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What are Fullerenes? Fullerenes are a group of polymorphic form of pure carbon compounds whose discrete molecule consists of hollow spherical cluster of a large number of carbon atoms.
Characteristics of Fullerenes: Each molecule is composed of groups of carbon atoms that are bonded to one another to form both hexagon (6-membered ring) and pentagon (5membered ring) geometrical configurations. But no two pentagons share a common side. Fullerene cages are about 7-15 angstroms in diameter ( 1A = 10-10m). In atomic terms, their sizes are enormous. But fullerenes are still small compared to many organic molecules. Chemically, they are quite temperatures of over 10000 C. stable; breaking the balls requires
At much lower temperatures (a few hundred oC) fullerenes will "sublime which means vapour will form directly from the solid. Fullerene-20 (C20) is the smallest number of carbon atoms containing fullerene. Giant fullerene with at least 600 Carbon atoms have been discovered.
Pentagon (C5)
The rugby-ball shaped C70has 12 pentagons and 25 hexagons Gives red color with dichlorobenzene
Hexagon (C6)
The soccer-ball shaped C60 has 12 pentagons and 20 hexagons Gives pink color with toluene
(i) preparation of superconductors, (ii) electronic devices, (iii) micro-electronic devices, (iv) preparation of ferromagnetic materials, and (v) as charge carriers in batteries.
Applications:
Set-up Assembly: The main part is the extra-pure spectroscopic grade graphite rods of 6 mm dia and 150 mm length fixed in copper holders. The facing sides of both the graphite rods are parallel. The arc chamber has a cooling coil attached to remove the heat produced. The power to the generator is a high current, low voltage power supply. Working method: The chamber is evacuated to 10-3 torr using a vacuum pump. The pump is disconnected and the chamber is now filled with 99.99% pure Helium gas to a pressure of 100 to 200 mm Hg. An arc is strike between two graphite electrodes kept at a distance of 2 mm apart by maintaining a voltage of 25 V. At the end of the reaction, the chamber is cooled down and the soot is collected from the inner walls.
Composition and separation of the soot from the DC Arc method
The soot contains (a) Carbon clusters mixture = 25-30%; and b) C60 and C70 fullerenes = 1.2-2.5%. Fullerenes can be separated from the carbon mixture by Soxhlet extraction with toluene followed by separation in a ultrasonicator bath. The obtained C60+C70 mixture is further separated by column chromatography using neutral alumina as the stationary phase and hexane as the mobile phase..
Resistance
Temp. (K)
Hydrophobic sites
al eric d ylin C
LUBRICANTS
Friction:
Resistance observed between two moving or sliding surfaces creating wear and tear.
Lubricant:
Any substance introduced between two moving or sliding surfaces with a view to reduce the frictional resistance between them is know as a lubricant.
Lubrication:
The process of introducing lubricant between moving/sliding parts is known as lubrication
Functions of Lubricant
o To reduce frictional resistance between surfaces and
reduce deformation, wear and tear between moving/sliding surfaces. To reduce loss of energy in the form of heat (Coolant). To reduce waste of energy i.e., to increase efficiency of machines. To reduce irregular expansion of metals. To reduce welding of the two surfaces. To reduce or avoid rough relative motions of moving / sliding parts. To reduce running and maintenance cost of the machine. To reduce the leakage of gases under high pressure like a seal or Teflon.
o o o o o o o
Mechanisms of Lubrication
1. Fluid-film (or) Thick-film (or) Hydrodynamic lubrication 2. Boundary lubrication (or) Thin-film lubrication 3. Extreme pressure lubrication
1. Fluid Film/Thick-Film/Hydrodynamic
Lubrication (~ 1000 )
Characteristics:
o The surfaces are separated by a thick-film (at least 1000 thick) and hence there is no direct surface to surface contact. o No welding of junctions. o Since thick film lubricant covers/fills the irregularities on the both surfaces, there is no direct contact between material surfaces and so the wear is reduced.
Lubricant oil covers the irregularities of the shaft as well as the bearing surfaces.
Mechanism of Boundary Lubrication/Thin-film Lubrication This Lubrication takes place due to:
o Adsorption of lubricating oils to both surfaces by physical/chemical means. o The adsorbed layers on the both metal surfaces carry the applied load. o Co-efficient of friction, f = 0.05 - 0.15 and distance between surfaces is to be the order of the distance of the asperities.
the
lubricant
(i) Long hydrocarbon chain with polar groups. (ii) Polar groups promote spreading and orientation over the metallic surfaces at high pressure. (iii) Lateral attraction between the chains. (iv) Active groups or atoms, which can form chemical linkages with metal or other surfaces.
Graphite and Molybdenum disulphide alone or oil suspension may be used because:
o They have Low internal friction o They can bear/withstand compression o They are thermally stable
3. Extreme-pressure Lubrication
When moving/sliding surfaces are under very high pressure and speed, a high local temperature is attained. In such conditions, liquid lubricants fail to stick and may decompose and even vaporize. To avoid this, special additives are added to mineral oils. These are called extreme-pressure additives.
Mechanism
The extreme-pressure additives form on metal surfaces more durable films, capable of withstanding very high loads and high temperatures. Examples:
Organic compounds containing chlorine, sulphur and phosphorus. o These compounds react with metallic surfaces, at prevailing high temperatures, to form metallic chlorides, sulphide or phosphides. o These metallic compounds possess high melting points.
CLASSIFICATION OF LUBRICANT
Based on Physical state, lubricants are classified as: a) Lubricating oils or liquid lubricants
b) Semi solid lubricants or greases c) Solid lubricants
Liquid lubricants are most widely used lubricants because they are
1. Cheap 2. Available in abundance 3. Quite stable under service conditions.
f) Antioxidants or inhibitors : Aromatic phenolic or amino compounds g) Corrosion preventers : Phosphorous or Antimony organic compounds h) Abrasion inhibitors i) Antifoaming agents j) Emulsifiers k) Deposit inhibitors : tricresyl phosphate : glycols and glycerol : sodium salts of sulphonic acid : detergents such as salts of phenol and carboxylic acids
Applications of Greases:
o o o o When oil cannot remain in place due to high load, low speed, intermittent operation, sudden jerks etc. Work at high temperature When external contamination may create problem When dripping or spurting of oil is undesirable
Types of greases:
o
o o o o o
Calcium based greases or cup-greases Soda-based greases Lithium-based greases Axle- greases lime with resin and fatty acids Graphite greases Soap stone
3. SOLID LUBRICANTS
Solid lubricants are used when:
o Other lubricants can not be used o Contamination undesirable o Too high temperature or load are involved o Combustible lubricants not acceptable
Properties of Lubricants
1. Viscosity: The property of a liquid or fluid by virtue of which it offers resistance to its own flow . - Viscosity should not be too low or too high.
Flash Point:
The lowest temperature at which the oil lubricant gives off enough vapour that ignites for a moment, when a tiny flame is brought near it. Fire Point: The lowest temperature at which the vapour of the oil burn continuously for at least five seconds, when a tiny flame is brought near it.
3. Oiliness: A measure of its capacity to stick on to the surfaces of machine parts under conditions of heavy pressure or load.
o For high pressure
5. Volatility:
o Good lubricant should have low volatility.
o It is measured by vaporimeter.
6. Emulsification:
o The property of oils to get intimately mixed with water forming
an emulsion. o Emulsions have a tendency to collect dirt, girt, foreign material etc., causing abrasion and wearing out of the lubricating parts of the machinery. o A good lubricating oil should form an emulsion with water which breaks off quickly.
7. Carbon residue:
Normally lubricants consist of high % of carbon containing compounds.
o Lubricants decompose due to raise in temp. and deposit
carbon creating problems to : a) IC engines and b) Air compressors. o A good lubricant should deposit least amount of the carbon .
8. Corrosion stability:
Corrosion Test: o A polished copper strip is placed inside a lubricating oil for a specified time and temperature and then checked for any tarnishing . o To prevent or retard corrosion effect of lubricating oils, additives such as Phosphorous, Arsenic, Antimony, Chromium, Bismuth or Lead are added.
9. Decomposition stability:
o Lubricating oils must be stable to decomposition at the operating temperatures by : a. Oxidation: To prevent it anti oxidant or inhibitor are used. b. Hydrolysis: Moisture in oils causes hydrolysis of esters c. Pyrolysis : At high temperature
abrasion and wear it may cause 14. Saponification number: o Number of milligrams of KOH required to saponify 1g of oil.
16. Neutralization Number: o Is a scale to determine the amount of acidic or basic constituents of an oil. o Acid Number: Amount of KOH required in milligrams to neutralize the fatty acids in 1g of oil. o Good lubricating oil acid number value < 0.1
C. Propellants
High oxygen containing fuels or mixture of fuels + oxidiser Controlled combustion Evolution of Huge volume of hot gases (temp= 3000oC & pressure: 300kg/cm2) Gases escape through a jet or nozzle at supersonic velocity.
o Safe to store
o Burning should be smooth
Examples :
H2O2, nitro methane, ethylene oxide, hydrazine, propyl nitrate a mixture of 21.4% MeOH and 78.4% H2O2 solution
Bipropellants
Fuel and oxidiser are separate compounds and injected separately to the combustion chamber from separate compartments Fuels: Liquid hydrogen, hydrazine, ethyl alcohol, aniline, kerosene. Ethanol mixed with 25% of water
Liquid propellants
High Not easy Delicate engine design Less economical Versatile Easy