Organic

Chemistry
William H. Brown
Christopher S. Foote
Brent L. Iverson
4-1

Acids
and
Bases
Chapter 4
4-2

Arrhenius Acids and Bases

In 1884, Svante Arrhenius proposed these

definitions
acid: a substance that produces H3O+ ions aqueous
solution
base: a substance that produces OH- ions in aqueous
solution
this definition of an acid is a slight modification of the
original Arrhenius definition, which was that an acid
produces H+ in aqueous solution
today we know that H+ reacts immediately with a water
molecule to give a hydronium ion
H+(aq) + H2O(l)

H3 O+(aq)
Hydronium ion

4-3

Brnsted-Lowry Definitions

Acid: a proton donor

Base: a proton acceptor
H O:

: :

+
H O H + :O

+ H O

H
Proton
donor

Proton
acceptor

H
Proton
donor

H O:

H
Proton
acceptor

H
+
H O H + :N

H
+
+ H N H
H

4-4

Conjugate Acids & Bases

conjugate base:
base the species formed from an acid when
it donates a proton to a base
conjugate acid: the species formed from a base when
it accepts a proton from an acid
acid-base reaction: a proton-transfer reaction
conjugate acid-base pair: any pair of molecules or ions
that can be interconverted by transfer of a proton
conjugate acid-base pair

conjugate acid-base pair

HCl(aq)
Hydrogen
chloride
(acid)

H2O(l)
Water
(base)

Cl-(aq)
+ H3 O (aq)
Chloride
Hydronium
ion
ion
(conjugate
(conjugate
base of HCl) acid of H2O)

4-5

Conjugate Acids & Bases

Brnsted-Lowry definitions do not require water as a
reactant
consider the following reaction between acetic acid
and ammonia
conjugate acid-base pair

conjugate acid-base pair

CH3 COOH + NH3
Acetic acid Ammonia
(acid)

(base)

CH3 COO
+
NH4
Acetate
Ammonium
ion
ion
(conjugate base (conjugate acid
acetic acid)
of ammonia)

4-6

Conjugate Acids & Bases

we can use curved arrows to show the flow of
electrons in an acid-base reaction
: :

H
+
:N H
H
Acetic acid
Ammonia
(proton donor) (proton acceptor)

: O:
H
CH3 -C-O: + H-N-H
H
Acetate ion Ammonium
ion
: :

: O:
CH3 -C-O H

4-7

Conjugate Acids & Bases

Many organic molecules have two or more sites

that can act as proton acceptors
in this chapter, we limit our discussion to carboxylic
acids, esters, and amides
in these molecules, the favored site of protonation is
the one in which the charge is more delocalized
question: which oxygen of a carboxylic acid is
protonated?
+ H

O
CH3 -C-O-H + H2 SO4

O
CH3 -C-O-H

O
+
or
CH3 -C-O-H + HSO4
H
A
B
(protonation
(protonation
on the
on the
carbonyl oxygen) hydroxyl oxygen)
4-8

Conjugate Acids & Bases

for protonation on the carbonyl oxygen, we can write
three contributing structures
two place the positive charge on oxygen, one places it
on carbon
+ H
O
CH3 -C-O-H

H
O
+
CH3-C-O-H
-C

A-1
(C and O have
complete octets)

A-2
(C has incomplete
octet)

H
O
+
CH3 -C=O-H

A-3
(C and O have
complete octets)

A-1 and A-3 make the greater contribution because all

atoms have complete octets
the positive charge is delocalized over three atoms
with the greater share on the two equivalent oxygens
4-9

Conjugate Acids & Bases

for protonation on the hydroxyl oxygen, we can write
two contributing structures
O

+
CH3 -C-O-H
H
B-1

O
+
CH3 -C-O-H
+
H
B-2
(charge separation and
adjacent positive charges)

B-2 makes only a minor contribution because of

charge separation and adjacent positive charges
therefore, we conclude that protonation of a carboxylic
acid occurs preferentially on the carbonyl oxygen
4-10

Conjugate Acids & Bases

Problem 4.3 Does proton transfer to an amide

group occur preferentially on the amide oxygen
or the amide nitrogen?
O
CH3 -C-N-H + HCl
H
Acetamide
(an amide)

+ H
O

CH3 -C-N-H or
H
A
(protonation
on the
amide oxygen)

OH
+
CH3-C-N-H + Cl H
B
(protonation
on the
amide nitrogen)

4-11

Pi Electrons As Basic Sites

Proton-transfer reactions occur with compounds

having pi electrons, as for example the pi
electrons of carbon-carbon double and triple
bonds
the pi electrons of 2-butene, for example, react with
HBr by proton transfer to form a new C-H bond
CH3 -CH=CH-CH3 + H-Br
2-Butene

+ H
CH3 -C-C-CH3 + Br

HH
sec-Butyl cation
(a 2 carbocation)

the result is formation of a carbocation,

carbocation a species in
which one of its carbons has only six electrons in its
valence shell and carries a charge of +1

4-12

Pi Electrons As Basic Sites

Problem 4.4 Draw Lewis structures for the two

possible carbocations formed by proton transfer
from HBr to 2-methyl-2-butene
CH3
CH3 -C=CH-CH3 + H-Br

2-Methyl-2-butene

4-13

Acids & Base Strengths

The strength of an acid is expressed by an

equilibrium constant
the acid dissociation of acetic acid is given by the
following equation
O
CH3COH + H2 O
Acetic acid Water

O
CH3CO
Acetate
ion

+ H3O
Hydronium
ion

4-14

Weak Acids and Bases

We can write an equilibrium expression for the

dissociation of any uncharged acid, HA, as:
+
A + H3 O

HA + H2 O
Keq =

[H3 O ][A ]
[HA][H2 O]

water is a solvent and its concentration is a constant

equal to approximately 55.5 mol/L
we can combine these constants to give a new
constant, Ka, called an acid dissociation constant
K a = Keq[H2 O] =

[H3 O ][A ]
[HA]
4-15

Acid
Weaker Ethane
acid
Ethylene
Ammonia
Hydrogen
Acetylene
Ethanol
Water

CH2=CH2
NH3
H2
HC CH
CH3CH2OH
H2 O

Methylammonium ion CH3NH3

Bicarbonate ion
Phenol
Ammonium ion
Hydrogen sulfide
Carbonic acid
Acetic acid
Benzoic acid
Phosphoric acid
Hydronium ion
Sulfuric acid
Hydrogen chloride
Stronger Hydrogen bromide
acid
Hydrogen iodide

pKa

Formula
CH3CH3

HCO3
C6H5 OH
+
NH4
H2 S
H2 CO3
CH3COOH
C6H5 COOH
H3 PO4
+
H3 O
H2 SO4
HCl
HBr
HI

51
44
38
35
25
15.9
15.7

10.64
10.33
9.95
9.24
7.04
6.36
4.76
4.19
2.1
-1.74
-5.2
-7
-8
-9

Conjugate Base
CH3CH2
Stronger
- conjugate
CH2 =CH
base
NH2
H
HC C
CH3CH2O
HO
CH3NH2
2-

CO3
C6H5 O
NH3
HS
HCO3
CH3COO
C6H5 COO
H2 PO4
H2 O
HSO4
Cl
Weaker
Br
conjugate
base
I

4-16

Acid-Base Equilibria

Equilibrium favors reaction of the stronger acid

and stronger base to give the weaker acid and
weaker base
CH3COOH

NH3

Acetic acid
Ammonia
(stronger base)
pKa 4.76
(stronger acid)

CH3 COO

NH4

Acetate ion Ammonium ion

(weaker base)
pKa 9.24
(weaker acid)

pKeq = 4.76 - 9.24 = -4.48

Ke q = 3.0 x 104

4-17

Acid-Base Equilibria

Consider the reaction between acetic acid and

sodium bicarbonate
we can write the equilibrium as a net ionic equation
we omit Na+ because it does not undergo any
chemical change in the reaction
O

HCO3
CH3COH +
Acetic acid
Bicarbonate ion
pKa 4.76
(stronger acid)

CH3CO +
H2 CO3
Acetate ion Carbonic acid
pKa 6.36
(weaker acid)

equilibrium lies to the right

carbonic acid forms, which then decomposes to
carbon dioxide and water
4-18

Molecular Structure and Acidity

The overriding principle in determining the

relative acidities of uncharged organic acids is
the stability of the anion, A-, resulting from the
loss of a proton
the more stable the anion, the greater the acidity of HA

Ways to stabilize anions include having the

negative charge
on a more electronegative atom
on a larger atom
delocalized through resonance
delocalized by the inductive effect
in an orbital with more s character

4-19

Molecular Structure and Acidity

A. Electronegativity of the atom bearing the
negative charge

within a period, the greater the electronegativity of the atom

bearing the negative charge, the more strongly its electrons are
held, the more stable the anion is, and the stronger the acid
Conjugate base

Acid
Methanol CH3 O H
pKa 16

Methylamine CH3 N H
pKa 38
H
H
Ethane CH3 C H
pKa 51
H

CH3 O

Methoxide ion

CH3 N Methylamide ion

H
H
CH3 C Ethyl anion
H

4-20

Molecular Structure and Acidity

B. Size of the atom bearing the negative charge

within a column of the Periodic Table, acidity is related to the size

of the the atom bearing the negative charge
atomic size increases from top to bottom of a column
the larger the atom bearing the charge, the greater its stability

CH3 S H

+ CH3 O

Methanethiol
Methoxide
pKa 7.0
ion
(stronger acid) (stronger base)

CH3 S

CH3 O H

Methanethiolate Methanol
ion
pKa 16
(weaker base) (weaker acid)

4-21

Molecular Structure and Acidity

C. Resonance delocalization of charge in A the more stable the anion, the farther the position of
equilibrium is shifted to the right
compare the acidity alcohols and carboxylic acids
ionization of the O-H bond of an alcohol gives an anion
for which there is no resonance stabilization
CH3CH2O-H + H2 O
An alcohol

CH3CH2O

+ H3 O

An alkoxide ion

pKa = 15.9

4-22

Molecular Structure and Acidity

ionization of a carboxylic acid gives a resonancestabilized anion
the pKa of acetic acid is 4.76
O
CH3 C

O
+ H2 O

OH

CH3 C

O
+

+ H3 O

CH3 C
O

equivalent contributing structures;

the carboxylate anion is stabilized by
delocalization of the negative charge.

carboxylic acids are stronger acids than alcohols as a

result of the resonance stabilization of the carboxylate
anion
4-23

Molecular Structure and Acidity

D. Electron-withdrawing inductive effect
the polarization of electron density of a covalent bond
due to the electronegativity of an adjacent covalent
H
F
bond
H C-CH2O-H
H

F C-CH2O-H
F

Ethanol
pK a 15.9

2,2,2-Trifluoroethanol
pK a 12.4

stabilization by the inductive effect falls off rapidly

with increasing distance of the electronegative atom
from
CF the
-CHsite
-OHof negative
CF -CH charge
-CH -OH CF -CH -CH -CH -OH
3

2,2,2-Trifluoroethanol
(pKa 12.4)

3,3,3-Trifluoro-1propanol
(pKa 14.6)

4,4,4-Trifluoro-1butanol
(pKa 15.4)

4-24

Molecular Structure and Acidity

we also see the operation of the inductive effect in the
acidity of halogen substituted carboxylic acids
O

OH
Butanoic
acid
pKa 4.82

Cl

Cl

OH

OH

OH

Cl
4-Chlorobutanoic 3-Chlorobutanoic 2-Chlorobutanoic
acid
acid
acid
pKa 4.52
pKa 3.98
pKa 2.83

4-25

Molecular Structure and Acidity

E. Hybridization

Water

HO-H

HO

15.7

Alkyne

HC C H

HC C

25

Ammonia H2 N-H

H2 N

38

Alkene

CH2 =CH-H

CH2 =CH

44

Alkane

CH3 CH2 -H

CH3 CH2

51

I
n
c
r
e
a
s
i
n
g
a
c
i
d
i
t

for anions differing only in the hybridization of the charged atom,

the greater the % s character to the hybrid orbital of the charged
atom, the more stable the anion
consider the acidity of alkanes, alkenes, and alkynes (given for
comparison are the acidities of water and ammonia)
Weak
Conjugate
pKa
Acid
Base

4-26

Lewis Acids and Bases

Lewis acid: any molecule of ion that can form a

new covalent bond by accepting a pair of
electrons
Lewis base: any molecule of ion that can form a
new covalent bond by donating a pair of
electrons
+ :B
Lewis Lewis
acid
base
A

+
A B

new covalent bond

formed in this Lewis
acid-base reaction

4-27

Lewis Acids and Bases

examples
:

H :Br :

: :

+
CH3 -C C-CH3

+ :Br : -

H H
secButyl cation Bromide
ion
(a carbocation)
CH3 CH2

F
B F

CH3 -C

C-CH3

H H
2-Bromobutane

CH3 CH2

F
+
:O:
+
:O B-F
CH3 CH2
F
F
CH3 CH2
Diethyl etherBoron trifluoride
A BF3-ether complex
(a Lewis base) (a Lewis acid)

4-28

Acids and
Bases
End Chapter 4

4-29