CHEMISTRY LABORATORY MANUAL

B.Tech.
(All branches)

1
 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.

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 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 Na 2S2O3 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.

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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

AIM
Determination of Dissolved oxygen in the given water sample.

APPARATUS
Burette, pipette, conical flask, beakers

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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 I 2 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

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.

5
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

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.

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………………………………………………………
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

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)

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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.
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.

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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
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

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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:

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 oft eh 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

10
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)

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 HCO 3¯
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)

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 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.
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

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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.
………………………………………………………
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 H2PO + H3O ;
4 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 ]

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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
pKa1

a/2 a 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.

14
 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
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)

15
 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?
2. Why is hydrogen electrode not used in pH measurements?
3. What is meant by pH of a solution?
4. Explain the construction of a pH meter along with the types of electrodes used.
5. Why cannot the third equivalence point of phosphoric acid be determined on
titrating pH metrically?
………………………………………………………
CONDUCTOMETRIC MEASUREMENTS

Conductometry deals with the measurement of electrical conductance of solutions

containing electrolytes (acids, bases and salts in water). These solutions conduct current
due to the movement of ions (cations and anions) towards oppositely charged electrodes.

The ratio of E/I (Potential/Current) is called as the resistance of the conductor to the
passage of electric current. The reciprocal of resistance is called as conductance. Its units
are ohm-1 or mho or Seimen (S)

The specific conductance of a conductor is defined as the conductance of a cube of unit

length. Its can also be defined as the conductance of a solution contained between two
parallel electrodes which have cross sectional area 1 cm2 and which are kept 1 cm apart.

The cell constant i.e. the ratio l/a cannot be determined from the geometrical dimensions
of the cell because the exact area of cross section of electrode or distance between them
cannot be measured accurately. Thus cell constant is determined by an indirect method.

Equivalent conductance is defined as the conductance of a solution containing one gram

equivalent of an electrolyte at any particular concentration, when placed between two
large electrodes 1 cm apart.
v = K x 1000/C
Molar conductance of an electrolyte at a particular dilution is the conductivity of the
solution containing 1 mole of the electrolyte when placed between two large electrodes 1
cm apart.

Effect of dilution on conductivity: The specific conductance decreases on diluting the

solutions. This is mainly due to the decrease in the concentration of ions per unit volume.

16
The molar conductance increases with dilution and attains a limiting value at infinite
dilution. This increase in case of weak electrolytes is attributed to increased dissociation
of electrolyte on dilution. In case of strong electrolyte, the increase is due to the increased
mobility of ions.

Effect of temperature on conductivity: Conductance increases with increase in

temperature. This is due to the increase in velocity of ions, decrease in viscosity of the
medium or decrease in the interaction between the ions. In case of weak electrolytes,
increase in the degree of ionization with increase in temperature also results in increased
conductance.

Other factors influencing conductance:

-Number of free ions in the solution: More the number of free ions greater the
conductance.
- Charge on the free ions: Greater the charge greater is the conductance.
- Mobility of the ions: Greater the mobility greater is the conductance.

EXPERIMENT NO: 6(A)

AIM
To find the cell constant of conductivity cell

THEORY
The cell constant i.e. the ratio l/a cannot be determined from the geometrical dimensions
of the cell because the exact area of cross section of electrode or distance between them
cannot be measured accurately. Thus cell constant is determined by an indirect method.
As
l/a = K/C
where,
C = Observed Conductance
l/a= cell constant
K = Specific Conductance

Or Cell constant = Specific Conductance / Observed Conductance

For determination of cell constant, a solution of known specific conductance is taken

whose conductance is determined using the given cell. Solution of KCl of known
concentration and known specific conductance are used for this purpose.

APPARATUS
Conductivity Bridge, conductivity cell, thermometer, beaker, burette, pipette, funnel.

CHEMICALS
0.01 N KCl solution, distilled water.

PROCEDURE

17
1. Wash the conductivity cell thoroughly with distilled water.
2. Rinse the conductivity cell repeatedly with KCl solution.
3. Take sufficient volume of KCl solution in a beaker and note down its temperature.
4. Connect the instruments to the mains and switch on the instrument using power
switch. Connect the electrode leads in the input sockets at the rear of the
instruments.
5. Set the Function switch to check position and adjust the display to 1.000 with the
CAL control at the back panel.
6. Dip the conductivity cell in KCl solution and adjust the temperature knob of the
conductivity Bridge at the temperature of the KCl solution.
7. Move the Function switch to conductance position and range position to
appropriate range.
8. Adjust the cell constant knob so that display reads the known value of the KCl
solution at that temperature.
9. Bring the Function switch to cell constant position and read the value of the cell
constant from the display window.

RESULT: The cell constant of the given cell is. ………cm-1

EXPERIMENT NO. 6(B)

AIM
Determine the strength of hydrochloric acid solution by titrating it against standard
sodium hydroxide solution conductometrically.

THEORY
Conductometric titration is the volumetric analysis based upon the measurement of the
conductance during the course of titration. Conductance of an aqeous solution containing
an electrolyte depends upon the-
-Number of free ions
-Charge on the free ions
-Mobility of the ions

When the solution of one electrolyte is added to another, a change in the conductance will
result due to the change in number of free ions or substitution of ions of one mobility by
the ions of another mobility.

Titration of a strong acid with a strong base

Before NaOH solution is added from the burette, the acid solution has high conductivity
due to the highly mobile H+ ions. When NaOH is added to the acid the highly mobile H+
ions are removed by combination with OH- ions to form feebly ionized water and hence
are replaced by less mobile sodium ions.

H+ Cl- + Na+ OH- Na+ Cl- + H2O

18
 (feebly ionized)
Thus, the conductance of the solution will decrease and continues decreasing with the
addition of NaOH until the equivalence point is reached. On further addition of NaOH,
the conductivity of the solution will increase due to addition of Na+ ions and highly
mobile hydroxyl (OH-) ions. If, we plot the conductance of the solution against the
volume of alkali added, two straight lines intersecting at a point will be obtained. This
point of intersection corresponds to the equivalence point since at this point there is no
excess of either acid or base.

APPARATUS
Conductometer, conductivity cell, beaker, burette, pipette, funnel etc.

CHEMICALS
0.1N NaOH , standard conductivity reagent (KCl solution ) and unknown HCl solution.

PROCEDURE
1. Determine the cell constant of the given conductivity cell as is done in the
previous experiments no. 6(A).
2. Rinse the conductivity cell with the solution whose conductivity is to be
measured.
3. Take 20 ml of the given HCl solution in a 100 ml beaker.
4. Wash the conductivity cell with distilled water and then rinse it with the given
HCl solution. Dip the cell in the solution taken in the beaker.
5. Connect the conductivity cell to the conductometer.
6. Set the function switch to check position. Display must read 1.000. If it does not,
set it with CAL control at the back panel.
7. Put the function switch to cell constant and set the value of cell constant
determined in step 1 with the help of cell constant knob.
8. Set the temperature control to the actual temperature of the solution under test.
9. Set the Function switch to conductivity and read the display. This will be exact
conductivity. Note it down.
10. Take alkali (NaOH) in the burette and add 0.5 ml of it in to the beaker containing
HCl. Stir and determine the conductivity.
11. Repeat the procedure of addition of 0.5 ml of NaOH and noting down the
conductivity in the observation table. Take 12 to 15 readings in this way. After
each addition, stir the solution gently.

OBSERVATIONS
Volume of unknown acid solution taken (V1)=50 ml
S.NO. Volume of NaOH added (ml) Specific conductance
(mho/cm)
1. 0.0
2. 0.5
3. 1.0
4. 1.5
5. 2.0
6. …… … and so on

19
CALCULATIONS

Plot a graph between specific conductance (along y- axis) and volume of NaOH added
(along x –axis). The point of intersection will give the amount of alkali required for
neutralization of the acid.

conductivity

Volume of NaOH

Suppose the volume of the alkali used = V2 ml

Applying normality equation.
N1V1 = N2V2
(HCl) (NaOH)
N1 = (0.1  V2 / 50)
Strength of HCl solution = Eq. wt  Normality
= 36.5  N1 g/ litre

RESULT: Strength of given HCl solution is……………g/litre.

………………………………………………………
VIVA VOCE
1. Define conductance, specific conductivity and equivalent conductivity. What are
their units?
2. How does specific conductance and equivalent conductance vary with dilution?
3. What is the effect of temperature on conductance?
4. Define cell constant.
5. What are the advantages of conductometric titrations
6. Why is KCl used as a standard for verification of cell constant?
7. Define ionic mobility.
………………………………………………………

20
 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.

--CH------CH2------CH------CH2------CH-

CH2---CH---CH2

--H2C-- CH CH---CH2--

SO3H- SO3H-

21
 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

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.

22
………………………………………………………
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.
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

23
 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?
2. Name few oils with high viscosity.
3. Define viscosity and its various units.
4. Why viscosity index is more important than the viscosity for a lubricant?
………………………………………………………

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.

24
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.

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?
2. What should be the flash point of good lubricant?
3. What are the factors that affects flash and fire point?
………………………………………………………
EXPERIMENT NO. 10

AIM
To determine the Iodine value of the oil.

APPARATUS
Burette, pipette, conical flask, beakers etc.

CHEMICALS REQUIRED
N/10 Na2S2O3 solution, Wij’s solution (Solution of ICl Glacial Acetic Acid), Potassium
Iodide Solution(10%), Chloroform or carbon tetrachloride, Starch Solution (Freshly
prepared).

25
THEORY:
Iodine value is the measure of unsaturation of fats and oils and is expressed in terms of
number of centigrams of Iodine absorbed per gram of sample (percentage Iodine
absorbed). Determination of Iodine value is done through Iodometric titration . A known
weight of the oil is dissolved in CHCl3 or CCl4 and treated with a known excess of Wij’s
solution. One molecule of ICl adds to the double bond.
After the completion of the reaction, KI is added and unreacted ICl liberates Iodine from
it
ICl + KI  I2 + KCl
The liberated I2 is titrated against Na2S2O3 using starch as indicator

PROCEDURE

Preparation of Wij’s Solution: It can be prepared by dissolving 1.6 g of Iodine

monochloride in 100 ml of analytical grade glacial acetic acid.

Determination of Iodine Value:

1] Remove the moisture present in the oil sample by straining it through a filter paper
2] Weigh about 5g of the sample oil and transfer it to a conical flask. Add 25ml of CCl4
and 25ml of Wij’s solution to it. In another flask take the same volumes of CCl4 and
Wij’s solution for blank determination.
3] Close the flask and mix the contents by swirling. Keep in dark for about 1hr at a
temperature below 300 C . The glass stopper may be moistened with KI solution.
4] Now add 20ml of KI Solution to both the flask and 100ml of distilled water.
5] Titrate the liberated Iodine with N/10 Na2S2O3 solution till the colour of the solution
becomes pale yellow.
6] Now add the indicator i.e. starch solution, the solution will turn blue.
7] Continue the Titration till the blue colour disappears.
8] Note down the volume of Na2S2O3 used, in both the cases, i.e. test solution and blank.

OBSERVATION AND CALCULATIONS

Weight of the weighing tube = w1g

Weight of the weighing tube + oil = w2g
Weight of the sample = (w2-w1)g
Volume of Na2S2O3 used to titrate excess Iodine in sample determination = X ml
Volume of Na2S2O3 used to titrate total Iodine in blank titration = Y ml
Volume of N/10 Na2S2O3 equivalent to Iodine (or ICl) consumed by (w2-w1)g of oil = (Y-
X)ml.
Iodine present in (Y-X) ml of N/10 solution = (Y-X) x 127 x Nx 1/103 g

(Equivalent weight of Iodine = 127 )

Therefore, Iodine value = (Y-X) x 127 x N x 1/103 x 100 cg/g = (Y-X) x 12.7 x N cg/g
(w2-w1) (w2-w1)

26
RESULT The Iodine value of the oil is ………cg/g

PRECAUTIONS
1]Wij’s solution should never be sucked through mouth. It should be added with the help
of burette.
2] Wij’s solution should be added in about 100% excess than the expected requirement.
3] Wij’s solution should be added in the two flasks simultaneously.
……………………………………………………......
VIVA VOCE
1. What do you mean by Iodine Value?
2. What is Wij’s Solution?
3. What is the significance of Iodine value?
4. What does high Iodine Value of oils indicates?
………………………………………………………

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.
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.

27
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.
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

28
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

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.

29
= (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.
………………………………………………………
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
2+
[Fe 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.

30
 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.
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.

31
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 ……
………………………………………………………
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.
………………………………………………………
ORE ANALYSIS

Volumetric analysis is widely employed for ores and alloy analysis. The solution of the
ore is prepared in the appropriate solvent and the ore is estimated by employing a suitable
titration.

EXPERIMENT NO.13

AIM
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.

THEORY

32
 The estimation of iron in an iron ore or alloy can be done by potassium dichromate
titration. The common iron ores are: Haematite (Fe2O3), Magnetite (Fe3O4), Siderite
(FeCO3). When the iron ore is dissolved in a suitable acid, the iron obtained is generally
in the form of Fe3+ ions. These Fe 3+ ions are reduced to Fe 2+ ions adding SnCl2 and
the resulting solution is titrated against K2Cr2O7 solution in the presence of acid.

REACTIONS

(i) Reduction of Fe3+ to Fe2+

2 FeCl3 + SnCl2 2FeCl2 + SnCl4

2 HgCl2 + SnCl2 Hg2Cl2 + SnCl4

(ii)Titration
Cr2O72- +6 Fe2++ 14H+ 2Cr3+ + 6 Fe3+ +7 H2O

Potassium ferricyanide is used as external indicator which gives a greenish blue colour
with Fe2+ ions due to formation of ferrous –ferricyanide.

3 Fe2++ 2 [Fe(CN)6]3- Fe3 [Fe(CN)6]2

Ferro-ferricyanide
(Blue-black coloured complex)
When all the Fe2+ are converted to Fe3+ ions at the end point, the indicator do not give
blue colour when treated with a drop of titration mixture.

INDICATOR
Potassium ferricyanide K3[Fe (CN)6]

END POINT
Blue to colourless

PROCEDURE
Preparation of the ore solution
1. Weigh out accurately 2g of ground dried ore on a watch Glass.
2. Transfer it carefully in to a 100 ml conical flask and add about 10 to 15 ml of
conc.HCl.
3. Warm the contents gently until the residue is not having any coloured material or
only a whitish silica precipitate remains.(Boiling should be avoided)
4. Transfer the residue and the washings in 250 ml measuring flask and make up the
solution to 250 ml.
Reduction of Fe 3+ to Fe 2+ in the ore solution
1. Pipette out 20 ml of the above solution in the conical flask.
2. Add 2-3 ml of con.HCl and heat the solution to boiling for 1-2 minutes.
3. Add SnCl2 solution to the hot solution dropwise, till the yellow colour of the
solution (due to FeCl3) gets discharged. Cool the solution under tap water and
dilute to 100 ml with distilled water.

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4. Add 1-2 ml of saturated HgCl2 solution in one lot to oxidize excess of SnCl2
solution. A white turbidity is obtained.
Titration with K2Cr2O7
1. Rinse and fill the burette with 0.1 N K2Cr2O7
2. Place small drops of potassium ferricyanide solution (1%) on a dry white tile by
means of a thin glass rod.
3. Titrate the solution in the conical flask (obtained in step II) with K2Cr2O7 solution.
4. After adding 1 ml K2Cr2O7 of solution in the conical flask, withdraw a drop of the
solution from the flask with a thin glass rod and mix it with one of the drop of
potassium ferricyanide on the tile. Appearance of blue colour indicates that end
point has not yet reached.
5. Continue the titration with K2Cr2O7 and repeat the process of withdrawing a drop
of solution and mixing it with K3[Fe (CN)6] on the tile. When the indicator drop
does not give blue colour, the end point is reached. Note the readings.
6. Repeat the titration to get the exact end point.
7. Take three concordant readings.

OBSERVATIONS
Weight of iron ore taken = w gm
Volume of the solution prepared = 250 ml
Weight of ore present in 1000 ml (x) = 1000/250 ×w = 4xw g

Observation table

S.No Volume of the Burette Readings Volume of

solution taken in the the titrant
titration flask (ml) Initial (ml) Final (ml) used (ml)
1.
2.
3.
CALCULATIONS:
(Fe2+) (K2Cr2O7)
N1V1 = N2V2
N1× 20 = 1/10× V2,
N1= V2/10×20 =V2/200

Strength of Fe2+ in the solution = N1 × eq. wt = V2/200 × 56 g/lit.

Hence, % of iron in iron ore = 56 V2/200×100/x

RESULT: The percentage of iron in iron ore =……………..

………………………………………………………
VIVA-VOCE
1. What is the purpose of adding HgCl2?
2. Why only a very small amount of SnCl2 is added during the reduction of Fe3+?
3. Why the solution is cooled when the reduction is complete?

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 4. Why K3[Fe(CN)6] cannot be used as internal indicator?
………………………………………………………
EXPERIMENT NO. 14(A)

AIM
To determine the surface tension of a given liquid by drop number method.

THEORY
When a liquid is allowed to flow through a capillary tube, a drop is formed at its lower
end. It increases to a certain size and falls off. The size of the drop depends on the radius
of the capillary and the surface tension of the liquid. The surface tension acting along the
circumference of the capillary tube supports the drop in the upward direction.

The measurement of surface tension of liquid is based on the fact that the drop of the
liquid at the lower end of capillary falls down when weight of drops becomes just equal
to the surface tension.

Now the force of gravity exerted on the drop is given by v.d.g.

Where v is the volume of the drop, d is the density and g is gravity, The
force of
gravity will pull down the drop.
The force tending to uphold the drop is given by 2r.
Where 2r is circumference of the capillary of radius r
When the two forces are balanced
2r = v.d.g. ……..eq.1

If n is the number of drops in volume V of the liquid then volume of each drop will be
v=V
n
From eq. 1 we have
2r = V.d.g. ………eq. 2
n
Consider two liquids of densities d1 and d2 having the surface tensions 1 and 2.
Let the no. of drops counted for the same volume V of the two liquids be n1 and n2
respectively. Then,
2r1 = V.d1.g. for 1st liquid ……eq.3
n1

2r2 = V.d2.g. for 2nd liquid ……eq.4

n2
Dividing eq.3 by 4, we have
1 = n2 x d1
2 n1 d2

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 Knowing surface tension of one liquid (reference liquid), the surface tension of
other can be calculated.

APPARATUS
Stalagmometer, beaker, rubber tubing, pinchcock, relative density bottle, thermometer.
PROCEDURE:
1. Clean the stalagmometer first with NaOH, then with chromic acid solution to
remove oil, grease etc. sticking on the inner capillary surface. Wash it with
distilled water which is used as reference liquid.
2. Immerse the lower end of the stalagmometer in a beaker containing distilled
water. Suck the water until it rises above the upper mark near the upper end of
bulb on stalagmometer.
3. Now Clamp the stalagmometer vertically on a stand and let the water flow down
& start counting the number of drops when the water meniscus just reaches the
mark A, and counting is stopped when the water meniscus passes the lower mark
B. (Control the rate of flow of water with the help of screw pinch cock so that the
number of drops per minute is about 15-20). The number of drops be nw
4. Repeat to get three readings.
5. Clean the stalagmometer and dry it. Fill it with the given liquid until it rises above
the mark A and count the number of drops when a fixed volume of liquid flows
between the mark A and B, as before. Let the number of drops be nl.
6. Weigh the relative density bottle and note down its weight. Let the weight be w1
7. Fill it with water and weigh it again. The weight of it is w2
8. Remove water and dry the relative density bottle. Now fill it with the given liquid
and weigh. The weight of it is w3

OBSERVATIONS

S.No. Water Acetic acid

No. of drops Mean No. of drops Mean
(nw) (nl)

CALCULATIONS
Weight of empty specific gravity bottle = w1 gm
Weight of empty specific gravity bottle with water =w2 gm
Weight of empty specific gravity bottle with liquid = w3 gm
Weight of water = (w2-w1) gm
Weight of Liquid = (w3-w1) gm

Relative density of the liquid = dl/dw =w3-w1 /w2-w1

Absolute surface tension of the liquid (l) is given by

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 l =nw/nl  dl/dw  w
where l, dl and n1 are surface tension, density and number of drops for liquid and w, dw
and nw are surface tension, density and number of drops for water.

SURFACE TENSION OF WATER AT DIFFERENT TEMPERATURES

Temp (C) 5 10 15 20 25 30 35 40
Surface tension 75.09 74.36 73.62 72.88 72.14 71.10 70.66 69.92
(dynes/cm)

RESULT: The surface tension of the given liquid is .............dynes cm-1

………………………………………………………
VIVA-VOCE
1. Why is the lower end or tip of the stalagmometer flattened?
2. What is the use of narrow capillary in the stalagmometer?
3. What is the effect of temperature on surface tension of the liquid?
4. Why the drops of liquid or bubbles of a gas are spherical in shape?
………………………………………………………
EXPERIMENT NO. 14 (B)

AIM
To determine the composition of a liquid mixture A and B (acetic acid and water) by
surface tension method.

THEORY
When the surface tensions of two liquids constituting the mixture do not differ greatly,
the surface tension of the mixture varies with composition. A number of known
concentration solutions of A (acetic acid) and B (water) are prepared and the number of
drops for each one of these is determined. The number of drops of unknown solution is
also determined. Let it be x. A graph is plotted between the numbers of drops against the
percent composition. From the graph the concentration of the unknown solution can be
determined.

APPARATUS
Stalagmometer, thermometer, beaker etc.

CHEMICALS REQUIRED
Pure A (acetic acid) pure B (water) and the given solution.

PROCEDURE
1. Prepare a number of solution of A and B containing 10%, 20%, 30%, 40% of the
component A.
2. Determine the number of drops for each of the solution by stalagmometer as
described in the previous experiment no.8. Also, determine the number of drops
of unknown mixture.

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OBSERVATIONS

Composition of the mixture

Number of drops
A B
10% 90%
20% 80%
30% 70%
40% 60%
Unknown ----

CALUCATIONS

Plot a graph between the numbers of drops against the percentage composition. The point
corresponding to the number of drops of the unknown mixture is found. A perpendicular
is drawn on the composition axis from that point and the values give the composition of
the unknown mixture.

RESULT: The composition of the given mixture is....................

………………………………………………………
VIVA VOCE
1. State the principle of this experiment.
2. Will there be change in surface tension if alcohol is mixed with water?
3. Why does surface tension change with composition?
4. Will the graph between % composition and number of drops pass through the
origin?
………………………………………………………

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