Chm096 Chapter 4 Acids and Bases

FOUNDATION CHEMISTRY II
CHM096
CHAPTER 4
ACIDS AND
BASES
TOPICS
4.1
Definitions Acids and Bases
4.2
Strength of Acids and Bases
4.3
pH- A Measure of Acidity
4.4
The Acid-Base Properties of Ions and Salts
4.5
Buffer Solutions
4.6
Acid Base Titration Curve
4.7
Indicators
2
TOPIC
4.1 DEFINITIONS OF ACIDS AND BASES
4.1

Properties of Acids
Sour taste
React with active metals
i.e., Al, Zn, Fe, but not Cu, Ag, or Au
2 Al + 6 HCl
2 AlCl3 + 3 H2
corrosive
React with carbonates, producing CO2
marble, baking soda, chalk, limestone
CaCO3 + 2 HCl CaCl2 + CO2 + H2O

Change color of vegetable dyes
blue litmus turns red
React with bases to form ionic salts
Common Acids
4.1

Structures of Acids
Binary acids have acid hydrogens attached to a

nonmetal atom
HCl, HF
Oxy acids have acid hydrogens attached to an

oxygen atom
H2SO4, HNO3
4.1

Structures of Acids
Carboxylic acids have
COOH group
HC2H3O2, H3C6H5O7
Only the first H in the
formula is acidic
the H is on the
COOH
4.1

Properties of Bases
Also known as alkalis

Taste bitter
alkaloids = plant product that is
alkaline
often poisonous
Solutions feel slippery
Change color of vegetable dyes
different color than acid
red litmus turns blue
React with acids to form ionic salts
neutralization
Common Bases
4.1

Structure of Bases
Most ionic bases contain OH ions

NaOH, Ca(OH)2
Some contain CO32 ions
CaCO3 ,NaHCO3
Molecular bases contain structures that react with H+
mostly amine groups -e.g CH3CH2NH2
4.1

Arrhenius Theory
An acid is a substance that, when dissolved in water,

increases the concentration of hydrogen ions.
A base is a substance that, when dissolved in water,
increases the concentration of hydroxide ions.
11
4.1

Arrhenius Theory
NaOH dissociates in water,

HCl ionizes in water,
producing H+ and Cl ions producing Na+ and OH ions
12
4.1

Arrhenius Theory
Hydronium Ion
The H+ ions produced by the acid are so reactive they
cannot exist in water
H+ ions are protons!!
Instead, they react with water molecules to produce

complex ions, mainly hydronium ion, H3O+
H+ + H2 O H3 O +
13
4.1

Arrhenius Theory
Arrhenius Acid-Base Reaction

The H+ from the acid combines with the OH from the
base to make a molecule of H2O
it is often helpful to think of H2O as H-O-H
The cation from the base combines with the anion from
the acid to make a salt
acid + base salt + water
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
14
4.1

Arrhenius Theory
Exercise 1
a) Which of the following are Arrhenius acids?
NaHSO4, HI, NaH, H3PO3
a) Which of the following are Arrhenius bases?
H3AsO4, HClO, KOH, H2NNH2
15
4.1

Arrhenius Theory
Limitations of Arrhenius Acid-Base Theory
Does not explain why molecular substances, such as

NH3, dissolve in water to form basic solutions even
though they do not contain OH ions
Does not explain how some ionic compounds, such as
Na2CO3 or Na2O, dissolve in water to form basic
solutions even though they do not contain OH ions
Does not explain why molecular substances, such as
CO2, dissolve in water to form acidic solutions even
though they do not contain H+ ions
Does not explain acidbase reactions that take place in
non-aqueous solution or in the absence of water
16
4.1

Brnsted-Lowry Theory
In a Brnsted-Lowry acidbase reaction,

a proton (H+) is transferred
An acid is a proton donor, must have a removable
(acidic) proton.
A base is a proton acceptor, must have a pair of
nonbonding electrons.
In a Brnsted-Lowry acid-base reaction, the acid
molecule gives an H+ to the base molecule
HA + :B :A + HB+
17
4.1

Brnsted-Lowry Acid
Brnsted-Lowry acids are H+ donors
any material that has H can potentially be a Brnsted-Lowry acid
When HCl dissolves in water, the HCl is the acid because

HCl transfers an H+ to H2O, forming H3O+ ions
water acts as base, accepting H+
HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)

acid
base
18
4.1

Brnsted-Lowry Bases
Brnsted-Lowry bases are H+ acceptors
any material that has atoms with lone pairs can potentially be a
Brnsted-Lowry base
When NH3 dissolves in water, the NH3(aq) is the base

because NH3 accepts an H+ from H2O, forming OH(aq)
water acts as acid, donating H+
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)

base
acid
19
4.1

Amphoteric Substances
Amphoteric substances can act as either an acid or a
base
because they have both a transferable H and an atom with
lone pair electrons
Water acts as base, accepting H+ from HCl

Water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
Therefore, water is amphoteric
20
4.1

Brnsted-Lowry Acid-Base Reactions

One of the advantages of Brnsted-Lowry theory is that
it allows reactions to be reversible
HA + :B :A + HB+
The original base has an extra H+ after the reaction, so it
will act as an acid in the reverse process
And the original acid has a lone pair of electrons after
the reaction so it will act as a base in the reverse
process
:A + HB+ HA + :B
21
4.1

Conjugate Acids and Bases

The term conjugate comes from the Latin word
conjugare, meaning to join together.
Reactions between acids and bases always yield their
conjugate bases and acids.
For the reaction: HA + :B :A + HB+

:A is the conjugate base of HA
HB+ is the conjugate acid of :B
22
4.1

23
4.1


H2O and HO constitute an
acid/conjugate base pair
NH3 and NH4+ constitute a

base/conjugate acid pair
24
4.1

Example 1
Write the formula for the conjugate acid of the following
H2O
H3O+
NH3
NH4+
CO32
HCO3
H2PO41
H3PO4
25
4.1

Example 2
Write the formula for the conjugate base of the following
H2O
HO
NH3
NH2
CO32
because CO32 does not have an H,

it cannot be an acid
H2PO41
HPO42
26
4.1

Exercise 2
Identify the Brnsted-Lowry acids and bases, and their

conjugates, in the reaction
a.
HSO4(aq) + HCO3(aq) SO42(aq) +
b.
HCO3 (aq) + H2O
H2CO3 (aq) +
H2CO3(aq)
HO (aq)
27
4.1

Exercise 3
Write the equations for the following species react with

water and label the conjugate acid and base
a) H2PO4-
b) HClO2
c) CH3NH2
d) C6H5NH3+
28
4.1

Conclusion
Comparing Arrhenius and Brnsted-Lowry Theory

Arrhenius theory
HCl(aq) H+(aq) + Cl(aq)
HF(aq) H+(aq) + F(aq)
BrnstedLowry theory
HF(aq) + H2O(l) F(aq) + H3O+(aq)
NaOH(aq) Na+(aq) + OH(aq)
NaOH(aq) Na+(aq) + OH(aq)
NH4OH(aq) NH4+(aq) +
OH(aq)
NH3(aq) + H2O(l) NH4+(aq) +

OH(aq)
29
4.1

Lewis Acids-Bases Theory
Lewis AcidBase theory focuses on transferring an

electron pair
lone pair bond
Does NOT require H atoms
The electron donor is called the Lewis Base

electron rich, therefore nucleophile (Nu- )
The electron acceptor is called the Lewis Acid

electron deficient, therefore electrophile (E+)
30
4.1

Lewis Acid
Lewis acids are defined as electron-pair acceptors.
Atoms with an empty valence orbital can be Lewis
acids.
31
4.1

Lewis Bases
Lewis bases are defined as electron-pair donors.
Anything that could be a Brnsted-Lowry base is a

Lewis base.
32
4.1

Lewis Bases
Anions are better Lewis Bases than neutral atoms or
molecules
N: < N:
Generally, the more electronegative an atom, the less
willing it is to be a Lewis Base
O: < S:
33
4.1

Lewis Acids-Bases Reaction

The base donates a pair of electrons to the acid
Generally results in a dative bond forming
H3N: + BF3 H3NBF3
No H transfer
The product that forms is called an adduct

Arrhenius and Brnsted-Lowry acidbase reactions are
also Lewis acidbase reactions
34
4.1

Molecules as Lewis Acids

Lewis Acids with Electron-Deficient Atoms
35
4.1

Molecules as Lewis Acids

Lewis Acids with Polar Multiple Bonds
H O H
O H
S
H O O
Acid
Base
Adduct
36
4.1

Metal Cations as Lewis Acids

M2+ + 6H2O
+
Lewis
Acid
M(H2O)6 2+ (aq)
6
Lewis
Base
Adduct
Lone electron pairs on the O atoms of water form

covalently bonds to the positively charged ion
37
4.1

Metal Cations as Lewis Acids

Ag+(aq) + 2 :NH3(aq) Ag(NH3)2+(aq)
Lewis
Acid
Lewis
Base
Adduct
Ag+ ion acts as a Lewis acid when it dissolves in water:

Ammonia is a stronger Lewis base than water because it
displaces H2O from a hydrated ion when aqueous NH3 is
added.
38
4.1

Example 4
Identify the Lewis Acid and Lewis Base in Each Reaction
Lewis
Base
Lewis
Acid
Lewis
Base
Lewis
Acid
39
4.1

Exercise 4
Identify the Lewis Acid and Lewis Base in Each Reaction
a) H+ + OH-
H2O
b) Cl- + BCl3
BCl4-
c) K+ + 6H2O
K(H2O)6 +
40
TOPIC
4.2 STRENGTH OF ACIDS AND BASES
41
4.2

Strong or Weak
A strong acid is a strong electrolyte

practically all the acid molecules ionize,
A strong base is a strong electrolyte
practically all the base molecules form OH ions,
either through dissociation or reaction with water,
A weak acid is a weak electrolyte
only a small percentage of the molecules ionize,
A weak base is a weak electrolyte
only a small percentage of the base molecules form
OH ions, either through dissociation or reaction with
water,
42
4.2

Strong Acid
Strong acids are

completely dissociated in
water.
HCl H+ + Cl
HCl + H2O H3O+ + Cl
Willing to donate H+
100% ionized in water
Strong electrolyte
Their conjugate bases

has a negligible tendency
to be protonated.
[H3O+] = [strong acid]
[X] means the molarity of X
0.10 M HCl = 0.10 M H3O+

43
4.2

Weak Acid
Weak acid only

dissociate partially in
water.
Donate a small fraction of
their H+
Less than 1% ionization to
water
HF H+ + F
HF + H2O H3O+ + F
Their conjugate bases

are weak bases.- slight
ability to remove protons
from water
[H3O+]
<< [weak acid]
0.10 M HF 0.10 M H3O+

44
4.2

Acid Ionization Constant, Ka
Acid strength measured by the size of the equilibrium

constant when reacts with H2O
HA(aq) + H2O() A(aq) + H3O+(aq)

The equilibrium constant for this reaction is called the
acid ionization constant, or acid dissociation
constant, Ka
[H3O+] [A-]
larger Ka = stronger acid Ka =
[HA]
45
4.2

Weak Acids
46
4.2

Negligible Acidity
Substances with negligible acidity do not dissociate in

water. Example CH4, contains H but does not
demonstrate any acidic behavior.
Their conjugate bases are exceedingly strong.
47
4.2

Exercise 5
Arrange in the increasing order of acidic strength

Acids
Acid dissociation constant, Ka
HCN
CH3COOH
HF
HBrO
7.2 x 10-10
1.8 x 10-5
6.7 x 10-4
2.5 x 10-9
48
4.2 Strength of Acids and Bases

Relative Strengths of Acids and Bases
We can think of proton transfer reactions as being
governed by the relative abilities of two bases to
abstract protons
HX (aq) + H2O (l)
H3O+ (aq) + X- (aq)
If H2O (the base in the forward reaction) is a much

stronger base than X- (the conjugate base of HX), then
H2O will abstract the proton from HX to produce H3O+
and XAs a result, the equilibrium will lie to the right. This
describes the behavior of a strong acid in water.
49
4.2

In any acid-base reaction, the equilibrium will favor the
reaction that moves the proton to the stronger base.
HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

H2O is a much stronger base than Cl-, so the equilibrium
lies so far to the right that K is not measured (K>>1)
50
4.2

When X- is a stronger base than H2O, the equilibrium will
lie to the left. This situation occurs when HX is a weak
acid
CH3CO2H (aq) + H2O (l) H3O+ (aq) + CH3CO2- (aq)

Acetate is a stronger base than H2O, so the equilibrium
favors the left side (K<1)
Conclusion: in every acid-base reaction the position of
the equilibrium favors transfer of the proton from the
stronger acid to the stronger base to form the weaker
acid and the weaker base
51
4.2
Examples of Strong and Weak Acids
52
4.2
53
4.2

Example 6
HSO4(aq) +
CO3(aq) SO42(aq) +
HCO3- (aq)
For the following proton-transfer reaction, use table to

predict whether the equilibrium lies predominantly to
the left (that is Kc < 1) or to the right (Kc >1)
54
4.2

Answer
CO32- appears lower in the right-hand column in Figure

16.4 and is therefore a stronger base than SO42-. CO32-,
therefore will get the proton preferentially to become
HCO3-, while SO42- will remain mostly unprotonated. The
resulting equilibrium will lie to the right favoring
products (that Kc >1)
55
4.2

Exercise 6
For each the following reactions, use table 16.4 to

predict whether the equilibrium lies predominantly to the
left or to the right
HPO42-(aq) +
H2O (l) H2PO4(aq) +
OH- (aq)
NH4+(aq) + OH (l) NH3 (aq) + H2O (aq)
56
4.2

Strong Bases
Bases react with water to produce hydroxide ion.

The most common soluble strong bases are the ionic
hydroxides of the alkali metal.
Metals from group 1A and 2A
NaOH, KOH completely dissociate into ions in aqueous

solution
0.3M NaOH consists of 0.3 M Na+ and 0.3 M OH57
4.2

Strong Bases
LiOH, RbOH are not commonly encountered in the

laboratory
Ca(OH)2, Sr(OH)2, Ba(OH)2 have limited solubilities
Ionic metal oxides, Na2O and CaO
The O2- reacts with water to form OH-, leaving virtually
no O2- remaining in the solution.
O2- (aq) + H2O (l) 2OH- (aq)
58
4.2

Weak Bases
In weak bases, only a small fraction of molecules accept

Hs
weak electrolyte
most of the weak base molecules do not take H from water
much less than 1% ionization in water
[HO] << [weak base]

Finding the pH of a weak base solution is similar to
finding the pH of a weak acid
59
4.2

Weak Bases
NH3 + H2O NH4+ + OH
60
4.2

Base Ionization Constant, Kb
Base strength measured by the size of the equilibrium

constant when a base B reacts with H2O
:B- + H2O OH + H:B+
The equilibrium constant is called the base ionization
constant, Kb
larger Kb = stronger base
The equilibrium constant

expression for this reaction is
[H:B+] [OH-]
Kb =
[:B-]
61
4.2

Weak Bases
62

Classifying the Relative Strengths of
Acids and Bases
Strong acids. Two types of strong acids, with examples
that you should memorize, are
The hydrohalic acids, HCl, HBr, and HI
Oxoacids in which the number of O atoms exceeds the number of
ionizable protons by two or more, such as HNO3, H2SO4,and
HClO4; for example, in H2SO4, 4 Os -2Hs = 2
63

Acids and Bases
Weak acids. There are many more weak acids than
strong ones. Four types, with example, are
The hydrohalic acid HF
Those acids in which H is not bonded to O or to halogen, such as
HCN and H2S
Oxoacids in which the number of O atoms, equals or exceeds by
one the number of ionizable protons,such as HClO, HNO2 and H3PO4
Carboxylic acids (general formula RCOOH) such as CH3COOH

64

Acids and Bases
Strong bases. Water-soluble compounds containing O2or OH- ion are strong bases. The cations are usually
those of the most active metals
M2O or MOH, where M = Group 1A (1) metal (Li, Na, K, Rb, Cs)
MO or M(OH)2 where M= Group 2A (2) metal (Ca, Sr, Ba)

[MgO and Mg(OH)2 are only slightly soluble in water, but the soluble
portions dissociates completely]
65

Acids and Bases
Weak bases. Many compounds with an electron-rich
nitrogen atom are weak bases (none are Arrhenius
bases). The common structural features is an N atom that
has a lone electron pair
Ammonia (NH3)
Amines (general formula RNH2, R2NH, or R3N), such as
CH3CH2NH2, (CH3)2NH, (C3H7)3N and C5H5N
66
4.2
Factors Affecting Acid Strength
67
4.2

The more polar the H-X bond and /or the weaker the H-X
bond, the more acidic the compound
So acidity increases from left to right across a row and

from top to bottom down a group
68

In oxyacids, in which an OH is bonded to another atom,
Y, the more electronegative Y is, the more acidic the acid
4.2
For a series of oxyacids, acidity increases

with the number of oxygens.
70
4.2

Resonance in the conjugate bases of carboxylic acids
stabilizes the base and makes the conjugate acid more
acidic
71
4.2

Exercise 7
Classify each of the following compounds as a strong

acid, weak acid, strong base, and weak base
a) H2SeO4
b) (CH3)2CHCOOH
c) KOH
d) (CH3)2CHNH2
72
4.2

Degree of Dissociation ()
Degree of dissociation is the fraction of the original solute

molecules that have dissociated or refer to the amount of solute
dissociated into ions per mole of molecules.
Figure below shows that the percentage dissociation of ethanoic
acid (CH3COOH) increases as the concentration decreases. The
percentage dissociation is defined as below
6.0
% dissociation
% dissociation = [HA] dissociated X 100

[HA] initial
5.0
4.0
3.0
2.0
1.0
0.05
0.10
0.15
Concentration of CH3COOH (M)

73
4.2

The relationship between concentration, the degree of dissociation and the

dissociation constant of a weak acid or a weak base can be derived as
shown below
(a) Consider a 1 dm3 solution of a weak acid HA with a concentration of c
mol dm-3
(b) If the degree of dissociation is , the concentration of undissociated acid
at equilibrium would be c(1-), we thus have
HA (aq) A- (aq) +
H+ (aq)
Initial (mol)
At equilb
Ka = [A-][H+]
[HA]
c(1- )
Ka = [c][c] = Ka = c2
c(1-)
(1-)
The above expression is known as the Ostwald dilution law. It can also be
applied to weak bases
Kb = c2
(1-)
74
=
4.2

For a weak acid , is very small

1 - 1 Ka = 2c
= Ka/c
[H+] = c = cKa/c = Kac
[H+] = c or [H+] = Kac
similar to weak base or [OH-] = c [OH-] = Kbc
The above equation show that the degree of dissociation at a given

temperature depends on the concentration of the given acid or base.
As the concentration of a weak acid or weak base decreases, the degree

of dissociation increases.
For example, at 298 K, of 0.100M CH3COOH is 1.34% but 0.0001M
CH3COOH is 13.4%
Thus, is not suitable to measure the strength of acid-base, but Ka or Kb

is suitable because the values of Ka or Kb do not change with
75
concentration at a constant temperature.
4.2

The formula [H+] = c or [H+] = Kac or [OH-] = c [OH-] = Kbc

Is important because the concentration of H+ for weak acid and OH- for
weak base can be calculated if the the value or Ka/Kb is given
Example
a) At 298 K, the degree of dissociation of 0.125M benzoic acid (C6H5COOH)
is 2.20 %. Calculate the dissociation constant, Ka
b) Calculate the degree of dissociation of the 0.1 M of ammonia solution
(Kb for ammonia at 298 K is 1.75 x 10-5)
Solution
a) Ka = c2 = 0.125 (0.022)2 = 6.19 x 10-5
(1-)
1- 0.022
b) [OH-] = Kbc = 1.75 x 10-5 x 0.1 = 1.32 x 10-3

[OH-] = c , thus = [OH-]/c = 1.32 x 10-3 / 0.1 = 0.0132 or 1.32%
76
4.2

Exercise 8
A 250 cm3 solution contains 0.123 mole of HF. Calculate

the degree of dissociation of HF if the Ka HF at 25 oC is
3.53 x 10-4
If the degree of dissociation of C2H5NH2 solution at

25oC is 1.25% and Kb is 5.40 x 10-4. Determine the
concentration of [OH-] produced in that solution
77
4.2
Autoionization of Water and The pH Scale

Water is an extremely weak electrolyte
In pure water, a few molecules act as bases and a few act
as acids.
This is referred to as autoionization. About 2 out of 2
billions of water molecules through this process
All aqueous solutions contain both H3O+ and OH
the concentration of H3O+ and OH are equal in water
[H3O+] = [OH] = 107M @ 25 C

+
H2O (l)
H 2O ( l )
H3O+ (aq)
OH- (aq)
78

Ion Product Constant of Water
The equilibrium expression for this process is
Kw = [H3O+] [OH-]
This special equilibrium constant is referred to as the
ion-product constant for water,
Kw. At 25C, Kw = 1.0 10-14

As [H3O+] increases, the [OH] must decrease so the
product stays constant
79
4.2

Acidic and Basic Solutions
All aqueous solutions contain both H3O+ and OH ions

Neutral solutions have equal [H3O+] = [OH]
[H3O+] = [OH] = 1.00 x 107
Acidic solutions have a larger [H3O+] > [OH]

[H3O+] > 1.00 x 107; [OH] < 1.00 x 107
Basic solutions have a larger [OH] > [H3O+]

[H3O+] < 1.00 x 107; [OH] > 1.00 x 107
80
4.2

Complete the table [H+] vs. [OH]

[H+] 100 101
+
H
OH
103
105
+
H
OH
107
+
H
109
1011
H+
OH OH
1013 1014
H+
OH
[OH]
81
4.2

Complete the table [H+] vs. [OH]
Acid
[H+] 100 101
+
H
OH
103
Base
105
+
H
OH
[OH]1014 1013 1011
109
107
109
+
H
OH
107
1011
1013 1014
H+
H+
OH
OH
105
103
101 100
Even though it may look like it, neither H+ nor OH will

ever be 0
The sizes of the H+ and OH are not to scale
because the divisions are powers of 10 rather than units82
4.2

Example 7
Calculate the [OH] at 25 C when the [H3O+] = 1.5 x 109

M, and determine if the solution is acidic, basic, or
neutral
83
4.2

Answer
Given:
Find:
Conceptual Plan:
[H3O+] = 1.5 x 109 M

[OH]
[H3O+]
[OH]
Relationships:
Solution:
Check: the units are correct; the fact that the

[H3O+] < [OH] means the solution is basic
84
4.2

Exercise 9
Determine the [H3O+] when the [OH] = 2.5 x 107 M
85
TOPIC
4.3 pH- A MEASURE OF ACIDITY
86
4.3
pH A Measure of Acidity
Definition
pH is defined as the
negative base-10 logarithm
of the concentration of
hydronium ion.
pH = -log [H3O+]
87
4.3
Definition
The acidity or basicity of a solution is often expressed as

pH
pH = log[H3O+]
exponent on 10 with a positive sign
pHwater = log[107] = 7
need to know the [H3O+] concentration to find pH
pH < 7 is acidic; pH > 7 is basic, pH = 7 is neutral
[H3O+] = 10pH
88
4.3
Definition
An acidic solution the [H3O+] > 1.0 x 10-7

Example: the pH of an acidic solution in which [H+] =
1.0 x 10-3
pH = -log(1.0 x 10-3) = -(-3.00) = 3.00
Conclusion: the pH decreases as [H+] increases

At 25oC the pH of an acidic solution is less than
7.00
89
4.3
[H3O+] and [OH] in a

Strong Acid or Strong Base Solution
There are two sources of H3O+ in an aqueous solution of
a strong acid the acid and the water
There are two sources of OH in an aqueous solution of
a strong acid the base and the water
For a strong acid or base, the contribution of the water

to the total [H3O+] or [OH] is negligible
the [H3O+]acid shifts the Kw equilibrium so far that [H3O+]water is
too small to be significant
except in very dilute solutions, generally < 1 x 104 M
90
4.3
Finding pH of a Strong Acid or

Strong Base Solution
For a monoprotic strong acid [H3O+] = [HA]
for polyprotic acids, the other ionizations can generally be
ignored
0.10 M HCl HAs [H3O+] = 0.10 M and pH = 1.00
For a strong ionic base, [OH] = (number OH)x[Base]

for molecular bases with multiple lone pairs available, only one
lone pair accepts an H, the other reactions can generally be
ignored
0.10 M Ca(OH)2 Has [OH] = 0.20 M and pH = 13.30
91
4.3
Example 8
Calculate the pH at 25 C when the [OH] = 1.3 x 102 M,

and determine if the solution is acidic, basic, or neutral
92
4.3
Answer
Given:
Find:
Conceptual Plan:
[OH] = 1.3 x 102 M

pH
[OH]
[H3O+]
pH
Relationships:
Solution:
Check: pH is unitless; the fact that the pH > 7

means the solution is basic
93
4.3
Exercise 10
Determine the pH @ 25 C of a solution that has [OH]

= 2.5 x 107 M
94
4.3
Example 9
Determine the [OH] of a solution with a pH of 5.40
95
4.3
Answer
Given:
Find:
Conceptual Plan:
pH = 5.40
[OH], M
pH
[H3O+]
[OH]
Relationships:
Solution:
Check: because the pH < 7, [OH] should be less than 1

x 107; and it is
96
4.3
Exercise 11
Consider two solutions, solution A and solution B. [H+]

in solution A is 500 times greater than in solution B.
What is difference in the pH values of the two
solutions?
97
4.3
pOH
Another way of expressing the acidity/basicity of a

solution is pOH
pOH = log[OH],
[OH] = 10pOH
pOHwater = log[107] = 7
need to know the [OH] concentration to find pOH
pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is neutral
pH + pOH = 14.0
98
4.3
pOH
99
4.3
Relationship between pOH and pH

pH + pOH = 14.00
at 25 C
you can use pOH to find pH of a solution
[H3O ][OH ] K w 1.0 1014

] 14.00
log
[H
O
]
log
[OH

log [H3O ][OH ] log 1.0 1014
pH pOH 14.00
100
4.3
Example 10
Calculate the pH at 25 C when the [OH] = 1.3 x 102 M,

and determine if the solution is acidic, basic or neutral
101
4.3
Answer
Given:
Find:
Conceptual Plan:
[OH] = 1.3 x 102 M

pH
[OH]
pOH
pH
Relationships:
Solution:
Check: pH is unitless; since t pH > 7, the solution

is basic
102
4.3
Example 12
Determine the pOH at 25 C of a solution that has

[H3O+] = 2.5 x 109 M
103
4.3
Answer
Given:
Find:
Conceptual Plan:
[H3O+] = 2.5 x 109 M

pOH
[H3O+]
pH
pOH
Relationships:
Solution:
Check: pH is unitless; the fact tHAt the pH < 7

means the solution is acidic
104
4.3
Example 12
Calculate the pH at 25 C of a 0.0015 M Sr(OH)2 solution

and determine if the solution is acidic, basic, or neutral
(Alterative Method)
105
4.3
Answer
[Sr(OH)2] = 1.5 x 103 M
Given:
pH
Find:
[OH]
Conceptual Plan: [Sr(OH) ]

2
Relationships:
[OH]=2[Sr(OH)2]
pOH
pH
pH + pOH = 14.00
Solution:
[OH]
= 2(0.0015)
= 0.0030 M
Check:
pH
= 14.00 2.52 = 11.48
pH is unitless; the fact that the pH > 7

means the solution is basic
106
4.3
Exercise 13
(a) Calculate the pH of a solution formed by mixing 10.0

mL of 0.015 M Ba(OH)2 with 40 mL of 7.5 x 10-3 M
NaOH
(b) Calculate the concentration of an aqueous solution

of Ca(OH)2 that has a pH of 12.05
107
4.3
Finding the pH of a Weak Acid

There are also two sources of H3O+ in an aqueous
solution of a weak acid the acid and the water
However, finding the [H3O+] is complicated by the fact HA
the acid only undergoes partial ionization
Calculating the [H3O+] requires the use of Ka for the
equilibrium :
HA + H2O A + H3O+
108
4.3
Example 13
Find the pH of 0.200 M HNO2(aq) solution @ 25

C, given that Ka for HNO2 = 4.6 x 104
109
4.3
Answer
represent the change

in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression
[HNO2]
initial
change
equilibrium
0.200
x
0.200 x
[NO2] [H3O+]
0
+x
x
0
+x
x
HNO2 + H2O(l) NO2(aq) + H3O+(aq)
110
4.3
Answer
because Ka is very
small, approximate initial
the [HNO2]eq =
change
[HNO2]init and
solve for x
equilibrium
[HNO2]
[NO2] [H3O+]
0.200
+x
+x
0.200
111
4.3
Answer
Ka for HNO2 = 4.6 x 104

check if the
[HNO2] [NO2] [H3O+]
approximation is
0.200
initial
0
0
valid by seeing if
x
+x
+x
x < 5% of [HNO2]init change
equilibrium
0.200
x
x
x = 9.6 x 103
the approximation is valid
112
4.3
Answer
substitute x
into the
equilibrium
concentration
definitions and
solve
Ka for HNO2 = 4.6 x 104
initial
change
equilibrium
[HNO2] [NO2] [H3O+]

0.200
0
0
x
+x
+x
0.190
0.0096 0.0096
x = 9.6 x 103
113
4.3
Answer
substitute
[H3O+] into the
formula for pH
and solve
initial
change
equilibrium
[HNO2]
[NO2]
[H3O+]
0.200
+x
+x
0.190
0.0096
0.0096
114
4.3
Determining [H3O+] of a Weak Acid from Ka

using the Direct Approach
For a weak acid HA with [HA] = c mol/L
[H3O+] [A-]
Ka =
[HA]
Since [A] = [H3O+]
[HA ] x Ka = [H3O+]
[H3O+] = c x Ka
[H3O+] = c x Ka
115
4.3
Example 14
What is the pH of a 0.012 M solution of nicotinic acid,

HC6H4NO2?
(Ka = 1.4 x 105 at 25 C)
Answer
[HC6H4NO2 ] = 0.012 M = c
[H3O+] = c x Ka
[H3O+] = 0.012 x 1.4 x 105 = 4.1 x 104 M
pH = log(4.1 x 104) = 3.39
116
4.3
Example 15
What is the Ka of a weak acid if a 0.100 M solution

has a pH of 4.25?
Answer
use the pH to find the
equilibrium [H3O+]
write the reaction for
the acid with water
Compute Ka
HA + H2O A + H3O+
Ka = [H3O+] / c
= (5.6 x 105)/0.100
= 3.1 x 108
117
4.3
Exercise 14
The acid-dissociation constant Ka of hypochlorous acid,

(HClO), is 3.0 x 10-8. Calculate the concentrations of H3O+
and pH if the initial concentration of HClO is 0.0090 M
118
4.3
Exercise 15
A 0.100 M solution of chloroacetic acid (ClCH2COOH) is

11.0% ionized. Using this information, calculate
[ClCH2COO-], [H+], [ClCH2COOH] , and Ka for
chloroacetic acid.
119
4.3
Exercise 16
How many moles of HF (Ka = 6.8 x 10-4) must be present

in 0.200 L to form a solution with a pH of 3.25?
120
4.3
pK
Another way of expressing the strength of a weak acid

or weak base is pK
pKa = log(Ka), Ka = 10pKa
The stronger the acid, the smaller the pKa
larger Ka = smaller pKa because it is the log
pKb = log(Kb), Kb = 10pKb
The stronger the base, the smaller the pKb

larger Kb = smaller pKb
121
4.3
Example 16
a) HF has Ka = 3.5 x 104. Calculate the pKa.

pKa = logKa = log(3.5 x 104) = 3.455
b) The pKb of ethylamine, C2H5NH2 = 3.25. What is its
Kb value?
pKb = 3.25 Kb = 10pKb = 103.25
= 5.62 x 104
122
4.3
Example 17
Find the pH of 0.100 M NH3(aq)
123
4.3
Answer
Kb for NH3 = 1.76 x 105
determine the value

of Kb from Table 15.8
because Kb is very
small, approximate
the [NH3]eq = [NH3]init
and solve for x
initial
change
equilibrium
[NH3]
[NH4+]
[OH]
0.100
+x
+x
0.100
124
4.3
Answer
From previous calculation, obtained: x = 1.33 x 103
125
4.3
Answer
Alterative method:
use the [OH] to
find the pOH
use pOH to find
pH
126
4.3
Example 18
Find the pH of a 0.0015 M morphine solution,

Kb = 1.6 x 106 using direct approximation
method
127
4.3
Answer
B + H2O BH+ + OH
Taking [B] = c, and [BH+] = [OH]
Kb =
[BH+][OH]
[OH]
=
[B]
[OH] = (c x Kb) = (0.0015 x 1.6 x 106 )

= 4.9 x 105
pOH = log(4.9 x 105) = 4.31
pH = 14 pOH = 14 4.31
= 9.69
128
4.3
Answer
Kb for morphine = 1.6 x 106

use the [OH] to
find the pOH
use pOH to find
pH
initial
change
equilibrium
[B]
[BH+]
[OH]
0.0015
+x
+x
0.0015
4.9E5
4.9E5
129
4.3
Relationship between Ka of an Acid and Kb of Its

Conjugate Base
Many reference books only give tables of Ka
values because Kb values can be found from them
when you add
equations, you
multiply the
Ks
At 25 oC, Kw = 1 x 10 14
130
4.3
Exercise 17
Find the pH of a 0.075 M ethylamine solution,

(C2H5NH2, Kb = 1.6 x 106)
131
4.3
Exercise 18
Codeine (C18H21NO3) is a weak organic base. A 5.0 x 10-3

M solution of codeine has a pH of 9.95.
a) Calculate the value of Kb for this substance.
b) Determine the degree of dissociation
c) What is the pKb for this base?
132
4.3
Exercise 19
A 0.035 M of Ephedrine (C10H15ON) has a pH of 11.33.

(a). Write the chemical equation and the Kb expression
for the ionization of ephedrine in aqueous solution.
(b). Calculate the equilibrium concentrations for all
species
(c). Calculate pKb for ephedrine
133
TOPIC
4.4 THE ACID-BASE PROPERTIES
OF IONS AND SALTS
134
4.4 The Acid-base Properties of Ions

and Salts
Salt Hydrolysis
Salts are water-soluble ionic compounds
Basic salts
Salts that contain the cation of a strong base and an anion that is the
conjugate base of a weak acid are basic
NaF solutions are basic
Na+ is the cation of the strong base NaOH
F is the conjugate base of the weak acid HF. F sligthly

hydrolyse in water to give OH
F(aq) + H2O(l) HF(aq) + OH(aq)
135

and Salts
Salt Hydrolysis
Acidic Salts
Salts that contain cations that are the conjugate acid of a weak base
and an anion of a strong acid are acidic
NH4Cl solutions are acidic
NH4+ is the conjugate acid of the weak base NH3
NH4+ under goes hydrolysis to produce slight excess of H+

NH4+ (aq) + H2O(l) NH4 OH(aq) + H+(aq)
Cl is the anion of the strong acid HCl. No hydrolysis.
Neutral Salts
Salts that contain cations that are the conjugate acid of a strong
base and an anion of a strong acid are neutral. Examples: NaBr,
KNO3
136

and Salts
Salt Hydrolysis
Example 19
Use the table to determine if the given anion is basic or
neutral
a)
NO3
the conjugate base of a

strong acid, HNO3,
therefore neutral
b)
NO2
the conjugate base of a
weak acid, HNO2
therefore basic
137

and Salts
Salt Hydrolysis
Example 20
Find the pH of 0.100 M NaCHO2(aq) solution
138

and Salts
Salt Hydrolysis
Na+ is the cation of a
strong base pH
neutral. The CHO2
is the anion of a
weak acid pH basic
write the reaction for
the anion with water
construct an ICE
table for the reaction
Answer
CHO2 + H2O HCHO2 + OH

initial
[CHO2]
[HCHO2]
[OH]
0.100
change
equilibrium
enter the initial

concentrations
assuming the [OH]
from water is 0
139

and Salts
in terms of x
sum the columns to
concentrations in
terms of x
Salt Hydrolysis
Answer
[CHO2] [HCHO2] [OH]
initial
0.100
change
equilibrium
Calculate the value of

Kb from the value of Ka
of the weak acid from
Table 15.5
substitute into the
expression
140

and Salts
Salt Hydrolysis
Answer
because Kb is very
small, approximate
the [CHO2]eq =
[CHO2]init and solve
for x
initial
change
equilibrium
[CHO2]
[HCHO2]
[OH]
0.100
+x
+x
0.100
Kb for CHO2 = 5.6 x 1011
141

and Salts
Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011
check if the
approximation is
valid by seeing if x
< 5% of [CHO2]init
initial
change
equilibrium
[CHO2]
[HCHO2]
[OH]
0.100
+x
+x
0.100
x = 2.4 x 106
142

and Salts
Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011
substitute x into
the equilibrium
concentration
definitions and
solve
initial
change
[CHO2]
[HCHO2]
[OH]
0.100
+x
+x
equilibrium
143

and Salts
use the [OH] to
find the [H3O+]
using Kw
substitute [H3O+]
into the formula
for pH and solve
Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011
initial
change
equilibrium
[CHO2]
[HCHO2]
[OH]
0.100
+x
+x
0.100
2.4E-6
2.4E-6
144

and Salts
Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011
use the [OH] to

find the pOH
use pOH to find
pH
initial
change
equilibrium
[CHO2]
[HCHO2]
[OH]
0.100
+x
+x
0.100
2.4E6
2.4E6
145

and Salts
check by
substituting the
equilibrium
concentrations
back into the
equilibrium
constant
expression and
comparing the
calculated Kb to
the given Kb
Salt Hydrolysis
Answer
[CHO2] [HCHO2]
0.100
initial
cHAnge
x
equilibrium 0.100
[OH]
+x
+x
2.4E6
2.4E6
Kb for CHO2 = 5.6 x 1011
though not exact, the

answer is reasonably
close
146

and Salts
Na+ is the cation of

a strong base pOH
neutral. Because
pOH is < 7, the
solution is basic. A
is basic.
Salt Hydrolysis
Example 21
If a 0.0015 M NaA solution has a pOH

of 5.45, what is the Ka of HA?
A + H2O HA + OH
write the reaction

for the anion with
water
construct an ICE
table for the
reaction
initial
enter the initial

concentrations
assuming the [OH]
from water is 0
equilibrium
[A]
[HA]
[OH]
0.100
change
147

and Salts
use the pOH to
find the [OH]
Salt Hydrolysis
Answer
use [OH] to fill

in other items
[A]
[HA]
[OH]
0.15
0
0
initial
3.6E6 +3.6E6 +3.6E6
cHAnge
0.15
3.6E-6
3.6E-6
equilibrium
148

and Salts
Salt Hydrolysis
Answer
calculate the
value of Kb of A
initial
change
equilibrium
[A]
[HA]
[OH]
0.15
3.6E6
+3.6E6
+3.6E6
0.15
3.6E-6
3.6E-6
149

and Salts
Salt Hydrolysis
Answer
use Kb of A to
find Ka of HA
initial
change
equilibrium
[A]
[HA]
[OH]
0.15
3.6E6
+3.6E6
+3.6E6
0.15
3.6E-6
3.6E-6
Kb 8.39 1011
150

and Salts
Exercise 20
An unknown salt is either KBr, NH4Cl, KCN, or K2CO3. If

a 0.100 M solution of the salt is neutral, what is the
identity of the salt?
Calculate the pH of a 0.050 M solution of sodium
butyrate. (pKa CH3CH2CH2COONa = 4.84)
151

and Salts
Polyatomic Cations as Weak Acids
Some cations can be thought of as the conjugate acid of

a weak base
others are the counter-ions of a strong base
Therefore, some cations can potentially be acidic. They

undergo hydrolysis
MH+(aq) + H2O(l) MOH(aq) + H3O+(aq)
The stronger the base is, the weaker the conjugate acid is
a cation that is the counter-ion of a strong base is pH neutral
a cation that is the conjugate acid of a weak base is acidic
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

because NH3 is a weak base, the position of this equilibrium
favors the right
152

and Salts
Metal Cations as Weak Acids
Cations of small, highly charged metals are weakly

acidic
alkali metal cations and alkali earth metal cations are pH neutral
cations are hydrated
Al(H2O)63+(aq) + H2O(l) Al(H2O)5(OH)2+ (aq) + H3O+(aq)
153

and Salts
Example 22
Determine if the given cation is acidic or neutral

a)
b)
c)
C5H5NH+
the conjugate acid of the weak base pyridine, C5H5N
therefore acidic
Ca2+
the counter-ion of the strong base Ca(OH)2,
therefore neutral
Cr3+
a highly charged metal ion, therefore acidic
154

and Salts
Classifying Salt Solutions as Acidic, Basic, or Neutral
If the salt cation is the counter-ion of a strong base and
the anion is the conjugate base of a strong acid, it will
form a neutral solution
NaCl
Ca(NO3)2
KBr
If the salt cation is the counter-ion of a strong base and

the anion is the conjugate base of a weak acid, it will
form a basic solution
NaF
Ca(C2H3O2)2
KNO2
155

and Salts
If the salt cation is the conjugate acid of a weak base
and the anion is the conjugate base of a strong acid, it
will form an acidic solution
NH4Cl
If the salt cation is a highly charged metal ion and the

anion is the conjugate base of a strong acid, it will
form an acidic solution
Al(NO3)3
156

and Salts
If the salt cation is the conjugate acid of a weak base
and the anion is the conjugate base of a weak acid,
the pH of the solution depends on the relative
strengths of the acid and base
NH4F because HF is a stronger acid than NH4+, Ka of NH4+ is
larger than Kb of the F; therefore the solution will be acidic
157

and Salts
Example 23
Determine whether a solution of the following salts is
acidic, basic, or neutral
a)
b)
c)
SrCl2
Sr2+ is the counter-ion of a strong base, pH neutral
Cl is the conjugate base of a strong acid, pH neutral
solution will be pH neutral
AlCl3
Al3+ is a small, highly charged metal ion, weak acid
Cl is the conjugate base of a strong acid, pH neutral
solution will be acidic
CH3NH3NO3
CH3NH3+ is the conjugate acid of a weak base, acidic
NO3 is the conjugate base of a strong acid, pH neutral solution
will be acidic
158

and Salts
Answer
d)
e)
NaCHO2
Na+ is the counter-ion of a strong base, pH neutral
CHO2 is the conjugate base of a weak acid, basic
solution will be basic
NH4F
NH4+ is the conjugate acid of a weak base, acidic
F is the conjugate base of a weak acid, basic
Ka(NH4+) > Kb(F); solution will be acidic
159

and Salts
Example 24
Determine whether a solution of the following salts is
acidic, basic, or neutral
KNO3
CoCl3
Ba(HCO3)2
CH3NH3NO3
160

and Salts
Answer
K+ is the counter-ion of a strong base, pH neutral
KNO3
CoCl3
Ba(HCO3)2
CH3NH3NO3
NO3 is the counter-ion of a strong acid, pH neutral

the solution is pH neutral
Co3+ is a highly charged cation, pH acidic
Cl is the counter-ion of a strong acid, pH neutral
the solution is pH acidic
Ba2+ is the counter-ion of a strong base, pH neutral
HCO3 is the conjugate of a weak acid, pH basic
the solution is pH basic
CH3NH3+ is the conjugate of a weak base, pH acidic
NO3 is the counter-ion of a strong acid, pH neutral

the solution is pH acidic
161
TOPIC
4.5 BUFFER SOLUTIONS
162
4.5 Buffer Solutions

Buffers
Buffers are solutions of a weak conjugate acid-base pair.
They are practically resist changes in pH when an acid or base is
added even strong acid or base.
They act by neutralizing acid or base that is added to the buffered
solution
Acidic buffers are made by mixing a solution of a weak acid with a
solution of a salt containing its conjugate base anion
Mixing acetic acid, HC2H3O2 with sodium acetate, NaC2H3O2
Basic buffers are prepared by mixing a solution of a weak base
with a solution of a salt containing its conjugate acid cation
Mixing aqueous NH3 with ammonium chloride solution NH4Cl
163

Making an Acid Buffers
H2O(l) + HC2H3O2 (aq) C2H3O2-(aq) + H3O+(aq)
164

Making a Basic Buffers
H2O(l) + NH3 (aq) NH4+(aq) + OH(aq)
165

How Acid Buffers Work: Base Addition
H2O(l) + HA (aq) A-(aq) + H3O+(aq)

Buffers work by applying Le Chteliers Principle to
weak acid equilibrium
Acid Buffer solutions contain significant amounts of
the weak acid molecules, HA
These molecules neutralize the added base OH(aq)
HA(aq) + OH(aq) A(aq) + H2O(l)
you can also think of the H3O+ combining with the OH to make H2O;
the H3O+ is then replaced by the shifting equilibrium
166

How Acid Buffers Work: Acid Addition
H2O(l) + HA (aq) A-(aq) + H3O+(aq)

The buffer solution also contains significant amounts
of the conjugate base anion, A
These ions combine with added acid, H+(aq) to make
more HA
H+(aq) + A(aq) HA(aq)
167

Common Ion Effect
Adding a salt, NaA containing the anion, A(aq) which is

the conjugate base of the acid (the common ion),
shifts the position of equilibrium to the left, lowering
the H3O+ ion concentration

This causes the pH to be higher than the pH of the
acid solution
168

Common Ion Effect
Consider a solution of acetic acid:
H2O(l) + HC2H3O2 (aq) C2H3O2-(aq) + H3O+(aq)

If acetate ion is added to the solution, Le Chtelier
says the equilibrium will shift to the left.
169

Example 25
In which of these solutions will HNO2 ionize less than it does in pure
water?
a. 0.1 M KNO3
b. 0.1 M NaCl
c. 0.1 M NaOH
d. 0.1 NaNO2
A formic acid solution has a pH of 3.25. Which of these substances
will raise the pH of the solution upon addition? Explain
a. HCl
b. NaBr
c. NaCHO2
d. KCl
170

Answer
In which of these solutions will HNO2 ionize less than it does in pure
water?
Answer: The only solution that HNO2 will ionize less in is (d). It is the
only solution that generates a common ion NO2- with nitrous acid
A formic acid solution has a pH of 3.25. Which of these substances
will raise the pH of the solution upon addition? Explain
Answer: Formic acid is HCHO2 which dissociates to H+ and CHO2-.

The only solution that generates a common ion (CHO2-) with
formic acid is (c) NaCHO2
171

Example 26
What is the pH of a buffer that is 0.100 M HC2H3O2 and
0.100 M NaC2H3O2?
write the reaction
for the acid with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[H3O+] from water
is 0
HC2H3O2 + H2O C2H3O2 + H3O+
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.100
0.100
172

Answer
in terms of x
sum the columns to
concentrations in
terms of x

initial
change
[HA]
[A]
[H3O+]
0.100
0.100
+x
equilibrium 0.100 x 0.100 + x
+x
x
substitute into the

expression
173

Answer
Ka for HC2H3O2 = 1.8 x 105
determine the value

of Ka
because Ka is very
small, approximate
the [HA]eq = [HA]init
and [A]eq = [A]init ,
then solve for x
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.100
0.100
+x
+x
0.100
0.100
174

Answer
check if the
approximatio
n is valid by
seeing if x <
5% of
[HC2H3O2]init
Ka for HC2H3O2 = 1.8 x 105
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.100
0.100
+x
+x
0.100
0.100
x = 1.8 x 105
175

Answer
substitute x
into the
equilibrium
concentrati
on
definitions
and solve
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.100
0.100
+x
+x
0.100
0.100
1.8E-5
x = 1.8 x 105
176

Answer
substitute
[H3O+] into the
formula for pH
and solve
[HA]
[A]
[H3O+]
0.100
initial
x
change
equilibrium 0.100
0.100
+x
+x
0.100
1.8E5
177

Example 27
What is the pH of a buffer that is 0.14 M HF

(pKa = 3.15) and 0.071 M KF?
write the reaction
for the acid with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[H3O+] from water
is 0
HF + H2O F + H3O+
initial
[HA]
[A]
[H3O+]
0.14
0.071
change
equilibrium
178

Answer
represent the
change in the
concentrations
in terms of x
sum the
columns to find
the equilibrium
concentrations
in terms of x
substitute into
the equilibrium
constant
expression
HF + H2O F + H3O+
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.14
0.071
x
0.14 x
+x
0.071 + x
+x
x
179

Answer
Ka for HF = 7.0 x 104

determine the
value of Ka
because Ka is
very small,
approximate the
[HA]eq = [HA]init
and [A]eq =
[A]init solve for x
initial
change
equilibrium
pKa for HF = 3.15
[HA]
[A]
[H3O+]
0.14
0.071
+x
+x
0.012
0.100
180

Answer
Ka for HF = 7.0 x 104

check if the
approximation
initial
is valid by
seeing if
x change
< 5% of
equilibrium
[HC2H3O2]init
[HA]
[A]
[H3O+]
0.14
0.071
+x
+x
0.14
0.071
x = 1.4 x 103
181

Answer
substitute x
into the
initial
equilibrium
concentration change
definitions
equilibrium
and solve
[HA]
[A]
[H3O+]
0.14
0.071
+x
+x
0.14
0.072
1.4E-3
x = 1.4 x 103
182

Answer
substitute
[H3O+] into
the formula
for pH and
solve
initial
change
equilibrium
[HA]
[A]
[H3O+]
0.14
0.071
+x
+x
0.14
0.072
1.4E3
183

Exercise 21
What is the pH of a buffer that is 0.12 M in lactic acid

CH3CH(OH)COOH, and 0.10 M in sodium lactate
CH3CH(OH)COONa. For lactic acid, Ka = 1.4 x 10-4
184

Henderson-Hasselbalch Equation
Calculating the pH of a buffer solution can be
simplified by using an equation derived from the Ka
expression called the Henderson-Hasselbalch
Equation
The equation calculates the pH of a buffer from the
pKa and initial concentrations of the weak acid and
salt of the conjugate base
as long as the x is small approximation is valid
185

Deriving the Equation
186

Example 28
What is the pH of a buffer that is 0.050 M

HC7H5O2 and 0.150 M NaC7H5O2?
187

Answer
assume the [HA] and
[A] equilibrium
concentrations are the
same as the initial

Ka for HC7H5O2 = 6.5 x 105
substitute into the

HendersonHasselbalch Equation
check the x is small

approximation
188

Example 29
What is the pH of a buffer that is 0.14 M HF

(pKa = 3.15) and 0.071 M KF?
189

Answer
find the pKa from the
given Ka
HF + H2O F + H3O+
assume the [HA]

and [A] equilibrium
concentrations are
the same as the
initial
substitute into the

HendersonHasselbalch
equation
check the x is
small
approximation
190

Henderson-Hasselbalch Equation for Basic
Buffers
The Henderson-Hasselbalch equation is written for a

chemical reaction with a weak acid reactant and its
conjugate base as a product
The chemical equation of a basic buffer is written with
a weak base as a reactant and its conjugate acid as a
product
B: + H2O H:B+ + OH
To apply the Henderson-Hasselbalch equation, the

chemical equation of the basic buffer must be looked
at like an acid reaction
H:B+ + H2O B: + H3O+
this does not affect the concentrations, just the way we are
191
looking at the reaction

Relationship between pKa and pKb
Just as there is a relationship between the Ka of

a weak acid and Kb of its conjugate base,
there is also a relationship between the pKa of
a weak acid and the pKb of its conjugate base
Ka Kb = Kw = 1.0 x 1014
log(Ka Kb) = log(Kw) = 14
log(Ka) + log(Kb) = 14
pKa + pKb = 14
192
Henderson-Hasselbalch Equation for Basic

Buffers
The Henderson-Hasselbalch equation is written

for a chemical reaction with a weak acid reactant
and its conjugate base as a product
The chemical equation of a basic buffer is written
with a weak base as a reactant and its conjugate
acid as a product
B: + H2O H:B+ + OH
We can rewrite the Henderson-Hasselbalch
equation for the chemical equation of the basic
buffer in terms of pOH

Example 30
What is the pH of a buffer that is 0.50 M NH3

(pKb = 4.75) and 0.20 M NH4Cl?
194

Answer
find the pKa of the

conjugate acid (NH4+)
from the given Kb
assume the [B] and
[HB+] equilibrium
concentrations are the
same as the initial
substitute into the
HendersonHAsselbalch equation
check the x is small
approximation
NH3 + H2O NH4+ + OH
195

Exercise 22
Find the pH of a buffer that consists of 0.50 M

methylamine (CH3NH2) and 0.60 M CH3NH3Cl (pKb of
CH3NH2 = 3.35)
196

Buffering Effectiveness
A good buffer should be able to neutralize moderate
amounts of added acid or base
However, there is a limit to how much can be added
before the pH changes significantly
The buffering capacity is the amount of acid or base

a buffer can neutralize
The buffering range is the pH range the buffer can be
effective
The effectiveness of a buffer depends on two factors
(1) the relative amounts of acid and base, and (2) the
absolute concentrations of acid and base
197

Buffering Capacity
a concentrated
buffer can
neutralize more
added acid or
base than a
dilute buffer
198

Effectiveness of Buffers
A buffer will be most effective when the

[base]:[acid] = 1
equal concentrations of acid and base
A buffer will be effective when
0.1 < [base]:[acid] < 10
A buffer will be most effective when the [acid]
and the [base] are large
199

Buffering Range
We have said that a buffer will be effective when
0.1 < [base]:[acid] < 10
Substituting into the Henderson-Hasselbalch equation
we can calculate the maximum and minimum pH at
which the buffer will be effective
Lowest pH
Highest pH
Therefore, the effective pH range of a buffer is pKa 1
When choosing an acid to make a buffer, choose one whose is pKa

closest to the pH of the buffer
200

Example 31
Which of the following acids would be the best choice
to combine with its sodium salt to make a buffer with
pH 4.25?
Chlorous acid, HClO2
Nitrous acid, HNO2

Formic acid, HCHO2
Hypochlorous acid, HClO
pKa = 1.95
pKa = 3.34
pKa = 3.74
pKa = 7.54
The pKa of HCHO2 is closest to the desired pH of the

buffer, so it would give the most effective buffering range
201

Answer
What ratio of NaCHO2 : HCHO2 would be required to
make a buffer with pH 4.25?
Formic acid, HCHO2, pKa = 3.74
To make a buffer with pH

4.25, you would use 3.24
times as much NaCHO2 as
HCHO2
202

Example 32
What ratio of NaC7H5O2 : HC7H5O2 would be required to
make a buffer with pH 3.75?
Benzoic acid, HC7H5O2, pKa = 4.19
to make a buffer with pH

3.75, you would use 0.363
times as much NaC7H5O2 as
203
HC7H5O2

Buffering Capacity
Buffering capacity is the amount of acid or base that
can be added to a buffer without causing a large
change in pH
The buffering capacity increases with increasing
absolute concentration of the buffer components
As the [base]:[acid] ratio approaches 1, the ability of
the buffer to neutralize both added acid and base
improves
Buffers that need to work mainly with added acid
generally have [base] > [acid]
Buffers that need to work mainly with added base
generally have [acid] > [base]
204
TOPIC
4.6 ACID-BASE TITRATION
CURVE
205
4.6 Acid-base Titration Curve

Titration
In an acid-base titration, a solution of unknown
concentration (titrant) is slowly added to a solution of
known concentration from a burette until the reaction
is complete
when the reaction is complete we have reached
the endpoint of the titration
An indicator may be added to determine the endpoint
an indicator is a chemical that changes color when
the pH changes
When the moles of H3O+ = moles of OH, the titration
has reached its equivalence point
206

Titration
207

Titration Curve
A plot of pH vs. amount of added titrant
The inflection point of the curve is the equivalence
point of the titration
Prior to the equivalence point, the known solution in
the flask is in excess, so the pH is closest to its pH
The pH of the equivalence point depends on the pH of
the salt solution
equivalence point of neutral salt, pH = 7
equivalence point of acidic salt, pH < 7
equivalence point of basic salt, pH > 7
Rapid pH change from about pH = 3 to pH = 11
208

Titration Curve
Unknown Strong Base Added to Strong Acid
209

Titration Curve for Strong Acid and Strong Base
Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
Because the solutions
are equal
concentration, and 1:1
stoichiometry, the
equivalence point is at
equal volumes
Before Equivalence
(excess acid)
After Equivalence
(excess base)
Equivalence Point
equal moles of
HCl and NaOH
pH = 7.00
210

Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
Initial pH = log(0.100) = 1.00
Initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 103
Before equivalence point
added 5.0 mL NaOH
5.0 x 104 mole NaOH added

mols before
mols change
mols end
molarity, new
HCl
NaCl
NaOH
2.50E-3
5.0E-4

HCl
NaCl
NaOH
mols before
2.50E-3
5.0E-4
mols change
5.0E-4
+5.0E-4
5.0E-4
mols end
2.00E-3
5.0E-4
molarity, new

HCl
NaCl
NaOH
mols before
2.50E-3
5.0E-4
mols change
5.0E-4
+5.0E-4
5.0E-4
mols end
2.00E-3
5.0E-4
molarity, new
0.0667
0.017

pHs after adding 10.0, 15.0 and 20.0 mL of NaOH.
We can calculate pH at each points in the same way
that we calculated the pH at 5 mL point.
Volume (mL)
pH10.0
10.0
15.0
20.0
1.37
1.60
1.95

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(aq)
To reach equivalence, the added moles NaOH = initial
moles of HCl = 2.50 x 103 moles
At equivalence, we have 0.00 mol HCl and 0.00 mol
NaOH left over
Because the NaCl is a neutral salt, the pH at
equivalence = 7.00


At equivalence point
added 25.0 mL NaOH

HCl
NaCl
NaOH
mols before 2.50E-3

0
2.5E-3
mols change 2.5E-3 +2.5E-3 2.5E-3
mols end
2.5E-3
molarity, new
0.050


After equivalence point
added 30.0 mL NaOH

0.100 mol NaOH
1L
moles added NaOH
L of added NaOH

mols before
mols change
HCl
NaCl
NaOH
2.50E-3
3.0E-3
2.5E-3 +2.5E-3 2.5E-3
mols end
2.5E-3
5.0E-4
molarity, new
0.045
0.0091

added
30.0
5.0
10.0
25.0
mL
mLNaOH
NaOH
25.0 mL35.0
0.100
M
HCl
0.00050
0.00100
0.00200
0.00150
equivalence
mol point
NaOH
0.00250
HCl
pH = 12.22
11.96
1.18
1.37
7.00
1.00
added 15.0
40.0 mL NaOH
0.00150 mol HCl
0.00100
NaOH
pH = 1.60
12.36
added 20.0
50.0 mL NaOH
0.00250 mol HCl
0.00050
NaOH
pH = 1.95
12.52

Example 33 Calculate the pH of the solution that
results when 10.0 mL of 0.15 M NaOH is added to 50.0
mL of 0.25 M HNO3
Example 34 Calculate the pH of the solution that
results when 100.0 mL of 0.15 M NaOH is added to
50.0 mL of 0.25 M HNO3

Answer
HNO3(aq) + NaOH(aq) NaNO3(aq) + H2O(l)

Initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 102
Before equivalence point added 10.0 mL NaOH
mols before
HNO3
NaNO3
NaOH
1.25E-2
1.5E-3
mols cHAnge 1.5E-3 +1.5E-3 1.5E-3

mols end
1.1E-3
1.5E-3
molarity, new
0.018
0.025

Answer
HNO3(aq) + NaOH(aq) NaNO3(aq) + H2O(l)
Initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 102
After equivalence point added 100.0 mL NaOH
HNO3
NaNO3
NaOH
mols before
1.25E-2
1.5E-2
mols change
cHAnge
1.25E-2 +1.25E-2 1.25E-2
mols end
1.25E-2
0.0025
molarity, new
0.0833
0.017

Titration of a Strong Base with a Strong Acid
If the titration is run so

that the acid is in the
burette and the base is
in the flask, the titration
curve will be the
reflection of the one
just shown

Titration of a Weak Acid with a Strong Base
Titrating a weak acid with a strong base results in
differences in the titration curve at the equivalence
point and excess acid region
The initial pH is determined using the Ka of the weak
acid
The pH in the excess acid region is determined as you
would determine the pH of a buffer
The pH at the equivalence point is determined using
the Kb of the conjugate base of the weak acid
The pH after equivalence is dominated by the excess
strong base
the basicity from the conjugate base anion is
negligible

Titrating Weak Acid with a Strong Base
The initial pH is that of the weak acid solution
calculate like a weak acid equilibrium problem
e.g 15 and 16
Before the equivalence point, the solution becomes a
buffer
Half-neutralization pH = pKa
At equivalence point, pH 9
and rapid change of pH from about pH = 7 to pH = 11

Titration of 25 mL of 0.100 M HCHO2 with 0.100 M NaOH
HCHO2(aq) + NaOH(aq) NaCHO2(aq) + H2O(aq)
Initial pH
[HCHO2] [CHO2] [H3O+]
initial
change
0.100
0.000
+x
+x
equilibrium 0.100 x
Ka = 1.8 x 104

HCHO2(aq) + NaOH(aq) NaCHO2 (aq) + H2O(aq)
Initial mol of HCHO2 = 0.0250 L x 0.100 mol/L = 2.50 x 103
Before equivalence
added 5.0 mL NaOH
HA
OH
mols
before
2.50E-3
mols
added
5.0E-4
mols after
2.00E-3 5.0E-4
Titrating Weak Acid with a

Strong Base
25.0
added 30.0
5.0 mL
mLNaOH
NaOH
10.0
initial HCHO2 solution
equivalence
point
0.00200
0.00050
molmL
NaOH
0.00150
HCHO
2xs
added
35.0
NaOH
0.00250 mol HCHO
2
0.00250
mol
CHO
pH
=
3.14
11.96
3.56
2
0.00100
mol NaOH xs
pH = 2.37
[CHO
2 ]init = 0.0500 M
pH = 12.22
[OH ]eq = 1.7 x 106
added
12.5 mL NaOH
pH
= 8.23
added
40.0 mL NaOH
0.00125 mol HCHO2
0.00150 mol NaOH xs
pH = 3.74 = pKa
pH = 12.36
half-neutralization
added 50.0
15.0 mL NaOH
0.00100 mol NaOH
0.00250
HCHO2xs
pH = 12.52
3.92
added 20.0 mL NaOH
0.00050 mol HCHO2
pH = 4.34

The initial pH is that of the weak acid solution
calculate like a weak acid equilibrium Example 15
& 16
Before the equivalence point, the solution

becomes a buffer
calculate mol HAinit and mol Ainit using reaction
stoichiometry
calculate pH with Henderson-Hasselbalch using
mol HAinit and mol Ainit
Half-neutralization pH = pKa

At the equivalence point, the mole HA = mol Base, so the
resulting solution has only the conjugate base anion in it
before equilibrium is established
mol A = original mole HA
calculate the volume of added base as you did in Example
4.8
[A]init = mol A/total liters
calculate like a weak base equilibrium problem
e.g., 21
Beyond equivalence point, the OH is in excess

[OH] = mol MOH xs/total liters
[H3O+][OH]=1 x 1014

Example 35: A 40.0 mL sample of 0.100 M HNO2 is titrated
with 0.200 M KOH. Calculate the volume of KOH at the
equivalence point.
write an equation
for the reaction for
B with HA
use stoichiometry
to determine the
volume of added B
HNO2 + KOH NO2 + H2O

Example 36 : A 40.0 mL sample of 0.100 M HNO2 is titrated with
0.200 M KOH. Calculate the pH after adding 5.00 mL KOH.
write an
equation for the
reaction for B
with HA
determine the
moles of HAbefore
& moles of
added B
make a
stoichiometry
table and
determine the
moles of HA in
excess and
moles A made
mols before
mols added
mols after
HNO2
NO2
OH
0.00400
0.00100
0.00300
0.00100

HNO2 + H2O NO2 + H3O+
Table 15.5 Ka = 4.6 x 104
write an
equation for
the reaction of
HA with H2O
determine Ka
and pKa for HA
use the
equation to
determine the
pH
HNO2
NO2
OH
mols before
0.00400
mols added
0.00100
0.00300
0.00100
mols after

Example 37: A 40.0 mL sample of 0.100 M HNO2 is titrated
with 0.200 M KOH. Calculate the pH at the half-equivalence
point.
write an equation
for the reaction for
B with HA
determine the
moles of HAbefore &
moles of added B
make a
stoichiometry
table and
determine the
moles of HA in
excess and moles
A made
at Half-equivalence, moles KOH = mole

HNO2
mols before
mols added
mols after
HNO2
NO2
OH
0.00400
0.00200 0.00200
0.00200
0

Answer
HNO2 + H2O NO2 + H3O+
write an
equation for the
reaction of HA
with H2O
Table 15.5 Ka = 4.6 x 10-4
determine Ka
and pKa for HA
use the
equation to
determine the
pH
HNO2
NO2
OH
mols before
0.00400
mols added
0.00200
0.00200
0.00200
mols after

Titrating Weak Base with a Strong Acid
At equivalence point, pH 5
Rapid change of pH range between pH = 3 to pH = 7

Titration Curve of a Weak Base with a Strong Acid

Example 38 : Titration of 25.0 mL of 0.10 M NH3 with 0.10
M HCl. Calculate the initial pH of the NH3(aq)

Answer
NH3(aq) + HCl(aq) NH4Cl(aq)
Initial: NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
[HCl] [NH4+]
[NH3]
initial
0.10
cHAnge
+x
+x
equilibrium
0.10x
pKb = 4.75
Kb = 104.75 = 1.8 x 105

Example 39 :Titration of 25.0 mL of 0.10 M NH3 (pKb =
4.75) with 0.10 M HCl. Calculate the pH of the solution at
equivalence.

Answer
Initial mol of NH3 = 0.0250 L x 0.100 mol/L = 2.50 x 103
At equivalence mol NH3 = mol HCl = 2.50 x 103
NH3
NH4Cl
HCl
mols before
2.50E-3
2.5E-3
mols change
2.5E-3 +2.5E-3 2.5E-3
mols end
2.5E-3
molarity, new
0.050
added 25.0 mL HCl

Answer
at equivalence [NH4Cl] = 0.050 M
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
[NH3]
[NH4+] [H3O+]
initial
0.050
change
+x
+x
equilibrium
0.050x
TOPIC
4.7 INDICATORS
4.7 Indicators
Many dyes change color depending on the pH of the
solution
These dyes are weak acids, establishing an
equilibrium with the H2O and H3O+ in the solution
HInd(aq) + H2O(l) Ind(aq) + H3O+(aq)
The color of the solution depends on the relative

concentrations of Ind:HInd
when Ind:HInd 1, the color will be mix of the colors of Ind
and HInd
when Ind:HInd > 10, the color will be mix of the colors of Ind
when Ind:HInd < 0.1, the color will be mix of the colors of
Hind
4.7 Indicators
Monitoring a Titration with an Indicator
For most titrations, the titration curve shows a very
large change in pH for very small additions of titrant
near the equivalence point
An indicator can therefore be used to determine the
endpoint of the titration if:
pKa of indicator pH at equivalence point
it changes color within the same range as the rapid change in
pH
4.7 Indicators
Acid-Base Indicators
4.7 Indicators
Acid-Base Indicators
4.7 Indicators
Phenolphthalein
4.7 Indicators
Methyl Red
H
C
(CH3)2N
H
C
H
C
C
C
H
(CH3)2N
OH-
CH
C
C
H
H
C
H
C
NaOOC
H
C
C
C
H
N
H
C
H
H3O+
H
C
H
C
C
H
CH
C
NaOOC
C
H
The titration curve of a strong acid with a strong base.
252
4.7 Indicators
Example 40
Which indicator or indicators listed in Table 16.1 would you use for the
acid-base titrations shown in
(a)
4.7 Indicators
Example
(b)
4.7 Indicators
Example
(c)
4.7 Indicators
Answer
(a) Near the equivalence point, the pH of the solution changes
abruptly from 4 to 10. Therefore, all the indicators except thymol
blue, bromophenol blue, and methyl orange are suitable for use in
the titration.
(b) Here the steep portion covers the pH range between 7 and 10;
therefore, the suitable indicators are cresol red and
phenolphthalein.
(c) Here the steep portion of the pH curve covers the pH range
between 3 and 7; therefore, the suitable indicators are
bromophenol blue, methyl orange, methyl red, and chlorophenol
blue.
End of Chapter 3
Please Read Chapter 4
Thank You
Question!
257

Chm096 Chapter 4 Acids and Bases

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FOUNDATION CHEMISTRY II

Definitions Acids and Bases

Strength of Acids and Bases

pH- A Measure of Acidity

The Acid-Base Properties of Ions and Salts

Acid Base Titration Curve

Definitions Acids and Bases

CaCO3 + 2 HCl CaCl2 + CO2 + H2O

Definitions Acids and Bases

Binary acids have acid hydrogens attached to a

Oxy acids have acid hydrogens attached to an

Definitions Acids and Bases

Carboxylic acids have

Definitions Acids and Bases

Also known as alkalis

Definitions Acids and Bases

Most ionic bases contain OH ions

Definitions Acids and Bases

An acid is a substance that, when dissolved in water,

Definitions Acids and Bases

NaOH dissociates in water,

Definitions Acids and Bases

Instead, they react with water molecules to produce

Definitions Acids and Bases

Arrhenius Acid-Base Reaction

Definitions Acids and Bases

Definitions Acids and Bases

Limitations of Arrhenius Acid-Base Theory

Does not explain why molecular substances, such as

Definitions Acids and Bases

In a Brnsted-Lowry acidbase reaction,

Definitions Acids and Bases

any material that has H can potentially be a Brnsted-Lowry acid

When HCl dissolves in water, the HCl is the acid because

HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)

Definitions Acids and Bases

When NH3 dissolves in water, the NH3(aq) is the base

NH3(aq) + H2O(l) NH4+(aq) + OH(aq)

Definitions Acids and Bases

Water acts as base, accepting H+ from HCl

Definitions Acids and Bases

Brnsted-Lowry Acid-Base Reactions

Definitions Acids and Bases

Conjugate Acids and Bases

For the reaction: HA + :B :A + HB+

Definitions Acids and Bases

Conjugate Acids and Bases

Definitions Acids and Bases

Conjugate Acids and Bases

NH3 and NH4+ constitute a

Definitions Acids and Bases

Write the formula for the conjugate acid of the following

Definitions Acids and Bases

Write the formula for the conjugate base of the following

because CO32 does not have an H,

Definitions Acids and Bases

Identify the Brnsted-Lowry acids and bases, and their

HSO4(aq) + HCO3(aq) SO42(aq) +

HCO3 (aq) + H2O

Definitions Acids and Bases

Write the equations for the following species react with

Definitions Acids and Bases

Comparing Arrhenius and Brnsted-Lowry Theory

NaOH(aq) Na+(aq) + OH(aq)