Lecture 10

ACID-BASE EQUILIBRIA
SOLUBILITY & COMPLEX-ION
EQUILIBRIA

1
 Contents

I-1The Arrhenius Theory: A Brief Review

I-2 Brønsted-Lowry Theory of Acids and Bases
I-3 The Self-Ionization of Water and the pH Scale
I-4 Strong Acids and Strong Bases
I-5 Weak Acids and Weak Bases
I-6 Polyprotic Acids
I-7 Ions as Acids and Bases
I-8 Molecular Structure and Acid-Base Behaviour

2
 Introduction

Gastric acid is a digestive fluid, formed

in the stomach. It is composed of
Citric acid hydrochloric acid (HCl) 0.05–0.1 M
(roughly 5,000–10,000 parts per
million), potassium chloride (KCl) and
3
sodium chloride (NaCl).
 I. 1 The Arrhenius Theory: A Brief Review

• Acids: substances that ionize in water to produce H+ ions*

– Acids have sour taste (i.e., acetic acid in vinegar
(CH3COOH and citric acid in lemons)
– React with certain metals (i.e., Zn, Mg, an Fe to produce
H2 (g))
– React with carbonates and bicarbonates (i.e., Na2CO3,
CaCO3, and NaHCO3) to produce CO2(g)

• Bases: are substances that ionize in water to produce OH-

– Have a bitter taste
– Feel slippery (i.e. soaps)
– Aqueous base solutions conduct electricity 4
 I. 1 The Arrhenius Theory: A Brief Review

H2O

HCl(g) → H+(aq) + Cl-(aq)

H2O
NaOH(s) → Na+(aq) + OH-(aq)

Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) → H2O(l) + Na+(aq) + Cl-(aq)

H+(aq) + OH-(aq) → H2O(l)

Arrhenius theory did not handle non OH- bases such as
ammonia very well.

5
I. 1 The Arrhenius Theory: A Brief Review

 The Arrhenius theory does have

limitations.
 One of the most glaring is in its
treatment of the weak base ammonia.
 The Arrhenius theory suggests that all
bases contain OH-.
 Where is the OH- in NH3 ?

6
 I. 2 Brønsted-Lowry Theory of Acids and Bases

• An acid is a proton donor.

• A base is a proton acceptor.
Conjugate base : formed by the removal of a proton from the acid
Conjugate acid : formed by the addition of a proton to the base.

The Solvated Proton

base acid
NH3 + H2O NH4+ + OH-

NH4+ + OH- NH3 + H2O

acid base ?? ??
 I. 2 Brønsted-Lowry Theory of Acids and Bases

Base Ionization Constant

conjugate conjugate
base acid acid base
NH3 + H2O NH4+ + OH-

[NH4+][OH-]
K c=
[NH3][H2O]

[NH4+][OH-]
Kb= Kc[H2O] = = 1.810-5
[NH3]
It is important to note that the stronger an acid, the weaker its
conjugate base 8
I. 2 Brønsted-Lowry Theory of Acids and Bases

Acid Ionization Constant

[CH3CO2-][H3O+]
Ka= Kc[H2O] = = 1.810-5
[CH3CO2H]

9
I. 2 Brønsted-Lowry Theory of Acids and Bases
 Example
Identifying Brønsted Lowry Acids and Bases and Their Conjugates

11
 I. 2 Brønsted-Lowry Theory of Acids and Bases

 To determine whether HClO4 or HCl is the stronger acid.

 Use a solvent that is a weaker base than water- a solvent that will
take protons from the stronger of the two acids more readily than
from the weaker one.
 In the solvent diethyl ether, (C2H5-O-C2H5), HClO4 is completely
ionized, but HCl is only partially ionized.
 HClO4 is a stronger acid than is HCl, and ClO4- is a weaker base than
Cl-.

12
I. 2 Brønsted-Lowry Theory of Acids and Bases

A Weak Base
13
I. 2 Brønsted-Lowry Theory of Acids and Bases

A Weak Acid

14
I. 2 Brønsted-Lowry Theory of Acids and Bases

A Strong Acid

15
 I. 3 The Self-Ionization of Water and the pH Scale

Express this autoionization of water in the Brønsted framework,

we write:

conjugate
conjugate
acid
base acid base
[H3O+][OH-]
H2O + H2O H3O+ + OH- Kc=
[H2O][H2O]
Kw+ is the- ion-product constant: which is the molar concentrations of
H & OH
KW= Kc[H2O][H2O] = [H3O+][OH-] = 1.010-14
16
I. 3 The Self-Ionization of Water and the pH Scale

pH and pOH
• The potential of the hydrogen ion was defined in 1909
as the negative of the logarithm of [H+].

pH = -log[H3O+] pOH = -log[OH-]

KW = [H3O+][OH-]= 1.010-14

-logKW = -log[H3O+]-log[OH-]= -log(1.010-14)

pKW = pH + pOH= -(-14)

pKW = pH + pOH = 14
17
I. 3 The Self-Ionization of Water and
the pH Scale

18
I.3 The Self-Ionization of Water and the pH Scale

19
I.4 Strong Acids and Bases

HCl CH3CO2H

Thymol Blue Indicator

pH < 1.2 < pH < 2.8 < pH

20
 Example
Calculating the pH of an Aqueous Solution of a Strong Base

21
 Example
Calculating the pH of an Aqueous Solution of a Strong Base

22
 Example
Example 2. What is the pH of a 0.020 M solution of
Ba(OH)2?
Example 3: Find the concentration of all species in solution
for a 0.45M solution of HNO3.

1. This is a strong base problem.

Ba(OH)2 (aq) → Ba2+(aq) + 2 OH‾(aq)

0.020 mol Ba(OH)2 2 mol OH -

x  0.040 M OH -  [OH-]
1 L soln 1 mol Ba(OH)2

pOH = - log[OH‾] = - log(0.040) = 1.40

pH = 14 – pOH = 14 – 1.40 = 12.60
23
 Example
This is a strong acid problem.

HNO3(aq) + H2O(l)  NO3‾(aq) + H3O+(aq)

[HNO3] = 0 M
[NO3‾] = [H3O+] = 0.45 M
[H2O] = 55.5 M
- 14
K 1.0 x 10
[OH-]  w

  2.2 x 10 - 14
M
[H3O ] 0.45

24
 I.5 Weak Acids and Weak Bases

[CH3CO2-][H3O+] [CH3NH3+][HO-]
Ka= = 1.810-5 Kb= = 4.310-4
[CH3CO2H] [CH3NH2]

pKa= -log(1.810-5) = 4.74 pKb= -log(4.210-4) = 3.37

25
I.5 Weak Acids and Weak Bases

26
 I.5 Weak Acids and Weak Bases

Metal Ions with Charge ≧2 Are Weak Acids

A proton can dissociate from M(H2O)wn+ to reduce
the positive charge on the metal complex.

27
 Example
Determining a Value of KA from the pH of a Solution of a
Weak Acid. Butyric acid, HC4H7O2 (or CH3CH2CH2CO2H) is
used to make compounds employed in artificial flavorings
and syrups. A 0.250 M aqueous solution of HC4H7O2 is
found to have a pH of 2.72. Determine KA for butyric acid.

28
 Solution
For HC4H7O2 KA is likely to be much larger than KW.
Therefore assume self-ionization of water is unimportant.

HC4H7O2 + H2O C4H7O2 + H3O+

Initial conc. 0.250 M 0 0

Changes -x M +x M +x M
Equilibrium (0.250-x) M xM xM
Concentration
[H3O+] [C4H7O2-] 1.910-3 · 1.910-3
Ka = =
[HC4H7O2] (0.250 – 1.910-3)

Ka= 1.510-5 Check assumption: Ka >> KW. 29

 Example
Percent Hydrolysis

30
Example

31
I.5 Weak Acids and Weak Bases

Percent Ionization HA + H2O H3O+ + A-

[H3O+] from HA
Degree of ionization =
[HA] originally
[H3O+] from HA
Percent ionization =  100%
[HA] originally

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

n n
Ka = H3O+ A- 1
n
HA V
32
 I.6 Polyprotic Acids

Phosphoric acid: A triprotic acid.

• Ka1 >> Ka2
• All H3O+ is formed in the first ionization step.
• H2PO4- essentially does not ionize further.
• Assume [H2PO4-] = [H3O+].
• [HPO42-]  Ka2 regardless of solution molarity.

H3PO4 + H2O H3O+ + H2PO4- Ka = 7.110-3

H2PO4- + H2O H3O+ + HPO42- Ka = 6.310-8

HPO42- + H2O H3O+ + PO43- Ka = 4.210-13

33
I.6 Polyprotic Acids

34
 I.6 Polyprotic Acids

Pyridoxal phosphate is the active form of vitamin B6 (pyridoxine or pyridoxal).

Pyridoxal 5'-phosphate (PLP) is a versatile catalyst, acting as a coenzyme in a
multitude of reactions, including decarboxylation, deamination and
transamination.
Vitamin B6 là một loại vitamin hòa tan
trong nước và là một phần của nhóm
vitamin B. Pyridoxal phosphat (PLP) là dạng
hoạt động và là tác nhân kép trong một số
phản ứng chuyển hóa axit amin. PLP cũng
cần thiết cho phản ứng lên men tạo glucose
từ glycogen. Pyridoxal phosphate

35
I.6 Polyprotic Acids

36
 Example
Calculating Ion Concentrations in a Polyprotic Acid
Solution. For a 3.0 M H3PO4 solution, calculate:
(a) [H3O+]; (b) [H2PO4-]; (c) [HPO42-] (d) [PO43-]

37
 Solution
H3PO4 + H2O H2PO4- + H3O+
Initial conc. 3.0 M 0 0
Changes -x M +x M +x M
Equilibrium (3.0-x) M xM xM
Concentration
[H3O+] [H2PO4-] x·x
Ka= = = 7.110-3
[H3PO4] (3.0 – x)

Assume that x << 3.0

x2 = (3.0)(7.110-3) x = 0.14 M

[H2PO4-] = [H3O+] = 0.14 M

38
 Solution
H2PO4- + H2O HPO42- + H3O+

Initial conc. 0.14 M 0 0.14 M

Changes -y M +y M +y M
Equilibrium (0.14 - y) M yM (0.14 +y) M
Concentration
[H3O+] [HPO42-] y · (0.14 + y)
Ka= = = 6.310-8
[H2PO4-] (0.14 - y)

y << 0.14 M y = [HPO42-] = 6.310-8

39
 Solution
HPO4- + H2O PO43- + H3O+

[H3O+] [HPO42-] (0.14)[PO43-] -13 M

Ka= = = 4.210
[H2PO4-] 6.310-8

[PO43-] = 1.910-19 M

40
 Problem
Problem 1: Find the concentration of all species in solution
for a 0.45M solution of HNO2.

Problem 2: What is the pH of a 0.35M solution of CH3NH2?

Problem 3: Find the concentration of all species in solution

for a 0.45M solution of KNO2.
41
 Solution
This is a weak acid problem. The Ka of HNO2 is 4.5 x 10-4.

HNO2(aq) + H2O(l)  NO2‾(aq) + H3O+(aq)

init 0.45 0 0
change -x +x +x
equil. 0.45 – x x x
Simplifies to: [NO2-][H3O ] (x)(x)
Ka    4.5 x 10 - 4
[HNO2] 0.45  x

x2 = 4.5 x 10-4(0.45) = 2.0 x 10-4

x  2.0 x 10 - 4  1.4 x 10 - 2 M  [H3O]  [NO2-]

[HNO2] = 0.45 – x = 0.45 – 1.4 x 10-2 = 0.44 M
Kw 1.0 x 10 - 14
[OH-]  
 -2
 7.1 x 10 - 13
M
[H3O ] 1.4 x 10 42
 Solution
This is also a hydrolysis problem. The K+ is a spectator because it is the weak
conjugate acid of a strong base. Nitrite ion will hydrolyze:
NO2‾(aq) + H2O(l)  HNO2(aq) + OH‾(aq)
init 0.45 0 0
change -x x x
equil 0.45 – x x x
Need to find Kb:
[HNO2][OH-] (x)(x) Kw 1.0 x 10 - 14
Kb  -   2.2 x 10 Kb 
- 11
  2.2 x 10 - 11
[NO2 ] 0.45  x Ka 4.5 x 10 - 4
Simplifies to: [HNO2][OH-] (x)(x)
Kb    2.2 x 10 - 11

[NO2-] 0.45
x- 2 = 2.2 x 10-11(0.45) = 1.0 x 10-11
x  1.0 x 10 - 11  3.2 x 10 - 6 M  [HNO2]  [OH ]

[NO2ˉ] = 0.45 – x = 0.45 – (3.2 x 10-6) = 0.45 M

[K+] = 0.45 M
[H2O] = 55.5 M 43
 Solution
This is a weak base problem. The Kb for CH3NH2 is found on Table 16.5
and has a value of 4.4 x 10-4.
CH3NH2 (aq) + H2O(l)  CH3NH3+ (aq) + OHˉ(aq)
init. 0.35 0 0
change -x x x
equil. 0.35 – x x x
[CH3NH3 ][OH-] (x)(x)
Kb    4.4 x 10 - 4
CH3NH2 0.35  x
[CH3NH3][OH-] (x)(x)
Kb    4.4 x 10 - 4 x2 = 4.4 x 10-4(0.35) = 1.5 x 10-4
CH3NH2 0.35
x  1.5 x 10  0.012 M  [CH3NH3]  [OH-]
-4

[CH3NH2] = 0.35 – x = 0.35 – 0.012 = 0.34 M

 Kw 1 x 10 - 14
[H3O ]  -   8.1 x 10 - 13
M [H2O] = 55.5 M
[OH ] 0.012 44
 I.7 Ions as Acids and Bases

CH3CO2- + H2O CH3CO2H + OH-

base acid
[NH3] [H3O+]
NH4+ + H2O NH3 + H3O+ Ka= +
=?
acid base [NH4 ]

[NH3] [H3O+] [OH-] KW 1.010-14 -10

Ka= = = = 5.610
[NH4+] [OH-] Kb 1.810-5
Ka Kb = Kw

45
I.7 Ions as Acids and Bases

Hydrolysis

• Water (hydro) causing cleavage (lysis) of a bond.

Na+ + H2O → Na+ + H2O No reaction

Cl- + H2O → Cl- + H2O No reaction

NH4+ + H2O → NH3 + H3O+ Hydrolysis

46
 I.8 Molecular Structure and Acid-Base Behavior

• Why is HCl a strong acid, but HF is a weak one?

• Why is CH3CO2H a stronger acid than
CH3CH2OH?

• There is a relationship between molecular

structure and acid strength.
• Bond dissociation energies are measured in the
gas phase and not in solution.

47
 I.8 Molecular Structure and Acid-Base Behavior

Strengths of Binary Acids

HI HBr HCl HF

Bond length 160.9 > 141.4 > 127.4 > 91.7 pm

Bond energy 297 < 368 < 431 < 569 kJ/mol

Acid strength 109 > 108 > 1.3106 >> 6.610-4

HF + H2O → [F-·····H3O+] F- + H3O+

ion pair free ions
H-bonding 48
 I.8 Molecular Structure and Acid-Base Behavior

 When comparing binary acids of elements

in the same row of the periodic table, acid
strength increases as the polarity of the
bond increases.
 When comparing binary acids of elements,
in the same group of the periodic table, acid
strength increases as the length of the
bond increases
49
 I.8 Molecular Structure and Acid-Base Behavior

Strengths of Oxoacids

• Factors promoting electron withdrawal from the

O-H bond to the oxygen atom:
– High electronegativity (EN) of the central atom.
– A large number of terminal O atoms in the molecule.

H-O-Cl H-O-Br
ENCl = 3.0 ENBr= 2.8
Ka = 2.910-8 Ka = 2.110-9

50
I.8 Molecular Structure and Acid-Base Behavior

O O

··
··
··
··
·· ·· ·· ··
H O S O H H O S O H
·· ·· ·· ·· ··
O
··
··
Ka 103 Ka =1.310-2
·· - ·· -
O O

··
··
··
··

·· 2+ ·· ·· + ··
H O S O H H O S O H
·· ·· ·· ·· ··
-
O
··
··

··
51
 I.8 Molecular Structure and Acid-Base Behavior
Strengths of Organic Acids
O

··
··
H H H
·· ··
H C C O H H C C O H
·· ··
H H H
acetic acid ethanol
Ka = 1.810-5 Ka =1.310-16

 The length of the carbon chain in a carboxylic acid has little effect on the
acid strength, as in a comparison of acetic acid and octanoic acid.
 Other atoms or groups of atoms substituted onto the carbon chain may
strongly affect acid strength 52
 I.8 Molecular Structure and Acid-Base Behavior

Strengths of Amines as Bases

 The fundamental factor affecting the strength of an
amine as a base concerns the ability of the lone pair of
electrons on the N atom to bind a proton taken from
an acid.

53
 I.8 Molecular Structure and Acid-Base Behavior

Strengths of Amines as Bases

 The withdrawal of electron charge density from the
group causes aniline to be a much weaker base than is
cyclohexylamine.

54
 I.9 Lewis Acids and Bases

 In 1923, G. N. Lewis proposed an acid-base theory

closely related to bonding and structure.
 The Lewis acid-base theory is not limited to reactions
involving H+ and OH-.
 It extends acid-base concepts to reactions in gases and
in solids.
 Important in describing certain reactions between
organic molecules.

 A Lewis acid is a species (an atom, ion, or molecule)

that is an electron-pair acceptor, and a Lewis base is a
species that is an electron-pair donor.
55
 I.9 Lewis Acids and Bases

The product of a Lewis acid –base reaction called an adduct

(or addition compound)

56
 Problem
According to the Lewis theory, each of the following is an
acid base reaction. Which species is the acid and which is
the base?

57
 Problem
Identify the Lewis acids and bases in these reactions

a
b
c
d

58
 Problem
a. From the following bases, select the one with the smallest Kb and
the one with the largest Kb and give reasons for your choices.

b. Predict which is the stronger acid, explain

(*) HClO2 or HClO3
(**) H2CO3 or HNO2
(***) H2SiO3 or H3PO4
c

59
Problem

60
 Problem
Estimate the pH of 0.15 M NH4Cl (aq). NH3: Kb = 1.8×10-5
[H3O+ ][NH3 ]
NH 4 + (aq)+H 2O(l) H3O+ (aq)+NH3 (aq) Ka 
[NH 4  ]
NH 4  H 3O  NH3
Initial 0.15 0 0
Change -x x x
Equilibrium 0.15 - x x x
Ka  Kw
Kb  1.01014
1.8105
=5.6  1010 

10 [H 3 O + ][NH 3 ]
5.6  10 = 
= 0.15- x 
x2 x2
0.15
[NH 4 ]
 x  0.15  5.6  1010  9.2  106
(less then 0.5% of 0.15, the approximation is valid)
[H 3 O  ]=x  9.2  10 6 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
 pH  log[9.2  106 ]  5.04 61
 Problem
Estimate the pH of 0.10 M methylammonium chloride, CH3NH3Cl (aq). CH3NH3+:
Kb= 3.6×10-4 or Ka = 2.8×10-11
[H3O+ ][CH3 NH 2 ]
CH3 NH3+ (aq)+H 2O(l) H3O+ (aq)+CH3 NH 2 (aq) Ka 
[CH3 NH3+ ]
CH 3 NH 3+ H3O  CH3 NH 2
Initial 0.10 0 0
Change -x x x
Equilibrium 0.10 - x x x
Ka  Kw
Kb  1.01014
3.6104
=2.8  1011 

11 [H 3 O + ][CH 3 NH 2 ]
2.8  10 = = 0.10- x 
x2 x2
0.10
[CH 3 NH 3+ ]
 x  0.10  2.8  1011  1.67  106
(less then 0.5% of 0.10, the approximation is valid)
[H 3 O  ]=x  1.67  106 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
62
 pH  log[1.67  106 ]  5.78
 Problem
Estimate the pH of 0.10 M NH4NO3 (aq). NH3: Kb = 1.8×10-5
[H3O+ ][NH3 ]
+
NH 4 (aq)+H 2O(l) +
H3O (aq)+NH3 (aq) Ka 
[NH 4  ]
NH 4  H 3O  NH3
Initial 0.10 0 0
Change -x x x
Equilibrium 0.10 - x x x

Ka  Kw
Kb  1.01014
1.8105
=5.6  1010 

10 [H 3 O + ][NH 3 ]
5.6  10 = 
= 0.10- x 
x2 x2
0.10
[NH 4 ]
 x  0.10  5.6  1010  7.5  10 6
(less then 0.5% of 0.15, the approximation is valid)
[H 3 O  ]=x  7.5  10 6 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
63
 pH  log[7.5  106 ]  5.12
 Problem
Estimate the pH of 0.15 M calcium acetate, Ca(CH3CO2)2 (aq).
CH3CO2-: Ka = 1.8×10-11
 [CH3COOH][OH  ]

H 2O(l)  CH3CO2 (aq) CH3COOH(aq)  OH (aq) K b 
[CH3CO2  ]
CH 3 CO 2 - OH - CH3 COOH
Initial 0.30 0 0
Change -x x x
Equilibrium 0.30 - x x x

Kb  Kw
Ka  1.01014
1.8105
=5.6  1010 

10 [CH 3 COOH][OH  ]

5.6  10 = = 0.30- x 
x2 x2
[CH 3 CO 2  ]
0.30

 x  0.30  5.6  1010  1.3  10 5

(less then 0.5% of 0.30, the approximation is valid)
[OH - ]=x  1.3  10 5 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
64
5
 pOH  log[1.3  10 ]  4.89  pH=9.11
 Problem
Estimate the pH of 0.02 M potassium fluoride, KF (aq).
HF: Ka = 3.5×10-4 [FH][OH ] 
 
H 2O(l)  F (aq) FH(aq)  OH (aq) K b 
[F ]
F- OH - FH
Initial 0.02 0 0
Change -x x x
Equilibrium 0.02 - x x x

Kb  Kw
Ka  1.01014
3.5104
=2.86  1011 
11 [FH][OH  ]
2.86  10 = = x2
x 
x2
[F ]
0.02- 0.02

 x  0.02  2.86  1011  7.56  107

(less then 0.5% of 0.02, the approximation is valid)
[OH - ]=x  7.56  10 7 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
65
7
 pOH  log[7.56  10 ]  6.12  pH=7.88
 Problem
Estimate the pH of a solution that is 0.5 M HNO2 and 0.1 M KNO2 (aq).
HNO2 :Ka = 4.3×10-4

  [H3O ][NO2  ]
HNO2 (aq)+H 2O(l) H3O (aq)+NO2 (aq) Ka 
[HNO2 ]
HNO 2 H 3O  NO 2 
Initial 0.5 0 0.1
Change -x x x
Equilibrium 0.5 - x x 0.1+x

4[H3 O  ][NO 2  ] x (0.1 x )

4.3  10 = = 0.5- x  0.1x
0.50
[HNO 2 ]
 x  2.2  103
(less then 0.5% of 0.50, the approximation is valid)
[H 3 O + ]=x  2.2  10 3 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
66
3
 pH  log[2.2  10 ]  2.66
 Problem
Estimate the pH of a solution that is 0.3 M CH3NH2 and 0.146 M
CH3NH3Cl(aq). CH3NH2 :Kb = 3.6×10-4
[OH- ][CH3 NH3+ ]
CH3 NH 2 (aq)+H 2O(l) -
OH (aq)+CH3 NH3 (aq) +
Kb 
[CH3 NH 2 ]
CH 3 NH 2 OH  CH3 NH3+
Initial 0.30 0 0.146
Change -x x x
Equilibrium 0.30 - x x 0.146+x

4 [OH - ][CH 3 NH 3+ ] x (0.146 x )

3.6  10 = K b  = 0.3- x  0.146x
0.30
[CH3 NH 2 ]
 x  7.4  104
(less then 0.5% of 0.30, the approximation is valid)
[OH - ]=x  7.4  10 4 >> autoprotlysis molarity (1.0  107 ),
meaning autoprotolysis contribution can be neglected.
67
 pOH  log[7.4  104 ]  3.13  pH=10.87
 II.1 Common-Ion Effect in Acid-Base Equilibria

The Common-Ion Effect

“The extent of ionization of a weak electrolyte is
decreased by adding to the solution a strong electrolyte
that has an ion in common with the weak electrolyte.”

Calculate the fluoride ion concentration and pH of a solution

that is 0.20 M in HF and 0.10 M in HCl.
Ka for HF is 6.8  10−4.

[H3O+] [F−]
Ka = = 6.8  10-4
[HF]
68
 II.1 Common-Ion Effect in Acid-Base Equilibria

The Common-Ion Effect

HF(aq) + H2O(l) H3O+(aq) + F−(aq)
Because HCl, a strong acid, is also present, the initial [H3O+]
is not 0, but rather 0.10 M.
[HF], M [H3O+], M [F−], M

Initially 0.20 0.10 0

Change −x +x +x
At Equilibrium 0.20 − x  0.20 0.10 + x  0.10 x

1.4  10−3 = x 69
II.1 Common-Ion Effect in Acid-Base Equilibria

The Common-Ion Effect

• Therefore, [F−] = x = 1.4  10−3

[H3O+] = 0.10 + x = 1.01 + 1.4  10−3 = 0.10 M
• So, pH = −log (0.10)  pH = 1.00

70
 II.2 Buffer Solutions

Buffers:
 Solutions of a weak
conjugate acid-base pair.
 They are particularly
resistant to pH changes,
even when strong acid or
base is added.

“Solutions which resist changes in pH when

small quantities of acid or alkali are added.”
 II.2 Buffer Solutions

Buffers

If a small amount of hydroxide is added to an equimolar solution of HF

in NaF, for example, the HF reacts with the OH− to make F− and water.
II.2 Buffer Solutions

Buffers

If acid is added, the F− reacts to form HF and water.

II.2 Buffer Solutions

Buffer Calculations

Consider the equilibrium constant expression for

the dissociation of a generic acid, HA:

HA + H2O H3O+ + A−

[H3O+] [A−]
Ka =
[HA]
II.2 Buffer Solutions

Buffer Calculations
Rearranging slightly, this becomes
[A −]
Ka = [H3O+]
[HA]
Taking the negative log of both side, we get
base
[A−]
−log Ka = −log [H3O+] + −log
[HA]
pKa
acid
pH
 II.2 Buffer Solutions

[base]
• So pKa = pH − log
[acid]
• Rearranging, this becomes
[base]
pH = pKa + log
[acid]

• This is the Henderson–Hasselbalch equation.

II.2 Buffer Solutions

77
 Problem
What is the pH of a buffer that is 0.12 M in lactic acid,
HC3H5O3, and 0.10 M in sodium lactate? Ka for lactic acid is
1.4  10−4.
 Solution
[base]
pH = pKa + log
[acid]
(0.10)
pH = −log (1.4  10−4) + log (0.12)
pH = 3.85 + (−0.08)

pH = 3.77
 II.2 Buffer Solutions

pH Range

• The pH range is the range of pH values over

which a buffer system works effectively.
• It is best to choose an acid with a pKa close to
the desired pH.
II.2 Buffer Solutions

When Strong Acids or Bases Are Added to a Buffer…

…it is safe to assume that all of the strong acid or
base is consumed in the reaction.
II.2 Buffer Solutions

Addition of Strong Acid or Base to a Buffer

1. Determine how the neutralization

reaction affects the amounts of the
weak acid and its conjugate base in
solution.
2. Use the Henderson–Hasselbalch
equation to determine the new pH of
the solution.
 Problem
Calculating pH Changes in Buffers
A buffer is made by adding 0.300 mol HC2H3O2 and 0.300
mol NaC2H3O2 to enough water to make 1.00 L of solution.
The pH of the buffer is 4.74. Calculate the pH of this solution
after 0.020 mol of NaOH is added.
 Solution
Before the reaction, since
mol HC2H3O2 = mol C2H3O2− pH = pKa = −log (1.8  10−5) = 4.74
The 0.020 mol NaOH will react with 0.020 mol of the acetic acid:
HC2H3O2(aq) + OH−(aq)  C2H3O2−(aq) + H2O(l)
HC2H3O2 C2H3O2− OH−

Before reaction 0.300 mol 0.300 mol 0.020 mol

After reaction 0.280 mol 0.320 mol 0.000 mol

Now use the Henderson–Hasselbalch equation to calculate the new pH:

(0.320)
pH = 4.74 + log pH = 4.74 + 0.06
(0. 200)
pH = 4.80
II-4 Neutralization Reactions and Titration Curves

Titration
A known concentration
of base (or acid) is slowly
added to a solution of
acid (or base).

The equivalence point of a

neutralization reaction is the
point at which both acid and
base have been consumed
and neither is in excess.
II-4 Neutralization Reactions and Titration Curves

A pH meter or indicators
are used to determine
when the solution has
reached the equivalence
point, at which the
stoichiometric amount of
acid equals that of base.

The equivalence point is located by noting the color change of the

acid-base indicator

The point in a titration at which the indicator changes color is

called the end point of the indicator.
 II-4 Neutralization Reactions and Titration Curves

Titration of a Strong Acid with a Strong Base

A graph of pH versus volume of titrant (the solution in the buret) is
called a titration curve.

The titration of a strong acid with a strong base 25.00 mL of 0.100

M HCl with 0.100 M NaOH.
II-4 Neutralization Reactions and Titration Curves

From the start of the titration to near the equivalence point, the88pH
goes up slowly.
II-4 Neutralization Reactions and Titration Curves
Titration of a Strong Acid with a Strong Base
 Just before and after the
equivalence point, the pH
increases rapidly.
 At the equivalence point,
moles acid = moles base, and
the solution contains only
water and the salt from the
cation of the base and the
anion of the acid.
 As more base is added, the
increase in pH again levels off.
II-4 Neutralization Reactions and Titration Curves

Titration curve for the titration of a weak acid with a strong

base 25.00 mL of 0.100 M CH3COOH with 0.100 M NaOH 90
 II-4 Neutralization Reactions and Titration Curves

Titration of a Weak Acid with a Strong Base

• Unlike in the previous case, the

conjugate base of the acid affects
the pH when it is formed.
• The pH at the equivalence point
will be >7.
• Phenolphthalein is commonly
used as an indicator in these
titrations.
II-4 Neutralization Reactions and Titration Curves

Titration of a Weak Acid with a Strong Base

At each point below the equivalence point, the pH of the

solution during titration is determined from the amounts
of the acid and its conjugate base present at that
particular time.
 Problem
Calculating Points on a Titration Curve: Weak Acid Titrated
with a Strong Base

What is the pH at each of the following points in the titration of 25.00

mL of 0.100 M CH3COOH with 0.100 M NaOH?

(a) before the addition of any NaOH (initial pH)

(b) after the addition of 10.00 mL 0.100 M NaOH (before equivalence
point)
(c) after the addition of 12.50 mL 0.100 M NaOH (half-neutralization)
(d) after the addition of 25.00 mL 0.100 M NaOH (equivalence point)
(e) after the addition of 26.00 mL 0.100 M NaOH (beyond equivalence
point).
93
Problem

94
II-4 Neutralization Reactions and Titration Curves

95
II-4 Neutralization Reactions and Titration Curves

Titration of a Weak Acid with a Strong Base

With weaker acids,

the initial pH is
higher and pH
changes near the
equivalence point
are more subtle.
 II-4 Neutralization Reactions and Titration Curves

Titration of a Weak Base with a Strong Acid

• The pH at the
equivalence point in
these titrations is < 7.
• Methyl red is the
indicator of choice.
II-4 Neutralization Reactions and Titration Curves

Titrations of Polyprotic Acids

In these cases
there is an
equivalence
point for each
dissociation.
II-5 Solutions of Salts of Polyprotic Acids

The neutralization of phosphoric acid by a strong base:

 The first equivalence point should come in a

somewhat acidic solution.
 The second in a mildly basic solution.
 The third equivalence point could be reached only in a
strongly basic solution.

99
Problem

100
 Problem

Classify the following solutions as acid or basic solution

NaHCO
NaHCO3
Na2CO3
NaH2PO4
Na2HPO4
Na3PO4

101
 Example
Calculate the pH of a buffer solution that is 0.04 M NH4Cl (aq) and 0.03
M NH3 (aq) at 25 oC. NH3: pKb = 4.75

[NH 4 + ][OH- ]
NH3 (aq)+H 2O(1) NH 4 + (aq)+OH - (aq) Kb =
[NH3 ]
[NH3 ]
[OH - ]=K b 
[NH 4  ]
 [NH3 ] 
log[OH ]=  logK b  log 
-
 
 [NH 4 ]

 [NH3 ]   [NH 4  ] 
pOH=pK b  log   
=pK b +log  
 [NH 4 ]   [NH 3 ] 
 0.04 
pOH  4.75+log    4.87  pH=9.13.
 0.03 
102
 Classroom Exercise
Calculate the pH of a buffer solution that is 0.15 M HNO2
(aq) and 0.2 M NaNO2 (aq) at 25 oC. HNO2: pKa = 3.37
[H3O+ ][NO2  ]
HNO2 (aq)+H 2O(1) H3O+ (aq)+NO2  (aq) Ka =
[HNO2 ]

[HNO 2 ]
[H 3O + ]=K a 
[NO 2  ]
 [HNO 2 ] 
log[H 3O ]=  logK a  log 
+
 
 [NO 2 ] 

 [HNO 2 ]   [NO 2  ] 
pH=pK a  log   
=pK a +log  
 [NO 2 ]   [HNO 2 
]
 0.2 
pH  3.37+log    3.49.
 0.15  103
 Calculating the pH change when acid or base added to a buffer
1.2 g (0.03 mol) of NaOH is dissolved in 500 mL of a buffer solution that is 0.04 M NaCH3CO2 (aq) and 0.08 M
CH3COOH (aq) with pH=4.45. Calculate the pH of the resulting solution and the change in pH. Assume volume
is not changed.

Moles of CH3COOH = 0.5 L  0.08 M = 0.04 mol

CH3COOH(aq)+OH CH3CO-2 (aq)+H2O(1)

The amount of acetic acid that reacts: 0.03 mol OH-  1 mol CH3COOH
1 mol OH - = 0.03 mol OH-
The amount of CH3COOH remaining is 0.04 - 0.03 mol = 0.01 mol
0.01 mol
Molarity of CH3COOH = 0.5 L = 0.02 M
Moles of CH3CO-2  0.5 L  0.04 M + 0.03 mol = 0.05 mol

Molarity of CH3CO-2  0.05 mol

0.5 L = 0.1 M

CH3COOH(aq)+H2O(1) H3O (aq)+CH3CO-2 (aq)

 [CH3CO2  ]initial   0.10 

pH  pK a +log   =4.75+log    5.45.
 0.02 
104
 [CH3COOH]initial 
 The Action of Buffers
An acid buffer solution consists of a weak acid and its
conjugate base: HA/A-; it has pH<7.0.

An base buffer solution consists of a weak base and its

conjugate acid: BH+/B; it has pH>7.0.

Blood and other cell fluids buffered at pH = 7.4.

Oceans are buffered at pH=8.4.

Thaønh phaàn vaø ñaëc ñieåm cuûa dung dòch ñeäm

Khi theâm bazô maïnh vaøo ñeäm, OH- phaûn öùng vôùi HX taïo X- vaø
nöôùc.
Tuy nhieân tæ leä [HX]/[X-] ít thay ñoåi, do ñoù pH oån ñònh.
Khi theâm acid maïnh vaøo ñeäm, H+ taùc duïng vôùi X- taïo HX. 105
 Acid Buffer Action

CH3COOH(aq)+H2O(1) H3O+ (aq)+CH3CO2 (aq)

HA H3O+  CH3COOH pH change very small.

BOH OH-  consumes H3O+CH3COOH  CH3CO2-

pH change very small.

Acid buffer action: the weak acid transfers protons to the OH- ions from added
strong base. The conjugate base of the weak acid accepts protons from the H3O+
ions supplied by a strong acid.

106
 Base Buffer Action
+ 
NH3 (aq)+H2O(1) NH4 (aq)+OH (aq)

HA H3O+  promotes NH3 to protonate and consumed by OH-

pH change very small.

BOH OH- stimulates NH3 to deprotonate  NH4+

pH change very small.

Base buffer action: the conjugate acid of the weak base transfers protons to the
OH- ions from added strong base. The weak base accepts protons from the H3O+
ions supplied by a strong acid.

107
 Design a Buffer with Specified pH
This is a problem of mixed solutions (both an acid and the salt of its
conjugate base are contained).

Acid buffer:
[H3O+ ][A- ]
HA(aq)+H 2O(1) H3O+ (aq)+A  (aq) Ka =
[HA]
[HA]
[H 3O ]=K a  
+

[A ]
 [HA] 
log[H 3O ]=  logK a  log   
+

 [A ] 
 [HA]   [A  ] 
pH=pK a  log    =pK a +log  
 [A ]   [HA] 
 [base]initial 
pH  pK a +log       Henderson-Hasselbalch equation .
 [acid]initial 
108
 Example
Calculate the pH of a buffer solution that is 0.04 M NaCH3CO2 (aq)
and 0.08 M CH3COOH (aq) at 25 oC. CH3COOH: pKa = 4.75

[H3O+ ][CH3CO2  ]
CH3COOH(aq)+H 2O(1) H3O+ (aq)+CH3CO2  (aq) Ka =
[CH3COOH]

[CH 3COOH]
[H 3O + ]=K a 
[CH 3CO 2  ]
 [CH 3COOH] 
log[H 3O ]=  logK a  log 
+
 
 [CH 3 CO 2 ] 
 [CH 3COOH]   [CH 3CO 2  ] 
pH=pK a  log    =pK a +log  
 [CH 3 CO 2 ]   [CH 3 COOH] 
 0.04 
pH  4.75+log    4.45.
 0.08  109
 Design a Buffer with Specified pH
Base buffer:

[OH- ][BH + ]
B(aq)+H 2O(1) OH - (aq)+BH + (aq) Kb =
[B]
[B]
[OH ]=K b 
-

[BH + ]
 [B] 
log[OH ]=  logK b  log 
-
+ 
 [BH ] 
 [B]   [BH + ] 
pOH=pK b  log  + 
=pK b +log  
 [BH ]   [B] 
 [acid]initial 
pOH  pK b +log    pH=14-pOH.
 [base]initial  110