UNIT – III

ASSOCIATIVE INTERACTIONS AND LUBRICANTS

Intermolecular interactions
H2O-H2S, HCl-HF, Ethanol-diethyl ether, Polyethylene-Teflon.

Lubricants- Mechanisms of lubrication

Fluid film, Boundary film & Extreme pressure.
Types of lubricants

Properties of lubricants and its significance

Physical properties – Viscosity & Viscosity Index.
Determination of viscosity
Lubricating oils – Acid value, Saponification value, Steam
emulsification number
Intermolecular Forces
 Dispersion Forces London dispersion

• American physicist Fritz London who, in 1928, first explained it

• molecule can develop a temporary,

instantaneous dipole if its
electrons are distributed
asymmetrically

• The presence of this dipole can, in

turn, distort the electrons of a
neighboring atom or molecule,
producing an induced dipole
 Dispersion Forces

very polarizable
Dispersion Forces
Dipole-Dipole Attractions
 Dipole-Dipole Attractions

Predict which will have the higher boiling point: N2 or CO. Explain your reasoning

CO and N2 are both diatomic molecules with masses of about 28 amu, so they
experience similar London dispersion forces. Because CO is a polar molecule, it
experiences dipole-dipole attractions. Because N2 is nonpolar, its molecules
cannot exhibit dipole-dipole attractions. The dipole-dipole attractions between
CO molecules are comparably stronger than the dispersion forces between
nonpolar N2 molecules, so CO is expected to have the higher boiling point.
Hydrogen Bonding
 Hydrogen Bonding

• Examples of hydrogen bonds include

• HF⋯HF, H2O⋯HOH, and H3N⋯HNH2,

• hydrogen bonds are denoted by dots

Q. Consider the compounds dimethylether (CH3OCH3), ethanol (CH3CH2OH),

and propane (CH3CH2CH3). Their boiling points, not necessarily in order, are

−42.1 °C, −24.8 °C, and 78.4 °C. Match each compound with its boiling point.

Explain your reasoning.

 Hydrogen Bonding

Ethane (CH3CH3) has a melting point of −183 °C and a boiling point of −89 °C.

Predict the melting and boiling points for methylamine (CH 3NH2). Explain your

reasoning
ion-dipole attraction
Relative strength of intermolecular forces
 Relative strength of intermolecular forces

H2O-H2S

HCl-HF,

Ethanol-diethyl ether,

Polyethylene-Teflon

Teflon
 Properties of liquid – IMF - Viscosity

(a) Honey and (b) motor oil are examples of liquids

high viscosities; they flow slowly
 cohesive forces
The various IMFs between identical molecules of a substance are examples
of cohesive forces

• The molecules within a liquid : surrounded by other molecules

• Attracted equally in all directions by the cohesive forces

• on the surface of a liquid : attracted only by about one-half

.
 cohesive forces

• Unbalanced molecular attractions on the surface molecules

contract to form a shape
Less number on the surface
the shape with the minimum surface area
• A small drop =
Looks spherical

• because in a
sphere, the ratio
of surface area
to volume is at a
minimum.
 Surface tension

• Surface tension : energy required to increase the surface area of a

liquid
• results from the cohesive forces between molecules at the surface of a
liquid

• water exhibits a distinctly high

surface tension due to strong
hydrogen bonding between its
molecules
 Surface tension

relatively “tough skin” that can withstand considerable force without breaking
 Lubricants and Lubrication
The substances which are used to decrease the force of friction between the moving parts of machine
in contact are known as Lubricants
 Harms from frictional resistance

• energy loss

• extra work has to be done.

• generation of heat in areas in contact

• heated parts may melt and get deformed, leading to seizure (welding of two

surfaces due to heat) of the system.

• breaking of asperities brings about abrasion or surface wear and tear.

 Functions of Lubricants

1. reduces frictional resistance:

2. surface deformation.

3. lubricating oil absorbs heat: acts as a coolant.

4. increase the efficiency of the machine.

5. Less maintenance cost and more life

7. carry away debris and contaminant

9. Reduce noise and prevent corrosion, rust.

9. Avoid seizure of the moving parts

 Mechanism of Lubrication

1. Fluid film or thick film or hydrodynamic lubrication

2. Thin film or boundary lubrication

3. Extreme pressure lubrication

Fluid film or thick film or hydrodynamic lubrication
Viscosity – Inter Molecular Forces
 Fluid film or thick film or hydrodynamic lubrication

• formation of an oil wedge

• consider the rotation of a shaft with respect to a stationary bearing

• lubricant is introduced in the annular space

• In the rest position, the shaft rests at the bottom of the bearing and all the
lubricant is squeezed out, resulting in contact between the two surfaces

• When torque applied: Formation of oil wedge and surface floats over the other
surface without mutual contact

• Lubricants: minimum viscosity and remain in its place and separate the sliding
surfaces
 Fluid film or thick film or hydrodynamic lubrication

Hydrocarbon oils:

Viscosity decreases with rise in temperature

To maintain viscosity in all temperature, blended with suitable long

chain polymers.

Hydrocarbon oils contain a small fraction of unsaturated hydrocarbons

To avoid oxidation of these unsaturated hydrocarbons antioxidants :

aminophenol
 Fluid film or thick film or hydrodynamic lubrication

Examples

• Delicate instruments like watches and clocks.

• Light machines like sewing machines and scientific instruments.

• Large plain bearings like pedestal bearings and main bearings of diesel

engines
Fluid film or thick film or hydrodynamic lubrication
Fluid film or thick film or hydrodynamic lubrication
 2. Thin Film Lubrication

thickness 20–30 Å
2. Thin Film Lubrication
 2. Thin Film Lubrication

For boundary lubrication, the lubricant should have the following characteristics

• Oiliness: capacity to stick to the metal surface should be good.

• long hydrocarbon chains: increases the lateral attraction - greater the van
der Waals

• polar groups and active groups needed: adsorb on surface or react

chemically

• high-viscosity index are required and resistance to oxidation.

• Cloud and pour point should be low.

 2. Thin Film Lubrication

good oiliness
Vegetable oils
animal oils and
glycerides of higher fatty acids,
and their soaps
for example,
oleic acid (C17H33COOH)

and stearic acid (C17H35COOH).

polar –COOH group reacts with the metal surface to form a
continuous film and the hydrocarbon chains of fatty acids are oriented
outwards in a perpendicular direction
 2. Thin Film Lubrication

Examples

• Lubrication of journal bearing in diesel engines

• Guide and guide shoe in two stroke engines.

• Hydraulic pumps such as the vane pump.

• Valve trains, especially cams and followers.

Extreme pressure lubrication

The coefficient of friction

is 0.1 to 0.4 cm/s

use in aircrafts and spacecraft

Extreme pressure lubrication
 Classification of lubricants

On the basis of their physical state, lubricants

1. Liquid lubricants or lubricating oils

2. Semi-solid lubricants or greases

3. Solid lubricants
 Liquid lubricants or lubricating oils

(i) Animal and vegetable oils

• glycerides of higher fatty acids

• Familiar due to oiliness; sustain at high T and load

• Used as blending agent along with mineral oil

to improve oiliness

Ex: olive oil, mustard oil, castor oil, palm oil, rapeseed oil, whale oil

Limitation: Expensive and High chance of oxidation/ hydrolysis

 Liquid lubricants or lubricating oils

(ii) Mineral oils or petroleum oils

• distillation of crude petroleum

• hydrocarbon chain: 12 to 50 carbon long

• Less oiliness and using animal oil to improve it

• Not expensive

• More stable
 Liquid lubricants or lubricating oils
(iii) Blended oil, doped oils or compound oils

adding certain additives

Antioxidants or inhibitors (Aminophenol)

Oiliness carriers (Veg. oil)

Viscosity index improvers (hexanol)

Pour point depressants (alkylated naphthalene, phenolic polymers and

polymethacrylates)
 Liquid lubricants or lubricating oils
(iii) Blended oil, doped oils or compound oils
Detergents and deflocculents (calcium and barium salts of phosphates and
sulphonates)
Dispersants (high-molecularweight amides and amide polymers.)

Metal deactivators (amines, sulphides or phosphides)

Antifoaming agents (glycol, glycerol and silicon polymers)

Rust and corrosion inhibitors

Extreme pressure additives (sulphurized fats, phosphorus compounds)

Abrasion inhibitors (tricresyl phosphate)

Emulsifiers (sodium salts of sulphonic acids and sodium salts of organic acids )
 Semi-solid lubricants

• Greases: oil + thickening agen

• colloidal structure or gel

• basic active ingredients – a lubricating oil, additive and

thickeners
Semi-solid lubricants
 Solid lubricants

• Very high temperatures and pressure

• MoS2 are used in vacuum

• Use in dust free zone

layered or lamellar structures

 Solid lubricants - Graphite

distance of 3.4 Å and are

held together by weak van der

Waals forces

soapy and slippery by nature

graphite with oil is called oildag Graphite is commonly used in air

compressors, food industry, ball
graphite with water is called aquadag bearings, railway track joints,
etc.
 Solid lubricants – MoS2

Sandwich like structure

MoS2 has low shear

strength in a direction parallel
to the layers due to poor
interlaminar attraction

low coefficient of friction

Not in wet; increase the friction

Use in vacuum and space.

 Lubricating Emulsions

Emulsion: colloidal solution of more than one immiscible liquid

dispersed in another in the form of droplets
 Lubricating Emulsions

Lubrication: Emulsion (oil in water or water in oil type)

• In machining operation: milling, boring, turning,

cutting

• gets heated to a high temperature

• Effective cooling and lubrication is needed

• Oil in water emulsions used for this purpose

• oil : lubricates and water : as a coolant

• Ex: Fatty acids = lard oil and sperm oil

Lubricating Emulsions
 Lubricating Emulsions
Preparation:

1. Water and oil

2. 1 to 10% of water insoluble emulsifiers like alkaline earth metal soaps

emulsifier : substance that essentially helps in the formation and
stabilization of an emulsion.

surface-active agents act as the interface between the two

immiscible liquids, like oil and water.

have a hydrophilic end that forms chemical bonds with water

and a hydrophobic end that forms chemical bonds with oils

 Properties of lubricants and its significance
Viscosity
resistance to its own flow

Liquid: consist of a series of parallel layers moving one above the

other.
coefficient of viscosity velocity difference

Distance between two layers

Force required to maintain this velocity difference

 Properties of lubricants and its significance
Viscosity
 Properties of lubricants and its significance

Viscosity

If v = 1cm/s and d = 1 cm, then

coefficient of viscosity

the force per unit area required to maintain a velocity difference of

unity between two parallel layers separated by unit distance

 Properties of lubricants and its significance

Viscosity index (VI)

• Empirical scale for viscosity of oil with T

• average decrease in viscosity of oil per degree rise in T

(100 °F and 210 °F)

• low-viscosity index: viscosity of a lubricant decreases rapidly with the

rise in T

• high-viscosity index: not rapid decrease of viscosity with rise in T

 Properties of lubricants and its significance
Determination of viscosity index
Two types of standard oils are used to determine VI

Paraffinic-based Pennsylvanian oils: High VI; H-oils and assigned VI = 100.

Naphthenic-based Gulf oils: Low VI; L-oils and assigned VI = 0.

For test oil:

Experiment viscosity at 100 °F and 210 °F are U and V respectively.

list of H-oils: viscosity at 210 °F is the same as that of the test oil at 210 °F
its corresponding viscosity at 100 °F = H.

list of L-oils, that oil is selected whose viscosity at 210 °F is the same as that of
the test oil at 210 °F and again its corresponding viscosity at 100 °F = L.
 Properties of lubricants and its significance
Determination of viscosity index
 Properties of lubricants and its significance
Determination of viscosity index

depends : molecular structure of the compound

Linear molecules have high-VI

Branched molecules have low-VI

(prevent the alignment of the neighbouring molecules)

increased by adding organic polymers like polyisobutylene, n-hexanol, etc.

(i) Viscosity of the lubricating oil decreases.

(ii) Solubility of the polymer in the lubricating oil increases, resulting in
increase in its viscosity.
two opposing effects: the viscosity of the lubricant remains constant
or the viscosity index of the lubricant increases
Redwood viscometer
 Redwood viscometer
• silver plated brass cup
• Orifice: opened and closed with the help of a ball valve
Oil cup: • upper open end of the cup is closed with a lid having holes,
• one for the thermometer
• and the other for the ball valve
• side wall of the cup : a pointer towards the upper side of the cup
oil filled to the pointer

• oil surrounded by a copper bath with water

Heating bath: • tap for emptying the water
• thermometer is for temp. of water
• Stirrer in the outer cylinder to make homogeneous

Spirit level: on the lid for levelling

Kohlrausch flask: calibrated flask at the bottom

 Pensky Marten apparatus
for finding Flash and Fire point
 Cloud Point and Pour point

Cloud Point Pour point

 Steam emulsion number (SEN)

• Emulsion (water in oil): poor lubricating and cause abrasion and

wearing
• good lubricating oil: forms an emulsion with water and breaks off quickly
TEST:
• 20 mL of oil is taken in a test tube and steam at 100 °C is bubbled in, till
the temperature rises to 90° C

• tube is kept in a bath maintained at 90 °C

• time in seconds: When the oil and water separates out into distinct layers

• That time = SEN

• good lubricant should have a low SEN

 Acid Value (total acid number (TAN)

number of milligrams of KOH needed to neutralise any acid in one gram of oil

A known weight of oil is dissolved in a neutral alcohol and titrated against 0.1 N
KOH using phenolphthalein as the indicator

Acid value of a lubricant should be less than 0.1. A value greater than 0.1
indicates that the oil has been oxidized.
 Saponification number

• An ester on alkaline hydrolysis gives alcohol and sodium or potassium salt of an

acid.

• The saponification number is defined as the number of milligrams of KOH

required to saponify the fatty acid present in 1 gram of oil.

• It is determined by refluxing a known quantity of oil with a known excess of

potassium hydroxide solution and titrating the unused alkali against an acid.
Saponification number
 Secondary Batteries
Lead acid battery
The main active materials required to construct a lead acid battery are

Lead Peroxide (PbO2)

The positive plate is made of lead peroxide. This is dark brown, hard

and brittle substance.

Sponge Lead (Pb)

The negative plate is made of pure lead in soft sponge condition.

Dilute Sulfuric Acid (H2SO4)

Cell notation Pb–PbSO4 / H2SO4 (5 M) / Pb – PbSO4–PbO2

Discharge
(Voltaic)

Recharge
(Electrolytic)
 Secondary Batteries
Lead acid battery
• Voltage of each cell 2 V; Total voltage of six cells in series 12 volts

discharging
• overall: Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(l)
charging

• Sulphuric acid gets diluted during discharging

Hydrometer

Charge indicator