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s-Block Elements

Characteristic Group 1 (Alkali metals) Group 2 (Alkaline earth metals)


(A) General
Introduction
1. Elements 3
Li, 11Na, 19K, 37Rb, 55Cs and 87Fr Be, 12Mg, 20Ca, 38Sr, 56Ba, 88Ra
4
present
2. Name They are known as alkali metals Oxides of calcium, barium and
because their oxides and strontium were known before these
hydroxides when treated with metals were discovered and since
water form alkaline solutions these oxides were alkaline and
found in the earth, the metals were
named as alkaline earth metals.
Now-a-days this term is extended to
all elements of group 2 or II-A
3. Electronic [Noble gas]ns1 [Noble gas] ns2
configuration
(B) Physical
Properties
1. Atomic radii Largest in their respective Large but smaller than the
periods. Down the group, the corresponding alkali metals. Down
atomic radius increases . the group, the atomic radius
increases .
2. Ionic Radii Ions are formed by the loss of one Ions are formed by the loss of two
electron Hence ionic radius is electrons. The trend remains the
smaller than atomic radius but same as above i.e. increases down
trend remains the same as above the group.
i.e. increases down the group.
3. Ionization Lowest in the their respective They have fairly low ionization
energy periods. Down the group it energies but greater than the
decreases corresponding elements of Group 1.
These decrease down the group.
4. Oxidation state +1 because they lose one electron +2 because they lose two electrons
to acquire stable noble gas to acquire stable noble gas
configuration. configuration.

5. Metallic These are typical soft metals and These are also metals. With respect
character can be easily cut with a knife. to to alkali metals they are less
Because of low ionization metallic and less electropositive.
energies, they are highly Their metallic character increases
electropositve. The electropositve down the group.
character increases down the
group.

[1]
Characteristic Group 1 (Alkali metals) Group 2 (Alkaline earth metals)
6. Melting points and Their melting point and boiling Their melting point and boiling
Boiling points point are low and decrease point are higher than alkali metals
because of smaller size and more
down the group because of large
closely packed crystal lattice.
size and weak intermetallic There is no regular trend down the
bonds. group.
7. Nature of the They form ionic bonds. The Because of small size and high
bonds formed tendency to form ionic bond I.E., Be has a tendency to form
covalent compounds.Mg also
increases down the group.
shows some tendency for
covalency. All other elements
form ionic compounds.
8. Density Their densities are quite low due These are denser than alkali metals
to their large size. Li, Na and K because of smaller size. Density
decreases from Be to Ca and than
are lighter than water. The
increases from Sr to Ra.
densities increases from Li to Cs
although density of potassium is
lower than that of sodium.
9. Flame colouration These metals or thier salts These metals also impart
impart characteristic colour to characteristic folour to the flame
which deepens from Ca to Ra
the flame. The colour deepens
because of the same reasons.
from Li toCs because for the Ca Sr
same excitation energy, the Brick red Crimson
electrons jump to different Ba Ra
energy levels. Apple green Crimson
Li Na
Crimson red Golden Yellow
K Rb Cs
PaleViolet Violet Violet
(C) Chemical
Properties
1. Reducting These metals are strong These are weaker reducing agents
character reducing agents. with respect to alkali metals
Their reducing power increases because of greater ionization
energies. The reducing power
down the group, increases down the group because
Exception. Li is the strongest of decrease in ionization energy.
reducing agent although it has
highest I.E. in the group.
Characteristic Group 1 (Alkali metals) Group 2 (Alkaline earth
metals)
2. Reaction with Li on heating forms lithium Be, Mg and Ca form their oxides
oxygen monoxide (Li2O), sodium forms (BeO, MgO and CaO), Sr and Ba
mainly sodium peroxide (Na2O2); form peroxides (SrO2, BaO2).
K, Rb and Cs form superoxide This shows that the reactivity
(MO ). increases down the group.
2

3. Reaction with These metals and their oxides Be + H2O   No reaction


water . react with water and form their Mg + H2O   MgO + H2
hydroxides (steam)
2M + 2H2O   2MOH + H2 M +2H2O(cold)   M(OH)2+
M2O + H2O   2MOH H2
The reactivity of these metals with (Ca, Sr, Ba)
water increases down the group. (i) Basic character. They are
(i) Basic character. All the weaker bases than alkali metal
hydroxides are basic in nature. hydroxides. The basic character
The basic strength increases down increases down the group.
the group. Be(OH)2 is amkphoteric.
(ii) Solubility in water. All these (ii) Solubility in water. Less
are soluble in water. soluble. The solubility increases
(iii) Stability. Except LiOH, all down the group because lattice
energy decreases whereas
other hydroxides are thermally
hydration energy remains almost
stable unchanged.

2LiOH  Li2O  H 2O
4. Reaction with On heating with H2, all alkali Except Be, all other combine
hydrogen metals form ionic hydrides with H2 directly on heating to
 form the hydrides (MH2). BeH2 is
2M + H2   2M+ H–
obtained as follows:
Ease of formation of hydrides 2 BeCl + LiAlH   2BeH +
2 4 2
decreases from Li to Cs. Li LiCl + AlCl3.
combines with H 2 at approx
8000 C .
The stability of hydrides decreases
from LiH to CsH.
Ionic nature of hydrides increases
from LiH to CsH.
Ionic hydrides are decomposed by
water.
M  H   H 2 O  MOH(aq)  H 2 
Alkali metal hydrides are strong
reducing agents and their reducing
nature increases from LiH to CsH.
Some Additional Characteristics of Alkali Metals

1. Photoelectric effect. Except Li (which has highest ionization energy), all metals of this group exhibit in a liquid
photoelectric effect which increases down the group.
2. Solubility inliquid ammonia. All alkali metals dissolve in liquid ammonia and produce intense blue solution. This
blue solution conducts electricity and possesses strong reducing power. All these properties of this solution are
explained due to the presence of ammoniated (solvated) electrons.

 M   NH3  x  e   NH3  y
M   x  y  NH3 
 The dilute solution of alkali metals in liquid ammonia is paramagnetic in nature.
 The paramagnetic character of the above solution decreases with increasing concentation
 The reducing power of alkali metals is enhanced in ammonia solution.
 On standing the blue solution slowly liberates hydrogen in the presence of impurities or catalyst such as Fe.
2M  2NH3 (l )  2MNH2  H 2 
 Li forms imide with ammonia Li2NH, while other alkali metals form amides MNH2.
 Highly pure dilute solution of sodium in pure liquid ammonia does not evolve hydrogen gas.
 The blue colour of the solution is due to absorption of red frequencies by ammoniated electrons.
 With increase in concentration of alkali metal in ammonia, cluster formation of metal ions takes place and
finally its colour appears like metallic copper.
 The high electrical conductivity of the ammonia solution is due to ammoniated electrons and ammoniated
metal ions.
 The ammonia solutions are sometimes called expanded metals because of considerable expansion of total
volume.
3. Reaction with alcohol and acetylene. They liberate H2 gas e.g.

2Na  2C2H5OH 
 2C2 H5ONa  H 2
Sod.ethoxide

 NaC  CNa  H 2
2Na  CH  CH 
Disod. acetylide
4. Effect of air and moisture. They are converted into oxides, hydroxides and carbonates.
1
O2
2 H 2O CO 2
2M  M 2 O  2MOH  M 2 CO3  H 2 O
That is why they are ketp under kerosene oil.
5. Hydration of ions. Alkali metals are highly hydrated in aqueous solutions. Smaller the size, greater is the hydration.
Hence hydrated ionic radii are in the order : Li+ > Na+ > K+ > Rb+ > Cs+. Ionic mobilities are in the opposite order.
Some Additional Characteristics of Alkaline Earth Metals and their Compounds
1. Formation of complexes. Due to smaller size and higher charge, beryllium and magnesium have the tendency
to form complexes.
2. Carbonates. Preparation (i) By passing CO2 through metal hydroxide
M  OH  2  CO2 
 MCO3  H 2O
(white ppt)
(ii) By treating the salt such as CaCl2 with sodium or ammonium carbonate

CaCl2  aq   Na 2CO3  aq  
 CaCO3  s   2NaCl  aq 
Properties
(i) Solubility : Solubility of carbonates (from CaCO3 to BaCO3) decreases down the group due to decrease
hydration energy
(ii) Stability : They decompose on heating to give metal oxide and CO2. The temp. of decomposition increases
from Be to Ba. BeCO3 is unstable.

MCO3 
 MO  CO2
3. Sulphates. Preparation - They are obtained by action of H2SO4 on metals, metal oxides, metal hydroxides
and metal carbonates.

 MSO4  H 2
M  H2SO4   MSO 4  H 2 O
MO  H 2SO 4 

M  OH  2  H 2SO 4 
 MSO4  2H 2O MCO3  H 2SO4 
 MSO4  CO2  H2O
Properties.
(i)Solubility : Solubility of sulphates (From CaSO4 to BaSO4) decreases down the group due to decrease of
hydration energy.
(ii) Stability : They are thermally stable due to their high lattice energy.
4. Structure of BeCl2. In the solid phase; it has a polymeric structure.
Cl Cl
Be Be Be
Cl Cl
The bridge Cl atoms are linked to Be atoms by three centre two electron (3c – 2e) bonds.
In the vapour phase, it forms dimers which dissociate to form linear monomers at 1200 K.
Cl
Cl – Be Be – Cl CL  Be  Cl
Cl Monomer
Dimer
Anomalous Behaviour of Lithium and its Diagonal Relationship with Mangesium
Due to small size and high ionization energy, Li differs from the rest members of its own group and resembles
diagonally with Mg as
(i) Lithium like Mg is harder while other alkali metals are soft.
(ii) With oxygen, Li forms monoxide while others form peroxides or superoxides.
(iii) Melting and boiling points of both Li and Mg are high with respect to other alkali metals.
(iv) Li like Mg forms ionic nitrides while other alkali metals do not.

6Li  N 2 
 2Li3 N; 3Mg  N 2 
 Mg 3 N 2
(v) Nitrates of Li and Mg on heating decompose to give NO2 and O2 (both) while other alkali metal nitrates
giveO2.

4LiNO3 
 2Li 2 O  4NO 2  O 2

2Mg  NO3 2 
 2MgO  4NO2  O2

 2NaNO 2  O2
2NaNO3 
(vi) Hydroxides and carbonates of both Li and Mg decompose on heating while corresponding salts of other
alkali metals are stable.
 Li 2 O  H 2 O; Mg  OH  2 
2LiOH   MgO  H 2 O

Li2 CO3 
 Li 2O  CO 2 ; MgCO3 
 MgO  CO 2
(vii) LiOH like Mg(OH)2 is a weak base while hydroxides of other alkali metals are strong bases.
(viii) Because of covalent character, chlorides of both Li and Mg are soluble in organic solvents while those of
other alkalimetals are insoluble.
(ix) Hydroxides, carbonates and fluorides of both Li and Mg are sparingly soluble in water whereas corresponding
salts of other alkali metals are soluble.
Anomalous Behaviour of Beryllium and its Diagonal Relationship with Aluminium
Beryllium differs from the rest members of its own group and resembles diagonally with Al in the following
characteristics:
(i) In HNO3, both form protective layer of oxide whereas other alkaline earth metals do not.
(ii) Both dissolve in strong alkalies to form complexes [Be(OH)4]2–, [Al(OH)4]–
(iii) Oxides of both (BeO, Al2O3) are hard, high melting insoluble solids, amphoteric in nature whereas oxides of
other alkaline earth metals are basic.
(iv) BeCl2 is covalent with polymeric structure like aluminium chloride which has a dimeric structure, Al2Cl6.
The chlorides of other alkaline metals are ionic and monomeric.
(v) Carbides of both Be and Al react with water producing methane gas whereas carbides of other alkaline
earth metals give acetylene gas.
 2Be  OH 2  CH 4
Be2C  4H 2O 

 4Al  OH 3  3CH 4
Al 4 C3  12H 2 O 

IMPORTANT COMPOUNDS
1. Sodum Carbonate or Washing Soda (Na2CO3.10H2O) : It is manufactured by ammonia soda process or
Solvay’s process :
NH 3  H 2 O  CO 2  NH 4 HCO3
Ammonium bicarbonate

NaCl  NH 4 HCO3  NaHCO3  NH 4 Cl


Sodium bicarbonate


2NaHCO3   Na 2 CO3  H2 O  CO2

2NaHCO3   Na 2 CO3  H 2 O  CO2
CaCO3

CO2 NaCO
2 3 CaO

Heat
NaCl NaHCO3 + NHCl
4 NHCl
4

NH3
2NHCl
4 + Ca(OH) 2
CaCl 2
Physical Properties:
(i) Sodium carbonate is a white crystalline solid. It is known in several hydrated forms.
(ii) On heating, the monohydrate changes into the anhydrous form which does not decompose on further heating
even to redness. It is the amorphous powder and called soda ash. It melts at 852°C.
(iii) It is solulbe in water with evolution of considerable amount of heat.
Na 2 CO3  2H 2 O ƒ 2NaOH  H 2 CO3
Chemical Properties
(i) Action of acid :
Na 2 CO3  HCl  NaHCO3  NaCl

NaHCO3  HCl  NaCl  H 2 O  CO2


(ii) Action of CO2 :
Na 2 CO3  H 2 O  CO 2  2NaHCO3
(iii) Action of silica :

Na 2 CO3  SiO2  Na 2SiO3  CO2 


(iv) Action of Slaked lime :

Na 2 CO 3  Ca  OH 2  2NaOH  CaCO3

(v) Action of sulphur dioxide:


H2O
Na 2 CO3  SO2   Na 2SO3  CO2 
Uses: Sodium carbonate is used :
(i) In laundaries and in softening of water as washing soda
(ii) In manufacture of glass, sodium silicate, paper, borax, soap powders, caustic soda, etc.
(iii) in textile and petroleum refining.
(iv) for the preparation of various carbonates of metals.

2. Sodium Bicarbonate (Baking Soda), NaHCO3


It is obtained as the intermediate product in the Solvay ammonia soda process. Normal carbonate can be
changed to bicarbonate by passing carbon dioxide through its saturated solution.

Na 2 CO3  CO 2  H 2 O  2NaHCO3
sparingly so lub le
Properteis : It is white crystalline solid, sparingly soluble in water. The solution is alkaline in nature due to
hydrolysis.
NaHCO3  H 2 O ƒ NaOH  H 2 CO3
On heating, it loses carbon dioxide and water forming sodium carbonate.

2NaHCO3   Na 2 CO3  H 2 O  CO2
Uses:
(i) It is used as a medicine (sodabicarb) to neutralize the acidity in the stomach.
(ii) It is largely used for making baking powder. Baking powder is mixture of potassium hydrogen tartrate and
sodium bicarbonate.
(iii) It is used in making effervescent drinks.
(iv) It is used in fire extinguishers.
(v) It is used for production of carbon dioxide.
3. Calcium Sulphate
It is found in nature as anhydride (CaSO4) and gypsum (CaSO4.2H2O).
It can be prepared by reacting any calcium salt with either sulphuric acid or a soluble sulphate.
CaCl2  H 2SO 4  CaSO4  2HCl

CaCl2  Na 2SO 4  CaSO 4  2NaCl


Properties :
(i) It is a white crystalline solid. It is sparingly soluble in water and solubility decreases as temperature increases.
(ii) It dissolve in dilute acids. It also dissolves in ammonium sulphate due to the formation of double sulphate,
(NH4)2SO4.CaSO4.H2O.
(iii) Effect of Temperature : Gypsum when heated first changes from monoclinic form to orthohombic without
loss of water. At 120°C, it loses three-fourth of its water of crystallisation and forms hemihydrates, (2CaSO4.H2O)
which is commonly known as Plaster of Paris. At 200°C, it becomes anhydrous. The anhydrous form is known
as burnt plaster or dead plaster.

Heated 120°C
CaSO 4.2H 2O CaSO 4.2H 2O 2CaSO 4.H2O
Gypsum (Ortho rhombic) (Plaster of paris)
(Monoclinic)

Strongly 200°C
heated
O2+SO2+CaO CaSO 4
Anhydrous
(burnt plaster)

(iv) A suspension of gypsum when saturated with ammonia and carbon dioxide forms ammonium sulphate, a
nitrogenous fertilizer.

2NH3  CaSO4  CO2  H2 O   NH4 2 SO4  CaCO3

(v) When strongly heated with carbon, it forms calcium sulphide.


CaSO4  4C  CaS  4CO
Uses : It is used
(i) for the manufacture of Plaster of Paris, cement, ammonium sulphate, sulphuric acid.
(ii) for preparing blackboard chalk.
(iii) in anhydrous form as drying agent.

1
4. Plaster of Paris, 2CaSO4.H 2O or CaSO 4 . H 2O (Calcium sulphate hemihydrate)
2
Preparation : It is obtained when gypsum, calcium sulphate dihydrate (CaSO4.2H2O), is heated at 120°C.
o
120 C
2 CaSO 4 .2H 2 O    2CaSO4 .H 2 O  3H 2 O
Gypsum Plaster of Paris

(Calcium sulphate hemihydrate)


Properties :
(i) Plaster of Paris is white powder.
(ii) It has the property of setting to a hard mass when a paste with water is allowed to stand aside for sometime.
Slight expansion occurs during the setting as water is absorbed to reform CaSO4.2H2O (gypsum). The setting
process is exothermic. The process of setting takes place in two stages. In the first stage, there is conversion of
Plaster of Paris into orthorhombic form of gypsum (setting step) and in the second stage orthrohmbic form
changes into monclinic form (hardening step).
Setting Hardening
2CaSO4.H2O H2O CaSO4.2H2O CaSO4.2H2O
Plasterof Paris Orthorohombic Monoclinic
The setting of plaster of paris may be catalysed by sodium chloride while it is retarded by borax or alum. Addition
of alum of Plaster of Paris makes the setting very hard. The mixture is known as Keene’s cement.
(iii) When plaster of Paris is heated at 200°C, it forms anhydrous calcium sulphate which is known as dead
plaster. It has no setting property as it takes up water only very slowly.
Uses : It is used
(i) in surgery for setting broken or dislocated bones.
(ii) in making casts for statues,toys, surgical instuments, etc.
(iii) in making casts in dentistry.
(iv) in making blackboard chalk.
5. Sodium Thiosulphate, Hypo, Na2S2O3.5H2O :
Preparation :
(i) By boiling solution of sodium sulphite with flowers of sulphur till the alkaline reaction has disappeared.
Boil
Na 2SO3  aq   S 
 Na 2S2O3
(flowers of Sod.thiosulphate
sulphur)
(ii) By Spring’s method : A mixture of solution of Na2S and Na2SO3 is treated with a calculated quantity
of iodine. Fractional crystallization of resulting solution gives crystals of Na2S2O3. 5H2O
Na 2SO3  Na 2S  I2  Na 2S2O3  aq   2NaI
Sodium Sod.
sulphite sulphide

Crystallization

Na2S2O3.5H2O
(hypo)

(iii) By passing a current of SO2 gas in a solution of sodium carbonate and sodium sulphide.
Na 2CO3  2Na 2S  4SO2  3Na 2S2O3  CO2
(iv) By boiling sulphur with NaOH solution :
6NaOH  aq   4S  Na 2S2O3  2Na 2S  3H 2O
Properties :
(i) It is colourless, crystalline, efflorescent solid. It melts at 48°C. It is extremely soluble in water and has a
tendency to form supersaturated solution.
(ii) Effect of heat.
215
Na 2S2O3.5H 2O s  
 Na 2S2O3 s   5H 2O
 223o C
4Na 2S2O3   3Na 2SO4  Na 2S5
(iii) Action of dilute acids : Sulphur is precipitated and SO2 gas is evolved.
Na 2S2O3  2HCl  2NaCl  H2O  SO2  S
(iv) Action with halogens : Chlorine oxidises it to sodium sulphate and sulphur is precipitated.
Na 2S2O3  Cl2  H2O  2HCl  Na 2SO4  S
Iodine oxidises sodium thiosulphate to sodium tetrathionate.

2Na 2S2O3  aq   I2  Na 2 S4O6  2N aI


(Brown) Sod. tetra Sod.iodide
thionate  colourless 
(colourless)
 This reaction is used in iodoetric titrations in voluetry. The indicator of the titration between iodine and hypo
is starch.
(v) Action of silver nitrate solution :
(a) When AgNO3 is in excess : A black precipitate of Ag2S is obtained.
Na 2S2O3  aq   2AgNO3  aq   2NaNO3  aq   Ag 2S2O3 
White ppt.
On standing
Ag 2S2O3  H 2O  Ag 2S   H 2SO4
Black ppt.
 Silver sulphide 
(b) When hypo is in excess : The white ppt. of Ag2S2O3 is dissolved in Na2S2O3 due to complex foration.
Na 2S2O3  aq   2AgNO3  aq   2NaNO3  aq   Ag 2S2O3
White ppt.
3Na 2S2O3  aq   Ag 2S2O3  2Na 3  Ag  S2O3 2   aq 
Excess hypo White ppt. Sod. argento thiosulphate
 water solub le coplex 
(vi) Reaction with silver halides : Silver halides (AgCl, AgBr and AgI) dissolve in hypo due to complex
formation.
AgBr  2Na 2S2O3  aq   NaBr  Na 3  Ag  S2O3  2   aq 
Light yellow ppt. Sod.arg ento thiosulphate
(vii) Reaction with copper sulphate : Cuprous thiosulphate is formed which dissolves in excess of hypo
to form a complex
CuSO4  Na 2S2O3  Na 2SO4  CuS2O3
Cupric thiosulphate
2CuS2O3  Na 2S2O3  Cu 2S2O3  Na 2S4O6
Cuprous
thiosulphate
3Cu 2S2O3  2Na 2S2O3  Na 4  Cu 6  S2O3 5   aq 
Sodium cuprothiosulphate
(viii) Reaction with ferric chloride : A violet or purple colour is obtained on adding hypo to FeCl3
solution. In the presence of excess of hypo, the purple colour disappears.
2FeCl3  3Na 2S2O3  Fe 2  S2O3 3  6NaCl
Ferric thiosulphate
Violet or purple colour
Fe 2  S2O3 3  Na 2S2O3  2FeS2O3  Na 2S4O6
Faintly
green colour

6. Magnesium sulphate (Epsom salt) MgSO 4 .7H2O :


Preparation :
(i) By dissolving magnesite or dolomite in dilute H2SO4.
MgCO3  H 2SO 4  MgSO 4  aq   H 2O  CO 2 
MgCO3.CaCO3  2H 2SO4  MgSO 4  aq   CaSO4  s   2H 2O  2CO 2
In the second case, white ppt. of CaSO4 is filtered off and the filtrate on crystallization gives MgSO4. 7H2O.
MgSO4 + 7H2O  Crystalisation
 MgSO4.7H2O
Properties :
It is a colourless, crystalline solid, soluble in water with evolution of heat. It loses its water of crystallization
on exposure to air, i.e., it shows efflorescence. It has a bitter taste.
Effect of temperature :
150C 200C
MgSO 4 .7H 2O   MgSO4 .H 2O 
 MgSO 4  H 2O
6H 2 O
Anhydrous
salt
, above
2MgSO 4 
200C
 2MgO  2SO 2  O2
With alkali sulphates, it forms double salts of type K 2SO4 .MgSO4 .6H2O.
 In MgSO4.7H2O, six H2O molecules are attached to Mg+2 while the seventh is attached with SO24  .
Uses :
(i) In medicine as a purgative.
(ii) In sizing and loading paper, silk and cotton.
(iii) In dyeing and tanning processes.
(iv) In ceramic, cement and match industries.
(iv) In the treatment of textile fibres to make them non-inflammable.
(v) As stimulant to increase bile secretions.
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