Group 1:

The alkali metals

2008 Pearson

CONTENTS
11.1 Introduction
11.2 Occurrence, extraction and uses
11.3 Physical properties
11.4 The metals
11.5 Halides
11.6 Oxides and hydroxides

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CONTENTS
11.7 Salts of oxoacids: carbonates and
hydrogencarbonates
11.8 Aqueous solution chemistry including
macrocyclic complexes
11.9 Non-aqueous coordination chemistry

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11.1 Introduction

We have already covered several aspects of the

chemistry of the alkali metals as follows:

Ionization energies of metals

Structures of metal lattices

Metallic radii, rmetal

Melting points and standard enthalpies of atomization

of metals
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11.2 Occurrence, extraction and uses

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 to form NaCl.
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11.2 Occurrence, extraction and uses

(a)

Uses of NaCl in the US in 2005;

(b) industrial uses of NaOH in Western Europe in 1995.

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11.3 Physical properties

Some physical properties of the alkali metals, M, and their ions, M+.

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11.3 Physical properties

Some physical properties of the alkali metals, M, and their ions, M+.

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MELTING POINTS

Melting points of solids refer to : M(s) M(l) , relatively low for this group

All structures are the same type (all metals have body
centred cubic structures) direct comparison is valid down
the group
Low values can be related to the relatively weak M-M
bonding; only one valence electron per M centre
Bcc lattice is non-closed-packed, and this contribute to low
melting points
Down the group M-M become weaker as ns-ns overlap
becomes less effective (more diffuse orbital as n increases)

IONIC RADII

CATION RADII;
General trends is an increase in cation size
down the group
Charge constant (M+), so a direct comparison
down the group is valid

From

Li to Na, extra quantum shell is

added, similarly from Na to K, K to Rb
and Rb to Cs

11.4 The metals

Appearance

The metals Li, Na, K and Rb are silvery-white, but Cs has a goldenyellow cast.

All are soft, Li the least so, and the trend is consistent with their
melting points.

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11.5 Halides

Standard enthalpies of formation (fHo) and lattice

energies (lattice Ho) of alkali metal halides, MX.
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11.6 Oxides and hydroxides

The structure of the suboxide Cs11O3 consists of three oxygencentred, face-sharing octahedral units. Colour code; Cs, blue; O, red.
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11.7 Salts of oxoacids: carbonates and

hydrogencarbonates

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11.7 Salts of oxoacids: carbonates and

hydrogencarbonates

Schematic representation of the Solvay process for the

manufacture of Na2CO3 and NaHCO3 from CaCO3,
NH3 and NaCl. The recycling parts of the process are
shown with blue, broken lines.

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11.7 Salts of oxoacids: carbonates and

hydrogencarbonates

Uses of Na2CO3 in the US in 2004.

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11.8 Aqueous solution chemistry including

macrocyclic complexes

In the solid state, hydrogen bonding results in anion association in

NaHCO3 and KHCO3 and the formation of (a) dimers in NaHCO3 and
(b) infinite chains in KHCO3. Colour code: C, grey; O, red; H, white.
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11.8 Aqueous solution chemistry including

macrocyclic complexes

A cryptand is a polycyclic ligand containing a cavity.

When the ligand coordinates to a metal ion, the complex

ion is called a cryptate.

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11.8 Aqueous solution chemistry including

macrocyclic complexes

A space-filling diagram of the [Na2]2- dimer, sandwiched between two

[BaL]+ cations in the complex [BaL]Na2MeNH2, where L is the ligand.
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11.8 Aqueous solution chemistry including

macrocyclic complexes

The structure of valinomycin

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11.8 Aqueous solution chemistry including

macrocyclic complexes

A space-filling representation of the [K (valinomycin)]+

ion which illustrates the hydrophobic exterior.
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11.9 Non-aqueous coordination chemistry

The structure of [{LiNHtBu}8] determined by X-ray diffraction;

hydrogen and methyl-carbon atoms have been omitted for clarity.
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THE END
2008 Pearson