Acid–Base Equilibria

in Aqueous Solutions
Chapter 5
Kimia Dasar II (CH1201)
2017-2018

References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill
MITopencourseware

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved.
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration

2
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration

3
Ionization of Water and pH Concept

• Lots of weak acids and bases

• How can we quantify their relative strengths?
• Need reference
• Choose H2O
• Water under right voltage
• Slight conductivity
• Where does conductivity come from?

4
Weak Acids and Bases
• Incompletely ionized
• Molecules and ions exist in equilibrium

HA(aq) + H2O ⇌ A–(aq) + H3O+(aq) HA = any weak acid

B (aq) + H2O ⇌ B H+(aq) + OH–(aq)

B = any weak base

Ex:

1. CH3COOH(aq) + H2O ⇌ CH3COO–(aq) + H3O+(aq)

2. HSO3–(aq) + H2O ⇌ SO32–(aq) + H3O+(aq)
3. NH4+(aq) + H2O ⇌ NH3 (aq) + H3O+ (aq)
5
Weak Acid/Base Equilibria
HA(aq) + H2O A–(aq) + H3O+(aq)

[ A ][H3O ]
- +
K c¢ =
[HA ][H2O]
• But [H2O] = constant (55.6 M ) so rewrite as
[ A ][H3O ]
- +
K c¢ ´ [H2O] = = Ka
[HA]

• Where Ka = acid ionization constant

6
Weak Acid/Base Equilibria
• Often simplify as
• HA (aq) A –(aq) + H+(aq)

[A - ][H+ ]
Ka =
[HA]
pK a = -log K a
-pK a
K a = 10

7
Table 16.2. Weak Monoprotic Acids at
25 °C

8
Learning Check
What is the pKa of HF if Ka = 3.5 × 10–4?

HF(aq) + H2O F–(aq) + H3O+(aq)

or
HF(aq) F–(aq) + H+(aq)

[F- ][H+ ]
Ka = = 3.5 × 10–4
[HF]
pKa = –log Ka = –log(3.5 × 10–4) = 3.46
9
Reaction of a Weak Base with Water
CH3COO–(aq) + H2O CH3COOH(aq) + OH–(aq)
NH3(aq) + H2O NH4+(aq) + OH–(aq)
or generally

B (aq) + H2O B H+(aq) + OH–(aq)

[BH ][OH ]
+ -
But [H2O] = constant
K c¢ =
[B ][H2O] so rewrite as
[BH ][OH ]
+ -
Kb = Where Kb = base ionization
[B ] constant

𝑝𝐾𝑏 = −𝐿𝑜𝑔 𝐾𝑏 𝐾𝑏 = 10−𝑝𝐾𝑏

10
Learning Check

What is the pKb of C5H5N if Kb = 1.7 × 10–9?

C5H5N(aq) + H2O C5H5NH+(aq) + OH–(aq)

_
+
[C 5H5NH ][OH ]
Kb = = 1.7 × 10–9
[C 5H5N]
pKb = –log Kb = –log(1.7 × 10–9) = 8.76

11
Table 16.3. Weak Bases at 25 °C

12
Conjugate Acid-Base Pairs and
Values of Ka and Kb
1. Consider ionization reaction of generic acid
and water
HA(aq) + H2O A–(aq) + H3O+(aq)
[A - ][H+ ]
Ka =
[HA]

2. Consider reaction of a salt containing anion

of this acid (its conjugate base) with water
A–(aq) + H2O HA(aq) + OH–(aq)

[HA][OH- ]
Kb =
[A - ]
13
 3. Now adding reactions we get

HA(aq) + H2O A–(aq) + H3O+(aq)

A–(aq) + H2O HA(aq) + OH–(aq)
2H2O H3O+(aq) + OH–(aq)
− + −
[A ][H ] [HA][OH ] + −
K a Kb =  −
= [H ][OH ] = K w
[HA] [A ]
For any conjugate acid base pair:
K a  K b = K w = 1.0  10 −-14 (at 25 °C) 14
 Equilibrium Calculations
• Need to develop strategy for dealing with weak
acid/base equilibrium calculations

Two general types of calculations:

1. Calculating Ka or Kb from initial concentrations
of acid or base and measured pH in solution

2. Calculating equilibrium concentrations given

Ka or Kb and initial concentrations

15
1. Calculating Ka and Kb from Initial
Concentrations and Equilibrium Data
• Need to evaluate mass action expression = reaction
quotient Q when the reaction is at equilibrium
• Since Q = Kc when at equilibrium
• Can either be given initial concentrations and one
equilibrium concentration
• Usually pH or pOH
• OR can be given initial concentrations and
% ionization
moles ionized per liter
% ionization =  100%
moles available per liter
16
Calculating Ka
• Niotinic acid (niacin) is a monoprotic acid with the
formula HC6H4NO2. A solution that is 0.012 M in
nicotinic acid has a pH of 3.39 at 25 °C. What are
the acid-ionization constant, Ka, and pKa for this
acid at 25 °C?
• What is the degree of ionization of nicotinic acid
in this solution?

HC6H4NO2 + H2O C6H4NO2– + H3O+

17
Calculating Ka (cont.)
[C 6H4NO2- ][H+ ]
Ka =
[HC 6H4NO2 ]

[HC6H4NO2] [C6H4NO2–] [H+] (M )

(M ) (M )
I 0.012 0 0
C –x +x +x
E 0.012 – x x x
• What is value of x? We know the pH so we can
calculate [H+] which is equal to x.
x = antilog(–pH) = 10–pH = 10–3.39
= 4.1 × 10–4 = [H+] 18
Calculating Ka (cont.)
x = 0.00041 is inserted into the ICE table.

[HC6H4NO2] (M ) [C6H4NO2–] [H+] (M )

(M )
I 0.012 0 0
C – 0.00041 + 0.00041 + 0.00041
E 0.012 – 0.00041 = 0.012 0.00041 0.00041

▪ Notice if Cinitial>> Ka, then equilibrium concentration of acid

is the initial concentration since x (in this case 0.00041)
must be zero when properly rounded to calculate
[HC6H4NO2]
19
Calculating Ka (cont)
• Now ready to calculate Ka.
x2 x2 (0.00041)2
Ka =  = = 1.4  10 −- 5
0.012 −- x 0.012 0.012
−-5
pK a = − log(1.4  10 ) = 4.85

• Next calculate:
moles ionized per liter
% ionization =  100%
moles available per liter
x 0.00041
= =  100% = 3.4%
c 0.012
20
2. Calculating Equilibrium Concentrations from
Ka (or Kb) and Initial Concentrations

Almost any problem where you are given Ka or Kb

falls into one of three categories:

1. Only solute is a weak acid

2. Only solute is a weak base
3. Two solutes, one a weak acid, the other its
conjugate base

21
Your Turn!
Hypochlorous acid, HClO, is a weak acid with
Ka = 3.0 × 10–8. What is the pH of a solution with an
initial concentration of 0.20 M hypochlorous acid ?
A. 3.41
B. 4.11
C. 6.82
D. 2.89

22
Your Turn! - Solution
[HOCl] [H3O+] [OCl–]
I 0.20 M 0 0
C –x +x +x
E 0.20 – x x x
éH O+ ùéOCl- ù
ë 3 ûë û x 2
K a = 3.0 ´ 10-8 = =
éHOClù 0.20 - x
ë û
Assume x is small
x2
3.0 ´ 10-8 = x 2 = 6.0 ´ 10-9
0.20 - x
x = 7.74 ´ 10-5 pH = –log (7.74 ´ 10-5 ) = 4.11
23
Your Turn!
The Ka for benzoic acid is 6.5 x 10-5. What is the pH
of a 0.10 M benzoic acid solution?

éH O+ ùéC H COO- ù
ë 3 û ë 6 5 û x 2
K a = 6.5 ´ 10-5 = =
A. 2.60 éC H COOHù 0.10 - x
ë 6 5 û
B. 4.19 Assume x is small
C. 2.09 x2
-5
6.5 ´ 10 = x 2 = 6.5 ´ 10-6
D. 1.59 0.10
x = 2.55 ´ 10-3 pH = –log (2.55 ´ 10-3 ) = 2.60

24
Simplifications in Acid-Base
Equilibrium Calculations
Morphine, C17H19O3N, is administered medically to
relieve pain. It is a naturally occurring base, or
alkaloid.
What is the pH of a 0.075 M solution of morphine at
25 °C?
The base ionization constant, Kb, is 1.6 × 10–6 at 25
°C.

C17H19O3N (aq) + H2O OH–(aq) + HC17H19O3N+(aq)

25
Acid-Base Calculations (cont)
[C17H19O3N] [HC17H19O3N+] [OH–] (M )
(M ) (M )
I 0.075 0 ~0
C –x +x +x
E 0.075 – x x x
[OH- ][HC17H19O3N+ ] x2
Kb = =
[C17H19O3N] 0.075 - x
▪ Assume x << 0.075 so 0.075 + x  0.075
▪ Inserting terms for Kb and x gives
x2 −6
= 1.6  10
0.075 26
Acid-Base Calculations (cont)
x 2 @ 1.6 ´10-6 ´ 0.075 = 1.2 ´ 10-7
x = 1.2  10 −7 = 3.5 × 10–4 M
• x  [OH–] = 3.5 × 10–4 M
• Check assumption 3.5 × 10–4 < 0.075
• pOH = –log (3.5 × 10–4) = 3.46
• pH = 14.00 – pOH
• = 14.00 – 3.46 = 10.54
• Notice if c >> Kb,
• Then [base]equilibrium  [base]initial
• Also if c >> Ka
• Then [HA]equilibrium  [HA]initial
27
Your Turn!
Calculate the pH for a solution of 0.025 M pyridine
(py). Kb = 1.7  10-9
py + H2O pyH+ + OH–
A. 5.23
épyH+ ùéOH- ù
B. 8.77 ë ûë û x2
K b = 1.7 ´ 10 =
-9
=
C. 8.81 é ù 0.025 - x
ëpy û
D. 5.19 Assume x is small
x2
-9
1.7 ´ 10 = x 2 = 4.25 ´ 10-11
0.025
x = 6.52 ´ 10-6 pOH = –log (6.52 ´ 10-6 ) = 5.19
pH=14.00 - pOH = 14.00 - 5.19 = 8.81
28
Equilibrium Calculations when
Simplifications Fail
Weak acid, HA, ionizes in water to give ions
HA(aq) + H2O A–(aq) + H3O+(aq)

[A ][H ] - +
Ka =
[HA]
[HA]equilibrium = [HA]initial – x

where x = amount dissociated to ions = [A–] = [H+]

• For the solutions we have looked at so far
• [HA]equilibrium  [HA]initial  c
29
• Simplifications work when
[HA]initial ≥ 400 x Ka

• Simplifications fail when

[HA]initial ≤ 400 x Ka

must solve with Quadratic equation

30
The Quadratic Equation
• For a quadratic equation in the form
ax + bx + c = 0
2

• The values of x that satisfy this equation are

-b ± b 2 - 4ac
x=
2a
• Take only the positive root for the answer
• Negative [HA] is meaningless
• Always gives you the correct answer
31
Learning Check
What is the pH of a 0.15 M solution of dichloro acetic
acid, HC2HCO2Cl2, in water? For dichloroacetic acid,
Ka = 5.0 × 10–2.
HC2HCO2Cl2(aq) + H2O C2HCO2Cl2–(aq) + H3O+(aq)

[C 2HCO2Cl2− ][H + ]
Ka = = 0.050
[HC 2HCO2Cl2 ]

[HC2HCO2Cl2 ] (M) [C2HCO2Cl2–] (M) [H3O+] (M)

I 0.15 0 0
C –x +x +x
E 0.15 – x x x 32
• Substituting equilibrium concentrations into equilibrium
law gives:
(x )(x )
= 0.050
0.15 − x
• Can we neglect x in denominator?
[HA]initial 0.15
= = 3.0
Ka 0.050
• Clearly not > 400!
• Can’t neglect x so multiply both sides by
(0.15 – x) to clear fractions

33
x = (0.15 - x )(0.050) = (0.15 ´ 0.050) - 0.050x
2

• Or in terms of general quadratic equation

ax 2 + bx + c = 0
x 2 + 0.050 x − 7.5  10 −3 = 0
• Where a = 1, b = 0.050, and c = –7.5 ×10–3
• Now put into quadratic formula
2
− b  b − 4ac
x =
2a
− 0.050  (0.050)2 − 4(1)( −7.5  10 −3 )
x =
2(1)
The two roots are: x = 0.065 M and x = – 0.115 M 34
Since only positive root has physical meaning, we
use this answer

• [H+] = x = 0.065 M

• [C2HCO2Cl2–] = x = 0.065 M

• [HC2HCO2Cl2] = 0.15 – 0.065 = 0.085 M

• pH = –log(0.065) = 1.19
35
Next Session

36
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration

37
Acid-Base Properties of Salt Solution
• Salt is formed by neutralization of an acid by a base.
• HCl + NaOH gives NaCl and H2O
• The pH of salt is not always neutral
• Salts that contain the conjugate acids of weak bases
produce acidic aqueous solution;
• Salts that contain the conjugate bases of weak acids
produce basic aqueous solution.
Note:
• all group 1 and 2 metals (Ex. Li+, Ca2+) and all metal cations
with charge +1 (Ex.Ag+) are neutral.
• Conjugate base from strong acid (HCl, HBr, HI, HClO4, HClO3,
H2SO4, HNO3) is really weak base or almost neutral.
38
How to predict acidic/basic
properties of salts ??
1. Write chemical equation of salt in water
2. Write the equilibrium equation of its cation or anion
Example:
NH4Cl is acid or base?
Answer:
Remember:
1. NH4Cl (salt) → NH4+ + Cl- Cl- + H2O → no reaction
neutral

2. NH4+ + H2O ⇌ NH3 + H3O+

Acidic

Thus, NH4Cl has acidic property. Later we can check its39pH.

Another way to check
acidic/basic properties of salts
• NH4Cl

• NH4+ Is NH4+ a conjugate acid of a weak base?

Is NH3 a weak base?

• Cl-

40
NH3 is weak base

41
42
• NH4Cl

• NH4+ Is NH4+ a conjugate acid of a weak base? YES

Is NH3 a weak base? YES
Acidic

• Cl- Is Cl- a conjugate base of a weak acid? NO

Is HCl a weak acid? NO
Neutral

So overall Acidic 43
Your Turn
• Predict whether the pH is acidic, basic, or neutral
for a solution of NaCH3CO2 ?
Ka of HCH3CO2 = 1.76 x 10-5
Answer:
• NaCH3CO2 → Na+ + CH3CO2−
neutral
• CH3CO2− + H2O ⇌ HCH3CO2 + OH−
Basic
Thus, NaCH3CO2 has basic property.

44
Or you can use another way
• Predict whether the pH is acidic, basic, or neutral
for a solution of NaCH3CO2 ?
Ka of HCH3CO2 = 1.76 x 10-5
Answer:
• Na+ Is Na+ a conjugate acid of a weak base? NO
Neutral

• CH3CO2- Is CH3CO2- a conjugate base of a weak acid?

Is HCH3CO2 a weak acid? YES YES
Basic
So overall Basic 45
General Rule for Compound XY
• X+ Is X+ a conjugate acid of weak base?
If yes, then acidic;
If No, neutral

• Y- Is Y- a conjugate base of weak acid?

If yes, then basic;
If No, neutral

• Overall: Acidic + Neutral = Acidic

Basic + Neutral = Basic
Neutral + Neutral = Neutral 46
Calculate pH of salt
solution
• Important = check what we have in solutions
example:
Calculate pH of 0,1 M NaCH3CO2 ?
Ka of HCH3CO2 = 1.76 x 10-5
Answer:
NaCH3CO2 → Na+ + CH3CO2-
0.1 M 0.1 M
CH3CO2- + H2O ⇌ HCH3CO2 + OH- Kb = Kw/Ka
I 0.1 - 0 0
C -x +x +x
E 0.1-x ≈ 0.1 x x 47
Calculate pH of salt
solution
• CH3CO2- + H2O ⇌ HCH3CO2 + OH- Kb = Kw/Ka
I 0.1 - 0 0
C -x +x +x
E 0.1-x ≈ 0.1 x x

𝑥2
Kb = = 5,68 x 10-10
0,1
x = 7.54 x 10-6
x = [OH-]
pOH = - log [OH-] =6 – log 7.54 = 5,12
pH = 14 – pOH = 8.88 (Basic)
48
Your Turn !
What is the pH of a 1.00 molar solution of NaCN(aq)?
The Ka for HCN = 6.2 × 10-10.

a. 2.40
b. 4.61
c. 9.40
d. 11.60
e. 13.00

49
Buffers
• A buffer solution is any solution that maintains an
approximately constant pH despite small additions
of acid and base.
• An acid buffer: consists of a weak acid and its
conjugate base supplied as a salt. It buffers on the
acidic side of neutral
• An basic buffer: consists of a weak base and its
conjugate acid supplied as a salt. It buffers on the
basic side of neutral.

50
Acid Buffer Example
• Mix acetic acid with an acetate salt and get dynamic
equilibrium:
• CH3CO2H (aq) + H2O (l) ⇌ H3O+ (aq) + CH3CO2- (aq)
• What happens if strong acid is added to a solution
containing approximately equal amounts of CH3CO2H
and CH3CO2- ?
back reaction

• The added H3O+ ions are effectively removed and the pH

stays constant.

51
Acid Buffer Example
• Mix acetic acid with an acetate salt and get dynamic
equilibrium:
• CH3CO2H (aq) + H2O (l) ⇌ H3O+ (aq) + CH3CO2- (aq)

• What happens if strong base such as OH- is

added?
• OH- removes a proton from CH3CO2H to form H2O
and CH3CO2-
• The added OH- ions are effectively removed and the
pH stays constant.

52
Acid Buffer Action
• The weak acid, HA, transfers protons to OH- ions
supplied by strong base.
• The conjugate base, A-, of the weak acid accepts
protons from the H3O+ ions supplied by a strong
acid.
• A strong acid and the salt of its conjugate base
don’t make a good buffer. Why?
• Strong acids goes to completion
Drives to right

53
Base Buffer Example
• NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)

• When strong acid is added, NH3 accepts protons

from incoming acid to make NH4+.

• When strong base is added, NH4+ donates a proton

to form NH3 and H2O. pH remains the same.

54
Base Buffer Action
• The weak base, B, accepts protons supplied by
strong acid.
• The conjugate acid, BH+, of the weak base
transfers protons to the OH- ions supplied by a
strong base

• A buffer is a mixture of weak conjugate acids

and bases that stabilize the pH of a solution
by providing a source or sink for protons.

55
How to Calculate pH of
Buffer solutions?
• Important :
1. Write the equilibrium equation on the system
2. Table of ICE (analyze what we have in initial
condition)
3. Get [H3O+] or [OH-] to calculate pH.

56
Learning Check
A buffered solution contains initial concentrations of
0.55 M acetic acid (CH3COOH, Ka = 1.8 × 10–5) and
0.45 M sodium acetate (CH3COONa). Calculate the pH
of this solution.
CH3COOH(aq) ⇌ CH3COO–(aq) + H+(aq)

− +
[C 2H3 O 2 ][H ]
Ka = = 1.8 × 10–5
[HC 2H3 O 2 ]

57
 Concentra- [HC2H3O2H] (M ) [C2H3O2–] (M ) [H+] (M )
tion (M)
Starting 0.55 0.45 0
Change –x +x +x
Equilibrium 0.55 – x  0.55 0.45+x  0.45 x

▪ Because Iniatial concentration ≥ 400 x Ka, x can

be neglected.
▪ Substitute equilibrium concentrations into equilibrium
law
(x )(0.45)
= 1.8  10 −5
0.55 58
• Solving for x gives

−5
(1.8  10 )(0.55) −5
x = = 2.2  10 M
0.45

• x = [H+] = 2.2 × 10–5

• 2.2 × 10–5 is much smaller than either 0.45 or 0.55 so

the assumption holds

• pH = –log(2.2 × 10–5) = 4.66

59
Your Turn!
Determine the pH of a buffer solution containing
0.250 M benzoic acid and 0.600 M sodium benzoate.
Ka for benzoic acid is 6.3 × 10–5

A. 10.18
B. 6.60
C. 3.82
D. 4.58

60
Learning Check
A student has available 1.00 L of the buffered
solution: 0.55 M acetic acid (CH3COOH, Ka = 1.8 ×
10–5) and 0.45 M sodium acetate (NaCH3COO).
What is the pH of this buffer after 0.060 mol of
OH– are generated by the reaction?

Answer:
Step 1. Calculate pH of buffer
•Before OH– is added the pH of the buffer is 4.66 or
• [H+] = 2.2 × 10–5 M

61
Learning Check (Cont.)
Step 2: Calculate moles of HA and A– from reaction
CH3COOH(aq) + OH–(aq) CH3COO–(aq) + H2O(aq)

[CH3COOH] OH–(aq) CH3COO–(aq)

mol mol mol
Initial 0.55 mol 0.060 mol 0.45
Change –0.060 –0.060 +0.060
Equilibrium = 0.49 0.00 = 0.51

▪ Now use these new concentrations to calculate the pH

using a new ICE table
Step 3: Calculate new pH
CH3COOH(aq) CH3COO–(aq) + H+(aq)
−
[C 2H3O2 ][H+ ] −5
Ka = = 1.8  10
[HC2H3O2 ]

[CH3COOH] [CH3COO–] [H+]

mol mol mol
I 0.49 0.51 ~0
C –x +x x
E 0.49 – x 0.51 + x x
≈ 0.49 ≈ 0.51
63
• Substitute equilibrium concentrations into equilibrium
law +
[H ](0.51)
= 1.8  10 − 5
0.49
• Solving for [H+] gives
−5
+ (1.8  10 )(0.49)
[H ] = = 1.73  10 − 5
0.51
• pH = –log(1.73 × 10–5) = 4.76

• Or pH has changed by only

• pH = 4.76 – 4.66 = 0.10 unit

Designing a Buffer
• One must consider the relationship between the
ratio of [HA] to [A-], the pKa, and the desired pH

𝐴− [𝐻3 𝑂+ ]
• HA (aq) + H2O (l) ⇌ H3O+ (aq) + A- (aq) 𝐾𝑎 =
[𝐻𝐴]
[𝐻𝐴]
• Rearrange: +
𝐻3 𝑂 = 𝐾𝑎 𝑥 −
𝐴
• Take logarithms of both sides:
[𝐻𝐴]
𝐿𝑜𝑔 𝐻3 𝑂+ = 𝐿𝑜𝑔 𝐾𝑎 + 𝐿𝑜𝑔 −
𝐴

65
 𝐴− [𝐻 𝑂 + ]
3
• HA (aq) + H2O (l) ⇌ H3O+ (aq) + A- (aq) 𝐾𝑎 =
[𝐻𝐴]
[𝐻𝐴] rearrange
𝐻3 𝑂+ = 𝐾𝑎 𝑥 −
𝐴
take logarithms of both sides
[𝐻𝐴]
𝐿𝑜𝑔 𝐻3 𝑂+ = 𝐿𝑜𝑔 𝐾𝑎 + 𝐿𝑜𝑔 −
𝐴
Multiply by minus (-)
[𝐻𝐴]
−𝐿𝑜𝑔 𝐻3 𝑂+ = −𝐿𝑜𝑔 𝐾𝑎 − 𝐿𝑜𝑔 −
𝐴

[𝐻𝐴]
𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 −
𝐴 Equilibrium concentration
66
• The values of [HA] and [A-] in the equation are at
equilibrium.

• A weak acid HA typically loses only a tiny fraction of

its protons.
• A weak base A- typically accepts only a tiny fraction
of protons.

• So initial concentration ≌ equilibrium concentration

67
 [𝐻𝐴]
𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 −
𝐴 Equilibrium concentration

𝐻𝐴 𝑜
𝑝𝐻 ≌ 𝑝𝐾𝑎 − 𝐿𝑜𝑔 − Initial concentration
𝐴 𝑜

Handerson-Hasselbalch Equation
[A - ] [BH+ ]
pH = pK a + log or pOH = pK b + log
[HA] [B ]
Note: This assumption is valid when [H3O+] is small compared to [HA] and [A-]
(i.e. less than 5% or initial conc. ≧ 400 Ka) 68
Example: Design a buffer
system with pH 4.60
• A buffer solution is most effective in the
range of pKa ± 1
Ionization Constants of Acids at 25 𝑜 𝐶
Acid HA 𝑨− 𝑲𝒂 𝒑𝑲𝒂
Benzoic 𝐶6 𝐻5 𝐶𝑂𝑂𝐻 𝐶6 𝐻5 𝐶𝑂𝑂 − 6.46 𝑥 10−5 4.19
Oxalic 𝐻𝐶2 𝑂4 − 𝐶2 𝑂4 2− 6.4 𝑥 10−5 4.19
Hydrazoic 𝐻𝑁3 𝑁3 − 1.9 𝑥 10−5 4.72
Acetic 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝐶𝐻3 𝐶𝑂𝑂− 1.76 𝑥 10−5 4.75
Propionic 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻− 1.34 𝑥 10−5 4.87
Pyridinium Ion 𝐻𝐶5 𝐻5 𝑁 + 𝐶5 𝐻5 𝑁 5.6 𝑥 10−5 5.25

Easy buffer to get your hands on

69
Example: Design a buffer
system with pH 4.60
• Acetic acid is suitable with a pKa of 4.75.
𝐻𝐴 𝑜
𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 −
𝐴 𝑜
𝐻𝐴 𝑜
𝐿𝑜𝑔 − = 𝑝𝐾𝑎 − 𝑝𝐻 = 4.75 − 4.60 = 0.15
𝐴 𝑜
The ratio is more important than the amounts
𝐻𝐴 𝑜 0.15
used.
−
= 10 = 1.4
𝐴 𝑜 However, the amounts used do affect the
capacity of the buffer to resist changes in pH.

Higher concentrations = more resistance to

change 70
Your Turn!
Blood plasma has a pH of 7.40. If we assume that
the buffer system is HCO3-/H2CO3 what ratios of base
and acid must it have. (Ka 𝐻2 𝐶𝑂3 = 4.2𝑥10−7 )

A. 1.02
B. 10.05
C. 6.38
D. Not enough information

71
Your Turn! - Solution
K a = 4.2 x 10-7
pK a = -log(4.2 x 10-7 ) = 6.38
éHCO- ù
ë 3û
pH = 6.38 + log
éH CO ù
ë 2 3û
éHCO- ù
ë 3û
7.40=6.38 + log
éH CO ù
ë 2 3û
éHCO- ù éHCO- ù
ë 3û ë 3û
log = 1.02 = 101.02 = 1.05x 101
éH CO ù éH CO ù
ë 2 3û ë 2 3û
72
Calculate pH of Buffer
(Homework)
Calculate the pH of a buffer solution that is 0.040 M
NH4Cl(aq) and 0.030 M NH3(aq).
Step 1: Equilibrium:
NH4+(aq) + H2O(l ) NH3(aq) + H3O+(aq)

+
[NH3 ][H ] −10
Ka = = 5.6  10
[NH+4 ]
pKa = –log(5.6 × 10–10) = 9.25

73
• Step 2: Calculate pH
[HA]initial [A - ]
[H ] = K a
+
or pH = pK a + log
[A ]initial
-
[HA]

[NH3 ] 0.030 M
pH = pK a + log = 9.25 + log
+
[NH4 ] 0.040 M

pH = 9.25 + log(0.75) = 9.13

74
For bases use Kb and equilibria to calculate [OH–], pOH,
and finally pH
NH3(aq) + H2O NH4+(aq) + OH–(aq)
+ −
[NH4 ][OH ]
Kb = = 1.8  10 −5
[NH3 ]
pKb = –log(1.8 × 10–5) = 4.74

Solving for [OH–] gives

- K b [NH3 ]
1.8 ´ 10 -5
´ 0.030 M -5
[OH ] = = = 1.35 ´ 10
+
[NH4 ] 0.040M
75
Calculate pOH
pOH = –log(1.35 × 10–5) = 4.87

Calculate pH
pH = 14.00 − 4.87 = 9.13

76
Calculate pH of Buffer (Homework)
Can 1.00 L of this buffer system deal with the addition
of 0.010 mol of H+? What is the final pH in this case?
NH3(aq) + H2O NH4+(aq) + OH–(aq)

+ −
[NH4 ][OH ]
Kb = = 1.8  10 −5
[NH3 ]

Moles [NH3] (mol) [NH4+] (mol) [HO–] (mol)

Before 0.030 0.040 ~0
Reaction –0.010
+0.010 x
(from H+)
After 0.030 – 0.010 0.040 + 0.010
x 77
= 0.020 = 0.050
• Now insert concentrations into Kb equation and solve
for [OH–]
- K b [NH3 ]
1.8 ´ 10 -5
´ 0.020 M -6
[OH ] = = = 7.2 ´ 10
[NH+4 ] 0.050 M
• pOH = –log(7.2 × 10−6) = 5.14
• pH = 14.00 – 5.14 = 8.86
•  pH = 8.86 – 9.13 = – 0.27 pH units

• If we added this 0.010 mol of H+ to 1.00 L of pure water,

the pH would be…
• pH = –log(0.010) = 2.00
• and  pH = 2.00 – 7.00 = –5.00 pH units
78
Polyprotic Acids
• Up until now, monoprotic acids
• Donate only one H+
• Polyprotic acids
• Donate more than one H+
• Many Polyprotic acids occur in nature
• Ascorbic acid (vitamin C) H2C6H6O6
• Oxalic acid (rhubarb) H2C2O4
• Citric acid (citrus fruit) H3C6H5O7
• Malic acid (apples) H2C4H4O5
• Tartaric acid (grapes) H2C4H4O6

79
Polyprotic Acids
• Some inorganic polyprotic acids:
• Phosphoric acid H3PO4
• Carbonic acid H2CO3
• Sulfuric acid H2SO4
• Sulfurous acid H2SO3
• These acids undergo ionization in steps
K a1
• H3PO4(aq) + H2O H3O+(aq) + H2PO4–(aq)
• H2PO4–(aq) + H2O H3O+(aq) + HPO42–(aq) K a2
• HPO42–(aq) + H2O H3O+(aq) + PO43–(aq) K a3

80
Polyprotic Acids
• Or in simpler terms
H3PO4(aq) H+(aq) + H2PO4–(aq)
[H+ ][H2PO −4 ]
K a1= = 7.5  10 − 3
[H3PO 4 ]

H2PO4–(aq) H+(aq) + HPO42–(aq)

[H+ ][HPO24− ]
K a2= = 6.2  10 − 8
[H2PO −4 ]

HPO42–(aq) H+(aq) + PO43–(aq)

[H+ ][HPO34− ]
K a3= = 3.6  10 −13
[HPO24− ]
81
Next Session

82
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration

83
Acid Base Titration
• An acid base titration is the addition of a volume of
base of known concentration to acid of unknown
concentration (or addition of acid to base).

• Tis technique can be used to determine the

concentration of an acid or base

84
Titration Curve
Equivalence point or
stoichiometric point
or end point
Equivalence (stoichiometric, s) point:
the theoretical volume at which the amount
of base added equals the amount of acid that
was originally present

End point:
the experimentally measured volume at which
the indicator changes color.

Endpoint should equal equivalence point.

85
Titration Curve
Equivalence point or
stoichiometric point
or end point
Before At After
Endpoint Endpoint Endpoint
buret

titrant

analyte

86
Figures by MIT OpenCourseWare
Titration Curve

Figures by MIT OpenCourseWare

87
Figures by MIT OpenCourseWare
Titration of Strong Acid with
Strong Base
A 50.00 mL sample of 0.100 M HCl is titrated with
0.200 M NaOH using phenol red as the indicator (pH
range 6.4 – 8.2)

1. Before titration begins = initial pH

• Determined by initial concentration of acid in flask
• [H+] = 0.100 M

• pH = – log[H+] = – log(0.100) = 1.00

• Initial pH is low

88
 H+(aq) + OH–(aq) → H2O(aq)
2. During titration: before equivalence
• 50.00 mL of 0.100 M HCl
• 10.00 mL of 0.200 M NaOH added
H+(aq) mmol OH–(aq) mmol
Before 50.0 mL  0.100 M = 10.0 mL  0.200 M =
5.00 mmol 2.00 mmol
Rxn –2.00 mmol –2.00 mmol
After = 3.00 mmol = 0.00 mmol
3.00 mmol
+
[H ] = = 0.0500 M
(50.00 + 10.00) mL
pH = – log(0.0500) = 1.30 89
3. At Equivalence Point
• 50.00 mL of 0.100 M HCl
• 25.00 mL of 0.200 M NaOH added
H+(aq) + OH–(aq) → H2O(aq)
H+(aq) mmol OH–(aq) mmol
Before 50.0 mL  0.100 M 25.0 mL  0.200 M
= 5.00 mmol = 5.00 mmol
Rxn –5.00 mmol –5.00 mmol
After = 0.00 mmol = 0.00 mmol

• All acid neutralized

• What pH?
90
3. At equivalence point
• What species are present?
• Na+, Cl–, and H2O

• What is pH?
• Na+ has no acid or base properties
• Cl– is anion of strong acid, so very weak base
• Neither Na+ nor Cl– affect pH
• So solution is neutral
• pH = 7.00
• True for equivalence point of all strong acids reacting
with strong bases
91
4. After equivalence point
• 50.00 mL of 0.100 M HCl
• 50.00 mL of 0.200 M NaOH added (Now OH– is in
excess)
H+(aq) + OH–(aq) → H2O(aq)

H+(aq) mmol OH–(aq) mmol

Before 50.0 mL  0.100 M 50.0 mL  0.200 M
= 5.00 mmol = 10.00 mmol
Rxn –5.00 mmol –5.00 mmol
After = 0.00 mmol = 5.00 mmol
92
4. After titration: after equivalence
• 50 mL of 0.200 M NaOH added
• First calculate pOH
- mmol OH- excess 5.00 mmol
[OH ] = =
volume of solution (mL) (50.0 + 50.0) mL
5.00 mmol
[OH ] =-
= 0.0500 M
100.0 mL
pOH = – log 0.0500 = 1.301
Next use Kw to determine pH and/or [H+]
pH = pKw – pOH = 14.00 – 1.301 = 12.70
[H+] = 10–12.70 = 2.0  10–13 M 93
Titration Curve of Strong Acid with
Strong Base

Steep

94
Titration of Weak Acid with
Strong Base

V>Veq Strong base in water

V=Veq A- A- A- A-

H H
V=V half eq
A A A- A-

H H H
0<V<Veq A A A A-

H H H H
V=0 A A A A
95
Titration of Weak Base
with Strong Acid

96
 Titration: Weak Acid with Strong
Base
A 25.00 mL sample of 0.200 M acetic acid (CH3COOH) is
titrated with 0.200 M NaOH.

Ka(CH3COOH) = 1.8  10–5

1. Before titration begins

CH3COOH → CH3COO– + H+
[CH3COOH] (M) [CH3COO–] (M) [H3O+] (M)
I 0.200 M 0 0
C –x +x +x
E 0.20 – x  0.20 x x
97
• Initial pH

[CH3COO− ][H+ ] (x )(x )

Ka = = = 1.8  10 −5
[CH3COOH] 0.200

(
x = 0.20 ´ 1.8 ´ 10
2 -5
)
x = [HA]i ´ K = 3.6 ´10 = 1.9 ´10
-6 -3

pH = –log 1.9 × 10–3 = 2.72

98
2. During titration: before equivalence (buffer problem)
• 25.00 mL of 0.200 M acetic acid
• 10 mL of 0.200 M NaOH added
OH– + CH3COOH → CH3COO– + H2O

CH3COOH OH– CH3COO–

Before 25.0 mL  10.0 mL  0
0.200 M = 0.200 M =
5.00 mmol 2.00 mmol
Rxn –2.00 mmol –2.00 mmol +2.00 mmol
After = 3.00 mmol = 0.00 mmol = 2.00 mmol
99
2. During titration: before equivalence

[CH3COOH] → [CH3COO–] + [H3O+]

I 3.00mmol/35.0mL 2.00mmol/35.0mL 0
C –x +x +x
E ≈3.00mmol/35.0mL ≈2.00mmol/35.0mL x

+
æ 2.00 mmol ö
[H ] çç ÷÷
[H + ][CH 3 COO − ] -5 è 35.00 mL ø
Ka = 1.8 ´ 10 =
[CH 3 COOH] æ 3.00 mmol ö
çç ÷÷
è 35.00 mL ø

( 3.00 mmol)
+
(
[H ] = 1.8 ´ 10 -5
) ´ (2.00 mmol) = 2.7 ´ 10 -5
M

100
2b. During titration: halfway to equivalence
• 25.00 mL of 0.200 M acetic acid
• 12.5 mL of 0.200 M NaOH added

OH– + CH3COOH → CH3COO– + H2O

CH3COOH + OH– → CH3COO–

Before 25.0 mL  12.5 mL  0
0.200 M = 0.200 M =
5.00 mmol 2.50 mmol
Rxn –2.50 mmol –2.50 mmol +2.50 mmol
After = 2.50 mmol = 0.00 mmol = 2.50 mmol

101
2b. During titration: halfway to equivalence
• 25.00 mL of 0.200 M acetic acid
• 12.5 mL of 0.200 M NaOH added

Ka =
+
[H ][CH3COO ] -
-5
= 1.8 ´ 10 =
( )
[H+ ] 2.50 mmol
[CH3COOH] 2.50 mmol

+ −5
[H ] = K a = 1.8  10

( )
pH = pK a = − log 1.8  10 −5 = 4.74

▪ True for any weak acid with strong base

▪ pH = pKa halfway to equivalence

102
3. At equivalence point—Stoichiometry
• 25.00 mL of 0.200 M acetic acid
• 25.00 mL of 0.200 M NaOH added
•
OH– + CH3COOH → CH3COO– + H2O

CH3COOH + OH– → CH3COO–

Before 25.00 mL  25.0 mL  0.00 mmol
0.200 M = 0.200 M =
5.00 mmol 5.00 mmol
Rxn –5.00 mmol –5.00 mmol + 5.00 mmol
After = 0.00 mmol = 0.00 mmol = 5.00 mmol

103
3. At equivalence point—Dilution Factor
• 25.00 mL of 0.200 M acetic acid
• 25 mL of 0.200 M NaOH added

• Total volume = 25.00 + 25.00 = 50.00 mL

Concentrations after reaction

mmol CH3COOH remaining 0.00 mmol

[CH3COOH] = = =0.00M
total solution Volume (mL) 50.00 mL
0.00 mmol
-
[OH ] = =0.00 M
50.0 mL
mmol CH3COO – formed 5.00 mmol
[CH3COO- ] = = =0.100 M
total Volume (mL) 50.00 mL
104
3. At the equivalence point—Weak Base
CH3COO– + H2O CH3COOH + OH–

[CH3 COOH][OH- ] Kw 1.0 ´ 10-14

Kb = = = = 5.6 ´ 10-10
[CH3COO- ] Ka 1.8 ´ 10-5

[CH3COO–] M [CH3COOH] M [OH–] M

I 0.100 M 0 0
C –x +x +x
E 0.100 – x  0.100 x x

[CH3 COOH][OH− ] x2
Kb = = 5.6  10 −10 =
[CH3COO− ] 0.100 105
3. At the equivalence point
CH3COO– + H2O CH3COOH + OH–

( )
x 2 = (0.100)  5.6  10 −10 = 5.6  10 −11

x = 5.6  10 −11 = 7.5  10 − 6 M

( −6
)
pOH = − log 7.6  10 M = 5.12
pH = pK w − pH = 14.00 − 5.12 = 8.88
So at the equivalence point, pH is determined by
the conjugate base equilibrium

106
4. After equivalence point—Stoichiometry

• 25.00 mL of 0.200 M acetic acid

• 35.00 mL of 0.200 M NaOH added

OH– + CH3COOH → CH3COO– + H2O

CH3COOH + OH– → CH3COO–

Before 5.00 mmol 7.00 mmol 0.00 mmol
Rxn –5.00 mmol –5.00 mmol + 5.00 mmol
After = 0.00 mmol = 2.00 mmol = 5.00 mmol

107
4. After equivalence point—Excess Base

• 25 mL of 0.200 M CH3COOH
• 35 mL of 0.200 M NaOH

• Excess mmol of OH– = 2.00 mmol

2.00 mmol
-
[OH ] = =0.0333 M
60.00 mL
pOH = − log(0.0333 ) = 1.48

pH = pK w − pH = 14.00 − 1.48 = 12.52

108
Your Turn!
What is the change in pH when 10.0 mL of 0.100 M
NaOH is added to 50.0 mL of 0.250 M acetic acid?
The acid ionization constant for acetic acid is 1.8 ×
10–5. The initial pH of the acetic acid is 2.67.
A. –1.01
B. 3.13
C. 1.01
D. –3.13

109
Your Turn! - Solution
• First, determine the initial mmoles of acid and base:

10.0 mL NaOH × 0.100 M = 1.00 mmol NaOH

50.0 mL CH3COOH × 0.250 M = 12.5 mmol CH3COOH

• mmol of acid remaining after addition of base:

12.5 mmol – 1.00 mmol = 11.5 mmol

• mmol of acetate ion produced:

1.00 mmol
110
Your Turn! - Solution cont.
pK a = 4.74
éCH COO- ùéH O+ ù
ë 5 ûë 3 û
pH = 4.74 + log
éCH COOHù
ë 3 û
Since you have a ratio you do not
need to calculate the molarity of the solution
é 1.0 mmol ù
= 4.74 + log ê ú = 3.68
ë11.5 mmol û
DpH = 3.68 – 2.67 = +1.01

111
Your Turn!
A 10.0 mL solution of 0.300 M NH3 is titrated with
0.100 M HCl. Calculate the pH after the addition of
10.0 mL of acid.
A. 9.55
B. 9.25
C. 8.95
D. 9.73
E. 8.77

112
Your Turn! - Solution
• First, determine the initial mmoles of acid and base:

10.0 mL NH3 × 0.300 M = 3.00 mmol NH3

10.0 mL HCl × 0.10 M = 1.0 mmol HCl

• mmol of base remaining after addition of base:

3.0 mmol – 1.00 mmol = 2.0 mmol

• mmol of ammonium ion produced:

1.00 mmol
113
Your Turn! - Solution cont.
pK a = 9.25
éNH ù
ë 3û
pH = 9.25 + log
éNH+ ù
ë 4û
Since you have a ratio you do not
need to calculate the molarity of the solution
é 2.0 mmol ù
= 9.25 + log ê ú = 9.55
ë 2.0 mmol û

114
Homework
• The titration of 25.00 mL of 0.100 M CH3CO2H with
0.100 M NaOH. Ka = 1.8 × 10−5 for CH3CO2H.

a) What is the initial pH before any amount of the NaOH

solution has been added?
b) Find the pH after 25.00 mL of the NaOH solution have
been added.
c) Find the pH after 12.50 mL of the NaOH solution has been
added.
d) Find the pH after 37.50 mL of the NaOH solution has been
added.

115