Revision Notes on Transition Elements:

Properties of Transition Elements:

1. Metals
2. Almost all: HARD, STRONG, High m.p., b.p.
3. Conduct heat & electricity
4. Form Alloys
5. Show variable oxidation states
6. At least one of the ions & compounds colored.
7. Form paramagnetic species because of partially filled shells
8. Form coordination compounds (complexes) and organometallic
compounds.

Physicochemical Properties
a. Melting and Boiling Points:

Melting and boiling points show no definite trends in the three transition
series.
The metals having the highest melting and boiling points are towards the
middle of each transition series.
b. Atomic (Covalent) and Ionic Radii:
Atomic and ionic radii values decrease generally, on moving from left to right
in the period.
The atomic radii for the elements from Cr to Cu are very close to one
another.
Radii of 5d series elements are virtually the same as those of corresponding
members of 4d series due to lanthanoid contraction.
c. Ionisation Potentials:
 First Ionization Potentials: I1 values for the first four 3d block elements
(Sc, Ti, V and Cr) differ only slightly from one another. The value of I I for
Zn is considerably higher. This is due to the extra-stability of 3d 10 level
which is completely filled in Zn-atom.
 Second ionisation potentials: The value of III for Cr and Cu are higher
than those of their neighbours. This is due to the fact that the electronic
configurations of Cr+ and Cu+ ions have extra stable 3d5 and 3d10
levels.There is a sudden fall in the values of ionisation potentials in going
from II B (Zn-group elements) to IIIA sub-group.
d. Oxidation States:
 The higher oxidation state of 4d and 5d series elements are generally
more stable than those of the elements of 3d series,
 In short it may be said that in going down a sub-group the stability of the
higher oxidation states increases while that of lower oxidation states
decreases.
 Transition elements cannot form ionic compounds in higher oxidation
states because the loss of more than three electrons is prevented by the
higher attractive force exerted (on the electrons) by the nucleus
Variable oxidation states:
1. Increase in the number of oxidation states from Sc to Mn.
All possible states exhibited by only Mn.
2. Decrease in the number of oxidation states from Mn to Zn, due to the
pairing of d-electrons occurs after Mn (Hund's rule).
3. Stability of higher oxidation states decreases along Sc to Zn. Mn(VII) and
Fe(VI) are powerful oxidizers.
4. Down the group, the stability of high oxidation states increases (easier
availability of both d and s electrons for ionization).
e. Colour: Transition elements with partially filled d orbitals form coloured
compounds.

f. Complex Formation: Transition elements show tendency to form

complex compounds due to.
 Small size and high effective nuclear charge
 Availability of low lying vacant d–orbitals which can accept lone pair of
electrons donated by a ligand.
Transition metal complexes:
 A transition metal complex is a species consisting of a transition metal
coordinated (bonded to) one or more ligands (neutral or anionic non-
metal species).
 Transition metal complexes are important in catalysis, materials
synthesis, photochemistry, and biological systems.
 Transition metal complexes display diverse chemical, optical and
magnetic properties.
Coordination numbers:
 Transition metal ions usually form complexes with a well defined
number of ligands.
 Complexes with coordination numbers four and six are most common,
although two and five coordination are also very well established.
 Coordination number and geometry are determined by a combination
of:
o Metal ion size.
o Ligand size
o Electronic factors (electron configuration, ligand type)
 

Ligands: an ion or molecule capable of donating a pair of electrons to the

central atom via a donor atom.
 Unidentate ligands: Ligands with only one donor atom, e.g. NH 3, Cl-, F- etc.
 Bidentate ligands: Ligands with two donor atoms, e.g. ethylenediamine,
C2O42-(oxalate ion) etc.
 Tridentate ligands: Ligands which have three donor atoms per ligand, e.g.
(dien) diethyl triamine.
 Hexadentate ligands: Ligands which have six donor atoms per ligand, e.g.
EDTA.
Chelating Ligands:
 Multidentate ligand simultaneously coordinating to a metal ion through
more than one site is called chelating ligand. Example: Ethylenediamine
(NH2CH2CH2NH2)
 These ligands produce a ring like structure called
chelate.
 Chelation increases the stability of complex.

Werner’s Theory:
 Metals possess two types of valencies i.e. primary (ionizable) valency and
secondary (non-ionizable) valency.
 Secondary valency of a metal is equal to the number of ligands attached
to it i.e. coordination number.
 Primary valencies are satisfied by negative ions, while secondary valencies
may be satisfied by neutral, negative or positive ions.

 Secondary valencies have a fixed orientation around the metal in space.

¿¿
Primary Valencies = Cl−¿¿
Secondary Valencies = 4 NH 3 and 2Cl
Coordination Sphere = ¿ ¿

Nomenclature of Complexes:
 Positive ion is named first followed by negative ion.
 Negative ligands are named by adding suffix - o.
 Positive ligands are named by adding prefix – ium.
 Neutral ligands are named as such without adding any suffix or prefix.
 Ligands are named in alphabetical order.
 Name of the ligands is written first followed by name of metal with its
oxidation number mentioned in roman numbers in simple parenthesis.
 Number of the polysyllabic ligands i.e. ligands which have numbers in their
name, is indicated by prefixes bis, tris etc,
 Number and name of solvent of crystallization if any, present in the
complex is written in the end of the name of complex.
 When both cation and anion are complex ions, the metal in negative
complex is named by adding suffix-ate.
 In case of bridging ligands:
Example simple ligands:

Neutral Molecules Anions Cations

−¿¿ +¿¿
Aqua H2 O Fluoro F NO Nitrosonium
−¿¿ +¿¿
Ammine NH 3 Chloro Cl [NH ¿ ¿ 2 NH 3] Hydrazinium
¿
−¿¿
Methylamine CH 3 NH 2 Bromo Br
−¿¿
Carbonyl CO Iodo I
−¿¿
Nitrosyl NO Hydroxo OH
−¿ ¿
Pyridine C 5 H 5N Cyano CN
−¿¿
Acetato CH 3 COO
Oxalato C 2 O4
2−¿ ¿

−¿ ¿
Mercapto HS
Imido NH
2−¿¿

Nitrido N
3−¿¿

2−¿ ¿
Sulfito SO 3
2−¿¿
Sulphato SO 4
−¿¿
Superoxo O2
2−¿¿
Oxo O
2−¿¿
Peroxo O2
2−¿ ¿
Thiosulphat S2 O 3
o
−¿¿
Thiocyano SCN

Isomerism in coordination compounds

Structural Isomerism
 Ionization Isomerism: Exchange of ligands between coordinate sphere and
ionization sphere
[Pt(NH3)4Cl2]Br2 & [Pt(NH3)4Br2]Cl2
 Hydrate Isomerism: Exchange of water molecules between coordinate
sphere and ionization sphere
[Cr(NH3)3(H2O)3]Br3 & [Cr(NH32)3(H2O)2 Br]Br2 H2O
 Linkage Isomerism: Ambient legend binds from the different binding sites
to the metal atom.
K2[Cu(CNS)4] & K2[Cu(SCN)4]
 Coordination Isomerism: Exchange of the metal atom between coordinate
sphere and ionization sphere when both are complex ions.
[Cr(NH3)6][CoF6] & [Co(NH3)6][CrF6].
 Ligand Isomerism: Different isomers of the same ligands attached to the
metal.
[Co(pn)2Br]Cl2 & [Co(tn)2Br]Cl2 Where,
pn = 1,2- Diaminopropane
tn = 1,3-Diaminopropane.

Stereoisomerism:
a.Geometrical Isomerism: When two similar ligands are on adjacent position
the isomer is called cis isomer while hen they are on opposite positions, the
isomer is called trans isomer.

b.Optical Isomerism: In order to show optical isomerism, the complex should

form a non superimposible mirror image which rotates the place of polarized
light in opposite direction.

Valence Bond Theory (VBT):

The idea that atoms form covalent bonds by sharing pairs of electrons was
first proposed by G. N. Lewis in 1902.
In 1927, Walter Heitler and Fritz London showed how the sharing of pairs of
electrons holds a covalent molecule together. The Heitler-London model of
covalent bonds was the basis of the VBT.
The last major step in the evolution of this theory was the suggestion by
Linus Pauling that atomic orbitals mix to form hybrid orbitals, such as the sp,
2 3 3 2 3
sp , sp , dsp , and d sp orbitals.

Hybridization:

Find out the hybridization of central metal ion using following steps:
 Write down the electronic configuration of metal atom.
 Find out oxidation state of metal atom.
 Write down the electronic configuration of metal ion.
 Write down the configuration of complex to find out hybridization.
Strong field ligands cause the pairing of electrons.
Strong Field Ligands: CO, CN-, NO2-, en, py, NH3.
Weak Filed Ligands: H2O, OH-, F-, Cl-, Br-,I -
When the d orbital taking part in hybridization is inside the s and p orbital
taking part in hybridization with respect to the nucleus, it is called an inner
orbital complex. Example: d2sp3 hybridization of [Co(NH3)6]3+ involves 3d, 4s
and 4p orbital, hence it is an inner orbital complex.
When the d orbital taking part in hybridization outside the s and p orbital
taking part in hybridization with respect to the nucleus, it is called an outer
orbital complex.
Example: sp3d2 hybridization of [CoF6]3- involves 4d, 4s and 4p orbital, hence
it is an inner orbital complex.

Geometry:

Coordination Number Hybridization Geometry

4 sp3 Tetrahedral

dsp2 Square Planar

6 d2sp3 & sp3d2 Octahedral

Magnetic Properties:
 Diamagnetic: All the electrons paired.
 Paramagnetic: Contains unpaired electrons.
Spin:
 Spin paired: All electrons paired.
 Spin free: Contains unpaired electrons.
Colour:
Compound must contain free electrons in order to show colour.

Crystal Field Theory (CFT):

This theory (CFT) largely replaced VB Theory for interpreting the chemistry
of coordination compounds.
It was proposed by the physicist Hans Bethe in 1929.
Subsequent modifications were proposed by J. H. Van Vleck in 1935 to allow
for some covalency in the interactions. These modifications are often
referred to as Ligand Field Theory.
•For a review on the evolution of bonding models see:
•The interactions between the metal ion and the ligands are purely
electrostatic (ionic).
•The ligands are regarded as point charges
•If the ligand is negatively charged: ion-ion interaction. If the ligand is
neutral : ion-dipole interaction
•The electrons on the metal are under repulsive from those on the ligands
•The electrons on metal occupy those d-orbitals farthest away from the
direction of approach of ligands/ labile
Strong field ligand causes greater repulsion and thus results in the formation
of low spin complexes by pairing of electrons.
 Weak field ligands result in the formation of high spin complexes
 Order of strength of ligands: CO > CN- > NO2- > en > py = NH3 > H2O >
OH- > F- > Cl- > Br- >I-

Octahedral Complexes: eg orbital are of higher energy than t2g orbital.

Not all d orbitals will interact to the same extent with the six point charges
located on the +x, -x, +y, -y, +z and -z axes respectively.
The orbitals which lie along these axes (i.e. x 2, y 2, z 2) will be destabilized
more that the orbitals which lie in-between the axes (i.e. xy, xz, yz).
If rather than a spherical field, discrete point charges (ligands) are allowed to
interact with the metal, the degeneracy of the d orbitals is removed (or,
better said, lifted). The splitting of d orbital energies and its consequences
are at the heart of crystal field theory.
Tetrahedral Complexes: eg orbitals are of lower energy than t 2g orbitals.

Δt = (4/9) Δo

Crystal Field Stabilization Energy:

System High Spin Low Spin
 Electronic CFSE Electronic CFSE
Configuration Configuration
Octahedral Complex

d4 t2g3 eg1 -(3/5)Δ0 t2g4 eg0 -(8/5)Δ0+P

d5 t2g3 eg2 0 t2g5 eg0 -(10/5)Δ0+2P

d6 t2g4 eg2 -(2/5)Δ0+P t2g6 eg0 -(12/5)Δ0+3P

d7 t2g5 eg2 -(4/5)Δ0+2P t2g6 eg1 -(9/5)Δ0+3P

Tetrahedral Complexes

d4 eg2 t2g2 -(2/5)Δt eg4 t2g0 -(12/5)Δt +2P

d5 eg2 t2g3 0 eg4 t2g1 -2 Δt +2P

d6 eg3 t2g3 -(3/5)Δt +P eg4 t2g2 -(8/5)Δt+2P

Outer sphere complex

Symmetric Field
•The 5Xd orbitals in an isolated gaseous metal are degenerate.
•If a spherically symmetric field of negative charges is placed around the
metal, these orbitals remain degenerate, but all of them are raised in energy
as a result of the repulsion between the negative charges on the ligands and
in the d orbitals. High spin
Octahedral Field
Paramagnetic

CFT-Octahedral Complexes
•For the Oh point group, the x2-y2, z2 orbitals belong to the Eg irreducible
representation and xy, xz, yz belong to the T2g representation.
•The extent to which these two sets of orbitals are split is denoted by Δ 0 or
alternatively 10Dq. As the baricenter must be conserved on going from a
spherical field to an octahedral field, the t2g set must be stabilized as much
as the eg set is destabilized.
Inner sphere complex
Stable
Low spin
Diamagnetic
g. Catalytic properties:
Transition metals and their compounds are known to act as good catalyst
due to
1. variable oxidation state, they form unstable intermediate compounds
and provide a new path with lower activation energy for the reaction
(Intermediate compound formation theory)
2. In some cases the finely divided metals or their compounds provide a
large surface area for adsorption and the adsorbed reactants react
faster due to the closer contact(Adsorption theory)
h. Magnetic Properties:
Magnetic moment is which is related to the number of unpaired electrons as
follows

n = number of unpaired electrons

B.M. = Bohr Magneton, unit of magnetic moment
More the magnetic moment more is the paramagnetic behaviour
i. Formation of Alloys:
As the transition elements have similar atomic sizes hence in the crystal
lattice, one metal can be readily replaced by another metal giving solid
solution and smooth alloys. The alloys so formed are hard and have often
high melting point.
j. Interstitial Compounds:
Transition metals form no. of interstitial compounds, in which they take up
atoms of small size e.g. H, C and N in the vacant spaces in their lattices. The
presence of these atoms results in decrease in malleability and ductility of
the metals but increases their tensile strength.
Exercise:
1. (a) (i) What is meant by the term d-block element? (1)
2+ ¿.¿
¿
(ii) Write the electronic configuration of Cu , Fe 2+¿∧Mn (3)
(iii) Explain why Fe2 +¿¿ ions are readily oxidised to Fe3 +¿¿ but Mn 2+¿¿ ions are
not readily oxidised to Mn3 +¿¿. (2)

CHROMIUM AND ITS COMPOUNDS

Chromium occurs naturally as a mineral ore but not as a free
element. The principal oxidation states of chromium are +2, +3 and
+6.
Extraction:
Chromium is extracted from its ore, chromite ( FeO . Cr 2 O3 ∨Fe Cr 2 O4)
consist of the following steps.
1. Concentration: the crushed ore is concentrated by gravity-
magnetic separation method to remove magnetite that is normally
associated with the ore.
2. The chromite concentrated ore is then heated with a mixture
of calcium carbonate and sodium carbonate in the presence of air.
The chromium is oxidised to sodium chromate (VI) while the iron
forms the stable iron (III) oxide.
4 FeCr 2 O4 ( s ) +8 Na2 CO 3 (s )+7 O2 ( g ) →8 Na2 Cr O4 ( s ) +2 Fe 2 O3 ( s ) +8 CO 2(g)

3. Leaching of the above mixture at relatively high

temperatures dissolves the chromate and leaves the insoluble iron
(III) oxide. The chromate is then converted to the dichromate by
oxidation using sulphuric.
2 Na2 Cr O 4 ( s )+ H 2 SO4 ( aq ) → Na2 Cr 2 O7 ( aq ) + Na2 SO4 ( aq ) + H 2 O(l)

4. The dichromate is now reduced to chromium (III) oxide using

carbon. The oxide is further reduced to chromium metal in an
aluminothermic reaction.
Na2 Cr 2 O7 ( aq ) +2C ( s ) → Cr 2 O3 ( s ) + Na2 CO 3 ( aq ) +CO (g)
Cr 2 O3 ( s ) +2 Al ( s ) → Al2 O3 ( s ) +2 Cr (s )

In Uganda, Chromite prospects are found in chlorite schists at Nakiloro

located 16 Km NE of Moroto town. The chromite here is associated with
platinum, a precious metal. There has been no chromite production in the
country.
PROPERTIES:
(a) Physical properties:
Chromium is a lustrous, brittle, hard metal. Its colour is silver-gray and it can
be highly polished. It does not tarnish in air, when heated it burns and forms
the green chromic oxide. Chromium is unstable in oxygen, it immediately
forms a thin oxide layer that is impermeable to oxygen and protects the
metal below.
(b) Chemical properties:
1. Reaction with air:
Chromium is inert under ordinary conditions due to the formation of a
protective layer of oxide.
On strong heating, chromium burns in oxygen to form chromium (III) oxide
and in chlorine to form chromium (III) chloride.
4 Cr ( s ) +3 O2 (g)→ 2 Cr2 O3 (s )
2 Cr ( s ) +3 Cl 2 (g)→ 2Cr Cl 3 (s)

2. Reaction with water:

Chromium is neither reacts with cold nor hot water. However, it
reduces steam to hydrogen.
2 Cr ( s ) +3 H 2 O ( g ) →Cr 2 O3 ( s ) +3 H 2 (g)

3. Reaction with alkalis:

Chromium reacts slowly with aqueous sodium hydroxide to liberate
hydrogen.
−¿(aq)+ 3 H2 ( g)¿
−¿ ( aq ) +6 H 2 O ( g) → 2Cr ( OH ) 4 ¿
2 Cr ( s ) +OH
4. Reaction with acids:
(i) Dilute sulphuric acid and hydrochloric acid react slowly with chromium in the cold but the rate
of reaction increases with increase in temperature and concentration to form chromium (II) compounds
with liberation of hydrogen.
2 +¿ ( aq ) +H 2 ( g)¿

Cr ( s )+ 2 H +¿ (aq )→ Cr ¿

(ii) Hot concentrated sulphuric acid reacts with chromium to form chromium (III) sulphate. The acid
is in turn reduced to sulphur dioxide.
2 Cr ( s ) +6 H 2 SO 4 (l)→ Cr2 ( SO 4 )3 (aq )+ 6 H 2 O ( g ) +3 SO2 ( g)
(iii) Cold dilute or concentrated nitric acid does not attack chromium due tyo formation of a
protective oxide layer of chromium (III) oxide .

Compounds of chromium:

a. Chromium (VI) oxide ( Cr O3)

It is prepared by adding concentrated sulphuric acid to a saturated solution of potassium dichromate
(VI). It is then crystallised from solution to form red needle shaped crystals.
K2Cr2O7 (aq)+ 2H2SO4 (l)→ 2CrO3 (s)+ 2KHSO4 (aq)+ H2O(l)
Chromium (VI) oxide is very soluble in water to form chromic (VI)
acid.
Chromium (VI) oxide is deliquescent and a very powerful oxidising agent.
When heated strongly, it melts at 192 ℃ and then decomposes on further
heating to form chromium (III) oxide and oxygen.
4 Cr O3 ( s ) → 2 Cr2 O3 ( s )+3 O2 (g)

b. Potassium Dichromate (K2Cr2O7)

Preparation
It is prepared from the ore called chromate or ferrochrome or chrome iron,
FeO.Cr2O3.
Step 1: Preparation of sodium chromate
4FeO.Cr2O3 + O2 → Fe2O3 + 4Cr2O3
4Na2CO3 + 2Cr2O3 + 3O2 → 4Na2CrO4 + 4CO2
Step 2: Conversion of sodium chromate into sodium dichromate.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
Step 3: Conversion of sodium dichromate into potassium dichromate.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Properties
1. Action of heat: When heated, it decomposed to its chromate
4K2Cr2O7 +Δ→ 4K2CrO4 + 2Cr2O3 + 3O2
2. Action of alkalis:
K2Cr2O7 + 2KOH → 2K2CrO4 + H2O
2K2Cr2O7 + H2SO4 → K2Cr2O7 + K2SO4 + H2O
3. Action of conc. H2SO4 solution:
(a) In cold conditions
K2Cr2O7 + 2H2SO4 → 2CrO3 + 2KHSO4 + H2O
(b) In hot conditions
2K2Cr2O7 + 8H2SO4 → 2K2SO4 + 2Cr2(SO4)3 + 8H2O + 3O2
4. Oxidising properties: It is a powerful oxidising agent.
In the presence of dil. H2SO4 it furnishes 3 atoms of available oxygen.
K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3O
Some of the oxidizing properties of K2Cr2O7 are
It liberates I2 from KI
K2Cr2O7 + 7H2SO4 + 6Kl → 4K2SO4 + Cr2(SO4)3 + 3l2 + 7H2O
It oxidises ferrous salts to ferric salts
K2Cr2O7 + 7H2SO4 + 6FeSO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3 + 2H2O
It oxidises S-2 to S
K2Cr2O7 + 4H2SO4 + 3H2S → K2SO4 + Cr2(SO4)3 + 7H2O + 3S
It oxidises nitrites to nitratesType equation here .
K2Cr2O7 + 4H2SO4 + 3NaNO2 → K2SO4 + Cr2(SO4)3 + 3NaNO3 + 4H2O
It oxidises SO2 to SO42–
K2Cr2O7 + H2SO4 + 3SO2 → K2SO4 + Cr2(SO4)3 + 3H2O
It oxidises ethyl alcohol to acetaldehyde and acetic acid.
Note:
Sodium dichromate (Na2Cr2O7.2 H2O) is hydrated and deliquescent whereas
Potassium dichromate (K2Cr2O7) is anhydrous and non-deliquescent with a
high melting point of400 ℃ . For this reason, potassium dichromate can be
used as a primary standard in volumetric analysis.
Potassium dichromate, as an oxidising agent in acidic medium, is used in
volumetric analysis to determine the amount (concentration) of reducing
−¿ ,H S, H O ,∧SO ¿
2 2 2 2

agents in solution e.g. Fe2 +¿, SO . Addition of iron (II) solution to acidified
2−¿ ,I ¿
3
¿

solution of potassium dichromate changes its colour from orange to green:

6¿
3+¿ ( aq) +7 H O ( l)¿
2
−¿ → 2Cr ¿

2−¿(aq)+ 14 H +¿ (aq ) +6 e ¿
¿
Cr 2 O7
3+¿ ( aq )+7 H O( l)¿
2
3+ ¿ (aq ) +6Fe ¿
2+ ¿( aq ) → 2Cr ¿

2−¿ ( aq ) +14 H + ¿ (aq )+6 Fe ¿

¿
Cr 2 O7
(orange) (green)
Acidified yellow solutions of Potassium/Sodium chromate (VI) are also
reduced to the green solutions containing chromium (III) ions.
3¿
3+¿ ( aq ) +4H O (l) ¿
2
−¿ → Cr ¿

2−¿(aq )+8 H+ ¿ ( aq )+ 3 e ¿
¿
Cr O 4
3+ ¿ (aq ) +4 H O (l )¿
2
3+¿ ( aq )+ 3Fe ¿
2+¿ ( aq ) →Cr ¿

2−¿ ( aq ) +8 H +¿ ( aq )+ 3 Fe ¿
¿
Cr O 4
(yellow) (green)
5. Chromyl chloride test:
When heated with conc. HCl or with a chloride in the presence of sulphuric
acid, reddish brown vapours of chromyl chloride are obtained.
K2Cr2O7 + 4KCl + 6H2SO4 → 2CrO2Cl2 + 6KHSO4 + 3H2O
Thus reaction is used in the detection of chloride ions in qualitative analysis.
c. Potassium chromate (VI)- K 2 Cr O4 :
Potassium chromate (VI) and sodium chromate (VI) are common laboratory
reagents which are yellow in colour.
Addition of acid to a yellow aqueous solution of chromate (VI) forms an
orange solution containing dichromate ions.
2−¿ (aq ) +H O ( l) ¿
2
+¿ ( aq ) ⇌Cr 2 O7 ¿

2 CrO 42−¿ ( aq)+2 H ¿

(yellow) (orange)
The above forward reaction is reversed on addition of an alkaline solution
+¿ ( aq ) ¿
2−¿ ( aq) +H ¿
−¿ (aq )→ 2CrO 4 ¿

Cr 2 O72−¿ ( aq) +OH ¿

(orange) (yellow)
Chromates (VI) solutions are also important reagents in qualitative analysis.
They are used to identify cations in solution which form coloured insoluble
chromate salts.
2−¿ ( aq ) →PbCr O4 ( s)¿
2+¿ ( aq ) +CrO4 ¿
Pb
(bright yellow)
2−¿ ( aq )→ BaCr O 4 (s )¿
2+¿ ( aq ) +CrO4 ¿
Ba
(pale yellow)
2−¿ (aq ) → Ag2 Cr O 4 (s )¿
+ ¿ ( aq ) +CrO 4 ¿
2 Ag
(red)
 −¿¿

Note: In the titration of Cl−¿∨ Br ¿ against Ag+¿¿ ions using potassium chromate
(VI) as indicator, formation of red precipitate shows the end point.
d. Chromium (III) oxide: (Cr 2 O3)
Chromium (III) oxide is a green solid which is found in nature as a
rare mineral eskolaite. It is normally prepared by;
i. Reducing sodium dichromate (VI) with carbon or sulphur.
Na2 Cr 2 O7 ( s ) + S ( s ) → Na2 SO4 ( s ) +Cr 2 O3 (s)

ii. Exothermic decomposition of ammonium dichromate.

( N H 4 ) 2 Cr 2 O7 ( s ) →Cr 2 O3 ( s ) + N 2 ( g ) +4 H 2 O(l)
iii. Decomposition of chromium (III) salts such as chromium (III)
nitrate:
4 Cr ( NO 3 )3 ( s ) ⟶ 2 Cr2 O3 ( s )+12 NO 2 ( g ) +3 O2 (g)

Chromium (III) oxide is an amphoteric oxide. Although insoluble in water, it

dissolves in acid to produce hydrated chromium ions.
3+ ¿( aq)¿
+¿ ( aq ) +9 H 2 O (l )→ 2 Cr ( H 2 O )6 ¿
Cr 2 O3 ( s ) +6 H
3+ ¿ ( aq )+ 3 H 2 O( l)¿
+¿ ( aq ) ⟶ 2 Cr ¿
or Cr 2 O 3 ( s ) +6 H

Chromium (III) oxide dissolves in alkalis to form basic salts.

3−¿(aq) ¿
−¿ ( aq ) +3 H 2 O(l)→ 2Cr ( OH )6 ¿
Cr 2 O3 ( s ) +6 OH
The basic salts dissolve in concentrated alkali to yield chromite ions.
When heated with finely divided carbon or aluminum metal it is reduced to
chromium metal.
Cr 2 O3 ( s ) +2 Al ( s ) → 2 Cr ( s ) + Al2 O3 ( s )

Heating chromium (III) oxide with chlorine and carbon yields

chromium (III) chloride and carbonmonoxide.
Cr 2 O3 ( s ) +3 Cl2 ( g ) +3 C ( s ) ⟶ 2Cr Cl 3 ( s ) +3 CO( g)

Uses:
 It is used as a pigment in paints, inks and glasses.
 It is used as a component in advanced electronics.
 It is used in the manufacture of light weight structural components in
aerospace crafts.
 It is used as a component in fuel cells.

It is used in ceramics.

e. Chromium (III) hydroxide: (Cr (OH )3)
Chromium (III) hydroxide is a green gelatinous precipitate formed
when a solution of alkali is added to a solution containing chromium (III) ions.
−¿ (aq )⟶ Cr ( OH )3 (aq) ¿

Cr 3+¿ (aq )+3 OH ¿

Chromium (III) hydroxide is amphoteric and dissolve in excess sodium

hydroxide to form the Cr (OH )3−¿¿
6 complex ion.
3−¿(aq) ¿

Cr (OH )3 ( s )+ 3OH −¿ (aq )⟶ Cr (OH ) ¿ 6

It dissolves in acids to form chromium (III) salts.

3+ ¿ ( aq )+ 3 H2 O(l) ¿

Cr (OH )3 ( s )+ 3 H +¿ (aq ) ⟶Cr ¿

f. Chromium (III) chloride: (Cr Cl 3)

Anhydrous chromium chloride is a violet solid whereas the hexahydrate salt is dark green. The
anhydrous salt is insoluble in water unless either a trace of chromium (II) chloride is present or
a reducing agent such as tin (II) chloride/tin metal in conc.HCl is added to reduce Cr 3+¿ ¿to Cr 2+¿ ¿
The solution of chromium (III) chloride contains the fairly acidic hexaaquachromium (III) ion-
3+¿¿
[ Cr ( H 2 O )6 ] .
+¿ (aq )¿
2+ ¿ ( aq )+ H 3 O ¿
[ ]
[ Cr ( H 2 O )6 ]
3+¿ ( aq ) +H 2 O ( l ) ⇌ Cr ( H 2 O)5 OH ¿

Treatment of this solution with a solution of silver nitrate, only a third of the chlorine
precipitates out as silver chloride. This means that only one third of the chlorine in this
compound is ionic. Therefore, the suggested formula for the hexahydrate is
−¿.2 H 2 O ¿
+ ¿.Cl ¿
[ Cr ( H 2 O )5 Cl 2 ]
Possible isomers for the ionic formula above are shown below. Note that in one of the isomers, all the
chlorine can be precipitated as silver chloride, while in the other only two thirds of the chlorine is
converted to the insoluble chloride.
3+¿. ¿¿¿ 2+¿. ¿¿¿
[ Cr ( H 2 O )6 ] [ Cr ( H 2 O )5 Cl ]
Grey-blue Light green
Chromium (III) chloride solution can conduct electricity and is decomposed
by electrolysis to form chlorine and metallic chromium.
Preparation:
i. Anhydrous chromium (III) chloride may be prepared by chlorination of
chromium metal directly or indirectly by carbothermic chlorination of
chromium(III) oxide at 650−800 ℃.
Cr 2 O3 ( s ) +3 Cl2 ( g ) +3 C ( s ) ⟶ 2Cr Cl 3 ( s ) +3 CO( g)
It may also be prepared by treating the hexahydrate with thionyl chloride.
Cr Cl 3 .6 H 2 O ( s ) +6 SOCl 2 ( aq ) ⟶ Cr Cl 3 ( aq ) +6 SO2 ( g )+12 HCl ( aq )
ii. Hydrated chromium (III) chloride can be prepared in the
laboratory by dissolving chromium metal or chromium (III) oxide in
hydrochloric acid.
Cr 2 O3 ( s ) +6 HCl ( aq )+ 9 H 2 O(l)→ 2Cr Cl3 .6 H 2 O(s)

g. Chromium (III) sulphate, (Cr 2 ( S O4 )3 . x H 2 O

Chromium (III) sulphate forms different hydrates with colours ranging from
violet to green.
Chromium sulphate is produced from chromate salts by reduction with
sulphur dioxide.
Na2 Cr 2 O7 ( s ) + SO2 ( g ) + H 2 O (l ) → Cr2 ( S O4 )3 ( s ) +2 NaOH (aq)
3+ ¿¿¿ ¿
Chromium (III) sulphate forms alum of formula K +¿Cr ¿ when
crystallised from aqueous solution in the presence of an equivalent
amount of potassium sulphate.
Chrome (III) alum is prepared by reduction of a solution of
potassium dichromate (VI), acidified with sulphuric acid, using
sulphur dioxide:
K 2 Cr2 O7 ( aq ) +3 SO2 ( g ) + H 2 SO 4 ( aq ) → K 2 SO 4 ( aq ) +Cr 2 ( S O4 )3 ( aq ) + H 2 O ( l )
On crystallization, purple octahedral crystals of chrome (III) alum separate
from solution.
h. Complexes of chromium (III):
(i) Tris (ethylenediamine) chromium (III) chloride:
This is a yellow-orange solid which is synthesized by refluxing chromium
chloride hexahydrate with ethylenediamine in the presence of zinc metal
(catalyst) and methanol.
Cr Cl 3 .6 H 2 O (s) + 3 ( H 2 NC H 2 C H 2 N H 2 ) → Cr ( H 2 NC H 2 C H 2 N H 2 )3 (s )+ 6 H 2 O(l)
The complex exhibits optical isomerism (enantiomers). The
optically active complexes results in the formation of racemic
mixtures (contain Left and Right handed enantiomers of non-
superimposable/chiral molecules)
Tris (ethylenediamine) chromium (III) chloride is used as a relaxation
reagent (improves spectral sensitivity) in C-13 NMR and an aid for structure
determination in aqueous solution.
(ii) Dichloro tetrammine chromium (III) ion:
This a type of complex that contains more than one type of ligand bonded to
the central chromium (III) ion. There are two forms of the complex ¿ ¿i.e. the
‘cis’ and ‘trans’ geometric isomers.
i. Chromium (II) compounds:
This is the least stable oxidation state of chromium, being powerfully
reducing.
Anhydrous chromium (II) chloride, Cr Cl 2 can be prepared by passing dry
hydrogen chloride over heated chromium metal.
Cr ( s )+ 2 HCl ( g ) →Cr Cl2 ( s ) + H 2 (g)

It can also be prepared by reducing chromium (III) chloride with either

hydrogen at 500 ℃, Lithium Aluminium Hydride or zinc metal.
2 Cr Cl 3 ( s ) + H 2 ( g ) →2 Cr Cl 2 ( s )+2 HCl(g)

4 Cr Cl 3 ( s ) + LiAl H 4 ( s ) → 4 Cr Cl 2 ( s )+ Al Cl 3 ( s ) + LiCl ( s )+2 H 2 ( g )

2 Cr Cl 3 ( s ) + Zn(s)→ 2 Cr Cl 2 ( s ) + ZnCl 2 (s)

Anhydrous chromium (II) chloride is a white hygroscopic solid which

readily dissolves in water to give a blue solution containing the tetrahydrate
2+¿¿
ion, Cr ( H 2 O ) 4 .
Commercial sample of the salt are often grey or green in colour.

Identification of Cr 3+¿ ¿ions in solution:

(i) To a solution containing Cr 3+¿ ¿ions (test solution), add sodium

hydroxide solution followed by hydrogen peroxide and boil for a few minutes.
A yellow solution containing sodium chromate (VI) is formed. On addition of
lead nitrate solution to this solution, a yellow precipitate of lead chromate is
formed.
(ii) To the test add potassium iodate. A light green precipitate is formed
insoluble on heating.
(iii) To the test solution add ammonium phosphate. A grey or pale green
precipitate is formed.
(iv) To the test solution add sodium tungstate. A thick cyan (red)
precipitate is formed insoluble on heating.
(v) To the test solution add sodium biselenite. A green or sky blue
precipitate is formed insoluble in excess reagent. There is no further reaction
even on heating.
(vi) To the test solution add sodium vanadate. A dark brown solution is
formed. On heating, a brown precipitate is formed in a green solution.
Uses of chromium compounds:
(i) In volumetric analysis for the estimation of Fe 2+ and I-.
(ii) In chrome tanning in leather industry.
(iii) In photography and in hardening gelatin film.
(iv) Formation of strong steel alloys (metal finishing industry)
(v) For chrome coating
(vi) As a refractory in furnaces

Exercise:
1. (a) State three characteristics of chromium as a transition metal.
(b) A solution of potassium dichromate (VI) was added to an acidified
solution of iron (II) sulphate.
i. state what was observed.
ii. write the ionic equation for the reaction that took place.
(c) i. write the structural formulae of the isomers of chromium (III)
chloride (CrCI 3 .6 H 2 O )
ii. State one way of distinguishing the isomers.
(d) Dilute sulphuric acid added to a solution of sodium chromate
followed by aqueous sodium hydroxide. (3)

MANGANESE AND ITS COMPOUNDS:

Occurrence:
Pyrolusite; MnO2
Hansmannite; Mn3 O4
Extraction of manganese from ore:
Reduction of Mn3 O4 with aluminium followed by distillation of manganese in
vacuo.
3 Mn3 O4 ( s ) +8 AI ( s ) → 4 AI 2 O3 ( s ) +9 Mn (s )

Properties of manganese:
 High melting point (1247° C )
  High boiling point (1962℃ ¿
 High density (7.42gcm−3 )
 Ionisation Energy (KJmol−1)

1st 2nd 3rd 4th 5th

I.E (KJ/mol) 717 1509 3248 4940 6990

 Atomic radius (pm)

2+¿¿ 3 +¿¿ 4+¿ ¿

Ion Mn Mn Mn

Radius (pm) 80 66 54

 Electrode Potential

Half reaction Mn (s)/Mn

2+¿ ¿¿
aq) Mn (s)/Mn 3+¿(aq)¿ Mn (s)/Mn 4 +¿(aq)¿
θ
E (Volts ) -1.18 -0.28 +1.52

 Electronegativity (1.55)
 Hard, brittle and not easily attacked by air at ordinary temperatures.
 Fairly reactive on heating and combines with non-metals ( O2 , N 2 , CI 2∧S )
and will liberate hydrogen from warm water.
 Reacts with dil. H2SO4 and dil. HCI to form Mn 2+¿(aq)¿ ions and liberating
hydrogen.
Uses:
 Ferromanganese alloy [Mn (80%); Fe (20%)] used in the manufacture
of alloy steels. Manganese confers hardness, toughness and
resistance to wear.
 Spiegeleisen [Mn (25%); Fe (70%); C (5%)] is added to molten steel to
remove combined oxygen and sulphur their by improving its
mechanical properties.
 Products of Manganese are used in the laboratory and manufactured
products as oxidizing agents;
(i) Potassium permanganate (KMnO4 ) is used as a volumetric
agent in redox analysis titrations.
(ii) Manganese (IV) oxide is used in zinc-carbon batteries
(oxidises hydrogen to water).
 (iii) Manganese (IV) oxide is used in paint dyes.
 Manganese compounds are found in fertilizers fungicide and
herbicides.
 Manganese is an essential trace element.
 Manganese activates the enzyme alkaline phosphatase in bone
formation and the enzyme organase in urea formation.
 Manganese is an important mineral in our bodies to prevent
deformation of the skeleton and sterility.
In Western Uganda, use of manganese oxide as a flux in production of iron
ore, especially in Mwenge, Kabarole district at the end of the second
millennium AD has been investigated and established.
Compounds of Manganese:
 Forms compounds in which exist in the +7, +6, +4, +3 and +2
oxidation states.
 +7 oxidation state is the most oxidising whereas +2 oxidation state is
the most stable.
 Reduction from +7 to +2 oxidation state can be achieve by using a
variety of reducing agents e.g. shaking Acidified solution of potassium
manganate(VII) with zinc amalgam. 2+¿ (aq )+8H O (l) ¿
2
2+¿ (aq )+5Zn ¿

−¿+ 16 H +¿( aq)+Zn ( s) →2 Mn ¿

¿
2 MnO4
(purple) (Colourless)

(A) Potassium Permanganate:

a. Preparation:
It is prepared from the mineral pyrolusite, MnO 2.
Step:1, Conversion of MnO2 (black powder) into potassium manganate (VI), a
green solid, by fusing the black powder with potassium hydroxide in the
presence of an oxidising agent e.g. potassium chlorate (V).
−¿+3 H O¿
2
2−¿ +CI ¿
−¿→3 MnO 4 ¿
−¿+CIO3 ¿
3 MnO2 ( s ) +6 OH
Or 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
Step:2, Oxidation of potassium manganate into permanganate
Chemical oxidation:
K2MnO4 is oxidised to KMnO4 by bubbling CO2 or Cl2 or ozone into the former.
3K2MnO4 + 2CO2 → 2KMnO4 + MnO2 + 2K2CO3
Electrolytic oxidation:
2K2MnO4 + H2O + O → 2KMnO4 + 2KOH
OR
The green solid is crushed and dissolved in water. The resultant solution is
boiled and potassium manganate (VI) disproportionates to give potassium
manganate (VII) and manganese (IV) oxide. Carbondioxide is bubbled
−¿ ¿
through the solution to remove hydroxyl¿ ions as ( HCO3 ) ions so as to allow
the reaction to go to completion. Note: potassium manganate (VI) is stable
under alkaline conditions.
−¿ ( aq )+ MnO 2 ( s )+ 4OH −¿¿ ¿
2−¿ ( aq ) +2 H 2 O ( l ) ⇌ 2 MnO 4 ¿
3 MnO4
−¿( aq)¿

OH −¿ ( aq)+ 4 CO (g)→ 4 HCO

2 3 ¿
(alkaline medium neutralized)
Filter resultant solution to remove MnO2 and evaporate filtrate until
crystallisation of potassium manganate (VII).

b. Properties
KMnO4 exists as deep purple prisms. It is moderately soluble in water at
room temperature and its solubility in water increases with temperature.
(i) Action of heat
When heated it decomposes to K2MnO4.
2KMnO4 → K2MnO4 + MnO2 + O2
(ii) Action of conc. H2SO4
With cold conc. H2SO4 it gives Mn2O7 which on warming decomposes to MnO2.
2MnO2 + 2H2SO4 → Mn2O7 + 2KHSO4 + 2H2O
2Mn2O7 + Δ → 4MnO2 + 3O2
With hot Conc. H2SO4 O2 is evolved
4KMnO4 + 6H2SO4 → 2K2SO4 + 4MnSO4 + 6H2O + 5O2

(iii) Oxidising properties

KMnO4 is a powerful oxidizing agent. The actual oxidizing action depends
upon the medium i.e. acidic, basic or neutral.
(a) In neutral solution, it acts as moderate oxidizing agent.
2KMnO4 + H2O → 2KOH + 2MnO2 + 3O
Some oxidizing properties of KMnO4 in neutral medium are
2KMnO4 + 3Na2S2O3 + H2O → 3K2SO4 + 8MnO2 + 3Na2SO4 + 2KOH
2KMnO4 + 4H2S → 2MnS + S + K2SO4 + 4H2O
(b) In strong alkaline solution, it is converted into potassium manganate (VI)
and then to manganese (IV) oxide. For example, in the oxidation of ethene
by alkaline potassium manganate (VII) to ethane-1,2-diol, the colour of
solution changes from purple to green and finally a brown residue of MnO2 is
formed.
−¿
−¿/ OH CH 2OH CH 2 OH ¿
CH 2=CH 2 MnO 4 →
¿
1
2−¿+ H O+ O ¿
2 2 2
−¿ ⟶ 2MnO 4 ¿
−¿+ 2OH ¿
2 MnO4
(purple) (green)
1
−¿+ O2 ¿
2
2−¿+ H 2 O ⟶ MnO 2 +2OH ¿
MnO 4
(brown)
(c) In acidic medium, Mn+7 is converted into Mn+2
2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5O
Some other reactions are
(i) 2KMnO4 + 3H2SO4 + 5H2S → K2SO4 + 2MnSO4 + 3H2O + 5S
Or
(ii) 2KMnO4 + 5SO2 + 2H2O → K2SO4 + 2MnSO4 + 2H2SO4
A Strip of filter paper impregnated with an acidified solution of potassium
permanganate is decolorized when gaseous reducing agent; H 2S or SO2 is
passed over it.
(iii) 2KMnO4 + 3H2SO4 + 5KNO2 → K2SO4 + 2MnSO4 + 3H2O + 5KNO3
−¿ (aq ) +3H O (l) ¿
2
2+¿ ( aq) +5NO ¿
3
( ) −¿ ( aq ) ⟶Mn ¿

−¿ ( aq ) +6 H +¿ aq + 5 NO ¿
¿
2 MnO4
2

(iv) 2KMnO4 + 3H2SO4 + 10HCl → K2SO4 + 2MnSO4 + 8H2O + 5Cl2

2+¿ ( aq) +5Cl ( g) +8H O (l) ¿
2 2
−¿ ( aq ) ⟶2Mn ¿

−¿ ( aq ) +16 H+ ¿ ( aq )+ 10Cl ¿
¿
2 MnO4
(v) 2KMnO4 + 3H2SO4 + 5C2H2O4 → K2SO4 + 2MnSO4 + 8H2O + 10CO2
A standard solution of potassium manganate (VII) can be used for estimating
oxalates.
 2+¿ ( aq)+ 4H O (l) ¿
2
−¿ ⟶ Mn ¿
+ ¿(aq)+ 5e ¿
−¿ ( aq ) +8 H ¿
MnO 4
−¿¿
2−¿(aq)⟶ 2 CO2 (g)+2 e ¿
C 2 O4

(vi) 2KMnO4 + 8H2SO4 + 10FeSO4 → K2SO4 + 2MnSO4 + 5Fe2 (SO4)3 + 8H2O

Potassium manganate (VII) is used in volumetric analysis but un like
potassium dichromate solution; it cannot be used as a primary standard
because it cannot be obtained in a high state of purity. Samples of the
substance are found to contain traces of manganese (IV) oxide. Potassium
manganate (VII) is normally standardised using a standard solution of
ammonium ferrous sulphate [ FeSO 4 .(NH 4 )2 SO 4 .12 H 2 O] acidified with dil. H2SO4.
Potassium manganate (VII) solution from the burette is run into an acidified
solution of Fe2 +¿¿in the conical flask. At the end point, the yellowish - green
solution turn to pink.
2+¿ ( aq)+ 4H O (l) ¿
2
−¿ ⟶ Mn ¿
+ ¿(aq)+ 5e ¿
( )
MnO 4−¿ aq +8 H ¿

3+ ¿ ( aq )+ e −¿ ¿ ¿

Fe2 +¿(aq )⟶ Fe
¿

(vii) 2KMnO4 + 3H2SO4 + 10Kl → K2SO4 + 2MnSO4 + 8H2O + 5l2

c. Uses
(i)Used in volumetric analysis for estimation of ferrous salts, oxalates,
iodides & H2O2.
(ii) Used as oxidizing agent in the laboratory as well as in industry.
(iii) Used as disinfectant and germicide.

Tests for Mn 2+¿¿ions:

 To a solution containing Mn 2+¿¿ions, add sodium hydroxide solution. A
white ppt of Mn ¿ is formed which slowly turns brown on the surface on
standing.
−¿ (aq ) ⟶ Mn¿ ¿

Mn 2+¿ ( aq)+ 2OH ¿

Brown manganese (III) oxide, Mn 2 O3 . x H 2 O , is formed on standing due to

aerial oxidation. Mn ¿ is insoluble in excess sodium hydroxide.
 To a solution containing Mn 2+¿¿ions, add a solution of sodium
bismuthate followed by dil. nitric acid. A purple solution is formed due
−¿¿
to the presence of MnO 4 ions.
3+¿ (aq )+7H O (l) ¿
2
−¿ (aq )+5 Bi ¿
+¿ (aq )⟶2 MnO ¿
−¿( aq)+14 H 4
¿
2+ ¿(aq )+5 BiO 3 ¿
2 Mn
(colourless) (purple)
Note: Sodium bismuthate (Na BiO3 ) acts as an oxidising agent.
(B) Potassium manganate (VI): ( K 2 MnO4 )
Potassium manganate (VI) can be made by strongly heating a mixture of
manganese (IV) oxide, potassium hydroxide and potassium chlorate in a
crucible and extracting the manganese (VI) compound with water.
3 MnO2 (s)+6 KOH (aq)+ KClO3 (aq)→ 3 K 2 MnO 4 (aq)+ KCl (aq)+3 H 2 O(l)
−¿ (aq )+3H O (l )¿
2
2−¿ (aq )+Cl ¿
−¿(aq)→ 3 MnO 4 ¿
OR 3 MnO2 (s)+6 OH −¿(aq)+ClO 3 ¿

The green solution containing MnO 42−¿¿ ion is unstable in acidic solution and
slowly undergoes disproportionation (species in one oxidation state
spontaneously and simultaneously changes into two species of different
oxidation states –one higher and one lower in oxidation number).
−¿ ( aq ) +MnO ( s )+ 2H O( l)¿
2 2
+¿ (aq ) →2 MnO 4 ¿

3 MnO4 2−¿ (aq )+4 H ¿

(C) Manganese (IV) Oxide ( MnO2):

Manganese (IV) oxide is a black powdery insoluble solid. It is a powerful
oxidising agent releasing chlorine from conc. HCI.
MnO2 ( s ) +4 HCI ( aq ) ⟶ MnCI 2 ( aq ) +2 H 2 O ( l ) +CI 2 (g)

Manganese (IV) oxide acts as a catalyst in the decomposition of hydrogen

peroxide into oxygen and water.
2 H 2 O2 (l)MnO 2 2 H 2 O ( l ) +O2 (g)
→

If a small quantity of manganese (IV) oxide is added to ice cooled

concentrated hydrochloric acid an anionic octahedral manganese (IV) chloro
complex ion is forced. If the mixture is filtered through glass wool the brown
colour of the complex can be seen.
2−¿ ( aq )+ 2H O (l ) ¿
2
−¿ ( aq ) →MnCl 6 ¿

MnO2 ( s ) +4 H +¿ ( aq)+6 Cl ¿

If the mixture is warmed, chlorine is formed as the complex decomposes to

manganese (II) compound.
−¿( aq)+CI 2 (g) ¿

Mn Cl 62−¿ (aq ) → MnCI (aq )+2 Cl

2 ¿

(D) Manganese (II) Oxide ( MnO ):

This is a greyish-green solid which is prepared by heating manganese (II)
oxalate.
Mn C 2 O4 ( s ) ⟶ MnO ( s ) +CO2 ( g ) +CO (g)
Manganese (II) oxide is attacked by acids to form salts. However, it does not
react with alkalis.
(E) Manganese Sulphide ( MnS ):
MnS is a pale pink solid formed when hydrogen sulphide is passed through an
aqueous solution containing Mn 2+¿¿ions in the presence of aqueous ammonia
and ammonium chloride.
(F) Manganese (II) Salts:
Manganese (II) salts are readily prepared by dissolving manganese (II)
carbonate in the appropriate dilute acid. e.g.
MnCO 3 ( s )+ 2 HCI ( aq ) ⟶ MnCI 2 ( aq ) + H 2 O ( l ) +CO 2 (g)
MnCO 3 ( s )+ H 2 SO 4 ( aq ) ⟶ MnSO4 ( aq ) + H 2 O ( l ) +CO 2 (g)
MnCO 3 ( s )+ 2 H NO 3 ( aq ) ⟶ Mn ( NO3 )2 ( aq ) + H 2 O ( l ) +CO 2 (g)

Solutions of manganese (II) salts contain the very pale pink hexa-aqua
manganese (II) ion, Mn ¿, which is quite stable in aqueous solution.
Manganese (II) solutions react with alkali solutions such as sodium hydroxide
and ammonia to produce manganese hydroxide which is insoluble in excess
reagents.
−¿ (aq ) ⟶ Mn¿ ¿
2+¿ ( aq ) + 2OH ¿
Mn
Manganese (II) hydroxide is almost white if oxygen is excluded but it
gradually turns brown to form hydrated manganese (III) oxide.
4 Mn ¿
The hydrated oxide Mn 2 O3 can also be written as a hydroxyl-oxide, MnO(OH ).
Reaction of Mn 2+¿¿ions with aqueous sodium carbonate solution produces a
precipitate of manganese carbonate.
2−¿(aq)→ MnCO3 ( s) ¿

Mn 2+¿ ( aq)+CO 3 ¿

Like manganese (II) hydroxide, manganese carbonate is readily oxidises to

brown manganese (III) oxidises.
Acidified Mn 2+¿ ( aq) ¿ is not oxidised by hydrogen peroxide but alkaline
manganese (II) hydroxide is oxidised to give brown hydrated manganese (III)
oxidised/hydroxide.
The hexa -aqua manganese (II) ion readily forms complexes with poly
dentate ligands.
 Mn ¿
(en=H 2 N CH 2 CH 2 N H 2)

Exercise:
1. Potassium manganate (VII) under acidic conditions oxidises ethane-
1,2-dioic to carbondioxide.
1
(a) Write equation for the reaction. (1 )
2
(b) Calculate the volume of 0.5M H 2 C2 O4 solution that will be
required to react completely with 20.0cm−3 of 0.2M potassium manganate
(VII) solution. (5)
(c) Explain why solutions of potassium manganate (VII) should
not be acidified using.
(i) Hydrochloric acid. (
1
1 )
2
(ii) Nitric acid. (1)

2. 6.30 g sample of hydrated ethanedioic acid, H 2 C2 O4 . x H 2 O , was dissolved

in water and the solution made up to 250cm3.
A 25.0 cm3 sample of this solution was acidified and titrated with 0.100 mol
−3 −3
dm potassium manganate (VII) solution. 20.0cm of this potassium
manganate (VII) solution was required to react fully with the ethanedioate
ions, C 2 O2−¿¿
4 , present in the sample.
−¿¿
(a) The MnO 4 ions in the potassium manganate (VII) oxidise the
ethanedioate ions.
(i) Explain, in terms of electron transfer, the meaning of the term oxidise in
the sentence above.
[1]
(ii) Complete and balance the ionic equation for the reaction between the
manganate (VII) ions and the ethanedioate ions.
−¿¿
2 MnO 4 (aq) + 5C 2 O2−¿¿
4 (aq) + .........H+(aq) → …….. (aq) + 10CO 2(aq) + .....
H2 O [3]

(b) (i) Calculate the number of moles of manganate(VII) used in the

titration.[1]
 (ii) Use the equation in (a)(ii) and your answer to (b)(i) to calculate the
number of moles of C 2 O2−¿¿
4 present in the 25.0cm3 sample of solution used.
[1]

(iii) Calculate the number of moles of H 2 C2 O4 . x H 2 O in 6.30 g of the

compound.
[1]
(iv) Calculate the relative formula mass of H 2 C2 O4 . x H 2 O .
[1]

(v) The relative formula mass of anhydrous ethanedioic acid, H 2 C2 O4, is 90.
Calculate the value of x in H 2 C2 O4 . x H 2 O .

IRON AND ITS COMPOUNDS:

Physical properties
Iron is a silvery-white or grayish metal. It is ductile and malleable. Ductile
means capable of being drawn into thin wires. Malleable means capable of
being hammered into thin sheets. It is one of only three naturally occurring
magnetic elements. The other two are nickel and cobalt
Iron has a very high tensile strength. Tensile means it can be stretched
without breaking. Iron is also very workable. Workability is the ability to
bend, roll, hammer, cut, shape, form, and otherwise work with a metal to get
it into a desired shape or thickness.
The melting point of pure iron is 1,536°C (2,797°F) and its boiling point is
about 3,000°C (5,400°F). Its density is 7.87 grams per cubic centimeter. The
melting point, boiling point, and other physical properties of steel alloys may
be quite different from those of pure iron.
Chemical properties
Iron is a very active metal. It readily combines with oxygen in moist air. The
product of this reaction, iron oxide (Fe 2 O 3 ), is known as rust. Iron also
reacts with very hot water and steam to produce hydrogen gas. It also
dissolves in most acids and reacts with many other elements.
Occurrence in nature
Iron is the fourth most abundant element in the Earth's crust. Its abundance
is estimated to be about 5 percent. Most scientists believe that the Earth's
core consists largely of iron. Iron is also found in the Sun, asteroids, and stars
outside the solar system.
The most common ores of iron are hematite, or ferric oxide ( Fe2 O3 ); limonite,
or ferric oxide (Fe 2 O 3 ); magnetite, or iron oxide (Fe 3 O 4 ); and siderite, or
iron carbonate ( Fe CO3 ). An increasingly important source of iron is taconite.
Taconite is a mixture of hematite and silica (sand). It contains about 25
percent iron.
The largest iron resources in the world are in China, Russia, Brazil, Canada,
Australia, and India. The largest producers of iron from ore in the world are
China, Japan, the United States, Russia, Germany, and Brazil.
In Uganda, hematite (90-98% Fe2 O3) occurs at Butare in Kabale district and
Kyamuzinda, Kashenyi and Kamena in Kisoro district with total resources in
excess of 50 million tons which contain negligible sulphur, phosphorus and
titanium. Other resources of up to 2 million tons of the ore have been
reported at Mugabuzi (Mbarara district), Nyaituma (Hoima district) and
Namugongo peninsula (Mayuge district). Other districts in Uganda that have
reported deposits of the ore include; Tororo, Kotido and Napak.
At Sukulu (Tororo district) magnetite occurs in residual soils with apatite
(phosphates). A resource of 45 million tons averaging 62% Fe, 2.6% P2 O 5 and
0.9% Ti O2 has been estimated.
There has been very limited production of iron ore in Uganda to-date mainly
for use as an additive in the steel scrap smelting in Jinja and for special
cement by Hima cement.
Isotopes
There are four naturally occurring isotopes of iron, iron-54, iron-56, iron-57,
and iron-58. Isotopes are two or more forms of an element. Isotopes differ
from each other according to their mass number. The number written to the
right of the element's name is the mass number. The mass number
represents the number of protons plus neutrons in the nucleus of an atom of
the element. The number of protons determines the element, but the
number of neutrons in the atom of any one element can vary. Each variation
is an isotope.
Six radioactive isotopes of iron are known also. A radioactive isotope is one
that breaks apart and gives off some form of radiation. Radioactive isotopes
are produced when very small particles are fired at atoms. These particles
stick in the atoms and make them radioactive.
Two radioactive isotopes of iron are used in medical and scientific research.
They are iron-55 and iron-59. These isotopes are used primarily as tracers in
studies on blood. A tracer is a radioactive isotope whose presence in a
system can easily be detected. The isotope is injected into the system. Inside
the system, the isotope gives off radiation. That radiation can be followed by
detectors placed around the system. Iron-55 and iron-59 are used to study
the way in which red blood cells develop in the body. These studies can be
used to tell if a person's blood is healthy.
Extraction
Iron goes through a number of stages between ore and final steel product. In
the first stage, iron ore is heated with limestone and coke (pure carbon) in a
blast furnace. A blast furnace is a very large oven, normally measuring 40m
high and 10m in diameter, in which the temperature may reach 1,500°C
(2,700°F). It is encased with steel whose inner side is lined with fire bricks. A
blast of hot air is introduced lower down in the furnace through several pipes
called tuyeres. At the bottom of the blast furnace is a well which holds
molten iron and slag for some time. Two tap holes exist, one which allows
slag to be tapped off and the other which lets out the denser molten iron.
Note that molten iron is much denser than slag.
A mixture of the ore Fe2 O3, Coke and Limestone are fed in continuously from
the top of the blast furnace. Preheated air at about 600 ℃ is introduced into
the furnace through pipes and reacts with the white hot coke to produce the
reducing gas, carbonmonoxide.
O2 ( g )+ C(s) →2 CO (g)
The carbonmonoxide produced then reduces iron (III) oxide to metallic iron
at a temperature of 700−1000℃ .
Fe2 O3 ( s ) +3 CO ( g ) → 2 Fe ( s )+3 CO 2 (g)
The limestone decomposes at about 800 ℃ and the calcium oxide reacts with
sandy impurities to form a slag of calcium silicate.
CaCO 3 ( s ) → CaO ( s )+CO 2 ( g)
CaO ( s )+ SiO2 (s)→CaSi O3 (s) (slag)
More carbonmonoxide is produced by the reduction of carbondioxide by coke
at a temperature of about 1200 ℃:
C ( s )+CO 2 (g)→ 2 CO(g)

The molten slag does not mix with iron and is less dense. Therefore, it floats
on top of the molten iron and can be easily tapped off separately. Molten
iron, on the other hand, can also be run off into moulds and allowed to cool
to form pig iron.

Pig iron produced by this method is about 91 to 92 percent pure. The main
impurity left is carbon from the coke used in the furnace. Pig iron is generally
too brittle (it breaks too easily) to be used in most products.
Most scientists believe that the Earth's core consists largely of iron.
A number of methods have been developed for purifying pig iron. A common
method used today is called the basic oxygen process. In this process, pig
iron is melted in a large oven. Then pure oxygen gas is blown through the
molten pig iron. The oxygen burns off much of the carbon in the pig iron:
Steel:
A small amount of carbon remains in the iron. The iron produced in this
reaction is known as steel.
The term "steel" actually refers to a wide variety of products. The various
forms of steel all contain iron and carbon. They also contain one or more
other elements, such as silicon, titanium, vanadium, chromium,
manganese, cobalt, nickel, zirconium, molybdenum, and tungsten.
Two other steel-like products are cast iron and wrought iron.
Cast iron is an alloy of iron, carbon, phosphorus and silicon. It is used to
make manhole covers, Drainage pipes, Bunsen burner bases, Gutters,
Radiators, Railings, Lamp posts etc.
Wrought iron contains iron and any one or more of many other elements.
In general, however, wrought iron tends to contain very little carbon.
Manufacture of steel:
a) Siemens-Martin Open Hearth Process: A mixture of impure molten
iron, scrap steel and limestone is heated in an open-hearth furnace by
producer gas (mixture of nitrogen and carbonmonoxide). The furnace
is lined with a mixture of calcium oxide and magnesium oxide, made
by strongly heating dolomite (CaCO 3 . Mg CO3). Haematite ( Fe2 O3)
converts impurities including carbon, silicon and phosphorus into their
respective oxides; carbonmonoxide, silicon dioxide and phosphorus (V)
oxide which combine with the lining to form a slag.
Fe2 O3 ( s ) +3 C ( s ) → 2 Fe ( s )+3 CO (s)
2 Fe2 O3 ( s ) +3 Si ( s ) → 4 Fe ( s ) +3 Si O2 (s)
5 Fe2 O3 ( s ) +6 P ( s ) →10 Fe ( s ) +3 P2 O5 ( g)
CaO ( s )+ SiO2 (s)→CaSi O3 (s) (slag)
An alloy of manganese, iron and carbon known as spiegeleisen is added,
together with other alloying metals, depending on the type of steel required.
However, modern developments of the open - hearth process include the use
of fuel oil instead of producer gas, and enrichment of the air supply with
oxygen to provide more efficient combustion. Pure oxygen is also injected
into the molten mixture of molten iron to speed up the oxidation of
impurities.

b) Bessemer Process: The Bessemer converter is charged with a

considerable tonnage of molten iron at a temperature of about 1200 ℃.
This is followed by blowing a blast of oxygen which has been diluted by
either steam or carbondioxide through the converter. It should be
noted that oxygen instead of producer gas is preferred since nitrogen
is retained by steel and makes it brittle. The oxygen is diluted by
 carbondioxide instead of steam since the latter would produce
hydrogen which would make the steel brittle.
Oxygen reacts with the impurities to convert them into their respective
oxides while at the same time increasing the temperature in the converter to
about 1900 ℃. After some time the flame at the top of the converter subsides
indicating that all the carbon has been removed. Slag is tapped off leaving
the purified molten iron which is then run off into moulds and mixed with
spiegeleisen and other ingredients according to the type of steel required.

Uses
It would be impossible to list all uses of iron and steel products. In general,
those products can be classified into categories: (1) automotive; (2)
construction; (3) containers, packaging, and shipping; (4) machinery and
industrial equipment; (5) rail transportation; (6) oil and gas industries; (7)
electrical equipment; and (8) appliances and utensils. (For more information
on specific kinds of steel alloys, see individual elements, such as titanium,
vanadium, chromium, manganese, molybdenum, and tungsten.)
Compounds
Some iron is made into compounds. The amount is very small compared to
the amount used in steel and other iron alloys. Probably the fastest growing
use of iron compounds is in water treatment systems. The terms ferric and
ferrous refer to two different forms in which iron occurs in compounds. Some
of the important iron compounds are:
 Ferric acetate [Fe ( C2 H 3 O2 )3 ]: used in the dyeing of cloth
 Ferric ammonium oxalate[Fe ( NH 4 )3 ( C 2 O4 )4 ]: blueprints
 Ferric arsenate [FeAs O 4 ]: insecticide
 Ferric chloride [Fe Cl 3 ]: water purification and sewage treatment
systems; dyeing of cloth; coloring agent in paints; additive for animal
feed; etching material for engraving, photography, and printed circuits
 Ferric chromate [Fe 2 ( CrO 4 )3 ]: yellow pigment (coloring) for paints and
ceramics
 Ferric hydroxide [Fe (OH )3 ]: brown pigment for coloring rubber; water
purification systems
 Ferric phosphate [Fe PO 4 ] : fertilizer; additive for animal and human
foods
 Ferrous acetate [Fe ( C2 H 3 O2 )2 ]: dyeing of fabrics and leather; wood
preservative
 Ferrous gluconate ¿]: dietary supplement in "iron pills"
 Ferrous oxalate[Fe C 2 O 4 ]: yellow pigment for paints, plastics, glass, and
ceramics; photographic developer.
 Ferrous sulfate (FeSO4 ): water purification and sewage treatment
systems; catalyst in production of ammonia; fertilizer; herbicide;
 additive for animal feed; wood preservative; additive to flour to
increase iron levels
Health effects

Iron is of critical importance to plants, humans, and animals. It occurs in

haemoglobin, a molecule that carries oxygen in the blood. Haemoglobin
picks up oxygen in the lungs, and carries it to the cells. In the cells, oxygen is
used to produce energy the body needs to survive, grow, and stay healthy.
Iron is available in a number of foods, including meat, eggs, and raisins.
An iron deficiency (lack of iron) can cause serious health problems in
humans. For instance, hemoglobin molecules may not form in sufficient
numbers. Or they may lose the ability to carry oxygen. If this occurs, a
person develops a condition known as anemia. Anemia results in fatigue.
Severe anemia can result in a lowered resistance to disease and an increase
in heart and respiratory (breathing) problems. Some forms of anemia can
even cause death.
Rusting of iron:
This metallic corrosion that is electrochemical in nature. In the presence of
air and water, iron corrodes due to the transfer of electrons along the metal
surface due to the potential difference arising from the difference in the
oxygen concentrations at the different positions of the metal surface. As a
result, iron (II) hydroxide forms on the surface and is later oxidised to
hydrated iron (III) oxide, Fe2 O3 . n H 2 O which is rust.
When the piece of iron material is tin-plated, rusting is prevented since the
iron surface is covered. When one point is scratched and the iron exposed ,
an electrochemical cell is set up. Since iron has a more electrode potential
than tin, the exposed part of iron becomes the negative pole. The negative
pole losses electrons (oxidises) to form Fe2 +¿¿ions which dissolve in
Type equation here . water to form iron (II) hydroxide which slowly dissolves in
oxygen to form hydrated iron (III) oxide (rust).
−¿¿

Cathode reaction: Fe ( s ) → Fe2 +¿ ( aq)+2 e ¿

−¿(aq) ¿

Anode reaction: 2 H 2 O ( l ) → 2 H +¿(aq )+2 OH ¿

−¿→ H 2 (g) ¿

2 H +¿ ( aq)+2 e ¿

−¿ ( aq ) →Fe (OH )2 (s ) →Fe 2 O3 . nH 2 O ¿

2 +¿ ( aq ) +2 OH ¿
Fe
Tin plating is only effective as long as the coating remains intact (unlike zinc-
plating). When a piece of galvanized (zinc plated) iron is scratched at a point,
the electrochemical cell set up has zinc as the negative pole and the
exposed iron as the positive pole (zinc has a more negative electrode
potential than iron).
Zinc (-ve pole) losses electrons to form Zn2+¿¿ ions which dissolve in water to
form zinc (II) hydroxide.
−¿¿
2 +¿ ( aq ) +2 e ¿
Zn ( s ) → Zn
−¿( aq)→ Zn( OH )2 (aq) ¿
¿
Zn2+¿(aq)+ 2OH
The electrons from the negative pole move to the pole (exposed iron). This
iron is stabilized further by surrounding negatively charged electrons and
this prevents the ionization of iron. Therefore, iron does not rust because
zinc provides “cathodic prevention”.
Compounds of iron:
Stable compounds of iron are in the +3 oxidation state. Compounds
in +2 oxidation state are reducing whereas those in the unstable
oxidation state of +6 are powerfully oxidising.
(a) Iron (VI) compounds:
Potassium ferrate (VI), K 2 FeO 4, can be prepared by fusing iron filings
and potassium nitrate. The solid dissolves in water to form a dark
red solution. The dark red colour is due to the presence of ferrate
(VI) , FeO 2−¿¿
4 (aq) ions.
Ferrate (VI) ions are powerful oxidising agents and will oxidise Cr 3+¿ ¿
to CrO 2−¿¿
4 .
2−¿¿¿
FeO 4
(b) Iron (III) compounds:
(i) Iron (III) oxide: ( Fe2 O3)
Iron (III) oxide is a rust red solid which occurs naturally as the ore Haematite.
It can be prepared in the laboratory by heating iron (III) hydroxide or iron (II)
sulphate.
2 Fe (OH )3 ( s ) → Fe2 O3 ( s ) +3 H 2 O ( l )
2 Fe SO 4 ( s ) → Fe 2 O3 ( s ) +SO 2 (g)+ SO 3 (g)
(ii) Iron (III) hydroxide: Fe ( OH )3
Iron (III) oxide is a gelatinous rust brown coloured compound obtained by
adding hydroxyl ions to a solution containing iron (III) ions.
−¿ ( aq ) →Fe ( OH )3 (s )¿

Fe3 +¿ ( aq)+3 OH ¿

(iii) Tri-iron tetroxide: ( Fe3 O4∨Fe 2 O3 . FeO )

This mixed oxide of iron is a black solid which occurs naturally as the ore
magnetite. It is prepared by passing steam over heated iron filings.
 3 Fe ( s ) +4 H 2 O ( g ) → Fe3 O4 ( s ) +4 H 2(g)
When reacted with the acids it gives a mixture of iron (II) and iron (III) salts in
the ratio of 1:2
Fe3 O4 ( s ) +4 H 2 SO4 ( aq ) → Fe 2 ( SO4 ) 3 (aq)+ Fe SO 4 ( aq ) + 4 H 2 O(l)

(iv) Iron (III) chloride: ( Fe Cl3 )

Iron (III) chloride is a dark red covalent solid which is prepared by synthesis
(direct combination of elements).
2 Fe ( s )+ 3Cl 2 ( g ) → 2 Fe Cl 3 (s)
When heated, the salt sublimes to form dimerized molecules, Fe2 Cl6 . Iron (III)
bromide is prepared and reacts similarly.
Iron (III) chloride crystallizes in water to give the hexahydrate, Fe Cl3 .6 H 2 O . It
dissolves in water to form a yellow solution containing a variety of complex
cations as given by the equilibrium reactions below.
−¿ ( aq )+ H 2 O (l)¿

Fe Cl3 +6 H 2 O(l)⇌ Fe ( H 2 O )5 Cl2 +¿ ( aq)+2 Cl ¿

−¿( aq ) +H O ( l) ¿
2
+¿ ( aq )+ Cl ¿
−¿ (aq ) ⇌ Fe( H 2 O )4 Cl2 ¿
2+¿ ( aq ) +2 Cl ¿
Fe ( H 2 O )5 Cl
Anhydrous iron (III) chloride is used as a catalyst in Friedel-Crafts reactions.
In this reaction iron (III) chloride acts as a halogen carrier from the acid
−¿¿
chloride forming the unstable complex ion, Fe Cl 4 .
2 RCOCl+ Fe2 Cl6 → 2¿
Note: Iron (III) iodide cannot be obtained in the pure state since a solution
containing Fe3 +¿¿ions readily oxidises iodide ions to iodine.
2+¿ ( aq ) +I ( aq) ¿
2
−¿ (aq )→ 2Fe ¿

2 Fe3+¿ (aq )+2 I ¿

This means that iodine is not a sufficiently powerful oxidising agent to

convert Fe2 +¿¿ to Fe3 +¿¿.
(v) Iron (III) sulphate: ( Fe2 ( SO 4 )3)
Iron (III) sulphate can be obtained by heating an aqueous acidified solution of
iron (II) sulphate with hydrogen peroxide (oxidising agent):
2 Fe SO4 ( aq ) + H 2 SO4 ( aq ) + H 2 O2 ( aq ) → Fe 2 ( SO 4 ) 3 ( aq ) +2 H 2 O(l)
 COBALT AND ITS COMPOUNDS:
Cobalt is a chemical element with symbol Co and atomic number 27. It is found in the
earth crust only in chemically combined form, save for small deposits found in alloys of
natural meteoric iron.
It is a hard lustrous bluish gray metal whose melting point is 1495 ℃ and boiling point
2927 ℃ . Cobalt has a density of 8.90 gcm−3at room temperature.
Occurrence:
The metal is found in metallic ores such as cobaltite (CoAsS) and as a byproduct of
Copper and Nickle mining. The following are some of the economic mineral deposits of
cobalt;
Name: Group: Formula
Erythrite Arsenate Co3 ( As O 4 )2 .8 H 2 O

Skutterudite Arsenide ¿
Cobaltite Sulpho salt CoAsS
Carrollite Sulphide Cu ¿ ¿
3+ ¿S 4 ¿
¿
Linnaeite Sulphide Co2+¿ Co 2

Asbolite (Asbolane) Oxide ( ¿ , Co )2−x Mn4 +¿ ( O ,OH ) .n H

4 2 O¿

Cobalt has only one isotope Co59 and has twenty two (22) radio isotopes where Co60 is
the most commonly used. Cobalt-60 has a half-life 5.27 years and powerful γ −rays
emitter.
The highest exploration priorities for cobalt in Uganda are at Kilembe and Bujagali
which lie on the Central African copper belt. Democratic Republic of Congo produces
60% of the worlds’ cobalt.

Uses of cobalt:
(i) Cobalt is primarily used in the manufacture of high resistant and high
strength alloys (super alloys of Ni, Co, Fe).
 (ii) The compounds cobalt silicate and cobalt (II) aluminate give a
distinctive blue colour to glass, ceramics, inks, paints and varnishes.
(iii) Cobalt-60 is a commercially important radioisotope, used as a
radioisotope tracer and production of high energy γ −rays used in the
treatment of cancer.
(iv) Cobalt is an active centre of a group of co-enzymes called
cobalamines. Vitamin B12, the best known example of the type is an
essential trace mineral for all animals.
(v) Cobalt in inorganic form is also a micro-nutrient for bacteria, algae and
fungi.
(vi) Cobalt is used for making rechargeable battery electrodes.
(vii) Cobalt is used in making of magnets.
(viii) Cobalt is used as a catalyst in many industrial chemical reactions.
(ix) Cobalt is used in making hard materials. e.g, carbides and diamond
tools.

Compounds:
Common oxidation states are +2 and +3, although compounds with oxidation states
ranging from -3 to +5 are also known.
A common oxidation state for simple compounds is +2. These salts form pink coloured
metal aqua complex, Co ¿, in water. Addition of chloride gives the intensely blue [
2−¿ ¿
Co Cl4 ¿ ¿ .
In a borax bead flame test, cobalt shows deep blue colour in both oxidising and
reducing flames.
(A): Oxides:
Cobalt (II) oxide (CoO) is green powdery compound and has a rock salt structure. It is
readily oxidised with water and oxygen to brown cobalt (III) hydroxide, Co ¿.
At temperatures of 600 ℃−700℃ , CoO oxidises to blue mixed oxide Co3 O4 which has a
spinel structure. Black cobalt (III) oxide Co2 O3 is also known.
Oxides of cobalt are anti-ferromagnetic at low temperatures.
(B): Cobalt (II) Sulphide (CoS):
This is a black solid which is precipitated when Sulphide ions , either from hydrogen
Sulphide under weakly acidic conditions with ethanoic acid or sodium Sulphide under
neutral to slightly alkaline conditions, reacts with Cobalt (II) ions.
2−¿(s )→ cos(s )¿
¿
Co2+¿(aq)+S
Cobalt (II) Sulphide can only be dissolved in nitric acid or aqua regis:
2+¿ (aq) +3S( s ) +2NO ( g) +4 H O (l )¿
2
+ ¿ (aq )→3 Co ¿

cos ( s )+ 2 NO 3−¿ ( aq)+ 8 H ¿

(C): Cobalt (II) halides:

Halide Colour

Cobalt (II) fluoride; Co F 2 Pink

Cobalt (II) Chloride; Co Cl2 Blue

Cobalt (II) Bromide; Co Br 2 Green

Cobalt (II) Iodide; Co I 2 Blue-Black

These halides exist in anhydrous and hydrated forms.

Whereas the anhydrous cobalt (II) chloride is blue, the hydrated forms Co Cl2 .2 H 2 O is
changes colour from sky blue to purple and finally to pink. Such striking changes in
colour make anhydrous cobalt (II) chloride an ideal humidity indicator in weather
instruments. Cobalt (II) chloride is also used as an absorbent of ammonia, gas masks,
electroplating hygrometers, manufacture of vitamin B12, solid lubricant, dye mordant
and as a fertilizer additive.
A solution of cobalt (II) chloride contains hexa-aqua cobalt (II) ions as shown in the
equation below;
−¿(aq) ¿

Co Cl2 ( s ) +6 H 2 O ( l ) ⇌ Co(H ¿¿ 2 O)62 +¿ ( aq)+2 Cl ¿

¿
Reaction of Co(H ¿¿ 2 O)62 +¿ ( aq) ¿ ¿ ions with concentrated hydrochloric acid to form a blue
solution containing the tetra cobaltate (II) ions.
−¿ (aq ) ⇌ ¿¿

Co(H ¿¿ 2 O)62 +¿ ( aq)+ 4 Cl ¿

¿
(pink) (blue)
−¿¿
The above equilibrium can be disturbed by changing the chloride [Cl ] ion
concentration.
Solutions containing cobalt (II) ions react with sodium hydroxide to form a bluish-pink
precipitate.
−¿ (aq ) →Co (OH )2 ( H 2 O )4 (s )+ 2 H2 O ( l ) ¿

Co(H ¿¿ 2 O)62 +¿ ( aq)+2 OH ¿

¿

(pink) (bluish-pink)
The precipitate dissolves partially in excess alkali and is oxidated to form the dark
brown cobalt (III) hydroxide.
 Co ( OH )2 ( H 2 O ) 4 ( s ) + H 2 O ( l ) +O2 (g)→ Co ( OH )3 (s)

(dark brown)
With ammonia solution, cobalt (II) ions form the bluish-pink precipitate of the hydrated
hydroxide;
+ ¿(aq) ¿
2 +¿ ( aq ) +2 NH 3 ( aq ) →Co ( OH ) 2 ( H 2O )4 ( s) +2 NH 4 ¿
Co(H ¿¿ 2 O)6 ¿
The precipitate dissolves in excess ammonia to form the yellowish-brown unstable
complex of hexa ammine cobalt (II) ions.
−¿(aq)¿
2+¿ ( aq ) +4 H 2O ( l ) +2OH ¿
Co ( OH )2 ( H 2 O ) 4 ( s ) +6 NH 3 ( aq ) → [ Co ( NH 3) 6 ]

(yellowish-brown)
The cobalt (II) ammonia complex oxidises in the presence of oxygen to reddish-brown
complex of hexa ammine cobalt (III) ions.
−¿ (aq) ¿
3+¿ (aq ) +e ¿
2+¿ ( aq ) → [ Co ( NH 3)6 ]
[ Co ( NH 3 )6 ]
¿

(yellowish-brown) (reddish-brown)
Cobalt (II) ions react with thiocyanate ions, in acidic or neutral conditions, to form
complexes.
−¿ ( aq ) ⇌¿¿
2+¿ ( aq ) +SCN ¿
[ Co ( H 2 O )6 ]
(red)
−¿ (aq ) ⇌ ¿¿
2+¿ ( aq ) +4 SCN ¿
[ Co ( H 2 O )6 ]
(blue)
(D): Cobalt Acetate/Ethanoate:
Anhydrous cobalt acetate is a red-violet (intense red) crystalline compound. The
hydrated form, Co(CH 3 COO)2 .5 H 2 O is a pink crystalline solid and is prepared by
reacting cobalt (II) oxide or hydroxide with acetic (ethanoic) acid.
CoO ( s )+ 2CH 3 COOH ( aq )+ 4 H 2 O (l ) →Co ( CH 3 COO )2 .5 H 2 O(aq)

Cobalt acetate is a precursor to various oil catalysts; catalysts that allow paints and
varnishes to harden.
Note:
Different cobalt (III) ion complexes can be isolated when cobalt (II) chloride is dissolved
in aqueous ammonia and then oxidised by air to the +3 oxidation state. These
complexes have different colours with different empirical formulas. The table below
shows the different formulae of the complexes and their colours.

Complex Colour

Co Cl3 .6 NH 3 (reddish-brown)

Co Cl3 .5 NH 3 . H 2 O (red)

Co Cl3 .5 NH 3 (purple)

Co Cl3 .4 NH 3 (green)
+¿¿
When a solution containing silver ( Ag ) ions is added to a solution of Co Cl3 .6 NH 3 and
Co Cl3 .5 NH 3 . H 2 O complexes, 3 moles of silver chloride are formed for each mole of
complex ion in solution.
−¿(aq )¿
3+¿ ( aq ) +3 Cl ¿
Co Cl3 .6 NH 3 ( aq ) ⇌ [ Co ( NH 3 )6 ]
−¿(aq) ¿
3 +¿ ( aq ) +3 Cl ¿
Co Cl3 .5 NH 3 . H 2 O ( aq ) ⇌ [ Co ( NH 3 )5 .(H 2 O) ]

However, 2 moles of silver chloride are formed for each mole of Co Cl3 .5 NH 3and 1 mole
of silver chloride for each mole of Co Cl3 .4 NH 3.
−¿(aq)¿
2 +¿ ( aq ) +2 Cl ¿
Co Cl3 .5 NH 3 ( aq ) ⇌ [ Co ( NH 3 )5 . ( Cl ) ]
−¿(aq)¿
+¿ ( aq ) +Cl ¿
Co Cl3 .4 NH 3 ( aq ) ⇌ [ Co ( NH 3 )4 . ( Cl2 ) ]

Measurement of conductivity of aqueous solutions of the complexes suggests that

Co Cl3 .6 NH 3 and Co Cl3 .5 NH 3 . H 2 O dissociate in water to give a total of 4 ions,
Co Cl3 .5 NH 3 dissociates to give 3 ions and Co Cl3 .4 NH 3 dissociates to give only 2 ions.

The cobalt (III) ion is coordinated to a total of 6 ligands in each complex. Any ion or
molecule with a pair of non-bonding electrons (lone pair of electrons) can be a ligand.
Many ligands are described as mono dentate (one toothed) because they ‘bite’ the
−¿¿ −¿¿ −¿¿ −¿¿
metal in only one place. Typical mono dentate ligands are; F , Cl , Br , OH , H 2 O
−¿ ¿ −¿¿ 2−¿ ¿
, NH 3, O2, CO , C O2 , CN , SCN , S2 O3 .

Other ligands can attach to the metal more than once. Ethylene diamine (en) is a typical
bidentate ligand.
H N −¿ CH CH ¨ − N̈ H ¿
2 2 2 2

Each end of this molecule contains a pair of non-bonding electrons that can form a
covalent bond to a metal ion. Ethylene diamine is also an example of a chelating ligand.
The term chelate (Greek=claw). Ethylene Diamine Tetra Acetate (EDTA) is an example
of a hexadentate ligand.

¿¿¿
Note:
The reduction potential for the reaction;
2+¿ ( aq) ¿
−¿→ Co ¿
θ
Co3+ ¿ (aq )+e ¿
E =+1.92V
is higher than that of the reaction;
1 −¿→ Cl −¿(aq)¿
¿
Cl ( g ) +e θ
E =+1.36 V
2 2
Consequently, Co3+ ¿ (aq ) ¿ ions would be reduced to Co2+¿(aq)¿ ions in the presence of
−¿(aq)¿
Cl ions. This implies that Cobalt (III) chloride is a less stable salt.
The reduction potential for the reaction;
1 −¿→ F −¿(aq )¿
¿
F ( g ) +e θ
E =+2.87 V is so high, Cobalt(III) fluoride is one of the few
2 2
simple stable Cobalt (III) compounds.
Isomerism of Cobalt (III) chloride complexes:
Cobalt shows a number of complexes that exhibit geometrical and structural isomerism,
just like chromium. A number of such complexes are formed when ammonia solution is
added to an aqueous solution of cobalt (III) chloride as shown in the table below.

Empirical formula Formula of complex No. of Colour Percentage

ions ionic chlorine
−¿¿

(i) Co Cl3 . ( NH 3 )6 [ Co ( NH 3 )6 ]
3+¿ 3 Cl ¿
4 Orange/yellow 100
−¿¿

(ii) Co Cl3 . ( NH 3 )5 [ Co ( NH 3 )5 Cl ]
2+¿ 2Cl ¿
3 Violet 67
−¿ ¿

(iii) Co Cl3 . ( NH 3 ) 4 [ Co ( NH 3 )4 ( Cl )2 ]
+¿ Cl ¿
2 Violet (cis) 33
−¿ ¿

(iv) Co Cl3 . ( NH 3 ) 4 [ Co ( NH 3 )4 ( Cl )2 ]
+¿ Cl ¿
2 Green (trans) 33

The formulas of the complexes are determined by reaction with silver nitrate solution.
Only the chloride which is no directly attached to the central complex metal cation will
precipitate as silver chloride.
Conductivity measurements in aqueous solution also allow the number of ions
generated to be calculated. i.e. four from compound (i), three from compound (ii) and
two from compound (iii) and (iv).
Tests for cobalt (II) ions:
(i) To the test solution add several drops of ammonium thiocyanate in acetone or
butanol. The bright blue colour is the indication of Co2+¿ ¿. OR
(ii) To the test solution add concentrated hydrochloric acid followed by ammonium
thiocyanate ( NH 4 SCN ) and pentanol in tetra chloromethane and shake the mixture well.
Formation of an upper blue layer confirms the presence of cobalt (II) ions.
(iii) To the test solution add sodium vanadate. A pale violet ppt is formed which
does not change on heating.
(iv) To the test solution add sodium biselenite. No reaction on initial addition of
reagent. However, a purple ppt of cobalt selenite is formed on strong heating.
(v) To the test solution add sodium silicate. A gelatinous magenta ppt is formed
which turns to a blue/violet colour on heating due to formation of the insoluble cobalt
silicate.

Exercise:
−¿¿
3 +¿3 CI ¿
1. 0.005 moles of the compound Co(N H 3 )x was heated in excess alkali and
3
the ammonia liberated was absorbed in 50cm of 0.5M sulphuric acid. The excess acid
remaining after absorption required 40.0 cm3 of 0.5M sodium hydroxide for
neutralization.
1
(a) Calculate the value of x . (3 )
2
1
(b) Give the name of the compound. ( )
2

NICKEL AND ITS COMPOUNDS:

Nickel exhibits the oxidation states +2, +3 and +4. The most stable
oxidation states +2. The melting point of nickel is about 1450 ℃ and has a
density of 8.9dm−3 .
Nickel is a hard silver white metal, which occurs as cubic crystals. It is
malleable, ductile and has superior strength and corrosion resistant. The
metal is a fair conductor of heat and electricity and exhibits magnetic
properties below 345℃ . Five isotopes of nickel are known.
In its metallic form nickel is chemically unreactive. It is insoluble in hot and
cold water and ammonia and is unaffected by concentrated nitric acid and
alkalis. It is however soluble in dilute nitric acid and sparingly soluble in
dilute hydrochloric acid and sulphuric acid.
In Uganda, prospects of Nickel/Zinc/Silver/Lead mineralization exist in the
Kitgum-Pader belt similar to the “Broken Hill (Australia)” type of deposits.
In 2011 SIPA conducted aerial surveys to collect airborne
magnetic/radiometric data sets over an area of 7296 sq.km in Northern
Uganda under the Kitgum-Pader Base and Precious Metal Project. Over
50,000 soil samples have so far been collected along with geological
mapping from the area have led to the discovery of two potentially economic
mineral systems; the intrusive nickel/copper sulphide mineralization at
Akelikongo and the Lead/Zinc/Silver mineralization at Pamwa.
Additional nickel and other mineral deposits have been reported in Karamoja
region.
Extraction: (Mond /Carbonyl process)-Ludwig Mond, 1899
The chief ores of nickel include millerite (NiS), Pentlandite (NiFe S2), Garnierite
[(NiMg) SiO3 . n H 2 O]. The ore is crushed, concentrated by floatation and the
roasted in air with silicon (IV) oxide. Silicon (IV) oxide removes iron as a slag
of iron silicates. Nickel (II) oxide formed during the roasting process is then
reduced by hydrogen gas at 200 ℃ to give nickel together with impurities
including iron and cobalt.
NiO ( s ) + H 2 ( g ) →∋ ( s ) + H 2 O(g)

The impure nickel reacts with carbon monoxide at 50 ℃−60℃ to form the gas
nickel carbonyl, leaving the impurities as solids.
¿ ( s ) + 4 CO (g)→∋ (CO )4 ( g)

The mixture of nickel carbonyl and hydrogen is the heated to 220 ℃−250 ℃
resulting in decomposition back to 99.99% pure nickel and carbon monoxide.
¿ ( CO )4 (g)→∋ ( s ) + 4 CO ( g)

Chemical properties:
(a) Reaction with water and air:
 Nickel does not react with water or air at ordinary temperatures. However,
nickel forms nickel (II) oxide when strongly heated in oxygen.
(b) Reaction with acids:
Nickel reacts with dilute acids slowly to form corresponding nickel (II) salts.
Concentrated nitric acid renders the metal passive.
Compounds of nickel:
1. Nickel (II) oxide is green powdery solid which becomes yellow on
heating. It is a basic oxide prepared by heating nickel (II) nitrate or nickel (II)
carbonate.
2∋ ( NO3 ) 2 ( s ) →2 NiO ( s ) +4 NO 2 ( g )+ O2 (g)
¿ CO 3 ( s ) → NiO ( s ) +CO 2 (g)
2+¿ ¿
It dissolves in dilute acids to form green ¿ ( H 2 O )6 ions.
2. Nickel (II) hydroxide; [Ni( OH )2] exists as green crystals which can be
precipitated by adding sodium hydroxide solution to an aqueous solution of
nickel (II) ions.
−¿(aq )→∋(OH )2 (s )¿

¿2 +¿ ( aq)+2 OH ¿

The hydroxide of nickel is basic and therefore reacts with acids to form
corresponding nickel (II) salts. It is soluble in excess ammonia solution
2+¿ ¿
forming a blue solution containing hexamine nickel (II) [ ¿ ( NH 3 )6 ] ion and
2 +¿¿
tetrammine diaqua nickel (II) [¿ ( H 2 O )2 ( NH 3 )4 ] ion.
−¿(aq)¿

¿ ( OH )2 (s)⇌ ¿2+¿ (aq )+2 OH ¿

2+ ¿(aq)¿
2 +¿ ( aq ) +6 NH 3 (aq )⇌∋( NH 3)6 ¿
¿
3. Nickel (II) carbonate is pale green and can be precipitated by addition
of sodium hydrogen carbonate solution to an aqueous solution containing
nickel (II) ions.
4. Nickel (II) sulphide is precipitated when hydrogen sulphide is passed
through an aqueous solution of ¿2 +¿¿in the presence of ammonia solution and
ammonium chloride solution.
5. Nickel (II) nitrate, chloride and sulphate are soluble salts which can be
prepared by action of respective acids on nickel (II) oxide, carbonate or
hydroxide followed by partial evaporation and crystallization. Nickel (II)
sulphate forms a double salt when crystallised in the presence of an
equivalent amount of ammonium sulphate; the double salt,
( NH 4 )2 SO 4 .∋ SO4 .6 H 2 O is used in aqueous solution as the electrolyte in nickel
plating.
Complexes of nickel
Nickel (II) complexes are fairly numerous and the majority of them are
2+¿ ¿ 2+¿ ¿
octahedral e.g. the green ¿ ( H 2 O )6 and the blue ¿ ( NH 3 )6 . Common square
planar complexes of nickel include ¿ ( CN )42−¿¿ and nickel dimethylglyoximate
which precipitates as a red solid when dimethylglyoxime is added to an
alkaline solution of nickel (II) salt.
−¿ (aq )→∋ (DMG )2 ( s) +2 H 2 O (l )¿

2 DMG+ ¿2+¿ (aq )+2 OH ¿

Uses of nickel and its compounds:

i. Nickel is used in the preparation of alloys such as stainless steel, tubing
used in desalination of sea water, armour plates and burglar proof
vaults.
ii. Electroplating. Nickel plating is used in protecting coating of other
metals. In wire form, nickel is used in pins, staples, jewelry and surgical
wire.
iii. Finely divided nickel catalyses’ the hydrogenation of vegetable oils.
iv. Nickel is used in colouring of glass to which it gives a green hue.
v. Nickel is used in making coins.
vi. Nickel electrodes are used to make certain types of fuel cells.
vii. Nickel is used in the petroleum and chemical industry.
viii. Nickel compounds are used as ingredients in some paints and dyes.
ix. Nickel acetate is used as a mordant in the textile industry.
x. The enzyme, urease which converts urea to ammonia and bicarbonate,
and is obtained from the bacterium helicobacter contains ¿2 +¿¿ ions.

Exercise:
1. (a) Z is a purple salt which dissolves in water to give a
solution which turns green on warming. When sodium hydroxide
solution is added to a solution of Z, a green precipitate Y is formed
soluble in excess of the alkali. On addition of hydrogen peroxide to
the alkaline solution, the colour turns yellow. On adding more
hydrogen peroxide and acidifying with dilute sulphuric acid, the
colour turns blue and later turns green with evolution of oxygen on
standing. The solution of Z gives a white precipitate with barium
chloride, which is insoluble in dilute hydrochloric acid.
(i) Identify X, Y and Z. (3)
(ii) Account for the colour changes involved. (4)
(b) The figure below shows the variation of colour
intensity when equimolar solutions of nickel (II) sulphate and
aqueous ammonia are mixed so that the sum of their concentrations
is always one mol per dm3.

Colour
intensity

0 0.14 0.86 1.0

−3
[NH ¿¿ 3]mol dm ¿
Determine the formula of the nickel-ammonia complex ion.
(3)
2. (a) Nickle (atomic number 28) is a transition element.
(i) Write the electronic configuration of nickel.
(1)
(ii) State, giving examples three properties
which qualify nickel as a transition element. (3)
(b) A solution of potassium hexacyanoferrate (II) was
added to a solution of nickel (II) sulphate.
 (i) State what was observed.
(1)
(ii) Write an ionic equation for the reaction that took
1
place. (1 )
2
(c) Name one reagent that is used to confirm the presence
of nickel (II) ions in solution. (1)

COPPER AND ITS COMPOUNDS

Occurrence:
Copper is found in several parts of Uganda but significant deposits are at
Kilembe, Kasese district, where copper/cobalt sulphide mineralization occurs.
Other areas where such mineralization have been noted at Bobong
(Karamoja), Kampono and Kitaka in Mbarara district. Copper is also reported
in Buhweju and Bushenyi districts. Although copper was first reported at
Kilembe in 1908, the deposit was not brought into production until 1956 on
completion of the railway line to Kasese. In July 1950,two Canadian
companies, Frobisher Limited and Ventures Limited, formed a joint venture,
named Kilembe Mines Limited (KLM) whose main objective was to mine
copper from under the Rwenzori Mountains near Kasese. KLM built and
operated a copper smelter in Jinja and maintained offices in Kampala.
Between 1957 and 1979 a total of 16.29 million tons of ore averaging 1.95%
Cu and 0.18% Co were mined and treated to yield 217,000 tons of blister Cu
which was exported, plus 1.1 million tons of cobaltiferous pyrites (iron
sulphite) which was stock piled.
The Kilembe Mine ceased its production in 1982 due to dilapidated
equipment, high inflation and insecurity and has since been on care and
maintenance.
In 2013, a consortium led by Tibet-Hima Mining Company Limited, won the
competitive bid to manage, rehabilitate and operate Kilembe Mines limited
for 25 years from 2013 until 2038.
Extraction of copper:
The chief ores include copper pyrites, CuFe S 2, copper glance, Cu2 S , cuprite,
Cu2 O , and malachite, Cu CO3 .Cu ( OH )2.
The pulverized ore is first concentrated by ore flotation process and roasted
in limited supply of air to convert the iron into iron (II) oxide:
2 CuFe S 2 ( s ) + 4 O2 ( g ) →Cu2 S ( s ) +3 SO 2 ( g ) +2 FeO (s)

Silicon (IV) oxide is added and the mixture in absence of air to convert iron
(II) oxide to slag of iron (II) silicate which is then poured away from copper (I)
sulphide, Cu2 S .
The copper (I) sulphide is reduced to copper by heating in a reduced amount
of air.
Cu2 S ( s ) +O2 ( g ) → 2 Cu ( s )+ SO2 ( g )

Copper is refined electrolytically to give a product of about 99.95% purity.

The impure copper is made the anode in an electrolytic cell which contains
pure strips of copper as the cathode immersed in an electrolyte of copper (II)
sulphate solution. During electrolysis copper is transferred from the anode to
the cathode. Sludge containing gold and silver is produced during the
process which helps to make the process economically feasible.
Physical properties of copper:
Copper has a melting point of 1083.4℃ , boiling point of 2567℃ . Copper is
reddish coloured and takes a bright metallic luster. It is malleable, ductile
and a good conductor of electricity and heat.
Chemical properties:
(a) Reaction with air and water:
The metal is slowly attacked by moist air and its surface is gradually
becomes covered by a green layer of copper carbonate. Copper is attacked
by air or oxygen at 300℃ to form a black layer of copper (II) oxide. At a
temperature of about 1000℃ copper (I) oxide layer is formed instead.
(b) Reaction with non-metals:
Copper is attacked by sulphur vapour to form copper (I) sulphide and by
halogens to form copper (II) halides except iodine which forms copper (I)
iodide.
(c) Reaction with acids:
Dilute acids have no action on copper especially in the
absence of strong oxidising agents. However, boiling hydrochloric acid
attacks the metal with evolution of hydrogen inspite of the positive electrode
potential exhibited by copper.
 −¿ (aq )+H (g) ¿
−¿ (aq )⇌ 2Cu Cl2
2
¿

2 Cu ( s )+2 H +¿ (aq )+4 Cl ¿

Hot concentrated sulphuric acid and so does concentrated

and dilute nitric acid react with the metal according to the equations below.
Cu ( s ) +2 H 2 S O4 ( l ) ⟶ CuS O4 ( s ) +2 H 2 O ( l )+ S O2 (g)
3 Cu ( s )+ 8 HN O3 ( aq ) →3 Cu ( NO3 ) 2 ( aq ) +4 H 2 O (l )+2 NO (g)

dil.
Cu ( s ) +4 HN O3 ( aq ) →Cu ( NO3 ) 2 ( aq ) +2 H 2 O ( l )+2 N O2 (g)

conc.
Uses of copper:
(i) Winding of dynamos.
(ii) Conveying electrical power.
(iii) Construction of condensers for chemical plants and car radiators.
(iv) Making of metal alloys e.g.;
1. Brass (Cu & Zn) which is used for making cartridge containers,
headlamps reflectors and the working parts of watches and clocks.
2. Bronze (Cu & Sn) used for fabricating bearings and ships’ fittings and
sports medals.
(v) Making catalysts (finely divided copper) in the industrial oxidation of
methanol to methanal.
COMPOUNDS OF COPPER:
A: Copper (I) compounds:
Aqueous solutions of copper (I) ions is unstable and disproportionates into
the copper (II) ion and copper.
−¿→Cu( s)¿

Cu+¿ ( aq)+ e ¿ θ
E =+0.52V
+¿ (aq )¿
−¿→Cu ¿
θ
Cu2+¿ (aq )+e ¿
E =+0.16 V
2+ ¿(aq) ¿

2 Cu+¿ (aq ) →Cu ( s )+Cu ¿ θ

E =+0.36 V
All the above cell reactions have positive values of e.m.f implying
that hydrated copper (I) ions are thermodynamically unstable in solution with
respect to copper and hydrated copper (II) ions.
 Therefore, the chemistry of copper (I) is largely that of its water
insoluble compounds and of its stable complexes.
(a) Copper (I) oxide ( Cu2 O )
Copper (I) oxide is a covalent brick red solid in which each
oxygen atom is being surrounded by four copper atoms and each copper
atom lying midway between two oxygen atoms (4:2 co-ordination). It is
prepared by adding an alkaline solution of sodium potassium tartrate to
copper (II) sulphate. This is followed by addition of hydrazine sulphate or
glucose (reducing agents) and boiling for a few minutes.
Cu SO4 ( aq ) +2 NaOH ( aq ) →Cu ( OH )2 ( s ) + Na2 SO4 (aq)
Cu ( OH )2 ( s ) + KNa C 4 H 4 O6 (aq)→ KNa [ Cu ( C 4 H 2 O6 ) ] (aq)+2 H 2 O ( l )

deep blue cplx soln

KNa [ Cu ( C 4 H 2 O6 ) ] ( aq ) + N 2 H 4 . H 2 SO 4 ( aq ) +2 NaOH ( aq ) → Cu2 O ( s ) + KNa C 4 H 4 O6 ( aq ) + Na2 SO 4 ( aq )+ N 2 (g)

Copper (I) oxide reacts with dilute sulphuric acid on warming to give a blue
solution of copper (II) sulphate and a deposit of copper (disproportionation
reaction).
2+ ¿ (aq )+Cu (s )+ H 2 O ( l )¿

Cu2 O ( s ) +2 H +¿ ( aq) →Cu ¿

Copper (I) oxide dissolves in concentrated hydrochloric acid with formation of

the dichlorocuprate (I) complex ions.
+ ¿ ( aq )+ H 2 O (l )¿
−¿ ( aq ) +2 H ¿
Cu2 O ( s ) + 4 HCl ( aq ) → 2Cu Cl2

(b) Copper (I) chloride (CuCl):

Copper (I) chloride is a white covalent solid which is insoluble in water. It can
be prepared by boiling a solution containing copper (II) chloride, excess
copper turnings and conc. hydrochloric acid. The resultant solution which
contains dichlorocuprate (I) complex ions is then poured into air-free distilled
water and copper (I) chloride precipitates as a white solid. The white solid is
then washed, dried and sealed in the absence of air so that it doesn’t oxidise
to the green copper (II) chloride.
−¿ ( aq ) ¿
−¿ (aq) ⇌2Cu Cl ¿
2

2+¿ ( aq ) ⇌2 Cu+ ¿ ( aq )+ 4 Cl ¿
¿
Cu ( s ) +Cu
Copper (I) chloride is commonly used together with ammonium chloride as a
catalyst in the dimerization of ethyne to but-1-ene-3-yne which is the
starting material in the production of rubber.
 2 ( HC ≡ CH ) CuCl , HCl , NH 4 Cl H 2 C=CH −C ≡ CH
→

In the laboratory a mixture of Copper (I) chloride and hydrochloric acid is

used for converting benzene diazonium chloride into chlorobenzene (Sand
Meyer reaction)
−¿ ( aq ) CuCl ,HCl C 6 H 5 Cl ( l )+ N 2 ( g)¿
+¿Cl ¿
C6 H5 N2
→

Ethyne can be purified by bubbling the gas in an ammoniacal solution of

copper (I) chloride. The precipitate of copper (I) carbide formed can then be
reacted with dilute acids to evolve pure ethyne.
(c) Copper (I) iodide (Cul):
Copper (I) iodide is a white solid which is prepared by adding a solution of
potassium iodide to an aqueous solution of a copper (II) salt.
−¿ ( aq )⟶ 2 CuI ( s )+ I2 ( aq)¿

2 Cu2+¿ ( aq) +4 I
¿

This reaction can be used to estimate the concentration of a copper (II) salt,
since quantitative formation of iodine can be determined by titration with
standard sodium thiosulphates solution.
−¿ ( aq )⟶ 2 CuI ( s )+ I2 ( aq)¿

2 Cu2+¿ ( aq) +4 I ¿

2−¿( aq ) ¿
−¿ ( aq )+ S4 O6 ¿
( aq ) +I ( aq ) →2 I ¿
2 S 2 O2−¿
3
2

(d) Copper (I) sulphate (Cu2 SO4 ):

A white solid which is stable in absence of moisture. It is formed
when solid copper (I) oxide is heated with anhydrous dimethyl sulphate:
Cu2 O ( s ) + ( CH 3 )2 SO4 ( l ) →Cu2 SO4 ( s )+ ( CH 3 )2 O(l)
Cu2 SO4 ( s ) + H 2 O ( l ) ⟶ Cu SO4 ( aq )+Cu( s)

B: Copper (II) compounds:

This is the mostcommon oxidation state of copper and soluble copper
(II) salts form blue aqueous solutions. The blue colour is attributed to the
2 +¿¿
presence of Cu ( H 2 O )6 ions in solution.

(a) Copper (II) oxide (CuO):

This is a black solid which may be obtained by heating copper (II) carbonate
or copper (II) nitrate.
 Cu CO3 ( s ) ⟶ CuO ( s ) +CO2 (g)
2 Cu ( NO 3 )2 ( s ) ⟶ 2 CuO ( s ) + 4 NO2 ( g ) +O2 (g)

Copper (II) oxide decomposes at a temperature of about 800 ℃ to form

copper (I) oxide and oxygen.
4 CuO ( s ) →2 Cu2 O ( s ) +O2 (g)

Dry hydrogen passed over heated black copper (II) oxide reduces it to the
brown metallic copper.
CuO ( s )+ H 2 ( g ) →Cu ( s ) + H 2 O ( l )

Copper (II) oxide is a basic oxide which reacts with warm dilute acids to form
respective.
CuO ( s )+ H 2 S O4 ( aq ) → Cu SO4 ( aq )+ H 2 O ( l )
CuO ( s )+ 2 HCl ( aq ) → CuCl 2 ( aq ) + H 2 O ( l )
CuO ( s )+ 2 HN O3 ( aq ) → Cu ( NO3 )2 ( aq )+ H 2 O ( l )

(b) Copper (II) hydroxide (Cu ( OH )2:

Copper (II) hydroxide is precipitated as a blue and basic hydroxide on
addition of a solution of an alkali to an aqueous solution containing copper
(II) ions.
−¿(aq)→ Cu (OH )2 (s )¿

Cu2+¿ (aq )+2 OH ¿

(blue ppt)
The ppt dissolves in excess ammonia to form a deep blue solution containing
tetrammine copper (II) complex ions.
−¿(aq) ¿
( aq ) +2 OH ¿
Cu ( OH )2 ( s ) +4 NH 3 ( aq ) → Cu ( NH 3 )2+¿
4

(c) Copper (II) sulphide: (CuS )

Copper (II) sulphide is a black solid which is prepared by bubbling
hydrogen in a solution containing copper (II) ions.
+ ¿(aq)¿

Cu2+¿ (aq )+H 2 S ( g ) →CuS ( s ) +2 H ¿

Exercise:
1. State what would be observed and write an ionic equation for the
reaction that takes place when;
(a) Aqueous copper (II) sulphate is added to a solution of
1
potassium iodide. (2 )
2
2. A sample of a hydrated double salt, Cu(NH 4 )x ( SO 4 )2 .6 H 2 O, was boiled with
an excess of sodium hydroxide. Ammonia was given off. The ammonia
produced was absorbed in 40.0cm3 cm3 of 0.400 mol cm3 hydrochloric acid.
The resulting solution required 25 cm3 of 0.12 mol dm−3 sodium hydroxide to
neutralise the excess acid.
(a) Write the ionic equation for the reaction between ammonium ions and
hydroxide ions. [1]
3
(b) (i) Calculate the amount, in moles, of hydrochloric acid in 40.0 cm cm3 of
0.400 mol cm3 dm−3solution. [1]
(ii) Calculate the amount, in moles, of sodium hydroxide needed to
neutralise the excess acid. This will be equal to the amount of hydrochloric
acid left in excess.
[1]
(iii) Calculate the amount, in moles, of hydrochloric acid that reacted with
ammonia. [1]
(iv) Calculate the amount, in moles, of ammonium ions in the sample of the
double salt. [1]
(v) The sample contained 0.413 g of copper. Use this information and your
answer to (iv) to calculate the value of x in Cu(NH 4 )x ( SO 4 )2 .6 H 2 O. [2]
(vi) Calculate the Mr of Cu(NH 4 )x ( SO 4 )2 .6 H 2 O.

Inner Transition Elements

The f-block elements are known as inner transition elements because they
involve the filling for inner sub-shells (4f or 5f)
a. Lanthanides:
It consists of elements that follows lanthanum and involve the filling of 4
subshell
Electronic Configuration : [Xe] 4fn+1 5d° 6s2 or [Xe] 4fn 5d1 6s2
Oxidation State: +3, +2 and +4.
Colouration: Many of the lanthanides ions are coloured in solid state as well
as in solutions. The colour is due to the f-f transition since they have partly
filled f-orbitals.
Lanthanide Contraction: The steady decrease in the size of lanthanide
ions (M3+) with the increase in atomic no. is called lanthanide contraction.
Causes: As we move down the group from left to right in a lanthanide
series, the atomic no. increases and for every proton in the nucleus the extra
electron goes to 4f orbital. The 4f orbital is too diffused to shield the nucleus
effectively, thus there is a gradual increase in the effective nuclear charge
experienced by the outer electrons. Consequently , the attraction of the
nucleus for the electrons in the outermost shell increases with the increase
of atomic number, thus size decreases.
Consequence of Lanthanide Contraction:
Separation of Lanthanides: Due to the similar sizes of the lanthanides, it
is difficult to separate them but due to lanthanide contraction their
properties slightly vary (such as ability to form complexes). The variation in
the properties is utilized to separate them.
Basic Strength of Hydroxide: Due to the lanthanide contraction, size of
M3+ ions decreases and there is increase in covalent character in M–OH and
hence basic character decreases.
Similarity of second and third transition series: The atomic radii of
second row transition elements are almost similar to those of the third row
transition elements because the increase in size on moving down the group
from second to third transition elements is cancelled by the decrease in size
due to the lanthanide contraction.

b. Actinides:
It consists of elements that follow Actinium and involve the filling of 5f
subshell.
These are radioactive substances.
7s2 is stable configuration for actinides.
Show +3,+4,+5,+6 & +7 oxidation state.
Lower ionization enthalpies than lanthinoids.

Revision Notes on Coordination Compounds

Revision Notes on Environmental Chemistry:

Components of Environment:
 Atmosphere: This comprises a blanket of gaseous layer around earth.
 Hydrosphere: This comprises about 96% of earth’s surface & includes all
sources of water like oceans rivers lakes, glaciers, ground water etc.
 Lithosphere: It refers to earth’s solid crust containing the outer mineral
cover. It comprises soil, minerals, organic matter etc.
 Biosphere: It refers to the domain of living organism in covalent with
atmosphere hydrosphere as well as lithosphere.
Environmental Pollution :
Process of contamination of the environment with harmful wastes arising
mainly from human activities.
 Pollutant: Any substance or species produced either by a natural source
or by human activity, which produces adverse effect on the environment.
 Contaminant: A substance which does not occurs in nature but is
introduced by human activity into the atmosphere affecting its
composition.
 Source: The site from which the pollution or contaminants originate.
 Sink: The material or medium which consumes or interacts with a long
lived pollutant is called sink.
 Receptor : Anything that is affected by the pollutants.
 Threshold limit value (TLV) : This indicates the permissible limit of a
pollutant in atmosphere to which a healthy worker is exposed during hours
a day or 40 hours a week for life time without any adverse effects. TLV are
determined by experimentation on animals, by use of medical knowledge,
epidemiology surveys & environmental studies.
Tropospheric pollution or Air pollution:
It is the atmosphere condition in which the presence of certain
concentration produce harmful effects on man and his environment. These
substances include:
(i) Gases such as oxides of sulphur, CO, oxide of N 2 and hydrocarbons
(ii) Particulate matter such as dust, smoke, fumes etc.
(iii) Radioactive material & many others.
Primary pollutants : These are the pollutants which are emitted directly
from the sources. Some examples are:
Particulate Matter : Such as ash, smoke, dust, fumes etc.
Inorganic gases : Such as sulphur dioxide, carbon monoxide etc.
Secondary PollutantsThese are the pollutants which are formed in the
atmosphere by chemical interaction among primary pollutants & normal
atmospheric constituents. Some examples are sulphur trioxide, nitrogen
dioxide, ozone, aldehyde, ketones, various sulphate & nitrate salts
Pollutant Source Sink Effect
Carbon (a) Incomplete Hydroxyl & Carbon
monoxide combustion of perhydroxyl radicals,monoxide is
(CO) carbonaceous atomic oxygen & poisonous as it
matter, automobile ozone help in the combines with
engines & also in oxidation ofhemoglobin of
defective furnaces, atmospheric CO into red blood cells
Incomplete CO2 . about 300 times
combustion of faster than O2,
fossil fuels, Soil is major sink for thus forming
agricultural , slash carboxyl
 matter and other CO. Some of the hemoglobin.
carbon microorganism present
in soil removes carbon
2C + O2 → 2CO
monoxide from air. This decreases
the transport of
(b) Dissociation of oxygen to the
carbon dioxide. body organs &
2CO2 2CO + cells.
O2
(c) Reaction of
carbon dioxide
with carbon
containing
compounds at high
temperature.
CO2 + C 2CO
Carbon It is released Ocean is a main sink CO2 causes
dioxide mainly into the for CO2. narcotic effect,
(CO2) atmosphere by the stimulation of
combustion of respiratory
fossil fuels (coal, center & leads to
oil etc) in factories Green plants for photo asphyxiation.
& also at homes. synthesis. The increasing
CO2 is also concentration of
produced by CO2 also changes
biological decay of climatic
plants conditions
especially by
raising the
general
temperature.

Oxides of Volcanic eruptions It causes cough,

sulphur (natural activity) & shortness of
(SOx) also through breath & spasm
combustion of of larynx, acute
sulphur bearing irritation to the
fuels such as coal membrane of
 & oil (human gas resulting
activity). tears & reduces
hearing ability.
This pollutant is
also produced SO2 irritates the
during roasting & respiratory
smelting of system of
sulphide ores animals &
(human activity) human, produces
leaf injuries
(called necrotic
A part of bloating) to
SO3 undergoes board leaved
photolytic & plants & gases. It
catalytic oxidation also causes
to form SO3. The deterioration of
SO2, so formed fabric (cotton,
gets converted to rayon) paper &
H 2 SO4 in the
leather.
presence of
moisture. This acid
comes down from
the atmosphere in
the form of
sulphuric acid rain.

Oxides of NO 2 is produced in Many natural (i) NO is

Nitrogen small amounts by processes act as sink biologically less
(NOx) microbiological for oxides of nitrogen. active & less
processes in soil. These oxides are toxic than NO 2.
However inherently unstable & Like CO it binds
significant amount decompose to N 2 & O2 hemoglobin &
of NO & NO 2 are after some time. decreases
emitted in to the Therefore, the oxygen transport
atmosphere by concentration of efficiency of
natural activity. nitrogen oxides in the blood.
atmosphere tends to (ii) Inhaling of
remains low. nitrogen oxides
by human results
 in pulmonary
edema &
hemorrhage.
(iii) The oxides
of nitrogen
cause damage to
plants. Exposure
of plants to
NOx causes leaf
spotting & break
down of plant
tissues.
(iv) The sunlight
reacts with NO 2
to produce
highly active
oxygen atoms.

Particulate matter:
 Soot: produced by incomplete combustion of carbonaceous fossils fuels
such as coal, fuel oil, natural gas, wood etc in insufficient supply of
oxygen.
 Metal particles: These are released by various metal finishing operation.
The micro particles of toxic metal & SO2 gas present in the polluted
atmosphere get absorbed on the particles rendering them highly toxic.
 Metal oxides : They are generated by combustion of fuels containing
metallic compounds.
 Lead salts: Their source is lead tetraethyl (Pb(C 2H5)4) which is added to
gasoline to improve its antiknock property. In order to avoid deposition of
PbO suitable amounts of C2H4Cl2 & C2H4Br2 are added to gasoline along
with Pb(C2H5)4.
 Fly ash: It originates from the combustion of high ash fossil. It contains
partially burnt particles of the fuels.
 Asbestos dust: It originates from industrial units manufacturing asbestos
sheets, gaskets ropes etc. Asbestos flowing & asbestos insulations also
contribute towards asbestos dust in the atmosphere.
 Solid Hydrocarbons: These are emitted from petroleum refineries &
comprise of paraffins, olefins & aromatics.
 Dust Particulates: Originate from natural, domestic, industrial or
agricultural sources. These are thrown into atmosphere by volcanic
eruptions, blowing of dust by wind, mining operations etc.
 Acid mist : Sulphuric acid mist is produced when SO 3 present in the
atmosphere comes in contact with moisture. Nitric acid mist is produced
when oxides of nitrogen, viz, NO & NO 2, undergo the series of reactions in
the atmosphere.
Harmful effects of particulates
 Effect on human beings: Affect the human respiratory system & cause
several respiratory illnesses. The particles with small size are more
harmful in this context. The particulates in fact, become the carriers of the
toxic substances from the atmosphere to the human & cause big health
hazards.
 Effect on visibility: Particulates in the atmosphere cause scattering &
absorption of sunlight & reduce the visibility.
 Effect on Materials : The adverse effect of particulates on materials
include corrosion of metals (when the atmosphere is humid), erosion &
soiling of building, sculptures & painted surfaces & soiling of clothes &
draperies.
Stratospherical Pollution: (ozone layer & its depletion):
Role of Ozone Layer: protecting earth from the UV radiation coming from
the sun.
Depletion of Ozone Layer : The equilibrium between formation &
destruction of ozone has been upset by influx of several substances into the
atmosphere which react with ozone to destroy it.
Effect of Depletion of Ozone layer: The influx of UV radiation reaching
the surface of earth would increase which would increase in risk to skin
cancer due to exposure to UV radiation, UV radiations also tend to damage
the immune system.
Acid Rain:
SO2, nitrogen oxides & acidic soots. Sulphurdioxide & nitrogen dioxide
interact with water vapours in presence of sunlight to form sulphuric acid &
nitric acid units.

Green House Effect & Global Warming:

The greenhouse gases (C O2,CH 4, O3, CFC’S) in the atmosphere form a thick
cover around the earth. About 75% of the solar energy reaching the earth is
absorbed by the earth surface. The IR radiations coming from sun are not
absorbed by atmospheric gases but Earth absorbs these IR radiations of
short wavelength. As a result of this the temperature of earth stands rising.
Eventually, earth starts emitting infrared radiations of longer wavelengths.
The partially radiated infrared radiations from the earth are absorbed by the
greenhouse gases. This results in excessive heating of Earth’s atmosphere.
Thus the greenhouse gases add to the heating of atmosphere. This causes
global warming. The atmosphere traps the sun’s heat near earth’s surface
and keeps it warm. The reemission of the earth’s energy absorbed by
CO2 and other greenhouse gases present near the earth’s surface and its
radiation back to the earth is called greenhouse effect.
Advantages of greenhouse effect :
 It is necessary for evaporation of water, formation of clouds, rainfall
etc.
 The warm atmosphere helps in rapid growth of plants, trees etc.
Harmful effects of greenhouse effect :
 High temperature of atmosphere may melt polar ice caps which are
likely to raise the level of sea thereby sinking most of the coastal areas
and causing large scale destruction.
 The high temperature may reduce crop product.
 The high temperature will reduce work efficiency of human being.
 Tropical rains and hurricane will become more frequent and also
stronger causing more devastation.
 The change in ocean temperature will adversely affect the warm life.

Water Pollution:
Pollutant Source

Microorganism Domestic sewage

Organic wastes Domestic sewage, animal waste, decaying animals,

plants and discharge from food processing factories

Plant nutrients Chemical fertilizers

Toxic heavy metals Industries and chemical factories

Sediments Erosion of soil by agriculture and strip mining

Pesticides Chemical used for killing insects, fungi & weeds

Radioactive Mining of Uranium containing minerals
substances

Heat Water used by industrial plants which is discharged

as hot water
Biochemical Oxygen Demand (BOD) : The measure of the total
contamination caused by compounds which can be oxidised in the presence
of microorganisms. The BOD is taken as a realistic measure of water quality –
clean water would have a BOD value of less than 5 ppm whereas highly
polluted river water could have a BOD value of 17 ppm or more.
Land Pollution :
Caused by pesticides and other chemicals which are added to the soil to
grow better crops.
Insecticides are the pesticides used to Control of insects by insecticides
helps to curb disease and protect crops. Organo chlorines are a group of
compounds which have been developed and used as insecticides. Examples:
DDT (dichlorodiphenyl trichloro ethane) organo chlorines are stable in the
environment, toxic to insects in small amounts, but much less go to humans,
and because they are organic compounds not very soluble in water. The
advantage of these insecticides is that, bring persistent
Fungicides are the pesticides used to check the growth of fungi. Fungi, are
plants without chlorophyll, they cannot use solar energy for preparing their
food. They live as saprophytes on decaying organic matter or as parasites
at the expense of living organisms. Hence they are considered to be a threat
to human interests
