PERIOD 3 ELEMENTS

Periodicity of the physical properties;

i. Atomic and ionic radii.
ii. Ionization energy and electron affinity.
iii. Electronegativity and electropositivity.
iv. Melting point and boiling point.
v. Electrical and thermal conductivity.
Data for some physical properties is shown in the table below:
ELEMENTS
Properties Na Mg Al Si P S Cl Ar

Melting point/oC 98 650 660 1410 44 119 -101 -189

∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛/KJmol-1 2.6 8.95 10.75 46.4 0.63 1.41 3.20 1.18

Boiling point/oC 890 1120 2450 2680 280 445 -34 -186

Thermal
conductivity 1.34 1.6 2.1 0.84 - Negligible

Type of element
metalloid

Metals
Non - metals

Giant
Bond type Metallic covalent Covalent

Giant
Structure Giant metallic Covalent Simple molecular
Definition of some terms
(i) Enthalpy of fusion. This is the enthalpy change that occurs when one mole of solid substances
change to the liquid state at the melting point.
(ii) Melting point. It is the constant temperature at which both the solid and liquid states of a
substance are in equilibrium.
(iii) First ionization energy. This is the minimum amount of energy required to remove an
electron completely from a gaseous atom to form a free unipositively charged gaseous ion.
Or This is the minimum amount of energy required to remove one mole of electrons completely
from one mole of gaseous atoms to form one mole of free unipositively charged gaseous ions.
Thus it is the energy change for the process below;
+ +
M(g) - e- 𝑀(𝑔) (or M(g) 𝑀(𝑔) + e-)
(iv) Electronegativity. It is a measure of the tendency (extent) of an atom of an element to attract
bonding electrons towards itself in a covalent bond.
−
i.e. X(g) + e- 𝑋(𝑔) HEA (electron affinity)

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(or it is the power of an atom of an element to attract electrons towards itself in a covalent bond).
(v) Electropositivity. It is the measure of the tendency for an atom of an element to lose bonding
electrons in a covalent bond.
+ +
i.e. M(g) - e- 𝑀(𝑔) or M(g) 𝑀(𝑔) + 𝑒−
(vi) Atomic radii. Covalent radius is half the inter nuclei distance between two covalently
bonded atoms. (i.e. Half the distance between the nuclei of two atoms which are covalently
bonded together)
(or Its half the distance of closest approach between the two nuclei of two covalently bonded
atoms)
i.e.

𝑑 r = Atomic radius
=𝑟
2
(vii) Ionic radii
This is the effective radius of an ion within a series of ionic crystals of which the ion is part.

General Trends in Physical Properties of Period 3 Elements

1. Ionisation energy, Electron affinity and Electro negativity
On the left hand side of the Periodic Table, the elements are metallic while on the right hand side
they are non-metallic.
The change from metallic to non-metallic properties is governed by the electronegativity which
increases from left hand side to the right hand side.
Elements on the left hand side have low ionization energies and low electron affinities hence low
electronegativity thus they have a greater tendency to metallic behaviour.
2. Melting points and boiling points
They generally rise with high values from sodium to silicon and then fall to low values from
phosphorous to argon. The high values on the left hand side are due to elements forming giant
structures (i.e. giant metallic such as in Na, Mg and Al, and giant covalent such as in Silicon).
The low values on the right hand side are due to elements possessing simple molecular
structures.
(a) Metallic structures. Sodium, magnesium, and aluminium have giant metallic structures. The
atoms in their structures are held by strong inter-particle metallic bonds which requires high
energy to be overcome in the solid to form liquid.
The melting points increase from sodium to aluminium. This is because as the valency of the
element increases the number of delocalized electrons participating in formation of the metallic
bonding increases and thus the melting points or boiling points will also rise. The melting point
of magnesium is higher than that of sodium because each atom of sodium contributes one
delocalized electron while that of magnesium contributes two delocalized electrons to the
formation of the metallic bond. The metallic bond in magnesium is stronger than that in sodium
and hence has a higher melting or boiling point.
However, the melting point of aluminium is close to that of magnesium because aluminium
contributes two delocalized electrons instead of three in the formation of the metallic bond. i.e.
aluminium does not fully contribute its three valence electron cloud due to the high charge
density of the aluminium ion being formed.
(b) Molecular structures

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 (i) Silicon has a giant covalent (molecular) structure. Each silicon atom is covalently bonded to
four other silicon atoms to give an infinite 3–dimensional (3D) giant covalent (or molecular)
structure which is tetrahedral in shape and contains short and strong covalent bonds due to the
relatively small atomic radius of silicon. These bonds cannot easily be weakened or broken
during melting or vapourisation. Thus very high temperatures are required to break these bonds.
(ii) Phosphorous, sulphur, chlorine and argon form simple molecular structures. Their molecules
are held by the Van der Waal’s forces of attraction that are weak and relatively easy to weaken or
break down and change a solid to a liquid or a liquid or gas. However, the magnitude and
strength of the Van der Waal’s forces increase with increase in the molecular mass. Thus sulphur
has the highest melting point because it exists as an octaatomic molecule with the highest
molecular mass followed by phosphorous that exists as a tetraatomic molecule, then chlorine
which exists as a diatomic molecule and monoatomic argon gas has the least.
This is shown in the table below.
Substances P4 S8 Cl2 Ar
R.F.M 124 256 71 40
Melting point (0C) 44 119 -109 -159
The melting point of argon is extremely low because atoms assume nearly the spherical shape.

Question:
Explain the trend in variation of melting points in the table given above.
The molecular shapes of silicon, sulphur, phosphorous and chlorine are shown below:
- Silicon
Si

Si
Si Si
Si
- Sulphur
S S S

S
S
S
S
- Phosphorous
P

P P
P
- Chlorine
Cl Cl

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 3. Atomic radii
The atomic radii decrease from Sodium to Argon. This is because the electrons are being added
in the same energy level (or shell) and the increase in screening effect is outweighed by the
increase in nuclear charge. The effective nuclear charge increases hence the outermost electrons
are more strongly attracted to the nucleus leading to a decrease in the radius of the atom.
There is also an increase in electronegativity on moving from Na to Ar.
4. Atomic conductance of heat and electricity
It is the highest for elements on the left hand side with metallic bonding due to presence of
delocalized electrons in their structures which increase from Na to Al because more electrons per
atom are contributed to the delocalized sea of electrons.
However nonmetals are poor conductors of both heat and electricity because they lack
delocalized electrons. This is because the energy required to remove electrons from the localized
covalent bonds is very high. However in silicon the energy to remove the electrons from the
covalent bond is much less than for other non-metals therefore it is a semi-conductor. The reason
above explains the difference both in thermal and electrical conductivity for both metals and
nonmetals.
Qn. Explain in terms of electronic structure why aluminium conducts electricity but the common
allotropes of phosphorous do not. (P has a half filled electronic structure which is stable unlike
Al. Thus valence electrons in aluminium can easily be delocalized unlike those in P)
Periodicity of the chemical properties
These properties include reactions of elements with
(i) Water (ii) Air (O2 and N2) (iii) Dilute Sodium hydroxide
(iv) Dilute hydrochloric acid and sulphuric acid (v) Halogens e.g. chlorine
Reaction with water Reaction with Reaction with dilute HCl
NaOH
Na Reacts vigorously in cold No reaction Violent reacts
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
Mg Reacts slowly in cold but vigorously with No reaction Vigorously reacts
steam Mg(s)+ 2HCl(aq) MgCl2(aq)+H2(g)
Mg(s) + 2H2O(l) Mg(OH)2(aq) + H2(g)
Mg(s) + H2O(g) MgO(s) + H2(g)
Al No reaction with cold but reacts with Dissolves both hot Reacts moderately
moderately with steam and conc. Then hot
2Al(s) + 3H2O(g) Al2O3(s) + 3 H2(g) and dilute.
Si No reaction with cold water but reacts Dissolves in hot No reaction
moderately with steam. and conc.
Si(s) + 2H2O(g) SiO2(s) + 2H2(g)
P No reaction with cold water but reacts Reacts with hot No reaction
slowly with steam. and conc.
S No reaction Reacts with hot No reaction
and conc.
Cl Reacts in cold water Reacts with both: No reaction
- Dilute and cold.
- Hot and conc.
Ar No reaction No reaction No reaction

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Reaction of Elements with water
a) Metals
- Sodium reacts vigorously with cold water darting in form of a silvery ball on the water surface
liberating hydrogen gas as a colourless gas and forming sodium hydroxide as an alkaline
solution. A lot of heat is liberated causing the sodium to melt into a silvery ball.
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
- Magnesium reacts very slowly with cold water. A very clean coil of magnesium dropped into
cold water eventually gets covered in small bubbles of hydrogen which float it to the surface.
Magnesium hydroxide is formed as a very thin layer on the magnesium and this tends to stop the
reaction. Magnesium reacts vigorously when heated in steam producing a white flame, forming
magnesium oxide as a white ash and hydrogen gas.
with cold water, Mg(s) + 2H2O(l) Mg(OH)2(aq) + H2(g)
with steam, Mg(s) + H2O(g) MgO(s) + H2(g)
- Aluminium doesn’t react with cold water due to formation of the oxide which is a protective
layer that coats the metal and prevents further reaction.
It reacts moderately only when heated with steam since the oxide layer is partly removed after its
formation, 2Al(s) + 3H2O(g) Al2O3(s) + 3H2(g)
b) Non – metals
- Silicon does not usually react with cold water but reacts moderately with steam. The common
shiny grey lumps of silicon with a rather metal-like appearance are fairly unreactive.
This form of silicon will react with steam at red heat to produce silicon dioxide and hydrogen.
But much more reactive forms of silicon will react with cold water to give the same products.
i.e. Si(s) + 2H2O(g) SiO2(g) + 2H2(g)
- Phosphorous does not react with cold water but reacts very slowly when heated with steam.
When vapourised, it reacts slightly with steam to form phosphorous(III) oxide P 2O3, that
dimerises in form of P4O6. 4P(s){or P4} + 6H2O(g) P4O6 (s) + 6H2(g)
- Sulphur does not react with either cold water or steam.
- Chlorine dissolves in water to some extent (slowly) to give a light green solution (in case it is
in large amounts). The reaction doesn’t go to completion hence it is reversible forming a mixture
of hydrochloric acid and chloric(I) acid (hypochlorous acid).
Cl2(g) + H2O(l) HOCl(aq) + HCl(aq)
The chloric(I) acid may be written as HClO. The form used in above equation more accurately
reflects the way the atoms are bonded.
In the presence of sunlight, the chloric(I) acid slowly decomposes to produce more hydrochloric
acid, releasing oxygen gas, and you may come across an equation showing the overall change:
2Cl2(g) + 2H2O(l) 4HCl (aq) + O2(g)
- Argon does not react with water under any conditions.

Reaction of Elements with strong alkalis (sodium hydroxide or potassium hydroxide)

e.g. with sodium hydroxide solution
a) Metals
- Sodium and Magnesium do not react with sodium hydroxide because they are basic elements
and their electroposivity is high, similar to that of the sodium in sodium hydroxide.
- Aluminium being amphoteric, dissolves or reacts with sodium hydroxide. Aluminium powder
reacts with hot dilute sodium hydroxide to form a hydrated complex ion, tetrahydroxoaluminate

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ion, [Al(OH)4 ]−
(aq) or lumps of aluminium react with hot concentrated sodium hydroxide to form
the anhydrous complex ion, dioxoaluminate(III) ion, AlO2-(aq) as shown in equations below:
with hot and dilute: 2Al(s) + 2NaOH(aq) + 6H2O(l) 2NaAl(OH)4(aq) + 3H2(g)
− −
i.e 2Al(s) + 2OH(aq) + 6H2O(l) 2[Al(OH)4 ] + 3H2(g)
(aq)
with hot and concentrated:
− −
2Al(s) + 2OH(aq) + 6H2O(l) 2[Al(OH)4 ] + 3H2(g) -------- (i)
(aq)
then 2[Al(OH)4]-(aq) 2 AlO2-(aq)+ 4H2O(l) ------------ (ii)
adding together equations (i) and (ii) we get over all equation as;
−
2Al(s) + 2𝑂𝐻(𝑎𝑞) + 2H2O(l) 2AlO2 -(aq) + 3H2(g)
Qn: Aluminium is should not be washed using alkaline solutions. Explain.
b) Non – metals
Silicon, Phosphorous and Sulphur react with hot and concentrated sodium hydroxide as shown
−
in the equations below: Si(s) + 2OH(aq) + H2O(l) SiO2−
3(aq) + 2H2(g)
− −
4P (s) + 3OH(aq) + 3H2O(l) 3H2PO2 (aq) + PH3(g)
(phosphinate) (phosphine)
− 2− 2−
either 3S(s) + 6OH(g) 2S(aq) + SO3(aq) + 3H2O(l)
or 3S(s) + 6NaOH(aq) 2Na2S(aq) + Na2SO3(aq) + 3H2O(l)
- Chlorine reacts with sodium hydroxide under two different conditions i.e. when cold and
dilute; and when hot and concentrated as;
Cold and dilute Cl2(g) + 2NaOH(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
Hot and concentrated. 3Cl2(g) + 6NaOH(aq) NaClO3(aq) + 5NaCl(aq) + 3H2O(l)
However chlorine dissolves much more (or is more soluble) in sodium hydroxide solution than in
water. This is because in water, chlorine partially dissolves forming a mixture of chloric(I) acid
Cl2 + H2O(l) HOCl(aq) + HCl(aq)
and hydrochloric acid;
In dilute alkali, chlorine first partially dissolves in water to form hydrochloric acid and chloric(I)
Cl + H2O(l) HOCl(aq) + HCl(aq)
acid; 2 The hydroxide ions from alkali then
- −
react with the acids formed; OH (aq) + HOCl(aq) H2O(l) + OC𝑙(𝑎𝑞)
also OH-(aq) + HCl(aq) H2O(l) + Cl-(aq)
The concentration of the acids in the equilibrium reaction decreases and thus the equilibrium for
dissolution in water shifts to the right hence making more chlorine to dissolve. Chlorine
therefore dissolves much more in sodium hydroxide solution than in water for this reason.
Iodine is more soluble in sodium hydroxide solution than in water for the same reason.
In general non–metals react with alkali to form oxo-anions i.e ions composed of non-metals and
oxygen or hydroxide ions. e.g. OCl-, 𝑆𝑂32− , etc.

Reaction of Elements with acids (hydrochloric and sulphuric acid)

a) Metals
- Sodium reacts violently while magnesium reacts moderately with dilute acids to form their
corresponding salts and hydrogen gas.
- Aluminium reacts slowly with hot dilute hydrochloric and sulphuric acid but more rapidly
when concentrated. However, with concentrated sulphuric acid, sulphurdioxide gas is evolved.
Thus aluminium is not readily attacked by both cold dilute sulphuric acid and hydrochloric acid
but reacts moderately with both concentrated hydrochloric acid and sulphuric acid;

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2Al(s) + conc 6HCl(aq)⟶ 2AlCl3(aq) + 3H2(g) 2Al(s) + conc 6H2SO4(l)⟶ Al2(SO4)3(aq) + 3SO2(g) + 6H2O(l)
However, aluminium is rendered passive by hot concentrated nitric acid due to formation of the
impervious (inert) oxide layer on its surface that stops the reaction.
b) Non-metals
- Sulphur is oxidized by hot concentrated sulphuric acid to sulphurdioxide and water.
S(s) + 2H2SO4(l) 3SO2(g) + 2H2O(l)
It is also oxidized by hot and concentrated nitric acid to form sulphuric acid, water and
nitrogendioxide gas. S(s) + 6HNO3(aq) H2SO4(aq) + 6NO2(g) + 2H2O(l)
- Silicon, phosphorous and chlorine do not react with acids because they are acidic in nature.
The only acid that reacts with silicon is hydrogen fluoride (hydrofluoric acid) forming
hexafluorosilicic acid. Formation of the soluble complex ion, SiF62- favours the reaction.
Si(s) + 6HF(l) H2SiF6(l)+2H2(g)

Reactions of Elements with oxygen

- Sodium burns in oxygen with an orange flame to produce a mixture of a yellow solid sodium
peroxide and a white powder of sodium oxide.
For the simple oxide (limited oxygen supply): 4Na(s) + O2(g) 2Na2O(s)
For the peroxide (excess oxygen supply): 2Na(s) + O2(g) Na2O2(s)
- Magnesium burns in oxygen with an intense white flame to give white solid magnesium oxide.
2Mg(s) + O2(g) 2MgO(s)
If magnesium is burnt in air rather than in pure oxygen, it also reacts with the nitrogen in the air
to form a mixture of magnesium oxide and magnesium nitride formed.
3Mg(s) + N2(g) Mg3N2(s)
The reaction with nitrogen is possible although nitrogen is generally inert due to its strong triple
bond. This is because burning magnesium liberates a lot of heat energy which can break the
triple bond in the nitrogen molecule forming magnesium nitride.
Magnesium nitride can be hydrolysed by water to form magnesium hydroxide and ammonia gas.
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(aq) + 2NH3(g)
Magnesium also continues to burn in a stream of carbondioxide gas to form a white ash of
magnesium oxide and a black solid of carbon. This is because, burning magnesium liberates a lot
of heat energy which breaks the double bond in the carbondioxide molecule (decomposes
carbondioxide) to form black carbon and oxygen gas. The oxygen gas then easily combines with
magnesium to form the white ash of magnesium oxide.
2Mg(s) + CO2(g) 2MgO(s) + C(s)
When the magnesium is heated in a glass tube, the magnesium also reacts with the glass. That
leaves dark grey products (including silicon and perhaps boron from the glass) as well as the
white magnesium oxide.
- Aluminium will burn in oxygen if it is powdered, otherwise the strong oxide layer on the
aluminium tends to inhibit the reaction. If aluminium powder is sprinkled into a bunsen flame,
white sparkles of aluminium oxide is formed.
4Al(s) + 3O2(g) Al2O3(s)
It also reacts with nitrogen gas in air to form its nitride.
2Al(s) + N2(g) ⟶ 2AlN(s)
- Silicon will burn in oxygen if heated strongly enough to form silicon(IV) oxide.
Si(s) + O2(g) SiO2(s)

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- White phosphorous catches fire spontaneously in air, burning with a white flame and
producing clouds of white smoke - a mixture of phosphorous(III) oxide and phosphorus(V)
oxide.
The proportions of these depend on the amount of oxygen available. In an excess of oxygen, the
product will be almost entirely phosphorous(V) oxide. They dimerise in the gaseous state.
for the phosphorous(III) oxide: P4(s) + 3O2(g) P4O6(g)
for the phosphorous(V) oxide: P4(s) + 5O2(g) P4O10(g)
- Sulphur burns in air or oxygen on gentle heating with a pale blue flame. It produces colourless
sulphur dioxide gas. S(s) + O2(g) SO2(g)
Sulphur dioxide can be converted further into sulphur trioxide in the presence of oxygen, but it
requires the presence of vanadium(V) oxide as a catalyst and high pressure.
2S(s) + 3O2(g) 2SO3(g)
- Chlorine doesn't react directly with oxygen. Despite having several oxides.
- Argon doesn't react either.

Reactions of Elements with chlorine (or other halogens)

- Sodium burns in chlorine with a bright orange flame. White solid sodium chloride is produced.
2Na(s) + Cl2(g) 2NaCl(s)
- Magnesium burns with its usual intense white flame to give white magnesium chloride.
Mg(s) + Cl2(g) MgCl2(s)
- Aluminium is often reacted with chlorine by passing dry chlorine over aluminium foil heated
in a long tube. The aluminium burns in the stream of chlorine to produce very pale yellow
aluminium chloride. This sublimes (turns straight from solid to vapour and back again) and
collects further down the tube where it is cooler. 2Al(s) + 3Cl2(g) 2AlCl3(s)
or dimerises in vapour. i.e. 2Al(s) + 3Cl2(g) Al2 Cl6 (g).
Note that: Aluminium reacts with molten sulphur directly when strongly heated.
2Al(s) + 3S(s) Al2S3(s)
The sulphide can be hydrolysed by water to form hydrogen sulphide gas.
Al2S3(s) + 6H2O(l) 2Al(OH)3 (aq) + 3H2S(g)
- Silicon. If chlorine is passed over silicon powder heated in a closed tube, it reacts to produce
silicon tetrachloride. This is a colourless liquid which vaporises and can be condensed further
along the apparatus. Si(s) + 2Cl2(g) SiCl4(l)
- White phosphorous burns spontaneously in chlorine to produce a mixture of two chlorides,
phosphorous(III) chloride and phosphorous(V) chloride (phosphorous trichloride and
phosphorous pentachloride). Phosphorous(III) chloride is a colourless fuming liquid.
P4(s) + 6Cl2(g) 4PCl3(l)
Phosphorous(V) chloride is an off-white (going towards yellow) solid.
P4(s) + 10Cl2(g) 4PCl5(s)
Note that: These equations are often written with symbol P rather than P4. It depends on the form
of phosphorous. If it is white phosphorous, P4 is the correct version. If it is red phosphorous, then
P is correct because it has a different (polymeric) structure. Red phosphorous is also less
commonly used in labs at this level because it isn't as excitingly reactive as white phosphorous.
- Sulphur. If a stream of chlorine is passed over some heated sulphur, it reacts to form an
orange, bad-smelling liquid, disulphur dichloride. 2S(s) + Cl2(g) S2Cl2(l)
- Chlorine and argon. Chlorine cannot react with itself, and argon doesn't react with chlorine
since it is an inert gas.

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 COMPOUNDS OF PERIOD 3 ELEMENTS
These include the following:
(i) Oxides (ii) Chlorides (iii) Hydrides
ELEMENTS
COMPOUNDS Na Mg Al Si P S Cl
Chlorides NaCl MgCl2 AlCl3 SiCl4 PCl3 S2Cl2 Cl2
PCl5 SCl2
Oxides Na2O MgO Al2O3 SiO P2O3 SO2 Cl2O
Na2O2 SiO2 P2O5 SO3 ClO2
Cl2O6
Cl2O7
Hydride NaH MgH2 AlH3 SiH4 PH3 H2S HCl

(1) OXIDES
PROPERTIES OXIDES
Formulae Na2O MgO Al2O3 SiO2 P2O3 SO2 Cl2O,Cl2O6
Na2O2 P2O5 SO3 ClO2,Cl2O7
Melting Point (0C) 1132 for 2852 2072 1710 P2O3 24 SO2 -72 Low
Na2O P2O5 340 SO3 17
sublimes
Boiling Point (0C) 1950 for 3600 2977 2230 P2O3 173 SO2 -10 Low
Na2O P2O5 360 SO3 45
State SOLID GAS
Bond Type Predominant
IONIC ionic COVALENT
Structure GIANT IONIC GIANT
SIMPLE MOLECULAR
COVALENT
Reaction with water Readily Sparingly No effect React
reacts reacts
Reaction with NaOH No effect React
Nature of Oxides Basic Amphoteric Acidic
Reaction with
React No effect
HCl(aq)
Trends in structure and properties
1. Variation in melting and boiling points.
Trend: Generally, the melting points (or boiling points) of the oxides of period 3 elements
decrease across the period.
Explanation: Sodium, magnesium and aluminium form ionic compounds with giant ionic
structures. Their oppositely charged ions are held together by strong electrostatic forces of
attraction that cannot easily be broken. These oxides therefore have high melting points and
boiling points and high enthalpy of vapourisation.
The strength of ionic bonds increases from the oxide of sodium to that of magnesium. This is
because across the period, the cationic radius decreases as the cationic charge increases. Thus
oppositely charged ions more strongly attract each other (i.e electrostatic forces of attraction)
from sodium oxide to magnesium oxide and more energy is required to break the ionic lattice of
magnesium oxide than sodium oxide leading to increase in melting (boiling) point as well as the
lattice energy. However aluminium oxide has an abnormally lower melting point than
magnesium oxide. This is because the aluminium ion has got a high charge density and high

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polarizing power. This creates a covalent character that reduces the strength of the ionic bond
and the electrostatic forces of attraction in aluminium oxide become weaker.
Silicon is in group IV and forms a giant covalent structure in silicon dioxide. Each Silicon atom
is tetrahedrally surrounded by four oxygen atoms to give it an infinite three dimensional giant
structure with a network of short and strong covalent bonds that cannot easily be broken.

The phosphorous, sulphur and chlorine form covalent oxides which are discrete molecules with
simple molecular structures held by weak intermolecular Vander Waal’s forces of attraction that
can easily be broken. Hence have low melting points and boiling points. However the magnitude
and strength of the Van der Waal’s forces increases with increase in molecular mass and this
leads to increase in their melting or boiling points increase.
2. Variation in the nature of oxides.
Trend: There is a change in nature of oxides from basic to amphoteric for the metals and then to
acidic for the non-metals across the period.
Explanation: This is due to the change from metallic to non-metallic character of the elements.
Or this is because the non-metallic character of the elements increases across the period (metallic
character of the elements decreases across the period).
i.e. The oxides change from basic to amphoteric and to acidic. This is due to a change from
metallic to non-metallic character across the period in the Periodic Table.
3. The oxides also have high electrical conductance in the molten form or aqueous state.
Question:
The table below shows melting points of the oxides in period 3 elements
Na2O MgO Al2O3 SiO2 P2O3 SO3
11930C 28520C 23450C 16500C 240C 170C
(i) Explain the values of the melting points of these oxides with reference to the bonding and structure.
(ii) Explain the trend in the nature of oxides given in the table. Write equations to illustrate your answers.
Preparation
(a) Oxides of sodium are prepared by heating of sodium;
In a limited supply of oxygen, sodium oxide is formed. 4Na(s) + O2(g) 2Na2O(s)
In excess supply of oxygen, sodium peroxide is formed. 2Na(s) + O2(g) Na2O2(s)

(b) Magnesium oxide is prepared by;

(i) Heating magnesium with steam.
Mg(s) + H2O(g) MgO(s) + H2(g)
(ii) Heating of magnesium with dry oxygen gas in air. 2Mg(s) + O2(g) 2MgO(s)
(iii) Decomposing magnesium carbonate, magnesium hydrogen carbonate, magnesium nitrate
and magnesium hydroxide. (Write the equations for the decomposition reactions)

(c) Aluminium oxide is prepared by;

(i) Heating aluminium in dry oxygen gas in air. 4Al(s) + 3O2(g) 2Al2O3(s)
(ii) Heating aluminium in steam.
(iii) Decomposing aluminium hydroxide or aluminium nitrate.

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(d) Oxides of silicon
(i) Silicon(VI) oxide can be prepared by:
- Heating silicon in dry oxygen gas (air).
- Passing steam over heated silicon forms silicon dioxide.
Si(s) + H2O(g) SiO2(s) + H2(g)
- Heating silane (silicon tetra hydride) with dry oxygen forms silicon dioxide.
SiH4(g) + 2O2(g) SiO2(s) + 2H2O(g)
(ii) Silicon monoxide can be prepared by heating silicon(IV) oxide in dry carbonmonoxide gas
forms silicon monoxide. SiO2(s) + CO(g) SiO(s) + CO2(g)

(e) Oxides of phosphorous are prepared by;

Heating phosphorous in a limited supply of dry oxygen forms phosphorous(III) oxide.
4P(s) + 3O2(g) 2P2O3(s) or P4O6(g)
In excess supply of dry oxygen, forms phosphorous(V) oxide.
4P(s) + 5O2(g) 2P2O5(s) or P4O10(g)

(f) Oxides of sulphur are prepared by;

Heating sulphur in a limited supply of dry oxygen. S(s) + O2(g) SO2(g)
In excess supply of dry oxygen with vanadium(V) catalyst and high pressure, sulphur trioxide is
formed. 2S(s) + 3O2(g) 2SO3(g) or 2SO2(s) + O2(g) 2SO3(g)
Reaction with Water
a) Na2O and Na2O2. They dissolve readily in water forming a strongly alkaline solution of
sodium hydroxide. Sodium peroxide dissolves with effervescence of a colourless gas.
Na2O(s) + H2O(l) 2NaOH(aq)
2Na2O2(s) + 2H2O(l) 4NaOH(aq) + O2(g)

b) MgO. Reacts slowly forming a weakly alkaline solution of magnesium hydroxide.

MgO(s) + H2O(l) Mg(OH)2(aq)

c) Al2O3 and SiO2 have no effect on water because they are weakly acidic or basic oxides.

d) P2O3 and P2O5 react with water to form weakly acidic solutions.
P2O3(s) + 3H2O(l) 2H3PO3(aq) Phosphorous acid or phosphoric(III) acid.
P2O5(s) + 3H2O(l) 2H3PO4(aq) Phosphoric acid or phosphoric(V) acid.

e) SO2 and SO3 react with water to form acidic solutions.

SO2(g) + H2O(l) H2SO3(aq)
Sulphurous acid or sulphuric(IV) acid
SO3(g) + H2O(l) H2SO4(aq) Sulphuric acid or sulphuric(VI) acid (reaction is
highly exothermic)

f) Cl2O (Chlorine monoxide) and Cl2O7 (Chlorine heptoxide), Cl2O6 (chlorine hexoxide) ClO2
(Chlorine dioxide) react with water forming oxy acids.
Cl2O(g) + H2O(l) 2HClO(aq) Chloric(I) acid or hypochlorous acid
Cl2O7(l) + H2O(l) HClO4(aq) Chloric(VII) acid or perchloric acid
Cl2O6(l) + H2O(l) HClO4(aq) + HClO3(aq)

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 2ClO2(g) + H2O(l) HClO3(aq) + HClO2(aq)
Reaction with strong alkali (sodium or potassium hydroxide)
a) Na2O and Na2O2 (No effect because they are basic oxides)

b) MgO (No effect because it is a basic oxide)

c) Al2O3 reacts with hot and dilute or concentrated alkali because it is amphoteric.
− −
with hot and concentrated alkali; Al2O3(s) + 2𝑂𝐻(𝑎𝑞) 2𝐴𝑙𝑂2(𝑎𝑞) + H2O(l)
− −
with hot and dilute: Al2O3(s) + 2𝑂𝐻(𝑎𝑞) + 3H2O(l) 2 [𝐴𝑙(𝑂𝐻)4 ](𝑎𝑞)
(or Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na Al(OH)4(aq) )
−
or Al2O3(s) + 6𝑂𝐻(𝑎𝑞) + 3H2O(l) 2 [𝐴𝑙(𝑂𝐻)6 ]3−
(𝑎𝑞)
d) SiO is a neutral oxide and has no effect.
SiO2 is an acidic oxide and reacts with hot concentrated sodium hydroxide
−
SiO2(s) + 2𝑂𝐻(𝑎𝑞) 𝑆𝑖𝑂32−(𝑎𝑞) + H2O(l)
(or SiO2(s) + 2NaOH(aq) Na2SiO3(aq) + H2O(l) )

e) P2O3 and P2O5 react with dilute NaOH. The reaction occurs via two stages as;
Stage 1: the oxide first dissolves in water present to form an acid.
Stage 2: the acids formed in stage 1 then reacts with NaOH.
Thus for P2O3 we have
P2O3(s) + 3H2O(l) 2H3PO3(aq)
then H3 PO3(aq) + NaOH(aq) NaH2PO3(aq) + H2O(l)
Combining the two above equations we obtain { eqn (i) + 2 x eqn (ii) }
P2O3(s) + H2O(l) + 2NaOH(aq) 2NaH2PO3(aq)

Similarly for P2O5 we have

P2O5(s) + 3H2O(l) 2H3PO4(aq)
then H3 PO4(aq) + NaOH(aq) NaH2PO4(aq) + H2O(l)
The overall equation is
P2O5(s) + 2NaOH(aq) + H2O(l) 2NaH2PO4(aq)
(Sodium dihydrogen phosphate)
f) SO2 and SO3 react with cold and concentrated NaOH as
For SO2(g) + NaOH(aq) NaHSO3(aq) with excess sulphurdioxide
−
(or SO2(g) + 𝑂𝐻(𝑎𝑞) HS𝑂3−(𝑎𝑞) )
−
also SO2(g) + 2𝑂𝐻(𝑎𝑞) S𝑂32−(𝑎𝑞) + H2O(l) with limited sulphurdioxide
− 2−
For SO3(g) + 2𝑂𝐻(𝑎𝑞) 𝑆𝑂4 (𝑎𝑞) + H2O(l)
(or SO3(g) + 2NaOH(aq) Na2SO4(aq) + H2O(l) )

g) Cl2O, Cl2O7 and ClO2 react with sodium hydroxide as follows:

− −
Cl2O(g) + 2O𝐻(𝑎𝑞) 2𝑂𝐶𝑙(𝑎𝑞) + H2O(l)
Chlorate(I)
− − −
2ClO2(g) + 2O𝐻(𝑎𝑞) 𝐶𝑙𝑂2(𝑎𝑞) + 𝐶𝑙𝑂3(𝑎𝑞) + H2O(l)
Chlorate(III) Chlorate(V)
− − −
Cl2O6(l) + 2O𝐻(𝑎𝑞) 𝐶𝑙𝑂3(𝑎𝑞) + 𝐶𝑙𝑂4(𝑎𝑞) + H2O(l)

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 Chlorate(V) Chlorate(VII)
− −
Cl2O7(l) + 2O𝐻(𝑎𝑞) 2𝐶𝑙𝑂4(𝑎𝑞) + H2O(l)
Chlorate(VII)
Reaction with mineral acids (nitric acid, sulphuric acid or hydrochloric acid)
Oxides of sodium and magnesium are basic while that of aluminium is amphoteric. Therefore,
they can react with acids to form their salts and water. The reactivity decreases across the period.
The oxides of other elements in Period 3 do not react with acids at all. However, aqueous
hydrogen fluoride (hydrofluoric acid) attacks silica (silicon dioxide) due to formation of the
hexachlorosilicic complex ion, SiF62-. SiO2(s) + 4HF(aq) SiF4(g) + 2H2O(l)
then SiF4(g) + 2HF(aq) H2SiF6(aq)
Overall equation is SiO2(s) + 6HF(aq) H2SiF6(aq) + 2H2O(l)
(2) CHLORIDES
PROPERTIES NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2 Cl2
PCl5 S2Cl2
Physical Solid Solid Solid Colourless PCl3(liquid) Liquids Gas
state at room fuming liquid
PCl5(Solid)
temperature
Melting 801 714 193 -68.74 PCl3 (-93.6) SCl2 (-121) -101.5
point /oC PCl5 (160.5) S2Cl2 (-80)
Boiling point 1465 1412 423 but 58 PCl3 (76) SCl2 (59) -34
/oC sublimes at 180 PCl5 (167) S2Cl2 (138)
Action of Melts Melts Sublimes and a
Heat (electrolyte) (electrolyte) non-electrolyte Vapourises Vapourises Decomposes Decomposes
Action of Dissolves Partially Hydrolyses Reacts React to Decomposes Reacts to
water and ionizes hydrolyses forming acidic violently and form H3PO4 form HCl
(Neutral (acidic solutions later or H3PO4 and HOCl
solution) solution) hydrolyses
Bond Ionic Predominantly Predominantly Covalent Covalent Covalent Covalent
ionic covalent
Structure Simple Simple Simple Simple
Giant ionic Giant ionic Giant ionic molecular molecular molecular molecular

1. Variation in the melting and boiling points.

Trend: Generally, the melting points (or boiling points) of the chlorides of period 3 elements
decrease from high values in sodium chloride to low values in chlorine across the periodic table.
Explanation: Sodium chloride, magnesium chloride and aluminium chloride have giant ionic
structures composed of oppositely charged ions attracted to each other by strong electrostatic
forces in ionic bonds that cannot easily be broken. Hence they have high melting points and
boiling points. For the same reason, they conduct electricity in molten or aqueous state. Sodium
chloride and magnesium chloride form predominantly ionic bonds while aluminium chloride
forms a predominantly covalent bond.
The melting points or boiling points decrease from sodium chloride to aluminium chloride due to
a change from ionic character to covalent character. This is because across the period, the
cationic radius decreases as the cationic charge increases. This leads to an increase in the charge
density and consequently an increase in the polarizing power due to presence of the polarizable
chloride ion. The large chloride ion is polarized by the aluminium ion leading to a greater

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covalent character which in turn reduces the ionic character. Thus the melting and boiling points
of aluminium chloride are abnormally low because it is predominantly covalent.
Both the sodium ion and magnesium ion have low charge density and low polarizing power
hence form predominantly ionic chlorides.
From silicon tetrachloride to chlorine, the substances have simple molecular structures composed
of small discrete molecules attracted to each other by weak Van der Waal’s forces that can easily
be broken. Thus they have low melting points and boiling points. However the magnitude and
strength of the Van der Waal’s forces increase with increase in molecular mass and hence
increase in their melting points and boiling points.
N.B. (a) The degree of covalent character is influenced by Fajan’s rules. i.e;
 The charges of the ions being high
 The cation having a small radius
 The anion having a large radius
The positive charge on the cation in an ionic compound can attract electrons towards it from the anion. This results
in the distortion of the electron cloud of the anion. This distortion is called polarisation.
The ability of a cation to attract electrons from the anion and distort its electron cloud is refered to as polarising
power.
The ease with which the anion gives in to polaristion is called the polarisability.
The degree of polarisation of an ionic bond is a measure of the degree of covalent character.
The measure of the polarisation power of a cation is its charge density.
Charge density = Charge of cation / Radius of cation
Ion Cationic Charge Charge Density =
radius Charge
Cationic radius
Na+ 0.095 +1 +1 = 10.5
0.095
Mg2+ 0.065 +2 +2 = 30.7
0.065
Al3+ 0.050 +3 +3 = 60
0.050
Thus;
(i) The higher the charge on cation or the smaller the radius, the higher the charge density.
(ii) The higher the charge density, the higher the polarising power.
(iii) The higher the polarising power, the higher the degree of covalent character.
The reverse is true for (i), (ii) and (iii).
(b) Aluminium chloride is predominantly covalent while magnesium chloride is slightly covalent hence they can
both dissolve in organic (nonpolar) solvents. Aluminium chloride undergoes association or dimerises when
dissolved in organic solvents to form Al2Cl6.
(c) In aqueous solution aluminium chloride is an electrolyte. When the anhydrous solid is heated at standard
pressure, it sublimes and also dimerises in the vapour to form Al2Cl6 2AlCl3(s) Al2Cl6 (g)
The structure of Al2Cl6 is as shown below;
Cl Cl
Cl
Al Al

Cl Cl Cl
2. Heat of formation.
Trend: The heat of formation of the chloride per mole of chloride atoms decreases from across
the periodic table.
Explanation: The highly electropositive elements on the left hand side of the Period react with
the highly electronegative chlorine atom to form stable ionic structures with a high negative heat

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of formation and become very stable. The electronegativity difference decreases from left to
right. Consequently the heat evolved also decreases as the bonding tends to be covalent.
Question: Explain the following observations.
(a) The melting point of magnesium oxide is greater than that of sodium oxide however melting
point of magnesium chloride is less than that of sodium chloride.
(b) Sodium chloride is a solid, disulphur dichloride is a liquid while chlorine is a gas at room
temperature.

Preparation
1) By direct combination. It involves heating of the element in dry chlorine gas. This method is
used to prepare NaCl, anhydrous MgCl2, anhydrous AlCl3, SiCl4, PCl3, PCl5 and S2Cl2.
2) Anhydrous magnesium chloride or anhydrous aluminium chloride is also prepared by heating
the element with dry hydrogen chloride gas since they are readily attacked by moisture in the air.
Aluminium chloride must be prepared under anhydrous conditions, the tube of soda lime being
used to keep out moisture as well as to absorb excess chlorine as shown in the diagram below
Aluminium chloride is a white solid which sublimes at a temperature of about 180 oC to form a
dimer at standard pressure.

3) Hydrated aluminium chloride is prepared by reaction of the excess aluminium metal with hot
dilute or hot concentrated hydrochloric acid.
It can also be prepared by reacting the excess oxide or hydroxide of aluminium with hot dilute
hydrochloric acid followed by evaporation of excess water and then crystallization.
Hydrated magnesium chloride can also be prepared in a similar way using excess magnesium
metal, magnesium oxide, magnesium carbonate of magnesium hydroxide but hydrochloric acid
should be cold and dilute. (Write equations for all the reactions)
4) Silicon tetrachloride, SiCl4, can also be conveniently prepared by heating silica and carbon in
a current of dry chlorine. SiO2(s) + 2C(s) + 2Cl2(g) SiCl4(l) + 2CO(g)
5) - Phosphorous trichloride is prepared industrially by the reaction of chlorine with
a refluxing solution of white phosphorous in phosphorous trichloride, with continuous removal
of PCl3 as it is formed (in order to avoid the formation of PCl5).
PCl3(l) + Cl2(g) PCl5(s)
In the laboratory it may be more convenient to use the less toxic red phosphorus. It is sufficiently
inexpensive that it would not be synthesized for laboratory use.
- Phosphorous(V) chloride is also obtained by heating dry chlorine gas with PCl3.
i.e. PCl3(l) + Cl2(g) PCl5(s)
6) Sulphur dichloride, SCl2 and disulphur dichloride, S2Cl2 are only obtained by passing dry
chlorine over molten sulphur. i.e. 2S(l) + Cl2(g) S2Cl2(l)
SCl2 is obtained by reacting dry chlorine with disulphur dichloride at 0oC.
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 i.e. S2Cl2(l) + Cl2(g) 2SCl2(l)
7) Chlorine gas is only prepared by heating lead(IV) oxide or potassium manganate(VII) crystals
or manganese(IV) oxide with concentrated hydrochloric acid and then dried using concentrated
sulphuric acid. 2KMnO4(s) + 16HCl(aq) 2KCl(aq) + 2MnCl2(aq) + 5Cl2(g) + 8H2O(l)
or PbO2(s) + 4HCl(aq) PbCl2(aq) + Cl2(g) + 2H2O(l)
The lead(II) chloride is dissolved when hot but will crystallize out on cooling.
Question:
Describe how anhydrous and hydrated AlCl3 can be prepared in the Laboratory.
Reaction with Water
1). Sodium chloride is purely ionic hence it only dissolves and ionizes in water.
+ −
i.e. NaCl(s) + (aq) 𝑁𝑎(𝑎𝑞) + 𝐶𝑙(𝑎𝑞)
2). Magnesium chloride undergoes partial hydrolysis in water producing magnesium hydroxide
and hydrochloric acid. Thus MgCl2(s) + H2O(l) Mg(OH)Cl(aq) + HCl(aq)
or MgCl2(s) + 2H2O(l) Mg(OH)2(aq) + 2HCl(aq)
The magnesium ion from the ionization of magnesium chloride in water undergoes hydration and
to form the hydrated complex ions (hexaaquamagnesium ions) which later undergo hydrolysis
forming an acidic solution. Thus the pH of the solution is less than 7.
i.e. Ionisation of salt in water; MgCl2(s) + (aq) Mg2+(aq) + 2Cl-(aq)
2+ [𝑀𝑔(𝐻2 𝑂)6 ]2+
followed by hydration of the magnesium ion; 𝑀𝑔(𝑎𝑞) + 6𝐻2 𝑂(l) (𝑎𝑞)

[Mg(H2O)6]2+ (aq) + 2H2O(l) [Mg(OH)2(H2O)4] (aq) + 2H3O+(aq)

then hydrolysis;
Stepwise; [𝑀𝑔(𝐻2 𝑂)]2+ (𝑎𝑞) + H2O(l)
+
[Mg (H2O)5(OH)]+(aq) + H3𝑂(𝑎𝑞)
then [𝑀𝑔(𝐻2 𝑂)5 (𝑂𝐻)]+ (𝑎𝑞) + H2O(l)
+
[Mg (H2O)4(OH)2](aq) + H3𝑂(𝑎𝑞)
Hydrolysis is due to the relatively high charge density and hence high polarizing power of the
magnesium ion.
3). If drops of water are added onto solid aluminium chloride, a violent reaction takes place
producing clouds of steamy (white) fumes of hydrogen chloride gas. Aluminium chloride readily
undergoes hydrolysis in water producing aluminium hydroxide and hydrochloric acid.
Thus AlCl3(s) + 3H2O(l) Al(OH)3(aq) + 3HCl(g)
However, if solid aluminium chloride is added to a large amount of water, it still splutters, but
instead of hydrogen chloride gas being given off, an acidic solution formed.
The aluminium chloride reacts with the water rather than just only dissolving in it.
AlCl3(s) + 6H2O(l) [Al(H2O)3(OH)3](aq) + 3HCl(g)
In the first stage, aluminium chloride completely ionizes to form ions in the aqueous solution.
Then the aluminium ion becomes heavily hydrated forming the hexaaquaaluminium ions
together with chloride ions. AlCl3(s) + (aq) Al3+(aq) + Cl-(aq)
3+
𝐴𝑙(𝑎𝑞) + 6𝐻2 𝑂(𝑙) (𝐴𝑙 (𝐻2 𝑂)6 3+
(𝑎𝑞)

Overall equation:
Due the relatively small but highly charged aluminium ion, it has a high charge density and
hence a high polarising power. Thus it undergoes hydrolysis (the ion draws electrons away from
its surrounding water molecules. The Aluminium to oxygen bond is strengthened while the
oxygen to hydrogen bond in the water molecule is weakened). This causes the water molecules
to release hydrogen ions (protons) making the solution acidic and having a pH less than 7.
Stepwise [ 𝐴𝑙(𝐻2 𝑂)6 ]3+
(𝑎𝑞) + 𝐻2 𝑂(𝑙) [𝐴𝑙 (𝐻2 𝑂)5 (𝑂𝐻)]2+ +
(𝑎𝑞) + H3 𝑂(𝑎𝑞)

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then [𝐴𝑙 (𝐻2 𝑂)5 (𝑂𝐻)]2+
(𝑎𝑞) + 𝐻2 𝑂(𝑙)
+
[Al(H2O)4(OH)2]+(aq) + H3 𝑂(𝑎𝑞)
+
and [Al(H2O)4(OH)2]+(aq) + 𝐻2 𝑂(𝑙) [Al(H2O)3(OH)3](aq) + H3𝑂(𝑎𝑞)
+
Overall equation is; [Al(H2O)6]3+(aq)+ 3𝐻2 𝑂(𝑙) [Al(H2O)3(OH)3](aq) + 3H3𝑂(𝑎𝑞)
which is also simply written without water molecules as;
[Al(H2O)6]3+(aq) [Al(H2O)3(OH)3](aq) + 3H+(aq)
Or AlCl3(s) + 6𝐻2 𝑂(𝑙) [Al(H2O)3(OH)3](aq) + 3HCl(aq)
The formation of H3O+ or H+ or HCl in water accounts for the acidity.
In summary: The small and highly positively charged aluminium ion in the hydrated complex
ion has a high charge density making it to possess a high polarizing power. The high polarizing
power leads to hydrolysis thus releasing of hydrogen ions from the water molecules in the
complex ion, which leads to the solution being acidic hence having a pH less than 7.
4). The non-metal chlorides react with water forming acidic solutions as
SiCl4(l) + 4H2O(l) SiO2.2H2O(s) + 4HCl(g)
or SiCl4(l) + 4H2O(l) Si(OH)4(aq) + 4HCl(aq)
The formation of HCl(aq) causes SiCl4 to fume in air.
PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(aq)
PCl5(s) + 4H2O(l) H3PO4(aq) + 5HCl(aq)
2SCl2(l) + 2H2O(l) S(s) + SO2(g) + 4HCl(aq)
2S2Cl2(l) + 2H2O(l) 3S(s) + SO2(g) + 4HCl(aq)
Cl2(g) + H2O(l) HOCl(aq) + HCl(aq)
Questions:
1. Explain briefly each of the following observations:
a) Aqueous solution of Aluminium chloride has a pH less than 7.
b) Aluminium chloride (or silicon(IV) chloride) fumes in moist air.
Aluminium chloride undergoes cationic hydrolysis producing hydrogen chloride gas that appears as white fumes.
AlCl3(s) + 3H2O(l) Al(OH)3(aq) + 3HCl(g)
2. Explain what will be observed when an aqueous of a solution of aluminium chloride is added:
a) drops of sodium hydroxide until in excess.
A white precipitate which is soluble in excess to form a colourless solution.
The white precipitate is due to formation of the insoluble aluminium hydroxide.
Al3+(aq) + 3OH-(aq) Al(OH)3(s)
Aluminium hydroxide being amphoteric reacts with hydroxide ions to form the soluble tetrahydroxoaluminate
complex ion as a colourless solution. Al(OH)3(s) + OH-(aq) Al(OH)4-(aq)
b) drops of ammonia until in excess.
A white precipitate which is insoluble in excess. The white precipitate is due to formation of the insoluble
aluminium hydroxide. Al3+(aq) + 3OH-(aq) Al(OH)3(s)
c) drops of sodium carbonate.
A white precipitate is formed and bubbles of a colourless gas.
The aqueous solution of aluminium chloride is acidic. The hydrogen ions present react with the carbonate ions to
liberate carbondioxide gas as a colourless gas and aluminium hydroxide as a white precipitate.
2Al3+(aq) + 3H2O(l) + 3CO32-(aq) 2Al(OH)3(s) + 3CO2(g)
d) drops of sodium hydrogen carbonate.
A white precipitate is formed and bubbles of a colourless gas.
The aqueous solution of aluminium chloride is acidic. The hydrogen ions present react with the hydrogencarbonate
ions to liberate carbondioxide gas as a colourless gas and aluminium hydroxide as a white precipitate.
Al3+(aq) + 3HCO3-(aq) Al(OH)3(s) + 3CO2(g)
e) magnesium powder or ribbon.
A white precipitate is formed and effervescence of a colourless gas.

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 The aqueous solution of aluminium chloride is acidic. The hydrogen ions present react with the magnesium ribbon
and they are displaced to liberate hydrogen gas as a colourless gas and aluminium hydroxide as a white
precipitate. 2Al3+(aq) + 6H2O(l) + 3Mg(s) 3Mg2+(aq) + 2Al(OH)3(s) + 3H2(g)
3. Pure aluminium carbonate does not exist.
Aluminium carbonate is an insoluble salt prepared by precipitation. An aqueous solution containing aluminium
ions is acidic. On addition of carbonate ions, they react with the hydrogen ions to release carbondioxide gas. Hence
the aluminium carbonate is not precipitated (formed) and will not exist.
2H+(aq) + CO32-(aq) H2O(l) + CO2(g)

(3) HYDRIDES
Formula NaH MgH2 AlH3 SiH4 PH3 H2S HCl
Appearance White solid White White White fumes
Physical state polymeric polymeric Colourless gas
Crystals Solid
Bpt (oC) 800 Low -112 -87.7 -61 -85
Mpt (oC) 300 327 150 -185 -132.8 -82 -114.2
Action of water Reacts Reacts Reacts No effect No effect Sparingly Very soluble
soluble
pH of aq
solution Alkaline Alkaline Alkaline Neutral Neutral Acidic Acidic
Bond Ionic Predominantly Predominantly Covalent Covalent Covalent Covalent
ionic ionic

Structure Giant Ionic Simple Molecular

Electronegativity 1.27 0.89 0.59 0.30 0.01 0.38 0.96

difference
Methods of Reacting Reacting Heating Reacting Reacting
metal with Passing hydrogen over Si Cl4 conc Fe(s) and conc H2SO4
preparation
hydrogen heated metal and NaOH dilute and NaCl
gas LiAlH4 and HCl(aq) crystals
phosphorous
Action of heat Decomposes Decomposes Decomposes
No action
The explanation for the variation in melting points and boiling points is similar to that of the
oxides of period 3 elements.
Preparation
a) NaH: By reacting Sodium metal with hydrogen gas. 2 Na(s) + H2(g) 2NaH(s)

b) MgH2: By passing hydrogen over heated Mg. Mg(s) + H2(g) MgH2(s)

However MgH2 is best prepared by reacting MgCl2 with LiAlH4.
i.e. 2MgCl2(s) + LiAlH4(s) 2MgH2(s) + LiCl(s) + AlCl3(s)

c) AlH3: By burning aluminium in dry hydrogen gas. 2Al(s) + 3H2(g) 2AlH3(s)

d) SiH4 (Silane); By reacting silane with Lithium aluminium tetrahydride.

SiCl4(l) + LiAlH4(s) SiH4(g) + LiCl(s) + AlCl3(s)

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e) PH3 (Phosphine): By reacting hot concentrated NaOH and Phosphorous
P4(s) + 3NaOH(g) + 3H2O(l) PH3(g) + 3NaH2PO2(aq)
− −
or 4 P(s) + 3𝑂𝐻(𝑎𝑞) + 3H2O(l) PH3(g) + H2𝑃𝑂2(𝑎𝑞) (Phosphinate)

f) H2S; By reacting Iron(II) sulphide with hydrochloric acid.

FeS + 2 HCl(aq) FeCl2(aq) + H2S(g)
g) HCl: By reacting sodium chloride crystals with concentrated sulphuric acid.
NaCl(s) + H2SO4(aq) NaHSO4(aq) + HCl(g)
Ionic Hydrides
These include NaH, MgH2 and AlH3
1. Reaction with water. They react with water with the negative hydride ion H - (from Na+H-)
abstracting H+ (protons) from water forming a colorless gas hydrogen. The reaction is slowest
with the hydride of aluminium.
Na𝐻(𝑠) + H2O(l) NaOH(aq) + H2(g)
MgH2(s) + 2H2O(l) Mg(OH)2(aq) (s) + 2H2(g)
AlH3(s) + 3H2O(l) Al(OH)3(aq) (s) + 3H2(g)
2. Action of heat. They are unstable to heat decomposing to their elements as
NaH(s) heat 2Na(s) + H2(g)
heat
MgH2(s) Mg(s) + H2(g)
heat
2AlH3(s) 2Al(s) + 3H2(g)
Covalent Hydrides
1. The non-metals have high electronegativity and have the tendency of forming covalent
hydrides. Consequently, they have low melting and boiling points.
2. Phosphorous and hydrogen almost have similar electronegativity therefore the magnitude of
partial charges in PH3 is small and the proton cannot easily be abstracted. Hence PH 3 does not
dissolve in water.
3. SiH4 is hydrolysed by water in the presence of an alkali. This is because the difference in
electronegativity between Si and H is very small (Si = 1.8 and H = 2.1). Therefore, the
magnitude of partial charge that exists in SiH4 is small as compared to SiCl4.
SiH4(g) + H2O(l) + 2OH-(aq)⟶ SiO32-(s) + 4H2(g)
4. From H2S to HCl, the acidity increases. The attraction for the electrons of the covalent bond in
the HCl molecule is greater than in H2S because chlorine is more electronegative.
i.e. the bond in H – Cl is more polar that in H2S due to the high electronegativity of chlorine.
HCl(g) + (aq) H+(aq) + Cl-(aq) or HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
H2S(g) + (aq) H+(aq) + HS-(aq) or H2S(g) + H2O(l) H3O+(aq) + HS-(aq)
This increases the partial charge on the attracted hydrogen and the covalent bond between
hydrogen and chlorine becomes weaker. The hydrogen is therefore more easily lost as a proton.
Hence HCl is more acidic than H2S.

Question:
Explain each one of the following observation.
(a) PH3 does not react with water whereas H2S and HCl does.
(b) An aqueous solution of HCl is more acidic than that of H2S.

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Extraction of aluminium
An ore is a naturally occurring impure chemical substance from which a metal can be extracted.
Aluminium is obtained by the electrolysis of molten aluminium oxide. The oxide is obtained
from the ore called bauxite which is impure aluminium oxide with formula Al2O3.2H2O. It
contains silicon(IV) oxide and iron(III) oxide as major impurities. Stages involved are:
Stage 1. Concentration of the ore by leaching: In this method, a suitable solvent is used to
dissolve the substance and the precipitate out the pure substance from solution.
The ore is first roasted to convert all the iron(II) present to iron(III) oxide.
It is then heated with concentrated sodium hydroxide. The aluminium oxide and silicon dioxide
(silica) dissolve to form a solution but the iron(III) oxide and other basic materials remain
undissolved. Thus
−
Al2O3(s) + 2OH(aq) + 3H2 O(l) 2[Al(OH)4 ]− (aq)
−
and SiO2(s) + 2OH(aq) SiO2−
3(aq) + H O
2 (l)
The basic insoluble materials are filtered off. The filtrate is then treated with carbon dioxide or
seeded with aluminium hydroxide to precipitate aluminium hydroxide. Silica remains dissolved
(in solution).
[Al(OH)4 ]−(aq) + CO2(g) 2Al(OH)3(s) + CO2− 3(aq) + H2 O(l)
− −
or [Al(OH)4 ](aq) Al(OH)3(s) + OH(aq) i.e. seeding where aluminium hydroxide
induces hydrolysis of the tetrahydroxoaluminate ion to precipitate aluminium hydroxide.
The aluminium hydroxide is then heated to obtain the concentrated aluminium oxide.
2Al(OH)3(s) heat Al2O3(s) + 3H2O(g)
Stage 2. Extraction by electrolysis of molten aluminium oxide: The oxide is then dissolved in
molten cryolite (Na3AlF6) and electrolysed at about 9000C using graphite (carbon) electrodes.
Cryolite helps in lowering the melting point of aluminium oxide and also acts as an electrolyte.

At the cathode: Aluminium is discharged as Al3+(l) + 3e- Al(l)

The molten aluminium collects at the bottom of the cell and is tapped off periodically.
At the anode: Oxygen is given off as 2O2- (l) O2(g) + 2e-
The oxygen reacts with the carbon (graphite) of the anode to form oxides of carbon at the high
temperatures involved. As a result the anodes are gradually burnt away and must be replaced
from time to time.
Low voltage is usually used to avoid the decomposition of the cryolite.
N.B: Aluminium is a silvery-white, lightweight metal. It is soft and malleable. Some of the many
uses for aluminium metal are in:
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  Transportation (automobiles, aircraft, trucks, railway cars, marine vessels, bicycles,
spacecraft, etc.) as sheet, tube, and castings.
 Packaging (cans, foil, frame of etc.).
 Food and beverage containers, because of its resistance to corrosion.
Chemical reactions or tests involving aluminium ions, Al3+ in solution include:
(a) Sodium hydroxide solution is added dropwise until in excess to an aqueous solution
containing aluminium ions: a white precipitate of the insoluble aluminium hydroxide is formed
which is soluble in excess to form a colourless solution due to formation of the soluble
complex of tetraaquaaluminium ion indicates the presence of aluminum.
Al3+(aq) + 3OH-(aq) Al(OH)3(s) then Al(OH)3(s) + OH-(aq) Al(OH)4 -(aq)
(b) Ammonia solution dropwise until in excess is added dropwise until in excess to an aqueous
solution containing aluminium ions: a white precipitate of the insoluble aluminium hydroxide
which is insoluble in excess is formed. Al3+(aq) + 3OH-(aq) Al(OH)3(s)
The precipitate is also formed even in presence of ammonium chloride.
Note that:
Hydroxides of aluminium, chromium and iron(III) are precipitated by ammonia even in presence
of ammonium chloride.
(c) Drops of sodium carbonate or hydrogen carbonate are added to an aqueous solution
containing aluminium ions: a white precipitate is formed with bubbles of a colourless gas.
(d) Magnesium is added to an aqueous solution containing aluminium ions: a white precipitate
is formed with effervescence of a colourless gas.
(e) Hydrogen sulphide gas is bubbled through an aqueous solution containing aluminium ions in
presence of ammonia and ammonium chloride; forms a white precipitate of the insoluble
aluminium hydroxide, owing to hydrolysis of the aluminum sulphide.
(f) Drops of litmus solution are added to an aqueous solution containing aluminium ions
followed by drops of dilute hydrochloric acid until acidic, then drops of ammonia until
alkaline. A blue solution (lake) is formed.
(g) Drops of disodium hydrogen phosphate solution are added to an aqueous solution
containing aluminium ions: a white gelatinous precipitate is formed.
Al2(SO4)3(aq) + 2Na2HPO4(aq) 2AlPO4(s) + 2NaHSO4(aq) + Na2SO4(aq)
(h) Drops of alizarin solution followed by ammonia solution are added to an aqueous solution
containing aluminium ions: a pink (solution) lake is formed.
(i) A drop of cobalt(II) nitrate solution is added to an aqueous solution containing aluminium
ions. Then moisten a piece of filter paper with this mixture and heat the paper strongly by
playing a flame on it directly; a bright blue ash of cobalt(II) aluminate is formed.
Questions:
1. Explain the following.
(a) AlCl3 is covalent whereas Al2O3 is ionic.
(b) AlF3 has a high melting point whereas AlCl3 is of a low melting point.
2. For the elements Na, Mg, Al, Si, P, S and Cl,
(a) write the formula of their; (i) Oxides (ii) Hydrides (iii) Chlorides

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(b) For each of the compounds mentioned above, write the equation for the reaction that occurs (if any) when
water is added to each of them. State whether the pH of the solution will be less than, greater than or equal to 7.

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