Department of Chemistry

University of Dhaka

2nd Year B. S. (Honours) Practical Class

Course Title: Inorganic Quantitative Analysis
Course No. CHL 242 (4 credits)

Books Recommended:

1. Vogel’s Textbook of Quantitative Inorganic Analysis, 3rd/4th edition, ELBS/Longman.

2. Elementary Quantitative Analysis – Theory and Practice, W. J. Blaedel and V. W.
Meloche, Harper & Row.
3. Quantitative Chemical Analysis, R. B. Fischer and D. G. Peters, W. B. Saunders Co.
4. Fundamentals of Analytical Chemistry, D. A. Skoog, D. M. West, F. J. Holler, and S. R.
Crouch, Thomson Asia Pvt. Ltd.
5. Analytical Chemistry, G. D. Christian, John Wiley & Sons, Inc.

Quantitative Classical Chemical Analysis

Titimetric Gravimetric

Acid-base Redox Complexometric Precipitation

Permangatimetric Dichromatometric Titrations Involving Iodine

Iodimetric Iodometric

The lab based on Inorganic Quantitative Analysis is virtually a 4 credit hours course with
120-140 hours duration and carries 100 marks. 40% of the total marks are taken as the
continuous assessment and 60% of the total marks are taken for final examination. The
continuous assessment of this course will be made through student attendance in classes,
observation of the student at work, viva voce (or presentation), and evaluation of practical
reports.

In this lab, students are supposing to work as groups; a group comprises two members
preferably having same mentality and attitude. Each group of the class has an assigned bench
space and desk.

1
Tools and their uses:
1. Balance - Measures mass of material.

2. Wash bottles - For dispensing small quantities of distilled water.

3. Graduated cylinder - Measures approximate volume of liquids.

4. Droppers - For addition of liquids, drop by drop.

5. Funnel - For funneling liquids from one container to another, or for filtering when
equipped with filter paper.

6. Filter paper – Used to separate fine solids from liquids.

7. Beaker - A liquid-measuring container.

8. Watch glasses - For holding small samples or for covering beakers or evaporating
dishes.

9. Pipette - Used to transfer measured substances into another vessel.

10. Graduated pipette - Measures solution volumes.

11. Conical Flask - Used in chemistry labs for titration. It is also suitable for heating liquids.

12. Volumetric flasks - To measure precise volumes of liquid or to make precise dilutions.

13. Burette - Measures volume of solution.

14. Ring stand (with rings or clamps) - For holding pieces of glassware in place.

15. Crucible - Used to heat a small amount of a solid substance at a very high temperature.

16. Clay triangle - A wire frame with porcelain used to support a crucible.

17. Tongs - Similar function to forceps, but are useful for larger items

18. Sintered glass crucible - A special funnel that is used for filtering solid matter out of a
solution. A chemist uses a sintered glass crucible, and not filter paper, whenever the
solid matter must be dried in an oven, as filter paper will burn in an oven.
19. Ashless filter paper - Mainly used for gravimetric methods in quantitative chemical
analysis. Ashless filter paper is pure cellulose and will decompose in the presence of heat
and air to water and carbon dioxide.

20. Buchner funnel – Used for suction filtration.

2
Measuring Beaker Funnel Conical Flask Volumetric flask
Cylinder

10

20

30

40

50

Burette Burette clamp Pipette Pipette filler Sintered glass

filtering crucible

Porcelain Buchner funnel Mortar and Pastel Tripod stand Retort ring
Crucible

Basic Lab Kit for Inorganic Quantitative Analysis

3
 Safety in the Laboratory

The Cardinal Rule for Safety in the Laboratory:

Work cleanly and deliberately; don’t rush; above all, think before you act.

The following rules have been drawn up to assist in protecting you and others when you are
working in laboratories of the Department of Chemistry at Dhaka University. They in no way
form a complete and absolute statement to cover all situations that you may encounter in your
laboratory work; rather, they are designed to cover most normal situations.

(i) Maintain your working area free of mobiles, purses, excess chemicals, equipment and
trash. All spills must be cleaned up immediately and floor around you must be kept dry.
Your work space must be left clean and neat at the end of each laboratory period. You
are responsible for cleaning all sinks and apparatus you have been working with. Any
borrowed equipment must be returned to its proper storage place in the laboratory.

(ii) Wear a lab coat at all times when you are in the laboratory to protect your clothes and
skins to get chemicals on them.

(ii) Wear eye protection at all times when you are in the laboratory. Do not forget that eyes
are one part of your body that often cannot heal themselves from an injury.

(iii) Do not place anything in your mouth while you are in the lab: no food, no finger-nails,
no ball-point pen, no smoke, nothing. The hazards of accidentally ingesting dangerous
substances while doing this are obvious. Carefully wash your hands after you have
finished your lab work.

(iv) Do not make practical joking, pushing, running, ‘horse play’ in any laboratory. Use
your common sense and good judgment. Good laboratory work can be a fun and
rewarding, but laboratories are dangerous places to play in.

(v) No unscheduled experiments until permission have been granted for that experiment.
Provided the experiment is safe and relevant to your study, permission will normally be
granted.

(vi) Seek your teacher’s permission if you need more work to do in any laboratory outside
of your regularly scheduled times. Never work alone in any laboratory.

(vii) Never substitute an unauthorized chemical in an experiment without getting specific

permission from your teacher.

(vii) If you get any chemicals in your eye, mouth, or any parts of your body that can cause
severe irritation or damage to the sensitive tissue of your body, washes it with water
until the irritation is cleared, and make sure that the incident is reported to your teacher.

4
 Quantitative Analysis

Quantitative analysis is concerned with the determination of the amount of a particular

substance present in a sample. The substance determined, often referred to as the analyte.
There are many methods of quantitative analysis: volumetric analysis (often called titrimetric
analysis), gravimetric analysis, colorimetric analysis, etc.
The term volumetric analysis refers to quantitative chemical analysis carried out by
determining the volume of a solution of accurately known concentration (standard solution),
which is required to react stoichiometrically with the solution of the substance to be
determined. The weight of the substance to be determined is calculated from the volume of
the standard solution used and the known
laws of stoichiometry. The standard
solution is usually added from a burette.
The process of adding the standard
solution until the reaction is just complete
is termed titration, and the substance to be
determined is titrated. The point at which
this occurs is called the equivalence point
or the theoretical (or stoichiometric) end
point. The completion of the titration
should, as a rule, be detectable by some
change produced by the standard solution
itself or more usually by the addition of an
auxiliary reagent, known as an indicator. Titration technique

To prepare standard solution, a quantity of the required substance is weighed out accurately
by an analytical balance, dissolved in a volumetric flask, and then the volume is made up to
the mark with distilled water. The substances used to prepare standard solutions in this way
are known as primary standard substances, which satisfy the following conditions:
(i) The substance must be chemically pure.
(ii) The composition of the substance must correspond exactly to the formula.
(iii) The substance must be stable on keeping, both in the solid state and in solution.
(iv) The molecular weight of the substance should be as large as possible.
Substances other than primary standard are known secondary standard substances, which are
to be are standardized against a primary standard substance. A solution of approximate
concentration of a secondary standard substance is first prepared. At the same time a standard
solution of some suitable primary substance is prepared as described above. One of these
solutions is then titrated with the other and the exact concentration of the approximately
prepared solution is then calculated.
Volumetric analysis can be classified into several categories such as neutralization,
oxidation-reduction, complex-formation and precipitation methods.

Neutralization method
The neutralization method comprises volumetric determination based on reactions of acids
with alkalies, i.e. neutralization of acids and bases:
H+(aq) + OH ‾(aq) → H2O(l)

5
The neutralization method is used for determining the amount of acid (alkalimetry) or alkali
(acidimetry) in a given solution. In this lab, experiments 1-3 are based on the principle of
neutralization method.

Experiment No. 1: (A) Preparation of a primary standard acid solution and

determination of the strength of a supplied alkali solution. (B) Determination of the
strength of a supplied secondary standard acid solution using the standard alkali
solution (solution given in A).

NaOH readily absorbs CO2 and water vapour from the air and hence there is a change of
weight therefore, it is a secondary standard substance. On the other hand, oxalic acid is a
crystalline substance, stable at atmospheric conditions and corresponds exactly to its formula
H2C2O4.2H2O, which can be obtained chemically pure. Thus oxalic acid can be used to
prepare a standard solution.
Procedure for (A): Prepare an approximately 0.05 M oxalic acid (H2C2O4.2H2O, mol. wt. =
126.07) solution in a 100 mL volumetric flask by weighing oxalic acid on a chemical
balance. Take 10.0 mL supplied alkali solution (NaOH solution) by a pipette into a conical
flask. Add approximately 25 mL distilled water and 2-3 drops of phenolphthalein indicator in
it. Then titrate the alkali solution with the
standard oxalic acid solution from a burette
until the colour of the solution disappears
(Record your burette reading to two ⇌
decimal places). Repeat the titration for at
least three times and the agreement between
the titrations should be within 0.1 mL.
Record your titration data in tabular form Phenolphthalein indicator
(Recommendation: all titration data in Colourless in acid Pink in alkali
quantitative analysis be recorded in
tabular form). Calculate the concentration of the alkali solution.
H2C2O4(aq) + 2NaOH(aq) → Na2C2O4(aq) + 2H2O(l)

Procedure for (B): Take 10.0 mL of standard alkali (from A) by a pipette into a conical
flask. Add approximately 25 mL distilled water and 2-3 drops of methyl orange indicator.

- -
O3S NH N N(CH3)2 O3S N N N(CH3)2

Methyl orange indicator

Pink in acid Yellow in alkali

Now titrate this with the supplied secondary standard acid solution (HCl solution) from a
burette until the solution becomes red colour. Repeat the titration for at least three times and
the agreement between the titrations should be within 0.1 mL. Calculate the concentration of
the acid solution.
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

[Note: Since your burette is graduated to 0.1 mL, you will read your burette to 0.01 mL. The
second decimal place is an estimate, but should be recorded.
The curved surface at the top of the liquid level is called a meniscus. You read the liquid level
(specifically when the solution is dilute) using the bottom of the meniscus.]

6
Calculation:
How to calculate concentration of a solution? Let us take an example from experiment no. 1
A, say 9.30 mL oxalic acid is required to titrate the 10.0 mL supplied alkali solution. What is
the concentration of the supplied alkali solution?

Number of moles solute

Strength (or concentration) of a solution = ------------------------------ moles/L (= M)
Volume of solution in liter
Now, number of moles of H2C2O4 = concentration × volume in liter
= 0.0500 × 9.30 × 10-3
= 0.4650 × 10-3
Therefore, number of moles of NaOH = 2 × 0.4650 × 10-3 = 0.9300 × 10-3
0.9300 × 10-3 mol
Concentration of supplied NaOH solution = --------------------- = 0.0930 M
10.0 × 10-3 L
This simple way of calculation of concentration of unknown solution should be followed.

Experiment No. 2 Determination of acetic acid content in commercial vinegar.

Commercially available vinegar contains 4-5% acetic acid, CH3COOH. The content of acetic
acid in vinegar may be determined by volumetric analysis (acidimetry-alkalimetry method).
The acetic acid content can be determined by titrating with a standard solution of NaOH.
CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l)

Procedure Take 10.0 mL supplied vinegar solution in a conical flask. Add approximately 25
mL distilled water and 2-3 drops of phenolphthalein indicator to it. Titrate with a standard
NaOH solution until the solution gives a faint permanent pink colour. Repeat the titration for
at least three times. Calculate the amount of acetic acid in the supplied vinegar solution.

Experiment No. 3 Determination of Na2CO3 and NaOH content in commercial caustic

soda.
Commercial caustic soda contains also sodium carbonate. The content of Na 2CO3 and NaOH
in commercial caustic soda may also be determined by acidimetry-alkalimetry method. First
the total alkali content (OH- + CO32-) can be obtained by titrating with a standard acid
solution. Then the CO32- ion in the solution may be precipitated by a dilute solution of BaCl2
and the remaining OH- in the solution is titrated with a standard acid solution.
Na2CO3(aq) + BaCl2(aq) → BaCO3(s) + 2NaCl(aq)

2NaOH(aq) + BaCl2(aq) → Ba(OH)2(aq) + 2NaCl(aq)

Procedure Take 10.0 mL of the supplied commercial caustic soda solution in a conical
flask. Add approximately 25 mL of distilled water and 2-3 drops of methyl orange indicator
in it. Titrate the solution of the conical flask with a standard hydrochloric acid solution.
Repeat the titration at least three times.

7
Take another portion of 10.0 mL of the supplied commercial caustic soda solution in a
conical flask. Warm the solution in conical flask to about 70 oC and add 1% BaCl2 solution
drop wise until the precipitation is over. Cool the content of the conical flask. Add 2-3 drops
of phenolphthalein indicator and titrate it with a standard hydrochloric acid. Repeat the
process for at least three times.

Calculate the amount of Na2CO3 and NaOH in the commercial caustic soda.

Problems
1. Decide whether aqueous solutions of the following salts will be acidic, basic, or neutral:
(a) NaCl, (b) Zn(NO3)2, (c) NH4NO3 and (d) KCN
2. Identify the Lewis acids and Lewis bases in each of the following reaction. Write out the
chemical equations using electron-dot formulae.
(a) B(OH)3 + H2O → B(OH)4- + H+, (b) BF3 + NH3 → BF3.NH3, and
(c) O2- + CO2 → CO32-
3. 50.0 mL of 0.10 M HCl neutralizes 25.0 mL of NaOH solution. Calculate the molarity of
the NaOH solution.
4. How many grams of MgO are required to react completely with 50.0 mL of 0.1 M HCl
according to the following reaction?
MgO + 2HCl → MgCl2 + H2O
5. What are the normalities of each of the following:
(a) 1.85 M HCl, (b) 0.5 M H2SO4 and (c) 1.50 M Ba(OH)2

Oxidation-Reduction method
Oxidation-reduction reactions are associated with transfer of electrons. In a reaction of this
type the oxidizing agent gains electrons and is reduced, and the reducing agent loses electrons
and is oxidized. The exchange of electrons leads to changes in the oxidation state of the
corresponding atoms or ions; the oxidation state of an oxidized atom or ion is increased, and
for a reduced atom or ion it is decreased. Obviously, the direction of an oxidation-reduction
reaction can be predicted only if some quantitative characteristic of the relative force of the
oxidizing and reducing agents involved is known. This characteristic is called the redox
potential. It follows that an oxidizing agent with a higher potential can oxidize any reducing
agent with a lower potential. Similarly, a reducing agent of a lower potential can reduce any
oxidizing agent of a higher potential.
Redox titration without an indicator is also possible if the colour of the titrating solution
undergoes a sharp change as a result of the reaction, for example, to determine aqueous
Fe(II) by permanganate solution in acidic media does not need any indicator. However, if
there is no sharp colour change during the reaction, a redox indicator is also used in this type
of titration. These are indicators, which change colour when the oxidation potential of the
titrated solution reaches a definite value. Experiments 4-8 are based on the principle of
oxidation-reduction method.

8
Experiment No. 4: Standardization of a permanganate solution with a standard oxalic
acid solution and hence determine the amount of Fe(II) from a given solution by the
standard permanganate solution.
Permanganate ion, MnO4- is a strong oxidizing agent in acid solution and often used in
titrimetric analysis. Potassium permanganate, KMnO 4, however, is not a primary standard
substance (because the available permanganate is not pure and moreover, it is easily
decomposed by reducing agents – ammonia, organic substances entering with water, etc.),
and therefore, permanganate solution needs standardization with a primary standard
substance. Arsenic oxide, As2O3 and sodium oxalate, Na2C2O4 are used as primary standard
substances for standardization of permanganate solution. In acidic solution, the reactions
between C2O42- or AsO33- and MnO4- ions can be represented as:
2MnO4- + 5C2O42- + 6H+ → 2Mn2+ + 10CO2 + 8H2O
2MnO4- + 5AsO33- + 6H+ → 5H3AsO4 + 2Mn2+ + 3H2O

Standardization of permanganate solution with oxalate is

carried out at 70oC. The rate of reaction at the beginning is 2+
MnO4-
Mn MnO2
slow, as observed by the fact that permanganate colour does
not disappear for many seconds. However, as soon as the
first few drops of permanganate solution are reduced to C2O42- C2O42-
3+
Mn(II) ion, the later quickly reacts with more permanganate, Mn
in the presence of oxalate yielding more Mn(II) and CO2.
This behavior is typical of an autocatalysis process, in which one of the reaction products
functions as a catalyst (in this case Mn(II) ion is the catalyst).
The standard permanganate solution is generally used in determining Fe(II), H2O2, NO2,
S2O82- etc. in samples. The molar reaction between Fe2+ and MnO4- ions in acid solution is
given below:
MnO4- + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O

Procedure: Prepare 100 mL 0.025 M sodium oxalate (or oxalic acid) standard solution in a
volumetric flask. Pipette out 10.0 mL sodium oxalate (or oxalic acid) solution in a conical
flask. Add 60 mL 1 M H2SO4 in the conical flask. Add 90-95% of the required amounts of
the standard potassium permanganate solution from a burette at a rate of about 25-35 mL/min
while stirring slowly. Warm the solution of the conical flask to 55-60oC and complete the
titration quickly by adding permanganate solution until a permanent faint pink colour is
obtained. Repeat the titration for at least three times. Calculate the concentration of the given
permanganate solution.
Pipette out 10.0 mL of the given Fe(II) solution into a conical flask. Add 15 mL 1 M H2SO4
solution and 30 mL distilled water in it. Titrate the solution of the conical flask with the
standard potassium permanganate solution until a permanent faint pink colour is obtained.
Carry out three such titrations. Calculate the amount of Fe(II) in the given solution.

Experiment No. 5: Determination of the amount of Fe(II) and Fe(III) in a given sample
using a standard dichromate solution.
The standard electrode potentials at 25oC of MnO4- and Cr2O72- ions are given below:
MnO4- + 8H+ + 5e = Mn2+ + 4H2O E0 = +1.52 V
Cr2O72- + 14H+ + 6e = 2Cr3+ + 7H2O E0 = +1.33 V

9
Though K2Cr2O7 is less powerful oxidizing agent, it has several advantages in titrimetric
analysis over KMnO4. Potassium dichromate is stable up to its fusion point and therefore, it is
an excellent primary standard substance. The aqueous solution of K 2Cr2O7 of exactly known
concentration can be prepared by weighing and the solution thus prepared is stable
indefinitely if protected from evaporation. Potassium dichromate solution is used in the
determination of Fe(II) and Fe(III) in iron ores.
Cr2O72- + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O
Fe(III) must be reduced to Fe(II) before titrating with standard dichromate solution. The
reduction is carried out by the addition of a very small excess of SnCl 2 solution to the hot
hydrochloric acid solution of the Fe(III) sample followed by the removal of the excess SnCl2
with HgCl2. The sequence of the reaction is as follows:
2Fe3+ + Sn2+ → 2Fe2+ + Sn4+
Sn2+ + 2Hg2+ → Sn4+ + Hg22+
However, if Sn2+ is too much, the second step will be replaced, at least partially, by the
reaction
Sn2+ + Hg2+ → Sn4+ + Hg(s)
The occurrence of the latter process ruins the determination of iron. Thus the quantity of
Sn(II) used in the first step is critical. Fortunately, the solution of Fe(III) in HCl media
becomes bright yellow (due to the formation of [FeCl4(H2O)2]-) when heated, this makes it
easier to detect the point when reduction of Fe3+ by SnCl2 is complete and this colour just
disappears. One or two drops more of the dilute SnCl2 solution is then added to ensure that a
slight excess of Sn(II) is present. If the procedure is performed properly, a silky white
precipitate Hg2Cl2 appears when HgCl2 is introduced. If a heavy precipitate forms (grey or
black),too much SnCl2 has been added and therefore, the reduction process must be repeated.
The titration is performed in presence of a mixture of H 2SO4 – H3PO4 acids. Sulphuric acid
provides mainly the necessary H+ ion while H3PO4 converts Fe3+ ion into the colourless
stable [Fe(HPO4)]+ complex, thus rendering the end-point more visible. Removal of Fe3+ by
complex formation also lowers the reduction potential of the Fe(III)–Fe(II) couple and thus
tend to increase the reducing power of the Fe2+ ion.
The usual indicator in the dichromate
2 -O3S N SO3-
titrations is diphenylamine, which is a
redox indicator (A redox indicator is H
an indicator which undergoes a Diphenylamine sulphonate
(Colourless)
definite color change at a specific
electrode potential) gives a very sharp K2Cr2O7 Oxidative coupling
reaction
colour change from colourless
through green to red-violet -
O3S N N SO3-
(diphenylbenzidine violet – a system
of conjugated double bond). This Diphenylbenzidine sulphonate
colour change occurs at ~0.78 V (Violet)

electrode potential.

10
Procedure: Prepare 250.0 mL 0.02 M K2Cr2O7 (mol. wt. of K2Cr2O7 = 294.18) solution by
weighing analytical grade potassium dichromate in a volumetric flask. Pipette out 10.0 mL of
the supplied iron solution into a conical flask. Add approximately 25 mL of distilled water,
15 mL of H3PO4 - H2SO4 mixture and a few drops of diphenylamine indicator, NH(C6H5)2, in
it. Titrate the solution slowly with standard (0.02 M) dichromate solution while stirring
constantly until the solution becomes bluish green or grayish blue coloured. Now, continue
the titration, adding dichromate solution dropwise maintaining an interval of few seconds
between each drop until addition of one-drop form permanent intense purple or violet-blue
colour. Carry out three such titrations. Calculate the amount of Fe(II) in the given solution.

Pipette out another portion of 10.0 mL of the given iron solution in a conical flask and add
10 mL of dilute HCl solution in it. Now reduce Fe(III) of the solution by heating the content
of the conical flask at about 90oC and add conc. SnCl2 solution in hot condition dropwise till
the yellowish colour of the solution has nearly disappeared. Complete the reduction by
adding dil. SnCl2 (1 conc. SnCl2: 2 dil. HCl) drop wise till the solution has a faint green
colour. A slight excess of SnCl2 is necessary for complete reduction of Fe(III) to Fe(II). Cool
the content of the conical flask rapidly under tap water at room temperature. Add 10 mL of
the saturated HgCl2 solution to remove the slight excess of SnCl2. A slight silky white
precipitate will form. Formation of a heavy (gray or black) precipitate indicates addition of
too much SnCl2 during reduction (if it is so, discard the run and follow a fresh reduction
process). If no precipitate forms on the addition of HgCl2 reduction of Fe(III) is probably
incomplete. Such a determination should also be rejected.
After the successful reduction of Fe(III) to Fe(II) allow the content of the conical flask to
stand for 5 minutes. Then dilute the solution with distilled water to about 50 mL add about 20
mL solution of H3PO4 - H2SO4 mixture. Add a few drops of diphenylamine indicator and
titrate it slowly with standard K2Cr2O7 solution till a permanent violet-blue or purple
coloration is obtained. Repeat the process for at least three times. Calculate the total iron
(Fe2+ and Fe3+) content of the supplied solution. Determine also the amount of Fe2+ and Fe3+
(g/L) in the supplied solution.

Problems:
1. Label the oxidizing and reducing agent of the following, giving reason to your answer.
(a) 2Al + 3F2 → 2AlF3
(b) PbS + H2O2 → PbSO4 + H2O
(c) Hg2+ + NO2- + H2O → Hg + 2H+ + NO3-
2. With examples distinguish between a “redox reaction” and a ‘disproportionation
reaction”.
3. Explain why standard KMnO4 solution cannot be prepared by weighing.
4. A sample of 0.2560 g of iron alloy dissolved in HCl was titrated to the end point with
36.6 mL of 0.100 M KMnO4. What is the percentage of iron in the alloy?
5. In determination Fe2+ by KMnO4 no indicator is needed but by K2Cr2O7 indicator is must
– why?
6. What is the purpose of adding mixed acids to titrate Fe(II) with K2Cr2O7 solution?
7. It is recommended to use only slight excess of SnCl2 during reduction of Fe(III) to Fe(II)
– why?
8. Why is it necessary to reduce Fe(III) to Fe(II) to titrate with a standard K2Cr2O7 solution?

11
Experiment No. 6: Standardization of sodium thiosulphate solution with standard
dichromate solution and determination of copper from a given solution by the standard
thiosulphate solution.
The oxidation and reduction processes involving iodine is called iodometric titrations. The
direct iodometric titration method (termed as iodimetry) refers to titrations with a standard
solution of iodine. The indirect iodometric titration method (termed as iodometry) deals with
the titration of iodine liberated in chemical reactions.
Sodium thiosulphate (Na2S2O3.5H2O) is available in a state of high purity but because of its
efflorescence nature the amount of water of crystallization in it has some degree of
uncertainity. Thiosulphate is also decomposed by atmospheric oxygen (2Na2S2O3 + O2 →
2Na2SO4 + 2S) as well by the action of microorganisms (thiobacteria). That is why sodium
thiosulphate is not used as a primary standard substance. Sodium thiosulphate can be
standardized with a standard solution of potassium dichromate or potassium iodate or iodine.
Potassium dichromate is reduced by an acid solution of potassium iodide and iodine is
liberated as shown below:
Cr2O72- + 6I- + 14H+ → 2Cr3+ + 3I2 + 7H2O
However, in a high acidic solution, iodide ion is oxidized to iodine by the oxygen of the air
O2 + 4H+ + 4I- → 2I2 + 2H2O, and the Cr(III) forms accelerates further the air-oxidation
of I-. This can be prevented by the addition of solid NaHCO3, reacts with acid, forming CO2,
which sweeps air out of the flask and solution.
Since the solubility of iodine in water is low, a considerable excess of KI must be used in
iodometric determination of oxidizing agents. The iodine liberated by the reaction then
dissolves by forming the unstable complex salt K[I3] with KI:
KI + I2 ⇌ K[I3] or I- + I2 ⇌ I3-
The liberated iodine (I2 or I3-) reacts with thiosulphate solution rapidly and stoichiometrically,
if the pH of the solution is less than 5:
2S2O32- + I2 → S4O62- + 2I- or
2S2O32- + I3- → S4O62- + 3I- S2O32- ion S4O62- ion
A very sensitive indicator for iodine is starch solution,
which forms an intense blue charge transfer compound
with even traces of iodine. The starch solution must be
+ I3- ⇄
added at the very end of the titration, when very little
iodine remains and the solution being titrated have a n
faint (straw yellow) colour. If the starch is added Starch
earlier, when there is still much iodine in solution,
the large amount of iodine-starch compound formed reacts slowly with the thiosulphate, so
that it is easy to add too much thiosulphate.
When an excess of potassium iodide is added to an acidic solution (pH ~ 3.5, adjusted by the
addition of CH3COOH) of Cu2+, two reactions occur simultaneously. First, the Cu2+ oxidizes
iodide to triiodide ion, and is itself reduced to Cu+. Second, the Cu+ immediately react with
iodide to form a precipitate of white Cu2I2.
2Cu2+ + 4I- ⇌ Cu2I2(s)↓ + I2
I- + I2 ⇌ I3-

12
By titrating the triiodide with a standard sodium thiosulphate solution in presence of starch
indicator, copper can be accurately determined. Keep in mind that Cu(II) is not normally a
strong enough oxidant to oxidize I-, but the oxidation occurs because of the insolubility of the
product, Cu2I2.
An error in the titration may arise from adsorption of triiodide ion by the CuI precipitate.
Triiodide ion is held so tenaciously on the surface of the precipitate that the reaction between
thiosulphate and triiodide is incomplete. The problem may be overcome by adding a small
excess of potassium thiocyanate to the mixture, which metathesizes CuI to Cu(SCN):
CuI(s) + SCN- ⇌ Cu(SCN)(s)↓ + I-
Since solid Cu(SCN) has almost no tendency to absorb iodide ions, the previously adsorbed
triiodide is released so that the thiosulphate titration can be finished. However, thiocyanate
should not be added at the beginning of the titration, for triiodide slowly oxidizes thiocyanate.

Procedure: Prepare a 250.0 mL of 0.02 M potassium dichromate solution. Standardize the

supplied thiosulphate solution following the procedure given below:
Take about 50 mL distilled water in a conical flask. Add 1-2 g pure sodium bicarbonate to it,
and shake the conical flask well to dissolve sodium bicarbonate. Add about 5 mL conc. HCl
slowly and gently rotating and flask (caution: the solution must be acidic). Then add 10 mL
10% iodate free potassium iodide (in acid solution iodate oxidizes I- to I2: IO3- + 5I- + 6H+
→ 3I2 + 3H2O). Now run in 10.0 mL standard potassium dichromate solution by a pipette,
mix the solution well and wash the sides of the flask with freshly boiled out (to remove
dissolve oxygen) distilled water. Cover the flask and leave it in dark (because light
accelerates the side reaction in which I- ions are oxidized to I2 by atmospheric oxygen:
4I- + 4H+ + O2 → 2I2 + 2H2O) for about 5 minutes. Dilute the solution with freshly boiled
out distilled water to about 150 mL.
Titrate the liberated iodine with the given thiosulphate solution from a burette. When most of
the iodine has reacted (the colour of the solution became yellowish green) add 1 mL starch
solution and rinse down the sides of the flask (the colour will change to a shade of blue).
Continue the addition of thiosulphate until one drop changes the colour to light green. Repeat
the titration for at least three times and the titrations should agree within 0.1 mL. Calculate
the strength of the given thiosulphate solution in molarity.
Take 10.0 mL of the supplied copper solution by a pipette in a conical flask. Add dropwise
sodium carbonate solution until a faint permanent blue precipitate appears. Dissolve the
precipitate by adding acetic acid dropwise. Then add 10 mL of 10% iodate free potassium
iodide solution. Titrate the liberated iodine with previously standardized sodium thiosulphate.
When the blue colour of the solution will start to fade (after addition of starch indicator) on
further addition of thiosulphate add then 10 mL of 10% NH 4SCN solution, the blue colour
will then intensify. Complete the titration with thiosulphate quickly. Repeat the process for
three times. Calculate the amount of copper (g/L) in the given solution.
[The important sources of error and their remedial measures in the iodometric method are the
following: (i) Loss of iodine by evaporation from the solution. This can be minimized by
having a large excess of iodide in order to keep the iodine tied up as tri-iodide ion. It should
also be apparent that the titrations involving iodine must be made in cold solutions in order to
minimize loss through evaporation, (ii) Atmospheric oxidation of iodide ion in acidic
solution. In acid solution, prompt titration of the liberated iodine is necessary in order to
prevent oxidation, and (iii) Starch solutions that are no longer fresh or improperly prepared.
The indicator will then not behave properly at the endpoint and a quantitative determination
is not possible.]

13
Problems:
1. Solid copper(I) oxide is oxidized to CuCl42- by aqua regia. Write the equation for the
oxidation half-reaction.
2. Write a half-reaction equation for the reduction of aqueous iodate ion (IO 3-) to solid
iodine (I2) in acidic solution.
3. 50.0 mL of 0.025 M K2Cr2O7 solution reacts completely with 40.0 mL of a Na2S2O3
solution. Calculate the molarity of the Na2S2O3 solution.
4. Why is it not possible to keep a standard solution of Na2S2O3 for a long period in the
laboratory?
5. Outline a procedure for standardization of a sodium thiosulphate solution with potassium
iodate.

Experiment No. 7: Iodometric determination of Iron(III).

Amount of iron(III) in a solution can also be determined by iodometric method. The reaction
given below is involved in this process:
2Fe3+ + 2I- → 2Fe2+ + I2
However, the values of the standard oxidation potentials of the Fe3+/Fe2+ (+0.771 V) and
I2/2I- (+0.540 V) couples are relatively close. So that Fe3+ can oxidize iodide ion to iodine,
but the reaction is not complete for quantitative use unless the liberated iodine is removed
from the system as fast as it is formed. Another way of using this reaction for quantitative
estimation of iron(III) is by adding a little cuprous iodide as a catalyst. In this case two
reactions occur simultaneously. First, the Fe3+ oxidizes Cu+ to Cu2+ ion, and is itself reduced
to Fe2+. Second, the Cu2+ immediately oxidizes iodide to iodine (more accurately I3- ion).
Fe3+ + Cu+ → Fe2+ + Cu2+
2Cu2+ + 2I- → 2Cu+ + I2
I2 + I- ⇌ I3-

This happens because the standard oxidation potential of the system Cu 2+/Cu+ (+0.117 V),
low enough compare to that of Fe3+/Fe2+ (+0.771 V). Thus, by titrating the triiodide with a
standard sodium thiosulphate solution in presence of starch indicator, iron(III) can be
quantitatively determined. It is necessary to maintain the following experimental conditions
to determine iron(III) accurately by this method:
• Iodide ion must be present in large excess to favour the forward reaction.
• The solution must be made strongly acidic with hydrochloric acid to prevent hydrolysis of
the ferric ion.
• Air should be displaced from the titration mixture by adding a little solid sodium
hydrogen carbonate before adding the iodide solution.
• Anions which form strong Fe(III) complexes should not be present.

Procedure: Transfer 10.0 mL of the supplied Fe(III) solution (approx. 0.02 M) in a 250 mL
glass-stopper conical flask. Dilute the solution to about 50 mL with water and then add 0.4 g
of pure NaHCO3 into the flask. Then make the solution sufficiently acidic with HCl. Add
1 mL of the cuprous iodide suspension and 10 mL of 10% iodate free KI solution, replace the
stopper, mix the solution and allow to stand it for at least 5 minutes in the dark. Titrate the
liberated iodine with freshly standardized Na2S2O3 solution until the colour of the iodine

14
fades. Add 8-10 drops of starch solution and continue the addition of thiosulphate solution
until the blue colour disappears with the last drop (ignore the blue colour if it reappears). In
this method the end point is faintly definite and permanent, although the starch coloration
reappears more rapidly than in the copper thiosulphate titration.
Preparation of cuprous iodide suspension: About 100 mL of 0.5 M copper sulphate solution
is treated with an excess of 10% KI solution (250-300 mL) and the free iodine is discharged
by the addition of Na2S2O3 solution in the presence of starch indicator. The precipitate is first
thoroughly washed by decantation and then shaken with 200 mL of distilled water and
decanted. Finally 100 mL suspension of cuprous iodide was made and is ready for use as a
catalyst in the iodometric determination of iron(III). [Note that the students need not to
prepare this solution it will be supplied].
If analar grade ferric alum is employed the method can also be used to standardize
thiosulphate solution.

Experiment No. 8: Iodimetric determination of sulfite.

The iodimetric determination of sulfite is based on the following reaction:
Na2SO3 + I2 + H2O → Na2SO4 + 2HI
However, it is found, in practice, that direct titration of sulfite with iodine gives very
inaccurate result because (i) the reaction is relatively slow, especially at the end of the
reaction, and (ii) partial oxidation of sulfite occurs by atmospheric oxygen during the
titration. These problems can be avoided by back titration. The SO32- solution is first treated
with an exact volume, known to be in excess of standard iodine solution, and excess iodine is
then titrated with thiosulphate solution.
Other reducing agent, such as various sulfides etc. can also be determined in exactly the same
way. In determination of sulfides or H2S, the S2- ions are oxidized to free sulfur on addition
of iodine solution, and the sulfur appears in the form of a fine suspension. This does not
influence the results of the determination.

(a) Preparation of iodine (~ 0.0125 M) solution.

Procedure: Dissolve 5 g of iodate free KI in 10-15 mL of water in a glass stopper 1 L
volumetric flask. Weigh out 3.1750 g of A R iodine on a watch glass on a rough balance and
transfer it by means of a small dry funnel into the concentrated KI solution. Insert the glass
stopper into the flask, and shake in the cold until all the iodine has dissolved. Allow the
solution to acquire room temperature, and make up to the mark with distilled water.

(b) Standardization of iodine solution.

Procedure: Transfer 10.0 mL of the iodine solution by a burette to a 250 mL conical flask,
dilute to 100 mL and add the standard thiosulphate solution (0.05 M) from a burette until the
solution has a pale yellow colour. Add 1-2 mL of starch solution, and continue the addition of
the thiosulphate solution slowly until the solution is just colourless. Repeat the titration for at
least three times and the titrations should agree within 0.1 mL. Calculate the concentration of
the iodine solution in molarity.

15
(c) Determination of sulfite.
Procedure: Pipette out 10.0 mL of the supplied solution in a conical flask. Add an exactly
measured volume (25.00 mL) of standard iodine solution (0.01 M) by means of a burette.
Cover the flask with a watch glass and leave it standing in the dark. After few minutes, titrate
the excess iodine with S2O32- solution. Repeat the titration at least thrice. Take the average of
the concordant readings and calculate the sulfite content (g/L) in the supplied solution.

Experiment No. 9: Determination of chloride in a given sample by Volhard’s method.

This method may be applied to determine halides except fluoride in acidic solution. The
halide solution is first treated with excess of standard silver nitrate solution, which forms a
precipitate of silver halide, and the remaining silver nitrate is determined by back titration
with standard thiocyanate solution. For the chloride estimation, the following two reactions
occur during the titration of remaining silver ions:
Cl-(aq) + Ag+(excess) → AgCl(s)↓ + Ag+(residual)
Ag+(residual) + SCN-(aq) → AgSCN(s)↓
When the remaining silver ion is titrated with thiocyanate in the presence of the AgCl
precipitate, the following reaction may occur:
AgCl + SCN- ⇌ AgSCN + Cl-

It is therefore, necessary to remove the silver chloride by filtration and then titrate the filtrate
and washings with thiocyanate solution. However, the filtration of the silver chloride is
avoided by adding a small amount of nitrobenzene (or carbon tetrachloride or chloroform) to
the titrated solution. The silver chloride particles become coated with a thin film of the liquid
nitrobenzene and are thereby protected from contact with the thiocyanate solution during the
back titration.
The most usual indicator in the Volhard’s method is ferric ammonium alum, NH 4Fe(SO4)2.
12H2O. Use of the Fe3+ as indicator is based on the formation of water-soluble ferric
thiocyanate, which has an intense red colour, with SCN- ions:
Fe3+ + SCN- + 5H2O ⇌ [Fe(NCS)(H2O)5]2+

The end-point may sometimes difficult to detect because of the reaction

AgCl + [Fe(NCS)(H2O)5]2+ → AgSCN + FeCl3 + H2O

In contrast to AgCl (SP ≈ 10-10), AgBr (SP ≈ 10-13) is less soluble than AgSCN (SP ≈ 10-12),
consequently the above reaction does not occur during the determination of bromide by
Volhard’s method and thus the end point is very distinct.

Procedure: Prepare 100.0 mL 0.01 M standard silver nitrate solution by diluting

quantitatively the supplied standard silver nitrate solution. Keep your prepared standard silver
nitrate solution in dark preferably wrapped the flask by black paper. Then standardize the
supplied thiocyanate solution with the standard silver nitrate solution as described below:
Pipette out 10.0 mL of the standard silver nitrate (you prepared) solution into a conical flask.
Add 5 mL of 6 M HNO3 and 1 mL of ferric alum indicator. Titrate the solution with the
supplied thiocyanate solution from a burette until a faint brown colour appears which no
longer disappears upon shaking. It is essential to shake vigorously during titration. To obtain

16
correct result, a blank titration may be done. Calculate the strength of supplied thiocyanate
solution.
To determine the chloride content of the supplied sample, pipette out 10.0 mL of the sample
solution into a conical flask and add 5 mL of 6 M HNO 3 in it. Add quantitatively a slight
excess of standard silver nitrate solution in it. Then add 2-3 mL of nitrobenzene and 1 mL of
ferric alum indicator and shake vigorously. Titrate the residual silver nitrate with the standard
thiocyanate solution until a permanent faint reddish brown coloration appears. Calculate the
amount of chloride (g/L) in the supplied solution.

Gravimetric Analysis
Experiment number 10-13 involves determination of elements or ions by Gravimetric
analytical method. This method of analysis is one of the most accurate and precise methods
of macro-quantitative analysis and can be carried out with relatively inexpensive apparatus.
In this process the analyte is selectively converted to an insoluble form. The separated
precipitate is dried or ignited, possibly to another form, and is accurately weighed. From the
weight of the precipitate and knowledge of its chemical composition the amount of analyte
may readily be calculated.
The following requirements should be met in order that a gravimetric method is successful:

• Precipitation should be carried out at as low a pH as is possible and from a hot fairly
dilute solution, with a dilute solution of precipitant.
• The precipitant must be added very slowly, drop by drop and in 50% excess to avoid the
losses due to the solubility of the precipitate.

• The solution should be stirred continuously with a glass rod in order to avoid high local
super saturations as the precipitant is added.
• Wherever needed steps (e.g. digestion, re-precipitation etc.) should be taken to diminish
the effect of co-precipitation and/or post-precipitation on the analytical result.

• The precipitate must be left to stand for several hours after addition of the precipitant.

• Filtration and washing must be completed during a single session. The liquid used for
washing may be pure water, a solution of the precipitant or an electrolyte solution.
• The precipitate must have adequate chemical stability and its composition should
correspond exactly to its chemical formula.

• The content of the element being determined in the precipitate should be as low as
possible.

Experiment No. 10: Determination of calcium as oxalate.

Ca2+ is precipitated in the form of calcium oxalate, CaC2O4. H2O. A solution of (NH4)2C2O4
is used; this reacts with Ca2+ as follows:
Ca2+(aq) + (NH4)2C2O4(aq) + H2O(l) → CaC2O4. H2O(s) + NH4+(aq)

17
The tendency of CaC2O4.H2O to form a microcrystalline
O
precipitate, which can pass through the filter, greatly
complicates the work. Therefore, it is very important in this C O
case to observe the most important condition for formation
Ca . H2O
of sufficiently coarse-grained precipitates; namely to
precipitate from a slightly supersaturated solution. This is C O
achieved by precipitation of CaC2O4 from an acid rather O
than a neutral solution.
Calcium oxalate.monohydrate
At a high enough solution acidity the C2O42- concentration falls so much that the solubility
product of CaC2O4 (= 2.6×10-9) is not reach and no precipitate is formed. However, if
aqueous ammonia is added drop by drop to this acid solution, the H + ion concentration
gradually falls while the C2O42- ion concentration rises. Eventually, the product of
concentrations [Ca2+][C2O42-] becomes greater than the solubility product of the precipitate
and the latter begins to form. Because the ammonia is added drop by drop the C2O42- ion
concentration rises very slowly and gradually. Therefore, the precipitation proceeds all the
time from a solution very slightly supersaturated with CaC 2O4, and the crystals are able to
grow sufficiently.
Calculations show that the precipitation is practically complete at pH > 3.3. To detect the
point when the solution pH becomes 4 the precipitation should be performed in presence of
methyl orange indicator, which changes its colour from red to yellow at approximately this
pH.

The CaC2O4 precipitate is appreciably soluble in water, and washing it with pure water would
result in noticeable loss. Therefore, C2O42- ions must be introduced into the washing liquid to
lower the solubility of the precipitate.

Procedure: Take 10.0 mL of calcium containing supplied solution in a beaker by a pipette.

Dilute the solution to about 150 mL and add a few drops of dil HCl. Add 3-4 drops of methyl
orange indicator to it. Heat the solution to boiling and add very slowly warm ammonium
oxalate solution (4% solution, about 50 mL). To the hot clear solution (about 80oC) add dilute
ammonia solution (1:1) drop wise with stirring until the mixture is neutral or faintly alkaline
(colour changes from red to yellow). Then allow the solution to stand for about 1-2 hours.
After the precipitate has settled test the solution for complete precipitation. Collect the
precipitate in a sintered glass crucible and wash it with 0.2% (NH 4)2C2O4 solution. Dry the
precipitate at 105oC for 2 hours in an oven. Weigh the cool dry precipitate as CaC2O4.H2O.
Calculate the amount of calcium (g/L) in the supplied solution.

Experiment No. 11: Determination of aluminium as 8-hydroxyquinolate.

The following reaction takes place when Al3+ is precipitated with 8-hydroxyquinoline, also
known as oxine:
Al3+(aq) + 3(C9H7NO)(aq) → Al(C9H6NO)3(s) + 3H+(aq)

The precipitate is a chelate compound (also called internal complex), in which one aluminium
atom replaces hydrogen atoms of the hydroxyl groups in three 8-hydroxyquinoline molecules,
and also forms coordination bonds with nitrogen atoms.

18
Since the reaction releases H+ ions into solution, the degree
of precipitation depends on the pH. Complete precipitation
occurs at pH = 4–10 from homogeneous solution. Addition N

of urea serves the purpose of both. Urea hydrolyses in

O
O
solution and generates ammonia, which neutralizes the H + Al
ions. N
N

CO(NH2)2 + H2O → 2NH3 + CO2 O

NH3 + H+ → NH4+
Tris(8-hydroxyquinolinato)-
aluminium(III)
The hydrolysis is slow at room temperature but fairly rapid at 100oC. Thus the pH can be well
controlled in effecting separation by controlling the temperature and duration of heating.
Precipitation is usually complete in 1-2 hours. During this slow growth the particles have
time to attain large sizes, which are easily filterable.

Procedure: Pipette out 10.0 mL supplied aluminium solution in a beaker and add 1-2 drops
of 6 M HCl in it. Then dilute the solution by distilled water to a volume of 100 mL. Add 6
mL oxine reagent and 5 g of urea. Cover the beaker with a watch glass and heat slowly at
95oC for 2 hours. Notice the colour of the supernatant liquid, which indicates the complete
precipitation (colour changes from greenish yellow to a pale orange yellow). Allow the
content of the beaker to cool and collect the precipitate in a sintered glass-filtering crucible.
Wash the precipitate with a little amount of hot water and finally with cold water. Dry the
precipitate at 130oC. Weigh the cool, and dry precipitate as Al(C9H6ON)3. Calculate the
amount of aluminium (g/L) in the supplied solution.

Experiment No. 12: Determination of sulphate as barium sulphate.

The method consists in slowly adding a dilute solution of barium chloride to a hot solution of
the sulphate slightly acidified with hydrochloric acid:
SO42-(aq) + Ba2+(aq) → BaSO4(s)
The precipitate is filtered off, washed with water, carefully ignited at a red heat, and weighed
as barium sulphate.
The solubility of barium sulphate in water is about 3 mg/L at the ordinary temperature; and
the solubility increases with increasing acidity of the solution. Therefore, it is customary to
carry out the precipitation reaction in weakly acid solution i.e. at about 0.05 M HCl
concentration and at boiling temperature.

A precipitate of BaSO4 normally consists of very small crystals and must be filtered through
sintered porcelain filtering crucible or an ash less filter paper of fine porosity and ignited at a
temperature of 500oC or above to free it from water. Using of a porcelain filtering crucible
and ignition of the precipitate in a calibrated muffle furnace certainly give better results,
however, good result can also obtained even with filter paper if the paper is first charring
without inflaming and then burning off the carbon at a low temperature with free access of

19
air. Otherwise partial reduction of barium sulphate precipitate may occur at high temperature
by the carbon of the filter paper:
BaSO4 + 4C → BaS + 4CO↑
This makes the results of the analysis low, since a mole of BaS weighs less than a mole of
BaSO4.
If a reduced precipitate is obtained, it may be re-oxidized by treatment with sulphuric acid,
followed by volatilization of the acid and reheating.

Procedure: Take 10.0 mL of supplied sulphate solution in a beaker. Add 0.5 mL

concentrated HCl and dilute the solution to about 200 mL with distilled water. Heat the
solution to boiling and add dropwise about 10 mL warm 5% barium chloride solution. Stir the
solution constantly during addition. Allow the precipitate to settle and test for complete
precipitation (To do this, add a drop of BaCl2 solution carefully down the side of the beaker
to the clear liquid above the precipitate and note whether any turbidity appears). If the
precipitation is incomplete add a further portion of barium chloride solution (about 3 mL)
with constant stirring. Now keep the covered solution hot (a low flame heating or steam bath
heating) but not boiling, for an hour. Filter the solution through an ashless filter paper
(Whatman No. 40). Use a rubber-tipped rod (policeman) to remove any precipitate adhering
to the walls of the beaker or to the stirring rod. The filtrate may be tested for complete
precipitation. Wash the precipitate in filter paper with water till it is free from chloride. Fold
the moist paper around the precipitate and place it in a dry, previously weighed porcelain
crucible. Burn carefully above a small flame first until the paper chars, raise the temperature
of the crucible to dull redness and burn off the carbon. Cool the content of the crucible and
weigh. Repeat the ignition and cool the crucible again until a constant weight is attained.
Calculate the amount of sulphate (g/L) in the given sample.

Experiment No. 13: Determination of phosphate as ammonium magnesium phosphate

hexahydrate, MgNH4PO4.6H2O.
The phosphate content of soluble salt of phosphoric acid such as Na 2HPO4.12H2O, etc., is
determined by this method. Phosphate may be precipitated as ammonium magnesium
phosphate, MgNH4PO4.6H2O, by magnesium chloride and ammonium chloride in
ammoniacal solution (magnesia mixture). The reaction can be represented by the equation:
H 2O
Na2HPO4(aq) + MgSO4(aq) + NH3(aq) → MgNH4PO4.6H2O(s) + Na2SO4(aq)
Nevertheless, the OH- ion concentration due to the ammonia is sufficient for the ionic product
[Mg2+][OH-] to exceed the solubility product of Mg(OH)2 (= 5×10-12 at 25oC). It follows that
Mg(OH)2 may be precipitate together with MgNH4PO4.6H2O which would make the result
wrong. To avoid this, the NH4Cl is added during the precipitation. However, a large excess of
NH4Cl should be avoided, as it favours the formation of the double salt Mg(NH 4)4(PO4)2.
To obtain good crystalline MgNH4PO4.6H2O precipitates; they are precipitated from
hydrochloric acid solutions containing magnesia mixture by slow addition of dilute ammonia
solution.

20
In acidic or even in neutral solution, the solubility of MgNH 4PO4 precipitate in water is high
and converted in MgHPO4 and Mg(H2PO4)2 as a result of hydrolysis. The process of
hydrolysis is very much suppressed by increase of the solution pH and therefore, at the end of
the precipitation an excess of ammonia solution is added. With the same object of
suppressing hydrolysis and decreasing solubility, dilute aqueous ammonia and not pure water
is used to wash MgNH4PO4.

Procedure: Take 10.0 mL of supplied solution containing not more than 0.07 g PO 43- in a
250 mL beaker. To it, add 50-60 mL of distilled water, 3 mL of concentrated HCl and a few
drops of methyl red indicator. Introduce 25 mL of magnesia mixture, followed by pure
concentrated ammonia solution slowly, whilst stirring the solution vigorously until the
indicator turns yellow (Avoid scratching the sides of the beaker with the stirring rod, for
wherever there is contact, an adhering crystalline deposit forms quickly). Continue to stir the
solution for 5 minutes, and finally add 5 mL concentrated ammonia solution in excess. Allow
the solution to stand in a cool place for at least 3 hours or preferably overnight. Filter through
a sintered glass or porcelain-filtering crucible. Wash the precipitate with small portions of
dilute ammonia solution (~0.8 M) until a few mL of the filtrate, when acidified with dilute
nitric acid and tested with silver nitrate solution, gives no test for chloride. Finally wash with
rectified spirit. Dry the precipitate in air and weigh as MgNH 4PO4.6H2O.
• A suitable phosphate solution for practice may be prepared by dissolving about 0.4 g,
accurately weighed A R anhydrous Na2HPO4 in 100 mL water.
• The magnesia mixture is prepared as follows: Dissolve 25 g MgCl2.6H2O and 50 g NH4Cl
in 250 mL of water. Add a slight excess of ammonia solution, allow standing overnight,
and filtering if a precipitate is present. Acidify with dil. HCl, add 1 mL concentrated HCl,
and dilute to 500 mL.

Problems:
1. Tungsten metal is produced from tungsten(VI) oxide by hydrogen reduction. How many
grams of tungsten can be obtained from 2.8132 g of tungsten(VI) oxide.
2. Sulphur in penicillin–V can be determined gravimetrically by precipitating sulphur as
BaSO4. An 8.47 mg sample of penicillin-V gave 5.46 mg BaSO4. What is the percentage
of sulphur in penicillin-V?
3. A 58.9 g aqueous solution of scandium chloride was treated with silver nitrate, which
gave 167.4 mg silver chloride. What are the mass percentages of Sc and Cl in scandium
chloride?
4. A 3.3438 g sample of iron ore is converted to a solution of iron(II) sulphate. 41.4 mL of
0.150 M K2Cr2O7 solution is required to titrate the iron(II) sulphate solution. What is the
percentage of iron in the ore?
5. How many milliliters of 0.150 M H2SO4 is required to react completely with 1.87 g of
NaHCO3?
6. A 0.6085 g sample of fertilizer containing (NH4)2SO4 was analyzed for nitrogen. The
sample was treated with NaOH and NH3 evolved was collected in 46.3 mL of 0.2130 M
HCl. The solution was then titrated for excess HCl with 44.3 mL of 0.1280 M NaOH.
What is the percentage of nitrogen in the fertilizer?

21
 Separation and quantitative determination of mixtures of cations using
titrimetric and gravimetric methods

Experiment No. 14: Determination of copper(II) and nickel(II) from a mixture.

This experiment demonstrates the possibility of iodometric determination of copper in
presence of nickel, and the reason for separation of copper from nickel during its estimation
by gravimetric method using dimethylglyoxime [CH3C(NOH)C(NOH)CH3 or simply
H2DMG] as the precipitating agent.
In the determination of copper by iodometric method, nickel does not interfere because Ni2+
is not reduced to Ni+ ion by I- ion. However, copper may coprecipitate with nickel in the
precipitation reaction with dimethylglyoxime from a solution at a pH 9. Therefore, Cu 2+ must
be separated from the solution before the addition of H2DMG to the solution. In practice Cu2+
is separated as CuS precipitate produced from homogeneous solution by the acid catalyzed
hydrolysis of thioacetamide.
H+
CH3CSNH2 + H2O → CH3CONH2 + H2S
Cu2+ + H2S → CuS(s)↓ + 2H+
The excess H2S must be boiled off, otherwise Ni2+ would precipitate out as NiS along with
Ni(HDMG)2 when the solution makes alkaline with aqueous ammonia.
When an excess of potassium iodide is added to an acidic solution of Cu 2+, the following
reactions occur simultaneously.
2Cu2+(aq) + 4I-(aq) ⇌ Cu2I2 (s)↓ + I2
I2 + I-(aq) ⇌ I3-(aq)
By titrating the triiodide with a standard sodium thiosulphate solution, copper can be
accurately determined.
The values of the standard oxidation potentials of the systems Cu 2+/Cu+ (+0.117 V) and I2/2I-
(+0.54 V) suggests that the reaction should proceed in the reverse direction:
2Cu+ + I2 → 2Cu2+ + 4I-
However, since iodide reacts quite completely with copper(I) to precipitate CuI, the
concentration of Cu+ is greatly diminished relative to that of Cu2+ and the oxidation potential
of the Cu2+/Cu+ (+0.81 V) becomes greater than that of I2/2I- (+0.54 V).

A large excess of KI is needed to make this reversible reaction proceed sufficiently fully in
the required direction; the greater the excess of KI, the lower the Cu 2+ concentration and the
higher the oxidation potential of the Cu2+/Cu+ system. Furthermore, the titration of triiodide
with thiosulphate further increases the concentration of I-, which favors the completeness of
the Cu2+-I- reaction.
As hydrogen ion does not appear as either reactant or product in the reaction of Cu2+ with I-
and therefore, pH nevertheless exerts an influence on the rate of the reaction as well as on the

22
accuracy of the determination. The hydrogen ion concentration must be greater than
approximately 10-4 M in order to suppress the occurrence of proton-transfer equilibria such as
[Cu(H2O)4]2+ + H2O ⇌ [Cu(H2O)3(OH)]+ + H3O+

[Cu(H2O)3(OH)]+ + H2O ⇌ [Cu(H2O)2(OH)2] + H3O+

The [Cu(H2O)3(OH)]+ and [Cu(H2O)2(OH)2] species react slowly with iodide. On the other
hand, if the concentration of hydrogen ion exceeds 0.3 M, the air oxidation of iodide is
induced by the copper(II)-iodide reaction.
Addition of a small amount of thiocyanate solution is also necessary prior to the end of the
titration to overcome the problem arises from adsorption of triiodide ion by the CuI
precipitate.
The nickel is precipitated by the addition of an ethanolic
solution of dimethylglyoxime to a hot, faintly acid
solution of the nickel salt, and then adding a slight excess
of aqueous ammonia solution. The precipitate is washed
with cold water and then weighed as nickel
dimethylglyoximate after drying at 110-120oC.

Ni2+ + 2H2DMG → Ni(HDMG)2 + 2H+

NH3 + H+ → NH4+ Ni(HDMG)2
A slight excess of the reagents exerts no action on the precipitate, but a large excess should
be avoided because: (i) of the possible precipitation of the dimethylglyoxime itself due to its
low solubility in water, and (ii) the increased solubility of the precipitate in water-ethanol
mixture.

Procedure: Take 10.0 mL of the supplied solution by a pipette in a conical flask. Add drop
wise sodium carbonate solution until a faint permanent blue precipitate appears. Dissolve the
precipitate by adding acetic acid drop wise. Then add 10 mL of 10% iodate free potassium
iodide solution. Titrate the liberated iodine with previously standardized sodium thiosulphate,
when the blue colour of the solution will start to fade (after addition of starch indicator), add
then 10 mL of 10% NH4SCN solution, the blue colour will then intensify. Complete the
titration with thiosulphate quickly. Repeat the process for three times. Calculate the amount
of copper in the given solution.
To determine nickel from the filtrate gravimetrically following the procedure given below:
Take 10.0 mL of the supplied solution by a pipette into a beaker and dilute it to about 100 mL
with distilled water. Acidify the solution with 5 mL 2M HCl and warm it. Then add
thioacetamide solution to precipitate copper ion as CuS. Make sure that the precipitation is
complete. Filter the precipitate and wash it with distilled water. (You may also determine
copper by dissolving the precipitate quantitatively by HCl and can compare the results). Boil
off thioacetamide from the filtrate and then add 30 mL of dimethylglyoxime solution. Then
add immediately concentrated ammonia (1:1) dropwise with constant stirring until the
precipitation is complete. Allow the precipitate to stand for about 30 minutes and then test for
complete precipitation Collect the precipitate in a previously weighed sintered glass crucible.

23
Wash the precipitate few times with distilled water and dry it in an oven at 120 oC until a
constant weight is attained. Weigh as Ni(HDMG)2 and determine the amount of nickel (g/L)
in the supplied solution.

Experiment No. 15: Determination of copper(II) and zinc(II) from a mixture.

This experiment is involving a typical application of iodometric determination of copper in
presence of zinc, and showing the cause for separation of copper from zinc during its
estimation by gravimetric method using diammonium hydrogen phosphate, (NH 4)2HPO4 as
the precipitating agent.

Zinc does not interfere during the determination of copper by iodometric method, because
Zn2+ is not reduced by I- ion. On the other hand, copper may coprecipitate with zinc in the
precipitation reaction with (NH4)2HPO4 from a solution at a pH 7. Therefore, Cu2+ must be
separated from the solution before the addition of (NH 4)2HPO4 to the solution. In practice
Cu2+ is separated as CuS precipitate produced from homogeneous solution by the acid
catalyzed hydrolysis of thioacetamide.
H+
CH3CSNH2 + H2O → CH3CONH2 + H2S
Cu2+ + H2S → CuS(s)↓ + 2H+
The excess H2S must be boiled off; otherwise Zn2+ would precipitate out as ZnS when the
solution makes neutral with aqueous ammonia.

The Zn2+ is precipitated as ZnNH4PO4.H2O and weighed as ZnNH4PO4 after drying at

105oC. The precipitant is (NH4)2HPO4, which exerts an important buffering action (due to
HPO42-/H2PO4-):
H2O
Zn2+ + HPO42- + NH4+ → ZnNH4PO4 + H+
HPO42- + H+ → H2PO4-
It is found that the most satisfactory results are obtained over the pH range 6.4–6.9 (optimum
pH is 6.6) and that when the pH exceeds 7.0 the precipitate is difficult to remove the beaker.

The ZnNH4PO4.H2O precipitate is appreciably soluble in water and converted in ZnHPO4 and
Zn(H2PO4)2 as a result of hydrolysis. Thus washing the precipitate with pure water would
result in noticeable loss. A dilute solution of the precipitant is usually used for washing the
precipitate.

Procedure: Take 10.0 mL of the supplied solution by a pipette in a conical flask. Add drop
wise sodium carbonate solution until a faint permanent blue precipitate appears. Dissolve the
precipitate by adding acetic acid drop wise. Then add 10 mL of 10% iodate free potassium
iodide solution. Titrate the liberated iodine with previously standardized sodium thiosulphate,
when the blue colour of the solution will start to fade (after addition of starch indicator). Add
10 mL of 10% NH4SCN solution; the blue colour will then intensify. Complete the titration
with thiosulphate quickly. Repeat the process for three times. Calculate the amount of copper
in the given solution.

24
Copper may be determined iodometrically by dissolving CuS precipitate (obtained during
separation) in acid.

For the determination of zinc, transfer 10.0 mL of supplied solution and dilute it to about 100
mL. Separate copper from it by precipitating as CuS. Discard the CuS precipitate. Destroy
excess thioacetamide by boiling off H2S from the filtrate. Add dilute ammonia (1:1) solution
to make the filtrate almost neutral and then add 25 mL 10% (NH4)2HPO4 drop wise with
stirring. A flocculent precipitate first forms which on heating on water bath (for 1 hour)
changes to crystalline ZnNH4PO4.H2O. Cool the solution to room temperature. Then filter the
precipitate through a weighed sintered glass crucible. Wash the precipitate with 1%
(NH4)2HPO4 till it is free from chloride. Finally, wash with 50% ethanol. Dry the precipitate
to a constant weight in an oven at 105oC. Weigh the precipitate as ZnNH4PO4 and determine
the amount of zinc (g/L) in the supplied solution.

Experiment No. 16: Determination of iron(III) and manganese(II) form a mixture.

This experiment involves separation and quantitative determination of iron(III) and
manganese(II) from a mixture using titrimetric and gravimetric methods. Determination of
iron is carried by dichromate method after reduction of Fe(III) to Fe(II) while manganese
gravimetrically as Mn(NH4)PO4.H2O with diammonium hydrogen phosphate as the
precipitating agent.

Separation of iron(III) can be achieved by selective precipitation followed by filtration. Ferric

ion is precipitated as hydrous ferric oxide from weakly acidic, neutral or slightly alkaline
solutions:
Fe3+ + 3OH- + xH2O → Fe(OH)3.xH2O
Thus by a careful control of the pH of the solution, a considerable selectivity in the
precipitation of the hydrous ferric oxide in the presence of other cations can be achieved. In
this experiment, hexamethylenetetramine is used as a precipitating agent in slightly acidic
medium. This relatively low pH allows the formation of Fe(OH) 3.xH2O precipitate from
homogeneous solution but prevents the precipitation of Mn(II). This is based on slow
hydrolysis of hexamethylenetetramine:

(CH2)6N4 + 10H2O ⇌ HCHO + 4NH3 + 4H2O

After separation, the Fe(OH)3.xH2O precipitate is dissolve in conc. HCl yielding a bright
yellow solution due to the formation of [FeCl4(H2O)2]-, from which iron(III) is determined by
dichromate method involving the following redox reactions:

2Fe3+(aq) + Sn2+(aq) → 2Fe2+(aq) + Sn4+(aq)

Sn2+(aq) + 2Hg2+(aq) → Sn4+(aq) + Hg22+(aq)
6Fe2+(aq) + Cr2O72-(aq) + 14H+(aq) → 6Fe3+(aq) + 2Cr3+(aq) + 7H2O(l)

Gravimetric estimation of manganese(II) involves in the precipitation of MnNH 4PO4.H2O in

slightly ammoniacal solution containing excess of ammonium salt, dry the precipitate at
100-105oC and weighed as MnNH4PO4.H2O.

25
 H2O
Mn2+ + HPO42- + NH4+ → MnNH4PO4.H2O

Procedure: Transfer 10.0 mL of the supplied solution of the mixture by a pipette into a
beaker and dilute it with distilled water to 100 mL. Make the solution almost neutral by
adding concentrated ammonia solution. Add 15 g NH 4Cl followed by an excess of 10%
solution of hexamine (Hexamethylenetetramine) drop wise with constant stirring until the
iron is precipitated as hydrous ferric oxide (ensure for complete precipitation). Leave the
beaker for about 20 minutes on water bath. Filter the precipitated and wash it with hot water
till it is free from manganese. Keep the filtrate to determine manganese form it
gravimetrically.

Dissolve the precipitate in a few mL of conc. HCl and make it to a constant volume. Take
10.0 mL of this prepared iron solution and titrate it against a standard K2Cr2O7 solution.
To determine manganese concentrates the filtrate to about 100 mL. Add about 20 mL 10%
solution (NH4)2HPO4 in excess. If a precipitate forms, dissolve it with few drops of HCl (1:3)
solution. Heat the solution to about 95oC for 15-20 minutes and then add aqueous NH3 (1:3)
solution dropwise in the hot solution with constant stirring until manganese phosphate
precipitate just begins to form. Continue heating and stirring till the precipitate becomes silky
crystalline in appearance. Add 1-2 drops of aqueous NH3 solution to test for complete
precipitation. Cool the solution in cold water for about an hour and then filter through a
sintered glass crucible. Wash the precipitate with 1% solution of NH 4NO3 to free it from
chloride. Dry the precipitate in an oven at 105oC till a constant weight is attained. Weigh as
MnNH4PO4.H2O and determine the amount of manganese (g/L) in the supplied sample.

Complexometric method
The formation of stable metal-complex ions by the titration of a metal ion solution with a
suitable standard solution of a complexing agent, or ligand, has gained increasing importance
as a method of volumetric analysis. The vast majority of complexation titrations are carried
out using a multidentate ligand, ethylenediaminetetraacetic acid, H4EDTA, as the
complexone. A water-soluble salt, Na2EDTA.2H2O (Na2H2Y) is preferred as the reagent for
practical purposes. Na2EDTA.2H2O ionizes in water to give 2Na+ and a strong chelating ion,
H2Y2- (Y = EDTA4-) having six potential groups – four carboxyl groups and two amine
groups for bonding a metal ion. In fact, H2Y2- ion forms very stable, one to one, six
coordinated complexes with a wide range of metal ions.
Most metal-EDTA titrations are performed in neutral or
alkaline solutions. The prominent EDTA species in neutral or
alkaline media are the HY3- and Y4- ions and thus the net
reactions become,
(n-4)+
Mn+ + HY3- ⇌ MY(n-4)+ + H+
Mn+ + Y4- ⇌ MY(n-4)+
depending on the exact solution pH.

26
The formation of hydrogen ions as a reaction product would cause the pH of the solution to
decrease and the desired titration reaction to cease or even reverse itself, unless the solution is
buffered against the pH change. Therefore, a buffered system is employed to keep the pH at
the desired value for the particular application. This buffer also serves as the auxiliary
complexing agent in order to prevent the undesired precipitation of metal hydroxides.
A very large number of metal ion indicators are employed for complexometric titrations. Two
most widely used metal ion indicators are,

Na+ -O
O- Na+

O-Na+

Eriochrome Black T Murexide Fast Sulphon Black F

Such indicators form complexes with specific metal ions at the desired pH; these differ in
colour from the free indicator and, in consequence, a sudden colour change occurs at the
equivalence point. The use of the metal ion indicator in an EDTA titration may be written as
K1
M + In ⇌ MIn
K2
M + EDTA ⇌ M-EDTA [K2 >>> K1]
K3
M-In + EDTA ⇌ M-EDTA + In

From the above discussion, it reveals that complexation titration with EDTA fulfill the same
requirements as all other volumetric methods of analysis. It is rapid, proceeds according to
well-defined stoichiometry, and possesses the desired characteristics for the application of the
various end point detection systems.

Experiment No. 17: Determination of copper(II) using Fast Sulphon Black F indicator.
This determination involves direct titration of copper(II) solution in a medium well buffered
at pH 10 with standard EDTA solution in presence of Fast Sulphon Black F indicator. A pH
of 10 is readily maintained with an ammonia-ammonium ion buffer. In ammoniacal solution
Fast Sulphon Black F form red complex with copper, therefore, the colour of the solution
prior to the equivalence point is red. However, at the end point of titration the colour of the
solution becomes bright green because the formation of the copper-EDTA complex frees the
H2In2- indicator ion.
At pH = 10, the predominant EDTA species is HY 3-, and the reactions take place during
titration may be written as
Cu2+ + H2In3- ⇌ CuH2In-
Red
CuH2In- + HY3- ⇌ CuY2- + H3In2-
Green

27
A much higher pH would incur the possibility of precipitation of Cu(OH) 2. For this particular
system, ammonia does not form a stable complex with copper.

Procedure: Pipette out 10.0 mL of supplied copper solution into a conical flask and dilute
the solution with 50 mL distilled water. Then add 5 mL of ammonia-ammonium ion buffer
(or concentrated ammonia) solution and 2-3 drops of Fast Sulphon Black F indicator. Titrate
the solution with a standard Na2EDTA solution (~0.01 M) until the colour changes from
purple to dark green. Calculate the amount of copper (g/L) in the given solution.

Experiment No. 18: Determination of zinc(II) using Eriochrome Black T as indicator.

This determination involves direct titration of zinc(II) solution with standard EDTA solution
in presence of an ammonia-ammonium ion buffer and Eriochrome Black T indicator. An
ammonia-ammonium ion buffer of approximately pH 9 or 10 serves as the auxiliary
complexing agent in order to prevent the precipitation of zinc hydroxide as well as to
maintain the desired pH. At this pH, the predominant EDTA species is HY 3-.
The colour of the solution prior to the equivalence point is wine red because of the formation
of zinc-Eriochrome Black T complex. However, when the first slight excess of Na 2EDTA
titrant is added, the colour of the solution becomes bright blue because the formation of the
zinc-EDTA complex frees the HIn2- indicator ion. The reactions are,
Zn2+ + HIn3- ⇌ ZnIn- + H+
Wine red
ZnIn- + HY3- ⇌ ZnY2- + HIn3-
Blue
Procedure: Pipette out 10.0 mL supplied zinc solution into a conical flask and dilute the
solution to 50 mL with distilled water. Then add 1 mL ammonia-ammonium chloride buffer
solution and 2-3 drops of indicator. Titrate the solution with a standard EDTA solution
(~0.01 M) till the colour changes from wine red to blue. Calculate the amount of zinc (g/L)
in the supplied solution.

Experiment No. 19: Determination of nickel(II) using Murexide as indicator.

This determination demonstrates a complexometric titration in which nickel, in an ammonia-
ammonium ion buffer solution, is titrated with a standard EDTA solution to an end point
determined with the aid of murexide indicator. An ammonia-ammonium ion buffer of
approximately pH 9 or 10 serves as the auxiliary complexing agent in order to prevent the
precipitation of nickel hydroxide as well as to maintain the desired pH. At this pH, the
predominant EDTA species is HY3-.
Between pH 9 and 11, nickel forms an orange-yellow complex with murexide. At the end
point the formation of nickel-EDTA complex frees the violet-coloured H3In2- indicator ion.
The end point colour change is therefore, from orange-yellow to violet.
Ni2+ + H3In2- ⇌ NiH2In- + H+
Orange-yellow
NiH2In- + HY3- ⇌ NiY2- + H3In2-
Violet

28
Procedure: Pipette out 10.0 mL supplied nickel solution into a conical flask and dilute to 50
mL with distilled water. Add 40 mg murexide/NaCl mixture and 10 mL of the 1 M NH4Cl
solution and than add conc. NH3 solution drop wise until the pH is ~7 as shown by the yellow
colour of the solution. Titrate with standard (~ 0.01 M) EDTA solution until the end point is
approached. Then add 10 mL of concentrated ammonia solution and continue the titration
until the colour changes from orange-yellow to violet. Calculate the amount of nickel (g/L) in
the supplied solution.

Experiment No. 20: Determination of hardness of the supplied water sample.

Water samples that do not readily produce lather with soap are called hard water. Principle
hardness causing cations are Ca2+ and Mg2+. The portion of the total hardness that can be
largely removed by boiling is known as temporary hardness. Boiling converts the
bicarbonates present into insoluble carbonates and hydroxides, which can be removed by
filtration.
Δ
Ca(HCO3)2 → CaCO3(s)↓ + H2O + CO2
Δ
Mg(HCO3)2 → Mg(OH)2(s)↓ + CO2
Permanent hardness is due to the presence of soluble calcium or magnesium sulfates in the
water. In contrast to temporary hardness, permanent hardness cannot be removed by boiling.
The sum of the permanent and temporary hardness is the total hardness of water.
Hardness of water can be determined complexometrically at pH 8-10, where EDTA (H2Y2-)
is used as complexing agent. It forms complexes with Ca2+ and Mg2+ represented by the
reactions:
M2+ + HY3- → MY2- + H+
An ammonia-ammonium ion buffer is used to maintain the pH of the solution at
approximately 8-10. When a small amount of the indicator solution (Eriochrome Black T) is
added to a hard water sample whose pH has been controlled by the addition of the buffer
solution, the indicator reacts with Mg2+ to produce wine red colour.
Mg2+ + HIn3- → MgIn- + H+
(Blue) (Red)
As EDTA is added, free Ca2+ ions are first complexed to CaY2-, this being the most stable
complex:
Ca2+ + HY3- → CaY2- + H+
Free Mg2+ ions then react to give MgY2- complex

Mg2+ + HY3- → MgY2- + H+

which is less stable than CaY2- complex but more stable than MgIn- complex. Therefore, if an
extra drop of EDTA is added after all the free Ca2+ and Mg2+ ions have been complexed,
EDTA takes up Mg2+ from the weak MgIn- complex to form stable MgY2- complex
simultaneously liberating the indicator in the free form:
MgIn- + HY3- → MgY2- + HIn3-
(Red) (Blue)
Completion of the above reaction makes the end point of the titration.

29
Parts per million (ppm) is the most commonly used unit of hardness and represent the number
of parts of calcium carbonate, equivalent to hardness causing ions present, per millions of
water.

(a) Determination of total hardness

Procedure: Take 50.0 mL of the supplied water sample into a conical flask. Acidify it with
dilute HCl and heat for a couple of minutes to drive off carbon dioxide. Cool and neutralize
the solution with NaOH solution. Add 1 mL ammonia-ammonium chloride buffer and 3-4
drops of Eriochrome Black T indicator. Then titrate the solution with a standard 0.01 M
EDTA solution until the colour changes from wine red to pure blue. Calculate the total
hardness of the water sample in parts of CaCO3 per million of water.

(a) Determination of permanent hardness

Procedure: Take 250 mL of sample water in a 500 mL beaker. Heat the water to boiling for
about 20-30 minutes. Cool and filter the water and collect the filtrate into a 250 mL
volumetric flask. Do not wash the filter paper. Dilute the filtrate to a constant volume with
distilled water and mix well. Then titrate 50.0 mL of the filtrate the same way as was done in
the case of total hardness. Calculate the permanent hardness of the supplied water as parts of
CaCO3 per million of water.

Note: One mole of EDTA is equivalent to one mole of calcium carbonate. The molar mass of
CaCO3 is 100 g mol-1.

(c) Determination of temporary hardness

Procedure: Calculate the temporary hardness by subtracting the permanent hardness from
the total hardness.

Experiment No. 22: Determination of sulphate.

The sulfate is precipitated as barium sulphate from the acid solution. The precipitate is
filtered off and dissolved in a measured excess of standard EDTA solution in the presence of
aqueous ammonia. The excess of EDTA is then back titrated with standard magnesium
chloride solution using Eriochrome Black T indicator. Aqueous ammonia also maintains the
pH 10 of the solution. At this pH, the predominant EDTA species is HY 3-. The reactions are:
SO42-(aq) + BaCl2(aq) → BaSO4(s)↓ + 2Cl-(aq)
NH3(aq)
BaSO4(s)↓ + HY3-(excess) → BaY2- + HY3-(residual) + SO42-
HY3-(residual) + Mg2+ → MgY2- + H+
Mg2+ + HIn3- ⇌ MgIn- + H+
Wine-red

Procedure: Pipette 20.0 mL of the supplied sulphate solution in a beaker and dilute it with
distilled water to about 50 mL. Adjust the pH of the solution to ~1 with 2 M HCl. Heat the
solution to boiling. Add rapidly 15 mL hot BaCl2 solution (~0.05 M) with vigorous stirring.
Heat the solution on a steam bath for at least one hour. Cool the solution and filter the
precipitate through a filter paper (Whatman No. 42). Wash the precipitate with cold distilled
water and then transfer the precipitate quantitatively to a beaker. Add 40.0 mL standard

30
EDTA solution and 5 mL concentrated ammonia solution to dissolute the precipitate, and boil
gently if needed. Cool the clear resultant solution. Make the solution to a constant volume.
Then titrate a known volume of the solution by adjusting the pH to 10 using 10 mL buffer
solution. Add a few drops of Eriochrome Black T indicator and titrate the excess of EDTA
with a standard magnesium chloride solution (~0.05 M) to a clear red colour. Calculate the
amount of sulphate (g/L) in the supplied solution.

Experiment No. 23: Determination of lead(II), zinc(II) and copper(II) in a mixture.

This experiment involves separation and quantitative determination of copper(II), zinc(II) and
lead(II), from a mixture using titrimetric and gravimetric methods. Lead is determined
gravimetrically as lead sulphate, while copper and zinc complexometrically and copper
iodometrically. Subtraction of copper from the total copper and zinc contents yields the
amount of zinc present in the mixture.
Because of its high solubility (58 g/100 g in water at 20oC) and availability, Pb(NO3)2 is used
in this experiment as a source of lead(II). Lead(II) may be separated quantitatively from other
metals as an insoluble sulphate when proper conditions are maintained. Precipitation of lead
sulphate is accomplished by the addition of concentrated sulphuric acid. Copper and zinc
sulphates are soluble and do not coprecipitate with lead.
Pb(NO3)2 + H2SO4 → PbSO4 + 2HNO3
The solubility of lead sulphate increases with temperature and is dependent upon the weight
percent of sulphuric acid in solution. In addition, PbSO 4 is somewhat soluble in nitric acid.
Evaporation of the solution to fumes of SO3 effectively removes nitric acid from solution
reducing the solubility of lead sulphate.
The basic reaction in the determination of copper using the iodometric method is represented
by the equation:
2Cu2+ + 4I- ⇌ 2CuI(s) + I2

This is a rapid, quantitative reaction in slightly acidic solutions, if there is a large excess of
iodide ion present and if the copper is in the form of a simple ion rather than a complex one.
The iodine that is liberated can be titrated in the usual manner with standard thiosulfate
solution. The reaction involving cupric ion and iodide takes place quantitatively since the
cuprous ion formed as result of the reduction is removed from the solution as a precipitate of
cuprous iodide.

(a) Determination of lead(II)

Procedure: Take 25.0 mL of the supplied solution (solution A) in a 250 mL beaker. Add 3-4
mL of conc. H2SO4 and evaporate the solution carefully on a low flame until white fumes are
evolved. Allow the solution to cool. Wash down the sides of the beaker with 10-20 mL of
distilled water and again evaporate to white fumes to ensure the expulsion of all nitric acid.
Cool, add 25 mL of water, heat nearly to boiling and stir for several minutes until all the
soluble salts dissolve into solution. Then add 40 mL of water, stir thoroughly and allow to
stand for at least one hour. Filter off the precipitate thorough a previously weighed sintered
glass crucible and wash 4-5 times with 10 mL portions of cold 1% H2SO4. Collect the filtrate
and washings in a 250 mL volumetric flask quantitatively and make the volume up to the
mark with distilled water (solution B). Then wash the precipitate with rectified sprit until free
from sulphate. Dry the precipitate at 150oC to a constant weight.

31
(b) Determination of copper(II) + zinc(II).
Procedure: Pipette out 5.0 mL of the solution (Solution B) in a 250 mL conical flask. Add
dilute ammonia drop wise until the precipitate formed just dissolves (avoid large excess of
ammonia). Dilute to 50 mL and titrate with 0.01 M Na2EDTA solution using murexide as
indicator.

(c) Determination of copper(II).

Procedure: Take 25.0 mL of the solution (solution B) with a pipette into a 250 mL conical
flask. Add dilute ammonia drop wise until a faint blue precipitate appears. Dissolve the
precipitate with a drop or two of dilute acetic acid. Add 20 mL of 10% KI solution and keep
in dark for 5 minutes. Titrate the liberated iodine with the standard thiosulphate solution until
the brown colour of iodine fades. Then add 1-2 mL starch solution and continue titration until
the blue colour commences to fade. Then add about 10 mL of KCNS or NH 4CNS solution.
Complete the titration as quickly as possible.
(Prepare a standard solution of K2Cr2O7 and standardize the supplied thiosulphate solution
with the standard K2Cr2O7 solution.)

Experiment No. 24: Spectrophotometric determination of iron(II) with 1,10-

phenanthroline.
The reaction between iron(II) and 1,10-phenanthroline to form a red complex serves as a
good, sensitive method of determining iron spectrophometrically. The molar absorptivity of
the complex, [(C12H8N2)3Fe]2+, is 11,100 at 508 nm. The intensity of the colour is
independent of pH in the range 2 to 9. The complex is very stable, and the colour intensity
does not change appreciably over very long periods of time. Beer’s law is obeyed.
The iron must be in the +2 oxidation state, and hence a reducing agent is added before the
colour is developed. Hydroxylamine, as its hydrochloride, can be used, the reaction being
2Fe3+ + 2NH2OH + 2OH- → 2Fe2+ + N2 + 4H2O
The pH is adjusted between 6 and 9 by addition of ammonia or sodium acetate.

Procedure:
Dissolve 0.1 g of 1,10-phenanthroline monohydrate in 100 mL of distilled water, warming to
effect solution if necessary.
Dissolve 10 g of hydroxylamine hydrochloride in 100 mL of distilled water.
Dissolve 10 g of sodium acetate in 100 mL of distilled water.
Weigh accurately about 0.07 g of pure iron(II) ammonium sulphate, dissolve in water, and
transfer the solution to a 1 L volumetric flask. Add 2.5 mL of concentrated sulphuric acid
and dilute the solution to the mark. Calculate the concentration of the solution in mg of iron
per mL.
Into five 100 mL volumetric flasks, pipette 1, 5, 10, 25, and 50 mL portions of the standard
iron solution. Put 50 mL of distilled water in another flask to serve as the blank, and a
measured volume of unknown in another. To each flask add 1 mL of the hydroxylamine
solution, 10 mL of the 1,10-phenanthroline solution, and 8 mL of the sodium acetate solution.
Then dilute all the solutions to the 100 mL marks and allow them to stand for 10 min.

32
Using the blank as the reference and any one of the iron solutions prepared above, measure
the absorbance at different wavelengths in the interval 400 to 600 nm. Take readings about 20
nm apart, except in the region of maximum absorbance where intervals of 5 nm are used. Plot
the absorbance vs. wavelength and connect the points to form a smooth curve. Select the
proper wavelength to use for the determination of iron with 1,10-phenanthroline.
Using the selected wavelength, measure the absorbance of each of the standard solutions and
the unknown. Plot the absorbance vs. the concentration of the standards. Note whether Beer’s
law is obeyed. From the absorbance of the unknown solution, calculate the concentration of
iron (mg/L) in the original solution.

33
 Na+
O
+ O O
Na O
S S
O
O

N
N OH
N N
OH O

S
Na+
O O

34