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CY6252 CHEMISTRY FOR TECHNOLOGISTS

UNIT 3

OILS, FATS, SOAPS & LUBRICANTS

LESSON PLAN
3.1) Chemical constitution of oils and fats
3.2) chemical analysis of oils and fats (Acid value, saponification value and iodine value)
3.3) Mechanism of lubrication ( Thick layer Thin layer extreme pressure)
3.4) Liquid lubricants - petrolubes
3.5) Properties Viscosity, Viscosity index, Flash & Fire point, Cloud & Pour point,
aniline point, carbon residue, oxidation stability
3.6) Semi solid lubricants Greases ( Na, Li, Ca, axle)
3.7) Properties of greases- Consistency test and drop point test
3.8) Solid lubricants Graphite , Molybdenum disulphide

3.1) STRUCTURE AND CHEMICAL CONSTITUTION OF OILS AND FATS


1. Oils and fats are glyceryl esters of higher fatty acids. In general, oils are unsaturated glycerides and fats
are unsaturated glycerides.

GLYCEROL

FATTY ACIDS

OIL / FATS

2. Fats: At normal temperature, fats are semisolids or solids. The arrangement of fatty acid chains allows
tight packing of molecules. This is the reason for the higher melting point of fats. (eg) Animal fats,
vanaspathi.
3. Oils: Oils are unsaturated glycerides. At normal temperature , they are liquids. The presence of cisdouble bond results in random conformation, leads to less dense packing of molecule. So, oils have low
melting point.
4. Fatty acids are long chain hydrocarbon (with C8 to C24) containing COOH group at the end. The fatty
acids may be saturated or unsaturated. The unsaturated acids have cis and trans forms.

5. Relationship between melting point and structure:


a) A longer carbon chain increases the melting point of the oil and fat.
b) Double bond decreases the melting point.
c) Cis isomers are having lower melting point than that of Trans isomers.

6. Differences between oils and fats


No
Fats
1
They are saturated glycerides.
2
They have high melting point.
3
They are solid or semi solid at room
temperature
4
Packing of molecules is dense.
5
(eg) Glyceryl palmitate, glyceryl stearate in
ghee, dalda, vanaspathy

Oils
They are partially unsaturated glycerides.
They have low melting point
They are liquid at room temperature
Packing of molecules is comparatively less dense.
Glyceryl trioleate, glyceryl linoleate present in
mustard oil, soyabean oil, castor oil

Similarities of oils and fats:


1. They are derived from fatty acids and glycerol.
2. Most of the physical and chemical properties are identical for oils and fats.
2

Properties of oils and fats:


Physical properties:
1. They are soluble in benzene, CCl4 and CHCl3.
2. Because of long hydrocarbon chain, they are insoluble in water.
3. They are poor conductors of heat and electricity.
4. When agitated with water in presence of an emulsifying agent, they form an emulsion.
5. They slowly dry and develop a hard surface film in contact with air.
Chemical properties
i) Hydrolysis:
a) When exposed to moist air or water, fats and oils undergo hydrolysis to yield glycerol and higher fatty
acids.
.

FATS / OILS

GLYCEROL

HIGHER FATTY ACID

ii) Saponification:
On alkali (KOH / NaOH) hydrolysis, they give glycerol and soap. This is also known as saponification.
CH2 - COOR
|
CH - COOR
|
CH2 - COOR
Oil

+ 3 M OH

CH2 - OH
|
CH OH + 3 R COO M
|
CH2 - OH
glycerol
metallic soap

alkali

iii) Reduction (Hydrogenolysis):


On passing excess of H2 through an oil or fat, it yields glycerol and a higher alcohol (One extra CH2 group
than the oil) . This is known as hydrogenolysis.
CH2 - COOR
|
CH - COOR
|
CH2 - COOR
Oil

+ H2

2500C

Catalyst

CH2 - OH
|
CH OH + 3 R CH2OH
|
CH2 - OH
glycerol
Higher alcohol

iv) Hydrogenation:
Unsaturated oil undergoes hydrogenation in presence of Ni at 180oC to give vanaspathi.
Unsaturated oil

Vanaspathi
3

v) Addition of Iodine:
Oils undergo addition reaction with I2 in presence of HgCl2 catalyst. This reaction is used to measure
number of double bonds in oil.
Number of iodine molecule absorbed
CH2 COO CH2 R1
|
CH - COO CH = CH CH2 R2
|
CH2 COO - CH2 R3
Oil

Number of double bonds present in the oil

+ I2

HgCl 2

CH2 COO CH2 R1


|
CH - COO CH - CH CH2 R2
|
|
I
I
CH2 COO - CH2 R3
Oil Iodine addition product

vi) Oxidation ( Polymerisation):


Oils having CH2- groups present in between C=C- bonds undergo oxidation followed by polymerization to
give a dry, tough and durable film.
vii) Drying:
a) Certain oils change into hard solids on exposure to air. These are called Drying oils (Eg. Linseed oil) and
used in paint and varnish industries. Drying is catalysed by metallic oxides.
b) Some oils thicken slowly and contain a smaller percentage of the glycerides of unsaturated acids than the
drying oils. These are called non- drying oils (eg. cottonseed oil) .
viii) Rancidification:
On long exposure to moist air, fats and oils develop an unpleasant , offensive smell. This is known as
rancidity. This is due to partial hydrolysis of oils, which release strongly smelling fatty acids.
(eg) Butter on hydrolysis yields volatile fatty acids having unpleasant odour.
Rancidification is temporarily prevented by keeping the oil / fat in refrigerator.
Uses of fats and oils
1. As food article
2. For toilet soap purposes
3. In medicine
4. As lubricants
5. As illuminant
6. Paint industry

3.2) CHEMICAL ANALYSIS OF OILS AND FATS


A) ACID VALUE
Acid value is the number of milligrams of KOH required to neutralize the free acid present in 1 g of the fat
or oil.
Significance of Acid value
1. The normal acid value for most samples lies within 0.5.
2. A high acid value indicates a stale oil or fat stored under improper conditions.
3. Low acid value indicates the freshness of oil.
4. Thus, acid value indicates the extent of rancidity.

ESTIMATION OF ACID VALUE OF OIL


AIM
To calculate the number of milligrams of potassium hydroxide required to neutralize the
free fatty acid in the given oil sample.
PROCEDURE

Titration - I
Standardisation of KOH
Burette solution

KOH

Pipette solution

20 ml of 0.1N Oxalic acid

Indicator

Phenolphthalein

End point

Appearance of pink colour

From the volume of the KOH solution in burette, KOH strength can be known.

Titration II
Determination of Acid value
Burette solution

Std. 0.1 N KOH

Pipette solution

5g Oil + 50 ml of neutralized alcohol. Heated for 10 minutes.

Indicator

Phenolphthalein

End point

Appearance of pink colour

FORMULA
Acid value = Titre value x Normality of KOH (0.1) x Equivalent weight of KOH (56)
Weight of the oil sample taken (5g)
RESULT
The acid value of the given oil sample was found to be___________.
5

B. SAPONIFICATION VALUE
It is the number of milligrams of KOH required to neutralize the fatty acids resulting from the complete
hydrolysis of 1 g of the oil or fat. It is also known as KOETTSTORFER number.
Significance of Saponification value
1. It predicts whether an oil or fat contains high proportion of lower or higher fatty acids.
2. Smaller the SAP value, higher will be the molecular weight of oil.
3. As mineral oils do not undergo saponification, this test is used to differentiate fatty oils and
mineral oils.
4. SAP value is indicating the extent of adulteration in a given oil.
5. It is used to determine the actual amount of KOH required for saponification.
ESTIMATION OF SAPONIFICATION VALUE OF AN OIL
AIM
To calculate the number of milligrams of potassium hydroxide required to neutralize the fatty acids
resulting from the complete hydrolysis of the given oil sample.
Principle reaction:
CH2 - COOR
|
CH - COOR
+ 3 M OH
|
CH2 - COOR
Oil
alkali

CH2 - OH
|
CH OH + 3 R COO M
|
CH2 - OH
glycerol
metallic soap

PROCEDURE
1) A known amount of the given oil sample is taken into a 250 ml conical flask.
2) 50 ml of 0.5 N alcoholic KOH solution is added in the flask and refluxed for one hour.
3) After cooling, the excess alkali in the solution is back titrated with 0.5 N HCl using phenolphthalein
indicator.
4) The disappearance of pink indicates the end point.

FORMULA
SAP value

Titre value x Normality of KOH (0.5) x Equivalent weight of KOH (56)


Weight of the oil sample taken

RESULT
The saponification value of the given oil sample was found to be_____________.
6

C. IODINE VALUE
Iodine value is the number of grams of iodine which combine with 100 grams of oil or fat.
Significance of Iodine value
1. It indicates the degree of unsaturation of acids in the oil or fat.
(eg) Oleic acid containing 1 double bond absorbs 90% of iodine, linoleic acid (2 double bonds) absorbs
181% iodine and linolenic acid (3 double bonds) absorbs 274% iodine.
2. Based on iodine value, the oils are sub-divided into three groups:
S.No
1
2
3

Type of oil
Drying oil
Semi drying oil
Non drying oil

Example
Linseed oil
Cottonseed oil
Castor oil

Iodine value
Above 140
Between 90 to 140
Below 90

ESTIMATION OF IODINE VALUE OF AN OIL


AIM

To determine the amount of unsaturation ( Iodine value) present in the given oil.
Principle reaction
CH2 COO CH2 R1
|
CH - COO CH = CH CH2 R2
|
CH2 COO - CH2 R3
Oil

+ I2

HgCl 2

CH2 COO CH2 R1


|
CH - COO CH - CH CH2 R2
|
|
I
I
CH2 COO - CH2 R3
Oil Iodine addition product

PROCEDURE

Burette solution
Pipette solution( In
iodine flask)

Additional solution
Indicator
End point

Std. 0.1 N Sodium thiosulphate


a) Known weight of oil + 10ml chloroform heated slightly and cooled
b) 25 ml Wijs solution (Iodine + Iodine monochloride + glacial acetic acid) is
added shaken vigorously kept in dark for an hour.
Diluted with 50 100 ml of water.
15 ml of 10% KI
Starch
Disappearance of blue colour

FORMULA

Iodine value

Titre value x Normality of thio (0.1) x Equivalent weight of Iodine (127)


Weight of the oil sample taken

RESULT

The iodine value of the given oil sample was found to be =___________.
7

3.3) LUBRICANTS - MECHANISM


1. The materials used between two moving parts to reduce the friction and heat are known as lubricants.
The process is known as lubrication.
CLASSIFICATION OF LUBRICANTS:

Lubricants
-----------------------------------------------------------------------------------------------------------------Liquid
Semi solid
Solid
1,Vegetable oil
1.Grease
1.Graphite
2. Animal oil
2. Vaseline
2. MoS2
3. Mineral oil
4. Synthetic oil
5. Blended oil
Functions: It reduces expansion due to heat - It reduces damages - It reduces corrosion - It reduces
maintenance cost. - It acts as seal proof for dust materials - It increases efficiency of machines.
Requirements: Good viscosity high viscosity index High flash & fire point Low cloud & Pour point
High aniline point Low carbon residue High corrosion resistance good oiliness.
MECHANISM OF LUBRICANTION
1. Thick layer mechanism (Hydrodynamic)
2. Thin layer mechanism (Boundary layer)
3. Extreme pressure mechanism
1. Thick layer mechanism: -( Hydro dynamic mechanism)
i). Condition:

It is applied in low load and high speed areas.

ii) Thickness of lubricant layer : Above 1000 Ao


iii) The co-efficient of friction is 0.001 0.03.
iv) Example : Mineral oils, blended with long chain polymers.
v) Used in : watches, clocks, guns, sewing machines, scientific instruments
vi) Mechanism:
a) The liquid lubricants is applied between rotating shaft and bearing which forms a hydro dynamic wedge
that prevents actual contact between shaft and bearing.
b) This happens because, the lubricating oil covers the irregularities of the sliding
surfaces and forms a thick layer in between them.

2. Thin layer mechanism: ( Boundary mechanism)


i). Condition:

It is applied in high load and low speed areas.

ii) Thinckness of lubricant layer : below 1000 Ao


iii) The co-efficient of friction is 0.05 0.15.
iv) Example : vegetable oils, animal oils
v) Used in : rollers, gears, tractors, railway track joints
vi) Mechanism:
a) The mechanism takes place either by adsorption or chemical reaction. Chemical reaction results in
formation of metallic soap.
b) The polar groups (- COOH) is mainly responsible for the lubricating property.
-COOH group present in oils react with the Metal to form soapy film.(e.g.) Stearic acid, C17H35COOH
c) COOH group moves inwardly, but alkyl groups are oriented outwards in a perpendicular direction.

3. Extreme pressure mechanism:


i). Condition:

It is applied in high load and high speed areas.

ii) Thinckness of lubricant layer : varies with application


iii) The co-efficient of friction varies with application.
iv) Example : oils blended with extreme pressure additives like organic sulphur
compounds, chloro compounds or phosphorous compounds
v) Used in : wire drawing, in machining tough tools etc,
vi) Mechanism:
a) It is mainly used in areas of high speed and heavy load where more heat is produced. In such cases the
liquid lubricants fail to stick and undergo decomposition or evaportation.
b) So, the compounds known as extreme pressure additives are added to mineral oils to improve oiliness and
maintain thick films.
c) Organic chloro compounds are added as pressure additives. They react with metal to form metallic
chloride. Metallic chlorides are having high load bearing, speed bearing capacity and high frictional
resistance.
9

3.4)LIQUID LUBRICANTS - petrolubes


The materials used between two moving parts to reduce the friction and heat are known as lubricants. The
process is known as lubrication.
Lubricants which are at liquid state at ordinary temperature are known as liquid lubricants.
Petrolubes (Mineral oil) : They are obtained from fractional distillation of petroleum.
These are most widely used liquid lubricants because,
i) Cheap
ii) Available in abundance
iii) Quite stable under service conditions.
But, they cannot be used as such. The impurities should be treated first.
No
1

Impurity
Wax

Drawbacks
Raises the pour point and the
lubricant cannot be used at low
temperatures.

Asphalt /
Naphthenic
impurity

Causes carbon deposition and sludge


formation.

Sulphur /
unsaturated
compounds

Get easily oxidized and hinders the


lubrication process.

Coloured
materials

Undesired stains in the metallic parts.

Removal
Method: Dewaxing
i)Wax is dissolved in propane or trichloro
ethylene solvent.
ii) After crystallization, wax is removed by
centrifugation.
iii) Solvents are removed from the oil by
distillation.
Method: Acid refining
i) Removed by con. Sulphuric acid refining
method.
ii) The undissolved portions are converted as
sludges and removed by filtration.
iii) The excess acid is neutralized with calculated
amount of alkali.
Method: Solvent refining
i) Unsaturated simple compounds are removed
by hydrogenation in presence of Nickel.
ii) Further, the oil is mixed with furfural or
nitrobenzene solvents in which the oil is
immiscible but the resin, asphalt, naphthene
impurities are highly soluble.
iii) On undisturbed standing, the liquid
separates into two layers.
iv) The oil layer is free from impurities.
v) The solvent layer contains all the unwanted
impurities. This is subjected to further
purification and can be used as a fuel oil
Removed by Fullers earth at 100 140oC.

After purification, animal and vegetable oil are added to it to increase the oiliness.

10

Furthermore, the petro lubes are blended with additives to get the required properties. Such lubricants are
known as blended petro lubes.
Blended oils (Blended petro lubes)
Two or more oils and other additives are mixed together to get required properties for a lubricating oil.
This is known as blending of oils.
No Additives

Uses

Example

1
2
3
4

Increase viscosity
Prevents oxidation
Decrease cloud and pour point
withstand high pressure

Poly styrene
Phenolic compounds
Para flow (poly alkyl benzene)
organic chloro compounds

Increase oiliness
Increase Viscosity index
Prevent corrosion
Avoid carbon deposition

Stearic acid
n- hexanol
Tri cresyl phosphate
Salts of phenol and carboxylic acid

5
6
7
8

Thickening agents
Anti-oxidants / Inhibitors
Pour point depressant
Extreme pressure
additives
Oiliness carrier
Viscosity index improver
Corrosion inhibitor
Deflocculants

3.5) PROPERTIES OF LIQUID LUBRICANTS


1. Viscosity
2. Viscosity index
3. Flash and fire point
4. Cloud and pour point
5. Aniline point
6. Carbon residue
7. Oxidation stability

1. Viscosity:
Definition: Viscosity is the measure of internal resistance of a liquid during its flow. Its unit is centipoises.
Significance: The viscosity of the lubricating oil should be moderate and good. If it is too high, it will
disturb the movement of machine. If it is too low, it cannot withstand high temperature and pressure, so
come out of the machine.

11

Determination:
The time taken for liquid to pass through the orifice of a standard viscometer is known as viscosity.
It is determined by using Redwood viscometer or Saybolt viscometer .
The time taken for 50ml of oil to pass through the Redwood viscometer is known as Redwood viscosity or
redwood second.
The time taken for 60ml of oil to pass through the Saybolt viscometer is known as Saybolt viscosity or
Saybolt second.
Component and working of Redwood viscometer:
The oil sample is taken in a graduated Oil cup. It is provided with a agate jet opening at the bottom. A
thermometer is provided to know the temperature of the oil sample. Oil cup is surrounded by a water bath .
The water bath is heated properly. A second thermometer is provided to indicate the temperature of the
water bath. A four bladed stirrer is used to maintain uniform temperature of the water bath. Levelling
screws are used to adjust the height and position of the entire apparatus.
A specially shaped 50ml Kohlrausch flask is used for receiving the oil from the jet outlet. The time taken for
50ml oil to be collected in the flask is known as redwood viscosity.

2. Viscosity index :( V.I )


Definition: It is average decrease in viscosity per 1o rise in temperature between 38oC 99oC.
Significance:
If the change is very rapid, the oil is known as low viscosity
index oil. E.g. Gulf coast oil. (Naphthenic hydrocarbon) Its
Viscosity index = 0.
If the change is very slow and less, the oil is high viscosity
index oil.
E.g. Pennsylvanian oil (Paraffinic hydrocarbon). Its VI =
100
Generally, V.I should be high in order to maintain proper
viscosity. To increase the viscosity, n-hexanol and poly
isobutylene are added.

Determination: The determination of viscosity of low index oil(L), high index oil(H) and the test unknown
oil (U)is done at 38oC using Redwood viscometer. The values are substituted in the formula,
At 38oC, V.I

= LU
LH

X 100
, With the condition such that, L = U = H at 99 oC

Where, L = Viscosity of low index oil at 38oC


H = Viscosity of high index oil at 38oC
U = Viscosity of unknown test oil at 38oC
12

3.Flash and Fire Point:


Definition:
Flash point: The lowest temperature at which an oil can produce sufficient amount of vapours which can
ignite for a moment, when a flame is brought near it.
Fire point: The lowest temperature at which oil can produce sufficient amount of vapours which can ignite
for at least for 5 seconds, when a flame is brought near it.
Fire point is 5o 40o C greater than flash point.
Significance:
It should be very high in order to avoid fire accidents.
Determination Using Pensky Martin method:
Pensky Martin apparatus is a beaker of 5.5cm
height and 5 cm diameter provided with a shutter lid.
There are there openings for oil filling, thermometer
and for introducing a flame.
Oil is taken in the apparatus and kept over a burner.
Periodically flame is inserted and observed for
ignition for a moment and then ignition for five
seconds. Thus flash and fire point is determined.

4. Cloud and pour point


Definition:
Cloud point: The temperature at which oil becomes hazy is cloud point.
Pour point: The temperature at which the oil stops flowing is pour point.
Significance: The cloud and pour point should be very low , otherwise at lower temperatures wax and
parafinnic impurities will solidify and clogging may happen. To decrease the cloud and pour point, Para
flow ( Poly alkyl benzene) is added.
Determination:
A flat bottom tube A is filled with oil and kept
inside an air jacket B.
The setup is immersed in freezing mixture C (
Ice + CaCl2). Thermo meter is introduced into
A and C.
Then the test tube is kept in horizontal
position.
The temperature at which oil becomes cloudy
and hazy, is known as cloud point. The
temperature at which oil stops flowing is pour
point.
13

5. Aniline point:
Definition: The minimum temperature at which equal volumes of the oil and aniline are in equilibrium is
known as aniline point. It indicates the deterioration of oil in contact with rubber materials .Higher the
aniline point less will be the damage to the rubber materials.
Significance: Naphthenic hydrocarbons present in oil have a tendency to dissolve rubber sealings, packings
etc., Higher aniline point indicates that the oil contains more paraffinic hydrocarbons than naphthenic
hydrocarbons. To avoid rubber damages and deterioration, a good lubrication oil should have high aniline
point.
Determination: Equal volumes of oil and aniline are mixed mechanically in a test tube. The mixture is
heated till a homogeneous solution is formed. Then it is allowed to cool. The temperature at which the two
phases ( oil and aniline) separate out is recorded as aniline point.

6. Carbon residue:
Definition: On heating, the lubricating oil decompose and deposits a certain amount of carbon on the
lubricated surface. This is known as carbon residue.
Significance: A good oil should have low carbon residue. Otherwise, it will lower the efficiency of the
internal combustion engines and air-compressors.
Determination:
The carbon residue of a lubricating oil is determined by Conradson method. Conradson apparatus contains
an inner silica crucible, middle Skidmore crucible and an outer iron crucible in order to attain controlled
heating.
A known quantity of oil sample is taken in silica crucible.
Skidmore crucible facilitates the escape of volatile matter.
Initially the setup is heated slowly for 10 minutes till flame
appears from the oil. Then it is heated strongly for another 15
minutes to remove all volatile impurities.
Then it is cooled and weight of the residue is measured.

% carbon residue =

Weight of the residue left in the apparatus


Weight of the sample oil taken

100

7. Oxidation Stability:
Definition: The property of lubricating oil to resist decomposition at the operating temperature is known as
decomposition stability. The decomposition may be due to oxidation, hydrolysis or pyrolysis.
Significance: A good lubricating oil should have high oxidation stability to have enhanced lubricating
property. For this, it should have very low sligh oxidation number.
Determination: Oxidation stability is measured by Sligh oxidation test. 10g oil is taken in a special flask
and oxygenated. It is heated for 2 hours at 200oC and cooled. Then petroleum naphtha is added and
allowed to stand for one hour. The precipitate formed is filtered, dried and weighed. From this sligh
oxidation number is measured.
Weight of the precipitate formed
X 100
Sligh oxidation number =
Weight of the sample oil taken
14

3.6) SEMI SOLID LUBRICANTS ( Grease)

Advantages of semi solid lubricants:


1. They can be used at high temperatures.
2. They act as seal proof for dust entry.
3. They are used in places where frequent lubrication is needed.
4. They can avoid the undesired squeezing problems which is a major drawback of liquid lubricant.

Definition:
When lubricating oil is mixed with metallic soap, they form grease. (eg) Na grease, Ca grease
The nature of the soap determines - a) The operating temperature of the grease
b) The water and oxidation resistance c) Stickiness of the grease d) Thickness of the grease
1) SODIUM GREASE (SODA BASE GREASE)
Preparation
Step 1: When oils and fats are undergoing saponification with NaOH, they form sodium soap.
CH2 - COOR
|
CH - COOR
|
CH2 - COOR
Oil

+ 3 Na OH

sodium hydroxide

CH2 - OH
|
CH OH + 3 R COO Na
|
CH2 - OH
glycerol
Sodium soap

Step 2 : Sodium soap + Lubricating oil Sodium Grease


Properties of Sodium grease:
1. It is yellow in colour.
2. It has fibrous texture.
3. It is soluble in water.
4. It can be used upto 175oC.
Uses of sodium grease:
1. It is used in ball bearing and roller bearing.
2. It is used in hotter zones.
3. It is used in heavy duty conveyors.
2) CALCIUM GREASE (LIME BASE GREASE/ CUP GREASE)
Preparation
Step 1: When oils and fats are undergoing saponification with Ca(OH)2, they form Calcium soap.
CH2 - COOR
|
2 CH - COOR
+ 3 Ca(OH)2
|
CH2 - COOR
Oil
calcium hydrodxide

CH2 - OH
|
2 CH OH
|
CH2 - OH
glycerol

+ 3 (R COO)2 Ca
Calcium soap

Step 2 : Calcium soap + Lubricating oil Calcium Grease


15

Properties of Calcium grease:


1. It is red in colour.
2. It has buttery texture.
3. It is insoluble in water.
4. It can be used upto 80oC.
5. Its drop point is lesser than soda grease.
Uses of Calcium grease:
1. It is used in Water pumps.
2. It is used in tractors.
3. It is used for other general purpose lubrication.
3) LITHIUM GREASE
Preparation
Step 1: When oils and fats are undergoing saponification with Li(OH)2, they form Lithium soap.
CH2 - COOR
|
2 CH - COOR
|
CH2 - COOR
Oil

+ 3 Li(OH)2

Lithium hydroxide

CH2 - OH
|
2 CH OH
|
CH2 - OH
glycerol

+ 3 (R COO)2 Li
Lithium soap

Step 2 :Lithium soap + Lubricating oil Lithium Grease


Properties of Lithium grease:
1. It is brown in colour.
2. It has buttery texture.
3. It is insoluble in water.
4. It can be used at very high and very low temperatures.
5. It is expensive and superior to other greases.
Uses of Calcium grease:
1. It is used in lower temperatures also.
2. It is used in aircraft applications where temperature reaches even to -55oC.
3. It is used only for special applications because of their high cost.

4) AXLE GREASE
Preparation:
They are derived from petroleum distillation by products. In small scale level, it is prepared by adding lime
to resin and fatty oils. The mixture is agitated thoroughly and allowed to stand. Fillers like talc, mica are
also added. Grease floats as stiff mass on the reaction mixture.
Properties of Axle grease:
1. It is dark brown to black in colour.
2. It is insoluble in water.
3. It is very cheap.
Uses of Axle grease:
1. It is used in the high load , low speed applications.
2. It is used for boat trailers.
3. It is used in metallic wires and ropes.
16

3.7) PROPERTIES OF GREASE:

1. Consistency (or) Yield value:


Definition: Consistency is defined as the distance (in 1/10th of a millimeter) that a standard cone vertically
penetrates into the grease under standard conditions of temperature (25oC), load (150 g) and time (5secs).
Significance: A grease should have high consistency to retain its lubricating nature.
Determination: The consistency is determined by penetrometer. The grease sample is taken in a sample cup
and it is placed under the standard cone. With the help of the mirror, the height of the cone is adjusted such
that its tip just touches the sample. The movement of the cone is controlled by a release button. The
apparatus contains circular graduated scale in 10th of millimeter. By applying a constant load of 150g,
scales initial reading is noted. All these parts are interconnected by clutch arrangement. Using the button,
the cone is released for exact 5 seconds. Now the reading in the gauge is noted. The difference of the two
readings gives the Penetration or yield value.

2. Drop point:
Defintion: The temperature at which the grease passes from the semi solid to the liquid state is known as
drop point.
Significance: The dropping point determines the maximum temperature upto which the grease can be
utilized. A good lubricant should have high drop point.
Determination:
The grease sample is taken in a metal cup. The cup
contains a tiny opening at its bottom. The cup is
enclosed in a glass case. A thermometer is inserted just
above the grease to monitor its temperature.
The entire setup is taken in a glass water beaker and
slowly heated at a rate of 1oC / minute. The water in the
bath is stirred constantly to maintain the temperature
rise uniformly.
As the temperature increases, the
grease sample passes from a semi solid to a fluid state.
The temperature at which its first drop falls from the
tiny opening is known as its drop point.
17

3.8) SOLID LUBRICANTS (e.g Graphite , Molybdenum disulphide)


Advantages of solid lubricants:
1. They can be used at very high temperature.
2. Used to avoid contamination.
3. To avoid accidents due to combustion.
1. GRAPHITE:
Structure:
i. )Graphite consists of flat layers of hexagonal arrangement of carbon atoms.
ii. ) Carbon atoms in hexagon are held by strong covalent forces (1.4Ao), while adjacent layers are held by
weak Vander walls force.
iii.) The distance between adjacent layers is 3.41 Ao . They can be easily slide over one another with very
little friction. They posses low coefficient of friction (0.05 0.001).
iv) Because of the above said reasons, graphite is acting as a lubricant.
Properties:
i. It is very soapy and non- inflammable.
ii. It can be used upto 375o C.
iii.Graphite is used either as dry powder or as a colloidal dispersion.
iv. Dispersion of graphite in water is aqua dag. Dispersion in oil is called oil dag.
Uses:
i. Oil dag is used in internal combustion engine.
ii. Aqua dag is used in air compressors and in processing equipments, food stuff industries.
iii. Graphite as a lubricant is used in lathe, machine work shop, open gears etc.
iv. Used in railway track joints.
Structure:

18

2. MOLYBDENUM DISULPHIDE ( MoS2)


Structure:
1.MoS2 has a sandwich like structure in which a layer of Mo atom lies between two Sulphur layers.
2. The atoms in the layers are bonded together by strong covalent bonds but the layers are held by weak
Vander walls forces.
No
1
2
3

Atoms
Mo - Mo
SS
Mo - S

Bond distance
3.15Ao
3.08Ao
3.13 Ao

3.The layers slide over one another due to the poor inter laminar attraction.
4. They posses low coefficient of friction.
Properties:
1. It gets oxidized above 800oC.
2. It is used either as dry powder or colloidal dispersion.
Uses:
1. Mainly used in heavy machines working under heavy load & high pressure.
2. Used in drilling machines, cutting zones and in railway tracks.
3. The MoS2 powder may be sprinkled on surfaces sliding at high velocities.
4. It is also used along with solvents and greases.
Structure:

19

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