Titration curve:
Titration results
are of plotted on graph called titration curves, which usually
contain the volume of the titrant as the independent variable and the pH of
the solution as the dependent variable (because it changes depending
on the composition of the two solutions).
The equivalence
point or end point on the graph is where all of the starting solution
(usually an acid)
has been neutralized by the titrant (usually a base). It can be calculated
precisely by finding the second derivative of the titration
curve and computing the points of inflection (where the graph
changes concavity); however, in most cases, simple visual inspection of
the curve will suffice (in the curve given to the right, both equivalence
points are visible, after roughly 15 and 30 mL of NaOH solution has
been titrated into the oxalic acid solution. To calculate the acid
dissociation constant (pKa), one must find the volume at the
half-equivalence point,that is where half the amount of titrant has been added
to form the next compound (here, sodium hydrogen oxalate, then disodium
oxalate). Halfway between each equivalence point, at 7.5 mL and 22.5 mL, the pH
observed was about 1.5 and 4, giving the pKa.
In monoprotic
acids, the point halfway between the beginning of the curve (before any titrant
has been added) and the equivalence point is significant: at that point, the
concentrations of the two species (the acid and conjugate base) are equal.
Therefore, the Henderson-Hasselbalch equation can be solved in this
manner:
Therefore,
one can easily find the pKa of the monoprotic acid by finding
the pH of the point halfway between the beginning of the curve and the
equivalence point, and solving the simplified equation. In the case of the
sample curve, the Ka would be approximately 1.78×10−5 from
visual inspection (the actual Ka2 is 1.7×10−5)
For polyprotic acids,
calculating the acid dissociation constants is only marginally more difficult:
the first acid dissociation constant can be calculated the same way as it would
be calculated in a monoprotic acid. The second acid dissociation constant,
however, is the point halfway between the first equivalence point and the
second equivalence point (and so on for acids that release more than two
protons, such as phosphoric acid).
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