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15

s-Block Elements

General Introduction of s-Block Elements


The components in the long form of the periodic table have been partitioned into four blocks in
particular s, p, d and f- blocks. The elements of Group 1 (I A) and 2 (II A) have their last electron in
s-orbital thus, they are called s-block elements.

Group 1 Elements : Alkali Metals


The Group 1 elements comprising Li, Na, K, Rb, Cs and Fr are commonly called alkali metals.
Francium is radioactive and has a very short life (half-life of 21 min). These are known as alkali metals
because their water soluble hydroxides are strongly alkaline. Sodium and potassium are abundant
and lithium, rubidium and caesium have much lower abundance.

Electronic Configuration of Alkali Metals


The general electronic configuration of alkali metals is [noble gas] ns1 (n = 2 to 7) .

Group 2 Elements : Alkaline Earth Metals


Group 2 elements are basically called alkaline earth metals as their oxides and hydroxides are
alkaline in nature and these metal oxides are found in the earth’s crust. Calcium and magnesium
rank fifth and sixth in abundance respectively in the earth’s crust. Strontium and barium have
much lower abundances. Beryllium is rare and radium is the rarest of all comprising only 10-10 per
cent of igneous rocks.

Electronic Configuration of Alkaline Earth Metals


The general electronic configuration of alkaline earth metals is [noble gas] ns 2 (n = 2 to 7).
s-BLOCK ELEMENTS 539
The high conductivity and paramagnetic properties
Chemical Properties of s-Block Elements
along with blue colour is attributed to the presence of
(i) Reaction with oxygen (air) Except Li, all alkali metals these ammoniated electron as well as ammoniated
are tarnish in air due to oxide formation at their cation.
surface and hence, they are stored in kerosene or
Alkaline earth metals are also soluble in liquid
paraffin oil.
ammonia and give bright blue solutions. When these
1
2 Li + O2 ¾® Li 2O (Oxide) metal-ammonia solutions are evaporated,
2 hexammoniates [ M(NH3 )6] are formed. The
2Na + O2 ¾® Na 2O2 (Peroxide) hexammoniates slowly decompose to give amides.
M + O2 ¾® MO2 (Superoxide) ( M = K, Rb, Cs) [ M (NH3 )6 ] ¾® [ M (NH3 )2 ] + 4 NH3 + H 2
Superoxide O-2 ion is stable only in the presence of Concentrated solutions of the metals in ammonia
large cations such as K, Rb, Cs. impart bronze colour due to the formation of metal
clusters and it is diamagnetic.
Alkaline earth metals get slowly oxidised on exposure to
air forming oxides. These oxides are basic in nature. Basic (vi) Reaction with nitrogen and carbon
nature of oxides increases on moving down the group. 6 H 2O
3 Ca + N 2 ¾® Ca3 N 2 ¾¾® 3Ca(OH)2 + 2NH3 ­
NOTE Oxide of Be, i.e. BeO is amphoteric in nature due to smaller
size of Be 2 + ion. (vii) Reactivity and electrode potential Reducing character
(ii) Basic strength of hydroxides Hydroxides of alkali or reactivity of alkali metals increases from Li to Cs, i.e.
metals are strongly basic and their basic strength Li < Na < K < Rb < Cs.
increases down the group. And hydroxides of alkaline Reducing character or reactivity of alkaline earth
earth metals are less basic than alkali metals of the metals increases from Be to Ba, i.e.
corresponding period. Be < Mg < Ca < Sr < Ba
CsOH > RbOH > KOH > NaOH > LiOH Mg(ClO4 )2 is used as drying agent under the name
(iii) Reaction with hydrogen Alkali metals react with anhydrone, it is a strong oxidising agent. So, it is not
hydrogen and form ionic hydrides, M + H - . used with organic material.
2 M + H 2 ¾® 2 MH (where, M = Li, Na, K etc)
Alkali metal hydrides attacked by water to give Anomalous Properties of Lithium
hydrogen. Lithium due to its
MH + H 2O ¾® MOH + H 2 ● exceptionally small size (like Mg) and

Except Be, all alkaline earth metals react with ● high polarising power (i.e. charge/radius ratio) (like Mg)
hydrogen to form ionic hydrides of MH 2 type. The
exhibits some properties which are different from those
hydride of Mg bears some covalent character in it due
of the other members of group 1 but similar to that of
to its smaller size.
magnesium (present diagonally in the following group,
(iv) Reaction with halogens Alkali metals combine readily i.e. group 2 ). The property of showing similarity in
with halogens to form halides. properties with the element present diagonally opposite
é where, M = Li, Na, K, Rb, Csù in the periodic table is called diagonal relationship.
2 M + X 2 ¾® 2 MX ê ú These properties are :
ë X = F, Cl, Br or I û
(a) Alkali metals do not react with nitrogen except Li.
Alkaline earth metals combine with halogens at
elevated temperature forming halides, MX 2. Beryllium Heat
6Li + N 2 ¾¾® 2Li3 N
halide is covalent while others are ionic. The solubility Lithium nitride
of halides (except fluoride) decreases on moving top to (Li metal is used as scavenger in metallurgy to
bottom in the group (Lower solubility of LiF in water is remove O2 and N 2 gases.)
due to its higher lattice energy).
3Mg + N 2 ¾¾® Mg3 N 2
(v) Solubility in liquid ammonia All alkali metals are Magnesium nitride
soluble in liquid ammonia. Dilute alkali (b) Alkali metal carbonates, nitrates and hydroxides do
metals-ammonia solution is of blue colour. These not decompose on heating into their oxides except
solutions are strong reducing agents due to the lithium.
presence of free electrons. Heat
Na 2CO3 ¾¾® No reaction
M + ( x + y ) NH3 ¾® [ M (NH3 )x ]+ +[e(NH3 ) y ]-
Ammoniated Ammoniated Heat
cation electron Li 2CO3 ¾¾® Li 2O + CO2
540 SELF STUDY GUIDE BITSAT

Heat
MgCO3 ¾¾® MgO + CO2 Properties
Heat O2 H2O CO2
4LiNO3 ¾¾® 2Li 2O + 4NO2 + O2 Na2O NaOH 2Na2CO3 + 2H2
Heat
2Mg (NO3 )2 ¾¾® 2MgO + 4NO2 + O2 H2O
NaOH
2NaNO3 ¾¾® 2NaNO2 + O2
HCl
(c) MgCl 2 and LiCl are deliquescent and crystallise as NaCl
their hydrates, LiCl × 2H 2O and MgCl 2 × 2H 2O. S Na2S
Na SiO2
Anomalous behaviour of Beryllium Si + 2Na2O
Al2O3
Beryllium due to its exceptionally small size (like Al) and Al + Na2O
high polarising power (like Al) shows similarities with
ROH
aluminium in its properties and this relationship is called NaOR
diagonal relationship. These properties are : NH3
NaNH2
● BeO like Al O , is amphoteric and covalent while oxides of
2 3
other alkaline earth metals are ionic and basic in nature.
Uses
● Both BeCl
2 and AlCl3 are soluble in organic solvents
because of covalent nature and both have a bridged (a) For extraction C, Be, Mg and Si.
polymeric structure. (b) As lab reagent.
● Beryllium hydroxide dissolves in excess of alkali to give a (c) In high temperature thermometers.
beryllate ion, [Be(OH)4 ]2- just as aluminium hydroxide
gives aluminate ion,[Al(OH)4 ]- . Compounds of Sodium
● Beryllium and aluminium ions have strong tendency to
Sodium Carbonate
form complexes, BeF 24- , AlF 36 - .
(Washing Soda, Na 2CO 3 ×10H2O)
● Carbides of Be are covalent and react with water to
Sodium carbonate is generally prepared by Solvay process.
produce methane gas whereas carbides of other
members are ionic and produce acetylene with water. 2NH3 + H 2O + CO2 ¾¾® (NH 4 )2 CO3
(NH 4 )2 CO3 + H 2O + CO2 ¾¾® 2NH 4HCO3
NH 4HCO3 + NaCl ¾¾® NH 4Cl + NaHCO3
Sodium (Na) Sodium hydrogen carbonate crystals separate out. These
Compounds found in nature are heated to obtain sodium carbonate.
NaCl, NaNO3, , Na 2SO4 ×10H 2O (Glauber’s salt) 150 ° C
2NaHCO3 ¾¾® Na 2CO3 + CO2 + H 2O
Na 2B 4O7 × 10H 2O (Borax)
In this process, NH3 is recovered when the solution
Extraction containing NH 4Cl is treated with Ca(OH)2 .
1. Castner’s Process
Uses of Na2 CO3
2NaOH r 2Na+ + 2OH –
(i) In laundries and in softening of water as washing soda.
At cathode 2Na+ + 2e – ¾® 2Na
(ii) In the manufacturing of glass, sodium silicate, paper,
At anode 4OH - ¾® 2H 2O + O2 + 4e – borax, soap powders, caustic soda, etc.
Oxygen and H 2O are produced during electrolysis. (iii) In textile and petroleum refining.
2. Down’s Process (iv) For the preparation of various carbonates of metals.
Cathode Fe Sodium Hydroxide (Caustic Soda, NaOH)
Anode Graphite Sodium hydroxide is prepared commercially by the
NaCl ¾® Na + + Cl – electrolysis of sodium chloride in Castner-Kellner cell
At cathode Na + + e - ¾® Na (or mercury cathode cell).
Hg
At anode
300 °C
2Cl – ¾¾® Cl 2 + 2e – At cathode Na + + e - ¾¾® Na -Hg (Amalgam)
Fusion temperature is reduced to 600°C by adding CaCl 2 , 1
At anode Cl - ¾¾® Cl 2 + e - (By-product)
KE. 2
s-BLOCK ELEMENTS 541
The amalgam is treated with water to give sodium Compounds of Magnesium
hydroxide and hydrogen gas.
2Na-Hg + 2H 2O ¾¾® 2NaOH + 2Hg + H 2 Magnesium Chloride (MgCl 2 × 6H 2O)
● Sodium hydroxide is white, translucent solid and Preparation
deliquescent. It is called caustic soda because it breaks MgCO3 + 2HCl ¾® MgCl 2 + CO2 + H 2O
down proteins of skin to a pasty mass.
MgO + 2HCl ¾® MgCl 2 (hydrated)
● On exposure to atmosphere, it absorbs moisture and
D
CO2 . 2NaOH + CO2 ¾® Na 2CO3 + H 2O MgO + C + Cl 2 ¾® MgCl 2 + CO2
● It reacts with metals like Zn, Al, Sn and Pb and evolve H 2 Burning
gas. Mg + Cl 2 ¾¾® MgCl 2 (anhydrous)
e.g. Zn + NaOH ¾® Na 2ZnO2 + H 2
Properties
● It also reacts with metallic salts to form hydroxides. It is
used in soap manufacturing, purification of bauxite, It is a colourless, crystalline, deliquescent and highly
manufacturing of rayon, etc. soluble in water.
D
Sodium Chloride 2(MgCl 2 × 6H 2O) ¾® MgO × MgCl 2 + 2HCl + 11 H 2O
(Common salt or rock salt, NaCl) Uses
The three major sources of NaCl are It is used in the preparation of metallic magnesium and in
(i) Sea water (3% NaCl) making Sorel cement.
(ii) Water of inland lake Magnesium Sulphate (MgSO4 × 7H 2O)
(iii) Salt mines Preparation
● It is a white crystalline solid, soluble in water.
MgCO3 + H 2SO4 ¾® MgSO4 + H 2O + CO2
● Pure NaCl is not hygroscopic. It shows hygroscopic Magnesite
nature due to the presence of chlorides of Ca and Mg MgCO3 × CaCO3 + 2H 2SO4 ¾®
as an impurity. Dolomite
● It is used as the starting material for the preparation
MgSO4 + CaSO4 ­ + 2H 2O + 2CO2
of NaOH, Na 2CO3 , NaHCO3 , etc. Commercial method
● It is used as a preservative for meat, fish, etc. It is
MgSO4 × H 2O + 6H 2O ¾® MgSO4 × 7H 2O
also used as a salting out of soap and in making (Epsom salt)
Properties
freezing mixtures.
It is a colourless crystalline solid, soluble in water.
Sodium Hydrogen Carbonate °C
MgSO4 × 7H 2O ¾150
¾¾ ® MgSO4 × H 2O
(Baking Soda, NaHCO 3 )
°C
It is prepared as an intermediate product in the Solvay ¾200
¾¾ ® MgSO4 + H 2O
ammonia soda process. D
2MgSO4 ¾
¾® 2MgO + 2SO2 + O2
NH3 + H 2O + CO2 + NaCl ¾® NaHCO3 ¯ + NH 4Cl
2MgSO4 + C ¾® 2MgO + 2SO2 + CO2
● It is a white crystalline solid, sparingly soluble in water.
● Its aqueous solution is alkaline in nature due to Uses
hydrolysis. It is used in
NaHCO3 + H 2O r NaOH + H 2CO3 1. Medicines (as purgative).
Heat 2. Dyeing and tanning processes.
2NaHCO3 ¾¾® Na 2CO3 + H 2O + CO2
3. Ceramic, cement, match industries.
● It is used as a medicine to neutralise acidity in stomach.
4. Treatment of textile fibres to make them non-
● It is used as a constituent of baking powder and in fire
inflammable.
extinguisher.
542 SELF STUDY GUIDE BITSAT

Compounds of Calcium Uses


It is used
Quicklime (CaO)
1. In the preparation of plaster of Paris.
Preparation 2. In the manufacturing of cement, H 2SO4 , (NH 4 )2 SO4 , etc.
D
CaCO3 ¾
¾® CaO + CO2 3. For glazing paper.
800-1000 °C

Properties Plaster of Paris (2CaSO4 × H2O)


It is white amorphous powder with melting point 2600°C. Preparation
Action of water
D
CaO + H 2O ¾® Ca(OH)2 2(CaSO4 × 2H 2O) ¾® 2CaSO4 × H 2O + 3H 2O
Gypsum Plaster of Paris
Basic nature
CaO + 2HCl ¾® CaCl 2 + H 2O Properties
CaO + CO2 ¾® CaCO3 It is a white powder, which sets to a hard mass when its
CaO + SiO2 ¾® CaSiO3 paste (with water) is allowed to stand.
2000 °C Plaster of Paris ¾® Gypsum ¾® Gypsum
CaO + 3C ¾¾® CaC 2 + CO2 (Orthorhombic) (Monoclinic)

CaO + 2NH 4Cl ¾® CaCl 2 + 2NH3 + H 2O Uses


Uses It is used
It is very useful as drying agent, in bleaching powder 1. in making chalks, casts in dentistry, etc.
production (as used for the preparation of slaked lime and 2. in surgery for setting broken/dislocated bones.
as a constituent of mortar).
3. in making casts for statues, toys etc.
Calcium Carbonate (CaCO3 ) Calcium Hydroxide or Slaked Lime [Ca(OH)2 ]
Preparation Preparation
(a) Ca(OH)2 + CO2 ¾® CaCO3 + H 2O It is prepared by adding water to quicklime as
(b) CaCl 2 + Na 2CO3 ¾® CaCO3 + 2NaCl 2CaO + 2H 2O ¾® Ca(OH)2 + 2H 2 ­
Properties Properties
CaCO3 is a white powder, insoluble in water but dissolves in 1. It is a white powder, sparingly soluble in water and the
the presence of CO2 . aqueous solution is called lime water while the
Excess
CO 2 aqueous suspension is called milk of lime. CO2 has the
Ca 2+ (OH- )2 + CO2 ¾® CaCO3 + H 2O ¾¾® Ca 2 + (HCO3- )2 ability to turn lime water milky as
(Insoluble ) (Soluble)
White ppt Ca(OH)2 + CO2 ¾® CaCO3 + H 2O
(Milky ppt)
Uses
This milkiness disappears with excess of CO2 as
It is used soluble calcium hydrogen carbonate is formed.
1. in manufacturing paints, quicklime, etc. CaCO3 + H 2O + CO2 ¾® Ca(HCO3 )2
2. in toothpastes and cosmetics. Soluble
3. as a building material. 2. Being basic in nature, it reacts with acids and acidic
gases forming their salts.
Calcium Sulphate (Gypsum) (CaSO4 × 2H2O) 3. On reaction with chlorine, it forms hypochlorite,
Preparation a constituent of bleaching powder, as
CaCl 2 + H 2SO4 ¾® CaSO4 + 2HCl 2Ca(OH)2 + 2Cl 2 ¾® CaCl 2 + Ca(OCl)2 + 2H 2O
CaCl 2 + Na 2SO4 ¾® CaSO4 + 2NaCl Uses
Properties Slaked lime is used in mortar production, lime water
● It is a white crystalline solid, sparingly soluble in water production, disinfectant, bleaching powder production, etc.
but dissolves in dilute acids. Portland Cement
Strong
heating It was discovered by an English Mason, Joseph Aspdin
● 2CaSO4 ¾¾® 2CaO + 2SO2 + O2 (1824). When the mixture of CaCO3 , clay and water is heated
● CaSO4 + 4C ¾® CaS + 4CO strongly and allowed to stand, it hardens to a stone like mass.
s-BLOCK ELEMENTS 543
It resembles with Portland rock (a famous building stone of Setting of Cement Paste of water and cement gets hard on
England) and so, it is named as Portland cement. It is a keeping it for some time. This is called setting of cement.
mixture of aluminates and silicates of Ca with small amount Mechanism of setting of cement is as follows:
of gypsum. Hydration
3CaO × Al 2O3 + 6H 2O ¾¾¾® 3CaO × Al 2O3 × 6H 2O
Chemical Composition Tricalcium aluminate (Colloidal gel)

CaO = 50-60%, SiO2 = 20-25%, Hydrolysis


3CaO × SiO2 + H 2O ¾¾¾¾® Ca(OH)2 + 2CaO × SiO2
Al 2O3 = 5 -10%, MgO = 2 - 3%, (ppt) Dicalcium silicate
Hydration
Fe 2O3 = 1-2%, SO3 = 1-2% 2CaO × SiO2 + xH 2O ¾¾¾® 2CaO × SiO2 × xH 2O
(Colloidal gel)
Formation of Constituents of Cement
Partial
5CaO + 5SiO2 ¾® 2CaO × SiO2 + 3CaO × SiO2 3CaO × Al 2O3 + 6H 2O ¾¾¾¾® 3Ca(OH)2 + 2Al (OH)3
hydrolysis (ppt)
Dicalcium silicate Tricalcium silicate (ppt)

3CaO + Al 2O3 ¾® 3CaO × Al 2O3 4CaO × Al 2O3 × Fe 2O3 + 6H 2 O ¾®


Tricalcium aluminate Tetracalcium aluminoferrite
4CaO + Al 2O3 + Fe 2O3 ¾® 4CaO × Al 2O3 × Fe 2O3 3CaO × Al 2O3 × 6H 2O + CaO × Fe 2O3
Dialuminium tetracalcium (Colloidal gel)
iron (III) oxide or celite

Practice Exercise
1. Which of the following ions forms a hydroxide which is 8. Which of the following pairs cannot exist together in
highly soluble in water? solution?
a. Ni2+ b. K + c. Zn2+ d. Al3+ a. Na 2CO3 and NaHCO3 b. NaHCO3 and NaOH
2. Solubility of alkaline earth metal sulphates decreases c. Na 2CO3 and NaOH d. NaOH and NaCl
down the group 2 because 9. Sodium peroxide, a yellow solid, when exposed to air
a. they become more ionic becomes white due to the formation of
b. lattice energy of sulphates does not vary significantly a. H2O2 b. Na 2O
c. hydration energy decreases rapidly from Be2+ to Ba 2+ c. Na 2O and O3 d. NaOH and Na 2CO3
d. lattice energy plays more predominant role than
hydration energy 10. The products obtained on heating LiNO 3 will be
3. Which of the following compounds has the lowest a. LiNO2 + O2 b. Li2O + NO2 + O2
anion to cation size ratio? c. Li3N + O2 d. Li2O + OH + O2
a. LiF b. NaF c. CsI d. CsF 11. Identify the correct formula for halides of alkaline earth
4. Which is the most basic among the following? metals.
a. Na 2O b. BaO c. As2O3 d. Al2O3 a. BaCl2 × 6H2O b. CaCl2 × 6H2O
5. The stability of the following alkali metal chlorides c. BaCl2 × 4H2O d. SrCl2 × 4H2O
follows the order
12. LiF is almost insoluble in water whereas LiCl is soluble
a. LiCl > KCl > NaCl > CsCl b. CsCl > KCl > NaCl > LiCl
c. NaCl > KCl > LiCl > CsCl d. KCl > CsCl > NaCl > LiCl not only in water but also in acetone. This is because of
a. high hydration enthalpy of Li+
6. When CO is passed over solid NaOH heated to b. low hydration enthalpy of Li+
200°C, it forms c. more ionic character in LiCl
a. Na 2CO3 b. H2CO3 c. HCOONa d. All of these
d. None of the above
7. Which of the following does not illustrate the
anomalous properties of lithium? 13. Consider the following statements.
a. Li is much softer than the other group 1 metals I. BeO is insoluble but BeSO4 is soluble in water.
b. The melting point and boiling point of Li are II. BaO is insoluble but BaSO4 is soluble in water.
comparatively high III. LiI is more soluble than KI in ethanol.
c. Li forms a nitride Li3N unlike group 1 metals The true statements are
d. The ion of Li and its compounds are more heavily a. I and II b. I and III c. II and III d. I, II and III
hydrated than those of rest of the group 1 elements
14. Which of the following statements is/are incorrect
regarding the s-block elements?

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