CHAPTER 4

Samman sammi
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GROUP VA & VIA

ELEMENT
IMPORTANT POINTS
INTRODUCTION

Elements of VA
N and P are non-metals, while others are metals.
Some elements show allotropy
Catenation is absent
Metallic character increases down the group
d orbital involve in bond formation
It show 3 and 5 oxidation states
 NITROGEN AND ITS
COMPOUNDS

 It is present in free state in air, 78% by volume.

 Nitrogen is chemically found in minerals
 It is present in the form of proteins, urea and amino
acids.
 OXIDES OF NITROGEN
Particular Nitrous oxide (N2O) Nitro Oxide Nitrogen Oxide (NO2)
(NO)
Pb(NO3)2
Zn+HNO3 → Cu+dilHNO3 →
→PbO+NO2+O2
ZnNO3+ N2O+ H2O Cu(NO3) 2
Preparation Cu+conc. HNO3
NH4NO2 → N2O+ +NO+H2O
→Cu(NO3)2
H2O N2O+O2 → NO
+NO2+H2O
Colour Colourless gas Colourless gas Reddish brown gas
Smell & Pleasant smell and
- Pungent smell
Taste taste
Fairly soluble in Sparingly Soluble and formed
Solubility
water soluble blue colour solution
Action of Form reddish
- -
O2 brown NO2
 QUESTION
 The gaseous oxides of N2 have positive
enthalpy changes of formation. Which one of
the following factors is the most significant.
a) Tendency of O2 to form O-2
b) High electron affinity of nitrogen atoms
c) High bond energy of the N2 molecule
d) High electron affinity of oxygen atoms
 QUESTION
 Why N2 gas is an unreactive gas?
a) Its molecule contains a triple bond
b) Bond energy of N2 molecule is high (994 KJ/mol)
c) Bond length is very short (0.11 nm)
d) Three P orbitals of nitrogen are half-filled
 CHEMICAL PROPERTIES OF
NITROUS OXIDE (N2O)

 It is not combustible but liberate N2 on

reaction with P and S.
 On reaction with red – hot Cu, it gives N2
Cu + N2O  CuO + N2
 CHEMICAL PROPERTIES OF
NITROGEN OXIDE (NO)
 It decomposes on heating into N2 and O2.
 It forms nitrosyl chloride on reaction with Cl2.
 It forms brown coloured FeSO4 . NO (ring
test) with FeSO4 .
 Ring test is confirmation of nitrates.
 With reducing agents like H2S, H2SO4 etc, it
gives N2O.
 With oxidizing agents like KMnO4, HNO3
gives N2O.
 CHEMICAL PROPERTIES OF
NITROGEN DI OXIDE (NO2)
 On cooling NO2 change into yellow liquid
which on freezing change into dinitrogen
tetraoxide.
 On decomposition, it forms O2.
 In absence of air, it forms HNO3 and HNO2
with water.
 On reaction with alkalies, it gives nitrates and
nitrites
 As strong oxidizing agent, it oxidizes H2S to
sulphur, FeSO4 to Fe2(SO4)3 and KI to I2.
ACIDS OF NITROGEN
 Brikland and Eyde’s procedure
 Another method for preparation of nitric acid is Brikland and
Eyde’s procedure.
 Oxidation of N2 with atmospheric O2 and then reaction with
water, produces nitric acid.

Reactivity of Nitric Acid With Metals
 Au, Pt & Ti do not react.
 Fe, Co, Ni, Cr & Al form oxides with HNO3
 W & U are changed into oxides.
 Mg, Ca & Mn gives H2
 Cu and Pb give NO and NO2 with dilute and conc. acid.
 Hg give HgNO3 and Hg2 (NO3)2 with dilute and conc. acid.
 Ag gives AgNO3 and NO.
 Zn gives products depending upon HNO3 concentration and
temperature.
 Very dilute HNO3 gives NH4NO3.
 Moderate dilute HNO3 gives N2O.
 Concentrated HNO3 gives N2O.
 PHOSPHORUS AND ITS COMPOUNDS
OCCURRENCE OF PHOSPHORUS

 P is found in combined state in form of

minerals.
 It is present in seed, yolk of eggs, nerves,
brain and bone marrows.
 Bone ash (80%Ca3 (PO4)2.
ALLOTROPES OF PHOSPHORUS
 Different crystalline forms of any substance are said to be
allotropes.

White Phosphorus Red Phosphorus Black Phosphorus

Very, reactive, poisonous,
Less reactive and
volatile, waxy and -
poisonous.
yellowish.

Soluble in C6H6 and CS2 Soluble Soluble

Exist in tetra atomic form Tetra atomic form -

Change into P2 at 700oC - -

Prepared by heating white Prepared by heating red

- phosphate in presence of S phosphate at high
and I at 250oC temperature and pressure
HALIDES OF PHOSPHORUS
OXIDES OF PHOSPHOROUS
ACIDS OF PHOSPHORUS
GENERAL TREND OF VI-A
ELEMENTS

Elements of VIA
All elements are non-metals except Po.
Al elements show allotropy
Catenation is present
M.P, B.P and atomic radii increases down the group
d orbital involve in bond formation
It shows -2 oxidation states.
 OCCURANCE OF GROUP VI-A
ELEMENT
 O2 comprises 50% of earth crust.
 Oxygen found in air in free state.
 Water contains 89% oxygen.
 CaCO3 contains 98% oxygen.
 Silica contains 53% oxygen.
 Sulphur is present in metallic ores.
 Sulphur also present in onions, garlic,
mustard, hair, oil, egg & proteins.
 COMPARISON OF S AND O
Oxygen Sulphur
Have six electrons in outer shell Similar to O
Form two covalent bonds Similar to O
Allotropes are O3 and O2 Three allotropes, rhombic, monoclinic and plastic
Polyatomic molecule Similar to O
Forms oxides Forms sulphides
Forms covalent bond with non metal Similar to O
Non metal Similar to O
Free state and combine state Similar to O
It is a gas It is solid
Sparingly soluble in H2O Insoluble
Helps in combustion Itself combustible
Paramagnetic in nature Diamagnetic
No reaction with O2 at all Forms SO2 and H2S at high temp
No reaction with acid Oxidized by H2SO4 and HNO3
No reaction with alkalies React with alkali and form sulphide and thiosulphate
Shows -2 oxidation state Shows -2, +2, +4 and +
 SULPHURIC ACID (H2 SO4)
 Discovered by Jabar–ibn–Hayan
 It was called oil vitriol
 Some H2 SO4 is present in water of some springs and rivers.
 Contract Process For Preparation
 SO2 is produced by burning of S or FeS and again oxidized
to SO3 in presence of V2O5 at 400 – 500C.
 SO2 absorbed by H2 SO4 and converts into oleum H2 S2O7.
 Water is added to H2 S2O7 and forms H2 SO4.
 Properties of H2 SO4
 Colourless oil liquid
 Specific gravity is 1.834 at 181C
 Freezing point 10.5 C
 Boiling point 338 C
 Soluble in water, exothermic reaction
 Pure is nonconductor, but dilute is good
 Corrosive to skin
 CHEMICAL PROPERTIES
 On heating changes into SO3 and H2O.
 Strong acid completely ionizes in water.
 Reacts with alkali to give salt and water.
 Reacts with carbonates and bicarbonates to give salt.
 Reacts with NH3 to give ammonium sulphate
 Reacts with benzene to give benzene sulphonic acid
 Reacts with metal in following manner:
 Cold and dilute acid give salt and H2
 Cold and concentrated acid do not react
 Hot and concentrated acid liberate SO2 and metallic sulphate
 Good dehydrating agent, removes water from organic compounds and
liberate CO, CO2 and black C.
 As an oxidizing agent oxidizes C and S to their oxides, H2S to S, HBr,
Hl to Br2 and l2 respectively.
 Reacts with BaCl2 and Pb (NO3)2 to give precipitation of BaSO4 and
PbSO4
 Reacts with KMnO4 and K2Cr2O7 and liberate O2
MINERALS OF GROUP VIA
ELEMENTS

Name Formula
Galena PbS
Zinc blende ZnS
Cinnabar HgS
Stibnite Sb2S3
Copper pyrite Cu2S
Iron pyrite FeS2 & Fe2S3
Gypsum CaSO4
Heavy spar BaSO4
 QUESTION
 Which one of the following is a correct
reaction of concentrated H2SO4.
a) It always gives H2 with metals.
b) It can dehydrate C2H5OH to CH2 = CH2
c) It gives SO2 by all metals
d) It oxidizes Cl- ion to Cl2