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Unit 5
Topic 17: Transition metals
By syed arham ahsan

Syed Arham Ahsan, IGCSE & IAL Chemistry

Contact: 01625-109261
 TRANSITION METALS
Transition metals:
Transition metals are d-block elements that form one or more stable ions with incompletely
filled d-orbitals.

Characteristics of transition metals:

Transition metals:
• are hard solids
• have high melting and boiling temperatures
• can act as catalysts
• form colored ions and compounds
• form ions with different oxidation numbers
• form ions with incompletely filled d-orbitals

Of the ten d-block elements in Period 4, the first and the last (scandium and zinc) do not
have some of these characteristics. So although, it is correct to describe them as d-block
elements, they are not considered to be transition metals.
Scandium and Zinc form only one stable ion; Sc3+ and Zn2+ respectively. However, neither of
these stable ions have an incompletely filled d-orbital and so, Scandium and Zinc cannot be
classified as transition metals.
Whenever a d-block element forms ions, it loses its electrons from the s-orbital first and then
from the d-orbital. This is because losing the 4s electrons makes an ion smaller than it would
be had it lost its 3d electrons. Thus, the lattice energy and hydration enthalpy are more
exothermic and the overall ΔH is more energetically favourable than it would be had it lost
its 3d electrons.
Questions:
Q. Using the data below, draw Borne-Haber cycles for the formation of:
1) MgCl
2) MgCl2
3) MgCl3

Value / kJmol-1
Enthalpy of atomization of Mg +148
First ionization energy of Mg +738
Second ionization energy of Mg +1451
Third ionization energy of Mg +7733
Enthalpy of atomization of Cl +123
First electron affinity of Cl -349
Lattice energy of MgCl -780
Lattice energy of MgCl2 -2526
Lattice energy of MgCl3 -4500
The highest oxidation number increases from Ti(+4) to Mn(+7) as all the 4s and 3d electrons
become involved in bonding. From Fe to Cu, the increasing nuclear charge means that the
electrons are attracted more strongly and are less likely to be involved in bonding. Therefore,
ions with higher oxidation number are less common.

Ligands and complexes:

Metal complexes / Complex compounds: It is a compound in which molecules or ions
known as ligands form dative covalent bonds with the central metal atom or ion.
Complex compounds can either be positively charged, negatively charged or neutral.

Ligands: A ligand is an ion or molecule that is bonded via a dative covalent bond to a metal
ion. An atom that is a ligand must have a lone pair of electrons.

Coordination number: It is the number of dative bonds in the complex.

Example: Hexaaquachromium(iii) ion has the formula [Cr(H2O)6]3+.

The structure of [Cr(H2O)6]3+ is shown below:
• The water molecules are called ligands.
• One of the lone pair of electrons on the oxygen atom of each water molecule forms a dative
covalent bond with an empty orbital in the Cr3+ ion.
• Six dative bonds form, so the ion has the coordination number 6.
• The ion, with its water molecules bonded to the central metal ion, is called a complex ion.

Monodentate ligands: The ion or molecule uses one pair of electrons to form a dative bond
with the central d-block ion.
For example: Cl-, Br-, I-, H2O, NH3, OH-, CN-.
In the example shown above, all the water molecules are monodentate ligands as the form
one dative covalent bond per molecule.

Bidentate ligands: Some molecules or ions have two lone pairs on different atoms and so can
form two dative bonds with the central metal ion. Such ligands are called bidentate ligands.
Example: 1,2-diaminoethane, NH2CH2CH2NH2 and ethanedioate ions, -OOCCOO-
 Figure: How monodentate ligands form dative covalent bonds with central metal ion, M.

Figure: Structure of [Cr(NH2CH2CH2NH2)3]3+

A given complex can have a maximum coordination number of 6. Since each bidentate
ligand forms two dative bonds per molecule, the central metal ion can accommodate a
maximum of 3 bidentate ligand around it when forming a complex.

Polydentate ligands: Other species can form five or six dative bonds with the central metal
ion. These are called polydentate ligands.
One of the best reagents for forming complexes of this type is the disodium salt of EDTA.
Each EDTA ligand can form six dative covalent bonds with the central metal ion and so, it is
known as a hexadentate ligand.

Figure: Ethylenediaminetetraacetate (EDTA) ion

Figure: how EDTA forms dative

bonds with central metal ion
The origin of color in complexes:
The d-orbitals in a transition metal ion are all at the same energy level, but they point in
different directions.

When six ligands approach the ion, they do so along the x-, y- and z-axes. This causes
greater repulsion with the two d-orbitals that point along the x-, y- and z-axes than with the
three that point between the axes. The energy level of the d-orbitals are split into a lower
group of three and upper group of two.

The energy difference between these two sets of d-orbitals in a typical octahedral complex
ion is equal to the energy of a photon in the visible region of the spectrum.
When white light shines through a solution of a complex ion of a transition metal, photons of
a particular frequency are absorbed and their energy promotes an electron from the lower
energy level to the upper energy level.
A color is removed from the white light and the solution has a complimentary color to the
light absorbed.

In color wheel, complimentary colors are the colors shown opposite to each other.

Ions with no d-electrons are not colored simply because they do not have any d-electrons to
promote. Therefore Sc3+ and Ti4+ are colorless as both have the electronic configuration of
[Ar]3d104s0.
Ions with 10 d-electrons are also not colored. Even though the energy levels of the d-orbitals
are split by the ligands, they are full, so promotion from a lower d-orbital to a higher d-
orbital is not possible. Therefore, Cu+ and Zn2+ (electronic configuration – [Ar]3d104s0) form
colorless complexes.

Effect of ligand on color:

Some ligands interact more strongly than others with the d-electrons and so, cause a greater
splitting.
A strong ligand splits the d-orbitals in the complex ion to a greater extent than a weak ligand
does.

If a stronger ligand replaces a weaker, the color absorbed moves anticlockwise towards the
high-energy (violet) end of the spectrum
For example:
[Cu(H2O)6]2+(aq) + 4NH3(aq) → [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
Blue Violet-blue

Relatively weaker H2O ligands have been replaced by the stronger NH3 ligands. The
absorption moves from orange towards yellow and the color of the complex changes from
blue to violet blue.
Effect of oxidation number of the transition metal ion on color:
An ion with a high charge density will attract a ligand strongly, so the splitting of the d-
orbitals will be greater.
For example:
The [Fe(H2O)6]2+ ion absorbs red light, which means that it is green.
The [Fe(H2O)6]3+ ion absorbs yellow light and it is pale purple-violet.

Effect of change in coordination number on color:

The d-splitting differs between that caused by an octahedral field and that caused by a planar
or tetrahedral field.
Thus, if the coordination number changes, the color will change.
For example:
Blue Yellow
[Cu(H2O)6]2+(aq) + 4Cl-(aq) → [CuCl4]2-(aq) + 6H2O(l)
Coordination number = 6 Coordination number = 4

Shapes of complexes:

Example:
Octahedral complexes:
Tetrahedral complexes:
The only tetrahedral complexes you are likely to encounter in the course are those in which
chloride ions act as ligands such as in the [CuCl4]2- ions.
Because chloride is a Period 3 element, its ions are much bigger than water molecules,
ammonia molecules and hydroxide ions. So, there is not usually enough room for the six
chloride ions to act as ligands.

Linear complexes:

Square planar complexes:

Reaction chart of transition metals:
Formula of Color of Reaction Reaction
Metal Ions precipitate precipitate with excess with excess
NaOH NH3

Cr3+ Cr(OH)3 Green [Cr(OH)6]3-(aq) [Cr(NH3)6]3+(aq)

Green solution Green solution

Ni2+ Ni(OH)2 Green No change [Ni(NH3)6]2+(aq)

Pale blue
solution
Fe2+ Fe(OH)2 Mud-green No change No change
(turns brown
in air)
Co2+ Co(OH)2 Blue No change [Co(NH3)6]2+(aq)
(turns pink Brown solution
in air)
Cu2+ Cu(OH)2 Blue No change [Cu(NH3)4]2+(aq)
Deep /
Royal blue
Fe3+ Fe(OH)3 Red-brown No change No change
Mn2+ Mn(OH)2 Beige/Off-white
(turns darker No change No change
brown in air)
Zn2+ Zn(OH)2 White [Zn(OH)4]2- [Zn(NH3)4]2+(aq)
Colorless Colorless
solution solution
Ag+ Ag(OH) Brown [Ag(NH3)2]2+(aq)
No change Colorless
solution

Types of reaction:
Deprotonation: One or more of the ligands gain or loses a hydrogen ion.
Ligand exchange: One or more of the ligands around the transition metal ion is replaced by a
different ligand.
Solutions of transition metal complexes:
[Cu(H2O)6]2+(aq) + H2O(l) ⇌ [Cu(OH)(H2O)5]+(aq) + H3O+(aq)
[Cu(OH)(H2O)5]+(aq) + H2O(l) ⇌ [Cu(OH)2(H2O)4](s) + H3O+(aq)
Since oxonium ions are formed, the solution formed when transition metal cations react with
water is acidic.
The position of equilibrium of the second reaction lies to the left. Only a small amount of
precipitate actually forms due to the reaction with water.
Hence, NaOH solution is added. The hydroxide ions react with the oxonium ions and shift
the position of equilibrium from left to right. Thus, the precipitate appears.
The reaction is a deprotonation reaction as two hydroxide ions from the water molecules
have removed hydrogen ions from two of the water ligands and converted them into water
molecules.
Overall, the reaction is:
[Cu(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Cu(OH)2(H2O)4](s) + 2H2O(l)

When a small amount of NH3(aq) is added to an aqueous solution of copper(ii) ions,

deprotonation occurs.
[Cu(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Cu(OH)2(H2O)4](s) + 2NH4+(aq)
Type of reaction: Deprotonation

If excess ammonia solution is added,

[Cu(H2O)6]2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4(H2O)2]2+(aq) + 2OH-(aq) + 2H2O(l)
Observation: The blue precipitate dissolves and deep blue solution is formed
Type of reaction: Ligand Exchange

Solution of Iron (ii) and Iron (iii) ions:

Iron(ii):
[Fe(H2O)6]2+(aq) + H2O(l) ⇌ [Fe(OH)(H2O)5]+(aq) + H3O+(aq)
[Fe(OH)(H2O)5]+(aq) + H2O(l) ⇌ [Fe(OH)2(H2O)4](s) + H3O+(aq)
Iron(iii):
[Fe(H2O)6]3+(aq) + H2O(l) ⇌ [Fe(OH)(H2O)5]2+(aq) + H3O+(aq)
[Fe(OH)(H2O)5]2+(aq) + H2O(l) ⇌ [Fe(OH)2(H2O)4]+(s) + H3O+(aq)
[Fe(OH)2(H2O)4]+(aq) + H2O(l) ⇌ [Fe(OH)3(H2O)3](s) + H3O+(aq)

Reaction of transition metal cations with NaOH/KOH solution:

i) Chromium(iii), Cr3+:
[Cr(H2O)6]3+(aq) + 3OH-(aq) ⇌ [Cr(OH)3(H2O)3](s) + 3H2O(l)
Few drops Green ppt.

[Cr(OH)3(H2O)3](s) + 3OH-(aq) ⇌ [Cr(OH)6]3-(aq) + 3H2O(l)

Excess Green solution

ii) Manganese(ii), Mn2+:

[Mn(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Mn(OH)2(H2O)4](s) + 2H2O(l)
Excess Off-white ppt.

iii) Iron(ii), Fe2+:

[Fe(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Fe(OH)2(H2O)4](s) + 2H2O(l)
Excess Mud-green ppt.

iv) Iron(iii), Fe3+:

[Fe(H2O)6]3+(aq) + 3OH-(aq) ⇌ [Fe(OH)3(H2O)3](s) + 3H2O(l)
Excess Red-brown ppt.

v) Cobalt(ii), Co2+:
[Co(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Co(OH)2(H2O)4](s) + 2H2O(l)
Excess Blue ppt.
vi) Nickel(ii), Ni2+:
[Ni(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Ni(OH)2(H2O)4](s) + 2H2O(l)
Excess Green ppt.

vii) Copper(ii), Cu2+:

[Cu(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Cu(OH)2(H2O)4](s) + 2H2O(l)
Excess Blue ppt.

viii) Zinc(ii), Zn2+:

[Zn(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Zn(OH)2(H2O)4](s) + 2H2O(l)
Few drops White ppt.

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

Excess Colorless solution

Reaction of transition metal cations with NH3 solution:

i) Chromium(iii), Cr3+:
Type: Deprotonation
[Cr(H2O)6]3+(aq) + 3NH3(aq) ⇌ [Cr(OH)3(H2O)3](s) + 3NH4+(aq)
Few drops Green ppt.
Type: Ligand Exchange
[Cr(OH)3(H2O)3](s) + 6NH3(aq) ⇌ [Cr(NH3)6]3+(aq) + 3OH-(aq) + 3H2O(l)
Excess Green solution

ii) Manganese(ii), Mn2+:

Type: Deprotonation
[Mn(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Mn(OH)2(H2O)4](s) + 2NH4+(aq)
Excess Off-white ppt. (darkens in air)
iii) Iron(ii), Fe2+:
Type: Deprotonation
[Fe(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Fe(OH)2(H2O)4](s) + 2NH4+(aq)
Excess Mud-green ppt.
(turns brown in air)

iv) Iron(iii), Fe3+:

Type: Deprotonation
[Fe(H2O)6]3+(aq) + 3NH3(aq) ⇌ [Fe(OH)3(H2O)3](s) + 3NH4+(aq)
Few drops Red-brown ppt.

v) Cobalt(ii), Co2+:
Type: Deprotonation
[Co(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Co(OH)2(H2O)4](s) + 2NH4+(aq)
Few drops Blue ppt. (turns pink in air)
Type: Ligand Exchange
[Co(OH)2(H2O)4](s) + 6NH3(aq) ⇌ [Co(NH3)6]2+(aq) + 2OH-(aq) + 4H2O(l)
Excess Brown solution

vi) Nickel(ii), Ni2+:

Type: Deprotonation
[Ni(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Ni(OH)2(H2O)4](s) + 2NH4+(aq)
Few drops Green ppt.
Type: Ligand Exchange
[Ni(OH)2(H2O)4](s) + 6NH3(aq) ⇌ [Ni(NH3)6]2+(aq) + 2OH-(aq) + 4H2O(l)
Excess Pale blue solution
vii) Copper(ii), Cu2+:
Type: Deprotonation
[Cu(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Cu(OH)2(H2O)4](s) + 2NH4+(aq)
Few drops Blue ppt.
Type: Ligand Exchange
[Cu(OH)2(H2O)4](s) + 4NH3(aq) ⇌ [Cu(NH3)4(H2O)2]2+(aq) + 2OH-(aq) + 2H2O(l)
Excess Deep blue solution

viii) Zinc(ii), Zn2+:

Type: Deprotonation
[Zn(H2O)6]2+(aq) + 2NH3(aq) ⇌ [Zn(OH)2(H2O)4](s) + 2NH4+(aq)
Few drops Blue ppt.
Type: Ligand Exchange
[Zn(OH)2(H2O)4](s) + 4NH3(aq) ⇌ [Zn(NH3)4(H2O)2]2+(aq) + 2OH-(aq) + 2H2O(l)
Excess Colorless solution
Naming transition metal complexes:
Ligand Type Example Name of the complex
H2O Aqua [Fe(H2O)6]2+
NH3 Ammine [Cu(NH3)]2+
Cl- Chloro [CuCl4]2-
OH- Hydroxo [Zn(OH)4]2-
CN- Cyano [Fe(CN)6]-4
CO Carbonyl [Ni(CO)4]
-
Cl , NH3 Mixed [Co(NH3)4Cl2]+
OH-, H2O Mixed [Fe(OH)2(H2O)4]+
H2O, NH3 Mixed [Cu(NH3)4(H2O)2]2+