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Chapter-13

s - and p - Block Elements

Elements of group I-A (Alkali Metals) and Group II-A constitute s-block. They have their valence electrons in s-
orbital. S-block has only metals however hydrogen and helium are exceptions, these two are non-metals.
Elements of group III-A, IV-A, V-A, VI-A, VII-A and VIII-A constitute p-block. They have their valence electrons
in p-orbital. P-block consists of metals as well as non-metals.

3rd Period (Sodium to Argon)

Trend in Physical properties:

Electronic configuration:
The 3rd shell starts from sodium and completes at argon.
11Na → 1s2, 2s2, 2p6, 3s1 = [Ne], 3s1
12Mg → 1s2, 2s2, 2p6, 3s2 = [Ne], 3s2
13Al → 2 2 6 2
1s , 2s , 2p , 3s , 3p 1
= [Ne], 3s2, 3p1
14Si → 2 2 6 2
1s , 2s , 2p , 3s , 3p 2
= [Ne], 3s2, 3p2
15P → 2 2 6 2
1s , 2s , 2p , 3s , 3p 3
= [Ne], 3s2, 3p3
16S → 1s2, 2s2, 2p6, 3s2, 3p4 = [Ne], 3s2, 3p4
17Cl → 2 2 6 2
1s , 2s , 2p , 3s , 3p 5
= [Ne], 3s2, 3p5
18Ar → 2 2 6 2
1s , 2s , 2p , 3s , 3p 6
= [Ne], 3s2, 3p6

Trend in atomic radii:

Generally atomic radii decrease in a period from left to right across the period due to increasing nuclear charge.
For Na, Mg and Al metallic radii are considered. For Si, P, S, and Cl covalent radii are considered while for Argon
van der waal radius is taken into consideration. Metallic radii and covalent radii are comparable while van der waal
is not comparable to them. Van der waal radius is bigger than metallic and covalent radius.

Na Si P S Si Ar
Mg Al

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Ionization energy:
“The energy required to remove the most loosely bound electron from an isolated atom (gaseous atom) or gaseous
ion to make cation is called Ionization Potential or Ionization Energy.”

Ionization energy is an endothermic process in which energy is absorbed so sign for this energy is +ve. This energy
is required to overcome the force of attraction of nucleus on the electron. After removal of first electron hold of
nucleus on remaining electrons increases so Second I.P is greater than First I.P because more energy is required to
remove the second electron and so on.
+ -
e.g (i) Na → Na + e (I.E)1 = +496 kJ/mol
(2,8,1) (2,8)
+ -
e.g (ii) Mg → Mg + e (I.E)1 = +738 kJ/mol
(2,8,2) (2,8,1)
+ 2+ -
Mg → Mg + e (I.E)2 = +1451 kJ/mol
(2,8,1) (2,8)

By I.E values we can determine number of valence electrons and valency of an atom. e.g.
1st I.E 2nd I.E 3rd I.E 4th I.E
Li 520 7,298 11,815 -
Be 899 1,757 14,848 21,006
nd
In case of Li there is a sudden jump in value of its 2 I.E which means this is electron of its inner shell so its valence
shell has only one electron and thus its valency is one.
In case of Be there is a sudden jump in value of its 3rd I.E which means this is electron of its inner shell so its
valence shell has two electrons and thus its valency is two.

Factors affecting I.E or I.P:

(i) Nuclear Charge: With increase in nuclear charge, hold of nucleus increases on electrons so more energy
will be required to remove electrons. Thus more is the nuclear charge more will be the I.E and vice versa.
(ii) Atomic Size: Smaller is the size of atom, more will be the hold of nucleus on electrons so more energy
will be required to remove electrons. Thus smaller is the atomic size more will be the I.E and vice versa.
I.E α 1/r2
(iii) Shielding Effect: Greater the shielding effect of lower shells less will be the hold of nucleus on electrons of
outer shell so low will be the I.E and vice versa.
(iv) Penetration Effect: Fraction of time which the electrons of outer orbitals spend near nucleus is
called penetration effect. The order of this effect and thus I.E is
s>p>d>f
(v) Electronic Configuration: Completely filled and half-filled orbitals are more stable and thus their electrons
are difficult to remove so their I.E is high. Thus elements of Groups 1A, IIA and VIIIA have extra ordinary
high I.E.

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Trend of 1st ionization energy in Periodic Table:

Generally I.E increases in a period from left to right due to decreasing atomic size and increasing nuclear
charge. But anomalies are observed at group IIA and VA they have extra ordinary high I.E. This is due to
the reason that they have completely filled or half-filled outer orbitals which are more stable and thus their
electrons are difficult to remove so their I.E are high. Group II-A has outer completely filled s-orbital while
group V-A has outer half-filled p-orbital so they have extraordinary high ionization energies.
e.g. trend of Ionization Energy in 2nd and 3rd period is
Groups IA IIA IIIA IVA VA VIA VIIA VIIIA
Elements of period II Li Be B C N O F Ne
Ionization Energy (kJ) 520 900 801 1086 1402 1314 1681 2081
Elements of period III Na Mg Al Si P S Cl Ar
Ionization Energy (kJ) 496 738 578 786 1012 1000 1251 1521

On other hand in a group I.E decrease from top to bottom due to increasing atomic size.

Electron Affinity:
“The energy released or absorbed when an electron is added to a gaseous atom or gaseous ion is called electron
affinity.”
e.g. (i) Cl + e- → Cl- ∆H E.A = -349 kJ/mol
e.g. (ii) O+e →O- -
∆H E.A(1) = -141 kJ/mol
O- + e- → O2- ∆H E.A(2) = +844 kJ/mol

Trend of Electron Affinity:

Elements of period III Na Mg Al Si P S Cl Ar

Electron affinity -53 230 -50 -120 -74 -200 -349 35

Generally electron affinities increase across the period (from left to right). However group II-A elements due to their
complete s-orbital have positive values for their first electron affinities. Similarly group VIII-A elements also have
positive values for their first electron affinities due to complete p-orbital.
Second electron affinities are positive for all elements.

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Electronegativity:
“The tendency of an atom to attract shared pair of electrons is called electronegativity.”

Trend in electronegativity:

Electronegativity increases across the period (from left to right) due to increasing nuclear charge and
decreasing atomic size.

Elements of period III Na Mg Al Si P S Cl Ar

Electronegativity 0.93 1.31 1.81 2.02 2.19 2.58 3.16 -

As Argon does not form covalent bonds hence it cannot be assigned electronegativity value.

Electrical Conductivity:
“The ability of a substance to conduct electricity is called electrical conductivity.”

Metals possess free electrons (valence shell electrons) so they conduct electricity but nonmetal cannot conduct
electricity as they do not possess free electrons. However carbon (graphite) has free p-electrons so it also conduct
electricity.

Trend in electrical conductivity:

Electrical conductivity increases from sodium to aluminum. Silicon is semiconductor. From Phosphorus to
Argon are non-metals and non-conductors.

Elements of period III Na Mg Al Si P S Cl Ar

Electrical conductivity 0.26 0.42 1.00 0.10 0 0 0 0

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Melting and Boiling Points:

“The temperature at which solid and liquid exist in equilibrium is called melting point.”

“The temperature at which vapour pressure of liquid becomes equal to atmospheric or external pressure is called
boiling point.”

Trend in Melting and Boiling Points:

The melting and boiling points increases across the period (from left to right) up to middle and then decreases.

Elements of period III Na Mg Al Si P S Cl Ar

Melting Point (K) 371 922 933 1683 317 392 172 84
Boiling Point (K) 1156 1380 2740 2628 553 718 238 87

Trend in Chemical Properties:

Reaction with Water:
Reactivity of elements with water in period from left to right decreases up to middle and then become
irregular.

Sodium reacts with cold water vigorously producing sodium hydroxide and hydrogen gas. Reaction is highly
exothermic.
2Na +2H2O→ 2NaOH + H2

Magnesium do not show appreciable reaction with cold water, it react with hot (boiling) water.
When a clean coil of magnesium is dropped in cold water it gets covered with bubbles of hydrogen which floats it to
the surface of water. As a result of reaction magnesium hydroxide is also produced which get deposited on the
surface of magnesium and thus stops further reaction.
Mg +2H2O→ Mg(OH)2 + H2
Magnesium burns in steam and produce magnesium oxide (white colour) and hydrogen gas.
Mg +H2O(g) → MgO + H2
Aluminum powder reacts with steam on heating. But reaction is very slow due to oxide layer on aluminum.
2Al + 3H2O(g) → Al2O3 +3 H2
Silicon reacts with steam at red heat.
Si + 2H2O(g) →SiO2 +2 H2

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Chlorine reacts with water and produces hydrochloric acid and hypochlorous acid. The reaction is reversible
Hypochlorous acid in presence of sunlight slowly decomposes to hydrochloric acid and oxygen gas.

2Cl2 +2 H2O ⇌ 2HCl +2 HOCl

2HOCl →2 HCl + O2
Overall reaction 2Cl2 + 2H2O → 4HCl + O2

Argon does not react with water.

Reaction with Oxygen:

Sodium (Group I-A) burns in oxygen with yellow flame and produces a mixture of sodium oxide and sodium
peroxide. Both are white solids.
4Na + O2 → 2Na2O (sodium oxide. It is normal oxide)
2Na + O2 → Na2O2 (sodium peroxide)
Magnesium (Group II-A) burns in oxygen with intense luminous flame and produce white solid magnesium oxide.
2Mg + O2 → 2MgO
Aluminum (Group III-A) will burn only if it is powdered, otherwise oxide layer on it prevents reaction.
4Al +3 O2 → 2Al2O3
Silicon (Group IV-A) burns only on very strong heating.
Si + O2 →SiO2
White Phosphorus (Group V-A) readily catches fire in air and burns with white smoke producing phosphorus (III)
oxide and phosphorus (V) oxide.
P4 + 3O2 → P4O6 also written as P2O3
P4 + 5O2 → P4O10 also written as P2O5
Sulphur burns in oxygen on gentle heating with a pale blue flame producing sulphur dioxide gas.
S + O2 → SO2
Argon does not react with oxygen.

Reaction with Chlorine:

Sodium (Group I-A) burns in chlorine with bright orange flame and produces a white solid sodium chloride.
2Na + Cl2 → 2NaCl
Magnesium (Group II-A) burns in chlorine with intense luminous flame and produce white solid magnesium
chloride.
Mg + Cl2 → MgCl2
Aluminum (Group III-A) will react with chlorine when dry chlorine is passed over aluminum foil placed in a long
tube. Reaction occurs on heating. Pale yellow aluminum chloride is produced.
2Al +3Cl2 → 2AlCl3
Silicon (Group IV-A) reacts with chlorine when chlorine is passed over heated powder of silicon. A colourless
liquid silicon tetra chloride is produced.
Si + 2Cl2 →SiCl4
White Phosphorus (Group V-A) burns in chlorine producing phosphorus (III) chloride and phosphorus (V) chloride.
P4 + 6Cl2 → 4PCl3
P4 + 10Cl2 → 4PCl5

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Sulphur reacts with chlorine if chlorine is passed over heated sulphur and disulphur chloride (Sulphuryl chloride) is
produced which is orange coloured liquid having foul smell.
2S + Cl2 → S2Cl2
Argon does not react with chlorine.

Compounds of Third Period:

Oxides of Third Period:
Binary compounds of oxygen are called oxides.

Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7

- - - - P4O6 SO2 Cl2O

Structure of oxides:
Oxides of sodium, magnesium and aluminum are giant ionic structures, oxide of silicon is giant molecular structure,
oxide of phosphorus is dimer, while oxides of sulphur and chlorine are discrete molecules.

Melting and Boiling points of oxides:

Melting and boiling points of oxides of sodium, magnesium and aluminum are high due to their giant ionic
structures. They have strong ionic bonds so high energy is required to break these bonds, thus their melting and
boiling points are high.
Melting and boiling points of oxide of silicon are high due to its giant molecular structure. It has strong covalent
bonds so high energy is required to break these bonds, thus its melting point and boiling point are high.
Melting and boiling points of oxides of phosphorus, sulphur and chlorine are low because they exist as discrete
molecule. They have weak van der Waal forces so little energy is required to overcome these forces, thus their
melting and boiling points are low. Strength of Van der Waal forces depends upon size, shape and polarity of
molecules.
Na2O MgO Al2O3 SiO2 P4O10 P4O6 SO3 SO2 Cl2O7 Cl2O
o
Melting Points ( C) 1280 2900 2040 1610 340 23.8 -17 -72 -92 -120.6
Boiling Points (oC) 1950 3600 2977 2230 360 173.1 45 -10 82 2

Electrical conductivity of oxides:

The covalent oxides do not conduct electricity as they do not possess free electrons also they do not have ions.
However ionic oxides in molten state or aqueous state conduct electricity due to movement of their ions.

Acidic and basic behaviour of oxides:

Across the period basic strength of oxides decreases while acid strength increases. Thus oxides of Na and Mg are
basic. Oxide of Al is amphoteric while oxides of Si, P, S, and Cl are acidic.

Sodium oxide reacts vigorously with water and produces alkaline solution.
Na2O(s) + H2O(l) → 2Na+(aq) + 2OH-(aq)
Or O2- + H2O → 2OH-
Sodium oxide being base also reacts with acids and produces salt and water.
Na2O(s) + 2HCl(aq) → 2NaCl(aq) + H2O(l)

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Magnesium oxide is slightly soluble in water. It also produces alkaline solution.

MgO(s) + H2O(l) ⇌ Mg+2(aq) + 2OH-(aq)
Magnesium oxide being base also reacts with acids and produces salt and water.
MgO(s) + 2HCl(aq) ⇌ MgCl2(aq) + H2O(l)
CaO also show same behaviour CaO(s) + 2HCl(aq) ⇌ MgCl2(aq) + H2O(l)
Aluminum oxide being amphoteric oxide reacts both with dilute acids and dilute alkalis.
Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)
Al2O3(s) + 2NaOH(aq) → 2NaAlO2(aq) + H2O(l)
Sodium aluminate
Silicon oxide does not react with water however it reacts with alkalis as it is weak acid.
SiO2(s) + 2NaOH(aq) → Na2SiO3 + H2O(i)
However CO2 can react with water CO2(g) + H2O(l) → H2CO3(aq) (Carbon belongs to 2nd period)
Oxide of nitrogen reacts with water and produces two acids.
2NO2(g) + H2O(l) → HNO2(aq) + HNO3(aq)
Oxides of P, S and Cl react with water and produce strongly acidic solution.
P4O10(s) + 6H2O(l) → 4H3PO4(aq) (Strong acid)
SO3(g) + H2O(l) → H2SO4(aq) (Strong acid)
Cl2O7(l) + H2O(l) → 2HClO4(aq) (Strong acid)
However Cl2O produce comparatively weak acid.
Cl2O(g) + H2O(l) → 2HClO(aq) (weak acid)
SO2 also react with water SO2(g) + H2O(l) → H2SO3(aq)

The following table is showing summery of trend in physical properties of oxides:

Formula of Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
Oxide P4O6 SO2 Cl2O
State of Solid Solid Solid Solid Solid Liquid Liquid
oxide Solid Gas Gas
Electrical Good Good Good Very poor Nil Nil Nil
Conductivity
Structure of Giant ionic Giant ionic Giant ionic Giant Discrete Discrete Discrete
Oxides Structure Structure Structure molecular molecules molecules molecules
Structure
Nature of Strongly Weakly Amphoteric Acidic Acidic Acidic Acidic
Oxide alkaline alkaline

Chlorides of Third Period:

The following table is showing summery of trend in physical properties of chloride:

Formula of Oxide NaCl MgCl2 Al2Cl6 SiCl4 PCl3 S2Cl2
State of Chlorides Solid Solid Solid Liquid Liquid Liquid
Melting points(oC) 801 708 192.4 - 69 - 93.6 - 80
Boiling points(oC) 1465 1418 423 57 74 136
Electrical Conductivity Good Good Very poor Nil Nil Nil
in liquid state
Structure of Giant ionic Giant ionic Molecular Discrete Discrete Discrete
Chlorides Structure Structure Structure molecules molecules molecules
Nature of Ionic Partly ionic Partly ionic Polar Polar Polar
Chlorides Covalent Covalent Covalent

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Addition of Dissolves Dissolves Dissolves Reacts with water Reacts with water Reacts with water
producing fumes producing fumes producing fumes
chlorides to water readily readily readily of HCl of HCl of HCl
Chlorides of Na and Mg are giant ionic, having ionic bonds which are strong so their melting and boiling points are
high. While chlorides of Al, Si, P and S are discrete molecules having weak van der Waal forces so their melting
and boiling points are low.

Hydroxide of Third Period:

Hydroxides are the compounds in which OH- (hydroxide) ion is attached to metals through ionic bonds or OH
(neutral) group attached to non metals through covalent bonds.
The ionic hydroxides are basic in nature e.g. NaOH and Mg(OH) 2.
Aluminum hydroxide Al(OH) 3 is amphoteric.
The covalent hydroxides are acidic in nature e.g. Si(OH)4 or H4SiO4 , H3PO4, H2SO4 and HClO4.
(Ortho Silicic acid)
OH O O O
│ ↑ ║ │
HO — Si — OH HO — P — OH HO — S — OH H — O — Cl — O
│ │ ║ │
OH OH O O

Sodium Hydroxide (NaOH):

Preparation:
Sodium hydroxide is prepared by electrolysis of brine (NaCl (aq)) in Nelson Cell.
2NaCl + 2H2O → 2NaOH + H2 + Cl2
Properties:
(i) It is white solid.
(ii) It is ionic in nature.
(iii) It has soapy touch i.e. slippery touch.
(iv) It has corrosive action for skin.
(v) It has bitter taste.
(vi) It is hygroscopic.
(vii) It is highly soluble in water and the process is highly exothermic due to formation of hydrates.
(viii) It is soluble in alcohol.

Uses:
(i) It is used in soap industry.
(ii) It is used for refining of petroleum.
(iii) It is used for reclaiming rubber.
(iv) It is used for making mercerized cotton.
(v) Its aqueous solution is used to open blocked drainage pipes.
(vi) It is used in acid base titration.

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Magnesium Hydroxide [Mg(OH)2]:

Preparation:
Magnesium hydroxide is obtained as white precipitate when caustic potash (KOH) solution is added to solution of
soluble magnesium salt.
KOH(aq) + MgCl2(aq) → Mg(OH)2(s) + 2KCl(aq)

Properties:
(i) It is white solid.
(ii) It is ionic in nature.
(iii) It has soapy touch.
(iv) It has corrosive action for skin.
(v) It has bitter taste.
(vi) It is hygroscopic.
(vii) It is soluble in water.
(viii) Its solubility in water tremendously increases by adding ammonium chloride to its solution. This is due
to the fact that ammonium ions remove OH- ions. So the equilibrium of Mg(OH)2 gets disturbed and
according to Le Chatelier’s Principle equilibrium shifts to the right.
Mg(OH)2 ⇌ Mg2+ + 2OH-
NH4Cl ⇌ NH4+ + Cl
NH4+ + OH- → NH4OH

Aluminum Hydroxide [Al(OH)3]:

Preparation:
(i) When some alkali solution is added to aqueous aluminum salt solution, aluminum hydroxide is
obtained as white gelatinous precipitate.
Al2(SO4)3 + 6NH4OH → 2Al(OH)3 + 3(NH4)2SO4
(ii) It can also be prepared by hydrolysis of AlCl 3.
AlCl3 + 3H2O → Al(OH)3 + 3HCl

Properties:
(i) It is soluble in acids and alkalis.
(ii) It is amphoteric.
2Al(OH)3 + 3H2SO4 → Al2(SO4)3 + 6H2O
2Al(OH)3 + 2NaOH → 2Na[Al(OH)4]
Use:
It is used to absorb various dyes forming a colouring matter known as “lakes”.

Silicon Hydroxide:

Silicon hydroxide is prepared by reaction of SiO2 with water at 800oC.

SiO2 + 2H2O ⇌ Si(OH)4
Silicon hydroxide is unstable so it is polymerized.

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Group I-A Elements

Elements of Group I-A are called alkali metals due to alkaline nature of their oxides and hydroxides.
The electronic configuration of group I-A elements is:

Alkali Metals
3Li 2 1 1
1s , 2s [He]2s
11Na 2 2 6 1 1
1s , 2s , 2p , 3s [Ne]3s
19K 2 2 6 2 6 1 1
1s , 2s , 2p , 3s , 3p , 4s [Ar]4s
37Rb 2 2 6 2 6 2 10 6 1 1
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s [Kr]5s
55Cs 2 2 6 2 6 2 10 6 2 10 6 1 1
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p , 6s [Xe]6s
87Fr 2 2 6 2 6 2 10 6 2 10 6 2 14 10 6 1 1
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p , 6s , 4f , 5d , 6p , 7s [Rn]7s

Occurrence:

Both alkali metals and alkaline earth metals are very reactive so they do not exist free in nature and exist in
combined state.

Sodium: Its compounds constitute about 3% of the earth crust. The most important ore of sodium is Rock
salt or Halite (NaCl). Its large deposits are found throughout world. In pakistan its deposit are found in khewra,
warcha and bahaderkhel (karak). It is also found in sea water.
Other ores of sodium are Chile saltpeter (NaNO3), Natron (Na2CO3.H2O), Trona (Na2CO3.2NaHCO3.2H2O) and
Borax (Tincal) [Na2B4O7.10H2O].

Potassium: Its important ore are Feldspar (KAlSi3O8), Sylvite (KCl) and Carnallite (KCl.MgCl2.6H2O).
Deposits of these ores are found in Germany, New Maxico and Searles Lake in California.

General Physical Properties of Alkali metals (group IA):

(i) Softness: They are soft and their softness increases down the group. Sodium is so soft that it can be cut
even by blunt knife.
(ii) Luster: They have silvery luster when freshly cut.
(iii) Nature: They are malleable.
(iv) Melting boiling points: They have low melting and boiling points and which decrease down the
group.
Element Li Na K Rb Cs
Melting Point (oC) 1085 97.8 63.7 38.9 28.7
Boiling Point (oC) 1330 892 760 688 670
(v) Electrical conductance: They are good conductor of heat and electricity.
(vi) Atomic radii: Their atomic radii increase down the group due to addition of more and more shells.
Element Li Na K Rb Cs
Atomic Radius (Ao) 1.55 1.90 2.35 2.48 2.67
(vii) Elctropositivity: They are highly electropositive and elctropositivity increases down the group.

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(viii) Electronegativity: Their electronegativities are very low. Their elctronegativities decreases down the
group.
Element Li Na K Rb Cs
Electronegativity (Pauling scale) 1.0 0.9 0.8 0.8 0.7
(ix) Ionization Energies: Their ionization energies are very low. So they can easily lose their electrons.
Ionization energy decreases down the group.
Element Li Na K Rb Cs
1st Ionization Energy(e.v) 5.4 5.1 4.3 4.2 3.9
(x) Density: Their densities increases down the group, however fluctuation occurs at potassium.
Element Li Na K Rb Cs
Density (g/cm3) 0.534 0,972 0.86 1.53 1.903
(xi) Reducing ability: They are good reducing agents.
(xii) Flame test: They give characteristic colours to Bunsen burner flame. When they are heated in the
flame their electrons jump to higher orbits. Then on dropping back they emit visible light of different
colours.
Element Li Na K Rb Cs
Colour of flame Crimson red Golden yellow Lilac/violet violet violet

Procedure:
Paste of salt is made in conc HCl then a wire of platinum is dipped in the paste and is then brought to
the blue flame of Bunsen burner. The colour of flame is observed and identification is made.

Chemical Properties:

Alkali metals are very reactive.

Reaction with water:

Alkali metals are very strong reducing agents so they react vigorously with water and reduce it to hydrogen
gas and themselves oxidize to metal hydroxide.
2Na + 2H2O → 2NaOH + H2
Reaction is highly exothermic so the hydrogen produced catches fire. Vigorousness of reaction increases
down the group.
Lithium show slow reaction. Sodium shows vigorous reaction, fizzing and skating about on the water.
Potassium shows more vigorous reaction. It cracks and pops as hydrogen burns. Rubidium and cesium
explode violently on contact with water.

Reaction with oxygen:

Alkali metals are very reactive with air. Reactivity increases down the group. So Li, Na and K are stored in kerosene
oil while Cs and Rb are stored in sealed glass tube to prevent air to contact.
Usually Lithium produces normal oxide 4Li + O2 → 2Li2O (oxidation number of oxygen is -2)
Sodium often produces peroxide 2Na + O2 → Na2O2 (oxidation number of oxygen is -1)
Potassium, Rubidium and Cesium produce superoxide K + O2 → KO2 (oxidation number of oxygen is -1/2)

Reaction with Nitrogen:

Only Lithium reacts with nitrogen of the air and produces lithium nitride. 6Li + N 2 → 2Li3N

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Reaction with chlorine:

Sodium burns in chlorine with orange flame. Other alkali metals also burn in chlorine and produce white solid metal
chloride. 2Na + Cl2 → 2NaCl
2K + Cl2 → 2KCl

Compounds of Alkali Metals (Group I-A):

Oxides:
Alkali metals on direct reaction with oxygen produce their oxides. Oxides of group I-A are basic in nature.

Reaction with water:

Normal oxides on reaction with water produce metal hydroxide. Li2O + H2O → 2LiOH
Na2O + H2O → 2NaOH
Peroxides on reaction with water produce metal hydroxide and hydrogen peroxide.Na 2O2 + 2H2O → 2NaOH + H2O2
Super oxides on reaction with water produce metal hydroxide and hydrogen peroxide and oxygen.
2KO2 + 2H2O → 2KOH + H2O2 + O2

Reaction with dilute acids:

Normal oxides on reaction with dilute acid produce metal chloride and water. Li2O + 2HCl → 2LiCl + H2O
Na2O + 2HCl → 2NaCl + H2O
Peroxides on reaction with dilute acid produce metal chloride and hydrogen peroxide. Na2O2 + 2HCl → 2NaCl + H2O2
Super oxides on reaction with dilute acid produce metal chloride and hydrogen peroxide and oxygen.
2KO2 + 2HCl → 2KCl + H2O2 + O2
 Potassium super oxide (KO2) is used in breathing equipments of mountaineers for getting oxygen from
carbon dioxide. 4KO2 + 2CO2 → 2K2CO3 + 3O2

Nitrates:

Effect of Heat on Nitrates:

Nitrates of alkali metals on heating decompose and produce metal nitrites and oxygen. 2NaNO3 → 2NaNO2 + O2
However nitrate of lithium on heating decompose to produce metal oxide, nitrogen dioxide (Brown colour gas) and
oxygen. 4LiNO3 → 2Li2O + 4NO2 +O2

(Brown)
Carbonates:

Effect of Heat on Carbonates:

Carbonates of alkali metals are thermally stable and they do not decompose on heating. However Lithium Carbonate
decomposes on heating. Li2CO3 → Li2O + CO2

 Carbonates of group I-A are more stable than that of group II-A. Cations of first group have less charge so
less charge density. Therefore, their polarizing power will be low so less covalent character and hence their
carbonates are more stable.

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Bicarbonates:

Effect of Heat on Hydrogen Carbonates:

Hydrogen Carbonates or Bicarbonates of alkali metals are thermally unstable and so they decompose on heating.
2NaHCO3 → Na2CO3 + CO2 + H2O
Thermal stability of hydrogen carbonates (bicarbonates) group I-A and group II-A increases down the group. Thus
LiHCO3 decompose easily and CsHCO3 decompose difficultly.
Explanation: A cation with high charge density causes significant polarization of anion. This creates some
covalent character in the compound that decreases the stability and assists in its thermal decomposition. This is due
to Fajans’ Rule. Which states, “Small size cations having high charge density tends to make covalent
compounds?”
As the size of cation increases down the group its charge density decreases accordingly. Therefore, its polarizing
power also decreases in the same order. This means covalent character decreases down the group and consequently
ionic character increases. And, therefore, thermal stability increases down the group.
 Hydrogen carbonates of group I-A are more stable than that of group II-A. Cations of first group have less
charge so less charge density. Therefore, their polarizing power will be low so less covalent character and
hence their hydrogen carbonates are more stable.
 Sodium bicarbonate (NaHCO3) is baking soda. It is used as source of CO2 in baking process.
Heat
2NaHCO3 Na2CO3 + CO2 + H2O
It is also used in fire extinguishers.

Peculiar Behaviour of Lithium:

Lithium being 1st member of the family shows some differences with rest of the members of its family.
(i) Melting and boiling point of Lithium are much higher than other members of its family.
(ii) Lithium is hard metal while other elements of the group are soft metals.
(iii) Lithium forms normal oxide while others form peroxide and superoxide.
(iv) LiOH is less basic than that of others.
(v) Lithium reacts with nitrogen and forms nitride while others do not.
(vi) Lithium reacts with carbon and forms carbide while others do not.
(vii) Carbonate and phosphate of Lithium are insoluble in water while that of others are soluble.
(viii) Li2CO3 is unstable and decomposes on heating while carbonates of other are stable even on heating.
Li2CO3 → Li2O + CO2
(ix) LiCl is somewhat covalent and is soluble in organic solvents, while chlorides of other are ionic and
soluble in water.
(x) Lithium reacts with water very slowly while other reacts violently.
(xi) Nitrate of Lithium produce oxide on heating while nitrates of others produce nitrite.
4LiNO3 → 2Li2O + 4NO2 + O2
2NaNO3 → 2NaNO2 + O2
(xii) LiOH is unstable and decomposes on heating while hydroxides of other are stable even on heating.
2LiOH → Li2O + H2O
+
(xiii) Lithium ion (Li ) is heavily hydrated than those of others.

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Group II-A Elements

Elements of Group I I-A are called alkaline earth metals. This is due to reason that they are earth making alkaline
metals. Their oxides and hydroxides are alkaline in nature.
The electronic configuration of group II-A elements is:

Alkaline Earth Metals

4Be 2 2 2
1s , 2s [He]2s
12Mg 2 2 6 2 2
1s , 2s , 2p , 3s [Ne]3s
20Ca 2 2 6 2 6 2 2
1s , 2s , 2p , 3s , 3p , 4s [Ar]4s
38Sr 2 2 6 2 6 2 10 6 2 2
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s [Kr]5s
56Ba 2 2 6 2 6 2 10 6 2 10 6 2 2
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p , 6s [Xe]6s
88Ra 2 2 6 2 6 2 10 6 2 10 6 2 14 10 6 2 2
1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p , 6s , 4f , 5d , 6p , 7s [Rn]7s

Occurrence:
Magnesium: It is very abundant in rocks of earth’s crust. It is found in sea water and springs water. Its mineral
are Dolomite (MgCO3.CaCO3), Magnesite (MgCO3), Epsom salt (MgSO4.7H2O), Soap stone
(Talc) [Mg2(Si2O5)2.Mg(OH)2], and Asbestos [CaMg3(SiO3)4].

Calcium: It is very abundant in rocks of earth’s crust. It is present in sea shells. Its important mineral are
Calcite or Lime stone or Marble (CaCO3), Gypsum (CaSO4.2H2O).

General Physical Properties of Alkaline earth metals (group II-A):

(i) Atomic radii: Their atomic radii increase down the group due to addition of more and more shells.
Element Be Mg Ca Sr Ba Ra
Atomic Radius (Ao) 1.12 1.60 1.74 1.91 1.97 2.22
(ii) Ionization Energies: Their ionization energies decrease down the group. However Ra shows slightly
higher ionization energy than that of Ba.
Element Be Mg Ca Sr Ba Ra
1st Ionization Energy(e.v) 9.3 7.6 6.1 5.7 5.2 5.3
(iii) Electronegativity: Their electronegativities are very low. Their elctronegativities decreases down the
group.
Element Be Mg Ca Sr Ba Ra
Electronegativity (Pauling scale) 1.5 1.2 1.0 1.0 0.9 0.9
(iv) Melting boiling points: Their melting and boiling points have no regular trend.
Element Be Mg Ca Sr Ba Ra
Melting Point (oC) 1289 651 851 771 727 700
Boiling Point (oC) 2500 1105 1494 1381 1850 1700
(v) Flame test: They give characteristic colours to Bunsen burner flame. When they are heated in the
flame their electrons jump to higher orbits. Then on dropping back they emit visible light of different
colours.
Element Mg Ca Sr Ba
Colour of flame Bright white Brick red Crimson red Green

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Chemical Properties:

Alkaline earth metals are reactive but less reactive than that of alkali metals.

Reaction with Water:

Alkaline earth metals react slowly with water. Their reactivity with water increases down the group. Be do
not react with water, Mg reacts with boiling water or steam and produce magnesium oxide and librates
hydrogen gas.
Mg(s) + H2O(g) → MgO(s) + H2
While others (Ca, Sr, Ba) can react with cold water and produce metal hydroxides along with hydrogen gas.
Ca(s) + 2H2O(g) → Ca(OH)2(aq) + H2
Reaction with Oxygen:

All they react with oxygen except Be and produce normal oxides. Be do not react due to having strong
protective layer of BeO, however powdered Be may react with oxygen.
2Ca(s) + O2(g) → 2CaO(s)
2Sr(s) + O2(g) → 2SrO(s)
Sr and Ba on heating in air produce peroxides. But this ability is not shown by Be, Mg and Ca
Heat
Sr(s) + O2(g) → SrO2(s)
 Solubility of oxides increases down the group.
 Oxides of group II-A are basic in nature.
 CaO is called quick lime. Its reaction with water produces Ca(OH)2 and the reaction is called slaking. Solid
Ca(OH)2 is called slaked lime while aqueous solution of Ca(OH) 2 is called lime water.

Reaction with Nitrogen:

All they react with nitrogen of the air on heating and produce their nitride. These nitrides are ionic and
solid. However nitride of Be is covalent.
Heat
3Mg(s) +N2(g) → Mg3N(s)

Compounds of Alkaline Earth Metals (Group II-A):

(i) Hydroxides:
Solubility:
Solubility of hydroxides of alkaline earth metals increases down the group. It means their solubility
products increase down the group.
(1) Be(OH)2 , Ksp = 1.6 10-26 (2) Mg(OH)2 , Ksp = 8.6 10-12 (3) Ca(OH)2 , Ksp = 1.3 10-4
(4) Sr(OH)2 , Ksp = 3.2 10 -4
(5) Ba(OH)2 , Ksp = 5.4 10-3
Explanation:
Solubility depends upon two factors Lattice energy and Heat of Hydration.
(a) Lattice energy: Higher is lattice energy lower will be the solubility.
(b) Heat of hydration: Higher is the heat of hydration higher will be solubility.

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Lattice energy decreases down the group so solubility should increase down the group. Heat of hydration
also decreases down the group so solubility should decrease down the group. The two factors are acting
oppositely. Lattice energy decreases gradually down the group. On other hand heat of hydration decreases
little down the group due to smaller size of hydroxyl ion, therefore, dominating factor is lattice energy.
Hence solubility of hydroxide increases down the group.
 Mg(OH)2 being less soluble in water produce suspension in water. The suspension of Mg(OH)2 is
called milk of magnesia. It is used for the treatment of acidity of stomach.
 Solid Ca(OH)2 is called slaked lime while aqueous solution of Ca(OH)2 is called lime water. It is
used for qualitative and quantitative analysis of CO2.

(ii) Sulphates:

Solubility:
Solubility of sulphates of alkaline earth metals decreases down the group. It means their solubility
products decrease down the group. CaSO4 is sufficiently soluble in water while BaSO4 is almost
insoluble in water.
Explanation:
Solubility depends upon two factors Lattice energy and Heat of Hydration.
(c) Lattice energy: Higher is lattice energy lower will be the solubility.
(d) Heat of hydration: Higher is the heat of hydration higher will be solubility.
Lattice energy decreases down the group so solubility should increase down the group. Heat of
hydration also decreases down the group so solubility should decrease down the group. The two factors
are acting oppositely. Lattice energy decreases gradually down the group, therefore, its effect is not
significant. On other hand heat of hydration decreases rapidly down the group, therefore, it is dominant
factor and thus solubility of sulphates decreases down the group.

(iii) Carbonates:
Solubility:
All the carbonates of alkaline earth metals are insoluble in water. However they are soluble in acids.
Thermal Stability:
Thermal stability of carbonates of alkaline earth metals increases down the group and it is evident
from their temperature of decomposition.
BeCO3 < 100oC MgCO3 = 540oC CaCO3 = 900oC SrCO3 = 1290oC
o
BaCO3 = 1360 C
Explanation:
Two factors are responsible for the stability of the carbonates.
(i) Smaller is the metal ion more is the lattice energy of the resulting metal oxide and hence higher is
the stability of the oxide and the carbonate forming this oxide will be less stable. Thus going down
the group stability of oxide decreases so stability of their carbonates increases.
(ii) A cation with high charge density causes significant polarization of anion. This creates some
covalent character in the compound that assists in its thermal decomposition. Thus, as size of
cation increases down the group, its charge density decreases accordingly. Therefore its polarizing
power also decreases in the same order. This means that the covalent character of carbonates
decreases down the group. Hence there is a corresponding increase in thermal stability of
carbonates going down the group.

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Thermal decomposition of carbonates produces metal oxide and carbon dioxide.

CaCO3(s) → CaO(s) + CO2(g)
(iv) Nitrates
Thermal Stability:
Thermal stability of nitrates of alkaline earth metals increases down the group.

Explanation:
Two factors are responsible for the stability of the nitrates.
(i) Smaller is the metal ion more is the lattice energy of the resulting metal oxide and hence higher is
the stability of the oxide and the nitrate forming this oxide will be less stable. Thus going down
the group stability of oxide decreases so stability of their nitrate increases.
(ii) A cation with high charge density causes significant polarization of anion. This creates some
covalent character in the compound that assists in its thermal decomposition. Thus, as size of
cation increases down the group, its charge density decreases accordingly. Therefore its polarizing
power also decreases in the same order. This means that the covalent character of nitrates
decreases down the group. Hence there is a corresponding increase in thermal stability of nitrates
going down the group.

Thermal decomposition of nitrates produces metal oxide, nitrogen dioxide and oxygen.
2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
(Brown)

Peculiar Behaviour of Beryllium:

Beryllium being 1st member of the family shows some differences with rest of the members of its family.
(i) Beryllium atom is very small so according to Fajan’s rule which states that small highly charged
cations tend to form polar covalent compounds thus its compounds are somewhat covalent.
(ii) It is as hard as iron while other members of the family are soft.
(iii) Melting and boiling point of Beryllium are much higher than other members of its family.
(iv) Halides of Beryllium are soluble in organic solvents while that of other are soluble in water.
(v) Oxide and hydroxide of Beryllium is amphoteric while that of others are basic in nature.
Be(OH)2 + 2HCl → BeCl2 + 2H2O
Be(OH)2 + 2NaOH → Na2[Be(OH)4]
(vi) It is the only member of the family which on reaction with alkalis liberates hydrogen.
Be + 2NaOH → Na2BeO2 + H2
(vii) Beryllium is resistant to complete oxidation due to its BeO coating.
(viii) It does not react even with boiling water.
(ix) Oxides, nitrides, sulphides, chlorides etc of group II-A are ionic but that of Be are covalent.
Explanation:
Polarizing power of both Be2+ as well as that of Cl- ion is so high. So Be2+ sufficiently pulls electrons
from Cl- ion, such that electron pair is effectively shared. This is the reason that BeCl 2 is covalent. This
is in accordance with Fajan,s rule.
(x) Alkaline earth metals impart colour to flame but Be does not impart any colour to the flame.
(xi) Oxide of Be is insoluble in water.

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Group IV-A Elements

This group of elements is placed in middle of periodic table.

The electronic configuration of group IV-A elements is:

Group IV-A
2 2 2
6C 1s , 2s , 2p [He]2s2, 2p2
14Si 1s2, 2s2, 2p6, 3s2, 3p2 [Ne]3s2, 3p2
32Ge 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p2 [Ar]3d10,4s2, 4p2
50Sn 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p2 [Kr]4d10,5s2,5p2
82Pb 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 4f14, 5d10, 6p2 [Xe]4f14,5d10,6s2,6p2

Melting and Boiling Points:

Element Melting Point (oC) Boiling Point (oC)

C 3600 4827
Si 1420 2355
Ge 937 2830
Sn 232 2560
Pb 328 1744

C, Si and Ge have giant atomic structure and they have strong covalent bonds so their melting points are high.
Decrease in melting point from C to Ge is due to increasing atomic size because of witch covalent bonds are
weakened. Sn and lead are metals and their atoms are bigger so their metallic bonding is weak hence their melting
points are low.

Metallic Character:
Metallic character decreases down the group. In group IV-A Change from non-metal occurs. C and Si are non-
metals, Ge is metalloid while Sn and Pb are metals.

Oxidation states:
C shows +4 (as in CCl4), -4 (as in Be2C), -1 (as in Na2C2) oxidation states.
Si shows +4 oxidation state.
Ge, S, and Pb show +2 and +4 oxidation states.
So the most common oxidation state of group elements is +4.

Inert Pair Effect:

“The tendency of an element not to involve its pair of electrons of s orbital in bond formation is called inert pair
effect.”

If hybridization occurs then electrons of s-orbital will not be inert and if no hybridization occurs then electrons of s-
orbital will be inert.

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(i) Promotion of one of s-electron to p-orbital followed by sp3 hybridization of orbitals needs energy to be
provided for the process.
(ii) Formation of four covalent bonds involving the hybrid orbitals releases energy.
If energy released in the formation of four covalent bonds is more than the energy absorbed in the promotion of
electron from s-orbital to p-orbital, then hybridization will occur and element will not show inert pair effect.
On other hand If energy released in the formation of four covalent bonds is less than the energy absorbed in the
promotion of electron from s-orbital to p-orbital, then no hybridization will occur and element will show inert pair
effect.
Inert pair effect increases down the group. As atomic radius increases down the group and bigger atoms make weak
covalent bonds so energy released during bond formation is less than the energy absorbed during promotion of
electron from s to p so no hybridization occurs and s-electrons remain inert.
Elements on the top shows no inert pair effect thus their oxidation state in the compounds will be +4 while lead
being larger atom often shows inert pair effect and in its most compounds its oxidation state is +2. Higher oxidation
state tends to covalent bond formation while lower oxidation state tends to ionic bond formation. So C forms
covalent bonds while Pb forms ionic bonds.

Chlorides:

Carbon, silicon and lead form tetra chlorides (CCl4, SiCl4 and PbCl4). As these elements are sp3 hybridized so their
tetra chlorides are tetrahedral. Stability of chlorides decreases from CCl 4 to PbCl4. Thus PbCl4 decomposes to give
PbCl2. PbCl4 → PbCl2 + Cl2.
Stability of +4 oxidation state decreases down the group so C and Si forms only CCl 4, SiCl4 while Pb often forms
PbCl2.
CCl4 does not react with water as water cannot reach to carbon as carbon is a small atom and four big Cl atoms are
around it. SiCl4 to PbCl4 reacts violently with water producing their oxides.
SiCl4 + 2H2O → SiO2 (White) + 4HCl

PbCl4 + 2H2O → PbO2 + 4HCl

(Brown)

PbCl2 is ionic so it just gets dissolves in water. PbCl2 ⇌ Pb2+ + 2Cl-

Oxides:
Group IV-A elements make two type of oxides i.e. monoxides (CO, SnO and PbO) and dioxides (CO2, SnO2 and PbO2).

Nature of oxides:
Carbon and Silicon are non-metals so their oxides are covalent in nature. Whereas Tin and Lead are metals so their
oxides are ionic in nature.

Acid base behaviour of oxides:

As metallic character increases down the group so acidic behaviour decreases down the group. Thus among dioxides
CO2 and SnO2 are acidic while are GeO2, SnO2 and PbO2 are amphoteric oxides. Among monoxides CO is neutral
oxide while GeO, SnO and PbO are amphoteric.

CO2 + H2O → H2CO3

(acid)

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CO2 + 2NaOH → 2Na2CO3

(acid)
SnO + HCl → SnCl2 + H2O
(base)
SnO + NaOH + H2O→ Na2Sn(OH)4
(acid)

Structure of carbon monoxide CO:

Carbon monoxide is a divalent molecule. Carbon and oxygen contributes unequal number of electrons in the bond
formation. There is a triple bond between the two atoms including two covalent and a coordinate covalent bond.

Structure of carbon dioxide (CO2)

It is most stable oxide of carbon. It has linear structure having two carbon-oxygen double covalent bonds. It has
linear structure. The bond length is 1.15oA or 1.15 x 10-10m. Carbon dioxide molecule is non-polar due to its linear
structure having zero dipole moment.
In solid state (i.e. dry ice) carbon dioxide has face-centered cubic structure.
Carbon in CO2 is sp hybridized. One of half-filled sp hybrid orbital of carbon overlaps with one of the half-filled p-
orbital of one oxygen atom. This overlapping take place on bond axis hence sigma bond is formed. The other half
filled sp hybrid orbital of carbon overlaps with one of the half-filled p-orbital of other oxygen atom. This
overlapping also take place on bond axis hence sigma bond is formed. Remaining two half-filled unhybridized p-
orbitals of carbon each laterally overlaps with half-filled p-orbital of each oxygen atom forming Pi-bonds with them.
π-bond π-bond
2Py 2Pz
Oxygen Carbon Oxygen
↑ ↑
2Px 2Py 2Pz sp sp 2Px 2Py 2Pz

↑↓ ↑ ↑ ↑ ↑ ↑↓ ↑ ↑
δ-bond δ-bond

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Structure of Silicon dioxide (SiO2):

Silicon atoms are bigger than carbon atoms so silicon oxygen bond length is more than that of carbon
oxygen bond length. Hence in this case lateral overlapping of orbitals will not be affective so only sigma bonds are
formed. Silicon dioxide has giant molecular structure in which each silicon atom is bonded to four oxygen atoms
and each oxygen atom is bonded to two silicon atoms.

│ │ │
O O O
│ │ │
Si Si Si

O O O O
O O O Structure of Silicon dioxide (SiO2)
│ │ │
Si Si Si

O O O O

O O O
│ │ │

Group VII-A Elements

The word halogen means salt former. Halogens belong to group VII-A. This group consists of the elements which
are given in the following table.
Group VII-A
9F 1s2, 2s2, 2p5 [He]2s2, 2p5
17Cl 1s2, 2s2, 2p6, 3s2, 3p5 [Ne]3s2, 3p5
2 2 6 2 6 2 10 5
35Br 1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p [Ar]3d10,4s2, 4p5
53I 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p5 [Kr]4d10,5s2,5p5
2 2 6 2 6 2 10 6 2 10 6 2 14 10 5
85At 1s , 2s , 2p , 3s , 3p , 4s , 3d , 4p , 5s , 4d , 5p , 6s , 4f , 5d , 6p [Xe]4f14,5d10,6s2,6p5

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General Properties:

(i) Their general electronic configuration is ns2, np5.

(ii) All halogens are non-metals.
(iii) They exists as discrete diatomic molecules F2, Cl2, Br2, I2, At2.
(iv) Their atomic radii increase down the group.
(v) Their electronegativities are high and decrease down the group. Fluorine has highest electronegativity
which is four.
Element F Cl Br I At
Electronegativity (Pauling scale) 4.0 3.0 2.8 2.5 2.2

(vi) Electron affinity is the energy released or absorbed when an electron is added to gaseous atom or ion.
It is the measure of attraction between incoming electron and nucleus. Higher is the attraction higher
will be the electron affinity.
Trend of electron affinity F < Cl > B r > I > At or At < I < Br < F < Cl

Element F Cl Br I At
Electron Affinity (kJ/mol) 328 349 325 295 270
Trend is not regular. Fluorine is showing exceptionally low value than chlorine. Due to its very smaller
atomic size valence shell is smaller so electrons present in it repel the incoming electron. Thus
difference between energy released due to attraction by nucleus and energy absorbed during repulsion
by the electrons is less and therefore, electron affinity of fluorine is less than chlorine.

(vii) Their melting and boiling points increases down the group. Thus from top to bottom they change from
gas to solid. Astatine is radioactive and its half life is 8.3hrs.
(viii)
Element State M.P B.P Colour
Fluorine gas -219.6oC -188.2oC pale yellow
Chlorine gas -101.0oC -34.7oC yellowish green
Bromine liquid -7.2oC 59oC dark red (vapours reddish brown)
Iodine solid 113.7oC 184oC dark crumbly (vapours violet)
Astatine solid 300oC 380oC black (vapours dark)

(ix) Bond Enthalpy is the energy required to break one mole chemical bonds in gaseous molecules to form
gaseous atoms. Cl2(g) → 2Cl(g) ∆H = 242 kJ/mol
Element F Cl Br I
Bond Enthalpy (kJ/mol) 158 242 193 151
F2 has abnormally low bond enthalpy than chlorine due to its smaller atomic size. Due to smaller size
distance between nuclei of two atoms will be less and hence repulsion between nuclei will be more. As
a result bond will be weaker.

(x) Halogens are good oxidizing agents; however their oxidizing power decreases down the group.
Their oxidizing power depends upon
(a) Dissociation energy more is dissociation energy less is oxidizing power.
(b) Electron affinity more is electron affinity more is oxidizing power.
(c) Reduction potential more is reduction potential more is oxidizing power.
Dominating factor is reduction potential.

Order of oxidizing power is F2 > Cl2 > Br2 > I2

Standard reduction potential (V) 2.87 1.36 1.06 0.54
Halogens take electrons from other elements and thus oxidize them.

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2Na + Cl2 → 2Na+ Cl-

e.g. (i) Fluorine and chlorine can oxidize coloured dyes to colourless. Thus they are used as bleaching
agents.
e.g. (ii) Chlorine water oxidizes KI to iodine and solution turns brown due to formation of iodine.
Cl2(g) + KI(aq) → KCl(aq) + I2(s)
In this reaction Cl2 has oxidized I- to I2. Similarly Cl2 can oxidize Br- to Br2.

(xi) Reducing power of halide ions depend upon their sizes. Larger is the size of halide ion more is its
reducing power. Larger ions can easily donate electron and thus can easily reduce other substances.
Order of reducing power is I- > Br - > Cl- > F-
Ionic radius (nm) 0.216 0.195 0.181 0.136
-
e.g. (i) Br ion reduces sulphate ion of sulphuric acid to SO2.
H2SO4 + 2H+ + 2Br - → Br2 + SO2 + 2H2O
+6 +4
Gain of 2 electrons, Reduction

e.g. (ii) I - ion is larger than Br – ion so it is stronger reducing agent than Br - ion. It reduces sulphate
ion of sulphuric acid to S-2 ion.

H2SO4 + 8H+ + 8I - → 4I2 + H2S + 2H2O

+6 -2
Gain of 8 electrons, Reduction

(xii) Halogens have irritating odours and they attack skin. Bromine causes burns that heal slowly
(xiii) They have high ionization energies, electron affinities and electronegativities.
(xiv) Common oxidation state for halogens is -1, but they also show +1, +3, +5, and +7 oxidation states in
their compounds. However fluorine does not show positive oxidation state as it has highest
electronegativity.
(xv) They form ionic compounds with group I-A and group II-A elements.
(xvi) Halogens directly react with hydrogen under different conditions to produce their hydrides (Hydrogen
halides).
H2 + F2 → 2HF vigorous reaction
H2 + Cl2 → 2HCl in presence of sunlight
H2 + Br2 → 2HBr in presence of sunlight
H2 + I 2 ⇋ 2HI in presence of sunlight

The order of reactivity of halogens towards this reaction is

F2 > Cl2 > Br2 > I2

As the size of halogen increases, the bond energy of H – X bond decreases and thus stability of halide
decreases also polarity of the bond decreases.

(a) The order of stability and polarity is HF > HCl > HBr > HI
(b) While order of reactivity of halogen acids is HI > HBr >HCl > HF

(c) Acidic strength of hydrogen halides increases down the group. As stability of halogen acids
decrease down the group accordingly their acidic strength increases down the group.
Order of acid strength HI > HBr >HCl > HF

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All halogen are highly soluble in water and are stronger acids. HF is also highly soluble in water
but it is weak acid.

(d) Bond enthalpies of hydrogen halides decrease down the group.

As down the group size of halogen increases so bond length increases and hold of nuclei decreases
on shared electrons so bond enthalpy decreases.
Also polarity of molecule decreases down the group so bond become weaker and thus bond
enthalpy decrease.

Hydrogen halide H–F H – Cl H – Br H–I

Bond Enthalpy (kJ/mol) 568 432 366 298

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