definition
1-Dynamic (shear) viscosity 
Laminar shear of fluid between two plates. Friction between the fluid and the
moving boundaries causes the fluid to shear. The force required for this
action is a measure of the fluid's viscosity.
• The dynamic (shear) viscosity of a fluid expresses its resistance to
shearing flows, where adjacent layers move parallel to each other with
different speeds.
• The magnitude   of this force is found to be proportional to the speed 
 and the area   of each plate, and inversely proportional to their
separation :

The proportionality factor μ in this formula is the viscosity (specifically,

the dynamic viscosity) of the fluid.

2-Kinematic viscosity
• The kinematic viscosity (also called "momentum diffusivity") is the ratio
of the dynamic viscosity μ to the density of the fluid ρ. It is usually
denoted by the Greek letter nu (ν).
 3- Bulk viscosity
• When a compressible fluid is compressed or expanded evenly, without shear, it may still exhibit a
form of internal friction that resists its flow. These forces are related to the rate of compression or
expansion by a factor σ, called the volume viscosity, bulk viscosity or second viscosity.
• The bulk viscosity is important only when the fluid is being rapidly compressed or expanded,
such as in sound and shock waves. Bulk viscosity explains the loss of energy in those waves, as
described by Stokes' law of sound attenuation.
• 
4- Viscosity in solids
• The viscous forces that arise during fluid flow must not be confused with the elastic forces that
arise in a solid in response to shear, compression or extension stresses. While in the latter the
stress is proportional to the amount of shear deformation, in a fluid it is proportional to the rate of
deformation over time.

• However, many liquids (including water) will briefly react like elastic solids when subjected to
sudden stress. Conversely, many "solids" (even granite) will flow like liquids, albeit very slowly,
even under arbitrarily small stress. Such materials are therefore best described as possessing both
elasticity (reaction to deformation) and viscosity (reaction to rate of deformation); that is, being  
viscoelastic.
• Indeed, some authors have claimed that amorphous solids, such as glass
 and many polymers, are actually liquids with a very high viscosity (e.g.
greater than 1012Pa·s).  
• Viscoelastic solids may exhibit both shear viscosity and bulk viscosity.
The extensional viscosity is a linear combination of the shear and bulk
viscosities that describes the reaction of a solid elastic material to
elongation. It is widely used for characterizing polymers. In geology,
earth materials that exhibit viscous deformation at least three orders of
magnitude greater than their elastic deformation.
 
5- Viscosity of slurry
• The term slurry describes mixtures of liquid and solid particles that retain
some fluidity. The viscosity of slurry can be described as relative to the
viscosity of the liquid phase:

• Where μs and μl are respectively the dynamic viscosity of the slurry and

liquid (Pa·s), and μr is the relative viscosity (dimensionless).
 Pour point
• The pour point of petroleum is an index of the lowest temperature at which the
crude oil will flow under specified conditions. The maximum and minimum
pour point temperatures provide a temperature window where petroleum,
depending on its thermal history, might appear in the liquid as well as the solid
state. The pour point data can be used to supplement other measurements of
cold flow behavior, and the data are particularly useful for the screening of the
effect of wax interaction modifiers on the flow behavior of petroleum.
• In any determination of the pour point, petroleum that contains wax produces an
irregular flow behavior when the wax begins to separate. Such petroleum
possesses viscosity relationships that are difficult to predict in pipeline
operation. In addition, some waxy petroleum is sensitive to heat treatment that
can also affect the viscosity characteristics. This complex behavior limits the
value of viscosity and pour point tests on waxy petroleum. However, laboratory
pump ability tests (ASTM D-3245, IP 230) are available that give an estimate of
minimum handling temperature and minimum line or storage temperature.
 Salt Content
• The salt content of crude oil is highly variable and results principally from
production practices used in the field and, to a lesser extent, from its handling
aboard the tankers bringing it to terminals. The bulk of the salt present will be
dissolved in coexisting water and can be removed in desalters, but small amounts of
salt may be dissolved in the crude oil itself.
• Salt may be derived from reservoir or formation waters or from other waters used in
secondary recovery operations. Aboard tankers, ballast water of varying salinity
may also be a source of salt contamination. Salt in crude oil may be deleterious in
several ways. Even in small concentrations, salts will accumulate in stills, heaters,
and exchangers, lead in got fouling that requires expensive cleanup. More
importantly, during flash vaporization of crude oil certain metallic salts can be
hydrolyzed to hydrochloric acid according to the following reactions:
2NaCl + H2O →2 HCl+ Na2O
MgCl2+ H2O →2 HCl + MgO
• The hydrochloric acid evolved is extremely corrosive, necessitating the injection of
a basic compound, such as ammonia, into the overhead lines to minimize corrosion
damage. Salts and evolved acids can also contaminate both overhead and residual
products, and certain metallic salts can deactivate catalysts.
• Thus knowledge of the content of salt in crude oil is important in
deciding whether and to what extent the crude oil needs desalting.

• The salt content is determined by potentiometric titration in a non

aqueous solution in which the conductivity of a solution of crude oil in a
polar solvent is compared with that of a series of standard salt solutions
in42 petroleum and petroleum products the same solvent (ASTM D-
3230). In this method, the sample is dissolved in a mixed solvent and
placed in a test cell consisting of a beaker and two parallel stainless steel
plates. An alternating voltage is passed through the plates, and the salt
content is obtained by reference to a calibration curve of the relationship
of salt content of known mixtures to the current.

• It is necessary, however, to use other methods, such atomic absorption,

inductively coupled argon plasma emission spectrophotometer, and ion
chromatography to determine the composition of the salts present. A
method involving application of extraction and volumetric titration is
also used (IP 77).
 Sulfur
The sulfur content of petroleum is an important property and varies
within the rough limits 0.1% w/w to 3.0% w/w, and sulfur content up
to 8.0% w/w has been noted for tar sand bitumen. Compounds
containing this element are among the most undesirable constituents
of petroleum because they can give rise to plant corrosion and
atmospheric pollution. Petroleum can evolve hydrogen sulfide during
distillation as well as low-boiling sulfur compounds.
• Hydrogen sulfide may be evolved during the distillation process
either from free hydrogen sulfide in the feed stocks or because of low
temperature thermal decomposition of sulfur compounds; the latter is
less likely than the former. Generally, however, the sulfur compounds
concentrate in the distillation residue, the volatile sulfur compounds
in the distillates being removed by such processes as hydrofining and
caustic washing.
• The sulfur content of fuels obtained from petroleum residua and the
atmospheric pollution arising from the use of these fuels is an important
factor in petroleum utilization, so that the increasing insistence on a low
sulfur-content fuel oil has increased the value of low-sulfur petroleum.
Sulfur compounds contribute to corrosion of refinery equipment and
poisoning of catalysts, cause corrosiveness in refined products, and
contribute to environmental pollution as a result of the combustion of fuel
products. Sulfur compounds may be present throughout the boiling range
of crude oil salt though, as a rule, they are more abundant in the higher-
boiling fractions.
• In some crude oils, thermally labile sulfur compounds can decompose on
heating to produce hydrogen sulfide, which is corrosive and toxic. A
considerable number of tests are available to estimate the sulfur in
petroleum or to study its effect on various products. Hydrogen sulfide in
petroleum is normally determined by absorption of the hydrogen sulfide in
a suitable solution that is subsequently analyzed chemically (Doctor
Method) (ASTM, D-4952, IP 30) or by the formation of cadmium sulfate
(IP 103).
 Distillation
The distillation tests give an indication of the types of products and the
quality of the products that can be obtained from petroleum, and the tests are
used to compare different petroleum types through the yield and equality of
the 300°C (572°F) residuum fraction. For example, the waxiness or viscosity
of this fraction gives an indication of the amount, types, and quality of the
residual fuel that can be obtained from the petroleum. In this respect, the
determination of the aniline point (ASTM D-611, IP 2) can be used to
determine the aromatic or aliphatic character of petroleum. Although not
necessarily the same as the wax content, correlative relationships can be
derived from the data.
The basic method of distillation (ASTM D-86) is one of the oldest methods
in use because the distillation characteristics of hydrocarbons have an
important effect on safety and performance, especially in the case of fuels
and solvents. The boiling range gives information on the composition, the
properties, and the behavior of petroleum and derived products during
storage and use. Volatility is the major determinant of the tendency of a
hydrocarbon mixture to produce potentially explosive vapors.
• Several methods are available to define the distillation
characteristics of petroleum and its various petroleum products. In
addition to these physical methods, other test methods based on gas
chromatography are also used to derive the boiling point
distribution of a sample (ASTM D-2887, ASTM D- 2887).
• Fractionation of the crude oil begins with a true boiling point (TBP)
distillation using a fractionating column with an efficiency of 14–
18 theoretical plates and operated at a reflux ratio of 5:1 (ASTM D-
2892).
• The TBP distillation may be used for all fractions up to a maximum
cut point of about 350°C atmospheric equivalent temperature
(AET), but a low residence time in the still (or reduced pressure) is
needed to minimize cracking. It is often useful to extend the boiling
point data to higher temperatures than are possible in the
fractionating distillation method previously described, and for this
purpose a vacuum distillation in a simple still with no fractionating
column (ASTM D-1160) can be carried out.
• This distillation, which is done under fractionating conditions
equivalent to one theoretical plate, allows the boiling point data to be
extended to about 600°C (1112°F) with many crude oils. This
method gives useful comparative and reproducible results that are
often accurate enough for refinery purposes, provided significant
cracking does not occur.
• Usually seven fractions provide the basis for a reasonably
thorough evaluation of the distillation properties of the
feedstock:
1- Gas, boiling range:< 15.5 °C (60°F)
2- Gasoline (light naphtha), boiling range: l5.5–149°C (60–300°F)
3- Kerosene (medium naphtha), boiling range: 149–232°C (300–450°F)
4- Gas oil, boiling range: 232–343°C (450–650°F)
5- Light vacuum gas oil, boiling range: 343–371°C (650–700°F)
6- Heavy vacuum gas oil, boiling range: 371–566°C (700–1050°F)
7- Residuum, boiling range: >566°C (1050°F)
• From 5 to 50 liters of crude oil are necessary to complete a full assay,
depending on the number of fractions to be taken and the tests to be
performed on the fractions.
• A more recent test method (ASTM D-5236) is seeing increasing use
and appears to be the method of choice for crude assay vacuum
distillations. Wiped-wall or thin-film molecular stills can also be used
to separate the higher-boiling fractions under conditions that
minimize cracking.

Carbon Residue 
• The carbon residues of petroleum and petroleum products serve as an
indication of the tendency of the sample to form carbonaceous
deposits (thermal coke) under the influence of heat.
• Tests for Conradson carbon residue (ASTM D-189, IP 13), Rams
bottom carbon residue (ASTM D-524, IP 14), the micro carbon
residue (ASTM D4530, IP 398), are sometimes included in inspection
data on petroleum.
• The data given indication of the amount of coke that will be formed
during thermal processes as well as an indication of the amount of
high-boiling constituents in petroleum.

• The determination of the carbon residue of petroleum or petroleum

product is applicable to relatively nonvolatile samples that
decompose on distillation at atmospheric pressure. Samples that
contain ash-forming constituents will have an erroneously high
carbon residue, depending on the amount of ash formed. All three
methods are applicable to relatively non volatile petroleum
products that partially decompose on distillation at atmospheric
pressure.

• Crude oils having a low carbon residue may be distilled to a

specified residue with the carbon residue test of choice then applied
to that residue.
 Asphaltenes
•Asphaltenes are molecular substances that are found in crude oil, along with 
resins, aromatic hydrocarbons, and saturates (i.e. saturated hydrocarbons
such as alkanes). Asphaltenes in the form of asphalt or bitumen products
from oil refineries are used as paving materials on roads, shingles for roofs,
and waterproof coatings on building foundations.
•Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and 
sulfur, as well as trace amounts of vanadium and nickel. The C: H ratio is
approximately 1:1.2, depending on the asphaltene source.
Occurrence
•Heavy oils, oil sands, bitumen and biodegraded oils (as bacteria cannot
assimilate asphalten, but readily consume saturated hydrocarbons and certain
aromatic hydrocarbon isomers - enzymatically controlled) contain much
higher proportions of asphaltenes than do medium-API oils or light oils.
Condensates are virtually devoid of asphaltenes.
 Measurement

• Asphaltene aggregation, precipitation or deposition can be

predicted by modeling or artificial intelligent methods. It also
can be measured using imaging methods or filtration.

Production problems
• Asphaltenes impart high viscosity to crude oils, negatively
impacting production; also the variable asphaltene
concentration in crude oils within individual reservoirs creates
a myriad of production problems.