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Chemical Characteristics

Solution in Liquid ammonia

❑ Alkali metals dissolve in liquid ammonia.

❑ S-block elements produce dark blue solution in

liquid ammonia (except Be, Mg).

M + (x + y)NH3 → [M(NH3)x]+ + [e(NH3)y]–

Chemical Characteristics

Solution in Liquid ammonia

❑ These solutions of metals in liquid ammonia act

as powerful reducing agents mainly due to

presence of solvated or ammoniated electrons.

Chemical Characteristics

Solution in Liquid ammonia

❑ If the blue solution is allowed to stand, the colour

slowly fades until it disappears owing to the

formation of a metal amide.

Chemical Characteristics

Solution in Liquid ammonia

❑ In concentrated solutions ammoniated electrons

associated to form electron-pairs and their

paramagnetic character decreases (becomes

diamagnetic.

❑ Evaporation of the ammonia from solutions of

Group 1 metals yields the metal.

General Characteristics

Oxides and Hydroxides

❑ The oxides are easily hydrolysed by water to form the

hydroxides

M2O + H2O → 2MOH

M2O2 + 2H2O → 2MOH + H2O2

2MO2 + 2H2O → 2MOH + H2O2 + O2

General Characteristics

Salts of Oxo-acids

❑ The solubility of carbonates, nitrates and

bicarbonates increase in the order:

❑ Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3,

LiNO3 < NaNO3 < KNO3 < RbNO3 < CsNO3 and

LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 < CsHCO3

Nature of Carbonates and bicarbonates

Cs2CO3 > Rb2CO3 > K2CO3 > Na2CO3 > Li2CO3

Nature of Nitrates

2MNO3 → 2MNO2 + O2
2LiNO3 → Li2O + 2NO2 + ½ O2
Nature of Sulphates

M2SO4 + 4C → M2S + 4CO

Nature of Perchlorates

LiClO4 > NaClO4 > KClO4 > RbClO4 > CsClO4

LiClO4 is ten times more soluble than NaClO4. It is

mainly due to extensive solvation of smaller Li+.

Solubility in Liquid Ammonia

M → M+ (in liquid ammonia) + e (ammoniated)

M + (x + y) NH3 → [M(NH3)x]+ + e(NH3)y
Abnormal Behaviour of Lithium

Lithium differs from alkali metals in the following respects:

• It is more harder and lighter than other alkali metals.

• It is not affected by air easily and does not lose its
lustre even on melting. The melting and boiling
points of lithium are comparatively high.
• It reacts slowly with water to liberate hydrogen.
Abnormal Behaviour of Lithium

Lithium differs from alkali metals in the following respects:

• 2LiOH → Li2O + H2O

• Li2CO3 → Li2O + CO2

• 4LiNO3 → 2LiO + 4NO2 + O2

• 2NaNO3 → 2NaNO2 + O2
Diagonal Relationship Similarities with Magnesium

Group 1 Group 2
Li Be
Na Mg
Diagonal Relationship Similarities with Magnesium

Reasons for the diagonal relationship are the following:

• Electronegativities of Li and Mg are quite

comparable. (Li = 1.00, Mg = 1.20)
• Atomic radii and ionic radii of Li and Mg are not very
much different.
Atomic radii (pm) Li 152 Mg 160
Ionic radii (pm) Li +76 Mg 2+72
• Atomic volumes of Li and Mg are quite similar.
Li 12.97 mL, Mg 13.97 mL
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Both Li and Mg are harder and have higher melting

points than the other metals in their respective
groups.
• Li like Mg decomposes water slowly to liberate
hydrogen.
2Li + 2H2O → 2LiOH + H2
Mg + 2H2O → Mg(OH)2 + H2
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Both the elements combine with nitrogen on heating.

6Li + N2 → 2Li3N
3Mg + N2 → Mg3N2
Li3N + 3H2O → 3LiOH + NH3
Mg3N2 + 6H2O → 3Mg(OH)2 + 2NH3
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Lithium forms only monoxide when heated in

oxygen. Mg also forms the monoxide.
4Li + O2 → 2Li2O
2Mg + O2 → 2MgO
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Lithium forms only monoxide when heated in

oxygen. Mg also forms the monoxide.
4Li + O2 → 2Li2O
2Mg + O2 → 2MgO
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Hydroxides of Li and Mg are weak bases and are

slightly soluble in water. Both decompose on
heating.
4LiOH → Li2O + H2O
Mg(OH)2 → MgO + H2O
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Lithium fluoride, phosphate, oxalate and carbonate,

like the corresponding salts of Mg, are sparingly
soluble in water.
• Carbonates of Li and Mg decompose on heating.
Li2CO3 → Li2O + CO2
MgCO3 → MgO + CO2
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Nitrates of Li and Mg decompose on heating giving

mixture of nitrogen dioxide and oxygen.
4LiNO3 → 2LiO + 4NO2 + O2
2Mg(NO3)2 → 2MgO + 4NO2 + O2
Diagonal Relationship Similarities with Magnesium

Lithium resembles magnesium in the following respects:

• Chlorides of both Li and Mg are deliquescent and

soluble in alcohol and pyridine. Lithium chloride like
magnesium chloride, (MgCl2.6H2O) separates out
from solutions as hydrated crystals, LiCl.2H2O)
• The bicarbonates of Li and Mg do not exists in solid
state, they exist in solutions only.
s-Block Elements

Some of important order of the properties of alkali metals and

their compounds are:
• LiOH < NaOH < KOH < RbOH < CsOH
Basic nature of hydroxides
Thermal stability of hydroxides

• CsH < KH < NaH < LiH

Stability of Hydrides

• Cs+ < Rb+ < K+ < Na+ < Li+

Ionic radii in water, i.e. hydrated ions
s-Block Elements

Some of important order of the properties of alkali metals and

their compounds are:
• Li+ < Na+ < K+ < Rb+ < Cs+
Molar conductivity of hydrated ions

• Li < Na < K < Rb < Cs

Reactivity towards water

• Cs < Rb < K < Na < Li

Reactivity towards hydrogen
s-Block Elements

Some of important order of the properties of alkali metals and

their compounds are:
• Li < K < Na < Rb < Cs
Density of alkali metals
• Li > Cs > Rb > K > Na
Reducing power in solution
• LiCl < NaCl < KCl < RbCl < CsCl
Ionic character
• LiCl < LiBr < LiI
Covalent character
s-Block Elements

Some of important order of the properties of alkali metals and

their compounds are:
• CsClO4 < RbClO4 < KClO4 < NaClO4 < LiClO4
Solubility in water
• Li2O < Na2O < K2O < Rb2O < Cs2O
Basic nature
• Li < Na < K < Rb < Cs
Atomic and ionic radii
• Cs < Rb < K < Na < Li
Ionisation energy
Example Metal M + N2 → Nitride → NH3, Metal M is :
A. Na
B. K
C. Li
D. Rb
Example Match List I with List II and select the correct matching:
List I List II
A. NaNO3 1. Baking soda
B. NaNH4HPO4 2. Glauber’s salt
C. NaHCO3 3. Chile salpetre
D. Na2CO3.10H2O 4. Microcosmic salt
E. Na2SO4.10H2O 5. Washing soda
A. A-1, B-2, C-3, D-4, E-5
B. A-5, B-4, C-3, D-2, E-1
C. A-3, B-4, C-1, D-5, E-2
D. A-4, B-3, C-2, D-1, E-5
Sodium and important compounds
Solvay Ammonia
Soda Process
Solvay Ammonia
Soda Process Saturation of brine with ammonia
Solvay Ammonia
Soda Process Saturation of brine with ammonia

NH3 + H2O → NH4OH

MgCl2 + 2NH4OH → Mg(OH)2 + 2NH4Cl
Solvay Ammonia
Soda Process Carbonation

NaCl + NH3 + H2O + CO2 = NaHCO3 + NH4Cl

Solvay Ammonia
Soda Process Filtration
Solvay Ammonia
Soda Process Ammonia recovery

NH4HCO3 → NH3 + H2O + CO2

Solvay Ammonia
Soda Process Flowsheet of Solvay process
11th
12th

Ashwani Sir
12th
11th

Ashwani Sir
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