Charact. Test

Refining-Petrochemicals-Chemicals-Engineering
———
PDVSA
Venezuela
MSc IN REFINING, ENGINEERING AND GAS
Module 2: Characterization of petroleum products
CHARACTERIZATION TESTS
OF PETROLEUM CUT AND PRODUCT PROPERTIES
OUTLINES OF THE QUALITY OF PETROLEUM PRODUCTS.......................................................... 1
I - TESTS RELATED TO THE VOLATILITY OF PETROLEUM PRODUCTS ............................... 3
ASTM distillation test ...............................................................................................................................4

Distillation of petroleum products at reduced pressures ..........................................................................6
Simulated distillation by gas chromatography.......................................................................................... 7
Volatility of liquefied petroleum gas (LPG)...............................................................................................8
Vapor pressure of liquefied petroleum gas (LPG)....................................................................................9
Reid vapor pressure...............................................................................................................................10
Flash point tests .....................................................................................................................................12
II - TESTS RELATED TO COMBUSTION OF PETROLEUM PRODUCTS ................................. 16

Octane number of automotive gasoline .................................................................................................17
Cetane number of diesel fuel .................................................................................................................23
Smoke point for aviation turbine fuels.................................................................................................... 27
Standard tests related to fuel combustion .............................................................................................28
III - TESTS RELATED TO STORAGE AND FLOWING OF PETROLEUM PRODUCTS .............. 31

Viscosity measurements of petroleum products .................................................................................... 32
Viscosity index .......................................................................................................................................34
Viscosity index calculation .....................................................................................................................35
S.A.E. viscosity grades of engine lubricating oils ..................................................................................39
Lubricating properties of diesel fuels .....................................................................................................40
Density of petroleum products ...............................................................................................................41
AN ENO - 02756_A_A - Rev. 0 04/06/2007
„ 2007 ENSPM Formation Industrie - IFP Training

II
Density and relative density of liquids by digital densitymeter ............................................................... 43

Tests related to cold conditions .............................................................................................................44
Cloud point and pour point of petroleum products ......................................................................... 46
Filterability limit temperature .......................................................................................................... 47
Freezing point of aviation fuels ...................................................................................................... 49
Propane dryness test (Cobalt bromide method) ............................................................................50
IV - TEST RELATED TO THE CORROSIVENESS OF PETROLEUM PRODUCTS AND TO

POLLUTION ............................................................................................................................ 53
Sulfur content of petroleum products by the Wickbold combustion method .......................................... 56
Sulfur in liquefied petroleum gas (Lamp Method) ..................................................................................57
Sulfur determination in all liquid petroleum products by the X-Ray fluorescence method ..................... 58
Sulfur trace analysis in light distillates by the microcoulometric method ............................................... 59
Neutralization number by color-indicator titration ..................................................................................60
Copper strip corrosion ...........................................................................................................................61
Mercaptan content .................................................................................................................................63
V- TESTS RELATED TO THE CHEMICAL NATURE OF PETROLEUM PRODUCTS AND TO

OXIDIZING CONDITIONS - STABILITY OF PRODUCTS ...................................................... 65
Hydrocarbon types in liquid petroleum products by fluorescent indicator adsorption (FIA) ................... 67
Refractive index for petroleum products ................................................................................................ 68
Aniline point ...........................................................................................................................................69
Water and sediments in petroleum products.......................................................................................... 70
Jet fuel behaviour in the presence of liquid water ..................................................................................72
Asphaltene precipitation with normal heptane .......................................................................................74
Vanadium content in heavy petroleum fractions by atomic absorption .................................................. 76
Vanadium and nickel content by I.C.P................................................................................................... 77
Insoluble content test .................................................................................................................................
Nitrogen determination in liquid petroleum hydrocarbons by oxidative combustion
and chemiluminescence detection .........................................................................................................78
Stability tests for motor gasolines, turbine fuels and distillates .............................................................. 79
Existent gum in fuels by jet evaporation ........................................................................................ 80
Oxidation stability of gasoline (induction period method) .............................................................. 81
Oxidation stability of aviation fuels (potential residue method) ...................................................... 82
Olefin and diolefin content .............................................................................................................83
Thermal oxidation stability of aviation turbine fuels ....................................................................... 85
Oxidation stability of diesel fuels.................................................................................................... 86
Residual fuel oil stability.................................................................................................................87
Stability and compatibility of residual fuels oils by spot test .......................................................... 87
Hot filtration test or insoluble content test...................................................................................... 88
Color - Stability of color - ASTM color scale .......................................................................................... 90
VI - SPECIAL TESTS FOR SOLID OR SEMI-SOLID PETROLEUM PRODUCTS ........................ 91

Needle penetration.................................................................................................................................92
Softening point .......................................................................................................................................93
02756_A_A © 2007 ENSPM Formation Industrie - IFP Training

1
OUTLINES OF THE QUALITY OF PETROLEUM PRODUCTS
The uses of the different petroleum products require each one to have certain properties such as:
– correct burning in an engine in the case of motor fuel

– being easily pumped at low temperatures in the case of jet fuel or diesel fuel
– not being too viscous in the case of heavy fuel
– etc.
Verification of the properties is carried out by means of standard tests that are measuring methods and
which operating procedures are precisely determined by well known organisations such as:
• A.S.T.M. American Society for Testing and Materials

• I.P. Institute of Petroleum
• I.S.O. International Standard Organisation
• AFNOR Association Française de NORmalisation
• CEN Comité Européen de Normalisation
These standard tests correspond either to the measurement of the physico-chemical properties or to the
simulation tests in which the products are put in conditions near to the ones of its use.
Quality requirements for petroleum products come in the form of specifications directly linked to the results
obtained from the standard tests.
For instance, in France, there are several types of requirement:
Customs requirements :
They are designed simply to distinguish between different taxable products and to avoid tax
evasion.
Administrative requirements :
These are determined by the "Direction des Hydrocarbures" (Hydrocarbon Management

Committee) and published in the "Journal Officiel", which draws up the legal tests that are
referred to in court. They tend to steer a course between the quality requirements of the user
and the capabilities of the refiners.
Union requirements :
These are fixed by documents drawn up by the Chamber of the Oil Refiners' Union, in close
collaboration with the aforesaid "Direction des Hydrocarbures" and apply to certain products.
They review, complete and adjust the official specifications to the user's best interest. These
are always stricter than the administrative specifications.
Internal requirements of an oil company :
These are even stricter than the preceding specifications and ensure the satisfaction of the
client of that particular company.

2
The standardized quality-control tests for petroleum products can be classified as follows:
• tests related to volatility

• tests related to combustion
• tests related to flowing, lubrication and storage
• tests related to handling under cold conditions
• tests related to corrosion and pollution
• tests related to chemical nature and stability
• tests related to bitumen
As the standardized tests are carried out in laboratories, the following criteria should be used
to judge the acceptability of results and to determine their accuracy.
Repeatability :
Duplicate results by the same operator in the same laboratory should not be considered
suspect unless they differ by more than repeatability amounts:
for instance: 6°C for a flash point (Pensky-Martens) above 105°C

0.35% for the viscosity of a clean lube oil
but 2% for the viscosity of a heavy fuel oil
Reproducibility :
The average of tests by an operator compared to the average of tests by another operator in
another laboratory should be considered as suspect if they differ by more than reproducibility
amounts:
for instance: 8°C for a flash point (P.M.) above 105°C

0.70% for the viscosity of a clean lube oil
but 7% for the viscosity of a heavy fuel oil

3
I - TESTS RELATED TO THE VOLATILITY

OF PETROLEUM PRODUCTS
• Each petroleum product has a different volatility range according to the conditions in which it is used.
• In order to measure the volatility of a product, standard tests therefore have the following aims:
– to define the overall volatility range of a product, as is the case for ASTM distillation
– to define more particularly the content of light and heavy elements in relation to the range
required, in order to limit the amounts acceptable
Limitation of light components Reid vapor pressure

Flash point
Limitation of heavy components ASTM final point

ASTM residue
...
Boiling point Limitation of

(°C) "heavy"
components
Volatility range
in relation to uses
Limitation of
"light"
D PPC 105 B
components
The following major tests are described hereafter:
– standard test designed to determine the boiling temperatures: ASTM distillation

(ASTM D 86)
– standard tests measuring the vaporization capacity of a product: gasoline Reid vapor
pressure (ASTM D 323), flash points (different methods)

4
ASTM DISTILLATION TEST
— ASTM D 86 —
This standard test is applied to all the main petroleum products except liquefied petroleum gases and
bitumen.
It consists in distilling 100 ml of product in standardized conditions and noting the temperatures corresponding
to the different volumes either evaporated or condensed and collected.
The manual equipment used is shown in the following diagram, but this test is now generally performed with
the use of automatic apparatus.
Thermometer
Flask (125 cm3)
Metal tube
Condenser
Sample and cooling bath
(100 cm3) (water or iced water)
Flask support
100 cm 3
Receiver 80
(gratuated cylinder) 60
40
D ANA 066 B
20
The ASTM distillation curve is drawn by plotting in the graph the temperatures recorded as a function of the
volumes distilled.
Temperature
End boiling point

EBP
rve
tion cu
Md istilla
AST
IBP
Initial boiling point
Losses Residue
D ANA 067 C
10 20 30 40 50 60 70 80 90 100
% distilled volume

5
Two important temperatures are recorded:
– initial boiling point (IBP) , recorded when the first liquid drop is observed
– final boiling point (End Boiling Point: EBP) which is the maximum temperature
observed during the test
The ASTM distillation of a petroleum product corresponds to its vaporisation under atmospheric pressure.
Temperatures obtained during the test are directly related to the normal boiling temperatures of the
components of the product: gasoline which is a mixture of components with normal boiling points between
0°C and 200°C has, for example, an initial boiling point (IBP) of 30°C and a final one (EBP) of 185°C.
This relation shows that any change in the volatility of a product will result in a modification of its ASTM
distillation curve:
– if the product becomes "lighter", the ASTM distillation temperatures decrease
– if the product becomes "heavier", the ASTM distillation temperatures

increase
If the product becomes lighter, then a higher distilled percentage will correspond to a given temperature t
of the ASTM distillation.
The special importance of the end boiling point is to be noted as it indicates the heaviest compounds in the
products and of the residue which characterizes the amount of components difficult to vaporize and likely to
decompose.
To sum up:
• the shape of the ASTM distillation curve indicates the volatility of the petroleum product
components
• when high volatility is required, the results must indicate a minimum distilled
percentage at a given temperature
• heavy components can be limited by fixing the End Point at a maximum temperature. In this
case, R (residue %) can also be limited to a given amount

6
DISTILLATION OF PETROLEUM PRODUCTS AT REDUCED PRESSURES
– ASTM D 1160 –
This standard method is applied to petroleum products which are thermally "cracked" by high temperature
when distilled at atmospheric pressure.
The sample is distilled between 1 and 50 mmHg. Most of the time, the pressure chosen is 1 mmHg (vacuum
regulator).
The vapor temperature, time and the observed pressure of the following volume percentage fractions
collected in the receiver: IBP, 5, 10, 30, 40, 50, 60, 70, 90, 95 and FBP are recorded.
The observed temperatures are converted in the equivalent atmospheric temperatures using tables or
equation.
18 1
19 3
4
17
16
15
5
DANA 006 C
14 13 12 11 10 9 8 7 6
1 - Potentiometer 6 - Surge tank 11 - Thermowell 16 - Relay
2 - Cold trap 7 - Vacuum pump 12 - Circulating pump 17 - Vacuum gage
3 - Vacuum regulator 8 - Anti drip chain 13 - Thermoregulator 18 - I.C. Kovar tipped
4 - Relay 9 - Cooling flow 14 - Immersion heater thermocouple
5 - Solenoid valve 10 - 750 Watt heater 15 - Thermometer 19 - Repressuring connection
Assembly of vacuum distillation apparatus

7
SIMULATED DISTILLATION BY GAS CHROMATOGRAPHY
GC - Simulated distillation is an analytical technique that gives the distillation curve of a petroleum sample
(correlation between % distilled and boiling point) from the chromatogram of the sample. The hydrocarbon
groups present in the sample are separated in a GC column, chiefly in terms of their boiling points. The
detector response (flame ionisation) is proportional to the weight of the hydrocarbon eluded, consequently the
weight distribution of the hydrocarbon groups will be proportional to the cumulative areas on the
chromatogram.
CALIBRATION - RETENTION TIME (RT) - BOILING POINT

The correlation between retention time (RT) and boiling point (BP) is achieved by injection a mixture of n-
paraffins with well defined boiling points. For a good analysis, chromatographic conditions (flow rate, oven
temperature programming, stationary phase) should be selected so that the function BP = f(RT) is linear over
the longest time interval possible.
CHROMATOGRAMS
The chromatograms obtained with methods adapted to each type of petroleum cut or product are used to
calculate the successive selected interval areas to which boiling points are assigned, often with known alcane
standard (e.g. n-C14 - n-C15 - nC16) or by correlations with conventional distillations. This produces the
desired SD curve for the sample: weight % = f(BP).
Internal standard
n-alkanes
C14 C15 C16
66 % at 575°C
Precolumn
purge
Injection
DANA 100 B
Time (min)
10 20 30 40
Chromatogram of petroleum residue with internal standard mixture
Simulated distillation does not involve any revolutionary GC technique. Nevertheless, in the space of a few
years, its use has been greatly developed in oil industry laboratories, facilitated by improved computing
capability for processing analytical data. This has led to considerable time saving and gains in precision,
compared to conventional distillation (ASTM D 86 - ASTM D 1160 - TBP distillation ASTM D 2982).
Simulated distillation applies to practically all petroleum cuts, from gasolines to residue. A great many
tests are available and are continually evoluing (ASTM D 3710, ASTM D 2887, Proposed test method ASTM
(D2) Nov. 1971, etc.).
8
VOLATILITY OF LIQUEFIELD PETROLEUM GAS (LPG)
– ASTM D 1837 –
This test is applied only to LPG and is similar to ASTM distillation.
100 ml of the LPG product are evaporated in a weathering tube. The vaporization is natural since LPG
components have negative boiling temperatures which are lower than the ambient temperature.
Slotted
cork
Armored
thermometer
100
90
80
70
Graduated
60
weathering tube
50
40
30
20
10
8
D ANA 021 B
Charcoal
The test determines the temperature reached when 95% of the product has evaporated that is to say when
5 cm 3 of liquid remain in the tube.
This temperature represents the boiling point of the residual liquid and gives an idea of its composition. The
higher the temperature, the greater the quantity of "heavy" components contained in the residual liquid.
The limitation of "heavy" hydrocarbons present in LPG (in fact, of butane in the propane-type LPG or of
pentane in the commercial butane) involves specifying a maximum temperature when 95 percent has
evaporated.
This limitation aims to:
- allow the user to withdraw all the fuel from the cylinder
- reduce condensation in the piping routing the gas to the burner

9
VAPOR PRESSURE OF LIQUEFIED PETROLEUM GAS (LPG)
– ASTM D 1267 –
This method covers the determination of the gage vapor pressure of LPG at 37.8°C (100°F) or 50°C.
The apparatus used is described in the diagram below.
Manometer The apparatus is completely filled with

the LPG sample to be tested. About
one-third of the volume of the sample is
immediately withdrawn to provide
adequate free space for product
expansion. The apparatus is then
Bleeder valve vigorously shaken and immersed in a
thermostatic bath.
After equilibrium, the LPG vapor

pressure is the pressure reading on the
pressure gage. This reading is called
Main chamber
"gage" because it takes into account
(80%) only the pressure difference above
100 °F atmospheric pressure.
37.8 °C
Straight-throw The result is given in bars or kPa at
37.8°C or 50°C according to the test
valve
temperature in the thermostatic bath.
The vapor pressure of a mixture is

Inlet valve directly linked to its composition and
thus this vapor pressure will be higher if
the mixture contains more volatile
D ANA 200 B
Expansion components.
chamber (20%)
The LPG vapor pressure specification limits the quantity of light components of an LPG product. This
specification is obviously related to the characteristics of the storage tanks (compressive strength).

10
REID VAPOR PRESSURE
— ASTM D 323 —
The Reid Vapor Pressure test is the measurement of the absolute pressure built up by the vapors of a given
petroleum product contained in a standardized bomb atvehicles. This test applies especially to automotive
gasolines.
The apparatus used is shown in the diagram below.
Reading
of RVP Manometer
Needle valve
Air chamber
(volume ≈ 4 V)
100 °F
37.8 °C
Gasoline chamber
(volume V)
D ANA 077 B
Apparatus for measuring Reid Vapor Pressure (RVP)
This test consists in filling the small lower chamber with the product and immersing the apparatus in a
constant temperature bath at 37.8°C. The needle valve is then opened thus enabling the manometer to
measure the pressure of the vapors released by the product. This pressure measured by a mercury
manometer is expressed in millibars.
The value of the Reid vapor pressure (RVP) is directly related to the amount of volatile components contained
in the product which have high vapor pressure.
In the case of automotive gasoline, the RVP is linked essentially to the butane content, which is
the most volatile component in the gasoline.
The RVP also characterizes the vaporization capacity of a fuel.

11
The GRABNER method is also used (ASTM DS191).
This method is a recent technique and has the following advantages:
– it requires only a small amount of product (1 cm3 instead of 150 cm3 for the RVP)
– it gives the temperature required to obtain a vapor pressure of 3.6 bar
This data is interesting for fuel injection engines because 3.6 bar is a realistic value for ramp and injectors.

12
FLASH POINT TESTS
The flash point is the lowest temperature to which a petroleum product must be raised and at which the
application of an ignition source (flame) causes the vapor above the sample to ignite under specified test
conditions.
At a temperature higher than the flash point, the vapors released by the petroleum product thus form a
flammable mixture, when mixed with air. However, this temperature is different from the auto ignition
temperature of a product, which is the temperature at which the product spontaneously ignites in air without
the presence of a flame.
For a given petroleum cut, the lighter (or volatile) components are easily vaporized and form a vapor
phase (air-hydrocarbons) rich in hydrocarbons above the liquid phase. When this vapor phase becomes
richer in light hydrocarbons the flash point temperature decreases. The standard flash point test results are
consequently very sensitive to the presence of volatile materials or contaminants or of too many light
components.
This is an important safety characteristic for the handling and storage of petroleum products, which
must be stored at a temperature lower than their flash point.
Several types of apparatus, to which different standards are applicable, are used to measure a flash point. It
is worth noting that different results may be obtained from the same product with these different types of
apparatus. Consequently one must indicate, along with the value of the measurement, the standard to which
it corresponds.
Tests can be carried out by closed cup or by open cup methods
Flash points by closed cup test
• Methods IP 170 - ABEL apparatus - for flash points between – 18 and 71°C: Jet A1,
kerosene
• IP 34 and ASTM D 93 - PENSKY-MARTENS apparatus - for flash points > 50°C: diesel fuel
• IF 170 - ABEL PENSKY apparatus for flash between + 5 and 50°C for kerosene (union
requirements)
• NF T 60-103 - LUCHAIRE apparatus, for flash points of diesel oils, home-heating and other
fuel oils
• IP 113 and NF M 07-011 - ABEL apparatus for flash points of cutback bitumen
Flash point by open cup test
• Method ASTM D 92 - CLEVELAND apparatus for flash points > 80°C (lube oils and industrial
greases).
Generally speaking the accuracy of results in closed cup tests is better than in open cup tests.

13
1- FLASH POINT "LUCHAIRE" NF T 60-103

This method is applied to petroleum products such as:
- lube oils
- diesel fuel oils
- domestic or home heating fuel oils
- other heavy fuel oils
A simplified diagram of the apparatus is shown hereafter:
Thermometer
Seal
Pilot flame
For this test, the sample is poured into a
Cover
cup with a chimney in the cover. The
Vapor outlet
sample is regularly heated. The flash
point is reached when the application of
Test cup the test flame causes the vapor above
the chimney to ignite.
The simultaneous sample temperature

+ 2 to3 °C read by submerging the thermometer in
per minute the product is called the flash point.
D ANA 068 B
Luchaire Apparatus
2- FLASH POINT BY TAG CLOSED

TESTER (ASTM D 56) 12
12
Cup thermometer 12
Bath thermometer
12
12
12
12
12
Flame size 12
12
12
bead
Applied to all petroleum products with a flash
12 12
12
12
12
Flame tipe 12
12
12 Oil chamber
point < 93°C, except cut-back asphalts.
12
12
12
12
12
12
12
In this method, the test cup is placed in the bath

containing water or a liquid mixture of water and Test cup
ethylene glycol.
The flame tip enables a small flame of specified

size to be applied above the cup at regular
intervals.
Gas burner
D ANA 1083 A

14
3- FLASH POINT BY CLEVELAND OPEN CUP (ASTM D 92)

Thermometer
This test is applied to very heavy

products such as fuel oils, lubricating oils
Pilot flame and bitumen for flash point > 80°C.
every 2°C step
The basic procedure of the test is the
same as that of the former test.
The main differences are:
- the absence of bath
- the open cup

+ 5 to 6 °C
per minute - the faster heating rate
D ANA 069 B The flame tip is applied at intervals

across the cup for a duration of about 1
Cleaveland apparatus (open cup) sec.
(Flash point > 80°C)
4- FLASH POINT BY PENSKY-MARTENS CLOSED TESTER (ASTM D 93)

This test covers the determination of liquids that tend to form a surface film under test conditions (flash points
> 50°C).
It is the most complete and most reliable test. A mechanical stirrer is placed in the sample in the closed cup
in order to prevent the formation of a surface film.
Stirrer drive
flexible shaft Thermometer
Flame exposure Shutter

Shutter and flame
device
exposure device
operating knob
Flame tip
inlet Cover
Closed up + 5 to 6°C
Flame pilot
per minute
inlet
Pilot flame
every 1 or 2°C
Stirrer
Air bath
(3 to 4 mm)
D ANA 070 B

15
5- ABEL APPARATUS (CLOSED CUP TEST): FOR FLASH POINTS BETWEEN – 18 AND
71°C - (IP 170)
Stirrer
Bath Sample
thermometer thermometer
Cover
Pilot flame
Air
bath Slide
Cover and flame exposure device
D ANA 071 B
+1 °C per minute
Pilot flame every 0.5°C
Water bath

16
II - TESTS RELATED TO COMBUSTION

Petroleum fuels are burnt under ridely differing conditions and each type of fuel must have combustion
characteristics appropriate to its use. Most of the commercial petroleum products (around 90% in weight) are
burnt to produce energy:
– mechanical energy in engines
– thermal energy in boilers, furnaces, etc.
The combustion quality is important for the users.
– the octane numbers (ASTM D 2699 and ASTM D 2700): Research method (RON) and
Motor method (MON) for spark-ignition engines.
Related to a combustion with no detonations.
– the cetane number (ASTM D 613) for diesel fuels in diesel engines with ignition by
compression.
Related to the ignition quality of diesel fuels in hot air compressed by the engine.
The terms Calculated cetane number (ISO 4264) and ASTM cetane number are used to
distinguish whether additives are used or not.
– the smoke point (ASTM D 1322) for aviation turbine fuels which give an indication of the
flame characteristics.
– the Conradson carbon residue (ASTM D 189) for home heating and diesel oils and also for
heavy fuel oils.
Related to carbon deposit formation.
The first quality criterion is the quantity of heat or energy available when a fuel is burnt. It is determined for
all fuels as the calorific value (ASTM 240 and NF 07-030). Although this property is an important one, the
calorific value is not generally specified, except for jet fuels (such as JET A1) which are concerned by a
minimum calorific value specification.

17
OCTANE NUMBER OF AUTOMOTIVE GASOLINE
The octane number is essential for automotive gasoline. It defines the fuel's ability to burn correctly in a
spark-ignition internal combustion engine.
For any given engine, malfunctioning due to the gasoline quality results in a metallic sound, a "knock", and in
the overheating of the engine.
1- THE KNOCK AND ITS CONSEQUENCES

The principle of the four-cycle engine and the combustion chamber pressure is shown in the following figure.
1st cycle : 2nd cycle : 3rd cycle : 4th cycle :

Induction Compression Combustion Exhaust
air/fuel and ignition expansion
Pressure (bar)
50
40 Maximum pressure
Opening UDC : Upper Dead Center
30 Spark/ignition EXHAUST LDC : Lower Dead Center
20 Closure 3 VALVE
10 INTAKE
Combustion 4
VALVE
5
1 bar 1 2
Atmospheric pressure
1
LDC LDC
UDC UDC UDC
Spark Degrees
D ANA 063 B
advance of crankshaft
0° 180° 360° 540° 720°
In classical running conditions, the following values can be observed:

– duration of combustion: 1 to 2 milliseconds
– spark advance : 4 to 25° of crankshaft
– maximum pressure : 35 to 50 bars

18
yy
;;
;;
yy
Knock is due to instantaneous ignition of the fuel at a given point in the combustion chamber. Normally,
combustion is rapid but gradual with propagation of the flame front produced by the spark from the plug.
Knock therefore occurs in the air fuel mixture which is last to be reached by the flame front.
yy
;;;;
yy
;;
yy
yy
;;
Spark
plug
yyyy
;;;;
;;
yy
yy
;;
Intak st
e Exhau
Flame front
Burnt
mixture
Knocking
zone
D ANA 062 B
Piston
This unburned part or residual charge, a mixture of air and vaporised hydrocarbons, finds itself under such
pressure and heat that it can suddenly ignite before being reached by the flame front.
The result is a localized increase in pressure followed by vibrations from the gaseous mass which, when, they
hit the piston head, cause the characteristic knock. It is represented in the two figures hereafter.
DIAGRAMS: pressure inside the combustion chamber in relation to time.
UDC UDC Consequences of intense,

prolonged knock
• Overloading of the cooling

system and temperature
elevation (cylinder head
gasket deterioration) which
can lead to engine failure.
• Mechanical damage:
Ignition Ignition
D ANA 064 B
Erosion of the cylinder head

and the piston
Deterioration of the spark
plugs and the valves
Normal combustion Combustion with knock

19
For a given gasoline quality, the knocking phenomenon depends on a number of important factors:
– the local weather conditions: pressure-temperature

– the shape of the combustion chamber
– the adjustment of the fuel/air ratio
– rotating speed of the engine
– the adjustment of spark advance
– the volumetric ratio or compression ratio of the engine which is defined as follows: the
piston moves (backward and forward) in the cylinder from the lower dead center (L.D.C.) to
the upper dead center (U.D.C.)
volume of chamber at L.D.C.

Compression ratio =
volume of chamber at U.D.C.
It is known that a high compression ratio increases the engine efficiency. Consequently, it reduces gasoline
consumption. But a high compression ratio leads to higher pressures during the combustion phase and
therefore promotes knocking conditions. The value of the compression ratio of the more common engines is
between 8 and 11. The chances of knocking are increased by a high rate of compression.
For a given engine running under given conditions, knocking occurrence depends on the quality of
the gasoline only.
Thanks to this knowledge, standardized methods of measuring and classifying gasolines according to their
antiknock properties have been drawn up.
2- THE CFR ENGINE, OCTANE NUMBER, DEFINITION AND MEASUREMENT

a - CFR engine
In order to study the anti-knock properties of a given gasoline, only one engine, that designed by the
Cooperative Fuel Research (CFR) is used. It is a single-cylinder engine which runs at a constant speed.
To start or to stop the knock, the variable single-cylinder rates of compression can be modified by
moving the cylinder and cylinder head together in relation to the engine frame. The measurement of the knock
is carried out by a detonation pickup, which is placed in the combustion chamber. The signal is amplified and
transmitted to a measuring device called a "knockmeter".
Pressure measurement
40 60
Plug Micrometer 80
20 C M E TE
NO R
K
100
0
Mobile cylinder
Carter fixe
D ANA 072 B
Knockmeter

20
The measuring procedure: two standard fuels are used:
– normal heptane which "knocks" easily, to which we attribute an octane number equal to 0,
– isooctane (2,2,4 trimethylpentane) which resists "knocking", to which an octane number of
100 is attributed
A mixture of these two fuels is made up, and by definition the octane number of the tested gasoline is the
volume percentage of isooctane in the mixture of normal H and Iso O.
e.g. A fuel is said to have an octane number of 96 if it triggers off knocking in the CFR engine, which is the
same as that of a mixture of 96 volume % isooctane and 4 volume % normal heptane.
b - Standard methods
Two principal methods are used for automotive gasoline.
— Research method of F1: Research Octane Number (RON) (ASTM D 2699)
The rotation speed is set at 600 r.p.m. and spark timing is fixed. The air fuel mixture is loaded at room
temperature.
— Motor method or F2: Motor Octane Number (MON) (ASTM D 2700)
Compared to the RON, the main differences are the speed of rotation of the CFR engine: 900 r.p.m. (instead
of 600 r.p.m.). The spark timing changes with the compression ratio and the intake mixture temperature is
held constant at about 150°C.
c - Gasoline sensitivity
Taking into account the more severe measurement conditions, the motor octane number is generally lower
than the research octane number.
We call the difference between the RON and MON figures the gasoline sensitivity.
A specification for MON or for sensitivity is a guarantee of satisfaction behaviour of the motor fuel in severe
conditions.
d - Octane number distribution in gasolines - DR measurement
When fierce acceleration occurs in a car (which is the driving phase where knocking is often observed) the
engine is essentially fed with the lighter components of the gasoline during this short transitory period. These
lighter components do not necessarily have the same octane number as that of the whole gasoline.
By taking into account this factor to forecast the behaviour of gasolines, ESSO STANDARD Co has
developed a new method, called the DR method:
DR = gasoline RON - light fractions RON

21
The DR 100 is often stated. In this case, the light fraction of the gasoline is the cut with an end boiling point
lower than 100°C. Generally, the DR is positive and the tendency is to manufacture gasolines with a DR as
low as possible, consequently with a good "octane" distribution.
In France, there is no official specification concerning the DR. However the average value of DR 100 is
around 7 points.
3- OCTANE NUMBER OF HYDROCARBONS

The following table gives the general octane number for the different hydrocarbon types.
Hydrocarbons
Hydrocarbons initial crude oils from conversion
PARAFFINS NAPHTENES AROMATICS OLEFINS
Isoparaffins
Normal paraffins
(branched
(straight chains)
chains)
Liquid density
low low medium high low
Research
octane number
very low high medium very high high
(RON)
Sensitivity
(RON – MON) very low very low low high very high
According to the proportions of the different families of hydrocarbons contained in gasolines, the fuel octane
numbers vary a great deal:
– the straight-run heavy gasolines from crude oils have a high normal paraffin content and a
low aromatic content. The corresponding octane number is low
– however the reformate gasolines produced by catalytic reforming have a high aromatic
content and thus a very high octane number
– gasolines from catalytic cracking contain aromatics, olefins and saturated hydrocarbons.
Their octane number is rather high

22
4 - ADDITIVES WHICH IMPROVE THE OCTANE NUMBER - SUSCEPTIBILITY OF

GASOLINES
As early as 1922, the researchers in the General Motors Company discovered that certain elements were
able to improve the anti-knock properties of automotive gasolines and in so doing, their octane number.
tetraethyl lead (T.E.L.) - boiling point 200°C

tetramethyl lead (T.M.L.) - boiling point 110°C
or a mixture of both
The addition of leaded components does not have the same effect on all gasolines: some increase their
octane number remarkably: they are said to have great lead susceptibility. On the other hand, others react
insignificantly, thus showing poor lead susceptibility. We call the octane number, before adding lead, the clear
octane number (clear RON).
Lead-based additives are no more used in many countries.
In fact, researchs performed since 1975 in order to reduce atmospheric pollution due to exhaust gases of
cars has led to a technical solution. A catalytic converter is placed on the exhaust system. It contains a
catalyst promoting chemical removal of toxic products contained in exhaust gases.
In Europe, legal directives pushed manufacturers to install catalytic converters on all new vehicles using
automotive gasoline.
Lead compounds released with combustion products are a poison for the catalyst. It is therefore the current
use of catalytic converters which has questioned the use of lead as an octane booster in automotive
gasolines.
The legal directives in use are:
– all new vehicles have catalytic converters as from January 1993

– lead phase out from automotive gasoline distributed in the European Union since
January 2000
The lead is eliminated from automotive gasoline in all European Union countries.
Lead face out leaded to the incorporation of a potassium-based additive to the automotive gasolines for valve
protection.

23
CETANE NUMBER OF DIESEL FUEL
— ASTM D 613 —
The cetane number is one of the very important properties of diesel fuel oils since it measures the ignition
quality of the fuel and influences fuel combustion in diesel engine combustion chambers. It is also a property
of home-heating fuels.
1- OPERATION OF A COMPRESSION-IGNITION ENGINE
80
COMPRESSION Pressure (bar)
RATIO 70
End of injection
Direct injection 60 Ignition delay
engine
15 to 20
50 100
Prechamber
Burnt fraction (%)

UDC
40
Beginning of combustion
engine
20 - 24
Beginning of injection
30
AIR TEMPERATURE 50
AT THE END 20
OF COMPRESSION
10
D PPC 049 B
400 to 600 °C Injection
0 0
Degrees of crankshaft
In this type of engine, the fuel is injected into the cylinder containing heated air during the compression phase.
Combustion is not instantaneous. There is a time gap between the beginning of fuel injection and the
beginning of combustion. This time gap is called the ignition delay.
This delay plays an important role in the running of which engines:
– under normal running conditions, a fuel with a short ignition delay enhances the silent and
easy running of the engine by restricting the sudden increase in pressure that corresponds
to the uncontrolled combustion of the fuel injected at each cycle
– under cold starting conditions, when fuel ignition conditions are less favorable (low air
temperature at the end of the compression cycle) a shorter ignition delay will also be
required.

24
2- THE MEASUREMENTS OF THE IGNITION DELAY - THE CETANE NUMBER

a - CFR diesel motor
The ignition delay cannot be measured directly but the performance of the fuel is evaluated in a standardized
engine (CFR Diesel Motor) and compared to reference mixtures which are:
– a normal paraffin: n-cetane (nC 16) which has a short ignition delay and by definition has a
cetane number of 100
– an aromatic compound (1-methylnaphthalene) with a similar boiling point and a lengthy

ignition delay which by definition has a zero cetane number
The cetane number of a gas oil corresponds to the volume percentage of cetane in the mixture of the two
reference fuels which has the same ignition delay in the CFR diesel engine as that of the gas oil tested.
b - Hydrocarbon cetane number
The following table gives the general cetane numbers vs the different hydrocarbon families:
Hydrocarbons
Hydrocarbons from initial crude oils from conversion
(crackings)
PARAFFINS NAPHTENES AROMATICS OLEFINS
Normal paraffins Isoparaffins

(straight chains) (branched chains)
Liquid
density low low medium high low
Cetane
very high low medium low low
number
We can see that the paraffinic gas oils obtained by straight-run distillation have a high cetane number. On the
contrary, gas oils rich in unsaturated compounds such as aromatics or olefins have low cetane numbers.
c - Calculated cetane number
Cetane number measurements is not systematically carried out by the CFR motor method. Some correlation
charts have been designed to give the calculated cetane number.

25
Density to ¡C F
49 15 ¡C 300 570
290 560
550
0.79
280 540 The chemical nature of diesel oil is
47
530 defined by its density. It is known
270 520 that paraffinic hydrocarbons have
ASTM 50 % distilled temperature

0.80 65 510
45
260 500
much lower density than aromatics
60 490
or naphthenic hydrocarbons.
43 0.81 250
480
55 The average volatility of the
41 0.82
50 240
470
diesel oil cut is given by its 50%
460 ASTM boiling point.
39 0.83 45
450
API gravity
230
With these two parameters, the
40 440
37 0.84 calculated cetane index (CI) can
35 220 430 be read as shown in the chart
35 0.85
420
(ASTM 976-91).
30
33 0.86
210 410 (Example: CI = 49 for 0.832 and
31 0.87
Calculed t 50 = 250°C)
cetane number 400
29 0.88
200
390
27 0.89
0.90 380
25
D ANA 073 B
0.91 190
23 370
The standard test ASTM D 4737-90 gives more accurate results, but in a more limited range, since it takes
into account 4 variables:
– API gravity (15°C)

– ASTM 50% distilled vol. temperature
It can be applied in the following range:
– CN: 32.5 – 56.5

15
– sp.gr4 : 0.805 – 0.895
– ASTM distillation:
• 10% point: 171 – 259°C

• 50% point: 212 – 308°C
• 90% point: 251 – 363°C

26
3 - DIESEL ENGINE POLLUTION

The compression-ignition engine is responsible for much lower emissions of carbon monoxide (CO, 20 to 50
times lower) and unburnt hydrocarbons (HC, 10 times lower) than the spark-ignition engine. The reason is the
oxygen excess (fuel/air ratio < 1). The amount of nitrogen oxides (NOx) in the exhaust gases is slightly less
high due to lower temperatures in the combustion chamber. On the other hand, the diesel engine emits
particulates (PAH: Polycyclic Aromatic Hydrocarbons) which are solids of around one micrometer in size.
The increasing severity of antipollution specifications for diesel engines requires the reduction of NOx and
particle emissions as top priority.
Several technical solutions can be considered:
– Exhaust Gas Recirculation (EGR) which delutes oxygen in the combustion chamber,
reduces flame temperature, and thus reduces NOx formation: NOx factor is divided by @ 2
when flame temperature is reduced by 50°C
– particulate traps in order to burn them continuously or at intervals
– two-way catalytic converter (oxidizing catalyst) which aims at transforming unburnt HC into
CO 2 + H2 O and CO into CO2 . At the same time it burns part of the PAH volatile fraction.
The European Directive fixed the following sulfur specifications for gas oils : 0.2% wt from 1/10/94, then
0.05% wt from 1/10/96, 0.035% wt since January 2000, 50 ppm since January 2005 and 10 ppm in
January 2009 .
This charge implies large modifications in the refineries:
– hydrogen need (available quantities of hydrogen has been reduced with the reduction of
aromatics in gasolines from year 2000)
– hydrodesulfurisation capacities
– gas purification plants capacities
“Denox” catalysis is in the development stage yet. It’s efficiency doesn’t exceed 50%. This catalysis type can
also be used for spark-ignition engines operating with air excess, which has been commercialised by
Mitsubishi in Japan only since early 1999. However, sulfur is detrimental for Denox catalyst.
It is important to note that concerning standard diesel fuels, the higher the sulfur content, the higher the
amount of particulates formed. This can be explained by the fact that part of the S is converted into SO2
and then into hydrated H2 SO4 which is collected together with the particulates (filtration).
In addition, the use of an oxidizing catalyst promotes the oxidation of SO2 into SO 3 and leads to a new
increase of particulate emission.
The reduction of the sulfur content in diesel fuels is mandatory for the depollution of diesel engines.

27
SMOKE POINT FOR AVIATION TURBINE FUELS
— ASTM D 1322 —
The petroleum product is burnt in an enclosed lamp with a standardized wick. The test tries to determine the
maximum flame height that can be achieved without smoking.
This flame height is estimated in mm to the nearest 0.5 mm by a reading on an incorporated scale. It is called
the smoke point of the tested sample.
Chimney
Flame
Scale
Air intake Wick guide

Wick
+
Wick hight
controlling equipment
(not represented)
Sample
Event (20 ml)
D ANA 074 B
LAMP BODY
WICK GUIDE
SMOKE POINT LAMP
The smoke point is related to the aromatics content.
50
40
s )
r a ffin % By comparison with the other hydrocarbon families,
a m e
P
olu the aromatics are richer in carbon and appear more
Smoke point (mm)
30 (V 50% radiant during combustion because of the presence

of fine carbonaceous particles. Aromatic products
will therefore produce easily smoking flames.
20
20 %
10 Thus, a high aromatic content will lead to a low
smoke point (flame height) and vice versa.
D ANA 075 B
0 5 10 15 20 25
Aromatics content (volume %)

28
STANDARD TESTS RELATED TO FUEL COMBUSTION
1- THE CALORIFIC VALUE (ASTM D 240)

The calorific value is the quantity of heat produced in certain conditions by the combustion of a kilo of
flammable product. It is measured in BTU/pound or in MJ/kg (MJ = megajoule).
For industrial fuels, knowledge of the calorific value is a fundamental, and paradoxically, this value is not
officially specified. As far as jet fuels are concerned, this property is systematically measured since it
determines the distances flown by the plane.
The ASTM standard describes a method which determines the heat of combustion by burning a sample in an
oxygen bomb calorimeter under controlled conditions. It is necessary to distinguish between:
– the Gross Heat of Combustion (GHC), or Gross Calorific Value (GCV), which is the heat
released by the combustion of a unit mass of fuel in a constant volume bomb with all the
water condensed to the liquid state
– the Net Heat of Combustion (NHC) or Net Calorific Value (NCV) measured at constant
pressure of 1 atm., with the water remaining in the vapor state
The NHC is obtained by calculation from the value of the GHC.
If the water is recovered as a liquid, the amount of heat will be higher. This is called the GHC (GCV).
If the water is recovered as a vapor, which is generally the case in industry, we obtain what is called the NHC
(NCV).
Generally we pay more attention to the NHC (NCV).
The usual NCVs of commercial fuels are as follows:
Home heating fuel 10,150 kcal/kg or 42.5 MJ/kg (18,300 Btu/pound)

Heavy fuel oil n°2 HS 9,400 kcal/kg or 39.4 MJ/kg (17,100 Btu/pound)
Heavy fuel oil n°2 VLSC 9,900 kcal/kg or 41.5 MJ/kg (18,000 Btu/pound)
The ASTM standard gives the accuracy of the method as:
repeatability : 50 kcal/kg
reproducibility : 100 kcal/kg
The difference between the combustion heat values of different fuels can be explained by the difference in the
chemical natures of the hydrocarbon components contained in the fuels.

29
The following table gives the same properties vs the chemical natures leading to different values of net heat
of combustion.
Aromatics and sulphur

Paraffinics Naphthenics
compounds
D CH 139 A
D CH 140 A
D CH 138 A
Specific gravity low medium high
Carbon
mass ratio (C/H) low medium high
Hydrogen
NHC high medium low
The heavy sulfur compounds are generally of an aromatic chemical nature and present similar properties to
those of aromatic hydrocarbons.
Furthermore, we must point out that the NHC of a petroleum product decreases when:
– the density increases

– the C/H ratio and the S% increase
The following table gives some properties of commercial fuel oils.
Heavy fuel oil with low

Usual values Home-heating fuel oil Heavy fuel oil HS
sulfur content
15
d4 0.830 - 0.880 1.035 0.945
C/H 6.3 8.5 7
Sulfur (wt %) < 0.2 3.6 <1
NHC (kcal/kg) 10 150 9 400 9 900

30
2 - THE CONRADSON CARBON RESIDUE TEST (ASTM D 189)

This standard test consists in measuring the mass of carbonaceous residue obtained from a sample of fuel
after heating, combustion and pyrolysis. The result is expressed in terms of the percentage or residue
mass/mass of sample.
The duration of initial heating is 10 min, combustion 13 min and pyrolysis 7 min.
The test measures the amount of non-vaporisable components in fuel which crack and form coke during this
test. It is intended to provide same indication of relative coke-forming propensities. The Conradson residue
figure includes the ashes.
Diesel fuel and home-heating fuel are especially concerned by this test, which is carried out on the 10%
left over from the distillation of these products.
This constraint on the diesel fuel quality aims at avoiding the fouling of the injectors and the combustion
chamber by cokable products.
Certain house hold heaters, burning distillate fuel oil -grade n°1- use a pot burner. This is type of hot plate
onto which the fuel vaporises. If the home-heating fuel contains non-vaporising products, they crack and form
coke which gradually fills the pot, thus making it impossible for the apparatus to work. Besides, CCR value is
related to unburned solid particle quantities in emission gases.
There are requirements on CCR value for heavy fuel oil, since it is related to combustion difficulties and
unburned particle emissions. CCR value is also a specification for lube base oils and an important
characteristic for conversion unit heavy feeds.
The apparatus for determining Conradson Carbon Residue (CCR) is described hereafter.
Hood
Iron cover
Horizontal
opening Iron cover
Iron crucible
Insulator Porcelain crucible
Pressed steel crucible
Dry sand
Heating : 10 minutes
D ANA 076 B
Combustion : 13 minutes
Pyrolysis : 7 minutes
This measurement also concerns the heavy fuel oils because of the relation it has with combustion trouble
and solid unburnt matter in fumes.
Conradson carbon residue is requested for specifications of lube base oils and of heavy feedstocks for
conversion processes.

31
III - TESTS RELATED TO STORAGE AND FLOWING

Viscosity is the main property related to the flowing and pumping of liquids. Besides, it characterizes the
spraying capacity of fuels in burners. This characteristic is also a fundamental quality for lube oils.
Likewise, operations which involve the storage of liquids in tanks must take into account the measurement of
weights and volumes which are determined by density.
Viscosity is linked to the resistance met by elementary particles in a fluid moving freely between each other.
Two different methods can be used to define viscosities:
– dynamic viscosity which characterizes the internal frictions between particles in the fluids
itself. Results are given in milli-Pascal-seconds, better known by the name of centipoises
(cP)
DYNAMIC VISCOSITY m Æ mPa • s or centipoises (cP)
– kinematic viscosity which takes into account both the internal frictions and the density of
the liquid. This density is involved when viscosity is determined by measuring the time
required for a fixed volume to flow through a hole or a tube under the pressure of a fixed
height of liquid. It is easy to understand in this case that the time measured depends not
only on the intrinsic viscosity of the liquid but also on its density. The kinematic viscosity
unit is the centistoke (cSt), which is expressed in mm2/second (the S.I. system uses the
m 2 /s)
KINEMATIC VISCOSITY n Æ mm2 /s or centistokes (cSt)
As reference, liquid water viscosity at 20°C is 1 cSt.
Generally speaking, liquid viscosity vary very quickly with temperature. Consequently, it is important to
make the measurements at perfectly controlled temperatures. The viscosity of petroleum products is most of
the time measured at 40°C, 50°C or 100°C.

32
VISCOSITY MEASUREMENTS OF PETROLEUM PRODUCTS
1 - KINEMATIC VISCOSITY OF LIQUID PETROLEUM PRODUCTS (ASTM D 445)

This method determines the kinematic viscosity of liquid petroleum products.
It consists in measuring the time it takes a fixed volume of liquid to flow under gravity through a calibrated
glass capillary tube under standard conditions and at fixed temperature.
The kinematic viscosity is calculated from the measured flow time by the following formula:
Kinematic viscosity (in cSt) = C . t
C: calibration constant of the viscosimeter, which depends on the size of the capillary tube,
t: flow time (seconds).
The apparatus comprises the following main devices:
Two types of tubes are generally used, depending on whether the product is clear or opaque:
– the Ubbelohde viscosimeter with suspended level for transparent liquids

– the Cannon-Fenske viscosimeter with U tube reversed flow for opaque liquids
Filling tube
Filling tube
Timing marks
Timing marks
Flow direction Flow direction

Capillary tube
D ANA 088 C
UBBELOHDE CANNON-FENSKE
— Clear liquid — — Unclear liquid —

33
After filling, the following figures show the states of the Ubbelohde viscosimeter when starting and stopping
the timer (chronometer < 0.2 s precision).
Measurement of the time it takes a

fixed volume of fluid to flow under
D ANA 086 B
gravity trough a calibrated glass
capillary tube at a fixed temperature.
2- VISCOSITY MEASUREMENTS WITH CONVENTIONAL VISCOSIMETERS

In the petroleum industry a number of conventional viscosimeters have been used almost since the beginning
of the industry, i.e. the Redwood, Saybolt and Engler viscosimeters. They are now being gradually
superseded by the kinematic viscosity methods described above. Nevertheless it is still customary to
characterize petroleum products in terms of conventional viscosities which can be converted into cSt through
conversion tables.
The most widely used are the ENGLER and SAYBOLT viscosimeters as shown below.
Filling
level
Thermometer Plug
ENGLER Mark SSU

degrees SSF
Liquid tested
Thermostatic Universal fl = 1.76 mm
water bath
200 cm3 Furol fl = 3.15 mm
Flow time Receiver Bottom of the

measurement thermostatic bath
60 cm3 Receiver
D ANA 087 B
ENGLER apparatus SAYBOLT apparatus
Viscosity is expressed by the name of the apparatus used to measure the flow time of a fixed volume of
product through a calibrated aperture.
– for the Engler viscosimeter : Engler degree (°E)
– for the saybolt viscosimeter : Seconds Saybolt Universal (SSU) if the "universal" aperture
(1.76 mm of diameter) is used and in Second Saybolt Furol (SSF) with the aperture of 3.15
mm
Conversion tables allow to get the correspondence between the various units of viscosity.

34
VISCOSITY INDEX
– ASTM D 2270 –
Viscosity is a fundamental property for lubricating oils and facilitates an oil film between two metallic surfaces
in friction movement. This essential function means that lube oils must have a minimum level of viscosity. On
the other hand the viscosity must remain low enough to avoid too much resistance during movement. These
requirements are not easy to meet in the case of engine lube oils which work at different temperatures. For
instance:
- winter start at - 15 °C
- lube oil in the engine crankcase during running: 80 °C
- cylinder oil film temperature during running: 170 to 200 °C
Consequently the relationship between viscosity and temperature is of significance for engine lubricating oils.
This characteristic is expressed by the viscosity index (or VI). A high viscosity index gives the least change
in viscosity with temperature.
The VI is closely linked to the chemical nature of the lube oils (see the diagram below).
Paraffins Naphthenes Aromatics

Normal paraffins Isoparaffins
(straight chains) (branched chains)
Viscosity for the

low low medium high
same volatility
Viscosity index very high high medium low
The viscosity index is calculated according to the ASTM D 2270 standard, specifying kinematic viscosity
measurements at 100°C (hot) and 40°C (cold) and procedures and tables are as follows.
Viscosity Index
nC 26H54 194
nC 44H90 190
iC 26 paraffins (1 pentyl) 100 to 200
C 26 naphthenic (1 cycle) 120 to 160
C 26 aromatic (1 cycle) 103
C 25 naphthenic (2 cycles) 114
C 25 aromatic (2 cycles) 74

35
VISCOSITY INDEX CALCULATION
VISCOSITY INDEX BELOW 100 VISCOSITY INDEX OF 100 AND OVER
in cSt in cSt
L
u OI
LL
D VI
=0
UN
H KN H
OW
NO O IL H
O IL H IL VI = 1
VI = 1 u 00
00 UNKNOW
y y N O IL
D ANA 018 B
D ANA 019 B
t t
40 °C 100 °C 40 °C 100 °C
y: Viscosity in hot conditions (100°C) of the oil whose viscosity index is to be calculated, in cSt (or mm2/s).
u: Viscosity in cold conditions (40°C) of the oil whose viscosity index is to be calculated, in cSt.
L: Viscosity in cSt, at 40°C, of an oil with 0 viscosity index having the same viscosity index at 100°C as the
oil to be tested.
H: Viscosity in cSt, at 40°C, of an oil with 100 viscosity index having the same viscosity index at 100°C as
the oil to be tested.
For 2 cSt < Y < 70 cSt

(see table 1)
The values of L and H and D are extracted from The value of H is extracted from tables
tables
D=L-H log H - log U

N=
log Y
L-U
VI = x 100 10N - 1
D VI = + 100
0,00715
The VI is rounded to be nearest whole number

(to the nearest even whole number when it ends in 0.5)

36
TABLE 1
BASIC VALUES FOR L, D AND H FOR KINEMATIC VISCOSITIES
IN 40-100°C SYSTEM
Kinematic Kinematic
viscosity viscosity
L D = (L – H) H L D = (L – H) H
at 100°C at 100°C
mm2/s mm2/s
2.00 7.994 1.600 6.394 6.00 57.97 19.78 38.19

2.10 8.640 1.746 6.894 6.10 59.74 20.57 39.17
2.20 9.309 1.898 7.410 6.20 61.52 21.38 40.15
2.30 10.00 2.056 7.944 6.30 63.32 22.19 41.13
2.40 10.71 2.219 8.496 6.40 65.18 23.03 42.14
2.50 11.45 2.390 9.063 6.50 67.12 23.94 43.18
2.60 12.21 2.567 9.647 6.60 69.16 24.92 44.24
2.70 13.00 2.748 10.25 6.70 71.29 25.96 45.33
2.80 13.80 2.937 10.87 6.80 73.48 27.04 46.44
2.90 14.63 3.132 11.50 6.90 75.72 28.21 47.51
3.00 15.49 3.334 12.15 7.00 78.00 29.43 48.57
3.10 16.36 3.540 12.82 7.10 80.25 30.63 49.61
3.20 17.26 3.753 13.51 7.20 82.39 31.70 50.69
3.30 18.18 3.971 14.21 7.30 84.53 32.74 51.78
3.40 19.12 4.196 14.93 7.40 86.66 33.79 52.88
3.50 20.09 4.428 15.66 7.50 88.85 34.87 53.98
3.60 21.08 4.665 16.42 7.60 91.04 35.94 55.09
3.70 22.09 4.909 17.19 7.70 93.20 37.01 56.20
3.80 23.13 5.157 17.97 7.80 95.43 38.12 57.31
3.90 24.19 5.415 18.77 7.90 97.72 39.27 58.45
4.00 25.32 5.756 19.56 8.00 100.0 40.40 59.60
4.10 26.50 6.129 20.37 8.10 102.3 41.57 60.74
4.20 27.75 6.546 21.21 8.20 104.6 42.72 61.89
4.30 29.07 7.017 22.05 8.30 106.9 43.85 63.05
4.40 30.48 7.560 22.92 8.40 109.2 45.01 64.18
4.50 31.96 8.156 23.81 8.50 111.5 46.19 65.32
4.60 33.52 8.806 24.71 8.60 113.9 47.40 66.48
4.70 35.13 9.499 25.63 8.70 116.2 48.57 67.64
4.80 36.79 10.22 26.57 8.80 118.5 49.75 68.79
4.90 38.50 10.97 27.53 8.90 120.9 50.96 69.94
5.00 40.23 11.74 28.49 9.00 123.3 52.20 71.10
5.10 41.99 12.53 29.46 9.10 125.7 53.40 72.27
5.20 43.76 13.32 30.43 9.20 128.0 54.61 73.42
5.30 45.53 14.13 31.40 9.30 130.4 55.84 74.57
5.40 47.31 14.94 32.37 9.40 132.8 57.10 75.73
5.50 49.09 15.75 33.34 9.50 135.3 58.36 76.91
5.60 50.07 16.55 34.32 9.60 137.7 59.68 78.08
5.70 52.64 17.36 35.29 9.70 140.1 60.87 79.27
5.80 54.42 18.16 36.26 9.80 142.7 62.22 80.46
5.90 56.20 18.97 37.23 9.90 145.2 63.54 81.67

37
Kinematic Kinematic
viscosity viscosity
L D = (L – H) H L D = (L – H) H
at 100°C at 100°C
mm2/s mm2/s
10.0 147.7 64.86 82.87 16.5 350.3 178.1 172.3

10.1 150.3 66.22 84.08 16.6 354.1 180.3 173.8
10.2 152.9 67.56 85.30 16.7 358.0 182.5 175.4
10.3 155.4 68.90 86.51 16.8 361.7 189.7 177.0
10.4 158.0 70.25 87.72 16.9 365.6 187.0 178.6
10.5 160.6 71.63 88.95 17.0 369.4 189.2 180.2
10.6 163.2 73.00 90.19 17.1 373.3 191.5 181.7
10.7 165.8 74.42 91.40 17.2 377.1 193.8 183.3
10.8 168.5 75.86 92.65 17.3 381.0 196.1 184.9
10.9 171.2 77.33 93.92 17.4 384.9 198.4 186.5
11.0 173.9 78.75 95.19 17.5 388.9 200.8 188.1
11.1 176.6 80.20 96.45 17.6 392.7 203.0 189.7
11.2 179.4 81.65 97.71 17.7 396.7 205.3 191.3
11.3 182.1 83.13 98.97 17.8 400.7 207.7 192.9
11.4 184.9 84.63 100.2 17.9 404.6 210.0 194.6
11.5 187.6 86.10 101.5 18.0 408.6 212.4 196.2
11.6 190.4 87.61 102.8 18.1 412.6 214.8 197.8
11.7 193.3 89.18 104.1 18.2 416.7 217.3 199.4
11.8 196.2 90.75 105.4 18.3 420.7 219.7 201.0
11.9 199.0 92.30 106.7 18.4 424.9 222.2 202.6
12.0 201.9 93.87 108.0 18.5 429.0 224.7 204.3
12.1 204.8 95.47 109.4 18.6 433.2 227.2 205.9
12.2 207.8 97.07 110.7 18.7 437.3 229.7 207.6
12.3 210.7 98.66 112.0 18.8 441.5 232.3 209.3
12.4 213.6 100.3 113.3 18.9 445.7 234.7 211.0
12.5 216.6 101.9 114.7 19.0 449.9 237.3 212.7
12.6 219.6 103.6 116.0 19.1 454.2 239.8 214.4
12.7 222.6 105.3 117.4 19.2 458.4 242.3 216.1
12.8 225.7 107.0 118.7 19.3 462.7 245.0 217.7
12.9 228.8 108.7 120.1 19.4 467.0 247.6 219.4
13.0 231.9 110.4 121.5 19.5 471.3 250.2 221.1
13.1 236.0 112.1 122.9 19.6 475.7 252.9 222.8
13.2 238.1 113.8 124.2 19.7 479.7 255.2 224.5
13.3 241.2 115.6 125.6 19.8 483.9 257.8 226.2
13.4 244.3 117.3 127.0 19.9 488.6 260.9 227.7
13.5 247.4 119.0 128.4 20.0 493.2 263.7 229.5
13.6 250.6 120.8 129.8 20.2 501.5 268.5 233.0
13.7 253.8 122.6 131.2 20.4 510.8 274.4 236.4
13.8 257.0 124.4 132.6 20.6 519.9 279.8 240.1
13.9 260.1 126.2 134.0 20.8 528.8 285.3 243.5
14.0 263.3 128.0 135.4 21.0 538.4 291.3 247.1
14.1 266.6 129.8 136.8 21.2 547.5 296.8 250.7
14.2 269.8 131.6 138.2 21.4 556.7 302.6 254.2
14.3 273.0 133.5 139.6 21.6 566.4 308.6 257.8
14.4 276.3 135.3 141.0 21.8 575.6 314.1 261.5
14.5 279.6 137.2 142.4 22.0 585.2 320.2 264.9
14.6 283.0 139.1 143.9 22.2 595.0 326.4 268.6
14.7 286.4 141.1 145.3 22.4 604.3 332.0 272.3
14.8 289.7 142.9 146.8 22.6 614.2 338.4 275.8
14.9 293.0 144.8 148.2 22.8 624.1 344.5 279.6
15.0 296.5 146.8 149.7 23.0 633.6 350.3 283.3
15.1 300.0 148.8 151.2 23.2 643.4 356.6 286.8
15.2 303.4 150.8 152.6 23.4 653.8 363.3 290.5
15.3 306.9 152.8 154.1 23.6 663.3 369.0 294.4
15.4 310.3 154.8 155.6 23.8 673.7 375.7 297.9
15.5 313.9 156.9 157.0 24.0 683.9 382.1 301.8
15.6 317.5 158.9 158.6 24.2 694.5 388.9 305.6
15.7 321.1 161.0 160.1 24.4 704.2 394.8 309.4
15.8 324.6 163.0 161.6 24.6 714.9 401.9 313.0
15.9 328.3 165.2 163.1 24.8 725.7 408.8 317.0
16.0 331.9 167.3 164.6 25.0 736.5 415.6 320.9
16.1 336.5 169.4 166.1 25.2 747.2 422.4 324.9
16.2 339.2 171.5 167.7 25.4 758.2 429.5 328.8
16.3 342.9 173.7 169.2 25.6 769.3 436.6 332.7
16.4 346.6 175.8 170.7 25.8 779.7 443.0 336.7

38
Kinematic Kinematic
viscosity viscosity
L D = (L – H) H L D = (L – H) H
at 100°C at 100°C
mm2/s mm2/s
26.0 790.4 449.8 340.5 45.0 2152 1371 780.9

26.2 801.6 457.2 344.4 45.5 2197 1403 794.5
26.4 812.8 464.4 348.4 46.0 2243 1434 808.2
26.6 824.1 471.8 352.3 46.5 2288 1466 821.9
26.8 835.5 479.1 356.4 47.0 2333 1498 835.5
27.0 847.0 486.6 360.5 47.5 2380 1530 849.2
27.2 857.5 492.9 364.6 48.0 2426 1563 863.0
27.4 869.0 500.6 368.3 48.5 2473 1596 876.9
27.6 880.6 508.3 372.3 49.0 2521 1630 890.9
27.8 892.3 515.9 376.4 49.5 2570 1665 905.3
28.0 904.1 523.5 380.6 50.0 2618 1699 919.6
28.2 915.8 531.2 384.6 50.5 2667 1733 933.6
28.4 927.6 538.8 388.8 51.0 2717 1769 948.2
28.6 938.6 545.7 393.0 51.5 2767 1804 962.9
28.8 951.2 554.5 396.6 52.0 2817 1839 977.5
29.0 963.4 562.3 401.1 52.5 2867 1875 992.1
29.2 975.4 570.1 405.3 53.0 2918 1911 1007
29.4 987.1 577.6 409.5 53.5 2969 1947 1021
29.6 998.9 585.3 413.5 54.0 3020 1984 1036
29.8 1011 593.4 417.6 54.5 3073 2022 1051
30.0 1023 601.6 421.7 55.0 3126 2060 1066
30.5 1055 622.3 432.4 55.5 3180 2098 1082
31.0 1086 643.2 443.2 56.0 3233 2136 1097
31.5 1119 664.5 454.0 56.5 3286 2174 1112
32.0 1151 686.0 464.9 57.0 3340 2213 1127
32.5 1184 708.0 475.9 57.5 3396 2253 1143
33.0 1217 730.2 487.0 58.0 3452 2293 1159
33.5 1251 752.8 498.1 58.5 3507 2332 1175
34.0 1286 776.8 509.6 59.0 3563 2372 1190
34.5 1321 799.9 521.1 59.5 3619 2413 1206
35.0 1356 823.4 532.5 60.0 3676 2454 1222
35.5 1391 847.2 544.0 60.5 3734 2496 1238
36.0 1427 871.2 555.6 61.0 3792 2538 1254
36.5 1464 896.5 567.1 61.5 3850 2579 1270
37.0 1501 921.8 579.3 62.0 3908 2621 1286
37.5 1533 946.8 591.3 62.5 3966 2664 1303
38.0 1575 972.3 603.1 63.0 4026 2707 1319
38.5 1613 998.3 615.0 63.5 4087 2751 1336
39.0 1651 1024 627.1 64.0 4147 2795 1392
39.5 1691 1052 639.2 64.5 4207 2858 1369
40.0 1730 1079 651.8 65.0 4268 2882 1386
40.5 1770 1106 664.2 65.5 4329 2927 1402
41.0 1810 1133 676.6 66.0 4392 2973 1419
41.5 1851 1162 689.1 66.5 4455 3018 1436
42.0 1892 1191 701.9 67.0 4517 3064 1454
42.5 1935 1220 714.9 67.5 4580 3110 1471
43.0 1978 1250 728.2 68.0 4645 3157 1488
43.5 2021 1280 741.3 68.5 4709 3204 1506
44.0 2064 1310 754.4 69.0 4773 3250 1523
44.5 2108 1340 767.6 69.5 4839 3298 1541
70.0 4905 3346 1558

39
S.A.E. VISCOSITY GRADES OF ENGINE LUBRICATING OILS
The S.A.E. viscosity grades are related to viscosity specifications:

- in cold conditions: W winter grades: 0 W, 5 W, 10 W, 15 W, 20 W, 25 W,
- and in hot conditions (100°C): 20, 30, 40, 40.
A "multigrade" lube oil complies with two viscosity grade specifications:
20 W 40 has the following meanings:

- viscosity below 9500 cP at - 15°C
- viscosity between 12.5 and 16.3 cSt at + 100°C
According to the table:
SAE Starting viscosity 1 Cold pumpability 2 Kinematic viscosity3 Viscosity HTHS4 at

viscosity in mPa (cP) in mPa (cP) in mm2/s (cSt) 150°C (en cP)
grade at temperature (°C) at temperature (°C)
Maxi Maxi Mini Maxi Mini
0W 6200 at – 35 60000 at – 40 3,8 — —
5W 6600 at – 30 60000 at – 35 3,8 — —
10 W 7000 at – 25 60000 at – 30 4,1 — —
15 W 7000 at – 20 60000 at – 25 5,6 — —
20 W 9500 at – 15 60000 at – 20 5,6 — —
25 W 13000 at – 10 60000 at – 15 9,3 — —
20 — — 5,6 < 9,3 2,6
30 — — 9,3 < 12,5 2,9
40 — — 12,5 < 16,3 2,9 (grades 0W-40,

5W-40 and 10W-40)
40 — — 12,5 < 16,3 3,7 (grades 15W-40,

20W-40, 25W-40, 40)
50 — — 16,3 < 21,9 3,7
60 — — 21,9 < 26,1 3,7
1- ASTM D5293
2- ASTM D4684
3- ASTM D445
4- ASTM D4683
Note : 1 cP = 1 m Pa/s ; 1 cSt = 1 mm2/s

40
LUBRICATING PROPERTIES OF DIESEL FUELS
— ISO 12156-1 norm —
Compression-ignition engines are provided with injection systems requiring fuel free of water and solid
particles. Thanks to lubricating properties of diesel fuels, injection systems are protected against wear.
Lubricating properties of diesel fuels decrease when sulfur content decreases, which causes wear of
injectors. Hence, specific additives have to be added to compensate for the loss of lubrication.
Since July 1999, a new specification related to the lubricating properties has been introduced. The
corresponding test is described by the ISO 12156-1 norm.
A ball in a sample of diesel fuel is pressed against a test plate. A reciprocating movement generates a friction
phenomena between the non rotating steel ball and the test plate. This results in a wear mark on the ball
which is measured. The higher the lubricating properties of the sample, the smaller the wear mark on the ball.
Test plate Heating device

Applied force
Test ball
Oscillation movement
Fuel sample
D ANA 119 B
High Frequency Reciprocating Ring (HFRR)
This apparatus called High Frequency Reciprocating Ring (HFRR) allows to assess the wear diameter.
European specification for diesel oil (EN 590) is: less than 460 m m at 60°C for wear diameter on the ball.

41
DENSITY OF PETROLEUM PRODUCTS
– ASTM D 1298 –
Density is the mass of a liquid product per unit volume generally recorded in kilograms per liter.
Because a liquid expands when the temperature rises, the value of density is given for a fixed temperature.
The chosen standard reference temperature is 15 °C and the density of the product is the mass of 1 liter of
the product at 15 °C (kg/liter).
Uses of other determinations related to density:
- specific gravity, called relative density, which is the ratio of the mass of a given volume of
liquid at 60 °F to the mass of an equal volume of pure water at the same temperature 60 °F.
60
Specific gravity is usually written spgr60,
15 °C
N.B. specific gravity 4 °C has the same value without unit as the density because 1 liter of
pure water at 4 °C weighs exactly 1 kg.
- API gravity, especially for crude oils, is another expression of density and is a special function
of spgr:
141.5
API° = - 131.5
spgr
The ASTM D 1298 method describes the measurement of density by using glass hydrometers.
When the test temperature is different from the standard temperature (15 °C), correction factors are used
on stadard tables ASTM 1250 to obtain the density (see example next page).
As shown in the figure, the hydrometer is placed

vertically in the sample cylinder. When the
Thermometer hydrometer has come to rest, estimate the
hydrometer scale reading to the nearest 0.0001 spgr
°C
110
Hydrometer or density.
°C100
110
Record the temperature to the nearest 0.2 °C.

100
Temperature Density
90
Report the results according to tables.

80
reading reading
70
Here are the approximate values of density of several

40
30
petroleum products (kg/lit. at 15 °C).

20
10
0
10
Mass in kg of 1 liter
at 15 °C
Commercial butane 0.570

Regular gasoline 0.720
Sample Premium gasoline 0.740
D ANA 113 B
product Diesel gas oil 0.850

Heavy fuel oil n°2 0.980

42
D PPC 1386 A

43
DENSITY AND RELATIVE DENSITY OF LIQUIDS

BY DIGITAL DENSITYMETER
– ASTM D 4052 –
The method covers the determination of density of petroleum distillates and viscous oils that can be handled
in a normal fashion as liquids. Its application is restricted to liquids with vapor pressures below 600 mmHg
(80 kPa).
Summary of the method and procedure
A quantity of less than 1 ml of the liquid is inserted into an oscillating sample tube and the change in
oscillating frequency f caused by the change in mass of the tube is used in conjuction with calibration data to
determine the density d of the sample.
The apparatus consists of a U-shaped mechanical oscillator sample tube of 2 mm inside diameter, plus the
electronic excitation, clock, calculating and digital display system. A constant temperature bath circulates a
liquid around the loop to maintain a constant desired temperature (15 to 70°C).
The complete scheme is shown below.
Excitation
device Capillary
tube Sample
D ANA 101 B
Outlet
Inlet
Fixed end
Double-wall sealed glass tube for heat control
Metal tube
Sealed glass tube

Measurement cell of the PAAR DMA 35 densimeter
The sample is injected into the loop with 1 or 2 ml syringe.
Calibration is done by using 2 pure components of known densities. For instance we use:
pure water at 20°C 0.9982 g/cm 3
dry air at 20°C 0.0012 g/cm 3
The computor will do all the calculations for the subsequent samples and the results are then displayed.
This method is very accurate and sensitive.
The density of all petroleum products is given to the fourth decimal place
Repeatability is given to be 0.001 and
reproducibility 0.005
in the range 0.68 to 0.97

44
TESTS RELATED TO COLD CONDITIONS
The first effect of a decrease in temperature on liquid petroleum products is mainly an increase in their
viscosity. If the temperature continues to decrease very fine particles of solid crystals appear inside the
liquid. In the case of transparent petroleum products, this looks like a milky cloud.
The crystal size increases and promotes a solid network which confines the liquid phase. The petroleum
product thickens, and if the phenomenon persists, it ceases to flow.
Due to the problems related to cold conditions petroleum products are divided into two categories:
– heated products which are maintained at a temperature high enough to avoid handling and
using troubles with high viscosity or the formation of crystals: heavy fuel oils, bitumen
– non-heated products, which can be used by clients without problems related to
atmospheric conditions; jet fuels, diesel fuels, domestic or heating fuels, base lube oils.
These products are stored in non-heated tanks, and whatever the ambient or the winter
temperature, they should not plug the transfer lines nor affect pumpability
Crystallization (or solidification) mainly concerns the paraffinic hydrocarbon family and more specifically the
n-paraffins.
The crystallization temperatures for some of them are given hereafter:
Crystallization Physical
temperature (°C) state at 20°C
nC 4 H 10 - 138 L
nC 8 H 18 - 57 L
nC 16H 34 + 18 L
nC 26H 54 + 56 S
nC 36H 74 + 76 S
nC 44H 90 + 86 S
These values are very high compared to the crystallization temperatures of components with the same
number of carbon atoms (C26) but of a different chemical nature:
Crystallization temperature (°C)

normal paraffin: nC26 + 56
branched chain paraffin: iC26 - 40 to + 30
naphthenic C26 around - 40
aromatic C 26 from - 60 to - 30

45
The following standard methods are used to avoid paraffin crystallization risks:
- cloud point of petroleum oils (ASTM D 2500 - ISO 3015),

- pour point of petroleum products (ASTM D 97 - ISO 3016),
- filterability limit temperature (CEN Method 116) similar to cold filter plugging point of
distillate fuels (IP 309),
- freezing point of aviation fuels (D 2386).
Other cold condition troubles may occur in the presence of water particularly in the case of liquefied
petroleum gases (LPG).
During cooling, particularly when high-pressure LPG (in tanks or bottles) containing water is expanded to the
lower pressure of utilization, crystalline compounds can be formed and can plug the transfer lines or the
pressure-reducing valves.
These crystals are formed with ice or with compounds of water and certain hydrocarbon components, called
"hydrate". The "hydrates" take up a large volume because of their low density. The "hydrates" formation risks
are higher in the use of commercial propane than in that of butane, due to the greater expansion of propane
after a lower storage temperature. Line temperatures of gaseous propane can be lowered much more than
those of gaseous butane.
In order to avoid these plugging effects which are very dangerous for the user, the freezing specifications are
much stricter for commercial propane. The corresponding standard methods are the NGPA Propane
dryness test (cobalt bromide method) or the French standard NF 41-004.
For butane, a simple visual test is sufficient in order to verify the absence of traces of water separated by
decantation.

46
CLOUD POINT AND POUR POINT OF PETROLEUM PRODUCTS
• CLOUD POINT
As already mentioned, a substantial lowering of the temperature will lead to the appearance of very fine solid
particles in the liquid, which we call crystals. This feature is particularly noticeable in the case of clear
products and is characterised by a "milky" clouding of the liquid. The temperature required for this is called
the CLOUD POINT (ASTM D 2500).
Thermometer
The petroleum sample is brought to a
temperature at least 15°C above the
approximate cloud point and poured into the test
jar up to the level mark. The test jar is then
corked and the thermometer position is adjusted
so that the thermometer bulb rests on the
bottom of the jar.
The sample is then gradually cooled by using a

refrigeration bath and the clearness of the
sample is monitored at every degree centigrade.
When such inspection first reveals a distinct

Refrigerating cloudiness or haze at the bottom of the test
D ANA 078 B
bath jar, the temperature reached is the cloud

point.
• THE POUR POINT

The same apparatus as for ASTM D 2500 is used and the Thermometer
sample is poured in. The thermometer position is different:
it is placed so that the bulb is immersed and the beginning
of the capillary is 3 mm under the sample surface.
The sample is heated and then cooled by using different

cooling baths at fixed decreasing temperatures.
Inspection starts at a temperature which is at least 15°C

above the approximate, pour point temperature.
During cooling, at each temperature reading that is a

multiple of 3°C, the test jar is removed and replaced in the
jacket until there is no movement in the jar when it is held
in a horizontal position for 5 seconds. Refrigerating
D ANA 079 B
bath
The pour point is the last temperature reading + 3°C.

47
FILTERABILITY LIMIT TEMPERATURE
– CEN Method 116 –

This method is similar to the IP 309 method for the Cold Filter Plugging Point (CFPP) of distillate fuels. It
describes a procedure to be applied to distillate fuels: automotive diesel fuels and gas oils. The test may also
be applied to home heating fuel oils.
The filterability limit temperature or the cold filter plugging point is the lowest temperature at which a fixed
volume of fuel, when cooled under standard conditions, will not flow through the filtration apparatus within a
limited flow time.
The aim of the method is to assess the lowest temperature at which the fuel flows freely. In the case of diesel
fuel oils the observed temperature is generally close to the operability limit of fuels during service. For home
heating fuels, a higher margin is generally observed.
Atmosphere
CFPP (°C) is the lowest
temperature at which a
fixed fuel volume is Vacuum
pumped through the 20 mbar
filter unit within a
limited flow time.
Pipette
Test tube
Annular chocks Cooling bath (– 34°C)

Jacket
Filter unit
Thermometer
Stainless steel wire mesh 45 µm
Filter
D ANA 080 B
unit

48
SUMMARY OF THE OPERATING PROCEDURE

- the sample to be tested is first filtered through dry filter paper and then poured in to the jar to
the etched mark (about 45 ml),
- the first test is carried out at a temperature that is a multiple of 1°C at 5°C above the cloud
point of the product,
- the 3-way cock is placed to vacuum position at the moment the time is measured,
- the flow time reading is recorded when the sample is drawn out through the filter to reach the
etched mark on the pipette. The 3-way cock is immediately replaced in the atmospheric
position,
- If the time reading is less than 60 seconds, the test is repeated at a temperature lower by 1°C,
- The CFPP is reached when, after 60 seconds, the sample has not filled the pipette up to the
etched mark. The temperature reading for the final test is the CFPP and is expressed in °C.

49
FREEZING POINT OF AVIATION FUELS
– D 2386 –
TEST APPARATUS
Brass stirrer
rod Thermometer
Brass packing
gland
Jacketed sample
tube
Unisilvered
vacuum flask
Refrigerant
D ANA 081 B
The jet fuel is simultaneously cooled and shaken vigorously in the apparatus in order to simulate the
freezing conditions encountered during flight. The temperature at which crystals of hydrocarbons appear
is recorded. This temperature is called crystallization point. The jacketed sample tube is then removed from
the refrigerant flask and the sample is allowed to warm slowly while being stirred continuously. The
temperature at which the crystals completely disappear is recorded as the freezing point.
The test is considered acceptable if the difference between the freezing point and the crystallization point is
less than 3°C.

50
PROPANE DRYNESS TEST (Cobalt bromide method)
– NGPA –
Although butane should not contain water that can be separated by decantation, the moisture
content chiefly concerns propane, which has to meet moisture detection requirements using the
cobaltous bromide test (NF M 41-004). If water is present in gaseous propane circuits at relatively
high pressure and low temperatures (in winter and in outside conditions) solid crystals called gas
hydrates may appear. These compounds are formed by the association of water and hydrocarbons
(ethane, propane) in solid form and may plug the circuit, when cooled after LPG vaporization and
depressurization from container pressure to ambiant pressure.
The graph below gives the area where hydrates are formed in function of temperature and pressure
together with the influence of hydrocarbon.
100
90
80
atm
70
60
50
40 ethane
30
20
liquid water
10 Pressure +
9 liquid HC
8
ane
7
prop HYDRATE
6
FORMATION
5 ZONE
4
tane
2
isobu liquid water
+
ne vapor HC
n-buta
1
+ vapor HC
solid water
0,9
0,8
0,7
0,6
°C
D TH 008 A
0,5
-5 0 5 10 15 20 30
0°C Temperature

51
In order to avoid risks of plugging, the water content of propane must not exceed 0.01%, whereas the
water content soluble at 15°C is 0.016%.
Even in the absence of visible traces of water, the risk exists and the test with cobaltous bromide is
used to guarantee a sufficiently low content.
To minimise these risks, distribution companies sometimes add methanol to propane in winter.
Due to the relatively large size of their molecules, n-butane and n-butenes rarely form hydrates when
they are pure. However the presence of lighter hydrocarbons in commercial products may hydrate
formation possible.
Propane and particularly commercial propane form hydrates very easily on account of the presence
of ethane. This also applies to propylene.
In addition, the higher vapor pressure of propane implies greater expansion. Consequently the
temperature of gaseous propane circuits can be lower than for gaseous butane.
SUMMARY OF THE PROCEDURE

The propane to be tested is directed in vapor phase from under specified conditions through a plug of
cotton impregnated with cobaltous bromide, used as an indicator.
The change in color from blue to pink indicates the presence of water in the propane. The whole
apparatus assembly must be thorougly dried before the test.
Removable cap (to be

removed during the test)
Pressure gas
0.10 bars
4 6
Window on bath sides 2 8

0 10
Cottom
Cottom impregnated
with cobaltous Needle
bromide valve
Cobaltous bromide
Glass tube indicator
To be connected
to propane
container
vapor outlet
Cooling coil Ice bath

D ANA 020 B
Indicator Assembled apparatus
The test is carried out in two stages:

– at 50 psi (3.5 bar g) for 30 minutes
– at 7 psi (0.5 bar g) for 5 minutes

52
The test result is recorded as being a "dry" or "wet" propane, according to the observed colors of
the indicator after the two test stages.
RESULTS
COTTON COLOR
At the end of the first stage BLUE LAVENDER OR PINK
LAVENDER
At the end of the second stage BLUE PINK BLUE
OR PINK
RESULT dry propane wet propane wet propane wet propane*
* when it can be assumed by an additional low pressure test that the apparatus (fittings and tubing)
does not contain water.
Water contents required for color changes are 0.03% wt for the first stage and 0.02% wt for the second
one (lower presence). But the implementation of the two stages are mandatory to clarify the origin of
water as follows:
– dry propane but polluted with water brought by the apparatus
– wet propane but hydrate formation which retain water (change of c olor is not detected)
Note: Another standard test by an ASTM method for dryness of propane (valve freeze method) is
ASTM D 2713. The liquid-phase sample is directed through a specific test valve and the time required
for the valve to freeze is recorded (the liquid propane ceases to flow). The valve does not freeze within
60 sec, the product is considered as a "pass".

53
IV - TESTS RELATED TO THE CORROSIVENESS

OF PETROLEUM PRODUCTS AND TO POLLUTION
The combustion of petroleum products releases hot gases or fumes into the atmosphere and they can contain
noxious compounds:
- sulphur oxides, SO2 and SO3, from the combustion of the sulphurized constituents,
- gaseous unburnt products, such as carbon oxide, hydrogen and hydrocarbons,
- solid unburnt products, mainly carbon particles (soot),
- nitrogen oxides, from the reaction of nitrogen compounds or atmospheric nitrogen with
oxygen, depending on flame reaction.
Although the presence of unburnt products is related to the quality of combustion, the presence of sulfur and
nitrogen oxides is inevitable, because it is due to the sulphur and nitrogen content in the petroleum
products 1.
In other respects, the petroleum products are stored and handled in metallic tanks or lines. It is important, for
safety reasons, to avoid the corrosion of materials and equipment by petroleum products.
This corrosiveness is related to petroleum product constituents having acidic characteristics.
POLLUTION AND CORROSION BY SULPHUR

The problems of air pollution and corrosiveness are due largely to the sulphur compounds present in
petroleum products.
1- AIR POLLUTION
Generally speaking, all the sulphur present in combustibles and petroleum fuels is converted into
gaseous sulphur oxide (SO2).
The combustion of 1 kg of heavy fuel oil with a sulphur content of 4 wt% produces 28 liters of SO2
resulting in a concentration which can reach 2 liters of SO2 per cubic meter of fumes in the air. This
gas is considered to be dangerous for human and plant life once there is a proportion of 5 cm3 per
cubic meter in the air (5 ppm in volume).
In order to remain below this limit, two possibilities exist:
- either to release the exhaust fumes with extremely high chimneys (industrial solution),
- or to burn low sulphur content fuel oils.
But exhaust fumes from vehicles are discharged at ground level and home heating boilers discharge
theirs at relatively low height. Despite these combined efforts, air pollution remains a difficult problem
and the only solution consists in reducing the sulphur content of fuels.
1High percentages which can be encountered in petroleum residues:

S wt%: 6
N wt%: 2
54
Several standard methods for measuring the sulphur content in petroleum products are described
hereafter:
- sulphur content by the Wickbold method - CEN 41 - (NF T 60-142 in France), for light
products and distillates, such as gasolines, kerosenes, diesel fuel oils and home
heating fuel oils.
ASTM methods for equivalent products are:
D 129 - general bomb method

D 1266 - lamp method
D 2785 - Wickbold and Beckmann combustion apparatus (trace quantities).
- sulphur in petroleum products (high temperature method), generally using and

induction-type furnace) ASTM 1552, for heavy fuels (French method: NF 07025),
- sulphur content by the lamp method (NF 41009), technically equivalent to ASTM D
2784, for the liquefied petroleum gases,
- sulphur determination by X-ray fluorescence for all petroleum products (ASTM D 2622),
- sulphur trace analysis in light distillates by the micro coulometric method.
2- CORROSION DUE TO SMOKE OR EXHAUST FUMES

Part of the SO 2 formed by the combustion of sulphur is converted into sulphur trioxide when it comes
into contact with the oxygen in the air. This conversion is further increased by combustion with excess
air (which is the case in industrial boilers). Taking into account the above example, the combustion of 1
kg of heavy fuel could lead to a maximum production of 1.5 liter of SO3.
This trioxide is very dangerous from the corrosion point of view because with steam (and water) it
forms the very corrosive sulphuric acid: H2SO4.
In order to prevent the corrosiviness of furnaces and boilers using high sulphur content combustibles,
the smoke must be released at a temperature high enough to prevent the condensation of sulphuric
acid. Unfortunately, this means that little heat can be recovered from the smoke and lowers the
performance of the furnaces.
The condensation limit temperature is 150-170°C for heavy fuel combustion.
In spite of the low sulphur content in automotive fuels, corrosion of this kind does occur in car exhaust
pipes through condensation of the acid, once the engine is switched off and the exhaust pipe allowed
to cool.
Sulfur compounds in:

SO2
- gasolines/gas oils COMBUSTION SO3
- fuels
+ humidity
D PCD 311 B
Sulfuric acid
H2SO4

55
3- CORROSION BY ACIDIC COMPOUNDS

There is a method for determining the total content of acidic compounds, in petroleum cuts, and the
corresponding standard test is:
- neutralization number by color-indicator (total acid number or strong acid number).
The acid number gives an indication of the corrosiveness of certain constituents in relation to the
choice of equipment, material, inhibitors and specific treatments with respect to the particular petroleum
product.
Other tests attempt to simulate the behaviour of corrosive petroleum products in contact with metallic
surfaces such as copper, at relatively high pressures and temperatures:
- detection of copper corrosion from petroleum products by the copper strip tarnish
test for petroleum products except LPG (from gasoline to distillate fuel and lubricating
oil) (ASTM D 154).
- copper strip corrosion by liquefied petroleum gases (ASTM D 1838).

56
SULFUR CONTENT OF PETROLEUM PRODUCTS

BY THE WICKBOLD COMBUSTION METHOD
– NF EN 24260 –
The Wickbold method is used to measure the total sulfur content of gasolines, white spirit, kerosenes, diesel
oils and home heating fuel oils.
PRINCIPE AND PROCEDURE

A fixed quantity of the product sample is burnt in a closed system. The sulfur oxides (SO2 and SO3), formed
during the combustion of the sulphur constituents of the product are absorbed and oxidized to sulphuric acid
(H 2SO4) in a hydrogen peroxide solution (H2O2).
The sulphate ions are titrated to determine the amount of sulphuric acid, by which the sulphur content of the
sample can be calculated.
The combustion is carried out in the Wickbold apparatus, of which a simplified description is given hereafter.
To vacuum
Liquid trap
Water exit
Combustion chamber Burner-atomizer

in quartz in metal
Oxygenated water
solution
Secondary
oxygen
ABSORBER Primary
oxygen
Cooling water of Hydrogen
combustion chamber
D ANA 102 B
Sample to
burn
Three way trap
To titration
The sample is injected into the flame of a burner fed by oxygen and hydrogen. The very high flame
temperature (about 1 800°C) enables the complete combustion of all the sulfur constituents present in the
sample.
Result: the result is expressed as the total sulfur weight percentage.

57
SULFUR IN LIQUEFIED PETROLEUM GAS

(Lamp Method)
– AASTM D 2784 –
– NF 41-009 –
This test determines the quantity of sulfur present in the form of hydrogen sulfide (H2S), mercaptans (RSH),
sulfides (RSR), carbonyl sulfide (COS) but not element sulfur.
The sample is burnt in a lamp in a closed system in a carbon dioxide-oxygen atmosphere. The sulfur oxides
are absorbed and oxidized to sulphuric acid in a hydrogen peroxide solution. The sulfur in then measured by
titration as in the Wickbold method.
The method is applied to liquefied petroleum gas (LPG).
Stainless steel
sample bomb To vacuum manifold
Relief valve
(300 psi)
Attach burner Stray trap
21 kg per sq cm Thermometer
here
Needle
valve Absorber
12
12
12
Chimney
12
12
12
12
12
12
12
Stainless steel 12
12
12
12
12
tubing and CO2-O2

connections to chimney
Sintered glass
CO2-O2 filter
to burner
D ANA 1056 A
Regulating valve maintained at

100° F by heating tape
(4-ft length, 140 W, 45 V) From CO2-O2
Controlled by a transformer manifold
LPG DISTRIBUTION AND LAMP DESCRIPTION

For very low sulfur contents (about < 5 ppm) a turbidimetric titration is carried out with the use of an
absorption cell and a photometer.
Result: sulfur contents is expressed in mg/kg, or in ppm, or in weight percentage.

58
SULFUR DETERMINATION IN ALL LIQUID PETROLEUM

PRODUCTS BY THE X-RAY FLUORESCENCE METHOD
– ASTM D 2622 –
This method covers the determination of total sulfur in liquid petroleum products. The applicable concentration
range varies with the instrumentation and will generally be situated from 50 ppm to 10%.
SUMMARY OF METHOD AND PROCEDURE

When X-rays are focused on any sample containing atoms whose atomic weight is higher than 20 they can be
absorbed by the 2 electrons near the nucleus at level K. The electrons leave their orbit and are ejected.
Electrons from the upper levels L or M will replace them and will then emit X-ray radiation called
fluorescence. The wave-length of this radiation is a characteristic of the atom from which it has been emitted.
The main advantage of this technique is that the electrons concerned are those near the nucleus. This means
the atom will give the same signal whatever the other atoms with which it is bounded.
It then permits a total atom determination.
In the case of sulfur in petroleum products the sample is placed in the X-ray beam and the intensity of the K
line of fluorescence at 5.373 A° is measured.
The apparatus is rather heavy and expensive as it includes:
- an X-ray tube with tungsten or chromium target,

- analysing crystals for resolution of wavelength,
- pulse height analyser for energy discrimination,
- detector designed for detection of long wavelength X-rays,
- a vacuum system or a helium flow circuit as X-rays are absorbed by air,
- the equipment is also well protected as the intensity of X-rays is high and can be very
dangerous for the body.
The results are obtained by counting the X-rays obtained for the sulfur atom.
A calibration curve is necessary for 2 reasons:
- the method is essentially a comparative method and is not absolute,

- there is sometimes an important matrix effect due to the absorption of the X-rays emitted
by the surrounding atoms.
Precision varies according to the sulfur content as it covers a very wide concentration range. As a rule it is
from 2 to 10%.
Knowledge of the presence of sulfur in petroleum products, especially fuels, helps to predict performance
characteristics and potential corrosion problems.

59
SULFUR TRACE ANALYSIS IN LIGHT DISTILLATES

BY THE MICROCOULOMETRIC METHOD
– ASTM D 3120 –
The test permits the determination of traces of total sulfur in light distillates. It covers the concentration range
from 0.5 to 100 ppm.

The liquid sample is injected into a combustion tube maintained at about 800°C having a flowing stream of
gas containing 80% oxygen and 20% inert gas (N 2 or Ar).
Oxidative pyrolysis converts the sulfur to sulfur dioxide which then flows into a titration cell where it reacts with
triiodine ion present in the electrolyte. The triiodine consumed is coulometrically replaced and the total
current required to replace it is a measure of the sulfur present in the sample injected.
The reaction occuring is:

-
I 3 + SO2 + H20 Æ SO3 + 3 I- + 2 H+
The trioodine ion is generated coulometrically:

-
3 I- Æ I3 + 2 e-
The apparatus includes a pyrolysis furnace which is connected to the titration cell. The electrodes are
connected to the electronic device to produce the electrolytic current and to measure and record the total
current.
Micro
coulometer
Recorder
Titration Syringe
(potential)
cells
D ANA 105 B
N2 O2
Combustion tube
800°C
The sample is injected with a 10 µl syringe. Calibration is made with a known or synthetic reference sample.
Precision of the method is generally better than 10% at the 10 ppm level.

60
NEUTRALIZATION NUMBER BY COLOR–INDICATOR TITRATION

(Acid number of petroleum products)
– ASTM D 974 –
This method covers the determination of acidic or basic constituents in petroleum products (including
lubricating oils, but excluding bituminous products and greases), soluble in mixtures of toluene and isopropyl
alcohol.
The constituents in new or used petroleum products or oils considered to have acidic characteristics mainly
include organic or inorganic acids, esters, phenolic compounds, heavy metal salts and addition agents such
as inhibitors and detergents.
These acidic characteristics can be measured as the total acid number (TAN).
The mixture (petroleum products + toluene + isopropyl alcohol) is titrated by a potassium hydroxide solution
(KOH).
A color change in the colored indicator solution indicates the end of neutralization.
The total acid number is then the quantity of base, expressed in mg of KOH, that is required to neutralize
all acidic constituents present in 1 g of petroleum product sample.
The method also determines the strong acid number which is the quantity of KOH, expressed in mg,
required to neutralize the "strong acidic compounds" extracted from 1 g of sample, by boiling water
extraction (water phase titration).

61
COPPER STRIP CORROSION

BY LIQUEFIED PETROLEUM GASES (LPG) - ASTM D 1838 -
BY PETROLEUM PRODUCTS - ASTM D 130 -
These methods cover the detection of the corrosiveness to copper of LPG and petroleum products by the
presence of corrosive constituents such as element sulphur (S) and hydrogen sulfide (H2 S).
SUMMARY OF METHODS AND PROCEDURE
Upper valve
Cover
A freshly polished copper strip is immersed in a
given quantity of sample and heated at a
Vapor phase temperature and for a time characteristic of the
product being tested.
Immersion tube
The bomb shown is used for LPG test (proof
Liquid level pressure: 1000 psig or 70 bar). In the case of the
other petroleum products:
- the test bomb has a similar shape (test

Copper strip pressure 7 bar)
- or the copper strip is placed in test

tubes in a thermostat bath.
The following table gives the test operating

conditions for different petroleum products.
Lower valve
D ANA 090 B
— Test bomb —
PRODUCTS TEST CONDITIONS
- LPG 1 hr in a bomb at 100°F (37.8°C)

- Aviation gasoline and aviation turbine fuel 2 hrs in a bomb at 212°F (100°C)
- Natural gasoline 3 hrs in a bomb at 104°F (40°C)
- Diesel fuel, fuel oil and automotive gasoline 3 hrs in a bath at 122°F (50°C)
- Cleaner solvents and kerosene 3 hrs in a bath at 212°F (100°C)
- Lubricating oils Various durations and elevated temperatures

62
The copper strip is then withdrawn, immersed in washing solvent, and dried. The interpretation of the test is
based on the inspection of signs of tarnishing or corrosion by comparison with the copper strip corrosion
of standard strip plaques, according to the following strip classifications table.
Classification Designation Description
Freshly polished strip
1 Slight tarnish a - Light orange, almost the same as a freshly

polished strip
b - Dark orange
...
2 Moderate tarnish a - Claret red

... b - Lavender
... c - Multicolored with lavender blue and/or silver
overlaid on claret red
d - Silvery
... e - Brassy or gold
...
3 Dark tarnish a - Magenta overcast on brassy strip

... b - Multicolored with red and green showing
(peacock), but no grey
4 Corrosion a - Transparent black, dark grey or brown with

peacock green barely showing
b - Graphite or lustreless black
c - Glossy or jet black
These classifications are given in increasing order of corrosiveness of the samples.
RESULTS
The corrosiveness of the sample is expressed as number 1, 2, 3 or 4 as shown in the table, depending on the
standard to which it conforms. The colorations a, b, c, d are interpreted according to the description in the
table or by reading the reverse side of the standard plaque.
The standard method IP 227 indicates corrosion tests for turbine aviation fuels on silver strip. The test
conditions are 4 h at 50°C. Results are also expressed as a number corresponding to standard silver
strip plaques.

63
MERCAPTAN CONTENT
I- DOCTOR TEST – IP 30 - ASTM D 235 – ASTM D 4952 - 89 –

This method is intended to qualitatively detect mercaptans in motor gasoline, kerosene and similar
petroleum products (with an ASTM end point lower than 300°C).
PROCEDURE
Shake vigorously together in a test tube 10 mL of the solvent being tested and 5 mL of sodium plumbite
solution for about 15 s. Add a small amount of pure, dry flowers of sulfur so that practically all of it floats on
the interface between the solvent and the sodium plumbite solution after shaking. Shake again for 15 s. Allow
to settle and observe within 2 min.
RESULTS
If the solution is discolored or if the yellow color of the sulfur film is noticeably masked, consider the test
positive and report the solvent as sour. If the sample remains unchanged in color and the sulfur film is bright
yellow or only slightly discolored with grey or flecked with black, consider the test negative and report the
solvent as sweet.
If the doctor test is positive, mercaptan content may be determined using Test Method D 3227 (Potentiometric
method).
This method is also used for detecting H2 S in commercial butane (liquefied petroleum gases) (ASTM
1838 - NF M 41-006)
IN SHORT
DOCTOR TEST IS POSITIVE: – presence of H2S and/or mercaptans

– change of color
DOCTOR TEST IS NEGATIVE: – very small quantities of H2S and/or mercaptans
(generally below 5 g/ton)

– no color change

64
II - MERCAPTAN SULPHUR IN GASOLINE, KEROSENE, AVIATION TURBINE AND

DISTILLATE FUELS - ASTM D 3227
The test covers the determination of sulphur as mercaptans R-S-H.
PRINCIPLE AND PROCEDURE

Mercaptans react with a silver nitrate solution and precipitate as silver mercaptide
Ag NO3 + R-S-H Æ R-S-Ag + HNO3

Silver nitrate precipitate
The reaction is titrated potentiometrically using the potential between two electrodes as an indicator. The end
point of the titration is shown by a considerable change in the cell potential. The quantity of Ag NO 3 required
to reach the end point for a fixed volume of the treated sample serves to calculate the weight of sulphur
present as mercaptans in the sample.
RESULTS
The result is expressed as mercaptan sulphur content wt% and the method is applicable to petroleum
products containing from 0.0003 wt% to 0.01 wt%.
The chief disadvantage where mercaptans are concerned is their extremely unpleasant odour. They are
generally non-corrosive.

65
V - TESTS RELATED TO THE CHEMICAL NATURE OF PETROLEUM

PRODUCTS AND TO OXIDIZING CONDITIONS - STABILITY OF PRODUCTS
The properties of petroleum products are obviously related to their chemical nature.
Crude oils are mixtures of many substances, whose proportions are as follows :
- hydrocarbons (from 93 to 99 wt%), divided into the main families : paraffinics, naphthenes,
aromatics,
- sulphur (0.04 t 6 wt%),
- oxygen (0.1 to 1.5 wt%),
- nitrogen (0.1 to 1.5 wt%),
- metals (0.005 to 0.015 wt%), mainly as vanadium.
Refining generally consists in modifying the chemical nature to some extent in order to manufacture the
commercial petroleum products.
In this particular case, it is necessary to carry out analyses, which are used either to orient the refining
processes or to check the base or finished petroleum products. Among these analyses, some tests related to
the chemical nature of products are described hereafter.
- determination of hydrocarbon structures
• hydrocarbon types in liquid petroleum products by fluorescent indicator

absorption - D 1319,
• refractive index
• aniline point - ASTM D 611 - for petroleum distillate fractions
- determination of specific compounds
• basic water and sediments - ASTM D 1797 - for crude oils only
• water in petroleum products - ASTM D 95
• jet fuel behaviour in the presence of liquid water
water reaction - ASTM 1094
water separation characteristics - WSIM
• sediment in crude and fuel oils - ASTM D 473
• asphaltene content in crude oils, diesel and fuel oils - IP 143
- element contents
• metals such as vanadium and Ni,

• nitrogen - ASTM D 4629
Vanadium is recovered as vanadium ashes from deposits on furnace walls or from flue gases and
specifications of fuel uses limit its content.
It is very useful to know these other element contents when using catalytic conversion processes on distillates
or residues.
Modern determination of the elements is mainly carried out by physical spectral analysis such as flame
emission or atomic absorption spectrometry, etc.

66
Moreover it is useful to know the behaviour of certain petroleum products (particularly when manufactured
partly through conversion processes which cause olefins formation) during storage with the presence of air
(oxidation) or under particular atmospheric conditions (wetness, warmnes). Among the most important
tests in this respect the following may be noted :
- stability test for motor gasolines, turbine fuels and distillates
• existent gum in fuels - ASTM D 381

• oxidation stability (induction period method) - ASTM D 625
• oxidation stability (potential residue method) - ASTM D 873
• oxidation stability (diesel) - ASTM D 227-4
- Olefin or diolefin content in petroleum distillates which have a tendency to form

gums
• Bromine number of petroleum distillates - ASTM D 1159

• Maleic anhydride value - UOP 325 - 58
• Diene value - UOP 326 - 65
- Thermal stability of jet fuels (JFTOT - ASTM 3241)
- Residual fuel oil stability (spot test - ASTM D 2781 and hot filtration test - SHFT
SMS 2966, no international standard at present) or Insoluble content (asphaltene precipitation
and solid impurities) in liquid fuels - NF M 07-063.
- Color-stability of color

67
HYDROCARBON TYPES IN LIQUID PETROLEUM PRODUCTS

BY FLUORESCENT INDICATOR ADSORPTION (F.I.A.)
– ASTM D 1319 –
This method can be applied to liquid petroleum products that distill below 315°C (600°F) and covers the
determination of % volumes of:
- saturates (paraffins and naphthenes)

- olefins
- aromatics
The sample is poured into the top of a special glass adsorption column packed with activated silica gel. When
all the sample has been adsorbed on the gel, isopropyl alcohol is added to desorb the sample and force it
down the column. The presence of a fluorescent indicator makes the boundaries of the aromatic, olefin and
saturate zones visible in different colours under ultraviolet light.
l1 Blue area Aromatics
l2 Yellow area Olefins
l3 Not fluorescent Saturated

area hydrocarbons
D ANA 106 B
The lengths l1 , l2 , l3 are proportional to the volume percentages of the three types of hydrocarbon. The
saturates, which have the lowest polarity, are displaced more easily by the isopropyl alcohol and the very
polar aromatic compounds are displaced less easily.

68
REFRACTIVE INDEX FOR PETROLEUM PRODUCTS
– ASTM D 1747 –
The test method covers the measurement of refractive indexes, to the fourth decimal place, of transparent and
light-coloured hydrocarbon liquids and melted solids having refractive indexes in the range 1.33 to 1.60.
The refractive index is the ratio of the velocity of light in air to its velocity in the substance examined.
It is defined as the sine of the angle of incidence divided by the sine of refraction as light passes from air
into the substance.

The refractive index is measured by the critical angle method using monochromatic light from a sodium lamp.
The instrument is previously ajusted by means of calibration obtained with certified liquid standards. The
apparatus is called a refractometer and is used only for this purpose. It contains a prism assembly which
can generally rotate until the refracted light is extinguished. Measurement is made with the eye. The prism is
thermostated as the refractive index varies with the temperature. A source of light is used which is generally a
sodium arc lamp. A thermomoter gives the exact temperature.
Two types of apparatus are currently available
- measurement after transmission of the light,

- measurement after reflexion of the light.
The second apparatus can be used for dark samples.
Recent refractometers are automatic and give a digital result making it unnecessary to look at the beam with
the eye and to move the prism.
The quality of the results depends upon :
- the darkness of the sample,

- the quality of the temperature controller,
- sometimes on the capability of the operator to see the beam clearly.
Automatic equipment has brought definite improvement, giving precision to the fourth decimal place.
The refractive index is a fundamental physical property that can be used in conjunction with others to
characterize pure hydrocarbons and their mixtures.
The use of the refractive index in correlative methods for the determination of composition of heavy distillates
requires its measurement with precision and sometimes at high temperatures (70°C).
The (n, d, M) method is still often used for the calculation of paraffins, aromatics and naphthenes in
heavy cuts.

69
ANILINE POINT
– ASTM D 611 –
The aniline point is defined as the lowest temperature at which equal liquid volumes of aniline and the
petroleum product are miscible. The measurement of the aniline point is carried out by slowly cooling the
mixture initially heated to a temperature higher than the expected aniline point. The complete miscibility is
observable when a distinct cloud appears inside the mixture.
The aniline point is related to the chemical nature of the petroleum cut and particularly to the aromatic
content. Aniline is a solvent with an aromatic character (aromatic amine) and thus gives a good miscibility
with aromatic petroleum products. These types of petroleum products have a low aniline point.
On the contrary a mixture with petroleum cuts rich in paraffins leads to two distinct phases due to their
different chemical nature. The miscibility temperature and consequently the aniline point, are higher.
Examples:
- aniline point of benzene: + 30°C
- aniline point of n-hexane: + 69°C

70
WATER AND SEDIMENTS IN PETROLEUM PRODUCTS
WATER IN PETROLEUM PRODUCTS AND BITUMINOUS MATERIALS BY

DISTILLATION - ASTM D 95 -
The water content limit is around 1.5% in weight

for heavy fuels. The actual content of heavy fuels
is generally below this figure. Condenser
Summary of method: the petroleum cut is

heated under reflux with a water-immiscible
solvent (xylene, light petroleum distillate) which
codistills with the water in the sample. The
condensation of vapors in a trap makes it
possible to read the volume of water and then to
record the result as wt % of the sample.
Trap
It is to be noted that if emulsified water in fuel is
generally favorable to combustion, free water
Sample
could on the contrary be a problem. Glass
still
D ANA 114 B
SEDIMENT IN FUEL OILS BY EXTRACTION - ASTM D 53 -
In this method, all matter which is insoluble in hot toluene is called sediment.
Stainless steel wire

The sample, in a refractory thimble, is extracted
Condenser by hot toluene until the residue reaches constant
weight.
Extraction
flash This weight, as wt % of the sample, is recorded
as sediment.
Water cup
The remaining residue is generally of mineral
Extraction origin (metallic particles, sand, etc.). The main
cartridge problems caused by this matter are:
D ANA 107 B
Solvent - filter plugging,

- burner erosion.
Top of
hot plate

71
WATER AND SEDIMENT IN CRUDE OILS AND FUEL OILS BY CENTRIFUGE

- ASTM D 1796 -
This method covers the determination of water and sediment by means of the centrifuge. It is applied mainly
to crude oils and called B.S.W. (Basic Sediments and Water).
The test result is recorded as volume % of water and sediments in the sample, but the water content and the
sediment content cannot be individually determined.
The sediments in this test include only the solid impurities, not the asphaltenes which remain in the solution
mixture of 50% sample and 50% toluene, used as solvent, at 50°C.
This B.S.W. measurement is of major importance in calculating the actual quantities of crude oils
which feed the refineries (B.S.W. generally below 1%).

72
JET FUEL BEHAVIOUR IN THE PRESENCE OF LIQUID WATER
Jet fuel behaviour can be assessed through two standard tests.
WATER REACTION OF AVIATION FUELS - ASTM D 1094

(This method is also used for aviation gasoline).
This test allows detection of surfactant compounds in jet fuels by their effect on the water-jet fuel
interface. As a matter of fact, the presence of surfactants gives rise to emulsions which may pass through the
separator filters entraining water and particles. The test, which aims at extracting water from the jet fuel,
consists in shaking the sample, according to a standardized technique, at room temperature in the presence
of phosphate buffer solution (prepared from K 2 H PO4, KH2 PO4 and water). The higher the surfactant
content, the more difficult the decantation. The change in volume of the aqueous layer, the appearance of
the interface and the degree of separation of the 2 phases are taken as indications of the water reaction of the
fuel.
Contrary to the Issue 14 (December 1990), the issue 15 (from September 1994) only contains one
specification concerning the test: the appearance of the interface using a standardized scale graduated
from 1 to 4: 1 b maximum.
Interface conditions Separation
Rating Appearance Rating Appearance
1 Clear and clean (1) Complete absence of all emulsions

and/or precipitates within either layer or
1b Small, clear bubbles covering not more upon the fuel layer
than an estimated 50 % of the interface
and no shreds, lace, or film at the (2) Same as (1), except small air bubbles or
interface small water droplets in the fuel layer
2 Shred, lace, or film at interface (3) Emulsions and/or precipitates within

either layer or upon the fuel layer,
3 Loose lace or slight scum or both and/or droplets in the water layer or
adhering to the cylinder walls, excluding
4 Tight lace or heavy scum or both the walls above the fuel layer
Microseparatometer (MSEP) (ASTM D 3948)
Like the Water Reaction, the MSEP indicates the ease of separation of emulsified water and Jet A1, which is
affected by the presence of surfactants.
The Microseparatometer is a portable apparatus which may be used both in site and in the lab. The test
duration is between 5 and 10 min.

73
The test consists in creating a water/fuel sample emulsion (50 ml of jet A1 + 50 µl of distilled water) in a
syringe using a high-speed mixer. The emulsion is then expelled from the syringe, using a standardized
process, through a standard fisher-glass coalescer. The effluent is then analyzed by light transmission. If the
coalescence is easy (i.e. if jet A1 easily liberates water), light transmission will be high and the result will be
expressed by a figure close to 100; on the other hand if the emulsion is difficult to break (difficult
coalescence), the result will be near 0.
Specifications are as follows:
85 minimum
70 minimum if the product contains an anti-static additive which reduces water coalescence
(S.D.A.: Static Dissipater Additives).
Settle free water is eliminated by drainage in storage. Separating filters are used during distribution
operations, to restrict the moisture content to 5 ppm. Shell water-detector pellets, which are naturally yellow
but turn green in the presence of moisture, are used as a final check.

74
ASPHALTENE PRECIPITATION WITH NORMAL HEPTANE
– IP 143 –
Residues consist of heavy hydrocarbons. Some of which have a very high molecular weight and are very
rich in carbon. Most of metals such as nickel and vanadium are concentrated in them. Their nature is still not
well defined and is very different from one crude to another. These compounds are called asphaltenes.
By definition, the asphaltene content of a petroleum product topped at a temperature of 260°C (gas oils,
diesel fuels, fuel oils, lubricating oils, bitumens and crude oils) is the percentage of wax-free material
insoluble in n-heptane but soluble in hot toluene (distillation under reflux with n-heptane and extraction
with toluene, or benzene).
(In some countries, n-pentane is used in place of n-heptane. In this case, "asphaltene content" is higher).
The composition of a residue can be represented as follows:
RESIDUE
MALTENES
ASPHALTENES
oil medium
Soluble Insoluble
in n-heptane in n-heptane
The presence within the oil medium of constituents with characteristics common to both asphaltenes and
to the rest of the oil medium causes the asphaltenes to remain suspended in the residues. These
hydrocarbons have a high molecular weight and a pronounced aromatic nature. The constituents, called
resins, have a double affinity for asphaltenes and for oil hydrocarbons, and this makes the asphaltenes more
or less soluble in the oil.
The following figure schematically illustrates the structure of residues.
Oil
Resin Asphaltene
D CH 141 B

75
On a microscopic scale, a residue therefore does not have the characteristics of a homogenous solution; it is
colloidal system. The continuous phase consists of the oil hydrocarbons, in which saturated hydrocarbons
(S) and aromatics (A) can sometimes be distinguished. The dispersed phase, on the other hand, is composed
of resin and asphaltene associations called micelles. Asphaltenes are also said to be peptized by the resins
and have thereby dispersed in the residue. These different factors can be seen in the following table:
RESIDUE
MALTENES ASPHALTENES
(oil medium)
OIL RESINS ASPHALTENES
Saturated HC + Aromatics 123
peptization
Continuous phase Dispersed phase
Micelles dispersed in the oil
The degree to which asphaltenes in residues can be peptized to from micelles depends on their nature, which
in turn is related to the source crude and to the thermal treatments they have undergone. Depending on its
composition, the oil medium peptizes or dissolves the asphaltenes in the residue to varying degrees.
A residue is stable and homogenous in aspect if the asphaltenes are entirely dispersed in the liquid
phase in the form of micelles. This can only occur if the available solvent power of the maltenes is greater
than the solvent power required by the asphaltenes. If this condition is not fulfilled the residue is unstable, i.e.
the non-dispersed asphaltene fraction precipitates and causes the formation of deposits. This
phenomenon is known as flocculation of the residue.

76
VANADIUM CONTENT IN HEAVY PETROLEUM

FRACTIONS BY ATOMIC ABSORPTION
– ASTM D 3605 –
The method covers the determination of vanadium, and also sodium, lead, calcium in fuels in the range 0.1 to
10 mg/l.

Each element placed in the appropriate situation is able to emit or to absorb specific wavelengths
characteristic of the element.
When elements are ionized by heat energy they absorb their own characteristic lights. When then elements
are placed in a beam of the corresponding wavelength, the beam will be absorbed and the absorbance will be
proportional to the number of atoms or ions encountered.
The measurements of vanadium by atomic absorption requires a lamp emitting vanadium rays.
The apparatus consists of an atomic absorption spectrometer which contains;
- a burner which in the case of vanadium will be fed by a mixture of nitrous oxide and acetylene,
- a nebuliser which sprays the droplets of the sample into the flame,
- one vanadium hollow cathode lamp to produce the correct wavelength,
- a monochromator capable of resolving the various wavelengths,
- an electronic detection system to measure with accuracy the absorbance of the light when the
sample is in the flame.
It is easily seen that the sample should be in liquid form to be pumped and sprayed.
Heavy residue should be diluted.
Different but known amounts of analyte are added to two portions of sample. These, tog ether with the
unaltered sample, are burned in the flame of the atomic absorption spectrometer that measures light
absorption by the atomized metal. The analysis of the sample portions with added analyte provides the
calibration information necessary to calculate the vanadium content of the sample.
Precision and sensitivity are not always good and this determination is better performed by I.C.P. (Inductive
Coupling Plasma), which is not yet standardized.

77
VANADIUM AND NICKEL CONTENT BY I.C.P.

The method is an emission spectroscopic method and the element to be analysed is excited until it emits its
electronic emission spectra.
With this method, the energy source is quite different from the others as it is an argon plasma inducted by a
high frequency (27 to 60 MHz) (Inductive Coupling Plasma).
As a result, very high energy is fed to the elements which enter the plasma and the population of atoms
excited and emitting their spectra is much larger than with the other sources.
This leads to higher sensitivity in detection.
The equipment is an inducting coupling plasma which uses a very high frequency electric field applied to a
flow of argon. The sample is liquid and injected into the plasma itself. A monochromator is used to separate all
the wavelengths. A detector gives a measure of the intensity of the light for a given wavelength. Several
elements may be analysed in a sample at one time.
The results are obtained with reference to standards:
- sensitivity is generally 10 times the atomic absorption,

- there is very little interference between elements,
- the concentration range is very wide.
Knowledge of the presence of trace metals (V, Ni, Na) is important in fuels mainly for corrosion or for
catalytic treatment purposes.

78
NITROGEN DETERMINATION IN LIQUID PETROLEUM HYDROCARBONS

BY OXIDATIVE COMBUSTION AND CHEMILUMINESCENCE DETECTION
– ASTM D 4629 –
The method covers the determination of the total trace nitrogen in liquid hydrocarbons boiling in the range
50°C to 400°C.
This test is applicable to naphthas, distillates and oils containing 0.5 to 100 ppm nitrogen.

The sample of liquid petroleum hydrocarbon is injected into a stream of inert gas (He or Ar). It is vaporised
and carried to a high temperature zone where oxygen is introduced. Combustion occurs and nitrogen is
converted to nitric oxide (NO). The water formed in combustion is absorbed. The gas containing NO is sent
to a zone where ozone (O 3) is produced. NO is converted into excited NO2, which emits a fluorescent light
while returning to normal state.
*
NO + O3 Æ NO2 + O2
*
NO 2 Æ NO2 + photon (h u)
The light is detected by a photomultiplier and the resulting signal is a measure of the nitrogen contained in the
sample.
The quantitative results are obtained after making a calibration curve with standards covering the range of
operation and consisting of nitrogen type and matrix similar to samples to be analysed.
For the high boiling point products boat injection should be used.
Precision depends greatly on the concentration and the matrix of the sample.
According to the concentration, the reproductibility is said to be:
Concentration (ppm) Reproductibility
1 0.85
10 3.0
100 10.0
Some process catalysts used in petroleum and chemical refining may be poisoned when trace amounts of
nitrogenous material are contained in the feedstock.
This method controls low nitrogen content in feeds and finished products.

79
STABILITY TESTS FOR MOTOR GASOLINES,

TURBINE FUELS AND DISTILLATES
Cat-cracked gasolines contain a large percentage of olefins and occasionally a small proportion of diolefins.
Steam cracked gasolines contain high percentages of olefins, diolefins, and styrenic compounds.
Chemically speaking, these products are less stable than the other elements in gasolines. In actual fact,
these compounds are polymerised through chemical reactions once they have come into contact with the
oxygen dissolved in the fuel. In other words, new, more complex molecules in the form of deposits, called
"gum" (residue), are formed from the amalgamation of a certain number of molecules.
This also depends on storage time.
THE FORMATION OF GUM

– only takes place ,when oxygen is present
– is at first very slow but then gathers speed. The delay before oxidation occurs corresponds to
the measurement of the induction period
– only increases if more oxygen is dissolved
– is accelerated by the action of heat and light
– is inhibited by additives

80
EXISTENT GUM IN FUELS BY JET EVAPORATION
– ASTM D 381 –
This is the gum present at the time when the measurement is made. It excludes, therefore, gum which might
form after prolonged storage.
The amount of existent gum is the residue obtained after the product has been blown by hot air or steam
and is measured in mg/per 100 ml. The operation is carried out at about 160°C for aviation and motor
gasolines (air jet) or at about 235°C for turbine fuels (steam jet).
Thermometers
Cotton or glass
wool filter Flowmeter
Air inlet
Steam supply Copper mesh Removable

adapter
Superheater
Metal block
bat
D ANA 109 B
Sample
Thermostat

81
OXIDATION STABILITY OF GASOLINE

(Induction period method)
– ASTM D 525 –
This feature is particularly important when products

have to undergo prolonged storage.
The gum is measured by aging the fuel rapidlly and then

placing it in an oxygen-pressurised apparatus (bomb) at
100°C.
The amount of residue obtained enables assessment of

the amount of potential gum, and then provides an
indication of the tendency of motor gasolines to form
gums during storage (see ASTM D 873 on the following
page).
In the induction period method the "break

point" time is the moment when a drop in the
oxygen pressure (2 psi in 15 min) can be
observed.
This corresponds to the deterioration of the product.
The result is recorded as the induction period at

100°C in minutes (period between the time when the
bomb is placed in the bath and the "break point" time).
D ANA 1084 A
Bomb for oxidation stability test of gasoline

82
OXIDATION STABILITY OF AVIATION FUELS

(Potential residue method)
– ASTM D 873 –
This method is applicable to aviation reciprocating, turbine and jet engine fuels.
The fuel is oxidized at 100°C in a pressurized oxygen atmosphere (pp O2 = 7 bars) in the same bomb as
that described in ASTM 525.
The amounts of soluble gum, insoluble gum and precipitate formed are weighed (soluble gum is
weighed by the same method as the one used in the ASTM 381 method by jet evaporation).
RESULTS
Calculate the results obtained by combining the separately determined residues and record the total result as
X hours potential gum, in mg/100 ml.
X hours represents the time of the chosen accelerated aging period.
Example: 16 hours potential gum: 6 mg/100 ml maximum for an aviation reciprocating fuel (USA military
grade 115-145).
D ANA 1084 A
Oxidation bomb
83
OLEFIN AND DIOLEFIN CONTENT
Some standard tests enable assessment in the laboratory of the olefin and diolefin content and consequently
indicate the tendency of a petroleum cut to form gums.
BROMINE NUMBER OF PETROLEUM DISTILLATES BY ELECTROMETRIC TITRATION -

ASTM D 1159
The petroleum sample - distillation range from C 5 to ASTM 90% less than 325°C - is mixed with
trichloroethane and a titration acid solvent, and maintained at a temperature between 0 and 5°C. Then a
bromide-bromate solution is added in small doses by means of a graduated buret.
The bromine atoms released in an acid medium react with the double bonds (only one per molecule in
the case of polyolefins).
The end point of titration is indicated when the presence of free bromine causes a sudden change in the
electrical conductivity of the system (electrometric titration).
By definition, the number of grams of bromine that will react with 100 g of the sample is recorded as the
bromine number.
Examples:
- pure 3 ethyl-1-pentene has a bromine number of 173,

- pure 2, 3-dimethyl - 1,3 butadiene has a bromine number of 186 (theoretically 389 for such a
diolefin),
- pure benzene has a bromine number of 0.
For commercial gasolines which come from a blend of straight-run, reformed and cracked gasolines, an
approximate value of olefin concentration can be calculated as follows:
BxM
olefins, wt% = f x
160
f : boiling range correction between 0.7 to 1

(0.7 for 250°C boiling range, 1 for 0°C boiling range)
B : bromine number
M : average molecular weight of olefins vs 50% boiling point (table below)
160 : molecular weight of Br2 (ASTM 875)
50% ASTM dist. Olefin molecular weight
50 77
75 87
100 99
125 113
150 128
175 144
200 161
225 180
250 200

84
MALEIC ANHYDRIDE VALUE: MAV - UOP method 325-58

The method gives an indication of the diolefin content of the sample. But some other compounds such as
styrenic and indenic, and polyaromatic ones can also react (vinyl aromatics, anthracene).
Maleic anhydride is refluxed with sample in boiling toluene for 3 hours (Diels Alder reaction).
H H MW = 98.06
C C
O C C O
MAV is recorded as mg of maleic anhydride reacting with 1 g of the sample.
DIENE VALUE BY MALEIC ANHYDRIDE ADDITION REACTION - UOP method 326-65

Diene value is defined as the number of grams of iodine equivalent to the amount of maleic anhydride that
reacts with 100 grams of sample, giving the formula:
M.A.V.
Diene value =
3.86
98.06 1
from 3.86 = x
253.82 10
With the molecular weight of iodine (I2) = 253.82

85
THERMAL OXIDATION STABILITY OF AVIATION TURBINE FUELS

(JFTOT procedure)
– ASTM D 3241 –
JFTOT stands for Jet Fuel Thermal Oxidation Tester.
This method is to assess the thermal stability of a jet fuel in the JFTOT. A sample of jet fuel is circulated for
2 h 30 min at 260°C at a fixed rate of 3 ml/min through a heated tube and then through a stainless steel filter
where degradation products are trapped.
The result of this test is expressed in terms of the deposit rating of the appearance of the heater tube
according to a standard scale and in terms of the degree of filter plugging, which is measured by the loss of
the DP charge of the filter (DP is measured in mm of mercury).
This test relates to the performance of jet fuel on board an aeroplane where it can come into contact with
heated metallic structures.
The test section compartment is represented below:
Cooling
Pump
Nitrogen Flowrate indicator

inlet
Test
filter
Piston
∆P
Heating tube
Fuel tank
(600 ml of Temperature
D ANA 110 B
sample) controller
Pre-filter
membrane

86
OXIDATION STABILITY OF DIESEL FUELS
– ASTM D 2274 –
This test consists in ageing an oil in order to quantify the sediment and gum precursors, particularly nitrogen
heterocyclic compounds (for instance, indole) and aromatics containing an olefin bond (for example: ).
The effects of such compounds can be:
- deposit formation in the tanks and tubing

- increased fouling of injectors and burners
- contribution to bad combustion (hence stronger pollutant emission) due to degradation of
the fuel by slow oxidation
• The oil (350 ml) is vacuum filtered and placed in an oxidation cell. it undergoes ageing by oxygen bubbling
(O2 flow rate = 3 l/h). The cell is immersed in a bath at 95°C for 16 hours.
• After cooling to room temperature, the cell content is vacuum filtered in a crucible, the cell and the oxygen
delivery tube are rinsed with n-heptane which is then filtered.
• After drying (oven at 100°C, for 1 hour) the crucible, the sediment B content is determined by weighting.
• The cell and the oxygen delivery tube are then washed with a mixture of acetone/methanol/benzene (gum
solvent) in order to dissolve any adherent gum. The gums C are measured by evaporating the solvent at
160°C by the air-jet method (ASTM D 381).
O2 delivery tube
(3 l/h)
Condensor * Water
Water The total insolubles (A) are calculated

as follows:
Test duration B+C

A = (g)
16 hours 3.5
for a sample of 100 ml
(The result is expressed in g/m 3: A must

be multiplied by 104).
Sample
(350 ml)
95 °C
D ANA 082 B
* The oxidation cell is equipped with a condenser in order to avoid evaporation losses.

87
RESIDUAL FUEL OIL STABILITY
Under certain conditions (prolonged heat, mixing of different fuels) the asphaltenes in heavy fuels are liable to
precipitate whilst being stored and in the transfer lines of products. Their stability is measured by using
different tests: the spot test and the hot filtration test.
STABILITY AND COMPATIBILITY OF RESIDUAL

FUELS OILS BY SPOT TEST
– ASTM D 4740 –
This method covers the determination of stability of residual fuel oil and compatibility of a residual fuel oil
with a blend stock.
Stability is defined by the absence of suspended solids in a finished example. Stability can also refer to the
resistance of the product (residual fuel or fuel oil mixture) to form suspended solids over a period of time. The
present test does not concern this second aspect.
Compatibility means the absence of suspended solids when equal volumes of a sample and a blend stock
are mixed together.
Operating procedures:
– stability procedure: a drop of preheated sample is put on a test paper and placed in a oven
at 100°C. After 1 hour, the test paper is removed from the oven and is examined
– compatibility procedure: a blend composed of equal volumes of the sample and of the blend
stock is tested in the same way that the stability procedure
Report:
The stability and/or the compatibility rating(s) is(are) reported by a figure from 1 to 5 explained in the following
table.
Rating Characterizing Features Compatibility
Spot No
1 Homogeneous spot (no inner ring)

2 Faint or poorly defined inner ring
3 Well defined, thin, inner ring, only slightly darker
than the background
4 Well defined inner ring, thicker than the ring in
D ANA 112 A
reference spot No. 3 and somewhat darker than

the background
5 Very dark solid or nearly solid area in the center.
The central area is much darker than the
background
Spot example Problems in
n°4 asphaltene deposits
Residual blended fuel oils are formed by the mixing of lube oils, resins and asphaltenes and the satisfactory
peptizability of the asphaltenes depends on the chemical structure (aromatic characteristics) of the oil and
particularly of the resins (micelle stability).

88
HOT FILTRATION TEST (SHFT - SMS 2696)
or INSOLUBLE CONTENT (asphaltene precipitation and solid impurities)

in liquid fuel oil - NF M 07-063 -
Both methods cover the determination of the amount of solid deposits on Whatman GF/A glass-fiber
filters, when a given quantity (up to 25 g) of heavy fuel sample is drained through three successive filters
with vacuum assistance. The test temperature is 50°C for SHFT and 100°C for NF 07-063. An aging
procedure could be used by storage for 24 hours at 100°C, in order to establish the final equilibrium of
asphaltenes in the oily medium.
Seam-heated jacket
Spring clip
Filters
SHFT
apparus
47 mm
Filter support
D ANA 1085 A
Funnel
O-ring seal
30
NF M 07-063 apparatus
30 Filter support
40
D ANA 111 A
Note:
The same weight of fuel is considered to be retained on the first two filters:
Dm (1st filter) – Dm (2nd filter) = (minsolubles + mfuel) 1 st filter – (mfuel) 2 nd filter = minsolubles
On the 3 rd filter, a higher weight of fuel is retained.

89
SPECIFIC FEATURES OF THE INSOLUBLE CONTENT TEST
– NF M 07-063 - IP 375 –
PRINCIPLE
Applied to liquid fuels and consist on assessing the amount of deposit constituted by:
- solid impurities due to contamination during handling (salt, sand, rust, coke, fibres, other
debris)
- asphaltene precipitation
Test temperature is 100°C for fuels with a maximum viscosity of 40 cSt at 100°C. For the other fuels,
temperature has to be adapted to the product tested, according to its flash point and its viscosity.
PROCEDURE
After filtration at 100°C, through 3 microfiber glasses (Whatmann GF/A) with well-defined characteristics and
masses, the two upper filters are carefully washed in pure dodecane and n-heptane in order to eliminate
traces of soluble hydrocarbons.
After drying, the mass increase of these two filters represents the insoluble content recorded as wt % of the
sample.
SOME COMMENTS
Straight-run distillation residues are considered as stable products. Very little insoluble content is found (0
up to 0.05 wt %).
Cracked fuels have increasingly insoluble contents according to the severity of cracking. If the conversion is
too high during thermal cracking, the insoluble content becomes very high and the fuel product is no more
stable.
In France, the specification for commercial No. 2 heavy fuel oil requires a wt % of 0.25 maximum.

90
COLOR - STABILITY OF COLOR - ASTM COLOR SCALE
– ASTM D 1500 –
This method covers the visual determination of the color of a wide variety of petroleum products such as
lubricating oils, heating oils, diesel fuel oils, and petroleum waxes. Color is determined with a colorimeter. A
sample of liquid is compared to glass color standards, using a light source. The scale ranges from light to
dark and is graduated from 0.5 to 8 at intervals of 0.5. The maximum difference between two determinations
is 0.5.
Usually, gas oils have a light yellow color, corresponding to 1 to 2 in the color scale. A color of 5 in the same
scale corresponds to a dark orange color.
Although color has no direct influence on the utilization qualities of gas oils, a change in color during storage
generally indicates chemical deterioration of the products, often accompanied by the formation of
"sediments" and "gums". This deterioration is related to the presence of nitrogen heterocyclic compounds
(for instance, indole) and aromatics containing an olefin bond, such as .
A number of accelerated ageing tests exist for gas oils. Additives can be used to improve color stability.
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 D ANA 083 B

91
VI - SPECIAL TESTS FOR SOLID OR SEMI-SOLID

PETROLEUM PRODUCTS
Standard tests for assessing behaviour during reheating.
Consistency of solid or semi-solid petroleum products from heavy cuts.
The products concerned are principally bitumen, wax and vaseline (petrolatum or jelly) and they are solid or
semi-solid at ambient temperature.
Tests have been designed to assess their behaviour when they are reheated. Two tests for bitumen are
described hereafter:
- needle penetration,
- softening point (Ring and Ball Temperature).

92
NEEDLE PENETRATION
– ASTM D 5-86 - NF T 66-004 –
The hardness of the bitumenous products is assessed by measuring the depth, in tenths of a millimeter, to
which a standard loaded needle penetrates the product at a specified temperature. The specifications are
usually based on a test lasting 5 seconds at a temperature of 25°C.
The lower the penetration value, the harder the product.
This tests is used for grading pure bitumen, but it can also be used to measure the consistency of vaseline,
wax, paraffin and grease by replacing the needle by a conical plunger.
Test procedure
At the start of the test, the needles just touches the surface of the product. When the button is pressed, the tip
of the needle penetrates the product and the depth of penetration is recorded on a dial in tenths of a
millimeter in 5 seconds.
Examples of pure bitumen:
- 180-220 = extremely soft bitumen

- 20-30 = extremely hard bitumen
100 g weight
Needle penetration
Push button 100 during 5 seconds
Needle Bitumen sample

D ANA 084 B
Water maintained at 25°C

93
SOFTENING POINT
Ring - and - Ball Apparatus
– ASTM D 36-86 - NF T 66-008 –
A steel ball is placed on a ring filled with bitumen. The ball and ring are then gradually heated in a beaker of
water until the bitumen softens sufficiently for the ball to carry the bitumen through the ring down to a
specified level. The temperature at which this occurs is the softening point.
A high softening point indicates that the bitumen is very heat-resistant.
Test procedure
Two standard rings (1) are placed on a marble plate,

filled with bitumen and allowed to cool until the bitumen
Ring Guide for centering is solid. The rings are then placed on a frame in a
the ball breaker of water (3) and a steel ball is placed in each
ring and centred by means of a guide (2).
The water is heated at a rate of 5°C/minute so that the

Steel ball bitumen softens and the ball gradually sinks through the
(3.5 g) ring. When the ball touches the plate below, the Ball and
Ring temperature (BRT) is reached.
Examples:
• 34 to 43°C for 180-220 bitumen

Thermometer • 55 to 63°C for 20-30 bitumen
Calibrated
steel ball
Water
Plate
D ANA 089 B
D ANA 085 B
Mantled device
"Ring and ball" apparatus

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Refining-Petrochemicals-Chemicals-Engineering

MSc IN REFINING, ENGINEERING AND GAS

Module 2: Characterization of petroleum products

OUTLINES OF THE QUALITY OF PETROLEUM PRODUCTS.......................................................... 1

I - TESTS RELATED TO THE VOLATILITY OF PETROLEUM PRODUCTS ............................... 3

ASTM distillation test ...............................................................................................................................4

II - TESTS RELATED TO COMBUSTION OF PETROLEUM PRODUCTS ................................. 16

III - TESTS RELATED TO STORAGE AND FLOWING OF PETROLEUM PRODUCTS .............. 31

AN ENO - 02756_A_A - Rev. 0 04/06/2007

„ 2007 ENSPM Formation Industrie - IFP Training

Density and relative density of liquids by digital densitymeter ............................................................... 43

IV - TEST RELATED TO THE CORROSIVENESS OF PETROLEUM PRODUCTS AND TO

V- TESTS RELATED TO THE CHEMICAL NATURE OF PETROLEUM PRODUCTS AND TO

VI - SPECIAL TESTS FOR SOLID OR SEMI-SOLID PETROLEUM PRODUCTS ........................ 91

02756_A_A © 2007 ENSPM Formation Industrie - IFP Training

OUTLINES OF THE QUALITY OF PETROLEUM PRODUCTS

– correct burning in an engine in the case of motor fuel

• A.S.T.M. American Society for Testing and Materials

For instance, in France, there are several types of requirement:

These are determined by the "Direction des Hydrocarbures" (Hydrocarbon Management

Internal requirements of an oil company :

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

• tests related to volatility

for instance: 6°C for a flash point (Pensky-Martens) above 105°C

for instance: 8°C for a flash point (P.M.) above 105°C

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

I - TESTS RELATED TO THE VOLATILITY

Limitation of light components Reid vapor pressure

Limitation of heavy components ASTM final point

Boiling point Limitation of

The following major tests are described hereafter:

– standard test designed to determine the boiling temperatures: ASTM distillation

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

ASTM DISTILLATION TEST

Flask (125 cm3)

End boiling point

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

Two important temperatures are recorded:

– if the product becomes "lighter", the ASTM distillation temperatures decrease

– if the product becomes "heavier", the ASTM distillation temperatures

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

DISTILLATION OF PETROLEUM PRODUCTS AT REDUCED PRESSURES

Assembly of vacuum distillation apparatus

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

SIMULATED DISTILLATION BY GAS CHROMATOGRAPHY

CALIBRATION - RETENTION TIME (RT) - BOILING POINT

Chromatogram of petroleum residue with internal standard mixture

VOLATILITY OF LIQUEFIELD PETROLEUM GAS (LPG)

This test is applied only to LPG and is similar to ASTM distillation.

This limitation aims to:

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

VAPOR PRESSURE OF LIQUEFIED PETROLEUM GAS (LPG)

The apparatus used is described in the diagram below.

Manometer The apparatus is completely filled with

After equilibrium, the LPG vapor

The vapor pressure of a mixture is

02756_A_A © 2005 ENSPM Formation Industrie - IFP Training

REID VAPOR PRESSURE