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Jess Sproul

Chapter 9 Notes

Chapter 9
Electrolyte Effects: Activity or
Concentration

9A-1: How Do Ionic Charges Affect


Equilibria?

The magnitude of the effect that the


electrolyte has is highly dependent on the
charge of the ions participating in the
equilibrium.
When only neutral species are involved in
the equilibrium, the electrolyte has no real
effect, no matter how concentrated.

9A-1: How Do Ionic Charges Affect


Equilibria? (cont.)
In the figure seen at the right,
the molar solubility of the doubly
charged ions in BaSO4 increases by
a factor of 2 in a solution of 0.02 M
KNO3 over a solution of pure water.
On the other hand, the molar
solubility of a solution of Ba(IO3)2 with
one singly and one doubly charged
ion only increases by a factor of 1.25
in a solution of 0.02 M KNO3 over a
solution of pure water. And finally,
the molar solubility of AgCl with two
singly charged ions only increases by
a factor of 1.2 in a solution of 0.02 M
KNO3 over a solution of pure water.

9A-2: What Is the Effect of Ionic


Strength on Equilibria? (cont.)

The ionic strength of a


solution of a strong
electrolyte consisting
solely of singly charged
ions is identical with its
total molar salt
concentration. But
when the ions are no
longer singly charged,
the ionic strength
increases.

Type
Electrolyte

Example

Ionic Strength*

1:1

NaCl

1:2

Ba(NO3)2,
Na2SO4

3c

1:3

Al(NO3)3,
Na3PO4

6c

2:2

MgSO4

*c = molarity of the salt

4c

9A-3: The Salt Effect


The

electrolyte effect results from the electrostatic


attractive and repulsive forces that exist between
the ions of an electrolyte and the ions involved in
an equilibrium. These forces cause each ion from
the dissociated reactant to be surrounded by a
sheath of solution that contains a slight excess of
electrolyte ions of opposite charge.

9A-3: The Salt Effect

The electrolyte effect results from the electrostatic attractive and repulsive forces
that exist between the ions of an electrolyte and the ions involved in an
equilibrium. These forces cause each ion from the dissociated reactant to be
surrounded by a sheath of solution that contains a slight excess of electrolyte
ions of opposite charge. These charged atmospheres lessen the charges on
the ions in equilibrium, the Ba2+ and SO42- in the figure, thus decreasing
their overall attraction to each other and increasing solubility.

9B: Activity Coefficients

The term activity, a, is used to account for the


effects of electrolytes on chemical equilibria.
The activity, or effective concentration, of species X
depends on the ionic strength of the medium and is
defined as
ax = x [X]
where ax is the activity of X, [X] is its molar
concentration, and x is a dimensionless quantity
called the activity coefficient.
The activity coefficient and the activity of X vary
with ionic strength.

9B-1: Properties of Activity


Coefficients

In dilute solutions, the activity coefficient for


a given species is independent of the nature
of the electrolyte and dependent only on
ionic strength.
For a given ionic strength, the activity
coefficient of an ion departs farther from
unity as the charge carried by the species
increases.
At any given ionic strength, the activity
coefficients of ions of the same charge are
approximately equal.
The activity coefficient of a given ion
describes its effective behavior in all
equilibria in which it participates.

9B-1: Properties of Activity


Coefficients (cont.)

9B-2) The Debye-Hckel Equation

The Debye-Hckel equation takes the ionic


atmosphere model and derives a theoretical
expression that permits the calculation of
activity coefficients of ions from their charge
and their average size.

9B-3: Equilibrium Calculations with


Activity Coefficients

Equilibrium
calculations with
activities yield
values that are
better in agreement
with experimental
results than those
obtained with molar
concentrations.

9B-4: Omitting Activity Coefficients


in Equilibrium Calculations
We shall ordinarily neglect activity coefficients
and simply use molar concentrations in
applications of the equilibrium law. This
simplifies calculations and decreases
necessary data. For most purposes, the error
introduced by this method is minimal.

Significant discrepancies occur when the ionic


strength is larger than 0.01 or when the ions
involved have multiple charges.
With dilute solutions of nonelectrolytes or of simply
charged ions, the use of concentrations in a masslaw calculation often provides reasonably accurate
results.