Dept.

of Chemistry, MIT, Mysore 1

MAHARAJA INSTITUTE OF TECHNOLOGY MYSORE

ENGINEERING CHEMISTRY
LABORATORY MANUAL
{As per Choice Based Credit System (CBCS) Scheme VTU, Belagavi}
Visvesvaraya Technological University
(I/II SEM, B.E.: Sub. Code: 18 CHEL 16/ 26)

Name:

Section:

Batch:

USN:

Department of Chemistry, MIT, Mysore

Belawadi, S. R. Patna Tq, Mandya – 571477
Dept. of Chemistry, MIT, Mysore 2

MAHARAJA INSTITUTE OF TECHNOLOGY MYSORE

Vision: “To be recognized as a premier technical and management institution

promoting extensive education fostering research, innovation and

entrepreneurial attitude"

Mission:

 To empower students with indispensable knowledge through dedicated

teaching and collaborative learning.

 To advance extensive research in science, engineering and

management disciplines.

 To facilitate entrepreneurial skills through effective institute-industry

collaboration and interaction with alumni.

 To instill the need to uphold ethics in every aspect.

 To mould holistic individuals capable of contributing to the

advancement of the society.

-sd-
Principal
Dept. of Chemistry, MIT, Mysore 3

DEPARTMENT OF CHEMISTRY
MAHARAJA INSTITUTE OF TECHNOLOGY MYSORE

VISION:
Foster technologically relevant chemical education in engineering
applications to bring about excellence in research and innovation.

MISSION:
 To endow relevant knowledge in chemical science with eminent teaching
and demonstration.

 To disseminate greater understanding through research in chemical and

related disciplines.

 To facilitate awareness of the impact of chemical attributes on our

environment.

-sd-
HOD
Dept. of Chemistry, MIT, Mysore 4

ENGINEERING CHEMISTRY LABORATORY

Semester I/II CIE MARKS 40

Course Code 18CHEL16/26 SEE Marks 60

Teaching Hours/
0:0:2 Exam Hours 03
week ( L: T:P)
CREDITS -01
Course Objectives:
To provide students with practical knowledge of quantitative analysis of materials by
classical and instrumental methods for developing experimental skills in building
technical competence.

Instrumental Experiments

1. Potentiometric estimation of FAS using standard K2Cr2O7 solution.

2. Conductometric estimation of acid mixture
3. Determination of Viscosity co-efficient of the given liquid using Ostwald’s
viscometer.
4. Colorimetric estimation of Copper
5. Determination of pKa of weak acid using pH meter
6. Flame Photometric Estimation of Sodium and Potassium
Volumetric Experiments

1. Estimation of Total hardness of water by EDTA complexometric method.

2. Estimation of CaO in cement solution by rapid EDTA method.
3. Determination of percentage of Copper in brass using standard sodium
thiosulphate Solution.
4. Determination of COD of waste water.
5. Estimation of Iron in haematite ore solution using standard K2Cr2O7 solution by
external Indicator method.
6. Estimation percentage of chlorine in the given sample of bleaching powder
(Iodometric method).
Course Outcomes:

On completion of this course, students will have the knowledge in,

 Handling different types of instruments for analysis of materials using small

quantities of materials involved for quick and accurate results
Dept. of Chemistry, MIT, Mysore 5
 Carrying out different types of titration for estimation of concerned in
materials using comparatively more quantities of materials involved for
good results.

Conduction of Practical Examination:

1. Examination shall be conducted for 100 marks, later reduced to 60 marks.

2. All experiments are to be included for practical examination.
3. One instrumental and another volumetric experiment shall be set.
4.Different experiments shall be set under instrumental and a common
experiment under Volumetric.
Reference Books:
1.G.H.Jeffery,J.Bassett,J Mendham and R.C.Denney,”vogel’s text book of
Quantitative chemical analysis”

2.O.P.Vermani & Narula,”Theory and practice in Applied chemistry”,new age

international publishers.

3. Gary D.Christian,”Analytical chemistry”,6 th edition,Wiley India.

CO’s DESCRIPTION OF THE OUTCOMES

Understand and apply the fundamental of chemical reaction

18CHEL16.1/26.1 procedural adaptation in practices and safe usage of equipment
in laboratory and present the findings appropriately.
Apply the principles related to chemistry to conduct
18CHEL26.2/26.2
investigation for given scenario under study.

Analyze the key input and outcomes of experiment on the given

18CHEL16.3/26.3 problem scenario, infer the correctness of the selected parameter
based on efficacy of solution and present them suitably.
Dept. of Chemistry, MIT, Mysore 6

DO’s and DONT’s:-

DO’s:

 Wear proper uniform with identity cards in the laboratory.

 Should maintain disciplines in the laboratory.
 Handle all the equipment’s and chemicals carefully.
 Follow the safety precautions while performing experiment.
 Enter the lab in-time as per the schedule.
 Comply the instructions given by the faculty and instructor.
 Arrange the chairs/equipments before you leave the lab.
 Keep your surrounding clean and tidy.

DONT’s:
 Do not walk around in the lab unnecessarily.
 Do not go out of the lab without permission.
 Do not eat, smoke or drink in the Laboratory.
 Do not walk bare footed in the Laboratory.
 Never do unauthorized experiment.
 Never taste any chemicals.
 Do not use any equipment or chemicals unless you are trained and
approved as a user by your supervisor.

Learn as much as you can while you are young. Since

Life becomes too busy later……

-Dana Stewart Scott
Dept. of Chemistry, MIT, Mysore 7

GENERAL INSTRUCTIONS

 Maintain silence in the laboratory.

 Keep your working table clean and tidy.
 Keep the reagents in their proper places after use to avoid misplace and
do not contaminate.
 Use Dustbin provided to put waste papers and filter paper.
 Do not pour concentrated acids into the sink. If they are to be poured,
flush them using water liberally.
 To turn out to be a better analyst, understand the theory behind the
reactions you carry out.
 Use the specified quantities of reagents.
 Do not use wet hand during weighing.
 Neatly written practical record for the experiment performed in the
previous class and manual book for the experiment to be performed shall
be produced at the beginning of practical class.
 Bring all the necessary things such as calculator, graph sheet, pencil,
scale etc., to perform the experiment in stipulated time.
 Confine long hair when in the lab so that it will not catch on fire or come

into contact with chemicals.

Dept. of Chemistry, MIT, Mysore 8
C O NT E N T S OF E XPE R I ME N T S

Part – A
INSTRUMENTAL ANALYSIS
Sl.
Date Title of the Experiments Marks
No.
1 Colorimetric estimation of copper.

2 Determination of pKa of a weak acid using pH meter.

3 Potentiometric estimation of FAS using standard

K2Cr2O 7 solution.

4 Conductometric estimation of an Acid mixture using

standard NaOH solution.

5 Determination of viscosity coefficient of a given liquid

using Ostwald’s Viscometer.
Flame Photometric estimation of Sodium and
6
Potassium in the given sample of Water.

Part – B
VOLUMETRIC ANALYSIS
Sl.
Date Title of the Experiments Marks
No.

1 Determination of Total Hardness of a sample of Water

using Disodium salt of EDTA.

2 Determination of CaO in the given sample of Cement

by Rapid EDTA method.

3 Determination of COD of the given Industrial Waste

water sample.

4 Determination of Percentage of Copper in Brass using

standard Sodium thiosuplhate solution.
Estimation percentage of chlorine in the given
5
sample of bleaching powder (Iodometric method).
Determination of Iron in a given sample of Haematite
6 ore solution using K2Cr2O7 crystals by external
indicator method.
Dept. of Chemistry, MIT, Mysore 9

INSTRUMENTAL
METHODS OF CHEMICAL
ANALYSIS

PART - A
Dept. of Chemistry, MIT, Mysore 10

OBSERVATIONS AND CALCULATIONS

Volume of NaOH
pH pH pH/V
added in ml
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
Dept. of Chemistry, MIT, Mysore 11
PART - A

INSTRUMENTAL METHODS OF CHEMICAL ANALYSIS

EXPERIMENT NO. 1 Date:

DETERMINATION OF pKa OF A WEAK ACID USING pH METER

THEORY:
The strength of an acid is experimentally measured by determining its
equilibrium constant or disassociation constant (Ka). Strong acids are
completely ionized in aqueous solution and hence it is impossible to
determine the disassociation constant of strong electrolytes. But in case of
weak electrolytes are partially ionized in aqueous solution and hence the
equilibrium constant of weak electrolytes can be experimentally determined.

Let us consider weak acid like formic acid, which ionizes, freely in aqueous
solution as,
ka
HCOOH (aq) + H2O (l) H3O+ (aq) + HCOO- (aq)

Ka =
HCOO  H O 

3


HCOOH 
pKa is a modern method of expressing the strength of weak acid ,
ie., pKa = - log10 Ka
pKa value is determined by measuring the changes in pH of acid solutions at different
amount of the base added. In the titration of an acid with a base, the pH of the solution rises
gradually at first and then more rapidly. At the equivalence point there is a very sharp
increase in pH for a very small quantity of base added. Beyond the equivalence point, the pH
increases slightly on addition of base. The titration curve is obtained by plotting change in pH
against different volume of the base added and from the graph, determined the equivalence
point of an acid. The pKa value of an acid can be calculated using Henderson equation ,

pH = pKa + 1og10 Salt 

Acid 
At half equivalence point [salt] = [acid] and hence pH at half
equivalence point gives the pKa value of weak acid, i.e. pH = pKa .
Dept. of Chemistry, MIT, Mysore 12

Scale :

X –axis, 1.0 cm = _______ ml of NaOH

Y –axis, 1.0 cm = _______ ΔpH/ΔV

Graph No.: 2
1

pH Scale :

X –axis, 1.0 cm = _______ ml of NaOH

pKa
Y –axis, 1.0 cm = _______ pH

HEP
Volume of NaOH added in ml
Dept. of Chemistry, MIT, Mysore 13

PROCEDURE:
Make up the given weak acid in a 100 ml standard flask to the
mark by adding distilled water and mix well for uniform concentration.
Pipette out 25 ml of the given weak acid into a clean 100 ml beaker.
Connect the combined electrode (i.e. glass and calomel electrode) to
the pH meter and immerse the electrode in to the acid taken in a beaker.
Measure the pH of the acid . Add 0.5 ml of sodium hydroxide solution taken
in a micro burette in to the acid, stir well and measure the pH of the acid
and continue the addition of sodium hydroxide until the sudden raise in the
pH of the acid occur. Then take few more readings and take the difference in
the pH of acid (pH) and the volume of sodium hydroxide added (V). Plot
the graph, pH/V against the volume of sodium hydroxide added (graph
No.1) and from the graph 1, determine the equivalence point of the acid. Plot
the graph, pH against the volume of sodium hydroxide added (graph No 2).
Determine the half equivalence point that gives the pKa value of weak acid
by using the graph 2.

RESULTS:

1. Equivalence Point =_________________ ml of NaOH

2. Half E.P =_________________ ml of NaOH

3. pH at H.E.P = pKa of the given acid =______________

Dept. of Chemistry, MIT, Mysore 14

Upper mark (A)

Lower mark (B)

Wider limb

Capillary Tube

Fig. Viscometer
Dept. of Chemistry, MIT, Mysore 15
EXPERIMENT NO.2 Date:

DETERMINATION OF VISCOSITY COEFFICIENT OF A GIVEN LIQUID

USING OSTWALD’S VISCOMETER

THEORY: Viscosity arises due to internal friction between moving layers of

molecules. A liquid flowing through a cylindrical tube of uniform diameter is
expected to move in the form of molecular layers. A layer close to the surface
is almost stationary while that at the axis of tube moves faster than any
other intermediate layer. A slow moving layer exerts a drag or friction on its
nearest moving layer backwards. This property of a liquid by which it
retards or opposes motion of a liquid between the layers is called viscosity.
The coefficient of viscosity is defined as the tangential force per unit area
required maintaining a unit velocity gradient between any two successive
layers of a liquid situated unit distance apart. The coefficient of viscosity of a
 P r4t
liquid is given by Poiseuille’s formula,   , Where P = h d g
8V l

 h d g r4t
 
8V l
Where  is the coefficient of viscosity of the liquid, V = volume of the
liquid, r = radius of the tube, 1 = length of the tube, P is the pressure
difference between the two ends of the tube, h = height of the capillary tube,
d = density of the liquid, and g = gravitational force. If equal volumes of two
different liquids are allowed to flow through the same tube under identical
 w tw d
conditions, then,  w
 L tLd L

Where, w = co – efficient of viscosity of the standard liquid (water),

and L = co – efficient of viscosity of the given liquid which can be
determined. Where, tw = time taken by the standard liquid (Water), tL = time
taken by the given liquid, dw = density of standard liquid (water),
dL = density of given liquid. Viscosity is a temperature dependent property
and is inversely proportional to the temperature (T), i.e.  α 1/ T. Hence the
measurements are carried out at constant temperature.
Dept. of Chemistry, MIT, Mysore 16

OBSERVATIONS AND CALCULATIONS

Trial Nos. I II III Average time

in sec
Time taken by water in sec ( tW )

Time taken by liquid in sec ( tL )

L =  w tLd L
twd w

Liquid Number =

Room Temperature = ……………ºC

Where tw = time taken by water =____________________ sec

tL = time taken by liquid = ____________________ sec

dw = density of water =____________________ g / cc

dL = density of liquid =____________________ g / cc

w = co – efficient of viscosity of water =___________________ milli poise

L = co – efficient of viscosity of liquid =___________________ milli poise

L =  w t L d L =______________________
twd w

= ...................milli poise

RESULT:
The viscosity co – efficient of given liquid = ________ milli poise
Dept. of Chemistry, MIT, Mysore 17

PROCEDURE:

1. Transfer the known volume (say 15 ml) of the given organic liquid taken
in a burette into the viscometer. Suck the organic liquid above the upper
mark ‘A’ in the viscometer and allow it to flow freely through a capillary.
Start the stop clock when the liquid level just crosses the upper mark ‘A’
and stop it when the liquid level just crosses the lower mark ‘B’ in the
viscometer. Note down the time of flow of liquid in seconds (tl) and repeat
the experiment to get agreeing values.

2. Pour out the organic liquid and rinse the viscometer in acetone again.
Dry it in an electric oven and fix the viscometer vertically to a stand.

3. Transfer a known volume (say 15 ml) of distilled water taken in a

separate burette into a viscometer. Note down the time of flow of water
(tw) in seconds as similar to the liquid and repeat the experiment to get
agreeing values.

4. Determine the viscosity co-efficient of the given organic liquid using the
relation,

L =  w t L d L and the given values of  , d and d .

w w L
twd w

Note: -Transfer the organic liquid into the bottle after the experiment is
completed and rinse the viscometer with acetone and keep it in an
electric oven.
Dept. of Chemistry, MIT, Mysore 18
OBSERVATIONS AND CALCULATIONS

Volume of Concentration of Concentration of Absorbance (A)

Copper sulphate copper sulphate in copper in mg / ml or
in ml mg / ml Optical density
0 0 0 0.0
5 3.93 x 5 = 19.65 05 x 1 = 05

10 3.93 x 10 = 39.30 10 x 1 = 10

15 3.93 x 15 = 58.95 15 x 1 = 15

20 3.93 x 20 = 78.60 20 x 1 = 20

25 3.93 x 25 = 98.25 25 x 1 = 25

Test solution 3.93x x1=

C=

Note: Molecular weight of copper sulphate = 249.54.

Calculation:

1. Atomic weight of copper = 63.54

1.0 ml of stock solution = 3.93 mg of copper sulphate

249.54 gm of CuSO4 = 63.54 g of copper

 3.93 mg of CuSO4 = 63.54× 3.93 = 1.0 mg of Copper.

249.54
1ml of Stock Solution (CuSO4) = 3.93 mg of CuSO4 = 1.0 mg of Cu

C= concentration of copper in test solution = ____________mg / ml

V ml of copper sulphate = C mg of copper

C
 V ml of copper sulphate = V =  = ________ml
1.0 1 .0

Hence, the volume of test solution given = V = ______________ ml

Dept. of Chemistry, MIT, Mysore 19
EXPERIMENT NO. 3 Date:

COLORIMETRIC ESTMATION OF COPPER

THEORY:

When a monochromatic light of intensity Io is incident on a

transparent medium, a part of light is absorbed by the media (Ia), a part of
light is reflected (Ir) and the remaining part of light is transmitted (It).

 Io = Ia + It + Ir (for a glass – air interface, Ir is negligible)

 Io = Ia + It

The ratio of It / Io = T called transmittance and log Io / It = A which is

called absorbance or optical density. The relationship between absorbance
(A), concentration (c) (expressed in mol / dm3) and path length (t) (expressed
in cm) is given by Beer – Lambert’s law.

A = log Io / It = ε ct.

Where ε is the molar extension coefficient which is a constant for a

given substance at a given wave length and t = the path length of the cell
tube which is also constant for given cell tube. Therefore, A  c. Hence plot
the graph, absorbance against concentration of the solution gives a straight
line.

A series of standard solution of copper salt and test solution is treated

with ammonia to get blue cuprammonium complex and is diluted to a
definite volume. The absorbance of each of these solution and test solution
is measured at 620 nm since the complex shows maximum absorbance at
this wavelength. The absorbance values are plotted against concentration of
copper get a calibration curve and concentration of copper in test solution is
determined from the graph.
Dept. of Chemistry, MIT, Mysore 20
Scale:

X –axis, 1.0 cm = ………… mg/ml of Cu

Y –axis, 1.0 cm = ………….Absorbance

Absorbance

Concentration of Cu in mg/ml

Results:

1. The volume of test solution given = ______________ ml

2. Absorbance of test solution = ______________

3. Concentration of copper in test solution = ______________ mg /ml

4. Concentration of copper sulphate solution = ______________ mg/ml

Dept. of Chemistry, MIT, Mysore 21
PROCEDURE:

Transfer the given copper sulphate solution (Stock solution) to a

burette and draw out 5,10,15, 20 and 25 ml of the solution into 50 ml
standard flasks. Add 5 ml of 1:1 ammonia solution to each of them and also
to the test solution given in a separate 50 ml standard flask. Make up the
solution to the mark by adding distilled water and mix well for uniform
concentration.

Switch on the colorimeter and select the wavelength or max = 620nm

and adjust zero absorbance for blank solution .Then measure the
absorbance for each standard solution and test solution. A straight line
graph is obtained by plotting absorbance against the concentration of
copper. From the graph, determine the concentration of copper in the test
solution and calculate the volume of copper sulphate in the given test
solution.

CuSO4 + 4NH3 [Cu (NH3)4] SO 4 (blue colour)

(Cuprammonium sulphate complex)

Preparation of blank solution: - Blank solution can be prepared by adding

5.0 ml of 1:1 ammonia and distilled water in 50 ml standard flask. Mix well
for uniform concentration.
Dept. of Chemistry, MIT, Mysore 22
OBSERVATIONS AND CALCULATIONS

Volume of E.M.F ΔE E Volume of E.M.F ΔE E

K2Cr2O7 in mv V K2Cr2O 7 in mv V

added added
in ml (V ) in ml (V )
0.0 5.5
0.5 6.0
1.0 6.5
1.5 7.0
2.0 7.5
2.5 8.0
3.0 8.5
3.5 9.0
4.0 9.5
4.5 10.0
5.0

Scale :
X –axis, 1.0 cm = _______ ml of K2Cr2O7

E
Y –axis, 1.0 cm = _______
V

Volume of K2Cr2O7 required = V K2Cr2O7 = ________ml

Dept. of Chemistry, MIT, Mysore 23

EXPERIMENT NO. 4 Date:

POTENTIOMETRIC ESTIMATION OF MOHR’S SALT (FAS) BY USING

STANDARD K2Cr 2O 7 SOLUTION

THEORY:
When the electrode is dipped in the solution, the potential of an
electrode depends on the concentration of the ions in the electrolyte.
Therefore determination of maximum potential can serve as an indicator in
potentiometric analysis. Determination of change of potential with
concentration gives more accurate results than volumetric analysis.

When the given electrode is combined with saturated calomel

electrode and dipped in the given electrolyte, an electro chemical cell is
formed. The emf of this cell is measured using potentiometer. During the
titration, the change in emf of the cell or concentration of ions in the
electrolyte can be measured. Then E / V is plotted against the volume of
the titrant, there will be a peak corresponding to the endpoint of the
reaction.
 emf of the cell is calculated using Nernst equation,

 0.0591 [Pr oducts ]

Ecell = Ecell log
n [Re ac tan ts ]

Where Ecell = emf of the cell, Ecell standard emf of the cell, n = number of
electrons involved in the reaction, [products] = concentration of the products
and [reactants] = concentration of the reactants.
Dept. of Chemistry, MIT, Mysore 24
Note:
1. Normality of K2Cr2O7 = N K 2Cr 2O 7 = 0.1 N
2. Equivalent weight of Mohr’s salt = 392

NK 2 Cr2 O 7 x VK 2 Cr2 O 7
 Normality of Mohr’s salt solution =
V Mohr ' s salt

N Mohr’s salt = =_____________ N

25
Weight per litre of
Mohr’s salt crystals = X = N Mohr’s Salt x equivalent weight of Mohr’s salt

X = _____________ x 392 = _____________ g

Weight per 100 ml of Mohr’s salt = X / 10 = …………...g

RESULT: Amount of Mohr’s salt present in the given solution …………..g.

Dept. of Chemistry, MIT, Mysore 25

PROCEDURE:
Make up the given Mohr’s salt solution in a 100 ml standard flask to
the mark by adding distilled water and mix well for uniform concentration
Pipette out 25 ml of Mohr’s salt solution in to a clean 100 ml beaker followed
by adding one t.t. of dilute sulphuric acid and stir well using a glass rod.
Connect the platinum and calomel electrodes to the potentiometer,
and immerse the electrodes in to the Mohr’s salt solution taken in a beaker.
Measure the emf of the solution. Add 0.5 ml of potassium dichromate
solution in to the Mohr’s salt solution, stir well and measure the emf of the
solution and continue the addition of potassium dichromate added until the
sudden raise in the emf of solution occur. Then take few more readings and
take the difference in the emf of solution (E) and the volume of potassium
dichromate added (V). Plot the graph, E / V against the volume of
potassium dichromate added. From the graph, determine the volume of
potassium dichromate required to rapid increase in the emf of the solution.
Calculate the weight per liter and weight per 100 ml of Mohr’s salt.

K2Cr2O 7 + 7H2SO4 + 6FeSO4 3Fe2(SO4)3 + K2SO4 +Cr2(SO4)3 + 7H2O

Dept. of Chemistry, MIT, Mysore 26

OBSERVATIONS AND CALCULATIONS

Estimation of Acid mixture

Vol. of NaOH Conductivity Vol. of NaOH Conductivity

in ml Ohm-1 cm-1 in ml Ohm-1 cm-1
0.0 5.5
0.5 6.0
1.0 6.5
1.5 7.0
2.0 7.5
2.5 8.0
3.0 8.5
3.5 9.0
4.0 9.5
4.5 10.0
5.0

V1 =Volume of NaOH required neutralizing HCl =……….ml

(V2 ─V1) =Volume of NaOH required neutralizing CH3COOH =……….ml

Scale :
X –axis, 1.0 cm = _______ ml of NaOH

Y –axis, 1.0 cm = _______ ohm-1 cm-1

Conductivity

V1 V2
Volume of NaOH added in ml
Dept. of Chemistry, MIT, Mysore 27

EXPERIMENT NO. 5 Date:

CONDUCTOMETRIC ESTIMATION OF AN ACID MIXTURE USING

STANDARD SODIUM HYDROXIDE SOLUTION
THEORY:

Measurement of conductivity can be employed to determine the end

point in acid-base titrations. In conductometric titrations there is a sudden
change in conductivity of the solution near the endpoint. The end point is
determined graphically by plotting conductivity (ordinate) against sodium
hydroxide (abscissa).
Conductometric titration may be applied for the determination of acids
present in a mixture. In the titration of a mixture of a weak acid (acetic
acid) and a strong acid (hydrochloric acid) with a strong base (sodium
hydroxide), the conductivity decreases upon adding sodium hydroxide to
acid mixture at the initial stages owing to the replacement of highly mobile
H+ ions (mobility: 350 ohm-1 m-1) by the less mobile Na+ ions (mobility:
50ohm-1m-1). This trend continues till all the H+ ions of hydrochloric acid
replaced [i.e., the strong acid is neutralized]. Continued addition of sodium
hydroxide raises the conductivity moderately, as the weak acid, acetic acid
is converted into its salt, sodium acetate. Further addition of sodium
hydroxide raises the conductivity steeply due to the presence of free OH-
ions (mobility: 198 ohm-1 m-1). The titration curves in the graph given depict
the location of the equivalence points.
PROCEDURE:
Make up the given acid mixture in a 100 ml standard flask to the
mark by adding distilled water and mix well for uniform concentration.
Pipette out 50 ml of the given acid mixture into a clean 100 ml beaker and
stir well using a glass rod.
Dip the conductivity cell in the acid mixture and measure the
conductivity of the acid mixture .Add 0.5 ml of sodium hydroxide solution
from a burette. After each addition, stir the solution gently and note down
the conductivity.
Dept. of Chemistry, MIT, Mysore 28

Estimation of HCl

Volume of NaOH required to neutralize HCl = V1 =…………..ml

N NaOH x V1 NaOH
Normality of HCl = ----------------------------
V Acid Mixture

0.2 x
=-------------------= ------------N
50
Weight per liter of HCl = X = N HCl X Equivalent weight of HCl

= --------------------X 36.5

X= -----------------------g

X
Weight per 100 ml of HCl = = ------------ = ---------- g
10 10

Estimation of CH3COOH

Volume of NaOH required to neutralizing CH3COOH = (V2 ─V1) =……….ml

N NaOH x (V2 ─V1) NaOH

Normality of CH3COOH = --------------------------------
V Acid Mixture

0.2 x
=----------------= ------------N
50
Weight per liter
of CH3COOH =Y=N CH3COOH X Equivalent weight of CH3COOH

= --------------------X 60

Y= -----------------g

Y
Weight per 100 ml of CH3COOH = = ------------ = ---------- g
10 10
Dept. of Chemistry, MIT, Mysore 29

As the titration proceeds, the conductivity first gradually decreases and then
increases slowly and finally increases sharply. Plot the graph conductivity
versus volume of sodium hydroxide added. From the graph determined the
volume of sodium hydroxide is required to neutralize hydrochloric acid [V1]
and acetic acid [V2 – V1] in an acid mixture. Calculate the weight per liter
and weight per 100 ml of hydrochloric acid and acetic acid respectively.

HCl + NaOH NaCl + H2O

CH3COOH + NaOH CH3COONa + H2O

RESULT:
1. Amount of HCl present in the given solution =…….………g

2. Amount of CH3COOH present in the given solution =……..……..g

Dept. of Chemistry, MIT, Mysore 30
OBSERVATION AND CALCULATION

Concentration of the standard solution = 100 ppm

Flame
Volume of sodium Concentration
Photometer
solution taken in ppm
Reading
5
10
15
20
Test solution
(‘a’ cm3)

25
Flame photometric reading

20

15

10

5
a
0
0 5 10 15 20 25
Volume of sodium solution

Unknown volume of NaCl solution =……… (a) cm3

Therefore, amount of sodium in the test solution = a x 100 ppm

50

= x 100 ppm
50

= ----------- ppm
Dept. of Chemistry, MIT, Mysore 31
EXPERIMENT NO. 6 Date:

FLAME PHOTOMETRIC ESTIMATION OF SODIUM OR POTASSIUM

IN THE GIVEN WATER SAMPLE

THEORY:
Flame photometry is an atomic emission technique used for the

detection of alkali and alkali earth metals. If a solution containing metallic

salts is sprayed into the flame, electrons in the metal ions of the vapour gain

thermal energy and get excited from lower energy level E1 to higher energy

levels En, where n = 1, 2, 3 …. From higher energy state these electrons

return to the ground state by emitting radiations (En – E1 = h) which are

the characteristic of each element.

Flame photometric determination of sodium and other elements such

as K, Ca, Li, etc is based on the fact that these elements impart

characteristic colors to the Bunsen flame and the brightness of the flame

varies with the concentration of these elements present in the sample. Flame

photometer correlates the emitted radiation with the concentration of these

elements. It is simple and rapid method for the estimation of alkali and

alkali earth metals. In a flame photometer a suitable filter for a particular

element is placed between the flame and the detector. The sample

containing the analyte is aspirated into the flame through atomizer.

Radiation from the resulting flame is collected by the lens and allowed to

pass through an optical filter, which permits only the characteristic

radiation of the element under determination to the photo cell. The output

from the photo cell indicates the concentration of the element.

Dept. of Chemistry, MIT, Mysore 32
Procedure:

Transfer from the burette 5, 10, 15 & 20 cm3 of standard sodium

solution into different 50 cm3 volumetric flask. Make up all the solutions
using distilled water. Stopper the flasks and shake well to get uniform
concentration. To the given test solution add distilled water up to the mark
and shake well. Switch on the instrument set the filter for 589nm and
adjust the air from the compressor to 10 lbs per sq inch using pressure
regulator knob. Put on the burner and adjust the flame to clear blue. Dip
the capillary tube to distilled water and set the reading to zero by means of
zero control knob. Then feed 100 ppm sodium solution and set the reading
to 100 by means of span knob. Repeat the process to confirm the accuracy
of the calibration.
Feed the standard sodium solutions one by one including the test
solutions and note readings. (Between two standard solutions dip the
capillary to distilled water so that reading should become zero). Prepare the
calibration graph by taking flame photometric reading against the volume of
the solution and estimate the amount of sodium in the given test solution.
Similar procedure is followed for the estimation of potassium from
potassium carbonate stock solution using the filter 766nm.

Result:

The amount of sodium present in the given test solution is----------- ppm
Dept. of Chemistry, MIT, Mysore 33
VOLUMETRIC METHODS OF CHEMICAL ANALYSIS

PART - B

INSTRUCTIONS TO THE STUDENTS:

 Read the procedure before commencement of the experiment and do

the experiment according to the procedure.
 Handle the glass wares with care.
 Apparatus used : Burette, Pipette, Standard flask, Conical flask,
Beaker, Funnel, Washing bottle for volumetric analysis.
 Wash the all apparatus with tap water and rinse them with distilled
water before commencement of the experiment.
 Wash all the apparatus with tap water again after the experiment is
completed and return them to the instructor.
DEFINITIONS

Standard solution :-Solution whose normality is known

Standardization :- Determination of the strength of given solution using

standard solution.
Estimation:- Determination of the weight of a given substance present in a
known volume of a solution.
Normality :- Number of gm equivalent weight of the substance present in
one liter of its solution.
Molarity :- Number of gm molecular weight of the substance present in one
liter of its solution.
Indicator:- It is a substance which shows the end point of the reaction by
its colour change.
Oxidation:- It is process of loss of electrons by atoms or ions.
Reduction:- It is process of gain of electrons by atoms or ions.
Oxidizing agent:- The substance which gain of electrons. E.g., K2Cr2O7,
KMnO4 etc.
Reducing agent:- The substance which loss of electrons. E.g., Mohr’s salt,
FeCl2 , hypo etc.
Dept. of Chemistry, MIT, Mysore 34

OBSERVATIONS AND CALCULATIONS:

Preparation of standard solution of disodium salt of EDTA

Weight of EDTA salt = ______________g

Weight of EDTA salt

Molarity of EDTA = x 4
Molecular weight of EDTA

x 4
MEDTA = = ____________ (a) M
372.24

Determination of total hardness of water

Burette : Standard EDTA solution

Conical flask: 25 ml of hard water + 5ml of NH4OH – NH4Cl buffer
Indicator : 2-3 drops of Eriochrome black – T
End point : Wine red to purple blue colour

Burette readings I II III

Final readings

Initial readings

Volume of EDTA
run down in mls

 Volume of EDTA required = V= ____________ml

NOTE: Molecular weight of CaCO3 = 100

1000 ml of 1M of EDTA = one g molecular weight of CaCO3 (100)

(a)  V  100
 V ml of (a) M EDTA = X = = ----------------------
1000

X = _________g of CaCO3
Dept. of Chemistry, MIT, Mysore 35

EXPERIMENT NO. 1 Date:

DETERMINATION OF TOTAL HARDNESS OF WATER

THEORY:
Hardness of water is due to the presence of dissolved salts of calcium

and magnesium. The total hardness of water is determined using ethylene

diamine tetra acetic acid (EDTA) which form complex with Ca2+ and Mg2+

ions. The EDTA molecule has two easily replaceable hydrogen atoms and

hence the EDTA form complex with metal ion present in water. Reaction can

be carried out quantitatively at a pH of 10 using Eriochrome black–T as

indicator. Since the reaction involves the liberation of H+ ions, a buffer

mixture has to be used to maintain a pH of 10. The buffer mixture used in

the titration is ammonium hydroxide and ammonium chloride. The total

hardness of the water is usually expressed in terms of ppm (ie, parts per

million) of CaCO3. EDTA is sparingly soluble in water and hence disodium

salt of EDTA is used as reagent for preparing the solution. The structures of

EDTA ( H4Y ) and disodium salt of EDTA (Na2H2Y) are given below.

CH2COOH CH2COOH CH2COONa CH2COOH

| | | |
N – CH2 – CH2 – N & N – CH2 – CH2 – N
| | | |
CH2COOH CH2COOH CH2COOH CH2COONa

EDTA(H4Y) Disodium salt of EDTA (Na2H 2Y)

Dept. of Chemistry, MIT, Mysore 36

 Weight of CaCO3 present

in 25 ml of hard water = X = _________g of CaCO3

 Weight of CaCO3 present in one million or

X  10 6
106 ml of hard water = Y =
25

 10 6
Y= = __________ppm
25

Thus total hardness of water in terms of ppm= Y = ________ppm of CaCO3

Note: Parts per million: ppm :- is the parts of CaCO3 equivalent

hardness present per million or 106 parts of water.
i e: 500 ppm = 500 part of CaCO3 equivalent hardness present per
million or106 parts of water.
Dept. of Chemistry, MIT, Mysore 37

PROCEDURE:

I. Preparation of standard solution of disodium salt of EDTA:

Weigh about 1.0 g of disodium salt of EDTA accurately using an

electronic balance. Transfer the crystals of EDTA in to a clean 250 ml

standard flask using a glass funnel. Dissolve the crystals by adding ½ t.t. of

ammonium hydroxide and little distilled water. Make up the solution to the

mark by adding distilled water and mix well for uniform concentration.

Calculate the molarity of EDTA solution.

II. Determination of total hardness of water:

Pipette out 25ml of the given water sample into a clean conical flask

and add 5 ml of buffer solution (ammonium hydroxide and ammonium

chloride). Add 2-3 drops of Eriochrome black–T indicator. Titrate this

against EDTA solution taken in a burette until the wine red colour changes

to purple blue. Note down the volume of EDTA added and repeat the

experiment for concordant values. Calculate the total hardness of water in

terms of ppm of CaCO3.

REACTIONS:

M2+(Ca2+or Mg2+) + In M – In (wine red colour)

(Hard water) (Indicator) (Metal ion – In complex)

M – In + Na2H2Y M – Y + 2 Na+ + 2H+ + In (blue)

(Metal ion – EDTA complex)

RESULT: The total hardness of the given water sample=……….ppm

Dept. of Chemistry, MIT, Mysore 38
OBSERVATIONS AND CALCULATIONS:

I . Preparation of standard solution of disodium salt of EDTA

Weight of EDTA salt = ______________g

Weight of EDTA salt

Molarity of EDTA =  4
Molecular weight of EDTA

x 4
MEDTA = = ____________ (a) M
372.24

II. Estimation of CaO in cement solution

Burette : Standard EDTA solution

Conical flask : 25 ml of cement solution + 5ml of 1:1 glycerol + 5ml
of di-ethylamine + 10 ml of 2N NaOH + shake well
Indicator : 2-3 drops of Pattern - Reeder’s indicator
End point : Wine red to purple blue colour

Burette readings I II III

Final readings

Initial readings

Volume of EDTA
run down in mls

 Volume of EDTA required = V= _________ ml

NOTE: 1. Weight of cement in 250 ml = W = __________g

2. Molecular weight of CaO = 56.08

1000 ml of 1M of EDTA = one gm molecular weight of CaO (56.08)

56.08 x (a) x V 56.08 x

V ml of (a) M EDTA = X = 
1000 1000

X = __________ g of CaO
Dept. of Chemistry, MIT, Mysore 39

EXPERIMENT NO. 2 Date:

DETERMINATION OF CaO IN THE GIVEN SAMPLE OF CEMENT

SOLUTION BY RAPID EDTA METHOD
Theory:
Cement contains oxides of calcium, aluminium, magnesium, iron and
small amount of silica. Calcium oxide is a prime constituent of cement and
the general composition of portland cement is given below.

CaO = 60 – 66%, SiO2 = 17 – 25%, Al2O3 = 3 – 8%, Fe 2O3 = 2 – 6%,

MgO = 0.1- 5.5%, SO3 = 1 – 3 % and Na2O & K2O = 0.5 – 1.5%

In the estimation of calcium in cement, the given cement sample is

treated with concentrated hydrochloric acid. The insoluble silica is filtered
off and the filtrate which contains calcium ions is titrated against EDTA at a
pH of 12 – 14 using Pattern-Reeder’s indicator. The latter is used in this
titration because Eriochrome black – T indicator forms a very weak complex
with calcium ions. Diethylamine is added to maintain a pH of about 12.5
and glycerol is added to get a sharp end point. This method facilitates the
determination of calcium only although Mg+2 ions are present in the cement
solution which can readily form complexes with EDTA (i.e.,Mg+2 ions do not
react with EDTA in the above conditions)

PROCEDURE:

I.Preparation of standard solution of disodium salt of EDTA:

Weigh about 1.0 g of disodium salt of EDTA accurately using an

electronic balance. Transfer the crystals of EDTA into a clean 250ml
standard flask using a glass funnel. Dissolve the crystals by adding ½ t.t. of
ammonium hydroxide and little distilled water. Make up the solution to the
mark by adding distilled water and mix well for uniform concentration.
Calculate the molarity of EDTA solution.
Dept. of Chemistry, MIT, Mysore 40

 Weight of CaO present in 25 ml of cement solution = X = _________g

X x 250
 Weight of CaO present in 250 ml of cement solution = Y =
25

Y =_______________

Y =________________g

 Percentage of CaO in the cement solution = Y x 100

Weight of cement in 250 ml ( W )

= ------------------------------

 Percentage of CaO in the cement solution= ___________

Dept. of Chemistry, MIT, Mysore 41

II. Estimation of calcium oxide:

Pipette out 25ml of the given cement solution into a clean conical
flask. Add 5ml of 1:1 glycerol, 5ml of diethyl amine and 10ml of 2N sodium
hydroxide. Add 2-3 drops of Pattern- Reeder’s indicator. Shake well and
titrate this against EDTA solution taken in a burette until wine red
colour changes to purple blue. Note down the volume of EDTA added and
repeat the experiment for concordant values. Calculate the percentage of
calcium oxide in the given cement solution.

REACTIONS:

(CaO + SiO2) + 2HCl CaCl2 + SiO2  + H 2O

Cement

Ca2+ + In Ca – In complex (wine red colour)

Ca – In + EDTA Ca – EDTA complex + In (blue colour)

RESULT: The Percentage of CaO present in the given cement

solution = ___________
Dept. of Chemistry, MIT, Mysore 42
OBSERVATIONS AND CALCULATIONS:

I. Preparation of Brass solution:

Weight of brass = W = __________g

II. Estimation of copper

Burette : Standard hypo solution

Conical flask : 25 ml brass solution + NH4OH drop wise till a bluish
white ppt. is formed. Dissolve the ppt. by adding dilute
acetic acid + ¼th t.t. of acetic acid in excess + One t.t. of
10% KI + shake well.
Indicator : 2 ml of freshly prepared starch.
End point : Disappearance of blue colour

Burette readings I II III

Final readings
Initial readings
Volume of hypo
run down in mls

 Volume of hypo required = V= _________ ml

NOTE: 1. Normality of hypo = 0.03N

2. One gm equivalent weight of copper = 63.54

 1000 ml of 1 N of hypo = one gm equivalent weight of copper (63.54)

V x 0.03 N x 63.54
 V ml of 0.05 N hypo = X = 1000

0.03 63. 54 
= 1000

X = ____________ g of copper

 Weight of copper present in 25 ml of brass solution = X = ___________g

Dept. of Chemistry, MIT, Mysore 43

EXPERIMENT NO. 3 Date:

DETERMINATION OF PERCENTAGE OF COPPER IN BRASS USING

STANDARD SODIUM THIOSULPHATE SOLUTION

THEORY:

The chief constituents of brass alloy are copper and zinc. It also contains
small quantities of tin, lead and iron. The percentage composition of a
typical brass alloy is given below.

Cu = 50 – 90 % , Zn = 20 – 40 % , Sn = 0 - 6% , Pb = 0 - 2% and
Fe = 0 – 1% .
A solution of brass is made by dissolving the sample in minimum amount of
nitric acid. Excess of nitric acid destroyed by boiling with urea. The solution
is neutralised and made in to slight acidic medium. Potassium iodide
solution is added and the cupric ion present in the brass solution oxidise
potassium iodide to iodine. The iodine liberated is titrated against sodium
thiosulphate using starch as indicator. The volume of sodium thiosulphate
consumed is measure of the amount of copper present in the solution and
sodium thiosulphate is commonly known as hypo.

PROCEDURE:

I. Preparation of Brass solution:

Weigh about 1.2 g of the brass pieces accurately using an electronic

balance and transfer it into a clean conical flask. Add two t.t. of 1:1 nitric
acid and cover the mouth of the flask with a glass funnel. Warm gently to
dissolve the brass piece completely and add two t.t of distilled water. Add
about two g of urea and continue the heating until the reddish brown fumes
of oxides of nitrogen are expelled completely. Cool the solution to room
temperature and transfer the solution of brass in to a clean 250 ml standard
flask. Make up the solution to the mark by adding distilled water and mix
well for uniform concentration.
Dept. of Chemistry, MIT, Mysore 44

X x 250
 Weight of copper present in 250 ml of brass solution = Y =
25

x 250
Y= 25

Y =__________ g

 Percentage of copper in the given brass sample =

( )

= __________________

= ________
Dept. of Chemistry, MIT, Mysore 45

II Estimation of copper:

Pipette out 25 ml of brass solution into a clean conical flask and add
dilute ammonium hydroxide drop by drop until bluish white precipitate is
formed. Dissolve the ppt. by adding dilute acetic acid drop by drop and then
add 1/ 4 t.t. of acetic acid in excess. Add one t.t. of 10% potassium iodide
solution and shake well. Titrate the liberated iodine against standard
sodium thiosulphate solution taken in a burette using starch as indicator
towards the end point. (Add starch when brown solution changes to whitish
yellow). Disappearance of blue colour is the end point. Note down the
volume of hypo added and repeat the experiment for concordant values.
Calculate the percentage of copper in the given sample of brass.

REACTIONS :
heat
Cu + 4 HNO3 Cu (NO3)2 + 2 H 2O + 2 NO2 
(Reddish brown)

2 Cu (NO3 )2 + 4 KI Cu2 I2  + 4 KNO 3 + I2  (Brown)

(Cuprous iodide)

2 Na2S2O 3 + I2 2 NaI + Na2S4O 6 (sodium tetra thionate)

(Hypo)

I2 + starch Starch-iodide complex (Deep blue)

RESULT: The Percentage of copper present in the given brass sample=………

Dept. of Chemistry, MIT, Mysore 46

OBSERVATIONS AND CALCULATIONS:

I. Preparation of standard potassium dichromate solution :

Weight of K2Cr2O7 crystals = _____________g

Weightof K 2 Cr2 O7  4
Normality of K2Cr2O 7 =
Equivalent weight of K 2 Cr2 O 7

x4
N K2Cr2O 7 =  __________(a) N
49

II. Estimation of iron

Burette : Standard K2Cr2O 7 solution

Conical flask : 25 ml of haematite ore solution + ¼ t.t concentrated
HCl + heat + SnCl2 drop wise till yellow colour changes to
colourless + 5.6 drops of SnCl2 in excess + cool the
solution to room temperature + 10 ml of saturated HgCl2
+ shake well + one t.t. of distilled H2O
Indicator : Potassium ferricyanide as external indicator
End point : Failure to observe blue colour when a drop of reacting
mixture is brought in contact with the indicator placed
on paraffined paper

Burette readings I II III

Final readings
Initial readings
Volume of K2Cr2O7
run down in mls

 Volume of K2Cr2O7 required = V = __________ ml

NOTE: 1. Weight of haematite ore in 250ml = W = ___________g

2. Equivalent weight of iron = 55.85
Dept. of Chemistry, MIT, Mysore 47

EXPERIMENT NO. 4 Date:

DETERMINATION OF IRON IN A GIVEN SAMPLE OF HAEMATITE ORE

SOLUTION USING K2CR2O7 CRYSTALS BY EXTERNAL INDICATOR
METHOD
THEORY:

Haematite is an important ore of iron containing mainly, ferric oxide

(Fe 2O3) and small amount of silica (SiO2). A known weight of the ore is

digested with hydrochloric acid and the insoluble residue mainly containing

silica is removed by filtration. The filtrate is diluted to 250 ml and is

supplied for the estimation. Iron is present in the solution as Fe3+ (ferric)

ions ant it is reduced to Fe2+ (ferrous) ions using stannous chloride (SnCl2)

in hot condition in presence of concentrated HCl. The excess of stannous

chloride is oxidized by adding with mercuric chloride solution. The ferrous

ions in the resulting solution are titrated against standard potassium

dichromate using potassium ferricyanide as external indicator. Potassium

ferricyanide produces an intense deep blue colour with ferrous ions due to

the formation of ferriferrocyanide complex.

PROCEDURE:

a) Preparation of standard solution of potassium dichromate:

Weigh about 1.2 g of potassium dichromate crystals accurately using

an electronic balance. Transfer the crystals of potassium dichromate into a
clean 250ml standard flask using a glass funnel. Dissolve the crystals by
adding distilled water and make up the solution to the mark by adding
distilled water. Mix well for uniform concentration and calculate the
normality of potassium dichromate solution.
Dept. of Chemistry, MIT, Mysore 48

1000 ml of 1 N of K2Cr2O7 = one gm equivalent weight of iron (55.85)

55.85 x (a) x V
 V ml of (a) N K2Cr2O7 = X =
1000

55.85 
X  __________ ___g of iron
1000

 Weight of iron present in 25 ml of haematite solution = X = _________g

 Weight of iron present in 250 ml of

X x 250
haematite solution = Y =  ________
25

Y = __________g

 Percentage of iron in the given

Y  100
haematite solution =
Weight of haematite ore in 250 ml (W )

= ______________________

= _____________
Dept. of Chemistry, MIT, Mysore 49

b) Estimation of iron:

Pipette out 25ml of the haematite ore solution into a clean conical
flask. Add ¼ t.t of concentrated hydrochloric acid and heat the solution
nearly to boiling. Add stannous chloride drop by drop taken in a separate
burette till yellow colour solution becomes colourless and then add
6-8 drops of stannous chloride in excess. Cool the solution to lab
temperature and add 10ml of saturated mercuric chloride at once. Shake
well and a silky white precipitate is formed. (If no ppt or black ppt is formed,
reject and repeat the experiment). Add one t.t. of distilled water and
titrate this against standard potassium dichromate solution taken in a
burette, using potassium ferricyanide as external indicator. The end point is
failure to observe blue colour when one drop of the titrated mixture is
brought in contact with a drop of the indicator placed on paraffin paper.
Note down the volume of potassium dichromate added and repeat the
experiment for concordant values. Calculate the percentage of iron in the
given sample of haematite ore solution.

REACTIONS:
heat
Fe 2O3 + 6HCl 2FeCl3 + 3 H2O
(Haematite ore) [Ferric chloride)

FeCl3 + SnCl2 2FeCl2 + SnCl4

SnCl2 +2 HgCl2 Hg2Cl2 + SnCl4

K2Cr2O7 + 14HCl + 6FeCl2 6 FeCl3 + 2KCl + 2CrCl3 + 7H2O

(Ferrous chloride)

3FeCl2 + 2 K3 [Fe(CN)6] 6KCl + Fe3 [Fe (CN)6]2 (deep blue)

(Potassium Ferricyanide) (Ferri Ferrocyanide complex)

RESULT: The Percentage of iron present in the given haematite ore

solution =…….
Dept. of Chemistry, MIT, Mysore 50
OBSERVATIONS AND CALCULATIONS:

I. Preparation of Mohr’s salt or ferrous ammonium sulphate (FAS)

solution:

Weight of FAS crystals =___________g

Weight of FAS  4
Normality of FAS =
Equivalent weight of FAS

x 4
N FAS = = __________(a) N
392

II. Estimation of COD or back titration

Burette : Standard FAS solution
Conical flask : 25 ml of waste water +25 ml of standard K2Cr2O7
solution + 10 ml of 1:1 H2SO4 [(Ag)2SO4 + HgSO4]
Indicator : 2 – 4 drops of ferroin indicator
End point : Blue green to reddish brown colour

Burette readings I II III

Final readings

Initial readings

Volume of FAS run down in mls

 Volume of FAS solution required for back titration = V1 = _____ ml

Dept. of Chemistry, MIT, Mysore 51

EXPERIMENT NO. 5 Date:

DETERMINATION OF CHEMICAL OXYGEN DEMAND (COD) OF THE

GIVEN INDUSTRIAL WASTE WATER SAMPLE

THEORY:

The chemical oxygen demand (COD) test is extensively employed for

the measurement of the pollution strength of industrial wastes. Chemical
oxygen demand is a measure of the total quantity of oxygen required for
oxidation of organic compounds of wastes to CO2 and water by a strong
oxidising agent. This parameter is particularly valuable in surveys designed
to determine the control losses to sewer systems. Results may be obtained
within a relatively short time and measures taken to correct error on the day
they occur.
Waste water contains organic impurities which include straight chain
aliphatic and aromatic compounds, such as alcohols, acids, amines,
pyridine and other oxidisable materials. They are oxidise more effectively
when silver sulphate is added as a catalyst. But silver sulphate reacts with
chlorides in the waste water to form precipitates which are oxidised partially
by this procedure. This difficulty is overcome by adding mercuric sulphate to
the sample.

PROCEDURE:

I. PREPARATION OF STANDARD MOHR'S SALT OR FAS SOLUTION:

Weigh about 1.0 g of Mohr's salt crystals accurately using an

electronic balance and transfer the crystals into a clean 250ml standard
flask using a glass funnel. Dissolve the crystals by adding ½ t.t. of dilute
sulphuric acid and little distilled water. Make up the solution to the mark by
adding distilled water. Mix well for uniform concentration and calculate the
normality of Mohr's salt solution.
Dept. of Chemistry, MIT, Mysore 52

IV Blank titration or (FAS > < K2Cr2O 7)

Burette : Standard FAS solution

Conical flask : 25 ml of K2Cr2O 7 solution + 10 ml of 1:1 H2SO4
Indicator : 2 – 4 drops of ferrion indicator
End Point : Blue green to reddish brown colour

Volume of FAS solution

required for blank titration = V2 = Final B.R - Initial B.R

V2 = ________=________ml

Volume of K2Cr2O7 required for the oxidation

of organic compounds of waste water = V2 – V1 = _________ = ______ ml

1000 ml of 1 N of FAS = 1000 ml of 1N K2Cr2O7 solution = 8 gms of oxygen

8  ( a ) V2  V1 8x
V2 – V1 ml of (a) N FAS = X = =
1000 1000

X = __________g of oxygen

 Amount of O2 required to oxidise organic

compounds present in 25 ml of waste water = X = _______g

 Amount of O2 required to oxidize organic

X  1000
compounds present in 1000ml of waste water = Y =
25

= _________

Y = ________g

 COD of waste water = Y x 1000 = _________ x 1000

 COD of waste water = ______ mg of oxygen
Dept. of Chemistry, MIT, Mysore 53

II Determination of COD of waste water or back titration:

Pipette out 25 ml of the industrial wastewater and 25ml of potassium

dichromate solution into a clean conical flask. Add 10 ml of 1:1 sulphuric
acid containing silver sulphate and mercuric sulphate. Add 2 -4 drops of
ferroin indicator and titrate against standard Mohr’s salt solution taken in a
burette until blue-green colour changes to reddish-brown. Note down the
volume of Mohr’s salt solution added for unreacted potassium dichromate
solution (V1) and repeat the experiment to get concordant values. Using
blank titre value determines the volume of potassium dichromate required
to oxidise organic compounds and calculate the COD of the given industrial
waste water.

III. Blank titration or Mohr’s salt > < K2Cr2O7:

Pipette out 25ml of standard potassium dichromate solution into a

clean conical flask and add 10ml of 1:1 sulphuric acid. Add 2 – 4 drops of
ferrion indicator and titrate this against Mohr’s salt solution taken in a
burette until blue–green colour changes to reddish brown. Note down the
volume of Mohr’s salt solution required for blank titration (V2).

REACTIONS:

Industrial wastewater + oxidising agent heat

(organic compounds) (K2Cr2O7) H2 SO4 H2O + CO2

K2Cr2O7 +7H2SO4 + 6FeSO4 3Fe2(SO4)3 + K2 SO4 + Cr2 (SO4)3 + 7H2O

(Excess)

Ferric ion indicator complex (Fe3+ ) FAS ferroin indicator (Fe 2+ )

(Blue green) K2Cr2O7 (Reddish brown)

RESULT: The COD value of the given waste water= ______ mg of oxygen
Dept. of Chemistry, MIT, Mysore 54

OBSERVATIONS AND CALCULATIONS:

IV. Preparation of bleaching powder solution:

Weight of bleaching powder taken = W = __________g

V. Estimation of chlorine:

Burette : Standard hypo solution

Conical flask : 25 ml bleaching powder solution + One t.t. of 2% KI
+ 5ml of glacial acetic acid, shake well.
Indicator : 2 ml of freshly prepared starch.
End point : Disappearance of blue colour

Burette readings I II III

Final readings
Initial readings
Volume of hypo
run down in ml

 Volume of hypo required = V= _________ ml

NOTE: 1. Normality of hypo = 0.05 N

2. One g equivalent weight of chlorine = 35.46

 1000 ml of 1 N of hypo = one gm equivalent weight of chlorine (35.46)

. .
 V ml of 0.05 N hypo = X =

. .
=

X = ____________ g of chlorine

 Weight of chlorine present in 25 ml of bleaching powder solution = X =

___________g
Dept. of Chemistry, MIT, Mysore 55

EXPERIMENT NO. 6 Date:

ESTIMATION OF PERCENTAGE OF CHLORINE IN BLEACHING

POWDER USING STANDARD SODIUM THIOSULPHATE SOLUTION
(Iodometric method)
THEORY:
Bleaching powder is mainly, a mixture of calcium hypo chlorite
[Ca(OCl)2] and the basic chloride [CaCl2, Ca(OH)2.H2O]. The active part of the
bleaching powder is hypochlorite from which the chlorine is liberated for
bleaching powder. The available chlorine means the chlorine liberated by the
reaction of dilute acids and is expressed as the percentage by weight of the
bleaching powder.The available chlorine can be estimated by iodometric
method. The bleaching powder solution of suspension is treated with an
excess of potassium iodide and strongly acidified with acetic acid.

Ca(OCl2) + 2CH3COOH Ca(CH3COO)2 + H2O + Cl2

Cl2 + 2KI 2KCl + I2

The liberated iodine is treated with standard solution of hypo

2Na2S2O3 + I2 NaI + Na2S4O 6

I2 + Starch Starch - Iodide complex (Deep blue)

PROCEDURE:

I. PREPARATION OF STANDARD BLEACHING POWDER SOLUTION:

Weigh about 2 g of the bleaching powder accurately using an electronic

balance and transfer it into a clean mortar. Add a little water and rub the
mixture into a smooth paste. Add a little more water and mix with the
pestle, allow the mixture to settle and transfer the milky liquid into 250 ml
standard flask. Grind the residue with a little more water and repeat the
operation until complete sample has been transferred to the flask in a state
of very fine suspension. Makeup to the mark with distilled water and mix
well for uniform concentration.
Dept. of Chemistry, MIT, Mysore 56

 Weight of chlorine present in 250 ml of bleaching powder solution =

X x 250
Y=
25

x 250
Y= 25

Y =__________ g

 Percentage of chlorine in the given bleaching powder sample

=
( )

= __________________

= ________
Dept. of Chemistry, MIT, Mysore 57

II ESTIMATION OF CHLORINE:

Pipette out 25 ml of bleaching powder solution into a clean conical

flask and add 10ml of 2% KI solution. Add 5ml of glacial acetic acid and
titrate the liberated iodine against standard sodium thiosulphate solution
taken in a burette using starch as indicator towards the end point.
Disappearance of blue colour is the end point. Note down the volume of
hypo added and repeat the experiment for concordant values. Calculate the
percentage of chlorine in the given bleaching powder.

Result: Percentage of chlorine in the given bleaching powder is ……….

Dept. of Chemistry, MIT, Mysore 58
VIVA QUESTIONS
Part-A
1. What is weak acid ?
2. What is pKa of a weak acid ?
3. Define pH.
4. What is Ka?
5. How are pH and pKa related?
6. What are the electrodes used in the measurement of pH for the determination of pKa?
7. Why half equivalent point is taking for calculating pKa value of weak acid?
8. What is viscosity?
9. What is viscosity coefficient of a liquid?
10. What is the SI unit of viscosity coefficient?
11. How does the viscosity vary with temperature?
12. Write the expression used to calculate the viscosity coefficient of liquid.
13. Why is the same volume of water and liquid used in the determination of viscosity?
coefficient of liquid?
14. Which reference electrode is used in the determination of ferrous ammonium sulphate
potent metrically?
15. What is meant by transmittance?
16. What is absorbance?
17. Define Bear – Lambert’s law.
18. What is the relation between absorbance and concentration?
19. What is a blank solution?
20. Which compound of copper is responsible for the deep blue colour in the colorimetric
determination of copper?
21. Why is ammonia added to copper sulphate solution in the colorimetric determination of
copper?
22. Why is the estimation of copper done at 620 nm wavelengths?
23. What is the wave length used in the colorimetric determination of iron?
24. Why is potassium thiocyanate solution added to ferric alum solution in the colorimetric
determination of iron?
25. Which compound of iron is responsible for the red colour in the colorimetric
determination of iron?
26. What is conductance?
27. What is the unit for conductance?
28. What is emf of the cell?
29. What is cell constant? Mention its unit.
30. Why is conductance of HCI decreases on adding NaOH before the end point?
31. Why is the conductance of HCI increases on adding NaOH after the end point?
32. What is an electrolyte?
33. What are types of electrolyte? And give example for each?

Part-B
1. What is an acid and base?
2. What is meant by titration?
3. What is end point?
4. What is a standard solution?
5. What is standardization?
6. What is estimation?
7. Define normality.
8. Define molarity.
10. What is an indicator? And mention the different types of indicators.
11. What is an oxidation and reduction?
12. What is an oxidising and reducing agents?
13. What is an hard water?
14. How is hardness of water caused?
15. What are the types of hard water?
Dept. of Chemistry, MIT, Mysore 59
16. What are the causes of temporary and permanent hardness of water?
17. How is temporary and permanent hardness of water removed?
18. How do you express the total hardness of water?
19. Name the metal ion indicator.
20. What is EDTA?
21. What are buffer solutions?
22. Mention types of buffer solutions.
23. Whyisammonia-sodiumhloridebuffer solution is added in the determination of total
hardness of water?
24. What is the end point in the determination of total hardness of water?
25. What are the constituents of cement?
26. Which indicator used in the determination of CaO in cement solution?
27. Why the diethylamine and glycerol added to the cement solution?
28. What is an ore?
29. What is the main constituent of haematite ore?
30. What is the role of stannous chloride in the determination of iron in haematite ore
solution?
31. Why is mercuric chloride added in the determination of iron in haematite ore solution?
32. What happens when the excess of stannous chloride is not removed in the
determination iron in haematite ore solution?
33. What is the indicator used in the determination of iron in haematite ore solution?
34. Whyis potassium ferricyanide cannot be used as an internal indicator in the analysis of
haematite ore?
35. What is the colour of K3[Fe(CN6] with ferrous ion?
36. Why is the colour of the indicator drop remains the same at the end point in the
determination of iron in haematite ore?
37. What is an alloy?
38. What are the constituents of brass?
39. How is a brass solution prepared?
40. What is the purpose of adding urea to the brass solution?
41. Why is ammonium hydroxide added to the brass solution in the determination of copper?
42. Why is acetic acid added to the brass solution in the determination of copper?
43. Why is KI added to the brass solution although copper is present in brass solution?
44. Why is the blue solution of brass turns brown upon the addition of KI solution?
45. Why is starch indicator added towards the endpoint in iodometric titrations?
46. What is the white precipitate left at the end point in the determination of copper in
brass?
47. What is hypo?
48. What is Mohr’s salt?
49. What are the salts present in Mohr’s salt?
50. Why is sulphuric acid added during the preparation of Mohr’s salt solution?
51. What is a hydrolysis?
52. What is chemical oxygen demand (COD)?
53. What is biological oxygen demand (BOD)?
54. What is the role of silver sulphate in the determination of COD?
55. What is role mercuric sulphate in the determination COD?
56. What is the indicator used in COD experiment?
57. What is the colour change at the end point in the determination of COD?
58. Why COD value always greater then BOD value.
59. What is the chemical name of bleaching powder?
60. How to prepare bleaching powder?
61. Which ions are present in bleaching powder solution?
62. How to estimate available chlorine in bleaching powder?
63. What happens when bleaching powder reacts with water?
64. Why is starch used in the estimation of chlorine in bleaching powder?
65. Give any two commercial uses of bleaching powder.
Dept. of Chemistry, MIT, Mysore 60

SCHEME OF VALUATION
DESCRIPTION Part-A Part-B Max. marks
Procedure write up 08 07 15
Conduction 26 26 52
Calculation, graph 09 09 18
works and Result
Viva- Voice 07 08 15

Part A
Potentiometry, Colorimetry Pka and Viscosity Conductometry
and Flame Photometry
Error (cm3) Marks Error (cm3) Marks Error (cm3) Marks
±0.5 13 + 13 ±5 13 + 13 ±0.5 13 + 13
±0.5 to 0.6 11 + 11 ±5.1 to 6 11 + 11 ±0.51 to 0.6 11 + 11
±0.6 to 0.7 9+9 ±6.1 to 7 9+9 ±0.61 to 0.7 9+9
±0.7 to 0.8 7+7 ±7.1 to 8 7+7 ±0.71 to 0.8 7+7
±0.8 to 1.0 5+5 ±8.1 to 10 5+5 ±0.81 to 1.0 5+5

> ± 1.0 Zero > ± 10 Zero > ±1.0 Zero

Graph:5 Pka: Two Graphs: 5+3 Graph: 4

Calculation: 3 Calculation: 4
Viscosity: 8

Part B
Total hardness, CaO in cement, Cu in Brass, Fe in Haematite and
COD
Error (cm3) Marks
±0.2 13 + 13
±0.3 11 + 11
±0.4 9+9
±0.5 7+7
± 0.6 5+5
> 0.6 Zero
Calculation: 08
Note: Best TWO TITRE values should be considered for valuation
Overwritten values are not considered for valuation.