THE p-BLOCK ELEMENTS.

Group-15 elements.
N, P, As, Sb, Bi
General characteristics:
El.confgn: ns2 np3
Extra stable due to half-filled p-confgn. Bcoz of the same reason, they have higher

ionisation enthalpies than gr-14 elements(Carbon family)

There is a very small in size from As to Bi due to completely filled d- and f- orbitals in
heavier memebers (they have poor shielding effect)
Physical properties
Metallic character increases down the group
Bi is a strong metal due to higher I.E. bcoz of its small size
Except nitrogen, all show allotropy.
Chemical Properties
Oxidat ion states = -3, +3 and +5.
The tendency to show -3 state decreases as we gown due to increase in size and metallic
character
The stabilit y o f +3 state increases down the group whereas that of +5 state decreases due to
INERT-PAIR effect
Bi shows +5 only wit h fluorine (BiF5) due to high polarizing power of fluorine.
Conseqences of inert-pair effect

Nitrogen compounds disproportionate in acid solutions.

3HNO2 HNO3 + H2O + 2NO

Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate

into +5 and 3 both in alkali and acid.

But the +3 oxidation state in case of arsenic, antimony and bismuth becomes increasingly
stable and do not ungergo disproportionation.
Anomalous properties of Nitrogen

It can show a maximum covalency of four only whereas others show 5 and 6. for
erxample:-PCl5 and PF6
This is due to the absence of vacant d-orbitals in N-atom

It forms strong p-p multiple bonds due to its small size. This is why it exists as a
diatomic molecule with a triple bond between two N-atoms.
Others do not form such bonds bcoz their atomic orbitals are so large and diffused that they
can not have effective overlapping.

Anomalous properties of Nitrogen

The bond enthalpy o f nitrogen mo lecule is very high due to the presence of triple bond

between the two atoms.

Other elements form only single bonds with their own atoms and other atoms too.

The N-N is weaker than P-P bcoz of high interelectronic repulsio ns of the non-bonding

electrons in N-N due to the small size of N-atom .

This is why N does not catenate.
Reactivity towards hydrogen:All the elements of Group 15 form hydrides of the type E H3 where E = N, P, As, Sb or Bi.

The stabilit y o f hydrides decreases fro m NH3 to BiH3 due to decrease in their bond

dissociat ion enthalpy.

Consequent ly, the reducing character of the hydrides increases.

Ammo nia is only a mild reducing agent while BiH3 is the strongest reducing agent amongst

all the hydrides.

Basicit y also decreases in the order

Facts of the hydrides

NH3 > PH3 > AsH3 > SbH3 > BiH3.
Stability decreases bcoz bde decreases
Basicity decreases bcoz electron density around the central atom decreases due to increase in
size
Reducing nature increases bcoz bde decreases
BDE decreases bcoz size of E increases
React ivit y towards oxygen

All these elements form two types o f oxides: E2O3 and E2O5.
The oxide in the higher oxidation state of the element is more acidic than that of lower
oxidat ion state.
Their acidic character decreases down the group.
The oxides of the type E2O3 of nitrogen and phosphorus are purely acidic,
that of arsenic and ant imo ny amphoteric and
those of bismuth(Bi2O3))is predominant ly basic.

React ivit y 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.

In case of nitrogen, only NF3 is known to be stable due to high poalrizing nature of F-atom

Trihalides except BiF3 are predominant ly covalent in nature. BiF3 is ionic due to high

matallic character of Bismuth.

React ivit y towards metals

All these elements react with metals to form their binary co mpounds exhibit ing 3 oxidat ion
state
Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide),
??? QUESTION ???
1.PH3 has lower boiling point than NH3. Why?
Unlike NH3, PH3 mo lecules do not form int ermo lecular hydrogen bonding in liquid state.
That is why the bo iling point of PH3 is lower than NH3.
2. NH3 is so lube in water whereas PH3 is inso luble.Why?

DINITROGEN (N2)
PROPERTIES OF N2
At higher temperatures, it directly combines with some metals to form predominantly ionic
nitrides and with non-metals, covalent nitrides.
6Li + N2 2Li3N
3Mg + N2 Mg3N2
Dinitrogen combines with dioxygen only at very high temperature (at about 2000 K) to
*
form nitric oxide, NO.
N2 + O2(g) 2NO(g)
USES OF N2
in the manufacture of ammo nia

in the manufacture of chemicals containing nitrogen, (e.g., calcium cyanamide).

It also finds use where an inert atmosphere is required (e.g., in iron and steel industry, inert

diluent for reactive chemicals).

Liquid dinitrogen is used as a refrigerant to preserve bio logical materials, food items and

in cryosurgery.

Evaluation Questions
Q. Write the reaction of thermal deco mposit ion of sodium azide.
Ans:-Thermal deco mposit ion of sodium azide gives dinitrogen gas.
2NaN3 2Na + 3N2
Q. Why is N2 less reactive at room tempearature?
AMMONIA
On a small scale ammo nia is obtained from ammo nium salts which deco mpose when

treated with caustic soda or lime.

2NH4Cl + Ca(OH)2 2NH3 + 2H2O + CaCl2

(NH4)2 SO4 + 2NaOH 2NH3 + 2H2O + Na2SO4
On a large scale, ammo nia is manufactured by Habers process.
N2(g) + 3H2(g) 2NH3(g); Enthalpy change = 46.1 kJ mo l1
Condit ions for better yield are:In accordance wit h Le Chateliers principle, high pressure would favour the formation o f
ammo nia.
The optimum condit io ns for the production of ammo nia are a pressure o f 200 at m, a
temperature of ~ 700 K and the use o f a catalyst such as iron oxide wit h small amounts of
K2O and Al2O3 to increase the rate of attainment of equilibrium.

Structure of ammonia
The ammonia molecule is trigonal pyramidal with the nitrogen atom at the apex. It has three
bond pairs and one lone pair of electrons as shown in the structure.

Properties of ammonia
*

*
*

Ammonia gas is highly soluble in water as it forms intermolecular H-bonds with water
molecules.
It is a Lewis base as it can donate the lone pair present on the N-atom.
It donates the electron pair forming linkages with metal ions and therefore form complex
compounds.
This finds applications in detection of metal ions
such as Cu2+, Ag+:
Cu2+ (aq) + 4 NH3(aq) [Cu(NH3)4]2+(aq)
Deep blue
AgCl(s) + 2NH3(aq) [Ag(NH3)2]Cl(aq)
White ppt Excess
Soluble

OXIDES OF NITROGEN

Oxides of Nitrogen possess planar structure due to the ability of N to form multiple bonds.
(Oxides of P have cage like structures since P can not form strong multiple bonds)

STRUCTURE-

Evaluation Questions

What is the covalence of N in (a)N2O5 and (b) N2O4?

Why does NO2 dimerize? Can NO dimerize?

Why is the precipitate of AgCl soluble in excess of ammonia?

Why is ammonia a Lewis base?

NITRIC ACID
Large Scale Manufacure:- Ostwald process.
Based on catalytic oxidation of ammonia.
Pt /Rh
4NH3 g + 5O2 g

4NO g + 6H2 O g
(from air) 500K; 9 bar
Nitric oxide thus formed combines with oxygen giving NO2.
2NO g + O2 g 2NO2 g
Nitrogen dioxide so formed, dissolves in water to give HNO3.
3NO2 g + H2 O 2HNO3 aq + NO g
NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto
~ 68% by mass. Further concentration to 98% can be achieved by dehydration with
concentrated H2SO4.

Lab. Preparation of Nitric acid:

In lab, nitric acid is prepared by heating potassium nitrate or sodium nitrate with conc.
sulphuric acid in a glass resort.
NaNO3 + H2SO4 NaHSO4 + HNO3
Shape of Nitric acid molecule

In the gaseous state, HNO3 exists as a planar molecule with the structure as shown.
H
O

O
Properties of Nitric acid
In aqueous solution, nitric acid behaves as a strong acid giving hydronium and nitrate ions.
HNO3(aq) + H2O(l) H3O+(aq) + NO3 (aq)

Concentrated nitric acid is a strong oxidising agent and attacks most metals except noble
metals such as gold and platinum. The products of oxidation depend upon the concentration
of the acid, temperature and the nature of the material undergoing oxidation.
3Cu + 8 HNO3(dilute) 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) Cu(NO3)2 + 2NO2 + 2H2O

Zinc reacts with dilute nitric acid to give N2O and with concentrated acid to give NO2.
4Zn + 10HNO3(dilute) 4 Zn (NO3)2 + 5H2O + N2O
Zn + 4HNO3(conc.) Zn (NO3)2 + 2H2O + 2NO2

Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric acid because of the
formation of a passive film of oxide on the surface.

Concentrated nitric acid also oxidises nonmetals and their compounds. Iodine is oxidised
to iodic acid, carbon to carbon dioxide, sulphur to H2SO4, and phosphorus to phosphoric
acid.
Properties of nitric acid-Contd..

Concentrated nitric acid also oxidises nonmetals and their compounds. Iodine is oxidised
to iodic acid, carbon to carbon dioxide, sulphur to H2SO4, and phosphorus to phosphoric
acid.
I2 +10HNO3 2HIO3 + 10 NO2 + H2O

C + 4HNO3 CO2 + 2H2O + 4NO2

S8 + 48HNO3(conc.) 8H2SO4 +48NO2 + 16H2O
P4 + 20HNO3(conc.) 4H3PO4 +20 NO2 + 4H2O
Chemistry of Brown ring test:-

Brown Ring Test: The brown ring test for nitrates depends on the ability of Fe2+ to reduce nitrates
to nitric oxide, which reacts with Fe2+ to form a brown coloured complex.
The test is usually carried out by adding dilute ferrous sulphate solution to an aqueous
solution containing nitrate ion, and then carefully adding concentrated sulphuric acid along
the sides of the test tube. A brown ring at the interface between the solution and sulphuric
acid layers indicate the presence of nitrate ion in the solution.
NO3 + 3Fe2+ + 4H+ NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO [Fe (H2O)5 (NO)]2+ + H2O
(brown)
Uses of Nitric acid

In the mfr. of ammonium nitrate for fertilizer.

In the mfr. of nitrates required for making explosives and pyrotechnics.

In making TNT, nitroglycerin

In pickling of stainless steel, etching of glass

As oxidizer in rocket fuels.

PHOSPHOROUS.

S.No White Phosphorous Red Phosphorous

1

Poisonous

Non-poisonous

Soluble in CS2

Insoluble in CS2

Glows in dark

Doesnt

White Phosphorous:P4 +3NaOH + 3H2O PH3 + 3NaH2 PO2

sodium hypophosphite
Reaction with Oxygen:-

P4 + 5O2 P4O10

Structure:- It consists of discrete P4 tetrahedron units.

Red Phosphorous:Red phosphorus is obtained by heating white phosphorus at 573K in an inert atmosphere for
several days.
Structure:- It has a chain-like structure.

Black phosphorous

has two forms alpha-black phosphorous and beta-black phosphorous.

PHOSPHINE:- (PH3)
Preparation:1.Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3P2 + 6H2O3Ca(OH)2 + 2PH3
Ca3P2 + 6HCl 3CaCl2 + 2PH3
2.In the laboratory, it is prepared by heating white phosphorus with concentrated NaOH solution
in an inert atmosphere of CO2.
P4 +3NaOH + 3H2O PH3 + 3NaH2 PO2
sodium hypophosphite

When pure, it is non inflammable but becomes inflammable owing to the presence of
P2H4 or P4 vapours. To purify it from the impurities, it is absorbed in HI to form phosphonium
iodide (PH4I) which on treating with KOH gives off phosphine.
PH4 I + KOH KI + H2O + PH3
Properties:1.

3CuSO4 + 2PH3 Cu3P2 + 3H2SO4

2.

3HgCl2 + 2PH3 Hg3P2 + 6HCl

3.
e.g.,

Phosphine is weakly basic and like ammonia, gives phosphonium compounds with acids
PH3 + HBr PH4 Br

Uses of Phopsphine:Holmes signals.

The spontaneous combustion of phosphine is technically used in

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.
Halides of Phosphorous:1.

PCl3:Preparation:P4 + Cl2 PCl3

P4 + 8SOCl2 4PCl3 + + 4SO2 + 2S2Cl2
Properties:(i)It fumes in moist air due to the formation of HCl.
PCl3 + 3H2O H3PO3 + 3HCl
(ii)It reacts with organic compounds containing OH group such as CH3COOH, C2H5OH.
3CH3COOH + PCl3 3CH3COCl +H3PO3
3C2H5OH+ PCl3 3C2H5Cl + H3PO3

Structure:_
It has a pyramidal shape as shown, in which phosphorus is sp3 hybridised.

Phosphorous Trichloride

..

Lone pair

P
Cl

Cl
Cl

2.PCl5:Preparation:(i)Phosphorus pentachloride is prepared by the reaction of white phosphorus with excess

of dry chlorine.
P4 + 10Cl2 4PCl5
(ii)It can also be prepared by the action of SO2Cl2 on phosphorus.
P4 + 10SO2Cl2 4PCl5 + 10SO2
Properties:(i)In moist air, it hydrolyses to POCl3 and finally gets converted to phosphoric acid.
PCl5 + H2O POCl3 + 2HCl
POCl3 + 3H2O H3PO4 + 3HCl
(ii)When heated, it sublimes but decomposes on stronger heating.
PCl5 PCl3 + Cl2
(iii)It reacts with organic compounds containing OH group converting them to chloro
derivatives.
3CH3COOH + PCl5 3CH3COCl +POCl3 + HCl

3C2H5OH+ PCl5 3C2H5Cl + POCl3 + HCl

(iv)Finely divided metals on heating with PCl5 give corresponding chlorides.
2Ag + PCl5 2AgCl + PCl3
Sn + 2PCl5 SnCl4 + 2PCl3
(v) In the solid state it exists as an ionic solid, [PCl4]+[PCl6] in which the cation, [PCl4]+ is
tetrahedral and the anion, [PCl6]octahedral.
Structure:- Trigonal bipyramidal

The three equatorial PCl bonds are equivalent, while the two axial bonds are longer than
equatorial bonds. This is due to the fact that the axial bond pairs suffer more repulsion as
compared to equatorial bond pairs.
Uses:It is used in the synthesis of some organic compounds, e.g., C2H5Cl, CH3COCl.

OXOACIDS OF PHOSPHOROUS:-

(i)The acids in +3 oxidation state of phosphorus tend to disproportionate to higher and lower
oxidation states. For example, orthophophorous acid (or phosphorous acid) on heating
disproportionates to give orthophosphoric acid (or phosphoric acid) and phosphine.
4H3PO3 3H3PO4 + PH3
(ii)The acids which contain PH bond have strong reducing properties.Thus, hypophosphorous
acid is a good reducing agent as it contains two PH bonds and reduces, for example, AgNO3 to
metallic silver.
4 AgNO3 + 2H2O + H3PO2 4Ag + 4HNO3 + H3PO4
Group 16 Elements
1.They have ns2np4 general electronic configuration.
2.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 orbital
electronic configurations.
3.Because of the compact nature of oxygen atom, it has less negative electron gain enthalpy than
sulphur.
4.Next to fluorine, oxygen has the highest electronegativity value amongst the elements.
5.Oxygen and sulphur are non-metals, selenium and tellurium metalloids, whereas polonium is a
metal. Polonium is radioactive and is short lived (Half-life 13.8 days).
6.The large difference between the melting and boiling points of oxygen and sulphur may be
explained on the basis of their atomicity; oxygen exists as diatomic molecule (O2) whereas
sulphur exists as polyatomic molecule (S8).
Oxidation states and trends in chemical reactivity:1. Since electronegativity of oxygen is very high, it shows only negative oxidation state as 2
except in the case of OF2 where its oxidation state is + 2
2.The stability of + 6 oxidation state decreases down the group and stability of + 4 oxidation
state increase (inert pair effect)
Anomalous behaviour of oxygen:1.The anomalous behaviour of oxygen, like other members of p-block

present in second period is due to its small size and high electronegativity. One typical example
of effects of small size and high electronegativity is the presence of strong hydrogen bonding in
H2O which is not found in H2S.
2.The absence of d orbitals in oxygen limits its covalency to four and in practice, rarely exceeds
two. On the other hand, in case of other elements of the group, the valence shells can be xpanded
and covalence exceeds four.
Reactivity with hydrogen:

All the elements of Group 16 form hydrides of the type H2E (E =O, S, Se, Te, Po)
H2O H2S H2Se H2Te
BDE Decreases
Stability decreases
Acidity increases
Reducing nature increases

Reactivity with oxygen:

All these elements form oxides of the EO2 and EO3 types where E = S, Se, Te or Po.
Ozone (O3) and sulphur dioxide (SO2) are gases while selenium dioxide (SeO2) is solid.
Reducing property of dioxide decreases from SO2 to TeO2; SO2 is reducing while TeO2 is
an oxidising agent
Both types of oxides are acidic in nature.

Reactivity towards the halogens.

The stability of the halides decreases in the order F > Cl > Br > I.
Amongst hexahalides, hexafluorides are the only stable halides.
They have octahedral structure.
Sulphurhexafluoride, SF6 is exceptionally stable for steric reasons.
Tetrafluorides, have sp3d hybridisation and thus, have trigonal bipyramidal structures in
which one of the equatorial positions is occupied by a lone pair of electrons. This
geometry is also regarded as see-saw geometry.

Dihalides have sp3 hybridisation and thus, have tetrahedral structure.

The well known monohalides are dimeric in nature. Examples are S2F2, S2Cl2, S2Br2,
Se2Cl2 and Se2Br2.
These dimeric halides undergo disproportionation as given below:
2Se2Cl2 SeCl4 + 3Se

Question:1.H2S is less acidic than H2Te. Why?

Due to the decrease in bond (EH) dissociation enthalpy down the group, acidic character
increases.
2. Why is H2O a liquid and H2S a gas ?

DIOXYGEN

Dioxygen can be obtained in the laboratory by the following ways:

(i) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
2KClO3

2 KCl + 3 O2

MnO2
(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);
2Pb3O4(s) 6PbO(s) + O2(g)
2HgO(s) 2Hg(l) + 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.
Properties
1.Molecular oxygen, O2 is unique in being paramagnetic inspite of having even number of
electrons .
2.Its combination with other elements is often strongly exothermic which helps in sustaining the
reaction. However, to initiate the reaction, some external heating is required as bond dissociation
enthalpy of oxgyen-oxygendouble bond is high (493.4 kJ mol1).
2.Some compounds are catalytically oxidised. For e.g.,
2SO2 + O2 2SO3
5HCl + O2 2Cl2 + 2H2O
CuCl2

Uses Of Dioxygen:- Self work

Oxides:A binary compound of oxygen with another element is called oxide.

Oxides can be simple (e.g., MgO, Al2O3 ) or mixed (Pb3O4, Fe3O4).
Acidic or Basic or Amphoteric or Neutral
Reactions to show that aluminium oxide is amphoteric:Al2O3+ 6HCl+ 9H2O 2[Al(H2O)6]Cl3 (aq)
Al2O3+ 6NaOH +3H2O Na3[Al(OH)6] (aq)

OZONE:-

Ozone is an allotropic form of oxygen. It is too reactive to remain for long in the atmosphere at
sea level. At a height of about 20 kilometres, it is formed from atmospheric oxygen in the
presence of sunlight. This ozone layer protects the earths surface from an excessive
concentration of ultraviolet (UV) radiations.
Preparation:-When a slow dry stream of oxygen is passed through a silent electrical discharge,
conversion of oxygen to ozone (10%) occurs. The product is known as ozonised oxygen.
3O2 2O3

H = +ve

Since the formation of ozone from oxygen is an endothermic process, it is necessary to use a
silent electrical discharge in its preparation to prevent its decomposition.

PROPERTIES OF OZONE:1.Ozone is thermodynamically unstable with respect to oxygen since its decomposition into
oxygen results in the liberation of heat (H is negative) and an increase in entropy (S is
positive). These two effects reinforce each other, resulting in large negative Gibbs energy change
(G) for its conversion into oxygen.

2.Due to the ease with which it liberates atoms of nascent oxygen (O3 O2 + [O] ), it acts as a
powerful oxidising agent.
For e.g., it oxidizes lead sulphide to lead sulphate and iodide ions to iodine.
PbS(s) + 4O3(g) PbSO4(s) + 4O2(g)
2I(aq) + H2O(l) + O3(g) 2OH(aq) + I2(s) + O2(g)
3. Estimation of ozone:-When ozone reacts with an excess of potassium iodide solution buffered
with a borate buffer (pH 9.2), iodine is liberated which can be titrated against a standard solution
of sodium thiosulphate. This is a quantitative method for estimating O3 gas.
4.Nitrogen oxides (particularly nitric oxide) combine very rapidly with ozone and there is, thus,
the possibility that nitrogen oxides emitted from the exhaust systems of supersonic jet
aeroplanes might be slowly depleting the concentration of the ozone layer in the upper
atmosphere.
NO + O3 NO2 + O2
Structure of Ozone:- Angular .

Uses of Ozone: It is used as a germicide, disinfectant and for sterilising water. It is also used for
bleaching oils, ivory, flour, starch, etc. It acts as an oxidising agent in the manufacture of
potassium permanganate.
SULPHUR
Yellow rhombic sulphur = Monoclinic sulphur
Transition temp = 369 K
Both rhombic and monoclinic sulphur have S8 molecules.

At elevated temperatures (~1000 K), S2 is the dominant species and is paramagnetic like O2

In vapour state sulphur partly exists as S2 molecule which has two unpaired electrons in the
antibonding * orbitals like O2 and, hence, exhibits paramagnetism.

Preparation:1.Sulphur dioxide is formed together with a little (6-8%) sulphur trioxide when sulphur is burnt
in air or oxygen:
S(s) + O2(g) SO2 (g)
2.In the laboratory it is readily generated by treating a sulphite with dilute sulphuric acid.
SO3 2- + 2H+(aq) H2O(l) + SO2 (g)
Properties:1.2NaOH + SO2 Na2SO3 + H2O
Na2SO3 + H2O + SO2 2NaHSO3
(Excess)
SO2(g) + Cl2 (g) SO2Cl2(l)
Charcoal
2. When moist, sulphur dioxide behaves as a reducing agent.
For example,
1.it converts iron(III) ions to iron(II) ions
2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 4H+
2. it decolourises acidified potassium permanganate(VII) solution;
convenient test for the gas.

this reaction is a

5SO2 + 2MnO4-+2H2O 5SO42- + 4H+ + 2Mn2+

Structure:- The molecule of SO2 is angular. It is a resonance hybrid of the two canonical forms:

Uses:-Sulphur dioxide is used (i) in refining petroleum and sugar (ii) in bleaching wool and silk
and (iii) as an anti-chlor, disinfectant and preservative. Sulphuric acid, sodium hydrogen sulphite
and calcium hydrogen sulphite (industrial chemicals) are manufactured from sulphur dioxide.
Liquid SO2 is used as a solvent to dissolve a number of organic and inorganic chemicals.

Oxoacids of Sulphur

SULPHURIC ACID:Sulphuric acid is manufactured by the Contact Process which involves three steps:
(i) burning of sulphur or sulphide ores in air to generate SO2.
S+ O2 SO2
(ii) conversion of SO2 to SO3 by the reaction with oxygen in the presence of a catalyst (V2O5)
2SO2 + O2 2SO3
(iii) absorption of SO3 in H2SO4 to give Oleum (H2S2O7).

SO3 + H2SO4 H2S2O7

H2S2O7 + H2O 2 H2SO4
The favourable conditions for maximum yield are a pressure of 2 bar and a temperature of 720
K.
PROPERTIES OF SULPHURIC ACID:1.It dissolves in water with the evolution of a large quantity of heat. Hence, care must be taken
while preparing sulphuric acid solution from concentrated sulphuric acid. The concentrated acid
must be added slowly into water with constant stirring.
2.The chemical reactions of sulphuric acid are as a result of the following characteristics: (a) low
volatility (b) strong acidic character (c) strong affinity for water and (d) ability to act as an
oxidising agent.
3. In aqueous solution, sulphuric acid ionises in two steps.
H2SO4 + H2O H3O+ + HSO4- ( Ka1 = very large )
HSO4- + H2O H3O+ + SO42- ( Ka 2 = very low)
The larger value of Ka1 means that H2SO4 is largely dissociated into H+ and HSO4- ions.
Greater the value of dissociation constant (Ka), the stronger is the acid.
2 MX + H2SO4 2 HX + M2SO4 (X = F, Cl, NO3)

4..

(M = Metal)

5. Concentrated sulphuric acid is a strong dehydrating agent.

C12H22O11

12C + 11H2O

c-H2SO4
6.Hot concentrated sulphuric acid is a moderately strong oxidizing agent.
Cu + 2 H2SO4(conc.) CuSO4 + SO2 + 2H2O
3S + 2H2SO4(conc.) 3SO2 + 2H2O
C + 2H2SO4(conc.) CO2 + 2 SO2 + 2 H2O
Uses :-

In the manufacture of fertilizers (e.g., ammonium sulphate, superphosphate). petroleum refining ,

manufacture of pigments, paints and dyestuff intermediates , detergent industry , metallurgical
applications (e.g.,cleansing metals before enameling, electroplating and galvanising, storage
batteries , in the manufacture of nitrocellulose products and, as a laboratory reagent.
QUESTIONS:What happens when
(i) Concentrated H2SO4 is added to calcium fluoride
(ii) SO3 is passed through water?
Answer:(i) It forms hydrogen fluoride
CaF2 + H2 SO4 CaSO4 + 2HF
(ii) It dissolves SO3 to give H2SO4 .
SO3 + H2O H2 SO4

GROUP 17 ELENTS- HALOGENS.

1. Outermost confioguration is ns2np5.
2. They have very high ionization enthalpy due to very small atomic size. The I.E. decreases as
we go down the group.
3.They have maximum negative electron gain enthalpy in the corresponding periods . This is
bcoz after gaining an electron they attain the stable noble gas configuration.
However, the negative electron gain enthalpy of fluorine is less than that of chlorine. It is due to
small size of fluorine atom. As a result, there are strong interelectronic repulsions in the
relatively small 2p orbitals of fluorine and thus, the incoming electron does not experience much
attraction.
4. All halogens are coloured. This is due to absorption of radiations in visible region which
results in the excitation of outer electrons to higher energy level. For example, F2, has yellow,
Cl2 , greenish yellow, Br2, red and I2, violet colour
5.The enthalpy of dissociation of F2 is less compared to that of Cl2

A reason for this anomaly is the relatively large electron-electron repulsion among the lone pairs
in F2 molecule due to smaller size of F-atom where they are much closer to each other than in
case of Cl2.
Cl Cl > Br Br > I I.
BDE decreases bcoz atomic size and hence bond length increase.
Cl2> Br2>F2>I2
Question?
Although electron gain enthalpy of fluorine is less negative as compared to chlorine, fluorine is a
stronger oxidising agent than chlorine. Why?
Ans:-

It is due to

(i) low enthalpy of dissociation of F-F bond

(ii) high hydration enthalpy of F

CHEMICAL PROPERTIES:1.Fluorine shows only -1 state . due to its high electronegativity.

2. The fluorine atom has no d orbitals in its valence shell and therefore cannot expand its octet.
3. Others show -1 , +1, +3, +5 and +7.
4. The chemical reactivity decreases down the group, bcoz the electronegativity decreases.
5. The Oxidising tendency also decreases down the group whereas the reducing tendency
increases.
There is a regular decrease in the first ionization energy as we go down this column. As a
result, there is a regular decrease in the oxidizing strength of the halogens from fluorine to
iodine.
F2 > Cl2 > Br2 > I2
oxidizing strength
This trend is mirrored by an increase in the reducing strength of the corresponding halides.

I- > Br- > Cl- > Freducing strength

6. A halide can oxidize any other halide having a higher atomic no.
F2+ 2X- 2F- + X2

( X = Cl/Br/I)

Cl2 + 2X- 2Cl- + X2

( X = Br/I)

2 I-(aq) + Br2(aq)

I2(aq) + 2 Br-(aq)

2F2 + 2H2O 4HF + O2

X2 + H2O HX + HOX (X= Cl /Br)
4I - + 4H+ + O2 2I2 + 2H2O

Anomalous proerties of Fluorine:1.It forms only one oxoacid while other halogens form a number of oxoacids (HOF).
2.Hydrogen fluoride is a liquid (b.p. 293 K) due to strong hydrogen bonding. Other hydrogen
halides are gases.
HYDRIDES:1.The order of boiling point is:HF > HI> HBr> HCl
HI has exceptionally higher bpt since it forms extensive H-bonding.
The remaining hydrides follow increase in bpt with increase in molar mass.
1. Acidic strength of these acids increases in the order:
Reason:- BDE decreases.
HF > HCl > HBr > HI
2. The stability of these halides decreases down the group
HF > HCl > HBr > HI.

Reason :- BDE decreases.

OXIDES:1. Fluorine forms two oxides OF2 and O2F2. However, only OF2 is thermally stable at 298 K.
These oxides are essentially oxygen fluorides because of the higher electronegativity of fluorine
than oxygen.
Uses:(i).Both OF2 and O2F2 are strong fluorinating agents.
(ii) O2F2 oxidises plutonium to PuF6 and the reaction is used in removing plutonium as PuF6
from spent nuclear fuel.
2.The thermal stability of oxides decreases in the order;
I > Cl > Br > F
Reason:- Metallic character decreases and hence ionic character decreases
3. ClO2 is used as a bleaching agent for paper pulp and textiles and in sewage-water treatment.
4.I2O5 is a very good oxidising agent and is used in the estimation of carbon monoxide.
5. The ionic character of the metal halides decreases in the order
MF >MCl > MBr > MI
Reason:- Electronegativity decreases.
If a metal exhibits more than one oxidation state, the halides in higher oxidation state will be
more covalent than the one in lower oxidation state. (Fajans rule)
For e.g., SnCl4, PbCl4, SbCl5 and UF6 are more covalent than SnCl2, PbCl2, SbCl3 and UF4
respectively.
QUESTION?:
Fluorine exhibits only 1 oxidation state whereas other halogens exhibit + 1, + 3, + 5 and + 7
oxidation states also. Explain.
Ans:-Fluorine is the most electronegative element and cannot exhibit any positive oxidation
state. Other halogens have d orbitals and therefore, can expand their octets and show + 1, + 3, +
5 and + 7 oxidation states also.

CHLORINE:Preparation:It can be prepared by any one of the following methods:

(i) By heating manganese dioxide with concentrated hydrochloric acid.
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
However, a mixture of common salt and concentrated H2SO4 is used in place of HCl.
4NaCl + MnO2 + 4H2SO4 MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) By the action of HCl on potassium permanganate.
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2

Manufacture of chlorine

(i) Deacons process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K.
4HCl + O2

2Cl2 + 2H2O

CuCl2
(ii) Electrolytic process: Chlorine is obtained by the electrolysis of brine (concentrated NaCl
solution). Chlorine is liberated at anode.

Properties
1. Reaction with meatls and non-meatlas:2Al + 3Cl2 2AlCl3;
2Na + Cl2 2NaCl;
2Fe + 3Cl2 2FeCl3 ;
P4 + 6Cl2 4PCl3
S8 + 4Cl2 4S2Cl2

2. Reaction with hydrogen and compounds of hydrogen:It has great affinity for hydrogen. It reacts with compounds containing hydrogen to form HCl.
H2 + Cl2 2HCl
H2S + Cl2 2HCl + S
C10H16 + 8Cl2 16 HCl + 10C
3.With excess ammonia, chlorine gives nitrogen and ammonium chloride whereas with excess
chlorine, nitrogen trichloride (explosive) is formed.
8NH3 + 3Cl2 6NH4Cl + N2;
(excess)
NH3 + 3Cl2 NCl3 + 3HCl
(excess)
4..With cold and dilute alkalis chlorine produces a mixture of chloride and hypochlorite but
with hot and concentrated alkalis it gives chloride and chlorate.
2NaOH + Cl2 NaCl + NaOCl + H2O
(cold and dilute)
6 NaOH + 3Cl2 5NaCl + NaClO3 + 3H2O
(hot and conc.)
5.With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 Ca(OCl)2 + CaCl2 + 2H2O
The composition of bleaching powder is Ca(OCl)2.CaCl2.Ca(OH)2.2H2O.
6.Chlorine water on standing loses its yellow colour due to the formation of HCl and HOCl.
Hypochlorous acid (HOCl) so formed, gives nascent oxygen which is responsible for oxidising
and bleaching properties of chlorine.
(i) It oxidises ferrous to ferric, sulphite to sulphate, sulphur dioxide to sulphuric acid and iodine
to iodic acid.
2FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2HCl
Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl

H2SO4 + 2HCl

SO2 + 2H2O + Cl2

I2 + 6H2O + 5Cl2 2HIO3 + 10HCl

(ii) It is a powerful bleaching agent; bleaching action is due to oxidation and therefore it is
permanent.
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 of Chlorine: It is used (i) for bleaching woodpulp (required for the manufacture of paper
and rayon), bleaching cotton and textiles, (ii) in the extraction of gold and platinum (iii) in the
manufacture of dyes, drugs and organic compounds such as CCl4, CHCl3, DDT, refrigerants, etc.
(iv) in sterilising drinking water and (v) preparation of poisonous gases such as phosgene
(COCl2), tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).
QUESTION:Write the balanced chemical equation for the reaction of Cl2 with hot and concentrated NaOH. Is
this reaction a disproportionation reaction? Justify.
3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O

Ans:-

Yes, chlorine from zero oxidation state is changed to 1 and +5 oxidation states.
Hydrogen Chloride
Preparation
In laboratory, it is prepared by heating sodium chloride with concentrated sulphuric acid.
NaCl + H2SO4

NaHSO4 + HCl

420K
NaHSO4 + NaCl Na2SO4 + HCl
823K
HCl gas can be dried by passing through concentrated sulphuric acid.
Properties

1.It reacts with NH3 and gives white fumes of NH4Cl.

NH3 + HCl NH4Cl
2.When three parts of concentrated HCl and one part of concentrated HNO3 are mixed, aqua
regia is formed which is used for dissolving noble metals, e.g., gold, platinum.
-

Au + 4H+ + NO3- + 4Cl- AuCl4 + NO + 2H2O

3Pt + 16H+ + 4NO3- +18Cl- PtCl62- + 4NO + 8H2O
3.Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates, hydrogen carbonates,
sulphites, etc
Na2CO3 + 2HCl 2NaCl + H2O + CO2

NaHCO3 + HCl NaCl + H2O + CO2

Na2SO3 + 2HCl 2NaCl + H2O + SO2
Uses of HCl:- It is used (i) in the manufacture of chlorine, NH4Cl and glucose (from corn
starch), (ii) for extracting glue from bones and purifying bone black, (iii)in medicine and as a
laboratory reagent.
QUESTION:When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride.
Why?
Ans:-Its reaction with iron produces H2.
Fe + 2HCl FeCl2 + H2
Liberation of hydrogen prevents the formation of ferric chloride.
Oxoacids of Halogens

INTERHALOGEN COMPOUNDS
The compounds of halogens formed amongst themselves are called interhalogen compounds.
1. The interhalogen compounds can be prepared by the direct combination or by the action of
halogen on lower interhalogen compounds
Cl2 + 3F2 2ClF3
(Excess)

I2 + 3Cl2 2ICl3
(Excess)

Br2 + 5F2 2BrF5

(Excess)
2. They are all covalent in nature.
3. More reactive than halogens (except Fluorine).
This is because XX`bond in interhalogens is weaker than XX bond in halogens except F
F bond.

3. They are diamagnetic as they do not contain any unpaired electron.

4. XX + H2O HX + HOX. (X= smaller halogen)

5.Shapes:XX3 -------------- Bent T- shaped
XX5 --------------- Square pyramidal
XX7 (IF7) ------- Pentagonal bipyramidal.

Shape of BrF3:- Bent T shaped.

Uses:
1. These compounds can be used as non aqueous solvents.
2. Interhalogen compounds are very useful fluorinating agents.
3. ClF3 and BrF3 are used for the production of UF6 in the enrichment of U-235.
U(s) + 3ClF3(l) UF6(g) + 3ClF(g)
GROUP 18 ELEMENTS.
1.Group 18 consists of six elements: helium, neon, argon, krypton, xenon and radon.
2.Electronic configuration is ns2np6
3.They have very high ionization enthalpy due to stable configuration.
4..All these are gases and chemically unreactive. They form very few compounds. Because of
this they are termed noble gases.
5.All the noble gases except radon occur in the atmosphere. Their atmospheric abundance in dry
air is ~ 1% by volume of which argon is the major constituent.

Helium and sometimes neon are found in minerals of radioactive origin e.g., pitchblende,
monazite, cleveite. The main commercial source of helium is natural gas.
Xenon and radon are the rarest elements of the group.
Radon is obtained as a decay product of Radium-226.
226
Ra

222

88

Rn + He
86

Because radon is highly radioactive, it is difficult to study the chemistry of radon.

6.They have very low melting and boiling points because the interatomic interaction in these
elements is weak dispersion forces. Helium has the lowest boiling point (4.2 K) of any known
substance. It has an unusual property of diffusing through most commonly used laboratory
materials such as rubber, glass or plastics.
7.In general, noble gases are least reactive. Their inertness to chemical reactivity is attributed to
the following reasons:
(i) The noble gases except helium (1s2) have completely filled ns2np6 electronic configuration in
their valence shell.
(ii) They have high ionisation enthalpy and more positive electron gain enthalpy.(since they do
not have any tendency to accept an additional electron as their outermost orbits are completely
filled)
8.Xenon has lower ionisation enthalpy, because of large size of xenon.
9. Xenon reacts with only oxygen and fluorine atoms because these two elements are of very
high polarizing capacity.
10.The fact that the first IE of xenon is comparable with that of molecular oxygen prompted Neil
Bartlett to study the chemistry of xenon compounds.(he understood this from the compound
O2PtF6, which he prepared )
The first compound of xenon prepared was XePtF6
Question?
Why are the elements of Group 18 known as noble gases ?

The elements present in Group 18 have their valence shell orbitals completely filled and,
therefore, react with a few elements only under certain conditions. Therefore, they are known as
noble gases.
(a) Xenon-fluorine compounds
Xenon forms three binary fluorides, XeF2, XeF4 and XeF6 by the direct reaction of elements
under appropriate experimental conditions.
XeF6 can also be prepared by the interaction of XeF4 and O2F2 at 143K.
XeF4 + O2 F2 XeF6 + O2
Properties:1.XeF2 is hydrolysed to give Xe, HF and O2.
2XeF2 (s) + 2H2O(l) 2Xe (g) + 4 HF(aq) + O2(g)

2.Xenon fluorides react with fluoride ion acceptors to form cationic species and fluoride ion
donors to form fluoroanions.
XeF2 + PF5 [XeF]+ [PF6] ;
XeF4 + SbF5 [XeF3]+ [SbF6]
XeF6 + MF M+ [XeF7] (M = Na, K, Rb or Cs)

(b) Xenon-oxygen compounds

Hydrolysis of XeF4 and XeF6 with water gives Xe03.
6XeF4 + 12 H2O 4Xe + 2Xe03 + 24 HF + 3 O2
XeF6 + 3 H2O XeO3 + 6 HF
Structures of xenon compounds:-

XeF4
F

..

Xe
F

.. F

Uses:1.Helium is a non-inflammable and light gas. Hence, it is used in filling balloons for
meteorological observations. It is also used in gas-cooled nuclear reactors. Liquid helium (b.p.
4.2 K) finds use as cryogenic agent for carrying out various experiments at low temperatures. It
is used to produce and sustain powerful superconducting magnets which form an essential part of
modern NMR spectrometers and Magnetic Resonance Imaging (MRI) systems for clinical
diagnosis. It is used as a diluent for oxygen in modern diving apparatus because of its very low
solubility in blood.
2.Neon is used in discharge tubes and fluorescent bulbs for advertisement display purposes.
3.Argon is used mainly to provide an inert atmosphere in high temperature metallurgical
processes (arc welding of metals or alloys) and for filling electric bulbs.
It is also used in the laboratory for handling substances that are air-sensitive.
4.Xenon and Krypton are used in light bulbs designed for special purposes.

Important chemical equations

1. NH4CI +NaNO2N2+2H2O+NaCl
2 (NH4)2Cr2O7 N2+4H2O+Cr2O3
3. 2NH4Cl+Ca(OH)22NH3+ H2O +CaCl2
4. 2FeCl3+3NH4OH Fe(OH)3+2NH4Cl
5. Cu2++4NH3[Cu(NH3)4]2+
6. 4NH3+5O2

Pt

500K ; 9 bar

4NO+6H2O

7. 2NO+O2 2NO2
8. 3NO2+H2O2HNO3+NO
9. 3Cu+8HNO33Cu(NO3)2+2NO+H2O
10. Cu+4HNO3Cu(NO3)2+2NO2+4H2O
11. I2+10 HNO3 2HIO3+10 NO2+4H2O
12. P4+20 HNO34H3PO4+20 NO2+4H2O
13. NO3- +3Fe3++4H+ NO+ 3Fe2++2H2O
14. [Fe(H2O)6]2++NO[Fe(H2O)5NO]2++H2O
15. P4+3NaOH+3H2OPH3+3NaH2PO2
16. PCl3+3H2OH3PO3+3HCl
17. PCl5+H2O POCl3+2 HCl
18. POCl3+3H2OH3PO4+3HCl
19. Al2O3+6HCl+9H2O2[Al(H2O)6]3++6Cl20 Al2O3. +6NaOH+3H2O.2Na3[Al(OH)6]
21. PbS+4O3PbSO4+4O2
22. 2I- +H2O+O3 2OH-+I2+ O2
23. 2Fe3+ + SO2 + 2H2O2Fe2++ SO42- +4H+
24. 2MCl+H2SO4 HCl+M2SO4 (M= any alkali or alkaline earth metal)
Conc.H2SO4
25. C12H22O11
26. C+Conc.H2SO4

12C+11H20
CO2+2SO2+2H2O

27. MnO2+4HClMnCl2+Cl2+2H2O
28. 2KMnO4+16HCl2KCl+2MnCl2+8H2O+5Cl2
29. 2NaOH+Cl2NaCl+NaOCl+ H2O
30. 6NaOH+3Cl25NaCl+NaClO3+3 H2O

31. 2Ca(OH)2+2Cl2Ca(OCl)2+CaCl2+2H2O
32. Na2SO3+Cl2+H2ONa2SO4+2HCl
33. I2+ 6H2O +5Cl22HIO3+10 HCl
34. Cl2+3F22ClF3
35. I2+3Cl22ICl3
36. Br2+3F22BrF3
37. Xe +F2

673k ; 1bar

Xe F2

38. Xe+ 2F2 873k,7bar Xe F4

39. Xe+3F2 573k,60-70bar Xe F6
40. XeF2+PF5[XeF]+[PF6]41. XeF6+NaFNa+[XeF7]42. XeF6+3H2OXeO3+6HF
HOTS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.

What is called inert pair effect?

As we go down a group in the p-block the stable oxidation state decreases by 2 units. Explain.
Why do the group 15 elements have very high I.E?
There is only very small increase in size from As Bi. Why?
Molecular nitrogen exist as a gas whereas phosphorus is solid at room temperature. Why?
PCl5 exists whereas NCl5 does not why?
N does not show allotropy. Why?
N does not catenate. Why?
Bi shows +3 states. Why
Why is NF3 stable whereas NCl3 is not?
Why is BiF3 highly ionic?
Which is more covalent BiF5 or Bif3?
NH3 is a Lewis base. Explain.
Why is NH3 a stronger base than BH3.
Arrange the hydrides of group 15 elements in the
(a) increasing order of basicity
(b) increasing order of stability (c) Increasing order of reducing nature
Complete (NH4)2 Cr2O7 ?
Molecular Nitrogen is highly unreactive. Why?
Explain Habers process. (optimum conditions and catalyst)
Silver chloride dissolves in aqueous ammonias. Explain.
Complete Cu2+(aq) + NH3(aq) ?
Shapes of oxides of nitrogen.

22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.

Why do NO2 and NO dimerise?

What is the covalence of N in (a) N2O5 (b) N2O4 ?
Explain Ostwald process of manufacturing HNO3.
Draw the shape of HNO3. Why is it monobasic?
Explain the chemistry of the Brown ring test.
Complete and balance P4 + NaOH + H2O ?
Why is white phosphorus less stable and more reactive?
Write any two differences between white and red phosphorus.
Mention any two uses of phosphine.
Bond angle in PH4+ is higher than that in PH3. Why?
Why does PCl3 fumes in moist air?
Complete and balance (a) P4 + SOCl2 ? (b) P4 + SO2Cl2 ? (c) HgCl2 + PH3?
(d) CuSO4 + PH3?
Why does PCl5 fumes in moist air?
Draw the shape of (a) PH3 (b) PCl3 (c) PCl5
Complete and balance (a) Ag + PCl5? (b) Sn + PCl5?
PCl5 in solid state exists as an ionic solid. Explain.
All the five bonds in PCl5 are not equivalent. Explain.
Draw the structure of (a) Phosphoric Acid (b) phosphorus Acid (c) Hypo phosphorus acid
Discuss the basicity of each of them.
Phosphorus acid disproportionates. Write the equation
Hypo Phosphorus acid is a better reducing agent than phosphorus acid.Explain.
How is N2 prepared in lab? (ans: NH4Cl + NaNO2 N2 + 2H20 + NaCl)
NH3 is a stronger base than BiF3. Why?
NH3 form intermolecular H-bond whereas PH3 does not. Why?
Write the equation for the reaction of PCl5 with heavy water. (ans: PCl5 + 4D2OD3PO4 +5DCl)
Hypo phosphorus acid is a reducing agent. Explain.
Group 16 elements have lower I.E than group 15 elements. Why?
Oxygen has less negative electron gain enthalpy than S. Why?
Oxygen is a gas at room temperature whereas Sulphur is a sold. Why?
Oxygen has lower melting point and boiling point than Sulphur. Why?
Oxygen shows -2 oxidation state preferably. Why?
OF2 exists whereas OCl2 does not. Why?
Oxygen does not show covalency beyond 4. Why?
OR
SF6 exists where as OF6 does not. Why?
OF2 is known as Oxyfluoride but not flourooxide. Why?

15th GROUP

QUESTIONS WITH ANSWERS

1.

The Bi (V) compounds are unknown except BiF5 .Why?

2.
as

Nitrogen exists as a gas in elemental state , whereas other elements of the group exist

Due to inert pair effect, +5 oxidation state of Bi is unstable

solid .Why?
Due to ability of nitrogen to form p- p multiple bond , it exists as discrete molecules
Of N2 .
3.
The tendency of catenation for Nitrogen is less than Phosphorous . Why?
N-N bond is weaker than P-P bond due to inter electronic repulsion between non
bonding pair of electrons in Nitrogen owing to its small size .
4.
Arrange the hydrides of 15th group elements in the decreasing order of the property
mentioned
a. Thermal stability
: NH3 > PH3>AsH3>SbH3>BiH3
b. Basic strength
: NH3 > PH3>AsH3>SbH3>BiH3
c. Reducing character : BiH3 > SbH3 >AsH3>PH3> NH3
5.
Arrange the oxide E2O3 of 15th group element in the decreasing order of acid strength
N2O3> P2O3>As2O3>Sb2O3>Bi2O3
6.
Nitrogen doesnt form pentahalides . Why?
Due to non availability of d orbitals in Nitrogen to expand its covalency beyond 4.
7.
NH3 has exceptionally higher boiling point compared to the other hydrides of 15th
group.Why?
Due to strong inter molecular association in NH3 through H- bonding
8.
NH3 is most basic among the hydrides of 15th group elements . Why?
Due to small size of Nitrogen the availability of lone pair electron in NH3 is more.
9.
BiH3 is the strongest reducing agent among the hydrides of 15th group elements .Why?
Bcause Bi-H bond is the weakest
10.
The pentahalides of 15th group elements are more covalent than their trihalides .Why?
The +5 oxidation state of the element in their penta halides is more polarizing than the
+3 state of elements in their trihalides .
11.
The thermal stability of BiH3 is the lowest among the hydrides of 15th group elements
Why?
Bi-H bond is the weakest bond due to its small bond dissociation enthalpy.
12
Dinitrogen ( N2) is inert at room temperature .Why?
Due to very high bond enthalpy of N= N
13.
How is Nitrogen prepared in pure form ?
By thermal decomposition of Sodium/Barium azide
Ba(N3)2
Ba + 3N2
2NaN3
2Na + 3N2
14.
How is NH3 manufactured by Haber process
N2 (g) + 3H2(g)
2NH3(g) Temperature : 700K Pressure : 200At.
Catalyst : Iron oxide Promoters : K2O and Al2O3

15.
16.
17.
18.
19.

20.
21.
22.
23.
24.
25.

26.
27.
28.
29.
30.
31.
32.

AgCl is soluble in NH3 . Why ?

Due to formation of a soluble complex with NH3. AgCl (s) + NH3(aq)
[Cu(NH3)4] 2+
2+
How does NH3 react with Cu (aq) ?
Cu2+ + 4NH3
[Cu(NH3)4]2+
NO2 undergoes dimerisation .Why?
NO2 is an odd electron molecule . So on dimerisation it is converted to N2O4 which
contains even no .of electrons . (Diagram)
NO being an odd electron molecule , doesnt undergo dimerisation . Why?
The unpaired electron in NO is delocalized and gets stabilized .(Diagram)
How is HNO3 manufactured by Ostwalds process .
Pt/Rh/ 500K ,9bar

4NH3(g) + 5O2 (g)

4NO(g)
2NO(g) + O2(g)
2NO2(g)
3NO2(g) + H2O (l)
2HNO3 (aq) + NO (g)
What is the Chemistry of Brown ring test ?
NO + 3Fe3+ + 2H2O
NO3- + 3Fe2+ + 4H+
2+
[Fe(H2O)6] + NO
[Fe(H2O)5(NO)]2+ + H2O
Methods of preparation of oxides of Nitrogen .(Table 7.3)
Reactions of con.HNO3 with Zn, Cu, I2, C, S8, P4
How does white P4 react with boiling NaOH ?
P4 + 3NaOH + 3H2O
PH3 + 3NaH2PO2
White Phosphorous is more reactive than red phosphorous .Why?
In white phosphorous there is angular strain in P4 molecule .so it is less stable and more
reactive compared to red phosphorous.
What are the differences between white phosphorous and red phosphorous?
a. White P consists of discrete tetrahedral P4 molecules whereas red p consists of chain
of P4 tetrahedra.
b. White P is soluble in CS2 while red P is insoluble in CS2 .
c. White P glows in darkness whereas red P doesnt glow .
d. white P is more reactive than red P
White P glows in darkness .Why?
Due to chemiluminescence .
White P catches fire spontaneously .Why?
Because its ignition temperature is lower than atmospheric temperature.
How are and Black Phosphorous prepared ?
Black P is prepared by heating red P in a sealed tube at 803k .
black P is prepared by heating white P under high pressure.
Impure PH3 is inflammable. Why?
Due to the presence of impurities like PH3 or P4 vapours which are inflammable .
How is PH3 purified ?
Impure PH3 is absorbed in HI to form PH4I which on treating with KOH gives off PH3.
How does Ca3P2 react with HCl?
Ca3P2 + 6HCl
3CaCl2 + 2PH3
How does PH3 react with a. CuSO4 b. HgCl2

3CuSO4 + 2PH3
Cu3P2 + 3H2SO4
3HgCl2 + 2PH3
Hg3P2 + 6HCl
33.
Show that PH3 is Basic .
PH3 is a Lewis acid due to the presence of a lone pair electron on P atom .It reacts with
acids like HI and gives salt .
PH4I
PH3 + HI
34.
Bond angle in PH4+ is higher than that in PH3 . Why?
In PH3 there are 3 bond pairs and 1 lone pair of electrons , whereas in PH4+ there are
only 4 bond pairs of electrons . Due to greater repulsion between lone pair and bond
pair in PH3 as compared to bond pair bond pair repulsion in PH4+ , the bond angle in PH3
is less than that in PH4+.
35.
PCl3 fumes in moist air .Why?
Due to formation of HCl gas with water.
PCl3 + 3H2O
H3PO3 + 3HCl
36.
What happens when PCl5 is heated ?
It decomposes to give PCl3 and Cl2 .
37.
Why does PCl5 fumes in moist air
Due to formation of HCl gas with water.
PCl5 + 4H2O
H3PO4 + 5HCl
38.
All the five P-Cl bonds in PCl5 are not equivalent . Why?
PCl5 has a triagonal bipyramidal structure with 3 P-Cl bonds in equatorial position and 2
P-Cl bonds in axial positions . Since axial bonds experience more repulsion from equatorial
bonds ,they are slightly longer than equatorial bonds .
39.
H3PO3 undergoes disproportionation .Why?
Due to less stability of +3 oxidation state of P compared to its +5 and -3 oxidation state .
4H3PO3
3H3PO4 + PH3
40.
H3PO2 is a reducing agent .Why?
Due to the presence of 2 P-H bonds.
Eg. 4AgNO3 + 2H2O + H3PO2
4Ag + 4HNO3 + H3PO4
41.
H3PO3 is a dibasic acid though there are 3 hydrogen atoms.Why?
In H3PO3 there are only 2 H atoms which are ionisable ( due to 2 P-OH bonds ).The third
H atom is bonded to P , so not ionisable .
42.
How Many types of salts are formed by the following acids?
a) H3PO3 - 2 types (basicity is 2)
b) H3PO4 -- 3 types (basicity is 3)
c) H3PO2 -- 1 type (basicity is 1)
43.
Solid form of PCl5 is conducting. Why?
In solid form PCl5 exists as an ionic compound [PCl4]+ [PCl6]44.
CN- is a known compound whereas CP- is not known.Why?
Nitrogen can form p- p bond with carbon .whereas Phosphorous cant form p- p
with carbon.
GROUP-16TH
1.
There is a large difference in melting and boiling points of oxygen and sulphur.Why?

Oxygen exists as a diatomic molecule O2 whereas Sulphur exists in a puckered

arrangement of S8 molecules . Therefore there is strong intermolecular force in sulphur .
2.
Name two compounds in which Oxygen shows positive oxidation state .
OF2(-2) and O2F2 (-1)
3.
In the elemental form O2 is a gas whereas other elements of the group are solids .Why?
Oxygen can form p- p multiple bond with itself and form O2 molecules . But other
members of the group cant form p- p multiple bonds with their atoms and so they form
puckered arrangement of their polyatomic molecules .
4.
Oxygen shows positive oxidation state in compounds with Fluorine. Why?
Oxygen is less electronegative than Fluorine .
5.
First ionization enthalpy of 16th group elements is less than that of 15th group elements.
Why?
15th group elements have extra stable half filled P orbitals as their valence orbital, so a
large amount of energy is required to remove one valence electron .
6.
H2O is a liquid whereas all the other hydrides of 16th group are gases. Why?
Due to strong intermolecular H-bonding in H2O
7.
Arrange the Hydrides of 16th group elements in increasing order of the property
mentioned below
a) Thermal stability : H2Po <H2Te<H2Se<H2S<H2O
b) Acid strength
: H2O<H2S<H2Se<H2Te<H2PO
c) Reducing property : H2O<H2S<H2Se<H2Te<H2PO
8.
The acid character of hydrides of 16th group elements increases down the group.Why/
Because the bond strength of E-H bond decreases down the group due to increase in
the size of the element .
9.
10.
11.

12.
13.
14.
15.

SF6 is exceptionally stable .Why?

Because Sulphur is stericaly protected by six Fluorine atoms.
What is the hybridization and shape of SF4 molecule ?
Sp3d and the shape is see-saw .
How are oxides classified ? Give one example for each .
a) Acidic : SO2
b) Basic : Na2O
c) Amphoteric : Al2O3
d) Neutral : CO
Give reactions to show the amphoteric nature of Al2O3
2[Al(H2O06]3+(aq)
Basic character : Al2O3 (s) + 6HCl(aq) + 9H2O(l)
Acid character : Al2O3(s) + 6NaOH(aq) + 3H2O
2 Na3[Al(OH)6](aq)
High concentrations of ozone can be dangerously explosive .Why?
This is due to liberation of large amount of heat during its decomposition to form O2 .
O3(g)
O2(g) + (O)
Why does O3 act as a powerful oxidizing oxidizing agent ?
Due to the ease with which it liberates atoms of nascent oxygen atom .
O3(g)
O2(g) + (O)
Give two examples to show the oxidizing property of ozone .

PbS (s) + 4O3(g)

PbSO4(s) + 4O2 (g)
2I-(aq) + O3(g) + H2O (l)
2OH-(aq) + I2 (s) + O2(g)
16.
How is O3 estimated quantitatively ?
O3 is treated with an excess of KI solution buffered with a borate buffer , the iodine so
liberated is estimated by titrating with a saturated solution of Sodium thiosulphate solution .
From the amount of iodine liberated the amount of O3 can be estimated .
2I-(aq) + O3(g) + H2O (l)
2OH-(aq) + I2 (s) + O2(g)
17.
How does the depletion of O3 take place in the upper atmosphere ?
The Nitrogen oxides emitted by supersonic jet aeroplanes depletes the O3 layer
NO2(g) + O2(g)
NO (g) + O3 (g)
18.
The O-O bonds in O3 are identical .Why?
Due to resonance both O-O bonds get partial double bond character and are identical.
19.

Sulphur in the vapour phase shows paramagnetism .Why?

In the vapour form sulphur exists as a diatomic molecule which contains two unpaired
electrons in the antibonding pi molecular orbital like O2 .
20.
The behavior of SO2 is like CO2 .Explain .
SO2 reacts with alkali solution in the similar way that CO2 reacts.
2NaOH + SO2
Na2SO3 + H2O
Na2SO3 + H2O + SO2
2NaHSO3
21.
How is SO2 gas detected ?
So2 gas on passing through acidified KMO4 solution , the purple colour of KMnO4 is
discharged .
-

5SO2(g0 + 2MnO4 (aq) + 2H2O

5SO42- (aq) + 2Mn2+ + 4H+
22.
Both S-O bonds in SO2 are identical. Why?
Due to resonance both S-O bonds are getting partial double bond character and are
identical. (Diagram)
23.
Structure of oxoacids of Sulphur (From Text Book )
24.
How is H2SO4 manufactured by Contact Process ?
S (s) + O2(g)
SO2(g)
2SO2(g) + O2 (g)

V2O5 / 720K , 2 bar

2SO3 (g)

SO3(g) + H2SO4
H2S2O7
H2S2O7 + H2O
2H2SO4
Reactions of Con H2SO4 refer text book
GROUP 17TH
1.
Mention one source each for F, Br& I
F- Fluorspar (CaF2) BrSea water I- Chile saltpeter.
2.
Halogens have very little tendency to lose electrons .Why?
Due to their high ionization enthalpy.
3.
Halogens have max. negative electron gain enthalpy. Why?

Due to a) Small size b) high effective nuclear charge c) they need one electron to
attain stable noble gas configuration .
4.
The electron gain enthalpy of Fluorine is less negative than Chlorine .Why?
Due to small size of Fluorine , there is strong inter electronic repulsion in the small 2p
orbital is high.
5.
All halogens are coloured .Why?
Due to absorption of radiation in the visible region which results in the excitation of
outer electrons to higher energy levels .
6.
The bond dissociation enthalpy of F2 is smaller than that of Chlorine .Why?
Due to large electron electron repulsion among the lone pairs of electrons in Fluorine
7.
Fluorine is a strong oxidizing agent than Chlorine .Why?
This is due to a). Low bond enthalpy of F2. b). high hydration enthalpy of F8.
Fluorine doesnt show positive oxidation state.Why?
Due to its highest electronegativity .
9.
Fluorine cant expand its covalency beyond one .Why?
Due to absence of vacant d orbital.
10.
The oxidizing tendency of halogens decreases down the group. Why?
Due to a) decreasing electron gain enthalpy b) decreasing hydration enthalpy of X11.
What happens when F2 gas is passed through solutions of a) KCl b)KBr c) KI
Fluorine being more reactive oxidizes the halides to the respective halogens .
2KF (aq) + Cl2(g)
KCl (aq) + F2 (g)
KBr (aq) + F2(g)
2KF(aq) + Br2(l)
KI(aq) + F2 (g)
2Kf(aq) + I2(g)
12.
How does F2 gas react with water ?
F2 oxidises water to oxygen gas; F2(g) + 2H2O (l)
4HF(aq) + O2(g)
Bcoz, F is more electroneg than O
13.
How do Chlorine and Bromine react with water ?
HCl (aq) + HOCl (aq)
Cl2(g) + H2O(l)
Br2(l) + H2O(l)
HBr(aq) + HOBr(aq)
14.
What are the reasons for the anomalous behavior of Fluorine ?
a) small size b) highest electronegativity c) low F-F bond dissociation enthalpy
d) non availability of vacant d orbitals in the valence shell.
15.
Most of the compounds of Fluorine are exothermic. Why?
Due to small size and strong bond formed by Fluorine with atoms of other elements .
16.
Fluorine forms only one oxoacid HOF . Why?
Due to absence of vacant d - orbitals in its valence shell.
17.
HF is a liquid . Why?
Due to strong intermolecular H-bonding
18.
Arrange the hydrides of 17th group elements in the increasing order of the property
mentioned .
Acid strength : HF <HCl<HBr<HI
Stability : HI<HBr<HCl<HF
19.
The stability of the hydrides of 17th group elements decreases down the group. Why?
Due to the decreasing bond strength of E-H bond .

20.
21.
22.

What is the use of O2F2 ?

Used for the removal of Pu from the spent nuclear of nuclear power plant .
What is the use of ClO2 ?
Used in the bleaching of paper pulp and textiles and in water treatment .

Name the oxide of halogens used in the estimation of CO.

I2O5
23.
Which is more covalent SnCl4 or SnCl2 and why?
SnCl4 , because the higher oxidation state of the metal is more polarizing than its lower
oxidation state .
24.
How does Cl2 reacts with a) cold dilute NaOH b) hot concentrated NaOH
Cold and dilute NaOH
2NaOH + Cl2
NaCl + NaOCl + H2O
Hot and concentrated NaOH
5NaCl + NaClO3 + 3H2O
6NaOH + 3Cl2
25.
How is Bleaching powder manufactured ? What is its composition ?
By passing Cl2 gas through dry slaked lime .
2Ca(OH) 2 +2Cl2
Ca(OCl)2 + CaCl2 + 2H2O
Composition is Ca(OCl)2.CaCl2.Ca(OH)2.2H2O
26.
Chlorine water loses its yellow colour on standing .Why?
Due to the formation of HCl and HOCl . Cl2 + H2O HCl +HOCl
26.
Give the reason for the bleaching and oxidizing properties of Chlorine .
Moist Chlorine gives HCl and HOCl . HOCl decomposes to give HCl and nascent oxygen
which is responsible for oxidizing and bleaching properties . Bleaching action is due to oxidation
Cl2 + H2O
2HCl + (O)
Coloured substance + (O)
colourless substance .
27.
Name two poisonous gases that can be prepared from Chlorine .
a) Phosgene (COCl2) b) Tear gas (CCl3NO2)
28.
How does moist Chlorine react with I2 ?
2HIO3 + 10HCl
I2 + 6H2O + 5Cl2
29.
What is aquaregia ? What is its use ?
Aquqregia is a mixture of Con.HCl and Con.HNO3 in the ratio 3:1. It is used for dissolving
noble metals like Gold and platinum.
Au + 4H+ + NO3- + 4ClAuCl4- + NO + 2H2O
30.
When HCl reacts with finely powdered Iron , it forms ferrous chloride and not ferric
chloride .Why?
HCl reacts with Iron and produces H2 .
Fe + 2HCl
FeCl2 + H2
Liberation of hydrogen prevents the formation of ferric chloride.
31.
Write the geometry of the following interhalogen compounds .
a) ClF (XX1) : Linear.
b) ClF3 (XX3) : Bent T shape.
c) BrF5 (XX5) : Square pyramidal
d) IF5 : Pentagonal bipyramidal .

32.
33.
34.

Interhalogen compounds are more reactive than halogens except F2 .Why?

X-X bond in interhalogens is weaker than X-X bond in halogens except F-F bond .
Name the interhalogen which is used in the enrichment of Uranium?
ClF3.
Write the produt of Hydrolysis of the following interhalgens .
HX + HOX
a) XX : XX + H2O
b) XX3 : XX3 + 2H2O
3HX + HOXO
c) XX5 : XX5 + 3H2O
5HX + HOXO2
d) XX7 : XX7 + 4H2O
7HX + HOXO3

GROUP 18TH
1.
The elements of group18 are known as noble gases . Why?
They have completely filled valence shell . So they react with a few elements only under
certain conditions .
2.
18th group elements have large positive values of electron gain enthalpy .Why?
Due to their stable electronic configuration they have no tendency to accept the
electron .
3.
18th group elements have very low melting and boiling points . why?
Due to very weak intermolecular interaction, i.e.,weak dispersion forces .
4.
Noble gases are liquefied at very low temperatures .Why?
Due to weak intermolecular forces .
5.
Noble gases are chemically inert .Why?
Due to a) completely filled valence shell. b) High ionization enthalpy c) positive
electron gain enthalpy .
6.
What inspired N. Bartlett for carrying out reaction between Xe and PtF6 ?
The first ionization enthalpy of molecular oxygen was almost identical with that of Xe .
7.
What was the compound prepared by N. Bartlett that led to the discovery of first noble
gas compound ?
O2+PtF68.
What was the first noble gas compound prepared ?
Xe+PtF69.
XeF2 is a linear molecule without bend .Why?
XeF2 has 3 lone pair and 2 bond pair electrons .The 2 bond pairs are occupying the axial
positions and 3 lone pairs are occupying the equatorial positions making 1200 with each other
and 900 with the bond pairs . Since the bond pairs are experiencing same amount of repulsion
from the lone pairs the molecule is linear without bend.
10.
Give reactions to show that Xe fluorides act as both Lewis Acid and Lewis Base
Lewis Acid : XeF6 + NaF
M+ [XeF7]Lewis Base : XeF2 + PF5
[XeF]+[PF6]11.
write a balanced reaction between water and a) XeF4 b) XeF6
6XeF4 + 12H2O
4Xe + 2XeO3 + 24HF + 3O2
XeF6 + 3H2O
XeO3 + 6HF
12.
Why is He used in diving apparatus ?
Because He gas is very light and its solubility in water is very less.

13.
14.
with

Why is it difficult to study the chemistry of Radon ?

Because it is radioactive .
Give the formula and describe the structure of a noble gas species which is isostructural
-

a) ICl4 b) IBr2 c) BrO3

a) XeF4 : Square pyramidal with 2 lone pairs above and below the plane .
b) XeF2 : Linear with 3 lone pairs occupying the equatorial position .
c) XeO3 : Pyramidal with a lone pair electron at the apex.
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