The chemistry of water

2. THE CHEMISTRY OF WATER

The formation energy of the . water
molecule, 242 kJ.mol-1 (58 kcal.mol-1 ), is.
high. Water is, therefore, extremely stable.
This stability, linked with its characteristic
electrical
properties
and
molecular

2.1.
WATER AS A SOLVENT

composition, makes water particularly

suitable for dissolving many substances
Most mineral substances are, in fact,
soluble in water as are also a large
number of gases and organic substances

genuine chemical reaction (solvation) takes

place. Complete solvation is dis solution.

To dissolve a substance is to destroy its 2.1.1. Solubility of the various phases

cohesion, which it owes to electrostatic or
. Gases
Coulomb forces which may be:
The solubility of gases obeys Henry's
laws (see page 276 and page 509).
. Interatomic
For example, at 10C, the solubility of
Strong chemical bonds: covalency bonds
principal
gases under a pressure of pure gas
(between atoms), electrovalency or ionic
equal to 102 kPa (1 bar), is:
bonds (atom-electrons).
. Intermolecular
Bonds of cohesion between molecules
(hydrogen bonds).
. Weak forces of attraction (London, Van
der Waals), which hold the whole substance
together.
The hydrating attraction of water (bipolar
molecule) has the effect of completely or
partially destroying (beginning with the
weakest) the various electrostatic links
between the atoms and molecules of the
substance to be dissolved, which are
replaced by new links with its own
molecules, and creating new structures; a

Gas
N2
O2
CO2
H2S
CH4
H2

Solubility
mg.l-1
23.2
54.3
2,318
5,112
32.5
1.6

Anhydrides (CO2 , SO2 ) and various

volatile acids (HCl) dissolve and then
combine. Their solubility coefficient is
much higher than that of other gases.
Oxygen is more soluble than nitrogen;
the dissolved gases extracted from a water
will be richer in oxygen than the initial
atmosphere from which they came.

Chap. l: Water, a fundamental element

. Liquids
As the water molecule is polar, the
solubility of a liquid in water depends on
the polarity of the molecules of the liquid
in question. For instance, molecules
containing the groups OH- (e.g., alcohol,
sugars), SH- and NH2- , being very polar,
are very soluble in water, whereas other
liquids (hydrocarbons, carbon tetrachloride,
oils and fats, etc.). which are non-polar, are
very sparingly soluble.
There may be partial miscibility; for
instance, two substances are miscible only
above a critical temperature (a temperature
above 63.5C for a mixture of water and
phenol) or below a minimum temperature
(trimethylamine is only soluble in all
proportions below 18.5C), or between two
critical temperatures, one upper and one
lower (the water-nicotine system).
2.1.2. Hydrophilization
The solubility of a substance may differ
in various solvents: for example, sodium
chloride is much more soluble in water than
in alcohol, whereas paraffin is soluble in
benzene but not in water.
Solubility in water depends on the nature
of the substance or at least on certain of its
constituent groups; the characteristic
groups are therefore classified as
hydrophilic
(OH-CO-NH2
etc.)
or
hydrophobic (CH3 -CH2 -C6 H5 ).
In some cases, solvation or simple
wetting take place with the aid of a third
constituent called a solubilizer for true
solutions, a peptizer for colloidal
suspensions, a stabilizer or emulsifier for
emulsions and suspensions, and a wetting
agent for surface effects.

These intermediary agents create

genuine links between the solvent and
substance to be dissolved, to be held in
dispersion or to be wetted (they lower the
surface tension).
The link on the solvent side is due to a
hydrophilic group, while the link on the
side of the substance to be transformed can
be a chemical link (action of bases and
strong acids) or a cohesion link. The latter
are formed from dissymetrical (semihydrophilic) molecules. One of the ends is
similar to water and hydrophilic, while the
other tends to associate (the action of
detergents, trisodium phosphate, wetting
agents) with the molecules of the substance
to be stabilized or to be adsorbed on its
surface. More hydrophilic aggregation or
adsorption complexes are then formed.
. Loss of hydrophilic properties
The intermediary agent can break the
link between the solvent and the substance
which is dissolved, dispersed or wetted.
Depending on the case in question, this
agent will be called a precipitant,
coagulant, flocculant, thickener or
wetting depressant. This break can be the
result of chemical action, for instance the
loss of OH- ions or of ionized groups. The
intermediary agent may destroy the semihydrophilic cohesion link by neutralizing
the hydrophilic part or by attracting the
hydrophobic part on the surface either of
air bubbles (flotation) or of a more or less
hydrophilic insoluble adsorbent.
The break may be the result of
neutralization of the electrostatic forces (by
the action of polyvalent cations and ionic
polyelectrolytes).

2. The chemistry of water

2.1.3. Activity and concentration

The relationship between solute and
solvent may be expressed in several ways:
- mole fraction: ratio of number of moles of
solute to total number of moles (solvent +
solute),
- molarity: number of moles dissolved in
one litre of solution.
The molecules of a solute behave in the
same way as a gas would in another gas,
and indeed it has been observed that when

2.2.
IONIZATION
An inorganic compound dissolved in
water dissociates to a greater or lesser
extent, with the formation of negatively
charged ions (anions) and positively
charged ions (canons). The dissolved
substance is called an electrolyte and
facilitates the flow of electric current:

the solute is greatly diluted, the law of ideal

gases holds good. When the concentration
becomes sizable, the dissolved molecules
are less active than the same number of
molecules of ideal gas. Concentration (c) is
replaced by activity [a]:
[a] = f(c)
f is called the activity coefficient and tends
towards 1 when the solution is very dilute.

Some acids or bases are entirely

dissociated even in relatively concentrated
solutions. They are called strong
electrolytes.

Other substances, such as acetic acid

CH3COOH, are only partially dissociated
in solution. These are weak electrolytes. In
this case we. must distinguish between total
acidity wich comprises all possible H+ ions
and free acidity which comprises
dissociated H+ ions.
Water, itself, is partially dissociated into
Where a single solution contains a ions according to the reversible reaction:
number of electrolytes, each is dissociated
to a certain extent and ions formed may
combine with one another to form new
This means that in water there are both
compounds.
For
example,
if
two H2 O. molecules and OH- (hydroxide ion)
compounds AB and CD are dissolved, the and H+ ions (in the hydrated H3 O+ form
solution will be found to contain molecules called hydronium ion).
AB, CD, AD and CB in equilibrium with
the ions A+, B-, C+ and D-. This equilibrium . Law of mass action
may change if insoluble compounds,
In the case of a chemical reaction at
complexes or gases form (Le Chatelier's equilibrium:
principle). For example, if the compound
AD is insoluble, the equilibrium is almost
entirely displaced to the right, in
accordance with the reaction:

Chap. l: Water, a fundamental element

where [A], [B], [C] and [D] represent
the activity of compounds in solution.
At equilibrium V1 = V2, therefore:

This is the law of mass action. K is

called the constant of thermodynamic
dissociation. To make it easier, we use
the designation pK = colog K. Tables
list the values of pK (see page 505).
Application of the law of mass action
to water: pH concept
Assuming that the coefficients of
ionic activity are equal to 1, we obtain:

Since the dissociation is always weak,

the concentration of the water
molecules is practically constant and we
may write:
(H+) [OH-] = Ke.
The value of the dissociation (or
ionization) constant of water is of the
order of 10-14 (mol.l-1 )2 at 23C. This
value varies with the temperature:
Temperature
C
0
18
25
50
100

Ionization
constant
Ke 1014
0.12
0.59
1.04
5.66
58.5

pKe
14.93
14.23
13.98
13.25
12.54

In pure water, we have:

(H+) = (OH-) = 10-7 mol.l-.
By convention, the exponent of the
concentration of H+ ions or pH
(hydrogen potential) is used:
pH = colog (H+)

The pH is measured by means of

coloured indicators or, preferably, by
an electrometric method (glasselectrode pH meter).
An acid medium is a solution in
which (H+) is greater than 10-7 mol.l-1
(pH < 7), an alkaline medium is one in
which (H+) is less than 10-7 mol.l-1 (pH
> 7).
. Strength of acids and bases in
aqueous solution
An acid is a substance capable of
losing protons, that is, H+ ions. A base
is a substance capable of accepting
these protons. There is, thus, in an
aqueous solution, an acid-base
equilibrium defined by the following
equation:
Applying the law of mass action and
taking the concentration of H2 O
molecules as a constant, we obtain:

KA , thus defined, is called the

affinity constant of the acid-base
couple.
The strength of an acid is
determined by the extent to which it
gives off H+ ions, that is, the larger the
value of KA or the smaller the value of
pKA the stronger the acid. The smaller
the value of KA , the stronger a base.
Thus, the ammonium ion NH4 + is a
weak acid with pKA = 9.2. The
corresponding base NH40H is a fairly
strong base.
The concept of pKA makes it
possible to calculate the pH of
mixtures of corresponding solutions of
acids, bases and salts:
- the pH of a solution of an acid with a
total concentration c is:
pH = 1/2 pKA 1/2 log c

2. The chemistry of water

- the pH of a solution of a base is:

pH =7+1/2 pKA + 1/2 logc
- the pH of a solution of a salt is:
pH = 1/2 pK1 + 1/2 pK2
K1 and K2 being the affinity constants of
the corresponding acid and base.
. Buffer solutions
In the case of a mixture of an acid of
concentration (A) and the corresponding
base, of concentration (B), if (A) = (B), this
solution is called a buffer solution.
Example: acetic acid - acetate.
A buffer solution is a solution the pH of
which varies little with the addition or
removal of H+ ions. These solutions are
useful when it is desired that a reaction
should take place with a constant pH.

Acetates,
acid
phthalates
and
monopotassium phosphates serve as the
basis for the preparation of a whole range
of buffer solutions.
Solubility
of
sparingly-soluble
compounds. Solubility product
The ionic equilibrium state of a sparingly
soluble or insoluble substance is:

The magnitude of KS, or solubility

product, is constant for a given temperature
and ionic strength of the solution. The less
soluble the substance, the smaller the value
of KS. For calcium carbonate, the solubility
of which is 12 mg.l-1 , the solubility product
KS is 10"z (mol.l-1 ). By analogy with the
pH, we write: pKs = colog 10-8.32 = 8.32.

However, very strong oxidants and

reducing
agents react remarkably quickly
2.3. OXIDATION-REDUCTION
on
water:
for example, chlorine easily
Water can take part, under certain
changes
into
the Clanion state according to
experimental conditions, in oxidationreduction with the following possible the following reaction:
reactions:

In the first case, the water is a donor of

electrons; it is a reducing agent: the
acceptor of electrons is an oxidant. In the
presence of water an oxidant releases
oxygen. In the second case, water is an
electron acceptor; it is an oxidant: the
electron donor is a reducing agent. In the
presence of water a reducing agent releases
hydrogen.
But reactions are very slow without
catalysts and in general the action of water
with respect to oxidation-reduction
reactions may be ignored.

oxygen is released and the medium

becomes acid.
Water can be broken down into oxygen
and hydrogen according to the following
reaction:
The
oxidation-reduction
neutrality
corresponds to the equal pressures of
oxygen and hydrogen, that is a pressure of
pH2 equal to 10-22 Pa.
The concept of oxidation-reduction
potential enables us to classify the various
oxidants and reducing agents in relation to
hydrogen and thus to each other (see page
249).