Aqueous Ionic Equilibrium

The Common-Ion Effect
Solutions consisting
of both an acid and
its conjugate base
are very important
because they are
very resistant to
changes in pH.
Chapter 16
Aqueous Ionic Equilibrium
Dr. Peter Warburton

peterw@mun.ca
http://www.chem.mun.ca/zcourses/1051.php
The Common-Ion Effect
Point of view of the acid
Lets consider a solution made of 0.10 moles of acetic

acid and 0.10 moles of sodium acetate with a total
volume of 1.00 L, making the initial [CH3COOH] =
[CH3COO-] = 0.10 mol/L.
Our reaction will be

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)
Ka = 1.8 x 10-5
First we must identify all potential acids and bases

in the system.
CH3COOH
acid
CH3COObase
Na+
neutral
(all in m ol/L)
Initial conc.
C onc. change
E quil. conc.
H2O
acid
or base
C H 3 C O O H (aq) +
0.10
-x
0.10 x
H 2 O (l)
N /A
N /A
N /A
H 3 O (aq)
0.0
+x
+x
+ C H 3 C O O (aq)
0.10
+x
0.10 + x
Note that the initial concentration of our product

CH3COO- is NOT ZERO!
3
Ka
[H 3O ][CH 3COO ]
(x)(0.10 x)
1.8 x 105
[CH 3COOH]
(0.10 x)
Ka
Lets check the

initial acid concentration / Ka ratio.
0.10 / 1.8 x 10-5 5500
Its probably safe to assume that
x << [HAc]i so [HAc]eqm [HAc]I
and x << [Ac-]i so [Ac-]eqm [Ac-]i
[H 3O ][CH 3COO ]
(x)(0.10 x)
1.8 x 105
[CH 3COOH]
(0.10 x)
At equilibrium,
[H3O+] = 1.8 x 10-5 mol/L
[CH3COO-] = 0.10 + 1.8 x 10-5 = 0.10 mol L-1
[CH3COOH] = 0.10 - 1.8 x 10-5 = 0.10 mol L-1
Assumption was valid! Check for yourself!
pH = - log [H3O+]
pH = - log 1.8 x 10-5
1.8 x 10-5 = x (0.10 + x) / (0.10 x)

1.8 x 10-5 = x (0.10) / (0.10)
x = 1.8 x 10-5 mol L-1
pH = 4.74
5
If we had started out with only 0.10 mol/L

acetic acid, the pH would be found from
(all in m ol/L)
Initial conc.
C onc. change
E quil. conc.
0.10
-x
0.10 x
Ka
H 2 O (l)
N /A
N /A
N /A
H 3 O (aq)
0.0
+x
+x
[H 3 O ][CH 3 COO ]
[CH 3 COOH]
1.8 x 10
+ C H 3 C O O (aq)
0.00
+x
+x
(x)(x)
(0.10 x)
The initial acid concentration / Ka will still be the

same, so we can assume
x << [HAc]i so [HAc]eqm [HAc]i
1.8 x 10-5 = x2 / (0.10 x)
1.8 x 10-5 = x2/ (0.10)
x = 1.8 x 10-6 mol L-1
x = 1.3 x 10-3 mol/L (cant be ve)
pH = - log [H3O+]
pH = - log 1.3 x 10-3
pH = 2.89
Without the acetate ion the pH of

0.10 M acetic acid is 2.89.
With an equal concentration of acetate ion
present, the pH of
0.10 M acetic acid 0.10 M acetate is 4.74
The acetate ion makes a large difference on

the equilibrium pH!
Adding the conjugate

base (a stress!) to the
equilibrium system of
an acid dissociation
shows the commonion effect, where the
addition of a common
ion causes the
equilibrium to shift.
This is an example of
Le Chataliers
Principle.
Addition of the weak

base to the acid
dissociation
Salts as source of a basic common-ion
10
Salts as source of a basic common-ion

On the left is a solution of 0.100 M CH3COOH while in
the middle is a 0.100 M CH3COONa solution. On
the right is a solution that is both 0.100 M CH3COOH
and 0.100 M CH3COONa which is a source of the
basic common ion CH3COO-. The acid reaction
has shifted back towards reactants!
11
12
Salts as source of an acidic common-ion
Salts as source of an acidic common-ion

On the left is a solution of
0.100 M NH3 while on the
right is a solution that is
both 0.100 M NH3 and
0.100 M NH4Cl which is
a source of the acidic
common ion NH4+.
The reaction has shifted
back towards reactants!
13
Buffer solutions
14
Buffer solutions
The system has enough of the
original acid and conjugate base molecules
in the solution to react with
added strong acid or added strong base,
so the new equilibrium mixture will be
very close in composition to the original
equilibrium mixture.
Solutions that contain both a weak

acid and its conjugate base are
buffer solutions.
These solutions are resistant to
changes in pH.
15
16
Buffer solutions
Buffer solutions
We saw 0.10 mol L-1 acetic acid 0.10 mol L-1

acetate mixture has a pH of 4.74 and is a buffer
solution!
[H 3 O ]

(all in mol/L)
Initial
Conc. changes
Equil. conc.

0.10
N/A
0.0
0.10
+x
N/A
-x
-x
0.10 + x
N/A
-x
0.10 - x
K a 1.8x10
If we rearrange the Ka expression

K a [CH 3 COOH]
[CH 3 COO ]
1.8x10
[CH 3 COOH]
[CH 3 COO ]
and make the assumption that x is much less

than 0.10, we see
[H 3 O ][CH 3 COO ]
If [CH3COOH] = [CH3COO-],
then [H3O+] = 1.8 x 10-5 = Ka
and pH = pKa = 4.74
[CH 3 COOH]
17
Buffer solutions
18
Buffer solutions
What happens if we add 0.01 mol of NaOH (strong
base) to 1.00 L of the acetic acid acetate buffer
solution, with no change in volume?
CH3COOH (aq) + OH- (aq) H2O (l) + CH3COO- (aq)
This reaction goes to completion and keeps
occurring until we run out of the limiting reagent OH(all in moles)
Initial
Change
Final (where x = 0.01
due to limiting OH-)

0.10
0.01
N/A
0.10
-x
-x
N/A
+x
0.10 x
0.01 x =
N/A
0.10 + x
= 0.09
0.00
= 0.11
New [CH3COOH] = 0.09 M and new [CH3COO-] = 0.11 M

19
20
Buffer solutions
Buffer solutions
(all in m ol/L)
Initial conc.
C onc. change
E quil. conc.
0.09
-x
0.09 x
Ka
H 2 O (l)
N /A
N /A
N /A
H 3 O (aq)
0.0
+x
+x
[H 3 O ][CH 3 COO ]
1.8 x 10
+ C H 3 C O O (aq)
0.11
+x
0.11 + x
(x)(0.11 x)
With the assumption

smaller
[CH 3 COOH] that x is much (0.09
x) than
0.09
mol
(an
assumption
we
always
need
to 5
[CH
COOH]
0.09
5
3
[H 3 O ] K a
1.8 x 10
1.5 x 10 M
check after
calculations
are
done!),
we
find
[CH COO ]
0.11
3
Note weve made the assumption that x << 0.09 M!

pH = - log [H3O+]
pH = - log 1.5 x 10-5
pH = 4.82
Adding 0.01 mol of OH- to 1.00 L

of water would have given us a
pH of 12.0!
There is no significant amount
of acid in water for the base to
react with.
21
Buffer solutions
Buffer solutions
What happens if we add 0.01 mol of HCl (strong acid)

to 1.00 L of the acetic acid acetate buffer solution,
with no change in volume?
CH3COO- (aq) + H3O+ (aq) H2O (l) + CH3COOH (aq)
This reaction goes to completion and keeps
occurring until we run out of the limiting reagent H3O+
(all in moles)
Initial
Change
Final (where x = 0.01
due to limiting OH-)
22
CH3COO- (aq) + H3O+ (aq) H2O (l) + CH3COOH (aq)

0.10
0.01
N/A
0.10
-x
-x
N/A
+x
0.10 x
0.01 x =
N/A
0.10 + x
= 0.09
0.00
= 0.11
New [CH3COOH] = 0.11 M and new [CH3COO-] = 0.09 M

23
(all in m ol/L)
Initial conc.
C onc. change
E quil. conc.
0.11
-x
0.11 x
Ka
H 2 O (l)
N /A
N /A
N /A
H 3 O (aq)
0.0
+x
+x
[H 3 O ][CH 3 COO ]
1.8 x 10
+ C H 3 C O O (aq)
0.09
+x
0.09 + x
(x)(0.09 x)
With the assumption

that x is much smaller than
[CH 3 COOH]
(0.110.09
x) mol
(an assumption we always need to check after
[CH
COOH]
0.11
5
5
3
are
[H 3 O ] K a calculations
1.8done!),
x 10 we find
2.2 x 10 M
[CH 3 COO ]
0.09
Note weve made the assumption that x << 0.09 M!

pH = - log [H3O+]
pH = - log 2.2 x 10-5
pH = 4.66
24
Buffer solutions
Be careful!
Adding 0.01 mol of H3O+ to 1.00 L

of water would have given us a pH
of 2.0!
In the previous two problems, the solution

volume did not change with the addition
of strong acid or base to the buffer.
This is unrealistic!
In reality, the solution concentrations will
change due to the chemistry of the acidbase reaction, and also due to the
physical change in volume due to
mixing!
There is no significant amount

of base in water for the acid to
react with.
25
Be careful!
26
Adding acid or base to a buffer
We do our first table in these buffer

problems in moles and then recalculate
the concentrations of the new buffer
solution.
If the volume does change on mixing the
buffer and the added acid or base, this
recalculation of concentration now
accounts for the concentration change
due to the mixing!
chemistry
in moles!
mixing
in mol L-1!
27
28
Problem
Problem
Calculate the pH of a 0.100 L buffer solution

that is 0.25 mol L-1 in HF and 0.50 mol L-1 in
(all in m ol/L)
H F (aq) +
H O (l)
H O (aq) +
F (aq)
NaF.
+
Initial conc.
C onc. change
E quil. conc.
0.25
-x
0.25 x
0.0
+x
+x
3.5x10
[F ]
0.50
+x
0.50 + x
[H 3 O ][F ]
K a [HF]
[HF]
3.5x10
[F ]
0.25
0.50
1.7 5 x10
N /A
N /A
N /A
K a 3.5x10
[H 3 O ]
so 3.5x10
pH = - log [H3O+]
pH = - log 1.75 x 10-4
pH = 3.76
(x)(0.50 x)
[HF]
(0.25 x)
With the assumption that x is much smaller

than 0.25 mol (an assumption we always need
to check after calculations are done!), we find
29
30
Problem
Problem
a) What is the change in pH on addition

of 40.0 mL of 0.0500 M of HNO3?
b) What is the change in pH on addition

of 150 mL of 0.020 M KOH?
[H 3 O ]
K a [HF]
[F ]
3.5x10
[HF]
[F ]
3.5x10
0.19
0.34
1.9 7 x10
pH = - log [H3O+]
pH = - log 1.97 x 10-4
pH = 3.71
[H 3 O ]
K a [HF]
[F ]
3.5x10
[HF]
[F ]
3.5x10
0.088
0.21 2
1.4 5 x10
pH = - log [H3O+]
pH = - log 1.45 x 10-4
pH = 3.84
31
32
Henderson-Hasselbalch equation
Predicting whether a solution is a buffer
Weve seen that, for solutions with both

members of a conjugate acid-base pair,
that
Any solution that becomes a mixture of a

conjugate acid-base pair will be a buffer.
[H 3 O ] K a
1) Weak acid-base conjugate pairs like

CH3COOH and CH3COO- or NH4+ and NH3.
[acid]
[base]
[acid]
logK
log[H 3 O ] log K a
[base]
2) Weak acid reacting with small amounts of

strong base like CH3COOH and NaOH.
3) Weak base reacting with small amounts of
strong acid like NH3 and HCl.
log
[acid]
[base]
pH = pKa + log [base] / [acid]

33
34

There is the hidden assumption that
the equilibrium concentrations of
acid and base are relatively
unchanged from the initial
concentrations.
That is we have assumed x is very
small compared to the initial
concentrations!

What if the assumption is not true?
Then the H-H equation gives you
the wrong pH.
Do not use the H-H equation unless
you are prepared to state the
assumption hidden within it and
check the assumption!
Better to do the ICE table
35
36
Preparing buffer solutions
How do we adjust the concentrations?
If we want to create a buffer

solution of a specific pH,
the logarithm equation tells
us we need to pick a
conjugate acid-base pair
with a pKa for the acid close
to the pH we want, and then
we adjust the amounts of
the conjugate acid and base.
37
Problem
38
Buffer capacity
Buffer capacity is the measure of the
ability of a buffer to absorb acid or base
without significant change in pH.
How many grams of (NH4)2SO4 (molar

mass is 132.141g mol-1) must be dissolved
in 0.500 L of 0.35 M NH3 to produce a
solution with pH = 9.00? Assume that the
solution volume remains at 0.500 L.
Kb for ammonia is 1.8 x 10-5.
Larger volumes of buffer solutions have

a higher buffer capacity, and buffer
solutions of higher initial concentrations
of the conjugate acid-base pair have a
larger buffer capacity.
Answer: 21 g
39
40
10
Buffer range
Buffer range
pH = pKa + log 10
pH = pKa + 1.0
As long as
0.10 < [base] / [acid] < 10
then the assumption that the
H-H equation is based upon
(x << [base] and x << [acid])
is likely to be valid.
OR
pH = pKa + log 0.10
pH = pKa - 1.0
41
Buffer range
42
Acid-base indicators
In general buffer solutions have a

useful range of pH that is pKa 1.0
For instance an acetic acid - acetate buffer
has a useful pH range of about
3.7 to 5.7
We often measure the pH of a solution with

a chemical acid-base indicator. Such
indicators are weak acids in their own
right (symbolized HIn) and indicate pH
because the acid form has a different
colour than the conjugate base form (In-)
HIn (aq) + H2O (l) H3O+ (aq) + In- (aq)

colour A
colour B
since pKa is 4.7 (Ka = 1.8 x 10-5)

43
44
11
Diprotic
indicators!

colour A
colour B
+
If we increase the [H3O ] we shift this reaction
towards reactants. The colour will be that of HIn.
If we decrease the [H3O+] we shift this reaction
towards products. The colour will be that of In-.
A [H3O+] in between these two extremes will give
a colour that is a mixture of the two colours
because both HIn and In- are present in
significant amounts!
45
46
colour A
colour B
More specifically, the
HIn and In- form a
buffer so the indicator
works in a pH range of
about 1 around the
pKHIn of HIn.
47
48
12
Since indicators work in a range

of about 2 pH units we often put
several indicators that have
different ranges in a single
solution to give a universal
indicator for pH range of about
1 - 12
49
Universal indicator
50
Neutralization reactions
A reaction of an acid and a base
often produces water and an
aqueous salt as products. Such
reactions are called neutralization
reactions, and can be categorized by
the strengths of the acid and base
involved.
51
52
13
Strong acid strong base neutralization
The reaction of a strong acid such as HCl and a

strong base such as NaOH becomes a reaction of
H3O+ and OH-,
If we mix equal numbers of moles of HCl and

NaOH, we will create twice as much water,
while leaving an excess of NEITHER ion.
Therefore while the overall reaction is
In this case the [H3O+] = [OH-] = 1.0 x 10-7 M

at 25 C (reaction goes to completion).
HCl (aq) + NaOH (aq) H2O (l) + NaCl (aq)

the actual net ionic equation is
H3O+ (aq) + OH- (aq) 2 H2O (l)
H3O+ (aq) + OH- (aq) 2 H2O (l)
is the reverse of the autoionization of water

reaction so
where the Na+ and Cl- ions are not involved (they are
neutral spectator ions which dont react with
water!)
Kn
3O
OH
1
Kw
1
1.0x10
14
1.0 x 10
14
53
at 25 C
54
Strong acid titration by strong base
Since the equilibrium constant is very

large, we see the reaction goes to
completion, and at the end, the
equilibrium mixture will consist of water
and an aqueous salt of ions that are
neutral in character because they
dont react with water.
The pH after the reaction will be 7
(a neutral solution).
55
Say we add the strong base to the strong

acid solution drop by drop. Each drop
of base (the titrant) will react with some
of the acid to completion until the added
base (the limiting reagent!) is all gone.
If we measure the pH after we add each
drop of base, we can plot a pH versus
total volume of added base graph.
This is called a titration curve.
56
14
Titration curve strong acid titrated by strong base
End point versus equivalence point

How do we know when weve reached the
end of our titration? We often will use an
indicator to tell us when the titrated
solution goes from basic to acidic. This
is the end point of the titration.
The end point DEPENDS

on the indicator we use!
57
58
Titration curve strong acid titrated by strong base

The equivalence point is that point in the
titration where we have added equal numbers
of MOLES of acid and base. For strong acid
strong base neutralizations
the equivalence point occurs

when the pH is 7
(a neutral solution)
59
Different
end points
depending
on
indicator
60
15
Titration curve strong base titrated by strong acid

Bromothymol blue is a good
indicator for strong acid-strong
base titrations because the end point
is very close to the equivalence
point.
Methyl red and phenolphtalein are
pretty good choices too because
the titration curve is very steep in
their effective pH ranges.
The curve looks

exactly the same, just
flipped vertically!
61
Millimoles (mmol)
62
Millimoles (mmol)
Since we often set up titrations where our

titrant concentration is less than 1 M
and total titrant volume used is less
than 50 mL this means we are adding
about 5.00 x 10-3 moles of acid or base in
our titration.
Because of this, we often do calculations
in millimoles
(1 mmol = 1 x 10-3 mol)
M = mol / L
M = mmol / mL
63
64
16
Problem
Problem answers
For the titration of 25.00 mL of 0.150 M HCl with

0.250 M NaOH, calculate
a) the initial pH;
b) the pH when the neutralization is 50.0%
complete;
c) the pH when the neutralization is 100%
complete; and
d) the pH when 1.00 mL of NaOH is added
beyond the equivalence point.
a) pH = 0.824 (Vtotal = 25.00 mL)

b) pH = 1.238 (Vtotal = 32.50 mL)
c) pH = 7.00 (Vtotal = 40.00 mL)
d) pH = 11.79 (Vtotal = 41.00 mL)
65
Weak acid strong base
66
Weak Acid Strong Base
Because a weak acid HA is largely undissociated in

water, while the strong base is completely
dissociated in water (becoming a source of OH-), the
neutralization reaction of a weak acid and strong
base becomes that of
CH 3 COOH
HA (aq) + OH- (aq) H2O (l) + A- (aq)
CH 3 COOH
H 3O
(aq) H 2 O (l) H 3 O
(aq) OH
(aq)
(aq) CH 3 COO
(aq) K a 1.8 x 10
1
2 H 2 O (l)
1.0 x 10
__________ __________ __________ __________ __________ __________ _

(aq) OH
(aq) H 2 O (l) CH 3 COO
(aq)
Kn Ka x
1
Kw
1.8 x 10
Acetic acid is a weak acid, so when it reacts with

NaOH, the net ionic equation is
Now remember that
Knet = K1 x K2 x K3 x x Kn
67
14
Kw
The equilibrium constant shows us the

reaction goes to completion, so for equal
numbers of moles of weak acid and strong
base, we expect only water and the aqueous
salt in the equilibrium mixture.
68
17
Weak acid strong base

CH 3 COOH
(aq) OH
(aq) H 2 O (l) CH 3 COO
Titration curve weak acid titrated by strong base
(aq)
Kn Ka x
1
Kw
1.8 x 10
However, the salt comprises of a neutral

cation (Na+ in this case) and a weakly
basic anion (CH3COO-), meaning the
equilibrium mixture will be BASIC and have
a pH greater than 7.
See slide 107 of last chapter!
In a weak acid titration by a strong base
this means the equivalence point is NOT
at pH = 7 but rather at pH > 7!
3. pH = pKa when moles

added OH- = initial
moles weak acid
4. buffer breaks!
2. creation of a buffer
Titration of
CH3COOH with
NaOH.
1. higher initial pH for a weak acid
69
Problem
6. Added strong
base dominates
weak base and
determines pH
5. pH > 7
because of water
hydrolysis by
conjugate base
70
Problem answers
For the titration of 20.00 mL of 0.150 M HF with

0.250 M NaOH, calculate
a) the initial pH; Ka = 6.6 x 10-4
complete;
c) the pH when the neutralization is 50.0%
complete; and
d) the pH when the neutralization is 100%
complete.
a) pH = 2.00 (Vtotal = 20.00 mL)

b) pH = 2.70 (Vtotal = 23.00 mL)
c) pH = 3.18 (Vtotal = 26.00 mL)
d) pH = 8.08 (Vtotal = 32.00 mL)
71
72
18
Weak base strong acid

NH
Because a weak base B is largely undissociated in

water, while the strong acid is completely
dissociated in water (becoming a source of H3O+),
the neutralization reaction of a strong acid and weak
base becomes that of
H3O+
(aq) + B (aq) H2O (l) +
BH+
H 3O
H 3O
(aq)
Ammonia is a weak base, so when it reacts with HCl,

the net ionic equation is
H3O+ (aq) + NH3 (aq) H2O (l) + NH4+ (aq)
Again
Knet = K1 x K2 x K3 x x Kn
(aq) H 2 O (l)
(aq) OH
(aq) NH
(aq)
NH
(aq) OH
(aq) K b 1.8 x 10
2 H 2 O (l)
(aq) NH
(aq) H 2 O (l)
1.0 x 10
H 3O
(aq) NH
(aq) NH
(aq) H 2 O (l)
14
Kw
Kn Kb x
1
Kw
1.8 x 10
Again the equilibrium constant shows us

the reaction goes nearly to completion, so
for equal number of reactant moles, we
expect only water and the aqueous salt in
the equilibrium mixture.
73
74
Titration curve weak base titrated by strong acid

Kn Kb x
1
Kw
1.8 x 10
However, the salt comprises of a neutral anion

(Cl- in this case) and a weakly acidic cation
(NH4+), meaning the equilibrium mixture will be
ACIDIC and have a pH less than 7.
In a weak base titration by a strong acid this
means the equivalence point is NOT at pH = 7
but rather at pH < 7!
75
76
19
Problem
Problem answers
For the titration of 50.00 mL of 0.106 M

NH3 with 0.225 M HCl, calculate
a) the initial pH; Kb = 1.8 x 10-5
complete;
c) the pH when the neutralization is 50.0%
complete; and
d) the pH when the neutralization is 100%
complete.
a) pH = 11.14 (Vtotal = 50.00 mL)

b) pH = 9.74 (Vtotal = 55.89 mL)
c) pH = 9.26 (Vtotal = 61.78 mL)
d) pH = 5.20 (Vtotal = 73.55 mL)
77
Solubility equilibria
78
Solubility equilibria
MmXx (s) m Mn+ (aq) + x Xy- (aq)
For a dissolution process, we give the

equilibrium constant expression the
name solubility product (constant)
Ksp. For
The equilibrium is
established when we have a
saturated solution of ions
forming the solid and solid
is dissociating to form the
ions in solution. The rates
of these processes must be
equal. (eqm definition)

Ksp = [Mn+]m [Xy-]x
79
80
20
Ksp is an equilibrium constant
Problem
Write the expressions of Ksp of:
K Ag Cl
a) AgCl
b) PbI2
K Pb I
c) Ca3(PO4)2 K Ca PO
d) Cr(OH)3
K Cr OH
Since Ksp is an equilibrium

constant we MUST
refer to a specific balanced equation
(by definition this balanced equation
is one mole of solid becoming
aqueous ions)
at a specific temperature.
sp
sp
3 2
2 3
sp
sp
81
82
Problem
If a saturated solution of BaSO4 is
prepared by dissolving solid BaSO4 in
water, and [Ba2+] = 1.05 x 10-5 mol L-1,
what is the Ksp for BaSO4?
BaSO
(s)
SO
K sp Ba
K sp x
if x Ba
K sp 1.1 x 10
K sp 1.05 x 10
83
Ba
-5
(aq) SO
SO
2
4
2
4
(aq)
1.05 x 10
-5
-10
84
21
Molar solubility
Molar solubility
If we know the Ksp value for a solid, we can

calculate the molar solubility, which is the
number of moles of the solid that can
dissolve into a given volume of solution
before the solution becomes saturated.
The molar solubility leads to the solubility
(by using the molar mass) which is the
mass of the solid that can dissolve in a
given volume of solution before the solution
becomes saturated.
Alternatively, if we know the

molar solubility
OR
the molar mass and the solubility
we can calculate
the Ksp for the solid.
85
Problem
Molar solubility
A good way to think about molar solubility is to treat
our solid dissolution AS IF there are two separate
processes:
2
M m X x (s)
M m X x (aq)
H O
M m X x (aq) m M
dissociati on
86
(aq) x X
(aq)
The molar solubility has the same value as the

concentration of aqueous MmXx after the first step.
We can figure out this concentration based on
concentrations of ions in the second step.
A handbook lists the aqueous solubility of

AgOCN as 7 mg per 100 mL at 20 C.
What is the Ksp of AgOCN at 20 C? The
molar mass of AgOCN is 149.885 g mol-1.
Answer: Ksp = 2 x 10-7
87
88
22
Problem
Problem
A handbook lists the aqueous solubility of

lithium phosphate (Li3PO4) as 0.034 g per
100 mL at 18 C. What is the Ksp of lithium
phosphate at 18 C? The molar mass of
Li3PO4 is 115.794 g mol-1.
Answer: Ksp = 2.0 x 10-9
Which has the greater molar solubility:

AgCl with Ksp = 1.8 x 10-10
or
Ag2CrO4 with Ksp = 1.1 x 10-12?
Answer: The molar solubility of AgCl is 1.3 x 10-5 M
while the molar solubility of Ag2CrO4 is 6.5 x 10-5 M.
Silver chromate has a higher molar solubility.
89
Problem
90
The common-ion effect
How many milligrams of BaSO4 (molar

mass is 233.391 g mol-1) are dissolved in a
225 mL sample of saturated aqueous
barium sulphate? Ksp = 1.1 x 10-10 at 25 C.

If we have dissolved a solid in pure water and
we add to this solution another solution
containing one of the common ions, then Le
Chataliers Principle tells us what will happen:
The presence of the common-ion in

the added solution will force the
dissolution reaction to the left,
meaning more solid will form!
Answer: mass = 0.55 mg
91
92
23
Precipitation
93
94

If instead of dissolving a solid in pure water we
try and dissolve it into a solution that already
contains one of the common ions, then Le
Chataliers Principle tells us what will happen:
The presence of the common-ion already in

solution will mean less reaction needs to
occur to establish equilibrium
concentrations of the ions, meaning less
solid will dissolve than would dissolve in
pure water!
95
96
24
Problem
Problem
Calculate the molar solubility

of MgF2 (Ksp = 7.4 x 10-11) in
pure water and in 0.10 mol L-1
MgCl2 at 25 C.
What is the the molar solubility of

Fe(OH)3 (Ksp = 4 x 10-38) in a
buffered solution with pH = 8.20 at
25 C.
Answer: The molar solubility is 2.6 x 10-4 M in

pure water and 1.4 x 10-5 M in 0.10 M
magnesium chloride.
Answer: The molar solubility is 1 x 10-20 M in

the buffered solution.
97
Solubility and pH
98
Solubility and pH
If a solid dissolves to give a basic anion in

solution, addition of strong acid will
increase the solubility of the solid.
CaCO3 (s) Ca2+ (aq) + CO32- (aq) Ksp = 2.8 x 10-9
Carbonate, CO32-, is a basic anion that

will react with a proton to give HCO3CO32- (aq) + H3O+ (aq) HCO3- (aq) + H2O (l)
99
CO32- (aq) + H3O+ (aq) HCO3- (aq) + H2O (l)

This reaction will shift to the right (products)
as the pH becomes more acidic which means
CO32- (aq) decreases. However, in our first
equilibrium IT ALSO MUST DECREASE so the
first equilibrium will also shift to the right to
compensate.
More solid will dissolve!

100
25
Adding equilibria
A better way to state the effect of pH on
solubility comes when we add dissolution
and weak base strong acid reactions
together:
CaCO3 (s) Ca2+ (aq) + CO32- (aq)
Ksp = 2.8 x 10-9
CO32- (aq) + H3O+ (aq) HCO3- (aq) + H2O (l)
K = Kb x 1/Kw = (2.1 x 10-4) x (1.0 x 1014)
K = 2.1 x 1010
101
Adding equilibria
102
Problem
CaCO3 (s) + H3O+ (aq)

Ca2+ (aq) + HCO3- (aq) + H2O (l)
K = K x Ksp = (2.1 x 1010) x (2.8 x 10-9)
K = 59
Will a precipitate of Fe(OH)3 form from a

solution that is 0.013 M Fe3+ in a buffer
solution that is 0.150 M acetic acid 0.250
M acetate?
Ksp Fe(OH)3 = 4 x 10-38 Ka = 1.8 x 10-5
Answer: Since Qsp is 1 x 10-29, then
precipitation will occur since Qsp>Ksp.
The solubility of the solid will

increase in the presence of H3O+!
103
104
26
Problem
Limitations of Ksp
What minimum [NH4+] must be present to

prevent precipitation of Mn(OH)2 (s) from a
solution that is 0.0050 M MnCl2 and 0.025
M NH3? For Mn(OH)2 Ksp = 1.9 x 10-13 and
Kb for NH3 is 1.8 x 10-5.
Answer: [NH4+] > 0.073 M
If our solid is more than slightly soluble

then we really should use the activities of
our ions in solution rather than
concentrations.
These two measures are nearly the same
for very dilute ion concentrations, but
can become quite different at higher
concentrations!
105
The diverse (uncommon) ion effect
106
The salt (uncommon ion) effect
The activities of ions tend

to be LESS than the
concentration value as
the total ionic
concentration increases.
107
Adding a salt that does NOT feature a

common ion to the solution will tend to
decrease the activity (the effective
concentration) of the ions in solution.
The ion concentrations appear smaller
than they should be at equilibrium so
more solid dissolves to reach the
appropriate equilibrium
concentrations.
108
27
Criteria for precipitation and its completeness
Can we predict if a solid will form if we mix

two solutions of different ions?
Consider the mixing of two different
solutions, one with Ca2+ ions and one with
F- ions. A formation of solid is the
dissolution reaction in reverse, so we can
express the reaction using the dissolution
equation
CaF2 (s) Ca2+ (aq) + 2 F- (aq) Ksp = [Ca2+ ][F-]2
109
110
When we mix the solutions

(BE CAREFUL mixing ALWAYS changes
the concentrations of both our ions!)
the system is most likely not at equilibrium.
Like in other equilibrum problems, we can use
a reaction quotient Qsp (often called the ion
product) to tell us in which direction the
system must go to reach equilibrium
Qsp = [Ca2+ ][F-]2
If Qsp > Ksp, the solution is supersaturated, so

the system is not at equilibrium. The
concentration of the ions is greater than it
would be at equilibrium, and so the reaction
wants to shift from ions towards the solid.
We expect precipitation to occur!
If Qsp = Ksp, the solution is saturated, and the
system is at equilibrium.
No precipitation occurs!
111
112
28
Mixing and equilibrium take time!

If Qsp < Ksp, the solution is unsaturated, so
the system is not at equilibrium. The
concentration of the ions is less than it
would be at equilibrium, and so the reaction
wants to shift from solid towards the ions.
No precipitation can occur!
We must wait
until dilution
is completed
and
equilibrium is
established
BEFORE
we say
precipitation
occurred!
113
114
Problem
Problem
Will a precipitate form when 0.150 L of

0.10 mol L-1 Pb(NO3)2 and 0.100 L of 0.20
mol L-1 NaCl are mixed?
How many drops (1 drop = 0.05 mL) of

0.20 M KI must we add to 100.0 mL of
0.010 M Pb(NO3)2 to get precipitation of
lead iodide to start?
Ksp of PbCl2 is 1.2 x 10-5

Answer: Qsp = 3.8 x
should occur.
10-4 >
Ksp of PbI2 is 7.1 x 10-9
Ksp so precipitation
Answer: We require at least 9 drops.
115
116
29
Complete precipitation
Problem
A typical Ca2+ concentration in seawater is
0.010 M. Will the precipitation of Ca(OH)2
be complete from a seawater sample in
which [OH-] is maintained at 0.040 M?
Generally we treat precipitation as

complete if 99.9% of the original ion
concentration has been lost to the
precipitate.
For example, if our initial [Pb2+] is 0.10 M,
then precipitation by adding I- is
complete when our solution contains a
[Pb2+] less than 1 x 10-4 M.
Ksp of Ca(OH)2 is 5.5 x 10-6

Answer: Since the final [Ca2+] is 3.4 x 10-3 M,
which is 34 % of 0.010 M, the precipitation is not
complete.
117
118
Selective precipitation
Problem
What [OH-] should be maintained in a
solution if, after precipitation of Mg2+ as solid
magnesium hydroxide, the remaining [Mg2+]
is to be at a level of 1g L-1?
Molar mass Mg is 24.305 g mol-1
Ksp of Mg(OH)2 is 1.8 x 10-11
Answer: [OH-] needed is 1.6 x 10-2 M.
119
If we have a solution with

both CrO42- ions and Br- ions
and add a large amount of Ag+ ions
at once,
then both Ag2CrO4 and AgBr
will precipitate
in our container at the same time.
120
30
If we slowly add the Ag+ solution instead

the solid with the significantly lower
molar solubility (AgBr in this case do
the calculations to check this for yourself)
In other words,
the concentration of Ag+
CAN NOT become large enough
to precipitate Ag2CrO4
until the AgBr
precipitation is complete.
will precipitate first

and consume the added Ag+
preferentially.
121
122
Problem
AgNO3 is slowly added to a solution with
[Cl-] = 0.115 M and [Br-] = 0.264 M. What
percent of the Br- remains unprecipitated
at the point at which AgCl (s) begins to
precipitate?
Ksp values
AgCl = 1.8 x 10-10 AgBr = 5.0 x 10-13
Answer: 0.12 % of Br- remains.
123
124
31
Formation of complex ions
Solubility of a solid increases if there is the

ability to form a complex ion.
An example of a complex ion is Ag(NH3)2+.
Such complexes affect solubility by reducing
the concentration of the cation so that the
dissolution reaction must shift to the
products to replace the cation concentration
to re-establish equilibrium.
Ag+ (aq) + 2 NH3 (aq) Ag(NH3)2+ (aq) Kf = 1.7 x 107

AgCl (s) Ag+ (aq) + Cl- (aq)
Ksp = 1.8 x 10-10
In the presence of ammonia, the dissolution of

AgCl can be expressed by the sum of these two
reactions
2 NH3 (aq) + AgCl (s) Ag(NH3)2+ (aq) + Cl- (aq)
K = Kf x Ksp = 1.7 x 107 x 1.8 x 10-10 = 3.1 x 10-3
125
126
127
128

We see the dissolution of AgCl
occurs to a greater level of
completion
in the presence of ammonia
(K = 3.1 x 10-3)
than it does in pure water
(Ksp = 1.8 x 10-10).
32
Problem
Problem
Will a precipitate of AgCl form from a 1.50

L solution that is 0.100 M AgNO3 and
0.225 M NH3 if 1.00 mL of 3.50 M NaCl is
added?
Ksp AgCl = 1.8 x 10-10
Kf [Ag(NH3)2+] = 1.6 x 107
What total concentration of NH3 is

necessary to keep AgCl from precipitating
from a solution that is 0.0075 M NaCl and
0.13 M AgNO3?
Ksp AgCl = 1.8 x 10-10
Kf [Ag(NH3)2+] = 1.6 x 107
Answer: Since Qsp is 2.3 x 10-8, then

precipitation will occur since Qsp>Ksp.
Answer: [NH3]free = 0.58 M and [NH3]complex

= 0.26 M, so [NH3]tot = 0.84 M
129
130
Problem
Whats the molar solubility of Fe(OH)3 in a
solution containing 0.100 M C2O42-?
Ksp Fe(OH)3 = 4 x 10-38
Kf [Fe(C2O4 )3]3- = 2 x 1020
Answer: The molar solubility is 4 x 10-6.
The solid is much more soluble because
the complex formation reaction removes a
lot of free Fe3+ that the solid must dissolve
to replace.
131
33

Aqueous Ionic Equilibrium

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The Common-Ion Effect

Dr. Peter Warburton

The Common-Ion Effect

Point of view of the acid

Lets consider a solution made of 0.10 moles of acetic

Our reaction will be

First we must identify all potential acids and bases

Note that the initial concentration of our product

Lets check the

1.8 x 10-5 = x (0.10 + x) / (0.10 x)

If we had started out with only 0.10 mol/L

The initial acid concentration / Ka will still be the

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

Without the acetate ion the pH of

The acetate ion makes a large difference on

Adding the conjugate

Addition of the weak

Salts as source of a basic common-ion

Salts as source of a basic common-ion

Salts as source of an acidic common-ion

Salts as source of an acidic common-ion

Solutions that contain both a weak

We saw 0.10 mol L-1 acetic acid 0.10 mol L-1

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

If we rearrange the Ka expression

and make the assumption that x is much less

CH3COOH (aq) + OH- (aq) H2O (l) + CH3COO- (aq)

New [CH3COOH] = 0.09 M and new [CH3COO-] = 0.11 M

With the assumption

Note weve made the assumption that x << 0.09 M!

Adding 0.01 mol of OH- to 1.00 L

What happens if we add 0.01 mol of HCl (strong acid)

CH3COO- (aq) + H3O+ (aq) H2O (l) + CH3COOH (aq)

New [CH3COOH] = 0.11 M and new [CH3COO-] = 0.09 M

With the assumption

Note weve made the assumption that x << 0.09 M!

Adding 0.01 mol of H3O+ to 1.00 L

In the previous two problems, the solution

There is no significant amount

Adding acid or base to a buffer

We do our first table in these buffer

Calculate the pH of a 0.100 L buffer solution

With the assumption that x is much smaller

a) What is the change in pH on addition

b) What is the change in pH on addition

Predicting whether a solution is a buffer

Weve seen that, for solutions with both

Any solution that becomes a mixture of a

1) Weak acid-base conjugate pairs like

2) Weak acid reacting with small amounts of

pH = pKa + log [base] / [acid]

pH = pKa + log [base] / [acid]

pH = pKa + log [base] / [acid]

Preparing buffer solutions

How do we adjust the concentrations?

If we want to create a buffer

How many grams of (NH4)2SO4 (molar

Larger volumes of buffer solutions have

In general buffer solutions have a

We often measure the pH of a solution with

HIn (aq) + H2O (l) H3O+ (aq) + In- (aq)

since pKa is 4.7 (Ka = 1.8 x 10-5)

_