Acids and Bases

Chapter 15

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 Acids

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.

4.3
Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

4.3
 A Brnsted acid is a proton donor
A Brnsted base is a proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base

15.1
 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

autoionization of water

+ + H -
H O + H O [ H O H ] O
H H H

conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
base

15.2
 The Ion Product of Water

[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]

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
[H+] = [OH-] neutral
At 250C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic

15.2
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

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

15.2
 pH A Measure of Acidity

pH = -log [H+]

Solution Is At 250C
neutral [H+] = [OH-] [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

pH [H+]

15.3
 pOH = -log [OH-]

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

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

pH + pOH = 14.00

15.3
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

15.3
 Strong Electrolyte 100% dissociation
H2O
NaCl (s) 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)
15.4
Weak Acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

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

H2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

15.4
Weak Bases are weak electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) 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.

15.4
15.4
Strong Acid Weak Acid

15.4
 What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid 100% dissociation.
Start 0.002 M 0.0 M 0.0 M
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
End 0.0 M 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 0.0 M 0.0 M
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
End 0.0 M 0.018 M 0.036 M
pH = 14.00 pOH = 14.00 + log(0.036) = 12.56
15.4
Weak Acids (HA) and Acid Ionization Constants

HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

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

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

Ka is the acid ionization constant

weak acid
Ka
strength

15.5
15.5
 What is the pH of a 0.5 M HF solution (at 250C)?
[H+][F-]
HF (aq) H+ (aq) + F- (aq) Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq)
Initial (M) 0.50 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.50 - x x x
x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 x 0.50
0.50 - x
x2
Ka = 7.1 x 10-4 x2 = 3.55 x 10-4 x = 0.019 M
0.50
[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72
[HF] = 0.50 x = 0.48 M
15.5
 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.

0.019 M Less than 5%
x = 0.019 x 100% = 3.8%
0.50 M 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
0.006 M More than 5%
x 100% = 12%
0.05 M Approximation not ok.

Must solve for x exactly using quadratic equation or method of

successive approximation. 15.5
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.

15.5
 What is the pH of a 0.122 M monoprotic acid whose
Ka is 5.7 x 10-4?
HA (aq) H+ (aq) + A- (aq)
Initial (M) 0.122 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.122 - x x x
x2
Ka = = 5.7 x 10-4 Ka << 1 0.122 x 0.122
0.122 - x
x2
Ka = 5.7 x 10-4 x2 = 6.95 x 10-5 x = 0.0083 M
0.122

0.0083 M More than 5%

x 100% = 6.8%
0.122 M Approximation not ok.
15.5
 x2
Ka = = 5.7 x 10-4 x2 + 0.00057x 6.95 x 10-5 = 0
0.122 - x
-b b2 4ac
ax2 + bx + c =0 x=
2a
x = 0.0081 x = - 0.0081

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

Initial (M) 0.122 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.122 - x x x

[H+] = x = 0.0081 M pH = -log[H+] = 2.09

15.5
 Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

15.5
Weak Bases and Base Ionization Constants

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

[NH4+][OH-]
Kb =
[NH3]

Kb is the base ionization constant

weak base
Kb
strength

Solve weak base problems like weak acids

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

15.6
15.6
Ionization Constants of Conjugate Acid-Base Pairs

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

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

H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka

15.7
15.8
 Molecular Structure and Acid Strength
H X H+ + X-

The The
stronger weaker
the bond the acid

HF << HCl < HBr < HI

15.9
 Molecular Structure and Acid Strength
- +
Z O H Z O - + H+

The O-H bond will be more polar and easier to break if:
Z is very electronegative or
Z is in a high oxidation state

15.9
 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from

the same group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z

O O

H O Cl O H O Br O

Cl is more electronegative than Br

HClO3 > HBrO3

15.9
 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different

numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

15.9
 Acid-Base Properties of Salts
Salts that Produce Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal
ion (except Be2+) and the conjugate base of a strong
acid (e.g. Cl-, Br-, and NO3-).
H 2O
NaCl (s) Na+ (aq) + Cl- (aq)

Salts that Produce Basic Solutions:

Salts derived from a strong base and a weak acid.
H2O
NaCH3COO (s) Na+ (aq) + CH3COO- (aq)

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

15.10
 Acid-Base Properties of Salts
Salts that Produce Acid Solutions:
Salts derived from a strong acid and a weak base.

H2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+,

Fe3+, Cr3+, and Be2+) and the conjugate base of a strong
acid.
Al(H2O)3+
6 (aq) Al(OH)(H2O)2+
5 (aq) + H (aq)
+

15.10
Acid Hydrolysis of Al3+

15.10
 Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:
Kb for the anion > Ka for the cation, solution will be basic
Kb for the anion < Ka for the cation, solution will be acidic
Kb for the anion Ka for the cation, solution will be neutral

15.10
 Example

Predict whether the following solutions will be

acidic, basic or nearly neutral:
A. NH4I B. NaNO2 C. FeCl3 D. NH4F
 Answers

A. NH4I
NH4 + will hydrolyze to NH3 and H+
I is a conjugate base of a strong acid and will
not hydrolyze
Therefore, it is acidic
 Answers

B. NaNO2

Na+ will not hydrolyze

NO2 is a conjugate base of a weak acid and will
hydrolyze forming HNO2 and OH-
Therefore, it is basic
 Answers

C. FeCl3

Fe+3 is highly charged and will hydrolyze to

produce H+ and
Cl- is a conjugate base of a strong acid and will
not hydrolyze
Therefore, it is acidic
 Answers
D. NH4F

NH4 + is a conjugate acid of a weak base and

will hydrolyze
F- is a conjugate base of a weak acid and will
also hydrolyze
Check the ka and kb values;
NH4 + ka = 5.6x10-10 > F- kb= 1.4x10-11
Therefore; it is acidic
 Exercise
Predict whether the following solutions will
be acidic, basic or nearly neutral:
A. LiClO4
B. Na3PO4
C. Bi(NO3)3
D. NH4CN
 Exercise
Predict whether the following solutions
will be acidic, basic or nearly neutral:
A. LiClO4 neutral
B. Na3PO4 basic
C. Bi(NO3)3 acidic
D. NH4CN NH4 + ka = 5.6x10-10
CN kb = 2.0x10-5
basic
Oxides of the Representative Elements
In Their Highest Oxidation States

CO2 (g) + H2O (l) H2CO3 (aq)

N2O5 (g) + H2O (l) 2HNO3 (aq)

15.11
 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- H O H


acid base
H H
+
H+ + N H H N H

H H
acid base
15.12
 Lewis Acids and Bases

F H F H
F B + N H F B N H

F H F H
acid base

No protons donated or accepted!

15.12
 Chemistry In Action: Antacids and the Stomach pH Balance

NaHCO3 (aq) + HCl (aq)

NaCl (aq) + H2O (l) + CO2 (g)

Mg(OH)2 (s) + 2HCl (aq)

MgCl2 (aq) + 2H2O (l)