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INORGANIC CHEMISTRY

Inorganic chemistry is the branch of chemistry


concerned with the properties and behavior of
inorganic compounds
*inorganic compounds are considered to be of a
mineral, not biological, origin.

The Groups IA Elements

Content

Introduction to group IA elements, general physical properties,


appearance melting point and electrical conductivities of group IA.

General chemical properties of alkali metals, reactions of group IA


elements with water and relative reactivities descending the group.

Compounds of the group IA elements hydroxides, oxides, halides,


hydrides and carbonates

Manufacturing of sodium by electrolysis and its industrial


applications

Introduction

The alkali metals lithium, sodium, potassium, rubidium, cesium


and francium

Natural occurrences

In nature : mineral and rocks


(not found free in nature easily oxidized)

Na and K common ; others quite rare

Radioactivity
Fr - heaviest element in group
- highly radioactive - form by particle emission from
actinium
K and Cs natural radioactive isotope

Element

Mineral

Lithium, Li
Sodium, Na
6th most abundant in
the earth crust

Potassium
8th most abundant in
the earth crust

Compound

Petalite
Spodumene

LiAlSi4O10

Caustic Soda
Rock salt
Saltpeter
Trona
Mirabilite
Albite

NaOH
NaCl
NaNO3

Potash
Sylvite
Carnalite
Orthoclase

K2CO3

Rubidium, Rb

Lepiodolite impurities

Cesium, Cs

Pollucite
Lepiodolite impurities

LiAlSi4O10

Na2CO3.NaHCO3.2H2O
Na2SO4.10H2O
NaAlSi3O8
KCl
KCl.MgCl2.6H2O
KAlSi3O8
CsAl4Si9O26.H2O

Table 1.1 Occurrence of Group IA elements

Physical properties

Silvery
Soft : can be cut with knife ; but Li is harder
- Na soft (cold butter)
- Cs slightly golden and melts in hand
- K squeezed like clay or dough
Metals are soft and relatively low melting point
Reason : - one valence electron, ns1
- distance between the nucleus and valence electron is far
- the attraction between them is relatively weak
- weak metallic bonding cause the crystal structure to be
deformed or broken down easily.
Low densities : lowest molar mass in their period and largest atomic
radii.
- Li floats on lightweight household oils

Element

Mp

Bp

Density,
g/mL

Standard
Reduction
Potential
(SRP), V

First
Ionization
energy,
KJ/mol

Lithium

180.5

1347

0.534

-3.05

520

Sodium

97.8

881

0.971

-2.71

496

Potassium

63.2

766

0.862

-2.92

419

Rubidium

39.0

688

1.53

-2.92

403

Cesium

28.5

705

1.87

-2.92

377

Good electrical and thermal properties


Solubility
- Salts with small anions are very soluble in water
- Salts with large and complex anions ; eg silicates and
aluminosilicates are not very soluble in water

Chemical properties

Lowest ionization energy : single electron in the outer shell easily to


remove
Li highest first ionization energy
most easily to oxidize
Reason :
- atomic radii increase down a group
- Li+ ion is so small
- the charge density (charge to radius ratio) and polarizing power of
the Li cation will very high
- the strength of interactions of the Li cation with the water molecules
in solution is stronger
- Li hydrated cations interact so strongly with water molecules ;

Very powerful reducing agents, extremely reactive and react


vigorously with water
Metal surface tarnishes rapidly exposed to air, cold water and even
ice
SRP (-2.7 to -3.0) strong tendency to form cations, 1+ ion in solution
- SRP are small (and negative)
Reason : elements are easily oxidized by losing one valence electron
- Li smallest SRP least tendency to be reduced/greatest tendency
to oxidized
Reactivity : Li<Na<K<Rb<Cs (increased down a group)
Enthalpy of hydration
- for the ions are high, especially Li+ ion due to its small ionic radius.
- decreases down a group : Li, Na, K hydrated ; Rb and Cs rare
hydrated
Can reduce O2, Cl2, NH3, and H2 to form oxides, amides and hydrides
Formed ionic compound

Anomalous behaviours of lithium.


Lithium

Other Group 1 Metals

Form normal oxide, Li2O

Na and K forms peroxide, and K,


Rb and Cs form superoxide

Form Lithium nitride, Li3N

Do not form M3N

Forms stable compounds with


small anions. For example, LiH is
stable up to 900 0C

NaH decomposes at 350 0C

Forms less stable compounds with MOH (M = Na, K, Rb, Cs) is very
large anions. For example, LiOH
stable
decomposes to Li2O
Strong tendency to form covalent
compounds

Less or tendency to form covalent


compounds

Reaction with water

General reaction :
2M + 2H2O

2MOH +

H2

Alkali metals reduced the hydrogen in water to form hydroxide and


hydrogen gas
Reactivity towards water
- Li react readily with vigorous bubbling - released hydrogen gas
- Na react rapidly to produce heat
- K causes the H2 to burst into flames and heat released
- Rb and Cs explosive in water
Relative reactivity : increase down the group
Alkali metal : kept under anhydrous nonpolar liquids eg : mineral oil
and paraffin to prevent air oxidation

Compounds of the elements


a)
Oxides
Oxide

Properties

oxide ;
M2O

White crystals

[O]2Li2O

Peroxide
M2O2

Basic oxide

Basic oxide

[O2]2Na2O2
Superoxide Basic oxide
MO2
[O2]KO2
RbO2
CsO2

Reaction
Preparation :
4Li + O2
(Lithium Oxide)
(limited oxygen)
Reaction:
Li2O + H2O
Preparation :
2Na + O2
Reaction:
Na2O2 + H2O
Preparation:
K + O2
Reaction:
2KO2 + 2H2O

Li2O

2LiOH
Na2O2
2NaOH + H2O2

KO2
2KOH + H2O2 + O2

Uses

Compounds of the elements


b)
Hydroxides
Hydroxide

Properties

Metal
hydroxide

-Strong
base
-Basicity
increases
down a
group
-White
crystalline
solid
-water
soluble
-Become
liquid when
expose to
air; except
LiOH

Reaction
Preparation:
2Na + 2H2O

2NaOH

Uses
+ H2

or from
Oxides or
Peroxides or
Superoxides
Reaction:
NaOH + HCl

Breathing equipment

NaCl + H2O

NaOH soap, bleach,


sodium phosphate,
and others
KOH liquid soap,
detergents, electrolyte
in storage batteries,
KOH aq remove CO2
and SO2 from air

Compounds of the elements


c)
Halides
Halides

Properties

Alkali
metal

-White
crystalline solid
-Thermally
stable
-Soluble in
water except LiF
-LiCl, LiBr and
LiI : soluble in
alcohol and less
polar solvent,
ethoxyethane

Reaction
Preparation:
1. 2M + Cl2
2. NaOH + HCl
Reaction:
2NaCl + 2H2O

2MCl
NaCl + H2O

2NaOH + Cl2 + H2

1.NaCl + CO2 + H2O + NH3


NaHCO3 + NHCl
2. 2NaHCO3

Uses

Na2CO3 + H2O

Uses :
NaCl : glazing the earthenware,
regenerating water softeners and
salting out of soap
KCl : fertilizer and others

(chlor-alkali
process)
Solvay process
to produce
Na2CO3

Compounds of the elements


d)
Hydrides
-

H atom tendency to accept electron to form 1s2


The electron affinity of H lower than Halide; small amount of energy released when
hydride ion formed.
Addition of electron causes electron-electron repulsion that increases the size of anion
By gaining an electron, H becomes anion, H- called hydride
Hydride forms only with least electronegative or highly electropositive metals.
Hydrides

LiH

NaH, KH

Properties

Reaction

-white
crystalline solid
-reactivity
increases down
a group

Preparation:
M + H2

Most stable,
melts at 700 0C,
decomposes at
1000 0C
-unreactive O2
and Cl2

8LiH + Al2H6

Decompose at
400 0C

2NaH

Uses

2MX (300-700 0C)

2LiAlH4 + 6LiCl

2Na + H2

LiAlH4 :
versatile
reducing agent

Hydrides

Properties
-base

Reaction
Reaction:
NaH + H2O

4NaH + (CH3)3BO3
+ 3CH3ONa
2NaH + B2H6

Uses

H2 + NaOH

NaBH4

2NaBH4

NaH good
reducing agent;
descaling iron and
making NaBH4

Compounds of the elements


e) Carbonates
Carbonate

Properties

Reaction

-Nature : Na2C03
, K2CO3
-Thermally
stable; except
Li2CO3
-Soluble in
water; except
Li2CO3 slightly
soluble

Li2CO3

Li2O + CO2

Dissolve in carbonic acid


form hydrogen carbonate
solution

Uses
Li2CO3 porcelain
enamels Li2CO3 and
glass
K2CO3 to produce KCN
and K2CrO4
Na2CO3 from solvay
process
Hydrate Na2CO3

Reactions Summary
1.

4M

O2

2M2O

limited O2

2.

4Li

O2

2Li2O

Excess O2 (Litihium
oxide)

3.

2Na

+ O2

Na2O2

sodium peroxide

4.

MO2

M = K, Rb, Cs ; excess
O2 (superoxide)

5.

2M

+ H2

2MH

Molten metals

6.

2M

+ X2

2MX

X = halogen

7.

2M

+ H 2O

2MOH + H2

K, Rb, Cs react
explosively

O2

Manufacturing of Sodium by electrolysis and its application


-

Sodium : commercially produced by electrolysis of molten NaCl in the


Downs Cell

Mixture of NaCl and NaCl2 is electrolysed instead of pure NaCl (melts at


801 0C)

The presence of CaCl2 reduces the melting point of the mixture to 580
0C, the eutectic mixture
Graphite electrode : anode
Cylindrical steel : cathode

Two electrode separated by an iron screen : to prevent molten Na


contact with Cl2 form in the electrolysis Process : molten Na produced
at cathode and floats to the surface of the liquid mixture because pure
Na has lower density than liquid salt mixture, NaCl-CaCl 2

Liquid Na drawn off the electrolytic chamber into container which cools
the liquid and finally freezes as solid sodium

Cl2 gas liberated at graphite anode and flow to the top of reaction
chamber into tank.

Fused NaCl contains sodium and chloride ions.


2NaCl

2Na+ +

2Cl-

ELECTROCHEMICAL CHANGES
At cathode Na+ ions migrate to cathode where they are reduced to Na.
2Na+ + 2e-

2Na (Reduction)

At anode Cl- ions migrate to anode and oxidised to form chlorine gas.
2Cl-

Cl2 + 2e-

Overall Reaction
2Na+ + 2e2Cl2Na+ + 2Cl-

(Oxidation)

2Na
Cl2 + 2e2Na + Cl2

Application of sodium :
- chemical industries eg : glass, rubber, pharmaceutical
- as reducing agent in metallurgy such as titanium
- to manufacture drugs and dye
- sodium arcs(luminous discharege of electric current crossing a
gap between two electrodes) highway lighting