UNIT - III

This document contains key points in Unit III. This may useful to revise the already learned
concepts in this unit

ASSOCIATIVE INTERACTIONS

Primary and secondary bond

In chemistry, bonding is the physical phenomenon; chemical bonding refers to the formation
of a chemical bond between two or more atoms, molecules, or ions to give rise to a chemical
compound. These chemical bonds are what keep the atoms together in the resulting
compound.
There are various kinds of bonds but they are all grouped under two main categories,
primary bond (intramolecular interactions or interatomic force) and secondary bonds
(intermolecular forces)

Primary bond- Intramolecular interactions: Primary bonds are strong in nature; they are
responsible for making of molecule. These bonds hold a set of atoms and create molecules.
These bonds have bond enthalpies in the order of 100 - 1000 kJ/mole, which is much greater
than the intermolecular forces. During chemical reactions, breaking and making of new bonds
are taking place. Generally intramolecular bonds remain intact during a physical change.

Primary bond

Ionic bond covalent bond coordinate bond metallic bond

Ionic bonds: Ionic bonds are also formed when there is a large electronegativity difference
between two atoms. Ionic bonds are result of exchange of one or more valence electrons from
one atom, typically a metal, to another atom, typically a non-metal. An atom that loses

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valence electrons and becomes a positively charged ion is known as a cation, while an atom
that gains electrons and becomes negatively charged is known as an anion. The electrostatic
force of attraction between the cation and anion gives strong ionic compounds. The
compound containing the bond is referred as ionic or electrovalent bond.
Eg NaCl, KCl, MgCl2, CaO, Al2O3 etc.,
In NaCl, Na is metal, Cl is non-metal

Covalent bond: Covalent bonds are formed when electrons are shared between elements
typically non-metals. Covalent bonds can be single, double, and triple bonds.
Eg, Cl2, H2O, N2 etc.,

Coordinate bond: (dative bond or coordinate covalent bond): A coordinate bond is a type of
covalent bond where both of the electrons that form the bond originate from the same atom.
Eg. NH4 ion, ammonia boron trifluoride, hydronium ion etc.,

Metallic bond: Metallic bonds are found only in metals; the constituent atoms lose valence
electrons and form ions. The collective sharing of a sea of valence electrons between several
positively charged metal ions is referred as metallic bond. These free electrons are
responsible for the high electric and thermal
conductivities of metals. For eg in zinc metal Zn atom
loses its two electrons and form Zn2+ ion, metallic bond is
formed between Zn2+ ion and sea of electrons.

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Secondary bonds (secondary forces or intermolecular forces or van der Waals forces)
The attractive forces which act between molecules are usually referred to as secondary bond.
Secondary bonds are bonds of a different kind to the primary ones. These bonds are due to
atomic or molecular dipoles, both permanent and temporary. The intermolecular interactions
are weak individually; due to cooperatives the energies of intermolecular energies in bulk
systems are significantly higher. The secondary forces have strong effect on the physical
properties of the compounds such as melting, boiling point vapour pressures, and viscosities.
Secondary bonds

Dipole-dipole interaction: It is result of electrostatic attraction between two permanent

dipoles. In asymmetric molecules a permanent positive and negative pole is formed due to
difference in electronegativities of the constituent elements and permanent dipoles is
developed (µ > 0). The molecule with dipoles is called polar molecules and is very abundant
in nature.
H-H - homonuclear diatomic molecule --- symmetrical molecule and is neutral (µ = 0)
H-Cl - hetronuclear diatomic molecule --- asymmetrical molecule and is ionic (µ > 0)
In HCl, hydrogen is covalently bonded to electronegative element Cl, the shared
electron pair is pulled close to the Cl atom resulting in formation of dipole. Polar molecules
have a partial negative end and a partial positive end. The positive end of a polar molecule
will attract the negative end of the other polar molecule.

Dipole-dipole interaction depends on orientation, orientation depends on temperature, and

hence dipole-dipole interaction depends on temperature. The interaction energy is
proportional to 1/ r6 where r is distance between the polar molecules.

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The dipole-dipole forces influence the physical properties of simple molecules, for eg dipole-
dipole interaction influences the boiling point of molecule.

dipole boiling point

Molecule moment (D) in K
CH3OCH3 1.3 248
CH3CHO 2.7 294
CH3CN 3.9 355
Induction force (dipole-induced dipole interaction): This type of attractive forces operate
between polar molecules having µ > 0 and the non-polar molecules having µ= 0. Permanent
dipole of the polar molecule induces dipole on the neutral molecule by polarizing its electron
cloud. The non-polar molecule is symmetric, so it can't have a permanent dipole, but this
distortion disrupts the symmetry and induces a small, temporary dipole moment in it. The
attractive forces between permanent dipole and induced dipole are called dipole-induced
dipole forces. When the polar molecule is taken away from non-polar molecule the induced
dipole disappear.

Eg, interaction between H2O (µ > 0) and O2 (µ= 0)

In this case also interaction energy is proportional to 1/ r 6 where r is the distance

between two molecules. A change in the dipole moment of one molecule by another is
called polarization. Interaction depends upon the dipole moment of the permanent dipole and
the polarizability of the neutral molecule. As the size of molecule/atom increase, the
influence of permanent dipole on it also increases, resulting in the increase in magnitude of
this force.

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The dispersion force (London dispersion or induced dipole-induced dipole interaction or
vander Waals interaction): This type of attractive forces operate between the non-polar
molecules having µ= 0, and is formed due to temporary dipoles. In a symmetric molecule the
electron cloud of a molecule may be distorted and a momentary dipole will be developed.
The momentary dipole induces a dipole on another molecule. The interaction between
momentary dipole- induced dipole is called London force. The interaction energy is
proportional to 1/ r6 where r is the distance between two molecules. This can also be seen in
atoms of inert gases, Eg-in Ne.

It is a major contribution to the intermolecular fore and is present in between any pair
of molecules, polar or non-polar, when they are near to each other, hence the secondary force
is also called vander Waals force. The force is temporary but they form and disappears
continuously, that results in overall bonding effect.
It explains the change in melting point, boiling point with respect to molecular size.
Bigger molecule is more polarisable so electron clouds gets easily distorted so it have
stronger London force and have high melting point, boiling point. For eg in the case of F2,Cl2,
Br2 and I2, F2 and Cl2 are gaseous state, Br2 is liquid state, I2 is solid state. I2 is bigger in size
(high molecular weight) therefore strong London force is operating and hence high boiling
point.

Molecule M.Wt boiling point in K

F2 38 65
Cl2 71 239
Br2 160 332
I2 254 458

The shape of the molecule affects the strength of dispersion forces; long molecules
like n-pentane tend to have stronger dispersion forces than shorter neopentane. This is due to

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the increased surface area in n-pentane that allows the molecules to make contact over the
entire surface area.
Hydrogen bonding: A hydrogen bond is a special type of dipole-dipole attraction. When a
hydrogen atom bonded to a strong electronegative atom interact with another electronegative
atom with a lone pair of electrons leading to the formation of hydrogen bond. High
electronegative element such as N, O, or F are capable of forming hydrogen bond. Because
of the difference in electronegativity, the H atom bears a large partial positive charge and the
N, O or F atom bears a large partial negative charge.
H-F – polar molecule (µ > 0)- hydrogen bond is present
H-Cl- polar molecule (µ > 0)- hydrogen bond is not present
Thus H-F molecule is associated through hydrogen bonding, while H-Cl molecule is
associated through dipole-dipole interaction. The H bond is
stronger than van der waals interaction and weaker than fully
covalent or ionic bonds. This type of bond can occur in
inorganic molecules such as water and in organic molecules
like DNA and proteins.
Two type of H-bonding are available

Intermolecular H-bonding Intramolecular H-bonding

Intermolecular H-bonding: H-bonding is

between two distinct molecules of same
or different compounds. For example, H-
bonding between two molecules of water
or between a molecule of water and a
molecule of ammonia.
Intramolecular H-bonding: The H- bond is among two parts of a
molecule, for example in o-nitrophenol H of OH group is attracted by
O of nitro group. Inter molecular H-bonding increases intermolecular
attraction hence increases boiling point, viscosity and surface tension.
Whereas, intramolecular H-bond tends to decrease the surface area of
molecule hence decreases boiling point and surface tension.

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Ion-dipole attractions: An ion-dipole interaction is the result of an electrostatic interaction
between a fully charged ion and a neutral molecule that has a permanent dipole (µ > 0). It is
commonly found in solutions, especially ionic compounds
dissolved in polar liquids. A positive ion attracts the
partially negative end of a neutral polar molecule, negative
ion attracts the partially positive end of a neutral polar
molecule. The attraction becomes stronger either the charge
on the ion increases, or as the magnitude of the dipole of
the polar molecule increases.

Eg, NaCl in water, the oxygen atom in the water molecule has a slight negative charge
and is attracted to the positive sodium ion. Similarly the hydrogen atom in the water molecule
has a slight positive charge and is attracted to the negative chloride ion.

Ion-dipole forces are stronger than dipole-dipole interactions because the charge of
any ion is much greater than the charge of a dipole. Ion-dipole bonding is also stronger than
hydrogen bonding.
Ion-induced dipole force: An ion-induced dipole force occurs when an ion interacts with a
non-polar molecule or atom (µ = 0). Like a dipole-induced dipole force, the charge of the
ion causes a distortion of the electron
cloud in the non-polar molecule, causing
a temporary partial charge. The
temporary partially charged dipole and
the ion are attracted to each other and
form interaction lasting for a very short
time.

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Eg. Fe2+ ion induce dipole on non-polar oxygen

Eg. Formation of I3- compound

Relative strength of intermolecular forces

Bond Energy kJ/mol

Metallic 80 to 600
Ionic 100 to-500
Covalent 100 to 500
H-bonding 40
Dipole-dipole 30
vander Waals 1 to 20

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 HCl-HF

H-F – polar molecule (µ > 0)- hydrogen bond is present

H-Cl- polar molecule (µ > 0)- hydrogen bond is not present
The elecronegativity order is F > O >N >Cl

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Thus H-F molecule is associated through strong hydrogen bonding, while H-Cl molecule is
associated through dipole-dipole interaction. HF is strongly associated than H-Cl, at room
temperature HF is liquid while H-Cl is gas. The atomic radius of the F atom is smaller than
the Cl atom and so the bond in HF is stronger, making it harder to dissociate.
Properties H-F H-Cl
Elecronegativity F=3.98 Cl=3.16
Size F atom is small Cl is higher than F
Hydrogen bonding 1H bond per molecule No H bonding
Bond length 0.917 A 1.275 A
Bond energy 571 KJ/mol 432 KJ/mol
State at RT Liquid gas
Melting point 190 K 159K
Boiling point 293 K 189K

H2O-H2S
H2O – polar molecule (µ > 0)- hydrogen bond is present
H2S – less polar molecule (µ > 0)- hydrogen bond is not present
The polarity of these bonds increases as the absolute value of the electronegativity difference
increases. The dipole moment of hydrogen sulphide is 0.97 D, less than that of H 2O (1.84 D),
meaning that it is a less polar molecule. Thus H2O molecule is associated through strong
hydrogen bonding, while H2S molecule is associated through dipole-dipole interaction.

Properties H2O H2S

Electronegative O=3.5 S=2.5
Size O atom is small S is higher than O
Hydrogen bonding 2H bond per molecule No H bond
Bond length 0.96 A 1.336 A
Bond energy O-H bonds, 458.9 kJ/mol O-S bonds, 340 kJ/mol
State at RT Liquid gas
Melting point 273 K 188 K
Boiling point 373K 273K

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 Ethanol-dimethy ether
CH3 CH2OH: polar molecule (µ > 0) – H-bond is present (dipole moment=1.69D)
CH3-O-CH3: less polar molecule (µ > 0) – H-bond is not present (dipole moment =1.30 D)
In ethanol H is bonded to high electronegative O atom and form H bond with another
molecule.

Properties CH3CH2OH CH3OCH3

Elecronegativity O=3.5 C=2.55
Hydrogen bonding 1H bond per molecule No H bond
State at RT liquid gas
Melting point 159.01 K 132 K
Boiling point 351.5 K 249 K

In ether H is bonded to C atom and no H bonding is possible, The O-C bond ether
have little polarity, the electronegativity difference between carbon and oxygen, gives rise to
a partial dipole moment along each of the two C-O bonds. The dipole - dipole interactions
are quite weak among the ether molecules, London dispersion interactions are more
significant.
Ethanol-diethy ether
CH3 CH2OH- polar molecule (µ > 0)- hydrogen bond is present (dipole moment=1.69D)
CH3CH2-O-CH2CH3- hydrogen bond is not present (dipole moment = 1.15 D)
Properties CH3CH2OH CH3CH2OCH2CH3
Elecronegativity O=3.5 C=2.55
Hydrogen bonding 1H bond per molecule No H bond
State at RT liquid liquid
Melting point 159.01 K 156.8 K
Boiling point 351.5 K 307.8 K

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 Polyethylene-Teflon
Polyethylene (PE): PE is non-polar, only the weakest London force is present. The shape of
the molecule affects the strength of dispersion forces. The PE molecules are longer in size,
due to the increased surface area, the polyethylene molecules make contact over the entire
surface area, the attractions at each contact point is added up. The magnitude of the
interaction energy increases. Thus the London force in PE is higher than the monomer
ethylene. Polyethylene has a melting point of around 400K.

Polytetrafluoroethylene (Teflon): Teflon is non-polar has a melting point of 600K. Because

teflon is a non-polar molecule, it can only experience dispersion forces.

The high melting point than PE is due the aggregate effect of carbon-fluorine bonds. The C−F
bond is a covalent bond, but has considerable ionic character making the carbon positively
polarized and the fluorine negatively polarized. This bond polarization results in a strong
electrostatic attraction between carbon and fluorine which accounts for the high bond strength
observed in teflon.

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 Surface tension

Due to molecular interaction, liquids possess certain properties such as cohesion and
adhesion.
Cohesive forces: When the attractive forces act between like molecules is referred as
cohesive forces.
Adhesive forces: When the attractive forces act between unlike molecules, they are said to
be adhesive forces.
Surface tension occurs due to unbalanced
cohesive forces at the interface of liquid and a gas
or at the interface of two liquids. Surface tension
results from the net inward force experienced by
the molecules on the surface of a liquid.
Molecule A is surrounded by various corresponding molecules and have balanced
cohesive forces on all sides and hence the net force is zero. While in molecule B the
downward attractive force (cohesive force) is greater than upward attractive force by the
vapour of molecule (adhesion) as a result, the molecules experience a net attractive force
towards the bulk of the liquid. The surface molecules always experience a downward pull and
hence they behave as if they are under tension. The tension is termed as surface tension and is
defined as the force along the line per unit length. Its SI unit is N/m.
As a general rule, stronger intermolecular forces result in higher surface tension. A
good example is water, where there are strong intermolecular forces and has high surface
tension. Liquids with lower intermolecular forces like oils have a resulting lower surface
tension.
Consequence of surface tension:
Rise of liquid in the capillary and meniscus:
Capillary action is the net result of two opposing sets of forces, cohesive forces and adhesive
forces. In water, adhesive force > cohesive force, water molecule adhere to the wall of glass,
which contains polar SiOH groups more than the strong intermolecular cohesion force and
forms concave meniscus.
If the adhesive force is stronger than the cohesive force, than the edges of the liquid
will be pulled above the surface of the liquid. This in turn helps to pull the liquid up the

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tube. Liquid with strong intermolecular forces will travel further up a narrow tube (have a
greater capillarity) than substances with weaker intermolecular forces.

In Hg cohesive force > adhesive force, Hg adhere to the wall less than to each other forming
convex surface.

Floating of metal needle on water:

A metal needle has higher density than that of water, so when it is dropped into water, it falls
down into the bottom of water. However, if we put it horizontally on the water it can float
almost forever due to the surface tension of water, the pressure exerted by the needle is
weaker than the surface tension.
Spherical shape of water molecule: Due to surface tension

Water have stronger intermolecular forces that results in higher surface tension, the inward
cohesive force pull to minimize the surface area of a liquid results in formation of spherical
particle. In spherical shape it acquires minimum surface area and hence low surface tension.

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 LUBRICANTS

Introduction
The surfaces of a moving part develop a resistance to their
movement. The resistance to the smooth flow is called friction.
The friction can be minimised by interposing a substance called
lubricant and the phenomenon is called lubrication.
Function of lubricants:
i. The lubricant forms an oil film on the surface of metals,
converting solid friction into liquid friction that prevent the contact between moving, sliding
and rubbing parts under all speeds, loads and temperature
ii. Reducing friction prevents heating and abrasion on the friction surface.
iii. Reduces wear and tear, surface deformations, loss of energy, thereby reducing
maintenance cost
iv. Serve as a coolant, sealant, corrosion resistor and shock absorber
Classification: Lubricants are classified into following classes based on their physical state
Lubricants

Liquid lubricant semi solid lubricant solid lubricant

LIQUID LUBRICANT
Liquid lubricant

Animal &vegetable oil petroleum oil blended oil synthetic lubricant

Animal &vegetable oil:
- Commonly used
- Good oiliness
Eg, Olive oil, palm oil, castor oil, lard oil and tallow oil etc,
-used as additives to petroleum oil to increase the oiliness, also used for preparing grease.
Disadvantages - costly, undergo oxidation, tend to hydrolyse in contact with moist air

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Petroleum oil (mineral oil):
- C12-C50 fraction is used
- Most widely used
- Stable under operation condition and cheap
Purification: Petroleum obtained by distillation has impurities, therefore it is removed before
use

Blended oil:
Petroleum oil + additives blended oil
No single oil can serve as a lubricant for many of modern machinery, for this purpose,
specific additives are added into petroleum oil to improve the desired properties and are
known as blended oils.
i) vegetable oil ( coconut or castor oil), fatty acid (palmitic or stearic acid) are added to
improve the oiliness of a lubricant
ii) aromatic, phenolic or amino compounds act as antioxidant
iii) sodium salt of sulphonic acid act as a emulsifying agent
iv) hexanol is added to improve the viscosity index of oil
v) polystyrene, polyester etc., act as thickening agent and gives high viscosity to the oil

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Synthetic lubricant:
At high temperature petroleum oil undergoes oxidation and cannot be used as
effective lubricant, similarly at low temperature the impurity wax will separate out, therefore
petroleum oil cannot be used as lubricant. In order to meet the greater variation in
temperature and operating conditions, synthetic lubricants are used.
Synthetic lubricants are used in jet engines and aircrafts; it works in the range of -26
o
C to 121 oC.
Eg. i). Dibasic acid ester
HOOC-(CH2)n-COOH + iso-octyl alcohol diester
(Adipic acid C8 (or)
Sebacic acid C9)
They are used in jet engines and military equipments
ii). Silicones are employed as high temperature lubricants
iii). Fluoro and chlorohydrocarbon, are used as lubricants in equipments for
manufacturing
and handling liquid oxygen and H2O2 due to their thermal stability, hydrolytic
stability
and fire resistance.
iv). Phosphate ester are fire resistant and are used as hydraulic fluids

SEMI-SOLID LUBRICANTS (GREASES):

Lubricating oil (base oil) + thickening agent (gelling agent) Greases
i) The thickening agent is usually alkali or alkaline earth metal soap
ii) The base oil may vary from petroleum (naphthenic or paraffinic) to synthetic oils like
esters, silicones or glycols.
iii) Lower viscous oil is used for the preparation of low temperature greases, whereas
higher viscous oil is used for the preparation of high-temperature grease.
iv) The properties of grease depends on alkali used and fatty acid present in the oil

Manufacturing of grease: Grease is prepared by saponification of fat with alkali followed

by adding hot lubricant oil under agitation.

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The fatty acids used are saturated palmitic acid, stearic acid etc. or unsaturated oleic acid.
Grease derived from unsaturated fatty acid has higher thermal stability and dropping point.
Properties and uses:
Type of grease Properties uses
Sodium soap highly soluble in water used in high-temperaature
grease have high dropping point lubrication in ball bearings.

Calcium-soap water-resistant, below 70°C, the used for lubrication of water

grease grease separates into soap and oil; pumps and general purposes.
low dropping point

Lithium-soap resistant to water and heat; used for lubrication of engines

grease superior to all other types at low temperatures

Barium-soap water-resistant, used for lubrication of

grease good adhesiveness automotives

Aluminium- highly adhesive, water-resistant used for lubrication of chains

soap grease and oscillating surfaces

Dropping point (Td) is the temperature at which the grease passes from semisolid to
the liquid on heating.

The dropping point determines the highest operating temperature at which grease can act as
the semi solid lubricant.
SOLID LUBRICANT
Oil and grease cannot be used in high temperature and high load condition eg in
aerospace devices, it move with high speed and develop high temperature for long time.
Therefore, solid film lubricants are selected. They have laminar structure; solid lubricants
prevent direct contact between two sliding surfaces even at very heavy loads. They are
efficient even at very high temperatures and oxidizing environment.
Eg, Graphite, MoS2 etc.,

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Graphite: Carbon in graphite is in sp2 hybridized state, each C atom make covalent bond with
another three C atom resulting in the formation of strong hexagonal layered structure. The
layers of graphite are held together by the weak vander Waals force and form laminar
structure and are slippery in character, so it is used as a lubricant.

Graphites are used in the form powder or as colloidal dispersion, colloidal dispersion is called
dag.
dag – deflocculated Acheson graphite
Graphite + water =aqua-dag
Graphite +oil =oil-dag
Graphite is ineffective in vacuum condition and above 370 oC, used for lubricating
i) Internal combustion engineering
ii) Air compression engine, and iii) Lathe
Molybdenum disulphide (MoS2):
MoS2 have a layered structure, in which a plane of molybdenum atoms is sandwiched
by planes of sulphide ions. Bulk MoS2 consists of stacked monolayers, which are held
together by weak van der Waals interactions. MoS2 is used as lubricating material due to its
layered structure and low coefficient of friction.

MoS2 is used as powder form or as dispersion in petroleum oil, 2-propanol, it is effective up

to 800 oC, used in air frame lubrication and wire-drawing dyes.

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PROPERTIES OF LUBRICANTS AND ITS SIGNIFICANCES:
1. Cloud & Pour point
2. Flash & Fire point
3. Viscosity & Viscosity Index
Cloud & Pour point: ( to assess the quality of oil at low temperature- effect of cooling on
oil)

When the oil is cooled, the temperature at which, the impurities wax and asphalt
crystallizing out gives a cloudy appearance is called cloud point.
Further cooling the temperature at which minute crystal of wax interlocked prevents
the flow of oil is called pour point.
Further cooling, the temperature at which the oil just solidifies is known as its solid
point.
Both cloud & pour point are used to assess the suitability of lubricants under cold
condition. Cloud point is helpful in deciding the lowest temperature up to which it can be
used without any clogging.
Determination of pour point:
The flat bottomed test tube (30 mm diameter
and 120 mm height) is taken and half of the level is
filled with oil, thermometer is inserted into it and is
placed in an air-jacket. The system is placed in a
freezing mixture (ice and salt). For every 1ºC fall of
temperature of the oil, the tube is withdrawn and is
replaced immediately. The temperature at which, a
cloudy appearance is noted as cloud point.
The cooling is continued, for every 3ºC fall of temperature of the oil, the tube is
withdrawn and is replaced immediately. The temperature at which, the oil does not flow in
the test tube even when positioned horizontally is taken as pour point.
Flash & Fire point: (to assess the quality of oil at high temperature- effect of heating on oil)

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Flash point is the lowest temperature at which vapours are given off by the oil to cause a
momentary flash when the vapour comes in contact with test flame.
Eg. Kerosene =73 oF
Power kerosene =90 oF
Further heating the temperature at which sufficient vapours are given off by the oil to burns at
least five seconds when the vapour comes in contact with test flame.
Fire point > flash point, Flash point indication of the tendency of the oil to volatilise. The
lubricant should possess the flash point at least above the temperature it is to be used.
High flash point: i) Evaporation loss less
ii) No vapour locks in engine
Low flash point: i) High evaporation loss
ii) Vapour lock in the engine
Oil of paraffin’s base have higher flash point than the oil of naphthalene base. Good
lubricants have high flash point and fire point.
Determination of flash & fire point:- Pensky Marten’s apparatus
The instrument consists of an oil cup made up
of brass and is meant for heating the lubricating oil,
the cup is of 5 cm in diameter and 5-6 cm in height.
The cup lid is provided with 4 holes of specified
dimensions. They are used for fitting a thermometer,
introducing the test flame, stirrer blades and for the
introduction of air. At the top of the cup, there is a
shutter with lever mechanism, with the help of the
shutter, the lid of the cup can be opened and the test
flame can be introduced over the oil surface.
The cup is filled with the sample of oil up to the filling mark and thermometer is
inserted in such a way not to touch the metallic cup. The oil is heated by means of electric
heater so that the sample of oil gives out vapour. The test flame is introduced above the lid, at
regular intervals, when the oil gives out vapour, the first flash is observed and the
temperature is noted as flash point of the oil. The process of heating and introducing the test

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flame is continued, the temperature at which sufficient vapours are given off by the oil to
burns at least five seconds is fire point.
Viscosity & Viscosity Index of oil
Viscosity: It is related to the ease with which molecules can move past each other. A low
viscous liquid flows very fast and vice versa. The operating characteristic of a liquid to be
used as a lubricant depends on its viscosity. Viscosity depends on molecule size and
attractive forces between molecules.
Eg: 1. Hexane- London force is present- viscosity is 3.26X10-4
Decane- London force is present- viscosity is 1.42X10-3

The high viscosity of n-decane is due to increase in size. The shape of the molecule
affects the strength of the intermolecular force; long molecule n-decane have increased
surface area which allows the molecules to make contact over the entire surface area and have
stronger dispersion forces than shorter n-hexane and hence high viscosity.
Eg: 2: Olive oil – viscosity- 84 cps
Glycerol (or glycerine)-viscosity – 1490 cps

Olive oil is bigger molecule than glycerol but only weak London force is present, but in the
case of glycerine both H bond and London force are present, therefore the viscosity of
glycerine is higher than olive oil.
Viscosity Index of oil; The viscosity of the oil also depends on temperature, higher the
temperature of oil, lower will be its viscosity. The change of viscosity with respect to
temperature is known as viscosity index (VI). If the viscosities of oil decrease rapidly with

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increase of temperature, the oil said to be having low viscosity index. If the viscosity of the
oil decrease marginally with increase of temperature, the oil said to be having high viscosity
index. Oil with high VI is preferred as lubricant, they will work at low temperatures and at
higher temperatures.
Viscosity of the oil at various temperatures is determined by Redwood viscometer.
The given quantity of oil is allowed to pass through a standard orifice under standard
conditions and the time taken is noted as viscosity in seconds.
Temperature Viscosity in seconds
(time flow)
T1 t1
T2 t2
T3 t2
- -
- -
- -

The setup consists of a silver oil cup, heating bath and stirrer. The silver cup is fitted
with thermometer and the oil is heated by making use of water bath. The oil cup is a silver
plated brass cylinder; the bottom part of the
cylinder is fitted with an agate jet, 1.82 mm
diameter and 10 mm in length. After reaching the
desired temperature the ball valve is lifted, the oil
flow through the orifice, the time required for
collecting 50 mL of the oil is noted as viscosity of
the liquid at a particular temperature. The
viscosity in seconds for the oil is noted at various
temperatures. A graph is plotted between viscosity
and the corresponding temperature.

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Determination of VI of oil:

To calculate V.I. of test oil, two types of standard oils are taken.
Pennysylvanian oils (contains straight chain paraffin’s) is assigned a value of V. I. = 100
Gulf oils (contains naphthenic) is assigned a value of V. I. = 0
Any test oil is compared at 38oC(100F) with a zero VI (Gulf oils) and 100 VI
(Pennysylvanian oils). The viscosity index of the test oil is given by the relation.

Where U =viscosity of test oil at 38 ºC

L = viscosity of standard oil at 38 ºC whose V. I. = 0
H = viscosity of standard oil at 38 ºC whose V. I. = 100

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LUBRICATING EMULSIONS
Emulsions are commonly used as lubricants and coolants in metal working and cutting
applications.
Emulsion:
Water + alcohol soluble -homogeneous system, number of phase =1
Water + oil insoluble- heterogeneous system, number of phase =2
Emulsion is two phase system consisting of two immiscible liquid, one dispersed as fine
droplet (dispersed or internal phase) in the other (continuous or external phase).

The emulsion system is unstable, to increase the stability, a third component called emulsifier
or emulsifying agent (surfactant) is added. Emulsifiers are molecules having hydrophilic and
hydrophobic part. The hydrophilic parts of the emulsifier like water, while the hydrophobic
part like oil. The emulsifier molecules get adsorbed at the interface of the two phases
resulting the formation of a protective film around the droplet and the system become stable.

Water-oil system

O/W system W/O system

O/W system: Less than 26 % of oil is dispersed in a continuous water phase

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Emulsifier: i) Sodium soap
ii) Sodium or potassium salt of sulphonic acid
W/O system; water is dispersed in a continuous oil phase (above 74% of oil)
Calcium stearate is used as emulsifier
Uses: i). Cooling & lubricating liquid for cutting tools
ii).Used as rust protection
iii).Used in heavy sliding components such as piston in diesel engine and internal
combustion engines.
Steam emulsification number
Steam emulsification number is the time (in seconds) required for an emulsion of lubricating
oil and water to separate into distinct layers at 90 oC.
Determination of steam emulsification number –ASTM method
Steam of 100 oC is bubbled through 20mL of lubricating oil taken in a test tube till its
temperature reaches 90 oC. The tube is then placed in a water bath maintained at 90 oC, the
time required (in seconds) for water and oil to separate into two distinct layers is noted as
steam emulsification number.
Significance of steam emulsification number:
Low SEN= fast separation of emulsion into water and oil, not ready to form emulsion.
High SEN=takes long time for the emulsion to separate into water and oil, readily form
emulsion
Good lubricating oil has low steam emulsification number; so that when it comes in contact
with water it does not form an emulsion.
An oil having high steam emulsification number is preferred for preparation of lubrication
emulsification like cutting fluids.
Mechanism of Lubrication
The mechanism of lubrication can be classified into the following types:

Fluid-film Boundary Lubrication Extreme-pressure lubrications

or or
Hydrodynamic lubrication Thin-film lubrication
Fluid-film or Hydrodynamic lubrication
In this case, hydrocarbon oil is used as lubricant, a film of fluid thickness not less than 1000
Å fills the space between the moving surfaces. After adding the lubricants the metal-metal

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contact becomes meta-oil-metal contact, thus metal-metal contact is prevented. The
lubricating fluids fill the irregularities on the surface and reduce the wear.

When a lubricant is applied to a shaft and bearing assembly, the rotating shaft pull the
converging wedge of lubricant between shaft and bearing. As the shaft gained velocity, the
lubricants flow between the two surfaces at greater rate, which is due to the highly viscous
nature of lubricant. The lubricant produces a liquid pressure in the lubricant wedge, which is
adequate to keep the two surfaces separated and the only friction in the system is the viscous
resistance of the fluid.

Before the beginning of rotation, the shaft rests on the bearing surface. As the rotation
commences, the shaft moves up the bore, until an equilibrium condition is achieved and now
the shaft is supported on a wedge of lubricant. The shaft and the bearing are held apart by
the pressure generated within the fluid-film lubricant. Journal bearings are designed in such
a way that under standard operating conditions, the load is supported by the constantly
generated fluid pressure without any contact between the bearing surfaces.
Boundary Lubrication or thin-film lubrication:
A very thin film of lubricant thickness 10 Å, is formed on the moving surface either by
physisorption or chemisorptions. These adsorbed layers avoid direct metal-to-metal contact
and the coefficient of friction of such lubricants varies between 0.05-0.15.

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 i. Long chain fatty acid esters and their soaps have polar groups which can attach to
the solid surfaces either by physisorption or chemisorptions and form a thin-film.
ii.The lubricant possesses high thermal stability and should not get detached from the
adsorbed surface at high temperature.
iii. At higher temperature, the long chain fatty acid may detach from the surface, so
mineral oil with fatty acids or soaps as additives are preferred as boundary lubricant.
iv. Graphite and MoS2 either as powder or molecular suspension can serve as
boundary lubricant
Extreme-pressure lubrications
When the moving/sliding are subjected to high pressure and speed, the local
temperature will increase due to excessive friction. In order to counteract these extreme-
pressure conditions, special additives known as extreme-pressure additives are added into
the mineral oil.

The additives in the form of organic phosphorus, sulphur, chloro compounds are
added to the mineral oils. They react with metal surfaces at high temperature forming
durable metallic thin films such as phosphates, sulphides, chlorides and reduce the friction.
These additives are ineffective on chemically inert surfaces like Ag, Cr and Ti.
Extreme-pressure lubrications are used in wire drawing dies, cutting fluids,
railway track joints and high-speed gears.

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