17 Acid and Base

1
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 properties of substances.
17 Acid and Base
2
Answer these questions
What are acids?
What are bases?
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?
Understand important properties of substances
17 Acid and Base
3
Arrhenius acids and bases
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
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.
17 Acid and Base
4
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, NH
3
or NH
4
OH? 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
5
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 + H
2
O H
3
O
+
+ Cl
HNO
3
+ H
2
O H
3
O
+
+ NO
3

HC
2
H
3
O
2
+ H
2
O H
3
O
+
+ C
2
H
3
O
2

H
2
O + NH
3
NH
4
+
+ OH
conjugate acids and bases
172
17 Acid and Base
6
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
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Evolution of the acid-base concept
year thinker Acid Base acid-base reaction
1884 Arrhenius ionize ionize H
+
+ OH = HOH
H
+
OH
1923 Bronsted- Proton proton HA + B = HB + A
Lowry Donor acceptor conjugation
1923 Lewis electrophil nucleophil E + Nu = E:Nu
17 Acid and Base
8
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
+
, BF
3
,
Lewis bases are nucleophils: NH
3
, H
2
O, PH
3
Acid base reactions:
BF
3
+ :NH
3
F
3
B:NH
3
Lewis at his desk.
He generalized an idea.
179
17 Acid and Base
9
Relative strengths
of acids and bases
HClO
4
ClO
4

H
2
SO
4
HSO
4

HI I
HBr Br
HCl Cl
HNO
3
NO
3

H
3
O+ H
2
O
HSO
4
SO
4
2

H
2
SO
3
HSO
3

H
3
PO
4
H
2
PO
4

HNO
2
NO
2

HF F
HC
2
H
3
O
2
C
2
H
3
O
2

Al(H
2
O)
6
3+
Al(OH)(H
2
O)
5
2+
H
2
CO
3
HCO
3

H
2
S HS
HClO ClO
HBrO BrO
NH
4
+
NH
3
HCN CN
HCO
3
CO
3
2

H
2
O
2
HO
2
HS S
2

H
2
O OH
ROH RO
174 & 175 Table 173
The stronger the acid, the
weaker its conjugate base.
17 Acid and Base
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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 HNO
3
and HNO
2
? H
2
SO
4
, H
2
SO
3
?
How about HClO
4
, HClO
3
, HClO
2
, 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
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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.
178
Able to predict acidity from molecular structure.
17 Acid and Base
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Self-ionization of water
Water molecules autoionize
2 H
2
O (l) = H
3
O
+
(aq) + OH (aq)
[H
3
O
+
] [OH]
K
c
=
[H
2
O] (= 1000/18 = 55.6)
K
w
= [H
2
O] K
c
= 1e14 only at 25
o
C, its T dependent.
The ion product, K
w
increases as T increases, and its value remains
the same in the presence of acid or base.
17 3
The molecule of life, H
2
O, and its acidity.
17 Acid and Base
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Solutions of strong acids and bases
Strong acids and strong bases completely ionize in their solutions.
HCl (aq) + H
2
O (l) H
3
O
+
(aq)+ Cl

(aq)
KOH (aq) K
+
(aq)+ OH

(aq)
In a 0.100 M HCl or HNO
3
solution,
[H
+
] = 0.100 M
and [OH

] = 1e14 / 0.100 = 1e13 M at 25

o
C
In a 0.100 M NaOH or KOH solution,
[OH

] = 0.100 M
and [H
+
] = 1e14 / 0.100 = 1e13 M at 25
o
C
In a 0.010 M Ca(OH)
2
solution,
[OH

] = 2*0.010 = 0.020 M
[H
+
] = 1e14 / 0.020 = 5e13 M at 25
o
C
17 Acid and Base
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Some strong acids and bases
Strong acids
Hydrogen halides
HCl HBr HI
Oxyacids of halogens
HClO
3
HBrO
3
HIO
3
HClO
4
HBrO
4
HIO
4
Other oxyacids
H
2
SO
4
HNO
3
Strong Bases
Hydroxides of alkali metals
NaOH KOH CsOH
Hydroxides of alkali earth
Ca(OH)
2
Sr(OH)
2
17 4
17 Acid and Base
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Neutralization Reactions
The neutralization reaction between strong acids and strong bases
has the net ionic reaction
H
3
O
+
(aq)+ OH

(aq) = 2 H
2
O
The anions are bystander ions. They do not participate the reaction.
These ions are
I

, Br

, Cl

, NO
3

, HSO
4

, CClO
4

, Na
+
, K
+
, Cs
+
, Ca
2+
etc.
When dried, the ions left behind in neutralization reactions form salts.
17 Acid and Base
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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
+
]; [H
+
] = 10
pH
pOH = log [OH

]; [OH

] = 10
pOH
pK = log [K]; K = 10
pK
pH = 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
[H
+
] = 0.79 0.63 0.50 0.40 0.32 0.25 0.20 0.16 0.13
(not linear; need not copy, figure out yourself)
For aqueous solution;
K
w
= [H
+
] [OH

]
- log K
w
= pH + pOH = 14 only at 25
o
C
173, p672
17 Acid and Base
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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
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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
+
], [Ca
2+
], and pOH at 25
o
C.
Solution:
pOH = log 0.025 = 1.60
pH = 14.00 1.60 = 12.40 only applicable at 25
o
C
[H
+
] = 10
12.40
= 4.0e13 M Note that 4.0e-13*0.025 = 1e-14
[Ca
2+
] =
[OH]
/
2
= 0.013 M
17 Acid and Base
19
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
20
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.
HCH
3
COO H
+
+ CH
3
COO

acetic acid, vinegar spirit

HNic H
+
+ Nic

HNic = Niacine, C
5
NH
5
COOH, 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. HNO
3
. Nicotine is a major chemical in
tobacco .
N
N
CH
3
N
COOH
<= Nicotine
Niacine =>
Vitamine B3
17 Acid and Base
21
Caffeine
Caffeine C
8
H
10
N
4
O
2
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
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Ionization of weak acids
Ionization of acetic acid, HCH
3
COO, HA
HA = H
+
+ A

same as HA + H
2
O = H
3
O
+
+ A

[H
+
] [A

] A

= CH
3
COO

(acetate)
K
a
= K
a
acid ionization constant, important for an acid
[HA] K
a
equilibrium constant with solvent effect
The pK
a
is defined similar to the pH,
pK
a
= log K
a
K
a
= 10
pKa
See Table 17-3 on page 678
17 Acid and Base
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Some weak acids and bases
Common Weak Acids
Formic acid HCOOH
Acetic acid CH
3
COOH
Trichloroacetic acid CCl
3
COOH
Hydrofluoric HF
Hydrocyanic HCN
Hydrogen sulfide H
2
S
Water H
2
O
Conjugate acids
of weak bases NH
4
+
Common Weak Bases
ammonia NH
3
trimethyl ammonia N(CH
3
)
3
pyridine C
5
H
5
N
ammonium hydroxide NH
4
OH
water H
2
O
HS
-
ion HS
-
conjugate bases of
weak acids e.g.: HCOO
-
17 Acid and Base
24
Determine K
a
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 K
a
? What is the percent
of ionization?
Solution:
HNic = H
+
+ Nic

0.012-x x x
x = [H
+
] = 10
3.39
= 4.1e-4
[HNic] = 0.012 0.00041 = 0.012
(4.1e-4)
2
K
a
= = 1.4e-5
0.012
Degree of ionization = 0.00041 / 0.012 = 0.034 = 3.4%
17 Acid and Base
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Application of K
a
The K
a
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
x
2
K
a
= = 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
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pH of a weak acid
The pH of C M acid HA (K
a
) solution.
Method:
HA = H
+
+ A

C-x x x
x
2
K
a
=
C x
x
2
+ K
a
x C K
a
= 0
K
a
+ K
a
2
+ 4 C K
a
x =
2
pH = log x
The pOH of C M base BOH (K
b
)
solution.
Method:
BOH = B
+
+ OH

C-y y y
y
2
K
b
=
C y
y
2
+ K
b
x C K
b
= 0
K
b
+ K
b
2
+ 4 C K
b
y =
2
pOH = -log y
17 Acid and Base
27
Using the quadratic formula
The K
a
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
x
2
K
a
= = 1.4e-5 x
2
+ 1.4e-5 x 1.4e-8 = 0
0.00100 x
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%
Deg.f ionizn
0.22 0.79%
0.012 3.4 %
0.001 11.1 %
x
2
+ K
a
x C K
a
= 0
K
a
+ K
a
2
+ 4 C K
a
x =
2
17 Acid and Base
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Degree of or percent ionization
Deg.f ionizn
0.22 0.79%
0.012 3.4 %
0.001 11.1 %
The degree or percent of ionization of a weak
acid always decreases as its concentration
increases, as shown from the table given earlier.
Concentration of acid
% ionization
17 Acid and Base
29
Polyprotic acids
Polyprotic acids such as sulfuric and carbonic acids have more than
one hydrogen to donate.
H
2
SO
4
= H
+
+ HSO
4

K
a1
very large completely ionized
HSO
4

= H
+
+ SO
4
2
K
a2
= 0.012
H
2
CO
3
= H
+
+ HCO
3

K
a1
= 4.3e-7
HCO
3

= H
+
+ CO
3
2
K
a2
= 4.8e-11
Ascorbic acid (vitamin C)
is a diprotic acid, abundant
in citrus fruit.
Others:
H
2
S, H
2
SO
3
, H
3
PO
4
, H
2
C
2
O
4
(oxalic acid)
C
17 Acid and Base
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Aspartame -
nutrasweet
A dipeptide methyl ester :
L-aspartyl-L-phenylalanine methyl ester
C
14
H
18
N
2
O
5
(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
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Species concentrations of diprotic acids
Evaluate concentrations of species in a 0.10 M H
2
SO
4
solution.
Solution:
H
2
SO
4
= H
+
+ HSO
4

completely ionized
(0.10.1) 0.10+y 0.10-y
HSO
4

= H
+
+ SO
4
2
K
a2
= 0.012
0.10y 0.10+y y Assume y = [SO
4
2
]
(0.10+y) y
= 0.012
(0.10-y)
[SO
4
2
] = y = 0.01M
[H+] = 0.10 + 0.01 = 0.11 M;
[HSO
4

] = 0.10-0.01 = 0.09 M
Y
2
+ 0.112 y 0.0012 = 0
- 0.112+0.112
2
+ + 4*0.0012
y = = 0.0098
2
If concentrationf H
2
SO
4
= 1.0 M,
what doUdo?
17 Acid and Base
32
Species concentrations of weak diprotic acids
Evaluate concentrations of species in a 0.10 M H
2
S solution.
Solution:
H
2
S = H
+
+ HS

K
a1
= 1.02e-7
(0.10x) x+y x-y Assume x = [HS

]
HS

= H
+
+ S
2
K
a2
= 1.0e-13
xy x+y y Assume y = [S
2
]
(x+y) (x-y) (x+y) y
= 1.02e-7 = 1.0e-13
(0.10-x) (x-y)
[H
2
S] = 0.10 x = 0.10 M
[HS

] = [H
+
] = x y = 1.0e4 M;
[S
2
] = y = 1.0e-13 M
0.1>> x >> y:
x+ y = x-y = x
x = 0.1*1.02e-7 = 1.00e-4
y = 1e-13
See Example 16.4
17 Acid and Base
33
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.
H
2
S = H
+
+ HS

K
a1
= 1.02e-7
HS

= H
+
+ S
2
K
a2
= 1.0e-13
H
2
O = H
+
+ OH
-
K
w
= 1e-14
H
2
O
H
2
O
H
2
S
HS
-
H
+
H
+
H
+
H
2
S
H
2
O
H
2
O
H
2
S
OH
-
OH
-
OH
-
S
2-
OH
-
S
2-
S
2-
H
+
H
2
S(g)
HS
-
17 Acid and Base
34
Base-ionization constant
For acid, HA
HA = H
+
+ A

[H
+
] [A

]
K
a
=
[HA]
The pK
a
is defined similar to the pH,
pK
a
= log K
a
K
a
= 10
pKa
From slide 3
For a base BOH,
BOH = B
+
+ OH

[B
+
] [OH

]
Kb =
[BOH]
The pK
b
is defined similar to pK
a
pK
b
= log K
b
, K
b
= 10
pKb
Whatever you have learned for
weak acids apply to weak bases
June 18
17 Acid and Base
35
Common weak bases
Substance Formula K
b
Ammonia NH
3
1.8e-5
aniline C
6
H
5
NH
2
4.2e-10
dimethylamine (CH
3
)
2
NH 5.1e-4
ethylamine C
2
H
5
NH
2
4.7e-4
Hydrozine N
2
H
4
1.7e-6
Hydroxylamine H
2
NOH 1.1e-8
methylamine CH
3
NH
2
4.4e-4
Pyridine C
5
H
5
N 1.4e-9
Urea NH
2
CONH
2
1.5e-14
no need to copy Table 16.2
Many drugs are salts of
weak bases, such as
Advil
Pseudoephedrine HCl
Buckley's mixture
Dextromethorphan
hydrobromide
Dristan
Traxodone HCl