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

Li > Na > K > Rb > 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

Reaction with Hydrogen

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
Li > Na > K > Rb > Cs
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

Reaction with Hydrogen

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

Reaction with Air / Oxygen : Group 1 Elements

Type of oxide formed depends on

1. supply of oxygen
2. reaction temperature

3. charge density of M+

49

Reaction with Air / Oxygen : Group 1 Elements

Lithium
when it is burnt in air, it forms normal
oxide only
4Li(s) + O2(g)

50

180 C

2Li2O(s)

lithium oxide

Reaction with Air / Oxygen : Group 1 Elements

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

Reaction with Air / Oxygen : Group 1 Elements

Potassium, rubidium and caesium

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

52

Reaction with Air / Oxygen : Group 1 Elements

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

Reaction with Air / Oxygen : Group 1 Elements

The electron cloud of the superoxide ion is greatly

distorted by the small lithium ion
54

Reaction with Air / Oxygen : Group 1 Elements

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

Reaction with Air / Oxygen : Group 1 Elements

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

56

Reaction with Air / Oxygen : Group 2 Elements

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

Trends and Interpretations

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

Trends and Interpretations

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

Solubility down the group

Trends and Interpretations

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

Trends and Interpretations

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

Solubility 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

Solubility / mol per 100 of

water

MgSO4

1800 104

CaSO4

11

104

SrSO4

0.71 104

BaSO4

0.009 104

down the group

down 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

In general,

Size and/or charge of the

anion
Polarizability of anion
Covalent character

Compounds

Solubility / mol per 100 of

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

Calcium Oxide / Quick Lime / Burnt Lime

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

Calcium Oxide / Quick Lime / Burnt Lime

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