Aqueous Solutions

and Chemical
Equilibria
Most analytical techniques require the state of
chemical equilibrium. At equilibrium, the rate
of a forward process or reaction and that of
the reverse process are equal.
As water slowly seeps over the limestone surface
(superficie calcarea) of the cave, calcium carbonate
dissolves in the water according to the chemical
equilibrium.

The flowing water becomes saturated with calcium

carbonate.
As carbon dioxide is swept away, the reverse reaction
becomes favored, and limestone is deposited in
formations whose shapes are governed by the path of
the flowing water.
 “Frozen Niagara” in
Mammoth Cave
National Park in
Kentucky.

Stalactites and stalagmites

are examples of similar
formations found where
water saturated with
calcium carbonate drips
from the ceiling to the floor
of caves over eons.
Il carbonato di calcio è il sale di calcio dell'acido
carbonico.
Puro, a temperatura ambiente è un solido bianco
poco solubile in acqua, cui impartisce una reazione
lievemente basica: 100 grammi in un litro di acqua
a 20 °C formano una sospensione il cui pH è circa 10!

Perché?

CO32- + H2O HCO3- + OH-

Come gli altri carbonati, subisce decomposizione per
riscaldamento o per contatto con sostanze acide,
liberando anidride carbonica.
Su questa sua caratteristica si basa il metodo per la sua
determinazione, detto analisi calcimetrica.

CaCO3 + HCl CO2 + H2O + CaCl2

 Il carbonato di calcio è il maggiore componente
del calcare sciolto nell'acqua e il principale responsabile della
sua durezza. In combinazione con il riscaldamento dell'acqua
per usi civili dà origine all'incrostazione calcarea.

CaCO3 CO2 + CaO

In natura, il carbonato di calcio è il

materiale che costituisce, in tutto o
in parte, una grande varietà di tipi di
rocce: il marmo, le rocce calcaree,
il travertino. I minerali costituiti da
carbonato di calcio sono
l'aragonite e la calcite.
 Acids and Bases

In 1923, J. N. Brønsted in Denmark and J. M. Lowry in England

proposed independently a theory of acid/base behavior that is
especially useful in analytical chemistry.
According to the Brønsted-Lowry theory, an acid is a proton
donor, and a base is a proton acceptor. For a molecule to behave
as an acid, it must encounter a proton acceptor (or base).
Likewise, a molecule that can accept a proton behaves as a base
if it encounters an acid.
An important feature of the Brønsted-Lowry concept is
the idea that the product formed when an acid gives up
a proton is a potential proton acceptor and is called the
conjugate base of the parent acid. For example, when
the species acid1 gives up a proton, the species base1
is formed, as shown by the reaction

Many solvents are proton donors or proton acceptors

and can thus induce basic or acidic behavior in solutes
dissolved in them.
 An acid that has donated a proton
becomes a conjugate base capable
of accepting a proton to reform the
original acid. Similarly, a base that
has accepted a proton
becomes a conjugate acid that can
donate a proton to form the original
base.

Water is the classic example of an amphiprotic solvent, that

is, a solvent that can act either as an acid or as a base
depending on the solute.
 Amphiprotic Species

The simple amino acids are an important class of

amphiprotic compounds that contain both a weak acid and
a weak base functional group. When dissolved in water, an
amino acid, such as glycine, undergoes a kind of internal
acid/base reaction to produce a zwitterion—a species that
has both a positive and a negative charge.
Other common amphiprotic solvents are methanol, ethanol,
and anhydrous acetic acid. In methanol, for example, the
equilibria are analogous to the water equilibria.
Amphiprotic solvents undergo self-ionization, or
autoprotolysis, to form a pair of ionic species.
Autoprotolysis is yet another example of acid/base
behavior, as illustrated

The extent to which water undergoes autoprotolysis at

room temperature is slight.
The first two are strong acids because reaction with the
solvent is sufficiently complete that no undissociated solute
molecules are left in aqueous solution.
The rest are weak acids, which react incompletely with water
to give solutions containing significant quantities of both the
parent acid and its conjugate base. Note that acids can be
cationic, anionic, or electrically neutral. The same holds for
bases.
The acids in Figure become progressively weaker from top to
bottom. Ammonium ion is an even weaker acid with only
about 0.01% of this ion being dissociated into hydronium ions
and ammonia molecules.
Perchlorate and chloride ions have no affinity for protons.
The tendency of a solvent to accept or donate protons determines
the strength of a solute acid or base dissolved in it. For example,
perchloric and hydrochloric acids are strong acids in water.

If anhydrous acetic acid, a weaker proton acceptor than water, is

substituted as the solvent, neither of these acids undergoes complete
dissociation. Instead, equilibria such as the following are established:

Perchloric acid is, however, about 5000 times stronger than

hydrochloric acid in this solvent.
Acetic acid thus acts as a differentiating solvent toward the
two acid revealing the inherent differences in their acidities.

Water, on the other hand, is a leveling solvent for

perchloric, hydrochloric, and nitric acids because all three
are completely ionized in this solvent and show no
differences in strength.
Types of Equilibrium Constants in
Analytical Chemistry
Applying the Ion-Product Constant for Water

Aqueous solutions contain small

concentrations of hydronium and hydroxide
ions as a result of the dissociation reaction

How much is the water concentration?

Suppose we have 0.1 mol of HCl in 1 L of water. The presence
of this acid will shift the equilibrium to the left. Originally,
however, there was only 10-7 mol/L OH- to consume the added
protons.
 Using Solubility-Product Constants

Most, but not all, sparingly soluble salts are essentially completely
dissociated in saturated aqueous solution. For example, when an
excess of barium iodate is equilibrated with water, the dissociation
process is adequately described by the equation

When we say that a sparingly soluble salt is completely

dissociated, we do not imply that all of the salt dissolves.
What we mean is that the very small amount that does go into
solution dissociates completely.
What does it mean to say that
“an excess of barium iodate
is equilibrated with water”?
It means that more solid barium
iodate is added to a portion of
water than would dissolve at the
temperature of the experiment.
Some solid BaIO3 is in contact
with the solution.
In other words, the number of
moles of Ba(IO3)2 divided by the
volume of the solid Ba(IO3)2 is
constant no matter how much
excess solid is present.
The Effect of a Common Ion on the Solubility of a Precipitate?

The solubility of an ionic precipitate decreases when a

soluble compound containing one of the ions of the
precipitate is added to the solution.

This behavior is called the common-ion effect.

If you do the exercise (at home) you can see that a 0.02 M excess of Ba 2+ decreases
the solubility of Ba(IO3)2 by a factor of about 5; this same excess of IO3+ lowers the
solubility by a factor of about 200.
The equation can frequently be
simplified by making the
additional assumption that
dissociation does not
appreciably decrease the molar
concentration of HA.