Volumetric Analysis

Acid-base reactions, or neutralization reactions, are commonly used to determine the

concentrations of acids (or bases) in solutions. When an acid is added to a base (or vice versa)
the solution becomes neutral (pH=7) when the moles of H + are equal to the moles of OH-.
Therefore, if the concentration and volume of one of the reactants in a neutralization reaction is
known, the concentration of the second
solution can be determined if its volume is
known. Because titrations involve the
measurement of volumes, they are referred to
as a type of volumetric analysis.

Titration is a very accurate form of analysis.

The basic steps of a titration are shown in
figure 1. The first step in a titration is to
measure out a known quantity of an acid or
base solution
of unknown concentration (the analyte). This
is measured into a conical flask using a
pipette. The volume added with the pipette is
referred to as an aliquot. An indicator is added Figure 1: Basic steps of a titration
to this solution.
A burette is filled with a standard solution (accurately known concentration - the titrant) and is
slowly dispensed from the burette into the conical flask. The concentration of the titrant must be
accurately known so that the concentration of the
unknown can be calculated. In order to do this, the Standard Solutions: A solution has been
reaction between the two solutions must also be standardised when it has been titrated
known. against a primary standard. A primary
The point in the titration where the acid and the base standard is a substance that can be obtained
in a pure form so that the number of moles
have reacted exactly with each other to produce a can be accurately determined from its mass.
neutral solution is called the equivalence point. The For example, sodium hydroxide is commonly
point where the indicator begins to change colour is used as a standard solution but it is too
called the end-point. The end-point is close to the difficult to obtain pure solid sodium
equivalence point. Titration is complete when there is hydroxide. It must first be standardised
against a primary standard such as hydrated
a permanent colour change. Toward the end of the oxalic acid (H2C2O4.2H2O).
titration you may need to add the titrant drop by drop,
otherwise you may go past the end point. The volume of titrant added is called the titre. This
volume is used for the calculations of the concentration of the unknown solution.
Example of an acid base titration.
To determine the concentration of a hydrochloric acid solution the following process was
completed.
20.00 mL of hydrochloric acid was pipetted into a conical flask, and two drops of phenolphthalein
indicator was added. A 0.1019 M sodium hydroxide solution was titrated until the resulting
solution turned a permanent pale pink colour. The process was repeated three times and the
average titre was 24.20 mL. Determine the concentration of the HCl solution.

Step 1: Write the neutralisation reaction and note the ratios (coefficients) for the reaction
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

Step 2: Calculate the moles of the standard (known solution), in this case the base NaOH.
n(NaOH) = C × V
= 0.1019 mol L–1 × 0.02420 L
= 2.466 × 10–3 mol

Step 3: Use the reaction ratios to calculate moles of the unknown solution (the HCl)
The reacting ratio (n(HCl):n(NaOH)) is = 1:1
therefore n(HCl) = n(NaOH)
n(HCl) = 2.466 × 10–3 mol
Step 4: Calculate the concentration of the unknown solution (HCl)
𝑛
𝐶(𝐻𝐶𝑙) =
𝑉
2.466 × 10−3 mol
𝐶(𝐻𝐶𝑙) =
0.020 𝐿
= 0.1233 mol L–1
The concentration of the hydrochloric acid is 0.1233 M.

Example 2.
Sulphuric acid is sold by chemical supply houses as an approximately 18M stock solution. In an
experiment, the 18M stock solution is diluted to approximately 0.3 M. A 25.0 mL aliquot (or
portion) of this diluted solution of sulphuric acid requires an average of 32.58 mL of 0.50 M
sodium hydroxide for a complete neutralization. What is the molarity of the sulphuric acid
solution?

TITRATION CURVES (pH Curves)

The end-point of a titration is very useful for determining concentrations of acids and bases,
however for some titrations involving weak acids and bases, further information can be obtained
from understanding pH changes during the titration. If the pH of an acid solution is plotted against
the amount of base added during a titration, the shape of the graph is called a titration curve. All
titration curves follow similar but slightly different patterns.

Titration curves for strong acid v strong base

We'll take hydrochloric acid and sodium hydroxide as typical of a strong acid and a strong base.

Adding a strong acid to a strong base Adding a strong base to a strong acid

You can see that the pH only falls a very This is very similar to the previous curve
small amount until quite near the except, of course, that the pH starts low and
equivalence point. Then there is a rapid increases as you add more sodium
decrease in the pH. hydroxide solution.
If you calculate the values, the pH falls all
the way from 11.3 when you have added Again, the pH doesn't change very much
24.9cm3 to 2.7 when you have added until you get close to the equivalence point.
25.1cm3. Then it rapidly increases until there is a
The pH falls until there is a significant significant excess of base. At this point the
excess of acid. At this point the rate at rate of change of the pH decreases.
which the pH changes decreases.
 Titration curves for weak acid v strong Titration curves for weak base v strong
base acid

As an example, consider a titration of sodium As an example, consider a titration of

hydroxide as the strong base against ethanoic hydrochloric acid as the strong acid and
acid as a weak acid. ammonia solution as the weak base.

NH3(aq) + HCl(aq) → NH4+(aq) + Cl-(aq)

Adding a strong base to a weak acid Adding a strong acid to a weak base

Because you have a weak acid, the beginning Because you have a weak base, the
of the curve is going to be different to starting beginning of the curve is going to be different
with a strong acid. to starting with a strong base.
• At the very beginning of the curve, the pH is • At the very beginning of the curve, the pH is
low and the pH starts by rising quite quickly high, and the pH starts by falling quite
as the strong base is added, but the curve quickly as the acid is added, but the curve
very soon gets less steep. This is because a very soon gets less steep. This is because a
buffer solution is being set up - composed of buffer solution is being set up - composed of
the excess weak acid (CH3COOH) and its the excess weak base, ammonia, and its
conjugate base (CH3COO-) forming an conjugate acid (ammonium anion) forming
equilibrium. This part of the curve is referred an equilibrium. This part of the curve is
to as the buffer region/zone. referred to as the buffer region/zone.
• At the half-equivalence point (marked with • At the half-equivalence point (marked with
an “x”, half the volume of the equivalence an “x”, half the volume of the equivalence
point), the amount of base added is exactly point), the amount of acid added is exactly
half the amount of acid that was initially half the amount of base which was initially
present, the pH will be equal to the pKa of present, the pOH will be equal to the pKb of
the weak acid. the weak base.
• Notice that the equivalence point is now • Notice that the equivalence point is now
somewhat basic (a bit more than pH 8), somewhat acidic (a bit less than pH 5),
because the acetate anion ((CH3COO-) isn't because pure ammonium isn't neutral.
neutral. However, the equivalence point still However, the equivalence point still falls on
falls on the steepest bit of the curve. That will the steepest bit of the curve. That will turn
turn out to be important in choosing a out to be important in choosing a suitable
suitable indicator for the titration. indicator for the titration.