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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

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