Analytical Chemistry

Dr. Yehia Mechref

Chapter 11
Solving Equilibrium Problems for Complex Systems
POLYFUNCTIONAL ACIDS AND BASES
Phosphoric acid is a typical polyfunctional acid. In aqueous solution it
undergoes the following three dissociation reactions:

K a1 =

H 3PO 4 + H 2 O H 2 PO 4 + H 3O +

[H 3O + ][H 2 PO 4 ]
[H 3PO 4 ]

= 7.11 10 3
Ka2 =

H 2 PO 4 + H 2 O HPO 24 + H 3O +

[H 3O + ][HPO 24 ]
[H 2 PO 4 ]

= 6.32 10 8
Ka3 =

HPO 24 + H 2 O PO 34 + H 3O +

[H 3O + ][PO 34 ]
[HPO 24 ]

= 4.52 10 13
Generally, Ka1>Ka2>Ka3
Generally, Ka1>Ka2 by a factor of 104 to 105 because of electrostatic
forces. That is, the first dissociation involves separating a single
positively charged hydronium ion from a singly charged anion.
In the second step, a hydronium ion is separated from doubly charged
anion, a process that requires considerably more energy.
A second reason that Ka1>Ka2 is a statistical one. In the firs step, a proton
can be removed from two locations, whereas in the second step, only
from one. Thus, the first dissociation is twice as probable as the second.
COMBINING EQUILIBRIUM-CONSTAT EXPRESSIONS

When two adjacent stepwise equilibria are added, the equilibrium

constant for the resulting overall reaction is the product of the two
constants. Thus for the first two dissociation equilibria for H3PO4 we
may write,

Analytical Chemistry

Dr. Yehia Mechref

H 3PO 4 + H 2 O H 2 PO 4 + H 3O +

H 2 PO 4 + H 2 O HPO 24 + H 3O +

H 3PO 4 + 2H 2 O HPO 24 + 2H 3O +
and
K a1K a 2 =

[H 3O + ]2 [HPO 24 ]
[H 3PO 4 ]

= 7.11 10 3 6.32 10 8 = 4.49 10 10

Similarly, for the rection

H 3PO 4 + 3H 2 O PO 34 + 3H 3O +

we may write
K a1K a 2 K a 3 =

[H 3O + ]3[PO 34 ]
[H 3PO 4 ]

= 7.11 10 3 6.32 10 8 4.5 10 10 = 2.00 10 22

Sodium carbonate is a polyfunctional base.
Carbonate ion, the conjugate base of the hydrogen carbonate ion, is
involved in the stepwise equilibria:
K b1 =

CO 32 + H 2 O HCO3 + OH

[OH ][HCO 3 ]
[CO 32 ]

= 2.13 10 4
K b2 =

HCO 3 + H 2 O H 2 CO 3 + OH

[OH ][H 2 CO 3 ]
[HCO 3 ]

= 2.25 10 8

Analytical Chemistry

Dr. Yehia Mechref

The overall basic dissociation reaction of sodium carbonate is described

by the equations
K b1K b 2 =

CO 32 + 2H 2 O H 2 CO 3 + 2OH

[OH ]2 [H 2 CO 3 ]
[CO 32 ]

= 2.13 10 4 2.25 10 8
= 4.79 10 12

CALCULATION OF THE pH OF SOLUTIONS OF NaHA

An Amphiprotic salt is a species that can act as an acid and as a base
when dissolved in a suitable solvent.

These salts are formed during neutralization titration of polyfunctional

acids and bases
Generally, when a 1 mol of NaOH is added to a solution containing 1 mol
of the acid H2A, 1 mol of NaHA is formed.
The pH of the solution is determined by two equilibria established
between HA- and water.
HA + H 2 O A 2 + H 3O +
and
HA + H 2 O H 2 A + OH
Therefore, a solution of NaHA will be acidic or basic , depending on the
relative magnitude of the equilibrium constants for these processes:

Ka2 =
K b2 =

[H 3O + ][A 2 ]
[HA ]

K w [OH ][H 2 A]
=
K a1
[HA ]

where Ka1 and Ka2 are the acid dissociation constants for H2A.
If Kb2 is greater than Ka2, the solution is basic otherwise, it is acidic.
Calculating the pH of a solution of NaHA.

Analytical Chemistry

Dr. Yehia Mechref

A solution of NaHA can be described in terms of mass balance:

CNaHA = [H2A] + [HA-] + [A2-]
And charge balance:
[Na+] + [H3O+] = [HA-] + 2[A2-] + [OH-]
Since the sodium ion concentration is equal to the molar analytical
concentration of the salt, the last equation can be rewritten as
CNaHA + [H3O+] = [HA-] + 2[A2-] + [OH-]
Moreover, the dissociation constants for H2A are;

[H 3O + ][HA ]
K a1 =
[H 2 A]
Ka2 =

[H 3O + ][A 2 ]

[HA ]
Thus, we have four equations and need one more to solve for the five
unknowns.
Kw = [H3O+] [OH-]
Subtracting the mass-balance equation from the charge balance equation.
CNaHA + [H3O+] = [HA-] + 2[A2-] + [OH-]
= [H2A] + [HA-] + [A2-]
CNaHA
[H3O+] = [A2-] + [OH-] - [H2A]
We then rearrange the acid-dissociation constant expression for H2A to
obtain
[ H 3O + ][ HA ]
[ H 2 A] =
K a1
and for HA to give,

[A 2 ] =

K a 2 [HA ]
[ H 3O + ]

Analytical Chemistry

Dr. Yehia Mechref

Substituting these equations and the expression for Kw into the equation
obtained from the subtraction of the mass-balance and charge-balance
equations.

[H 3O + ][HA ]
[H3O ] =
+
K a1
[ H 3O + ]
[ H 3O + ]
Multiplication by [H3O+] gives
+

K a 2 [HA ]

Kw

[H 3O + ]2 [HA ]
[H3O ] = K a 2 [HA ] + K w K a1
We rearrange to obtain,
+ 2

+ 2 [ HA ]
+ 1 = K a 2 [HA ] + K w
[ H 3O ]
K a1

This equation can be rearranged to

+

[ H 3O ] =

K a 2 [HA ] + K w
1 + [HA ] / K a1

Under most circumstances, we can assume that

[HA ] C NaHA
Thus,
[ H 3O + ] =

K a 2 C NaHA + K w
1 + C NaHA / K a1

Frequently,
the ratio CNaHA/Ka1 is much larger than unity and
Ka2 CNaHA is considerably greater then Kw,
thus the above equation can be rewritten as
[H 3O + ] K a1K a 2

Analytical Chemistry

Dr. Yehia Mechref

EXAMPLE
Calculate the hydronium ion concentration of a 0.100 M NaHCO3
solution.
First, we examine the assumptions.
The dissociation constants for H2CO3 are
Ka1 = 4.45 x 10-7
Ka2 = 4.69 x 10-11
CNaHA/Ka1 = 2.2 x 105
Ka2 CNaHA = 4.69 x 10-12, is almost 100 times larger than Kw.
Thus, [H 3O + ] = 4.45 10 7 4.69 10 11 = 4.6 10 9

EXAMPLE
Find the hydronium ion concentration of 0.100 M NaH2PO4 solution
Ka1 = 7.11 x 10-3
Ka2 = 6.32 x 10-8
CNaHA/Ka1 = 14
Ka2 CNaHA = 6.32 x 10-9, is substantially larger than Kw.
Thus the second assumption is valid but not the first,
Thus,
K a 2 C NaHA
[ H 3O + ] =
1 + C NaHA / K a1

6.32 10 8 0.1
1.00 + (1.00 10 2 ) /(7.11 10 3 )

= 1.62 10 5