p – BLOCK ELEMENTS

Group 15 Elements
❖ Elements: nitrogen (N), phosphorus (P), Arsenic (As), antimony (Sb), Bismuth (Bi)
❖ General electronic configuration: [noble gas]ns2np3 where n = 2,3,4,5,6
❖ Electronic configuration of elements:
o Nitrogen (7) : [He]2s22p3 o Bismuth (83): [Xe] 4f145d10 6s26p3
o Phosphorus (15): [Ne] 3s 3p 2 3 o Moscovium(115):[Rn]5f146d107s27
o Arsenic (33): [As]3d 4s 4p
10 2 3 p3
o Antimony (51): [Kr] 4d 5s 5p
10 2 3

❖ Occurrence:
o Nitrogen: 78% in air, nitrates of sodium (NaNO3 → Chile saltpetre) and nitrates of potassium (KNO3 →
Indian saltpetre), as proteins in plants and animals.
o Phosphorus: minerals of apatite family Ca9(PO4)6CaX2 where X = F, Cl, Br, in bones and living cells of
animals and plants
o Arsenic, Antimony and Bismuth: these are found mainly in the sulphide ores
❖ Atomic and ionic radii: covalent and ionic radii increase from nitrogen to bismuth.
o Nitrogen to phosphorus covalent radii increases
o As to Bi- covalent radii increases in small amount because poor shielding of completely filled d and/or
f orbitals.
❖ Ionization enthalpy: it will decrease from nitrogen to bismuth because of increase in atomic radii. Due to
half-filled p –orbital and small size, ionization enthalpy of this group is much more than 16th and 14th
group elements.
❖ Electronegativity: decreases from nitrogen to bismuth due to increases in atomic size. In case of heavy
elements i.e., As to Bi the decreases in electro negativity are very less because poor shielding of completely
filled d and/or f orbitals.
❖ Physical properties:
o All the elements are polyatomic in nature.
o Physical state
▪ Nitrogen is gas where as other elements are solids.
▪ Non – metals → nitrogen, phosphorus
▪ Metalloids → arsenic and antimony ▪ Metal → bismuth
o Boiling and Melting point → boiling point increases from nitrogen to bismuth. But melting point
increases arsenic and the decreases to bismuth because of presence of complete d and/or f orbitals.
o All elements show allotropic nature except nitrogen.
Chemical properties:
o Oxidation states:
▪ Common oxidation states are – 3, +3 and +5
▪ – 3 oxidation state decreases from nitrogen to bismuth due to increase in size and metallic
character.
▪ + 5 oxidation state stability decreases down the group and + 3 oxidation state increase down the
group because of inert pair effect.
▪ Nitrogen shows +1, +2, +3, +4, and +5 oxidation states when it reacts with oxygen. In acidic
medium due to disproportionate nitrogen shows +1 to +4 oxidation state. It will restrict into
covalency up to 4 because of the presence of one s and three p orbitals.
▪ Phosphorus will have +5 and – 3 oxidation states due to disproportionate in alkali and acid.
▪ +3 states are stable in case of As, Sb and Bi.
o Reactivity:
▪ Reactivity towards hydrogen:
• All of these element form EH3 type of hydride compounds.
• The stability of hydride decreases from nitrogen to bismuth due to decrease in bond
dissociation enthalpy due to increase of atomic size.
• Reducing property increases from nitrogen to bismuth because of decrease in bond
dissociation enthalpy. i.e., NH3 is less reducing agent than BH3.
• Basicity decreases from nitrogen to bismuth, i.e., NH3 > PH3 > AsH3 > SbH3> BiH3
▪ Reactivity towards oxygen:
• All of these element forms E2O3 and E2O5 type of oxide compounds.
• The higher oxidation states of these compounds are acidic which decreases from
nitrogen to bismuth.
• E2O3 compounds of N & P are acidic, As & Sb are amphoteric and Bi is basic in nature.
• Acidic nature of pentoxide of group 15 elements decreases from N to Bi
■ Reactivity towards halogens:
• These elements react to form two series of halides: EX3 and EX5.
• Nitrogen does not form pentahalide due to non-availability of the d orbitals in its valence shell.
• Pentahalides are more covalent than trihalides. Since +5 state will have more polarising power
than in +3 oxidation state.
 • In case of nitrogen, only NF3 is known to be stable.
• Trihalides except BiF3 are predominantly covalent in nature.
■ Reactivity towards metals:
• All these elements react with metals to form their binary compounds exhibiting –3 oxidation state
Ex: Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide), Na3As (sodium arsenide),
Zn3Sb2 (zinc antimonide) and Mg3Bi2(magnesium bismuthide).
Anomalous properties of N2: Nitrogen shows anomalous properties because of the following properties:
• Smaller is size, high electronegativity, high ionization enthalpy, non – availability of d – orbitals.
The anomalous properties of nitrogen are
▪ It can form p - p with another nitrogen atom or any other elements due to its small size and
high electro negativity.
▪ It exists as diatomic molecule with triple bond between two N atoms.
▪ Its bond enthalpy is very high than other members of the group due to smaller size and higher
electro negativity.
▪ It hardly for N – N single bond because of high inter electronic repulsion of the non – bonding
electrons, owing to the small band length. There by catenation tendency is weaker in
nitrogen.
▪ Due to non – availability of d – orbitals it never forms d - d and d - p multiple bonds with
transition metals and restricts its valence to four.

DINITROGEN
Properties:
• It is colourless, odourless, tasteless and non – toxic gas.
• It shows two isotopic forms 14N and 15N.
• It has high solubility in water.
• It has low freezing and boiling point.
• It is inert at room temperature due to high bond enthalpy. Its reactivity increases with increasing in
temperature.
Preparations:
1. Laboratory preparation: aqueous solution of ammonium chloride is treated with sodium nitrite.
The impurities i.e., NO and HNO3 are removed by passing the gas into aqueous solution of H2SO4
containing K2Cr2O7.
NH4Cl (aq) + NaNO2(aq) →N2 + 4H2O + NaCl (aq)
2. By thermal decomposition method:
▪ Thermal decomposition of ammonium dichromate also gives Dinitrogen along with chromic
oxide. (NH4)2Cr2O7 + heat strongly → N2 + 4H2O + Cr2O3.
▪ Thermal decomposition of sodium or barium azide. Ba(N3)2 → Ba + 3N2
3. Commercial Method: the liquefaction and fractional distillation of air. Liquid dinitrogen (b.p. 77.2 K) distils out
first leaving behind liquid oxygen (b.p. 90 K).

Chemical properties:
Dinitrogen is reactive only at high temperature due to high bond enthalpy.
• With metals: it reacts with metals at high temperature forms ionic nitrides. 6Li + N2 + heat → 2Li3N,
and 3Mg + N2 + heat → Mg3N2.
• With non – metals: it reacts with non – metals at high temperature form covalent nitrides.
• It reacts with hydrogen to give ammonia in the presences of finely divided iron as catalyst at 773K
under 200 atm. pressure. N2(g) + 3H2(g) + heat (773K) → 2NH3(g)
• It reacts with oxygen at 2000K to form nitric oxide. N2(g) + O2(g) + heat (2000K) → 2NO(g)
Uses:
• Liquid nitrogen is used as refrigerant to preserve biological materials, food and in cryosurgery.
• Dinitrogen is used in the manufacturing of ammonia by Haber’s process.
• It is used to create inert atmosphere for iron and steel industries.
AMMONIA
Properties:
• Molecular formula: NH3
• Molecular mass:17
• Discovered by Joseph Priestley in 1774
• It is pungent, colourless gas.
• Its freezing point is 198.4K and boiling point is 239.7K
• It is highly soluble in water and becomes weak base due to formation of OH – 1 ions.
• Due to hydrogen bonding in solid and liquid state its melting point and boiling points are high.
• It is having trigonal pyramidal structure where nitrogen is at middle with three bonded pair of
electrons and one lone pair of electrons on nitrogen atom.
MANUFACTURING OF AMMONIA BY HABER’S PROCESS:

Principle: Manufacturing of AMMONIA by Haber’s process is basically

depends on the Le - Chatelier's principle, according to which, nitrogen
and hydrogen is compressed at a pressure of 200atm, under the
temperature of 700K(5000C), using iron oxide with small amount of as
K2O and Al2O3 catalyst, to yield 12 – 15% of ammonia.
Note: finely divided iron as catalyst molybdenum [Mo] as promoter.
Reaction: N2 + 3H2 2NH3: H = – 90.2kJ/mol

Chemical properties:
• Reaction with metal salts: it reacts with metal salts and makes the metals to precipitate as metal
hydroxides due to its weak basic nature. ZnSO4(aq) + 2NH4OH(aq) → Zn(OH)2 (s) + (NH4)2SO4(aq)
• Due to presence of lone pair of electrons on nitrogen which will be donated to transition metal to form
coordination compounds which is used to detect the metal ions in salts.
CuSO4 (aq) + 4NH3 (aq) → [Cu (NH3)4] SO4 (deep blue)
Uses of ammonia:
• In the manufacturing of various fertilizers like ammonium nitrate, urea, ammonium phosphate and
ammonium sulphate
• In the manufacturing of nitric acid
• Liquid ammonia is used as refrigerant.

NITRIC ACID
Laboratory preparation: Nitric acid is usually prepared by heating potassium nitrate with concentrated
Sulphuric acid. The reaction is:
NaNO3 + H2SO4 → NaHSO4 + HNO3
Ostwald’s process of manufacturing of nitric acid:
The conversion of ammonia into nitric acid in this process is done through the following steps:
Step1: →Oxidation of ammonia to nitric oxide
Ammonia is oxidized by air in the presence of Pt catalyst at 800°C to give nitric oxide.
4 NH 3( g ) + 5O2 ( g ) ⎯⎯ ⎯ ⎯ ⎯→ 4 NO + 6 H 2O; H = −90kJ
Pt − Rh at 500 K 9 bar

Step 2:→Oxidation of NO to NO2

The nitric oxide is oxidised by air at temperature below 100°C, to give nitrogen dioxide (NO 2)
2 NO( g ) + O2 ( g )  2 NO2 ( g )
Step 3:→Formation of nitric acid
Nitrogen dioxide is then converted to nitric acid by absorbing NO 2 in water, in the presence of air.
3NO2 ( g ) + H 2O(l ) → 2 HNO3( aq ) + NO( g )
Step 4 → purification of nitric acid: the aqueous HNO3 is concentrated by distillation up to 68% by mass and
further concentrated to 98% by dehydration with conc. H 2SO4
Physical properties of nitric acid
 Pure nitric acid is a colorless fuming liquid with a pungent odor. Impure
acid or pure acid on standing develops yellow color due to the presence of
dissolved oxides of nitrogen (mainly NO2).
 It is completely soluble in water and forms a constant boiling mixture
(120.5°C) with water, containing 68% (by mass) of nitric acid.
 Pure acid has a density of 1.54 g/mL. The constant boiling mixture has a
density of 1.4 g/mL at 20°C.
 Anhydrous nitric acid boils at 355.6 K (83.6°C) and freezes to a white solid at 231.4 K (- 41.7°C).
 It has a corrosive action on the skin and causes yellow blisters.
 Structure of gaseous nitric acid: it is planer in nature

Chemical properties of nitric acid:

❖ Acidic nature: Nitric acid is a strong monobasic acid. It ionizes in water readily as follows:
HNO3(l) + H2O(l) → H3O+ (aq) + NO3 – (aq)
❖ Oxidizing property: it is very good oxidizing agent. The products of oxidation depend on the
concentration of the acid, temperature and nature of the material undergoing oxidation.
Oxidation of metals:
  Dilute nitric acid: 3Cu + 8HNO3(dilute) → 3Cu(NO3)2 + 2NO + 4H2O
4Zn + 10HNO3(dilute) → Zn(NO3)2 + N2O + 5 H2O
 Concentrated nitric acid: Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O
Zn + 4HNO3 → Zn(NO3)2 + 2NO2 + 2 H2O
 Iodine to iodide → I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O
 Carbon to carbondioxide → C + 4HNO3 → CO2 + 4NO2 + 2H2O
Note:
 Dilute or concentrated nitric acid will not reacts with noble metals like Pt, Au
 Al and Cr are not dissolved in concentrated nitric acid because these metals will become passive film
of oxide on the surface and protect the inner metal.
❖ Brown ring test:
❖ It is confirmatory test for nitrate ion.
❖ Procedure; take the salt solution in a test tube add freshly prepared ferrous sulphate solution, then
slowly adding concentrated sulfuric acid and a brown ring in the test tube formed, which indicate the
presence of the nitrate ion.
❖ This test depends on the ability of Fe2+ to reduce nitrate to nitric oxide which reacts with Fe2+ to form
a brown coloured complex.
NO3- + 3Fe2+ + 4H+ → NO + 3Fe3+ + 2H2O

[Fe (H2O)6 ]2+ + NO → [Fe (H2O)5 (NO)]2+ + H2O

(brown)

STRUCTURE OF OXIDES OF NITROGEN

 PHOSPHORUS
❖ It is a non – metal
❖ Its atomic number is 15
❖ Atomic mass is 30.97
❖ Electronic configuration [Ne]3s23p3
❖ Discovered by German alchemist Hennig Brand in 1669.
❖ The phosphorus was isolated from urine
❖ Robert Boyle in 1680 used to burn the sulphure tipped wooden splints which are leads today to use in
match sticks.
❖ There are three principal allotropic forms of Phosphorus. These are white phosphorus, red phosphorus
and black phosphorus.

WHITE OR RED PHOSPHORUS RED PHOSPHORUS

Translucent white waxy solid. Iron grey lustre
Carbon disulphide soluble Carbon disulphide insoluble
It glows in dark It does not glow in the dark
Less stable at room temperature and More stable at room temperature and
more reactive because of the angular less reactive because of less angular
strain with bond angle 600 strain with bond angle
It is discrete tetrahedral shape It is a chain of tetrahedral linked.
It is monomeric in nature It is polymeric in nature
It catches fire in air to give dense It will not catches fire in air
white fumes of P4O10

Phosphine
Laboratory Preparation: it is obtained by heated white phosphorus with conc. NaOH solution in an inert
atmosphere of CO2
P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2 (sodium hypophosphite)
The phosphine is purified by absorbing it on HI to form phosphonium iodide which on treating with KOH
gives off pure phosphine. PH4I + KOH → KI + H2O + PH3
• Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3P2+6H2O→3Ca(OH)2+2PH3
Ca3P2 + 6HCl → 3CaCl2 + 2PH3

Physical properties:
❖ It is a colourless gas with rotten fish smell
❖ It is highly poisonous.
 ❖ It gets explodes when comes in contact with oxidising agents like HNO 3, Cl2, and Br2 vapours
❖ It is slightly soluble in water and decomposes in the presence of light giving red phosphorus and
hydrogen.
❖ Basic nature of phosphine: it is weak base gives phosphonium compound with acids
PH3 + HBr → PH4Br
• When absorbed in copper sulphate or mercuric chloride solution, the corresponding phosphides are
obtained.
3CuSO4 + 2PH3 → Cu3 P2 + 3H2SO4
3HgCl2 + 2PH3 → Hg3P2 + 6HCl
Uses:
• The spontaneous combustion of phosphine is technically used in Holme’s signals.
• Containers containing calcium carbide and calcium phosphide are pierced and thrown in the sea
when the gases evolved burn and serve as a signal.
• It is also used in smoke screens.
• It is used as a powerful reducing agent.
PHOSPHORUS TRICHLORIDE AND PHOSPHORUS PENTACHLORIDE
[PCl3 and PCl5]
Preparation:
❖ When dry chlorine gas is passed over white phosphorus in limited quantity, we get PCl3.
P4 + 6Cl2 → 4PCl3
❖ When dry chlorine gas is passed over white phosphorus in excess quantity, we get PCl5.
P4 + 10Cl2 → 4PCl5
❖ by the action of thionyl chloride with white phosphorus gives PCl3.P4 + 8SOCl2→ 4PCl3 + 4SO2 + 2S2Cl2
❖ by the action of sulphuryl chloride on white phosphorus gives PCl5. P4 + 10SO2Cl2 → 4PCl5 + 10SO2
Properties: action on water (hydrolysis)
❖ PCl3 on hydrolysis in moisture to give orthophosphorous acid. PCl 3 + 3H2O → H3PO3 + 3HCl
❖ PCl5 on hydrolysis gives POCl3 which finally gets converted to phosphoric acid.
PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO4 + 3HCl
❖ Both PCl3 and PCl5 reacts with organic compounds containing –OH group such as CH3COOH, C2H5OH.
3CH3COOH + PCl3 → 3CH3COCl + H3PO3 : CH3COOH + PCl5 → CH3COCl + POCl3 + HCl
3C2H5OH + PCl3 → 3C2H5Cl + H3PO3 : C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl
Structure of PCl3 & PCl5
• Phosphorus trichloride has a pyramidal shape, in which phosphorus is sp3 hybridised.
• Phosphorus pentachloride has a trigonal bipyramidal structure. The three equatorial P–Cl bonds are
equivalent, while the two axial bonds are longer than equatorial bonds.

Oxoacids:
Reducing Property:
The oxoacids are said to be having reducing property if they have P – H in them, i.e., more number of
P – H bond more will be the oxoacids are said to have strong reducing property. i.e., among oxoacids of
phosphorus, hypophosphorous acid is said to have strong reducing property because it contains two P – H
bonds. i.e., hypophosphorous acid reduces silver nitrate solution to silver.
4AgNO3 + 2H2O + H3PO2 → 4Ag + 4HNO3 + H3PO4
Basicity: the P – H bond is strong bond which cannot be easily ionisable, so that formation of H + will not
takes place, which implies that basicity i.e., acidic character will be very less, but from P – OH, bond H+ are
formed very easily, thereby basicity of the molecule will increases. i.e., orthophosphoric acid is stronger acid
among the oxoacids of phosphorus because it contains three P – OH, bonds.

It contains two Due to one

Hypophosph P – H bonds so it P – OH, bond it
H3PO2
orous acid is stronger is monobasic
reducing agent. acid
 It contains one P
– H bond so it is
weak reducing Due to two
Orthophosp
H3PO3 agent P – OH, bond it
horous acid is dibasic acid

It doesn’t
contains any P – Due to three
Orthophosp H bond so it is P – OH, bond it
H3PO4 not a reducing
horic acid agent
is tri basic
acid

O.S.of Characteristics bonds and

Name Formula Preparation
Phosphorus their number

Hypophosphorus One P – OH, Two P – H

H3PO2 +1 white P4 + alkali
(phosphinic) One P = O
Orthophosphorous Two P – OH, One P – H
H3PO3 +3 P2O3
(phosphonic) One P = O
Two P – OH, Two P – H
Pyrophosphorous H4P2O5 +3 PCl3 + H3PO3
Two P = O, One P-O-P
Four P – OH, Two P=O
Hypophosphoric H4P2O6 +4 red P4 + alkali
One P-P

Three P – OH,
Orthophosphoric H3PO4 +5 P4O10+H2O
One P=O

four P – OH, Two P=O heat phosphoric

Pyrophosphoric H4P2O7 +5
One P-O-P acid
Three P – OH, Three P=O phosphorus
Metaphosphoric (HPO3)n +5 Two P-O-P acid + Br2 heat
in a sealed tube

16TH GROUP ELEMENTS

General introduction:
General outer electronic configuration of group 16 elements is ns2np4
Atomic Atomic Electronic Oxidation
Element Symbol Nature state
no. mass configuration
Oxygen O 8 16.00 [He]2s22p4 Gas/ non metal – 2, –1, 1, +2
Sulphur S 16 32.06 [Ne]3s23p4 Solid/non metal –2, +2, +4, +6
Selenium Se 34 78.96 [Ar]3d104s24p4 Solid/metalloid –2, +2, +4, +6
Tellurium Te 52 127.60 [Kr]4d105s25p4 Solid/metalloid –2, +2, +4,+ 6
Solid/metal/ +2, +4
Polonium Po 84 210.00 [Xe]4f145d106s26p4
Radioactive
Livermorium Lv 116 292 [Rn] 5f146d107s27p4 Solid/Radioactive -
Occurrence:
o Oxygen: 46.6% by mass of the earth 20.946% in dry air
o Sulphure: 0.03 – 1 % of mass of earth Sulphate and sulphides ore forms.
o Selenium: found mainly in the sulphide ores
o Tellurium: found mainly in the sulphide ores
o Polonium: Decay product of Th and U mineral
Atomic and Ionic Radii: Atomic and ionic radii increase from top to bottom in the group.
Ionisation Enthalpy:
o Ionisation enthalpy decreases down the group. It is due to increase in size.
o The elements of this group have lower ionisation enthalpy values compared to those of Group15 in the corresponding
periods. This is due to the fact that Group 15 elements have extra stable half-filled p orbitals electronic
configurations.
Electron Gain Enthalpy:
 o Because of the compact nature of oxygen atom, it has less negative electron gain enthalpy than sulphur.
o from sulphur onwards the value again becomes less negative up to polonium.
Electronegativity:
o oxygen has the second highest electronegativity value amongst the elements.
o Within the group, electronegativity decreases with an increase in atomic number hence metallic nature increases
from oxygen to polonium

Oxidation States:
o Due the presence of two umpired electrons and high electronegativity they show – 2 oxidation states
commonly. But it will decrease from oxygen to polonium.
o With fluorine, the oxidation state of oxygen is +2, where as other elements are +2, +4, +6, but +4 and
+6 are more stable and common oxidation states.
o Sulphur, selenium and tellurium shows +4 oxidation with oxygen and +6 oxidation state with
fluorine.
o The stability of +6 state decreases down the group where as +4 oxidation state increases due to inert
pair effect.
o +4 and +6 oxidation state of these elements shows covalent type of bonding.
Physical properties:
o Oxygen and sulphure are non - metals, selenium and tellurium are metalloids, polonium is
radioactive element.
o These elements exhibit allotropy.
o Melting and boiling point increases down the group.
o Large difference between m.p and b.p is seen between oxygen and sulphure due to their atomicity i.e.,
oxygen exists as diatomic molecule, where as sulphure exists as polyatomic molecule.
Chemical properties
o Reaction with hydrogen:
o These elements react with hydrogen and forms H2E type of compounds.
o Due to decrease in the bond enthalpy for the dissociation of H – E bond,
▪ Acidic nature increases down the group
▪ Thermal stability of hydrides decreases down the group
▪ Reducing property increases down the group except water.
o Reaction with Halogen
o These elements react with halogens to from EX6, EX4 and EX2 type of compounds.
o Due to increases the atomic size of halogens, stability of these halides decreases, i.e.,
F – > Cl – > Br – > I –.
o Hexahalides
▪ Hexafluoride are stable halides.
▪ All hexafluorides are gaseous in nature.
▪ These hexafluorides are having octahedral structure.
▪ SF6 is said to be more stable due to steric reasons.
o Tetrahalides
▪ SF4 is gas, SeF4 is liquid and TeF4 is solid at room temperature.
▪ These tetrahalides will have sp3d type of hybridization.
▪ These tetrahalides will show trigonal bipyramidal structure in which one of the
equatorial positions is occupied by a lone pair of electrons.
▪ The geometry of these tetrhalides are regarded as see saw geometry.
o Dihalides
▪ Selenium does not for dichlorides and dibromides, were as all other elements forms.
▪ All dihalides have sp3 type of hybridization with tetrahydral structure.
o Monohalides
▪ These halides commonly form dimers.
▪ Example: S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
▪ These monohalides with undergo Disproportionation 2Se2Cl2 → SeCl4 + 3Se
Anomalous behaviour of oxygen: this behaviour of oxygen is due to
o Small in atomic size
o High Ionization enthalpy
o High in electronegativity
o Absence of d – orbtials.
Anomalous behaviour of oxygen due to small in size and high electronegativity it forms
strong hydrogen bond in H2O, there by it is liquid at room temperature where as H2S is gas
at room temperature.
 Anomalous behaviour of oxygen due to absence of d – orbitals it shows only covalence of
four in practice rarely exceeds two, where as other elements valence shell expands and
covalence exceeds more than four.

Dioxygen
i. Preparation with KClO3 → when potassium chlorate is heated in the presence of MnO2 decomposes
to liberate dioxygen 2KClO3 + MnO2(catalyst) + heat → 2KCl + 3O2
ii. By the thermal decomposition of the oxides of metals low in the electrochemical series and higher oxides of some
metals. 2Ag2O(s) → 4Ag(s) + O2(g); 2HgO(s) → 2Hg(l) + O2(g) ; 2Pb3O4(s) → 6PbO(s) + O2(g); 2PbO2(s) → 2PbO(s) +
O2(g)
iii. Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely divided metals and
manganese dioxide. 2H2O2(aq) → 2H2O(1) + O2(g)
iv. On large scale it can be prepared from water or air. Electrolysis of water leads to the release of hydrogen at the
cathode and oxygen at the anode.
v. Industrially, dioxygen is obtained from air by first removing carbon dioxide and water vapour and then, the remaining
gases are liquefied and fractionally distilled to give dinitrogen and dioxygen.
Reaction with
❖ Aluminium: when it is burnt in the presence of oxygen, it forms aluminium oxide
4Al + 3O2 → 2Al2O3
❖ Methane: when methane is burnt in the presence of oxygen in under go combustion forming carbon
dioxide and water. CH4 + 2O2 → CO2 + 2H2O
❖ Carbon: when carbon is burnt it forms carbon dioxide C + O 2 → CO2
❖ 2ZnS + 3O2 → 2ZnO + 2SO2
❖ Catalytic oxidation 2SO2 + O ⎯ V2O5⎯⎯→ 2SO3 ; 4HCl + O2 ⎯⎯ CuCl2→ 2Cl2 + 2H2O

Ozone
Preparation: When slow dry stream of oxygen is passed through a silent electrical discharge, ozone is
obtained. The product is known as ozonised oxygen.
3O2 → 2O3, ∆H = +140kJ/mol
The formation of ozone from oxygen is an endothermic reaction.
The silent electrical discharge is used because to prevent decomposition of oxygen.
Properties: Due to its easy decomposition nature it liberates dioxygen and nascent oxygen; thereby it can be
used as very good oxidising agent.

❖ It oxidizes lead sulphide to lead sulphate PbS + 4O3 → PbSO4 + 4O2

❖ It oxidizes iodie ions to iodine: 2HI + O3 + H2O → 2H2O + I2 + O2

Oxides of oxygen
❖ The binary compound of oxygen with another element is called oxide.
❖ Oxides are classified into four types
❖ Basic oxides: these are the oxides which when dissolved in water to give basic oxide solution.
Example: Na2O, CaO, BaO etc.
❖ Acidic oxides: these are the oxides which when dissolved in water to give acidic oxide solution.
Example: SO2, Cl2O7, CO2, NO2 etc.
❖ Neutral oxides: these are the oxides which when dissolved in neither water neither give acidic nor
basic oxide solution. example: CO, NO, N2O
❖ Amphoteric oxides: these are the oxides which when dissolved in water gives either acidic or basic
oxide solution. Al2O3
Al2O3 + 6HCl + 9H2O → 2[Al(H2O)]Cl3 basic nautre

SULPHUR
❖ It shows two types of allotropic forms i.e., yellow rhombic i.e.,  - Sulphur and monoclinic
Sulphur i.e.,  - Sulphur.
❖ Properties of rhombic and monoclinic Sulphur
Properties Rhombic Sulphur Monoclinic Sulphur
Other name  - Sulphur  - Sulphur
Colour Yellow coloured Colourless
Melting point 385.8K 393K
Sp. Gravity 2.06 1.98
Shape Needle shaped
 Stability Stable below 369K More stable above 369K
Solubility In CS2 In CS2

❖ Preparation:
o  - Sulphur or rhombic Sulphur: it is obtained by evaporation of solution of roll
Sulphur in CS2.
o  - Sulphur or monoclinic Sulphur: it is obtained when rhombic Sulphur is melted in
a dish which on cooled till to obtained crust. When the liquid from the crust is
removed by pouring out through two holes, and finally when crust is removed we get
colourless needle shaped crystals.
❖ Stability:
o  - Sulphur or rhombic Sulphur is stable below 369K, where as above 369K it
converts into monoclinic Sulphur.
o The temperature i.e., at 369K both the forms of Sulphur are stable this temperature is
known as transition temperature.
❖ Structure:
o Both rhombic and monoclinic Sulphur have S8 molecules which are packed together
to give different crystal structures:
o The puckered and crown shape structure are shown below with their molecular
dimensions

COMPOUNDS OF SULPHUR
Sulphur Dioxide:
Preparation: when any sulphite is treated with conc. H2SO4, sulphur dioxide is liberated
SO32 – (aq) + 2H+ (aq) → H2O + SO2
Reaction with
❖ Sodium hydroxide: (NaOH); when is treated with NaOH solution, sodium sulphite is formed, which
reacts with more sulphur dioxide to form sodium bisulphite
2NaOH + SO2 → Na2SO3 + H2O
Na2SO3 + SO2 + H2O → NaHSO3
❖ Chlorine: when SO2 is treated with chlorine in the presence of charcoal (catalyst), sulphuryl chloride
SO2 + Cl2 → SO2Cl2
❖ Reducing property:
o It reduces Fe(III) ions to Fe(II) ions: 2Fe3+ + SO2 + H2O → 2Fe2+ + SO42 – + 4H+
o It reduces Mn(VII) i.e., MnO4 – to Mn2+ : i.e., potassium permanganate solution is decolorized
by treating with SO2.
5SO2 + 2MnO4 – + 2H2O → 5SO4 2 – + 4H+ + 2Mn2+
Sulphuric acid
It is manufactured by the process known as contact process.
Step – 1: Sulphur production chamber:
S + O2 → SO2
4FeS2 + 11O2 → Fe2O3 + 8SO2
Step – 2: Purification of Sulphur dioxide:
Step – 3: Catalytic oxidation of SO2 to SO3
It is the key reaction for the production of the conc. H2SO4.
2SO2 + O2  2SO3; H = - 196.6kJ/mol
It is an exothermic reversible reaction, therefore, according to Le Chatelier’s; low temperature and high
pressure are the favorable conditions for maximum yield of the product. Therefore
 o Pressure should be 2 -3 bar,
o Temperature 720K
o Catalyst: V2O5
Step – 4: Absorption tower: SO3 is made to absorb by conc. H2SO4 to from oleum or fuming Sulphuric acid
or pyrosulphuric acid.
SO3 + conc. H2SO4 → H2S2O7
Step – 5: Dilution chamber: Oleum is diluted with calculated amount of water in order to get the desired
concentrated Sulphuric acid:
H2S2O7 + H2O → 2H2SO4

Acidic nature: it is very strong acid because when dissolved in water it ionizes in two steps and liberates
hydrogen ion [H+], the two steps are as follows
H2SO4 (aq) + H2O(l) → H3O+(aq) + HSO4 – (aq), Ka = very large
HSO4 – (aq) + H2O(l) → H3O+(aq) + SO4 2 – (aq), Ka = 1.2 x 10 – 2
The value of Ka is more than 10; it means that it is more acidic in nature.

Dehydrating nature of H2SO4: it acts as very good dehydrating agent,

❖ It is used to dry many wet gases which will not react with water.
❖ It reacts with carbohydrates (sucrose) and makes then charged remove water to form carbon.
C12H22O11 + Conc. H2SO4 → 12C + 11H2O

Oxidizing property: it is strong oxidising agent i.e., it oxidizes metal, non – metals by reducing to SO2
❖ copper metal to copper sulphate: Cu + 2H2SO4(conc.) → CuSO4 + SO2 + H2O
❖ sulphure to sulphure dioxide : 3S + 2H2SO4(conc.) → 3SO2 + 2H2O
❖ carbon to carbon dioxide: C + 2H2SO4(conc.) → CO2 + 2SO2 + 2H2O

Reaction With Metal Halides (halide = F,Cl): it reacts with metal halides to form corresponding metal
sulphates with the formation of volatile acids i.e., HX
2MX + H2SO4 → 2HX + M2SO4 here M is metal, X is halogen
❖ sodium chloride to sodium sulphate with the liberation of hydrogen chloride gas
2NaCl + H2SO4 → Na2SO4 + 2 HCl
❖ potassium fluoride to potassium sulphate with the liberation of hydrogen fluoride gas
2KCl + H2SO4 → K2SO4 + 2 HCl
Oxides of sulphure
 17TH GROUP ELEMENTS
General introduction
❖ These group elements are known as halogens meaning ‘halo’ means ‘salt’ and ‘gens’ means
‘born’.
❖ These elements are having outer electronic configuration ns2np5.
❖ Some general characters of halogens are as follows:
Electronic
Atomic Atomic
Elements Symbol configuration Nature Oxidation states
No. mass

Fluorine F 9 19.00 [He]2s22p5 Gas/non metal –1

Chlorine Cl 17 35.45 [Ne]3s23p5 Gas/non – metal –1, +1, +3, +5, +7
Bromine Br 35 79.90 [Ar]3d104s24p5 Liquid/non metal –1, +1, +3, +5, +7
Iodine I 53 126.90 [Kr]4d105s25p5 Solid/non metal –1, +1, +3, +5, +7
Astatine At 85 210 [Xe]4f145d106s26p5 Solid/metalloid –1, +1, +3, +5, +7

Occurrence:
❖ It is present form of fluorides i.e., fluorspar CaF2, cryolite Na2AlF6 and fluoroapatite 3Ca3(PO4)2. CaF2
❖ It is present in the form of chlorides in sea water i.e., chlorides of Na, K, Mg, Ca.
❖ It is present in the form of bromides in sea water i.e., bromides of Na, K, Mg, Ca.
❖ It is found in various seaweeds, i.e., contain upto 0.5% of iodine and Chile saltpetre contains 0.2% of
NaI
❖ It is
a radioactive element.
Oxidation states:
❖ All these halides show common oxidation state of – 1.
❖ Except fluorine, chlorine, bromine and iodine shows +1, +3, +5 and +7 oxidation states.
❖ The higher oxidation state of these halogens can be explained as follows

Anomalous behaviour of fluorine:

o Small in atomic size
o Higher electronegativity
o Low bond dissociation energy
o Absence of d – orbtials.
o Ionization enthalpy, electronegativity and electrode potential are all higher than expected.
o Covalent and ionic radii, MP, BP enthalpy of bond dissociation, electron gain enthalpy are quite lower
than expected.
o HF is liquid due to hydrogen bonding other hydrogen halides are gaseous.
o HF is weakest of all the halogen acids due to higher strength of HF bond
o F2 has the highest electrode potential 2.87V hence a powerful oxidising agent that it can even oxidizes
inert gas.
Reactivity towards hydrogen:
 These elements react with hydrogen to form corresponding hydrogen halides.
 The tendency of reactivity towards hydrogen decreases from fluorine to iodine due to
increasing in atomic size.
 The bond enthalpy of H – X bond decreases from fluorine to iodine is due to increasing in
atomic size thereby stability of hydrogen halides increases. i.e., HF > HCl > HBr > HI.
 Since bond enthalpy of H – X bond decreases from fluorine to iodine, reducing property
increases i.e., HF is weak reducing agent where as HI strong reducing agent.
Reactivity towards oxygen:
 They form corresponding oxides but these oxides are highly unstable in nature.
 Fluorine: forms OF2 and O2F2 but OF2 is thermally stable at 298K. Both are fluorinating
agent. O2F2 oxidizes Pu to PrF6, this reaction is used to remove Pu as puF6 from spent
nuclear fuel.
 Chlorine oxide: Cl2O, ClO2, Cl2O6, Cl2O6 Cl2O7. Highly reactive oxidising agent and
explosive. ClO2 ; bleaching agent for paper pulp, textile and in water treatment.
 Bromine oxide: Br2O, BrO2, BrO3; stable at low temperature powerful oxidizing agent
 Iodine oxide: I2O4, I2O5, I2O7; insoluble solids. I2O5 good oxidizing agent and used in
estimation of CO
CHLORINE
Laboratory preparation:
 Hydrochloric acid reacts with potassium permanganate to liberate chlorine gas
2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2
Physical properties:
 Greenish yellow gas,
 MP = - 340C,
 Pungent smell causes suffocation and tightness in the throat on inhaling.
Chemical properties:
 Reaction wit non – metals: Sulphur:
Chlorine reacts with sulphur to give sulphur monochloride: S8 + 4Cl2 → 4S2Cl2
 Reaction with metal: (Aluminium)
Chlorine reacts with aluminium to give aluminium chloride: 2Al + 3Cl2 → 2AlCl3
 Reaction with hydrogen sulphide: [H2S]:
Chlorine oxidizes hydrogen sulphide to sulphur in the presence of water
H2S + Cl2 → 2HCl + S
 Ammonia:[NH3]
o Chlorine reacts with excess of ammonia to give ammonium chloride with liberation of
Nitrogen gas : 8NH3 (excess) + 3Cl2 → 6NH4Cl + N2
o When excess chloride reacts ammonia to gives nitrogen chloride an explosive.
NH3 + 3Cl2 (excess) → NCl3 + 3HCl
 Reaction with sodium hydroxide:
o Chlorine reacts cold and dilute sodium hydroxide to give sodium hypochlorite
Cl2 + 2NaOH (cold/diluted) → NaCl + NaOCl + H2O
o Chlorine reacts with hot and concentrated sodium hydroxide gives sodium chlorate.
3Cl2 + 6NaOH (hot/conc.) → 5NaCl + NaClO3 + 3H2O
 Formation of bleaching powder: chlorine reacts with slacked lime to give bleaching
powder. The composition of bleaching power is Ca(OCl2). CaCl2. Ca(OH)2. 2H2O
2Ca(OH)2 + 2Cl2 → Ca(OCl)2 + CaCl2 + 2H2O
 Oxidising property: chlorine in water forms hydrochloric acid and hypochlorous acid,
which decomposes to give nascent oxygen. Therefore chlorine acts as an oxidising agent.
o Ferrous sulphate: chlorine oxidizes ferrous to ferric and sulphite to sulphate.
2FeSO4 + H2SO4 + Cl2 → Fe2(SO4)3 + 2HCl
o Bleaching property: chlorine is a powerful bleaching agent, where the bleaching
action is due to oxidation.
Cl2 + H2O → 2HCl + (O)
Coloured substance + (O) → colourless substance.
It bleaches vegetable or organic matter in the presence of moisture, bleaching effect of
chlorine is permanent.

Uses:
 Used for bleaching wood pulp, cotton and textiles.
 Manufacture of bleaching powder.
 Preparation of poisonous gases: phosgene (COCl2) tear gas (CCl3NO2) mustard gas
(ClCH2CH2SCH2CH2Cl).
 In the manufacture of dyes, drugs, CCl4, CHCl3, DDT refrigerants
 In sterilizing drinking water
 In extraction gold and platinum.
 HYDROGEN CHLORIDE
 First time HCl was prepared by Johann Rudoif Glauber in 1648.
 Laboratory preparation: when sodium chloride is heated with concentrated Sulphuric acid in a
round bottom flask, hydrogen chloride is formed.
2NaCl + H2SO4 → Na2SO4 + 2HCl
This gas is purified and dry by passing it through conc. Sulphuric acid
 Physical properties: colourless, pungent smelling, non combustible gas, BP = 189K, FP = 159K
 Acidic nature: HCl is a monoprotic acid. In water, H+ ion of acid combines with water to the form
hydronium ion. HCl + H2O → H3O+ + Cl – , Ka = 107 High value of Ka indicates that it is a strong acid
in water.
o Reaction with NH3: Ammonia being base reacts with acid HCl to form salt i.e., ammonium
chloride. NH3 + HCl → NH4Cl
Aqua regia:
 It is a mixture of conc. HNO3 and conc. HCl in 1:3 volumes.
 It dissolves noble metals like gold, platinum due to liberation of atomic chlorine from soluble
compounds.

Uses:
 Manufacturing of chlorine, NH4Cl and glucose from corn starch
 Purification of bone black
 Laboratory reagent
 Manufacturing of fertilizers and dyes
 Refining ores of tin etc.
INTERHAOGEN COMPOUNDS
 Compounds formed between different halogen atoms are known as interhalogen compounds
 The binary compounds have formula XY, XY3, XY5 and XY7 where X = is heavier halogen atom and Y
= is smaller halogen atom
 As the radius ratio increase between X and Y the number of atoms per molecule also increases. Ex:
IF7

Preparations:
 ClF3: when chlorine gas is heated with excess of fluorine at 573K.

 ICl: by mixing equimolar proportion of chlorine and iodine.

 BrF5: when bromine is treated with excess of fluorine.

Oxoacids of halogens:
 A halogen oxoacids is an acid which has hydrogen, oxygen and halogen atoms.
 fluorine forms only one oxoacids: hypofluorous acid (HOF)
 chlorine, bromine and iodine form four series of oxoacids
o hypohaous acid : HXO o halic acid : HXO3
o halous aicd : HXO2 o perhalic acid : HXO4
They are stable only in solutions of as salts

Properties:
 all are covalent, polar compounds and are diamagnetic in nature
 they are volatile solids or liquid example ClF → gas
Interhalogen compounds have physical and chemical properties similar to those of free halogens, in
general they are more reactive than halogen except fluorine. This is because interhalogens bond i.e., X – Y is
weaker then X – X bonds in halogen except F – F bond.
All interhalogen compounds undergo hydrolysis giving halide ion derived from the smaller halogen and
a hypohalite when XY, halite when XY3, halite XY5 and perhalate when XY4 anion are derived from the larger
halogen.
 NOBLE GASES
Electronic Physical
Element At. No At. Mass Occurrence
configuration properties
Atmosphere → 1% Mono atomic
Helium [He] 2 4 by volume except Colouless,
radon odourless and
He and Ne found tasteless gases
Neon [Ne] 10 20.15 in minerals of Low MP and BP
radioactive due to only weak
elements. example dispersion force
Argon [Ar] 18 39.95
pitchblende, Lowest boiling
Krypton [Kr] 36 83.8 monazite, cleveite point element is
Xenon [Xe] 54 131.3 Helium is natural He [4.2K]
gas Sparingly soluble
Most abundant in water
noble gas is argon Note: He has a
Radon [Rn] 86 222 rarest noble gas is unusual property
xenon of diffusion
through rubber
glass and plastics
CHEMICAL PROPERTIES
Reasons for least reactivity of noble gases
1. noble gases except helium have completely filled ns2np6 valence shell electronic configuration

2. there fore they have high ionization enthalpy and high positive electron gain enthalpy

Non fluorine compounds

In 1962 Neil Bartlett observed that PtF6 a powderful oxidising agent combines with molecular oxygen to form
dioxygen hexafluroroplatinate an ionic compound
Xe + PtF6 → Xe[PtF6]
The first ionization energy of Xe [1170kJ/mo] and oxygen [1166 kJ/mol] are closed to one another. The
molecular diametic of xenon and oxygen are also similar, on this assumption Bartlett treat xenon with PtF6 is
gas phase one similar conditions to obtain Xenon hexafluoroplatinate.
Later few more xenon fluoro and krypton fluoro compounds were also prepared.
Preparation of xenon hexafluoride: XeF6 is prepared by heating a mixture of xenon and fluorine in the ratio
of 1:20 at 573K under a pressure of 60 – 70 bar. It is also prepared by the interaction of XeF4 and O2F2 at
143K. Xe + 3F2 → XeF6
Preparation of xenon trioxide: When XeF4 or XeF6 is completely hydrolysed with water XeO3 is formed.
XeF6 + 3H2O → XeO3 + 6HF
Preparation of XeO2F2: When XeF6 is subjected to partial hydrolysis with water XeO2F2 is formed.
XeF6 + 2H2O → XeF2O2 + 4HF
Uses of noble gases:
Helium
✓ Helium is very light and non-inflammable. Hence it is used for filling airships and weather observation
balloons.
✓ A mixture of helium and oxygen is used by sea divers, because at high pressure also it is not absorbed
in blood.
✓ In the treatment of asthma.
✓ Liquid helium is used to obtain very low temperatures (upto 4K).
✓ Because of its high thermal conductivity and inert nature, helium is used in vacuum tubes, radio
tubes; signal lamps as well as gas cooled nuclear reactors.
✓ It is used to provide inert atmosphere in the welding and metallurgy of metals like Mg, A1 and Ti.
Neon:
✓ Neon is used for filling discharge tubes needed for advertisement and optical decorations. This is due
to the emission of orange red glow when neon is subjected to electric discharge.
✓ It is also used in safety devices, electrical instruments like voltage stabilizers and rectifiers.
✓ It is used in the beacon lights for pilots because these lights can penetrate through fog and mist also.
Argon:
✓ Argon is used to fill incandescent and fluorescent discharge lamps.
✓ It is used to provide inert atmosphere for welding and several metallurgical processes.
✓ Argon gas is also used in gas chromatography.
✓ It is mixed with neon to obtain different colours in neon sign lamps.
Krypton:
✓ Krypton is used in filling discharge tubes and electric bulbs.
✓ It is also used in high efficiency miner's cap lamps.
✓ Krypton-85 is used to measure thickness of sheets of metals and plastics.
✓ It is used in the signal lights on runways of airports because it produces a bright white light during
electric discharge.
Xenon:
✓ A mixture of Xe and Kr is used in flash bulbs used in high speed photography.
✓ Liquid Xenon is used in research laboratories for the detection of mesons and gamma photons.
Radon:
✓ It is used in the treatment of cancer by radiotherapy because it emits a-radiations.
✓ It is used for photographing the interior of opaque materials like steel castings.
✓ It is also used in radioactive research.