5.

4 TRANSITION METAL
 The Definition

• Transition metal is element that can form one or

more stable ions with a partially filled d-subshell.
OR
• transition metal is "an element whose atom has
an incomplete d sub-shell, or which can give rise
to cations with an incomplete d sub-shell.”
• it is found in the d-block in the middle of the
periodic table
• most of the elements in the d-block are transition
elements.
TRANSITION METALS IN PERIODIC TABLE
Electronic Configurations of the Transition
Metals
• The transition metals in the first row of the d-
block all have their highest energy electrons in
the 4s and 3d subshells.
• To work out the electronic configuration, first find
the total number of 4s and 3d electrons by
subtracting 18 from the element’s atomic
number.
• Eg: Cobalt: Atomic number = 27, so 27-18=9
• To fill up the electron subshells, the 4s subshell is
always filled first (except Cr and Cu)
 PRACTICES

• Write down the electronic configuration for

these block d elements:
a) Ti b) Cr c) Fe

d) V e) Ni f) Mn

g) Cu h) Co i) Zn
 Sc and Zn
Not a Transition Metal!
• d-orbitals can hold 10 electrons.
• A transition metal must form at least one ion that has
between 1 and 9 electrons in the d-orbital, but not Sc
and Zn.
• Scandium only forms one ion, Sc3+, which has an empty
d-subshell.
Sc = [Ar] 3d1 4s2, so when it loses 3 electrons to form
Sc3+, it ends up with electronic configuration [Ar].
• The same thing apply to zinc
• Write down the electronic configuration for Zn and find
the ion of Zn.
Special Chemical Properties Of Transition
Metals
• They can form complex ions
– Iron forms a complex ion with water- [Fe(H2O)6]2+

• They form coloured ions in solution

– Fe2+ ions are pale green and Fe3+ ions are yellow

• The can acts as good catalysts

– Iron is the catalyst used in the Haber process

• They can exist in variable oxidation states

– Iron can exist in +2 oxidation state as Fe2+ ions and in +3
oxidation state as Fe3+ ions
 COMPLEX IONS AND COLOUR
• Def: A complex ion is a metal ion surrounded by dative covalently
bonded ligands
• A dative covalent bond is a covalent bond in which both electrons
in the shared pair come from the same atom
• Ligand is an atom, ion or molecule that donates a pair of electrons
to a central metal ion
• In most of the complex ions, the coordination number will be 4 or 6
• If the ligands are small, 6 can fit around the central metal ion
• But if the ligands are larger, like Cl-, only 4 can fit around the central
metal ion.
• Only one ligand can be swapped for another ligand and it causes a
colour change
 COMPLEX IONS AND COLOUR

• Small Ligands : H2O, CN-, or NH3

– When transition metal compounds dissolve in
water, they form metal-aqua complex ions which
have 6 water molecules forming dative covalent
bonds with each metal ion.
– Eg: [Fe(H2O)6]2+

• Large Ligand : Cl-

– Eg: CrCl4-
6 Dative Covalent Bonds Mean an
OCTAHEDRAL Shape

[Fe(H2O)6]2+
6 Dative Covalent Bonds Mean an
OCTAHEDRAL Shape

Exercise:
• Draw the shape of
[Cu(NH3)4(H2O)2]2+

[Cr(NH3)6]3+
4 Dative Covalent Bonds USUALLY Mean a
TETRAHEDRAL Shape

BUT NOT ALWAYS,

In few complexes, 4 dative
Covalent bonds form a SQUARE
PLANAR shape

[CuCl4]2-

[Pt(NH3)2Cl2]
SOME Complexes Have 2 Dative Covalent
Bonds and Form a LINEAR Shape

[Ag(NH3)2]+
Complex Ions Have an Overall Charge or
Total Oxidation State
• The overall charge on the complex ion is its
total oxidation state
• It is put outside the square brackets
Oxidation state of the metal ion =
total oxidation state – sum of the oxidation states of the ligands

• Eg: [Fe(CN)6]4- (aq)

Ligands Form Bonds Using Lone Pairs of
Electrons
• A ligand must have at least one lone pair of
electrons
• Ligands with one lone pair are called
monodentate or unidentate
• Eg: H2O, NH3, Cl-, CN-
• Ligands with two lone pairs are called bidentate
• Eg: ethane-1,2-diamine and ethanedioate.
• Bidentate ligands can form two dative covalent
bonds with a metal ion
 BIDENTATE

In ethanedioate it is these
In ethane-1,2-diamine both these 2 lone pairs interact with
pairs of electrons interact with the metal ion.
same metal ion
Ligands Form Bonds Using Lone Pairs of
Electrons
• Ligands with more than two lone pairs are
called polydentate
• Eg: EDTA4- has six lone pairs
• It can form six dative bonds with a metal ion
• Other example: Haemoglobin-contains a
molecule with 4 nitrogens that each forms a
dative covalent bond with Fe2+
 POLYDENTATE

EDTA-ethylene diamine tetraacetic acid

EDTA4- forming six dative bond with
metal
POLYDENTATE HAEMOGLOBIN

Haemoglobin carries oxygen in blood

Ligands Split the 3d Subshell into Two Energy
Levels – coloured metals
The bonding of a ligand to a transition metal has some effects
on the metal’s electrons
i) Normally the 3d orbitals of a transition element ion all
have the same energy
ii) In a complex, there’s repulsion between the electrons in
the ligands and the 3d electrons of the metal. This
increases the energy of all the 3d orbitals-BUT SOME ARE
INCREASED MORE THAN OTHERS
iii) This splits the 3d orbitals into two different energy levels.
iv) Electrons tend to occupy the lower orbitals-but they can
jump up to higher orbitals by absorbing energy equal to
the energy gap, ∆E.
v) They get this energy from visible light.
VISIBLE LIGHT
• Is the
electromagnetic
radiation that can
be detected by
human eye

• It extends from a
wavelength of
about 780 nm at
the red end of the
spectrum to one of
the UV light
(380nm)
 The Colours of Compounds are the
Complement of Those That are Absorbed
• When visible light hits a
complex transition metal ion,
some frequencies are
absorbed.

• Electrons use the energy to

jump to the higher orbitals-
the frequencies absorbed
depend on the size of the
energy gap

• The rest of the frequencies

are transmitted-which means
the colour is actually made
up of all the frequencies that
are not absorbed.
 The Colours of Compounds are the
Complement of Those That are Absorbed
• This colour is the complement of the absorbed colour.
• Eg: [Cu(H2O)6]2+ absorbs yellow light, so the colour
human eye can see is actually blue.
• The central metal ion, the ligands and the coordination
number affect the size of the energy gap, so they can
affect the colour
• If there are no 3d electrons, there are no electrons to
jump and so no energy is absorbed.
• If the 3d subshell is full, there’s no room in the upper
orbitals for any electrons to jump to, so no energy will
absorbed
IDENTIFICATION OF TRANSITION METAL
COMPLEXES
1. CHANGES IN OXIDATION STATE

COMPLEX [Fe(H2O)6]2+ (aq)  [Fe(H2O)6]3+ [V(H2O)6]2+  [V(H2O)6]3+ (aq)

OXIDATION +2 +3 +2 +3
STATE

COLOUR Pale Green Yellow Violet Green

2. CHANGES IN COORDINATION NUMBER

• This always involves a change of ligand too

COMPLEX [Cu(H2O)6]2+ + 4 Cl-  [CuCl4]2- + 6H2O

COORDINATION NUMBER 6 4

COLOUR yellow
blue
 3. CHANGES IN LIGAND

• This can cause a colour change even if the oxidation state and
coordination number remain the same

COMPLEX [Ni(H2O)6]2+ + 6 NH3  [Ni(NH3)6]2+ + 6 H2O

OXIDATION STATE +2 +2

COLOUR green blue

LIGAND REACTIONS
Ligands can Exchange Places with One
Another
• Ligand exchange always causes a colour change
1) If the ligands are of similar size, (H2O and NH3),
then the coordination number of the complex ion
does not change, and does the shape.

[Cr(H2O)6]3+ (aq) + 6 NH3 (aq)  [ Cr(NH3)6]3+ (aq) + 6H2O (l)

octahedral octahedral
violet purple
Ligands can Exchange Places with One
Another

2) If the ligands are different sizes, (H2O and Cl-) there’s

a change of coordination number and a change of
shape.

[Cu(H2O)6]2+ (aq) + 4Cl- (aq)  [CuCl4]2- (aq) + 6H2O (l)

Octahedral Tetrahedral
blue yellow
 Ligands can Exchange Places with One
Another
3) Sometimes the substitution is only partial
[Cu(H2O)6]2+ (aq) + 4 NH3 (aq)  [ Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l)

elongated
octahedral octahedral

blue deep blue

[Cr(H2O)6]3+ (aq) + SO42-(aq)  [ Cr(H2O)5(SO4)]+ (aq) + H2O (l)

octahedral distorted
octahedral
violet green
 Different Ligands Form Different
Strength Bonds
• Ligand exchange reactions can be easily reversed,
except if the new complex ion is much more stable
than previous one.
1. If the new ligands form stronger bonds with the central
metal ion than the old ligand did, the change is difficult
to reverse
Eg: CN- ion form stronger dative covalent bonds with Fe3+
ions than water molecule, so it’s hard to reverse this
reaction
[Fe(H2O)6]3+ (aq) + 6CN- (aq)  [Fe(CN)6]3- (aq) + 6 H2O (l)
Different Ligands Form Different Strength
Bonds
2. Bidentate ligands form more stable complexes than
monodentate ligands, so a change like below equation is
difficult to reverse:

[Ni(H2O)6]2+ (aq) +3H2NCH2CH2NH2 (aq) 

[Ni(H2NCH2CH2NH2)3]2+ (aq) + 6 H2O (l)

Different Ligands Form Different
Strength Bonds
3. A polydentate ligand, like EDTA forms even more stable
complexes. So a change like below equation is very hard
to reverse:
[Cu(H2O)6]2+ (aq) + EDTA4- (aq)  [Cu(EDTA)]2- (aq) + 6H2O (l)

When bidentate ligands take the place of monodentate

ligands there are generally MORE PRODUCT molecules
than REACTANT molecules.
This means the TOTAL ENTROPY CHANGE for the
reaction is likely to be POSITIVE, so the reaction would
expected to “go”
The same happens when a polydentate ligand replaces
monodentate or bidentate ligands.
 Adding Alkali to Metal Aqua-Ions
Forms Precipitates
• Adding OH- ions to solutions of metal aqua-
ions produces insoluble metal hydroxides.

1. In water, metal aqua 3+ ions form the equilibrium:

[M(H2O)6]3+ + H2O ↔ [ M(H2O)5(OH)]2+ + H3O+

If OH- is added to the equilibrium H3O+ ions are removed—

this shift the equilibrium to the right.
Adding Alkali to Metal Aqua-Ions
Forms Precipitates
2. Now another equilibrium is set up in the solution:

[M(H2O)5(OH)]2+ (aq) + H2O (l) ↔ [M(H2O)4(OH)2]+ (aq) + H3O+(aq)

Again the OH- ions remove H3O+ ions from the solution,
pulling the equilibrium to the right.

3. This happen one last time—until just left with insoluble

uncharged metal hydroxide:

[M(H2O)4(OH)2]+ (aq) + H2O (l) ↔ [M(H2O)3(OH)3] (s) + H3O+ (aq)

Precipitates Form with NaOH and NH3 Solution
• When OH- ions is added to a solution of metal aqua-ions they
form precipitates
• Eg: NaOH and NH3

When ammonia dissolves in water it sets up this equilibrium:

NH3 + H2O ⇌ NH4+ + OH-
Hydroxide ions are formed from the reaction with water.
So adding a small amount of ammonia solution gives the same results as
sodium hydroxide

• When excess ammonia is added, a further reaction happens

• With excess OH- the H2O ligands get displaced and with excess
NH3, both H2O and OH- ligands are displaced by NH3 ligands.
• This produces a soluble metal ion complex
Precipitates Form with NaOH and NH3 Solution
Metal Aqua-ion With OH- or NH3 With excess OH- With excess NH3

[Cu(H2O)6]2+ Cu(H2O)4(OH)2 No change [Cu(NH3)4(H2O)2]2+

Blue solution Blue precipitate Deep blue solution
[Fe(H2O)6]2+ Fe(H2O)4(OH)2 No change No change
Green solution Green ppt
[Fe(H2O)6]3+ Fe(H2O)3(OH)3 No change No change
Yellow solution Brown ppt
[Cr(H2O)6]3+ Cr(H2O)3(OH)3 [Cr(OH)6]3- [Cr(NH3)6]3+
Violet solution Green ppt Green solution Purple solution
[Mn(H2O)6]2+ Mn(H2O)4(OH)2 No change No change
Pale pink solution Brown ppt
[Ni(H2O)6]2+ Ni(H2O)4(OH)2 No change [Ni(NH3)6]2+
Green solution Green ppt Blue solution
[Zn(H2O)6]2+ Zn(H2O)3(OH)3 [Zn(OH)4]2- [Zn(NH3)4]2+
colourless White ppt Colourless solution Colourless solution
CHEMISTRY OF CHROMIUM AND COPPER
 COPPER AND CHROMIUM
• Copper ions usually show oxidation states of +1 or +2
1. Cu2+ ions are stable in aqueous solution. They’re reduced to Cu
metal by more electropositive metals, like Zinc or Nickel.
(Displacement rxn)
2. Solid copper(I) compounds are stable, but aqueous Cu+ ions are
unstable and disproportionate in aqueous solution
3. Copper(I) ions can form some stable complexes if there are suitable
ligands
- The ligands stabilise the copper(I) and prevent it from
disproportionating ([CuCl2]-)
4. Copper(I) complexes are not colored because they have full 3d
subshell
5. But solid copper(I) compounds can be coloured
- eg: copper(I)oxidered
 COPPER AND CHROMIUM

• Copper(I) ions are unstable and will

disproportionate in aqueous solution to give
copper and copper(II) ions.

2Cu+ (aq)  Cu2+ (aq) + Cu (s)

 COPPER AND CHROMIUM

• Chromium ions usually exist in the +2, +3 or

+6 oxidation states
• Cr is used to make stainless steel. It is also
added to steel to make it harder
• The +3 state is the most stable, followed by +6
then +2
 COPPER AND CHROMIUM

Both these ions are

good oxidising
agents because they Oxidation state Formula of ion Colour of ion in water
can be easily +6 Cr2O72- (aq) Orange
reduced to Cr3+
+6 CrO42- (aq) Yellow
+3 Cr3+ (aq) Green (Violet)
+2 Cr2+ (aq) Blue

When Cr3+ ions are surrounded by 6 water ligands,

they’re violet. But when water ligands are usually
substituted with impurities in water e.g: Cl-, this makes
the solution look green
 COPPER AND CHROMIUM
chromium hydroxide is amphoteric

1. It is important to note that these are

reactions and NOT ligand exchanges
2. The ligands are chemically modified by the
acid or alkali
3. Chromium can still undergo ligand exchange
when it is mixed with excess ammonia.
[Cr(H2O)6]3+ + 6 NH3  [Cr(NH3)6]3+ + 6H2O
Violet purple
 COPPER AND CHROMIUM
chromium hydroxide is amphoteric

Amphoteric substances can react with both

acids and alkalis

[Cr(H2O)3(OH)3] (aq)
With alkali with acid
+3OH- +3H+

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

UAMZ-INTECUiTM-2011