CHEMISTRY 15

ACIDS AND BASES

Operational Definition
Acid
-

substance that taste sour

turns blue litmus paper to red
reacts with active metals to evolve hydrogen gas

Base
-

feels slippery
taste bitter
turns red litmus paper into blue
neutralizes acids

This definition is limited to aqueous solutions.

Definition in Terms of Structure
1. Arrhenius definition first proposed in 1884; the oldest, most restrictive and
simplest definition:
Acid a neutral molecule that dissolves in water to give H+ ions and an
anion; it increases the [H+] of water
Base a neutral molecule that dissociates in water to give OH- and a
cation; it increases the [OH-] of water
Some examples of Arrhenius acids:

hydrogen chloride

nitric acid

acetic acid

benzenesulfonic acid

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

The common structural feature in these compounds is a hydrogen atom

bonded to an electronegative atom. It is this hydrogen atom that is released
as H+ when dissolved in water.
Some examples of Arrhenius bases:
NaOH
Ca(OH) 2

KOH
Ba(OH) 2

All these compounds contain a hydroxide ion (OH-).

An acid-base reaction in the Arrhenius sense is the coming together of H+ and
OH- to form water resulting in the destruction (neitralization) of the acid and
the base. An example is shown below:
() + () + + 2

The reaction results in the formation of water and a salt.

The acids and bases referred to in the operational definition are Arrhenius
acids and bases. The H+ ions impart the familiar acidic properties while the
OH- is responsible for the characteristic behaviour of a base.
2. Bronsted-Lowry definition suggested independently by Bronsted (Denmark)
and Lowry (England) in 1923; more general than the Arrhenius definition.
Acid a substance that donates a proton (H+).
Base a substance that accepts a proton
A Bronsted-Lowry acid must have a hydrogen atom bonded to an
electronegative atom. It is this hydrogen atom that is donated as a proton.
Arrhenius acids are also Bronsted-Lowry acids.
A Bronsted-Lowry base must have an available electron pair to share with a
proton.
The generalized Bronsted-Lowry acid-base reaction is shown below:

acid

base

conjugate base

conjugate acid

As to whether is it the forward or backward reaction that is going to be

favored depends upon the relative strengths of the pairs of reacting acid and
base. The strength of an acid depends upon its tendency to give up a proton,
while the strength of a base depends on its tendency to accept a proton. The
dissociation constant in water is frequently used as a measure of the relative
strength of acids and bases. The stronger the acid, the more it readily
donates a proton (large K a ). The stronger the base, the more readily it
accepts a proton (large K b ).

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For a reaction of an acid and a base, the equilibrium favors the presence of
the weaker base. Acid-base reactions run downhill to favour the formation
of the weaker base and weaker acid. H-A and :A- are a conjugate acid-base
pair; :B and H-B+ are likewise a conjugate acid-base pair. The stronger the
acid, the weaker its conjugate base and the stronger the base, the weaker its
conjugate acid.
Strong acids and bases are those that are almost completely ionized in water
(K a >2). For a strong acid, the only acid present in solution is H 3 O+. the only
base present in solutions of a strong base is OH-. Some examples are the
following:
Strong acids:

Strong bases:

HCl (hydrochloric acid)

HNO3 (nitric acid)
HClO4 (perchloric acid)

NaOH (sodium hydroxide)

KOH (potassium hydroxide)
Ca(OH) 2 (calcium hydroxide)

Weak acids and bases have their equilibria toward the left. These have small
acidity constants (K a ) and basicity constants (K b ), respectively.
The dissociation of a weak acid HA in water is shown by the equation below:
+ 2 + 3 +

The ionization constant expression for this reaction is:

=

[ ][3 + ]
[]

For a weak base B, the dissociation in water takes place according to the
equation:
+ 2 + +

The ionization constant expression for this reaction is:

=

[ + ][ ]
[]

3. Lewis definition proposed by G.N. Lewis in 1923; it is the broadest definition

and includes all other definitions.
Acid a substance that accepts an electron pair; must have a vacant
orbital which it can use to form a covalent bond with the electron pair
of the base.
Base a substance that donates an electron pair; must have an
available electron pair.

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

Examples of Lewis acids:

1. Molecules with an atom having less than an octet of electrons
AlCl 3 , BF 3
2. Molecules in which the central atom has available d orbitals and may
acquire more than an octet of electrons
SiF 4 , SnCl 4
3. Molecules with multiple bonds between atoms of dissimilar
electronegativity
..
..
..
..
4. Cations
Examples of Lewis bases:
1. Anions
2. Molecules with an atom having an unshared electron pair(s)
Examples of Lewis acid-base reactions:

1.

coordinate covalent bond

2.

+
Lewis acid

3. Ag+
+
Lewis acid

-OH

Lewis base
2NH 3
Lewis base

[H 3 N-Ag-NH 3 ]+

Any reaction that leads to the formation of a coordinate covalent bond is a

Lewis acid-base reaction.

Calculations Involving Acid-Base Equilibria

I.

pH of Strong Acids and Bases

Sample problem 1
What is the pH of a 0.05 M HNO 3 solution?

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

Solution:
HNO 3 is a strong acid, therefore, 0.05 M yileds 0.05 M of H 3 O+ ions and 0.05 M
NO 3 - ions.
3

0.05

[H 3 O+] = 0.05 M

3 + +

0.05

0.05

pH = -log [H+]
pH = -log 0.05
pH = 1.3
Sample problem 2
What is the pH of 0.012 M Ba(OH) 2 ?
Solution:
Ba(OH) 2 is a strong base, therefore:
()2

0.012

2+ +

0.012

0.012 M Ba(OH) 2 yields 0.024 M OH- ions, therefore

[ ] = 0.024

0.012

= [ + ] + = 1.0 1014
[+ ] =

1.0 1014
=
[ ]
0.024

[ + ] = 4.17 1014

= log 4.17 1014

Alternative solution:

= 12.4

= log[ ]
= log 0.024
= 1.6

+ = 14
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 = log[ ]
= 14
= 14 1.6
= 12.4

II.

pH and K a of Weak Acids and Bases

1. What is the pH of 1.0 M formic acid?
= 1.8 104

Solution:
The equation for the dissociation is:
2 + 2 3 + + 2
and K a is :

[3 + ][2 ]
[2 ]

Let x = the amount (moles/liter) of HCO 2 H that dissociates

At equilibrium,
[2 ] = [3 + ] =

[2 ] = 1.0 = 1.0,
Therefore,

2 = 1.8 104

= 1.34 102

= log(1.34 102 )
= 2 log 1.34
= 1.87

2. Calculate the OH- ion concentration of 0.80 M CH 3 NH 2 .

= 3.7 104
Solution:
The equation for the dissociation is:
3 2 + 2 3 3 + +
0.80 x

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

The dissociation constant is :

[ ]3 3 +
=
[3 2 ]

At equilibrium,
3 3 + =
[ ] =
[3 2 ] = 0.80
()()
2
=

(0.80 ) 0.80

2
= 3.7 104
0.80
= 0.017

[ ] = 0.017

3. A student prepared a 0.10 M acetic acid solution and experimentally

measured the pH of this solution to be 2.88. Calculate K a for acetic acid
and its % dissociation.

Solution:
The equation for the dissociation is:
3 2 + 2 3 + + 3 2
=

[3 + ][3 2 ]
[3 2 ]

pH= -log [H+] = 2.88

[H+] = antilog (-pH)
[H+] = antilog (-2.88) = 1.32 10 -3

At equilibrium, [H+] = [CH 3 CO 2 -] = 1.32 10 -3

[CH 3 CO 2 H] = 0.10 - 1.32 10 -3 = 0.10
Therefore,
=

% =

(1.32 103 )2
= 1.7 105
0.10

100

1.32 103
100
0.10
= 1.32 %
4. What are the concentrations of all species in a 0.5 M HCN solution?
K a = 4.93 1010
=

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

Solution:
Equation for dissociation:
+ 2 3 + +
=

[3 + ][ ]
[]

Let x = amount of HCN that dissociates.

At equilibrium,
[] = 0.50
[ + ] =
[ ] =
[ ] = 1.0

1014

()()
= 4.93 1010
(0.50 )
0.50

2
= 4.93 1010
0.50
2 = 2.46 1010
= 1.57 105

Therefore,

[] = 0.50

[ + ] = 1.57 105

[ ] = 1.57 105

[ ] = 6.37 1010

BUFFERS
A buffer is a solution that is able to absorb small additions of concentrated
acids and bases without giving rise to a significant change in the pH of the solution.
An acidic buffer has a pH < 7 and consists of a solution of a weak acid (HA)
and its salt or anion (conjugate base, A-).
The anion is able to neutralize or use up H+ ions from additional acid:

+ 3 + + 2

The acid is able to neutralize or use up OH- ions from the additional base:

+ + 2

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An alkaline or basic buffer has a pH > 7 and consists of a solution of a weak

base (B) and its salt or cation (conjugate acid, BH+).
The cation is able to neutralize or use up OH- ions from additional base:

+ + + 2

The base is able to neutralize or use up H+ ions from additional acid:

Sample Problems:

+ 3 + + + 2

1. A buffer solution of pH 4.80 is to be prepared from propionic acid and sodium

propionate. The sodium propionate concentration is 0.50 mol/li. What should
be the concentration of the acid?
= 1.34 105

Solution:
The equilibrium involved is
3 2 2 3 2 2 + +
[3 2 2 ][+ ]
=
[3 2 2 ]
[3 2 2 ][ + ]
[3 2 2 ] =

Upon ionization, sodium propionate yields the propionate anion:

3 2 2 + 3 2 2 + +
0.5 M

0.5 M

0.5 M

0.5 M sodium propionate contains 0.5 mol/li of propionate ions.

The [H+] can be determined from the pH.
pH = 4.80
[H+] = antilog (-4.80)
[H+] = 1.58 10-5 M
So,
(0.50) 1.58 105
= 0.59
1.34 105
2. A buffer was prepared by mixing 200 mL of 0.6 M NH 4 Cl solution.
a) What is the pH of this buffer, assuming a final volume of 500 mL? (K b = 1.8
10-5)
b) What will be the pH after 0.02 mole of H+ is added?
[3 2 2 ] =

General Chemistry and Chemical Education Division, Institute of Chemistry, UPLB

Solution:
a)

The equilibrium involved is:

3 + 2 4 + +
4 + [ ]
=
[3 ]
[3 ]
[ ] =
4 +
mol 3 = 200 mL 0.6 mol/ 1000 mL = 0.12 mol
mol 4 + = 300 mL 0.3 mol/ 1000 mL = 0.09 mol
[3 ]= 0.12 mol/0.5 L = 0.24 M
4 + = 0.09 mol/0.5 L = 0.18 M
Thus,

pOH = - log 2.4 10-5

pOH = 4.62
pH = 14 4.62
pH = 9.38

[ ] =

(0.24)(1.8 105 )
0.18

b)

Upon addition of H 3 O+, it reacts with the base:

3 + 3 + 4 + + 2
This uses up some of the NH 3 and forms a corresponding amount of NH 4 +
The concentration of acid that was added is given by:
[H 3 O+] = 0.02 mol/0.5 L = 0.04 M
The concentration of NH 3 will be reduced by 0.04 M while the NH 4 +
concentration increases by 0.04 M.
[NH 3 ] = 0.24 0.04 (amount that reacts with the added acid) = 0.20
[NH 4 +] = 0.16 + 0.04 (amount that is formed from the added acid) = 0.22
(0.20)(1.8 105 )
[ ] =
= 1.6 105
0.22
pOH = 4.79; thus, pH = 9.20

POLYPROTIC ACIDS
Polyprotic acids are acids that contain more than one atom of H that can be
released as a proton upon dissociation. The following are some examples:
1. H 2 SO 4
2 4 + + 4
4 + + 4 2

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2. H 3 PO 4
3 4 + + 2 4
2 4 + + 4 2
4 + + 4 3

1 = 7.5 103
2 = 6.2 108
3 = 2.2 1012

2 3 + + 3
3 + + 3 2

1 = 4.3 107
2 = 5.6 1012

3. H 2 CO 3

Notice that the first dissociation step occurs with the largest value of K a and
that each successive step occurs with an ever-decreasing value of K a . it is
easiest to remove an H+ ion from an uncharged species. It becomes
progressively more difficult to remove an H+ as the negative charge on the ion
increases.

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