P-block element

(1) Members at the top and on the right of the p-block are nonmetals (C, N, P, O,
F, S, Cl, Br, I, At).

(2) Those on the left and at the bottom are metals (Al, Ga, In,Tl, Sn, Pb, Sb Bi, Po).
(3) Between the two, from the top left to bottom right, lie an ill-defined group of
metalloid elements (B, Si, Ge, As, Te)

BORON FAMILY(Group 13 or IIIA)(B, Al, Ga, In, Tl, )

PHYSICAL :
1. Valence Shell EC : ns2np1
2. Abundance : B : less than 0.0001% of earth crust, Al : 3rd most abundant metal in earth
crust(8.3%),first being O(45.5%) and second Si(27.7%). Ga, In and Tl are less abundant element
3. Atomic and Ionic Radii : Smaller than respective Group 2 elements. Increases down the
group (Exception Ga Al - due to d-block contraction)
4. Ionisation energy : IE1 less than respective Group 2 elements(upto Ga) due to ns2 stability of
the latter. But have less IE1 than respecitve Group 14 elements. In the group Ga > Al due d-
block contraction and Tl has very high IE(2nd to B) due to lanthanoid contraction. Order :
B>Tl>Ga>Al>In
5. Electronegativity : More than respective Group 2 elements but less than group 14 elements.
EN decreases fromB to Al and thereafter increase marginally. This is due to d and f-block
contractions.
6. Metallic/Non-metallic character : B is a hard and black coloured metalloid existing as many
allotropes. Others are metals.Al shows some similarities with B. Ga, In and Tl are shows
exclusively
metallic character.
7. Oxidation State(OS) : +1 and +3. B and Al shows +3 state. Boron show covalent bonding
becausehigh IE1, IE2 and IE3 values. Compounds of other elements have appreciable ionic
character. Alcompounds are predominantly covalent with appreciable ionic character. The
stability of +1 stateincreases down the group(Inert Pair Effect). Ga, In and Tl show both +1 and
+3 states. +3 state of Tl is highly unstable. TlCl3 does not exist at room temperature. Tl3+ is
therefore a strong oxidisingagent(Standard Reduction Potential = + 1.26V). +3 state compounds
have more covalent characterwhile +1 state have greater ionic character(Fajan’s rule). TlCl is
stable and ionic.BCl3 and AlCl3 are Lewis acids as they are electron deficient covalent
molecules(sextet). BF3 can formadduct with NH3.Trichlorides are hydrolysed in water/base to
form [M(OH)4]– where M is sp3 hybridised. AlCl3 inacidic aq. solution exist as [Al(H2O)6]3+ ion.
8. MP/BP : B has very high mp due to covalent network structure in its crystalline structure. MP
decreases upto Ga(300C) and increases. Ga is a liquid metal during summer. BP decreases
regularlydown the group.
9. Density : Increases regularly down the group.
CHEMICAL:
1. Reactivity with Air :
Crystalline B and Al are resistant to air attack. Al forms a protective oxide layer. However
amorphous B and Al on heating in air forms B2O3 and Al2O3 respectively. Tl doesnot form oxide.
At high temperature they react with N2 to form nitrides.
Al + N2 AlN

B + N2 BN

Nature of Oxides: B2O3 is acidic while Al2O3 and Ga2O3 are amphoteric while other oxides are
basic.
Al2O3 + HCl AlCl3 + H2O

Al2O3 + NaOH NaAlO2 + H2O

2. Formation of Hydroxides :(Reactivity with water)

B does not react with water. Al-Hg reacts with water forming Al(OH)3 and H2.. Pure Al does not
reactdue to formation of Al(OH)3 protective layer. The oxides react with water to form their
hydroxides.Although B2O3 reacts with water butAl2O3 does not react with water.
M2O3 + H2O M(OH)3
B(OH)3 is acidic. It actually written as H3BO3(orthoboric acid). Al(OH)3 and Ga(OH)3 is
amphoteric while other hydroxides are basic. Tl(OH)3 does not exist due to inert pair effect. As
we go down the group M–O bond energy decreases and OH– are easily produced. In case of
B(OH)3, B-O is stronger and does not produce OH–. In stead it produces H+ ions in water.
3. Reactivity towards acids and alkalies:
B does not react with acid or alkali. Al dissolves both in acid and strong bases.
2Al + 6HCl 2AlCl3 + 3H2
2Al + 2NaOH + 6H2O 2Na[Al(OH)4] + 3H2
OR 2Al + 2NaOH + 2H2O 2NaAlO2 + 3H2
NaAlO2 and Na[Al(OH)4] are formula written for sodium aluminate or sodium metaaluminate.
The other formula for the aluminate is Na2O.Al2O3 or Na2Al2O4.
4. FORMATION OF HYDRIDES:
Elments do not combine directly with hydrogen.
Boron hydrides : Boranes. Hydrides of other metals AlH3, GaH3 and TlH3 are polymeric.

BORANES: There are two types of boranes having formula BnHn+4 : B2H6, B3H7, B4H8 etc.
and BnHn+6 : B4H10, B5H11, B6H12 etc.
Out of all boranes diborane(B2H6) is most significant.
DIBORANE:
Preparation : (1) 4BF3 + 3 LiAlH4 2 B2H6 + 3 LiF + 3AlF3 (ether is used as solvent)
(2) 2NaBH4 + I2 B2H6 + 2NaI + H2 (polyether as solvent)
(3) 2BF3 + 6 NaH ----450K----> B2H6 + 6NaF
Properties : (1) Diborane is colourless, highly toxic gas with BP 180K. It is spontaneously
inflammable
on exposure to air.
(2) It burns in oxygen releasing great amount of energy.
B2H6 + 3O2 B2O3 + 3H2O + 1976 kJ
(Higher boranes are liquids/solids used as high energy fuels)
(3) Boranes readily undergo hydrolysis to give boric acid.
B2H6 + 6H2O 2 H3BO3 + 6H2
(4) Formation of adduct with trimethyl amine and CO.
B2H6 udergoes cleavage reaction with Lewis bases like Me3N and CO to form adducts.
B2H6 + 2 Me3N 2 BH3.NMe3; B2H6 + 2CO 2 BH3.CO
(5) Formation of complex hydride: (metal borohydrides)
2NaH + B2H6 2Na[BH4] B2H6 + LiH Li[BH4]
Borohydrides are used as powerful RAs in organic reactions.
(6) Diborane reacts with ammonia to give first B2H6.2NH3 whose formula is [BH2(NH3)2]+[BH4]–
Further heating produces borazine(borazone), B3N3H6 also called ‘inorganic benzene’.
3 B2H6 + 6NH3 3 [BH2(NH3)2]+[BH4]– -----heat--- 2 B3N3H6 + 12H2

( Borazine)

Structure of diborane –

B2H6 cannot have a ethane(C2H6) type of structure as each boron as 3 electrons in the valence
shell.Hence it is an electron deficient molecule.
Two B atoms and 4 H atoms lie in one plane having 4 normal 2-electron-2-centred(2e-2c) B–H
bonds. These are called the terminal H atoms. The other two H atoms lie perpendicular to the
plance carryingother atoms - one above the plane and the other below. Each of these H atoms are
linked both the B atomswith 2-electron-3-centred(2e-3c) bonds or banana shaped bonds. These
two H atoms are called bridging Hatoms. Each B uses sp3 hybrid orbitals out of which one is
vacant. The 2e-3c bonds(banana bonds) areformed by the overlap of one empty hybrid orbital of
one B, one s-orbital of H carrying one electron and onehybrid orbital of the other B carrying one
electron. The planar B-H bonds and the bridging B-H bonds havedifferent length and strengths.
The bond angles are also different. In diborane, each B is approximately sp3 hybridised.

Bonding in diborane.

pπ-pπ back bonding.: B uses vacant p-orbital while halogen(X) useslone pair orbital for the
back bonding. Back bonding is most effective inBF3 due to small size of F. So the vacant p-
orbital is least available for accepting electron.
BCl3 < AlCl3 < GaCl3 < InCl3 < TlCl3
As size of element increases back bonding becomess less effective and the lewis acid strength
increase.
Q: Why BX3 does not form dimer like AlCl3.?
Answer : Due to considerable back bonding in BX3, dative bond between one X with other B not
possible.
Q: Why does BCl3 on hydrolysis does not produce [B(H2O)6]3+ like other elements ?
Answer: Due to absence of vacant d orbitals B cannot expand its valence state.
DIAGONAL RELATIONSHIP OF B WITH Si :
1. Both are metalloids 2. Both are semiconductors
3. Hydrides are stable and inflammable
4. Halides are volatile and hygroscopic and readilty react with water.
5. Oxides are acidic
6. Both react with Mg to give borides and silicides which on hydrolysis give boranes and silanes
reaspectively.
IMPORTANT COMPOUNDS OFBORON

Orthoboric acid
Orthoboric acid, H3BO3 is a white crystallinesolid, with soapy touch. It is sparingly soluble
in water but highly soluble in hot water
Boric acid is a weak monobasic acid. It isnot a protonic acid but acts as a Lewis acid
by accepting electrons from a hydroxyl ion:
B(OH)3 + 2HOH [B(OH)4]– + H3O+
On heating, orthoboric acid above 370K forms metaboric acid, HBO2 which on further
heating yields boric oxide, B2O3.

H3BO3 HBO2 B2O3

GROUP 14 ELEMENTS: THE CARBON FAMILY
General electronic configuration of carbon family is ns2np2.
Covalent radius:-Covalent radius expected to increase from Cto Si, From Si to Pb
small increase is found.
Ionization Enthalpy:-The first ionization enthalpies of group 14 elements are high-
er than those of the corresponding group 13 elements.
Electronegativity:-Group 14 elements are smaller in size as compared to group 13
elements that’s why this group elements are slightly more electronegative than
group 13
Chemical properties:- Carbon and silicon mostly show +4 oxidation state.
Germanium forms stable compounds in +4 state and only few compounds in +2
state. Tin forms compounds in both oxidation states. Lead compounds in +2 state
are stable and in +4 state are strong oxidizing agents.
Exception:-Pb4 and SnF4 are ionic in nature. Except CCl4 other tetrachlorides are
easily hydrolysed by water.
Since carbon does not have d-orbitals and hence cannot expand its coordination
number beyond 4.
CCl4 +H2O No Reaction
SiCl4+4H2O Si(OH)4 (Silicic acid) +4HCl
Allotropes of Carbon:-The three types of allotropes are –

1-Diamond

2-Graphite

3-Fullerence
IMPORTANT COMPOUNDS OF CARBON-
Oxides of Carbon-
Preparation of Carbon Monoxide-

On commercial scale, passage of steam over hot coke produces The mixture of CO and H2 thus produced is
known as watergas or synthesis gas.

When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer gas.
2C(s) +O 2(g) +4N2 (g) 2CO(g)  4N2 (g)
