s­Block Elements

(Alkali and Alkaline Earth Metals)

AIEEE Syllabus
General introduction, electronic configuration and general trends in
physical and chemical properties of elements, anomalous properties of the
CHAPTER
3
first element of each group, diagonal relationships. Preparation and
properties of some important compounds ­ sodium carbonate, sodium
chloride, sodium hydroxide and sodium hydrogen carbonate; Industrial uses
of lime, limestone, Plaster of Paris and cement; Biological significance of
Na, K, Mg and Ca.

THIS CHAPTER
GROUP­1. ALKALI METALS COVERS :
l Group­1. Alkali Metals
Elements Symbol Atomic number Ø Chemical
Reactivity
Lithium Li 3
Ø Diagonal
Sodium Na 11 Relationship :
Potassium K 19 Similarities with
Rubidium Rb 37 Magnesium
Caesium Cs 55 l Group­2. Alkaline
Earth Metals
Francium Fr 87
Ø Similarities
(Diagonal
Physical Properties relationship)
between
Important physical properties of Alkali metals are given below :
Beryllium and
1. Physical State Aluminium
Ø Sodium
(a) Soft, silvery white metal having a high and bright lusture when freshly
Hydroxide
cut. (NaOH)
(b) They all form body centred lattices. Ø Sodium
Carbonate
(c) Softness increases with increase of atomic number because there is (Na2CO3.10H2O)
a continuous decrease of metallic bond strength on account of an l Sodium Chloride
increase in atomic size. (NaCl)
Ø Magnesium
2. Atomic and Ionic radii
Chloride,
(a) Atoms are largest in their period. MgCl 2.6H2O
Ø Magnesium
(b) Atomic as well as ionic size increases from Li to Fr due to the presence Sulphate,
of one extra shell of electrons. Epsomsalt,
MgSO4.7H2O
3. Density
Ø Biological Role of
(a) Li, Na, K, are lighter than water. Sodium,
Potassium,
(b) Density increases on moving down from Li to Cs but K is lighter than Magnesium and
sodium. Calcium

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4. Ionisation energies and Electropositive character

(a) Due to their large size, ionisation energy is relatively low.
(b) As the ionisation potential decreases from Li to Cs, the electropositive character increases.
5. Oxidation States
Alkali metal can lose their electron quite easily to form univalent positive ion. Thus show only +1 oxidation
state.
6. Flame Colouration
The alkali metals and their salts impart a characteristic colour to the flame.
Li Na K Rb Cs
Crimson red Yellow Violet Red violet Blue
7. Reducing Power
The reducing power of a metal is related to its oxidation potential which represents the tendency of element
to lose electron and get oxidised.
All alkali metals have low I.E. leading to a high oxidation potential.
(a) Reducing nature (in solution is) :–
Li > Cs > Rb > K > Na
(b) In gaseous state
Li < Na < K < Rb < Cs
8. Solution in Liquid Ammonia
(a) The alkali metals dissolve in liquid ammonia without the evolution of hydrogen. The colour of the dilute
solution is blue. The solutions are good conductors of electricity and have strong reducing properties.
(b) The dissolution of metal in NH3 yields ammoniated cation and electron.
M ¾® M+ + e–
or M + (x + y) NH3 ¾® [M (NH3)x]+ + [e (NH3)y] –
solvated electron.

Chemical Reactivity
Alkali metals are highly reactive due to low ionisation energy.
1. Reaction with Oxygen
(a) Alkali metal ignites in oxygen and form oxides.

2 O 2 O 2 O
M ¾¾
¾ ® M2O ¾¾
¾ ® M2O 2 ¾¾
¾ ® MO2
Oxide Peroxide Superoxide

(b) Li forms stable oxide (Li2O), Na forms peroxide(Na2O2) and rest of the metal forms superoxides.
(c) Oxides of alkali metals are basic in nature and basic character increases from Li to Cs as ionic character
increases.
(d) Peroxides and superoxides behave as strong oxidising agents. Superoxides on treatment with dil. acids
form H2O2 , O2 and hydroxide.
KO2 + 2H2O ¾® 2KOH + H2O2 + 3O2
2. Reaction with Water
(a) Hydrogen is liberated.
2M + 2H2O ¾® 2MOH + H2.
(b) Basicity of hydroxides increases down the group, due to increase in electropositive character.

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3. Reaction with Hydrogen

(a) Alkali metal hydrides are formed when metals are heated with H2.
2Na + H2 ¾® 2NaH.
(b) Metal hydrides are ionic. They are good reducing agents. Reducing power increases down the group.
4. Reactivity with Halogen
(a) Halides are ionic compounds having negative enthalpies of formation.
(b) The most negative enthalpy of formation occur with fluorides. The negative value decreases as
Fluorides > Chlorides > Bromides > Iodides.
Thus fluorides are most stable.
(c) LiF is insoluble in water due to very high lattice energy.
CsI is insoluble in water due to very low hydration energy.
Rest of halides are soluble in H2O.
5. Metal Hydroxides
(a) Basic strength of hydroxide increases with the increasing electropositivety of metal.
CsOH > RbOH > KOH > NaOH > LiOH.
(b) Solubility of hydroxides increases with increasing ionic character.
CsOH > RbOH > KOH > NaOH > LiOH.
6. Nature of Carbonates and Bicarbonates
(a) Carbonates are highly stable towards heat and readily soluble in water.
(b) As the electropositive character increases from Li to Cs, the stability of carbonates also increases.
Cs2CO3 > Rb2CO3 > K2CO3 > Na2CO3 > Li2CO3.
(c) Li2CO3 decomposes on heating and it is insoluble in water.
(d) Aqueous solution of carbonates are alkaline.
(e) Bicarbonates MHCO3 are known in solid state except of lithium.

Diagonal Relationship : Similarities with Magnesium

Lithium shows resemblance with magnesium, an element of group 2. This resemblance is termed as diagonal
relationship

Group 1 Group 2

Li Be

Na Mg
Reasons for the diagonal relationship are the following :
1. Electronegativities of Li and Mg are quite comparable (Li = 1.00, Mg = 1.20),
2. Atomic radii and ionic radii of Li and Mg are not very much different.
Atomic radii (Å) Li 1.52 Mg 1.60
Ionic radii (Å) Li+ 0.76 Mg2+ 0.72
(i) Atomic volumes of Li and Mg are quite similar.
Li 12.97 mL/mole Mg 13.97 mL/mole

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3. Both have high polarising power (ionic potential)

Ionic charge
Polarising power (F) =
(Ionic radius) 2

Cations with large ionic potentials have a tendency to polarise the anions and to give partial covalent
character to compounds.
4. Nitrates of lithium like magnesium decompose to give oxide, whereas all other alkali metal nitrates give
nitrite.

GROUP­2. ALKALINE EARTH METALS

Elements Symbol Atomic number

Beryllium Be 4
Magnesium Mg 12
Calcium Ca 20
Strontium Sr 38
Barium Ba 56
Radium Ra 88

Physical Properties
The important physical properties of Alkaline earth metal are given below
1. Atomic radii and Ionic radii
Atomic and ionic size increases from Be to Ra due to presence of an extra shell at each step.
2. Density
(a) These metals are denser than alkali metals due to their greater nuclear charge and smaller size.
(b) Density decreases slightly upto calcium and then increases upto radium.
3. Ionisation Energy and Electropositive Character
(a) Ionisation energy of these metals are higher than alkali metals yet these are sufficiently low to make M2+
ion.
(b) These metals are thus strongly electropositive in nature but less than corresponding alkali metal.
(c) IE1 and IE2 of metals decreases from Be to Ba. Due to presence of full filled electronic configuration
ionisation energy is very high.
4. Oxidation states
All metal show a stable oxidation state of +2.
5. Flame Colouration
Ca, Sr, Ba, Ra impart a characteristic colour to the flame, whereas Be and Mg do not show flame clouration
due to high ionisation energy.
Ca – brick red, Sr – crimson, Ba – green, Ra – crimson
6. Reducing Nature
(a) The alkaline earth metals have the tendency to loose electrons and change into bivalent cation.
M ¾® M2+ + 2e–
Hence they act as strong reducing agents.
(b) The reducing nature increases as the atomic number increases.

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Chemical Properties
The important chemical properties of alkaline earth metals are discussed below

1. Reaction with Oxygen

(a) Except Ba and Ra, all other metals when burnt in oxygen form oxide of type MO.

2M + O2 ¾® 2MO

2O 2 O
Ba ¾¾
¾ ® BaO ¾¾
¾ ® BaO 2
high temp.

(b) BeO is amphoteric in nature while other oxides are basic in nature.

MO + H2O ¾® M(OH)2 + heat.

(c) Basic nature of oxide increases from Be to Ba.

2. Action of Water

(a) Mg decomposes boiling water.

(b) Be is not attacked by water at any temperature.

(c) Ca, Sr, Ba, Ra decomposes cold water with evolution of H2 gas.

M + 2H2O ® M(OH)2 + H2.

(d) Be(OH)2 is amphoteric, but other hydroxides are basic. The basic strength increase from Be to Ba.

(e) Solubility of hydroxides also increases from Be(OH)2 to Ba(OH)2.

3. Hydride formation

(a) Except Be, all other metals directly combines with hydrogen to form hydrides of the type MH2.

(b) BeH2 and MgH2 are covalent hydride while other hydrides are ionic in nature.

(c) Ionic hydrides are violently decomposed by water evolving hydrogen.

CaH2 + 2H2O ¾® Ca(OH)2 + 2H2

4. Halides

(a) Metals directly combines with X2 to form halides

M + X2 ¾® MX2.

(b) BeX2 is covalent in nature, whereas other metal halides are ionic solids.

(c) These halides are hygroscopic in nature and readily form hydrates e.g., MgCl2.6H2O, BaCl2.2H2O etc.

5. Carbonates and Bicarbonates

(a) Carbonates of metals are insoluble in water, they dissolve in presence of CO2 only.

MCO3 + H2O + CO2 ¾® M(HCO3)2.

(b) Solubility of carbonates decreases on moving down the group, while stability increases.

6. Sulphates
MO + H2SO4 ¾® MSO4 + H2O.

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AIEEE/State CET s­Block Elements (Alkali and Alkaline Earth Metals)

(a) Solubility of sulphates decreases on moving down the group.

BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4.
(b) Solubility depends upon hydration energy of cation which is maximum in Be2+.
7. Complex Formation
Be2+ and Mg2+ due to their small size show some tendency of complex formation.
Ex. [BeF3]–, [BeF4]2– and [Be(H2O)4]2+, chlorophyll (Complex of Mg2+)
8. Organometallic Compounds
Be and Mg forms a number of compounds with M – C bonds.
e.g., Grignard reagent.

Similarities (Diagonal relationship) between Beryllium and Aluminium

Beryllium shows some similarities in properties with aluminium, the second typical element of group 13 of the
next higher period.

Group 2 Group 13

Second period Be B

Third period Mg Al

The following are the causes of diagonal relationship :

(a) The polarising power of Be2+ and Al3+ ions is high. Consequently the compounds develop covalent nature.
(b) The standard oxidation potential values of both the elements are very close to each other.
(c) The electronegativity values of both the elements are the same.

Sodium Hydroxide (NaOH)

Preparation :
Sodium hydroxide is prepared mainly by following processes.

1. Soda lime process, Causticisation process or Gossage process

o
80 - 90 C
Na2CO3 + Ca(OH)2 ¾¾ ¾¾ ¾® 2NaOH + CaCO3

2. Castner Kellner process ­ Electrolytic process

Electrolyte ® Brine (NaCl Solution in water)
Anode ® Graphite
Cathode ® Iron rods and Mercury (acts as intermediate cathode by induction).
Reaction :

NaCl ® Na+ + Cl–

At anode :
Cl– ® Cl + e–

Cl + Cl ® Cl2
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At cathode

Na+ + e– + Hg ® Na – Hg
2Na – Hg + 2H2O ® 2NaOH + H2 + 2Hg
(sodium amalgam)

Properties : Sodium hydroxide is white hygroscopic solid used in many processes as a solvent. Its important
properties are discussed below:

SiO2
Na2SiO3 + H2 O
Zn
Na2ZnO2
S
Na2S + Na2S2O3
P
NaOH– NaH2PO2 + PH3
cold, dilute
Cl2 NaCl + NaClO
hot, conc.
NaCl + NaClO3
FeCl3
Fe(OH)3

Sodium Carbonate (Na2CO3.10H2O):

Preparation : Sodium carbonate is mainly prepared by Solvay's process.

Solvay’s ammonia process ­

CO2 + H2O ® H2CO3

H2CO3 ® H+ + HCO3–
NH3+ H+ ® NH4+
NH4+HCO3– + NaCl ® NaHCO3 + NH4Cl
o
250 C
2NaHCO3 ¾¾ ¾® Na2CO3 + H2O + CO2 (recycled)
2NH4Cl + CaO ® CaCl2 + H2O + 2NH3 (recycled)
Properties : Sodium carbonate is a white crystalline solid, efflorescent, whose important properties are as
follows:

Dry air
1. Na2CO3.10H2O ¾¾ ¾® Na2CO3.H2O + 9H2O
2. Fe2(SO4)3 + 3Na2CO3 ® Fe2(CO3)3 + 3Na2SO4
Fe2(CO3)3 + 3H2O ® 2Fe(OH)3 + 3CO2
3. Na2CO3 + H2O + CO2 ® 2NaHCO3

Sodium Chloride (NaCl) :

Preparation: Salty water is subjected to evaporation in open fields which leaves behind the residue of impure
sodium chloride as deposits, which is further purified by saturating with Hydrogen chloride gas. Due to common
ion effect, the ionic product of NaCl increases above the solubility product and crystals of pure NaCl is thrown
out.
Properties : Sodium chloride is a white crystalline solid, insoluble in alcohol, hygroscopic.
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Sodium Bicarbonate
It is obtained as an intermediate product in the Solvay ammonia soda process
Na2CO3 + CO2 + H2O ® 2NaHCO3
Properties :
(a) Crystalline solid, solution is alkaline in nature
NaHCO3+ H2O NaOH + H2CO3
(b) On heating, it releases carbon dioxide and water forming sodium carbonate
2NaHCO3+ H2O ® Na2CO3 + H2O + CO2

Calcium oxide, Quick lime (CaO) :

Preparation : Calcium oxide is mostly prepared by decomposition of calcium carbonate.

CaCO3 ¾1000 °C
¾ ¾ ¾¾® CaO + CO2
Properties : Calcium oxide is white amorphous powder. The important reactions of CaO are given below:

H2O
Ca(OH)2
HCl
CaCl2
SiO2 CaSiO3
CaO–
P2O5
Ca3(PO4)2
CO2
CaCO3
C
CaC2 + CO

Calcium Hydroxide, Slaked lime, (Ca(OH)2 ) :

Preparation : Calcium hydroxide is mostly prepared from quick lime
CaO + H2O ® Ca(OH)2
Properties : Calcium hydroxide is a white amorphous solid. The important properties of calcium hydroxide
are given below

CO2
CaCO3
NH4Cl
CaCl2 + NH3
Ca(OH)2– Cl2
CaOCl2
Cl2
CaCl2
Red heat

Calcium Carbonate, Lime stone or Marble (CaCO3) :

Preparation : Calcium carbonate is majorly prepared by
(a) Ca(OH)2 + CO2 ® CaCO3 + H2O
(b) CaCl2 + (NH4)2CO3 ® CaCO3 + 2NH4Cl
Properties : Calcium carbonate is a white powder. It is insoluble in water
CaCO3 + H2O + CO2 ® Ca (HCO3)2
1000 °C
CaCO3 ¾¾ ¾¾® CaO + CO2

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Calcium Sulphate (CaSO4 ) :

Preparation : Calcium sulphate is obtained by adding calcium chloride in sulphuric acid or sodium sulphate
CaCl2 + H2SO4 ® CaSO4 + 2HCl
Properties : Calcium sulphate is a white crystalline solid. It is sparingly soluble in water. It is found in nature
as anhydrite (CaSO4) and gypsum (CaSO4.2H2O). Gypsum when heated converts into CaO.

120 º C
(a) 2[CaSO4.2H2O] ¾¾ ¾¾® [(CaSO4)2.H2O] + 3H2O
(Plaster of Paris)
200 ºC
[(CaSO4)2.H2O] ¾¾ ¾¾® 2CaSO4 + H2O
(Anhydrite)
D
(b) 2CaSO4 ¾¾® 2CaO + 2SO2 + O2.

Cement : Composition­CaO­50­60%; MgO­2­3%, SiO2­20­25%; Fe2O3­1­2%; Al2O3­5­10%; SO3 1­2%.

In general silica and alumina should be present in the ratio of 2.5 to 4.0. Similarly the ratio of lime to the total
mixture of SiO2, Al2O3 and Fe2O3 should be 2 : 1.

Magnesium Chloride, MgCl2.6H2O

Preparation :
1. By heating and cooling the carnallite when whole of KCl is deposited while MgCl2.6H2O remains in the
fused state.
2. By dissolving Mg, MgO, Mg(OH)2 or MgCO3 in dil. HCl acid.

Properties :
1. Highly deliquescent solid
2. The molecule of hexahydrate can be removed by heating

HCl(g)
MgCl2.6H2O ¾¾ ¾ ¾® MgCl2

Magnesium Sulphate, Epsom salt, MgSO4.7H2O

Preparation :
1. By heating dolomite with dil. H2SO4

MgCO3 + H2SO4 ¾
¾® MgSO4 + H2O + CO2
2. By boiling Kieserite in water and cooling the resulting solution

MgSO4∙H2O + 6H2O ¾
¾® MgSO4∙7H2O

Properties :
1. Upon heating to 150°C, it changes to monohydrate which on further heating changes to anhydrous state
at 200°C.
2. It is reduced by lamp black

2MgSO4 + C ¾
¾® 2MgO + 2SO2 + CO2
3. Forms double salts with alkalimetal sulphates

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Biological Role of Sodium, Potassium, Magnesium and Calcium

1. Sodium and potassium are the most common cations in biological fluids.
2. Na+ is an extracellular ion and K+ an intracellular ion
3. Na+ takes parts in maintenance of electric potential across the cell membrane, also help in retaining water
in blood.
4. The main pigment for absorption of light in plants is chlorophyll which contains magnesium.
5. Calcium ions are also involved in enzymatic system and play roles in regulating muscle contraction,
transmitting nervous pulses and acts as an agent of blood coagulation.

q q q

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