APCH 231

TITRIMETRIC METHODS OF ANALYSES

A quantitative determination performed by measuring the amount of some substance

required to react with the analyte is called a titrimetric determination.

The components of a sample that are to be determined are often referred to as the
analytes. The substance reacting with the analyte is called the titrant or standard
solution and its amount is usually determined by measuring the volume of a solution of
known concentration needed to react completely with the analyte. Such a procedure is
referred to as a volumetric titration.
A primary standard is one whose concentration will be known when a solution is
prepared from a known mass of standard dissolved in a known volume of solution.
A secondary standard is one whose concentration has to be determined by titration.

Make sure you know what the requirements of a primary standard are.

Basic requirements
All successful titrations are based on reactions that are stoichiometric, quantitative, fast
and for which there is a suitable means for estimating the equivalence point. The
equivalence point of a titration refers to that point of a titration when just enough titrant
has been added to react completely with the analyte. That is, an amount of titrant has
been added equivalent to the amount of analyte present. The end point refers to the
experimental estimation of the equivalence point.
If the equivalence point is considered to be the true value, the endpoint is the
experimental value, and any difference between them is called the titration error.
There are numerous ways in which endpoints are determined, but this will be discussed
later.

Question
1. Potassium permanganate (KMnO4) is a powerful oxidizing agent that can be used
in volumetric titrations. A 0.02 M permanganate solution can be prepared by
dissolving 1.6 g of KMnO4 in 50 ml of distilled water, boiling for 1 hour,
allowing cooling and then filtering. Permanganate solutions are a very dark
purple colour and do not usually require indicators for signaling the endpoint
when all the titrant has been oxidized by the permanganate, the next drop of
permanganate gives the titration mixture a slight purple colour.
a)

Would a permanganate solution prepared as described above require

standardizing? Explain your answer.

b)

When using permanganate to signal its own endpoint will the endpoint be
exactly the same as the equivalence point? Explain.

CALCULATING AMOUNT AND CONCENTRATION

There are three different ways in which titrations are used to determine the amount of an
analyte:

A direct titration method

A replacement or indirect titration method

A back titration method

Direct Titration Method

In this method, the titrant reacts directly with the analyte and a simple relationship exists
between the amount of titrant used and the amount of analyte present:

Amount analyte = amount titrant x reacting ratio

Once the amount of the analyte has been calculated (in moles or millimoles) it can be
converted to mass (by multiplying by its MM) and finally a percentage as follows:

% analyte = mass of analyte / mass of sample x 100

Question

2. A 300.0 mg sample containing phosphoric acid and inert material was diluted
with water and titrated with 0.05000 M NaOH. The endpoint was reached after
29.00 mL of titrant was added. Calculate the % H3PO4 in the sample.

Replacement or Indirect Titration

This method employs a preliminary reaction in which the analyte is replaced by an
equivalent amount of another substance which is then determined by titration.
The titrant and analyte do not react with each other, but are related through the
other substance.

e.g. Determination of iron

Fe3+ + 2I-
Analyte
I2

+ 2S2O32-
Titrant

2Fe2+

I2

2I-

S4O62-

Question

3.

Calcium can be determined volumetrically using permanganate solutions. The

calcium in a solution of a sample is precipitated as calcium oxalate and filtered.
The pure calcium oxalate is then dissolved in dilute sulfuric acid solution and the
mixture is titrated with standard permanganate solution. The relevant reactions
are:
Ca2+(aq) + C2O42-(aq) CaC2O4(s)
2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq) 2Mn2+(aq) + 8H2O(l) + 10CO2(g)

A Cal-C-Vita tablet was dissolved in distilled water and made up to a final

volume of 250.0 ml. Three 25.00 ml aliquots of this solution were taken and
treated with about 10 ml of an approximately 0.1 M solution of sodium oxalate.
After filtering and washing, the calcium oxalate was transferred to a beaker and
dissolved in 25 ml of 1 M H2SO4 solution. The mixture was diluted to about 100
ml, warmed to about 60OC and titrated with standard (0.01959 M) permanganate
solution. The average titration volume was found to be 12.75 ml.

a)

Is this a direct or indirect determination? Explain briefly.

b)

Was it important to measure the volume of sodium oxalate solution

accurately? Explain briefly.

c)

Why was it important to warm the oxalate solution before titrating with
permanganate?

d)

Calculate the mass of Ca in the Cal-C-Vita tablet.

Back Titration Method

Some titrations cannot be performed directly. There are number of reasons for this and
can include the lack of a suitable indicator or, for example, the formation of a precipitate.
In some cases the problem may be overcome by adding an excess of reagent and then
analyzing the amount of this that remains unreacted. This is the principle of a back
titration since the analyte concentration is calculated by working backwards - that is, by
determining the molar quantity of one of the initial reagents and not the analyte itself
directly.

In a back titration method, the analyte is found by difference. A known excess of

some reagent is added to the analyte solution. A portion of this reagent reacts with
the analyte; the rest is determined by titration.
A long-used back-titration method for chloride involves the addition of a known excess
of silver nitrate which reacts to form insoluble silver chloride, followed by titration of the
remaining silver nitrate with potassium thiocyanate.
The direct titration of Cl- in acidic solution using AgNO3 is not entirely satisfactory, due
to the lack of a good indicator (there are some available but they are only moderately
effective). On the other hand, Fe3+ is an excellent indicator for the back titration with
thiocyanate.
The ionic reactions for this process are
Cl-

Analyte

Ag+ +
Excess
Fe3+

Ag+

AgCl(s) Analyte reaction (precipitation)

known amount white precipitate

SCN- AgSCN(s)
titrant

Titration reaction

white

+ SCN- Fe(SCN)2+

Indicator reaction

Reddish-brown

Thus, like a replacement titration method, two potentially different reaction

stoichiometries must be taken into account.

The relationships are summarized in the following equations:

Amount analyte = amount reagent used x reacting ratio (analyte/reagent)
amount reagent used = amount reagent added - amount reagent remaining
amount reagent remaining = amount titrant x reacting ratio(reagent/titrant)

Question

4. The Kjeldahl method is still (after about 120 years of use) one of the most widely
used methods for the determination of nitrogen in organic substances such as
protein (for example in meat, milk and cereals). The solid sample is digested in
boiling concentrated sulfuric acid (dont try this at home!).
The organic matter is decomposed and the nitrogen in the sample is converted to
the ammonium ion NH4+. When the digestion is complete the mixture is made
basic by the addition of sodium hydroxide solution and the ammonia is distilled
into a receiver containing an accurately known amount of hydrochloric acid
which absorbs the ammonia. The excess acid is titrated with a standard solution
of sodium hydroxide. The relevant reactions are:
Organic substance (CHNO) NH4+ + CO2 + H2O
NH4+ + OH- NH3 + H2O
NH3 + HCl NH4+ + ClHCl + NaOH NaCl + H2O
After determining the amount of NH4+ produced in the digestion, the amount of N
can be determined and from this the amount of protein can be found: most
proteins from a similar source contain very nearly the same percentage of N by
mass for example, protein from flour contains 17.5%(m/m) N whereas protein
from dairy products contains 15.6%(m/m) N and the protein from eggs contains
only 14.9%(m/m) N.
a)

Is the Kjeldahl an example of a direct, indirect or back titration? Explain

briefly.

b)

A sample (0.7121 g) of flour was analysed by the Kjeldahl method. The

ammonia produced during the digestion was distilled into 20.00 ml of
0.04977 M HCl. The excess HCl was titrated with 3.97 ml of 0.04012 M
NaOH. Calculate:

i.)

The number of moles of ammonia distilled into the HCl.

ii.)

The number of moles of N in the sample.

iii.)

The mass of N in the sample

iv.)

The mass of protein in the sample.

v.)

The percentage by mass of protein in the flour sample.

INDICATORS
Acid-Base Indicators
A non-instrumental method of pH measurement much used in simple titrations is the use
of indicators. These are organic dyes which change colour at or near the equivalencepoint of a neutralization to indicate the end of the reaction.
Many substances, change color in response to acid or base. The pigment in red cabbage is
a natural substance very commonly used to show color change. Phenolphthalein is one of
the most common indicators used for beginning chemistry, because its color change is
very obvious which makes it easy to use.
Different dyes will change color at different pH's (the value can be calculated from the
equilibrium constant for the indicator). Here is a small sample of some common acidbase indicators, and the range at which their pH changes color.

When doing a titration, the color of the dye will change at the endpoint. The equivalence
point in an acid-base titration is the point at which the amount of H3O+ and OH- are
equal.
When conducting a titration, one must select the proper indicator so that the pH at its
endpoint will match the equivalence point of the titration. There is a rapid change in pH
as you approach the equivalence point. By measuring or calculating the titration curve
you can determine which indicator will work best.
Acid-Base indicators are dyes that are themselves weak acids and bases. However, the
conjugate acid-base forms of the dye have different colors. The actual chemical structures
of the dyes is often quite complex; however, we can use the generic symbol for the
indicator as HIn. The Brnsted-Lowry equation for the indicator is:
HIn + H2O

H3O+ + In-

Suppose that we increase the concentration of H3O+ in a more acidic solution. Then if we
apply le Chtelier's principle, there will be more H3O+ (because we added more), but the
system will respond to:

use up some of the added H3O+, at the same time

removing some of the In-, and

making more HIn.

Thus we will see the color of the HIn form.

Now suppose that we decrease the concentration of H3O+ (which we could do by adding
more OH- in a more basic solution). Applying LeChtelier's principle, there will be less
H3O+ (because we removed it), but the system will respond to try and:

make some more H3O+, at the same time

making more In-, and

removing some of the HIn.

Thus we will see the color of the In- form.

In summary: at a low pH, an indicator is almost entirely in the HIn form. As the pH
increases, the intensity of the colour of In- increases as the equilibrium shifts to the
right.
The indicator must be present at relatively low concentrations so as not to interfere with
the normal titration curve. This is shown in the curve which follows.

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