LIST OF EXPERIMENTS

1. To determine the total residual chlorine in water.

2. Determination of Dissolved oxygen in the given water sample.
3. To determine the temporary, permanent and total hardness of a sample of
water by complexometric titration method.
4. To determine the type and extent of alkalinity of given water sample.
5. To prepare and describe a titration curve for phosphoric acid – sodium
hydroxide titration using pH-meter.
6. (a) To find the cell constant of conductivity cell.
(b) Determine the strength of hydrochloric acid solution by titrating it
against standard sodium hydroxide solution conductometrically.
7. To determine the ion exchange capacity of a given cation exchanger.
8. Determination of viscosity of given oil by means of Redwood viscometer I.
9. To determine flash point and fire point of an oil by Pensky Martin’s
Apparatus.
10. To determine the Iodine value of the oil.
11. Determination of amount of oxalic acid and H2SO4 in 1 L of solution
using N/10 NaOH and N/10 KMnO4 solution.
12. To determine the number of water molecules of crystallization in Mohr’s
salt (ferrous ammonium sulphate) provided standard potassium dichromate
solution (0.1N) using diphenylamine as internal indicator.
13. To determine the ferrous content in the supplied sample of iron ore by
titrimetric analysis against standard K2Cr2O7 solution using potassium
ferricyanide [K3Fe(CN)6] as external indicator.
14. (a) To determine the surface tension of a given liquid by drop number
method.
(b) To determine the composition of a liquid mixture A and B (acetic acid
and water) by surface tension method.

1
 EXPERIMENT NO.1
AIM
To determine the total residual chlorine in water .

APPARATUS
Burette, pipette, conical flask and beakers

CHEMICALS REQUIRED
N/50 Na2S2O3, Glacial acetic acid, 10% KI

THEORY
The estimation of residual chlorine is based on oxidation of KI by residual chlorine that
is by iodometric titration.
When the water sample containing residual chlorine is treated with KI, the
residual chlorine (both free and combined) oxidizes KI and liberates I2 in equivalent
amount.
Cl2 + 2KI → 2KCl + I2
2OCl¯ + 2KI → 2KCl + I2 + O2
HOCl + 2KI + HCl → 2 KCl + I2 + H2O
NHCl2 + 2KI + 2HCl → 2KCl + I2 + NH3

The liberated I2 is titrated against hypo solution, using starch as indicator.

2Na2S2O3 + I2 → Na2S4O6 + 2NaI
I2 + Starch → deep blue complex
The end point is disappearance of blue colour.

PROCEDURE
1] Pipette out 100 ml of the given water sample in conical flask and add 5 ml of 10%
KI solution and about 3 ml of glacial acetic acid to maintain pH upto 3-4.
2] Cover the flask and shake it well to mix the solution.
3] Using a wash bottle rinse the sides of the flask.
4] Titrate it with N/50 Na2S2O3 solution from the burette till the solution becomes straw
yellow.
5] Add 2 ml of the starch solution. The solution will turn blue.
6] Continue titration with Na2S2O3 till the blue colour disappears.
7] Note the final reading and repeat to get three concordant readings.

2
OBSERVATIONS
Normality of Na2S2O3 solution = N/50

S No Volume of the solution Burette reading Volume of the titrant used

taken in the titration Initial Final (Final-initial) (ml)
flask(ml)
1.
2.
3.

CALCULATIONS
N1V1 = N2V2
Water Na2S2O3
N1 x 100 = 1/50 x V2
N1 = V2/5000
Total chlorine residual = N1 x Eq. wt.
= N1 x 35.5 g/L
= N1 x 35.5 x 1000 mg/L
RESULT Amount of total residual chlorine in given water sample = ………. mg/L

PRECAUTIONS
1] Chlorine vapours are harmful so the solution should not be sucked into the pipette with
mouth.
2] The titration should be completed rapidly in order to avoid atmospheric oxidation of
iodide
3] First disappearance of blue colour maybe taken as end point.
……………………………………………………......
VIVA VOCE
1. Why Cl2 is added to water?
2. What is the action of Chlorine on pathogen?
3. Why and how pH is adjusted between 3 and 4?
4. Why starch is added in the end part of the solution?
5. Write the reaction between KI and I2.
6. What is the necessity of adding KI ?
7. What is the difference between Iodometric and Iodimetric titrations?
………………………………………………………..
EXPERIMENT NO. 2

3
AIM
Determination of Dissolved oxygen in the given water sample.

APPARATUS
Burette, pipette, conical flask, beakers

CHEMICALS REQUIRED
Na2S2O3 (N/100), MnSO4 solution, KI, Starch, conc. H2SO4, Alkaline Iodide-azide
solution, Starch.

THEORY
Oxygen itself is not a pollutant in water but its deficiency in water is an indicator
of several types of pollution in water.
Dissolved oxygen (DO) is determined by Winkler’s method or iodometric
titration. The DO in water oxidizes KI and an equivalent amount of iodine is liberated.
This iodine is titrated against a standard hypo solution. However, since DO in water is in
molecular state and is not capable of reacting with KI, therefore an oxygen carrier such as
Manganese hydroxide is used.
The method involves introducing a concentrated solution of MnSO4, NaOH and
KI, Azide reagent, into the water sample. The white precipitate of Mn(OH)2 which is
formed, is oxidized by oxygen in water sample to give a brown precipitate of basic
manganic oxide [MnO(OH)2]. This MnO(OH)2 in acidic medium dissolves and liberates
free iodine from the added KI in a equivalent amount of dissolved oxygen in water
sample. This liberated iodine is then titrated against Na2S2O3 solution using starch as
indicator. The reactions involved are:

MnSO4 + 2NaOH → Mn(OH)2 + Na2SO4

4Mn(OH)2 + O2 → 2MnO(OH)2
Basic manganic oxide
2MnO(OH)2 + H2SO4 → MnSO4 + 2H2O + [O]
2KI + H2SO4 + [O] → K2SO4 + H2O + I2
2Na2S2O3 + I2 → Na2S4O6 + 2NaI

The nitrite present in water, interfere with the titration as these can also liberate I2 from
KI.
2HNO2 + H2SO4 + 2KI → 2NO + K2SO4 +2H2O +I2

Thus to destroy nitrite, sodium azide is used.

2NaN3 + H2SO4 → 2HN3 + Na2SO4

(Hydrazoic acid)
HNO2 + HN3 → NO2 + N2 + H2O
4
PROCEDURE

1] A known amount of sample water say 300 ml is taken in a stoppered bottle avoiding
contact with air.
2] Add 0.2 ml of MnSO4 solution to it by means of a pipette, dipping the end well below
the surface of water. Also add 2 ml of alkaline iodide azide solution to it.
3] Stopper the bottle and shake thoroughly. Allow the brown precipitate of MnO(OH)2
formed, to settle down.
4] When some portion of the liquid below the stopper is clear, add 2 ml of conc H2SO4
with the help of pipette. Stopper and mix till the precipitate is completely dissolved. The
characteristic brown colour of iodine is produced.
5] Transfer 100 ml of the above solution in a 250 ml flask with a pipette. Titrate the
liberated I2 with standardized Na2S2O3 solution until the sample solution becomes pale
yellow.
6] Add 2 ml of starch solution, the solution will turn blue.
7] Continue titration till the blue colour disappears.
8] Repeat to get another reading.

OBSERVATIONS

Volume of the water sample taken for titration = 100 ml

S No Volume of the solution Burette reading Volume of the titrant used

taken in the titration Initial Final (Final-initial) (ml)
flask(ml)
1.
2.
3.

Normality of Na2S2O3 used = N/100

CALCULATIONS

N1V1 = N2V2
Hypo O2 in water
1/100 x V1 = N2 x 100
N2 = V1/10000
Strength of dissolved oxygen = N2 x Eq. wt.
= V1/10000 x 8 g/L
= V1/10000 x 8 x 1000 mg/L
= 0.8 x V1 ppm

RESULT

5
The amount of dissolved oxygen in water = ………ppm

PRECAUTIONS
1] The water should be taken in the stoppered bottle very carefully without trapping air
bubbles which could raise oxygen level by aerating the sample.
2] MnSO4 and alkaline iodide-azide solutions are added to the water sample just below
the surface of water.
3] Whole of the precipitate of MnO(OH)2 should be dissolved in H2SO4.

………………………………………………………
VIVA VOCE
1. Why MnSO4 is use in this experiment?
2. Why azide is added to reaction mixture?
3. Why DO is required in water?
4. What is the reaction involved in the process?
5. What is the role of basic of MnO(OH)2?
………………………………………………………

EXPERIMENT NO. 3
AIM
To determine temporary, permanent and total hardness of a given water by
complexometric titration method.

CHEMICALS REQUIRED
0.01 M EDTA, Eriochrome Black-T(EBT), Water sample, buffer solution.

THEORY
The hardness of water can be determined by complexometric titration. EDTA is used as
complexing reagent. It forms stable complexes with Ca2+ and Mg2+ and number of other
metal ions in the solution. The Ca2+ and Mg2+ present in water are titrated with EDTA
using Eriochrome black T as indicator. The structure of EDTA is

HOOCCH2 CH2COOH
N-CH2-CH2-N
HOOCCH2 CH2COOH

EDTA is generally used in the form of its disodium salt or tetra sodium salt on account of
their greater solubility in aqueous medium. EDTA is generally written by the formula
H4Y or Na2H2Y. It reacts with divalent ions in 1:1 ratio

6
M2+ + H2Y2- → MY2- + 2H+
or
M + H2Y2- → MY(n-4) + 2H+
n+

Estimation of hardness by EDTA method is based on the following principle:

I. First, the indicator Eriochrome black T, which is a blue coloured dye, forms an
unstable complex with Calcium and Magnesium ions in hard water at a pH of 9-10. The
complex is wine red in colour.
Mg2+/Ca2+ + EBT → [Mg/Ca-EBT]
Unstable complex (wine red)
II. As this solution is titrated against EDTA, the free Ca2+ and Mg2+ ions in water form
stable metal-ion EDTA complex
[Mg2+/Ca2+] + EDTA → [Mg/Ca-EDTA]
Stable complex (Colourless)

Once the free metal ions are complexed , the EDTA replaces the Ca2+ and Mg2+
ions from the unstable indicator complex also, to form a stable complex, with the result,
the indicator is set free. Since the free indicator is blue in colour at the above mentioned
pH, the end point is the appearance of blue colour.
[Mg/Ca-EBT] + EDTA → [Mg/Ca-EDTA] + EBT
Wine red Blue
Thus the amount of EDTA used corresponds to the hardness of water.
The temporary hardness is removed by boiling and after the removal of precipitate by
filtration, the permanent hardness in the filtrate is determined by titration with EDTA as
above. Temporary hardness is given by the difference of total hardness and permanent
hardness. Hardness in water is generally expressed in calcium carbonate equivalents.

PROCEDURE
I. Preparation of Standard Hard Water
Dissolve 1g of pure dry CaCO3 in minimum quantity of dilute HCl and then evaporate
the solution to dryness on a water bath
Dissolve the residue in distilled water to make 1litre solution. Each ml of this solution
thus contains 1 mg of CaCO3 equivalent of hardness.
II. Standardization of EDTA Solution
Rinse and fill the burette with EDTA solution.
Pipette out 25 ml of standard hard water into volumetric flask and add 20ml of distilled
water and 10ml of buffer solution.
Add 2-3 drops of indicator EBT.
Titrate against 0.01 M EDTA solution till the colour of the solution changes from wine
red to blue.
Note the final reading and repeat to get 3 concordant readings.
III. Measurement of Total Hardness
Pipette out 25 ml of sample water into volumetric flask and add 20ml of distilled water
and 10ml of buffer solution.
7
Add 2-3 drops of indicator EBT.
Titrate against 0.01 M EDTA solution till the colour of the solution changes from wine
red to blue.
Note the final reading and repeat to get 3 concordant readings.
IV. Measurement of Permanent Hardness
Take 250ml of the water sample in a large beaker and boil it till the volume is reduced to
1/4th
Filter, wash the precipitate with distilled water, collecting filterate and washing in a
250ml measuring flask.
Make up the volume to 250 ml with distilled water, then titrate 25 ml of boiled water
sample as described in para (II) by adding distilled water, buffer and indicator.

OBSERVATIONS
Volume of hard water taken for each titration = 25ml
Molarity of EDTA = 0.01 M

OBSERVATION TABLE

EDTA Vs. Standard Hard Water (V1)

S No. Vol of the solution taken Burette readings Volume of titrant used
in the titration flask (ml) Initial Final (final-initial) (ml)
1.
2.
3.

EDTA Vs. Sample Water (V2)

S No. Vol of the solution taken Burette readings Volume of titrant used
in the titration flask (ml) Initial Final (final-initial) (ml)
1.
2.
3.

EDTA Vs. Boiled Water (V3)

S No. Vol of the solution taken Burette readings Volume of titrant used
in the titration flask (ml) Initial Final (final-initial) (ml)
1.
2.
3.

CALCULATIONS
1] Standardization of EDTA
EDTA forms 1:1 complex with Ca2+ and Mg2+,
Therefore, 1000 ml of 1M EDTA = 1 mol of CaCO3 = 100g of CaCO3
8
 1ml of 0.01M EDTA = 100 x 1/1000 x 1/100 g of CaCO3 = 1mg of CaCO3
25 ml of standard hard water = V1 ml of 0.01 M EDTA = 1.00 x V1 mg of CaCO3
1 ml of 0.01 M EDTA = 25/V1 mg CaCO3 equivalents

2] Calculation of Total Hardness

25 ml of sample water requires = V2 ml of 0.01 M EDTA
= V2 x 25 / V1 mg CaCO3 eq
Total hardness = 1000 x V2 /V1 mg/L

3] Calculation of permanent hardness

25 ml of boiled water requires = V3ml of 0.01 M EDTA
= V3 x 25 / V1 mg CaCO3 eq
Total hardness = 1000 x V3 /V1 mg/L

4] Calculation of temporary hardness

Temporary hardness = Total hardness – permanent hardness
RESULT
The total hardness of water is……mg/L
The permanent hardness of water is……mg/L
The temporary hardness of water is……mg/L
………………………………………………………
VIVA VOCE
1.What is temprorary and permenent hardness of water
2.What is the principle of EDTA titration
3.What are disadvantages of water
………………………………………………………
EXPERIMENT NO.4
AIM
To determine the type and extent of alkalinity of given water sample

APPARATUS
Burette, pipette, conical flask, beakers.

CHEMICALS REQUIRED
N/10 HCl, Phenolphthalein, and methyl orange

THEORY
Determination of alkalinity due to different ions is based on the titration of water sample
against a standard acid making selective use of indictors. The indicators used are
phenolphthalein and methyl orange. The reactions taking place may be represented by the
following equations:
9
OH¯ + H+ → H2O
CO32- + H+ → HCO3¯ P M
HCO3¯ + H+ → H2CO3

The volume of the acid used up to phenolphthalein end point corresponds to the reaction
(a) and (b) that is complete neutralization of OH¯ ions and neutralization of CO32- ions up
to HCO3¯ stage. (half neutralization of CO32- ions)
The volume of the acid used up to methyl orange end point corresponds to the reaction
(a), (b) and (c) i.e. complete neutralization of OH¯, CO32- and HCO3¯ ions.
Thus from the respective volumes of the acid used, the respective strengths of the various
ions can be determined.
A known volume of the sample is titrated against a standard acid using
phenolphthalein as indictor and alkalinity is found out in terms of CaCO3 equivalents by
using normality equation. This alkalinity is called phenolphthalein alkalinity (P).
Similarly the sample is titrated against a standard acid using methyl orange as indicator
and alkalinity is calculated in terms of CaCO3 equivalents. This alkalinity is called
methyl orange alkalinity (M) or total alkalinity of water sample.
From the measurement of P and M, it is possible to calculate the magnitude of
various forms of alkalinity present in water sample,
Alkalinity due to HCO3¯ only
Alkalinity due to CO32- only
Alkalinity due to CO32- and HCO3¯
Alkalinity due to CO32- and OH¯
Alkalinity due to OH¯ only

Case (i): When P=0, this implies that volume of the acid used till phenolphthalein end
point is 0. This can only happen if CO32- and OH¯, both are absent. Whatever alkalinity
is present is due to HCO3¯ ions and can be detected using methyl orange as indicator.

Case(ii): When P= ½ M, this implies that only CO32- ions are present. Neutralization
using phenolphthalein as indicator reaches upto HCO3¯ stage. Same amount of acid will
be further used when methyl orange is used as indicator to neutralize HCO3¯ to H2O and
CO2. The strength of CO32- will be given by M or 2P.

Case(iii): When P < ½ M, this implies that besides the CO32- ions, HCO3¯ ions are also
present. The acid used until P corresponds to half neutralization of CO32- ions. Further
titration using methyl orange as indicator corresponds to neutralization of HCO3¯
obtained from CO32- ions and HCO3¯ originally present in the reaction mixture.
Alkalinity due to CO32- = 2P
Alkalinity due to HCO3¯ = (M-2P)

10
Case(iv): When P > ½ M , this implies that apart from CO32- ions, OH¯ ions are also
present. OH¯ will be completely neutralized by the acid, whereas CO32- will be
neutralized up to the HCO3¯ stage using phenolphthalein as indicator. On further
titrations with the acid using methyl orange as indicator, the neutralization of HCO3¯
takes place.
Alkalinity due to CO32- = 2 (M-P)
Alkalinity due to OH¯ = M-2(M-P) = (2P-M)

Case(v): When P=M, implies that only OH¯ ions are present. Alkalinity due to OH¯ =
P=M.
Thus on the basis of the analysis of water with respect to phenolphthalein alkalinity and
methyl orange alkalinity, the alkalinity due to different ions can be calculated. The results
are summarized in the following table.

Alkalinity OH¯ (ppm) CO32- (ppm) HCO3¯ (ppm)

P=0 NIL NIL M
P= ½ M NIL 2P NIL
P< ½ M NIL 2P (M-2P)
P> ½ M (2P-M) 2(M-P) NIL
P=M P=M NIL NIL

INDICATORS Phenolphthalein and methyl orange

END POINT Pink to colourless (Phenolphthalein), yellow to red (Methyl orange)

PROCEDURE
Rinse and fill the burette with N/10 HCl.
Pipette out 20 ml of water sample into a conical flask. Add 1-2 drops of phenolphthalein.
Titrate the water sample in conical flask with N/10 HCl till the pink colour just
disappears.
Note down the reading.
Add methyl orange to the same solution .
Titrate it using N/10 HCl till a red colour is obtained.
Record the observation and repeat to get three concordant readings.

OBSERVATIONS

(a) Using phenolphthalein

Normality of the acid used = N/10

S No Volume of the solution Burette reading Volume of the titrant used

taken in the titration Initial Final (Final-initial) (ml)
flask(ml) V1 V2 (V2 - V1)
1.
11
 2.
3.

Volume of the acid used = (V2 - V1) ml

(b) Using methyl orange

Normality of the acid used = N/10

S No Volume of the solution Burette reading Volume of the titrant used

taken in the titration Initial Final (Final-initial) (ml)
flask(ml) V2 V3 (V3 – V1)
1.
2.
3.

CALCULATIONS
1. Phenolphthalein alkalinity interms of CaCO3 equivalents:
N1V1 = N2W2 (W2 = 20 ml)
(Acid) (Water)
1/10 x (V2 - V1) = N2 x 20
N2 = 1/10 x (V2 - V1)/20 = (V2 - V1)/200
Strength in terms of CaCO3 equiv. = N2 x Eq wt of CaCO3
= ((V2 - V1)/200) x 50 g/L = X g/L
Therefore, P= X x 1000 mg/L = X x 1000 ppm

2. Methyl orange alkalinity in terms of CaCO3 equivalents:

N1' V2 = N2'W2'
(Acid) (Water)
1/10 x (V3 – V1) = N2' x 20
N2' = 1/10 x (V3 – V1)'/20 = (V3 – V1)/200
Strength in terms of CaCO3 equiv. = N2' x Eq wt of CaCO3
= ((V3 – V1)/200) x 50 g/L = Y g/L
Therefore, M= Y x 1000 mg/L = Y x 1000 ppm

RESULT

Phenolphthalein alkalinity = …………….. ppm of CaCO3

Methyl orange alkalinity = …………….. ppm of CaCO3
(To find out the alkalinity in terms of individual ions we find out to which case the values
of P and M falls and from the table we calculate the amount of individual ions as below)
Alkalinity due to OH- ions = ………ppm
Alkalinity due to CO32- ions = ………ppm
Alkalinity due to H CO3- ions = ………ppm
Report Alkalinilty of different water samples separately.
12
………………………………………………………
VIVA VOCE
1. What is the source of alkalinity in water?
2. In what forms phenolpthalein exists in acidic and basic medium?
3. What is the structural formula of phenolphthalein?
4. Why HO- and HCO3- do not exist together?
5. What is your observation when P=0, P= ½ M, P< ½ M, P> ½ M, P=M?
………………………………………………………
pH METRIC MEASUREMENTS

The titration of a triprotic acid with a strong base will have three equivalence points one
for each of the three neutralization points.
[H2PO4-] [H3O+]
- +
H3PO4 + H2O H2PO4 + H3O ; Ka1 = = 7.5 x 10-3
[H3PO4]

[HPO42-] [H3O+]
- 2- +
H2PO4 + H2O HPO4 + H3O ; Ka2 = = 6.2 x 10 -8
-
[H2PO4 ]

[PO43-] [H3O+]
2- 3- +
HPO4 + H2O PO4 + H3O ; Ka3 = = 4.4 x 10-13
2-
[HPO4 ]

In practice HPO42- is too weak an acid for feasible titration in aqueous solution because
its dissociation constant is so small and close to ionic product of water, that the pH
change at the equivalence point can scarcely be distinguished from the titration of pure
water. In general, for the titration curve of a polyprotic acid to show separate well defined
equivalence point breaks, the individual Ka values all must be larger than about 10-9 and
differ from one another by at least a factor of 103.

In figure given below, the rate of pH change is smallest where the volume of NaOH
added equals a/2 and a+[(b-a)/2]. These points are halfway to the first and second
equivalence points respectively, where the buffer capacity of the titrant solution is
greatest. The rate of pH change is greatest at the equivalence points a and b, where the
buffer capacity is smallest.

pH

pKa2
Equivalence pt. 1
Equivalence pt. 2
13
 pKa1

a/2a a + (b-a) b
2
Volume of NaOH added →

Thus, the slope of the pH versus added base curve is smallest at the titration points
halfway to equivalence, where the buffer capacity is maximum and largest at the
equivalence points where the buffer capacity is minimum.

The point where [H2PO4-]/ [H3PO4] is equal to 1 occurs halfway to the first equivalence
point , when half of the NaOH moles needed to complete the neutralization of the first
acidic proton having added into the solution.

At this point, we have for Ka1

[H2PO4-] [H3O+]
Ka1 = = [H3O+]1/2 eq.pt. or pKa1 = pH1/2 eq. pt.
[H3PO4]

Thus, a measurement of pH at half equivalence point from graph gives Ka1 directly.
Similarly, a measurement of pH halfway between the first and second equivalence point
gives Ka2 directly.

EXPERIMENT NO. 5

AIM
To prepare and describe a titration curve for phosphoric acid – sodium hydroxide titration
using pH-meter.

APPARATUS
pH meter, reference electrode, beaker, burette, stirrer etc.

CHEMICALS
N/10 NaOH and phosphoric acid.

THEORY
Neutralisation of phosphoric acid takes place in steps.
H3PO4 + NaOH → NaH2PO4 + H2O
NaH2PO4 + NaOH → Na2HPO4 + H2O
14
Na2HPO4 + NaOH → Na3PO4 + H2O

The solution remains acidic after the first neutralization step. After the second
neutralization step, it becomes mildly alkaline and strongly alkaline after the third
neutralization step.

PROCEDURE
1. Calibrate the pH meter with glass electrode in the buffer solution of known pH.
2. Wash the glass electrode and reference electrode with distilled water and then
rinse with the acid solution.
3. Take 5 ml of phosphoric acid solution in a 400 ml beaker. Add sufficient water so
as reference and glass electrodes are completely dipped.
4. Note down the pH of the pure acid solution.
5. Now add 1 ml of N/10 NaOH from the burette in the beaker. Stir the contents and
note the pH of the solution.
6. Continue adding NaOH solution from the burette and note down the pH after each
addition.
7. Near the equivalence point the change in pH is much more rapid than in any other
region. Two end points would be observed.

OBSERVATION

S.No. Vol. of NaOH added (ml.) pH Potential (mV)

1. 0 (only phosphoric acid)

2. 1
3. 2

GRAPH
Draw a graph between pH and volume of NaOH added as shown in theory.

RESULT: The Ka1 and Ka2 of Phosphoric acid were experimentally found to be ………
………………………………………………………
VIVA VOCE
1. What is an electrochemical cell? An electrochemical cell is a device capable
of either generating electrical energy from chemical reactions or facilitating
chemical reactions through the introduction of electrical energy.
2. Why is hydrogen electrode not used in pH measurements? This method is not
appropriate for daily use because of the effort and expense involved, with the
inconvenience of handling hydrogen gas and great influence of highly oxidizing
or reducing substances in the test solution.

15
 3. What is meant by pH of a solution? The pH of a solution is a measure of
the molar concentration of hydrogen ions in the solution and as such is a
measure of the acidity or basicity of the solution.
4. Explain the construction of a pH meter along with the types of electrodes
used. pH meter is nothing else, but precise voltmeter, that measures EMF of the
pH electrode.
5. Why cannot the third equivalence point of phosphoric acid be determined on
titrating pH metrically? The pKa value for the third stage cannot be determined,
as phosphoric acid is never fully dissociated in aqueous solution.
………………………………………………………
EXPERIMENT NO 7

AIM
To determine the ion exchange capacity of a given cation exchanger.

APPARATUS
A cation exchange resin column ( a burette with a glass wool plug at the lower end
having dimensions 20 cm. length and 7-8 mm. diameter), conical flask, burette, pipette,
measuring flask, pH paper.

CHEMICALS REQUIRED
0.1N NaCl, 0.1N NaOH Solution, 0.1N HNO3 solution, Phenolphthalein.

THEORY
The Cation exchange resins consist of cross-linked, long chain organic polymers with
microporous structures having –COOH or –SO3H as functional groups are commercially
available as their sodium salts and can be represented as RSO3¯ Na +. Resins usually
consist of styrene-divinylbenzene copolymer. Other polymers like methacrylic acid-
divinylbenzene or phenol formaldehyde polymers are also used. These are first converted
to their H+ form by passing 0.1 N HCl solution or 0.1 N HNO3 solution
HNO3
RSO3¯Na+ RSO3¯ H+
The H ion of the resin is then exchanged for Na+ ions by passing a solution of NaCl
+

RSO3¯ H+ + NaCl → RSO3¯Na+ + HCl

The hydrogen ions are released in equivalent amounts of sodium ion .
The HCl so released is titrated against standard NaOH solution.
The exchange capacity of a cation exchanger then is measured by determining the
number of milligram equivalence of sodium ion which are absorbed by 1 g of the resin in
the hydrogen form.

16
 --CH------CH2------CH------CH2------CH-

CH2---CH---CH2

--H 2C-- CH CH---CH2--

SO3H- SO3H-

Structure of cation exchanger

PROCEDURE
1] Take a weighed quantity ( eg. 5 gms.) of the given cationic resin sufficient to produce
8-10 cm long column and stir it with 100 – 200 ml of the distilled water to form a slurry.
2] Fill the chromatography column (or a burette having a glass wool plug) with the slurry
and allow it to settle down , as described in column chromatography.
3] Pass about 50ml of 0.1 N HNO3 through the column to convert the resin into H+ from
till the pH paper starts showing acidic reaction .
4] Wash the column with distilled water several times till the pH paper shows no change
of colour , when tested with the washings (the reddish colour of pH paper indicates that
some HNO3 is still present and washing is not complete ).
5] Add 0.1 N solution of NaCl (250 ml) and allow it to pass through column at a rate 2
ml/min. Collect the effluent in a 250 ml conical flask.
6] Check the effluent (solution) frequently with pH paper when it shows no change in
colour, it suggests that replacement is complete. The collection of effluent is stopped at
this stage.
7] The solution (Acid) collected in the conical flask is titrated against 0.1N NaOH using
phenolphthalein as indicator. Record the volume of 0.1 N NaOH used for titration

OBSERVATIONS AND CALCULATIONS

Normality of NaOH = 0.2 N
Volume of NaOH consumed = Vml
Weight of resin packed in the column = W g

Capacity of cation exchanged resin = Volume of NaOH (V) x Normality of NaOH

W
= V x 0.2 m eq/g
W
RESULT The capacity of cation exchanger is ------- m eq/g

17
PRECAUTIONS
1. For preparing all the solutions and rinsing the glass wares only distilled water
should be used.
2. The rate of effluent coming out of the chromatographic column should be
adjusted to 3-4 ml per min.
3. Avoid the drying out of column as air spaces in column obstruct the exchange of
ions.
………………………………………………………
VIVA VOCE
1. What is the principle of ion exchange chromatography.
2. How do you understand that complete exchange of ion take place for HNO3
solution
3. Write down the reaction associated with the whole reaction process.
4. What is the mechanism of ion exchange process.
………………………………………………………
EXPERIMENT NO 8

AIM
Determination of viscosity of given oil by means of Redwood viscometer I.

APPARATUS AND CHEMICALS

Redwood viscometer and stopwatch and oil.

THEORY
Kinematic viscosity is a measure of time for a fixed volume of liquid to flow by gravity
through capillary. The viscosity of the oil is determined by following relation.

η = At – B/t
where A and B are constants and t is time in seconds
A = 0.0026 and B = 1.79 when t<100
A = 0.00247 and B = 0.5 when t>100
PROCEDURE
1] Clean the viscometer cup and properly dry it to remove any trace of the solvent.
2] Level the viscometer with the help of leveling screws.
3] Fill the outer bath with water for determining the viscosity at the test temperatures
(40oC, 50 oC and 60 oC).
4] Place the ball valve on the jet to close it and pour the test oil into the cup up to the tip
of the indicator.

18
5] Place a clean dry Kohlrausch flask immediately below and directly in line with
discharging jet.
6] Insert a thermometer and a stirrer in the cup and cover it with a lid.
7] Heat the water filled in the bath slowly with constant stirring. When the oil in the cup
attains a desired temperature stop the heating.
8] Lift the ball valve and start the stop watch. Oil flows from the jet into the flask.
9] Stop the stopwatch when the lower meniscus of the oil reaches the 50 ml. mark on the
neck of the receiving flask. (Replace the ball valve in position immediately so as to
prevent overflow.
10] Record the time taken for 50 ml of the oil to collect in the flask.
11] Similarly repeat the procedures (step 4-10) for the test temperatures 50 oC and 60 oC.

OBSERVATIONS

S.No. Temperature oC t ime Viscosity, (Stokes )

(seconds)
1. 40 oC
2 50 oC
3 60 oC

Calculate the viscosity by using equation:

η = At – B/t Values of A and B is given in the as

A = 0.0026 and B = 1.79 when t<100
A = 0.00247 and B = 0.5 when t>100

Also plot a graph between viscosity and temperatures

RESULT Viscosity of the oil sample with the help of Redwood viscometer at …..0 C is
…..Stokes

PRECAUTIONS
1] The oil should be filtered through a muslin cloth to remove solid particles that may
clog the jet.
2] The receiving flask should be placed in such a way that the oil stream from the jet
strikes the neck of the receiving flask and does not cause foaming.
3] After each reading the oil should be completely drained out of the receiving flask.
………………………………………………………
VIVA VOCE
1. What is the effect of temperature on viscosity? The higher the temperature is,
the lower a substance's viscosity is.
2. Name few oils with high viscosity.

19
 3. Define viscosity and its various units. The property of a fluid that resists the
force tending to cause the fluid to flow.
Unit - Dynamic viscosity - Poiseuille = 10 poise
Kinematic viscosity - stokes
4. Why viscosity index is more important than the viscosity for a lubricant?
Viscosity index (VI) is an arbitrary measure for the change of viscosity with
variations in temperature. The lower the VI, the greater the change of viscosity of
the oil with temperature and vice versa. It is used to characterize viscosity
changes with relation to temperature in lubricating oil.
………………………………………………………
EXPERIMENT NO.9

AIM
To determine flash point and fire point of an oil by Pensky Martin’s Apparatus

APPARATUS AND CHEMICALS REQUIRED

Pensky Martin’s flash and fire point apparatus, oil.

THEORY
Flash point is the lowest temperature at which the lubricating oil gives off enough vapors
that ignite for a moment when a tiny flame is brought near it. Fire point is the longest
temperature at which the vapors of the oil burn continuously for at least five seconds
when a tiny flame is brought near it.

PROCEDURE
1] Clean and dry all parts of the apparatus
2] Fill the oil cup with the test oil up to the mark.
3] Fix the lid on the top through which are inserted a thermometer and a stirrer. Ensure
that the flame exposure device is fixed on the top.
4] Start the heating so that the temperature of the test oil increases by about five to six
degrees per minute while the stirrer is rotated at approximately sixty revolutions per
minute.
5] At every one degree rise of temperature introduce the flame for a moment to the oil
vapor. This is done by operating the shutter. On moving the knob of the shutter, the test
flame is lowered in the oil vapors through the opening. The moment knob is released the
test flame springs back to it’s original position and the opening is closed.
6] When the test flame causes a distinct flash when it comes in contact with the vapors of
the oil, the temperature is noted. This temperature is the flash pont of oil.
7] Further heat the test oil at the rate of 10C /min and continue applying the test flame as
described above.
8] The temperature at which the vapors of the oil give a clear and distinct blue flash for 5
sec is recorded as the fire point of the oil.

20
RESULT The flash point of the given oil is = …..0C
The fire point of the given oil is = …..0C

PRECAUTIONS
1] The apparatus should be thoroughly dried because the moisture affects the flash point
as steam prevents vapours from igniting.
2] The thermometer bulb should dip into the oil.
3] For introducing the flame, the shutter should be drawn open slowly and closed quickly.
4] While applying the test flame, stirring should be discontinued.
5] Samples of very viscous materials may be warmed until they are reasonably fluid
before they are tested.
………………………………………………………
VIVA VOCE
1. What is the significance of flash and fire point? The fire point of a fuel is the
temperature at which the vapour produced by that given fuel will continue to burn
for at least 5 seconds after ignition by an open flame. At the flash point, a lower
temperature, a substance will ignite briefly, but vapor might not be produced at a
rate to sustain the fire.
2. What should be the flash point of good lubricant? above its working
temperature
3. What are the factors that affects flash and fire point?
Pressure – The flash point temperature increases with increasing pressure and
decreases with decreasing pressure.
Oxidant – The flash point temperature of a pure liquid or mixture is greatly
influenced by the type of oxidant atmosphere (i.e. flash point of a chemical in air will be
different than the flash point of the same chemical in another oxidant like chlorine).
Others - Tester configuration, sample size, ignition source, temperature control,
sample homogeneity, drafts, and operator bias.
………………………………………………………
EXPERIMENT NO. 11
AIM
To determine the amount of oxalic acid and sulphuric acid in 1 litre of solution. Given
0.1 N NaOH solution and 0.1 N KMnO4 solution.

APPARATUS
Burette, pipette, titration flask, beakers, stand

CHEMICALS REQUIRED
NaOH (N/10), N/10 KMnO4 solution, oxalic acid, phenolphthalein, conc. H2SO4

THEORY
This Involves double titration.
21
Ist Titration: NaOH reacts with oxalic acid as well as H2SO4 according to the following
equations:
COOH COONa
l .2H2O + 2NaOH → l + 4H2O
COOH COONa

H2SO4 + 2NaOH → Na2SO4 + 2H2O

By titrating NaOH against the given mixture of oxalic acid and sulphuric acid, the total
normality of oxalic acid and H2SO4 can be found out.
2nd Titration: The mixture solution is titrated with 0.1 N KMnO4 solution which will
react with oxalic acid (redox titration) in the presence of H2SO4.

2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]

COOH 60-70°C
l + [O] → 2CO2 + H2O] X 5
COOH ∆
_____________________________________________________________________
2KMnO4 + 3H2SO4 + 5H2C2O4 → K2SO4 + 2MnSO4 + 8H2O + 10CO2

Thus from second titration, normality of oxalic acid alone can be found out and hence its
strength is determined.
From the normality of the solution obtained in the first titration, the normality of
oxalic acid is subtracted and hence the normality of H2SO4 and its strength can be found
out.
The reaction of oxalic acid with KMnO4 is very slow therefore the oxalic acid
solution is heated to 60-70°C initially. Once the reaction has started, the rate
automatically increases due to the formation of Mn2+ ions which catalyze the reaction
(auto catalysis).

INDICATOR Phenolphthalein (Ist Titration)

KMnO4 is self-indicator (2nd Titration)

END POINT Colourless to Pink (Ist Titration)

Colourless to Pink (2nd Titration)

PROCEDURE
Ist Titration
1] Rinse the apparatus thoroughly. Take NaOH in the burette and pipette out 10 ml of
mixture in the titration flask.
2] Add a drop of phenolphthalein and run NaOH from the burette.

22
3] Titrate till end point is achieved and note down the volume of NaOH used.
4] Repeat to get concordant reading.
2nd Titration
1] Rinse the apparatus thoroughly. Take KMnO4 in the burette. Since it is a colored
solution we note the upper meniscus for taking the initial reading.
2] Pipette out 10 ml of the mixture in the titration flask. Add half a test tube (almost 10
ml) of H2SO4 and then heat the conical flask slowly until the moisture appears on the
neck of the flask or it is unbearable to touch (60-70°C)
3] Titrate to achieve the end point and note volume of KMnO4 used.
4] Repeat to get concordant reading

OBSERVATIONS
Observation Table I
NaOH versus mixture

S No Volume of the solution Burette readings Volume of the titrant used

taken in the titration Initial Final (Final-initial reading) (ml)
flask(ml)
1.
2.
3.
Observation Table II
KMnO4 versus mixture (only oxalic acid reacts)

S No Volume of the solution Burette readings Volume of the titrant used

taken in the titration Initial Final (Final-initial reading) (ml)
flask(ml)
1.
2.
3.

CALCULATIONS
23
Ist Titration

N1V1 = N2V2
(H2SO4 + oxalic acid) (NaOH)
N1 = 0.1 x V2 / 10
IInd Titration
N'1V'1 = N'2V'2
(Oxalic acid) (KMnO4)
N'1 = 0.1 x V'2 / 10
Normality of oxalic acid + H2SO4 = N1
Normality of oxalic acid = N'1

Strength of oxalic acid = N'1 x Eq. wt.

= N'1 x 63 g/l
Normality of H2SO4 = (N1 - N'1)

Strength of H2SO4 = (N1 - N'1) x Eq. wt.

= (N1 - N'1) x 49

RESULT = Amount of oxalic acid present in the given mixture = ……….g/l

Amount of H2SO4 present in the given mixture = ……….g/l
PRECAUTIONS
1] All the apparatus should be washed before use.
2] Rinse the burette with KMnO4 and pipette with the given solution.
3] Titration flask should not be rinsed with the given solution and only with distilled
water.
4] Never use a pinch cock burette as KMnO4 attacks rubber.
5] Read upper meniscus because KMnO4 is a coloured solution.
6] Sulphuric acid should be added in excess, otherwise a brown precipitate of MnO2 may
appear.
7] Always use freshly prepared KMnO4 solution.
………………………………………………………
VIVA VOCE
1. What is meant by redox reaction?
2. Which mineral acid is most suitable for carrying out KMnO4 titration?
3. Why the titration involving KMnO4 are carried out in acidic medium?
4. Why the oxalic acid solution is heated before titration with KMnO4 solution.
5. Why is brown turbidity sometimes seen while titrating KMnO4 solution with
oxalic acid.
6. Why does color of KMnO4 disappears slowly in the beginning and quite fast
afterwards when titrated against a hot solution of oxalic acid containing dil.
H2SO4.
24
………………………………………………………
EXPERIMENT NO.12
AIM
To determine the number of water molecules of crystallization in Mohr’s salt (ferrous
ammonium sulphate) provided standard potassium dichromate solution (0.1N) using
diphenylamine as internal indicator.

THEORY
Mohr’s salt is [FeSO4 (NH4)2SO4. 6H2O]. Potassium dichromate oxidizes FeSO4 present
in Mohr’s salt to Fe2(SO4)3 in the presence of dil.HCl.
Cr2O7 2- + 14H+ + 6e- 2Cr3+ + 7H2O
[Fe2+ Fe3++e-] x 6

Cr2O72- + 14H+ + 6Fe2+ 2Cr3+ + 6Fe 3+ + 7H2O

In this titration diphenylamine is used as an internal indicator. At the end point all the
ferrous ions present in the solution get completely oxidized to ferric ions by chromate
ions and as soon as a slight excess of dichromate is added, it will bring about the
oxidation of diphenylamine and results in the formation of a blue coloured complex.
This indicates the end point of the titration.

2 NH oxidation N N N
with Cr2O7 2-
diphenylamine (colourless) Diphenyl benzidine (Blue complex)
+ 2H+ + 2e-
From this titration, strength of anhydrous Mohr’s salt can be calculated. Then applying
the following relation, the number of water molecules of crystallization may be found.

Strength of hydrated salt / Strength of anhydrated salt=284+18x / 284

Given strength of hydrated salt = 20 g/litre.

APPARATUS
Burette, pipette, 2 beakers, titration flask, stand.

INDICATOR USED
Diphenylamine.

END POINT
Colourless to deep blue.

PROCEDURE
1. Rinse the burette with K2Cr2O7. Take K2Cr2O7 in the burette and note down initial
reading.

25
2. Pipette out 10 ml. of Mohr’s salt solution in the titration flask. Add 5 ml of dil.
H2SO4 and 2-3 ml of 1:1 H3PO4 –H2O to the flask. Also add a drop of indicator.
3. Start titrating at regular intervals.
4. When end point is reached, note down the final reading of the burette.
5. Repeat to get 3 concordant readings.

OBSERVATIONS
Normality of K2Cr2O7 solution = 0.1 N

Observation table
S.No Volume of the solution taken Burette Readings Volume of titrant used
in the titration flask (ml) (ml)=(Final–Initial readings)
Initial Final
1.
2.
3.

CALCULATIONS
(Mohr’s solution) (K2Cr2O7)
N1 V1 = N2 V2
N1 10 = 1/10 V2
N1 (Mohr’s solution) = V2/100

Strength of anhydrated Morh’s salt = Normality Eq. Wt

= N1 284
= y g / litre
Strength of hydrated salt = 20 g / litre

Strength of hydrated salt / Strength of anhydrated salt = 284+18x / 284

Calculate the value of x.
X is the number of water molecules of crystallization.

RESULT
The number of water molecules of crystallization is ……
………………………………………………………
26
VIVA-VOCE
1. Define redox titrations.
2. Why K2Cr2O7 does not act as self indicator?
3. Why H3PO4 is added when diphenylamine is used as an indicator?
4. How does diphenylamine act as an internal indicator?
5. K2Cr2O7 is used as an oxidizing agent only in presence of acid. Explain.
………………………………………………………

27