17 Acids and Bases

A group of chemical properties is related to acidity. According to these

properties, a substance can be called an acid or a base.
The word acid comes from Latin acere meaning sour. A base is an
alkaline, which is derived from Arabic alqali.
Presence of acids and bases have been recognized by ancient people.
Lavoisier named oxygen as the element from which acids are derived.
Liebig (German) proposed that an acid contains hydrogen.
Many chemical reactions are called acid-base reactions; they are not
necessarily neutralizations.
The acid-base concept is interesting, especially the way it evolved.
Understand acid or base, important
17 Acidproperties
and Baseof substances.

Answer these questions

What are acids?
What are bases?

Understand important properties of substances

What are acid-base reactions?

What are neutralization reactions?
What are the relationships between acids and bases?
What is the role of the solvent in acid or base solutions?
How does the acid-base concept evolve and why?
What are Arrhenius acid, Bronsted-Lowry acid and Lewis acids?
What is the relationship between conjugate acids and bases?
What does pH mean and how is the pH scale related to acidity?
What are salts?
17 Acid and Base

Arrhenius acids and bases

Sevante Arrhenius proposed that substances exists as ions in
solution in his dissertation, which was awarded a fourth class (D)
in 1884. He was unable to find a job in his native Sweden.
He was awarded the Nobel Prize in 1903 for his electrolytic
dissociation theory.
The fundamental concept: (Text PHH: 17-1)
Acid - any substance which delivers hydrogen ion (H+) to the solution.
HA H+ + A
Base - any substance which delivers hydroxide ion (OH) to the solution.
BOH X+ + OH

17 Acid and Base

Problems with Arrhenius theory

Like Daltons atomic theory, Arrhenius theory have problems today:
Acidity did not show in other solvent. What is the solvent role?
Some salts produce acidic or basic solutions, not neutral. Why?
Which is the base, NH3 or NH4OH? Is OH really the only base?
How can H+ be stable? Are proton donated?

Some chemists want students to learn Brnsted-Lowry theory of acids

and bases before learning Arrhenius theory, because the former is
more general.
Question the established theory.
17 Acid and Base

Brnsted-Lowry theory of acids and bases

An acid is a substance from which a proton can be removed.
Acids are proton donors.
A base is a substance that can remove a proton from an acid.
Bases are proton acceptors.
Because of strong desire for protons, bases rip protons off acids.
Acid-base reactions are competitions for protons.
HCl + H2O H3O+ + Cl
HNO3 + H2O H3O+ + NO3
HC2H3O2 + H2O H3O+ + C2H3O2
H2O + NH3 NH4+ + OH

172

conjugate acids and bases

17 Acid and Base

Problems with B-L theory

The theory works very nicely in all protic solvent, but fails to explain
acid-base behavior in aprotic solvents and non-solvent situations.
A more general concept on acid and base was proposed by G.N.
Lewis at about the same time Bronsted-Lowry theory was proposed.

Question the established theory.

17 Acid and Base

Evolution of the acid-base concept

year

thinker

Acid

Base

acid-base reaction

1884

Arrhenius

ionize
H+

ionize
OH

H+ + OH = HOH

1923

BronstedLowry

Proton
Donor

proton
acceptor

HA + B = HB + A
conjugation

1923

Lewis

electrophil nucleophil

17 Acid and Base

E + Nu = E:Nu

Lewis acids and bases

Gilbert Newton Lewis (1875-1946) influential
American chemist. His theories include the
Lewis dot structure taught in Chem120 and
covalent bond theories.
Lewis acids are electrophils: H+, Na+, BF3,
Lewis bases are nucleophils: NH3, H2O, PH3
Acid base reactions:
BF3 + :NH3 F3B:NH3
Lewis at his desk.
He generalized an idea.

179

17 Acid and Base

Relative strengths
of acids and bases

HClO4
ClO4
H2SO4
HSO4
HI
I
HBr
Br
The stronger the acid, the
HCl
Cl
weaker its conjugate base.
HNO3
NO3
H3O+
H2 O
HClO ClO
HSO4
SO42
HBrO
BrO
NH4+ NH3
H2SO3
HSO3
HCN
CN
H3PO4
H2PO4
HCO3 CO32
HNO2 NO2
H2O2 HO2
HF
F
HS
S2
HC2H3O2
C2H3O2
H2O
OH
Al(H2O)63+
Al(OH)(H2O)52+
ROH RO
H2CO3
HCO3
9
174 & 175 Table
17 Acid and Base
H2S 173
HS

Skills regarding strength of acids

What are strong acids?
What are strong bases?
Which is the strongest acid, HF, HCl, HBr, or HI?
How about HNO3 and HNO2? H2SO4, H2SO3?
How about HClO4, HClO3, HClO2, HClO, and HCl?
What is the strongest acid in an aqueous solution?
What is leveling effect?
Order a given list according to the strength.
Interpret reactions as due to strength of acids and bases.
Explain strength with related acids and bases.
17 Acid and Base

10

Molecular structure and acid strength

A strong acid loses its proton easily. A strong base holds onto a proton
tightly.
The more polarized is the
HX
bond in an acid, the easier the molecule releases H+ thus a stronger acid.
The weaker the H X bond, the easier the molecule releases H + thus a
stronger acid.
The bond strength and the polarity are related to electronegativity and
electrostatic interactions size of the ions.
Able to predict acidity from molecular structure.
178

17 Acid and Base

11

Self-ionization of water
Water molecules autoionize
2 H2O (l) = H3O+ (aq) + OH (aq)
[H3O+] [OH]
Kc =
[H2O] (= 1000/18 = 55.6)
Kw = [H2O] Kc = 1e14 only at 25oC, its T dependent.
The ion product, Kw increases as T increases, and its value remains
the same in the presence of acid or base.
The molecule of life, H2O, and its acidity.
17 3

17 Acid and Base

12

Solutions of strong acids and bases

Strong acids and strong bases completely ionize in their solutions.
HCl (aq) + H2O (l) H3O+ (aq)+ Cl (aq)
KOH (aq) K+ (aq)+ OH (aq)
In a 0.100 M HCl or HNO3 solution,
[H+] = 0.100 M
and
[OH] = 1e14 / 0.100 = 1e13 M at 25oC
In a 0.100 M NaOH or KOH solution,
[OH] = 0.100 M
and
[H+] = 1e14 / 0.100 = 1e13 M at 25oC
In a 0.010 M Ca(OH)2 solution,
[OH] = 2*0.010 = 0.020 M
[H+] = 1e14 / 0.020 = 5e13 M at 25oC
17 Acid and Base

13

Some strong acids and bases

Strong acids
Hydrogen halides
HCl
HBr

Strong Bases
HI

Oxyacids of halogens
HClO3 HBrO3 HIO3
HClO4 HBrO4 HIO4

Hydroxides of alkali metals

NaOH KOH CsOH
Hydroxides of alkali earth
Ca(OH)2 Sr(OH)2

Other oxyacids
H2SO4 HNO3

17 4

17 Acid and Base

14

Neutralization Reactions
The neutralization reaction between strong acids and strong bases
has the net ionic reaction
H3O+ (aq)+ OH (aq) = 2 H2O
The anions are bystander ions. They do not participate the reaction.
These ions are
I, Br, Cl, NO3 , HSO4 , CClO4 , Na+, K+, Cs+, Ca2+
etc.
When dried, the ions left behind in neutralization reactions form salts.

17 Acid and Base

15

The pH scale
Sorensen introduced the pH scale in 1909 using the symbol p H.
The p is from the German word potenz, power of (10).
pH = log [H+];
pOH = log [OH];
pK = log [K];

[H+] = 10 pH
[OH] = 10 pOH
K = 10 pK

pH = 0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.8
[H+] = 0.79 0.63 0.50 0.40 0.32 0.25 0.20 0.16
(not linear; need not copy, figure out yourself)

0.9
0.13

For aqueous solution;

Kw = [H+] [OH]
- log Kw = pH + pOH = 14 only at 25oC
173, p672

17 Acid and Base

16

pH meter and pH electrodes

The pH meter is based on the principle to be
discussed in electrochemistry.
This topic is also related to the equilibrium
constant K and Gibbs free energy, G.

17 Acid and Base

17

Neutrality
In a neutral solution, [H+] = [OH]. (Different from Fig. 17-5)
In an acidic solution, [H+] > [OH], and a basic solution, [H+] < [OH].

In a saturated CaO (same as Ca(OH)2) solution, [OH] = 0.025.

Calculate pH, [H+], [Ca2+], and pOH at 25oC.
Solution:
pOH = log 0.025 = 1.60
pH = 14.00 1.60 = 12.40
only applicable at 25oC
[H+] = 1012.40 = 4.0e13 M Note that 4.0e-13*0.025 = 1e-14
[Ca2+] = [OH] / 2= 0.013 M
17 Acid and Base

18

Answer these questions review

What are acid-base reactions?
What are neutralization reactions?
What is the role of the solvent in acidity?
What does pH mean and how is the pH scale related to acidity?
What are salts?

17 Acid and Base

19

Acid-Base Equilibria
Strong acids and bases completely ionize in their aqueous solutions.
HCl H+ + Cl
KOH K+ + OH
Weak acids and bases ionize but not completely in their solutions.
HCH3COO H+ + CH3COO acetic acid, vinegar spirit
HNic H+ + Nic
HNic = Niacine, C5NH5COOH, a water-soluble vitamin required by the body for
health, growth and reproduction; part of the vitamin B complex. It was first prepared in
pure form by oxidizing nicotine using conc. HNO3. Nicotine is a major chemical in
tobacco .

CH3
N

<= Nicotine

Niacine =>
Vitamine B3

17 Acid and Base

COOH
20

Caffeine
Caffeine C8H10N4O2 is a weak
base, (pH of 1% soln 6.9)
taste bitter smell like tea, a
cardiac stimulant, (boost of
energy), mild diuretic, addictive,
operates using the same
mechanisms that amphetamines,
cocaine and heroin use to
stimulate the brain.
Crystals are hexagonal prisms by
sublimation, mp 238C. Sublimes
178. Fast sublimation is
obtained at 160-165 under
1 mm Hg pressure.
Many organic bases are
interesting drugs, and their
chemistry is fascinating.

17 Acid and Base

21

Ionization of weak acids

Ionization of acetic acid, HCH3COO, HA
HA = H+ + A

same as HA + H2O = H3O+ + A

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

A = CH3COO (acetate)
Ka acid ionization constant, important for an acid
Ka equilibrium constant with solvent effect

The pKa is defined similar to the pH,

pKa = log Ka

See Table 17-3 on page 678

Ka = 10 pKa

17 Acid and Base

22

Some weak acids and bases

Common Weak Acids
Formic acid
Acetic acid
Trichloroacetic acid
Hydrofluoric
Hydrocyanic
Hydrogen sulfide
Water

HCOOH
CH3COOH
CCl3COOH
HF
HCN
H2S
H2O

Conjugate acids
of weak bases

NH4+

Common Weak Bases

ammonia
trimethyl ammonia
pyridine
ammonium hydroxide
water
HS- ion

NH3
N(CH3)3
C5H5N
NH4OH
H2O
HS-

conjugate bases of
weak acids e.g.:

HCOO-

17 Acid and Base

23

Determine Ka and percent ionization

Nicotinic acid, HNic, is a monoprotic acid. A solution containing
0.012 M HNic, has a pH of 3.39. What is its Ka? What is the percent
of ionization?
Solution:
HNic = H+ + Nic
0.012-x x
x
x = [H+] = 103.39 = 4.1e-4
[HNic] = 0.012 0.00041 = 0.012
(4.1e-4)2
Ka = = 1.4e-5
0.012
Degree of ionization = 0.00041 / 0.012 = 0.034 = 3.4%
17 Acid and Base

24

Application of Ka
The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing 0.22
M HNic. What is its pH? What is the degree of ionization?
Solution:
HNic = H+ + Nic
0.22-x
x
x
x2
Ka = = 1.4e-5
0.22 x
(use approximation, small indeed)
x = (0.22*1.4e-5) = 0.0018

pH = log (0.0018) = 2.76

Degree of ionization = 0.0018 / 0.22 = 0.0079 = 0.79%

compare with 3.4% when the solution was 0.012 M
17 Acid and Base

25

pH of a weak acid
The pH of C M acid HA (Ka) solution.
Method:
HA =
C-x

H + + A
x
x

The pOH of C M base BOH (Kb)

solution.
Method:
BOH = B+ + OH
C-y
y
y

x2
Ka =
Cx
x 2 + Ka x C Ka = 0
Ka + Ka2 + 4 C Ka
x =
2
pH = log x

y2
Kb =
Cy
y 2 + Kb x C Kb = 0
Kb + Kb2 + 4 C Kb
y =
2
pOH = -log y

17 Acid and Base

26

Using the quadratic formula

The Ka of nicotinic acid, HNic, is 1.4e-5. A solution containing
0.00100 M HNic. What is its pH? What is the degree of ionization?
Solution:
HNic = H+ + Nic
0.001-x x
x
x2
Ka = = 1.4e-5
0.00100 x

x 2 + Ka x C Ka = 0
Ka + Ka2 + 4 C Ka
x =
2

x2 + 1.4e-5 x 1.4e-8 = 0

1.4e5 + (1.4e5)2 + 4*1.4e-8

x = = 0.000111 M
2

pH = log (0.000111) = 3.95

Degree of ionization = 0.000111/ 0.001 = 0.111 = 11.1%
17 Acid and Base

Deg.f ionizn
0.22
0.012
0.001

0.79%
3.4 %
11.1 %
27

Degree of or percent ionization

% ionization
The degree or percent of ionization of a weak
acid always decreases as its concentration
increases, as shown from the table given earlier.

Deg.f ionizn
0.22
0.012
0.001

0.79%
3.4 %
11.1 %

Concentration of acid
17 Acid and Base

28

Polyprotic acids
Polyprotic acids such as sulfuric and carbonic acids have more than
one hydrogen to donate.
H2SO4 = H+ + HSO4
HSO4 = H+ + SO42

Ka1 very large completely ionized

Ka2 = 0.012

H2CO3 = H+ + HCO3
HCO3 = H+ + CO32

Ka1 = 4.3e-7
Ka2 = 4.8e-11

Ascorbic acid (vitamin C)

is a diprotic acid, abundant
in citrus fruit.
Others:
H2S, H2SO3, H3PO4, H2C2O4 (oxalic acid)
17 Acid and Base

29

Aspartame nutrasweet
A dipeptide methyl ester :
L-aspartyl-L-phenylalanine methyl ester
C14H18N2O5 (molar mass = 294.31)
Aspartame has two ionizable protons

1965. Jim Schlatter synthesized

it and discovered it sweet leaving
no bitter after tast.

17 Acid and Base

30

Species concentrations of diprotic acids

Evaluate concentrations of species in a 0.10 M H2SO4 solution.
Solution:
H2SO4 = H+ +
(0.10.1) 0.10+y

HSO4
0.10-y

completely ionized

SO42
y

Ka2 = 0.012
Assume y = [SO42]

HSO4 = H+ +
0.10y
0.10+y
(0.10+y) y
= 0.012
(0.10-y)
[SO42] = y = 0.01M
[H+] = 0.10 + 0.01 = 0.11 M;
[HSO4] = 0.10-0.01 = 0.09 M

Y2 + 0.112 y 0.0012 = 0
- 0.112+0.1122 + + 4*0.0012
y = = 0.0098
2

If concentrationf H2SO4 = 1.0 M,

what doUdo?
31
17 Acid and Base

Species concentrations of weak diprotic acids

Evaluate concentrations of species in a 0.10 M H2S solution.
Solution:
H2S = H+ +
(0.10x) x+y
HS
xy

= H+
x+y

HS
x-y
+

S2
y

(x+y) (x-y)
= 1.02e-7
(0.10-x)
[H2S] = 0.10 x = 0.10 M
[HS] = [H+] = x y = 1.0e4 M;
[S2] = y = 1.0e-13 M
See Example 16.4

Ka1 = 1.02e-7
Assume x = [HS]
Ka2 = 1.0e-13
Assume y = [S2]
(x+y) y
= 1.0e-13
(x-y)

0.1>> x >> y:
x+ y = x-y = x
x = 0.1*1.02e-7 = 1.00e-4
y = 1e-13

17 Acid and Base

32

Beware of Misconceptions
These equations show dynamic equilibria at the molecular level in a
system. These equations are not separate reactions, but they
indicate possible combination and dissociation in both directions.
H2S = H+ +

HS Ka1 = 1.02e-7

HS = H+ +

S2

H2O = H+ +

OH- Kw = 1e-14

Ka2 = 1.0e-13
H2S(g)

HS
H2 S
OH- +
H2O
+
H
+
H
H
OH
H2 O H S
H
O
+
2
H2S
H
H2O
2
22S
OH
OH
S
2S
HS17 Acid and Base

33

Base-ionization constant
For a base BOH,

For acid, HA

BOH = B+ + OH

HA = H+ + A

[B+] [OH]
Kb =
[BOH]
The pKb is defined similar to pKa
pKb = log Kb,

Kb = 10

pKb

Whatever you have learned for

weak acids apply to weak bases

[H+] [A]
Ka =
[HA]
The pKa is defined similar to the pH,
pKa = log Ka

Ka = 10 pKa

From slide 3

17 Acid and Base

June 18
34

Common weak bases

Substance
Ammonia
aniline
dimethylamine
ethylamine
Hydrozine
Hydroxylamine
methylamine
Pyridine
Urea

Formula
NH3
C6H5NH2
(CH3)2NH
C2H5NH2
N2H4
H2NOH
CH3NH2
C5H5N
NH2CONH2

Kb
1.8e-5
4.2e-10
5.1e-4
4.7e-4
1.7e-6
1.1e-8
4.4e-4
1.4e-9
1.5e-14

Many drugs are salts of

weak bases, such as
Advil
Pseudoephedrine HCl
Buckley's mixture
Dextromethorphan
hydrobromide
Dristan
Traxodone HCl

no need to copy Table 16.2

17 Acid and Base

35