1.

12
Acids and Bases:
The Arrhenius View

Definitions
Arrhenius
An acid ionizes in water to give protons. A
base ionizes in water to give hydroxide ions.
Brnsted-Lowry
An acid is a proton donor. A base is a proton
acceptor.
Lewis
An acid is an electron pair acceptor. A base
is an electron pair donor.

Arrhenius Acids and Bases

An acid is a substance that ionizes to give
protons when dissolved in water.

H + + .. A

A base is a substance that ionizes to give

hydroxide ions when dissolved in water.

.
OH
.
.

M+ + .. OH
.
.

Arrhenius Acids and Bases

Strong acids dissociate completely in water.
Weak acids dissociate only partially.

H + + .. A

Strong bases dissociate completely in water.

Weak bases dissociate only partially.

.
OH
.
.

M+ + .. OH
.
.

Acid Strength is Measured by pKa

H + + .. A

Ka =

[H+][A]
[HA]

pKa = log10Ka

1.13
Acids and Bases:
The Brnsted-Lowry View
Brnsted-Lowry definition
an acid is a proton donor
a base is a proton acceptor

A Brnsted Acid-Base Reaction

A proton is transferred from the acid to the
base.

B .. + H A
base

acid

+
B

H + .. A

A Brnsted Acid-Base Reaction

A proton is transferred from the acid to the
base.

B .. + H A
base

acid

+
B

H + .. A

conjugate conjugate
acid
base

Proton Transfer from HBr to Water

hydronium ion

H
..
.. O .. + H Br ..
.
.
H
base

acid

H
+
..

.. O H + .. Br ..
.
.
H
conjugate conjugate
acid
base

Equilibrium Constant for Proton Transfer

H
..
+
.. O H + .. Br ..
.
.
H

H
..
.. O .. + H Br ..
.
.
H
Ka =

[H3O+][Br]
[HBr]

Takes the same form as for Arrhenius Ka, but

H3O+ replaces H+. H3O+ and H+ are considered
equivalent, and there is no difference in Ka
values for Arrhenius and Brnsted acidity.

Equilibrium Constant for Proton Transfer

H
..
+
.. O H + .. Br ..
.
.
H

H
..
.. O .. + H Br ..
.
.
H
Ka =

[H3O+][Br]
[HBr]

pKa = log10 Ka

Water as a Brnsted Acid

H
..

.. N .. + H OH
.
.
H
base

acid

H
.. N
H

..
H + .. OH
.
.

conjugate conjugate
acid
base

stronger
acid

Dissociation Constants (pKa) of Acids*

Acid
HI

-10.4

Conj. Base

-5.8

Br

H2SO4

-4.8

HSO4

HCl
+
H3O

-3.9

Cl

-1.7

H2O

HBr

weaker
acid

pKa

strong acids are stronger than hydronium ion

*ForamoredetailedlistclickhereforTable1.8

stronger
acid

Important Generalization!
Acid
HI

-10.4

Conj. Base

-5.8

Br

H2SO4

-4.8

HSO4

HCl
+
H3O

-3.9

Cl

-1.7

H2O

HBr

weaker
acid

pKa

The stronger the acid, the weaker the conjugate base.

*ForamoredetailedlistclickhereforTable1.8

Dissociation Constants (pKa) of Acids*

Acid
+

H3O
HF

pKa

Conj. Base

1.7

H2O

3.5

CH3CO2H

4.6

CH3CO2

+
NH4

9.2

NH3

H2O

15.7

HO

weak acids are weaker than hydronium ion

*ForamoredetailedlistclickhereforTable1.8

Dissociation Constants (pKa) of Acids*

Acid

pKa

Conj. Base

CH3OH

15.2

CH3O

H2O

15.7

HO

CH3CH2OH
(CH3)2CHOH
(CH3)3COH

~16

CH3CH2O

~17

(CH3)2CHO

~18

(CH3)3CO

alcohols resemble water in acidity; their conjugate

bases are comparable to hydroxide ion in basicity
*ForamoredetailedlistclickhereforTable1.8

Dissociation Constants (pKa) of Acids*

Acid
NH3
(CH3)2NH

pKa

Conj. Base

~36

NH2

~36

(CH3)2N

ammonia and amines are very weak acids;

their conjugate bases are very strong bases
*ForamoredetailedlistclickhereforTable1.8

Dissociation Constants (pKa) of Acids*

Acid
HC
H

pKa
26

CH
H

H2C

43

H
CH2

CH3CH3

HC

H
H

Conj. Base

H
45
62

CH

H2C

CH3CH2

Most hydrocarbons are extremely weak acids.

*ForamoredetailedlistclickhereforTable1.8

1.14
What Happened to pKb?

About pKa and pKb

A separate basicity constant Kb is not
necessary.
Because of the conjugate relationships in the
Brnsted-Lowry approach, we can examine
acid-base reactions by relying exclusively on
pKa values.

H
Example

N
H

Which is the stronger base, ammonia (left) or

pyridine (right)?
Recall that the stronger the acid, the weaker
the conjugate base.
Therefore, the stronger base is the conjugate
of the weaker acid.
Look up the pKa values of the conjugate acids
of ammonia and pyridine in Table 1.8.

Example
H
H

+
N

pKa = 9.3

weaker acid

pKa = 5.2

stronger acid

+
N
H

Therefore, ammonia is a
stronger base than pyridine