CHEMICAL EQUILIBRIUM

CHEMICAL ACTIVITY AND

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Concentration and Activity

Consider the reaction:

Equilibrium constant (K) is expressed as

This equation is a limiting law (it only applies to

infinitely dilute solutions)
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Presence of diverse salts (not containing ions to the

equilibrium involved) will cause in solubility of the ppt.
Activity is the effective
concentration of an ion
In the presence of an
electrolyte

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Relationship between a and Concentration

a = c ( is an activity coefficient).
In dilute solutions, the solvent interactions with
analytes are small. So essentially, a = c.
So, in order to consider the solvent effects
we need to calculate the ionic strength of
the solution containing the analyte.
The conversion from activity to concentration
is important in many reactions and
equilibrium expressions.

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Ionic strength can be important in many

scientific applications.
Ionic strength can be a factor in many reactions
where ions are produced. \What would the be
the ionic strength, if their solution was 0.010 M
Na3PO4 and 0.024 M NaCl?

=0.084 M
= { (.030)x 12 + (.010)x 32 + (.024)x 12 + (.024)x12}
Na+
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PO43-

Na+

Cl-

Calculating the Ionic Strength I

The concentration and charge are
the key forces, non-ionic not
considered.
Without a measured value of a
approximations can be
calculated using the DebyeHckel equation.

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 2011 Pearson Education, Inc.

Factors Affecting Activity

Ionic strength (I): More ions in a solution cause
solute-solvent interactions to increase. Higher I
values generally see activity decrease.
Solvent Choice: Higher dielectric constants
(polarity) cause more interactions with solutes.
Charge of ion (z): Higher charged ions have
more interactions with solvent, and other ions;
decreases a.
Effective radius: A slight decrease in activity as
ion size decreases
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It will get you coming and going

Equilibrium
When using activities, we obtain the thermodynamic
equilibrium constant Ko

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Chemical Equilibrium Constant K

This is based on concentration instead of
activity
It can therefore vary with ionic strength (but can
sometimes be useful when determined under
the same conditions of an analysis of a material
It is possible to convert K to Ko

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Example:
1. Calculate the solubility of Ba(IO3)2 in a
0.033 M solution of Mg(IO3)2. The
thermodynamic solubility product for
Ba(IO3)2 is 1.57 x 10-9.
2. Use activities to calculate the hydronium
ion concentration in a 0.120 M solution of
HNO2 that is also 0.050 M in NaCl.
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Seatwork:
1. Calculate the ionic strength of a solution
that is:
a. 0.030 M in FeSO4.
b. 0.30 M in FeCl3 and 0.20 M in
FeCl2.
2. Calculate the solubility of AgIO3 in a
0.0167 M solution of Ba(NO3)2.

2011 Pearson Education, Inc.