Chemistry of the

Main Group
Elements
Prepared by: Kevin Nick S. Bandibas
The Main Group Elements
The Alkali Metals (Group 1A)

• Valence electron configuration = ns1

• Largest element in their respective period (periodic
trends = left to right decreasing atomic size)
• Lower densities than most metals
• Low MP and BP that decreases with increasing atomic
number
Properties of Alkali Metals
 The Alkali Metals (Group 1A)

• Naturally occurring as part of various minerals and

seawater.
• Do not occur naturally in elemental state

Rock salt (NaCl) Sylvite (KCl) Sylvinite (NaCl/KCl) Carnallite

(KCl.MgCl2. 6H2O)
The Alkali Metals (Group 1A)

• Unusually soft for a metal – can easily be cut with a knife

• Silvery-white/lustrous except Cs (golden yellow appearance)
The Alkali Metals (Group 1A)

• Na and K were discovered by Humphry Davy (1807)

• Li was discovered by Johan August Arfwedson (1817)
The Alkali Metals (Group 1A)

• Cs and Rb were discovered spectroscopically in

mineral spa waters by Robert Bunsen and Gustav
Kirchoff (1860)
• Fr –occurs naturally as 233Fr, but only as the decay
product of 227Ac in Uranium ores
- very low natural abundance; <30 g in Earth’s crust
- half-life of 21.8 minutes
The Alkali Metals (Group 1A)

• Almost all compounds are ionic, except for some Li and

Na organometallic compounds.

• Same charge and similar size of NH4+, Ag+, Tl+ result in

similar compounds, often isomorphous with alkali metal
analogs.
Electrolytic Process
• Used in the extraction of alkali metals
• Li – extracted from LiCl
- LiCl from silicate mineral spodumene (LiAlSi2O6)
• Na – extracted from NaCl (Downs process)
• K – extracted from KCl
• Rb and Cs – extracted from the by-products of Li
extraction from spodumene: RbCl and CsCl
Electrolysis of Alkali Metals
• Reduction potentials are so negative that the metals
cannot be obtained by electrolysis from aqueous
solutions; water reduction occurs instead

• All can be obtained by electrolysis of their molten salts

Downs Process
A schematic representation of the
electrolysis cell used in the Downs
process to produce sodium
commercially from NaCl. The
products (Na and Cl2) must be kept
separate from each other to prevent
recombination into NaCl.
Major Uses of the Alkali Metals
and Their Compounds

Uses of (a) NaCl and (b) Na2CO3 in the US in 2009. Source: US Geological Survey
Major Uses of the Alkali Metals
and Their Compounds
• K and Na are essential for human life
• [Na+]:[K+] ratio; responsible for the transmission of
nerve impulses.
• K – an essential plant nutrient
• K+ salts – widely used as fertilizers
• Na and Li – batteries
• Na[BH4] and Li[AlH4] – reagents for organic synthesis
Reactivities of Alkali Metals

• Powerful reducing agents

• Occur in nature as monocation (+1)
- Li+, Na+, K+, Rb+, Cs+, and Fr+
• All react with halogens, hydrogen, and water.
- 2M + X2 → 2MX X = F, Cl, Br, and I

- 2M + H2 → 2MH
- 2M + 2H2O → 2MOH + H2
Reactivities of Alkali Metals

• Violently reactive metals (except Li)

Reactivities of Alkali Metals
• Na, K, Rb, and Cs can be obtained by thermal
decomposition of their azide

• Only Li reacts with N2(g) at room temperature:

• Sodium also produces Na2O along with Na2O2

Learning Task

• Which is paramagnetic peroxide or superoxide? Explain.

Alkali Metals in NH3(l)
• All alkali metals (plus Ca, Sr, and Ba) dissolve in liquid
ammonia to form solvated electron solutions.

• Dilute Solutions
- dark blue in color (λ=1500 nm); diagnostic of a
“solvated electron”
- paramagnetic
- useful reducing agent (Birch Reduction)
Alkali Metals in NH3(l)
• All alkali metals (plus Ca, Sr, and Ba) dissolve in liquid
ammonia to form solvated electron solutions.

• Concentrated Solutions
- metallic bronze color
- conductivity like a molten metal
- weakly paramagnetic
Alkali Metals in NH3(l)
• With Fe3+ catalyst, the amide is formed.

- an analogous reaction occurs with amines (RNH2)

• LiNH2 uniquely decomposes to the immide on heating.

- this is an example of first-element uniqueness.

First-Element Uniqueness

• 1st Elements of the Main Group – unique chemistry not

shown by the heavier elements of the same group.
• Li – smallest alkali element; highest charge density;
anomalous behavior.
• Li compounds tend to be more covalent than
comparable alkali metals compounds
• Li exhibits diagonal relationship to Mg
First-Element Uniqueness

• Thermal decomposition of ionic nitrates give nitrite but

more covalent lithium nitrates decomposes to the
oxide.
Lithium Properties
• Very important metal
• Strong polarizing power
• Forms bonds with highly covalent character
• Used in ceramics, Li2CO3
• Lubricants
• Medicine (Lithium carbonate, treatment for bipolar disorder; high doses
damages the Central Nervous System)
• Lithium batteries – long lasting
• Li2O lightens and strengthens aircraft aluminum
• Armor plate
• LiOH – CO2 absorber in space capsules and submarines
Group 1 Organometallic
Compounds
• Li and Na organometallic compounds – important in
organic synthesis
• Li organometallic compounds:
- more covalently bonded
- more soluble in organic solvents
• LiR (R – alkyl group) are formed by reacting organic halides
with metallic lithium
RCl + 2Li → LiR + LiCl
C6H6
Group 1 Organometallic
Compounds
• Li compounds are flammable; add LiBr and LiI to form
stable complexes

• LiCH3 and LiC2H5 – tetramers which are highly basic

and nucleophilic, reactive towards electron acceptors
and proton donors.
Aqueous Solution Chemistry of
Alkali Metals
• Li salts are mostly sparingly soluble in water
• For large anions, the Li salts are soluble
• In dilute solutions, alkali metal ions rarely form
complexes, but where these are formed,
- e.g. with [P2O7]4- and [EDTA]4-
- stability constant: Li+ > Na+ > K+ > Rb+ > Cs+
- strength of adsorption: Li+ < Na+ < K+ < Rb+ < Cs+
Macrocyclic Complexes:
Alkalides and Electrides
Qualitative Analysis of Alkali
Metals