Petroleum Engineering Department

PETROLEUM PROPERTIES
Lecture 2

Composition and physical properties of petroleum

By: Foad Yousefi

2020
 Petroleum Properties Lecture 2

Products Composition

1. Liquefied Petroleum Gas (LPG)

Used for heating, cooking, making plastics

Small alkanes (1 to 4 carbon atoms)

Commonly known by the name’s methane, ethane, propane, butane

Often liquefied under pressure to create LPG (liquefied petroleum gas)

2. Gasoline

Motor fuel

Liquid

Mix of alkanes and cycloalkanes (5 to 7 carbon atoms)

Boiling range = 90-220 degrees Fahrenheit / 27-93 degrees Celsius

3. Kerosene

Fuel for domestic heater; material for making other products

Liquid

Mix of alkanes (10 to 15 carbons) and aromatics

Boiling range = 315-450 degrees Fahrenheit / 177-293 degrees Celsius

4. Fuel oil

Used for industrial fuel; starting material for making other products

Liquid

Long chain (16 to 40 carbon atoms) alkanes, cycloalkanes, aromatics

Boiling range = 650-800 degrees Fahrenheit / 315-565 degrees Celsius

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5. Residual oil

Coke, asphalt, tar, waxes; material for making other products

Solid

Multiple-ringed compounds with 40 or more carbon atoms

Boiling range = greater than 800 degrees Fahrenheit / 565 degrees Celsius

Physical properties

Molecular Weight

Molecular weight or molar mass shown by M is a number that 1 mol of any substance has
equivalent mass of Mg. In the SI system the unit of M is kg/k-mol and in the English system the
unit is lb/lb-mol, while in the cgs system the unit of M is g/mol. As an example, methane has the
molecular weight of 16 g/mol.

Molecular weight of a pure compound is determined from its chemical formula and the atomic
weights of its elements. The atomic weights of the elements found in a petroleum fluid are C =
12.011, H = 1.008, S = 32.065, O = 16.0, and N = 14.01, as given by the IUPAC standard. As an
example, the molecular weight of methane (CH4) is calculated as 12.011 + 4 × 1.008 = 16.043
kg/k-mol or 16.043 g/tool (0.01604 kg/mol) or 16.043 lb/lb-mol. Molecular weight is one of the
characterization parameters for hydrocarbons.

Boiling Point

The boiling point of a pure compound at a given pressure is the temperature at which vapor and
liquid exist together at equilibrium. If the pressure is 1 atm, the boiling point is called the normal
boiling point. However, usually the term boiling point, Tb, is used instead of normal boiling point
and for other pressures the term saturation temperature is used. In some cases, especially for heavy
hydrocarbons in which thermal cracking may occur at high temperatures, boiling points at
pressures other than atmospheric is specified. Boiling points of heavy hydrocarbons are usually
measured at 1, 10, or 50 mm Hg. The boiling point, when available, is one of the most important
characterization parameters for hydrocarbons and is frequently used in property estimation
methods.

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Density, Specific Gravity, and API Gravity

Density is defined as mass per unit volume of a fluid. Density is a state function and for a pure
compound depends on both temperature and pressure and is shown by ρ. Liquid densities decrease
as temperature increases but the effect of pressure on liquid densities at moderate pressures is
usually negligible. At low and moderate pressures (less than a few bars), saturated liquid density
is nearly the same as actual density at the same temperature. However, liquid density at the
reference conditions of 20 C (293 K) and 1 atm is shown by d and it is used as a characterization
parameter in this chapter. Parameter d is also called absolute density to distinguish from relative
density. Liquid density for hydrocarbons is usually reported in terms of specific gravity (SG) or
relative density defined as

Since the standard conditions adopted by the petroleum industry are 60 F (15.5 C) and 1 atm,
specific gravities of liquid hydrocarbons are normally reported at these conditions. At a reference
temperature of 60 F (15.5 C the density of liquid water is 0.999 g/cm3 (999 kg/m3) or 8.337
lb/gal(U.S.). Therefore, for a hydrocarbon or a petroleum fraction, the specific gravity is defined
as

Water density at 60 F is 0.999 or almost 1 g/cm3; therefore, values of specific gravities are nearly
the same as the density of liquid at 15.5 C (289 K) in g/cm3 . The Society of Petroleum Engineers
usually uses γ for the specific gravity and in some references it is designated by S. However, in
this book SG denotes the specific gravity. Since most of hydrocarbons found in reservoir fluids
have densities less than that of water, specific gravities of hydrocarbons are generally less than 1.
Petroleum Institute (API) defined the API gravity (degrees API) to quantify the quality of
petroleum products and crude oils. The API gravity is defined as

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Liquid hydrocarbons with lower specific gravities have higher API gravity. Aromatic
hydrocarbons have higher specific gravity (lower API gravity) than do paraffinic hydrocarbons.
For example, benzene has SG of 0.8832 (API of 28.72) while n-hexane with the same carbon
number has SG of 0.6651 (API gravity of 81.25). A liquid with SG of 1 has API gravity of 10.

Crude oil classificated by API gravity according to distillate pressure as follows:

1- When the distillate at atmospheric pressure (Press. = 1 atm ) as follows :

I. API gravity > 40 paraffinic (or light) based crude oil

II. API gravity = 33 - 40 mixed (or intermediate) based crude oil

III. API gravity < 33 naphthenic (asphaltic or heavy) based crude oil

2- When the distillate at vacuum pressure (Press. = 40 mmHg) as follows:

I. API gravity > 30 paraffinic (or light) based crude oil

II. API gravity = 20 - 30 mixed (or intermediate) based crude oil

III. API gravity < 20 naphthenic (asphaltic or heavy) based crude oil

The definition of specific gravity for gases is somewhat different. It is defined as relative density
of gas to density of air at standard conditions. In addition, density of gases is a strong function of
pressure. Since at the standard conditions (15.5 C and 1 atm) the density of gases are estimated
from the ideal gas law, the specific gravity of a gas is proportional to the ratio of molecular weight
of gas (Mg) to the molecular weight of air (28.97).

Therefore, to obtain the specific gravity of a gas, only its molecular weight is needed. For a
mixture, Mg can be determined from the gas composition.

Sulfur Content
Crude oil naturally contains sulfur compounds. Crudes are classed as sweet or sour depending on
their sulfur content. If a crude has less than 0.5% sulfur in it, it is considered to be “sweet crude

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oil ". If has greater than 2.5% sulfur, it is “sour crude oil ". A crude with a sulfur content between
these two endpoints is called “intermediate ".

Refractive Index

Refractive index or refractivity for a substance is defined as the ratio of velocity of light in a
vacuum to the velocity of light in the substance (fluid) and is a dimensionless quantity shown by
n:

In other words, when a light beam passes from one substance (air) to another (a liquid), it is bent
or refracted because of the difference in speed between the two substances. In fact, refractive index
indicates the degree of this refraction. Refractive index is a state function and depends on the
temperature and pressure of a fluid. Since the velocity of light in a fluid is less than the velocity of
light in a vacuum, its value for a fluid is greater than unity. Liquids have higher values of refractive
index than that of gases. For gases the values of refractive index are very close to unity. however,
in a substance the velocity of light depends on the nature of the substance (molecular structure) as
well as the frequency of the light. For this reason, standard values of refractive index must be
measured at a standard frequency. Usually the refractive index of hydrocarbons is measured by the
sodium D line at 20 C and 1 atm. The instrument to measure the refractive index is called a
refractometer.

In some references the values of refractive index are reported at 25 C however, in this book the
refractive index at 20 C and 1 atm is used as a characterization parameter for hydrocarbons and
petroleum fractions. refractive index is a very useful characterization parameter for pure
hydrocarbons and petroleum fractions, especially in relation with molecular type composition.
Values of n vary from about 1.3 for propane to 1.6 for some aromatics. Aromatic hydrocarbons
have generally higher n values than paraffinic compounds.

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The Watson characterization factor (Kw)

Since the early years of the petroleum industry it was desired to define a characterization parameter
based on measurable parameters to classify petroleum and identify hydrocarbon molecular types.
The Watson characterization factor denoted by Kw is one of the oldest characterization factors
originally defined by Watson et al. of the Universal Oil Products (UOP) in mid 1930. For this
reason the parameter is sometimes called UOP characterization factor and is defined as

Tb1/ 3
Kw = where Tb = normal boiling point oR
SG
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(1.8Tb )1/ 3
Kw = where Tb = normal boiling point K
o

SG
Where

Tb = normal boiling point K

Crude oil classificated by Watson characterization factor as follows:

1. K = 12.15 – 12.9 paraffinic (or light) based crude oil

2. K = 11.5 – 12.1 mixed (or intermediate) based crude oil

3. K = 10.5 – 11.45 naphthenic (asphaltic or heavy) based crude oil

Vapor Pressure

In a closed container, the vapor pressure of a pure compound is the force exerted per unit area of
walls by the vaporized portion of the liquid. Vapor pressure, pvap, can also be defined as a pressure
at which vapor and liquid phases of a pure substance are in equilibrium with each other. The vapor
pressure is also called saturation pressure, psat, and the corresponding temperature is called
saturation temperature. In an open air under atmospheric pressure, a liquid at any temperature
below its boiling point has its own vapor pressure that is less than 1 atm. When vapor pressure
reaches 1 atm, the saturation temperature becomes the normal boiling point.

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Vapor pressure increases with temperature and the highest value of vapor pressure for a substance
is its critical pressure (Pc) in which the corresponding temperature is the critical temperature (Tc).

Vapor pressure is a very important thermodynamic property of any substance and it is a measure
of the volatility of a fluid. Compounds with a higher tendency to vaporize have higher vapor
pressures. More volatile compounds are those that have lower boiling points and are called light
compounds. For example, propane (C3) has boiling point less than that of n-butane (n-C4) and as
a result it is more volatile. At a fixed temperature, vapor pressure of propane is higher than that of
butane. In this case, propane is called the light compound (more volatile) and butane the heavy
compound. Generally, more volatile compounds have higher critical pressure and lower critical
temperature, and lower density and lower boiling point than those of less volatile (heavier)
compounds.

Acentric Factor

Acentric factor is a parameter that was originally defined by Pitzer to improve accuracy of
corresponding state correlations for heavier and more complex compounds. Acentric factor is a
defined parameter and not a measurable quantity. It is a dimensionless parameter represented by
ω and is defined as

• P𝑟 vap = reduced vapor pressure, Pvap /Pc, dimensionless

• Pvap = vapor pressure at T = 0.7 Tc

• Pc = critical pressure, bar

• T = absolute temperature, K

• Tc = critical temperature, K

Acentric factor is defined in a way that for simple fluids such as argon and xenon it is zero and its
value increases as the size and shape of molecule changes. For methane ω = 0.001 and for decane
it is 0.489. Values reported for acentric factor of pure compounds are calculated based on Eq. (6),
which depends on the values of vapor pressure. For this reason, values reported for the acentric

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factor of a compound may slightly vary from one source to another depending on the relation used
to estimate the vapor pressure. In addition, since calculation of the acentric factor requires values
of critical temperature and pressure, reported values for ω also depend on the values of Tc and Pc
used. Low-vapor-pressure compounds reduce evaporation losses and chance of vapor lock.
Therefore, for a fuel there should be a compromise between low and high vapor pressure.

Flammability Range

To have a combustion, three elements are required: fuel (hydrocarbon vapor), oxygen (i.e., air),
and a spark to initiate the combustion. One important parameter to have a good combustion is the
ratio of air to hydrocarbon fuel. The combustion does not occur if there is too much air (little fuel)
or too little air (too much fuel). This suggests that combustion occurs when hydrocarbon
concentration in the air is within a certain range. This range is called flammability range and is
usually expressed in terms of lower and upper volume percent in the mixture of hydrocarbon vapor
and air. If the calculated vol% of hydrocarbon in the air is within the flammability range then the
mixture is flammable by a spark or flame.

Pour Point

The pour point of a petroleum fraction is the lowest temperature at which the oil will pour or flow
when it is cooled without stirring under standard cooling conditions. Pour point represents the
lowest temperature at which an oil can be stored and still capable of flowing under gravity. Pour
point is one of low temperature characteristics of heavy fractions. When temperature is less than
pour point of a petroleum product it cannot be stored or transferred through a pipeline. Test
procedures for measuring pour points of petroleum fractions are given under ASTM D 97 (ISO
3016 or IP 15) and ASTM D 5985 methods.

Reid Vapor Pressure

Reid vapor pressure is the absolute pressure exerted by a mixture at 37.8 C (311 K or 100 F) at a
vapor-to-liquid volume ratio of 4. The RVP is one of the important properties of gasolines and jet
fuels and it is used as a criterion for blending of products. RVP is also a useful parameter for
estimation of losses from storage tanks during filling or draining. For example, according to
Nelson method losses can be approximately calculated as follows:

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 Petroleum Properties Lecture 2

Losses in vol% = (14.5 RVP - 1)/6, where RVP is in bar. The apparatus and procedures for standard
measurement of RVP are specified in ASTM D 323 or IP 402 test methods. In general, true vapor
pressure is higher than RVP because of light gases dissolved in liquid fuel. True vapor pressure is
important in the calculations related to losses and rate of evaporation of liquid petroleum products.
Because RVP does not represent true vapor pressure, the current tendency is to substitute RVP
with more modern and meaningful techniques.

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