Aqueous Inorganic Chemistry

Aqueous Inorganic Chemistry
12.3A
Vocabulary
• strengths and limitations
• similar and dissimilar
• consequent changes
• entropy, free energy
• limitations of the theory
• sufficiently acidic
• replacement of…
• a cyclic structure
• more favourable
Learning Objectives
• recognise various acid-base theories (Arrhenius, Bronsted-Lowry
and Lewis) and understand the conditions in which each may be
used, their strengths and limitations
• recognise and know the structure of metal-aqua ions
• understand the acid behaviour of these ions and their reactions with
ammonia solution, hydroxide and carbonate solutions to produce
insoluble hydroxides and complex ions
• understand ligand substitution with similar and dissimilar sized
ligands, and possible consequent changes of co-ordination number
• be able to explain ligand substitutions in terms of complex ion
stability
• recognise the existence of bi- and multidentate ligands and
understand the chelate effect in terms of entropy and free energy
change
Acid – base theories
• The Arrhenius Theory of acids and bases
– Limitations of the theory: Hydrochloric acid is
neutralised by ammonia gas → there aren't
any hydrogen ions or hydroxide ions in
solution - because there isn't any solution.
The Arrhenius theory wouldn't count this as
an acid-base reaction, despite the fact that it
is producing the same product as when the
two substances were in solution.
• The Brønsted-Lowry Theory of acids and
bases
– Doesn't go against the Arrhenius theory - it
just adds to it.
– Conjugate pairs
– Limitations of the theory: Doesn’t include
coordination compounds
• The Lewis Theory of acids and bases
– An acid is an electron pair acceptor.
– A base is an electron pair donor.
Lewis
7
Lewis Acid-Base
• In the Lewis theory of acid-base reactions,
bases donate pairs of electrons and acids
accept pairs of electrons.
8
Acid-Base Theories
Lewis
Brønsted-Lowry
Arrhenius
Metal-aqua ions
• Aqua = water
• A metal ion in aqueous solution (aqua ion)
is a cation dissolved in water [M(H2O)n]z+.
Metal aqua ions:
Metal ions in aqueous solution exist as aqua ions, where

water molecules act as ligands, and coordinate to the
metal ion via the oxygen donor atoms as shown for the
[Al(H2O)6]3+ hexaaqua ion below:
Figure 1. The aluminum(III) hexaaqua

ion, present in aqueous solution and
in many salts such as [Al(H2O)6]Cl3.
Metal ions can have varying numbers of water molecules
coordinated to them, ranging from four for the very small
Be(II) ion, up to 9 for the large La(III) ion.
coordination number = 4 coordination number = 9

Diagrammatic representation of the inner and outer
sphere of waters around a metal ion in solution:
BULK inner-sphere of
SOLVENT waters coordin-
ated to the metal
ion via M-O bonds
n+
outer-sphere of
more structured
waters held to the
inner-sphere by
H-bonding and
electrostatic
BULK BULK attraction
SOLVENT SOLVENT
Metal aqua ions as Brønsted acids:
Metal aqua ions can act as Brønsted acids, which means
that they can act as proton donors.
[Fe(H2O)6]3+(aq)  [Fe(H2O)5OH]2+(aq) + H+(aq)
Thus, if one dissolves a ferric salt, such as FeCl3.6H2O

in water, a fairly acidic solution of pH about 2 will result.
In fact, the orange color of such solutions is due to the

presence of the [Fe(H2O)5OH]2+ ion, and the [Fe(H2O)6]3+
cation is actually a very pale lilac color.
Reactions
• The aqua ions undergo hydrolysis.
• The first hydrolysis step is given
generically as:
[M(H2O)n]x+ + H2O ⇌ [M(H2O)n−1(OH)]y+ + H3O+
Reactions
With hydroxide:
Can be reversed
with an acid
Reactions
With ammonia solution
Reactions
• In some cases, ligand exchange
Reactions
• M3+ with carbonate solutions
• The 3+ hexaaqua ions are sufficiently
acidic to react with carbonate ions to
release carbon dioxide gas. You also get a
precipitate of the metal hydroxide.
Reactions
• M2+ with carbonate solutions
• The 2+ hexaaqua ions aren't strongly
acidic enough to release carbon dioxide
from carbonates. In these cases, you still
get a precipitate:
Ligand Substitution
• Replacing water with chloride ions
– add concentrated hydrochloric acid to a
solution containing hexaaqua ions.
– the six water molecules are replaced by four
chloride ions.
– the reaction taking place is reversible.
• Notice the change in the co-ordination

• The high chloride ion concentration
pushes the position of the equilibrium to
the right according to Le Chatelier's
Principle.
• This reaction can be easily reversed by
adding water to the solution. Adding water
to the right-hand side of the equilibrium
has the effect of moving the position of
equilibrium to the left.
• Replacing water molecules by ammonia
– Ammonia as a base: If you add a small
amount of ammonia solution you get
precipitates of the metal hydroxide.
– Ammonia as a ligand: In some cases, these
precipitates redissolve when you add more
ammonia to give solutions in which a ligand
exchange reaction has occurred.
Past exam question and
solution
• Video (from 7:34 until 14:58)
• https://www.youtube.com/watch?v=HN-
9ESoJlm4
• Replacement of the water by sulphate ions
– One of the water molecules is replaced by a
sulphate ion.
• A ligand exchange reaction in the test for
iron(III) ions.
– Test for iron(III) ions in solution.
– Adding thiocyanate ions, SCN- to a solution
containing iron(III) ions, you get an intense
blood red solution containing the ion
[Fe(SCN)(H2O)5]2+
The stability of complex ions
• Ligand substitutions occur because one
complex is more stable than the other.
• This can be explained by a stability
constant K (= the equilibrium constant).
– The larger the value of the stability constant,
the further the reaction lies to the right. That
implies that complex ions with large stability
constants are more stable than ones with
smaller ones.
The stability constant
value
ion Kn log Kn
(mol-1 dm3)
[Cu(NH3)(H2O)5]2+ K1 1.78 x 104 4.25
[Cu(NH3)2(H2O)4]2+ K2 4.07 x 103 3.61
[Cu(NH3)3(H2O)3]2+ K3 9.55 x 102 2.98
[Cu(NH3)4(H2O)2]2+ K4 1.74 x 102 2.24

The chelate effect
• A chelate: any of complex compounds
consisting of a central metal atom
attached to a large molecule, called a
ligand, in a cyclic or ring structure.
• Chelates are much more stable than
complex ions formed from simple
monodentate ligands. This is known as the
chelate effect.
The chelate effect
ion log K
[Cu(NH3)2(H2O)4]2+ 7.86
[Cu(H2O)4(en)]2+ 10.6
But why?
The chelate effect
• The enthalpy changes of the two reactions
are fairly similar.
– In each case you are breaking two bonds
between copper and oxygen atoms and
replacing them by two bonds between copper
and nitrogen atoms.
– The enthalpy change does not explain what
causes the difference in the extent to which
the two reactions happen.
The chelate effect
• The 1,2-diaminoethane equilibrium leads
to an increase in entropy.
– There are only two species on the left-hand
side of the equation, but three on the right. In
the other reaction, there is no change in the
total number of species before and after
reaction, and so no increase in entropy.
• Any change which increases the amount
of disorder increases the tendency of a
reaction to happen.
• Complexes involving multidentate ligands are more
stable than those with only unidentate ligands in them.
• The underlying reason for this is that each multidentate
ligand displaces more than one water molecule. This
leads to an increase in the number of species present in
the system, and therefore an increase in entropy.
• An increase in entropy makes the formation of the
chelated complex more favourable.
The chelate effect
Very little difference between mono and bidentate ligands

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Aqueous Inorganic Chemistry

Metal ions in aqueous solution exist as aqua ions, where

Figure 1. The aluminum(III) hexaaqua

coordination number = 4 coordination number = 9

[Fe(H2O)6]3+(aq)  [Fe(H2O)5OH]2+(aq) + H+(aq)

Thus, if one dissolves a ferric salt, such as FeCl3.6H2O

In fact, the orange color of such solutions is due to the

• Notice the change in the co-ordination

[Cu(NH3)(H2O)5]2+ K1 1.78 x 104 4.25

[Cu(NH3)2(H2O)4]2+ K2 4.07 x 103 3.61

[Cu(NH3)3(H2O)3]2+ K3 9.55 x 102 2.98

[Cu(NH3)4(H2O)2]2+ K4 1.74 x 102 2.24

Very little difference between mono and bidentate ligands

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