Chapter 13: Acids and Bases

Section 13.1 The Nature of Acids and Bases

Models of Acids and Bases

• Arrhenius: Acids produce H+ ions in solution,

bases produce OH– ions.
• Brønsted–Lowry: Acids are proton (H+)
donors, bases are proton acceptors.
HCl + H2O → Cl– + H3O+
acid base

1
 Acid in Water

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

acid base conjugate conjugate
acid base

• Conjugate base is everything that remains of the acid molecule

after a proton is lost.
• Conjugate acid is formed when the proton is transferred to the
base.

2
Section 13.2 Acid Strength
• Strong acid:
 Ionization equilibrium lies far to the right.
 Yields a weak conjugate base.
• Weak acid:
 Ionization equilibrium lies far to the left.
 Weaker the acid, stronger its conjugate base.

3
HA(aq) + H2O(l) H3 O+(aq) + A-(aq)
 Weak acid:

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

[H3O+] [A-] [H+] [A-]

Ka = =
[HA] [HA]
acid dissociation constant (acid ionization constant -- equilibrium constant)
4
Water as an Acid and a Base

• Water is amphoteric:
 Behaves either as an acid or as a base.
• At 25°C:
Kw = [H+][OH–] = 1.0 × 10–14
• No matter what the solution contains, the product of [H+]
and [OH–] must always equal 1.0 × 10–14 at 25°C. 5
Three Possible Situations

• [H+] = [OH–]; neutral solution

• [H+] > [OH–]; acidic solution
• [H+] < [OH–]; basic solution

Concept Check

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

acid base conjugate conjugate
acid base
What is the equilibrium constant expression for an acid
acting in water?

 
H3O   A 
K =
HA  6
7
If the equilibrium lies to the right, the value for Ka is
__________.
large (or >1)

If the equilibrium lies to the left, the value for Ka is

___________.
small (or <1)

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

If water is a better base than A–, do products

or reactants dominate at equilibrium?

Does this mean HA is a strong or weak acid?

Is the value for Ka greater or less than 1?

8
Consider a 1.0 M solution of HCl.
Order the following from strongest to weakest base and
explain:
The bases from
H2O(l) strongest to weakest
A–(aq) (from weak acid HA) are: A-, H2O, Cl-.
Cl–(aq)
Consider a solution of NaA where A– is the anion from weak
acid HA:
A–(aq) + H2O(l) HA(aq) + OH–(aq)
[HA] [OH-]
base acid conjugate conjugate Kb =
acid base [A-]

a) Which way will equilibrium lie?

right Not sure
b) Is the value for Kb greater than or less than 1?
greater than 1 Not sure

c) Does this mean A– is a strong or weak base?

strong base 9
Acetic acid (HC2H3O2) and HCN are both weak acids. Acetic
acid is a stronger acid than HCN.

Arrange these bases from weakest to strongest and explain

your answer:

H 2O Cl– CN– C2H3O2– Cl–, H2O, C2H3O2–,

CN–

Discuss whether the value of K for the reaction:

HCN(aq) + F–(aq) CN–(aq) + HF(aq) [CN-] [HF] [H+]
K= - - +
[HCN ] [F ] [H ]
Ka(HCN)
is >1 <1 =1 =
Ka(HF)

(Ka for HCN is 6.2×10–10; Ka for HF is 7.2×10–4.)

Explain your answer. 10

Calculate the value for K for the reaction:

HCN(aq) + F–(aq) CN–(aq) + HF(aq)

(Ka for HCN is 6.2×10–10; Ka for HF is 7.2×10–4)

K = [CN-][HF]/[HCN][F-]
= [H+][CN-][HF]/[HCN][F-][H+]
K = Ka(HCN)/Ka(HF) = [6.2 x 10-10]/[7.2 x 10-4]
K = 8.6 x 10–7 = Ka(HCN)/Ka(HF)

Section 13.3 The pH scale

• pH = –log[H+]
• A compact way to represent solution acidity.
• pH decreases as [H+] increases.
• Significant figures:
 The number of decimal places in the log is equal to the
number of significant figures in the original number. 11
pH Range

• pH = 7; neutral
• pH > 7; basic
 Higher the pH, more basic.
• pH < 7; acidic
 Lower the pH, more acidic.

Exercise
Calculate the pH for each of the following
solutions.
a) 1.0 × 10–4 M H+ pH = 4.00
b) 0.040 M OH– pH = 12.60

The pH of a solution is 5.85. What is

the [H+] for this solution?
[H+] = 1.4 × 10–6 M 12
pH and pOH

• Recall:
Kw = [H+][OH–]

–log Kw = –log[H+] – log[OH–]

pKw = pH + pOH

14.00 = pH + pOH

Calculate the pOH for each of the following solutions.

a) 1.0 × 10–4 M H+
pOH = 10.00
b) 0.040 M OH–
pOH = 1.40 13
 The pH of a solution is 5.85. What is the [OH–] for this
solution?
pH = –log[H+] and pOH = –log[OH–] and
14.00 = pH + pOH
14.00 = 5.85 + pOH; pOH = 8.15
[OH–] = 10–8.15 = 7.1 × 10–9 M

Section 13.4 Calculating the pH of Strong Acid Solutions

Thinking About Acid–Base Problems

• What are the major species in solution?

• What is the dominant reaction that will take place?
 Is it an equilibrium reaction or a reaction that will go
essentially to completion?
 React all major species until you are left with an
equilibrium reaction.
• Solve for the pH if needed.
14
Concept Check

Consider an aqueous solution of 2.0 x 10–3 M HCl.

What are the major species in solution? H+, Cl–, H2O
What is the pH? pH = 2.70

Calculate the pH of a 1.5 x 10–11 M solution of HCl.

pH = 7.00
Watch for student to say pH = -log(1.5 x 10-11) = 10.82.
This answers neglects that water is a major species and it turns
out to be the major contributor of H+. If students think about this
problem and consider major species, they will answer this
correctly.
Major species are H+, Cl-, and H2O.
Dominant reaction is: H2O + H2O  H3O+ (aq) + OH- (aq)
Water is a major contributor. Thus , pH = 7.00.

Calculate the pH of a 1.5 x 10–2 M solution of HNO3.

pH = -log(1.5 x 10-2) = 1.82 15

Section 13.5 Calculating the pH of Weak Acid Solutions
Solving Weak Acid Equilibrium Problems
1. List the major species in the solution.
2. Choose the species that can produce H+, and write balanced
equations for the reactions producing H+.
3. Using the values of the equilibrium constants for the reactions
you have written, decide which equilibrium will dominate in
producing H+.
4. Write the equilibrium expression for the dominant equilibrium.
5. List the initial concentrations of the species participating in the
dominant equilibrium.
6. Define the change needed to achieve equilibrium; that is, define x.
7. Write the equilibrium concentrations in terms of x.
8. Substitute the equilibrium concentrations into the equilibrium
expression.
9. Solve for x the “easy” way, that is, by assuming that [HA]0 –
x about equals [HA]0.
10. Use the 5% rule to verify whether the approximation is valid. 16
11. Calculate [H+] and pH.
Consider a 0.80 M aqueous solution of the weak acid HCN
(Ka = 6.2 x 10–10).
What are the major species in solution?
HCN, H2O
Consider this

HCN(aq) + H2O(l) H3O+(aq) + CN–(aq) Ka = 6.2 x 10-10

H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Kw = 1.0 x 10-14
• Which reaction controls the pH? Explain.

Calculate the pH of a 0.50 M aqueous solution of the weak acid HF.

(Ka = 7.2 x 10–4)

HF(aq) + H2O  H3O+(aq) + F-(aq) Using an assumption that

0.5 – x is approximately
0.5 - x x x equal to 0.5

x2
= 7.2 x 10–4 x ≈ 1.897 × 10-2 pH ≈ 1.72 17
0.5 - x
Percent Dissociation (Ionization)
amount dissociated (mol/L)
Percent dissociation =  100%
initial concentration (mol/L)
• For a given weak acid, the percent dissociation increases as
the acid becomes more dilute (why? See next page).
Exercise
A solution of 8.00 M formic acid (HCHO2) is 0.47% ionized in water.
Calculate the Ka value for formic acid.
Ka = 1.8 x 10–4
If 8.00 M of the acid is 0.47% ionized, then 0.038 M dissociates.

HCHO2(aq) + H2O  H3O+(aq) + CHO2-(aq)

I 8.00 0 0
C -0.038 +0.038 +0.038
E 7.96 0.038 0.038

Ka = (0.038)2/7.96 = 1.8 x 10–4 18

Calculate the pH of an 8.00 M solution of formic acid. Use the
data from the previous slide to help you solve this problem.
pH = -log[H+] = -log[0.038] = 1.42

The value of Ka for a 4.00 M formic acid solution should be:

higher than lower than the same as
the value of Ka of an 8.00 M formic acid solution. Explain.

The percent ionization of a 4.00 M formic acid solution should be:

higher than lower than the same as
the percent ionization of an 8.00 M formic acid solution. Explain.
higher;
To make 4.00 M solution from 8.00 M solution, we must add
water (dilute). With a larger volume, Le Chatelier's principle
tells us that equilibrium will shift to the right. Thus, percent
ionization will increase. However, this increase is offset by
the dilution factor, and the solution has an overall lower
19
concentration of H+.
The pH of a 4.00 M formic acid solution should be:
higher than lower than the same as
the pH of an 8.00 M formic acid solution. Explain.

Calculate the percent ionization of a 4.00 M formic acid

solution in water.
% Ionization = 0.67%

Dominant reaction:

HCHO2(aq) + H2O  H3O+(aq) + CHO2-(aq)

I 4.00 0 0
C -x +x +x
E 4.00-x x x

Ka = 1.8 x 10-4 = (x)2/(4.00-x)

x ≈ 0.027; (0.027/4.00) x 100 = 0.67% 20

 Calculate the pH of a 4.00 M solution of formic acid.
Dominant reaction: HCHO2(aq) + H2O  H3O+(aq) + CHO2-(aq)
From preview exercise, x = [H3O+] = [H+] = 0.027; pH = 1.57

Section 13.6 Bases

• Arrhenius: bases produce OH– ions.
• Brønsted–Lowry: bases are proton acceptors.
• In a basic solution at 25°C, pH > 7.
• Ionic compounds containing OH– are generally considered
strong bases.
 LiOH, NaOH, KOH, Ca(OH)2
• pOH = –log[OH–]
• pH = 14.00 – pOH

Calculate the pH of a 1.0 x 10–3 M solution of sodium

hydroxide. pH = 11.00
Calculate the pH of a 1.0 x 10–3 M solution of calcium
hydroxide. pH = 14 – (-log (2.0 × 10-3) = 11.30 21
• Equilibrium expression for weak bases uses Kb.
NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)
[NH4+] [OH–]
Kb =
[NH3]

• pH calculations for solutions of weak bases are very similar to

those for weak acids.
• Kw = [H+][OH–] = 1.0 × 10–14
• pOH = –log[OH–]
22
• pH = 14.00 – pOH
 Calculate the pH of a 2.0 M solution of ammonia (NH3).
(Kb = 1.8 × 10–5)
NH3(aq) + H2O  NH4+(aq) + OH-(aq)
I 2.0 0 0 x2 / (2.0 – x) = 1.8 × 10-5
E 2.0 – x x x x = 0.0060 M
pOH = -log(0.0060); pH = 14.00 – 2.22 = 11.78

Section 13.7 Polyprotic Acids

• Acids that can furnish more than one proton.

• Always dissociates in a stepwise manner, one proton at a time.
• The conjugate base of the first dissociation equilibrium
becomes the acid in the second step.
• For a typical weak polyprotic acid:
Ka1 > Ka2 > Ka3
• For a typical polyprotic acid in water, only the first
dissociation step is important to pH. 23
24
Exercise

Calculate the pH of a 1.00 M solution of H3PO4.

Ka1 = 7.5 x 10-3
Understand why only the first
Ka2 = 6.2 x 10-8
dissociation reaction is
Ka3 = 4.8 x 10 -13
important

H3PO4(aq) + H2O  H3O+(aq) + H2PO4-(aq)

I 1.0 0 0
E 1.0 – x x x

x2 / (1.0 – x) = 7.5 × 10-3

x2 + 0.0075x – 0.0075 = 0
x1 = -0.09; x2 = 0.0829
pH = - log (0.0829) = 1.08

H2PO4-(aq) + H2O  H3O+(aq) + HPO42-(aq)

25
HPO4 2-(aq) + H 2O  H 3 O+(aq) + PO4 3-(aq)
 Calculate the equilibrium concentration of PO43- in a 1.00 M
solution of H3PO4.
Ka1 = 7.5 x 10-3; Ka2 = 6.2 x 10-8
Ka3 = 4.8 x 10-13 [PO43-] = 3.6 x 10-19 M

From the previous exercise, the students should see that

[H+] = [H2PO4-] = 0.0829 M (from the first dissociation reaction).

Using the Ka2 expression, students can solve for [HPO42-] = 6.2 x 10-8 M.
H2PO4-(aq) + H2O  H3O+(aq) + HPO42-(aq)
I 0.0829 0.0829 0
C -x +x +x
E 0.0829 - x 0.0829 + x x
Many students will use “0” as the initial value of [H3O+].

Using the Ka3 expression, students can solve for the phosphate ion concentration.
HPO42-(aq) + H2O  H3O+(aq) + PO43-(aq)
I 6.2 x 10-8 0.0829 0
C -y +y +y
E 6.2 x 10-8 - y 0.0829 + y y

Make sure the students understand that [H3O+] can only have one value; that is, there
are not different [H3O+]’s for the different dissociations. 26
Section 13.8 Acid-Base Properties of Salts

Salts

• Ionic compounds.
• When dissolved in water, break up into its ions (which can
behave as acids or bases).

The salt of a strong acid and a strong base gives a neutral solution.
 KCl, NaNO3

Those ions have no affinity for H+ or OH-. Therefore, no effect on [H+]

27
Salts that produce basic solutions
A basic solution is formed if the anion of the salt is
the conjugate base of a weak acid.

NaF, KC2H3O2

F-(aq) + H2O  HF(aq) + OH-(aq)

[HF] [OH-] [HF] [OH-] [H+] Kw

Kb = = =
[F-] [F-] [H+] Ka(HF)

Kw
General formula Kb(A-) =
Ka(HA)

Salts that produce acidic solutions

An acidic solution is formed if the cation of the salt is
the conjugate acid of a weak base.
NH4Cl 28
Qualitative Prediction of pH of Salt Solutions (from Weak Parents)

29
30
Exercise
HC2H3O2 Ka = 1.8 x 10-5
HCN Ka = 6.2 x 10-10

Calculate the Kb values for: C2H3O2− and CN−

Kb (C2H3O2-) = 5.6 x 10-10
Kb (CN-) = 1.6 x 10-5

Arrange the following 1.0 M solutions from lowest to highest pH.

HBr NaOH NH4Cl
NaCN NH3 HCN
NaCl HF
Justify your answer.
HBr, HF, HCN, NH4Cl, NaCl, NaCN, NH3, NaOH

The order is: HBr (strong acid), HF (Ka = 7.2 x 10-4), HCN (Ka = 6.2 x 10-10), NH4Cl
(Ka = 5.6 x 10-10), NaCl (neutral), NaCN (Kb = 1.6 x 10-5), NH3 (Kb = 1.8 x 10-5),
NaOH (strong base). Have the students use the Ka and Kb values to decide. They
31
need not calculate the pH values to answer this question.
 Consider a 0.30 M solution of NaF. The Ka for HF is 7.2 x 10-4.
What are the major species?
Na+, F-, H2O
Let’s Think About It…
• Why isn’t NaF considered a major species?
• What are the possibilities for the dominant reactions?

The possibilities for the dominant reactions are:

1. F–(aq) + H2O(l)  HF(aq) + OH–(aq)

2. H2O(l) + H2O(l)  H3O+(aq) + OH–(aq)

3. Na+(aq) + H2O(l)  NaOH + H+(aq)

4. Na+(aq) + F–(aq)  NaF

32
• How do we decide which reaction controls the pH?

F–(aq) + H2O(l)  HF(aq) + OH–(aq)

H2O(l) + H2O(l)  H3O+(aq) + OH–(aq)

• Determine the equilibrium constant for each reaction.

The Ka for HF is 7.2 x 10-4.

Kb = 1.4 × 10-11 for the first equilibrium

33
Calculate the pH of a 0.75 M aqueous solution of NaCN.
Ka for HCN is 6.2 x 10–10.

CN-(aq) + H2O  HCN(aq) + OH-(aq)

H2O + H2O  H3O+(aq) + OH-(aq)

The primary reaction is the first one, and the Kb value is 1.6 x 10-5.
This is many times larger than the K value for the second reaction
(Kw).

CN–(aq) + H2 O  HCN(aq) + OH–(aq)

Initial 0.75 M 0 ~0

Change –x +x +x

Equilibrium 0.75 – x x x
Kb = 1.6 x 10–5
pH = 11.54 34
Section 13.9 Effect of Structure on Acid-Base Properties

Models of Acids and Bases

• Two factors for acidity in binary compounds:

 Bond Polarity (high is good)
 Bond Strength (low is good)

Bond Strengths and Acid

Strengths for Hydrogen
Halides

35
Oxyacids

• Contains the group H–O–X.

• For a given series the acid
strength increases with an
increase in the number of
oxygen atoms attached to the
central atom.
• The greater the ability of X to
draw electrons toward itself,
the greater the acidity of the
molecule.

Several Series of
Oxyacids and Their
Ka Values

36
Comparison of Electronegativity of X and Ka Value

O
O H2SO4 and B(OH)3 (or Si(OH)4):
S OH Cl OH which one is more acidic?
O O
OH O Ka1
H2SO4  H+ + HSO4-
OH OH
Ka2
Si OH B 37
HO OH HO OH HSO4 
- H+ + SO4 2-
 -
OH O

B B + H+
HO OH HO OH

O O
S OH - + H+
O S O
O
OH OH

Pauling's rules

(1) For the oxoacid OpE(OH)q, pKa  8-5p

(2) The successive pKa values of polyprotic acids (q>1),

increase by 5 units for each successive proton transfer.
38
 Molecular
structures and
the strength of
oxo and
hydroxoacids

The pKa value of

H3PO3 was
reported to be 1.8.
Predict its
structure.
39
Section 13.10 Acid-Base Properties of Oxides

Oxides
• Acidic Oxides (Acid Anhydrides):
 O – X bond is strong and covalent.
SO2, NO2, CO2

• Basic Oxides (Basic Anhydrides):

 O – X bond is ionic.
K2O, CaO CO2 + H2O  C(O)(OH)2 acid
SO3 + H2O  S(O)2(OH)2 acid

Hydrolysis process
of an anhydrous BaO + H2O  Ba(OH)2 base
oxide
H2O H
H H
+O O

A O A O- A O
H 40
A: metal or non-metal atoms
 CO2 + H2O  H2CO3 O C O
C OH
O
OH
OH2

BaO + H2O  Ba(OH)2 Ba O

Ba OH

OH
OH2

A O H

A = non metals A = alkali metals, alkaline earth metals

O
O S O H H+ + HSO3- Na O H Na+ + OH-

HO

41
Amphoteric oxides

42
Section 13.11 The Lewis Acid-Base Model

Lewis Acids and Bases

• Lewis acid: electron pair acceptor

• Lewis base: electron pair donor
3+
H H
Al3+ + 6 O Al O
H H 6
Lewis acid Lewis base

43
dative bond

44