Chapter 6

by

Dr. Nor Nadiah Mohamad Yusof

Have a sour taste. Vinegar owes its taste to acetic acid.

Citrus fruits contain citric acid.
React with certain metals to produce
hydrogen gas.
React with carbonates and bicarbonates
to produce carbon
dioxide gas

Bases

Have a bitter taste.

Feel slippery. Many soaps contain bases.

Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

A Brnsted acid is a proton donor

A Brnsted base is a proton acceptor

base
base

acid

acid

base

acid

conjugate
acid

conjugate
base

Acid-Base Properties of Water

H+ (aq) + OH- (aq)

H2O (l)

autoionization of water
H

O
H

+ H

[H

O
H

+ H

base
H2O + H2O
acid

conjugate
acid
H3O+ + OHconjugate
base

The Ion Product of Water

H2O (l)

H+ (aq) + OH- (aq)

[H+][OH-]
Kc =
[H2O]

[H2O] = constant

Kc[H2O] = Kw = [H+][OH-]
The ion-product constant (Kw) is the product of the molar
concentrations of H+ and OH- ions at a particular temperature.
Solution Is
At 250C
Kw = [H+][OH-] = 1.0 x 10-14

[H+] = [OH-]

neutral

[H+] > [OH-]

acidic

[H+] < [OH-]

basic

What is the concentration of OH- ions in a HCl solution

whose hydrogen ion concentration is 1.3 M?
Kw = [H+][OH-] = 1.0 x 10-14
[H+] = 1.3 M

-14
K
1
x
10
w
-15 M
=
=
7.7
x
10
[OH-] =
[H+]
1.3

pH A Measure of Acidity
pH = -log [H+]

[H+] = [OH-]

At 250C
[H+] = 1 x 10-7

pH = 7

acidic

[H+] > [OH-]

[H+] > 1 x 10-7

pH < 7

basic

[H+] < [OH-]

[H+] < 1 x 10-7

pH > 7

Solution Is
neutral

pH

[H+]

pOH = -log [OH-]

[H+][OH-] = Kw = 1.0 x 10-14

-log [H+] log [OH-] = 14.00

pH + pOH = 14.00

The pH of rainwater collected in a certain region of the

northeastern United States on a particular day was 4.82.
What is the H+ ion concentration of the rainwater?
pH = -log [H+]
[H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M
The OH- ion concentration of a blood sample is 2.5 x 10-7
M. What is the pH of the blood?
pH + pOH = 14.00
pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60
pH = 14.00 pOH = 14.00 6.60 = 7.40

Strong Electrolyte 100% dissociation

NaCl (s)

H 2O

Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated

CH3COOH

CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

HCl (aq) + H2O (l)

H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l)

H3O+ (aq) + NO3- (aq)

HClO4 (aq) + H2O (l)

H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l)

H3O+ (aq) + HSO4- (aq)

Weak Acids are weak electrolytes

H3O+ (aq) + F- (aq)

HF (aq) + H2O (l)

HNO2 (aq) + H2O (l)

H3O+ (aq) + NO2- (aq)

HSO4- (aq) + H2O (l)

H3O+ (aq) + SO42- (aq)

H2O (l) + H2O (l)

H3O+ (aq) + OH- (aq)

Strong Bases are strong electrolytes

NaOH (s)
KOH (s)

H 2O
H2O

Ba(OH)2 (s)

Na+ (aq) + OH- (aq)

K+ (aq) + OH- (aq)

H 2O

Ba2+ (aq) + 2OH- (aq)

Weak Bases are weak electrolytes

F- (aq) + H2O (l)
NO2- (aq) + H2O (l)

OH- (aq) + HF (aq)

OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:

The conjugate base of a strong acid has no measurable

strength.

H3O+ is the strongest acid that can exist in aqueous

solution.

The OH- ion is the strongest base that can exist in aqeous
solution.

Strong Acid

Weak Acid

What is the pH of a 2 x 10-3 M HNO3 solution?

HNO3 is a strong acid 100% dissociation.
Start 0.002 M
HNO3 (aq) + H2O (l)
End 0.0 M

0.0 M
0.0 M
H3O+ (aq) + NO3- (aq)
0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7

What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?
Ba(OH)2 is a strong base 100% dissociation.
Start 0.018 M
Ba(OH)2 (s)
End 0.0 M

0.0 M
0.0 M
Ba2+ (aq) + 2OH- (aq)
0.018 M 0.036 M

pH = 14.00 pOH = 14.00 + log(0.036) = 12.56

Weak Acids (HA) and Acid Ionization Constants

HA (aq) + H2O (l)
HA (aq)

H3O+ (aq) + A- (aq)

H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]
Ka is the acid ionization constant

Ka

weak acid
strength

What is the pH of a 0.5 M HF solution (at 250C)?

+][F-]
[H
= 7.1 x 10-4
Ka =
HF (aq)
H+ (aq) + F- (aq)
[HF]
HF (aq)
Initial (M)
Change (M)
Equilibrium (M)

0.50

0.00

0.00

-x

+x

+x

0.50 - x

x2
= 7.1 x 10-4
Ka =
0.50 - x
Ka

H+ (aq) + F- (aq)

x2
= 7.1 x 10-4
0.50

[H+] = [F-] = 0.019 M

[HF] = 0.50 x = 0.48 M

Ka << 1

0.50 x 0.50

x2 = 3.55 x 10-4

x = 0.019 M

pH = -log [H+] = 1.72

When can I use the approximation?

Ka << 1

0.50 x 0.50

When x is less than 5% of the value from which it is subtracted.

x = 0.019

0.019 M
x 100% = 3.8%
0.50 M

Less than 5%
Approximation ok.

What is the pH of a 0.05 M HF solution (at 250C)?

x2
Ka
= 7.1 x 10-4 x = 0.006 M
0.05
More than 5%
0.006 M
x 100% = 12%
0.05 M
Approximation not ok.
Must solve for x exactly using quadratic equation or method of
successive approximation.

Solving weak acid ionization problems:

1. Identify the major species that can affect the pH.

In most cases, you can ignore the autoionization of

water.

Ignore [OH-] because it is determined by [H+].

2. Use ICE to express the equilibrium concentrations in terms

of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve for x
by the approximation method. If approximation is not valid,
solve for x exactly.
4. Calculate concentrations of all species and/or pH of the
solution.

What is the pH of a 0.122 M monoprotic acid whose

Ka is 5.7 x 10-4?
HA (aq)

Initial (M)
Change (M)
Equilibrium (M)

0.122

0.00

0.00

-x

+x

+x

0.122 - x

x2
= 5.7 x 10-4
Ka =
0.122 - x
Ka

H+ (aq) + A- (aq)

x2
= 5.7 x 10-4
0.122

0.0083 M
x 100% = 6.8%
0.122 M

Ka << 1

0.122 x 0.122

x2 = 6.95 x 10-5

x = 0.0083 M

More than 5%
Approximation not ok.

x2
= 5.7 x 10-4
Ka =
0.122 - x
ax2 + bx + c =0
x = 0.0081
HA (aq)
Initial (M)
Change (M)

Equilibrium (M)

x2 + 0.00057x 6.95 x 10-5 = 0

-b b2 4ac
x=
2a
x = - 0.0081
H+ (aq) + A- (aq)

0.122

0.00

0.00

-x

+x

+x

0.122 - x

[H+] = x = 0.0081 M

pH = -log[H+] = 2.09

Ionized acid concentration at equilibrium

percent ionization =
x 100%
Initial concentration of acid

For a monoprotic acid HA

Percent ionization =

[H+]

[HA]0

x 100%

[HA]0 = initial concentration

Weak Bases and Base Ionization Constants

NH3 (aq) + H2O (l)

NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]
Kb is the base ionization constant
Kb

weak base
strength

Solve weak base problems like weak acids

except solve for [OH-] instead of [H+].

Ionization Constants of Conjugate Acid-Base Pairs

HA (aq)

A- (aq) + H2O (l)

H2O (l)

H+ (aq) + A- (aq)

OH- (aq) + HA (aq)

H+ (aq) + OH- (aq)

Ka

Kb
Kw

KaKb = Kw
Weak Acid and Its Conjugate Base
Kw
Ka =
Kb

Kw
Kb =
Ka

Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water
A Brnsted acid is a proton donor
A Lewis acid is a substance that can accept a pair of electrons
A Lewis base is a substance that can donate a pair of electrons

H+ + OH
acid base

H+ +
acid

H
N H

H
base

H O H

+
H N H
H

Lewis Acids and Bases

F B

N H

acid

base

F
F B
F

H
N H
H

No protons donated or accepted!

The common ion effect is the shift in equilibrium caused by the

addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses

the ionization of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s)

Na+ (aq) + CH3COO- (aq)

CH3COOH (aq)

H+ (aq) + CH3COO- (aq)

common
ion

Consider mixture of salt NaA and weak acid HA.

NaA (s)

Na+ (aq) + A- (aq)

HA (aq)

H+ (aq) + A- (aq)

[H+]

Ka [HA]
=
[A-]

-log [H+] = -log Ka - log

[HA]
[A-]

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

[A-]
pH = pKa + log
[HA]

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

Henderson-Hasselbalch
equation
[conjugate base]
pH = pKa + log
[acid]

pKa = -log Ka

What is the pH of a solution containing 0.30 M HCOOH

and 0.52 M HCOOK?
Mixture of weak acid and conjugate base!
HCOOH (aq)
Initial (M)

Change (M)
Equilibrium (M)
Common ion effect
0.30 x 0.30
0.52 + x 0.52
HCOOH pKa = 3.77

H+ (aq) + HCOO- (aq)

0.30

0.00

0.52

-x

+x

+x

0.30 - x

0.52 + x

[HCOO-]
pH = pKa + log
[HCOOH]
[0.52]
= 4.01
pH = 3.77 + log
[0.30]

A buffer solution is a solution of:

1. A weak acid or a weak base and
2. The salt of the weak acid or weak base

Both must be present!

A buffer solution has the ability to resist changes in pH upon
the addition of small amounts of either acid or base.
Consider an equal molar mixture of CH3COOH and CH3COONa
Add strong acid
H+ (aq) + CH3COO- (aq)
Add strong base
OH- (aq) + CH3COOH (aq)

CH3COOH (aq)
CH3COO- (aq) + H2O (l)

Which of the following are buffer systems? (a) KF/HF

(b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution

(b) HBr is a strong acid

not a buffer solution
(c) CO32- is a weak base and HCO3- is it conjugate acid
buffer solution

Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer

system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
NH4+ (aq)
[NH3]
pH = pKa + log
[NH4+]
start (moles)
end (moles)

H+ (aq) + NH3 (aq)

pKa = 9.25

0.029
0.001
NH4+ (aq) + OH- (aq)
0.028
0.0

pH = 9.25 + log

[0.30]
[0.36]

= 9.17

0.024
H2O (l) + NH3 (aq)
0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

[NH4

+]

0.028
0.025
=
[NH3] =
0.10
0.10

[0.25]
pH = 9.25 + log
= 9.20
[0.28]

Maintaining the pH of Blood

Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.
Equivalence point the point at which the reaction is complete

Indicator substance that changes color at (or near) the

equivalence point
Slowly add base
to unknown acid
UNTIL
The indicator
changes color
(pink)

Strong Acid-Strong Base Titrations

NaOH (aq) + HCl (aq)
OH- (aq) + H+ (aq)

H2O (l) + NaCl (aq)

H2O (l)

0.10 M NaOH added to 25 mL of 0.10 M HCl

Weak Acid-Strong Base Titrations

CH3COOH (aq) + NaOH (aq)

CH3COONa (aq) + H2O (l)

CH3COOH (aq) + OH- (aq)

CH3COO- (aq) + H2O (l)

At equivalence point (pH > 7):

CH3COO- (aq) + H2O (l)

OH- (aq) + CH3COOH (aq)

Strong Acid-Weak Base Titrations

HCl (aq) + NH3 (aq)
H+ (aq) + NH3 (aq)

NH4Cl (aq)
NH4Cl (aq)

At equivalence point (pH < 7):

NH4+ (aq) + H2O (l)

NH3 (aq) + H+ (aq)

Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M

NaOH solution. What is the pH at the equivalence point ?
start (moles)

0.01
0.01
HNO2 (aq) + OH- (aq)
0.0
0.0

NO2- (aq) + H2O (l)

end (moles)
0.01
0.01
Final volume = 200 mL
[NO2-] =
= 0.05 M
0.200
NO2- (aq) + H2O (l)
OH- (aq) + HNO2 (aq)
Initial (M)
Change (M)

0.05

0.00

0.00

-x

+x

+x

Equilibrium (M) 0.05 - x

[OH-][HNO2]
x2
-11
=
2.2
x
10
Kb =
=
[NO2-]
0.05-x

pOH = 5.98

0.05 x 0.05 x 1.05 x 10-6 = [OH-]

pH = 14 pOH = 8.02

Acid-Base Indicators
HIn (aq)
H+ (aq) + In- (aq)
[HIn]
10 Color of acid (HIn) predominates
[In ]
[HIn]
-) predominates
Color
of
conjugate
base
(In

10
[In-]

The titration curve of a strong acid with a strong base.

Which indicator(s) would you use for a titration of HNO2

with KOH ?
Weak acid titrated with strong base.
At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein