Activity and the Systematic

Treatment of Equilibrium

Effect of Ion Strength on Solubility of

Salts
The region surrounding ions in solution is referred to
as the ionic atmosphere.
The greater the ionic strength of a solution, the
higher the charge in the ionic atmosphere.
Each ion-plus-its ionic atmosphere contains less NET
charge, so there is less attraction between any
particular cation and anion.
This leads to a decreased tendency to come together
and increases solubility.
* Increasing ionic strength promotes dissociation of
salts into ions.
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Effect of Ionic Strength on the Solubility

of Salts
The ionic strength of a solution increases as salt is
added to the solution.
Adding an inert salt (one whose ions do not react
with the compound of interest) to a solution of a
sparingly soluble salt increases the solubility of the
sparingly soluble salt.
The presence of other ions in solution decreases the
attraction between the ions of the sparingly soluble
salt because the oppositely charged ions of the inert
salt surround the ions of the sparingly soluble salt
and decrease its apparent charge.
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What is Meant by Ionic Strength

Ionic strength, , is a measure
concentration of ions in solution.

of

the

total

*Multiply charged ions increase ionic strength more

than singly charged ions.
= (c1z12 + c2z22 + . . .) = cizi2
where ci is the concentration of the ith species and zi
is its charge. The summation is over all ions in
solution.
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Calculation of Ionic Strength

What is the ionic strength of a 0.1 M solution of Na2SO4

= (cizi2)
Na2SO4 2 Na+ + SO42[Na] = 2 x 0.1 = 0.2 M
[SO42-] = 0.1 M

= [(0.2)(1)2 + (0.1)(2)2] = 0.3 M

Limitation: may overestimate the true ionic
strength due to ion pair formation

What is Meant by Ionic Strength

For 1:1 electrolytes (i.e., electrolytes involving singly
charged cation and anions), the ionic strength equals
the molarity ( = M).
For other electrolytes, the ionic strength is greater
than the molarity.
The ionic strength of solutions containing salts
whose ions are multiply charged is very difficult to
quantify because these salts are not completely
dissociated and generally exist as a soluble ion pair
M2+X2-(aq).
To calculate ionic strength you would need to know
the extent of dissociation (or the concentration of ion
pairs).
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Activity
According to the simple form of the law of mass
action for the following reaction equilibria
aA + bB cC + dD
The equilibrium constant is given by
K = [C]c[D]d/[A]a[B]b
However, the equilibrium constant is not truly
constant and varies with the concentration of
electrolytes in solution.
In order for this expression for the equilibrium
constant to hold we must replace concentrations by
activities.
K = ACcADd /AAaABb
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Activity Coefficients
The expression for the equilibrium constant does not
predict any effect of ionic strength of a chemical
reaction. To account for the effect of ionic strength,
concentrations must be replaced by activities
activity AC = C[C]
The activity coefficient, c, is a measure of the
deviation of behavior from ideality.

Activity Coefficients
The accurate form of the equilibrium constant
K = ACc ADd/ AAa ABb
= Cc[C]c Dd[D]d / Aa[A]a Bb[B]b
At low ionic strength, s 1 and K can be written
fairly accurately in terms of concentrations.

Activity Coefficients of Ions

Activity coefficients are related to ionic strength by
the extended Debye-Hckel equation
log = (-0.51 z2 ) /(1 + ((/305)) at 25C
z is the charge of the ion, and is the size of the ion
in pm (and is the effective radius of the hydrated ion)
Smaller highly charged ions bind solvent molecules
more tightly and have larger hydrated radii than
larger or less highly charged ions.
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Effect of Ionic Strength, Ion charge, and

Ion Size on the Activity Coefficient
Over the range of ionic strengths from 0-0.1 M
1. As ionic strength, , the activity coefficient, , .
1 as 0.
2. As the charge, z, of an ion , the deviation of
from 1 increases.
i.e. Activity corrections are larger for more highly
charged ions, but do not depend upon the sign of the
charge. ( - or +)
3. The smaller the hydrated radius, , of the ion, the
more important the activity effects become.
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Effect of Ionic Strength, Ion charge, and

Ion Size on the Activity Coefficient

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Activity Coefficients of Nonionic

Compounds
The activity coefficients of neutral molecules are

~1
in solutions with an ionic strength of < 0.1 M.
* We will assume that the activity of a neutral
molecule is equal to its concentration
AC = [C].

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Activity Coefficients of Nonionic

Compounds
For gases, the activity is refereed to its fugacity.
The fugacity is given by
AC = CPC
where C is its fugacity coefficient.
When a gas behaves ideally (i.e., at pressures 1
bar), C = 1.
We will assume that the fugacity of a gas is equal
to its partial pressure
AC = PC.

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pH Revisited
The definition of pH given previously is not correct.
The accurate definition is in terms of activity.
pH = -logAH+ = -log{ H+[H3O+]}
A pH meter measures activity not concentration.
As for other reactions, the extent of ionization of H2O
is influenced by the ionic strength of the solution.
*Thus pH depends upon the concentration(s) of other
electrolytes in solution.
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Systematic Treatment of Equilibrium

Many chemical systems are exceedingly complex
because of the large number of reactions and
species involved.
Need to treat equilibria systematically in order to
solve problems where many reactions/species are
involved.
Many equations in many unknowns that are
derived from
1. The equilibrium expressions for the reactions
involved
2. Charge balance
3. Mass balance(s)
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Charge Balance
The charge balance is derived from the fact that
solutions have no net charge.
The sum of the (+) charges in solution = the sum of
the (-) charges in solution.
If we know all of the charged species that exist in
solution, then it is straightforward to write the
charge balance equation.

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Charge Balance
* The coefficient in front of each species always
equals the magnitude of the charge on the ion.
In general terms, charge balance is given by
p1[C1] + p2[C2] + . . . = n1[A1] + n2[A2] + . . .
or pi[Ci] = ni[Ai]
where [Ci] = concentration of cation i
pi = the (+) charge on cation i
[Ai] = concentration of anion i
ni = the (-) charge on anion i

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Charge Balance
Write a charge balance equation for the dissociation of
sulfuric acid in aqueous solution
H2SO4 H+ + HSO4- + SO42H2O H+ + OHThe sum of the (+) charges in solution = the
sum of the (-) charges in solution
[H+] = [HSO4-] + 2[SO42-] + [OH-]

Example:
Write the charge balance equation for a solution that contains the following ionic
species, H+, OH-, Na+, HSO4-, and SO42-.
Total (+) charge in solution = Total (-) charge in solution
[H+] + [Na+] = [OH-] + [HSO4-] + 2 [SO42-] .

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Example:
Write the charge balance equation for a solution that contains 0.100 M H3PO4.
To determine all of the ionic species in solution we need to recognize that . . .
2 H2O() H3O+(aq) + OH-(aq)
H3PO4(aq) + H2O() H3O+(aq) + H2PO4-(aq)
H2PO4-(aq) + H2O() H3O+(aq) + HPO42-(aq)
HPO42-(aq) + H2O() H3O+(aq) + PO43-(aq)
Total (+) charge in solution = Total (-) charge in solution
[H3O+] = [OH-] + [H2PO4-] + 2 [HPO42-] + 3[PO43-].

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Mass Balance
The mass balance, also referred to as the material
balance, arises because we must have
conservation of matter in chemical reactions.
i.e., matter is neither created nor destroyed in a
chemical reaction, it merely changes form.
The quantity of all species in a solution containing a
particular atom (or group of atoms) must equal the
amount of the atom (or group) placed in solution.

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Example:
The fizz (carbonation) in soft drinks in maintained by complex equilibria involving
carbonic acid, H2CO3. Consider a solution of 0.050 M H2CO3. Write a mass
balance equation for the CO2 group.
H2CO3(aq) + H2O() HCO3-(aq) + H3O+(aq)
HCO3-(aq) + H2O() CO32-(aq) + H3O+(aq)
HCO3-(aq) CO2(aq) + OH-(aq)
H3O+(aq) + OH-(aq) 2 H2O()
mass balance for CO2 group is given by
0.050 M = [H2CO3] + [HCO3-] + [CO32-] + [CO2]
When in a closed container, soft drinks are able to maintain their fizz because
CO2 cannot escape solution, but pop loses its fizz when opened to the
atmosphere because the CO2 evaporates and the above equilibria for the first
three reactions are pushed to completion by Le Chteliers principle.

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Mass Balance
Ce(OH)3 Ce3+ + 3 OHMass Balance
[OH-] = 3 [Ce3+]
In words: the concentration of hydroxide
ions is 3 times the concentration of cerium

Solubility Using a Mass

Balance

Determine the solubility of

tributylammonium
bromide in a saturated solution with the pH
fixed to 9.50
R3NHBr R3NH++ Br- Ksp = 4.0 x 10-8
R3NH+ R3N + H+ Ka = 2.3 x 10-9
Ksp = [R3NH+][Br-]
Ka = [R3N][H+] / [R3NH+]

Two equations with three unknowns?

Solubility Using a Mass

Balance

Cannot use a charge balance because pH is

fixed by an external mechanism
Mass Balance
[Br-] = [R3NH+] + [R3N]
From the equation for the acid dissociation constant

[R3N] = Ka [R3NH+] / [H+] = 2.3 x 10-9[R3NH+] / 1 x 10-9.5

[R3N] = 7.273 [R3NH+]
Substitute into mass balance equation

[Br-] = [R3NH+] + 7.273 [R3NH+]

[Br-] = 8.273 [R3NH+]

Solubility Using a Mass

Balance
Substitute for [Br-] and [R3NH+] in Ksp relationship

([R3NH+])(8.273 [R3NH+]) = 4.0 x 10-8

[R3NH+] = (4.0 x 10-8) / 8.273 = 7.0 x 10-5

From stoichiometry solubility = [Br -]

[Br-] = [R3NH+] + [R3N]

= 7.0 x 10-5 + (7.273 x 7.0 x 10-5)
= 5.79 x 10-4 M
Correct for significant figures

Solubility of R3NHBr = 5.8 x 10-4 M

Example:
Calculate the concentrations of all species present in a solution
containing 1.0M HCl and 0.010M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is
negligible (i.e., we can ignore reactions such as Cd 2+ + 2x H2O =
Cd(OH)x2-x + x H3O+).
equilibria present
Cd2+(aq) + Cl-(aq) CdCl+(aq)
K1 = [CdCl+] / [Cd2+][Cl-] = 21
CdCl+(aq) + Cl-(aq) CdCl2(aq)
K2 = [CdCl2] / [CdCl+][Cl-] = 7.9
CdCl2(aq) + Cl-(aq) CdCl3-(aq)
K3 = [CdCl3-] / [CdCl2][Cl-] = 1.23

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Example:
Calculate the concentrations of all species present in a solution
containing 1.0M HCl and 0.010M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is
negligible (i.e., we can ignore reactions such as Cd2+ + 2x H2O = Cd(OH)x2-x
+ x H3O+).
equilibria present
CdCl3-(aq) + Cl-(aq) CdCl42-(aq)
K4 = [CdCl42-] / [CdCl3-][Cl-] = 0.35
mass balances
[Cl-] + [CdCl+] + 2[CdCl2] + 3[CdCl3-] + 4[CdCl42-] = 1.00
[Cd2+] + [CdCl+] + [CdCl2] +[CdCl3-] + [CdCl42-] = 0.010

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Example:
Calculate the concentrations of all species present in a solution
containing 1.0M HCl and 0.010M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is
negligible (i.e., we can ignore reactions such as Cd2+ + 2x H2O = Cd(OH)x2-x
+ x H3O+).
equilibria present
CdCl3-(aq) + Cl-(aq) CdCl42-(aq)
K4 = [CdCl42-] / [CdCl3-][Cl-] = 0.35
mass balances
[Cl-] + [CdCl+] + 2[CdCl2] + 3[CdCl3-] + 4[CdCl42-] = 1.00
[Cd2+] + [CdCl+] + [CdCl2] +[CdCl3-] + [CdCl42-] = 0.010

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Example:
Calculate the concentrations of all species present in a solution containing 1.0 M
HCl and 0.010 M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is negligible
(i.e., we can ignore reactions such as Cd2+ + 2x H2O Cd(OH)x2-x + x H3O+).
Assume that most of the chlorine present is as free Cl-. This should be
reasonable because the total Cl- concentration is 100 times as large as that of
Cd.
[Cl-] = 1.0
from reaction 1
21 = [CdCl+]/[Cd2+][Cl-]
or [CdCl+] = 21[Cd2+]

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Example:
Calculate the concentrations of all species present in a solution containing 1.0 M
HCl and 0.010 M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is negligible
(i.e., we can ignore reactions such as Cd2+ + 2x H2O Cd(OH)x2-x + x H3O+).
from reaction 2
7.9 = [CdCl2]/[CdCl+][Cl-]
or [CdCl2] = 7.9[CdCl+] = 7.9(21)[Cd2+] = 166[Cd2+]
from reaction 3
1.23 = [CdCl3-]/[CdCl2][Cl-]
or [CdCl3-] = 1.23[CdCl2] = 1.23(166)[Cd2+] = 204[Cd2+]

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Example:
Calculate the concentrations of all species present in a solution containing 1.0 M
HCl and 0.010 M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is negligible
(Cd2+ + 2x H2O Cd(OH)x2-x + x H3O+).
from reaction 4
0.35 = [CdCl42-]/[CdCl3-][Cl-]
or [CdCl42-] = 0.35[CdCl3-] = 0.35(204)[Cd2+] = 71[Cd2+]
substitute into mass balance for Cd2+
[Cd2+] + 21[Cd2+] + 166[Cd2+] + 204[Cd2+] + 71[Cd2+] = 0.010
[Cd2+] = 2.16 x 10-5M 2.2 x 10-5M

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Example:
Calculate the concentrations of all species present in a solution containing 1.0M
HCl and 0.010M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is negligible
(Cd2+ + 2x H2O Cd(OH)x2-x + x H3O+).
substitute into other equations to derive all concentrations
[CdCl+] = 4.53 x 10-4 M 4.5 x 10-4 M
[CdCl2] = 3.58 x 10-3 M 3.6 x 10-3 M
[CdCl3-] = 4.41 x 10-3 M 4.4 x 10-3 M
[CdCl42-] = 1.53 x 10-3 M 1.5 x 10-3 M
The formation of coordination complexes can have a large effect on the solubility
of a compound in water by consuming one of the ions through complex
formation.

Example:
Calculate the concentrations of all species present in a solution containing 1.0M
HCl and 0.010M Cd(NO3)2
Because the solution is strongly acidic, hydrolysis of the metal ion is negligible
(Cd2+ + 2x H2O Cd(OH)x2-x + x H3O+).
Because the question asks for the concentrations of all species, the
concentrations of H3O+, OH-, and NO3- should also be determined as these
species will be present in the solution
[H3O+] = 1.0 M (because HCl(aq) + H2O( ) H3O+(aq) + Cl-(aq))
[OH-] = Kw/[H3O+] = (1.0 x 10-14/1.0)M = 1.0 x 10-14 M
[NO3-] = 2(0.010 M) = 0.020 M
(because Cd(NO3)2(aq) Cd2+(aq) + 2 NO3-(aq) in H2O)

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