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Monoprotic Acid Distribution Diagram (PK 4) : Acid-Base Distribution Diagrams (Not in Textbook!) Chemistry BC2001x

This document discusses acid-base distribution diagrams, which visualize how the concentration of acid and conjugate base varies with pH. It provides examples of distribution diagrams for monoprotic acids and diprotic acids. For monoprotic acids, the diagram shows the fraction of acid (HA) and conjugate base (A-) across the pH range. For diprotic acids, it shows how the fraction of each species (H2A, HA-, A2-) varies depending on whether the acidity constants (Ka1 and Ka2) differ significantly or only by a factor of 100.

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Pawan Babel
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54 views

Monoprotic Acid Distribution Diagram (PK 4) : Acid-Base Distribution Diagrams (Not in Textbook!) Chemistry BC2001x

This document discusses acid-base distribution diagrams, which visualize how the concentration of acid and conjugate base varies with pH. It provides examples of distribution diagrams for monoprotic acids and diprotic acids. For monoprotic acids, the diagram shows the fraction of acid (HA) and conjugate base (A-) across the pH range. For diprotic acids, it shows how the fraction of each species (H2A, HA-, A2-) varies depending on whether the acidity constants (Ka1 and Ka2) differ significantly or only by a factor of 100.

Uploaded by

Pawan Babel
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Acid-Base Distribution Diagrams (not in Textbook!

) Chemistry BC2001x
Distribution diagrams are a useful tool to visualize how the balance in concentration between
acid and conjugate base varies with pH. The details of the equations are not important; what
matters are the graphs and how they display what species dominates under what conditions.
Monoprotic acids
Let fB = fraction in basic form (A), and and fA = fraction in acidic form (HA)
fB = [A]/{[A]+[HA]}, so 1/fB = {[A]+ [HA]}/[A-] = 1 + [HA]/[A]
Ka = [H+][A]/[HA] [HA]/[A] = [H+]/Ka
thus 1/fB = 1 + [H+]/Ka = {Ka + [H+]}/Ka invert this:
fB = Ka/{Ka + [H+]} and (1 fB) = fA = [H+]/{Ka + [H+]}

Monoprotic Acid Distribution Diagram (pKa = 4)


1

fA
0.8 fB

0.6
fraction

0.4

0.2

0
0 2 4 6 8 10 12 14
pH

The shapes of these curves are the same for all weak acids; they simply shift left or right,
crossing at pH = pKa. Note that the actual amounts of acid or base present do not enter into these
equations: the graphs work for concentrated and dilute solutions alike!
This graph shows that the two species interconvert over a fairly narrow range of pH. If the pH is
more than a couple units from pKa, one or the other species dominates. This can also be inferred
from the equation for Ka, but the plot may make this easier to visualize. For the above system,
with pKa = 4, if the pH is 2 or less, we can say that essentially all the acid is in the form HA, [A]
is very small. Conversely, if pH is 6 or greater, essentially all is in the form A, [HA] is very
small, less that 1% of [A].
Diprotic Acids. With two hydrolysis reactions with acidity constants Ka1 and Ka2, we can write
Ka1 = [H+][HA]/[H2A] [H2A]/[HA ] = [H+]/Ka1
Ka2 = [H+][A2]/[HA] [A2]/[HA] = Ka2/[H+]
and Ka1 Ka2 = [H+]2[A2]/[H2A] [A2]/[H2A] = Ka1 Ka2/[H+]2
Let f2 = fraction in form (H2A), f1 = fraction in form (HA), and f0 = fraction in form (A2).
f2 = [H2A]/{[H2A] + [HA] + [A2]}
1/ f2 = {[H2A] + [HA] + [A2]}/[H2A] = 1 + [HA]/[H2A] + [A2]/[H2A]
= 1 + Ka1/[H+] + Ka1Ka2/[H+]2 = {[H+]2 + Ka1[H+] + Ka1Ka2}/[H+]2
invert to find f2; similar derivations for f1 and f0. Look at two cases.
Distribution Diagram First, consider a diprotic acid with
1.0 non-overlapping stages of
ionization: Ka1 and Ka2 differ by a
lot (factor of 10,000 or more;
0.8
pKs differ by 4 or more). Here
pKa1 = 3 and pKa2 = 10.
H2A
0.6 This plot resembles two
fraction

HA-
monoprotic acids: one changes
A2-
from acidic to basic over the
0.4 range pH 1 to 5 (crossing at 3),
the other changes over the range 8
to 12 (crossing at 10).
0.2
In other words, the first ionization
step is essentially complete before
0.0 the second one starts. This is why
0 2 4 6 8 10 12 14 in a titration of such an acid, there
pH is a distinct jump in pH at V1e.

Compare with an acid with Ka1 and Distribution Diagram


Ka2 not very far apart; here they 1.0
differ by a factor of 100 (pKa1 = 3
and pKa2 = 5). The curves again
cross at pKa1 and pKa2. What differs 0.8
is that before the H2A fraction has
fallen close to zero, the A2 fraction H2A
0.6
has begun to rise. This is why there
fraction

HA-
is not a steep jump at V1e. A2-
For pH between about 3 and 5, all 0.4
three species are present in
significant amounts. But as above,
when the pH is a couple units to the 0.2
acidic side of pKa1, essentially all is
in the form H2A, whereas when the
0.0
pH is a couple of units to the basic
side of pKa2, it is essentially all A2. 0 2 4 6 8 10 12 14
pH

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