TRANSITION ELEMENTS

A transition element is an element that forms at least one stable ion or atom with a
partially filled 3d – orbital
d – block element
d – block element is an element that has its highest energy electrons in the d – orbital.
Or
It is an element that fills its last electron in the d – orbital
They are found between the highly reactive s-block metals and the less reactive p-
block elements in the periodic table.

A table showing the d – block elements

Element Symbol Atomic Electronic configuration
number
Scandium Sc 21 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑14𝑠2
Titanium Ti 22 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑24𝑠2
Vanadium V 23 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑34𝑠2
Chromium Cr 24 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑54𝑠1
Manganese Mn 25 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑54𝑠2
Iron Fe 26 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑64𝑠2
Cobalt Co 27 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑74𝑠2
Nickel Ni 28 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑84𝑠2
Copper Cu 29 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑104𝑠1
Zinc Zn 30 1𝑠22𝑠22𝑝63𝑠23𝑝63𝑑104𝑠2

Scandium is not transition because the stable ion of scandium, Sc 3+, has no
electrons in the 3d - sub-energy level.
Zinc is not transition because the stable ion of zinc, Zn2+, has a fully filled 3d - sub
energy level.

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 Periodic trends
Atomic radius
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 21 22 23 24 25 26 27 28 29 30
number
Atomic 0.144 0.132 0.122 0.117 0.117 0.116 0.116 0.115 0.117 0.125
radius
(nm)

0.15

0.145
Sc
0.14
Atomic radius (nm)

0.135
Ti
0.13

0.125 Zn
V
0.12
Cr Mn Co Cu
Fe Ni
0.115

0.11
21 22 23 24 25 26 27 28 29 30
Atomic number

The atomic radius decreases very slightly from scandium to nickel.

This is because the increase in nuclear charge due addition of protons to the nuclei
of the atoms is almost balanced by the increase in the screening effect due addition
of electrons to the 3d sub energy level which is the penultimate energy level so that
the increase in the nuclear charge is only very slight.
The slight increase in atomic from nickel to zinc is because the penultimate sub
energy level is getting filled with electrons which increases the screening effect
slightly more than increase in nuclear charge
Qn: Across the transition elements, atomic radius remains almost constant.
Explain
Solution

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Across the transition element series, the nuclear charge increases due to
addition of a proton to the nucleus of each successive element. The electrons
are added to the inner (penultimate) 3d sub-energy level, thus the screening
effect increases. The increase in nuclear is balanced by the increase in
screening effect. Thus nuclear attraction for the outermost electrons remains
almost constant.

Melting points
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 21 22 23 24 25 26 27 28 29 30
number
Melting 1540 1680 1917 1890 1240 1535 1490 1452 1083 419
points (ºC)

2000 V Cr
1800

1600 Ti Fe
Co
Meltimg points (oC)

Sc Ni
1400

1200 Mn Cu
1000

800

600
Zn
400
21 22 23 24 25 26 27 28 29 30
Atomic number

Generally, the melting points increase from scandium to vanadium and decrease
from chromium to zinc with manganese having a lower melting point than expected.
From scandium to vanadium, the number of unpaired 3d-orbital electrons that take
part in metallic bonding increases, therefore the strength of the metallic bond
increases resulting in increase in melting point.
From chromium to zinc, the number of unpaired 3d-electrons taking part in metallic
boding decreases resulting into decrease the strength of metallic bond hence
decrease in melting point from chromium to zinc.

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Manganese and zinc have low melting points than expected because of the half-
filled and the fully filled 3d-orbitals in manganese and zinc respectively are
relatively stable and thus the electrons are not readily available for inter-atomic
bonding.

PROPERTIES OF TRANSITION ELEMENTS

1. Paramagnetic
Atoms and cations of transition elements are weakly attracted into a magnetic field.
The property arises because of the presence of unpaired electrons in the transition
metal atoms and ions.
These unpaired electron spin to generate a magnetic field that can be attracted by
an external magnetic field.
Paramagnetism increases with increase in the number of unpaired electrons. Hence
it increases from scandium to maximum at manganese due to increase in the number
of unpaired electrons and then decreases to zinc due to electron pairing.
Paramagnetic effect

0 1 2 3 4 5 4 3 2 1 0
No. of unpaired electrons

Compounds of scandium and zinc are not paramagnetic because they don’t have
unpaired electrons and their magnetic moment is zero.

2. They have Catalytic activity

Transition metals and their compounds are used as catalysts. This is due to;
Presence of partially filled d – orbitals which allows the reacting particles to form
partial bonds with them forming an unstable catalyst – reactant complexes that are
more reactive.
Possession of variable oxidation states which enables them to take part in electron
transfer reactions forming activated complexes of the reactants.

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 These activated complexes can then react with each other to form the product which
then leaves the catalyst.

3. Variable oxidation states

Oxidation state is the charge left on a given atom when all other atoms in the
compound are removed as ions.

Or
Is the charge that an atom would have if all the bonds in the compound were fully
ionic.

It can be negative, zero or positive.

Variable oxidation states are possible in these elements because of the presence of
empty orbitals and unpaired electrons. The energy difference between 3d and 4s –
orbitals is almost the same hence their electrons require little energy to promote in
the empty orbitals to be used as valence electrons

The oxidation state of an element in a given compound can be calculated if the

oxidation states of other elements in a compound are known.

Examples

Determine the oxidation state of

(a) Manganese in 𝐾𝑀𝑛𝑂4

𝐿𝑒𝑡 𝑡ℎ𝑒 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑛𝑔𝑎𝑛𝑒𝑠𝑒 𝑏𝑒 𝑥

1 + 𝑥 + (−2𝑥4) = 0

𝑥−7=0

𝑥 = +7

∴ 𝑇ℎ𝑒 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑛𝑔𝑎𝑛𝑒𝑠𝑒 𝑖𝑛 𝐾𝑀𝑛𝑂4 𝑖𝑠 + 7

(b) Chromium in 𝐶𝑟2 𝑂72−

𝐿𝑒𝑡 𝑡ℎ𝑒 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚 𝑏𝑒 𝑦

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 2𝑦 + (−2𝑥7) = −2

2𝑦 − 14 = −2

2𝑦 = 12

𝑦 = +6

∴ 𝑇ℎ𝑒 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑠𝑡𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑟𝑜𝑚𝑖𝑢𝑚 𝑖𝑛 𝐶𝑟2 𝑂72− 𝑖𝑠 + 6

Assignment

Determine the oxidation state of

(a) Manganese in 𝑀𝑛𝑂2

(b) Manganese in 𝑀𝑛𝑂22−

(c) Chromium in 𝐶𝑟𝑂42−

(d) Iron in 𝐹𝑒(𝐶𝑁)4−

6

(e) Zinc in 𝑍𝑛(𝑁𝐻3 )2+

4

4. Coloured compounds and ions

The formation of coloured compounds and ions is associated with the presence of
partially filled 3d – orbitals in the transition metal atoms and ions and the ability to
promote electrons into these partially filled orbitals.
The energy used in the promotion of the electron is obtained by absorbing light of a
particular wavelength hence colour.
The colour absorbed will be missing in the transmitted light, while the compound
appears to have the colour of the light filtered through.
Cations with empty or fully filled 3d – orbitals do not possess colours because
promotion of electrons is not possible.

5. Interstitial compounds
Transition metals have metal lattices with spaces in between the atoms called
interstitial spaces.
These spaces can be occupied by atoms with small enough atomic radii such as
carbon and nitrogen resulting into an interstitial alloy or compound. e.g. carbon in
steel are interstitial alloys.

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 6. Complex formation
Complex ion is an ion consisting of a central metal ion datively bonded to electron
rich molecules or ions called ligands.
The number of ligands coordinated (bonded) to the central metal ion is called the
coordination number. The coordination number of a central metal ion is always
the same no matter the ligands its bonds with.
Question
State the coordination number of the following complexes
[𝐶u(𝑁𝐻3)4]2+ 4
[Cr(H2 O)6 ] 3+
6
[𝐶𝑟(𝐻2 𝑂)4 𝐶𝑙2 ] +
6

Formation of complexes is favoured by

(i) Availability of vacant or partially filled d – orbitals in the transition metal
ions which can accommodate the lone pairs of electrons from the ligands.
(ii) Small ionic radius of the central metal ions
(iii) High charge of the central metal ions. High charge with small ionic radius
gives the ion a high charge density resulting into strong attraction for the lone
pairs of electrons on the ligands in order to form a stable complex.

Nomenclature of complexes
1. The cation is always named first before the anion.
2. The names of the ligands precede the names of the central metal ion or atom
3. The ligand name is preceded by the prefix showing the number of ligand species
present in the complex. The Greek prefixes mono-, di-, tri-, tetra-, penta-, hexa-
, and so on are used when these ligands are relatively simple.
4. when the prefixes di-, tri- are already included in the name of the ligand, the name
of the ligand in placed in a bracket with bis-, tris-, and tetrakis- instead of di-, tri-
, tetra-
5. The names of anionic ligands end in – o for example
Change the ending as follows: -ide to -o; -ate to -ato and -ite to–ito
Ligand Name Ligand Name
𝐶𝑁− cyano 𝑂𝐻− hydroxo
−
𝐵𝑟− bromo 𝐶𝑙 chloro
−
𝐼− iodo 𝐹 fluoro

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 𝑆𝑂42− sulphato 𝑁𝑂3− nitrato
𝑁𝑂2− nitrito 𝑂2− oxo

6. For neutral ligands, the common names are used with a few exceptions which
include
Ligand Name
𝑁𝐻3 Ammine
𝑁𝑂 Nitrosyl
𝐻2𝑂 Aqua
𝐶𝑂 Carbonyl

7. Cationic ligands end in −𝑖𝑢𝑚 𝑒𝑔 𝑁𝐻2 − 𝑁𝐻3+ ℎ𝑦𝑑𝑟𝑎𝑧𝑖𝑛𝑖𝑢𝑚

8. In case there are more than one type of ligands, they are named as anionic ligands,
neutral ligands and then cationic ligands. With each category if there is more than
one type still, they are named in alphabetical order.
9. Metals forming complex cations or neutral compounds are given their standard
names whereas metals forming complex anions have their names changed ending
in –ate. Ferrate for iron, Cuprate for copper, Stannate for tin, Argentate for silver
10.The oxidation number of the central metal atom or ion is written in Roman
numerals in brackets immediately after its name.

Examples

[𝐶𝑜(𝑁𝐻3 )6 ]3+ Hexaamminecobalt(III) ion

2+
[𝐶𝑢(𝑁𝐻3 )4 ] Tetraamminecopper(II) ion
𝑁𝑖(𝐶𝑂)4 Tetracarbonylnickel(0) complex
2+
[𝑍𝑛(𝐻2 𝑂)2 (𝑁𝐻3 )2 ] Diamminediaquazinc(II) ion
[𝐶𝑢(𝑁𝐻3 )4 (𝐻2 𝑂)2 ]𝑆𝑂4 Diaquatetraamminecopper(II) sulphate
[𝑃𝑡𝐶𝑙6]2− Hexachloroplatinate(II) ion
3−
[𝐹e(𝐶𝑁)6] Hexacyanoferrate(III) ion
[Cr(H2 O)4 Cl2 ] +
Dichlorotetraaquachromium(III) ion
[Cu(en)2 ]2+ Bis(ethylenediamine)copper(II) ion
Question
State the oxidation state, determine the coordination number of the central atom and
name the following complexes

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 (i) [CrCl2 (H2 O)4 ] +
(ii) [Ag(NH3 )2 ] +
(iii) [Fe(SCN)(H2 O)5 ] 2+
(iv) [V(CN)6 ] 3−
(v) [Co(Cl)4 ] 2−

Isomerism in Transition Complexes

Isomerism among transition metal complexes arise as a result of different
arrangements of their constituent ligands. Transition complexes exhibit the
following isomers
a) Geometric isomerism
This is due to arrangement of ligands in space around the central metal ion resulting
to cis and trans isomers e.g. [Cu(NH3 )2 Cl2 ] has the following geometric isomers.

b) Ionization isomerism
This type of isomerism is as a result different ions being directly attached to the
central metal ion or free in solution e.g. Co(NH3 )5 BrSO4 has the two ionization
isomers.
i) [Co(NH3 )5 Br] 2+ SO2− 4 (bromopentaamminecobalt(III) sulphate)
In this isomer the bromide ion (Br − ) is directly coordinated to the cobalt(III) ion
while SO2−4 ion is free in solution and therefore it can be separated from the solution
by adding barium nitrate or chloride solution to form a white precipitate while
addition of silver nitrate solution does not precipitate out silver bromide (a yellow
precipitate) because it is not free.
Ba2+ (aq) + SO2− 4 (aq) → BaSO4 (s)
ii) [Co(NH3 )5 SO4 ]+ Br − (sulphatopentaamminecobalt(III) bromide)

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In this isomer the sulphate ions are directly coordinated to the cobalt(III) ions while
the bromide ions are free in solution. Therefore, addition of barium nitrate or
chloride solution, no precipitate is formed while addition of silver nitrate solution
produces a yellow precipitate of silver bromide.
Ag + (aq) + Br − (aq) → AgBr(s)

c) Hydration isomerism
In this isomerism, the isomers differ in the number of water molecules directly
bonded to the central metal ion and those that are free e.g. CrCl3 . 6H2 O has the
following isomers
Isomer Number of No. of free Color of
free ions chloride ions isomers
(a) [Cr(H2 O)6 ]𝐶𝑙3 4 3 Violet
(b) [Cr(H2 O)5 Cl]𝐶𝑙2 . 𝐻2 𝑂 3 2 Light green
(c) [Cr(H2 O)4 𝐶𝑙2 ]Cl. 2𝐻2 𝑂 2 1 Dark green

The isomers have different conductivities in aqueous solution depending in the

number of free ions present. Therefore, isomer (a) has the highest conductivity
because it has 4 free conducting ions, followed by isomer (b) and isomer (c) has the
least because it has only two conducting ions
When 3 moles of silver nitrate solution are separately added to the three isomers,
Isomers precipitate different amount of silver chloride depending on the free
chloride ions in the isomer.
Isomer (a) precipitate 3 moles of silver chloride
[Cr(H2 O)6 ]𝐶𝑙3 (aq) + 3Ag + (aq) → [Cr(H2 O)6 ] 3+ (aq) + 3AgCl(s)
Isomer (b) precipitates 2 moles of silver chloride
Isomer (c) precipitates 1 mole of silver chloride

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 CHEMISTRY OF INDIVIDUAL ELEMENTS
CHROMIUM
Atomic number: 24

Electronic configuration: 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑 5 4𝑠1

Occurance

It occurs naturally as chromite or chrome iron ore, 𝑭𝒆𝑪𝒓𝟐 𝑶𝟒 𝒐𝒓 𝑭𝒆𝑶. 𝑪𝒓𝟐 𝑶𝟑

Extraction
(i) Thermit process
Chromium(III) oxide is mixed with aluminium and the mixture fired by a
piece of burning magnesium ribbon inserted into sodium peroxide.
𝐶𝑟2 𝑂3 (𝑠) + 2𝐴𝑙(𝑠) → 𝐴𝑙2 𝑂3 (𝑠) + 2𝐶𝑟(𝑠)
(ii) Electrolysis
At the cathode

𝐶𝑟 3+ (𝑎𝑞) + 3𝑒 → 𝐶𝑟(𝑠)
(iii) Carbon reduction
Chromite is heated with carbon in the electric furnace
𝐹𝑒𝐶𝑟2 𝑂4 (𝑠) + 4𝐶(𝑠) → 𝐹𝑒(𝑙) + 2𝐶𝑟(𝑙) + 4𝐶𝑂(𝑔)

Reactions of chromium

a) With air
Chromium is unaffected by air at ordinary temperature.
Heated chromium reacts with air to form chromium(III) oxide
4Cr(𝑠) + 3𝑂2(𝑔) → 2𝐶𝑟2𝑂3(𝑠)

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b) With water
Heated chromium reacts with steam to form chromium(III) oxide and hydrogen
gas
2𝐶𝑟(𝑠) + 3𝐻2 𝑂(𝑔) → 𝐶𝑟2 𝑂3 (𝑠) + 3𝐻2 (𝑔)
c) With chlorine
Heated chromium reacts with dry chlorine to form chromium(III) chloride
2𝐶𝑟(𝑠) + 3𝐶𝑙2 (𝑔) → 2𝐶𝑟𝐶𝑙3 (𝑠)

d) With alkalis
Chromium reacts with hot concentrated sodium hydroxide solution forming a
green solution of sodium chromate(III) and hydrogen gas
2𝐶𝑟(𝑠) + 2𝑂̅𝐻 + 6𝐻2 𝑂(𝑙) → 2𝐶𝑟(𝑂𝐻)− 4 (𝑎𝑞) + 3𝐻2 (𝑔)
𝑂𝑟
2𝐶𝑟(𝑠) + 2𝑂̅𝐻 + 2𝐻2 𝑂(𝑙) → 2𝐶𝑟𝑂2− (𝑎𝑞) + 3𝐻2 (𝑔)

e) With hydrogen chloride

Heated chromium reacts with dry hydrogen chloride gas to form chromium(II)
chloride
𝐶𝑟(𝑠) + 2𝐻𝐶𝑙(𝑔) → 𝐶𝑟𝐶𝑙2 (𝑠) + 𝐻2 (𝑔)
f) With acids
Chromium reacts with warm dilute sulphuric and hydrochloric acids to give the
corresponding chromium(II) salts and hydrogen gas
𝐶𝑟(𝑠) + 2𝐻+ (𝑎𝑞) → 𝐶𝑟 2+ (𝑎𝑞) + 𝐻2 (𝑔)
Chromium is oxidized by hot concentrated sulphuric acid to chromium(III)
sulphate and the acid reduced to sulphur dioxide and water
2𝐶𝑟(𝑠) + 6𝐻2 𝑆𝑂4 (𝑙) → 𝐶𝑟2 (𝑆𝑂4 )3 (𝑎𝑞) + 3𝑆𝑂2 (𝑔) + 6𝐻2 𝑂(𝑙)
Chromium is rendered passive by concentrated nitric acid

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 unstable and strong reducing
agents.
𝐶𝑟 2+ (𝑎𝑞) → 𝐶𝑟 3+ (𝑎𝑞) + 𝑒 −

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Oxidizing agents like chlorine can oxidise chromium(II) to chromium(III)
2𝐶𝑟 2+ (𝑎𝑞) + 𝐶𝑙2 (𝑔) → 2𝐶𝑟 3+ (𝑎𝑞) + 2𝐶𝑙 − (𝑎𝑞)

Chromium(II) chloride
It’s a white solid prepared by heating chromium metal in dry hydrogen chloride
𝐶𝑟(𝑠) + 2𝐻𝐶𝑙(𝑔) → 𝐶𝑟𝐶𝑙2 (𝑠) + 𝐻2 (𝑔)

Chromium(II) hydroxide
It’s a yellow solid precipitates when a little alkali is added to solution of
chromium(II) salt
𝐶𝑟 2+ (𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)2 (𝑠)

Chromium(III) compounds
Chromium(III) oxide
It is a green ionic and amphoteric solid that can be obtained by heating
chromium(III) hydroxide or ammonium dichromate
2𝐶𝑟(𝑂𝐻)3 (𝑠) → 𝐶𝑟2 𝑂3 (𝑠) + 3𝐻2 𝑂(𝑙)
(𝑁𝐻4 )2 𝐶𝑟2 𝑂7 (𝑠) → 𝐶𝑟2 𝑂3 (𝑠) + 𝑁2 (𝑔) + 4𝐻2 𝑂(𝑙)
It is and amphoteric oxide
It reacts with acids to form corresponding chromium(III) salts
𝐶𝑟2 𝑂3 (𝑠) + 6𝐻+ (𝑎𝑞) → 2𝐶𝑟 3+ (𝑎𝑞) + 3𝐻2 𝑂(𝑙)

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

𝐶𝑟2 𝑂3 (𝑠) + 2𝑂̅𝐻 + 3𝐻2 𝑂(𝑙) → 2𝐶𝑟(𝑂𝐻)− 4 (𝑎𝑞)
𝑂𝑟
𝐶𝑟2 𝑂3 (𝑠) + 2𝑂̅𝐻 → 2𝐶𝑟𝑂2− (𝑎𝑞) + 𝐻2 𝑂(𝑙)

Chromium(III) hydroxide
It is a green amphoteric solid formed by precipitation when a little alkali is added to
a solution chromium(III) salt
𝐶𝑟 3+ (𝑎𝑞) + 3𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)3 (𝑠)

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

𝐶𝑟(𝑂𝐻)3 (𝑠) + 3𝐻+ (𝑎𝑞) → 𝐶𝑟 3+ (𝑎𝑞) + 3𝐻2 𝑂(𝑙)

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It reacts with alkalis to form chromate(III) salts
𝐶𝑟(𝑂𝐻)3 (𝑠) + 𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)− 4 (𝑎𝑞)

In presence of alkali, it is oxidised by hydrogen peroxide or sodium peroxide to a

yellow chromate(VI)

𝐶𝑟(𝑂𝐻)3 (𝑠) + 3𝐻2 𝑂2 (𝑎𝑞) + 4𝑂̅𝐻(𝑎𝑞) → 2𝐶𝑟𝑂42− (𝑎𝑞) + 8𝐻2 𝑂(𝑙)

Or

𝐶𝑟(𝑂𝐻)− ̅
4 (𝑎𝑞) + 3𝐻2 𝑂2 (𝑎𝑞) + 2𝑂 𝐻(𝑎𝑞) → 2𝐶𝑟𝑂42− (𝑎𝑞) + 8𝐻2 𝑂(𝑙)

This is a test used in qualitative analysis to confirm 𝐶𝑟 3+

A further test is done by adding hydrogen peroxide on acidified dichromate(VI) or

chromate(VI) followed by ether or butanol

Observation

An intense blue coloration of chromium peroxide or peroxochromic acid (𝐶𝑟𝑂5 ) is

seen in the organic layer

𝐶𝑟2 𝑂72− (𝑎𝑞) + 4𝐻2 𝑂2 (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 2𝐶𝑟𝑂5 (𝑎𝑞) + 5𝐻2 𝑂(𝑙)

𝐶𝑟𝑂42− (𝑎𝑞) + 2𝐻2 𝑂2 (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 2𝐶𝑟𝑂5 (𝑎𝑞) + 5𝐻2 𝑂(𝑙)

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 and
forming a green precipitate.

[𝐶𝑟(𝐻2 𝑂)6 ]3+ (𝑎𝑞) + 3𝐻2 𝑂 → [𝐶𝑟(𝐻2 𝑂)3 (𝑂𝐻)3 ](𝑠) + 3𝐻3 𝑂+ (𝑎𝑞)

14
Chromium(VI) compounds

Chromium(VI) oxide or chromium trioxide (𝑪𝒓𝑶𝟑)

Chromium(VI) oxide is a dark red that can be prepared by adding concentrated
sulphuric acid to a saturated solution of potassium dichromate and then cooled
𝐶𝑟2 𝑂72− (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 2𝐶𝑟𝑂3 (𝑠) + 𝐻2 𝑂(𝑙)

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

4𝐶𝑟𝑂3 (𝑠) → 2𝐶𝑟2 𝑂3 (𝑠) + 3𝑂2 (𝑔)

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

𝐶𝑟𝑂3 (𝑠) + 𝐻2 𝑂(𝑙) → 𝐻2 𝐶𝑟𝑂4 (𝑙)

It also reacts with alkalis to form chromates(VI)

𝐶𝑟𝑂3 (𝑠) + 2𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟𝑂42− (𝑎𝑞) + 𝐻2 𝑂(𝑙)

Chromates(VI)
These are salts derived from chromic(VI) acid.
The insoluble chromates can be prepared by precipitation reactions.
𝐵𝑎2+ (𝑎𝑞) + 𝐶𝑟𝑂42− (𝑎𝑞) → 𝐵𝑎𝐶𝑟𝑂4 (𝑠)
𝑃𝑏 2+ (𝑎𝑞) + 𝐶𝑟𝑂42− (𝑎𝑞) → 𝑃𝑏𝐶𝑟𝑂4 (𝑠)
𝐴𝑔+ (𝑎𝑞) + 𝐶𝑟𝑂42− (𝑎𝑞) → 𝐴𝑔2 𝐶𝑟𝑂4 (𝑠)
All the above chromates are yellow except silver chromate which is a dark red
solid.
Chromates are stable in alkaline medium. In acidic medium, they convert to
dichromates
2𝐶𝑟𝑂42− (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 𝐶𝑟2 𝑂72− (𝑎𝑞) + 𝐻2 𝑂(𝑙)

Dichromtes(VI)
These are orange coloured salts containing the dichromate ion, 𝐶𝑟2 𝑂72−
Dichromates can be obtained by adding dilute sulphuric acid to a solution of a
chromate
2𝐶𝑟𝑂42− (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 𝐶𝑟2 𝑂72− (𝑎𝑞) + 𝐻2 𝑂(𝑙)

15
Dichromates are stable in acidic medium. In alkaline medium they convert to
chromates
𝐶𝑟2 𝑂72− (𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 2𝐶𝑟𝑂42− (𝑎𝑞) + 𝐻2 𝑂(𝑙)

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

𝐶𝑟2 𝑂72− (𝑎𝑞) + 14𝐻+ (𝑎𝑞) + 6𝑒 − → 2𝐶𝑟 3+ (𝑎𝑞) + 7𝐻2 𝑂(𝑙)

However, they are not strong enough to oxidise chlorides to chlorine therefore they
can be used in the presence of hydrochloric acid in volumetric analysis.

Examples of reactions where dichromates act as oxidizing agents

(a) Oxidation of iron(II) to iron(III)
6𝐹𝑒2+(𝑎𝑞) + 𝐶𝑟2𝑂72−(𝑎𝑞) + 14𝐻+(𝑎𝑞) → 6𝐹𝑒3+(𝑎𝑞) + 2𝐶𝑟3+(𝑎𝑞) + 7𝐻2𝑂(𝑙)
Observation: The orange solution turns green

(b) Oxidation of iodide ions to iodine

6𝐼−(𝑎𝑞) + 𝐶𝑟2𝑂72−(𝑎𝑞) + 14𝐻+(𝑎𝑞) → 3𝐼2(𝑎𝑞) + 2𝐶𝑟3+(𝑎𝑞) + 7𝐻2𝑂(𝑙)
Observation: The orange solution turns brown

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

3𝑆𝑛2+(𝑎𝑞) + 𝐶𝑟2𝑂72−(𝑎𝑞) + 14𝐻+(𝑎𝑞) → 3𝑆𝑛4+(𝑎𝑞) + 2𝐶𝑟3+(𝑎𝑞) + 7𝐻2𝑂(𝑙)
Observation: The orange solution turns green

(d) Oxidation of ethanol to ethanal and ethanoic acid

3CH3CH2OH(𝑎𝑞)+𝐶𝑟2𝑂72−(𝑎𝑞)+8𝐻+(𝑎𝑞)→3CH3CHO(𝑎𝑞)+2𝐶𝑟3+(𝑎𝑞)+
7𝐻2𝑂(𝑙)
3CH3CHO(𝑎𝑞)+𝐶𝑟2𝑂72−(𝑎𝑞)+8𝐻+(𝑎𝑞)→3CH3COOH(𝑎𝑞)+2𝐶𝑟3+(𝑎𝑞)+ 4𝐻2𝑂(𝑙)
Observation: The orange solution turns green

Qualitative analysis of 𝑪𝒓𝟑+

1. Sodium hydroxide solution
Observation: Green precipitate soluble in excess to
form a green solution
𝐶𝑟 3+ (𝑎𝑞) + 3𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)3 (𝑠)
𝐶𝑟(𝑂𝐻)3 (𝑠) + 𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)− 4 (𝑎𝑞)

16
 2. Ammonia solution
Observation Green precipitate insoluble in excess
𝐶𝑟 3+ (𝑎𝑞) + 3𝑂̅𝐻(𝑎𝑞) → 𝐶𝑟(𝑂𝐻)3 (𝑠)
3. Sodium hydroxide and hydrogen peroxide
Observation: A yellow solution on warming
2𝐶𝑟 3+ (𝑎𝑞) + 3𝐻2 𝑂2 (𝑎𝑞) + 10𝑂̅𝐻(𝑎𝑞) → 2𝐶𝑟𝑂42− (𝑎𝑞) + 8𝐻2 𝑂(𝑙)
4. Sodium hydroxide, hydrogen peroxide, butanol and dilute sulphuric
acid
Observation: A blue solution in the organic layer
2𝐶𝑟 3+ (𝑎𝑞) + 3𝐻2 𝑂2 (𝑎𝑞) + 10𝑂̅𝐻(𝑎𝑞) → 2𝐶𝑟𝑂42− (𝑎𝑞) + 8𝐻2 𝑂(𝑙)
𝐶𝑟𝑂42− (𝑎𝑞) + 𝐻2 𝑂2 (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 2𝐶𝑟𝑂5 (𝑎𝑞) + 5𝐻2 𝑂(𝑙)
Or
𝐶𝑟2 𝑂72− (𝑎𝑞) + 4𝐻2 𝑂2 (𝑎𝑞) + 2𝐻+ (𝑎𝑞) → 2𝐶𝑟𝑂5 (𝑎𝑞) + 5𝐻2 𝑂(𝑙)

MANGANESE
Atomic number: 25

Electronic configuration: 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟔 𝟑𝒔𝟐 𝟑𝒑𝟔 𝟑𝒅𝟓 𝟒𝒔2

It is a grey or silvery white brittle metal that occurs naturally as pyrolusite, MnO2

It’s obtained by electrolysis of Mn2+

Or by thermit process

3𝑀𝑛3 𝑂4 (𝑠) + 8𝐴𝑙(𝑠) → 4𝐴𝑙2 𝑂3 (𝑠) + 9𝑀𝑛(𝑙)

Reactions of manganese

With air
Heated manganese burns in air to form a mixture of trimanganese tetraoxide.
3Mn(𝑠) + 2𝑂2(𝑔) → 𝑀𝑛3𝑂4(𝑠)

With water
Heated manganese reacts with steam to form trimanganese tetraoxide and
hydrogen gas
3Mn(𝑠) + 4𝐻2O(𝑔) → 𝑀𝑛3𝑂4(𝑠) + 4𝐻2(𝑔)

17
 With acids
Manganese reacts rapidly with cold dilute hydrochloric acid and sulphuric acid to
form the corresponding manganese(II) salt and hydrogen gas
Mn(𝑠) + 2𝐻+(𝑎𝑞) → 𝑀𝑛2+(𝑎𝑞) + 𝐻2(𝑔)

Manganese reacts with cold dilute nitric acid to form manganese(II) nitrate, nitrogen
monoxide and water
3Mn(𝑠) + 8𝐻𝑁𝑂3(𝑎𝑞) → 3𝑀𝑛(𝑁𝑂3)2(𝑎𝑞) + 2𝑁𝑂(𝑔) + 𝐻2𝑂(𝑙)

Manganese is oxidized by hot concentrated sulphuric acid to manganese(II) sulphate

and the acid reduced to sulphur dioxide and water
Mn(𝑠) + 2𝐻2𝑆𝑂4(𝑎𝑞) → 𝑀𝑛𝑆𝑂4(𝑎𝑞) + 2𝑆𝑂2(𝑔) + 2𝐻2𝑂(𝑙)

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

the acid reduced to nitrogen dioxide and water
Mn(𝑠) + 4𝐻𝑁𝑂3(𝑎𝑞) → 𝑀𝑛(𝑁𝑂3)2(𝑎𝑞) + 2𝑁𝑂2(𝑔) + 2𝐻2𝑂(𝑙)

Chlorine

Heated manganese reacts chlorine to form manganese(II) chloride

Mn(𝑠) + 𝐶𝑙2(𝑔) → 𝑀𝑛𝐶𝑙2(𝑠)

COMPOUNDS OF MANGANESE
Manganese exhibits oxidation states of +2, +3, +4, +5, +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
𝑀𝑛(𝑂𝐻)2(𝑠) → 𝑀𝑛𝑂(𝑠) + 𝐻2𝑂(𝑙)
𝑀𝑛𝐶𝑂3(𝑠) → 𝑀𝑛𝑂(𝑠) + 𝐶𝑂2(𝑔)

18
𝑀𝑛𝐶2𝑂4(𝑠) → 𝑀𝑛𝑂(𝑠) + 𝐶𝑂2(𝑔) + 𝐶𝑂(𝑔)

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

𝑀𝑛O(𝑠) + 2𝐻+(𝑎𝑞) → 𝑀𝑛2+(𝑎𝑞) + 𝐻2𝑂(𝑙)

Manganese(II) hydroxide, Mn(OH)2

Obtained as a white precipitate when sodium hydroxide or ammonia solution is
added to a solution of manganese(II) salt
𝑀𝑛2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑀𝑛(𝑂𝐻)2(𝑠)

The white precipitate turns brown due to oxidation by oxygen from air to form
hydrated manganese(IV) oxide
2𝑀𝑛(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 2𝑀𝑛𝑂2. 𝐻2O(𝑠)

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

Manganese(II) salts
Most manganese(II) salts are pink. Manganese(II) carbonate is red. Though
practically are taken to be white/colourless
Manganese(III) compounds
Compounds of manganese in this state are uncommon because of disproportionation
2𝑀𝑛3+(𝑎𝑞) + 2𝐻2𝑂(𝑙) → 𝑀𝑛2+(𝑎𝑞) + 𝑀𝑛𝑂2(𝑠) + 4𝐻+(𝑎𝑞)

Manganese(IV) compounds
Manganese(IV) oxide, MnO2
Anhydrous manganese(IV) oxide is a black solid prepared by heating manganese(II)
nitrate
Mn(𝑁𝑂3)2(𝑠) → 𝑀𝑛𝑂2(𝑠) + 2𝑁𝑂2(𝑔)

Also by oxidation of manganese(II) salts using sodium hypochlorite and sodium

hydroxide
𝑀𝑛2+(𝑎𝑞) + 𝑂𝐶𝑙−(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑀𝑛𝑂2(𝑠) + 𝐶𝑙−(𝑎𝑞) + 𝐻2𝑂(𝑙)

Manganese(IV) oxide is essentially ionic.

19
It dissolves in cold concentrated hydrochloric acid to form
hexachloromanganate(IV)
𝑀𝑛𝑂2(𝑠) + 4𝐻+ + 6𝐶𝑙−(𝑎𝑞) → 𝑀𝑛𝐶𝑙62−(𝑎𝑞) + 2𝐻2𝑂(𝑙)

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

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

Manganese(IV) oxide reacts with hot concentrated sulphuric acid to liberate oxygen
2𝑀𝑛𝑂2(𝑠) + 2𝐻2𝑆𝑂4(𝑙) → 2𝑀𝑛𝑆𝑂4(𝑎𝑞) + 𝑂2(𝑔) + 2𝐻2𝑂(𝑙)

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

𝑀𝑛𝑂2(𝑠) + 𝐶2𝑂42−(𝑎𝑞) + 4𝐻+(𝑎𝑞) → 𝑀𝑛2+(𝑎𝑞) + 2𝐶𝑂2(𝑔) + 𝐻2𝑂(𝑙)

Determination of the percentage of manganese(IV) oxide in 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
𝑀𝑛𝑂2(𝑠) + 4𝐻𝐶𝑙(𝑎𝑞) → 𝑀𝑛𝐶𝑙2(𝑎𝑞) + 𝐶𝑙2(𝑔) + 2𝐻2𝑂(𝑙)

The chlorine liberated is bubbled through excess potassium iodide solution to

liberate iodine

𝐶𝑙2(𝑔) + 2𝐼−(𝑎𝑞) → 𝐼2(𝑎𝑞) + 2𝐶𝑙−(𝑎𝑞)

A known volume of the solution containing the liberated iodine is then titrated with
a standard solution of sodium thiosulphate using starch indicator
𝐼2(𝑎𝑞) + 2𝑆2𝑂32−(𝑎𝑞) → 2𝐼−(𝑎𝑞) + 𝑆4𝑂62−(𝑎𝑞)

The mass of manganese(IV) oxide is calculated and the percentage of the ore
calculated as
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑎𝑛𝑎𝑔𝑎𝑛𝑒𝑠𝑒(𝐼𝑉)𝑜𝑥𝑖𝑑𝑒
Percentage of manganese(IV)oxide =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑜𝑟𝑒
Manganese(VI) compounds
Sodium and potassium manganate(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.
2𝑀𝑛𝑂2(𝑠) + 4𝐾𝑂𝐻(𝑠) + 𝑂2(𝑔) → 2𝐾2𝑀𝑛𝑂4(𝑠) + 2𝐻2𝑂(𝑙)

20
It is also formed by fusing manganese(IV) oxide and sodium peroxide

𝑀𝑛𝑂2(𝑠) + Na2𝑂2(s) → 2Na2𝑀𝑛𝑂4(𝑠)

Manganate(VI) ions only stable in alkaline medium.

In acidic or neutral medium, it undergoes disproportionation

3𝑀𝑛𝑂42−(𝑎𝑞) + 4𝐻+ → 2𝑀𝑛𝑂4−(𝑎𝑞) + 𝑀𝑛𝑂2(𝑠) + 2𝐻2𝑂(𝑙)
Or
3𝑀𝑛𝑂42−(𝑎𝑞) + 2𝐻2𝑂(𝑙) → 2𝑀𝑛𝑂4−(𝑎𝑞) + 𝑀𝑛𝑂2(𝑠) + 4𝑂̅𝐻(𝑎𝑞)
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
3𝑀𝑛𝑂42−(𝑎𝑞) + 2𝐶𝑂2(𝑔) → 2𝑀𝑛𝑂4−(𝑎𝑞) + 𝑀𝑛𝑂2(𝑠) + 2𝐶𝑂32−(𝑎𝑞)

Manganese(VII) compounds
Potassium manganate(VII)
It is dark purple crystalline compound soluble in water forming a purple solution.
It is prepaered in the laboratory by fusing manganese(IV) oxide with potassium
hydroxide and potassium chlorate(V)
2𝑀𝑛𝑂2 (𝑠) + 2𝐾𝑂𝐻(𝑙) + 𝐾𝐶𝑙𝑂3 (𝑙) → 2𝐾𝑀𝑛𝑂4 (𝑙) + 2𝐾𝐶𝑙(𝑙) + 𝐻2 𝑂(𝑙)
Uses of potassium manganate(VII)
• It is used in the laboratory for preparation of chlorine gas and testing for the
presence of sulphur dioxide, unsaturated hydrocarbons.
• 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 manganate(VII) during the reaction.
Hydrochloric acid is not used because it is easily oxidized to chlorine.
2𝑀𝑛𝑂4−(𝑎𝑞) + 16𝐻+(𝑎𝑞) + 10𝐶𝑙−(𝑎𝑞) → 2𝑀𝑛2+(𝑎𝑞) + 8𝐻2𝑂(𝑙) + 5𝐶𝑙2(𝑔)

Advantages of using potassium permanganate in volumetric analysis

• It is a self- 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

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Why potassium manganate(VII) is not used as a primary standard
• It is always found contaminated with manganese(IV) oxide
• It is not highly stable. In light, a solution of acidified potassium
manganate(VII) will decompose to form manganese(IV) oxide
4𝑀𝑛𝑂4−(𝑎𝑞) + 4𝐻+(𝑎𝑞) → 2𝑀𝑛𝑂2(𝑠) + 2𝐻2𝑂(𝑙) + 3𝑂2(𝑔)

Even in alkaline medium, decomposition will occur as follows

4𝑀𝑛𝑂4−(𝑎𝑞) + 2𝐻2𝑂(𝑙) → 4𝑀𝑛𝑂2(𝑠) + 4𝑂̅𝐻(𝑎𝑞) + 3𝑂2(𝑔)

Oxidizing properties potassium manganate(VII)

In neutral or slightly alkaline medium manganate(VII) is reduced to manganese(IV)
oxide
𝑀𝑛𝑂4−(𝑎𝑞) + 2𝐻2𝑂(𝑙) + 3𝑒− → 𝑀𝑛𝑂2(𝑠) + 4𝑂̅𝐻(𝑎𝑞)

For example, oxidation of iodide to iodate

2𝑀𝑛𝑂4−(𝑎𝑞) + 𝐻2𝑂(𝑙) + 𝐼−(𝑎𝑞) → 𝑀𝑛𝑂2(𝑠) + 2𝑂̅𝐻(𝑎𝑞) + 𝐼𝑂3−(𝑎𝑞)

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

𝑀𝑛𝑂4−(𝑎𝑞) + 𝑒− → 𝑀𝑛𝑂42−(𝑎𝑞)

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

solution turns from purple to colourless
𝑀𝑛𝑂4−(𝑎𝑞) + 8𝐻+ + 5𝑒− → 𝑀𝑛2+(𝑎𝑞) + 4𝐻2𝑂(𝑙)

a) Oxidation of nitrites to nitrates

2𝑀𝑛𝑂4−(𝑎𝑞) + 6𝐻+ + 5𝑁𝑂2− → 2𝑀𝑛2+(𝑎𝑞) + 3𝐻2𝑂(𝑙) + 5𝑁𝑂3−(𝑎𝑞)

b) Oxidation of hydrogen peroxide to oxygen

2𝑀𝑛𝑂4−(𝑎𝑞) + 16𝐻+ + 5𝐻2𝑂2(𝑙) → 2𝑀𝑛2+(𝑎𝑞) + 8𝐻2𝑂(𝑙) + 5𝑂2(𝑔)

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

2𝑀𝑛𝑂4−(𝑎𝑞) + 16𝐻+ + 5𝑆𝑛2+(𝑎𝑞) → 2𝑀𝑛2+(𝑎𝑞) + 8𝐻2𝑂(𝑙) + 5𝑆𝑛4+(𝑎𝑞)

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

22
𝑀𝑛𝑂4−(𝑎𝑞) + 8𝐻+ + 5𝐹𝑒2+(𝑎𝑞) → 2𝑀𝑛2+(𝑎𝑞) + 4𝐻2𝑂(𝑙) + 5𝐹𝑒3+(𝑎𝑞)

Observation: The solution turns from purple to brown

e) Oxidation of hydrogen sulphide to sulphur
2𝑀𝑛𝑂4−(𝑎𝑞) + 16𝐻+ + 5𝑆2−(𝑎𝑞) → 2𝑀𝑛2+(𝑎𝑞) + 8𝐻2𝑂(𝑙) + 5𝑆(𝑠)

Observation: The solution turns from purple to colourless with formation of a yellow
deposit (solid)

Qualitative analysis of 𝑴𝒏𝟐+

1. Sodium hydroxide solution
Observation: A white precipitate that rapidly turns
brown on standing.
𝑀𝑛2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑀𝑛(𝑂𝐻)2(𝑠)
2Mn(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 2𝑀𝑛𝑂2.𝐻2O(𝑠)
Or
4Mn(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 2𝑀𝑛2𝑂3.2𝐻2𝑂(𝑠)
2. Ammonia solution
Observation: A white precipitate that rapidly turns
brown on standing.
𝑀𝑛2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑀𝑛(𝑂𝐻)2(𝑠)
4Mn(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 2𝑀𝑛2𝑂3.2𝐻2𝑂(𝑠)
3. Sodium bismuthate, NaBiO3
Add concentrated nitric acid followed by solid sodium bismuthate
Observation: A purple solution is formed.
2𝑀𝑛2+(𝑎𝑞) + 5𝐵𝑖𝑂3−(𝑎𝑞) + 14𝐻+(𝑎𝑞) → 2𝑀𝑛𝑂4−(𝑎𝑞) + 5𝐵𝑖3+(𝑎𝑞) + 7𝐻2𝑂(𝑙)
4. Lead(IV) oxide and warm
Add concentrated nitric acid followed by solid lead(IV) oxide
Observation: A purple solution is formed.
2𝑀𝑛2+(𝑎𝑞) + 5𝑃𝑏𝑂2(𝑠) + 4𝐻+(𝑎𝑞) → 2𝑀𝑛𝑂4−(𝑎𝑞) + 5𝐵𝑖3+(𝑎𝑞) + 2𝐻2𝑂(𝑙)

23
 IRON
Atomic number: 26

Electronic configuration: 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟔 𝟑𝒔𝟐 𝟑𝒑𝟔 𝟑𝒅6 𝟒𝒔2

Extraction of iron
The chief ore from which iron is extracted is haematite, 𝐹𝑒2𝑂3.
The other ores of iron are
Magnetite, 𝐹𝑒3𝑂4
Iron pyrites 𝐹𝑒𝑆2
Siderite or spathic iron, 𝐹𝑒𝐶𝑂3

Extraction of iron from haematite

The iron ore is crushed into small particles which are roasted in air to drive out water
and other volatile impurities as well as oxidizing iron(II) oxide to iron(III) oxide.
A mixture of the roasted ore, coke and limestone are fed into the blast furnace from
the top.
Hot compressed air is driven into the furnace from the bottom

Coke burns in the hot air to form carbon dioxide

C(𝑠) + 𝑂2(𝑔) → 𝐶𝑂2(𝑔)
Carbon dioxide is reduced by the unburnt coke to carbon monoxide
C(𝑠) + 𝐶𝑂2(𝑔) → 2𝐶𝑂(𝑔)
The carbon monoxide then reduces the iron ore to molten iron

24
𝐹𝑒2𝑂3(𝑠) + 3𝐶𝑂(𝑔) → 2𝐹𝑒(𝑠) + 3𝐶𝑂2(𝑔)

Limestone decomposes to calcium oxide and carbon dioxide

𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

Calcium oxide reacts with silicon(IV) oxide (the impurity) to form molten slag
of calcium silicate.

CaO(𝑠) + 𝑆𝑖𝑂2(𝑠) → 𝐶𝑎𝑆𝑖𝑂3(𝑙)

Note: Extraction of iron from spathic iron or pyrites requires the ores to be first
roasted in air and then fed in the blast furnace with coke and limestone

4Fe𝐶𝑂3(𝑠) + 𝑂2(g) → 2𝐹𝑒2𝑂3(𝑠) + 4𝐶𝑂2(𝑔)

4FeS2(𝑠) + 9𝑂2(g) → 2𝐹𝑒2𝑂3 (𝑠) + 8S𝑂2(𝑔)

Reactions of iron
With air
Heated iron reacts with air to form triiron tetraoxide
3Fe(𝑠) + 2𝑂2(𝑔) → 𝐹𝑒3𝑂4(𝑠)

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

4𝐹𝑒(𝑠) + 3𝑂2 (𝑔) + 2𝑥𝐻2 𝑂(𝑙) → 2𝐹𝑒2 𝑂3 . 𝑥𝐻2 𝑂(𝑠)

With water
Heated iron reacts with steam to form triiron tetraoxide and hydrogen gas

3Fe(𝑠) + 4𝐻2(𝑔) ⇋ 𝐹𝑒3𝑂4(𝑠) + 4𝐻2(𝑔)

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

4𝐹𝑒(𝑠) + 3𝑂2 (𝑔) + 2𝑥𝐻2 𝑂(𝑙) → 2𝐹𝑒2 𝑂3 . 𝑥𝐻2 𝑂(𝑠)

With acids

25
Dilute acids
Iron reacts with cold dilute sulphuric and hydrochloric acids to form hydrogen gas
the corresponding iron(II) salt.
Fe(𝑠) + 2𝐻+(𝑎𝑞) → 𝐹𝑒2+(𝑎𝑞) + 𝐻2(𝑔)

Iron reacts with dilute nitric acid to form a mixture of products.

4Fe(𝑠) + 10𝐻𝑁𝑂3(𝑎𝑞) → 4𝐹𝑒(𝑁𝑂3)2(𝑎𝑞) + 𝑁𝐻4𝑁𝑂3(𝑎𝑞) + 3𝐻2𝑂(𝑙)

Concentrated acids
Hot concentrated sulphuric acid oxidizes iron to iron(III) sulphate and the acid is
reduced to sulphur dioxide and water
2Fe(𝑠) + 6𝐻2𝑆𝑂4(𝑙) → 𝐹𝑒2(𝑆𝑂4)3(𝑎𝑞) + 3𝑆𝑂2(𝑔) + 6𝐻2𝑂(𝑙)

Concentrated nitric acid renders iron passive.

With sulphur
When a mixture of iron and sulphur is heated, a red glow is observed and black solid
is formed
𝐹𝑒(𝑠) + 𝑆(𝑠) → 𝐹𝑒𝑆(𝑠)

With chlorine
Heated iron reacts with dry chlorine to form iron(III) chloride
2Fe(𝑠) + 3𝐶𝑙2(𝑔) → 2𝐹𝑒𝐶𝑙3(𝑠)

With hydrogen chloride

Heated iron reacts with dry hydrogen chloride gas to form iron(II) chloride and
hydrogen gas
Fe(𝑠) + 2HCl(𝑔) → 𝐹𝑒𝐶𝑙2(𝑠) + 𝐻2(𝑔)

Compounds of iron
The principal oxidation states of iron are +2 and +3. The loss of two electrons from
the 4s orbital gives iron(II) ion, 𝐹𝑒2+, while the loss of two electrons from the 4s and
one electron from the 3d orbitals gives iron(III) ion.
Because the 3d orbital is half filled, the iron(III) ion and the compounds are more
stable than the iron(II) ion and compounds. This is why iron(II) compounds easily
oxidize to iron(III) compounds.

26
 Iron(II) compounds
Iron(II) oxide
It is a black solid that can be obtained by heating iron(II) oxalate in the absence of
air.
𝐹𝑒𝐶2𝑂4(𝑠) → 𝐹𝑒𝑂(𝑠) + 𝐶𝑂(𝑔) + 𝐶𝑂2(𝑔)

It is a basic solid that readily reacts with dilute acids to form iron(II) salts and water
𝐹𝑒𝑂(𝑠) + 2𝐻+(𝑎𝑞) → 𝐹𝑒2+(𝑎𝑞) + 𝐻2𝑂(𝑙)
Iron(II) hydroxide
It is obtained as a green precipitate by adding an alkali such as sodium hydroxide
solution to a solution of iron(II) salt.
𝐹𝑒2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)2(𝑠)

It is basic and reacts with dilute acids to form iron(II) salts and water
Fe(𝑂𝐻)2(𝑠) + 2𝐻+(𝑎𝑞) → 𝐹𝑒2+(𝑎𝑞) + 2𝐻2𝑂(𝑙)

Iron(II) sulphate-7-water
In the laboratory, it is prepared by the action of dilute sulphuric acid on iron filings
and crystallizing the salt from the solution.
Fe(𝑠) + 𝐻2𝑆𝑂4(𝑎𝑞) → 𝐹𝑒𝑆𝑂4(𝑎𝑞) + 𝐻2(𝑔)
𝐹𝑒𝑆𝑂4(𝑎𝑞) + 7𝐻2𝑂(𝑙) → 𝐹𝑒𝑆𝑂4.7𝐻2𝑂(𝑠)

Hydrated iron(II) sulphate decomposes when heated, first to white anhydrous

iron(II) sulphate.
𝐹𝑒𝑆𝑂4. 7𝐻2O(𝑠) → 𝐹𝑒𝑆𝑂4(𝑠) + 7𝐻2𝑂(𝑙)

On strong heating, it decomposes to iron(III) oxide, sulphur dioxide and sulphur

trioxide. 2𝐹𝑒𝑆𝑂4(𝑠) → 𝐹𝑒2𝑂3(𝑠) + 𝑆𝑂2(𝑔) + 𝑆𝑂3(𝑔)

Iron(III) compounds
Iron(III) oxide
It can be obtained as a brown solid by heating iron(II) sulphate or Iron(II) hydroxide
2𝐹𝑒𝑆𝑂4(𝑠) → 𝐹𝑒2𝑂3(𝑠) + 𝑆𝑂2(𝑔) + 𝑆𝑂3(𝑔)
2Fe(𝑂𝐻)3(𝑠) → 𝐹𝑒2𝑂3(𝑠) + 3𝐻2𝑂(𝑙)

27
It is basic and readily reacts with hot dilute acids to form iron(III) salts and water
𝐹𝑒2𝑂3(𝑠) + 6𝐻+(𝑎𝑞) → 2𝐹𝑒3+(𝑎𝑞) + 3𝐻2𝑂(𝑙)

Iron(III) hydroxide
It precipitated as a brown solid when an alkali such as sodium hydroxide is added to
an aqueous solution of iron(III) salt.
𝐹𝑒3+(𝑎𝑞) + 3𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)3(𝑠)

It is basic and reacts with dilute acids to form iron(III) salts and water
Fe(𝑂𝐻)3(𝑠) + 3𝐻+(𝑎𝑞) → 𝐹𝑒3+(𝑎𝑞) + 3𝐻2𝑂(𝑙)

Iron(III) chloride
Anhydrous iron(III) chloride is prepared as a black sublimate by passing dry
chlorine over heated iron wire.
2Fe(𝑠) + 3𝐶𝑙2(𝑔) → 2𝐹𝑒𝐶𝑙3(𝑠)

It is a covalent solid which exists as a dimer, 𝐹𝑒2𝐶𝑙6, in the vapour phase.

Hydrolysis of iron(III) salts in water

Solutions of iron(III) salts are acidic. This is because of hydrolysis of the hydrated
iron(III) cation.
The iron(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.

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

Qualitative analysis of 𝑭𝒆𝟐+

1. Sodium hydroxide solution

Observation: Green precipitate insoluble in excess that turns brown on standing
𝐹𝑒2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)2(𝑠)
4Fe(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) + 2𝐻2𝑂(𝑙) → 4𝐹𝑒(𝑂𝐻)3(𝑠)
Or
4Fe(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 𝐹𝑒2𝑂3.2H2O(𝑠)

2. Ammonia solution

28
 Observation: Green precipitate insoluble in excess that turns brown on standing
𝐹𝑒2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)2(𝑠)
4Fe(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) + 2𝐻2𝑂(𝑙) → 4𝐹𝑒(𝑂𝐻)3(𝑠)
Or
4Fe(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 𝐹𝑒2𝑂3.2H2O(𝑠)
3. Potassium hexacyanoferrate(III) solution
Observation: A dark blue precipitate
𝐹𝑒2+(𝑎𝑞) + 𝐾+(𝑎𝑞) + [𝐹𝑒(𝐶𝑁)6]3−(𝑎𝑞) → 𝐾𝐹𝑒[𝐹𝑒(𝐶𝑁)6](𝑠)

Qualitative analysis of 𝑭𝒆𝟑+

1. Sodium hydroxide solution
Observation: Brown precipitate insoluble in excess

𝐹𝑒3+(𝑎𝑞) + 3𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)3(𝑠)

2. Aqueous ammonia
Observation: Brown precipitate insoluble in excess

𝐹𝑒3+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐹𝑒(𝑂𝐻)3(𝑠)

3. Potassium (or ammonium) thiocyanate solution

Observation: A blood red coloration (solution)

𝐹𝑒3+(𝑎𝑞) + 𝑆𝐶𝑁−(𝑎𝑞) → [𝐹𝑒(𝑆𝐶𝑁)]2+(𝑎𝑞)

4. Potassium hexacyanoferrate(II) solution

Observation: A dark blue precipitate

𝐹𝑒3+(𝑎𝑞) + 𝐾+(𝑎𝑞) + [𝐹𝑒(𝐶𝑁)6]4−(𝑎𝑞) → 𝐾𝐹𝑒[𝐹𝑒(𝐶𝑁)6](𝑠)

COBALT
Atomic number: 27

Electronic configuration: 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟔 𝟑𝒔𝟐 𝟑𝒑𝟔 𝟑𝒅7 𝟒𝒔2

29
Reactions of cobalt

With air
Heated cobalt reacts with to form tricobalt tetraoxide
3Co(𝑠) + 2𝑂2(𝑔) → 𝐶𝑜3𝑂4(𝑠)

With water
Heated cobalt reacts steam to form tricobalt tetraoxide and hydrogen gas
3𝐶o(𝑠) + 4𝐻2𝑂(𝑔) → 𝐶o3𝑂4(𝑠) + 4𝐻2(𝑔)

With chlorine
Heated cobalt reacts with dry chlorine to form cobalt(II) chloride
Co(𝑠) + 𝐶𝑙2(𝑔) → 𝐶𝑜𝐶𝑙2(𝑠)

With acids
Dilute acids
Cobalt reacts slowly with hot dilute hydrochloric and sulphuric acid liberating
hydrogen gas and forming the corresponding cobalt(II) salts in solution
Co(𝑠) + 2𝐻+(𝑎𝑞) → 𝐶𝑜2+(𝑎𝑞) + 𝐻2(𝑔)
Concentrated acids
Cobalt is oxidized by hot concentrated sulphuric acid to cobalt(II) sulphate and the
acid reduced to sulphur dioxide and water
Co(𝑠) + 2𝐻2𝑆𝑂4(𝑙) → 𝐶𝑜𝑆𝑂4(𝑎𝑞) + 𝑆𝑂2(𝑔) + 2𝐻2𝑂(𝑙)

Cobalt is rendered passive by concentrated nitric acid

With alkalis
Cobalt has no reaction with alkalis

Compounds of cobalt
Cobalt has two principle oxidation states, +2 and +3 oxidation states
The +2 oxidation state is the most stable
The +3 oxidation state is mainly found in complexes

30
Cobalt (II) compounds
Cobalt(II) oxide
It is a green solid that can be obtained by heating cobalt(II) hydroxide, carbonate or
nitrate.
𝐶𝑜𝐶𝑂3(𝑠) → 𝐶𝑜𝑂(𝑠) + 𝐶𝑂2(𝑔)
2Co(𝑁𝑂3)2 → 2CoO(𝑠) + 4𝑁𝑂2(𝑔) + 𝑂2(𝑔)

Cobalt(II) oxide is basic. It reacts with dilute acids forming pink solutions of
cobalt(II) salts

𝐶𝑜𝑂(𝑠) + 2𝐻+(𝑎𝑞) → 𝐶𝑜2+(𝑎𝑞) + 𝐻2𝑂(𝑙)

Cobalt(II) hydroxide
It is formed as a blue precipitate when aqueous sodium hydroxide is added to a
solution of cobalt(II) salt.
𝐶𝑜2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐶𝑜(𝑂𝐻)2(𝑠)

It is also basic reacting with dilute acids to form cobalt(II) salts

𝐶𝑜(𝑂𝐻)2(𝑠) + 2𝐻+(𝑎𝑞) → 𝐶𝑜2+(𝑎𝑞) + 2𝐻2𝑂(𝑙)

Cobalt(II) chloride
The anhydrous salt is blue obtained by heating cobalt in dry chlorine or hydrogen
chloride
𝐶𝑜(𝑠) + 𝐶𝑙2(𝑔) → 𝐶𝑜𝐶𝑙2(𝑠)

The hydrated salt is red or pink

Cobalt(II) chloride turns pink in water due to formation of the hydrated ion
[𝐶𝑜(𝐻2𝑂)6]2+
When concentrated hydrochloric acid or a saturated solution of potassium chloride
is added to the solution, it changes from pink to blue

[𝐶𝑜(𝐻2𝑂)6]2+(𝑎𝑞) + 4𝐶𝑙−(𝑎𝑞) ⇋ [𝐶𝑜𝐶𝑙4]2−(𝑎𝑞) + 6𝐻2𝑂(𝑙)

This is called ligand exchange. This chloride ions have replaced water molecules as
ligands in the complex resulting in colour change.
Diluting the solution results in reforming the pink solution.

31
Cobalt (III) compounds
Cobalt(III) is the stable form in many complexes such as [𝐶𝑜(𝐻2 𝑂)6 ]3+ ,
[𝐶𝑜(𝑁𝐻3 )6 ]3+ , [𝐶𝑜(𝐶𝑁)6 ]3−

Qualitative analysis of Co2+ in solution

1. Sodium hydroxide solution
Observation: Blue precipitate insoluble in excess, turning dark
brown/pink on standing.
𝐶𝑜2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐶𝑜(𝑂𝐻)2(𝑠)
4 𝐶𝑜(𝑂𝐻)2(𝑠) + 𝑂2(𝑔) → 2𝐶𝑜2𝑂3.2𝐻2𝑂(𝑠)
2. Ammonia solution
Observation: Blue precipitate insoluble in excess and turns brown/pink
on standing
But concentrated ammonia solution gives a blue precipitate, soluble in
excess forming a yellow solution which turns red on standing
[Due to oxidation of hexaamminecobalt(II) complex to hexaammine
cobalt(III)]
𝐶𝑜2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝐶𝑜(𝑂𝐻)2(𝑠)
𝐶𝑜(𝑂𝐻)2(𝑠) + 6𝑁𝐻3(𝑎𝑞) → [𝐶𝑜(𝑁𝐻3)6]2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞)
4[Co(𝑁𝐻3)6]2+(𝑎𝑞) + 𝑂2(𝑔) + 2𝐻2𝑂(𝑙) → 4[𝐶𝑜(𝑁𝐻3)6]3+(𝑎𝑞) + 4𝑂̅𝐻(𝑎𝑞)
3. Potassium thiocyanate solution
Drops of concentrated hydrochloric acid are added first
Observation: Blue solution (of tetrathiocyanatocobaltate(II) complex)
𝐶𝑜2+(𝑎𝑞) + 4𝑆𝐶𝑁−(𝑎𝑞) → [𝐶𝑜(𝑆𝐶𝑁)4]2-(𝑎𝑞)
If ether is added to the resulting solution, the blue colour forms in the
organic layer
4. Potassium nitrite solution
Ethanoic acid is added first
Observation: A yellow precipitate (potassium hexanitritocobaltate(III)
𝐶𝑜2+(𝑎𝑞) + 3𝐾+ + 7𝑁𝑂2−(𝑎𝑞) + 2𝐻+(𝑎𝑞) → 𝐾3[𝐶𝑜(𝑁𝑂2)6](𝑠) + 𝑁𝑂(𝑔)+𝐻2𝑂(𝑙)
5. Potassium cyanide solution
Observation: Reddish brown precipitate soluble in excess forming a
reddish brown solution (containing hexacyanocobaltate(II) ion)
𝐶𝑜2+(𝑎𝑞) + 2𝐶𝑁−(𝑎𝑞) → 𝐶𝑜(𝐶𝑁)2(𝑠)
−
Co(𝐶𝑁)2(𝑠) + 4𝐶𝑁 (𝑎𝑞) → [𝐶𝑜(𝐶𝑁)6]4−(𝑎𝑞)

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 NICKEL
Atomic number: 28

Electronic configuration: 𝟏𝒔𝟐 𝟐𝒔𝟐 𝟐𝒑𝟔 𝟑𝒔𝟐 𝟑𝒑𝟔 𝟑𝒅8 𝟒𝒔2

Reactions of nickel

With air
Heated nickel reacts with air to form nickel(II) oxide, a green solid.
2𝑁𝑖(𝑠) + 𝑂2(𝑔) → 2𝑁𝑖𝑂(𝑠)

With water
Heated nickel reacts with steam to form nickel(II) oxide and hydrogen gas.
𝑁𝑖(𝑠) + 𝐻2O(𝑔) → 𝑁𝑖𝑂(𝑠) + 𝐻2(𝑔)

With acids
Nickel reacts with hot dilute acids with nitric acid inclusive to form corresponding
nickel(II) salts and hydrogen gas
𝑁𝑖(𝑠) + 2𝐻+(𝑎𝑞) → 𝑁𝑖2+(𝑠) + 𝐻2(𝑔)

Nickel is rendered passive by concentrated nitric acid

With chlorine
Heated nickel reacts with dry chlorine to form nickel(II) chloride
𝑁𝑖(𝑠) + 𝐶𝑙2(𝑔) → 𝑁𝑖𝐶𝑙2(𝑠)

Compounds of nickel
Nickel usually forms compounds in the +2 oxidation state.
Nickel(II) compounds are generally green

Nickel(II) oxide
It is a green solid that can be obtained by heating nickel(II) carbonate or nitrate or
hydroxide.
𝑁𝑖(𝑂𝐻)2(𝑠) → 𝑁𝑖𝑂(𝑠) + 𝐻2𝑂(𝑙)
𝑁𝑖𝐶𝑂3(𝑠) → 𝑁𝑖𝑂(𝑠) + 𝐶𝑂2(𝑔)
It is a basic solid that reacts with dilute acids to form the corresponding nickel(II)
salts and water

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𝑁𝑖O(𝑠) + 2𝐻+(𝑎𝑞) → 𝑁𝑖2+(𝑎𝑞) + 𝐻2𝑂(𝑙)

Qualitative analysis of Ni2+ in solution

1. Sodium hydroxide solution
Observation: Green precipitate insoluble in excess
𝑁𝑖2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑁𝑖(𝑂𝐻)2(𝑠)
2. Ammonia solution
Observation: Green precipitate soluble in excess forming a forming a
blue solution
𝑁𝑖2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞) → 𝑁𝑖(𝑂𝐻)2(𝑠)
𝑁𝑖(𝑂𝐻)2(𝑠) + 6𝑁𝐻3(𝑎𝑞) → [𝑁𝑖(𝑁𝐻3)6]2+(𝑎𝑞) + 2𝑂̅𝐻(𝑎𝑞)
3. Potassium hexacyanoferrate(II) solution
Observation: Green precipitate soluble in ammonia solution
2𝑁𝑖2+(𝑎𝑞) + [𝐹𝑒(𝐶𝑁)6]4−(𝑎𝑞) → 𝑁𝑖2[𝐹𝑒(𝐶𝑁)6] (𝑠)
4. Dimethylglyoxime (Butanedione dioxime)
Add ammonia solution followed by dimethyl glyoxime
Observation: Red precipitate

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