AL Chemistry Section 9 / SHAO / P.

1
S-block Elements

The elements
Variation in physical properties
1. Atomic radius
In both groups, atomic radius increases regularly with atomic number because
1. nuclear charge increases as passing down a group, thus nuclear attraction becomes stronger,
2. electrons are added into the inner shells, shielding effect becomes stronger.
The second factor is more significant than the first one, there is a steady decrease in effective nuclear
charge. The nuclear attraction acting on the valence electrons become weaker on passing down the
group, causing the electron cloud to contract and the atomic radius decreases.

☯ 1. Compare the atomic radius of alkali metals and alkaline earth metals.
The atomic radii of alkali metals are larger than that of alkaline earth metals of the same period
because the increase in nuclear charge has a greater effect than the increase in shielding effect.
Effective nuclear charge increase across the period and the electrons experience a greater
attraction.

II. Ionic radius

On passing down the groups, the ionic radius increases.
☯2. Compare the ionic radii of these metals with their corresponding atomic radii.
Ionic radii of metals are smaller than their corresponding atomic radii. Electrons are removed
on forming cation, the shielding effect decreases. Nuclear charge remain unchanged and thus
effective nuclear charge increases on forming cation and the electrons experience a greater
attraction.

III. Melting point and boiling point

On passing down the groups, effective nuclear charge decreases. The nuclear attraction becomes
weaker, i.e. the metallic bond strength increases and smaller amount of energy is required to
separate the atoms on melting or vaporizing. Therefore, melting point, boiling point, enthalpy of
fusion and vaporization decrease on passing down the group.
☯4 Compare the m.p. and b.p. of alkali metals and alkaline earth metals.
In both groups, the b.p. is higher than the m.p., since similar bonds remain in liquid state as in solid
state, while on vaporization, nearly all metallic bonds must be broken.

IV. Atomic volume

This is governed by the atomic radius and the metallic bond strength.
On passing down the groups, atomic radius increases and metallic bond strength decreases (i.e. atoms
are held less tightly together), therefore atomic volume increases.
 Al Chemistry Section 9 / SHAO / P.2

☯5. Compare the atomic volume of alkali metals and alkaline earth metals.
Atomic volume is the volume occupied by one mole of atoms. It depends on the atomic radius and
the strength of metallic bonding. Atoms of alkaline earth metal have smaller atomic radius than
alkali metal of the same period and they are packed more closely as it has a stronger metallic
bond. Thus alkaline earth metals have a smaller atomic volume.

V. Density
On passing down the group, atomic mass increases and atomic volume increases, but the second
factor is more significant than the first one, thus density decreases on passing down the group.
Atomic volume for alkali metals is the greatest among all groups of metals, its density is the lowest,
in fact, densities of sodium and potassium are less dense than water so that when they reacts with
water, they would float on the surface of the water.
☯6 Compare the density of alkali metals and alkaline earth metals.
Alkali metal has a greater atomic volume than alkaline earth metal of the same period and at the
same time, it is lighter than alkaline earth metal. Thus the density of alkali metals is smaller than
that of alkaline earth metals.

VI Ionization energy
Electronic configuration of alkali and alkaline earth metals are ns1and ns2 respectively. The removal
of second electron of alkali metals and third electrons of alkaline earth metals require exceptionally
high energy.
☯7. There is a huge ‘jump’ from 1st I.P. to 2nd I.P. for alkali metals and from 2nd I.P. to 3rd I.P. for alkaline
earth metals, why ?
The electron being removed in both cases is in inner shell / lower energy level. The electron
experience a much greater attraction from the nucleus and thus has a larger I.P.

On passing down the group, I.P. decreases because effective nuclear charge decreases.
Summary

Groups I and II
Atomic and
m.p. and b.p. ;
ionic radii ;
density and
atomic volume
I.P.
m.p. and b.p. ;
Atomic and density and
ionic radii ; I.P.
atomic volume
 Al Chemistry Section 9 / SHAO / P.3

Variation in chemical properties

Owing to the low value of 1st I.P., alkali metals are relatively more easily to form X+, and the resulting
compound is very stable. The sum of the 1st and 2nd I.P. of alkaline earth metals is not too low, yet the
lattice energy recorded on forming the ionic compounds is large enough for the formation of X2+

I. With air
All tarnish readily in air, forming a film of oxides , showing that they have a great affinity towards
oxygen. Reactivity towards air increases down the group. Sodium and potassium tarnish so readily
that they must be stored under paraffin oil.

While burning in sufficient amount of oxygen (or in air), different metals would give different types
of oxides:

Kind of oxides Elements which form this types of oxide in adequate supply of air
normal oxides O2- Li, Mg, Ca, Sr
peroxides O22- Na, Ba
seperoxides O2- K, Rb, Cs

☯8. Draw the dot and cross diagram for oxide, peroxide and superoxide ion.

.. 2- .. .. 2-

:O: : O .. O :
XX
Oxide ion .X .X Peroxide ion

Owing to the extremely small size of Li+, it is not possible for sufficient number of peroxide ions to
surround the Li+ ion without causing repulsion between the anions and give a stable lattice, therefore
only normal oxide exists. The ionic size of K, Rb and Cs get larger, they are able to form stable
structure with the largest superoxide ion.
☯9. Explain why group IIA metals can form normal oxide only, except barium peroxide ?

Peroxide ion and superoxide ion are relatively unstable than oxide ion. Electron cloud of the ions
will be distorted by the cation if it has strong polarizing power and become less stable.
Ba2+ has the largest ionic size among group IIA and thus has weakest polarizing power and
peroxide ion is stable.
OR
Ionic sizes of group IIA are much smaller than that of group IA. They form unstable peroxide and
superoxide because these large anions will have great repulsion among themselves as they
surround the cation, therefore the compounds are unstable. Ba2+ has the largest size in group IIA
and thus form stable peroxide. [Ba2+ is slightly larger than K+]

In case of Li, Mg, Ca, Sr and Ba, the final products may be a mixture of nitrides, carbonates
together with the oxide.
 Al Chemistry Section 9 / SHAO / P.4

II. With water

Except beryllium, all react readily with cold water to liberate hydrogen, a solution or suspension of
hydroxides is also formed. The rate of reaction increases on passing down the group. Reactivity of
alkali metals towards water is much higher than alkaline earth metals.
2 M + 2 H2O 2 MOH + H2
M + 2 H2O M(OH)2 + H2

Magnesium reacts with hot water and steam to give magnesium hydroxide and magnesium oxide
respectively.
Mg + H2O(g) MgO + H2

III. With non-metals

All combine directly with highly electronegative non-metals, e.g. X2, S, O2, P, and even H2
at suitable temperature.
Li, Mg, Ca, Sr and Ba also combine directly with nitrogen.
Ca + H2 CaH2 calcium hydride
2K+S K2S potassium sulphide
3 Mg + N2 Mg3N2 magnesium nitride

IV. With acid (dil.sulphuric acid or hydrochloric acid)

All react with acid violently or explosively to liberate hydrogen.
2 M + 2 H+ 2 M+ + H2 make sure you know how to write ionic equation
M + 2 H+ M2+ + H2

But reactions between sulphuric acid and Ca, Sr, Ba become less vigorous after the reaction starts due
to the formation of insoluble layer of sulphates.
Ca + H2SO4 CaSO4(s) + H2

The Compounds
Oxides
All are white crystalline solid, ionic and strongly basic in character. They are hydrolysed by water to form
corresponding hydroxides. Degree of hydrolysis increases down the group, since oxide become more
ionic.
O2- + H2O 2 OH-

☯ 10. Compare the basic strength of Na2O and MgO

Na2O is more basic. Na+ has a weaker polarizing power than Mg2+ (as the latter one has a higher
charge/radius ratio / charge density), electron in O2- ion is more available to attack hydrogen in
water molecule. More hydroxide ion is thus formed.
 Al Chemistry Section 9 / SHAO / P.5

Hydrides
It is formed by heating the element in hydrogen gas (at 400℃ or above). All are white crystalline solid,
ionic and strong reducing agents. They are hydrolysed by water to form hydrogen gas and solution or
suspension of hydroxides.
H- + H2O H2 + OH-

During the hydrolysis, hydride ion reduces water to hydrogen while itself is oxidized simultaneously.
Readiness of hydrolysis increases down the group since the hydride is more ionic. And, as expected, the
reaction is more vigorous for alkali metals than for alkaline earth metals.

Chlorides
All are white crystalline solid, soluble in water to form hydrated ion.
NaCl(s) + aq. Na+(aq) + Cl-(aq)
Hydrated sodium and chloride ion
No hydrolysis and thus a neutral solution

But for MgCl2, which is partially ionic, hydrolysed by water to give a slightly acidic solution.
MgCl2(s) + 6 H2O Mg(H2O)62+ + 2 Cl-(aq)
Mg(H2O)62+ + H2O Mg(H2O)5(OH)+ + H3O+
Ionic chlorides are reduced electrically to give metals at the cathode. This is the industrial preparation of
alkali metals and alkaline earth metals.

Other compounds (carbonate, sulphates, etc.)

I. Thermal stability
For a large polarizable anion (e.g. HCO3-, CO32-,NO3-, SO42-), the stability depends on the
polarizing power of the cation. If the cation can distort the electron cloud of the anion so much that
the bonds (e.g. C-O bond in carbonate) is weakened, the bond will be easily broken on heating to
give metallic oxides and gas(es) (CO2 for carbonate).
∆
MgCO3 MgO + CO2
∆
MgSO4 MgO + SO3
∆
2 Mg(NO3)2 2 MgO + 2 NO2 + O2
∆
2 NaNO3 2 NaNO2 + O2
☯ 11. Compare the thermal stability of Na2CO3 and MgCO3.
Na2CO3 is thermally stable because polarizing power of Na+ is weaker than Mg2+ (as the latter one
has a higher charge/radius ratio / charge density), electron cloud of the carbonate ion is much
distorted by Mg2+ that the C – O bond is weakened and thus more easily broken when heated

Polarising power of cation decreases on passing down the group as the size of the cation become
larger. Most group I salts are thermally stable except for those of lithium.
While group II salts are relatively less stable to heat. (Note that only lithium carbonate is thermally
unstable among group I carbonates.).
Extra notes : Some sodium and potassium salts are decomposed when heated :
∆
2 NaNO3 2 NaNO2 + O2
∆
2 NaHCO3 Na2CO3 + CO2 + H2O
 Al Chemistry Section 9 / SHAO / P.6
II. Solubility in water
For an ionic compound to dissolve in water, the crystal lattice must be broken down into its
constituent ions, thus lattice energy must be supplied. At the same time, the ions are hydrated by
water with subsequent liberation of hydration energy. The solubility of an ionic compound can be
regarded as a competition between these two energies. If the hydration energy is greater than the
lattice energy of the compound, the compound can probably dissolve.

Lattice energy depends on the sum of the ionic radii while the hydration energy depend on ionic
radius of the individual ions; both would decrease as size of ions increases. Hydration energy of a
compound is contributed by both the cation and anion.

For a compound with large anion (e.g. carbonate, sulphate, iodide, etc.)
Hydration energy contributed by anion is small, i.e. the hydration energy mainly contributed by the
cation. Thus on passing down the group, hydration energy decrease greatly / tremendously. While
the sum of ionic radii only increase slightly as the size of anion is large, the decrease in lattice
energy is small. Thus, the solubility of the compounds become lower on passing down the group.

Compounds Solubility / x 10-3 mol/dm3 It is normally described as

MgSO4 3600 soluble
CaSO4 11 sparingly soluble
SrSO4 0.62 insoluble
BaSO4 0.009 insoluble
For a small anion (e.g. fluoride and hydroxide)
Lattice energy decrease more rapidly than the hydration energy on passing down the group as the
percentage increase in sum of ionic radii is large while the hydration energy now mainly depends on
the small anion. The change in lattice energy mainly determines the solubility of the salt and this on
passing down the group.

Compounds Solubility / x 10-2 mol/dm3 It is described as

Mg(OH)2 0.020 insoluble
Ca(OH)2 1.5 slightly soluble
Sr(OH)2 3.4 soluble
Ba(OH)2 15 soluble

An increase in charge will increase lattice energy to a greater extent than hydration
energy, thus salts of alkaline earth metals are generally less soluble than that of alkali metals.
Similarly, doubly charged anions give more insoluble compounds.
Compounds Solubility / x10-1 mol/dm3
MgCl2 5.6
CaCl2 5.4
SrCl2 3.5
BaCl2 1.5
 Al Chemistry Section 9 / SHAO / P.7

General characteristics
I Fixed oxidation state
The only possible positive oxidation state shown by the elements is equal to the total number of
electron in the outermost shell. This oxidation state corresponds to the loss of sufficient number of
electrons to achieve the octet configuration ns2np6, thus only forms compounds in which they obtain
the octet configuration.
The loss of more than the valence electron requires too much ionization energy, thus prevents these
metals from showing an oxidation number other than the one equal to their group number.

II. Ability to form complexes

Owing to the lack of underlying (inner) low energy vacant orbital, s-block elements rarely form
complexes. (See Section 11 Transition metals) The cations which form stable complexes normally
carrying a high charge / radius ratio, resulting in larger electrostatic attraction between the central ions
and the ligands.
Group I metal ions cannot form hydrated ions of definite formula in aqueous solution, though they can
by hydrated to certain extent. Lithium ion, which has the smallest size, show certain degree of
hydration in crystal of its salts. The degree of hydration then decreases on passing down the group.
Group II metals ions has higher charge/radius ratio and they have higher tendency to form complexes.

Abnormality of lithium and its compounds among group IA

1 Lithium carbonate and hydroxide are decomposed by heat.
2
Lithium carbonate, hydroxide and fluoride are insoluble in water.
3
Lithium forms only normal oxide when reacting with oxygen.
4
Lithium forms nitride when heated in air.
5 Lithium ion is highly hydrated in water, resulting in lowest mobility.
6 Lithium hydroxide is not a strong base.
7 Almost all lithium salts are hydrated in its crystal lattice.
8
Lithium possesses a very negative E∘(reduction potential), but react more slowly than any other
elements in group IA.
Li(s) Li+(aq)

very negative hydration energy

due to small size of Li+ ion.

Li(g) Li+(g)

Reasons : Exceptional small size of Li+

Forming nitride
 Al Chemistry Section 9 / SHAO / P.8

Born Haber Cycle for the formation of Li3N

Diagonal relationship between magnesium and lithium

1. Both only form normal oxide.

2. Both give nitrides when heating in air.

3. Carbonates, sulphates, hydroxides are decomposed by heat to metallic oxides.

4. Carbonates, hydroxides are insoluble in water.

Reasons: Effective nuclear charge increases on passing along the period but decreases on passing
down the group, so Li+ and Mg2+ have similar effective nuclear charge which in turn affecting its
polarizing power.