Laboratory Manual for Undergraduates

(CY 1002)

DEPARTMENT OF CHEMISTRY
INDIAN INSTITUTE OF TECHNOLOGY
MADRAS
CHENNAI - 600 036
 FOREWORD

Twenty first century can be called as an era of “Materials”.

Sustained efforts on new innovations and developments in
Materials Science and Technology have made and continue to
make notable contributions to the needs and comforts of both
society and common man. Chemistry which is primarily an
experimental science is at the back of all this.

Laboratory work and experiments are an integral part of learning

chemistry. Experience of experimentation is a delightful way of
appreciating concepts and consequences of chemistry and its
practice.

The experiments included in this manual have been carefully

designed and developed by a dedicated team from our
department with a view to provide an opportunity to the young
and enthusiastic first year undergraduate students, a taste of
experimental chemistry, its range, variety, principles underlying
in them and utility value.

I thank profusely the entire team of colleagues, staff and

research scholars of my department who have worked for this
and wish all the student participants a useful and enjoyable
experience.

Head, Department of Chemistry

 CONTENTS

Expt.No. Title Page No.

1. Reaction Kinetics 1
2. Preparation of gold nano particles 6
3. Acid strength in a citrus fruit 11

4. Estimation of Cu by colorimetry & Iron by

redox titration. 16
5. Estimation of Ni by gravimetry 20
6. Synthesis of Cu Oxalate complex 22

7. Base catalyzed aldol condensation 24

8. Halogen addition to C=C bonds 26
9. Qualitative Analysis of organic compounds 28
 Undergraduate Laboratory Safety Precautions

Safety Instructions
Safety signs and instructions from demonstrators and academic
supervisors must be strictly obeyed.

Eating and Drinking

These activities are strictly forbidden in all laboratory areas or in
adjacent rooms.

Supervision of Laboratory work

No one is to perform experimental work unless a demonstrator or a
member of the academic staff is present in the laboratory.

Eye protection
All persons must wear approved safety spectacles or goggles in
chemical laboratories.

Protective clothing
All persons carrying out experimental work must wear the appropriate
protective clothing.

Reporting Accidents, Fire and Dangerous Occurrence

All accidents resulting in injury, property damage or fire that might
cause injury, must be reported to the supervisor.

In the event of Fire

1. Leave the building immediately by the nearest exit.
2. Never use lifts.
3. The person or persons responsible for starting and /or discovering
the fire must be available to brief with the Institute security officer.
 Physical Chemistry Experiments

Expt:1
REACTION KINETICS - FIRST ORDER RATE CONSTANT

Aim: To determine the first order rate constant at room temperature

for the hydrolysis of methyl acetate catalysed by hydrogen ions.

Glasswares Required:
 Stoppered bottle (250 mL).
 Burette (50 mL)
 Conical flask (250 mL)
 Pippette (2 mL and 5 mL).
Chemicals required:
 NaOH solution (0.2N)
 HCl Solution (0.5N)
 Methyl acetate (2 mL)
 Phenolphthalein (few drops)
Principle:

Various chemical reactions take place at different rates. The

rate of any particular reaction depends on certain parameters, the most
important one being the concentration and temperature. At constant
temperature, study of the influence of concentration on the rate of a
reaction enables us to determine the order of the preaction.
If the rate of a reaction (R) is given by R  kC C C , the overall
q r

1 2 3
order n = p + q + r and k is called the rate constant.

The hydrolysis of methyl acetate catalyzed by hydrogen ions (eqn.1)

forms a convenient system for kinetic investigation at room
temperature.

H  (Catalyst )
CH3COOCH3 H2O CH3COOH  CH3OH
(1)


1
In the above reaction, the concentration of water is practically constant
throughout the reaction. The rate of the reaction is thus directly
proportional to the concentration of the ester, i.e. the reaction is
pseudo first order, since [H+] is also a constant.

The progress of the reaction is followed by determining the change in

the concentration of methyl acetate as a function of time. This is done
in an indirect way as follows. For each mole of ester hydrolyzed, one
mole of acetic acid is produced. The rate of hydrolysis of methyl
acetate is equal to the rate of formation of acetic acid.
This is represented as:

𝑑[𝐶𝐻3𝐶𝑂𝑂𝐻] 𝑑[𝐶𝐻3𝐶𝑂𝑂𝐶𝐻3]
=− = 𝑘[𝐶𝐻3𝐶𝑂𝑂𝐶𝐻3] (2)
𝑑𝑡 𝑑𝑡

In eqn. (2) k is the rate constant for the reaction and depends on
temperature, [H+] and the solvent used for the reaction. k can be
calculated more easily from the integrated form of eqn. (2).

If "a" is the initial concentration of the ester, and x is the amount of

the ester decomposed at any time t,

2.303 𝑎 1 𝑎
𝑘= log = ln (3)
𝑡 𝑎−𝑥 𝑡 𝑎−𝑥

From this kinetic equation (eqn. 3) for a first order reaction, the rate
constant k can be calculated.

The determination of (a-x) at various time intervals (t) and substitution

in the kinetic equation (eqn.3) would yield a set of values of k, which
can be averaged.

Alternatively, a plot of log (a-x) against 't' would yield a straight line
and the rate constant 'k' can be calculated from the slope.

2
Procedure

1. Pipette out 2 mL of methyl acetate into the given stoppered

bottle and shake the bottle to ensure through mixing and start
the stop watch as soon as the ester is added.
2. Immediately withdraw 5 mL of reaction mixture by means of
a pipette and transfer it into the conical flask with about 20
mL of ice-cold distilled water.
3. Add a drop of phenolphthalein to the conical flask and titrate
against standard NaOH (approximately 0.1 N) taken in the
burette.
4. The first appearance of a pale pink color is taken as the end
point. Note down the titre value (V0). This value corresponds
to time, t =0. Discard the reaction mixture in the conical flask
and clean the conical flask for the next titration.
5. At definite intervals of time say, 10, 20, 30, 40, 50, 60
minutes’ pipette out 5 mL of the reaction mixture, deliver it
into ice-cold distilled water and titrate against standard NaOH.
6. Note the titre value (Vt) in each case into your record book.

(V∞ - V0) corresponds to the initial concentration (a) of the ester,

(V∞-Vt ) corresponds to the concentration of the ester at any time, i.e.,

(a-x). The kinetic equation in terms of the titre values reduces to

2.303 v  v0
k log
t v  vt (4)

3
The titre values are used instead of concentration since they are
directly proportional to each other.

Determination of V∞ :

1. Add 100 mL of 0.5 N HCl in to a 250 mL stoppered bottle.

2. Pipette out 2 mL of methyl acetate into the given stoppered

bottle
3. Keep the bottle in a water bath maintained at 80 °C for 30
minutes. This enables the entire methyl acetate to hydrolyze
yielding an equivalent quantity of acetic acid (CAUTION:
Hold the stopper while the bottle is being heated lest it would
pop off).
4. Cool to room temperature and then withdraw 5 mL of the
reaction mixture into the conical flask, add phenolphthalein
indicator and titrate against the NaOH solution. Note the titre
value (V∞).
Graph:

1. Plot of log (V∞-Vt) against ‘t’would yield a straight line.

‘k’can be evaluated from the slope.

2. Plot (V∞-Vt) versus time and from this graph, determine the
time required for the concentration ‘a’ to drop to 90% a.

Calculate the value of k from this and also by using eqn. (3).

4
 Rough Observations

S.No. Time Burette Readings Volume of

( mins) Initial Final NaOH (ml)
(mL) (mL)
1 0
2 10
3 20
4 30
5 40
6 50
7 60

5
Expt: 2

Verification of Beer-Lambert law using gold nanoparticles

Aim : Preparation of gold nano particles using the citrate method and
verification of Beer- Lambert law.
Glass wares Required:
 Standard Flask (5 mL) - 5 Nos.
 UV cuvette- 1 No.
 Flat bottomed flask (50 mL)- 1No.
 Measuring Cylinder (25 mL)- 1No.
 Graduated pipette (1 mL, 2mL and 5mL each one).
Chemicals required:
 Chloro auric acid solution
 Tri sodium citrate

Principle
The Beer-Lambert law, also known as the Beer's law or the Lambert-
Beer law or the Beer-Lambert-Bouguer law in various books, is the
linear relation between the absorbance and concentration of an
absorbing species. It relates to the absorption of light to the properties
of the material through which the light is traveling.

In practice, Beer's Law is accurate enough for a range of species,

solvents and concentrations, and is a widely used relationship in
quantitative spectroscopy. Most often, it is used in a quantitative way
to determine concentrations of an absorbing species in solution.

Absorbance is measured in a spectrophotometer by passing a

collimated beam of light at wavelength λ through a plane parallel slab
of material that is normal to the beam.

For liquids, the sample is held in an optically flat, transparent

container called a cuvette. Absorbance (A) is calculated from the ratio
of light intensity passing through the sample (I0) to the intensity that is
incident on the sample (I).
6
 A  log   I0 
10 
 I 
According to this law, when light passes through a material, there
exists a linear dependence between the absorbance (A) of light and the
product of absorption coefficient (α) with the path length (l) of the
light (distance though which light travels in the material).

Absorption coefficient of a material in turn depends on the molar

absorptivity or molar extinction coefficient or molar absorption
coefficient (ε) and the concentration (c) of the absorbing species in the
material. Thus, according to Beer-Lambert law, absorbance is given
by

A  cl
where ε is constant, for a given wavelength of light, and can be
obtained from the absorbance values of solutions with different
concentrations. Absorbance is unit less, while the units of ε, l, c are
L.mol-1.cm-1, mol. L-1 and cm-1, respectively.

The Beer-Lambert law was independently discovered (in various

forms) by Pierre Bouguer before 1729, Johann Heinrich Lambert in
1760 and August Beer in 1852. Beer extended the exponential
absorption law to include the concentration of solutions in the
absorption coefficient
.
Appearance of wine-red colour in step 6 indicates the formation of
colloidal gold or gold nanoparticles. The recorded UV-Vis spectrum
of the solution, step 10, shows the absorbance at a λmax of ~520 nm, as
shown in Fig. 1. This feature is attributed to the plasmon resonance
of gold nanoparticles. Read more about plasmon resonance in a book
on nanomaterials.

7
 Absorbance (a.u.)

500 600 700

-1
Wavelength (cm )
Fig. 1 UV-Vis spectrum of as prepared gold nanoparticles.
Absorbance (a.u.)

0.06 0.12 0.18 0.24 0.30 -1 0.36

Au concentration (mol.L )
Fig. 2 Plot of absorbance vs. concentration of gold nanoparticles.

Fig. 2 shows the plot of absorbance vs. concentration for the gold
nanoparticles of different dilutions. It can be observed that all the data
points fit into a straight line, thus conforming to the Beer-Lambert
law. Slope of the above plot gives the absorption coefficient of the
gold nanoparticles.

For the calculation of absorption coefficient, path length is taken as

equal to the width of the cuvette used for recording the UV-Vis
spectrum (we have taken it as 1 cm). From the above data, the value of
absorption coefficient is calculated as ~3.36 L.mol-1.cm-1. By making
use of the above plot (Fig. 2), we can calculate the concentration of
gold nanoparticles of an unknown dilution.
8
You may want to know that light attenuation in this particular case is
not truly due to optical absorption alone as there is a scattering
component. At the limit of small particles (as in this case, where the
particle size is ~ 20 nm), scattering is disregarded.

Scattering and absorbance together is called extinction and the Y axis

will be labeled as “Extinction” in the case of larger particles.

Procedure

1. Prepare 10 mM HAuCl4 solution in a 5 mL standard flask by

dissolving 17 mg of HAuCl4·3H2O in water. (Stock Solution)

2. Prepare ~0.5% solution of trisodium citrate in a 10 mL sample

bottle flask by dissolving 25 mg of Na3C6H5O7 in 5 mL of
water. (Stock solution)

3. Take 0.5 mL of 10 mM HAuCl4 solution in a 50 mL flat

bottomed flask using a 1 mL pipette and add 13 mL of
distilled water to it using a 25 mL measuring jar.

4. Heat the solution over a heating mantle and bring the solution
just to a boil (marked by the appearance of bubbles from the
colourless solution).

5. To the boiling solution, add 1 mL of ~0.5 % trisodium citrate

solution using a 1 mL pipette.

6. Continue heating (with boiling) till the colour turns to wine-

red. (This may take about 1-2 minutes)

7. Remove the flask from the mantle and keep it for cooling in
air, for about 15-20 minutes.

8. To account for loss of water during boiling, make the solution

to 14.5 mL (i.e. to the original volume) in a 25 mL measuring
jar.

9. Calculate the concentration of gold nanoparticles in the

solution in terms of gold.

9
 10. Prepare the following solutions of different concentrations.

 5 mL prepared solution
 4 mL prepared solution + 1 mL distilled water
 3 mL prepared solution + 2 mL distilled water
 2 mL prepared solution + 3 mL distilled water
 1 mL prepared solution + 4 mL distilled water

11. Collect the absorbance at 520 nm of undiluted solution and

those of the above diluted ones, with distilled water as the
reference, using a UV-Vis absorption spectrometer.

12. Plot a graph of absorbance vs. concentration with the obtained

values and verify Beer-Lambert Law.

Rough Observation

Volume of Volume of Gold

S.No prepared Distilled water concentration Absorbance
Solution (mL) (moles/Litre)
(mL)
1. 5 0

2. 4 1

3. 3 2

4. 2 3

5. 1 4

10
Expt:3
ACID STRENGTH IN A CITRUS FRUIT

Aim: To determine the acid strength in a citrus fruit juice using

conductometry.

Glass wares Required:

 Standard Flask (250 mL- 2Nos)
 Beakers (100 mL- 2 Nos.)
 Pipette (25 mL, 20mL and 10mL - one each).
 Burette (25 mL and 10mL - one each)

Chemicals required:
 NaOH solution
 HCl solution (0.02N)
 Citrus fruit Juice
 Buffer tablets (pH 4, pH 7 and pH 10)
 0.01N KCl solution

Principle
Citrus fruits contain fairly a large amount of citric acid. It is often a
good source of Vitamin C (Ascorbic acid) too. A simple acid-base
titration with a strong base can be performed to determine its acid
strength. However, some citrus fruits are colored and in such a case
conventional titration using indicator-dyes is not possible. Various
instrument based titrations like conductometric, pH metric or
spectrophotometric methods then become essential.

The present experiment is aimed at introducing two instruments for

carrying out acid-base titrations: a pH meter and a conductivity bridge.

First part of the experiment involves the use of pH meter for titration
of a strong acid with a strong base of unknown strength. A pH meter is
a potentiometer, which uses a glass electrode sensitive to H+ ion
concentration. If a strong acid is titrated against a strong base (in the

11
burette), the pH of the solution varies as a sigmoidal curve with a very
sharp increase of pH at the end point.

Second part of the experiment is the conductometric titration of the

citrus fruit juice, (which, in all likely hood, is supplied to you after
dilution in water), with a standard sodium hydroxide solution
(standardized in the first part of the experiment. A solution containing
ions conduct electricity due to movement of ions to oppositely
charged electrodes under the influence of an electric field. More the
concentration of free ions in a solution, more the conductance.

The conductance of a weak acid is usually low as free ions furnished

in the solution is less. On titrating with a strong hydroxide solution
(fully ionized), an initial decrease of conductivity is observed due to
mutual suppression of ionization of the acid and the salt that is
formed. However, after a few drops of titrant addition, the less
ionizable acid is progressively replaced by its completely ionizable
sodium salt, the conductance starts to increase linearly.

Once the end point is reached and all the acid has been converted to its
salt, addition of further sodium hydroxide results in a much rapid
increase in the conductance as OH- ion conducts more than the acid
anion. The end point is thus the point where this change in slope takes
place.

Procedure: PART -I

Calibration of pH meter

1. Switch on the pH meter and allow it to stabilize for 10

minutes.

2. Adjust the temperature compensate to 25°C.

3. Insert the pH probe into the buffer solution of pH 4 and note

the reading if not correct adjust the screw on the side of the
pH meter.

4. Similarly do the same for pH 7.

12
Part I: Standardization of the Sodium hydroxide solution.

5. Wash the glass electrode by distilled water and immerse it

into a standard acid solution and note the pH.

6. Add small aliquots of sodium hydroxide solution of unknown

strength from a burette, stir the solution well, and note the pH
and the burette reading. Continue further till there is almost no
change in pH.

7. Plot “pH” vs. “volume of base”. The point of inflection of the

sigmoid curve, which is expected at pH 7, is the end point.
Calculate the strength of the sodium hydroxide solution.

Rough Observation

Volume of Volume of
pH
NaOH(ml) pH NaOH (mL)
0.0 8.0
1.0 9.0
2.0 10.0
3.0 11.0
4.0 12.0
5.0 13.0
6.0 14.0
7.0 15.0

13
Procedure: PART -II

Calibration of Conductometer:

1. Switch on the Conductometer and allow it to stabilize for 10

minutes.

2. Insert the conductometry probe into standard 0.01 N KCl

solution and adjust the knob and set the reading to 1413 μS at
25°C).

Part-II: Determination of strength of the citrus fruit juice.

1. Switch on the conductivity bridge and allow it to stabilize for

10 minutes.

2. Take the given juice solution in a beaker and note its

conductance.

3. Titrate with standard NaOH solution and note the burette

readings and conductance after each addition.

4. An initial dip in conductance is observed which soon

increases linearly with volume of base added. At the end point
you will observe a faster increase of conductance with base
addition.

5. Stop the titration after 8/10 readings after the end point.

6. Plot Conductance Vs Volume of base added. Find the end

point and estimate the strength of the juice solution given.

14
 Rough Observation

Vol. of Conductance Vol. of Conductance

NaOH (mL) Ohm-1 NaOH (mL) ohm-1
0.0 2.75
0.25 3.0
0.50 3.25
0.75 3.5
1.0 3.75
1.25 4.0
1.5 4.25
1.75 4.5
2.0 4.75
2.25 5.0
2.50

15
 Inorganic Experiments
Expt:4a

Estimation of Cu2+ ion by colorimetry & Fe2+ ion by redox

titration

Aim : To determine the concentration of Cu2+ ion by colorimetry.

Principle: The given Cu2+ ion solution is treated with excess 1:1 NH3
solution to form complex and made up to a known volume. The
absorbance of the complex in the visible region is measured at 610 nm
using a colorimeter. From the calibration plot drawn with the
absorbance of standard solutions, we can find out the concentration of
copper in the given unknown solution.

Glass wares required:

 Standard flask (25 mL) – 6 Nos.

 Burette (25 mL) – 1 No.
 Colorimeter tube – 1 No.
 Measuring Jar (10 mL) – 1No.
 Beaker (100 mL) – 1 No.
 Dropper – 1No.

Chemicals required:

 Copper Sulphate (5000ppm) standard solution

 Ammonia Solution (1:1)

Procedure:

Five different known concentration of Copper – Ammonia complex

solution were prepared by the following method:

16
Flask No. Vol. of Vol. of 1:1 Vol. to Conc. in
Cu2+ (5000 NH4OH# be made mg/L
ppm) soln*. up
1 1 5 25
2 2 5 25
3 3 5 25
4 4 5 25
5 5 5 25

*The quantity mentioned should be exactly taken from

burette
#Ammonia should be taken only using measuring
cylinder. Caution! Never use pipette for ammonia.
Their absorbance at 610 nm was measured using a
colorimeter. A plot is drawn with absorbance in Y axis and Copper
concentration in mg/l in X axis.
To the unknown solution given in the 25 mL standard flask 5
mL of 1:1 NH3 solution is added and then it is made up to 25 mL mark
using droppers.
After making up the solution is mixed well. Required quantity
is transferred into the colorimeter tube and absorbance at 610 nm is
measured.
Using the above calibration plot and the value of absorbance
for the unknown, the concentration of copper ion in the given solution
is calculated.

Expt:4b Estimation of Fe2+ ion by Redox Titration

17
Aim: To determine the normality of the given unknown Fe2+ ion
solution.

Principle: The given unknown Fe2+ ion solution is made up to a

known volume and then titrated with standard potassium dichromate
solution in acid medium with ortho phosphoric acid and Diphenyl
ammine as indicator. End point is the appearance of violet colour.
Glasswares required:
 Standard flask (100 mL) – 1 No.
 Pipette (10 mL) – 1No.
 Burette (25 mL) – 1No.
 Conical Flask (250 mL) – 1No.

Chemicals required:
 Standard Potassium Dichromate solution (0.05N)
 Unknown Ferrous ammonium sulphate solution (roughly 0.5N
solution)
 Sulphuric acid (2N)
 Orthophosphoric acid
 Diphenylamine indicator (1% in conc. sulphuric acid)

Procedure:

The given Fe2+ ion solution is made up to 100 mL in a standard flask

and shaken well.

10 mL of this solution is pipette out into a 250 mL conical flask. To

this 5 mL of 2N Sulphuric acid, 2 mL of Ortho Phosphoric acid and 2
drops of Diphenylammine indicator were added.

This solution is titrated against standard 0.05N Potassium dichromate

solution till violet color appears. From the titre value the normality of
the given unknown Fe2+ solution is calculated.

18
 Rough Observation

Volume of 5000 ppm Concentration

S.No Absorbance
Copper Solution ( mL) (mg/L)
1. 1 200

2. 2 400

3. 3 600

4. 4 800

5. 5 1000

6. Unknown sample ?

Rough Observation

Vol. of Fe2+
Volume of
solution
Sl.No. Burette Reading K2Cr2O7
Pipetted out
( V1 mL)
(V2 mL)
Initial Final
1 10

2 10

3 10

19
Expt 5:
Gravimetric analysis

Aim: To estimate the Ni2+ ion in the given unknown solution by

precipitating the Ni2+ ion as Nickel-DMG complex and performing
gravimetric analysis.

Principle:

Nickel is precipitated by the addition of an ethanolic solution of 1%

dimethyl glyoxime (DMG) to a hot, faintly acid solution of the nickel
salt, and then adding a slightly excess of dilute ammonia solution (free
from carbonate). The pink coloured precipitate is washed with cold
very dilute (1:100) ammonia and then with cold water. Dry the nickel
dimethylglyoximate after at 110-120oC for 30 minutes. Cool in a
desiccator to room temperature and then weigh. Repeat drying for
constant weight.

Glasswares required:
 Beaker with glass rod (250 mL) – 1No.
 Watch glass – 1No.
 Measuring cylinder (10 mL) – 1No.
 Sintered Crucible (G3) – 1No.
 Desiccator – 1No.

Chemicals required:
 Hydrochloric acid (1:1)
 DMG solution (1% in absolute ethanol)
 Ammonia Solution (dilute)
 1:100 very dilute ammonia for washing

Procedure:

1. Dilute the given unknown Ni2+ solution to 100 mL.

20
 2. Heat the solution to 70-80oC, using electrical hot plate then
carefully shift the solution to water bath and add a slight
excess of the dimethylglyoxime (~10 mL) reagent and
immediately add dilute ammonia solution (slightly excess)
drop wise, directly to the solution with constant stirring until
precipitation takes place.

3. Allow this to stand in steam bath for 15 minutes.

4. Cool to room temperature and filter through pre weighed

sintered crucible (Empty weight of the crucible to be taken
first).

5. Keep the G3 sintered crucible in the suction setup and first

wash it by draining 20 mL very dilute ammonia (1:100)
solution through it by applying vacuum. Then transfer the
precipitate quantitatively into the sintered crucible carefully
without any loss.

6. Wash the precipitate with very dilute 1:100 ammonia and then
with cold water.

7. Dry it at 110-120°C for 20 min.

8. Cool the crucible in desiccator and then weigh the crucible

with precipitate. Repeat until constant weight is attained.

9. Weigh as Ni(C4H7O2N2)2, which contains 20.32% Ni.

Rough Observation

Weight of Sintered Crucible with NiDMG complex :

Weight of empty Sintered Crucible :
Weight of NiDMG precipitate :

Weight of Nickel in given unknown solution = weight of

NiDMG X 0.2032 =
21
 Expt:6

Synthesis of copper oxalate complex K2[Cu(C2O4)2].2H2O

Aim : Synthesis of copper oxalate and determination of the its

oxalate content.

Glasswares required:
 Beaker (100 mL) with glass rod – 2Nos.
 Sintered Crucible (G3) – 1No.
 Conical flask (250 mL) – 1No.
 Burette (50 mL) – 1No.

Chemicals required:
 Copper sulphate solid
 Potassium oxalate solid
 Acetone
 Sulphuric acid (4N)
 Potassium permanganate solution (0.05N)

Principle:
In acid solution, permanganate, MnO - [Mn(VII)]
4 is reduced to
Mn(II). The half reaction is:
MnO - + 8H+ + 5e- → Mn2+ + 4 H O Eo = 1.51 V
4 2
In basic or neutral solution, permanganate is reduced to manganese
(IV) oxide. The half reaction is
MnO - + 4H+ + 3e- → MnO + 2H O Eo = 1.70 V
4 2 2
Sodium oxalate or oxalic acid is often used to standardize
permanganate. The relevant half reaction is
C2O42- → 2CO2 + 2e- Eo = -0.49 V
Therefore, the reaction with permanganate is favourable, i.e.,
2 MnO - + 5C O 2- + 16 H+ → 2Mn2+ + 10CO + 8H O, E ° = 1.02 V
4 2 4 2 2

22
 Procedure

1. Dissolve 2 g of CuSO4.5H2O in 5 mL water and heat the

solution to 70°C.
2. Add the hot solution with stirring to 15 mL solution of
potassium oxalate, containing 6g of K2C2O4.H2O.
3. Allow the solution to cool and filter the precipitate through a
pre weighed sintered (G-3) crucible. Wash with ice cold
water, followed by ice cold acetone. Dry the product at 50-60O
C and weigh. Note the yield.
Analysis

1. Weigh accurately about 0.1g of the dried copper oxalate

complex into a conical flask
2. Add 10 mL of 4N H2SO4, dilute to 50 mL. Heat to boiling.
3. Titrate the hot solution with 0.05N KMnO4.and note the end
point which is the appearance of permanent pink color.
1000 mL 1N KMnO4 = 44.01g of C2 O 42-
44.01 𝑁𝐾𝑀𝑛𝑂4
% of [C2O4]2– in the complex = 1000 × × 𝑉𝐾𝑀𝑛𝑂4 × 100
𝑊𝑐

(Wc = Weight of the copper oxalate complex)

Rough Observation

Weight of Volume
complex of
Sl.No. Burette Reading % of C2O4
taken KMnO4
(Wc gms) (VKMnO4)
Initial Final
1
2
3

23
 Organic Experiments

Expt: 7
BASE CATALYZED ALDOL CONDENSATION

Aim: Synthesis of dibenzalpropanone by Aldol condensation

Glasswares required:
 Watch glass– 1No.
 Glass rod – 1No.
 Conical flask (250 mL) – 1No.
 Boiling tube – 1No.

Chemicals Required:
1. Acetone (0.7 mL)
2. Benzaldehyde (2.5 mL)
3. NaOH soln. (2.35g in 23 mL water)
4. Ethanol (15 mL)

Procedure:

1. To a 250 mL conical flask add 23mL of 10% NaOH and 15

mL of ethanol. Then cool the mixture in an ice bath.

2. To the resultant solution, add 2.5 mL benzaldehyde, then add

0.7 mL acetone slowly over 15 minutes. Then, stir the reaction
mixture with a glass rod vigorously till the product precipitate
is formed.

3. A yellow solid will appear slowly and after 30 mins, it was

filtered through by Buckner Funnel through Whattman’s filter
paper.

4. Wash with water, dry, weigh and recrystallize from ethanol.

5. Find out the melting point of recrystallized aldol product.

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 Reaction:

Benzaldehyde Acetone Dibenzal acetone (or)

Dibenzylidene acetone

Mechanism:

25
Expt : 8
HALOGEN ADDITION TO C=C BOND

Aim : Bromination of cis or trans-stilbene

Glasswares required:
 Double neck RB flask (100 mL)
 Water condenser
 Dropping funnel (10 mL)
 Measuring cylinder (20 mL)

Chemicals Required:
 Cis or trans-Stilbene - 1.8 g
 33% HBr in acetic acid - 5.2 mL
 30% Hydrogen peroxide - 7 mL
 Ethanol - 15 mL

Procedure:

1. Add stilbene (cis or trans) (1.80 g) and ethanol (15 mL) to a

two neck 100 mL round-bottom flask fitted with reflux
condenser and a dropping funnel and reflux on a water bath.

2. Add 5.2 mL of HBr (33%) and hydrogen peroxide (H2O2,

30%) (7 mL) using dropping funnel sequentially to this
refluxing solution of stilbene.

3. The colourless solution will become deep orange in colour,

within 15-20 minutes, the orange colour will disappear. This
indicates the bromination of stilbene.

4. Allow the solution to cool to precipitate stilbene

dibromide.Filter the precipitate, wash with two or three small
portions (3 mL or less) of ethanol until the organic color is
removed and dry.

26
 5. Find out the melting point of the formed product.

6. Based on the melting point of the product, identify the

stereochemistry of the product and stilbene.
Reaction

trans- stilbene meso-1,2- dibromo-1,2- diphenylethane

cis -stilbene

Caution:

Care must be taken while handling the solution of hydrogen bromide

and hydrogen peroxide. Avoid contact with skin. Do not inhale. In
case of accidental touch, wash with plenty of water immediately.

Mechanism:

27
Expt: 9 QUALITATIVE ANALYSIS OF ORGANIC
COMPOUND

TESTS FOR FUNCTIONAL GROUPS

Experiment Observation inference

Test for Acids: A brisk effervescence

a) NaHCO3 test: with the evolution of
Sample + 1 mL of CO2. Presence of Acid
NaHCO3 solution
b) NaOH test:
0.1 g of substance (3 On acidifying with
drops) + 1 mL 10% conc. HCl, the acid is
NaOH solution. precipitated. Presence of Acid
Shake well. All
organic acids
dissolve when shaken
with NaOH.

Test for Aldehydes

and Ketones:
a)Borsche's test: Orange solution Presence of Aldehyde
Substance + ~1 mL (or) precipitate or Ketone
Borsche‟s reagent,
heat and add 1 mL
Conc.HCl.
b) Fehling’s
Solution Test: (for
Aliphatic Aldehydes Red Precipitate Presence of Aliphatic
only) Aldehyde or aldose
Sample + ~1 mL ( like Glucose)
each of Fehling‟s
solution “A” & “ B”.
Heat it for 2-3 mins.

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c) Tollen’s Reagent
test:(Aldehyde only)
Sample + ~1 mL Bright silver mirror Presence of
Tollen‟s reagent, forms on the sides Aldehyde or Aldose
Heat the test tube in a of the test tube. (like Glucose)
water bath for 5 mins.
d) Legal’s test: (for
ketones only)
Sample + 2 mL water
+ 5 drops of Sodium
nitroprusside solution Presence of ketone
Red colour
+ 5 drops NaOH+ 5
changes to purple
drops CH3 COOH

Test for Phenol

Sample +1 mL of A violet colour Presence of phenol
neutral Ferric
chloride

Test for Amines

a)Solubility test: Substance is soluble
0.1g substance +~ 1 and reappears on Presence of Amine
mL dil HCl. Shake adding NaOH
well.
b) Dye Test:
Sample +~ 3 mL dil. A Scarlet red dye
HCl, cool(in ice), add A Primary Amine
1 mL NaNO2 solution
and 1 mL alkaline – β
-naphthol

29
 APPENDIX-I

S.No Solution Weight/Volume Required

1. NaOH (0.1 N) 8.0 g / 2 lit
2. HCl (0.5 N) 90 mL / 2 lit
HCl (0.1N) 18 mL / 2 lit
3. NaCl (1%) 2g / 200 mL
4. I2 (0.005M) 2g KI+water+1.27g I2,
makeup to 1 lit
5. KI (0.1 N) 8.3 g /500 mL
6. Na2S2O3.5H2O (1.0N) 248.18g / 1 lit
7. Sat. I2 in CCl4 10g I2 /500 mL CCl4
8. H2SO4 (0.5 N) 14 mL / 1 lit
9. KNO3 (0.1 N) 5.055 g / 500 mL
10. HCOOH (0.5 M) 9.55 mL / 500 mL
11. KBr (1.0 M) 59.5g / 500 mL
12. CuSO4.5H2O (0.1N) 24.971g/1 lit
13. FeSO4.(NH4)2SO4.6H2O 196.1 g / 1lit add 5 mL conc
( 0.5 N) sulphuric acid
14. KCl (0.01 N) 0.746 g / 1 lit
15. KMnO4 (0.1 N) 3.1606 g/1 lit
16. K2Cr2O7 (0.1 N) 4.903g/ 1 lit

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 APPENDIX -II

Preparation of Indicators and reagents

S.No Indicator Preparation of solution

1. Diphenylamine Dissolve 1 g of substance in 100 mL
of Conc.H2SO4
2. Phenolphthalein Dissolve 5 g of Phenolphthalein in
100 mL of 50% alcohol
3. Fehling‟s A A blue aqueous solution of
copper(II) sulfate,
4. Fehling‟s B A clear solution of aqueous
potassium sodium tartrate (also
known as Rochelle salt) and a
strong alkali (commonly sodium
hydroxide).
5. Borsche‟s reagent Alcoholic solution of
2,4-Dinitrophenylhydrazine
and con.H2SO4
6. Tollen‟s reagent It is usually ammoniacal silver
nitrate, but can also be other
mixtures, as long as aqueous
diamminesilver(I) complex is
present.

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NOTES

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