Engineering Chemistry

Laboratory Manual

Department of Chemistry
GITAM Institute of Technology

GITAM
(Deemed to be University)
Accredited by NAAC with ‘A+’ Grade

Visakhapatnam – Hyderabad – Bengaluru

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 INDEX

1. General Instructions 05

2. Introduction 06

3. Description of apparatus used in titrimetry 09

4. Determination of sodium carbonate in soda ash 13

5. Determination of Iron(II) using potassium permanganate 16

6. Estimation of calcium in Portland cement 19

7. Determination of volume strength of hydrogen peroxide 22

8. Determination of chromium(VI) using ferrous ammonium sulphate 24

9. Determination of copper(II) using sodium thiosulphate 27

10. Estimation of active chlorine content in Bleaching powder 31

11. Determination of hardness of a water sample 34

12. Determination of viscosity of a liquid 37

13. Determination of surface tension of a liquid 39

14. Determination of Iron(II) by potentiometric method 41

15. Determination of strength of an acid by pH – metric method 44

16. Estimation of Zinc In Zinc ore by EDTA Method 47

17. Determination of sulphuric acid present in Lead acid storage battery

through acid base Titration. 50

18. Preparation of Urea Formaldehyde And Phenol Formaldehyde Resin 52

19. Preparation of Phenol formaldehyde resin 54

20. Synthesis of Titanium dioxide nanoparticles 56

21. Synthesis and characterization of Nano-sized ZnO by precipitation method 57

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 1. GENERAL INSTRUCTIONS
1. Study theory behind the experiment before attending the Laboratory.

2. Keep the work bench and sink (wash basin) neat and clean. Do not allow used filter
papers, broken pieces of glass, used match sticks, etc., to lie on the work bench –
throw them into the available dust bin nearby.

3. Keep the apparatus clean and arrange them properly.

4. Handle the chemicals and reagent bottles carefully.

5. Take the prescribed quantities of chemicals and reagents only.

6. Do not pour any excess reagent, taken by chance, back into the reagent bottle, as it
is likely to contaminate the entire solution in the reagent bottle.

7. Close the reagent bottles with their lids and keep them in their proper places, after
use.

8. Water is a precious commodity; do not waste it; close the water tap immediately
after use.

9. It is said, ‘Prevention is better than cure’ - take care to prevent fire accidents in the
Lab.

10. If any piece of apparatus is broken, promptly bring it to the notice of either Staff
Members or Lab Assistant.

11. Make it a habit to record all observations in your Observation Note Book, as and
when you carry out an experiment; writing observations on loose bits of paper is a
bad habit.

12. Do not forget to bring your Laboratory Record while attending the lab.

13. Always wear shoes and laboratory apron while you are in the lab.

14. Wash chemical spills on your body, if any, immediately with plenty of tap water.

15. Before leaving the Laboratory, wash the apparatus clean, keep them in proper place
and make your work bench tidy.

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 2. INTRODUCTION
The objective of a chemical analysis is to detect and identify different constituents
present and finally determine their relative amounts in a substance. The process of
detection and identification is commonly known as Qualitative Chemical Analysis
(Qualitative Analysis) while the determination of the amounts of the constituents as
Quantitative Chemical Analysis (Quantitative Analysis). Depending upon the technique
used for the determination of the amount, the quantitative chemical analysis can be broadly
divided into Gravimetric Analysis and Titrimetric (Volumetric) Analysis; the name
Titrimetric Analysis is preferred over Volumetric Analysis as the later, now a day, means
determination of volume of a gas evolved in a chemical reaction.

Gravimetric analysis is the process of isolating and weighing an element or a definite

compound of the element in a pure form. The element or compound is precipitated from
the solution of a weighed portion of the substance being examined. On the other hand,
titrimetric analysis essentially consists in determining the volume of a solution of accurately
known concentration which is required to react quantitatively with a known volume of the
solution of the substance being determined. A solution of accurately known strength
(concentration) is called the Standard solution; it contains a definite number of gram
equivalents or gram moles per liter of the solvent. The weight of the constituent aimed to
be determined is then calculated from the volume of the standard solution consumed and
known laws of chemical equivalence. Generally, a standard solution is prepared by
dissolving a primary standard substance in water (solvent). In order to serve as a primary
standard substance, it has to satisfy the following requirements:

a) It must be easy to obtain, to purify, to dry (preferably at 110 - 1200 C), and to
preserve in a pure state.

b) The substance should be unaltered in air during weighing; it should not be

hygroscopic, efflorescent, oxidized by air or affected otherwise.

c) It must be a high purity substance; impurities should not exceed 0.01 – 0.02 per cent.

d) It should have reasonably high equivalent weight so that the weighing errors are
negligible.

e) It should be readily soluble under conditions it is employed.

f) The reaction of the standard solution with the analyte solution should be
stoichiometric and practically instantaneous.

In practice, an ideal primary standard substance which satisfies all the above criteria is
difficult to obtain and a compromise between the above ideal requirements is usually
necessary. Some of the commonly employed primary standard substances are: Na2CO3, KCl,
K2Cr2O7, Na2C2O4, KBrO3, KIO3, (NH4)2 Ce(NO3)6, and As2O3. Hydrated salts, as a rule, do not
make good standards, because of the difficulty of efficient drying. However, salts which do
not effloresce, such as oxalic acid H2C2O4 2H2O and copper sulphate CuSO4 5H2O are found
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to be satisfactory secondary standards. The solutions prepared from less stable compounds
need to be standardized using a primary standard solution before use.

The Standard Solution (Titrant) is usually added from a burette. The process of adding
the standard solution to the analyte (titrand) solution taken in the conical flask
(titration/reaction vessel) until the reaction is just complete is termed as Titration. The
point at which the reaction is just complete is called Equivalence Point or Theoretical (or
Stoichiometric) End Point. The completion of the reaction should be detectable by some
change, unmistakable to the eye, produced by the standard solution itself (e.g., KMnO4) or
more usually by the addition of an auxiliary reagent, known as Indicator. After the reaction
is practically complete, the indicator would give a clear visual change (colour change or
formation of turbidity) in the solution being titrated (titrand/analyte). The point at which
this occurs is called the End Point of the titration.

For the purpose of discussion, the titrimetric analysis can be divided into four main types:

1. Neutralisation reactions or Acidimetry and Alkalimetry. These include the titration of

free bases or those formed by hydrolysis of salts of weak acids, with a standard acid
(Acidimetry) as well as the titration of free acids, or those formed by the hydrolysis of salts
of weak bases with a standard base (Alkalimetry). In these reactions, hydrogen and
hydroxide ions combine to form water.
H+ + OH- H2O
HCl + NaOH NaCl + H2O

2. Oxidation – reduction or Redox reactions. These are the reactions involving change in
oxidation number or transfer of electrons among the reacting substances. In these
reactions, the substance which loses electrons is called a Reducing agent or Reductant
while that which gains electrons an Oxidising agent or Oxidant; the overall reaction
between the reductant and the oxidant is called Redox reaction.

2 FeIII Cl3 + SnII Cl2 2FeIICl2 + SnIV Cl4

Oxidant Reductant

3. Complex formation reactions. These depend upon the combination of ions or molecules,
other than hydrogen and hydroxide ions, to form a soluble, slightly dissociated ion or
compound.
CuSO4 + 4KCN K2[Cu(CN)4] (Complex) + K2SO4

Ag+ + 2CN- [Ag(CN)2]- (Complex)

4. Precipitation reactions. These reactions involve precipitation of sparingly soluble

compounds from solutions of the two reactants.

AgNO3 + NaCl AgCl + NaNO3

Solution Solution Precipitate Solution

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 Usually, the strength of a solution is expressed either in Molarity or in Normality. A
molar solution (1M) is one which contains one gram molecular weight (gram mole) of the
reagent per liter of the solution. Similarly, a normal solution (1N) of a substance contains
one gram equivalent weight of it per liter of the solution. Even though the gram molecular
weight of a reagent does not vary, the gram equivalent weight varies with the type of the
reaction; the same compound possesses different gram equivalent weights in different
contexts.

In neutralization reactions, the gram equivalent weight of an acid is obtained by

dividing the gram molecular weight of it by the number of replaceable hydrogen ions that it
contains. For example, the gram equivalent weight of HCl is its gram molecular weight
divided by 1 (36.45/1), while that for H2SO4 is its gram molecular weight divided by 2 (98/2
= 49). Similarly, the gram equivalent weight of a base is obtained by dividing its molecular
weight by the number of replaceable hydroxide ions that it contains. For example, the gram
equivalent of Ba(OH)2 is its gram molecular weight divided by 2, as it contains two
replaceable hydroxide ions.

With reference to redox reactions, the gram equivalent weight of an oxidant is

obtained by dividing its gram molecular weight by the number of electrons that it gains
while that of a reductant by dividing its gram molecular weight by the number of electrons it
loses in the reaction. For example, thallous chloride (TlCl) is a reductant and thallium (I)
loses two electrons in the process of oxidation and hence its gram equivalent weight is
obtained by dividing its gram molecular weight by 2 (239.83/2 = 119.92). The case of KMnO4
is very interesting: as an oxidant, it may gain one, three, four or five electrons depending
upon the condition of the reaction medium and the reductant; accordingly its gram
equivalent weight varies as 158/1, 158/3, 158/4 and 158/5 respectively.

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 3. DESCRIPTION OF APPARATUS USED IN TITRIMETRY
(VOLUMETRY)
While carrying out experiments in titrimetric analysis in the Chemistry Lab, you are
going to use the following glass apparatus.

Burette: The commonly used laboratory burette (Fig. 1) is a long glass tube of uniform bore
throughout its length. It has a holding capacity of 50 mL and is graduated up to 1/10th of a
milliliter, from top to bottom. At its lower end, a stopcock with nozzle is fixed to facilitate
control of flow of a solution at the desired rate. You have to note the following points
whenever you use a burette.

a) The burette should always be kept absolutely clean. For this purpose, it should be
cleaned with chromic acid, thoroughly washed with tap water and then rinsed with
distilled water.

b) Before starting the titration, it should be rinsed with the standard solution, filled
with the same solution up to the zero mark, taking care to avoid air gaps in the
nozzle and air bubbles in the stem and then fixed to burette stand, vertically (Fig. 2).

c) While noting down the burette readings, the lower meniscus of the solution in the
burette has to be kept at the eye level to avoid parallax error; with dark coloured
solutions like potassium permanganate, the lower meniscus may not be clearly
visible and in such instances the upper meniscus is the choice.

Volumetric or transfer or single mark Pipette: It is a long narrow tube having cylindrical
bulb in the middle, tapering into a fine nozzle at its lower end and an etched circular mark a
little above the bulb on the upper truncated end. The volume of liquid delivered on starting
from the etched mark to the tip of the nozzle is printed on the bulb of the pipette, in
milliliters. As it is useful in transferring the same volume of a liquid always, it is called single
mark pipette
(Fig.3). Caution: Do not blow off the little amount of liquid that remains at the tip of the
nozzle, after transfer.

Volumetric Flask: A volumetric flask is a flat-bottomed, pear shaped vessel with a long
narrow neck fitted with leak proof lid at the top (Fig. 5B). A thin line etched around the neck
indicates the volume that it holds at a certain definite temperature (both the capacity and
temperature are clearly marked on the flask). It is used in preparation of standard solutions
and dilution of a sample to a definite volume. Flasks with capacities ranging from 5mL to 2
Liters are in use.

Graduated pipette: It is similar to a burette with a nozzle, but lacks a stopcock (Fig. 4). The
regulation of flow of a liquid can be manipulated with forefinger kept at its top end. Just like
a burette, it is useful in transferring variable volumes. There are pipettes with different total
capacities starting from 1 mL and above.

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Measuring Jar or Measuring Cylinder: This is a cylindrical jar provided with a sturdy base. It
is graduated from bottom to top (Fig. 6). Usually, the cross-sectional area of the cylinder is
relatively large and hence is useful for transfer of approximate volumes of reagents only.
Jars with holding capacity ranging from 10mL to 2 Liters are available.

Beaker: Beaker is a flat bottomed wide cylinder with or without a spout at the top (rim)
(Fig. 7). Beakers with capacities ranging from 5mL to 2 Liter are in use. However, 250mL and
400 mL beakers are more common in student laboratories. They are useful in preparation
and handling of reagents, titrimetric and gravimetric analysis.

Conical flask or Erlenmeyer’s Flask: It is a cone shaped flask mostly used as a reaction
vessel in carrying out a titration (Fig. 5A). Even though flasks with capacities ranging from 10
mL to 1 Liter are available, 250mL and 500mL flasks are more commonly used.

Wash Bottle: A wash bottle is a flat bottomed flask designed to deliver a fine jet of distilled
water or other liquid. This is used as a small size reservoir for storing and transfer of distilled
water. It finds wide application in cleaning laboratory ware also. Both glass and squeeze
type polythene bottles (Fig. 8) are known but, the latter type finds wider application. They
are available from 100mL to 1 Liter capacities.

Glazed Tile: It is a ceramic plate glazed white on one side. It helps to perceive the colour
change at the end point of a titration by providing a glossy white back ground.

Pictures of Some Apparatus and Equipment Used in the Lab

Fig. 1: Burette Fig. 2: Burette and Clamp fixed

to Stand

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 Fig. 4: Graduated A B C
Fig. 3: Volumetric Pipette Fig. 5: Different types of Flasks
Pipettes A - Conical Flask; B - Volumetric Flask;
C – Round bottomed flask.

Fig. 6: Measuring Cylinders Fig. 7: Beaker Fig. 8: Polythene Wash Bottles

Fig. 9: Ostwald’s Viscometer Fig. 10: Stalagmometer Fig. 11: Watch Glass

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Fig. 12: Digital Potentiometer connected to Indicator and Reference Electrodes placed in
Analyte solution

Fig. 13: Titration vessel & double junction electrode as connected to Digital pH meter

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 4. DETERMINATION OF SODIUM CARBONATE IN
SODA ASH
AIM: To determine the amount of Na2CO3 present in the given 100mL sample solution
using standard HCl solution.

APPARATUS: 50mL burette, burette stand and clamp, 10mL pipette, 250mL conical flask,
250 mL beaker, glazed tile, measuring jar, etc.

REAGENTS: Standard Na2CO3 solution, HCl solution, soda ash sample solution and Methyl
orange indicator solution.

THEORY: Anhydrous Na2CO3, known as soda ash, is a salt formed from H2CO3, a very weak
acid and NaOH, a strong base. Determination of Na2CO3 with a strong acid is a
neutralization type of chemical reaction. In this reaction, two moles of HCl are consumed by
one mole of Na2CO3 ; in fact, the base liberated by the hydrolysis of Na2CO3 is neutralised
with HCl.

2HCl + Na2CO3 2NaCl + H2O + CO2

Methyl orange is used as internal indicator in this titration and its colour transition
from yellow to orange red takes place in the pH-range of 3.1 to 4.4; the indicator exhibits
yellow colour having pH greater than 4.4 and pink colour having pH less than 3.1. As the pH-
transition of the said titration at the equivalence point also comes in this range, methyl
orange suites as an internal indicator in the present context.

PART-A
STANDARDIZATION OF HCl SOLUTION USING STANDARD SOLUTION OF Na2CO3

All the given glass apparatus are washed thoroughly with tap water, rinsed with
distilled water and the washings and rinsings are thrown out into the sink. The burette is
first rinsed with the given HCl solution and then filled with the same solution up to the zero
mark without any air bubbles. The burette is then clamped to burette stand. The pipette is
rinsed with the given standard Na2CO3 solution and 10 mL of the Na2CO3 solution is pipetted
out into a clean 250 mL conical flask. 30 mL of distilled water is added to the solution in the
conical flask using a 50 mL measuring jar and two drops of methyl orange indicator solution
is added to the conical flask. The solution attains yellow colour at this stage. The contents of
the conical flask are titrated against HCl solution taken in the burette. The titration is
continued until the colour of the solution in the conical flask changes from yellow to orange
red, which marks the end point of the titration. The burette readings are noted down to the
nearest 0.05 mL in Table-A. The titrations are repeated with fresh 10 mL portions of
standard sodium carbonate solution, following the above procedure, until two successive
titers are concordant. The data are entered in Table-A and the concentration of HCl solution
is calculated as shown under the Table – A.

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 Table-A: Standardisation of HCl solution using standard Na2CO3 solution

Volume of standard Burette readings, mL Volume of HCl

S.No. Na2CO3 solution rundown from
pipetted, mL Initial Final burette, mL
( V1) (V2)
1 10.00
2 10.00
3 10.00

CALCULATIONS: The concentration of HCl solution is calculated making use of the formula,

N 1 V1 = N 2 V 2 where

V1= Volume of Na2CO3 solution pipetted = 10.00 mL

V2 = Volume of HCl solution rundown from burette= mL
N1 = Normality of standard Na2CO3 solution =
N2 = Normality of HCl solution = (given)
As V1 , V2 and N1 are known, Normality of HCl solution is calculated as N2 = N 1 V1
V2
Therefore, the concentration of HCl solution, N2 = N

PART-B
DETERMINATION OF Na2CO3 IN THE GIVEN SODA ASH SAMPLE SOLUTION USING
STANDARD HCl SOLUTION

The soda ash sample solution, given in 100 mL volumetric flask, is made up to the
mark with distilled water. The solution is homogenized thoroughly by shaking, after closing
the volumetric flask with its lid. The burette is again filled with the standardized HCl solution
up to the zero mark and clamped to the burette stand. The pipette is washed with distilled
water and then rinsed with the given soda ash sample solution. Now 10 mL of the sample
solution is pipetted out into a clean 250 mL conical flask and 30 mL of distilled water is
added using a measuring jar, followed by 2 drops of methyl orange indicator. The solution is
yellow in colour at this stage. The contents of the conical flask are titrated against HCl
solution taken in the burette. The titration is continued until the colour of the solution in the
conical flask changes from yellow to orange red, which marks the end point. The readings of
the burette are noted down to the nearest 0.05 mL in table-B. The titrations are repeated
with fresh 10 mL portions till two successive titers are concordant. The results are entered
in Table–B and the concentration and amount of Na2CO3 in the given sample of soda ash
solution is calculated as shown under the Table – B.

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 Table-B: Determination of sodium carbonate in the given soda ash sample

S.No. Volume of soda ash Burette readings Volume of HCl

sample solution rundown from burette,
pipetted, mL Initial Final mL
( V3) (V2 )
1 10.00
2 10.00
3 10.00

CALCULATIONS: The strength of Na2CO3 in the sample is calculated by making use of the
formula,
N2 V2 = N3 V3 where,

V2 =Volume of HCl consumed for 10.00 mL of soda ash sample solution = mL

V3 =Volume of soda ash sample solution pipetted = 10.00 mL
N2 =Normality of HCl =
N3 = Normality of Na2CO3 in the soda ash sample solution, which can be calculated as
V2! , N2 and V3 are known.
N3 = N2 V2 =
V3
Therefore, the strength of Na2CO3 in the sample, N3 = N

Amount of Na2CO3 in the given sample (100 mL) = N3 x Eq.Wt. of Na2CO3 x 100 = N3 x 53
1000 10
= N3 x 5.3

Table: C Percentage Error Table

Roll/Regd. Number Flask Amount of Na2CO3 , g % Error

Number Given Reported

REPORT: Amount of Na2CO3 present in the given 100ml soda ash sample:__________gms.

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 5. DETERMINATION OF IRON(II) USING POTASSIUM
PERMANGANATE
AIM: To determine the amount of iron(II) present in the given sample solution using
standard potassium permanganate solution.

APPARATUS: 50 mL burette, burette stand & clamp, 250 mL conical flask, glazed tile, 10 mL
pipette, 100 mL volumetric flask, 50 mL measuring jar, beaker and wash
bottle.

CHEMICALS REQUIRED: Standard oxalic acid solution, potassium permanganate solution,

iron(II) test sample solution and 1:1 H2SO4 solution.

INDICATOR: KMnO4 acts as a self indicator.

END POINTS: Colourless to permanent pale pink in Part-A and colourless/pale yellow to
permanent pale pink in Part-B

THEORY : Reaction between KMnO4 and Fe(II) is an example of a redox reaction where
Mn(VII) in KMnO4 oxidises Fe(II) to Fe(III) and itself gets reduced from Mn(VII) to
Mn(II)state. The titration is carried out in H2SO4 medium.

2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5 (O)

10FeSO4 + 5H2SO4 + 5 (O) 5 Fe2 (SO4)3 + 5H2O

----------------------------------------------------------------------------------------------------------------
2KMnO4 + 10FeSO4 + 8H2SO4 K2SO4 + 2MnSO4 + 5Fe2 (SO4)3 + 8H2O

According to the above equation 2 moles of KMnO4 react with 10 moles of FeSO4.
The self colour of KMnO4 solution is used to locate the end point. As potassium
permanganate is not a primary standard, its solution has to be standardised using standard
oxalic acid solution.

PART – A

STANDARDISATION OF KMnO4 SOLUTION BY USING STANDARD SOLUTION

OF MOHR’S SALT

All the glass apparatus are washed with tap water and rinsed with distilled water.
The burette is rinsed with the given KMnO4 solution and filled with the same solution up to
the zero mark, avoiding air bubbles in it. The pipette is rinsed with standard Mohr’s salt
solution and 10 mL of the same solution is pipetted out into a clean 250 mL conical flask. To
this 40 mL of distilled water and 5 mL of 1:1 dilute sulphuric acid solution are added. The
contents of the conical flask are titrated against potassium permanganate solution taken in
the burette until the colour of the solution in the conical flask changes from colourless/pale
yellow to permanent pale pink. The above process is repeated, each time pipetting 10 mL

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portions of standard Mohr’s salt solution, until two successive concurrent titers are
obtained. The results are entered in Table-A and the concentration of permanganate is
calculated as shown under table-A.

Table-A :
Standardisation of KMnO4 solution using standard Mohr’s Salt solution

S.No Volume of Mohr’s Salt Burette Readings Volume of KMnO4 solution

solution pipetted out , mL rundown from burette, mL
(V1) Initial Final (V2 )
1. 10.00
2. 10.00
3. 10.00

CALCULATIONS: The concentration of permanganate solution is calculated using the

equation,
N1V1 = N2V2 where,

N1 = Normality of standard Mohr’s Salt solution = (given)

V1 = Volume of Mohr’s Salt solution pipetted out = 10.00 mL
V2 = Volume of KMnO4 solution rundown from burette = mL and
N2 = Normality of KMnO4 solution
As N1 , V1 and V2 are known the normality of permanganate, N2 can be calculated as

N2 = N1V1 =
V2
Normality of KMnO4 solution N2 =

PART - B
DETERMINATION OF IRON(II) IN THE SAMPLE USING STANDARD KMnO4 SOLUTION

The given iron(II) sample solution in 100 mL volumetric flask is made up to the mark
with distilled water and it is homogenized properly. The burette is filled with KMnO4
solution and clamped to the burette stand. The pipette is first washed with distilled water
and then rinsed with the given iron(II) sample solution and 10 mL of the same solution is
pipetted out into a clean 250 mL conical flask. To this 40 mL of distilled water and 5 mL of
1:1 H2SO4 solutions are added. The contents of the conical flask are then directly titrated
against KMnO4 solution until the colour of the solution in the conical flask changes from
colourless to permanent pale pink. The burette readings are noted down to the nearest 0.05
mL in Table-B. The titrations are repeated with fresh 10 mL portions of iron(II) sample
solution until two successive concurrent titers are obtained. The results are entered in
Table–B and the concentration and amount of iron(II) in the sample solution are calculated
as shown under the Table – B.

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 Table-B :
Determination of iron(II) using standard potassium permanganate solution

S.No Volume of Fe(II) Burette Readings Volume of KMnO4

sample solution solution rundown from
pipetted out, mL Initial Final burette, mL
(V3) ( V2 )
1. 10.00
2. 10.00
3. 10.00

CALCULATIONS: The concentration of iron(II) in the sample solution is calculated from the
equation N2V21 = N3V3 where
N2 = Normality of KMnO4 solution =
V2 = Volume of KMnO4 rundown from burette = mL
V3 = Volume of iron(II) sample solution pipetted out = 10.00 mL and
N3 = Normality of iron(II) in sample solution.
Therefore, N3 = N2 V2 = N
V3
The amount of iron(II) present in the given sample of 100 mL = N3 x Eq. Wt. of Fe(II) x100
1000
= N3 x 55.85 = g
10

Table: C Percentage Error Table

Roll/Regd. Flask Amount of iron(II), g % Error

Number Number
Given Reported

REPORT: Amount of iron(II) present in the given 100 mL sample solution _________ g

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 6. ESTIMATION OF CALCIUM IN PORTLAND CEMENT
AIM: To estimate the amount of calcium (as oxide) present in the given 100 mL Portland
cement sample solution using standard solution of KMnO4.

APPARATUS: 50 mL burette, burette stand & clamp, 10 mL pipette, 250 mL conical flask,
beaker, 100 mL volumetric flask, measuring cylinder, glazed tile, wash bottle,
quantitative filter papers, etc.

CHEMICALS REQUIRED: Portland cement sample, HCl, Ammonium hydroxide, 6%

Ammonium oxalate, standard Oxalic acid, KMnO4 and 1:1 H2SO4
solutions.

INDICATOR: KMnO4 acts as a self indicator.

END POINT: Colourless to permanent pale pink.

THEORY: Portland cement, on boiling with dilute hydrochloric acid decomposes yielding
soluble chlorides of calcium, iron and aluminium and insoluble silica.

Portland cement + Dil. HCl Boiling CaCl2 + FeCl3 + AlCl3 + H2O + SiO2
Solid Solution Solution Ppt.

The solution containing the metal ions is separated from the insoluble silica (SiO2) by
filtration through a quantitative filter paper. Calcium in the filtrate is then selectively and
quantitatively precipitated as CaC2O4 at near neutral pH using ammonium oxalate,
(NH4)2C2O4 as precipitating agent. The CaC2O4 precipitate is then filtered through a
quantitative filter paper, freed from other metal ions by repeated washing with distilled
water and dissolved in dilute sulphuric acid. This dissolution results in the liberation of oxalic
acid from CaC2O4.

CaC2O4 + H2SO4 CaSO4 + H2C2O4

Precipitate Solution ------Solution---------

Further, it may be seen from the above stoichiometric reaction that the amount of
oxalic acid so liberated is equivalent to the amount of calcium initially present. The solution
is quantitatively transferred into a volumetric flask and made up to the mark with distilled
water and homogenized. An aliquot of this solution is used for the estimation of calcium in
Portland cement. The reaction between oxalic acid and potassium permanganate is an
example of a redox reaction and Mn(VII) in KMnO4 oxidizes the H2C2O4 to CO2 and itself
gets reduced from Mn(VII) to Mn(II) state in H2SO4 medium.

2KMnO4 + 3H2SO4 + 5H2C2O4 K2SO4 + 2MnSO4 + 8H2O + 10CO2

According to the above reaction 2 moles of KMnO4 react with 5 moles of H2C2O4. The
titration is initiated at a temperature of about 70 – 80oC. Although the reaction mixture is
heated to 70oC, the rate of reaction is initially slow but gets efficiently catalysed by the in-

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situ generated Mn+2 ions in the solution; Mn+2 acts as an auto catalyst. The self colour of
KMnO4 is used to locate the end point, as all other reactants and products are colourless;
KMnO4 acts as a self indicator. The given KMnO4 solution is first standardized using standard
oxalic acid solution as the former is not a primary standard.

PART – A
STANDARDISATION OF KMnO4 SOLUTION USING STANDARD OXALIC ACID SOLUTION

All the given glass apparatus are washed with tap water and then rinsed with distilled
water. The burette is rinsed with the given KMnO4 solution and is filled with the same
solution. Pipette is rinsed with the given standard oxalic acid solution and 10 mL of standard
oxalic acid solution is pipetted out into a clean 250 mL conical flask followed by the addition
of 45 mL distilled water and 5mL of 1:1 diluted H2SO4. The colourless contents of the conical
flask are heated to 70 – 80oC. Now the hot contents of the flask are titrated with KMnO4
solution, taking all the precautions until a permanent pale pink colour appears which
indicates the end point of the titration. The burette readings are noted in Table–A and
titrations are continued with 10 mL portions of oxalic acid until 2 successive titers are
concurrent. The burette readings are tabulated in Table–A and the concentration of KMnO4
solution calculated as shown under Table–A.

Table-A: Standardisation of KMnO4 solution with standard oxalic acid solution

S.No Volume of Oxalic acid Burette Readings Volume of KMnO4
solution pipetted out, mL solution rundown, mL
( V1 ) Initial Final ( V2 )

CALCULATIONS: The strength of KMnO4 solution is calculated using the equation,

N1V1 = N2V2 where
N1 = Normality of standard oxalic acid solution = (given)
V1 = Volume of oxalic acid pipetted out = 10.00 mL
V2 = Volume of KMnO4 solution rundown from burette = mL and
N2 = Normality of KMnO4 and N2 calculated as N2 = N1V1
V2
Therefore, normality of KMnO4 solution N2 =
PART- B
ESTIMATION OF CALCIUM IN PORTLAND CEMENT USING STANDARD KMnO4SOLUTION

PROCEDURE: The burette is filled with KMnO4 solution, the initial reading set to zero
without any air bubbles and clamped to the stand. Pipette is rinsed with the sample solution
prepared from calcium oxalate and 10 mL of the same solution is pipetted out into a clean
250 mL conical flask. To this 45 mL of distilled water and 5mL of 1:1 diluted H2SO4 are added
and the solution is heated to about 70 – 80oC. The hot contents of the conical flask are then
titrated against KMnO4 solution taken in the burette, until the colour of the solution

- 20 -
changes from colourless to permanent pale pink. The burette readings are noted down to
the nearest 0.05 mL in Table–B. The above process is repeated with fresh 10 mL portions
obtained from the cement sample until two successive titers are concurrent. The results are
also entered in Table-B. The final calculations are carried out as shown under Table – B and
the amount of calcium reported in terms of CaO.

Table-B: Estimation of calcium in Portland cement with standard solution of KMnO4

S.No Volume of Sample solution Burette Readings Volume of KMnO4

pipetted out, mL solution rundown
(V3) Initial Final from burette, mL
( V 2)
1. 10.00
2. 10.00
3. 10.00

CALCULATIONS: The concentration of oxalic acid in the sample solution obtained from
calcium fraction is calculated using the equation,
N2V2l = N3V3 where,
N2 = Normality KMnO4 =
V2 = Volume of KMnO4 rundown = mL
V3 = Volume of Sample solution Pipetted = mL and
N3 = Normality of oxalic acid in Sample solution
Therefore, N3 = N2V2
V3
From the balanced chemical equations shown in the earlier part, it may be understood that
Normality of Calcium in the sample solution = Normality of oxalic acid in the sample
solution.

Equivalent weight of CaO = Mol.Wt.of CaO

2
Amount of Calcium present in the given 100ml Portland cement sample as expressed in
terms of CaO = Normality of H2C2O4in sample x Eq.Wt.of CaO x 100 = N3 x 2.804
1000
Table: C Percentage Error Table
Roll/Regd. No. Flask No. Amount of Ca present as CaO, g % Error
Given Reported

REPORT: The amount of calcium, as CaO, present in the given sample of cement = g

-----00000-----

- 21 -
 7. DETERMINATION OF VOLUME STRENGTH OF
HYDROGEN PEROXIDE
AIM: To determine the amount and volume strength of H2O2 present in the given sample
solution using standard KMnO4 solution.

APPARATUS : 50 mL burette, burette stand and clamp, 250 mL conical flask, glazed tile,
10 mL pipette, 100 mL volumetric flask, wash bottle, beaker, measuring jar,
etc.

CHEMICALS REQUIRED: Standard oxalic acid, KMnO4, H2O2 and 5N sulphuric acid solutions.

INDICATOR: KMnO4 serves as a self indicator

END POINT: Colourless to permanent pale pink

THEORY: The reaction between H2O2 and KMnO4 is also an example of a redox reaction
wherein KMnO4 oxidizes hydrogen peroxide to water and oxygen; Mn(VII) in permanganate
gets reduced to Mn(II) state, in the process.

2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5 (O)

5H2O2 + 5(O) 5H2O + 5O2

----------------------------------------------------------------------------------------------------------
2KMnO4 + 3H2SO4 + 5H2O2 K2SO4 + 2MnS4 + 5O2 + 8H2O

According to the above equation 5 moles of H2O2 react with 2 moles of KMnO4. The
self colour of KMnO4 solution is used to locate the end point because all the other reactants
and products are almost colourless. Moreover, initially the rate of the reaction is very slow
and it gets catalyzed by the in-situ generated Mn+2 which acts as a catalyst and hence Mn+2
plays the role of an auto- catalyst in this reaction also.

DETERMINATION OF VOLUME STRENGTH OF HYDROGEN PEROXIDE USING STANDARD

KMnO4 SOLUTION
Procedure:
The given H2O2 sample solution is made up to the mark with distilled water in the
100 mL volumetric flask and homogenized properly. Burette is filled with KMnO4 solution.
Pipette is washed with tap water, rinsed with distilled water and then with H2O2 sample
solution. Now 10 mL of the sample solution is pipetted out into a clean 250 mL conical flask.
To this 40 mL of distilled water followed by 5 mL of 1:1 diluted H2SO4 are added. The
contents of the conical flask are titrated, at room temperature, against KMnO4 solution until
the colour of the solution changes from colourless to permanent pale pink. The burette
readings are noted down to the nearest 0.05 mL in the Table–B. The titrations are repeated
with fresh 10 mL aliquots of H2O2 until two successive titers are concurrent and the readings
are recorded in Table-B. The amount of H2O2 present in the given sample is calculated as
shown under Table–B.

- 22 -
 Table-A: Determination of volume strength of H2O2 using standard KMnO4 solution
S.No Volume of H2O2 Burette Readings Volume of KMnO4
solution pipetted, mL solution rundown
(V3) Initial Final from burette, mL
(V2)
1. 10.00
2. 10.00
3. 10.00

CALCULATIONS: The concentration of H2O2 in the sample, N3 , is calculated by substituting

the known values of N2, V2l, and V3 in the equation,
N3 = N2V2l / V3 where
N2 = Normality of KMnO4 solution=
V2 = Volume of KMnO4 rundown from burette = mL
V3 = Volume of H2O2 solution pipetted out = 10.00 mL and
N3 = Normality of H2O2
Therefore, the calculated concentration of H2O2 in the sample solution = N
Amount of H2O2 in 1 litre of solution = N3 x Eq.Wt. of H2O2 = N3 x 17.01 g = Y
The amount of H2O2 present in the given 100ml of H2O2 sample solution,
Z = Y x 100 =
1000
Calculation of volume strength of H2O2:

The basic chemical reaction and calculations involved are:

2H2O2 2H2O + O2
(2 Moles) (2Moles) (1 Mole)

Therefore, 2 moles of H2O2 give rise to 1 mole of O2 and it is also well known that 1 gm
mole of oxygen gas at STP occupies 22.4 liters. Therefore,

2 x 34.02 (=68.04) gm of H2O2 is equivalent to 22.4 liters of O2 or

1 gm of H2O2 is equivalent to 22.4 x 1 liters of O2 = 0.3292 Lt = X L
68.04
Volume strength of H2O2 = (Weight of H2O2 per L) x X = Y x X = Y x 0.3292 = Lt.

Table: B Percentage Error Table

Roll/Regd. Flask Amount of H2O2 , g % Error
No. No.

Given Reported

REPORT: The amount of H2O2 present in given 100ml sample solution, Z .

-----00000----

- 23 -
 8. DETERMINATION OF CHROMIUM(VI) USING
FERROUS AMMONIUM SULPHATE
AIM: To determine the amount of chromium(VI) present in the given sample solution using
ferrous ammonium sulphate solution of known concentration.

APPARATUS : 50 mL burette, stand & clamp, 10 mL pipette, 250 mL conical flask, 50 mL

measuring jar, beaker, 100 mL volumetric flask, glazed tile, wash bottle, etc.

CHEMICALS REQUIRED: Ferrous ammonium sulphate, standard potassium dichromate,

and 1:1 H2SO4 solutions and syrupy phosphoric acid (H3PO4).

INDICATOR: Diphenylamine (DPA)

END POINT: Bluish green to bluish violet

THEORY: The reaction between K2Cr2O7 and Fe(II) is another example of a redox reaction.
In the presence of H2SO4, K2Cr2O7 oxidises Fe(II) to Fe(III) and Cr(VI) in dichromate gets
reduced to Cr(III) state.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2 (SO4)3 + 4H2O + 3 (O)

6FeSO4 + 3H2SO4+ 3(O) 3Fe2(SO4)3 + 3H2O

---------------------------------------------------------------------------------------------------------------------
K2Cr2O7 + 6FeSO4 + 7H2SO4 K2SO4 + 3Fe2 (SO4)3 + 7H2O

According to the above reaction 1 mole of K2Cr2O7 reacts with 6 moles of FeSO4.
Diphenylamine (DPA) is used as internal indicator to locate the end point. Premature end
points result due to the closeness of redox potential of the indicator system to that of
Fe(III)/Fe(II) system. However stiochiometric end point can be achieved by adding syrupy
phosphoric acid to the reaction mixture; phosphoric acid removes ferric iron as phosphato
complex and thereby lowers the redox potential of Fe(III)/Fe(II) system, providing sufficient
difference in the redox potentials of the two systems concerned such that premature end
points are avoided. Therefore, in the presence of H3PO4 , once all the Fe(II) ions react
completely with dichromate, the next drop of dichromate oxidizes the indicator and the
oxidized form of the indicator is violet blue in colour. Hence the colour transition at the
end point is from bluish green to bluish violet.
As ferrous ammonium sulphate is not a primary standard, its solution has to be
standardized using a standard solution like that of potassium dichromate.

PART – A
STANDARDISATION OF IRON(II) SOLUTION USING STANDARD K2Cr2O7 SOLUTION

All the glass apparatus are washed with tap water first and then rinsed with distilled
water. The burette is rinsed with the given standard potassium dichromate solution and
filled with the same solution up to the zero mark without any air bubbles. It is clamped to
the burette stand. Pipette is rinsed with iron(II)) solution and 10 mL of the same solution is

- 24 -
pipetted out into a clean 250 mL conical flask. To this 40 mL of distilled water, 5 mL of 1:1
diluted H2SO4 and 3 mL of syrupy phosphoric acid are added followed by 2 drops DPA
indicator. The colourless solution in the conical flask is titrated against standard K2Cr2O7
solution until the colour changes from bluish green to bluish violet. The burette readings are
noted down to the nearest 0.05 mL in the Table–A. The titrations with 10 mL parts of iron(II)
solution are repeated until two successive concurrent titers are obtained and the readings
are entered in the same table. The concentration of iron(II) is calculated as shown under
Table-A.

Table-A: Standardisation of iron(II) using standard potassium dichromate solution

S.No Volume of Fe(II) Burette Readings Volume of

solution pipetted, mL K2Cr2O7 solution
(V2) Initial Final rundown from
burette, mL
(V1)
1.
2.
3.

CALCULATIONS: The concentration of iron(II) is calculated using the equation,

N1V1 = N2V2 where
N1 = Normality of K2Cr2O7 =
V1 = Volume of K2Cr2O7 rundown from burette= mL
V2 = Volume of Fe(II)solution pipetted out = mL and
N2 = Normality of Fe(II)solution, which can be calculated as, N2 = N1V1 =
V2
Therefore, Normality of Fe(II) solution N2 =

PART – B
DETERMINATION OF CHROMIUM(VI) IN THE SAMPLE SOLUITON USING STANDARD
IRON(II) SOLUTION

The given chromium(VI) sample solution in 100 mL volumetric flask is made up to the
mark with distilled water and shaken thoroughly for complete homogenization. The burette
is rinsed with the given chromium(VI) sample solution and filled with the same solution up
to zero mark avoiding air bubbles and clamped to the burette stand. 10 mL of iron(II)
solution is pipetted out into a clean 250 mL conical flask. To this 10 mL of distilled water, 5
mL of 1:1 diluted H2SO4 and 3 mL of syrupy phosphoric acid are added followed by 2 drops
of DPA indicator. The solution in the conical flask is titrated against chromium(VI) sample
solution taken in the burette until the colour of the solution changes from bluish green to
bluish violet and the burette readings are noted down to the nearest 0.05 mL in Table B.
Titrations with fresh 10.0 mL aliquots of iron(II) are repeated following the above procedure
until two successive concurrent titers are obtained and the readings are also noted down in
Table-B.

- 25 -
 Table-B: Determination of chromium(VI) with standard iron(II) solution

S.No Volume of iron(II) Burette Readings Volume of

sample solution Chromium(VI)
pipetted out, mL Initial Final solution rundown
( V2 ) from burette, mL
( V3 )
1.
2.
3.

CALCULATIONS : Finally the amount of chromium(VI) in the given sample solution is

Calculated using the formula,
N2V2 = N3V3 where
N2 = Normality of iron(II) solution=
V2 = Volume of iron(II) pipetted out= 10.00 mL
V3 = Volume of chromium(VI) rundown from burette =
N3 = Normality of chromium(VI) sample solution = N2V2
V3

Normality of chromium(VI) in the sample solution N3 =

Finally the amount of chromium(VI) present in the given sample solution is

calculated using the formula
N3 x Eq. Wt. of Cr(VI) x 100 = N3 x 17.33 = 1.733 x N3
1000 10

Table: C Percentage Error Table

Roll/Regd. No Flask No. Amount of Chromium(VI), g % Error
Given Reported

REPORT: The amount of Cr(VI) in the given sample solution is ________ gm.

-----00000----

- 26 -
 9. DETERMINATION OF COPPER(II) USING SODIUM
THIOSULPHATE
AIM : To determine the amount of copper(II) present in the given sample solution using
sodium thiosulphate (hypo) solution (IODOMETRIC METHOD).

APPARATUS: 250 mL conical flask, 50 mL burette, burette stand and clamp, glazed tile,
10 mL pipette, 100 mL volumetric flask, 50 mL measuring jar, Wash bottle, etc.

CHEMICALS REQUIRED: Standard copper sulphate solution, sodium thiosulphate (hypo),

and 10% potassium iodide solutions.

INDICATOR: 1 % Starch solution

END POINT: Blue to pale cream colour

THEORY: Copper(II) cannot be titrated with hypo as there is no direct reaction between
Cu(II) and hypo. However Copper(II) directly oxidizes iodide to iodine and the liberated
iodine can be titrated with sodium thiosulphate solution quantitatively. Therefore, Cu(II) is
indirectly estimated iodometrically by adding potassium iodide solution to Cu(II) solution
and titrating the liberated iodine with hypo provided, the Cu(II) solution is free from mineral
acids. The basic reactions involved are:

+2 +1
2CuSO4 + 4KI 2CuI + I 2 + 2 K2SO4
(Oxidant) (Reductant)

KI + I2 KI3 (Potassium triiodide)

KI3 + 2Na2S2O3 Na2S4O6 + 2NaI + KI

Oxidant Reductant Sodium
tetrathoinate

According to the above reaction, 2 equivalents of CuSO4 liberate 2 equivalents of

molecular iodine, which in turn oxidize 2 equivalents of Na2S2O3. If free mineral acids are
present as impurities in the Cu(II) solution, they cause interference in the above reaction; in
the presence of mineral acids, iodide gets oxidised to iodine by the dissolved oxygen present
in the medium. However the above interference can be overcome by adding a small amount
of Na2CO3 and dissolving the precipitated copper carbonate in dilute acetic acid; sodium
carbonate neutralizes the mineral acid and the slight excess of carbonate causes
precipitation of a small amount of CuCO3 which dissolves in dilute CH3COOH. As sodium
thiosulphate (Hypo) is not a primary standard its solution has to be standardized with a
primary standard solution like potassium iodate. But as copper(II) in the sample is to be
determined, and to avoid methodical errors, a standard solution of copper(II) is prepared
from Analytical Grade CuSO4.5H2O ( a secondary standard substance) to standardize hypo
solution.

- 27 -
 PART - A
STANDARDISATION OF HYPO USING STANDARD COPPER SULPHATE SOLUTION

All the given glass apparatus are washed with tap water and then rinsed with
distilled water. The burette is rinsed with hypo and filled with the same solution up to the
zero mark avoiding air bubbles and it is clamped to burette stand. The given standard
copper(II) solution is made up to the mark with distilled water and homogenized. The
pipette is rinsed with standard copper(II) solution and 10 mL of the same solution is
pipetted out into a clean 250 mL conical flask. To this sodium carbonate solution is added
drop wise until the solution becomes turbid. And then dilute Acetic acid (1:1) is added drop
wise to re-dissolve the precipitate obtained and the solution becomes the clear. To this 10
mL of 10 % KI solution is added. The blue Cu(II) solution becomes dark brown in color due to
the liberation of iodine. To this 30 ml of distilled water is added now and allowed to stand
for about two minutes to ensure complete liberation of iodine. Now the contents of the
conical flask are then titrated against hypo taken in the burette until it becomes straw
yellow in colour. Then 1 mL of starch indicator is added. The conical flask contents now
attains blue or violet colour. The titration with hypo is continued until the blue colour
disappears sharply with one drop addition of hypo. The burette readings are noted down to
the nearest 0.05 mL in Table-A. The above procedure is continued with fresh 10 mL portions
of copper(II) solution until two successive concurrent titers are obtained and the readings
are entered in Table-A.

Table-A: Standardisation of hypo with standard Cu(II) solution.

Volume of copper(II) Burette Readings Volume of hypo

S.NO solution pipetted, mL Rundown, mL
Initial Final
(V1) (V2)

CALCULATIONS: The concentration of hypo can be calculated using the equation,

V1N1 = V2 N2 where

V1 = Volume of standard Cu(II) solution pipetted = 10.00 mL

N1 = Normality of standard Cu(II) solution =
V2 = Volume of hypo solution rundown form burette =
N2 = Normality of hypo solution
Therefore, normality of hypo solution, N2 is calculated by substituting the known
values of N1, V1 and V2 in the equation, N2 = V1 N1 / V2

Concentration of Hypo solution, N2 = N

- 28 -
 PART - B
DETERMINATION OF COPPER (II) IN SAMPLE SOLUTION USING STANDARD HYPO
SOLUTION

The given sample of copper (II) solution is made up to the mark of the volumetric
flask by adding distilled water and homogenized. Burette is filled with the hypo solution up
to the zero mark avoiding air bubbles and clamped to the burette stand. 10 mL of copper(II)
sample solution is pipetted down into a clean 250 mL conical flask using a 10 mL pipette,
which was initially washed with tap water, distilled water and then rinsed with the
copper(II) sample solution, following the usual procedure. To this sodium carbonate solution
is added drop wise until the solution becomes turbid. And then dilute Acetic acid (1:1) is
added drop wise to re-dissolve the precipitate obtained and the solution becomes the clear.
To this 10 ml of 10% KI solution is added, immediately followed by 30 ml of distilled water
and the flask is closed the reaction is allowed to complete by giving 2 minutes time. Now the
contents of the conical flask is then titrated against hypo solution until it attains straw
yellow colour. At this stage 1 mL of starch indicator is added and the titration with hypo is
continued until the blue colour gets discharged with just 1 drop of hypo. The burette
readings are noted down to the nearest 0.05 mL in Table–B. The above procedure is
continued with 10 mL portions of sample solution until two successive concurrent titers are
obtained and the readings are also entered in Table-B.

Table-B: Determination of Copper(II) in the given sample solution

Volume of copper(II) Burette Readings Volume of hypo

S.NO sample solution rundown, mL
Initial Final
pipetted, mL (V3) (V2)

CALCULATIONS : The concentration of Cu(II) in the sample is calculated using the formula
V2l N2 = V3 N3 where

V 2= Volume of hypo rundown from burette =

N2 = Normality of hypo =
V3 = Volume of Cu(II) sample solution pipetted out =10.00 mL
and N3 = Normality of Cu(II) in sample solution

Therefore, [Cu(II)] in the sample, N3 = V2l N2 =

V3

Finally, the amount of Cu(II) present in the given sample is calculated using the formula,

= N3 x Eq.Wt. of Cu(II) x 100 = N3 x63.55 = 6.355 x N3 =

1000 10

- 29 -
 Table: C Percentage Error Table

Roll/Regd. No. Flask No. Amount of Copper(II), g % Error

Given Reported

REPORT: The amount of Copper(II) present in the sample solution is g.

-----00000----

- 30 -
 10. ESTIMATION OF ACTIVE CHLORINE CONTENT IN
BLEACHING POWDER
AIM: To estimate the amount of active chlorine content present in the given bleaching
powder sample using standard hypo solution (IODOMETRIC METHOD).

APPARATUS : 250 mL conical flask, 10 mL pipette, 50 mL burette, burette stand with clamp,
Glazed tile, 100 mL volumetric flask, measuring jar, wash bottle, etc.

CHEMICALS REQUIRED: Standard copper sulphate solution, 10 % KI solution, hypo solution,

glacial acetic acid and bleaching powder sample.

INDICATOR: 1% Starch solution

END POINT: blue to colourless

THEORY: The available chlorine content in a bleaching powder sample can be estimated
with hypo by iodometric method based on the redox reaction which involves the conversion
of elemental iodine to iodide ions as given by

I2 + 2e- 2I-

Bleaching powder contains a mixture of Ca(OCl)Cl and basic calcium chloride

CaCl2. Ca(OH)2 H2O. The active component of bleaching powder is hypochlorite ion which is
responsible for the bleaching action of bleaching powder. Bleaching powder hydrolyses in
water forming hypochlorous acid, which is a good disinfectant.

Ca (OCl)Cl + H2O Ca (OH)2 + Cl2

Cl2 + H2O HOCl + HCl

Hypochlorous acid
(Germicide)
Hypochlorous acid inactivates certain enzymes in the cells of microorganisms leading to
their death. Available chlorine in bleaching powder can be determined by treating a
suspension of bleaching powder in water with potassium iodide In presence of acetic acid,
which liberates active chlorine, which in turn liberates iodine from iodide quantitatively.

Ca(OCl)Cl + 2H+ Ca+2 + Cl2 + H2O

Cl2 + 2KI 2KCl + I2

Hence, available chlorine can be determined iodometrically by adding KI and acetic

acid to a suspension of the bleaching powder in distilled water. The liberated chlorine, in the
presence of acetic acid, releases iodine from potassium iodide solution quantitatively and
the liberated iodine is titrated against hypo solution of known concentration.

- 31 -
 I2 + 2Na2S2O3 Na2S4O6 + 2NaI
As the hypo solution is not a primary standard, it is standardized with standard
copper(II) solution, as was mentioned earlier.

PART – A
STANDARDISATION OF HYPO SOLUTION USING STANDARD COPPER(II) SOLUTION

The given glass apparatus are washed with tap water and then rinsed with distilled
water. Burette is rinsed with hypo solution and filled with the same solution up to the zero
mark without any air bubbles and clamped to the burette stand. Pipette is rinsed with
standard copper(II) solution and 10 mL of the same solution is pipetted out into a clean 250
mL conical flask. To this 10 mL of 10% KI solution is added immediately followed by 40 mL of
distilled water. The flask is closed with its lid and the reaction is allowed to complete by
giving 2 minutes time. Now the contents of the conical flask is titrated against hypo solution
taken in the burette until the solution turns straw yellow in colour. At this stage about 2 mL
of 1% starch indicator is added; the colour of the solution turns blue. The titration against
hypo is continued until the blue colour disappears with 1 drop addition of hypo. The burette
readings are noted down to the nearest 0.05 mL in Table A and the above process is
continued taking 10 mL aliquots of copper(II) solution until 2 successive concurrent titers
are obtained and the readings are entered in Table-A. From the known concentration of
copper(II) solution the concentration of hypo is calculated as shown under the same table.

Table-A: Standrdisation of hypo solution using standard copper(II) solution

S.No Volume of copper(II) Burette Readings Volume of hypo
solution pipetted out, mL solution rundown
(V1) Initial Final from burette, mL (V2)
1.
2.

CALCULATIONS: The concentration of hypo is calculated using the formula,

N1V1 = N2V2
where N1 = Normality of standard Cu(II) solution;
V1 = Volume of Cu(II) solution pipetted out = 10.00 mL;
V2 = Volume of hypo solution run down from burette and
N2 = Normality of hypo solution.
Therefore, the concentration of hypo, N2 = N1V1 / V2 = N

PART – B
ESTIMATION OF AVAILABLE CHLORINE CONTENT IN THE BLEACH USING STANDARD HYPO

The given bleaching powder sample solution in 100 mL volumetric flask is shaken
thoroughly for complete homogenization. The burette is filled with the hypo solution up to
the zero mark without any air bubbles and clamped to burette stand. The pipette is rinsed
with bleaching powder sample solution and 10 mL of the same solution is pipetted out into
a clean 250 mL conical flask. To this 10 mL of glacial acetic acid and 10 mL of 10% KI solution

- 32 -
are added followed by 40 mL of distilled water down the inner wall of the conical flask. The
contents of the conical flask are mixed well by swirling the conical flask. (Liberation of iodine
from potassium iodide by active chlorine is almost instantaneous.) The dark brown solution
in the conical flask is titrated against hypo solution taken in the burette until the colour of
the solution changes from dark brown to light yellow. At this stage 2 mL of 1% starch
indicator is added. The solution turns blue and the titration of the blue coloured solution
with hypo is continued until the blue colour of the solution disappears. The readings are
entered in Table-B. The above process is continued taking fresh 10 mL aliquots of the bleach
sample solution until two successive concurrent titers are obtained and the readings are
recorded in Table-B and the available chlorine content is calculated as shown under it.

Table-B: Estimation of available chlorine content in bleach

S.No Volume of bleach Burette Readings Volume of hypo

solution pipette, mL rundown from burette, mL
( V3) Initial Final ( V2)
1.
2.
3.

CALCULATION: The concentration of available chlorine is calculated using the equation,

N2V2 = N3V3 where
N2 = Normality of hypo solution =
V2 = Volume of hypo rundown from burette = mL
V3 = Volume of bleach sample solution pipetted out = 10.00 mL and
N3 = Normality of ‘Available Chlorine’ in bleaching powder sample solution, which is
calculated as N3 = N2V2 =
V3
Normality of available chlorine content in bleaching powder sample solution, N3 =

Available Chlorine present in 100 mL bleaching powder sample solution,

X = N3 x Eq. Wt. of Cl x 100
1000
= N3 X 35.45 / 10 = 3.545 x N3
Amount of bleach sample taken , Y = g
% of available Chlorine in bleaching powder = X x 100 =
Y
Table: C Percentage Error Table
Roll/Regd. Flask No. % of Available chlorine % Error
No.
Given Reported

REPORT: Percentage of available chlorine content in bleaching powder =

-----00000----

- 33 -
 11. DETERMINATION OF HARDNESS OF
A WATER SAMPLE
AIM: To determine the total hardness of an underground water sample using standard
EDTA solution.

APPARATUS : 50 mL burette, stand and clamp, glazed tile,10 mL pipette, 250 mL beakers,
50 mL measuring jar, 250 mL conical flask, 100 mL volumetric flask , wash
bottle, etc.

CHEMICALS REQUIRED: Standard zinc sulphate solution, EDTA solution, pH-10 buffer and
water sample.

INDICATIOR: EBT (Eriochrome Black – T)

END POINT: Wine red to blue.

THEORY: Hardness, soap consuming capacity, of water is mainly due to the presence of
bicarbonates, carbonates, sulphates, chlorides, and nitrates of calcium and magnesium.
When these metals are present as their bicarbonates in water, they cause temporary
hardness to water. When water containing these bicarbonates is boiled, the bicarbonates
are converted into their corresponding insoluble carbonate or hydroxides, as the case may
be, and hence can be removed by sedimentation or filtration. Sulphates, chlorides and
nitrates of calcium, magnesium, zinc, etc., cause permanent hardness to water which cannot
be removed by mere boiling. Conventionally, water hardness is expressed in terms of CaCO3
in parts per million (p p m). Hardness of water can be determined using standard EDTA
solution as titrant and EBT as indicator. NH4OH – NH4Cl buffer solution is added to maintain
a pH of 9-10, as EDTA forms stable complexes with calcium and magnesium at this pH. EBT
functions as a metal ion indicator to locate the end point by forming a relatively less stable
complex with metal ion compared to that formed by EDTA. In the present context, at the
equivalence point, once all the free calcium and magnesium ions in water are completely
removed by complexation with EDTA, the calcium and magnesium ions in Ca/Mg- EBT
complex get preferably complexed by EDTA as the latter is stronger ligand than EBT and the
EBT indicator is set free imparting blue color to the solution.
pH-10 At end point
Ca+2 / Mg +2 + EBT Ca+2 / Mg +2- EBT ( Ca/Mg – EDTA) + EBT
Blue (Wine-red coloured EDTA ( Colourless & more Blue
less stable complex) stable complex)

PART – A
STANDARDISTATION OF EDTA USING STANDARD ZINC SULPHATE SOLUTION

All the given glass apparatus are washed with tap water first and then rinsed with
distilled water. Burette is rinsed with EDTA solution and filled with the same solution up to
the zero mark without any air bubbles and then clamped to the burette stand. Pipette is first
rinsed with standard Zn(II) solution and 10 mL of it is pipetted out into a clean 250 mL

- 34 -
conical flask. To this solution, 30 mL of distilled water and 1 mL of pH - 10 Buffer solution,
followed by 2 drops of EBT indicator are added. The colour of the solution is wine red at this
stage. The solution is titrated against EDTA solution taken in the burette until the colour of
the solution turns from wine red to blue. The burette readings are noted down to the
nearest 0.05 mL in Table-A. The titrations are repeated taking fresh 10 mL aliquots of zinc(II)
solution and following the above procedure until two successive concordant titers are
obtained and the readings are recorded in Table-A.

Table-A: Standardisation of EDTA solution using standard zinc(II) solution.

Volume of standard Burette Readings Volume of EDTA

zinc(II) solution solution rundown
S.NO
pipetted out, mL Initial Final from burette, mL
(V1) (V2)
1
2
3

CACULATIONS: As zinc(II) and EDTA react in 1 : 1 mole ratio, the concentration of EDTA is
calculated using the formula,

V1 M1 = V2 M2
where,
V1 = Volume of Zn(II) solution pipette out = 10.00 mL
M1 = Molarity of Zn(II) solution =
V2 = Volume of EDTA solution rundown from the burette
and M2 = Molarity of EDTA solution

Therefore, Molarity of EDTA solution is calculated as, M2 = V1 M1 V2

PART – B

DETERMINATION OF TOTAL HARDNESS OF A WATER SAMPLE USING

STANDARD EDTA SOLUTION

The standardized EDTA solution in the burette is filled with the beaker containing
EDTA solution and the burette is washed with tap water and then rinsed with distilled
water. The burette is now rinsed with newly prepared standard 0.01 M EDTA solution and is
filled with the same solution up to the zero mark without any air bubbles and clamped to
the burette stand. 50 mL of water sample is taken into a clean 250 ml conical flask by
means of 50 mL measuring jar. To this 1 mL of buffer solution followed by 2 drops of EBT
indicator is added. The colour of the solution is wine red at this stage. This solution is
titrated against 0.01 M EDTA taken in the burette until the colour of the solution turns from
wine red to clear blue and the burette readings are noted down to the nearest 0.05 mL in
Table-B. The above process is continued with fresh 50 mL portions of water sample until two

- 35 -
successive concurrent titers are obtained and the readings are recorded in Table-B. The
hardness concentration in water sample is calculated and reported as shown under Table-B.

Table-B: Determination of hardness of a water sample using 0.01M EDTA solution

Volume of Burette Readings Volume of 0.01 M EDTA

water solution rundown from
S.NO.
sample, mL Initial Final burette, mL
(V4) (V3)
1. 50
2. 50
3. 50

CALCULATIONS: According to law of equivalence

V3 M3 = V4 M4
where,
V3 = Volume of 0.01 M EDTA rundown from the burette,
M3 = 0.01 M
M4 = Molarity of hardness in water and
V4 = Volume of water sample taken = 50 mL
Therefore hardness concentration in water, M4 = 0.01 x V3
50
Finally the total hardness of water sample is calculated using the formula,
M4 x Mol.Wt.of CaCO3x 1000 = M4 x 100 x 1000 = ppm

REPORT: The total hardness of water sample is ppm.

-----00000----

- 36 -
 12. DETERMINATION OF VISCOSITY OF A LIQUID
AIM: To determine the viscosity of the given liquid using Ostwald’s viscometer

APPARATUS: Ostwald’s viscometer, stop watch, specific gravity bottle, pipette, clean
flexible rubber tubing, pinch cock, etc.

REAGENTS: Distilled water and organic solvent.

THEORY: Determination of viscosity using Ostwald’s viscometer is based on Poiseuille’s

equation, which relates the rate of flow of a liquid through a capillary tube with the
coefficient of viscosity. The Poiseuille’s equation for viscosity can be expressed as:

   
η = (1)


where v is volume of the liquid (of viscosity η) flowing in time ‘t’ through a capillary tube of
radius ‘r’, and length ι, when a pressure difference ‘ρ‘ is maintained between the two ends
of the tube.

The determination of absolute viscosity by means of Poiseuille’s expression requires a

knowledge of v, r, t, ι and ρ. But in practice this method of determination of η is tedious.
Hence a simpler method of comparing the viscosities of two liquids can be followed. If t1 and
t2 are the flow times required for equal volume of two liquids to flow through the same
length of capillary tube, then

η 1/ η2 = ρ1 t1 / ρ2 t2 (2)

As ρ = h d g and h and g are constant under the conditions, equation (2) becomes

η 1/ η2 = d1 t1 / d2 t2 (3)

where d1 and d2 are the respective densities of the two liquids, and can be readily measured
or obtained.

PROCEDURE:

The viscometer (Fig. 9) is cleaned first with chromic acid, followed by tap water and
then with distilled water. It is finally washed with alcohol and ether and then dried. A piece
of clean rubber tubing is attached to the end ‘a’ and the viscometer is clamped to the stand
vertically. Sufficient volume of distilled water is introduced in bulb ‘e’ so that the bent
portion of the tube and half or a little more than half of bulb ‘e’ are filled up. With the help
of the rubber tube attached to the upper arm “a”, water is sucked until it raises much above
the upper mark “c” and is allowed to flow under its own weight. The time required for the

- 37 -
flow of water from ‘c ’ to ‘d ’ is noted using a stopwatch. The same procedure is repeated
three times, the data are entered in Table-1 and the mean value is calculated. The
viscometer is cleaned with alcohol and ether and dried. The same procedure is repeated
with an identical volume of the given liquid and the time of flow of liquid is measured and
the values are recorded in Table-1. The relative density of the given liquid is determined
using pycnometer.

Table - 1 : Determination relative viscosity of a liquid

Water Given liquid

Trial No. Time of Flow, t1 Time of Flow, t2
Seconds Seconds
1.
2.
3.
----------------------- ----------------------
Mean value

CALCULATIONS: Finally the relative viscosity of the given liquid, η2 is calculated by

substituting the known values of d1, d2 and η1 in the equation
η2 = η1 d2 t2 / d1 t1
where
η1 = Viscosity of water = poise
η2 = Viscosity of the given liquid = poise
d1 = Density of water= gm/cm3
d2 = Density of the given liquid = gm/cm3
t1 = Mean value of time of flow of water= sec
t2 = Mean value of time of flow of the given liquid= sec

Precautions
1. The viscometer should be thoroughly cleaned.
2. Viscometer must be kept in vertical position
3. Same volumes of liquid and water are to be taken while performing the experiment

REPORT: The relative viscosity of the given liquid with respect to water at room
temperature is ---------------- poise.

-----00000----

- 38 -
 13. DETERMINATION OF SURFACE TENSION OF
A GIVEN LIQUID
AIM: To determine the surface tension of the given liquid at room temperature using a
Stalagmometer.

APPARATUS: Stalagmometer, beaker, clean rubber tubing, pinch cock, relative density
bottle and thermometer.

REAGENTS: Distilled water and an organic solvent.

THEORY: Surface tension is a manifestation of the forces of attraction that hold the
molecules together in the liquid state; thus, liquid droplets tend to become spheres – the
form of least surface area – because of the mutual cohesion of the molecules. When a liquid
is allowed to flow down through a capillary tube, a drop is formed at its lower end. The drop
increases to a certain size and then falls down. The size of the drop formed 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 a liquid is based on the fact that the drop of
the liquid formed at the lower end of capillary falls down when the weight of the drop
becomes equal to the surface tension. The surface tension of the given liquid γ2 is
determined relative to that of water γ1 at room temperature by using stalagmometer. The
number of drops formed for the same volume of water and the given liquid are counted and
let they be n1 and n2 respectively. Now if the densities of water and the given liquid at room
temperature are determined separately using a specific gravity bottle, then the surface
tension γ2 of the given liquid can be calculated using the relationship

γ1/ γ2 = n2 d1/ n1 d2
where, d1 and d2 are the densities of water and the given liquid respectively.

PROCEDURE:

The stalagmometer is cleaned thoroughly first with chromic acid solution, tap water
and finally with distilled water, and then dried. The upper end of the stalagmometer is fitted
with a rubber tube and pinch cock set. The lower end of the stalagmometer is immersed in a
beaker containing distilled water. The distilled water is sucked into the stalagmometer until
the level rises a little above the mark ‘C’ and the pinchcock screw is tightened. The lower
end of the stalagmometer is raised much above the level of the distilled water in the beaker
and the stalagmometer is fixed to its stand vertically. By careful manipulation of the screw
of the pinch cock, the water in the stalagmometer is allowed to flow down at a rate of 15 –
20 drops per three minutes. Counting of the drops is started when the meniscus just
reaches the upper mark ‘C’ and stopped when the meniscus just passes the lower mark ‘D’

- 39 -
and the number of drops fallen down is noted in Table 1.The same procedure is repeated
thrice, the number of drops in each case and the mean of the three values is also recorded
in Table 1. The stalagmometer is once again cleaned and dried. The entire procedure is
repeated with the given sample liquid and the corresponding data also entered in Table1.
The density of the given liquid sample d2 is determined using a specific gravity bottle.

Table 1: Determination of surface tension of a liquid

Trial. No Distilled Water Given liquid

No. of drops, n1 No. of drops, n2
1.
2.
3.
-------------------- --------------------
Mean value

CALCULATIONS: As γ1 , n1 , d1 and d2 are known, the surface tension of the given liquid γ2 ,
is calculated using the formula,

γ2 = γ1 n1 d2 / n2 d1 where

γ1 = Surface tension of water = ………….. dynes/cm

γ2 = Surface tension of the given liquid =
n1 = Mean value of No. of drops of water =
n2 = Mean value of No. of drops of the given liquid =
d1= density of water = g/cm3
d2 = density of the given liquid = g/cm3

Precautions:

1. The stalagmometer and specific gravity bottle should be cleaned properly and dried
before use.
2. The stalagmometer should be fixed to its stand vertically
3. The number of drops formed must be 15 to 20 per 3 minutes

REPORT: The relative surface tension of the given liquid with respect to water at room
temperature is Dynes/cm

-----00000----

- 40 -
14. DETERMINATION OF IRON(II) PRESENT IN MOHR’S
SALT BY POTENTIOMETRIC METHOD
AIM: To determine the amount of iron(II) present in Mohr’s salt solution by titration with
standard potassium dichromate solution using potentiometric method.

APPARATUS: Potentiometer, calomel electrode, platinum electrode, beaker, (KCl salt

bridge), spirit lamp and plastic stirrer.

REAGENTS: Standard (N/20) potassium dichromate solution and Mohr’s salt solution.

THEORY: The principle behind potentiometric titration of iron(II)solution with potassium

dichromate { Cr(VI)} solution can be explained using modified Nernst equation, viz.,

. 

E = EoOxd/Red + log10 (1)
  

where E, Eo, [Oxd], [Red] and ‘n’ are the Experimental electrode potential at room
temperature, Standard reduction potential, concentration of Oxidised form, concentration
of Reduced form and number of electrons involved in the redox process of the system
respectively. Considering the present titration, the two systems of relevance, viz.,
Fe(III)/Fe(II) and Cr(VI)/Cr(III) have Eo values of 0.76 V, 1.36 V respectively, with a large
potential difference of 0.6 V and hence, quantitative oxidation of Fe(II) to Fe(III) by Cr(VI)
should be possible. Basing on equation (1), the expressions for the experimental potentials
(EMFs) of the two systems at room temperature may be written as

. 
EFe(III)/Fe(II) = EoFe(III)/Fe(II) + log10 , EoFe(III)/Fe(II) = 0.76 V (2)
 

. 
E Cr(VI)/Cr(III) = EoCr(VI)/Cr(III) + log10 , Eo Cr(VI)/Cr(III) = 1.36 V (3)
 

At the beginning of the titration, only Fe(III) and Fe(II) species are present in the
titration vessel and the potential displayed by the meter is mainly due to that of Fe(III)/Fe(II)
system only. As the titration progresses, more of Fe(III) is formed, Fe(III)/Fe(II) ratio
increases and there will be slow but steady increase in the potential. Once all the Fe(II) is
quantitatively oxidized, to Fe(III) by Cr(VI) at the equivalence point, the next added drop of
Cr(VI) causes a sudden large jump in potential (EMF) as the response of the potentiometer
is now mainly due to that of Cr(VI)/Cr(III) system (1.36 V).

The titration is accomplished using an inert indicator electrode (Platinum electrode), a

Reference electrode (Calomel electrode) and a digital potentiometer (Milli-Volt meter)
(Fig. 12). The relevant electrochemical cell reaction of the reductant may be represented as

Pt/Fe(III)/Fe(II) soln., 1N H2SO4 // KCl (sat),Hg2Cl2 (s)/ Hg(l)

- 41 -
PROCEDURE:

10 mL of the given Mohr’s salt solution is pipetted out into a clean 100 mL beaker. 5
mL of 1:1 sulphuric acid and 35 mL of distilled water are added to it using a measuring jar.
The end terminals of the indicator electrode (platinum) and reference electrode (calomel)
are connected to the proper terminals of the potentiometer after placing the electrodes in
the titration vessel (Fig.12). The contents of the beaker are then titrated against standard
dichromate solution taken in the burette. A pilot titration is carried out by adding 1.00 mL
portions of dichromate solution each time into the reaction vessel. The solution is
thoroughly mixed after each addition of the titrant (K2Cr2O7) solution, making use of a
plastic stirrer and the corresponding burette readings and emf (potential) values, as
displayed by the potentiometer, are recorded in Table 1. After reaching a certain stage in
the titration process, a sudden and large change in potential will be noticed, indicating
overstepping of the equivalence point. The process up to this stage, which locates the
approximate equivalence point, is known as pilot titration. An Accurate titration, on similar
lines to the pilot titration, is carried out until a volume 1 mL before the equivalence point is
reached. After this stage, the titration is continued by adding 0.1 mL increments of
dichromate solution (instead of 1 mL), until the equivalence point is crossed. The procedure
is continued until 3 more mL of the titrant is added after the equivalence point, adding
fractions of 1 ml increments of the titrant. All these observations are recorded in Table 2. A
graph is then drawn between volume of dichromate solution taken on X-axis and the
corresponding potentials on Y–axis, for the accurate titration. From the graph, the correct
equivalence point is ascertained and the concentration of iron(II) calculated as shown under
table 2.

Pilot titration of Mohr’s salt solution with standard solution of potassium dichromate
10.0 mL Mohr’s Salt Solution + 5 mL of 1:1 H2 SO4 + 35 mL of distilled water = 50 mL
Table 1: Readings of Pilot titration
S.No Volume of Potential,
dichromate mV
solution, mL
1
2
---
n

Accurate titration of Mohr’s salt solution with standard solution of potassium dichromate
10.0 mL of Mohr’s Salt Solution + 5 mL of 1:1 H2 SO4 + 35 mL of distilled water = 50 mL
Table 2. Readings of Accurate titration
S.No Volume of Potential,
dichromate mV
solution, mL
1
2
---
n

- 42 -
CALCULATIONS: The concentration of iron(II) in Mohr’s salt solution is calculated using the
formula V1N1 = V2 N2 where,
V1 = Volume of Mohr’s salt solution pipetted = 10.00 mL
N1 = Normality of iron in Mohr’s salt solution = ?
V2 = Volume of dichromate solution = mL
N2 = Concentration of dichromate solution = N (will be given)
As V1, V2 and N2 are known, Normality of iron(II) in Mohr’s salt solution, N1 may be
calculated as
N1 = V2 N2 /V1

Amount of Iron(II) present in Mohr’s salt per 1 liter = N1 x Eq. wt. of iron(II)
= N1 x 55.845 = g

Therefore, amount of iron(II) present in 100 ml = N1 x 55.845 = N1 x 5.584 = g.

10

Table 3: Report Table

Roll No. / Flask No. Amount of iron(II) present in 100 mL of Percentage

Regd.No. Mohr’s salt solution, g error
Given Reported

REPORT: Amount of iron(II) present in 100 mL of the given Mohr’s salt solution

Precautions
1. The platinum electrode should be activated by strong heating using spirit lamp before
starting the titration.

2. The solution should be thoroughly stirred with a plastic stirrer after each addition of the
titrant.

-----00000----

- 43 -
 15. DETERMINATION OF STRENGTH OF
HYDROCHLORIC ACID BY pH-METRIC METHOD
AIM: To determine the strength of hydrochloric acid using standard sodium hydroxide by
pH - metric method.

APPARATUS: pH meter, combined electrode/glass electrode and calomel electrode, 100 mL

beaker, 10 mL micro burette and plastic stirrer.

REAGENTS: Distilled water, standard 0.1N NaOH solution, HCI sample solution, standard
Buffer solutions of pH 4 and 9.2

THEORY: For many purposes, especially when dealing with small concentrations, it is
cumbersome to express concentrations of H+ and OH- ions in terms of gram equivalents per
liter. A very convenient method to express the concentrations of these ions was proposed
by S.P.L. Sorensen in 1909. He introduced the H+ ion exponent, pH, defined by the
relationships:
pH = - log10 [H+] = log10 1/[H+] or [H+] = 10-pH

The quantity of pH is thus the logarithm (to base 10) of the reciprocal of the H+ ion
concentration, [H+], or is equal to the logarithm of the [H+] with negative sign. This method
of expression has the advantage that all states of acidity and alkalinity between 1N in [H+] to
1N in [OH-] can be expressed by a series of positive numbers between zero and 14. Thus, a
neutral solution with [H+] = 10-7 has a pH of 7; a solution 1N in [H+] has a pH of zero; and a
solution 1N in [OH-] possesses a pH of 14.

The common lab pH meter (Fig. 13) is an electronic digital milli voltmeter, scaled to
read pH directly with a resolution of 0.01 pH unit and an accuracy of ± 0.01 unit. The reading
displayed by the meter is a direct measure of the potential difference registered between a
glass electrode and calomel electrode (reference electrode) immersed in the test solution.
The basic electrochemical cell involving glass electrode (Indicator electrode), calomel
electrode (reference electrode) and test solution may be represented as:

Ag/AgCl(s), HCl/glass /Test solution// | KCI (sat), Hg2CI2 (s) |Hg(l)

The strength of given Hydrochloric acid solution can be determined using standard
sodium hydroxide solution following the pH - metric method.

PROCEDURE:

The given hydrochloric acid sample solution in 100ml volumetric flask is made up to the
mark with distilled water and homogenised. 10 mL of the solution is pipetted out in to a
clean 100 mL beaker. 40 mL of distilled water is added to this solution. Meanwhile the pH
meter is switched on and is allowed to stabilize for about 10 minutes. The instrument is
calibrated with standard buffers of pH 4.0 and 9.2, after connecting the combined electrode,
or else, glass electrode calomel electrode combination to the pH meter. The cleaned glass

- 44 -
and calomel electrodes or the combined electrode is dipped into the HCL solution in the 100
mL beaker and the solution is stirred and the reading displayed by the pH - meter noted. The
contents of the beaker are then titrated against standard sodium hydroxide solution taken
in the burette. A pilot titration is carried out by adding 1.00 mL increments of the titrant
(sodium hydroxide) solution each time. The solution is thoroughly mixed after each addition
of the titrant, making use of a plastic stirrer and the corresponding pH values as displayed
by the pH - meter are recorded in Table 1. After reaching a certain stage in the titration
process, a sudden and large change in pH will be noticed indicating overstepping of the
equivalence point. The process up to this stage, which locates the approximate equivalence
point, is known as pilot titration. An Accurate titration, on similar lines to the pilot
titration, is carried out until a volume 1 mL before the equivalence point is reached. After
this, the titration is continued by adding 0.1 mL increments of the titrant solution until the
equivalence point is crossed. The process is continued until 3 more mL of the titrant is
added, after the equivalence point. All the relevant observations are recorded in Table 2. A
graph is then drawn between volume of titrant (sodium hydroxide) solution taken on X-axis
and the corresponding pH values on Y–axis, for the accurate titration. From the graph, the
correct equivalence point is ascertained and the concentration of hydrochloric acid in the
sample is calculated as shown under table 2.

Pilot titration of hydrochloric acid solution with standard sodium hydroxide solution

10 mL of hydrochloric acid + 40 mL of distilled water = 50 mL

Table 1: Pilot titration of HCl with NaOH

S.No Volume of NaOH pH

Solution added, mL
1
2
--
n

Accurate titration of hydrochloric acid solution with standard sodium hydroxide solution

10 mL of hydrochloric acid + 40 mL of distilled water = 50 mL

Table 2: Accurate titration of HCl with NaOH

S.No Volume of NaOH pH

Solution added, mL
1
2
--
N

- 45 -
CALCULATIONS: The concentration of HCl in the given sample solution is calculated using
the formula V1N1 = V2 N2 where,
V1 = Volume of sodium hydroxide = mL
N1 = Normality of sodium hydroxide = (will be given)
V2 = Volume of hydrochloric acid = 10.00 mL
N2 = Normality of hydrochloric acid = ?
As V1, V2 and N1 are known, Normality of HCl in the given sample solution, N2 , may be
calculated as
N2 = V1 N1 /V2
Amount of hydrochloric acid present in 100 ml of the given solution is equal to

Normality of HCI x Eq. Wt. of HCI(36.45)

10
= N2 x 3.645

Amount of Hydrochloric acid present in 100 ml of the given solution is: –----- g

Table: 3 Report Table

Roll No. / Flask No. Amount of Hydrochloric acid Percentage
Regd.No. present in 100 ml of the solution, g error
Reported Given

REPORT: Amount of hydrochloric acid present in 100 mL of the given solution

-----00000----

- 46 -
 16. ESTIMATION OF ZINC IN ZINC ORE BY
EDTA METHOD
Aim: Estimation of Zinc present in Zinc ore solution by titrating against a standardized
EDTA solution using Eriochrome Black- T as indicator.

Theory: Zinc in a given ore sample solution can be determined by using the complexometric
method, in which the Disodium salt of EDTA is employed (soluble in water) and it can be
represented as follows.
(EDTA – Ethylene Diamine Tetra Acetic acid)
HOOCH2C CH2COONa

N-CH2 - CH2 -N

NaOOCH2C CH2COOH

EDTA forms complexes with Mn+ (Ca+2/Mg+2/Za+2 etc.,)when the pH is in the range of
around 9.5 to 10.5 and to maintain the pH, a basic buffer solution is used (NH4OH + NH4Cl
buffer serves pH 9.5 to 10.5). The metal-EDTA complexes are colourless, therefore it is
necessary to use indicator to locate the end point. In this titration Eriochrome black – T is
used as indicator, which forms an unstable wine red coloured complex with zinc. When once
all the zinc ions are completely removed by EDTA, free indicator is left in the solution which
imparts blue colour to the solution. So the colour change at the end point is wine red to
blue.

Zn2+ (aq) +In2- pH−10

⎯⎯ ⎯→ [Zn-In] + EDTA4- (aq) ⎯⎯ ⎯→ Zn(EDTA)
pH−10 2-
(aq) + In2-

Unstable wine Stable complex Free indicator

red coloured Blue in colour
complex
Part – I:
Standardisation of di-sodium salt of EDTA solution by titrating against a standard
solution of zinc sulphate.

Procedure:
10.0 ml of standard zinc sulphate solution is pipetted out into a clean conical flask
carefully. To this 2 or 3 ml of ammonia - ammonium chloride buffer solution (pH 9.5 – 10.5)
and 2 or 3 drops of Eriochrome Black – T indicator are added. The burette is filled with
EDTA solution, after rinsing with same and the initial reading is noted. Now the contents
are titrated with EDTA solution until the colour changes from wine red to blue which is the
end point of the reaction. The final reading of the burette is noted. A number of titration
are carried out until 3 or 4 concurrent readings are obtained. The results are tabulated in
Table– I.

- 47 -
 Table – I
Standardization of EDTA solution with standard zinc sulphate solution

Morality of standard solution of EDTA ____________ M

Indicator: Eriochrome Black – T.
Colour change at the end point: Wine red to blue

Volume of Zinc sulphate Burette readings Volume of EDTA solution

S.No. solution taken in ml. Initial Final consumed in ml.

Calculations:

By the law of equivalence V1 M1/n1 = V2 M2/n2

M1 = Molarity of EDTA solution = ?

V1 = Volume of EDTA solution = ml.
n 1 = Number of moles of EDTA =
M2 = Molarity of zinc sulphate solution = M
V2 = Volume of zinc sulphate solution = ml.
n2 = Number of moles of zinc sulphate =
∴ M 1 = V 2 M 2 n 1 / N 2 V1

The Molarity of EDTA solution = _____________ M

Part -II:
Estimation of Zinc present in Zinc ore solution by titrating against a standardized
EDTA solution using Eriochrome Black- T as indicator.
Procedure:

The given zinc ore solution (as sulphate) is diluted up to the mark of volumetric flask with
distilled water carefully. The flask is stoppered tightly and is shaken thoroughly about 3-5
minutes for complete homogenization. 10.0 ml of the zinc ore solution is pipetted out into a
clean conical flask carefully. To this 2 or 3 ml of ammonia - ammonium chloride buffer
solution (pH 9.5 – 10.5) and 2 or 3 drops of Eriochrome Black – T indicator are added. The
burette is filled with EDTA solution, after rinsing with same and the initial reading is noted.
Now the contents are titrated with EDTA solution until the colour changes from wine red to
blue which is the end point of the reaction. The final reading of the burette is noted. A
number of titration are carried out until 3 or 4 concurrent readings are obtained. The
results are tabulated in Table– II.

- 48 -
 Table – II
Titration of standard EDTA solution with zinc ore solution
Morality of standard solution of EDTA ____________ M
Indicator: Eriochrome Black – T.
Colour change at the end point: Wine red to blue

Volume of Zinc ore solution Burette readings Volume of EDTA solution

S.No. taken in ml. Initial Final consumed in ml.

Calculations:
By the law of equivalence V3 M3/ n 3 = V4 M4/ n 4
M3 = Molarity of EDTA solution = M
V3 = Volume of EDTA solution = ml.
n 3 = Number of moles of EDTA =
M4 = Molarity of zinc ore solution = ?
V4 = Volume of zinc ore solution = ml.
n 4 = Number of moles of zinc sulphate =
∴ M 4 = V 3 M 3 n 4 / n 3 V4

The Molarity of zinc ore solution = _____________ M

Molecular weight of zinc = atomic weight = 65.39

Amount of zinc present in 1 liter of solution = {Normality of zinc ore solution x molecular
weight of zinc} = g

Amount of zinc present in the given 100 ml of zinc ore solution ={ amount present in 1 liter
of the solution / 10 } = g

Table – III
Percentage Error Table

Roll No. / Amount of zinc present in the given100 Percentage

Regd. No. Flask No. ml of ore solution in Grams. of error
Reported Given

Report: The amount of zinc present in the given 100 ml of an unknown solution is
_________ g.

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17. DETERMINATION OF SULPHURIC ACID PRESENT IN LEAD
ACID STORAGE BATTERY THROUGH ACID BASE TITRATION

Aim: Determination of % sulphuric acid present in Lead acid storage battery through acid
base titration using standard sodium hydroxide solutions.

Importance of acid in lead acid storage battery

Electrochemical reactions in lead acid storage battery

Pb+PbO2+H2SO4 2PbSO4+2H2O + Electrical energy (During discharging)

2PbSO4+2H2O + Electrical energy Pb+PbO2+H2SO4 ((During charging)

The above reaction states that during the discharge of the battery it consumes sulphuric
acid, the state of the discharging of the battery can be checked by measuring the density of
battery. The density of sulphuric acid in healthy battery should be more than 1.2 gm/cm3
(20-21%).

Theory: A reaction between sulfuric acid and sodium hydroxide is of an acid-base type, or is
also known as a neutralization reaction. In this process, both compounds undergo a reaction
to neutralize the acid and base properties. The products of this process are salt and water.
The balanced equation of this reaction is:

H2SO4 + 2NaOH → Na2SO4 + 2H2O

In this reaction salt and water are formed, which is an example of neutralization reaction.
All the reactants and products are colourless, so phenolphthalein indicator is used to locate
the end point of the reaction. The colour change of phenolphthalein is from colorless in
acidic medium to pink in alkaline medium.

Procedure: The given acid solution is made up to the mark of volumetric flask with
distilled water carefully. The flask is stoppered and shaken thoroughly about 2 to 3 minutes
for complete homogenization. The burette is rinsed with the given acid solution and filled
with same without air bubbles. 10ml standard sodium hydroxide solution is pipetted out
into a clean conical flask carefully and 50.0 mL of distilled water is added with measuring jar.
Two drops of phenolphthalein indicator is added directly to the contents of conical flask.
The conical flask contents are titrated with given acid solution after noting the initial
reading. The titration is continued till the colour changes from pink to colourless. The final
reading of burette is noted. A number of titrations are repeated for getting concurrent
results. The results are tabulated in table no. I.

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 Table – I
Titration of Sulphuric Acid solution with standard sodium hydroxide solution
Volume of standard Burette reading Volume of Sulphuric acid
S.No. sodium hydroxide solution solution consumed in
Initial Final
taken in ml. (V2) (V1) ml.

Calculations:
By the law of equivalence V1N1 = V2N2
N 1 = Normality of Sulphuric Acid solution = ?
V1 = Volume of Sulphuric Acid solution = ml.
N 2 = Normality of Sodium hydroxide solution = N
V2 = Volume of Sodium hydroxide solution = ml.
∴ N1= V2N2 / V1
∴ The Normality of Acid solution is_____________ N.
Equivalent weight of Sulfuric acid =Molecular weight / 2=98/2=49
Amount of Sulphuric Acid present in 1000 ml of the solution = {Normality of Sulfuric acid
solution X Equivalent weight of Sulphuric Acid} = gm.
Amount of Sulphuric Acid present in the given 100 ml of solution =
{Amount present in 1000 ml of solution / 10} = gm
Sp ecific G ravity: Tare an empty dry 100 mL beaker over a balance Transfer carefully
10ml (or 25ml) of Acid solution using a volumetric pipette into the beaker. Note the volume
used and weight read out. Repeat this for 2 more times to have 3 weight readings and
average out the result.
Specific gravity= Mass (g)/Volume (mL) =
1 mole H2SO4 in 1000 mL weigh 98g
If test solution has X moles H2SO4 in 1000ml (XM)
The weight of H2SO4 molecules in 1000mL is X x 98 = Yg

Percentage Concentration [%]= (% weight of acid molecules in 100mL×100/Weight of 100

mL acid)
Report: Amount of Sulfuric acid present in the given 100 mL of solution…………….gm.
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 18. PREPARATION OF UREA FORMALDEHYDE
AIM: To prepare urea formaldehyde resin.

APPARATUS REQUIRED: Beaker, glass rod, funnel, filter paper and chemical balance.

CHEMICALS: Urea, formaldehyde sol., conc. H2SO4, distilled water.

THEORY: Amino resins are condensation products obtained by the reaction of

formaldehyde with nitrogen bearing compounds such as aniline, amides for ex:-
melamine formaldehyde, urea formaldehyde etc.
Urea formaldehyde is prepared by condensation reaction between urea
and formaldehyde in acidic or alkaline medium.
The first product formed during the formation of resin is monomethylol and
dimethylolureas.
NH-CH2OH NH-CH2OH
HCHO
NH2CONH2+HCHO C=O C=O

NH2 NH-CH2OH
Urea Formaldehyde Monomethylol Dimethylol
Urea Urea
Polymerization can take place from mono or dimethylol urea or possibly through both, with
the formation of long chains

PROCEDURE:
1. Place about 5 ml of 40% formaldehyde solution in 100 ml beaker.
2. Add about 2.5 g of urea with constant stirring till saturated solution is obtained.
3. Add a few drops of conc. H2SO4, with constant stirring.
4. A voluminous white solid mass appears in the beaker.
5. Wash the white solid with water and dry it in the folds of filter paper.
6. Weight the yield of product
PRECAUTIONS:
1. While adding concentrated H2SO4, it is better to stay little away from
the beaker since the reaction sometimes becomes vigorous.
2. The reaction mixture should be stirred continuously.

OBSERVATIONS:
Mass of the beaker(W1)= ---------------------------- g.
Mass of the beaker with urea formaldehyde(W2)= -------------------------- g.
Therefore, mass of urea formaldehyde (W2 –W1)= -------------------------g.

REPORT:The yield of urea formaldehyde = --------------- g

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PROPERTIES:
1. They have good electrical insulating properties.
2. They are resistant to oil, grease and weak acids.
3. They are hard, resist abrasion and scratching.
4. They have good adhesive properties.

USES:
1. They are used adhesive applications for the production of plywood and laminating.
2. They are used for the manufacture of cation exchange resins.
3. These also find use in the manufacture of electrical switches, plugs and insulating
foams.
4. Their applications also include the treatment of textile fibers for
improving their shrink and crease resistance.

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 19. PREPARATION OF PHENOL
FORMALDEHYDE RESIN

AIM: To prepare phenol formaldehyde resin.

APPARATUS: Beaker, glass rod, funnel, filter paper, and chemical balance.

CHEMICALS: Phenol formaldehyde, conc.HCl, glacial acetic acid, distilled water.

THEORY: Phenolic resins are condensation polymerization of phenolic derivatives (like

phenol, resorcinol) with aldehyde (like formaldehyde, furfural). Most important member of
this class is bakelite or phenol formaldehyde resin.
Phenol formaldehyde is prepared by condensing phenol with formaldehyde in
presence of acidic or alkaline catalyst. The initial reaction result in the formation of o- and p-
hydroxy methyl phenol, which reacts to form linear polymer navalac.
During molding hexamethyline tetramine [ (CH2)6N4] is added which convert the
fusible novalac in to hard infusible and insoluble solid of cross – linked structure known as
Bakelite.

PROCEDURE:
1. Place 5 ml of glacial acetic acid and 2.5 ml of 40% formaldehyde
solution in a 100 ml beaker.
2. Add 2 g of phenol to it.
3. Wrap a cloth loosely round the beaker. Add a few ml of conc. HCl
in to the mixture carefully and heat it’s lightly.
4. A large mass of plastic pink in colour is formed.
5. A residue is washed with water and filtered.
6. The product dried and yield is weighed.

PRECAUTIONS:
1. While adding conc.HCl, it is better to stay little away from the beaker
since the reaction sometimes becomes vigorous.
2. The reaction mixture should be stirred continuously.

OBSERVATIONS:
Mass of the beaker (W1)= ---------------------------- g.
Mass of the beaker with phenol formaldehyde (W2)= ------------------------- g.
Therefore, mass of phenol formaldehyde (W2 –W1) = ------------------------ g.

RESULT: The yield of phenol formaldehydes= ------------------ g

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PROPERTIES:
1. Phenol formaldehyde molding resins have excellent heat resistance.
2. These have high dimensional stability.
3. Phenolic resins have good dielectric properties.
4. They have hard, rigid and scratch resistant.

USES:
1. They are used for making electric insulator parts like switches, plugs,
switch board, heater, handles etc.
2. These are also used in varnishes, paints and protective coatings.
3. These are used in the protection of ion exchange resins for water softening.
4. Phenolic resins are used for improving impregnating paper, wood and other fillers.

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 20. SYNTHESIS OF TITANIUM DIOXIDE NANOPARTICLES
Aim: To prepare Titanium dioxide nanoparticles
Reagents
Titanium tetrachloride (TiCl4), 99%;
Titanium isopropoxide (C12H28O4Ti), 99.8%;
Urea (CO(NH2)2), 99%;
Ammonium chloride (NH4Cl), 99.5%;
Glacial acetic acid, 99.5%;
Methanol, 99.5%;
Ethanol 99.8%.

Compounds Amounts
TiCl4 : 05 mL
C2H5OH : 50 mL
H2O : 200 mL

Procedure:
Ethanol and titanium tetrachloride are introduced into a beaker; the solution is
stirred for 30 min. During this period, a yellow sol phase is formed. Double distilled water is
added to form clear and colorless solution. The solution is again stirred for 30 min at room
temperature and then the formed gel is dried at 50oC for 24 h and characterized by SEM and
TEM.

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 21. SYNTHESIS AND CHARACTERIZATION OF
NANO-SIZED ZnO BY PRECIPITATION METHOD
AIM: Synthesis and Characterization of Nano-sized ZnO by precipitation method

Materials Required
Zinc nitrate hexahydrate (Zn(NO3)2.6H2O), 99% , sodium carbonate (Na2CO3), 99% and
Ethanol (C2H5OH, 95%,).

Procedure for Preparation of ZnO nanoparticles

Two solutions are prepared
Solution A: 0.1 mol Zn (NO3)2.6H2O is prepared by dissolving 29.75g of Zinc nitrate
hexahydrate in 200 ml distilled water; and
Solution B: 0.12 mol Na2CO3 is prepared by dissolving 12.72 g of sodium carbonate in 240
ml distilled water.
After that solution A is added to solution B drop wise under vigorous stirring. The
white precipitate is collected by filtration and rinsed with distilled water three times. The
solid is then washed with ethanol and dried at 100°C for 6 h. Finally, ZnO nanoparticles are
obtained after annealing of the solid in air at 250, 300, 350, 400, 500, and 600°C for 2 h,
respectively.

Characterization
• The optical properties of prepared ZnO NPs are analyzed by UV-visible
Spectrophotometer (Shimadzu, UV-2450). A broad absorption peak is observed in
each spectrum at 355-380 nm which is a characteristic band for the pure ZnO.
• The FT-IR shows a broad absorption band related to Zn-O vibration band at 500 cm-1.
• The SEM results show the formation of spherical shaped nano particles.

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