Acid-Base Equilibria and

Solubility Equilibria

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The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses the ionization of

a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

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 Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
-] pH = pKa + log
[A [acid]
-log [H+] = -log Ka + log
[HA]

[A-]
pH = pKa + log pKa = -log Ka
[HA]
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A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
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Example 17.2

(a) Calculate the pH of a buffer system containing 1.0 M

CH3COOH and 1.0 M CH3COONa. Ka of CH3COOH is 1.8 x
10-5 .

Answer: pH = 4.74

(b) What is the pH of the buffer system after the addition of 0.10
mole of gaseous HCl to 1.0 L of the solution? Assume that
the volume of the solution does not change when the HCl is
added.
Answer: pH = 4.74

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Example 17.2
Strategy
(a) The pH of the buffer system before the addition of HCl can
be calculated from the ionization of CH3COOH. Note that
because both the acid and the sodium salt of the acid are
present, the initial concentrations of CH3COOH and
CH3COO− (from CH3COONa) are both 1.0 M. The Ka of
CH3COOH is 1.8 x 10-5 (see Table 16.3).
(b) It is helpful to make a sketch of the changes that occur in
this case.

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Example 17.2
Solution (a) We summarize the concentrations of the species
at equilibrium as follows:

CH3COOH(aq) H+(aq) + CH3COO-(aq)

Initial (M): 1.0 0 1.0
Change (M): -x +x +x
Equilibrium (M): 1.0-x x 1.0+x

[H + ][CH 3COO- ]
Ka =
[CH 3COOH]
(x)(1.0+x)
1.8 × 10-5 =
(1.0-x)

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Example 17.2

Assuming 1.0 + x ≈ 1.0 and 1.0 - x ≈ 1.0, we obtain

(x)(1.0+x) x(1.0)
-5
1.8 × 10 = 
(1.0-x) 1.0

or
x = [H+] = 1.8 x 10-5 M
Thus,
pH = -log (1.8 x 10-5 ) = 4.74

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Example 17.2
(b) When HCl is added to the solution, the initial changes are

HCl(aq) → H+(aq) + Cl-(aq)

Initial (mol): 0.10 0 0
Change (mol): -0.10 +0.10 +0.10
Final (mol): 0 0.10 0.10

The Cl- ion is a spectator ion in solution because it is the

conjugate base of a strong acid. The H+ ions provided by the
strong acid HCl react completely with the conjugate base of
the buffer, which is CH3COO-. At this point it is more
convenient to work with moles rather than molarity. The
reason is that in some cases the volume of the solution may
change when a substance is added. A change in volume will
change the molarity, but not the number of moles.
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Example 17.2

The neutralization reaction is summarized next:

CH3COO-(aq) + H+(aq) → CH3COOH(aq)

Initial (mol): 1.0 0.10 1.0
Change (mol): -0.10 -0.10 +0.10
Final (mol): 0.90 0 1.1

Finally, to calculate the pH of the buffer after neutralization of

the acid, we convert back to molarity by dividing moles by 1.0 L
of solution.

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Example 17.2

CH3COOH(aq) H+(aq) + CH3COO-(aq)

Initial (M): 1.1 0 0.90
Change (M): -x +x +x
Equilibrium (M): 1.1-x x 0.90+x

[H + ][CH 3COO- ]
Ka =
[CH 3COOH]
-5 (x)(0.90+x)
1.8 × 10 =
(1.1-x)

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Example 17.2
Assuming 0.90 + x ≈ 0.90 and 1.1 - x ≈ 1.1, we obtain

(x)(0.90+x) x(0.90)
-5
1.8 × 10 = 
(1.1-x) 1.1
or

x = [H+] = 2.2 x 10-5 M

Thus,
pH = -log (2.2 x 10-5 ) = 4.66

Check The pH decreases by only a small amount upon the

addition of HCl. This is consistent with the action of a buffer
solution.
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 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

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Example 17.3
Describe how you would prepare a “phosphate buffer” with a
pH of about 7.40.

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Example 17.3
Strategy

For a buffer to function effectively, the concentrations of the acid

component must be roughly equal to the conjugate base
component. According to Equation (17.3), when the desired pH
is close to the pKa of the acid, that is, when
pH ≈ pKa,
[conjugate base]
log  0
[acid]

or
[conjugate base]
 1
acid
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Example 17.3
Solution

Because phosphoric acid is a triprotic acid, we write the three

stages of ionization as follows. The Ka values are obtained from
Table 16.4 and the pKa values are found by applying Equation
(17.2).

H3 PO 4 (aq ) ƒ H + (aq ) + H 2 PO -4 (aq ) K a1 = 7.5 × 10-3 ; pK a1 = 2.12

H 2 PO -4 (aq) ƒ H + (aq) + HPO 42- (aq) K a 2 = 6.2 × 10-8 ; pK a 2 = 7.21
HPO 2-
4 ( aq ) ƒ H +
(aq ) + PO 3-
4 (aq ) K a 3 = 4.8 × 10-13 ; pK a 3 = 12.32

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Example 17.3

The most suitable of the three buffer systems is HPO2-

4 /H2 PO-
4,
because the pKa of the acid H2PO-4 is closest to the desired pH.
From the Henderson-Hasselbalch equation we write

[conjugate base]
pH = pK a + log
[acid]
[HPO 2-4 ]
7.40 = 7.21 + log
[H 2 PO -4 ]
[HPO 2-4 ]
log -
= 0.19
[H 2 PO 4 ]

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Example 17.3

Taking the antilog, we obtain

[HPO 2-4 ] 0.19

-
= 10 = 1.5
[H 2 PO 4 ]

Thus, one way to prepare a phosphate buffer with a pH of 7.40

is to dissolve disodium hydrogen phosphate (Na2HPO4) and
sodium dihydrogen phosphate (NaH2PO4) in a mole ratio of
1.5:1.0 in water. For example, we could dissolve 1.5 moles of
Na2HPO4 and 1.0 mole of NaH2PO4 in enough water to make
up a 1-L solution.

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 Titrations (Review)
In a titration, a solution of accurately known concentration is
gradually added to another solution of unknown concentration
until the chemical reaction between the two solutions is
complete.

Equivalence point – the point at which the reaction is complete

Indicator – substance that changes color at (or near) the

equivalence point

Slowly add base

to unknown acid
UNTIL
the indicator
changes color
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(pink)
Alternative Method of Equivalence Point Detection

monitor pH
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Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

OH- (aq) + H+ (aq) H2O (l)

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Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

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Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4+ (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

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 Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
-  10 Color of acid (HIn) predominates
[In ]
[HIn]
 10 Color of conjugate base (In -) predominates
[In-]

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Solutions of Red Cabbage Extract

pH
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The titration curve of a strong acid with a strong base.

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Example 17.5
Which indicator or indicators listed in Table 17.1 would you use
for the acid-base titrations shown in

(a) Figure 17.4?

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Example 17.5

(b) Figure 17.5?

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Example 17.5

(c) Figure 17.6?

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 Solubility Equilibria

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+][Cl-] Ksp is the solubility product constant

MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2

Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]
Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2
Dissolution of an ionic solid in aqueous solution:

Q < Ksp Unsaturated solution No precipitate

Q = Ksp Saturated solution
Q > Ksp Supersaturated solution Precipitate will form
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31
Molar solubility (mol/L) is the number of moles of solute
dissolved in 1 L of a saturated solution.
Solubility (g/L) is the number of grams of solute dissolved in
1 L of a saturated solution.

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Example 17.6
The solubility of calcium sulfate (CaSO4) is found to be
0.67 g/L. Calculate the value of Ksp for calcium sulfate.

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Example 17.7
Using the data in Table 17.2, calculate the solubility of
copper(II) hydroxide, Cu(OH)2, in g/L.

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Solubility is the maximum amount of solute that will dissolve
in a given quantity of solvent at a specific temperature.

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 Precipitation Diagram (from Masterton
Textbook)

Shaded – insoluble in water at 25 deg. Celsius

Unshaded – soluble in water at 25 deg. Celsius
Example 17.8
Exactly 200 mL of 0.0040 M BaCl2 are mixed with exactly
600 mL of 0.0080 M K2SO4. Will a precipitate form?

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 The Common Ion Effect and Solubility

The presence of a common ion decreases the solubility of the

salt.

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Example 17.9
Calculate the solubility of silver chloride (in g/L) in a 6.5 x 10-3 M
silver nitrate solution.

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 pH and Solubility
• The presence of a common ion decreases the solubility.
• Insoluble bases dissolve in acidic solutions
• Insoluble acids dissolve in basic solutions

Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)

At pH less than 10.45

Ksp = [Mg2+][OH-]2 = 1.2 x 10-11 Lower [OH-]
Ksp = (s)(2s)2 = 4s3 OH- (aq) + H+ (aq) H2O (l)
4s3 = 1.2 x 10-11 Increase solubility of Mg(OH)2
s = 1.4 x 10-4 M At pH greater than 10.45
[OH-] = 2s = 2.8 x 10-4 M Raise [OH-]
pOH = 3.55 pH = 10.45 Decrease solubility of Mg(OH)2
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 Complex Ion Equilibria and Solubility
A complex ion is an ion containing a central metal cation
bonded to one or more molecules or ions.
Co2+ (aq) + 4Cl- (aq) CoCl42- (aq)

The formation constant or stability constant (Kf) is the

equilibrium constant for the complex ion formation.

[CoCl42- ]
Kf =
Co(H2O)2+ [Co2+][Cl-]4
6 CoCl2-
4

stability of
Kf
HCl complex

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43
Example 17.10
A 0.20-mole quantity of CuSO4 is added to a liter of 1.20 M NH3
solution. What is the concentration of Cu2+ ions at equilibrium?

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Example 17.10
Strategy The addition of CuSO4 to the NH3 solution results in
complex ion formation

Cu2+(aq) + 4NH3(aq) Cu(NH3 )24(aq)

From Table 17.4 we see that the formation constant (Kf) for this
reaction is very large; therefore, the reaction lies mostly to the
right. At equilibrium, the concentration of Cu2+ will be very small.
As a good approximation, we can assume that essentially all
the dissolved Cu2+ ions end up as Cu(NH3 )24 ions. How many
moles of NH3 will react with 0.20 mole of Cu2+? How many
moles of Cu(NH3 )24 will be produced? A very small amount of
Cu2+ will be present at equilibrium. Set up the Kf expression for
the preceding equilibrium to solve for [Cu2+ ].
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Example 17.10
Solution The amount of NH3 consumed in forming the complex
ion is 4 x 0.20 mol, or 0.80 mol. (Note that 0.20 mol Cu2+ is
initially present in solution and four NH3 molecules are needed
to form a complex ion with one Cu2+ ion.) The concentration
of NH3 at equilibrium is therefore (1.20 - 0.80) mol/L soln or
0.40 M, and that of Cu(NH3 )24is 0.20 mol/L soln or 0.20 M, the
same as the initial concentration of Cu2+ . [There is a 1:1 mole

ratio between Cu2+ and Cu(NH3 )24.] Because Cu(NH3 )24
does dissociate to a slight extent, we call the concentration of
Cu2+ at equilibrium x and write
[Cu(NH 3 ) 24 ]
Kf =
[Cu 2+ ][NH 3 ]4
13 0.20
5.0 × 10 =
x(0.40) 4
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Example 17.10
Solving for x and keeping in mind that the volume of the
solution is 1 L, we obtain

x = [Cu2+] = 1.6 x 10-13 M

Check

The small value of [Cu2+] at equilibrium, compared with 0.20 M,

certainly justifies our approximation.

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Effect of Complexation on Solubility
AgNO
Add3 +
NHNaCl
3

AgCl 3)2+
Ag(NH 48
49
Qualitative
Analysis of
Cations

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 Flame Test for Cations

lithium sodium potassium copper

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