CARBIDES ,

FULLERENES &
FLUROCARBONS
Submitted by-
Priyanshi Tiwari
Sakshi Mishra
Saman Arif
Shweta K.K
 CARBIDES
The binary compounds of carbon formed with metals
and metalloids are called carbides.The carbides are
classified as follows :
 Saline Carbides are largely ionic solids ; they are
formed by the elements of group 1&2 and Al.
 Metallic Carbides have a metallic conductivity and
lustre ; they are formed by d block elements.
 Metalloid Carbides are hard covalent solids formed by
B & Si.
(i) Saline Carbides
Carbides formed with highly electropositive metals are
called saline carbides.
Saline carbides of the Group 1 and 2 metals may be divided
into three subcategories:
1. Graphite intercalation compounds, such a KC8.
2. Dicarbides (or ‘acetylides’), which contain the dicarbide
anion.
3. Methides which formally contain the carbide anion.
• Graphite intercalation compounds
1. They are formed by a redox process, and
specifically by the reaction of graphite with alkali
metal vapour or with metal ammonia solution.
2. A series of alkali metalgraphite intercalation
compounds can be prepared with different
metal:carbon ratios, including KC8 and KC16.
3. They are formed by group 1 metals. For example –
KC8.
• Dicarbides
1. They contain dicarbide C22- ion and are formed
by a broad range of electropositive metals.
2. Some dicarbides have a structure related to
rock salt, but replacement of the spherical
chloride ion by the elongated [C=C]2- anion
leads to elongation of crystal results in
tertragonal symmetry.
3. The C-C bond is significantly longer in
lanthanoid dicarbides. Be2C & Al4C3 are borderline
between saline & metalloids.
• Methides
Crystal structures of methides
are used to indicate the
existence of directional
bonding to the C atom in
carbides (as distinct from the
non-directional character
expected of purely ionic
bonding).
 (ii) Metallic Carbides
 They are sometimes referred as interstitial carbides. Examples.,
Co6Mo6C & Fe3Mo3C.
 The hardness and other properties of metallic carbides
demonstrate that strong metal-carbon bonding is present in them.
 Some of these carbides are economically and technologically
useful materials.
 Metallic carbides of composition MC have a fcc or hcp
arrangement of metal atoms with C atom in octahedral holes.
 The C atoms in carbides of composition M2C occupy only half the
octahedral holes between the closed packed metal atoms.
 However the bonding can be expressed in terms of delocalized
M.Os formed from the C2s & C2p orbitals and d orbitals of the
surrounding metal atoms.
 It has been found that rc /rm<0.59.(Applicable on N/O metal comp.
(iii) Metalloid Carbides
• They are also called covalent carbides formed with B & Si.
• Silicon carbide (SiC) is known as carborandum is prepared bt
reduction of silicon dioxide (SiO2) with elemental carbon in an
electric furnance.
• SiC is extremely hard & chemically inert possessing a diamond
like tetrahedral structure. It is used industrially as an abrasive.
• Boron carbide (B4C) has similar properties & is prepared by
reduction of boron oxide (B2O3) with C in electric furnance.
• In B4C structure, the boron atoms occur in icosohedral group of
12, and the C atom occur in linear chains of three.
• Another boron carbide BC3, which has a graphite like structure is
produced from reaction of Benzene (C6H6) and Boron trichloride
(BCl3) at 800°C.
 FULLERENES
 fullerene is an allotrope of carbon whose molecule consists of carbon atoms
connected by single and double bonds so as to form a closed or partially
closed mesh, with fused rings of five to seven atoms. The molecule may be a
hollow sphere, ellipsoid, tube, or many other shapes and
sizes. Graphene (isolated atomic layers of graphite), which is a flat mesh of
regular hexagonal rings, can be seen as an extreme member of the family.
 Fullerenes with a closed mesh topology are informally denoted by
their empirical formula Cn, often written Cn, where n is the number of
carbon atoms. However, for some values of n there maybe more than
one isomer.
 The family is named after buckminsterfullerene(C60), the most famous
member, which in turn is named after Buckminster Fuller.
 The discovery of fullerenes greatly expanded the number of known
allotropes of carbon, which had previously been limited to
graphite, diamond, and amorphous carbon such as soot and charcoal.
• Carbon also exists in several less crystalline forms, as
well as the fullerenes and related compounds.

(a) Carbon clusters

Key point: Fullerenes are formed when an electric arc is discharged
between carbon electrodes in an inert atmosphere.

• When an electric arc is struck between carbon electrodes in

an inert atmosphere, a large quantity of soot is formed
together with significant quantities of C60 and much
smaller quantities of related fullerenes, such as C70, C76,
and C84.
• The fullerenes can be dissolved in a
hydrocarbon or halogenated hydrocarbon
andd separated by chromatography on an
alumina column.
• The ctureturecture of C60 has been
determined by X-ray crystallography On the
solid at low temperature and electron
diffraction in the gass phase.
• Some of the most interesting consequences of
fullerene re-search have been the identification
of carbon nanotubes.
• Graphene has very high electrical conductivity,
opacity, and strength and is being investigated for
use in electronic devices, bat-teries, and for gas
storage.
• The method that produces the cleanest graphene
surface is exfoliation, where the surface is
mechanically ripped from a graphite crystal.

(b) Metal
complexes
The polyhedral fullerenes undergo reversible multielectron reduction
and form complexes with d-metal organometallic compounds and with OsO4.
• In addition to complexes formed with the metal
atom outside the fullerene cage, endohedral
fullerenes are formed in which one or more atoms
are accommodated inside the C60 shell.

APPLICATIONS OF
FULLERENE
•One of the most important uses of Fullerene is medicine.

•Fullerenes are active molecules.

• Fullerene molecule can be used as an
antioxidant because it can easily react with
radicals due to the high affinity of the electron.

• It has also been shown that the Fullerenereagent

forms a protective layer on the DNA and extends the
DNA life of the endosomes.
 FluorocarbonS
Fluorocarbon molecules and polymers are resistant to oxidation.
Fluorocarbons find many useful applications . The
Direct reaction of an aliphatic hydrocarbon with an oxidizing
Metal fluoride leads to the formation of strong CF bonds
(456 kJ /mol’)and produces HF as a byproduct:
RH(l) + 2CoF (s) -- RF(sol) +2CoF (s) + HF(sol)
R =Alkyl or aryl
When R is aryl, CoF3
yields the cyclic saturated fluoride
C6H6 + 18CoF3  C6 F12 + 18CoF2. + 6HF
The strongly oxidizing fluorinating agent used in these reac-
tions, CoF3,is regenerated by the reaction of CoF2 with fluorine:
2CoF2 + F2  2CoF3
Another important method of CF bond formation is halogen
exchange by the reaction of a nonoxidizing fluoride, such as
HF, with a chlorocarbon in the presence of a catalyst, such
as SbF3
CCl 4 + HF  CCl 4 + HCl
CHCl3 + 2HF  CHClF 2 + 2HCl
These processes used to be performed on a large scale to produce the
chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that
were used as refrigerant fluids, the propellant in spray cans, and in the
blowing agent in plastic foam products. These applications have been
banned in some countries and are being phased out worldwide because
of the role of CFCs
and HCFCs in ozone depletion.
 They are being replaced by hydrofluorocarbons
(HFCs) after investment by the chemical industry
because, in contrast to the simple one-step synthesis
of CFCs and HCFCs, HFC production is a complex
multistage process.
For example, the preferred route to CF3CH2F, which
is
one of the preferred CFC replacements is
The polymerization of tetrafluoroethene is carried out
with a radical initiator:
nC F  -(CF -CF -)-n
2 4 2 2

Polyteptrafluoroethene (PTFE) is sold under many

trade names, one of which is Teflon (DuPont). Its
depolymerization at high temperatures is the most
convenient method of preparing tetrafluoroethene in
the laboratory:
-(CF – CF -)-n  n(C H )
2 2 2 4

Although tetrafluoroethene is not highly toxic, a

byproduct,
1,1,3,3,3-pentafluoro-2-trifluoromethyl-1-propene, is
toxic and its presence dictates care in handling crude
tetrafluoroethene.
The synthesis of fluorocarbon compounds, such as
polytetrafluoroethene (PTFE), is of great technological importance
because these compounds are useful in applications ran-
ging from coaltings for nonstick cookware and halogen-resistant
laboratory vessels to the volatile fluorocarbons used as
refrigerants in air conditioners and refrigerators. Fluoro-
carbon derivatives have also been the topic of considerable
exploratory synthetic research because their derivatives often
have unusual properties. Hydrofluorocarbons are used as
replacements for chlorofluorocarbons as refrigerants and
propellants. They are also used as anaesthetics, where they are
less flammable than their nonfluorinated counterparts.
Tetrafluorethane, CHF2CHF2, is an important solvent for the
extraction of natural prod-ucts such as vanilla and taxol, which is
used in chemotherapy.