P- BLOCK ELEMENTS

Group 13 elements.

Continuation
…
GENERAL TRENDS IN PHYSICAL PROPERTIES

1) Atomic and Ionic Radii:

The atomic radii of Group 13 elements are lesser than their
corresponding group 2 elements. This is because the effective nuclear
charge increases which makes the size of the atom [Link] atomic
and ionic radii down the group increase due to the addition of a new
shell. However, there is a deviation on moving from Aluminium (143
pm) to Gallium (135 pm). This arises due to the poor shielding of the
intervening d-orbitals in Gallium, making the size smaller than
Aluminium.
Boron< Aluminium > Gallium < Indium< Thallium
• Ionization Energy
Down the group, the values of Ionization Enthalpy do not decrease smoothly.
From Boron to Aluminium, the Ionization Enthalpy increases as expected. But
from Aluminium to Gallium, the Ionization Enthalpy increases slightly. The
first Ionization Enthalpy of Thallium is greater than Aluminium.
Reason: This trend is observed due to the poor shielding of d and f orbitals.
Gallium is smaller than Aluminium due to poor d shielding, therefore, IE1 of
Aluminium < IE1 of Gallium. Similarly, Thallium has intervening f orbitals
which are very poor at shielding, thereby increasing the IE1 of Thallium.
• Electronegativity
The electronegativity first decreases from B to Al, then it increases slightly from
Aluminium to Tl. This can be attributed to the poor shielding of the intervening d
and f orbitals.
• Density
The elements of Group 13 have higher densities than group 2 elements. This is
because they have smaller sizes, and hence small volumes. The density increases
from B to Tl.
• Melting Point
M.P decrease from B to Ga and then increases from G to Tl.
• Metallic Character
- Metallic character of B < Al-: due to smaller size and huge ionisation
potential of B and Al.
- Metallic character of Al > Ga > In > Tl-: Al follows s-block elements
while Ga, In and Tl follow d-block elements. s-electrons screen the
nucleus more effectively, than d-electrons . Thus d-orbital electrons
are more firmly held than s-orbital electrons and metallic character
decreases from Al to Tl.
• What is inert pair effect?
The normal oxidation state results by the Group 13 elements in the group are
+3, and +1. As we go down the group of the Boron family, the tendency to form
+1 ion increases. This is due to the inert pair effect. To elucidate, consider B3+
and B+. It is shown experimentally that B3+ is more stable than B+. Now
consider, Tl3+ and Tl+. It was seen that Tl+ is more stable than Tl3+. This can be
explained using the inert pair effect. It is the non-participation of the s-orbital
during chemical bonding due to the poor shielding of the intervening electrons.
Simply put, for elements like Indium and Thallium, d and f orbitals are filled with
electrons. Since d and f orbitals’ shielding ability is very poor, the nuclear charge
that seeps through attracts the s orbital closer to the nucleus. This makes the s
orbital reluctant to bond, thereby only the p electrons are involved in bonding.
 TRENDS IN CHEMICAL REACTIVITY
1) Reactivity of Group 13 towards Acids and Alkalis
• Boron does not react with non-oxidising acids like HCl, but at higher temperatures, it reacts with strong
oxidizing acids like a mixture of hot concentrated H2SO4 and HNO3 to give boric acid.
B(s) + 3HNO3 (aq) → H3BO3 (aq) + 3NO2 (g)
• Boron resists the action of alkalis (NaOH and KOH) up to 773 K, above which they form borates.
2B(s) + 6KOH(s) → 2K3BO3(s) + 3H2(g)
• All the other elements of group 13 react both with non-oxidising and oxidising acids liberating hydrogen
gas.
• Note: The action of concentrated HNO3 renders Aluminium and Gallium passive by forming a protective
layer of oxide.
• Aluminium and Gallium can also react with alkalis liberating hydrogen gas.
2Al(s) + 2NaOH (aq) + 6H2O (l) → 2Na [Al (OH) 4] (aq) + H2 (g)
2) Reactivity of Group 13 towards Halogens
• They react with halogens at high temperatures to form trihalides MX3.

2M(s) + 3X2 (g) → 2MX3 ; (where X=F,Cl,Br,I)

• Tl however, only forms TlF3 and TlCl3.
• Note: Tl also forms mono-halides.
3) Reactivity towards metals-:
• Only boron combines with metals to form borides. The rest of the elements of group 13 are reluctant to
combine with metals. This portrays the non-metallic character of Boron.
3Mg + 2B → Mg3B
4) Reactivity towards water-:
• Boron does not react with water or steam, however, at very high temperatures it reacts with steam.
2B + 3H2O → B2O3 + 3H2
• If the oxide layer is absent, Aluminium decomposes cold water to yield hydrogen gas. Gallium and Indium
do not react with water unless oxygen gas is present. Thallium forms TlOH in moist air.
4Tl + 2H2O + O2 → 4TlOH
 PHYSICAL PROPERTIES OF BORON

• Boron is an extremely hard solid only second to diamond in

hardness.
• It has high m.p and b.p i.e 2453K and 3923K .
• It is a poor conductor of electricity.
IMPORTANT COMPOUNDS OF BORON
1) Borax-: It is also known as sodium tetraborate decahydrate (Na. B4O7.10H2O).
Borax occurs naturally as tincal. It is obtained from the mineral colemanite by
boiling it with a solution of Na2CO3.
Ca2B6O11 + 2Na2CO3 → Na2B4O7 + 2NaBO2 + 2CaCO3
Colemanite Borax
-Properties-:
i. Aqueous solution of boron is alkaline due to hydrolysis.
Na2B4O7 + 7H2O → 2NaOH + 4H3BO3
Strong alkali weak acid
ii. Boron when heated with ethyl alcohol and concentrated H2SO4, it gives volatile
vapors of triethyl borate which burn with green edged flame.
iii. This is used as test for borate radical in quantitative analysis
iv. The borax bead is used to detect colored radicals. It is transparent glassy mass.
2] Orthoboric acid (H3BO3)
Orthoboric acid is a white crystalline solid, with a soapy touch. It is
obtained from borax by treading with dil. HCl or dil. H2SO4.
Na2B4O7 + 2HCl + 5H2O → NaCl +
4H3BO3
It can also be obtained from mineral colemanite by passing SO2
through mixture of powdered mineral and boiling water.
Ca2B6O11 + 4SO2 + 11H2O → 2Ca(HSO3)2 +
6H3BO3

ii. On heating it at 370K, it forms metaboric acid (HBO2) which on

further heating ( 433K) gives boric oxide (B2O3).
H3BO3 Δ → HBO2 Δ → B2O3
• Distinction between Boric acid and a Borate-:
Boric acid reacts with methyl alcohol forming methyl borate which is a volatile
ester and burns with a green edged flame.
H3BO3 + 3CH3OH → B(OCH3)3 + 3H2O
In case of borate, no volatile ester is formed with methyl alcohol at room
temperature and no green edged flame is produced. However, green edged flame
is produced when a paste of borate and conc. H₂SO₄ is heated after the
addition of a little methyl alcohol.
3] Diborane (B2H6)
It is the simplest boron hydride. It is prepared by treating boron trifluoride with LiAlH4 in
diethyl ether.
4BF3 + 3LiAH4 → 2B2H6 + 3LiF + 3AlF3

In laboratory the diboron is prepared by the oxidation of sodium borohydride wit h iodine.
2NaBH4 + I2 → B2H6 + 3NaI + H2
In industry it is prepared by the reaction of BF3 with NaH.
2BF3 + 6NaH → B2H6 + 6NaF
- Uses
It is used as a catalyst in polymerisation reactions, as a reducing agent in organic reactions, for preparing
hydrocarbons, alcohols, ketones, acids, etc., through hydroboration method and for making high energy
fuels and propellents.
- Structure-:
• The structure of Diborane molecule consists of four hydrogen atoms and that of
two boron atoms coming on the same plane. In between these planes, there are
said to be two dividing atoms of hydrogen.
• The boron atom is known to be sp3 hybridized and has four hybrid orbitals. From
these four hybrid orbitals, three of the orbitals have one electron each, and of
which one is an empty orbital. The two electrons of the hybrid orbitals in each of
the boron atoms form 2 bonds with the 1s hydrogen atoms. The two atoms of
boron left with that of each unpaired electron orbital and empty orbital forms the
two bridgings (B–H–B) bonds with that of the two 1s hydrogen atoms, is also
called as the banana bond.
• Properties of Diborane
i. Diborone is colorless, highly toxic gas. It has boiling point of 180K. It catches fire
spontaneously when it is exposed to atmospheric air. It burns in oxygen. The
reaction is highly exothermic.
B2H6 + 3O2 → B2O3 + 3H2O + ΔH = -1976KJmol-1
ii. It is readily hydrolysed by water to form boric acid.
B2H6 + 6H2O → 2H3BO3 + 6H2
iii. With lewis bases, diborane first undergoes cleavage to form borane (BH3) which
then reacts to form adducts.
B2H6 + 2NMe3 → 2BH3.NMe3
B2H6 + 2CO → [Link]
iv. It reacts with strong alkalies to form metaborates.
B2H6 + 2KOH + 2H2O → 2KBO2 + 6H2
v. When diborane reacts with LiH in presence of ether it farms lithium borohydride.
2LiH + B2H6 Ether → 2LiBH4
• 4) Alums:

• The name alum is given to the double salt of potassium aluminium sulphate

[K2SO4. Al2(SO4)3.24.H2O]. Now a days it is used for all the double salts with M'2SO4.M"2(SO4)3.24H2O,

where M' is univalent metal ion or [NH4]+ and M" is trivalent metal ion.

• Examples:

Potash alum [K2SO4.Al2(SO4)3.24.H2O]; Sodium alum [Na2SO4.Al2(SO4)3.24.H2O] , Ammonium alum

[(NH4)2SO4.Al2(SO4)3.24.H2O], Chrome alum [K2SO4.Cr2(SO4)3.24.H2O].

Alums in general are more soluble in hot water than in cold water and in solutions they exhibit the
properties of constituent ions.
• Preparation:
The alunite the alum stone is the naturally occurring form and it is
K2SO4. Al2(SO4)3.4Al(OH)3. When alum stone is treated with excess of
sulphuric acid, the aluminium hydroxide is converted to aluminium sulphate.
A calculated quality of potassium sulphate is added and the solution is
crystallised to generate potash alum. It is purified by recrystallisation.

K2SO4.Al2(SO4)3 .4Al(OH)3 + 6H2SO4 → K2SO4 + 3Al2(SO4)3 + 12 H2O

K2SO4 + Al2(SO4)3 + 24 H2O → K2SO4.Al2(SO4)3.24 H2O
• Uses of Alum:
· It is used for purification of water
· It is also used for water proofing and textiles
· It is used in dyeing, paper and leather tanning industries
· It is employed as a styptic agent to arrest bleeding.
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