1

Group 16 Elements-Chalcogens
Oxygen, sulphur, selenium, tellurium and polonium constitute Group 16 of the periodic table.
Oxygen ,O [He]2S22p4 Electronic Configuration- ns2 np4
2 4
Sulphur, S [Ne]3S 33p Atomic and Ionic Radii ↑- number of shells ↑
Selenium, Se [Ar]3d104s24p4 Ionisation Enthalpy↓- size↑
10 2 4
Tellurium, Te [Kr]4d 5s 5p Electron Gain Enthalpy↓ -size↑
Polonium, Po [Xe]4f145d106s26p4
1.Ionisation enthalpy of gp 16 is less than gp15. Group 15 elements have extra stable half- filled p
orbitals, hence high ionization enthalpy
2. Oxygen has less negative electron gain Due to small size of oxygen,the added e- suffer
enthalpy than sulphur. more e- -e- repulsion in 2p orbital. Sulphur being
bigger, no repulsion occurs in 3p orbital.
3.The stability of +6 oxidation state decreases Due to inert pair effect, +4 is more stable than +6
and that of +4 state increases down the group for heavier members.
4.S has a strong tendency for catenation S–S single bond is stronger than the O-O single
properties than O bond. Because of small size of O, lp of e- on two O
atoms repelthe bp of O-O bond, hence O-O bond
is weak.
5. Oxygen exists as diatomic gas (O2), sulphur as O has small size, high electronegativity, form
polyatomicsolid (S8). pπ -p π multiple bonds (form O=O bond), hence
diatomic.
Due to small size, O2 molecules are held by weak
van der waals force, hence exist as gas.
S has large size, low electronegativity, does not
form pπ -p π multiple bonds, it form S-S single
bond, hence polyatomic.
Due to large size, S8 molecules are held by strong
van der waals force, hence exist as solid.
6. The tendency to exhibit –3 oxidation state Due to increase in size and electronegativity
decreases down the group decreases.

7. O shows only –2 oxidation state except in (
OF2 ). Other elements of the group exhibit + 2, +
4, + 6 oxidation states.
8. State reason for the anomalous properties of
O. (or) How does first member of group16 differ
from the rest?
9. SF6 is known, SH6 is not known.
10.SCl6 is not known, but SF6 is known
11. S forms SF6 but On cannot form OF6.
12. The compounds of F with O are called
fluorides of oxygen and not the oxides of fluorine.
(or) OF2 should be called oxygen fluoride and not
O has high electronegativity and absence of d -
orbitals. Other members have d orbitals.
(1) small size (2) high electronegativity,(3) high
ionisation enthalpy (4) non-availability of d
orbitals (5) form pπ -p π multiple bonds
F being the strongest oxidizing agent,oxidizes S to
maximum O.S of +6. H is a weak oxidizing agent
F being the strongest oxidizing agent,oxidizes S to
maximum O.S of +6.Cl is a weak oxidizing agent. S
cannot hold six large sized Cl atoms around it.
Due to absence of vacant d- orbitals in O.
F is more electronegative than O
fluorine oxide.
13. H2O has high b.pt. than H2S and then the
b.pt.increases down the group[ from H2S to H2Te]
14.H2O is liquid and H2S a gas
15. Inspite of nearly the same electronegativity, O
forms H-bonding while cl does not.
16. Thermal stability decreases from H2O to H2Te
[H2O > H2S > H2Se > H2Te]
17. Reducing character increases from H2O to
H2Te [H2O < H2S < H2Se < H2Te]
18.Acidic character increases from H2O to H2Te
[H2O < H2S < H2Se < H2Te]
19. H2S is less acidic than H2Te.
20. H2S is acidic while H2O is neutral.(or) H2S is
stronger acid than H2O.
21. SF6 is chemically inert (or) SF6 is less reactive SF6 has octahedral structure. S atom is well
than SF4 (or) SF6 is not easily hydrolysed.
22. Sulphur vapours S2 [and O2] are paramagnetic. It has 2 unpaired electrons in the antibonding π*
23. Ozone is a good oxidizing agent.
Q. Ozone is thermodynamically unstable. Why?
24. Comment on the nature of two S–O bonds
formed in SO2 molecule. Are the two S–O bonds
in this molecule equal?
25. How is the presence of SO2 detected?
26. What happens when sulphur dioxide is passed
through an aqueous solution of Fe(III) salt?
H2O has high b.pt. than H2S because it form
intermolecular hydrogen bond.
B.pt increases from H2S to H2Te because as size
increases, van der waals force increases.
There is intermolecular H-bonding in H2O, due to
small size and high electronegativity of O.But
there is no H- bonding in H2S.
O has smaller size than Cl.
Size of central atom ↑s, E-H bond length ↑s, their
bond dissociation enthalpy ↓s and hence thermal
stability ↓s
Size of central atom ↑s, E-H bond length ↑s, their
bond dissociation enthalpy ↓s, reducing character
↑s (ability to donate hydrogen ↑s)
Size of central atom ↑s, E-H bond length ↑s, their
bond dissociation enthalpy ↓s, acidic character ↑s
Size of central atom ↑s, bond dissociation enthalpy
↓s, acidic character ↑s [Te –large size, low bond
dissociation enthalpy of Te-H bond, more acidic]
S –large size, low bond dissociation enthalpy of S-
H bond, more acidic.
protected by 6 F atoms.Itis stable for steric
reasons. SF4 has see-saw geometry.
molecular orbitals
Due to the ease with which it liberates atoms of
nascent oxygen (O3 → O2 + O)
PbS + 4O3 → PbSO4 + 4O2
2I– + H2O + O3 → 2OH– + I2 + O2
Since decomposition of O3 into oxygen
[ 2O3 →3O2 ] results in ΔH = –ve and ΔS = +ve,
hence results in large -ve ΔG *ΔG = ΔH-T ΔS+.
Therefore, high concentrations of ozone can be
dangerously explosive.
Both the S-O bonds are covalent and equal bond
strength due to resonance.
SO2 decolourises acidified potassium
permanganate solution.
5SO2+ 2MnO4- + 2H2O → 5SO42− + 4H+ + 2Mn2+
SO2 is a reducing agent, reduces Fe3+ to Fe2+
2Fe3+ + SO2 + 2H2O → 2Fe2+ + SO4 2 −+ 4H+
27. Why is Ka2 << Ka1 for H2SO4 in water?
H2SO4 + H2O → H3O+ + HSO4− ; Ka1 = very large
( Ka1 >10)
HSO4 + H2O→ H3O+ + SO42− ; Ka2 > = 1.2 × 10−2
Q. How is O3 estimated quantitatively?
Q. Which of the following does not react with
oxygen directly? Zn, Ti, Pt, Fe
Q. Complete the following reactions:
(i) C2H4 + 3O2 →2CO2 + 2H2O
(ii) 4Al + 3O2 →2Al2O3
H2SO4 is a very strong acid in water, hence it
largely dissociated into H3O+ and HSO4- .The
ionization of HSO4-to H3O+ and SO42- is very very
small. That is why Ka2 << K a1. Negatively charged
HSO4- has a less tendency to donate H+ to water
as compared to neutral H2SO4 .
When ozone reacts with an excess of KI solution
buffered with a borate buffer (pH 9.2), iodine is
liberated which can be titrated against a std
solution of sodium thiosulphate.
2I–+ H2O + O3 → 2OH– + I2 + O2
Pt

Group -17 elements

9-Fluorine-F [He]2s22p5 General electronic configuration- ns2 np5 [7 V e- - 1electron
short of the next noble gas]
17-Chlorine-Cl [Ne]3s23p5 Atomic / Ionic Radii ↑- No. of shells ↑
10 2 5
35-Bromine-Br [Ar]3d 4s 4p Ionisation Enthalpy ↓- size↑
10 2 5
53-Iodine-I [Kr]4d 5s 5p Electron Gain Enthalpy ↓-size↑
14 10 2 5
85-Astatine-At [Ar]4f 5d 6s 6p Electronegativity ↓, Common oxidation states -1,+1,+3,+5,+7
Group 17 elements are collectively known as the halogens -salt producers.
1.Sea is the greatest source of some halogens. Sea water contains chlorides, bromides and iodides of
Comment. Na, K, Mg and Ca but mainlyNaCl. Deposits of dried
up seas contain NaCl and carnallite, KCl.MgCl2.6H2O.
Certain forms of marine life contain iodine in their
systems; various seaweeds contain 0.5% of iodine.
2. Halogens have maximum negative electron Halogens have the smallest size and high effective
gain enthalpy in the respective periods of the nuclear charge, hence they readily accept one
periodic table. electron to acquire noble gas electronic confign.
3. Negative electron gain enthalpy of fluorine Due to small size of fluorine atom, the added electron
is less than that of chlorine. experience strong interelectronic repulsions in the
small 2p orbitals.
4. Halogens are strong oxiding agent. Due tolow bond dissociation enthalpy, high
electronegativity, large negative electron gain
enthalpy, halogens have a strong tendency to accept
electrons and thus got reduced, thus act as strong
oxidizing agent
5. Fluorine is anomalous in many properties. Due to small size, high electronegativity and absence

6. Although electron gain enthalpy of fluorine
is less negative as compared to chlorine,
fluorine is a stronger oxidising agent than
chlorine.
7.Considering the parameters such as bond
dissociation enthalpy, electron gain enthalpy
and hydration enthalpy, compare the oxidising
power of F2 and Cl2.
8.Bond dissociation enthalpy of F2 is less than
that of Cl2
9.Flourine exhibit only –1 oxdn state whereas
other halogens exhibit + 1,+ 3,+ 5 and +7
oxdn states also
10.Flourine forms only one oxoacid, HOF
11.All halogens are coloured.
12.Most of the reactions of fluorine are
exothermic.
13.ClF3 exists but FCl3 does not.
14.The order of stability of halides
H–F > H–Cl > H–Br > H–I.
15.Increasing order of acidic strength
HF<HCl<HBr< HI
16.HI in aqueous solution is strong acid than
HF
17.HF is the weakest acid among HX inspite
of the fact that F is most electronegative.
18.Metalfluorides are more ionic than its
chlorides.
19.HF has higher boiling point than HCl. (or)
HF is a liquid, other hydrogen halides are
gases.(or)HF is least volatile whereas HCl is
most volatile
20.The order of boiling point –HF
>HI>HBr>HCl
21.OF2 is oxygen fluoride and not fluorine
oxide.
of d-orbitals, low bond dissociation enthalpy of F-F
bond.
Due to (i) low bond dissociation enthalpy of F-F bond
(ii) high hydration enthalpy of F−
Although F has less negative electron gain enthalpy
than chlorine,F2 is a stronger oxidising agent than
Cl2. due to (i) low bond dissociation enthalpy of
F-F bond (ii) high hydration enthalpy of F−
(iii) high E0 value [reduction potential]
(i) small size (ii)large electron-electron repulsion
among the lone pairs in F2
F is the most electronegative element and has no d -
orbitals in its valence shell and cannot expand its octet,
hence cannot exhibit any positive oxdn state. Other s
have d orbitals, can expand their octet.
Due to small size, high electronegativity and absence
of d-orbitals.
Due to absorption of radiations in visible region which
results in the excitation of outer electrons to higher
energy level.
Due to small and strong bond formed by it with other
elements.
Cl has vacant d-orbitals, show +3 oxdn state. But F
has no vacant d orbital, most electronegative, cannot
show +veoxdn state.
As size↑, bond dissociation enthalpy [H-X]decreases.
As size↑ ,bond length↑ , bond dissociation enthalpy↓,
therefore acidic strength ↑
Due to large size of I, low bond dissociation enthalpy
of H-I bond, HI is more acidic
F-small size, highest bond dissociation enthalpy in
HF
Greater the difference in electronegativity, more will
be its ionic character, F being more electronegative
than Cl
Due to intermolecular hydrogen bonding in
HF,highBpt. There is no H-bonding in HCl-least van
der waals force, less Bpt
HF has B.pt due to H-bonding.Bpt↑from HCl to HI
due to size↑, van der waals force↑ , Bpt↑
F is more electronegative than oxygen
22.Write two uses of ClO2
23.SnCl4, PbCl4, SbCl5 and UF6 are more
covalent than SnCl2, PbCl2, SbCl3 and UF4
24.Interhalogens compounds.
Eg: ICl, IF3, BrF5
25.Interhalogens compounds are more
reactive than halogens. (or)
ICl is more reactive than I2
26.The order of acidic strength of oxoacids of
halogens-HOF>HOCl>HOBr> HOI
27.Arrange HClO4, HClO3, HClO2,HClO in
order of acidic strength (ii) oxidizing power.
Give reason
28.Give two examples to show the anomalous
behaviour of fluorine.
29.Give the reason for bleaching action of Cl2.
30.Name two poisonous gases which can be
prepared from chlorine gas.
31.WhenHCl reacts with finely powdered
iron, it forms ferrous chloride and not ferric
chloride.
It is used as a bleaching agent for paper pulp and
textiles and is used for purifying drinking water.
Higher the +veoxdn state of central atom, more will
be its polarizing power and greater is its covalent
character.[Fajans rule]
Halogens combine amongst themselves to form a no. of
compounds known as interhalogens compounds.
X-X’ bond in interhalogens are weaker than X-X
bond in halogens [due to less extent of overlapping
between the orbitals of dissimilar atoms].
Greater the electronegativity of halogens, greater is
acidic strength of oxoacids.[F> Cl >Br> I]
Acidic strength HClO4> HClO3> HClO2>HClO
Reason-Stability of conjugate acid ClO4- >ClO3- >ClO2- >
ClO-. As the no. of oxygen atom increases , -ve charge
can be more stabilized through resonance.
Oxidising power :HClO4˂ HClO3˂ HClO2˂HClO
Forms only one oxoacid, HOF
HF is liquid, form intermolecular H-bonding.
Bleaching action of Cl2 is due to oxidation.
Cl2 + H2O → 2HCl + O
Coloured substance + O → Colourless substance
Phosgene, mustard gas and tear gas.
HCl reacts with Fe produces H2. Fe + 2HCl → FeCl2 + H2
Liberation of H2 prevents the formation of FeCl3

Group 18 elements
2-Helium, He 1s2 General electronic configuration- ns2np6 [except helium- 1s2]
10-Neon, Ne [He]2s22p6 Atomic radii ↑
2 6
18-Argon, Ar [Ne]3s 3p Ionisation enthalpy↓ - size↑
10 2 6
36-Krypton, Kr [Ar]3d 4s 4p
54-Xenon, Xe [Kr]4d105s25p6
86-Radon, Rn [Xe]4f145d106s26p6 Radon is radioactive-difficult to study

1.What inspired N. Bartlett for carrying In 1962, Neil Bartlett first prepared a red compound
out reaction between Xe and PtF6? O2+PtF6− . He realised that the first ionisation enthalpy
of O2 was same as xenon. Then he prepared red colour

2.Why are the elements of Group 18
known as noble gases ?
3.Noble gases are inert [least reactive].
4.Noble gases exhibit very high ionisation
enthalpy.
5.Noble gases have large positive values of Due to stable electronic configuration.
electron gain enthalpy.
6.Noble gases are monoatomic
7.Noble gases have comparatively largest
atomic size.
8.Noble gases have very low boiling
points.
9.Of the noble gases, only xenon is known
to form real chemical compounds.
10.Noble gases form compounds with
fluorine and oxygen only.
11.It has been difficult to study the
chemistry of radon
12.Xenon readily forms compounds but
krypton does not form compounds easily.
13.He and Ne does not form compounds
with fluorine.
14.Xenon does not form compounds such
as XeF3 and XeF5
15.Helium is used in diving apparatus.
16.Helium is used for inflating aeroplane
tyres & filling balloons for meteorological
observations
17. Does the hydrolysis of XeF6 lead to a
redox reaction?
18.Which one of the following does not
compound Xe+PtF6− by mixing PtF6 and xenon.
completely filled valence shell orbitals(stable
configuration) and hence unreactive.
(i) Noble gases have completely filled valence shell.
(ii) They have high ionisation enthalpy and more positive
electron gain enthalpy.
Due to stable electronic configuration.
They have stable electronic configuration, they cannot
form covalent bonds.
In noble gases, we can measure only van der waals radii
which are larger than covalent radii.
Noble gases being monoatomic ,haveweak dispersion
forces.
Due to low ionization enthalpy of xenon, it is possible to
excite the paired electrons from np to nd orbitals
Because fluorine and oxygen arestrong oxidizing agents
(most electronegative elements)
Radon is radioactive with very short half-life.
Xenon has lower ionisation enthalpy than krypton
Stable configuration, high ionization enthalpy, absence
of vacant d-orbitals.
By the promotion of 1, 2 or 3 electrons from p-orbital
to the vacant d-orbital in the valence shell results in 2,
4or 6 half filled orbitals. Thus Xe can combine with only
even no. of fluorine and not odd.
Due to low solubility of helium in blood.
Helium is a non-inflammable and light gas.
No, the oxidation states of all the elements remain the
same.
NeF2
exist? (i) XeOF4 (ii) NeF2 (iii) XeF2 (iv)
XeF6
Q. Give the formula and describe the structure of a noble gas species which is isostructural with:
(i) ICl4– = XeF4 [square planar](ii) IBr2– = XeF2[linear](iii) BrO3– = XeO3[pyramidal]

Simple Oxides
A binary compound of oxygen with another element is called oxide.
Oxides can be simple (e.g., MgO, Al2O3 ) or mixed (Pb3O4, Fe3O4).
Simple oxides can be classified on the basis of their acidic, basic or amphoteric character.
Acidic oxide: An oxide that combines with water to give an acid (e.g., SO2, Cl2O7, CO2, N2O5 ).
Eg: SO2 + H2O → H2SO3 [acid]
General rule: Non-metal oxides are acidic and oxides of some metals in high oxidation state have acidic
character (e.g., Mn2O7, CrO3, V2O5).
Basic oxides: The oxides which give a base with water. (e.g., Na2O, CaO, BaO).
Eg: CaO + H2O → Ca(OH)2 [Base]
General rule : Metallic oxides are basic.
Amphoteric oxides: Metallic oxides that show characteristics of both acidic as well as basic oxides.
Eg: Al2O3 ,ZnO
Al2O3 + 6HCl + 9H2O → 2 * Al(H2O)6 ]3+ + 6Cl−
Al2O3 + 6NaOH + 3H2O → 2Na3[Al(OH)6]

Neutral oxides: Oxides which are neither acidic nor basic. Eg: CO, NO and N2O.

Ozone
It is formed from atmospheric oxygen in the presence of sunlight. This ozone layer protects the earth’s
surface from an excessive concentration of ultraviolet (UV) radiations.
Preparation
Dry stream of oxygen is passed through a silent electrical discharge to give ozone [ozonised oxygen].
3O2 → 2O3
It is an endothermic process, it is necessary to use a silent electrical discharge to prevent decomposition
of O3.

Reasons for ozone layer depletion.

 Nitric oxide combine very rapidly with ozone. Thus NO emitted from the exhaust systems of
supersonic jet aeroplanes slowly depletes the ozone layer.
NO + O3 → NO2 + O2
 Use of freons [used in aerosol sprays and as refrigerants] depletes the ozone layer.

Sulphur – Alltropic Forms - yellow rhombic(α-sulphur) and monoclinic (β -sulphur)

  The stable form at room temperature is rhombic sulphur, which transforms to monoclinic
sulphur when heated above 369 K.
Rhombic sulphur (α-sulphur)
 yellow in colour, m.p. 385.8 K and specific gravity 2.06.
 Rhombic sulphur crystals are formed on evaporating the solution of roll sulphur in CS2.
 It is insoluble in water . It is readily soluble in CS2.
Monoclinic sulphur (β-sulphur)
 Its m.p. is 393 K and specific gravity 1.98.
 It is soluble in CS2.
 Monoclinic sulphur is prepared by melting rhombic sulphur in a dish and cooling, till crust is
formed. Two holes are made in the crust and the remaining liquid poured out. On removing the
crust, colourless needle shaped crystals of β-sulphur are formed.
 It is stable above 369 K and transforms into α-sulphur below 369K.
 α-sulphur is stable below 369 K and transforms into β-sulphur above 369K.
 At 369K ,both α- and β-sulphur are stable. This temperature is called transition temperature.

Q. Care must be taken while preparing sulphuric acid solution from concentrated sulphuric acid.
H2SO4 dissolves in water with the evolution of a large quantity of heat( highly exothermic). The
concentrated acid must be added slowly into water with constant stirring.