The s block elements

Introduction

 These include the elements in group I and group II of the Periodic Table.
 They are called s block elements because their outermost electrons are being filled in s
sub energy level.

The chemistry of group I elements

 The members of Group I include:

Lithium; Li Potassium; K Caesium; Cs
Sodium; Na Rubidium; Rb Francium; Fr

 The some of the physical properties of the elements are:

Element Outermost 1st I.E 2nd I.E Atomic M.pt B.pt Density S.E.P
E.C (kJ (kJ radius (℃) (℃) (𝒈𝒄𝒎−𝟑 ) 𝑬𝜽
mol-1) mol-1) (nm) (Volts)
Li 2𝑠 2 520 7300 0.155 180 134 0.53 −3.04
Na 3𝑠 2
496 4600 0.190 98 883 0.97 −2.71
K 4𝑠 2 418 3100 0.235 64 774 0.86 −2.92
Rb 5𝑠 2 403 2700 0.248 39 688 1.53 −2.92
Cs 6𝑠 2
374 2400 0.267 28 678 1.87 −3.02
Fr 7𝑠 2

Some general remarks about the elements

 They are called alkali metals since:
(i) their hydroxides dissolve in water to form alkalis.
(ii) elements react with water to form alkalis.
 Their general outermost electronic structure is 𝑛𝑠1 ; where 𝑛 is the principal quantum
number denoting the outermost energy level.

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 All show a fixed oxidation state of +1. This is because loss of the one outermost
s−electron leaves a fully filled and stable outermost sub energy level (i.e. an inert gas
electronic structure is formed).
 As the atomic number increases (i.e. down the group, from lithium to caesium);
(i) the atomic radius increases and the outermost 𝑠 − electrons (valence electrons)
become more distant from the nucleus.
(ii) both first ionization energy and electropositvity decrease.
(iii) reactivity of the elements increases.
 The elements are strongly electropositive due to low first ionization energy as a result
of their large atomic radii. The inner fully filled energy levels effectively shield the
valency electron. As a result, the valency electron is weakly attracted by the nucleus
and is easily lost with formation of positive ions.
 The second ionization energies are much greater than the first ionization energies.
Explanation:
This is because the second electron is being removed from a fully filled and stable sub
energy level. Also, after the removal of the first electron, the number of protons are
more than the number of electrons. Effective nuclear charge increases. The remaining
fewer electrons are strongly attracted by the same number of protons, thus, a
relatively high amount of energy is required to remove an electron
 The melting points and boiling points are generally low.
Explanation
This is because each atom contributes one electron for metallic bonding and their
atomic radii are large. Thus, the elements form weak metallic bonds.
The strength of metallic bond formed decreases from lithium to caesium due to
increase in atomic radii. Thus, the force of attraction between the bonding/delocalized
electrons and the large cations reduces.
 The weak melting bonds in the elements explains why they are soft and can be cut by a
knife.
The other physical properties are:
The elements are:
 shiny (lustrous) when freshly cut.
 good electrical and thermal conductors. This is
due to the presence of delocalised electrons.
 less dense than water and thus, float on
Sodium metal being cut by a water.
knife

 The elements are good reducing agents as a result of being highly electropositive.

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 The standard electrode potential (S.E.P), 𝐸 𝜃 , measures the tendency for the reduction
process to occur.
+ −
A high negative value for S.E.P indicates that the process, 𝑀(𝑠) ⟶ 𝑀 (𝑎𝑞) + 𝑒 , takes
place easily/readily (i.e. indicates that the metal is a good reducing agent/good
electron donor).
Generally, the S.E.P values become more negative down the group, with lithium having
the most negative value of S.E.P.
Lithium forms lithium ion with a very small ionic radius and hence, high charge
density/polarizing power. In aqueous solution, the cation is heavily hydrated and
releases a lot of heat energy. The hydration energy more than offsets its relatively
high enthalpy of atomization and first ionization energy resulting from its very small
atomic radius. Therefore lithium is a better reducing agent than the other group
metals in aqueous solution but a poorer reducing agent when solvation cannot take
place.
Down the group, the magnitude of atomization energy, first ionization energy and
hydration energy decrease. This is due to increase in atomic radius in the same order.
However, the magnitude of atomization energy and first ionization energy decrease
more rapidly than the magnitude of hydration energy, and this makes the S.E.P values
become more negative as the group is descended.
 Lithium, the first member in the Group, behaves differently from the rest of the
other group members and in some respects it closely resembles Group II elements of
the Periodic Table. It is said to have a diagonal relationship with magnesium.
Reason/explanation:
Lithium atom has the smallest atomic radius. The atom forms a cation with a very small
ionic radius and hence, highest charge density/polarizing power. The S.E.P value for
lithium is the most negative.
 Due to their high reactivity, the elements are found in combination with other
elements or radicals. For example, sodium occurs as sodium carbonate, sodium chloride
etc.
 Francium is a radioactive element which occurs in uranium and thorium ores.

Reactions of group I elements

 Because of their large atomic radii, the elements have:

(i) low first ionization energy
(ii) low enthalpy of atomization
The two factors make the elements form stable ions more readily than any other
element and consequently, they are the most reactive metals in the Periodic Table.
Reactivity of the metals increases as the group is descended. This is due to increase in
atomic radius which increases the ease of electron loss in the same order.

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1. Reaction with air
 In damp air, all tarnish (i.e. become dull in appearance) due to formation of oxide layer
on their surfaces.
 Prolong exposure of the elements results into a series of reactions and a carbonate is
formed. K, Rb and Cs readily catch fire on exposure.
 The elements readily burn in air with different flames forming different oxides.
 All form monoxides in limited supply of oxygen.
4M(s) + O2(g) →2M2O(s),
 In excess supply of air;
(i) sodium forms sodium peroxide: 2Na(s) + O2(g) → Na2O2(s).
(ii) potassium, caesium and rubidium form superoxides (or hyperoxides) in addition to
the peroxides.
For example:
2K(s) + O2(g) → K2O2 (s) (peroxide)
K(s) + O2(g) → KO2 (s) (superoxide)

A violent reaction of potassium with air gives a lilac flame

Note
Lithium forms only a normal oxide (monoxide) because its cation has a
very small ionic radius. Thus, the cation cannot surround itself with
sufficient peroxide or superoxide ions to give stable crystal lattices. As
a result only the monoxide exists. The other metals form cations with
larger ionic radii and thus, are able to form stable crystal lattices with
either the peroxide ions or superoxide ions.

2. Reaction with Water

 All liberate hydrogen from cold water and a metal hydroxide is formed in solution.
2M(s) + 2H2O(l) →2MOH(aq) + H2(g)

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 Potassium reacting with water
The vigour of reactivity with water increases down the group. This is due to
electropositivity which increases in the same order. The resultant solutions formed are
alkaline to litmus.
 Lithium reacts slowly with cold water but vigorously with steam to form an oxide and
hydrogen.
2Li(s) + H2O(g) →Li2O(s) + H2(g)

3. Reaction with non-metals

 All the metals react with dry halogens, sulphur, hydrogen and nitrogen when strongly
heated to form corresponding ionic compounds; halides, sulphides, hydrides and
nitrides respectively.
For example: 2𝑁𝑎(𝑠) + 𝐶𝑙2 (𝑔) ⟶ 2𝑁𝑎𝐶𝑙(𝑠)
 Lithium is the only metal that reacts directly with dry nitrogen on strong heating.
6Li + N2 (s) → 2Li3N(s); lithium nitride (white solid)

4. Reaction with hydrogen chloride and ammonia

 All burn in a stream of dry hydrogen chloride and dry ammonia when heated to form
the corresponding ionic compounds; the chlorides and amides.
For example:
2Na(s) + 2HCl(g) → 2NaCl(s) + H2(g)
2Na(s) + 2NH3(g) → 2NaNH2(s) + H2(g)

Compounds of group I elements

 The compounds are generally ionic in character, crystalline solids, stable in air and
soluble in water.
 Compounds of lithium have some covalent character. This is due to the small ionic
radius of lithium ion which gives it high charge density/polarizing power. Hence, the

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 cation greatly polarise the accompanying anions. The other form cations with large ionic
radii and thus, low charge density. This makes the cations not to polarize the
neighbouring anions appreciably.

A. Oxides
 All the oxides are basic and dissolve in cold water to form strongly alkaline solution.
For example:
K2O(s) + H2O(l) →2KOH(aq)
2K2O2(s) + 2H2O(l) →4KOH(aq) + O2(g)
2KO2(s) + 2H2O(l) → 2KOH(aq) + H2O2(aq)+O2(g)
 The peroxides and superoxides are powerful oxidizing agents.
For example, chromium(III) hydroxide can be oxidized to sodium chromate by fusing it
with sodium peroxide.
For example: 2Cr(OH)3(s) + 3Na2O2(s) → 2Na2CrO4(aq) + 2NaOH(aq)+H2O(l)

B. Hydroxides
 All readily dissolve and completely dissociate in water to form strongly alkaline
solutions. A lot of heat is produced during the process.
Heat of solution is negative (i.e. the
process is exothermic).
∆𝐻𝑠𝑜𝑙𝑛 = 𝐿𝑎𝑡𝑡𝑖𝑐𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 + ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦

 The solubility of the hydroxides in water increases from lithium hydroxide to caesium
hydroxide and so does the basic strength of the aqueous solution they form. This is
because of the increase in the ionic character of the hydroxides resulting from the
decrease in the charge density of the cations.
 The hydroxides are deliquescent except, lithium hydroxide. Lithium hydroxide is
slightly soluble in water.
 Aqueous solutions of sodium hydroxide and potassium hydroxide neutralise acids,
evolve ammonia from ammonium salts on warming, precipitate insoluble metal
hydroxides from their salts in aqueous solution and, readily absorb carbon dioxide from
air and react with it to form carbonates (or hydrogencarbonates) and water.

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 For example:
2NaOH(aq)+ CO2(g) → Na2CO3(aq) + H2O(l)
The reaction of sodium hydroxide and potassium hydroxide with carbon dioxide from
air makes:
(i) the alkalis not regarded as primary standards.
(ii) the aqueous solutions of the alkalis for use in volumetric analysis be prepared using
freshly boiled distilled water; which is carbon dioxide free.

Trial Questions
1. Give reasons for the following procedures as used in volumetric analysis/analytical
chemistry. Illustrate your answers with equations where possible.
(a) Sodium hydroxide is not suitable as a primary standard in volumetric analysis.
(b) Aqueous solutions of sodium hydroxide for use in volumetric analysis should be
prepared using freshly boiled distilled water.
2. State two large uses of the hydroxides of group I elements of the Periodic Table.

Manufacture of sodium hydroxide

Sodium hydroxide is obtained by electrolysis of brine (concentrated sodium chloride

solution) in either Castner-Kellner cell or a diaphragm cell. Chlorine and hydrogen are
important bi-products of both methods.

(a) The Castner-Kellner cell

 Brine is electrolyzed in a cell made up of mercury cathode and titanium/graphite as
the anode.
 At the cathode, sodium ions are discharged in preference to hydrogen ions. Thus,
solid sodium is formed.
𝑁𝑎+ (𝑎𝑞) + 𝑒 − ⟶ 𝑁𝑎(𝑠)
 The sodium formed dissolves in the mercury to form am alloy, sodium amalgam which
is reacted with water to form sodium hydroxide with evolution of hydrogen. Liquid
mercury is regenerated for re-use in the cell. Thus, hydrogen is also a product at
the cathode.
𝑁𝑎(𝑠) + 𝐻𝑔(𝑙) ⟶ 𝑁𝑎/𝐻𝑔(𝑙)
2𝑁𝑎/𝐻𝑔(𝑙) + 2𝐻2 𝑂(𝑙) ⟶ 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2 (𝑔) + 2𝐻𝑔(𝑙)
 Solid sodium hydroxide is obtained by careful evaporation to dryness of the
resultant solution.
 At the anode, chloride ions are discharged in preference to the hydroxide ions.
Thus, chlorine is formed at the anode.
2𝐶𝑙 − (𝑎𝑞) ⟶ 𝐶𝑙2 (𝑔) + 𝑒 −
 The setup of the cell is as follows:

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(b) The Diaphragm cell
 Brine is electrolyzed in a cell made up of iron/steel cathode and titanium/graphite
as the anode separated by an asbestos diaphragm.
 At the anode compartment, chloride ions are discharged in preference to the
hydroxide ions. Chlorine gas is formed.
2𝐶𝑙 − (𝑎𝑞) ⟶ 𝐶𝑙2 (𝑔) + 𝑒 −
 The remaining solution seeps/passes through the asbestos diaphragm into the
cathode compartment.
 At the cathode compartment, hydrogen ions are discharged to form hydrogen gas.
2𝐻 + (𝑎𝑞) + 2𝑒 − ⟶ 𝐻2 (𝑔)
 The solution in the cathode compartment contains sodium hydroxide mixed with
sodium chloride as an impurity.
 The resultant solution from the cathode compartment is concentrated by
evaporation so that sodium chloride crystallizes out leaving a concentrated solution
of sodium hydroxide.
 The setup of the cell is as follows:

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 Note:
 Potassium hydroxide can be made by both cells using concentrated potassium
chloride solution in place of brine.
 The diaphragm in the diaphragm cell mechanically separates the anode and the
cathode products since they react as below:
𝐶𝑙2 (𝑔) + 2𝑁𝑎𝑂𝐻(𝑎𝑞) ⟶ 𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙)

C. Carbonates
 All the carbonates are ionic except lithium carbonate which is mainly covalent.
Thus, lithium carbonate decomposes when heated to form lithium oxide and carbon
dioxide. The rest are unaffected by heat.
𝐿𝑖2 𝐶𝑂3 (𝑠) ⟶ 𝐿𝑖2 𝑂(𝑠) + 𝐶𝑂2 (𝑔)
 The most important of the carbonates are sodium carbonate and potassium carbonate.
 Sodium carbonate has the following applications:
(i) Anhydrous sodium carbonate is used as a primary standard in volumetric
analysis. Anhydrous potassium carbonate is deliquescent and cannot be used for
this purpose.
(ii) Hydrated sodium carbonate (washing soda) is used in water treatment. It
precipitates out dissolved calcium and magnesium ions in hard water. Washing
soda also neutralises the pH of water during water treatment.
(iii) It is used in the manufacture of glass, paper, soaps and detergents. Potassium
carbonate can also be used for this purpose.
 On a large scale, sodium carbonate is made by Solvay (ammonia-soda) process. During
the process, insoluble sodium hydrogencarbonate formed is strongly heated to form
anhydrous sodium carbonate.
ℎ𝑒𝑎𝑡
2𝑁𝑎𝐻𝐶𝑂3 (𝑠) → 𝑁𝑎2 𝐶𝑂3 (𝑠) + 𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙)
 Potassium carbonate cannot be obtained by Solvay process because potassium
hydrogencarbonate is too soluble in water to be precipitated.
 The carbonates dissolve in water to form an aqueous solution whose 𝑝𝐻 > 7.
Explanation:
Consider sodium carbonate which is a salt formed from a strong base (sodium
hydroxide) and a weak acid (carbonic acid).
When dissolved in water, the salt dissociates into sodium and carbonate ions. The
carbonate ions hydrolyze in water forming a weak carbonic acid and hydroxide ions.
−
𝐶𝑂32− (𝑎𝑞) + 2𝐻2 𝑂(𝑙) ⇌ H2 CO3 (aq) + 2O𝐻 (aq)
The hydrolysis reaction disturbs the equilibrium, 𝐻2 𝑂(𝑙) ⇌ H+ (aq) + O𝐻− (aq) due to the
removal of hydrogen ions. Thus, more water molecules ionize in order to restore the
equilibrium. The ionization reaction produces an excess of hydroxide ions which make
the resultant solution react alkaline and have a pH above 7.

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 The above hydrolysis reaction explains why:
(i) An aqueous solution of sodium (potassium) carbonate behaves like as alkali in acid-
base titrations.
(ii) Use of aqueous sodium (potassium) carbonate solution to precipitate some insoluble
carbonates gives a basic carbonates instead.
For example:
2𝐶𝑢2+ (𝑎𝑞) + ⏟𝐶𝑂2− −
3 (𝑎𝑞) + 2O𝐻 (aq) ⟶ ⏟ CuC𝑂3 . 𝐶𝑢(𝑂𝐻)2 (𝑠) 𝑜𝑟 Cu2 (OH)2 CO3 (s)
𝑠𝑜𝑑𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑏𝑎𝑠𝑖𝑐 𝑐𝑜𝑝𝑝𝑒𝑟(𝐼𝐼) 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒
(𝑔𝑟𝑒𝑒𝑛 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)

D. Hydrogencarbonates
 Lithium hydrogencarbonate only exists in aqueous state while sodium
hydrogencarbonate and potassium hydrogencarbonate exist in solid state.
 The hydrogencarbonates of sodium and potassium are:
(i) thermally unstable and decompose into the metal carbonate, carbon dioxide and
water on strong heating.
(ii) slightly soluble in water.
 Aqueous solutions of the hydrogencarbonates are alkaline due to hydrolysis.
𝐻𝐶𝑂3− (𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ H2 CO3 (aq) + O𝐻 − (aq)
 However, they are less alkaline than corresponding carbonates. Because of this, normal
carbonates are precipitated by use of sodium (potassium) hydrogencarbonate solution
but not sodium (potassium) carbonate solution, which would form basic carbonates.
𝐶𝑢2+ (𝑎𝑞) + 2𝐻𝐶𝑂−3 (𝑎𝑞) ⟶ CuC𝑂3 + H2 𝑂(𝑙) + CO2 (g)
 Sodium hydrogencarbonate is used as primary standard in volumetric analysis, since it
is stable during storage. It is also used in baking powder.

E. Nitrates
 The nitrates of all the group members exist and are thermally stable.
 However, at very high temperatures, the nitrates melt and decompose to give a nitrite
and oxygen except, lithium nitrate forms lithium monoxide, nitrogen dioxide and oxygen
on strong heating.
For example:
2𝑁𝑎𝑁𝑂3 (𝑠) → 2𝑁𝑎𝑁𝑂2 (𝑠) + 𝑂2 (𝑔)
4𝐿𝑖𝑁𝑂3 (𝑠) → 2𝐿𝑖2 𝑂(𝑠) + 4𝑁𝑂2 (𝑔) + 𝑂2 (𝑔)
 The nitrates of potassium and sodium occur naturally as Chile saltpetre and saltpetre
(nitre) respectively and are purified by fractional crystallization; where the salt with
the least solubility at lower temperatures crystallizes out first as the hot saturated
solution of the salt mixture is cooled slowly.
 Both potassium and sodium nitrates are used as nitrogenous fertilisers and to prepare
nitric acid in the laboratory.

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F. Halides
 All form halides which are ionic except, lithium halides which are covalent.
 Lithium chloride dissolves in organic solvents (such as ethanol or methylbenzene) more
than in pure water. This is due the covalent nature of the chloride.
 The halides have a number of applications which include:
(i) Fused sodium chloride is used to produce sodium, sodium hydroxide, chlorine,
sodium chlorate(I) and chlorate(V) by electrolysis.
(ii) Potassium chloride is used as a fertiliser and a source potassium hydroxide.
(iii) Sodium chloride used in making soap and sodium carbonate.
(iv) Potassium iodide used is in the laboratory to confirm the presence of lead(II)
ions and copper(II) ions. Formation of a bright yellow precipitate confirms
lead(II) ions in solution while formation of a white precipitate in a brown
solution confirms copper(II) ions.
𝑃𝑏 2+ (𝑎𝑞) + 2𝐼 − (𝑎𝑞) ⟶ 𝑃𝑏𝐼2 (𝑠)
⏟
𝑦𝑒𝑙𝑙𝑜𝑤 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
2+ (𝑎𝑞) − (𝑎𝑞)
2𝐶𝑢 + 4𝐼 ⟶ 𝐶𝑢2 𝐼2 (𝑠)
⏟ + 𝐼⏟
2 (𝑎𝑞)
𝑤ℎ𝑖𝑡𝑒 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑏𝑟𝑜𝑤𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(v) Potassium iodide is also used to increase the solubility of iodine in pure water
during volumetric analysis.
The increased solubility of iodine in aqueous potassium iodide is due to the
reaction between iodide ions (from potassium iodide) and iodine molecules to
form triiodide ions; which are soluble in water.
𝐼 − (𝑎𝑞) + 𝐼2 (𝑠)⇌ 𝐼3− (𝑎𝑞)
The low solubility of iodine in pure water is because iodine molecules do not
react with water molecules. Also, iodine molecules are non-polar with weak van
der Waals forces and thus, do not form bonds with water molecules which are
polar and having strong hydrogen bonds.
(vi) Potassium bromide is used as anticonvulsant and a sedative.

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The chemistry of group II elements

Introduction
 The groups II elements include beryllium (Be), magnesium (Mg), calcium (Ca), strontium
(Sr), barium (Ba) and radium (Ra).

Beryllium Magnesium Calcium

Strontium Barium

 Radium is rare because it is radioactive.

 They are metals and are referred to as alkaline–earth metals because their oxides are
alkaline (that is, dissolve in water to form alkaline solutions) and their salts (sulphates,
chlorides and carbonates) are wide spread on the Earth’s crust.

Some of the physical properties of Group II elements

Element Outermost Atomic M.pt(℃) B.pt S.E.P Ionisation energy
EC radius (℃) (Volts) 1st 2nd 3rd
(nm)
Be 2𝑠 2
0.112 1280 2770 −1.85 900 1800 14800
Mg 3𝑠 2
0.160 650 1110 −2.37 740 1450 7730
Ca 4𝑠 2
0.197 840 1440 −2.87 590 1150 4910
Sr 5𝑠 2
0.215 768 1380 −2.89 550 1060 4300
Ba 6𝑠 2
0.221 714 1640 −2.91 500 970
Ra 7𝑠 2 −2.92

Some general remarks about the elements

 Their general outermost electronic structure is 𝑛𝑠 2 .
 All show a fixed oxidation state of +2. This is because the loss of the two outermost
s−electrons leaves an outermost sub energy level which is fully filled and stable (i.e. an
inert gas electronic structure is formed).

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 The elements never form 𝑀3+ ions because the third ionization is very high, since the
third electron is being removed from a fully filled and energetically stable sub energy
level. Also, the increased effective nuclear charge strongly attracts and holds the
remaining few electrons.
 The formation of 𝑀2+ ions by the elements is energetically favourable. This is because
the inner fully filled energy levels of electrons effectively shield the outermost 𝑛𝑠 2
electrons from the nuclear attraction. Thus, outermost 𝑛𝑠 2 electrons are weakly
attracted by the nucleus and are easily lost.
 As the atomic number increases (i.e. down the group);
(iv) The atomic radius increases and the outermost 𝑠 − electrons (valence electrons)
become more distant from the nucleus.
(v) Both first and second ionization energies decrease. The second ionisation energy is
much higher than the first ionisation energy because after the removal of the
first electron, the number of protons become more than the number of electrons.
Effective nuclear charge increases. The remaining fewer electrons are strongly
attracted by the same number of protons, thus, a relatively high amount of energy
is required to remove an electron.
As compared to group I metals, the first ionisation energies of group II metals are
much higher. This is because group II metals have relatively smaller atomic radii
than the corresponding alkali metals.
(vi) Electrode potential becomes more negative.
(vii) Reactivity of the elements increases.
 The elements reactive by reducing. They less reactive (reductive) than group I
elements. This is because of their much smaller atomic radii which makes both
ionization and atomization energies so high.
 The group II elements are metals with giant metallic structures. Their atoms are held
by strong metallic bonds. A lot of heat energy is required to break the strong bonds.
This makes their melting and boiling points high.
 Their densities, melting point and boiling point are much higher than those of the
corresponding group I elements. This is because:
(i) Alkaline-Earth metals use two electrons per atom in forming metallic bonds while
group I elements use only one electron per atom for metallic bond formation.
(ii) Alkaline-Earth metals have much smaller atomic radii than their corresponding
elements in group I, as a result their atoms are closely packed together in the
lattices.
The above two factors make the metallic bonds in group II elements much stronger
than those in group I elements.
 On descending the group, the melting point, boiling point and hardness of alkaline-earth
metals decrease.

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 This is because as the atomic radius down the group, the bonding electrons get further
from the attracting nucleus. Therefore the atoms will be less strongly held together as
the group is descended (i.e. metallic bond strength decreases down the group). The
melting point of magnesium is lower than that of calcium. This is because the two
elements adopt different structures/ different crystal structures. Magnesium has
hexagonal close packed arrangement while calcium has a body centred cubic
arrangement
Alternatively:
As the group is descended, the cation radius increases. The charge density of the
cations decreases in the same order and hence, the bonding/valence electrons become
less strongly attracted. Strength of the metallic bonds formed decreases and hence,
melting point decreases down the group. The melting point of magnesium is lower than
that of calcium. This is because the two elements adopt different structures.

 All the elements are soft and can be cut by a knife. This is because of weak metallic
bonds in their structures.
 The metals are good conductors of heat and electricity. This is due to the presence of
delocalized electrons. Conductivity increases as the group is descended from beryllium
to barium. This is due to increase in atomic radii in the same order which makes the
outermost electrons to be weakly attracted by the nucleus and hence, easily
delocalized.
 Beryllium differs considerably in its chemistry from the rest of the other elements
and resembles aluminium.
Reason/explanation:
Beryllium atom has a small atomic radius. The atom forms a cation with a very small
ionic radius and high charge density and hence high polarizing power.

 The standard electrode potential values (𝐸 𝜃 ) become more negative as the group is
descended. (Refer to the previous notes on alkali metals for explanation).
 All are highly reactive and are thus, never found in a free state in nature. On a large
scale, the metals are obtained by electrolysis of the molten chlorides.

Chemical properties of Group II Elements

1. Reaction with air
All metals:
(a) tarnish in air forming a film of oxide, which later forms hydroxide and carbonate on
prolonged exposure. This makes them lose the shiny appearance.
(b) burn brilliantly when heated in air to from an oxide along with some nitride.

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 M(s) + O2(g) → 2MO(s); 3M(s) + N2(g) → M3N2(s)
For example;
Ca(s) + O2(g) → 2CaO(s); 3Ca(s) + N2(g) → Ca3N2(s)
If the product is made damp and warmed, ammonia is evolved.
For example: Ca3N2(s) + 6H2O(l) → 3Ca(OH)2(aq) + 2NH3(g)
The oxides sparingly dissolve in water to give alkaline solutions.
For example: CaO(s) + H2O(l) → Ca(OH)2(aq)
Question:
Reactivity of the elements increases down the group from beryllium to barium. Explain
this observation.

2. Reaction with water

The reactivity with water is not as vigorous as it is with alkali metals. It occurs at
different rates depending on the conditions.
Beryllium is unaffected by water at all conditions.
Clean magnesium reacts with cold water slowly forming magnesium hydroxide and hydrogen.
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g)
However, strongly heated magnesium burns brilliantly in steam to give its oxide and
hydrogen gas.
Mg(s) + H2O(g) → MgO(s) + H2(g)
Calcium, strontium and barium react with cold water to form a metal hydroxide in solution
and hydrogen gas is evolved.
M(s) + 2H2O(l) → M(OH)2(aq) + H2(g); 𝑀 = 𝐶𝑎; 𝑆𝑟 𝑜𝑟 𝐵𝑎
Reactivity increases down the group.
This is because the solubility of hydroxide formed increases in the same order and the
metals became more reducing down the group (atomic radius increases down the group).

3. Reaction with Acids

(a) With dilute hydrochloric acid and dilute sulphuric acid
All the metals liberate hydrogen from dilute hydrochloric and dilute sulphuric acids
forming the corresponding salts in solution.
𝑀(𝑠) + 2𝐻 + (𝑎𝑞) ⟶ 𝑀2+ (𝑎𝑞) + 𝐻2 (𝑔);
With beryllium the reaction takes place on warming while others react vigorously in the
cold/at room temperature.
The reaction of calcium, strontium and barium with dilute sulphuric acid occurs for a short
time and stops. This is because the sulphate formed in each case is insoluble and forms a
coating on the metal. This prevents further contact between the metal and the acid for
the reaction to progress.
M(s) + H2SO4(aq) → MSO4(s) + H2(g); 𝑀 = 𝐶𝑎; 𝑆𝑟 𝑜𝑟 𝐵𝑎

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(b) With concentrated sulphuric acid
All are oxidized by hot concentrated sulphuric acid to their respective metal sulphates in
solution. The acid is reduced to sulphur dioxide gas and water.
M(s) + 2H2SO4(l) → MSO4(aq) +2H2O(l)+ SO2(g)
The rate of the reaction decreases down the group due decrease in the solubility of the
sulphates being formed.
(c) With nitric acid
(i) Very dilute nitric acid has no effect on beryllium, strontium, and barium but reacts
with magnesium and calcium slowly at room temperature to give some hydrogen.
For example: Mg(s) + 2H+ (aq) → Mg2+(aq) + H2(g)
(ii) Concentrated nitric acid renders beryllium passive.
The rest of the elements are oxidized by hot concentrated nitric acid to their
respective nitrates in solution. The acid is reduced to oxides of nitrogen and water.
For example:
3Mg(s) + 8HNO3(aq) →3Mg(NO3)2 + 4H2O(l) + 2NO(g)
Mg(s)+ 4HNO3(aq) → Mg(NO3)2 + 2H2O(l) + 2NO2(g)

4. Reaction with aqueous alkalis

Beryllium being amphoteric, reacts with hot concentrated sodium (potassium) hydroxide
solution to evolved hydrogen gas and beryllate ions are left in solution
Be(s) + 2𝑂𝐻 − (aq) + 2H2O(l) → Be(OH)2−4 (aq) + H2(g)
The rest do not react with alkalis at all conditions.

5. Reaction with non-metals

All the metals react when heated with dry halogen (chlorine or bromine), sulphur,
phosphorus and carbon to form the corresponding compounds. Except beryllium, the rest
react directly when strongly with dry hydrogen under pressure to form ionic hydrides.
M(s) + X2(g) → MX2(s); (X= Cl or Br) M(s) + S(g) → MS(s)
3M(s) + 2P(s) → 𝑀3 𝑃2(s) M(s) + 2C(s) → MC2(s); M= Mg, Ca, Sr or Ba
2Be(s) + C(s) → Be2C(s)
Calcium carbide yields ethyne on hydrolysis with water while beryllium carbide gives
methane on the same treatment.
Note
 The calcium carbide can also be obtained by heating the oxide with carbon (coke) at
20000 𝐶
very high temperatures. 𝐶𝑎𝑂(𝑠) + 3𝐶(𝑠) → 𝐶𝑎𝐶2 (𝑠) + 𝐶𝑂(𝑔)
 Hydrolysis of beryllium carbide proceeds faster in dilute acids and is more rapid in
hot concentrated solutions of alkalis.
Be2C(s) + 4𝐻 + (𝑎𝑞) → 2𝐵𝑒 2+ (aq) + CH4(g)
Be2C(s) + 4𝑂𝐻 − (𝑎𝑞) +4H2O(l) → 2Be(OH)2− 4 (aq) + CH4(g)

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Uses of group II elements
Group II elements of the Periodic Table have a wide range of applications which include:
Element Use(s)
Beryllium  Making containers for uranium-238 since it does not absorb neutrons
and therefore, does not become radioactive
 As an alloying agent when low density is a primary requirement
 Making windows for X-ray tubes since they can easily be penetrated
by X-rays
Magnesium  Make alloys e.g. duralumin and magnalium
 Sacrificial anode to prevent iron from rusting
 In flares and distress signals due to its intense white light it forms
when burning
 Source of light in photography
 Extraction of titanium, chromium
Calcium  In extraction of certain elements from their stable compounds for
example chromium from chromium(III) oxide.
Strontium  In fire works
 Used in producing ferrite magnets and refining zinc
Barium  Often used for spark-plug electrodes and in vacuum tubes as a drying
and oxygen-removing agent.

Compounds of Group II Elements

The compounds of alkaline-earth metals are white and ionic. Those of beryllium have
considerably covalent character.
The covalent nature of most of the compounds of beryllium is brought about by the fact
that beryllium ion has small ionic radius and this gives the cation a high charge density and
hence, high polarising power.
The ionic character in the compounds increases as the group is descended. This is due to
increase in the ionic radius of the metal ions, M2+ (where M is group II metal).
The compounds of group II elements are less ionic, less soluble, less stable to heat
compared to those of corresponding group I members.

A. Hydrides
 The hydrides are ionic solids except beryllium hydride and magnesium hydride which
are both covalent.
 Beryllium hydride is made by reacting beryllium chloride with lithium
tetrahydroaluminate(III) (or simply lithium aluminium hydride), 𝐿𝑖𝐴𝑙𝐻4 .
2𝐵𝑒𝐶𝑙2 (𝑠) + 𝐿𝑖𝐴𝑙𝐻4 (𝑠) ⟶ 2𝐵𝑒𝐻2 (𝑠) + 𝐿𝑖𝐶𝑙(𝑠) + 𝐴𝑙𝐶𝑙3 (𝑠)
 The hydrides react with water to form a metal hydroxide in solution with evolution of
hydrogen gas.

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 𝑀𝐻2 (𝑠) + 2𝐻2 𝑂(𝑙) ⟶ 𝑀(𝑂𝐻)2 (𝑎𝑞) + 𝐻2 (𝑔)

B. Oxides
 All the elements form normal oxides of the general formula MO.
 However, strontium and barium form peroxides when burnt in excess. This is because
their cations are have larger ionic radii and this allows formation of stable lattices with
the peroxide ions. The peroxides have the general MO2 and contain the anion 𝑂22− .
 The normal oxides can be obtained in the following ways:
(i) Burning the metals directly in air (oxygen).
(ii) Heating the metal hydroxide, carbonate or nitrate strongly in an open vessel to
allow the corresponding gases to escape.
Mg(OH)2(s) → MgO(s) + H2O(g); MgCO3 (s) → MgO(s) + CO2(g)
2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g)
Note:
Barium carbonate requires very high temperatures to decompose thus, its oxide is made
by heating its nitrate.
 All the oxides are white crystalline solids.
 Beryllium oxide is partially covalent and is amphoteric while the rest are ionic and
basic.

Reactions of the oxides

 Beryllium oxide is insoluble in water (due to its high covalent character); the rest react
with water to form the corresponding hydroxide in solution. A lot of heat is evolved.
𝑀𝑂(𝑠) + 𝐻2 𝑂(𝑙) ⟶ 𝑀(𝑂𝐻)2 (𝑎𝑞)
 The peroxides of barium (BaO2) and strontium (SrO2) dissolve in water forming the
corresponding hydroxides and hydrogen peroxide.
For example: BaO2(s) + 2H2O(l) →Ba(OH)2(aq) + H2O(aq)
 Barium peroxide reacts dilute sulphuric acid at 0℃ to form hydrogen peroxide in
addition to barium sulphate. This reaction is used in the lab preparation of hydrogen
peroxide.
BaO2(s) + H2SO4(aq) →BaSO4(s) + H2O2(aq)
 The normal oxides of group II elements also react with heated carbon to form
carbides. The most important and common carbide is calcium carbide.
 The basic oxides react with acidic oxides such as carbon dioxide, sulphur trioxide,
silicon dioxide and phosphorus(V) oxide to form the corresponding salts on heating.
For example: SiO2(g) +CaO(s) → CaSiO3(s/l)

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C. Hydroxides, M(OH)2
 All the hydroxides are white solids prepared by precipitation method.
Precipitation method involves adding aqueous sodium hydroxide solution to an aqueous
solution of the soluble salt of the metal.
𝑀2+ (𝑎𝑞) + 2𝑂𝐻 − (𝑎𝑞) ⟶ 𝑀(𝑂𝐻)2 (𝑠)
 Beryllium hydroxide is essentially covalent and amphoteric. The rest are ionic and
basic.
The amphoteric nature of beryllium hydroxide can be illustrated as follows:
As an acid: 𝐵𝑒(𝑂𝐻)2 (𝑠) + 2𝑂𝐻 − (𝑎𝑞) ⟶ 𝐵𝑒(𝑂𝐻)2−
4 (𝑎𝑞)
+ 2+
As a base: Be(OH)2(s) + 2H (aq) →Be (aq) + 2H2O(l).
Thus, the hydroxide resembles aluminium hydroxide, in this respect.
 At very high temperatures, the hydroxides decompose to give metal oxides and water
vapour.
M(OH)2(s) →MO(s) + 2H2O(g)
Question:
Explain why hydroxides of group II metals are decomposed by heat whereas
hydroxides of group I metals are not.

 Solubility of the hydroxides increases down the group; beryllium hydroxide is insoluble
in water and barium hydroxide is sparingly soluble/fairly soluble in water.
Hydroxide Be(OH)2 Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2
Solubility (g/100g Insoluble 0.002 0.15 0.9 4.0
of water at 20oC)
Trend:
The solubility of the hydroxides increases in the order:
Be(OH)2< Mg(OH)2 < Ca(OH)2 < Sr (OH)2 <Ba(OH)2
Explanation:
Beryllium hydroxide is covalent and this makes it insoluble in water.
From beryllium hydroxide to barium hydroxide, the charge on the cation remains the
same but the radius increases. Thus, both lattice energy and hydration energy
decrease in the same order. But the lattice energy decreases more rapidly than the
hydration energy. This makes the heat of solution to become more negative from
Be(OH)2 to Ba(OH)2 and hence, solubility increases.
The solubility also increases from Be(OH)2 to Ba(OH)2 due decrease in the charge
density (polarizing power) of the cation from beryllium ion to barium ion. This makes
the hydroxides to become more ionic form Be(OH)2 to Ba(OH)2.

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 Note:
The hydroxides of group II metals are much less soluble in water the corresponding
hydroxides of group I metals. Thus, the hydroxides of group II metals are less basic
than those of group I elements.

Uses of the hydroxides of group II elements

 Calcium hydroxide is the most important and has the following uses:
 To remove acidic gases in industries and treating acidic soils.
 Softening water and production of ammonia.
 Making bleaching powder (e.g. calcium hypochlorite), sodium hydroxide, sodium
carbonate, mortar and calcium hydrogensulphite used in paper industries.
 Refining sugar (sucrose); strontium hydroxide can also be used for this purpose.
 Magnesium hydroxide is to make indigestion tablets since magnesium is non-toxic.

D. Carbonates, MCO3 and hydrogencarbonate, M(HCO3)2

 All form carbonates of the general formula MCO3.
 The carbonates are insoluble in water and thus, are prepared by precipitation method.
Use of aqueous sodium hydrogencarbonate is preferred to aqueous sodium carbonate
during the precipitation process.
For example:
4𝑀𝑔2+ (𝑎𝑞) + ⏟
3𝐶𝑂2− −
3 (𝑎𝑞) + 2O𝐻 (aq) + 4𝐻2 𝑂(𝑙) ⟶ ⏟
3MgC𝑂3 . 𝑀𝑔(𝑂𝐻)2 . 4𝐻2 𝑂(𝑠)
𝑠𝑜𝑑𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑏𝑎𝑠𝑖𝑐 𝑚𝑎𝑔𝑛𝑒𝑠𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒
(𝑤ℎ𝑖𝑡𝑒 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)
Or 2𝑀𝑔2+ (𝑎𝑞) + ⏟
𝐶𝑂2− −
3 (𝑎𝑞) + 2O𝐻 (aq) ⟶ ⏟
MgC𝑂3 . 𝑀𝑔(𝑂𝐻)2 (𝑠)
𝑠𝑜𝑑𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑏𝑎𝑠𝑖𝑐 𝑚𝑎𝑔𝑛𝑒𝑠𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒
(𝑤ℎ𝑖𝑡𝑒 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)
𝑀𝑔2+ (𝑎𝑞) + 2⏟𝐻𝐶𝑂− 3 (𝑎𝑞) ⟶ MgC𝑂3 (𝑠)
⏟ + 𝐻2 𝑂(𝑠) + 𝐶𝑂2 (𝑔)
𝑠𝑜𝑑𝑖𝑢𝑚 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒 𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑎𝑔𝑛𝑒𝑠𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑤ℎ𝑖𝑡𝑒 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)

 All carbonates are thermally unstable (i.e. decompose on heating).

MCO3(aq)→ 𝑀𝑂(𝑠)
⏟ + CO2(g)
𝑟𝑒𝑠𝑖𝑑𝑢𝑒
 The decomposition temperature increases as the from beryllium carbonate to barium
carbonate.
Carbonate BeCO3 MgCO3 CaCO3 SrCO3 BaCO3
Decomposition temperature 25 540 900 1290 1360

Explanation:
Beryllium carbonate is thermally unstable and decomposes at room temperature. This is
because beryllium ion has a very small ionic radius. Thus, the cation has a high charge
density and hence, high polarizing power. Beryllium ion greatly polarizes the electron
cloud of the carbonate ion making the carbonate covalent and thermally unstable.

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 As the group is descended, the radius of the cation increases but the cationic charge
remains the same. The charge density and hence, the polarising power of the cations
decrease. The ability of the cation to polarize the carbonate ions decreases in the
same order. This makes the ionic character and hence, thermal stability of the
carbonates to increase from beryllium carbonate to barium carbonate.
 The hydrogencarbonates only exist in aqueous solution and are very unstable.
Both magnesium hydrogencarbonate and calcium hydrogencarbonate cause temporary
hardness of water and can be decomposed by boiling of water. This sets water free of
hardness.
𝑏𝑜𝑖𝑙
For example: Ca(HCO3)2(aq) → CaCO3(s) + CO2(g) + H2O(l)

Uses of the carbonates of group II elements

 Calcium carbonate is used in Solvay process (ammonia-soda process), as flux in the iron
and steel industry, in glass industry, in neutralising acidic soils, in making quicklime,
cement, tiles, laboratory mortar and pestle.
 CaCO3.MgCO3 is used as building stones.

E. Nitrates, M(NO3)2
 All the elements form nitrates.
 The nitrates are prepared in the laboratory by action of dilute nitric acid on either the
metal oxide, hydroxide or carbonate and then crystallising the resultant hot saturated
solution by cooling.
 All the nitrates decompose on strong heating to give metal oxide, nitrogen dioxide and
oxygen.
2M(NO3)2(s) → 2MO(s)+ 4NO2(g) +O2(l)

Uses of the nitrates of group II elements

 The nitrates are used as fertilisers, for example, calcium nitrate mixed with calcium
oxide.
 They are also used in fireworks for example, barium nitrate gives a green flame and
strontium nitrate gives a crimson flame.
 An aqueous solution of barium nitrate acidified with dilute nitric acid is used in the
detection and identification of sulphate ions in solution.

F. Chlorides, MCl2.
 Anhydrous chloride is obtained by heating the metal in a current of dry chlorine or dry
hydrogen chloride.
For example: Mg(s) + Cl2 (g) → MgCl2(s) ; Mg(s) + 2HCl(g) → MgCl2(s)+ H2(g)

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 Anhydrous beryllium chloride is a covalent polymeric solid while the rest are
predominantly ionic. This is because charge density and hence, the polarizing power of
the cations decrease down the group. This can be seen in the melting points of the
chlorides.
Chloride BeCl2 MgCl2 CaCl2 SrCl2 BaCl2
o
M.pt ( C) 405 708 722 873 962

The structure of polymerized beryllium chloride is as follows:

 Hydrated chlorides can be made by reacting the metal, its oxide, hydroxide or
carbonate with dilute hydrochloric acid and carefully evaporating the resultant solution
to dryness.
𝑀𝑂(𝑠) + 2𝐻𝐶𝑙(𝑎𝑞) ⟶ 𝑀𝐶𝑙2 (𝑎𝑞) + 𝐻2 𝑂(𝑙)
For example, the chloride of magnesium can be obtained as MgCl2. 6H2O.
 When the hydrated chlorides of magnesium and calcium are heated, some hydrolysis
takes place to give basic chlorides and evolve hydrogen chloride gas. Strong heating
causes the formation of an oxide.
For example:
𝑔𝑒𝑛𝑡𝑙𝑒 ℎ𝑒𝑎𝑡𝑖𝑛𝑔
𝑀𝑔𝐶𝑙2 . 6𝐻2 𝑂(𝑠) → 𝑀𝑔(𝑂𝐻)𝐶𝑙(𝑠) + 𝐻𝐶𝑙(𝑔) + 5𝐻2 𝑂(𝑙)
𝑠𝑡𝑟𝑜𝑛𝑔 ℎ𝑒𝑎𝑡𝑖𝑛𝑔
𝑀𝑔(𝑂𝐻)𝐶𝑙(𝑠) → 𝑀𝑔𝑂(𝑠) + 𝐻𝐶𝑙(𝑔)
Hydrated calcium chloride behaves in a similar way but is less hydrolysed compared to
hydrated magnesium chloride.
 The chlorides of beryllium and magnesium hydrolyse in water forming acidic solutions.
The rest are resistant to hydrolysis since they are ionic. In fact, beryllium chloride
fumes readily in moist air due to evolution of hydrogen chloride gas.
𝐵𝑒𝐶𝑙2 (𝑠) + 2𝐻2 𝑂(𝑠) ⟶ 𝐵𝑒(𝑂𝐻)2 (𝑠) + 2𝐻𝐶𝑙(𝑔)
 Beryllium chloride readily dissolves in the organic solvents (such as ethanol) and this
further confirms its covalent character.
 In vapour phases, beryllium chloride dimerises to form Be2Cl4.

Uses of the chlorides of group II elements

 Anhydrous calcium chloride is used as a drying agent.
 Barium chloride solution acidified with dilute hydrochloric is used confirm the presence
of sulphate ions in aqueous solution.
 Fused chlorides are sources of a number of metals.

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G. Sulphates, MSO4.
 The sulphates of group II metals occur naturally except, beryllium sulphate; for
example, CaSO4.2H2O (gypsum in soils, rocks and tap water) and MgSO4.7H2O (in
Epsom salt in tap water).
 BeSO4 and MgSO4 are prepared in the laboratory by reacting the metal, oxide,
hydroxide or carbonate with dilute sulphuric acid.
For example: 𝐵𝑒(𝑠) + ⏟
𝐻2 𝑆𝑂4 (𝑎𝑞) ⟶ 𝐵𝑒𝑆𝑂4 (𝑎𝑞) + 𝐻2 𝑂(𝑔)
(𝑤𝑎𝑟𝑚)
 CaSO4, SrSO4 and BaSO4 are insoluble in water and are prepared by precipitation
method.
For example, barium sulphate can be made by adding a solution of a soluble sulphate or
dilute sulphuric acid to an aqueous solution of a soluble salt of barium.
Ba2+(aq) + SO42-(aq)→ BaSO4(s)
 The solubility of sulphates in water decreases down the group.
(BeSO4 and MgSO4 are very soluble; CaSO4 is only sparingly soluble and the rest are
insoluble in water)
Sulphate BeSO4 MgSO4 CaSO4 SrSO4 BaSO4
Solubility (g/100g 43.00 33.50 0.18 0.10 0.0024
of water at 25oC)

Explanation:
This is because both the lattice energy and hydration energy decrease from BeSO4 to
BaSO4.
Lattice energy of the sulphates decreases less rapidly down the group since the radius
of the anion is so large compared to the radius of the cation. Thus, the increase in the
radius of the cations does not greatly affect the lattice energy. However, the
hydration energy of the sulphates of group II elements decreases more rapidly down
the group due to increase in the cationic radius.
This makes the heat of solution become less exothermic down the group and thus, the
solubility of the sulphates decreases down the group.
 The solubilities of their carbonates, oxalates (ethanedioates) and chromates vary in a
similar way as that of the sulphates. This is because these anions are large compared
to the constituent cations. Thus, the effect of the radius of the cations on the lattice
energy of such salts can be regarded as insignificant and ignored.

Note:
Because both barium sulphate and barium chromate have low solubility in water, barium ions
can be identified by precipitating it as barium sulphate or barium chromate.
𝐵𝑎2+ (𝑎𝑞) + 𝑆𝑂42− (𝑎𝑞) ⟶ ⏟
𝐵𝑎𝑆𝑂4 (𝑠) ; 𝐵𝑎2+ (𝑎𝑞) + 𝐶𝑟𝑂42− (𝑎𝑞) ⟶ ⏟ 𝐵𝑎𝐶𝑟𝑂4 (𝑠)
𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡 𝑦𝑒𝑙𝑙𝑜𝑤 𝑝𝑝𝑡

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Uses of sulphates of group (II) elements
 The sulphates have a number of applications. These include:
(i) Aqueous solution of magnesium sulphate is used in the lab to distinguish between
carbonate and hydrogencarbonate ions in solution.
Observations:
 Immediate white precipitate confirms carbonate ions in solution.
𝑀𝑔2+ (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞) ⟶ 𝑀𝑔𝐶𝑂3 (𝑠)
 No observable change at room temperature (or white precipitate on
boiling/heating) confirms hydrogencarbonate ions in solution.
𝑏𝑜𝑖𝑙
𝑀𝑔2+ (𝑎𝑞) + 2𝐻𝐶𝑂3− (𝑎𝑞) → 𝑀𝑔𝐶𝑂3 (𝑠) + 𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙)
(ii) MgSO4.7H2O is used in medicine as an intestine purgative, a filler in making
glazed paper and, in tanning and dyeing.
(iii) CaSO4. H2O forms plaster of paris used in building, making cast and keeping the
broken limbs/bones in place while healing. The dihydrate is used in the
manufacture of fertilisers (for example ammonium sulphate).
(iv) Both MgSO4.7H2O and CaSO4.2H2O are present in hard water and are useful
for healthy bone and teeth growth, hardening of shells of water animals like
snails.
(v) BaSO4 is used in ‘X-rays meals’ since it is relatively opaque to the rays, in paint
manufacture and, as a filler for paper and rubber.

Effects of heat on the sulphates

 On gentle heating, hydrated sulphates (BeSO4.4H2O, MgSO4.7H2O, CaSO4.2H2O) lose
their water of crystallisation and form powder (anhydrous salts).
 On strong heating to high temperatures, the sulphates decompose leaving metal oxides
as a residue and oxides of sulphur (SO2, SO3) are evolved.
 Thermal stability of ionic compounds depends on majorly two factors; ionic charge and
ionic radius.
 The higher the charge on the ions, the greater will be the electrostatic forces of
attraction between the oppositely charged ions and the more stable the compound
will be due to greater lattice energy.
For example magnesium sulphate is more stable on heat than magnesium hydroxide;
since the sulphate ion is doubly charged while the hydroxide ion is singly charged.
 The smaller the ionic radii, the more closely the ions will approach each other in the
crystal lattice and the more stable will the compound be due to greater lattice
energy.
For example magnesium oxide is more stable than magnesium sulphate because the
oxide ion is much smaller than the sulphate ion. This explains why the sulphates of

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 group II elements readily decompose leaving the metal oxides. Sulphates of group I
metals however are not decomposed by heat.
H. Orthophosphates, M3(PO4)2
 The only most important orthophosphate is calcium calcium phosphate(V) (calcium
orthophosphate); Ca3(PO4)2. The salt naturally occurs in rock phosphate.
 The salt is precipitated by mixing a solution containing calcium ions with disodium
hydrogenphosphate(V) solution and an alkali. The alkali liberates the phosphate ions in
solution.
HPO42-(aq)+ OH-(aq) → PO43-(aq) + H2O(l)
3Ca2+(aq) + 2PO43-(aq) → 𝐶𝑎
⏟ 3 (𝑃𝑂4 )2 (𝑠)
𝑤ℎ𝑖𝑡𝑒 𝑠𝑜𝑙𝑖𝑑
Overall equation: 3Ca2+(aq)+ 2HPO42-(aq)+ 2OH-(aq) → Ca3(PO4)2(s) +2H2O(l)
 The salt is used as a fertilizer but has a slow action due to its low solubility in pure
water.
Explanation:
The low solubility of the salt in pure water is due to the strong attraction between
the highly charged phosphate ions and calcium ions. This gives the salt a high lattice
energy that cannot be offset by the hydration energy of the ions produced.
In pure water, the salt establishes the following equilibrium:
Ca3(PO4)2(s) + (aq) ⇌ 3Ca2+(aq) + 2PO43-(aq)………………………………….(∗)
However, the salt readily dissolves in aqueous solutions of strong acids like dilute
hydrochloric acid or nitric acid.
This is because the phosphate ions in solution combine with hydrogen ions from the
acid to form a weak acid called phosphoric(V) acid.
3H+(aq)+ PO43-(aq) → H3PO4(aq)
The removal of phosphate ions to form a weak acid disturbs the equilibrium position
in (∗). In order to restore the equilibrium position, more solid calcium phosphate
dissolves. This makes the salt readily dissolve in aqueous solutions of strong acids
than in pure water.
For similar reasons, calcium carbonate and calcium oxalate are insoluble in pure
water but readily dissolve in aqueous solutions of hydrochloric and nitric acids.

 Calcium phosphate(V) can be converted to a better fertilizer; super phosphate of lime

(calcium dihydrogenphosphate(V)) by treating it with 70% sulphuric acid.
Ca3(PO4)2(s) + 2H2SO4(aq) →Ca(H2PO4)2(s) + 2CaSO4(s)
Calcium dihydrogenphosphate(V) is a better fertiliser because it is more soluble and
thus, it action is rapid.
 Triple super phosphate (one containing no CaSO4) is made by treating calcium
phosphate(V) with phosphoric acid.
Ca3(PO4)2(s) + 4H3PO4(aq) → 3Ca(H2PO4)2(s)

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Effects of ionic radii and ionic charge of the cations of group II elements on their
compounds
 The cations of group II elements are doubly charged and have much smaller ionic radii
than their corresponding cations of group I elements which are singly charged.
Thus, cations of group II elements have a much higher charge density and hence, much
higher polarizing power than their corresponding cations of group I elements.
 As a result, compounds of group II elements exhibit the following properties:
(i) The salts of group II elements are less thermally stable than the corresponding
salts of group I elements.
For example, magnesium carbonate decomposes on heating whereas sodium
carbonate does not.
Explanation:
Cations of group II elements are more highly charged with smaller ionic radii than
the corresponding cations of group I elements. Thus, cations of group II elements
have higher charge density than the corresponding cations of group I elements.
Hence, cations of group II elements greatly polarize the neighbouring anions than
the cations of group I elements can do.
This makes the salts of group II elements less ionic (more covalent) while the salts
of group I elements are more ionic. The less ionic/more covalent a salt is, the less
stable to heat the salt is.

(ii) The salts of group II elements are generally less soluble in water than the
corresponding salts of group I elements.
This is because the solubility of salts depends on the magnitude of both lattice
energy and hydration energy.
The higher the magnitude of lattice energy, the lower the solubility of the salt.
This is because the heat of solution of such a salt will be less negative/ more
positive.
Group II elements form cations which are doubly charged with much smaller ionic
radii than those of the corresponding cations of group I elements.
Thus, the cations of group II elements strongly attract and hold the neighbouring
anions more than the corresponding cations of group I elements can do. This
makes salts of group II elements to have a much higher lattice energy which
cannot be easily offset by the hydration energy of the ions produced. This
reduces the solubility of the salts of group II elements as compared to that of
group I elements.

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 (iii) Salts of group II elements generally have lower melting and boiling points than
the corresponding salts of group I elements.
Cations of group II elements are more highly charged with much smaller ionic
radii than the corresponding cations of group I elements. Thus, cations of group
II elements have higher charge density than the cations of group I elements.
The cations of group II elements greatly polarize the neighbouring anions than
the cations of group I elements can do.
Salts of group II elements are less ionic (more covalent) and the salts of group
I elements are more ionic/less covalent. The less ionic/more covalent a salt is,
the lower the melting and boiling points of the salt.

(iv) Soluble salts of group II elements tend to go under hydrolysis in aqueous

solution. Hydrolysis is much more pronounced in soluble salts of beryllium and to
a less extent in soluble salts of magnesium.
Be(H2O)42+(aq)+ H2O(l)⇌[Be(H2O)3(OH)]+(aq)+ H3O+(aq)
Similarly for magnesium salts,
Mg(H2O)62+(aq)+ H2O(l)⇌[Mg(H2O)5(OH)]+(aq)+H3O+(aq)
The ability for the soluble salts of group II elements to undergo hydrolysis
decreases down the group. This is because of decrease in charge density of the
cation resulting from increase in cation radius in the same order as the charge
on the cations remain the same.
The resultant solutions of soluble salts of beryllium and magnesium are normally
acidic to litmus due to hydrolysis of the cations.
Cations of group I elements do not undergo hydrolysis in aqueous solution. This
is because of their low charge density/polarizing power brought about by their
low charge and large ionic radii.

Manufacture of cement
 Cement is a complex mixture of calcium silicates, aluminates, ferrites of calcium and
other ingredients. It’s a fine powder which sets a few hours when mixed with water
and then hardens in a few days into a solid, strong material. Thus, cement is a binder.
 The common raw materials used in cement manufacture are limestone, sea shells, chalk
or marl combined with shale, clay, slate, blast furnace slag, silica sand and iron ore.
 Cement can be manufactured through either dry process or wet process. The two
processes are essentially the alike except in the wet process, the raw materials are
ground with water before being fed into the kiln.
 Steps involved in cement production are:
 The basic raw materials mainly limestone, clay and other materials obtained from
quarrying are crushed through several stages to form a homogeneous mixture.

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  The crushed material is mixed with other ingredients such as iron ore or fly ash and
ground to form a homogenous mixture (‘kiln feed’ or ‘raw feed’ or ‘slurry’) which is
fed into a rotary cement kiln and heated to a temperature of about 1500oC.
Some reactions that take place in the kiln are:
𝐶𝑎𝐶𝑂3 (𝑠) ⟶ 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)
𝐶𝑎𝑂(𝑠) + 𝑆𝑖𝑂2 (𝑠) ⟶ 𝐶𝑎𝑆𝑖𝑂3 (𝑠)
𝐶𝑎𝑂(𝑠) + 𝐴𝑙2 𝑂3 (𝑠) ⟶ 𝐶𝑎(𝐴𝑙𝑂2 )2 (𝑠)
 In the kiln, certain elements are oxidised and driven off in form of gases. The
remaining elements form clinker which comes out as grey balls.
 Clinker is cooled, powdered and mixed with small amounts of gypsum and limestone
to form a fine and homogeneous powder called cement.
The gypsum slows down the reaction between cement and water (i.e. slows down the
setting properties when water is added to cement).

Write short notes on each of the following terms:

(a) Mortar
(b) Concrete

Complex compounds
 A complex is either an ion or a neutral compound consisting of a metal cation or atom
directly bonded to a number of neutral molecules with lone pairs of electrons or
negatively charged ions via dative/co-ordinate bonds.
 A complex ion is a positive or negative ion in which an atom or group of atoms with a
negative charge or lone pair of electrons form dative bonds with the central metal ion.
 The neutral molecules or negatively charged ions are called ligands.
 Examples of some common complexes formed by group II elements are:
Complex 𝑩𝒆(𝑯𝟐 𝑶)𝟐+
𝟒 𝑩𝒆(𝑶𝑯)𝟐−𝟒 𝑩𝒆(𝑵𝑯𝟑 )𝟐+
𝟒 𝑩𝒆𝑭𝟐−
𝟒 𝑴𝒈(𝑯𝟐 𝑶)𝟐+𝟔
C.N (no of ligands 4 4 4 4 6
directly bonded
to the central
atom/ion)

 Complex formation is favoured by:

(i) Availability of empty orbitals (of suitable energy) to accommodate lone pairs of
electrons from the ligands.
(ii) Charge density of the cation; cations with high charge density strongly attract
and hold the lone pairs from the ligands.
(iii) Cation radius; the smaller the cation ionic, the higher the charge density.
 Group II elements have a tendency to form complexes.
The tendency decreases in the order: 𝐵𝑒 > 𝑀𝑔 > 𝐶𝑎 > 𝑆𝑟 > 𝐵𝑎

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 Explanation:
The radius of the cations increases from 𝐵𝑒 2+to 𝐵𝑎2+ but the charge on the cations
remains the same. The charge density of the cations and hence, the attraction for the
lone pairs of electrons on the ligands decrease from 𝐵𝑒 2+to 𝐵𝑎2+ .
Beryllium forms the largest number of complexes because it forms beryllium ion with a
very small ionic radius. Thus, the cation has a high charge density and hence, high
polarizing power.
Magnesium forms a fair number of complexes but are less stable. Calcium, strontium
and barium form very few complexes.

Identification of group II cations in aqueous solution.

Table showing effect of different reagents when separately treated with aqueous
solutions containing magnesium, calcium and barium ions.

Reagent added to Cation in aqueous solution

the aqueous solution Mg 2+
Ca2+ Ba2+
Addition of dilute White White precipitate White precipitate
sodium hydroxide precipitate insoluble in excess insoluble in excess
solution insoluble in
excess
Addition of dilute White No precipitate No precipitate
ammonia solution precipitate
insoluble in
excess
Addition of sodium No precipitate White precipitate White precipitate
sulphate solution or
dilute sulphuric acid
Addition of sodium White White precipitate White precipitate
(ammonium) precipitate
carbonate solution
Addition of No precipitate White precipitate White precipitate
ammonium insoluble in ethanoic dissolves in
(potassium) oxalate acid. hot/warm ethanoic
solution followed by (The precipitate acid
ethanoic acid dissolves in mineral
acids)

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 Addition of No precipitate Yellow precipitate Yellow precipitate
potassium chromate soluble in ethanoic insoluble in ethanoic
solution followed by acid acid.
ethanoic acid (The ppt is also
insoluble in excess
sodium hydroxide
solution)
Addition of little White
solid ammonium precipitate
chloride followed by insoluble in
3-4 drops of excess ammonia
disodium solution.
hydrogenphosphate (The precipitate
solution followed by however
excess ammonia dissolves in
solution. dilute
This is the hydrochloric or
confirmatory test and dilute nitric
for magnesium ions acid)
in aqueous solution.

Some ionic equations for reactions taking place during the identification of the cations in
aqueous solution are:
𝑀(𝑂𝐻)2 (𝑠) ; 𝑀2+ (𝑎𝑞) + 𝑆𝑂42− (𝑎𝑞) ⟶ ⏟
𝑀2+ (𝑎𝑞) + 2𝑂𝐻 − (𝑎𝑞) ⟶ ⏟ 𝑀𝑆𝑂4 (𝑠)
𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡 𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡

𝑀𝐶𝑂3 (𝑠); 𝑀2+ (𝑎𝑞) + 𝐶2 𝑂42− (𝑎𝑞) ⟶ ⏟

𝑀2+ (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞) ⟶ ⏟ 𝑀𝐶2 𝑂4 (𝑠)
𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡 𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡
𝐵𝑎𝐶2 𝑂4 (𝑠) + 2𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) ⟶ 𝐵𝑎(𝐶𝐻3 𝐶𝑂𝑂)2 (𝑎𝑞) + 𝐶2 𝑂42− (𝑎𝑞)

𝑀2+ (𝑎𝑞) + 𝐶𝑟𝑂42− (𝑎𝑞) ⟶ 𝑀𝐶𝑟𝑂4 (𝑠); 𝑀𝑔 (𝑎𝑞) + 𝑁𝐻4 (𝑎𝑞) + 𝐻𝑃𝑂4 (𝑎𝑞) ⟶ 𝑀𝑔𝑁𝐻
2+ + 2− +
⏟ ⏟ 4 𝑃𝑂4 (𝑠) + 𝐻 (𝑎𝑞)
𝑦𝑒𝑙𝑙𝑜𝑤 𝑝𝑝𝑡 𝑤ℎ𝑖𝑡𝑒 𝑝𝑝𝑡

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