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Physical and Chemical Properties of crude oil

The appearance of crude petroleum varies From yellow low or green colored
mobile liquid to darker and of ten almost black syrupy fluids and sometimes
solidifying to a black paste this great variety in appearance is a obviously
caused by difference in composition . Some oils may be particularly rich in
hydrocarbons with a low M. wt and others rich in hydro carbons of
complicated large molecules .

(1) Physical Properties of crude oil:

A – Specific gravity:

Density and Sp.gr are principally of importance in connection with weigh

calculations and as a check on plant operation and gives a rough indication of
the composition of the products e.g whether paraffins or aromatics hydro
carbons are predominants . As a general rule, for given number of carbon
atoms, paraffins have the lowest Sp. gr , while aromatics the highest Sp. gr ,
naphthenes have Sp. gr , lying between them. For each group Sp.gr , increase
with the M . wt .
The terms specific gravity, density are often rather loosely used and in order to
avoid confusion, it is considered advisable to give here The following
definitions :

(a) Density :

Mass per unit volume under specified conditions of pressure and temperature ,
It is usually determined at atmospheric pressure and at a temp of 15º C (60 F º)

(b) Specific Gravity :

The ratio of the densities of a body and water under Specified conditions of
pressure and temperature and it's dimensionless and at 60/60 Fº
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(c ) Gravity API :

It refers to the API system and it has empirical for mula as follow :

141.5
ºAPI = 131.5 - ‫ــــــــــــــــــــــــــــــــــــــــ‬
Sp. gr @ 60/60 Fº

A point which is of great technical intersest is the relationship between sp . gr ,

and temp, so an accurate temp, correction is of great importance in connection
with the calculations of tank stock, product yield

(B) Boiling point :

The difference in the boiling point of individual hydrocarbons is the basis of

the dist, technique by which crude oil fractionated into cuts of different
volatility.

For all homologous series of hydrocarbons the boiling point increases with the
number of carbon atom in the molecule. Aromatics have, in general higher
boiling point than the corresponding apothems and paraffin's.
In case of mixtures (at constant P ) , a temp range may be indicated where both
liquid and vapor are in equilibrium with each other the lower limit is the " dew
point" and the upper limit is " dew point " of the mixtures .

( C ) Melting point :

The crystatization of solid from a liquid oil fraction seriously hampers its flow
and may give rise to blocking of lines and clogging of filters, so melting point
is very important from a view point of oil processing and the application of the
product.
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The melting points of homologues hydrocarbons increase with M. wt.

In general Iso paraffin have, in general, a lower melting point than normal
paraffins of same number of carbon atom .

( D ) Viscosity :

Viscosity of an oil product is very important from a technical point of view It is

plays an important part in calculation of pipelines and the design of furnaces
and heat exchangers and is further one of the leading properties in lub oil and
fuel oil and fuel oil prices are frequently based on visc.
Viscosity depend on the type of components and temp. Viscosity of paraffins
is approximately a function of the density. Aromatics with a low M . wt often
have a lower visc. than in the corresponding paraffins, whereas the high
molecular aromatics of lub oil are more viscous than the paraffins.

( E ) Solubility characteristics :

The Solubility characteristics of the various hydrocarbons types play an

Important part in the extraction processes like extraction of Aromatics which
Dissolve In polar solvent like phenol much better than paraffins and
naphthenes.

( S ) Chemical properties :

In general paraffin hydrocarbons are usually chemically inert so a number of

processes is applied in petroleum refining by chemical means for conversion
paraffin like Isomerization, alkylation, Aromatization. also naphthenes. can be
converted by chemical means .
It is very difficult to discuss the chemical reaction in which various
hydrocarbons can enter so, only a few important groups of reactions will be
considered, namely:

(1) reaction under the influence of heat ( thermal reactions pyrolysis )

(2) reaction under the influence of oxygen ( oxidation reactions )
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Thermal reactions:

Thermal stability of hydrocarbons decreases, in general, as M. wt increase.

When considering individual members of the various groups with the same
carbon atom the stability of heat increase the order:

- n- paraffins
- Iso - paraffins
- Olefins
- Naphthenes
- Alkyl aromatics

Oxidation Reaction:
The influence of oxygen on hydrocarbons is important in connection with the
storage stability of petroleum products .Most pure paraffin's naphthenes and
Aromatic are not affected by oxygen under atmospheric pressure and temp and
therefore stable in storage.

It should be mentioned that olefins and practically di-olefins are easily

oxidized and converted into polymers.

Many so calld " impurities " like nitrogen , oxygen and Sulphur compounds
occurring in relatively small % in crude oil may give troubles when present in
certain product , especially when the product have been aged during storage
(oxidation) .

(3) Compounds other than hydrocarbon present in crude oil :

(a) Sulphur Compound:

Two types of Sulphur Compound are present in crude oil , the corrosive ones,
such as free Sulphur, H2S and RSH.
The non corrosive Sulphur like thiophenes, ( R – S - R ) and ( R –S –S – R )
but thy may on decomposition at higher temp causes corrosion Apart from the
smell the unpleasant smell which some Sulphur Compounds may caused to
products and when Sulphur present large quantity in fuel, Sulphur oxides will
formed and H2SO4 is formed also which may cause corrosion in parts of
combustion engine. also Sulphur Compounds are undesirable in illuminating
kerosene, which cause a which spot on lamp chimney .
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(b) Oxygen Compounds

Some crude oils contain naphthenic acid which contain CooH group , these
acids are sometimes, highly corrosive and also have a bad smell .
Another, oxygen Compounds are phenols and these phenolic Compounds
contribute to the colour in stability of the kerosene distillates

( C ) Nitrogen Compounds

Nitrogen Compounds cause discoloration of heavy gasoline and kerosene.

Too high a content of nitrogen Compounds in gasoline may have a bad effect
on the engine fouling characteristics of the product .
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Evaluation of crude Oil

The object of "crude Oil evaluation" is to know it's general characteristics and
also . to collect data on the yields and properties of the products which can be
obtained from it. schemes for processing the oil in the refinery and the design
of processing equipment are based in this information .

The evaluation of crude Oil classified to:

(1) Determination the general characteristics of crude.

(2) Determination base of crude.
(3) Distillation process.

(a) General characteristics of crude :

These tests are carried out:

(1) Sp. gravity @ 60/60ºF

(2) API
(3) Water content
(4) Salt content
(5) Sulphur content
(6) Nitrogen content
(7) Asphaltenes
(8) C.C.R
(9) V. pressure
(10) ASTM Distillation
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(11) Viscosity
(12) T.A.N.
(13) Pour point
(14) Trace elements
(15) H2S & RSH.
(16) G.C Analysis
For the above tests it carried out by standard methods using ASTM or IP or
UOP
(b) Determination the base of crude :
(1) American bureau of mines method :

This method depend on taking two cuts, the first which called ( key fraction I )
and it's boiling range 250ºC -------------- 275ºC at atmosphere distillation and
the second cuts called ( key fraction II ) and it's boiling range 275ºC --300ºC
At Vaccum distillation ( 40 mm Hg )
The following table illustrate the types of crude

API for II API for I Type

30 and higher 40 and higher Paraffinic
20 ------- 30 40 and higher Paraffinic – Medium
30 and higher 33 ---------- 40 Medium – Paraffinic
20 -------- 30 33 ---------- 40 Medium
20 and lower 33 ---------- 40 Medium – Naphtenic
20 -------- 30 and lower 33 Naphtenic - Medium
and lower 20 and lower 33 Naphtenic
and lower 20 40 and higher Paeaffinc - Naphtenic
33 and higher 33 and lower Naphtenic - Paeaffinc
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2 ) UOP 375/86 method :

This method depend on calculate characterization factor (k) according to the

method and from it's value we can determine the base of crude as follows :

10.5 --------- 11.42 Naphtenic

11.5 --------- 12.1 Medium
10.15 --------- 12.9 Paraffinic

(C ) Distillation of crude:
The crude is distilled in special apparatus (T.B.P Distillation apparatus ) which
contain a column equipped with mineral material at which elevated vapours
contact with drawn liquids and apparatus is similar to distillation unit,- controll
of P , T , F and reflux.

the distillation begin at atmospheric pressure and temp raised gradually and we
collect cuts about 1 % volume and recording temp of top and bottom for each
cut unit we reach to 300ºC of the bottom.

The distillation begin again at vacuum ( 40 mm Hg ) and collect cuts about 1 %

volume and also recording temp of top and bottom and we continue distillation
unit we reach to 300ºC of the bottom ( rearranged at atmospheric pressure ).
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at this point the crude contain quantity of waxes not to distill easy with T.B.P
column which must replaced l by another column and continue distillation at
vaccum up to 1 mm Hg until reach to temp of 500 ºC we collect cuts which
represent I % vol.

For the data we obtained we can draw . T.B.P curve of the crude through
which many data known and also we can collect data on yield and properties
of products.