Chapter 10: The s-Block Elements

• General Electronic Configuration of s-Block Elements

For alkali metals [noble gas] ns1
For alkaline earth metals [noble gas] ns2
• Group 1 Elements: Alkali metals
Electronic Configuration, ns1, where n represents the valence shell.
These elements are called alkali metals because they readily dissolve in water to form soluble
hydroxides, which are strongly alkaline in nature.

• Atomic and Ionic Radii

Atomic and ionic radii of alkali metals increase on moving down the group i.e., they increase
in size going from Li to Cs. Alkali metals form monovalent cations by losing one valence
electron. Thus cationic radius is less as compared to the parent atom.
• Ionization Enthalpy
The ionization enthalpies of the alkali metals are generally low and decrease down the group
from Li to Cs.
Reason: Since alkali metals possess large atomic sizes as a result of which the valence s-
electron (ns1) can be easly removed. These values decrease down the group because of
decrease in the magnitude of the force of attraction with the nucleus on account of increased
atomic radii and screening effect.
• Hydration Enthalpy
Smaller the size of the ion, more is its tendency to get hydrated hence more is the hydration
enthalpy.
Hydration enthalpies of alkali metal ions decrease with increase in ionic sizes.
Li+ > Na+ > K+ > Rb+ > Cs+
• Density
These are light metals with low densities. Lithium is the lightest known metal. On moving
down the group, ‘density increases from Li to Cs. This is because, down the group, both the
atomic size and atomic mass increases but the effect of increase in atomic mass is more as
compared to increase in atomic size.
The density of potassium is lesser than that of sodium because of the abnormal increase in
size on moving down from Na to K.
• Melting and boiling points
The melting and boiling points of alkali metals are quite low and decrease down the
group due to weakening of metallic bond.
Fr is a liquid at room temperature.
• Softness
These are soft. malleable and ductile solids which can be cut with knife. They possess
metallic lustre when freshly cut due to oscillation of electrons.
• Ionisation enthalpy
The first ionisation enthalpy of alkali metals is the lowest amongst the elements in their
respective periods and decreases on moving down the group.
The second ionisation enthalpies of all the alkali metals are very high because by releasing an
electron, ions acquire noble gas configuration. so removal of second electron is difficult.
• Electropositive character
Due to low ionisation enthalpies, alkali metals are strongly electropositive or metallic in
nature and electropositive nature increases from Li to Cs due to decrease in ionization
enthalpy.
• Oxidation state
The alkali metal atoms show only +1 oxidation state, because their unipositive ions attain the
stable noble gas configuration.
The alkali metal ions attain noble gas configuration with no unpaired electrons so. they are
diamagnetic in nature. Alkali metals however have paramagnetic nature due to one unpaired
electron.
• Electrical conductivity
Due to the presence of loosely held valence electrons which are free to move throughout the
metal structure. the alkali metals are good conductors of heat and electricity. Electrical
conductivity increases from top to bottom in the order

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

• Reducing character
All the alkali metals are good reducing agents due to their low ionisation energies. Their
reducing character follows the order

Na < K < Rb < Cs < Li

• Chemical Properties of Alkali Metals

(i) Reaction with air:
When exposed to air surface of the alkali metals get tarnished due the formation of oxides
and hydroxides.
Alkali metals combine with oxygen upon heating to form different oxides depending upon
their ionic size.

(ii) Reaction with water:

Alkali metals react with water to form hydroxide and dihydrogen
 (iii) Reaction with hydrogen:
The alkali metals combine with hydrogen at about 673 K (lithium at 1073 K) to form
hydrides.
2M + H2 ————-> 2M+
The ionic character of hydrides increases from Li to Cs.
(iv) Reaction with halogens
Alkali metals combine with halogens directly to form metal halides.
2M + X2————–> 2MX
They have high melting and boiling points.
Order of reactivity of M:

(v) Reducing nature:

The alkali metals are strong reducing agents. In aqueous solution it has been observed that the
reducing character of alkali metals follows the sequence Na < K < Rb < Cs < Li, Li is the
strongest while sodium is least powerful reducing agent. This can be explained in terms of
electrode potentials (E°). Since the electrode potential of Li is the lowest. Thus Li is the
strongest reducing agent.
(vi) Solubility in liquid ammonia:
The alkali metals dissolve in liquid ammonia to give deep blue solution. The solution is
conducting in nature.
M+ (x + y) NH3 ———-> [M (NH3) X]+ + [e (NH3) y]–
When light falls on the ammoniated electrons, they absorb energy corresponding to red
colour and the light which emits from it has blue colour. In concentrated solution colour
changes from blue to bronze. The blue solutions are paramagnetic while the concentrated
solutions are diamagnetic.

Anomalous Behaviour of Lithium

Lithium shows anomalous behaviour due to the following reasons:

1. It has the smallest size in its group.

2. It has very high ionization enthalpy and highest electronegativity in the group.

3. Absence of d-orbitals inits valence shell.

As a result, it differs from the other alkali metals in the following properties :

 Lithium is harder than other alkali metals, due to strong metallic bond.
 Lithium combines with O2 to form lithium monoxide, Li2O whereas other alkali metals form
peroxides (M2O2) and superoxides (MO2).
 Lithium, unlike the other alkali metals, reacts with nitrogen to form the nitride.

 Li2CO3 ,LiF and lithium phosphate are insoluble in water while the corresponding salts of
other alkali metals are soluble in water.
 Li2CO3 decomposes on heating to evolve CO2 whereas other alkali metal carbonates do not.
 Lithium nitrate on heating evolves O2 and NO2 and forms Li2O while other alkali metal
nitrates on heating form their respective nitrites.

Diagonal Relationship
Lithium shows diagonal resemblance with magnesium [the element of group 2] and this
resemblance is due to similar polarising power, i.e.,[ionic charge / (ionic radius)2] of both
these elements.
Lithium resembles magnesium in the following respects :

1. The atomic radius of lithium is 1.31 Å while that of magnesium is 1.34 Å.

2. The ionic radius of Li+i on is 0.60 Å, which is very close to that of Mg2+ ion (0.65 Å).
3. Lithium (1.0) and magnesium (1.2) have almost similar electronegativities.
4. Both Li and Mg are hard metals.
5. LiF is partially soluble in water like MgF2.
6. Both combine with O2 to form monoxides, e.g., Li2O and MgO.
7. Both LiOH and Mg(OH)2 are weak bases.
8. Both LiCI and MgCl2 are predominantly covalent.
9. Both Li and Mg combine with N2 to form their respective nitrides, Li3N and Mg3N2.
10. Both lithium and magnesium nitrates on heating evolve NO2 and O2 leaving behind their
oxides.

Compounds of Sodium

1. Sodium Chloride, Common Salt or Table Salt [NaCI]

Sea water contains 2.7 to 2.9% by mass of the salt. Sodium chloride is obtained by
evaporation of sea water but due to the presence of impurities like CaCl2 and MgCl2 it has
deliquescens nature. It is purified by passing HCI gas through the impure saturated solution
of NaCl and due to common ion effect, pure NaCl gets precipitated. 28% NaCl solution is
called brine.
2. Sodium Hydroxide or Caustic Soda [NaOH]
Methods of preparation
(i) A 10% solution of Na2CO3 is treated with milk of lime.

(ii) Electrolytic process involves Nelson cell and Castner-Kellner cell.

A brine solution is electrolysed using a mercury cathode and a carbon anode. Sodium metal
discharged at the cathode combines with Hg to form Na-amalgam. Chlorine gas is evolved at
the anode.

The amalgam is treated with water to give sodium hydroxide and hydrogen gas.

2Na-Hg + 2H2O → 2NaOH + 2Hg + H2

Physical properties
Sodium hydroxide is a white translucent solid. It is readily soluble in water. Crystals of
NaOH are deliquescent.
Chemical properties
1. It is a hygroscopic, deliquescent white solid, absorbs CO2 and moisture from the
atmosphere

3. Sodium Carbonate or Washing Soda (Na2CO3 . 10H2O)

Solvay process
CO2 gas is passed through a brine solution saturated with NH3

Sodium bicarbonate is filtered and dried. It is ignited to give sodium carbonate.

Properties
1. Sodium carbonate crystallises from water as decahydrate which effloresces on exposure to
dry air forming monohydrate which on heating change to anhydrous salt (soda-ash).
Uses
1. It is used in water softening, laundering and cleaning.
2. It is used in paper, paints and textile industries

4. Sodium Bicarbonate or Baking Soda (NaHCO3) Preparation

It is obtained as an intermediate product in Solvay process.

Properties

Uses
1. It is used as a constituent of baking powder which is a mixture of sodium bicarbonate,
starch and potassium bitartrate or cream of tartar and in medicine to remove acidity of the
stomach (as antacid).
2. NaHCO3 is a mild antiseptic for skin infections.
3 It is used in fire extinguisher.
Alkaline Earth Metals [Group-ll]
Group-II elements are Be. Mg, Ca. Sr. Ba and Ra. which have two electrons in their valence
shell. These are commonly called alkaline earth metals because their oxides are alkaline in
nature and are found in earth’s crust.

Mg is present in chlorophyll and Ca is present in bones as calcium phosphate.

General Characteristics of Alkaline Earth Metals

(i) Electronic configuration [noble gas] ns2

(ii) Atomic radii and ionic radii The atomic radii and ionic radii of these elements are quite
large but smaller than those of the corresponding alkali metals. due to increased nuclear
charge of these elements. The atomic as well as ionic radii go on increasing down the group
due to the gradual addition of extra energy level.
(iii) Density These are much denser than alkali metaIs because of their smaller size and
greater nuclear charge and mass. The density. however. first decreases from Be to Ca and
then steadily increases from Ca to Ra due to difference in type of crystal structure.
(iv) Melting and boiling points These metals have higher melting and boiling points than
those of alkali metals because of greater number of bonding electrons.
The melting and boiling points decrease down the group with the exception of magnesium,
(v) Metallic properties These are silvery white metals. soft in nature but harder than alkali
metals due to stronger metallic bonding.
(vi) Ionization enthalpy The first ionisation enthalpy of alkaline earth metals are higher than
those of the corresponding alkali metals due to smaller size and ns2 configuration.

The second ionisation enthalpy values are higher than their first ionisation enthalpy values
but much lower than the second ionisation enthalpy values of alkali metals.

On moving down the group. due to increase in atomic size, the magnitude of ionisation
enthalpy decreases.

(vii) Electropositive character These are strong electropositive elements due to their large
size and comparatively low ionisation enthalpy.
On moving down the group, the electropositive character increases due to increase in atomic
radii and decrease in ionisation enthalpy.

(viii) Oxidation state Alkaline earth metals uniformly show an oxidation state of +2.
In the solid state, the dipositive ions (M2+) form strong lattices due to their small size and
high charge (i.e., high lattice enthalpy).
[In the aqueous solution, the M2+ cations are strongly hydrated due to their small size and
high charge. The hydration energy released by the M2+ cation is very high]
(ix) Flame colouration Alkaline earth metals salts impart characteristic colours to the flame.
As we move down the group from Ca to Ba, the ionisation enthalpy decreases, hence the
energy or the frequency of the emitted light increases. Thus,

Be and Mg because of their high ionisation energies, do not impart any characteristic colour
to the flame.

(x) Crystal lattice Be and Mg crystallise in hcp, Ca and Sr in ccp and Ba in bee lattice.

Chemical Properties of Alkaline Earth Metals

Alkaline earth elements are quite reactive due to their low ionisation energies but less
reactive than alkali metals. Reactivity of the group.2
elements increases on moving down the group because their ionisation enthalpy decreases.

(i) Reaction with water Group-2 elements are less reactive with water as compared to alkali
metals.
M + 2H2O → M(OH)2 + H2 (where, M = Mg, Ca, Sr or Ba)
Be does not react even with boiling water and Ba react vigorously even with cold water.
Thus. increasing order of reactivity with water is

Mg < Ca < Sr < Ba

A suspension of Mg(OH)2 in water is called milk of magnesia.

Ca(OH)2 solution (lime water) and Ba(OH)2 solution (baryta are used for the detection of CO2,
(ii) Reaction with oxygen The affinity towards oxygen increases down the group. Thus. Be.
Mg and Ca when heated with O2 form monoxides while Sr. Ba and Ra form peroxides.

(iii) Reaction with acids Alkaline earth metals except Be, displace H2 from acids.

Reactivity increases down the group from Mg to Ba. Only Mg displaces H2 from a very dilute
HNO3.
(iv) Reaction with hydrogen Except Be, all other elements of group-2 combine with
hydrogen on heating to form hydride (MH2).
M + H2 → MH2
BeH2 and MgH2 are covalent and polymeric whereas the hydrides of Ca, Sr and Ba are ionic
in nature.
(v) Reaction with halogens All the elements of group-2 combine with halogens at high
temperature, forming their corresponding halides (MX2).

Beryllium halides (BeF2, BeCI2, etc) are covalent, hygroscopic and fume in air due to
hydrolysis, BeC12 exists as a dimer, The halides of other alkaline earth metals are fairly ionic
and this character increases as the size of the metal increases.
The halides are soluble in water and their solubility decreases in the order

MgX2 > CaX2 > SrX2 > BaX2

(vi) Reaction with nitrogen These metals react with nitrogen to form nitrides of the types
M3N2which are hydrolysed with water to evolve NH3.
3M + N2 → M3N2
M3N2 + 6H2O → 3M(OH)2 + 2NH3
(vii) Reaction with carbon These metals when heated with carbon, form their respective
carbides of the general formula MC2 (except Be).

All these carbides are ionic in nature and react with H2O to form acetylene (except Be2C
which gives methane).
CaC2 + 2H2 → Ca(OH)2 + HC = CH
(viii) Reducing character All the alkaline earth metals are strong reducing agents because of
their lower electrode potentials but these are weaker than the corresponding alkali metals.
As we move down the group from Be to Ra, the reducing character increases due to decrease
in ionisation enthalpy.

(ix) Solubility in liquid ammonia Like Alkali Metals, these metals also dissolve in liquid
ammonia by giving coloured solutions.
M +(x+ y)NH3 [M(NH3)x]2+ + 2[e(NH3)y]–
The tendency to form ammoniates decreases with increase in size of the metal atom (i.e., on
moving down the group).

(x) Complex formation It is favoured in case of alkaline earth metals because of their small
sizes as compared to the alkali metals. Both Mg2+ and Ca2+ form six coordinate complexes
with EDTA (ethylenediamminetetracetic acid) which are used to determine the hardness of
water.
(xi) Basic strength of oxides and hydroxides BeO and Be(OH)2 are amphoteric while the
oxides and hydroxides of other alkaline earth metals are basic. The basic strength, however,
increases from Be to Ba.
The basic character of hydroxides of group – 2 elements is lesser than those of group-l
hydroxides because of the larger size of later than former group.

(xii) Thermal stability and nature of bicarbonates and carbonates Bicarbonates of these
metals do not exist in solid state but are known in solution only. When these solutions are
heated, these get decomposed to evolve CO2.
 The carbonates of alkaline earth metals can be regarded as salts of weak carbonic acid
(H2CO3) and metal hydroxide, M(OH)2. The carbonates decompose on heating forming metal
oxide and CO2.

Anomalous Behaviour of Beryllium

Beryllium, differs from the rest of the members of its group due to the following reasons

1. Beryllium has a small atomic and ionic size.

2. It has no vacant d-orbitals.
3. It has a high charge density.
The points of difference are :

(i) Hardness Beryllium is denser and harder than other members of the family.
(ii) Melting point Beryllium has high melting point i.e., 1551 K while that of magnesium is
924 K
(iii) Ionisation potential It has higher ionisation potential as compared to the rest of the
members of this group.
(iv) Reaction with acids Due to lower oxidation potential of Be, it does not liberate
hydrogen from acids readily.
(v) Reaction with water Beryllium does not react with water even at higher temperature
while other members of the family liberate hydrogen by reacting with water at room
temperature.
(vi) Amphoteric in character Oxide (BeO) and hydroxide [Be(OH)2] of beryllium are
amphoteric in character and dissolve in acids to form salt and beryUate in alkali.
(vii) Formation of carbides Beryllium when heated with carbon form Be2C which on
reaction with water gives methane. While other members of the group form ionic carbide
MC2 (acetylide) which on reaction with water evolve acetylene.

Diagonal Relationship Between Be and AI

The main identical physical and chemical properties of Be with aluminium are given below

(i) Action of air Both the metals are stable in air.

(ii) Action with water Be and Al do not decompose water even at 373 K It is due to their less
electropositive character.
(iii) Electropositive character Beryllium like aluminium is less electropositive due to their
small ionic radii.
(iv) Complex formation Beryllium and aluminium form a number of complexes. Both form
fluoro complex anions like BeF2-4 and AlF3-6 in solution.
(v) Reaction with alkali Beryllium and aluminium react with sodium hydroxide liberating
hydrogen.
 (vi) Passive nature Both these metals are rendered passive on reaction with concentrated
nitric acid due to the formation of oxide layer on their surfaces.
(vii) Amphoteric character of oxides Oxides of both Be and Al are amphoteric in nature.
So. they dissolve.both in acids as well as in alkalies.

Application of Alkaline Earth Metals and their Compounds

1. Beryllium (Be) is used in corrosion resistant alloys.
2. Alloy of Mg with aluminium is used as structural material because of its high strength. low
density and ease in machining.
3. Strontium carbonate is used for the manufacture of glass for colour TV picture tubes.
4. Hydrated calcium chloride, CaCI2 . 6H2O is widely used for melting ice on roads, particularly
in very cold countries, because a 30% eutectic mixture of CaCl2 / H2O freezes at -55°C as
compared with NaCI / H2O at -18°C.
5. Barium sulphate being insoluble in water and opaque to X-rays is used under the name
barium meal to scan the X-ray of the human digestive system.
6. Magnesium is present in chlorophyll, a green pigment in plant, essential for photosynthesis.
7. Anhydrous CaCl2 because of its hygroscopic nature is a good drying agent but it cannot be
used to dry alcohols/ammonia/amines.
8. Magnesium perchlorate Mg(CIO4)2 is used as a drying agent under the name anhydrone.
Note Kidney stones generally consist of calcium oxalate. CaC2O4 . H2O which dissolves in
dilute strong acids but remains insoluble in bases.

Compounds of Calcium
1. Calcium Oxide or Quick Lime or Lime [CaO] Preparation
By the thermal decomposition of calcium carbonate.

Properties
1. It is a basic oxide.
2. Its aqueous suspension is known as slaked lime

3. On heating with ammonium salts, it gives ammonia.

4. It reacts with carbon to form calcium carbide

5. It is used as basic flux, for removing hardness of water, for preparing mortar (CaO + sand
+ water).

2. Calcium Hydroxide or Slaked Lime or Lime Water [Ca(OH)2]

Preparation
By dissolving quicklime in water.

CaO + H2O Ca(OH)2;

ΔH = – 63 kj

Properties
1. Its suspension in water is known as milk of lime.

2. It gives CaCO3 (milky) and then Ca(HCO3)2 with CO2,

3. It reacts with Cl2 to give bleaching powder, CaOCI2

Ca(0H)2 + Cl2 → CaOCI2 + H2O

3. Calcium Carbonate or Limestone or Marble or Chalk [CaCO3]

Preparation
By passing CO2 through lime water.
Ca(0H)2 + CO2 → CaCO3 ↓ + H2O
Properties
It is insoluble in H2O but dissolves in the presence of CO2, due to the formation of calcium
bicarbonate.

4. Gypsum, Calcium Sulphate Dihydrate (CaSO4 * 2H2O)

It is also known as alabaster.

On heating at 390 K, it gives plaster of Paris.

It is added to cement to slow down its rate of setting.

5. Plaster of Paris or Calcium Sulphate Hemihydrate (CaSO4 * 1 / 2 H2O)

When it is mixed with water, it forms first a plastic mass which sets into a solid mass with
slight expansion due to dehydration and its reconversion into gypsum. It is obtained when
gypsum is heated at 393 K.

CaSO4 * 2H2O → CaSO4 * 1 / 2 H2O + 3 / 2 H2O

Above 393 K no water of crystallization is left and anhydrous calcium sulphate is obtained. It
is known as dead burnt plaster.
6. Bleaching Powder (CaOCI2)
It is also called calcium chloro hypochlorite or chloride of lime.

Preparation
Ca(OH)2 + CI2 → CaOCI2 + H2O
Properties
1. Its aqueous solution gives Ca2+, CI– and OCl– ions.
2. With limited quantity of dil H2SO4 it gives nascent oxygen which is responsible for its
oxidising and bleaching action.
2CaOCI2 + H2SO4 → CaC12 + CaSO4 + 2HCIO
HCIO HCI + [O]

3. With excess of dil H2SO4 (or CO2) it forms C12, which is known as available chlorine.
CaOC12 + H2SO4 → CaSO4 + H2O + Cl2
CaOC12 + CO2 → CaCO3 + C12
The average percentage of available chlorine is 35-40%. Theoretically it should be 49~o.
which diminishes on keeping the powder due to following change

6CaOC12 → 5CaCl2 + Ca(CIO3)2

Uses It is used for bleaching, as disinfectant and germicide in sterlisation of water. for
making wool unshrinkable and in the manufacture of chloroform.

7. Cement
Cement is an important building material. It is a product obtained by combining materials
such as limestone (provides lime and clay provides alumina and silica, Si02 along with the
oxides of iron and magnesium.) The average composition of portland cement is

CaO, 50-60%; SiO2, 20-25%; Al2O3, 5-10%; MgO, 2-3%; Fe2O3, 1-2% and SO3, 1-2%.
A mixture of lime (CaO) and sand in the ratio 1 : 3 with enough water to make a thick paste
is called mortar.

By ash, a waste product of steel industry. has properties similar to cement and can be added
to cement to reduce its cost without affecting its quality.