GROUP IIIA

Group IIIA of the periodic table consists of Boron (B), Aluminium (Al), Gallium
(Ga), Indium (In) and Thallium (Tl). Except boron all these elements are metals.
The metallic or electropositive character increase from boron ( a non - metal ) to
thallium ( a metal) on moving down . The metallic property in-group III A elements
are less pronounced as compared to those in group IA and II A elements, since the
elements of this group donate electrons with difficulty .
The elements have two s-electrons and one p-electron in their valence shell. Since p-
electron is held less tightly as compared to the s-electrons, the first ionisation energy
of each element ( except boron) is rather low. The second and third ionistion energies
are considerably higher. Ionisation energy decreases boron to aluminium, but does
not changes much from Al to Tl . Although the valence shell configuration of all
elements is same ( ns
2
p
1
) , the underlying core is different . The B and Al have inert
gas core, Ga and In have noble gas plus d
10
core and Tl has noble gas plus 4f
14
3d
10

core. Because of this difference , the atomic size and ionisation energy do not follow
the expected periodic trend. For example , increase in atomic radii from B to Al is not
followed by a further increase in Ga, because of higher effective nuclear charge for
Ga, as the additional 3d
10
electrons do not shield the nuclear charge effectively so
that the outer electrons are more strongly held. The atoms with a d
10
inner shell are,
therefore, smaller and have higher ionisation energies . Tl, because of the inclusion of
even more poorly shielding 4f electrons , in addition to d
10
has a smaller size and
higher ionisation energy . Thus first ionisation energies are low, comparable to those
of s-block elements , but second and third are considerably high. The sum of the first
three ionisation energies is very high and decreases from B to Al as expected, but
increase for Ga and Tl, due to decrease in their size.
Boron and Aluminium are expected to show an oxidation state of +3, because they
dont show this due to inert pair effect, while other members (Ga, In and Tl) show +
1 and +3 oxidation states due to inert pair effect. The inert pair effect increases
from Ga to Tl, so the stability of +3 oxidation state decreases from Ga to Tl and
stability of +1 state increases from Ga to Tl. Tl (III) compounds are less stable and
tend to change to Tl (I) compounds. Hence Tl (III) compounds are oxidizing agents
.
o The two s-electrons in the outermost orbit of Ga , In and Tl tend to remain
paired and do not participate in bonding or compound formation . This is
called inert pair effect. The inert pair effect means non-participation of the ns
2

electrons in chemical bonding of p-block and is much more pronounced in
Group IV A and V A . For example, Pb (II) is more stable than Pb (IV) state in
Group IV A and Bi (III) is more stable in VA. The inert pair effect also
indicates that the energy required to involve the ns
2
electrons in bonding
increases down the group.
The first ionization energy for boron is about 800 kJ mole
-1
, which is lower than that
for beryllium. This shows that monovalent boron, B
+
should be obtainable . But it is
not so. All known compounds of boron are trivalent. The balance of Energy required
to produce an sp
2
hybrid atomic orbitals, and (b) energy released in the formation of
three covalent bonds in BX
3
compounds leads to a much more stable system than
would be obtained by the formation of a single B+X
-
ionic compound .
All monomeric tri-covalent boron compounds are planar and in these systems, boron
has an incomplete octet, as a result of which boron has electron acceptor properties.
Since sum of the first three ionization energies for the elements are high, and that of
boron is exceptionally high, the total energy required to produce B
3+
ion is much more
than would be compensated by lattice energies of ionic compounds or by hydration of
B
3+
ions in solution. Consequently boron has no cation (B
3+
) chemistry . The
extremely high ionization energies associated with the formation of simple M
3+

coupled with the small ionic radius for M
3+
ions suggest a predominant covalent
character for compounds of III A group elements. However, the large hydration
energies of the ions of these elements compensate for the adverse ionization factor
and hydrated ions of the type [ M(H
2
O)
6
]
3+
are known for all the elements except
boron.
The ionic radius of Tl
+
is almost similar to that of bigger alkali ions. Hence Tl (I)
compounds resemble those of alkali metals . For example, the carbonates , nitrates
, sulphates, phosphates and cyanide and alums of K
+
and Tl
+
are often
isomorhpous. The standard oxidation potentials of these elements are quite high
except for boron, which does not exist as B
3+
ions in aqueous solution. Aluminium is
a strong reducing agent, even better than carbon. Thats why it is used as a
reducing agent to obtain Cr, Mn and V etc. by Thermite process.
When the elements of III A group form trihalides, trihydrides trialkyls, they
have only six electrons in their valence shell and are still capable of accepting a
pair of electrons. Thus they behave as Lewis acids. There are some notable
distinctions between the acceptor behavior of boron and other elements. These
are partly due to the reduced ability of the heavier elements to form multiple
bonds and their ability to attain a co-ordination number greater than 4. The
maximum covalency of boron is 4, while that of Al is 6. Boron halides are
momomeric and other elements can make up this deficiency through
dimersation. Hence the halides of Al, Ga and In are all dimeric. The shortening
of B-X bonds in boron trihalides is because of the ability of three - co- ordinated
boron to accept electrons from the fully filled pp orbitals of the halogens through
back donation. The bond is formed using the vacant pp orbital of boron. This is
most significant in BF
3
. The reduced tendency among the heavier elements to
form p - p is probably due to
o An increase in size of the central atom
o Less effective overlapping of more diffused 3p , 4p etc. orbitals and
subsequent weaker bonds
o Repulsion between filled inner orbitals of large M and X atoms.
Boron is a high melting, covalently bonded, refractory material even harder than
carborundum. The great hardness of the crystalline form indicates the powerful
bonding forces between the boron atoms . The crystalline boron has low electrical
conductivity. Other Group III A elements are silvery white and comparatively soft.
They have relatively low melting points. Gallium has the lowest melting point 29.8C
and so may be considered as liquid at room temperature. The softness and low
melting point is due to less rigid metallic bonding in their crystals.
The non-metallic boron differs sharply from other elements (metals) of the group in
its chemical reactivity which depends upon whether amorphous form or the
crystalline form (Boron occurs in these two allotropic forms). Amorphous boron is
very reactive, while crystalline form is quite unreactive. Conc. HNO
3
and conc.
H
2
SO
4
, both oxidize amorphous boron to boric acid, H
3
BO
3
. Crystalline boron is
hardly affected by these reagents, probably due to its structure.
Aluminium is rather inactive than expected from its electrode potential. This is
due to a thin film of oxide which normally covers its surface .
The metals react with halogens and sulphur to yield compounds with an oxidation
number of +3 . They react with water in different ways. Al reacts with water on
heating, while in the absence of oxygen even boiling water does not react with Ga and
In. Tl reacts with water in the presence of air to yield a strong hydroxide, TlOH and to
evolve H
2
. Like alkali metals, thallium is stored in air tight containers under
kerosene, glycerine or vaseline.
Al, Ga and In react with dilute mineral acids such as HCl, H
2
SO
4
. Tl does not react
with these acids due to the formation of sparingly soluble film of TlCl or Tl
2
SO
4
(Salt
passivation). Al readily dissolves in hot and conc. HCl or aqueous alkali at room
temperature . Al also dissolves in hot H
2
SO
4
.

Aluminium easily removes oxygen from the oxides of other metals. The reaction of
aluminium with metal oxides is highly exothermic.

The reduction of metals oxides by aluminium is called aluminothermy. This process is
used for the preparation of those metals that are reduced with difficulty and have high
melting points the examples are Ti, W, Zr, V.
Hardest element of III A group is boron. All halides of boron are electron deficient
compounds ( Lewis acids ) and triagonal planar in shape having sp
2
hybridization .
All halides of boron undergo hydrolysis to yield orthoboric acid (the stable oxy acid
of boron, H3BO3) and hydrogen halide. Lewis acid nature of BF
3
is less than
expected because of back donation of electrons by F. Due to this back bonding and
resonance the B-F bond in BF3 gets a bond order of 1.33. The tendency of accepting
electron pair of boron halides follows the order BF
3
< BCl
3
< BBr
3
> BI
3
. Expect the
BI
3
, this order is reverse of what is expected on the basic of electronegativity. The
trifluorides are all non-volatile ionic solids only slightly soluble in water. Other
halides are largely covalent, relatively volatile and their vapour consist of dimeric
molecules. They readily dissolve in non-polar solvents like benzene in which they are
present as dimeric molecules. Anhydrous trichlorides fume in air (moist) because of
hydrolysis. The tribromides and triiodides are also hydrolysed.
Binary compounds of boron with hydrogen are known as boranes and all boranes are
electron deficient compounds, spontaneously catch fire in air and undergo hydrolysis
with water to yield boric acid. Hydrogen bridge in B
2
H
6
is known as banana bond
or tau bond. Borazine or Borazole or inorganic benzene ( B
3
N
3
H
6
) is isoelectronic
with benzene. In it hybridization at B and N is sp2. Hybridization of boron atom in
diborane (B
2
H
6
) is sp
3
. Borazine has a little aromatic character. Borazine nucleus
undergoes addition reaction with molecules containing acidic hydrogen such as HCl,
H
2
O, CH
3
OH, CH
3
COOH etc. The B - N distance in borazine is a shorter than
expected for a single bond, which is probably due to delocalised pp - pp bonding.
However decalisation is less than in benzene.
Diborane is used as rocket fuel. Boron nitride has a structure similar to graphite.
Hybridization at B and N in it is sp2. Boron nitride is also known as white graphite.
A hard substance known as borazone is obtained when boron nitride is heated at 3000
C and 10,000 atm. pressure . The hardness of the four hardest known substances
follows the order:
Diamond > Borazone > Carborundum > Corundum.
Aluminium is the most abundant metal in the earth crust. The principal ore of
aluminium is bauxite, Al
2
O
3
.2H
2
O. Aluminium is bluish white metal with a brilliant
lusture, which is soon destroyed by the formation of a layer of oxide on it. Aluminium
is not affected by dry air but in moist air an oxide film is formed over its surface. It
burns is oxygen forming brilliant light. The reaction is highly exothermic and used
for reducing oxides of iron, chromium and manganese. The aluminium metal is
praised for its lightness, high thermal and electrical conductivity, high ductility, high
resistance to corrosion and high reflectivity for light and heat. Mixed with iron oxide,
aluminium powder forms thermite, which is used for welding purposes. Aluminium
has a great affinity for oxygen and this fact is used in the extraction of chromium and
manganese from their oxides. Aluminium is mainly used in making alloys with light
weight and good strength. Aluminum metal is soluble in both acids and alkalies with
the liberation of H
2
gas.
The reduction potential of Al
3+
ion is sufficiently negative (-1.66 V). All aluminium
salts are soluble in water or in dilute acids. Aluminium forms a number of double salts
with other cations. These are called alums.
The common alloys of aluminium are aluminium bronze (88 - 90% Cu, 12-10%
Al),
Magnalium (5-30% Mg, 95 - 70% Al) and Duralumin (95 % Al, 4% Cu, 0.5%
Mg and 0.5% Mn). Almasilicon and Alpax are the important alloys of
aluminium with silicon. Gold containing 1% Al is green in colour; with 10% Al it
is white as well as brittle. Gold containing 22% Al is deep purly. The m.p. of
this alloy is 20C higher than that of pure gold.
The most stable compound of aluminium is Al
2
O
3
. A mixture of aluminium powder
and aluminium nitrate is called ammonal. A mixture of aluminium powder and
barium peroxide is called ignition mixtrue. Aluminium oxide is used for preparing
artificial gems. Al
2
O
3
is used as an absorbent in column chromatography. Both
boron and aluminium form electron deficient compounds. Aluminium is usually
extracted from bauxite by electrolytic reduction. Important minerals of aluminium are
bauxite (Al
2
O
3
. 2H
2
O), diaspore (Al
2
O
3
. H
2
O), Corundum (Al
2
O
3
), Felspar
(KAISi
3
O
8
) and Cryolite ( Na
3
AlF
6
). Bauxite is purified by Baeyers process, Halls
process and Serpecks process. In the electrolytic reduction of alumina, cryolite and
fluorspar are added to reduce the m.p. of alumina.
Al
2
O
3
is not a good conductor or electricity. It is dissolved in cryolite to make it a
good conductor. Aluminium does not react with HNO
3
. A mixture of ferric oxide
(Fe
2
O
3
) and Al powder in the ratio 3:1 is called thermite. Al is the metal which is
present in silver paints. All double sulphates with similar composition and properties
are called alums. Common alum is K
2
SO
4
. Al
2
(SO
4
)
3
.24H
2
O. Al
2
O
3
is a while
deliquescent crystalline compound which sublimes at 456 K. Al
2
O
3
exists as dimer
Al
2
Cl
6
and is covalent in solid state but dissociates into ions in solution. It also acts
as Lewis acid.
Each metal ion in alums is surrounded by 6 water molecules.
Artifical gems or precious stones are prepared by dissolving alumina with metal
oxide in oxyhydrogen blow pipe flame. The formula of alum stone is K
2
SO
4
.
Al
2
(SO
4
)
3
. 4Al(OH)
3
. An Alum shale is aluminium silicate containing iron pyrites
(FeS
2
). Ruby (red) and Sapphire (blue) stones are the purest and natural form of
alumina (Al2O3). Aluminium sulphate present in alum undergoes hydrolysis to form
acidic solution. AlCl
3
is used as a catayst in aa Friedel Crafts reaction and in
cracking of petroleum.

group IV A
The IV A group of periodic table contains C, Si, Ge, Sn and Pb. They have ns
2
np
2
as
the general outer configuration. IV group is regarded as a transitional group between
metals (electropositive) and non-metals (electronegative).
Their Atomic size, Atomic Volume, Metallic character, Basic nature of the Oxides
increases from Carbon to Lead. Carbon and Silicon are non- metals, Germanium is
metalloid while Tin and Lead are metals.
Ionization potential, Electron affinity, m.p. and b.p decreases from top to bottom
(down the group). Carbon is most electronegative element of the group. Ionization
energy of the Carbon is very high. With the exception of Carbon density increases
from Silicon to Lead.
Each element of this group has 4 electrons in the outermost shell of their atoms. The
atoms of these elements could therefore accept or donate 4 electron each, exhibiting
thereby the oxidation numbers of - 4 and + 4 respectively. All the elements of this
group exhibit +2 and + 4 oxidation states. The +2 Oxidation State is more stable in
the heavier elements due to inert pair effect.
The oxidation number of - 4 and + 4 are characteristic of non metals Carbon and
Silicon alone. They exhibit the maximum valence of 4 with respect to both hydrogen
and oxygen. In addition they can also form a few unstable compounds with the
oxidation number of +2 in oxides and sulphides.
Tin and lead form stable compounds in +2 oxidation state which are more stable than
those in oxidation state of + 4. Moreover, tin and lead can exist in the form of
positive ions or cations.
The elements of this group can utilize all the four valence shell electrons for bonding.
They form molecules having 4 covalent bonds in which octet rule is obeyed.
Elements of IV A group show Catenation. Carbon has maximum catenation power
and then Silicon. The property of catenation is responsible for the existence of
numerous compounds of Carbon. The highest catenation power of carbon is due to its
small size and high bond energy. The property of catenation decreases rapidly for
Silicon and Germanium, while it is very feeble in tin and almost nil in lead. In Tin
and Lead, the linkage usually involves no more than two atoms. The decrease in
catenation is due to decrease in strength of the M - M bonds. The polarity of C - H
bonds is less than the polarity of Si - H bond.
Compounds of Ge (II) are unstable and readily oxidized to Ge (IV) due to inert pair
effect. Compounds of Ge(II) are thus powerful reducing agents. Sn (II) tends to be
oxidized to Sn (IV) and hence Sn (II) is strongly reducing. Pb(II) is more stable than
Pb(IV) which is strongly oxidizing.
In all compounds carbon has a covalency of 4 and cases in which carbon has other
than this covalency are rare. Ionic bonds of carbon are rare. Unstable carbonium ions
and carbanions are, however known but such species do not have the charge localized
on any carbon atom. The ion C
4+
is unknown and C
4 -
is rare.
Carbon is harder than silicon. Carbon in the from of graphite and gas carbon is a
good conductor of electricity. Silicon is a bad conductor of electricity. Carbon and
hydrogen have almost same electronegativities. The hydrides of silicon are called
silanes. The latter are good reducing agents. Silianes undergo hydrolysis due to the
polar nature of Si - H bond. Maximum covalency of Carbon is 4 and that of the
Silicon is 6. This shows stability of carbon compounds and instability of silicon
compounds. Carbon is limited to 4 electrons in its valence shell. So it exhibits a
maximum covalency of 4. The valence shells of silicon and other elements have d-
orbitals and can thus expand their shells beyond octet. Thus they exhibit covalency of
greater than 4. While carbon forms no complex compounds, Silicon and other
elements form complex compounds of the type SiF
4
2-
, SnCl
6
2-
, PbCl
4
2-
etc.
IV group elements form the corresponding dioxides. They are CO
2
, SiO
2
, GeO
2
,
SnO
2
and PbO
2
. Out of these CO
2
and SiO
2
are acidic while GeO
2
, SnO
2
and PbO
2

are amphoteric.
Carbon forms two oxides CO and CO
2
, which are gases at ordinary temperatures.
Silicon forms solid SiO
2
. It has high m.p. and b.p. Purest form of SiO
2
is quartz.
The reaction of carbon and oxygen at higher temperature yielding CO and CO
2
is
highly exothermic. The relative yield of two oxides depends on temperature. The
highest the temperature the greater is the proportion of CO.
CO burns with blue flame and extremely poisonous due to its high affinity for oxygen
. It combines with haemoglobin of the blood to give carboxy haemoglobin. It is
neurtral to litmus. Exhaust pipes of autos contain CO. CO reacts with Cl
2
in
sunlight to form poisonous COCl
2
( Phosgene or carbonyl chloride). CO is a good
reducing agent .
CO also acts as an unsaturated compound because the four valencies of carbon are not
satisfied in it. Thus it forms addition compounds with a number of substances. CO
reacts with many metals to form metal carbonyls. In carbonyls the oxidation state of
metals is always zero. The poisonous nature of CO is also due to its ability to form a
bond with iron atom in the haemoglobin of blood.
CO
2
is product of combustion of carbon and its compounds, CO2 is not poisonous,
but it does not support life. Solid CO2 is known as dry ice. The latter mixed with
ether is used as refrigerant. CO
2
is neither combustible nor supporter of combustion.
Air contains 0.03% of CO
2
by volume . CO
2
is about 1.5 times heavier than air .
Aerated water contains CO
2
under pressure . Dry ice undergoes sublimation at 78 C.
A mixture of 90% O
2
and 10% CO
2
is called carbogen which is used for artificial
respiration . CO
2
turns lime water milky. CO
2
is acidic to litmus. Presence of about
15% CO
2
in air acts as fire extinguisher. Oxygen gas is liberated during
photosynthesis.
Silicon is relatively unreactive except at high temperatures. It is unaffected by
oxygen, water and steam probably due to the formation of protective surface layer of
SiO
2
. Germanium is more reactive than silicon. It reacts with water and dilute acids
and alkalies only in the presence of an oxidizing agents such as H
2
O
2
or NaOCl. Tin
and lead are reactive as well as electropositive.
All the elements of VIA group form tetra halides of the type MX
4
. The stability
decreases from CX
4
to PbX
4
. All the tetra halides are liquid at room temperature and
covalent in nature. With the exception of carbon all the elements of IVA group react
with alkalies to form H
2
gas.
The existence of an element in different forms is called allotropy. Carbon exists in
different allotropic forms. Diamond and graphite are the crystalline forms while
coal, coke, wood charcoal, animal charcoal, gas carbon, lampblack, petroleum
coke and sugar charcoal are amorphous forms of carbon. Graphite and gas carbon
are good conductor of electricity. Diamond is the hardest form of carbon. Lamp
black is the softest. Sugar charcoal is the purest form of carbon. Diamond has
tetrahedral structure (sp
3
hybridization) and graphite has hexagonal structure (sp
2

hybridization). Diamond is big three- dimensional polymer with a large number of
carbon atoms arranged tetrahedrally. That is why it is hardest substance known. The
density of diamond is 3.51 g/ cc. The refractive index of diamond is 2.45. Diamond
is very hard due to strong sigma bonds. Graphite is soft due to the presence of weak
vander Walls forces between various hexagonal layers. Diamond is insoluble in any
solvent.
The C - C covalent distance in graphite is 1.42 A. The layer structure of graphite is
the cause of softness and lubricating properties of graphite. Lead pencil is a mixture
of graphite with variable quantities of clay depending upon the hardness required.
Because of the presence of free electrons graphite is good conductor of, heat and
electricity. Graphite forms a yellow mass known as graphitic acid (C
11
H
4
O
5
) when
heated with conc. HNO
3
. Diamond glitter because of high refractive index. Diamond
is used as precious stones for jewellery. The famous Kohinoor diamond (106 carats)
occurs in India. A carat is equal to 0.2 gm (= 200mg). Diamond on heating at 1800-
2000C in vacuum gives graphite.
The similarity in electronegativity between carbon and hydrogen shows that C- H
bond would normally have low polarity . Thus they exert no strong inductive effects
on the other bonds involving carbon The C-C bonds are also not weakened by
electron withdrawal by hydrogen . Thus carbon atoms form stable links through
chains and rings of infinite length.
The ability of carbon to be more than divalent gives it characteristic to form long
chains and branched chains permitting a wide variety of structures . The smaller size
of carbon (77 pm) allows effective sideways overlapping of orbitals giving p bonds .
Carbons can form stable multiple bonds of the pp- pp type. Thus carbon forms the
largest number of hydrides known as hydrocarbons .
Silianes are much more reactive than hydrocarbons because of larger size of silicon
atom (117 pm) which facilitates attack by nucleophiles. Greater plarity of Si-X bond (
X = H, C,O,N, F, Cl , Br , I ) and availability of low lying d-orbitals, decreases the
activation energy of the reaction. In general , C-X bond energy is less than Si-X bond
energy ( X = O, N, F, Cl, Br, I ) . All silanes are spontaneously inflammable in air
and react vigorously with aqueous alkali forming silicate and evolving H
2
.
The decrease in thermal stability of the hydrides is due to the fact that M-H bond
energies decrease from carbon to lead. C-H> Si-H> Ge-H > Pb-H. The difference in
the stability of the hydrides of carbon and silicon is, however, not due to the weaker
Si-H bond, but rather a result of inductively weakened Si-Si bond due to electron
withdrawal by hydrogen. The decreasing stability of the germanes, stannanes and
plumbanes is primarily due to decrease in M-H bond energies. The tetrahalides of the
type MX4 are all known except PbBr
4
and PbI
4
,which are not expected to be stable
due to the strong oxidizing power of Pb ( 4 +) and the reducing power of Br- and I- .
In general, stability of halides decreases on moving down the group and also as the
halogen changes from fluorine to iodine. All the tetrahalides are covalent and sp
3

hybridised (tetrahedral) compounds (except SnF
4
and PbF
4
) and have polymeric
partly ionic structures. No dihalides of carbon and silicon are known. The dihalides
of Ge, Sn and Pb are known. The dihalides are much less volatile than tetrahalides
and become increasingly powerful reducing agent from Ge to Pb.
The three important crystalline forms of silica are quartz, tridymite and
crystobalite. Amorphous forms of silica are agate, jaspur and onyx. Transparent
quartz is used in making optical instruments and lenses. Sand (SiO
2
) is an important
flux in metallurgy. Quartz glass used in the manufacture of optical instruments and
chemical apparatus is called vitreosil .
Fuel is a substance, which burns in air to give heat energy. Fuels may be solid
(e.g coke, coal, wood), liquid (petrol, kerosene. alcohol etc) and gaseous (e.g.
water gas. coal gas, producer gas etc). All fuels have greater affinity for oxygen
and burn to give heat energy. Water gas CO+ H
2
, producer gas is CO+N
2
and
carburetted water gas is water gas mixed hydrocarbons. Semi water gas is the
product formed by passing a mixture of steam and air over incandescent coke. It
is a mixture of CO
2
+ N
2
+ H
2
. Approximate composition of water gas is H
2

50% , CO = 40% and rest is a mixture of CO
2
, CH
4
and N
2
. The calorific value
of water gas is high (2700 k.cals/ m
3
). The calorific value of producer gas is low
(900 k.cals / m
3
). The composition of producer gas is CO = 30 -35% . N
2
= 50-
55% and rest is a mixture of CH
4
, CO2 and H2. The calorific value of coal gas is
4500-5900 k.cals/ m
3
. It is a good gaseous fuel as it contains 95% of combustible
gases. Petrol gas is a mixture of CH
4
, C
2
H
6
, C
2
H
4
etc .
Cement is finely powdered mixture of calcium aluminates and silicates . It is called
Portlant cement because it resembles to a famous variety of building stone quarried
near Portland in England. Cement was first prepared by Joseph Aspidin .
Portland cement is a mixture of limestone is : CaO
2
= 20-25% , Al
2
O
3
= 5-10% ,
MgO = 2-3% , Fe
2
O
3
= 1-2% and SO
3
= 1-2% . For a good quality cement the ratios
between silica and alumina should be 2.5 - 4.0. The ratios between the weight of CaO
and other oxides (SiO
2
+ Al
2
O
3
+ Fe
2
O
3
) should be close to 2. The MgO content
should be less than 5% . The mixture of calcium silicate and calcium aluminate
produced in the manufacture of cement clinker. Cement clinker is mixed with 2-3% of
gypsum to regulate the time of setting. The setting of cement is due to hydration of
calcium silicates and aluminates .
Chemical composition of ordinary glass is Na
2
SiO
3
. CaSiO
3
. 4SiO
2
. Raw materials
used for the manufacture of glass are Na
2
CO
3
, CaCO
3
and SiO
2
( soda ash, limestone
and silica ). The process of gradual cooling of glass is known as annealing. Lenses,
prisms and optical instruments are made with flint glass. It has high refractive index.
UV rays can be checked by Crookes glass . Pyrex glass has a very low coefficient of
thermal expansion . It is mainly a mixture of sodium borosilicate and aluminium
borosilicate. Different coloured glasses are obtained by the addition of metallic oxides
to glass.

Colour
Substance
Used
Colour Substance Used
Violet
Blue
Green
Lemon
Yellow
MnO
2

CoO
2
CuO
CuO ,Cr
2
O
3

CdS
Red
OrangeRed
Black
Milky
Glass
Cu
2
O & SeO
SeO
Fe O
3
& CuO in
excess
SnO and Ca
3
(PO4)
2


Semiconductors are those solid substances which are insulators under normal
conditions but conduct electricity by the passage of electrons with the increases in
temperature or by the presence of impurities. Silicon and Germanium are
semiconductors.
Tin exists in three allotropic forms - grey, white and rhombic.White variety is the
most stable variety of tin . The crumbling of tin to a powder is known as tin pest, tin
disease or tin plague. Tin is weakly electropositive and relatively less active metal.
Tin is not attacked by organic acids.Thus it is used in tinning of cooking utensils. Tin
is the only element which has maximum number of isotopes (ten). The process of
depositing a thin protective layer over sheets ,of iron is called tin plating.Important
alloys of tin are,
Bronze (75 - 90% Cu, 10 - 20% Sn), Solder (76% Sn, 33% Pb), Bell metal (25% Sn,
75% Cu), Gun metal (88%Cu, 10% Sn 2% Zn) and Babbit metal (90% Sn, 7% Sb,
3% Cu). SnO
2
is amphoteric. SnCl
2
is soluable in water , alcohol and ether.
Important ores of lead are galena (PbS) and cerlussite (PbCO
3
). Water containing
dissolved air dissolves lead, forming water soluble lead hydroxide. This solvent
effect of water is known as plumbo solvency. Litharge or massicot is PbO, red lead is
Pb
3
O
4
or PbO
2
. 2PbO (double oxide). Lead is soluble in acetic acid. Pb(CH
3
COO)
2
is
called sugar of lead. Tetra ethyl lead is an anti knock compound. Basic lead
carbonate is known as white lead.
Group 5
th

Nitrogen is very important element in mans environment . It is one of the five major
elements required by living systems, in parts because of its presence in all amino
acids, the building blocks from which proteins are cinstructed . Nitrogen is one of
three major elements present in commercial fertilizeres ( the other two being P and
K . ) Nearly all chemical explosives contain nitrogen .
Phosphorus is also a major element essential to living systems . The phosphate
linkages hold together the skeletons of enormous molecules of deoxy ribose nucleic
acid (DNA) that contain the genetic code in animal cells. A series of adenosine
phosphate compounds store and later release the energy obtained when high energy
compounds such as glucose are oxidised in the body . Phosphorus is the tenth
element in order of abundance in the earths crust and occurs to the extent of
1120 ppm. All the known minerals of phosphorus are orthophosphate.
Arsenic , antimony and bismuth are much less abundant in the earths crust and much
less important than nitrogen and phosphorus . The first two elements in the group ,
nitrogen and phosphorus are typical non-metals , arsenic and antimony are
metalloids , while bismuth is a metal.
Each of these elements has 5 electrons in the outermost shell (ns
2
p
3
), so they are
short of three electrons to attain an octaelectronic noble gas configuration . All these
elements are capable of completing their outermost shell. For example , in compounds
with hydrogen these elements are strictly trivalent. The electronegativity of these
elements , however , decreases with increase in their atomic number . Atoms of
these elements can also give up electrons. In oxy compounds and in compounds with
halogens ( except for Iodine ) and sulphur , these elements exhibit valence of +3 and
+5 .
All hydroxides formed by group VA elements in pentavalent state are acidic in
nature. The strength of these acids decreases down the group. HNO
3
>H
3
PO
4

>H
3
AsO
4
>H
3
SbO
4
>H
2
BiO
4
. Thus HNO
3
is a strong acid , H
3
PO
4
is moderately
weak acid , H
3
AsO
4
is a weak acid, while the remaining two acids are extremely
weak.
Nitrogen and phosphorus exist as anion in all their compounds , while As, Sb and
Bi have a tendency to form cation , For example , these three elements are
present in aqueous solution as cations, As
3+
, Sb
3+
and Bi
3+
, with oxidation
number of +3 , in a very insignificant amount , since their salts undergo
hydrolysis.
Though the elements have been placed in the same group VA, they differ from one
another in many properties . The N and P have noble gas core beneath the valence
shell of 5 elements , while As, Sb and Bi possess 18 electrons in their penultimate
shell . due to this difference in electronic configuration , they have different
properties.
All members of the nitrogen family exhibit multiple oxidation states between -3 and
+5 as is expected from the electronic configuration of their atoms . Common
oxidation states of VA group elements are -3 , +3 and +5 . Nitrogen itself shows all
the integral oxidation states of -2 , -1 , -1/3 , +1 , +12 , +4 etc.more electrons , either
by gaining three more electrons , either by gaininig three electrons or by sharing
electron pair with a less electronegative atom. In + 3 oxidation state one pair of s-
electrons is inert and the three unpaired p-eletrons are used for chemical bonding to
more electronegative element . The +5 oxidation state involves the use of all the 5
valence electrons to form covalent bonds. The higher positive oxidation states are
represented by halogen and oxygen derivatives of the elements .
Compounds such as NH
3
, PH
3
, AsH
3
, SbH
3
etc show -3 oxidation states . NH
2
-
NH
2
exhibits -2 and NH
2
OH
-1
oxidation state. N
2
O and NO show + 1 and +2
oxidation states respectively . Species such as NO
2
,P
4
O
6
,As
4
O
6
, Sb
4
O
6
and Bi
2
O
3

show +3 oxidation state . NO
2
, P
4
O
8
, Sb
2
O
4
etc. show +4 oxidation state and species
such as N
2
O
5
, NO
3
-
, P
4
O
10
, As
2
O
5
, Sb
2
O
5
and Bi
2
O
5
show +5 oxidation states .
The ionisation energies are high as would be expected from the electronic
configuration of the elements ( stability of half filled p-orbitals ) and those for the
removal of s-electrons encrease between Sb and Bi, just as they increase between In
and Tl and between Sn and Pb , Bi like Pb, shows the 6s inert pair effect .
The standard electrode potentials for As, Sb and Bi are quite close together. The
decreasing ionisation energies of the ions being offset by the increase in ionic radii
and decrease in heat of hydration of the cation formed .
The gain of three electrons to form anion of the type N
3
-
is favourable for N and that
too only by metals which have low ionisation energies and form nitrides with high
lattice energies . For example , Li
3
N , Be
3
N
3
etc.
The formation of p
3-
from P is very difficult , because addition of three electrons to a
neutral atom requires a huge amount of energy . The elements As, Sb and Bi show no
tendency to form anion by gaining electrons . This is probably due to the fact that
increasing size of the atom makes it difficult for the nucleus to hold extra electrons.
The loss of all the 5 electrons is more difficult to achieve because of the large
ionisation energies involved . The M
5+
ions, therefore, do not exist. Even the
formation of M
3+
ion needs considerable amount of energy because it requires
destruction of the stable half filled p
-
subshell . The heavier elements however,form
compounds containing cationic species , in which charge corresponds to M
3+
, for
example , BiF3. In this type of compounds , the pair of s-electrons become inert
because of their ability to penetrate towards the nuclear charge . The tendency of the
pair of electrons to remain inert increases as we go sown the group.
The most common mode of bonding by the elements in VA group is the use of their
three unpaired electrons to form 3 covalent bonds and to form molecules such as NH
3

, PH
3
, PCl
3
etc. Here the elements may be in - 3 or +3 in NCl
3
or NF
3
, but -3 in NH
3
.
For As and Bi, the +5 state is often less stable than the +3 state. Thus arsenates and
bismuthates are oxidising agents and are reduced to arsenite , As (III) or Bi (III) .
Preference of As for the +3 state may be attributed to the poor shielding of the
nucleus afforded by the inner 3d-electrons,as a result of which it is more difficult the
promotion of one of the 4s -electrons . For Sb, the poor shielding of the 4d-electrons
is offset by the greater distance of the valence electrons from the nucleus . Atoms of
high atomic number generally form weak covalent bonds and the preference of
bismuth as Bi (III) is probably due to the fact that it more stable in ionic compounds
than entirely in covalent form.
Nitrogen does not posses d-orbitals in valence shell and so its covalency is limited to
four. No pentavalent compound of nitrogen is therefore known . N can , however ,
achieve a formal oxidation state of +5 as in NO
3
-
ion. The inability of N to unpair
and promote its 2s-electron results in that N ( +5) is less stable than N ( +3 ) . Thus
HNO
3
is a strong oxidising agent . However , P ( + 5) is more stable than P ( + 3)
and hence phosphoric acid , H
3
PO
4
shows no oxidising properties.
Catenation in nitrogen is limited to two or three atoms . Hydrazine , NH
2
- NH
2
,
the simplest catenated N-N compound is unstable with respect to
disproportionation to elements . The higher homologues become increaseingly
unstable . The P-P compounds are comparatively more stable . In As , Sb and Bi
, the property of catenation is still less and decrease in the order P > N > As >>
Sb >>> Bi .
Maximum co-ordination number for N is 4 and thus the only regular stereo
chemical arrangements that it can exhibit are tetrahedral , pyramidal, planar,
angular and linear as in NH
3
+
, NH
3
, NO
3
-
, ClNO and NO
3
+
respectively .
Phosphorus , like N, can complete as octet of 4 tetrahedrally arranged electron pairs
either by forming three covalent bonds giving pyramidal structure as in PCl
3
or by
forming 4 covalent bonds in ions such as PH
4
+
, which is similar to NH
4
+
.
Distortios because of lone electron pair repulsion similar to those in N compounds are
also operative in P compounds . The H-P-H bond angle in PH
3
is 93 and H-N-H
bond angle in NH
3
is 107 . Because P=O bond repels the P-X bonds more than the
single bonds repel each other , the X -P-X angle is always less than the tetrachedral
angle (109 28 ) in PX
3
compounds ( X = F , Cl , Br etc) .
The tetrahedral geometry in N compounds can be achieved by (a) Forming 4 covalent
bonds and losing an electron as NH
4
+
. (b) Forming three covalent bonds and
donating a lone pair of electrons to form a fourth bond as in H
3
N. BF
3
. In both cases
there is a tetrahedral distribution of 4 bonds about the nitrogen atom . Pyramidal
geometry is most common for N and the bond angle X-N-X in majority of compounds
is close to 108 . The nitrogen atom is pyramidal in hydrazine and its derivatives. The
X-N-N bond is 110 - 112 . Rotation about the N-N bond is prevented by the lone
pair on each nitrogen atom . The lone pair repulsion are also responsible for the long
N-N bonds . The bond is shortened when the lone pairs are involved in bonding , as in
N
2
H
5
+
and N
2
H
6
2+
.
In all nitrogen compounds where the nitrogen octet is comleted by the formation of
three electron pair bonds, the N atom has a pair of non-bonding (lone pair ) electrons .
As a result of non-bonding pair all NR
3
type of compounds act as Lewis bases and
form complexes with Lewis acids. Substituted ammonias of the type of NR
3
are also
pyramidal .
Trigonal planar compounds of nitrogen contain three sigma and one pi bonds . The p
bond can be localised in one direction or delocalised . Examples of trigonal planar
species of N are NO
3
-
, O
2
N - X ( X = F , Cl , OH , C
6
H
5
, CH
3
, OCH
3
etc).
An important difference in stereochemistry of N and other elements of the group is
the possibility of utilizing the low lying d-orbitals by these elements . Thus they can
expand their valence shell and can have co-ordination numbers more than 4. For
example , PH
3
, AsCl
3
are atrigonal pyramidal in shape , PCl
4
3+
is tetrahedral , PCl
3
is
trigonal , PO
4
3-
is tetrahedral , PF
5
, AsF
5
, SbCl
5
are trigonal bipyramidal and PC
6
-
,
SbCl
6
-
are octahedral in shape .
Gaseous nitrogen is generally inert because of great strength of the N N bond or due
to its high bond energy . Very symmetrical electron distribution in the molecule and
the absence of the bond polarity are also responsible for its inert nature. When these
are modified as in isoelectronic NO
+
, the reactivity is considerably increased .
White p is considerably more reactive than red phosphorus . Most reactive element of
the group is phosphorus and its reactivity is due to very small bond ( 60) or small
bond strain .
Phosphorus forms binary compounds with all elements except Sb, Bi and the inert
gases .
Arsenic and antimony are unaffected in dry air at room temperature. At high
temperature , oxides of the form M
2
O
3
are formed . Aqueous solutions of oxidising
acids are able to dissove the elements but non-oxdising acids do not react . None of
the elements reacts with alkalies.
Compared to the amphoteric oxides of As and Sb and the acidic oxides of N and P,
the bismuth oxide , Bi
2
O
3
is basic. Direct reactions of Bi with O
2
, S and X
2
at
elevated temperatures yields Bi
2
O
3
, Bi
2
S
3
and BiX
3
respectively.
VA group elements are called pnicogens and their compounds as pnictides .
Most common valence of VA group elements is +5 . In bismuth stable oxidation
state is +3 because of inert pair effect . All the binary compounds of VA elements
are covalent , except BiF
2
and SbF
3
. Arsenic undrgoes sublimation at high
temperature and low pressure . Phosphorus is more reactive than nitrogen . In fact ,
the most reactive element of VA group is phosphorus because of its low bond
dissociation energy . Except Bismuth all elements exhibit allotropy.
Despite its ready availability in the atmosphere , nitrogen is relatively less abundant in
the rocks and soil of the earth. It does not generally occur in nature in the form of
inorganic compounds . The only major minerals containing nitrogen are KNO3 (
saltpetre) and NaNO3 (chile saltpetre ) . There is a continuous interchange of
nitrogen between the atmosphere and the biosphere and is called Nitrogen cycle. P u r
e N i t r o g e n can be obtained by thermal decomposition of sodium azide . 2NaN
3

2Na + 3N
2
. Most important elements for life process is nitrogen contain about
16% N in them .
N
2
can be obtained by heating a mixture of NH
4
Cl and NaNO
3
or NH
4
NO
2
or
decomposition of ammonium dichromate, ( NH
4
)
2
Cr
2
O
7
. N
2
is less soluble in water
than O
2
.
Solid nitrogen exists in two allotropic crystalline forms : a -nitrogen ( cubic ) and b -
nitrogen ( hexagonal ).
Nitrogen exists as discrete diatomic molecule , N
2
in the gaseous , liquid and solid
state .
Inspite of its high electronegativity ( 3.0) , nitrogen is relatively inert chemically . It
reacts with simple substances ( except for Li) either at high temperatures or in the
presence of catalysts . The chemical inertness is due to high strength of N N bond
and high bond dissociation energy . Because of the stability of N
2
molecule , a
number of nitrogen compounds are endothermic . N
2
being a gas , the entropy of
formation of such compounds is negative ( Exothermic ) .
Most nitrogen compounds are thermally unstable and decompose relatively easily on
heating . This explains why N
2
is present in the earth mainly in the free form .
Phosphorus does not occur in free state in nature because of its high reactivity .
Important minerals of phosphorus are phosphorus rock , Ca
3
(PO
4
)
2
.
Fluorapatite,CaF
2
.Ca
3
(PO
4
)
2
and chlorapatite,Ca Cl
2
. Ca
3
(PO
4
)
2
. is the chief
constituent of teeth and bones . Phosphorus can be obtained by the reduction of
phosphate mineral such as bone as h with silica and coke in an electric furnace at
1500C . White P is the most reactive form of P. Red P is the most stable form of P.
White P contains P4 molecules and red P contains polymerised P units . In white P,
the 4 atoms are pointed towards the 4 corners of a regular tetrahedron. White P is
reactive because of small bond angle (60) or bond strain . White P is the commonest
form of P. It is most volatile , reactive solid but thermodynamically the least stable .
The thermodynamically most stable form of P is black P. The P-P-P bond angle in
white P is 60. The P-P bond distance is 221 p.m. The low bond angle indicates
considerable strain in the molecules in white P. Red P is more dense than white P, has
a higher m.p. and is much less reactive . White P is more volatile than red P because
P4 molecules are held by weak vander Waals forces . White P is always kept under
water because of its high reactivity and because its ignition temperature is very low,
being 30 C. White P is soluble in non polar solvents such as C
6
H
6
, CS
2
etc. Red P is
soluble in conc. HNO
3
or alcoholic KOH. White P becomes yellow because of slow
oxidation to P
2
O
5
. Red P is used in match industry . White P is poisonous and causes
phossy jaw.So it is banned in match industry . Strike any where matches contain P4S
3

.The head of safety match stick contains KNO
3
or KNO
2
or red lead with grounded
glass and antimony sulphide. Sides of match box contain red P and sand powder or
powdered glas. Black P has a graphite like appearance and a flaky layer lattice . The
elements of VA group form trioxides and pentoxides . Pentoxides are more acidic
than trioxides (N
2
O
5
> N
2
O
3
). The acidic nature increases as the oxidation
number of the element increases. For example , NO is neutral , N
2
O
3
is weakly
acidic and N
2
O
5
is strongly acidic . N
2
O
5
is the most acidic oxide in V group . It is
formed by N. The most acidic oxide in the Iind period is also formed by N. Dimeric
pentoxides are P
4
O
10
, As
4
O
10
and Sn
4
O
10
,while dimeric trioxides are P
4
O
6
, As
4
O
6

and Sb
4
O
6
. In P
4
O
6
each P atom is linked by three oxygen atoms and in P
4
O
10
, each P
atom is linked by 4-oxygen atoms .P
4
O
10
is a powerful drying and dehydrating agent .
Bi
2
O
3
is basic , but As
4
O
6
and Sb
4
O
6
are amphoteric oxides . Oxides of an element
in its highest oxidation state tend to be most strongly acidic and the least stable .
Thus As
4
O
6
is amphoteric and stable state decreases with increase in atomic
number . Thus Bi
2
O
5
has not been prepared in pure state. P
4
O
6
is acidic, As
4
O
6

and Sb
4
O
6
are amphoteric and Bi
2
O
3
is basic .
In a period , on going to right , the nature of the oxides of elements changes from
strong basic to strong acidic.

Nitrogen forms 5 oxides with oxygen . These are neutral or non- salt forming
oxides ( N
2
O and NO) and acidic oxides ( N
2
O
3
, NO
2
and N
2
O
5
) .The acids and
salts corresponding to the acidic oxides are HNO
2
, and nitrite for N
2
O
3
and nitric acid
(HNO
3
) and nitrates for N2O5 respectively . NO2 forms a mixture of HNO
2
and
HNO
3
. Salts of nitric acid are called nitrates and these decompose on heating to
yield oxygen .
The compounds of N and O are expected to be quite different from the oxides of
other elements in the VA group because the ability to form multiple bonds (pp -pp ) is
much less for the elements such as As, Sb and Bi .
In nitrogen oxides ( N
2
O , NO, N
2
O
3
, NO
2
( N
2
O
4
) , N
2
O
5
) , the nitrogen exhibits +ve
oxidation states of +1 to +5 . All the oxides have positive free energies of formation
because of high dissociation energy of nitrogen and oxygen molecules . All are
gases except N
2
O
5
, which is a white solid and sublimes at 305K. The reduction
potential for each of the oxidation states of nitrogen is positive . Thus each
positive oxidation state can be reduced and will serve as oxidiseng agen .
With oxygen , phosphorus forms two oxides , P
2
O
3
and P
2
O
5
which are acidic in
nature . The corresponding acid of P
2
O
5
is orthophosphoric acid , H3PO4. Salts of this
acid are called orthophosphates. H
3
PO
4
does not exhibit oxidising properties . It
is tribasic moderately weak acid and forms neutral salts like orthophosphates and acid
salts such as hydrogen orthophosphates and dihydrogen orthophophates.
Strong oxidising agents such as HNO
3
and conc. H
2
SO
4
oxidise phosphorus to
H
3
PO
4
.
P + 5HNO
3
H
3
PO
4
+ 5NO
2
+ H
2
O
Paramagnetic oxides of nitrogen are NO and NO
2
. Coloured gaseous oxide of
nitrogen is NO
2
. Most acidic oxide of nitrogen is N
2
O
5
. Thermally most stable
oxide of nitrogen is NO. The oxide of nitrogen that can not decolourise acidic
KMnO
4
is N
2
O
5
.
N
2
O can obtained by heating NH
4
NO
3
. N
2
O supports combustion at 500C because of
dissociation . It is also called laughing gas and has a linear shape .It is used in making
whipped cream . It is also used as anesthetic. NO ( nitric oxide ) is colourless gas but
gives brown fumes on exposure to air due to the formation of NO
2
.NO dissolves in
FeSO
4
solution and gives brown solution of FeSO
4
solution and gives brown solution
of FeSO
4
.NO( Brown ring test for NO
3
). N
2
O and NO can be seperated by passing
through FeSO
4
solution . NO also supports combustion .NO
2
is a reddish brown gas,
which dissolves in water giving a mixture of HNO
2
and HNO
3
. SO it may be regarded
as mixed anhydride of HNO
2
and HNO
3
.NO
2
is a powerful oxidising agent . It
supports combustion above 650 C. NO
2
is paramagnetic but N
2
O
4
is diamagnetic
due to pairing of unpaired electrons . N
2
O
3
is pale blue in liquid state. It is
anhydride of HNO
2
. N
2
O
5
is anhydride od HNO
3
. In solid state it exists as NO
2
+
,
N
2
O
5
is the strongest oxidising, agent among all the oxides of nitrogen . All oxides of
nitrogen are monomeric (NO, N
2
O , N
2
O
3
, NO
2
( N
2
O
4
) , and N
2
O
5
, while oxides of
other elements ate dimeric (P
4
O
6
, P
4
O
10
etc.) .
The per nitric acid (H
2
N
2
O
2
) is hydrate of N
2
O. It is unstable and explodes
violently when dry . The acid and its salts (hyponitrites ) are reducing agents . It is
dibasic acid .
The nitrous acid is also unstable and known only in solution . It is monobasic acid and
its salts are called nitrites. These salts are stable . The acid and its salts act as
oxidising as well as reducing agents .
Nitric acid (HNO
3
) , also known as aqua fortis, is manufactured by Birkland and
Eyde process (arc prcess ) or by Ostwalds process. In arc process raw material is dry
air , while in Ostwalds process it is ammonia . In Ostwalds process oxidation of NH
3

is carried out in presence of platinum gauze . Pure HNO
3
is colouless liquid but turns
yellow due to dissolved oxides of nitrogen . 96 - 98% HNO3 is called fuming nitric
acid . HNO
3
reacts with all metals , except Au, Pt , Rh, Ir and Ta .Cold conc. HNO
3

makes al ,Fe , Cr stainless steel passive . The ability of nitric acid , in presence of
H
2
SO
4
, to nitrate many organic compounds is due to the formation of NO
2
+ ion.
Nitric acid is a powerful oxidising agent . Thus non-metals such as S, P, I
2
etc
oxidised to their respective oxyacids when heated with conc. HNO
3
.
When nitric acid reacts with metals , the products of reaction ( other than metal
nitrates ) are largely determined by (a) Position of the metal in the
electrochemical series (b) Concentration of the acid (c) Temperature . The
reaction products may contain one or more of the substances HNO
2
, NO
2
, NO,
N
2
O , N
2
, NH
2
OH or NH
3
. H
2
is produced only when dilute HNO
3
reacts with
Mg , Mn or Zn. Metals above hydrogen in the electrochemical series react to
yield products such as H
2
, N
2
, NH
3
, NH
2
OH or N
2
O when treated with nitric
acid .
Nitrous acid plays an important role in reaction between nitric acid and noble metals
such as Cu , Ag and Hg . Copper is not attacked by HNO
3
in presence of urea or H
2
O
2

, because these compounds destroy any HNO
2
as soon as it is formed .
With Cu, dilute HNO
3
gives NO, but conc. HNO
3
gives NO
2
. With Zn, cold dilute
HNO
3
gives N
2
O , but hot conc. HNO
3
gives NO
2
. With Sn , Mg or Zn , cold dilute
HNO
3
gives NH
4
NO
3
but conc. HNO
3
gives hydrated oxide. With Ag , Co , Ni and
Pb , cold dilute HNO
3
gives NO, but conc. HNO
3
gives NO
2
.
The metals such as Mn, Mg react with cold dilute HNO
3
to form metal nitrate and H
2

. The metals such as Fe , Zn etc. react with very dilute HNO
3
to form metal nitrate
and NH
4
NO
3
. Metals such as Pb , Cu , Ag and Hg react with dilute HNO3 to form
metal nitrate and NO. Fe and Zn react with dilute HNO
3
to form metal nitrate and
NO
2
. Sn reacts with dilute HNO
3
to form Sn ( NO
3
)
2
+ NH
4
NO
3
. Al does not react
with dilute or conc. HNO
3
. Au , Pt etc do not react with even conc . HNO
3
. Fe
becomes passive with conc. HNO3 . Zn, Fe , Pb , Cu , Ag and Hg react with conc.
HNO
3
to form metal nitrate and NO
2
.Sn reacts with conc. HNO
3
to form H
2
SnO
3
+
NO
2
.In general reaction of dilute HNO
3
on metals above hydrogen in the
electrochemical series can be represented as ,
3Zn +8HNO
3
3Zn(NO3)
2
+ 2NO+ 4H
2
O
The reaction of dilute HNO
3
on metals below hydrogen can be represented as ,
3 Cu + 8HNO
3
3 Cu(NO
3
)
2
+ 2NO + 4H
2
O
Cold dilute HNO
3
reacts with Mg and Mn to liberate H
2
.

Very dilute and cold HNO
3
reacts with Zn , Fe and Sn in the following manner .

Dilute and cold HNO
3
reacts with Zn as under ,

Concentrated HNO
3
reacts with metals above hydrogen in the following manner ,


Concentrated HNO
3
reacts with metals below hydrogen as follows .

Vapours of concentrated HNO
3
react with Zn and Cu in the following manner.

HNO
3
reacts with non metals in the following manner,

Oxidising properties of HNO
3
are shown by reactions of the type.

Nitric acid acts as nitrating agent in presence of conc. H
2
SO
4
.Nitric acid is slowly
decomposed by light giving NO
2


Action of heat on HNO
3
can be represented as ,

Aqua regia is a mixture of 3 parts conc. HCl and 1 part conc. HNO
3
.

Action of heat on some nitric acid salts ( nitrates ) can be represented as follows :

Conc. HNO
3
produces yellow stains on the skin because of formation of
xanthoproteins .
The oxyacids of phosphorus are more than those of any other element .
The structure of the acids are such that each P atom is tetrahedrally surrounded by 4
neighbouring atoms . That is , it is 4 co- ordinate.
Each oxyacid contains atleast one P = O unit . All P atoms in the oxyacids have
atleast one P-OH linkage . The basicity of the acid is equal to the number of such H
atoms bonded to P through oxygen .
Some oxyacids have one or more P-H links, Such directly bonded H-atoms are
not acidic, because they are not ionisable . The H atom directly bonded to P
confer strong reducing properties on the molecules . Catenation takes place
through P-O-P links or directly through P-P bonds . Oxyacids containing P in the
lower oxidation states of +1 and +3 tend to disproportionate, as a result , some P
atoms attain the relatively stable + 5 state.
Hypophosphorus acid ( H
3
PO
3
) is generally prepared as its barium salt by heating
white P with aqueous Ba (OH)
2
. The free acid is obtained by treating the barium salt,
barium hypophosphite with calculated amount of dilute H
2
SO
4
. Pure H3PO
2
is white
crystalline solid . It is a monobasic acid. H
3
PO
2
and its salts , known as
hypophosphites are strong reducing agents . They decompose on heating and liberate
PH
3
.
Phosphorus acid (H
3
PO
3
) can be obtained by the hydrolysis of PCl
3
in cold water. It
is moderately strong dibasic acid and forms normal salts as Na
2
HPO
3
and acidic salts
such as NaH
2
PO
3
. Its salts are known as phosphites . H
3
PO
3
decomposes on heating
to yield PH
3
and H
3
PO
4
. The acid and its salts are good reducing agents. Phosphorus
acid is an extermely hygroscopic white crystalline solid.
Phosphoric acid or orthophosphoric acid ( H
3
PO
4
) can be prepared by heating Ca
3

(PO
4
)
2
with H
2
SO
4
(b) Dissolving P
2
O
5
in hot water (c) Hydrolysis of PCl
5
(d)
Refluxing red P with excess conc. HNO
3
on a water both . It is hydrate of P
2
O5
(P
4
O
10
). Dehydration on H
3
PO
4
gives pyrophosphoric acid , H
4
P
2
O
7
. Commercial
phosphoric acid has about 85% and H
3
PO
4
is called syrupy phosphoric acid . It is
syrupy because of extensive hydrogen bonding . Phosphoric acid is tribasic acid and
forms three series of salts . The acidic NaH
2
PO
4
, neutral or weakly basic NaHPO
4

and basic Na
3
PO
4
.
Dilute aqueous solutions of the acid are strongly acidic but only one of the hydrogen
atoms is readily ionisable. Solutions of H
2
PO
4
are weakly acidic, those of HPO
2
-4

weakly alkaline and those containing PO
3
-4
ions are strongly alkline due to hydrolysis
. On heating to 220 C, H
3
PO
4
gives pyrophophoric acid and at 316C it gives
meta phosphoric acid .
Hypophosphoric ( H
4
P
2
O
4
) can be prepared by oxidising phosphorus acid with
iodine. The acid shows no reducing properties and decomposes on heating above its
m.p. (346K). It undergoes rearrangement and disproportionation even at room
temperature.
Pyrophosphoric acid (H
4
P
4
O
7
) can be obtained by heating H
3
PO
4
to 220 C. It is
tetrabasic acid, which on heating to 316C gives metaphosphoric acid , HPO
3
.
The metaphosphoric acid (HPO
3
) can be obtained by heating ammonium phosphate .
It can also be obtained by heating microcosmic salt , NaNH4 .It is known as glacial
phosphoric acid . It is a monobasic acid .
As
4
O
6
dissolves in water to give a weakly acidic solution of arsenious acid . The acid
forms salts with alkalies most of which are meta-arsenates, for example , NaAsO
3
.
Arsenic acid ( H
3
AsO
4
) is weaker than H
3
PO
4
and is obtained by the oxidation of
As
4
O
6
with conc. HNO
3
. H
3
AsO
4
is a strong oxidising agent . This reflects the
greater stability of As (III) compared to As(V) . Sb
4
O
6
is much less soluble in water
than As4O6, but its saturated solution is acidic .Very little is known about H
3
SbO
4

and their salts.No oxyacids of bismuth are known , Bi
2
O
3
is not acidic and is
insoluble in alkalies .
All the possible simple trrihalides of elements of VA group are known . The number
of pernahalides is limited . Nitrogen does not form penta halides , because its
maximum covalency is 4 . Bismuth only forms BiF
5
, because of marked instability of
Bi (V) . AsBr
5
, SbBr
5
, AsI
5
and SbI
5
do not exist , because of reducing character of
Br- and I- and oxidising properties of As (V) and Sb (V).
All the possible trihalides of N, P , as Sb and Bi are known . They are all covalent ,
except BiF
3
, which shows ionic character . The stability of MX
3
increases as one
moves down a group .
NF
3
is a colourless gas , NCl
3
is an oily liquid , which may explode violently on
heating , Nbr
3
and NI
3
are unstable. The instability of the nitrogen halides is due to
enormous strength of N N bond . NF
3
is stable probably due to ionic resonance of
the molecule .
Trihalides of P, As, Sb and Bi (except BiF
3
) can be prepared by direct combination of
elements . The group VA element should be in excess otherwise pantahalides are
formed . The tihaledes are all hydrolysed with water . The products formed are
different. On hydrolysis NCl
3
gives NH
3
and HOCl, but PCl
3
gives H
3
PO
3
. The
hydrolysis of As Cl
3
is complete but reversible . Both SbCl
3
and BiCl
3
are hydrolysed
to the insoluble basic chlorides .
Phosphours trihalides act as electron pair donors. All the known pentahalides can be
prepared by halogenation of the trihalides. PF
5
is chemically reactive gas. PX
5
are
readily hydrolysed. PF
5
appears to be stable but Pcl
5
dissociates reversible to Pcl
3
and
Cl
2
. Pbr
5
undergoes dissociation in the liquid state . In the vapour state PF
5
, Pcl
5
,
PCl
3
F
2
molecules have a trigonal bipyramidal structure. Pcl
5
is molecular in the has
phase and ionic in the solid phase, [PCl
4
]+[PCl
6
]-. Pbr
5
is also ionic in solid state but
exists as [PBr
4
]+[Br]-. Four pentahalides of As Sb and Bi are known. These are
AsF
5
, SbF
5
, BiF
5
and SbCl
5
. AsCl
5
is relatively unstable is comparision to Pcl
5
,
probably due to incomplete shielding of the nucleus, as a result of which energy of 4s
2

electrons is decreased making it more difficult to promote one of the 4s
2
electrons for
the formation of AsCl
5
.
The hybridisation of elements in trihalides is sp
3
and the shape of trihalides is
pyramidal. The hybridisation of elements is pentahalides is sp
3
d and the shape of
pentahalides is trigonal bipyramidal.
All the elements of VA group form volatile hybrides of the type NH
3
. Nitrogen and
phosphorus also form hydrides, N
2
H
4
and P
2
H
4
. In addition nitrogen also forms H N
(hydrazoic acid) . The trihydrides are all colourless gases. The st6ability ease of
formation and basicity all decrease repidly with increase is atomic number. The
much greater stabilty of NH
3
greater solubility greater basically high melting
and boiling points, large heat of vapourisation, high dielectric constant high
polarity and ease of liquefaction can all be attributed to the much greater
electronegativity of N with its lone pair of electrons ready for donation or
hydrogen bonding.
All the trihydrides are pyramidal molecules and the bond angle decreases on moving
down the group or as the electronegativity of the central atom decreases. The
decrease in electronegativity down the group causes the bond pair to come closer to
the H-atom. Thus repulsion between bond pairs in the vicinity of the central atom
decreases and hence bond angle decreases.
The thermal stability of MH
3
hydrides decreases with increase in size of M. The
hydrides are good reducing agents (except for NH
3
in acid solution). The
reducing power increases as we go down the group. Ammonia is rather inert to
oxidation.
Basic character of hydrides decreases in the order NH
3
> PH
3
> AsH
3
> SbH
3
> BiH
3
.
Stability of hydrides decreases in the order NH
3
> PH
3
> AsH
3
> SbH
3
> BiH
3
.
Decomposition temperature decreases in the oreder NH
3
> (1573K) > PH
3
(673K) >
AsH
3

(553K ) > SbH
3
(423K) > BiH
3
(Unstable ).
Solubility in water decreases in the oreder NH
3
> PH
3
> AsH
3
> SbH
3
> BiH
3
.
Reducing nature increase from NH3 to BiH3 .
Bond angle decreases from NH
3
(107) to BiH
3
(90)
Ease of formation of hydrides decreases in the order N > P > As > Sb > Bi.
Volatility of hydrides increases in the NH
3
< SbH
3
< AsH
3
< PH
3
.
Acidity of triooxides decreases in the oreder N
2
O
3
> P
4
O
6
> As
4
O
6
> Sb
4
O
6
> Bi
2
O
3
is
strongly acidic and Bi
2
O
3
is basic .
Strength of oxyacids decreases in the order HNO
3
> H
3
PO
4
> H
3
asO
4
.
Ionic nature of trihalides increases in the order NF
3
< PCl
3
< AsCl
3
< SbCl
3
< SbCl
3
<
BiCl
3

Poisonous nature of hydrides increases in the order NH
3
< PH
3
< AsH
3
< SbH
3
< BiH
3

.
Most poisonous compound of nitrogen is KCN . Nitrogen compound used as
smelling salt is ammonium carbonate . HNO
2
acts as oxidising , reducing and
complexing agent . Nitrogen is the most abundant gas in the atmosphere .
Nitrogen is capable of forming 3 covalent and 1 co-ordinate covalent bond . The
oxide of nitrogen produced during lightening in atmosphere is nitric oxide which
reacts further with oxygen to form NO
2
. NO is paramagnetic and contains three
electron bond . The ionic character of halides increases with increase with increase
in atomic number in VA group . As the oxidation number of the central atom in
oxyacids of VA group elements increases , the nature of the acid changes from
reduding to oxidising . Antidote of arsenic compounds is Fe (OH)3. NH3 may be
manufactured by Haber process or cyanamide process . A mixuture of CaCN
2
+ C is
called nitrolim and used as fertilizer .Superphosphate of lime is Ca (H
2
PO
4
)
2
.H
2
O
+2CaSO
4
. 2H
2
O.NH
3
can be absorbed by quick lime ( CaO) . Conc. H
2
SO
4
, forms
ammonium sulphate , CaCl
2
forms CaCl
2
. 8NH
3
and P
4
O
10
forms ammonium
phosphate . Ammonium nitrate is the explosive fertilizer of nitrogen . Au, Pt, Pd etc
. are soluble in aqua regia. NOCl formed dissolves the noble metals . Formula of nitre
cake is NaHSO
4
. NCl
3
is explosive liquid . Black phosphorus is semiconductor and
good conductor of electricity . Most abundant allotrope of P is white phosphorus .
Violet P is the dense variety of phosphorus ( density = 2.35). Liquid ammonia is used
as refriherant because of its high heat of vapourisation . Conc . HNO
3
turns skin
yellow due to conversion of proteins into xantho protein . Before opening liquid NH
3

bottle,it is to be cooled because it has high vapour pressure. The disease developed
by the constant touch with white P is called Phosy Jaw .N
2
is neutral and
paramagnetic .Chemical used in smoke screens is Ca
3
P
2
. ( Calcium phosphide ).PH
3

forms vortex rings when omes in contact with air due to combustion . White P is
used as rat poison . When 100 ml of air is inhaled , it contains about 80 ml of N
2
.
Nitrous oxide is soluble in alcohol . Phosphorous atom differs by phosphide ion by 3
electrons . Strike anywhere matches contain red P on the tip of the stick .