VOLUMETRIC [TITRIMETRIC] ANALYSIS

This is an aspect of quantitative analysis, which involves measuring the

volumes of solutions of reactants in a chemical reaction, so as to determine
the amounts of reactants in such solutions.
TYPES OF VOLUMETRIC ANALYSIS:
 Acid – Base titration
 Oxidation – Reduction titration
 Precipitation titration
 Complexometric titration
QUALITIES OF VOLUMETRIC REACTIONS:
 Fast or instantaneous. Ionic reactions satisfy this.
 Simple and can be represented by a balanced equation.
 There must be a marked change in the physical or chemical properties of the
solution at end-point.
 A suitable indicator to detect sharply the end-point of the reaction must be used.
ADVANTAGES OF VOLUMETRIC ANALYSIS:
 The apparatus required, though delicate, are simple to handle and less expensive
 The analysis can be carried out relatively fast].
 The skills and techniques needed to use the apparatus and carry out the
operation can easily be acquired.
DISADVANTAGES OF VOLUMETRIC ANALYSIS:
 It has a lower degree of accuracy than other methods of analysis because of
various errors associated with it.
DEFINITION OF TERMS:
1] MOLAR SOLUTION:
This is a solution containing one mole of the solute in 1dm 3 of the solution.
2] STANDARD SOLUTION:
This is a solution which contains a specific mass [a known amount] of a
substance in a given volume of a solution. OR
A standard solution is a solution with a known concentration.
NOTE: To standardize a solution simply means to determine the
concentration of that solution by means of another solution whose
concentration is accurately known.
ACID – BASE TITRATION
Titration is a process by which the gradual addition of a standard solution from
the burette, to a definite volume of another solution in the conical flask,
enables equivalent volumes to be determined, usually by the use of an
indicator.
The purpose of any acid – base titration is therefore the determination of the End – point.
This is characterized by a colour change when appropriate indicators are used.
END-POINT/EQUIVALENCE POINT/NEUTRAL POINT
This is the point at which the amount of acid present in a burette exactly neutralizes the
amount of base in a conical flask.
At end – point chemical reactions are assumed complete. Therefore the number of
moles of the acid and that of the base in the solution are exactly in the same ratio as
required in the balanced equation of the reaction.
MATERIALS REQUIRED THE TITRATION
Burette[one]; Pipette[one]; Conical flasks[three]; White tile[one]; Retort Stand and
Clamp[one]; Funnel[one]; Indicator; A clip; Wash Bottle containing distilled water;
Two beakers labeled A and B.
PROCEDURE FOR TITRATION.
1. Clamp the cleaned burette vertically and firmly on the retort stand with the side of
the graduation marks on the burette opposite you. Insert a clip if necessary on the
rubber tubing near the jet. The jet of the burette should be 0.6cm 3 above the tip
of the conical flask which is to be placed on the retort stand.
2. Close the tap of the burette and fill the burette with the acid by means of a funnel
until the level of the acid solution is a little above the zero mark on the burette.
3. Remove the funnel immediately and open the tap or clip. Ensure that the acid
solution fills the jet and no air bubbles exist in the burette.
4. Gently close the tap or the clip as soon as the jet of the burette is completely
filled with the acid solution. Refill the burette if necessary.
5. Place a piece of paper behind the meniscus so that the acid level is clearly shown.
Record this volume of the burette as INITIAL OR FIRST BURETTE READING.
6. Rinse the pipette with the base that is to be measured. This is to ensure that all
traces of distilled water have been removed.
7. Dip the tapering end (jet) of the pipette into the beaker containing the solution of
the base, then draw by sucking the solution until the level is about 2cm 3 above the
mark on the pipette.
8. Close the mouth of the pipette with the index or fore finger and apply gently
pressure. Raise the graduation mark to the eye level and by gently releasing the
index finger pressure; allow the solution to run out until the lower part of the
meniscus falls on the mark.
9. Transfer the pipette and its solution into a clean dry conical flask and remove the
index finger from the mouth or the pipette to drain off for about 15 seconds. Add
two or three drops of the appropriate indicator.
10. Place the conical flask containing the base on the white tile at the base of the
retort stand.
11. Gradually run in the acid solution from the burette into the conical flask by
manipulating the burette tap or clip with the thumb, index finger and the second
finger of the left hand while using the right hand to hold the neck of the conical
 flask and constantly swirl the flask during the addition of the acid from the
burette.
12. Stop the titration the moment the addition of a single drop of the acid solution
from the burette causes the solution to change colour. This colour change indicates
that the end – point of the reaction has been reached. Record this volume of the
burette known as FINAL BURETTE READING.
13. The difference between the final and the initial burette readings gives THE
VOLUME OF THE ACID USED [TITRE VALUE]. This is the first titration-the
ROUGH TITRE.
14. Perform two or more accurate titrations to obtain two consistent/ concordant titre
values, which agree within ±0.15cm 3
or even less.
15. Set out your result in the form below:

TITRATION RESULTS / TABULATION OF RESULTS / RECORDING OF RESULTS

VOLUME OF PIPETTE USED;-------------------------Cm 3
INDICATOR
USED:------------------------------------------------------------------------
COLOUR CHANGE AT END-POINT:------------------------------------------------------
Rough or 1st 2nd 3rd
Trial titration titration titration
FINAL BURETTE READING [Cm ] 3
e.oo f.oo g.oo h.oo
INITIAL BURETTE READING [Cm3] a.oo b.oo c.oo d.oo
VOLUME OF ACID USED [TITRE] [Cm ] 3
[e-a] [f-b] [g-c] [h-d]

AVERAGE VOLUME [AVERAGE TITRE/MEAN TITRE] OF THE ACID:

Calculate the average volume of the acid used from two or more concordant titre
values that agree within ±0.15cm 3
or even less.
Average volume of acid used = (f-b)(g-c) + (h-d) +
3
= Y.00Cm 3

Therefore Y.00Cm of the acid solution required 25Cm 3 of the base for complete
3

neutralization.

PRECAUTIONS DURING ACID – BASE TITRATIONS

Errors that are introduced during titrations can be eliminated if the following
precautions are noted:
A] PRECAUTIONS TO ENSURE THAT CORRECT VOLUMES ARE MEASURED AND
DELIVERED BY THE PIPETTE AND BURETTE
I] Ensure that the burette is rinsed with the acid and the pipette is rinsed with the
base. This is to avoid diluting the concentrations of the acid and the base with the
drops of water that may remain on the inner walls.
2] Do not rinse the conical flask with the base to avoid increasing the volume,
concentration and the number of moles of the base put into it by the pipette
3] Do not blow the last drop of the base at the tip of the pipette into the base in the
conical flask. This is to avoid increasing the volume of the base delivered by the
pipette.
4] Remove air columns and bubbles from the pipette and burette in order to obtain
accurate volume of solutions. Air bubbles decrease the volumes of base and acid
actually expected to be delivered.
5] Always remove the funnel from the burette before titrating to avoid an increase in
the volume of the solution in the burette due to drains from the funnel.
6] Burette and pipette should be in a vertical position when reading volumes of
solutions in them in order to avoid the error of parallax.
7] While taking readings, always allow the meniscus to be at eye level and then read the
bottom of the meniscus so as to ensure accurate readings.
8] The average of at least two concordant titre values should be taken in order to
obtain accurate volume of the acid used.
9] Avoid acid overflowing the burette over the sides into the conical flask to avoid
increasing the number of moles or concentration of base and acid.
B] PRECAUTIONS TO ENSURE SHARP END – POINTS
1] Swirl the conical during titration in order to ensure the uniformity of the solution
of the solution in the flask.
2] Always use just a small quantity of the appropriate indicator during acid- base
titrations to obtain a sharp end-point.
3] Avoid running in the acid at a fast rate so that some of the acid used is not left on
the sides of the burette.
4] Always place the conical flasks on a white tile below the titration flask to avoid
overshooting the end-point.
5] Wash the sides of the conical flask with distilled water in a wash bottle only just
before the end – point. This is because water has no effect on the number of moles of
the base pipette into it but has on the concentration.
SOURCES OF ERROR IN VOLUMETRIC ANALYSIS
1] Inability to read volume of acids in the burette correctly. This leads to inconsistent
burette readings.
2] Inability to recognize the correct colour change at end – point.
3] Poor manipulation of the pipette such that either more or less than the volume of
the pipette is delivered each time.
4] Running in the acid at a very fast rate. Some of the acid will be left behind on the
walls of the burette as the column of the acid runs down fast.
 5] Rinsing the conical flask with the solution to be used before adding the measured
volume from the pipette.
6] Allowing funnel in the burette during titration.
7] Viewing the meniscus of the solution in the burette or pipette at varying heights
leading to parallax error.
8] Presence of air columns and bubbles between the tap or the clip and the jet of the
burette.
9] Presence of air columns and bubbles in the pipette.
10] The use of wrong indicator during titration.
11] Addition of too much indicator to the solution to be titrated. This will need a
certain amount of the acid to be added to cause the colour change to take place.
12] Inability to pipette the base to the mark.
13] Blowing out the last drop of the solution in the pipette while emptying the solution
inside the conical flask.
14] Irregular draining of the burette.
15] Tapping the nozzle of the pipette on the conical flask.
NOTE
The burette is said to be the least accurate instrument of measurement because of
the following reasons:
1] IRREGULAR DRAINING.
2]ESTIMATION OF THE BURETTE READINGS: The second decimal place
in the burette reading can only be obtained approximately since the reading
is obtained only by estimation.
3] ERROR OF DROP: This may arise in the titration because this is the least
amount that can be added. A drop from a burette is approximately 0.05Cm 3

ACID- BASE INDICATORS

These are weak organic compounds capable of changing colours according
to the pH of the solution in which they are added.
They are used to indicate whether a solution is acidic, alkaline or neutral and are employed
during acid – base titrations to detect the end – point.

COMMON LABORATORY INDICATORS AND THEIR COLOUR CHANGES

COLOUR CHANGES pH RANGE
ACIDIC NEUTRAL ALKALINE OF COLOUR
NAME OF INDICATOR SOLUTION SOLUTION SOLUTION CHANGE
LITMUS RED PURPLE BLUE 6.0 – 8.0
METHYL ORANGE RED / PINK ORANGE YELLOW 3.1 – 4.4
SCREENED METHYL ORANGE PURPLE GREY GREEN 2.5 – 4.0
METHYL RED PINK RED YELLOW 4.4 – 6.0
PHENOLPHTHALEIN COLOURLESS COLOURLESS PINK 8.3 – 10.0
 BROMOTHYMOL BLUE YELLOW GREEN BLUE 6.0 – 9.8

THE CHOICE OF AN INDICATOR IN ACID – BASE TITRATION

For an accurate result during titration, a wise choice of a suitable indicator is necessary. A
good and suitable indicator must show a clear and sharp colour change at end – point of the
titration.
ACID – BASE pH OF THE SUITABLE
TITRAION EXAMPLE SOLUTION AT END - INDICATOR
POINT
STRONG ACID & DIL.HCl & NaOH 7 ANY INDICATOR
STRONG BASE
STRONG ACID & DIL.H2SO4 & Na2CO3 5–6 METHYL ORANGE OR
WEAK BASE METHYL RED
WEAK ACID & CH3COOH & NaOH 8–9 PHENOLPHTHALEIN
STRONG BASE
WEAK ACID & H2C2O4 & AQUEOUS Variable b/c the pH of NO SUITABLE
WEAK BASE AMMONIA the solution changes INDICATOR. pH meter
very slowly over a wide is used.
range
WRONG CHOICE OF INDICATORS
 If dilute solutions of acids and alkalis are used, the colour change of methyl orange
is very difficult to observe. For such solutions, screened methyl orange is better.
 The end – point of the titration between a weak acid and a weak base is difficult to
be indicated by any single indicator. This is because the change is so small that it
does not correspond with the pH zone of any of the indicators. Universal indicator
is often used.
 In the titration between weak acid and strong base, if methyl orange or litmus were
used, an end – point would be indicated when the actual end – point has been
exceeded. This is when the solution is predominantly acid.
 If phenolphthalein is used, the titration between a strong acid and a weak base, the
end – point will appear when only half of the weak base e.g Na2CO3 has been used
up. Instead of the reaction:
2HCl + Na2CO3 ---------- 2NaCl + H2O + CO2
Taking place, the following reaction will take place:
HCl + Na2CO3 --------------- NaHCO3 + NaCl
This reaction produces a weak acid , NaHCO3 and phenolphthalein is sensitive to
weak acids.
 EXERCISES
Q1] The following materials were provided for a titration experiment:
Solution A, containing 10.9g/dm3 of an acid, H2Y. Solution B, containing 1.0mol / dm 3 of
sodium trioxocarbonate (IV), 25Cm3 pipette; 50Cm3 burette.
a]I )State the Liquid that was put in the burette for the titration
II) State the Liquid to which the indicator was added.
III) Name the apparatus used for accurate measurement of portions of solution B
for the titration.
IV) List three precautions necessary to ensure accuracy of the measurement
indicated above.
V) State three possible sources of error in the measurement above.
VI) Suggest with a reason, an indicator for the reaction. Give the colour change of
the indicator at the end – point.
b)I)Why was it necessary to use just a small quantity of the indicator during acid –
base titrations?
II) Give the reason why an indicator was used in the titration.
III) State the colour of the indicator in: solution A; solution B; and at end-point
IV) What was the colour of the solution in the conical flask before and after adding
the indicator?
V) What was the colour of the solution in the conical flask at end-point?
VI) What term is used to describe the stage indicated by a change in colour of
indicator
in the conical flask?
VII) Why was the acid solution run into the conical flask from a burette and not from
a measuring cylinder?
VIII) What colour would be observed on adding few drops of methyl orange to the:
I] portion in the conical flask
II] solution A
III] a titration mixture of A and B at the end- point.
IX) State the colour of phenolphthalein in Na2CO3 solution.
X) Is phenolphthalein a suitable indicator for this titration? Give reason for your
answer.
C]I)State the Reason why the titration was carried out three times
II) State why the titration was repeated three times
III) Mention three precautions taken during the titration
IV) Name other pieces of laboratory apparatus required for acid-base titration.
 V) Name three pieces of glassware that would be required in a set-up for obtaining pure
water from the titration mixture.
D] I) after the burette had been washed and rinsed with water, what final cleaning step
should be taken before filling it with the acid?
II) State five measures taken during titration experiments to ensure accurate results
III) Explain why the end-point would not be affected if 5.0Cm 3 of distilled water were
added to the mixture while the titration was in progress.

E)I)The following table shows the pH ranges of indicators P, Q, and R

INDICATOR P Q R

pH working range of indicators 3.1- 4.4 6.0 – 7.6 8.0 – 9.6

Select the indicator(s) that would be suitable for titrating:

I] a strong acid with a strong base;
II] a strong acid with a weak base;
IV] a Weak acid with strong base
State the Colour of the titration mixture at end-point
F] Outline a suitable procedure for preparing accurately 0.10mol / dm 3 solution of sodium
trioxocarbonate (IV), using the materials provided.
G] 22.55 Cm3 of solution A neutralized 25.00 Cm3 of 0.10mol / dm3 of Na2CO3 solution.
Calculate the; 1]Concentration of solution A in mol / dm 3
ii]Molar mass of the acid, H2Y.
Equation for the reaction: Na2CO3 + H2Y ---------- Na2Y + H2O + CO2