UNIT 10 THE s-BLOCK ELEMENTS

The s-block elements are those in which the last electron enters the outermost s-orbital. As the s-
orbital can accommodate only two electrons, two groups (1 & 2) belong to the s-block.
Group 1 consists of the elements: lithium, sodium, potassium, rubidium, caesium and francium.
They are collectively known as the alkali metals because they form hydroxides on reaction with
water which are strongly alkaline in nature. Group 2 consist of beryllium, magnesium, calcium,
strontium, barium and radium. These elements with the exception of beryllium are commonly
known as the alkaline earth metals because their oxides and hydroxides are alkaline in nature and
these metal oxides are found in the earth’s crust. The general electronic configuration of group I
is ns2.

GROUP 1 ELEMENTS (ALKALI METALS)

Electronic Configuration - The general electronic configuration is ns1. The loosely held s-
electron in the outermost valence shell of these elements makes them the most electropositive
metals. They readily lose electron to give monovalent M+ ions.
Atomic and Ionic Radii - The alkali metal atoms have the largest sizes in a particular period of
the periodic table. The atomic and ionic radii of alkali metals increase on moving down the
group i.e., they increase in size while going from Li to Cs. The monovalent ions (M+) are smaller
than the parent atom.
Ionization Enthalpy - The ionization enthalpies of the alkali metals are considerably low and
decrease down the group from Li to Cs. This is because the atomic size increases and the
outermost electron is very well screened from the nuclear charge.
Hydration Enthalpy - The hydration enthalpies of alkali metal ions decrease with increase in
ionic sizes.
Li+> Na+ > K+ > Rb+ > Cs+
PHYSICAL PROPERTIES-

• All the alkali metals are silvery white, soft and light metals.
• Because of the large size, these elements have low density which increases down the
group from Li to Cs. However, potassium is lighter than sodium.
 • The melting and boiling points of the alkali metals are low because they have weak
metallic bonding due to the presence of only a single valence electron in them.
• The alkali metals and their salts impart characteristic colour to an oxidizing flame. This is
because the heat from the flame excites the outermost orbital electron to a higher energy
level. When the excited electron comes back to the ground state, there is emission of
radiation in the visible region of the spectrum.
Metal Li Na K Rb Cs
Colour Crimson Yellow Violet Red Blue red violet
Alkali metals can therefore, be detected by the respective flame tests.
• These elements when irradiated with light, the light energy absorbed may be sufficient to
make an atom lose electron. This property makes caesium and potassium useful as
electrodes in photoelectric cells.

CHEMICAL PROPERTIES-

The alkali metals are highly reactive due to their large size and low ionization enthalpy. The
reactivity of these metals increases down the group.
(i) Reactivity towards air: The alkali metals tarnish in dry air due to the formation of their
oxides which in turn react with moisture to form hydroxides. Lithium forms monoxide, sodium
forms peroxide, the other metals form superoxides. The superoxide O2– ion is stable only in the
presence of large cations such as K, Rb, Cs.

(M = K, Rb, Cs)
Because of their high reactivity towards air and water, alkali metals are normally kept in
kerosene oil.
(ii) Reactivity towards water: The alkali metals react with water to form hydroxide and
dihydrogen.
Lithium reaction with water is less vigorous than that of sodium due to small size and very high
hydration energy of lithium.
(iii) Reactivity towards dihydrogen: The alkali metals react with dihydrogen to form hydrides.
All the alkali metal hydrides are ionic solids with high melting points.

(iv)Reactivity towards halogens: The alkali metals react with halogens to form ionic halides.
M+X–. However, lithium halides are covalent because of the high polarisation capability of
lithium ion (The distortion of electron cloud of the anion by the cation is called polarisation).
(v) Reducing nature: The alkali metals are strong reducing agents as they can easily lose one
electron. Lithium is the most and sodium the least powerful reducing agent. With the small size
of its ion, lithium has the highest hydration enthalpy which accounts for its high negative
electrode potential (Eo) value and its high reducing power.
(vi)Solutions in liquid ammonia: The alkali metals dissolve in liquid ammonia giving deep blue
solutions which are conducting in nature.

The blue colour of the solution is due to the ammoniated electron which absorbs energy in the
visible region of light and thus imparts blue colour to the solution. The solutions are
paramagnetic. In concentrated solution, the blue colour changes to bronze colour and becomes
diamagnetic.

USES -
Lithium metal is used to make useful alloys, for example with lead to make ‘white metal’
bearings for motor engines, with aluminium to make aircraft parts, and with magnesium to make
armour plates. Lithium is also used to make electrochemical cells. Liquid sodium metal is used
as a coolant in fast breeder nuclear reactors. Potassium has a vital role in biological systems.
Potassium chloride is used as a fertilizer. Potassium hydroxide is used in the manufacture of soft
soap. It is also used as an excellent absorbent of carbon dioxide. Caesium is used in devising
photoelectric cells.
GENERAL CHARACTERISTICS OF THE COMPOUNDS OF THE ALKALI METALS

1. Oxides and Hydroxides- On combustion in excess of air, lithium forms mainly the oxide,
Li2O (plus some peroxide Li2O2), sodium forms the peroxide, Na2O2 (and some superoxide
NaO2) whilst potassium, rubidium and caesium form the superoxides, MO2. Formation of
superoxide increases down the group because large anion (superoxide ion) is stabilized by large
cation. through lattice energy effects. These oxides are easily hydrolysed by water to form the
hydroxides

Sodium peroxide is widely used as an oxidising agent in inorganic chemistry.

2. Halides- The alkali metal halides, MX, (X=F, Cl, Br, I) are all high melting, colourless
crystalline solids. The melting and boiling points always follow the trend: fluoride > chloride >
bromide > iodide because as the size of ion increases, internuclear distance increases and force
of attraction decreases. All these halides are soluble in water. The low solubility of LiF in water
is due to its high lattice enthalpy whereas the low solubility of CsI is due to smaller hydration
enthalpy of its two ions.

3. Salts of Oxo-Acids- Oxo-acids are those in which the acidic proton is on a hydroxyl group
with an oxo group attached to the same atom e.g., carbonic acid, H2CO3; sulphuric acid, H2SO4.
The alkali metals form salts with all the oxo-acids. They are generally soluble in water. Their
carbonates (M2CO3) and in most cases the hydrogen carbonates (MHCO3) also are highly stable
to heat.

ANOMALOUS PROPERTIES OF LITHIUM

The anomalous behaviour of lithium is due to the: exceptionally small size its small size, high
polarising power, high ionisation enthalpy and non-availability of d orbitals.
• Lithium is much harder. Its m.pt and b.pt are higher than the other alkali metals.
 • Lithium is strongest reducing agent among all the alkali metals.
• Lithium mainly form covalent compounds.
• On combustion in air it forms mainly monoxide, Li2O
• LiCl is deliquescent and crystallizes as a hydrate, LiCl.2H2O whereas other alkali metal
chlorides do not form hydrates.
• Lithium hydrogen carbonate is not obtained in the solid form while all other elements
form solid hydrogen carbonates.
• Lithium unlike other alkali metals forms no ethynide on reaction with ethyne.
• LiF and Li2O are comparatively much less soluble in water than the corresponding
compounds of other alkali metals.

DIAGONAL RELATIONSHIP (Similarities between Lithium and Magnesium)

The similarity in the properties of definite pairs of diagonally adjacent elements in the second
and third periods of the periodic table is called diagonal relationship.
The similarity between lithium and magnesium arises because of their similar sizes.
• Both lithium and magnesium are harder and lighter than other elements in the respective
groups.
• Lithium and magnesium react slowly with water.
• Their oxides and hydroxides are much less soluble and their hydroxides decompose on
heating.
• Both form a nitride, Li3N and Mg3N2, by direct combination with nitrogen.
• The oxides, Li2O and MgO do not combine with excess oxygen to give any superoxide.
• The carbonates of lithium and magnesium decompose easily on heating to form the
oxides and CO2.
• Solid hydrogen carbonates are not formed by lithium and magnesium.
• Both LiCl and MgCl2 are soluble in ethanol.
• Both LiCl and MgCl2 are deliquescent and crystallize from aqueous solution as hydrates,
LiCl·2H2O and MgCl2·8H2O.
GROUP 2 ELEMENTS (ALKALINE EARTH METALS)

The group 2 elements comprise beryllium, magnesium, calcium, strontium, barium and radium.

Electronic Configuration - Their general electronic configuration may be represented as ns2.

Atomic and Ionic Radii - The atomic and ionic radii of the alkaline earth metals are smaller
than those of the corresponding alkali metals in the same periods. This is due to the increased
nuclear charge in these elements. Within the group, the atomic and ionic radii increase with
increase in atomic number.
Ionization Enthalpies - The alkaline earth metals have low ionization enthalpies due to fairly
large size of the atoms. Since the atomic size increases down the group, their ionization enthalpy
decreases . The first ionisation enthalpies of the alkaline earth metals are higher than those of the
corresponding Group 1 metals. This is due to their small size as compared to the corresponding
alkali metals. Second ionisation enthalpies of the alkaline earth metals are smaller than those of
the corresponding alkali metals.
Hydration Enthalpies - The hydration enthalpies of alkaline earth metal ions decrease with
increase in ionic size down the group.
Be2+> Mg2+ > Ca2+ > Sr2+ > Ba2+
The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions
due to small size of their cation and more positive charge.

PHYSICAL PROPERTIES

• The alkaline earth metals, in general, are silvery white, lustrous and relatively soft but
harder than the alkali metals.
• The melting and boiling points of these metals are higher than the corresponding alkali
metals due to smaller sizes.
• Because of the low ionisation enthalpies, they are strongly electropositive in nature. The
electropositive character increases down the group from Be to Ba.
• Calcium, strontium and barium impart characteristic brick red, crimson and apple green
colours respectively to the flame. In flame the electrons are excited to higher energy levels
 and when they drop back to the ground state, energy is emitted in the form of visible light.
• The electrons in beryllium and magnesium are too strongly bound to get excited by flame.
Hence, these elements do not impart any colour to the flame.
• The alkaline earth metals like those of alkali metals have high electrical and thermal
conductivities which are typical characteristics of metals.

CHEMICAL PROPERTIES
The alkaline earth metals are less reactive than the alkali metals. The reactivity of these elements
increases on going down the group.
(i) Reactivity towards air and water:

➢ Beryllium and magnesium are kinetically inert to oxygen and water because of the
formation of an oxide film on their surface.
➢ Magnesium is more electropositive and burns with dazzling brilliance in air to give MgO
and Mg3N2.

(ii) Reactivity towards the halogens: All the alkaline earth metals combine with halogen at
elevated temperatures forming their halides.

(iii) Reactivity towards hydrogen: All the elements except beryllium combine with hydrogen
upon heating to form their hydrides, MH2.

(iv) Reactivity towards acids: The alkaline earth metals readily react with acids liberating
dihydrogen. M + 2HCl → MCl2 + H2
(v) Reducing nature: Like alkali metals, the alkaline earth metals are strong reducing agents.
However their reducing power is less than those of their corresponding alkali metals as their size
is small and ionization enthalpy is more.
(vi) Solutions in liquid ammonia: Like alkali metals, the alkaline earth metals dissolve in liquid
ammonia to give deep blue-black solutions forming ammoniated ions.
USES -

Copper-beryllium alloys are used in the preparation of high strength springs. Metallic beryllium
is used for making windows of X-ray tubes. Magnesium forms alloys with aluminium, zinc,
manganese and tin. Magnesium-aluminium alloys being light in mass are used in air-craft
construction. Magnesium (powder and ribbon) is used in flash powders and bulbs, incendiary
bombs and signals. A suspension of magnesium hydroxide in water (called milk of magnesia) is
used as antacid in medicine. Magnesium carbonate is an ingredient of toothpaste. Radium salts
are used in radiotherapy, for example, in the treatment of cancer.

GENERAL CHARACTERISTICS OF COMPOUNDS OF THE ALKALINE EARTH

METALS
The alkaline earth metals form compounds which are predominantly ionic but less ionic than the
corresponding compounds of alkali metals. This is due to increased nuclear charge and smaller
size.
(i) Oxides and Hydroxides: The alkaline earth metals burn in oxygen to form the monoxide,
MO. All these oxides except BeO are basic in nature and react with water to form sparingly
soluble hydroxides.
MO + H2O → M(OH)2
The BeO is essentially covalent in nature. BeO is amphoteric in nature. The alkaline earth metal
hydroxides are, however, less basic and less stable than alkali metal hydroxides.
(ii) Halides: Except for beryllium halides, all other halides of alkaline earth metals are ionic in
nature. Beryllium halides are essentially covalent. Beryllium chloride has a chain structure in the
solid state as shown below:

In the vapour phase BeCl2 tends to form a chloro-bridged dimer.

Cl
Cl Be Be Cl
Cl
(iii) Salts of Oxoacids: The alkaline earth metals also form salts of oxoacids. Some of these are:
Carbonates: Carbonates of alkaline earth metals are insoluble in water. The solubility of
carbonates in water decreases as the atomic number of the metal ion increases. All the carbonates
decompose on heating to give carbon dioxide and the oxide. The thermal stability increases with
increasing cationic size because the electropositive character increases.
Sulphates: The sulphates of the alkaline earth metals are all white solids and stable to heat.
BeSO4, and MgSO4 are readily soluble in water; the solubility decreases from CaSO4 to BaSO4.
The greater hydration enthalpies of Be2+ and Mg2+ ions overcome the lattice enthalpy factor and
therefore their sulphates are soluble in water.
Nitrates: The nitrates are made by dissolution of the carbonates in dilute nitric acid.

ANOMALOUS BEHAVIOUR OF BERYLLIUM

The anomalous behaviour of beryllium is due to the: exceptionally small size its small size, high
polarizing power, high ionization enthalpy and non-availability of d orbitals.
➢ Beryllium has exceptionally small atomic and ionic sizes and thus does not compare well
with other members of the group.
➢ Because of high ionization enthalpy and small size it forms compounds which are largely
covalent.
➢ Beryllium does not exhibit coordination number more than four as in its valence shell
there are only four orbitals. The remaining members of the group can have a coordination
number of six by making use of d-orbitals.
➢ The oxide and hydroxide of beryllium, unlike the hydroxides of other elements in the
group, are amphoteric in nature.

DIAGONAL RELATIONSHIP (between Beryllium and Aluminium)

The ionic radius of Be2+ is nearly the same as that of the Al3+ ion. Hence beryllium resembles
aluminium in some ways.

➢ Like aluminium, beryllium is not readily attacked by acids because of the presence of an
oxide film on the surface of the metal.
➢ The chlorides of both beryllium and aluminium have Cl– bridged chloride structure in
vapour phase.
 ➢ Both the chlorides are soluble in organic solvents and are strong Lewis acids. They are
used as Friedel Craft catalysts.
➢ Beryllium and aluminium ions have strong tendency to form complexes, BeF42–, AlF63–.

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