S BLOCK Elements Jee

s-Block Elements
The s-block elements
s-Block Elements
Similarities
Highly reactive metals
Strong reducing agents
Form ionic compounds
Fixed oxidation state
Group I : +1
Group II : +2
Variation in Physical Properties of s-block

Elements
1. Atomic Radius and Ionic Radius
2. Ionization Enthalpies
3. Hydration Enthalpies
4. Melting Points
5. Electronegativity
Atomic and Ionic Radii

The atoms and ions of alkali metals are largest in their
corresponding periods.
Atomic size
Li < Na < K < Rb < Cs
Ionic Radius
Li+ < Na + < K + < Rb + < Cs +
Atomic volume
Li < Na < K < Rb < Cs
Charge density
Li > Na > K > Rb > Cs
Atomic Radius and Ionic Radius

Group I
element
Atomic radius
(nm)
Group II
element
Atomic radius
(nm)
Li
0.152
Be
0.112
Na
0.186
Mg
0.160
0.231
Ca
0.197
Rb
0.244
Sr
0.215
Cs
0.262
Ba
0.217
down the groups

the outermost electrons are further away from the nuclei
Group II < Group I
ENC from left to right across the periods
On moving down the groups,

first sharply (e.g. from Li to K)
then slowly (e.g. from K to Fr)

There is a sharp in NC from 19K to
37Rb
Outermost e is drawn closer to the
nucleus
The inner d-electrons (of Rb, Cs, Sr, Ba) have poor shielding effect on the
outermost electrons transition contraction
7
Ionisation Enthalpy
Ionization Enthalpy
Group I
element
1st IE
2nd IE
Group II
element
1st IE
2nd IE
3rd IE
Li
519
7 300
Be
900
1 760
14 800
Na
494
4 560
Mg
736
1 450
7 740
418
3 070
Ca
590
1 150
4 940
Rb
402
2 370
Sr
548
1 060
4 120
Cs
376
2 420
Ba
502
966
3 390
Both atomic radius and ENC down the groups

Atomic radius is more important
IE down the groups
Ionization Enthalpy
Group I
element
1st IE
2nd IE
Group II
element
1st IE
2nd IE
3rd IE
Li
519
7 300
Be
900
1 760
14 800
Na
494
4 560
Mg
736
1 450
7 740
418
3 070
Ca
590
1 150
4 940
Rb
402
2 370
Sr
548
1 060
4 120
Cs
376
2 420
Ba
502
966
3 390
For Group I elements, 2nd IE >> 1st IE because

the 2nd electron is closer to the nucleus and is poorly shielded by other electrons in
the same shell which is completely filled.
10
For Group II elements, 3rd IE >> 2nd IE

Similar reasons can be applied
Ionization Enthalpy
Variations in the
first and second
ionization
enthalpies of
Group I elements
11
Ionization Enthalpy
Variations in the first,

second and third
ionization enthalpies
of Group II elements
12
Electronegativity
13
Electronegativity
Relatively LOW Electronegativity
These metals have more tendency to lose electron rather than to gain an
electron.
The electronegativity values decreases down the group from Li to Cs
14
ELECTRONEGATIVITY
Group I
element
Electronegativity
value
Group II
element
Electronegativity
value
Li
1.0
Be
1.5
Na
0.9
Mg
1.2
0.8
Ca
1.0
Rb
0.8
Sr
1.0
Cs
0.7
Ba
0.9
All have low electronegativity => Electropositive

EN down the group
EN : Group II > Group I ( greater ENC)
Hydration
16
Hydration enthalpy
Hydration enthalpy (Hhyd) is the amount of energy
released when one mole of aqueous ions is formed from
its gaseous ions.
M+(g) + aq M+(aq)
H = Hhyd
M2+(g) + aq M2+(aq)
H = Hhyd
17
always has a negative value
Hydration energies
Group I
Alkali metal ions are highly hydrated.
The smaller the ionic size, the higher the degree of hydration.
Primary and secondary shell of hydration
Li ion is very small, it is heavily hydrated.
Li ion is tetrahedrally surrounded by four water molecules using its four sp3
hybrid
Group 2
They have higher hydration energies than Alkali metals due to smaller sizes
18
Hydration energies
In aqueous solutions, degree of hydration decreases from Li+ to Cs+ due
to increase in size
Ionic radii of hydrated alkali metal ions also decreases from Li+ to Cs+
Formation of hydrated salts :

Li > Na > K Salts.
Rb and Cs salts are not hydrated
Ionic Mobility : Cs+ > Rb+ > K + > Na + > Li +
19
Hydration energies
Hydration
Group I
ion
Enthalpy
(kJ mol1)
Hydration
Group
II ion
enthalpy
(kJ mol1)
Li+
519
Be 2+
2 450
Na+
406
Mg2+
1 920
K+
322
Ca2+
1 650
Rb+
301
Sr2+
1 480
Cs+
276
Ba2+
1 360
20
Group II > Group I

Group II ions have higher charge and small
size
higher charge density
stronger ion-dipole interaction
Melting & Boiling Point

The melting points of s-block elements depend on the metallic bond strength
which in turn depends on
1.
charge density of cations
2.
number of valence electrons participating in the sea of electrons
3.
packing efficiency of the crystal lattices
21
Group I
Melting
Group II
Melting
element
Point (C)
element
Point (C)
Li
180
Be
1280
Na
97.8
Mg
650
63.7
Ca
850
Rb
38.9
Sr
768
Cs
28.7
Ba
714
Fr
24
Ra
697
down the groups

ionic radii down the groups
charge density
interaction between ions and electron sea
Group II > Group I
(a) Group II cations have higher charge density
(b) More valence electrons are involved in the sea of electrons
(c) Packing efficiency : Group II > Group I
22
STRUCTURE
Group
I
Densities of Li, Na, K

are lesser than that
of water
Densit
y (g
cm3)
Group
II
Densit
y (g
cm3)
Li
0.53
Be
1.86
Na
0.97
Mg
1.74
0.86
Ca
1.55
Rb
1.53
Sr
2.54
Cs
1.90
Ba
3.59
Fr
Ra
Density
Alkali metals have low density.
The reason this is that they have large atomic sizes.
Density gradually increases on moving down the group from Li to

Cs
Li < Na < K < Rb < Cs.
Anomaly: K is lighter than Na
24
Effect of light
Alkali metals when irradiated with light emit electrons with ease
due to low ionization enthalpies.
This phenomenon is used in photoelectric cells, particularly
caesium and potassium are used as electrodes in photoelectric
cells.
25
Flame Colouration
26
Flame Colouration
Most s-block elements and their compounds give a
characteristic flame colour in the flame test
Group I
element
Li
Na
K
Rb
Cs
27
Flame colour
Crimson
Golden yellow
Lilac
Bluish red
Blue
Flame Colouration
Most s-block elements and their compounds give a
characteristic flame colour in the flame test
Group II
element
Be
Mg
Ca
Sr
Ba
28
Flame colour
Brick red
Blood red
Apple green
Ca, Sr, Ba
Beryllium and magnesium atoms are

smaller and their electrons being
strongly bound to the nucleus are not
excited to higher-energy levels.
Flame Colouration
Mechanism : 1. In the hotter part of the flame,
Na(g)
heat
Ground state
[Ne] 3s1
Na(g)*
[Ne] 3p1
2. In the cooler part of the flame,

Na(g)*
29
[Ne] 3p1
cool
Na(g)
[Ne] 3s1
+ golden yellow light

Visible
region
Flame Colouration
Mechanism : For salts of s-block elements,
the metal ions of the salts are first converted to metal
atoms
Na2CO3(s)
Na+Cl
Na(g)
30
Na(g)*
Conc. HCl
heat
heat
cool
Na+Cl (more volatile)
Na(g) + Cl(g)
Na(g)*
Na(g)
+ golden yellow light
Complex Formation
31
Complex formation
In order to form complex compounds, a metal must possess the
following characteristics.
Small size
High effective nuclear charge
Tendency to accept electrons (i.e., presence of vacant orbitals)
Since alkali metals have none of these characteristics they have little
tendency to form complexes.
Lithium and Beryllium forms certain complexes. (Due to their small sizes)
The complex forming tendency fall markedly down the groups as the
atomic size increases
32
Complex formation : Weak Tendency

Reasons
1. Absence of low-lying vacant d-orbtals to accept lone pairs

from ligands.
For Na+, 1s2, 2s2, 2p6, 3s, 3p, 3d
High-lying relative to 2p
For Fe2+, 1s2, 2s2, 2p6, 3s2, 3p3, 3d6

Low-lying relative to 3p
33
Complex formation : Weak Tendency

Reasons
2. s-block cations (M+, M2+) have relatively low charge densities

less polarizing and less able to accept lone pairs from ligands.
34
Complex formation :
Owing to its high charge density, Be2+ can form
complexes
35
Electropositive Character
The electropositive character increases down the
group from Li to Cs because ionization enthalpy
decreases down the group

Li > Na > K > Rb > Cs.
Eo
36
Group I
(V)
Group II
(V)
Li
-3.04
Be
-1.69
Na
-2.72
Mg
-2.37
-2.92
Ca
-2.87
Rb
-2.99
Sr
-2.89
Cs
-3.02
Ba
-2.90
Metallic charater (Reactivity)

down the groups
Group I > Group II
Reducing Property
Powerful reducing agents
Li > Na < K = Rb > Cs (E0)
Reasons
Heat of sublimation
Ionisation enthalpy
Hydration energy
37
Reaction with Hydrogen
38

Alkali metals react with hydrogen to form ionic hydrides M+H-.
The reaction of alkali metals with hydrogen decreases from Li
to Cs
Group I
2M(s) + H2(g)
300C 500C
2MH(s)
Group 1 : Hydrides
The order and reactivity with hydrogen
The ionic character of the bonds in these hydrides Increases from
LiH to CsH
LiH < NaH < KH < RbH < CsH
Stability
LiH > NaH > KH > RbH > CsH
40
LAH
Dry ether
4LiH + AlCl3
LiAlH4 + 3LiCl
Powerful reducing agent

Tetrahedral
Selective reducing agent
Reduces carbonyl compounds to alcohols.
It reacts violently with water, so it is necessary to use absolutely

dry organic solvents
Also reduces several inorganic substances
41
Sodium tetrahydridoborate (sodium borohydride)
NaBH4
Can be used even in aqueous solutions
Na and K hydrides are useful
42
Alkaline earth metals react with hydrogen to form ionic

hydrides M2+ (H-)2
Group II
M(s) + H2(g)
43
600C 700C
MH2(s)
Group 2: Hydrides
Form hydrides of type MH2
Be, Mg Little tendency
Polymeric hydrides (BeH2 )

Three centre two electron bond
BeH2 is covalent
MgH2 is partially ionic
Ca, Ba, Sr ionic hydrides
44
Reactions of hydrides
MOH(aq) + H2(g)
MH(s)
MCl(aq) + H2(g)
H (a strong base) tends to react with protonic
reagents to release H2
Reactivity down the groups
45
Reaction with Air / Oxygen
46
Reaction with Air / Oxygen

Group I Elements
All alkali metals form more than one type of

oxide on burning in air (except lithium)
Group II Elements
47
All alkaline earth metals react slowly with air

to form oxides
On burning in air, they form both oxide and

nitride
Reaction with Air / Oxygen : Group 1 Elements
Three types of oxides:
normal oxides
peroxides
superoxides
Abundant supply
O2
oxide
ion
48
1
O2
2
O22
peroxide
ion
2O2
2
superoxide
ion

Type of oxide formed depends on
1. supply of oxygen
2. reaction temperature
3. charge density of M+
49
Lithium
when it is burnt in air, it forms normal
oxide only
4Li(s) + O2(g)
50
180 C
2Li2O(s)
lithium oxide
Sodium
when it is burnt in an abundant

supply of oxygen
forms both the normal oxide and the
peroxide
4Na(s) + O2(g)
2Na2O(s) + O2(g)
excess
51
180 C
2Na2O(s)
sodium oxide
300 C
2Na2O2(s)
sodium peroxide
Potassium, rubidium and caesium

form All three types of oxides when
burnt in sufficient supply of oxygen
52

Group I
element
Normal oxide
Peroxide
Superoxide
Li
Li2O
Na
Na2O
Na2O2
K2O
K2O2
KO2
Rb
Rb2O
Rb2O2
Cs
Cs2O
Cs2O2
RbO2
CsO2
Cations with high charge densities (Li+ or Na+) tend to polarize the
large electron clouds of peroxide ions and/or superoxide ions
Making them decompose to give oxide ions
53
The electron cloud of the superoxide ion is greatly

distorted by the small lithium ion
54

Group I
element
Normal oxide
Peroxide
Superoxide
Li
Li2O
Na
Na2O
Na2O2
K2O
K2O2
KO2
Rb
Rb2O
Rb2O2
RbO2
Cs
Cs2O
Cs2O2
CsO2
Super oxides are generally bright coloured
They exhibit paramagnetic character due to unpaired electron

55

KO2 used as oxygen generators and CO2 scrubbers
in spacecrafts and submarines
4KO2 + 2H2O 4KOH + 3O2
2KOH + CO2 K2CO3 + H2O
56

Supero
Group II
element
Normal oxide
Peroxide
Be
BeO
Mg
MgO
Ca
CaO
Sr
SrO
Ba
BaO
xide
All these oxides are basic in nature (except beryllium

oxide which is amphoteric)
57
Solubility
G0 = H0 - TS0
General rule:
Compounds that contain widely differing radii are soluble in water
Difference in size favours solubility (>80pm)
Thermodynamics of dissolution
Entropy favours dissolution
Hydration energy of a smaller ion is larger
LH = 1 / (r+ + r- )
and
HydH = (1 / r+ ) + (1 / r- )
Ion size assymmetry results in exothermic dissolution
If both are small, both LH and HydH may be large, but enthalpy of
dissolution may not be very exothermic
58
Solubility
The solubility of compounds increases with increase in ionic size of
metal
Fluorides, oxides, hydroxides
The solubility of compounds decreases with increase in ionic size of

metal
Carbonates, sulphates, nitrates, halides (except fluorides)
59
Processes involved in Dissolution and their Energetics
60
Two processes are

1.
Breakdown of the ionic lattice
2.
Hydration
Hsolution
Na+(aq)
NaCl(s)
Na+(g)
o
solution
Cl-(aq)
Cl -(g)
o
hydration
= (-772 +776) kJ mol1

61
= +4 kJ mol1
o
lattice
o
0 , we expect the solids to dissolve in
If Hsolution
water
Solubility as
o
Hsolution
becomes more ve (less +ve)
o
Hsolution
Solids (e.g. NaCl) with small +ve
values
are also soluble in water if the dissolution involves an
increase in the entropy of the system.
o
solution
62
o
solution
TS
o
solution
o
solution
o
solution
o
solution
TS
o
solution
Spontaneous dissolution
TS
o
is always positive
solution
Dissolution with slightly positive

can be spontaneous
63
o
solution
Trends and Interpretations

1. The solubility of Group(II) sulphate decreases down the group
On moving down the group, cationic radius(r+)
both
However,
64
o
L and
o
hydration
become less -ve
o
L less rapidly than
o
hydration
rSO 2 r
4
H
o
L
1
rSO 2 r
constant
o
solution
less ve down
the group
o
hydration
less ve down
the group
o
lattice
+ve constant
Solubility down the group

65
rSO 2 r
4
H
o
L
constant
rSO 2 r
4
o
solution
less ve down
the group
66
(-ve)
o
hydration
more rapidly
down the group
(+ve)
o
lattice
less rapidly
down the group

2. The solubility of Group(II) hydroxides increases down the group
On moving down the group, cationic radius(r+)
both
However,
67
o
L and
o
hydration
become less -ve
o
L more rapidly than
o
hydration
o
solution
more ve down
the group
(-ve)
o
hydration
less rapidly
down the group
(+ve)
o
lattice
more rapidly
down the group
less +ve down

the group
68
General Rules
For s-block compounds with small anions (e.g. OH, F),
solubility in water down the group
For s-block compounds with large anions (e.g. SO42, CO32-),
solubility in water down the group
For s-block compounds with medium size anions (e.g. Br),
solubility in water exhibits irregular pattern down the group
69
Group II compounds with doubly-charged anions (MX)

are less soluble than those with singly-charged anions
(MY2)
Reasons :
1. HL of MX > HL of MY2
2. HL is the major factor affecting solubility
Hsolution of MX is more positive
Solubility : MX < MY2
70
Solubility : Group I > Group II

Reasons :
For a given anions, both HL and Hhydration become more

ve from Group I to Group II
However, HL is the major factor affecting solubility
Hsolution : Group I is less positve than Group II
Solubility : Group I > Group II
71
Thermal Stability
G0 = H0 - TS0
The G0 for the decomposition of a solid becomes negative when

TS0 > H0
H0 depends on
(example carbonates)
= Enthalpy of decomposition + (Lattice Enthalpy of Carbonate - Lattice

Enthalpy of Oxide)
Enthalpy of decomposition is generally large and positive
Metals having small cations, increases the lattice enthalpy of oxide

more than that of the carbonate / sulphate / hydroxide / peroxide
Therefore, Lattice enthalpy plays an important role in deciding the
stability.
72
Thermal decomposition reactions

Metal carbonates
M2CO3(s)
MCO3(s)
heat
heat
M2O(s) + CO2
MO(s) + CO2
Metal hydroxides
2MOH(s)
M(OH)2(s)
73
heat
heat
M2O(s) + H2O(g)
MO(s) + H2O
Relative thermal stability can be measured in two ways

A higher decomposition temperature
a greater thermal stability
BeCO3(s)
MgCO3(s)
CaCO3(s)
SrCO3(s)
BaCO3(s)
74
100C
BeO(s) + CO2(g)
540C
MgO(s) + CO2(g)
900C
CaO(s) + CO2(g)
1290C
SrO(s) + CO2(g)
1360C
BaO(s) + CO2(g)
Relative thermal stability can be measured in two ways

By comparing the standard enthalpy changes of thermal decomposition
reactions
M(OH)2(s) MO(s) + H2O(g) H > 0
A more positive H value
75
a thermally more stable compound
Be(OH)2(s)
Mg(OH)2(s)
MgO(s) + H2O(g)
Ca(OH)2(s)
Sr(OH)2(s)
SrO(s) + H2O(g)
Ba(OH)2(s)
BeO(s) + H2O(g)
H = +54 kJ mol1
H = +81 kJ mol1
CaO(s) + H2O(g)
H = +109 kJ mol1
H = +127 kJ mol1
BaO(s) + H2O(g)
H = +146 kJ mol1
Factors affecting thermal stability

1.
Polarizing power of cation
2.
Polarizability of polyatomic anion
3.
Lattice enthalpy of metal oxide produced
76
Interpretation of trends in thermal stability of

carbonates and hydroxides
1.
Group I > Group II

(a)
M2+ ions have higher charge densities than M+ ions
M2+ ions are more polarizing than M+ ions
Can polarize more the electron cloud of

polyatomic anions
Polarizability as the size of anion

77
Interpretation of trends in thermal stability of carbonates and

hydroxides
1.
Group I > Group II

(b) M2+ ions have higher charge densities than M+ ions
Lattice enthalpy : MO > M2O
Energetic stability : MO > M2O
78
CaCO3(s)
Na2CO3(s)
more favourable
heat
less favourable
heat
CaO(s) + CO2(g)
more stable
Na2O(s) + CO2(g)
less stable
Thermal stability of carbonates : Group I > Group II

79
Interpretation of trends in thermal stability of

carbonates and hydroxides
2.
Thermal stability down the groups
size of cations down the groups

(a)
groups
(b)
80
charge density/polarizing power of cation down the

lattice enthalpies of MO/M2O down the groups
MgCO3(s)
more polarized
BaCO3(s)
less polarized
more favourable
heat
less favourable
heat
MgO(s) + CO2(g)
more stable
BaO(s) + CO2(g)
less stable
Thermal stability of carbonates

down the groups
81
Effect of sizes of the cations on thermal stability of the

carbonates and hydroxides of both Groups I and II metals
82
Reaction with Water
83
Action of Water
Both alkali and alkaline metals react with water
Respective Hydroxides and Hydrogen gas are formed
Reactivity increases down the group

Type : Slow to explosive reactions
Na
84
Reactions with water or steam

Group I
2M(s) + H2O(l)
heat
2MOH(aq) + H2(g)
Group II
M(s) + 2H2O(l)
heat
M(OH)2(aq) + H2(g)
Mg reacts with steam but not cold water

Mg(s) + H2O(g)
heat
MgO(s) + H2(g)
Be has no reaction with either water or steam
Reaction with ammonia

Exhibited both by Group I and II metals
All show Blue colour

Ammoniated electron is present in these solutions, as the
electron is solvated by ammonia
Intensity of blue color increases with metal concentrations

High electrical conductivity
This solution show Magnetic properties
Reducing property of solution of metal in ammonia (selective

reducing action in organic chemistry)
These solution scan be used to prepare any desired oxide, by
passing calculated quantities of oxygen gas through the solutions
86
Hydroxides
87
Group 1 Hydroxides of type MOH

These hydroxides are Strong bases
Basic strength / basic character / solubility in water / thermal
stability
LiOH < NaOH < KOH < RbOH < CsOH
LiOH decomposes on heating to give water and Li2O
88
Group 2: Hydroxides of type M(OH)2

All group 2 metals form hydroxides
Reaction of oxides with water gives hydroxides
Be(OH)2
Amphoteric
Mg(OH)2
Ca(OH)2 , Sr(OH)2 , Ba(OH)2
Weakly Basic
Strongly Basic
Weaker bases than alkali metal hydroxides

Higher IE, smaller ionic size, higher charge on metal ion.
89
Group 2: Hydroxides
The solubility of the hydroxides in water increases with
increase in atomic number of the cation.

Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba (OH)2
insoluble
insoluble
sp. soluble
soluble
soluble
The solubility of hydroxides depend mainly on two facts.
The lattice energy required to dissociate the components of hydroxide.

This decreases from beryllium to barium.
The hydration energy of cation M2+.
This decreases from beryllium to barium as the size of cation increases.
Both lattice and hydration energies decrease down the group, the decrease
in lattice energy is more rapid than the hydration energy and so their
90
solubility increases on descending the group.
Compounds
Solubility / mol per 100 of

water
Mg(OH)2
0.02 103
Ca(OH)2
1.5 103
Sr(OH)2
3.4 103
Ba(OH)2
15 103
Compounds

water
MgSO4
1800 104
CaSO4
11
104
SrSO4
0.71 104
BaSO4
0.009 104
down the group
down the group
Compounds

water
Mg(OH)2
0.02 103
Ca(OH)2
1.5 103
Sr(OH)2
3.4 103
Ba(OH)2
15 103
In general,
Size and/or charge of the

anion
Polarizability of anion
Covalent character
Compounds

water
MgSO4
1800 104
CaSO4
11 104
SrSO4
0.71 104
BaSO4
0.009 104
Solubility in water
Group I: Carbonates
Type M2CO3
Solubility in Water:
Increases as the size (atomic number) of cation increases.
Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
Low
--------------High-------------------------------
Thermal Stability
Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
Low
93
--------------High-------------------------------
Group II: Carbonates

All form carbonates of the type MCO3
Solubility in Water:
Insoluble in neutral medium, soluble in acidic medium
Solubility decreases down the group

BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3
Carbonates are more soluble in a solution containing CO2 Bicarbonates
All carbonate solutions undergo the above reaction

Bicarbonates cannot be obtained in solid form but are known in solution state
only.
Na, K, Rb, Cs bicarbonates are the only ones that can be obtained in solid
94
state.
Group II: Carbonates

Thermal Stability
Increases down the group
BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3

BeCO3 must be stored under CO2
95
Reaction with Nitrogen
96
Alkali Metal : Reaction with Nitrogen family

Lithium forms Nitrides (exceptions w.r.t alkali metal reactions)
Other metals form Azides (MN3)
They form binary compounds with other family members of N
The binary compounds undergo hydrolysis in water to form

ammmonia, phosphine, asine, stibine etc
97
Alkaline Earths : Reaction with nitrogen family

All metals form nitrides M3N2
Ease of formation of nitrides decreases down the group
These nitrides are stable up to 10000C

Get hydrolysed in water to give ammonia
98
Halides
99
Group 1 : Halides
MX
2M(s) + Cl2(g)
heat
2MCl(s)
Ionic compounds , high lattice energies,

Stability
The order of enthalpy of formation of a metal halide is
Fluoride > Chloride > Bromide > Iodide

Fluorides are highly stable
100
Group 1: Halides
Trends in melting and boiling points of halides:
For a given alkali metal, the melting points and boiling points:
Fluoride > Chloride > Bromide > Iodide

For a given halogen, the melting and boiling points
Lithium
< Sodium > Potassium > Rubidium > Caesium
Due to covalent character of Li compound
101
Halides : Ionic Character

The order of ionic character is
LiX < NaX < KX < RbX < CsX
MF > MCI > MBr > MI

(same metal, different halogen)
102
Group 2: Halides
MX2
M(s) + Cl2(g)
heat
MCl2(s)
When crystallized from solutions they form hydrated salts

Anhydrous CaCl2, SrCl2 and BaCl2 can be prepared by heating the
hydrated salts.
103
Group 2: Halides
Alkaline earth metals combine with halogen on heating
to form MX2 type salts.
Be Halides are covalent
Other halides are ionic
Ionic Character
BeX2 < MgX2 < CaX2 < SrX2 < BaX2
MI2 < MBr2 < MCl2 < MF2
104
Structure of BeCl2 molecules
A) At high temperatures, BeCl2 occurs as a gaseous molecule with only four

electrons around Be.
B) In the solid state, BeCl2 occurs in long chains with each Cl bridging two
105 atoms, which gives each Be an octet.
Be
Group 2: Halides
Except BeCl2, all other halides are hygroscopic
Extent of hydration decreases down the group
Be and Mg halides hydrolyse on heating
Ca, Sr, Ba halides get dehydrated on heating
Calcium chloride has a strong affinity for water
Solubility order
Fluorides are readily soluble
106
BeF2 > MgF2 > CaF2 < SrF2 < BaF2

BeX2 > MgX2 > CaX2 > SrX2 > BaX2
MF2 < MCl2 < MBr2 < MI2
Reactions of chlorides
Group I
No significant reactions with water, acids or alkalis
Group II
Do not undergo significant hydrolysis except BeCl2 and
MgCl2
More favoured in alkaline solutions
BeCl2(aq) + 2H2O(l) Be(OH)2(aq) + 2HCl(aq)
MgCl2(aq) + H2O(l) Mg(OH)Cl(aq) + HCl(aq)

Basic salt
107
Group II Sulfates
Obtained by action of dil sulfuring acid on
Metal
Metal oxide
Metal hydroxide
Carbonate
Sulfates of Be, Mg, Ca crystalise as Hydrated salts

BeSO4 . 4H2O MgSO4 . 7H2O
CaSO4 . 2H2O
Sulfates of Sr and Ba crystallise without water of crystallisation
108
Group II Sulfates
Solubility in water
BeSO4 > MgSO4 > CaSO4 >
fairly soluble
SrSO4 > BaSO4
completely insoluble
Thermal stability increases down the group
109
BeSO4 < MgSO4 < CaSO4 < SrSO4 < BaSO4
Nitrates
Group 1 : All form nitrates of type MNO3
Group 2 : All form nitrates of type M(NO)2
All are ionic
All are soluble in water
110
General Reactions of Alkali Metals
111
Important Reactions of the Alkaline Earth Metals - I
The metals reduce O2 to form the oxide:

2 M(s) + O2 (g)
MO(s)
Barium also forms the peroxide BaO (s).
The Metals of higher atomic weight reduce water to form

hydrogen gas:
M(s) + 2 H2O(l) M(OH)2 (aq) + H2 (g)
M = Ca, Sr and Ba
Be and Mg form an adherent oxide coating that allows only
slight reaction.
112
Important Reactions of the Alkaline Earth Metals - I
The metals reduce halogens to form ionic halides:
M(s) + X2(-)
MX2 (s)
X = F, Cl, Br, I
Most of the metals reduce hydrogen to form ionic hydrides.
M(s) + H2 (g) MH2 (s)
113
all except Be
Important Reactions of the Alkaline Earth Metals - II

Most of the metals reduce nitrogen to form ionic nitrides:
3 M(s) + N2 (g)
M3N2 (s)
all except Be
Except for amphoteric BeO, the oxides are basic:
MO(s) + H2O(l)
M(OH)2 (aq)
All carbonates undergo thermal decomposition to the oxide:
MCO3 (s) MO + CO2
This reaction is used to produce CaO (lime) in huge amounts from naturally occurring
limestone, and was the reaction used to generate carbon dioxide to smother the graphite
fire in the Chernobyl reactor.
114
General Reactions of Alkaline Earth Metals
115
Diagonal relationship
116
Reaction
Other Group I
elements
Lithium
Magnesium
Combination with O2
Peroxides and
superoxides
Li2O (normal oxide)
MgO (normal oxide)
Combination with N2
No reaction
Li3N
Mg3N2
Action of heat on
carbonate
No reaction
(thermally stable)
Decomposes to give
Li2O and CO2
Decomposes to give
MgO and CO2
Action of heat on
hydroxide
No reaction
(thermally stable)
Decomposes to give
Li2O and H2O
Decomposes to give
MgO and H2O
Action of heat on
nitrate
Decomposes to give
MNO2 and O2
Decomposes to give
Li2O, NO2 and O2
Decomposes to give
MgO, NO2 and O2
Hydrogen carbonates
Exist as solids
Only exist in solution
Solubility of salts in
water
Most salts are more

soluble than those of
Li, Mg.
Fluoride, hydroxide, carbonate, phosphate,

ethanedioate are sparingly soluble.
Solubility of salts in
organic solvents.
Halides only slightly

soluble in organic
solvents
Halides (with covalent character) dissolve in

organic solvents
117
118
Similarities of Be and Al
Be and Al have the same electronegativity (Be I.0 and AI 1.5) and their
charge/radius ratios are very
The standard oxidation potentials of both Be and are of nearly the same order (Be
= 1.97V; Al= l.7V)
Since the polarizing power of both Be and Al are nearly the same, the covalent
character of their compounds also similar.
Both Be and Al are rendered passive on treatment with conc. HNO 3.
Unlike alkaline earth metals Be does not get readily attacked by dry air. (like Al)
Both Be and Al reacts very slowly with dilute mineral acids due to the presence of
oxide layer.
Both Be and Al react with alkalis liberating H2.
Both Be and AI form carbides which on hydrolrolysis liberate methane.
Both form nitrides when heated in nitrogen which give ammonia by the reaction
with water.
Both form oxides which are amphoteric.
119
Halides of both Be and AI contain halogen bridge bonds
120
121
Compounds of Na
122
Na2CO3 Solvay Process
123
124
C a r b o n a t i n g To w e r
125
Sodium Carbonate
126
Caustic Soda NaOH - Nelson Cell
127
NaOH by Castner Kellner Cell
128
NaOH by Castner Kellner Cell

Castner-Kellner method also known as Mercury Cathode Method.
In this method, the electrolytic cell contains three compartments.
(i) Mercury in the outer compartment acts as a cathode while in middle
compartment acts as an anode due to induction.
(ii) Graphite rods in the outer compartments acts as anode while the iron
rods in the middle compartment acts as a cathode.
Sodium liberated at mercury cathode in the out compartments dissolve in

mercury forming sodium amalgam which moves into middle compartment
where it react with water at cathode forming NaOH, H2 and Hg.
Cl2 gas is liberated at graphite anodes in the outer compartment.
129
Sodium Hydroxide
130
Sodium Hydroxide
131
Sodium Hydroxide
Sodium Beryllate
Sodium Aluminate
Sodium Stannite
Sodium Plumbite
Sodium Zincate
132
Sodium Hydroxide
133
Sodium Sulphate - Salt Cake anhydrous Na2SO4

- Glaubers Salt Na2SO4 .10 H2O
Preparation
The salt cake (anhydrous sodium sulphate) is dissolved in water and the solution
is subjected to crystallization.
Above 32 C the anhydrous salt separates.
Below 32 C, the decahydrate salt crystallises out from the aqueous solution.
Saturated solution of the decahydrate, on cooling below 12 C, gives crystals of

heptahydrate.
Properties
Pb ( NO3 ) 2 Na2 SO4 PbSO4 2 NaNO3

BaCl 2 Na2 SO4 BaSO4 2 NaCl
Sr ( NO3 ) 2 Na2 SO4 SrSO4 2 NaNO3
Uses: It is used in textile industry, medicines as purgative, manufacture

of glass plates and sodium salts.
134
Sodium Bicarbonate, Baking Soda, Na2HCO3

Preparation
By passing CO2 through Sodium Carbonate solution but industrially it is
manufactured by Solvay's process.
Properties
It is sparingly soluble in Water
Solution is alkaline in nature
Uses
On heating, it decomposes to give sodium carbonate.

The metal salts which gives basic metal carbonate with sodium carbonate
gives normal carbonates.
Sodium bicarbonate is used, as an antacid in medicine, in dry fire

extinguishers, in baking powders and as mild antiseptic for skin infections.
135
Compounds of Alkaline Earth Metals
136
Magneisum Oxide - MgO Magnesia

Preparation:
1. Calcination of Magnesite (MgCO3)

MgCO3 MgO + CO2
2. Heating Mg(NO3)2 or Mg(OH)2
Mg(NO3)2 MgO + 4 NO2 + O2

Mg(OH)2 MgO + H2O
Properties:
Light infusible white solid
They have high MP 3073K
Used as refractory material due to the above property

137
Magneisum Oxide - MgO Magnesia

Chemical properties
Hydrolyses in water to form insoluble Mg(OH)2
2MgO H 2 O 2Mg(OH) 2
Being basic, reacts with acids to form respective salts
MgO 2HCl MgCl 2 H 2 O
Gives Mg on reduction with Carbon at high tempertaures
MgO + C Mg + CO
MgO 3C MgC 2 CO
Uses:
Sorels cement used in Dentistry
MgCl2. 5MgO.xH2O
As an antacid
As an insulator when mixed with asbestos
138
Magnesium Hydroxide Mg(OH)2

Preparation:
1. By the hydrolysis of MgO
2. By treating MgCl2 with Ca(OH)2
MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2
White powdery substance
Sparingly soluble in water
Used as an Antacid under the name Milk of Magnesia
139
Magnesium Carbonate MgCO3

Preparation:
Hot Magnesium sulfate with sodium bicarbonate
MgSO4 2 NaHCO3 MgCO3 Na2 SO4 H 2O CO2

Basic magnesium carbonate
H 2O
MgSO4 Na2CO3 MgCO3 .Mg (OH ) 2 Na2 SO4 CO2

(Basic Magnesium Carbonate / Magnesia alva)
MgCO3 .Mg (OH ) 2 3CO2 H 2O Mg ( HCO3)2
Mg ( HCO3)2 MgCO3 H 2O CO2
A solution containing 12% MgCO3 per 100 cc of water containing dissolved

CO2 in called Fluid Magnesia
140
Magnesium Sulphate MgSO4.7 H2O Epsom Salt

Preparation
From Magnesite : heating with dil. Sulfuric acid
MgCO3 H 2 SO4 MgSO4 CO2 H 2O

From Dolomite
MgCO3.CaCO3 2H 2 SO4 MgSO4 CaSO4 2CO2 2H 2O
From Keiserite (commercial method). Boil with water and cool
MgSO4.H 2O H 2O MgSO4.7 H 2O
Properties
Colourless efflorescent solid
C
C
C
MgSO 4 .7H 2 O 30
MgSO 4 .6H 2 O 150
MgSO 4 .H 2 O 200
MgSO 4
141
Magnesium Sulphate MgSO4.7 H2O Epsom Salt

On heating, it decomposes
C
4MgSO 4 250
4MgO 2SO 2 2SO 3 O 2
On heating with Carbon, it gets reduced
2MgSO 4 C 2MgO 2SO 2 CO 2

It forms double salts with alkali metal sulfates
K 2SO 4 .MgSO 4 .6H 2 O
142
Calcium Oxide / Quick Lime / Burnt Lime

Preparation: Decomposition of Limestone
C
CaCO 3 900
CaO CO 2
Reacts with water with a hissing noise to form Slaked lime Ca (OH)2
(Rxn is known as Slaking of lime) H = -15 kcal/mol
CaO H 2 O Ca (OH) 2
Milk of lime : paste of lime in water
Lime water : Clear filtrate
Limelight in oxy hydrogen flame
143

CaO gives Calcium Silicate with silica and Calcium Phosphate with P4O10
CaO SiO2 CaSiO3

6CaO 2 P2O5 2Ca3 ( PO4 ) 2
Forms Calcium Carbide on heating with carbon (2000 deg C)
C
CaO 3C 2000
CaC 2 CO
Calcium Carbide + water gives Calcium Cyanamide

CaC 2
C
N 2 1000
CaCN 2
Calcium cyanamide
144
Calcium Cyanamide + C = Nitrolim - a Fertiliser

Uses
It is used as a drying agent.

It is used in the manufacture of bleaching powder.
It is used in the manufacture of calcium. carbide, cement, glass, lime
mortar, etc.
It is used in the purification of sugar.
145
Calcium Hydroxide / Slaked Lime / Milk of Lime

Preparation:
Slaking of lime
Properties
White amorphous solid
Sparingly soluble in water
On heating, loses water molecule to form Lime CaO
Action of CO2
Ca (OH) 2 CO 2 CaCO 3 H 2 O
CaCO 3 H 2 O CO 2 Ca (HCO 3 ) 2
Insoluble
So luble
Similar reaction with SO2 gas is seen when Calcium bisulphite is

146
formed
Calcium Hydroxide / Slaked Lime / Milk of Lime

Reaction with Ammonia
Ca (OH) 2 2NH 4 Cl Heat
CaCl 2 2NH 3 H 2 O
Reaction with Chlorine

3Ca(OH)2 + 2Cl2
below 35oC
slaked lime
Ca(OCl)2.Ca(OH)2.CaCl2. 2 H2 O +
H2 O
bleaching powder
Bleaching powder is a calcium salt of hypochlorous acid (HOCl)
Ca(OCl)2
Uses: It is used
1. for absorbing acid gases.

2. in the manufacture of bleaching powder and caustic soda.
3. in the production of lime mortar for construction of buildings, whitewashing buildings
4. in glass making, tanning industry and for purification of sugar
5. for the preparation of NH3 from NH4Cl in Solvay process
147
6. as lime water in laboratories
Gypsum CaSO4.2H2O
Preparation
CaCl 2 H 2SO 4 CaSO 4 2HCl

CaCl 2 Na 2SO 4 CaSO 4 2NaCl
Properties
White crystalline solid
Solubility decreases on increase in temperature
Action of heat Calcium sulphate hemihydrate (plaster of paris) is formed
C
2[CaSO 4 .2H 2 O] 120
(CaSO 4 ) 2 .H 2 O 3H 2 O
Plaster of Paris
C
[(CaSO 4 ) 2 .H 2 O] 200
2CaSO 4 H 2 O
Dead burnt plaster

148
heated
2CaSO 4 Strongly
2CaO 2SO 2 O 2
Calcium Carbonate, CaCO3

Naturally found as limestone, marble, chalk
Preparation
Ca (OH) 2 CO 2 CaCO 3 H 2 O
CaCl 2 Na 2 CO 3 CaCO 3 2NaCl

White fluffy powder insoluble in water. But dissolves in water in the
presence of carbon-di-oxide to form calcium bicarbonate
CaCO 3 H 2 O CO 2 Ca (HCO 3 ) 2
149
Mortar
It is also known as lime mortar.
It is an intimate mixture of 1 part of slaked lime, 3 parts of sand and
water made into paste.
This is used to bind the bricks firmly.
Setting of mortar involves the following steps.
(i) Mortar loses water on account of evaporation.
(ii) Carbon dioxide is absorbed from the air converting into calcium
carbonate which acts as a binding material.
(iii) Slaked lime reacts with silica forming calcium silicate which gives
hardness.
150
Cement
The name portland cement was given to it by Joseph Aspidin (a mason!)
because when it is mixed with sand and water it hardens like the lime
stone querried at Portland in England.
Composition :
CaO 50 to 60 %; SiO2: 20 to 25%; Al2O3 : 5 to 10 %; MgO :2 to 3%; Fe2O3 I
to 2% and SO3 1 to 2%.
If lime is excess the cement cracks during setting but if it is less the
cement will be weak.
Excess of Al2O3 will make cement quick drying
The raw materials for the manufacture of cement are limestone and
alumino silicates (clay, sand and shales). When the powdered raw
materials are heated in a rotary kiln, sintered clinker will be obtained.
151
The setting of cement by mixing with water is due to hydration of the

molecules and their rearrangement.
S - Block Metals in Biological Systems
152
Biological functions of Sodium and Potassium ions
Sodium and potassium are the most common cations in biological fluids.
Sodium ion is the major cation of extracellular fluids of animals and in blood plasma,
including human beings which is known to activate certain enzymes in the animal
body
These ions participate in the transmission of nerve signals.
They also regulate flow of water across cell membranes and in transport of sugars,
amino acids into the cells.
Potassium ions are the most abundant cations within cell fluids, where they activate
many enzymes that participate in oxidation of glucose to produce adenosine
triphosphate (ATP).
A typical 70 kg adult contains about 90 g of Na+ ions and 170 g of K+ ions.
The daily requirement of sodium and potassium is about 2 g each.
153
Biological functions of Magnesium and Calcium
Magnesium is an important constituent of chlorophyll.
Mg2+ and Ca2+ ions are also responsible for the transmission of electrical
impulses along the nerve fibre and the contraction of muscles
Calcium ions are essential for the formation of bones and teeth
It also plays important roles in maintaining rhythm of heart, clotting of blood,

neuromuscular function, interneuronal transmission, cell membrane integrity,
etc.
The calcium concentration in plasma is regulated at about 100 mg L-1. It is

maintained by two hormones, calcitonin and parathyroid hormone.
The substance present in bones is continuously solubilized and redeposited to

the extent of 400 mg per day in man.
All this calcium passes through the plasma.
154
The END

S BLOCK Elements Jee

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s-Block Elements

The s-block elements

Variation in Physical Properties of s-block

Atomic and Ionic Radii

Li < Na < K < Rb < Cs

Li+ < Na + < K + < Rb + < Cs +

Li < Na < K < Rb < Cs

Li > Na > K > Rb > Cs

Atomic Radius and Ionic Radius

down the groups

On moving down the groups,

then slowly (e.g. from K to Fr)

Both atomic radius and ENC down the groups

For Group I elements, 2nd IE >> 1st IE because

For Group II elements, 3rd IE >> 2nd IE

Variations in the first,

The electronegativity values decreases down the group from Li to Cs

Li > Na > K > Rb > Cs

All have low electronegativity => Electropositive

always has a negative value

Formation of hydrated salts :

Group II > Group I

Melting & Boiling Point

charge density of cations

number of valence electrons participating in the sea of electrons

packing efficiency of the crystal lattices

down the groups

Densities of Li, Na, K

Density gradually increases on moving down the group from Li to

Anomaly: K is lighter than Na

Beryllium and magnesium atoms are

2. In the cooler part of the flame,

+ golden yellow light

Na+Cl (more volatile)

+ golden yellow light

Complex formation : Weak Tendency

1. Absence of low-lying vacant d-orbtals to accept lone pairs

For Fe2+, 1s2, 2s2, 2p6, 3s2, 3p3, 3d6

Complex formation : Weak Tendency

2. s-block cations (M+, M2+) have relatively low charge densities

decreases down the group

Metallic charater (Reactivity)

Reaction with Hydrogen

Reaction with Hydrogen

Powerful reducing agent

It reacts violently with water, so it is necessary to use absolutely

Sodium tetrahydridoborate (sodium borohydride)

Reaction with Hydrogen

Alkaline earth metals react with hydrogen to form ionic

Polymeric hydrides (BeH2 )

Ca, Ba, Sr ionic hydrides

Reaction with Air / Oxygen

Reaction with Air / Oxygen

All alkali metals form more than one type of

All alkaline earth metals react slowly with air

On burning in air, they form both oxide and

Reaction with Air / Oxygen : Group 1 Elements

Three types of oxides:

Reaction with Air / Oxygen : Group 1 Elements

Reaction with Air / Oxygen : Group 1 Elements

Reaction with Air / Oxygen : Group 1 Elements

when it is burnt in an abundant

Reaction with Air / Oxygen : Group 1 Elements