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PROPERTIES OF

CRUDE OILS and


PETROLEUM
PRODUCTS

Reproduced by Solomon Associates with the expressed permission of Haverly Systems, December 2007

Copyright 1987 - 2007 Haverly Systems Inc.


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Haverly Systems Inc.


Tel (201) 627-1424

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P.O. Box 1110
Denville, New Jersey 07834
Fax (201) 625-2296 E-mail info@haverly.com

Table of Contents
INTRODUCTION..................................................................................................................................... 3
DISTILLATION ..................................................................................................................................... 11
GRAVITY & DENSITY .......................................................................................................................... 14
SULFUR ............................................................................................................................................... 16
MERCAPTAN SULFUR ........................................................................................................................ 19
HYDROGEN SULFIDE ......................................................................................................................... 19
THIOPHENES ....................................................................................................................................... 19
NITROGEN ........................................................................................................................................... 21
OCTANE ............................................................................................................................................... 23
FLASH POINT ...................................................................................................................................... 26
REID VAPOR PRESSURE .................................................................................................................... 27
SMOKE POINT ..................................................................................................................................... 28
LUMINOMETER NUMBER ................................................................................................................... 28
ANILINE POINT .................................................................................................................................... 30
REFRACTIVE INDEX............................................................................................................................ 32
COLD PROPERTIES ............................................................................................................................ 33
POUR POINT .................................................................................................................................... 33
CLOUD POINT .................................................................................................................................. 35
FREEZE POINT ................................................................................................................................ 35
COLD FILTER PLUG POINT ............................................................................................................. 35
CETANE NUMBER ............................................................................................................................... 37
CETANE INDEX.................................................................................................................................... 38
DIESEL INDEX ..................................................................................................................................... 38
VISCOSITY ........................................................................................................................................... 40
VISCOSITY INDEX ............................................................................................................................... 43
NEUTRALIZATION & TOTAL ACID NUMBER ..................................................................................... 45
WAX...................................................................................................................................................... 46
METALS ............................................................................................................................................... 47
CARBON RESIDUE .............................................................................................................................. 49
SULFUR IN CARBON RESIDUE .......................................................................................................... 49
ASPHALTENES & RESINS .................................................................................................................. 51
n-PENTANE INSOLUBLES .................................................................................................................. 53
PENETRATION .................................................................................................................................... 53
SOFTENING POINT ............................................................................................................................. 53
DUCTILITY ........................................................................................................................................... 53

INTRODUCTION
The principal elements in petroleum fuels are carbon and hydrogen. Sulfur, nitrogen and oxygen are also
present in lower concentrations and a range of other elements, notably metals, are found in trace
quantities. These elements are linked together in a wide variety of molecular forms: for example, more
than 600 different hydrocarbons have been identified in petroleum.
Except for a few of the lightest compounds (boiling temperatures below several hundred degrees F) the
mixture is never separated into pure compounds. Rather the crude oil is separated by atmospheric and
vacuum distillation into fractions consisting mostly of those compounds boiling between initial and final
boiling point temperatures for the fraction.
There are four principal categories in which the molecules can be grouped.
1. Saturated Hydrocarbons
The term saturated is applied to hydrocarbons that contain only single carbon-carbon bonds.
Normal Paraffins are molecules in which carbon atoms are arranged in a straight chain. In most
crude oils they are present in a continuous homologous series CnH2n+2 in which the maximum
number of carbon atoms n is usually around 40. The members with carbon atoms 1 to 4 are gases,
(methane, ethane, propane butane) under ambient conditions; those with carbon number 5 to 18
are liquids, with n>18 are solids.
Iso-paraffins are branched structures with side chains attached to the main carbon atom
backbone. In crude oil, the highest number of carbon atoms in the molecule rarely exceeds 25.
Naphthenes (cycloparaffins) are molecules in which the carbon atoms are arranged in a ring. They
are very important constituents of petroleum and account for about half the mass of an average
crude oil. Practically all the naphthenes found in fuels are based on species having five and sixmembered rings. The types found in distillate fuels consist of one or two fused rings with paraffinic
side chains. The larger naphthenes, which are found in residual products, comprise up to five fused
rings and have longer paraffinic side chains than mono and bicyclic types.
2. Unsaturated Hydrocarbons
The term Unsaturated is applied to hydrocarbons that contain one or more carbon-carbon double bond.
Olefins contain on double bond. They are relatively unstable and as a result are generally not
present in crude oils. However, they are produced in crude oil processing, especially in conversion
units.
Aromatics are compounds with one or more benzene rings such as toluene (one benzene ring) or
naphthalene (two benzene rings sharing a common bond). Benzene is the simplest aromatic
molecule and has its carbon atoms arranged in a six-membered ring. More complex aromatics
consist of several fused benzene rings with side chains attached. Molecules comprising of up to
five fused rings have been identified in heavier fuels although single and double-ringed species are
always predominant.
Naptheno aromatics are a combination of fused aromatic and naphthenic rings with side chains
that are predominantly methyl, CH3, groups; they are a major constituents of heavier fuel fractions.
The number of fused rings varies from two to five.

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Saturated Hydrocarbon Constituents


Normal Paraffins

Iso-paraffins

Naphthenes

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Unsaturated Hydrocarbon Constituents


Olefins

Butylene

Aromatics

Naphtheno Aromatics

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Hetro-Atomic Constituent

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3. Hetro-Atomic Molecules
Some constituents of petroleum fuels contain elements in addition to carbon and hydrogen, notably
sulfur, nitrogen or oxygen.
Sulfur compounds form the most important group with respect to both quantity and their effect on
fuel performance.
Nitrogen is present in all crude oils, up to a maximum of about 1% by weight. Molecules in which
the nitrogen is bound can constitute 15% by weight of the oil.
Oxygen compounds are present in low concentrations in crude oils. During processing, the majority
decompose to form ring compounds with a carboxylic acid group, COOH, attached in a side chain
and a re generally called naphthenic acids.
More details on these elements are covered later in this course manual.
4. Complex Species
The structure of this group of compounds is chemically less well defined and are broken down into two
broad groups; Resins and Asphaltenes.
They are aromatic materials with polar groups attached which can be precipitated by the addition of
liquid propane. The part of the precipitate that is dissolved by n-heptane is defined as the resins; the
insoluble part is defined as the asphaltenes.
Both asphaltenes and resins are confined to residual streams. The asphaltenes are a particularly
important class of compound and give residual products unique characteristics in relation to distillate
fractions. When precipitated they form dark brown to black solids. Asphaltenes are composed of a
number of sheets that comprise an arrangement of condensed aromatic and naphthenic rings with a
number of side chains. Sulfur, nitrogen and oxygen are also contained within the structure. Several
sheets link together to form the asphaltene molecule. Bonding of the sheets is accomplished either by
covalent bonding, or by strong associative forces.
Asphaltenes have high molecular weight and typically contain seven to eight unit sheets. The unit sheets
comprise up to 16 condensed aromatic rings which mean that asphaltenes, as a class, are very aromatic
materials. The total number of sulfur, nitrogen and oxygen atoms associated with each unit sheet is
nearly always less than five. Additionally, a significant fraction of a crude oils inherent content of
vanadium and nickel is likely to be associated with its asphaltenes.
When resins are precipitated, their appearance varies from dark yellow, viscous liquids to amorphous,
dark-colored solids. Their structure is broadly similar to that of the asphaltenes but they are smaller and
less aromatic and typically consist of only one unit sheet. Resins generally contain more oxygen, and
less sulfur and nitrogen than asphaltenes; their hydrogen content is higher owing to their lower
aromaticity.
CATEGORIZING CRUDE OILS
Crude oils are often grouped into types. There is no standard industry definition of crude oil types.
Frequently used types are: (1) heavy vs. light crudes, (2) low or sweet vs. high or sour sulfur crudes
and (3) paraffinic vs. naphthenic crudes.

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Heavy crudes are ones with a high proportion of high-boiling, high-specific-gravity components and a
large percent of residuum. Light crudes have a high proportion of naphthas and middle distillates and
little residua.
Industry sometimes uses 1 wt% Sulfur as the criteria of sweet (less that 1%) versus sour (greater than
1%) crude oil.
A crude oil predominantly of paraffin type compounds is called a paraffinic crude oil. One with
predominantly ring compounds is called a naphthenic crude oil. Actually some crudes may have more
aromatic than naphthene type compounds but it is still called a naphthenic crude. Crude oils with high
aromatics content are not typically spoken of as aromatic crudes. Of course a crude oil may be largely
paraffinic in one fraction while largely naphthenic in another.
The proportion of paraffins, naphthenes and aromatics strongly influence many of the properties. For
example, for the same number of carbon atoms in a molecule the aromatics have the highest boiling
point, cycloparaffins in between boiling points and paraffins the lowest. For compounds of similar boiling
points paraffins have the lowest density, the highest smoke point, the highest pour and cloud points, the
highest viscosity index, the highest aniline point, and the lowest viscosity.
In general aromatics are the opposites of paraffins with naphthenes in between. Paraffins are the easiest
to crack, aromatics the hardest. Paraffins make good waxes and lube oils while aromatics make good
asphalt. Crudes that are excellent for making asphalts are generally naphthenic crudes and they may be
high in sulfur, nitrogen and metals. In naphthas, the naphthenes can be converted to aromatics by
catalytic reforming. Also, the structure of the paraffin may affect some properties significantly.
Branched-chain paraffins in the gasoline boiling range have much higher octanes than the straight-chain
paraffins. Iso-octane has an octane number of 100 while normal heptane has an octane number of zero.
Both are paraffins. Also branched paraffins tend to have lower smoke points than straight chained
paraffins. In general aromatics are desirable in gasoline because of their octane and undesirable in
diesel fuels because of their low Cetane. However, air-pollution regulations now limit the content of
aromatics in gasoline.

CRUDE OIL PRODUCTS


Lower boiling fractions are typically used for refinery fuel gas, LPG, gasoline and naphtha solvents.
Medium boiling fractions (300 to 700 degrees F) are known as mid-distillates and have uses as kerosene,
jet fuel, diesel fuel and heating oil. Heavier fractions (boiling between 700 and 1000 F) are separated by
a vacuum distillation unit and find uses as fuels, waxes and lubricating oils. Residual fractions from
vacuum distillation (material not distilled off at 1000 F) are used in heavy fuels and asphalt products.
Lighter fractions, such as mid-distillates, may be blended with heavier fractions to improve the properties
of products being made.
Many of the fractions also are used as feeds to various refinery processes. A cracking process changes
the chemical composition and boiling range of the mixture. A naphtha fraction may be fed to a catalytic
reformer as a means of improving the octane and making a better gasoline blending stock. All distillates
boiling above 400 F are potential feed stocks to a cracker, although the most common cracker feedstock
is vacuum gas oil, boiling between 700 and 1000 F. Even deasphalted oil bright stocks have been fed
to crackers with some deasphalting units having been designed specifically to produce this type of
cracker feedstock. Residuals may also be fed to a coker unit producing coke for metallurgical use,
electrodes or just common fuel. By-products from cracking include a whole range of boiling point
materials which can be further processed to add to the supply of materials used to make products.

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DISTILLATION
TBP
TBP stands for the true boiling point data. The tests are run in a column with high reflux and good
separation. This is often done in a column with fifteen theoretical plates and a reflux ratio of 5 to 1
according to ASTM D2892. TBP represents an accurate measure of the volume which will distill vs.
temperature. TBP data is used for the crude assay input. When used in connection with a distillate cut
one may want data for the initial temperature, the final temperature and the temperatures at which
specified amount of the cut has distilled over (typically 5%, 10%, 30%, 50%, 70%, 90% and 95%). In
refinery production equipment one would not expect to get as accurate separation as the TBP data.
ASTM Distillations
Typically in an operating refinery a simpler, quicker distillation test is used to help monitor operation and
to conform to product specifications. Two ASTM tests are in common use. One is the ASTM D86 test,
the other the ASTM D1160 test.
D86: The D86 test is done at atmospheric pressure with little reflux ratio. It is basically a batch
distillation where 100 ml of sample is distilled under prescribed conditions and observations are
made of the temperature readings and volumes of condensate. A mercury-in-glass thermometer
(or equivalent in automatic equipment) records the vapor temperature at the vapor outlet. This
temperature is actually 0-32 degrees F below true temperature for observed ASTM D86
temperatures between 200 and 700-degree F, respectively. The standard test procedure (and
product specification based thereon) provides for using the temperature as recorded without any
such adjustment. Adjustments to temperatures are made when pressure is not 760 mm Hg.
D1160: In this test the distillation is done at predetermined and accurately controlled reduced
pressure. It would be used for fractions which may decompose when distilled at atmospheric
pressure. A thermocouple is used to measure temperatures. The results are likely to be closer to
TBP than the D86 test. Observed temperatures are converted to atmospheric pressure equivalent
by use of a formula or chart as given in the ASTM Manual of Hydrocarbon Analysis for D1160.
D2887: Simulated distillation (SD) by gas chromatography appears to be the most simple,
reproducible, and consistent method to describe the boiling range of a hydrocarbon fraction. This
method is applicable to all petroleum fractions with a final boiling point of at least 1000 deg F or
less at atmospheric pressure. The method is also limited to samples having an initial boiling point
of at least 100 deg F. Simulated distillations are plotted in weight percent.

Conversion of Distillation Results. Methods are available for estimating ASTM distillation data from
TBP data and vice versa. One method for D86 is the API Procedure 3A1.1 (1987). It coverts each
temperature (initial, 5%, etc.) from one system to the other without regard to data points at the other
temperatures. The method does not give consistently good results.
Another method for D86 is the API Procedure 3A1.1 (1980). It was adapted from Edmister and Pollock,
Chem. Engr. Progr. 44 905 (1948). One first converts the 50% point and then calculated the differences
to other points based on corresponding differences in the originating data. For example, convert the
50% TBP temperature to 50% ASTM. Then take the difference in temperatures between the 30% and
50% TBP data, convert it to ASTM using the charts and apply this difference to the 50% ASTM point to
get the 30% ASTM point.
The basic approach in the second method appears to be sounder than the first. However some believe
that a better method for D86 is based on Edmister-Okamoto correlation in Petroleum Refiner, August
1959. This approach is similar to the second method but uses different correlations. For example the
50% point has a much bigger adjustment for higher temperatures. CAL II uses this latter method.
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Volume distilled for corrected D86 ASTM temperatures (add 0-32) can be correlated to TBP volume at
the same temperature.
To convert D1160 ASTM data to TBP and vice versa one can use the API procedure 3A2.1. In it, the
50% points for ASTM and TBP are the same. The 50% to 70% and the 70% to 90% differences are the
same. The 50% to 30% and 30% to 10% differences are only slightly different while the 10% to 0% have
significant differences (up to 18 degrees F). The basic approach is similar to the second and third
methods above but with less adjustment.

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GRAVITY & DENSITY


Description
These relate to the weight per unit volume. This may be expressed as Specific Gravity (weight of
material compared to an equal volume of water), Density (weight per standard volume) or API Gravity.
All of these measures vary with temperature so the temperature of the sample is part of the definition.
API gravity is defined at 60 degrees F. Density may be measured at 0 or 4 degrees C or 60 degrees F or
another temperature. Specific gravity is the ratio of the weights of a standard volume of the material at a
given temperature compared to the weight of the same volume of water at a temperature. The two
temperatures are often, but not always, specified the same. API gravity is related to specific gravity (or
vice versa) by the following formula:
API = (141.5/Sp.gr at 60F/60F) - 131.5
Since the specific gravity of water is 1.0, its API gravity is ten (10).
Range
Gravity is widely used in crude assay calculation and is needed for whole crude and over the full range of
distillates and residues.
Typical Values
Most petroleum fractions and crude oils are lighter than water, i.e., have API gravities greater than 10
and specific gravities less than 1.0. However, many crude residuals and some highly cracked heavy
cycle oils are heavier than water.
Whole crude oils in the marketplace range from 10 to 66 API. However, benchmark crude oil has a
gravity around 33 API. Two-thirds of all crudes of commerce are between 25 and 40 API. Generally the
API gravity is an indication of the proportion of lighter distillates to resid in the crude. High API indicates
a higher proportion of light material. Also a crude oil (or portion of the crude oil) with a high proportion of
aromatics and naphthenes will have a higher density (lower API) than a crude with mostly paraffins.

Test Methods
ASTM D 1298
or

Standard Test Method for Density, Relative Density (Specific Gravity),


API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method.

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SULFUR
Description
This is the weight percent of sulfur in the material. Sulfur may be present in Crude Oils and petroleum
products as dissolved sulfur and hydrogen sulfide or as organic compounds such as thiophenes, sulfonic
acids mercaptans, alkyl sulfates and alkyls sulfides. See the diagram on following page which depicts the
structural formulas for some of these compounds. Many of these compounds occur naturally in crude
petroleum whereas others are formed during processing.
For any given crude the higher boiling fractions almost always have higher sulfur content than lower
boiling fractions. Residues have higher sulfur contents than distillates. See an attached example of
sulfur curve.
Sulfur in Petroleum is undesirable for a number of reasons: corrosion, odor, air pollution, poor burning or
explosive characteristics, and catalyst poisoning. Sulfur compounds are not only corrosive to refinery
equipment but can cause corrosion and wear in engines, boilers, and furnaces. In the case of motor and
aviation gasoline, sulfur inhibits the effectiveness of lead antiknock as octane boosters and contributes to
the depletion of lubricating oil additives.
Legal limits of the sulfur content of fuel products for environmental reasons makes high sulfur crude oils
more costly for a refiner to process.
Range Of interest for whole crude and over the full range of distillates and residues. Whole crude
concentrations range from less than 0.1 wt% to 7 wt%.
Typical Values
There is no general accepted criterion for classifying a crude oil as either high- or low-sulfur crude but the
following are guidelines proposed by Nelson as a criterion for low-sulfur crudes:
Crude Oil, API
12
15
20
25
30
35
40
45

Sulfur Content, Wt%


< 0.93
< 0.88
< 0.75
< 0.60
< 0.46
< 0.35
< 0.25
< 0.15

Note that high-sulfur crudes are not necessarily sour crudes. The term sour can only be applied to
those crudes which contain more than 0.05 cu. ft of dissolved hydrogen sulfide per gallon of oil (0.374
liters/liter).
This level of dissolved H2S makes sour crudes dangerously toxic.
Test Methods
ASTM D 129/IP 61

Test for Sulfur in Petroleum Products (General Bomb Method)

ASTM D 1551/IP 63

Test for Sulfur in Petroleum Oils (Quartz-Tube Method)

ASTM D 1552

Test for Sulfur in Petroleum Products (High-Temperature Method)

ASTM D 2662

Test for Sulfur in Petroleum Products (X-Ray Spectrographic


Method)
ASTM D 1266/ IP 107
Test for Sulfur in Petroleum Products (Lamp Method)

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MERCAPTAN SULFUR
Description
Mercaptans often have an objectionable odor, can be corrosive and have an adverse effect on some fuel
systems. As an example, the smell of skunk is butyl mercaptans. Methyl mercaptan is added to
odorless natural gas so customers can smell when gas may be leaking. Mercaptans are undesirable in
aviation fuels because they react with certain elastomers.
Range Mercaptan sulfur compounds are generally found concentrated in the gasoline boiling range
fractions. They may be present in kerosene and light mid-distillates.
Typical Values See Sulfur.
Test Methods
ASTM D 1219/IP 104
ASTM D 3227
ASTM D 484/IP 30

Test for Mercaptan Sulfur in Aviation Turbine Fuels


(Color-Indicator Method)
Test for Mercaptan Sulfur in Gasoline, Kerosine, Aviation Turbine
and Distillate Fuels (Potentiometric Method)
Doctor Test Method

HYDROGEN SULFIDE
Description
The hydrogen sulfide gas associated with some crude oils within the reservoir is normally removed along
with light hydrocarbon gases during the gas separation stage of production. Some oil companies
measure Hydrogen sulfide both dissolved and evolved. Dissolved Hydrogen sulfide in crude oil is
stripped at room temperature with nitrogen and absorbed in a cadmium sulfate scrubber. The crude oil
sample is then heated and the hydrogen sulfide evolved is absorbed in a second scrubber. Hydrogen
sulfide found in the first scrubber is reported as dissolved Hydrogen sulfide and the total in the two
scrubbers is reported as evolved Hydrogen sulfide.
Hydrogen sulfide was used in the past as a refinery fuel but when it burned in furnaces, sulfur dioxide is
formed. Air quality regulations now limit SO2 emissions to the extent that most of the H2S must be kept
out of the fuel systems.
Test Methods
ASTM D 130/IP 154
ASTM D 853
ASTM D 2385
ASTM D 2420

Detection of Copper Corrosion from Petroleum products


(Copper Tarnish Test)
Test for Hydrogen Sulfide and Sulfur Dioxide Content of
Industrial Aromatic Hydrocarbons.
Test for Hydrogen Sulfide in Natural Gas
(Cadmium Sulfate-Iodometric Titration Method)
Test for Hydrogen Sulfide in Liquefied Petroleum Gases
(Lead Acetate Method)

THIOPHENES
Description
Thiophene is a ring compound comprising one sulfur atom and four carbon atoms in the ring plus four
hydrogen atoms. It has a boiling point and some chemical properties similar to benzene.

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NITROGEN
Description
The importance of nitrogen in petroleum is due to its adverse effect on processing catalysts and on the
stability of finished oils. High nitrogen content can result in high hydrogen consumption in hydroprocesses such as residual hydrodesulfurization.
The nitrogen content of crude oils ranges between 0.01 and 0.9 weight percent. Most of the compounds
containing nitrogen have boiling points above 750 F. A distinction is made between those compounds in
which the nitrogen can be made to react chemically as a base, called basic nitrogen, and those which
do not do so.
The basic nitrogen compounds include pyridines and quinolines, e.g.,

Non-basic nitrogen containing series include pyrroles, indoles, carbazoles and benzcarbazoles, e.g.

Although the nitrogen contents of California crudes are generally the highest in the world, there are very
few crudes in which the nitrogen content is negligible. In general, the more asphaltic crude oils contain
greater amounts of nitrogen and the bulk of the nitrogen is in the high molecular weight portion of the
oils.
Range Of interest for heavy distillates and resids.
Typical Values
The higher boiling fractions contain most of the nitrogen.
distillates.
Test Methods
ASTM D 3228
ASTM D 4629

Residues contain more nitrogen than

Standard Test for Total Nitrogen in Lubricating Oils and Fuel Oils
By Modified Kjeldahl Method
Standard Test for Organically bound Trace Nitrogen in Liquid Petroleum
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Hydrocarbons by Oxidative Combustion and Chemiluminescence

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OCTANE
Description
The power obtained from a conventional reciprocating engine is limited by two distinct types of abnormal
combustion known as knock and rumble. When the fuel-air mixture in the cylinder of a spark-ignition
engine burns spontaneously in localized areas instead of progressing from the spark, this explosive
decomposition produces a characteristic noise or knock. Rumble, on the other hand, is caused by
multiple pre-ignition of the fuel-air mixture during the compression stroke and is also recognized by a
characteristic noise sometimes referred to as wild ping. In both cases, the accompanying pressure
surge cannot be converted into mechanical work by the piston, which must move in a fixed time/position
relationship, and is lost as heat to the engine cooling system and the exhaust gas. In addition to the loss
of power and fuel economy, knocking can result in engine damage and may burn a hole in the piston.
For these reasons, the antiknock quality of gasolines is one of their most important properties.
Octane number is a measure of the resistance of the petroleum fraction to knock in a gasoline engine.
Octane numbers may be measured by the Research method (RON by ASTM D 908) or the Motor
method (MON by ASTM D 357) and may be done Clear (i.e., without any lead additive) or with some
lead added.
The test fuel is compared to blends of two pure hydrocarbons, normal heptane and isooctane (2, 2, 4trimethylpentane). Normal heptane is quite low in its resistance to knock and has been arbitrarily
assigned an octane value of zero; isooctane has good antiknock properties and has, therefore, been
assigned a value of 100. The octane number of a fuel is defined as the volume percentage of isooctane
in a blend of n-heptane which is equal to the test fuel in knock intensity under standardized test
conditions.
Because some hydrocarbons have better antiknock properties than pure isooctane, it became necessary
to extend the octane scale above 100. In these cases, the antiknock ratings are expressed as either
performance numbers or quantities of tetraethyl lead (TEL) in isooctane and converted to equivalent
octane numbers via the Wiese scale. The performance number is an indication of the relative power
obtainable from an engine using the test fuel as compared with operation of the same engine with leaded
isooctane, operating at equal knocking intensity.
The Research method involves testing at lower engine speeds than the Motor method. The research
octane number (RON), which is also referred to as F-1 octane number, is representative of the fuel
performance during city driving when the speed is generally low and acceleration frequent. On the other
hand, the motor octane number (MON), or F-2 number, indicates the relative fuel performance at high
speeds. Generally, RON is greater than the MON and the difference between the two ratings is known
as the sensitivity or spread of the fuel. Commercial gasoline often have motor octane values about 8
numbers below their research octane values.
There is also a Road Octane test which often gives values between the Research and Motor numbers.
Road Octane may also be approximated by (RON+MON)/2. In the USA the published octane at the
pump is the average of RON and MON.
Sensitivity
Of the two types of octane numbers, the research number is most often reported and correlations
developed for estimating octane numbers from other physical and chemical properties are usually based
on the research number. Since the RON and MON are related by chemical composition, the MON can
be estimated from the RON of the gasoline.

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Susceptibility
The octane number response to lead alkyls varies with the hydrocarbon composition of the gasoline and
is known as the TEL or lead susceptibility. Although the octane number usually increases with increasing
concentrations of lead alkyls, this response is not linear, i.e., it is not proportional to the lead level. As
the lead level concentration increases, its effectiveness as an octane booster decreases, i.e., the
marginal gain in octane number per unit of additional lead alkyl decreases.
Addition of lead to the gasoline (tetra-ethyl lead, or in some cases, tetra-methyl lead) reduces the effect
of the free radicals and improves the octane rating of the gasoline. The amount of change in the octane
for a compound (or mixture of compounds) from addition of lead is called susceptibility. Lead increases
the octane most for low octane paraffin compounds. The effect of lead is reduced in the presence of
sulfur (particularly mercaptans, mono sulfides and disulfides) and Olefins.
Octane Blending Values
When gasoline components are blended together, the octane number of the blends may be greater than,
equal to, or less than that calculated from the volumetric average of the octane numbers of the blend
components. Blending deviations become more pronounced with increasing differences in the
component properties such as antiknock rating and hydrocarbon type. Deviations of several octane
numbers between observed and calculated octane numbers have occurred when blending common fuel
components. Thus, economic calculations designed to optimize refinery operations or refinery blending
would always be subject to question without the preparation and testing of the blends being considered.
Before the development of octane prediction equations, operating personnel relied on correction factors
based on their experience. Although these corrections are useful in certain situations, they are not
universally applicable.
One octane prediction equation is the DuPont Interaction Blending approach which uses the following
model (equation) to describe nonlinear gasoline blending behavior:
Octane No.

a1 X1 + a2 X2 + b1,2X1X2

where:
a1
a2
X1
X2
b1,2

=
=
=
=
=

octane number of component 1


octane number of component 2
Volume fraction of component 1
Volume fraction of component 2
Interaction coefficient for components 1 and 2.

The interaction equation is accurate over the entire range of composition. The curve was developed
using only the data from the two components and the 50:50 blend. Octane measurements for the 25:75
and 75:25 blends were predicted almost exactly by the curve which is described by the following
equation:
MON = 70.1X1 + 84.4X2 + 10.4X1X2
Interaction octane blending equations describe the octane blending behavior of gasoline components
quite accurately as evidenced by the small residual standard errors obtained in blending studies for 15
different refineries. In these studies the standard error for the research octane number ranged from 0.17
to 0.45 and for the motor octane it varied from 0.14 to 0.49.
The principal advantages of the interaction approach over previous gasoline blending methods are
summarized below:
The interaction approach provides a complete description of blending behavior over the entire
composition range.

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Accuracy of the interaction model approaches experimental error quite closely for octane number,
RVP, ASTM distillation, and V/L ratio.
The model can be expanded easily to include new gasoline components.
The equations can be made self-consistent so that the octane number calculated for a blend
containing light and heavy cat cracked gasoline will be identical to the octane number calculated
for the same blend containing the equivalent amount of full-boiling cat cracked gasoline.
Generalization of octane blending behavior is facilitated by separating the total nonlinearity into
many small parts - the interactions between all the pairs of the major component types.
Range
Research Octane is normally higher than Motor Octane. Octanes are higher for leaded naphthas. Leaded
Octane is not of interest where lead is not being added to gasoline. Octane is only of interest for gasoline
blending materials (roughly C4 through 405 degrees F).
Typical Values
Straight chained paraffins have low octane numbers and branched paraffins have high octanes. nHeptane has an octane number of zero while iso-octane has an octane number of 100. Aromatics can
have very high octanes (over 100). For example, toluene has an octane of 105.3.
Test Methods
ASTM D 908

Research Octane Gasoline engines

ASTM D 357

Motor Octane Gasoline Engines

ASTM D 2700

Motor Octane for Aviation fuels

ASTM D 909

Motor Octane Super Charge Method


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FLASH POINT
Description
The Flash Point of a petroleum fraction is that temperature at which its vapors, existing above the
surface of the liquid, will ignite by an open flame but not sustain continued combustion. The flash point of
a fuel, therefore, indicates the maximum temperature at which the oil can be stored and handled without
it being a serious fire hazard.
The test may be conducted using either an open cup or a closed cup method. Closed cup (ASTM D56)
is normally used for light materials, Pensky-Martens (ASTM D93) for middle distillates and Cleveland
open cup (ASTM D92) for the heaviest materials. The closed cup method will give lower temperatures
than the open cup method. The flash point of a material is close to the flash point of the lowest flash
material present in an appreciable amount and therefore is related to the initial boiling point of the
material. Flash point is related to safety (likely explosion) or ease of igniting the material in use.
Fire Point is also related and is the temperature at which oil in an open container gives off vapors at a
rate to continue burning after a flame is applied.
Product specifications involving flash or fire point based on user requirements and climatic conditions in
consumption areas are often set by regulatory agencies. For example, the Canadian Railroads require a
minimum of only 125 F flash point; but most consumers around the world require 150 F minimum. Either
specification is easily met and exceeded by most refiners. Most jet fuel consumers (JP-1 and JP-1A)
require the old kerosene specification of 110 F since this level has been accepted by regulatory
agencies. But most refiners make much higher, usually about 125 F because it is economical to do so.
This is because the fraction which makes the lower flash is more valuable in gasoline. This situation
may change as new environmental regulation in the USA force lower endpoint gasoline blends. US
military requirements for JP-5 is 140 F minimum. JP-5 usually meets arctic diesel specifications.
Range
Of interest especially on whole crude, naphthas, kerosene, mid distillates and fuel oils. Generally of
interest for distillates up to about 650 degrees F.
Typical Values
The flash and fire points of most whole crude oils and naphthas are at room temperature or below. The
flash point of distillates (but not whole crude oils) can be estimated from the ASTM 10% temperature by
procedure 2B7.1 of the API Technical Data Book. The associated chart gives the following:
ASTM 10% temperature degrees F 200
Flash, Closed cup degrees F
15

250
58

300
98

350 400
132 163

450
195

500
220

Petroleum ether (boiling range 95-140)= -60 flash; Hexane (boiling point 155)= <0; Heptane (205)= 23;
mineral spirits (360-400)= 140; kerosene (350-515)= 140.
Test Methods
ASTM D 56

Standard Test Method for Flash Point by Tag Closed Tester.

ASTM D92

Standard Test Method for Flash Point by Pensky-Martens Closed Tester.

ASTM D 93

Standard Test Method for Flash Point by Cleveland Open Tester.

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REID VAPOR PRESSURE


Description
Reid Vapor Pressure (RVP) is used to characterize the volatility of gasoline and crude oils. It is also a
convenient approximation of the absolute vapor pressure. RVP is the pressure of a 4/1 ratio of vapor to
liquid heated to 100 degrees F. True vapor pressure is generally 5% to 9% higher the RVP. The vapor
pressure of a material is an important consideration for transport safety, storage tank requirements,
probability of losses, gasoline vapor lock and the starting characteristics of the fuel. It is also now a
mandatory gasoline specification that is being lowered by air pollution authorities in some countries. In
the USA RVP of gasoline is now 9 psi in the summer and the limit will decrease.
Range
Of interest for naphthas (to 450 deg F, 230 deg C) and for whole crude.
Typical Values
.Lower boiling materials have higher values.
C3
190 psi
(1310 kpa)
nC4
52 psi
( 359 kpa)
nC8
0.74 psi
( 5.1 kpa)
Test Methods
ASTM D 323

Standard Test Method for Vapor Pressure of Petroleum Products.

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SMOKE POINT
Description
The combustion characteristics of turbine fuels and kerosenes are directly related to the hydrocarbon
composition of fuels. For example, aromatics tend to burn with a smoky flame and release a greater
portion of their chemical energy as undesirable thermal radiation than other hydrocarbon types.
Smoke Point is the maximum flame height, expressed in millimeters, at which a fuel can be burned in a
standard wick-fed lamp without smoking. A high smoke point indicates a fuel of low smoke-producing
tendency.
The Smoke Point for the same boiling range distillate is greatest with straight chain paraffins, lower with
branched paraffins, considerably lower with naphthenes and much lower still with aromatics.
Naphthalenes or bicyclic aromatics produce more soot, smoke, and thermal radiation than monocyclic
aromatics.
Range
Of interest for all burning oils such as kerosene and jet fuels. Jet fuel usually requires a smoke point of
at least 20 mm.
Typical Values
Mixtures of Toluene (an aromatic) and iso-octane (a branched paraffin) have smoke points as follows:
Vol. % Paraffin
Smoke Point, mm
Test Methods
ASTM D 1322

60%
14.7

75%
20.2

85%
25.8

90%
30.2

95%
35.4

100%
42.8

Test for Smoke Point of Aviation Turbine fuels.

LUMINOMETER NUMBER
Description
The Luminometer number measures the flame -radiation characteristics of a fuel. The test was
developed because combustion chamber life is shortened in certain jet engines if a fuel produces
luminous flames that result in high-liner temperatures. A low Luminometer number indicates that a large
portion of the chemical energy of the fuel is released as thermal radiation and therefore, a higher
number indicates a fuel of good combustion quality.
Range Kerosene and jet fuel fractions.
Typical Values
As given in ASTM 1322, the smoke point in mm (SP) can be estimated from luminometer numbers (LN) ,
or vice versa, by the following equations:
SP = 4.16 + .331 * LN + .000648 * LN ** 2
LN = -12.03 + 3.009 * SP - .0104 * SP ** 2
LN between 10 and 80 gives SP between 7.5 and 35 respectively.
Test Methods
ASTM D 1740

Test for Luminometer Number of Aviation Turbine fuels.

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ANILINE POINT
Description
Aniline point is the lowest temperature at which a petroleum fraction is completely miscible with an
equal volume of aniline. Mixed aniline point is a mixture of one volume sample, one volume n-heptane
and two volumes aniline. The mixed aniline point test is used for lighter materials where the aniline point
is below the temperature where aniline crystallizes out of the mixture. Aniline point is inversely related to
the amount of aromatics in the material. Paraffins have the highest aniline point, cycloparaffins and
olefin in the middle and aromatics the lowest. Aniline Point also increases with molecular weight. Diesel
index can be calculated and heating value estimated from a combination of the aniline point and gravity.
Aniline point is used to characterize the quality or chemical nature of naphthas and some heavier
distillates. It is often used to help predict the behavior of a feed in a cracker (fluid or hydro) and the
quality of the streams produced by the cat cracker. Feeds with higher aniline numbers (less aromatic
and therefore less refractory) are generally considered more desirable.
Range
May be desirable over the entire range of distillates
Typical Values
Hexane
Heptane
Benzene
Low Aromatics Naphtha (145-175 F boiling range)
Low Aromatics Naphtha (200-220 F boiling range)
30 % Aromatics Naphtha (320-380 F boiling range)`
High Aromatics Naphtha (360-540 F boiling range)
Low Aromatics Kerosene (350-575 F boiling range)
Low Aromatics Kerosene (400-480 F boiling range
.
Test Methods
ASTM D 611

146
127
57* ( * by the mixed aniline test)
134
120
105
76*
160
190

Test Methods for Aniline Point and Mixed Aniline Point of Petroleum
Products and Hydrocarbon Solvents

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REFRACTIVE INDEX
Description
The Refractive Index is the ratio of the velocity of light in air to its velocity in the material. It can be
used, together with density and viscosity, to calculate the paraffin to naphthene ratio in white oils. It also
is a measure of aromaticity and unsaturation and some refiners use it as a means of process control.
Typical Values
Refractive index can be estimated for petroleum fractions from their mean average boiling point and
specific gravity by the method given in procedure 2B5.1 of the API Technical Data Book. Care must be
taken that Refractive Index results are at consistent temperatures.
.
Test Methods
ASTM D 1747

Test for Refractive Index of Viscous Materials.

ASTM D 1218

Test for Refractive and Dispersion of Hydrocarbon Liquids.

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COLD PROPERTIES
The congealing properties of an oil are related to its hydrocarbon composition. In general, symmetrical
molecules, e.g., normal paraffins, have high congealing temperatures whereas the presence of side
chains, i.e., branching discourages crystallization. Since petroleum oils contain components with a wide
range of molecular sizes and configurations, they do not have sharply defined freezing points. They
become semi-plastic when cooled to sufficiently low temperatures.
Under low-temperature conditions, the paraffinic constituents of a fuel tend to precipitate as wax. The
temperature at which the precipitation occurs depends upon the origin, type, and boiling range of the
fuel. The more paraffinic the fuel, the higher the precipitation temperature and the less suitable for low
temperature operation. Therefore, the freeze, pour and cloud are a relative measure of wax in an oil.

POUR POINT
Description
The pour point is the temperature below which the liquid no longer pours freely (i.e., no noticeable flow
when the sample is held horizontal for a period of five seconds).
After preliminary heating, the sample is cooled at a specified rate and examined at 3 deg C intervals for
flow characteristics. The lowest temperature at which movement of the oil is observed is recorded as the
pour point.
For material from waxy crudes, pour point is primarily a function of wax crystallizing out of solution and
forming a matrix of wax crystals which trap the lower freeze point oils, making it difficult for the entire
mass to flow. Some heavier and higher viscosity materials will exhibit a pour point which is primarily a
function of the viscosity rather than actual freezing out of components. As temperature is lowered, the
material becomes more viscous and harder to pour. Pour point can vary with the previous thermal
history of the oil--particularly when wax crystallization is a major factor and especially for wide boiling
cuts such as whole crude oil.
Range
Values are of interest for crude oils, residues and distillates with boiling ranges starting as low as 300+
degrees F.
Typical Values
For a given sample, Pour Point is below Freeze Point and below Cloud Point. Pour Point may be a
negative 100 degrees F or so for light distillates and occasionally as much as positive 200 degrees F for
heavy Residues. The pour point/boiling point relationship curve is exponential upward in shape when the
viscosity effect predominates or a straight line or slightly downward curvature when the wax effect
predominates.
Pour point can be estimated from viscosity at 100 F, specific gravity and molecular weight (which also
can be estimated) by the method of Chapter 2 of the API Technical Data Book.
Test Methods
ASTM D 97

Test Method for Pour Point of Petroleum Oils

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CLOUD POINT
Description
Petroleum oils begin to form wax crystals and become cloudy in appearance as they are cooled toward
their pour points. The Cloud Point temperature is that which a clear liquid becomes cloudy as it is cooled.
It is caused by waxes starting to crystallize out of solution. The temperature differential between cloud
and pour depends on the nature of the petroleum components with Cloud Point typically 4 to 5 deg C
above Pour Point In highly Paraffinic and Waxy crude oils Cloud can go below the Pour Point
temperature.
When the temperature of the oil is decreased below the Cloud Point the formation of Wax crystals is
accelerated. These crystals can clog fuel system lines and filters which can cause aircraft and diesel
engines to stall which makes Cloud Point a very important measurement particularly in cold climates.
The Cold Test is the temperature at which an oil becomes solid and is generally considered to be 5 deg
F lower than Pour Point.
Range Primarily of interest for distillates 200-720 degrees F.
Typical Values
For a given sample, Cloud Point is almost always below Freeze Point and usually 4 to 5 (occasionally up
to 8) degrees C above Pour Point.
Test Methods
ASTM D 2500

Test Method for Cloud Point of Petroleum Oils

FREEZE POINT
Description
The Freezing Point of a pure compound is the temperature at which the compound will freeze (i.e.,
becomes a solid). The Freezing Point of a mixture is the temperature at which crystals formed by
cooling disappear as the temperature rises.
The Freeze Point test is particularly important property for aviation and jet fuel since it must be low
enough to ensure adequate flow of fuel to the engine during long flights at high altitudes. Maximum
Freezing point values are specified for all aviation and jet fuels as an indication of the lowest
temperature at which the fuel can be used without risk of separation of solidified hydrocarbons (wax).
Range Primarily of interest for lighter distillates such as jet fuels (200-720 degrees F).
Typical Values
For a given sample, the Freeze Point will be above the pour point for a mixture. The Freeze Point is
almost always above the Cloud Point.
Test Methods
ASTM D 2386

Test Method for Freeze Point of Petroleum Oils.

COLD FILTER PLUG POINT


Description
The CFPP is the temperature at which a standard filter would become blocked by wax crystals. The
CFPP temperature is lower than Cloud Point but usually above Pour Point. CFPP can be reduced by the
addition of additives which stop the growth of wax crystals that plug the filters.

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CETANE NUMBER
Description
In most diesel engines, the ignition delay period is shorter than the duration of injection. The total
combustion period can be divided into four stages;
a. ignition delay
b. rapid pressure rise
c. constant pressure or controlled pressure rise
d. burning on the expansion stroke
Because the rapid pressure rise represents uncontrolled and inefficient combustion, it is desirable to limit
ignition delay to a minimum. This can be achieved mechanically by selection of a spray pattern
configuration properly tailored to the combustion chamber. Ignition delay also can be reduced by the use
of high - fuel injection pressures and high - fuel/air turbulence to promote rapid fuel jet breakup and
thorough fuel distribution.
The nature of the fuel is also an important factor in reducing the ignition delay. Viscosity, gravity, and
mid boiling point are influential. Composition is also important since straight chain paraffins ignite readily
under compression, but branched chain and aromatics react poorly. It is therefore desirable to have a
numerical basis for evaluating the fuel ignition delay and measuring or predicting this property.
Cetane Number is determined in a diesel test engine much like octane numbers are determined for
gasolines. It is the numerical result of an engine test designed to evaluate fuel ignition delay. This is a
measure of the anti-knock ignition quality of Diesel fuels. To establish the Cetane number scale, two
reference fuels were selected. One, normal Cetane C16H34 which has excellent ignition qualities and
consequently, a very short ignition delay. The second fuel, alphamethylnaphthalene, has poor ignition
qualities and was assigned a cetane number of zero. In 1962, alphamethylnaphthalene was replaced as
a primary reference fuel by heptamethylnonane which has a cetane number of 15 as determined by use
of the two original primary reference fuels.
The cetane number of a diesel fuel is defined as the whole number nearest to the value determined by
calculation from the percentage by volume of normal cetane (Cetane No.=100) in a blend with
heptamethylnonane (Cetane No.=15) which matches the ignition quality of the test fuel when compared
by this method. The matching blend percentages to the first decimal are inserted in the following
equation to obtain the cetane number.
Cetane No. = (percent n-cetane) + 0.15 * (percent heptamethylnonane)
Low to medium cetane number fuels offer better fuel economy but fuels with higher cetane numbers
provide easier starting, lower temperature starting and smoother operation. Lower cetane numbered
fuels are poor burning in a diesel engine and may cause engine deposits and smoke.
Range Diesel fuels with boiling temperatures ranging from 300 to 715 degrees F.
Typical Values
Kerosene
Premium Diesel
Railroad Diesel
Marine Distillate Diesel
Test Methods
ASTM D 613

50
47
40
38

High speed city buses


High speed buses, trucks, tractors, light marine engines
Medium speed buses, railroad, marine & stationary engines
Low speed buses, heavy marine and large stationary engines

Test for Ignition Quality of Diesel Fuels by the Cetane Method.

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CETANE INDEX
Description
Since the determination of cetane number by engine testing requires special equipment and can be time
consuming as well as costly, alternate methods have been developed for calculating estimates of cetane
number.
Cetane Index is calculated from API Gravity (G) and mid-boiling Point in degrees F (M) by ASTM D976
which gives the formula:
Cetane Index = -420.34 + .016 G**2 + 0.192 G Log M + 65.01 (Log M)**2 - .0001809 M**2
An equation in metric units and a nomograph are also presented. They point out that calculated Cetane
Index is a useful tool for estimating Cetane Number if laboratory data is not available but may not always
be a valid substitute.
The calculated Cetane Index is applicable to straight-run fuels, catalytically cracked stocks and blends of
the two. It is not applicable for fuels containing cetane-improving additives nor pure hydrocarbons,
synthetic fuels, alkylates, or coal-tar products. The correlation can also be quite inaccurate when used for
crude oil, residuals and products having a volatility below 500 deg F end point.
Range
Same as Cetane Number
Typical Values
The Cetane Index is usually within 2 numbers of the measured cetane number.

DIESEL INDEX
Description
Another scale used to predict the ignition quality of diesel fuels, the Diesel Index, was actually developed
prior to the adoption of the cetane number scale. The Diesel index is defined as the API gravity times the
aniline point in degrees F divided by 100.
DI = (API * AP) / 100
Diesel Index and Cetane Number correlate but Diesel Index tends to be the higher above 38 and lower
below 38.
Range
Same as Cetane Number
Typical Values
Cetane Number
Diesel Index

30
26

35
34

40
42

45
49

50
56

55
64

60
72

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VISCOSITY
Description
The viscosity of an oil is a measure of its resistance to flow, that is, its readiness to flow when acted upon
by an external force. The coefficient of absolute viscosity or, simply, the absolute viscosity of a fluid is a
measure of its resistance to internal deformation or shear. Molasses, for example, is a highly viscous
fluid whereas water is comparatively less viscous. On the other hand, the viscosity of gases is quite
small compared to that of water. As noted below, the viscosity is an important property of crude oils and
most petroleum products.
The absolute viscosity may be defined as the shear stress at a point divided by the velocity gradient at
the point. Stated in another way, the viscosity is in force in dynes required to move a plane of 1 square
centimeter in area, at a distance one centimeter from another plane of 1 square centimeter in area,
through a distance of 1 centimeter in 1 second. In the centimeter-gram-second (cgs) system, the unit of
absolute viscosity is called a poise and is equal to 1 g/(cm)(sec) or 100 centipoises. The English units
commonly employed are slugs per foot second or pound force seconds per square foot.
The kinematic viscosity is the ratio of the absolute viscosity to the mass density, both at the same
temperature and pressure. In the metric system, the unit of kinematic viscosity corresponding to the
poise is the stoke, which is equal to 1 square centimeter per second, or 100 centistokes. The conversion
from absolute viscosity to kinematic viscosity is given by the following equation:

____

where

= kinematic viscosity, stokes


= absolute viscosity, poises
= density (in vacuo), grams per cubic centimeter

There are a number of methods of measuring Viscosity. These include Kinematic (ASTM D 445),
Saybolt Universal (SSU), Saybolt Furol (SSF), Redwood 1 and 2, and Engler. Kinematic is reported in
centistokes. It is generally the current preferred method for crude assays. Saybolt Universal and
Saybolt Furol are reported in seconds--the time to flow out of a specific size container with a specific size
orifice. The Furol size orifice is larger than the Universal size orifice and therefore SSF is more suitable
for higher viscosity material (the heavier cuts) and the lower temperatures. Redwood is reported in
seconds, Engler in degrees. The Redwood and the Engler instruments are not considered as accurate.
Kinematic viscosity is usually preferred today but test results are often converted to Saybolt units for
reporting by use of the standard ASTM charts. The Kinematic test measures the time for the liquid to
flow under gravity through a glass viscometer. Because some residues deposit wax from solution around
100 degrees F there are some who prefer to measure viscosity at 180 degrees F. It is important that the
temperature chosen for viscosity measurement be sufficiently warmer than the pour point to insure that
the liquid is Newtonian. Redwood no. 1 is normally at 140 degrees F.
A log-log function of kinematic viscosity vs. the log of absolute temperature plot (or the equivalent
formula as contained in ASTM Standard D341-87) can be used to convert available viscosity data from
the temperature measured to the temperature required in the crude assay library.

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Crude Oils
Viscosity measurements on crude oils are used principally in the design of field gathering systems and
the lines and pumps between refinery storage and the processing facility. In these systems viscosity and
pour point measurements provide the data for solving transportation problems associated with crude oils.
Aviation Fuels
The viscosity of aviation fuels is limited to ensure that adequate fuel flow and pressure are maintained
under all operating conditions and that fuel injection nozzles and system controls will operate down to
design temperature conditions. Viscosity can also affect significantly the lubricating properties of the fuel
which has an influence on the pump service life.
Diesel Fuels
The viscosity of diesel fuels is important primarily because of its effect on the handling of the fuel by the
pump and injector system. Diesel fuel viscosity exerts a strong influence on the shape of the fuel spray
and, when the viscosity is either below or above that required for good engine operation, the fuel is not
properly distributed. This results in poor combustion, accompanied by loss of power and economy, and
can contribute to excessive engine wear.
Heating Oils
Viscosity is one of the more important heating oil characteristics. It is indicative of the rate at which the
oil will flow in the fuel systems and the ease with which it can be atomized in a given type of burner.
Since the viscosities of heavier residual fuel oils are high, this property tends to be particularly relevant
to its handling and utilization characteristics.
Lube Oils
To meet a particular application, viscosity is generally the most important controlling property for
manufacture and selection of lubricating oils. The viscosity of a new oil is of fundamental importance
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with respect to performance in a specific type of equipment or machine element and is always described
or specified by the buyer, the seller, or both.
Range
Viscosity data is generally of most interest for the middle and heavy distillates (say 400+ degrees F) and
residua. Viscosity increases exponentially as the mid temperature of the cut increases.
Typical Values
The kinematic viscosity of whole crudes are often in the range of 2 to 6 centistokes at 104 degrees F. A
few crudes have lower values. A significant number of crudes have values 6 to 10, others 10 to 100, still
others in the hundreds and a few heavy crudes have viscosities in the thousands.
Test Methods
To measure the absolute viscosity of fluids, especially gases and vapors, requires elaborate equipment
and considerable experimental skill. On the other hand, a rather simple instrument can be used for
measuring the kinematic viscosity of oils and other viscous liquids. The viscosity of oils is usually
measured by recording the time required for a given volume of fluid at a constant temperature to flow
through a small orifice of standard dimensions. The two standard test methods in the USA are:
D 445

ASTM Standard Test Method for Kinematic Viscosity of Transparent and


Opaque Liquids (and the Calculation of Dynamic Viscosity)

D 2170

ASTM Standard Test Method for Kinematic Viscosity of Asphalts


(Bitumens)

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The older, empirical procedures such as the Saybolt Universal and Saybolt Furol systems, and the
Saybolt thermoviscometer is being superseded by the kinematic system in the United States. Other
viscometers somewhat similar to the Saybolt, but not used to any extent in the U.S., are the Engler, the
Redwood Admiralty, and the Redwood.

VISCOSITY INDEX
The viscosity of petroleum base oils decreases with a rise in temperature, but this rate of change
depends on the composition of the oil. The viscosity index is an empirical number which indicates the
effect of change of temperature on the viscosity of an oil. It compares the rate of change of viscosity of
the sample with the rates of change of two types of oil having the highest and lowest viscosity indices at
the time (1929) when the viscosity index scale was first introduced. A standard paraffinic oil was given a
viscosity index (VI) of 100 and a standard naphthenic oil a VI of 0. Equations were evolved connecting
the viscosity and temperature for these two types of oil and, from these equations, tables were prepared
showing the relationship between viscosities at 100 F (37.8 C) and 210 F (98.9 C) for oils with a VI
between 0 and 100. With these tables and the viscosities at 100 F and 210 F of an oil, the viscosity
index can be calculated. A high viscosity index denotes a low rate of change of viscosity with
temperature.
VI is of particular interest to the lubricating oil manufactures, the automotive industry and to some of the
more sophisticated and informed consumers. The VI scale was developed to compare relative
performance of different lube oils, particularly in automotive engines which encounter many cold starts
and high operating temperatures after starting, as opposed to stationary engines where lube oil
temperatures can be maintained relatively constant.
The VI scale was an arbitrary development where 100 was assigned to a lube oil which showed relatively
little change in viscosity with temperature. This was a highly paraffinic lube oil made from a highly
paraffinic Pennsylvania crude oil. Zero VI was assigned to a low cold-test lube oil that showed a large
change in viscosity with temperature. This was a naphthenic lube oil made from a highly naphthenic
crude oil produced in the US Gulf Coast. Today some lube oils have been developed which exceed 100
VI. These are the so-called multi-grade oils which are actually blends of lighter grades of lube distillate
base stocks plus additives which make the oils perform at higher temperatures like a heavier grade.

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NEUTRALIZATION & TOTAL ACID NUMBER


Description
Neutralization number is the milligrams of potassium hydroxide required to neutralize the total acidity.
The acidity is primarily from carboxylic acids which are predominantly in naphthenic crude oils and are
sometimes called naphthenic acids. Naphthenic type acids corrode carbon steel badly and especially at
the flash zone temperature of 700F encountered in crude distillation. Crude oils with substantial
naphthenic acids may require use of austenitic 318 or 347 stainless steel in the flash zone.
Total Acid number (TAN) is the quantity of base (KOH) to neutralize the acid within a sample. Total
Base number is the quantity of acid required to neutralize any bases within a sample. The Neutralization
number includes both the Acid Number and the Base number. This was carried out according to ASTM D
664
which involved two titrations, one with acid and one with a base using Potentiometric Titrations.
ASTM D 664 was renamed from Neutralization number to Total Acid Number where only the total acid
number is measured and ASTM Test Method D 4739 was developed as an alternative to the base
number portion of Test Method d 664. Base numbers obtained by this method may or may not be
numerically the same as those obtained by the base number portion of D 664.
Range
Used especially on whole crude and on cuts used to make transportation fuels because there are
specifications on the products. The data is useful for the full range of distillate and residua.
Typical Values
A crude is considered highly Acidic with a TAN of around 3 mg. Between levels of 0.5 and 3 mg crudes
are considered Acidic. Below 0.5 mg crudes are considered normal and with levels below 0.05 mg they
are considered to have very low acidity.
Test Methods
ASTM D 664

Standard Test for Acid Number of Petroleum Products (Potentiometric Titration).

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WAX
Description
This is the amount of wax (wt%) in the petroleum fraction. The wax content affects the pour, cloud and
freeze points and viscosity (if not Newtonian) of the material. A petroleum fraction's wax value is a
function of the solvent used to extract it and the temperature at which the wax content is measured. A
determination or test conducted at a relatively low temperature will yield a much greater wax content
than one conducted at a higher temperature.
Lighter fuel products should exhibit a clear and bright appearance at the lowest ambient temperature that
the fuel may be expected to encounter. In diesel it is important to prevent fuel-filter plugging with wax.
In many cold climates kerosene is added to diesel by oil marketers and/or consumers in order to keep
wax in solution and thereby minimize possible problems. Likewise, wax is not desirable in lubricating oils;
therefore, product specifications are established to prevent any possible problems. Specifications are
usually established to provide for maximum product pour points rather than wax content per se.
Range
For light distillates, cloud point may be the preferred inspection. For home heating oil and automotive
diesel fuel, wax should normally be below 15%. Wax content is of interest generally for vacuum distillate
cuts.
Typical Values
In distillates, the wax content for most crudes tends not to exceed a few percent (sometimes essentially
zero) for cuts below 550 F. For cuts above 550 F, many crudes have percent wax exceeding 10%, quite
a few exceed 20% and some exceed 40%. For a majority of crudes looked at, the highest concentration
of wax occurred in cuts around 650 F with cuts higher than that still at wax percent levels nearly as high
as the peak. This tended to be true up into the heavy distillate range.
In resids, the wax content varies considerably among crudes and values below 1% and above 50% are
seen with many different crudes in the 5 to 30% range. There is a general tendency in about 3/4ths of
the crudes looked at for wax percent in the resid to be less for higher temperature resids. But the wax
percent for about 1/5th of the crudes were higher at higher resid cut points and some crudes had about
the same wax percent over a range of resid cut temperatures.

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METALS
Description
Traces of many metallic elements can be found in most crude oils although many are contaminants
picked up as emulsified formation with water, particles of soil from the reservoir etc. Vanadium and
Nickel compounds, however, have been identified in Petroleum.
The metals content in crude oils ranges from a few parts per million to over 1,000 ppm, and, in-spite of
their relative low concentrations , the organo-metallic are of considerable importance. Small quantities of
such metals as arsenic, iron, nickel, vanadium and copper can have a deleterious effect on refinery
processing catalysts, such as reforming and catalytic cracking catalysts. Vanadium in gas turbines fuels
can also form low melting compounds which cause severe corrosive attack on the high temperature
alloys for the turbine blades. Sodium can cause problems in furnace brickwork.
Vanadium and Nickel occur principally as vanadyl and nickel complexes which are stable and distill at
temperatures above 500 deg C (930 deg F). Since most of the organo-metallic compounds are found in
the higher-boiling fractions, distillation concentrates these metallic constituents of the crude in residue.
Vacuum gas oils up to 1000 deg F TBP cut point contain less than one part per million of volatile nickel
and vanadium. Any higher values than this are caused by entrained residium.
For calculation purposes it can be assumed that all of the vanadium, nickel, iron and copper are in the
600+ deg F residue. Whenever possible, the metal contents of catalytic cracking feed stocks should be
determined experimentally due to the possibility metallic compounds either volatilized or entrained
during crude distillation and appear in the higher-boiling distillates.
Range
For calculation purposes it can be assumed that all of the vanadium, nickel, iron and copper are in the
600+ deg F residue. When ever possible, the metal contents of catalytic cracking feed stocks should be
determined experimentally due to the possibility metallic compounds either volatilized or entrained
during crude distillation and appear in the higher-boiling distillates.
Typical Values
From a few parts per million to over 1000 ppm are possible.
Test Methods
ASTM D 5863

Determination of Nickel, Vanadium, Iron and Sodium in Crude Oils and


Residual Fuels by Flame Atomic Absorption Spectrometry.

ASTM D 5708

Determination of Nickel, Vanadium and Iron in Crude Oils and Residual


Fuels by Inductively coupled Plasma Atomic Emission Spectrometry.

ASTM D 2788

Test for Trace Metals in Gas Turbine Fuels.

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CARBON RESIDUE
Description
The Carbon Residue tests give the weight percent of the residue left after vaporization and pyrolysis of a
petroleum fraction. The test is done by heating the sample in a crucible or other container to drive off all
the volatiles. Some of the residue will crack giving off more volatile material and if oxygen is present
carbon will be oxidized to gas. The residue may not be all carbon as it would include non-volatile ash
and metals in the sample.
The Conradson and Ramsbottom carbon test procedures limit, by the design of the test equipment, the
presence of air which would oxidize the carbon. The MCRT test method is done in a nitrogen
atmosphere to exclude the presence of air.
All of the tests serve as an approximation of the carbon or coke yield from cracking. A reasonable
amount of carbon is desirable and necessary in a heat-balanced unit such as fluid cat cracking since the
coke on the catalyst is burned in the regenerator thus heating the catalyst which provides the heat input
for the endothermic cracking reactions. The test also is a rough approximation of the tendency of the
fuel to form deposits in vaporizing type burners.

Range
Of interest for heavy distillates and residues.
Typical Values
ASTM provides (D524) a conversion chart between the first two test values which is suitable for some
materials. Some representative values from the curve are:
CONRADSON
RAMSBOTTOM
.
Test Methods
ASTM D 189

20.0 10.0 4.0 2.0 1.00 .40 .20 .10 .040 .020 .010
20.0 8.7 3.1 1.6 .80 .38 .24 .16 .092 .070 .057

Test Methods for Conradson Carbon Residue of Petroleum Products

ASTM D 524

Test Methods for Ramsbottom Carbon Residue of Petroleum Products

ASTM D 4530

Test Methods for Micro Carbon Residue of Petroleum Products

SULFUR IN CARBON RESIDUE


Description
This is the weight percent sulfur in the carbon residue.

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ASPHALTENES & RESINS


Description
The residue of a crude consists of asphaltenes, resins and oil. Asphaltenes are heavy hydrocarbon
molecules that are in colloidal suspension in the oil, stabilized by resins adsorbed on their surface. The
oil can be roughly thought of as the part that might be distilled off without cracking it first or, more
accurately, the part which is not asphaltenes or resins or the part of the residue which is soluble in
propane. The asphaltene content of residual oils is important in determining yields and product qualities
for solvent deasphalters, thermal visbreakers and hydrodesulfurization units.
Asphaltenes are very complex polyaromatics--with a molecular weight between 3000 and 10,000
(typically 7000). They have high carbon to hydrogen ratios and are sometimes spoken of as "chicken
wire or coal like" structures. The molecular structure is one of 3 to 11 unit sheets. Unit sheets are held
together by either covalent bonding or by strong associative forces. Each sheet may have 7 to 16
condensed aromatic rings, 2 to 6 naphthene rings, several sulfur atoms, a nitrogen atom and perhaps
other atoms such as oxygen, nickel or vanadium. Some paraffinic side chains may be present. Polar
groups are attached. Asphaltenes exist in crude oils and residuals therefrom as dark brown to black
colloidal suspensions. They can be precipitated from the oil by adding a light hydrocarbon (propane) in a
ratio of several times the volume of the oil. The amount of Asphaltenes is defined as that part of the
precipitate which is insoluble in hot normal heptane.
Resins is that part of the propane precipitate which dissolves in normal heptane. The structure is broadly
similar to that of the asphaltenes but the molecules are less complex and less aromatic and may contain
more oxygen and less sulfur and less nitrogen than asphaltenes. They typically consist of only one unit
sheet so have lower molecular weights. When precipitated by propane their appearance may vary from
a dark yellow, viscous liquid to an amorphous, dark-colored solid.
Resins can be of type A or type B. The amounts of these are determined by thin layer chromatography
on the residue using three solvents. N-heptane first elutes the saturates, then toluene elutes the
aromatics and finally a chloroform/methanol or toluene/ethanol mixture separates resins A from resins
B. Resins A contain lower molecular weight polar compounds. Resins B are higher molecular weight
and more like asphaltenes.
The asphaltene content of a resid is a measure of the quality of asphalt that might be expected from that
crude oil. High asphaltene content is not desirable for cat cracking feed stocks. Asphaltenes and resins
can be separated from the heavier oils by adding a light solvent which causes them to precipitate. This
process is used on vacuum residua to separate the lube oil bright stocks from asphaltenes and resins. It
can be used to improve the quality of cat cracker feedstock. Propane is the solvent normally used in the
process; and, dewaxing can also be accomplished with the same solvent.
Range A property of residues--particularly of interest regarding asphalt production or use of residue (or
processing for use) in cat cracking or lube manufacture.
Typical Values
Since asphaltenes and resins are in the "bottom of the barrel", the percent in the residue will increase as
the resid is cut deeper. Asphaltenes for residues cut not over 1000 F run from under 1 wt% in some
residues, to 15% or over in a modest number of residues and to over 30% in a very few residues.
Generally to make asphalt, one looks for a crude oil with a substantial yield of residue with low wax, high
asphaltene percent and low penetration for deep cut resids.
Test Methods
ASTM D 3279

Standard Test Method for n-Heptane Insolubles

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n-PENTANE INSOLUBLES
Description
This is the amount of insolubles after a residue is extracted with n-pentane. We observe crudes where
this amount is three or more times greater than the amount of insolubles from n-heptane (asphaltenes)
and others where the amount is less.

PENETRATION
Description
This indicates the softness of heavy petroleum materials such as asphalt. The penetration test measures
the distance a needle of specified size penetrates into the material under a load of 100 grams for 5
seconds at 77 oF typically.
Range Resid Materials being used to make asphalt.
Typical Values
1050 F + resids from different crudes can have penetration values over a wide range such as between
13 (or lower) and >300. A wide range of grades may be requested by the market in the 40 to 250
penetration range. A refinery might make two runs--one of 40 and one of 250 penetration and then
individual orders blended directly in the tankcar or truck to fill specific orders.
Test Methods
ASTM D 5, 1321

Standard Test Method for Penetration of Bituminous Materials

SOFTENING POINT
Description
This measures the temperature at which an asphalt or resid will soften. The softening point is the
temperature at which a 3.5 gram ball of specified size will fall 25 mm through a sample placed in a ring
of specified size.
Range Resid materials particularly residues to be used for asphalt.
Typical Values
Commercial grades of asphalt typically have softening points 80 to 340F. Many resids would have
softening points in the 100-150 degrees F range. Typically, softening point is higher for deeper cut resids
but in a few crudes, the softening point can be cut lower for a deeper cut resid.
Test Methods
ASTM D 36

Standard Test Method for Softening Point Bitumen (Ring-and-Ball Apparatus)

DUCTILITY
Description
This is a test of asphalts and is a measure of the ability to stretch or elongate. The test is an indication of
the ability of the asphalt to flow and thereby mend a rupture in the surface of the material. In the test, a
briquette of asphalt is pulled apart at a uniform rate (5cm per minute) and the elongation that takes place
before rupture is the ductility measured in centimeters. The test is usually conducted at 77F

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