Chemistry 201

Lecture 16

Polyprotic acids and bases

Applications

NC State University
Titration curve summary

[OH-]/[HA]0
 use rxn table
goes 100%
calc pH or pOH

Strong Strong
Acid Base
use rxn table use rxn table
goes 100% Weak Weak goes 100%
buffer : H-H Acid Base buffer : H-H
base : pOH acid : pH
Examples: Weak acid and weak base
For a reaction of a weak acid and a weak base
we need to calculate the equilibrium constant
from the known Kas. We take the example of
ammonium acetate.

We see that the overall reaction is composed

of two acid-base equilibria
for acetate

for ammonia
Examples: Weak acid and weak base
Therefore, the overall equilibrium constant for
the reaction is

Now, that we can see how to calculate the

Equilibrium constant, we can solve any acid-base
Reaction problem using the standard methods
That we have used.
Step. 1. determine dilutions
Step. 2. set up the reaction table
Step. 3. solve for the unknown and then calculate pH
Examples: Weak acid and weak base
Therefore, the overall equilibrium constant for
the reaction is

In this case we can look up the pKas

pKa for acetic acid/acetate is 4.74
pKa for ammonium ammonia is 9.25

pK = pKa1 pKa2 = 4.74 9.25 = -4.51

K = 10-pK = 104.51 = 3.23 x 104

Examples: Weak acid and weak base
200.0 mL of 0.30 M NaH2PO4 was added to
200.0 mL of 0.30 M NaHS. What are the
concentrations of all species at equilibrium?
Examples: Weak acid and weak base
200.0 mL of 0.30 M NaH2PO4 was added to
200.0 mL of 0.30 M NaHS. What are the
concentrations of all species at equilibrium?
Solution: Look up the Ka for each reaction involved
in this acid-base equilibrium.
Examples: Weak acid and weak base
Species
Initial 0.15 0.15 0.0 0.0
Difference -x -x x x
Final 0.15-x 0.15-x x x
 Examples: Weak acid and weak base
Species
Initial 0.15 0.15 0.0 0.0
Difference -x -x x x
Final 0.15-x 0.15-x x x

Shortcut: realize that you can take the square of both sides
 Strong Strong
Acid Base

Weak Weak
Acid Base

if conjugates if not conjugates

use H-H calc. K
calc pH calc concs.
Polyprotic acids: Phosphoric acid

Note that each K value is over 1,000 times smaller than the
preceding value. This is the case for most polyprotic acids,
and it is why polyprotic acids can be treated in a relatively
simple manner. The large decrease in K means that a
negligible amount of each acid reacts in each step, so the
concentration of any species is the concentration
determined in the first step in which it is produced.
Polyprotic acids: Phosphoric acid
The point is that we can calculate the pH for each
equilibrium separately.
Determine [H3O1+], [H2PO41-], and [H3PO4] from the first
acid dissociation. These concentrations are not affected by
subsequent steps because the subsequent equilibrium
constants are so small.

Set up the reaction table for the second reaction using the
[H3O1+] and [H2PO41-] determined in Step 1 as the initial
conditions. Solve the equilibrium problem for [HPO42-],
which will be shown to equal K2.

Set up the reaction table for the third reaction using [H3O1+]
and [HPO42-] determined in Steps 1 and 2 as initial
concentrations. Solve the equilibrium problem for [PO43-]
Polyprotic bases: Sulfide

We can treat polyprotic bases in the same way as acids.

The equilibrium constants are separated by orders of
magnitude. They can be solved sequentially.
Figure 7.7
Figure 7.7

Amphiprotic acid
 Amphiprotic Acids
Amphiprotic acids have two equilibria. In theory this can require
solution of two variables. This is possible because each
equilibrium constant gives a constraint (two equations and
two unknowns).

However, there is a simpler solution. Mass balance requires

 Amphiprotic Acids
The trick to solving these equations for the pH is to write
The equation in terms of HA-.
 Amphiprotic Acids
Finally we observe that the maximum value of HA- will be
formed when

which gives the following simple result

and
Buffers formed from polyprotic acids

The buffer region of a polyprotic acid is within 1 pH

unit of each pKa of the acid. The example on the
next page shows a diprotic acid with two different
buffer regions. There are also two equivalence
points.
Figure 7.4
Carbonic acid: major determinant
of ocean chemistry
Carbonic acid has two acidity constants. When
CO2 is taken up by water it reacts to form hydrogen
carbonate. HCO3- is the major form of this acid.

The balance of carbonate and hydrogen carbonate

is very important for life in the ocean.
Coral reefs are highly colored
collections of CaCO3
Diatoms are microorganisms that
fix CO2 and produce O2
 Amphiprotic carbonic acid
The pKas of carbonic acid are pKa1 = 6.35 and
pKa2 = 10.35. We see an interesting situation
where:
1. Neither pKa is in the buffer range for the current
ocean pH (pH ~ 8.1)
2. The amphiprotic pH of carbonic acid is the
average of the two values, which is 8.35.
Once we understand these two facts we can see
the following. The ocean despite its large size is
not particularly strongly buffered. Therefore, as
CO2 dissolves it pulls the equilibrium of the CO32-
towards HCO3-.
Thinking about ocean acidification
The two equilibria are:

The current ocean pH = 8.35 is outside the buffer

range for both. However, the addition of CO2 will
clearly shift the pH lower according to H-H. Thus,
the equilibrium of the second reaction will shift
accordingly. The net result is an increase in
[HCO3-] at the expense of [CO32-].
 Acid catalysis: General description
Acid catalysis involves the acceleration of a reaction in rate
by protonation. For example, in solvent S, the reaction rate
may be proportional to the concentration of protonated
solvent molecules [SH+]. The acid catalyst (AH) contributes to
the rate acceleration by shifting the chemical equilibrium
between solvent S and AH in favor of the SH+species.

S + AH SH+ + A-

For example in an aqueous buffer solution the reaction rate

for reactants R depends on the pH of the system but not on
the concentrations of different acids.
Zeolites are SiO2 structures that can have Al-OH doping to
create acidic sites that can help to catalyze reactions.
Acid catalysis: zeolites
 Goals
Calculate pH change when acid or base is
added to a buffer
Find solution composition at a given pH
Review methods for acid-base problems
Consider implications for polyprotic acids and
bases