EXPERIMENT NO.

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Object: Introduction to safety and working in chemical laboratory.

Theory: The real understanding of the principles which includes all laboratory techniques and
procedure is possible only if a student plans his/her work carefully in advance and work
purposefully during each laboratory period. For efficient working in the laboratory following
points must be bore in mind.

1. Careful planning in advance will enable you to work fast and efficiently.

2. While performing the experiment record all the observations on left hand side page of
practical notebook and get it signed by the instructor/faculty members.

3. Be aware of what you are doing and why you are doing it. As you work, think over the
probable questions, if after your determined efforts you cannot answer them, do not hesitate to
ask your teacher.

4. Always follow the experimental instructions exactly

5. All glassware’s must be scrupulously clean, if not, then clean it with chromic acid (potassium
dichromate + sulphuric acid), washed with tap water and-then rinsed with distilled water.

6. It should be regarded a normal practice that all determinations are performed in duplicate
While working in the laboratory suitable precautions should be observed to prevent accidents:

1. Never work alone in the laboratory unless a demonstrator or teaching assistant is present.

2. To protect clothing from spoilage and damage by chemicals and accidents, the laboratory
coat (white) should be worn while working in the laboratory.

3. Read the label carefully before using the chemical from the container.

4. Under no circumstances should the working surface of the bench become cluttered with
apparatus, if they will be needed at a later stage, it may be placed at the back of the bench.

5. Never taste any chemical unless instructed to do so.

6. Do not add any porous pieces or any solid to a boiling liquid; add only after allowing the
liquid to cool a little.

Even after all precautions, if accident occurs, do not panic and inform the instructor at once
and act as suggested below:

1. Small Burns: Immediately plunge the burned area for 4 -5 min. Into the cold the cold
water, preferably with ice in it, then gently dry and apply an ointment.
2. Severe Burns: Do not apply any ointment but seek medical treatment at once.
3. Acid Burns: Wash with plenty of water, then with very dilute sodium bicarbonate
solution and finally with distilled water

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 4. Base Burns: Wash with plenty or water, then with very dilute acetic acid solution and
finally with distilled water
5. Reagents sucked in Mouth: If the reagent is sucked, spit at once and wash the mouth
thoroughly with water.

TERM USED IN CHEMICAL ANALYSIS:

Chemical analysis is carried out in two ways:

1. Qualitative analysis 2. Quantitative analysis

1. Qualitative analysis is the detection of ions or radicals in an inorganic salt whereas
quantitative analysis involves the determination of quantity of a particular component
present in a substance. Quantitative analysis can be carried out in two ways:
(i) Gravimetric analysis (ii) Volumetric analysis

When the analysis is based on the measurement of weight then it is called gravimetric
analysis. On the other hand when it is based on measuring the volume of the solution of a
substance then it is called volumetric analysis,

TERMS USED IN VOLUMETRIC ANALYSIS

1. Titration: The process of finding out the volume of one of the solution required to react
completely with the definite volume of the other solution is known as titration. Titration
can be classified into four categories:

(i) Acid – Base titration/ Neutralization titration

(ii) Redox Titration/ oxidation- reduction titration
(iii) Precipitation Titration
(iv) Complexometric titration

2. Titrant: The solution of known strength is called the titrant.

3. Titrand: The solution which contains a substance to be estimated or whose strength is
to be estimated.
4. End point and Equivalence point: The point at which the completion of reaction
occurs is called equivalence point whereas an end point is an observable physical
change that occurs near the equivalence point.
5. Indicator: The substance which indicates the end point of titration is called indicator.
The indicator indicates the completion of reaction by change in colour at the end point.
There are three types of indicators

(i) Self Indicator: If one the reacting solution is strongly coloured and is
decolorized or changes into a deterrent colour by the substance that is being
determined then it is called self indicator Or it can defined as either titrant or
titrand changes its colour at the end point eg. Potassium permanganate.

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 (ii) Internal Indicator: Internal indicator are the substances which are added into
the conical flask in which titration is carried out. Eg. Phenolphthalein, methyl
orange, Diphenylamine

(iii) External Indicator: External indicator is the substance, which is not addedinto
the conical flask taken outside on the white tile or spot plate. Eg. Potassium
ferricyanide

6. Normality Equation: According to the law of equivalence, the substances react with
each other in a definite ratio by mass. For example, if an acid titrated against a base
then at the end point according to normality equation.

Number of gram equivalents of acid = Number of gram equivalents of the base

N 1 V1 = N2 V2

When N1 and N2 are normality’s of acid and base and V1 and V2 are the volumes of acid and
base respectively. This is known as the normality equation and is not fundamental principle of
chemistry.

7. Strength: The amount of substance dissolved in I litre of solution, when expressed in

grams is termed as strength of a solution. Strength of solution can also be expressed in
any of the following ways:

(i) Normality: It is the number of gram equivalents of the substance dissolved per
litre of the solution. It is denoted by N. If one gram equivalent of a substance is
dissolved per litre of the solution, it is called normal solution.
(ii) Molarity: It is the number of moles of the solute present per litre of the solution
it is denoted by M. Is denoted by m.
(iii) Molality: It is the number of moles of the substance dissolved in 1000gm or
1kg of the solvent. It is denoted by m.
(iv) Formality: It is the number of gram formula weight of the substance dissolved
in one litre of the solution. It is denoted by F.

8. Equivalent Weight: The equivalent weight of a substance is define as the number of

parts by weight of it that combine with or displace one part by weight of hydrogen or
eight part of oxygen or 35.5 parts by weight or chlorine. Equivalent weight expressed
in grams is called gram equivalent weight.

(i) Equivalent weight of an acid

Molecular weight of acid

Number of replaceable hydrogen atoms in one molecule of acid (Basicity of acid)

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 (Basicity - number of replaceable hydrogen atoms in an acid. Example HCL, H 2SO4,
H3PO4 are monobasic, dibasic and tribasic as they contain 1, 2 and 3 replaceable
hydrogen atoms respectively)

(ii) Equivalent weight of a base

Molecular weight of base

Number of replaceable OH – groups present in one molecule of acid (Acidity of base)

(Acidity = number of replaceable hydrogen OH groups in one molecule of a base. Example

NaOH, Ba (OH)2 and Al (OH)3 are mono, di and tri acid bases they contain 1 2 and 3 replaceable
OH groups respectively)

(iii) Equivalent weight of an oxidizing or reducing agent

= Molecular mass of the substance

Number of electrons gained / lost by one molecule in the redox reaction

9. Standard Solutions: A solution of known concentration is known as standard solution.

There are many types of substances which are generally employed for preparing
solution as explained below.

(i) Primary standard substance: Any substance whose standard solution can be
prepared directly by dissolving and accurately weighting its amount and making
up the solution to a known volume by dilution with water. A primary standard
substance possesses the following characteristics:
• It should be easily available in highly pure state. The impurities. If present must
be inert with respect to the substance with which it is brought to react.
• It should have a high equivalent weight or molar mass so that error due to
weighing is minimized.
• It should be readily soluble in water or the desired solvent.
• It should neither be hygroscopic not efflorescent.
• It should be stable at oven temperature used for drying. The hydrated
substances are seldom used as primary standards.
• It should be stable and unaffected by air.
• Its composition should not change on standing during storage.
• Crystalline oxalic acid, anhydrous sodium carbonate, dried KCL AgNO 3
FeSO4( NH4)2SO4.6H2O are used as primary standards.

(ii) Secondary Standard Substance: The substances which do not fulfil the above
requirements and their standard solutions are not prepared directly by weighing
are called secondary standard standard substances.

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 To prepare the standard solution of secondary standard and approximate weight
of the substance is dissolved in a known volume of the solvent (water) Then the
exact strength of the solution is found by titrating it against some primary
standard. The process is called standardization.

The common Secondary standards are:

• Alkali hydroxides like NaOH, KOH etc. As they are hygroscopic and their
weight keep on changing during weighing.
• KMnO4 as it is not available in pure form and is associated with manganese
dioxide which catalyzes the auto decomposition of permanganate solution on
standing.
• Inorganic acids HCl, H2SO4 etc. Because their concentrations are known only
approximately.

Multiple Choice Questions:

1. Phenolphthalein changes colour in

i)Acids ii)alkalis iii)water iv) salt solutions
a)
2. Which of the following combinations cannot produce a buffer solution?
i) HNO2 and NaNO2
ii) HCN and NaCN
iii) HClO4 and NaClO4
iv) NH3 and (NH4)2SO4

3. A pipette is used to transfer a base into a flask kept below a burette filled with acid. The
pipette, the flask and the burette should, respectively, be rinsed with....
i)Distilled water, base and acid.
ii)Base, Distilled water and acid.
iii)Acid, Base, Distilled water.
iv)Distil water in all cases.

4. Properties of a primary standard for use in acid-base titrations include……

i) Stability and high purity
ii) High purity and low solubility
iii) Reactive with air and low molar mass
iv) None of the above

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 EXPERIMENT NO: 2

Object: Determination of chloride content in the given sample by Mohr’s Method.

(Argentometric titration).

Apparatus: Pipette, burette, conical flask.

Theory: Chloride are present in water usually as NaCl, MgCl2, CaCl2 and may be due to
leaching of marine sedimentary deposits, pollution from sea water, industrial or domestic
wastes etc. Although chlorides are not harmful as such, their concentration over 250 ppm
imparts a salty taste to the water, thus rendering the water unacceptable for drinking purposes
from aesthetic point of view. Presence of chloride is also undesirable in boiler feed water
because they leads to problems like priming and foaming salts like MgCl2 may undergo
hydrolysis under high pressure and temperature prevailing in the boiler, generating
hydrochloric acid, which causes corrosion in boiler parts. Chloride in form of MgCl2 and
CaCl2 cause permanent hardness.

When silver nitrate solution is added to a solution of NaCl containing a few drops of
potassium chromate, white silver chloride is precipitated initially. As soon as all the chloride
ions have been precipitated out, even a drop of silver nitrate added in excess gives a red
precipitate of silver chromate, indicating the end point. This method is based on the fact that
silver chloride is more insoluble than silver chromate because the solubility product of silver
chloride (1.2 x 10-10) is ower than that of silver chromate( 1.7 x 10-10 ). Hence so long the
chloride ions are available the less soluble silver chloride is precipitated and no silver chromate
is formed. In fact silver chromate, even if formed, will immediately change to silver chloride
by interaction with chloride ions.

Ag2CrO4 + 2 Cl- 2 AgCl + CrO42-

As soon as all chloride ions used, even a slight excess of Ag+ produces insoluble silver
chromate, which is red in colour.
NaCl + AgNO3 AgCl + NaNO3
White ppt

2AgNO3 + K2CrO4 Ag2CrO4 + 2KNO3

Silver chromate
(red colour)
However, it should be noted that the water sample used for chloride determination should be
practically neutral or only faintly alkaline (pH 7-8) since silver chromate is readily soluble in
dilute acids, whereas in strongly alkaline solutions. Ag2O may get precipitated as AgOH and
in ammonia solutions, AgCl itself is soluble.

Procedure:
1. Standard N/20 NaCl solution:- Weight 0.2922g of pure and dry A.R. (Analytical Reagent)
NaCl (Mol. Wt. =58.44) in a clean and dry watch glass. Dissolve it in distilled water and make
up the volume up to the mark in a 100ml standard flask.

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2. Standardization of AgNO3 solution: Fill the burette with unknown AgNO3 solution and
note the initial reading. Pipette out 10ml of standard 0.05N sodium chloride solution into a
conical flask and add 1ml of indicator [K 2CrO4] solution. Add silver nitrate solution slowly
from a burette, swirling the liquid constantly; a white precipitate of AgCl is obtained. After
the addition of few ml of AgNO3, a red colour appear in the flask but disappears quickly upon
shaking. As the end point is approached, the red colour disappears slowly. Continue the
addition of AgNO3 solution drop by drop, till a permanent reddish brown colour is obtained.
The colour persists even after shaking. This will be the end point. Note the reading and repeat
the titration until concordant reading obtained.
3. Titration against unknown sample (NaCl): Repeat the above procedure with the unknown
sample provided
4. Blank Correction with distilled water: Take 10ml of distilled water sample in a conical
flask and add 1ml of indicator [K2CrO4] to it. Titrate it against AgNO3 solution till red colour
is obtained having the same intensity as in (1)
Observations:
1. Blank Correction with distilled water
S.N. Volume of distilled Burette reading Volume of AgNO3 Blank
water sample Initial Final Used Correction
(BC) Reading
taken
1 10

2 10

3 10

2. Titration of silver nitrate with sodium chloride (0.05N)

S.N. Volume of known Burette reading Volume of Final
NaCl solution Initial Final AgNO3 Concordant Reading =
V *
– BC= V
Used (V2*) reading
2 2
taken (V1)
1 10 0

2 10 0

3 10 0

3. Titration of silver nitrate with unknown sample

S.N. Volume of Burette reading Volume of Final
unknown NaCl Initial Final AgNO3 Concordant Reading =
reading V3
*
– BC= V3
solution taken Used
(V4) (V3*)
1 10 0
2 10 0

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 3 10 0
Calculations:

V1 = Volume of NaCl taken = 10 ml

N1 = Normality of NaCl taken = 0.05N

V2 = Volume of AgNO3 consumed = -----ml

N2 = Normality of AgNO3 solution = ------N

Since N1V1 = N2V2

Normality of NaCl provided x volume = Normality of AgNO3 x volume

N2 = N1V1/ V2

Similarly N 3 V3 = N4 V4

N3 = Normality of AgNO3 which is equal to N2 = ----- N

V3 = Volume of AgNO3 used = --------ml

N4 = Normality of unknown solution = ---------N

V4 = Volume of unknown sample taken = --------ml

N4 = N3 V3 (N3 = N2)

V4

Strength = N4 x Eq. wt. of Cl- g/l

(Equivalent weight of Cl- = 35.5)

Strength = N4 x 35.5 g/l

Result:
Chloride present in the unknown sample = -----------g/l

= -----------mg/l

= -----------ppm

Precautions:
1. The end point should be noted when a tinge of brownish red colour persists.
2. Store AgNO3 in a coloured bottle.
3. The reaction mixture should be briskly shaken during the titration.

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Multiple Choice Questions:

1.The titration in which insoluble colored precipitates are formed at end point is known as
i)Neutralization titration ii) Complexometric titration
iii)Precipitation titration iv) Redox titration
2. The pH of the sample in Mohr’s Method lies between
i)4-5 ii)8-9 iii)7-8 iv)9-10
3. Presence of chloride is undesirable in boiler feed water because
i)They cause priming and foaming ii)They undergo hydrolysis and cause corrosion
iii)They cause permanent hardness iv)All of the above
4. Sample required for blank correction reading in Argentometric titration is
i) Sodium Chloride solution ii)Distilled water
iii) Brine solution iv)Silver salt solution

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 EXPERIMENT NO. 3

Object: Determination of iron content in the given sample by using external indicator.

Apparatus: Burette, pipette, Standard flask, Spot plate, Glass rod, Conical flask.

Theory: Iron content can be determined by taking ferrous ammonium sulphate as sample. This
titration can be categorized under redox titration. Ferrous ions present in Mohr’s Salt are
oxidized to ferric ions by potasssium dichromate (strong oxidizing agent) in the presence of an
acid (dil HCl or dil H2SO4) Each molecule of K2Cr2O7 gives up three atoms of oxygen, which
are used for oxidation of ferrous ion to ferric ion, leaving ammonium sulphate unchanged. Also
in the presence of acid (H+ ions), each chromium atom reduces from Cr6+ to trivalent Cr3+ ion
( by gaining three electron form reducing agent). The reaction takes place in the following
manner.

K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4 H2O + 3[O]

Or [Cr2O7]2- + 8H+ 2Cr3+ + 4H2O + 3[O]

Hence complete reaction is:

K2Cr2O7 + 6FeSO4 + 7H2SO4 K2SO4 + Cr2(SO4)3 + 7H2O + 3Fe(SO4)3

Or [Cr2O7]2- + 14H+ + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

An external indicator ( 0.1 % potassium ferricyanide) is taken on white tile. From time to time
during titration, a drop of titrated solution is mixed with an indicator on tile. If much ferrous
ions (Fe2+) are present a strong blue color appears due to the formation of ferroferricyanide
complex.

2K3[Fe(CN)6] + 3FeSO4 Fe3[Fe(CN)6]2 + 2K2SO4

Ferrous ferricyanide ( Dark blue complex)

As the titration proceeds, blue colour becomes fainter because ferrous ion present in Mohr’s
salt keepon oxidizing to ferric ion. At the end point yellowish brown colored complex of
ferriferricyanide is formed indicating that all the ferrous ion are oxidized to ferric ions by
potassium dichromate.

3Fe2(SO4)3 + 2[K3Fe(CN)6] 3 K2SO4 + 2Fe[Fe(CN6)]

Ferri ferricyanide(Yellowish Brown)

If potassium ferricyanide (indicator) is used internally then some of the ferrous ions of FAS
form ferroferricyanide complex ( which is blue in color) and some of the ferrous ions of FAS
will undergo oxidation in presence of K 2Cr2O7 forming ferriferricyanide (whch is yellow in
color). At the same time the reduction of chromium form +6 state in K 2Cr2O7 to +3 state in
Cr2(SO4)3 occurs, which is of light green color. Thus,due to the formation of different colors
i.e.yellow color is masked by green and blue color and therefore we are unable to detect the
end point.

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Procedure :

Standard (N/20) solution of Ferrous Ammonium Sulphate:

Weight 1.9600 g of pure A.R. grade Ferrous ammonium sulphate (Eq. wt. = 392.12) and
transfer into a 100ml volumetric flask. Add 5ml of conc.H2SO4 dissolve the salt completely
and then make up to the mark with distilled water.

Titration of K2Cr2O7 solution with known ferrous ammonium sulphate solution:

Rinse the burette with potassium dichromate solution and fill it. Pipette out 10ml of ferrous
ammonium sulphate solution of known concentration in a clean conical flask and add to it about
equal volume of 2N H2SO4 with the help of measuring cylinder. Put a series of drops of external
indicator (0.1% potassium ferricyanide solution) with the help of a glass rod, on a tile. Run
K2Cr2O7 solution from the burette into the conical flask having acidified Mohr’s salt solution.
After adding one ml of K2Cr2O7 solution, with drawn a drop of the solution form conical flask
with a thin glass rod and mix it with one drop of Potassium ferricyanide on the tile. The
appearance of blue colour shows the presence of ferrous ions in the solution that is being titrated
and indicates that the end point has not yet reached. Now add another ml of K2Cr2O7 again and
do the test with another drop of potassium ferricyanide. Continue the addition of the dichromate
in one ml lots till no blue colour is obtained.

Supposed in experiment there is a blue colour on the addition of 18ml of potassium dichromate
solution, but no blue colour on the addition of 19ml of potassium dichromate solutions. It
means that the end point lies between 18ml and 19ml. Now repeat the titration by adding 18ml
of potassium dichromate without withdrawing any drop of the reaction mixture. After this add
0.1 ml of potassium dichromate solution every time and test a drop of the reaction mixture with
potassium ferricyanide. Continue adding dichromate in 0.1ml lots till a drop of the reaction
mixture does not give a blue colour with potassium ferricyanide. Repeat this titration to yield
concordant reading.

Titration of k2Cr2O7 solution with unknown ferrous ammonium sulphate solution:

The titration will be carried out exactly in the same way as mentioned above except in place of
known ferrous ammonium sulphate solution, unknown ferrous ammonium sulphate solution
will be taken.

Observations:

a) Titration of K2Cr2O7 solution with known ferrous ammonium sulphate solution:

S.N. Volume of Known FAS Burette reading Volume of Concordant

solution taken Initial Final K2Cr2O7 Used Reading
1 10 ml
2 10ml
3 10ml

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b) Titration of K2Cr2O7 solution with unknown ferrous ammonium sulphate solution:

S.N. Volume of unknown FAS Burette reading Volume of

solution taken Initial Final K2Cr2O7 Concordant
Used Reading

1 10 ml

2 10ml

3 10ml

Calculation:

N1 = Normality of known ferrous ammonium sulphate

V1 = Volume of known ferrous ammonium sulphate solution taken.

V2= Volume of K2Cr2O7 used.

N2 = ? (Normality of K2Cr2O7)

Volume x Normality of known solution = Volume x Normality of K 2Cr2O7

N1V1 = N2V2

0.05 x 10 = N2 x V2

N2 = 0.05 x 10

V2

Normality of known K2Cr2O7 …………….N

In the titration against unknown

N3 V 3 = N4 V 4 (N2 = N3)

Where , N4 = Normality of unknown ferrous ammonium sulphate

V4 = Volume of unknown ferrous ammonium sulphate solution taken.

V3 = Volume of K2Cr2O7 used.

N3 = Volume of K2Cr2O7 used. Which is equal to N2

N4 = N3 V3

V4

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By substituting the values in the above equation we calculate the normality of unknown ferrous
ammonium sulphate.

Strength of unknown solution = 392.12 x N4 g/l

(Equivalent weight of Mohr’s = 392.12)

392.12 g of FAS contain = 56g of Fe

Result:

Strength of ferrous contents in unknown solution = 56 x N4 g/l

Precautions:

1. The glass rod must be washd each time before use for withdrawing a drop from the titration
flask.

2. Always uses dilute H2SO4 as a reducing agent because K2Cr2O7 acts as an oxidant in acidic
medium.

Multiple Choice Questions:

1. The formula of Mohr’s salt is…………………….

2. What is the oxidation state of chromium in K2Cr2O7?

i) +6 ii) +3 iii) +2 iv) + 4

3. What is the oxidation state of chromium in Cr2(SO4)3?

i) +6 ii) +3 iii) +2 iv) + 4

4. The ............... of chromium form +6 state in K2Cr2O7 to +3 state in Cr2(SO4)3 occurs.

13
 EXPERIMENT NO. 4

Object: Determination of total, permanent and temporary hardness in water sample using
EDTA as standard solution.

Apparatus: Burette, conical flask, funnel, volumetric flask(250 ml).

Theory: Hardness is defined as the soap precipitating power of the water. Any salt which
precipitates soap is responsible for hardness. As soaps are sodium or potassium salts of higher
fatty acids and the sodium and potassium salts do not precipitate soap therefore they do not
cause any hardness. The divalent salts e.g. Ca(HCO 3)2, Mg(HCO3)2, CaSO4, MgSO4, CaCl2
and MgCl2 etc, are generally found in appreciable amount and are thus considered reasonable
for hardness in ground water, the presence of FeSO 4, Al2(SO4)3 also cause hardness although
their presence are not very common.

C17H35COONa + NaCl C17H35COONa + NaCl

Soap or any no ppt
Soluble salts
Exchange of sodium ion, thus sodium ion is not responsible for hardness.

Hardness may be of two types- Temporary hardness ( cause due to bicarbonate of Ca2+ & Mg2+
) and permanent hardness (caused due to chloride and sulphate of Ca2+ & Mg2+)

Both temporary and permanent hardness of water are expressed in their equivalents of
CaCO3 in parts per million (1,00,000 parts of water). This is referred to as degree of hardness
of water.

EDTA (versanate) forms a stable and soluble complex with a large number of metal ions
responsible for hardness. This method is the best method available for the estimation of
hardness as it is simple, inexpensive and gives accurate results. The determination is based
upon the fact that when EBT is added to water sample at pH10 (ammonia buffer) gives wine
red coloured unstable complex with calcium and magnesium ions present in water due to the
formation of less stable metal- indicator complexes. The addition of versenate solution results
in the formation of more stable metal- EDTA complexes as compared to metal indicator
complexes. The versenate first reacts with hardness producing metal ions present in water and
when they are consumed it reacts with metal ions released from the less stable metal-indicator
which gives rise to its original blue colour at the end point.

The formula of the versenate is:

HOOCCH2 CH2COONa HOOCCH2 CH2COO-

NCH2CH2N NCH2CH2N +2 Na+

NaOOCCH2 CH2COOH -OOCCH2 CH2COOH

The above equation can be written as:

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Na2H2Y H2Y2- + 2Na+

(Solid) ( in solution)

M2+ + H2Y2+ MY2- + 2H+ (M2+ = Ca2+ or Mg2+)

The metal ions get attached in place of hydrogen atoms of the carboxylic acid groups present
in the versenate forming stable complexes and not through the carboxylate ions created by the
ionization of Na+ in solution.

EBT polymerize in strongly acidic solutions to a red brown product and hence the indicator is
generally used in EDTA titration with solutions having pH greater than 6.5. The sulphuric acid
group loses its proton much before the pH range of 7 – 12. The sulphuric acid group losses its
proton much before the pH ranges of 7 – 12. The dissociation of the hydrogen atoms of the
phenolic groups only should therefore be considered and hence in solution it can be represented
by the formula H2D. Initially, when it is added to hard water along with buffer solution of pH
= 10, the reaction is;

M2+ + H2D- MD- + 2H+

(Blue colour) (Red colour)

MD- + H2Y2- MY2- + H2D-

(Red) (Colourless) (Colourless) (Blue)

On addition of EDTA, the red colour diminishes and ultimately at the end point changes from
wine red to sky blue.

Method:

1. Preparation of Standard CaCl2 solution:

Weight out accurately about 0.05g of pure CaCO3 on a watch glass and transfer it into a well
clean conical flask rinsed with distilled water. Add 3ml of dilute hydrochloric acid to dissolve
all the CaCO3, add distilled water, heat for 5 minutes to remove CO 2, cool and neutralize the
excess of acid with pure dilute ammonia using litmus paper as indicator which changes from
red to blue. Transfer it to a clean 250mL Volumetric flask rinsed with distilled water 2 or 3
times, transfer the washings also to the volumetric flask and make the volume upto the mark
by adding distilled water.

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2. Standardization of Versenate Solution:

Take 50 ml of standard CaCl2 solution in a conical flask. Add 3-4 drops of indicator (EBT) and
10ml of buffer solution containing (NH4OH + NH4Cl) to hold the pH around 10. Titrate it
against EDTA solution (0.01M) till colour just changes from wine red to sky blue and note
down the burette readings.

3. Determination of Hardness:

i. Total hardness: Take 50ml of water sample in the conical flask. Add 3-4 of the indicator
(EBT) and 10ml of buffer solution to hold the pH around 10, the colour of the solution will be
wine red if any hardness is present. Now add the reagent (EDTA solution) from the burette
until the wine red colour just changes to sky blue.

ii. Permanent Hardness: Take 50ml of the hard water sample in a beaker, boil it to reduce its
volume to approximately less than half (to ensure that the temporary hardness is completely
removed), cool and filter into a conical flask rinsed with distilled water. Wash the beaker with
distilled water two or three times and filter the washing also in the same flask to ensure that no
permanent hardness producing salts are left in the beaker. Make up the volume upto 50ml. Add
10ml buffer solution and 3-4 drops of indicator to it. Titrate the filter with the versenate solution
and note down the end point when the colour changes from wine red to sky blue.

Observations:

Weight of empty watch glass = W1…….g

Weight of watch glass + CaCO3 = W2……..g

Weight of CaCO3 = W2 – W1=……..g

1. Standardization of EDTA solution:

S.N. Volume of CaCl2 solution Burette reading Volume of EDTA

taken Initial Final Used
1 50 ml

2 50ml Xml

3 50ml
Volume of 50ml of standard CaCl2 solution = Xml EDTA solution used

2. Determination of total hardness:

S.N. Volume of hard water Burette reading Volume of EDTA

solution taken Initial Final Used
1 50 ml

2 50ml Yml

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 3 50ml

Volume of 50ml of hard water = Yml EDTA solution used

3. Determination of permanent hardness water:

S.N. Volume of boiled hard Burette reading Volume of EDTA

water solution taken Initial Final Used
1 50 ml

2 50ml Zml

3 50ml
Volume of 50ml of boiled hard water = Zml EDTA solution used

Calculation:

Now

250 ml of CaCl2 solution contains = 0.05g of CaCO3

1ml of CaCl2 solution contains = 0.05g/ 250ml of CaCl2 ( CaCO3 = CaCl2)

50 ml of CaCl2 solution contains = 0.05 x 50 = 0.01g of CaCl2
250
Xml of EDTA solution = 0.01 g of CaCl2
1ml of EDTA solution = 0.01g of CaCl2

Total Hardness:
So
Yml of EDTA solution used for 50ml of hard water = 0.01 x Y g of CaCl2
X
EDTA solution which is used for 1ml hard water sample = 0.01 x Y g of CaCl2

X 50
106 ml of hard water = 0.01 x Y x 106 g of CaCO3
X 50
Total hardness of given water sample = -------------ppm

17
Permanent Hardness :
Similarly for permanent hardness
Zml of EDTA solution used for 50ml boiled hard water = 0.01 x Z g of CaCO3
X
EDTA solution which is used for 1 ml boiled hard water = 0.01 x Y of CaCl2

X 50
106 ml of hard water = 0.01 x Z x 106 g of CaCl2
X 50

Result:-
1) Total hardness _______________ppm
2) Permanent hardness _____________ppm
3) Temporary hardness_____________(1 – 2)ppm
Standard result of hardness can be classified on the basis of their hardness value
S. No. Classification mg/l or ppm grains/gal
1. Soft Water 0 – 17.1 0 -1
2. Slightly Hard 17.1 – 60 1 – 3.5
3. Moderately Hard 60 – 120 3.5 – 7.0

4. Hard 120 – 180 7.0 – 10.5

5. Very Hard 180 & above 10.5& above]
Multiple Choice Questions:
1 A water sample contains 222 ppm of calcium chloride. The hardness in term of calcium
carbonate will be
1)400ppm ii) 20oF iii)40oF iv).400mg/l
2. Titraion of hardwater against EDTA involved
i)Redox titration ii) Complexometric titration
iii)Neutralisation titration iv) Precipitation titration
3. EBT has following linkage in its structure
i)-COOH ii) -C≡N iii)-N=C iv)-N=N-

4. The color of metal –EDTA complex is

i)Blue ii)Wine red iii)Yellow iv) Colorless

18
 EXPERIMENT NO. 5
Object: Determination of alkalinity in the given water sample.

Apparatus: Burette, Conical Flask, Pipette.

Theory: The alkalinity of water may be defined as its capacity to neutralize acids. It is due to
the presence of HCO3-, CO32-and OH- of Na+, K+, Ca2+ & Mg2+ . Some of the salts not all
which causes alkalinity also causes hardness. However presence of otheer bases such as
borates, silicates phosphates can also contributes to alkalinity through to a smaller extent.

The alkalinity of water can be considered to be mainly due to

Caustic alkalinity (due to OH- and CO32- ions )

Bicarbonate alkalinty also called temporary hardness (due to HCO3- ions)

Highly alkaline waters may lead to caustic embrittlement and also may cause deposition of
precipitates and sludges in the boiler tubes and pipes. Bicarbonates of calcium and magnesium
induces temporary hardnesss in water, which if untreated, causes scale formation in boilers.
The possible combinations of ions causing alkalinity in water are:

OH- only or

CO32- only or

HCO3-only or

OH- & CO32-together or

HCO3-& CO32- together

The possibility of OH- and HCO3- ions together is ruled out, because they combine
instantaneously to form CO32- ions.

OH- + HCO3- CO32- + H2O

NaOH +| NaHCO3 Na2CO3 + H2O

Thus OH- and HCO3- ions cannot exist together in water. On the basis of same reasoning, all
the three ( OH-, CO32-, HCO3-) cannot exist together.

The type and extent of alkalinity present in the water sample can be determined by titration an
aliquot of the sample against a standard acid, using phenolphthalein and methyl orange as
indicators. The determination is based on the following reactions:

1) [OH-] + [H+] H2O

2) [CO3-] + [H+] [HCO3-]

3) [HCO3-] + [H+] H2O + CO2

19
Action of Indicator ( Modern Quinoid Theory) :

Phenolphthalein: ( pH 8- 9.6) It possesses a benzenoid structure in acidic medium, where as

it changes to pink coloured quinoid in alkaline medium having quinoid form.

Methyl Ornage: (pH 3.1-4.4) It also exists in two aromatic forms. In alkaline solution it exists
in benzzenoid form and is yellow in colour. In acidic solution it exists in red colour having
quinoid structure.

The titration of the water sample against a standard acid up to phenolphthalein end point marks
the completion of reaction (1) and (2) i.e. complete neutralization of OH- ions and
neutralization of CO32- up to HCO3- stage ( half neutralization of CO32- ions). On the other
hand the volume of acid used up to methyl orange end-point marks the completion of reaction
(1), (2) and (3). Hence, the amount of acid used after the phenolphthalein end point corresponds
to one-half of normal carbonate plus all the bicarbonates while the total amount of acid used
represents the total alkalinity ( due to OH-, HCO3-, CO32-)

Table I represents various forms of alkalinity present in water sample

20
P= Phenolphthalein end-point , M= Methyl orange end-point
Alkalinity OH- (ppm) CO32- (ppm) HCO3- (ppm)
P=0 NIL NIL M
P=1/2M NIL 2P NIL
P<1/2M NIL 2P (M-2P)
P>1/2M (2P-M) 2(M-2P) NIL
P=M P=M NIL NIL
Procedure:
Transfer 50 ml of the water sample into a conical flask and add 1 ml of phenolphthalein
indicator. Titrate the sample with the standard HCl until the pink colour just disappears. Note
the titrate vaulue as the phenolphthalein end-point, (P). Add 1ml of methyl orange indicator to
the same solution and continue the titration until a sharp colour change from yellow to red takes
place. Note the titrate value from the beginning of the experiment as methyl orange end-point
(M)

Observations:

S.N. Vol. of the water Burette Reading Volume of N/50 HCl rundown
sample taken
Initial [P] Xml [M] Yml

1 50 0

2 50 0

3 50 0

Calculations:

Now [P] = X mL [M] = Y mL

Since [P] < ½ [M] the sample should contain only CO32- and HCO3- and it does not contain
OH- further

Similarly 2[P] should correspond to CO32- thus volume of N/50 HCl is equivalent to

CO32- = 2[P] = 2 X ml

Similarly 2[P] should correspond to HCO3- So volume of N/50 HCl equivalent to

HCO3- = [M – 2P] = [Y-2X] mL

Now for CO32-

N1 V 1 = N2 V2

N1 = Normality of water sample

21
V1 = Volume of water sample taken

N2 = Normality of HCl

V2 = Volume of HCl used

N1 x 50 = N2 x 2P [ {2P}= XmL ]
50
Or N1 = N2 x 2X = 2X
50 50 2500

The Strength of CO32- = N1 x 30 g/L [ equivalent weight of CO32- = 30]

Or strength of CO32- = N1 x 30 x 1000 mg/L

[ 30g of CO32- = 50g of CaCO3 ]

Strength of CO32- in term of CaCO3 = Strength of CO32- x 50 m/L

30
For HCO3- -

N3 = Normality of water sample

V3 = Volume of water sample taken

N4 = Normality of HCl

V4 = Volume of used HCl

N4 V4 = N3 V3

N3 x 50 = N x [ M – 2P ] [ {P} = X mL, {M} = YmL ]

50
N3 x 50 = N x [ Y – 2X ] = N x [ Y - 2X ]
50 50 50

The strength of HCO3- = N3 x 61 g/L [ 61 of HCO3-= 50g of CaCO3]

Or strength of HCO3- = N3 x 61 x 1000 mg/L

[ 61g of HCO3-= 50g of CaCO3 ]

Strength of HCO3- in term of CaCO3 = Strength of HCO3- x 50 g/L

61
Result:

Alkalinity with respect to CO32- = ……. mg/L

Alkalinity with respect ot HCO3- = …… mg/L

22
Total Alkalinity =………….. [ 1+2 ] mg/L

Multiple Choice Questions:

1. Which of the following cannot exist together in water with OH -

i) CO32- ii) HCO3- iii)both of the above iv) none of the above

2. Which of the following are draw backs of highly alkaline water

i)Carcinogenic disease formation ii)Deposition of sludges
iii)Caustic embrittlement iv)All the above

3. Which of the chromo groups is present in methyl orange

i)Azo group ii) keto group iii)Imino group iv) benzyne group

4. Which of the chromophoric group is present in phenolpthalein indicator

i) keto group ii) Azo group iii) imino group iv)none of the above

23
 EXPERIMENT NO. 6

Object: Determination of available chlorine in bleaching powder.

Apparatus: Burette, pipette , conical flask, Pestle mortar, Volumetric flask

Theory and significance: The available chlorine is the amount of chlorine liberated by the
action of dilute mineral acids on bleaching powder and it expressed in terms of percentage
weight of bleaching powder. Commercially Bleaching powder contains 36 – 40% available
chlorine and it deteriorates on storage due to continuous decomposition, so available chlorine
is determined as soon as the sample is prepared.

Bleaching powder is a mixture of many constituents. The main constituents of bleaching

powder are calcium hypochlorite Ca(OCl)2, basic calcium chloride [CaCl2.Ca(OH)2.H2O],
calcium hydroxide [Ca(OH)2] and some free slaked lime. The active constituent is Calcium
hypochlorite, which on treatment with HCl generates Hypochlorous acid, which is mainly
responsible for the disinfecting and bleaching action.
CaOCl2 + HCl CaCl2 + H2O + Cl2
( Available chlorine)

Cl2 + H2O HCl + HOCl

(Hypochlorous acid)

The disinfecting action of HOCl, take place by direct chemical reaction of HOCl with the
enzymes in the cell of microorganisms. The effectiveness of HOCl is supported by Chlorine
concentration and pH. pH should be greater than 8 for the efficient working of HOCl. At lower
pH, HOCl will be dissociated into hypochlorite ion, which is less effective than HOCl in
disinfecting action.
If pH<8 then HOCl H+ + OCl-
(hypochlorite ion)

The available chlorine is estimated by Bunsen’s method. In this method, a suspension of

bleaching powder is treated with dilute acetic acid in presence of KI solution. The liberated
chlorine from bleaching powder reacts with KI to form an equivalent amount of Iodine, which
is titrated against sodium thiosulphate solution using starch as an indicator

CaOCl2 + CH3COOH (CH3COO)2Ca + H 2O + Cl2

Cl2 + 2KI 2KCl + I2

I2 + 2Na2S2O3 Na2S4O6 + 2NaI

(Sodium tetrathionate)
Procedure:
The following solutions are supplied
1. Standard N/20 Iodine solution.

2. Sodium thiosulphate solution (to be standardized)

(a) Standardization of Sodium thiosulphate solution (Iodimetric titration)

24
Take the given Sodium thiosulphate solution in a burette. Pipette out 10ml of standard iodine
solution in a conical flask. Add about 3ml of HCl to it, the solution turns brown due to the
liberation of iodine since reaction is not instantaneous hence 4-5minutes must be allowed for
the complete liberation of iodine. Titrate it against Sodium thiosulphate to a light yellow colour.
Add 5-6 drops of starch indicator when yellow colour turns to blue. Continue the addition of
Sodium thiosulphate drop-wise till the blue colour disappears. Note down the volume of the
sodium thiosulphate used.
(b). Determination of available chlorine (Iodometric titration)

Weight out accurately 1.0g of bleaching powder in watch glass and transfer it to a mortar. Add
a few ml of distilled water. Grind it to a smooth thick paste and dilute it with more distilled
water. Transfer the suspension completely to 100ml volumetric flask with small portions of
distilled water and make the volume up to the mark. Shake it vigorously and pipette out 10ml
of homogeneous suspension in a conical flask. Add about 1 g of solid KI and about 5ml of
glacial acetic acid. Titrate the liberated iodine against Sodium thiosulphate as above. Note
down the volume of Sodium thiosulphate used.
Observations:
Weight of empty watch glass = W1 g
Weight of watch glass + bleaching powder = W2 g

Weight of bleaching powder = W2 - W1 = W g

Standardization of sodium thiosulphate solution:

S.N. Volume of Iodine Burette reading Volume of sodium

(V2) Initial Final thiousulphate Used
(V1)
1 10 0

2 10 0

3 10 0

Determination of Available chlorine:

S.N. Volume of bleaching Burette reading Volume of sodium

powder solution (V4) Initial Final thiousulphate Used
(V1)
1 10 0

2 10 0

3 10 0

25
Calculation:
According to normality equation,
N1 V1 = N2 V2

N1 = Normality of Sodium thiosulphate.

V1 = Volume of Sodium thiosulphate solution used.
N2 = Normality of iodine solution.
V2 = Volume of iodine solution taken.
N1 = N2 V2 = N x 10 = 2N
V1 20 V1 4V1
Let the weight of Bleaching powder dissolved in 100ml = ….….W g (W=1.0 g)
Strength of bleaching powder = 10 x W g/L
Let V3 ml be the volume of 2N (N1=N3) Sodium thiosulphate required for 10ml
4V1

(V4) bleaching powder suspension and N4 be the normality of Iodine liberated by bleaching
powder.
Now according to normality equation,
N3 V3 = N4 V4
N3 = Normality of Sodium thiosulphate which is equal to N 1

V3 = Volume of Sodium thiosulphate solution used.

N4 = Normality of bleaching powder solution.
V4 = Volume of bleaching powder solution taken.
N3 V3 = N4 V 4
Or N 4 = N3 V3 =2N x V3 N1 = N3 = 2N
V4 4V1 V4 4V1

Thus normality of chlorine = 2N x V3 [ Normality of Iodine = Normality of available

chlorine]
4V1 V4
Strength of available chlorine = 2N x V3 x 35.5 g/L
4V1 V4

26
 = 2N x V3 x 35.5 x 100
4V1 V4 1000

% of available chlorine = 2N x V3 x 35.5 x 100 x 100

4V1 V4 W x 1000
[W = 1.0 g]
Result: - The given bleaching powder sample contains…..……… % available chlorine.
Precautions:
1. The suspension of bleaching powder is very unstable and hence should be titrated
immediately after its preparation.
2. The solution should not be sucked in to the pipette with mouth as chlorine vapours are
harmful.

Multiple Choice Questions:

1. The indicator used in Iodometric titration is
i) Starch ii) K3Fe(CN)6 iii) K2CrO4 iv) Na2S2O3

2. In the titration of bleaching powder with hypo solution, what is the role of glacial acetic
acid…………………………
3. The yellow color of solution in iodometric titration is due to
i)low concentration of I2 ii)Liberation of I2
iii)Formation of Starch-Iodide complex iv)None of the above

4. The bleaching action of HOCl depends on

i)pH ii) concentration of I2 iii)Mineral acids iv) Conc. of Hypochlorite ion

27
 EXPERIMENT NO. 7
Object: Determination of coefficient of viscosity of the given liquid by Ostwald’s Viscometer
method.

Apparatus: Ostwald’s viscometer, stop watch, specific gravity bottle, pipette, distilled water,
rubber tubing.

Theory:

(i) Ostwald’s Viscometer: It consists of a capillary tube connected at its upper end with a
bulb B and its lower end with a U-tube provided with
bulb A. Bulb A is of larger size than B (Fig. 1) Marks
C and D are etched on the capillary tube above and
below the bulb B. The bulbs are necessary to
maintain the hydrostatic pressure during flow of
liquid. Through the capillary the liquid flows with a
measurable speed.

(ii) Relative Density Bottle: The density of liquid is conveniently measured by means of a
relative density bottle or specific gravity bottle. It is a
round bottomed glass vessel, fitted with a glass cork
containing a fine capillary Fig. 2.

The Ostwald’s Viscometer method is based on poiseuille’s equation. This related the rate of
flow of a liquid through a capillary tube with the coefficient of viscosity and is expressed by
the equation,

𝜋𝑟 4 𝑡𝑃
𝑛=
8𝑉𝑙
V= Volume of the liquid of viscosity n flowing in time t, through a capillary tube of radius r
and length 𝑙

P= Hydrostatic pressure of the liquid.

28
Thus the determination of the absolute viscosity by means by Poiseuille’s expression involves
the determination of V, r, t, 𝑙, and P.

The method is however tedious and laborious one. Hence, a simpler method is used wherein
we compare the viscosities of the two liquids. If the coefficient of viscosity of one liquid is
known, then that of the other can be calculated. If t1 and t2 are the flow times required to flow
for equal volumes of two liquids through the same length of a capillary tube then from equation
we have

𝜂1 = 𝜋𝑃1 𝑟 4 𝑡1 /8𝑉𝐼
𝑟 4 𝑡2
𝜂2 = 𝜋𝑃2
8𝑉𝐼
𝜂1 𝑃1 𝑡1
=
𝜂2 𝑃2𝑡2

P=hdg

Where h is the height of the liquid column (It is constant for all the liquids if taken for identical
points and liquids are taken in equal volumes for a particular set of observations.)

g = acceleration due to gravity

d = density of the liquid

Since in this case for two liquids h and g are same hence,

𝜂1 𝑑1 𝑡1
=
𝜂2 𝑑2 𝑡2

This will give us the relative viscosity of the given liquid. Relative viscosity has no units. The
𝑑1 𝑡1
absolute viscosity 𝜂 = . .𝜂1
𝑑2 𝑡2

Procedure:

1. Clean the viscometer with chromic acid (𝐾2 𝐶𝑟2 𝑂7 + 𝐶𝑜𝑛𝑐. 𝐻2 𝑆𝑂4 ) and then wash it several
times with distilled water. It is finally washed with alcohol and ether and then dried.

2. Attach a piece of clean rubber tube to the end C and clamp the viscometer vertically in air.

3. Now introduce a sufficient volume of the given liquid with the help of a pipette in bulb B so
that the bend portion of the U-tube and more than half of bulb B are filled up.

4. Through the rubber tube, suck up the liquid until it rises above the mark X. Make sure that
there is no air bubble inside the liquid.

5. Now, allow the liquid to fall freely through the capillary upto the mark X. Start the stop
watch and note the time 𝑡1 for the flow of the liquid from mark X to mark Y.

29
 6. Repeat the experiment thrice. The values should be concordant.

7. Remove the liquid and clean and dry the viscometer again.

8. Repeat the experiment by taking the same volume fo the distilled water and note down the
time taken 𝑡2 for flow of water from mark X to Y. Repeat thrice.

9. Weigh the relative density bottle and note down its weight.

10. Fill it with the given liquid and weigh it again.

11. Remove the liquid. Wash it with chromic acid and then distilled water. Dry in the oven.
Now fill it with the distilled water and weight it

Observations :

Room temperature =……….. ℃

Observation Table:

S. Given liquid Water

No.

Time of Flow Mean (𝑡1 ) Time of flow Mean (𝑡2 )

1.

2.

3.

Weight of empty specific gravity bottle =…..𝜔1 𝑔

Weight of empty specific gravity bottle + given liquid =…..𝜔2𝑔

Weight of empty specific gravity bottle + distilled water =…..𝜔3𝑔

Calculation:

𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑑1 𝜔2−𝜔1

= =𝜔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑑2 3 −𝜔1

30
 𝜂1 𝑑 𝑡
Relative viscosity of the given liquid = = 𝑑1 Χ 𝑡1
𝜂2 2 2

𝑑1 𝑡1
Absolute Viscosity = Χ Χ𝜂2
𝑑2 𝑡2

Result: The relative viscosity of the given solution is ... at…………. ℃

The absolute viscosity of the given solution is…..… Pas at ……..…℃

Multiple Choice Questions:

1. Which property measures the resistance of a liquid to flow?

a) Density b) Viscosity c) Volume d) Solubility

2. What is viscosity index?

a. effect of pressure on changes in viscosity
b. effect of temperature on changes in viscosity
c. effect of resistance between two surfaces
d. none of the above
3. What is coefficient of viscosity?
4. What is SI unit of Viscosity?

31
 EXPERIMENT NO. 8
Object: To determine the surface tension of the given liquid at room temperature by
stalagmometer using drop number method.

Apparatus: Stalagmometer, distilled water, unknown liquid, beaker, rubber tube with screw
pinch cock, clamp stand, specific gravity bottle or pyknometer.

Theory: Surface tension is defined as the attractive force exerted upon the surface molecules
of a liquid by the molecules beneath that tends to draw the surface molecules into the bulk of
the liquid and makes the liquid assume the shape having the least surface area. It is a physical
property of every liquid due to the intermolecular attraction among the molecules, which is
equal to the amount of force per unit area.

ɣ = F/ L

Gamma represents surface tension, F represents force, and L represents the length along which
the force is felt. Its SI unit is N/m and CGS unit is dyne /cm.

Surface tension forces are due to intermolecular forces between the liquid's molecules at the
liquid's outer boundaries. The molecule in the interior of liquid attracted by surrounding
molecules in all direction by cohesive forces and hence resultant force on that molecule is zero
(Fig.1). However, the molecules at the surface do not have other like molecules on all sides
around them and they are pulled inwards the liquid core by non-zero net force (Fig. 1)
Consequently, they cohere more strongly to
those associated with them directly on the
surface and form a surface "film"(called
Surface Strain or Stretching). Nevertheless,
these surface molecules are in the energetically
unfavourable state, which forces liquid to
minimize the surface area. The geometrical
requirement of smallest surface area at the
fixed volume is satisfied by the sphere. It is the
reason why the free drops of water form
spherical droplets.
Figure 1: Forces on the Molecule

The surface tension of the given liquid is determined relative to water at the room-temperature
by using stalagmometer. The no. of drops for the same volume of water and the given liquid
are counted and let these be as n1 and n2 respectively. Now if d1 and d 2 are densities of
water and the given liquid at the room temperature as determined separately by using specific
gravity bottle or pyknometer, then the surface-tension y 2 of the given liquid can be calculated
by using the simplified relationship as:
 1 n 2 d1
= 
 2 n1 d 2

32
Description of the apparatus:The stalagmometer consists of a bulbed dropping tube with a
capillary. The lower end of capillary is well ground, polished and flattened
in order to provide larger dropping surface. There are two marks A and C
above and below the bulb B. The upper end of the apparatus is connected
with a rubber tube with a screw pinch cock in order to control the rate of flow
so that spherical drop may be formed. Hence by simply counting the number
of drops for the given liquid and water and knowing their density, we can
find the relative surface tension of the liquid. The drop-count method isa very
convenient and quick process and can also be employed for determinations
at different temperatures by placing the whole apparatus in a thermostat.
Figure 2: Stalagmometer

Procedure:

1. Clean the stalagmometer, a specific gravity bottle or pyknometer thoroughly first with
chromic acid solution, then wash with distilled water and finally dry in electric oven.

2. By immersing lower end in a beaker containing distilled water, suck up water until it rises
above the mark A and tighten the screw of the screwpinch.

3. Now loosen the screw of the screw-pinch care-fully so that the liquid drops start falling at
an interval of about 2-3 seconds in successive drops. Counting of drops is started when the
water meniscus just reaches the upper mark A, and stopped when the meniscus just passes the
lower mark C. Repeat to get three readings and take the mean value.

4. Clean the stalagmometer and dry it. Fill it with liquid until it rises above the upper mark A
and count the number of drops as before.

5. Clean and dry the specific gravity bottle or pyknometer and measure the density of liquid.

Observations:

Room Temp. = ...........................  C .

Density of water at room temp. = d1

Weight of empty specific gravity bottle or pyknometer = w1 g

Weight of specific gravity bottle or pyknometer with water = w2 g

Weight of specific gravity bottle or pyknometer with liquid for the same volume as that of
water = w3 g

Weight of water = ( w2 − w1 )= m1 g (say)

33
Weight of liquid =( w3 − w1)= m2 g

No. of drops
Liquids Mean value
(1) (2) (3)
Water n1
Given Liquid n2

Calculations:

Density of the given liquid relative to water at room temperature.

m2
= d2
m1

 1 n2 d1
= 
 2 n1 d 2
Also
n1 d 2
 2 = Y1  
n2 d1

Where  1 = surface tension of water at room temp. (say 72 dynes/cm at 25°C)

Substituting the values of  1 , n1 , n2 , d1 and d 2 , the surface-tension of the given liquid at room
temperature thus becomes known

Result: The relative surface tension of liquid with respect to water at room temperature is.........

Precautions:

1. The stalagmometer and specific gravity bottle or pyknometer should be cleaned properly
and dried before use.

2. Fit the stalagmometer vertically.

3. The rate of the fall of drops should be adjusted in a way of having interval of at least 2-3
second in successive drops. The number of drops per minute must be in between 15-20.

4. The drops should fall from the tip of the stalagmometer under their own weight rather than
pushing them by force.

5. Wash and dry the stalagmometer after use.

Multiple Choice Questions:

1. At the boiling point , what is its surface tension of water?

i) zero ii) one iii) three iv) ten

2. What is the surface of water in contact with glass wall?

34
i) Concave ii) Convex iii) flat

3..What is the surface of mercury in contact with glass wall?

i) Convex i) Concave iii) flat

4.. How does soap affect the surface tension of water?

35
 EXPERIMENT NO. 9
Object: To determine pH of acidic solution using a pH meter and titration of such a solution
pH-metrically.

Materials: pH meter, Glass electrode HCl, 0.05 N NaOH.

Theory: The concept of pH was first introduced by Danish chemist Søren Peder Lauritz
Sørensen at the Carlsberg Laboratory in 1909. pH is a measure of the acidity or basicity of an
aqueous solution. pH is defined as a negative decimal logarithm of the hydrogen ion activity
in a solution.

pH = - log [H+]

Pure water is said to be neutral, with a pH close to 7.0 at 25 °C. Solutions with a pH less than
7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline.

In this method, we use combined electrode (a device having two electrodes together). In
combined electrode, glass electrode has balloon shaped structure at bottom made up of very
thin glass. This thin glass has a property to from a gel layer when it comes in contact of an aq.
medium

Functioning: When we dip the electrode in unknown solution, thin glass forms the inner gel
layer (due to standard HCl solution) and outer gel layer (due to unknown solution). These two
gel layers have two different potentials (Inner potential and outer potential). The potential
difference indicates the value of pH. On titration, the outer potential changes hence difference
between two potentials also gets changed, which gives a new pH value.

In case of strong acid and strong base titration, the equivalence point is at pH equal to 7. From
sigmoid curve (Obtained in the case of strong acid – strong base titration) we can calculate the
volume of NaOH used to neutralize the unknown HCl.

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When an alkali is added to an acid solution the pH of solution increases slowly, but at the
vicinity of the equivalence point, the rate of change of pH of the solution is very rapid. From
the sharp break in the curve, we can read the equivalence point using sigmoidal curve, through
which the strength can be calculated by using normality equation.

Strength of HCl can be determined by titrating it with a standard NaOH solution (Acid-Base
titration). This determination can be done by pH-metric titration.

Nature of Graph:

pH

Vol. of NaOH

pH- metric titration is different from ordinary acid-base titration as we do not use indicators
hence it is based on equivalence point not on end point.

As in earlier stage of titration, strong acid is neutralized by small amount of strong base
resulting in a slow change in pH. Then pH changes sharply near the equivalence point (at pH=7)
and again there is a slow change in pH value on addition of NaOH as system has been changed
into basic medium.

pH-metric titration is more accurate than an ordinary acid-base titration because it is based on
equivalence point (the point when N1V1 is exact equal to N2V2) where as ordinary acid-base
titration is based on end point calculation (point when mili equivalent of one compounds is
slightly more than other).

Procedure:

Calibration of Electrodes:

The electrode should be calibrated before beginning measurements or when pH readings are
suspect. Once the calibration has been carried out, do not change electrodes without further
calibration.

Following procedure is adopted.

a) Dip the combined electrode in a 4 pH buffer solution.

b) Set the “TEMPERATURE C” control to the buffer solution temperature.
c) Set the function selector switch to pH position and adjust “CALIBRATE” control until
the meter displays the precise pH value of the buffer solution.
d) Now set the function selector switch to STANDBY.

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 e) Remove the electrode from the buffer solution: wash with distilled or deionised water.
f) Dip the combined electrode into another buffer solution (says 9.2pH value).
g) Set the “TEMPERATURE C” control to the temperature of the selected buffer
solution.
h) Set the function selector switch to pH position. Adjust the “SLOPE” correction control
using a screwdriver, until the meter displays the pH value of the selected buffer
solution. Check that the correct readings are obtained with both solutions without
further adjustment.
pH Measurement:

To measure pH value of the solution, after calibrating the electrode proceed as follows:

a) Remove the electrode from the buffer solution, was with distilled or de-ionised water,
and immerse in the solution under test (2).
b) Set the “TEMPERATURE C” control to the temperature of the test solution.
c) Set the function selector switch to the pH position.The meter will display pH value of
the test solution.
d) Between measurements leave the electrode immersed in distilled water and function
selector switch to “STANDBY” position.
In beaker (1) add sufficient water so that glass electrode as well as the reference electrode
are completely dipped. In beaker (2) take 100 ml of HCl solution. Note the pH of pure acid
solution. Now add 1ml of 0.05N NaOH from the burette in the beaker. Stir the content well
and note the reading. Note the pH of the solution on each addition upto say 35ml of NaOH.

Volume of acid taken= 100ml (say)

Volume of 00, 01, 02, 03, 04, 05, 06, 07, 08, 09, 10, 11, 12, 13, 14, 15, 16, 17,
Alkali 18……..
added(ml)

pH

Calculation:

A curve in plotted with pH values as ordinate and the voume of alkali added (ml) as
abscicca.

Find out the end point suppose it is equivalent to x ml of NaOH.

From normality equation

N1V1 = N 2V 2

(Acid) (Alkali)

N1 x 100 = 0.05 x X

Strength of HCl solution = 0.05 x X x 36.5

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 100

Result: The strength of given acid solutionis …………………..g/l.

Precautions:

1.The temperature control knob of the pH meter should be adjusted to the room
temperature.
2.After addition of alkali, solution should be properly stirred.
3.The pH should be first standardized by taking the buffer of a known pH.
4.Soak the electrode in water for some hours (preferably over night before use).
5.
Quiz Questions:

1.The Reference electrode used in pH meter is

i) Glass electrode ii) Hydrogen electrode
iii)Quinhydrone electrode iv)Silver electrode

2.The least count of pH meter is

i)0.1 ii)0.01 iii)0.001 iv) none of the above
3. Why electrode is dipped in buffer solution before titration in pH metric titration?
4. Give the cell diagram of the electrode used…………………................................

EXPERIMENT NO. 10

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Object: Preparation of Phenol – formaldehyde resin (Bakelite resin)

Apparatus requirement:
a). Beaker, glass rod, funnel and filter paper
b). Chemical. Phenol, Formaldehyde (40% of solution), conc. HCl and glacial acetic acid and
hexa methylene tetramine.

Theory:
Phenol and formaldehyde react to form methylol derivate which act as monomers for
subsequent polymerization.

The nature of product depends on the nature of the catalyst (acidic or basic)

1) In presence of acid catalysts, the methylol derivatives condense with phenol to form the
dihydroxy diphenyl methane. These on further condensation gives low molecular weight linear
polymers which are fusible and soluble and are known as Novalacs.

2) In presence of alkaline catalyst, methyl phenol can condense either through methylene
linkages or through ether linkages to form Resols.

Further heating of novolac in the presence of a catalyst, Hexamethylene tetramine ( it

produces HCHO), induces three dimensional, cross – linked networked polymer, Bakelite,
which is hard rigid and infusible solid.

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Bakelite is a hard, rigid, scratch resistant, infusible, water resistant solid. They possess
excellent electrical insulating character.

Bakelite is used for making electric insulator parts like switches , plugs, heater handles etc.
They are used for making moulded articles (like telephone parts etc.), as adhesive and in paints
and varnishes.

Procedure:

a). Take 2 grams of phenol and 5 ml of glacial acetic acid in 250 ml beaker.
b). Add 2.5 ml of 40% formaldehyde solution into it.
c). Wrap a cloth loosely round the beaker.
d). Slowly add a few ml of conc. HCl into the mixture carefully and heat it slightly.
e) Formation of Novolac takes place which on further heating in presence of hexamethylene
tetramine results in the formation of cross – linked, pink coloured polymer, Bakelite.
f). Wash the product, several times with distilled water.

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g). Dry and measure the weight of this pink plastic.
h). Calculate the yield.

Precaution :
Add conc. HCl carefully for the formation of Bakelite as it is a vigorous reaction.

Multiple Choice Questions

1 The Catalyst used for formation of Bakelite is

i)(CH2)4N4 ii)(CH2)6N4 iii)(CH2)6N3 iv)(CH2)6N2
2 Bakelite is a
i)Phenol-Formaldeyde resin ii) Cross linked polymer
ii) Pink colored plastic iv) All of the above

3 Thermoplastic product formed by the condensation of methylol derivative and phenol

in presence of acid catalyst is
i)Bakelite ii)Resol iii) Trimethylol phenol iv) Novolac

4 Bakelite is said to be a cross linked polymer as

i)Its combining monomer have one active site
ii) Its combining monomer have two active site
iii) Its combining monomer have more than two active site
iv) Its combining monomer have 3- D structure

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