Ionic Strength and Activity Coefficients
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ScribdTranslationsIonic Strength and Activity Coefficients
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ScribdTranslationsACTIVITY
The activity tox of a species is given by the expression:
ax x X
Where [X] is the molar concentration and x it is a dimensionless number called
activity coefficient.
the activity coefficient xand the activity of X varies with ionic strength
of the solution.
Ionic strength is defined by the equation:
1
(c1 Z 12 c 2Z 22 c3 Z 32 ...)
2
Where c1, c2, c3... represent the molar concentrations of the different
ions in the solution and Z1, Z2, Z3,... are their respective loads. The calculation of
ionic strength requires taking into account all ionic species of the
solution, and not just the reactants.
Example No. 1
Calculate the ionic strength of a 0.0100 M solution of NaNO.3y 0.0200 M in
Mg(NO3)2.
In this case, the contribution of the H is disregarded.+ and the OH- to the ionic strength,
due to the fact that their concentrations are very small compared to those of the
two sales.
The molarities of Na+NO3- y Mg2+they are 0.0100; 0.0500 and 0.0200,
respectively. Therefore
C Na (1)2 0.0100 1 0.0100
C NO 12 0.0500 1 0.0500
3
C Mg 2 (2) 2 0,0200 2 2 0.0800
Sum 0.1400
1
0.1400 0.0700
2
THE DEBYE-HÜCKEL EQUATION
0.509ZA2
log A
1 3.28 A
Where
A activity coefficient of species A
ZAload of species A
ionic strength of the solution
A effective diameter of the hydrated ion in angstroms
The constants 0.509 and 3.28 apply when the solutions are
they find 25oC.
Example No. 2
Calculate the activity coefficient and the activity of a ZnSO solution.4
5.00X10-4M.
To obtain the activity coefficients of Zn2+and of the OS42-it must be calculated
first the ionic strength; for this it is assumed that the concentrations of H+ y
OH- they are despicable regarding the concentrations of Zn2+and SO42-,
thus, the ionic strength is
1 4 2 4 2 3
5.00 10 2 5.00 10 2 2.00 10
2
A= 0.4 for the SO42-y A= 0.6 for Zn2+Substituting in the equation of
Debye-Hückel for the sulfate ion and for the zinc ion
0.509 2 2 2.00 10 3
log 2
SO 4
8.59 10 2
1 3,28 0.4 2.00 10 3
SO42
0.820
a SO 20.820 5.00 10 4 4.10 10 4
4
PROPERTIES OF THE COEFFICIENTS OF
ACTIVITY
The activity coefficient of a species can be imagined as a
measure of the effectiveness with which this species influences the balance in
the one who participates. In very diluted solutions, where the ionic strength is
minimum, the ions are sufficiently separated in such a way that their
behaviors do not affect each other. In this way, the effectiveness
of a common ion at the equilibrium position depends only on its
molar concentration and is independent of the rest of the ions. In these
circumstances, the activity coefficient becomes equal to one and [X] and
identical reasons.
When the ionic strength increases, the behavior of an individual ion
is influenced by the nearest neighboring ions. The result is a
decrease in ion activity to alter the position of the equilibrium
chemical. Its activity coefficient then becomes less than one.
For high ionic strengths, the activity coefficients of some
species increase and can become greater than one.
PROPERTIES OF THE COEFFICIENTS OF
ACTIVITY
2. In dilute solutions, the activity coefficient of a species
dada is independent of the specific nature of the electrolyte and
it depends only on the ionic strength.
3. For a given ionic strength, the activity coefficient of an ion is
deviates more from the unit as the load carried by the species increases.
increase. The activity coefficient of an uncharged molecule is
approximately one, independent of the ionic strength.
4. The activity coefficients of ions with the same charge are
approximately the same as any given ionic force.
5. The product of the activity coefficient and the molar concentration of a
the ion given describes its effective behavior in all equilibria
in which he/she participates.