The p-block elements

Group 15 elements- N, P, As, Sb, Bi

Electronic configuration – ns2np3

Atomic and ionic radii :- increases down the group. From As to Bi only a small
increase due to presence of d or f (poor shielding effect) orbitals.

Ionisation Enthalpy :- greater than group 14 due to stable electronic

configuration.

Electronegativity :- decreases down the group.

Metallic character :- increases from top to bottom. Thus As and Sb are

metalloids while Bi is a typical metal.

Chemical Properties
Oxidation state :- common are -3, +3 and +5. The tendency to show -3 and +5
decreases down the group. Heavier elements show +3 due to inert pair effect.
Anomalous behavior of nitrogen :- is due to small size, high electronegativity,
absence of d orbitals, high I.E and ability to form multiple bonds.

Reactivity with Hydrogen :- form hydrides of formula MH3 and are pyramidal in
shape. Due to lone pair of electrons, hydrides act as Lewis bases and basic
character decreases in the order NH3> PH3> AsH3> SbH3> BiH3( increase in size).
Hydrides are good reducing agents and reducing character decreases in the
order BiH3> SbH3> AsH3> PH3> NH3 (bond dissociation energy increases)

Reactivity towards oxygen :- forms oxides of formula E 2O3 and E2O5. The acidity
of oxides decreases down the group. Thus oxides of N 2 and P are strongly
acidic, Sb amphoteric and that of bismuth weakly basic.

Reactivity with halogens :- forms halides of type MX 3 (pyramidal) and MX5

(triagonal pyramidal). Except nitrogen and bismuth others forms pentahalides.
Nitrogen do not form penta halides due to absence of d orbitals and bismuth
due to inert pair effect. Except BiF3 others are covalent.
Reactivity with metals :- exhibit -3 oxidation state. Eg :- Ca3N2,Ca3P2, Zn3Sb2
Dinitrogen
Preparation
1. NH4Cl (aq) + NaNO2(aq) N2(g) + 2H2O(l) + NaCl (lab method)
2. (NH4)2Cr2O7 Cr2O3 + N2 + 4H2O
3. Ba(N3)2 Ba + 3N2 (pure form)
Nitrogen is commercially prepared by fractional distillation of air.

Chemical Properties
The low reactivity of nitrogen is due to small size and high dissociation energy
of the molecule. At higher temperatures it reacts with metals and non-metals.
6Li + N2 2Li3N, N2(g) + 3H2(g) 2NH3(g), N2+O2 2NO
Uses of nitrogen:- manufacture of ammonia, for inert atmosphere, refrigerant,
cryosurgery

Ammonia:-
Preparation:- 2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2
Manufacture:- Haber’s process
N2(g) + 3H2(g) 2NH3(g)
According to Le Chatelier’s principle, low temperature and high pressure will
favour forward reaction. But the optimum conditions are 700k and 200atm and
catalysts like Fe with promoters K2O and Al2O3.
Chemical Properties
1. Basic nature:- NH3 + H2O NH4+ + OH-
2. Tendency to form complexes:- act as Lewis base due to presence of lone pair
of electrons. Therefore it donates electrons and form linkage with metal ions
forming complexes.
Eg:- Cu2+ + 4NH3 [Cu(NH3)4]2+, AgCl + 2NH3 [Ag(NH3)2]Cl
Uses:- to produce nitrogenous fertilizers, nitric acid, refrigerant

Oxides of Nitrogen
Nitrous oxide:- prepared by heating ammonium nitrate NH 4NO3 N 2O +
2H2O.
Nitric Oxide :- 2NaNO2 + 2FeSO4 + 3H2SO4 Fe2(SO4)3 + 2NaHSO4 + 2H2O +
2NO
Dinitrogen trioxide :- 2NO + N2O4 2N2O3
Nitrogen dioxide :- 2Pb(NO3)2 4NO2 + 2PbO
Dinitrogen tetraoxide ;- By cooling nitrogen dioxide it dimerises to tetraoxide
Dinitrogen pentoxide:- 4HNO3 + P4O10 4HPO3 + 2N2O5
The first two are neutral while others are acidic. NO 2 dimerise due to odd
electrons.
Nitric Acid (HNO3)
Nitrogen forms oxo acids like H2N2O2 (hypo nitrous acid), HNO2 (Nitrous acid)
and HNO3(nitric acid).
Nitric acid (HNO3)
Preparation
NaNO3 + H2SO4 NaHSO4 + HNO3
Manufacture Ostwald’s process
(i) Ammonia is oxidized to nitric oxide 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g
(ii) NO reacts with oxygen to form NO2 2NO(g) + O2(g) 2NO2(g)
(iii) NO2dissolves in water to form nitric acid
3NO2(g) + H2O(l) 2HNO3 + NO(g)
NO is recycled and nitric acid is concentrated to 68% by distilling and to 98%
with sulphuric acid.
Properties
[Link] nature:- HNO3 + H2O H3O+ + NO3-
2. Oxidising property:- product depends on concentration of the acid and
nature of metal.
3Cu + 8HNO3 (dil) 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc) Cu(NO3)2 + 2NO2 + 2H2O
4Zn + 10HNO3(dil) 4Zn(NO3)2 + 5H2O + N2O
Zn + 4HNO3(conc) Zn(NO3)2 + 2NO2 + 2H2O
Metals like Cr, Al do not dissolve in conc acid due to formation of passive oxide
film. It oxidizes C to CO2, I2 to iodic acid, P to H3PO4 etc.
Brown ring test:- To a solution of nitrate, added ferrous sulphate and conc
sulphuric acid along the sides of the test tube. A brown ring at the interface
between the solution and sulphuric acid indicates nitrate ion.
NO3- + 3Fe2+ + 4H+ NO + 3Fe3+ + 2H2O
[ Fe(H2O)6]2+ + NO [Fe(H2O)5(NO)]2+ + H2O
Uses:- manufacture of fertilizers, preparation of nitroglycerin, trinitrotoluene
and oxidizer in rocket fuels

Phosphorus
The allotropic forms are white (tetrahedral), red and black phosphorous. White
is less stable (bond angle 60), glows in dark and readily catches fire(P 4 + 5O2
P4O10). Red is obtained by heating white and is less reactive. It has polymer
structure consisting chains of P4. Black has two forms –alpha and beta.

Phosphine
Preparation:- By reaction of calcium phosphide with water or dilute HCl
Ca3P2 + 6H2O 3Ca(OH)2 + 2PH3 CaP2 + 6HCl 3CaCl2 + 2PH3,
P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2 (lab method)
Properties ( rotten fish smell)
1. It is slightly soluble in water and decomposes to give red phosphorous and
H 2.
2. It is weakly basic and gives phosphonium compounds with acids.
PH3 + HBr PH4Br
Uses:- Holme’s signals, smoke screens

Phosphorus Halides:- PX3 and PX5

Phosphorus trichloride (PCl3)
Preparation
P4 + 6Cl2 4PCl3; P4 + 8SOCl2 4PCl3 + 4SO2 + 2S2Cl2
Properties
SP3 hybridised with pyramidal shape. It hydrolyse to give phosphorus acid
PCl3 + 3H2O H3PO3 + 3HCl
PCl3 fumes in moisture due to hydrolyses giving fumes of HCl
Phosphorus Pentachloride (PCl5)
Preparation
P4 + 10Cl2 4PCl5; P4 + 10SO2Cl2 4PCl5 + 10SO2
Structure
SP3d hybridised with triagonal bipyramidal structure. The equatorial bonds
repel axial bonds and therefore PCl5 decomposes to PCl3 on heating.
Properties
Hydrolyse to give phosphoric acid.
PCl5 + 4H2O H3PO4 + 5HCl

Oxoacids of Phosphorous
Hypophosphorus or Phosphinic acid – H 3PO2 ( monobasic), Orthophosphorus
acid or Phosphonic acid – H3PO3 (Dibasic acid), Pyrophosphorus acid – H4P2O5
(Dibasic acid), Hypophosphoric acid H4P2O6 (Tetrabasic acid), Orthophosphoric
acid – H3PO4(Tribasic acid), Pyrophosphoric acid – H4P2O7 (Tetrabasic acid) and
Metaphosphoric acid (HPO3)n.
Orthophosphorus acid on heating gives phosphoric acid and phosphine
4H3PO3 3H3PO4 + PH3
Orthophosphorus acid has only two O-H bonds (dibasic or diprotic) while
phosphoric acid has three O-H bonds (tribasic or triprotic).
H3PO2 is reducing since it conatins two P-H bonds

Group 16 Elements:- O, S, Se, Te, Po ( Chalcogens)

Electronic Configuration- ns2 np4

1. Atomic radius:- less than group 15 and increases down the group.
2. Ionisation Enthalpy:- less than group 15 and decreases down the group.
[Link] gain enthalpy:- Due to small size Oxygen has less value than Sulphur.
From sulphur to polonium it decreases.
4. Electronegativity:- decreases down the group.

Chemical Properties
1. Oxidation state:- common is -2. They also show +2, +4 and +6. The stability
of +4 increases down the group due to inert pair effect.
2. Reactivity with Hydrogen:- forms hydrides of general formulae H 2E. The
volatility increases from H2O to H2S and then decreases. The low volatility of
H2O is due to inter molecular H-bonding. The acidic nature increase from H 2O
to H2Te (less bond dissociation enthalpy). The thermal stability decreases from
H2O to H2Te. All except water are reducing agents and it increases from H 2S to
H2Te. H2O is a liquid while H2S is a gas due to H-bonding.
[Link] with Oxygen:- forms oxides of formulae EO 2 and EO3. SO2 is a gas
while SeO2 and TeO2 are solids. SO2 is reducing while TeO2 is oxidizing agent.
4. Reactivity with halides:- forms halides of formula EX 6(octahedral) , EX4(see-
saw) and EX2. Monohalides are dimeric in nature and undergo
disproportionation reaction.
2SeCl2 SeCl4 + 3Se

Dioxygen
Preparation
1. 2KClO3 2KCl + 3O2; 2. 2HgO 2Hg + O2;
3. 2H2O2 2H2O + O2
Industrially prepared by fractional distillation of air or by electrolysis of water.
Properties
2Ca + O2 2CaO; 2ZnS + 3O2 2ZnO + 2SO2

Simple Oxides:- are binary compounds of oxygen with other elements. They
are classified as
(i) acidic oxides:- oxides that dissolves in water to give acid. Eg:- SO 2, CO2, Cl2O7
(ii) basic oxides:- Oxides that dissolves in water to give base Eg:- CaO
(iii) Amphoteric oxides:- shows both acidic and basic nature Eg:- Al 2O3
(iv) Neutral oxides:- oxides which are neither acidic or basic Eg:- CO, NO, N 2O
Ozone
Preparation:- By passing silent electrical discharge through oxygen
3O2 2O3
Properties
1. Oxidizing agent:- PbS + 4O3 PbSO4 + 4O2
2. Estimation:- When ozone reacts with buffered KI solution, I 2 is liberated
which can be estimated using sodium thiosulphate.
2I- + H2O + O3 2OH- + I2 + O2
3. NO + O3 NO2 + O2 (NO from exhaust)
4. Its shape is angular and is resonance stabilized

Uses:- germicide, disinfectant, sterlisation, bleaching, oxidizing agent

Sulphur
The main allotropic forms of sulphur are
i) rhombic(alpha):- It is the stable form of sulphur. It is yellow in colour and
exists as S8 (puckered ring structure).
(ii) monoclinic (beta):- This is formed by heating rhombic sulphur to about
369K. Monoclinic sulphur also exists as S8 with puckered ring structure.
In vapour state sulphur exist as S 2 which has two unpaired electrons, hence
exhibit paramagnetism.

Sulphur Dioxide (SO2)

Preparation
1. S + O2 SO2 2. SO32- + 2H+ H2O + SO2 (lab method)
3. 4FeS2 + 11O2 2Fe2O3 + 8SO2 (roasting of sulphide ore - commercial
method)
Properties
1. Acidic character:- SO2 + H2O H2SO3 (Sulphurous acid);
2NaOH + SO2 Na2SO3 + H2O; Na2SO3 + H2O + SO2 2NaHSO3
[Link] Chlorine:- SO2 + Cl2 SO2Cl2 (Sulphuryl chloride)
3. With oxygen:- 2SO2 + O2 2SO3
3+
4. Reducing agent:- 2Fe + SO2 + 2H2O 2Fe2+ + SO42- + 4H+
5SO2 + 2MnO4- + 2H2O 5SO42- + 4H+ + 2Mn2+
5. Its shape is angular and is resonance stabilized

Uses:- Anti- chlor, disinfectant, preservative, bleaching

Oxoacids of Sulphur:- Sulphurous acid(H2SO3), Sulphuric acid (H2SO4),
Peroxodisulphuric acid (H2S2O8), Pyrosulphuric acid or oleum (H2S2O7), H2S2O3
(Thiosulphuric acid), H2S2O4 (Thiosulphuric acid), H2S2O5 (Disulphurous acid) and
H2SO5 (Caro’s acid).

Sulphuric acid
Manufacture- Contact process
It involves the following steps
(i) Burning sulphur or sulphide ores in air to produce SO 2
(ii) Oxidation of SO2 to SO3 in presence of V2O5 2SO2 + O2 2SO3
Since reaction is exothermic and proceeds with decrease in volume, low
temperature and high pressure will favour forward reaction. But the optimum
temp is 720K and pressure is 2bar.
(iii) Absorption of SO3 in H2SO4 to give Oleum SO3 + H2SO4 H2S2O7
Dilution of oleum gives H2SO4.
Properties
The extensive use of sulphuric acid is due to (a) low volatility (b) acidic
character (c) affinity for water (d) oxidizing agent
1. Acidic character:- forms two salts- Bisulphates (HSO4-) and sulphates (SO42-)
2. Dehyrating agent:- C12H22O11 12C + 11H2O
3. Oxidising agent:- Cu + 2H2SO4 CuSO4 + SO2 + 2H2O
Uses:- manufacture of fertilizers, paints, pigments, nitrocellulose products, lab
reagent, storage batteries, petroleum refining

Group 17 Elements- F, Cl, Br, I, At (Astatine radioactive)

Electronic Configuration:- ns2 np5
Atomic and ionic radii:- smallest and increases down the group
Ionisation enthalpy:- High and decreases down the group.
Electronegativity:- Maximum and decreases down the group. Fluorine is the
most electronegative element in the periodic table.
Electron Gain Enthalpy:- maximum since they have one electron less than
noble gas configuration. Electron Gain Enthalpy decreases down the group. F 2
has low value due to small size as the result of which there is strong repulsion
between 2p electrons.
Chemical Properties
Anomalous behavior of fluorine due (i) small size (ii) high electronegativity (iii)
low F-F bond dissociation enthalpy (iv) non availability of d orbitals.
1. Oxidation state;- common oxidation state is -1. F 2 shows only -1 but others
show +1, +3, +5 and +7.
2. Reactivity with Hydrogen:- except HF all others are gases. HF is a liquid due
to association through H-bonding. The acidic character decreases in the order
HI> HBr> HCl> HF which is explained by the strength of the bond.(HI least bond
dissociation energy)
[Link]:- F2 forms two- F2O andO2F2. Cl2 forms different oxides with oxidation
number +1 to +7. All are powerful oxidizing agents.
Eg:- Cl2O, ClO2, Cl2O6, Cl2O7, BrO3 etc
4. Reactivity with metals:- form metal halides. Eg:- Mg + Br 2 MgBr2

Chlorine (Scheele)
Preparation
1.MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
2. 2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2
Manufacture
1. Deacons process:- 4HCl + O2 2Cl2 + 2H2O ( oxidation of HCl by oxygen
in presence of CuCl2 )
[Link] Process:- by electrolysis of conc NaCl solution where Chlorine is
liberated at anode.
Chemical Properties
1. With metals and non-metals:- Chlorides are formed.
2Fe + 3Cl2 2FeCl3 , P4 + 6Cl2 4PCl3
2. With Hydrogen:- HCl is formed H2 + Cl2 2HCl ; H2S + Cl2 2HCl + S
3. With NH3:- excess ammonia yields ammonium chloride
8NH3 + 3Cl2 6NH4Cl + N2
Excess chlorine gives nitrogen trichloride NH3 + 3Cl2 NCl3 + 3HCl
4. With alkali:- 2NaOH ( dil) + Cl2 NaCl + NaOCl + H2O
6NaOH(conc)+3Cl2 5NaCl+NaClO3+3H2O;
With slaked lime bleaching powder is obtained
2Ca(OH)2 + 2Cl2 Ca(OCl)2 + CaCl2 + 2H2O
5. Oxidising agent:- It oxidizes Fe2+ to Fe3+, SO2 to H2SO4
6. Bleaching agent:- due to oxidation. Cl2 + H2O 2HCl + O;
coloured substance + O colourless substance
Uses:- bleaching wood pulp and cotton, manufacture of organic compounds,
sterlising drinking water

Hydrogen Chloride
Preparation
1. NaCl + H2SO4 NaHSO4 + HCl; NaHSO4 + NaCl Na2SO4 + HCl

Properties
1. Aqua regia (3parts conc HCl + 1part conc HNO 3 ) is used for dissolving noble
metal Au + 4H+ + NO3- + 4Cl- AuCl4- + NO + 2H2O;
3Pt + 16H+ + 4NO3- + 18Cl- 3PtCl62- + 4NO + 8H2O
2. It decomposes salts of weaker acids:-
Na2CO3 + 2HCl 2NaCl + H2O + CO2
Oxoacids:- Fluorine forms HOF, Chlorine forms HOCl, HClO 2, HClO3 and HClO4,
Bromine forms HBrO3 and HBrO4 while iodine forms HIO3 and HIO4.
HOX- Hypohalous acid, HXO2- Halous acid, HXO3- Halic acid, HXO4- perchloric
acid

Interhalogen compounds
Halogens combine among themselves to form interhalogen compounds. These
can be prepared by direct combination or action of halogen on lower
interhalogen compounds.
Cl2 + F 2 2ClF; I2 + 3Cl2 2ICl3; Br2 + 5F2 2BrF5;
ClF + F2 ClF3
All interhalogens are covalent compounds. These are more reactive than
halogens due to less bond energy.
XX’3—T-shape XX’5 -- Square pyramidal XX’7--Pentagonal bipyramidal
Uses;- fluorinating agent

Group 18 Elements, He, Ne, Kr, Xe and Rn

electronic configuration-ns2np6
Occurance:- All except radon are present in the atmosphere. Radon obtained
226 222
as the decay product of radium. 88Ra 86Rn + 2He4
Argon constitute about 1 percent in dry air.
Atomic radii;- Increases down the group
Ionisation Enthalpy:- High and decreases down the group
Electron Gain Enthalpy:- large positives value due to stable electronic
configuration.
Physical properties
Helium has lowest boiling point of any known substance. Generally noble gases
have low boiling point due to weak dispersion forces.
Chemical Properties
Noble gases are less reactive due to stable electronic configuration.
(a) Xenon-Flourine compounds
Xe + F2 XeF2; Xe + 2F2 XeF4; Xe + 3F2 XeF6
XeF2 —Linear XeF4 —Square planar XeF6 —Distortred octahedral
(b) Xenon- Oxygen compounds
6XeF4 + 12H2O 4Xe + 2XeO3 + 24HF + 3O2; XeF6 + H2O XeOF4 + 2HF;
XeF6 + 3H2O XeO3 + 6HF; XeF6 + 2H2O XeO2F2 + 4HF;
XeO3 - Pyramidal ; XeOF4 - Square pyramidal; XeO4 – Tetrahedral
Uses:-
Helium:- non-inflammable, filling balloons, nuclear reactors, cryogenic agent,
superconducting magnets, diving apparatus( low solubility in blood).
Neon:- discharge tubes, fluorescent bulbs
Argon:- inert atmosphere in metallurgy, filling electric bulbs