IITM COLLEGE OF ART, SCIENCES and COMMERCE

B.Sc. 2nd semester

Lecture Notes
Section-C
( P- Block elements , Boron family , Carbon family)

Group 13 to 18 constitute p-block elements. The general configuration for all the
atoms belonging to p-block is ns2np1-6.The s and p block elements together forms
representative elements.
The s-block and p-block elements are so called because their valence electrons are
in an s orbital or p orbital respectively. They are also called Typical Elements to
distinguish them from the transition and inner transition series

Characteristic Properties of Elements in p-Block of Modern Periodic

Table:
Atomic and Ionic Radii - As we move down the group in the p-block one additional
shell than the previous element gets included into the following element. This at last
increases the nuclear and the ionic radius of each next element down the group,
which at last demonstrates that the nuclear and the ionic radii increment down the
group. The pattern is not same over the period. As we move towards right in a period
the Atomic radii and the Ionic radii of pblock elements diminishes. The atomic radius
increases enormously from Boron to Aluminium. This expansion is because of more
prominent screening impact created by the eight electrons exhibited in the
penultimate shell.
Ionization Energies - There are high ionization possibilities in p-block elements. The
ionization energies of p-block elements increase towards right in a period because of
effectively expanding atomic charge. As indicated by the general patterns the
ionization energy values diminishes down the group yet don't diminish smoothly.
Ionization Energies in Non-metals is higher than metals. It is most extreme for a noble
gas since noble gasses have totally filled configuration. A few elements at the base of
a group like Lead, Tin, Thallium, Bismuth, and so forth acts nearly as a metal with low
ionization energies.
 Melting and Boiling Points – The melting and boiling points decrease from top to
bottom in a group. The decrease in melting points do not show a regular pattern.
However, the decrease in boiling point follow a regular trend down the group.
Oxidation States – The oxidation state is related to the number of electrons in the
valence shell. The valence shell configuration of group 13 is ns2np1.Since there are
three electrons in the valence shell, +3 is the most common oxidation state in their
compounds. However , on moving down the group +1 oxidation state becomes more
stable than +3 oxidation state. In fact , Tl prefers to form compounds in +1 oxidation
state rather than in +3 oxidation state. This can be explained as:
Except B and Al, all the elements have either d-electrons (Ga ,In) or both d and f
electrons(Tl) in there inner electrons. We know that d and f electrons have poor
screening effect. Due to this, the nuclear force of attraction increases ad holds the
outer ns2 electrons tightly . The two electrons in the s-subshell are inert as they do
not get paired. This is called inert pair effect. Only 1 electron in p subshell take part
in bond formation .Thus the oxidation state decrease by two units in the group top to
bottom.
Electropositive Character – Electropositive character decreases in a period as the
nuclear charge increases and size decreases from left to right in the period. Thus,
group 13 is less electropositive and less metallic than the elements of group 1and 2.B
is non metal . Electropositive character increases from top to bottom as the size
increases and ionization energy decreases from B to Tl.
Covalent Character – From the electronic configuration of these elements, all of
them would be expected to form M 3+ type ions and the compounds would be ionic.
However, the second and third ionisation energies of boron are so high that it has
little tendency to form B3+ ion and other elements have higher tendency to form such
ions under suitable conditions due to lower ionisation energies. Thus these elements
form ionic compounds. Further if trivalent ions are formed, the smaller ions will have
more polarising power and will tend to give covalent compounds. This tendency goes
on decreasing down the group. That is why B gives covalent compounds, Al forms
both covalent and ionic compounds and the higher members result mainly in ionic
compound formation.
Anomalous Properties of Boron :
• Though aluminium is a metal, Boron is a non-metal.
• Aluminium is a good conductor of electricity but Boron is not.
• Boron exists in two structures amorphous and crystalline. Aluminium is a delicate
metal and does not exist in various structures.
• The boiling point and melting point of boron are much higher as compared to those of
aluminium.
• Boron frames just covalent compounds while aluminium shapes even some ionic
compounds.
• The oxides and hydroxides of boron are acidic in nature though those of aluminium
are amphoteric.
• The trihalides of boron (BX3) are monomers whereas, aluminium halides subsists as
dimers (Al2X6).
• The hydrides of boron are quite inert while those of aluminium are flimsy
o.

Diagonal Resemblance of Boron With Silicon :

• Boron and Silicon show the distinctive properties of non-metals. These don't shape
cations. Both exist in crystalline and amorphous structures.
• Boron Oxide (B2O3) and silica (SiO2) are both acidic and break up in solutions that
are alkaline in nature to frame borates and silicates separately.
• B2 O3 + 6NaOH → 2Na BO3 + 3H2O
• SiO2 + 2NaOH → Na2SiO3 + H2O
• Silicates and borates have tetrahedral SiO4 and BO4 auxiliary units individually.
• The chlorides of both Si and B get hydrolyzed by water to form respective silicic acid
and boric acid.
BCl3 + 3H2O → H3BO3 + 3HCl
SiCl4 + 3H2O → H2SiO3 + 4HCl
• The hydrides of Boron and Silicon are very stable. Various unstable hydrides are
additionally known which burst into flames on introduction to air and are effortlessly
hydrolyzed.
• Both these elements are semiconductor by nature.

HYDRIDES OF BORON: DIBORANE

Boron forms a large number of polymeric hydrides called boranes, e.g. B 2H6, B4H10,
B5H9, B5H11 etc. Diborane (B2H6) is an important member of this series.
Preparation of diborane (B2H6):
Diborane can be prepared by the following methods:
(i) By the action of ionic hydrides like NaH or CaH2 on BCl3
6NaH + 3BCl3 → B2H6 + 6NaCl
3CaH2 + 2BCl3 → B2H6 + 3CaCl2
(ii) By the reduction of BF3 with Li H, Li (BH4) or Na (BH4)
8BF3 + 6LiH→ B2H6 + 6LiBF4
BF3 + 3Na(BH4) → 2B2H6 + 3Na F
(iii) By the reduction of BCl3 with Li [AlH4]
4BCl3 + 3Li(AlH4) → 2B2H6 + 3LiCl + 3AlCl3
(iv) By the reduction BCl3 vapours with molecular hydrogen
2BCl3 (vapours) + 6H2→ B2H6 + 6HCl

Properties: It is an inflammable colourless gas, extremely toxic and reactive and

stable only at low temperatures in absence of moisture.
(A) Decomposition:
(i) By heat:
When heated between 100֠C and 250̊C, it changes into a number of boranes:
2B2H6→ B4H10 + H2
5B2H6→ B10H14 + 8H2

(ii) By water:
B2H6 is readily decomposed (hydrolysed) by water into boric acid and H2.
B2H6 + 6H2O → 2H3BO3 + 6H2O
(iii) By aqueous alkalies:
On passing B2H6 into an aq. solution of alkalies, e.g. KOH, at 0 ̊ C, potassium

hypoborate, K2 [B2H6O2], is obtained solution. B2 H6 + 2KOH → K2[B2

H6O2] (pot. hypoborate) On diluting this solution, potassium metaborate is formed.

K2[B2H6O2] + 2H2O → 2KBO2 + 5H2

Evolution of H2 in alkaline medium makes it a useful reducing agent.
(B) Combustion:
B2H6 is an extremely reactive gas hence under controlled conditions, if reacted
with O2, gives large amount of energy at room temperature
B2H6 + 3O2 → B2O3 + 3H2O + Energy (Rocket fuel)
(C) Action of halogens and halogen acids:
Under different conditions it reacts with halogens (except iodine) and halogen acids.
250C
B2H6 + 6Cl2 → 2BCl3 + 6HCl (vigorous reaction)
B2H6 + Br2 → B2H5Br + HBr (slow reaction)
. B2 H6 + HX → B2H5 X (X = Cl, Br, I) + H2.
 (D) Reaction with alkali metal hydrides:
Alkali hydrides suspended in ether react with diborane and give alkali metal
borohydrides which are used as reducing agents.
B2H6 + 2LiH → 2Li[BH4]
B2H6 + 2NaH → 2Na[BH4]
(E) Reaction with ammonia:
Under different experimental conditions, diborane reacts with ammonia giving various
products:
(i) At low temperature of about 1200C, excess of ammonia gives an addition compound,
diammoniate of diborane.
B2 + H6 + 2NH3 → B2H6.2NH3 (white non-volatile solid)
(ii) At high temperature, B2H6 and NH3 in 1:2 ratio, react together to form borazine (or
borazole) B3N3H6
3B2H6 + 6NH3 → 2B3N3H6 + 12H2

Structure of diborane:

The electron diffraction and infra-red spectroscopic studies of B2H6 molecule have
shown that this molecule has hydrogen bridge structure (Fig1 a) in which two irregular
BH4 tetrahedra have one edge in common and thus two B atoms (B1 and B2 ) and
four terminal Hatoms (Ht) are coplanar (lie in the same plane) while remaining two
bridging H-atoms (Hb) are located at the centre above and below the plane, the two
planes are perpendicular to each other.
Bridged structure of diborane

The structure of Diborane molecule consists of four hydrogen atoms and that of two
boron atoms coming on the same plane. In between these planes, there are said to
be two dividing atoms of hydrogen.
The boron atom is known to be sp3 hybridized and has four hybrid orbitals. From
these four hybrid orbitals, three of the orbitals have one electron each, and of which
one is an empty orbital. The two electrons of the hybrid orbitals in each of the boron
atoms form 2 bonds with the 1s hydrogen atoms. The two atoms of boron left with
that of each unpaired electron orbital and empty orbital forms the two bridgings (B–H–
B) bonds with that of the two 1s hydrogen atoms, is also called as the banana bond.

BORAZINE :
Inorganic benzene is also known as borazine which is an inorganic and a cyclic
compound. There are three BH units and three NH units alternate. The chemical
formula of inorganic benzene is:
B3N3H6
 Why is borazine called “inorganic benzene”?
Borazine is called “inorganic benzene” because the compound is isoelectronic and
isostructural with benzene. The other similarities are it is a colourless liquid with
aromatic smell. Borazine is said to be aromatic because the number of pi electrons
obeys 4n+2 rule and the B-N bond lengths are all equal.
Preparation of Borazine :
There are three different ways to prepare inorganic benzene and they are:
• Stock and Pohlands method:

• 3B2H6+6NH3→3[B2H6.NH3]→2B3N3H6+12H.

• The yield obtained by this method is low because there is a simultaneous formation of
solid polymeric by-products
.Heating BCl3 with NH4Cl:
• 3NH4Cl + 3BCl3 → B3N3H3Cl3

• B3N3H3Cl3+ NaBH4 → B3N3H6 + B2H6

STRUCTURE OF BORAZINE:
Borazine is isoelectronic with benzene and has similar connectivity, so it is sometimes
referred to as "inorganic benzene". This comparison is not rigorously valid due to the
electronegativity difference between boron and nitrogen. X-ray crystallographic
structural determinations show that the bond lengths within the borazine ring are all
equivalent at 1.429 Å, a property shared by benzene. However, the borazine ring
does not form a perfect hexagon. The bond angle is 117.1° at the boron atoms and
122.9° at the nitrogens, giving the molecule distinct symmetry.
 The electronegativity of boron (2.04 on the Pauling scale) compared to that of
nitrogen (3.04) and also the electron deficiency on the boron atom and the lone pair
on nitrogen favor alternative mesomer structures for borazine.

CHEMICAL PROPERTIES :
• It reacts with water and alcohol to give addition product , which above 100 ̊ C
releases H2 gas.
B3N3H6 + 3H2O → [BH(OH)NH2]3 → [B(OH)NH]3 + 3H2
B3N3H6 + 3ROH → [BH(OR)NH2]3 → [B(OR)NH]3 + 3H2
• On heating , borazine gives a product similar to naphthalene,biphenyl etc.
TRIHALIDES OF BORON –
Lewis Acid Character
The halides react with water to form boric acid..All three lighter boron trihalides (BF 3,
BCl3, and BBr3) form stable adducts with common Lewis bases.The sequence for the
Lewis acidity is BF3 < BCl3 < BBr3,where BBr3 is the strongest Lewis acid. This trend
is commonly attributed to the degree of -bonding in the planar boron trihalid that
would be lost upon pyramidization(The conversion of a molecule’s trigonal planar
geometry to a tetrahedral one) of the the BX3molecule. Boron tribromide (BBr3) is a
colorless, fuming liquid that is an excellent demethylating or dealkylating agent. Boron
tri chloride (BCl3) is a colourless, dangerously reactive gas that is a valuable reagent
in organic synthesis. Boron trifluoride (BF3) is a pungent, colorless, corrosive, toxic
gas that forms white fumes in moist air.
Boron Halides
Boron undergoes halogenation to form trihalides with the molecular
structure BX3, as in the following:
2B + 3Br2 → 2BBr3
In its most familiar compounds, boron has the formal oxidation state III, or +3. These
include oxides, sulfides, nitrides, and halides. The trihalides form planar trigonal
structures and are Lewis acids because they readily form adducts with electron-pair
donors, which are called Lewis bases. For example, fluoride (F–) and boron trifluoride
(BF3) combine to give the tetrafluoroborate anion, BF4–. Boron trifluoride is used in
the petrochemical industry as a catalyst.
The halides react with water to form boric acid: BX3+ 3H2O → B(OH)3+ 3HX

where X can be Cl, Br, or I.

Lewis Acidity of Boron Halides

All three lighter boron trihalides, BX3 (X = F, Cl, Br), form stable adducts with common
Lewis bases. Their relative Lewis acidities can be evaluated in terms of the relative
exothermicities of the adduct-forming reaction. Such measurements have revealed
the following sequence for the Lewis acidity: BF3 < BCl3 < BBr3 (in other words, BBr3
is the strongest Lewis acid).
This trend is commonly attributed to the degree of π-bonding in the planar boron
trihalide that would be lost upon pyramidalization (the conversion of the trigonal
planar geometry to a tetrahedral one) of the BX3 molecule, which follows this trend
BF3 > BCl3 > BBr3 (that is, BBr3 is the most easily pyramidalized). The criteria for
evaluating the relative strength of π-bonding are not clear, however. One suggestion
is that the F atom is small compared to the larger Cl and Br atoms, and the lone pair
electron in the 2pzorbital of F is readily and easily donated, and overlaps with the
empty 2pz orbital of boron. As a result, the pi donation of F is greater than that of Cl or
Br. In an alternative explanation, the low Lewis acidity for BF3 is attributed to the
relative weakness of the bond in the adducts F3B-L.
Boron Tribromide
Boron tribromide (BBr3) is a colorless, fuming liquid compound that contains boron
and bromine. The reaction of boron carbide with bromine at temperatures above 300
°C leads to the formation of boron tribromide. The product can be purified by vacuum
distillation.
BBr3 is decomposed by water and alcohols. It is an excellent demethylating or
dealkylating agent for the cleavage of ethers, also with subsequent cyclization
(formation of cyclic molecules), often in the production of pharmaceuticals. The
mechanism of ether dealkylation proceeds via the formation of a complex between
the boron center and the ether oxygen followed by the elimination of an alkyl bromide
to yield a dibromo(organo)borane. The dibromo(organo)borane can then undergo
hydrolysis to give a hydroxyl group, boric acid, and hydrogen bromide as products.
The electronics industry uses boron tribromide as a boron source in pre-deposition
processes for doping in the manufacture of semiconductors.
Boron Trichloride
Boron trichloride (BCl3) is a colorless gas that is a valuable reagent in organic
synthesis, but is also dangerously reactive. Boron trichloride is produced industrially
by direct chlorination of boron oxide and carbon at 500 °C. The synthesis is
analogous to the Kroll process for the conversion of titanium dioxide to titanium
tetrachloride. In the laboratory, BF3 reacts with AlCl3 to create BCl3 via halogen
exchange. Boron trichloride does not form dimers, although there is some evidence
that may indicate dimerization at very low temperatures (20 K). NMR studies of
mixtures of boron trihalides shows the presence of mixed halides, which may indicate
a four center intermediate (that is, a dimer). The absence of dimerization contrasts
with the other trihalides of group 13, which contain four or six coordinate metal
centers.
Boron trichloride is a starting material for the production of elemental boron. It is also
used in the refining of aluminium, magnesium, zinc, and copper alloys to remove
nitrides, carbides, and oxides from molten metal. It has been used as a soldering flux
for alloys of aluminium, iron, zinc, tungsten, and monel. Aluminum castings can be
improved by treating the melt with boron trichloride vapors.
Boron Trifluoride
Boron trifluoride (BF3) is a pungent, colorless, toxic gas that forms white fumes in
moist air. The molecule is isoelectronic with the carbonate anion, CO 32−.
BF3 is commonly referred to as “electron deficient” because of its exothermic
reactivity toward Lewis bases. BF3 is manufactured by the reaction of boron oxides
with hydrogen fluoride. Since boron trifluoride is corrosive, the metals suitable for
handling boron trifluoride include stainless steel, monel, and hastelloy. In the
presence of moisture, boron trifluoride corrodes stainless steel.
Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and
polypropylene show satisfactory resistance.

HALIDE OF ALUMINIUM
Aluminium chloride (AlCl3) is a compound of aluminium and chlorine . The
solid has a low melting and boiling point, and is covalently bonded. It sublimes
at 178 ° C. Molten AlCl3 conducts electricity poorly, unlike more ionic halides
such as sodium chloride. It exists in the solid state as a six-coordinate layer
lattice.
Aluminium chloride is highly deliquescent, and it can explode in contact with water
because of the high heat of hydration. It partially hydrolyses with H2O, forming some
hydrogen chloride and/or hydrochloric acid.
Aluminium also forms a lower chloride, aluminium(I) chloride (AlCl), but this is very
unstable and only known in the vapour phase.
reaction of the elements, aluminium and chlorine. It is commercially available in large
quantities.

Structure

Al atoms in AlCl3 complete their octets by forming dimers, i.e.it has dimeric structure
in which the configuration of chlorine atoms about Al atoms is roughly tetrahedral. In
the crystalline state it has layered lattice structure with six coordination no. around. It
has polymeric structure at room temperature. At melting point (192.4) C it changes to
dimer Al̊ 2Cl6 where c.no. of Al is 4
Al2Cl6 has bridged structure. Each Al is tetrahedrally surrounded by 4 Cl atoms. At
still higher temp. Al2Cl6 dissociates to form monomer AlCl3. It is a planar triangular
with c.no. of Al 3

:
 AlCl3 exists as dimer but BF3 doesn’t???
BCl3 and AlCl3 both are the example of electron deficient compounds, as there are
only six electrons in the valency shell of central atom after the formation of the
molecule, thus, both the compounds have strong tendency to gain (two) electrons, so
that their octet is completed. In both the cases central atom undergoes sp2
hybridisation and both acquire trigonal planar geometry. The sp2 hybridisation
involves one s and two p orbitals, and one p orbital remains unhybridised, this
unhybridised p orbital lies perpendicular to the (trigonal) plane of the molecule
which being empty, may recieve two electrons from a suitable donor so as to
complete it’s octet. Now, remember, Chlorine atoms attached to the central atom
possess lone pairs (three).
The electron deficiency (octet) of Boron in BCl3 is compensated (completed) by
formation of co-ordinate bond between the lone pair of peripheral Chlorine atom and
the empty unhybridised p orbital of Boron atom, forming pπ– pπ bonding. Thus, the
electron deficiency of BCl3 is compensated by formation of pπ–pπ bonds within the
molecule so no dimer forms.
However, the electron deficiency of Aluminium atom in AlCl3 is compensated
(completed) by formation of co-ordinate bond between lone pair of Chlorine atom of
another AlCl3 molecule and the empty unhybridised p orbital of Aluminium atom,
thus forming dimer.
So, it is interesting to know that both BCl3 & AlCl3 are
1. halides of group 13 elements
2. Electron deficient
3. sp2 hybridised
4. Have empty one p orbital perpendicular to the plane of the molecule. But, former
doesn't forms dimer and later forms a dimer, because both the molecules
compensate their electron deficiency by different ways. Now, then the question arises
is; why both these species are completing it's octet by different ways? This is
because, Boron atom is so small that it cannot accommodate four bigger sized
Chlorine atoms, however, Aluminium being bigger atom can do that efficiently and
thus
compensates it's electron deficiency by forming dimer.
 CARBON FAMILY

Group 14 include Carbon (C) , Silicon (Si), Germanium(Ge) ,tin(Sn) ,lead(Pb) and
ununquadium (uuq) which is radioactive.
Occurrence
 Carbon is the 17th most abundant element by weight in the earth crust.
 It occurs in the native state in form of coal ,graphite and diamond.
 In combined state it occurs widely as metal carbonates, hydrocarbons ,carbohydrates
and carbon dioxide in air.
 Silicon is the second most abundant element by weight in the earth crust. It widely
occurs in form of silica , and in a wide variety of silicates and clays.
 Germanium occurs in traces and is mainly recovered from flue dust arising from
roasting of zinc ore.
 Germanium and silicon are used to make transistors and Semiconductor devices.
 The natural abundance of tin and lead are 2ppm and 13 ppm. Tin occurs mainly as
tinestone or cassitertite.
 The principal ore of lead is galena. Other words of lead are anglestite and cerussite.
Electronic configuration :
The general valence shell electronic configuration of elements of group 14 is
ns2 np2 where n is the number of the outermost principal shell.

Covalent radii :
The covalent radii of group 14 elements are smaller than those of the elements of
group 13. When we move from group 13 to group 14 within the same period ,the
effective nuclear charge increases and hence the covalent radius decreases due to
stronger attractive influence of the nucleus on the outer electrons.
Covalent radii of group 14 elements regularly increases as we move down the
group.It is due to addition of a new energy shells in each succeeding element. The
increase in covalent radius from Silicon onwards is however small due to ineffective
shielding of the valence electrons by the intervening d and f orbitals.
Ionisation enthalpy
The first ionisation enthalpies of group 14 elements are higher than those of elements
of group 13. Because of greater nuclear charge and smaller size of the atoms of
group 14 elements.
The first ionisation enthalpy decreases steadily on moving down the group from
carbon to tin. The decrease is very sharp from carbon to silicon while there is a slight
increase in the first ionization enthalpy of lead as compared to that of tin. The
decrease in ionization enthalpy down the group from C to Sn is due to increase in
atomic size and screening effect of the inner electrons which outweigh the effect of
increased nuclear charge. The small increase in ionization enthalpy from Sn to Pb is
due to a considerable increase in nuclear charge which outweights the shielding
effect of all the electrons in the inner shells including those of 4f and 5d electrons.

Electronegativity :
The elements of group 14 are more electronegative than group 13 elements because
of smaller size.
Electronegativity decreases down from Carbon to Silicon and remains constant from
Si to Sn and then slightly increases for Pb.
Metallic Character :
They are less electropositive and hence less metallic then group 13 elements
because of smaller atomic size and higher ionization enthalpy.
On moving down the group metallic character increases. Carbon is strictly non-
metallic, silicon is non-metal , germanium is a metalloid where tin and lead are soft
metal with low melting point.
Melting and boiling point :
The melting and boiling point of group 14 elements are much higher than those of
corresponding elements of group 13. The atoms of group 14 form four covalent bonds
with each other and hence there exist strong binding forces between their atoms both
in the solid as well as in the liquid state.The melting point and boiling point decreases
as we move down the group due to corresponding decrease in the interatomic forces
of attraction.
ALLOTROPES
Carbon has multiple allotropes. The most common is graphite, which is carbon in the
form of stacked sheets. Another form of carbon is diamond, but this is relatively
rare. Amorphous carbon is a third allotrope of carbon; it is a component of soot.
Another allotrope of carbon is a fullerene, which has the form of sheets of carbon
atoms folded into a sphere. A fifth allotrope of carbon, discovered in 2003, is
called graphene, and is in the form of a layer of carbon atoms arranged in a
honeycomb-shaped formation.
Silicon has two known allotropes that exist at room temperature. These allotropes are
known as the amorphous and the crystalline allotropes. The amorphous allotrope is a
brown powder. The crystalline allotrope is gray and has a metallic luster
Tin has two allotropes: α-tin, also known as gray tin, and β-tin. Tin is typically found in
the β-tin form, a silvery metal. However, at standard pressure, β-tin converts to α-tin,
a gray powder, at temperatures below 13.2° Celsius/56° Fahrenheit. This can cause
tin objects in cold temperatures to crumble to gray powder in a process known as tin
pest or tin rot.

Anomalous Behaviour Of Carbon :

Carbon, the first member of group 14 ,shows an anomalous behaviour i.e. differ from
rest of the members of its family.
The main reason for this difference are :
1) exceptionally small atomic size
b) higher electronegativity
c)higher ionisation enthalpy
d) absence of d orbital in the valence shell
The main point of differences are:
1) Carbon in form of diamond is very hard as compared to other members of group
14.
2) It has higher melting point and boiling point than other members of the group14.
3) Carbon has only 4 valence orbitals ,therefore ,at the maximum, it can
accommodate 4 pairs of electrons around it. The maximum covalency of carbon is 4.
The other elements of this group due to the presence of d- orbital can expand their
covalency to 6.
4) Due to small size and high electronegativity , carbon has a strong tendency to form
pπ- pπ multiple bonds either with itself or with the other items such as oxygen,
nitrogen and sulphur.
The remaining elements do not form pπ- pπ bonds because their atomic orbitals are
too large and diffused to have effective overlapping. Instead due to the presence of d-
orbitals, they have a tendency to form dπ-pπ bonds. Even this tendency to form dπ-
pπ bonds decreases down the group from Si to Pb as the size of the d- orbitals
increases.
Catenation : Carbon has the property of catenation which may be defined as the
ability of like atoms to link with one another through covalent bonds. This is due to
 smaller size and higher electronegativity of carbon atoms and unique strength of
carbon carbon bonds. The property of catenation mainly depends upon the strength
of element – element bond. Since the bond energy of C-C bond is very large, carbon
forms long straight or branched chains or rings of different sizes and shapes.
However ,as we move down the group, the element- element bond energies
decrease rapidly ,and therefore, the tendency for catenation decreases in the order
C >> Si > Ge≅ Sn >> PX
CARBIDES :
o Carbides are generally formed at high temperatures (> 1500 °C).
o Carbides are generally quite stable and exhibit high melting points.
o Carbides can be classified as salt-like, interstitial, and covalent.

Types of Carbides :
Carbides are compounds composed of carbon and less electronegative elements and
they are distinguished by their chemical bonding (ionic, covalent). They are generally
prepared from metals or metal oxides at high temperatures (1500 °C or higher) by
combining the metal with carbon. Carbides are used in key industrial applications.
Saline Carbides :
Salt-like (saline) carbides are composed of the highly electropositive atoms, such as
the alkali, alkali earth, and group-III metals, mixed with carbon. Aluminum forms
carbides, but other elements from group XIII do not. These materials have isolated
carbon centers, often described as “C4-” in the metanides, “C22-” in the acetylides, and
“C34-” in the sesquicarbides.
 Methanides are carbides that decompose in water and generate water; aluminum
carbide (Al4C3) and beryllium carbide (Be2C) are examples of this class of carbides.
 Acetylides are formed from alkali, alkali earth, and lanthanoid metals with the
acetylide anion C22-. Lanthanoids also form carbides with the formula M2C3. Metals
from group XI also form acetylides, such as copper(I) acetylide and silver acetylide.
Carbides of the actinide elements, which have the structure MC2 and M2C3, are also
described as salt-like derivatives of C22-.
 The polyatomic ion C34- is referred to as an allylenide or sesquicarbide and is found in
Li4C3 and Mg2C3. The allylenide is linear and isoelectronic with CO2.
 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 (B4C), on the other hand, has an unusual structure that
includes icosahedral boron units linked by carbon atoms. In this respect, boron
carbide is similar to the boron-rich borides. Both silicon carbide (also known as
carborundum) and boron carbide are very hard and refractory materials. Both
materials have important industrial applications.

Interstitial Carbides :
Interstitial carbides describe the carbides of the group-IV, -V, and VI transition metals.
These carbides are metallic and refractory. They are formed so that the carbon atoms
fit into octahedral interstices in a close-packed metal lattice when the metal atom’s
radius is greater than ~135 pm. When the metal atoms are cubic-close-packed (ccp),
then filling all of the octahedral interstices with carbon achieves 1:1 stoichiometry with
3since the octahedral interstices lie directly opposite each other on either side of the
layer of metal atoms, filling only one of these with carbon achieves 2:1 stoichiometry.
As a result of the packing, they are quite stable and have very high melting points and
low electrical resistance.
FLUOROCARBONS :
These are most amazing compounds of fluorine and have recently gained much
importance because of their interesting uses. Fluorocarbons are derivatives of
hydrocarbons in which hydrogen atoms are replaced by fluorine atoms.
Fluorocarbons containing 1-20 carbon atoms have been prepared recently.
PREPARATION :
 By direct reaction between carbon and gaseous fluorine
C + 2F2 → CF4
 By action of SbF3 on chloro derivatives
3CCl4 + 2SbF3 → 3CCl2F2 + 2SbCl3
 By fluorination of CH4 in presence of nitrogen
CH4 + F2 → CH3F + HF

SILICATES :
Silicates are the minerals containing silicon and oxygen in tetrahedral
SiO44- units which are linked together in several patterns. Depending on the way the
tetrahedral units are linked, the silicates are classified into the following types.
1. Ortho silicates (or Nesosilicates)
2. Pyro silicate (or Sorosilicates)
3. Cyclic silicates (or Ring silicates)
4. Chain silicates (or pyroxenes)
5. Sheet or phyllosilicates
6. Three dimensional (or tecto) silicates

Ortho silicates (or Neso or Island silicates) are the simplest silicates which contain
discrete SiO44- tetrahedral units. Structural unit of ortho silicate unit is shown below.

7.
8. The ortho silicate ion is the strong conjugate base of weak orthosilicic acid as well as
it will not persist in aqueous solutions. Hence in nature, ortho silicate minerals are
rare and only found with cations which form highly insoluble salts.
9. Examples of Ortho silicates:
10. 1) Phenacite (also known as phenakite) - Be2SiO4
11. 2) Willemite - Zn2SiO4 - A minor silicate ore of zinc. Highly fluorescent (green) under
shortwate UV.
12. Note: The Be2+ and Zn2+ ions are tetrahedrally surrounded by the oxygen atoms of
silicate.
Pyro silicate (or Soro silicate or disilicate) contain Si2O76- ions which are formed
by joining two tetrahedral SiO44- which share one oxygen atom at one corner (one
oxygen is removed while joining). Structure of pyrosilicate is shown below.

13. The pyrosilicate ion is less basic than orthosilicate ion. There only one mineral in
nature containing pyrosilicate ion.
14. E.g. 1) Thortveitite - Sc2Si2O7

Cyclic silicates contain (SiO3)n2n- ions which are formed by linking three or more
tetrahedral SiO44- units cyclically. Each unit shares two oxygen atoms with other
units.
 E.g.
1) Benitoite - BaTi(SiO3)3 : containing three tetrahedra arranged cyclically [Si3O9)6-
].
2) Beryl - Be3Al2(SiO3)6 : containing six-silicate rings [Si6O18)12-]. It is an
aluminosilicate. Each aluminium is surrounded by 6 oxygen atoms octahedrally. Well-
known varieties of beryl include emerald and aquamarine.
Chain silicates or pyroxenes contain (SiO3)n2n- ions which are formed by linking
‘n’ number of tetrahedral SiO44- units linearly. Each unit shares two oxygen atoms
with other units.

Examples of chain silicates:

1) Spodumene - LiAl(SiO3)2 - a pyroxene mineral consisting of lithium
aluminium inosilicate
2) Diopsite - CaMg(SiO3)2
3) Wollastonite - Ca3(SiO3)3
Note: The formula of cyclic silicates as well as chain silicates is (SiO3)n2n-. Hence
these are considered as an oligomers of the unknown SiO32- ion.
The general formula of Sheet or Phyllo or two dimensional (2-D) silicates is
(Si2O5)n2n- . Each SiO4 tetrahedron shares three oxygen atoms with others and thus
by forming two-dimensional sheets. These silicates can be cleaved easily just like
graphite. The layers are held together by weak van der Waal's forces.
 E.g.
1) Talc - Mg3Si4O10(OH)2 : It is the main ingredient of soap stone. It is the
softest material with a smooth and greasy touch.
2) Micas : General formula is X2Y4–6Z8O20(OH,F)4
Where X = K, Na, or Ca
Y = Al, Mg, or Fe
Z = Si or Al
E.g. Muscovite mica - KAl2(AlSi3O10)(F,OH)2 - split into thin layers extremely
easily
and Lepidolite - KLi2Al(Al,Si)3O10(F,OH)2
3) Clay : It is an aluminosilicate with sheet structure.
4) Kaolinite - AlSiO5(OH)5

THREE DIMENSIONAL SILICATES (TECTO SILICATES)

The general formula of three dimensional (3-D) or tecto or Framework
silicates is (SiO2)n . All the oxygen atoms of SiO4 are shared with other tetrahedra
and thus by forming three-dimensional network.
E.g. SiO2 - Quartz, Tridymite and Crystobalite - These are the crystalline forms of
silica.
When SiO44- units are replaced by AlO45- units, three
dimensional aluminosilicates are formed.
E.g. Feldspar, Zeolites, Ult etc.,

SOME POINTS :
* Silicate minerals are very common in the Earth crust since Oxygen and Silicon
are the most abundant elements.
* The degree of polymerization is denoted by Oxygen to Silicon ratio (O/Si).
Greater the degree of polymerization, lower will be the O/Si ratio. The values of O/Si
for ortho silicates (lease polymerized) = 4:1 while for tecto silicates (most polymerized
silicate) = 2:1.
* With increase in the degree of polymerization, there is decrease in the charge
per silicon atom as well as the basicity of silicate mineral. Indeed, silica (SiO 2) is an
acidic oxide.
 * The basic silicate minerals readily react with weak acids and undergo
weathering.

Silicones - structure and uses :

A silicone or polysiloxane is any of a number of polymers that include any synthetic
compound made up of repeating units of siloxane, which is a chain of
alternating silicon atoms and oxygen atoms, combined with carbon, hydrogen, and
sometimes other elements.
They are typically heat-resistant and either liquid or rubber-like, and are used in
sealants, adhesives, lubricants, medicine, cooking utensils, and thermal and electrical
insulation.
Some common forms include silicone oil, silicone grease, silicone rubber, silicone
resin, and silicone caulk

The silicones are a group of organosilicon polymers. They have a wide variety of
commercial uses.

Preparations :
The complete hydrolysis of SiCl4 yields silica SiO2, which has a very stable three-
dimensional structure. The fundamental research of F.S. Kipping on the hydrolysis of alkyl-
substituted chlorosilanes led, not to the expected silicon compound analogous to a ketone,
but to long-chain polymers called silicones.

The starting materials for the manufacture of silicones are alkyl-substituted chlorosilanes.
Thus the hydrolysis of trialkylmonochlorosilane R3SiCl yields hexa- alkylsiloxane.
 The dialkyldichlorosilane R2SiCl2 on hydrolysis gives rise to straight chain polymers
and, since an active OH group is left at each end of the chain, polymerisation continues
and the chain increases in length.
The hydrolysis of alkyl tricholorosilane RSiCl3 gives a very complex cross- linked polymer.

Uses :
1. Silicones act as excellent insulators for electric motors and other appliances as they can
withstand high temperatures.
2. Straight chain polymers of 20 to 500 units are used as silicone fluids. They are water
repellent because of the organic side group. These polymers are used in waterproofing
textiles, as lubricants and as polish.
3. Silicone rubber retain their elasticity even at low temperatures and resist chemical
attack. They are mixed with paints to make them damp-resistant.
4. Silicone resins, a cross-linked polymer used as non-stick coating for pans and are used
in paints and varnish.
5. Silicone oils are highly stable and non-volatile even on heating. Hence used for high
temperature oil bath, high vacuum pump etc.
 IITM COLLEGE OF ART, SCIENCES and COMMERCE
B.Sc. 2nd semester
Lecture Notes
Section-C

P-block elements (Nitrogen family, Oxygen family and Halogen family)

The general valence shell electronic setup of group fifteen elements is ns2, np1-6.
Group 15 elements include nitrogen, phosphorus, arsenic, antimony and bismuth.
Nitrogen is the real constituent of the air and records for 78% of it by volume. It is the
primary member of this group and happens in a free state as a diatomic gas, N2.
Phosphorus is a fundamental constituent of animal and plant matter. Phosphate groups
are constituents of nucleic acids, that is, DNA and RNA. Around 60% of bones and
teeth are made out of phosphates. Phosphoproteins are available in egg yolk, milk, and
bone marrow. The rest of the elements of the group, that is, arsenic, antimony, and
bismuth, mostly happen as sulfides. For example, Stibnite, Arsenopyrite, and bismuth
glance.

Oxides of Nitrogen
Nitrogen reacts with oxygen and results in a number of nitrogen oxides. The oxidation
states of all these oxides are pretty different. They are in the range of +1 to +5. We will
look at some of the important oxides below.

1) Dinitrogen Oxide, N2O

This is a colourless and non-flammable gaseous compound that has neutral properties.
We know it by the common name, laughing gas. We can prepare it by the
decomposing ammonium nitrate under high temperature.T his compound is insoluble
in water and works as a powerful oxidizer at higher temperatures. It has a slightly
sweet odour and appears as a colourless gas. When inhaled in a small amount it
causes mirth and euphoria. It is the world’s number one inhaled anaesthetic as it
works as a quick pain reliever. It can cause a narcotic effect at higher concentrations
and lead to death by asphyxia. Laughing gas formula is written as N2O
NH4NO3 → N2O + 2H2O
2) Nitrogen Monoxide, NO

This is a colourless and gaseous compound. We can usually prepare it by reducing

dilute nitric acid with copper.
2NaNO2 + 2FeSO4 + 3H2SO4 → Fe2(SO4)3 + 2NaHSO4 + 22H2O + 2NO

3) Dinitrogen Trioxide, N2O3

Dinitrogen trioxide is a deep blue solid. It has acidic properties. It is prepared by mixing
equal parts of nitric oxide and nitrogen dioxide and by further cooling the mixture below
−21 °C (−6 °F).
NO + NO2 → N2O3

4) Nitrogen Dioxide, NO2

Nitrogen dioxide is a common oxide of nitrogen. It is a reddish-brown toxic gas. We can

know its presence with a sharp odour.

It has angular structure with O-N-O bond angle 134 ̊ .As it has unpaired electron , it
has tendency to dimerise.
5) Dinitrogen Tetroxide, N2O4

It has planar structure and nitrogen – nitrogen bond is long and weak.
Dinitrogen tetroxide is a colourless solid that we can find in equilibrium with nitrogen
dioxide. It is a powerful oxidizer and is a common reagent in the production of many
chemical compounds.
N2O4 ⇌ 2NO2

6) Dinitrogen Pentoxide, N2O5

2
Dinitrogen pentoxide is a colourless solid. Its characteristic property is that it sublimes
slightly above room temperature. It is unstable. It is a potentially dangerous oxidizer.
We can prepare it by dehydrating nitric acid (HNO3) with phosphorus (V) oxide:
P4O10 + 12HNO3 → 4H3PO4 + 6N2O
X- ray studies of this molecule has confirmed that in solid state N2O5 exists as NO2+
NO3- called Nitronium nitrate. In vapour state, it consists of N2O5 molecule.

PHOSPHOROUS:
This element exists in a few allotropic forms. The main allotropes of phosphorus
include the white phosphorus, red phosphorus and black phosphorus. In addition to
these, there also exists a violet phosphorus. However, that is not a significant allotrope.
So, let us start with the various allotropes of phosphorus now.
White Phosphorus
It is a common allotrope of phosphorus. White phosphorus is a waxy and translucent
solid. It is very delicate and needs proper handling. It is insoluble in water. However, it
dissolves in carbon disulphide or carbon tetrachloride. It breaks down in boiling caustic
soda in a latent air and produces sodium hypophosphite and phosphine.
 Structure of White Phosphorus

In the above diagram, we see the structure of white phosphorus. As we can see, it has
a tetrahedral shape. Every phosphorus particle has a covalent bond with three different
atoms of phosphorus. There exist weak Van Der Waals forces of attraction between
these particles. We must remember that this element is very reactive and too harmful.
 The melting point is quite low at 44°C.
 As we see, the bond angle in a P4 particle is 60°. This is comparatively very less as
compared to a normal bond angle or a hypothetical bond angle. Therefore, it has
a strain in itself. This is why white phosphorus is highly unstable and reactive.
 White phosphorus catches fire suddenly in the air at around 35°C. As you can notice,
this temperature is marginally higher than the normal room temperature. This is the
reason why it is kept in water. After combustion, it produces phosphorus pentoxide.
P4 + 5O2 → 2P2O5 or P4O10
 When it comes in contact with moist air, white phosphorus undergoes an oxidation
reaction. This reaction leads to a sparkling discharge of light. As an outcome, it
sparkles oblivious.
 White phosphorus displays chemiluminescence.

Red Phosphorus
 We can obtain red phosphorus by heating white phosphorus to around 250°Celsius
within the sight of daylight.

 Red phosphorus is iron-grey in colour. It is a radiant and bright crystalline solid.

 It is non-poisonous and does not have any odour. Red Phosphorus does not dissolve
I water and also in carbon tetrachloride.
 It doesn’t break up in boiling caustic soda-like white phosphorus. In fact, it
disintegrates in alcoholic potash.
 We can find it in the state of a polymeric solid.

 It is steady under ordinary conditions and doesn’t catch fire in the air.
 However, it experiences burning when we warm it to around 400°C.
 Red phosphorus doesn’t show chemiluminescence.

 Black Phosphorus
 We can prepare black phosphorus from white phosphorus by heating it to 470K at
inert temperature.


 Black phosphorus is the most stable allotrope of phosphorus. It has a layered
structure. It is a very highly polymerised form of the element.
 We can find black phosphorus in two main forms. They are alpha black phosphorus
and beta black phosphorus.


 While beta black phosphorus forms when white phosphorus is heated at 473K, alpha
black phosphorus forms when we heat red phosphorus at 803K.
 Beta black phosphorus conducts electricity while alpha black phosphorus doesn’t
conduct electricity.

Uses of Phosphorus
Phosphorus compounds assume a vital part of life forms. Phosphorus forms a basic
constituent in the animal and plant matter.We find it present in blood, bones and the
brain of all the animals and also, in living cells. A few of its compounds find applications
in industries. The most essential of these chemicals are orthophosphoric acid and
phosphatic composts.

Oxides of Phosphorus
Phosphorus forms two common oxides, phosphorus(III) oxide (or tetraphosphorus
hexoxide), P4O6, and phosphorus(V) oxide (or tetraphosphorus decaoxide), P4O10.
Both oxides have a structure based on the tetrahedral structure of elemental white
phosphorus. Phosphorus(III) oxide is a white crystalline solid that smells like garlic
and has a poisonous vapour. It oxidizes slowly in air and inflames when heated to
70 °C (158 °F), forming P4O10. It is the acid anhydride of phosphorous acid, H3PO3,
that is produced as
1)Phosphorus Oxide
P4O6 dissolves slowly in cold water. Phosphorus(V) oxide is a white flocculent
powder that can be prepared by heating elemental phosphorus in excess oxygen. It
is very stable and is a poor oxidizing agent. The P4O10 molecule is the acid
anhydride of orthophosphoric acid, H3PO4. When P4O10 is dropped into water, it
makes a hissing sound, heat is liberated, and the acid is formed. Because of its
great affinity for water, P4O10 is used extensively as a drying agent for gases and for
removing water from many compounds

.P4O10 + 6H2O → 4H3PO4

Preparation

It is obtained by the combustion of phosphorus in a limited supply of air at low

temperature.
P4 + 3 O2 → P4O6
By-products include red phosphorus sub oxide

Chemical Properties
Phosphorus trioxide reacts with water to form phosphorous acid, reflecting the fact
that it is the anhydride of that acid.[2]
P4O6 + 6 H2O → 4 H3PO3
It reacts with hydrogen chloride to form H3PO3 and phosphorus trichloride.
P4O6 + 6 HCl → 2 H3PO3 + 2 PCl3
With chlorine or bromine it forms the corresponding phosphoryl halide, and it reacts
with iodine in a sealed tube to form diphosphorus tetra iodide.[1]
P4O6 reacts with ozone at 195 K to give the unstable compound P4O18.[3]

2) Phosphorus Tetraoxide

Diphosphorus tetraoxide, or phosphorus tetroxide is an inorganic

compound of phosphorus and oxygen. It has the empirical chemical formula P
2O
Solid phosphorus tetroxide (also referred to as phosphorus(III,V)-oxide) consists of
variable mixtures of the mixed-valence oxides P4O7, P4O8 and P4O9

Preparation
Phosphorus tetroxide is obtainable by thermal decomposition of phosphorus trioxide,
which disproportionate above 210 °C to form phosphorus tetroxide, with elemental
phosphorus as a by-product:

3) Phosphorus Pentoxide:
Phosphorus pentoxide is a chemical compound with molecular formula P4O10 (with
its common name derived from its empirical formula, P2O5). This white crystalline
solid is the anhydride of phosphoric acid. It is a powerful desiccant and dehydrating
agent.
Preparation

P4O10 is prepared by burning tetra phosphorus with sufficient supply of oxygen:

P4 + 5 O2 → P4O10
For most of the 20th century, phosphorus pentoxide was used to provide a supply of
concentrated pure phosphoric acid. In the thermal process, the phosphorus
pentoxide obtained by burning white phosphorus was dissolved in dilute phosphoric
acid to produce concentrated acid.[6] Improvements in filter technology is leading to
the "wet phosphoric acid process" taking over from the thermal process, obviating
the need to produce white phosphorus as a starting material.[7] The dehydration of
phosphoric acid to give phosphorus pentoxide is not possible as on heating
metaphosphoric acid will boil without losing all its water.

Oxoacids of Phosphorus :

In simple terms, oxoacids are the acids containing oxygen. Phosphorus is one such
element that forms a number of oxoacids. A few common oxyacid include H3PO4,
H3PO3, etc.
In oxoacids of phosphorus, we see that the phosphorus is tetrahedrally surrounded by
other atoms. Generally, it is clear that there are at least one P=O bond and one P–OH
bond in these acids. P–P or P–H bonds are also present besides the P=O bonds and
P–OH bonds in oxoacids of phosphorus. In these cases, the oxidation state of
phosphorus is less than +5.
These acids are generally seen to jump to higher and lower oxidation states. For
example, upon heating, phosphorous acid disproportionates to result in phosphoric
acid and phosphine.
The P-H bonds in oxoacids are not ionisable to give H+ ions. On the other hand, the H
atoms attached to oxygen in P-OH form are ionisable. Hence, we can say that basicity
is the property exhibited by the H atoms that are attached to oxygen.
As a result, phosphorous acid, H3PO3 is dibasic as it has two P-OH bonds. Similarly,
phosphoric acid, H3PO4 is tribasic as it has three P-OH bonds. The oxoacids of
phosphorus that have P-H bonds exhibit strong reducing properties. For example,
hypophosphorous acid containing two P-H bonds is a very good reducing agent.
4AgNO3 + 2H2O + H3PO2 → 4Ag + 4HNO3 + H3PO4
Few Popular Oxoacids of Phosphorus

Name Formula

Hypophosphoric acid H4P2O6

Metaphosphoric acid HPO2

Pyrophosphoric acid H4P2O7

Hypophosphorous acid H3PO2

Phosphorous acid H3PO3

Peroxophosphoric acid H3PO5

Orthophosphoric acid H3PO4

1) Phosphorus acid, H3PO3

Phosphorous acid is a diprotic acid. This means that it ionizes two protons. We can
describe it in a better manner by the structural formula HPO(OH)2. We can prepare
phosphorous acid by the hydrolysis of phosphorus trichloride with acid or steam.
PCl3 + 3H2O → HPO(OH)2 + 3HCl
2) Orthophosphoric acid, H3PO4

Phosphoric acid is a triprotic acid. This means that it can ionise three protons. It is a
non-toxic acid, when pure. It is solid at the room temperature and pressure. We can
prepare phosphoric acid by adding sulfuric acid to tricalcium phosphate rock:
Ca5(PO4)3X + 5H2SO4 + 10H2O → 3H3PO4 + 5CaSO4.2H2O + HX
(X can be F, Cl, Br, and OH).

3) Metaphosphoric Acid (HPO3)n

We can obtain it by warming orthophosphoric acid to around 850 K. It does not exist as
a monomer. It exists as a cyclic trimer, cyclic tetramer or polymer.
4) Hypo phosphorous acid (HPA

Hypophosphorous acid (HPA), or phosphinic acid, is a phosphorus oxyacid and a

powerful reducing agent with molecular formula H3PO2. It is a colorless low-melting
compound, which is soluble in water, dioxane, and alcohols.

5) Pyro phosphoric acid,

Pyrophosphoric acid, also known as diphosphoric acid, is the inorganic compound
with the formula H4P2O7 or, more descriptively, [(HO)2P(O)]2O. Colorless and
odorless, it is soluble in water, diethyl ether, and ethyl alcohol. The anhydrous acid
crystallizes in two polymorphs, which melt at 54.3 °C and 71.5 °C. The compound is
not particular useful, except that it is a component of polyphosphoric acid and the
conjugate acid of the pyrophosphate anion. Anions, salts, and esters of pyro
phosphoric acid are called pyrophosphates.

6)Hypophosphoric Acid
Hypophosphoric acid is a mineral acid with the formula H4P2O6, with phosphorus in
a formal oxidation state of +4. In the solid state it is present as the dihydrate,
H4P2O6·2H2O. In hypophosphoric acid the phosphorus atoms are identical and
joined directly with a P−P bond.
Chemical formula: H4P2O6
Molar mass: 161.98 g/mol
 Oxygen family( Group-16)
Group 16 consists of elements oxygen, sulphur, selenium, tellurium, and
polonium,The four members are called chalcogens,because these are ore forming
elements.Polonium is radioactive element with short half life period.
The general configuration of oxygen family is ns2np6..The

The group 16 elements of modern periodic table consist of 5 elements oxygen,

sulphur, selenium, tellurium and polonium. The elements in this group are also
known as the chalcogens or the ore-forming elements because a large number of
elements can be extracted from the sulphide or oxide ores.

Occurrence of group 16 elements of the modern periodic table

Oxygen is abundantly found on the earth. Estimating the proportions of different
types of atoms found in the universe, oxygen was claimed as the fourth abundant
element after hydrogen, helium, and neon. It constitutes about 89% of water, 46% of
the earth crust and 20 % of the air.

Electronic
Period Element Symbol Atomic Number
Configuration

2 Oxygen O 8 [He] 2s2 2p4

3 Sulphur S 16 [Ne] 3s2 3p4

4 Selenium Se 34 [Ar] 3d10 4s2 4p4

5 Tellurium Te 52 [Kr] 4d10 5s2 5p4

6 Polonium Po 84 [Xe]4f14 5d10 6s2 6p4

Oxygen:
The chemical symbol for oxygen is given as O. It is a colourless and odourless gas
used in the respiration process by humans, which is converted into carbon dioxide.
Oxygen exists as a diatomic molecule (O2). Oxygen is also found as a triatomic
molecule (O3) in traces, it is known as ozone. Oxygen combines readily with many
elements. During the combination with some elements, the evolution of heat energy
takes place, this process is known as combustion.

Sulphur:
Sulphur is denoted by the symbol S. It is a non-metal which ranks ninth on the basis
of cosmic abundance. About 1 atom in every 20,000-30,000 atoms is a sulphur
atom. Sulphur is found in the combined state as well as in the free state. About 0.09
% of sulphur is found in seawater in the form of sulphates. The meteorite contains 12
% of sulphur, a large amount of sulphur is found from the underground deposits of
pure sulphur present in dome-like structures. Here sulphur is formed by the action of
anaerobic bacteria on the sulphate minerals such as gypsum.

Selenium:
Selenium is rarer than oxygen or sulphur. It is found in the free state as well as in the
combined state with heavy metals (as lead, silver, or mercury) in a few minerals.
Grey metallic form of the selenium is the most stable form of the element under
normal conditions.
 Tellurium:
Tellurium is a chemical element having atomic number 52 and has the properties
between metals and non-metals. It is one of the rarest stable elements found in the
earth’s crust. It is often found in a free state and in compounds with elements such
as copper, lead, silver or gold.

Polonium:
It is the rarest element among the group 16 elements. It is a radioactive element.
Polonium is sometimes used in scientific applications for alpha radiation

Atomic and Physical Properties and the Trends of Group 16

elements

 Atomic and Ionic Radii: The atomic and ionic radius increases as we move from
Oxygen to Polonium.
 Ionization Enthalpy: Ionization enthalpy decreases with increase in the size of the
central atom. Therefore, it decreases as we move from Oxygen to Polonium since the
size of the atom increases as we move down.
 Electron Gain Enthalpy: The elect
 ron gain enthalpy decreases with increase in the size of the central atom moving
down the group. Oxygen molecule has a less negative electron gain enthalpy than
sulfur. This is on the grounds that Oxygen, because of its compressed nature
encounter more repulsion between the electrons effectively present and the
approaching electron.
 Electronegativity: The electronegativity decreases as we move down the group.
Therefore, it decreases as we move from oxygen to polonium due to increase in
nuclear size.Learn about Electronegativity here in detail.
 Nature of the Group 16 Elements: Oxygen and Sulfur are non-metals, Selenium
and Tellurium are metalloids and Polonium is a metal under typical conditions.
Polonium is a radioactive element.
 Allotropy: Each one of the element of group 16 displays allotropy. Oxygen has two
allotropes: Oxygen and Ozone. Sulphur exists as many allotropic forms but only two
of them are stable, which are: Rhombic Sulphur and Monoclinic Sulphur. Selenium
and Tellurium are found in both amorphous and crystalline forms.
 The Melting and Boiling Points: As the atomic size increases from oxygen to
tellurium, the melting and boiling points also increase. The huge distinction between
the melting and boiling points of oxygen and sulfur might be clarified on the premise
that oxygen exists as a diatomic atom while sulfur exists as a polyatomic particle.
 Oxidation States: The group 16 elements have a configuration of ns2 np4 in their
outer shell, they may accomplish noble gas configuration either by the gain of two
electrons, framing M-2 or by sharing two electrons, in this manner shaping two
covalent bonds.
Thus, these elements indicate both negative and positive oxidation states. The regular
oxidation states showed by the elements of group 16 incorporate -2, +2, +4 and + 6.
Chemical Properties
The group sixteen elements react with hydrogen to form hydrides of the sort H2E,
where E could be any element- oxygen, sulfur, selenium, tellurium or polonium.
The Physical States of Hydrides of Group 16 Elements

Water is an odourless and colourless liquid but the hydrides of the various elements of
this group are poisonous gases which are colourless with disagreeable smells.
The boiling point of these hydrides extraordinarily diminishes from water to hydrogen
sulfide, and after that increases. Water has an anomalously high boiling point since its
particles are bonded with each other by the hydrogen bonds in both its liquid as well as
solid states.

Oxoacids of Sulfur
:
1) Sulphuric Acid, H2SO4

Sulphuric acid is possibly the most common oxoacid. We have seen a lot of
applications of this acid, haven’t we? It is a diprotic acid. It signifies its property of
ionising into two protons. In sulphuric acid, one atom of sulphur bonds to two hydroxyl
groups. The other two oxygen atoms form pie bonds with the atom.
Thus, sulphuric acid exhibits tetrahedral geometry. As the bond length of the sulphur-
oxygen bond (S=O) is quite less as compared to the bond length of S-OH, the oxygen
atoms repel the OH groups. Hence, the bond angle of O=S=O bond is greater than the
HO-S-OH bond angle. We produce it industrially by the contact process.

2) Sulphurous Acid, H2SO3

Sulphurous acid is a diprotic acid and thus, gives rise to two protons. In sulphurous
acid, one atom of sulphur bonds with two hydroxyl groups. Also, one oxygen atom
forms a pie bond with the sulphur atom. We prepare this by dissolving sulfur dioxide in
water. As of this date, we do not have any evidence of the existence of sulphurous acid
in solution phase. However, the molecule is capable to be isolated in its gaseous
phase.
3) Peroxodisulphuric Acid, H2S2O8

Peroxodisulphuric acid contains sulphur in +6 oxidation state. Thus, it acts as a very

strong oxidizing agent. It is, also, very explosive in nature. We know it by the common
name, Marshall’s acid.
It contains one peroxide group that acts as a bridge between the two sulphur atoms.
Each atom connects to one hydroxyl group (S-OH bond) and two oxygen atoms (S=O
bond) other than the peroxide group. We can prepare it by the reaction of the
chlorosulfuric acid with hydrogen peroxide. The reaction is given as follows:
2ClSO3H + H2O2 → H2S2O8 + 2HCl

4)-Pyrosulphuric Acid, H2S2O7

Pyrosulphuric acid is also known as oleum. Its molar mass is 178.13 g/mol. It is an
anhydride of sulphuric acid, is a colourless, crystalline solid and has a melting point of
36°C. It can be prepared by reacting excess sulphur trioxide with sulphuric acid. The
reaction goes like this:
H2SO4 + SO3 → H2S2O7
It reacts with bases to form salts which are called pyrosulphates. We use it in
the manufacturing of explosives and dyes. it is also used in petroleum refining. It is a
strong dehydrating agent and is corrosive in nature. It can cause burns on the skin and
irritation to the eyes. Long exposure can prove to be fatal.
 Group -17 (Halogen Family)
The group 17 elements include fluorine(F), chlorine(Cl), bromine(Br), iodine(I) and
astatine(At) from the top to the bottom. They are called “halogens” because they give
salts when they react with metals.

Electronic Configuration of Group 17 Elements

The valence shell electronic configuration of these electrons is ns2np5. Thus, there are
7 electrons in the outermost shell of these elements. The element misses out on the
octet configuration by one electron. Thus, these elements look out to either lose
one electron and form a covalent bond or gain one electron and form an ionic bond.
Therefore, these are very reactive non-metals.

Atomic Properties :

1) Ionic and Atomic Radii

The nuclear and atomic radii of these elements keep on increasing as we move down
the group. This happens because of the addition of an extra energy level. They have
the minimal atomic radii compared to the other elements in the related periods. This
can be attributed to the fact that their atomic charge is quite powerful.
2) Ionisation Enthalpy
These elements have higher ionization enthalpy. This value keeps on diminishing as
we move down the group. This happens because of the increase in the size of the
nucleus. However, it is interesting to note that fluorine has the highest ionization
enthalpy than any other halogen, thanks to its minute size!
3) Electron Gain Enthalpy
The electron gain enthalpy of these elements becomes less negative upon moving
down the group. Fluorine has lesser enthalpy than chlorine. We can attribute it to the
small size and the smaller 2p sub-shell of the atom of fluorine.
4) Electro-Negativity
The halogens exhibit high electro-negativity values. However, it diminishes slowly on
moving down the group from fluorine to iodine. this can be attributed to the increase in
nuclear radii upon moving down the group.

Physical Properties :
.Physical state:
The group 17 elements are found in diverse physical states. For example, Fluorine
and Chlorine are gases. On the other hand, Bromine is a liquid and Iodine is solid.
 Colour: These elements have a variety of colours. For example, while Fluorine is
pale yellow in colour, Iodine is dark violet in colour.
 Solubility: Florine and Chlorine are soluble in water. On the other hand, Bromine and
Iodine are very less soluble in water.
 Melting and boiling points: Melting and boiling points of these elements increase as
we move down the group from Fluorine to Iodine. Thus, Fluorine has the lowest
boiling and melting points.

 Chemical Properties.:

1) Oxidising Power
All the halogens are great oxidizing agents. Of the list, fluorine is the most powerful
oxidizing agent. It is capable of oxidizing all the halide particles to halogen. The
oxidizing power reduces as we move down the group. The halide particles also act as
reducing agents. However, their reducing capacity decreases down the group as well.

2) Reaction with Hydrogen

All halogens react with hydrogen and produce acidic hydrogen halides. The acidity of
these hydrogen halides reduces from HF to HI. Fluorine reacts violently and chlorine
requires the sunlight. On the other hand, bromine reacts upon heating and iodine
needs a catalyst
.
3) Reaction with Oxygen
Halogens react with oxygen to form oxides. However, it has been found that the oxides
are not steady. Beside oxides, halogens also form a number of halogen oxoacids and
oxoanions.

4) Reaction with Metals

As halogens are very reactive, they react with most of the metals instantly and form the
resulting metal halides. For example, sodium reacts with chlorine gas and forms
sodium chloride. This process is an exothermic one and gives out a bright yellow light
and a lot of heat energy
.
2Na(s) + Cl2(g) → 2NaCl(s

Metal halides are ionic in nature. This is because of the high electronegative nature of
the halogens and high electropositivity of the metals. This ionic character of the halides
reduces from fluorine to iodine.

Interhalogen Compounds
We can refer to the Interhalogen Compounds as the subordinates of halogens. These
are the compounds having two unique sorts of halogens. For example, the common
interhalogen compounds include Chlorine monofluoride, bromine trifluoride, iodine
pentafluoride, iodine heptafluoride, etc.

Types of Interhalogen Compounds

We can divide interhalogen compounds into four types, depending on the number
of atoms in the particle. They are as follows:
 XY Compounds
 Compounds XY3
 Compounds XY5
 XY7 Compounds

In these notations, we must understand that “X” is the bigger (or) less electronegative
halogen. On the other hand, “Y” represents the smaller (or) more electronegative
 halogen. We can calculate the number of particles in the atom by the concept of
the radius ratio. The formula for the same is as follows:
Radius Ratio = Radius of Bigger Halogen Particle/Radius of Smaller Halogen Molecule
With an increase in the radius proportion, we see that the number of atoms per
molecule also increases. Therefore, we can make out that Iodine heptafluoride
possesses the greatest number of particles per atom. This is because it has a
magnificent radius proportion.

Preparation

We can manufacture these interhalogen compounds by two main methods. One of

them includes the direct mixing of halogens and the other includes a reaction of
halogens with the lower Interhalogen compounds.
 The halogen atoms react to form an interhalogen compound. One example includes
the reaction when a volume of chlorine reacts with an equal volume of fluorine at
473K. The resultant product is chlorine monofluoride.
 In other cases, a halogen atom acts with another lower interhalogen to form an
interhalogen compound. For example, fluorine reacts with iodine pentafluoride at
543K. This gives rise to the compound of Iodine Heptafluoride.

Properties

 We can find Interhalogen compounds in vapour, solid or fluid state. A lot of these
compounds are unstable solids or fluids at 298K. a few other compounds
are gases as well. As an example, chlorine monofluoride is a gas. On the other
hand, bromine trifluoride and iodine trifluoride are solid and liquid respectively.
 These compounds are covalent in nature. We can attribute it to the lesser
electronegativity between the bonded molecules. Examples include Chlorine
monofluoride, Bromine trifluoride and Iodine heptafluoride. These compounds are
covalent in nature.
 These interhalogen compounds are diamagnetic in nature. This is because they have
bond pairs and lone pairs.
 Interhalogen compounds are very reactive. One exception to this is fluorine. This is
because the A-X bond in interhalogens is much weaker than the X-X bond in
halogens, except for the F-F bond.
 We can use the VSEPR theory to explain the unique structure of these interhalogens.
In chlorine trifluoride, the central atom is that of chlorine. It has seven electrons in its
outermost valence shell. Three of these electrons form three bond pairs with three
fluorine molecules leaving four electrons.

Common Shapes of these Compounds

Applying the VSEPR theory, we can see that it forms a trigonal bipyramid. The lone
pairs take up the tropical positions. On the other hand, bond pairs take up the other
three positions. The axial bond pairs bend towards the tropical position. This happens
in order to minimize the repulsions that happen due to lone pair-lone pair bonds. Thus,
it has the shape of a bowed T.
 Chlorine Pentafluoride

Let us now take the case of Iodine Pentafluoride. The central atom in Iodine
pentafluoride is the iodine atom. It has one lone pair and five bond pairs. This is the
reason it has a square pyramidal shape. Similarly, let us consider the case of Iodine
heptafluoride. It has seven bond pairs and has the shape of pentagonal bipyramid.

Uses of Interhalogen Compounds

 We use interhalogen compounds as non-watery solvents.

 Also, we use these compounds as a catalyst in a number of reactions.
 We use UF6 in the enrichment of 235U. We can produce this by using ClF3 and BrF3.
U(s) + 3ClF3(l) → UF6(g) + 3ClF(g)

Oxoacids of halogens

Halogens produce several oxoacids. These are nothing but the acids containing oxygen
in the acidic group.
An oxoacid is a compound having hydrogen, oxygen, and no less than one other
element. These do not have any lesser than one hydrogen molecule bound to oxygen.
This hydrogen is capable of separating into the H+ cation and the anion of the acid.
The fluorine atom is extremely small and thus, it is highly electronegative. Therefore, it
can form a single oxoacid, HOF which is fluoric(I) acid or hypofluorous acid. The other
elements of the halogen family produce several oxoacids.
We cannot isolate them in the pure state. They are stable in aqueous solution. They
are also very stable in their salt forms. Halogens generally form four series of oxoacids
namely hypohalous acids (+1 oxidation state), halous acids (+3 oxidation state), halic
acids (+5 oxidation state) and perhalic acids (+7 oxidation state).

Structures of the Oxoacids of Halogens

We can see that the focal halogen molecule is sp3 hybridised in these oxoacids. We
can find an X-OH bond in each oxoacid. In the majority of these oxoacids, “X = O”
bonds are available. Hypohalous acids incorporate hypofluorous acid, hypochlorous
acid, hypobromous acid and hypoiodous acid. The halogen has the oxidation condition
of +1 in hypohalous acids.
Some More Examples
Chlorine is capable of forming four types of oxoacids. They are HOCl (hypochlorous
acid), HOClO (chlorous acid), HOClO2(chloric acid) and lastly HOClO3 (perchloric acid).
Bromine forms HOBr (hypobromous acid), HOBrO2(bromic acid) and
HOBrO3 (perbromic acid). Iodine forms HOI (hypoiodous acid), HOIO2 (iodic acid) and
HOIO3 (periodic acid).
The central atom in the oxoacids is sp3 hybridized. Every oxoacid has essentially one X-
OH bond. Whereas most oxoacids have X=O bonds present in them.
 IITM COLLEGE OF SCIENCES,ARTS AND COMMERCE
B.Sc. 2nd semester
QUESTION BANK
INORGANIC CHEMISTRY

SHORT ANSWER TYPE QUESTIONS:

1. What are conditions of H- bonding?

2. Why does BeCl2 give acidic solution in water?
3. Out of MgCO3 and CaCO3 which will give color flamation?
4. Why Li is best reducing agent in group 1?
5. What is Freon?
6. What is the formula of hydrazoic acid?
7. What kind of hydrogen bonding is present in o-nitrophenol?
8. Why do noble gases are monoatomic?
9. Why do boron and aluminium forms covalent compounds?
10.What happens when phosphorous trioxide is treated with cold H2O?
11.Give cause of anomalous behaviour of Li.
12.BF3 exists while BH3 does not exist , why?
13.H3PO4 is a tribasic acid , why?
14.Why does acetic acid exists in dimeric form?
15.Write the reaction by which first noble gas was formed.
16.Define catenation.
17.Why is H3PO2 monobasic?
18.Give two uses of H2

SECTION – A
1. What are semiconductors? Explain what is meant by n-type and p-type
2. Semiconductors?
3. What are van der waals forces? Discuss with examples.
4. Discuss various types of van der waals forces with examples.
5. Explain the difference between intermolecular hydrogen bonding and
intramolecular hydrogen bonding.
6. Water has maximum density at 4’C. Explain.
7. How does band theory explain electrical conductivity of metals?
8. Discuss intrinsic and extrinsic semiconductors.
9. o- nitrophenol is steam volatile while p-nitrophenol is not. Explain.
10.Give some applications of semiconductors.
11.Which one has high boiling point? Ethyl alcohol or dimethyl ether ?
12.What is Hydrogen bond? Discuss the effect of hydrogen bonding on
properties of substances.

SECTION – B
1. Account for the increasing stability of peroxides and superoxides as the
size of alkali metals increases.
2. Draw and discuss the structure of XeO3 , XeF4 , XeOF4 , . XeO2F2.
3. Alkali metals are more reactive than alkaline earth metals. Why?
4. What is diagonal relationship? Explain by taking the examples of Be and
Al.
5. Why do noble gases form compounds only with F2 and O2 ?
6. Explain the following:
(a) Be and Mg do not impart any characteristics flame coloration.
(b) Li forms normal oxide , Na the peroxide and K the superoxide.
7. Give the reactions of partial and complete hydrolysis of XeF6 with SiO2?
8. Write the functions of alkaline earth metals in biosystem.
What are the factors responsible for late discovery of compounds of
noble gases?
9. How the hydrides of s-block elements act as powerful reducing agents?
10.Explain the complexing ability of alkaline earth metals.
11.Explain the following:
(a) LiF is insoluble in water wheras other alkali metals fluorides are
soluble.
(b) Alkali metals salts imparts color to the flame.
(c) He and Ne do not form compounds.
 SECTION – C
1. Why BF3 is weaker lewis acid than BCl3 ?
2. Draw structure of borazine. Why is it called inorganic benzene?
3. Why does AlCl3 exist as dimer while BCl2 exist as monomer?
4. What are silicones? Give their preparations, properties and uses.
5. What are carbides? Discuss interstitial carbides.
6. How does CaC2 and Al4C3 differ?
7. Discuss the structure and bonding in diborane (B2H6).
8. Write 4 diagonal similarities of boron with silicon.
9. Discuss the action of diborane with
(a) ammonia
(b) alkalies.

SECTION – D
1. Explain why ICl7 does not exist while IF7 exist?
2. Draw the structure of P4O6 and P4O8.

3. Give reasons:
(a) HNO2 is weaker acid than HNO3.
(b) H3PO3 is dibasic acid.
(c) H3PO4 is stronger than H3PO3
4. Write three chemicals equations where hydrogen peroxide acts as
oxidizing agent.
5. Differentiate between the structure of white phosphorous and red
phosphorous.
6. Explain why H2SO4 is highly viscous?
7. Discuss the acidic, oxidising and reducing nature of H2O2 with suitable
example.
8. Draw the structure of sulphuric acid , Caro’s acid and sulphurpus acid. ,
Marshall’s acid.
9. Why are interhalogen compounds more reactive than halogens?
10. Explain the structure of ClF3.
11.“Halogens are most reactive elements as a family.” Comment.
12. Describe the structure of H3PO3.
13.Compare the acidic strength of following:
14. HClO , HClO2 , HClO3 , HClO4
15.Write the names and structures of three oxides of nitrogen.
16. Discuss the structure of N2O4