Acids and Bases

1
 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.
2
 Acid - Base

HCl(g) + NH3(g)  NH4Cl(s)

3
 Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water

A Brønsted 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 4
 Lewis Acids and Bases

F H F H
F B + F B

••
N H N H
F H F H
acid base

No protons donated or accepted!

5
 A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base

6
 Acid-Base Properties of Water

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

autoionization of water

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

conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
7
base
 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 25 0C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic

8
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 1 x 10 -14
w -15 M
[OH-] = = = 7.7 x 10
[H+] 1.3

9
 pH – A Measure of Acidity

pH = -log [H+]

Solution is At 25 0C
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+]

10
Other important relationships
pOH = -log [OH-]

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

-log [H+] – log [OH-] = 14.00

pH + pOH = 14.00

11
 Measure of pH

pH paper
pH meter

Red cabbage 12
Litmus paper
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

13
 Strong Electrolyte – 100% dissociation
H 2O
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)
14
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

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

15
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.

16
17
Strong Acid (HCl) Weak Acid (HF)

18
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) = 12.6 19
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

20
21
What is the pH of a 0.5 M HF solution (at 25 0C)?
[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 22
 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 25 0C)?

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

23
successive approximations.
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.

24
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.
25
 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

26
 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

27
 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+].

28
29
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
30
 Diprotic and Triprotic Acids
• May yield more than one hydrogen ion per molecule.
• Ionize in a stepwise manner; that is, they lose one proton at
a time.
• An ionization constant expression can be written for each
ionization stage.
• Consequently, two or more equilibrium constant expressions
must often be used to calculate the concentrations of
species in the acid solution.

31
32
Molecular Structure and Acid Strength
H X H+ + X-

The The
stronger weaker
the bond the acid

HF << HCl < HBr < HI

acidity
increases

33
34
 Molecular Structure and Oxoacid Strength
d- d+
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

35
 Molecular Structure and Oxoacid 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

acidity
HClO3 > HBrO3 increases

36
 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

37
 Acid-Base Properties of Salts
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-).
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Basic Solutions:
Salts derived from a strong base and a weak acid.
H 2O
NaCH3COOH (s) Na+ (aq) + CH3COO- (aq)

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

38
 Acid-Base Properties of Salts
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+,

Cr3+, and Be2+) and the conjugate base of a strong acid.

Al(H2O)3+
6 (aq) Al(OH)(H2O)52+(aq) + H+ (aq)

39
Acid Hydrolysis of Al3+

40
 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

41
42
Oxides of the Representative Elements
In Their Highest Oxidation States

Na2O (s) + H2O (l) 2NaOH (aq)

CO2 (g) + H2O (l) H2CO3 (aq)
43
N2O5 (g) + H2O (l) 2HNO3 (aq)
 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)

44
Acid-Base Equilibria and
Solubility Equilibria

45
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)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

46
 Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
-] pH = pKa + log
[A [acid]
-log [H+] = -log Ka + log
[HA]

[A-]
pH = pKa + log pKa = -log Ka
[HA]
47
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) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log = 4.01
[0.30]
HCOOH pKa = 3.77
48
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) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
49
 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

50
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 its conjugate acid
buffer solution

51
 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) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]

start (moles) 0.029 0.001 0.024

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

+]
0.028 0.025 [0.25]
[NH4 = [NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28] 52
Chemistry In Action: Maintaining the pH of Blood

Red blood cells in

a capillary

53
 Titrations (Review)
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
54
(pink)
Alternative Method of Equivalence Point Detection

monitor pH
55
Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

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

56
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)

57
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

58
 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) NO2- (aq) + H2O (l)
end (moles) 0.0 0.0 0.01
0.01
Final volume = 200 mL [NO2-] = = 0.05 M
0.200
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Initial (M) 0.05 0.00 0.00

Change (M) -x +x +x
Equilibrium (M) 0.05 - x x x
[OH-][HNO2] x2
Kb = = = 2.2 x 10 -11 pOH = 5.98
[NO2-] 0.05-x
pH = 14 – pOH = 8.02
0.05 – x  0.05 x  1.05 x 10-6 = [OH-] 59
 Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
-  10 Color of acid (HIn) predominates
[In ]
[HIn]
 10 Color of conjugate base (In -) predominates
[In-]

60
Solutions of Red Cabbage Extract

pH
61
The titration curve of a strong acid with a strong base.

62
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

63
 Solubility Equilibria

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+][Cl-] Ksp is the solubility product constant

MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2

Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]
Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2
Dissolution of an ionic solid in aqueous solution:

Q < Ksp Unsaturated solution No precipitate

Q = Ksp Saturated solution
Q > Ksp Supersaturated solution Precipitate will form
64
65
Molar solubility (mol/L) is the number of moles of solute
dissolved in 1 L of a saturated solution.
Solubility (g/L) is the number of grams of solute dissolved in
1 L of a saturated solution.

66
 What is the solubility of silver chloride in g/L ?

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10

Initial (M) 0.00 0.00 Ksp = [Ag+][Cl-]
Change (M) +s +s Ksp = s2
Equilibrium (M) s s s = Ksp
s = 1.3 x 10-5
[Ag+] = 1.3 x 10-5 M [Cl-] = 1.3 x 10-5 M

1.3 x 10-5 mol AgCl 143.35 g AgCl

Solubility of AgCl = x = 1.9 x 10-3 g/L
1 L soln 1 mol AgCl

67
68
If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M
CaCl2, will a precipitate form?

The ions present in solution are Na+, OH-, Ca2+, Cl-.

Only possible precipitate is Ca(OH)2 (solubility rules).
Is Q > Ksp for Ca(OH)2?

[Ca2+]0 = 0.100 M [OH-]0 = 4.0 x 10-4 M

Q = [Ca2+]0[OH-]02 = 0.10 x (4.0 x 10-4)2 = 1.6 x 10-8

Ksp = [Ca2+][OH-]2 = 8.0 x 10-6

Q < Ksp No precipitate will form

69
What concentration of Ag is required to precipitate ONLY AgBr in
a solution that contains both Br- and Cl- at a concentration of
0.02 M?

AgBr (s) Ag+ (aq) + Br- (aq) Ksp = 7.7 x 10-13

Ksp = [Ag+][Br-]
Ksp 7.7 x 10 -13
-11 M
[Ag+] = = = 3.9 x 10
[Br-] 0.020

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10

Ksp = [Ag+][Cl-]
Ksp 1.6 x 10-10 -9 M
[Ag+] = = = 8.0 x 10
[Cl-] 0.020

AgCl AgBr
3.9 x 10-11 M < [Ag+] < 8.0 x 10-9 M
70
 The Common Ion Effect and Solubility

The presence of a common ion decreases the solubility of the

salt.

What is the molar solubility of AgBr in (a) pure water and (b)
0.0010 M NaBr?

NaBr (s) Na+ (aq) + Br- (aq)

AgBr (s) Ag+ (aq) + Br- (aq) [Br-] = 0.0010 M
Ksp = 7.7 x 10-13 AgBr (s) Ag+ (aq) + Br- (aq)
s2 = Ksp [Ag+] = s
s = 8.8 x 10-7 [Br-] = 0.0010 + s  0.0010
Ksp = 0.0010 x s
s = 7.7 x 10-10 71
 pH and Solubility
• The presence of a common ion decreases the solubility.
• Insoluble bases dissolve in acidic solutions
• Insoluble acids dissolve in basic solutions
remove
add
Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)

At pH less than 10.45

Ksp = [Mg2+][OH-]2 = 1.2 x 10-11 Lower [OH-]
Ksp = (s)(2s)2 = 4s3 OH- (aq) + H+ (aq) H2O (l)
4s3 = 1.2 x 10-11 Increase solubility of Mg(OH)2
s = 1.4 x 10-4 M At pH greater than 10.45
[OH-] = 2s = 2.8 x 10-4 M Raise [OH-]
pOH = 3.55 pH = 10.45 Decrease solubility of Mg(OH)2
72
 Complex Ion Equilibria and Solubility
A complex ion is an ion containing a central metal cation
bonded to one or more molecules or ions.
Co2+ (aq) + 4Cl- (aq) CoCl42- (aq)

The formation constant or stability constant (Kf) is the

equilibrium constant for the complex ion formation.

[CoCl42- ]
Kf =
Co(H2O)2+ [Co2+][Cl-]4
6 CoCl2-
4

stability of
Kf
HCl complex

73
Effect of Complexation on Solubility
AgNO
Add3 +
NHNaCl
3

AgCl 3)2+
Ag(NH 74
75
76
Qualitative
Analysis of
Cations

77
 Flame Test for Cations

lithium sodium potassium copper

78
 Chemistry In Action: How an Eggshell is Formed

Ca2+ (aq) + CO32- (aq) CaCO3 (s)

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

H2CO3 (aq) H+ (aq) + HCO3- (aq)

HCO3- (aq) H+ (aq) + CO32- (aq)

electron micrograph
79