Chapter 19

Ionic Equilibria in Aqueous Systems

19-1
Ionic Equilibria in Aqueous Systems

19.1 Equilibria of Acid-Base Buffer Systems

19.2 Acid-Base Titration Curves

19.3 Equilibria of Slightly Soluble Ionic Compounds

19.4 Equilibria Involving Complex Ions

19.5 Application of Ionic Equilibria to Chemical Analysis

19-2
Figure 19.1
The effect of addition of acid or base to …

acid added base added

Figure 19.2 an unbuffered solution

acid added base added

or a buffered solution
19-3
Table 19.1
The Effect of Added Acetate Ion on the Dissociation of Acetic Acid

[CH3COOH]initial [CH3COO-]added % Dissociation* pH

0.10 0.00 1.3 2.89

0.10 0.050 0.036 4.44

0.10 0.10 0.018 4.74

0.10 0.15 0.012 4.92

[CH3COOH]dissoc
* % Dissociation = x 100
[CH3COOH]initial

19-4
Figure 19.3 How a buffer works.

Buffer after addition of H3O+ Buffer with equal Buffer after addition of OH-
concentrations of
conjugate base and acid

H3O+ OH-

H2O + CH3COOH H3O+ + CH3COO- CH3COOH + OH- H2O + CH3COO-

19-5
Sample Problem 19.1 Calculating the Effect of Added H3O+ or OH-
on Buffer pH
PROBLEM: Calculate the pH:
(a) of a buffer solution consisting of 0.50M CH3COOH and 0.50M CH3COONa
(b) after adding 0.020mol of solid NaOH to 1.0L of the buffer solution in part (a)
(c) after adding 0.020mol of HCl to 1.0L of the buffer solution in part (a)
Ka of CH3COOH = 1.8x10-5. (Assume the additions cause negligible volume
changes.
PLAN:
We know Ka and can find initial concentrations of conjugate acid and base.
Make assumptions about the amount of acid dissociating relative to its initial
concentration. Proceed step-wise through changes in the system.
SOLUTION: (a)
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
Initial 0.50 - 0.50 0
Change -x - +x +x
Equilibrium 0.50-x - 0.50 +x x

19-6
Sample Problem 19.1 Calculating the Effect of Added H3O+ and OH-
on Buffer pH
continued (2 of 4)

[H3O+] = x [CH3COOH]equil ≈ 0.50M [CH3COO-]initial ≈ 0.50M

[H3O+][CH3COO-] [CH3COOH]
Ka = [H3O+] = x = Ka = 1.8x10-5M
[CH3COOH] [CH3COO ]-

Check the assumption: 1.8x10-5/0.50 X 100 = 3.6x10-3 %

(b) 0.020 mol

[OH-]added = = 0.020M NaOH
1.0L soln

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

Before addition 0.50 - 0.50 -
Addition - 0.020 - -
After addition 0.48 0 0.52 -

19-7
Sample Problem 19.1 Calculating the Effect of Added H3O+ and OH-
on Buffer pH
continued (3 of 4)
Set up a reaction table with the new values.

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

Initial 0.48 - 0.52 0

Change -x - +x +x
Equilibrium 0.48 -x - 0.52 +x x

0.48
[H3O+] = 1.8x10-5 = 1.7x10-5 pH = 4.77
0.52
0.020 mol
(c) [H3O+]added = = 0.020M H3O+
1.0L soln
Concentration (M) CH3COO-(aq) + H3O+(aq) CH3COOH(aq) + H2O (l)

Before addition 0.50 - 0.50 -

Addition - 0.020 - -
After addition 0.48 0 0.52 -

19-8
Sample Problem 19.1 Calculating the Effect of Added H3O+ and OH-
on Buffer pH
continued (4 of 4)
Set up a reaction table with the new values.

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

Initial 0.52 - 0.48 0

Change -x - +x +x
Equilibrium 0.52 -x - 0.48 +x x

0.52
[H3O+] = 1.8x10-5 = 2.0x10-5 pH = 4.70
0.48

19-9
The Henderson-Hasselbalch Equation

HA + H2O H 3 O+ + A -

Ka = [H3O+] [A-]

[HA]
Ka [HA]
[H3O+] =
[A-]
[A-]
- log[H3O+] = - log Ka + log
[HA]

[base]
pH = pKa + log
[acid]

19-10
Buffer Capacity and Buffer Range
Buffer capacity is the ability to resist pH change.

The more concentrated the components of a buffer, the greater

the buffer capacity.

The pH of a buffer is distinct from its buffer capacity.

A buffer has the highest capacity when the component

concentrations are equal.

Buffer range is the pH range over which the buffer acts effectively.

Buffers have a usable range within ± 1 pH unit of the pKa of

its acid component.

19-11
Figure 19.4 The relation between buffer capacity and pH change.

19-12
Preparing a Buffer

1. Choose the conjugate acid-base pair.

2. Calculate the ratio of buffer component concentrations.

3. Determine the buffer concentration.

4. Mix the solution and adjust the pH.

19-13
Sample Problem 19.2 Preparing a Buffer

PROBLEM: An environmental chemist needs a carbonate buffer of pH 10.00

to study the effects of the acid rain on limsetone-rich soils. How
many grams of Na2CO3 must she add to 1.5L of freshly prepared
0.20M NaHCO3 to make the buffer? Ka of HCO3- is 4.7x10-11.

PLAN: We know the Ka and the conjugate acid-base pair. Convert pH to

[H3O+], find the number of moles of carbonate and convert to mass.
SOLUTION:
[CO32-][H3O+]
HCO3-(aq) + H2O(l) CO32-(aq) + H3O+(aq) Ka =
[HCO3-]
[CO32-](0.20)
pH = 10.00; [H3O+] = 1.0x10-10 4.7x10-11 = [CO32-] = 0.094M
1.0x10-10

moles of Na2CO3 = (1.5L)(0.094mols/L) = 0.14

105.99g
0.14 moles = 15 g Na2CO3
mol
19-14
Figure 19.5
Colors and approximate pH range of some
common acid-base indicators.
pH

19-15
Figure 19.6 The color change of the indicator bromthymol blue.

basic

acidic change occurs

over ~2pH units
19-16
Figure 19.7 Curve for a strong acid-strong
base titration

19-17
Figure 19.8 Titration of 40.00mL of 0.1000M HPr with
0.1000M NaOH
Curve for a
weak acid-
strong base
titration

pKa of HPr = pH = 8.80 at

4.89 equivalence point

[HPr] = [Pr-] methyl red

19-18
Sample Problem 19.3 Calculating the pH During a Weak Acid-
Strong Base Titration

PROBLEM: Calculate the pH during the titration of 40.00 mL of 0.1000M

propanoic acid (HPr; Ka = 1.3x10-5) after adding the following
volumes of 0.1000M NaOH:
(a) 0.00mL (b) 30.00mL (c) 40.00mL (d) 50.00mL
PLAN: The amounts of HPr and Pr- will be changing during the titration.
Remember to adjust the total volume of solution after each addition.
SOLUTION: (a) Find the starting pH using the methods of Chapter 18.
Ka = [Pr-][H3O+]/[HPr] [Pr-] = x = [H3O+] [Pr-] = x = [H3O+]
x = 1.1x10-3 ; pH = 2.96

(b) Amount (mol) HPr(aq) + OH-(aq) Pr-(aq) + H2O (l)

Before addition 0.04000 - 0 -
Addition - 0.03000 - -
After addition 0.01000 0 0.03000 -

19-19
Sample Problem 19.3 Calculating the pH During a Weak Acid-
Strong Base Titration
continued
0.001000 mol
[H3O+] = 1.3x10-5 = 4.3x10-6M pH = 5.37
0.003000 mol

(c) When 40.00mL of NaOH are added, all of the HPr will be reacted and the [Pr -]
will be (0.004000 mol)
= 0.05000M
(0.004000L) + (0.004000L)
Ka x K b = K w Kb = Kw/Ka = 1.0x10-14/1.3x10-5 = 7.7x10-10

pH = 8.80
(d) 50.00mL of NaOH will produce an excess of OH-.
M = (0.00100)
mol XS base = (0.1000M)(0.05000L - 0.04000L) = 0.00100mol
(0.0900L)
[H3O+] = 1.0x10-14/0.01111 = 9.0x10-11M M = 0.01111

pH = 12.05

19-20
Titration of 40.00mL of 0.1000M NH3 with
Figure 19.9 0.1000M HCl

pKa of NH4+ =
9.25

Curve for a
weak base-
strong acid
titration pH = 5.27 at
equivalence
point

19-21
Figure 19.10 Curve for the titration of a weak polyprotic acid.

pKa = 7.19

pKa = 1.85
Titration of 40.00mL of 0.1000M
H2SO3 with 0.1000M NaOH

19-22
Figure 19.11 Sickle shape of red blood cells in sickle cell anemia.

19-23
Ion-Product Expression (Qsp)
and Solubility Product Constant (Ksp)

For the hypothetical compound, MpXq

At equilibrium Qsp = [Mn+]p [Xz-]q = Ksp

19-24
Sample Problem 19.4 Writing Ion-Product Expressions for Slightly
Soluble Ionic Compounds

PROBLEM: Write the ion-product expression for each of the following:

(a) Magnesium carbonate (b) Iron (II) hydroxide
(c) Calcium phosphate (d) Silver sulfide

PLAN: Write an equation which describes a saturated solution. Take

note of the sulfide ion produced in part (d).
SOLUTION:
(a) MgCO3(s) Mg2+(aq) + CO32-(aq) Ksp = [Mg2+][CO32-]

(b) Fe(OH)2(s) Fe2+(aq) + 2OH- (aq) Ksp = [Fe2+][OH-] 2

(c) Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43-(aq) Ksp = [Ca2+]3[PO43-]2

(d) Ag2S(s) 2Ag+(aq) + S2-(aq)

S2-(aq) + H2O(l) HS-(aq) + OH-(aq) Ksp = [Ag+]2[HS-][OH-]

Ag2S(s) + H2O(l) 2Ag+(aq) + HS-(aq) + OH-(aq)

19-25
Table 19.2 Solubility-Product Constants (Ksp) of Selected Ionic
Compounds at 250C

Name, Formula Ksp

Aluminum hydroxide, Al(OH)3 3 x 10-34

Cobalt (II) carbonate, CoCO3 1.0 x 10-10

Iron (II) hydroxide, Fe(OH)2 4.1 x 10-15

Lead (II) fluoride, PbF2 3.6 x 10-8

Lead (II) sulfate, PbSO4 1.6 x 10-8

Mercury (I) iodide, Hg2I2 4.7 x 10-29

Silver sulfide, Ag2S 8 x 10-48

Zinc iodate, Zn(IO3)2 3.9 x 10-6

19-26
Sample Problem 19.5 Determining Ksp from Solubility

PROBLEM: (a) Lead (II) sulfate is a key component in lead-acid car batteries.
Its solubility in water at 250C is 4.25x10-3g/100mL solution. What is
the Ksp of PbSO4?
(b) When lead (II) fluoride (PbF2) is shaken with pure water at 250C,
the solubility is found to be 0.64g/L. Calculate the Ksp of PbF2.

PLAN: Write the dissolution equation; find moles of dissociated ions;

convert solubility to M and substitute values into solubility product
constant expression.

SOLUTION: (a) PbSO4(s) Pb2+(aq) + SO42-(aq) Ksp = [Pb2+][SO42-]

4.25x10-3g 1000mL mol PbSO4

= 1.40x10-4M PbSO4
100mL soln L 303.3g PbSO4
Ksp = [Pb2+][SO42-] = (1.40x10-4)2 = 1.96x10-8

19-27
Sample Problem 19.5 Determining Ksp from Solubility

continued

(b) PbF2(s) Pb2+(aq) + 2F-(aq) Ksp = [Pb2+][F-]2

0.64g mol PbF2

= 2.6x10-3 M
L soln 245.2g PbF2

Ksp = (2.6x10-3)(5.2x10-3)2 = 7.0x10-8

19-28
Sample Problem 19.6 Determining Solubility from Ksp

PROBLEM: Calcium hydroxide (slaked lime) is a major component of mortar,

plaster, and cement, and solutions of Ca(OH)2 are used in
industry as a cheap, strong base. Calculate the solubility of
Ca(OH)2 in water if the Ksp is 6.5x10-6.
PLAN: Write out a dissociation equation and Ksp expression; Find the molar
solubility (S) using a table.
SOLUTION: Ca(OH)2(s) Ca2+(aq) + 2OH-(aq) Ksp = [Ca2+][OH-]2

Concentration (M) Ca(OH)2(s) Ca2+(aq) + 2OH-(aq)

Initial - 0 0
Change - +S + 2S
Equilibrium - S 2S

Ksp = (S)(2S)2 = 1.2x10x-2M

19-29
Table 19.3 Relationship Between Ksp and Solubility at 250C

No. of Ions Formula Cation:Anion Ksp Solubility (M)

2 MgCO3 1:1 3.5 x 10-8 1.9 x 10-4

2 PbSO4 1:1 1.6 x 10-8 1.3 x 10-4

2 BaCrO4 1:1 2.1 x 10-10 1.4 x 10-5

3 Ca(OH)2 1:2 5.5 x 10-6 1.2 x 10-2

3 BaF2 1:2 1.5 x 10-6 7.2 x 10-3

3 CaF2 1:2 3.2 x 10-11 2.0 x 10-4

3 Ag2CrO4 2:1 2.6 x 10-12 8.7 x 10-5

19-30
Figure 19.12 The effect of a common ion on solubility

CrO42- added
PbCrO4(s) Pb2+(aq) + CrO42-(aq) PbCrO4(s) Pb2+(aq) + CrO42-(aq)

19-31
Sample Problem 19.7 Calculating the Effect of a Common Ion on
Solubility

PROBLEM: In Sample Problem 19.6, we calculated the solubility of Ca(OH)2

in water. What is its solubility in 0.10M Ca(NO3)2? Ksp of
Ca(OH)2 is 6.5x10-6.
PLAN: Set up a reaction equation and table for the dissolution of Ca(OH)2.
The Ca(NO3)2 will supply extra [Ca2+] and will relate to the molar
solubility of the ions involved.
SOLUTION: Concentration(M) Ca(OH)2(s) Ca2+(aq) + 2OH-(aq)

Initial - 0.10 0
Change - +S +2S

Equilibrium - 0.10 + S 2S
Ksp = 6.5x10-6 = (0.10 + S)(2S)2 = (0.10)(2S)2 S << 0.10

Check the assumption:

= 4.0x10-3
4.0x10-3 x 100 = 4.0%
0.10M
19-32
Figure 19.13 Test for the presence of a carbonate.

19-33
Sample Problem 19.8 Predicting the Effect on Solubility of Adding
Strong Acid

PROBLEM: Write balanced equations to explain whether addition of H3O+ from a

strong acid affects the solubility of these ionic compounds:
(a) Lead (II) bromide (b) Copper (II) hydroxide (c) Iron (II) sulfide

PLAN: Write dissolution equations and consider how strong acid would affect
the anion component.
SOLUTION: (a) PbBr2(s) Pb2+(aq) + 2Br-(aq) Br- is the anion of a strong acid.
No effect.

(b) Cu(OH)2(s) Cu2+(aq) + 2OH-(aq)

OH- is the anion of water, which is a weak acid. Therefore it will shift the
solubility equation to the right and increase solubility.

(c) FeS(s) Fe2+(aq) + S2-(aq) S2- is the anion of a weak acid and will
react with water to produce OH-.
FeS(s) + H2O(l) Fe2+(aq) + HS-(aq) + OH-(aq)
Both weak acids serve to increase the solubility of FeS.
19-34
Sample Problem 19.9 Predicting Whether a Precipitate Will Form

PROBLEM: A common laboratory method for preparing a precipitate is to mix

solutions of the component ions. Does a precipitate form when
0.100L of 0.30M Ca(NO3)2 is mixed with 0.200L of 0.060M NaF?
PLAN: Write out a reaction equation to see which salt would be formed. Look
up the Ksp valus in a table. Treat this as a reaction quotient, Q,
problem and calculate whether the concentrations of ions are > or <
Ksp. Remember to consider the final diluted solution when calculating
concentrations.
SOLUTION: CaF2(s) Ca2+(aq) + 2F-(aq) Ksp = 3.2x10-11

mol Ca2+ = 0.100L(0.30mol/L) = 0.030mol [Ca2+] = 0.030mol/0.300L = 0.10M

mol F- = 0.200L(0.060mol/L) = 0.012mol [F-] = 0.012mol/0.300L = 0.040M

Q = [Ca2+][F-]2 = (0.10)(0.040)2 = 1.6x10-4

Q is >> Ksp and the CaF2 WILL precipitate.

19-35
Figure 19.14 Cr(NH3)63+, a typical complex ion.

19-36
Figure 19.15
The stepwise exchange of NH3 for H2O in M(H2O)42+.

NH3

M(H2O)42+ 3NH3

M(H2O)3(NH3)2+

M(NH3)42+

19-37
19-38
Sample Problem 19.10 Calculating the Concentration of a Complex Ion

PROBLEM: An industrial chemist converts Zn(H2O)42+ to the more stable

Zn(NH3)42+ by mixing 50.0L of 0.0020M Zn (H2O)42+ and 25.0L of
0.15M NH3. What is the final [Zn (H2O)42+]?
Kf of Zn(NH3)42+ is 7.8x108.
PLAN: Write the reaction equation and Kf expression. Use a reaction table
to list various concentrations. Remember that components will be
diluted when mixed as you calculate final concentrations. It is
obvious that there is a huge excess of NH3 and therefore it will drive
the reaction to completion.
SOLUTION:
Zn(H2O)42+(aq) + 4NH3(aq) Zn(NH3)42+(aq) + 4H2O(l)

[Zn(NH3)42+] [Zn(H2O)42+]initial = (50.0L)(0.0020M)

Kf = = 1.3x10-3 M
[Zn(H2O)42+][NH3]4 75.0L
[NH3]initial = (25.0L)(0.15M) = 5.0x10-2 M
75.0L

19-39
Sample Problem 19.10 Calculating the Concentration of a Complex Ion

continued

Since we assume that all of the Zn(H2O)42+ has reacted, it would use 4
times its amount in NH3.
[NH3]used = 4(1.3x10-3M) = 5.2x10-3M
[Zn(H2O)42+]remaining = x(a very small amount)

Concentration(M) Zn(H2O)42+(aq) + 4NH3(aq) Zn(NH3)42+(aq) + 4H2O(l)

Initial 1.3x10-3 5.0x10-2 0 -

Change ~(-1.3x10-3) ~(-5.2x10-3) ~(+1.3x10-3) -
Equilibrium x 4.5x10-2 1.3x10-3 -

[Zn(NH3)42+] (1.3x10-3)
Kf = = 7.8x10 =8 x = 4.1x10-7M
[Zn(H2O)42+][NH3]4 x(4.5x10-2)

19-40
Sample Problem 19.11 Calculating the Effect of Complex-Ion Formation
on Solubility

PROBLEM: In black-and-white film developing, excess AgBr is removed from

the film negative by “hypo”, an aqueous solution of sodium
thiosulfate (Na2S2O3), through formation of the complex ion
Ag(S2O3)23-. Calculate the solubility of AgBr in (a) H2O; (b) 1.0M
hypo. Kf of Ag(S2O3)23- is 4.7x1013 and Ksp AgBr is 5.0x10-13.
PLAN: Write equations for the reactions involved. Use Ksp to find S, the molar
solubility. Consider the shifts in equilibria upon the addition of the
complexing agent.

SOLUTION: AgBr(s) Ag+(aq) + Br-(aq) Ksp = [Ag+][Br-] = 5.0x10-13

(a) S = [AgBr]dissolved = [Ag+] = [Br-] Ksp = S2 = 5.0x10-13 ; S = 7.1x10-7M

(b) AgBr(s) Ag+(aq) + Br-(aq)

Ag+(aq) + 2S2O32-(aq) Ag(S2O3)23-(aq)

AgBr(s) + 2S2O32-(aq) Br -(aq) + Ag(S2O3)23-(aq)

19-41
Sample Problem 19.11 Calculating the Effect of Complex-Ion Formation
on Solubility
continued

[Br-][Ag(S2O3]23-
Koverall = Ksp x Kf = = (5.0x10-13)(4.7x1013) = 24
[AgBr][S2O32-]2

Concentration(M) AgBr(s) + 2S2O32-(aq) Br-(aq) + Ag(S2O3)23-(aq)

Initial - 1.0 0 0
Change - -2S +S +S
Equilibrium - 1.0-2S S S

S2 S
Koverall = = 24 = (24)1/2
(1.0-2S)2 1.0-2S

S = [Ag(S2O3)23-] = 0.45M

19-42
Figure 19.16 The amphoteric behavior of aluminum hydroxide.

3H2O(l) + Al(H2O)3(OH)3(s) Al(H2O)3(OH)3(s) Al(H2O)3(OH)4-(s) + H2O(l)

19-43
Sample Problem 19.12 Separating Ions by Selective Precipitation

PROBLEM: A solution consists of 0.20M MgCl2 and 0.10M CuCl2. Calculate

the [OH-] that would separate the metal ions as their hydroxides.
Ksp of Mg(OH)2= is 6.3x10-10; Ksp of Cu(OH)2 is 2.2x10-20.
PLAN: Both precipitates are of the same ion ratio, 1:2, so we can compare
their Ksp values to determine which has the greater solubility.
It is obvious that Cu(OH)2 will precipitate first so we calculate the
[OH-] needed for a saturated solution of Mg(OH)2. This should
ensure that we do not precipitate Mg(OH)2. Then we can check how
much Cu2+ remains in solution.
SOLUTION:
Mg(OH)2(s) Mg2+(aq) + 2OH-(aq) Ksp = 6.3x10-10

Cu(OH)2(s) Cu2+(aq) + 2OH-(aq) Ksp = 2.2x10-20

[OH-] needed for a saturated Mg(OH)2 solution =

= 5.6x10-5M

19-44
Sample Problem 19.12 Separating Ions by Selective Precipitation

continued

Use the Ksp for Cu(OH)2 to find the amount of Cu remaining.

[Cu2+] = Ksp/[OH-]2 = 2.2x10-20/(5.6x10-5)2 = 7.0x10-12M

Since the solution was 0.10M CuCl2, virtually none of the Cu2+ remains
in solution.

19-45
Figure 19.17
The general procedure for separating ions in qualitative analysis.

Add Add
precipitating precipitating
ion ion
Centrifuge

Centrifuge

19-46
Figure 19.18 A qualitative analysis scheme for separating cations
into five ion groups.

Acidify to Add
Add
Add pH 0.5; NH3/NH4+
(NH4)2HPO4
add H2S buffer(pH 8)
6M HCl
Centrifuge

Centrifuge

Centrifuge

Centrifuge
19-47
Extra: A qualitative analysis scheme for Ag+,Al3+,Cu2+, and Fe3+
Step 1
Add Step 2
NH3(aq) Add HCl

Centrifuge
Centrifuge
Step 3 Add
NaOH
Step 4 Step 5
Add HCl, Dissolve in
Na2HPO4 HCl and
add KSCN
Centrifuge

19-48
Figure B19.1 A view inside Carlsbad Caverns, New Mexico

19-49
Figure B19.3 Formation of acidic precipitation.

19-50
Figure B19.4

A forest damaged by acid rain

19-51
Figure B19.5 The effect of acid rain on marble statuary.

1944 1994

Location: New York City

19-52