Unique properties of p block elements and their

compounds
Elias lectures 2016 CML 514 IITD
Name The p - block elements Helium
Symbol Electronic configuration, Atomic number and He
Elec. Config. atomic weights 1s2
At. No At. Wt.. 2 4.00

Boron Carbon Nitrogen Oxygen Fluorine Neon

B C N O F Ne
[He]2s22p1 [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p6
5 10.81 6 12.01 7 14.01 8 16.00 9 19.00 10 20.18
Aluminum Silicon Phosphorus Sulfur Chlorine Argon
Al Si P S Cl Ar
[Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6
13 26.98 14 28.09 15 30.97 16 32.06 17 35.45 18 39.95
Gallium Germanium Arsenic Selenium Bromine Krypton
Ga Ge As Se Br Kr
[Ar]4s24p1 [Ar]4s24p2 [Ar]4s24p3 [Ar]4s24p4 [Ar]4s24p5 [Ar]4s24p6
31 69.72 32 72.64 33 74.92 34 78.96 35 79.90 36 83.80
Indium Tin Antimony Tellurium Iodine Xenon
In Sn Sb Te I Xe
[Kr]5s25p1 [Kr]5s25p2 [Kr]5s25p3 [Kr]5s25p4 [Kr]5s25p5 [Kr]5s25p6
49 114.82 50 118.71 51 121.76 52 127.60 53 126.90 54 131.29
Thallium Lead Bismuth Polonium Astatine Radon
Tl Pb Bi Po At Rn
[Xe]6s26p1 [Xe]6s26p2 [Xe]6s26p3 [Xe]6s26p4 [Xe]6s26p5 [Xe]6s26p6
81 204.38 82 207.20 83 208.98 84 209 85 210 86 222
World chemicals turnover in 2010 was valued at 2353 billion Euros with
China being the major producer of most of the bulk chemicals.

Among industrially important inorganic chemicals and chemical compositions, those

based on the p block elements constitute a major component if one keeps the
organic carbon based compounds aside.

Among the top fifteen bulk inorganic chemicals/elements produced by

chemical industries across the world, ten belong to the p block.

materials for infrastructure clay bricks (200 billion bricks per year),
cement (3600 mmt)
glass (56 mmt)
Natural zeolites (3 mmt).

Three major organic chemicals produced in the word in 2013

ethylene (156 mmt)
propylene (80 mmt)
methanol (65 mmt)
1million metric ton (mmt) =1 000 000 000 kilograms (10 crore kg!)
 S. No Bulk Inorganic Year of Quantity Major uses and applications
Chemical/Element/ reference (world production
Composition in million metric
tons)
1 Cement 2013 3600 Construction
2 Iron (steel) 2013 958(1528) Construction, ships, containers etc
3 Calcium carbonate/ 2008 285 Metallurgy, building products, pulp
Lime stone and paper
4 Sulfuric acid 2010 198 Production of phosphate fertilizers
from Fluorapatite
5 Ammonia 2013 140 Fertilizers (80%), nitric acid
synthesis
6 Sulfur 2010 77 Sulfuric acid manufacture
7 Sodium carbonate 2012 62 Glass, detergents and cleaners, as
source of sodium ion
8 Nitric acid 2013 60 Ammonium nitrate for use in
fertilizers and explosives
9 Sodium hydroxide 2004 60 Paper, detergents, Bayer process for
aluminum
10 Glass 2010 56 Construction, buildings, automobile

11 Chlorine 2010 56 Ethylene dichloride, propylene

oxide, isocyanates
12 Hydrogen 2013 50 Ammonia and methanol synthesis,
petroleum refinery
13 Phosphoric acid 2009 46 Phosphate fertilizers
14 Aluminum 2012 45 Construction, airplanes etc
15 Hydrochloric acid 2005 20 PVC manufacture

1million metric ton (mmt) =1 000 000 000 kilograms ( 10 crore kg!)
 Common inorganic fertilizers

The multibillion dollar chemical equation!

Ca5(PO4)3X + 5 H2SO4 + 10 H2O → 3 H3PO4 + 5 CaSO4·2 H2O + HX
X=F (fluorapatite) OH hydroxyapatite)
Examples of pesticides/nerve gases based on phosphorus and chlorine
 Solar energy materials
Name Bandgap Conv. Type Advantages Disadvantages
(300K) eV efficiency
Material (%)
c-Si 1.1 19-22.5 Wafers (cut High conversion Very expensive, loss
from efficiency, long life. of material during
Monocrystalline silicon cylindrical Performs in low light cutting of ingots
ingots)

p-Si 1.1 13.0-16.0 casting Process simple and less Less efficient due to
molten costly than c-Si. Lower lower purity , lower
Polycrystalline silicon silicon heat tolerance than c-Si. space efficiency

a-Si 1.7-1.8 11.1 Thin films Mass production easy, Mostly small scale
flexible, cheap applications (e.g.
Amorphous silicon calculators)
CdTe 1.4 16.5-17.0 Thin films Cost efficient . large scale Cadmium is highly
installation possible toxic, degrades
Cadmium telluride
GaAs 1.424 28.8 Thin films world record for the High cost
highest-efficiency single-
Gallium Arsenide junction solar cell
CIGS 1. to 19.5-20.8 Thin films Flexible substrate, more Less toxic than CdTe,
1.7 efficient than CdTe Degrades
Copper indium gallium
selenide
Multi Junction (MJ) 40.7 Thin films Highest conversion Most expensive.
Indium gallium phosphide; 1.9 efficiency. Application Degrades fast
Indium gallium arsenide; preferred in space
1.4
Germanium
0.7
The complete spectrum of sunlight, from infrared to ultraviolet, covers a bandgap range
from approximately 0.5 eV to about 2.9 eV (red light 1.7 eV and blue light 2.7 eV).
Common explosives and their velocities
of detonation

Higher velocity of detonation (VoD)

Higher density
Zero oxygen balance (OB%) indicating a good fuel to
oxidizer ratio. This indicates the degree to which an
explosive can be oxidized.
Higher value of heat of explosion Qv.
Higher volume of gases generated.
 Nuclear materials based on the p block

Lead can effectively attenuate certain kinds of radiation because of its relatively
high density (11.3) and high atomic number. It is quite effective at stopping gamma
rays, and X-rays. Lead’s high density is caused by the combination of its high atomic
mass and the relatively small size of its bond lengths and atomic radius. Lead is
ineffective in stopping beta particles because they can produce secondary radiation
when passing through elements with a high atomic number and density
(Bremsstrahlung). Instead, plastic can be used to form an efficient barrier for dealing
with high-energy beta radiation before the radiation reaches the lead barrier.

isotope Cross section for Half life Natural abundance

thermal neutron
capture (barn)
Indium -115 100 4.41×1014 years 95.71%
Boron-10 200 Non radioactive 19.9%
Cadmium- 113 30,000 7.7 x 1015 years 12.22%
Xenon- 135 2,600,000 9.14 hours 0 (Xe-135 is a decay
product of I-135)
 Transparent conducting oxides (TCOs)

Transparent conducting oxides (TCOs) are electrical conductive materials with

comparably low absorption of electromagnetic radiation within the visible
region of the spectrum. Indium tin oxide is one of the most widely
used transparent conducting oxide because of its unique properties such
as good electrical conductivity (~104 S/cm), very high optical transparency
(75-90%), as well as the ease with which it can be deposited as a thin
film. Indium tin oxide is a mixture of In2O3 (90%) and SnO2 (10%). The
conductive and highly transparent surface created by ITO when applied as a
coating to glass or other transparent surfaces, reflect infrared rays while
allowing visible and UV light to pass. ITO which has a stability upto 150 °C is
omnipresent in modern touch screen technology starting from automatic
teller machines, touch screen mobile phones and tablet PCs. It is also used in
flat panel LCD, OLED plasma and electro-chromatic displays, solar panels and
even on the energy efficient windows of modern aircrafts for easy deicing.
 Inorganic polymers

Among the three, the one which has the highest market in terms of quantity are
the silicones. The global market for silicones in terms of revenues was estimated to
be worth $13,000 million in 2011 and is expected to reach $19,000 million by 2017.
The silicone market is dominated by elastomers and fluids, together accounting for
over 80% of the overall market. Silicones possess superior properties and
characteristics which are extremely useful in the automotive, construction, medical
and personal care and, electrical and electronics end-user industries
 Industrial success of Silicones : PDMS

Hydrophobicity Oxygen permeability

Wide temp range Low glass transition temp
Antifrothing Non toxicity

First human foot print on

moon
Moon temperature
(-153 to +107 °C)
Light Emitting Diodes

Semicond Wavele VF @
Colour
uctor ngth 20mA
850- Infra-
GaAs 1.2v
940nm Red
630-
GaAsP Red 1.8v
660nm
605-
GaAsP Amber 2.0v
620nm
GaAsP: 585-
Yellow 2.2v
N 595nm
550-
AlGaP Green 3.5v
570nm
430-
SiC Blue 3.6v
505nm
GaInN 450nm White 4.0v

The main P-type dopant used in the manufacture of Light Emitting Diodes is
Gallium and that the main N-type dopant used is As giving the resulting
compound of Gallium Arsenide (GaAs) . Gallium Arsenide on its own as the
semiconductor compound radiates large amounts of infra-red radiation from
its junction when a forward current is flowing through it. But by adding
Phosphorus, as a third dopant the wavelength of the emitted radiation is
reduced to below 680nm giving visible red light to the human eye.
Similarly GaN radiates blue / UV light. By introducing indium as a dopant one
can get blue, green, yellow etc – by varying the band gap.
 Energy Efficiency
& Energy Costs Light Emitting Incandescent Compact
Diodes (LEDs) Light Bulbs Fluorescents
Life Span (average) 50,000 hours 1,200 hours 8,000 hours
Watts of electricity used 6 - 8 watts 60 watts 13-15 watts
(equivalent to 60 watt bulb).
Kilo-watts of Electricity used 329 KWh/yr. 3285 KWh/yr. 767 KWh/yr.
(30 Incandescent Bulbs per year equivalent)
Annual Operating Cost $32.85/year $328.59/year $76.65/year
(30 Incandescent Bulbs per year equivalent)
Environmental
Impact

Contains the TOXIC Mercury No No Yes

Carbon Dioxide Emissions 451 4500 1051
(30 bulbs per year) pounds/year pounds/year pounds/year
 As reagents and catalysts

Lewis acid catalysts based on main group metals such as aluminum, boron,
silicon, tin and antimony (BF3, SnCl4, SiF4, SbF5 and AlCl3 ) are used extensively
in reactions such as Friedel-Crafts and the aldol reaction, and various pericyclic
processes that proceed slowly at room temperature, such as the Diels-Alder
reaction, Claisen rearrangement and acetal formation.

The unusual catalytic activity shown by aluminosilicates such as zeolites and clays
(e.g. montmorillonite) are unique to the p block elements. The open framework
stable structures such as zeolites and ALPO can acts as dehydration and shape
selective catalysts. Also of importance are methylating agents such as AlMe3 and
its partially hydrolyzed product methyl alumoxane (MAO) which find application
as cocatalysts in olefin polymerization reactions
 Si 50% - Al 50%
Cations Na, Ca
Linde A
Polar Ring 8
3-D straight channels

Si 93 %
ZSM 5 non-polar Ring 10
Hydrophobic
1-D channels

Si x% - Al y%
Cations Na, Ca
Faujasite Polar
Ring 12
3-D entangled
channels
 ZSM-5: Shape Selectivity in Catalysis

+
(a)

(b) CH3 OH +

(a) reactant selectivity for cracking of a straight-chain versus branched C7.

(b) product selectivity for p-xyl ene over o- and m- forms
 Ammonium phosphates as Forest Fire retardants

Patent Phos check

Diammonium phosphate Ammonium polyphosphate

45% Diammonium phosphate,
Ammonium sulfate 45% Diammonium sulfate,
Sodium calcium borate Monoammonium phosphate,
Sodium carbonate Attapulgus clay,
Rhodamine B- 0.05% Guar gum,
Red dye
 Periodicity of properties of p block
elements

F2=2.87

Li= -3.0

Inert pair efffect

Atomic radii of the elements
First Ionization energies

highest
 net positive charge experienced by an
electron in a multi-electron atom

Atomic
Radii
amount of energy released when an electron is added to a neutral atom
 First Ionization He
Energy
He Atomic radii

B C N O F Ne B C N O F Ne
Increases Decreases

high
atomic
radii

Tl Pb

Electronegativity
&
Effective Nuclear He
charge
B C N O F Ne
Increases

Decreases
Decreases
 Valence shell electron pair repulsion theory (VSEPR)
The rules are based on the Points on a sphere model as it envisages the
arrangement of electron pairs as points on a spherical core. The rules have been
quite successful in predicting the shape of compounds whose central atom is a p
Ronald Gillespie block element and not very useful in the case of compounds of transition metals .
Mc Master Univ., Canada

The "AXE method" of electron counting

A represents the central atom and always has an implied subscript one.
X represents the number of ligands (atoms bonded to A).
E represents the number of lone pairs surrounding the central atom.

The electrons are arranged in pairs that are either bonding (shared) pairs [X] or
non bonding (unshared) pairs [E]. In the usual σ - π treatment this usually means
ignoring the π bonds temporarily since they will follow the σ bonds and therefore
the two bonding pairs of a double bond or three bonding pairs of a triple bond are
all primarily considered as a single point on the sphere.
e.g. H2O AX2E2 2 bonding pairs and 2 lone pairs on Oxygen as central atom
O=PCl3 AX4 4 bonding pairs π bond ignored with phosphorus as central atom
 The rules
The pairs of electrons in the valence shell adopt that arrangement which
maximizes their distances apart. This in other words means that the bonding
and non bonding electron pairs are arranged as far apart from each other as
possible on the surface of a sphere with the atom A at the centre of the sphere.

Rules which take care of the deviations observed from the ideal geometry
Rule 1: A non bonding lone pair [E] occupies more space on the surface of the central
atom than a bonding pair [X]. In other words, lone pair- lone pair repulsion is greater
than lone pair- bond pair repulsion which is greater than bond pair-bond pair
repulsion. Lone pairs choose the largest site, e.g., equatorial in trigonal bipyramid and axial in pentagonal
bipyramid. If all sites are equal, lone pairs will be better placed trans to each other.
Rule 2: The strengths of the repulsions between bonds of different multiplicity
decreases in the order: triple–double > double– double > double–single >
single–single.

Rule 3: Bonding pairs to electronegative substituents occupy less space than

those to more electropositive substituents. Therefore angles between the single
bonds, decrease with increasing electronegativity of the substituent.
This decrease in domain size with increasing electronegativity of the substituent happens as more of the bonding
electron density is shifted to the electronegative substituent. In other words, the repulsion between single bonds
decreases with increasing electronegativity of the substituent and/or decreasing electronegativity of the central atom.

O O O

C C C N N
Cl F
H H Cl Cl F F Cl F
Cl F
116o 111o 108o 107o 102o
Shapes of compounds having odd number of electrons

The odd electron also has an influence on the molecular geometry similar to a
normal lone pair but of relatively lesser strength. As a result, the geometry
will be midway between the molecule with a full electron pair and the
molecule with one less electron pair on the central atom.
Nitrogen dioxide (NO2) (AX2E0.5) bent shape with an ONO angle 134°.

NO2− which is AX2E is also bent but has an ONO angle approximately of 120°
while NO2+ (AX2) is linear .

Similarly ClO2 (AX2E1.5) with a lone pair and an unpaired electron has OClO angle of 117.6°
while ClO2− with two lone pairs (AX2E2) has a OClO angle of 111°.

Exceptions to the VSEPR rules

1. Metal complexes and organometallic compounds based on transition elements

2. Many triatomic alkaline earth metal dihalides, although expected to be linear have
been found to be bent (approximate X-M-X angles: CaF2, 145°; SrF2, 120°; BaF2,
108°; SrCl2, 130°; BaCl2, 115°; BaBr2, 115° and BaI2, 105°). Gillespie has proposed that the
reason for the same is due to loss of spherical symmetry of the inner shell of the metal
atom due to polarising effect of the relatively electronegative halide substituent’s.
Li2O also is linear although it is expected to be bent and this has been ascribed to the
bonding being more ionic resulting in repulsion between the lithium atoms.
 3. The silyl ether O(SiH3)2 has a relatively larger Si-O-Si angle (144.1°), while
similar bond angles of Cl2O (110.9°) and (CH3)2O (111.7°) are in the
expected range.

Gillespie's rationalization for this observation is that the localization of the lone
pairs, and therefore their ability to repel other electron pairs, is greatest when
the ligand has an electronegativity similar to or greater than, that of the central
atom. When the central atom is more electronegative, as in O(SiH3)2, the lone
pairs are less well-localised and have therefore a weaker repulsive effect.

4. Some molecules in which the central atom is from periods 3 and 4 and in which
the ligands are less electronegative, do not have sufficient space in their valence
shell to accommodate six bonding domains and a large lone pair domain. In such
molecules the lone pair is squeezed into a spherical domain surrounding the core
and inside the bonding domains (stereochemically inactive s orbital) which
therefore have an octahedral arrangement. Thus some AX6E molecule such as
SeCl62- and TeBr62- have a regular octahedral shape but with longer than normal
bonds.
 Some new developments

The electron pair domain model

proposed by Gillespie and Harigittai in 1991 followed by Gillespie and Robinson in 1996.
This model was based not on pairs of electrons but on a region in space where there is
more probability of finding an electron pair (bonding or lone pair).
An electron pair domain is a region in space where there is an enhanced probability of
finding an electron pair.
An electron pair domain extends around the most probable position of finding an
electron pair as determined by the Pauli principle and the probability decreases on
increasing the distance from the most probable position.

A lone pair domain can in general be thought of as more spread out and larger than a
bonding pair domain as the electrons of a lone pair are subject to the attraction of only
one atomic nucleus while those of a bonding air are subject to the attraction of two
nuclei taking part in the bond formation.
A bonding pair domain therefore taken up less space around a nucleus compared to a
lone pair domain because the former is stretched out more towards the ligand/
substituent of the central atom. Why a lone pair occupies more space than a bonding
pair is well explained by the domain concept.
Ligand close packing model

The basis of this model is that the bond angles are determined by the
packing of the ligands or substituents around a central atom. Irrespective of
having lone pairs or not, the distance maintained between the substituents
on a central atom will be almost same while the bond lengths and bond
angles will be different as shown in the following examples.
 Arrive at the shape of the following compounds using VSEPR theory

NSF3 IOF4− IO2F52− XeOF5− XeOF3-

Td Sq. Py PBP Pent Pyr Sq.Pl

ICl2 +, ICl2− IF4+, IF4− XeF5+, XeF5−

bent Lin. See saw Sq. PL Sq. Pyr Pent.Pl

IO3− IF52− [C6H4C(O)O] I(OAc)3 Kr2F3+

Tr.Pyr Pent.Pl Sq. Pyr
 Kr2F3+

Inorg. Chem., 2001, 40 (13), pp 3002–3017 Around central F : Td

Around Krypton : TBP
Arrangement Bonding Lone Occupancy/ Shape of the Examples
pairs pairs Steric number molecule
X E
Linear 2 0 2 Linear AX2 CO2, CS2, HCN, BeCl2, N2O, NO2+,
NCF, NCBr

Triangular 3 0 3 Triangular planar SO3, BF3, COCl2, NO3−, CO32−,

AX3 BO33-
2 1 3 Bent SO2, O3, NOCl, SnCl2, PbF2, NOF
(V shape) AX2E
Tetrahedral 4 0 4 Tetrahedral AX4 CH4, SiCl4, SO2Cl2, POCl3, XeO4,
NSF3, ClO4−. PO43-
3 1 4 Triangular NH3, PCl3, SOCl2, IO3−
Pyramidal AX3E
2 2 4 Bent AX2E2 H2O, SCl2, NSF, ICl2+, SeCl2,
[I(C6H5)2] + , Kr2F3+
Trigonal 5 0 5 Trigonal PF5, SF4O
bipyramid Bipyramidal AX5
4 1 5 See saw SF4, XeO2F2, IF4+, IOF3, IO2F2−
AX4E
3 2 5 Bent T shape ClF3, BrF3, XeOF2,
AX3E2 I(Ph)[(CF3C(O)O)]2
2 3 5 Linear XeF2, I3−, ICl2−, BrF2−. (C6F5)2Xe
AX2E3
Arrangement Bondi Lone Occupancy Shape of the Examples
ng pairs / molecule
pairs E Steric
X number
Octahedral 6 0 6 Octahedral SF6, PF6−, SiF62− ,AlF63− , IF6+
AX6
5 1 6 Square pyramidal BrF5, XeF5+ , IOF4−, TeF5− , SbF52−
AX5E [C6H4C(O)O] I(OAc)3
4 2 6 Square planar XeF4, IF4− , XeOF3−
AX4E2
Pentagonal 7 0 7 Pentagonal IF7, IO2F52−
bipyramid bipyramid IOF6-, TeF7-, CH3OTeF6-,
AX7 (CH3O)2TeF5- BiF72-, SbF72-
6 1 7 Pentagonal XeOF5−, IOF52− [IF5(C6H5)]−
Pyramid XeF6 ( monocapped octahedron)
AX6E
5 2 7 Pentagonal planar XeF5−, IF52−
AX5E2 X X
X X
Square 8 0 0 Square antiprism IF8-, XeF8, XeF8 2- (AX8E)
antiprism AX8 A

X
X
X
X
 Platonic Solids
423 BC 347 BC

Archimedian Solids