CARBON

Allotropes of Carbon
• Carbon exists as many allotropic forms which can be classified
as crystalline and amorphous forms.
• CRYSTALLINE FORMS: Diamond , Graphite , Fullerene etc.
• AMORPHOUS FORMS: Charcoal, Coal, Lamp Black, Coke,
Gas Carbon etc.

Crystalline Allotropes of Carbon

i. Diamond:
It is the purest form of carbon and it is formed from coal beads in
the earth when high pressure is developed or applied. It occurs in
the form of transparent octahedral crystals and when uncut do not
shine. They are cut at proper angles which is a very specialized job.
This imparts large total internal reflection which lends them the
usual shine.
 Properties
• It is the hardest substance known and can scratch marble and
glass.
• It is transparent to X-rays.
• It has very high refractive index (2.417).
• Its density is also very high (3.51 at 15⁰C).
• It is a bad conductor of heat and electricity.
• It changes to graphite above 1800⁰C.
• It is resistant towards almost all chemical reagents but is
oxidized to carbon dioxide when heated to about 900⁰C in the
presence of air. i.e. C + O2 900⁰C CO2
 Structure
It has three dimensional structure in which each carbon atom
is joined to four other carbon atoms by covalent bond. Each
carbon – carbon bond is 1.54 A⁰ and the bond angle is 109.5⁰.
Each carbon atom lies at the corner of regular tetrahedron.
These covalent bonds are very strong which can explain the
hardness and high density of diamond. Its melting point is very
high (3500⁰C). Since ,all electrons are used for bonding and there
is no free electron, it is bad conductor of electricity.
 Uses of Diamond
• It is used for cutting glass, marble and graphite.
• It is used as precious stone in jewelry as a gem because of
brilliant shining property.
• It is used for grinding and polishing of hard surfaces.

ii. Graphite
Graphite is another crystalline allotropic form of carbon. It is
also called as ‘ Black lead’. It is prepared artificially by heating the
mixture of sand and coke in electric furnace at about 3000⁰C.
SiO2 + 3 C (coke) 2CO + SiC (silicon carbide)
SiC Si + C (graphite)
Properties
• It is soft to touch, dark grey substance and has metallic luster.
• It’s specific gravity is 2.2
• It is good conductor of heat and electricity.
• It marks paper black , hence it is called black lead. The lead of
pencil is a mixture of graphite and clay.
• It is resistant towards almost all chemical reagents but burns
in air an strong heating to yield carbon dioxide.
C + O2 CO2
• When heated with conc. HNO3, a yellow mass called graphite
acid ( C11H4O5) is obtained.
• With alkaline permanganate , it is oxidized to oxalic acid and
metallic acid [ C6 (COOH)6 ]
Structure
Graphite is a two dimensional layer structure. In each layer, the
carbon atoms are arranged in regular hexagonal rings. Each
carbon atom is joined to three other carbon atoms by covalent
bond. Each carbon – carbon bond length is 1.42 A⁰ and bond
angle is 120⁰. The two successive layers of graphite are 3.40 A⁰
apart. These layers can slip over each other. Thus graphite is soft.
Each carbon atom has one electron free which can move from
one point to the other. Thus, graphite is a very good conductor of
electricity.
Uses:
• It is used in making electrodes and carbon arcs.
• It is used for covering moulds during electro- deposition of
copper.
• It is used in making graphite crucibles.
• It is used as lubricant for high speed machines.
• It is used for making ‘Lead Pencil’.
iii. Fullerene
It constitute a new family of carbon allotropes consisting of large
spheroidal molecules of composition , C2n,where n≥30. These were
first prepared by evaporation of graphite using a powerful laser. Unlike
graphite or diamond, the fullerene dissolve in organic solvent.
Fullerenes are the only pure form of carbon.
Structure
Of all the fullerenes, C60 is the most stable. It looks like a soccer ball
and is sometimes called bucky ball. It contains 20 six membered rings
and 12 five membered rings. Six membered rings are fused both to
other six membered rings and five membered rings, but the five
membered rings are connected to only six membered rings.
All the carbon atoms are identical and they undergo sp2 –
hybridization. Each carbon atom forms three σ- bonds with other
three carbon atoms. The remaining electron of each carbon is
delocalized in molecular orbitals, which give aromatic character to the
molecule.
 The soccer ball shaped molecule has 60 vertices with a carbon
atom at each vertex. It contains both single and double bonds
with carbon – carbon distances of 145.3 and 138.3 pm
respectively. It is also called as Buckminster fullerene. All the
carbon atoms are equivalent and the strain caused by the
distortion of the bonds from coplanarity is equally distributed
among all the carbon atoms. So, the molecule is quite stable.
C70 fullerene is like a rugby ball which consist of 25 six membered
rings and 12 five membered rings.
Properties of C60 Fullerene
• It is very finely divided black powder (solid).
• It is odourless and sublimes at 800K.
• It is soluble in organic solvents.
• It can be hydrogenated by using strong hydrogenating agents. The
colour of the hydrogenated fullerene changes from black to brown,
then to red, orange, and light yellow with increasing hydrogen
content.
• When fullerenes are co- evaporated with metals like Li, Na, K, Ca and
Rb, endohedral fullerenes are obtained.
• They can be reduced electrochemically and react with group I alkali
metals, forming solids such as K3C60, which behaves as
superconductor below 18K.
• It forms platinum complexes.
• C60 behaves like an electron deficient alkenes and reacts readily with
electron rich species.
Uses:
• They can be used as organic photovoltaics (OPV).
• Due to high electron affinities of fullerenes, it can be used to
design molecular wires that can conduct electricity very
efficiently.
• They can be used to store hydrogen.
• They can be used as medicine carrier because they can
enclose atom.
• Fullerene derivative can be used in the photodynamic cancer
therapy as antibacterial agents and medication of
neuroprotective action.
• Endohedral fullerenes containing K element can be used in
the preparation of nano size ball- bearing.
Amorphous allotropes of Carbon
i. Charcoal
It is amorphous form of carbon and is soft, black and highly
porous. Different types of charcoal are as follows.
a. Wood Charcoal : It is made by the destructive distillation of
wood. It is highly porous and has vast internal surface area.
In this surface area, charcoal absorbs many times its volume
of gases.
Uses:
• As a fuel.
• For purifying drinking water.
• As a gun-powder material for blasting mines etc.
• For decolorizing sugar and other chemicals.
b. Animal Charcoal: It is also called bone black. It is the residue
obtained from the destructive distillation of bones. It consists of
approximately 10% carbon , which is easily wetted by liquids. Animal
charcoal gives carbon dioxide on heating, the residue left is called
bone ash.
Uses:
• For refining sugar.
• In the manufacture of superphosphate of lime ( fertilizer) and
phosphorus.
• For decolouring organic chemicals.
c. Sugar Charcoal: It is obtained by the action of concentrated H2SO4
on sugar. It is the purest form of amorphous carbon.
C12H22O11 conc. H SO 12C (sugar charcoal) + 11 H2O
2 4

Uses:
• To remove coloring matter.
• As black pigment.
 Activated Charcoal : All forms of charcoal are highly porous substance
and can adsorb many times their own volume of gases. Their adsorption
capacity can be further increased by heating charcoal at 1000⁰C in a
current of super heated steam. This treatment removes the impurity such
as residual hydrocarbons, oxygen etc. sticking on the surface and blocking
the capillary pores. Charcoal thus prepared is called activated charcoal.
ii. Lamp Black :
It is obtained by burning natural gases and other carbon compounds in a
limited supply of air. The soot obtained is made to stick on the wet
blanket hung in the chamber. After drying , the soot is removed from the
blanket. The black soot is one of the purest varieties of amorphous
carbon containing 98.6% carbon and 1.4% hydrogen.
Uses:
• In the compounding of rubber for tyres to make a tougher product.
• In the printers ink.
• In the manufacture of shoe polish.
• In the manufacture of black paint.
iii. Gas carbon:
A black deposit obtained on the roof and sides of retort during
the destructive distillation of coal ( in the manufacture of oil gas)
is called gas carbon. It is good conductor of electricity and used
for making electrodes in dry cell.
iv. Coke:
It is residue obtained in destructive distillation of coal. It is pure
form of carbon. It can be used as reducing agent in metallurgy
and as a fuel.
v. Coal:
It is formed by slow decomposition of vegetable matter under
the influence of high temperature and high pressure and in the
absence of air. This process is called carbonization. It can be used
as fuel, as reducing agent and in the manufacture of producer
gas.
Properties of Carbon monoxide ( CO )
Physical Properties
• It is a colorless, tasteless gas with slight smell.
• It is slightly lighter than air and its vapour density is 14.
• It is very slightly soluble in water. 130 volumes of water can
dissolve only 3 volumes of the gas at 0⁰C.
• It can be liquefied at -191.5⁰C and solidified at -200⁰C.
• It is highly poisonous gas. It’s 1 part in 1000 parts of air causes
severe headache and 1 % kills a person.
Chemical Properties
1. Action towards litmus : It is neutral towards litmus.
2. Combustibility: It is non- supporter of combustion but burns
itself in the presence of air or oxygen to produce carbon
dioxide with blue flame.
2CO + O2 2CO2
3. Formation of addition products:
Carbon monoxide is an unsaturated compound and gives
addition reaction. It is because oxidation number of carbon in
CO is +2 and can extend to +4.
• Action with hydrogen: When CO and hydrogen gas are passed
over catalyst ( ZnO & Cr2O3) at 300⁰C and 200 atm, methyl
alcohol is formed.
CO + H2 ZnO + Cr2O3 CH3OH(methyl alcohol)
300⁰C and 200 atm
• Action with sulphur: When CO and sulphur vapour are heated
together, carbonyl sulphide is produced.
CO + S ∆ O=C=S (carbonyl sulphide)
• Action with chlorine: A mixture of CO and chlorine gas reacts
in the presence of sunlight to yield phosgene gas which is very
poisonous. CO + Cl2 ∆ COCl2 (Phosgene)
• Formation of metal carbonyl : CO combines with transition
metals like nickel, iron, cobalt to form addition compound
called metal carbonyls.
Ni + 4 CO 80⁰C Ni(CO)4 (nickel tetra carbonyl)
Nickel tetracarbonyl decomposes when heated at 180⁰C to yield
back nickel. So, this process is used for the purification of nickel.
Fe + 5 CO Fe(CO)5 (iron pentacarbonyl)
2Co + 8 CO [Co(CO)4]2 ( dicobalt octacarbonyl)
• Action with sodium hydroxide :Sodium formate is obtained
when CO is passed through heated caustic soda at 200⁰C
under pressure.
CO + NaOH 200⁰C HCOONa (sodium formate)
• Action with Hemoglobin: Blood contains hemoglobin, a red
pigment. CO combines with hemoglobin to form stable
carboxyhaemoglobin.
 Hemoglobin + CO Carboxy hemoglobin
This prevents hemoglobin to carry oxygen to the different parts of
body from lungs and causes suffocation and even death. Thus CO gas
is a poisonous gas.
4. Reducing character: CO is easily oxidized to CO2, so it behaves as
a very good reducing agent.
• Reduction of metal oxide:
PbO + CO ∆ Pb + CO2
ZnO + CO ∆ Zn + CO2
Fe3O4 + 4 CO ∆ 3Fe + 4CO2
• Reduction of Tollen’s Reagent : Ammonical silver nitrate solution
is called Tollen’s reagent. When CO is passed through it, silver is
obtained in the form of mirror.
2[Ag(NH3)2]+OH- + CO 2Ag + CO2 + H2O + 4NH3
Tollen’s reagent (silver mirror)
• Reduction of Fehling’s Solution: CO reduces Fehling’s solution and forms
red ppt. of Cu2O.
Cu(OH)2 + CO Cu2O + H2O + CO2
(Red ppt.)
Uses of CO:
• As its burning is an exothermic reaction, it is used as a fuel in combination
with hydrogen (water gas).
• It is very good reducing agent and is used in metallurgical operations.
• It is used for the extraction of Nickel and Iron by forming their volatile
carbonyls.
• After combination with chlorine, a poisonous gas phosgene is produced
which is used in warfare.
Test of CO
• It burns with blue flame.
• When a filter paper soaked in platinic chloride is brought in contact with
CO, it turns green, pink or black due to reduction of the metal chloride by
CO.