I.

Introduction

Through the refining process, crude oil is converted into a variety of petroleum

products that are initially defined by their boiling ranges. The chemistry of ideal combustion

of fuels provides insights into engine air-fuel ratios and assessment of exhaust products. The

importance of octane rating is shown through an analysis of combustion in SI engines, While

an analysis of CI engine combustion shows the importance of cetane rating. Other important

fuel properties are also discussed.

Lubricants are not just oils for car engines; there are many different types including

metalworking fluids, transformer oils, gear and hydraulic oils. Fluid oils and greases, both

solid and semi solid, are also used for lubrication.Additives are blended with base oils and

the combination, quality and quantity of the additives and base oils determine the quality and

the properties of the finished lubricant.

SAE viscosity rating and API service classification are presented as means of

specifying lubricating oils for engines. A typical engine lubricating system is described.

II. Properties of Fuels

Density, Specific volume and Specific Gravity

The density, or more precisely, the volumetric mass density, of a substance is

its mass per unit volume. The symbol for density is ρ. The density of fuel is “the mass of fuel

per unit volume”. When it comes to fuel, higher density means more value of money.

The specific volume of a substance is the ratio of the substance's volume to its mass.

1
Density - ρ - and specific volume of some commonly used fuels

2
 Specific Gravity - SG - is a dimensionless unit defined for liquids as "the ratio of the

density of the substance to the density of water at a specified temperature". For gases the

Specific Gravity is related to air.

3
 Flash Point

The flash point of a volatile material is the lowest temperature at which vapours of

the material will ignite, when given an ignition source. The flash point is a general indication

of the flammability or combustibility of a liquid. Below the flash point, insufficient vapour is

available to support combustion.

There are two basic types of flash point measurement: open cup and closed

cup. In open cup devices, the sample is contained in an open cup which is heated and, at

intervals, a flame brought over the surface. The measured flash point will actually vary with

4
the height of the flame above the liquid surface and, at sufficient height, the measured flash

point temperature will coincide with the fire point. The best-known example is the Cleveland

open cup (COC).

Cleveland Open Cup (COC) Pensky-Martens Flash point tester

There are two types of closed cup testers: non-equilibrial, such as Pensky-Martens,

where the vapours above the liquid are not in temperature equilibrium with the liquid, and

equilibrial, such as Small Scale (commonly known as Setaflash), where the vapours are

deemed to be in temperature equilibrium with the liquid. In both these types, the cups are

sealed with a lid through which the ignition source can be introduced. Closed cup testers

normally give lower values for the flash point than open cup (typically 5–10 °C or 9–18 °F

lower) and are a better approximation to the temperature at which the vapour pressure

reaches the lower flammable limit.

5
 Examples:

Fire Point

The fire point of a fuel is the lowest temperature at which the vapour of that fuel will

continue to burn for at least 5 seconds after ignition by an open flame of standard dimension.

At the flash point, a lower temperature, a substance will ignite briefly, but vapor might not be

produced at a rate to sustain the fire. Most tables of material properties will only list material

flash points. Testing of the fire point is done by open cup apparatus.

Autoignition Temperature

The autoignition temperature or kindling point of a substance is the lowest

temperature at which it spontaneously ignites in normal atmosphere without an external

source of ignition, such as a flame or spark. This temperature is required to supply

the activation energy needed for combustion. The temperature at which a chemical ignites

decreases as the pressure or oxygen concentration increases. It is usually applied to a

combustible fuel mixture.

6
  The ignition temperature of a substance is the least temperature at which the

substance starts combustion.

 Substances which spontaneously ignite in a normal atmosphere at naturally

ambient temperatures are termed pyrophoric.

7
 Autoignition Equation

2
π T −T
[
t ig = kρc ig ' ' 0
4 q ]
Where: t ig= time it takes for a material to reach its autoignition
temperature
T ig= autoignition temperature

q ' ' = heat flux

k = thermal conductivity
ρ = density

c = specific heat capacity of the material of interest

T 0= is the initial temperature of the material

Pour Point
Pour Point is the temperature at which a liquid becomes semisolid and loses its

flowing characteristics. As the paraffin content is high in crude oil, thus it has a high Pour

Point. Due to the paraffin in the oil, it begins to precipitate when the temperature is lowered

down to a certain level. However, oils or synthetic fibers that have high Pour Point suffer

from severe screening effect and excessive pressure.

Measuring the pour point of petroleum products

 Manual method

ASTM D97, Standard Test Method for Pour Point of Crude Oils. The specimen is

cooled inside a cooling bath to allow the formation of paraffin wax crystals. At about 9 °C

above the expected pour point, and for every subsequent 3 °C, the test jar is removed and

8
tilted to check for surface movement. When the specimen does not flow when tilted, the jar is

held horizontally for 5 sec. If it does not flow, 3 °C is added to the corresponding

temperature and the result is the pour point temperature.

 Automatic method

The D5949 test method determines the pour point in a shorter period of time than

manual method D97. Less operator time is required to run the test using this automatic

method. Additionally, no external chiller bath or refrigeration unit is needed. D5949 is

capable of determining pour point within a temperature range of −57 °C to +51 °C. Results

can be reported at 1 °C or 3 °C testing intervals.

Under ASTM D5949, the test sample is heated and then cooled by a Peltier device at

a rate of 1.5±0.1 °C/min. At either 1 °C or 3 °C intervals, a pressurized pulse of compressed

gas is imparted onto the surface of the sample. Multiple optical detectors continuously

monitor the sample for movement. The lowest temperature at which movement is detected on

the sample surface is determined to be the pour point.

Octane Ratiing

An octane rating, or octane number, is a standard measure of the performance of an

engine or aviation fuel. The higher the octane number, the more compression the fuel can

withstand before detonating (igniting). In broad terms, fuels with a higher octane rating are

used in high-performance gasoline engines that require higher compression ratios. In

contrast, fuels with lower octane numbers (but higher cetane numbers) are ideal for diesel

engines, because diesel engines (also referred to as compression-ignition engines) do not

compress the fuel, but rather compress only air and then inject fuel into the air which was

heated by compression. Gasoline engines rely on ignition of air and fuel compressed together

9
as a mixture, which is ignited at the end of the compression stroke using spark plugs.

Therefore, high compressibility of the fuel matters mainly for gasoline engines. Use

of gasoline with lower octane numbers may lead to the problem of engine knocking.

Measurement Methods

 Research Octane Number (RON)

The most common type of octane rating worldwide is the Research Octane
Number (RON). RON is determined by running the fuel in a test engine with a
variable compression ratio under controlled conditions, and comparing the
results with those for mixtures of iso-octane and n-heptane. The Compression
ratio is varied during the test in order to challenge the fuel's antiknocking
tendency as an increase in the compression ratio will increase the chances of
knocking.

 Motor Octane Number (MON)

Another type of octane rating, called Motor Octane Number (MON), is
determined at 900 rpm engine speed instead of the 600 rpm for RON. [1] MON
testing uses a similar test engine to that used in RON testing, but with a
preheated fuel mixture, higher engine speed, and variable ignition timing to
further stress the fuel's knock resistance. Depending on the composition of the
fuel, the MON of a modern pump gasoline will be about 8 to 12 octane lower
than the RON, but there is no direct link between RON and MON. Pump
gasoline specifications typically require both a minimum RON and a
minimum MON.

 Anti-Knock Index (AKI) or (R+M)/2

In most countries in Europe (also in Australia, Pakistan and New Zealand) the
"headline" octane rating shown on the pump is the RON, but in Canada, the
United States, Brazil, and some other countries, the headline number is the
simple mean or average of the RON and the MON, called the Anti-Knock
Index (AKI), and often written on pumps as (R+M)/2. It may also sometimes
be called the Posted Octane Number (PON).

10
 Difference between RON, MON, and AKI
Because of the 8 to 12 octane number difference between RON and MON
noted above, the AKI shown in Canada and the United States is 4 to 6 octane
numbers lower than elsewhere in the world for the same fuel. This difference
between RON and MON is known as the fuel's Sensitivity, and is not typically
published for those countries that use the Anti-Knock Index labelling system.

 Observed Road Octane Number (RdON)

Another type of octane rating, called Observed Road Octane Number (RdON),
is derived from testing gasolines in real world multi-cylinder engines,
normally at wide open throttle. It was developed in the 1920s and is still
reliable today. The original testing was done in cars on the road but as
technology developed the testing was moved to chassis dynamometers with
environmental controls to improve consistency.

 Octane Index

The evaluation of the octane number by the two laboratory methods requires a
standard engine, and the test procedure can be both expensive and time-
consuming. The standard engine required for the test may not always be
available, especially in out-of-the-way places or in small or mobile
laboratories. These and other considerations led to the search for a rapid
method for the evaluation of the anti-knock quality of gasoline. Such methods
include FTIR, near infrared on-line analyzers and others. Deriving an equation
that can be used for calculating the octane quality would also serve the same
purpose with added advantages. The term Octane Index is often used to refer
to the calculated octane quality in contradistinction to the (measured) research
or motor octane numbers. The octane index can be of great service in the
blending of gasoline. Motor gasoline, as marketed, is usually a blend of
several types of refinery grades that are derived from different processes such
as straight-run gasoline, reformate, cracked gasoline etc. These different
grades are considered as one group when blending to meet final product
specifications. Most refiners produce and market more than one grade of

11
 motor gasoline, differing principally in their anti-knock quality. The ability to
predict the octane quality of the blends prior to blending is essential,
something for which the calculated octane index is specially suited.

 Aviation gasoline octane ratings

Aviation gasolines used in piston aircraft engines common in general aviation

have a slightly different method of measuring the octane of the fuel. Similar to
an AKI, it has two different ratings, although it is referred to only by the lower
of the two. One is referred to as the "aviation lean" rating and is the same as
the MON of the fuel up to 100.[8] The second is the "aviation rich" rating and
corresponds to the octane rating of a test engine under forced induction
operation common in high-performance and military piston aircraft. This
utilizes a supercharger, and uses a significantly richer fuel/air ratio for
improved detonation resistance. The most commonly used current
fuel, 100LL, has an aviation lean rating of 100 octane, and an aviation rich
rating of 130.

The RON/MON values of n-heptane and iso-octane are exactly 0 and 100, respectively, by the
definition of octane rating. The following table lists octane ratings for various other fuel

12
13
 Centane Number

Cetane rating, also known as cetane number is a measurement of the quality or

performance of diesel fuel. The higher the number, the better the fuel burns within the engine

of a vehicle. The cetane number is similar to the octane rating in that it is a rating assigned to

a fuel to rate the quality of its combustion. The difference is that octane rating

rates gasoline whereas cetane rates diesel. The main difference between cetane and octane

ratings is that the octane rating represents how well a fuel can resist pre-ignition due to

compression—ensuring the fuel ignites only from a spark from the spark plug. Just as higher

performance gasoline vehicles require fuels with a higher octane rating, high performance

diesel vehicles require fuel with a higher cetane rating. Alkyl nitrates (principally 2-

ethylhexyl nitrate) and di-tert-butyl peroxide are used as additives to raise the cetane number.

Cetane is the chemical compound with chemical formula n-C16H34, today named

hexadecane according to IUPAC rules. It is an unbranched alkane, a saturated hydrocarbon

chain with no cycles. Cetane ignites very easily under compression, so it was assigned a

cetane number of 100, while alpha-methyl naphthalene was assigned a cetane number of 0.

All other hydrocarbons in diesel fuel are indexed to cetane as to how well they ignite under

compression. The cetane number therefore measures how quickly the fuel starts to burn

(auto-ignites) under diesel engine conditions. Since there are hundreds of components in

diesel fuel, with each having a different cetane quality, the overall cetane number of the

diesel is the average cetane quality of all the components (strictly speaking high-cetane

components will have disproportionate influence, hence the use of high-cetane additives).

14
Measurement Methods

 Ignition Quality Tester (IQT)

Another reliable method of measuring the derived cetane number (DCN) of
diesel fuel is the Ignition Quality Tester (IQT). This instrument applies a
simpler, more robust approach to CN measurement than the CFR. Fuel is
injected into a constant volume combustion chamber at approximately 575 °C
and 310 psi. The time between the start of injection and the recovery of the
combustion chamber pressure to 310 psi is defined as the ignition delay. This
measured ignition delay is then used to calculate the DCN of the fuel. The
fuel's DCN is then calculated using an empirical inverse relationship to
ignition delay.

 Fuel ignition tester

Another reliable method of measuring the derived cetane number of diesel

fuel is the Fuel Ignition Tester (FIT). This instrument applies a simpler, more
robust approach to CN measurement than the CFR. Fuel is injected into a
constant volume combustion chamber in which the ambient temperature is
approximately 575 °C. The fuel combusts, and the high rate of pressure
change within the chamber defines the start of combustion. The ignition delay
of the fuel can then be calculated as the time difference between the start of
fuel injection and the start of combustion. The fuel's derived cetane number
can then be calculated using an empirical inverse relationship to ignition
delay.

 Cetane index

Another method that fuel-users control quality is by using the cetane index
(CI), which is a calculated number based on the density and distillation range
of the fuel. There are various versions of this, depending on whether metric or
Imperial units are used, and how many distillation points are used. These days
most oil companies use the '4-point method', ASTM D4737, based on density,
10% 50% and 90% recovery temperatures. The '2-point method' is defined
in ASTM D976, and uses just density and the 50% recovery temperature. This

15
 2-point method tends to overestimate cetane index and is not recommended.
Cetane index calculations can not account for cetane improver additives and
therefore do not measure total cetane number for additized diesel fuels. Diesel
engine operation is primarily related to the actual cetane number and the
cetane index is simply an estimation of the base (unadditized) cetane number.
Cetane Numbers of Various Diesel Fuels

Normal modern highway diesels run best with a fuel rated between 45 and 55.
Following is a list of cetane numbers varying grades and types of compression ignition diesel
fuels:

 Regular diesel-48
 Premium diesel-55
 Biodiesel (B100)-55
 Biodiesel blend (B20)-50
 Synthetic diesel-55

Conradson Carbon residue

Conradson carbon residue, commonly known as "Concarbon" or "CCR" is a

laboratory test used to provide an indication of the coke-forming tendencies of an oil.

Quantitatively, the test measures the amount of carbonaceous residue remaining after the

oil's evaporation and pyrolysis.

Carbon residue of the fuel is indicative of carbon depositing tendencies of the fuel.

Conradson carbon residue (CCR) for biodiesel is more important than that in diesel

fuel because it show a high correlation with presence of free fatty acids, glycerides, soaps,

polymers, higher unsaturated fatty acids, inorganic impurities and even on the additives used

for pour point depression. Two methods are used to measure carbon residue:

1.100 per cent residual.

16
 2.10 per cent residual.

Since most of the biodiesel boils at almost the same temperature it is difficult to get a

10 per cent residual upon distillation. Though the 10 per cent CCR test is easier to do, more

work need to be done before we use it in Indian specifications for biodiesel.

The carbon residue (ASTM D189; ASTM D524) of heavy oil is a property that can be

correlated with several other properties of the oil and may be used to evaluate the

carbonaceous depositing characteristics of heavy oil during thermal recovery.

There are two older well-used methods for determining the carbon residue: the

Conradson method (ASTM D189) and the Ramsbottom method (ASTM D524). Both are

equally applicable to heavy oil but the metallic constituents will give erroneously high

carbon residues. The metallic constituents must first be removed from the oil or they can be

estimated as ash by complete burning of the coke after carbon residue determination. There is

no exact correlation between the two methods but it is possible to interconnect the data

(ASTM, 2012).

Another method (ASTM D4530) requires smaller sample amounts and was originally

developed as a thermogravimetric method. The carbon residue produced by this method is

often referred to as the microcarbon residue. Agreements between the data from the three

methods are good, making it possible to interrelate all of the data from carbon residue tests

(Long and Speight, 1989)

Test Method (For Conradson method)

A quantity of sample is weighed, placed in a crucible, and subjected to destructive

distillation. During a fixed period of severe heating, the residue undergoes cracking and

coking reactions . At the termination of the heating period, the crucible containing the

17
 carbonaceous residue is cooled in a desiccator and weighed. The residue remaining is

calculated as a percentage of the original sample, and reported as Conradson carbon residue.

Conradson Carbon Residue Apparatus

Calculation
Calculate the carbon residue of the sample or of the 10 % distillation residue as
follows:
Carbon residue = ( A x 100)/W

where: A= mass of carbon residue

W= mass of sample

18
 III.Properties of Lubricants

A good lubricant generally possesses the following characteristics:

 A high boiling point and low freezing point (in order to stay liquid within a wide

range of temperature)

 A high viscosity index

 Thermal stability

 Hydraulic stability

 Demulsibility

 Corrosion prevention

 A high resistance to oxidation

A lubricant is a substance, usually organic, introduced to reduce friction between

surfaces in mutual contact, which ultimately reduces the heat generated when the surfaces

move. It may also have the function of transmitting forces, transporting foreign particles, or

heating or cooling the surfaces. The property of reducing friction is known as lubricity.

Density

Density means the volume weight of a substance. In oils, it is usually indicated in the

temperature of +15°C or +20°C, in units kg/m3. Lubricant densities range between about 700

and 950 kg/m3, depending on the quality, viscosity and additive content of the lubricant.

Viscosity

Viscosity is a measure of the internal friction of a fluid. It is the most important

physical property of a fluid in the context of lubrication. The viscosity of a lubricant varies

with temperature and pressure and, in some cases, with the rate at which it is sheared.

19
 Kinematic viscosity is a measure of a fluid's internal resistance to flow under

gravitational forces. It is determined by measuring the time in seconds, required for a fixed

volume of fluid to flow a known distance by gravity through a capillary within a calibrated

viscometer at a closely controlled temperature.

ν=μ/ρ

where ν = kinematic viscosity, μ = absolute or dynamic viscosity, ρ = density. In the

SI-system the unit is m2/s.

Classification of Oil by Viscosity

SAE viscosity numbers with a W (for winter) are classified by their behavior at low

temperatures. Those without a W are classified by their viscosities at 100 C.

Viscositiy index

MacCoull equation:

20
 ln ln (v+0.7)= A+B ln (T)

where: v =kinematic viscosity of the oil

T= absolute temperature of the oil
The equation is not valid as the temperature of an oil approaches its pour point, or at
very low viscosities (approaching 1.0 mm^2/s). A and B are constants for a specific oil.

API service Classifications

The API service classification consist of two letters. The first letter is either a C (for

Commercial use or Compression-ignition engines) or an S (for Service station or Spark-

ignition engines). The second letter denotes the severity of service, with higher letters

indicating more severe service. Thus, an SG oil would be for use in SI engines with more

severe operating conditions than for an SF oil.

Dropping Point

The dropping point of a lubricating grease is an indication of the heat resistance of

the grease and is the temperature at which it passes from a semi-solid to a liquid state under

specific test conditions. It is dependent on the type of thickener used and the cohesiveness of

the oil and thickener of a grease.  The dropping point indicates the upper temperature limit at

which a grease retains its structure though is not necessarily the maximum temperature at

which a grease can be used.

ASTM Test Procedures

21
 The dropping point test procedures are given in ASTM standards D-566 and D-2265.

The test apparatus consists of a grease cup with a small hole in the bottom, test tube,

two thermometers, a container, stirring device if required and an electric heater. The inside

surfaces of the grease cup are coated with the grease to be tested. A thermometer is inserted

into the cup and held in place so that the thermometer does not touch the grease. This

assembly is placed inside a test tube. The test tube is lowered into the container which is

filled with oil in D-566 and has an aluminum block in D-2265. Another thermometer is

inserted into the oil/block.

To execute a test, the oil/block is heated, while being stirred, at a rate of 8 °F (4.4 °C)

to 12 °F (6.7 °C) per minute until the temperature is approximately 30 °F (17 °C) below the

expected dropping point. The heat is reduced until the test tube temperature is at most 4 °F

(2.2 °C) less than the oil/block temperature. Once the temperature has stabilized the sample is

inserted. The dropping point is the temperature recorded on the test tube thermometer, plus a

correction factor for the oil/block temperature, when a drop of grease falls through the hole in

the grease cup. If the drop trails a thread, the dropping temperature is the temperature at

which the thread breaks. D-2265 explains that the dropping point is useful to assist in

identifying the type of grease, and for establishing and maintaining benchmarks for quality

control. It adds that the results are not sufficient to assess service performance because

dropping point is a static test.

ASTM standards D-

566 Apparatus

22
 IV. Summary

Through the refining process, crude oil is converted into a variety of petroleum

products that are distinguished primarily by their boiling ranges. They have different

properties like density, specific gravity, flash point, fire point, Cetane number and Octane

number. They are applied in many ways according to their properties.

Octane number measures the performance of  gasoline while cetane number measure

the performance of the diesel. The fuel having high octane number has the low cetane

number and high cetane number fuel has low octane number. This is one reason why we

can’t use petrol in a diesel engine and diesel in petrol engine. Octane rating and volatility can

be lower for gasolines used at higher elevations, and gasoline volatility must be increased for

cold weather starting.

A review of lubrication theory led to a discussion of boundary, mixed film and

hydrodynamic modes of lubrication. Oiliness is an important oil property in boundary

lubrication. The SAE viscosity classification system and the API service classification

system were discussed as the means for engine manufacturers to specify the lubricating oils

to be used in their engines.

23
 V. Reference

https://en.wikipedia.org/wiki/Flash_point

https://www.britannica.com/science/flash-point

https://en.wikipedia.org/wiki/Autoignition_temperature#Autoignition_equation

https://en.wikipedia.org/wiki/Pour_point

https://www.petropedia.com/definition/2987/pour-point

https://www.sunocoracefuels.com/tech-article/specific-gravity-matter

https://en.wikipedia.org/wiki/Octane_rating

https://en.wikipedia.org/wiki/Cetane_number

https://energyeducation.ca/encyclopedia/Cetane_number

https://www.thoughtco.com/what-is-cetane-85603

https://www.sciencedirect.com/topics/engineering/carbon-residue

https://pentasflora.com/wp-content/uploads/2014/02/D189-Carbon-Residue.pdf

https://en.wikipedia.org/wiki/Lubricant

https://www.sciencedirect.com/science/article/pii/B9780750651547501182

https://www.neste.com/companies/products/lubricants/basic-consepts-lubricants

https://www.yumpu.com/en/document/read/37468848/chapter-5-fuels-and-lubricants-51-

introduction

24