Polyprotic Acids
Polyprotic Acids
A polyprotic acid has more than one
ionizable proton (H+).
e.g. H2SO4, H2CO3, H3AsO4
Each successive Ka value get smaller (Ka1
> Ka2 > Ka3). Therefore, the first
dissociation step makes the most
significant contribution to the
equilibrium concentration of [H+].
Sulfuric acid is unique in being a
strong acid in its first dissociation
step and a weak acid in its second
step.
A polyprotic acid always dissociates in a
stepwise manner, one proton at a time.
Example of Diprotic acid
H2CO3(aq) HCO3- + H+
Ka1= 4.3 x 10-7
HCO3-(aq) CO32- + H+
Ka2 = 5.6 x 10-11
CO2(aq) + H2O(l) H+(aq) + HCO3-(aq)
Example of triprotic acid
The relative acid strengths are
H3PO4 >> H2PO4- >> HPO42-
LeChâtelier
For 1.0 M or larger solutions of sulfuric
acid, the large concentration of H3O+
from the first dissociation step
represses the second step, which can be
neglected as a contributor of H3O+ ions.
For dilute solutions of sulfuric acid, the
second step does make a significant
contribution, ICE tables must be used to
obtain the total H3O+ concentration.
The pH of a polyprotic acid
Calculate the pH of a 5.0-M H3PO4 solution
and the equilibrium concentrations of the
species H3PO4, H2PO4-, HPO42-, and PO43-.
The major species in solution are
• H3PO4 and H2O
Problem
Calculate the pH of 1.0 M H2SO4
H2SO4 HSO4- + H+ Ka is very large
HSO4- ⇌ SO42- + H+ Ka = 1.2x10-2
The main difference from sulfuric acid from
other problems will be the first step.
1.0 M H2SO4 means 1.0 M H+ and 1.0 M
HSO4- is formed.
Now to the second dissociation
Cont.
HSO4- SO42- + H+
I 1.0 M 0 1.0 M
C -x +x +x
E 1.0 –x x 1.0 + x
Ka2 = [x(1.0 + x)] / (1.0-x) = 1.2 x 10 -2
x = 1.2 x 10-2
[H+ ] = 1.0 M + x = 1.0 + (1.2 x 10 -2)
= 1.0 M and pH = 0.00
The pH of Sulfuric acid
Calculate the pH of a 1.00 x 10-2 M H2SO4
solution
The major species in solution are
H+, HSO4- and H20
HSO4- SO42- + H+
I 0.0100 M 0 0.0100 M
C -x +x +x
E 0.0100 –x x 0.0100 + x
Problem
Calculate the pH, [H+], [HSO4-], [SO42- ] of
0.20 M H2SO4
Calculate the pH of a 5.0 M H3PO4 solution
and the equilibrium concentrations of the
species H3PO4, H2PO4-, HPO42-, and PO43-.
Ka1 = 7.5 x 10-3
Ka2 = 6.2 x 10-8
-13
Salts
Salts and pH
Salts are made of conjugate acids and bases.
The conjugate acid/bases of strong acids or
base will be neutral, excluding H2SO4.
To be a strong acid or base, the conjugate
base or acid must have no affinity for
protons or hydroxide.
That is to say it won’t run the reverse
reaction under any conditions.
Salts of weak acids and bases
Conjugate bases/acids of weak acids and
bases will run the reverse reactions.
Conjugate base of weak acids are weak
bases
HF ⇌ H+ + F-
F- + H2O ⇌ HF + OH-
Conjugate acids of weak bases are weak
acids
NH3 ⇌ NH4+ + OH-
+ +
pH of salt
Salts are made by joining the conjugate
acids and bases
Would potassium chlorite be acidic or
basic?
KClO2 ⇌ K+ + ClO2-
Potassium is neutral (KOH = strong base),
chlorite is basic (HClO2 = weak acid)
Therefore it is basic
Conjugate base of a strong acid has virtually
no affinity for protons in water
Ex: Cl- and NO3- when placed in H2O; they do
not combine with H+ and have no effect on the
pH
Cations such as K+ and Na+ from strong bases
have no affinity for H+, so too they have no
effect on the pH of an aqueous solution
Salts that consist of the cations of strong
bases and the anions of strong acids have no
effect on [H+] when dissolved in water.
Ka and Kb
The Ka and Kb of a weak acid and its conjugate
base or a weak base and its conjugate acid are
related and easily calculated from one another
For a weak acid and its conjugate base or a
weak base and its conjugate acid only
Ka x Kb = Kw
For any salt whose cation has neutral
properties (such as Na and K) and whose anion
is the conjugate base of a weak acid, the
aqueous solution will be basic.
Salt as Weak Bases
Calculate the pH of a 0.30 M NaF solution.
The Ka value for HF is 7.2 x 10-4.
The major species in solution are
Na+, F- and H2O
Since HF is a weak acid, the F- ion must
have a significant affinity for protons, and
the dominant reaction will be
F-(aq) + H2O(l) ⇌ HF(aq) + OH-(aq)
The corresponding ICE table is
F-(aq) + H2O(l) ⇌ HF(aq) + OH-(aq)
I 0.30 - 0 0
C -x - +x +x
E 0.30 -x - x x
x 2.0 x 10-6
The approximation is valid by the 5% rule, so
pOH = 5.69
pH = 14.00 – 5.69 M
As explained the solution is basic
Base Strength in Aqueous
Solutions
Consider
(aq)
Since HCN is a weak acid, CN- appears to
be a strong base showing a very high
affinity for H+ compared to H2O
(aq)
Problem
Calculate the Ka of NH4Cl solution. The Kb
value for NH3 is 1.8 x 10-5.
Calculate the Kb of NaF solution. The Ka
value for HF is 7.2 x 10-4.
Hydrated metal ions
Charged metals ions also produce an acidic
solution.
The metal itself does not act as a Brønsted-
Lowry acid, but instead forms a hydrate that
acts as a Brønsted-Lowry acid.
Typically the higher the charge on the metal
ion, stronger the acidity of the hydrated ion.
Cu2+ + 5 H2O Cu(H2O)52+
Cu(H2O)52+ ⇌ CuOH(H2O)42+ + H+
Acidity of hydrated metal ions
M = metal
For Mn+, a small, highly charged ion,
M(H2O)xn++ H2O ⇌ M(H2O)x-1OH(n-1) + H3O+
Calculate the pH of a 0.010 M AlCl 3 solution.
The Ka value for Al(H2O)63+ is 1.4 x 10-5.
