58572
58572
58572
UNIT 3
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
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.
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
FATS / OILS
GLYCEROL
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
+ 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
+ I2
HgCl 2
Titration - I
Standardisation of KOH
Burette solution
KOH
Pipette solution
Indicator
Phenolphthalein
End point
From the volume of the KOH solution in burette, KOH strength can be known.
Titration II
Determination of Acid value
Burette solution
Pipette solution
Indicator
Phenolphthalein
End point
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
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
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
PROCEDURE
Burette solution
Pipette solution( In
iodine flask)
Additional solution
Indicator
End point
FORMULA
Iodine value
RESULT
The iodine value of the given oil sample was found to be =___________.
7
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:
Impurity
Wax
Drawbacks
Raises the pour point and the
lubricant cannot be used at low
temperatures.
Asphalt /
Naphthenic
impurity
Sulphur /
unsaturated
compounds
Coloured
materials
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
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.
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
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 =
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
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
CH2 - OH
|
2 CH OH
|
CH2 - OH
glycerol
+ 3 (R COO)2 Ca
Calcium soap
+ 3 Li(OH)2
Lithium hydroxide
CH2 - OH
|
2 CH OH
|
CH2 - OH
glycerol
+ 3 (R COO)2 Li
Lithium soap
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
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
18
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