Alkali metals

The six elements belonging to group 1 of the periodic table, namely lithium (Li),
sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr) are called
alkali metals. They constitute alkali metals because they readily dissolve in water to
form hydroxides, which are strongly alkaline in nature. They also form alkaline
oxides. The element francium is radioactive.
Occurrence
Lithium occurs mainly as silicate minerals such as spodumene [LiAl(SiO 3)2],
lepidolite [(Li,Na,K)2Al2,(SiO3)3 (F,OH)2] etc. It is the 35th most abundant element by
weight.
Compounds of sodium and potassium have been known from ancient times. Sodium
and potassium are seventh and eighth most abundant elements by weight in the
Earth's crust and together make up over 4% of the Earth's crust by weight. NaCl and
KCl also occur in large amounts in seawater. Rock salt (NaCl) is the major source of
sodium. Potassium occurs mainly as deposits of KCl (sylvite), which is a mixture of
KCl and NaCl (sylvinite) and double salt KCl.MgCl2.6H2O (carnallite).
Rubidium and cesium are obtained as a by-product of lithium processing. Francium
being radioactive does not occur appreciably in nature.
Electronic configurations
All the alkali metals have one electron in their outermost 's' orbitals preceded by the
noble gas configuration. Thus, the general configuration of alkali metals may be
written as [Noble gas] ns1 where 'n' represents the valence shell. The electronic
configurations of alkali metals are:
The electronic configurations of alkali metals
Element

Electronic
Symbo Atomi
configuratio
l
c No.
n

Lithium

Li

[He]2s1

Sodium

Na

11

[Ne]3s1

Potassiu
m

19

[Ar]4s1

Rubidium

Rb

37

[Kr]5s1

Cesium

Cs

55

[Xe]6s1

Francium

Fr

87

[Rn]7s1

General Characteristics of Alkali Metals

Atomic and ionic radii
Being the first elements of each period, alkali metals have the largest atomic and
ionic radii in their respective periods. As we move within a period, the atomic radius
and ionic radius tend to decrease due to increase in the effective nuclear charge. On
moving down the group, there is increase in the number of shells and, therefore,
atomic and ionic radii increase.
Physical property

Li

Na

Rb

Cs

Atomic radius (pm)

152 186 227 248 264

Ionic radius (pm)

76

102 138 152

167

Ionization energies

Alkali metals have the lowest ionization energy in each period. Within the
group, as we go down, the ionization energies of alkali metals decrease due to
their atomic size being the largest in their respective periods. In large atoms the
valence electrons are loosely held by the nucleus and are easily lost, leading them
to have low ionization energies and acquiring stable noble gas configurations. On
moving down the group, the atomic size increases and the number of inner shells
also increases, increasing the magnitude of screening effect and consequently, the
ionization energy decreases down the group.

The second ionizations energies of alkali metals are very high. The removal of
an electron from alkali metals causes the formation of monovalent cations having
very stable electronic configurations (same as that of noble gases). Therefore, it
becomes very difficult to remove the second electron from the stable noble gas
configurations, giving very high second ionization energy values (IE2).

Physical property

Li

Na

Rb

Cs

Ionization Energy
I

520

496

419

403

376

KJ mol -1 II

7298 4562 3051 2633 2230

Melting and boiling points

All alkali metals are soft and have low melting and boiling points. As alkali metals
have only one valence electron per metal atom, the energy binding the atoms in the
crystal lattice of the metal is low. Consequently, the metallic bonds in these metals
are not very strong and their melting and boiling points decrease on moving down
the group.
Physical property

Li

Na

Rb

Cs

Melting point (K)

453.5

370.8

336.2

312.0

301.5

Boiling point (K)

1620

1154.4

1038.5

961.0

978.0

Density
The densities of alkali metals are low as compared to other metals, with Li, Na and K
being even lighter than water (K is lighter than Na). While alkali metals do have close
packing of metal atoms in their lattice the large size of their atoms cause them to
have low densities. As we move down the group from Li to Cs, even though there is
an increase in atomic size, the simultaneous increase in atomic mass compensates
more than the increase in atomic size. The densities (mass/volume) of alkali metals
thus gradually increase from Li to Cs. However, potassium is lighter than sodium
probably due to increase in atomic size of potassium.
Physical property

Li

Na

Rb

Cs

Density (g cm -1)

0.53

0.97

0.86

1.53

1.90

Electropositive or metallic character

The electropositive character of an element is expressed in terms of the tendency of

its atom to release electrons:
All the alkali metals are strongly electropositive or metallic in character, since they
have low ionization energies and their atoms readily lose the valence electron. As the
ionization energies decrease down the family, the electron releasing tendency or
electropositive character is expected to increase down the family.
Physical property
Eo value (V)

Li
- 3.03

Na
- 2.71

K
- 2.93

Rb

Cs

- 2.93

- 2.92

Oxidation states
All alkali metals have only one electron in their valence shell. They exhibit an
oxidation state of +1 in their compounds and can lose the single valence electron
readily to acquire the stable configuration of a noble gas. Thus, they form
monovalent ions, M+ (e.g., Li+, Na+, K+, Rb+, Cs+). Since the second ionization
energies are very high, they cannot form divalent ions. Thus, alkali metals are
univalent and form ionic compounds.
Characteristic flame coloration
As the alkali metals have very low ionization energies, the energy from the flame of a
bunsen burner is sufficient to excite the electrons of alkali metals to higher energy
levels. The excited state being unstable, these electrons return to their original energy
levels, emitting extra energy, which gives characteristic flame colorations. The
different colors of the alkali metals can be explained on the basis of amount of energy
absorbed for excitation of the valence electron.
Physical property
Flame colour

Li

Na

Rb

Cs

crimson red yellow pale violet violet bluish

Photoelectric effect
When electromagnetic radiation strikes on the surface of alkali metals, they emit
electrons. This is called the photoelectric effect. This occurs as alkali metals have low
ionization energies, which allows the electrons to be easily ejected when exposed to
light. Among alkali metals, cesium has lowest ionization energy and hence it can
show photoelectric effect to the maximum extent.
Nature of the compounds
The compounds of the alkali metals are ionic in nature. Alkali metals form cations
readily by losing the valence electrons (due to the low ionization energies and large
atomic sizes). They go on to form ionic bonds with the non-metals of the 'p' block.
Lattice energies
The lattice energies of alkali metal salts are very high because strong electrostatic
forces of attraction hold up the cations and anions formed.
Lattice energy gives a measure of the forces of attraction between the ions. It is
defined as the amount of energy required to break one mole of a crystal into its free
ions.
The larger the forces of attraction, the greater will be lattice energy. The lattice
energy also depends upon the size of the ion and its charge. For the cation of same

valency, ionic solids having the same anion will display a decrease in the lattice
energy with increase in size of the cation. This is due to decrease in forces of
attraction between them.
Chemical properties of alkali metals
Alkali metals exhibit a high chemical reactivity because of their

low ionization energies

low heat of atomization.

Since the value of ionization energy decreases down the group (from Li to Cs) the
reactivity of alkali metals increases from Li to Cs. All alkali metals are highly reactive
towards the more electronegative elements such as oxygen and halogens. Some
characteristic chemical properties of alkali metals are described.

Action with Air

Formation of oxides
All the alkali metals on exposure to air or oxygen burn vigorously, forming oxides on
the surface of the metals. Lithium forms monoxide (Li2O), sodium forms the
peroxide (Na2O2) and the other elements form superoxides.
(MO2: M = K, Rb, Cs).

The fact that a small cation can stabilize a small anion and a large cation can stabilize
a large anion explains the formation and stability of these oxides. The size of Li + ion
is very small and it has a strong positive field around it. It can combine with only
small anion, O2- ion, resulting in the formation of monoxide (Li2O). Conversely, the
Na+ ion is a larger cation and has a weak positive field around it and thus can
stabilize a bigger peroxide ion, O22- or [-O-O-]2- which is also surrounded by a weak
negative field. Similarly, the other ions K+, Rb+, Cs+are still larger, having very weak
positive field. Thus these ions stabilize a bigger superoxide O 2- anion and form
superoxides.
The alkali metal oxides are basic in nature because they dissolve in water to form
alkali metal hydroxides.
Peroxides give hydrogen peroxide also

Action with Hydrogen

Formation of hydrides
All alkali metals react with hydrogen to form hydrides that are ionic in nature
(M+H-).

Reactivity of alkali metals with hydrogen increases from Li to Cs.

Ionic character of the hydrides increases from Li to Cs. The decrease in

ionization energy down the group permits easy availability of electrons to
hydrogen, forming H- ion.

Stability of hydrides decreases from Li to Cs because the M-H bond becomes

weak as the size of the alkali metal increases from Li to Cs. This causes the
stability of hydrides to decrease.

The hydrides behave as strong reducing agents and their reducing nature
increases down the group.

Action of Halogens
Formation of halides
Alkali metals combine readily with halogens to form ionic halides M +X-. For example,

Reactivity of alkali metals with halogen increases down the group because of
corresponding increase in electropositive character (decrease in ionization energy).
All metal halides are ionic crystals. Lithium iodide is slightly covalent as it has the
smallest cation, which exerts maximum polarizing power and iodide ion being the
largest anion can be polarized to the largest extent.
All alkali metal halides are soluble in water except LiF, as it has a high lattice energy
combined with a small cation and anion, making it insoluble in water.
Action Towards Water
Formation of hydroxides
Hydroxides and hydrogen gas result from the reaction of alkali metals with water.

Sodium and the other members of the family react so rapidly with water that the
hydrogen gas evolved immediately catches fire. Only lithium reacts slowly. Thus,
alkali metals are normally kept in kerosene oil and cannot be kept either in air or in
water.
The hydroxides of alkali metals are strongly basic as the M-OH bond in the
hydroxides of alkali metals is very weak and can easily ionize to form M+ and
OH- ions. Further, the strength of the base increases as the ionization energy
decreases down the group because the bond between metal and oxygen becomes
weaker. This increases the basic strength of the hydroxides accordingly. Thus, NaOH
is a stronger base than LiOH and so on.
Solutions in liquid ammonia
Alkali metals dissolve in liquid ammonia to give deep blue solutions that are
conducting in nature. This happens because the alkali metal atom readily lose the
valence electron in ammonia solution. Both the cation and the electron combine with
ammonia to form ammoniated cation and ammoniated electron.

The ammoniated electron is responsible for the blue color of the solution. The
solution is made conducting in nature by both ammoniated cation and ammoniated
electron.
On standing, the solution slowly liberates hydrogen as:

Hydration of ions
The alkali metal ions are highly hydrated. The smaller the size of the ion, the greater
is the degree of hydration. Thus, Li+ ion gets much more hydrated than Na+ ion which
in turn is more hydrated than K+ion and so on. The extent of hydration decreases
down the group.
As a result of larger hydration of Li+ ion than Na+ ion, the effective size of Li+ion is
more than that of Na+ion. Further the ionic radii in water (called hydrated ionic
radii) decreases in the order:
Li+ > Na+ > K+ > Rb+ > Cs+

As a result, the hydrated Li+ ion being largest ionic size, has the lowest mobility in
water. On the other hand, the hydrated Cs+ ion being smallest in size has the highest
mobility in water.
Reducing nature
Alkali metals are strong reducing agents as indicated by the large negative values of
their reduction potentials. This is so because of the ease with which they lose
electrons. All of them are better reducing agents than hydrogen (E = zero). Therefore,
these metals react with compounds containing acidic hydrogen atoms such as alcohol
and acetylene, liberating hydrogen.