11.

3 Relative stability of +2 and +4

Oxidation States of Group 14
Elements
Oxidation States
 The valence electronic configuration of Group 14 is 𝒏𝒔𝟐 𝒏𝒑𝟐 .
 The element has oxidation state of :
 +2 = when two p-electrons are used in bonding
 +2 for C and Si are covalent
 +2 for Ge is covalent with ionic character
 +2 for Sn and Pb are predominantly ionic
 +4 = when all four valence electrons are used in bonding
 +4 oxidation states is covalent
 ( not favourable to lose or gain 4 electrons to form 𝑋 4+ /𝑋 4−
ions)
Relative stability of +2 and +4 Oxidation
States
 +4 Oxidation state
 Relative stability decreases down the group
 +2 Oxidation state
 Relative stability increases down the group

 Deduced from standard electrode potential:

 𝐺𝑒 4+ 𝑎𝑞 + 2𝑒 − ↔ 𝐺𝑒 2+ 𝑎𝑞 𝐸 ο = −1.60𝑉
 𝑆𝑛4+ 𝑎𝑞 + 2𝑒 − ↔ 𝑆𝑛2+ (𝑎𝑞) 𝐸 ο = +0.15𝑉
 𝑃𝑏 4+ 𝑎𝑞 + 2𝑒 − ↔ 𝑃𝑏 2+ (𝑎𝑞) 𝐸 ο = +1.69𝑉
+4 Oxidation State
 For the first four elements, they are more stable in +4 compared to in
+2.
 Thus, their +2 compounds are good reducing agent (oxidized readily)
 2𝐶𝑂 𝑔 + 𝑂2 → 2𝐶𝑂2 (𝑔)
 𝑆𝑛2+ 𝑎𝑞 + 𝐼2 𝑎𝑞 → 𝑆𝑛4+ 𝑎𝑞 + 2𝐼 − (𝑎𝑞)

+2 Oxidation State
 Lead is more stable in +2 thus lead (IV) is good oxidizing agent
(readily to be reduced)
Inert pair effect

 Lead is positioned in period 6 thus has valence electronic

configuration of 6𝑠 2 6𝑝2
 Energy difference btw 6s and 6p is high
 Difficult for 6s electrons to be promoted to 6p orbitals
 6s electrons remain as inert pair an not involved in
chemical bonding (inert pair effect)
 Therefore ,lead tends to be in +2 oxidation state.
Oxides of Group 14 Elements

 Group 14 elements form both monoxide (+2 oxidation

state) and dioxide (+4 oxidation state).
 Tendency to form stable dioxides decreases down the
group
 Oxides become more basic going down the group
( increase of metallic character)
 Oxides (+4) more acidic than oxide (+2)
Bonding and Thermal Stability of
Monoxides
 CO
 Neutral, toxic gas
 Simple covalent molecules
 Since +4 is more stable, oxidized readily to 𝐶𝑂2

 SiO
 Simple covalent molecules
 Exist in gaseous phase when temp is > 2000 d.Celsius
 GeO and SnO
 Ionic with covalent character
 Since +4 is more stable, oxidized readily to respective dioxide.

2𝐺𝑒𝑂 𝑠 + 𝑂2 𝑔 → 2𝐺𝑒𝑂2 (𝑠)

2𝑠𝑛𝑂 𝑠 + 𝑂2 𝑔 → 2𝑆𝑛𝑂2 (𝑠)

 PbO
 Ionic, with covalent character
 Stable yellow solid
 When heated to 400 C , red dilead (II) lead(IV) oxide,𝑃𝑏3 𝑂4 is formed
 At 470 C, PbO reformed
Acid-Base Property of Monoxides
 CO and SiO are neutral

 GeO, SnO, PbO are amphotheric.

 - Dissolve in hot, dilute acids
 𝐺𝑒𝑂 𝑠 + 2𝐻 + 𝑎𝑞 → 𝐺𝑒 2+ 𝑎𝑞 + 𝐻2 𝑂(𝑙)
 Sn𝑂 𝑠 + 2𝐻 + 𝑎𝑞 → 𝑆𝑛2+ 𝑎𝑞 + 𝐻2 𝑂(𝑙)
 Pb𝑂 𝑠 + 2𝐻 + 𝑎𝑞 → 𝑃𝑏 2+ 𝑎𝑞 + 𝐻2 𝑂(𝑙)

 - Dissolve in hot, concentrated alkalis

2−
 𝐺𝑒𝑂 𝑠 + 2𝑂𝐻 − 𝑎𝑞 + 𝐻2 𝑂(𝑙) → 𝐺𝑒 𝑂𝐻 4 (aq) germanate(II) ion
2−
 Sn𝑂 𝑠 + 2𝑂𝐻 − 𝑎𝑞 + 𝐻2 𝑂 𝑙 → 𝑆𝑛 𝑂𝐻 4 𝑎𝑞 stanate(II) ion
2−
 Pb𝑂 𝑠 + 2𝑂𝐻 − 𝑎𝑞 + 𝐻2 𝑂(𝑙) → 𝑃𝑏 𝑂𝐻 4 (𝑎𝑞) plumbate(II) ion
Bonding and Thermal Stability of the
Dioxides
 𝐶𝑂2
 Thermally stable oxide
 Simple covalent, non-polar molecule ( C atom is sp
hybridized )

 𝑆𝑖𝑂2
 Thermally stable solid with high melting point
 Giant covalent lattice ( Si atom is 𝑠𝑝3 hybridized )
 𝐺𝑒𝑂2 𝑎𝑛𝑑 𝑆𝑛𝑂2
 Structure : between giant covalent structure and giant
ionic structure
 Thermally stable

 Pb𝑂2
 Brown solid
 Structure : between giant covalent and ionic structure
 Thermally unstable
 Decomposes to PbO and 𝑂2 when heated to 300 C
 2𝑃𝑏𝑂2 𝑠 → 2𝑃𝑏𝑂 𝑠 + 𝑂2 (𝑔)
Acid-Base Property of Dioxides
 𝐶𝑂2
 Slightly soluble in water to form carbonic acid,𝐻2 𝐶03
 Dissolves in dilute alkalis to form carbonates
 𝐶𝑂2 𝑔 + 2𝑂𝐻 − 𝑎𝑞 → 𝐶𝑂3 2− 𝑎𝑞 + 𝐻2 𝑂(𝑙)

 𝑆𝑖𝑂2
 Insoluble in water
 Dissolves in hot, concentrated alkalis to form silicates
 𝑆𝑖𝑂2 𝑠 + 2𝑂𝐻 − 𝑎𝑞 → 𝑆𝑖𝑂3 2− 𝑎𝑞 + 𝐻2 𝑂(𝑙)
 𝐺𝑒𝑂2 , 𝑆𝑛𝑂2 , 𝑃𝑏𝑂2
 Amphoteric
 React with alkalis to form 𝑴(𝑶𝑯)𝟔 𝟐− ions.
 𝐺𝑒𝑂2 𝑠 + 2𝑁𝑎𝑂𝐻 𝑎𝑞 + 2𝐻2 𝑂(𝑙) → 𝑁𝑎2 𝐺𝑒(𝑂𝐻)6 (𝑎𝑞)

 React with hot, concentrated HCl

 𝐺𝑒𝑂2 𝑠 + 4𝐻𝐶𝑙 𝑎𝑞 → 𝐺𝑒𝐶𝑙4 (𝑙) + 2𝐻2 0(𝑙)
 𝑆𝑛𝑂2 𝑠 + 4𝐻𝐶𝑙 𝑎𝑞 → 𝑆𝑛𝐶𝑙4 (𝑙) + 2𝐻2 0(𝑙)

 React with cold, concentrated HCl

 𝑃𝑏𝑂2 𝑠 + 4𝐻𝐶𝑙 𝑎𝑞 → 𝑃𝑏𝐶𝑙4 (𝑙) + 2𝐻2 0(𝑙)

 React with hot, concentrated HCl

 𝑃𝑏𝑂2 𝑠 + 4𝐻𝐶𝑙 𝑎𝑞 → 𝑃𝑏𝐶𝑙2 𝑠 + 𝐶𝑙2 (𝑔) + 2𝐻2 0(𝑙)