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4.

Transition Metals
General properties of transition metals
transition metal characteristics of elements Sc
Cu arise from an incomplete d sub-level in
atoms or ions
Sc 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1
Ti 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
2
V 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
3
Cr 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
5
Mn 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
5
Fe 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
6
Co 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
7
Ni 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
8
Cu 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
10
Zn 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
Sc
3+
[Ar] 4s
0
3d
0
Ti
3+
[Ar] 4s
0
3d
1
V
3+
[Ar] 4s
0
3d
2
Cr
3+
[Ar] 4s
0
3d
3
Mn
2+
[Ar] 4s
0
3d
5
Fe
3+
[Ar] 4s
0
3d
5
Co
2+
[Ar] 4s
0
3d
7
Ni
2+
[Ar] 4s
0
3d
8
Cu
2+
[Ar] 4s
0
3d

Zn
2+
[Ar] 4s
0
3d
10
When
forming
ions lose
4s before
3d
Why is Zn not a transition metal?
Zn can only form a +2 ion. In this ion the Zn
2+
has a complete d orbital and so does
not meet the criteria of having an incomplete d orbital in one of its compounds.
these characteristics include
complex formation,
formation of coloured ions,
variable oxidation state
catalytic activity.
Complex formation
complex :is a central metal ion surrounded by ligands.
ligand.: An atom, ion or molecule which can donate a lone electron pair
Co-ordinate bonding is involved in complex formation.
Co-ordinate bonding is when the shared pair of electrons in the covalent bond
come from only one of the bonding atoms.
Co-ordination number: The number of co-ordinate bonds formed to a central
metal ion
ligands can be unidentate (e.g. H
2
O, NH
3
and Cl
-
)
which can form one coordinate bond per ligand or
bidentate (e.g. NH
2
CH
2
CH
2
NH
2
and ethanedioate
ion C
2
O
4
2-
) which have two atoms with lone pairs
and can form two coordinate bonds per ligand
or multidentate (e.g. EDTA
4-
which can form six
coordinate bonds per ligand).
haem is an iron(II) complex
with a multidentate ligand.
A complex with bidentate
ligands e.g.
[Cr(NH
2
CH
2
CH
2
NH
2
)
3
]
3+
It has a coordination number of 6
Cu(H
2
O)
6
2+
+ 3NH
2
CH
2
CH
2
NH
2
[Cu(NH
2
CH
2
CH
2
NH
2
)
3
]
2+
+ 6H
2
O
Cu(H
2
O)
6
2+
+ 3C
2
O
4
2-
[Cu(C
2
O
4
)
3
]
4-
+ 6H
2
O
Cu(H
2
O)
6
2+
+ EDTA
4-
[Cu(EDTA)]
2-
+ 6H
2
O
Equations to show formation of bidentate and mutidentate complexes
CH
2
CH
2
N N
CH
2
CH
2
CH
2
CH
2
C
C
C
C
O
O
O
-O
-O O-
O-
O
The EDTA
4-
anion has the formula
with six donor sites(4O and 2N) and forms a 1:1
complex with metal(II) ions
3-
C
C O
O
C
C
O
O
C
C
O
O
Cr
O
O
O
O
O
O
3+
H
2
C
NH
2
NH
2
CH
2
H
2
C
NH
2
NH
2 CH
2
CH
2
NH
2
NH
2
Cr
CH
2
A complex with
bidentate ethanedioate
ligands e.g. [Cr(C
2
O
4
)
3
]
3-
Learn the two bidentate ligands
mentioned above but it is not
necessary to remember the
structure of EDTA
There are 3 bidentate
ligands in this complex
each bonding in twice
to the metal ion
Cu
OH
2
OH
2
O H
2
O H
2
OH
2
OH
2
2+
1 N !o"#$% c&e're(ise)or*
Formation of coloured ions
Colour changes arise from changes in
1. oxidation state,
2. co-ordination number
3. ligand.
Colour arises from electronic transitions from the
ground state to excited states: between different d
orbitals
A portion of visible light is absorbed to promote d
electrons to higher energy levels. The light that is not
absorbed is transmitted to give the substance colour.
Changing colour
Changing a ligand or changing the coordination number will alter the energy split between the d- orbitals,
changing E and hence change the frequency of light absorbed.
Ligands cause 5 d orbitals to
split into two energy levels
Co(H
2
O)
6
2+
+ 4Cl
-
[CoCl
4
]
2-
+ 6H
2
O
pink blue
[Co(NH
3
)
6
]
2+
(aq) [Co(NH
3
)
6
]
3+
(aq) +e
-
yellow brown
Compounds without colour
Scandium is a member of the d block, its ion
(Sc
3+
) hasn't got any d electrons left to move
around. So there is not an energy transfer equal to
that of visible light
In the case of Zn
2+
ions and Cu
+
ions the d shell is full
e.g.3d
10
so here there is no space for electrons to
transfer. So there is not an energy transfer equal to that
of visible light
O
2
In this
equation only
oxidation state
is changing
Co(H
2
O)
6
2+
+ 6 NH
3
Co(NH
3
)
6
2+
+ 6H
2
O
Pink yellow brown
In this equation both ligand and co-
ordination number are changing
In this equation only the ligand is changing
How colour arises
Shapes of complex ions
transition metal ions
commonly form octahedral
complexes with small
ligands (e.g. H
2
O and NH
3
).
Ni
NH
3
NH
3
H
3
N
H
3
N
NH
3
NH
3
2+
transition metal ions
commonly form
tetrahedral complexes
with larger ligands
(e.g.Cl
-
).
2-
Cu
Cl Cl
Cl
Cl
square planar
complexes are also
formed, e.g.
cisplatin
Ag
+
commonly forms
linear complexes
e.g. [Ag(NH
3
)
2
]
+
,
[Ag(S
2
O
3
)
2
]
3-
and
[Ag(CN)
2
]
-
(all
colourless).
Ag H
3
N NH
3
+
2
Pt
Cl
Cl
N H
3
N H
3
2-
Equation to learn!
This equation links the colour and frequency of
the light absorbed with the energy difference
between the split d orbitals
E = hv.
v = frequency of light absorbed (unit s
-1
or Hz)
h=plancks constant 6.63 10
34
J s
E energy difference between split orbitals (J)
A solution will appear blue if it absorbs orange light. The
energy split in the d orbitals E will be equal to the
frequency of orange light(5 x10
14
s
-1
) x plancks constant
E in a blue solution = hv
= 6.63 10
34
x 5 x10
14
= 3.32 10
19
J
N !o"#$% c&e're(ise)or*
3
Variable oxidation states
Transition elements show variable oxidation states
When transition metals form ions they
lose the 4s electrons before the 3d
Reducing Chromium
Cr
3+
(green) and then Cr
2+
(blue) are formed by reduction of
Cr
2
O
7
2-
(orange) by the strong reducing agent zinc in (HCl) acid
solution. Fe
2+
is a less strong reducing agent and will only
reduce the dichromate to Cr
3+
Cr
2
O
7
2-
+ 14H
+
+ 3Zn 2Cr
3+
+ 7H
2
O + 3 Zn
2+
Cr
2
O
7
2-
+ 14H
+
+ 4Zn 2Cr
2+
+ 7H
2
O + 4 Zn
2+
Cr
2
O
7
2-
+ 14H
+
+ 6Fe
2+
2Cr
3+
+ 7H
2
O + 6 Fe
3+
Orange green
The Fe
2+
and Cr
2
O
7
2-
in acid solution reaction can be used
as a quantitative redox titration. This does not need an
indicator
General trends
Relative stability of +2 state with respect to +3 state increases across the period
Compounds with high oxidation states tend to be oxidising agents e.g MnO
4
-
Compounds with low oxidation states are often reducing agents e.g V
2+
& Fe
2+
Keeping the zinc/dichromate under a
hydrogen atmosphere is needed to reduce
to Cr
2+
absorption of visible light is used in spectrometry to
determine the concentration of coloured ions
method
Add an appropriate ligand to intensify colour
Make up solutions of known concentration
Measure absorption or transmission
Plot graph of results or calibration curve
Measure absorption of unknown and compare
If visible light of increasing frequency is passed through a
sample of a coloured complex ion, some of the light is
absorbed.
The amount of light absorbed is proportional to the
concentration of the absorbing species
Some complexes have only pale colours and do not
absorb light strongly. In the cases a suitable ligand is
added to intensify the colour.
Spectrophotometry
Manganate redox titration
The redox titration between Fe
2+
with MnO
4

(purple) is a very
common exercise. This titration is self indicating because of the
significant colour change from reactant to product
MnO
4
-
(aq) + 8H
+
(aq) + 5Fe
2+
(aq) Mn
2+
(aq) + 4H
2
O (l) + 5Fe
3+
(aq)
Purple colourless
Choosing correct acid for manganate titrations.
The acid is needed to supply the 8H
+
ions. Some acids are not suitable as they set up alternative redox
reactions and hence make the titration readings inaccurate.
Only use dilute sulphuric acid for manganate titration
Insufficient volumes of sulphuric acid will mean the solution is not acidic enough and MnO
2
will be produced
instead of Mn
2+
MnO
4
-
(aq) + 4H
+
(aq) + 3e- MnO
2
(s) + 2H
2
O
The brown MnO
2
will mask the colour change and lead to a greater (inaccurate) volume of Manganate being
used in the titration
Using a weak acid like ethanoic acid would have the same effect as it cannot supply the large amount of
hydrogen ions needed (8H
+
)
It cannot be conc HCl as the Cl
-
ions would be oxidised to Cl
2
by MnO
4
-
as the E
o
MnO
4
-
/Mn
2+
> E
o
Cl
2
/Cl
-
MnO
4
-
(aq) + 8H
+
(aq) + 5e

Mn
2+
(aq) + 4H
2
O(l) E+1.51V
Cl
2
(aq) +2e

2Cl

(aq) E +1.36V
This would lead to a greater volume of manganate being used and poisonous Cl
2
being produced
It cannot be nitric acid as it is an oxidising agent. It oxidises Fe
2+
to Fe
3+
as E
o
NO
3
-
/HNO
2
> E
o
Fe
3+
/Fe
2+
NO
3
-
(aq) + 3H
+
(aq) + 2e

HNO
2
(aq) + H
2
O(l) E
o
+0.94V
Fe
3+
(aq)+e

Fe
2+
(aq) E
o
+0.77 V
This would lead to a smaller volume of manganate being used
The purple colour of manganate can make it
difficult to see the bottom of meniscus in
the burette
If the manganate is in the burette then the
end point of the titration will be the first
permanent pink colour
Colourless purple
N !o"#$% c&e're(ise)or*
4
Other useful manganate titrations
With hydrogen peroxide
Ox H
2
O
2
O
2
+ 2H
+
+ 2e
-
Red MnO
4
-
(aq) + 8H
+
(aq) + 5e
-
Mn
2+
(aq) + 4H
2
O
Overall 2MnO
4
-
(aq) + 6H
+
(aq) + 5H
2
O
2
5O
2
+ 2Mn
2+
(aq) + 8H
2
O
Ox C
2
O
4
2-
2CO
2
+ 2e
-
Red MnO
4
-
(aq) + 8H
+
(aq) + 5e
-
Mn
2+
(aq) + 4H
2
O
Overall 2MnO
4
-
(aq) + 16H
+
(aq) + 5C
2
O
4
2-
(aq) 10CO
2
(g) + 2Mn
2+
(aq) + 8H
2
O(l)
With ethanedioate
With Iron (II) ethanedioate both the Fe
2+
and the C
2
O
4
2-
react with the MnO
4
-
1MnO
4
-
reacts with 5Fe
2+
and 2 MnO
4
-
reacts with 5C
2
O
4
2-
MnO
4
-
(aq) + 8H
+
(aq) + 5Fe
2+
Mn
2+
(aq) + 4H
2
O + 5Fe
3+
2MnO
4
-
(aq) + 16H
+
(aq) + 5C
2
O
4
2-
10CO
2
+ 2Mn
2+
(aq) + 8H
2
O
So overall
3MnO
4
-
(aq) + 24H
+
(aq) + 5FeC
2
O
4
10CO
2
+ 3Mn
2+
(aq) + 5Fe
3+
+ 12H
2
O
So overall the ratio is 3 MnO
4
-
to 5 FeC
2
O
4
The reaction between MnO
4
-
and
C
2
O
4
2-
is slow to begin with (as
the reaction is between two
negative ions) To do as a titration
the conical flask can be heated to
60
o
C to speed up the initial
reaction.
be able to perform calculations for these titrations and for
others when the reductant and its oxidation product are given.
A 2.41g nail made from an alloy containing iron is
dissolved in 100cm
3
acid. The solution formed
contains Fe(II) ions.
10cm
3
portions of this solution are titrated with
potassium manganate (VII) solution of 0.02M.
9.80cm
3
of KMnO
4
were needed to react with the
solution containing the iron.
What is the percentage of Iron by mass in the nail?
Manganate titration example
MnO
4
-
(aq)
+ 8H
+
(aq)
+ 5Fe
2+
Mn
2+
(aq)
+ 4H
2
O + 5Fe
3+
Step1 : find moles of KMnO
4
moles = conc x vol
0.02 x 9.8/1000
= 1.96x10
-4
mol
Step 2 : using balanced equation find moles Fe
2+
in 10cm
3
= moles of KMnO
4
x 5
= 9.8x10
-4
mol
Step 3 : find moles Fe
2+
in 100cm
3
= 9.8x10
-4
mol x 10
= 9.8x10
-3
mol
Step 4 : find mass of Fe in 9.8x10
-3
mol
mass= moles x RAM = 9.8x10
-3
x 55.8 = 0.547g
Step 5 ; find % mass
%mass = 0.547/2.41 x100
= 22.6%
N !o"#$% c&e're(ise)or*
A 1.412 g sample of impure FeC
2
O
4
.2H
2
O
was dissolved in an excess of dilute
sulphuric acid and made up to 250 cm
3
of
solution. 25.0 cm
3
of this solution
decolourised 23.45 cm
3
of a 0.0189 mol
dm
3
solution of potassium
manganate(VII).
What is the the percentage by mass of
FeC
2
O
4
.2H
2
O in the original sample?
Step1 : find moles of KMnO
4
moles = conc x vol
0.0189 x 23.45/1000
= 4.43x10
-4
mol
Step 2 : using balanced equation find moles FeC
2
O
4
.2H
2
O in 25cm
3
= moles of KMnO
4
x 5/3 (see above for ratio)
= 7.39x10
-4
mol
Step 3 : find moles FeC
2
O
4
.2H
2
O in 250 cm
3
= 7.39x10
-4
mol x 10
= 7.39x10
-3
mol
Step 4 : find mass of FeC
2
O
4
.2H
2
O in 7.39x10
-3
mol
mass= moles x Mr = 7.39x10
-3
x 179.8 = 1.33g
Step 5 ; find % mass
%mass = 1.33/1.412 x100
= 94.1%
5
Oxidation in alkaline solution
When transition metals in low oxidation states are in alkaline
solution they are more easily oxidised than when in acidic solution
[M(H
2
O)
6
]
2+
(aq) [M(OH)
4
]
2-
(aq)
excessNaOH
Acidified
Not easy to oxidise
alkaline
easier to oxidise
It is easier to remove an electron
from a negatively charged ion
The metal ions can be oxidised by using
oxidising agents such as hydrogen peroxide
and sometimes by standing in air
Chromium and cobalt compounds can be oxidised by using the oxidising agent hydrogen peroxide
Cr(OH)
6
3-
(aq)
H
2
O
2
CrO
4
2-
(aq) Cr(H
2
O)
6
3+
Excess
NaOH
2 [Cr(OH)
6
]
3-
+ 3H
2
O
2
2CrO
4
2-
+2OH
-
+ 8H
2
O
Co(H
2
O)
4
(OH)
2
(s)
blue precipitate
Co(H
2
O)
3
(OH)
3
(s)
brown precipitate
H
2
O
2
Green solution yellow solution
Ammonical oxidation of Cobalt Ammonia ligands make the Co(II) state unstable
and easier to oxidise. Air oxidises Co(II) to Co(III).
[Co(NH
3
)
6
]
2+
(aq) [Co(NH
3
)
6
]
3+
(aq) + e
Brown solution yellow solution
[Co(H
2
O)
6
]
2+
(aq)
pink solution
O
2
Excess NH
3
Co(H
2
O)
4
(OH)
2
(s)
blue precipitate
little OH
-
or NH
3
Co(H
2
O)
3
(OH)
3
(s)
brown precipitate
O
2
Reduction :H
2
O
2
+ 2e
-
2OH
-
Oxidation: [Cr(OH)
6
]
3-
+ 2OH
-
CrO
4
2-
+ 3e
-
+ 4H
2
O
Re :H
2
O
2
+ 2e
-
2OH
-
Ox: Co(H
2
O)
4
(OH)
2
+ OH
-
Co(H
2
O)
3
(OH)
3
+ e
-
+ H
2
O
2Co(H
2
O)
4
(OH)
2
+ H
2
O
2
2Co(H
2
O)
3
(OH)
3
+ 2H
2
O
Half equations in alkaline conditions:
These are more difficult to do than half
equations under acidic conditions. The
easiest way of doing it is to balance as
if under acidic conditions then add OH
-
ions to both sides to convert to
alkaline
[Cr(OH)
6
]
3-
+ 2OH
-
CrO
4
2-
+ 3e
-
+ 4H
2
O
For change Cr(OH)
6
3-
CrO
4
2-
Add H
2
O to balance O: [Cr(OH)
6
]
3-
CrO
4
2-
+ 2H
2
O + 3e
-
Add H
+
to balance H: [Cr(OH)
6
]
3-
CrO
4
2-
+ 2H
2
O + 2H
+
+ 3e
-
[Cr(OH)
6
]
3-
+2OH
-
CrO
4
2-
+ 2H
2
O + 2H
+
+2OH
-
+ 3e
-
Add OH
-
to both sides
to cancel out H
+
:
H
2
O
2
could also bring
about the oxidation
Chromate/ dichromate equilibrium
2 CrO
4
2-
+ 2H
+
Cr
2
O
7
2-
+ H
2
O
Yellow solution orange solution
The chromate CrO
4
2-
and dichromate Cr
2
O
7
2-
ions can be converted
from one to the other by the following equilibrium reaction
This is not a redox reaction as both
the chromate and dichromate ions
have an oxidation number of +6. This
is an acid base reaction
Addition of acid will by application of le chatelier push the equilibrium to the dichromate
Addition of alkali will remove the H
+
ions and, by application of le chatelier, push the equilibrium to
the chromate
The O
2
half equation for these reactions is:- O
2
+ 2H
2
O + 4e
-
4OH
-
[Co(NH
3
)
6
]
2+
[Co(NH
3
)
6
]
3+
+e
-
Overall 4[Co(NH
3
)
6
]
2+
O
2
+ 2H
2
O4[Co(NH
3
)
6
]
3+
+4OH
-
Be able to combine the H
2
O
2
and O
2
half equations with other oxidation reactions
N !o"#$% c&e're(ise)or*
6
Transition metals and their compounds can
act as heterogeneous and homogeneous
catalysts.
Catalysis
A heterogeneous catalyst is in a different phase from the reactants
A homogeneous catalyst is in the same phase as the reactants
Surface area:
Increasing the surface area of a solid catalyst will
improve its effectiveness. A support medium is often
used to maximise the surface area and minimise the
cost (e.g. Rh on a ceramic support in catalytic
converters).
Heterogeneous catalysts are usually solids
whereas the reactants are gaseous or in solution.
The reaction occurs at the surface of the catalyst.
Heterogeneous catalysis
Adsorption of reactants at active sites on the surface
may lead to catalytic action. The active site is the place
where the reactants adsorb on to the surface of the
catalyst. This can result in the bonds within the reactant
molecules becoming weaker, or the molecules being held in
a more reactive configuration. There will also be a higher
concentration of reactants at the solid surface so leading to
a higher collision frequency
Transition Metals can use the 3d and 4s e- of atoms on the
metal surface to form weak bonds to the reactants.
Steps in Heterogeneous Catalysis
1. Reactants form bonds with atoms at active sites on
the surface of the catalyst (adsorbed onto the
surface)
2. As a result bonds in the reactants are weakened
and break
3. New bonds form between the reactants held close
together on catalyst surface
4. This in turn weakens bonds between product and
catalyst and product leaves (desorbs)
Strength of adsorption
The strength of adsorption helps to determine the
effectiveness of the catalytic activity
Some metals e.g. W have too strong adsorption and
so the products cannot be released
Some metals e.g. Ag have too weak adsorption, and
the reactants do not adsorb in high enough
concentration
Ni and Pt have about the right strength and are most
useful as catalysts
Catalysts increase reaction rates without getting used up. They do this by providing an
alternative route with a lower activation energy
V
2
O
5
is used as a catalyst in the Contact Process.
Overall equation : 2SO
2
+ O
2
2SO
3
step 1 SO
2
+ V
2
O
5
SO
3
+ V
2
O
4
step 2 2V
2
O
4
+ O
2
2V
2
O
5
Examples of heterogeneous catalysts
Learn the equations for this mechanism. Note the oxidation
number of the vanadium changes and then changes back. It is
still classed as a catalyst as it returns to its original form
Cr
2
O
3
catalyst is used in the manufacture of
methanol from carbon monoxide and hydrogen
CO + 2H
2
CH
3
OH
Fe is used as a catalyst in the Haber Process
N
2
+ 3H
2
2NH
3
Poisoning Catalysts
catalysts can become poisoned by impurities
and consequently have reduced efficiency
Poisoning has a cost implication e.g. poisoning by sulphur
in the Haber Process and by lead in catalytic converters
in cars means that catalysts lose their efficiency and may
need to be replaced
Leaded petrol cannot be used in cars fitted with a catalytic
converter since lead strongly adsorbs onto the surface of
the catalyst
It is important to ensure the purity of the
reactants if poisoning can occur
When catalysts and reactants are in the same phase,
the reaction proceeds through an intermediate species
Homogeneous catalysis
The intermediate will often have a different oxidation state
to the original transition metal. At the end of the reaction
the original oxidation state will reoccur. This illustrates
importance of variable oxidation states of transition
metals in catalysis
N !o"#$% c&e're(ise)or*
Examples of homogeneous catalysts
The reaction between I
-
and S
2
O
8
2-
catalysed by Fe
2+
overall S
2
O
8
2-
+ 2I
-
2SO
4
2-
+ I
2
Catalysed alternative route
stage 1 S
2
O
8
2-
+ 2Fe
2+
2SO
4
2-
+ 2Fe
3+
stage2 2I
-
+ 2Fe
3+
2Fe
2+
+ I
2
The uncatalysed reaction is very slow because the reaction
needs a collision between two negative ions. Repulsion
between the ions is going to hinder this meaning high
activation energy
Learn these 2 examples and equations carefully
Both of the individual stages in the catalysed mechanism
involve collision between positive and negative ions and will
have lower activation energies.
The autocatalysis by Mn
2+
in titrations of C
2
O
4
2-
with MnO
4
-
overall 2 MnO
4
-
+ 5 C
2
O
4
2-
+ 16 H
+
2Mn
2+
+ 10 CO
2
+ 8 H
2
O
Catalysed alternative route
Step 1 4Mn
2+
+ MnO
4
-
+ 8 H
+
5Mn
3
+ + 4 H
2
O
Step 2 2Mn
3+
+ C
2
O
4
2-
2Mn
2+
+ 2 CO
2
The initial uncatalysed reaction is slow because the reaction needs
a collision between two negative ions which repel each other
leading to a high activation energy
As the Mn
2+
ions are produced act as an autocatalyst and the
reaction starts to speed up as they bring about the alternative
reaction route with lower activation energy.
The reaction eventually slows as the MnO
4
-
concentration drops
This is an example of autocatalysis where one of the
products of the reaction can catalyse the reaction
Mixture with only
reactants showing
effect of
autocatalysis
Mixture with
added
catalyst Mn
2+
at start
Following the reaction rate
This can be done by removing samples at set times and titrating to work out the concentration of MnO
4
-
.
It could also be done by use of a spectrometer measuring the intensity of the purple colour. This method has the
advantage that it does not disrupt the reaction mixture, using up the reactants and it leads to a much quicker
determination of concentration
Autocatalytic Reaction between Ethanedioate and Manganate ions
Reaction between iodide and persulphate ions
Fe
3+
ions can also act as the catalyst because the two steps in the catalysed mechanism can occur in any order
7
Constructing a catalysed mechanism for a reaction
Example
The following reaction is catalysed by Co
2+
ions in an acidic solution. SO
3
2
+ O
2
SO
4
2
.
Write a mechanism for the catalysed reaction by writing two equations involving Co
2+
and Co
3+
ions
Split full equation into its
two half equations
SO
3
2
+ O
2
SO
4
2
SO
3
2
+ H
2
O SO
4
2
+ 2H
+
+ 2e
-
O
2
+ 2H
+
+ 2e
-
H
2
O
Add in cobalt to make two
new redox equations.
Making sure the oxidised
cobalt equation is
combined with the original
reduced half equation and
vice versa
Co
2+
Co
3+
+ e-
Co
3+
+ e- Co
2+
O
2
+ 2H
+
+ 2Co
2+
H
2
O + 2Co
3+
2Co
3+
+ SO
3
2
+ H
2
O SO
4
2
+ 2H
+
+ 2Co
2+
Check your two mechanism
equations add up to the original full
non catalysed equation
N !o"#$% c&e're(ise)or*
8
Other applications of transition metal complexes
Fe(II) in haemoglobin enables oxygen to be transported in the blood . Haem is an iron(II) complex with a multidentate ligand.
CO is toxic to humans as CO can from a strong coordinate bond with haemoglobin. This is a stronger bond than that made
with oxygen and so it prevents the oxygen attaching to the haemoglobin..
The Pt(II) complex cisplatin is used as an anticancer drug.
Pt
2+
Cl
-
Cl
-
N H
3
N H
3
Pt
2+
NH
3
Cl
-
Cl
-
N H
3
cisplatin transplatin
The cisplatin version only works as two chloride ions are displaced and the
molecule joins on to the DNA. In doing this it stops the replication of
cancerous cells.
It can also prevent the replication of
healthy cells by bonding on to
healthy DNA which may lead to
unwanted side effects like hair loss
In the body one Cl ligand is subsituted by a water molecule
Pt(NH
3
)
2
Cl
2
+ H
2
O [Pt(NH
3
)
2
Cl(H
2
O)]
+
+ Cl

Be able to apply your knowledge of bonding to given information in the


question to explain how it bonds to DNA molecule- generally a
combination of dative covalent bonding and hydrogen bonding
Silver Chemistry
A2 questions often link
module 2 halide silver
nitrate chemistry to
transition metals
Reactions of halides with Silver nitrate
Fluorides produce no precipitate
Chlorides produce a white precipitate
Ag
+
(aq) + Cl
-
(aq) AgCl(s)
Bromides produce a cream precipitate
Ag
+
(aq) + Br
-
(aq) AgBr(s)
Iodides produce a pale yellow precipitate
Ag
+
(aq) + I
-
(aq) AgI(s)
The silver halide precipitates can be treated
with ammonia solution to help differentiate
between them if the colours look similar:
[Ag(NH
3
)
2
]
+
AgBr AgCl
Dilute
NH
3
colourless solution
NaBr
Cream
precipitate
Ag
Aldehydes
Conc NH
3
white
precipitate
[Ag(H
2
O)
2
]
+
aq
Conc HNO
3
Dilute
NH
3
NaCl
colourless
solution
Ag
+
commonly forms linear complexes
e.g. [Ag(H
2
O)
2
]
+
[Ag(NH
3
)
2
]
+
,
[Ag(S
2
O
3
)
2
]
3-
and [Ag(CN)
2
]
-
All are colourless solutions.
Ag H
3
N NH
3
+
Silver behaves like the transition metals in that it can form complexes and can show catalytic behaviour
(although it adsorbs too weakly for many examples)
Silver is unlike the transition metals in that it does not form coloured compounds and does not have variable
oxidation states
Silver complexes all have a +1 oxidation state with a full 4d subshell (4d
10
). As it is 4d
10
in both its atom and
ion, it does not have a partially filled d subshell and so is not a transition metal by definition. It is not
therefore able to do electron transitions between d orbitals that enable coloured compounds to occur.
Ag O H
2
OH
2
+
[Ag(NH
3
)
2
]
+
is used in Tollens reagent to
distinguish between aldehydes and ketones .
Aldehydes reduce the silver in the Tollens
reagent to silver
Silver chloride dissolves in dilute ammonia to form a complex
ion
AgCl(s) + 2NH
3
(aq) [Ag(NH
3
)
2
]
+
(aq) + Cl
-
(aq)
Colourless solution
Silver bromide dissolves in concentrated ammonia to form a
complex ion
AgBr(s) + 2NH
3
(aq) [Ag(NH
3
)
2
]
+
(aq) + Br
-
(aq)
Colourless solution
Silver iodide does not react with ammonia it is too insoluble.
Red eq: [Ag(NH
3
)
2
]
+
+ e
-
Ag +2NH
3
Ox eq: CH
3
CHO + H
2
O CH
3
CO
2
H + 2H
+
+ 2e
-
N !o"#$% c&e're(ise)or*
[M(H
2
O)
6
]
2+
+ H
2
O [M(H
2
O)
5
(OH)]
+
+ H
3
O
+

Reactions of Inorganic Compounds in Aqueous Solution


Lewis acids and bases
definitions: Lewis acid: electron pair acceptor
Lewis base: electron pair donator
In the formation of complex ions the ligand is the Lewis
base as it donating a pair of electrons in the dative
covalent bond and the metal ion is the Lewis acid
Metal-aqua ions
Metal aqua ions are formed in aqueous solution
[M(H
2
O)
6
]
2+
, limited to M = Fe (green) , Co(pink) and Cu (blue);
[M(H
2
O)
6
]
3+
, limited to M = Al (colourless), Cr (ruby) and Fe (violet)
In solution Cr(III) often appears green and
Fe(III) appears yellow/brown due to
hydrolysis reactions. The ruby and violet
colour is only really seen in solid hydrated
salts that contain these complexes
Acidity or hydrolysis reactions
[M(H
2
O)
6
]
3+
+ H
2
O [M(H
2
O)
5
(OH)]
2+
+ H
3
O
+
The following equilibria happen in aqueous solutions of metal ions
The equilibria lead to generation of acidic
solutions with M
3+
ions, and very weakly
acidic solutions with M
2+
ions. The 3+ ions
are noticeably more acidic
The acidity of [M(H
2
O)
6
]
3+
is greater than that of [M(H
2
O)
6
]
2+
in terms of the greater polarising power
(charge/size ratio) of the 3+ metal ion. The greater the polarising power, the more strongly it attracts the water
molecule. This weakens the O-H bond so it breaks more easily
Reaction with limited OH
-
and limited NH
3
The bases OH
-
and ammonia when in limited
amounts form the same hydroxide
precipitates. They form in deprotonation
acid base reactions
M(OH)
2
(H
2
O)
4 (s)
: Cu blue ppt, Co blue ppt, Fe (II) green ppt
M(OH)
3
(H
2
O)
3 (s)
:Cr (III) green ppt, Fe(III) brown ppt, Al white ppt
[Cu(H
2
O)
6
]
2+
(aq)
+ 2OH
-
(aq)
Cu(H
2
O)
4
(OH)
2 (s)
+ 2H
2
O
(l)
[Cr(H
2
O)
6
]
3+
(aq)
+ 3OH
-
(aq)
Cr(H
2
O)
3
(OH)
3 (s)
+ 3H
2
O
(l)
[Co(H
2
O)
6
]
2+
(aq)
+ 2NH
3 (aq)
Co(H
2
O)
4
(OH)
2 (s)
+ 2NH
4
+
(aq)
[Fe(H
2
O)
6
]
3+
(aq)
+ 3NH
3 (aq)
Fe(H
2
O)
3
(OH)
3 (s)
+ 3NH
4
+
(aq)
This process can happen step wise removing one proton at a time. Be able to write equations for this too
e.g. [Cr(H
2
O)
6
]
3+
(aq)
+ OH
-
(aq)
[Cr(H
2
O)
5
(OH)]
2+
(aq)
+ H
2
O
(l)
Reaction with excess OH
-
With excess NaOH, the Cr and Al hydroxides dissolve.
Cr becomes [Cr(OH)
6
]
3-
(aq) green solution
Al becomes [Al(OH)
4
]
-
(aq) colourless solution
These hydroxides are classed as amphoteric as
they dissolve in both acids and bases
Cr(H
2
O)
3
(OH)
3 (s)
+ 3OH
-
(aq )
[Cr(OH)
6
]
3-
(aq)
+ 3H
2
O
(l)
Al(H
2
O)
3
(OH)
3 (s)
+ OH
-
(aq )
[Al(OH)
4
]
-
(aq)
+ 3H
2
O
(l)
Cr(H
2
O)
3
(OH)
3 (s)
+ 3H
+
(aq )
[Cr(H
2
O)
6
]
3+
(aq)
Al(H
2
O)
3
(OH)
3 (s)
+ 3H
+
(aq )
[Al(H
2
O)
6
]
3+
(aq)
Reaction with excess NH
3
With excess NH
3
ligand substitution reactions occur with Cu, Co and Cr and their precipitates dissolve
The ligands NH
3
and H
2
O are similar in size and are
uncharged. Ligand exchange occurs without change of
co-ordination number for Co and Cr
Cr becomes [Cr(NH
3
)
6
]
3+
purple solution
Co becomes [Co(NH
3
)
6
]
2+
pale yellow solution
This substitution may, however, be incomplete
as in the case with Cu
Cu becomes [Cu(NH
3
)
4
(H
2
O)
2
]
2+
deep blue solution
Remember this Co complex is oxidised to +3 on
standing in air
Cr(OH)
3
(H
2
O)
3(s)
+ 6NH
3 (aq)
[Cr(NH
3
)
6
]
3+
(aq)
+ 3H
2
O
(l)
+ 3OH
-
(aq)
Cu(OH)
2
(H
2
O)
4(s)
+ 4NH
3 (aq)
[Cu(NH
3
)
4
(H
2
O)
2
]
2+
(aq)
+ 2H
2
O
(l)
+ 2OH
-
(aq)
Co(OH)
2
(H
2
O)
4(s)
+ 6NH
3 (aq)
[Cr(NH
3
)
6
]
2+
(aq)
+ 4H
2
O
(l)
+ 2OH
-
(aq)
[Cr(H
2
O)
5
(OH)]
2+
(aq)
+ OH
-
(aq)
[Cr(H
2
O)
4
(OH)
2
]
+
(aq)
+ H
2
O
(l)
Here the NH
3
and OH
-
ions are acting as
bronsted-lowry bases accepting a proton
In these reactions NH
3
is
acting as a lewis base
donating an electron pair
N !o"#$% c&e're(ise)or*
10
Reactions with chloride ions
Addition of a high concentration of chloride ions (from conc HCl or
saturated NaCl) to an aqueous ion lead to a ligand substitution
reaction.
The Cl
-
ligand is larger than the uncharged H
2
O and NH
3
ligands and that ligand exchange can involve a change of
co-ordination number
Additon of conc HCl to aqueous ions of Cu
and Co lead to a change in coordination
number from 6 to 4
[CuCl
4
]
2-
yellow/green solution
[CoCl
4
]
2-
blue solution
[Cu(H
2
O)
6
]
2+
+ 4Cl
-
[CuCl
4
]
2-
+ 6H
2
O
Reactions with carbonate solution
The 2+ ions react differently to the 3+ ions with carbonate solutions
The 2+ ions with carbonate solution results in MCO
3
ppt being formed (Cu blue/green, Co pink, Fe(II) green )
Cu
2+
(aq)
+ CO
3
2-
(aq)
CuCO
3 (s)
These are
precipitation
reactions
The 3+ ions with carbonate solution form a M(OH)
3
ppt and CO
2
gas is evolved
MCO
3
is formed with 2+ ions but M
2
(CO
3
)
3
is not formed with 3+ ions. The difference
is explained by the greater polarising
power of the 3+ ion due to its higher
charge density.
Al forms white ppt of Al(OH)
3
(H
2
O)
3
+ CO
2
Cr (III) forms green ppt of Cr(OH)
3
(H
2
O)
3
+ CO
2
Fe(III) forms brown ppt of Fe(OH)
3
(H
2
O)
3
+ CO
2
2[Cr(H
2
O)
6
]
3+
(aq)
+ 3CO
3
2-
(aq)
2Cr(OH)
3
(H
2
O)
3(s)
+3CO
2
+ 3H
2
O
(l)
The substitution of unidentate ligand with a bidentate or a multidentate ligand leads to a more stable complex.
Stability of complexes
[Cu(H
2
O)
6
]
2+
(aq)
+ EDTA
4-
(aq)
[Cu (EDTA)]
2-
(aq)
+ 6H
2
O
(l)
The copper complex ion has changed from having unidentate ligands to a multidentate ligand
In this reaction there is an increase in the entropy because there are more moles of products than
reactants (from 2 to 7), creating more disorder.
This chelate effect can be explained in terms of a positive entropy change in these reactions as more
molecules of products than reactants
These are classed as acidity reactions
These are
tetrahedral in
shape
Fe
2+
(aq)
+ CO
3
2-
(aq)
FeCO
3 (s)
2[Fe(H
2
O)
6
]
3+
(aq)
+ 3CO
3
2-
(aq)
2Fe(OH)
3
(H
2
O)
3(s)
+3CO
2
+ 3H
2
O
(l)
[Co(H
2
O)
6
]
2+
+ 4Cl
-
[CoCl
4
]
2-
+ 6H
2
O
Co
2+
(aq)
+ CO
3
2-
(aq)
CoCO
3 (s)
2[Al (H
2
O)
6
]
3+
(aq)
+ 3CO
3
2-
(aq)
2Al(OH)
3
(H
2
O)
3(s)
+3CO
2
+ 3H
2
O
(l)
[Cu(H
2
O)
6
]
2+
+ CO
3
2-
CuCO
3
+ 6H
2
O
[Co(H
2
O)
6
]
2+
+ CO
3
2-
CoCO
3
+ 6H
2
O
[Fe(H
2
O)
6
]
2+
+ CO
3
2-
FeCO
3
+ 6H
2
O
Be careful: If solid copper chloride (or any other metal )is
dissolved in water it forms the aqueous [Cu(H
2
O)
6
]
2+
complex
and not the chloride [CuCl
4
]
2-
complex
Free energy G will be negative as S is positive and H is small
The enthalpy change is small as there are similar numbers of bonds in both complexes
The stability of the EDTA complexes has many applications. It can be added to rivers to remove
poisonous heavy metal ions as the EDTA complexes are not toxic. It is in many shampoos to remove
calcium ions present in hard water, so helping lathering.
N !o"#$% c&e're(ise)or*
11
Ethanedioate
A 6 coordination number
complex with bidentate
ethanedioate ligands e.g.
[Cr(C
2
O
4
)
3
]
3- Cu(H
2
O)
6
2+
+ 3C
2
O
4
2-
[Cu(C
2
O
4
)
3
]
4-
+ 6H
2
O
C
2
O
4
2-
Cr(H
2
O)
6
3+
+ 3C
2
O
4
2-
[Cr(C
2
O
4
)
3
]
3-
+ 6H
2
O Octahedral shape with
90
o
bond angles
Partial substitution of ethanedioate ions may
occur when a dilute aqueous solution containing
ethanedioate ions is added to a solution
containing aqueous copper(II) ions. In this
reaction four water molecules are replaced and
a new complex is formed.
2-
OH
2
O
O
C
C
O
O
Cu
O
O
C
C
O
O
OH
2
3-
C
C O
O
C
C
O
O
C
C
O
O
Cr
O
O
O
O
O
O
Cu(H
2
O)
6
2+
+ 2C
2
O
4
2-
[Cu(C
2
O
4
)
2
(H
2
O)
2
]
2-
+ 4H
2
O
It has a coordination number of 6
Octahedral shape
Bond angle around Cr 90
o
3+
H
2
C
NH
2
NH
2
CH
2
H
2
C
NH
2
NH
2 CH
2
CH
2
NH
2
NH
2
Cr
CH
2
There are 3 bidentate ligands in this
complex each bonding in twice to the
metal ion
Ethane-1-2-diamine is a common bidentate ligand.
Ethane-1-2-diamine, as a base, can also carry out the deprotonation reactions
(similar to those of ammonia) forming hydroxide precipitates.
2[Al(H
2
O)
6
]
3+
(aq)
+ 3 H
2
NCH
2
CH
2
NH
2 (aq)
2Al(H
2
O)
3
(OH)
3 (s)
+ 3 [H
3
NCH
2
CH
2
NH
3
]
2+
(aq)
Cu(H
2
O)
6
2+
+ 3NH
2
CH
2
CH
2
NH
2
[Cu(NH
2
CH
2
CH
2
NH
2
)
3
]
2+
+ 6H
2
O
[Co(NH
3
)
6
]
2+
+ 3NH
2
CH
2
CH
2
NH
2
[Co(NH
2
CH
2
CH
2
NH
2
)
3
]
2+
+ 6NH
3
This reaction has an increase in entropy because of in the increase
in moles from 4 to 7 in the reaction. S is positive.
Its enthalpy change H is close to zero as the number of dative
covalent and type (N to metal coordinate bond) are the same so
the energy required to break and make bonds will be the same.
Therefore Free energy G will be negative and the complex
formed is stable
Ethane-1-2-diamine
More on some common ligands
N !o"#$% c&e're(ise)or*
12
Sometimes a compound containing a complex may have Cl
-
ions acting as ligands inside the complex and
Cl
-
ions outside the complex attracted ionically to it. If silver nitrate is added to such a compound it will only
form the silver chloride precipitate with the free chloride ions outside of the complex.
e.g. Co(NH
3
)
6
Cl
3
reacts on a 1:3
mole ratio with silver nitrate as
there are three free Cl
-
ions. So
all 3 Cls are outside the complex
e.g. Cr(NH
3
)
5
Cl
3
reacts on a 1:2
mole ratio with silver nitrate as
there are two free Cl
-
ions. So 1
Cl is a ligand and 2 are outside
the complex
Cr
NH
3
N H
3
N H
3
NH
3
NH
3
Cl
-
2+
2Cl
-
e.g. Cr(NH
3
)
4
Cl
3
reacts on a
1:1 mole ratio with silver
nitrate as there is one free
Cl
-
ion. So 2 Cls are ligands
and 1 is outside the complex
Cr
NH
3
N H
3
N H
3
Cl
-
NH
3
Cl
-
+
Cl
-
EDTA titrations
The formation of the stable EDTA complex with metal ions can with the choice of suitable indicator be
done in a quantitative titration.
[Cu(H
2
O)
6
]
2+
+ EDTA
4-
[Cu(EDTA)]
2-
+ 6H
2
O Always the same 1:1 ratio with any metal ion
A river was polluted with copper(II)
ions. 25.0 cm
3
sample of the river
water was titrated with a 0.0150
mol dm
3
solution of EDTA
4
, 6.45
cm
3
were required for complete
reaction.
Calculate the concentration, in mol
dm
3
, of copper(II) ions in the river
water.
Step1 : find moles of KMnO
4
moles = conc x vol = 0.0150 x 6.45/1000
= 9.68x10
-5
mol
Step 2 : using balanced equation find moles Cu
2+
1:1 ratio
= 9.68x10
-5
mol
Step 3 : find conc Cu
2+
in 25cm
3
= 9.68x10
-5
/0.025
= 0.00387 moldm
-3
Quantitative calculations with complex ions
Using Silver nitrate to work out formulae of chloride containing complexes
N !o"#$% c&e're(ise)or*
Co
NH
3
N H
3
N H
3
NH
3
NH
3
NH
3
3+
3Cl
-
13
[M(H
2
O)
6
]
2+
[Cu(H
2
O)
6
]
2+
blue sol
[Fe(H
2
O)
6
]
2+
green sol
[Co(H
2
O)
6
]
2+
pink sol
M(OH)
2
(H
2
O)
4
Cu(OH)
2
(H
2
O)
4
blue ppt
Fe(OH)
2
(H
2
O)
4
green ppt
Co(OH)
2
(H
2
O)
4
blue ppt
Few drops OH
-
or NH
3
[Cu(NH
3
)
4
(H
2
O)
2
]
2+
deep blue solution
[Co(NH
3
)
6
]
2+
yellow/light brown solution
Air or H
2
O
2
M(OH)
3
(H
2
O)
3
Fe(OH)
3
(H
2
O)
3
brown ppt
Co(OH)
3
(H
2
O)
3
brown ppt
H
+
excess NH
3
Air or H
2
O
2
[Co(NH
3
)
6
]
3+
brown sol
excess OH
-
CO
3
2-
MCO
3
CuCO
3
blue/green ppt
FeCO
3
green ppt
CoCO
3
pink ppt
Conc Cl
-
[MCl
4
]
2-
[CuCl
4
]
2-
green sol
[CoCl
4
]
2-
blue sol
water
2+ Ion Summary
[M(H
2
O)
6
]
3+
[Cr(H
2
O)
6
]
3+
violet sol
[Fe(H
2
O)
6
]
3+
yellow sol
[Al(H
2
O)
6
]
3+
colourless sol
M(OH)
3
(H
2
O)
3
Cr(OH)
3
(H
2
O)
3
green ppt
Fe(OH)
3
(H
2
O)
3
brown ppt
Al(OH)
3
(H
2
O)
3
white ppt
Few drops
OH
-
or NH
3
[Cr(NH
3
)
6
]
3+
violet sol
H
+
excess NH
3
H
2
O
2
CrO
4
2-
yellow sol
excess OH
-
CO
3
2-
[Cr(OH)
6
]
3-
green sol
[Al(OH)
4
]
-
colourless sol
(+ CO
2
)
Cr
2
O
7
2-
orange sol
OH
-
H
+
3+ Ion Summary
N !o"#$% c&e're(ise)or*
Cr
2
O
7
2-
(aq)
+6
Orange
solution
+3
+2
[Cr(H
2
O)
6
]
3+
(aq)
violet
solution
[Cr(H
2
O)
6
]
2+
(aq)
blue
solution
Zinc and HCl
Zinc and HCl
Hydrogen atmosphere
Excess
NaOH
[Cr(OH)
6
]
3-
Green
solution
H
2
O
2
CrO
4
2-
(aq)
Yellow
solution
acid
alkali
Or Fe
2+
acidified
with HCl
Cr(H
2
O)
3
(OH)
3
s)
Limited
NaOH
or NH
3
Green
precipitate
[Cr(NH
3
)
6
]
3+
purple
solution
14
Chromium summary
Excess
NH
3
Cr(OH)
6
3-
(aq)
H
2
O
2
CrO
4
2-
(aq)
Green solution
Reduction :H
2
O
2
+ 2e
-
2OH
-
Oxidation: [Cr(OH)
6
]
3-
+ 2OH
-
CrO
4
2-
+ 3e
-
+ 4H
2
O
2 [Cr(OH)
6
]
3-
+ 3H
2
O
2
2CrO
4
2-
+2OH
-
+ 8H
2
O
yellow solution
Reducing Chromium
Cr
3+
(green) and then Cr
2+
(blue) are formed by reduction of Cr
2
O
7
2-
(orange) by the strong reducing agent zinc in (HCl) acid solution.
Fe
2+
is a less strong reducing agent and will only reduce the
dichromate to Cr
3+
Cr
2
O
7
2-
+ 14H
+
+ 3Zn 2Cr
3+
+ 7H
2
O + 3 Zn
2+
Cr
2
O
7
2-
+ 14H
+
+ 4Zn 2Cr
2+
+ 7H
2
O + 4 Zn
2+
Cr
2
O
7
2-
+ 14H
+
+ 6Fe
2+
2Cr
3+
+ 7H
2
O + 6 Fe
3+
Orange green
The Fe
2+
and Cr
2
O
7
2-
in acid solution reaction can be used
as a quantitative redox titration. This does not need an
indicator
Keeping the zinc/dichromate under a hydrogen
atmosphere is needed to reduce it to Cr
2+
,
because O
2
in air will oxidise Cr
2+
up to Cr
3+
O
2
Oxidising Chromium
Chromate/ dichromate equilibrium
2 CrO
4
2-
+ 2H
+
Cr
2
O
7
2-
+ H
2
O
Yellow solution orange solution
The chromate CrO
4
2-
and dichromate Cr
2
O
7
2-
ions can be converted
from one to the other by the following equilibrium reaction
This is not a redox reaction as both
the chromate and dichromate ions
have an oxidation number of +6. This
is an acid base reaction
Addition of acid will by application of le chatelier push the equilibrium to the dichromate
Addition of alkali will remove the H
+
ions and, by application of le chatelier, push the equilibrium to
the chromate
N !o"#$% c&e're(ise)or*