Sheet - 02 _ p-Block Group 15th - 18th

(Inorganic Chemistry)
P-BLOCK ELEMENT
NITROGEN FAMILY
GROUP-15 ELEMENTS (N, P, As, Sb, Bi)
Occurrence :
Nitrogen : Molecular nitrogen comprises 78% by volume of the atmosphere. It occurs as
sodium nitrate, NaNO3 (called Chile saltpetre) and potassium nitrate (Indian saltpetre).
Phosphorus :
(i) It is eleventh most abundant element in earth's crust occurs in minerals of the apatite
family, Ca9 (PO4 )6 . CaX 2 (X = F, Cl or OH) (e.g., fluorapatite Ca9 (PO4 )6 ⋅ CaF2 ) and also
found as chlorapatite Ca9 (PO4 )6 ⋅ CaCl2 ).
(ii) Arsenic , antimony and bismuth are found mainly as sulphide minerals.
Electronic Configuration :
The valence shell electronic configuration of these elements is ns2 np3 .
Atomic and Ionic Radii :
Covalent radius : N < P < As < Sb < Bi
Ionisation Enthalpy :
N > P > As > Sb > Bi (IE1 values)
Electronegativity :
N > P > As > Sb = Bi
Metallic Character
N<P As< Sb<Bi
None Metalloid Metals
metal
Physical Properties :
(i) All the elements of this group are polyatomic. Dinitrogen is a diatomic gas while all others
are solids.
(ii) Metallic character increases down the group.
(iii) The boiling points, in general, increase from top to bottom in the group but the melting
point increases upto arsenic and then decreases upto bismuth.
(iv) Except nitrogen all the elements show allotropy.
P → exists in three allotropic form as white, red and black
As, Sb → exist as yellow and grey
Bi → exist as 𝛼, 𝛽, 𝛾, 𝛿 allotropic form
Catenation
The group 15 elements also show catenation property but to much smaller extent than carbon.
APNI KAKSHA 1
For example hydrazine (H2NNH2) has two N atoms bonded together HN3 has three N atoms.
+
HN3 H − N̈ = N = N̈:
• Among group 15 elements P has the maximum tendency for catenation forming cyclic as well
as open chain compounds consisting of many phosphorous atoms.
P2 H4 has two P atoms bonded together the lesser tendency of elements of group 15 to show
catenation in compression to carbon is their low dissociation enthalpies.
C−C 353.3 kJ/mole
N−N 160.8 kJ/ mole
P−P 201.6 kJ/ mole
As − As 147.4 kJ/ mole
Chemical Properties :
Oxidation states and trends in chemical reactivity
(i) The common oxidation states of these elements are −3, +3 and +5 .
(ii) The tendency to exhibit -3 oxidation state decreases down the group due to increase in size
and metallic character. Bismuth hardly forms any compound in -3 oxidation state.
(iii) The stability of +5 oxidation state decreases down the group. The only well characterised
Bi(V) compound is BiF5 .
(iv) The stability of +5 oxidation state decreases and that of +3 state increases (due to inert pair
effect) down the group.
(v) Nitrogen exhibits +1, +2, +4 oxidation states also when it reacts with oxygen. Phosphorus
also shows +1 and +4 oxidation states in some oxoacids.
(vi) In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in acid
solution. For example,
(i) 3HNO2 → HNO3 + H2 O + 2NO
(vii) Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate
into +5 and -3 both in alkali and acid.
Heal
(ii) 4H3 PO3 ⟶ 3H3 PO4 + PH3
(viii) +3 oxidation state in case of arsenic, antimony and bismuth becomes increasingly stable
with respect to disproportionation.
(ix) Nitrogen is restricted to a maximum covalency of 4 since only four (one 𝑠 and three p)
orbitals are available for bonding.
(x) The heavier elements have vacant d orbitals in the outermost shell which can be used for
bonding 6 (covalency) and hence, expand their covalency as in PF6− .
Anomalous properties of nitrogen
APNI KAKSHA 2
(i) Nitrogen has unique ability to form p𝜋 − p𝜋 multiple bonds with itself and with other
elements having small size and high electronegativity (e.g., C, O ).
(ii) Heavier elements of this group do not form pp-pp bonds as their atomic orbitals are so
large and diffuse that they cannot have effective overlapping.
(iii) Nitrogen exists as a diatomic molecule with a triple bond (one 𝑠 and two p) between the
two atoms.
N2 bond enthalpy (941.4 kJ mol−1 ) is very high.
(iv) Phosphorus, arsenic and antimony form single bonds as P-P, As-As and Sb-Sb while
bismuth forms metallic bonds in elemental state.
(i) Reactivity towards hydrogen:

NH3 > PH3 > AsH3 > SbH3 ≥ BiH3 .
(ii) Reactivity towards oxygen: All these elements form two types of oxides: E2 O3 and E2 O5 .
Their acidic character decreases down the group. The oxides of the type E2 O3 of nitrogen and
phosphorus are purely acidic, that of arsenic and antimony amphoteric and those of bismuth
predominantly basic.
(iii) Reactivity towards halogens: These elements react to form two series of halides: EX3 and
EX5 . In case of nitrogen, only NF3 is known to be stable. Trihalides except BiF3 are
predominantly covalent in nature.
(iv) Reactivity towards metals: All these elements react with metals to form their binary
compounds exhibiting -3 oxidation state, such as, Ca3 N2 (calcium nitride) Ca3 P2 (calcium
phosphide), Na3 As (sodium arsenide), Zn3 Sb2 (zinc antimonide) and Mg 3 Bi2 (magnesium
bismuthide).
DINITROGEN
Preparation :
(a) Commercial preparation :
Dinitrogen is produced commerciallyby 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 ).
(b) Laboratory preparation :
(i) Dinitrogen is prepared by treating an aqueous solution of ammonium chloride with sodium
nitrite.
NH4 Cl(aq) + NaNO2 (aq) → N2 ( g) + 2H2 O(ℓ) + NaCl(aq)
APNI KAKSHA 3
Small amounts of NO and HNO3 are also formed in this reaction; these impurities can be
removed by passing the gas through aqueous sulphuric acid containing potassium dichromate.
(ii) Dinitrogen can also be obtained by the thermal decomposition of ammonium dichromate.
Heat
(NH4 )2Cr2 O7 ⟶ N2 + 4H2 O + Cr2 O3
Note : Very pure nitrogen can be obtained by the thermal decomposition of sodium or barium
azide.
Δ
Ba(N3 )2 ⟶ Ba + 3 N2
300∘ C
2NaN3 ⟶ 2Na + 3 N2
(c) Other preparation
2NH3 + 3NaOCl ⟶ N2 + 3NaCl + 3H2 O
2NH3 + 3Ca(OCl)2 ⟶ 2 N2 + 3CaCl2 + 6H2 O
8NH3 + 3Br2 ⟶ N2 + 6NH4 Br
2NO + 2Cu ⟶ 2CuO + N2
(red, overheated) (Black)
Cl2 passed into liquor NH3
3Cl2 + 2NH3 ⟶ N2 + 6HCl
6NH3 + 6HCl ⟶ 6NH4 Cl
-------------------------------
3Cl2 + 8NH3 ⟶ N2 + 6NH4 Cl
In this method conc. of NH3 should not be lowered down beyond a particular limit.
3Cl2 + NH3 ⟶ NCl3 + 3HCl
(Trimendously explosive)
Physical properties :
(i) Dinitrogen is a colourless, odourless, tasteless and non-toxic gas.
(ii) Nitrogen atom has two stable isotopes: 14
N and 15
N.
(iii) It has a very low solubility in water (23.2 cm3 per litre of water at 273 K and 1 bar
pressure)
(iv) Dinotrogen has low freezing and boiling points.
Chemical properties
Reaction with metal : At higher temperatures, it directly combines with some metals to form
predominantly ionic nitrides and with non-metals, covalent nitrides. A few typical reactions
are:
APNI KAKSHA 4
Heat
6Li + N2 ⟶ 2Li3 N
Heat
3Mg + N2 ⟶ Mg 3 N2
Reaction with metal : It combines with hydrogen at about 773 K in the presence of a catalyst
(Haber's Process) to form ammonia:
773k
N2 ( g) + 3H2 ( g) ⇌ 2NH3 ( g)
Dinitrogen combines with dioxygen only at very high temperature (at about 2000 K ) to form
nitric oxide, NO.
Heat
NO2 + (g) ⇌ 2NO(g)
Absorption on calcium carbride
N2 can be absorbed by calcium carbide at the temperature around 1000∘ C.
Ques. Why dinitrogen is inert at room temperature ?

Ans. Dinitrogen is inert at room temperature because of the high bond enthalpy of N ≡ N bond.
Reactivity, however, increases rapidly with rise in temperature.
TYPES OF NITRIDE
Salt like or ionic : Li3 N, Na3 N, K 3 N(?), Ca3 N2 , Mg 3 N2 , Be3 N2
Covalent : AlN, BN, Si3 N4 , Ge3 N4 , Sn3 N4
AMMONIA
APNI KAKSHA 5
Preparation :
(i) Ammonia is present in small quantities in air and soil where it is formed by the decay of
nitrogenous organic matter e.g., urea.
NH2 CONH2 + 2H2 O ⟶ (NH4 )2 CO3 ⇌ 2NH3 + H2 O + CO2
(ii) Small scale preparation By the decomposition of ammonium salts when treated with
caustic soda or calcium hydroxide.
2NH4 Cl + Ca(OH)2 → 2NH3 + 2H2 O + CaCl2
(NH4 )2 SO4 + 2NaOH → 2NH3 + 2H2 O + Na2 SO4
(iii) Large scale manufacturing (Haber's Process)
N2( g) + 3H2 ( g) ⇌ 2NH3 ( g); Df H Θ = −46.1 kJ mol−1
❖ According to Le Chatelier's principle, high pressure and low temperature would favour the
formation of ammonia.
❖ The optimum conditions for the production of ammonia are a pressure of 200 × 105 Pa (about
200 atm ), a temperature of ∼ 700 K.
❖ Use of a catalyst such as iron oxide with small amounts of K 2 O and Al2 O3 to increase the rate
of attainment of equilibrium.
❖ The flow chart for the production of ammonia is shown in figure. Earlier, iron was used as a
catalyst with molybdenum as a promoter.
Other prepration :
(i) Nitrate or nitrite reduction : NO3− /NO−
2 + Zn or Al + NaOH ⟶ NH3 + [Zn(OH)4 ]
2−
or
APNI KAKSHA 6
[Al(OH)4 ]−
(ii) Metal nitride hydrolysis : N3− + 3H2 O ⟶ NH3 ↑ +3OH −
Properties :
(i) Ammonia is a colourless gas with a pungent odour.
(ii) Its freezing and boiling points are 198.4 and 239.7 K respectively.
(iii) In the solid and liquid states, it is associated through hydrogen bonds.
(iv) Ammonia gas is highly soluble in water.
Basic character :
Its aqueous solution is weakly basic due to the formation of OH − ions.
NH3 ( g) + H2 O(ℓ) ⇌ NH4+ (aq) + OH − (aq)
It forms ammonium salts with acids, e.g., NH4 Cl, (NH4 )2 SO4 , etc.
As a weak base, it precipitates the hydroxides (hydrated oxides in case of some metals) of many
metals from their salt solutions.
For example,
ZnSO4 (aq) + 2NH4 OH(aq) ⟶ Zn(OH)2 ( s) + (NH4 )2 SO4 (aq)
(White ppt)
FeCl3 (aq) + NH4 OH(aq) ⟶ Fe2 O3 ⋅ xH2 O(s) + NH4 Cl(aq)
(brown ppt)
Note -1: Other reactions
CH3 COOH is strong acid in liq. NH3 while in water is weak acid.
̅ + H+
AcOH ⇌ AcO
4NH3 + H + ⟶ NH4+
H2 O + H + ⟶ H3 O+
Basisity order NH3 > H2 O
more solvation of H + in NH3 .
Note - 2 : Hydrolysis and Ammonolysis occurs is a same way.
Δ
SiCl4 + 4H2 O ⟶ 4HCl + Si(OH)4 ⟶ SiO2 + 2H2 O
Δ
SiCl4 + 8NH3 ⟶ 4NH4 Cl + Si(NH2 )4 ⟶ Si3 N4 + NH3 ↑
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4 Cl
vapour respectively.
Uses :
(i) Ammonia is used to produce various nitrogenous fertilisers.
(ii) In the manufacture of some inorganic nitrogen compounds, the most important one being
APNI KAKSHA 7
nitric acid.
(iii) Liquid ammonia is also used as a refrigerant.
OXIDES OF NITROGEN
Nitrogen forms a number of oxides in different oxidation states. The names, formulas,
preparation and physical appearance of these oxides are given in Table.
Oxides of Nitrogen
Oxidation state Physical

Common Methods of
Name Formula of nitrogen Appearance and
Prepration
Chemical nature
Heat
Dinitrogen oxide NH4 NO3 ⟶ Colourless gas,
N2 O +1
[Nitrogen oxide] N2 O + 2H2 O neutral
2NaNO2 + 2FeSO4 + 3H2 SO4 Colourless gas,

Nitrogen monoxide
NO +2 → Fe2 (SO4 )3 + 2NaHSO4
[Nitrogen (II) oxide ] neutral
+2H2 O + 2NO
Dinitrogen trioxide 250 K Blue solid, acidic

N2 O3 +3 2NO + N2 O4 ⟶ 2 N2 O3
[Nitrogen (III) oxide] Blue liquid (−30∘ C)
Nitrogen dioxide 2 Pb(NO3 )2 ⟶ Brown gas.

NO2 +4 673 K
[Nitrogen (IV) oxide] 4NO2 + 2PbO + O2 Acidic
Nitrogen tetroxide Cool Colourless solid /

N2 O4 +4 2NO2 ⇌ N2 O4
[Nitrogen (IV) oxide] Heal liquid, acidic
Nitrogen pentaoxide 4HNO3 + P4 O10 Colourless solid,

N2 O5 +5
[Nitrogen (V) oxide] → 4HPO3 + 2 N2 O5 acidic
Preparations:
1. N2 O
(i) NH4 NO3 ⟶ N2 O + H2 O
(ii) Zn + HNO3 ⟶ Zn(NO3 )2 + N2 O + H2 O
(dil.& cold)
APNI KAKSHA 8
2. NO
(i) Cu + HNO3 (1: 1) ⟶ Cu(NO3 )2 + NO + H2 O
hot
(ii) KNO3 + FeSO4 + H2 SO4 ⟶ Fe2 (SO4 )3 + K 2 SO4 + NO + H2 O
Δ
FeSO4 + NO ⟶ FeSO4 ⋅ NO ⟶ FeSO4 + NO↑
(iii) Oswald process-Restricted oxidation of NH3 . Industrial process.
3. N2 O3
(i) HNO3 + As2 O3 ⟶ H3 AsO4 + N2 O3
(ii)
4. NO2
Δ 1
(i) M(NO3 )2 ⟶ MO + 2NO2 + 2 O2
M = Pb, Cu, Ba, Ca

(ii) (Cu, Pb, Ag) + HNO3 ⟶ M-nitrate +NO2 + H2 O
(hot & conc.)
N2 O5
5. (i) 2HNO3 + P2 O5 ⟶ 2HPO3 + N2 O5
(ii) 4AgNO3 + 2Cl2 (dry gas) ⟶ 4AgCl + 2 N2 O5 + O2
Properties:
(I) Decoposition Behaviour
500∘ C−900∘ C
(i) N2 O ⟶ 2 N2 + O2
800∘ C
(ii) 2NO ⟶ 2 N2 + O2
Room temp.
(iii) N2 O3 ⟶ NO2 + NO
(Blue liq.) at (−30∘ C)
620∘ C
(iv) 2NO2 ⟶ 2NO + O2
11∘ C
N2 O4 ⟶ 2NO2
(white solid) Brown gas at (−11∘ C)
30∘ C 40∘ C 1
(v) N2 O5 ⟶ N2 O5 ⟶ 2NO2 + 2 O2
APNI KAKSHA 9
Colourless yellow
Solid liq.
(II) Reaction with H2O&NaOH
H2 O NaOH
(i) N2 O : Fairly soluble in water and
produces neutral solution
(ii) NO : Sparingly soluble in water

and produces neutral soln.
(iii) N2 O3 : 2HNO2
Hence it is known as
NaNO2 anhydride of HNO2 NaNO2
(iv) NO2 : HNO2 + HNO3
called as mixed anhydride NaNO2 + NaNO3
(v) N2 O5 : 2HNO3
called as anhydride of NaNO3 HNO3
Other properties:
Hence it is better supporter for combustion

S + N2 O ⟶ SO2 + N2
P + N2 O ⟶ P2 O5 + N2
Mg + N2 O ⟶ MgO + N2
Na + N2 O ⟶ Na2 O + N2
Cu + N2 O ⟶ CuO + N2
H2 + N2 O ⟶ H2 O + N2
NOTE: -
1
(i) It burns : NO + 2 O2 ⟶ NO2
(ii) It supports combustion also for molten sulphur and hot phosphorous.
S + 2NO ⟶ SO2 + N2
5
2P + 5NO ⟶ P2 O5 + N2
2
(iii) It is being absorbed by FeSO4 solution.

(iv) It is having reducing property.
APNI KAKSHA 10
KMnO4 + NO + H2 SO4 ⟶ K 2 SO4 + MnSO4 + HNO3 + H2 O

(v) NO shows oxidising property also.
SO2 + 2NO + H2 O ⟶ H2 SO4 + N2 O
H2 S + 2NO ⟶ H2 O + S ↓ +N2 O
3SnCl2 + 2NO + 6HCl ⟶ 3SnCl4 + 2NH2 OH
(Used for NH2 OH preparation)
(vi) NO combines with X2 (X2 = Cl2 Br2 F2 ) to produce NOX
2NO + X2 ⟶ 2NOX
N2 O3 : No more properties.
(1) It is having oxidising property.
S + NO2 ⟶ SO2 + NO
P + NO2 ⟶ P2 O5 + NO
C + NO2 ⟶ CO2 + NO
SO2 + NO2 + H2 O ⟶ H2 SO4 + NO
H2 S + NO2 ⟶ H2 O + S ↓ +NO
NO not formed : 2KI + 2NO2 ⟶ I2 + 2KNO2
(2) Reducing property of NO2 .
KMnO4 + NO2 + H2 SO4 ⟶ K 2 SO4 + MnSO4 + HNO3 + H2 O
O03 + 2NO → ⏟02
O + N2 O5
not the reduction product of 𝑂3
N2 O5 :
I2 + 5 N2 O5 ⟶ I2 O5 + 10NO2
I2 O5 is used for the estimation of CO
I2 O5 + 5CO ⟶ I2 + 5CO2
N2 O5 + NaCl ⟶ NaNO3 + NO2 Cl
This likes proves that N2O5 is consisting of ion pair of NO2+ &NO−
3
OXOACIDS OF NITROGEN
H2 N2 O2 (hyponitrous acid), HNO2 (nitrous acid) and HNO3 (nitric acid). Amongst them HNO3
is the most important.
NITROUS ACID (𝐇𝐍𝐎𝟐 )
Preparation
dilacid
(a) M-nitrite HClor ⟶ HNO2
2 SO4
(b) N2 O3 + H2 O ⟶ 2HNO2
APNI KAKSHA 11
Properties
(a) Oxidising property : Because of its easy oxidation to liberate nascent oxygen, it acts
as a strong oxidant 2HNO2 ⟶ H2 O + 2NO + (O)
2KI + 2HNO2 + 2HCl ⟶ 2KCl + 2H2 O + 2NO + I2
SnCl2 + 2HNO2 + 2HCl ⟶ SnCl4 + 2NO + 2H2 O
SO2 + 2HNO2 ⟶ H2 SO4 + 2NO
H2 S + 2HNO2 ⟶ 2H2 O + S ↓ +2NO
2FeSO4 + 2HNO2 + H2 SO4 ⟶ Fe2 (SO4 )3 + 2NO + 2H2 O
(b) Reducing property : Nitrous acid also acts as a reducing agent as it can be oxidised into
nitric acid.
HNO2 + (O) ⟶ HNO3
2KMnO4 + 5HNO2 + 3H2 SO4 ⟶ K 2 SO4 + 2MnSO4 + 5HNO3 + 3H2 O
K 2 Cr2 O7 + 3HNO2 + 4H2 SO4 ⟶ K 2 SO4 + Cr2 (SO4 )3 + 3HNO3 + 4H2 O
H2 O2 + HNO2 ⟶ H2 O + HNO3
HNO2 + C2 H5 NH2 ⟶ C2 H5 OH + N2 + H2 OS
<5∘ C
HNO2 + C6 H5 − NH2 ⋅ HCl ⟶ C6 H5 N = NCl + 2H2 O
Benzene diazonium chloride
NITRIC ACID
It was named aqua fortis (means strong water) by alchemists.
Preparation :
Laboratory Method : By heating KNO3 or NaNO3 and concentrated H2 SO4 in a glass retort.
KNO3 /NaNO3 + H2 SO4 → KHSO4 /NaHSO4 + HNO3
Large scale preparation (Ostwald's process) :
(i) This method is based upon catalytic oxidation of NH3 by atmospheric oxygen.
Pt/Rh-gauge catalyst
4NH(g) + 5O2 ( g) 4NO(g) + 6H2 O(g)
500 K,9 bar
(ii) Nitric oxide thus formed combines with oxygen giving NO2 .
2NO(g)O2 ( g) ⇌ 2NO(g)
(iii) Nitrogen dioxide so formed, dissolves in water to give HNO3 .
3NO2 ( g) + H2 O(ℓ) ⟶ 2HNO3 (aq) + NO(g)
APNI KAKSHA 12
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
H2 SO4 .
Birkel and Eyde Process or arc process
3000∘ C
step 1 N2 + O2 Electric Arc - heat
step 2 NO + O2 ⟶ NO2
step 3 NO2 + H2 O ⟶ HNO2 + HNO3
step 4 HNO2 ⟶ HNO3 + NO + H2 O
Properties
Physical properties
(i) It is a colourless liquid (f.p. 231.4 K and b.p. 355.6 K ).
(ii) Nitric acid usually acquires yellow or brown colour due to its decomposition by sunlight
into NO2 .
Sunlight
4HNO3 ⟶ 4NO2 + 2H2 O + O2
The yellow or brown colour of the acid can be removed by warming it to 60 − 80oC and
bubbling dry air through it.
Chemical properties
Acidic character in aqueous solution, nitric acid behaves as a strong acid giving hydronium and
nitrate ions.
HNO3 (aq) + H2 O(ℓ) → H3 O+ (aq) + NO−
3 (aq)
Oxidising nature: Nitric acid acts as a strong oxidising agent as it decomposes to give nascent
oxygen easily.
2HNO3 ⟶ H2 O + 2NO2 + O
Or 2HNO3 ⟶ H2 O + 2NO + 3O
(i) Oxidation of non-metals : The nascent oxygen oxidises various non-metals to their
corresponding oxyacids of highest oxidation state.
(1) Sulphur is oxidised to sulphuric acid
S + 6HNO3 ⟶ H2 SO4 + 6NO2 + 2H2 O
conc.and hot
(2) Carbon is oxidised to carbonic acid
APNI KAKSHA 13
C + 4HNO3 → H2 CO3 + 4NO2 + 2H2 O

(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO3 → 2H3 PO4 + 10NO2 + 2H2 O
conc. and hot
(4) Iodine is oxidised to iodic acid
I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2 O
conc. and hot
(ii) Oxidation of metalloids

Metalloids like non-metals also form oxyacids of highest oxidation state.
(1) Arsenic is oxidised to arsenic acid
2As + 10HNO3 → 2H3 AsO4 + 10NO2 + 2H2 O
or As + 5HNO3 → H3 AsO4 + 5NO2 + H2 O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO3 → H3 SbO4 + 5NO2 + H2 O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3 → H2 SnO3 + 4NO2 + H2 O
(iii) Oxidation of Compounds:
(1) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3 → H2 SO4 + 2NO2
(2) Hydrogen sulphiode is oxidised to sulphur
H2 S + 2HNO3 → 2NO2 + 2H2 O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H2 SO4
6FeSO4 + 3H2 SO4 + 2HNO3 → 3Fe2 (SO4 )3 + 2NO + 4H2 O
(4) Iodine is liberated from KI.
6KI + 8HNO3 → 6KNO3 + 2NO + 3I2 + 4H2 O
(5) HBr, HI are oxidised to Br2 and I2 , respectively.
2HBr + 2HNO3 → Br2 + 2NO2 + 2H2 O
APNI KAKSHA 14
Similarly, 2HI + 2HNO3 → I2 + 2NO2 + 2H2 O

(6) Ferrous sulphide is oxidised to ferric sulphate
FeS + HNO3 → Fe2 (SO4 )3 + 8NO2 + 4H2 O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO3 + 14H → NH2 OH + NH3 + 5H2 O
Hydroxylamine
NH3 + HNO3 → NH4 NO3
------------------------------------------------
7SnCl2 + 14HCl + 3HNO3 → 7SnCl4 + NH2 OH + NH4 NO3 + 5H2 O
(ii) Reaction with metal concentrated nitric acid is a strong oxidising agent and attacks most metals
except noble metals such as gold and platinum.
Au & Pt dissolve in aqua regia a mixture of 25% conc. HNO3&75% conc. HCl.
Ex. 3Cu + 8HNO3 (dilute) → 3Cu(NO3 )2 + 2NO + 4H2 O
Cu + 4HNO3 (conc.) → Cu(NO3 )2 + 2NO2 + 2H2 O
4Zn + 10HNO3 (dilute ) → 4Zn(NO3 )2 + 5H2 O + N2 O
Zn + 4HNO3 (conc. ) → Zn(NO3 )2 + 2H2 O + 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.
Action on Proteins :
Nitric acid attacks proteins forming a yellow nitro compound called xanthoprotein. It,
therefore, stains skin and renders wool yellow. This property is utilized for the test of proteins.
ALLOTROPIC FORMS OF PHOSPHORUS
Phosphorus is found in many allotropic forms, the important ones being white, red and black.
White phosphorus dissolves in boiling NaOH solution in an inert atmosphere giving PH3.
P + 3NaOH + 3H2 O ⟶ PH + 3NaH2 PO2
(Sodium hypophosphite)
It readily catches fire in air to give dense white fumes of P4 O10 .
APNI KAKSHA 15
P4 + 5O2 → P4 O10
It consists of discrete tetrahedral P4 molecule as shown in Fig.
Red phosphorus : It is polymeric, consisting of chains of P4 tetrahedra linked together in the
manner as shown in Fig.
Black phosphorus :
(i) It has two forms a-black phosphorus and 𝛽-black phosphorus.
(ii) 𝛼-Black phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K.
(iii) It can be sublimed in air and has opaque monoclinic or rhombohedral crystals.
(iv) It does not oxidise in air. 𝛽-Black phosphorus is prepared by heating white phosphorus at
473 K under high pressure.
(v) It does not burn in air upto 673 K.
Comparison between White and Red Phosphorus
Property White phosphorus Red phosphorus
Physical state Soft waxy solid. Brittle powder.
Colour White when pure. Red.
Attains yellow colour
On standing.
Odour Garlic Odourless.
Solubility in water Insoluble. Insoluble.
Solubility in CS2 Soluble Insoluble.
Physiological action Poisonous. Non-poisonous.
Chemical activity Very active. Less active.
Stability Unstable. Stable
Phosphorescence Glows in dark Does not glow in dark.
Molecular formula P4 Complex polymer.
APNI KAKSHA 16
Prepration of white 'P'

1200∘ C
(i) ⏟
Bone ash or Apatite rock {Ca3 (PO4 )2 + 3SiO2 ⟶ 3CaSiO3 + P2 O5
Both have same formula
1500∘ C
2P2 O5 + 10C ⟶ P4 + 10CO ↑
(Coke) White ‘P’
(ii) Ca3 (PO4 )2 + 3H2 SO4 (conc.) ⟶ 3CaSO4 + 2H3 PO4
−H2 O
H3 PO4 3⟶∘ HPO3
P H C
meta phosphoric acid

1000∘ C
12C + 4HPO3 ⟶ 2H2 ↑ +12CO ↑ +P4
Coke white 'P'
PHOSPHINE
Preparation
(i) Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3 P2 + 6H2 O → 3Ca(OH)2 + 2PH3
Ca3 P2 + 6HCl → 3CaCl2 + 2PH3
(ii) Laboratory prepration it is prepared by heating white phosphorus with concentrated NaOH
solution in an inert atmosphere of CO2 .
P4 + 3NaOH + 3H2 O ⟶ PH + 3NaH2 PO2
(sodium hypophosphite)
Pure PH3 is non inflammable but becomes inflammable owingto the presence of P2 H4 or P4
vapours. To purify it from the impurities, it is absorbed in HI to form phosphonium iodide
(PH4 I) which on treating with KOH gives off phosphine.
Other preparation
APNI KAKSHA 17
PH4 I + KOH ⟶ KI + PH3 + H2 O

(PH3 + HI) } Purest PH3
2AlP + 3H2 SO4 ⟶ Al2 (SO4 )3 + PH3 ↑
Δ
4PO3 ⟶ PH3 + 3H3 PO4
Δ
2H3 PO2 ⟶ PH3 + 3H3 PO4
Phyiscal Properties :
(i) It is a colourless gas with rotten fish smell and is highly poisonous.
(ii) It explodes in contact with traces of oxidising agents like HNO3 , Cl2 and Br2 vapours.
(iii) It is slightly soluble in water but soluble in CS2. The solution of PH3 in water decomposes in
presence of light giving red phosphorus and H2 .
Chemical Properties :
(i) It absorbed in copper sulphate or mercuric chloride solution, the corresponding phosphides
are obtained.
3CuSO4 + 2PH3 → Cu3 P2 + 3H2 SO4
3HgCl2 + 2PH3 → Hg 3 P2 + 6HCl
Phosphine is weakly basic and like ammonia, gives phosphonium compounds with acids e.g.,
PH3 + HBr → PH4 Br
150∘
(ii) PH3 + O2 ⟶ P2 O5 + H2 O
(iii) PH3 + 3Cl2 ⟶ PCl3 + 3HCl
electrical
(iv) PH3 + 4 N2 O ⟶ H3 PO4 + 4 N2
sparking
(v) PH3 + 6AgNO3 ⟶ [Ag 3 P ⋅ 3AgNOA3 ↓] + H3 NO3

yellow ppt.
Ag 3 P ⋅ 3AgNO3 + 3H2 O ⟶ 6Ag ↓ +3HNO3 + H3PO3

Black ppt.
(vi) PH3 + 4HCHO + HCl ⟶ [P(CH2 OH)4 ] + Cl−

white/colourless solid
which is used for making
fire-proof cotton fabrics
Note :
Like NH3 , PH3 also can form addition product.
CaCl2 ⋅ 8NH3 Cu2 Cl2 ⋅ 2PH3 , AlCl3 ⋅ 2PH3 , SnCl4 ⋅ 2PH3

PH3 can be absorbed by Ca(OCl)Cl.
APNI KAKSHA 18
PH3 + 3Ca(OCl)Cl + 3H2 O ⟶ PCl3 + 3HCl + 3Ca(OH)2

2NH3 + 3Ca(OCl)Cl ⟶ N2 + 3CaCl2 + 3H2 O
Uses :
(i) 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.
(ii) It is also used in smoke screens.
PHOSPHORUS HALIDES
Phosphorus forms two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br).
PHOSPHORUS TRICHLORIDE
Preparation
(i) By passing dry chlorine over heated white phosphorus.
P4 + 6Cl2 → 4PCl3
(ii) By the action of thionyl chloride with white phosphorus.
P4 + 8SOCl2 → 4PCl3 + 4SO2 + 2 S2 Cl2
Properties
(i) It is a colourless oily liquid
(ii) Hydrolyses in the presence of moisture.
PCl3 + 3H2 O → H3 PO3 + 3HCl
(iii) It reacts with organic compounds containing −OH group such as CH3COOH, C2H5OH.
3CH3 COOH + PCl3 → 3CH3 COCl + H3 PO3
3C2 H5 OH + PCl3 → 3C2 H5 Cl + H3 PO3
PHOSPHORUS PENTACHLORIDE
Preparation
(i) By the reaction of white phosphorus with excess of dry chlorine.
P4 + 10Cl2 → 4PCl5
(ii) By the action of SO2 Cl2 on phosphorus.
P4 + 10SO2 Cl2 → 4PCl5 + 10SO2
Properties :
(i) PCl5 is a yellowish white powder
(ii) It hydroslysis in moist air to POCl3 and finally gets converted to phosphoric acid.
APNI KAKSHA 19
PCl5 + H2 O → POCl3 + 2HCl

POCl3 + 3H2 O → H3 PO4 + 3HCl
(iii) When heated, it sublimes but decomposes on stronger heating.
heat
PCl5 ⟶ PCl3 + Cl2
(iv) It reacts with organic compounds containing −OH group converting them to chloro
derivatives.
C2 H5 OH + PCl5 → C2 H5 Cl + POCl3 + HCl
CH3 COOH + PCl5 → CH3 COCl + POCl3 + HCl
(v) Finely divided metals on heating with PCl5 give corresponding chlorides.
2Ag + PCl5 → 2AgCl + PCl3
Sn + 2PCl5 → SnCl4 + 2PCl3
Uses :
It is used in the synthesis of some organic compounds, e.g., C2 H5 Cl, CH3 COCl.
OXIDES OF PHOSPHORUS
It forms three important oxides which exist in dimeric forms.
PHOSPHORUS TRIOXIDE (𝐏𝟒 𝐎𝟔 )
Preparation
Phosphorus trioxides is formed when phosphorus is burnt in a limited supply of air.
P4 + 3O2 (limited) ⟶ P4 O6
Properties
(a) Heating in air : On heating in air, it forms phosphorus pentoxide.
P4 O6 + 2O2 ⟶ P4 O10
Phosphorus (V) oxide
(b) Action of water : It dissolves in cold water to give phosphorus acid.
P4 O6 + 6H2 O (cold) ⟶ 4H3 PO3
Phosphorus(V)acid
It is, therefore, considered as anhydride of phosphorus acid.
Note: With hot water, it gives phosphoric acid and inflammable phosphine.
PHOSPHORUS (V) OXIDE (𝐏𝟒 𝐎𝟏𝟎 )
Preparation :
It is prepared by heating white phosphorus in excess of air.
Δ
P4 + 5O2 (excess) ⟶ P4 O10
APNI KAKSHA 20
Properties
(a) It is snowy white solid.
(b) Action with water : It readily dissolves in cold water forming metaphosphoric acid.
P4 O10 + 2H2 O( Cold ) ⟶ 4HPO3
Metaphosphoric acid.
With hot water it gives phosphoric acid.

P4 O10 + 6H2 O(Hot) ⟶ 4H3 PO4
Phosphoric acid
(c) Dehydrating nature : Phosphorus pentoxide has strong affinity for water and, therefore, acts
as a powerful dehydrating agent. It extracts water from many inorganic and organic
compounds.
(d) P4 O10 is a very strong dehydrating agent and extracts water from many compounds
including sulphuric acid and nitric acid.
Structure
(a) Its structure is similar to that of P4 O6 .
(b) In addition, each phosphorus atom forms a double bond with oxygen atom.
OXOACIDS OF PHOSPHORUS :
The important oxoacids of phosphorus with their formulae, methods of preparation and the
presence of some characteristic bonds in their structures are given in a table.
Oxoacids of Phosphorus
Oxidation Characteristic
Name Formula State of Bonds and Preparation
Phosphorus their number
Hypophosphorus One P − OH
H3 PO2 +1 Two P − H White P4 + alkali
(Phosphinic)
One P = O
Orthophosphorous Two P − OH
H3 PO3 +3 One P − H P2 O3 + H2 O
(Phosphonic)
One P = O
Two P − OH
Pyrophosphorous H4 P2 O5 +3 Two P − H PCl3 + H3 PO3
Two P = O
APNI KAKSHA 21
Four P − OH
Hypophosphoric H4 P2 O6 +4 Two P = O Red P4 + alkali
One P − OH
Three P − OH
Orthophosphoric H3 PO4 +5 P4 O10 + H2 O
One P = P
Four P − OH
Heat phosphoric
Pyrophosphoric H4 P2 O7 +5 Two P = H
acid
One P − O − P
Three P − OH Phosphorous acid
Metaphosphoric (HPO3 )n +5 Three P = O +Br2 , heat in a
Three P − O − P sealed tube
Heating Effect :
Graham salt
Graham's salt is the best known of these long chain polyphosphates, and is formed by
quenching molten NaPO3 . Graham's salt is soluble in water. These solutions give precipitates
with metal ions such as Pb2+ and Ag + but not with Ca2+ and Mg 2+ . Graham's salt is sold
commercially under the trade name Calgon. In industry it is incorrectly called sodium
hexametaphosphate crystallizing. It is widely used for softening water.
>240∘ C 625∘ C rapid
NaH2 PO4 ⟶ (NaPO3 )3 ⟶ NaPO3 ( liquid melt ) ⟶ (NaPO3 )n
cooling
Sodium trimetaphosphate (Graham's salt) (glass)
OXYGEN FAMILY
GROUP 16 ELEMENTS (O, S, Se, Te, Po)
This is sometimes known as group of chalcogens.
Occurrence
Oxygen is the most abundant of all the elements on earth crust. Oxygen forms about 46.6% by
mass of earth's crust. Dry air contains 20.946% oxygen by volume.
APNI KAKSHA 22
Electronic Configuration
ns 2 np4 is the general valence shell electronic configuration.
Atomic and Ionic Radii : Covalent radius : O < S < Se < Te
Ionisation Enthalpy : O > S > Se > Te > Po (IE1 values)
Electron Gain Enthalpy : S > Se > Te > Po > O
Electronegativity : O > S > Se > Te
Metallic Character : O < S < Se < Te < Po
Melting and Boiling points: M.P. : Te > Po > Se > S > O
B.P. : Te > Po > Se > S > O
Elemental State
Oxygen exist as diatomic molecular gas in this case there is p𝜋 − p𝜋 overlap thus two O atoms
form double bond O = O. The intermolecular forces in O2 are weak VB forces. ∴ O2 exist as gas .
On the other bond, other elements of family do not form stable p𝜋 − p𝜋 bonds and do not exist
as M2 molecules. Other atoms are linked by single bonds and form poly atomic complex
molecules for eg.
S − S8, Se − Se8
Catenation
In this group only S has a strong tendency for catenation oxygen has this tendency to a limited
extent.
H2 O2 H − O − O − H (Poly oxides)
H2 S 2 H − S − S − H (Polysulphides or polysulphones)
H2 S 3 H − S − S − S − H
H2 S 4 H − S − S − S − S − H
Physical Properties
(i) Oxygen and sulphur are non-metals, selenium and tellurium metalloids, whereas polonium
is a metal.
(ii) Polonium is radioactive and is short lived (Half-life 13.8 days).
(iii) All these elements exhibit allotropy.
Amongst tetrafluorides, SF4 is a gas, SeF4 a liquid and TeF4 a solid. These fluorides have sp3 d
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. All elements except selenium form dichlorides and dibromides. These dihalides are
formed by 𝑠𝑝3 hybridisation and thus, have tetrahedral structure. The well known monohalides
APNI KAKSHA 23
are dimeric in nature. Examples are S2 F2 , S2 Cl2 , S2 Br2 , Se2 Cl2 and Se2 Br2 . These dimeric
halides undergo disproportionation as given below : 2Se2 Cl2 → SeCl4 + 3Se
DIOXYGEN
(a) Laboratory method
(i) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
Heat
2KClO3 ⟶ 2KCl + 3O
MnO2
(ii) By the thermal decomposition of the oxides of metals low in the electrochemical series and
higher oxides of some metals.
2Ag 2 O(s) → 4Ag(s) + O2 ( g); 2 Pb3 O4 ( 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.
2H2 O2 (aq) → 2H2 O(ℓ) + O2 ( g)
(b) Large scale preparation : 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.
(c) Industrially method : 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.
Properties
(i) Dioxygen is a colourless and odourless gas.
(ii) Its solubility in water is to the extent of 3.08 cm3 in 100 cm3 water at 293 K which is just
sufficient for the vital support of marine and aquatic life.
(iii) It liquefies at 90 K and freezes at 55 K.
(iv) Oxygen atom has three stable isotopes: 16
O, 17
O and 18
O. Molecular oxygen, O2 is unique
in being paramagnetic inspite of having even number of electrons.
(v) Dioxygen directly reacts with nearly all metals and non-metals except some metals ( e.g., Au,
Pt) and some noble gases. Some of the reactions of dioxygen with metals, non-metals and other
compounds are as follows :
2Ca + O2 → 2CaO
4Al + 3O2 → 2Al2 O3
P4 + 5O2 → P4 O10
C + O2 → CO2
APNI KAKSHA 24
2ZnS + 3O2 → 2ZnO + 2SO2

CH4 + 2O2 → CO2 + 2H2 O
Some compounds are catalytically oxidised. For example,
v2 O 5
2SO2 + O2 ⟶ 2SO3
CuCl2
4HCl + O2 ⟶ 2Cl2 + 2H2 O
Uses:
(i) It's importance in normal respiration and combustion processes, oxygen is used in
oxyacetylene welding, in the manufacture of many metals, particularly steel.
(ii) Oxygen cylinders are widely used in hospitals, high altitude flying and in mountaineering.
(iii) The combustion of fuels, e.g., hydrazines in liquid oxygen, provides tremendous thrust in
rockets.
SIMPLE OXIDES
A binary compound of oxygen with another element is called oxide. In many cases one element
forms two or more oxides. The oxides vary widely in their nature and properties. Oxides can be
simple (e.g., MgO, Al2 O3 ) or mixed (Pb3 O4 , Fe3 O4 ).
Types of simple oxide :
Acidic oxide : An oxide that combines with water to give an acid is termed acidic oxide (e.g.,
SO2 , Cl2 O7 , CO2 , N2 O5 ).
SO2 + H2 O → H2 SO3
As a general rule, only non-metal oxides are acidic but oxides of some metals in high oxidation
state also have acidic character (e.g., Mn2 O7 , CrO3 , V2 O5 ).
Basic oxide : The oxides which give a base with water are known as basic oxides (e.g.,
Na2 O, CaO, BaO). In general, metallic oxides are basic. For example, CaO combines with water to
give Ca(OH)2, a base.
CaO + H2 O → Ca(OH)2
Amphoteric oxide : Some metallic oxides exhibit a dual behaviour. They show characteristics
of both acidic as well as basic oxides. Such oxides are known as amphoteric oxides.
Al2 O3 ( s) + 6HCl(aq) + 9H2 O(ℓ) → 2[Al(H2 O)6 ]3+ (aq) + 6Cl− (aq)
Al2 O3 ( s) + 6NaOH(aq) + 3H2 O(ℓ) → 2Na3 [Al(OH)6 ](aq)
Neutral oxide: There are some oxides which are neither acidic nor basic. Such oxides are
known as neutral oxides. Examples of neutral oxides are CO, NO and N2 O.
OZONE
Ozone is an allotropic form of oxygen.
Threats to ozone layer
(i) Experiments have shown that 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(g) + O3 ( g) → NO2 ( g) + O2 ( g)
APNI KAKSHA 25
(ii) Another threat to this ozone layer is probably posed by the use of freons which are used in
aerosol sprays and as refrigerants.
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 ΔH − (298 K) = +142 kJ mol−1
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. If concentration of
ozone greater than 10 percent is required, a battery of ozonisers can be used, and pure ozone
(b.p. 385 K ) can be condensed in a vessel surrounded by liquid oxygen.
Is separated by passing into spiral tube cooled by liq.
2 F2 + 2H2 O ⟶ 4HF + O2
Note: ] Ozonised Oxygen air. Ozone condenses at − 112.4∘ C.
F2 + 3H2 O ⟶ 6HF + O3
[b.p. of O2 − 183∘ C; b.p. of liq. Air is − 190∘ C]
Properties
(i) Pure ozone is a pale blue gas, dark blue liquid and violet-black solid.
(ii) It is diamagnetic gas.
(iii) Ozone has a characteristic fishy smell and in small concentrations it is harmless.
Toxic effect :
(a) Toxic enough (more toxic than KCN ). It's intense blue colour is due to the absorption of red
light.
(b) However, if the concentration rises above about 100 parts per million, breathing becomes
uncomfortable resulting in headache and nausea.
Oxidizing properties
It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07 V.
O3 + 2H + + 2e ⟶ O2 + H2 O E ∘ = +2.07 V
It is next to F2 . [above 2.07 V, only F2 , F2 O are there]
It is not really surprising, therefore, high concentrations of ozone can be dangerously explosive.
Due to the ease with which it liberates atoms of nascent oxygen (O3 → O2 + O), it acts as a
powerful oxidising agent. For example, it oxidises lead sulphide to lead sulphate and iodide ions
to iodine.
PbS(s) + 4O3 ( g) → PbSO4 ( s) + 4O2 ( g)
2I − (aq) + H2 O(ℓ) + O3 ( g) → 2OH − (aq) + I2 ( s) + O2 ( g)
(i) Metal Sulphides to Sulphates.
MS + 4O3 ⟶ MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]
(ii) 2HX + O3 ⟶ X2 + H2 O + O2 [X = Cl, Br, I]
(iii) NaNO2 + O3 ⟶ NaNO3 + O2
Na2 SO3 + O3 ⟶ Na2 SO4 + O2
Na2 AsO3 + O3 ⟶ Na2 AsO4 + O2
APNI KAKSHA 26
(iv) Moist S, P, As + O3 ⇒
S + H2 O + 3O3 ⟶ H2 SO4 + 3O2
2P + 3H2 O + 5O3 ⟶ 2H3 PO4 + 5O2
2As + 3H2 O + 5O3 ⟶ 2H3 AsO4 + 5O2
(v) Moist I2 ⟶ HIO3 whereas dry iodine ⟶ I4 O9 (yellow)
I2 + 5O3 + H2 O ⟶ 2HIO3 + 5O2
2I2 + 9O3 ⟶ I4 O9 + 9O2
(vi) 2 K 2 MnO4 + O3 + H2 O ⟶ 2KMnO4 + 2KOH + O2
2 K 4 [Fe(CN)6 ] + O3 + H2 O ⟶ 2 K 3 [Fe(CN)6 ] + 2KOH + O2
2FeSO4 + O3 + H2 SO4 ⟶ Fe2 (SO4 )3 + O2 + H2 O
(vii) (a) 2KI (acidified) +O3 + 2HCl ⟶ I2 + 2KCl + H2 O + O2

(b) 2KI (neutral) +O3 + H2 O ⟶ I⏟
2 + 2KOH + O2 O3 𝑖𝑠 𝑒𝑠𝑡𝑖𝑚𝑎𝑡𝑒𝑑 𝑏𝑦 𝑡ℎ𝑖𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
KI+KOI
2KI + KOI + 2HCl ⟶ 2KCl + I2 + H2O

I2 + 2 S2 O2− 2−
3 ⟶ S4 O6 + 2I
KI + 3O3 ⟶ KIO3 + 3O2
alk. { }
KI + 4O3 ⟶ KIO4 + 4O2
(viii) Hg loses its fluidity (tailing of Hg )
2Hg + O3 ⟶ Hg 2 O + O2
similarly 2Ag + O3 ⟶ Ag 2 O + O2
Brown
(ix) BaO2 + O3 → BaO + 2O2
H2 O2 + O3 ⟶ H2 O + 2O2
Na2 O2 + O3 + H2 O ⟶ 2NaOH + 2O2
(x) 2KOH + 5O3 ⟶ 2KO3 + 5O2 + H2 O
In all above reaction 𝐎𝟑 gives up 𝐎𝟐 but some reactions are there which consumes all 𝐎-atom.
(i) 3SO2 + O3 ⟶ 3SO3
(ii) 3SnCl2 + 6HCl + O3 ⟶ 3SnCl4 + 3H2 O
Uses :
(i) Sterilising water
(ii) Detection of position of the double bond in the unsaturated compound.
(iii) It is used as a germicide, disinfectant and for sterilising water.
APNI KAKSHA 27
(iv) It is also used for bleaching oils, ivory, flour, starch, etc.
(v) It acts as an oxidising agent in the manufacture of potassium permanganate.
Ques. Ozone is thermodynamically unstable with respect to oxygen. Explain ?

Sol. Because its decomposition into oxygen results in the liberation of heat ( ΔH is negative) and an
increase in entropy ( ΔS is positive). These two effects reinforce each other, resulting in large
negative Gibbs energy change (ΔG) for its conversion into oxygen.
HYDROGEN PEROXIDE (𝐇𝟐 𝐎𝟐 )

Method of preparation:
(i) Na2 O2 + H2 O (ice cold water) ⟶ 2NaOH + H2 O2
(ii) BaO2 + H2 So4 ⟶ BaSO4 + H2 O2
Instead of H2 SO4 , H3 PO4 is added now-a-days because H2 SO4 catalyses the decomposition of
H2 O2 whereas H3 PO4 favours to restore it.
3BaO2 + 2H3 PO4 → Ba3 (PO4 )2 + 3H2 O2 and Ba3 (PO4 )2 + 3H2 SO4 → 3BaSO4 + 2H3 PO4
(reused again)
(iii)
Properties:
(i) Colourless, odourless liquid (b.p. 152∘ )
(ii) Acidic nature: H2 O2 + 2NaOH ⟶ Na2 O2 + H2 O
H2 O2 + Na2 CO3 ⟶ Na2 O2 + CO2 + H2 O
(iii) It is oxidant as well as reductant.
H2 O2 + 2H + + 2e → 2H2 O [reaction in acidic medium]
H2 O2 + 2e → 2OH − [rxnn in alkali medium]
Oxidising Properties:
(i) PbS + 4H2 O2 ⟶ PbSO4 + 4H2 O (Used in washing of oil painting)
(ii) NaNO2 + H2 O2 ⟶ NaNO3 + H2 O
Na2 SO3 + H2 O2 ⟶ Na2 SO4 + H2 O
APNI KAKSHA 28
2KI + H2 O2 ⟶ 2KOH + I2
H2 S + H2 O2 ⟶ S ↓ +2H2 O
H2 SO4 + 2FeSO4 + H2 O2 ⟶ Fe2 (SO4 )3 + 2H2 O
2 K 4 [Fe(CN)6 ] + H2 O2 + H2 SO4 ⟶ 2 K 3 [Fe(CN)6 ] + K 2 SO4 + 2H2 O
Reducing properties:
(a) Ag 2 O + H2 O2 ⟶ 2Ag + H2 O + O2
(b) O3 + H2 O2 ⟶ H2 O + 2O2
(c) MnO2 + H2 O2 + H2 SO4 → MnSO4 + 2H2 O + O2
(d) PbO2 + H2 O2 → PbO + H2 O + O2
(e) Pb3 O4 + 4HNO3 ⟶ 2 Pb(NO3 )2 + PbO2 + 2H2 O
PbO2 + H2 O2 ⟶ PbO + H2 O + O2
PbO + 2HNO3 ⟶ Pb(NO3 )2 + H2 O
Pb3 O4 + H2 O2 + 6HNO3 ⟶ 3 Pb(NO3 )2 + 4H2 O + O2
(f) X2 + H2 O2 ⟶ 2HX + O2 [X = Cl, Br]
(g) 2[Fe(CN)6]3− + 2OH − + H2 O2 ⟶ 2[Fe(CN)6 ]4− + 2H2 O + O2
(h) NaOCl + H2 O2 ⟶ NaCl + H2 O + O2
(i) NaIO4 + H2 O2 ⟶ NaIO3 + H2 O + O2
Uses : (i) As a rocket propellant:
NH2 ⋅ NH2 + 2H2 O2 ⟶ N2 + 4H2 O [highly exothermic and large increase in volume]
(ii) In detection of Cr +3 , Ti+4 etc.
Ti(SO4 )2 + H2 O2 + 2H2 O ⟶ H2 TiO4 + 2H2 SO4
Yellow or orange
Pertitanic acid
ALLOTROPIC FORMS OF SULPHUR
>36 K
𝛼 − sulphur ⇌ 𝛽 − sulphur
3696 K
At 369 K both the forms are stable. This temperature is called transition temperature.
Rhombic sulphur ( 𝜶-sulphur)
(i) This allotrope is yellow in colour, m.p. 385.8 K and specific gravity 2.06 .
(ii) Rhombic sulphur crystals are formed on evaporating the solution of roll sulphur in CS2.
(iii) It is insoluble in water but dissolves to some extent in benzene, alcohol and ether.
(iv) It is readily soluble in CS2.
Monoclinic sulphur ( 𝜷-sulphur)
(i) Its m.p. is 393 K and specific gravity 1.98.
(ii) It is soluble in CS2.
APNI KAKSHA 29
Structure of 𝜶 and 𝜷 sulphur

Both rhombic and monoclinic sulphur have S8 molecules. These S8 molecules are packed to give
different crystal structures. The 𝑆8 ring in both the forms is puckered and has a crown shape.
S8 ring in rhombic sulphur S6 form
Several other modifications of sulphur containing 6-20 sulphur atoms per ring have been
synthesized in the last two decades. In cyclo- S6 , the ring adopts the chair form. At elevated
temperatures (∼ 1000 K), S2 is the dominant species and is paramagnetic like O2 .
Note: Viscosity of 'S' with temperature : m.p. of ' 𝐒 ′ ⟶ 𝟏𝟏𝟐. 𝟖∘ 𝐂.
> 112.8∘ C to 160∘ C ⇒ slow decreases due to
S8 rings slip and roll over one another easily.
> 160∘ C, increases sharply due to breaking of
S8 rings into chains and polymerses into large size chain.
Amorphous forms are
(i) Plastic sulphur (ii) Milk of sulphur (iii) Colloidal sulphur
SULPHUR DIOXIDE
Preparation
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)
laboratory method by treating a sulphite with dilute sulphuric acid.
SO2− +
3 (aq) + 2H (aq) → H2 O(ℓ) + SO2 ( g)
other preparation :
Cu + 2H2 SO4 (conc.) ⟶ CuSO4 + 2H2 O + SO2
Hg + H2 SO4 ⟶ HgSO4 + H2 O + SO2
2Ag + H2 SO4 ⟶ Ag 2 SO4 + H2 O + SO2
S + 2H2 SO4 ⟶ 3SO2 + 2H2 O
APNI KAKSHA 30
(CharcoalC + 2H2 SO4 ⟶ CO2 + 2SO2 + 2H2 O

NaHSO3 + H2 SO4 ⟶ NaHSO4 + H2 O + SO2
Industrial method, by-product of the roasting of sulphide ores.
4FeS2 ( s) + 11O2 ( g) → 2Fe2 O3 ( s) + 8SO2 ( g)
The gas after drying is liquefied under pressure and stored in steel cylinders.
Properties
(i) Sulphur dioxide is a colourless gas with pungent smell.
(ii) It is highly soluble in water.
(iii) It liquefies at room temperature under a pressure of two atmospheres and boils at 263 K.
(iv) Acdic character sulphur dioxide, when passed through water, forms a solution of
sulphurous acid.
SO2 ( g) + H2 O(ℓ) ⇌ H2 SO3 (aq)
It reacts readily with sodium hydroxide solution, forming sodium sulphite, which then reacts
with more sulphur dioxide to form sodium hydrogen sulphite.
2NaOH + SO2 → Na2 SO3 + H2 O
Na2 SO3 + H2 O + SO2 → 2NaHSO3
V2 O5
SO2 ( g) + O2 ( g) ⟶ 2SO3 ( g)
Reducing properties
When moist, sulphur dioxide behaves as a reducing agent.
2Fe3+ + SO2 + 2H2 O → 2Fe2+ + SO2−
4 + 4H
+
5SO2 + 2MnO− 2− +
4 + 2H2 O → 5SO4 + 4H + 2Mn
2+
Bonding in 𝐒𝐎𝟐 : The molecule of SO2 is angular. It is a resonance hybrid of the two canonical forms:
Uses:
(i) It is used refining petroleum and sugar
(ii) It is used in bleaching wool and silk
(iii) It is used 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.
HYDROGEN SULPHIDE ( 𝐇𝟐 S) SULPHURATED HYDROGEN
APNI KAKSHA 31
Preparation
By the action of dil. HCl or H2 SO4 on iron pyrites.
FeS + H2 SO4 ⟶ FeSO4 + H2 S ↑
Properties
(a) It burn in air with blue flame
2H2 S + O2 ⟶ 2H2 O + S
If the air supply is in excess
2H2 S + 3O2 ⟶ 2H2 O + 2SO2
(b) It is a mild acid.
H2 S ⟶ H + + SH −
SH − ⟶ H + + S −2
(c) It act as a reducing agent. It reduces halogen into corresponding hydroacid.
H2 S + X2 ⟶ 2HX + S
Tests of 𝐇𝟐 𝐒
(a) Unpleasant odour resembling that of rotten eggs.
(b) It turns lead acetate into paper black
(CH3 COO)2 Pb + H2 S ⟶ PbS ↓ +2CH3 COOH
Black
Uses
(a) It is mainly employed in salt analysis for the detection of cation.
(b) Reducing agent for H2 SO4 , KMnO4 , K 2 Cr2 O7 , O3 , H2 O2 , FeCl3
Note: Drying agent for this gas : fused CaCl2 , Al2 O3 (dehydrated) P2 O5 etc.
But not H2 SO4 , because
H2 SO4 + H2 S ⟶ 2H2 O + SO2 + S
SULPHURIC ACID
Industrial Manufacturing (Contact process)
Steps involved :
(i) Burning of sulphur or sulphide ores in air to generate 𝐒𝐎𝟐 .
(ii) Conversion of 𝐒𝐎𝟐 to 𝐒𝐎𝟑 by the reaction with oxygen in the presence of a catalyst
(𝐕𝟐 𝐎𝟓 ) :
The key step in the manufacture of H2 SO4 is the catalytic oxidation of SO2 with O2 to give SO3 in
the presence of V2 O5 (catalyst).
V2 Os
2SO2 ( g) + O2 ( g) ⟶ 2SO3 ( g)Δr H Θ = −196.6 kJ mol1
The reaction is exothermic, reversible and the forward reaction leads to a decrease in volume.
(iii) The SO3 gas from the catalytic converter is absorbed in concentrated H2 SO4 to produce
oleum. Dilution of oleum with water gives H2 SO4 of the desired concentration.
SO3 + H2 SO4 → H2 S2 O7
(Oleum)
APNI KAKSHA 32
FLOW DIAGRAM FOR THE MANUFACTURE OF SULPHURIC ACID

The sulphuric acid obtained by Contact process is 96 − 98% pure.
P2 O5 is stronger dehydrating agent than H2 SO4 : H2 SO4 + P2 O5 ⟶ 2HPO3 + SO3
Properties
(i) Sulphuric acid is a colourless, dense, oily liquid with a specific gravity of 1.84 at 298 K.
(ii) The acid freezes at 283 K and boils at 611 K.
(iii) It dissolves in water.
Chemical properties
The chemical reactions of sulphuric acid are as a result of the following characteristics:
(1) Acidic character :
In aqueous solution, sulphuric acid ionises in two steps.
4 (aq): K a1 = Very large (K a1 > 10)
H2 SO4 (aq) + H2 O(ℓ) → H3 O+ (aq) + HSO−
HSO− + 2−
4 (aq) + H2 O(ℓ) → H3 O (aq) + SO4 (aq); K a2 = 1.2 × 10
−2
(2) Dehydrating Propert :

Concentrated sulphuric acid is a strong dehydrating agent.
(3) Oxidizing Nature :

Hot concentrated sulphuric acid is a moderately strong oxidising agent. In this respect, it is
intermediate between phosphoric and nitric acids.
APNI KAKSHA 33
Cu + 2H2 SO4 (conc.) → CuSO4 + SO2 + 2H2 O

HBr/HI + H2 SO4 (conc.) → Br2 /I2 + SO2 + H2 O
3 S + 2H2 SO4 (conc.) → 3SO2 + 2H2 O
C + 2H2 SO4 (conc.) → CO2 + 2SO2 + 2H2 O
2P + 5H2 SO4 (conc.) → H3 PO4 + 5SO2
𝐇𝟐 𝐒𝐎𝟒 &𝐒𝐎𝟑 :
Uses:
(i) petroleum refining
(ii) manufacture of pigments, paints and dyestuff intermediates
(iii) detergent industry
(iv) metallurgical applications (e.g., cleansing metals before enameling, electroplating and
galvanising
(v) storage batteries
(vi) in the manufacture of nitrocellulose products and
(vii) as a laboratory reagent.
SODIUM THIOSULPHATE
Prepn :
boiling eapporation
(i) Na2 SO3 sol n . +S (powder) ⟶ Na2 S2 O3 ⟶ monoclinic crystal
roasting
Na2 SO4 + 4C ⟶ Na2 S +
(ii)
(iii) 6NaOH + 4 S ⟶ Na2 S2 O3 + 2Na2 S + 3H2 O

3Ca(OH)2 + 12 S ⟶ CaS2 O3 + 2CaS5 + 3H2 O
(iv) Na2 SO3 + Na2 S + I2 ⟶ Na2 S2 O3 + 2NaI
APNI KAKSHA 34
Props:
Δ
(i) 4Na2 S2 O3 ⟶ Na2 S5 + 3Na2 SO4
Δ
(ii) Na2 S2 O3 + 2H + ⟶ H2 S2 O3 ⟶ H2 O + SO2 + S ↓ (White turbidity)
Reaction:
(i) Na2 S2 O3 + I2 ⟶ S4 O2−
6 + 2I
−
+Cl − water ⟶ SO2−

4 + S + 2HCl
+Br2 − water ⟶ SO2−

4 + S + 2HBr
+4OI − + 2OH − ⟶ 2SO2− −

4 + 4I + H2 O
+4Cl2 + 5H2 O ⟶ Na2 SO4 + 8HCl + H2 SO4
APNI KAKSHA 35
HALOGEN FAMILY
GROUP 17 ELEMENTS (F, CI, Br, I, At)
The electronic configuration of outermost shell 17th group element is (ns2 np 5 ).
Atomic and ionic radii : F < Cl < Br < I
Ionisation Enthalpy : F > Cl > Br > I
Electron Gain Enthalpy: Cl > F > Br > I
Electronegativity : F > Cl > Br > I
Physical Properties
(i) Their melting and boiling points steadily increase with atomic number.
(ii) All halogens are coloured. For example, F2 has yellow gas, Cl2 greenish yellow gas, Br2 red
liquid and I2 violet coloured solid.
(iii) Fluorine and chlorine react with water. Bromine and iodine are only sparingly soluble in
water but are soluble in various organic solvents such as chloroform, carbon tetrachloride,
carbon disulphide and hydrocarbons to give coloured solutions.
(iv) Bond energy order; Cl2 > Br2 > F2 > I2
Chemical Properties
Oxidation states :
(i) All the halogens exhibit -1 oxidation state. However, chlorine, bromine and iodine exhibit
+1, +3, +5 and +7 oxidation states also as explained below:
Halogen atom 1 unpaired electron accounts 1
In ground state For -1 or + 1 oxidation states
(other than fluorine)
First excited state 3 unpaired electron accounts

For +3 oxidation states
Second excited state 5 unpaired electron accounts
Third excited state 7 unpaired electron accounts or
(ii) The higher oxidation states of chlorine, bromine and iodine are realised mainly when the
halogens are in combination with the small and highly electronegative fluorine and oxygen
atoms. e.g., in interhalogens, oxides and oxoacids.
(iii) The oxidation states of +4 and +6 occur in the oxides and oxoacids of chlorine and bromine.
(iv) The fluorine atom has no d orbitals in its valence shell and therefore cannot expand its
octet. Being the most electronegative, it exhibits only -1 oxidation state.
APNI KAKSHA 36
Chemical reactivity
(i) All the halogens are highly reactive.
(ii) They react with metals and non-metals to form halides and the reactivity of the halogens
decreases down the group. i.e. the order is F2 > Cl2 > Br2 > I2
(iii) The ready acceptance of an electron is the reason for the strong oxidising nature of
halogens. 𝐹2 is the strongest oxidising halogen and it oxidises other halide ions in solution or
even in the solid phase.
In general, a halogen oxidises halide ions of higher atomic number.
F2 + 2X − → 2 F − + X 2 (X = Cl, Br or I)
Cl2 + 2X − → 2Cl− + X 2 (X = Br or I)
Br2 + 2I − → 2Br − + I2
(1) Reactivity towards water
2 F2 ( g) + H2 O(𝑙) → 4H + (aq) + 4 F − (aq) + O2 ( g)
X2 ( g) + H2O(𝑙) → HX(aq) + HOX(aq)
( where X = Cl or Br)
4I(aq) + 4H + (aq) + O2 ( g) → 2I2 ( s) + 2H2 O(𝑙)
(2) Reactivity towards hydrogen :
They all react with hydrogen to give hydrogen halides but affinity for hydrogen decreases from
fluorine to iodine.
(i) The acidic strength order : HF < HCl < HBr < HI
(ii) The stability order of these halides : H − F > H − Cl > H − Br > H − I.
(3) Reactivity towards oxygen :
(i) Halogens form many oxides with oxygen but most of them are unstable. Fluorine forms two
oxides OF2 and O2 F2 . However, only OF2 is thermally stable at 298 K. These oxides are
essentially oxygen fluorides because of the higher electronegativity of fluorine than oxygen.
Both are strong fluorinating agents. O2 F2 oxidises plutonium to PuF6 and the reaction is used
in removing plutonium as PuF6 from spent nuclear fuel.
(ii) Chlorine, bromine and iodine form oxides in which the oxidation states of these halogens
range from +1 to +7 .
(iii) A combination of kinetic and thermodynamic factors lead to the generally decreasing order
of stability of oxides formed by halogens, I > Cl > Br.
(iv) The higher oxides of halogens tend to be more stable than the lower ones.
(v) Chlorine oxides, Cl2 O, ClO2 , Cl2 O6 and Cl2 O7 are highly reactive oxidising agents and tend to
explode. ClO2 is used as a bleaching agent for paper pulp and textiles and in water treatment.
(vi) The bromine oxides, Br2 O, BrO2 , BrO3 are the least stable halogen oxides (middle row
anomally) and exist only at low temperatures. They are very powerful oxidising agents.
(vii) The iodine oxides, I2 O4 , I2 O5 , I2 O7 are insoluble solids and decompose on heating. I2 O5 is a
very good oxidising agent and is used in the estimation of carbon monoxide.
(4) Reactivity towards metals :
Halogens react with metals to form metal halides.
Mg(s) + Br2 (𝑙) → MgBr2 ( s)
The ionic character of the halides decreases in the order MF > MCl > MBr > MI where M is
monovalent metal.
APNI KAKSHA 37
FLUORINE
Method of 𝐏𝐫𝐞𝐩𝐧 :
Moissan process : [By electrolysis of KHF2 (which is obtained from CaF2 )]
CaF2 + H2 SO4 ⟶ CaSO4 + 2HF KF decreases the m.p.of
HF + KF ⟶ KHF2 { the mix. depending upon }
Electrolysis
KHF2 ⟶ H2 (at cathode) + F2 (at anode) the composition.
CHLORINE
Preparation
(i) By electrolysis of aq. NaCl :
2NaCl + 2H2 O ⟶ 2NaOH + H
⏟2 + Cl
⏟2
at cathode (anode)
Electrolysis
2NaCl ⟶ 2Na + Cl2
(Malten) (cathode) (anode)
(ii) By heating manganese dioxide with concentrated hydrochloric acid.

MnO2 + 4HCl → MnCl2 + Cl2 + 2H2 O
However, a mixture of common salt and concentrated H2 SO4 is used in place of HCl.
4NaCl + MnO2 + 4H2 SO4 → MnCl2 + 4NaHSO4 + 2H2 O + Cl2
(iii) By the action of HCl on potassium permanganate.
2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2 O + 5Cl2
MANUFACTURE OF CHLORINE
(i) Deacon's process : By oxidation of hydrogen chloride gas by atmospheric oxygen in the
presence of CuCl2 (catalyst) at 723 K.
CuCl2
4HCl + O2 ⟶ 2Cl2 + 2H2 O
(ii) Electrolytic process : Chlorine is obtained by the electrolysis of brine (concentrated NaCl
solution).
Chlorine is liberated at anode. It is also obtained as a by-product in many chemical industries.
Properties
(i) It is a greenish yellow gas with pungent and suffocating odour.
(ii) It is soluble in water. Chlorine reacts with a number of metals and non-metals to form
chlorides.
2Al + 3Cl2 → 2AlCl3 ; P4 + 6Cl2 → 4PCl3
2Na + Cl2 → 2NaCl; S8 + 4Cl2 → 4 S2 Cl2
2Fe + 3Cl2 → 2FeCl3 ;
APNI KAKSHA 38
Reaction with hydrogen

It has great affinity for hydrogen. It reacts with compounds containing hydrogen to form HCl.
H2 + Cl2 → 2HCl
H2 S + Cl2 → 2HCl + S
C10 H16 + 8Cl2 → 16HCl + 10C
Reaction with amonia
With excess ammonia, chlorine gives nitrogen and ammonium chloride whereas with excess
chlorine,
nitrogen trichloride (explosive) is formed.
8NH3 + 3Cl2 → 6NH4 Cl + N2 ; NH3 + 3Cl2 → NCl3 + 3HCl
(excess) (excess)
Reaction with alkalies
2NaOH + Cl2 → NaCl + NaOCl + H2 O
(cold and dilute)
6NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2 O
(hot and conc.)
5X − + XO− +
3 + 6H ⟶ 3X 2 + 3H2 O
[X = Cl, Br, I]
Reaction with slaked lime
With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 → Ca(OCl2 ) + CaCl2 + 2H2 O
The composition of bleaching powder is Ca(𝐎𝐂𝐥)2 ⋅ CaCl2 ⋅ 𝐂𝐚(𝐎𝐇)2 ⋅ 𝟐𝐇2 𝐎.
Note : 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.
It is a powerful bleaching agent; bleaching action is due to oxidation.
Cl2 + H2 O → 2HCl + O
Coloured substance + O → Colourless substance
Uses: 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 (CCl3 NO2 ), mustard gas (ClCH2 CH2 SCH2 CH2 Cl).
APNI KAKSHA 39
40∘ C
𝐏𝐫𝐞𝐩𝐧 . Cl2 ( g) + Ca(OH)2 ⟶ Ca(OCl)Cl + H2 O
Slaked lime
(a) On long standing it undergoes
(i) auto oxiation 6Ca(OCl)Cl ⟶ Ca(ClO3 )2 + 5CaCl2
CoCl2
(ii) 2Ca(OCl)Cl ⟶ 2CaCl2 + O2
Cat.
(iii) Ca(OCl)Cl + H2O ⟶ Ca(OH)2 + Cl2
Oxidising Prop.:
CaOCl2 + H2 S ⟶ S + CaCl2 + H2 O
CaOCl2 + 2FeSO4 + H2 SO4 ⟶ Fe2 (SO4 )3 + CaCl2 + H2 O
CaOCl2 + KNO2 ⟶ CaCl2 + KNO3
3CaOCl2 + 2NH3 ⟶ 3CaCl2 + 3H2 O + N2
CaOCl2 + 2KI + 2HCl ⟶ CaCl2 + 2KCl + H2 O + I2
CaOCl2 + 2KI + 2AcOH ⟶ CaCl2 + 2KOAc + H2 O + I2
CaOCl2 + Na3 AsO3 ⟶ Na3 AsO4 + CaCl2
Reaction with acid:
CaOCl2 + 2HCl ⟶ CaCl2 + H2 O + Cl2 ; Ca(OCl)Cl + H2 SO4 ⟶ CaSO4 + H2 O + Cl2
Ca(OCl)Cl + CO2 ⟶ CaCO3 + Cl2
Note: ClO2 does not dimerise because odd e' undergoes delocalisation (in its own vaccant 3 d-orbital)
Cl2 O4 (Cl. ClO4 ) is not the dimer of ClO2 . Actually it is Cl-perchlorate.
HYDROGEN CHLORIDE
Preparation
Laboratory method: it is prepared by heating sodium chloride with concentrated sulphuric acid.
420 K
NaCl + H2 SO4 ⟶ NaHSO4 + HCl
823 K
NaHSO4 + NaCl ⟶ Na2 SO4 + HCl
HCl gas can be dried by passing through concentrated sulphuric acid.
Properties
(i) It is a colourless and pungent smelling gas.
(ii) It is easily liquefied to a colourless liquid (b.p.189 K) and freezes to a white crystalline solid
(f.p. 159 K ).
(iii) It is extremely soluble in water
(iv) Acidic character : It ionises as follows
HCl(g) + H2 O(𝑙) → H3 O+ (aq) + Cl− (aq)K a = 107
Its aqueous solution is called hydrochloric acid. High value of dissociation constant (Ka)
indicates that it is a strong acid in water. It reacts with NH3 and gives white fumes of NH4 Cl.
NH3 + HCl → NH4 Cl
Note: Aqua regia
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 + 2H2 O
3Pt + 16H + + 4NO− − 2−
3 + 18Cl → 3PtCl6 + 4NO + 8H2 O
APNI KAKSHA 40
Reaction with salts

Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates, hydrogencarbonates,
sulphites, etc.
Na2 CO3 + 2HCl → 2NaCl + H2 O + CO2
NaHCO3 + HCl → NaCl + H2 O + CO2
Na2 SO3 + 2HCl → 2NaCl + H2 O + SO2
Uses: (i) It is used in the manufacture of chlorine, NH4 Cl and glucose (from corn starch)
(ii) It is used for extracting glue from bones and purifying bone black
(iii) It is used in medicine and as a laboratory reagent.
(iv) It bleaches vegetable or organic matter in the presence of moisture. Bleaching effect of
chlorine is permanent.
INTERHALOGEN COMPOUNDS
When two different halogens react with each other, interhalogen compounds are formed. They
can be assigned general compositions as XX ′ , XX3′ , XX5 ′ and XX7′ where X is halogen of larger
size and X ′ of smaller size and X is more electropositive than X ′ .
Preparation
The interhalogen compounds can be prepared by the direct combination or by the action of
halogen on lower interhalogen compounds. The product formed depends upon some specific
conditions, Fore.g.,
Properties
(i) These are all covalent molecules and are diamagnetic in nature.
(ii) They are volatile solids or liquids at 298 K except ClF which is a gas.
(iii) Their physical properties are intermediate between those of constituent halogens except
that their m.p. and b.p. are a little higher than expected.
(iv) Their chemical reactions can be compared with the individual halogens. In general,
interhalogen compounds are more reactive than halogens (except fluorine). This is because
X − X ′ bond in interhalogens is weaker than X − X bond in halogens except F − F bond.
(v) All these undergo hydrolysis giving halide ion derived from the smaller halogen and a
hypohalite (when XX ′ ), halite (when XX3′ ), halate (when XX5′ ) and perhalate (when XX7′ )
anion derived from the larger halogen.
XX ′ + H2 O → HX ′ + HOX
APNI KAKSHA 41
PSEUDO HALOGEN
There are univalent ion consisting of two or more atoms of which at least one is N, that have
properties similar to those of the halide ions. E.g.
(i) Na-salts are soluble in water but Ag-salts are insoluble in water.
(ii) H-compounds are acids like HX.
(iii) Some anions can be oxidised to give molecules X2 .
Anions : Acids Dimer
CN− HCN (CN)2
SCN− HSCN(thiocyanic acid) (SCN)2
SeCN− (SeCN)2
OCN − HOCN (cyanic acid)
NCN2− ( Bivalent ) H2 NCN (cyanamide)
ONC − HONC (Fulminic acid)
N3− HN3 (Hydrazoic acid)
CNΘ shows maximum similarities with Cl− , Br − , Γ

(i) forms HCN
(ii) forms (CN)2
(iii) AgCN, Pb(CN)2, are insoluble
(iv) Interpseudo halogen compounds ClCN, BrCN, ICN can be formed
(v) AgCN is insoluble in H2 O but soluble in NH3
(vi) forms large no.of complex.e.g.
[Cu(CN)4 ]3− &[CuCl4 ]−3
[Co(CN)6 ]−3 &[CoCl6 ]−3
APNI KAKSHA 42
NOBLE GASES FAMILY

GROUP 18 ELEMENTS (He, Ne, Ar, Kr, Xe, Rn)
Occurrence
(i) All the noble gases except radon occur in the atmosphere.
Relative abundance : Ar is highest (Ne, Kr, He, Rn)
(ii) Their atmospheric abundance in dry air is ∼ 1% by volume of which argon is the major
constituent.
(iii) Helium and sometimes neon are found in minerals of radioactive origin e.g., pitchblende,
monazite, cleveite.
(iv) The main commercial source of helium is natural gas.
(v) Xenon and radon are the rarest elements of the group.
(vi) Radon is obtained as a decay product of 226 Ra.
226 222 4
88 Ra → 86 Rn + 2 He
(vii) He liquid can exist in two forms. I-form when changes to II-form at 𝜆-point temperature
many physical properties change abruptly.
e.g.
(i) Sp. heat changes by a factor of 10
(ii) Thermal conductivity increases by 106 and it becomes 800 times faster than Cu
(iii) It shows zero resistance
(iv) It can flow up the sides of the vessel
General electronic configuration of 18 group element is ns2 np6 except helium which has 1 s 2 .
Ionisation Enthalpy
He > Ne > Ar > Kr > Xe > Rn(I. E. order)
Atomic Radii
He < Ne < Ar < Kr < Xe < Rn (atomic radius order)
Electron Gain Enthalpy
They have large positive values of electron gain enthalpy due to stable electronic
configurations, and there for have no tendency to accept the electron
Melting point and boiling point
He < Ne < Ar < Kr < Xe < Rn (Melting point order)
(−269∘ C)
B.P. order : He < Ne < Ar < Kr < Xe < Rn (Boiling point order)
Density order :
He < Ne < Ar < Kr < Xe < Rn (Density order)
APNI KAKSHA 43
Physical properties :
(i) All the noble gases are monoatomic.
(ii) They are colourless, odourless and tasteless.
(iii) They are sparingly soluble in water.
(iv) They have very low melting and boiling points because the only type of interatomic
interaction in these elements is weak dispersion forces.
(v) Helium has the lowest boiling point (4.2 K) of any known substance.
(vi) It has an unusual property of diffusing through most commonly used laboratory materials
such as rubber, glass or plastics.
Chemical Properties
In general, noble gases are least reactive. Their inertness to chemical reactivity is attributed to
the following reasons:
(i) The noble gases except helium (1𝑠 2 ) have completely filled 𝑛𝑠 2 𝑛𝑝6 electronic configuration
in their valence shell.
(ii) They have high ionisation enthalpy and more positive electron gain enthalpy.
Note: The reactivity of noble gases has been investigated occasionally, In March 1962, Neil Bartlett,
then at the University of British Columbia, observed the reaction of a noble gas. First, he
prepared a red compound which is formulated as O2 + PtF6 − . He, then realised that the first
ionisation enthalpy of molecular oxygen (1175kJmol−1 ) was almost identical with that of
xenon (1170 kJ mol−1 ). He made efforts to prepare same type of compound with Xe and was
successful in preparing another red colour compound Xe+ PtF6− by mixing PtF6 and xenon. After
this discovery, a number of xenon compounds mainly with most electronegative elements like
fluorine and oxygen, have been synthesised. The compounds of krypton are fewer. Only the
difluoride (KrF2 ) has been studied in detail. Compounds of radon have not been isolated but
only identified (e.g., RnF2 ) by radiotracer technique. No true compounds of Ar, Ne or He are yet
known.
FLUORINEDES OF XENON
Preparation
673 K,1 bar
Xe(g) + F2 ( g) ⟶ XeF2 ( s)
(xenoninexcess)
873 K,7bar
Xe(g) + 2 F2 ( g) ⟶ XeF4 ( s)
(1:5 ratio)
573 K,60−70bar
Xe(g) + 3 F2 ( g) ⟶ XeF6 ( s)
(1:20ratio)
143 K
XeF4 + O2 F2 ⟶ XeF6 + O2
APNI KAKSHA 44
Physical properties
XeF2 , XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K.
Chemical properties
(i) Hydrolysis:
2XeF2 ( s) + 2H2 O(𝑙) → 2Xe(g) + 4HF(aq) + O2 ( g)
6XeF4 + 12H2 O → 4Xe + 2XeO3 + 24HF + 3O2
XeF6 + 3H2 O → XeO3 + 6HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2 F2 .
XeF6 + H2 O → XeOF4 + 2HF
XeF6 + 2H2 O → XeO2 F → +4HF
Note : Hydrolysis in alkaline medium
2XeF2 + 4OH − ⟶ 2Xe + 4 F − + 2H2 O + O2
XeF6 + 7OH − ⟶ HXeO−
4 + 3H2 O + 6 F
−
Xenate ion
2HXeO− − 4
4 + 2OH ⟶ XeO6 ↓ +Xe + 2H2 O + O2
(ii) As fluorinating agents: They are powerful fluorinating agents.

2SF4 + XeF4 ⟶ 2SF6 + Xe
Pt + XeF4 ⟶ PtF4 + Xe
(iii) As fluoride donar
XeF2 + MF5 ⟶ [XeF]+ [MF6 ]− (M = As, Sb, P)
XeF6 + BF3 ⟶ [XeF5 ]+ [BF4− ]
XeF6 + HF ⟶ [XeF5 ]+ [HF2 ]−
(iv) As Fluoride acceptor
XeF6 + MF ⟶ M + [XeF7 ]− (M = Na, K, Rb, Cs)
Δ
2Cs + [XeF7 ]− 50∘ C XeF6 + Cs2 [XeF8 ]
XeF4 + MF ⟶ M + + XeF5−
(alkali metals fluoride)
(v) Reaction with 𝐒𝐢𝐎𝟐
SiO2 also converts XeF6 into XeOF4
2XeF6 + SiO2 ⟶ SiF4 ↑ +2XeOF4
violet
Similarly, XeO3 + XeOF4 ⟶ 2XeO2 F2 ∣ XeO3 + 2XeF6 ⟶ 3XeOF4
APNI KAKSHA 45
(vi) Oxdizing properties

H2 reduces Xe - fluorides to Xe
XeF2 + H2 ⟶ Xe + 2HF and so on
Xe - fluorides oxidise Cl− to Cl2 and I− to I2
XeF2 + 2HCl ⟶ 2HF + Xe + Cl2
XeF4 + 4KI ⟶ 4KF + Xe + 2I2
Uses of helium :
(i) He a non-inflammable and light gas. Hence, it is used in filling balloons for meteorological
observations.
(ii) It is also used in gas-cooled nuclear reactors.
(iii) It is used in cryoscopy to obtain the very low temperature required for superconductor and
laser
(b.p. 4.2 K ) finds use as cryogenic agent for carrying out various experiments at low
temperatures.
(iv) 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.
(v) It is used as a diluent for oxygen in modern diving apparatus because of its very low
solubility in blood. He is used in preference to N2 to dil. O2 in the gas cylinders used by divers.
This is because N2 is quite soluble in blood, so a sudden change in pressure causes degassing
and gives bubbles of N2 in the blood. This causes the painful condition called bends. He is
slightly soluble so the risk of bends is reduced.
USES OF NEON :
(i) Ne is used in discharge tubes and fluorescent bulbs for advertisement display purposes.
(ii) Neon bulbs are used in botanical gardens and in green houses.
USES OF ARGON :
(i) 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.
(ii) It is also used in the laboratory for handling substances that are air-sensitive.
USES OF XENON AND KRYPTON :
There are no significant uses of Xenon and Krypton. They are used in light bulbs designed for
special purposes.
APNI KAKSHA 46
SOLVED EXAMPLE
1. Though nitrogen exhibits +5 oxidation state, it does not form pentahalide. Give reason.
Sol. Nitrogen with n = 2, has s and p orbitals only. It does not have d orbitals to expand its
covalency beyond four. That is why it does not form pentahalide.
2. PH3 has lower boiling point than NH3 . Why?
Sol. Unlike NH3 , PH3 molecules are not associated through hydrogen bonding in liquid state. That is
why the boiling point of PH3 is lower than NH3 .
3. Write the reaction of thermal decomposition of sodium azide.
Sol. Thermal decomposition of sodium azide gives dinitrogen gas.
2NaN3 → 2Na + 3 N2
4. Why does NH3 act as a Lewis base ?
Sol. Nitrogen atom in NH3 has one lone pair of electrons which is available for donation. Therefore,
it acts as a Lewis base.
5. NH3 can't be dried by H2 SO4 , P2 O5 and anh. CaCl2
Sol. because : 2NH3 + H2 SO4 ⟶ (NH4 )2 SO4
H2 O + NH3 + P2 O5 ⟶ (NH4 )3 PO4
CaCl2 + 8NH3 ⟶ CaCl2 ⋅ 8NH3

forms adduct
Quick lime is used for this purpose
CaO + H2 O ⟶ Ca(OH)2 (base) } Hence no

interaction
NH3 (base)
6. Why does NO2 dimerise ?
Sol. NO2 contains odd number of valence electrons. It behaves as a typical odd molecule. On
dimerisation, it is converted to stable N2 O4 molecule with even number of electrons.
7. In what way can it be proved that PH3 is basic in nature?
Sol. PH3 reacts with acids like HI to form PH4 I which shows that it is basic in nature.
PH3 + HI → PH4 I
Due to lone pair on phosphorus atom, PH3 is acting as a Lewis base in the above reaction.
8. Why does PCl3 fume in moisture ?
Sol. PCl3 hydrolyses in the presence of moisture giving fumes of HCl.
PCl3 + 3H2 O → H3 PO3 + 3HCl
APNI KAKSHA 47
9. Are all the five bonds in PCl5 molecule equivalent? Justify your answer.
Sol. PCl5 has a trigonal bipyramidal structure and the three equitorial P − Cl bonds are equivalent,
while the two axial bonds are different and longer than equitorial bonds.
10. How do you account for the reducing behaviour of H3 PO2 on the basis of its structure?
Sol. In H3 PO2 , two H atoms are bonded directly to P atom which imparts reducing character to the
acid.
11. Elements of Group 16 generally show lower value of first ionisation enthalpy compared to the
corresponding periods of group 15 . Why?
Sol. Due to extra stable half-filled p orbitals electronic configurations of Group 15 elements, larger
amount of energy is required to remove electrons compared to Group 16 elements.
12. H2 S is less acidic than H2 Te. Why?
Sol. Due to the decrease in bond (E − H) dissociation enthalpy down the group, acidic character
increases.
13. Which form of sulphur shows paramagnetic behaviour ?
Sol. In vapour state sulphur partly exists as 𝑆2 molecule which has two unpaired electrons in the
antibonding 𝜋 ∗ orbitals like O2 and, hence, exhibits paramagnetism.
14. What happens when
(i) Concentrated H2 SO4 is added to calcium fluoride
(ii) SO3 is passed through water?
Sol. (i) It forms hydrogen fluoride
CaF2 + H2 SO4 → CaSO4 + 2HF
(ii) It dissolves SO3 to give H2 SO4 .
SO3 + H2 O → H2 SO4
15. Halogens have maximum negative electron gain enthalpy in the respective periods of the
periodic table. Why?
Sol. Halogens have the smallest size in their respective periods and therefore high effective nuclear
charge.
As a consequence, they readily accept one electron to acquire noble gas electronic
configuration.
16. Although electron gain enthalpy of fluorine is less negative as compared to chlorine, fluorine is
a stronger oxidising agent than chlorine. Why?
Sol. It is due to
(i) low enthalpy of dissociation of F-F bond
(ii) high hydration enthalpy of F −
APNI KAKSHA 48
17. Fluorine exhibits only -1 oxidation state whereas other halogens exhibit +1, +3, +5 and +7
oxidation states also. Explain.
Sol. 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.
18. Write the balanced chemical equation for the reaction of Cl2 with hot and concentrated NaOH.
Is this reaction a disproportionation reaction? Justify.
Sol. 3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2 O
Yes, chlorine from zero oxidation state is changed to -1 and +5 oxidation states.
19. CaF2 used in HF prep n . must be free from SiO2 . Explain.
Ans. CaF2 + H2 SO4 ⟶ CaSO4 + HF
If SiO2 present as impurity
4HF + SiO2 ⟶ SiF4 + 2H2 O Hence presence of one molecule SiO2
}
SiF4 + 2HF ⟶ H2 [SiF6 ] Consume 6 molecule of HF
HF can not be stored in glass vessel due to same reason.
20. When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride.
Why?
Sol. Its reaction with iron produces H2 .
Fe + 2HCl → FeCl2 + H2
Liberation of hydrogen prevents the formation of ferric chloride.
21. Discuss the molecular shape of BrF3 on the basis of VSEPR theory.
Sol. The central atom Br has seven electrons in the valence shell. Three of these will form
electronpair bonds with three fluorine atoms leaving behind four electrons. Thus, there are
three bond pairs and two lone pairs. According to VSEPR theory, these will occupy the corners
of a trigonal bipyramid.
The two lone pairs will occupy the equatorial positions to minimise lone pair-lone pair and the
bond pair-lone pair repulsions which are greater than the bond pair-bond pair repulsions. In
addition, the axial fluorine atoms will be bent towards the equitorial fluorine in order to
minimize the lone-pair-lone pair repulsions. The shape would be that of a slightly bent ' T '.
APNI KAKSHA 49
22. Why are the elements of Group 18 known as noble gases ?

Sol. 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 now
known as noble gases.
23. Noble gases have very low boiling points. Why?
Sol. Noble gases being monoatomic have no interatomic forces except weak dispersion forces and
therefore, they are liquefied at very low temperatures. Hence, they have low boiling points.
24. Does the hydrolysis of XeF6 lead to a redox reaction?
Sol. No, the products of hydrolysis are XeOF4 and XeO2 F2 where the oxidation states of all the
elements remain the same as it was in the reacting state.
25. Standard electrode potential values, E Θ for Al3+ /Al is −1.66 V and that of Tl3+ /Tl is +1.26 V.
Predict about the formation of M 3+ ion in solution and compare the electropositive character of
the two metals.
Sol. Standard electrode potential values for two half cell reactions suggest that aluminium has high
tendency to make Al3+ (aq) ions, whereas Tl3+ is not only unstable in solution but is a powerful
oxidizing agent also. Thus Tl+ is more stable in solution than Tl3+ . Aluminium being able to
form +3 ions easily, is more electropositive than thallium.
26. White fumes appear around the bottle of anhydrous aluminium chloride. Give reason.
Sol. Anhydrous aluminium chloride is partially hydrolysed with atmospheric moisture to liberate
HCl gas. Moist HCl appears white in colour.
27. Boron is unable to form BF63− ion. Explain.
Sol. Due to non-availability of d orbitals, boron is unable to expand its octet. Therefore, the
maximum covalence of boron cannot exceed 4 .
28. Why is boric acid considered as a weak acid?
Sol. Because it is not able to release H + ions on its own. It receives OH − ions from water molecule to
complete its octet and in turn releases H + ions.
29. Select the member(s) of group 14 that (i) forms the most acidic dioxide, (ii) is commonly found
in +2 oxidation state, (iii) used as semiconductor.
Sol. (i) carbon
(ii) lead
(iii) silicon and germanium
30. [SiF6 ]2− is known whereas [SiCl6 ]2− not. Give possible reasons.
Sol. The main reasons are :
APNI KAKSHA 50
(i) six large chloride ions cannot be accommodated around Si4+ due to limitation of its size.
(ii) interaction between lone pair of chloride ion and Si4+ is not very strong.
31. Diamond is covalent, yet it has high melting point. Why?
Sol. Diamond has a three-dimensional network involving strong C − C bonds, which are very
difficult to break and, in turn has high melting point.
32. SiH4 is more reactive than CH4 . Explain
Reasons
(i) Si𝛿+ − H 𝛿− in C𝛿− − H 𝛿+
C - more electronegative than H
Si less electronegative than H
So bond polarity is reversed when Nu− attacks, it faces repulsion in C but not in Si
(ii) Silicon is having vacant d orbital which is not in case of carbon
(iii) Silicon is larger in size compared to C. By which the incoming Nu− doesn't face any steric
hindrance to attack at Si whereas CH4 is tightly held from all sides.
APNI KAKSHA 51
EXERCISE-I
Only one option is correct :
1. PH3 (Phosphine) when passed in aqueous solution of CuSO4 it produce -
(A) Blue precipitate of Cu(OH)2
(B) dark blue solution of [Cu(PH3 )4 ]SO4
(C) Black precipitate of Cu3 P2
(D) Colorless solution of [Cu(H2 O)4 ]+
Δ
2. H3 PO2 ⟶ (X) + PH3 ; is
(A) Dehydration reaction
(B) Oxidation reaction
(C) Disproportionation reaction
(D) Dephosphorelation reaction
3. Which of the following species is not a pseudohalide?
(A) CNO− (B) RCOO− (C) OCN− (D) N3−
4. An orange solid (X) on heating, gives a colourless gas (Y) and a only green residue (Z). Gas (Y)
on treatement with Mg, produces a white solid substance
(A) Mg 3 N2 (B) MgO (C) Mg 2 O3 (D) MgCl2
5. Conc. HNO3 is yellow coloured liquid due to
(A) dissolution of NO in conc. HNO3
(B) dissolution of NO2 in conc. HNO3
(C) dissolution of N2O in conc. HNO3
(D) dissolution of N2O3 in conc. HNO3
6. A gas at low temperature does not react with the most of compounds. It is almost inert and is
used to create inert atmosphere in bulbs. The combustion of this gas is exceptionally an
endothermic reaction. Based on the given information, we can conclude that the gas is
(A) oxygen (B) nitrogen (C) carbon mono-oxide (D) hydrogen
7. When chlorine gas is passed through an aqueous solution of a potassium halide in the presence
of chloroform, a voilet colouration is obtained. On passing more of chlorine water, the voilet
colour is disappeared and solution becomes colourless. This test confirms the presence of in
aqueous solution.
(A) chlorine (B) fluorine (C) bromine (D) iodine
140∘ C 220∘ C 320∘ C
8. H3 PO2 ⟶ A ⟶ B ⟶
Compound (C) is
(A) H2 PO3 (B) H3 PO3 (C) (HPO3 )n (D) H4 P2 O7
APNI KAKSHA 52
9. An explosive compound (A) reacts with water to produce NH4OH and HOCl. Then, the
compound (A), is
(A) TNG (B) NCl3 (C) PCl3 (D) HNO3
10. An inorganic compound (A) made of two most occuring elements into the earth crust, having a
polymeric tetra-headral network structure. With carbon, compound (A) produces a poisonous
gas (B) which is the most stable diatomic molecule. Compounds (A) and (B) will be
(A) SiO2 , CO2 (B) SiO2 , CO (C) SiC, CO (D) SiO2 , N2
11. A sulphate of a metal (A) on heating evolves two gases (B) and (C) and an oxide (D). Gas (B)
turns K 2 Cr2 O7 paper green while gas (C) forms a trimer in which there is no S − S bond.
Compound (D) with HCI, forms a Lewis acid (E) which exists as a dimer. Compounds (A), (B),
(C), (D) and (E) are respectively
(A) FeSO4 , SO2 , SO3 , Fe2 O3 , FeCl3 (B) Al2 (SO4 )3 , SO2 , SO3 , Al2 O3 , FeCl3
(C) FeS, SO2 , SO3 , FeSO4 , FeCl3 (D) FeS, SO2 , SO3 , Fe2 (PO4 )3 , FeCl2
12. A tetra-atomic molecule (A) on reaction with nitrogen(I)oxide, produces two substances (B)
and (C). (B) is a dehydrating agent in its monomeric form while substance (C) is a diatomic gas
which shows almost inert behaviour. The substances (𝐴) and (𝐵) and (𝐶) respectively will be
(A) P4 , P4 O10 , N2 (B) P4 , N2 O5 , N2 (C) P4 , P2 O3 , Ar (D) P4 , P2 O3 , H2
13. First compound of inert gases was prepared by scientist Neil Barthlete in 1962. This compound
is
(A) XePtF6 (B) XeO3 (C) XeF6 (D) XeOF4
14. Carbongene has X% of CO2 and is used as an antidote for poisoning of Y. Then, X and Y are
(A) X = 95% and Y = lead poisoning (B) X = 5% and Y = CO poisoning
(C) X = 30% and Y = CO2 poisoning (D) X = 45% and Y = CO poisoning
15. The correct order of acidic strength of oxides of nitrogen is
(A) NO < NO2 < N2 O < N2 O3 < N2 O5
(B) N2 O < NO < N2 O3 < N2 O4 < N2 O5
(C) NO < N2 O < N2 O3 < N2 O5 < N2 O4
(D) NO < N2 O < N2 O5 < N2 O3 < N2 O4
T1 T2 redhot
16. H3 BO3 ⟶ X ⟶ Y ⟶ B2 O3
If T1 < T2 then X and Y respectively are
(A) X = Metaboric acid and Y = Tetraboric acid
(B) X = Tetraboric acid and Y = Metaboric acid
(C) X = Borax and Y = Metaboric acid
(D) X = Tetraboric acid and 𝑌 = Borax
APNI KAKSHA 53
17. When conc. H2 SO4 was treated with K 4 [Fe(CN)6 ], CO gas was evolved. By mistake, somebody
used dilute H2 SO4 instead of conc. H2 SO4 then the gas evolved was
(A) CO (B) HCN (C) N2 (D) CO2
18. An inorganic white crystalline compound (A) has a rock salt structure. (A) on reaction with
conc. H2 SO4 and MnO2 , evolves a pungent smelling, greenish-yellow gas (B). Compound (A)
gives white ppt. of (C) with AgNO3 solution. Compounds (A), (B) and (C) will be respectively
(A) NaCl, Cl2 , Agcl (B) NaBr, Br2 , NaBr
(C) NaCl, Cl2 , Ag 2 SO4 (D) Naz CO3 , CO2 , Ag 2 CO3
19.
Compound (A) is
(A) a linear silicone (B) a chlorosilane
(C) a linear silane (D) a network silane
20. When oxalic acid reacts with cone. H2 SO4 , two gases produced are of neutral and acidic in
nature respectively. Potassium hydroxide absorbs one of the two gases. The product formed
during this absorption and the gas which gets absorbed are respectively
(A) K 2 CO3 and CO2 (B) KHCO3 and CO2
(C) K 2 CO3 and CO (D) KHCO3 and CO
21. Conc. H2 SO4 cannot be used to prepare HBr from NaBr because it
(A) reacts slowly with NaBr (B) oxidises HBr
(C) reduces HBr (D) disproportionates HBr
22. Ammonia can be dried by
(A) conc. H2 SO4 (B) P4 O10 (C) CaO (D) anhydrous CaCl2
23. When chlorine reacts with a gas X, an explosive inorganic compound Y is formed. Then X and Y
will be
(A) X = O2 and Y = NCl3 (B) X = NH3 and Y = NCl3
(C) X = O2 and Y = NH4 Cl (D) X = NH3 and Y = NH4 Cl
24. HNO3 + P4 O10 ⟶ HPO3 + A; the product A is
(A) N2 O (B) N2 O3 (C) NO2 (D) N2 O5
25. Which of the following is the correct order of acidic strength?
(A) Cl2 O7 > SO3 > P4 O10 (B) CO2 > N2 O5 > SO3
(C) Na2 O > MgO > Al2 O3 (D) K 2 O > CaO > MgO
N2
26. Ca + C2 ⟶ CaC2 ⟶ A
Compound (A) is used as a/an
APNI KAKSHA 54
(A) fertilizer (B) dehydrating agent

(C) oxidising agent (D) reducing agent
27. A gas which exists in three allotropic forms a, b and g is
(A) SO2 (B) SO3 (C) CO2 (D) NH3
28. A red coloured mixed oxide (X) on treatment with cone. HNO3 gives a compound (Y). (Y) with
HCl, produces a chloride compound (Z) which can also be produced by treating (X) with cone.
HCl.
Compounds (X), (Y), and (Z) will be
(A) Mn3 O4 , MnO2 , MnCl2 (B) Pb3 O4 , PbO2 , PbCl2
(C) Fe3 O4 , Fe2 O3 , FeCl2 (D) Fe3 O4 , Fe2 O3 , FeCl3
29. One mole of calcium phosphide on reaction with excess of water gives
(A) one mole of phosphine (B) two moles of phosphoric acid
(C) two moles of phosphine (D) one mole of phosphorus penta-oxide
>240∘ C 625∘ C rapid
30. NaH2 PO4 ⟶ (NaPO3 )3 ⟶ NaPO3 (liquid melt) ⟶ D (glass)
cooling
Sodium trimetaphosphate
Compound (D) is known as
(A) Microcosmic salt (B) Graham's salt
(C) Reimann's salt (D) Switzer's Salt
31. Three allotropes (A), (B) and (C) of phosphorous in the following change are respectively
(A) white, b-black, red (B) b-black, white, red

(C) red, b-black, white (D) red, violet, b-black
32. When an inorganic compound reacts with SO2 in aqueous medium, produces (A). (A) on
reaction with Na2 CO3 , gives compound (B) which with sulphur, gives a substance (C) used in
photography.
Compound (C) is
(A) Na2 S (B) Na2 S2 O7 (C) Na2 SO4 (D) Na2 S2 O3
33. B(OH)3 + NaOH ⇌ NaBO2 + Na[B(OH)4 ] + H2 O
How can this reaction is made to proceed in forward direction?
(A) addition of cis 1,2 diol (B) addititon of borax
APNI KAKSHA 55
(C) addition of trans 1,2 diol (D) addition of Na2 HPO4

34. Which is the compound responsible for the flickering light called will-o-the-wisp, some times
seen in the Marsh.
(A) PH3 (B) P2 H4 (C) H2 S (D) PH3 + H2 S
35. The gun powder is consisting of '__________ '+ sulphur + Charcoal what is the missing substance
for gun powder
(A) LiNO3 (B) NH4 NO2 (C) KNO3 (D) (A) and (B) mixture
36. An aqueous solution of borax is
(A) Neutral (B) Amphoteric (C) Basic (D) Acidic
37. Boric acid is polymeric due to
(A) Its acidic nature (B) The presence of hydrogen bonds
(C) Its monobasic nature (D) Its geometry
38. The type of hybridisation of boron in diborane is
(A) sp (B) sp2 (C) sp3 (D) dsp2
39. Thermodynamically the most stable form of carbon is
(A) Diamond (B) Graphite (C) Fullerenes (D) Coal
40. Elements of group 14
(A) Exhibit oxidation state of +4 only
(B) Exhibit oxidation state of +2 and +4 only
(C) Form M 2− and M 4+ ions
(D) Form M 2+ and M 4+ ions
41.
if A is a basic gas then identified (A) and (B)

(A) NH3 , NH4 Br (B) NH3 , N2 O (C) NH3 , N2 O5 (D) None of these
Question No. 50 to 55 (6 questions)
Questions given below consist of two statements each printed as Assertion (A) and Reason (R);
while answering these questions you are required to choose any one of the following four
responses:
(A) if both (A) and (R) are true and (R) is the correct explanation of (A)
(B) if both (A) and (R) are true but (𝑅) is not correct explanation of (A)
APNI KAKSHA 56
(C) if (𝐴) is true but (𝑅) is false

(D) if (A) is false and (R) is true
42. Assertion: Borax bead test is applicable only to coloured salt.
Reason: In borax bead test, coloured salts are decomposed to give coloured metal meta
borates.
43. Assertion: Aluminium and zinc metal evolve H2 gas from NaOH solution
Reason: Several non-metals such as P, S, Cl, etc. yield a hydride instead of H2 gas from NaOH
44. Assertion: Conc. H2 SO4 cannot be used to prepare pure HBr from NaBr
Reason: It reacts slowly with NaBr.
45. Assertion: Oxygen is more electronegative than sulphur, yet H2 S is acidic, while H2 O is neutral.
Reason: H − S bond is weaker than O − H bond.
46. Assertion: Chlorine gas disproportionates in hot & conc. NaOH solution.
Reason: NaCl and NaOCl are formed in the above reaction.
47. Assertion: Liquid IF5 conducts electricity.
Reason: Liquid IF5 self ionizes as, 2IF5 ⇌ IF4+ + IF6−
APNI KAKSHA 57
EXERCISE-II
One or more than one option may be correct :
1. When a compound X reacts with ozone in aqueous medium, a compound Y is produced. Ozone
also reacts with Y and produces compound Z. Z acts as an oxidising agent, then X, Y and 𝑍 will
be
(A) X = HI, Y = I2 and Z = HIO3 (B) X = KI, Y = I2 and Z = HIO3
(C) X = KI, Y = I2 and Z = HIO4 (D) X = HI, Y = I2 and Z = HIO4
2. Which of the following statements is/are correct regarding B2 H6 ?
(A) banana bonds are longer but stronger than normal B − H bonds
(B) B2 H6 is also known as 3e − 2e compound
(C) the hybrid state of B in B2 H6 is sp3 while that of sp2 in BH3
(D) it cannot be prepared by reacting BF3 with LiBH3 in the presence of dry ether
3. Which of the following statements is/are correct regarding inter-halogen compounds of ABx
types?
(A) x may be 1,3,5 and 7
(B) A is a more electronegative halogen than B
(C) FBr3 cannot exit
(D) The interhalogens are generally more reactive than the halogens (except F2 ) due to weaker
A- X bonds compared to X − X bond.
4. When an inorganic compound (X) having 3e − 2e as well as 2e − 2e bonds reacts with
ammonia gas at a certain temperature, gives a compound (Y) iso-structural with benzene.
Compound (X) with ammonia at a high temperature, produces a hard substance (𝑍). Then
(A) (X) is B2 H6
(B) (Z) is known as inorganic graphite
(C) (Z) having structure similar to graphite
(D) (Z) having structure similar to (X)
5. Boric acid
(A) exists in polymeric form due to inter-molecular hydrogen bonding.
(B) is used in manufacturing of optical glasses.
(C) is a tri-basic acid
(D) with borax, it is used in the preparation of a buffer solution.
6. The correct statement(s) related to allotropes of carbon is/are
(A) graphite is the thermodynamically most stable allotrope of carbon and having a two
dimensional sheet like structure of hexagonal rings of carbon (sp2 )
APNI KAKSHA 58
(B) diamond is the hardest allotrope of carbon and having a three dimensional network
structure of C(sp3 )
(C) fullerene (C60 ) is recently discovered non-crystalline allotrope of carbon having a
footballlike structure.
(D) Vander Waal's force of attraction acts between the layers of graphite 6.14Å away from each
other
7. Al2 (SO4 )3 + NH4 OH ⟶ X, then
(A) X is a white coloured compound
(B) X is insoluble in excess of NH4 OH
(C) X is soluble in NaOH
(D) X cannot be used as an antacid
8. The species that undergo(es) disproportionation in an alkaline medium is/are
(A) Cl2 (B) MnO2−
4 (C) P4 (D) ClO−
4
9. Select correct statement(s):

(A) Borax is used as a buffer
(B) 1M borax solution reacts with equal volumes of 2MHCl solution
(C) Titration of borax can be made using methyl orange as the indicator
(D) Coloured bead obtained in borax-bead test contains metaborate
10. Which of the following is / are correct for group 14 elements?
(A) The stability of dihalides are in the order CX2 < SiX2 < GeX2 < SnX2 < PbX2
(B) The ability to form pp-pp multiple bonds among themselves increases down the group
(C) The tendency for catenation decreases down the group
(D) They all form oxides with the formula MO2.
11. Zeolite is used in which of the following cases:
(A) Conversion of alcohols into gasoline
(B) Cracking of hydrocarbon
(C) Isomerisation of hydrocarbons
(D) Softning of hard water
12. Which of the following oxides are mixed oxide:
(A) PbO2 (B) SnO2 (C) Pb2 O3 (D) Pb3 O4
13. Which of the following oxide(s) gives brown ppt on reaction with conc. HNO3 :
(A) PbO (B) SnO (C) Pb2 O3 (D) Pb3 O4
APNI KAKSHA 59
14. Which of the following reaction produces PH3 :

(A) Ca3 P2 + H2 O → (B) P4 + NaOH →
Δ
(C) PH4 I + KOH → (D) H3 PO2 ⟶
15. Which of the following element of chalcogen group can form MX2 type of compound where
X = Cl and Br :
(A) O (B) S (C) Se (D) Te
Δ
16. Ca2 B6 O11 + Na2 CO3 ⟶ [X] + CaCO3 + NaBO2 (Unbalanced equation)
Correct statement for [X]
(A) Structure of anion of crystalline (X) has one boron atom sp3 hybridised and other three
boron atoms sp2 hybridised
(B) (X) with NaOH (aq.) gives a compound which on reaction with H2 O2 in alkaline medium
yields a compound used as brightner in soaps
(C) Hydrolysis of (X) with HCl or H2 SO4 yields a compound which on reaction with HF gives
fluoroboric acid
(D) [X] on heating with cobalt salt in oxidising flame gives blue coloured bead
2000∘ Clo
17. (A) + 2C (B) + 2CO ↑
250∘ C
2000∘ Cto
(B) + Carbon → (C)
2500∘ C
If A is an example of 3 − d silicate then select the correct statements about (C)

(A) Central atom of C is sp3 hybridised
(B) (C) is non planar and all atoms are sp3 hybridised
(C) C has diamond like structure, and it is colourless when impurity is present but yellow solid
at room temperature
(D) (C) is silicon carbide ( SiC) and it is not being affected by any acid except H0 PO4
APNI KAKSHA 60
EXERCISE-III
Paragraph for Question No. 1 & 2
1. When D react with C2 H5 OH then product will be

(A) C2 H5 Cl, H3 PO4 (B) C2 H5 Cl, H3 PO3
(C) CH3 COCl, H3 PO3 (D) Only H3 PO3
2. B can be absorbed by :
(A) Ca(OCl)Cl (B) H2 S (C) Both (D) None
Paragraph for Question No. 3 to 6
373 K
HCOOH ⟶ H2 O + (X)
𝐶𝑜𝑛𝑐.H2 SO4
423−1273 K
C(s) + H2 O ⟶ (X) + H2 ( g)
3. Select the correct statement about (X)

(A) (𝑋) is a colourless, odourless and almost water insoluble gas
(B) X is highly poisonous and burns with blue flame
(C) When (X) gas is passed through PdCl2 solution giving rise to balck ppt
(D) All of these
4. Mixture of (X) gas +H2 is called
(A) Water gas or synthesis gas
(B) Producer gas
(C) Methane gas
(D) None of these
5. In second reaction when air is used instead of steam a mixed of (X) gas and N2 is produced
which is called
(A) Water gas (B) Synthesis gas (C) Producer gas (D) Carbon dioxide gas
6. Select the correct statement about (X)
(A) (X) gas is estimatate by I2 O5 (B) Cu2 Cl2 is absorber of (X) gas
(C) (X) gas is the purifying agent for Ni (D) All of these
APNI KAKSHA 61

Read the following write-ups and answer the questions at the end of it.
Silicons are synthetic polymers containing repreated R 2 SiO units. Since, the empirical formula
is that of a ketone (R 2 CO), the name silicone has been given to these materials. Silicones can be
made into oils, rubbery elastomers and resins. They find a variety of applications because of
their chemical inertness, water repelling nature, heat-resistance and good electrical insulating
property.
Commercial silicon polymers are usually methyl derivatives and to a lesser extent phenyl
derivatives and are synthesised by the hydrolysis of
R 2 SiCl2 [R = methyl (Me) or phenyl (𝜙)]
7. If we mix Me MiCl3 SithMe2 SiCl2 , we get silicones of the type:
(A)
(B)
(C) both of the above

(D) none of the above
APNI KAKSHA 62
8. If we start with MeSiCl3 as the starting material, silicones formed is:
(A)
(B)
(C) both of the above

(D) none of the above

CO gas is absorbed by aqueous suspension of cuprous chloride forming the complex like
[CuCl(CO)(H2 O)2 ].
9. Comment on the shape of the above complex.
(A) Tetrahedral (B) TBP (C) Square planar (D) Can not be predicted
10. Choose the correct statement regarding the above molecule
(A) Cl-atom is separated by equal angle from both of the water molecule
(B) Magnetic moment of the above complex is 1.73 B.M.
(C) There are two stereo isomer for the above complex.
(D) Both (A) and (C)
Paragraph for Question No. 11 to 12
There are some deposits of nitrates and phosphates in earth's crust. Nitrates are more soluble
in water. Nitrates are difficult to reduce under the laboratory conditions but microbes do it
easily. Ammonia forms large number of complexes with transition metal ions. Hybridization
easily explains the ease of sigma donation capability of NH3 and PH3 . Phosphine is a flammable
gas and is prepared from white phosphorous.
11. Among the following, the correct statement is

(A) Phosphates have no biological significance in humans
(B) Between nitrates and phosphates, phosphates are less abundant in earth's crust
(C) Between nitrates and phosphates, nitrates are less abundant in earth's crust
(D) Oxidation of nitrates is possible in soil
APNI KAKSHA 63
12. White phosphorus on reaction with NaOH gives PH3 as one of the products. This is a
(A) dimerization reaction (B) disproportionation reaction
(C) condensation reaction (D) precipitation reaction
13. Match List-I with List-II

List-I (Chemical reaction) List-II (Name of process)
800∘ C/Pt
(I) 4NH3 + 5O2 ⟶ 4NO + 6H2 O (a) Contact process
230∘ C/CuCl2
(II) 4HCl + O2 ⟶ 2Cl2 + 2H2 O (b) Ostwald's process
450−500∘ /V2 O5
(III) 2SO2 + O2 ⟶ 2SO3 (c) Deacon's process
Fe+Mo
(IV) 2 N2 + 3H2 ⟶ 2NH3 (d) Haber's process
(A) I-a, II-b, III-d, IV-c (B) I-b, II-c, III-a, IV-d
(C) I-a, II-d, III-c, IV-b (D) I-a, II-c, III-b, IV-d
14. Column-I Column-II

(P) Dry ice (1) Used as antidote for CO-poisoning
(Q) Carbongene (2) Used as nonstick coating
(R) Carborundum (3) Used as refrigerant
(S) Teflon (4) Used as abrasive
Code:
P Q R S P Q R S
(A) 4 1 3 2 (B) 4 2 1 3
(C) 3 1 4 2 (D) 1 4 3 2
15. Column-I Column-II

Compound Correct statement for compounds given
(P) SnCl2 (1) Used in printing technology
(Q) Butter of tin (2) Used for gilding purpose (in joining gold pieces)
(R) Mosaic gold (3) Reducing agent
(S) Pink salt (4) Mordant
Code:
P Q R S P Q R S
(A) 4 3 2 1 (B) 3 4 2 1
(C) 2 1 3 4 (D) 1 3 4 2
APNI KAKSHA 64
16. Column-I (Metal) Column-II (Correct statements)

(P) Fe (1) Produces NO with 20%HNO3
(Q) Cu (2) Produces NH4 NO3 with 6%HNO3
(R) Pb (3) Produces NO2 with 70%HNO3
(S) Sn (4) Produces NH4 NO3 with 20%HNO3
Code:
P Q R S
(A) 2,1 1 3,4 2,3
(B) 2,3 1,3 1,3 2,3,4
(C) 1,3 1,2 3,4 2
(D) 1,4 2,3 1,3 1,4
17. Column-I (Reactions) Column-II (Correct statements)

(P) XeF2 + PF5 → (1) Fluoride of Xe acts as fluoride acceptor
(Q) XeF4 + Pt → (2) Fluoride of Xe undergoes disproportion
(R) XeF4 + H2 O → (3) Fluoride of Xe acts as fluorinating agent
(S) XeF6 + CsF → (4) Fluoride of Xe act as fluoride donor
Code:
𝑃 𝑄 𝑅 𝑆 𝑃 𝑄 𝑅 𝑆
(A) 4 2 3 1 (B) 3 2 1 4
(C) 4 3 2 1 (D) 3 4 2 1
18. Column-I (Substances) Column-II (Can be prepared by)

(P) O3 (1) Acidification of BaO2 with H3 PO4
(Q) Bleaching powder (2) Birkeland Eyde process
(R) H2 O2 (3) Dry O2 is passed through a silent electrical
discharge
(S) HNO3 (4) Cl2 gas is passed through slaked lime
Code:
P Q R S P Q R S
(A) 3 4 1 2 (B) 1 3 4 2
(C) 2 1 3 4 (D) 4 1 2 3
APNI KAKSHA 65
EXERCISE-IV (JEE-MAINS)
1. Which products are expected from the disproportionation of hypochlorous acid:
[AIEEE-2002]
(1) HClO3 and Cl2 O (2) HClO2 and HClO
(3) HCl and Cl2 O (4) HCl and HClO3
2. Identify the incorrect statement among the following : [AIEEE-2002]

(1) Ozone reacts with SO2 to give SO3
(2) Silicon reacts with NaOH (aq.) in the presence of air to give Na2 SiO3 and H2 O
(3) Cl2 reacts with excess of NH3 to give N2 and HCl
(4) Br2 reacts with hot and strong NaOH solution to given NaBr, NaBrO4 and H2 O
3. Aluminium is industrially prepared by: [AIEEE-2002]

(1) Fused cryolite (2) Bauxite ore
(3) Alunite (4) Borax
4. For making good quality mirrors, plates of float glass are used. These are obtained by floating
molten glass over a liquid metal which does not solidify before glass. The metal used can be :
[AIEEE-2003]
(1) Sodium (2) Magnesium (3) Mercury (4) Tin
5. What may be expected when phosphine gas is mixed with chlorine gas: [AIEEE-2003]
(1) PCl5 and HCl are formed and mixture cools down
(2) PH3 ⋅ Cl2 is formed with warming up
(3) The mixture only cools down
(4) PCl3 and HCl are formed and the mixture warms up
6. Graphite is a soft solid lubricant extremely difficult to melt. The reason for this anomalous
behavour is that graphite : [AIEEE-2003]
(1) Has molecules of variable molecular masses like polymers
(2) Has carbon atoms arranged in large plated of rings of strongly bonded carbon atoms with
weak interplate bonds
(3) Is a non crystalline substance
(4) Is an allotropic form of diamond
APNI KAKSHA 66
7. Concentrated hydrochloric acid when kept in open air sometimes produces a cloud of white
fumes. This is due to : [AIEEE-2003]
(1) Strong affinity of HCl gas for moisture in air results in forming of droplets of liquid solution
which appears like a cloudy smoke
(2) Due to strong affinity for water, conc. HCl pulls moisture of air towards self. The moisture
forms droplets of water and hence the cloud
(3) Conc. HCl emits strongly smelling HCl gas all the time
(4) Oxygen in air reacts with emitted HCl gas to form a cloud of Cl2 gas
8. Aluminium chloride exists as dimer, Al2 Cl6 in solid state as well as in solution of non-polar
solvents such as benzene. When dissolved in water, it gives- [AIEEE-2004]
(1) Al3+ + 3Cl− (2) [Al(H2 O)6 ]3+ + 3Cl−
(3) [Al(OH)6 ]3− + 3HCl (4) Al2 O3 + 6HCl
9. The soldiers of Napolean army while at Alps during freezing winter suffered a serious problem
as regards to the tin buttons of their uniforms. White Metallic tin buttons get converted to grey
powder.
This transformation is related to:- [AIEEE-2004]
(1) An interaction with water vapour contained in humid air
(2) A change in crystalline structure of tin
(3) A change in the partial pressure of O2 in air
(4) An interaction with N2 of air at low temperature
10. Which one of the following statements regarding helium is incorrect [AIEEE-2004]
(1) It is used to produce and sustain powerful superconducting magnets
(2) It is used as a cryogenic agent for carrying out experiments at low temperatures
(3) It is used to fill gas balloons instead of hydrogen because it is lighter then hydrogen and
noninflammable
(4) It is used in gas-cooled nuclear reactors
11. The number of hydrogen atoms attached to phosphorus atom in hypophosphorous acid is :
[AIEEE-2005]
(1) Zero (2) Two (3) One (4) Three
APNI KAKSHA 67
12. Heating an aqueous solution of aluminium chloride to dryness will give :- [AIEEE-2005]
(1) AlCl3 (2) Al2 Cl6 (3) Al2 O3 (4) Al(OH)Cl2
13. Which one of the following is the correct statement [AIEEE-2005]

(1) Boric acid is a protonic acid
(2) Beryllium exhibits coordination number of six
(3) Chlorides of both beryllium and aluminium have bridged chloride structures in solid phase
(4) B2 H6 , 2NH3 is known as "inorganic benzene"
14. In silicon dioxide : [AIEEE-2005]

(1) Each silicon atom is surrounded by four oxygen atoms and each oxygen atom is bonded to
two silicon atoms
(2) Each silicon atom is surrounded by two oxygen atoms and each oxygen atom is bonded to
two silicon atoms
(3) Silicon atom is bonded to two oxygen atoms
(4) There are double bonds between silicon and oxygen atoms
15. Regular use of which of the following fertilizer increases the acidity of soil : [AIEEE-2007]
(1) Potassium nitrate (2) Urea
(3) Superphosphate of lime (4) Ammonium sulphate
16. The stability of dihalides of Si, Ge, Sn and Pb increases steadily in the sequence: [AIEEE-2007]
(1) GeX2 << SiX 2 << SnX 2 << PbX 2 (2) SiX 2 ≪< GeX 2 ≪< PbX 2 << SnX 2
(3) SiX 2 << GeX 2 ≪ SnX 2 << PbX2 (4) PbX 2 ≪ SnX 2 ≪ GeX 2 ≪ SiX 2
17. Among the following substituted silanes the one which will give rise to cross linked silicone
polymer on hydrolysis is [AIEEE-2008]
(1) R 4 Si (2) RSiCl3 (3) R 2 SiCl2 (4) R 3 SiCl
18. Which one of the following reactions of Xenon compounds is not feasible ? [AIEEE-2009]
(1) 2XeF2 + 2H2 O → 2Xe + 4HF + O2 (2) XeF6 + RbF → Rb[XeF7 ]
(3) XeO3 + 6HF → XeF6 + 3H2 O (4) 3XeF4 + 6H2 O → 2Xe + XeO3 + 12HF + 1.5O2
APNI KAKSHA 68
19. Which of the following statement is wrong ? [AIEEE-2011]

(1) Single N − N bond is weaker than the single P − P bond
(2) N2 O4 has two resonance structures
(3) The stability of hydrides increases from NH3 to BiH3 in group 15 of the periodic table
(4) Nitrogen cannot form dp-pp bond
20. Which of the following statements regarding sulphur is incorrect? [AIEEE-2011]

(1) At 600∘ C the gas mainly consists of S2 molceules
(2) The oxidation state of sulphur is never less than +4 in its compounds
(3) S2 molecule is paramagnetic
(4) The vapour at 200∘ C consists mostly of 𝑆8 rings
21. Boron cannot form which one of the following anions? [AIEEE-2011]
(1) B(OH)−
4 (2) BO−
2 (3) BF63− (4) BH4−
22. In view of the signs of Δr G∘ for the following reactions

PbO2 + Pb → 2PbO, Δr G∘ < 0
SnO2 + Sn → 2SnO, Δr G∘ > 0,
Which oxidation states are more characteristic for lead and tin ? [AIEEE-2011]
(1) For lead +4 , for tin +2 (2) For lead +2 , for tin +2
(3) For lead +4 , for tin +4 (4) For lead +2 , for tin +4
23. The number of S − S bonds in SO3 , S2 O3 2− , S2 O6 2− and S2 O8 2− respectively are :-

[Jee Main(Online)-2012]
(1) 1,0,1,0 (2) 0,1,1,0 (3) 1,0,0,1 (4) 0,1,0,1
24. Which one of the following depletes ozone layer? [Jee Main(Online)-2012]
(1) NO and freons (2) SO2 (3) CO (4) CO2
25. In which of the following arrangements, the sequence is not strictly according to the property
written against it ? [Jee Main(Online)-2012]
(1) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power
(2) B < C < O < N : increasing first ionisation enthalpy
(3) NH3 < PH3 < AsH3 < SbH3 : increasing basic strength
(4) HF < HCl < HBr < HI : increasing acid strength
APNI KAKSHA 69
26. The formation of molecular complex BF3 − NH3 results in a change in hybridisation of boron :-
JEE(Main) Online-2012]
(1) from sp3 to sp3 d (2) from sp2 to dsp2
(3) from sp3 to sp2 (4) from sp2 to sp3
27. The catenation tendency of C, Si and Ge is in the order Ge < Si < C. The bond energies (in
kJmol − 1 ) of C − C, Si − Si and Ge − Ge bonds are respectively: [JEE(Main) Online-2013]
(1) 348,260,297 (2) 348,297,260
(3) 297,348,260 (4) 260,297,348
28. The gas evolved on heating CaF2 and SiO2 with concentrated H2 SO4 , on hydrolysis gives a white
gelatinous precipitate. The precipitate is: [Jee Main(Online)-2014]
(1) silica gel (2) silicic acid
(3) hydrofluosilicic acid (4) calciumfluorosilicate
29. Which of the following series correctly represents relations between the elements from X to Y ?
X→Y [Jee Main(Online)-2014]
(1) 18 Ar → 54 Xe Noble character increases
(2) 3 Li → 19 K Ionization enthalpy increases
(3) 6 C → 32 Ge Atomic radii increases
(4) 9 F→ 35 Br Electron gain enthalpy with negative sign increases
30. Which of the following statements about the depletion of ozone layer is correct?
[Jee Main(Online)-2014]
(1) The problem of ozone depletion is more serious at poles because ice crystals in the clouds
over poles act as catalyst for photochemical reactions involving the decomposition of ozone by
Cl− and ClO− radicals
(2) The problem of ozone depletion is less serious at poles because NO2 solidifies and is not
available for consuming ClO∘ radicals
(3) Oxides of nitrogen also do not react with ozone in stratosphere
(4) Freons, chlorofluorocarbons, are inert chemically, they do not react with ozone in
stratosphere
APNI KAKSHA 70
31. Which of the following xenon-OXO compounds may not be obtained by hydrolysis of xenon
fluorides ? [Jee Main(Online)-2014]
(1) XeO2 F2 (2) XeO3 (3) XeO4 (4) XeOF4
32. Hydrogen peroxide acts both as an oxidising and as a reducing agent depending upon the
nature of the reacting species. In which of the following cases H2 O2 acts as a reducing agent in
acid medium ? [Jee Main(Online)-2014]
(1) MnO−
4 (2) SO3 2− (3) KI (4) Cr2 O7
33. Consider the reaction [Jee Main(Online)-2014]

H2 SO3(aq) + Sn4+ 2+ − +
(aq) + H2 O(n) → Sn(aq) + HSO4(aq) + 3H(aq)
Which of the following statements is correct?

(1) H2 SO3 is the reducing agent because it undergoes oxidation
(2) H2 SO3 is the reducing agent because it undergoes reduction
(3) Sn4+ is the reducing agent because it undergoes oxidation
(4) Sn4+ is the oxidizing agent because it undergoes oxidation
34. In the following sets of reactants which two sets best exhibit the amphoteric character of
Al2 O3 ⋅ xH2 O ? [JEE(Main) Online-2014]
Set-1 : Al2 O3 ⋅ xH2 O(s) and OH − (aq)
Set-2 : Al2 O3 ⋅ xH2 O(s) and H2 O(ℓ)
Set-3 : Al2 O3 ⋅ xH2 O(s) and H + (aq)
Set-4 : Al2 O3 ⋅ xH2 O(s) and NH3 (aq)
(1) 1 and 2 (2) 2 and 4 (3) 1 and 3 (4) 3 and 4
35. Which of the following compounds has a P-P bond :- [Jee Main(Online)-2015]
(1) H4 P2 O5 (2) (HPO3 )3 (3) H4 P2 O7 (4) H4 P2 O6
36. Chlorine water on standing loses its colour and forms :- [Jee Main(Online)-2015]
(1) HCl and HClO2 (2) HCl only
(3) HOCl and HOCl2 (4) HCl and HOCl
37. Which among the following is the most reactive ? [Jee Main-2015]
(1) I2 (2) IC1 (3) Cl2 (4) Br2
APNI KAKSHA 71
38. Which one has the highest boiling point ? [Jee Main-2015]
(1) Kr (2) Xe (3) He (4) Ne
39. From the following statements regarding H2 O2 , choose the incorrect statement :
[Jee Main-2015]
(1) It has to be stored in plastic or wax lined glass bottles in dark
(2) It has to be kept away from dust
(3) It can act only as an oxidizing agent
(4) It decomposes on exposure to light
40. The reaction of zinc with dilute and concentrated nitric acid, respectively produces :
[JEE Main-2016]
(1) NO2 and N2 O (2) N2 O and NO2
(3) NO2 and NO (4) NO and N2 O
41. The non-metal that does not exhibit positive oxidation state is : [JEE Main-2016]
(1) Oxygen (2) Fluorine (3) Iodine (4) Chlorine
42. Which intermolecular force is most responsible in allowing xenon gas to liquefy?
[JEE (Main) Online 2016]
(1) Ionic (2) Instantaneous dipole-induced dipole
(3) Dipole – dipole (4) Ion – dipole
43. The following statements concern elements in the periodic table. Which of the following is
true? [JEE (Main) Online 2016]
(1) The group 13 elements are all metals.
(2) For group 15 elements, the stability of +5 oxidation state increases down the group.
(3) All the elements in Group 17 are gases.
(4) Elements of group 16 have lower ionization enthalpy values compared to those of group 15
in the corresponding periods.
APNI KAKSHA 72
44. Assertion : Among the carbon allotropes, diamond is an insulator, whereas, graphite is a good
conductor of electricity. [JEE (Main) Online 2016]
Reason : Hybridization of carbon in diamond and graphite are sp3 and sp2 , respectively.
(1) Assertion is incorrect statement, but the reason is correct.
(2)Both assertion and reason are correct, and the reason is the correct explanation for the
assertion.
(3) Both assertion and reason are incorrect.
(4) Both assertion and reson are correct, but the reason is not the correct explanation for the
assertion.
45. Identify the incorrect statement : [JEE (Main) Online 2016]

(1) S8 ring has a crown shape.
(2) The 𝑆 − 𝑆 − 𝑆 bond angles in the 𝑆8 and 𝑆6 rings are the same
(3) 𝑆2 is paramagnetic like oxygen
(4) Rhombic and monoclinic sulphur have 𝑆8 molecules.
46. The product obtained when chlorine reacts with cold and dilute aqueous NaOH are :
[JEE-Main 2017]
(1) ClO− and ClO3− (2) ClO−
2 and ClO3
−
(3) Cl− and ClO− (4) Cl− and ClO2−
47. In graphite and diamond, the percentage of p-characters of the hybrid orbitals in hybridisation
are respectively : [Main-2018(Online)]
(1) 33 and 25 (2) 33 and 75 (3) 50 and 75 (4) 67 and 75
48. In the following sets of reactants which two sets best exhibit the amphoteric character of
Al2 O3 ⋅ xH2 O ? [Main-2018(Online)]
Set-1 : Al2 O3 ⋅ xH2 O(s) and OH − (aq)
Set-2 : Al2 O3 ⋅ xH2 O(s) and H2 O(ℓ)
Set-3 : Al2 O3 ⋅ xH2 O(s) and H − (aq)
Set-4 : Al2 O3 ⋅ xH2 O(s) and NH3 (aq)
(1) 1 and 2 (2) 2 and 4 (3) 1 and 3 (4) 3 and 4
APNI KAKSHA 73
49. The compound that does not produce nitrogen gas by the thermal decomposition is
[Main-2018(Online)]
(1) (NH4 )2 SO4 (2) Ba(N3 )2 (3) (NH4 )2 Cr2 O7 (4) NH4 NO2
50. Good reducing nature of H3 PO2 is attributed to the presence of : [Main-2019(Online)]

(1) Two P-H bonds (2) One P − OH bond
(3) One P − H bond (4) Two P-OH bonds
51. Among the following reactions of hydrogen with halogens, the one that requires a catalyst is :
[Main-2019(Online)]
(1) H2 + Br2 → 2HBr (2) H2 + F2 → 2HF
(3) H2 + I2 → 2HI (4) H2 + Cl2 → 2HCl
52. The pair that contains two P − H bonds in each of the oxoacids is: [Main-2019(Online)]
(1) H4 P2 O5 and H3 PO3 (2) H4 P2 O5 and H4 P2 O6
(3) H3 PO2 and H4 P2 O5 (4) H3 PO3 and H3 PO2
53. Iodine reacts with concentrated HNO3 to yield Y along with other products. The oxidation state
of iodine in Y is : [Main-2019(Online)]
(1) 5 (2) 1 (3) 3 (4) 7
54. The element that does NOT show catenation is: [Main-2019(Online)]
(1) Si (2) Ge (3) Pb (4) Sn
55. Chlorine on reaction with hot and concentrated sodium hydroxide gives :
(1) ClO−
3 and ClO2
−
(2) Cl− and ClO2−
(3) Cl− and ClO− (4) Cl− and ClO3−
56. The element that shows greater ability to form p − 𝜋p𝜋 multiple bond, is:
[Main-2019(Online)]
(1) Si (2) C (3) Sn (4) Ge
APNI KAKSHA 74
Topic – 1 : Group -15 Elements (Nitrogen Family)

57. White phosphorus reacts with thionyl chloride to give [Main July 28, 2022 (II)]
(A) PCl5 , SO2 and S2 Cl2
(B) PCl3 , SO2 and S2 Cl2
(C) PCl3 , SO2 and Cl2
(D) PCl5 , SO2 and Cl2
58. Which oxoacid of phosphorous has the highest number of oxygen atoms present in its chemical
formula? [Main July 27, 2022 (I)]
(A) Pyrophosphorous acid
(B) Hypophosphoric acid
(C) Phosphoric acid
(D) Pyrophosphoric acid
59. A ⎯⎯ ⎯
573K
→Redphorus ⎯⎯⎯⎯⎯
heat ;803K
underpressure
→B
Red phosphorus is obtained by heating "A" at 573 K, and can be converted to "B" by heating at
803 K under pressure. A and B, respectively, are [Main June 30, 2022 (I)]
(A) β-black phosphorus and white phosphorus.
(B) white phosphorus and β-black phosphorus.
(C) α-black phosphorus and white phosphorus.
(D) white phosphorus and α-black phosphorus.
60. Phe oxoacid of phosphorus that is easily obtained from a reaction of alkali and white
phosphorus and has two P − H bonds, is : [Main June 29, 2022 (I)]
(A) Phosphonic acid
(B) Phosphinic acid
(C) Pyrophosphorus acid
(D) Hypophosphoric acid
61. The number of non-ionisable protons present in the product B obtained from the following
reaction is ______ . [Main July 26, 2022 (II)]
C2 H5 OH + PCl3 → C2 H5 Cl + A
A + PCl3 → B
APNI KAKSHA 75
62. Consider the following reactions : [Main June 25, 2022 (II)]
PCl3 + H2 O ⟶ A + HCl
A + H2 O ⟶ B + HCl
number of ionisable protons present in the product B ________ .
63. Match List-I with List –II [Main March 16, 2021]
List-I List-II
Name of oxo acid Oxidation state of ' 𝐏 '
(A) Hypophosphorous acid (I) +5
(B) Orthophosphoric acid (II) +4
(C) Hypophosphoric acid (III) +3
(D) Orthophosphorous acid (IV) +2
(V) +1
Choose the correct answer from the options given below:
(A) (A)-(IV), (B)-(V), (C)-(II), (D)-(III) (B) (A)-(V), (B)-(IV), (C)-(II), (D)-(III)
(C) (A)-(V), (B)-(I), (C)-(II), (D)-(III) (D) (A)-(IV), (B)-(I), (C)-(II), (D)-(III)
64. Given below are two statements: [Main June 28, 2022 (I)]
Statement I: The pentavalent oxide of group- 15 element. E2 O5 is less acidic than trivalent
oxide. E2 O3 of the same element.
Statement II : The acidic character of trivalent oxide of group 15 elements E2 O3 decreases
down the group. In light of the above statements choose most appropriate answer from the
options given below:
(A) If both Statement -1 and Statement -2 are correct, and Statement -2 is the correct
explanation of the Statement - 2.
(B) If both Statement -1 and Statement -2 are correct, but Statement -2 is not the correct
explanation of the Statement - 1.
(C) If Statement - 1 is correct but Statement -2 is incorrect.
(D) If Statement -1 is incorrect but Statement - 2 is correct,
APNI KAKSHA 76
Topic – 2
Group – 16 Element (Oxygen Family)
65. Which of the following oxoacids of sulphur contains " S " in two different oxidation states?
[Main June 28, 2022 (II)]
(A) H2 S2 O3 (B) H2 S2 O6
(C) H2 S2 O7 (D) H2 S2 O8
66. Reaction of an inorganic sulphite X with dilute H2 SO4 generates compound Y. Reaction of Y
with NaOH gives X. Further, the reaction of X with Y and water affords compound Z. Y and Z,
respectively, are: [Main Sep. 06, 2020 (II)]
(A) SO2 and Na2 SO3 (C) SO2 and NaHSO3
(B) SO3 and NaHSO3 (D) S and Na2 SO3
67. Copsider the following sulphure based oxoacids.

H2 SO3 , H2 SO4 , H2 S2 O8 and H2 S2 O7 .
Amongst these oxoacids, the number of those with peroxo (O − O) bond is
[Main July 29, 2022 (II)]
68. Among the following allotropic forms of sulphur, the number of allotropic forms, which will
show paramagnetism is [Main Feb. 24, 2021 (II)]
(A) α-sułphur (B) β-sulphur (C) S2 -form
APNI KAKSHA 77
Topic-3
Group – 17 Elements (Halogen Family)
69. Concentrated HNO3 reacts with Iodine to give [Main July 28, 2022 (II)]
(A) HI, NO2 and H2 O (C) HIO3 , NO2 and H2 O
(B) HIO2 , N2 O and H2 O (D) HIO4 , N2 O and H2 O
70. The interhalogen compound formed from the reaction of bromine with excess of fluorine is a:
[Main July 25, 2022 (I)]
(A) hypohalite (C) perhalate
(B) halite (D) halite
71. Which one of the following correctly represents the order of stability of oxides, X2 O; (X =
halogen ) ? [Main Aug. 31, 2021 (II)]
(A) Br > Cl > I (C) Cl > I > Br
(B) Br > I > Cl (D) I > Cl > Br
72. Arrange the following bonds according to their average bond energies in descending order: C −
Cl, C − Br, C − F, C − I [Main Jan. 08, 2020 (II)]
(A) C − F > C − Cl > C − Br > C − I (B) C − Br > C − I > C − C - > C − F
(C) C − I > C − Br > C − Cl > C − F (D) C − Cl > C − Br > C − I > C − F
73. The number of interhalogens from the following having square pyramidal structure is :
ClF3 , IF7 , BrF5 , BrF3 , I2 Cl6 , IF5 , CIF, CIF5 [Main July 28, 2022 (I)]
74. The number of halogen/(s) forming halic (V) acid is [Main Aug. 31, 2021 (I)]
75. Chlorine reacts with hot and concentrated NaOH and produces compounds (X) and (Y).
Compound (X) gives white precipitate with silver nitrate solution. The average bond order
between Cl and O atoms in (Y) is _______ . [Main Jan. 07, 2020 (I)]
76. Given below are two statements: one is labelled as Assertion A and the other is labelled as
Reason R. [Main June 27, 2022 (II)]
Assertion A : Flourine forms one oxoacid.
Reason R : Flourine has smallest size amongst all halogens and is highly electronegative.
APNI KAKSHA 78
Topic-4: Group-18 Element (Noble Gases)

77. Match List-I with List-II: [Main July 25, 2022 (II)]
List-I List-II
(Molecule) (hybridization; shape)
(A) XeO3 (I) sp3 d; linear
(B) XeF2 (II) sp3 ; pyramidal
(C) XeOF4 (III) sp3 d3 ; distorted octahedra
(D) XeF6 (IV) sp3 d2 ; sqaure pyramidal
78. The reaction in which the hybridisation of the underlined atom is affected is :
[Main Sep. 04, 2020(II)]
(A) H3 PO2 ⎯⎯⎯⎯⎯⎯

→ (B) H2 SO4 + BaCl ⎯⎯⎯
→
Disproportionation 420K
(D) NeF4 + SbF5 ⎯⎯

→
+
(C) NH3 ⎯⎯
H
→
79. Thesum of number of lone pairs of electrons present on the central atoms of XeO3 , XeOF4 and
XeF6 is _______ . [Main July 25, 2022 (II)]
APNI KAKSHA 79
EXERCISE-V (JEE-ADVANCED)
(IIT JEE ASKED QUESTIONS)
Fill in the blanks
1. The hydrolysis of alkyl substituted chlorosilanes given..... [1991]
2. The hydrolysis of trialkychlorosilane R 3 SiCl, yields ...... [1994]
3. One recently discovered allotrope of carbon (e.g., C60 ) is commonly known as .... [1994]
True/False
4. Carbon tetrachloride burns in air when lighted to give phosgene. [1983]
5. Graphite is a better lubricant on the moon than on the earth. [1987]
6. All the Al − Cl bonds in Al2 Cl6 are equivalent. [1989]
7. Diamond is harder than graphite. [1993]
8. The basic nature of the hydroxides of group 13 (Gr. IIIB) decreases progressively down the
group. [1993]
9. The tendency for catenation is much higher for C than for Si. [1993]
10. Complete and balance the following chemical equations - [IIT-1998, 2 M]
(i) P4 O10 + PC15 ⟶
(ii) SnCl4 + C2 H5 Cl + Na ⟶
11. Work out the following using chemical equations [IIT- 1998, 2M]
"Chlorination of calcium hydroxide produces bleaching powder"
12. Hydrogen peroxide acts both as an oxidizing and as a reducing agent in alkaline solution
towards certain first row transition metal ion. Illustrate both these properties of H2 O2 using
chemical equations - [IIT- 1998, 4 M]
13. In the contact process for industrial manufacture of sulphuric acid, some amount of sulphuric
acid is used as a starting material. Explain briefly. What is the catalyst used in the oxidation of
SO2 ? [IIT- 1998,4 M]
14. Give reasons in one or two sentences for each of the following: [1985]
(i) Graphite is used as a solid lubricant,
(ii) Fluorine cannot be prepared from fluorieds by chemical oxidation.
15. Write balanced equations for : [1990]
(i) The preparation of crystalline silicon from SiCl4
(ii) The preparation of phosphine from CaO and white phosphorus
(iii) The preparation of ammonium sulphate from gypsum, ammonia and carbon dioxide.
APNI KAKSHA 80
16. Anhydrous AlCl3 is covalent. From the data given below, predict whether it would remain
covalent or become ionic in aqueous solution. [1997]
Ionisation energy for Al = 5137 kJ mol−1
ΔHhydration for Al3+ = −4665 kJ mol−1
ΔHhydration for Cl− = −381 kJ mol−1
17. Aluminium sulphide gives a foul odour when it becomes damp. Write a balanced chemical
equation for the reaction. [1997]
18. Draw the structure of a cyclic silicate, (Si3 O9 )6− with proper labelling - [IIT-1998]
19. Give reasons for the following in one or two sentences only. [IIT- 1999]
20. Give reason : [IIT- 2000]
Why elemental nitrogen exists as a diatomic molecule whereas elemental phosphorus is a tetra
atomic molecule.
21. Give an exapmle of oxidation of one halide by another halogen. Explain the feasibility of the
reaction. [IIT- 2000]
22. Compounds X on reduction with LiAlH4 gives a hydride Y containing 21.72% hydrogen
alongwith other products. The compound Y reacts with air explosively resulting in boron
trioxide. Identify X and Y. Give balanced reactions involved in the formation of Y and its
reaction with air Draw the structure of Y. [IIT- 2001]
23. Starting from SiCl4 , prepare the following in steps not exceeding the number given in
parenthesis (reactions only) [IIT- 2001]
(i) Silicon (1)
(ii) Linear silicon containing methyl group only (4)
(iii) Na2 SiO3 (3)
24. Write the balanced chemical equation for developing photographic films. [IIT- 2001]
25. Identify (X) in the following synthetic scheme and write their structures. [IIT- 2001]
26. Write the balanced equations for the reactions of the following compounds with water
[2002]
(i) Al4 Cl3 (ii) CaNCN (iii) BF3 (iv) NCl3 (v) XeF3
27. Write the balanced equations for the reactions of the following compounds with water:
[IIT- 2002]
(i) Al4 C3 (ii) CaNCN (iii) BF3 (iv) NCl3 (v) XeF4
APNI KAKSHA 81
28. Identify the following: [IIT- 2003]
Also mention the oxidation state of S in all the compounds.

29. Arrange the following oxides in the increasing order of Bronsted basicity. [IIT- 2004]
Cl2 O7 , BaO, SO3 , CO2 , B2 O3
30. When zeolite, which is hydrated sodium aluminium silicate, is treated with hard water, the
sodium ions are exchanged with : [1990]
(A) H + ions (B) Ca2+ ions (C) SO4 2− ions (D) Mg 2+ ions
31. Which of the following halides is least stable and has doubtful existence ? [1996]
(A) CCl4 (B) Gel4 (C) Snl4 (D) Pbl4
32. The number of P − O − P bonds in cyclic tetrametaphosphoric acid is - [IIT-2000]
(A) Zero (B) Two (C) Three (D) Four
33. The correct order of acidic strength is - [IIT- 2000]
(A) Cl2 O7 > SO2 < P4 O10 (B) CO2 > N2 O5 > SO3
(C) Na2 O > MgO > Al2 O3 (D) K 2 O > CaO > MgO
34. Amongst H2 O, H2 S, H2 Se and H2 Te, the one with the highest boiling point is - [IIT- 2000]
(A) H2 O because of hydrogen bonding
(B) H2 Te because of higher molecular weight
(C) H2 S because of hydrogen bonding
(D) H2 Se because of lower molecular weight.
35. Ammonia can be dried by - [IIT- 2000]
(A) Conc. H2 SO4 (B) P4 O10 (C) CaO (D) Anhydrous CaCl2
36. Which of the following are hydrolysed - [REE 2000]
(A) NCl3 (B) BCl3 (C) CCl4 (D) SiCl4
37. The set with correct order of acidity is - [IIT- 2001]
(A) HClO < HClO2 < HClO3 < HClO4
(B) HClO4 < HClO3 < HClO2 < HClO
(C) HClO < HClO4 < HClO3 < HClO2
(D) HClO4 < HClO2 < HClO3 < HClO
38. The reaction, 3ClO− (aq) ⟶ ClO−
3 (aq) + 2Cl (aq) is an example of -
−
[IIT- 2001]
(A) Oxidation reaction (B) reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction
APNI KAKSHA 82
39. The number of S-S bonds in sulphur trioxide trimer, (S3 O9 ) is - [IIT- 2001]
(A) Three (B) Two (C) One (D) Zero
40. Statement-I : Between SiCl4 and CCl4 , only SiCl4 reacts with water [IIT- 2001]
Because :
Statement-II : SiCl4 is ionic and CCl4 is covalent
(A) If both assertion and reason are correct and reason is the corect explanation of the
assertion
(B) If both assertion and reason are correct, but reason is not the correct explanation of the
assertion
(C) If assertion is correct, but reason is incorrect
(D) If assertion is incorrect, but reason is correct.
41. Polyphosphates are used as water softening agents because they - [IIT- 2002]
(A) Form soluble complexes with anionic species
(B) Precipitate anionic species
(C) Form soluble complexes with cationic species
(D) Precipitate cationic species
42. Identify the correct order of solubility of Na2 S, CuS, and ZnS in aqueous medium- [IIT- 2002]
(A) CuS > ZnS > Na2 S (B) ZnS > Na2 S > CuS
(C) Na2 S > CuS > ZnS (D) Na2 S > ZnS > CuS
43. Identify, the correct order of acidic strength of CO2 , CuO, CaO, H2 O − [IIT- 2002]
(A) CaO < CuO < H2 O < CO2 (B) H2 O < CuO < CaO < CO2
(C) CaO < H2 O < CuO < CO2 (D) H2 O < CO2 < CaO < CuO
44. H3 BO3 is - [IIT- 2002,3]
(A) Monobasic acid and weak Lewis acid (B) Monobasic and weak Bronsted acid
(C) Monobasic and strong Lewis acid (D) Tribasic and weak Bronsted acid
45. When I − is oxidised by MnO−
4 in alkaline medium, I converts into -
−
[IIT- 2003]
(A) IO−
3 (B) I2 (C) IO−
4 (D) IO−
46. Column-I (Change) Column-II (Given change is done by)
(A) Bi3+ ⟶ (BiO)+ (P) Heat [IIT- 2003]
(B) [AlO2 ]− ⟶ Al(OH)3 (Q) Hydrolysis
(C) SiO4−
4 ⟶ Si2 O7
6−
(R) Acidification
(D) (B4 O2−
7 ) ⟶ [B(OH)3 ] (S) Dilution by water
APNI KAKSHA 83
47. (Me)2 SiCl2 on hydrolysis will produce - [IIT- 2003]

(A) (Me)2 Si(OH)2 (B) (Me)2 Si = O
(C) [−O − (Me)2 Si − O −]n (D) Me2 SiCl (OH)
48. Which is the most thermodynamically stable allotropic form of phosphorus? [IIT- 2004]
(A) Red (B) White (C) Black (D) Yellow
49. When PbO2 reacts with conc. HNO3 the gas evolved may be : [IIT- 2004]
(A) NO2 (B) O2 (C) N2 (D) N2 O
50. Which of the following is not oxidised by O3 ? [IIT- 2005]
(A) KI (B) FeSO4 (C) KMnO4 (D) K 2 MnO4
51. Which blue-liquid is obtained on reacting equimolar amounts of two gases at −30∘ C ?
(A) N2 O (B) N2 O3 (C) N2 O4 (D) N2 O5
[IIT- 2005]
52. B(OH)3 + NaOH ⇌ NaBO2 + Na[B(OH)4 ] + H2 O how can this reaction is made to proceed in
forward direction? [IIT- 2006]
(A) Addition of cis 1, 2 diol (B) Addition of borax
(C) Addition of trans 1, 2 diol (D) Addition of Na2 HPO4
53. Among the following, the paramagnetic compound is - [IIT- 2007]

(A) Na2 O2 (B) O3 (C) N2 O (D) KO2
54. Statement-I : Boron always forms covalent bond [IIT-2007]

Because :
Statement-II : The small size of B3+ favours formation of covalent bond.
(A) Statement-I is True, Statement-II is Ture, Statement-II is a correct explanation for
Statement-I
(B) Statement-I is Ture, Statement-II is Ture, Statement-II is not a correct explanation for
Statement-II
(C) Statement-I is Ture, Statement-II is False
(D) Statement-I is False, Statement-II is Ture
APNI KAKSHA 84
55. Statement-I : In water, orthoboric acid behaves as a weak monobasic acid. [IIT-2007]
Statement-II : In water, orthoboric acid acts as a proton donor.
(A) Statement-I is True, Statement-II is Ture, Statement-II is a correct explanation for
Statement-I
(B) Statement-I is Ture, Statement-II is Ture, Statement-II is not a correct explanation for
Statement-II
(C) Statement-I is Ture, Statement-II is False
(D) Statement-I is False, Statement-II is Ture
Comprehension # 1 (Q. 56 to 58)

The noble gases have closed-shell electronic configuration and are monoatomic gases under
normal conditions. The low boiling point of the lighter noble gases are due to weak dispersion
forces between the atoms and the absence of other interatomic interactions. The direct reaction
of xenon with fluorine leads to a series of compounds with oxidation number +2, +4 and +6 .
XeF4 reacts violently with water to give XeO3 . The compounds of xenon exhibit rich
stereochemistry and their geometries can be deduced considering the total number of electron
pairs in the valence shell. [IIT- 2007]
56. Argon is used in arc welding because of its -

(A) Low reactivity with metal (B) Ability to lower the melting point of metal
(C) Flammability (D) High calorific value
57. The structure of XeO3 is -
(A) Linear (B) Planar (C) Pyramidal (D) T-shaped
58. XeF4 and XeF6 are expected to be -

(A) Oxidising agent (B) Reducing agent
(C) Unreactive (D) Strongly basic
Comprehension # 2 (Q.59 to 61)

There are some deposits of nitrates and phosphates in earth's crust. Nitrates are more soluble
in water. Nitrates are difficult to reduce under the laboratory conditions but microbes do it
easily. Ammonia forms large number of complexes with transition metal ions. Hybridization
easily explains the ease of sigma donation capability of NH3 and PH3 . Phosphine is a flammable
gas and is prepared from white phosphorous. [IIT- 2008]
APNI KAKSHA 85
59. Among the following, the correct statement is :-

(A) Phosphates have no biological significance in humans
(B) Between nitrates and phosphates, phosphates are less abundant in earth's crust
(C) Between nitrates and phosphates, nitrates are less abundant in earth's crust
(D) Oxidation of nitrates is possible in soil
60. Among the following, the correct statement is :-

(A) Between NH3 and PH3 , NH3 is a better electron donor because the lone pair of electrons
occupies spherical ' s ' orbital and is less directional
(B) Between NH3 and PH3 , PH3 is a better electron donor because the lone pair of electrons
occupies sp3 orbital and is more directional
(C) Between NH3 and PH3 , NH3 is a better electron donor because the lone pair of electrons
occupies sp3 orbital and is more directional
(D) Between NH3 and PH3 . PH3 is a better electron donor because the lone pair of electrons
occupies spherical ' s ' orbital and is less directional.
61. White phosphorus on reaction with NaOH gives PH3 as one of the products. This is a :-
(A) dimerization reaction (B) disproportionation reaction
(C) condensation reaction (D) precipitation reaction
62. The reaction of P4 with 𝑋 leads selectively to P4 O6 . The X is [JEE 2009]
(A) DryO2 (B) A mixture of O2 , and N2
(C) Moist O2 (D) O2 in the presence of aqueous NaOH
63. The reaction of white phosphorus with aqueous NaOH gives phosphine along with another
phosphorus containing compound. The reaction type ; the oxidation states of phosphorus in
phosphine and the other product are respectively [JEE 2012]
(A) redox reaction ; -3 and -5
(B) redox reaction ; +3 and +5
(C) disproportionation reaction ; -3 and +1
(D) disproportionation reaction ; -3 and +3
64. Bleaching powder contains a salt of an oxoacid as one of its components. The anhydride of that
oxoacid is : [JEE 2012]
(A) Cl2 O (B) Cl2 O7 (C) ClO2 (D) Cl2 O6
APNI KAKSHA 86
65. With respect to graphite and diamond, which of the statement(s) given below is (are) correct ?
(A) Graphite is harder than diamond. [JEE 2012]
(B) Graphite has higher electrical conductivity than diamond.
(C) Graphite has higher thermal conductivity than diamond.
(D) Graphite has higher C − C bond order than diamond.
66. Concentrated nitric acid, upon long standing, turns yellow-brown due to the formation of -
(A) NO (B) NO2 (C) N2 O (D) N2 O4
[JEE 2013]
67. The correct statement(s) about O3 is(are) [JEE 2013]
(A) O − O bond lengths are equal
(B) Thermal decomposition of O3 is endothermic
(C) O3 is diamagnetic in nature
(D) O3 has a bent structure
Comprehension # 3 (Q. 68 and 69)

The reaction of Cl2 gas with cold dilute and hot concentrated NaOH in water give sodium salt of
two (different) oxoacids of chlorine P and Q respectively. The Cl2 gas reacts with SO2 gas , in
presence of charcoal to give a product R. R reacts with white phosphorous to give a compound
S. On hydrolysis, 𝑆 gives as oxoacid of phosphorous 𝑇.
68. R, S and T, respectively are - [JEE 2013]
(A) SO2 Cl2 , PCl5 and H3 PO4 (B) SO2 Cl2 , PCl3 and H3 PO3
(C) SOCl2 , PCl3 and H3 PO2 (D) SO2 Cl2 , PCl5 and H3 PO4
69. P and Q, respectively, are the sodium salts of -
(A) Hypochlorus and chloric acid (B) Hypochlorus and chlorus acid
(C) Chloric and perchloric acids (D) Chloric and hypochlorus acids
70. The unbalanced chemical reactions given in List-I show missing reagent or condition (?) which
are provided in List-II. Match List-I with List-II and select the correct answer using the code
given below the lists :A [JEE 2013]
List-I List-II
?
(P) PbO2 + H2 SO4 ⟶ PbSO4 + O2 + other product (1) NO
?
(Q) Na2 S2 O3 + H2 O ⟶ NaHSO4 + other product (2) I2
? ∘
(R) N2 H4 ⟶ N2 + other product (3) Warm
?
(S) XeF2 ⟶ Xe + Other product (4) Cl2
APNI KAKSHA 87
Code:
𝑃 𝑄 𝑅 𝑆 𝑃 𝑄 𝑅 𝑆
(A) 4 2 3 1 (B) 3 2 1 4
(C) 1 4 2 3 (D) 3 4 2 1
71. Under ambient conditions, the total number of gases released as products in the final step of
the reaction scheme shown below is [JEE Adv. 2014]
(A) 0 (B) 1 (C) 2 (D) 3
72. The product formed in the reaction of SOCl2 with white phosphorous is [JEE Adv. 2014]
(A) PCl3 (B) SO2 Cl2 (C) SCl2 (D) POCl3
73. The correct statements(s) for orthoboric acid is / are - [JEE Adv. 2014]
(A) It behaves as a weak acid in water due to self ionization
(B) Acidity of its aqueous solution increses upon addition of ethylene glycol
(C) It has a three dimensional structure due to hydrogen bonding.
(D) It is a weak electrolyte in water
74. The correct statement(s) regarding, (i) HClO, (ii) HClO2 , (iii) HClO3 and (iv) HClO4 , is(are)
(A) The number of Cl = O bonds in (ii) and (iii) together is two [JEE Adv. 2015]
(B) The number of lone pairs of electrons on Cl in (ii) and (iii) together is three
(C) The hybridization of Cl in (iv) is sp3
(D) Amongst (i) to (iv), the strongest acid is (i)
75. When O2 is adsorbed on a metallic surface, electron transfer occurs from the metal to O2 . The
TRUE, statement (s) regarding this adsorption is (are) [JEE Adv. 2015]
(A) O2 is physisorbed (B) heat is released
(C) occupancy of 𝜋2p
∗
of O2 is increased (D) bond length of O2 is increased
76. Under hydrolytic conditions, the compounds used for preparation of linear polymer and for
chain termination, respectively, are [JEE Adv. 2015]
(A) CH3 SiCl3 and Si(CH3 )4 (B) (CH3 )2 SiCl2 and (CH3 )3 SiCl
(C) (CH3 )2 SiCl2 and CH3 SiCl3 (D) SiCl4 and (CH3 )3 SiCl
APNI KAKSHA 88
77. Three moles of B2 H6 are completely reacted with methanol. The number of moles of boron
containing product formed is - [JEE Adv. 2015]
78. The increasing order of atomic radii of the following group 13 elements is : [JEE Adv. 2016]
(A) Al < Ga < In < Tl (B) Ga < Al < In < Tl
(C) Al < In < Ga < Tl (D) Al < Ga < Tl < In
79. The crystalline form of borax has [JEE Adv. 2016]
(A) Tetranuclear [B4 O5 (OH)4 ]2− unit
(B) All boron atoms in the same plane
(C) Equal number of sp2 and sp3 hybridized boron atoms
(D) One terminal hydroxide per boron atom
80. The nitrogen containing compound produced in the reaction of HNO3 with P4 O10
(A) can also be prepared by reaction of P4 and HNO3 [JEE Adv. 2016]
(B) is diamagnetic
(C) contains one N − N bond
(D) reacts with Na metal producing a brown gas
PARAGRAPH Q.81 to 82
Upon heating KClO3 in the presence of catalytic amount of MnO2 , a gas W is formed. Excess
amount of W reacts with white phosphorus to give X. The reaction of X with pure HNO3 gives Y
and Z. [JEE(Advanced) 2017]
81. W and X are, respectively
(A) O2 and P4 O6 (B) O3 and P4 O10 (C) O3 and P4 O6 (D) O2 and P4 O10
82. Y and Z are, respectively
(A) N2 O4 and HPO3 (B) N2 O3 and H3 PO4
(C) N2 O5 and HPO3 (D) N2 O4 and H3 PO3
83. The compound(s) which generate(s) N2 gas upon thermal decomposition below 300∘ C is (are)
[JEE(Advanced) 2018]
(A) NH4 NO3 (B) (NH4 )2 Cr2 O7 (C) Ba(N3 )2 (D) Mg 3 N2
84. A tin chloride Q undergoes the following reactions (not balanced) [JEE(Advanced) 2019]
Q + Cl− → X
Q + Me3 N → Y
Q + CuCl2 → Z + CuCl
X is a monoanion having pyramidal geometry. Both Y and Z are neutral compounds.
Choose the correct option(s)
APNI KAKSHA 89
(1) There is a coordinate bond in Y

(2) The central atom in 𝑍 has one lone pair of electrons
(3) The central atom in 𝑋 is 𝑠𝑝3 hybridized
(4) The oxidation state of the central atom in Z is +2
85. With reference to aqua regia, choose the correct options(s) [JEE(Advanced) 2019]
(1) Reaction of gold with aqua regia produces NO2 in the absence of air
(2) Reaction of gold with aqua regia produces an anion having Au in +3 oxidation state
(3) Aqua regia is prepared by mixing conc. HCl and conc. HNO3 in 3: 1(v/v) ratio
(4) The yellow colour of aqua regia is due to the presence of NOCl and Cl2
86. The amount of water produced (in g ) in the oxidation of 1 mole of rhombic sulphur by conc.
HNO3 to a compound with the highest oxidation state of sulphur is (Given data : Molar mass of
water = 18 g mol−1 ) [JEE(Advanced) 2019]
87. At 143 K, the reaction of XeF4 with O2 F2 , produces a Xenon compound Y. The total number of
lone pair(s) of electron present on the whole molecule of Y is [JEE(Advanced) 2019]
88. A colorless aqueous solution contains nitrates or two metals, X and Y. When it was added to an
aqueous solution of NaCl, a white precipitate was formed. This precipitate was found to be
partly soluble in hot water to give a residue P and a solution Q. The residue P was soluble in aq.
NH3 and also in excess sodium thiosulfate. The hot solution Q gave a yellow precipitate with KI.
The metals X and Y, respectively, are. [JEE(Advanced) 2020]
(A) Ag and Pb (B) Ag and Cd (C) Cd and Pb (D) Cd and Zn
89. The correct statement(s) related to oxoacids of phosphorous is(are) [JEE(Advanced) 2021]
(A) Upon heating, H3 PO3 undergoes disproportionation reaction to produce H3 PO4 and PH3 .
(B) While H3 PO3 can act as reducing agent, H3 PO4 cannot.
(C) H3 PO3 is a monobasic acid.
(D) The H atom of P − H bond in H3 PO3 is not ionizable in water.
90. Ozonolysis of ClO2 produces an oxide of chlorine. The average oxidation state of chlorine in this
oxide is. [JEE(Advanced) 2021]
APNI KAKSHA 90
91. Dissolving 1.24 g of white phosphorous in boiling NaOH solution in an inert atmosphere gives a
gas Q. The amount of CuSO4 (in g ) required to completely consume the gas Q is______.
[Given: Atomic mass of H = 1, O = 16, Na = 23, P = 31, S = 32, Cu = 63]
92. The reaction of HClO3 with HCl gives a paramagnetic gas, which upon reaction with O3
produces. [JEE(Advanced) 2022]
(A) Cl2 O (B) ClO2 (C) Cl2 O6 (D) Cl2 O7
93. Match the reactions (in the given stoichiometry of the reactants) in List-I with one of their
products given in List-II and choose the correct option. [JEE(Advanced) 2023]
List-I List-II
(P) P2 O3 + 3H2 O → (1) P(O)(OCH3 )Cl2
(Q) P4 + 3NaOH + 3H2 O → (2) H3 PO3
(R) PCl5 + CH3 COOH → (3) PH3
(S) H3 PO2 + 2H2 O + 4AgNO3 → (4) POCl3
(5) H3 PO4
(A) P → 2; Q → 3; R → 1; S → 5 (B) P → 3; → Q → 5; R → 4; → 2
(C) P → 5; Q → 2; R → 1; S → 3 (D) P → 2; Q → 3; R → 4; S → 5
94. Consider the following molecules: Br3 O8 , F2 O, H2 S4 O6 , H2 S5 O6 , and C3 O2 . Count the number
of atoms existing in their zero oxidation state in each molecule. Their sum is
APNI KAKSHA 91
ANSWER KEY
EXERCISE-I
1. C 2. C 3. B 4. A 5. B 6. B 7. D
8. C 9. B 10. B 11. A 12. A 13. A 14. B
15. B 16. A 17. B 18. A 19. A 20. A 21. B
22. C 23. B 24. D 25. A 26. A 27. B 28. B
29. C 30. B 31. A 32. D 33. A 34. B 35. C
36. C 37. B 38. C 39. B 40. D 41. A 42. A
43. B 44. C 45. A 46. C 47. A
EXERCISE-II
1. A,B 2. A,B,C 3. A,C,D 4. A,B,C 5. A,B,D 6. A,B
7. A,B,C 8. A,B,C 9. A,B,C,D 10. A, C, 11. A,B,C,D
12. C,D 13. C,D 14. A,B,C,D 15. A,B,D 16. B,C,D
17. A,B,C,D
EXERCISE-III
1. B 2. A 3. D 4. A 5. C 6. D 7. A
8. B 9. A 10. A 11. C 12. B 13. B 14. C
15. B 16. B 17. C 18. A
EXERCISE-IV(JEE-MAIN)
1. 4 2. 4 3. 2 4. 3 5. 4 6. 2 7. 3
8. 2 9. 2 10. 3 11. 2 12. 3 13. 3 14. 1
15. 4 16. 3 17. 2 18. 3 19. 3 20. 2 21. 3
22. 4 23. 2 24. 1 25. 3 26. 4 27. 2 28. 2
29. 3 30. 1 31. 3 32. 1 33. 1 34. 3 35. 4
36. 4 37. 2 38. 2 39. 3 40. 2 41. 2 42. 2
43. 4 44. 4 45. 2 46. 3 47. 4 48. 3 49. 1
50. 1 51. 3 52. 3 53. 1 54. 3 55. 4 56. 2
Topic – 1
Group -15 Elements (Nitrogen Family)
57. B 58. D 59. D 60. B 61. 2 62. 2 63. C
64. A
Topic – 2
65. A 66. C 67. 1 68. 1
APNI KAKSHA 92
Topic-3
69. C 70. B 71. D 72. A 73. 3 74. 3
75. 1.67 76. A
Topic-4
Group-18 Element (Noble Gases)
77. A 78. D 79. 3
EXERCISE-IV (JEE- ADVANCED)

Fill in the blanks
1. Silicones 2. R 3 Si(OH) 3. Buckminstre fullerene
True/False
4. F 5. T 6. 𝐹 7. T 8. 𝐹 9. T
Subjective
10. (i) P4 O10 + 6PCl3 ⟶ 10POCl3
(ii) SnCl4 + 2C2 H5 Cl + 2Na ⟶ Na2 SnCl6 + C4 H10
11. 3Ca(OH)2 + 2Cl2 ⟶ Ca(OCl)2 + Ca(OH)2 CaCl2 ⋅ 2H2 O
Bleaching powder is a mixture of CaOCl2

And hydrated basic calcium chloride.
12. When H2 O2 acts as oxidizing agent, therefore, following reaction takes place:
H2 O2 + 2e− ⟶ 2OH −
while, regarding is action on reducing agent, the following reaction takes place :
H2 O2 + 2OH − ⟶ O2 + 2H2 O + 2e−
Oxidizing character:
2Cr(OH)3 + 4NaOH + 3H2 O2 ⟶ 2Na2 CrO4 + 8H2 O
Reducing character:
2K 3 [Fe(CN)6 ] + 2KOH + H2 O2 ⟶ 2 K 4 [Fe(CN)6 ] + 2H2 O + O2
13. In SO3 + H2 O ⟶ H2 SO4 reaction, H2 SO4 is obtained in misty form and reaction is
explosive (highly exothermic). By adding H2 SO4 the above reaction is prevented.
H2 SO4 + SO3 ⟶ H2 S2 O7 (oleum)
APNI KAKSHA 93
H2 S2 O7 + H2 O ⟶ 2H2 SO4
The catalyst used is V2 O5 and K 2 O is used as promotor for the oxidation of SO2 into SO3 .
14. (i) Graphite, hexagonal planes are held by weak van der Waals forces. Since these forces
are overcome, one plane slides over the other. This explains the lubricating properties of
graphite.
(ii) Fluoride has negative oxidation potential
2 F − ⟶ F2 + 2e− , EOP = −2.87 volts
Hence, fluoride is the poorest reducing agent.
Hence, 𝐹2 can't be prepared by oxidation of HF by even strong oxidising agents such as
KMnO4 , MnO2 etc.
Δ
15. (i) 3SiCl4 + 4Al ⟶ 4AlCl3 + 3Si
vapour molten volatilized
Δ
(ii) 15CaO + 4P4 ⟶ 5Ca3 P2 + 3P2 O5 ↑
[Ca3 P2 + 6H2 O → 3Ca(OH)2 + 2PH3 ↑] × 5
15CaO + 4P4 + 30H2 O → 15CaO(OH)2 + 3P2 O5 ↑ +10PH3 ↑
(iii) 2NH3 + CO2 + H2 O → (NH4 )2 CO3
CaSO4 + (NH4 )2 CO3 → CaCO3 ↓ (NH4 )2 SO4
gypsum
CaSO4 + 2NH3 + CO2 + H2 O → CaCO3 ↓

+(NH4 )2 SO4
16. Total hydration energy of Al3+ and 3Cl− ions of AlCl3
(ΔHhydration )
= ( Hydration energy of Al3+ + 3 × hydration energy of Cl− )
= [−4665 + 3(−381)]kJmol−1 = 5808 kJ mol−1
This amount of energy is more than that required for the ionisation of Al into Al3+
(Ionisation energy of Al to Al3+ ). Due to this reason, AlCl3 becomes ionic in aqueous
solution. In aqeous solution, it exists in ionic form as below :
AlCl3 + 6H2 O ⟶ (Al(H2 O)3+
6 + 3Cl
−
17. Al2 S3 + 6H2 O → 2Al(OH)3 ↓ +3H2 S

foul odour
Foul odour, on damping of Al2 S3 is due to formation of H2 S gas.
18. In cyclic (Si3 O9 )6− , three tetrahedral of SiO4 are joined together by sharing of two
oxygen atoms per tetrahedral.
Structure of (Si3 O6−
9 )
APNI KAKSHA 94
In it dark circles (·) represent Si and open circles (O) represent oxygen atom or iron.
19. BeCl2 is hydrolysed due to high polarising power and presence of vacant p-orbitals in Be
atom. (Be = 1 s 2 , 2 s 2 , 2p1x , 2p0y , 2p0z )
20. In nitrogen, d-orbitals are not present, so in it the possiblity of intramolecular
multiplicityy exists which leads to the completion of octet through 𝜋-bond between two
nitrogen atoms. In phosphorus, d-orbitals are present, so in it due to large size of P, the
P − P bonds are longer and hence intramolecular multiplicity is ruled out. So, for the
completion of octet, it forms the bonds with three other ' P ' atoms. Hence due to this
reason it shows molecular formula as P4.
21. 2I − (aqueous) +Cl2 ⟶ I2 + 2Cl− (aqueous)

(i) 2I− (aqueous) ⟶ I2 (s) +2e−
(ii) Cl2 ( g) + 2e− ⟶ 2Cl− (aq)
Thus, I − is oxidised into I2 by Cl2 due to higher oxidised potential of Cl2 than I2
22. X: BCl3
Y: B2 H6
4BCl3 + 3LiAlH4 ⟶ 3AlCl3 + 3LiCl + 2 B2 H6
X
B2 H6 + 3O2 ⟶ B2 O3 + 3H2 O (exothermic)
Y
23. (i) 3SiCl4 + 4Al ⟶ 3Si + 4AlCl3 (in one step)
(ii) SiCl4 + 2Mg ⟶ 2MgCl2 + Si
Si + Cu ⟶ Si − Cu
2CH3 Cl + Si − Cu ⟶ (CH3 )2 SiCl2 + Cu
(CH3 )2 SiCl2 + 2H2 O ⟶ (CH3 )2 Si(OH)2 + 2HCl
APNI KAKSHA 95
(iii) SiCl4 + 4H2 O ⟶ Si(OH)4 + 4HCl

Si(OH)4 ⟶ SiO2 + 2H2 O
Δ
SiO2 + Na2 CO3 1673 K Na2 SiO3 + CO2
24. Unreacted AgBr is removed by hypo (Na2 S2 O3 )

AgBr + 2Na2 S2 O3 ⟶ Na3 [Ag(S2 O3 )2 ] + NaBr
25. 14CO2
26. (i) Al4 Cl3 + 12H2 O ⟶ 4Al(OH)3 + 3CH4 ↑

(ii) CaNCN + 3H2 O ⟶ CaCO3 ↓ +2NH3
(iii) 4BF3 + 3H2 O ⟶ H3 BO3 + 3HBF4
boric acid foricacid
(iv) NCl3 + 3H2 O ⟶ NH3 + 3HOCl

hypochlorous acid
(v) 2XeF4 + 3H2 O ⟶ Xe + XeO3 + F2 + 6HCl

xenon trioxide
27. (i) Al4 C3 + 12H2 O ⟶ 4Al(OH)3 + 3CH4

(ii) CaNCN + 3H2 O ⟶ CaCO3 + 2NH3
(iii) BF3 + 3H2 O ⟶ H3 BO3 + 3HF
3HF + 3BF3 ⟶ 3HBF4
4BF3 + 3H2 O ⟶ H3 BO3 + 3HBF4
28. Oxidation state
(A) : NaHSO3 + 4
(B) : Na2 SO3 + 4
(C) : Na2 S2 O3 + 2
(D) : Na2 S4 O6 + 2.5
29. Cl2 O7 < SO3 < CO2 < B2 O3 < BaO
objective
44. A 45. A
46. (A) → Q, S;; B ) → R, S;; (C) → P; (D) → Q, R
47. C 48. C 49. B 50. C 51. B 52. A 53. D
APNI KAKSHA 96
54. A
Boron always forms covalent bond because boron requires very high energy of form B 3+
and again B3+ due to its very small size having high polarising power thus cause greater
polarisation and eventually significant covalent characteristics-Fajans rule.
55. C
Comprehension # 𝟏(𝐐. 𝟓𝟔 to 58)

56. A 57. C 58. A
Comprehension # 𝟐(𝐐. 𝟓𝟗 to 61)
59. C 60. C 61. B 62. B 63. C 64. A 65. B,D
66. B 67. A,C,D
Comprehension # 3 (Q. 68 and 69)
75. B, C, D 76. B 77. 6
78. B
Sol. The order of radius of 13th group elements is Ga < Al < In < Tl.
Reason ⇒ Due to poor shielding effect of d-orbital, radius of Ga is smallar than Al.
79. (A, C, D)
(A) Having [B4 O5 (OH)4 ]2− tetranuclear (boron) unit

(B) All boron atoms not in same plane
(C) Two boron are sp2 hybridised and two boron are sp3 hybridised
(D) One terminal hydroxide per boron atom is present.
80. B,D
dehydration HNO3
Sol. P4 O10 + 4HNO3 ⟶ 4(HPO3 ) + 2 N2 O5
(requiredproduct)
(A) P4 + 20HNO3 → 4H3 PO4 + 20NO2 ↑ +4H2 O

(B) N2 O5 is diamagnetic in nature
APNI KAKSHA 97
(D) Na + N2 O5 → NaNO3 + NO2 ↑

81. D 82. C 83. B, C 84. 1,3 85. 2,3,4 86. 1 87. 19
88. A 89. A,B,D 90. 6 91. 2.38 92. C 93. D 94. 6
APNI KAKSHA 98
SOLUTION JEE MAINS

Topic – 1
Group -15 Elements (Nitrogen Family)
57. (B) When white phosphorous reacts with SOCl2 , it form phosphorous trichloride.
P4 + 8SOCl2 → 4PCl3 + 4SO2 + 2 S2 Cl2
58. (D) Pyrophosphoric acid is H4 P2 O7 with highest number of oxygen atoms.
59. (D) Red phosphrous is obtained by heating white phosphorous at 573 K in inert atmosphere.
When red phosphorous is heated in a sealed tube at 803 K, we get α-black phosphorous.
β-Black phosphorous is prepared by heating white phosphorous at 473 K under high pressure.
60. (B) P4 + 3NaOH + 3H2 O → PH3 + 3NaH2 PO2

The oxoacid formed in the product of above reaction is sodium salt of phosphinicacid.
61.
Number of non-ionisable protons in 'B' are 2.
62.
Number of ionisable protons in B = 2
APNI KAKSHA 99
63. (C)
Name of oxo acids Oxidation state
Hypophosphorous acid (H3 PO2 ) +1
Orthophosphorous acid (H3 PO3 ) +3
Hypophosphoric acid (H4 P2 O6 ) +4
Orthophosphoric acid (H3 PO4 ) +5
64. (A) As positive oxidation state increase, the acidic character increases.
Pentavalent oxides, E2 O5 has E in +5 oxidation state. Trivalent oxides; E2 O3 has E in +3
oxidation state. So, Acidic character E2 O5 > E2 O3 Down the group non-metallic/acidic
character decreases.
Topic – 2
65. (A) Sulphur have a general tendency to form two double bond.
66. (c) X = Na 2SO3
SO32− + H2SO4 →  H2SO3  → H2O + SO2

(X) (Y)
SO2 + 2NaOH → Na 2SO3 + H2O

(X)
Na 2SO3 + SO2 + H2O → 2NaHSO3

(X) (Y) (Z)
APNI KAKSHA 100

67. If (O.S )actual > (O. S)actual [Peroxy linkage]

(O. S)actual = (O. S)max [ Oxy linkage ]
(O. S)actual < (O. S)max [ Non metal-non-metal bond]
Max O.S of sulphure = +6
For H2 SO3
x + 2 − 6 = 0 ⇒ x = +4
For H2 SO4
x + 2 − 8 = 0 ⇒ x = +6
For H2 SO4
x + 2 − 8 = 0 ⇒ x = +6
For H2 S2 O8
2x + 2 − 16 = 0 ⇒ x = 7
For H2 S2 O7
2x + 2 − 14 = 0 ⇒ x = +6
68. (1) α-sulphur and β-sulphur are diamagnetic. S2 -form is paramagnetic.
Topic-3
69. (C) The reaction involved is:
I2 + 10HNO3 (conc) → 2HlO3 + 10NO2 + 4H2 O
APNI KAKSHA 101

70. (B) Br2 + Excess F2 → BrF5

[Hint: Due to high reactivity of BrF5 , it absorbs moisture from surrounding resulting into
formation of HBrO3 ]
71. (D) The stability of oxides of halogens decreases in the order I > Cl > Br
The stability of oxides of iodine is greater than those of chlorine and bromine. Iodine oxygen
bond is stable due to greater polarity of the bond while the stability of the chlorine oxygen
bond is due to multiple bond formation involving d-orbitals of the chlorine atom. Bromine
being in between, lacks both these characteristics. Thus the stability of oxides of halogens
decreases as mentioned above.
1
72. (A) Generally, bond energy ∝ Bond length
So, bond energy order is : C-F > C − Cl > C − Br > C − I

73. (3) AB5 species have square pyramidal structures. Hence, BrF5 , IF5 and ClF5 .
74. (3) The number of halogen forming halic (V) acid is 3. HClO3 , HBrO3 and HIO3 are those acids.
75. 3Cl2 + 6NaOH → 5NaCl+ NaClO3 + 3H2O

Hot \& conc. (X) (Y)
NaCl+ AgNO3 → AgCl + NaNO3

(X) (white ppt.)
Average bond order between Cl and O
5
atom in NaClO3 = 3 = 1.67
76. (A) Due to small size and high electronegativity of fluorine it can not expand its oxidation state
and show only one oxoacid i.e., HOF
Topic-4
Group-18 Element (Noble Gases)
77. (3) S. N of Xe = 4(3 B ⋅ P + 1ℓ. P)
(A) Steric number of Xe = 4 (3B.p. +11 .p.)
Hybridization = sp3 ; shape = pyramidal geometry = tetrahedral
(B) Steric number of Xe = 5 (2B.p. +31. p.) Hybridization = sp3 d; shape = linear geometry =
trigonal bipyramidal
APNI KAKSHA 102
(C) Steric number of Xe = 6 (5B.p. +11. p.) Hybridization = sp3 d2 ; shape = square pyramidal
geometry = octahedral
(D) Steric number of Xe = 7 (6B.P. +11. p.) Hybridization = sp3 d3 Shape = distorted
octahedral
(A) (a) H3 PO2 ⎯⎯⎯⎯⎯⎯ → H3 PO + PH3 (B) H2 SO4 + NaCl ⎯⎯⎯ → Na2 SO4 + 2HCl
Disproportionation 420K
78.
sp3 sp3 sp3 sp3 sp3
⎯ [XeF]+ [SbF6 ]−
(D) XeF4 + 5bF5 ⎯→
+
(C) NH3 ⎯⎯
H
→NH4+
sp3 sp3 sp3d2 sp3d
79. S. N of Xe = 4(3 B. P + 1ℓ. P)
APNI KAKSHA 103

APNI KAKSHA 104

SOLUTION JEE ADVANCED

86. (1) α-sulphur and β-sulphur are diamagnetic. S2 -form is paramagnetic.
87. XeF4 + O2 F2 → XeF6 + O2 x
Shape of XeF6 is distorted octahedral contains one lone pair e− s on central atom 3 lone pair e− s
on each F atom surrounded by Xe.
Total no. of lone pairs: 1 + 18 = 19
88. (A) X: Ag, Y: Pb
AgNO3 ⎯⎯→
NaCl
AgCl (s); PbNO3 ⎯⎯→
NaCl
PbCl2(s)
AgCl(s) + NH3(aq) →  Ag(NH3 )2 

+
(P) soluble
PbCl2 ( s) + KI ⟶ PbI2
(Q) yellow ppt.
AgCl(s) + Na2 S2 O3 ⟶ Na3 [Ag(S2 O3 )2 ] + NaCl
Δ
89. (a) 4H3 PO3 ⟶ 3H3 PO4 + PH3 (correct)
(b) H3 PO4 has "P" in its highest oxidation state, hence cannot act as a reducing agent (correct)
(c) So, it is dibasic acid (incorrect)
(d) The hydrogen which is directly attached to phosphorous does not ionized in water.
90. 2ClO2 + 2O3 → Cl2 O6 + 2O2
APNI KAKSHA 105

Cl2 O6 ⇒ 2x + 6(−2) = 0
91. (2.38) P4 + 3NaOH + 3H2O

(White phosphorous)
⎯⎯⎯⎯Inert
atmosphere
→ PH3  + 3NaH2PO2
phosphine
PH3 : a non-inflammable gas in its Phosphine in water.

When PH3 is absorbed in CuSO4 solution cupric phosphide forms: 2PH3 + 3CuSO4 ⟶ CuP2 +
3H2 SO4 1 mol of P4 = 31 × 4 = 124 g
∴ 1.24 g of white phosphorous = 0.01 mol
∴ 0.01 mol∘ P4 forms 0.01 mol∘ PH3
No. of moles of CuSO4 is required for complete
3
consumption of 0.01 mol = 0.01 × 2 = 15 × 10−3
M.W. of CuSO4 = 159 g/mol

∴ Amount of CuSO4 required = 15 × 10−3 × 159 = 2.38 g
92. (C) 2HClO3 + 2HCl ⟶ 2ClO2 + Cl2 + 2H2 O

(paramegnetic)
2ClO2 + 2O3 ⟶ Cl2 O6 + 2O2
93. Correct option is (D) 𝐏 → 𝟐; Q → 𝟑; 𝐑 → 𝟒; 𝐒 → 𝟓

P2 O3 + H2 O → H3 PO3
P4 + NaOH + H2 O → PH3 + NaH2 PO2
H3 PO2 + H2 O + AgNO3 → H3 PO4 + HNO3 + Ag ↓

Hence :-
P→2
Q→3
R→4
S→5
APNI KAKSHA 106

94.
Total atom with zero oxidation number state are 6 .
APNI KAKSHA 107

Sheet - 02 _ p-Block Group 15th - 18th

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(Inorganic Chemistry)

(i) Reactivity towards hydrogen:

Ques. Why dinitrogen is inert at room temperature ?

Oxidation state Physical

2NaNO2 + 2FeSO4 + 3H2 SO4 Colourless gas,

Dinitrogen trioxide 250 K Blue solid, acidic

Nitrogen dioxide 2 Pb(NO3 )2 ⟶ Brown gas.

Nitrogen tetroxide Cool Colourless solid /

Nitrogen pentaoxide 4HNO3 + P4 O10 Colourless solid,

M = Pb, Cu, Ba, Ca

(ii) NO : Sparingly soluble in water

Hence it is better supporter for combustion

(iii) It is being absorbed by FeSO4 solution.

KMnO4 + NO + H2 SO4 ⟶ K 2 SO4 + MnSO4 + HNO3 + H2 O

C + 4HNO3 → H2 CO3 + 4NO2 + 2H2 O

(ii) Oxidation of metalloids

Similarly, 2HI + 2HNO3 → I2 + 2NO2 + 2H2 O

It readily catches fire in air to give dense white fumes of P4 O10 .

Comparison between White and Red Phosphorus

Property White phosphorus Red phosphorus

Physical state Soft waxy solid. Brittle powder.

Colour White when pure. Red.

Attains yellow colour

Odour Garlic Odourless.

Solubility in water Insoluble. Insoluble.

Solubility in CS2 Soluble Insoluble.

Physiological action Poisonous. Non-poisonous.

Chemical activity Very active. Less active.

Stability Unstable. Stable

Phosphorescence Glows in dark Does not glow in dark.

Molecular formula P4 Complex polymer.

Prepration of white 'P'

meta phosphoric acid

PH4 I + KOH ⟶ KI + PH3 + H2 O

(v) PH3 + 6AgNO3 ⟶ [Ag 3 P ⋅ 3AgNOA3 ↓] + H3 NO3

Ag 3 P ⋅ 3AgNO3 + 3H2 O ⟶ 6Ag ↓ +3HNO3 + H3PO3

(vi) PH3 + 4HCHO + HCl ⟶ [P(CH2 OH)4 ] + Cl−

CaCl2 ⋅ 8NH3 Cu2 Cl2 ⋅ 2PH3 , AlCl3 ⋅ 2PH3 , SnCl4 ⋅ 2PH3

PH3 + 3Ca(OCl)Cl + 3H2 O ⟶ PCl3 + 3HCl + 3Ca(OH)2

PCl5 + H2 O → POCl3 + 2HCl

With hot water it gives phosphoric acid.

Sodium trimetaphosphate (Graham's salt) (glass)

2ZnS + 3O2 → 2ZnO + 2SO2

(vii) (a) 2KI (acidified) +O3 + 2HCl ⟶ I2 + 2KCl + H2 O + O2

2KI + KOI + 2HCl ⟶ 2KCl + I2 + H2O

Ques. Ozone is thermodynamically unstable with respect to oxygen. Explain ?

HYDROGEN PEROXIDE (𝐇𝟐 𝐎𝟐 )

Structure of 𝜶 and 𝜷 sulphur

S8 ring in rhombic sulphur S6 form

(CharcoalC + 2H2 SO4 ⟶ CO2 + 2SO2 + 2H2 O

FLOW DIAGRAM FOR THE MANUFACTURE OF SULPHURIC ACID

(2) Dehydrating Propert :

(3) Oxidizing Nature :

Cu + 2H2 SO4 (conc.) → CuSO4 + SO2 + 2H2 O

(iii) 6NaOH + 4 S ⟶ Na2 S2 O3 + 2Na2 S + 3H2 O

+Cl − water ⟶ SO2−

+Br2 − water ⟶ SO2−

+4OI − + 2OH − ⟶ 2SO2− −

+4Cl2 + 5H2 O ⟶ Na2 SO4 + 8HCl + H2 SO4

First excited state 3 unpaired electron accounts