“p- Block Elements”

Introduction:
 Elements of groups 13 to 18.
 General electronic configuration: (ns2np1-6) where ‘n’ stands for outermost shell.
 This block includes metals, nonmetals and metalloids.
 The maximum oxidation state (group oxidation state) shown by a p-block element = sum of s- and p-
electrons.
 The 1st member of each group varies from other group members: Small size (related properties) and
absence of d-orbital (co-valency not more than four).
 The 1st member of each group differs from other group members: ability to form pπ-pπ multiple
bonding.
 Inert pair effect: Due to poor shielding of d- and f-electrons, the inertness of valence s-electrons of
heavier elements to take part in bonding is called inert pair effect.

“Group 13”

Elements Symbols At. No. Electronic Configuration

Boron B 5 [He] 2s22p1
Aluminium Al 13 [Ne] 3s23p1
Gallium Ga 31 [Ar] 3d104s24p1
Indium In 49 [Kr] 4d105s25p1
Thalium Tl 81 [Rn] 5d10 6s26p1

PHYSICAL PROPERTIES:
 Atomic and Ionic radii: Increases on moving down the group due to addition of new shells.
Exception: Atomic radius of Al(143pm) is slightly more than that of Ga (135pm).
Explanation: The d- orbital do not screen the nucleus effectively due to their shapes and poor
penetration power and Ga have 10 electrons in core d- orbital so effective nuclear charge in Ga
becomes more than in Al and its atomic radius decreases slightly.
 Ionization Enthalpy: Decreases on moving down a group.
Exception: The ionization enthalpy of Ga is higher than that of Al.
Explanation: Due to the shielding effect of 10 d electrons in Ga it atomic size is smaller in
comparison to Al. So ionization energy of Ga is greater than Al.
 Melting and boiling points: All the elements of 13 group are soft and with low melting points, Ga
has very low melting point (303K) and therefore could exist in liquid state during summer.
Exception: Boron has very strong melting point.
Explanation: Boron has strong crystalline lattice and therefore has strong melting point.
CHEMICAL PROPERTIES:
 Oxidation State:- The elements of group 13 show trivalency by sharing three of its valence
electrons, so they have +3 oxidation state. Ga, In and Tl also show +1 oxidation
state and +1 oxidation state becomes more stable Ga <In<Tl. For Tl compounds, +1 oxidation state is
more predominant, this is due to inert pair effect where ns electrons are not able to participate.

 Reactivity towards Air: On heating boron and aluminium form tri oxide and with nitrogen form
nitrides.
4 B + 3O2  2 B2 O3( s )
4 Al + 3O2  2 Al 2 O3( s )
2 B + N 2  3BN ( s )
2 Al + N 2  2 AlN
Nature of oxides of 13 group elements is as follow:
B2 O3 Al 2 O3 , Ga 2 O3 In2 O3 , Tl 2 O3
 Acidic Amphoteric Basic
 Boron is unreactive in crystalline form and aluminium is also stable due to the formation of
thin layer of Al 2 O3 .Passive nature of Al and B.
 Al is used to store food although very reactive.

 Reactivity towards acids and bases:

 Boron is unreactive even at moderate temperature.
 Aluminium is amphoteric in nature. i.e. react with both acids and bases:
2 Al + 6 HCl ( aq )  2 Al (3aq ) + 6Cl (aq ) + 3H 2 ( g )
Acid
2 Al + 2 NaOH ( aq ) + 6 H 2 O  2 Na  [ Al (OH ) 4 ]  + 3H 2 ( g )
Base Sod. Tetrahydroxoalluminate(IV)
 Passivity:- HNO3 makes Al passive by oxide layer formation.
2 Al ( s ) + 3 / 2O2 ( g )  Al 2 O3( s ) H  1670 KJ / mol
(From HNO3)
 Reactivity towards halogens: Forms trihalides.
3M + 3X 2  2 MX 3( g )
[M= Elements of 13 group, X= F, Cl, Br, I]

“ANOMALOUS PROPERTIES OF BORON”

 Formation of Hydrides: The groups 13 elements from hydrides of MH3 type, but the hydrides of
boron have the general formulae BnHn+4 and BnHn+6 and the compounds are called
“Boranes”. Example: B2H6, B4H10, B5H11 etc.
 Formation of Halides: The group 13 elements form trihalides with general formula MX3. The
monomeric trihalides being electrons deficient act as lewis acids.
BF3 + : NH 3  F3 B  NH 3

“Some important compounds of Boron”

1. “BORAX”
Introduction: [Na2B4O7.10H2O] White crystalline solid] Borax contains the tetranuclear units
[B4O5(OH)4]−2 and therefore its correct formula is Na2[B4O5(OH)4].8H2O.
Preparation:
From boric acid:- Borex is formed when boric acid neutralizes with sodium carbonate.
4 H 3 BO3 + Na 2 CO3  Na 2 B4 O7 + 6 H 2 O + CO2
Properties:
1. Borax dissolves in water to give alkaline solution due to hydrolysis.
Na 2 B4 O7 + 2 H 2 O  H 2 B4 O7 + 2 NaOH
2. On heating borax decomposes and swells losing water of crystallization. On further heating, it melts
and forms a clear transparent dead of basic oxide and sodium metabarate.
Na 2 B4 O7 .10 H 2 O Heat
 Na 2 B4 O7 + 10 H 2 O
Na 2 B4 O7 Heat
 NaBO2 + B2 O3
Sod. Metaborate Boron Oxide
Uses of Borax:
Borax is used in,
 Borax bead test for qualitative analysis.
 Manufacture of enamels and glazes for earthen pots.
 Candle industry.

2. “ORTHOBORIC ACID”
[H3BO3, White crystalline solid, with soapy touch.]
Preparation:-
1. From Borax: It is prepared by acidifying an aqueous solution of borax.
Na 2 B4 O7 + 2 HCl + 5 H 2 O  4 H 3 BO3 + 2 NaCl
Na 2 B4 O7 + H 2 SO4 + 5 H 2 O  4 H 3 BO3 + Na 2 SO4

2. From hydrolysis of boron compounds: It can also prepared by the hydrolysis of boron compounds
([Link], hydrides, nitrides etc. )
BCl 3 + 3H 2 O  H 3 BO3 + 3HCl
BN + 3H 2 O  H 3 BO3 + NH 3
Properties:
1. It is sparingly soluble in cold water but fairly soluble in hot water.
2. On heating, orthoboric acid loses molecules of water in stages at different temperature and forms
different products.
H 3 BO3 373K
 HBO2 433 K
 H 2 B4 O7 Re dHot
 B2 O3
Meta boric acid Tetraboric acid Boron tri oxide
3. Acidic character: Boric acid is a week monobasic acid. Boric acid does not act as a protic acid
but behaves as a Lewis acid by accepting a pair of electrons from OH− ion.
B(OH ) 3 + 2 H –O–H  [ B (OH )4] + H 3 O 
Uses of Orthoboric acid: Orthoboric acid is used in:
 Manufacturing of pigments and borax.
 Medicines as an eye wash and food industry as food preservative.

3. “DIBORANE(B2H6)

Preparation:-
1. It is prepared bythe oxidation of sodium borohydride with iodine.
2NaBH 4 + I 2 PolyEther
  B2 H 6 + 2NaI + H2
2. It can also be prepared by the treatment of boron trifluoride or trichloride with LiAlH4 in diethyl
ether.
4BF3 + 3LiAlH4  2 B2 H 6 + 3LiF + AlF3
4BCl 3 + 3LiAlH4  2 B2 H 6 + 3LiCl + AlCl 3
3. Industrial Prepration:- It is prepared by the reaction of BF3 with LiH or NaH at 450K.
2BF3 + 6 NaH 450  K
 B2 H 6 + 6 NaF
Properties:
1. Diborane is a coloureless, highly toxic gas with b.p. 180K and m.p. 108K.
2. Diborane catches fire spontaneously upon exposure to air and releases an enormous amount of
energy.
2 B2 H 6 + 3O2  B2 O3 + 3H 2 O H 0  1976 KJ / mol
3. Hydrolysis: On hydrolysis liberate H2 gas.
B2 H 6 + 6 H 2 O  2 H 3 BO3 + 6H 2 
4. Reaction with Ammonia:- On reaction with NH3 gives different products depending upon the
conditions.
3B2 H 6 + 6NH 3   B3 N 3 H 6 + 6H2
450 K

Borazine
B2 H 6     ( BN ) x
ExcessofNH 3

Borazine has structure similar to benzene and therefore, it is called inorganic benzene.
5. Diborane gives addition reaction Lewis bases (L) to give birane adducts BH3L.
B2 H 6 + 2CO  2 BH 3 CO
Borine Carbonyl
 B2 H 6 + 2NMe3  2 BH 3 NMe3
Uses of Diborane:- Diborane is used
 For preparing a number of other hydrides as LiAlH4, NaBH4.
 As a fuel for supersonic rockets.
 As a reducing agent in organic reactions.

Structure of diborane:- The electron diffraction studies have shown bridged structure for diborane. In
this structure there are two types of hydrogen atoms.
(i) Four terminal hydrogen are bonded by normal covalent bonds formed by sharing of one electron
each by B and H atoms.
(ii) The other two H atoms are known as bridged hydrogens and are bonded by three centre electron
pair bonds, which involve one electron pair only but binds three atoms B, H, and B.
The two B atoms and four terminal hydrogen atoms present in the same plane while the two
bridging H- atoms are in a plane perpendicular to the rest molecule.

Group: 14

Elements Symbols At. No. Electronic Configuration

Carbon C 6 [He]2s22p2
Silicon Si 14 [Ne] 3s23p2
Germanium Ge 32 [Ar] 3d104s24p2
Tin Sn 50 [Kr] 4d105s25p2
Lead Pb 82 [Rn] 4f145d106s26p2

PHYSICAL PROPERTIES:-
1. Atomic Radii: Atomic radii increase on going down the group, due the increase in the no. of shells.
2. Ionization Enthalpy: The first ionization enthalpies of 14 group elements are higher than the
corresponding members of group 13 elements, due to the higher nuclear
charge and smaller size.
On moving down the group, the ionization enthalpies decreases due to increases in atomic size
and screening effect which overweight the effect of increases in nuclear charge.
3. Electronegativity :- The elements of group 14 are slightly more electronegative than group 13
elements, due to small size.
On going down the group electronegativity first increases from C to Si and then Si to Pb are
almost the same.
4. Melting and boiling points:- The atoms of group 14 form covalent bonds with each other
consequently, the melting and boiling points of group 14 elements are
much higher in comparison to group 13 elements.
5. Metallic character:- On moving down the group the metallic character increases from carbon to
lead.
C Non metal
Si Non metal
Ge Metalloid
Sn Metal
Pb Metal
 Due to large ionization enthalpies the group 14 elements are less metallic than the elements of
group 13.
CHEMICAL PROPERTIES:-
1. Oxidation State:- The elements of group 14 show tetravalency by sharing four of its valence
electrons, so they have +4 oxidation state. Ge, Sn, Pb also show +2 oxidation state
and +2 oxidation state becomes more stable Ge<Sn<Pb. For lead compounds, +2 oxidation state is
more predominant, this is due to inert pair effect.
Inert Pair Effect:- The inability of s electrons of the valence shell to participate in bonding is known as
inert pair effect. Eg. The pair of electrons, 5s in tin and 6s in lead behaves as inert.
Explanation:
 Carbon show only tetra covalency while other elements exceed its covalency more than 4.
Why?
Explanation: Carbon does not have d- orbital while in other elements empty d- orbital present, due to
this their halides undergo hydrolysis and have tendency to form complexes by accepting
electron pairs from donor species.
Eg. SiF62 , [GeCl 6 ] 2 , [ Sn(OH ) 6 ] 2 etc.
The hybridization of the central atom is sp3d2.
2. Reactivity towards oxygen:- All the elements of group 14 from oxides with oxygen. They formed
two type of oxides.
(i) Monoxides (MO):- CO GeO SnO, PbO
Neutral Acidic Amphoteric
(ii) Dioxide (MO2):- CO2, SiO2, GeO2 SnO2,PbO2
Acidic Amphoteric
3. Reactivity towards water:- Only Sn react with steam to form SnO2 and H2.
Sn + H 2 O  SnO2 + 2H 2
Heat

C, Si, Ge, and Pb are not affected by water and lead is not affected due to a protective oxide film.
4. Reactivity towards halogen:- The elements can form halides of formulae MX2, MX4 [where X= F, Cl,
Br, I.] which are mostly covalent.

“UNIQUE CHARACTER OF CARBON”

Carbon being the first member of group 14 shows many unique characters.
1. Catenation:- The property of forming bonds with atoms of the same elements is called catenation.
Carbon shows maximum catenation and on moving down the group the tendency
decreases.
C—C C—C
| |
C—C—C—C—C—C—C—C—C C—C—C—C—C—C—C—C—C
| Straight Chain
C—C—C
|
C
Branched Chain
The tendency of catenation depends upon the strength of M—M bond and the strength of M—M
bond decreases due to increase in size of the atom.
C>>Si>Ge=Sn>Pb
2. Tendency to form multiple bonding:- Carbon has unique ability to form pЛ- pЛ multiple bonds
with itself and with other atoms of small size and high electronegativity.
Eg. C=C, C≡C, C=S, C=O, C≡N.

“ALLOTROPES OF CARBON”
The different forms of the same element having different physical properties but almost similar
chemical properties are known as allotropes.
Carbon exists in two types of allotropic forms:
(i) Crystalline:- Diamond, graphite are well known and third form fullerene was discovered by H.W.
 Kroto, E. Smally and R. F. Curl.
(ii) Amorphhous:- Coal, wood charcoal, lamp black, gas carbon, coke etc.

“DIAMOND”
Structure:
1. Each carbon atom is sp3 hybridized.
2. Each carbon atom is bonded to four other carbon atoms by single covalent bonds.
3. C—C bond length is 154pm.
 The three dimensional network of strong covalent bonds makes diamond an extremely
hard crystal with very high melting point(3843K).
 It is used as abrasive.

“GRAPHITE”
Structure:-
1. Graphite has layered structure.
2. Different layers are held together by Vander waals force.
3. The distance between two layers is 340pm.
4. Each layer is composed of planar hexagonal rings of carbon atoms.
5. C—C bond length within the layer is 141.5pm.
6. Each carbon atom is sp2 hybridized.
7. Each carbon atom is bonded to three other carbon atoms by single covalent bonds.
8. The fourth electron form a Л bond, the electrons are delocalized over the whole sheet.
9. Due to these delocalized electrons, graphite conducts electricity. So it is used as electrodes.
 Graphite cleaves easily between the layers it is very soft and slippery, so graphite used as
a dry lubricant in machines at high temperature.

“SOME IMPORTANT COMPOUNDS OF C AND Si”

“CARBON MONOXIDE”
PREPARATION:-
1. Carbon monoxide is prepared by incomplete comdustion of carbon or carbon containing
compounds in a limited supply of oxygen.
C + ½ O2 → CO
2. Pure CO can be prepared on a laboratory scale by heating formic acid with H2SO4 at about 373 to
413K.
HCOOH H  CO + H 2 O
2 SO4

PROPERTIES:-
1. CO is colourless, odourless, and sparingly soluble in water.
2. Toxic Nature:- It is highly toxic in nature. The toxic nature of CO is due to its ability to
form a complex with hemoglobin in red blood cells. Hemoglobin in blood combines with O2 and
forms oxyhemoglobin by a reversible reaction.
Hemoglobin + O2  Oxyhemoglobin
Oxyhemoglobin gives to different body cells. Therefore, if CO is present, it will forms
about 300 times more stable compound with hemoglobin and destroy the oxygen carrying ability
of the blood. As a result, blood will not take up oxygen easily, causing suffocation and finally
death.
3. Reducing Character:- It is a powerful reducing agent and reduces many oxides to metals.
Eg. ZnO + CO  Zn + CO2
Fe2 O3 + 3CO  2 Fe + 3CO2
USES OF CARBON MONOXIDE:-
1. Carbon monoxide is used as an industrial fuel in the form of water gas and producer gas.
(a) Water Gas:- Mixture of CO and H2 which is prepared by passing air over red hot coke.
C + H 2 O  CO + H 2
Steam Water Gas
 (b) Producer Gas:- Mixture of CO and N2 which is prepared by passing air over red hot coke at
about 1300K.
2C + O2 + 2N 2 1300  K
 2CO + 2N 2
Producer Gas
Both water gas and producer gas contain CO which can undergoes further oxidation to form CO2 and
liberates enormous amount of heat.

“CARBON DIOXIDE”
PREPARATION:-
1. CO2 is prepared by burning carbon, hydrocarbon or carbon monoxide in excess of air.
C + O2  CO2
CH 4 + 2O2  CO2 + 2 H 2 O
2CO + O2  2CO2
2. Lab Method:- It is prepared by the action of dil HCl on carbonates such as CaCO3.
CaCO3 + 2 HCl  CO2 + CaCl 2 + H2O
PROPERTIES:-
1. CO2 is colourless, odourless gas about 1.5 times heavier than air.
2. CO2 form carbonic acid with water which is a weak dibasic acid and dissociates in two steps:
H 2 CO3( aq ) + H2O(l )  HCO3( aq ) + H 3 O(aq )
HCO3( aq ) + H2O(l )  CO(aq
2 
) + H 3 O( aq )

H 2 CO3 / HCO3 buffer system helps to maintain pH of blood 7.20 to 7.42.

3. Photosynthesis:- CO2 is absorbed by plants in presence of chlorophyll and sunlight to form
glucose and oxygen.
l & h
6CO2 + 6 H 2 O Chlorophyl
  C 6 H 12 O6 + 6O2
4. CO2 can be readily liquefied under a pressure of 50 to 60 atm at room temperature. When liquid CO2 is
allowed to evaporate rapidly it changes to a solid called dry ice. It is used as refrigerant.
A mixture of dry ice and ether can generate a low temperature of about -1800C, which is
used in the liquefication of other gases.
5. Action of Ammonia:- Gives urea.
2NH 3 + CO2  NH 2 CONH 4  NH 2 CONH 2 + H2O
Urea

“SILICON DIOXIDE”
Silicon dioxide is commonly known as silica. Silica occurs in several crystallographic forms such as
quartz, tridymite and cristobolite. Each of these have different structures at high and low temperature and
they are interconvertible.
Structure of Silicon dioxide(SiO2):-
(i) SiO2 is covalent three dimensional network solid.
(ii) Each silicon atom is tetrahedrally surrounded by four oxygen atoms, thus there are no discrete SiO2
unit.
| | | | |
—Si —O —Si —O— Si —O— Si —O —Si —
| | | | |
O O O O O
| | | | |
—Si —O —Si —O —Si —O —Si —O —Si —
| | | | |
O O O O O
| | | | |
—Si —O— Si—O— Si—O— Si—O— Si—
| | | | |
  Silica in its normal form is almost non reactive.
Explanation:- Due to very high Si—O bond enthalpy. It resists the attack by halogens, dihydrogen and
acids etc. even at high temperature.
However it is attacked by HF and NaOH.
SiO2 + 2 NaOH  Na 2 SiO3 + H2O
SiO2 + 4 HF  SiF4 + 2H2O

“SILICONS”
Silicons are polymeric compounds containing Si—O—Si linkage. These have general formula (R2SiO)n.
These have high thermal stability and are called high temperature polymer.
PREPARATION:- There are obtained by the reaction of alkyl halide with silicon in presence of metallicCu
which acts as a catalyst.
4 RCl + Si CuPowderat
  570 K
 R2 SiCl 2
The polymers are obtained by the hydrolysis of the above chloro derivatives as:
R R
| |
 HCl
Cl —Si—Cl + H2O   HO—Si—OH
| |
R R
When two molecules of dialkyl silinol combine, we get dimmer with the elimination of a molecule
of water.
R R R R
| | | |
 H 2O
HO—Si—OH + HO—Si—OH  HO—Si—O—Si—OH
| | | |
R R R R
Dimer
Since an active —OH group is left on each end of the chain, polymerization reaction continues and
the length of the chain increases. It forms linear silicone. Silicones being surrounded by non polar alkyl
groups which are water repelling in nature.

“SILICATES”
The silicates are the compounds of silicon and oxygen. These are of two types. Terminal —Si—O
bonds involving oxygen bonded to silicon and no other atoms and bridging — Si—O—Si bonds
involving oxygen bonded to two silicon atoms.
The basic building unit of all silicates is the tetrahedral SiO44 tetrahedral the four oxygen ions are
arranged at the four corners of the tetrahedron with silicon atoms at centre. Two important man made
silicates are glass and cement.