Calculation of concentrations of all species in a

polyprotic acid
Let’s start off by assuming a general polyprotic acid H3A with the following ionization
equilibria.

H3A + H2O ¾ H3O+ + H2A- Ka1 = 1.0×10-4

H2A- + H2O ¾ H3O+ + HA2- Ka2 = 2.5×10-9
HA2- + H2O ¾ H3O+ + A3- Ka3 = 1.7×10-14

We start by calculating the [H3O+] and [H2A-] from the first equilibrium with an initial
concentration of acid of 0.10 M.

⎡⎣H3O + ⎤⎦ ⎡⎣H2 A− ⎤⎦
K a1 = = 1.0 × 10−4
[ H3 A ]
HA H3O+ A-
I 0.10 1.0×10-7 0
C -x +x +x
E 0.10-x 1.0×10-7 + x x

Making the standard assumptions, we get:

x2
Ka = = 1.0 × 10−4
0.10
x= ( 0.10 ) (1.0 × 10−4 ) = 3.2 × 10−3

The assumptions are valid here and we can say that:

⎡⎣H3O + ⎤⎦ = ⎡⎣H 2 A − ⎤⎦ = 3.2 × 10 −3 M

Now we look at the second equilibrium. The values we just calculated are the initial
values for the second equilibrium.

⎡⎣H3O + ⎤⎦ ⎡⎣HA2 − ⎤⎦
Ka2 = = 2.5 × 10 −9
⎡⎣H 2 A ⎤⎦
−
Our ICE table is then:

H2A- H3O+ HA2-

I 3.2×10-3 3.2×10-3 0
C -x -x +x
E 3.2×10-3 + x 3.2×10-3 + x x

Our K in this case is smaller than in the first equilibrium so the x should be smaller than
the [H3O+]. We should be able to neglect x in this case.

Ka2 =
( 3.2 × 10 + x ) ( x ) ≈ ( 3.2 × 10 ) ( x ) = x = 2.5 × 10
−3 −3
−9

( 3.2 × 10 − x )−3
( 3.2 × 10 x ) −3

We see that the doubly ionized form of the acid has a concentration equal to the second
Ka.

And now for the third equilibrium:

⎡⎣H3O + ⎤⎦ ⎡⎣ A3 − ⎤⎦
Ka2 = = 1.7 × 10 −14
⎡⎣HA ⎤⎦
2−

In this case the [H3O+] is not going to be any different than from the first ionization.
Also, the concentration of HA2- is not going to change by much. This is, again, because
the Ka3 is so small. We can then use the previous results to set up the ICE table.

HA2- H3O+ A3-

I Ka2 3.2×10-3 0
C -x -x +x
E Ka2 + x 3.2×10-3 + x x

Solving the equilibrium gives:

Ka3 =
( 3.2 × 10 −3
)
+ x (x)
≈
(3.2 × 10 ) ( x ) = 1.7 × 10
−3
−14

( Ka 2 − x ) ( Ka 2 )
K a 2K a 3
x= = ⎡⎣ A3 − ⎤⎦
⎡⎣H3O ⎤⎦+

The pH can be found from this information:

(
pH = − log ⎡⎣H3O + ⎤⎦ = − log 3.2 × 10 −3 = 2.50 )
If we have a polyprotic acid with 4 protons the previous is still valid:

[H4 A]e ≈ [H4 A]i

⎡⎣H3O + ⎤⎦ = ⎡⎣H3 A− ⎤⎦ =
e e
[H4 A]i Ka1
⎡⎣H2 A2 − ⎤⎦ = K a 2
e

K K
⎡⎣HA3 − ⎤⎦ = a 2 +a 3
e ⎡⎣H3O ⎤⎦
e

K a 2K a 3 K a 4
⎡⎣ A4 − ⎤⎦ = 2
e
⎡⎣H3O + ⎤⎦
e

This trend will continue for a pentaprotic and a hexaprotic and so on acid.