THIRD SHORT PERIOD OF PERIODIC TABLE

The period runs from sodium to Argon. The table below shows some physical
parameters of the elements involved.
Elements Na Mg Al Si P S Cl Ar
Melting point 98 651 660 1410 44 114 -101 -189
Electronegativity 0.9 1.2 1.5 1.8 2.1 2.5 3.0
Ionization energy 502 745 587 799 1020 1000 1260 1530

Atomic radius 1.57 1.36 1.28 1.17 1.10 1.04 0.99

Electron Affinity -20 +67 -30 -135 -60 -200 -364
Oxidation states +1 +2 +3 +4 +3, +5 2,+4,+ +1,+3,-
6, 1,+5, +7
Structure Close Close Close Giant Discrete molecular structure
packed packe d packed molecu
lar

1. Melting point

This is a constant temperature at which an element in its solid state changes to liquid
state under constant pressure. The abrupt change in melting point is explained as:

• From sodium- aluminium, the strong metallic bonds have to be broken down.
The strength of the metallic bond increases due to increase in the number of
electrons used per atom and also due to decrease to metallic radius.

• From Aluminium- Silicon, the increase is due to the strong covalent bonds that
have to be broken for a giant atomic structure of Silicon where each silicon atom
contributes four electrons towards covalent bonding.

• From Silicon-phosphorous, the decrease is due to change from giant atomic

structure to molecular discrete structure where the molecules are held by weak van
der waals forces of attraction

• From phosphorous-Sulphur, these are discrete molecules which are as P4 and S8

held by weak Van der waals force whose magnitude increases with increase in
 molecular mass. Since the molar mass of S8 is greater than that of P4 therefore an
increase in melting point.

• From Sulphur-chlorine, the diatomic molecule has a lower molar mass than
sulphur therefore the magnitude of the van der waals forces are weaker hence low
melting point.

Qn: Explain the trend of the following parameters across period 3 of the periodic table

(a) Ionization energy

(b) Electron affinity

(c) Electronegativity

REACTIONS OF PERIOD 3 ELEMENTS

1. With Chlorine

Sodium and Magnesium when heated react with chlorine to form ionic chlorides

2Na (s) + Cl2 (g) 2NaCl (s)

Mg (s) + Cl2 (g) MgCl2 (s)

Aluminium forms a covalent chloride which dimerises in the vapour phase

2Al (s) + 3Cl2 (g) 2AlCl3 (s)

Vaour phase
2AlCl3 (s) Al2Cl6 (g)

Qn: Explain why aluminium chloride is covalent.

Soln: This is because the aluminium ions have a high charge density which greatly
polarizes the chloride ions to form a covalent compound hence reducing the charge
separation.

Silicon, phosphorous and Sulphur also react with chlorine to form covalent chlorides
with simple molecular structure.
Si (s) + 2Cl2 (g) SiCl4 (l)

2P (s) + 5Cl2 (g) 2PCl5 (s)

2P (s) + 3Cl2 (g) 2PCl3 (g)

2S (l) + Cl2 (g) S2Cl2 (l)

2. Oxygen

All the elements except chlorine react with oxygen to form oxides.

2Na (s) + O2 (g) Na2O2 (s)

2Mg (s) + O2 (g) 2 MgO (s)

4Al (s) + 3O2 (g) 2Al2O3 (s)

Si (s) + O2 (g) SiO2 (s)

P4 (s) + 3O2 (g) P4O6 (s)

P4 (s) + 5O2 (g) P4O10 (s)

S (s) + O2 (g) SO2 (g)

3. Hydrogen

Sodium and Magnesium burn vigorously in hydrogen gas to form ionic hydrides.

2Na (s) + H2 (g) 2NaH (s)

Mg (s) + H2 (g) MgH2 (s)

Aluminium, Silicon and Phosphorous do not react with hydrogen gas.

Chlorine and Sulphur form the corresponding covalent hydrides. Chlorine reacts in
presence of Sunlight or ultraviolet light.

Cl2 (g) + H2 (g) 2HCl (g)

S (l) + H2 (g) H2S (g)

4. WITH Acids

Sodium, Magnesium and Aluminium react with dilute acids to form salts and hydrogen
gas i.e. hydrochloric acid and sulphuric acid.

Other elements do not react with dilute mineral acids.

Concentrated Nitric acid reacts violently with sodium and magnesium to form the
nitrate, water and nitrogen dioxide

Na (s) + 2HNO3 (aq) NaNO3 (aq) + NO2 (g) + H2O (l)

Aluminium forms a layer of the oxide that prevents further reaction

Silicon and Chlorine do not react with concentrated nitric acid

Phosphorous and Sulphur are oxidized to their respective oxides and itself reduced to
nitrogen dioxide.

S (s) + 4HNO3 (aq) SO2 (g) + 4NO2 (g) + 2H2O (l)

P4 (s) + 10HNO3 (aq) + H2O (l) 4H3PO4 (aq) + 5NO2 (g) + 5NO (g)

COMPOUNDS OF PERIOD 3 ELEMENTS

1. Chlorides
Chlorides NaCl MgCl2 AlCl3 SiCl4 PCl3 , S2Cl2, Cl2
PCl5
b.p.t 1465 1418 423 57 74, 164 138 -35
mpt 808 714 192 -68 160 -76 -101
Bond ionic Ionic
Covalent

structure Giant Giant Simple

ionic ionic molecular structure

Reaction of the chlorides with water

Sodium chloride dissociates in water to form neutral aqueous solution.

Aluminium chloride undergoes hydrolysis due to high charge density and aluminium
ions become heavily hydrated in solution as Al (H2O)63+

The hydrated ions undergo hydrolysis to release a proton in solution which causes the
solution to be acidic

Al(H2O)63+ (aq) [Al(H2O)5OH]2+ (aq) + H+ (aq)

The other chlorides react with water to form hydrogen chloride

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

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

2S2Cl2 (s) + 2H2O (l) 3S (s) + SO2 (g) + 4HCl (aq)

Cl2 (g) + H2O (l) HCl (aq) + HOCl (aq)

2. Oxides

Reaction with water

Sodium oxide is highly soluble in water

Na2O (s) + H2O (l) 2NaOH (aq)

Magnesium Oxide is slightly soluble in water

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

Silicon (IV) oxide and aluminium oxide do not react with

water.

Oxides of Phosphorous, chlorine and Sulphur are acidic oxide.

P4O10 (s) + 6H2O (l) 4H3PO4 (aq)

SO2 (g) + H2O (l) H2SO3 (aq)

SO3 (g) + H2O (l) H2SO4 (aq)

Cl2O7 (l) + H2O (l) 2HClO4 (aq)

Reaction with sodium hydroxide solution

Sodium and Magnesium oxide are basic oxides therefore they do not react with sodium
hydroxide solution

Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2[Al (OH)4]- (aq)

SiO2 (s) + 2OH- (aq) SiO32- (aq) + H2O (l)

SO2 (g) + 2OH- (aq) SO32- (aq) + H2O (l)

Cl2O7 (l) + 2OH- (aq) 2ClO4- (aq) + H2O (l)

3. Hydrides
Hydrides NaH MgH 2 AlH 3 SiH 4 PH 3 H 2S HCl

Bond
Ionic Covalent
Structure Giant ionic Simple molecular

The ionic hydrides react with water to form hydroxide and hydrogen gas

NaH (s) + H2O (l) NaOH (aq) + H2 (g)

MgH2 (s) + 2H2O (l) Mg(OH)2 (s) + 2H2 (g)

AlH3 (s) + 3H2O (l) Al(OH)3 (s) + 3H2 (g)

Phosphine does not react with water. Hydride of silicon reacts with water in presence
of a strong base. i.e.
SiH4 (g) + 2OH- (aq) + H2O (l) SiO32- (aq) +4H2 (g)

Hydrogen Sulphide and Hydrogen chloride react with water to form acidic solution.

EXTRACTION OF ALUMINIUM

Ore : Bauxite Al2O3. 2H2O

Bauxite is roasted to convert Iron (II) Oxide (impurity) to Iron (III) Oxide and drive off
the water of crystallization.

The roasted ore is Crushed to powder and heated with concentrated sodium hydroxide
solution to remove aluminum oxide from the impurities.

The amphoteric ore and the acidic silicon (IV) Oxide (impurity) dissolve in the alkali to
form complex salts while the Iron (III) oxide remains undissolved.

Al2O3 (s) + 2OH- (aq) + 3H2O (l) 2Al(OH)4- (aq)

SiO2 (s) + 2OH- (aq) SiO32- (aq) + H2O (l)

The mixture is filtered and the filtrate diluted with water. Carbon dioxide gas is passed
through the mixture to precipitate pure aluminium hydroxide.

2Al(OH)4- (aq) + CO2 (g) 2Al(OH)3 (s) + CO32- (aq) + H2O (l)

Or. The solution is seeded by adding a little aluminium hydroxide to the aluminate to
precipitate aluminium hydroxide.

Al (OH)4- (aq) Al(OH)3 (s) + OH- (aq)

The insoluble hydroxide is filtered off, washed and dried. Pure aluminium hydroxide is
then heated to form pure aluminium oxide

2Al(OH)3 (s) Al2O3 (s) + 3H2O (g)

The oxide is then dissolved in molten cryolite to increase conductivity. A small amount
of Calcium fluoride is added to lower the melting point of the electrolyte. Also
Aluminium fluoride is added to lower the solubility of the molten aluminium.

The mixture is electrolyzed between the graphite electrodes at 900oC using a low
voltage to avoid the decomposition of Cryolite and high charge density.

Aluminium ions are discharged at the cathode while oxygen is liberated at the anode.

Cathode:

Al3+ (l)+ 3e Al (l)

Anode:

2O2- (l) O2 (g) + 4e

N.B. The disadvantage of using low voltage is that a lot of energy is used and anode is
replaced several time since it burns off in oxygen produced.

Qn: During the extraction of aluminium, the ore is first purified.

(a) (i) Write the name and formula of the ore

(ii) Name two main impurities in the ore.

(b) Describe briefly how purification process is carried.

(c) Write an equation to show how anhydrous aluminium chloride can be

obtained from aluminium.

(c) Explain briefly Aluminium utensils should not be washed using Soap.

(d) State any four uses of aluminium

TRANSITION METAL ELEMENTS

Introduction:

Some statistic about types of elements of the periodic table up to atomic number to 103

(a) Non- metals = 19

(b) Metalloid = 3

(c) Metals = 81

Of the metals, the following are the division:

(i) Non- metals – 22

(ii) Transition metals – 59

Transition metals are divided into two:

(a)d- block transition elements located in period 4, 5 and 6

(b) f- block transition elements located in period 6 and 7

Electronic Configuration
After the second energy level, an overlap starts occurring between 3d-subshell which is
nearer the nucleus than 4s- subshell but at a higher energy level. Thus after filling 3S
and 3P subshells further electrons after the 4S- subshell (2electrons) later 3d- subshell.

From the electronic configuration, a transition metal is defined as that element having a
partially filled 3d-subshell (between 1-9 electrons) therefore Zinc is not regarded as
transition metal.

However, anomalous behavior occurs between Chromium (Z=24) and Copper (Z=29)
because configuration giving half filled d-subshell are thermodynamically more stable.

Transition metals form ions by losing electrons from 4S-subshell rather than the
3dsubshell.

The table below shows the electronic configuration of the short series of the transition
metals
Element Symbol Atomic Configuration
number
Scandium Sc 21 1S22S22P63S23P64S23d1
Titanium Ti 22 [Ar]4S23d2
Vanadium V 23 [Ar]4S23d3
Chromium Cr 24 [Ar]4S13d5
Manganese Mn 25 [Ar]4S23d5
Iron Fe 26 [Ar]4S23d6
Cobalt Co 27 [Ar]4S23d7
Nickel Ni 28 [Ar]4S23d8
Copper Cu 29 [Ar]4S13d10
Zinc Zn 30 [Ar]4S23d10

Qn: (a) Explain why Fe2+ is easily oxidized to Fe3+

(b) Write the electronic configuration of the following ions

(i) Fe2+ (ii) Fe3+ (iii) Cr3+

Soln: (a) Because Fe3+ is has 3d5 subshell electrons which is thermodynamically stable
compared to Fe2+ with 3d6 which is unstable.

(b) (i) 1S22S22P63S23P63d6 (ii) 1S22S22P63S23P63d5 (iii) 1S22S22P63S23P63d3

PHYSICAL PROPERTIES OF TRANSITION METALS

The physical properties of transition metals do not vary greatly and many of them show
a regular trend. Some of the properties include:
1. Metallic character.

The transition metals are true metals and many of them are widely used industrially.
They are hard, strong and lustrous and have high melting and boiling point and high
enthalpies of atomization. These properties suggest presence of strong metallic bonding.

The strong metallic bonding is due to availability of d-electrons.e.g Sodium with only
3Selectron available for bonding therefore it has a low melting point compared to iron
with two 4S-electrons and a maximum of six 3d-electrons. 2. Metallic radius,
density and atomic volume

The metallic radius decreases from scandium to nickel and it slightly increases from
nickel to Zinc.

As atomic number increases, the nuclear charge increases. However, the electrons are
being added to inner 3d-subshell therefore these electrons are poorly shielded from the
nuclear charge hence the nuclear attraction for the outer most electron increases
resulting into decrease in atomic radius/ metallic radius.

The slightly increase from nickel to Copper is because the 3d-subenergy level in copper
is fully filled with electrons and this increases the shielding of the outer electrons from
the nuclear charge hence atomic radius increases.

The decrease in radius coupled with increasing atomic mass causes an increase in the
density and decrease in atomic volume in passing from Scandium to Nickel.

3. Ionization energy

There is a fairly general increase in ionization energy in passing from Scandium to

nickel due to increasing nuclear charge holding the electrons more strongly resulting
into decrease in atomic radius.

Qn. The table below shows the electronegativity values for elements in d-block of the
periodic table
Element Sc Ti V Cr Mn Fe Co Cu Zn
At. No. 21 22 23 24 25 26 27 29 30
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.9 1.6
(a) Plot a graph of electronegativity against atomic number

(b) Explain the trend of your graph in (a)

GENERAL CHARACTERISTICS OF TRANSITION METALS

1. Variable oxidation states

 The elements exist in variable oxidation states in variety of the compounds due to
availability of the 3d-electrons which can participate in bond formation by either ionic
or covalent

The commonest stable oxidation states are in red as shown in the table
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4
+5 +5 +5
+6 +6
+7
Some of the compounds with the oxidation state include:

Ti V Cr Mn Fe Co Ni Cu
TiO,TiCl2 VCl2, CrCl2, MnO,MnCl2, FeCl2 CoO,CoCl2, NiO CuO
Ti2O3, V2O3, Cr2O3,CrCl3 MnCl3, FeCl3 Co(NH3)63+ Ni2O3.xH2O Cu2O
TiCl3 VO2 CrCl4, MnO2, CuCl
TiO2, V2O5 CrO3, MnO42MnO4- CuCl2
TiCl4 Cr2O72-

The relative stability of these oxidation states is also indicated by the standard reduction
electrode potential.

Since Zinc has one oxidation state, it is regarded non-transition metal.

Qn: (a) Define the following terms;

(i) Oxidation state

(ii) Oxidising agent

(b) Determine the oxidation state of the transition metalin the following complex

(i) K2Cr2O7 (iii) [Co (NH3)5SO4]Br

(ii) MnO42- (iv) [CuCl2(CH3NH2)2]

2. Paramagnetism

A substance that can be drawn into a strong magnetic field is known as paramagnetic
substance.
Transition metals are paramagnetic due to the presence of unpaired 3d-electrons. Every
spinning electron acts as a tiny magnet. However, in an orbital with 2 paired electrons,
the magnetic moment of one electron cancels out. Paramagnetism arises due to spinning
of unpaired electrons about their axes which generates electric current

Paramagnetism increases with increase in the number of unpaired 3d-electrons.

3. Formation of Coloured Compounds

The 3d-electrons in isolated metal atom are degenerate.i.e. energetically alike. However,
in presence of ligands, the orbitals overlap differently and split into two levels of
different energy. This excites electrons from a lower to higher level of energy. The
frequency of light absorbed from this energy transition is from the visible region of the
spectrum hence this appears as colour. The remaining visible light which is not
absorbed is reflected as that colour shown by a transition metal/ion.

Examples of hydrated ions include

V(H2O)62+ - Violet Mn(H2O)62+ - pale pink Fe(H2O)62+ - Pale green

Zn(H2O)62+ - Colourless Sc(H2O)62+ - Colourless Cr(H2O)63+ - Blue-

green

N.B. Scandium and Zinc form colourless compounds therefore they are regarded as
nontransition metals.

Qn: (a) State two factors that affect the colour of transition metal compounds

Nature of Ligand and Oxidation state of the metal

(b) Explain why compounds of s-block elements don’t form coloured compounds

4. Catalytic activity

Transition elements and their compounds act as catalysts in several chemical processes

Homogeneous catalysis (where the catalyst are in the same phase with the reactants),
due to variable oxidation state transition metals/ ions form with the activated complex
thus providing an alternative reaction path way of lower reaction energy e.g.

S2O82- (aq) + 2I- (aq) Fe2+ (aq) 2SO42- (aq) + I2 (aq)

Heterogeneous catalysis (where the catalyst and reactants are in different phases), finely
divided solid transition metals/ compound provide an active interface for adsorption of
the reactant where they are bound to the surface by van der waals forces.

Examples include; V2O5- contact process, Iron- Haber process etc

5. Complex formation

Transition metals form complexes due to:

• Small and highly charged ions

• Presence of vacant 3d-orbitals to accommodate lone pairs of electrons from the

ligands

A ligand is an ion or molecule with lone pairs of electrons linked to the central metal
ion by a dative bond

Co-ordination number is the number of ligands molecules that form dative bonds with
central metal ion in the complex ion.

A metal complex or co-ordination compound is a chemical system composed of electron

donor and electron acceptor.

Ligands are classified on basing on the number of atoms directly bonded to the central
metal i.e.

(a) Monodentate ligands / Unidentate ligands

These are ligands with one donor atom per ligand molecule.e.g.NH3, H2O, CH3NH2, Cl-

(b) Polydentate/ Chelating ligands

These are ligands with two or more donor atoms per ligand molecule e.g.

H2NCH2CH2NH2 (Ethane-1,2-diamine) -with two donor atoms therefore it is called

bidentate

H2COOHCH2COOH

NCH2CN H
CH2COOH
CH2COOH (EDTA)-Ethylenediamine tetraacetic
acid
Also ligands can be classified based on charges;

• Neutral ligand Anionic ligands Cationic ligand

H2O- aqua Cl- -chloro

NH3-ammine Br- -bromo

CO-carbonyl SO42- - Sulphato

NO-nitrosyl OH- -hydroxo

H2NCH2CH2NH2 (en)-ethane-1,2-diamine CN- - cyano

NO2- Nitro

H- -hydrido

Nomenclature of Complexes

(a) Cationic complexes

(i) Name and number of ligands

(ii) Name central atom with its oxidation state

(iii) If different ligands exist, list them in order of anion, neutral and cation.
If the ligands are of the same nature, use the alphabetical order Examples
include:

• [Cu(NH3)4]2+Tetraamminecopper(II)ion

• [Cr(H2O)4(NH3)2]3+ diamminetetraaquachromium(III)ion

• [Pt(NH3)2NO2Cl]2+ chloronitrodiammineplatinum(IV) ion

• [Co(NH3)5SO4]Br Sulphatopentaammine cobalt(III)bromide

(b) Anionic complexes

Name of the central atom ends in –ate or-ic for an acid followed by it oxidation state.

Examples include:

[CuCl4]2- tetrachlorocuprate (II)ion

SiF62- Hexafluorosilicate(IV)ion
[Cr(OH)5NH3]3- pentahydroxoamminechromate(II)ion

[CoCl4(H2O)2]-tetrachlorodiaquacobaltate(III)ion

LiAlH4Lithiumtetrahydridoaluminate(III)

(c) Neutral complexes

These are formed between the central metal atom and a neutral ligand e.g.

• Ni(CO)4 Tetracarbonylnickel.

• V(CO)6 hexacarbonylvanadium.

ISOMERISM

The following are the kinds of isomerism in complexes;

(a) Ionisation isomerism

This occurs when an ion can occupy positions inside and outside complex ion .i.e. acts
as a free ligand

Example

[Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br

Bromopentaamminecobalt(III)sulphate
Sulphatopentaamminecobalt(III)bromide

These isomers can be differentiated by use of acidified barium nitrate solution and the
observations are:

[Co(NH3)5Br]SO4 – white precipitate is formed

[Co(NH3)5SO4]Br - No observable change

The sulphate ions in bromopentaamminecolbalt(III)sulphate are uncomplexed therefore

they are free to react with barium nitrate solution to precipitate the sparingly soluble
barium sulphate i.e.

Ba2+ (aq) + SO42- (aq) BaSO4 (s)

Qn: Hydrated Chromium(III)chloride forms three isomers which form a white

precipitate with silver nitrate solution.

(a) Write the formula and I.U.P.A.C name of each isomer

(b) Describe how the isomer can be distinguished.

Soln:

(a) [Cr(H2O)6]Cl3 Hexaaquachromium(III)chloride -violet

[Cr(H2O)5Cl]Cl2.H2O Chloropentaaquachromium(III)chloride -light green

[Cr(H2O)4Cl2]Cl.2H2O Dichlorotetraaquachromium(III)chloride -dark green

(b) Add excess 1M Silver nitrate solution to equimolar solution of each

isomer. The number of moles of silver chloride precipitated by isomer is in the
ratio of 3:2:1.

Or: Conductivity measurements

Conductivity depends on the number of conducting ions present in solution. The isomer
with more ions gives the highest conductivity.

(b) Geometrical isomerism

The isomers differ in the spatial arrangement of two ligand molecules in square planar
or octahedral complex giving rise to cis and trans isomers.

Read on the structure of complexes:

❖ Linear structure formed by complexes with coordination number 2

❖ Tetrahedral/ square planar formed by complexes with co-ordination

no. 4

❖ Octahedral formed by complexes with co-ordination no.6

STABILITY CONSTANT

Consider;

Mn+ (aq) + 6L (aq) [ML6]n+ (aq)

The equilibrium expression is written as:

Keq = where Keq is the stability constant

A ligand with a higher stability constant substitutes/ displaces others from the complex
Qn: To an aqueous solution of copper (II) sulphate, concentrated hydrochloric acid
was added followed by aqueous ammonia solution

(a) State what was observed

(b) Explain your observation in above in (a)

Soln:

(a) A blue solution turns to yellow finally deep blue.

(b) In dilute solution of copper(II) sulphate, the blue colour is due to

[Cu(H2O)6]2+ . On addition of concentrated hydrochloric acid the aqua ligand
are displaced to form a yellow tetrachlorocuprate (II) complex.

[Cu(H2O)6]2+ (aq) + 4Cl- (aq) CuCl42- (aq) + 6H2O (l)

On addition of ammonia molecules with a higher stability constant displaces the chloro
ligands to form tetraamminecopper(II)ions which is deep blue.

CuCl42- (aq) + 4NH3 (aq) [Cu(NH3)4]2+ (aq) + 4Cl- (aq)

COPPER

Extraction :

Ores:

• Copper Pyrites (CuFeS2)- principal ore

• Copper glance(Cu2S)

• Cuprite(CuO)

• Malachite (CuCO3.Cu(OH)2)

(a) Concentration of the ore (Froth floatation/ selective wetting)

The ore is crushed to powder and mixed with water containing a frothing agent such as
pine oil. Air is blown through the mixture to agitate the ore.

High density impurities become wet and sink to the bottom. Particles of the ore rise to
the surface and adhere to the air bubbles. They float on the surface as a froth which is
skimmed off, filtered and dried.

(b) Roasting
The concentrated ore is roasted in air to convert pyrites into iron(II)oxide,
copper(I)sulphide and sulphur dioxide gas

2CuFeS2 (s) + 4O2 (g) Cu2S (s) + 2FeO (s) + 3SO2 (g)

(c) Smelting

The mixture is heated in furnace with silicon (IV) oxide in absence of air. Iron(II)oxide
reacts to form a slug of Iron(II)silicate

FeO (s) + SiO2 (s) FeSiO3 (l)

The molten slug floats on the molten Copper(I)sulphide and can be trapped off.

(d) Conversion to blister copper

Copper(I)sulphide is heated in air to form copper(I)oxide and sulphur dioxide gas.

2Cu2S (s) + 3O2 (g) 2Cu2O (l) + 2SO2 (g)

The mixture of copper(I)oxide and unchanged copper(I)sulphide is then heated strongly

in absence of air to form blister copper.

2Cu2O (l) + Cu2S (s) 6Cu (l) + SO2 (g)

The molten copper is run off into moulds.

(e) Purification/Refining of blister copper

Copper (II) sulphate solution is electrolysed using blister copper as the anode and pure
copper as cathode. The pure copper dissolves from the anode into solution and it is
deposited at the cathode

At anode: Cu (s) Cu2+ (aq) + 2e

At cathode: Cu2+(aq) + 2e Cu (s)

The anode loses mass and cathode gains an equal mass of copper.

PROPERTIES OF COPPER

Copper has a low Electropositivity and thus it is an inert and not attacked by dilute
mineral acids and water.

(a) It is oxidized by hot concentrated sulphuric acid to copper (II) sulphate, sulphur
dioxide and water

Cu (s) + 2H2SO4 (aq) CuSO4 (aq) + SO2 (g) + 2H2O (l)

 (b) It is oxidized by cold and hot concentrated nitric acid as shown below
respectively

3Cu (s) + 8HNO3 (aq) 3Cu(NO3)2 (aq) + 2NO (g) + 4H2O (l)

Cu (s) + 4HNO3 (aq) Cu(NO3)2 (aq) + 2NO2 (g) + 2H2O (l)

(c) When heated, copper reacts with oxygen and dry chlorine as:

300 C
o

2Cu (s) + O2 (g) 2CuO (s)

1000oC
4Cu (s) + O2 (g)2Cu2O (s)

Cu (s) + Cl2 (g) CuCl2 (s)

(d) Hot copper foil glows red in sulphur vapour forming copper(I) sulphide

2Cu(s) + S(g) Cu2S(s)

COMPOUNDS OF COPPER

Common oxidation states are +1 and +2.

Copper (I) is less stable compared to copper(II) despite the stable electronic
configuration of copper (I) ions. With respect to copper, both copper (I) and Copper (II)
ions are unstable i.e.

Cu+ (aq) + e Cu (s) H =−602KJmol−1

Cu2+ (aq) + 2e Cu (s) H =−795KJmol−1

The enthalpy of conversion of Cu+ to Cu2+ is -409KJmol-1and this shows that Cu+ ions
are thermodynamically unstable with respect to both Cu and Cu2+

Copper (I) Compounds

They are unstable in aqueous solution and undergo disproportionation

(a) Copper (I) Oxide

It is prepared by reduction of copper (II) sulphate with Aldehydes in the presence of an

alkali

It is a basic oxide and can be reduced to copper by hydrogen and carbon

Cu2O (s) + 2H+ (aq) Cu (s) + H2O (l) + Cu2+ (aq)

Cu2O (s) + C (s) 2 Cu (s) + CO (g)

(b) Copper (I) chloride

It is prepared by boiling copper (II) chloride with copper in presence of concentrated

hydrochloric acid.

CuCl2 (aq) + Cu (s) 2CuCl (s)

It dissolves in excess hydrochloric acid to form a colourless solution

CuCl (s) + Cl- (aq) [CuCl2]- (aq)

It dissolves in excess aqueous ammonia (concentrated) to form complex

CuCl (s) + 2NH3 (aq) [Cu(NH3)2] + (aq) + Cl – (aq)

Qn: 8.0g of a copper ore was leached with dilute sulphuric acid and the resultant
solution diluted to 250cm3. Excess 10% potassium iodide was added to 30cm3 of the
solution. The iodine liberated 23.5cm3 of 0.05M sodium thiosulphate solution for
complete reaction.

(a) Write all the equations of reactions involved.

(b) Calculate the percentage of copper in ore

(c) Describe the application of copper (I) compounds in distinguishing

organic compounds and synthesis

(d) Explain the similarity between silver (I) and copper (I) ions

Qn: A double salt Cu(NH3)xCly.zH2O where x,y and z are whole numbers. The molar
mass of salt is 277.5g. The chloride in 1.388g of the salt is precipitated as silver
chloride. After washing and drying the mass of the precipitate was 2.870g. When
1.388g of the salt is boiled with excess sodium hydroxide solution, the ammonia
liberated neutralizes 10cm3 of 1.0M hydrochloric acid. Determine the formula of the
salt.

Copper (II) compounds

(a) Copper(II) oxide

This a black basic oxide obtained by the action of heat on copper (II) nitrate, carbonate,
sulphate or copper (II) hydroxide
CuCO3 (s) CuO (s) + CO2 (g)

It reacts with dilute mineral acids to form copper (II) salts and water

CuO (s) + 2 H+ (aq) Cu2+ (aq) + H2O (l)

It is reduced to copper by carbon, hydrogen, methane and ammonia

3CuO (s) + CH4 (g) 3Cu (s) + 2H2O (l)+ CO

CuO (s) + C (s) Cu (s) + CO (g)

(b) Copper (II) hydroxide

This a pale blue precipitate formed when dilute sodium hydroxide solution is added to a
solution of Copper (II) ions

Cu2+ (aq) + 2OH– (aq) Cu(OH)2(s)

It dissolves in ammonia solution due to formation of a soluble complex. i.e.

Cu (OH)2(s) + 4NH3 (aq) [Cu(NH3)4]2+ (aq) + 2OH- (aq)

(c) Copper (II) chloride

The anhydrous chloride is prepared by reacting dry chlorine gas with heated copper
metal

Cu (s) + Cl2 (g) CuCl2 (s)

The chloride dissolves in concentrated hydrochloric acid to form a yellow- green

solution of tetrachloro cuprate(II)

CuCl2 (s) + 2Cl- (aq) [CuCl4]2- (aq)

An aqueous solution of copper (II) salts are slightly acidic because the Cu2+ ions have a
high charge density therefore they are heavily hydrated as [ Cu(H2O)6]2+ and this
undergoes hydrolysis to release hydrogen ions in solution which causes the solution to
be acidic

[Cu(H2O)6]2+ (aq) [Cu(H2O)5OH]+ (aq) + H+ (aq)

The copper (II) salt in solution reacts with:

• Potassium ferrocyanide solution to form brown precipitate

• Excess potassium cyanide solution to form a colourless solution

 • Potassium iodide solution to form a white precipitate and brown stains

IRON electronic configuration 1S22S22P63S23P64S23d6

Extraction

Ore:

Haematite (Fe2O3)

Spathic (siderite) (FeCO3)

Magnetite(Fe3O4)

Iron pyrites (FeS2)

The mixture of haematite, coke and limestone are fed into the furnace from top. Air
enriched with oxygen is passed into the bottom of the furnace whose temperature varies
from about 2000oC -200oC at the top

Coke is constantly used to generate carbon monoxide gas

C (s) + O2 (g) CO2 (g)

C (s) + CO2 (g) 2CO (g)

The reaction is exothermic and thus increases the temperature of the furnace. Carbon
monoxide reduces iron (III) oxide to iron

Fe2O3 (s) + 3CO (g) 2Fe (l) + 3CO2 (g)

Limestone decomposes to form calcium oxide which removes the major impurity,
Silicon (IV) Oxide as a slag of calcium silicate.

CaCO3 (s) CaO (s) + CO2 (g)

CaO (s) + SiO2 (s) CaSiO3 (l)

The slag is less dense than the molten iron hence it protects it from re-oxidation. The
excess hot gases pass out of the furnace while the iron and slag are periodically tapped
off from the bottom

N.B. The pig iron can be converted to steel by open-hearth process where the carbon is
converted to gaseous oxide by heating and other impurities form oxides which react
with limestone to form slag

N.B. If Iron (II) carbonate or Sulphide is used; it is concentrated by froth floatation and
roasted in air to convert it to an oxide
2FeCO3 (s) + ½ O2 (g) Fe2O3 (s) + 2 CO2 (g)

PROPERTIES OF IRON

(a) When heated, iron reacts with oxygen to form black solid of triiron tetraoxide

3Fe (s) + 2O2 (g) Fe3O4 (s)

(b) Red hot iron reacts with stream as shown by the equation

3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

Iron slowly reacts with cold water in the presence of oxygen to form hydrated iron (III)
oxide

2Fe (s) + xH2O (l) + O2 (g) Fe2O3.xH2O (l)

(c) When heated iron reacts with sulphur, chlorine, hydrogen chloride, carbon and
carbon monoxide

Fe (s) + S (s) FeS (s)

2Fe (s) + 3 Cl2 (g) 2FeCl3 (s) (d) It liberate

hydrogen gas when reacted with dilute mineral acids Fe (s) + 2H+

(aq) Fe2+ (aq) + H2 (g)

Hot concentrated sulphuric acid oxidizes it to iron (III) sulphate and itself reduced to
sulphur dioxide and water

2Fe (s) + 6H2SO4 (l) Fe2(SO4)3 (aq) + 3SO2 (g) + 6H2O (l)

Concentrated nitric acid renders iron passive due to the formation of layer of the oxide.

COMPOUNDS OF IRON

Oxidation states are +2 and +3

The +3 oxidation state is more stable compared to +2 (why?).

Iron (II) compounds

(a) Iron (II) oxide

This a black basic oxide prepared by thermal decomposition of iron (II) oxalate in
absence of air
FeC2O4 (s) FeO (s) + CO2 (g) + CO (g)

It reacts with dilute mineral acids to form iron (II) salt and water

FeO (s) + 2H+ (aq) Fe2+ (aq) + H2O (l)

The salts solutions are pale green and are readily oxidized by atmospheric oxygen to the
corresponding iron (III) salts. However, they are stable in presence of an acid. It rapidly
turns brown on exposure to air

½O2 (g) + 2FeO (s) Fe2O3 (s)

(b) Iron (II) hydroxide

This a green precipitate formed by action of dilute sodium hydroxide or ammonia

solution on a solution containing Fe2+

On exposure to air, it turns brown due to the formation of Iron (III) hydroxide

2Fe(OH)2 (s) + ½O2 (g) + H2O (l) 2Fe(OH)3 (s)

An aqueous solution of iron (II) salts contains [Fe(H2O)6]2+ and don’t undergo
hydrolysis due to low charge density

(c) Iron (II) sulphate (FeSO4.7H2O)

It is prepared by warming Iron with excess dilute sulphuric acid and evaporate the
resultant solution to crystallize pale green crystal. The crystals are efflorescent and
oxidized on exposure to air with formation of brown patches of iron (III) sulphate

Ammonium ferrous sulphate is normally preferred to standardize potassium

permanganate because it is resistant to atmospheric oxidation, non-efflorescent and has
higher relative molecular mass.

(d) Oxidation reactions

(i) Hot concentrated nitric acid

A green solution turns yellow with effervescence of a colourless gas which forms brown
fumes in air

3Fe2+ (aq) +4H+ (aq) + NO3- (aq) 3Fe3+ (aq) + NO (g) + 2H2O (l)

2NO (g) + O2 (g) 2NO2 (g)

(ii) Chlorine gas

The green solution turns yellow

2Fe2+ (aq) + Cl2 (g) 2Fe3+ (aq) + 2Cl- (aq)

(iii) Hydrogen peroxide

The green solution turns yellow

H2O2 (aq) + 2H+ (aq) + 2Fe2+ (aq) 2Fe3+ (aq) + 2H2O (l)

(iv) Potassium dichromate

6Fe2+ (aq) + Cr2O72- (aq) + 14H+ (aq) 6Fe3+ (aq) + 2Cr3+ (aq) + 7H2O
(l)

(d) Potassium hexacyanoferrate (III) solution. It forms a dark blue precipitate

Iron (III) compounds

The iron (III) ions have a high charge density and are heavily hydrated therefore in
aqueous solution they exist as [Fe(H2O)6]3+ hence it undergoes hydrolysis to release
protons which cause the solution to be acidic

[Fe(H2O)6]3+ (aq) [Fe(H2O)5OH]2+ (aq) + H+ (aq)

Complete hydrolysis is represented as

[Fe(H2O)6]3+ (aq) [Fe(H2O)3(OH)3] (s) + 3H+ (aq)

(a) Iron (III) oxide

It is prepared by thermal decomposition of iron (II) sulphate or iron (III) hydroxide

2Fe(OH)3 (s) Fe2O3 (s) + 3H2O (g)

2FeSO4 (s) Fe2O3 (s) + SO2 (g) + SO3 (g)

It is basic and dissolves in dilute mineral acids

Fe2O3 (s) + 6HCl (aq) 2FeCl3 (aq) + 3H2O (l)

The oxide can be reduced by hydrogen, carbon and carbon monoxide to form iron

2Fe2O3 (s) + 3C (s) 4Fe (s) + 3CO2 (g)

(b) Iron (III) sulphate

Obtained by oxidation of iron (II) sulphate using concentrated sulphuric acid

2FeSO4 (aq) + 2H2SO4 (aq) Fe2(SO4)3 (aq) + SO2 (g) + 2H2O

(l)

Qn: Sodium carbonate solution was added to aqueous solution of iron (III) sulphate.
Bubbles of a colourless gas and a brown precipitate were observed. Explain this
observation

Soln: Due to high charge density, the hydrated ion undergoes hydrolysis to form
insoluble iron (III) hydroxide and hydrogen ions which cause the solution to be acidic
i.e.

[Fe(H2O)6]3+ (aq) [Fe(H2O)3(OH)3] (s) + 3H+ (aq)

The hydrogen ions react with carbonate ions from sodium carbonate to form carbon
dioxide gas which is a colourless gas.

H+ (aq) + CO32- (aq) CO2 (g) + H2O (l)

REDUCTION OF Fe3+ TO Fe2+

(i) Zinc and hydrochloric acid

Zn (s) + 2Fe3+ (aq) 2Fe2+ (aq) + Zn2+ (aq)

(ii) Hydrogen sulphide gas

The brown solution turns pale green and yellow solid is deposited

S2- (aq) + 2 Fe3+ (aq) 2Fe2+ (aq) + S (s)

(iii) Sulphur dioxide

The brown solution turns pale green

SO2 (g) + 2Fe3+ (aq) + 2H2O (l) 2Fe2+ (aq) + SO42- (aq) + 4H+ (aq)

N.B. Fe3+ ions are confirmed by use of potassium hexacyanoferrate (II) solution, a dark
blue precipitate is observed.

ZINC

The following a reasons why zinc is referred to as a non- transition metal

• It forms colourless compounds in aqueous state

 • It exhibits only one oxidation state

• It is not paramagnetic

• It does not act as catalyst or has limited catalytic activity However, like other

transition elements, Zinc forms complexes.

Extraction

Ore: - zinc blende (ZnS)

-Zincite(ZnO)

Concentration of ore

Zinc blende is crushed into powder and mixed with water containing a frothing agent.
Air is bubbled through the mixture. The low density ore floats as a froth which is
skimmed off.

Roasting

The concentrated ore is roasted in air to form the oxide

2ZnS (s) + 3 O2 (g) 2ZnO (s) + 2 SO2 (g)

Zinc oxide is then mixed with coke and limestone in a blast furnace. The oxide is
reduced to zinc metal by carbon monoxide

ZnO (s) + CO (g) Zn (g) + CO2 (g)

The metal distils off with other blast furnace gases. The mixture of gases is allowed to
cool (quenched) to obtain crude zinc which is purified by redistillation.

The major impurities are lead (II) sulphide, Cadmium and iron.

Reactions of Zinc

(a) It burns in oxygen to form zinc oxide and a little nitride

Zn (s) + ½O2 (g) ZnO (s)

3Zn (s) + N2 (g) Zn3N2 (s)

(b) Steam reacts with heated Zinc form Zinc oxide and Hydrogen gas

Zn (s) + H2O (g) ZnO (s) + H2 (g)

 (c) Warm dilute mineral acids readily react with Zinc to liberate hydrogen
gas

Zn (s) + 2H+ (aq) Zn2+ (aq) + H2 (g)

Hot concentrated sulphuric acid oxidizes zinc to zinc sulphate

Zn (s) + 2H2SO4 (aq) ZnSO4 (aq) + SO2 (g) + 2H2O (l)

(d) It reacts with sodium hydroxide solution in presence of water to form

zincate and hydrogen

Zn (s) + 2H2O (l) + 2OH- (aq) [Zn(OH)4]2- (aq) + H2 (g)

Compound of Zinc

Zinc oxide and zinc hydroxide are amphoteric compounds

ZnO (s) + 2H+ (aq) Zn2+ (aq) + H2O (l)

ZnO (s) + 2OH- (aq) + H2O (l) [Zn (OH)4]2- (aq)

The hydroxide dissolves in excess ammonia solution to form a complex colourless

solution

Zn(OH)2 (s) + 4 NH3 (aq) [Zn (NH3)4]2+ (aq)

N.B In aqueous solution salts of Zinc are colourless due to [Zn(H2O)4]2+ and are
confirm by use of disodium hydrogen phosphate where they form a white precipitate
soluble in ammonia solution

Question:

(a) Name one ore of zinc and give its formula

(b) (i) Describe briefly how the ore you have named in (a) is concentrated

(ii) What further treatment of the ore is required immediately after concentration?

(c) Outline the process, giving equations for the production of zinc metal
from the treated ore

(d) Zinc belongs to d-block in the periodic table yet it is not a transition
metal. Explain this statement.

(e) A piece of zinc metal was suspended in a solution of copper (II) sulphate
in water. State what was observed and write the equation for the change that
took place.
MANGANESE

ORES

• Pyrolusite-MnO2

• Hausmannite-Mn3O4

The extraction is done by reduction of the oxide using aluminium followed by vacuum
distillation

Direct reduction of manganese (IV) oxide is explosive thus the oxide is heated in
oxygen to be converted to trimanganese tetraoxide

CHEMICAL PROPERTIES OF MANGANESE

1. When heated, manganese reacts with non-metals as

3Mn (s) + 2O2 (g) Mn3O4 (s)

3Mn (s) + N2 (g) Mn3N2 (s)

Mn (s) + Cl2 (g) MnCl2 (s)

Mn (s) + S (s) MnS (s)

2. Manganese reacts with hot water to form sparingly soluble Manganese (II)
hydroxide and hydrogen gas

Mn (s) + H2O (g) Mn (OH)2 (s) + H2 (g)

3. Dilute hydrochloric and sulphuric acid form pink solution of manganese (II)
salts and hydrogen gas.

Qn: 4.0g impure manganese was dissolved in 20cm3 of 0.2M sulphuric acid.

(a) State what was observed

(b) Calculate the percentage purity of manganese in the impure sample

Compounds of Manganese

Oxidation states are +2, +3, +4, +6, and +7 but +2 is the most stable oxidation state due
to thermodynamically stable half filled 3d- orbital
Mn2+

(a) Potassium permanganate

A mixture of potassium hydroxide, potassium chlorate and manganese (IV) oxide is

fused. Hot water is added and carbon dioxide gas passed through the solution until it is
purple( green traces are removed)

6KOH (aq) + KClO3 (aq) + 3MnO2 (s) 3K2MnO4 (aq) + 3H2O (l) +
KCl (aq)
2- -
Carbon dioxide turns MnO4 to MnO4 by disproportionation
3MnO42- (aq) + 4H+ (aq) 2MnO4- (aq) + MnO2 (s) +2H2O (l)

In neutral or alkaline solution the manganate (VII) is reduced to manganese (IV) oxide

MnO4- (aq) + 4H+ (aq) + 3e MnO2 (s) + 2H2O (l)

In presence of manganese (IV) oxide, manganate (VII) is reduced to manganate (VI)

2MnO4- (aq) + MnO2 (s) + 4OH- (aq) 3MnO42- (aq) + 2H2O (l)

(b) Manganese (IV) oxide

It is black solid obtained by thermo-decomposition of manganese (II) nitrate

Mn (NO3)2 (s) MnO2 (s) + 2NO2 (g)

It oxidizes :

❖ Warm concentrated hydrochloric acid to chlorine

MnO2 (s) + 4HCl (aq) MnCl2 (aq) + Cl2 (g) + 2H2O (l)

❖ Oxalic acid or oxalate ions in presence of an acid to form carbon dioxide

MnO2 (s) + C2O42- (aq) +4H+ (aq) MnO (s) + 2CO2 (g) + 2H2O (l)

❖ Hot concentrated sulphuric acid to form oxygen, manganese (II) sulphate

and water

2MnO2 (s) + 2H2SO4 (aq) O2 (g) + 2MnSO4 (aq) +2H2O (l)

(c) Manganese (II) oxide

It is prepared by thermo-decomposition of manganese (II) carbonate or Manganese (II)

oxalate
MnCO3 (s) MnO (s) + CO2 (g)

The oxide is basic and reacts with oxygen at high temperatures to form trimanganese
tetraoxide

MnO (s) + H+ (aq) Mn2+ (aq) + H2O (l)

6MnO (s) + O2 (g) 2 Mn3O4 (s)

The mixed oxide reacts with acid to form manganese (II) ions and Manganese (III) salts
which disproportionate to form manganese (II) salts and manganese (IV) oxide

Mn3O4 (s) + 8H+ (aq) Mn2+ (aq) + 2Mn3+ (aq) + 4H2O (l)

2Mn3+ (aq) + 2H2O (l) Mn2+ (aq) + MnO2 (s) + 4H+ (aq)

(d) In an aqueous solution, the salts exist as [ Mn (H2O)6]2+ which is a pale pink
solution. The solution forms a white precipitate on addition of sodium hydroxide which
is immediately turns brown due to aerial oxidation

Mn2+ (aq) + 2OH- (aq) Mn(OH)2 (s)

4Mn(OH)2 (s) + O2 (g) 2Mn2O3.2H2O (s)

When hydrogen sulphide gas is bubbled through a solution of Manganese (II) ions in
presence of Ammonia, a pink precipitate of manganese (II) sulphide is formed.

Manganese (II) ions are oxidized to manganate (VII) by strong oxidizing agent such as
lead (IV) oxide or Sodium bismuthate (V) in presence of concentrated nitric acid

2Mn2+ (aq) + 5BiO3- (aq) + 14H+ (aq) 2MnO4- (aq) + 5Bi3+ (aq)
+ 7H2O(l)
2Mn2+ (aq) + 5PbO2 (s) +2H+ (aq) - 2+
2MnO4 (aq) +5Pb (aq) + 2H2O (l)

CHROMIUM

It exists as the chrome iron ore

The following are some of the reactions of chromium:

(a) Non-metal

Chromium reacts with non-metals when heated

4Cr(s) +3O2 (g) 2Cr2O3 (s)

(b) Acids

Dilute mineral acids react to form blue solution of chromium (II) salt which turns green
in air due to oxidation

Cr (s) + 2H+ (aq) Cr2+ (aq) + H2 (g)

2Cr2+ (aq) +2 H+ (aq) + ½ O2 (g) 2Cr3+ (aq) + H2O (l)

Hot concentrated sulphuric acid oxidizes Chromium to Chromium (III) sulphate and
itself reduced to sulphur dioxide gas and water

2Cr (s) + 12H+ (aq) + 3SO42- (aq) 2Cr3+ (aq) + 3SO2 (g) + 6H2O (l)

(c) Sodium hydroxide solution

It reacts with hot sodium hydroxide solution to form a chromite and hydrogen gas

2Cr (s) + 6OH- (aq) 2CrO33- (aq) + 3H2 (g)

Qn:

(a) Discuss the reaction of chromium with:

(i) Air (ii) Sulphuric acid

(b) Compare the chemistry of Chromium and Aluminium in terms of the following
themes

(i) Reaction with sodium hydroxide solution

(ii) Nature of the oxide

(iii) Nature of the chlorides

Compounds of chromium

Oxidation states are +2 , +3 and +6

Chromium (III) compounds

The compounds exist as [Cr(H2O)6]3+ and due to high charge density the solution are
acidic due to hydrolysis.
 [Cr(H2O)6]3+ (aq)

[Cr(H2O)5OH]2+(aq) + H+(aq)

Chromium (III) Oxide

It is prepared by thermo-decomposition of Chromium (III) hydroxide as a green

insoluble solid

2Cr(OH)3 (s) Cr2O3 (s) + 3H2O (l)

The oxide is stable and resistant to reduction by hydrogen and carbon monoxide

It is an amphoteric oxide i.e.

Cr2O3 (s) + 6H+ (aq) 2Cr3+ (aq) + 3H2O (l)

Cr2O3 (s) + 6OH- (aq) 2CrO33- (aq) + 3H2O (l)

Chromium (III) hydroxide

It is precipitated as a green solid on addition of sodium hydroxide solution to a solution

containing Chromium (III) ions

Cr3+ (aq) + 3OH- (aq) Cr(OH)3 (s)

It is an amphoteric hydroxide and thus dissolves in sodium hydroxide solution to form a

green solution

Cr(OH)3 (s) + OH- (aq) Cr(OH)4- (aq)

It is oxidized by hydrogen peroxide in alkaline medium to form a yellow chromate (VI)

solution

2Cr3+ (aq) + 3H2O2 (aq) + 10 OH- (aq) 2CrO42- (aq) + 8H2O (l)

It dissolves in excess ammonia solution to form a violet solution of

hexaamminechromium(III) complex

Cr(OH)3 (s) + NH3 (aq) [Cr(NH3)6]3+ (aq) +3 OH- (aq)

Chromium (VI) oxide

This is a dark red solid precipitated when concentrated sulphuric acid is added to a
saturated solution of potassium dichromate and cooled

Cr2O72- (aq) + 2H+ (aq) 2CrO3 (s) + H2O (l)

It is deliquescent and soluble in water to form chromic (VI) acid

CrO3 (s) + H2O (l) H2CrO4 (aq)

It is an acidic oxide which dissolves in alkaline solution to form chromate

CrO3 (s) + 2OH- (aq) CrO42-(aq) + H2O (l)

Chromate (VI)

These are yellow salts of Chromic (VI) acids which are isomorphic to sulphate ions

It is prepared by the action of alkaline sodium hydroxide solution on dichromate

Cr2O72- (aq) + 2OH- (aq) 2CrO42- (aq) + H2O (l)

In acidic medium, the orange dichromate is formed

2CrO42- (aq) + 2H+ (aq) Cr2O72- (aq)+ H2O

Qn: (a)A solution of potassium chromate was added to barium chloride solution
followed by dilute nitric acid. State what was observed and write the equation of the
reaction

(b) The Ksp of silver chloride and silver chromate is 1.0X10-12 and 1.0X10-10
respectively.

(i) State which salt is precipitated first if 0.1M KCl and 0.1MK2CrO4 are
separately added to silver nitrate solution

(ii) Explain the trend in the solubility of the chromates of group (II) of the
periodic table.

Dichromate

It is prepared by acidifying a solution of chromate

It can be acidified by dilute sulphuric acid and hydrochloric acid unlike permanganate
which is only acidified by sulphuric acid.

It oxidizes I- , SO32- , Sn2+, NO2- , H2S and Fe2+ in acidic medium

Dichromates in dilute acidified solution react with hydrogen peroxide solution to form a
blue chromium pentaoxide

Cr2O72- (aq) + 2H+ (aq) + 4 H2O2 (aq) 2CrO5 (s) + 5H2O (l)

COBALT
The oxidation states are +2 and +3 but +2 is more stable than +3 due to low ionization
enthalpy

Cobalt is a blue metal and less reactive than Iron

Reactions of Cobalt

1. When heated slowly reacts with air to form a mixture of oxides

2Co (s) + O2 (g) 2CoO (s)

3Co (s) + 2O2 (g) Co3O4 (s)

2. Liberates hydrogen from dilute hydrochloric acid and Sulphuric acid

Co (s) + 2H+ (aq) Co2+ (aq) + H2 (g)

Dilute nitric acid forms cobalt forms Cobalt (II) nitrate , nitrogen dioxide and water

Co (s) + HNO3 (aq) Co(NO3)2 (aq) + 2NO2 (g) + 2H2O (l)

The metal is rendered passive by concentrated nitric acid due to a layer of Co3O4

When heated under pressure, cobalt reacts with carbon monoxide to form a neutral
carbonyl

2Co (s) + 8CO (g) Co2(CO)8

It does not react with sodium hydroxide, water and halogens.

Compounds of Cobalt

Cobalt (II) Oxide

Green basic oxide obtained by thermal decomposition of nitrate, carbonate, hydroxide

in absence of air

2CoCO3 (s) CoO (s) + CO2 (g)

The green solid dissolves in an acid to a pink solution

CoO (s) + 2H+ (aq) Co2+ (aq) + H2O (l)

Cobalt (II) hydroxide

Blue basic hydroxide obtained by precipitation as

Co2+ (aq) + 2OH- (aq) Co(OH)2 (s)

The blue turns pink then brown in air due to aerial oxidation

It dissolves in excess ammonia solution to form a pale yellow solution which turns pink
due to aerial oxidation

Co (OH)2(s) + 6NH3 (aq) [Co (NH3)6]2+ (aq) + 2OH- (aq)

[Co (NH3)6]2+ (aq) [Co(NH3)6]3+ (aq) + e

Cobalt (II) Chloride

It is prepared by reacting dilute hydrochloric acid with Cobalt (II) oxide or hydroxide or
carbonate

CoCO3 (s) + 2HCl (aq) CoCl2 (aq) +CO2 (g) + H2O (l)

CoO (s) + 2HCl (aq) CoCl2 (aq) + H2O (l)

The anhydrous salt is blue but in aqueous solution exist as [Co (H2O)6]2+ which is pink.

The aqua ligands in the hydrated complex can be substituted by NH3, CN- and Cl- due to
higher stability constant

[Co(H2O)6]2+ (aq) + 4Cl- (aq) CbolCule42- (aq) + 6H2O (l)

Pink

[Co(H2O)6]2+ (aq) + 6NH3 (aq) [Co(NH3)6]2+ (aq) + 6H2O (l)

Pale yellow

Co2+ (aq) + 2CN- (aq) Co(CN)2 (s)

Reddish brown

A solution of cobalt (II) ions react with hydrogen peroxide in presence of an acid to form cobalt (III)

2Co2+ (aq) + H2O2 (aq) + 2H+ (aq) 2Co3+ (aq) + 2H2O (l)
Pink Brown

N.B. Cobalt (III) compounds are more stable when complexed.

Qn: An aqueous solution of cobalt (III) salt is CoCl3.6NH3 whose concentration is 1M.
The complex was reacted with 1M silver nitrate solution to precipitate 1M of silver
chloride.

(a)(i) Identify the complex

(ii) Write the structural formulae for the possible isomers
and give their I.U.P.A.C name

(iii) State the type of isomerism indicated (b) Explain:

(i) Why Cu2+ is colourless while Cu(H2O)42+ ion is blue and that of Cu(NH3)42+ is
deeper blue.

(ii) Aluminium hydroxide dissolves in sodium hydroxide solution while Magnesium

hydroxide does not

(iii)Copper (I) chloride and Lead (II) chloride are both insoluble in water but dissolves
in concentrated hydrochloric acid

(iV) A blue solution of Copper (II) chloride turns green on addition of chloride ions