B.

INORGANIC CHEMISTRY
 Deals with trends and properties of elements of the periodic table.
 The topics to be covered are:
9. Chemical Periodicity of period 3
10. Chemistry of Group II elements
11. Chemistry of Group IV elements
12. Chemistry of Group VII elements
13. Nitrogen and sulphur
9.0 CHEMICAL PERIODICITY OF PERIOD 3
Objectives

By the end of the subtopic, you should be able to:

 Describe the variations in atomic radius, ionic radius, ionisation energy, melting
point and electrical conductivity of period 3 elements.
 Explain the variation in atomic radius, ionic radius and first ionisation energy.
 Interpret the variation in melting point and electrical conductivity in terms of
bonding and structure.
 Describe the reactions if any, of elements with oxygen, chlorine and water.
 Explain the variation in oxidation number of oxides and chlorides.
 Describe the acid base behaviour of oxides.
 Describe the reactions of oxides and chlorides with water.
 Suggest the type of bonding present in chlorides and oxides from their physical
and chemical properties.
 Introduction

 A group is vertical column of elements in the periodic table that share similar chemical
properties. Elements in the same group have the same number of valence electrons.
 A period is horizontal row of elements in the periodic table with the same highest principal
quantum number.
 Elements in the same period show periodic changes in their physical and chemical quantities.
 Period 3 elements are: Na(s), Mg(s), Al(s), Si(s), P(s), S(s), Cl 2(g), Ar(g)
Table 9.1: Chemical periodicity of the elements
Element Standard state Chemical structure Appearance Electrical
conductivity
Sodium Na(s) Metallic bonding Shiny, soft metal +

Magnesium Mg(s) Metallic bonding Shiny metal +

Aluminium Al(s) Metallic bonding Shiny metal +

Silicon Si(s) Giant covalent Shiny black solid Semi-conductor

Crystal
Phosphorus P4(s) White Simple Covalent Waxy solid -
phosphorus molecule Polymeric red
P(s) Red powder
phosphorus

Sulphur S8 Simple covalent Bright yellow -

molecule crystalline solid

Chlorine Cl2(g) Simple covalent Yellow-green gas -

molecule
Argon Ar(g) Single atom Colourless gas -
 Melting and boiling points

 Rise from Na to Si, and then fall to low values.

 Strong metallic bonding in Na, Mg and Al cause high melting and boiling points. The strength of
the metallic bonding depends on the number of outer electrons - the greater the number, the
stronger the bond.
 The strength of the metallic bond increases from Na to Al, same as the melting points and
boiling points.
 Silicon has a giant covalent structure, leading to very high melting and boiling points.
 P, S and Cl have simple molecular structures, held together by Van der Waals forces only, so
melting and boiling points are low.
 Ar exists as atoms, not molecules. This means that the Van der Waals forces are very weak,
giving it a very low melting and boiling point.
Electrical conductivity
 Relatively high for metals - Na, Mg and Al (due to the de-localised electrons in metallic
structures). Lower in metalloids (Si) and almost negligible –metals (P, S, Cl and Ar).
First ionisation energy
 The general trend is for an increase across a period, due to the increasing nuclear charge
making it more difficult to remove an electron.
 Anomalies on the trend occur; these are due to:
 Full sub-shell stability - it is comparatively harder to remove an electron from a full sub-shell.
 Half-shell stability - it is comparatively harder to remove an electron from a half-empty p sub-shell.
 p-electrons being easier to remove than s-electrons, due to being at higher energy level.
 This produces the pattern shown below (figure 9.1)

1600
FIRST IONISATION ENERGY (KJ

1400
1200
1000
MOL-1)

800
600
400
200
0
Na Mg Al Si P S Cl Ar
ELEMENT

Fig 9.1: Trends in first ionization energy across period 3

 Atomic radius

 It decreases across the period.

 If we move from one element to the next across the third period, electrons are being added to the same third shell at about
the same distance from the nucleus, whilst protons are being added to the nucleus.
 The increased nuclear change pulls the electrons in the third shell closer to it, hence atomic radii decrease.

0.25

0.2
0.186 0.192

ATOMIC RADIUS (NM)

0.160
0.15 0.143
0.117 0.110
0.1 0.104 0.099

0.05

0
Na Mg Al Si P S Cl Ar

ELEMENT

Fig 9.2 Trends in atomic radius across Period 3

Electronegativity

 This is the ability to attract electrons within a bond.

 Bonding, as we move across the period, electronegativity increases to
Chlorine.
 Argon has little or no electronegativity since as a noble gas, it has only
completed shells of electrons and so does not form bonds at all readily.
 Trend in oxidation number of the
period 3 oxides and chlorides
 Across the period, the oxidation number increases along with increasing variation in oxidation number.
 Oxidation numbers of the oxides are always positive since oxygen is the 2nd most electronegative element.
 Metals only display one possible oxidation number, which corresponds to the loss of all their valence electrons.
 Non-metals in group 3 are able to expand their octet using vacant d-orbitals. The oxidation number thus depends
on the number of electrons used for bonding.

Fig 9.3: Phosphorus and sulphur molecules

Table 9.2 Chemical reactions of elements with oxygen
Element Reactions and Observations Equations Appearance of oxides
Na - Vanishes rapidly in air. 1 White ionic solid
2𝑁𝑎 𝑠 + 𝑂2 𝑔 ⟶ 𝑁𝑎2 𝑂(𝑠)
- Burns with a brilliant yellow flame. 2
Mg - Tarnishes slowly in air. 1 White ionic solid
𝑀𝑔 𝑠 + 𝑂2 𝑔 ⟶ 𝑀𝑔𝑂(𝑠)
- Burns with a bright white light, very exothermic 2

Al - Protected from further oxidation with Al2O3. 3 White Ionic Solid with some
2𝐴𝑙 𝑠 + 𝑂 𝑔 ⟶ 𝐴𝑙2 𝑂3 (𝑠)
- Requires a temperature of > 800°C to convert 2 2 covalent character
much of Al to Al2O3.
Si - No observable reactions. 𝑆𝑖 𝑠 + 𝑂2 𝑔 → 𝑆𝑖𝑂2 (𝑠) Giant covalent crystal
- Silicon dioxide can be formed if silicon is
heated strongly enough.
P - White Phosphorous P4 catches fire 4𝑃 𝑠 + 3𝑂2 𝑔 → 𝑃4 𝑂6 (𝑠) White simple covalent
spontaneously in air with a bright white flame molecules
due to strained bond angles. 4𝑃 𝑠 + 5𝑂2 𝑔 → 𝑃4 𝑂10 (𝑠)
- Red Phosphorous P8 burns on heating with a
soft orange flame.
S - Burns on gentle heating with a pale blue 𝑆 𝑠 + 𝑂2 𝑔 → 𝑆𝑂2 (𝑔) Colourless simple covalent
flame. 1 gas
𝑆𝑂2 𝑔 + 𝑂2 𝑔 ⟶ 𝑆𝑂3 (𝑔)
2
Cl - No observable reactions. - -
Ar - No observable reactions. - -
Table 9.3 Chemical reactions of elements with chlorine
Element Reactions and Observations Equations Appearance of chlorides
Na - Burns readily, very exothermic. 1 White ionic solid
𝑁𝑎 𝑠 + 𝐶𝑙2 𝑔 ⟶ 𝑁𝑎𝐶𝑙(𝑠)
2
Mg - Burn readily, very exothermic. 𝑀𝑔 𝑠 + 𝐶𝑙2 𝑔 ⟶ 𝑀𝑔𝐶𝑙2 (𝑠) White ionic solid
Al - Slow reaction at room 3 Pale yellow powder
𝐴𝑙 𝑠 + 𝐶𝑙2 𝑔 ⟶ 𝐴𝑙𝐶𝑙3 (𝑠)
temperature. 2 Dimerises at high
- Chlorine is usually passed over temperature
heated aluminium foil. 2𝐴𝑙𝐶𝑙3 𝑔 ⟶ 𝐴𝑙2 𝐶𝑙6 (𝑔)

Si - Slow reaction at room 𝑆𝑖 𝑠 + 2𝐶𝑙2 𝑔 ⟶ 𝑆𝑖𝐶𝑙4 (𝑠) Colourless volatile simple

temperature. covalent molecule
- Chlorine is usually passed over
heated silicon powder.
P - White Phosphorous P4 burns 2𝑃 𝑠 + 3𝐶𝑙2 𝑔 ⟶ 2𝑃𝐶𝑙3 (𝑙) Colourless simple
vigorously due to strained bond 2𝑃 𝑠 + 5𝐶𝑙2 𝑔 ⟶ 2𝑃𝐶𝑙5 (𝑠) covalent molecule
angles. Pale white solid
S - Chlorine is usually passed over 2𝑆 𝑠 + 𝐶𝑙2 𝑔 → 𝑆2 𝐶𝑙2 (𝑙) Smelly orange simple
heated Sulphur. covalent liquid
Cl - No observable reactions. - -
Ar - No observable reactions. - -
Table 9.4 Chemical reactions of elements with water
Element Reactions and observations Equations
Na - Rapid and violent reaction, very exothermic. 1
𝑁𝑎 𝑠 + 𝐻2 𝑂 𝑙 → 𝑁𝑎𝑂𝐻 + 𝐻 𝑔
- Effervescence of a colourless and odourless gas. 2 2

Mg - Slow reaction with cold water. 𝑀𝑔 𝑠 + 2𝐻2 𝑂 𝑙 → 𝑀𝑔 𝑂𝐻 2 𝑠 + 𝐻2 (𝑔)

- Rapid reaction with steam.
- Effervescence of a colourless and odourless gas 𝑀𝑔 𝑠 + 𝐻2 𝑂 𝑔 → 𝑀𝑔𝑂 𝑠 + 𝐻2 (𝑔)

Al - No observable reactions due to Al2O3 layer. -

Si - No observable reactions at room temperature. 𝑆𝑖 𝑠 + 𝐻2 𝑂 𝑔 → 𝑆𝑖𝑂2 𝑠 + 2𝐻2 𝑂(𝑔)
- Reaction only occurs with steam and high
temperatures.

P - No observable reactions. -
S - No observable reactions. -
Cl - Disproportionates in water to form an acidic 𝐶𝑙2 𝑔 + 𝐻2 𝑂 𝑙 ⇌ 𝐻𝐶𝑙 + 𝐻𝑂𝐶𝑙
solution.
Ar - No observable reactions. -
 Properties of oxides

Table 9.5 Properties of oxides

Element Standard Chemical structure Solubility Acidity pH
state

Sodium Na2O(s) Giant ionic lattice Soluble Basic 13

Magnesium MgO(s) Giant ionic lattice Sparingly soluble Basic 9

Aluminium Al2O3(s) Giant ionic lattice Insoluble Amphoteric -

Silicon SiO2(s) Giant covalent Insoluble - -
Phosphorus P4O6(s) Simple, discrete covalent Soluble Acidic 2
P4O10(s) molecules 2

Sulphur SO2(g) Simple, discrete covalent Soluble Acidic 2

SO3(l) molecules 1
 Across the period, the bonding gradually changes from ionic to covalent.
 This is due to the decrease in the difference in electronegativity between each element and
oxygen across the period.
 Metals have low ionisation energies and tend to lose electrons to oxygen to form ionic compounds.
 Non-metals tend to have higher ionisation energies and tend to form covalent bonds with oxygen.
Trend in melting point
 High melting points for Na2O, MgO and Al2O3 as they are all giant ionic lattices and require a large
amount of energy to overcome the lattice energy.
 The melting point of MgO is higher than that of Na2O as Mg2+ has a higher charge than Na+, hence
the lattice energy for MgO is higher than that of Na2O.
 Anomaly: Melting point of Al2O3 is lower than that of MgO due to the high charge density of Al3+,
which polarises the O2- ion and confers covalent character to Al2O3. The lattice energy of Al2O3 is
thus smaller than that of MgO.
 Silicon dioxide has a very high melting point as it exists as a giant covalent crystal with high bond
dissociation energies of the Si-O bonds. A large amount of energy is required to overcome the
bond dissociation energy, resulting in a high melting point.
 Oxides of phosphorus and sulphur have low melting points as they exist as simple covalent
molecules held together with weak van der Waals attraction.
 P4O10 sublimes at 360°C.
 Acid-base reactions of the oxides and
hydroxides
Table 9.6 Acid-base reactions of oxides and hydroxides
Oxide Reaction with H2O Reaction with H+ Reaction with OH- pH
Na2O Reacts violently with water to form a strong Dissolves in acids to produce a salt - 13
alkaline solution. solution via neutralization.
𝑁𝑎2 𝑂 𝑠 + 𝐻2 𝑂 𝑙 → 2𝑁𝑎𝑂𝐻 𝑁𝑎2 𝑠 + 2𝐻 + → 2𝑁𝑎+ + 𝐻2 𝑂(𝑙)

NaOH - Dissolves in acids to produce a salt - 13

solution via neutralisation.
𝑁𝑎𝑂𝐻 + 𝐻 + → 𝑁𝑎+ + 𝐻2 𝑂(𝑙)

MgO Slow reaction, limited solubility. Magnesium Dissolves in acids to produce a salt - 9
hydroxide formed is also only sparingly soluble. solution via neutralization.
𝑀𝑔𝑂 𝑠 + 𝐻2 𝑂 𝑙 → 𝑀𝑔(𝑂𝐻)2 𝑀𝑔𝑂 𝑠 + 2𝐻 + → 𝑀𝑔2+ + 𝐻2 𝑂(𝑙)
𝑀𝑔 𝑂𝐻 2 𝑠 ⇌ 𝑀𝑔2+ + 2𝑂𝐻 −
Mg(OH)2 - Dissolves in acids to produce a salt - 9
solution via neutralisation.
𝑀𝑔(𝑂𝐻)2 + 2𝐻 + → 𝑀𝑔2+ + 2𝐻2 𝑂(𝑙)

Al2O3 Insoluble due to high lattice energy. Dissolves in acids to produce a salt Dissolves in excess bases to form a -
solution via neutralisation. colourless solution
𝐴𝑙2 𝑂3 𝑠 + 6𝐻 + → 𝐴𝑙 3+ + 3𝐻2 𝑂(𝑙) 𝐴𝑙2 𝑂3 𝑠 + 2𝑂𝐻 − + 3𝐻2 𝑂(𝑙)
→ + 2[𝐴𝑙(𝑂𝐻)4 ]−
Oxide Reaction with H2O Reaction with H+ Reaction with OH- pH
Al(OH)3 Insoluble due to high lattice energy. Dissolves in acids to produce a salt Dissolves in excess bases to form a -
solution via neutralisation. colourless solution.
𝐴𝑙 𝑂𝐻 3 𝑠 + 3𝐻 + → 𝐴𝑙3+ + 3𝐻2 𝑂(𝑙) 𝐴𝑙 𝑂𝐻 3 𝑠 + 𝑂𝐻 − → [𝐴𝑙(𝑂𝐻)4 ]−

SiO2 Insoluble due to high bond dissociation - Dissolves in hot, concentrated and -
energy. excess strong bases via neutralisation.
𝑆𝑖𝑂2 𝑠 + 2𝑂𝐻 − → 𝑆𝑖𝑂3 2− + 𝐻2 𝑂(𝑙)
P4O6 Reacts with cold water to form an acidic - Dissolves in bases to produce a salt 2
solution of dibasic phosphorous acid solution via neutralization.
𝑃4 𝑂6 𝑠 + 6𝐻2 𝑂 𝑙 → 4𝐻3 𝑃𝑂3 𝑃4 𝑂6 𝑠 + 8𝑂𝐻 − → 4𝐻𝑃𝑂3 2− + 2𝐻2 𝑂(𝑙)
P4O10 Reacts violently with water to form an acidic - Dissolves in bases to produce a salt 2.15
solution of tribasic phosphoric acid. solution via neutralization.
𝑃4 𝑂10 𝑠 + 6𝐻2 𝑂 𝑙 → 4𝐻3 𝑃𝑂4 𝑃4 𝑂10 𝑠 + 12𝑂𝐻 − → 4𝑃𝑂4 3− + 6𝐻2 𝑂(𝑙)
𝐻2 𝑆𝑂3 ⇌ 𝐻2 𝑃𝑂4 − + 𝐻 +
SO2 Reacts with water to form an acidic solution - Reacts with bases to produce a salt 1.8
of dibasic sulphurous acid. solution via neutralization.
𝑆𝑂2 𝑔 + 𝐻2 𝑂 𝑙 → 𝐻2 𝑆𝑂3 𝑆𝑂2 𝑔 + 2𝑂𝐻 − → 𝑆𝑂3 2− + 𝐻2 𝑂(𝑙)

𝐻2 𝑆𝑂3 ⇌ 𝐻𝑆𝑂3 − + 𝐻 +
SO3 Reacts violently with water to form an acidic - Reacts with bases to produce a salt 1
solution of dibasic sulphuric acid. solution via neutralization.
𝑆𝑂3 𝑔 + 𝐻2 𝑂 𝑙 → 𝐻2 𝑆𝑂4 𝑆𝑂3 𝑔 + 2𝑂𝐻 − → 𝑆𝑂4 2− + 𝐻2 𝑂(𝑙)

𝐻2 𝑆𝑂4 ⇌ 𝐻𝑆𝑂4 − + 𝐻 +
 Properties of chlorides

Table 9.7 Properties of chlorides

Element Standard Chemical structure Solubility Acidity pH in solution
state
Sodium NaCl(s) Giant ionic lattice Soluble Neutral 7
Magnesium MgCl2(s) Giant ionic lattice Soluble Hydrolyses slightly 6.5

Aluminium AlCl3(s) Giant ionic lattice/Simple, Soluble Hydrolyses to a large 3

discrete covalent extent
molecules in gaseous
state.
Silicon SiCl4(s) Simple, discrete covalent Soluble Forms HCl 1
molecules in gaseous state

Phosphorus PCl3(l) Simple, discrete covalent Soluble Forms HCl 1

PCl5(s) molecules in gaseous state 1
 Across the period, the bonding involved gradually changes from ionic to covalent.
 This is due to the decrease in the difference in electronegativity between each element and chlorine
across the period.
 Metals have low ionization energies and tend to lose electrons to oxygen to form ionic compounds.
 Non-metals tend to have higher ionisation energies and tend to form covalent bonds with oxygen.

Trend in melting point

 High melting points for NaCl, MgCl2 and AlCl3 as they are all giant ionic lattices and require a large
amount of energy to overcome the lattice energy.
 The melting point of MgCl2 is lower than that of NaCl as Mg2+ has a higher charge density than Na+,
allowing it to polarise the Cl- ion.
 Deviation: Melting point of AlCl3 is lower than that of MgCl2 due to the high charge density of Al3+,
which polarises the Cl- ion and confers covalent character to AlCl3. The lattice energy of AlCl3 is thus
smaller than that of MgCl2.
 Since Al is electron deficient, AlCl3 sublimes at 180°C to form a dimer Al2Cl6.
2𝐴𝑙𝐶𝑙3 ⇌ 𝐴𝑙2 𝐶𝑙6 Δ𝐻 < 0
 Silicon Dichloride and Phosphorous trichloride exist as simple discrete covalent molecules held together
by weak dispersion forces between molecules. Since less energy is required to overcome these forces,
they have considerably lower melting points compared to the metallic chlorides.
 PCl5 exists as exist as simple discrete covalent molecules held together by weak dispersion forces
between molecules.
 Reaction of chlorides with water

Table 9.8 Reactions of chlorides with water

Chloride Observations Reactions pH
NaCl Solid dissolves in 𝑁𝑎𝐶𝑙 𝑠 ⟶ 𝑁𝑎+ + 𝐶𝑙 − 7
water to form a
colourless solution. Na+ has a very low charge density to undergo
hydrolysis.
MgCl2 Solid dissolves in 𝑀𝑔𝐶𝑙2 𝑠 + 6𝐻2 𝑂 𝑙 → [𝑀𝑔(𝐻2 𝑂)6 ]2+ + 2𝐶𝑙 − 6.5
water to form a
colourless solution. [𝑀𝑔(𝐻2 𝑂)6 ]2+ + 𝐻2 𝑂 𝑙 ⇌ [𝑀𝑔(𝐻2 𝑂)5 𝑂𝐻]+ + 𝐻3 𝑂+
Magnesium has a high charge density and undergoes
slight hydrolysis to yield a weakly acidic solution.
Chloride Observations Reactions pH
AlCl3 Addition of water drop wise In limited H2O. 3
causes white fumes of HCl to 𝐴𝑙𝐶𝑙3 𝑠 + 3𝐻2 𝑂 𝑙 → 𝐴𝑙 𝑂𝐻 3 𝑠 + 3𝐻𝐶𝑙(𝑔)
be produced along with an
insoluble white solid. In excess H2O
𝐴𝑙𝐶𝑙3 𝑠 + 6𝐻2 𝑂 𝑙 → 𝐴𝑙 𝐻2 𝑂 6 3+ 3𝐶𝑙 −
[𝐴𝑙(𝐻2 𝑂)6 ]3+ + 𝐻2 𝑂 𝑙 ⇌ [𝐴𝑙(𝐻2 𝑂)5 (𝑂𝐻)]2+ + 𝐻3 𝑂+

Aluminium has a very high charge density and undergoes hydrolysis to yield an acidic
solution by polarising and breaking the O-H bonds.

Adding an excess of a strong base, drop-wise causes deprotonation until a white precipitate
is formed.
Addition of excess water [𝐴𝑙 𝐻2 𝑂 5 (𝑂𝐻)] + 𝑂𝐻 𝑙 ⇌ [𝐴𝑙 𝐻2 𝑂 4 (𝑂𝐻)2 ]+ + 𝐻2 𝑂(𝑙)
2+ −
causes the solid to dissolve to
form a colourless solution. [𝐴𝑙 𝐻2 𝑂 4 (𝑂𝐻)2 ]+ + 𝑂𝐻 − 𝑙 ⇌ [𝐴𝑙 𝐻2 𝑂 3 (𝑂𝐻)3 ] + 𝐻2 𝑂(𝑙)

Adding an excess of a strong base causes the white precipitate to dissolve to form a
colourless solution.
[𝐴𝑙 𝐻2 𝑂 3 (𝑂𝐻)3 ]+ + 𝑂𝐻 − 𝑙 ⇌ [𝐴𝑙 𝑂𝐻 4 ]− + 3𝐻2 𝑂(𝑙)

SiCl4 Violent reaction producing Complete Hydrolysis 1

white fumes of HCl gas 𝑆𝑖𝐶𝑙4 𝑙 + 4𝐻2 𝑂 𝑙 → 𝑆𝑖𝑂2 . (𝐻2 𝑂)2 +4𝐻𝐶𝑙

PCl3 Complete hydrolysis 1

𝑃𝐶𝑙3 𝑙 + 3𝐻2 𝑂 𝑙 → 𝐻3 𝑃𝑂3 + 3𝐻𝐶𝑙
PCl5 Complete hydrolysis 1
𝑃𝐶𝑙5 𝑠 + 4𝐻2 𝑂 𝑙 → 𝐻3 𝑃𝑂4 + 5𝐻𝐶𝑙

Adding water drop wise

𝑃𝐶𝑙5 𝑠 + 𝐻2 𝑂 𝑙 → 𝐻𝑂𝐶𝑙3 + 2𝐻𝐶𝑙(𝑔)
 Assessment Exercise 9.0 Periodicity

1. State and explain the following trends:

a. atomic size across Period 3
b. first ionisation energy across Period 3
c. electronegativity across Period 3
d. melting point from sodium to aluminium
e. electrical conductivity from sodium to aluminium [10]
2. Explain the following:
a. The melting point of silicon is the highest in Period 3..
b. The melting point of phosphorus is lower than silicon.
c. The melting point of phosphorus is lower than that of Sulphur.
d. The boiling point of chlorine is greater than that of argon, but lower than that of Sulphur.
e. Neither silicon nor sulphur conducts electricity. [10]