p-Block

P BLOCK ELEMENTS
 G -15 : NITROGEN FAMILY
• Two of the most dissimilar nonmetallic elements are in the same group:
reactive phosphorus and unreactive nitrogen.
• Of the other members of the group, arsenic and antimony are
metalloids, and the last member of the group, bismuth, exhibit weakly
metallic behavior.
 G -15 : NITROGEN FAMILY
• Molecular nitrogen comprises 78% by volume of the atmosphere.

• In the earth’s crust, nitrogen occurs as sodium nitrate, NaNO3(Chile

saltpetre) and KNO3 (Indian saltpetre).

• Both nitrogen and phosphorus are found in the proteins and nucleic
acids in plants and animals.

• Nitro compounds are used to manufacture explosive (TNT and

dynamite).
 G -15 : NITROGEN FAMILY

• Phosphorus occurs in minerals of the apatite family, Ca9(PO4)6.CaX2

(X = F, Cl or OH) (e.g., fluorapatite Ca9(PO4)6. CaF2) which are the

main components of phosphate rocks..
G -15 : NITROGEN FAMILY
 ANOMALOUS PROPERTIES OF N
➔ Small size
➔ High EN
➔ High IE
➔ Absence of d-orbitals in valence shell

Only pπ-pπ multiple bonds

No dπ-pπ

Lack of catenation

Exceptionally high bond

enthalpy of N2 (942 KJ/mol)

Nitrogen Bonds Bond Carbon Bonds Bond Energy

Energy ([Link]-1) ([Link]-1)
N―N 167 C - C 346
N≡N 942 C ≡ C 835
 NITROGEN VS PHOSPHORUS CHEMISTRY
• Bond energy of single N–N bond is less than the single P–P bond
because of high interelectronic repulsion of the non-bonding electrons,
owing to the small bond length.

Nitrogen Bonds Bond Energy Phosphorus Bonds Bond Energy

([Link]-1) ([Link]-1)
N―N 167 P―P 200
N≡N 942 P≡P 481
N―O 201 P-O 335
dπ-pπ BOND IN PHOSPHORUS COMPOUNDS
 OXIDATION STATES
• The common oxidation states of these elements are -3, +3 and +5.

• Tendency to exhibit -3 decreases down the group: increase in metallic

character.

• In the case of N, all oxidation states from +1 to +4 tend to

disproportionate in acid solution

3HNO2 → HNO3 + H2O + 2NO

• Similarly, in case of P nearly all intermediate oxidation states

disproportionate into +5 and –3 both in alkali and acid.

• Whereas considering the case of As, Sb and Bi the +3 state is stable with
respect to disproportionation.
 OXIDATION STATES
• Nitrogen shows all the oxidation states from -3 to +5.

Compounds Oxidation Sates

1. NH3 (Azane) –3

2. NH2–NH2 (Hydrazine) –2

3. NH2OH (Hydroxylamine) –1

4. N2 (Nitrogen) 0

5. N2O (Nitrous Oxide) +1

6. NO (Nitric Oxide) +2
7. N2O3 (Dinitrogen trioxide) +3

8. NO2 (Nitrogen dioxide) +4

9. N2O5, HNO3 (Nitric acid) +5

INERT PAIR EFFECT
 REACTIVITY TOWARDS HYDROGEN
• All the elements of Group 15 form hydrides of the type EH3 where
E=N, P, As, Sb or Bi..
• Basic Character Decreases
• Thermal Stability Decreases
• Reducing Character Increases
• Arrhenius acidity Increases
 DRAGO’S RULE
Drago’s rule states that , if:

A. the central atom has at least one lone pair of electron on it

B. the central atom belongs to group 13,14 ,15 or 16 and is from 3rd to
7th period.
C. if electronegativity of side element is 2.5 or less
D. no. of sigma bonds + lone pair=4

then, THERE IS NO NEED TO CONSIDER HYBRIDIZATION OF THAT ELEMENT.

 DRAGO’S RULE

This is because hybridization requires some energy. This energy is

obtained from repulsion P has EN of 2.1 also since atomic size is large
energy is not available for hybridization
 DRAGO’S RULE

S S S
Sp 3
–S

P–

P–
P–
S

S
S
Here lp are in S orbital
lp not easily donated as they are held
tightly by nuclease so do not act as Lewis
base.
PH3 + dil HCl → No reaction
PH3 + H2O → No reaction
PH3 + conc HCl → PH4Cl
 MELTING AND BOILING POINTS OF EH3
Boiling point

PH3 < AsH3 < NH3 < SbH3 < BiH3

Melting point

PH3 < AsH3 < SbH3 < NH3 < BiH3

OXIDES OF GROUP 15

More acidic than A2O3

→ Note : as O.N. ­↑ acidity of oxide ↑

→ Nitrogen can form number of oxides
N2O NO N2O3 NO2

N2O4 N2O5
→ Oxides of Sb and Bi exist as Oxo-
halides
 HALIDES OF GROUP 15

• Only NF3 stable among NX3 • No NCl5

NCl3, NBr3, NI3 are explosive due to absence of d orbital

• Mainly covalent except BiF3 • Pentahalides more covalent than trihalides

Fajan’s Rule
 COMPOUNDS OF GROUP 15 WITH METALS

• All these elements react with metals to form their binary compounds
exhibiting –3 oxidation state, such as, Ca3N2 (calcium nitride) Ca3P2

(calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2 (zinc

antimonide) and Mg3Bi2 (magnesium bismuthide).

 STRUCTURE OF OXIDES OF NITROGEN

1. Nitrous oxide (laughing gas) diamagnetic

2. Nitric oxide Neutral
Paramagnetic
3. Dinitrogen trioxide
4. Nitrogen dioxide Diamagnetic
Blue
dimerizes
Paramagnetic
5. Dinitrogen tetroxide Yellow Brown
acidic

diamagnetic

diamagnetic
OXIDES OF GROUP 15
OXIDES OF NITROGEN
 METHOD OF PREPARATION OF OXIDES OF GROUP 15

1. N2O (laughing
gas)

2. NO
(gas)
 METHOD OF PREPARATION OF OXIDES OF GROUP 15

3. NO + NO2 → N2O3
N2O3 Both have unpaired e–

4.

NO2

5.
N2O5

Meta phosphoric acid

Q.1. Among the 15th group elements, as we move from
nitrogen to bismuth, the pentavalency becomes less
pronounced and trivalency becomes more pronounced
due to

(a) Non metallic character

(b) Inert pair effect
(c) High electronegativity
(d) Large ionization energy

Ans.
(b)
Q.2. Which of the following statements is not correct
for nitrogen?

(a) Its electronegativity is very high

(b) d-orbitals are available for bonding
(c) It is a typical non-metal
(d) Its molecular size is small

Ans. (b)
Q.3. Collectively the elements of group 15
are called –

(a) pnicogens
(b) pnicopens
(c) nicopen
(d) None of these

Ans.
(a)
Q.4. Ionic radii (in Å) of As3+, Sb3+ and Bi3+ follow the
order

(a) As3+ > Sb3+ > Bi3+

(b) Sb3+ > Bi3+ >As3+
(c) Bi3+ > As3+ > Sb3+
(d) Bi3+ > Sb3+ > As3+

Ans.
(d)
Q.5. Which one of the following elements is most
metallic ?

(a) P
(b) As
(c) Sb
(d) Bi

Ans. (d)
Q.6. Which of the follow group 15 element forms metallic
bonds in elemental state ?

(a) As
(b) P
(c) Sb
(d) Bi

Ans.
(d)
Q.7. The three important oxidation states of
phosphorus are

(a) –3, +3 and +5

(b) –3, +3 and –5
(c) –3, +3 and +2
(d) –3, +3 and +4

Ans. (a) –3, +3,

+5
Q.8. Which of the following statement is incorrect for group
15 elements ?

(a) Order of ionization enthalpies is ΔiH1 < ΔiH2 < ΔiH3

(b) The boiling point and melting point increases from top to
bottom in the group
(c) Dinitrogen is a gas while all others are solids
(d) All statements are correct

Ans. (b)
Q.9. Nitrogen is relatively inactive element
because

(a) its atom has a stable electronic

configuration
(b) it has low atomic radius
(c) its electronegativity is fairly high
(d) dissociation energy of its molecule is
fairly high

Ans. (d)
Q.10. Which of the following has the highest pπ – pπ
bonding tendency ?

(a) N
(b) P
(c) As
(d) Sb

Ans. (a)
Q.11. Pick out the wrong statement.

(a) Nitrogen has the ability to form pπ-pπ bonds with

itself.
(b) Bismuth forms metallic bonds in elemental state.
(c) Catenation tendency is higher in nitrogen when
compared with other elements of the same group.
(d) Nitrogen has higher first ionisation enthalpy when
compared with other elements of the same group

Ans. (c)
Q.12. Nitrogen forms N2, but phosphorus is converted into
P4 from P, the reason is

(a) Triple bond is present between phosphorus atom

(b) pπ – pπ bonding is strong
(c) pπ – pπ bonding is weak
(d) Multiple bond is formed easily

Ans. (c)
Q.13. What causes nitrogen to be chemically
inert ?

(a) Multiple bond formation in the molecule

(b) Absence of bond polarity
(c) Short internuclear distance
(d) High bond energy

Ans. (d)
Q.14. Pentavalence in phosphorus is more stable when
compared to that of nitrogen even though they belong to
same group. This is due to

(a) dissimilar electronic configuration

(b) due to presence of vacant d-orbitals
(c) reactivity of phosphorus
(d) inert nature of nitrogen

Ans.
(b)
Q.15. Which one has the lowest boiling
point ?

(a) NH3
(b) PH3
(c) AsH3
(d) SbH3

Ans.
(b)
 PROPERTIES OF NITROGEN

⮚ Colourless, odourless, tasteless, non-toxic gas

⮚ Very low solubility in water
⮚ Inert at low temperature
⮚ Two stable isotopes: 14N and 15N
 PREPARATION OF NITROGEN

• An electrical charge triggered by

automobile impact causes sodium
azide to explode and convert to
nitrogen gas inside the airbag.
PREPARATION OF NITROGEN
REACTIONS OF NITROGEN
COMPOUNDS OF NITROGEN: AMMONIA
AMMONIA PREPARATION
AMMONIA AS A LIGAND

[Cu(NH3)4]2+

(deep blue)
 NITRIC ACID - HNO3

• Laboratory grade nitric acid contains ~ 68% of the HNO3 by mass.

• It is a colourless (f.p. 231.4 K and b.p. 355.6 K) but converts

to yellowish liquid with time. Why?
PREPARATION OF NITRIC ACID - LABORATORY METHOD
conc
↑

↑
PREPARATION OF NITRIC ACID - INDUSTRIAL METHOD
PREPARATION OF NITRIC ACID - INDUSTRIAL METHOD
NITRIC ACID AS OXIDIZING AGENT: OXIDATION OF METALS

1. Very dilute HNO3 → Only Mn and Mg are capable of producing H2

w/v <
rest metal give H2O as HNO3 strong [0] agent
1%
→ Zn gives NH4NO3

2. dilute a) Ag, Hg, Cu, Pb → NO↑ + Metal nitrate

HNO3
w/v < b) Fe, Zn → N2O↑ + Metal nitrate
20%
c) Sn → NH4NO3 + Metal nitrate

3. Conc
HNO3 a) Ag, Hg, Cu, Pb → NO↑ + Metal nitrate
w/v >
20% b) Sn → NH4NO3 + Metal nitrate

Meta stannic acid

NITRIC ACID AS OXIDIZING AGENT: OXIDATION OF NON-METALS

Concentrated nitric acid also oxidises non - metals and their compounds.
 NITRIC ACID AS OXIDIZING AGENT: BROWN RING TEST
• The brown ring test for nitrates depends on the ability of Fe2+ to reduce nitrates
to nitric oxide, which reacts with Fe2+ to form a brown colored complex.

• The test is usually carried out by adding dilute

ferrous sulphate solution to an aqueous solution
containing nitrate ion, and then carefully adding
concentrated sulphuric acid along the sides.

• Exception: Salts of cations which form precipitate with SO42- ion.

E.g. Ca+2 and Ba+2
OXOACIDS OF NITROGEN
 ALLOTROPES OF PHOSPHORUS
Allotropes of Phosphorus
 WHITE PHOSPHOROUS
• Translucent white waxy solid
• Poisonous - Caused “Phossy Jaw” in matchstick industry workers
• Insoluble in water but soluble in carbon disulphide
• Catches fire in air to give dense white fumes of P4O10

• Glows in dark (chemiluminescence and not

phosphorescence).
• Dangerously reactive in air
• Glows with a white light and spontaneously
bursts into flame
 RED PHOSPHORUS

• Obtained by heating white phosphorus at 573K in an inert atmosphere

for several days.
• Non- Poisonous –
• Insoluble in water as well as in carbon disulphide
• less reactive than white phosphorus
• It does not glow in the dark.
 BLACK PHOSPHORUS

• Black phosphorus has two forms α-black phosphorus and β-black

phosphorus.
• α-Black phosphorus is formed when red phosphorus is heated in a
sealed tube at 803K
• β-Black phosphorus is prepared by heating white phosphorus at 473K
under high pressure.
BLACK PHOSPHORUS
BLACK PHOSPHORUS
COMPOUNDS OF PHOSPHORUS: PHOSPHORUS HALIDES

• In liquid or gas
• In gaseous and liquid phases, it has a
phases due to
trigonal bipyramidal structure
Pseudo Berry
with distinct bond lengths.
Rotation the
• In the solid state it exists as an bond lengths
ionic solid. [PCl4]+[PCl6]- in which are same
the cation, [PCl4]+ is tetrahedral
and the anion, [PCl6]- octahedral.
COMPOUNDS OF PHOSPHORUS: PHOSPHORUS HALIDES
 PHOSPHINE
• Colourless gas with decomposed fish smell
• Highly poisonous
• It explodes in contact with traces of oxidising agents like HNO3,Cl2 and Br2
vapours.
• It is slightly soluble in water (NH3 is highly soluble).
PH3(aq) 🡪 Red P + H2

• Phosphine is weakly basic and like ammonia, gives phosphonium

compounds with acids e.g.
PH3 + HBr 🡪 PH4Br

• When absorbed in copper sulphate or mercuric

chloride solution, the corresponding phosphides are obtained.
3CuSO4 + 2PH3 🡪 Cu3P2 + 3H2SO4
3HgCl2 + 2PH3 🡪 Hg3P2 + 6HCl
 PHOSPHINE: PREPARATIONS
Calcium Phosphide

Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3

Ca3P2 + 6HCl → 3CaCl2 + 2PH3

White Phosphorous

P4 + 3NaOH + 3H2O 🡪 PH3 + 3NaH2PO2

sodium hypophosphite

• Impurities of P2H4 and P4

• Absorbed in HI to form phosphonium iodide (PH4I)and the salt

is treated with KOH

PH4I + KOH 🡪 KI + H2O + PH3

COMPOUNDS OF PHOSPHORUS: OXYACIDS
HYPOPHOSPHORIC ACID
• PF5 has trigonal bipyramidal structure in gas as well as in solid state.

This is because F is EN and has high electron density due to which it is polarizable and
develops covalent nature. (Hybridization sp3d)

• PCl5 in gas and liquid state is covalent but in solid state it is ionic

Sp3 Sp3d2

PCl5 splits into more stable octahedral and tetrahedral structure

• PBr5 in gas and liquid state is covalent but in solid state it is ionic

Sp3

PI5 does not exist due to greater size of I atoms

Sp3
 EXISTENCE OR NON-EXISTENCE OF MOLECULE

• IF7 exist but ICl7 , IBr7 does not exist.

• SF6 exist but SCl6 , SBr6 does not exist.

• SiF6–2 exist but SiCl6–2, SiBr62– does not exist.

• AlF6–3 eixst but AlCl6–3, AlBr6–3 does not exist.

• AlBr4– exist but BBr4– , BI4– does not exist.

[Link] brown ring test for NO2- and NO3- is due to the
formation of complex ion with a formula

a) [ Fe(H2O)5NO ]2+
b) Mg3N2
c) NH3
d) MgO

Ans.
(a)
2. The P-P-P bond angle in white phosphorus is

a) 120°
b) 109° 28′
c) 90°
d) 60°

Ans.
(d)
3. Brown colour in HNO3 can be removed by

a) Adding Mg power
b) Boiling the acid
c) Passing HN3 through acid
d) Passing air through warm acid

Ans.
(d)
4. Read P can be obtained white P by

a) Heating in an atmosphere over 573K

b) Distilling it in a inert atmosphere
c) Dissolving it in CS2 and crystallizing
d) Melting it and pouring the liquid into
water

Ans.
(a)
5. In nitrogen family, the H-E-H bond angle in the hydrides
gradually becomes closer to 90° on going from N to Sb. This
shows that gradually

a) The basic strength of the hydrides increases

b) Bond energies of M-H bonds increases
c) Almost pure p-orbitals are used for E-H bonding
d) The bond pairs of electrons become nearer to the central
atom

Ans.
(c)
6. Of the following compounds, the most
acidic is

a) As2O3
b) P2O3
c) Sb2O3
d) Bi2O3

Ans.
(b)
7. Phosphorus penta-oxide is widely used as

a) reducing agent
b) oxidizing agent
c) dehydrating agent
d) both b and c

Ans.
(d)
8. Ammonia compound which on heating does not
give NH3

a) (NH4)2SO4
b) (NH4)2CO3
c) NH4NO2
d) NH4Cl

Ans.
(c)
9. Which of the following is metaphosphoric
acid?

a) H3P3O9
b) H5P3O10
c) H9P2O7
d) H3PO4

Ans.
(a)
G-16: OXYGEN FAMILY / CHALCOGENS
 G-16: OXYGEN FAMILY

• Group 16 of the periodic table has the elements: Oxygen, sulphur,

selenium, tellurium and polonium.
• This is also known as group of chalcogens.
• Oxygen and sulphur are non-metals, selenium and tellurium
metalloids, whereas polonium is a metal.
• All these elements exhibit allotropy.
• Oxygen is the most abundant of all the elements on earth. Oxygen forms
about 46.6% by mass of earth’s crust. Dry air contains 20.946% oxygen
by volume.
 G-16: SULPHUR

• The abundance of Sulphur in the earth’s crust is only 0.03-0.1%.

• Combined sulphur exists primarily as sulphates such as:
• Gypsum CaSO4.2H2O,

• Epsom salt MgSO4.7H2O,

• Baryte BaSO4

• Sulphides such as galena PbS, zinc blende ZnS, copper pyrites CuFeS2
G-16: OXYGEN FAMILY
 OXYGEN VS SULPHUR CHEMISTRY

• The O=O double bond is much stronger than the O ― O single bond.
• This is in contrast to sulfur and the other members of the group, where
the energy of two single bonds is greater than that of one double bond.
• For this reason, multiple bonding is only common for oxygen.

Nitrogen Bonds Bond Energy Carbon Bonds Bond

([Link]-1) Energy ([Link]-1)
O―O 142 S―S 268
O=O 494 S=S 425
 OXYGEN VS SULPHUR CHEMISTRY
• Compounds containing two oxygen atoms singly bonded together are
usually strong oxidizing agents. Such behavior can be explained by the
weakness of the oxygen-oxygen single bond compared to its bonds to
other elements.

• This is in contrast to sulfur and the other members of the group, where
the energy of two single bonds is greater than that of one double
bond.

Nitrogen Bonds Bond Energy Carbon Bonds Bond Energy

([Link]-1) ([Link]-1)
O ― O 142 S ― S 268
O ― Cl 218 S ― Cl 271
O ― H 459 S ― H 363
 COMPOUND OF G 16 - HYDRIDES

Basic Character Decreases

Thermal Stability Decreases

Reducing Character Increases

COMPOUND OF G 16 - HYDRIDES
 COMPOUND OF G 16 - OXIDES

SO2 Reducing SO3

Agent SeO3
SeO2
TeO3
TeO2 Oxidizing
agent

Inert pair effect Ti4+ → Ti2+

 HALIDES OF GROUP 16
• Halides of the type, EX6, EX4, and EX2

• Stability order F- > Cl- > Br- > I-

• Amongst hexahalides (EX6), hexafluorides(EF6) are the only stable

halides. All hexafluorides are gaseous in nature. They have octahedral
structure. Sulphur hexafluoride, SF6 is exceptionally stable for steric
reasons.
• All elements except oxygen form
dichlorides and dibromides.

• Monohalides are dimeric in nature.

S2F2, S2Cl2 , S2Br2, Se2Cl2 and Se2Br2

• These dimeric halides undergo

disproportionation as given below:
2Se2Cl2 → SeCl4 + 3Se
 DIOXYGEN
• Dioxygen is a colorless, odorless gas that condenses to a pale blue
liquid.
• Almost all elements will react with oxygen at room temperature or when
heated.
• The main exceptions are the "noble" metals, such as platinum, and
the noble gases.
 PARAMAGNETIC NATURE OF OXYGEN
• Molecular orbital energy level diagram showing the combination of the
2p atomic orbitals on the dioxygen molecule..
 ANOMALOUS BEHAVIOUR OF OXYGEN

⮚ Small size
⮚ High EN
⮚ High IE
⮚ Absence of d-orbitals in valence shell

Only pπ-pπ multiple bonds

No dπ-pπ

Lack of catenation

Strong Hydrogen Bonding

OXYGEN: PREPARATION

Δ
+ +
Δ Δ 2
 OXYGEN: PREPARATION
• Hydrogen peroxide is readily decomposed into water and dioxygen by
catalysts such as finely divided metals and manganese dioxide

• Electrolysis of water leads to the release of hydrogen at the cathode and

oxygen at the anode

• Fractional Distillation of Air: Carbon dioxide and water vapour are

removed from air and then, the remaining gases are liquefied and
fractionally distilled to give dinitrogen and dioxygen.
 REACTIVITY OF OXYGEN

• Dioxygen directly reacts with nearly all metals and non-metals except some
metals (e.g., Au, Pt) and some noble gases.
• Its combination with other elements is often strongly exothermic which
helps in sustaining the reaction.
• To initiate the reaction, some external healing is required as bond
dissociation enthalpy of oxygen-oxygen double bond is high (493.4 kJ mol-
1).
ACIDIC VS BASIC OXIDES
ACIDIC, BASIC AND AMPHOTERIC OXIDES IN PERIODIC TABLE

Al(OH)3 + 3HCl → AlCl3 + 3H2O

Al(OH)3 + NaOH → Na[Al(OH)4]
NATURE OF OXIDE VS OXIDATION STATE OF ELEMENT
 OZONE
• Ozone is an allotropic form of oxygen. It is formed from atmospheric
oxygen in the presence of sunlight. It is too reactive and degrades at
ground level.
• This ozone layer protects the earth’s surface from an excessive
concentration of ultraviolet (UV) radiations.
 OZONE LAYER DEPLETION
• Nitrogen oxides (particularly NO) combine very rapidly with ozone.
• There is 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)
 OZONE PREPARATION

• Pure ozone is a pale blue gas, dark blue liquid and violet-black solid

• 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 ozonized oxygen.
3O2 ⟶ 2O3 ΔH⊝ (298 K) = 142 kJ mol - endothermic process
1
 OZONE REACTIVITY
• Ozone is thermodynamically unstable with respect to oxygen since its
decomposition into oxygen ΔH is negative and ΔS is positive

• These two effects results in large negative Gibbs energy change (∆G) for its
conversion into oxygen.

• Due to the ease with which it liberates atoms of nascent oxygen (O3 ⟶ O2 + O),
it acts as a powerful oxidizing agent.
PbS(s) + 4O3(g) ⟶ PbSO4(s) + 4O2(g)

2I-(aq) + H2O(I) + O3(g) ⟶ 2OH-(aq) + I2(s) + O2(g)

 OZONE APPLICATIONS
• Used as a germicide, disinfectant and for sterilizing water.

• Also used for bleaching oils, ivory, flour, starch, etc.

• Acts as an oxidizing agent in the manufacture of potassium

permanganate.
 SULPHUR — ALLOTROPIC FORMS
• Rhombic Sulphur(Sα) • Monoclinic Sulphur(Sβ)

• Needle like, long crystals.

• Rhombic octahedral
crystals
• Prepared by melting
• Formed on evaporating rhombic sulphur in a
the solution of roll dish and cooling till crust
sulphur in CS2 is formed
 SULPHUR — ALLOTROPIC FORMS
• Both rhombic and monoclinic sulphur have S8 molecules which is
puckered and has a crown shape.

• In cyclo-S6 , the ring adopts the chair form

• At elevated temperatures (~1000 K), S2 is the dominant species and is

paramagnetic like O2
 PREPARATION OF SO2
• Colorless gas with pungent smell and is highly soluble in
water
Burning Sulphur

Sulphite + Acid

Industrial:
Burning Sulphide
ore
 REACTION OF SO2

Water

Base

Cl2 sulphuryl chloride

Reducing agent

SO2 : Reduction ⇒ TEMPORARY

Bleaching agent
Cl2 : Oxidation ⇒ PERMANENT
 OXOACIDS OF SULPHUR

Sulphuric acid Sulphurous acid Hyposulphuous acid

Peroxydisulfuric Acid Pyrosulfuric acid or

Or Marshall’s acid oleum
 OXOACIDS OF SULPHUR

Caro’s acid Thiosulphuric Pyrosulphurous

acid acid

Polythionic acid
SULPHURIC ACID PREPARATION - CONTACT PROCESS

This reaction is reversible in

nature.

Sulphur trioxide cannot be

dissolved in water directly as
it leads to the formation of fog.
 SULPHURIC ACID - PROPERTIES

• Strong acidic character K = very large (Ka1 >10)

Ka2 = 1.2 × 10–2

• Strong affinity for water C12H22O11 → 12C + 11H2O

• Ability to act as an oxidizing agent

Cu + 2H2SO4 (conc.) → CuSO4 + SO2 + 2H2O

S + 2H2SO4(conc.) → 3SO2 + 2H2O

C + 2H2SO4 (conc.) → CO2 + 2SO2 + 2H2O

1. Group 16 Elements is also called

a) Pnicogens.
b) Picogens.
c) Halogens.
d) Chalcogens

Ans.
(d)
2. There is a large difference between melting and boiling
point of Oxygen and Sulphur is because

a) Oxygen is more electronegative than sulphur.

b) Sulphur have less ionisation enthalpy than Oxygen.
c) Oxygen exist as diatomic but sulphur as polyatomic.
d) None of these

Ans.
(c)
3. Oxygen shows +2 oxidation state with which of the
following elements?

a) Sulphur.
b) Fluorine.
c) Selenium.
d) Tellurium

Ans.
(b)
4. The correct order of acidic strength

a) H2O>H2Te>H2S>H2Se.
b) H2Te<H2Se<H2S<H2O.
c) H2Se>H2Te>H2S>H2O.
d) H2Te>H2Se>H2S>H2O.

Ans.
(d)
5. The correct order of thermal stability is

a) H2Te>H2Se>H2S>H2O
b) H2S>H2O>H2Se>H2Te
c) H2O>H2S>H2Se>H2Te.
d) None of these.

Ans.
(c)
6. The correct order for reducing property

a) H2O>H2S>H2Se>H2Te.
b) H2O<H2S<H2Se<H2Te
c) H2S>H2Se>H2O>H2Te
d) H2Te>H2O>H2Se>H2S

Ans.
(b)
7. The hybridisation of SF4 is

a) sp3d
b) sp3d2
c) sp3
d) sp

Ans.
(a)
8. The geometry of SeF4 is

a) Linear.
b) Square planar.
c) Trigonal bi-pyramidal.
d) Tetrahedral.

Ans.
(c)
9. The correct order of reducing property of
dioxides are

1.TeO2>SeO2>SO2
2.SO2>SeO2>TeO2
3.SeO2>TeO2>SO2
[Link] of these.

Ans.
(b)
G-17: HALOGEN FAMILY
 G-17: HALOGEN FAMILY
• Members of G-17: Fluorine, chlorine, bromine, iodine and astatine.

• Known as the halogens (salt producers)

• F and Cl are much more abundant compared to Br and I in following

forms:
1. Fluorspar CaF2

2. Cryolite Na3AlF6

3. Fluoroapatite 3Ca3(PO4)2.CaF2
4. Sodium Chloride NaCl
5. Carnallite, KCl.MgCl2.6H2O
G-17: HALOGEN FAMILY
 G-17: HALOGEN FAMILY

• Lower value of bond dissociation energy of fluorine is due to the high inter
electronic repulsions between nonbonding electrons of the 2p-orbital of
small sized fluorine
HALOGENS ARE COLORED DUE TO ABSORPTION OF
RADIATIONS IN VISIBLE REGION
 CHEMICAL PROPERTIES
Oxidation states Fluorine: Only –1

Chlorine, bromine and iodine: -1, +1, +3, +5 and +7

 CHEMICAL PROPERTIES

Oxidizing Agents
F2 + 2X– → 2F– + X2 (X = Cl, Br or I)

Cl2 + 2X–→ 2Cl– + X2 (X = Br or I)

Br2 + 2I–→ 2Br– + I2

 CHEMICAL PROPERTIES

Reaction with water

2F2 (g) + 2H2O(l) → 4H+ (aq) + 4F– (aq) + O2 (g)

Cl2 (g) + H2O (l) → HCl (aq) + HOCl (aq)

Br2 (g) + H2O (l) → HBr(aq) + HOBr (aq)

4I– (aq) + 4H+ (aq) + O2 (g) → 2I2 (s) + 2H2O(l)

 ANOMALOUS BEHAVIOUR OF FLUORINE

⮚ Small size
⮚ High EN
⮚ High IE
⮚ Absence of d-orbitals in valence shell

Higher ionisation enthalpy,

and electrode potential

Lower m.p. and b.p., enthalpy

of bond dissociation and
electron gain enthalpy
 HYDRIDES OF GROUP 17

Thermal Stability Decreases

Reducing Character Increases

 OXIDES OF GROUP 17
Fluorine • OF2 and O2F2 (unstable at Room Temperature)
• Strong Fluorinating agents

Chlorine • Cl2O, ClO2, Cl2O6 and Cl2O7

• Highly reactive oxidising agents and tend to explode.
• ClO2 is used as a bleaching agent
 OXIDES OF GROUP 17
• Br2O, BrO2, BrO3
Bromine
• Least stable halogen oxides (middle row anomaly). They
are very
• powerful oxidizing agents.

• I2O4, I2O5, I2O7 are insoluble solids and decompose on

Iodine
heating.
• I2O5 is a very good oxidizing agent; used in the estimation
of carbon monoxide.

• I > Cl > Br
Stability of
• Higher oxidation states of halogens tend to be more
Oxides
stable than the lower ones.
 METAL SALTS OF GROUP 17

Mg + Br2 ⟶ MgBr2
2Na + Cl2 ⟶ 2NaCl
Ionic character of the
halides
MF > MCl > MBr > MI where M is a
monovalent metal

Ionic Character for

different O.S. of metals
SnCl2 > SnCl4
 CHLORINE
Physical Properties
• Pungent and suffocating odour.
• It is about 2-5 times heavier than air. It can be liquefied easily into
greenish yellow liquid

Uses

• Manufacture of dyes, drugs and organic compounds such as

CCl4,CHCl3, DDT, refrigerants, etc.

• Sterilizing drinking water

• Preparation of poisonous gases such as phosgene (COCl2), tear

gas(CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).
 PREPARATION OF CHLORINE

Small Scale

MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O

4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2

2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2

NaClO + 2HCl → NaCl + Cl2 + H2O

 PREPARATION OF CHLORINE

Industrial Scale Deacon’s Process

Oxidation of hydrogen chloride gas by atmospheric oxygen in the presence

of CuCl2(catalyst) at 723 K
4HCl + O2 🡪 2Cl2 + 2H2O

Electrolytic Process

• Electrolysis of brine (concentrated NaCl

solution)
• Chlorine is liberated at anode
 REACTIVITY OF CHLORINE
2Al + 3Cl2 → 2AlCl3
Metals
2Na + Cl2 → 2NaCl
2Fe + 3Cl2 → 2FeCl3

Non-metals P4 + 6Cl2 → 4PCl3

S8 + 4Cl2 → 4S2Cl2

H2 + Cl2 🡪 2HCl
H containing
compounds H2S + Cl2 🡪 2HCl + S
C10H16 + 8Cl2 🡪 16HCl 10C
 REACTIVITY OF CHLORINE
Alkalies 2NaOH + Cl2 → NaCl + NaOCl + H2O
(cold and dilute)
6NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2O
(hot and conc.)
2Ca(OH)2 + 2Cl2 → Ca(OCl)2 + CaCl2 + 2H2O
Bleaching Powder

Oxidizing Agent 2FeSO4 + H2SO4 + Cl2 → Fe2 (SO4)3 + 2HCl

Na2SO3 + Cl2 + H2O → Na2SO4 + 2HCl

SO2 + 2H2O + Cl2 → H2SO4 + 2HCl

I2 + 6H2O + 5Cl2 → 2HIO3 + 10HCl

 HYDROGEN CHLORIDE

Physical • Colourless and pungent smelling gas

Properties • Easily liquefied to a colourless liquid
• White crystalline solid

420K
Lab NaCl + H2SO4 NaHSO4 + HCl + NaHSO4
Preparation
NaCl 823K Na2SO4 + HCl

Strong Acid HCl(g) + H2O(l) 🡪 H3O+ (aq) + Cl-(aq)

NH3 + HCl → NH4Cl

 HYDROGEN CHLORIDE - AQUA REGIA

• Three parts of concentrated HCl and one part of concentrated HNO3

HNO3 + 3HC1 ⎯→ 2H2O + NOCl + 2
(Cl)
(Conc.)
Au + 3[Q] ⎯→ AuCl3
Gold
(II) Chloride
Pt + 4[Cl] ⎯→ PtCl4

Platinium (IV) Chloride

 OXOACIDS OF HALOGENS

• Acid Strength: HOCl < HClO2 < HClO3 < HClO4

• Acid Strength: HClO4 > HBrO4 > HIO4
• Oxidizing Nature: HClO > HClO2 > HClO3 > HClO4
 INTERHALOGEN COMPOUNDS: PROPERTIES
Type Formula Physical state and colour Structure
 INTERHALOGEN COMPOUNDS
Preparation

Reactivity

• 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.
XX’ + H2O 🡪 HX + HOX
GROUP 18 INERT GASES
 GROUP 18 INERT GASES

• Group 18 consists of six elements: helium, neon, argon, krypton,

xenon and radon.
• Helium and sometimes neon are found in minerals of radioactive origin
e.g., pitchblende, monazite, cleveite. The main commercial source of
helium is natural gas.
• Except radon all occur in the atmosphere in
which argon is the major constituent.
• Xenon and radon are the rarest elements of the
group.
• Radon is obtained as a decay product of 226Ra.
GROUP 18 PROPERTIES
 PHYSICAL PROPERTIES

• Colourless, odourless and tasteless.

• Sparingly soluble in water.
• Very low melting and boiling points because the only type of
interatomic interaction in these elements is weak dispersion forces.
• Helium has the lowest boiling point (4.2 K) of any known substance. It
has an unusual property of diffusing through most commonly used
laboratory materials such as rubber, glass or plastics.
 CHEMICAL REACTIVITY

• Noble gases are least reactive due to:

❑ Completely filled ns2 and np6 configuration.
❑ High ionization enthalpy and more positive electron gain
enthalpy.
• Under extreme conditions, krypton reacts with fluorine to form KrF2
• First laboratory compound of Noble gases to be prepared was Xe+PtF6-.
• Thereafter a number of xenon compounds mainly with most
electronegative elements like fluorine and oxygen, have been
synthesized like XeF4 and XeOF4
COMPOUNDS OF XENON WITH FLUORINE

XeF4 + O2F2 🡪 XeF6 + O2

 COMPOUNDS OF XENON WITH FLUORINE

XeF2 Linear XeF4 Square planar XeF6 Distorted octahedral

XeOF4 Square pyramidal XeO3 Pyramidal

 COMPOUNDS OF XENON WITH FLUORINE

Powerful fluorinating agents.

• React with fluoride ion acceptors to form cationic species and fluoride
ion donors to form fluoro anions.
 HYDROLYSIS OF XENON FLUORIDES

XeF2

XeF4

XeF6
colourless
explosive solid

• Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2

1. Colour of F2 gas

a) Orange.
b) Dark blue.
c) Greenish yellow.
d) Pale yellow

Ans.
(d)
2. Which of the following oxides are insoluble
solids

a) I2 O 4
b) I2 O 5
c) I2 O 7
d) All of the above

Ans.
(d)
3. The X-X bond dissociation enthalapy down
the group

a) Br-Br > F-F > Cl-Cl > I-I

b) I-I > Cl-Cl > Br-Br > F-F
c) Cl-Cl > F-F > Br-Br > I-I
d) None of these

Ans.
(c)
4. The order of acidic strength is

a) H-I > H-Br > H-Cl > H-F

b) H-Cl > H-Br > H-I > H-F
c) H-F > H-Cl > H-Br > H-I
d) None of these

Ans.
(a)
5. Halogens combine among themselves to form a
number of compound known as

a) Intrahalogen compounds.
b) Polyhalogens componds.
c) Dihalogen compounds.
d) Interhalogen compounds.

Ans.
(d)
6. The trend of ionic character of the Monovalent atom(M)
with halogens

a) M-I>M-Br>M-Cl>M-F
b) M-Br>M-I>M-F>M-Cl
c) M-Cl>M-F>M-I>M-Br
d) M-F>M-Cl>M-Br>M-I

Ans.
(d)
7. The highest ionisation energy in the
following

a) Helium
b) Xenon
c) Krypton
d) Neon

Ans.
(a)
8. Xe (g) + 2F2 (g) ⟶ ? (In the proportion
1:5)

a) XeF2
b) XeF4
c) XeF7
d) None of these

Ans.
(b)
9. The structure of XeF4 is

a) Linear
b) Pyramidal
c) Trigonal planar
d) Square planar

Ans.
(d)
10. The structure of XeOF4

a) T shape
b) V shape
c) Square pyramidal
d) Triangular pyramidal

Ans.
(c)
11. Hydrolysis of XeF4 with water gives

a) XeO3
b) XeO4
c) XeO5
d) None of these

Ans.
(a)
Thank You