CHM826: METAL IONS IN SOLUTION II (2CU)

INTRODUCTION

Most chemical reactions and many determinations are carried out in a solvent. The properties of
these solvents are important to the success or failure of any determination. Water (aqueous solvent)
is usually used for simple chemical study due to its excellent solvent action particularly on solute
with ionic lattice. Moreover, it is non-flammable, none toxic and readily available. These factors
determine the choice of water as solvent for many simple laboratory works. However, for more
advanced work and for organic chemists, other solvents are often used instead of water due to the
fact that many organic compounds do not dissolve in water but are readily soluble in non-polar
organic solvent such as benzene, carbon tetrachloride, ethers and so on.

In general, a substance tends to dissolve readily in solvent with similar structure and polarity,
though water dissolve many organic compounds whose molecules contain an OH group such as
sugars, alcohol, acids etc. Other non-aqueous solvents are necessary to get long aliphatic such as
paraffin wax or fats into solution. Some of these solvents and their properties are discuss here.

DEFINITION AND CLASSIFICATION OF NON-AQUEOUS SOLVENTS

Non-aqueous solvent are molecular liquids other than water. Non-aqueous solvents are often
mixed with water or some other non-aqueous solvents, to obtain desirable solvent properties. These
mixtures of solvents are called mixed solvents. Non-aqueous solvents are broadly classified into
two (2) main classes viz: protic or protonic and aprotic solvent.

1. Protic or protonic solvents: these are solvents containing ionisable hydrogen and are acidic
in nature. Examples are mineral acids such as HNO3, HCl, HF, and NH3 even though it is
basic but it can furnish hydrogen when stronger base is present.
2. Aprotic solvents: these are non-aqueous solvents that do not contain a replaceable
hydrogen. This class of solvent is further subdivided into three categories:
(a) Non-polar or very weakly polar solvents: these are non-dissociated liquids which do
not solvate. Example are CF4 and hydrocarbons
(b) Generally polar: they are non-dissociative but strongly solvating liquids. Examples
include CH3CN, DMSO and SO2.

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 (c) Highly polar auto ionizing: solvents for example inter halogen compounds like BrF3
and IF3

CHARACTERISTICS OF NON-AQUEOUS SOLVENTS

1) The temperature over which it exist as liquid: solvents that are liquid at room temperature
and 1atm are most useful because they are easily handled, but it is also important to be able
to carry out measurement or reactions at temperatures well above and below the room
temperature.
S/N SOLVENT FORMULA TEMPERATURE RANGE
(OC)
1. Water H2O 0 – 100
2. Acetonitrile CH3CN −45 – 82
3. Dimethyl formamide HCON(CH3)2 −61 – 161
4. Dimethyl sulfoxide (CH3)2SO 18 – 189
5. Chloronitrate ClNO3 −17 – 18 (in a vacuum)
6. Sulphuric acid H2SO4 −14 – 26
7. Phosphorous POCl2 1 – 118
oxydichloride
8. Ammonia NH3 −78 – (−33)
9. Hydrogen fluoride HF −83 – 20

2) Its dielectric constant: a very strong factor in the ability of a solvent to dissolve an ionic
solid is its dielectric constant (E). the dielectric constant has an inverse relationship with force of
attraction between the cations and anions immersed in a medium and the two are related by the
equation of the inverse square law:-
𝑞+ 𝑞−
𝐹=
4𝜋𝐸𝑟 2
Where r is distance between q+ and q−, and this means that the higher the value of the
dielectric constant for a given solvent the better its strength to dissolve the ionic solid since
the force of attraction between the cation and anion of the solid will be weakened.

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 3) Its donor acceptor property: The ability of a solvent to solvate the dissolved particle is
also important in determining the ability of the solvent to keep the dissolved solute in
solution. For ionic solute there are both anions and cations that needs to be solvated. The
cations are often smaller for example in NaCl, FeCl2 KOH and their solvation is of great
importance. The solvated cations are essentially complexes in which the ligands are the
solvent molecules. The order of coordinating ability towards a typical cation for some
common solvents are given as follows:
DMSO > DMF = H2O > Acetone > CH3CN > TMSO2 > CH3NO2 > C6H5NO2 > CH2Cl2.
In the presence of solvated cation, the positive end of the solvent orient themselves towards
the anions. It is worthy to note that the dielectric constant and ability to solvate are related
property and tend to increase simultaneously, although the relationship cannot be
quantified. The more polar the molecules of the solvent are, the higher the dielectric
constant tend to be and the better its ability to use the negative and positive region to solvate
an ion.
NaCl → Na+ Cl−

Cl-   Cl-
H H
O



H  H

O Na+ O



H  H



O
- Cl-
Cl H H

Fig 1: solvation process
The donor acceptor property comes in the sense that the donor should be able to donate a
lone pair of electrons (for solvating the cation) and accept the lone pair of electrons (for
solvating the inion) for it to be a good solvent
4) Protonic acidity or basicity: This refers to the extent of dissociation which determine the
number of H+ released in solution (acidity) especially for solvents with more than H+ ion
in their molecule, or the extent and the number of H+ accepted (basicity). This is in
accordance with Brɸnsted’s Lorry’s definition of acids and bases.

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 5) Nature and extent of auto ionization: auto dissociation or self-ionization mainly occur in
protnic solvents. For example:
2H2O → H3O+ + OH-
2HCl → H2Cl + Cl−
2HF → H2F + F−
2HNO3→ H2NO3 + NO3−
2H2SO4 → H3SO4+ + HSO4−
2NH3 → NH4 + NH2−

However some aprotic solvent especially the interhalogen compounds undergo auto
dissociation but such solvents are highly reactive and therefore difficult to handle,
examples are given by:
2BrF3 ↔ BrF2+ + BrF4-
2IF5 ↔ IF4+ + IF6-
The significance of auto ionization is that the solutes encounter not only the solvent but
also the cation and anion resulting from auto dissociation and this facilitate solvent-solute
interaction and therefore aid the dissociation of solute.

WHY DO WE NEED NONE AQUEOUS SOLVENTS AS INORGANIC CHEMISTS?

There are two main reasons why it is sometimes necessary to use solvents other than water for the
preparation of metal complexes. The reasons are:

1. The metal ion has strong affinity for water

2. The ligand is not water soluble

Metal ion with high affinity for water

A few metal ions that have high affinity for water and thus form strong metal-oxygen bond are
Al3+, Fe3+ and Cr3+. Addition of basic ligands to aqueous solution of these ions generally results in
the formation of gelateneous precipitate rather than a complex containing the added ligands. The
metal-oxygen bond remains intact but the oxygen-hydrogen bond is broken. The hydrated metal
ions behave as protic acids. For example, the aqueous reaction between chromium (III) ions and
ethylenediamine give [Cr(H2O)3(OH)3] and enH

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[Cr(H2O)6]3+ + 3en → [Cr(H2O)3(OH)3] + 3enH
Violet Green
If instead, the anhydrous chromium (III) salt and non-aqueous solvent is used, the reaction yields
the desired complex ion [Cr(en)3]3+

Ether
CrCl3 + 3en [Cr(en)3]Cl3
Purple Yellow
Another example is the preparation of [Cr(en)3Cl2]Cl

CrCl3 + 3en DMF en/DMF

[Cr(DMF)3Cl3] [Cr(en)2Cl2]

Other examples of non-aqueous solvents include dimethylsulphoxide (DMSO), acetone and

acetonitrile. Example of complexes that involve the use of DMSO are as follows:

2FeCl3 DMSO [Fe(DMSO)6]Cl3 + [Fe(DMSO)4Cl2]Cl

3CoCl2 DMSO [Co(DMSO)2Cl2] + [Co(DMSO)Cl3]- + CoCl42-

2NiCl2 DMSO [Ni(DMSO)6]2+ + [NiCl4]2-

EtOH/H2O
[Fe(H2O)6] + 3bipy [Fe(bipy)3]2+ + 6H2O

Preparation of [Cu(H2O)4(ac)2], [Co(CH3CN)2Cl4]2- and [FeCl2(CH3CN)4][FeCl4] involves the use

of acetone and acetonitrile respectively.

The ligands are not water soluble

Some ligands are insoluble in aqueous medium, often suffices to dissolve in organic solvent-water
mixture and add to an aqueous solution of the metal salt. Metal complexes of bipyridiene and 1,10-
phenanthroline are generally prepare in this way. The addition of the alcoholic solution of the
ligand to an aqueous solution of the metal salt readily yields the complexes. For example,

EtOH/H2O
[Fe(H2O)6] + 3bipy [Fe(bipy)3]2+ + 6H2O

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 EtOH/H2O
[Fe(H2O)6] + 3phen [Fe(phen)3]2+ + 6H2O

Structures of some non-aqueous solvents

O CH3
O

S N H
H3C C C
H3C CH3
H3C CH3
DMSO
O Propan-2-one
N,N-Dimethyl-formamide

H3C C N
Acetonitrile
N N N N
[2,2']Bipyridinyl [1,10]Phenanthroline

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