Aqueous Ionic

Equilibria

Agenda
Formal vs equilibrium concentration
Acid equilibria
Base equilibria
Ka, Kb and Kw
Common ion effect
Buffers
Acid-Base Titrations

Note to Students
This chapter is considered the hardest in CHY102.

Many students struggle with this chapter and the

average mark on Test #2 is typically lower than
on Test #1.
To prepare for the test, and for your future careers
as engineers, please practice with lots of
questions in your textbook and Mastering
Chemistry. Come to our office hours with
questions well before the test!
The last section of these notes is a self-study
section that provides two worked examples
calculating a titration curve. We will not go over
3
the self-study section during class.

Coverage
Sections you should know:
16.2 Buffers: Solutions That Resist pH Change
16.3 Buffer Effectiveness: Buffer Range and Buffer Capacity
16.4 Titrations and pH Curves
Things to exclude:
16.1 The Danger of Antifreeze
16.5 Solubility Equilibria and the Solubility Product Constant
16.6 Precipitation
16.7 Qualitative Chemical Analysis
16.8 Complex-Ion Equilibria

Formal and
equilibrium
concentrations

Formal vs. Equilibrium

Conc.
Formal concentration
cX = moles of X, regardless of chemical form, in
1 L soln
Equilibrium concentration
[X] = actual moles of X in 1 L soln at
equilibrium

Acid examples
e.g. Strong acid: 1.0 molL-1 HCl (formal) is

really

1.0 molL-1 H+ (aq)

1.0 molL-1 Cl-(aq)
cHCl = [H+] = [Cl-]

e.g. Weak acid: 0.100 M acetic acid (formal

conc.) is

[HOAc] = 0.096 molL-1

[OAc-] = 4.210-3 molL-1
cHOAc = [HOAc] + [OAc-]
7

Base examples
e.g. Strong base: 1.0 molL-1 NaOH (formal) is

really

1.0 molL-1 Na+ (aq)

1.0 molL-1 OH-(aq)
cNaOH = [Na+] = [OH-]

e.g. Weak base: 0.100 molL-1 NH3 (formal

conc.) is

[NH3] = 0.096 molL-1

[NH4+] = 4.210-3 molL-1
cNH3 = [NH3] + [NH4+]
8

LC: Formal Concentration

What is true about [HF] in a solution that is
formally 1.0 M HF?

HF(aq)+H2O(l)

A.
B.
C.
D.

H3O+(aq)+F(aq)

[HF] > 1.0 molL-1

[HF] = 1.0 molL-1
[HF] < 1.0 molL-1
Not enough information given.

Acid equilibria

10

Acid dissociation
constant, Ka

11

Note on abbreviations
Generic weak acid: HA
HA = acid
A- = conjugate base (anion)
Acetic acid: CH3COOH
HOAc = CH3COOH

acetic acid

OAc- = CH3COO-

acetate (an anionic base)

Ac = CH3CO-

acetyl group (a radical)

12

Getting Ka from pH
e.g. The pH of a soln of acetic acid with a

formal conc of 0.020 molL-1 is 3.23. Find

Ka.
H+(aq)+OAc(aq)
HOAc(aq)
Ka

OAc H

HOAc

[H+] = 10-pH = 10-3.23 = 5.8910-4 molL-1

13

Regarding H+
Actually two sources of H+
Water dissociation: H2O(l) H+(aq) + OH-(aq)
HOAc dissociation: HOAc(l) H+(aq) + OAc-(aq)
Total [H+] = [OAc-] + [OH-] (by charge balance)

BUT: [OH-] << [OAc-]

Recall: pOH = 14.00 pH = 14.00 3.23 =
10.77
[OH-] = 10-pOH = 10-10.77 = 1.7010-11 <<
5.8910-4
Therefore: assume all [H+] is from weak acid
14

Construct Equilibrium
Table
HOAc(aq)
I

OAc(aq)+H+(aq)

0.020

C
E
Formal concentration of HOAc is 0.020 mol/L
It will serve as the initial concentration (formally)
15

Construct Equilibrium
Table
HOAc(aq)
I

0.020

OAc(aq)+H+(aq)
0

C
E
Using the same formalism, initial H+ and OAcconcentrations are initially zero
16

Construct Equilibrium
Table
HOAc(aq)
I
C
E

0.020

OAc(aq)+H+(aq)
0

0
5.8910-4

When equilibrium is established, [H+] = 5.8910-4,

as calculated from the pH
17

Construct Equilibrium
Table
HOAc(aq)
I

0.020

C
E

-5.8910-4
0.0194

OAc(aq)+H+(aq)
0
+5.8910-4
5.8910-4

0
+5.8910-4
5.8910-4

and from that we can calculate the rest of the

table.
18

Calculate Ka
OAc H 5.89 10 5.89 10

Ka

HOAc

0.0194

= 1.810-5

19

Percent Ionization

20

Concentration and % I
%I depends on both Ka and cHA
[H+] increases with cHA
But %I decreases

21

Example
At equilibrium, [H+] = [A-] = x and [HA] = cHA x

Ka

H A

HA

x2
c HA x

x 2 K a x - c HA K a 0

K a K a 4c HA K a
x
2
2

Ka = 1.810-5 for HOAc

For cHOAc = 0.20 mol/L, [H+] = 0.0019 mol/L

%I = 0.94% (compare 3.0% for 0.020 mol/L)

22

Acetic Acid, Ka = 1.810-5

pH

% Ionisation

23

LC: Percent Ionization

What is the percent ionization if a 0.010 M
aqueous solution of a weak acid HX has a pH of
4.00? Assume acid was dissolved in pure water.
A.
B.
C.
D.

0.010%
0.10%
1.0%
10%

24

LC: Percent Ionization

What is the percent ionization if a 0.010 M
aqueous solution of a weak acid HX has a pH of
4.00? Assume acid was dissolved in pure water.
C. 1.0%
[H+] = 10-pH =10-4.00 = 1.010-4 M
% ionization = (1.010-4/0.010)100%
= 1.0 %
25

LC: Finding pH from Ka

What is the pH of 0.035 mol/L HF (K a = 6.8104
)?
A. 2.13
B.
2.23
C. 2.31
D. 2.34

26

LC: Solving for pH

Using the quadratic formula, with Ka=

6.810-4

x K a x 0.035K a 0
2

K a K a2 4(0.035) K a
x
4.55 10 3
2

Other root is unphysical

pH = -log([H+]) = -log(4.55 10-3) = 2.34

(D)
27

NOTE: Simplifying
assumption
If x << 0.035, then 0.035-x 0.035
Equilibrium expression then becomes

Ka

H F

HF

x2
6.8 10 4
0.035

0.035 6.8 10

4.87 10

pH = -log([H+]) = -log(4.55 10-3) = 2.31

(C)

28

Checking Assumption
Rule of thumb: If [H+] > 0.05cHA, use

quadratic formula

100% 4.9 103 100% 14%

H

cHA

0.035

Always check simplifying assumptions

Quadratic formula always gives the correct

answer

29

Base equilibria

30

Base Dissociation
Constant, Kb
Bq is a weak base with a charge q = 0,-1,-2,-3

Bq(aq) + H2O(l) HBq+1(aq) + OH-(aq)

Base dissociation constant, Kb

[HBq 1 ][OH ]
Kb
[Bq ]

31

Base Dissociation
Constant, Kb

32

pH of a Weak Base

33

pH of a Weak Base
What is pH of 5.0% NaClO? (Kb=3.310-7;
=1.07 g/mL)
Convert 5.0 % NaClO into molL-1

5.0gNaClO 1molNaClO
1.07gsoln

100gsoln
74.4gNaClO 1.00 10 3 Lsoln

cClO- = 0.719 mol L-1

34

pH of a Weak Base
ClO(aq)+H2O(l)
I
C

0.719
-x

0.719 - x

----

HClO(aq)+OH(aq)
0
+x

0
+x

[HClO][OH ]
x2
7
Kb

3.3
10
0.719 x
[ClO ]
35

pH of a Weak Base
Using the quadratic formula,
7
7 2
3.3 10 3.3 10 40.7193.3 10 7
x
2
x = 4.8610-4 mol L-1 = [OH-]
Want pH, so find [H+]

[OH-][H+] = Kw = 1.010-14
[H+] = (1.010-14)/(4.8610-4) = 2.0510-11 mol L-1
pH = -log[H+] = -log(2.0510-11) = 10.69
36

Ka, Kb and Kw

37

Relationship Between Ka
and Kb
KaKb = Kw

H A OH HA

KaKb
HA
A

= [OH-][H+] = Kw

Given Ka you can calculate Kb of the

conjugate base

38

Use of the Ka-Kb Relation

e.g. Ka of HCO3- is 5.610-11. What is Kb of

CO32-?
Kb = Kw/Ka = (1.010-14)/(5.610-11)
= 1.810-4

39

LC: Ka and Kb
Ka for HCN is 4.910-10 at 25 C. Calculate Kb for
CN-.
A.
B.
C.
D.

2.910-5
4.910-5
2.010-5
2.010-9

40

LC: Ka and Kb
Ka for HCN is 4.910-10 at 25 C. Calculate Kb for
CN-.
C. 2.010-5
Kb = Kw/Ka = 1.010-14/4.910-10
= 2.040810-5 = 2.010-5

41

Same thing but with pKs

We have seen that:
KaKb = Kw
-log(KaKb) = -logKw
-logKa + -logKb = -logKw
therefore,
pKa + pKb = pKw
at 25C,

pKa + pKb = 14.00

42

The Common Ion

Effect

43

Common Ion Effect

Dissociation of weak electrolyte is inhibited by

addition of a strong electrolyte sharing a

common ion
Aspect of le Chateliers Principle
HOAc(aq) OAc-(aq) + H+(aq)
HCl(aq) Cl-(aq) + H+(aq)

44

Example
%I of 0.100 mol/L HOAc (Ka=1.810-5) is 1.3% in
water. What is it in 0.100 M NaOAc? (NaOAc
completely dissociates.)

45

Make the usual table...

HOAc(aq)
I

0.100

H+(aq)+OAc(aq)
0

0.100

C
E
cHOAc = 0.100 mol/L
cOAc- = 0.100 mol/L (from NaOAc)
Initial conc. of H+ formally zero
46

Make the usual table...

HOAc(aq)

H+(aq)+OAc(aq)

0.100

0.100

C
E

-x

+x

+x

To reach equilibrium, we need some H+

Comes from HOAc dissociation
And produces some OAc47

Make the usual table...

HOAc(aq)

H+(aq)+OAc(aq)

0.100

0.100

C
E

-x

+x

+x

0.100 + x

0.100 - x

The equilibrium concentrations are therefore...

48

Set up Ka expression and

solve
[H ][OAc ] x 0.100 x
5
Ka

1.8 10
0.100 x
[HOAc]
Assuming x<<0.100,
x = 1.810-5 = [H+]
%I = 0.018% (compare: 1.3% in water)
Adding OAc- shifts equilib towards reactants

49

Buffers
The previous example was a buffer
In this section well learn what they are and an easier
way to calculate their pH

50

Buffers
The previous example was a buffer
In this section well learn
What a buffer is and what it does
How its made
How it works
And an easier way to calculate its pH

51

Buffer
Solution that resists changes in pH upon

addition of a small amount of strong acid or

base
Composition
Mixture of similar concs of weak acid + conj

base

Preparation (3 methods)
Mix weak acid with a salt of its conjugate base

e.g. CH3CO2H and CH3CO2Na

Partially react weak acid with strong base

e.g. CH CO H and NaOH
3
2
Partially react weak base with a strong acid

52

How Buffers Work:

Two coupled equilibria:

HA(aq) H+(aq) + A-(aq)

and
A-(aq) + H2O(l) OH-(aq) + HA(aq)

Adding OH- consumes HA, produces AResults in smaller pH rise than expected

Adding H+ consumes A-, forms HA

Smaller pH decrease than expected
53

Selecting a Buffer
Buffers are most effective when [HA] = [A -]
Rearranging Ka

[HA]
[H ] K a
[A ]

If [HA] = [A-] then [H+] = Ka

Choose acid with pKa closest to the pH of

interest

e.g. NH4+ has pKa= -log(5.610-10) = 9.25

NH4+/NH3 is good buffer for pH 9 range
54

LC: Selecting a Buffer

Which of the following weak acids would be the
best to use to make a buffer solution of pH =
4.8?
A.Acetic acid (Ka = 1.7510-5)
B.Formic acid (Ka = 1.810-4)
C.Dihydrogen phosphate (Ka = 6.210-8)
D.Nitrous acid (Ka = 4.510-4)

55

LC: Selecting a Buffer

Which of the following weak acids would be the
best to use to make a buffer solution of pH =
4.8?
A. Acetic acid (Ka = 1.7510-5 ; pKa = 4.76)

56

Henderson-Hasselbalch Equation
A convenient way to calculate pH of buffer:

H K

HA

HA

logH log K a
A

logH logK a logHA logA

A
pH pK a log

HA

57

Henderson-Hasselbalch Equation
If % ionization is small, then
[HA] ca
(a stands for acid)
[A-] cb
(b stands for base)

and so the equation becomes

cb

pH pK a log
ca

Known as Henderson-Hasselbalch equation

Under most normal buffer conditions, formal

concentrations are good enough to determine buffer pH

58

Using HendersonHasselbalch
What is the pH of a solution that is formally

0.10 mol/L NH3 and 0.15 mol/L NH4+ (Ka =

5.610-10)?
cb

pH pK a log
ca

pKa log5.6 10 10 9.251

0.10
pH 9.251 log
9.07
0.15
59

Check assumptions
Is NH4+ appreciably dissociated?
[H+] = 10-9.07 = 8.510-10
% ionization = (8.510-10/0.15)100% << 1%
Is NH3 appreciably hydrolysed?

[OH-] = Kw/[H+] = (1.0010-14/8.510-10) = 1.210-5

% ionization = (1.210-5/0.10)100% <<1%
Neither is appreciably dissociated
That is the case for most normal buffers
60

LC: HendersonHasselbalch
What is the pH of a buffer solution that is 0.10
mol/L in acetic acid and 0.50 mol/L in sodium
acetate?
Ka = 1.810-5
A.
B.
C.
D.

2.87
4.05
4.74
5.44
61

LC: Henderson-Hasselbalch
What is the pH of a buffer solution that is 0.10
mol/L in acetic acid and 0.50 mol/L in sodium
acetate?
Ka = 1.810-5
cb

pH pK a log
D. 5.44

ca

pK a log 1.8 105 4.7447

0.50
pH 4.7447 log
5.44
0.10

62

Creating a buffer
e.g. What mass of NaOAc (82.0 g/mol) would

you add to 1.00 L of 0.25 mol/L HOAc (Ka =

1.810-5) to obtain a pH-5.00
cb buffer?

pH pK a log
ca
ca
pH

Taking antilogs of both sides

10
K a
cb
Solving for cb

K a ca
cb pH
10

63

Creating a buffer

1.8 10 0.25

0.45
5

cb

1.0 10 5

cOAc- must be 0.45 mol/L

If volume remains 1.00 L after NaOAc added,

then 0.45 mol of NaOAc needed

Mass of 0.45 mol of NaOAc is
(0.45 mol)(82.0 g/mol) = 37 g

64

Adding Strong Acid/Base to Buffer

A 0.500-L volume of buffer is 0.50 mol/L NH3
and 0.30 mol/L NH4Cl (Ka=5.610-10). What is
the pH after adding 0.200 L of 0.50 mol/L HCl?
Divide question into three parts:
stoichiometric calculation for rxn
dilution calculation to find final conc NH3 and
NH4+
H-H calculation for pH
65

The stoichiometric
calculation
What reacts with HCl?
HCl (aq) + NH3 (aq) NH4Cl (aq)
Moles NH3 before reaction:
(0.50 mol/L)(0.500 L) = 0.25 mol

Moles NH4+ before reaction:

(0.30 mol/L)(0.500 L) = 0.15 mol

Moles of HCl before reaction:

(0.50 mol/L)(0.200 L) = 0.10 mol

66

The stoichiometric
calculation
During rxn, HCl completely consumed to form

NH4+
Moles after rxn,
moles NH3 = 0.25 mol - 0.10 mol = 0.15
mol
moles NH4+ = 0.15 mol + 0.10 mol = 0.25
mol
moles HCl = 0

67

Dilution calculation
Formal concs after rxn

cNH3 = (0.15 mol)/(0.500L + 0.200L) = 0.214

mol/L
cNH4+ = (0.25 mol)/(0.500L + 0.200L) = 0.357
mol/L

68

Henderson-Hasselbalch
calc
cb

pH pK a log
ca
0.214
pH 9.251 log
9.03
0.357

69

Acid-Base
Titrations

70

Acid-Base Titrations
Analyte is acid and titrant a base, or vice

versa
Analyte may be weak or strong
Titrant is always strong
We will calculate the titration curve for two
types of titration:
strong acid (analyte) titrated with a strong

base, and
weak acid (analyte) titrated with a strong base

71

Titration Curves
Graph of pH vs

volume of titrant
added
Equivalence point is the

inflection point
The end point
determined by indicator
Indicator chosen to
change colour at the
equivalence point
72

Titration of weak & strong

acids
End point
for weak
acid with
methyl red

Titration
error

73

Titration of weak &

strong acids
Weak acids have higher initial pH than strong

acids
Due to incomplete dissociation

Rapid rise near equiv pt smaller for weak acid

pH at equiv pt > 7.00 for weak acid
Conjugate base stronger for weak acid

Important considerations for choosing

indicator

74

Ka and titration curves

75

Bases titrated with strong

acid

76

Summary
Understand formal vs equilibrium

concentration
Know how to set up and solve
Weak acid equilibria
Weak base equilibria

Know relationship between Ka, Kb and Kw

Understand common ion effect & buffers
Go through self-study section on acid-base

titrations
Slides 78-98 (following)
77

Suggested practice
problems
Review questions 2 19
Problems by topic 29, 33, 37, 41, 45, 47, 49,

53, 55, 59, 61, 65, 67, 69, 71, 75, 77, 79, 81,
87159, 161

78

Self-study

Calculating
titration curves
Self-study section
A nice application of acid-base equilibrium
calculations

79

Self-study

Example 1: Strong acid

titrated with strong base
Sketch the titration curve for 50.00 mL of 0.100 mol/L
HCl titrated with 0.100 mol/L NaOH

80

Self-study

The Five Regions

Five regions of titration curve
Initial pH
Equivalence point
Just before equivalence point
Just after equivalence point
Post-equivalence (asymptote)
Remember: NaOH and HCl react at

equivalence to form a neutral salt (NaCl)

81

Self-study

Region 1: Initial pH
Initial pH means pH before any NaOH added
[H+] = cHCl
HCl is a strong acid
All the HCl is dissociated in water

pH = -log([H+]) = -log(0.100) = -1.000

We can plot the first point on the graph:

(VNaOH = 0 mL, pH = 1.000)

82

Self-study

Region 2: Equivalence
point

83

Self-study

Region 2: Equivalence
point

At equivalence pt, solution is NaCl(aq)

Neutral; i.e. [H+] = [OH-] = 1.010-7 mol/L
pH = 7.00
Plot the equivalence point at

(VNaCl = 50.00 mL, pH=7.00)

84

Region 3: Just before

equiv pt

Self-study

What is the pH after 49.90 mL of 0.100 M NaOH

has been added?
Between initial and equiv point, HCl in excess
moles NaOH added:
(49.9010-3 L)(0.100 M) = 4.9910-3 mol
moles HCl at start: 5.0010-3 mol
excess moles HCl: 1.010-5 mol

85

Region 3: Just before

equiv pt

Self-study

Excess HCl will be dissociated

Dont forget dilution!
moles H+ = 1.010-5 mol
[H+]=(1.010-5 mol)/{(50.00 + 49.90)10-3 L}

= 1.010-4 mol/L
pH = -log(1.010-4) = 4.00
Plot a point at
(VNaOH = 49.90 mL, pH = 4.00)

86

Region 4: Just after

equiv pt

Self-study

Beyond the equivalence point, NaOH is in excess

What is the pH after 50.10 mL NaOH added?
Excess moles of NaOH

(50.1010-3 L)(0.100 M) - (50.0010-3 L)(0.100 M)

= 1.010-5 mol
[OH] = (1.010-5 mol)/(100.1010-3 L) = 9.9910-5 M
pOH = 4.00
pH = 14.00 - 4.00 = 10.00
Plot a point at (VNaOH = 50.10 mL, pH = 10.00)
87

Region 5: PostEquivalence

Self-study

What is the highest pH possible?

pH asymptotically approaches pH of titrant as

V
pH of titrant is 14.00 + log(0.100) = 13.00
pH should not rise above 13.00

88

Self-study

The pH Curve
14
12

The shape is sketched from the four

previously calculated points and the
asymptotic approach to pH 13 (the
pH of the titrant)

pH

10
8
6
4
2
0
0

10

20

30

40

50

60

70

Volume of NaOH Added (mL)

89

Example 2: Weak
acid titrated with
strong base

Self-study

Sketch the pH curve for the titration of 50.00 mL of

0.100 mol/L HOAc (Ka=1.810-5) with 0.100 mol/L
NaOH

90

Self-study

Weak acid + strong base

Must consider acid & base equilibria
Not necessary in previous example
Requires one more calculation than previous

example

91

Self-study

The Six Regions

Six regions of weak acid/strong base titration
curve
Initial pH
Equivalence point
Just before equivalence point
Just after equivalence point
Post-equivalence (asymptote)
Buffer region (mid-way between initial and
equivalence)
92

Self-study

Region 1: Initial pH
pH is found from an equilibrium calculation

[A ][H ]
Ka
1.8 10 5
[HA]
If a conc, x, of HA dissociates, then
x2
Ka
1.8 10 5
0.100 x
If x << 0.100, then
x 1.8 10 5 0.100 -31.34 10 3
And so the pH = -log(1.3410 ) = 2.87 (VNaOH =
0)
93

Self-study

Region 2: Equivalence

94

Self-study

Region 2: Equivalence
Perform a Kb calculation to find [OH-]

[HOAc][OH ] K w
10
Kb

5.6

10
[OAc ]
Ka
If x mol/L of OAc- react with water, then

x2
Kb
5.6 10 10
0.0500 x
x = 5.2910-6 = [OH-], so pOH = 5.28
pH = 14.00 - 5.28 = 8.72

(basic, as expected)
95

Region 3: Just before

equiv pt

Self-study

After addition of 49.90 mL NaOH

excess HOAc is 1.010-5 mol
cHOAc = (1.010-5 mol)/(0.100 L) = 1.010-4 mol/L
Mol OAc-: (49.9010-3L)(0.100 mol/L)=4.9910-3 mol
cOAc-= (4.9910-3 mol)/(99.9010-3 L) = 0.04995 mol/L
Find pH by equilib calc; if x M HOAc dissociates,

x0.04995 x
5
Ka

1.8
10
4
1.0
10
x x = 3.610-8
Solving (assume x<<0.0001):
pH = -log(3.610-8) = 7.44

96

Regions 4&5: Postequivalence

Self-study

After the equivalence point, OH- is in excess

pH is determined by OH- from excess NaOH
Same as for strong acid
After addition of 50.10 mL of NaOH, excess

OH- is 1.010-5 mol, and [OH-] = 1.010-4

mol/L
pOH = 4.00 and pH = 10.00
Plot point at (50.10 mL, 10.00)
Also, curve asymptotically approaches pH of
titrant, as for HCl (Region 5)
97

Self-study

Region 6: Buffer region

Mid-point between initial and equivalence

(25.00 mL)
Half HOAc consumed (now OAc-)
Solution is a buffer
Use Henderson-Hasselbalch
cb equation

pH pK a log
ca
cb = ca, so pH = pKa = -log(1.810-5) = 4.74
Plot point at (25.00 mL, 4.74)
98

Self-study

Comparison of titration
curves
14
12
10
pH

8
6

Weak acid + strong base

Strong acid + strong base

2
0
0

10

20

30

40

50

60

70

Volume of NaOH Added (mL)

99