ACID-BASE THEORY

EVALUATION OF ACIDS

REVIEW OF
MAJOR THEORIES
YOU SHOULD HAVE STUDIED THESE IN GENERAL CHEMISTRY

BRONSTED - LOWRY THEORY

base

acid

HA

conjugate
base

conjugate
acid

BH

-H+
+H+

acid = proton donor

base = proton acceptor

Everything is defined
in terms of the proton,
the only recognized type
of acid in B-L theory.

LEWIS ACID - BASE THEORY

more general than Bronsted theory

B:

BASE
electron-pair donor

Subtances other
than proton donor
and acceptors are
recognized as
acids and bases.

ACID
electron-pair acceptor

Some Lewis Acids:

Fe3+ BF3

H3O+

Some Lewis Bases:

NH3 H2O BH4-

pKas AND ACID STRENGTH

pKa - An alternative to Ka to describe acid strength.

DEFINITION OF pKa

(A concise way to state the strength of an acid.)

HA + H2O

H3O+ + A-

[H3O ] [A ]
Ka =
[HA]
+

Compare the
definition of pH
pH = - log[H+]

You should already

know what a Ka is !

pKa = - log Ka

COMPARISON OF pKa and Ka VALUES

pKa = - log Ka
pKa

Ka

strong acids

-2
102

weak acids

2
10-2

10-6

10

12

10-10

The smaller the value of the pKa

the stronger the acid.

We will use pKa to describe the strengths of acids.

It is a single number, without exponents.

14
10-14

EVALUATION OF ACID STRENGTH

EVALUATION OF ACID STRENGTH

HA + H2O

H3O+ +

A-

In water, all acids form hydronium ion,

the important factor of difference is
the conjugate base.
The difference between a strong acid
and a weak acid is in the stability of
the conjugate base.
- WEAK ACID has
A
strong conj. base
E
N
E
R
G
Y

(=higher energy)

HA

ionization
easier

STRONG ACID has

weak conj. base
(=lower energy)

SOLVATION FOLLOWS IONIZATION

AE
N
E
R
G
Y

WEAK
ACID

solvation

A-

HA

STRONG
ACID

endothermic

solvation
exothermic

Note that the ions have a higher energy than the un-ionized acid,
but solvation can make the process involving the lower energy ion
(stronger acid) exothermic.

FACTORS THAT INCREASE ACIDITY

STABILIZATION OF A CONJUGATE BASE

We will study the factors that lead

to lower energy (stabilization) in
the conjugate base.

STABILIZATION
FACTORS
1 Resonance
2 Electronegativity

stabilization

3 Size of Atoms
4 Hybridization

A-

5 Inductive Effects
6 Charge

HA

Stabilization of the
conjugate base
makes the acid
stronger.

7 Solvation
8 Steric Effects*
* usually destabilize

RESONANCE
More resonance structures, or
better resonance structures,
for the conjugate base lead to
a stronger acid.

RESONANCE EFFECTS
increasing quality
of resonance

pKa Values

R OH

18

R CH3

45

R NH2

28

OH

10

CH3

30

NH2

25

R C NH2

15

O
R C OH

CH3O C CH3

25

O
R C CH3

20

O
R C CH2
C O
R

RESONANCE IN THE ACETATE ION

equivalent structures
charge on oxygens

O
CH3

C O H

-H+

CH3

C
O_

base

acetic acid

O
CH3

C
O

acetate ion

PHENOLATE ION RESONANCE

_
O

_
O

More structures,
but not better
than acetate.

_
Non-equivalent structures
charge on carbon and oxygen

ELECTRONEGATIVITY
When comparing two acids in the same period ...
placing the negative charge on a
more electronegative element in the
conjugate base leads to a stronger acid

EFFECT OF ELECTRONEGATIVITY
increasing
electronegativity

pKa Values

O
CH4

>45

RCH3

45

R C CH3
O

NH3

34

RNH2

35

R C NH2 15
O

H2O

16

ROH

18

R C OH

HF

3.5
H

conjugate
bases :

H C
H

H N
H

H O

20

ELECTRONEGATIVITY VALUES
( a reminder )

H
2.2

C
2.5

N
3.0

Si
1.9

P
2.2
F

increase
periodic chart trends

O
3.5
S
2.5

F
4.0
Cl
3.0

Br
2.8
I
2.5

SIZE
When comparing two acids in the same group ...
placing the negative charge on a larger atom
in the conjugate base leads to a stronger acid.

EFFECT OF ATOMIC SIZE

increasing
atom size

pKa Values

O
HF

3.5

HOH

16

R C OH
O

HCl

-7

HSH

R C SH
S

HBr -9

HSeH

R C

HI

HTeH

-10

F1.36 A

Cl1.81 A

I-

Br 1.95 A

SH

2.16 A

DEPENDENCE OF ACIDITY ON SIZE AND ELECTRONEGATIVITY

PERIOD

Acidity
Electronegativity

CH4

NH3

H2O

HF

SiH4 PH3

H2S

HCl

50

36

35

27

25

23

16
7

3.2
-7

GeH4 AsH3 H2Se HBr

3.7

-8

3.0

-9

H2Te

HI

GROUP
Size Acidity

HYBRIDIZATION
More S character in the orbital bearing the
negative charge in the conjugate base
leads to a stronger acid.

EFFECT OF HYBRIDIZATION
:

pKa values
H

sp3

H C H ca. 50
H

sp3

H C C H

C:

35

sp2
sp

H C C H

C:

25

electrons have lower

energy in sp hybrid closer to nucleus

H O H -1.74
H

H H

sp2

pKa values

:
sp

C:

R C O H
+
R

-7

INDUCTIVE EFFECTS
Small, but they can add up.

TYPES OF INDUCTIVE EFFECTS

ELECTRON
WITHDRAWING
GROUPS

Cl

ELECTRON
DONATING
GROUPS

CH3

F, Cl, Br, N, O
electronegative elements
take electron density
from cabon

R, CH3, B, Si
alkyl groups and elements
less electronegative than carbon
donate electron density to carbon

These electron withdrawing and donating groups work through

the sigma bond system, unlike the similarly named resonance
groups that work through the

system.

INDUCTIVE EFFECTS
HALOACIDS

-
C
Cl

Chlorine helps
to stabilize -CO2by withdrawing
electrons

Cl

O
O

O
C
O

The effect diminishes with distance

- it carries for about 3 bonds.

INDUCTIVE EFFECTS - 1
increasing
electronegativity

multiple
substituents

pKa Values

CH2COOH

3.13

CH3 COOH

4.75

Br

CH2COOH

2.87

Cl CH2 COOH

2.81

Cl
Cl

CH2COOH

F CH2COOH

2.81
2.66

Cl CH

COOH

1.29

Cl C COOH

0.65

Cl
Cl

INDUCTIVE EFFECT IN CHLOROACETIC ACIDS

elpot values shown
+33

O
CH3
pKa

red=neg
blue=pos

OH
4.8

Cl

+43

+37

O
CH2

Cl O
OH
2.8

Cl

C C
Cl

OH
0.7

INDUCTIVE EFFECTS - 2
pKa Values
H COOH
CH3

COOH

3.75

CH3CH2CH2 COOH

4.8

4.75

CH2CH2CH2 COOH

4.5

Cl
CH3CH2

COOH

4.87

CH3

COOH

4.0

CH COOH

2.9

CH CH2
Cl

CH3CH2CH2

COOH

4.81

Cl

CH3
CH3

C COOH
CH3

CH3CH2

distance

5.02
probably a solvation effect

SOLVATION

SOLVATION LOWERS ENERGY

Cl- (g) + n H2O

Cl- (aq) + HEAT (H)

Solvation is a type of weak bonding.

Energy is released when an ion is solvated.
This lowers the energy of the ion.
O H
(g)

+ n H2O

O HH H O
H

(aq)

Cl-

H O
H O HH O

Cl-

Cl

E
N
E
R
G
Y

solvated ion

WATER IS A POLAR SOLVENT

It can solvate both cations and anions

CATIONS

Polar bonds in
water make it a
polar molecule.

H
+

ANIONS

O H +

SIZE AND SOLVATION

CH3

COOH

4.75

CH3CH2

COOH

CH3CH2CH2

COOH

4.87
4.81

CH3
CH3

CH3

Notice that these are all similar

.but this one has a larger pKa

This is probably a solvation effect.

Solvation lowers the energy of the ion.

H
O H

Stronger
Acid

H O
H
O H

O H

unbranched

H
H O

O H

H O

5.02

C COOH

steric hindrance
H O
O

The bulky
t -butyl group
is not as well
solvated.

-O

H
H O
H

H O
O H
H

Weaker
Acid

HALOGEN OXYACIDS
A highly-charged (+) atom in the center and
multiple opportunities for back-bonding
resonance make for a strong acid.

inductive
effect

HALOGEN OXYACIDS

HOI

pKa

10

HOBr

8.7

HOCl

7.3

HClO2

HClO3

-1

HClO4

-8

more oxygen =
more resonance
(backbonding)

pKa HCl = 7

Cl O H

+1

O Cl O H

+2

O Cl O H

+3

O Cl O H
O

larger charge
on the central
atom (Cl)

SULFUR OXYACIDS
pKa values

H2S
H2SO3

H S

7 (14)
1.8 (7.2)

H2SO4

-3 (2)

FSO 3H

-12

O
+1
H O S O H

+
H O S O H
2
O
- -O
+2
F S O H

An added
inductive
effect.

O-

EFFECT OF CHARGE
CONJUGATE ACIDS OF BASES

CHARGE versus NO CHARGE

conjugate acid
(extra proton)

H O H

16

+
H O H -1.74
H
+
R O H
R
+
R C O H

-3.5

-6

OH

+
R C O H
R

-7

neutral molecule

pKa Values
34

H N H

Ar NH2

H
H

Ar NH3
+

H N H

25
4

9.24

H
R NH3

+
R C N H

10
-10

Conjugate acid
protons are always
stronger acids
than any protons
in the original
compound.

CONJUGATE ACIDS
weak base = strong conjugate acid
The conjugate acid of a weak base will be a
strong acid.

strong base = weak conjugate acid

The conjugate acid of a strong base will be a
weak acid.
The strongest bases usually carry a negative charge.
Weaker bases are usually neutral molecules with an
unshared pair of electrons.

COMPARATIVE TRENDS

COMPARATIVE EFFECTS ON pKa VALUES

25

sp

sp2

35

sp3

CH4

Hybridization

Electronegativity
NH3

50

CH3

H2O

34

NH2

30

10
O

O
CH3

CH3

20

NH2

CH3

15
Br

Inductive
Effect

HF

HCl -7

Size

HBr -9
HI -10

OH

4.8
I

Resonance

16

OH

25

O
CH3

The direction of the

arrows indicates an
increase in acidity.

Cl
F

CH2 COOH

3.1

CH2 COOH

2.9

CH2 COOH Cl

2.8

CH2 COOH

2.7

Multiple Inductive
Cl
CHCOOH Cl C
Cl

1.3

Cl

COOH

0.7

GENERALIZATION
MAJOR EFFECTS
Electronegativity
Size
Hybridization
Resonance
Highly-(+)-charged atom

MINOR EFFECT
Inductive Effects

These five can

cause big changes
in the pKa.

Smaller changes,
unless several add
together.

The effects are purposely not listed in an exact order of

importance from top to bottom; it is not really possible
to establish an exact order.

CLASSIFICATION OF WEAK AND STRONG ACIDS

BY FUNCTIONAL GROUP
weak acids
40

strong acids
20

10

OH

R C CH3

C C

R CH3

di- and trinitrophenols

R OH

R C NH2

R NH2

pKa
HCl

C C H

O
R

O
CH2

R C
R

HBr
HI
H2SO4

OH

HClO4
HNO3

alkanes

alkenes
amines

alcohols
ketones
amides
alkynes

phenols
-diketones

carboxylic
inorganic
acids
acids
nitrophenols oxyacids

NITROPHENOLS

NITROPHENOLS
Placing a nitro group on the benzene ring
of a phenol increases its acidity.
The effect is largest when the nitro group
is placed in an ortho or a para position on
the ring, and considerably smaller for the
meta position.
Multiple nitro groups at the ortho and para
positions can increase the pKa of a phenol
to the point that it becomes a very strong
acid.

pKa VALUES OF NITROPHENOLS

OH

7.2
NO2

OH

10

OH

9.3

OH

NO2

0.4
NO2

NO2

7.3
NO2

OH

O2N

O2N

OH

4.0

NO2

RESONANCE IN p--NITROPHENOL
O

_
_

NO2

NO2

When in an ortho
or para position
a nitro group can
participate in
resonance.

_
O

extra
structure

_
O

_
_
NO2

NO2

SUBSTITUTED BENZOIC ACIDS

pKa VALUES OF SUBSTITUTED BENZOIC ACIDS

o-

CH3
COOH
R
R=H
4.2

m-

p-

3.9

4.3

4.4

CH3O

4.1

4.1

4.5

Cl

2.9

3.8

4.0

O2N

2.2

3.5

3.4

Electron-donating groups have only a small effect.

Electron-withdrawing groups considerably increase
the strength of the acid, especially when placed in the
ortho position.

SUMMARY

ELECTRON-WITHDRAWING EFFECTS
STRENGTHEN ACIDS
O (-)

O (-)
C

R C
O-

O-

O-

R S OO

Any effect that bleeds electron density away from

the negatively-charged end of the conjugate base will
stabilize (lower the energy) of the conjugate base and
therefore make the acid stronger.

Conversely ..

ELECTRON-DONATING EFFECTS
WEAKEN ACIDS
O (-)

O (-)
C

R C
O-

O-

O-

O-

R S OO

Any effect that pushes extra electron density toward

the negatively-charged end of the conjugate base will
destabilize (increase the energy) of the conjugate base
and make the acid weaker.