Group 14: Carbides and Compounds of Silicon

Group 14
Carbides and
Compounds of Silicon
Introduction
 The group 14 elements are the second group in the p-block of
the periodic table. It is also called the carbon group. The
members of this group are:
 Carbon (C)
 Silicon (Si)
 Germanium (Ge)
 Tin (Sn)
 Lead (Pb)
Electronic Configuration of Group 14 Elements
• The group 14 elements have a general electronic configuration of ns 2np2.
• These elements have 2 electrons in the outermost p orbitals.
CARBIDES
 Carbides are compounds composed of carbon
and less electronegative elements.
 They are generally prepared from metals or

metal oxides at high temperatures (1500 °C or
higher) by combining the metal with carbon.
 Carbides are classified based on the type of

bonding in them.
1. Ionic carbides (Saline/Salt like carbides)
2. Covalent Carbides
3. Interstitial carbides
Titanium carbide
Ionic carbides
 Salt-like (saline) carbides are composed of the
highly electropositive atoms, such as the alkali,
alkali earth, group-III metals, mixed with carbon
and some metals like Zn,Cd & some lanthanides.
 Aluminium forms carbides, but other elements
from group XIII do not.
 They are transparent crystalline structures and o not
conduct electric current in solid state.
 These are readily hydrolysed by water or dilute
acids to give hydrocarbons.
 Based on the hydrocarbons formed, ionic carbides
are classified into
i. Methanides
ii. Acetylldes
iii. Allylides
Methanides
o These carbides give methane on hydrolysis. They contain “C4-” ions
Acetylides
o Acetylides are formed from alkali, alkali earth, and lanthanoid metals with the
acetylide anion C22-.
o They yield acetylene on hydrolysis
o Example: CaC2
Allylides
o The polyatomic ion C34- is referred to as an allylenide or sesquicarbide.
o They give methyl acetylene/allylene on hydrolysis.
COVALENT CARBIDES
 Covalent carbides are found in carbides of silicon and
boron.
 The reason these two elements form “covalent”
carbides is due to their similar electronegativity and
size to carbon. Because of this, their association is
completely covalent in character.
 Silicon carbide has two similar crystalline forms,
which are both related to the diamond structure.
 Boron carbide (B44C), on the other hand, has an
unusual structure that includes icosahedral boron units
linked by carbon atoms.
• Both silicon carbide (also known as carborundum)
and boron carbide are very hard and refractory
materials. Both materials have important industrial
applications.
Boron Carbide
 Both the carbides prepared by reducing oxides with “C” in an electric furnace .
SiO2 +3C SiC +2CO
2Si + C2H2 2SiC +H2

 The C-Si distance is 1.90 A° . The diamond type structure of carborundam explains
its hardness, high dissociation temperature & chemical inertness.
 SiC has better thermal conductivity at high temperatures, therefore widely used as
abrasive and refractive bricks.
 B4c3 has a complex lattice and even harder than SiC hence used as an abrasive and a shield
from radiation.
INTERSTIAL CARBIDES
 Interstitial carbides are derived primarily from
relatively large transition metals that act as a
host lattice for the small carbon atoms, which
occupy the interstices of the close-packed metal
atoms.
 Interstitial carbides are characterized by

extreme hardness but at the same time extreme Zirconium carbide
brittleness. ZrC
 They have very high melting points (typically

about 3,000–4,000 °C [5,400–7,200 °F]) and
retain many of the properties associated with
the metal itself, such as high conductivity of
heat and electricity as well as metallic lustre
 Most interstitial carbides do not react with

water and are chemically inert. Tungsten carbide W2C
Applications of Carbides.
1. Calcium carbide is used in the preparation of acetylene which is further

used in the preparation of other organic compounds like ethanol and
vinyl plastics.
2. Silicon carbide is used in production of ceramics and electronics
components, igniters in pilot lights for gas heaters, due better thermal
conductivty.
3. First commercial LEDs were based on SiC.
4. Tunsten carbide is used for cutting tools and the preparation of dyes and
the tips of ball point pens.
LED from SiC

W2C
SILANES
 Silanes are saturated hydrides of silicon. They
have general formula of (Si n H2n) with a
maximum value of 6.
Preparation of Silanes
 Silanes have been prepared by the reaction
of magnesium silicide (Mg2Si) with acids or
by the reduction of silicon chlorides with
LiAlH4.
Mg2Si + 4HCl SiH4 +2MgCl2

(Magnesium silicide)
LiAlH4 + SiCl4 SiH4 + AlCl3 + LiCl
 Disilanes can be prepared by the action of

Conc HCl on lithium silicide(Li6Si2)
Li6Si2 + 6HCl Si2H6 + 6LiCl
Applications of Silanes
• Silanes are used in some fiberglass and composites to improve mechanical
strength, and electrical properties.
• Paints, inks and coatings often use silanes to increase resistance to abrasions as
well as increased adhesion, thermal stability and crosslinking.
• Silanes also are used in adhesives and sealants that increase adhesion, temperature
and chemical resistance.
• They are good water repellants and hence used as water proofing agents in textile
industry.
Silicones
o Silicones are the polymers which are also known by the name polysiloxanes.
o It is a chain of alternating oxygen and silicon atoms that are frequently combined
with hydrogen and carbon.
o The general formula of silicone is (R2SiO)x, where R belongs to any one of the
organic groups.
o These compounds have high thermal stabilty due to Si-O-Si chains and also
called as high temperature polymers
Classification of Silicones
Depending on the type of Linkage they are classified into 3 types
1. Linear
2. Cyclic
3. Cross linked
Linear silcones
Dimethyl dichloro silanes reacts with water to produce dimethyl silanol.

The dimethyl silanol on polymerization lose a water molecule to form linear silicones.
Cyclic Silicones
Cross Linked Silicones
GRAPHITIC COMPOUNDS
Graphite intercalation compounds (GICs) are complex materials having a formula
CXm where the ion Xn+ or Xn− is inserted (intercalated) between the oppositely charged
carbon layers.
These materials are deeply colored solids that exhibit a range of electrical and redox
properties of potential applications.
Potassium Graphite
Preparation and Properties of Graphitic Compounds
(C8K)
• Graphite on treatment with potassium at 300° C gives the intercalation compound
of composition C8K.
• The potassium is absorbed into the graphite and the material changes color from
black to bronze.
• The bond between anionic graphite layers and potassium cations is ionic.
• The bronze-colored material KC8 is one of the strongest reducing agents known. It
has also been used as a catalyst in polymerizations and as a coupling reagent for
aryl halides to biphenyls
• KC8 is a superconductor with a very low critical temperature
 These intercalation alkali metal compounds
are more conducting than graphite
 They are paramagnetic in nature while
graphite is diamagnetic
 The electrical conductance decreases with
increase in temperature.
 They are highly reactive compounds
 Graphite can form intercalation compounds
with oxy acids, metal halides and halogens
also.
Superconducting graphitic
intercalation compounds

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Group 14

 They are generally prepared from metals or

 Carbides are classified based on the type of

2Si + C2H2 2SiC +H2

 Interstitial carbides are characterized by

 They have very high melting points (typically

 Most interstitial carbides do not react with

1. Calcium carbide is used in the preparation of acetylene which is further

LED from SiC

Mg2Si + 4HCl SiH4 +2MgCl2

 Disilanes can be prepared by the action of

Depending on the type of Linkage they are classified into 3 types

Dimethyl dichloro silanes reacts with water to produce dimethyl silanol.

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