GROUP 1 – THE ALKALI METALS

The group 1 elements, otherwise known as alkali metals are the most reactive elements,
excellent conductors of electricity and are typically soft. They have one loosely held
valence electron in their outermost shell and typically form univalent, ionic and colorless
compounds. They are called s-block elements because their outermost electron is contained
in s-subshell. Group 1 elements include Li, Na, K, Rb, Cs and Fr. The physical and
chemical properties are closely related to their electronic structures and sizes. Li, the first
element in the group shows considerable difference behaviour from the rest of the group
member.

ELECTRONIC CONFIGURATION OR STRUCTURE

Element Symbol Electronic Structure

3
Lithium Li [He]2s1 or 1s22s1
11
Sodium Na [Ne]3s1 or 1s22s22p63s1

19
Potassium K [Ar]4s1 or 1s22s22p63s23p64s1
37
Rubidium Rb [Kr]4s1 or 1s22s22p63s23p63d104s24p65s1

55
Caesium Cs [Xe]6s1
87
Francium Fr [Rn]7s1

Because of the similarities in the electronic structures of these elements, they have many
similarities in their chemical behavior apart from Li.

The metal ions of group 1 element have inert gas configuration, thus have no unpaired
electron, hence are diamagnetic and colourless. In fact, all the compounds formed by group
1 metals are white except those with acid radicals such as chromates and permanganates
OCCURRENCE AND ABUNDANCE

 Li is the 35th most abundant element by weight and is mainly obtained as the silicate
minerals, spodumene – Li Al(SiO3)2 and Lepidolite –Li2Al2(SiO3)3(FOH)2.
 Na is 7th most abundant element by weight in the earth’s crust and its largest source is
rock salt (NaCl).
 K is 8th most abundant element by weight in the earth’s crust and occurs mainly as
deposits of sylvite (KCl); sylvinite (a mixture of KCl and NaCl) and carnallite (double
salt KCl·MgCl2·6H2O). Soluble Potassium salts are collectively called ‘potash’.
 Rb – there is no convenient source
 Cs – present in pollucite, CsAl(SiO3)2·H2O and as by-products from Li processing.
 Fr is a rare radioactive element, does not occur appreciably in nature, hence very little
of its chemistry is known.

EXTRACTION OF THE METALS

The metals may all be isolated by electrolysis of a fused salt, usually the fused halide, often
impurity added to lower the melting point.

Na is made by the electrolysis of a molten mixture of 40% NaCl and 60% CaCl2 in a Downs
cells. The mixture melts of about 600°C compared with 803°C for pure NaCl. CaCl2 is
therefore added to lower the operation temperature.

Li can be obtained from electrolysis of molten LiC – KCl mixture.

The modern method of obtaining potassium is to reduce molten KCl with Na vapor at
850°C in a large fractionating lower. This gives K of 99.5% purity.

850°C
Na + KCl NaCl + K
Rb and Cs are produced in a similar way by reducing the chlorides with Ca at 750°C under
reduced pressure.

750°C
2CsCl + Ca CaCl2 + 2Cs

PHYSICAL PROPERTIES

 Members of the group are typical metal hence, good conductor of heat and
electricity
 There is a decrease in electrostatic force of attraction between the valence electron
and the nuclei of the atoms down the group.
 Atomic radius and ionic radius of the elements increase down the group due to
increase in electron shell. However, the ionic radius of a cation is usually smaller
than its atomic radius of the same atom.
 The electron affinity, first ionization energy and electronegativity decrease down
the group.
 The group 1 atoms are the largest in their horizontal period in the periodic table
because atomic size and ionic size decrease across the periods due to increase in
valence electron.
 Hardness and density decrease down the group.
 The atom become larger in descending the group from L1 to Cs, so the bonds are
weaker, the cohesive energy decreases and the softness of the metals increases.
 Melting and boiling points decrease down the group as a result of increase of atomic
radii. For example melting point and boiling point of Li and Cs are 181°C , 28.5°C
and 1347°C, 705°C respectively.
 Most of their compounds are soluble in water because they form ionic compounds.
 Salts of group 1 metals are stable to heat except lithium
 They all impact a characteristic colour to the bursen flame, a property associated
with the outermost ‘s’ electrons. They give characteristic flame colouration.
 Li – Crimson
Na – Yellow
K – Lilac
Rb – Red-violet
Cs – Blue

CHEMICAL PROPERTIES

All alkali metals are chemically reactive. They are strong reducing agents. They form ionic
compounds because of their low electro-negativities. Some chemical reactions of alkali
metals include:

a) Reaction with water

Group 1 metals all react with water, liberating hydrogen and forming the hydroxides.
The reaction becomes increasingly violent on descending the group. The reactions are
exothermic.
Thus, Li reacts gently; Na melts on the surface of the water and may catch fire.
Potassium which liberates less energy reacts violently and catches fire.
2Li + 2H2O 2LiOH + H2
2Na + 2H2O 2NaOH + H2
2K + 2H2O 2KOH + H2

NaOH is often called caustic soda and KOH called caustic potash because of their
corrosive properties. These alkalis are the strongest bases known in aqueous solution.
The hydroxides of Na, K, Rb and Cs are very soluble in H2O, but LiOH is much less
soluble.
b) Reaction with air (oxygen)
The metals all burn in air to form oxides of various types: monoxides (normal oxides);
peroxides and superoxides.
Li forms the monoxide Li2O (and some peroxides Li2O2);
 Na forms the peroxides Na2O2 (and some monoxide Na2O) and
others form superoxides of the type MO2.
4Li + O2 2Li2O (Lithium oxide/Lithium monoxide)
Or Na

2Na + O Na2O2 (Sodium peroxide)

Or Li

K + O2 KO2 (potassium superoxide)

All the three oxides are crystalline solids and they react vigorously with H2O to give
hydroxides as follows:
Monoxide: Li2O + H2O 2LiOH

cold
Peroxide: Na2O2 + 2H2O 2NaOH + H2O2

warm
2Na2O2 + 2H2O 4NaOH + O2

Superoxide: 2KO2 + 2H2O 2KOH + H2O2 + O2

c) Reaction with dinitrogen

Li is the only element in the group that reacts with dinitrogen to form a nitride.
6Li + N2 2Li3N
Lithium nitride, Li3N is ionic (3Li+ and N3-) and is ruby read. It has two characteristics
reactions which are of interest.
a) Decomposes on heating at high temperature
heat
2Li3N 6Li + N2

b) Reacts with water, giving ammonia

Li3N + 3H2O 3LiOH + NH3
d) Reaction with Hydrogen
They react with hydrogen, forming ionic or salt-like hydrides M+H-
The ease of formation of hydride decreases from Li to Cs.
e) Reaction with liquid ammonia
The alkali metals react with liquid ammonia to form a metal amide and hydrogen in
the presence of catalysts such as Fe.
M + NH3 MNH2 + ½ H2
f) Reaction with carbon/ethyne (acetylene)
If Li is heated with carbon, an ionic carbide Li2C2 is formed. The other metals do not
react with C directly, but do form similar carbides when ethyne is passed through a
solution of the metal in liquid ammonia.
2Li + 2C Li2C2
Liq. NH3
2Na + C2H2 NaC≡ CNa + H2

Liq. NH3
Na + C2H2 NaC ≡ CH + ½ H2

ANOMALOUS BEHAVIOUR OF LITHIUM

The properties of Li and its compounds differ from those of the other Group 1 elements.
Apart from having the same oxidation number as the rest of Group 1, Li and its compounds
show closer similarities with Group 2 elements (particularly Mg) than they show towards
their own group. Some of the differences or anomalous properties display by Li which
make it resembles Mg and differ from other members of Group 1 include:

1) The melting point and boiling point of Li metal are much higher than those for the
other Group 1 element, e.g. the melting and boiling points of Li are 181°C and 1347°C
while that of Cs are 28.5°C and 705°C respectively.
2) Li is much harder than the other Group 1 metals.
3) Li has small atomic and ionic radii.
4) Li reacts the least readily with oxygen, forming the normal oxide. It forms a peroxide
only with great difficulty, and the higher oxides are unstable.
5) Unlike Group 1, but like Group 2, Li forms a Nitride, Li3N. None of the other Group
1 element forms a nitride.
6) The hydroxide of Li and Mg are much less soluble in H2O, hence less basic while
hydroxides of Na, K, Rb and Cs are very soluble in H2O.
7) Li only forms a bicarbonate in solution, while other members of the group form stable
solid bicarbonate.
8) Like Group 2 metals, Li reacts directly with carbon to form an ionic carbide. None of
the other Group 1 element do this.
9) Li2CO3 (lithium carbonate), Li3PO4 (lithium phosphate) and LiF (lithium fluoride) are
all insoluble in water and LiOH (lithium hydroxide) is only sparingly soluble like
magnesium salts which are insoluble or sparingly soluble. The rest of Group 1 elements
form soluble compounds.
10) Lithium nitrate decomposes to form oxide nitrogen and oxygen while the nitrates of
other members of Group 1 decompose to produce nitrite and oxygen.

The similarity between Li (the first member of Group 1) and Mg (the second element in
Group 2) is called a diagonal relationship. Diagonal relationships also exist between other
pairs of elements such as Be and Al; B and silicon.

The diagonal relationship can be defined as the resemblance of each of the first three
elements of the second row (period 2) of the periodic table to the elements located
diagonally to the right of it in the third row (period 3).

Period 2: Li Be B C

Period 3: Na Mg Al Si

The diagonal relationship arises because of the effects of both size and charge.
In descending a group, the atoms and ions increase in size. On moving from left to right in
the periodic table, the size decreases. Thus, on moving diagonally, the size remains nearly
the same. For example, Li is smaller than Na, and Mg is also smaller than Na, and hence
Li and Mg are similar in size.

The sizes of Li+ = 0.76Å and Mg2+ = 0.72Å are close and so in situation where size is
important, their behavior should be similar.

It is sometimes suggested that the diagonal relationship arises because of a diagonal

similarity in electronegativity values.

Li Be B C
1.0 1.5 2.0 2.5

Na Mg Al Si
0.9 1.2 1.5 1.8