Properties of Petroleum (Oil and gas) and Petroleum Products

by Prof. Dr. Ibtisam Kamal

Lec. 4

Thermal properties of Crude oil/ Definitions and Empirical Equations

Property

Heat of
combustion

Caloric value

Gross caloric
value
&
Net caloric
value

Thermal
conductivity

Specific heat

Definition

The energy released as heat when a compound

undergoes complete combustion with oxygen
under standard conditions. The chemical
reaction is typically a hydrocarbon reacting with
oxygen to form carbon dioxide, water and heat
The quantity of heat liberated by the complete
combustion of unit weight of the fuel in air or
oxygen, with subsequent cooling of the products
of combustion to the initial temperature of the
fuel.
The calorific value increasing with increasing
amounts of hydrogen. Moisture if present,
considerably reduces the calorific value of a fuel.
The gross calorific value
(the higher heating value)
The quantity of heat liberated by the complete
combustion of unit weight of the fuel with
subsequent cooling of the products of
combustion to the initial temperature of the
fuel.
Net calorific value
The heat produced when unit mass of fuel is
burnt completely and products of combustion
are allowed to escape.
Under normal working conditions, water
vapours produced during combustion are not
condensed and escape as such along with the
hot gases.Hence lesser amount of heat is
available, which is called Lower or net calorific
value.
Thermal describes the transport of energy in
the form of heat through a body of mass as the
result of a temperature gradient.
The quantity of heat required to raise a unit
mass of material 10 temperature.

Empirical Equations
cal/gram
d: density
Dulong formula
Calorific value =
1/100[8080 C + 34500 {H O/8 }
+2240 S]
kcal/kg
where C, H, O, S refer to % of carbon,
hydrogen, oxygen and sulphur
respectively.
Net calorific value=
Gross calorific value - Latent heat of
water vapours.
NCV=
GCV- weight of hydrogen x 9 x Latent
heat of water vapours
Latent heat of water vapours is 587
kcal/kg

BTU F1hr1ft1 . t ,F
t: Temp. oF

kcal/(kgC). d:Density, t: Temp. oC

Latent heat of
vaporization

Heat absorbed or released as the result of a

phase change
kcal/kg. d:Density, t: Temp. oC

Autoignition

The Autoignition Temperature

The minimum temperature required to ignite a
gas or vapor in air without a spark or flame.

Ex: Naphtha= 2250C , Kerosene= 295

0
C , Petroleum= 400, Coke=700 0C

The flammable
(explosive)
range

The range of a gas or vapor concentration that

will burn or explode if an ignition source is
introduced. Limiting concentrations are
commonly called the lower explosive or
flammable limit (LEL/LFL) and the upper
explosive or flammable limit (UEL/UFL

Very important for promote safety

storage,shipment and use of crude oil
& Light petroleum distillates include:
LPG, gasoline, light and heavy
naphtha, kerosene, and light gas oil
(LGO).

Flash Point

The flash point of a fuel is the temperature to

which the fuel must be heated to produce a
vapour/air mixture above the liquid fuel that is
ignitable when exposed to an open flame under
specified test conditions

Fire Point
.

Fire point is the lowest temperature, at which

the application of a test flame to the oil sample
surface causes the vapour of the oil to ignite and
burn for at least five seconds

Found in Mat. Safety Data Sheets

Flash point is used as an index of fire
hazard.
Many fresh crude oils have flash
points below 10C.
For Gasoline= -45 oF, Kerosene=100162 oF
In general the fire points can be
assumed to be about 10 C higher
than the flash points.

Cloud Point & Pour Point

In the petroleum industry, cloud point refers to the temperature below which wax in the fuel
form a cloudy appearance. The presence of solidified waxes thickens the oil and clogs fuel
filters and injectors in engines. The wax also accumulates on cold surfaces (e.g. pipeline or heat
exchanger fouling) and forms an emulsion with water. Therefore, cloud point indicates the
tendency of the oil to plug filters or small orifices at cold operating temperatures .
So, the cloud point is the lowest temperature at which wax crystals begin to form by a gradual
cooling under standard conditions. As temperature decreases below the cloud point, formation
of wax crystals is accelerated. Therefore, low cloud point products are desirable under lowtemperature conditions.
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 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. Presence of wax

and heavy compounds increase the pour point of petroleum fractions.

Cloud Point & Pour Point Determination

The apparatus used for the Cloud and Pour Point determination is shown below. The test
sample is first poured into a test jar to a level approximately half full. A cork carrying the test
thermometer is used to close the jar. The thermometer bulb is positioned to rest at the bottom
of the jar. The entire test subject is then placed in a constant temperature cooling bath on top
of a gasket to prevent excessive cooling.
At every 1 C, the sample is taken out and inspected for cloud then quickly replaced. The wax
crystals typically first form at the lower circumferential wall with the appearance of a whitish or
milky cloud. The cloud point is the temperature at which these crystals first appear. When no
movement is detected after 5 seconds from taking out the sample and tilted it horizontally, the
test is stopped. 3C is added to the temperature where no movement was observed and this is
the pour point. The pour point of petroleum fractions has been correlated to viscosity,
molecular weight, and specific gravity in the following form:

Tp : pour point temperature in kelvin , SG : specific gravity at standard temperature, M :

molecular weigh, 38(100) : kinematic viscosity at 38 o C(100o F) in cSt.

Cloud Point and Pour Point Apparatus (ASTM D2500)

Optical Properties
Refractive Index (RI)
The refractive index is a fundamental physical property of a substance, it is often used to identify a
particular substance, confirm its purity, or measure its concentration. The refractive index is the degree
to which light bends (refraction) when passing through a medium. Values of refractive index can be
measured very accurately and are used to correlate density and other properties of hydrocarbons with
high reliability.
The refractive index of light crude oils can be directly measured using conventional refract meter . The
refracto meter finds the critical angle of an incident beam of monochromatic light (sodium-D line with a
wavelength of 589nm) passing through the synthetic sapphire prism into the liquid sample. However,
direct measurements of the refractive index of many crudes, natural bitumen, and heavy fuels are
unattainable since these liquids are too opaque so RI is only measured for fairly dilute solution; in these
cases RI is determined for a series of oil/solvent mixtures and the results are extrapolated (in an
assumption of a certain mixing rule) to determine the value for the crude oil .

Refracto meter

Typical Curve showing the Refractive Index of oil/ solvent

mixture versus oil volume fraction

The Snells law is used to calculate the refractive index as follow:

.
The refractive index for some materials measured at 200C are listed in the following table:
Material
vacuum
Air
Water
Ethanol
Aceton
Toluene
Glycerol
Benzene
Silicon oil
Sodium chloride
Diamond

Refractive Index
1
1.02
1.33
1.36
1.36
1.497
1.47
1.501
1.52
1.54
2.42

On another hand, the refractive index of hydrocarbons varies with chemical structure. The
values of refractive Index follows the order :
and it increases with molecular wt.
Typical relation between the refractive index of the distilled narrow fractions with mid percent
boiling temperature of mixed crude oils is shown below. It is noted that the refractive index
increases with the increase of mid percent boiling point temperature of the fractions because
the refractive index of high molecular weight hydrocarbon is higher than that for low molecular
weight fractions. Typical correlation for variation of RI with API of a crude oil sample is also
shown.

The refractive index of narrow fractions

index up to 200C distilled from two crude oils

The relation between API and refractive

Vapor Pressure
Definitions:
Vapor Pressure
Is the pressure exerted by a vapor in equilibrium with its solid or liquid phase.
Reid Vapor Pressure (RVP)
Is the measure of the absolute vapor pressure exerted by a liquid at 100oF (37.8 oC) at a vaporto-liquid ratio of 4:1.

True Vapor Pressure (TVP)

Is vapor Pressure of a mixture including any dissolved gases that may be present.
In general, Vapor Pressure is an important physical property of volatile liquids. Vapor pressure
of crude oils is of importance to the crude producer and the refiner for general handling and
initial refinery treatment. Vapor pressure is also used as an indirect measure of the
evaporation rate of volatile petroleum solvents. It is critically important for both automotive
and aviation gasolines, affecting starting, warm-up, and tendency to vapor lock with high
operating temperatures or high altitudes. Maximum vapor pressure limits for gasoline are
legally mandated in some areas as a measure of air pollution control.
Reid vapor pressure (RVP) is defined as the absolute vapor pressure exerted by a liquid at 100
F (37.8 C) as determined by the test method ASTM-D-323. The test method applies to volatile
crude oil and volatile non viscous petroleum liquids with initial boiling point above 0C (32F)
except liquefied petroleum gases.
The Reid vapor pressure (RVP) differs slightly from the true vapor pressure (TVP) of a liquid due
to small sample vaporization and the presence of water vapor and air in the confined space of
the test equipment. That is, the RVP is the absolute vapor pressure and the TVP is the partial
vapor pressure. True vapor pressure is usually 5-9% > RVP.
Crude oil vapor pressure testing
The most commonly used method for crude oils has been the Reid vapour pressure as
determined by ASTM method D 323. It is measured by saturating a known volume of oil in an
air chamber of known volume and measuring the equilibrium pressure which is then corrected
to one atmosphere (101.3 kPa).
The adjacent drawing depicts the apparatus used for measuring the Reid vapor pressure of
gasolines and other products having a vapor pressure below atmospheric pressure. The streams
are flashed at 1 atm and 32 to 40 F (0 to 4 C) and the resulting liquid product is then
combined with air at the rate of 4 parts air and 1 part liquid. Next the system is flashed at
constant volume at 100 F (by immersing the apparatus in an electrically heated water bath).
After 5 minutes, the assembly is removed, shaken and the pressure gauge is read . The resulting
gauge pressure is the Reid vapor pressure

RVP bomb

Because of the presence air (and its of water vapor content) in the vapor space within the test
method's sample container, as well as some small amount of sample vaporization during the
warming of the sample to 37.8 C (100 F), the RVP differs by a small amount from the TVP of
the sample.

True Vapour Pressure of Refined Petroleum Stocks ( gasoline)