The p-Block Elements

The Elements of the P-Block

 The elements belonging to groups 13 to 18
 The p-block includes all the noble gases except
helium, all the nonmetals except hydrogen, all the
metalloids, and even a few metals.
 Lighter elements behave as non-metals and tend to
form acidic/neutral oxides while the heavier
elements tend to be metallic forming basic oxides.
 O, Si, and Al – are the most abundant elements in
Earth’s crust
 C, N, O, P, S, and Cl – are among the elements
making up the bulk of living matter
 C and S can occur in the free state
 The p-block elements have relatively little in
common except that their outer elections are in p
orbitals.
 This contrasts with the considerable similarities in
properties of the elements of the s-block and also
between those of the d-block. The p-block is more
notable for trends.
 The elements of the p-block have large variations in
their characteristics.
 Each group in the p-block has its own characteristic
properties and hence they are called as
representative elements.
 Valence electron configuration: ns2np1-6
 Highest Oxidation state is equal to the number of
valence electrons.
 The number of possible oxidation states increases from
left to right across the period.
 The stability of the oxidation state two less than the
group valency increases as we go down the group.
 Second row anomaly: The 2nd period elements differ
from others in the group on account of :
 Small Size.
 Absence of valence d-orbitals.
This is reflected mainly in the limitation of covalency,
hypervalent molecules and the type of  bonding(p -p
 or d -d ).
 Boron Group Compounds

B, Al, Ga, In, Tl

Can be rememberd as –
BAGIT (or BAG IT )

Valence electron configuration: ns2np1

 Properties and Trends
in Group 3A Element
Property Boron Aluminium Gallium Indium Thallium
B Al Ga In Tl
Atomic number 5 13 31 49 81
–1
Atomic mass(g mol ) 10.81 26.98 69.72 114.82 204.38

Electronic [He]2 s22p 1 [Ne]3s2 3p1 [Ar]3d104s2 4p 1 [Kr]4d 105s2 5p 1 [Xe]4f145d106s26p 1

Configuration
Atomic radius/pma (88) 143 135 167 170

Ionic radius (27) 53.5 62.0 80.0 88.5

M3+/pm b
Ionic radius - - 120 140 150
M+/pm
Ionization Δi H1 801 577 579 558 589
enthalpy (kJ Δi H2
2427 1816 1979 1820 1971
mol–1) Δi H3 3659 2744 2962 2704 2877
Electronegativityc 2.0 1.5 1.6 1.7 1.8

Density /g cm–3 2.35 2.70 5.90 7.31 11.85

at 298 K
Melting point / K 2453 933 303 430 576

Boiling point / K 3923 2740 2676 2353 1730

EV/ V for (M3+/M) - –1.66 –0.56 –0.34 +1.26

EV / V for (M+/M) - +0.55 -0.79(acid) –0.18 –0.34
–1.39(alkali)
a b c
Metallic radius, 6-coordination, Pauling scale,
 Physical Characteristics
 Atomic sizes are slightly smaller than the corresponding IInd
group elements.
Atomic size increases down the group except for Ga.
Ionic sizes are smaller than the corresponding IInd group
elements.
Ionic size increases down the group without exception.
The melting points and boiling points decrease on moving
down the group. However, the decrease in melting points is not
as regular as in boiling points.
Electronegativity decreases down the group, except for Ga.
The first ionization energies of group 13 elements are less
than the corresponding members of the alkaline earths. Why?
Ionization energy decreases sharply from B to Al and then the
ionization energy of Ga is unexpectedly higher than that of Al.
The second and third ionisation energies increase and not
decrease as we move towards the heavier elements. Why?
Element IE1 IE2 IE3
B 800.6 2427 3660
Al 577.5 1817 2745
Ga 578.8 1979 2963
In 558.3 1821 2704
Tl 589.4 1971 2878

2nd and 3rd ionization energies would be expected

to continually decrease moving down the group
 Oxidation States
 The lighter group 13 elements (B, Al) exist in compounds in a +3
oxidation state although boron is a typical non-metal.
 Boron forms only covalent compounds while the rest can form
ionic compounds.
 Gallium is also found in a +3 oxidation state, but is sometimes
found in a +1 oxidation state
 Indium is more commonly found in the +1 oxidation state, while
thallium is only found in this state (e.g. TlBr)
 Stability of +1 oxidation state: Al<Ga<In<Tl.
Inert
Thepair
compounds with
effect: the +1 oxidation
apparent stabilitystate arevalence
of the more ionic than thein
s electrons
ones with +3 state.
heavier p-block elements which stabilizes an oxidation number that is
2 less than the element’s group number
 Hydrides of Group 13 Elements
 The Hydrides are sp2 hybridised and there is evidence
for oligomerization of many of these hydrides, to yield
bridged compounds 3c-2e bond
-

H H H (bridging)
2c, 2e bond
-

(terminal) B B the bridging H atom

H H H is labeled m-H

 Because of its electron-deficient nature, heavier boron

hydrides are extensively bridged structures (need to be
in order to obtain octets of electrons)
 Diborane, B2H6
Commercial preparation:
2BF3 + 6NaH  B2H6 + 6NaF (at 450K)

Lab Preparation:
2NaBH4 + I2  B2H6 +2NaI + H2
4BF3 + 3LiAlH4  2B2H6 + 3LiF + 3AlF3 (Diethyl ether as solvent)

Colourless, toxic gas

Spontaneously flammable in air releasing huge amounts of heat.

B2H6 + 3O2  B2O3 +3H2O (same with higher boranes)

Readily hydrolysed to give boric acid

B2H6 + 6H2O  2B(OH)3 + 6H2
 Hydrides of Group 13 Elements
 Group 13 hydrides are susceptible to attack by
Lewis bases
 The size of the Lewis base can impose different
reaction pathways

+ - rel. small base rel. large base

H NH3 H H H H
NH3 H H NPh3 H
E E E E 2 E
H NH3 H H H H H
H NPh3

Asymmetric E = B or Ga Symmetric
Cleavage Cleavage
 Diborane, B2H6 (as lewis acid)
 Boranes react with alkali metal hydrides in diethyl ether to
form hydridoborates, the most important being
tetrahydridoborates or borohydride complexes.

Alkali borohydrides are used as reducing agents.

 Diborane with CO :
B2H6 + 2CO  2BH3.CO
 Diborane reacts with trimethylammine to give adduct .
B2H6 + 2NMe3  2BH3.NMe3
 Diborane reacts with ammonia to give adduct which changes
to borazine at 450 K.
3B2H6 + 6NH3  3[BH2(NH3)2]+1 [BH4]-1  2 B3N3H6 + 12H2
 Boron Nitrides
 Borazine, (HBNH)3 is structurally similar to benzene
and known as inorganic benzene.
H H
H N H H H benzene is aromatic
B B and requires special
N N conditions for chemical
H B H H H reaction
H H

 However, they react very differently

 Benzene is quite stable
 (HBNH)3 is (comparatively) susceptible to nucleophilic
and electrophilic attack
 Other Hydrides of Group 13
Elements
 Aluminum hydride exists as a three-dimensional network of
octahedral aluminum centers (3c-2e- Al-H-Al bonds)
H H H H H H
Al H Al H Al
H H H H H H
 The most important tetrahydrido compound is a complex
hydride of aluminium, Li[AlH4] is known. It is prepared by
reaction of AlCl3 with excess of LiH in ether.

 Ga2H6 has recently been characterized; structurally similar to

B2H6
 Hydrides of In and Tl have not been characterized.
 Halides of Group 13 Elements
 All of them form trihalides except TlI3 and all show Lewis
acid characteristics.
 Studies on the thermodynamics of formation of boron
trihalide-Lewis base adducts indicate that stability increases
in the order: L.BF3 < L.BCl3 < L.BBr3
X X
+ X B N B X
X X
N

How does this trend agree with electronegativities of X?

X X
 Boron trihalides are monomeric under ordinary conditions B
X
 In the trigonal
Rem: correct Lewis F
F planar BX3Fstructure,
F p-bonding
F F exists,
B-X most
distance
structure shows all B B B X = F: 131 pm
important
Bonds and electrons for smaller elements X = Cl: 174 pm
F F F X = Br: 189 pm
X = I: 210 pm
 Bonding in Al2Cl6

The trihalides of group 13 fume in water to form the hydroxides due to

their covalent nature and finally give the tetrahedral [M(OH)4]-1 ions:
MX3 + 3H2O  M(OH)3 + 3HX

The trihalides of group 13 react with alkalis to precipitate as their

hydroxides and dissolve in excess as the tetrahedral [M(OH)4]-1 ions:
GaCl3 + 3NaOH  Ga(OH)3↓ + 3NaCl
Ga(OH)3 + NaOH  Na[Ga(OH)4]
 Oxides and hydroxides
♣Almost all the elements of group 13 form oxides and hydroxides of the
composition M2O3 and M(OH)3 respectively.
♣Boron is unreactive in crystalline form. Aluminium forms a very thin
oxide layer on the surface which protects the metal from further attack.
Amorphous boron and aluminium metal on heating in air form B2O3 and
Al2O3 respectively. With dinitrogen at high temperature they form
nitrides.
4E(s) + 3O2  2E2O3(s)

2E(s) + N2  2EN(s)
♣The nature of these oxides / hydroxides change from weakly acidic to
amphoteric and amphoteric to basic in moving down the group from B to
Tl. WHY?
 Behaviour in aqueous solutions
Al, Ga, In and Tl exhibit a well-defined aqueous chemistry in their
tripositive states. Species like [M(OH)4]-, [M(H2O)2(OH)4]-, [M(OH2)6]3+ for
M = Al, Ga, In, exist in aqueous solution. Al, Ga. In and Tl ions exist as
octahedral aqua ions, [M(OH2)6]3+ in aqueous solution and many salts like
halides, sulphates, nitrates and perchlorates exist as hydrates. Why does
Boron not show the same ionic species?

Aluminium sulphate forms double salts with sulphates of other metals

and is called alum, having the general formula M2SO4. Al2(SO4)3.12H2O,
where M is a univalent cation, Na+ or K+. Alums are extensively used in the
softening of hard water and as mordant in dyeing and printing of textiles.
A mordant helps to bind the dye to the fabric. The trivalent metal cations
of about the same size as that of Al3+ are capable of replacing aluminium in
alums.
Examples: Ti3+, Cr3+, Mn3+, Fe3+ and Co3+.
 Anomalous Behavior of Boron
1. Boron is a non-metal whereas aluminium is a metal.
2. Boron is a bad conductor of electricity whereas aluminium is a good
conductor.
3. Boron exists in two forms-crystalline and amorphous. Aluminium is a soft
metal and does not exist in different forms.
4. The melting point and boiling point of boron are much higher than those of
aluminium.
5. Boron forms only covalent compounds whereas aluminium forms even
some ionic compounds.
6. The hydroxides and oxides of boron are acidic in nature whereas those of
aluminium are amphoteric.
7. The trihalides of boron (BX3) exist as monomers. On the other hand,
aluminium halides exist as dimers (Al2X6).
8. The hydrides of boron are quite stable while those of aluminium are
unstable.
 Diagonal resemblance of boron
with silicon
1. Boron and silicon exhibit the typical properties of non-metals. These do not
form cations. Both exist in amorphous as well as crystalline forms.
2. Boron oxide (B2O3) and silica (SiO2) both are acidic and dissolve in alkali
solutions to form borates and silicates respectively.
B2O3 +6NaOH  2 Na2BO3 + 3H2O
SiO2 + 2NaOH  Na2SiO3 + H2O
Borates and silicates have tetrahedral BO4 and SiO4 structural units respectively.
3. The chlorides of both B and Si get hydrolyzed by water to boric acid and silicic
acid respectively.
BCl3 + 3H2O  H3BO3 +3HCl
SiCl4 + 3H2O  H2SiO3 +4HCl
4. The hydrides of Boron and Silicon are quite stable. Numerous volatile hydrides
are also known which catch fire on exposure to air and are easily hydrolyzed.
5. Both elements are semiconductors.
 Comparison of Group 13 Trends
 Boron
– Forms covalent bonds exclusively
– Forms trivalent compounds that act as Lewis acids
– Commonly exist in polyhedral structures
– Oxide (B2O3) and hydroxide (B(OH)3) are both modest Lewis acids
– Tetrahydride (BH4-) is a strong reducing agent
 Aluminum
– Exists in ionic compounds (Al3+)
– Oxide and hydroxide are amphoteric (can act as acid or base)
– Hydride anion (AlH4-) is a good reducing agent (though not as
strong as BH4-). Example LiAlH4
 Ga, In, Tl inert pair effect
– Readily yield cations (+1,+3)
– +1 compounds are increasingly stable down the group
– Only gallium forms a hydride (GaH4-) but it is not a good reducing
agent.
 Borax
Na2B4O7·10 H2O, a hydrated borate, is the primary source of boron.
In fact it contains the tetranuclear units [B4O5(OH)4]2- and correct formula;
therefore, is Na2 [B4O5 (OH)4 ].8H2O.
Boric acid