Alkali metals

Periodic discussion and general characteristics of

alkali metals:
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 are as follows:
 Electronic
Element Symbol Atomic No.
configuration
Lithium Li 3 [He]2s1

Sodium Na 11 [Ne]3s1

Potassium K 19 [Ar]4s1

Rubidium Rb 37 [Kr]5s1

Cesium Cs 55 [Xe]6s1

Francium Fr 87 [Rn]7s1
GENERAL CHARACTERISTICS OF ALKALI METALS:
i. 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.
ii. 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.
iii. 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.
iv. 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.
v. 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+). Thus,
alkali metals are univalent and form ionic compounds.
vi. 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 colours of the alkali metals can be explained on the basis
of amount of energy absorbed for excitation of the valence electron.
Element Li Na K Rb Cs

Flame
crimson red yellow violet Dark red bluish
colour
vii. Soft metals:
All the alkali metals are soft and can be cut with the help of knife.
Softness of alkali metals is due to weak metallic bonding in them
because of the larger atomic size of the atom. On moving down the
group, metallic bonding weakens and hence softness increases.
viii. 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.

ix. Reducing agents:

Due to low ionization energies alkali metals have larger tendency to loose
their outermost electron and hence behave as strong reducing agent.
Chemical characteristics
1. Action with air
They burn in air imparting characteristic colour. The product varies with the nature
of metal. Lithium forms monoxide and some peroxide. 4Li + O2 ⎯⎯⎯→ 2Li2O
Sodium forms peroxide and some monoxide. 2Na + O2 ⎯⎯⎯→ Na2O2
K, Rb and Cs form superoxides. K + O2 ⎯⎯⎯→ KO2
2. Action with water:
All alkali metals react with water forming corresponding hydroxides and hydrogen
gas.
2Li + 2H2O ⎯⎯⎯→ 2LiOH + H2
2Na + 2H2O ⎯⎯⎯→ 2NaOH + H2
2K + 2H2O ⎯⎯⎯→ 2KOH + H2
3. Action with hydrogen: All alkali metals react with hydrogen at elevated
temperature forming ionic or salt like hydrides of type M+H- . The reactivity
decreases down the group. 2Na + H2 ⎯⎯⎯→ 2NaH Sodium hydride
4. Action with other nonmetals:
All alkali metals react with all halogens, sulphur and phosphorous forming
corresponding halides, sulphides and phosphides.
2M + X2 ⎯⎯⎯→ 2MX
2M + S ⎯⎯⎯→ M2S
3M + P ⎯⎯⎯→ M3P

5. Action with ammonia: All alkali metals dissolve in liquid ammonia

forming ammoniated metal ions and ammoniated electrons.
M ⎯⎯⎯→ M+ + e–
M+ + x NH3 ⎯⎯⎯→ M+ (NH3)x
e– + y NH3 ⎯⎯⎯→ e–(NH3)y
M + (x + y) NH3 ⎯⎯⎯→ M+(NH3)x + e–(NH3)y
ammoniated cation ammoniated electron
The metal is recovered when the solution is evaporated. On long
standing, the solution gives metal amide and hydrogen. The process is
fast in presence of catalyst like Fe, Pt, etc.
2M + 2NH3 ⎯⎯⎯→ 2MNH2+ H2
 Sodium
• Occurrence
The abundance of sodium in Earth’s crust is nearly 2.5%. Sea water is rich
source of sodium along with Potassium.
Chile salt petre (NaNO3), rock salt or common salt (NaCl), Borax
Na2B4O7.10H2O, soda feldspar (NaAlSi3O8) etc. are important minerals of
sodium.
 Extraction of Sodium by Down’s Process
• Principle:
Down’s cell is a special type of cell that is made for extraction of sodium.
During the extraction of sodium metal, following difficulties are seen:
a. Sodium ores like NaCl, Na2CO3 are very stable.
b. The chemical reduction of those sodium salts is not possible since sodium
itself is a good reducing agent.
c. The electrolytic reduction of its aqueous solution is also very difficult
because H+ is reduced faster than Na+ and hence H2 is produced before than
Na.
d. Reducing of its molten salt by electrolysis is also very difficult because the
melting point of NaCl is around 800°C but boiling point of sodium metal is
883°C which can be corrosive for the cell causing the fog of sodium and there
is the chance of short circuit also.
• Hence, to overcome such difficulties, the Down’s cell was brought in the
use. NaCl was mixed with CaCl2 in the ratio of 2:3 by mass which reduces
the working temperature to 600°C. This cell consists of graphite anode &
iron cathode. The cell consists of one inlet through which the electrolyte is
poured into the cell. Then the electricity is passed into the electrodes
which initiate the electrolysis. The chlorine gas collected at anode escapes
through the hood as byproduct and the sodium metal is extracted in the
cathode. Sodium, having low density than its salt, floats and can be easily
collected over kerosene.
• At anode:
Cl–– e– ——–> Cl
2Cl ———>Cl2
• At cathode:
Na++ e– ———> Na
 Advantages of Down’s Process

➢Sodium metal obtained is of high purity (about 99.5%)

➢The starting material, sodium chloride is very cheap.
➢Chlorine is obtained as a valuable by-product.
➢This process is relatively cheaper.
Properties of Sodium

Physical properties
➢Sodium is silvery white soft solid and can be cut out with knife.
➢It is less dense than water. Density of sodium is 0.7gm/cm3
➢It is good conductor of heat and electricity.
Chemical properties of Sodium
i. Action with oxygen
Sodium is silvery white when freshly cut but rapidly tarnished in air due to
the formation of a thin oxide layer on its surface.
4Na + O2 2Na2O
The oxide absorbs moisture and form hydroxide which further absorbs CO2
from air to form sodium carbonate.
Na2O +H2O 2NaOH
2NaOH + CO2 Na2CO3 + H2O
When sodium is heated in air, it burns with golden yellow flame forming
peroxide and some monoxide.
2Na + O2 Δ Na2O2
Contd…
ii. Action with water
Sodium reacts with water vigorously forming sodium hydroxide and
hydrogen gas
2Na + 2H2O 2NaOH + H2

iii. Action with hydrogen

Sodium reacts with hydrogen at elevated temperature forming white
crystalline ionic or salt like hydride.
2Na + H2 Δ 2NaH
sodium hydride
Contd…
iv. Action with other non-metals
Sodium reacts with all halogens, sulphur and phosphorus forming halides,
sulphides and phosphides respectively.
2Na + X2 2NaX
2Na + S Na2S
3Na + P Na3P
v. Action with ammonia
a. It dissolves in ammonia to give blue solution.
b. When sodium is heated with ammonia gas, sodium amide (sodamide) is
formed with the evolution of hydrogen gas.
2Na + 2NH3 Δ 2NaNH2 + H2
Contd…

vi Action with mineral acids

Sodium reacts violently with acids liberating hydrogen gas.
2Na + 2HCl 2NaCl +H2
 Uses of Sodium

➢Sodium as well as sodium amalgam are used as reducing agents in

organic synthesis.
➢It is used in laboratory for Wurtz reaction, Fittig reaction, for detection of
foreign elements in organic compounds by Lassaigne’s method etc.
➢It is used in sodium vapour lamp.
➢It is used as catalyst for the preparation of artificial rubber.
Q. Sodium can not be extracted by electrolysis of aqueous sodium chloride,
why?
Answer
During electrolysis of aqueous sodium chloride, Sodium ion and Hydrogen
ion are formed as cation.
2NaCl Ionization 2Na+ + 2Cl-
H2O Ionization H+ + OH-
Hydrogen ion (H+) & Sodium ion (Na+) being cation moves towards
cathode. The stanard reduction potential of H+ is more than that of Na+. So,
H+ is discharged at cathode in preference than Na+.
At Cathode,
2H+ + 2e- H2
Hence, Hydrogen gas is formed rather than sodium
Physical Properties of Sodium hydroxide

• Sodium hydroxide is a white crystalline solid that melts at 318 °C and with
a boiling point of 1,388 °C .
• It is highly soluble in water and the process is exothermic.
• It is a white crystalline deliquescent solid. A deliquescent solid is a
substance which absorbs moisture from air to such an extent that is
converted to an aqueous form.
 Chemical Properties of Sodium Hydroxide (NaOH)
Precipitation reaction
1. Action with Copper sulphate: Copper sulphate reacts with
sodium hydroxide to form a blue precipitate of copper hydroxide and
sodium sulphate.
CuSO4 + NaOH → Cu(OH)2 + Na2SO4
bluish white
2. Action with Ferrous sulphate solution: Ferrous sulphate reacts
with sodium hydroxide to form a dirty green precipitate of ferrous
hydroxide and sodium sulphate.

2NaOH + FeSO4 → Na2SO4 + Fe(OH)2

dirty green
3.Reaction with Ferric chloride: Ferric chloride reacts with
sodium hydroxide to form a brown precipitate of ferric hydroxide
and sodium chloride.
FeCl3(aq) + 3NaOH(aq)→ Fe(OH)3(s)+ 3NaCl(aq)
Reddish brown
Action with carbon monoxide: Sodium hydroxide does not reacts
with carbon monoxide under normal condition but reacts at high
temperature and pressure to give sodium salt of formic acid which
on acidification gives formic acid.
NaOH +CO → HCOONa
sodium formate

HCOONa +H2SO4→HCOOH + NaHSO4

formic acid(methanoic acid)
 Uses of Sodium Hydroxide
➢ It is used for making soaps and detergents.
➢ It is used for making artificial textile fibers.
➢ It is used in the manufacture of paper.
➢ It is used in purifying bauxite ore from which aluminium metal is
extracted.
Sodium carbonate: Sodium carbonate is the most
important carbonate of metals. It occurs as
anhydrous form, Na2CO3 which is called light ash or
soda ash.
• monohydrate form of sodium carbonate
(Na2CO3.H2O) is called heavy wash.
• Its heptahydrate form (Na2CO37H2O) also exist.
• Its decahydrate form (Na2CO3.10H2O) also exist.
(common washing soda is decahydrate crystalline
solid)
Action of sodium carbonate with carbon dioxide: when
carbon dioxide is passed through aqueous sodium carbonate,
precipitate of sodium bicarbonate is obtained.
Na2CO3 + H2O+ CO2 → 2NaHCO3
( sodium hydrogen carbonate)

Action with water: it is soluble in water due to hydrolysis

and forms sodium hydroxide and carbonic acid. The reaction
is exothermic and resulting solution is alkaline.
Na2CO3 + H2O ⇌ H2CO3+ 2NaOH
Action with Sulphur dioxide: When SO2 gas is passed
into aqueous Na2​CO3​, product formed is Na2​SO3​, the
type of the reaction is

Na2​CO3​+H2​O+SO2→Na2​SO3​+CO2​+H2​O
(sodium sulphite)
Precipitation reaction:
1. Action with calcium chloride
A simple demonstration of how a precipitate is
evidence of a chemical reaction taking place is
performed by mixing solutions of calcium chloride
and sodium carbonate to form the precipitate
calcium carbonate (CaCO3).
CaCl2(aq) + Na2CO3(aq) → CaCO3(s) + 2NaCl(aq)
Action with magnesium Chloride :
MgCl2 (aq) + Na2CO3 (aq) → MgCO3 (s) + 2 NaCl (aq)

Action with magnesium sulphate

Na2CO3 (aq) + MgSO4 (aq) → Na2SO4 (aq) + MgCO3 (s)
Uses of sodium carbonate
1. sodium carbonate is used for the manufacture of
sodium silicate(Na2SiO3) which is called as water
glass(water soluble).
2.It is used in the manufacture of pulp and paper, (rayon)
and soap etc.
3. It is used for softening of hard water because it
precipitates soluble Mg and Ca as carbonate.
4. It is used as laboratory reagent.
5. It is used in food processing, PH moderator and
swimming pool.