THE PERIODIC TABLE: CHEMICAL PERIODICITY

Content
• Periodicity of physical properties of the elements: variation with proton number across the third
period (sodium to argon) of:
(i) atomic radius and ionic radius
(ii) melting point
(iii) electrical conductivity
(iv) ionisation energy
• Periodicity of chemical properties of the elements in the third period
(i) Reaction of the elements with oxygen and chlorine
(ii) Variation in oxidation number of the oxides (sodium to sulfur only) and of the chlorides
(sodium to phosphorus only)
(iii) Reactions of these oxides and chlorides with water
(iv) Acid/base behaviour of these oxides and the corresponding hydroxides

Learning Outcomes
Candidates should, for the third period (sodium to argon), be able to:
(a) describe qualitatively (and indicate the periodicity in) the variations in atomic radius, ionic
radius, melting point and electrical conductivity of the elements (see the Data Booklet)
(b) explain qualitatively the variation in atomic radius and ionic radius
(c) interpret the variation in melting point and in electrical conductivity in terms of the presence
of simple molecular, giant molecular or metallic bonding in the elements
(d) explain the variation in first ionisation energy
(e) describe the reactions, if any, of the elements with oxygen (to give Na2O; MgO; Al2O3;P4O6;
P4O10; SO2; SO3), and chlorine (to give NaCl; MgCl2; AlCl3; SiCl4; PCl3; PCl5)
(f) state and explain the variation in oxidation number of the oxides and chlorides
(g) describe the reactions of the oxides with water
[treatment of peroxides and superoxides is not required]
(h) describe and explain the acid/base behaviour of oxides and hydroxides, inCluding, where
relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and acids
(i) describe and explain the reactions of the chlorides with water
(j) interpret the variations and trends in (f), (g), (h), and (i) in terms of bonding and
electronegativity
(k) suggest the types of chemical bonding present in chlorides and oxides from observations of
their chemical and physical properties

In addition, candidates should be able to:

(l) predict the characteristic properties of an element in a given Group by using knowledge of
chemical periodicity
(m) deduce the nature, possible position in the Periodic Table, and identity of unknown elements
from given information of physical and chemical properties

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INTRODUCTION
• Elements in the periodic tables are arranged according to their proton numbers.
• The vertical columns are called Groups.
Elements in the same group will have the same number of valence electrons and outermost
electronic configuration. Consequently, they show many similarities in their physical and
chemical properties.

Gp 2: Be (1s2 2s2), Mg (1s2 2s2 2p6 3s2), Ca (1s2 2s2 2p6 3s2 3p6 3d10 4s2)
Gp 17: F (1s2 2s22p5), Cl (1s2 2s2 2p6 3s23p5), Br (1s2 2s2 2p6 3s2 3p6 3d10 4s24p5)

• The horizontal rows in the table are called Periods.

Elements in the same period have the same number of quantum shells but different number
of valence electrons. Consequently, they have different physical and chemical properties, but
trends become apparent in these properties as we move across a period.

We will study the trends in properties of Period 3 elements:

Na (1s2 2s2 2p6 3s1), Mg (1s2 2s2 2p6 3s2), Al (1s2 2s2 2p6 3s23p1) … … S (1s2 2s2 2p6 3s23p4),
Cl (1s2 2s2 2p6 3s23p5), Ar (1s2 2s2 2p6 3s23p6)

▪ Physical Properties (section 2)

2a. ionisation energy
2b. atomic radius and ionic radius
2c. melting point
2d. electrical conductivity
2e. electronegativity

▪ Chemical Properties (section 3)

3a. Reaction of the elements with oxygen and chlorine
3b. Variation in oxidation number of oxides and chlorides
3c. Reactions of chlorides with water
3d. Reactions of oxides with water
3d. Base/acid behaviour of these oxides and the corresponding
hydroxides/acids

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PERIODICITY OF PHYSICAL PROPERTIES OF PERIOD 3 ELEMENTS

1a. Ionisation Energy

2000

Ionisation Energy
Ar
1500 Cl
P
S
1000 Si
Mg

500
Al
Na

0
11 12 13 14 15 16 17 18
Proton No.

 1st Ionisation energies generally increase across the period.

Trend
Expn • Across the period, nuClear charge increases (as no. of protons increases)
• while shielding effect remains approximately the same (as successive electrons are
added to the same outermost shell).
• Hence effective nuClear charge increases.
• Energy needed to remove the outermost electrons increases.

 Exception 1: ns2 np1 configuration - 1st IE of Al is lower than that of Mg

• Mg: 1s2 2s2 2p6 3s2 Al: 1s2 2s2 2p6 3s2 3p1
• Less energy is needed to remove the 3p electron from Al
• as it experiences increased shielding from the inner filled 3s sub-shell.

 Exception 2: ns2 np4 configuration - 1st IE of S is lower than that of P.

• P: 1s2 2s2 2p6 3s2 3px1 3py1 3pz1 S: 1s2 2s2 2p6 3s2 3px2 3py1 3pz1
• Less energy is needed to remove an electron from the paired 3px electron in S
• as it experiences inter−electron repulsion
• arising from 2 electrons occupying the same 3px orbital.

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 Specialist’s Notes:
To explain trends in Ionisation Energy, we have to examine
 Energy required to  Effective  NuClear Charge
remove outermost e- NuClear Charge  Shielding effect

The 3 main trends to explain are

▪ Across the Period ▪ Down the Group ▪ Between Period
(Gp 17I & gp I)

There are 2 exceptions observed across the period

▪ Electronic configuration must be shown (to substantiate explanation)
 Remember the exception based on e- configuration rather than Gp No.
▪ Note precision of keywords for complete explanation

1b. Atomic Radii

Na
Atomic Radii

Mg
Al

Si
P
S
Cl

11 12 13 14 15 16 17
Proton No.

 Across the period from Na to Cl, atomic radii decreases.

▪ NuClear charge increases across the period while
▪ screening effect remains approximately constant (as successive electrons are added to
the same outermost shell).
▪ Hence, effective nuClear charge increases.
▪ And the electron shells are more strongly attracted towards the nuCleus.

Ionic Radii
Ionic Radii

P3‾
S2‾ Cl‾

Na+
Mg2+
Al3+ Si4+

11 12 13 14 15 16 17
Proton No.

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 Note: Si forms Si4+ and Ne doesn’t form any ions.

There are 2 trends that can be observed in the above graph:

 Across the period, ionic radii decreases for ions with the same isoelectronic
configuration.
▪ Na+, Mg2+, Al3+ and Si4+ cations are isoelectronic ([Ne]: 1s2 2s2 2p6)
while P3-, S2- to Cl- anions are isoelectronic ([Ar]: 1s2 2s2 2p6 3s2 3p6)
▪ As nuClear charge increases,
▪ number of electrons and screening effect remain the same (since ions are isoelectronic).
▪ effective nuClear charge increases.

 Anions have larger radii than cations.

▪ Anions have an additional shell of electrons compared to cations of the same period
e.g. Na+: 1s2 2s2 2p6 P3‾: 1s2 2s2 2p6 3s2 3p6

In addition, compared to graph in 2a,

 Cations have smaller radii than their respective atoms ( rNa+  rNa )
▪ as there is 1 shell of electrons less in cations.

 Anions have larger radii than their respective atoms ( rCl−  rCl ).
▪ There are more electrons than protons in the anions thus net attractive force for the valence
electrons by the nuCleus decreases.
▪
Specialist’s Notes:

To explain trends in size, we examine in the following order:

1st factor – No. of electron shell

(when no. of electron shell is the same)

2nd factor – Effective NuClear charge
(check NuClear charge & Shielding effect)

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1c. Melting Point
Si

Melting Point
Mg

Al
P S
Cl
Ar
Na
11 12 13 14 15 16 17 18
Proton No.

 Na to Al
▪ They have giant metallic structure consisting of cations and a sea of delocalised mobile
electrons held together by strong metallic bonds.
▪ Large amount of energy is needed to overcome the strong metallic bonds thus they have
high melting point.
Melting points increases from Na to Al
▪ As the number of valence electrons holding the cations together increases,
▪ strength of metallic bonds increases.

 Si
▪ Si has a giant molecular structure consisting of Si atoms held together by covalent bonds
(covalently bonded to 4 other Si atoms in a tetrahedral arrangement).
▪ Large amount of energy is needed to break the strong covalent bonds thus Si has very
high melting point.

 P, S, Cl and Ar
▪ They have simple molecular structure consisting of P4, S8 and Cl2 molecules or Ar atoms*
and held together by weak dispersion forces.
▪ Smaller amount of energy is needed to break the weak dispersion forces thus they have
low melting points.
Melting points increases in the following order: Ar < Cl2 < P4 < S8.
▪ As size of electron Cloud increases, the larger electron Cloud becomes more easily
polarized/polarizable,
▪ strength of dispersion forces increases.

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Specialist’s Notes:

To explain differences in Melting/Boiling Points, we have to examine

 3 point introduction – X and Y has (STRUCTURE) with (PARTICLES)
held together by (BONDS).

 Compare strength of different bonds

i.e. Ionic, metallic, covalent bonds are stronger than
IMF (dispersion, pd-pd, H-bond)
If same bonds present, recall factor examining strength of different
bonds.

 More/Less energy required to break the stronger/weaker

(bonds) in X.

Special cases (not exhaustive)

▪ Packing for melting point
▪ Formation of Intra-molecular H-bond

1d. Electrical Conductivity

Al
Electrical Conductivity

Na Mg

Si
P S Cl Ar

11 12 13 14 15 16 17 18

Proton No.

 Na, Mg and Al have high conductivity.

▪ The metal cations are in a sea of delocalised mobile electrons that can act as charge
carriers to conduct electricity.
Conductivity of the metals increases from Na, Mg to Al
▪ Due to increasing number of valence electrons contributing to the sea of delocalised
electrons.

 Si have low/partial conductivity.

▪ Si is a semi-conductor/metalloid with properties of metals and non-metals.
(FYI: Ge, SiC are also examples of semi-conductors; Electrical conductivity increases
with increasing temperature.)

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  P,S and Cl have zero conductivity.
▪ They exist as simple molecules.
▪ Their valence electrons are localised in covalent bonds
▪ thus do not have mobile electrons to conduct electricity

Specialist’s Notes:

To explain electrical conductivity, we have to identify charge carriers.

Examples of charge carriers
 delocalised mobile valence e-
▪ in giant metallic structure
▪ in the plane of graphite (no electrical conductivity perpendicular to
plane)

 mobile ions
▪ in molten/aq ionic compounds (no electrical conductivity in solid
state).

Special cases
▪ Silicon (semiconductor/metalloid)

2e. Electronegativity
The electronegativity of an atom is a measure of its ability to attract the electrons in a covalent
bond to itself.
Cl
P S
Al Si
Na Mg
Electronegativity

11 12 13 14 15 16 17
Proton No.
 Across the period, electronegativity increases
▪ as effective nuClear charge increases.

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Specialist’s Notes:

A useful way to remember this trend is to remember

Fluorine is the most electronegative element in the Periodic Table.

Other important trends

▪ Hydrogen is the least electronegative non-metal element.
(Metals are less electronegative than non-metals/hydrogen. That’s why metal hydrides have H at
a special oxidation state of -1).
Nitrogen, Oxygen and Fluorine are the three most electronegative elements (that’s able to form
hydrogen bond due to the higher –/+ present).
Consequently, Oxygen is more electronegative than Chlorine

This trend in electronegativity has an important implication on the nature of bonding and hence
chemical reactions of Period 3 chlorides and oxides (sections 3c and d).

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PERIODICITY OF CHEMICAL PROPERTIES OF PERIOD 3 ELEMENTS
3a. Reaction of elements with O2 and Cl2
Reaction with oxygen
• Burns vigorously with an intense yellow flame
Na • Forms white ionic solid of sodium oxide
2Na (s) + ½ O2 (g) → Na2O (s)
• Burns vigorously with a bright white flame
Mg • Forms white ionic solid of magnesium oxide
Mg (s) + ½ O2 (g) → MgO (s)
• Vigorous initial reaction, forming a layer of Al2O3 which prevents
Reaction with chlorine
• Reacts vigorously with a bright orange flame
• Forms white ionic solid of sodium chloride
Na (s) + ½ Cl2 (g) →NaCl (s)
• Reacts vigorously with a bright white flame
• Forms white ionic solid of magnesium chloride
Mg (s) + Cl2 (g) → MgCl2 (s)
• Reacts vigorously

Al
further reaction • Forms pale yellow covalent* solid of aluminium chloride
• Forms white ionic solid of aluminium oxide 2Al (s) + 3Cl2 (g) → 2AlCl3 (s)
2Al (s) + 3/2O2 (g) → Al2O3 (s) 2AlCl3 (s) → Al2Cl6 (s)
• No reaction at room temperature • Reacts slowly on heating
• Burns with oxygen on strong heating • Forms colourless covalent liquid of silicon chloride
Si
• Forms white giant covalent solid of silicon oxide Si (s) + 2Cl2 (g) → SiCl4 (l)
Si (s) + O2 (g) → SiO2 (s)
• Reacts rapidly with oxygen with a pale bluish green flame • Burns spontaneously to give PCl3
• Ignite when exposed to air, no heating required • Forms colourless covalent liquid of phosphorus trichloride
• Forms white covalent phosphorus trioxide solid and / or P4 (s) + 6Cl2 (g) → 4PCl3 (l)
P
phosphorus pentoxide solid • With excess Cl2, PCl3 is oxidized to form off-white solid of PCl5
P4 (s) + 3O2 (g) → P4O6 (s) PCl3 (l) + Cl2 (g) → PCl5 (s)
P4 (s) + 5O2 (g) →P4O10 (s)
• Burns slowly with a pale blue flame
• Forms colourless covalent sulfur dioxide gas
S
S (s) + O2 (g) → SO2 (g)
SO2 is oxidised to SO3 with excess O2

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 Observe across the period, Na, Mg, Al are metals, Si is a metalloid and P,S are non-metals.
Look for patterns and study the reactions on the previous page in three groups instead of 6 separate reactions!
Note – key points:  rate (vigorous/slow),  colour of flame, colour of product, structure &  state of compound formed.
Na, Mg, Al (metals) Si (metalloid) P,S (non-metals)

 Burns vigorously No reaction at rm temp. Reacts rapidly Burns slowly

With oxygen

*exception: Al forms Al2O3 (corrosion Burns with strong heating

resistant)
 Na – intense yellow, Mg – bright white. – Pale bluish green flame Pale blue flame
 White White White C’less*
 Ionic (cpd between metals + non-metal). Giant Covalent Covalent Covalent
 Solid of Na2O, MgO, Al2O3 Solid of SiO2. Solid (III)P4O6/(V)P4O10 Gas*
(IV)
SO2/ (VI)SO3

 Reacts vigorously Reacts slowly on heating Burns spontaneously

With chlorine

 Na – orange, Mg – bright white. – –

 White *Exception Colourless Colourless / off-white
AlCl3 pale-
yellow*
 Ionic Covalent* Covalent Covalent / covalent
 Solid Solid Liquid SiCl4 Liquid (III)PCl3/ solid* (v)PCl5
(dimerises (simple molecular structure!)
via dative
bond)

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3b. Variation in oxidation number of oxides and chlorides
Formula of chlorides NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5 S2Cl2 SCl2

Oxidation number of elements +1 +2 +3 +4 +3 +5 +1 +2

Formula of oxides Na2O MgO Al2O3 SiO2 P4O6 P4O10 SO2 SO3

Oxidation number of elements +1 +2 +3 +4 +3 +5 +4 +6

• Oxidation numbers of the elements are positive values

o As Cl and O are more electronegative than the elements.

• Maximum oxidation number of the elements increases across the period from +1 to +6
o As oxidation number depends on the number of valence electrons used for bonding.

• P and S can have variable oxidation states

o As they can expand their octet structure by exciting the paired 3s and 3p valence electrons to the empty and energetically accessible 3d
orbitals.

P*: 1s2 2s2 2p 6 3s1 3p x1 3p y1 3p z1 3d x2 1

S*: 1s2 2s2 2p6 3s1 3p x1 3p y1 3p z1 3dx2 1 3d y2 1

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3c. Structure and bonding of chlorides and their reactions with water

Across the period

• The elements changes from metallic to non-metallic nature and
• The electronegativity difference between the element and chlorine decreases.
 The bond character of the chlorides changes from ionic to covalent
 The chlorides become more acidic.

Chloride (Structure) Reaction with water & Equations (state symbols are required)

NaCl • NaCl undergoes hydration (dissolves in water) to form a neutral solution of hydrated ions (pH = 7)
(Giant Ionic structure) NaCl (s) + aq →Na+ (aq) + Cl‾ (aq)

• Compound undergoes hydration to form hydrated ions

• Mg2+ hydrated ions undergoes very slight hydrolysis with water to give a weakly acidic solution (pH ≈ 6.5)
MgCl2
(Giant Ionic structure) o Mg2+ has a smaller size and higher charge than Na+ thus has higher charge density (see expn below)
MgCl2 (s) + 6H2O (l) → [Mg(H2O)6]2++ 2Cl‾ (aq) Note: Mg2+ (aq)  [Mg(H2O)6]2+ (aq)
[Mg(H2O)6] (aq) + H2O (l) → [Mg(H2O)5OH] (aq) + H3O (aq)
2+ + +

AlCl3 • In excess water, AlCl3 undergoes hydration to give the hydrated ions
(Simple molecular structure) AlCl3 (s) + 6H2O (l) → [Al(H2O)6]3+ (aq) + 3Cl‾ (aq) Note: Al3+ (aq)  [Al(H2O)6]3+(aq)
• [Al(H2O)6]3+ then undergoes further hydrolysis to give [Al(H2O)5OH]2+ (aq)
*Exists as pale yellow solid [Al(H2O)6]3+ (aq) + H2O (l) → [Al(H2O)5OH]2+ (aq) + H3O+ (aq)
of AlCl3 at room o Al3+ in [Al(H2O)6]3+ has a small size and high charge, thus has a high charge density and is highly
temperature but dimerises polarising. Thus it is able to polarise the O-H bond in H2O, causing H+ to be released to give an acidic
to form Al2Cl6 via dative
solution (pH  2−3)
bonds above its melting
point.
• (*Exception) In limited water, AlCl3 undergoes hydrolysis, producing fumes of HCl gas.
Cl Cl Cl
AlCl3 (s) + 3H2O (l) → Al(OH)3 (s) + 3HCl (g)
Al Al
Cl Cl Cl

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 Chloride (Structure) Reaction with water

• Compound undergoes hydrolysis to give a highly acidic solution (pH  1− 2) and white fumes of HCl gas

SiCl4 (l) + 2H2O (l) → SiO2 (s) + 4HCl (g)

SiCl4
(Simple molecular structure) FYI: SiCl4 (l) first hydrolyse to give Si(OH)4 which then rearrange to give the more stable SiO2
SiCl4 (l) + 4H2O (l) → Si(OH)4 (s) + 4HCl (g)
Si(OH)4 (s) → SiO2 (s) + 2H2O (l)

PCl3, PCl5 • PCl3/ PCl5 undergoes hydrolysis to give a highly acidic solution (pH  1− 2) and white fumes of HCl gas.
(Simple molecular structure) H3PO3 and H3PO4 are formed respectively.

PCl3 (l) + 3H2O (l) → H3PO3 (aq) + 3HCl (g)

PCl5 (s) + 4H2O (l) → H3PO4 (aq) + 5HCl (g)

• (*Exception) When water is cold water or in limited amount, PCl5 produces POCl3 (l)
PCl5 (s) + H2O (l) → POCl3 (l) + 2HCl (g)
POCl3 (l) + 3H2O (l) → H3PO4 (aq) + 3HCl (g)

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 Observe across the period, NaCl, MgCl2 are ionic compounds, AlCl3, SiCl4, PCl3 and PCl5 are (simple) covalent compounds.
Look for patterns and study the reactions on the previous page in two groups instead of 5+ separate reactions!
Note – key points:  nature of solid  type of reaction(s),  eqn (state symbols)  pH of solution formed.
NaCl MgCl2, AlCl3 SiCl4, PCl3 and PCl5

 Ionic compound Ionic compound, (simple) covalent (simple) Covalent compound

 Hydration (i) Hydration followed by Hydrolysis
(ii) hydrolysis (due to high charge density)
 NaCl (s) + aq (i) Solid + 6 H2O(l) Cpd + H2O → something + HCl (g)/(aq)
→Na+(aq) + Cl‾ (aq) → [M(H2O)6]x+ (aq) + x Cl‾ (aq)
Cpd Something
(ii) [M(H2O)6]x+ (aq) + H2O (l)
→ [M(H2O)5OH](x-1)+ (aq) + H3O+ (aq) SiCl4 (l) SiO2 (s) (not Si(OH)4)
(III) PCl3 (l) (III) H3PO3 (aq)
(V) PCl5 (s) (V) H3PO4 (aq)
(V) PCl5 (s) (V) POCl3 (l)
+ cold/limited water
(V) POCl3 (l) (V) H3PO4 (aq)
AlCl3 (s) Al(OH)3 (s) (not
*limited amount of Al2O3)
water
 7 MgCl2: 6.5 , AlCl3: 2-3 1-2

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3d. Structure and bonding of oxides and their reactions with water: Acid - Base behaviour of oxides and their corresponding hydroxides
Across the period,
• element changes form metallic to non-metallic nature and
• the difference in electronegativity between the oxide and the element decreases.
 The bond character of the oxides changes from ionic to giant covalent (SiO2) to simple covalent
 The nature of the oxide also changes from basic (in Na2O & MgO) to amphoteric (in Al2O3) to acidic (in SiO2, P4O6, P4O10, SO2, and SO3

Compound
Reaction with H2O Acid-Base behaviour of oxides
(Structure)
Na2O • Very soluble in water • Basic oxide which reacts vigorously with acids to form a salt
(Giant ionic o Aqeuous ions can form extensive ion-dipole and water.
structure ) interaction with water molecules (energy released is Na2O (s) + 2Hʉ (aq) → 2Naʉ (aq) + H2O (l)
sufficient to overcome ionic bonds i.e. hydration
energy is more exothermic than lattice energy).
• Strong alkaline solution obtained (pH ≈ 13) which will react
with acids to give a salt and water.
Na2O (s) + H2O (l) → 2NaOH (aq)
NaOH (aq) + Hʉ (aq) → Naʉ (aq) + H2O (l)
MgO • Slightly soluble in water due to high |L.E.| (strong ionic • Basic oxide which reacts readily with acids to form a salt and
(Giant ionic bonds). water.
structure) • Weak alkaline solution obtained (pH ≈ 9) which will react MgO (s) + 2Hʉ (aq) → Mg2ʉ (aq) + H2O (l)
with acids to give a salt and water.
MgO (s) + H2O (l) Mg(OH)2 (aq)
Mg(OH)2 (aq) + 2Hʉ (aq) → Mg2ʉ (aq) + 2H2O (l)
Al2O3 • Insoluble in water (pH = 7) due to high |L.E.| because • Amphoteric oxide (reacts with both acids and bases) to form
(Giant Ionic energy released when forming ion-dipole interaction with salt and water.
structure) water molecules is insufficient to overcome strong ionic Al2O3 (s) + 6H+ (aq) → 2Al3+ (aq) + 3H2O (l)
bonds in Al2O3. Al2O3 (s) + 2OH‾ (aq) + 3H2O (l) → 2[Al(OH)4]‾ (aq) *
Recall for solubility, we have to compare strengths of

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 δ-
δ+ δ+
δ+ δ+
δ-

δ+ δ+
δ- δ+ δ+
δ- δ- δ-
δ+ δ+
δ+ δ+
δ-

δ+ δ+ δ+ δ+

δ-
Solute (only) Solvent (only) Solute and Solvent
Interaction present between
Strong Ionic bonds Hydrogen bonds Ion-dipole interactions

Weaker - Stronger
It will be soluble if…
Stronger - Weaker
It will be insoluble if…
When different ionic salts Na2O, MgO, Al2O3 are dissolved…
Factors affecting strength of | q+ q- | | H hyd | 
|q|
interaction | L.E. |  No change
r+ + r- r
Across the period, Ionic The ionic bonds The ion-dipole bonds formed
charges of the cation becomes stronger becomes stronger too.
No change
increases from Na2O, MgO,
Al2O3…
As it is observed that solubility decreases across the Period from Na2O, MgO, Al2O3, the increase in ionic bond strength is more
significant than the increase in ion-dipole bond strength.

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Keywords for explanation for
Solubility: Solute is able to form extensive/strong (interaction) with (solvent) molecules.
Insolubility:  energy released when forming (weak) (interaction) between (solute) and (solvent).
 is insufficient to overcome
 the strong (interaction) (originally present) between (solute and/or solvent).
Alternatively, since for ionic cpds  H sol =  ΔHhyd - L.E. We can attribute the insolubility of Al2O3 and lower solubility of MgO to their large |L.E.|.

Compound
Reaction with H2O Acid-Base behaviour of oxides
(Structure)
SiO2 • Insoluble in water (pH = 7) because energy released when • Acidic oxide which reacts with only concentrated alkalis or at
(Giant molecular forming weak dispersion forces between SiO2 and H2O high temperature to give a salt and water.
structure) molecules is insufficient to overcome the strong covalent SiO2 (s) + 2OH‾ (aq) → SiO32‾ (aq) + H2O (l)
bonds between Si and O atoms.
P4O6, P4O10 • Reacts with water to give a highly acidic solution (pH = 1-2) • Acidic oxide which reacts with alkalis to give a salt and water
(Simple molecular P4O6 (s) + 6H2O (l) → 4H3PO3 (aq) P4O6 (s) + 8OH‾ (aq) → 4HPO32‾ (aq) + 2H2O (l)
structure) P4O10 (s) + 6H2O (l) → 4H3PO4 (aq) P4O10 (s) + 12OH‾ (aq) → 4PO43‾ (aq) + 6H2O (l)

• Which reacts with alkalis to give a salt and water

H3PO3 (aq) + 2 OH- (aq) → HPO32‾ (aq) + 2 H2O (l)
H3PO4 (aq) + 3 OH- (aq) → PO43‾ (aq) + 3H2O (l)
SO2, SO3 • Reacts with water to give a highly acidic solution (pH = 1-2) • Acidic oxide which reacts with alkalis to give a salt and water
(Simple molecular SO2 (g) + H2O (l) → H2SO3 (aq) SO2 (g) + 2OH‾ (aq) → SO32‾ (aq) + H2O (l)
structure) SO3 (g) + H2O (l) → H2SO4 (aq) SO3 (g) + 2OH‾ (aq) → SO42‾ (aq) + H2O (l)

• Which reacts with alkalis to give a salt and water

H2SO3 (aq) + 2 OH- (aq) → SO32‾ (aq) + 2 H2O (l)
H2SO4 (aq) + 2 OH- (aq) → SO42‾ (aq) + 2 H2O (l)

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Observe across the period, Na2O, MgO, Al2O3 are ionic compounds, SiO2 is giant covalent compound and, P4O6, P4O10, SO2 and SO3 simple covalent
compounds.
Look for patterns and study the reactions on the previous page in two main groups instead of 8 separate reactions!
Note – key points:  nature of solid  acid-base properties  solubility/pH
 eqn for reactions of hydroxides/acids  eqn for reactions of oxides
P4O6, P4O10,
Na2O, MgO Al2O3 SiO2,
SO2, SO3

 Ionic compound Ionic compound (giant) Covalent (simple) Covalent

compound compound
 Basic Amphoteric* Acidic

 V. soluble, sparingly soluble to Insoluble (due to large |L.E.|) Insoluble (due to Reacts with water to
form hydroxide strong covalent form acid.
pH 9 to pH 13 pH 7 bonds) pH 1-2
pH 7
(III) H3PO3
P4O6,
(V) H3PO4
P4O10,
(IV) SO2 H3SO3
(VI) SO3 H3SO4
 Hydroxide reacts with acid to NIL NIL Acid reacts with alkali
form salt + water to form salt + water
M(OH)x + x H+ → Mx+ + xH2O HA + OH–
→ A– + H2 O

 oxide + x H+ → Mx+ + xH2O Basic (metal): Only with conc alkali Oxide + OH–
(as above) Al2O3 (s) + 6H+ (aq) → 2Al3+ (aq) + 3H2O (l) at highT to form SiO32- → A- + H2 O
Acidic: (as above)
Al2O3(s) + 2OH– (aq) + 3H2O(l)
→ 2[Al(OH)4]– (aq) *

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SPECIALIST’S NOTES

DIAGONAL RELATIONSHIP – DEDUCING PROPERTIES OF PERIOD 2 ELEMENTS

Consider the Period 2 elements in the periodic table:

Nuclear charge increase

I II III IV
Atomic
radii Li Be B C
increase
Na Mg Al Si

It is observed that 3 diagonally adjacent pairs of elements of the second and third period
(Li/Mg, Be/Al, B/Si) have similar properties – this concept is called diagonal relationship.

Recall
▪ Across the period, nuclear charge increases.
▪ Down the group, shielding effect increases.

This diagonal relationship exists mainly for these 3 pairs of elements because the
approximately equal and opposite effects from the increase in nuclear charge and increase
in shielding ‘cancels out’ each other. Hence these 3 pairs of elements have similar
effective nuclear charge.

The result is that Period 2 elements will have similar physical and chemical properties as
their diagonal elements (e.g. electronegativity, melting points, ionization energies,
electronegativity, polarising powers, reaction of chlorides and oxides etc.) rather than those
of the same group.

For example, Be reacts more similarly to Al than other Gp 2 elements.

▪ BeF2, BeCl2 and AlCl3 have simple molecular structures and dimerises readily.

▪ While other Gp 2 chlorides e.g. MgCl2 are ionic.

▪ BeCl2 and AlCl3 undergoes hydration followed by hydrolysis with water to form fairly
acidic solutions.
▪ BeCl2(s) + 4H2O(l) → [Be(H2O)4]2+(aq) + 2Cl‾(aq)
[Be(H2O)4]2+(aq) + H2O(l) → [Be(H2O)3OH]+(aq) + H3O+(l)

▪ While other Gp 2 chlorides e.g. MgCl2 undergoes hydration followed by very slight
hydrolysis. The remaining Gp 2 chlorides are expected to undergo hydration only (as
their charge density is lower).

▪ BeO and Al2O3 are amphoteric.

BeO (s) + 2HCl (aq) → BeCl2 (aq) + H2O (l)
BeO (s) + 2NaOH (aq) + H2O (l) → Na2Be(OH)4 (aq)
▪ While other Gp 2 oxides are MgO is basic and reacts with acids only.

Note
• We deduce the chemical and physical properties of period 2 elements from the diagonal
relationship of period 3 elements not vice versa.
• This relationship does not exist for elements in other periods as the combined effects of
charge and radius do not cancel out each other.

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21
4. INORGANIC QUALITATIVE ANALYSIS (TESTS FOR CATIONS AND ANIONS)

In analytical chemistry, there are two forms of analysis

• Quantitative analysis determines the amount of certain components in the substance
e.g. volumetric analysis (titrations) or gravimetric analysis.
• Qualitative analysis gives an indication of the identity of the chemical species in the
sample.

The reactions we have learnt in Inorganic Chemistry can help us to explain some of the tests
and observations often encountered in inorganic qualitative analysis.

These tests can be Classified broadly as

1. Tests for cations

• Addition of NaOH(aq)
• Addition of NH3(aq)
• Test for acidic cations

2. Tests for anions

• Addition of dilute acids (check for gas evolved/effervescence + colour change)
• Precipitation via addition of Ba2+ (aq), addition of Pb2+ (aq) and Ag+ (aq)

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1.1 Test for cations – Addition of NaOH(aq) and NH3 (aq)

Reaction with
cation NaOH (aq) NH3(aq)
aluminium, white ppt. white ppt.
3+
( soluble in excess insoluble in excess
Al aq)
ammonium, ammonia produced on heating -
+
NH4 (aq)
barium, no ppt. no ppt.
2+
(
(if reagents are pure)
Ba aq)
calcium, white. ppt. with high [Ca2+(aq)] no ppt.
2+
(
Ca aq)
chromium(III), grey-green ppt. soluble in grey-green ppt.
3+
( excess giving dark green insoluble in excess
Cr aq) solution
copper(II), pale blue ppt. blue ppt. soluble in excess
2+
( insoluble in excess giving dark blue solution
Cu aq),
iron(II), green ppt. green ppt.
2+
( insoluble in excess insoluble in excess
Fe aq)
iron(III), red-brown ppt. red-brown ppt.
3+
( insoluble in excess insoluble in excess
Fe aq)
lead(II), white ppt. white ppt.
2+
( soluble in excess insoluble in excess
Pb aq) PS3 –
magnesium, white ppt. white ppt. Conso
2+ insoluble in excess insoluble in excess lidate .
Mg (aq)
manganese(II), off-white ppt. off-white ppt. insoluble
2+
( insoluble in excess in excess
Mn aq)
zinc, white ppt. white ppt.
2+
( soluble in excess soluble in excess
Zn aq)

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How to remember this table (and explain the observations)?

1. NH4+ is the only cation that liberates a (pungent) gas on warming with aq NaOH (or any other
base).
Equation: NH4+ + OH- → NH3 + H2O
Type of reaction: Acid-base reaction
Test for ammonia: Turns moist red litmus paper blue

2. The identity of the ppt. formed in NaOH(aq) and NH 3(aq) are M(OH)n (metal hydroxide ppt).
In NaOH(aq) In NH3(aq)
Equation: Equations:
Mn+ (aq) + nOH- (aq) M(OH)n (s) 1. NH3 + H2O NH4+ + OH-
Type of reaction: Precipitation 2. M (aq) + nOH- (aq)
n+
M(OH)n (s)

Type of reaction: Precipitation

3. Most TM cations form coloured ppt. Most other metal ions form white ppt (*except #3).
Common colours of TM cations are as follows.
[Topic: TM]
Cr(OH)3 Grey-Green Fe(OH)2 Green Mn(OH)2 Off-white
Cu(OH)2 Blue Fe(OH)3 Red-brown *Zn is not a TM!

Explanation: To be taught in TM.

4. Ba2+ and Ca2+ form little or no ppt. [Topic: Gp 2/Periodicity]

Recall Mg(OH)2 is sparingly soluble (pH 8-9).
While Ca(OH)2, Sr(OH)2 and Ba(OH)2 are completely soluble (pH 10-13).
Explanation: Down the group, |L.E.| decreases due to increasing ionic radius, hence solubility
increases.

5. Pb2+, Al3+, Zn2+ (white) and Cr3+ (grey-green) are the only four cations that form a ppt soluble
in excess NaOH(aq). [Topic: Periodicity]
Equations:
1. Formation of ppt: Mn+ (aq) + nOH- (aq) M(OH)n (s)
2. Soluble ppt: M(OH)n + mOH- (aq) [M(OH)n]x- (aq)
Explanation: Pb(OH)2, Al(OH)3, Zn(OH)2 and Cr(OH)3 are amphoteric.
They react with more hydroxide to form [Pb(OH)4]2-, [Al(OH)4]-, [Zn(OH)4]2-, [Cr(OH)6]3- respectively.

6. Cu2+ (blue) and Zn2+ (white) are the only two cations that form a ppt. soluble in excess NH3
(aq). [Topic: TM]

Equations:
1. Formation of ppt: NH3 + H2O NH4+ + OH-
M (aq) + nOH- (aq)
n+
M(OH)n (s) – eqm1
n+
2. Soluble ppt: M (aq) + 4 NH3 (aq) [M(NH3)4]n+ (aq)
Explanation (revisit after TM):

• When excess aq NH3 is added, Mn+ combines with NH3 to form [M(NH3)4]n+.
• Hence [Mn+ (aq)] 
• POE of eqm 1 shifts to the left.
• ppt. dissolves.
• (to explain why ppt. completely dissolves/Clear solution formed),
I.P  as [Mn+]  and I.P. falls below Ksp(M(OH)2)

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1.2 Test for cations – Test for acidic cations Fe3+/Cr3+/Al3+

These cations produce an acidic solution.

Equation: [M(H2O)6]3+ + H2O [M(H2O)5(OH)]2+ + H3O+

OR [M(H2O)6]3+ [M(H2O)5(OH)]2+ + H+

Type of reaction: hydrolysis

Explanation: Due to their high charge density, these ions have a high polarizing power. Thus they are
able to polarise the O-H bond in H2O, causing H+ to be released to give an acidic solution.

Observation/Test:
1. Forms H2 with reactive metals e.g. Mg/Zn
2H3O+ + Zn → Zn2+ + H2 + 2H2O OR 2H+ + Zn → Zn2+ + H2
2. Forms CO2 with carbonates
2H3O+ + CO32- → CO2 + 3H2O OR 2H+ + CO32- → CO2 + H2O

2 Test for anions

Ion Reaction
Carbonate, CO32- CO2 liberated by dilute acids 
Chromate (VI), CrO42- yellow solution turns orange with H+(aq);
gives yellow ppt. with Ba2+(aq);
gives bright yellow ppt. with Pb2+(aq) 

Chloride, Cl- gives white ppt. with Ag+(aq) (soluble in NH3(aq)); 

gives white ppt. with Pb2+(aq) 

Bromide, Br- gives pale cream ppt. with Ag+(aq) (partially soluble in NH3(aq)); 
gives white ppt. with Pb2+(aq) 

Iodide, I- gives yellow ppt. with Ag+(aq) (insoluble in NH3(aq)); 

gives yellow ppt. with Pb2+(aq) 

Nitrate, NO3- NH3 liberated on heating with OH–(aq) and Al foil 

Nitrite, NO2- NH3 liberated on heating with OH–(aq) and Al foil; 

NO liberated by dilute acids 
(colourless NO → (pale) brown NO2 in air)

Sulfate, SO42- gives white ppt. with Ba2+(aq) or with Pb2+(aq) 

(insoluble in excess dilute strong acids) 

Sulfite, SO32- SO2 liberated with dilute acids; 

gives white ppt. with Ba2+(aq)  (soluble in dilute strong acids )

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1. In the presence of dilute acid, three anions: carbonate CO 32-, nitrite NO2- and
sulfide SO32- give off gases.

Equation: e.g. CO32- + 2H+ → H2CO3 CO2 + H2O

Type of reaction: acid base reaction

Anion Gas Chemical test (for the gas) & result

Effervescence of
CO32- Forms white ppt (CaCO3)with limewater (CaOH)2.
CO2
NO2 evolved.
NO2- (NO that further Brown gas evolved.
oxidises to NO2)

SO32- SO2 evolved. Turns orange K2Cr2O7 green.

Note:
1. Effervescence = gas is insoluble in water; Evolved = gas is soluble in water
2. Sulfate and nitrates are stable in acids! (That’s why we have HNO 3 and H2SO4!)

2. In the presence of dilute acid, a colour change is observed for yellow chromate CrO 42- to
orange dichromate Cr2O72-.

Equation: 2 H+ + 2CrO42- Cr2O72- + H2O

Type of reaction: acid base reaction (not redox because O.S. of Cr stays as +6)

solid
3. For precipitation tests via addition of Ba2+ (aq), addition of Pb2+ (aq)
and Ag+ (aq), recall the following solubility rules:

Soluble salts: Insoluble salts:

All Na+ (all Gp I), NH4+ Sulfate SO42- : Ba2+, Pb2+
and nitrates Gp 17 Halides X- : Pb2+, Ag+
All CO32- (‘cept Gp I etc.)
**CO32-,SO32-,CrO42-: Ba2+, Pb2+, Ag+

a. Addition of Ag+ (aq)

Test: Addition of aqueous AgNO3 followed by dilute (or conc) NH3

Observation:

Cl- White ppt dissolves in dilute NH3 to give colourless solution

Cream ppt insoluble in dilute NH3.
Br-
Cream ppt dissolves in conc NH3 to give colourless solution
I- Yellow ppt remains insoluble in dilute and concentrated NH3.

Explanation: See Gp 17 notes

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b. Addition of Ba2+(aq)

Test: Addition of aqueous Ba(NO3)2 or BaCl2 followed by dilute acid HNO3 or HCl
Observation:

SO42- White ppt formed, insoluble in excess acid.

White/white/yellow ppt formed, soluble in excess acid
CO32-,SO32-,CrO42-
(see test 2.1)

c. Addition of Pb2+(aq)

Test: Addition of aqueous Pb(NO3)2

Observation:

Cl- White ppt formed.

*Note: PbX2 ppt dissolves
Br- White ppt formed. upon heating and needle-
like crystals reappear
I- Yellow ppt formed. upon cooling.

SO42- and White ppt formed.

SO32- (PbSO3 will be soluble in excess acid.)

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4. Devarda’s alloy test – a special test for nitrates and nitrites
Test: 1. Addition of Al powder, followed by aq NaOH.
2. Warm the mixture gently

Observation:
Ammonia gas evolved (turns moist red litmus paper blue).

Type of Reaction: Redox

(Al acts as a reducing agent to reduce N from +5 in NO3-/+3 NO2- to -3 in NH3).

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Summary of chlorides

Chloride NaCl MgCl2 AlCl3 SiCl4 PCl3, PCl5

Oxidation No +1 +2 +3 +4 +3 & +5
Structure Ionic lattice Simple molecular

Strong ionic bonds between Strong covalent bonds between atoms

Bonds
oppositely charged ions Weak dispersion forces between molecules

Melting Pt High. Increases with increasing lattice energy Low. Increases with increasing number of electrons

Reaction with Dissolve readily in water Dissolve readily in water Hydrolyses to form
Hydrolyses to form strongly acidic solution
H2 O (hydration) (hydration) with slight hydrolysis acidic solution

pH of solution pH = 7 (Neutral) pH ≈ 6.5 pH = 2 – 3 pH = 1 – 2

Summary of oxides

Oxides Na2O MgO Al2O3 SiO2 P4O6, P4O10 SO2, SO3

Oxidation
+1 +2 +3 +4 +3, +5 +4, +6
Number
Structure Ionic lattice Giant molecular Simple molecular
Strong covalent bonds
Strong covalent bonds between atoms
Bonds Strong ionic bonds between oppositely charged ions
between atoms Weak dispersion forces
between molecules
High. Strong covalent bonds Low. Increases with
Melting Point High. Increases with increasing lattice energy to 4 other atoms in a increasing number of
tetrahedral lattice electrons
Readily soluble Sparingly soluble in
Reaction with Insoluble in water due to strong bonds between atoms Reacts readily with water
with water to form water to form a weak
H2 O (i.e. ionic and covalent bonds) to form acidic solution
alkaline solution alkaline solution
pH of solution 13 9 7 1-2
Acid- Base Basic. Reacts with acid to form a salt and Amphoteric. Reacts with acid and
Acidic. Reacts with alkali to form a salt and water
nature water base to form a salt and water

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