Group 4 Elements, carbon, Silicon, germanium, tin and lead

Members
Elements symbol
Carbon C
Silicon Si
Germanium Ge
Tin Sn
Lead Pb
Physical properties
 Carbon and silicon are nonmetals.
 Germanium is a metalloid
 Tin and lead are metal

Electron configuration
General electron configuration of group 4 elements is ns2np2

Oxidation states
The common oxidation state of group IV elements is +2 and +4

Stability of oxidation states

Oxidation state +2 become more stable down the group
Oxidation state +4 become less stable down the group.

For instance carbon burns in oxygen to form carbon (IV) oxide (CO2) whereas lead form Lead (II)
oxide (PbO).

Secondly, CCl4 is stable whereas PbCl4 easily decomposes on heating giving lead (II) chloride
and chlorine
PbCl4 (g) (heat) →PbCl2 (s) + Cl2 (g)
Reasons for variation of stability of oxidation states
Down the group IV; +2 oxidation state become more stable due to inert pair effect i.e. the two
s-electron do not participate in the bonding due to increase in the energy difference between
ns and np electrons.

Properties of compound with +2 and +4 oxidation states

(i) Compounds in oxidation state +4 are predominantly covalent because formation
M4+ requires a lot energy whereas compound in oxidation state +2 are ionic

This explains the fact that PbCl4 is soluble in organic solvents like ethanol whereas PbCl2 does
not.

Note that
a. covalent compounds are soluble in organic solvents whereas ionic compounds do not.
b. Covalent compound have low melting and boiling points whereas ionic compounds have
high melting and boiling point.
c. Covalent compounds do not conduct electricity whereas ionic compounds do. On this
basis compound in oxidation state +4 show properties of covalent compounds because
they are predominately covalent.
Chemical properties
(a) Reaction with water
Carbon does not react with cold water but reacts with steam to form water gas
C(s) + H2O(g) → CO(g) + H2(g)

Silicon, germanium and Tin do not react with water up to 1000C because they are protected
by thin layer of oxide. But they react with steam at very high temperatures to form dioxides

Ge(s) + 2H2O(g) → GeO2(s) +2H2(g)

Lead reacts with soft water (water that contains oxygen) to form lead II hydroxide.
Pb(s) + 2H2O(g) + O2(g) → Pb(OH)2(s)

Reaction with acids

(i) Dilute non oxidizing acid like HCl.
C, Si, and Ge do not react

Sn liberates hydrogen
Sn(s) + 2H+(aq) Sn2+(aq) + H2(g)

Pb lead does not react with dilute hydrochloric acid and sulphuric acid due to formation
of insoluble salts.
(ii) Nitric acid
With concentrated nitric acid.

C, Si, Ge and Sn react to form dioxide

C(s) + 4HNO3(aq)→ CO2(g) +4NO2(g) + 2H2O(l)

Pb reacts to form lead II nitrate and nitrogen dioxide.

Pb(s) + 4HNO3(aq) → Pb(NO3)2(aq) + 2NO2(aq)+ 2H2O(l)

With 50% nitric acid.

Pb reacts to form lead II nitrate and nitrogen monoxide.
3Pb(s) + 8HNO3(aq) → 3Pb(NO3)2(aq) + 2NO(aq)+ 4H2O(l)

(iii) With sulphuric acid

Dilute sulphuric acid
C, Si and Ge do not react.
Sn and Pb reacts dilute concentrated sulphuric acid liberating hydrogen.
Pb (s) + H2SO4(aq) → PbSO4(s) + H2(g)

With hot Concentrated sulphuric acid

C, Si and Ge react to form dioxides
C(s) + 2H2SO4(aq) → CO2(g) + 2SO2(g) +2H2O(l)

Sn and Pb reacts hot concentrated sulphuric acid liberating sulphur dioxide .

Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) +2H2O(l)

Sn(s) + 2H2SO4(aq) → SnSO4(s) + SO2(g) +2H2O(l)

(iv) With acetic or ethanoic acid

C, Si Ge and Sn do not react.
Pb reacts ethanoic acid in presence of air giving lead II ethanoate and water
Pb (s) + 4CH3COOH(aq) + O2(g) → Pb(CH3COO-)2(aq) +2H2O(l)

Reaction with sodium hydroxide

C does not react.

Si Ge and Sn react liberating hydrogen and silicate (IV), germates (IV) and stannates (IV)
respectively

Si (s) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 2H2(l)

 Lead reacts to form plumbates (II).
Pb(s) + 2NaOH(aq) → Na2PbO2(aq) + 2H2(g)

Unique characteristics of carbon

1. Forms gaseous oxides, the rest form solid oxides

Note that
a. Carbon dioxide is a gas because its molecules are bonded by weak van der Waal forces.

b. Silicon dioxide is a solid of high melting point because each silicon atom is bonded to
four oxygen atom by strong covalent bonds.

2. Catenation: carbon forms chains, rings and branches with single, double and triple
bonds while others do not

3. Forms compounds mainly with oxidation sate (IV); other elements form compounds
with oxidation states +2 and +4.

4. Carbon tetrachloride and carbon tetrahydride do not hydrolyze in water. Chlorides of

other elements hydrolyze in water.

5. Carbon form CF4 and not CF6-2

Reason for uniqueness of carbon

 Has a very small atomic radius
 Has high electronegativity
 Lacks easily accessible d-orbital in its valence shell.

Allotropes of carbon
Allotropy is the existence of two or more different physical forms in the same state of a
chemical element.

An allotrope is any of the different physical form in the same state into which a chemical
element can exist.

Carbon exists in two main allotropes, i.e. graphite and diamond.

a. Graphite
In graphite, each carbon atom is covalently bonded to 3 carbon atoms to form a layer of
hexagons. Each layer is bonded to another by weak van der Waal forces.

Properties of graphite as a result of its structure

1. Has open structure and low density.
2. It is slippery and used as a lubricant.
3. Has unbonded π-electron that is free to move about making graphite a good conductor
of electricity and heat

b. Diamond
Structure of diamond

Each carbon atom is bonded tetrahedrally to four carbon atoms to form a 3D compact structure
by strong covalent bonds. As a result diamond has a high density, melting and boiling point. It is
the hardest substance known.

Diamond is used as an ornament, and to drill and cut other substances.

Differences between diamond and graphite

1. The density of graphite (2.3 gcm-3) that of diamond (3.5 g cm-3)
2. Diamond is very hard while graphite is soft
3. Graphite is slippery while diamond is not
4. Graphite conducts electricity while diamond does not.

Experiment to show that graphite and diamond are allotropes of carbon

When equal masses of graphite and diamond are burn in air, they give equal volume of carbon
dioxide.

Compounds of carbon
1. Hydrides: they include alkanes, alkenes, alkyne and aromatic compounds studied in organic
chemistry
2. Halides of carbon
Carbon forms all the four tetrahalides: CF4, CCl4, CBr4 and CI4
Comments
a. The melting points of halides increase with molecular. All tetrahalides are volatile liquids
b. The stability of the halides decrease from CF4 > CCl4 > CBr4 > CI4 due to decrease in the
bond strengths as electronegativity of the halogen decrease.
c. CCl4 is a good solvent, being very stable and heavier than air; is used in fire extinguisher
to protect the burning substance from oxygen.
d. CCl4 is not hydrolyzed by water due to lack of accessible d-orbital to accommodate the
lone pair of electron from water and weaken the C-X bond.

3. Oxides f carbon
(a) Carbon monoxide (CO)

Preparation
By dehydration of methanoic acid with concentrated sulphuric acid.
HCO2H(l) + Conc. H2SO4(l) → CO(g) + H2O(l)

Uses of carbon monoxide

(i) It reduces most metal oxides to metals.
Fe2O3 (s) + 3CO (g) → 2Fe (s) + 3CO2 (g)
NiO (s) + CO (g) → Ni (s) + CO2 (g)

This property is employed industrially in the extraction of iron and nickel.

It is used to purify nickel: it forms a volatile carbonyl that decompose to give a pure
metal 0
90 C
Ni (s) + 4CO(g) Ni(CO)4(g)
0
180 C
Ni(CO)4(g) Ni (s) + 4CO (g)

(ii) It is used preparation of carbonyl chloride that is used in the production of

polyurethane form of plastics and pesticides.
CO (g) + Cl2 (g) → COCl2 (g)
[carbonyl chloride]

(iii) It reacts with fused NaOH under pressure to give sodium methanoate. Methanoic
 acid is produced from this salt by the addition of dilute HCl.

NaOH (l) + CO (g) → HCOONa (s)

then HCOO- (aq) + H+ (aq) → HCOOH (l)

Methanoic acid is used to produce insecticides and for dyeing, tanning, and
electroplating.

(b) Carbon dioxide (CO2)

Preparation
By decomposition of calcium carbonate
CaCO3(s) (heat) → CaO(s) + CO2(g)
Limestone quick lime

Uses of carbon dioxide

a. Flavors fizzy drinks.
b. It is heavy and stable so is used in fire extinguishers to displace oxygen from burning
objects.

Carbonic acid
Preparation
By reacting carbon dioxide and water. There is however, equilibrium in solution of carbonic
acid, hydrogen ions, hydrogen carbonate and carbonate ions.
CO2 (g) + H2O (l) ↔ H2CO3 (aq)
H+(aq) + HCO3- (aq) ↔ 2H+ (aq) + CO32- (aq)

Structure of carbonic acid

Has 3 resonance hybrid whose bond lengths are intermediate between a C=O and C-O bonds

Carbonates and hydrocarbonate

 Both react with acids to liberate carbon dioxide
CO32- (aq)+ 2H+ (aq) → H2O (l) + CO2 (g)
HCO3- (aq)+ H+ (aq) → H2O (l) + CO2 (g)
 CO32- forms white ppt with Mg2+ whereas HCO3- does not.
Silicon
Existence
Exists as silica, SiO2 or sand used for building or making glass.

Chemical properties of SiO2

Reaction with NaOH
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
SiO2(s) + 2-OH (aq) → SiO32- (aq) + H2O (l).

Chemical properties of SiO2

(a) Reaction with NaOH
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
SiO2(s) + 2-OH (aq) → SiO32- (aq) + H2O (l).

(b) Reaction with HF

SiO2(s) + 4HF(g) → SiF4(aq) + H2O(l)
SiF4(aq) + 2HF(aq) → H2SiF6(aq)

(c) Reaction of silicon with acids

Silicon does not react with most acids under normal conditions but is dissolved by hydrofluoric acid,
HF, to form fluorosilicic acid, a reaction apparently driven by the stability of the Si(IV) fluoride complex
[SiF6]2-.
Si(s) + 6HF(aq) → 2H2(g) +H2SiF6 (aq) (fluorosilicic acid)

Germanium, tin and lead

Points to note
a. They form compounds with oxidation states +2 and + 4. The stability of compounds with
oxidation states +2 increases down the group due to ‘inert pair effect’ while those of
oxidation states +4 decreases down the group.

b. Compounds with oxidation state +2 are reducing. For instance tin II ions reduce iron III ions
to iron II ions.
Sn2+(aq) + Fe3+(aq) → Sn4+(aq) + Fe2+(aq)

c. Compounds with oxidation state +4 are oxidizing. For instance lead IV oxide ions oxidizes HCl
ions to chlorine
PbO2 (s)+ 4HCl (aq) → PbCl2(s) + 2H2O (l) + Cl2 (g)

d. Compounds with oxidation state +4 are predominantly ionic whereas those in oxidation state
+4 are predominantly covalent. This explains the fact that PbCl2 is soluble in water but
insoluble in ethanol whereas PbCl4 is soluble in ethanol
Chemical properties
The principal reactions of germanium and tin are similar, both elements exhibiting oxidation
state of 4

The principal reactions of lead are summarized below

a. Lead IV halide
Lead forms ionic Pb4+(F-)4, and covalent liquid PbCl4.
The tetra-bromide and tetra-iodide do not exist, presumably because bromine and iodine
are not sufficiently strong oxidizing agents to convert Pb 2+ to Pb4+.

Lead IV chloride
Preparation
By reacting lead IV oxide with cold concentrated hydrochloric acid.
PbO2 (s) + 4 HCl (aq) (conc. and cold) → PbCl4(aq) +2H2O(l)

Effect of Heat on Lead (IV) chloride

Decomposes on heating liberating chlorine
PbCl4 (g) (heat) → PbCl2 (s) + Cl2 (g)

Hydrolysis of lead (IV) chloride

Lead tetrachloride is readily hydrolyzed by water (white fumes of HCl and brown
precipitate of PbO2 are observed)
PbCl4 (s) + 2H2O (l) → PbO2 (s) + 4HCl (aq)
 Reaction of lead (IV) chloride with sodium hydroxide solution
Lead(IV) chloride react with sodium hydroxide to produce lead(IV) oxide, sodium chloride and
water. Sodium hydroxide - diluted solution.

PbCl4 + 4NaOH → PbO2 + 4NaCl + 2H2O

The compound PbO2 reacts with the sodium hydroxide to produce the hexahydroxoplumbate
(IV) ion [Pb(OH)6]2−, soluble with the water.
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]

b. Lead II halide
Preparation
By reacting soluble salt like lead nitrate with soluble halide
Pb2+(aq) + 2X-(aq) → PbX2(s) ( X = F, Cl, Br, I).
E.g. Pb2+(aq) + 2Cl-(aq) → PbCl2(s)

Properties
Except the iodide, which is yellow, they are white solids. Lead (II) chloride forms chloro-
complexes, e.g., [PbCl4]2-, with Cl- ions and because of this, it is soluble in concentrated
hydrochloric acid.

Reaction of lead (II) chloride with sodium hydroxide solution

Lead II chloride reacts with sodium hydroxide solution to form lead (II) hydroxide which dissolves in
excess sodium hydroxide to form sodium plumbate (II)
PbCl2 (s) + 2OH-(aq)  Pb(OH)2(s) + 2Cl-(aq)
Then
Pb(OH)2(s) + 2OH-(aq)  Pb(OH)42-(aq)

c. Lead IV oxide
Preparation
(i) Lead (IV) oxide, PbO2, is a brown solid obtained by oxidation of a soluble lead (II) salt
with hot sodium chlorate (I).

Pb2+(aq) + H2O(l) + ClO- (aq) → PbO2(s) + Cl-(aq) + 2H+(aq)

(ii) By action of nitric acid on trilead tetra oxide, Pb3O4.

Pb3O4 (s) + 4HNO3 (aq) → 2Pb(NO3)2(aq) + PbO2(s) + 2H2O(l)

Chemical properties of lead (IV) oxide

(i) Decomposes on heating
2PbO2 (s) + heat → 2PbO (s) + O2 (g)
(ii) Reacts with cold concentrated hydrochloric acid to form a yellow liquid lead (IV)
chloride and water
PbO2(s) + 4HCl (aq) → PbCl4(l) + 2H2O(l)
 Lead(IV) chloride react with ammonium chloride to form a yellow solid of ammonium
hexachloridoplumbate(IV).
PbCl4 + 2NH4Cl → (NH4)2[PbCl6]

(iii) Oxidize hot concentrated hydrochloric acid to chlorine

PbO2(s) + 4HCl(aq) → PbCl2 (s) + 2H2O(l) + Cl2(g)

React with the sodium hydroxide to produce the hexahydroxoplumbate (IV) ion [Pb(OH)6]2−,
soluble with the water.
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]

Qualitative analysis of Pb2+

1. Forms a white precipitate with sodium hydroxide soluble in excess
Pb2+(aq) + 2OH-(aq) → Pb(OH)2 (s) + 2OH-(aq) →Pb(OH)42- (aq)
2. Forms white precipitate with ammonia solution insoluble in excess
Pb2+(aq) + 2OH-(aq) → Pb(OH)2 (s)
3. Forms yellow precipitate with potassium iodide
Pb2+(aq) + 2I-(aq) → PbI2 (s)
4. Forms white precipitate hydrochloric acid soluble on warming
Pb2+(aq) + 2CI-(aq) → PbCI2 (s)
5. Forms white precipitate with sulphate ions
Pb2+(aq) + SO42-(aq) → PbSO4 (s)
Revision questions

Trial 1
Explain the following observation:
(a) Graphite and copper are both good conductors of electricity. (4 marks)
(b) Lead (II) chloride is insoluble in water whereas lead (IV) chlorides readily dissolve in the
same solvent. (2marks)
(c) Carbon which is in the same group as lead in the periodic table shows one valence of 4 in its
compounds but lead shows two valences of 2 and 4.
(d) Lead IV chloride readily decomposes to lead (II) chloride when heated but lead II chloride is
not affected by heat. (2marks)

(e) The solubility of lead (II) halides increase in order PbI2<PbBr2<PbCl2.

(f) When dilute hydrochloric acid is added to a solution of lead ethanoate, a white precipitate is
formed. The precipitate is soluble in excess concentrated hydrochloric acid. (4marks)

(g) Crystals of lead (II) chloride can be prepared in the laboratory by heating lead (II) oxide
with dilute hydrochloric acid and cooling. When lead (II) oxide is treated with concentrated
hydrochloric acid under the same conditions, no crystals form. Give a reason for this
observation and illustrate your answer with equations.

Trial 2
(a) (i) Define the term allotrope.
(ii) Give evidence that shows that graphite and diamond are allotropes of carbon.
(b) b. Explain the following:
(i) Graphite conducts heat and electricity yet it is a non-metal.
(ii) Diamond is a very hard element.
(c) Some properties of graphite and diamond are shown in the table below:

Allotrope Density g/cm3 Heat of combustion at 298K (KJ/mol.)

Graphite 2.25 -393.5
Diamond 3.51 -395.4

(i) Calculate the heat of conversion of graphite to diamond and state the allotrope that is more
stable at room temperature (298 K). Give your reasoning.
(ii) State what would happen to the total volume of the system if a given mass of diamond is
converted completely into graphite. Explain your answer.
(iii) Suggest, with a reason, one condition required for the converting of graphite to diamond.
(iv) Calculate the change in volume when one gram of graphite is converted completely into
diamond.
(iv) Give one use of diamond and graphite.
Trial 3
State four properties in which carbon differs from the rest of members in group (IV). (4 marks)

Trial 4
Carbonates are salts of carbonic acid which its self is obtained when carbon dioxide dissolves in
water.
(a) Write the structural formulae of carbon dioxide and carbonate ions. On the structure you
have written, indicate the type of bonding.
(b) The bond length of carbon-oxygen single bond and carbon-oxygen double bond are 0.143 nm
and 0.122 nm respectively. (2 marks)
(i) Estimate the bond lengths in carbonate ions and carbon dioxide. Give reason for your
answers. (4 marks)
(ii) Write the structural formula of carbonic acid and estimate the oxygen-carbon bond length.
(2 marks)
(iii) Give approximate value of the OCO bond angle in the structure you gave in (ii) and explain
your answer.
(c)Write the formulae of two ions which are isoelectric (contain equal number of electrons) with
carbonate ions
(2 marks)
3
(d) The solubility of carbon dioxide in water is 0.51 cm /g at s.t.p. Assuming the density of
water is 1 g cm-3, calculate the solubility of carbon dioxide in mol dm-3 at s.t.p (1mole of a gas
occupies 22.4 l at s.t.p). (3 marks)
(e) A sample of potassium carbonate was dissolved in water and the pH of solution determined.
Was the pH of solution greater or less than 7? Explain your answer. (2 marks)
(f) Explain why it’s possible to get two end-points when carbonate ions are titrated against an
acid. (2 marks)

Trial 5
Write an ionic equation for the reaction between sodium hydroxide and silicon (IV) oxide.

Trial 6
Carbon, silicon, tin and lead are elements of group (IV) of the periodic table.
(i) How do these elements react with sodium hydroxide?

Trial 7
Carbon, silicon, tin and lead are elements of in group IV of the periodic table.
(a) State:
(i) the common oxidation states shown by elements in group IV of the P.T. (1 marks)
(ii) how the stability of the oxidation states of group (IV) elements varies down the group.
(illustrate your answer with the chlorides of carbon and lead). (03 marks)
(b) Give a reason for your answer in (a) (ii). (01 mark)
Trial 8
(a) When red lead Pb3O4 was reacted with nitric acid, a solid was formed.
Write the equation for the reaction. (2 marks)
(b) The mixture from (a) was filtered and the residue warmed with concentrated hydrochloric
acid,
(i) What was observed? Explain your answer. (1 marks)
(ii) Write the equation for the reaction. (1½ mark)
(c) The filtrate from (a) was divided into two parts.
(i) To the first part was added aqueous potassium iodide. State what was observed and
write the equation for the reaction. (2 marks)
(ii) The second part was evaporated to dryness and heated strongly. Explain what was
observed and write the equation for the reaction that took place. (2½ marks)

Trial 9
A sample of lead (IV) oxide was treated with warm concentrated hydrochloric acid.
(i) State what was observed. (1½ marks)
(ii) Write the equation for the reaction. (02 marks)

Trial 10
Write down the equations for the reactions between:
i. The oxides of group (IV) elements and sodium hydroxide. (06 marks )
ii. Lead IV oxide and concentrated hydrochloric acid. (1½ marks)

(b) Write the ionic equation for the reaction between sodium hydroxide and lead (II) oxide.
(1 ½ marks)

Trial 11

a. State two industrial uses of tin.

b. Tin is said to be enantiotropic, explain what this means.

(c) How would you convert a solution containing tin (II) ions into a solution containing tin (IV)
ions?

(d) Pure tin was reacted with chlorine to give a colorless liquid that fumed in moist air. A
solution of 0.162 g of the liquid in water was equivalent to 24.00 cm3 of exactly 0.1 M sodium
hydroxide solution using methyl orange as the indicator. Calculate the percentage purity of the
liquid in tin compound.

Trial 12
Give a comparative account of the Chemistry of the oxides and chlorides of silicon, germanium,
tin and lead, paying particular attention to: -
 (a) the formation, composition and stability of oxides.
(b) the formation, hydrolytic behavior and stability of chlorides.

Trial 13
7. Give a concise account of the Chemistry of elements of group 4 of the periodic table (carbon,
silicon, germanium, tin and lead) referring your answer to all the following aspects:
(a) The variation in the first ionization energy.
(b) The hydrolysis of the tetrachloride.
(c) The acid-base character of the oxides of the elements in the oxidation states II and IV.
(d) The relative stabilities of II and IV oxidation states of elements in oxides and chlorides.
(e) Show how the electron pair repulsion theory can be used to predict the shape of the silicon
tetrachloride molecule.

Trial 14
(a) Carbon, silicon, germanium, tin and lead are elements of group IV in the periodic table.
(i) Describe the types of chlorides formed by these elements.
(ii) Show how the chlorides of these elements react with water.
(b) Describe the trends in the basicity of the oxides of group IV elements and write equations to
show how the oxides of carbon, silicon and germanium react with sodium hydroxide.
(c)When a mixture of carbon and an oxide of a group II element was heated to a very high
temperature, a compound X was formed. X reacted with cold water to give a gas Y that
decolourised chlorine water.
(i) Identify the element in group (II) and substances Xand Y.
(ii) Write equations leading to the formation of Y.

Trial 15
(a) Illustrate the transition from non metallic to metallic character of carbon, silicon and tin by
describing the structure of and giving one chemical property of, any one type of these
elements.
(b) One of the products of the reaction between magnesium silicide (Mg2Si) and sulphuric acid
is a gas X. A 0.620 g sample of X occupied 224 cm3. When hydrolysed, this sample yielded
1568 cm3 of hydrogen and a residue (SiO2) which, after it had been strongly heated, weighed
1.200 g. (All gas volumes corrected to S.T.P.)
(i) What is the molecular formula of X?
(ii) Write an equation for the hydrolysis of X.

Trial 16
(a) (i) State two important oxidation states exhibited by carbon, silicon, tin and lead.
(ii) Describe how the stability of the two states varies from carbon to lead. Use the oxides
of the elements to illustrate your answer.
 (iii) Explain the inert pair effect in group (IV) elements.

(b) State what would happen if tetrachloromethane, silicon (IV) chloride, tin(IV) chloride and
lead (IV) chloride are separately shaken with water. Write equations to illustrate your answer
where necessary.

(c) (i) Write equations to show how lead (II) chloride can be prepared in the laboratory. State
the conditions for the reaction.
(ii) What type of bonding exists in lead (II) chloride?
(iii) State two physical properties that show that lead (II) chloride exhibits the type of
bonding you have stated in (ii) above.

Trial 17
12. C, Si, Ge, Sn and Pb are elements of group (IV) of the periodic table.
(a) Explain the following trends among the group (IV) elements:
(i) electropositivity. (4marks)
(ii) stability of +2 oxidation state. (2 ½ marks)
(b) State four properties in which carbon differs from the rest of the members of group (IV).
(4 marks)
(c) Explain why carbon tetrachloride molecule is nonpolar yet the bonds in carbon
tetrachloride are polar. (3 marks)
(d) A sample of lead (IV) oxide was treated with warm concentrated hydrochloric acid
(i) State what was observed. (1.5 marks)
(ii) Write an equation for the reaction. (2 marks)

Trial 18
13. Carbon, silicon, tin and lead are elements of in group (IV) of the periodic table
(a) State
(i) The common oxidation state shown by the elements of group (IV). (1 mark)
(ii) How the stability of the oxidation states of group (IV) elements varies down the group.
(Illustrate your answer with the chlorides of carbon and lead). (03 marks)
(b) Give a reason for your answer in (a)(i) . (01 mark)
(c) Discuss the reactions of the chlorides of each element with water (06 marks)
(d) Write down equations for the reactions between:
i. The oxide of each element and sodium hydroxide. (06 marks)
ii. Lead (IV) oxide and concentrated hydrochloric acid. (1½ marks )
Suggested answers

Trial 1

(a) Both copper and graphite conduct electricity because they both possess mobile electrons.
The mobile electrons of copper are the delocalized valence electrons whereas those of
graphite are those of unbounded p-electrons.

(b) Lead (II) chloride is ionic whereas lead (IV) chloride is covalent. Lead (IV) chloride is
formed by sharing electrons because the amount of energy required to form Pb4+ is too
much.

(c) Carbon form compound with oxidation state +4 because there is very little difference
between 2s2 and 2p2 electron is small. The energy difference between 6s2 and 6p2 is big
that sometimes lead form Pb2+ ions by inert pair effect when only 6p2 electron take part in
the chemical reaction.

(d) Lead (II) oxidation state is more stable due to inert pair effect.

(e) Because the lattice energy decrease in order PbI2>PbBr2>PbCl2 and the ionic charater
increase in order PbI2<PbBr2< PbCl2 because electrogativity of chloride is in order Cl>
Br> I

(f) A white precipitate of PbCl2 is formed with dilute HCl which dissolves in concentrated
HCl due to formation of a soluble complex.

Pb2+(aq) + 2Cl-(aq) → PbCl2(s)

PbCl2(s) + 2Cl-(aq) → PbCl42-(aq)

(g) Lead (II) oxide forms insoluble lead (II) chloride with dilute hydrochloric acid which
dissolves in concentrated hydrochloric acid to form a soluble complex.

Pb2+(aq) + 2Cl-(aq) → PbCl2(s)

PbCl2(s) + 2Cl-(aq) → PbCl42-(aq)

Trial 2 (b)

(i) Graphite has mobile unbounded p-electrons that conduct heat and electricity

(ii) Each carbon atom is bonded to four carbon atoms by strong covalent bonds to form a
compact solid

(c)(i) +1.9kJmol-1

(ii) graphite is more stable because it contains less energy.

(iii) heat or pressure

(iv) volume decrease by 0,16cm3

Trial 4

(a)

(b) (i) Bond length in CO2 = 0.122nm

Bond length in CO32- = 0.136 and average between two single bond and 1 double bond

(ii)

(iii) Bond angle = 1200 dueto uniform repulsion between the bonds

(c) SO32-

(d) 0.0446moldm-3

(e) pH will be more than 7 due to hydrolysis of carbonate ions to form hydroxide ions

CO32-(a) + H2O(l) ↔ HCO3- (aq) + OH-(aq)

(f) The first end point occurs due to formation of hydrogen carbonate ions (HCO3-) and the
second one due to formation of carbon dioxide and water.

Trial 8

(a) Pb3O4 (s) + 4HNO3(aq) → PbO2 (s) + 2Pb(NO3)2(aq) + 2H2O(l)

(b) Green gas and white solid that dissolve in excess acid to form colorless solution

PbO2(s) + 4HCl(aq) → PbCl2 (s) + Cl2(g) + 2H2O(l)

Then

PbCl2(s) + 2Cl- (aq) → PbCl42-(aq)

(c) (i) yellow ppt

 Pb2+(aq) + 2I-(aq) → PbI2(s)

(ii) orange residue and brown fumes

2Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g)

Trial

(b) Tin exists in more than one crystal (allotropic) form that can be inter-converted by
temperature changes, i.e., the white form is the normal form at room temperature.
α-tin β-tin γ-tin
Grey White Grey

Trial 11

(c) By oxidation with acidified potassium permanganate or dichromate solution or iron (III)
salt.

(d) SnCl4(aq) + 2H2O(l) → SnO2(s) + 4HCl(aq)

Moles of HCl produced = moles of NaOH =

Moles of SnCl4 =

Mass of pure SnCl4 = 0.0006 x(119 + 35.4 x 4) = 0.15636

% of SnCl4 = 96.5%

Trial 14 (c)
(i) Element is calcium, X is CaC2 and Y is HCCH.
(ii) Ca (s) + 2C (s) →CaC2 (s)
then CaC2 (s) + 2H2O (l) → Ca(OH)2 (aq) + Y (HCCH) (g)
Trial 15 (b)
(i) SiH4
(ii) SiH4 (g) + 2H2O (l) → SiO2 (s) + 4H2 (g)
Trial 16
(a) Write the outermost electronic configuration of group (IV) elements. (01 marks)
ns2np2
(b) Describe the reaction of:
(i) Carbon, silicon, tin and lead with water (6½ marks)
Carbon does not react with cold water but reacts with steam to form water gas
C(s) + H2O(g) → CO(g) + H2(g)
Silicon, germanium and Tin do not react with water up to 1000C because they are
protected by thin layer of oxide. But they react with steam at very high temperatures to
 form dioxides

Ge(s) + 2H2O(g) → GeO2(s) +2H2(g)

Lead reacts with soft water (water that contains oxygen) to form lead II hydroxide.
Pb(s) + 2H2O(g) + O2(g) → Pb(OH)2(s)

(ii) Lead with ethanoic acid (2½ marks)

Pb reacts ethanoic acid in presence of air giving lead II ethanoate and water
Pb (s) + 4CH3COOH(aq) + O2(g) → Pb(CH3COO-)2(aq) +2H2O(l)

(iii) Chlorides of lead with sodium hydroxide solution (04marks)

Lead II chloride reacts with sodium hydroxide solution to form lead (II) hydroxide which dissolves
in excess sodium hydroxide to form sodium plumbate (II)
PbCl2 (s) + 2OH-(aq)  Pb(OH)2(s) + 2Cl-(aq)
Then
Pb(OH)2(s) + 2OH-(aq)  Pb(OH)42-(aq)

Lead(IV) chloride react with sodium hydroxide to produce lead(IV) oxide, sodium chloride and
water. Sodium hydroxide - diluted solution.

PbCl4 + 4NaOH → PbO2 + 4NaCl + 2H2O

The compound PbO2 reacts with the sodium hydroxide to produce the hexahydroxoplumbate
(IV) ion [Pb(OH)6]2−, soluble with the water.
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]

(iv) Silicon with acids (03 marks)

Silicon does not react with most acids under normal conditions but is dissolved by hydrofluoric
acid, HF, to form fluorosilicic acid, a reaction apparently driven by the stability of the Si(IV) fluoride
complex [SiF6]2-.
Si(s) + 6HF(aq) → 2H2(g) +H2SiF6 (aq) (fluorosilicic acid)

(c) Carbon does not react with chlorine but reacts readily with fluorine.
Explain this observation. (03 marks)

Fluorine is a stronger oxidizing agent than chlorine, has very low F-F bond energy and form stronger
C-F bond the C-Cl bond, these factors promote reaction of fluorine with carbon.

Trial 17
Carbon, silicon, tin and lead are elements in group IV of the periodic table.
(a) State
(i) the common oxidation state of group (IV) elements of the periodic table
(01marks)
 ns2np2
(ii) how the stability of the oxidation states of group IV element vary down
the group. (Illustrate your answer with the chloride of carbon and lead)
(03marks)
Oxidation state +2 become more stable down the group
Oxidation state +4 become less stable down the group.
This can be illustrated by chlorides of carbon and lead as follows:
CCl4 is stable whereas PbCl4 easily decomposes on heating giving lead (II) chloride
and chlorine
PbCl4 (g) (heat) →PbCl2 (s) + Cl2 (g)

(b) Give a reason for your answer in (a)(ii)

(01marks)
Down the group IV; +2 oxidation state become more stable due to inert pair effect i.e. the
two s-electron do not participate in the bonding due to increase in the energy difference
between ns and np electrons.
(c) Discuss the reaction of the chloride of each element with water
(06marks)
Tin (II) chloride partially hydrolyze in water liberating HCL
SnCl2(s) + H2O(l) →Sn(OH)Cl (s) + HCl (aq)
Lead (II) chloride sparingly dissolves in water to form lead and chloride ions
PbCl2(s) + aq →Pb2+(aq) + 2Cl-(aq)
Tetrahalides with exception of CCl4 hydrolyze in water to give dioxide and white fumes
of HCl
MCl4 (s) + 2H2O (l) → MO2 (s) + 4HCl (aq)

(d) Write equations for the reactions between

(i) the oxide of each element and sodium hydroxide
(06marks)
NaOH (l) + CO (g) → HCOONa (s)
CO2(g) + 2NaOH(aq) → Na2CO3(aq) + H2O(l)
2CO2(g) + 2NaOH(aq) → 2NaHCO3(aq)
SiO2(s) + 2OH-(aq) → SiO32-(aq) + H2O(l)
SnO(s) + 2NaOH(aq) → Na2SnO2 (aq) + H2O(l)
PbO(s) + 2NaOH(aq) → Na2PbO2 (aq) + H2O(l)
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]
(ii) lead (IV) oxide and cold concentrated hydrochloric acid
 (1 ½ marks)
PbO2 (s) + 4HCl (aq) (conc. and cold) → PbCl4(aq) +2H2O(l)
(ii) Lead (IV) oxide and warm concentrated hydrochloric acid (1 ½
marks)
PbO2 (s) + 4 HCl (aq) (hot) → PbCl2(aq) +2H2O(l) + Cl2(g)