Lecture 23

Fractional Composition
Readings
Chapter 10-4 and 10-5

Principle Species
At any pH we can ask
What is the principle species in solution?
For monoprotics this should be easy:
pH > pKa

Base form dominant

pH = pKa

Both are present equally

pH < pKa

Acid form dominant

FA
pH pK a log
FHA

We can define i as the fraction of

any given protic species in solution.
For a monoprotic we have a
formal or total conc
F = [HA] + [A ] and so
HA = [HA]/F and A = [A ] / F

More basic

More acidic
1

pH

14
pKa

Fractions of a Triprotic
qualitatively

[H3A] = [H2A ]

[H2A ] = [HA2- ]

[HA2- ] = [A3- ]

quantitatively

Ka2

Ka1

pH < pKa1
H3A is dominant

Ka3

pH > pKa3
A3- is dominant

Developing Fractional Equations

To express fractions of each species (i), need to develop the equations.
We can do this for a diprotic and then extend the equation by inspection.
Solve for all protic species in terms of
F [H 2 A] [HA ] [A 2- ]
fully protonated form, H2A
Equilibria

Acid Hydrolysis

H2A H+ + HAHA- H+ + A2-

[H ][HA ]
K a1
[H 2 A]
[H ][A2 ]
K a2
[HA ]

[HA ] K a1

[H 2 A]
[H ]

[HA ]
[H 2 A]
[A ] K a2
K
K

a1 a2
[H ]
[H ]2
2

Then, formal concentration in all protic forms can be expressed in terms of H2A

K a1[H2 A]
[H2 A]
F [H2 A]
K a2K a1 2

[H ]
[H ]
Rearrange by gathering terms to get:

[H 2 A]
2

{[H
]

K
[H
] K a1K a2 }
a1
2
[H ]

The Fractions
So lets calculate the fraction present in the fully protonated form
2
A]
]
[H
[H
[H 2 A]
F 2 {[H ]2 K a1[H ] K a1K a2 } H 2 A 2 2
F
[H ] K a1[H ] K a1K a2
[H ]

While the fraction present in the singly deprotonated form is:

HA

[HA ] K a1[H 2 A]

F
[H ]F

[H 2 A]
[HA ] K a1
[H ]

from

K a1[H ]
2
[H ] K a1[H ] K a1K a2
And the fraction present in the fully deprotonated form is:

[A2 ]
K a1K a2

2
F
[H ] [H ]K a1 K a1K a2

from

[H 2 A]
[A ] K a1K a2 2
[H ]
2

Notice the denominator is always the same, and the numerator runs though each
value of the denominator. The i depends only on pH and Ka.

Using the Fractions

Note that

H A HA A
2

[H 2 A] [HA ] [A2 ]

1
F

When we know F and i (from the pH and the Ka) we get

H A F [ H 2 A]
2

HA F [ HA ]

A F [A ]
2

Fumaric acid

(n-1) -

Fractional Composition
[ H ]n
Hn A n
[ H ] K1[ H ]n 1 K1 K 2 [ H ]n 2 ...( K1 K 2 ...K n )
[ H ]n 1 K1
Hn 1 A n
[ H ] K1[ H ]n 1 K1 K 2 [ H ]n 2 ...( K1 K 2 ...K n )

( K1 K 2 K 3 ...K n )
n
n 1
n2
[ H ] K1[ H ] K1 K 2 [ H ] ...( K1 K 2 ...K n )

What are the i good for?

Buffers
Know target pH, can calculate actual concentration of each species present, and so more
accurately prepare buffer, especially if it has a pKa < 4 or pKa > 12.

[ A ] FA [ H ] [OH ]

[ HA] FHA [ H ] [OH ]

[HA] FHA [A-] FA_

When [HA] & [A-] > 10-3M

and 4 pKa 12
FA
pH pK a log
FHA

Acid or Base Hydrolysis

If we do not know the pH we use hydrolysis equation.
Knowing the pH, we can use i and calculate exact distribution of each species.
Amphoterics
Once we have pH we can calculate the concentration of all protic forms.

K1 K 2 [ HA ] K1 K w
K1 [ HA ]

Analysis of a Triprotic - Cysteine

A2pKa3 = 10.77

NH3

HC-CH2SH

pKa2 = 8.36

CO2H

pKa1 = 1.71

HA
H2A
H3A+

Consider a solution that is 0.050 M

in the HA form.
What is the pH?

NH3+
HC-CH2S

How much of each protic species is

present?

CO2

Without a pH we can not use the equations, so we must first use the amphoteric eq,
and treat this as a mono-amphoteric problem;

K a2K a3F K w K a2
H
K a2 F

= 2.74 x 10-10 M and pH = 9.56

Then to determine how much of each species is present

we use the fractional comp eq

i to Determine Protic Forms

A

[A2 ]
K a1K a2K a3
K a1K a2K a3

0.055

3
-20
2

2.623 10
F
[H ] [H ] K a1 [H ]K a1K a2 K a1K a2K a3

Now F is the formal conc in all forms = 0.05M

So then [A2-] = FA2- = 2.8 mM

[HA ] [H ]K a1K a2

0.89
-20
F
2.623 10

So then [HA-] = FHA = 45 mM

HA

[H 2 A]
[H ]2 K a1
H2A

0.056
-20
2.623 10
F

H A
3

So then [H2A] = FH2A = 2.8 mM

[H 3 A+ ]
[H ]3
10

7.8
10
F
2.623 10 -20
So then [H3A+] = FH3A = 3.9 x 10-11 M

Reiteration of [H+] Calculation

Now we have a better value for [HA ] in the amphoteric eq.to replace F with.

K a2K a3 HA K w K a2
[HA] = 0.045 M H
= 2.74 x 10-10 M
K a2 HA

So there is no change in the pH even with this more accurate estimate of [HA]. Using
FHA in the amphoteric eq is a good approx for getting pH.
We also see that the approximation that we can ignore the other reactions is quite
accurate, since so little H3A+ is formed.
However, we see that the approximation that very little H2A and A2- forms is not very
accurate. [H2A] = [A2-]

Question:
What fraction of the diprotic acid H2A (pKa1 =5.45 and pKa2 = 10.55) is in the form
H2A, HA- and A2- at pH = 5 and pH = 10?