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pKa concepts

Ionization = the process in which ions are formed


from neutral compounds;
Dissociation = the separation of the ions of an
electrovalent compound as a result of the action
of a solvent (usually water)

For a weak acid, which dissociates as follows:


HA H+ + A-

An interesting and extremely useful relationship between


pH and pKa can be obtained simply by taking logarithms
(to the base 10) of the previous equation:
log10Ka = log10[H+] + log10[A- ] - log10[HA]
Therefore
-log10[H+] = -log10Ka + log10[A-] - log10[HA]
Note: log a log b = log (a/b)
giving the Henderson-Hasselbalch equation:

The most convenient form of this Henderson-Hasselbalch


equation, is

Using pKa and pH relationship


By using pKa values, we are able to express the
strength of an acid (i.e. its tendency to dissociate)
with reference to the pH scale.
If Ka is large, then pKa will have a low numerical
value. E.g.,
Hydrochloric acid, HCl has a pKa = -3
Acetic acid, CH3COOH has a pKa = 4.77

A strong acid is one which is largely, or


completely, dissociated, and which therefore has
a high Ka value (and low pKa).
A weak acid is one that is only slightly dissociated
in solution, and has a low Ka value.

if we consider the situation where the acid


is one-half (50%) dissociated,
or where
[A-] = [HA]
(that is 50% negatively charged and 50% uncharged)
then, substituting in the
Henderson-Hasselbalch Equation
pH = pKa + log(A-/HA)
pH = pKa + log(1)
Therefore

pH = pKa + 0

and

pH = pKa

How to use H-H equation


When pH = pKa, the charged and uncharged
species have ~equal concentrations.
When pH > pKa, the ionized (charged) form is
dominant, so there will be more negative sites,
therefore, as pH increases, CEC increases

When pH < pKa, the un-ionized, uncharged form


is dominant, so there will be fewer negative
sites,
thus, as pH decreases, CEC decreases (and AEC
increases)

Why care about pKa in soils?


CEC increases as pH increases
Early studies showed soil CEC was constant from
pH 2.5 5
At pH > 5 the CEC of soil increased, especially in
soils containing organic matter or non 2:1 clays

Organic and inorganic components of soil


have functional groups that dissociate at
various pHs, leaving them with a negative
charge that can attract cations

Acidity of various soil functional groups


Some inorganic surface functional groups are
more likely to deprotonate or dissociate than
others
pKa of Al(OH2)+ = ~5, (Al-OH-Si)+0.5 = ~7, SiOH = ~9.5

2:1 silicate minerals have more Si-OH groups and


contribute less to pH-dependent charge than 1:1
minerals and metal oxides

SOM contributes the most negative charge


85-90% of charge due to deprotonation of COOH and
phenolic OH groups which have pKas of 4 6 and 9 - 11

http://www.biologie.uni-hamburg.de/b-online/ge16/10.gif

Colloid

Negative
charge

Positive
charge

% constant

% variable

Humus

200

10

90

Vermiculite

120

95

Smectite

100

95

Illite

40

80

20

Kaolinite

12

95

Fe & Al
Oxides

100