CHEMICAL PROPERTIES

Oxidation state and trends in chemical reactivity

Due to small size of boron, the sum of its first three ionization enthalpies is very
high. This prevents it to form +3 ions and forces it to form only covalent
compounds. But as we move from B to Al, the sum of the first three ionization
enthalpies of Al considerably decreases, and is therefore able to form Al3+ ions. In
fact, aluminium is a highly electropositive metal.
Down the group, due to poor shielding effect of intervening d and f orbitals, the
increased effective nuclear charge holds ns electrons tightly (responsible for inert
pair effect) and thereby, restricting their participation in bonding. As a result of
this, only p-orbital electron may be involved in bonding. In fact in Ga, In and Tl, both
+1 and +3 oxidation states are observed. The relative stability of +1 oxidation state
progressively increases for heavier elements: Al<Ga<In<Tl. In thallium +1 oxidation
state is predominant whereas the +3 oxidation state is highly oxidising in character.
The compounds in +1 oxidation state, as expected from energy considerations, are
more ionic than those in +3 oxidation state.

In trivalent state, the number of electrons around the central atom in a molecule of
the compounds of these elements (e.g., boron in BF3) will be only six. Such electron
deficient molecules have tendency to accept a pair of electrons to achieve stable
electronic configuration and thus, behave as Lewis acids. The tendency to behave as
Lewi’s acid decreases with the increase in the size down the group. BCl3 easily
accepts a lone pair of electrons from ammonia to form BCl3.NH3.
I.E1 : B>Tl>Ga>Al>In E.N : B>Tl>In>Ga>Al
I.E2 ; B>Ga>Tl>In>Al M.P : B>Al>Tl>In>Ga
I.E 3 : B>Ga>Tl>Al>In B.P : B>Al>Ga>In>Tl
*The above order indicates that Al is most electro -ve and can form Al +3
ions easily.

*M+3/M value is +ve for Tl and -ve for Al,Ga,In.

*M+/M value +ve for Al and -ve for other elements.

*M/M3+ -ve for Tl.

*Concerning M /M value Al prefer metallic state.
+

*COMMENT:The above SRP data indicates that Tl prefers metallic state while
others not.{Tl+3/Tl}

*Gl exist in liquid state over a wide range of temperature.Therefore used in

measuring the high temperatures.

*The reluctance of paired up S-electrons to participate in chemical bonding is inert

pair effect.

*Tendency to exhibit inert pair effect Tl>In>Ga.

* First element in every group resembles In a different manner due to
the following reasons.
i) Small atomic radius ii) High Ionization Enthalpy
iii) High electronegativity iv) Lack of d-orbitals

(i) Reactivity towards air

 Boron is unreactive in crystalline form. Aluminium forms a very thin oxide layer
on the surface which protects the metal from further attack. Amorphous boron and
aluminium metal on heating in air form B2O3 and Al2O3 respectively. With dinitrogen
at high temperature they form nitrides.

The nature of these oxides varies down the group. Boron trioxide is acidic and
reacts with basic (metallic) oxides forming metal borates. Aluminium and gallium
oxides are amphoteric and those of indium and thallium are basic in their
properties.

(ii) Reactivity towards acids and alkalies

Boron does not react with acids and alkalies even at moderate temperature; but
aluminium dissolves in mineral acids and aqueous alkalies and thus shows
amphoteric character. Aluminium dissolves in dilute HCl and liberates dihydrogen.

concentrated nitric acid renders aluminium passive by forming a protective

oxide layer on the surface.
Aluminium also reacts with aqueous alkali and liberates dihydrogen.

(iii) Reactivity towards halogens

These elements react with halogens to form trihalides (except Tl I3).
2E(s) + 3 X2 (g) _ 2EX3 (s) (X = F, Cl, Br, I)

*The trihalides of B are used in synthetic chemistry as typical Lewis’s acids.

*B trichloride is better Lewis Acid than rest of trihalides of boron.

IMPORTANT TRENDS AND ANAMOLOUS PROPERTIES OF BORON

 The tri-chlorides, bromides and iodides of all these elements being covalent in
nature are hydrolysed in water. Species like tetrahedral [M(OH)4]– and octahedral
[M(H2O)6]3+, except in boron, exist in aqueous medium.
The monomeric trihalides, being electron deficient, are strong Lewis’s acids.
Boron trifluoride easily reacts with Lewis bases such as NH3 to complete octet
around boron.
F3B + :NH3 _ F3B _NH3
It is due to the absence of d orbitals that the maximum covalence of B is 4.
Since the d orbitals are available with Al and other elements, the maximum
covalence can be expected beyond 4. Most of the other metal halides (e.g., AlCl3) are
dimerised through halogen bridging (e.g., Al2Cl6). The metal species completes its
octet by accepting electrons from halogen in these halogen bridged molecules.

USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS

Boron being extremely hard refractory solid of high melting point, low density
and very low electrical conductivity, finds many applications. Boron fibres are used
in making bullet-proof vest and light composite material for aircraft. The boron-10
(10B) isotope has high ability to absorb neutrons and, therefore, metal borides are
used in nuclear industry as protective shields and control rods. The main industrial
application of borax and boric acid is in the manufacture of heat resistant glasses
(e.g., Pyrex), glass-wool and fibreglass. Borax is also used as a flux for soldering
metals, for heat, scratch and stain resistant glazed coating to earthenwares and as
constituent of medicinal soaps. An aqueous solution of orthoboric acid is generally
used as a mild antiseptic.
Aluminium is a bright silvery-white metal, with high tensile strength. It has a
high electrical and thermal conductivity. On a weight-to-weight basis, the electrical
conductivity of aluminium is twice that of copper. Aluminium is used extensively in
industry and everyday life. It forms alloys with Cu, Mn, Mg, Si and Zn. Aluminium
and its alloys can be given shapes of pipe, tubes, rods, wires, plates or foils and,
therefore, find uses in packing, utensil making, construction, aeroplane and
transportation industry. The use of aluminium and its compounds for domestic
purposes is now reduced considerably because of their toxic nature.

GROUP 14 ELEMENTS:THE CARBON FAMILY

Carbon, silicon, germanium, tin lead and flerovium are the members of group
14. Carbon is the seventeenth most abundant element by mass in the earth’s crust.
It is widely distributed in nature in free as well as in the combined state. In
elemental state it is available as coal, graphite and diamond; however, in combined
state it is present as metal carbonates, hydrocarbons and carbon dioxide gas
(0.03%) in air.

*Most versatile element in the world.

Its combination with other elements such as dihydrogen, dioxygen, chlorine and
sulphur provides an astonishing array of materials ranging from living tissues to
drugs and plastics.
Naturally occurring carbon contains two stable isotopes:12C and 13C. In addition to
these, third isotope, 14C is also present. It is a radioactive isotope with half-life 5770
years and used for radiocarbon dating. Silicon is the second (27.7 % by mass) most
abundant element on the earth’s crust and is present in nature in the form of silica
and silicates. Silicon is a very important component of ceramics, glass and cement.
Germanium exists only in traces. Tin occurs mainly as cassiterite, SnO2 and lead as
galena, PbS. Flerovium is synthetically prepared radioactive element.
Ultrapure form of germanium and silicon are used to make transistors and
semiconductor devices.
Symbol of Flerovium is Fl. It has atomic number 114, atomic mass 289 gmol-1
and electronic configuration [Rn] 5f14 6d10 7s2 7p2. It has been prepared only in small
amount. Its half life is short and its chemistry has not been established yet. The
important atomic and physical properties along with their electronic configuration
of the elements of group 14 leaving flerovium.

Electronic Configuration
The valence shell electronic configuration of these elements is ns2np2. The inner
core of the electronic configuration of elements in this group also differs.

Covalent Radius
There is a considerable increase in covalent radius from C to Si, thereafter
from Si to Pb a small increase in radius is observed. This is due to the presence of
completely filled d and f orbitals in heavier members.

Ionization Enthalpy
The first ionization enthalpy of group 14 members is higher than the
corresponding members of group 13. The influence of inner core electrons is visible
here also. In general the ionisation enthalpy decreases down the group. Small
decrease in _iH from Si to Ge to Sn and slight increase in _iH from Sn to Pb is the
consequence of poor shielding effect of intervening d and f orbitals and increase in
size of the atom.

Electronegativity
Due to small size, the elements of this group are slightly more electronegative
than group 13 elements. The electronegativity values for elements from Si to Pb are
almost the same.

Physical Properties
All members of group14 are solids. Carbon and silicon are non-metals,
germanium is a metalloid, whereas tin and lead are soft metals with low melting
points. Melting points and boiling points of group 14 elements are much higher than
those of corresponding elements of group 13.

*I.E: C>Si>Ge>Pb> *E.N:C>Pb>Si=Ge=Sn *Ge is a metalloid.

*C and Si are non-metals *Density decreases C-Si increases Ge-Pb.
*Lowest M.P:Sn *Highest M.P:C>Si>Ge>Pb>Sn * Lowest B.P:Pb.
*Resistivity least for Pb more for C.
CHEMICAL PROPERTIES
The group 14 elements have four electrons in outermost shell. The common
oxidation states exhibited by these elements are +4 and +2. Carbon also exhibits
negative oxidation states. Since the sum of the first four ionization enthalpies is
very high, compounds in +4 oxidation state are generally covalent in nature. In
heavier members the tendency to show +2 oxidation state increases in the sequence
Ge<Sn<Pb. It is due to the inability of ns2 electrons of valence shell to participate in
bonding.
Carbon and silicon mostly show +4 oxidation state. Germanium forms stable
compounds in +4 state and only few compounds in +2 state. Tin forms compounds in
both oxidation states (Sn in +2 state is a reducing agent). Lead compounds in +2
state are stable and in +4 state are strong oxidising agents. In tetravalent state the
number of electrons around the central atom in a molecule (e.g., carbon in CCl4) is
eight. Being electron precise molecules, they are normally not expected to act as
electron acceptor or electron donor species. Although carbon cannot exceed its
covalence more than 4, other elements of the group can do so. It is because of the
presence of d orbital in them. Due to this, their halides undergo hydrolysis and have
tendency to form complexes by accepting electron pairs from donor species. For
example, the species like, SiF6 2-, [GeCl6]2-, [Sn(OH)6]2- exist where the hybridisation of
the central atom is sp3d2.

i)Reactivity towards oxygen

All members when heated in oxygen form oxides. There are mainly two types of
oxides, i.e., monoxide and dioxide of formula MO and MO2 respectively. SiO only
exists at high temperature. Oxides in higher oxidation states of elements are
generally more acidic than those in lower oxidation states. The dioxides — CO2, SiO2
and GeO2 are acidic, whereas SnO2 and PbO2 are amphoteric in nature. Among
monoxides, CO is neutral, GeO is distinctly acidic whereas SnO and PbO are
amphoteric.

(ii) Reactivity towards water

Carbon, silicon and germanium are not affected by water. Tin decomposes steam
to form dioxide and dihydrogen gas.
Sn + 2H2O ___ SnO2 + 2H2
Lead is unaffected by water, probably because of a protective oxide film
formation.

(iii) Reactivity towards halogen

These elements can form halides of formula MX2 and MX4 (where X = F, Cl, Br, I).
Except carbon, all other members react directly with halogen under suitable
condition to make halides. Most of the MX4 are covalent in nature. The central metal
atom in these halides undergoes sp3 hybridisation and the molecule is tetrahedral in
shape. Exceptions are SnF4 and PbF4, which are ionic in nature. PbI4 does not exist
because Pb—I bond initially formed during the reaction does not release enough
energy to unpair 6s2 electrons and excite one of them to higher orbital to have four
unpaired electrons around lead atom. Heavier members Ge to Pb are able to make
halides of formula MX2. Stability of dihalides increases down the group. Considering
the thermal and chemical stability, GeX4 is more stable than GeX2, whereas PbX2 is
more than PbX4. Except CCl4, other tetrachlorides are easily hydrolysed by water
because the central atom can accommodate the lone pair of electrons from oxygen
atom of water molecule in d orbital. Hydrolysis can be understood by taking the
example of SiCl4. It undergoes hydrolysis by initially accepting lone pair of electrons
from water molecule in d orbitals of Si, finally leading to the formation of Si(OH)4 as
shown below :

IMPORTANT TRENDS AND ANAMALOUS BEHAVIOUR OF

CARBON
Carbon also differs from rest of the members of its group. It is due to its
smaller size, higher electronegativity, higher ionisation enthalpy and unavailability
of d orbitals. In carbon, only s and p orbitals are available for bonding and,
therefore, it can accommodate only four pairs of electrons around it. This would
limit the maximum covalence to four whereas other members can expand their
covalence due to the presence of d orbitals.
Carbon also has unique ability to form p_– p_ multiple bonds with itself and with
other atoms of small size and high electronegativity. Few examples of multiple
bonding are: C=C, C _ C, C = O, C = S, and C _ N. Heavier elements do not form p_–
p_ bonds because their atomic orbitals are too large and diffuse to have effective
overlapping. Carbon atoms have the tendency to link with one another through
covalent bonds to form chains and rings. This property is called catenation. This is
because C—C bonds are very strong. Down the group the size increases and
electronegativity decreases, and, thereby, tendency to show catenation decreases.
This can be clearly seen from bond enthalpies values. The order of catenation is C >
> Si > Ge _ Sn. Lead does not show catenation.

Due to property of catenation and p_– p_ bond formation, carbon is able to show
allotropic forms.

ALLOTROPES OF CARBON
Carbon exhibits many allotropic forms; both crystalline as well as amorphous.
Diamond and graphite are two well-known crystalline forms of carbon. In 1985,
third form of carbon known as fullerenes was discovered by H.W.Kroto, E.Smalley
and R.F.Curl. For this discovery they were awarded the Nobel Prize in 1996.
DIAMOND
It has a crystalline lattice. In diamond each carbon atom undergoes sp3
hybridisation and linked to four other carbon atoms by using hybridised orbitals in
tetrahedral fashion. The C–C bond length is 154 pm. The structure extends in space
and produces a rigid three dimensional network of carbon atoms. In this structure
(Fig. 11.3) directional covalent bonds are present throughout the lattice. It is very
difficult to break extended covalent bonding and, therefore, diamond is a hardest
substance on the earth. It is used as an abrasive for sharpening hard tools, in
making dyes and in the manufacture of tungsten filaments for electric light bulbs.
GRAPHITE
Graphite has layered structure (Fig.11.4). Layers are held by van der Waals
forces and distance between two layers is 340 pm. Each layer is composed of planar
hexagonal rings of carbon atoms. C—C bond length within the layer is 141.5 pm.
Each carbon atom in hexagonal ring undergoes sp2 hybridisation and makes three
sigma bonds with three neighbouring carbon atoms. Fourth electron forms a _ bond.
The electrons are delocalized over the whole sheet. Electrons are mobile and,
therefore, graphite conducts electricity along the sheet. Graphite cleaves easily
between the layers and, therefore, it is very soft and slippery. For this reason
graphite is used as a dry lubricant in machines running at high temperature, where
oil cannot be used as a lubricant.

FULLERENES
Fullerenes are made by the heating of graphite in an electric arc in the presence
of inert gases such as helium or argon. The sooty material formed by condensation
of vapourised Cn small molecules consists of mainly C60 with smaller quantity of C70
and traces of fullerenes consisting of even number of carbon atoms up to 350 or
above. Fullerenes are the only pure form of carbon because they have smooth
structure without having ‘dangling’ bonds. Fullerenes are cage like molecules. C60
molecule has a shape like soccer ball and called Buckminsterfullerene (Fig. 11.5).
It contains twenty six- membered rings and twelve five-membered rings. A six
membered ring is fused with six or five membered rings but a five membered ring
can only fuse with six membered rings. All the carbon atoms are equal and they
undergo sp2 hybridisation. Each carbon atom forms three sigma bonds with other
three carbon atoms. The remaining electron at each carbon is delocalised in
molecular orbitals, which in turn give aromatic character to molecule. This ball
shaped molecule has 60 vertices and each one is occupied by one carbon atom and
it also contains both single and double bonds with C–C distances of 143.5 pm and
138.3 pm respectively. Spherical fullerenes are also called bucky balls in short.

It is very important to know that graphite is thermodynamically most stable

allotrope of carbon. Other forms of elemental carbon like carbon black, coke, and
charcoal are all impure forms of graphite or fullerenes. Carbon black is obtained by
burning hydrocarbons in a limited supply of air. Charcoal and coke are obtained by
heating wood or coal respectively at high temperatures in the absence of air.
USES OF CARBON
Graphite fibres embedded in plastic material form high strength, lightweight
composites. The composites are used in products such as tennis rackets, fishing
rods, aircrafts and canoes. Being good conductor, graphite is used for electrodes in
batteries and industrial electrolysis. Crucibles made from graphite are inert to
dilute acids and alkalies. Being highly porous, activated charcoal is used in
adsorbing poisonous gases; also used in water filters to remove organic
contaminators and in airconditioning system to control odour. Carbon black is used
as black pigment in black ink and as filler in automobile tyres. Coke is used as a
fuel and largely as a reducing agent in metallurgy. Diamond is a precious stone and
used in jewellery. It is measured in carats (1 carat = 200 mg).