12.

3 Applied Chemistry

Transition Elements

Objective:

By the end of this topic learners should be able to:

 Describe the occurrence, relative stability and colour of chromium aqueous ions and
compounds containing the metal in the +3 and +6 oxidation states.
 Explain uses of chromium and its compounds.
 Describe the use of dichromate (VI) as an oxidising agent.
 Describe the chromate (VI) to dichromate (VI) interconversion.
 Describe the occurrence, relative stability and colour of iron compounds.
 Describe the effect of pH and the cyanide ligand on stability of iron and its ions.
 Explain the biochemical importance of iron in haemoglobin and in cytochrome
 Analyse the rusting of iron and its prevention
 Distinguish between Fe2+and Fe3+ (aq) using Fe(CN)63- and SCN -, respectively.
 Describe the use of iron and its compounds.
 Describe the occurrence, production and purification of nickel from its sulphide ore
 Explain the use of nickel in alloys (e.g. alnico) and as a hydrogenation catalyst.
 Describe the occurrence and relative stability and colour of manganese ions and
compounds containing the metal in the +2, +4, +6 and +7 oxidation states.
Demonstrate the redox reactions involving MnO2, MnO42- and MnO-4
 Describe the occurrence, production and purification of copper,
 Describe the occurrence and relative stability of ions and compounds containing the
metal in the +1 and +2 oxidation states, including the disproportionation and
stabilisation of Cu+
 Describe the reaction of Cu2+ with I-
 Explain uses of copper and its compounds as in brass, bronze, other alloys, and in the
test for aldehydes.
 Describe the occurrence and extraction of platinum.
 Identify elements which occur together with platinum.
 Suggest the uses of platinum group metals.
 Describe the occurrence, relative stability and colour of cobalt ions and compounds
containing the metal in its +2 and +3 oxidation states,
 Explain the effect of ligands and/or temperature on the stability and geometry of cobalt
complexes, using as examples[Co(H2 O)6]2+ [CoCl4]2, and [Co(NH3)6]2+ [Co(NH3)6]3+
 Explain the uses of cobalt as in alloys, anhydrous cobalt (II) ions as a test for water and
its biochemical importance.
1. Chromium
Occurrence and Extraction of Chromium
 Chromium is almost never found in its elemental state in nature. Commonly it is found
in numerous ores, usually in the mineral chromite. Chromite is the complex of FeCr 2O3,
or iron chromium oxide. Chromium is also found in other minerals, including
magnesiochromite (MgCr2O4).
 Chromite is found in earth's mantle. South Africa and Zimbabwe hold about 90% of the
world's chromite reserves and resources. Through the refining processes, chromite
produces both ferrochromium and metallic chromium.
 Chromite, FeCr2O4, is the most commercially useful ore, and is extensively used for
extraction of chromium. Chromium is produced in two forms:
a. Ferrochrome by the reduction of chromite with coke in an electric arc furnace. A
low-carbon ferrochrome can be produced by using ferrosilicon instead of coke as the
reductant. This iron/chromium alloy is used directly as an additive to produce
chromium-steels which are "stainless" and hard.
b. Chromium metal by the reduction of Cr2O3. This is obtained by aerial oxidation of
chromite in molten alkali to give sodium chromate, Na2CrO4, which is leached out
with water, precipitated and then reduced to the Cr(III) oxide by carbon. The oxide
can be reduced by aluminium (aluminothermic process) or silicon:

i. C r 2 O3 +2 Al → 2 Cr+ A l 2 O3
ii. 2 C r 2 O3+ 3 Si → 4 Cr+3 SiO2

 Pure chromium has a blue-white colour. It is very brittle and corrosion resistant. It has
three common oxidation states: +2, +3, and +6. The metal ore (principally chromite,
FeCr2O4), is refined by heating in the presence of Si or Al.
Redox chemistry
 Its electronic configuration is [Ar] 3d5 4s1
 Chromium forms stable ions in three different oxidation states, +2, +3 and +6.
 In aqueous solutions, the ions formed are:
Table 12.3.1 showing oxidation states and their colour

Oxidation state +6 +3 +2
Colour Orange Green Blue
Ion Cr2O72- Cr3+ Cr2+

 θ
E values for the interconversion between these oxidation states are shown below
Redox potential and chemistry of chromium
Table 12.3.2 showing redox potential and chemistry of chromium

Reaction of chromium system E /V

θ
Reaction of other systems
1

1 +1.33
3+¿ ( aq ) +3 H O( l)¿
2 2
−¿ ⇌Cr ¿
+¿ (aq ) +3 e ¿
2−¿ ( aq ) + 7 H ¿
Cr O
2 2 7

1
0.00 −¿⇌ H 2 ( g)¿
+¿ ( aq ) +e 2
¿
H

−¿ ¿

-0.13
2−¿ (aq ) 4 H O ( l) +3 e ¿
−¿ ( aq ) ⇌Cr O4 2
¿
3+¿ ( aq ) +8 OH ¿
Cr

2+¿ (aq )¿

-0.41
−¿⇌ Cr ¿

Cr 3+¿ (aq )+e ¿

−¿⇌Cr ( s)¿

Cr 3+¿ (aq )+3 e ¿

-0.74
−¿⇌Cr (s )¿

Cr 2+¿ (aq )+2 e ¿

-0.91

 θ
E values can be used to predict how chromium metal would react with hydrogen under
standard conditions.
 The actual formula of the +2 and +3 complex ions depends on the acid used (Cl - and
SO42- will also behave as ligands).
  In aqueous alkaline solutions, the ions formed are:
Colour and oxidation states of Chromium
Table 12.3.3 colour and oxidation states of Chromium

Oxidation state +6 +3

Colour Orange Green

Ion CrO42- Cr(OH)63-

 The +6 chromium complexes can be readily interconverted using acid and alkali:

2CrO42-+ 2H+⇌ Cr2O72-+ H2O

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

a) In acidic solution

 All chromium (VI) compounds can be reduced to the +3 and then the +2 oxidation state
by strong reducing agents such as zinc in acid solution.
 The chromium is first reduced to the +3 oxidation state:

Cr2O72-(aq) + 14H+(aq) + 6e ⇌ 2Cr3+(aq) + 7H2O(l)

Zn(s) ⇌ Zn2+(aq) + 2e

Overall : Cr2O72-(aq) + 14H+(aq) + 3Zn(s) ⇌ 2Cr3+(aq) + 7H2O(l) + 3Zn2+(aq)

 It is then further reduced:

Cr3+(aq) + e ⇌ Cr2+(aq)

Zn(s) ⇌ Zn2+(aq) + 2e

Overall: Zn(s) + 2Cr3+(aq) ⇌ Zn2+(aq) + 2Cr2+(aq)

 The colour change observed on adding zinc in acid solution to dichromate ions is
orange (Cr2O72-) to green (Cr3+) to blue (Cr2+).
 Cr2+is unstable and is easily oxidised back to Cr3+
 Other, milder reducing agents will reduce the +6 oxidation state to +3 but no further.
 Fe2+ is an example:

Fe2+(aq) ⇌ Fe3+(aq) + e-

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

 This reaction can be used in titrations to determine the concentration of Fe 2+ ions in a

sample.

b) In alkaline solution

 In alkaline solution, it is possible to oxidise the +3 oxidation state to the +6 oxidation

state.
 The chromium ion forms the [Cr(OH)6]3- complex in alkaline conditions. This complex can
be oxidised to the +6 oxidation state by adding H2O2. Hydrogen peroxide, which is a
reducing agent in acidic solution, is an oxidising agent in alkaline solution.

[Cr(OH)6]3-(aq) + 2OH-(aq) ⇌ CrO42-(aq) + 4H2O(l) + 3e-

H2O2(aq) + 2e-⇌ 2OH-(aq)

2[Cr(OH)6]3-(aq) + 3H2O2(aq) ⇌ 2CrO42-(aq) + 8H2O(l) + 2OH-(aq)

 The green [Cr(OH)6]3- ion is oxidised to the yellow CrO42- ion in alkaline solution.
 The relative tendency of species to undergo oxidation and reduction often depends on
the pH of the solution. The interconversion of the chromium (III) and chromium (VI)
oxidation states is an important example:
 Figure 12.3.1 Summary of variation of oxidation states
 Remember, oxidation is an increase in oxidation number and reduction is a decrease in
oxidation number.
 In general, oxidation is favoured by alkaline conditions and reduction is favoured by
acidic conditions.

Uses of Chromium
 The main use of the chromium metal is in the production of non-ferrous alloys, the use
of pure chromium being limited because of its low ductility at ordinary temperatures.
 Alternatively, the Cr2O3 can be dissolved in sulphuric acid to give the electrolyte used to
produce the ubiquitous chromium-plating which is at once both protective and
decorative.
 The sodium chromate produced in the isolation of chromium is itself the basis for the
manufacture of all industrially important chromium chemicals.
 More than half the production of chromium goes into metallic products, and about
another third is used in refractories. It is an ingredient in several important catalysts.
 The chief use of chromium is to form alloys with iron, nickel or cobalt. The addition of
chromium imparts hardness, strength, and corrosion resistance to the alloy. In the
stainless steels, chromium makes up 10% or more of the final composition.
  Because of its hardness, an alloy of chromium, cobalt and tungsten is used for high-
speed metal-cutting tools.
 When deposited electrolytically, chromium provides a hard, corrosion-resistant, lustrous
finish. For this reason it is widely used as body trim on automobiles and other vehicles.
 The extensive use of chromite as a refractory is based on its high melting point, its
moderate thermal expansion and the stability of its crystalline structure.

2. Iron
Occurrence and Extraction of Iron

 Iron is a metal in the first transition series and forms much of the Earth’s outer and inner
core.
 It constitutes about 6% of the earth’s crust. Its main ores are:
i. Haematite, Fe2O3
ii. Magnetite, Fe3O4
iii. Siderite, FeCO3
iv. Limonite, 2Fe2O3.3H2O
 Iron is mined as oxides, haematite (Fe2O3) and magnetite (Fe3O4), and as iron pyrites
(FeS2).
 Iron is obtained by the reduction of the mined oxides by carbon monoxide.
θ −1
Fe2 O3 ( s ) +3 CO ( g ) → 2 Fe ( s )+3 CO 2 ( g ) ; ∆ H =−27 kJ mol

 The process takes place in a blast furnace in which hot air is blown into the bottom and
iron ore, coke and limestone are fed from the top.
 Figure 12.3.2 Blast furnace, showing reactions which occur in different temperature
zones.At the bottom of the furnace, coke is oxidised exothermically to produce carbon
dioxide
θ −1
C ( s )+O2 ( g ) →CO 2 ( g ) ; ∆ H =−391 kJ mol

 Higher up, carbon dioxide reacts with coke to form carbon monoxide. The reaction is
endothermic
θ −1
CO 2 ( g ) +C ( s ) → 2CO ( g ) ; ∆ H =+173 kJ mol

 Limestone fed from the top of the furnace dissociates to form calcium oxide and carbon
dioxide.
θ −1
CaCO 3 ( s ) ⇌ CaO ( s )+CO 2 ( g ) ; ∆ H =+178 kJ mol
 Calcium oxide combines with silicon(IV) oxide and aluminium oxide (impurities), to form
a molten slag of calcium silicate (IV) and calcium aluminate (III) which falls down the
stack.
CaO ( s )+ SiO 2 ( s ) →CaSiO3 ( l )
CaO ( s )+ Al 2 O3 ( s ) →CaAl 2 O4 ( l )

 The blast furnace runs continuously. Iron and slag are tapped off at the bottom of the
furnace.
 The iron obtained from the blast iron is known as cast iron.

Cast Iron

 Iron leaving the blast furnace is cast (poured and hardened) into solid blocks called pigs.
Pig or cast iron contains approximately 4% carbon.
 The presence of carbon lowers the melting temperature of iron, increases its hardness
and decreases its ductility.
 If pig iron is processed (purified) to remove carbon dioxide, malleable iron is produced.
It is called wrought iron; it can easily be forged and welded.

Steel

 Most of the iron produced by blast furnaces is made into steel.

 However, the properties of a variety of steel differ due to the presence of small,
controlled proportions of elements such as carbon and other transition metals.
 To make steel, impurities in cast iron (carbon, phosphorous and sulphur) are removed
by converting them into their oxides. Gaseous oxides escape and other oxides are
removed by a combination with calcium oxide to form slag.

Biological importance of iron

  It plays a central role in almost all living cells as a cofactor.
 It is a component of haemoglobin and myoglobin.
 Iron is involved in the electron-transport chain.

Iron in haemoglobin

 Iron is contained in haemoglobin. Haemoglobin is responsible for carrying oxygen from

the lungs to the cells of the body.
 The molecule consists of a central Fe2+ ion with a coordination number of six. This
complex is called ‘haem’.
 Four of the coordination sites are taken up by a tetradentate ligand called porphyrin,
the 5th coordination site is taken up by a nitrogen atom acting as a ligand. The nitrogen
atom is part of a complex ion called globin.
 The sixth coordination site can accept oxygen as a ligand. The Fe2+-O2 bond is weak,
allowing the oxygen molecule to be given up easily when it reaches areas of low oxygen
concentration.

Figure 12.3.3 the haem complex

Chemistry of Iron
 Tests for iron ions

 Fe2+ and Fe3+ exist in aqueous solution as hexaaqua ions, pale green [Fe(H2O)6]2+ and pale
brown [Fe(H2O)6]3+. However dilute solutions are difficult to tell apart.
 To distinguish between dilute solutions of [Fe(H2O)6]2+ and [Fe(H2O)6]3+, dilute alkali is
added. It precipitates the hydroxides of the ions which have different colours.

−¿ ( aq )⟶ Fe( OH )2 ( s )+ 6H 2 O ( l )¿
2+¿ ( aq ) +2 OH ¿
[ Fe ( H 2 O )6 ]
Iron(II) hydroxide (green)

−¿ ( aq ) ⟶ Fe (OH )3 (s )+ 6 H2 O(l) ¿
3+ ¿ ( aq ) +3 OH ¿
[ Fe ( H 2 O )6 ]
Iron(III) hydroxide (brown)

 Fe2+ and Fe3+ ions are also distinguished using the following tests:
 To test for Fe3+, Addition of potassium thiocyanate (K+ + SCN-) to [Fe(H2O)6]3+ to produce
pentaaquathiocyanate iron(III) ion.

−¿ (aq ) ⟶ ¿¿¿
3+ ¿ ( aq ) +SCN ¿
[ Fe ( H 2 O )6 ]
Pentaaquathiocynate iron (III) ion (blood red)
1. To test Fe2+, Addition of potassium hexacynaoferrate (III) to form prussian blue
which has a deep blue colour.
3−¿ (aq )⟶ ¿¿ ¿
2+¿ ( aq ) + [ Fe ( CN ) 6]
[ Fe ( H 2 O )6 ] ¿

Prussian blue
Acidity of aqueous iron ions
 Solutions of Fe2+ are not significantly acidic.
 Solutions of Fe3+ (pKa =2.2) are considerably acidic. This is because the Fe3+ ion is highly
charged than the Fe2+, making it strongly polarising.
 In solutions containing the hexaaqua ion, [Fe(H2O)6]3+, the iron ion strongly attracts
electrons from the oxygen atoms of the water ligands thus weakening the O-H bonds in
the water molecules.
 The water ligands then readily donate the H+ ions to the solvent water molecules to
form H3O+, making the solution more acidic.

Figure 12.3.4 Rusting of Iron & Rust Prevention

Figure 12.3.5 Rusting metallic pole

 Rust is hydrated iron(III) oxide (Fe2O3.xH2O) which is formed by the conversion of

metallic iron in the presence of oxygen and water.
 Rusting is a redox reaction.
 The chemical equation for its formation is:
4 Fe(OH )2 +O2 + x H 2 O⟶ 2 Fe2 O3 .(x + 4)H 2 O
 Rusting in iron occurs when a cell is setup (galvanic cell).
 In an iron surface is covered with water which contains dissolved oxygen, the following
reactions take place:
−¿ ¿
2+¿ ( aq ) + 2e ¿
Fe ( s ) ⟶ Fe
1 −¿ ⟶ 2OH −¿( aq)¿
¿
O ( aq ) + H 2 O+ 2 e
2 2

 The electrons produced by the first reaction flow through the iron and take part in the
second reaction.
 Fe2+(aq) and OH-(aq) ions diffuse away through the solution and where they meet, they
react to give iron (II) hydroxide:
−¿ ( aq ) ⟶ Fe (OH )2 ( s)¿

Fe2 +¿ (aq )+2 OH ¿

 Fe ( OH )2 is then oxidised by dissolved oxygen to iron(III) hydroxide which forms

hydrated iron(III) oxide(rust):

1
2 Fe(OH )2 + H 2 O+ O2 ⟶ Fe 2 O3 +3 H 2 O
2

 Rusting only takes place in the presence of air and water and is accelerated by dissolved
ionic salts which enhance the electrical conductivity of the water.

Factors Affecting Rusting

 Moisture: Iron exposed to rains is the most common reason.

 Acid: It accelerates rusting. When exposed to acid rains, iron rusts faster. On the other
hand, alkalis inhibit rusting.
 Salt: Iron tends to rust faster in sea, due to the presence of salt.
 Impurity: Pure iron rusts slower than the iron mass which contains a mixture of metals.

Preventive Measures

 Measures used to prevent rusting are:

 i. Coating and painting: Iron surface is often painted with the coatings of varnish or
paint to isolate it from the environment. Window grills, bodies of automobiles, iron
bridges and rails are painted regularly to protect them from rusting.
ii. Applying a layer of grease: Grease or a layer of oil is also applied to iron surfaces,
primarily on machines and industry tools. This serves dual purpose of a lubricant
reducing friction as well as rust prevention.
iii. Galvanisation: It is a process of depositing a thin layer of a non-reactive metal like
zinc on the surface of iron. This metallic layer prevents the iron to come in contact
with air and moisture. Buckets, drums, roofs, pipes etc. are galvanized to prevent
rusting.

Figure 12.3.6 Galvanisation of Iron

Uses of Iron

 Iron is usually made into steel, which is essential in the construction of buildings,
automobiles and ships. Cosmetics, paint, fertilizers, paper, glass and plastic also contain
iron.
 Figure 12.3.7 Steel beams of a bridge

 Traces of this element are present in the bloodstream of animals and humans as part of
the haemoglobin molecule.

3. Vanadium
 Vanadium is has the same colour for each of the ions in their different oxidation states:
 Vanadium (II) , V2+, is purple
 Vanadium(III), V3+, is green
 Oxovanadium(IV), VO 2+ , is blue - (this is an oxidation number of 4+)
 Dioxovanadium(V) VO2+, is yellow - (this is an oxidation number of 5+)

Experiment 25.5.1

Aim: To illustrate the presence of different oxidation states for vanadium, and to show how it is
possible to change from one state to another.

Starting with a solution containing vanadium (V) in acid, powdered zinc is used as a reducing
agent. Colour changes indicate the formation of different oxidation states. Changes between
various oxidation states are shown by using a variety of oxidising and reducing agents.
Apparatus/Materials

100cm3conical flask, spatula, measuring cylinder(25cm3), safety gloves and spectacles,

ammonium polytrioxovanadate(V), Ammonium metavanadate(NH4VO3), dilute sulphuric acid
(1M H2SO4), concentrated sulphuric acid(H2SO4), test tubes, zinc dust(Zn), Bunsen burner,
tripod, gauze, test tube rack, filter funnel and paper, potassium manganate (VII) solution,
potassium permanganate (0.02M KMnO4), sodium sulphite (Na2SO3), potassium iodide solution
(0.05M KI), sodium thiosulphate solution (0.1M Na2S2O3)

Procedure

The table below assists in identifying the different oxidation states of vanadium.

Table 12.3.4 VO2+ VO+ V3+ V2+

Showing
different
oxidation states
and their colour
changesHydrate
d Ion
Colour yellow Blue Green Violet
Oxidation state 5 4 3 2
Name Dioxovanadium(V) Oxovanadium(IV) Vanadium(III) Vanadium(II)
 The VO3- ion in the ammonium salt is converted to VO2+ by acid:
+¿ ( aq ) +H O (l) ¿
2
+ ¿ ( aq ) ⇌VO 2 ¿
−¿ ( aq ) +2 H ¿
VO3

1. Place 0.25g of ammonium trioxovanadate(V) in a conical flask and add about 25cm 3
of dilute sulphuric acid.
2. Carefully add about 5cm3 of concentrated sulphuric acid and swirl the flask until a
clear yellow solution is obtained.
3. Pour 2cm3 of the obtained vanadium (V) solution into each of two test tubes.
4. Add 1g of zinc dust to the conical flask. Swirl the flask at intervals and record any
observed colour changes in a copy of table 1.
5. After the solution becomes violet, filter about 3cm3 into each of the three test-tubes.
 6. Add excess of acidified potassium manganate (VII) solution to one of the test tubes,
shaking after each addition, until further change is observed.
7. Keep the other test-tubes.
8. Add a little sodium sulphite to the test-tube containing vanadium(V). If cloudy, filter.
Boil carefully in a fume cupboard to remove excess sulphur dioxide and add about
the same volume of vanadium (II) solution, record the observations.
9. Add 2cm3 of potassium iodide solution to the test tube containing vanadium (V) and
mix. Then add 2cm3 of sodium of sodium thiosulphate solution. Record the
observations.

Expected Observations and Results

Table 12.3.5 showing expected results

Test Expected Observations Reaction

Ammonium vanadate + White solid dissolves to a yellow VO3-⟶VO2+
Acid solution.
2+ ¿ ¿

Vanadium (V) + zinc Zinc effervesces and the yellow solution

3+¿ ⟶V ¿
2+¿⟶ V ¿

V O2+¿⟶ VO ¿

becomes green, blue, green again and

eventually turned violet.
+ ¿¿

Vanadium (II) + manganate Violet solution becomes green, blue,

2+ ¿→ VO ¿
3+¿ →VO 2
¿
2+ ¿→V ¿
V
(VII) green, yellow and eventually turns pink
2+ ¿¿
Vanadium (V) + sulphite Yellow solution becomes blue. On VO2+¿→ VO ¿

addition of Vanadium(II), the mixture

+ Vanadium (II)
3+ ¿ ¿
2+ ¿→V ¿
2 +¿+V ¿
turns green. VO
2+ ¿¿
Vanadium (V) + iodide + Yellow solution becomes muddy brown. VO2+¿→ VO ¿

Thiosulphate On addition of thiosulphate it gives a

clear blue solution
3+¿ ¿
Vanadium (II) + Violet solution becomes green. V 2+ ¿→V ¿

concentrated sulphuric acid

4. Nickel

Occurrence and extraction

 It is a silver white crystalline metal that occurs combined with other elements in ores.
Two important groups of ores are:
i. Laterites: oxide or silicate ores such as garnierite.
ii. Sulphides: these are ores such as pentlandite, which contain about 1.5%, nickel
associated with copper, cobalt and other metals. Canada is the world's leading
nickel producer and the Sudbury Basin of Ontario contains one of the largest nickel
deposits in the world.
 Roasting the sulphide ores gives the oxide which is used in steel making or converted
into metallic nickel by reduction with carbon.
 The ‘’Mond process’’ involves the conversion of nickel oxides to pure metal.
i. In the first step of the process, nickel oxide is reacted with water gas, a mixture
of H2 and CO, at atmospheric pressure and a temperature of 50 °C. The oxide is
thus reduced to impure nickel. Reaction of this impure material with residual
carbon monoxide gives the toxic and volatile compound, nickel tetracarbonyl,
Ni(CO)4. This compound decomposes on heating to about 230 °C to give pure
nickel metal and CO, which can then be recycled. The actual temperatures and
pressures used in this process may vary slightly from one processing plant to the
next. However the basic process as outlined is common to all.
ii. The process can be summarized as follows:
 Redox chemistry

Reactions of nickel E /V
θ
Reaction of other systems
Ni(OH)3(s) + e-⇌ Ni(OH)2(s) + OH-(aq) +0.48
0.00 1
H+(aq) + e-⇌ H2(g)
2
Ni2+(aq) +2e-⇌ Ni(s) -0.25
Ni(CN)42-(aq) + e-⇌ [Ni(CN)3]2-(aq) + CN-(aq) -0.40
 The chemistry of nickel is dominated by the +2 oxidation state with many nickel(II)
complexes known. Ni(II) is the only stable oxidation state of nickel in aqueous solution.

Table 12.3.6 showing redox potentials

 Nickel dissolves in dilute acids, liberating hydrogen.

 The reaction; Ni(OH)3(s) + e-⇌ Ni(OH)2(s) + OH-(aq), occurs in the nickel-cadmium
rechargeable battery.

Nickel complexes

Table 12.3.7 showing nickel complexes

Complex Geometry Colour

¿¿ octahedral Green

¿¿ Octahedral Blue

[¿(CN )6 ]
2−¿¿
Square planar Yellow

[¿ Cl4 ]
2−¿¿
Tetrahedral Blue
 Properties

Figure 12.3.8 an aqueous solution containing the Ni 2+ ion

 Nickel is a hard silver white metal, which occurs as cubic crystals. It is malleable, ductile
and has superior strength and corrosion resistance.
The metal is a fair conductor of heat and electricity and exhibits magnetic properties
below 345°C. Five isotopes of nickel are known.
 In its metallic form nickel is chemically unreactive. It is insoluble in cold and hot 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 and sulphuric
acids.

Uses of Nickel and its Compounds

 The primary use of nickel is in the preparation of alloys such as stainless steel, which
accounts for approximately 67% of all nickel used in manufacture. The greatest
application of stainless steel is in the manufacturing of kitchen sinks but it has numerous
other uses as well.
 An alloy of nickel and copper for example is a component of the tubing used in the
desalination of sea water. Nickel steel is used in the manufacture of armour plates and
 burglar proof vaults. Nickel alloys are especially valued for their strength, resistance to
corrosion and in the case of stainless steel for example, aesthetic value.
 Electroplating is another major use of the metal. Nickel plating is used in protective
coating of other metals. In wire form, nickel is used in pins, staples, jewellery and
surgical wire. Finely divided nickel catalyses the hydrogenation of vegetable oils.
 Nickel is also used in the colouring of glass to which it gives a green hue.

5. Copper

Occurrence

 Copper occurs both in combined state and free state with a low crustal abundance of
0.007%. It also contains many ores.

 The important ores of copper are copper pyrites, CuFeS2, Cuprite Cu2O Cuprite and
CuCO3.Cu (OH) 2 which is known as Malachite.

 Copper in Zimbabwe is mined at Mhangura.

Extraction

 Copper is extracted from a chief ore known as copper pyrites.

 The extraction of copper from sulphide ores, not containing other metals is achieved
from copper pyrites. It relatively straightforward roasting in air process

 The roasting of the sulphide ores causes partial oxidation to the oxide, which then
undergoes an internal redox reaction to give "blister" copper.

2 Cu2 S+3 O2 → 2 Cu2 O+ S O2

2 Cu2 O+Cu2 → 6 Cu+ SO 2

 Further purification of blister copper is done by an electrolysis treatment.

  The cathodic copper that is formed is >99.99% pure.

Refining

 Blister copper consists of about 2% of impurities consisting of silver, Gold, Zinc and
Nickel.

 Blister copper is purified by electrolytic method.

 A block of impure copper is made to be the anode, a strip of pure copper is made the
cathode and the electrolyte is CuSO4 containing dilute H2SO4.

 On passing current, impure copper dissolves and equivalent amount of pure copper is
deposited at cathode.

 Impurities are collected below anode as sludge.

Figure 12.3.9showing purification of blister copper by electrolysis

 When the electricity is passed through the electrolyte, the copper ions on the anode
dissolve into the solution, and are attracted to the cathode.
  At the cathode they pick up 2 electrons and become copper metal.

Anode reaction
−¿¿
2+¿+2 e ¿
Cu →Cu

Cathode reaction
−¿→ Cu¿
¿
Cu2+¿+2 e

Chemical properties and uses

 Copper shows two important oxidation numbers, +1 in copper (l) compounds

d10configuration and +2 in copper (Il) compounds d9 configuration.

 Most copper (l) compounds are white and diamagnetic in the solid state as expected
from the d10 configuration.

 Hydrated copper (ll) salts are paramagnetic they are usually blue-green in the solid
state. and blue in dilute aqueous solution, the blue colour being attributed to the ion ¿
 The above values show that copper (I) salts are unstable in aqueous solution: Cu + can
undergo a disproportionation reaction reactions 2 and 5 in the table in which one ion
oxidises another as shown below:
Reaction of copper systems E0/V Reactions of other systems

+1.23 1 +¿+2 e −¿⇋ H 2 O ¿

¿
O +2 H
2 2
¿
+¿+e ⇋ Cu ¿ +0.52
Cu

+0.40 1 −¿⇋2 O H −¿¿

¿
O2 +2 H 2 O+2 e
2
−¿−⇋Cu¿

Cu2+¿+2 e ¿ +0.34

+¿ ¿
−¿−⇋C u ¿

Cu2+¿+e ¿ +0.15

1
0.00 −¿2 ⇋ H 2 ¿
+¿+e 2
¿
H

2+ ¿( s) ¿

Cu+¿ ( aq) ⇋ Cu(s)+C u ¿

 Adding white Cu2SO4 to water produces solution a blue solution not the expected
colourless solution and a red-brown precipitate of copper metal.

 A disproportionation is defined as a reaction in which a reactive species oxidises and

reduces itself.
The equilibrium constant for the disproportionation of Cu+ reaction is

K c =¿ ¿

 A comparison of the E0 values quoted suggests that Cu+ might be stabilised with respect
to Cu2+and Cu solid if the concentration or Cu+ could be reduced to a value low that the
order of the values previously quoted became reversed.

 In equilibrium terms, this means that Cu+ ions are removed from the disproportionation
equilibrium mixture, causing Cu(s) to reduce Cu2+ thereby producing more Cu+.
  Copper (I) can be stabilised by forming complexes from suitable ligands such as
copper(I) chloride which dissolves in concentrated hydrochloric acid to form the stable
dichlorocuprate (I) complex ion.

The colour of copper (I) compounds

 Copper (I) compounds and copper (I) complex ions do not show the same variety of
colours observed in copper (II) compounds and complex ions.

 The lack of a variety of coloured compounds arises from the fundamental electronic
configuration of the Cu+ ion, which is [Ar] 3d10, giving a completely filled 3d sub–
shell identical to that of the zinc ion Zn2+ , which is colourless.

 There is no electrons that can be promoted to a higher level when the 3d sub–shell is
split when the central metal ion interacts with the ligands.

Reactions of copper (II) ions in solution

 The simplest ion that copper forms in solution is the typical blue hexaaquacopper (II) ion
[Cu (H2O)6]2+.

i. Hexaaquacopper (II) ions with Hydroxide Ions

 Hydroxide ions remove hydrogen ions from the water ligands attached to the copper
ion. Once a hydrogen ion has been removed from two of the water molecules.

 A complex with no charge is left which is known as a neutral complex.

 This is insoluble in water and a precipitate is formed which is blue in colour.

¿
 Figure 12.3.9showing reaction of hexaaquacopper (II) ions with Hydroxide Ion

ii. Hexaaquacopper (II) ions with ammonia solution

 The ammonia acts as both a base and a ligand.

 Hydrogen ions are pulled off the hexaaqua ion, exactly as in the hydroxide ion case to
give the same neutral complex.

 That precipitate dissolves if you add an excess of ammonia. The ammonia replaces
water as a ligand to give tetraamminediaquacopper(II) ions.

 Only 4 of the 6 water molecules are replaced.

Figure 12.3.10 showing ligand exchange

iii. Hexaaquacopper (II) ions with carbonate ions

  Reaction of hexaaquacopper (II) ions will react with a carbonate ion to yield copper
carbonate with a blue precipitate

Figure 12.3.11 showing CuCO3

iv. Ligand exchange reaction involving chloride ions

 If concentrated hydrochloric acid is added to a solution containing hexaaquacopper (II)

ions, the six water molecules are replaced by four chloride ions.

Figure 12.3.12 showing colour change during ligand exchange involving chloride ions

v. Reaction of hexaaquacopper (II) ions with iodide ions

  Reaction of hexaaquacopper (ii) ions with iodide ions is known as the Iodometric
determination of copper.

 The reaction is based on the oxidation of iodides to iodine by copper (II) ions, which get
reduced to Cu+.

 Comparing the standard potentials for both half reactions (Cu2+/Cu+ E0=0.17 V,
I2/I- E0=0.54 V) indicates that iodine should be acting as the oxidizer.

 However, that's not the case, as copper (I) iodide is very weakly soluble (K sp = 10-12).

 The Ksp value means concentration of Cu+ in the solution is very low and the standard
potential of the half reaction Cu2+/Cu+ in the presence of iodides is much higher and is
around 0.88 V.

 The reaction is given by:

 In effect reaction taking place in the solution is

−¿→2 CuI(s )+ I2 ¿

2 C u2+ ¿+ 4 I ¿

 To calculate the amount of iodine liberated, a titration method is used with sodium
thiosulphate solution.
−¿ ¿
2−¿+ 2 I ¿
¿
2 S 2 O2−¿+
3
I →S 2 4 O6

 A standard indicator for iodine titrations is used to determine the end point is starch.

Uses of Copper

 Due to copper being ductile and electrical and thermal conductivity, copper is used in
the production of electrical conductors, switches, transformers, and
telecommunications.

 Copper is resistant to corrosion which makes copper an ideal material for the
production of roofing and plumbing applications.

 Copper can be combined with other metals to make alloys.

  The most common well known copper alloys are brass and bronze.

 Some copper alloys are:

o Brass =copper + zinc

o Bronze =copper + tin

o Cupro-nickel =copper + nickel

 Copper alloys are used in a range of applications. Which include

o Power transmission lines o Electrical wiring, cables and bus

bars
o Architectural applications
o High conductivity wires
o Cooking utensils
o Electrodes
o Spark plugs

Test for Aldehydes

 A test for aldehydes is known as the Fehling's test.

 The Fehling's reagent is a blue coloured basic solution of bistartratocuprate (II) complex.

 Only aldehydes can reduce Fehling’s reagent a deep blue solution to give a red cuprous
oxide precipitate.

Figure 12.3.13 showing reduction of copper in the Fehling’s test

6. Manganese
Occurrence

 Manganese is the 12th most abundant element and 3rd most abundant transition metal
in the earth’s crust.
 A number of forms of manganese occur in nature, these include pyrolusite (MnO 2),
manganate (Mn2O3.H2O), and hausmannite (Mn3O4) rhodochrosite (MnCO3).
 Manganese in Zimbabwe is mined in Kwekwe, Gweru, Makonde, and Mberengwa.
 Manganese is obtained by reduction with Aluminium, or in a Blast furnace.

Oxidation States of Manganese

 In its compounds manganese exhibits oxidation states from +2 to +7. The common
oxidation states are +2, +4, and +7
 The relative stabilities of different oxidation states are best understood in terms of
standard electrode potentials, E0 values.
 The most stable oxidation state for manganese is +2, which has a pale pink colour.
 Common compounds of manganese +2 are manganese (II) sulphate (MnSO) and
manganese (II) chloride (MnCl).
 The +2 oxidation of manganese results from removal of the two 4s electrons, leaving a
high spin ion in which all five of the 3d orbitals contain a single electron.
 Compounds of Mn3+ are very powerful oxidizing agents.
 Solid compounds of manganese(III) are characterised by their preference for distorted
octahedral coordination and their strong purple-red colour.
 The +3 oxidation state is seen in compounds like manganese (III) acetate.
 Permanganate +7 oxidation state compounds are purple and can give glass a violet
colour. Potassium permanganate, sodium permanganate, and barium permanganate are
all potent oxidizers.

Colour of Manganese ions

 Manganese ions are coloured, both in the solid state and in solution.
 Their colour entirely due to the uneven absorption of light in the visible region of the
electromagnetic spectrum.
 In order to absorb light in the first place, the metal ion has to contain not only at least
one d electron, but also a space in the higher d orbital.
 The absence of colour in Mn(ll) compounds is due to the fact that five d-orbitals in
Mn(ll) compounds contains just one electron. In a particular ion, these five electrons
tend to align their spins parallel to each other.
 If an electron were to move from one of the lower set of orbitals to the higher set, it
would have to change the direction of its spin, because an orbital cannot be occupied by
two electrons unless their spins are opposite.
 The changing of an electron's spin in isolation of other spin changes is almost totally
forbidden by the rules of quantum mechanics.
 Thus, Mn (II) compounds have only a very pale pink colour.

Figure 12.3.14showing colour of manganese ions A) Mn 2+B)Mn3+C)Mn4+ D) Mn7+

Chemical properties and uses of manganese.

MnO2

 Manganese(IV) oxide is an excellent catalyst for the decomposition of hydrogen

peroxide.
 In small quantities manganese(IV) oxide is added to ice–cooled concentrated
hydrochloric acid an anionic octahedral manganese(IV) chloro complex ion is formed.
 −¿ ¿
2 Cl ⇋ C l 2+2 e E0/V = – 1.36
2+¿ +2 H O ¿
2
−¿⇋ Mn ¿

MnO2 + 4 H +¿+2 e ¿
E0/ V= +1.23

Mn O2 +4 H ⇋ MnC l 2 +C l 2 +2 H 2 O

MnO42-

 MnO42– is a tetrahedral dark green compound that can be made by strongly heating a
mixture of manganese (IV) oxide, potassium hydroxide and potassium chlorate (V) in a
crucible and extracting the manganese (VI) compound with water.
 The manganate(VI) ion, MnO42– is unstable, in acid solution, and slowly
undergoes disproportionation
 Adding dilute sulphuric acid to the crucible fusion extract will hasten the process
 The feasible and spontaneous disproportionation reaction of MnO42– can be explained by
considering the standard electrode potentials standard reduction potential involved.
2−¿¿
– ⇋ Mn O
Mn O −¿+e
4
4 ¿
EØ = +0.56V

+¿+ +2 e –⇋ MnO 2 +2 H 2 O ¿
¿
Mn O2−¿+4
4
H
EØ = +1.70V, in acid solution

EØreaction = EØreduction – EØoxidation = +1.70 – 0.56 = +1.14V

 The greater stability of the manganate (VI) ion in alkali can also be explained by
considering the electrode potential for in an alkaline solution.
2−¿¿
– ⇋ Mn O
Mn O −¿+e
4
4 ¿
EØ = +0.56V
−¿ ¿
2−¿+2 H 2 O+2 e – ⇋ Mn O2 +4 OH ¿ Ø
MnO O4 E = +0.59V, in alkaline solution

EØreaction = EØreduction – EØoxidation = +0.59 – 0.56 = +0.03V

 Based on the above reactions an EØreaction+1.14V,is well above 0V, therefore very feasible in
the other equation the EØreactionis +0.03V is just above 0, therefore just feasible.
 On the basis of equilibrium arguments, the MnO42– ion is far more likely to exist more
stable, in a very high pH solution.
 MnO4–

 MnO4– is a tetrahedral deep purple manganate (VII) ion.

 Potassium manganate (VII), KMnO4 is used to titrate (i) iron(II) ions, (ii) ethanedioates, (iii)
hydrogen peroxide and (iv) nitrate(III) ions (old name 'nitrite').
 The Mn2+ ions formed are almost colourless (very pale pink), so the end–point is the first
permanent faint pink due to the first trace of excess of the brilliant purple manganate(VII)
ion.
 Example of iron (II) titration with Potassium manganate (VII)
3+ ¿+ 4H O ¿
2
2+¿ +5F e ¿

−¿+8 H +¿+ 5 Fe2 +⇋ M n ¿

¿
Mn O 4

 Potassium manganate (VII), is strong enough to oxidise chloride ions.

 Reaction of Potassium manganate (VII) and concentrated hydrochloric acid onto the damp
crystals is another way of making chlorine in the laboratory.

Uses of manganese

 Manganese produced is used in the form of ferromanganese and silico manganese alloys
for iron and steel manufacture.
 Manganese dioxide, MnO2 is used as a reagent in organic chemistry for the oxidation of
benzylic alcohols. Manganese dioxide has been used since antiquity to oxidize and
neutralize the greenish tinge in glass from trace amounts of iron contamination.
 MnO2 is also used in the manufacture of oxygen and chlorine and in drying black paints.

7. Platinum Group
 Platinum group is a six member group of metals, in order of increasing atomic weight
ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium(Os), iridium (Ir),
and platinum (Pt).
 Platinum minerals usually occur in highly disseminated in sulphide ores, particularly
the nickel mineral pentlandite, (Ni, Fe)9S8.
 The most common platinum-group minerals include laurite, RuS2; irarsite,
(Ir,Ru,Rh,Pt)AsS; osmiridium, (Ir,Os); cooperite, (PtS); and braggite, (Pt,Pd)S.
 In Zimbabwe Platinum is mined at Mimosa, Zimplats and Unki mine.

Figure 12.3.15 showing Zimplats

Extraction

Foam flotation

 The platinum ore is crushed and milled, which increases the surface area of the metal
and
making it easier to extract all the valuable metals.
 Froth flotation is a method of separating materials on the basis of their physical
properties.
 In Platinum mining the crushed solid mixture is immersed in water which also contains
dissolved reagents to separate out Individual compounds, which are then removed as
slurry. Platinum is third densest metal in the crust so it will sink to the bottom of the
tank removed.

Drying and purification

 The wet platinum slurry is heated in special types of furnaces which maintain a
temperature of 1500 degrees Celsius.
 At the same time, air is blown through the mixture so that any impurities such as iron or
sulphur are removed.

Electrolysis

 The platinum and aqua regia solution is then subject to an electrical current, the
solution itself acts as an electrolyte a liquid or molten solid which allows the passing of
electricity.
 The platinum metal is attracted to the negative terminal (the cathode) where it is
collected. Platinum has a very high melting point other impurities can be burned off
leaving pure platinum metal.
The overall process involves several inter-related and complex processes which employ
both physical and chemical techniques.
 Other valuable metals can be extracted in tandem with platinum which makes the
whole process much more cost effective.

Uses of Platinum group metals

 The platinum group metals are used in a wide variety of industries.

 Examples of uses of platinum group metals are:
 Manufacturing of auto catalysts or the catalytic converter which is installed in the
exhaust line of the vehicle between the engine and the silencer.
 Its main function is to convert over 90 per cent of hydrocarbons, carbon monoxide and
oxides of nitrogen from gasoline engines into less harmful carbon dioxide, nitrogen and
water vapour.
 Platinum can be used to manufacture jewellery; it is made in a purity of at least 85 per
cent platinum.
  Other platinum group metals - palladium, ruthenium and iridium - and copper and
cobalt are commonly alloyed with platinum to optimise its working characteristics and
wear properties.
 Platinum can be used to manufacture jewellery because of its strength and resistance to
tarnish.
 Platinum group metals combine to make platinum and palladium alloys of exceptional
hardness and durability, making them the best coating for industrial crucibles which are
required to withstand extremely high temperatures in the manufacture of chemicals
and synthetics.
 Platinum-based catalysts, which in recent years have included rhodium as well, for the
commercial production of nitric acid, an essential ingredient in nitrogen fertiliser.
 Rhodium alloyed with other platinum group metals is used for furnace windings,
thermocouple elements, bushings for glass fibre production, electrodes for aircraft spark
plugs and laboratory crucibles.
 Rhodium is useful as an electrical contact material as it has a low electrical resistance, a
low and stable contact resistance and is highly resistant to corrosion.

8. Cobalt

Occurrence

 Cobalt is fairly rare, comprising only 0.003% of the Earth's crust. As is more with metals
to the right of the transition group, its common ores are sulphides and arsenides:
smaltite, CoAs2 cobaltite, CoAsS linnaeite.

Extraction

 Cobalt ores are usually mined along with ores of copper, nickel or lead. The ores are
roasted to give the oxides which are then leached with dilute sulphuric acid.
 Adding sodium chlorate(l) to the resulting solution of CoSO4 precipitates Co(OH)3.This is
dehydrated by heating, and the oxide so formed is reduced by charcoal to the metal.
Oxidation states of cobalt

 The main oxidation states of cobalt are Co2+ and Co3+.

 Cobalt (ll) is more stable than cobalt(lll), which is a powerful oxidizing agent that can
oxidize water and liberates oxygen.
 Metallic occurs; in two allo-tropic forms, hexagonal and cubic, which are stab e at room
temperature
 Cobalt has a relative molecular mass of 58.93 and is silvery grey solid at room
temperature.

Cobalt compounds

 Cobalt (Il) compounds include those formed with the reactive gases called halogens—
fluorine (COF2), chlorine (CoCl2), bromine (CoBr2), and iodine (Col). Halogen compounds
are generally stable.
 Cobalt (Il) carbonate (CoC03) is also very stable and Cobalt (Il) hydroxide, gradually
changes in air to cobalt (Ill) hydroxide (Co(OH)3.
 Most simple cobalt (Ill) compounds with halogens are unstable, except when molecules
of ammonia are added to form complex compounds.
 The exception is cobalt (Ill) fluoride, CoF3, this is a brown powder used to add fluorine
atoms to carbon compounds to make very stable and unreactive gases called
fluorocarbons.
 Cobalt (Il) nitrate, is also stable. Cobalt (Ill) nitrate is not, except when ammonia (or a
similar ligand) is added to the molecule.
 Cobalt forms three main oxides. Cobalt (Ill) oxide, C0203, is a black compound formed
when cobalt metal is heated slightly in plenty of air.
 At temperatures of 4000C to 8500C C0304 is produced. Above 11000C cobalt (Il) oxide, or
cobalt monoxide (CoO) forms.
The cobalt oxide used in industry contains a mixture of these compounds.
 Chemical Properties

 Ligand metal bond in the +3 oxidation state of cobalt is kinetically inert, whereas in the
+2 state it can easily be replaced. This fact, coupled with the ease of oxidation of
complexed Co(ll), was made use of in the preparation of many classic Co(lll) complexes.
 Apart from the floro complex [CoF6]3-all Co(lll) complexes are "low spin". Having their six
d electrons paired in the three lower energy d orbitals.

i. A ligand exchange reaction with HCl

 If hydrochloric acid is added to cobalt(II) sulphate solution the blue
tetrachlorocobaltate(II) complex ion is formed.

ii. Ligand Exchange of hexaaquacobalt (II) ions with ammonia solution

 When excess ammonia is added to a cobalt (II) salt solution, the hexamine complex is
formed however this is unstable in the presence of dissolved oxygen and is oxidised to
the cobalt(III) complex.
 This change in cobalt's oxidation state from +2 to +3 via an oxidising agent is a common
if a complexing agent.
 The ammonia acts as both a base and a ligand.

 Pink hexaaquacobalt (II) ion changes colour to brown hexaamminecobalt(II) ion.

 The cobalt (III) complex is stabilised compared to the cobalt(II) complex by the change of
ligand from water to ammonia.

Uses of Cobalt and its alloys

  Cobalt is used in electroplating, a process in which a layer of material is applied to an
object to give it a particular aesthetic or protective quality. Cobalt provides objects with
an attractive surface that prevents rusting.
 Cobalt improves the performance of rechargeable batteries and plays an important role
in hybrid electric vehicles.
 Cobalt alloys are used in orthopaedic implants alongside titanium and stainless steel.
The Idaho Cobalt Project states that approximately 70 percent of hip replacements use
cobalt-chrome femoral stems.
 Cobalt-60, a radioactive form of the element, can treat some forms of cancer. The
substance can also sterilize medical supplies.
 Cobalt chloride, sulphate, acetate or nitrate can correct mineral deficiency in grazing
animals living on cobalt-deficient soil. Cobalt is an essential part of vitamin B12
(cobalamin).
 Cobalamin is necessary for DNA synthesis, formation of red blood cells, and
maintenance of the nervous system, growth and development of children.
 Cobalt salts are used to produce vivid shades of blue in porcelain, glass, pottery and
tiles.

Cobalt water test

 Water can be detected using blue anhydrous cobalt(II) chloride. This turns pink in the
presence of water.
 The reaction is as follows:

CoC l 2 ⇋ CoC l 2 .2 H 2 O ⇋ CoC l 2 6. H 2 O

 Colour change is from blue to blue.

 If pink CoCl2.6H2O is heated gently up to 150°C it will gradually lose water forming the
violet CoCl2.2H2O, then blue anhydrous CoCl2. This can again be reversed by adding
water.
 This colour change can be explained by the fact that the colour of transition metal
complexes is due to electronic transitions between different d-orbitals.
 Water produces larger splitting between the energy levels than chloride (H 2O is a
‘stronger-field’ ligand than Cl) so the energy differences between different electronic
energy levels are smaller in complexes with lots of chlorides as ligands, so this has a
significant effect on the colour.