This is due to the difference in the number of chloride ions that are

exchanged with the molecules in the complex compound.

Chemistry of the individual elements

1. Titanium

Reactions of titanium

a. With air
Heated titanium burns in oxygen to form titanium(IV) oxide

b. With chlorine
Heated titanium burns in dry chlorine to form titanium(IV) chloride

c. With acids
Titanium is oxidized by hot concentrated sulphuric acid to titanium(IV)
sulphate and the acid reduced to sulphur dioxide and water.

Compounds of titanium
Titanium forms compounds in which it shows +2; +3; and +4 oxidation
states.

The +2 oxidation state is unstable and uncommon.

In the +3 oxidation state, titanium still has one electron in the 3d-orbital
and because of this titanium(III) compounds are coloured are
paramagnetic

In the +4 oxidation state, titanium has lost all the electrons in the 3d-
orbital. Thus, titanium(IV) compounds are neither coloured nor
paramagnetic.

TRANSITION CHEMISTRY NOTES Page 8 of 49

 Titanium(iv) compounds

Titanium(IV) chloride
This can be prepared by heating titanium in a stream of dry chlorine.

It is a colourless fuming liquid that is readily hydrolysed in water.

Question

(a) Write the electronic configuration of titanium (atomic number 22)

(b) Describe the reaction of titanium with
(i) Air
(ii) Chlorine
(iii) Sulphuric acid
(c) Water was added to titanium(IV) chloride, state what was observed and
write equation for the reaction
(d) Titanium(III) chloride is violet while titanium(IV) chloride is colourless.
Explain the observation.

2. Vanadium

Reactions of vanadium

a. With chlorine
Heated vanadium reacts with chlorine to form vanadium(IV) chloride, a
dark red covalent liquid

b. With air
Heated vanadium reacts with air to form vanandium(V) oxide, an orange
solid

TRANSITION CHEMISTRY NOTES Page 9 of 49

 Compounds of vanadium
Vanadium forms compounds in the +2, +3, +4, and +5 oxidation states.
The +4 is the most stable oxidation state. As with all the transition
elements, the covalent character of the compounds increases with
increasing oxidation number.

All the oxidation states of vanadium can be observed in the aqueous

species formed when a solution of ammonium vanadate(V) is treated with
dilute sulphuric acid and zinc metal.

Summary of the colour changes

Species
Oxidation state +5 +4 +3 +2
Colour Yellow Blue Green Violet

3. Chromium

Reactions of chromium

a. With air
Heated chromium reacts with air to form chromium(III) oxide

b. With water
Heated chromium reacts with steam to form chromium(III) oxide and
hydrogen gas

TRANSITION CHEMISTRY NOTES Page 10 of 49

 c. With chlorine
Heated chromium reacts with dry chlorine to form chromium(III) chloride

d. With alkalis
Chromium reacts with hot concentrated sodium hydroxide solution
forming a green solution of sodium chromate(III) and hydrogen gas

Or

e. With hydrogen chloride

Heated chromium reacts with dry hydrogen chloride gas to form
chromium(II) chloride

f. With acids
Chromium reacts with warm dilute sulphuric and hydrochloric acids to
give the corresponding chromium(II) salts and hydrogen gas

Chromium is oxidized by hot concentrated sulphuric acid to

chromium(III) sulphate and the acid reduced to sulphur dioxide and
water

Chromium is rendered passive by concentrated nitric acid

TRANSITION CHEMISTRY NOTES Page 11 of 49

 Compounds of chromium
Chromium forms compounds in the +2, +3, and +6 oxidation stated. The
+3 oxidation state is the most stable.

Chromium(II) compounds
Compounds of chromium in this oxidation state are very unstable and
strong reducing agents being converted into the more stable
chromium(III) compounds

Oxidizing agents like chlorine can oxidisechromium(II) to chromium(III)

Chromium(II) chloride
It’s a white solid prepared by heating chromium metal in dry hydrogen
chloride

Chromium(II) hydroxide
It’s a yellow solid precipitates when a little alkali is added to t solution of
chromium(II) salt

Chromium(III) compounds

Chromium(III) oxide
It is a green ionic and amphoteric solid that can be obtained by

 Heating chromium in air

 Heating chromium(III) hydroxide

TRANSITION CHEMISTRY NOTES Page 12 of 49

  Heating ammonium dichromate

It reacts with acids to form corresponding chromium(III) salts

It reacts with hot concentrated alkalis to give chromate(VI) salts

Or

When heated aluminium, it is reduced to chromium

Chromium(III) hydroxide
It is a green amphoteric solid formed by precipitation when a little alkali
is addedto a solution chromium(III) salt

It reacts with dilute acids to form chromium(III) salts

It reacts with alkalis to form chromate(III) salts

Or

TRANSITION CHEMISTRY NOTES Page 13 of 49

 Chromium(III) salts
These are generally prepared by reacting chromium(III) oxide or
hydroxide with acids.

Solutions of chromium(III) salts are acidic. This is because of hydrolysis

of the hydrated chromium(III) cation.

The chromium(III) cation has a high charge density thus becomes

heavily hydrated in solution. The coordinating water molecules are
polarized weakening the oxygen-hydrogen bond so that the proton can
easily be lost to the solution, making it acidic.

Chromium(VI) compounds

Chromium(VI) oxide,
Chromium(VI) oxide is a dark red that can be prepared by adding
concentrated sulphuric acid to a saturated solution of potassium
dichromate

When heated it decomposes to give chromium(III) oxide and oxygen gas

It is an acidic oxide that dissolves in water to form chromic(VI) acid

It also reacts with alkalis to form chromates(VI)

Chromates(VI)
These are salts derived from chromic(VI) acid. They are generally
insoluble in water except sodium, potassium and ammonium chromates

The insoluble chromates can be prepared by precipitation reactions.

TRANSITION CHEMISTRY NOTES Page 14 of 49

 All the above chromates are yellow except silver chromate which is a
dark red solid.

The chromate ions has a tetrahedral structure

Chromates are only stable in alkaline medium. In acidic medium, they

convert to dichromates

Dichromtes(VI)
These are orange coloured salts containing the dichromate ion,

In solution, dichromates can be obtained by adding dilute sulphuric acid

to a solution of a chromate

Dichromates are only stable in acidic medium and in alkaline medium

they convert to chromates

Potassium dichromate(VI) is used as an oxidizing agent in volumetric

analysis and organic syntheses

Dichromate(VI) ions are strong oxidizing agents in acid medium

TRANSITION CHEMISTRY NOTES Page 15 of 49

 However, they are not strong enough to oxidise chlorides to chlorine
therefore they can be used in the presence of hydrochloric acid unlike
manganate(VII)

Examples:

(a) Oxidation of iron(II) to iron(III)

Observation

The orange solution turns green

(b) Oxidation of iodide ions to iodine

Observation

The colourless solution (of potassium iodide) turns brown

(c) Oxidation of hydrogen sulphide to sulphur

Observation

The orange solution turns green, and a yellow precipitate is formed

(d) Oxidation of sulphur dioxide to a sulphate

Observation

The orange solution turns green

(e) Oxidation of sulphites to sulphates

Observation

The orange solution turns green

TRANSITION CHEMISTRY NOTES Page 16 of 49

 (f) Oxidation of tin(II) to tin(VI)

Observation

The orange solution turns green

Qualitative analysis of
1. Sodium carbonate solution

Observation

A green solid and bubbles (effervescence) of a colourless gas

Equation

2. Sodium hydroxide solution

Observation

A green precipitate soluble in excess to form a green solution

Equation

3. Ammonia solution

Observation

A green precipitate insoluble in excess

Equation

TRANSITION CHEMISTRY NOTES Page 17 of 49

 4. Sodium hydroxide and hydrogen peroxide

Observation

A yellow solution on warming

Equation

5. Sodium hydroxide, hydrogen peroxide, butanoland dilute sulphuric acid

Observation

A blue solution in the organic layer

Equations

4. Manganese

Reactions of manganese
a. With air

Heated manganese burns in air to form a mixture of

trimanganesetetraoxide.

b. With water

TRANSITION CHEMISTRY NOTES Page 18 of 49

 Heated manganese reacts with steam to form trimanganesetetraoxide
and hydrogen gas

c. With acids

Manganese reacts rapidly with cold dilute hydrochloric acid and

sulphuric acid to form the corresponding manganese(II) salt and
hydrogen gas

Manganese reacts with cold dilute nitric acid to form manganese(II)

nitrate, nitrogen monoxide and water

Manganese is oxidized by hot concentrated sulphuric acid to

manganese(II) sulphate and the acid reduced to sulphur dioxide and
water

Manganese is oxidized by cold concentrated nitric acid to manganese(II)

nitrate and the acid reduced to nitrogen dioxide and water

d. Chlorine

Heated manganese reacts chlorine to form manganese(II) chloride

TRANSITION CHEMISTRY NOTES Page 19 of 49

 Compounds of manganese
Manganese exhibits oxidation states of +2, +3, +4, +6 and +7 in various
compounds.

In the +2 oxidation state, the two 4s electrons are lost, leaving a half-
filled 3d orbital which is stable. This makes the +2 oxidation state the
most stable oxidation state of manganese

Manganese(II) compounds

Manganese(II) oxide, MnO

It’s a green solid obtained by heating manganese(II) hydroxide,
manganese(II) carbonate or manganese(II) oxalate in absence of air to
prevent further oxidation

It is a basic oxide, dissolving in acids to form manganese(II) salts

Manganese(II) hydroxide Mn(OH)2

It can be obtained as a white precipitate when sodium hydroxide or
ammonia solution is added to a solution of o manganese()II salt

The white precipitate turns brown due to oxidation by oxygen from air to
form hydrated manganese(IV) oxide

Note: hydrated manganese(IV) oxide is brown while anhydrous

manganese(IV) oxide is black

Manganese(II) salts
Most manganese(II) salts are pink. Manganese(II) carbonate is red

Manganese(II) chloride crystals can be obtained by heating

manganese(IV) oxide with concentrated hydrochloric acid.

TRANSITION CHEMISTRY NOTES Page 20 of 49

 The pink crystals form from the solution on cooling

Manganese(II) sulphate crystals can be obtained by heating

manganese(IV) oxide with concentrated sulphuric acid

The pink crystals form from the solution on cooling

Manganese(II) nitrate can be obtained by reacting dilute nitric acid and

manganese(II) carbonate followed by crystallization.

Manganese(II) carbonate can be obtained by adding sodium hydrogen

carbonate to a solution of manganese(II) salt.

Manganese(III) compounds
Compounds of manganese in this state are uncommon because of
disproportionation

Manganese(IV) compounds

Manganese(IV) oxide, MnO2

Anhydrous manganese(IV) oxide is a black solid that can be prepared by
heating manganese(II) nitrate

It can also be prepared by oxidation of manganese(II) salts using sodium

hypochlorite and sodium hydroxide

 Manganese(IV) oxide is essentially ionic and amphoteric. It dissolves in

cold concentrated hydrochloric acid to form hexachloromanganate(IV)
complex

TRANSITION CHEMISTRY NOTES Page 21 of 49

  Manganese(IV) oxide oxidizes hot concentrated hydrochloric acid to
chlorine

 Manganese(IV) oxide reacts with hot concentrated sulphuric acid to

liberate oxygen

 Manganese(IV) oxide oxidizes oxalates to carbon dioxide in acidic

medium

Determination of the percentage of manganese(IV) oxide the pyrulosite

 A known mass for pyrulosite (ore) is dissolved in excess hot concentrated
hydrochloric acid
 Manganese(IV) oxide reacts with hydrochloric acid to liberate chlorine

 The chlorine liberated is bubbled through excess potassium iodie

solution to liberate iodine

 A known volume of the solution containing the liberated iodine is then

titrated with a standard solution of sodium thiosulphate using starch
indicator

 The mass of manganese(IV) oxide is calculated and the percentage of the

ore calculated as

TRANSITION CHEMISTRY NOTES Page 22 of 49

 Manganese(VI) compounds
Sodium and potassium maganate(IV) are dark green crystals. Potassium
manganate(VI) can be obtained by fusing potassium hydroxide with
manganese(IV) oxide in the presence of excess oxygen.

Manganate(VI) is only stable in alkaline medium. In acidic or neutral

medium, it undergoes disproportionation

Or

Even bubbling carbon dioxide through a solution of manganate(VI)

causes the colour of the solution to change from green to purple with
formation of a black solid

Manganese(VII) compounds
Potassium manganate(VII) is the most important compound manganese
in the +7 oxidation state.

It is dark purple crystalline compound soluble in water forming a purple

solution.

It is used in the laboratory for preparation of chlorine gas and testing for
the presence of sulphur dioxide, unsaturated hydrocarbons and
hydrogen sulphide

It is used in volumetric analysis and organic chemistry as an oxidizing

agent

It can be used in neutral, alkaline and acidic medium. Only sulphuric

acid is used to acidify potassium manganate(VII).

Nitric acid is not used because it is also an oxidizing agent hence will
compete with potassium during the reaction.

Hydrochloric acid is not used because it is easily oxidized to chlorine by

potassium manganate(VII)

TRANSITION CHEMISTRY NOTES Page 23 of 49

 Advantages of using potassium permanganate in volumetric analysis
 It acts as a its own indicator
 It a high formula mass which minimizes the weighing errors
 It is highly soluble in water
 Most of its reaction can occur fast enough at room temperature
 It oxidizes a wide range of substances

Why potassium manganate(VII) is not used as a primary

 it always found contaminated with manganese(VI) oxide
 It is not highly stable. In light, a solution of acidified potassium
manganate(VII) will decompose to form manganese(IV) oxide

Even in alkaline medium, decomposition will occur as follows

Oxidizing properties potassium manganate(VII)

In neutral or slightly alkaline mediummanganate(VII) is reduced to
manganese(IV) oxide

For example, oxidation of iodide to iodate

Overall equation

In strongly alkaline medium, manganate(VII) is reduced to green

manganate(VI)

In strongly acidic medium, manganate(VII) is reduced to manganese(II)

ions. Unless stated, the solution turns from purple to colourless

TRANSITION CHEMISTRY NOTES Page 24 of 49

 Examples

a. Oxidation of nitrites to nitrates

b. Oxidation of hydrogen peroxide to oxygen

c. Oxidation of tin(II) to tin(IV)

d. Oxidation of iron(II) to iron(III)

Observation

The solution turns from purple to brown

e. Oxidation of hydrogen sulphide to sulphur

Observation

The solution turns from purple to colourless with formation of a yellow

deposit (solid)

Qualitative analysis of
1. Sodium carbonate solution

Observation

TRANSITION CHEMISTRY NOTES Page 25 of 49

 A brown precipitate that rapidly turns brown on standing. (This is due to
aerial oxidation of manganese(II) hydroxide to hydrated manganese(IV)
oxide)

Equations

2. Ammonia solution

Observation

A brown precipitate that rapidly turns brown on standing. (This is due to

aerial oxidation of manganese(II) hydroxide to hydrated manganese(IV)
oxide)

Equations

3. Conc. Nitric acid and solid sodium bismuthate

Observation

A purple solution is formed.

(Manganese(II) ions are oxidized to manganate(VII) ions by sodium

bismuthate in acidic medium)

Equation

4. Conc. Nitric acid and solid lead(IV) oxide and warm

Observation

TRANSITION CHEMISTRY NOTES Page 26 of 49