Titration curve

Terms to remember:

Titration- method of determining the amount of acid/base present in a solution using an indicator.

Analyte- the substance being tested, or that which amount is to be measured

Titrant a standardized solution used to determine test the analyte. Usually as substance that neutralizes the analyte.

Indicator are organic dyes which is sensitive to the changes in pH

Equivalence point it is a condition in titration when the concentration of H+ ion is equal to the hydroxide ion

End point occurs when equivalence point is achieved

Inflection point - a point of a curve at which a change in the direction of curvature occurs.

In general, a titration involves the addition of either a strong acid, strong base or both (must go to completion) as
follows:

Acid + base water + salt

H+ + OH- HOH

When OH- ions are added during titration it is neutralized by H+ ions to produce H2O. The presence of an
indicator will tell if the condition of the analyte changes.

For strong acid and strong base:

Formula Equation: HCl + NaOH HOH + NaCl

(strong acid) (strong base) water + salt

Complete Ionic Equation: H+ + Cl- Na+ + OH- HOH + Na+ + Cl-

Net Ionic Equation: H+ + OH- HOH

pH at equivalence point: 7.00

inflection

in this case the acid is being added to the base.. that is why the
curve started from on top (pH=14.00). As the acid is added the
pH value slowly goes down until quite near the equivalence
point.

Then there is a really steep plunge. If you calculate the values,

the pH falls all the way from pH = 11.3 when you have added
24.9 cm3 to 2.7 when you have added 25.1 cm3.d will reach (1
ml = 1 cm3 )

The middle of the inflection is the equivalence point. Notice that

there is only one inflection because there is only one H+ ion
given up by HCl
 in this case the base is being added to the acid..
notice that the curve started from the bottom .
because the pH of an acid is low. As the base is
added the pH value slowly goes up until quite near
the equivalence.

Then there is a steep rise at pH 1.8 when the base as

it gets close to the equivalence point.

However, Titrations do not always yield an equivalence point with a pH of 7.

Titration curves for strong acid with weak base

This time we are going to use hydrochloric acid as the strong acid and ammonia solution as the weak base.

Because you have got a weak base, the beginning of

the curve is obviously going to be different. However,
once you have got an excess of acid, the curve is
essentially the same as before.

At the very beginning of the curve, the pH starts by

falling quite quickly as the acid is added, but the curve
very soon gets less steep. This is because a buffer
solution is being set up - composed of the excess
ammonia and the ammonium chloride being formed.

Notice that the equivalence point is now somewhat

acidic (a bit less than pH 5), because pure ammonium
chloride isn't neutral. However, the equivalence point
still falls on the steepest bit of the curve. That will
turn out to be important in choosing a suitable
indicator for the titration.

Why is the curve started from top?

Running base into acid:

Still the pH below 7 since we are using a weak base. Notice

that the curve began at the bottom. Why?

At the beginning of this titration, you have an excess of

hydrochloric acid. The shape of the curve will be the same as
when you had an excess of acid at the start of a titration
running sodium hydroxide solution into the acid.

It is only after the equivalence point that things become

different.

A buffer solution is formed containing excess ammonia and

ammonium chloride. This resists any large increase in pH -
not that you would expect a very large increase anyway,
because ammonia is only a weak base.

Titration curves for weak acid and strong base

Running acid into the base

pH at equivalence point is at is 9.2 upon adding 25 ml of

acid.

Why pH 9.2 ? because we are dealing with strong base

Running base into the acid

The start of the graph shows a relatively rapid rise in pH

but this slows down as a buffer solution containing
ethanoic acid and sodium ethanoate is produced. Beyond
the equivalence point (when the sodium hydroxide is in
excess) the curve is just the same as that end of the HCl -
NaOH graph.
Adding hydrochloric acid to sodium carbonate solution

Na2CO3 + HCl NaCl + CO2 + H2O

If you had the two solutions of the same concentration, you would have to use twice the volume of hydrochloric acid to
reach the equivalence point - because of the 1 : 2 ratio in the equation.

This is because carbonate (CO3-2) being divalent anion requires to H + ions to be neutralize. Therefore ;

Notice that the there are two inflection points. This

accounted for 2 H+ ions responsible for the production
of CO2. With this there will be 2 equivalence points (A &
B), one for the for each H+ ion. Therefore there will be 2
pKa values for each.

The graph is showing two end points - one at a pH of 8.3

(little more than a point of inflexion), and a second at
about pH 3.7. The reaction is obviously happening in
two distinct parts.

In the first part, complete at A in the diagram, the sodium carbonate is reacting with the acid to produce sodium
hydrogencarbonate:

Na2CO3 + HCl NaHCO3 + NaCl

You can see that the reaction doesn't produce any carbon dioxide.

In the second part, the sodium hydrogencarbonate produced goes on to react with more acid - giving off lots of CO2.

NaHCO3 + HCl NaCl + CO2 + H2O

That reaction is finished at B on the graph.

This is also good a way to explain the 3 pKa values of H3PO4.

H3PO4 + NaOH NaH2PO4 + H2O

NaH2PO4 + NaOH Na2HPO4 + 2H2O

NaHPO4 + NaOH Na3PO4 + 2H2O