LAKSHYA JEE AIR (2025)

P-Block
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.
CaX2 (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 ns2np3.
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
(1.9) (1.9)
Metallic Character:
NP As  Sb  Bi
Non-metal Metalloid Metals

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 , , ,  allotropic form

Catenation:
* The group 15 elements also show catenation property but to much smaller extent than carbon. For example
hydrazine (N2H4) has two N atoms bonded together HN3 has three N atoms.
+
H–N=N=N
PHYSICS WALLAH 1
 p-BLOCK
* Among group 15 elements P has the maximum tendency for catenation forming cyclic as well as open
chain compounds consisting of many phosphorous atoms.
P2H4 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,
3HNO2 → HNO3 + H2O + 2NO
(vii) Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and
–3 both in alkali and acid.
4H3PO3 ⎯⎯⎯
Heat

→ 3H3PO4 + 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:

(i) Nitrogen has unique ability to form p – p 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 p–p 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.

PHYSICS WALLAH 2
 p-BLOCK
(ii) Reactivity towards oxygen: All these elements form two types of oxides: E2O3 and E2O5.
Their acidic character decreases down the group. The oxides of the type E2O3 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: EX 3 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, Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide), Na3As (sodium
arsenide), Zn3Sb2 (zinc antimonide) and Mg3Bi2 (magnesium bismuthide).
DINITROGEN:
Preparation:
(a) Commercial preparation:
Dinitrogen is produced commercially by 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.
NH4Cl(aq) + NaNO2(aq) → N2(g) + 2H2O() + NaCl (aq)
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.
(NH4)2Cr2O7 ⎯⎯⎯
Heat
→ N2 + 4H2O + Cr2O3
Note: Very pure nitrogen can be obtained by the thermal decomposition of sodium or barium azide.

Ba(N3)2 ⎯⎯ → Ba + 3N2
2NaN3 ⎯⎯⎯
300ºC
→ 2Na + 3N2

(c) Other preparation

2NH3 + 3NaOCl ⎯→ N2 + 3NaCl + 3H2O
2NH3 + 3Ca(OCl)2 ⎯→ 2N2 + 3CaCl2 + 6H2O
8NH3 + 3Br2 ⎯→ N2 + 6NH4Br
2NO + 2Cu ⎯→ 2CuO + N2
(red, overheated) (Black)
Cl2 passed into liquor NH3
3Cl2 + 2NH3 ⎯→ N2 + 6HCl
6NH3 + 6HCl ⎯→ 6NH4Cl
--------------------------------------
3Cl2 + 8NH3 ⎯→ N2 + 6NH4Cl
In this method conc. of NH3 should not be lowered down beyond a particular limit.
3Cl2 + NH3 ⎯→ NCl3 + 3HCl

(Trimendously explosive)

PHYSICS WALLAH 3
 p-BLOCK
Physical properties:
(i) Dinitrogen is a colourless, odourless, tasteless and non-toxic gas.
(ii) Nitrogen atom has two stable isotopes: 14N and 15N.
(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:
6Li + N2 ⎯⎯⎯
Heat
→ 2Li3N
3Mg + N2 ⎯⎯⎯Heat
→ Mg3N2
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.
CaC2 + N2 ⎯⎯⎯
1100ºC
→ CaNCN + C

nitrolim
It is a very good fertiliser.
2ϴ
N⎯CN
Cyanamide ion
ϴ ϴ
N=C=N
(Ca(NCN) + C) + 3H2O ⎯→ CaCO3 + 2NH3 + C
Slowly decomposes
NH2–CO–NH2
(Intermidiate fomed)
Qus. 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 : Li3N, Na3N, Ca3N2, Mg3N2, Be3N2
Covalent : AlN, BN, Si3N4, Ge3N4, Sn3N4
M = Sc, Ti, Zr, Hf, la
Interstitial :
HCP of FCC

Ammonia:
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.
NH2CONH2 + 2H2O ⎯⎯→ (NH4)2CO3 2NH3+ H2O + CO2

PHYSICS WALLAH 4
 p-BLOCK
(ii) Small scale preparation by the decomposition of ammonium salts when treated with caustic soda or
calcium hydroxide.
2NH4Cl + Ca(OH)2 → 2NH3 + 2H2O + CaCl2
(NH4)2SO4 + 2NaOH → 2NH3 + 2H2O + Na2SO4
(iii) Large scale manufacturing (Haber’s Process)
N2(g) + 3H2(g) 2NH3(g); fHΘ = – 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 × 10 5 Pa (about 200 atm), a
temperature of ~700 K.
* Use of a catalyst such as iron oxide with small amounts of K2O and Al2O3 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.

Flow chart for the manufacture of ammonia

Other preparation:
(i) Nitrate or nitrite reduction : NO3− / NO−2 + Zn or Al + NaOH ⎯→ NH3 + [Zn(OH)4]2– or [Al(OH)4]–
(ii) Metal nitride hydrolysis : N3– + 3H2O ⎯→ 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) + H2O() NH+4 (aq) + OH– (aq)
It forms ammonium salts with acids, e.g., NH4Cl, (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) + 2NH4OH(aq)⎯⎯→Zn(OH)2(s)+ (NH4)2SO4(aq)
(White ppt)
FeCl3(aq) + NH4OH(aq)⎯⎯→Fe2O3.xH2O(s)+ NH4Cl(aq)
(brown ppt)
PHYSICS WALLAH 5
 p-BLOCK
Note-1: Other reactions
CH3COOH is strong acid in liq. NH3 while in water is weak acid.
AcOH Ac O + H+
4NH3 + H+ ⎯→ NH+4
H2O + H+ ⎯→ H3O+
Basisity order NH3 > H2O
more solvation of H+ in NH3.
Note-2: Hydrolysis and Ammonolysis occurs is a same way.

SiCl4 + 4H2O ⎯→ 4HCl + Si(OH)4 ⎯⎯ → SiO2 + 2H2O

SiCl4 + 8NH3 ⎯→ 4NH4Cl + Si(NH2)4 ⎯⎯ → Si3N4 + NH3
Rate of hydrolysis and Ammonolysis will be affected by the presence of HCl vapour & NH4Cl 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 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
Common Methods of Physical Appearance and
Name Formula state
Preparation Chemical nature
of nitrogen
Dinitrogen oxide NH4NO3 ⎯⎯⎯
Heat
→ Colourless gas,
N2O +1
[Nitrogen oxide] N2O + 2H2O neutral
2NaNO2 + 2FeSO4 + 3H2SO4
Nitrogen monoxide
NO +2 →Fe2(SO4)3 + 2NaHSO4 Colourless gas, neutral
[Nitrogen (II) oxide]
+ 2H2O + 2NO
Blue solid, acidic
Dinitrogen trioxide
N2O3 +3 2NO + N2O4 ⎯⎯⎯
→ 2N2O3
250K
Blue liquid (–30ºC)
[Nitrogen (III) oxide]

Nitrogen dioxide 2Pb(NO3)2 ⎯⎯⎯

673K
→ Brown gas.
NO2 +4
[Nitrogen (IV) oxide] 4NO2 + 2PbO + O2 Acidic
Nitrogen tetroxide Cool Colourless solid / liquid,
N2O4 +4 2NO2 N2O4
Heal
[Nitrogen (IV) oxide] acidic
Nitrogen pentaoxide 4HNO3 + P4O10
N2O5 +5 Colourless solid, acidic
[Nitrogen (V) oxide] → 4HPO3 + 2N2O5

PHYSICS WALLAH 6
 p-BLOCK
Structure of Oxides of Nitrogen
Formula Resonance structures Bond Parameters

N2O

NO

N2O3

NO2

N2O4

N2O5

Preparations:
1. N2O
(i) NH4NO3 ⎯→ N2O + H2O
(ii) Zn + HNO3 ⎯→ Zn(NO3)2 + N2O + H2O
(dil.& cold)
2. NO
(i) Cu + HNO3 (1 : 1) ⎯→ Cu(NO3)2 + NO + H2O
hot
(ii) KNO3 + FeSO4 + H2SO4 ⎯→ Fe2(SO4)3 + K2SO4 + NO + H2O

FeSO4 + NO ⎯→ FeSO4 . NO ⎯⎯ → FeSO4 + NO
(iii) Oswald process–Restricted oxidation of NH3.
Industrial process.
4NH3 + 5O2 ⎯⎯⎯⎯⎯
6 atm
750ºC, Pt-Cat
→ 4NO + 6H2O
3. N2O3
(i) HNO3 + As2O3 ⎯→ H3AsO4 + N2O3
NO + NO2
(ii) Cu + HNO3(6M) ⎯→ Cu(NO3)2 + Cool(-30ºC)

Blue liq (N2O3)

4. NO2
 1
(i) M(NO3)2 ⎯⎯ → MO + 2NO2 + O2
2
M = Pb, Cu, Ba, Ca
(ii) (Cu, Pb, Ag) + HNO3 ⎯→ M-nitrate + NO2 + H2O
(hot & conc.)
PHYSICS WALLAH 7
 p-BLOCK
5. N2O5
(i) 2HNO3 + P2O5 ⎯→ 2HPO3 + N2O5
(ii) 4AgNO3 + 2Cl2(dry gas) ⎯→ 4AgCl + 2N2O5 + O2

Properties:
(I) Decoposition Behaviour
500ºC−900ºC
(i) N2O ⎯⎯⎯⎯⎯ → 2N2 + O2
(ii) 2NO ⎯⎯⎯
800ºC
→2N2 + O2
(iii) N2O3 ⎯⎯⎯⎯ ⎯
Room temp.
→NO2 + NO
(Blue liq.) at (–30°C)
(iv) 2NO2 ⎯⎯⎯
620ºC
→ 2NO + O2
N2O4 ⎯⎯⎯ 11ºC
→ 2NO2
(white solid) Brown gas
at(–11ºC)
1
(v) N2O5 ⎯⎯⎯
30ºC
→ N2O5 ⎯⎯⎯
40ºC
→ 2NO2 + O2
2
Colourless yellow
Solid liq.

(II) Reaction with H2O & NaOH

H2O NaOH
(i) N2O: Fairly soluble in water and
produces neutral solution -------
(ii) NO: Sparingly soluble in water
and produces neutral soln. -------
(iii) N2O: 2HNO2
Hence it is known as
NaNO2 anhydride of HNO2 NaNO2
(iv) NO2: HNO2 + HNO3
called as mixed anhydride NaNO2 + NaNO3
(v) N2O5: 2HNO3
called as anhydride of NaNO3
HNO3

Other properties:
Mixture contains
N2O : 2N2O ⎯→ 2N2 + O2 33% O2 compared
To 20% in air

Hence it is better supporter for combustion

S + N2O ⎯→ SO2 + N2
P + N2O ⎯→ P2O5 + N2
Mg + N2O ⎯→ MgO + N2
Na + N2O ⎯→ Na2O + N2
Cu + N2O ⎯→ CuO + N2
H2 + N2O ⎯→ H2O + N2

PHYSICS WALLAH 8
 p-BLOCK
NOTE:
1
(i) It burns : NO + O2 ⎯→ NO2
2
(ii) It supports combustion also for molten sulphur and hot phosphorous.
S + 2NO ⎯→ SO2 + N2
5
2P + 5NO ⎯→ P2O5 + N2
2
(iii) It is being absorbed by FeSO4 solution.
(iv) It is having reducing property.
KMnO4 + NO + H2SO4 ⎯→ K2SO4 + MnSO4 + HNO3 + H2O
(v) NO shows oxidising property also.
SO2 + 2NO + H2O ⎯→ H2SO4 + N2O
H2S + 2NO ⎯→ H2O + S + N2O
3SnCl2 + 2NO + 6HCl ⎯→ 3SnCl4 + 2NH2OH
(Used for NH2OH preparation)
(vi) NO combines with X2 (X2= Cl2, Br2, F2) to produce NOX
2NO + X2 ⎯→ 2NOX
N2O3: No more properties.

(1) It is having oxidising property.

S + NO2 ⎯→ SO2 + NO
P + NO2 ⎯→ P2O5 + NO
C + NO2 ⎯→ CO2 + NO
SO2 + NO2 + H2O ⎯→ H2SO4 + NO
H2S + NO2 ⎯→ H2O + S + NO
CO + NO2 ⎯→ CO2 + NO
NO not formed: 2KI + 2NO2 ⎯→ I2 + 2KNO2

(2) Reducing property of NO2.

KMnO4 + NO2 + H2SO4 ⎯→ K2SO4 + MnSO4 + HNO3 + H2O

not the reduction product of O3

N2O5:
I2 + 5N2O5 ⎯→ I2O5 + 10NO2
I2O5 is used for the estimation of CO
I2O5 + 5CO ⎯→ I2 + 5CO2
N2O5 + NaCl ⎯→ NaNO3 + NO2Cl
This likes proves that N2O5 is consisting of ion pair of NO+2 & NO3−

OXOACIDS OF NITROGEN
H2N2O2 (hyponitrous acid), HNO2 (nitrous acid) and HNO3 (nitric acid). Amongst them HNO3 is the most
important.

PHYSICS WALLAH 9
 p-BLOCK
NITROUS ACID (HNO2)
Preparation:
(a) M-nitrite ⎯⎯⎯⎯⎯
dil.acid
HCl or H SO
→ HNO2
2 4

(b) N2O3 + H2O ⎯⎯⎯→ 2HNO2

Properties:
(a) Oxidising property: Because of its easy oxidation to liberate nascent oxygen, it acts as a strong
oxidant
2HNO2 ⎯⎯⎯→ H2O + 2NO + (O)
2KI + 2HNO2 + 2HCl ⎯⎯⎯→ 2KCl + 2H2O + 2NO + I2
SnCl2 + 2HNO2 + 2HCl ⎯⎯⎯→ SnCl4 + 2NO + 2H2O
SO2 + 2HNO2 ⎯⎯⎯→H2SO4 + 2NO
H2S + 2HNO2 ⎯⎯⎯→ 2H2O + S  + 2NO
2FeSO4 + 2HNO2 + H2SO4 ⎯⎯⎯→ Fe2(SO4)3 + 2NO + 2H2O
(b) Reducing property: Nitrous acid also acts as a reducing agent as it can be oxidised into nitric acid.
HNO2 + (O) ⎯⎯⎯→ HNO3
2KMnO4 + 5HNO2 + 3H2SO4 ⎯⎯⎯→ K2SO4 + 2MnSO4 + 5HNO3 + 3H2O
K2Cr2O7 + 3HNO2 + 4H2SO4 ⎯⎯⎯→ K2SO4 + Cr2 (SO4)3 + 3HNO3 + 4H2O
H2O2 + HNO2 ⎯⎯⎯→ H2O + HNO3
HNO2 + C2H5NH2 ⎯⎯⎯→ C2H5OH + N2 + H2O
5ºC
HNO2 + C6H5 - NH2 · HCl ⎯⎯⎯ → C6H5 N = NCl + 2H2O
Benzene diazonium chloride

NITRIC ACID (HNO3)

It was named aqua fortis (means strong water) by alchemists.

Preparation:
Laboratory Method: By heating KNO3 or NaNO3 and concentrated H2SO4 in a glass retort.
KNO3 / NaNO3 + H2SO4 → 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
4NH3 (g) +5O2(g) ⎯⎯⎯⎯⎯⎯⎯
500K, 9bar
→ 4NO(g) +6H2O(g)
(ii) Nitric oxide thus formed combines with oxygen giving NO2.
2NO(g) + O2(g) 2NO2 (g)
(iii) Nitrogen dioxide so formed, dissolves in water to give HNO3.
3NO2(g) + H2O()⎯⎯→2HNO3(aq) +NO(g)
NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto ~ 68% by mass.
Further concentration to 98% can be achieved by dehydration with concentrated H2SO4.

Birkel and Eyde Process or arc process:

step 1 N2 + O2 ⎯⎯⎯⎯
3000ºC
⎯
Electric Arc
→ 2NO + Heat
step 2 NO + O2 ⎯→ NO2
step 3 NO2 + H2O ⎯→ HNO2 + HNO3
step 4 HNO2 ⎯→ HNO3 + NO + H2O
PHYSICS WALLAH 10
 p-BLOCK
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.
4HNO3 ⎯⎯⎯⎯ Sunlight
→ 4NO2 + 2H2O + 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) + H2O() → H3O+(aq) + NO3− (aq)
Oxidising nature: Nitric acid acts as a strong oxidising agent as it decomposes to give nascent oxygen
easily.
2HNO3 ⎯→ H2O + 2NO2 + [O]
or 2HNO3 ⎯→ H2O + 2NO + 3[O]
(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 ⎯→ H2SO4 + 6NO2 + 2H2O
conc.and hot
(2) Carbon is oxidised to carbonic acid
C + 4HNO3 → H2CO3 + 4NO2 + 2H2O
(3) Phosphorus is oxidised to orthophosphoric acid.
2P + 10HNO3 → 2H3PO4 + 10NO2 + 2H2O
conc. and hot
(4) Iodine is oxidised to iodic acid
I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O
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 → 2H3AsO4 + 10NO2 + 2H2O
or As + 5HNO3 → H3AsO4 + 5NO2 + H2O
conc. and hot
(2) Antimony is oxidised to antimonic acid
Sb + 5HNO3 → H3SbO4 + 5NO2 + H2O
conc. and hot
(3) Tin is oxidised to meta-stannic acid.
Sn + 2HNO3 → H2SnO3 + 4NO2 + H2O

(iii) Oxidation of Compounds:

(1) Sulphur dioxide is oxidised to sulphuric acid
SO2 + 2HNO3 → H2SO4 + 2NO2
(2) Hydrogen sulphiode is oxidised to sulphur
H2S + 2HNO3 → 2NO2 + 2H2O + S
(3) Ferrous sulphate is oxidised to ferric sulphate in presence of H2SO4
6FeSO4 + 3H2SO4 + 2HNO3 → 3Fe2(SO4)3 + 2NO + 4H2O
PHYSICS WALLAH 11
 p-BLOCK
(4) Iodine is liberated from KI.
6KI + 8HNO3 → 6KNO3 + 2NO + 3I2 + 4H2O
(5) HBr, HI are oxidised to Br2 and I2, respectively.
2HBr + 2HNO3 → Br2 + 2NO2 + 2H2O
Similarly, 2HI + 2HNO3 → I2 + 2NO2 + 2H2O
(6) Ferrous sulphide is oxidised to ferric sulphate
FeS + HNO3 → Fe2(SO4)3 + 8NO2 + 4H2O
(7) Stannous chloride is oxidised to stannic chloride is presence of HCl.
2HNO3 + 14H → NH2OH + NH3 + 5H2O
Hydroxylamine
NH3 + HNO3 → NH4NO3
------------------------------------------------------------------------------
7SnCl2 + 14HCl + 3HNO3 → 7SnCl4 + NH2OH + NH4NO3 + 5H2O
(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 + 8 HNO3(dilute) → 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) → Cu(NO3)2 + 2NO2 + 2H2O
4Zn + 10HNO3(dilute) → 4 Zn(NO3)2 + 5H2O + N2O
Zn + 4HNO3(conc.) → Zn(NO3)2 + 2H2O + 2NO2
Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric acid because of the formation of a passive
film of oxide on the surface.

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.
P4 + 3NaOH + 3H2O ⎯⎯→ PH3 + 3NaH2PO2
(Sodium hypophosphite)
P
60º
P P
It readily catches fire in air to give dense white fumes of P4O10.
P
White
Phosphorus
P4 + 5O2 → P4O10
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.
P P P

P P P P P P

P P

Red Phosphorus
PHYSICS WALLAH 12
 p-BLOCK
Black phosphorus:
(i) It has two forms a-black phosphorus and -black phosphorus.
(ii)-Black phosphorus is formed when red phosphorus is heated in a sealed tube at 803K.
(iii)
It can be sublimed in air and has opaque monoclinic or rhombohedral crystals.
(iv)It does not oxidise in air. -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.

Prepration of white ‘P’:

(i) Bone ash or Apatite rock
Ca3(PO4)2 + 3SiO2 3CaSiO3 + P2O5
Both have same formula

2P2O5 + 10C P4 + 10CO 

(Coke) White ‘P’

(ii) Ca3(PO4)2 + 3H2SO4 (conc.) ⎯→ 3CaSO4 + 2H3PO4

H3PO4 ⎯⎯⎯
320ºC
−H O
→ HPO3
2

meta phosphoric acid

12C + 4HPO3 ⎯⎯⎯
1000ºC
→ 2H2  + 12CO +P4
Coke white 'P'

Reactions of 'P':
P + H2SO4 (hot & conc.) ⎯→ H3PO4 + SO2 + H2O
P + KIO3 + H2SO4 ⎯→ H3PO4 + I2 + K2SO4
Reaction with hot metal —
3Na + P ⎯→ Na3P
3Mg + 2P ⎯→ Mg3P2
3Ca + 2P ⎯→ Ca3P2
2Cu + 2P ⎯→ Cu3P2
Al + P ⎯→ AlP
Ca3P2 + H2O ⎯→ M(OH)n + PH3
or Mg3P2
or AlP
PHYSICS WALLAH 13
 p-BLOCK
PHOSPHINE
Preparation:
(i) Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
Ca3P2 + 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 + 3H2O ⎯⎯→ PH3 + 3NaH2PO2
(sodium hypophosphite)
Pure PH3 is non inflammable but becomes inflammable owingto the presence of P 2H4 or P4 vapours. To
purify it from the impurities, it is absorbed in HI to form phosphonium iodide (PH4I) which on treating
with KOH gives off phosphine.

Other preparation:
PH4I + KOH ⎯→ KI + PH3 + H2O
(PH3 + HI) Purest PH3
2AlP + 3H2SO4 ⎯→ Al2(SO4)3 + PH3


4H3PO3 ⎯⎯ → PH3 + 3H3PO4

2H3PO2 ⎯⎯ → PH3 + 3H3PO4

Physical 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 → Cu3P2 + 3H2SO4
3HgCl2 + 2PH3 → Hg3P2 + 6HCl
Phosphine is weakly basic and like ammonia, gives phosphonium compounds with acids e.g.,
PH3 + HBr → PH4Br
(ii) PH3 + O2 ⎯⎯⎯
150º
→ P2O5 + H2O
(iii) PH3 + 3Cl2 ⎯→ PCl3 + 3HCl
(iv) PH3 + 4N2O ⎯⎯⎯⎯
electrical
sparking
→ H3PO4 + 4N2
(v) PH3 + 6AgNO3 ⎯→ [Ag3P • 3AgNO3] + H3NO3
yellow ppt.
Ag3P • 3AgNO3 + 3H2O ⎯→ 6Ag + 3HNO3 + H3PO3
Black ppt.
(vi) PH3 + 4HCHO + HCl ⎯→ [P(CH2OH)4]+Cl–
white/colourless solid
which is used for making
fire-proof cotton fabrics
PHYSICS WALLAH 14
 p-BLOCK
Note:
Like NH3, PH3 also can form addition product.

CaCl2•8NH3, Cu2Cl2•2PH3, AlCl3•2PH3, SnCl4•2PH3

PH3 can be absorbed by Ca(OCl)Cl.

PH3 + 3Ca(OCl)Cl + 3H2O ⎯→ PCl3 + 3HCl + 3Ca(OH)2
2NH3 + 3Ca(OCl)Cl ⎯→ N2 + 3CaCl2 + 3H2O

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 + 2S2Cl2

Properties:
(i) It is a colourless oily liquid
(ii) Hydrolyses in the presence of moisture.
PCl3 + 3H2O → H3PO3 + 3HCl
(iii) It reacts with organic compounds containing –OH group such as CH3COOH, C2H5OH.
3CH3COOH + PCl3 → 3CH3COCl + H3PO3
3C2H5OH + PCl3 → 3C2H5Cl + H3PO3

PHOSPHORUS PENTACHLORIDE
Preparation:
(i) By the reaction of white phosphorus with excess of dry chlorine.
P4 + 10Cl2 → 4PCl5
(ii) By the action of SO2Cl2 on phosphorus.
P4 + 10SO2Cl2 → 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.
PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO4 + 3HCl
PHYSICS WALLAH 15
 p-BLOCK
(iii) When heated, it sublimes but decomposes on stronger heating.
PCl5 ⎯⎯ ⎯
heat
→ PCl3 + Cl2
(iv) It reacts with organic compounds containing –OH group converting them to chloro derivatives.
C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl
CH3COOH + PCl5 → CH3COCl + 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., C2H5Cl, CH3COCl.

OXIDES OF PHOSPHORUS
It forms three important oxides which exist in dimeric forms.

PHOSPHORUS TRIOXIDE (P4O6)

Preparation:
Phosphorus trioxides is formed when phosphorus is burnt in a limited supply of air.
P4 + 3O2 (limited) ⎯⎯→ P4O6

Properties:
(a) Heating in air: On heating in air, it forms phosphorus pentoxide.
P4O6 + 2O2 ⎯⎯→ P4O10
Phosphorus (V) oxide
(b) Action of water: It dissolves in cold water to give phosphorus acid.
P4O6 + 6H2O (cold) ⎯⎯→ 4H3PO3
Phosphorus(III)acid
It is, therefore, considered as anhydride of phosphorus acid.
Note: With hot water, it gives phosphoric acid and inflammable phosphine.

PHOSPHORUS (V) OXIDE (P4O10)

Preparation: It is prepared by heating white phosphorus in excess of air.

P4 + 5O2 (excess) ⎯⎯ → P4O10

Properties:
(a) It is snowy white solid.
(b) Action with water: It readily dissolves in cold water forming metaphosphoric acid.
P4O10 + 2H2O (Cold) ⎯⎯→ 4HPO3
Metaphosphoric acid.
With hot water it gives phosphoric acid.
P4O10 + 6H2O (Hot) ⎯⎯→ 4H3PO4
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.
PHYSICS WALLAH 16
 p-BLOCK
(d) P4O10 is a very strong dehydrating agent and extracts water from many compounds including sulphuric
acid and nitric acid.
2HClO4 ⎯⎯⎯
P4O10
−H O
→ Cl2O7
2

Chlorine (VII) oxide

2CH3CONH2 ⎯⎯⎯
P4O10
−H2O
→ CH3CN
Acetamide Methyl cyanide

Structure:
(a) Its structure is similar to that of P4O6.
(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
Name Formula Oxidation Characteristic Preparation
State of Bonds and
Phosphorus their number
Hypophosphorus H3PO2 +1 One P – OH White P4 + alkali
(Phosphinic) Two P – H
One P = O
Orthophosphorous H3PO3 +3 Two P – OH P2O3 + H2O
(Phosphonic) One P – H
One P = O
Pyrophosphorous H4P2O5 +3 Two P – OH PCl3 + H3PO3
Two P – H
Two P = O
Hypophosphoric H4P2O6 +4 Four P – OH Red P4 + alkali
Two P = O
One P – OH
Orthophosphoric H3PO4 +5 Three P – OH P4O10 + H2O
One P = O
Pyrophosphoric H4P2O7 +5 Four P – OH Heat phosphoric acid
Two P = O
One P – O – P
Metaphosphoric (HPO3)n +5 Three P – OH Phosphorous acid + Br2, heat in
Three P = O a sealed tube
Three P – O – P

Heating Effect:
H3PO2 ⎯⎯⎯
140ºC
→ PH3 + H3PO4
H3PO4 ⎯⎯⎯⎯
gentle heat
200ºC
→ H4P2O7 ⎯⎯⎯⎯
strong heat
320ºC
→ (HPO3)n
orthophosphoric acid Pyrophosphoric acid metaphosphoric acid
PHYSICS WALLAH 17
 p-BLOCK
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.

• Electronic Configuration:
ns2np4 is the general valence shell electronic configuration.

• Atomic and Ionic Radii: Covalent radius : O < S < Se < Te < Po
• Ionisation Enthalpy : O > S > Se > Te > Po (IE1 values)
• Electron Gain Enthalpy : S > Se > Te > Po > O
• Electronegativity : O > S > Se > Te > Po
• 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 p – p overlap thus two O atoms form double
bond O = O. The intermolecular forces in O2 are weak Vander waals force O2 exist as gas. On the other
hand, other elements of family do not form stable p – p 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.
H2O2 H – O – O – H (Poly oxides)
H2S2 H – S – S – H (Polysulphides or polysulphones)
H2S3 H – S – S – S – H
H2S4 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 sp3d hybridisation
and thus, have trigonal bipyramidal structures in which one of the equatorial positions is occupied by a
lone pair of electrons. This geometry is also regarded as see-saw geometry. All elements except selenium
form dichlorides and dibromides. These dihalides are formed by sp3 hybridisation and thus, have tetrahedral
structure. The well known monohalides are dimeric in nature. Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and
Se2Br2. These dimeric halides undergo disproportionation as given below: 2Se2Cl2 → SeCl4 + 3Se

PHYSICS WALLAH 18
 p-BLOCK
DIOXYGEN
(a) Laboratory method
(i) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
2KClO3 ⎯⎯⎯
Heat
MnO
→ 2KCl + 3O2
2

(ii) By the thermal decomposition of the oxides of metals low in the electrochemical series and higher
oxides of some metals.
2Ag2O(s) → 4Ag(s) + O2(g) ; 2Pb3O4(s) → 6PbO(s) + O2(g)
2HgO(s) → 2Hg() + O2(g) ; 2PbO2(s) → 2PbO(s) + O2(g)

(iii) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely divided
metals and manganese dioxide.
2H2O2(aq) → 2H2O() + 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: 16O, 17O and 18O. 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 → 2Al2O3
P4 + 5O2 → P4O10
C + O2 → CO2
2ZnS + 3O2 → 2ZnO + 2SO2
CH4 + 2O2 → CO2 + 2H2O
Some compounds are catalytically oxidised. For example,
2SO2 + O2 ⎯⎯⎯
V2O5
→ 2SO3
4HCl + O2 ⎯⎯⎯
CuCl2
→ 2Cl2 + 2H2O

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.

PHYSICS WALLAH 19
 p-BLOCK
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,
Al2O3) or mixed (Pb3O4, Fe3O4).

Types of simple oxide:

Acidic oxide: An oxide that combines with water to give an acid is termed acidic oxide
(e.g., SO2, Cl2O7, CO2, N2O5).
SO2 + H2O → H2SO3
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., Mn2O7, CrO3, V2O5).

Basic oxide: The oxides which give a base with water are known as basic oxides (e.g., Na2O, CaO, BaO).
In general, metallic oxides are basic. For example, CaO combines with water to give Ca(OH)2, a base.
CaO + H2O → 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.
Al2O3(s) + 6HCl(aq) + 9H2O() → 2[Al(H2O)6]3+(aq) + 6Cl–(aq)

Al2O3(s) + 6NaOH(aq) + 3H2O() → 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 N2O.

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)
(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 H0 (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.
Note:
2F2 + 2H2O ⎯→ 4HF + O2 Ozonised Is separated by passing into spiral tube cooled by liq.
Oxygen air. Ozone condenses at –112.4ºC.
F2 + 3H2O ⎯→ 6HF + O3
[b.p. of O2 –183ºC; b.p. of liq. Air is –190ºC]

PHYSICS WALLAH 20
 p-BLOCK
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 + H2O E° = +2.07 V
It is next to F2. [above 2.07 V, only F2, F2O 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) + H2O()+ 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 + H2O + O2 [X = Cl, Br, I]
(iii) NaNO2 + O3 ⎯→ NaNO3 + O2
Na2SO3 + O3 ⎯→ Na2SO4 + O2
Na2AsO3 + O3 ⎯→ Na2AsO4 + O2
(iv) Moist S, P, As + O3 
S + H2O + 3O3 ⎯→ H2SO4 + 3O2
2P + 3H2O + 5O3 ⎯→ 2H3PO4 + 5O2
2As + 3H2O + 5O3 ⎯→ 2H3AsO4 + 5O2
(v) Moist I2 ⎯→ HIO3 whereas dry iodine ⎯→ I4O9 (yellow)
I2 + 5O3 + H2O ⎯→ 2HIO3 + 5O2
2I2 + 9O3 ⎯→ I4O9 + 9O2
(vi) 2K2MnO4 + O3 + H2O ⎯→ 2KMnO4 + 2KOH + O2
2K4[Fe(CN)6] + O3 + H2O ⎯→ 2K3[Fe(CN)6] + 2KOH + O2
2FeSO4 + O3 + H2SO4 ⎯→ Fe2(SO4)3 + O2 + H2O
(vii) (a) 2KI (acidified) + O3 + 2HCl ⎯→ I2 + 2KCl + H2O + O2
(b) 2KI (neutral) + O3 + H2O ⎯→ I2 + 2KOH + O2

KI + KOI O3 is estimated by this reaction

2KI + KOI + 2HCl ⎯→ 2KCl + I2+ H2O

I2 + 2S2O32− ⎯→ S4 O62− + 2I–

KI + 3O3 ⎯→ KIO3 + 3O2
alk.
KI + 4O3 ⎯→ KIO4 + 4O2
PHYSICS WALLAH 21
 p-BLOCK
(viii) Hg loses its fluidity (tailing of Hg)
2Hg + O3⎯→ Hg2O + O2
similarly 2Ag + O3 ⎯→ Ag2O + O2
Brown
(ix) BaO2 + O3 → BaO + 2O2
H2O2 + O3 ⎯→ H2O + 2O2
Na2O2 + O3 + H2O ⎯→ 2NaOH + 2O2
(x) 2KOH + 5O3 ⎯→ 2KO3 + 5O2 + H2O

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 + 3H2O

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.
(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.

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

Sol. Because its decomposition into oxygen results in the liberation of heat (H is negative) and an increase in
entropy (S is positive). These two effects reinforce each other, resulting in large negative Gibbs energy
change (G) for its conversion into oxygen.

HYDROGEN PEROXIDE (H2O2)

Method of preparation:
(i) Na2O2 + H2O (ice cold water) ⎯→ 2NaOH + H2O2
(ii) BaO2 + H2SO4 ⎯→ BaSO4 + H2O2
Instead of H2SO4, H3PO4 is added now-a-days because H2SO4 catalyses the decomposition of H2O2
whereas H3PO4 favours to restore it.
3BaO2 + 2H3PO4 → Ba3(PO4)2 + 3H2O2 and Ba3(PO4)2 + 3H2SO4 → 3BaSO4 + 2H3PO4
O OH O
C2H5 Et Et

(iii) + H2O2

O OH O

Properties:
(i) Colourless, odourless liquid (b.p.152°)
(ii) Acidic nature : H2O2 + 2NaOH ⎯→ Na2O2 + H2O
H2O2 + Na2CO3 ⎯→ Na2O2 + CO2 + H2O
(iii) It is oxidant as well as reductant.
H2O2 + 2H+ + 2e → 2H2O [reaction in acidic medium]
H2O2 + 2e → 2OH– [rxnn in alkali medium]
PHYSICS WALLAH 22
 p-BLOCK
Oxidising Properties:
(i) PbS + 4H2O2 ⎯→ PbSO4 + 4H2O (Used in washing of oil painting)
(ii) NaNO2 + H2O2 ⎯→ NaNO3 + H2O
Na2SO3 + H2O2 ⎯→ Na2SO4 + H2O
2KI + H2O2 ⎯→ 2KOH + I2
H2S + H2O2 ⎯→ S  + 2H2O
H2SO4 + 2FeSO4 + H2O2 ⎯→ Fe2(SO4)3 + 2H2O
2K4[Fe(CN)6] + H2O2 + H2SO4 ⎯→ 2K3[Fe(CN)6] + K2SO4 + 2H2O

Reducing properties:
(a) Ag2O + H2O2 ⎯→ 2Ag + H2O + O2
(b) O3 + H2O2 ⎯→ H2O + 2O2
(c) MnO2 + H2O2 + H2SO4 → MnSO4 + 2H2O + O2
(d) PbO2 + H2O2 → PbO + H2O + O2
(e) Pb3O4 + 4HNO3 ⎯→ 2Pb(NO3)2 + PbO2 + 2H2O
PbO2 + H2O2 ⎯→ PbO + H2O + O2
PbO + 2HNO3 ⎯→ Pb(NO3)2 + H2O
Pb3O4 + H2O2 + 6HNO3 ⎯→ 3Pb(NO3)2 + 4H2O + O2
(f) X2 + H2O2 ⎯→ 2HX + O2 [X = Cl, Br]
(g) 2[Fe(CN)6]3– + 2OH– + H2O2 ⎯→ 2[Fe(CN)6]4– + 2H2O + O2
(h) NaOCl + H2O2 ⎯→ NaCl + H2O + O2
(i) NaIO4 + H2O2 ⎯→ NaIO3 + H2O + O2
Uses: (i) As a rocket propellant:
NH2.NH2 + 2H2O2 ⎯→ N2 + 4H2O [highly exothermic and large increase in volume]
(ii) In detection of Cr+3, Ti+4 etc.
Ti(SO4)2 + H2O2 + 2H2O ⎯→ H2TiO4 + 2H2SO4
Yellow or orange
Pertitanic acid

ALLOTROPIC FORMS OF SULPHUR

369K
 – sulphur  – sulphur
369K

At 369 K both the forms are stable. This temperature is called transition temperature.

Rhombic sulphur (-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 (-sulphur):

(i) Its m.p. is 393 K and specific gravity 1.98.
(ii) It is soluble in CS2.

PHYSICS WALLAH 23
 p-BLOCK

Structure of  and  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.

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.

SO32− (aq) + 2H+(aq) → H2O() + SO2(g)

Other preparation:
Cu + 2H2SO4 (conc.) ⎯→ CuSO4 + 2H2O + SO2
Hg + H2SO4 ⎯→ HgSO4 + H2O + SO2
2Ag + H2SO4 ⎯→ Ag2SO4 + H2O + SO2
S + 2H2SO4 ⎯→ 3SO2 + 2H2O
(Charcoal)C + 2H2SO4 ⎯→ CO2 + 2SO2 + 2H2O
NaHSO3+ H2SO4 ⎯→ NaHSO4 + H2O + SO2

Industrial method, by-product of the roasting of sulphide ores.

4FeS2(s) + 11O2(g) → 2Fe2O3(s) + 8SO2(g)
The gas after drying is liquefied under pressure and stored in steel cylinders.

PHYSICS WALLAH 24
 p-BLOCK
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) +H2O() H2SO3(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 → Na2SO3 + H2O
Na2SO3 + H2O + SO2 → 2NaHSO3
SO2(g) + Cl2 ⎯⎯⎯⎯→
in presence
of charcoal
SO2Cl2()

SO2 (g)+ O2 (g) ⎯⎯⎯

V2O5
→ 2SO3 (g)

Reducing properties:
When moist, sulphur dioxide behaves as a reducing agent.
2Fe3+ + SO2 + 2H2O → 2Fe2+ + SO24− + 4H+
5SO2 + 2MnO−4 + 2H2O → 5SO24− + 4H+ + 2Mn2+

Bonding in SO2: The molecule of SO2 is angular. It is a resonance hybrid of the two canonical forms:
S S

O O O O
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 (H2S) SULPHURATED HYDROGEN

Preparation:
By the action of dil. HCl or H2 SO4 on iron pyrites.
FeS + H2 SO4 ⎯⎯⎯→ FeSO4 + H2S

Properties:
It is a colourless gas having an offensive smell of rotten eggs.
(a) It burn in air with blue flame
2H2S + O2 ⎯⎯⎯→ 2H2O + S
If the air supply is in excess
2H2S + 3O2 ⎯⎯⎯→ 2H2O + 2SO2
(b) It is a mild acid.
H2S ⎯⎯⎯→ H+ + SH–
SH– ⎯⎯⎯→ H+ + S–2
(c) It act as a reducing agent. It reduces halogen into corresponding hydroacid.
H2S + X2 ⎯⎯⎯→ 2HX + S
PHYSICS WALLAH 25
 p-BLOCK
Tests of H2S:
(a) Unpleasant odour resembling that of rotten eggs.
(b) It turns lead acetate into paper black
(CH3COO)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 H2SO4, KMnO4, K2Cr2O7, O3, H2O2, FeCl3

Note: Drying agent for this gas: fused CaCl2, Al2O3 (dehydrated) P2O5 etc.
But not H2SO4, because
H2SO4 + H2S ⎯→ 2H2O + 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 (V2O5):
The key step in the manufacture of H2SO4 is the catalytic oxidation of SO2 with O2 to give SO3 in the
presence of V2O5 (catalyst).
2SO2 (g) + O2 (g) ⎯⎯⎯
V2O5
→ 2SO3 (g) r HΘ = –196.6 kJ mol–1
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 H2SO4 to produce oleum.
Dilution of oleum with water gives H2SO4 of the desired concentration.
SO3 + H2SO4 → H2S2O7
(Oleum)

Flow diagram for the manufacture of sulphuric acid

The sulphuric acid obtained by Contact process is 96-98% pure.

P2O5 is stronger dehydrating agent than H2SO4 : H2SO4 + P2O5 ⎯→ 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.
PHYSICS WALLAH 26
 p-BLOCK
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.
H2SO4(aq) + H2O() → H3O+(aq) + HSO−4 (aq): K a1 = Very large ( K a1 > 10)

HSO−4 (aq) + H2O() → H3O+(aq) + SO24− (aq); K a 2 = 1.2 × 10–2

(2) Dehydrating Propert:

Concentrated sulphuric acid is a strong dehydrating agent.
C12H22O11 ⎯⎯⎯
H2SO4
Conc.
→ 12C +11H2O

C6H12O6 ⎯⎯⎯→
H2SO4
−6H O
6C
2

(COOH)2 ⎯⎯⎯
H2SO4
−H2O
→ CO + CO2

HCOOH ⎯⎯⎯
−H O
→ CO
2

(3) Oxidizing Nature:

Hot concentrated sulphuric acid is a moderately strong oxidising agent. In this respect, it is intermediate
between phosphoric and nitric acids.
Cu + 2H2SO4(conc.) → CuSO4 + SO2 + 2H2O
HBr /HI + H2SO4 (conc.)→Br2/I2 + SO2 + H2O
3S + 2H2SO4(conc.) → 3SO2 + 2H2O
C + 2H2SO4(conc.) → CO2 + 2SO2 + 2H2O
2P + 5H2SO4 (conc.) → H3PO4 + 5SO2

H2SO4 & SO3:

Both gas

SO2 + Cl2 ⎯→ SO2Cl2

H2SO4 + 2PCl5 ⎯→ SO2Cl2 + 2POCl3 + 2HCl

good chlorinating agent
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.

PHYSICS WALLAH 27
 p-BLOCK
SODIUM THIOSULPHATE
Prepn.:
(i) Na2SO3 soln. + S (powder) ⎯⎯⎯
boiling
→ Na2S2O3 ⎯⎯⎯⎯→
eavporation
monoclinic crystal
Na2SO4 + 4C Na2S + 4CO
Salt cake Coke
(ii) SO2 passed into it

Na2S2O3 [3SO2 + 2Na2S ⎯→ 2Na2S2O3 + S]

(iii) 6NaOH + 4S ⎯→ Na2S2O3 + 2Na2S + 3H2O

3Ca(OH)2 + 12 S ⎯→ CaS2O3 + 2CaS5 + 3H2O
(iv) Na2SO3 + Na2S + I2 ⎯→ Na2S2O3 + 2NaI

Props: (i) 4Na2S2O3 ⎯⎯ → Na2S5 + 3Na2SO4

(ii) Na2S2O3 + 2H+ ⎯→ H2S2O3 ⎯⎯ → H2O + SO2 + S  (White turbidity)
Reaction: (i) Na2S2O3 + I2 ⎯⎯⎯⎯⎯→ S4 O62− + 2I–

Na2S2O3 + Cl – water ⎯→ SO24− + S + 2HCl

Na2S2O3 + Br2 – water ⎯→ SO24− + S + 2HBr

Na2S2O3 + 4OI– + 2OH– ⎯→ 2SO24− + 4I– + H2O

Na2S2O3 + 4Cl2 + 5H2O ⎯→ Na2SO4 + 8HCl + H2SO4

HALOGEN FAMILY
GROUP 17 ELEMENTS (F, Cl, Br, I, At)
Electronic Configuration:
The electronic configuration of outermost shell 17th group element is (ns2np5).
• 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

PHYSICS WALLAH 28
 p-BLOCK
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 ns ns nd
In ground state 1 unpaired electron accounts
(other than fluorine) For – 1 or + 1 oxidation states
3 unpaired electron accounts
First excited state For + 3 oxidation states
5 unpaired electron accounts
Second excited state
For + 5 oxidation states

Third excited state 7 unpaired electron accounts

For + 7 oxidation states

(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.

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– → 2F– + X2 (X = Cl, Br or I)
Cl2 + 2X– → 2Cl– + X2 (X = Br or I)
Br2 + 2I– → 2Br– + I2
(1) Reactivity towards water:
2F2(g) + H2O(l) → 4H+(aq) + 4F–(aq) + O2(g)
X2(g) + H2O(l) → HX(aq) + HOX(aq)
(where X = Cl or Br)
4I– (aq) + 4H+(aq) + O2(g) → 2I2(s) + 2H2O(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 O2F2. However, only OF2 is thermally stable at 298 K. These oxides are essentially oxygen
fluorides because of the higher electronegativity of fluorine than oxygen. Both are strong fluorinating
agents. O2F2 oxidises plutonium to PuF6 and the reaction is used in removing plutonium as PuF6 from
spent nuclear fuel.
PHYSICS WALLAH 29
 p-BLOCK
(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, Cl2O, ClO2, Cl2O6 and Cl2O7 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, Br2O, 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, I2O4, I2O5, I2O7 are insoluble solids and decompose on heating. I2O5 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.

FLUORINE
Method of Preparation:
Moissan process: [By electrolysis of KHF2 (which is obtained from CaF2)]
CaF2 + H2SO4 ⎯→ CaSO4 + 2HF KF decreases the m.p. of
HF + KF ⎯→ KHF2 the mix. depending upon
the composition.
KHF2 H2(at cathode) + F2(at anode)

CHLORINE
Preparation:
(i) By electrolysis of aq. NaCl:
2NaCl + 2H2O ⎯→ 2NaOH + H2 + Cl2
at cathode (anode)

2NaCl ⎯⎯⎯⎯
Electrolysis
→ 2Na + Cl2
(Molten) (cathode) (anode)
(ii) By heating manganese dioxide with concentrated hydrochloric acid.
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O
However, a mixture of common salt and concentrated H2SO4 is used in place of HCl.
4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2

(iii) By the action of HCl on potassium permanganate.

2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 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.
4HCl + O2 ⎯⎯⎯
CuCl2
→ 2Cl2 + 2H2O

PHYSICS WALLAH 30
 p-BLOCK
(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 → 4S2Cl2
2Fe + 3Cl2 → 2FeCl3;

Reaction with hydrogen:

It has great affinity for hydrogen. It reacts with compounds containing hydrogen to form HCl.
H2 + Cl2 → 2HCl
H2S + Cl2 → 2HCl + S
C10H16 + 8Cl2 → 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 → 6NH4Cl + N2 ; NH3 + 3Cl2 → NCl3 + 3HCl
(excess) (excess)

Reaction with alkalies:

2NaOH + Cl2 → NaCl + NaOCl + H2O
(cold and dilute)
6 NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2O
(hot and conc.)
5X – + XO3– + 6H+ ⎯→ 3X2 + 3H2O
[X = Cl, Br, I]
Reaction with slaked lime:
With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 → Ca(OCl2) + CaCl2 + 2H2O
The composition of bleaching powder is Ca(OCl)2 .CaCl2.Ca(OH)2.2H2O.
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 + H2O → 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 (CCl3NO2), mustard gas
(ClCH2CH2SCH2CH2Cl).

Cl
Bleaching Powder : Ca
OCl
PHYSICS WALLAH 31
 p-BLOCK
40C
Prepn. : Cl2(g) + Ca(OH)2 ⎯⎯⎯ → Ca(OCl)Cl + H2O
Slakedlime

(a) On long standing it undergoes

(i) auto oxiation 6Ca(OCl)Cl ⎯→ Ca(ClO3)2 + 5CaCl2
(ii) 2Ca(OCl)Cl ⎯⎯⎯
CoCl2
Cat.
→ 2CaCl2 + O2
(iii) Ca(OCl)Cl + H2O ⎯→ Ca(OH)2 + Cl2

Oxidising Prop.:
CaOCl2 + H2S ⎯→ S + CaCl2+ H2O
CaOCl2 + 2FeSO4 + H2SO4 ⎯→ Fe2(SO4)3 + CaCl2 + H2O
CaOCl2 + KNO2 ⎯→ CaCl2 + KNO3
3CaOCl2 + 2NH3 ⎯→ 3CaCl2 + 3H2O + N2
CaOCl2 + 2KI + 2HCl ⎯→ CaCl2 + 2KCl + H2O + I2
CaOCl2 + 2KI + 2AcOH ⎯→ CaCl2 + 2KOAc + H2O + I2
CaOCl2 + Na3AsO3 ⎯→ Na3AsO4 + CaCl2

Reaction with acid:

CaOCl2 + 2HCl ⎯→ CaCl2 + H2O + Cl2 ; Ca(OCl)Cl + H2SO4 ⎯→ CaSO4 + H2O + Cl2
Ca(OCl)Cl + CO2 ⎯→ CaCO3 + Cl2
Note: ClO2 does not dimerise because odd e' undergoes delocalisation (in its own vaccant 3d-orbital)
Cl2O4 (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.
NaCl + H2SO4 ⎯⎯⎯
420K
→ NaHSO4 + HCl
NaHSO4 + NaCl ⎯⎯⎯ 823K
→ Na2SO4 + 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) + H2O(l) → H3O+ (aq) + Cl–(aq) Ka = 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 NH4Cl.
NH3 + HCl → NH4Cl

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 + 2H2O
3Pt + 16H+ + 4NO3– + 18Cl– → 3PtCl62– + 4NO + 8H2O

PHYSICS WALLAH 32
 p-BLOCK
Reaction with salts:
Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates, hydrogencarbonates, sulphites, etc.
Na2CO3 + 2HCl → 2NaCl + H2O + CO2
NaHCO3 + HCl → NaCl + H2O + CO2
Na2SO3 + 2HCl → 2NaCl + H2O + SO2

Uses: (i) It is used in the manufacture of chlorine, NH4Cl 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.,
Cl2 + F2 ⎯⎯⎯
473K
→ 2CIF ; I2 + 3Cl2 ⎯→ 2ICl3
(equalvolume)

Cl2 + 3F2 ⎯⎯⎯

573K
→ 2CIF3 ; Br2 + 3F2 ⎯→ 2BrF3
(excess) (diluted with water)

I2 + Cl2 ⎯→ 2ICl; Br2 + 5F2 ⎯→ 2BrF5

(equimolar) (excess)

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 XX'7 ) anion derived from
the larger halogen.
XX + H2O → HX + HOX

PHYSICS WALLAH 33
 p-BLOCK
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) H2NCN (cyanamide)
–
ONC HONC (Fulminic acid)
–
N3 HN3 (Hydrazoic acid)

CN shows maximum similarities with Cl–, Br–, I–

(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 H2O but soluble in NH3
(vi) forms large no.of complex.e.g. [Cu(CN)4]3– & [CuCl4]–3
[Co(CN)6]–3 & [CoCl6]–3

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 226Ra.
222
88 Ra ⎯⎯
→86 Rn
226
+ 42 He
(vii) He liquid can exist in two forms. I-form when changes to II-form at -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
PHYSICS WALLAH 34
 p-BLOCK
Electronic Configuration:
General electronic configuration of 18 group element is ns2np6 except helium which has 1s2.

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)

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 (1s2) have completely filled ns2np6 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 (1175 kJmol–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.

PHYSICS WALLAH 35
 p-BLOCK
FLUORINEDES OF XENON
Preparation:
Xe(g) + F2 (g) ⎯⎯⎯⎯
673K,1bar
→ XeF2(s)
(xenoninexcess)

Xe(g) + 2F2 (g) ⎯⎯⎯⎯

873K,7bar
→ XeF4(s)
(1:5ratio)
573K,60−70bar
Xe(g) + 3F2 (g) ⎯⎯⎯⎯⎯ ⎯ → XeF6(s)
(1:20ratio)

XeF4 + O2F2 ⎯⎯⎯

143K
→ XeF6 + O2

Physical properties:
XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298 K.

Chemical properties:
(i) Hydrolysis:
2XeF2(s) + 2H2O(l) → 2Xe (g) + 4 HF(aq) + O2(g)
6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
XeF6 + 3H2O → XeO3 + 6 HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2.
XeF6 + H2O → XeOF4 + 2HF
XeF6 + 2H2O → XeO2F→ + 4HF
Note: Hydrolysis in alkaline medium
2XeF2 + 4OH– ⎯→ 2Xe + 4F– + 2H2O + O2
XeF6 + 7OH– ⎯→ HXeO4– + 3H2O + 6F–
Xenate ion
2HXeO4 + 2OH– ⎯→ XeO64–  + Xe + 2H2O + 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)

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 ⎯→ 2XeO2F2 + XeO3 + 2XeF6 ⎯→ 3XeOF4
PHYSICS WALLAH 36
 p-BLOCK
(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.

PHYSICS WALLAH 37
 p-BLOCK
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 + 3N2

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 H2SO4, P2O5 and anh.CaCl2

Sol. because : 2NH3 + H2SO4 ⎯→ (NH4)2SO4
H2O + NH3 + P2O5 ⎯→ (NH4)3PO4
CaCl2 + 8NH3 ⎯→ CaCl2.8NH3
forms adduct
Quick lime is used for this purpose
CaO + H2O ⎯→ 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 N2O4 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 PH4I which shows that it is basic in nature.
PH3 + HI → PH4I
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 + 3H2O → H3PO3 + 3HCl

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 H3PO2 on the basis of its structure?
Sol. In H3PO2, two H atoms are bonded directly to P atom which imparts reducing character to the acid.
PHYSICS WALLAH 38
 p-BLOCK
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. H2S is less acidic than H2Te. 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
* orbitals like O2 and, hence, exhibits paramagnetism.

14. What happens when

(i) Concentrated H2SO4 is added to calcium fluoride
(ii) SO3 is passed through water?
Sol. (i) It forms hydrogen fluoride
CaF2 + H2SO4 → CaSO4 + 2HF
(ii) It dissolves SO3 to give H2SO4.
SO3 + H2O → H2SO4

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–

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 + 3H2O
Yes, chlorine from zero oxidation state is changed to –1 and +5 oxidation states.

19. CaF2 used in HF prepn. must be free from SiO2. Explain.

Ans. CaF2 + H2SO4 ⎯→ CaSO4 + HF
If SiO2 present as impurity
4HF + SiO2 ⎯→ SiF4 + 2H2O 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.
PHYSICS WALLAH 39
 p-BLOCK
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’.

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 XeO2F2 where the oxidation states of all the elements remain
the same as it was in the reacting state.

PHYSICS WALLAH 40
 p-BLOCK

EXERCISE #1
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 Cu3P2 (D) Colorless solution of [Cu(H2O)4]+


2. H3PO2 ⎯⎯ → (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) Mg3N2 (B) MgO (C) Mg2O3 (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. H3PO2 ⎯⎯⎯ → A ⎯⎯⎯ → B ⎯⎯⎯ →
Compound (C) is
(A) H2PO3 (B) H3PO3 (C) (HPO3)n (D) H4P2O7

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. A sulphate of a metal (A) on heating evolves two gases (B) and (C) and an oxide (D). Gas (B) turns K 2Cr2O7
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, Fe2O3, FeCl3 (B) Al2(SO4)3, SO2, SO3, Al2O3, FeCl3
(C) FeS, SO2, SO3, FeSO4, FeCl3 (D) FeS, SO2, SO3 , Fe2(PO4)3, FeCl2

PHYSICS WALLAH 41
 p-BLOCK
11. 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, P4O10, N2 (B) P4, N2O5, N2 (C) P4, P2O3, Ar (D) P4, P2O3, H2

12. First compound of inert gases was prepared by scientist Neil Barthlete in 1962. This compound is
(A) XePtF6 (B) XeO3 (C) XeF6 (D) XeOF4

13. The correct order of acidic strength of oxides of nitrogen is

(A) NO < NO2 < N2O < N2O3 < N2O5 (B) N2O < NO < N2O3 < N2O4 < N2O5
(C) NO < N2O < N2O3 < N2O5 < N2O4 (D) NO < N2O < N2O5 < N2O3 < N2O4

14. When conc. H2SO4 was treated with K4[Fe(CN)6], CO gas was evolved. By mistake, somebody used dilute
H2SO4 instead of conc. H2SO4 then the gas evolved was
(A) CO (B) HCN (C) N2 (D) CO2

15. An inorganic white crystalline compound (A) has a rock salt structure. (A) on reaction with conc. H 2SO4
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, Ag2SO4 (D) Na2CO3, CO2, Ag2CO3

16. Conc. H2SO4 cannot be used to prepare HBr from NaBr because it
(A) reacts slowly with NaBr (B) oxidises HBr
(C) reduces HBr (D) disproportionates HBr

17. Ammonia can be dried by

(A) conc. H2SO4 (B) P4O10 (C) CaO (D) anhydrous CaCl2

18. 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 = NH4Cl (D) X = NH3 and Y = NH4Cl

19. HNO3 + P4O10 ⎯→ HPO3 + A ; the product A is

(A) N2O (B) N2O3 (C) NO2 (D) N2O5

20. Which of the following is the correct order of acidic strength?

(A) Cl2O7 > SO3 > P4O10 (B) CO2 > N2O5 > SO3
(C) Na2O > MgO > Al2O3 (D) K2O > CaO > MgO

21. A gas which exists in three allotropic forms a, b and g is

(A) SO2 (B) SO3 (C) CO2 (D) NH3

22. 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) Mn3O4, MnO2, MnCl2 (B) Pb3O4, PbO2, PbCl2
(C) Fe3O4, Fe2O3, FeCl2 (D) Fe3O4, Fe2O3, FeCl3
PHYSICS WALLAH 42
 p-BLOCK
23. 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
24. NaH2PO4 ⎯⎯⎯⎯ → (NaPO3)3 ⎯⎯⎯ → NaPO3 (liquid melt) ⎯⎯⎯→
rapid
cooling
D(glass)
Sodium trimetaphosphate
Compound (D) is known as
(A) Microcosmic salt (B) Graham’s salt (C) Reimann’s salt (D) Switzer's Salt

25. Three allotropes (A), (B) and (C) of phosphorous in the following change are respectively
473 K
A B
1200 atm

573 K
C
CO2 – atm
(A) white, b-black, red (B) b-black, white, red (C) red, b-black, white (D) red, violet, b-black

26. When an inorganic compound reacts with SO2 in aqueous medium, produces (A). (A) on reaction with
Na2CO3, gives compound (B) which with sulphur, gives a substance (C) used in photography.
Compound (C) is
(A) Na2S (B) Na2S2O7 (C) Na2SO4 (D) Na2S2O3

27. Which is the compound responsible for the flickering light called will-o-the-wisp, some times seen in the
Marsh.
(A) PH3 (B) P2H4 (C) H2S (D) PH3 + H2S

28. The gun powder is consisting of '______' + sulphur + Charcoal what is the missing substance for gun
powder
(A) LiNO3 (B) NH4NO2 (C) KNO3 (D) (A) and (B) mixture

29. A + Br2 → N2 + (B)

NaOH

(A)
if A is a basic gas then identified (A) and (B)
(A) NH3, NH4Br (B) NH3, N2O (C) NH3, N2O5 (D) None of these

30. Assertion: Conc. H2SO4 can not be used to prepare pure HBr from NaBr
Reason: It reacts slowly with NaBr.
(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)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true

PHYSICS WALLAH 43
 p-BLOCK
31. Assertion: Oxygen is more electronegative than sulphur, yet H2S is acidic, while H2O is neutral.
Reason: H–S bond is weaker than O–H bond.
(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)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true

32. Assertion: Chlorine gas disproportionates in hot & conc. NaOH solution.
Reason: NaCl and NaOCl are formed in the above reaction.
(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)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true

33. Assertion: Liquid IF5 conducts electricity.

Reason: Liquid IF5 self ionizes as, 2IF5 IF4+ + IF6–
(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)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true

PHYSICS WALLAH 44
 p-BLOCK

EXERCISE #2
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 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.

3. The species that undergo(es) disproportionation in an alkaline medium is/are

(A) Cl2 (B) MnO2–
4 (C) P4 (D) ClO4–

4. Which of the following reaction produces PH3 :


(A) Ca3P2 + H2O → (B) P4 + NaOH → (C) PH4I + KOH → (D) H3PO2 ⎯⎯ →

5. Which of the following element of chalcogen group can form MX 2 type of compound where X = Cl and
Br:
(A) O (B) S (C) Se (D) Te


6. Ca2B6O11 + Na2CO3 ⎯⎯ → [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 H2O2 in alkaline medium yields a
compound used as brightner in soaps
(C) Hydrolysis of (X) with HCl or H2SO4 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

PHYSICS WALLAH 45
 p-BLOCK

EXERCISE #3
Paragraph for Question No. 1 & 2
A + alkaline solution → B + C
6Cl2 3Cl2

(D) (F) 3H O (D) E+F

2 CH3COOH

1. When D react with C2H5OH then product will be

(A) C2H5Cl, H3PO4 (B) C2H5Cl, H3PO3 (C) CH3COCl, H3PO3 (D) Only H3PO3

2. B can be absorbed by :
(A) Ca(OCl)Cl (B) H2S (C) Both (D) None

Paragraph for Question No. 3 to 6

HCOOH ⎯⎯⎯⎯⎯
373K
Conc.H SO
→ H2O + (X)
2 4

423−1273K
C(s) + H2O ⎯⎯⎯⎯ ⎯→ (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 I2O5 (C) (X) gas is the purifying agent for Ni
(B) Cu2Cl2 is absorber of (X) gas (D) All of these

Paragraph for Question No. 7 to 8

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.

7. 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

PHYSICS WALLAH 46
 p-BLOCK
8. 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

9. Match List-I with List-II

List-I (Chemical reaction) List-II (Name of process)
800C/Pt
(I) 4NH3 + 5O2 ⎯⎯⎯⎯ → 4NO + 6H2O (a) Contact process
230C/CuCl2
(II) 4HCl + O2 ⎯⎯⎯⎯⎯ → 2Cl2 + 2H2O (b) Ostwald's process
450–500/V2O5
(III) 2SO2 + O2 ⎯⎯⎯⎯⎯⎯
→ 2SO3 (c) Deacon's process
Fe+Mo
(IV) 2N2 + 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

10. Column-I (Metal) Column-II (Correct statements)

(P) Fe (1) Produces NO with 20% HNO3
(Q) Cu (2) Produces NH4NO3 with 6% HNO3
(R) Pb (3) Produces NO2 with 70% HNO3
(S) Sn (4) Produces NH4NO3 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

11. 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 + H2O → (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

12. Column-I (Substances) Column-II (Can be prepared by)

(P) O3 (1) Acidification of BaO2 with H3PO4
(Q) Bleaching powder (2) Birkeland Eyde process
(R) H2O2 (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

PHYSICS WALLAH 47
 p-BLOCK

EXERCISE #4 (JEE MAIN)

1. Which products are expected from the disproportionation of hypochlorous acid: [AIEEE-2002]
(A) HClO3 and Cl2O (B) HClO2 and HClO (C) HCl and Cl2O (D) HCl and HClO3

2. Identify the incorrect statement among the following: [AIEEE-2002]

(A) Ozone reacts with SO2 to give SO3
(B) Silicon reacts with NaOH(aq.) in the presence of air to give Na2SiO3 and H2O
(C) Cl2 reacts with excess of NH3 to give N2 and HCl
(D) Br2 reacts with hot and strong NaOH solution to given NaBr, NaBrO4 and H2O

3. 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]
(A) Sodium (B) Magnesium (C) Mercury (D) Tin

4. What may be expected when phosphine gas is mixed with chlorine gas: [AIEEE-2003]
(A) PCl5 and HCl are formed and mixture cools down
(B) PH3 & Cl2 is formed with warming up
(C) The mixture only cools down
(D) PCl3 and HCl are formed and the mixture warms up

5. Concentrated hydrochloric acid when kept in open air sometimes produces a cloud of white fumes. This is
due to: [AIEEE-2003]
(A) Strong affinity of HCl gas for moisture in air results in forming of droplets of liquid solution which
appears like a cloudy smoke
(B) Due to strong affinity for water, conc. HCl pulls moisture of air towards self. The moisture forms
droplets of water and hence the cloud
(C) Conc. HCl emits strongly smelling HCl gas all the time
(D) Oxygen in air reacts with emitted HCl gas to form a cloud of Cl2 gas

6. Which one of the following statements regarding helium is incorrect [AIEEE-2004]

(A) It is used to produce and sustain powerful superconducting magnets
(B) It is used as a cryogenic agent for carrying out experiments at low temperatures
(C) It is used to fill gas balloons instead of hydrogen because it is lighter then hydrogen and
noninflammable
(D) It is used in gas-cooled nuclear reactors

7. The number of hydrogen atoms attached to phosphorus atom in hypophosphorous acid is :

[AIEEE-2005]
(A) Zero (B) Two (C) One (D) Three

8. Regular use of which of the following fertilizer increases the acidity of soil : [AIEEE-2007]
(A) Potassium nitrate (B) Urea
(C) Superphosphate of lime (D) Ammonium sulphate

9. Which one of the following reactions of Xenon compounds is not feasible? [AIEEE-2009]
(A) 2XeF2 + 2H2O → 2Xe + 4HF + O2
(C) XeO3 + 6HF → XeF6 + 3H2O
(B) XeF6 + RbF → Rb[XeF7]
(D) 3XeF4 + 6H2O → 2Xe + XeO3 + 12HF + 1.5O2
PHYSICS WALLAH 48
 p-BLOCK
10. Which of the following statement is wrong? [AIEEE-2011]
(A) Single N–N bond is weaker than the single P–P bond
(B) N2O4 has two resonance structures
(C) The stability of hydrides increases from NH3 to BiH3 in group 15 of the periodic table
(D) Nitrogen cannot form dp-pp bond

11. Which of the following statements regarding sulphur is incorrect? [AIEEE-2011]

(A) At 600°C the gas mainly consists of S2 molceules
(B) The oxidation state of sulphur is never less than +4 in its compounds
(C) S2 molecule is paramagnetic
(D) The vapour at 200°C consists mostly of S8 rings

12. In view of the signs of rG° for the following reactions

PbO2 + Pb → 2 PbO, rG° < 0
SnO2 + Sn → 2 SnO, rG° > 0,
Which oxidation states are more characteristic for lead and tin? [AIEEE-2011]
(A) For lead + 4, for tin + 2 (B) For lead + 2, for tin + 2
(C) For lead + 4, for tin + 4 (D) For lead + 2, for tin + 4

13. The number of S–S bonds in SO3, S2O32 − , S2O62 − and S2O82 − respectively are:
[JEE Main(Online)-2012]
(A) 1, 0, 1, 0 (B) 0, 1, 1, 0 (C) 1, 0, 0, 1 (D) 0, 1, 0, 1

14. Which one of the following depletes ozone layer? [JEE Main(Online)-2012]
(A) NO and freons (B) SO2 (C) CO (D) CO2

15. In which of the following arrangements, the sequence is not strictly according to the property written
against it? [JEE Main(Online)-2012]
(A) CO2 < SiO2 < SnO2 < PbO2 : increasing oxidising power
(B) B < C < O < N : increasing first ionisation enthalpy
(C) NH3 < PH3 < AsH3 < SbH3 : increasing basic strength
(D) HF < HCl < HBr < HI : increasing acid strength

16. Which of the following series correctly represents relations between the elements from X to Y?
X→Y [JEE Main(Online)-2014]
(A) 18Ar → 54Xe Noble character increases
(B) 3Li → 19K Ionization enthalpy increases
(C) 6C → 32Ge Atomic radii increases
(D) 9F → 35Br Electron gain enthalpy with negative sign increases

17. Which of the following statements about the depletion of ozone layer is correct?
[JEE Main(Online)-2014]
(A) 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
(B) The problem of ozone depletion is less serious at poles because NO2 solidifies and is not available for
consuming ClO• radicals
(C) Oxides of nitrogen also do not react with ozone in stratosphere
(D) Freons, chlorofluorocarbons, are inert chemically, they do not react with ozone in stratosphere

PHYSICS WALLAH 49
 p-BLOCK
18. Which of the following xenon-OXO compounds may not be obtained by hydrolysis of xenon fluorides?
[JEE Main(Online)-2014]
(A) XeO2F2 (B) XeO3 (C) XeO4 (D) XeOF4

19. 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 H2O2 acts as a reducing agent in acid
medium? [JEE Main(Online)-2014]
(A) MnO4– (B) SO32 − (C) KI (D) Cr2O72 −

20. Consider the reaction [JEE Main(Online)-2014]

4+ 2+ +
H2SO3(aq) + Sn(aq) + H2O(n) → Sn(aq) + HSO4(aq)
–
+ 3H(aq)
Which of the following statements is correct?
(A) H2SO3 is the reducing agent because it undergoes oxidation
(B) H2SO3 is the reducing agent because it undergoes reduction
(C) Sn4+ is the reducing agent because it undergoes oxidation
(D) Sn4+ is the oxidizing agent because it undergoes oxidation

21. Which of the following compounds has a P-P bond :- [JEE Main(Online)-2015]
(A) H4P2O5 (B) (HPO3)3 (C) H4P2O7 (D) H4P2O6

22. Chlorine water on standing loses its colour and forms :- [JEE Main(Online)-2015]
(A) HCl and HClO2 (B) HCl only (C) HOCl and HOCl2 (D) HCl and HOCl

23. Which among the following is the most reactive? [JEE Main-2015]
(A) I2 (B) ICl (C) Cl2 (D) Br2

24. Which one has the highest boiling point? [JEE Main-2015]
(A) Kr (B) Xe (C) He (D) Ne

25. From the following statements regarding H2O2, choose the incorrect statement: [JEE Main-2015]
(A) It has to be stored in plastic or wax lined glass bottles in dark
(B) It has to be kept away from dust
(C) It can act only as an oxidizing agent
(D) It decomposes on exposure to light

26. The reaction of zinc with dilute and concentrated nitric acid, respectively produces:
[JEE (Main) 2016]
(A) NO2 and N2O (B) N2O and NO2 (C) NO2 and NO (D) NO and N2O

27. The non-metal that does not exhibit positive oxidation state is : [JEE (Main) 2016]
(A) Oxygen (B) Fluorine (C) Iodine (D) Chlorine

28. Which intermolecular force is most responsible in allowing xenon gas to liquefy?
[JEE (Main) Online 2016]
(A) Ionic (B) Instantaneous dipole- induced dipole
(C) Dipole – dipole (D) Ion - dipole
PHYSICS WALLAH 50
 p-BLOCK
29. The following statements concern elements in the periodic table. Which of the following is true?
[JEE (Main) Online 2016]
(A) The group 13 elements are all metals.
(B) For group 15 elements, the stability of +5 oxidation state increases down the group.
(C) All the elements in Group 17 are gases.
(D) Elements of group 16 have lower ionization enthalpy values compared to those of group 15 in the
corresponding periods.

30. Identify the incorrect statement: [JEE (Main) Online 2016]

(A) S8 ring has a crown shape.
(B) The S–S–S bond angles in the S8 and S6 rings are the same
(C) S2 is paramagnetic like oxygen
(D) Rhombic and monoclinic sulphur have S8 molecules.

31. The product obtained when chlorine reacts with cold and dilute aqueous NaOH are:
[JEE-Main 2017]
– – –
(A) ClO and ClO3 (B) ClO2 and ClO3– –
(C) Cl and ClO –
(D) Cl and ClO2–
–

32. In graphite and diamond, the percentage of p-characters of the hybrid orbitals in hybridisation are
respectively: [Main-2018(Online)]
(A) 33 and 25 (B) 33 and 75 (C) 50 and 75 (D) 67 and 75

33. The compound that does not produce nitrogen gas by the thermal decomposition is
[Main-2018(Online)]
(A) (NH4)2SO4 (B) Ba(N3)2 (C) (NH4)2Cr2O7 (D) NH4NO2

34. Good reducing nature of H3PO2 is attributed to the presence of : [Main-2019(Online)]

(A) Two P–H bonds (B) One P–OH bond (C) One P–H bond (D) Two P–OH bonds

35. Among the following reactions of hydrogen with halogens, the one that requires a catalyst is :
[Main-2019(Online)]
(A) H2 + Br2 → 2HBr (B) H2 + F2 → 2HF (C) H2 + I2 → 2HI (D) H2 + Cl2 → 2HCl

36. The pair that contains two P–H bonds in each of the oxoacids is: [Main-2019(Online)]
(A) H4P2O5 and H3PO3 (B) H4P2O5 and H4P2O6 (C) H3PO2 and H4P2O5 (D) H3PO3 and H3PO2

37. Iodine reacts with concentrated HNO3 to yield Y along with other products. The oxidation state of iodine
in Y is: [Main-2019(Online)]
(A) 5 (B) 1 (C) 3 (D) 7

38. Chlorine on reaction with hot and concentrated sodium hydroxide gives : [Main-2019(Online)]
– – – – – –
(A) ClO3 and ClO2 (B) Cl and ClO2 (C) Cl and ClO (D) Cl and ClO3–
–

PHYSICS WALLAH 51
 p-BLOCK
JEE MAINS PYQ-2021-22
39. The number of bridged oxygen atoms present in compound B formed from the following reactions is:
Pb(NO3)2 ⎯⎯⎯
673 K
→ A + PbO + O2

A ⎯⎯⎯⎯
Dimerise
→B
(A) 0 (B) 1 (C) 2 (D) 3

40. Consider the following reaction:

A + alkali → B (Major Product)

If B is an oxoacid of phosphorus with no P–H bond, then A is:

(A) White P4 (B) Red P4 (C) P2O3 (D) H3PO3

41. Polar stratospheric clouds facilitate the formation of:

(A) CIONO2 (B) HOCl (C) ClO (D) CH4

42. The gas produced by treating an aqueous solution of ammonium chloride with sodium nitrite is
(A) NH3 (B) N2 (C) N2O (D) Cl2

43. Given below are two statements: one is labelled as Assertion A and the other is labelled as Reason R.
Assertion A: Flourine forms one oxoacid.
Reason R: Flourine has smallest size amongst all halogens and is highly electronegative In the
light of the above statements, choose the most appropriate answer from the options given below.
(A) Both A and R are correct and R is the correct explanation of A.
(B) Both A and R are correct but R is NOT the correct explanation of A.
(C) A is correct but R is not correct.
(D) A is not correct but R is correct

44. On the surface of polar stratospheric clouds, hydrolysis of chlorine nitrate gives A and B while its reaction
with HCl produces B and C. A, B and C are, respectively
(A) HOCl, HNO3, Cl2 (B) Cl2, HNO3, HOCl
(C) HClO2, HNO2, HOCl (D) HOCl, HNO2, Cl2O

45. Heating white phosphorus with conc. NaOH solution gives mainly
(A) Na3P and H2O (B) H3PO and NaH
(C) P(OH)3 and NaH2PO4 (D) PH3 and NaH2PO2

46. Among the given oxides of nitrogen; N2O, N2O3, N2O4 and N2O5, the number of compound/(s) having N–
N bond is:
(A) 1 (B) 2 (C) 3 (D) 4

47. Which of the following oxoacids of sulphur contains “S” in two different oxidation states?
(A) H2S2O3 (B) H2S2O6 (C) H2S2O7 (D) H2S2O8

48. Nitrogen gas is obtained by thermal decomposition of

PHYSICS WALLAH 52
 p-BLOCK
(A) Ba(NO3)2 (B) Ba(N3)2 (C) NaNO2 (D) NaNO3
49. Given below are two statements:
Statement-I: The pentavalent oxide of group- 15
element. E2O5. is less acidic than trivalent oxide.
E2O3. of the same element.
Statement-II: The acidic character of trivalent
oxide of group 15 elements. E2O3. decreases down the group.
In light of the above statements. Choose most
appropriate answer from the options given below:
(A) Both Statement I and Statement II are true. (B) Both Statement I and Statement II are false.
(C) Statement I true. but statement II is false. (D) Statement I is false but statement II is true.

50. The oxoacid of phosphorus that is easily obtained from a reaction of alkali and white phosphorus and has
two P-H bonds, is:
(A) Phosphonic acid (B) Phosphinic acid
(C) Pyrophosphorus acid (D) Hypophosphoric acid

51. Match List-I with List-II

List-I List-II
(a) N2 (g) + 3H2 (g) → 2NH3 (g) (I) Cu
(b) CO(g) + 3H2 (g) → CH4 (g) + H2O(g) (II) Cu / ZnO − Cr2O3
(c) CO(g) + H2 (g) → HCHO(g) (III) Fex Oy + K2O + Al2O3
(d) CO(g) + 2H2 (g) → CH3OH(g) (IV) Ni
Choose the correct answer from the options given below:
(A) (a)- (II), (b) - (IV), (c) - (I), (d) - (III) (B) (a)- (II), (b) - (I), (c) - (IV), (d) - (III)
(C) (a)- (III), (b) - (IV), (c) - (I), (d) - (II) (D) (a)- (III), (b) - (I), (c) - (IV), (d) - (II)

52. The interhalogen compound formed from the

reaction of bromine with excess of fluorine is a :
(A) hypohalite (B) halate (C) perhalate (D) halite

53. Given below are two statements:

Statement-I: α and β forms of sulphur can change reversibly between themselves with slow heating or
slow cooling.
Statement-II: At room temperature the stable crystalline form of sulphur is monoclinic sulphur.
In the light of the above statements, choose the correct answer from the options given below:
(A) Statement-I is false but Statement-II is true.
(B) Both Statement-I and Statement-II are true.
(C) Both Statement-I is true but Statement-II is false.
(D) Both Statement-I and Statement-II are false.

54. Compound A used as a strong oxidizing agent is amphoteric in nature. It is the part of lead storage batteries.
Compound A is :
(A) PbO2 (B) PbO (C) PbSO4 (D) Pb3O4

55. Which of the following compound CANNOT act as a Lewis base?

PHYSICS WALLAH 53
 p-BLOCK
(A) NF3 (B) PCl5 (C) SF4 (D) ClF3
56. Chemical nature of the nitrogen oxide compound obtained from a reaction of concentrated nitric acid and
P4O10 (in 4 : 1 ratio) is:
(A) acidic (B) basic (C) amphoteric (D) neutral

57. Match List-I with List-II:

List-I List-II
Industrial Process Application
(a) Haber's process (i) HNO3 synthesis
(b) Ostwald's process (ii) Aluminium extraction
(c) Contact process (iii) NH3 synthesis
(d) Hall-Heroult process (iv) H2SO4 synthesis
Choose the correct answer from the options given below:
(A) (a)-(ii), (b)-(iii), (c)-(iv), (d)-(i) (B) (a)-(iii), (b)-(iv), (c)-(i), (d)-(ii)
(C) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) (D) (a)-(iv), (b)-(i), (c)-(ii), (d)-(iii)

58. Match List-I with List-II:

List-I List-II
(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)-(v), (b)-(i), (c)-(ii), (d)-(iii) (B) (a)-(iv), (b)-(i), (c)-(ii), (d)-(iii)
(C) (a)-(iv), (b)-(v), (c)-(ii), (d)-(iii) (D) (a)-(v), (b)-(iv), (c)-(ii), (d)-(iii)

59. A group 15 element, which is a metal and forms a hydride with strongest reducing power among group 15
hydrides. The element is:
(A) Sb (B) P (C) As (D) Bi

60. Which one of the following group-15 hydride is the strongest reducing agent?
(A) AsH3 (B) BiH3 (C) PH3 (D) SbH3

61. The number of ionisable hydrogens present in the product obtained from a reaction of phosphorus
trichloride and phosphonic acid is:
(A) 3 (B) 0 (C) 2 (D) 1

62. Number of Cl = O bonds in chlorous acid, chloric acid and perchloric acid respectively are:
(A) 3, 1 and 1 (B) 4, 1 and 0 (C) 1, 1 and 3 (D) 1, 2 and 3

63. The oxidation states of 'P' in H4P2O7, H4P2O5 and

H4P2O6, respectively, are:
(A) 7, 5 and 6 (B) 5, 4 and 3 (C) 5, 3 and 4 (D) 6, 4 and 5

64. The number of non-ionisable hydrogen atoms present in the final product obtained from the hydrolysis of
PCl5 is:
PHYSICS WALLAH 54
 p-BLOCK
(A) 0 (B) 2 (C) 1 (D) 3
65. The incorrect statement is:
(A) Cl2 is more reactive than ClF.
(B) F2 is more reactive than ClF.
(C) On hydrolysis ClF froms HOCl and HF.
(D) F2 is a stronger oxidizing agent than Cl2 in aqueous solution

66. The number of S = O bonds present in sulphurous acid, peroxodisulphuric acid and pyrosulphuric acid,
respectively are:
(A) 2, 3 and 4 (B) 2, 4 and 3 (C) 1, 4 and 4 (D) 1, 4 and 3

67. Which one of the following correctly represents the order of stability of oxides, X2O; (X = halogen)?
(A) I > Cl > Br (B) Cl > I > Br (C) Br > Cl > I (D) Br > I > Cl

68. Which one of the following is formed (mainly) when red phosphorus is heated in a sealed tube at 803 K?
(A) Yellow phosphorus (B) β-Black phosphorus
(C) α-Black phosphorus (D) White phosphorus

69. In polythionic acid, H2SxO6 (x = 3 to 5) the oxidation state(s) of sulphur is/are:

(A) 0 and +5 only (B) +5 only (C) +6 only (D) +3 and +5 only

70. Which one of the following is used to remove most of plutonium from spent nuclear fuel?
(A) I2O5 (B) BrO3 (C) O2F2 (D) ClF3

71. The correct order of melting points of hydrides of group 16 elements is:
(A) H2S < H2Se < H2Te < H2O (B) H2O < H2S < H2Se < H2Te
(C) H2S < H2Te < H2Se < H2O (D) H2Se < H2S < H2Te < H2O

72. Match List - I with List - II.

List –I List – II
(Processes/Reactions) (Catalyst)

2SO2(g) + O2(g) → 2SO3(g)

(a) (I) Fe(s)

4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)

(b) (II) Pt(s)-Rh(s)

N2(g)+3H2(g) → 2NH3(g)
(c) (III) V2O5

Vegetable oil(l) + H2 → Vegetable ghee(s)

(d) (IV) Ni(s)

Choose the correct answer from the options given

below:
(A) (a)- (III), (b)- (I), (c)- (II), (d)- (iv) (B) (a)- (iii), (b)- (ii), (c)- (i), (d)- (IV)
(C) (a)- (IV), (b)- (III), (c)- (I), (d)- (II) (D) (a)- (IV), (b)- (II), (c)- (III), (d)- (I)

PHYSICS WALLAH 55
 p-BLOCK
73. Which oxoacid of phosphorous has the highest number of oxygen atoms present in its chemical formula?
(A) Pyrophosphorous acid (B) Hypophosphoric acid
(C) Phosphoric acid (D) Pyrophosphoric acid
74. Match List-I with List-II
List-I List-II
Reaction Catalyst
4NH3(g) + 5O2(g) → 4NO(g) + H2O(g)
(a) (I) NO (g)

N2(g) + 3H2(g) → 2NH3(g)

(b) (II) H2SO4

C12H22O11(aq) + H2O(l) → C6H12O6 Fructose)

(c) (III Pt (s)
)
(d) IV Fe(s)
2SO2(g) + O2(g)→ 2SO3(g)

Choose the correct answer from the options given below:

(A) (a)– (II), (b)– (III), (c)– (I), (d)– (IV) (B) (a)– (III), (b)– (II), (c)– (I), (d)– (IV)
(C) (a)– (III), (b)– (IV), (c)– (II), (d)– (I) (D) (a)– (III), (b)– (II), (c)– (IV), (d)– (I)

75. Match List-I with List-II, match the gas evolved during each reaction.
List-I List-II
(a)
( NH4 )2 Cr2O7 ⎯⎯→
 (I) H2

KMnO4 + HCl →
(b) (II) N2

Al + NaOH + H2O →
(c) (III) O2

(d)  (IV) Cl2

NaNO3 ⎯⎯ →
Choose the correct answer from the options given
below:
(A) (a) – (II), (b) – (III), (c) – (I), (d) – (IV) (B) (a) – (III), (b) – (I), (c) – (IV), (d) – (II)
(C) (a) – (II), (b) – (IV), (c) – (I), (d) – (III) (D) (a) – (III), (b) – (IV), (c) – (I), (d) – (II)

76. White phosphorus reacts with thionyl chloride to give

(A) PCl5, SO2 and S2Cl2 (B) PCl3.SO2 and S2Cl2
(C) PCl3, SO2 and Cl2 (D) PCl5, SO2 and Cl2

77. Concentrated HNO3 reacts with Iodine to give

(A) HI, NO2 and H2O (B) HIO2, N2O and H2O
(C) HIO3, NO2 and H2O (D) HIO4, N2O and H2O

78. Dinitrogen and dioxygen. the main constituents of air do not react with each other in atmosphere to form
oxides of nitrogen because
(A) N2 is unreactive in the condition of atmosphere.
(B) Oxides of nitrogen are unstable.
(C) Reaction between them can occur in the presence of a catalyst.
(D) The reaction is endothermic and require very high temperature.

79. Dinitrogen is a robust compound, but reacts at high altitude to form oxides. The oxide of nitrogen that can
damage plant leaves and retard photosynthesis is:
PHYSICS WALLAH 56
 p-BLOCK
− −
(A) NO (B) NO3 (C) NO2 (D) NO2

80. Among the following allotropic forms of sulphur, the number of allotropic forms, which will show
Paramagnetism is ________.
(A) α-sulphur (B) β-sulphur (C) S2-form (D) None
81. Consider the following reactions:
PCl3 + H2O ⎯⎯→ A + HCl
A + H2O ⎯⎯→ B + HCl
number of ionisable protons present in the product B_______.

82. The number of non-ionisable protons present in the product B obtained from the following reaction
is_____.
C2H5OH + PCl3 → C2H5Cl + A

A + PCl3 → B

83. The number of interhalogens from the following having square pyramidal structure is:
ClF3, IF7, BrF5, BrF3, I2Cl6, IF5, ClF, ClF5

84. Consider the following sulphur based oxoacids. H2SO3, H2SO4, H2S2O8 and H2S2O7.
Amongst these oxoacids, the number of those with peroxo(O-O) bond is______.

85. The reaction of white phosphorus on boiling with alkali in inert atmosphere resulted in the formation of
product 'A'. The reaction 1 mol of 'A' with excess of AgNO3 in aqueous medium gives ________ mol(s) of
Ag. (Round off to the Nearest Integer).

86. A xenon compound 'A' upon partial hydrolysis gives XeO2F2 . The number of lone pair of electrons present
in compound A is (Round off to the Nearest integer)

87. The number of halogen (s) forming halic (V) acid is _____.

PYQ-2023
88. Given below are two statements:
Statement-I: Chlorine can easily combine with oxygen to form oxides; and the product has a tendency to
explode.
Statement-II: Chemical reactivity of an element can be determined by its reaction with oxygen and
halogens.
In the light of the above statements, choose the correct answer from the options given below
(A) Statement I is true but Statement II is false
(B) Statement I is false but Statement II is true
(C) Both the Statements I and II are true
(D) Both the Statements I and II are false

89. Which of the Phosphorus oxoacid can create silver mirror from AgNO3 solution?

(A) H 4 P2O6 (B) H 4 P2O5 (C) H4 P2O7 (D) ( HPO3 )n

PHYSICS WALLAH 57
 p-BLOCK

90. "A" obtained by Ostwald's method involving air oxidation of NH3, upon further air oxidation produces "B".
"B" on hydration forms an oxoacid of Nitrogen along with evolution of "A". The oxoacid also produces
"A" and gives positive brown ring test.
Identify A and B, respectively.
(A) NO2, N2O5 (B) N2O3, NO2 (C) NO2, N2O4 (D) NO, NO2
91. Which element is not present in Nessler's reagent?
(A) Iodine (B) Potassium (C) Oxygen (D) Mercury

92. Reaction of thionyl chloride with white phosphorus forms a compound [A], which on hydrolysis gives [B],
a dibasic acid. [A] and [B] are respectively
(A) PCl5 and H3PO4 (B) PCl3 and H3PO3 (C) P4 O6 and H3PO3 (D) P4 O6 and H3PO3

93. Given below are two statements:

Statement-I: Nickel is being used as the catalyst for producing syn gas and edible fats.
Statement-II: Silicon forms both electron rich and electron deficient hydrides.
In the light of the above statements, choose the most appropriate answer from the options given below:
(A) Both the statements I and II are incorrect
(B) Statement I is correct but statement II is incorrect
(C) Statement I is incorrect but statement II is correct
(D) Both the statements I and II are correct

94. Bond dissociation energy of "E-H" bond of the " H2 E " hydrides of group 16 elements (given below),
follows order.
A. O B. S C. Se D. Te
Choose the correct from the options given below:
(A) A  B  D  C (B) D  C  B  A (C) A  B  C  D (D) B  A  C  D

95. Formulae for Nessler's reagent is:

(A) KHgI3 (B) K 2 HgI4 (C) KHg 2 I2 (D) HgI 2

96. KMnO4 oxidises I–in acidic and neutral/faintly alkaline solution, respectively, to
(A) I2 & IO3− (B) I2 & I2 (C) IO3− & I2 (D) IO3− & IO3−

97. Sum of oxidation states of bromine in bromic acid and perbromic acid is _________

PYQ-2024
98. Assertion (A): PH3 has lower boiling point than NH3.
Reason (R) : In liquid state NH3 molecules are associated through vander Waal's forces, but PH3 molecules
are associated through hydrogen bonding.
In the light of the above statements, choose the most appropriate answer from the options given below:
(A) (A) is not correct but (R) is correct
(B) Both (A) and (R) are correct and (R) is the correct explanation of (A)
(C) Both (A) and (R) are correct but (R) is not the correct explanation of (A)
(D) (A) is correct but (R) is not correct

PHYSICS WALLAH 58
 p-BLOCK
99. Among the following oxides of p-block elements, number of oxides having amphoteric nature is
_________.
Cl2O7, CO, PbO2, N2O, NO, Al2O3, SiO2, N2O5, SnO2

100. The strongest reducing agent among the following is:

(A) BiH3 (B) PH3 (C) NH3 (D) SbH3
101. Element not showing variable oxidation state is:
(A) Chlorine (B) Bromine (C) Iodine (D) Fluorine

102. From the given list, the number of compounds with +4 oxidation state of Sulphur is ________.
SO3, H2SO3, SOCl2, SF4, BaSO4, H2S2O7

103. Given below are two statements:

Statement-I: Oxygen being the first member of group 16 exhibits only –2 oxidation state.
Statement-II: Down the group 16 stability of +4 oxidation state decreases and +6 oxidation state increases.
In the light of the above statements, choose the most appropriate answer from the options given below:
(A) Statement I is incorrect but Statement II is correct.
(B) Statement I is correct but Statement II is incorrect
(C) Both Statement I and Statement II are incorrect
(D) Both Statement I and Statement II are correct

104. 1 mole of PbS is oxidised by "X" moles of O3 to get " Y " moles of O2. X + Y = _______.

105. Given below are two statements:

Statement-I: Fluorine has most negative electron gain enthalpy in its group.
Statement-II: Oxygen has least negative electron gain enthalpy in its group.
In the light of the above statements, choose the most appropriate from the options given below
(A) Both Statement I and Statement II are false (B) Both Statement I and Statement II are true
(C) Statement I is false but Statement II is true (D) Statement I is true but Statement II is false

106. Anomalous behavior of oxygen is due to its

(A) large size and high electronegativity (B) small size and high electronegativity
(C) large size and low electronegativity (D) small size and low electronegativity

107. The oxidation number of iron in the compound formed during brown ring test for NO3− ion is

108. Assertion (A): There is a considerable increase in covalent radius from N to P. However from As to Bi
only a small increase in covalent radius is observed.
Reason (R): Covalent and ionic radii in a particular oxidation state increases down the group. In the light
of the above statements, choose the most appropriate answer from the options given below:
(A) Both (A) and (R) are true and (R) is the correct explanation of (A)
(B) (A) is false but (R) is true
(C) (A) is true but (R) is false
(D) Both (A) and (R) are true but (R) is not the correct explanation of (A)

109. Reduction potential of ions are given below:

PHYSICS WALLAH 59
 p-BLOCK

ClO−4 lO−4 BrO−4

E 0 = 1.19 V E 0 = 1.65 V E 0 = 1.74 V
The correct order of their oxidising power is:
(A) BrO−4  IO−4  ClO−4 (B) BrO−4  ClO−4  IO−4
(C) IO−4  BrO−4  ClO−4 (D) ClO−4  IO−4  BrO−4
110. Assertion A: H2Te is more acidic than H2S.
Reason R: Bond dissociation enthalpy of H2Te is lower than H2S.
In the light of the above statements, choose the most appropriate from the options given below:
(A) Both A and R are true and R is the correct explanation of A.
(B) A is true but R is false.
(C) Both A and R are true but R is NOT the correct explanation of A.
(D) A is false but R is true.

111. Choose the correct statements about the hydrides of group 15 elements.
(I) The stability of the hydrides decreases in the order NH3  PH3  AsH3  SbH3 >BiH3
(II) The reducing ability of the hydride increases in the order NH3< PH3<AsH3<SbH3<BiH3
(III) Among the hydrides, NH3 is strong reducing agent while BiH3 is mild reducing agent.
(IV) The basicity of the hydrides increases in the order NH3  PH3  AsH3  SbH3  BiH3
Choose the most appropriate from the options given below:
(A) I and II only (B) I and IV only (C) II and III only (D) III and IV only

112. Give below are two statements:

Statement-I: Noble gases have very high boiling points.
Statement-II: Noble gases are monoatomic gases. They are held together by strong dispersion forces.
Because of this they are liquefied at very low temperature. Hence, they have very high boiling points.
In the light of the above statements, choose the correct answer from the options given below:
(A) Statement I is false but Statement II is true. (B) Both Statement I and Statement II are false.
(C) Statement I is true but Statement II is false. (D) Both Statement I and Statement II are true.

113. Choose the correct statements from the following

A. All group 16 elements form oxides of general formula EO2 and EO3 , where E = S,Se,Te and Po .
Both the types of oxides are acidic in nature.
B. TeO2 is an oxidising agent while SO2 is reducing in nature.
C. The reducing property decreases from H 2 S to H2Te down the group.
D. The ozone molecule contains five lone pairs of electrons.
Choose the correct answer from the options given below:
(A) B and C only (B) C and D only (C) A and B only (D) A and D only

114. Statement-I: S8 solid undergoes disproportionation reaction under alkaline conditions to form S2− and
S2O32 − .
Statement-II: ClO−4 can undergo disproportionation reaction under acidic condition.
In the light of the above statements, choose the most appropriate answer from the options given below:

PHYSICS WALLAH 60
 p-BLOCK
(A) Statement I is incorrect but statement II is correct
(B) Statement I is correct but statement II is incorrect
(C) Both statement I and statement II are incorrect
(D) Both statement I and statement II are correct

PHYSICS WALLAH 61
 p-BLOCK

EXERCISE #5 (JEE ADVANCED)

1. Complete and balance the following chemical equations – [IIT-1998, 2 M]
(i) P4O10 + PCl5 ⎯→ (ii) SnCl4 + C2H5Cl + Na ⎯→

2. Work out the following using chemical equations [IIT- 1998, 2M]
"Chlorination of calcium hydroxide produces bleaching powder"

3. 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 H2O2 using chemical equations –
[IIT- 1998, 4 M]

4. 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]

5. 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.

6. 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.

7. Give reason:
Why elemental nitrogen exists as a diatomic molecule whereas elemental phosphorus is a tetra atomic
molecule. [IIT- 2000]

8. Give an example of oxidation of one halide by another halogen. Explain the feasibility of the reaction.
[IIT- 2000]

9. 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]

10. Write the balanced chemical equation for developing photographic films. [IIT- 2001]

11. Identify (X) in the following synthetic scheme and write their structures. [IIT- 2001]
* *
BaCO3 + H2SO4 ⎯→ X (gas) ( C denotes C14)

12. Write the balanced equations for the reactions of the following compounds with water [2002]
(i) Al4Cl3 (ii) CaNCN (iii) BF3 (iv) NCl3
(v) XeF3

PHYSICS WALLAH 62
 p-BLOCK
13. Identify the following: [IIT- 2003]
Na 2CO3 ⎯⎯⎯
→ (I) ⎯⎯⎯⎯
SO 2
→ (II) Na2CO3
⎯⎯⎯⎯
elementalS

→ (III) ⎯⎯→ (IV)
I2

(aq)

Also mention the oxidation state of S in all the compounds.

14. Arrange the following oxides in the increasing order of Bronsted basicity. [IIT- 2004]
Cl2O7, BaO,SO3, CO2, B2O3

15. The number of P—O—P bonds in cyclic tetrametaphosphoric acid is – [IIT-2000]

(A) Zero (B) Two (C) Three (D) Four

16. The correct order of acidic strength is – [IIT- 2000]

(A) Cl2O7 > SO2 < P4O10 (B) CO2 > N2O5 > SO3
(C) Na2O > MgO > Al2O3 (D) K2O > CaO > MgO

17. Amongst H2O, H2S, H2Se and H2Te, the one with the highest boiling point is – [IIT- 2000]
(A) H2O because of hydrogen bonding (B) H2Te because of higher molecular weight
(C) H2S because of hydrogen bonding (D) H2Se because of lower molecular weight.

18. Ammonia can be dried by – [IIT- 2000]

(A) Conc. H2SO4 (B) P4O10 (C) CaO (D) Anhydrous CaCl2

19. 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

20. The reaction, 3ClO– (aq) ⎯→ ClO3– (aq) + 2Cl– (aq) is an example of – [IIT- 2001]
(A) Oxidation reaction (B) reduction reaction
(C) Disproportionation reaction (D) Decomposition reaction

21. The number of S–S bonds in sulphur trioxide trimer, (S3O9) is – [IIT- 2001]
(A) Three (B) Two (C) One (D) Zero

22. 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

23. Identify the correct order of solubility of Na2S, CuS, and ZnS in aqueous medium– [IIT- 2002]
(A) CuS > ZnS > Na2S (B) ZnS > Na2S > CuS (C) Na2S > CuS > ZnS (D) Na2S > ZnS > CuS

24. Identify, the correct order of acidic strength of CO2, CuO, CaO, H2O – [IIT- 2002]
(A) CaO < CuO < H2O < CO2 (B) H2O < CuO < CaO < CO2
(C) CaO < H2O < CuO < CO2 (D) H2O < CO2 < CaO < CuO

PHYSICS WALLAH 63
 p-BLOCK
25. When I– is oxidised by MnO4– in alkaline medium, I– converts into – [IIT- 2003]
(A) IO3– (B) I2 (C) IO4– (D) IO –

26. 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–
⎯→ Si2O76–
(r) Acidification
(D) (B4O72–) ⎯→ [B(OH)3] (s) Dilution by water

27. Which is the most thermodynamically stable allotropic form of phosphorus? [IIT- 2004]
(A) Red (B) White (C) Black (D) Yellow

28. When PbO2 reacts with conc. HNO3 the gas evolved may be : [IIT- 2004]
(A) NO2 (B) O2 (C) N2 (D) N2O

29. Which of the following is not oxidised by O3? [IIT- 2005]

(A) KI (B) FeSO4 (C) KMnO4 (D) K2MnO4

30. Which blue-liquid is obtained on reacting equimolar amounts of two gases at – 30ºC? [IIT- 2005]
(A) N2O (B) N2O3 (C) N2O4 (D) N2O5

31. Among the following, the paramagnetic compound is – [IIT- 2007]

(A) Na2O2 (B) O3 (C) N2O (D) KO2

Comprehension # 1 (Q. 32 to 34)

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]
32. 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

33. The structure of XeO3 is –

(A) Linear (B) Planar (C) Pyramidal (D) T-shaped

34. XeF4 and XeF6 are expected to be –

(A) Oxidising agent (B) Reducing agent (C) Unreactive (D) Strongly basic

Comprehension # 2 (Q.35 to 37)

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]
PHYSICS WALLAH 64
 p-BLOCK
35. 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

36. 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 sp 3
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.

37. 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

38. The reaction of P4 with X leads selectively to P4O6. The X is [JEE 2009]
(A) Dry O2 (B) A mixture of O2, and N2
(C) Moist O2 (D) O2 in the presence of aqueous NaOH

39. 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

40. Bleaching powder contains a salt of an oxoacid as one of its components. The anhydride of that oxoacid is:
[JEE 2012]
(A) Cl2O (B) Cl2O7 (C) ClO2 (D) Cl2O6

41. Concentrated nitric acid, upon long standing, turns yellow-brown due to the formation of -
(A) NO (B) NO2 (C) N2O (D) N2O4 [JEE 2013]

42. 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. 43 and 44)

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 Cl 2 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.
43. R, S and T, respectively are - [JEE 2013]
(A) SO2Cl2, PCl5 and H3PO4 (B) SO2Cl2, PCl3 and H3PO3
(C) SOCl2, PCl3 and H3PO2 (D) SO2Cl2, PCl5 and H3PO4
PHYSICS WALLAH 65
 p-BLOCK
44. 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

45. 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 + H2SO4 ⎯⎯
?
→ PbSO4 + O2 + other product (1) NO
(Q) Na2S2O3 + H2O ⎯⎯
?
→ NaHSO4 + other product (2) I2
o
(R) N2H4 ⎯⎯
?
→ N2 + other product (3) Warm
(S) XeF2 ⎯⎯
?
→ Xe + Other product (4) Cl2
Codes :
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

46. 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]
Complete
Hydrolysis
XeF6 P + other product

OH– / H2O

slow disproportionation in OH–/H2O

products
(A) 0 (B) 1 (C) 2 (D) 3

47. The product formed in the reaction of SOCl2 with white phosphorous is [JEE Adv. 2014]
(A) PCl3 (B) SO2Cl2 (C) SCl2 (D) POCl3

48. 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)

49. 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

50. The nitrogen containing compound produced in the reaction of HNO3 with P4O10
(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
PHYSICS WALLAH 66
 p-BLOCK
PARAGRAPH Q.51 to 52
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]
51. W and X are, respectively
(A) O2 and P4O6 (B) O3 and P4O10 (C) O3 and P4O6 (D) O2 and P4O10

52. Y and Z are, respectively

(A) N2O4 and HPO3 (B) N2O3 and H3PO4 (C) N2O5 and HPO3 (D) N2O4 and H3PO3

53. The compound(s) which generate(s) N2 gas upon thermal decomposition below 300°C is (are)
[JEE(Advanced) 2018]
(A) NH4NO3 (B) (NH4)2Cr2O7 (C) Ba(N3)2 (D) Mg3N2

54. A tin chloride Q undergoes the following reactions (not balanced)

Q + Cl– → X [JEE(Advanced) 2019]
Q + Me3N → Y
Q + CuCl2 → Z + CuCl
X is a monoanion having pyramidal geometry. Both Y and Z are neutral compounds.
Choose the correct option(s)
(A) There is a coordinate bond in Y
(B) The central atom in Z has one lone pair of electrons
(C) The central atom in X is sp3 hybridized
(D) The oxidation state of the central atom in Z is +2

55. With reference to aqua regia, choose the correct options(s) [JEE(Advanced) 2019]
(A) Reaction of gold with aqua regia produces NO2 in the absence of air
(B) Reaction of gold with aqua regia produces an anion having Au in +3 oxidation state
(C) Aqua regia is prepared by mixing conc. HCl and conc. HNO3 in 3 : 1 (v/v) ratio
(D) The yellow colour of aqua regia is due to the presence of NOCl and Cl2

56. With respect to hypochlorite, chlorate and perchlorate ions, choose the correct statement(s).
[JEE Advanced 2020]
(A) The hypochlorite ion is the strongest conjugate base.
(B) The molecular shape of only chlorate ion is influenced by the lone pair of electrons of Cl.
(C) The hypochlorite and chlorate ions disproportionate to give rise to identical set of ions.
(D) The hypochlorite ion oxidizes the sulfite ion.

57. The correct statement(s) related to oxoacids of phosphorous is(are) [JEE Advanced 2021]
(A) Upon heating, H3PO3 undergoes disproportionation reaction to produce H3PO4 and PH3.
(B) While H3PO3 can act as reducing agent, H3PO4 cannot.
(C) H3PO3 is a monobasic acid.
(D) The H atom of P-H bond in H3PO3 is not ionizable in water.

58. Ozonolysis of ClO2 produces an oxide of chlorine. The average oxidation state of chlorine in this oxide is
_____. [JEE Advanced 2021]

PHYSICS WALLAH 67
 p-BLOCK
59. The reaction of Xe and O2F2 gives a Xe compound P. The number of moles of HF produced by the complete
hydrolysis of 1 mol of P is _____. [JEE Advanced 2022]

60. The compound(s) which react(s) with NH3 to give boron nitride (BN) is(are) [JEE Advanced 2022]
(A) B (B) B2H6 (C) B2O3 (D) HBF4

61. The reaction of HClO3 with HCl gives a paramagnetic gas, which upon reaction with O3 produces
[JEE Advanced 2022]
(A) Cl2O (B) ClO2 (C) Cl2O6 (D) Cl2O7

62. The reaction of Pb(NO3)2 and NaCl in water produces a precipitate that dissolves upon the addition of HCl
of appropriate concentration. The dissolution of the precipitate is due to the formation of
[JEE Advanced 2022]
2–
(A) PbCl2 (B) PbCl4 (C) [PbCl4] (D) [PbCl6]2–

63. 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) P2O3 + 3H2O → (1) P(O)(OCH3)Cl2
(Q) P4 + 3NaOH + 3H2O → (2) H3PO3
(R) PCl5 + CH3COOH → (3) PH3
(S) H3PO2 + 2H2O + 4AgNO3 → (4) POCl3
(5) H3PO4
(A) P→2; Q→3; R→1; S→5 (B) P→3; Q→5; R→4; S→2
(C) P→5; Q→2; R→1; S→3 (D) P→2; Q→3; R→4; S→5

64. Based on VSEPR model, match the xenon compounds given in List-I with the corresponding. geometries
and the number of lone pairs on xenon given in List-II and choose the correct option.
[JEE Advanced 2024]
List-I List-II
(P) XeF2 (1) Trigonal bipyramidal and two lone pair of electrons
(Q) XeF4 (2) Tetrahedral and one lone pair of electrons
(R) XeO3 (3) Octahedral and two lone pair of electrons
(S) XeO3F2 (4) Trigonal bipyramidal and no lone pair of electrons
(5) Trigonal bipyramidal and three lone pair of electrons
(A) P-5, Q-2, R-3, S-1 (B) P-5, Q-3, R-2, S-4 (C) P-4, Q-3, R-2, S-1 (D) P-4, Q-2, R-5, S-3

PHYSICS WALLAH 68
 p-BLOCK

Answer Key

EXERCISE #1
1. (C) 2. (C) 3. (B) 4. (A)
5. (B) 6. (B) 7. (D) 8. (C)
9. (B) 10. (A) 11. (A) 12. (A)
13. (B) 14. (B) 15. (A) 16. (B)
17. (C) 18. (B) 19. (D) 20. (A)
21. (B) 22. (B) 23. (C) 24. (B)
25. (A) 26. (D) 27. (B) 28. (C)
29. (A) 30. (C) 31. (A) 32. (C)
33. (A)

EXERCISE #2
1. (A,B) 2. (A,C,D) 3. (A,B,C) 4. (A,B,C,D)
5. (A,B,D) 6. (B,C,D)

EXERCISE #3
1. (B) 2. (A) 3. (D) 4. (A)
5. (C) 6. (D) 7. (C) 8. (B)
9. (B) 10. (B) 11. (C) 12. (A)

EXERCISE #4 (JEE MAIN)

1. (D) 2. (D) 3. (C) 4. (D)
5. (C) 6. (C) 7. (B) 8. (D)
9. (C) 10. (C) 11. (B) 12. (D)
13. (B) 14. (A) 15. (C) 16. (C)
17. (A) 18. (C) 19. (A) 20. (A)
21. (D) 22. (D) 23. (B) 24. (B)
25. (C) 26. (B) 27. (B) 28. (B)
29. (D) 30. (B) 31. (C) 32. (D)
33. (A) 34. (A) 35. (C) 36. (C)
37. (A) 38. (D) 39. (A) 40. (B)
41. (B) 42. (B) 43. (A) 44. (A)
45. (D) 46. (C) 47. (A) 48. (B)
49. (D) 50. (B) 51. (C) 52. (B)
53. (C) 54. (A) 55. (B) 56. (A)
57. (C) 58. (A) 59. (D) 60. (B)
61. (C) 62. (D) 63. (C) 64. (A)
65. (A) 66. (C) 67. (A) 68. (C)
69. (A) 70. (C) 71. (A) 72. (B)
73. (D) 74. (C) 75. (C) 76. (B)
77. (C) 78. (D) 79. (C) 80. (A)

PHYSICS WALLAH 69
 p-BLOCK
81. (2) 82. (2) 83. (3) 84. (1)
85. (4) 86. (19) 87. (3) 88. (C)
89. (B) 90. (D) 91. (C) 92. (B)
93. (B) 94. (C) 95. (B) 96. (A)
97. (12) 98. (D) 99. (3) 100. (A)
101. (D) 102. (3) 103. (C) 104. (8)
105. (C) 106. (B) 107. (1) 108. (D)
109. (A) 110. (A) 111. (A) 112. (B)
113. (C) 114. (B)

EXERCISE #5 (JEE ADVANCED)

1. (i) P4O10 + 6PCl3 ⎯→ 10POCl3 (ii) SnCl4 + 2C2H5Cl + 2Na ⎯→ Na2SnCl6 + C4H10

2. 3Ca(OH)2 + 2Cl2 ⎯→ Ca(OCl)2 + Ca(OH)2 CaCl2 · 2H2O

Bleaching powder is a mixture of CaOCl2

And hydrated basic calcium chloride.

3. When H2O2 acts as oxidizing agent, therefore, following reaction takes place:
H2O2 + 2e– ⎯→ 2OH–
while, regarding is action on reducing agent, the following reaction takes place :
H2O2 + 2OH– ⎯→ O2 + 2H2O + 2e–
Oxidizing character :
2Cr(OH)3 + 4NaOH + 3H2O2 ⎯→ 2Na2CrO4 + 8H2O
Reducing character:
2K3 [Fe(CN)6] + 2KOH + H2O2 ⎯→ 2K4 [Fe(CN)6] + 2H2O + O2

4. In SO3 + H2O ⎯→ H2SO4 reaction, H2SO4 is obtained in misty form and reaction is explosive (highly
exothermic). By adding H2SO4 the above reaction is prevented.
H2SO4 + SO3 ⎯→ H2S2O7 (oleum)
H2S2O7 + H2O ⎯→ 2H2SO4
The catalyst used is V2O5 and K2O is used as promotor for the oxidation of SO2 into SO3.

5. (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
2F— ⎯→ 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.


6. (i) 3SiCl4 + 4Al ⎯⎯ → 4AlCl3 + 3Si
vapour molten volatilized

PHYSICS WALLAH 70
 p-BLOCK

(ii) 15CaO + 4P4 ⎯⎯ → 5Ca3 P2 + 3P2O5
[Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3] × 5
15CaO + 4P4 + 30H2O → 15CaO(OH)2 + 3P2O5  + 10 PH3 
(iii) 2NH3 + CO2 + H2O → (NH4)2CO3
CaSO4 + (NH4)2 CO3 → CaCO3  (NH4)2SO4
gypsum

CaSO4 + 2NH3 + CO2 + H2O → CaCO3 

+ (NH4)2SO4

7. In nitrogen, d-orbitals are not present, so in it the possiblity of intramolecular multiplicity exists which
leads to the completion of octet through -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.

8. 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

9. X : BCl3
Y : B2H6
4BCl3 + 3LiAlH4 ⎯⎯→ 3AlCl3 + 3LiCl + 2B2H6
X
B2H6 + 3O2 ⎯⎯→ B2O3 + 3H2O (exothermic)
Y

10. Unreacted AgBr is removed by hypo (Na2S2O3)

AgBr + 2Na2S2O3 ⎯→ Na3[Ag(S2O3)2] + NaBr

11. 14CO2

12. (i) Al4Cl3 + 12H2O ⎯→ 4Al(OH)3 + 3CH4

(ii) CaNCN + 3H2O ⎯→ CaCO3  + 2NH3
(iii) 4BF3 + 3H2O ⎯→ H3BO3 + 3HBF4
boricacid fluoboricacid

(iv) NCl3 + 3H2O ⎯→  + 3HOCl

hypochlorousacid

(iv) 2XeF4 + 3H2O ⎯→ Xe + XeO3 + F2 + 6HCl

xenon trioxide

13. Oxidation state

(I) NaHSO3 + 4 (II) Na2SO3 + 4 (III) Na2S2O3 + 2 (IV) Na2S4O6 + 2.5

PHYSICS WALLAH 71
 p-BLOCK
14. Cl2O7 < SO3 < CO2 < B2O3 < BaO 15. (D) 16. (A)
17. (A) 18. (C) 19. (A) 20. (C)
21. (D) 22. (C) 23. (D) 24. (A)
25. (A) 26. (A) → Q, S; (B) → R, S; (C) → P; (D) → Q, R
27. (C) 28. (B) 29. (C) 30. (B)
31. (D) 32. (A) 33. (C) 34. (A)
35. (C) 36. (C) 37. (B) 38. (B)
39. (C) 40. (A) 41. (B) 42. (A,C,D)
43. (A) 44. (A) 45. (D) 46. (C)
47. (A) 48. (B,C)

49. (B)
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 smaller than Al.

50. (B,D)
P4O10 + 4HNO3 ⎯⎯⎯⎯⎯⎯
dehydrationHNO3
→ 4(HPO3 ) + 2N2O5
(requiredproduct)

(A) P4 + 20 HNO3 → 4H3PO4 + 20NO2  + 4H2O

(B) N2O5 is diamagnetic in nature
O O
(C) N2O5 → N N
O O O
(D) Na + N2O5 → NaNO3 + NO2 
(Brown gas)

51. (D) 52. (C) 53. (B,C) 54. (A,C)

55. (B,C,D) 56. (A,B,D) 57. (A,B,D) 58. (6)
59. (4) 60. (A,B,C) 61. (C) 62. (C)
63. (D) 64. (B)

PW Web/App - https://smart.link/7wwosivoicgd4
Library- https://smart.link/sdfez8ejd80if

PHYSICS WALLAH 72