Chemistry (s and p-Blocks)

UNIT-11 s and p-Blocks

1. CHEMISTRY OF S AND P BLOCK ELEMENTS INCLUDING NOBLE GASES

PROPERTIES AND APPLICATION OF MAIN GROUP ELEMENTS

Introduction:
The elements in the long form of the periodic table have been divided into four blocks — s, p,
d and f- block elements. This classification is based on the type of the atomic orbital in which the
outermost electron is located. The s orbital can accommodate two electrons, while the three p orbitals
can accommodate a maximum of six electrons. Thus there are two groups of s - block elements —
Groups 1 and 2 whose electronic configurations are represented as [Noble gas] ns1 and [Noble gas] ns2
respectively. There are six groups of p - block elements — Groups 13 to 18. The s and p block elements
are collectively called the main – group elements or representative elements. The d and f - block
elements are located between the s and p - block elements.
The s - block elements are located on the left of the periodic table and comprise of highly reactive
metals. The p -block elements comprise of both metals and non-metals.

CLASSIFICATION OF PERIODIC TABLE :

Classification - 1
s-Block Elements p-Block Elements d-Block Elements f-Block Elements
Group 1 & 2 Group 3 to 12 Group 13 to 18
Alkali and Alkaline Transition Elements Inner transition Elements
Earth Metals
Classification - 2
Inert Gases s & p block elements d-Block Elements f-Block Elements
2 6 1 2 1-5 1-9 1-2
ns p ns , ns , np (n-1)d ns (n-2)f1-14 (n-1)d0-1 ns2
exception Zn, Cd, Hg 4f - Lanthanides
Group 12 58 - 71
5f - Actinides
90-103
Inert Gases Representative Transition Elements Inner transition Elements
Elements

I. s - block elements:
 The elements of groups 1 and 2 are called the s- block elements because the outermost
electron(s) occupy the s -orbital.
 They are highly electropositive metals and form ionic compounds.
 They are referred to as alkali and alkaline- earth metals respectively. Due to their high
reactivity the metals do not occur in the free state in nature but are present in form of
halides, silicates, nitrates (Group1) and silicates, carbonates, sulphates and phosphates
(Group 2).
The elements show similarities in physical and chemical properties within a group — however
the first elements exhibit considerable differences from the rest of the elements of the same group. This
anomalous behaviour is mainly due to the following factors —

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 Chemistry (s and p-Blocks)

(1) Comparatively higher value of the first ionization energy and electronegativity
(2) Small size
(3) High polarizing power of the cation, consequently a greater tendency to form covalent
compounds (Fajan’s rules) and complexes,
(4) Inability to display a coordination number exceeding 4 due to non-availability of d - orbitals
in the valence shell.
Diagonal Relationship
A close similarity is observed in certain cases between the first element of a group with the
second element of the following group. This is referred to as the diagonal relationship and is observed
in the following pairs.

Li Be B C

Na Mg Al Si
Reason
In a period the atomic size and electropositive character decreases. Ionisation potential and
electronegativity increases.
Down a group atomic size and electropositive character increases. But Ionisation potential and
electronegativity decreases.
On moving in a diagonal these properties cancel each other. Therefore, similarly in behaviour.
[e.g.. ionic size of Li+ =76pm & that of Mg2+=72pm]
Group 1 — the Alkali Metals
 The elements in this group are lithium, sodium, potassium, rubidium, caesium and the
radioactive, francium.
 They have one electron in their valence shell (ns1 configuration).
 Due to similarity in electronic configuration, they exhibit similarities in chemical properties.
They are soft, highly reactive, univalent metals, excellent conductors of heat and electricity
and form colourless ionic compounds.
 Lithium shows considerable differences from the lower members and exhibits diagonal
relationship with magnesium.
The physical properties of alkali metals are summarized in Table.
Table: Physical Properties of Group 1 Elements
Property Li Na K Rb Cs
Atomic Number 3 11 19 37 55
Electronic Configuration 1 1 1 1 1
[He]2s [Ne]3s [Ar]4s [Kr]5s [Xe]6s
Covalent radius (pm) 123 156 203 216 235
+ 60 95 133 148 169
Ionic radius (M ) (pm)
-1 520 496 419 403 376
Ionization Energy (KJmol )
-1 60 53 48 47 46
Electron Affinity (KJmol )
Electronegativity 0.912 0.869 0.734 0.706 0.659
0 180.5 97.8 63.2 39 28.5
Melting Point ( C)
0 1347 881 766 688 705
Boiling Point ( C)
0 +
E (M M) (V) against S.HE, -3.04 -2.71 -2.92 -2.92 -2.92

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 Chemistry (s and p-Blocks)

General Group Trends

1. Size & Density
On moving down the group the size of the atom increases as additional shells are introduced to
accommodate the electrons. This out-weighs the effect of increased nuclear change. Formation
of the cation involves removal of the outermost shell of electrons; the effective nuclear charge
also increases and the electrons are held tightly. Thus the cation is smaller than the neutral atom.
Even so, the cations are quite large and an increase in size is observed on descending the group.
The atoms are large and the atomic mass is low; thus the Group 1 elements have low densities.
2. Ionization Energy
The first ionization energies of the atoms are the lowest in the corresponding period. The atoms
are large and the outermost electron is loosely held. Moreover; loss of this electron gives a stable
noble gas configuration. On moving down the group, the ionization energy decreases as the size
increases.
The second ionization energy is extremely high as it is difficult to remove an electron from a
cation having noble gas configuration. The elements form unipositive cations, they are highly
electropositive and the metallic character increases down the group.
3. Melting and Boiling Points
These metals are soft and can be cut with a knife. At room temperature they adopt a body-cent
red cubic lattice. They have one electron that can participate in metallic bond formation and thus
they have low cohesive energy, which is reflected in low melting and boiling points. On moving
down the group, the metallic bonding becomes weaker and the melting and boiling points decrease.
4. Electronegativity and Type of Bond
These elements have low electronegativity; consequently when they react with other elements a
large electronegativity difference is possible and ionic bonds are formed.
5. Flame Colours
The alkali metal atoms have low ionization energy and may emit electrons when irradiated with
light, hence they find use in photocells. Electrons may also be excited to higher energy levels,
for example in the flame test. When an alkali metal salt is introduced to a Bunsen burner flame,
a characteristic colour is observed. (Li – red, Na – golden- yellow, K – lilac). The colour arises
from electronic transitions, which occur due to excitation of electrons from valence shell to higher
excited state energy levels. When the excited electrons return to the original level, the extra
energy is emitted and lies in the visible range of the electromagnetic spectrum.

Chemical Properties:
 The alkali metals are very similar in their chemical properties, which are governed by the
ease with which they can lose their valence electron. They are excellent reducing agents
and react with water forming hydrogen.
2 Na + 2H2O 2NaOH + H2
 The reaction is highly exothermic.
 They react with oxygen to form oxides, peroxides or superoxides depending on the metal.
Lithium forms the oxide (Li2O), sodium, the peroxide (Na2 O2) while others form the
superoxide (M O2, M = K, Rb, Cs). Lithium is the only element that forms a nitride by direct
combination with nitrogen.
 Alkali metals react with sulphur forming sulphides e.g. Na2 S and polysulphides Na2 Sn
where n = 2 to 6. The polysuphides have zig – zag chain of sulphur atoms.

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 Chemistry (s and p-Blocks)

S S S

S S S
 The metals react with hydrogen forming ionic hydrides, M+ H-. The stability of the hydrides
decreases down the group. The hydrides are ionic solids and are the only example of
species containing H- ion. During electrolysis hydrogen is liberated at the anode. They
react with water liberating hydrogen.
LiH + H2O LiOH + H2.
Lithium hydride reacts with aluminum hydride to form lithium aluminium hydride, an
excellent and useful reducing agent in organic chemistry
4 LiH + AlCl3 LiAlH4 + 3 LiCl.
Sodium hydride reacts with trimethyl borate to form another useful compound, sodium
borohydride
4 NaH + B(OCH3)3  NaBH4 + 3 NaOCH3.
 The alkali metals react violently with halogens to form halides. The reactivity of an alkali
metal towards a particular halogen increases down the group. The reactivity of halogen
towards an alkali metal follows the order: F2 > Cl2 > Br2 > I2. The general reactions of alkali
metals are summarized in Table.

Table: Reaction of Group 1 Metals

Reagent Reaction Remarks

O2 M+ O2  MxO y x = 2, y = 1for Li (monoxide); x = 2, y =2
for Na (peroxide)
x = 1, y = 2 for others (superoxide)
S 2M + S  M2S Polysulphides also formed
H 2O M + 2H2O  MOH + H2 Slow for Li, explosive for K
H2 2M + H2  2MH Ionic hydrides formed
X2 (halogen) 2M + X 2  2MX All halogens react
N2 6Li + N2  2Li3N Only Li reacts
ROH 2M + 2ROH  2MOR + H2 Slow for Li, Vigorous for others
+
NH3 M + NH3(e)  [M(NH3)x] + e (NH3) Excellent reducing agents
–

Solvation of Alkali Metal Ions

Solvent molecules always surround a metal ion in solution. This is referred to as solvation. If the
solvent is water, then it is called hydration. The alkali metal ions are extensively hydrated. A small ion has
high charge density and attracts the solvent molecules strongly, resulting in extensive hydration. The
energy evolved during hydration is called hydration energy.
Li + being smallest is most heavily hydrated and has highest hydration energy. The extent of
hydration decreases down the group. Hydration directly affects ionic mobility. Li +, the smallest ion is
expected to be highly mobile, but in fact the reverse is time. This is because the hydrated radius of Li+
is the largest and is least mobile and least conducting in solution.
The decrease in hydration from Li + to Cs + is revealed by the fact that most crystalline salts of
lithium are hydrated. Most salts of alkali metals are soluble in water. For any substance to dissolve the
hydration energy must exceed lattice energy.

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 Chemistry (s and p-Blocks)

Solution of Metals in Liquid Ammonia

The alkali metals dissolve in liquid ammonia and other amines to give blue solution believed to
contain solvated electrons.
Na + x NH3 Na+ + e (NH3)-x
Due to the presence of these solvated electrons, dilute solution of alkali metals conduct electricity
far better than completely dissociated electrolytes.
As the concentration of the metal increases the conductivity decreases initially and then increases.
At sufficiently high concentrations the solution develops a bronze metallic luster and the conductivity
approaches the value of a molten metal. The dilute solutions are paramagnetic but the paramagnetism
decreases with increase in concentration. The blue colour is attributed to the solvated electrons. These
solutions are excellent reducing agents.
RC CR + e– RC C– + ½ H2
S + 2e– S2–
The solutions undergo slow decomposition to give amides.
M + NH3  MNH2 + ½ H2
The Group 2 metals and some lanthanides also dissolve in liquid ammonia.
Alkyls and Aryls
Lithium shows a stronger tendency to covalency than the other alkali metals. It forms covalent
alkyls and aryls.. These compounds are frequently tetrameric or hexameric and are made by reaction
of lithium with the alkyl / aryl halide.
RCl + Li  Li R + LiCl.
The methyl derivative is tetrameric [(LiCH3)4], covalent and soluble in organic solvents. The four
Li atoms occupy the corners of a tetrahedron with the methyl groups above the face of the tetrahedron.
The classical theories of bonding cannot explain the formation of these compounds, which involve multi-
centred bonds. These compounds are starting materials for synthesis of organometallic and organic
compounds. The alkyls of Na, K, Rb and Cs are ionic.

Complexation Behaviour of Alkali Metals

The alkali metals generally have weak complexing ability. This is because the factors that favour
complexation viz, small size, high nuclear charge and availability of empty orbitals of low energy are
lacking in alkali metals.
Aqua complexes like [Li(H2O) 4]+, [Cs(H2O) 6]+ are known. A number of chelates are known e.g.
those with salicylaldehyde and acetyl acetone.
An important development in the field of alkali metal chemistry is the discovery of complexes with
cyclic ethers and cryptands (cryptates) i.e. with macro cyclic molecules containing nitrogen and oxygen.
The cyclic ethers are called crown ethers; they have varying sizes of rings and form complexes with
alkali metal ions by donating electron density through the oxygen atoms. Examples of such molecules
are shown in Fig.

N N

(a) (b)
Fig.: a. A crown ether b. A cryptand

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 Chemistry (s and p-Blocks)

The cryptates are more selective and stronger complexing agents than the crown ethers, with eight
donor atoms (nitrogen and oxygen) surrounding the metal ion completely. The ability of crown ether or
a cryptands to trap a metal ion depends on the size of both the cavity and the metal ion.

Biological Importance
 Living organisms need about 15 metals for different biological processes. Some of the alkali
metals are biologically active.
 Sodium and potassium ions act as charge carriers and are involved with balancing the
electrical charges associated with negatively charged macromolecules in the cell.
 Na+ is the major cation in the extra cellular fluid and its concentration is about 0.15 M, it
is actively expelled from the cell where its concentration is about 0.01 M .K+ is the major
cation inside the cell (0.15 M) whereas its concentration in the extra cellular fluid is about
0.03 M. This uneven concentration of Na+ and K+ on either side of the cell wall is controlled
by the sodium-potassium pump and a large amount of energy is needed to maintain this
disequilibrium.
 The energy is provided by hydrolysis of ATP. Na+ and K+ are also involved in maintaining
the osmotic pressure inside the cell, thereby keeping it turgid.
 The different ratio of Na+ to K+ inside and outside the cell produces a characteristic
electrical potential across the cell membrane and muscle cells.
 They also activate specific enzymes. Lithium salts are used as anti-depressants. The
exact mode of action is however not clear.

Group 2 — the Alkaline Earth Metals

This group comprises of six metallic elements – beryllium, magnesium, calcium, strontium and
barium. Calcium and magnesium are amongst the most abundant elements in the earth’s crust; strontium,
barium and beryllium are less abundant. All isotopes of radium are radioactive (longest lived isotope,
226
Ra has half of 1600 years).
Selected physical properties of the alkaline earth metals are given in Table.

Table: Physical Properties of Group 2 Elements

Property Be Mg Ca Sr Ba Ra
Electronic Configuration 2 2 2 2 2 2
[He]2s [Ne]3s [Ar]4s [Kr]5s [Xe]6s [Rn]7s
Ionic radius (pm) 31 65 99 113 135 –
Covalent radius (pm) 89 136 174 191 198 –
-1 900 738 590 549 502 509
Ionization Energy (KJmol ) (I)
-1 -50 -40 -30 -30 -30 -30
Electron Affinity (KJmol )
0 1287 649 839 768 727 700*
Melting Point ( C)
0 2500 1105 1494 1381 1850* 1700*
Boiling Point ( C)
Electronegativity 1.576 1.293 1.034 0.963 0.881 0.9
0 2+
E (M + 2e  M) (V) Against S.H,E -1.97 -2.36 -2.84 -2.89 -2.92 -2.92
–

* Approximate value

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 Chemistry (s and p-Blocks)

Physical Properties
The atoms have two electrons in their outermost shell. They are divalent, reactive metals, though
less reactive than the elements of Group 1. The atoms of the Group 2 elements are smaller than the
neighbouring Group 1 elements as a consequence of the greater nuclear charge of the former. As a
result of their smaller size they are denser than the alkali metals and have greater ionization energy.
The Group 2 metals have two electrons, which can participate in metallic bond formation and thus
have higher cohesive energy and much higher melting and boiling points than Group 1 metals. The
melting points do not vary regularly as the metals adopt different crystal structures in the solid state.
The metals of this group form ionic compounds. Beryllium, however, due to its small size and
moderately higher value of electronegativity has a tendency to form covalent compounds. The general
group trends in Group 2 are very similar to those in Group 1.
Chemical Properties
The elements, with the exception of beryllium have very similar chemical properties. Much of their
chemistry is governed by their tendency to form M2+ ions, which have noble gas configuration.
They are good reducing agents. The reduction potential of beryllium is less than those for the rest
of the group. This indicates that beryllium is less electropositive (metallic) than others.
The heavier members react with water to evolve hydrogen and form metallic hydroxides.
Ca + 2H2O  Ca(OH)2 + H2
Magnesium is less reactive and decomposes hot water
Mg + 2H2O  Mg(OH)2 + H2
Or Mg + H2O  MgO + H2
The hydroxide of beryllium is amphoteric while the other hydroxides are basic and basic character
increases down the group as the metallic character increases. The metals react with acids forming
hydrogen.
Mg + 2HCl  MgCl2 + H2
Beryllium reacts slowly and is rendered passive by concentrated nitric acid as a protective oxide
film coats it. It is amphoteric and reacts with strong bases to evolve hydrogen.
Be + 2NaOH + 2H2O  Na2 [Be(OH)4] + H2
The elements burn in air to form the corresponding oxides and nitrides.
2 Be + O2  2 BeO
3 Be + N2  Be3N2
Beryllium nitride is covalent. All nitrides decompose to its elements on heating and react with
water to give ammonia.
Ca3N2 + 6 H2O  3 Ca(OH)2 + 2 NH3
The tendency to form peroxides increase with the size of cation. This is because a large cation
is stabilized by a large anion which gives rise to a species with high lattice energy. The peroxides contain
the O2- ion and liberate hydrogen peroxide with acids.
BaO2 + H2SO4  BaSO4 + H2O2
The halides are formed by direct combination or by action of halogen acids or metals. The halides
of beryllium are hygroscopic and fume in air due to hydrolysis. Anhydrous beryllium halides are polymeric
Beryllium chloride in the vapour state contains both the monomer and the dimer.
Cl
Cl — Be — Cl Cl — Be Be — Cl
Cl

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 Chemistry (s and p-Blocks)

In the solid-state beryllium chloride has a polymeric structure containing bridging chlorine atoms.

Cl Cl Cl
Be Be Be Be
Cl Cl Cl
The halides are deliquescent and form hydrates. Calcium chloride is widely used as a drying
agent.
All the group 2 metals except beryllium combine with hydrogen at high temperature to form
hydrides, MH2
Mg + H2   MgH2
Beryllium hydride can be obtained by reducing beryllium chloride with lithium aluminum hydride.
2 BeCl2 + LiAlH4   2 BeH2 + LiCl + AlCl3
The hydrides are reducing agents and react with water and acids to produce hydrogen.
CaH2 + 2H2O  Ca(OH)2 + H2
The hydrides of calcium, strontium and barium are ionic and contain the hydride ion (H–). The
hydrides of beryllium and magnesium are covalent and polymeric (BeH2)n. has a chain structure containing
chains with hydrogen bridges between beryllium atoms

H H H
Be Be Be Be
H H H

Each beryllium atom is bonded to two hydrogen atoms and each hydrogen atom to two beryllium
atoms. Now, beryllium has only two valence electrons and hydrogen only one, it is apparent that there
are not sufficient electrons to form so many electron pair bonds. The monomeric BeH2, if formed with
normal bonds, would have only four electrons in the valence shell of the beryllium atom and would be
electron deficient and unstable. It polymerizes to remedy the electron deficiency. The bonds formed
cannot be explained by the classical theories of bonding. They are “banana shaped” molecular orbitals
holding three atoms Be ---- H ---- Be together and are called 3 centred – 2- electron (3c – 2e) bonds.
It is an example of a cluster compound.
The metals and their oxides directly combine with carbon forming carbides.
2 BeO + 2C  Be2C + 2CO
Ca + 2C  CaC2
CaO + 3C  CaC2 + CO
Be2C is ionic and hydrolyses to give methane
Be2C + 4H2 O  2 Be(OH)2 + CH4
The other carbides produce ethyne
CaC2 + 2H2O  Ca(OH)2 + HC  CH.
The general reactions of Group 2 metals are summarized in Table.

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 Chemistry (s and p-Blocks)

Table: Reaction of the Group 2 metals

Reagent Reaction Remarks
O2 2M + O2  2MO All metals react at high temperature,
Ba also forms BaO2
X M+ X  MX All metals undergo this reaction
H2 O M + 2H2 O  M(OH)2 + H2 Be reacts with steam, Mg with hot H2O,
others with cold H2O
HCl M + 2HCl  MCl2 + H2 All metals liberate hydrogen from acids

H2 M + H2  MH2 M = Ca, Sr, Ba

N2 3M + N2  M3N2 All metal reacts at high temperature
X2 M + X2  MX2 Halides are formed by all metals
(X = F, Cl, Br, I)

Solubility, Lattice Energy and Hydration Energy

Interesting trends are observed in solubility of many Group 2 compounds. The metal ions are
easily hydrated eg. MgCl2. 6H2O, CaCl2. 6H2O, BaCl2 . 2H2O. Because of small size and high nuclear
charge, Group 2 cations have higher hydration energy than Group 1 cations (Table). The lattice energies
of many compounds are high.
Table: Enthalpies of Hydration of M2+ ions &
Lattice Energies of some compounds (KJ mol-1)

Hhyd MO MCO3 MF2

2+
M
Be -2494 - - -
Mg -1921 -3923 -3178 -2906
Ca -1577 -3517 -2986 -2610
Sr -1443 -3312 -2718 -2459
Ba -1305 -3120 -2614 -2367

To predict the solubility of a substance in water it is necessary to know the relative values of
hydration energy and lattice energy. Both hydration energy and lattice energy decrease with increase in
size of metal ion. Decrease in lattice energy favours solubility whilst decrease in hydration energy
disfavors solubility. If on descending the group the hydration energy decreases more rapidly than the
lattice energy, the solubility decreases; this is observed in most cases, except for fluorides and hydroxides.
The solubility of the sulphates decreases down the groups. This is because the sulphate anion is large
and relatively small variation in size of the cation does not significantly alter the lattice energy. Due to
small size Be2+ and Mg2+ have high hydration energies and BeSO4 and MgSO4 are soluble in water.
CaSO4 is slightly soluble whereas SrSO4 and BaSO4 are almost insoluble.
Thermal Stability of Oxo-salts
The thermal stability of the oxo salts like carbonates, sulphates and nitrates increase on moving
down the group i.e. with increase in electro positive character. The carbonates, sulphates and nitrates
all decompose give the corresponding oxides.
CaCO 3  CaO + CO2
BaSO4  BaO + SO3
2Ca (NO3)2  2 CaO + 4NO2 + O2
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Organometallic Compounds
Beryllium and magnesium form an appreciable number of compounds with the M—C bond. The
most important organomagnesium compounds are the Grignard Reagents represented by the formula
RMgX (R= alkyl or aryl). They are made by the slow addition of an alkyl or aryl halide to a continuously
stirred mixture of magnesium turnings in dry diethyl ether in the absence of air. These are versatile
reagents and are widely used to synthesize a vast range of organic compounds like alcohols, aldehydes,
ketones, carboxylic acids, esters and amines.
They are also good starting materials for synthesis of many organometallic compounds. Some
examples are: -
BeCl2
RMgBr   BeR 2
LiR
RMgBr   MgR2
BCl3
RMgBr   BR3
SiCl4
RMgBr   RSiCl3  R 2SiCl2  R3 SiCl  SiR 4
Grignard reagents cannot be stored. They are made and used as and when needed without
isolating them.
All metals of this group form dialkyls and diaryls of the formula MR2. The dimethyl derivative of
beryllium is dimeric in the vapour state and polymeric in the solid state having a chain structure like the
hydrides. The bonding too is similar involving three-centred -two electron bonds.
Complexes
Due to smaller size and higher nuclear charge, the Group 2 metals form more complexes
compared to their Group 1 counterparts. Beryllium being smaller forms a greater number of complexes
than the heavier members; the complexes are tetrahedral in structure with beryllium displaying a coordination
number of 4.This is understandable as beryllium does not have vacant d orbitals and cannot expand its
octet. Among the best known complexes of beryllium are the tetrafluoroberyllates [BeF4]2- and dioxalatoberyl
late [Be(C2O4)2 ]2-

O
F O C
] 2– ] 2–

C O
Be Be
F F O O

F O C O
2–
[BeF4]
C
||
O
In hydrated salts like BeCO3.4H2O and BeSO4.4H2O, beryllium exists as the tetraaquaberyllium
ion, [Be(H2O)4]2+.
The most important compound of magnesium containing organic species is chlorophyll, which is
responsible for life on earth. It is a green pigment in plants that absorbs sunlight and makes energy
available for photosynthesis. It converts carbon dioxide in presence of water to glucose in sunlight.
chlorophyll
6CO 2  6H2O 
Sunlight
C6H12O 6  6O 2

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 Chemistry (s and p-Blocks)

The magnesium is coordinated to four cyclic nitrogen atoms in a reduced porphyrin ring system
(Fig.)

Fig.: Chlorophyll

Calcium and the lower members form complexes with strong complexing agents like
ethylenediamine-tetraacetic acid (EDTA). EDTA forms complexes with coordination number six with both
calcium and magnesium; this fact is utilized in estimation of hardness of water. The amount of Ca2+ and
Mg2+ (responsible for harness) is determined by titration with EDTA. They also form complexes with
polyphosphates that is used in water softening. Stable solid complexes with crown ethers and crypts
have been isolated.

Biological Importance
Mg2+ and Ca2+ are important in biology. Mg2+ is an essential constituent of chlorophyll. Mg2+ ions
are present in animal cells whilst Ca2+ ions are present in the extra cellular fluid. Calcium salts are quite
insoluble and hence calcium is found in hard tissues — nails, bone and teeth. Mg2+ ions form a complex
with ATP and are constituents of enzymes for reactions involving ATP. They are also involved for
transmission of nerve impulses. Ca2+ ions are involved in blood clotting and muscle-contraction and
maintain correct rhythm of the heartbeat.

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 Chemistry (s and p-Blocks)

2. P-BLOCK ELEMENTS

General Trend
 The elements in which the outermost electron enters one of the p-orbitals are referred to
as p-block elements.
 There are six groups of p-block elements (Groups 13, 14, 15, 16, 17 and 18).
2
 The general outer electronic configuration is ns np1-6.
 The covalent radii and metallic character increase on moving down the group and decrease
on moving across a period.
 The ionization enthalpy, electronegativity and oxidizing power increase across a period
and decrease down the group.
 Unlike the s-block elements, which are all reactive metals, the p-block elements comprise
of both metals and non-metals.
 Since the chemical behavior of metals and non-metals vary, a regular gradation of properties
is not observed in p-block elements.
Difference in Chemical Behaviour of the First Element
It is interesting to note that the first member of each group differs in many respects from the other
members. These differences are quite striking in Groups 13-16. The cumulative effects of small size,
high electro-negativity and non-availability of d-orbitals for the first member are responsible for these
differences.
Due to non-availability of d-orbitals, the first member can display a maximum coordination number
of 4, whereas the others can display higher coordination numbers. Hence we come across species like
[SiF6]2-, PCl5, PF5, SF6, but analogous species for carbon, nitrogen and oxygen are not known. The first
member, by virtue of having small size and high electronegativity, can form p - p bonds with itself or
other elements e.g. C = C, C  C, N  N, C = O, C  N, N = O etc. The heavier members do not display
p - p multiple bonding but can show p - d bonding.

Inert Pair Effect

 The p-block elements display two oxidation states. This is in sharp contrast to the s-block
elements that display only one oxidation state, the group number.
 The higher oxidation state is equal to the group number minus 10 (i.e. number of s and
p electrons in the valence shell) and the lower one is two units less than the group number
(i.e. number of p-electron in the valence shell).
 The lower oxidation state becomes more stable on descending the group. This is referred
to as the inert pair effect.
 The higher oxidation state is displayed only when both the ns and np electrons are
involved in bond-formation. On the other hand, the lower oxidation state is observed when
only the np electron(s) participate in bond formation. On moving down the group the ns
electrons tend to remain inert and do not participate in bond formation. This reluctance of
the outermost s orbital electron pair to participate in bond formation is called inert pair
effect.
 The reason for this effect is explained in terms of bond energy. On one hand energy is
needed to uncouple the s-electrons and on the other hand energy is released during bond
formation. If the energy released is sufficient to unpair the s-electrons, then they participate
in bond formation, otherwise they do not. The bond energy decreases down the group and
hence inert pair effect is prominent for the lower members.

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 Chemistry (s and p-Blocks)

Group-wise systematic study of p-block elements

Group-13
 The elements in this group are boron, aluminium, gallium, indium and thallium.
 The general electronic configuration is ns2np1.
 Boron is a non-metal while the others are fairly reactive metals.

Physical Proportion
Some important physical constants of the Group 13 elements are shown in table.
Table: Physical properties of Group 13 Elements

Property B Al Ga In Tl
Electronic Configuration 2 1 2 1 10 10 14
[He]2s 2p [Ne]3s 3p [Ar]3d [Kr]4d [Xe]4f
2 1 2 1 10 2 1
4s 4p 5s 5p 5d 6s 6p
Atomic radius (pm) 85 143 135 167 170
Ionization Energy (I) 801 578 579 558 589
(KJmol-1)
Electronegativity 2.05 1.61 1.75 1.65 1.79
0 2180 660 29.8 157 304
Melting Point ( C)
Boiling Point (0C) 3650 2467 2403 2080 1457

The elements of Group 13 have smaller atomic radii and higher electronegativities as compared
to s-block elements. However, these properties do not vary in a regular manner. The atomic radius of
gallium (135 pm) is slightly less than that of aluminum (143 pm). This is because Ga follows the d-block
elements and the inner core of Ga contains ten ‘d’ electrons that do not shield the nuclear charge
efficiently. Therefore, the effective nuclear charge of Ga is more than that of Al so that the outer electrons
are attracted towards the nucleus and the size is smaller than expected.
The electronegativity and ionization energy consequently are higher than expected. Similarly, the
inclusion of fourteen ƒ’ electrons on the inner core affect the size and ionization energy of Tl.

Oxidation states and Bond Type

 The common oxidation states are +3 and +1.
 The stability of the +1 oxidation state, due to inert pair effect, increases down the group.
Compounds of Ga (I), In (I) and Tl (I) are known Tl (I) compounds are more stable than
Tl (III) and the latter are oxidizing in nature. Ga (I) compounds are reducing indicating that
Ga (III) is more stable.
 The higher oxidation state is generally covalent. Boron is always covalent and does not
form B3+ ion. Some compounds of Al and Ga like AlCl3 and GaCl3 are covalent in the
anhydrous state.
 However the M3+ ions are associated with high hydration energies, which compensate the
high ionization energies, and hydrated cations are known.

Chemical Proportion
Boron’s chemistry is so different from that of the other elements in this group that it deserves
separate discussion.
Chemically boron is a non-metal, it has a tendency to form covalent bonds and displays similarities
with silicon, which will be discussed later.

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 Chemistry (s and p-Blocks)

All elements except thallium when treated with halogens, oxygen or sulphur form halides (MX3 )
oxides (M2O3) and sulphides (M2S3). Thallium forms TlX, Tl2O and Tl2S. Aluminum has a very high affinity
for oxygen (enthalpy of formation of Al2O3 is – 1676 KJ mol-1) and is used to remove oxygen from other
metal oxides. This forms the basis of the Thermite process for extracting many metals from their oxides.
3 MnO2 + 4Al  2Al2O3 + 3Mn
Fe2O3 + 2Al  Al2O3 + 2Fe
Boron and aluminium form nitrides by direct combination with nitrogen at very high temperature.
They form carbides on heating with carbon.Aluminium carbide (Al4C3) on hydrolysis given methane.
Al4C3 + 12H2O  4Al(OH)3 + 3CH4
Boron carbide (B2C3) is a hard, high melting, inert compound used as an abrasive. Boron combines
with many metals to form borides e.g. MgB2, VB, Fe2B where it displays negative oxidation state. The
reactions of the elements with acids differ. Boron reacts only with oxidizing acids to form boric acid
2B + 3H2SO4  2H3BO3 + 3SO2
B + 3HNO3  H3BO3 + 3 NO2
Boric acid is better represented as B(OH)3 and does not contain replaceable hydrogen. The other
elements react with dilute mineral acids to evolve hydrogen
2M + 6HCl  2MCl3 + 3H2
Al is rendered passive with concentrated nitric acid. Boron liberates hydrogen when fused with
alkali.
2B + 6NaOH  2Na3BO3 + 3H2
Aluminium and gallium dissolve in alkali to form tetrahydroxoaluminate (III) and tetrahydroxogallate
(III) respectively.
M + 4NaOH  Na[M(OH)4] + 2H2
Thus, we see that elements of Group 13 are quite reactive. We will now study some important
compounds.

Hydrides
The elements form tri-hydrides (MH3), the stability decreases on moving down the group. They
are electron deficient compounds. Boron forms a series of volatile hydrides called boranes (by analogy
with alkanes and silanes). They fall into two series:
Bn Hn+4 : B2H6, B5H9, B6H10, B8H12, B10H14
Bn Hn+6 : B4H10, B5H11, B6H12, B9H15
They are named by indicating the number of boron atoms. If two or more boranes have the same
number of B atoms, then the H atoms are also specified, e.g. B5H9 and B5H11 are named pentaborane
– 9 and pentaborane – 11 respectively.
Diborane is the simplest and most extensively studied hydride. It is an important reagent in
synthetic organic chemistry. It may be prepared by various ways:
Diethyl Ether
4BF3 .OEt 2  3LiAlH4   2B2H6  3LiF  3AlF3  4Et 2O
Boron tri-fluoride etherate
Diglyme
2NaBH4  I2   B2H6  2Nal  H2
Sodium borohydride
2NaBH4 + H2SO4 / 2H3PO4  B2H6 + 2H2 + Na2SO4 / 2Na2HPO4
It is a colourless gas, which burns in air and is readily hydrolyzed.
B2H6 + 3O2  B2O3 + 3H2O

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 Chemistry (s and p-Blocks)

B2H6 + 6H2O  2H3BO3 + 6H2

Diborane undergoes addition reaction with alkenes and alkynes in ether at room temperature to
form organo-boranes.
6RCH = CH2 + B2H6   2B(CH2CH2R)3
This is known as hydroboration reaction. The structure of diborane is of great interest as it is an
electron deficient compound having only twelve electrons, which are insufficient to form the required
number of bonds. Each boron has three electrons and can form a BH3 unit each but how will the two
units be held together?

133 pm
H H H
119 pm
B B
H H H

Diborane is found to have a bridge structure in which each B atom is bonded to two H atoms
(called terminal H atom) by regular electron pair bonds. The resulting two BH2 units are bridged by two
H atoms (the bridge H atoms), which are at a plane perpendicular to the rest of the molecule and prevent
rotation between the two B atoms. The structure has been confirmed by electron diffraction, infrared and
Raman spectroscopic methods. Four hydrogen atom are in an environment different from the other two
– this is confirmed by Raman spectra and by the fact that diborane cannot be methylated beyond the
tetra methyl derivative without breaking the molecule into BMe3
The terminal B- H bond distances are the same as in non-electron deficient compounds. These
are normal two centre - two – electron bonds (2c-2e). Electron deficiency is thus associated with the
bridge bonds. The four bridge bonds involve only four electrons – a pair of electrons is involved in binding
three atoms – B, H and B. These bonds are called three-centre-two-electron-bonds (3c-2e).
Each B atom is sp3 hybridized giving four sp3 hybrid orbitals. B has three valence electrons so
three orbitals are filled singly. Two of the sp3 hybrid orbitals on each B overlap with the 1s orbitals of H
forming four 2c – 2e bonds.
Then one singly filled sp3 hybrid orbital on one B atom, and one vacant sp3 hybrid orbital on
another B atom overlap with a singly filled 1s orbital on one H atom to form a bonding orbital shaped
like a banana embracing all three nuclei Another 3c – 2e bond is formed similarly (fig.)

H H H H
H H
B B B B
H H
H H H H

Fig. : Formation of banana-shaped three-centre-two-electron bond in Diborane

Most syntheses of the higher boranes involve heating B2H6, sometimes with hydrogen. Most of
the higher boranes are liquids but B6 H10 and B10 H14 are solids. They were considered to be potential
rocket fuels, but interest in this was soon diverted as it was found that on combustion they formed a
polymer, which blocked the nozzles.
The higher boranes have an open cage structure (fig). The structures involve 2c – 2e bonds
between B and H and B – B and 3c – 2e bonds involving B-H-B and B-B-B. Closed 3c-2e bonds of the
type are also known.

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 Chemistry (s and p-Blocks)

B4H10 B5H9
Fig. : Structures of Some Boranes
Borohydrides
Borohydrides like NaBH4, Al(BH4)3 contain the tetrahydroborate (III) anion, BH4. In these compounds
boron has a complete octet and thus they are more stable than the boranes. Sodium borohydride is
obtained by the reaction between sodium hydride and methyl borate.
4NaH+B(OMe)3  NaBH4 + 3CH3ONa
Other borohydrides may be obtained from NaBH4–. The BH4 ion has a tetrahedral structure,
NaBH4 is a useful reagent used in reduction of aldehydes and ketones.
Hydrides of other members
Other members of Group 13 form a few hydrides which are polymeric in nature e.g. (AlH3)n,
(GaH3)n and (InH3)n and contain M-H-M bridges. Their stability decreases on moving down the group.
(AlH3)n is the best known and is prepared by the action of pure H2SO4 or AlCl3 on lithium aluminium
hydride in ether.
2LiAlH4 + H2SO4  2/n (AlH3)n + LiSO4 + 2H2
3LiAlH4 + AlCl3  4/n (AlH3)n + LiCl.
It is a colourless and thermally unstable solid and reacts violently with water.
2(AlH3)n + 6nH2O  2nAl(OH)3 + 9nH2
A complex hydride of aluminium, lithium aluminium hydride is well known. It is prepared from
lithium hydride and aluminium chloride in ether.
Ether
4LiH  AlCl3   LiAlH4  3LiCl
It is a powerful reducing agent and is widely used in organic chemistry. The borohydrides of
aluminium, beryllium and the transition metals are covalent. In Al (BH4 )3 each BH-4 unit forms two
hydrogen bridges while in Be(BH4)2 each BH-4 unit forms three hydrogen bridges (Fig. )

Fig: Structures of (a) Al(BH4)3 (b) Be(BH4)2

Oxides, oxoacids and hydroxides
Trioxides of all elements (M2O3) are known Thallium forms the monoxide. On moving down the
group, the basicity of the oxide increases along with increase in metallic character of the element. Thus
B2O3 is acidic, Al2O3 and Ga2O3 amphoteric while In2O3 and Tl2O3 are basic. Tl2O is strongly basic; it
dissolves in water forming TlOH, which is as strong a base as KOH. B2O3 is obtained by direct combination
or by dehydration of boric acid.

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 Chemistry (s and p-Blocks)

2B  3O2 
 B2O3
100 C red heat
2H3BO3   2HBO2   B 2O3
Orthoboric acid –2H2O metaboric acid -H2O
Being the oxide of a non-metal it is acidic in nature. It is the anhydride of boric acid. When fused
with metal oxides or salts it forms metaborates. The metaborates of transition metals have characteristic
colours and form the basis of borax-bead test of identification of metals.

CoO  B2O3 
 Co(BO2 )2 deep blue

CuSO4  B2O3 
 Cu(BO2 )2  SO3
Blue

Cr2O3  3B2O3 
 2Cr(BO2 )3
Green
However when B2O3 is treated with strongly acidic compounds like phosphorus pentoxide, it is
forced to behave as a base.
B2O3 + P2O5   2BPO4
Aluminium oxide occurs in nature as bauxite and corundum and also as gemstones – ruby,
emerald, sapphire etc. the colour is due to transition metal ions like iron, chromium, titanium etc.
Anhydrous aluminium oxide exists in two forms- -Al2O3 and r-Al2O3. r-Al2O3 is obtained by dehydration
of Al(OH)3 below 450°C and unlike -Al2O3 it is soluble in acids, absorbs water and is used in
chromatography.
2Al(OH)3   Al2O3 + 3H2O
On heating to 1250°C it changes to the á form which high melting, hard and inert.
Aluminium hydroxide is amphoteric and dissolves in both acids and bases.
Al(OH)3 + 3HCl  AlCl3+3H2O
Al(OH)3 + NaOH  Na [Al(OH)4] or NaAlO2.2H2O
In sodium hydroxide it forms sodium tetrahyodroxoaluminate (III), commonly referred to as sodium
aluminate. If this solution is acidified Al(OH)3 is reprecipitated. The sequence of reactions may be
represented as

The structure of sodium aluminate is complicated and varies with pH and concentration. Polymeric
species with OH bridges are formed between pH 8-12. Above pH13, the tetrahedral [Al(OH)4]-ion exists
in dilute solutions white dimeric species are found in concentrated solutions (fig.)
2–
OH ]
–
OH OH ]

Al Al Al
HO OH HO O OH
OH OH OH
(a) (b)
Fig: Hydro complexes of Aluminium at (a) pH8-12 (b) above pH 13

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 Chemistry (s and p-Blocks)

Ga2O3 and Ga(OH)3 are amphoteric like Al2O3 and Al (OH)3. In2O3, Tl2O3 and Tl2O are basic.
When a metal exists in two oxidation states, the lower oxidation state is more basic. Thus TlOH is a
stronger base than Tl(OH)3.
The most common oxo acid of boron is orthoboric acid which is a flaky solid having a two –
dimensional layer structure (fig.). The BO3 units are linked by hydrogen bonds and individual layers are
held by weak forces, making the substance flaky and waxy.

Fig: Hydrogen bonded structure of Boric acid

It is a very weak monobasic acid (pKa= 9.25). It is not a proton donor but an OH- acceptor - thus
it acts as a Lewis acid. It is frequently represented as B(OH)3

B(OH)3  2H2O 
 H3O [B(OH)4 ]


Its acid strength is enhanced in presence of cis-diols like glycerol, mannitol and sorbitol. The cis-
diols form stable complexes with the metaborate ion, this shifts the equilibrium to the right making boric
acid ionize to its full capacity.

C O O C
+
B(OH)3+2 C—C H3 O + B
C O O C
OH OH
+2H2O

Salts of boric acid are called the borates. Orthoborates contain discrete BO33- units where the
boron atom is sp2 hybridized. In metaborates the simple units join together to give chain and ring
structure. The most common borate is borax Na2B4O7.10H2O (Sodium metaborate). The structures of
some borates are shown in Fig.

B
B B
B B
B B

(a) (b)

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 Chemistry (s and p-Blocks)

OH
|
HO HO B O
B—O B—O O
O HO — B O B — OH
O B O
O
B—O B—O B
HO OH |
OH
(c) (d)
Fig. : Structures of (a) Metaborate chain (b) Metaborate ring
(c) Complex metaborate (d) Borax
Halides
Tri-halides (MX3 ) are known for all elements except TlI3 . Due to inert pair effect Tl(I) is stable
and Tl(III) is oxidizing in nature. It oxidizes iodide to iodine. Thallium (III) chloride and bromide are also
unstable. The halides of boron are covalent. BF3 is the most important halide and is prepared by the
following reaction:
B2O3  3CaF2  3H2SO4 (Conc.) 

 2BF3  3CaSO4  3H2O

Na2B4 O7  6CaF2  8H2SO4 (Conc.) 


 4BF3  6CaSO4  6NaHSO4  7H2O
BF3 is an electron deficient compound and boron has a sextet of electrons around itself (instead
of an octet) VSEPR theory predicts a planar triangle structure with bond angle of 1200

1s 2s 2p
Electronic configuration
of B atom (ground state)

B atom (excited state)

sp2 hybridization
The B-F bond lengths (130 pm) are shorter than the sum of covalent radii of B (80 pm) and F
(72pm). The bond energy is also higher than that of a single bond. This implies development of double
bond character in the B-F bond. The vacant 2p orbital on B overlaps with one of the filled 2p orbital of
fluorine to form a dative  bond (p -p bond) fig.

F F F F
F

B F B B B B

F F F F F F F F F

Fig. : Structure of BF3

As a result of this  bond formation, the boron atom attains an octet of electrons and remedies
the electron deficiency. All bond lengths are identical indicating resonance between three forms (fig.).As
may be expected from their electron deficient nature, the tri-halides of boron act as Lewis acids and

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 Chemistry (s and p-Blocks)

accept electron pairs from Lewis bases like ammonia, amines and ethers. The electrons are donated
to the vacant 2p orbital and the resultant adducts have tetrahedral structure.

F F X = NH3, Et2O, RNH2, F etc.

–

X
In these compounds the B-F bond length is longer than that in BF3 as there is no vacant 2p orbital
on B and the dative bond cannot be formed. Fluorine is the most electro-negative halogen and the order
of acid strength of BX3 is expected to be BF3 > BCl3 > BBr3 > BI3 but the reverse is true. These
compounds act as Lewis acids because of their electron deficiency. We have seen that an internal
compensation of electron deficiency is achieved by dative bond formation. In order to form a strong dative
bond, it is essential that the orbitals of the combining atoms be matched in size so as to allow effective
overlap. The 2p orbital of fluorine is matched in size with the 2p orbital of boron resulting in a strong bond
and reduction of electron deficiency on boron. As the size of the halogen increases, the orbitals become
larger and more diffuse to allow effective overlap with the 2p orbital of boron. Thus the electron deficiency
on boron increases and the relative acid strength follows the order: BF3 < BCl3 < BBr3 < BI3. The boron
halides undergo hydrolysis; the hydrolysis of BF3 is partial and the hydrolysis products, boric acid and
hydrogen fluoride, combine to give fluoroborate ion
BF3 + 3H2O  H3BO3 + 3HF
4HF + H3BO3  H+ + BF4– + 3H2O
4BF3 + 3H2O  H3BO3 + 3H+ + 3[BF4]–
The other tri-halides are hydrolyzed completely to give boric acid and the corresponding hydrogen
halide.
BX3 + 3H2O  H3BO3 + 3HX
The fluorides of the other elements are ionic and high melting solids. The other halides are largely
covalent; the trichlorides of aluminium and gallium exist as bridged dimers.

Cl Cl Cl
Al Al
Cl Cl Cl
Each aluminium atom acquires an octet by accepting an unshared electron pair from the other
AlCl3 molecule. However, these dissolve in water, the high hydration enthalpy allows the formation of
[M(H2O)6]3+ and 3 Cl– ions. Anhydrous aluminium chloride is used as a catalyst in Friedel -Craft’s
reaction. TlI3 is an unusual compound where in Tl is present in +I oxidation state and it is bound to the
linear triiodide ion (I–3). It is represented as Tl+I–3. Boron forms dihalides of the formula B2X4, the dichloride
is obtained from BCl3
Elec. discharge
2BCl3  2Hg 
Low pressure
 B2Cl4  Hg2Cl2

It exists in non-eclipsed and planar conformations with free rotation about the B-B bond (fig.)
Gallium and indium form di-halides, GaCl2 and InCl2 they are better represented as M+ [MCl4]–, i.e. they
contain M(I) and M(III).
Boron forms some monohalides which are polymeric and are represented as (BX)n, Chlorides
with n=4, 8, 9, 10, 11 and 12 are reported, B4Cl4, B8Cl9 are crystalline solids having closed cage of boron
atoms (fig.)

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 Chemistry (s and p-Blocks)

Cl Cl

B—B

Cl Cl
Non-eclipsed
Cl Cl

B—B

Cl Cl
Planar
B4Cl 4 B8Cl 8 B9Cl 9 B2Cl 4
Fig.: Structures of (BCl)n

Each boron atom is bonded to three other boron atoms and one chlorine atom by multi-centred
bonding.
Boron-nitrogen compounds
The B-N bond is isoelectronic with the C-C bond and parallels between boron-nitrogen compounds
with organic compounds are known. One of the best known of these pairs is benzene and the isoelectronic
borazine also known as inorganic benzene, B3N3H6

H H
C B
HC CH HN NH
| | | |
HC CH HB BH
C N
H H
The compounds are structurally similar and also exhibit similar physical properties. However, the
chemical properties are widely different. The nature of the -bond in borazine and benzene differ. In
benzene the  – bond is formed by sideways overlap of the 2p orbitals of carbon atoms and the two
atoms involved in  bond formation do not differ in electro negativity. In borazine the nitrogen atom
donates an unshared electron pair to a vacant p orbital on B, thereby forming a  bond

The polarity of the B-N bond is less than what is expected on basis of electro negativity difference
between boron and nitrogen. This is because during  - bond formation the electron density shifts
towards the more electronegative atom, nitrogen while the reverse happens during  bond formation. The
molecule however is polar and undergoes addition reactions.

This is in sharp contrast to benzene, which does not undergo addition reaction.

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 Chemistry (s and p-Blocks)

Another interesting compound is boron nitride, BN. Like carbon it exists in two forms – a diamond
– like form and another form like graphite, which comprises of six-membered rings fused together (Fig.)
| | | | | |
B B B C C C
N N N N C C C C
| | | | | | | |
B B B B C C C C
N N N C C C
| | | | | |
B B B C C C
N N C C
| | | |
Boronnitride Graphite
Fig. : Similarity in structures of Boron Nitride and Graphite
Organometallic compounds
Tri-alkyl and tri-aryl derivatives of boron, aluminium, gallium and indium are known. The tri-alkyl
derivatives of aluminium are important and are obtained by treating aluminium chloride with the appropriate
Grignard reagent.
AlCl3 + 3RMgI    AlR3
These are electron deficient compounds and exists as bridged dimers

H3C CH3 CH3

Al Al
H3C CH3 CH3
The terminal Al-C bond lengths are shorter than the bridge Al – C bond lengths. The bridge bonds
are three – centre – two – electron bonds.
Aluminium tri-ethyl is referred to as Ziegler catalyst and is used to carry out polymerization of
ethene to give polythene Polymerization is quicker if TiCl4 (Natta Catalyst) is used along with Ziegler
catalyst and the reaction does not require high pressure.
Complex formation
The Group 13 elements form complexes more readily than the s-block elements. Because of lack
of d orbitals, boron exhibits a coordination number of 4 and forms tetrahedral complexes like NaBH4,
HBF4, BF3.NH3 etc. The lower members form octahedral complexes also e.g. [AlCl6]2– [GaCl6]2– etc.
Apart from complexes, aluminium forms double sulphates (alums) of the general formula
M2SO4.Al2(SO4).24H2O where M is a monovalent metal or ammonium eg. K2SO4.Al2(SO4).24H2O is
potash alum. Aluminium can be replaced by cations of comparable size and charges like iron, chromium
etc.
Group 14
The elements in this group range from a non-metal, carbon to the metals tin and lead, with the
intervening element – germanium showing semi metallic behaviour. Carbon has been known from pre
history as the charcoal resulting from partial combustion of organic matter. Carbon is an essential
constituent of all living matter. Silicon is the second most abundant element in the earth’s crust; tools
made of flint (a form of SiO2) were used in the Stone Age. Tin and lead have also been known since
ancient times Germanium was a “missing element” in Mendeleev’s periodic table. He named this element
as “ekasilicon” and predicted its properties that later matched with those of germanium. All the elements
have an outer electronic configuration of ns2 np2 and some important physical constants are summarized
in Table.

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 Chemistry (s and p-Blocks)

Table: Physical properties of Group 14 elements

Property C Si Ge Sn Pb
2 2 2 2 10 10 14
Electronic Configuration [He]2s 2p [Ne]3s 3p [Ar]3d [Kr]4d [Xe]4f
2 2 2 2 10 2 2
4s 4p 5s 5p 5d 6s 6p
Covalent radius (pm) 77 118 122 140 146
Ionization Energy (I) (KJmol-1) 1086 786 762 709 716
Electronegativity 2.54 1.92 1.99 1.82 1.85
0
Melting Point ( C) 4100 1420 945 232 327
0
Boiling Point ( C) Sublimes 3280 2850 2623 1751
M – M bond energy (KJmol-1) 348 297 260 240 -

The general trends observed in size and ionization energy follow the same order as in group 13.
The main isotope of carbon present in the earth is 12C (in the modern system of atomic mass
this is taken as the standard), two other isotopes 13C and 14C are also known. 13C NMR spectroscopy
is common for characterization of organic compounds.
14
C is obtained from nitrogen in the atmosphere by thermal neutrons in presence of cosmic
radiation.
14 1 14
N 0n 
 6 C  11H

The 14C produced is oxidized to 14CO2 which is radioactive and this alongwith non-radioactive
CO2 is incorporated into plants by photosynthesis. The ratio of 14C to 12C in a living plant is the same
as that in the atmosphere. When the plant dies the amount of 14C diminishes by radioactive decay and
this loss is not compensated by assimilation of 14CO2 from the atmosphere. The ratio of 14C to 12C
decreases. The half-life of 14C is 5730 years and by measuring the remaining amount of 14C it is possible
to know the age of the substance (i.e. time of its death). This is called “radiocarbon dating’.

Allotropy of Carbon
Until 1985, only two allotropes of carbon were known – diamond and graphite. Diamond is the
hardest substance known, having a very rigid structure. Each carbon atom is sp3 hybridized and linked
to four other atoms. Graphite has a layer – structure in which weak van der Waal’s forces hold individual
layers of fused six membered rings together. The carbon atoms are sp2 hybridized and out of four
valence electrons, three are involved in -bond formation the fourth electron is involved in delocalized -
bonding. The layers slide over one another and the  electrons move within each layer making graphite
a conductor of electricity and conferring lubricating properties. Some physical properties in table.
Table: Physical properties of Diamond and Graphite

Property Diamond Graphite

Density (gcm )
–3
3.51 2.26
11 -5
Electrical Resistivity (?m) 1 × 10 1.3 × 10
C-C distance (pm) 154.4 141.5 (Intra Layer)
335.4 (Inter Layer)

At room temperature graphite is thermodynamically more stable and can be converted to diamond
at high pressure and temperature. Artificial diamonds are prepared from graphite.

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 Chemistry (s and p-Blocks)

A fascinating discovery was the synthesis of spheroid carbon- cage molecules called fullerenes.
These were first prepared by evaporation of graphite using laser. A more practical method is to heat
graphite in an electric are in an inert atmosphere (helium or argon). A sooty material so formed consists
of C60 with smaller amounts of C70 and other fullerenes containing even number of carbon atoms. Unlike
diamond and graphite fullerenes dissolve in organic solvents like toluene. C60 is the most stable fullerene
containing twenty six-membered rings and twelve five-membered rings. The six- membered rings are
fused to other six membered and five- membered rings while five- membered rings and connected to
only six- membered rings(Fig.). Two types of bond lengths are noted, the C-C bond lengths at fusion of
two six membered rings is 135.5 pm while the C-C distances at fusion of five and six membered rings
is 146.7 pm. Thus there is greater  character in the bonds obtained by fusion of six membered rings.
The smallest known fullerene is C20 obtained from the hydrocarbon C20H20 by a two- step reaction.
First, the hydrogens are replaced by bromine, this is followed by debromination. The Nobel Prize for
Chemistry (1996) was shared by R.F. Curl, H. Kroto and R.E. Smalley for the discovery of fullerenes.
Silicon and germanium predominantly crystallize in diamond structure and both are
semiconductors. Tin exists in a diamond form () and metallic form () while lead is metallic.

Fig. : Diamond, Graphite, Fullerenes

Oxidation states and Bond Type
The commonly observed oxidation states in this group are +4 and +2. Carbon and silicon are
generally tetravalent but on descending the group the stability of the +4 oxidation state decreases due
to inert pair effect. The +2 oxidation state becomes important progressively and lead is predominantly
divalent. Therefore Pb(IV) compounds like PbCl4 and PbO2 are highly oxidizing and PbO2 may oxidize
hydrochloric acid to chlorine.
PbO2 + 4HCl  PbCl2 + 2H2O + Cl2
The lower oxidation state is more ionic as M4+ is smaller than M2+ and covalency is favoured by
large charge on cation and small size. In tetravalent compounds the Group 14 element is sp3 hybridized.
Carbon has greater electronegativity and may form carbide ion, C4– and C22–
Catenation and multiple bond formation
Carbon has a remarkable property of forming long chains and rings when bound to itself. This
is called catenation and is attributed to the strength of the C-C bond, The M – M bond strength decreases
down the group and tendency for catenation also decreases. Carbon also forms p – p bonds with itself
and other electronegative elements e.g. C=C, CC, C=O, C=S and CN linkages are known. The other
elements do not form such bonds. The reluctance of the silicon atom to form multiple bonds is revealed
by the fact that silicon adopts a diamond – like structure and not graphite – like structure; CO2 is a gas
comprising of discrete stable O=C=O units whilst SiO2 is a high-melting solid having a net-work three-
dimensional structure of Si-O-Si linkage.

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 Chemistry (s and p-Blocks)

Chemists have been exploring the tendency of the silicon atom to form multiple bonds. Transient
reaction species containing the Si = C bond have been known since 1966 and the first such species,
Me2Si = CHMe was isolated a decade later. In view of the extensive chemistry of alkenes it was natural
to search for analogous compounds containing the > Si = Si < bond. The first such compound,
tetramesityldisilene, was isolated in 1981 as orange crystals following photolysis of cyclotrisilane.

Mes Mes Mes Mes Mes

| | |
Cl — Si — Mes Mes — Si — Si — Mes Si = Si
|
Cl Si Mes Mes
Mes Mes
where, Mes = Mesityl
The Si = Si distance in such compounds lies in the range 214 to 216pm considerably shorter than
the normal single bonded Si—Si distance. Disilenes are chemically very reactive and it is possible to add
reagents like halogens, HX and EtOH across the Si = Si double bond. The 3p orbitals of Si are larger
and more diffused than the 2p orbitals of C; therefore the -bond formed between the Si atoms is weaker
than that between the C atoms.
Intercalation compounds
The structure of graphite indicates loosely bound layers separated by a large distance. Many
molecules can be inserted in the space between the layers forming intercalation compounds of varying
composition. The interlayer distance increases in these compounds. If the graphite sheets remain flat,
then the new compound retains the structure and conductivity of graphite. If the attacking species add
electrons, the conductivity increases.
Heating graphite 3000 C in presence of vapors of K, Rb and Cs gives bronze coloured compounds
C8M, on heating further at reduced pressure, some of the metal is lost and intercalation compounds are
formed which vary in colour, depending on the number of layers invaded by the metal.

C8M C24M C36M

Bronze (every steel blue (every blue (every
layer is occupied second layer is occupied) third layer is occupied)

C48M
Black (every
fourth layer is occupied)
Intercalation compounds of graphite are known with FeCl3, chlorine, bromine, some metal oxides
and sulphides. The intercalated compounds exhibit interesting properties.

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 Chemistry (s and p-Blocks)

Chemical properties
The chemical reactivity increases down the group. Some reactions of Group 14 elements are
shown in table.
Table : Some Reactions of Group 14 Elements
HCl (hot, concentrated) M + 2HCl  MCl2 + H2 M = Sn, Pb
H2SO 4 (hot, concentrated) M + 2H2SO4  MO 2 + 2SO 2 + 2H2O M = Sn, Pb, C slow for Ge
HNO 3 concentrated 3 M + 4HNO 3  3MO 2 + 4NO + 2H2 O M = Ge, Sn
3 Pb + 2HNO 3  3PbO + 2NO + 4H2O
NaOH (aq) Si + 2NaOH+H2O  Na2SiO 3 + 2H2 -
O2 / air (heat) M + O2  MO 2 M=C, Si, Ge, Sn
2Pb + O 2 2PbO
Cl2 (heat) M+ 2Cl2  MCl4 M=C, Si , Ge, Sn
Pb + Cl2  Pb Cl2

Compounds
Carbides
Compounds of carbon with a less electronegative element are called carbides. This excludes
binary compounds of carbon with N, P, O, S and halogens. Depending on the bond – type carbides are
classified as – ionic, interstitial or covalent.
(a) Ionic (salt – like) carbides
These are formed with electropositive metals and may contain different carbide anions. The
bonding is predominantly ionic with some covalent character. The most well characterized carbide ions
are C4– and C22–. Species containing C4– are represented by Al4C3 and Be2C. These are called methanides
as they hydrolyze to give methane.
Al4C3 + 12H2O  4Al(OH)3 + 3CH4
Be2C + 4H2O  2Be(OH)2 + CH4
2–
The C ion is found in CaC2, carbides of Cu, Ag, Au and some lanthanides. The most important
2
carbide is CaC2, which is obtained by strongly heating lime with coke. It is structurally similar to NaCl (Fig.)
CaO + 3C  CaC2 + CO
It is called acetylide as it yields ethyne on hydrolyses
CaC2 + 2H2O  Ca(OH)2 + C2H2
4-
The C 3
ion is found in Mg2C3, which yields propyne (H3C – C  CH) on hydrolysis.

Fig: Structure of Calcium carbide

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 Chemistry (s and p-Blocks)

(b) Interstitial carbides

They are formed with transition metals like Cr, Mn, Fe, Co, Ti and W and with some lanthanides.
They are generally high melting and hard. The C atoms occupy octahedral voids in the metal lattice and
do not affect the conductivity of the metal. The ability of carbon atoms to enter the metal lattice without
distortion indicates that the interstices should be fairly large (possible if atomic radius of metal > 135 pm).
For smaller metals i.e. those of the 3d series, inclusion of carbon results in distortion of the lattice, giving
rise to complicated structures.
(c) Covalent carbides
These are formed when carbon combines with an element of comparable electro-negativity e.g.
SiC and B4C SiC (Carborundum) is very hard, un-reactive and a good refractory material. B4C is better
represented as B12C3. They are hard, infusible and inert macromolecules.

Hydrides
All the elements form covalent hydrides but the number of hydrides formed, their stability and
ease of formation decreases down the group. Carbon forms a large number of hydrides involving chains,
rings and multiple bonds between carbon atoms. These hydrides form the basis of organic chemistry.
Silicon forms a limited number of hydrides, the silanes (represented by the formula Sin H2n+2).
Monosilane, SiH4, is the most stable and is tetrahedral, like methane. Silanes containing up to eight
silicon atoms have been synthesized but their stability decreases with increase in chain – length. The
hydrides are prepared as a mixture when magnesium silicide is treated with dilute acids.
Mg2Si + H2SO4  SiH4 + higher silanes
Monosilane can be prepared by reaction of SiCl4 with lithium aluminium hydride or sodium hydride
SiCl4 + Li[AlH4]  SiH4 + LiCl + AlCl3
SiCl4 + 4NaH  SiH4 + 4NaCl
Silanes are more reactive than the corresponding alkanes. Various reasons are attributed to this.
The Si –Si bond is slightly weaker than the C-C bond (bond energies are 340 & 368 KJmol-1 respectively).
The Si-H bond is weaker than the C-H bond (bond energies 393 & 435 KJmol-1 ). The electronegativity
values of Si, C and H are 1.8, 2.5 and 2.1 respectively so the polarity of Si-H and C-H bonds differ and
are depicted as Si – H and C-H. Silicon is more susceptible to nucleophilic attack than carbon as the
larger size of silicon provides greater surface area for the nucleophile to attack. Silicon has vacant low-
lying d orbitals, which can accept electron pairs from nucleophiles and form reactive intermediates.
Silanes decompose to give silicon of high purity by elimination of SiH2. The following mechanism has
been suggested.

H H H H H
| | | | |
H — Si Si — H H — Si Si — H H — Si — H
| | | |
H
H H H H
+ : SiH2

Si + H2

Germanes containing unto five germanium atoms and represented by the formula Gen H2n+2 are
known. They are less stable than the silanes. Tin forms only two hydrides SnH4 and Sn2H6 while lead
form the unstable PbH4.

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 Chemistry (s and p-Blocks)

Halides
Tetra-halides (MX4 ) of all elements are known; but Pb (IV) readily oxidizes iodide and hence the
compound PbI4 is not known. The stability of the tetra-halides decreases down the group. The fluorides,
by virtue of high electronegativity of fluorine, are the most ionic. SnF4 and PbF4 are high melting solids;
the others are covalent, tetrahedral and volatile. The halides of carbon are inert towards water, however
the halides of silicon readily hydrolyze.
SiCl4 + 4H2O  Si(OH)4
The hydrolysis proceeds via an intermediate where silicon has a coordination number of five.
Cl Cl Cl
| H | Cl –HCL |
Si +O Si Si
| H |
Cl Cl Cl Cl Cl Cl
Cl OH
O

H H
This process continues till Si-OH bonds replace all the Si-Cl bonds. Since carbon does not have
d orbitals it cannot form such an intermediate and therefore tetra-halides of carbon do not hydrolyze.
Germanium, tin and lead form both tetra-halides and di-halides. The tetra-halides have a tendency
to hydrolyze, but the hydrolysis can be suppressed by adding the appropriate halogen acid

H2O 
 SnCl4 Sn(OH)4 HCl



The halides of Si, Ge, Sn and Pb can increase the coordination number to 6 by forming complexes
like [SiF6]2–, [SnCl6]2– etc where the vacant d orbitals are used.
There is an increase in stability of dihalides on moving down the group
SiX2<< GeX2 < SnX2 < PbX2
SiF2 can be made at high temperature by the reaction

SiF4 + Si 
 2SiF2



Divalent germanium halides are stable. GeF2 is polymeric having fluorine bridges. Tin (II) halides
are well – characterized and the most important one is SnCl2. it undergoes partial hydrolysis and is
soluble in organic solvents. It is a mild reducing agent as shown by the following reactions:
2FeCl3 + SnCl2  2FeCl2 + SnCl4
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4
Hg2Cl2 + SnCl2  2Hg + SnCl4
Lead (II) halides are the most stable di-halides of this group. In fact, lead is the only element of
this group with well- defined cation, Pb2+. All lead halides are insoluble in water. In qualitative analysis Pb
(II) is precipitated in group I of qualitative analysis as PbCl2 and is confirmed as the yellow PbI2 (s).
Fluorocarbons
Fluorocarbons are the equivalents of hydrocarbons where some or all hydrogen atoms are
replaced by fluorine eg. CF4, C2F4 etc. Replacement of hydrogen by fluorine increases the thermal
stability and chemical inertness as the C-F bond is much stronger than the C-H bond (bond energies
489 and 414 KJ mol-1). The fluorocarbons are prepared by treating the corresponding hydrocarbons with
fluorine.
C8H18 + 9F2   C8F18 + 18HF
Fluorinating agents like CoF3, AgF2 and MnF3 may also be used. Fluorocarbons of chain length
of several hundred-carbon atoms are known. They are resistant to attack by acids, alkalis, oxidizing and

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 Chemistry (s and p-Blocks)

reducing agents. They are attacked by molten sodium. On burning they split at the C-C bond and not
at C-F bond.
The best-known fluorocarbon is polytetrafluoroethylene (Teflon).
High temp
nC2F4 
Pr essure
 (–CF2 – CF2 )n &
Teflon has a low coefficient of friction. It is thermally and chemically inert and a good insulator.
It is used as a coating material in non-stick utensils, razors and bearings.
Mixed chlorofluorocarbons eg. CFCl3, CF2Cl2 and CF3Cl are called Freons. They are inert and
non-toxic and widely used as refrigerants and propellants in aerosol. Their use in aerosols has been
banned as they cause considerable environment damage. They persist unchanged on the atmosphere
for a considerable period of time and are known to damage the ozone layer. Freons are also responsible
for the ‘greenhouse effect’ alongwith carbon dioxide.

Oxides
The oxides of carbon involve p-p bonding between carbon and oxygen. The two important
oxides of carbon are carbon monoxide (CO) and carbon dioxide (CO2). Both are colourless and odourless
gases. Carbon monoxide is obtained when carbon is burnt in a limited supply of air and by the dehydration
of formic acid by concentrated sulphuric acid
HCOOH + H2SO4  CO + H2O
It is a neutral oxide of carbon and is highly toxic as it binds to haemoglobin in preference to
oxygen. Thus haemoglobin cannot act as an oxygen carrier and oxygen is not available to tissues.
Carbon monoxide evolves a considerable amount of heat on burning and is an important fuel,
2CO + O2   2CO2 + 565 K Jmol-1
Producer gas, water gas and coal gas contain carbon monoxide. Carbon monoxide is an important
ligand and forms carbonyl complexes with many transition metals in low oxidation states e.g. V(CO)6
Cr(CO)6, Mn2(CO)10, Fe(CO)5, Fe2(CO)9, Co2(CO)8, Ni(CO)4 etc. The metal–carbon -bond involves
donation of an electron pair from CO to the metal, M CO. This -bond is strengthened by formation of
a back bond by overlap of filled orbital of the metal with the vacant   molecular orbital of carbon
monoxide. In carbonyls CO acts as both an electron donor i.e. Lewis base (-bond formation) and
electron acceptor i.e. Lewis acid (-bond formation). A schematic representation of the orbital overlaps
leading to M – CO bonding is depicted in Fig.

– M + + C O M C O
 bond

–
+ + – – –
+
M C O M C O
+ –
– – + + +
 bond

Fig: Schematic representation of Orbital overlaps in metal carbonyls. The -bond is formed by
overlap of filled orbital on CO with vacant orbital on M. The -bond involves overlap of filled orbital on
M with vacant orbital on CO.
Carbon monoxide acts as a terminal ligand when bonded to only one metal, the M-CO bond is
linear. It can also act as a bridging ligand and be bonded to two different metal atoms simultaneously.
(Fig.)

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 Chemistry (s and p-Blocks)

O
O O O
C
C C
C
Ni O C — CO CO — C O
C C C C
C
C
O O O
O O
O
(a) (b)
Fig: Structures of (a) Ni(CO)4 – only terminal CO groups are present
(b) CO2(CO)8 – having both terminal and bridging CO groups
Carbon dioxide is familiar as a compound in the earth’s atmosphere. It has been recognized as
a “greenhouse gas”, responsible for global warming. It can be liquefied under pressure and the solid form
is called “dry ice” which is used as a fire extinguisher. It is an acidic oxide of carbon. Plants to synthesize
carbohydrates in the process of photosynthesis use carbon dioxide.
Carbon dioxide exhibits unique properties and behaves as a supercritical fluid above its critical
temperature and pressure (31.1ºC and 73 arm respectively). It expands to fill a container like a gas but
the density is like that of a liquid. Supercritical carbon dioxide is becoming an important commercial and
industrial green solvent as it is non-toxic and is a byproduct of other industrial processes. It is used as
a solvent in “dry cleaning” of textiles instead of the toxic tetrachloroethylene. It is also used as an
extraction solvent in the perfumery industry. The relatively low supercritical temperature and reactivity of
carbon dioxide allows the fragrance compounds to be extracted without denaturing and thereby not
affecting their odours. Due to its non- toxicity coffee manufacturers use it as a decaffeinating solvent.
Si, Ge, Sn and Pb all form dioxides (MO2). Silicon dioxide (silica) exists as an infinite three-dimensional
network of silicon and oxygen atoms linked by a single bond. Each silicon atom is tetrahedrally surrounded
by four oxygen atoms (fig.). The network structure of SiO2 arises due to silicon’s inability to form p-p bond.
Silica is a high-melting solid existing in three crystalline forms–quartz, tridymite and cristobalite.

Si O Si O Si

O O O

Si O Si O Si

O O O

Si O Si O Si

Fig: Two-dimensional structure of SiO2

Silica is very unreactive. It reacts only with HF and caustic alkali.
4HF + SiO2  SiF4 + 2H2O
SiO2 + NaOH  (Na2SiO3)n + Na4SiO4
The last reaction illustrates its acidic nature. Quartz is important as a piezo- electric material and
is used in gramophone pick- ups, cigarette and gas-lighters and for making crystal oscillators in radios
and computers.

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 Chemistry (s and p-Blocks)

The dioxides of Ge, Sn and Pb are solids and the basicity increases on moving down the group.
GeO2 is acidic, SnO2 amphoteric and PbO2 basic. PbO2 contains Pb(IV) and is an oxidizing agent.
The lower oxides GeO, SnO and PbO are more basic and ionic than the higher oxides. Lead also
forms a mixed oxide, Pb3O4 (red lead). It is represented as 2PbO. PbO2 and contains Pb (II) and Pb (IV).
The interconversion of various oxides of lead is shown by the following chemical reactions :
2PbO2   2PbO + O2
400  415C
6PbO  O2   2Pb3 O4
500C
2Pb3O4  6PbO  O2
Silicates
Silicates are important rock forming minerals and comprise of tetrahedral SiO4 units linked together
by sharing corners and edges. Due to the great strength of the Si-O bond, these minerals are insoluble.
The main structural principles of silicates have been determined by X-ray crystallography. The electro
negativity difference between oxygen and silicon suggests that the bonds are 50% ionic and 50%
covalent. The radius ratio Si4+: O2- is 0.29 suggesting that silicon adopts a coordination number of four
and is sp3 hybridized giving SiO44- units. These may exist as discrete units or polymerize by sharing
oxygen atoms. Some silicon atoms may be replaced by aluminium to give aluminosilicates.
Silicates are classified on the basis of the number of oxygen atoms shared per SiO44-tetrahedron.
The classification of silicates alongwith some important examples are shown in table while some structures
are depicted in Fig.
Table: Classification of Silicates
General
Type Examples Remarks
Formula
Orthosilicates 4- No corners shared; Discrete
SiO4 M2 [SiO4 ], M=Zn, Willemite
M=Be, Phenacite tetrahedral units
M=Mg, Forsterite
M[SiO4 ] M=Zr, Zircon
Pyrosilicates 6- 2 tetrahedra linked by one oxygen
Si2O7 Se2Si2 O7 Thortveitite
Cyclic Silicates (SiO3)n 2n- Ca3[Si3O9] Wollastonite 2 oxygen atoms per tetrahedron are
Ba, Ti [Si3O9] Benitonite shared
Be3Al2 [Si6O18 ] Beryl
Chain Silicates (SiO3)n 2n- Spodumene LiAl (SiO3 )2 2 oxygen atoms per tetrahedron
a) pyroxene Enstatite Mg2 (SiO3 )2 shared – single chain structures
b) Amphibole (Si4O11 )n 6n- Tremolite Ca2Mg5 (Si4 O11 )2 Some tetrahedra share 2 oxygens,
(OH)2 some 3; double chain fibrous
II III minerals
Crocidolite Na2 Fe3 Fe2
(Si4O11)2 (OH)2 (Asbestos)
Sheet Silicates 2n- Clay, White asbestos, Mica, 3 oxygen atoms per tetrahedron
(Si2O5 )n
Talc shared minerals are soft & cleave
into sheets
3 dimensional silicates - Feldspar, Zeolite, ultramarine 4 oxygen atoms per tetrahedron
shared. Some Si atoms replaced by
Al

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 Chemistry (s and p-Blocks)

Tetrahedral unit
(a) (b) (c)

(d) (e) (f)

4 -
Fig: Some typical silicate structures (a) Orthosilicate SiO4 (b) Pyrosilicate Si2O76-
(c-d) Cyclosilicates (SiO3)n2n- (e) Chain Silicate (SiO3)n2n- (f) Sheet Silicate (Si2O5)n2n-
The importance of silicates becomes apparent if we realize that asbestos, mica, zeolites, igneous
rocks are all silicates. The cement, glass and ceramic industry are also based on silicates.
Organometallic compounds.
The elements have a fairly extensive organometallic chemistry. Due to inert pair effect the divalent
state is more stable for the heavier members, however all organometallic compounds of tin and lead
contain the element in the tetravalent state.
Alkyl silicon chlorides (RSiCl3, R2SiCl2, R3SiCl and SiR4) are well – known. They are starting
materials for an important class of organo silicon polymers referred to as silicones. Silicones contain
long chains or rings of alternating silicon and oxygen atoms with alkyl or aryl groups attached to silicon.
They are prepared by hydrolysis of alkyl substituted chlorosilanes or alkyl silicon chlorides.
R R

Cl Si Cl + 2H2O HO Si OH + 2HCl

R R

R R R R

HO Si O H + HO Si OH HO Si O Si OH
H2 O

R R R R
Polymerization

R R R

O Si O Si O Si O

R R R

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 Chemistry (s and p-Blocks)

The chain size can be limited by adding R3SiCl. This hydrolyses to give R3SiOH, which has only
one active -OH group. It attaches itself to one side of the chain and since there is no functional – OH
group on this side of the chain, the chain cannot grow at this end. Eventually the other end also gets
blocked. Hydrolysis under controlled conditions gives cyclic polymers having three to six silicon atoms.
R R

R O R R Si O Si R
Si Si
R R
O O
O O
Si
R Si O Si R
R R

R R
Cross- linked polymers are also known and are obtained when some RSiCl3 is hydrolyzed
alongwith R2SiCl2.
Silicones are thermally and chemically inert due to stable Si-O linkage and a strong Si-C bond.
They have oxidative stability, resistance to low and high temperature, excellent water repellency, good
dielectric properties, desirable anti-foam and non-stick properties and physiological inertness. They can
be made in the form of fluids, greases, emulsions, elastomers and resins (depending on chain length
and extent of cross- linkage). They are used as water repellents for treating masonry, buildings and
fabrics Due to their anti - foam properties and non- toxicity they are used to reduce the froth in refining
of cooking oil, fermentation processes, textile dyeing and sewage disposal. Other applications include
their use as hydraulic fluids, light duty lubricants dielectric insulating material and non- stick coating
material for utensils. Silicones are the most important inorganic polymers and their worldwide production
is about 550,000 tons .Over 100 different silicone products are commercially available. Another important
organometallic compound is tetraethyl lead Pb(Et)4. This was used as an “anti-knock” agent to increase
the octane number of petrol. Its use has been banned now as burning “leaded fuel” releases large
amounts of toxic lead salts. Organotin compounds (R2SnX2 and R3SnX) are used to stabilize PVC
plastics and as fungicides and pesticides.
Complex formation
Carbon has a maximum coordination number of four and can accommodate eight electrons in
the valence shell. It cannot increase its coordination number and forms no complexes. The other members
have vacant d orbitals and can increase their coordination number to six and form complexes like [SiF6]2,
[GeF6]2-, [GeF4.(NMe3)2], [SnCl6]2- and [PbCl6]2-.
VSEPR theory suggests an octahedral structure based on sp3d2 hybridization.
3s 3p 3d
Outer electronic
Configuration of
Si (ground state)

Si atom (excited state)

SiF4 (Si gains 4

electrons from
4 F atoms
2 coordinate bonds
2–
[SiF6] (Si gains
4 electrons more
2 pairs from
2 F atoms) 3 2
sp d hybridization

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 Chemistry (s and p-Blocks)

Internal  – bonding using d orbitals

Lateral overlaps of p orbitals give a p-p bond. This is common for carbon and we have already
seen that a few compounds containing> Si = Si< are known. Under suitable conditions p and d orbitals
undergo lateral overlap to give a p- d bond. The compounds trimethylamine (CH3) 3N and trisilylamine
(SiH3 )3N have similar formulae but their shapes are completely different (fig). The former has a pyramidal
structure based on sp3 hybridization of nitrogen. The electronic structure of N in trimethylamine is

1s 2s 2p

The three unpaired electrons in 2p orbitals form bonds with – CH3 groups. However trisilylamine
has a planar structure based on sp2 hybridization. The lone pair of electrons occupies a p orbital
perpendicular to the plane of the molecule and overlaps with empty d orbital on the silicon atoms (fig).
The electronic structure of N atom becomes
1s 2s 2p

2
sp hybridization
The unshared electron pair present in the 2p orbital of N is donated to a vacant 3d orbital on Si
to form a p-d bond. This is not possible in (CH3) 3N as carbon does not have d orbitals.

–
+
H3Si SiH3 Si
– + +
N Si + – +
N N
H3 C CH3 Si
–

+ – + –
+
CH3 SiH3
(a) (b) (c)
Fig: Shapes of (a) Trimethylamine (b) Trisilyamine (c) p -d  bonding in trisilylamine

Group 15
The elements in this group are nitrogen, phosphorous, arsenic, antimony and bismuth. Nitrogen
is the most important component of the earth’s atmosphere (78.1% by volume). Both nitrogen and
phosphorous are essential constituents of plant and animal tissues. The last three elements had long
been isolated and studied extensively by alchemists.
The elements span the range from non-metallic (nitrogen and phosphorous) to the metallic
(bismuth). Arsenic and antimony have intermediate properties and are referred to as metalloids. The
elements have five electrons in their outermost shell. Some selected physical properties are shown in
table.

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 Chemistry (s and p-Blocks)

Table: Physical Properties of Group 15 Elements

Property N P As Sb Bi
Atomic Number 7 15 33 51 83
2 3 2 3 10 10 14
Electronic Configuration [He]2s 2p [Ne]3s 3p [Ar]3d [Kr]4d [Xe]4f
2 3 2 3 10 2 3
4s 4p 5s 5p 5d 6s 6p
Covalent Radius (pm) 70 110 121 141 148
Ionization Energy (KJ mol-1) 1402 1012 947 834 703
Electron Affinity (KJmol-1) -7 72 78 103 91
Electronegativity 3.06 2.05 2.21 1.98 2.01
0
Melting Point ( C) -210 44 * 631 271
0
Boiling Point ( C) -195.8 280.5 * 1587 1564

Nitrogen is a colourless diatomic gas having a triple bond, which confers unusual stability. For
more than a century the only isolable chemical species containing only nitrogen were N2 and the azide
ion, N3–. In 1999 the product N5+ was reported to be formed in the following reaction.
N2F+ [AsF6]– + HN3   N5+ [AsF6]– + HF
The N5+ ion is stable below – 78oC and has a V – shaped structure as shown

N ]+
N N

N N

The N22 – ion has also been characterized in 2002. In SrN2 the bond distance is 122.4 pm.

Allotropy
Phosphorous has many allotropes, the most common being while phosphorous existing as
discrete tetrahedral P4 molecules in the gaseous, liquid and solid states. It is soft, waxy and highly
reactive and glows in moist air emitting a greenish – yellow light. This phenomenon is called
phosphorescence and is the origin of the name of the element. It is stored under water. At very high
temperature P4 molecules dissociates to P2:
P

P P 2P P

P
Condensation of the vapours gives brown phosphorous, which probably contains P2 molecules.
If white phosphorous is heated in absence of air, red phosphorous is obtained. It exists in a variety of
polymeric modifications. The most thermodynamically stable form is black phosphorous obtained by
heating white phosphorous at high pressure. It is inert having a layer structure examples of these
structures are shown in fig.

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 Chemistry (s and p-Blocks)

Orthorbombic

Rhombohedral Cubic

Fig: Allotropes of Phosphorus

Arsenic, antimony and bismuth exist in several allotropic modifications. Arsenic vapour contains
tetrahedral As4 molecules. In the solid state it exists in a yellow form comprising of As4 molecules and
a stable grey () form having a rhombohedral structure. Antimony exists in  form and another form
having hexagonal close packed structure. Bismuth exists in  – form and a form having body- centred
cubic structure.
Bismuth is the heaviest element to have a stable, non-radioactive nucleus. All other heavier
elements are radioactive. The liquid form of bismuth expands on solidification.
Oxidation states and bond type
The elements exhibit a maximum oxidation state of five towards oxygen by utilizing all valence
electrons towards bond formation. Trivalency is important for heavier members (inert pair effect). They
show oxidation states of three and five towards halogens and sulphur and three towards hydrogen.
Nitrogen exhibits a range of oxidation slates from -3 to +5 e.g. NH3 (-3), N2H4 (-2), NH2OH (-1), N2 (O),
N2O (+1), NO (+2), HNO2 (+3), NO2(+4) and HNO3 (+5). It exists in three anionic forms N3- (nitride), N-
3
(azide) and N2-2. Nitrides are known for lithium, magnesium and aluminium. Phosphides and arsenides
(Na3P, Ca3As2) are also known.
Most compounds of this group are covalent. The electronic configuration is s2p3 and in compounds
where the oxidation number is +3 e.g. NH3, the element has a lone pair of electrons, which can be
donated, thus such compounds behave as Lewis bases.
The formation of M5+ ions is not energetically feasible but M3+ ions are known for Sb and Bi. The
fluorides SbF3 and BiF3 are ionic solids. The M3+ ion in aqueous solution undergoes partial hydrolysis to
give the oxoion.
H2O
Sb3+ / Bi3  

HCl
 SbO / BiO
  

Nitrogen cannot expand its coordination number beyond four, as only four orbitals are available
in the valence shell. The other elements utilize d orbitals to form species like PCl5, PF6– etc. These are
based on sp3d and sp3d2 hybridization.

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 Chemistry (s and p-Blocks)

Nitrogen can form p-p multiple bonds with itself or with oxygen and carbon. Hence it forms
many compounds for which counterparts among the heavier members are not known. These include
NO–3, NO2–, CN–, N 3–, N2, N2O, NO and NO2. Because nitrogen can form multiple bonds, the oxides N2
O3 and N2O5 exist as monomers while the analogous compounds of P, As and Sb exist as dimers.

Chemical properties
Nitrogen is rather unreactive. The other elements are fairly reactive and some reactions are
shown in table.
Table: Some Reactions of Group 15 Elements

Reagent Reaction Remarks

O2 M+O 2  MxO y N forms NO, P forms P4O 6 & P4O 10, As & Sb

yield M4O 6 while Bi forms Bi2O 3
F2 M + F2  M Fx M = As, Sb, Bi
x=5 for As, Sb, x = 3 for Bl
X2 M + X2  MXx M= P, As, Sb, Bi
(X=Cl, Br, I) x=3 & 5 for P
x=3 for Bi
S M+S  MxS y M= P, As, Sb, Bi
x=4 for P, 2 for others
y=5 for P, 3 for others
KOH P + KOH + H2 O  KH2PO2 + PH3 As reacts with fused KOH giving K3AsO 3 & H2 .
others do not react
H2SO 4 (conc.) As + H2SO4  H3ASO3 P forms H3PO 4 Sb & Bi form M2 (SO 4)3

General trends are not as apparent as in other groups as one encounters with a variety of
elements – non-metals, metalloids and metals.

Compounds
Hydrides
All elements form volatile hydrides of the formula MH3. Nitrogen also forms hydrazine, N2H4 and
hydrazoic acid N3H (fig.)

N H H H

H H N—N—H N—N—N
H H
Ammonia Hydrazine Hydrazoic Acid

Fig: Some hydrides of Nitrogen

On moving down the group from NH3 to BiH3, the central atom becomes larger and effective
overlap with the small 1s orbital of hydrogen decreases. Thus the stability of the hydrides decreases
down the group and their reducing power increases. The bond angle decreases down the group. Some
properties of the hydrides are shown in Table.

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 Chemistry (s and p-Blocks)

Table: Some Properties of Group 15 Hydrides

0 0
m.p. ( C) b.p. ( C) Bond energy Bond Angle Bond length (pm)
-1
(KJmol )
0
NH3 -77.8 -34.5 389 107 48’ 101.7
0
PH3 -133.5 -87.5 318 93 36’ 141.9
0
AsH3 -116.3 -62.4 247 91 48’ 151.9
0
SbH3 -88 -18.4 255 91 18’ 170.7

VSEPR theory predicts pyramidal structure (sp3 hybridization with lone pair on central atom).

ns np
Electronic
Configuration
of M

MH3 molecule

3
sp hybridization
Due to the presence of the lone pair, the bond angle is less than the normal tetrahedral bond
angle. On moving down the group, the electronegativity of the central atom decreases, the bond- pair
tends to move away from the central atom, the lone pair is more tightly held causing greater distortion
and is reflected by the decrease in bond angle down the group. The lone pair on the central atom can
be donated and the elements act as Lewis bases. However, on descending the group, as the lone pair
is more tightly held, the donor properties of the hydrides decreases. Thus phosphine is a much weaker
base than ammonia.
Ammonia is one of the most highly- produced inorganic chemicals. The Haber- Bosch Process
manufactures most of it synthetically from nitrogen and hydrogen. A small amount is obtained during coal
gas purification and during production of coke from coal. The worldwide production in 2004 was 109,000,000
tons, the chief producer being China followed by India. About 80% or more of the ammonia produced is
used for fertilizing agricultural crops. The main fertilizers manufactured from ammonia are urea, ammonium
nitrate, ammonium phosphate and ammonium sulphate. Ammonia is also used for the production of
many inorganic and organic chemicals, plastics, fibres, explosives and intermediates for dyes and
pharmaceuticals. Synthetic ammonia is the key to the production of most nitrogen compounds as shown
below.

HYDRAZINE HYDROXYLAMINE

AIR NITROGEN AMMONIA NITRIC OXIDE NITROGEN DIOXIDE

AMMONIUM SALTS NITRITES NITRATES

UREA

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 Chemistry (s and p-Blocks)

Hydrazine is prepared by the action of sodium hypochlorite on ammonia in presence of a small

amount of glue or gelatin, which suppresses the side reactions:
NH3 + NaOCl  NH2Cl + NaCl + H2O
NH3 + NH2Cl + NaOH ---- N2H4 + NaCl +H2O
Side reactions: Hydrazine
N2H4 + 2NH2Cl  N2 + 2NH4Cl
3NH2Cl + 2NH3  N2 + 3NH4Cl
Oxidation of hydrazine is highly exothermic
N2H4 + O2   N2 + 2H2O H = – 622 KJ mol-1
Advantage has been taken of this reaction in the major use of hydrazine and its methyl derivative,
in rocket fuels. Hydrazine is a convenient reducing agent. It can also act as a coordinating ligand forming
complexes with transition metals. Phosphorous forms an unstable hydride diphosphine, P2H4, which has
very little similarity with hydrazine.
Hydrogen azide (hydrazoic acid HN3) is an unstable compound, which decomposes on heating
2HN3  H2 + 3N2
It is slightly more stable in aqueous solution and behaves as weak acid forming salts known as
azides. Sodium azide is obtained by reaction of sodamide with nitrous oxide.
2NaNH2 + N2O  NaN3 + NaOH + NH3
2NaN3 + H2SO4  2HN3 + Na2SO4
The acid and some its salts are explosive in nature. Ionic azides are more stable than covalent
azides as a greater number of resonating structures can be drawn for the former.

Halides
Two series of halides are known – the trihalides (MX3) and pentahildes (MX5). The trihalides are
known for all the elements and can be prepared by direct combination. But if the halogen is in excess
than the pentahalide is formed in addition. The trihalides are all covalent apart from BiF3 that is ionic.
SbF3 and the other halides of bismuth have partial ionic character. The central atom is sp3 hybridized
and the shape is pyramidal (like NH3).
Apart from NF3 that is very stable the trihalides hydrolyze but the products vary.
NCl3 + 3H2O  NH3 + 3HOCl
PCl3 / AsCl3 + 3H2O  H3PO3 / H3AsO3 + 3HCl
SbCl3 / BiCl3 + H2O  SbOCl / BiOCl + 2HCl
The different products obtained in case of hydrolysis of NCl3 and PCl3 is due to a difference in
mechanism, which results in formation of different intermediates.

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 Chemistry (s and p-Blocks)

H
|
H—O

N N
Cl Cl +H2O Cl Cl (Hydrogen bonded intermediate)
Cl Cl

N
Cl H +HCl
Cl NH3 + 2HOCl

OH2

P P P
Cl Cl +H2O Cl Cl Cl OH + HCl
Cl Cl Cl
2H2O
P
OH OH +2 HCl
OH
In a case of SbCl3 and BiCl3 the hydrolysis is incomplete and may be repressed on adding HCl.
Nitrogen does not form pentahalides due to non – availability of d orbitals. Due to inert pair effect
pentahalides of bismuth are less stable and only BiF5 is known. The pentahalides of phosphorous are
well characterized. In the gaseous phase they have trigonal bipyramidal structure (fig.)

Cl Cl

P
P
Cl Cl Cl
Cl Cl
Cl
Fig: Structures of PCl3 and PCl5
This structure is retained in the solid state for PF5 but PCl5 dimerises in the solid state and exists
as [PCl4]+[PCl6]-
Phosphorous pentachloride is the most important pentahalide and is obtained by treating
phosphorous trichloride with chlorine.
PCl3 + Cl2  PCl5
It hydrolyses readily.
PCl5 + H2O  POCl3 + 2HCl
POCl3 + 3H2O  H3PO4 + 3HCl
Phosphoric acid
It is widely used in organic synthesis as a halogenating agent.
ROH + PCl5  RCl + POCl3 + HCl
RCOOH + PCl5  RCOCl + POCl3 + HCl

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 Chemistry (s and p-Blocks)

Nitrogen oxides and oxo acids

The common oxides and oxoacids of nitrogen are summarized in Table and their structures are
also depicted there.
Table: Oxides of Nitrogen

Formula Name Structure Remarks

N 2O Nitrous Oxide N N O Oxidn.state + 1
(O.S.)
NO Nitric Oxide N O O. S + 2
Bond order 2.5 Paramagnetic
N2O3 Nitrogen Sesquioxide O O O.S + 3
N—N Dissociates readily to NO &
NO 2
O
NO2 Nitrogen Dioxide N O.S + 4
Paramagnetic
O O
Following equilibrium presents
2NO2 = N2O 4
N2O4 Dinitrogen Tetraoxide O O O.S + 4
Dissociates to NO2
N—N
O O
N2O5 Dinitrogen Pentoxide O O O.S + 5
N-O-N may be bent. Exists as
N—O— N + –
NO 2 NO 3 in solid state
O O

They all exhibit p-p multiple bonding between nitrogen and oxygen atoms. The other elements
of Group 15 cannot form such bonds and consequently nitrogen forms a number of compounds for
which P, As, Sb or Bi analogues are not known. Oxides in lower oxidation state are neutral while those
in higher oxidation states are acidic.
Nitrous oxide, N2O, is obtained by the thermal decomposition of ammonium nitrate
NH4NO3  N2O + 2H2O
It is used as a mild dental anaesthetic and propellant for aerosols. On atmospheric decomposition
it releases nitrogen and oxygen that are environment friendly . However N2O contributes to green house
effect.
Nitric oxide is obtained by the action of dilute nitric acid on copper.
3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O
It is released during combustion of fossil fuels and is present in exhausts of automobiles and
power plants. It is also obtained by action of lightning on atmosphere nitrogen and oxygen. The NO is
slowly oxidized to NO2, these two gases are collectively referred to as NOx and contribute to the problem
of acid rain and destruction of ozone layer. It is a neutral oxide and is an important intermediate for
manufacture of nitric acid by catalytic oxidation of ammonia. It is an odd electron molecule and forms
coordination complexes with metal ions. One such complex [Fe(H2O)5NO]2+ is responsible for the colour
in the “brown ring” test for nitrates.
Nitrogen dioxide, NO2 is a toxic gas obtained by thermal decomposition of lead nitrate.
2Pb(NO3)2  2PbO + 4NO2 + O2

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It is an odd electron molecule and dimerizes to give N2O4. At ordinary temperature and pressure,
both exist in significant amounts in equilibrium:

N2O4 (g) 

 2NO2 (g)



Colourless, diamagnetic N2O4 has a weak N-N bond that can readily dissociate on warming to
give the brown, paramagnetic NO2. N2O4 is an acidic oxide and dissolves in water to give a mixture of
nitrous and nitric acids.
N2O4 + H2O  HNO2 + HNO3
The two important oxo acids of nitrogen are nitrous acid, HNO2 and nitric acid, HNO3. Nitrous acid
is a weak acid and is obtained by acidifying a nitrite or by passing an equimolar mixture of NO and NO2
into water.
Ba(NO2)2 + H2SO4  2HNO2 + BaSO4 (s)
NO + NO2 + H2O  2HNO2
The acid disproportionates on heating
3HNO2  HNO3 + 2NO + H2O
Nitrous acid and nitrites are good oxidizing agents and oxidize iodide to iodine, Fe (II) to Fe (III)
and Sn (II) to Sn (IV), e.g.
2KI + 2HNO2 + 2HCl  2H2O + 2NO + 2KCl + I2
However, strong oxidizing agents like KMnO4 oxidize nitrites to nitrates.
2KMnO4 + 5 KNO2 + 6HCl  2MnCl2 + 5KNO3 +3H2O + 2KCl
The nitrite ion forms complexes with metals. Coordination to metal ions occurs either through
nitrogen or oxygen.
Nitric acid is of immense industrial importance. It is synthesized by the Ostwald (Nobel Prize
1909) process through the following set of reactions.
4NH3 + 5O2  4NO + 6H2O (Pt-Rh catalyst)
1000C
2NO  O2   2NO2
3NO2 + H2O  2HNO3 + NO
In the first step, a catalyst specific for NO formation is taken; other wise NH3 is oxidized to N2
4NH3 + 3O2  2N2 + 6H2O
HNO3 is a strong acid undergoing complete dissociation in dilute aqueous solution.
HNO3 + H2O  H3O+ + NO3–
It is an excellent oxidizing agent particularly when hot and concentrated. A mixture of concentrated
HNO3 and concentrated HCl in 1:3 ratios is called aqua regia and noble metals like gold and platinum
dissolve in it. The reactions of HNO3 with some metals and non-metals are summarized in table.

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 Chemistry (s and p-Blocks)

Table: Some Reactions of Nitric Acid

Reactant Reaction Remarks

M = Mg, Mn M + 2HNO3  M(NO3 )2 + H2 Very Dilute Acid
M = Zn, Fe, Sn 4M + 10HNO3  4M(NO3 )2 + 5H2O + N2 O Dilute acid
5M + 12HNO3  5M(NO3 )2 + N2 + 6H2O (Oxidizing agent)
4M + 10HNO3  4M(NO3 )2 + NH4NO3 + 3H2O Very dilute acid
M = Cu, Bi, Hg, Ag 3M + 8HNO3  3M(NO3 )2 + 2NO + 4H2O Dilute acid
M + 4HNO3  M(NO3 )2 + 2NO2 + H2 O Conc. Acid
P P4 + 20HNO3  4H3 PO4 + 20NO2 + 4H2O Conc. Acid
C6 H6 C6 H6 + HNO3  C6H5NO2 + H2 O Conc. Acid
Reaction assisted by adding
conc. H2 SO4

A mixture of concentrated nitric acid and sulphuric acid contains the nitronium ion NO2+ and is
used to nitrate organic compounds.
The major use of nitric acid (~ 75%) is in the manufacture of ammonium nitrate, most of which
is used as a fertilizer. Other uses include manufacture of caprolactam (one of the starting materials for
synthesis of Nylon), manufacture of industrially useful organic nitro compounds (nitroglycerine, nitrocellulose
etc) and manufacture of nitrates for use in explosives, pyrotechnics etc.

Oxides and Oxo Acids of other elements

Phosphorous, arsenic and antimony form oxides in both +3 and +5 oxidation states, whereas only
one oxide of bismuth, Bi2O3 is known. Except for Bi2O3 all other oxides are dimeric. They are obtained
by direct combination. The structures of oxides of phosphorous are shown in fig.
O

P P
O O O O

O O
O O
P P P P
O O
O P O O P O

O
P4O6 P4O10
Fig: Oxides of Phosphorus

The four apical bonds in P4O10 have appreciable double bond character due to p-d overlap.
The basic strength of the oxides increases on moving down the group. The oxides of P and As
are acidic, those of Sb amphoteric and bismuth oxide is basic. Oxides in higher oxidation slates are more
acidic.

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 Chemistry (s and p-Blocks)

Oxoacids of Phosphorous, Arsenic & Antimony

The oxoacids of arsenic and antimony are not well – characterized but their salts are known.
Phosphorous forms two series of oxo acids – phosphoric acid series containing P (V) and phosphorous
acid series containing P (III)
The following generalization can be made:
b) P is sp3 hybridized.
c) Acidic hydrogens are attached to oxygen
d) The bond between P and non-hydroxylic oxygen has appreciable double bond character.
e) The P-H bond confers reducing properties.
Some properties of the oxoacids of phosphorous are summarized in table.

Table: Oxoacids of Phosphorous

Formula Name of Acid Preparation Remarks

H3PO 2 Hypophosphorous White P 4 + alkali Monobasic Reducing
pKa =1.244
H3PO 3 Orthophosphorous P 4O6 or PCl3 + H2O Dibasic, Reducing
pK1 = 1.26
pK2= 6.70
(HPO2)n Metaphosphorous PH3 + O 2 (low pressure) Polymerizes
Structure not known
H4P2O 6 Hypophosphoric Red P + alkali Tetrabasic
pK1 = 2.2
pK2 = 2.8
pK3 = 7.3
pK4 = 10.0
H3PO 4 Orthophosphoric P 4O10 + H2O Tribasic
pK1 = 2.15
pK2 = 7.20
pK3 = 12.37
H4P2O 7 Pyrophasphoric Heat Phosphates or H3PO 4 Tetrabasic
pK1 = 1.0
pK2 = 1.8
pK3 = 6.6
pK4 = 9.6
0
(HPO3)n Metaphosphoric Heat H3PO 4 to 350 C Ring Structure

Some condensed phosphoric acids are known. The PO4 tetrahedra are linked to form chains and
structures of some of these are shown in Fig.

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 Chemistry (s and p-Blocks)

O O O

P P P
HO OH HO O OH
OH OH OH
Orthophosphoric acid Pyro (Dipoly) phosphoric acid

O O

O OH
HO P O P OH
P
O O
O O
O O
P P
HO P O P OH
HO O OH

O O
Cyclotriphosphoric acid Cyclotetraphosphoric acid
Fig: Some oxoacids of Phosphorus
The P – O – P linkage is very important in the biological system, as it is the prime store of energy.
The energy of the bond (29 KJ mol-1) is released by the hydrolysis of adenosine triphosphate.
The world production of phosphates is about 50,000,000 tons. Phosphates find various uses in
the food industry, in water softening, in fertilizers, toothpastes and detergents.
Phosphazenes
Nitrogen and phosphorous show little tendency to catenate by themselves. However they bond
together to form cyclic and long chain polymers called phosphazenes (earlier referred to as phosphnitrilic
polymers) containing alternate phosphorous and nitrogen atoms. In these compounds phosphorous and
nitrogen are present in +5 and +3 oxidation states respectively. They may be prepared by the reaction
between phosphorous pentachloride and ammonium chloride in dichloromethane at 120 to 150 C.
n PCl5 + n NH4Cl  (NPCl2)n + 4n HCl + Cl4P (NPCl2)n.NPCl3
Cyclophosphazene polyphosphazene
The reaction produces a mixture of ring compounds and short linear chains. Among the ring
compounds the trimer and tetramer have been well characterized. The former exists as planar six
membered rings with equal P—N distance (~158pm), considerably shorter than the P – N single bond
(~ 177pm). This indicates a structure similar to benzene. The compound displays aromaticity though
less than benzene. The compound can be expressed as a resonance hybrid, the N atoms are sp2
hybridized and the P atoms are sp3 hybridized.

Cl Cl Cl Cl
P P
N N N N

P P P P
Cl N Cl Cl N Cl
Cl Cl Cl Cl

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 Chemistry (s and p-Blocks)

The tetramer has a puckered structure.

A few chain polymers are:

Cl Cl Cl Cl Cl Cl Cl Cl Cl

Cl --- P = N --- P Cl2 Cl --- P = N – P = N – P Cl2 Cl --- P = N --- P = N --- P = N --- P Cl2

Cl Cl Cl Cl Cl Cl Cl Cl Cl
(a) (b) (c)

Other atoms or groups can replace the Cl atoms. The amino, alkoxy, phenoxy and flouro derivatives
are stable and attracting interest as rigid plastics, plastic films, foams, fibres and elastomers. Such
molecules (molar mass > 500,000) are water repellent, flame resistant, flame resistant have good
dielectric strength and are flexible at low temperatures. Due to these unique properties they have many
potential uses but their cost is prohibitive. After silicones they are the most important inorganic polymers.

Group 16
The first two elements of this group, sometimes referred to as the “chalcogen” group, are familiar
as oxygen, the colourless gas, vital for life and comprising about 21% of the earth’s atmosphere and
sulphur, a yellow non-metallic solid. The third element, selenium is not as well known, but is important
in xerography processes. Tellurium is of less commercial importance, used in small amounts in metal
alloys, tinting of glass and as catalysts in rubber industry. All isotopes of polonium (discovered by Marie
Curie) are radioactive. Non -metallic character is maximum in oxygen and sulphur, weaker in selenium
and tellurium whereas polonium is metallic. Some selected physical properties are shown in Table.

Table: Physical properties of Group 16 elements

Property O S Se Te Po
Atomic Number 8 16 34 52 84
2 4 2 4 10 10 14
Electronic Configuration [He]2s 2p [Ne]3s 3p [Ar]3d [Kr]4d [Xe]4f
2 4 2 4 10 2 4
4s 4p 5s 5p 5d 6s 6p
Covalent radius (pm) 66 104 117 137 146
st -1
Ionization Energy (I ) (KJmol ) 1314 1000 941 869 812
-1
Electron Affinity (KJmol ) 141 200 195 190 180
Electronegativity 3.61 2.58 2.42 2.15 2.10
0
Melting Point ( C) -218.8 112.8 217.0 452.0 250.0
0
Boiling Point ( C) 183.0 444.7 685.0 990.0 962.0

Allotropic forms
Oxygen exists primarily as the diatomic O2 that is paramagnetic, but traces of triatomic O3
(ozone) are found in the upper atmosphere and in the vicinity of electrical discharges. Ozone is diamagnetic
and is formed when oxygen absorbs ultraviolet radiation from the sun.
h
O2  2O

O2  O  O3

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 Chemistry (s and p-Blocks)

Ozone also absorbs ultraviolet radiation and decomposes back to oxygen

2O3  3O2
In the upper atmosphere a steady- state concentration of ozone is achieved which protects the
earth’s surface from ultraviolet radiation. Recently there has been a serious concern about the depletion
of the ozone layer. Oxides of nitrogen (from high- flying aircraft) and chlorine atoms (from decomposition
of chlorofluorocarbons used as aerosols, refrigerants etc.) catalyze the decomposition of ozone.
NO2 + O3  NO3 + O2
NO3  NO + O2
NO + O3  NO2 + O2
Net 2O3  3O2
h
Chlorofluorocarbons  Cl
Cl + O3  ClO +O2
ClO + O  Cl + O2
Net O3 + O  2O2
Ozone is a more powerful oxidizing agent than oxygen. Some diatomic and triatomic ions of
oxygen are known e.g. O2_ (Superoxide), O22_ (Peroxide), O3_ (Ozonide)
More allotropes are known for sulphur than for any other element. The most stable form at room
temperature is orthorhombic or -sulphur. This consists of S8 molecules, arranged in a puckered ring

S S
S

S S
S S S

At 96o C, orthorhombic sulphur is converted to monoclinic or â-sulphur in which the S8 sings are
arranged to give a different structure. Heating sulphur results in interesting changes in viscosity. At 119oC,
a yellow liquid is obtained whose viscosity decreases up to 155obecause of increased thermal motion.
The viscosity increases sharply above 159oC till about 2000C, when it again decreases with the liquid
acquiring a reddish tinge at high temperature. This variation in viscosity involves the tendency of S-S
bonds to break and reform at high temperature. Above 159oC, the S8 rings open giving chains, these
react among themselves to give S16 chains, S24 chains and so on. At about 180oC, when the liquid has
maximum viscosity, chains exceeding 200,000 sulphur atoms are known. The longer the chain, the
greater is the viscosity. At higher temperatures, these chains breaks and the viscosity decreases. When
molten sulphur is poured into cold water, a rubbery solid, plastic sulphur or -sulphur is obtained.
General group Trends
The size of the Group 16 elements increases down the group as extra shells of electrons are
added. The ionization enthalpy decreases as the size of the atom increases. The ionization enthalpies
of the Group16 elements are strikingly less than these of the corresponding Group 15 elements. This
is attributed to the fact that Group15 elements have ns2 np3 configuration, the p orbitals are half filled
conferring extra stability and consequently removal of an electron is difficult. The electronegativities
decrease with increasing atomic number. Thus in view of the fall in electronegativity, metallic character
within the group increases with increase in atomic size.
The large difference in melting and boiling points between oxygen and sulphur can be explained
on the basis of their structure. Oxygen exists as diatomic molecules and the bond energy of O=O is very
high (498 KJ mol-1). The molecules are held by weak van der Waal’s forces. Sulphur exists as S8, the

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 Chemistry (s and p-Blocks)

S-S bond energy (264 KJ mol-1) is greater than O-O bond energy (142 KJ mol-1). Thus sulphur has
greater catenation power than oxygen and higher melting and boiling points.
Oxidation states and Bond type
The elements have outermost electronic configuration of ns2 np4 and can achieve noble gas
configuration by gaining two electrons forming M2- ion or by acquiring a share in two electrons by forming
two covalent bonds. The M2- ion is known for oxygen (which is highly electronegative) and to a lesser
extent for sulphur. Sulphur, selenium and tellurium show +2, +4 and +6 oxidation states. The +4 and +6
oxidation states are realized by utilizing vacant d orbitals. Oxygen always displays -2 oxidation state in
metallic and non-metallic oxides except in OF2 where it shows +2 oxidation state. This is because
fluorine is more electronegative than oxygen.
Oxygen, and to a lesser extent, sulphur differ from other members in their ability to catenate and
form peroxides H-O-O-H and polysulphides, H2Sn (n=2 to 8) respectively.
The tendency to form multiple bonds decreases down the group. Carbon dioxide (O=C=O) is
very stable, carbon disulphide is moderately stable, the corresponding selenium compound is less stable
whereas the tellurium compound is not known.
The bond between sulphur and oxygen are shorter than a single bond. In addition to the ó - bond
between the elements, a ð-bond is formed by overlap of filled 2p orbitals of oxygen with a vacant 3d-
orbital of sulphur. This is called a pð -dð bond. The sizes and energies of the 2p orbital of oxygen and
3d orbital of sulphur are comparable allowing effective overlap.

2p 3d
of O of S
(Filled) (Vacant)

Compounds Hydrides
Binary hydrides of general formula H2X are known for all elements. They are angular in shape (sp3
hybridization with two lone pairs) (Fig). The bond angles decrease down the group (Table).
Table: Some Properties of Group 16 Hydrides

0 Enthalpy of formation
Boiling Point ( C) -1 Bond angle (H-M-H)
(KJmol )
H 2O 100 -242 104.5°
H 2S -60 -20 92°
H2Se -42 +81 91°
H2Te -2.3 +154 90°

The bond angle is lower than the tetrahedral bond angle (109.50) due to greater repulsion between
the lone pairs. On moving down the group, the electro negativity of the Group 16 element decreases,
the bond pair moves away from the central atom, the lone pair is more tightly held causing greater
distortion. For lower hydrides, the bond angle approaches 900 suggesting that almost pure p-orbitals are
used in bond formation. The thermal stability and bond enthalpy of the hydrides decreases down the
group and the acidic nature increases. The abnormally high boiling point of water is due to intermolecular
hydrogen bonding.

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 Chemistry (s and p-Blocks)

Oxygen forms another hydride, H2O2 (Fig)

94°
O
H
97° 97°
O H
109.5°

H H
(a) (b)
Fig: The Structures of (a) H2 O (b) H2 O2
It decomposes readily and is a strong oxidizing agent
H2O2   2H2O + O2
Halides
The elements form a number of compounds with halogens (Table)
Table: Binary Halides of Group 16 Elements
Fluorides Chlorides * Bromides * Iodides *
O OF2, O2 F2 Cl2O, ClO2 Br2 O, BrO2 I2 O4, I2O5
Cl2O6 Cl2 O7 BrO3 I4 O9
S S2F2, SF2, SF4 , SF6 , S2Cl2, SCl2 S2Br2 -

S2F10 SCl4
Se Se2f2 , SeF4 Se2Cl2, SeCl2 Se2Br2 , SeBr2 -

SeF6 SeCl4 SeBr4

Te TeF4, TeF6 TeCl2 , TeCl4 TeBr2 , TeBr4 Tel2 , Tel4
Po - PoCl2 , PoCl4 PoBr2, PoBr4 PoI4
* in case of oxygen, oxides
The binary compounds of oxygen with halogens are covalent. The structures of some halides are
shown in Fig.
F F
Cl
F F F
S S S S S
F F F
Cl Cl Cl
F F
(a) (b) (c) (d)
Fig: The structures of some sulphur halides
The highest oxidation state of +6 is realized only with fluorine, SF6 is inert due to a sterically
hindered sulphur atom in an octahedral structure (sp3d2 hybridization). It is unaffected by water as the
protected sulphur atom does not allow hydrolysis, a thermodynamically favoured reaction. On the other
hand SeF6 and TeF6 are more reactive and TeF6 is hydrolyzed due to large size of Te. This allows the
formation of an intermediate with higher coordination number.

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 Chemistry (s and p-Blocks)

Oxides
Oxygen reacts with practically all elements in the periodic table, except lighter noble gases, to
form oxides. Oxides may be classified as:
iii) Normal oxides - Here oxygen shows oxidation state of –2. They may be ionic or covalent
eg. CaO, CO2,
iv) Peroxides - These contain O-O linkage eg. H2O2, Na2O2
v) Suboxides - They involve bonds between atoms of the element, in addition to bonds
between element and oxygen e.g. C3O2 (O=C=C=C=O)
vi) Superoxides - They contain O-2 ion and are formed by some alkali metals eg. KO2
Oxides may also be classified as acidic, basic, neutral or amphoteric depending on their reaction
with water.
Acidic oxides (oxides of non-metals) dissolve in water giving acidic solution and react with bases
forming salt and water eg CO2, SO2, SO3, and NO2 etc.
SO3 + H2O  H2SO4
SO3 + 2NaOH  Na2SO4 + H2O
Basic oxides (oxides of metals) may dissolve in water to give alkaline solutions. They all dissolve
in acids to give salt and water eg. Na2O, MgO etc.
Na2O + H2O  2NaOH
Na2O + 2HCl  2NaCl + H2O
Amphoteric oxides dissolve in both acids and bases eg. Al2O3, ZnO etc.
ZnO + 2HCl  ZnCl2 + H2O
ZnO + 2NaOH + H2O  Na2 [Zn(OH)4]
Al2O3 + 6HCl  2AlCl3 +3H2O
Al2O3 + 2NaOH + 3H2O  2Na [Al(OH)4]
Neutral oxides have neither acidic nor basic properties eg. CO, N2O.
The elements of Group 16 form several oxides, which are listed in table, whilst the structures of
some important ones are shown in Fig.

Table: Oxides of Group 16 Elements

Element MO 2 MO3 Other Oxides

S SO2 SO 3 S n O (n=2, 6 to 10)
Se SeO2 SeO 3
Te TeO 2 TeO3 Te O
Po PoO2 Po O

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 Chemistry (s and p-Blocks)

O
S O O O
98º 90º
O O Se Se Se
90º

O O
(a) (b)

O O
O
O
S S S
O
O O O O
S
O O
O
(c) (d)

Fig: The Structures of (a) SO2 (gaseous) (b) SeO2 (solid)

(c) SO3 (gaseous) (d) Trimer of SO3 (solid)

The dioxides and trioxides of S and Se have been well characterized. Sulphur dioxide and
selenium dioxide are acidic in nature whereas tellurium dioxide is amphoteric. This illustrates increase
in basic character on descending a group. SO2 contains sulphur in +4 oxidation state and may act as
both reducing and oxidizing agent depending on the other reactant. The following reactions illustrate this.
a) As reducing agent:
K2Cr2O7 + 3SO2 + H2SO4  K2SO4 + Cr2 (SO4)3 + H2O
2FeCl3 + SO2 + 2H2O  2FeCl2 + H2SO4 + 2HCl
b) As oxidizing agent:
2SO2 + H2S  H2SO4 + 3S
SO2 + C  CO2 + S
The most important trioxide is SO3, which is used in the manufacture of H2SO4. It is an acidic
oxide and a powerful oxidizing agent and can oxidize HBr to Br2 and P to P4O10.

Oxoacids of Sulphur
Sulphur forms a large number of oxoacids which are listed in Table. Many do not exist in the free
state but are known as anions of salts. The oxidation state of sulphur may vary form - 2 to +6.

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 Chemistry (s and p-Blocks)

Table: Oxoacids of Sulphur

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 Chemistry (s and p-Blocks)

Sulphurous Acid (H2SO3)

Though SO2 is highly soluble in water, most of it is present as SO2 . H2O (hydrate) and H2SO3
exists in minutes amounts. However its salts, sulphites (SO32-) and hydrogen sulphites (HSO3-) are well
known. Sulphurous acid possesses both oxidizing and reducing properties. It reduces iodine to HI,
KMnO4 to MnSO4 (decolorizes KMnO4) and K2Cr2O7 to Cr2(SO4)3 (turns K2Cr2O7 green).
H2SO3 + H2O + I2  H2SO4 + 2HI
2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO4 + 2H2SO4
K2Cr2O7 + 3SO2 + H2SO4   K2SO4 + Cr2(SO4)3 + H2O
In the presence of strong reducing agents it behaves as an oxidizing agent.
2H2S + H2SO3  3H2O + 3S
The sulphite ion has a pyramidal structure that is tetrahedral with one position occupied by a lone
pair. The bond angle O-S-O is slightly distorted (1060) due to lone pair. The bond length (151 pm)
indicates double bond character.
Electronic structure of sulphur atom excited state

O O (-) sp3 Forms -

O Hybridization bond
(-)

Sulphuric acid is a very important industrial chemical. It is a colourless, viscous liquid, a strong
acid oxidizing agent and a powerful dehydrating agent. Some reactions of H2SO4 are shown in Table.

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 Chemistry (s and p-Blocks)

Table: Some Reactions of Sulphuric Acid

Reactant Reaction Remarks

Zn Zn + H2SO4  ZnSO4 + H2 Dilute Acid
Cu Cu + 2H2 SO4  CuSO4 + 2H2 O + SO2 Concentrated acid
C C + H2 SO4  CO + SO2 + H2 O Concentrated Acid
(oxidizing agent)
NaBr 2NaBr + 2H2 SO4  2NaHSO4 + Br2 Concentrated Acid
(oxidizing agent)
NaI Similar reaction
Sugar C12 H22O11  12C + 11H2 O Concentrated Acid
(dehydrating agent)

H2SO4 is a dibasic acid forming two series of salts, hydrogen sulphate (HSO4-) and sulphate
(SO42-). The SO42- ion has a tetrahedral structure

O O (-)
O
(-)
The worldwide production of sulphuric acid is ~ 180 million tons. It is used in fertilizer production,
in the manufacture of chemicals, polymers, soaps and detergents, paints pigments dye intermediates
and in petroleum refining.

Compounds of Sulphur and Nitrogen

Compounds containing sulphur –nitrogen rings are an area of considerable interest. N and S are
diagonally related in the periodic table and have comparable charge densities and electronegativities. The
compounds formed have unusual structures, which cannot be explained by the usual bonding theories.
The best known is tetrasulphur tetranitride, S4N4 that is obtained as follows:
6SCl2 + 16NH3  S4N4 + 2S + 14 NH4Cl
CCl4
6S2Cl2  16NH3   S 4N4  8S  12NH4 Cl
6S2Cl2 + 4 NH4Cl  S4N4 + 8S + 16 HCl
S4N4 is a thermo chromic solid i.e. changes colour with temperature – colourless at liquid nitrogen
temperature, orange at room temperature and red at 1000C. It is stable in air, but may detonate with
shock or friction, it exists as a cradle –shaped ring (Fig). The average S-N bond length (162 pm)
indicates delocalized double bond character. The S ---- S distances at top and bottom of cradle are ~258
pm indicating weak S-S bonding. S4N4 is thus a cage structure.

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 Chemistry (s and p-Blocks)

S S

N N
N N

S S
Fig: The Structure of S4 N4
S4N4 is slowly hydrolyzed by water, but reacts rapidly with warm NaOH when the cage breaks.
S4N4 + 6NaOH + 3H2O  Na2S2O3 + 2Na2SO3 + 4NH3
Reduction of S4N4 with tin (II) chloride gives tetrasulphur tetraimide, S4(NH)4 isoelectronic with S8
and existing in a crown configuration.
S4N4 on oxidation with chlorine produces trithiazyl trichloride.
3S4N4 + 6 Cl2  4N3S3Cl3
If S4N4 is vaporized under reduced pressure and passed through silver wool, disulphur dinitrogen,
S2N2 is obtained
S4N4 + 4Ag  S2N2 + 2Ag2S + N2
It is a crystalline solid having a cyclic structure

Anomalous Behaviour of Oxygen

Oxygen differs in certain aspects form the other members of the group. This is mainly due to its
small size, high electronegativity and non-availability of d orbitals. The main differences are
 Oxygen is a diatomic gas, others are polyatomic solids
 Oxygen always shows negative oxidation state (-2) except in compounds with fluorine,
where it shows positive oxidation state (eg. In OF2, oxidation state is +2)
 Oxygen has a tendency towards extensive hydrogen bond formation.

Group 17
The elements in this group are non-metallic in nature. The group comprises of fluorine, chlorine,
bromine, iodine and astatine. The last element is radioactive. They are collectively known as halogens
(Greek, halos + gen, salt former). The most common compound containing a halogen is sodium chloride
(common salt), known since antiquity. Due to high reactivity, halogens do not occur free in nature but
in form of salts (halides).
The elements have seven electrons in their outermost shell (ns2 np5 ). They acquire noble gas
configuration by either gaining an electron to form halide ion, or acquiring a share in one electron by
forming a covalent bond. All natural halogens are diatomic. Some physical properties of halogens are
summarized in Table.

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 Chemistry (s and p-Blocks)

Table: Physical properties of Group 17 elements

Property F Cl Br I
Atomic Number 9 17 35 53
Electronic Configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d10 5s 25p5
2 5 2 5 10 2 5

Covalent radius (pm) 64 99 114 133

st -1
Ionization Energy (I ) (KJ mol ) 1681 1251 1140 1008
-1
Electron Affinity (KJ mol ) 333 349 325 295
Electronegativity 4.19 2.87 2.68 2.36
0
Melting Point ( C) -218.6 -101 -7.25 113.6 *
Boiling Point (0 C) -188.1 -34 59.5 185.2
-1
H dissociation (KJ mol ) 158.6 242.6 192.8 151.1

General group Trends

The halogens are all coloured. Fluorine and chlorine are pale –yellow and yellowish –green gases
respectively; bromine is a dark-red liquid and iodine a black, lustrous solid that readily sublimes giving
a purple vapour.
The halogens are the smallest atoms in the respective periods of the periodic table and the size
increases with increase in atomic number. The halogens have very high electronegativity values, which
decrease with increase in size. Fluorine is the most electronegative element in the periodic table.
Halogens need one electron to complete the octet, thus the electron affinity values are high. The
electron affinity decreases from chlorine to iodine. The electron affinity of fluorine is less than that of
chlorine; this is because of the small size of the fluorine atom, which makes the incoming electron
encounter a lot of electron – electron repulsion.
The X-X bond dissociation enthalpy decreases from Cl2 to I2. The value for F2 is abnormally low
and it is likely that the weakness of the F-F bond is largely a consequence of repulsions between the
nonbonding electron pairs. The low bond enthalpy is responsible for the high reactivity of fluorine.

Oxidation States
Fluorine is the most electronegative element and always shows an oxidation state of -1. This
oxidation state is the most common and stable state for all halogens. The other members display
positive oxidation states (+1) with oxygen or fluorine. They can also display oxidation states of +3, +5
and +7 by utilizing vacant d orbitals. Positive oxidation states are displayed in halogen oxides and
interhalogens. Oxidation states of +4 and +6 are less common and displayed in ClO2, BrO2, I2O4, Cl2O6
and BrO3.

Oxidizing Power
The halogens are good oxidizing agents. Generally speaking, a higher member displaces a lower
from the halide. The following reactions illustrate this point.
F2 + 2X-  2F- + X2 (X=Cl, Br, I)
- -
Cl2 + 2X  2Cl + X2 (X=Br, I)
Br2 + 2I-  2 Br- + I2
The oxidizing power decreases down the group, which is reflected in their decreasing reduction
potential values.

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 Chemistry (s and p-Blocks)

Element F2 Cl2 Br2 I2

E0(V) 2.87 1.40 1.09 0.62
½ X2  2X- (aq)
The strength of an oxidizing agent depends on several energy terms. The reaction represents the
oxidizing action of a halogen and is best represented in the form of a Born - Haber Cycle
½ X2 (standard state) + e-  X- (aq)

H Hd
½ X2 (standard state) ½ X2 (g) X (g)
 

 E V EA

H hyd
X (aq)
–
X (g)
–

V
If the standard state of the halogen is solid i.e. for I2, H is the sum of enthalpy of fusion and
enthalpy of vaporization. For a liquid halogen, i.e. Br2, H is enthalpy of vaporization. Energy is absorbed
in steps II and III and released in IV and V. From Hess’s law E is given by:
E = H + Hd + EA + H hyd
Where Hd = enthalpy of dissociation
EA = electron affinity
Hhyd = enthalpy of hydration
For F2 and Cl2 which exist as gases, H is omitted. The enthalpy changes associated with the
reaction (I) decrease from fluorine to iodine (Table). The high oxidizing power of fluorine is attributed to
low enthalpy of dissociation and high enthalpy of hydration.
Table: Enthalpy Values for ½ X2  X– (aq)

Molecule ½Hvap ½Hdissoc Electron ½Hhyd Total H

(KJmol -1) (KJmol -1) affinity (KJmol -1) (KJmol -1)
(KJmol-1)
F2 - +79.4 -333 -460 -713.6
Cl2 - +121.3 -349 -348 -575.7
Br2 +15 +96.4 -325 -318 -531.6
I2 +30 +75 -295 -305 -4950

Some important reactions of halogens are listed in Table.

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Table: Some Reactions of Halogens

Reaction Remarks
X2 + H2  2HX All halogens
nX2 + 2M  2MX n Most metals form halides, reaction with F2 vigorous
3X2+ 2P  2PX3 All halogens, similar reaction with As, Sb, Bi
5X2+ 2P  2PX5 F 2, Cl 2 and Br2
X2 + 2S  S 2X2 Cl 2 and Br2
2Cl2 + S  SCl4
3F2 + S  SF6
+ -
X2 + H2O  H + X + HOX Cl 2 and Br2
+ -
F2 + 2H2O  4H + 4F + O2
X2 + SO 2  SO2 X2 F 2 and Cl2
X2 + CO  CoX 2 Cl 2 and Br2
X2 + H2S  2HX + S All halogens
3X2 + 8NH3  N2 + 6NH4X F2, Cl 2, Br2

Basic Properties of Halogens

Metallic character increases down the group and decreases across a period. It has been seen
in Groups 14, 15 and 16 that the last member (Pb, Bi, Po) has metallic character. This is not very
apparent in halogens as very little is known about the last element, astatine. However, there are certain
evidences to show existence of halogen cations.
Fluorine is the most electronegative element; it has no tendency to display positive oxidation
state. ClF ionizes to form Cl+ and F- Br+ exist in complexes like [Br (Pyridine)]+ NO3-. ICN on electrolysis
liberates iodine at anode, indicating formation of I+. Many pyridine complexes of I+ are known eg. [I (py)]+
NO3-, [I (py)2]+ ClO4- and [I(py)]+ CH3COO-, (py = pyridine).
Iodine dissolves in oleum to give a blue solution that contains I2+ and I3+
2I2/3I2 + 6H2S2O7  2I2+/2I3+ + 2HS3O10- + 5H2SO4 + SO2
Molten iodine conducts electricity and it has been shown that I3+ and I3- are present

3I2 
 I3  I3


Many other compounds containing Cl3+, Br3+, I3+, I5+ have been prepared.
Cl2 + ClF3 + AsF5  [Cl3]+ [AsF6]- + F2
Br2 + BrF3 + AsF5  [Br3]+ [AsF6]- + F2
I2 + ICl + AlCl3  [I3]+ [AlCl4]-
2I2 + ICl + AlCl3  [I5]+ [AlCl4]-
ICl is an electrophilic iodinating agent, believed to contain I+
When a solution of iodine in an inert solvent is passed through a cation-exchange resin, some
iodine is retained by the resin, indicating the presence of I+
H+ Resin- + I2  I+ Resin– + HI
The structures of the triatomic and penta-atomic cations are shown in Fig.

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 Chemistry (s and p-Blocks)

]+ ]+

   
  

Fig: The structures of I3 and I5

Compounds
Hydrogen Halides
Binary compounds of hydrogen and halogen are formulated as HX and in the anhydrous state are
referred to as hydrogen halides. Their aqueous solutions are called hydrohalic acids. The halogens react
with hydrogen forming HX. The reaction with fluorine is violent and explosive while that with iodine is slow
illustrating decrease in reactivity on moving down the group. At room temperature HF is a liquid due to
strong intermolecular hydrogen bonding, while others are gases. The melting and boiling points shows
a gradual increase in the order HCl < HBr < HI.
The hydrogen halides are covalent in the gaseous state, but in aqueous solution they ionize and
behave as strong acids (except HF, which is a weak acid, pKa = 3.2 at 250 C). The
ionization may be represented as
HX + H2O  H3O+ + X– (X= Cl, Br, I)
As fluorine is the most electronegative element, the H-F bond has maximum ionic character and
HF should be the strongest acid, however the reverse is true. The paradox arises due to the fact that
acid strength which is given by the following reaction
HX (hydrated) + H2O  H3O+ + X- (hydrated)
It involves various enthalpy parameters as shown:

Thus acid strength = H dehyd + Hd + I.E. + E.A. + Hhyd of H+ and X–

Where
Hdehyd = enthalpy of dehydration
Hd = enthalpy of dissociation
I.E. = ionization enthalpy
E.A. = electron affinity
Hhyd = enthalpy of hydration
For HF, the enthalpy of dehydration and enthalpy of dissociation are very high. The high enthalpy
of hydration of F- cannot compensate for the same and the total enthalpy change for HF is least negative.

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Due to strong hydrogen bonding between F- and H3O+ (F- ----- H+–OH2), ion pairs of the type H3O+F– are
formed, lowering the concentration of H3O+ and decreasing acidity. As the concentration of HF increases,
the tendency to form H3O+ increases:

H3O+F– + HF 
 H O+ +HF –
 3 2

Halogen Oxides
A large number of halogen oxides are known (Table), some of which are unstable.

Table: Compounds of Halogens with Oxygen

The binary compounds of fluorine and oxygen are referred to as fluorides. The most stable oxide
is I2O5. The oxides of chlorine and bromine decompose readily. The bonds are largely covalent due to
small electronegativity difference, however some ionic character is noted in iodine oxides. ClO2 and Cl2
O find some practical importance as bleaching agents and germicides, while I2O5 is used in estimation
of carbon monoxide
I2O5 + 5CO  I2 + 5CO2
The reaction is quantitative and the liberated iodine may be estimated by titration with sodium
thiosulphate
I2 + 2Na2S2O3  2NaI + Na2S4O6
The structures of some halogen oxides are shown in Fig.

O O O

F 103º F Cl 111º Cl O 118º O

(a) (b) (c)

O O O O

O — Cl — Cl — O  — O — 

O O O O
(d) (e)

Fig: The structures of (a) OF2 (b) Cl2O (c) ClO2 (d) Cl2O6 (e) I2O5

The structure of OF2, Cl2O and Br2O are all related to a tetrahedron with two positions occupied
by lone pair of electrons (like H2O). Repulsion between the lone pairs reduces the bond angle in F2O from
the tetrahedral angle of 109o 281 to 1050. In Cl2O and Br2O, the bond angles increase due to steric
crowding of the large halogen atoms.

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Oxoacids of Halogens
Four series of oxoacids of halogens are known (Table).
Table: Oxo acids of Halogens

HOX HXO 2 HXO3 HXO 4

Oxidation State +1 +3 +5 +7
of Halogen
HOF
HOCl HClO 2 HClO3 HClO 4
HOBr HBrO2 HBrO 3 HBrO 4
HOI HIO 3 HIO 4

The structures of the ions formed are shown in fig.

X X X X
O O O O O

O O O
OX OX2 OX3 OX4
Fig: The Structures of Oxo anions
The halogen atom is sp3 hybridized, there is significant p – d -bonding involving filled 2p orbital
of oxygen and vacant d orbitals on halogens. Many of the oxoacids are known in solution, or in form of
salts. Fluorine being more electronegative than oxygen does not form any oxoacid except the unstable
HOF, which is obtained by passing F2 over ice
50C
F2  H2O  HOF  HF
It is difficult to prepare and isolate because of its reactivity towards H2O and F2
HOF + H2O  HF + H2O2
HOF + F2   HF + OF2
The oxoacids of chlorine are well known and arise from disproportionation of chlorine and related
reactions:
Cl2 + 2H2O Cold
  HOCl + H3O+ + Cl–

Cl2 + HCO3– Cold

  HOCl + CO2 + Cl–

3Cl2 + 6OH– Hot

  ClO3– + 5 Cl– + 3H2O

4KClO3 Heat
  3KClO4 + KCl
In basic solution chlorine dioxide disproportionate to form chlorate and chlorite and the latter is
used to form the free acid.
2ClO2 + 2OH–  ClO2– + ClO3– + H2O
Ba(ClO2)2 + H2SO4  2HClO2 + BaSO4 (s)

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The acid strength of oxoacids increases with increase in oxidation number of the order of acid
strength is
HOCl < HOClO < HOClO2 < HOClO3
As the oxidation state of the halogen increases, the number of oxygen atoms attached to the
halogen increases. As oxygen is more electronegative, the halogen – oxygen bond is polarized leaving
a small positive charge on the halogen. This now attracts the electrons of O-H bond towards itself,
facilitating loss of hydrogen as proton. Greater the number of oxygen atoms, more is the acidity

– – –
O O O

H O Cl+ H O Cl+ H O Cl+ O–

– –
O O

Acid strength of oxoacids with halogen in the same oxidation state, decreases with decrease in
electro-negativity of the halogen.
HOI < HOBr < HOCl
Sodium hypochlorite (NaOCl) is used in bleaching cotton fabrics, wood pulp and is a disinfectant.
Anhydrous perchloric acid (HClO4) is a very powerful oxidizing agent. Periodic acid (HIO4) is used to
oxidize alkenes to glycols.

Interhalogens
Halogens react with each other to form interhalogens. These are subdivided into four types. AX,
AX3, AX5, AX7 (Table)

Table: Some interhalogen compounds

AX AX3 AX5 AX7
ClF ClF3 ClF5 IF7
BrF BrF3 BrF5
BrCl IF3 IF5
ICl I2Cl6
IBr
IF (unstable)

The total number of halogen atoms is even as this gives rise to diamagnetic species. They are
generally more reactive than the parent halogens (except fluorine) as A-X bond is weaker than X-X bond.
The interhalogens can be prepared in a variety of ways, including direct reaction of the elements (the
favoured product often depends on ratio of halogens used) and reaction of metal halides or other
halogenating agents. Examples include
Cl2 + F2  2ClF (T = 2250C)
I2 + 5F2  2IF5 (Room Temperature)
I2 + 3XeF2  2IF3 + 3Xe (T< –300 C)
I2 + AgF  IF + AgI (T = 00 C)

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Some interhalogens may serve as intermediates in synthesis of other interhalogens

ClF + F2  ClF3 (T = 200 – 3000 C)
ClF3 + F2  ClF5 (hv, Room Temperature)
Several interhalogens undergo auto ionization in the liquid state and are used as non-aqueous
solvents

3IX 
 I2X+ + IX2– (X= Cl, Br)

2BrF3 


 BrF2+ + BrF4

2IF5 


 IF4+ + IF6–
The interhalogens are hydrolyzed to give halide and oxohalide; the larger halogen forms the
oxohalide
H2 O
BrF5   5F  BrO3
H2 O
ICI   CI  OI
The shapes of some interhalogens are given in table.

Table: Shapes of interhalogens on basis of VSEPR Theory

Molecules No. of electron No. of Bond Pairs No. of lone Shape

pairs around A pairs
AX 4 1 3 Linear
AX3 5 3 2 T – Shaped
SX5 6 5 1 Square
Pyramid
AX7 7 7 0 Pentagonal
bipyramidal

The structure can be derived by VSEPR theory. As expected interhalogens of the types AX are
linear. Interhalogens of the type AX3 (ClF3) are T-shaped, where the central halogens ‘A’ (Cl) is sp3d
hybridized with two lone pairs of electrons (Fig). ICl3 exists as a dimer, (ICl3)2, in the solid state in which
two T-shaped ICl3 units are joined together.

F F

F Cl Cl Cl
Cl Cl F  
Cl Cl Cl

F F
(a) (b) (c)

Fig : The structures of Cl F3 and (ICl3)2

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Interhalogens of the type AX5 and AX7 have square pyramidal and pentagonal bipyramidal structures
respectively (Fig)

F F

F F F F
 
F F F F

F
F
(a) (b)
Fig: The structures of (a) I F5 and (b) I F7
In AX5 the central halogen is sp3d2 hybridized and there is one lone pair of electrons whereas in
AX7 the central halogen has sp3d3 hybridization.
Ternary interhalogens have recently been reported e.g. IFCl2, IFCl.

Polyhalides and polyhalonium ions

Halide ions associate with molecules of halogens or interhalogens to form polyhalides. The
solubility of iodine is enhanced in potassium iodide due to formation of triiodide ion, I3–.
KI + I2  KI3
More complex ions like I5–, I 7– are known. Polyhalides containing two or three different halogens
are known eg [ICl2]–, [BrF4]–, [BrICl]– etc. polyhalonium cations eg. [ICl2]+, [BrF2]+ are obtained as a result
of auto ionization of ICl3 and BrF3. Other cations e.g. Br3+, I3+ [ClF6]+ etc. are also known.

Pseudohalogens
Parallels have been observed between the chemistry of the halogens and other dimeric species.
Such molecules are called pseudohalogens eg. Cyanogens (CN) 2, thiocyanogen (SCN) 2 and
selenocyanogen (SeCN) 2. A pseudohalogen is a univalent chemical aggregate, comprising of two or
more electronegative atoms, which in the free state show properties similar to halogens. They combine
with hydrogen to form an acid and with silver, a salt insoluble in water. The anions of pseudohalogens
are called pseudohalides. The most important pseudohalide is CN- and its similarity with Cl- is shown
in Table.
Table: Comparison of a Pseudohalogen with a Halogen

Characterstics Examples
Halogen Pseudohalogen
Neutral diatomic species Cl2 (CN)2
- -
Anion Cl CN
Acid with hydrogen HCl HCN
Insoluble Salts AgCl AgCN
Interhalogen compound ICl, BrCl ClCN, BrCN, ICN
3- 3-
Anionic Complexes [CoCl6] [Co (CN)6]
2- 2-
[CuCl4] [Cu (CN)4]

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 Chemistry (s and p-Blocks)

Group 18
The elements in Group 18, long designated as the “inert” or “rare” gases, no longer satisfy these
labels. They are known to form chemical compounds and are rather abundant. They are better referred
to as “noble” gases due to their reluctance to react under normal conditions. This group comprises of
helium, neon, argon, krypton, xenon and radon. Apart from radon, which is radioactive, the others are
present in the atmosphere.
Helium has two electrons, which forms a complete shell 1s2. The others have a complete octet
of electrons and the configuration is ns2 np6. This configuration is very stable and is related to their un-
reactivity. These elements have an electrons affinity of nearly zero and very high ionization energy. Under
normal conditions these elements have very little tendency to gain or lose electrons.
Important properties of noble gases are summarized in Table.
Table: Physical properties of the Noble Gases

Property He Ne Ar Kr Xe Rn
Atomic Number 2 10 18 36 54 86
Electronic Configuration 1s 2 [He]2s 22p6 [Ne]3s 2 3p6 [Ar]3d10 4s 2 4p6 [Kr]4d10 5s 25p6 [Xe]4f14 5d10 6s 26p6
Vander Waal’s radius (pm) - 131 174 189 210 215
Ionization Energy (Kjmol–1 ) 2372 2081 1521 1351 1170 1037
0 - -248.6 -189.4 -157.2 -111.8 -71.0
Melting Point ( C)
0 -269 -246.1 -185.9 -153.4 -108.1 18.1
Boiling Point ( C)

Physical Properties
The elements exist as colourless, monoatomic gases. Individual atoms are held by weak vander
waals forces, hence melting points and boiling points are very low. In fact the boiling point of helium is
the lowest of any element.
Chemistry
The first chemical compounds containing noble gases were known as clathrates or cage
compounds where noble gas atoms were trapped in the crystal lattice of other compounds. When water
or solutions containing quinol (p- dihydroxybenzene) were crystallized under high pressures of certain
gases, the molecules of the gas were trapped in the cavities in the hydrogen-bonded lattice. Clathrates
of argon, krypton and xenon have been prepared. No clathrates are known for helium and neon, which
are too small to be trapped.
Even though clathrates of three noble gases were known, no real compounds containing covalently
bonded noble gas atoms were synthesized till 1962. Neil Bartlett (1962) observed that PtF6 changed
colour on exposure to air. He attributed this to the formation of O2+ [PtF6]–He noted the similarity in
ionization energies of xenon (1170 KJ mol-1) and oxygen molecule (1175 KJ mol-1) and repeated the
experiment, reacting Xe with PtF6. He obtained a yellow solid and formulated it as Xe+ [PtF6]-. The
reaction was found to be more complicated.

Xe[PtF6] + PtF6 [XeF]+ [PtF6]– + PtF5

60ºC

+
[XeF] [Pt2F11]
–

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This opened the field for the study of chemistry of noble gases. In a matter of months XeF2 and
XeF4 were characterized.
The known noble gas compounds of xenon are the most diverse followed by some compounds
of krypton. The study of radon chemistry is hampered by its radioactivity. The first stable compound of
argon, HarF has been reported recently (2000). The ionization energies of the lighter noble gases are
too high to allow formation of compounds. Most compounds of noble gases are restricted to the highly
electronegative elements, fluorine and oxygen.

Compounds of Xenon
Some compounds of xenon are shown in Table.
Table: Some Compounds of Xenon

Compounds Oxidation state Number of electron pairs around Xe Structure

Bond Pairs Lone Pairs Total
XeF2 +2 2 3 5 Linear
XeF4 +4 4 2 6 Square planar
XeF6 +6 6 1 7 Distorted octahedral
XeO 3 +6 6 1 7 Pyramidal (3Xe=0 bonds)
SeO 2F2 +6 6 1 7 See – saw (2Xe=0 bond)
XeOF4 +6 6 1 7 Square pyramid (one Xe=0 bond)
XeO 4 +8 8 0 8 Tetrahedral (4Xe = 0 bonds)

Xenon and fluorine combine on heating in a sealed nickel vessel at 400oC, the product depends
on the F2/Xe ratio
2:1
XeF2

Xe + F 2

1:5
XeF4
6 atmospheres

1:20
XeF6
50-60
atmospheres
The fluorides are strong oxidizing and fluorinating agents as indicated by the following reactions
XeF2 + H2  2HF + Xe
XeF4 + 2H2  4HF + Xe
XeF6 + 3H2  6HF + Xe
XeF2 + 2HCl  Cl2 + 2HF + Xe
XeF4 + 4KI  2I2 + 4KF + Xe
XeF4 + 2SF4  Xe + 2SF6
XeF4 + Pt  Xe + PtF4
XeF4 + 2C6H6  Xe + 2C6H5F + 2HF

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The fluorides differ in their reactivity with water. XeF2 undergoes slow hydrolysis in neutral or
acidic medium, but rapid hydrolysis in alkaline medium.
2XeF2 + 2H2O  2Xe + 4HF + O2
The reactions of XeF4 and XeF6 are violent and the explosive XeO3 is formed.
2XeF6 + 12H2O  4Xe + 2XeO3 + 24HF + 3O2
2XeF6 + 6H2O  2XeO3 + 12HF
With small amounts of water, partial hydrolysis occurs to give XeOF4
XeF6 + H2O  XeOF4 + 2HF
XeF6 is highly reactive and combines with silica
2XeF6 + SiO2  2XeOF4 + SiF4
2XeOF4 + SiO2  2XeO2F2 + SiF4
2XeO2F6 + SiO2  2XeO3 + SiF4
XeO3 undergoes alkaline hydrolysis to give the xenate ion, HXeO4- which disproportionate to give
perxenate (XeO64-) and Xe
XeO3 + NaOH  Na+HXeOH4-
2HXeO4- + 2OH-  XeO4-6 + Xe + O2 + 2H2O
Perxenates are powerful oxidizing agents XeF2 acts as a fluoride ion donor and reacts with
covalent pentafluorides forming species of the type [XeF]+ [MF6]-, [XeF]+ [M 2F11]- and [Xe2F3]+ [MF6]-, (M=
P, As, Sb, Nb, Ta, Ru, Rh, Ir, Pt). XeF4 reacts less readily with PF5,
AsF5 and SbF5 . XeF6 reacts both as fluoride ion donor and acceptor forming species like [XeF5]+
[MF6]- (M = As, Pt) and M+[XeF7]- (M= Rb, Cs)
The structures of some xenon compounds are shown in Figure. XeF2 and XeF4 have structures
entirely in accordance with VSEPR description. XeF2 is linear (Xe is sp3d hybridized and there are three
lone pairs on Xe). XeF4 is planar (sp3d2 hybridized Xe with two lone pairs).

F
F F
F F
F F
Xe Xe Xe
F F
F F
F
(a) (b) (c)

Fig: The structures of xenon fluorides

The structure of XeF6 cannot be interpreted by VSEPR theory, which predicts sp3d3 hybridization
with one lone pair occupying a definite position on xenon. However no definite location of the lone pair
is noted. The structure seems to be distorted octahedral with the lone pair apparently emerging from the
centre of one of the faces.
Positive ions containing xenon are also known. The compound [XeF]+ [RuF6]- has the linear XeF+
ion attached to the fluorine of the anion. The anion comprises of Ru, octahedrally surrounded by six F
atoms.

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 Chemistry (s and p-Blocks)

F F

Xe F
F Ru
F F

F
The chemistry of krypton is much more limited. The only known neutral fluoride is KrF2, which
is useful as a fluorinating agent. It can raise metals to unusual oxidation states.
8KrF2 + 2Au  2KrF+ AuF6- + 6Kr + F2
KrF+ AuF6  AuF5 + Kr + F2
The first compound containing the Kr-O bond was [Kr( OTeF5)3] which is unstable.
The radioactivity of radon has made the study of its chemistry difficult. RnF2 and a few other
compounds have been observed through tracer studies.

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