13-1 General Approach

to Acid-Base Systems
We first illustrate a general approach to find the concentrations of species in mixtures of
acids and bases. Consider a solution made by dissolving 20.0 mmol sodium tartrate
15.0 mmol pyridinium chloride and 10.0 mmol KOH in a volume
of 1.00 L. The problem is to find the pH and concentrations of all species in the solution.
The chemical reactions and equilibrium constants at 0 ionic strength are
(13-1)
(13-2)
(13-3)
(13-4)
The charge balance is
(13-5)
and there are several mass balances:
There are 10 independent equations and 10 species, so we have enough information to solve
for all the concentrations.
There is a systematic way to handle this problem without algebraic gymnastics.
Step 1 Write a fractional composition equation from Section 10-5 for each acid or base
that appears in the charge balance.
Step 2 Substitute the fractional composition expressions into the charge balance and
enter known values for and Also, write
At this point, you will have a complicated equation in which the only variable
is
Step 3 Use your trusty spreadsheet to solve for
Here is a recap of the fractional composition equations from Section 10-5 for any mono
protic acid HA and any diprotic acid
Monoprotic system: (13-6a)
(13-6b)
Diprotic system: (13-7a)
(13-7b)
(13-7c)
In each equation, is the fraction in each form. For example, is the fraction of diprotic
acid in the form When we multiply times (the total or formal concentration of
H2A), the product is the concentration of A2.
F
H
A2. A2 2A

i A2
[A2] A2FH
2A

K
1K2FH
2A

[H]2 [H]K1 K1K2

[HA] HAFH
2A

K
1[H]FH
2A

[H]2 [H]K1 K1K2

[H2A] H
2AFH2A
[H]2FH
2A

[H]2 [H]K1 K1K2

[A] AFHA
Ka
F
HA
[H] Ka
[HA] HAFHA
[H]FHA
[H] Ka
H
2A.
[H].
[H].
[Na], [K], [Cl]. [OH] Kw/[H].
[H2T] [HT] [T2] 0.020 0 M [PyH] [Py] 0.015 0 M
[Na] 0.020 0 M [K] 0.010 0 M [Cl] 0.015 0 M
[H] [PyH] [Na] [K] [OH] [HT] 2[T2] [Cl]
H
2O T H OH Kw 1014.00
PyH T Py H Ka 105.20
HT T T2 H K
2 104.366
H
2T T HT H K1 103.036
pK1 3.036, pK2 4.366 pKa 5.20
H2T PyHCl
NH Cl

D-Tartaric acid Pyridinium chloride

HO OH
CO
HO2C 2H
(NaHT), (PyHCl),
The approach to equilibrium problems in this
chapter is adapted from Julian Roberts,
University of Redlands.
For this example, we designate the two acid
dissociation constants of as and . We
designate the acid dissociation constant of
as K
PyH a.
K2
K1
H
2T
There is a factor of 2 in front of [ T2] because
the ion has a charge 2.
1 M T2 contributes a charge of 2 M.
“Independent” equations cannot be derived
from one another. As a trivial example, the
equations and are not
independent. The three equilibrium expressions
for and for a weak acid and its
conjugate base provide only two independent
equations because we can derive from
and : K
Kw b Kw/Ka.
Ka
Kb
Kw
Kb
Ka, ,
a b c 2a 2b 2c
F
HA [HA] [A]
F
H
A [H2A] [HA] [A2]
2

Table 11-6 gave fractional composition

equations for H3A.