BCHEL 148 (English)

BCHEL-148
Indira Gandhi National

Open University
School of Sciences
ORGANOMETALLICS,
BIOINORGANIC CHEMISTRY,
POLYNUCLEAR HYDROCARBONS AND
UV, IR SPECTROSCOPY: Lab
SECTION A
UNIT 1
Paper Chromatographic Separation and Identification of Metal Ions 5
Experiment 1: Separation and Identification of Cations of Analytical
Group I 8
Experiment 2: Separation and Identification of Cations of Analytical
Group II 11
UNIT 2
Inorganic Preparations and Measurement of their Conductivities 15
Experiment 3: Preparation of Tetraamminecarbonatocobalt(III) Nitrate 21
Experiment 4: Preparation of Tetraamminecopper(II) Sulphate
Monohydrate 23
Experiment 5: Preparation of Potassium Trioxalatoferrate(III)
Trihydrate 25
Experiment 6: Comparison of the conductance of the complexes
(prepared by Experiments 3 to 5) with M/1000 solution of
NaCl, MgCl2 and LiCl3 30
SECTION B
Experiment 7: Systematic Qualitative Analysis of Carboxylic Acids and
Phenols and Preparation of their Derivatives 35
Experiment 8: Systematic Qualitative Analysis of Aldehydes and

Ketones
and Preparation of their Derivatives 51
Experiment 9: Systematic Qualitative Analysis of Amides, Nitro and

Amino Compounds and Preparation of Their Derivatives 61
Experiment 10: Identification of Unknown Organic Samples 78

Course Design Committee
Dr Pritam Mukhopadhyay , School of Sciences,

Associate Professor, School of Physical IGNOU, New Delhi 110068
Sciences, Jawaharlal Nehru University.
New Delhi Prof. M.S. Nathawat
Prof. Sunita Malhotra
Dr. Preeti Malhotra,
Department of Chemistry, Prof. Bharat Inder Fozdar
University of Delhi, Delhi Prof. Javed A. Farooqi
Prof. Sanjiv Kumar
Dr. Sushmita Choudhury (Retd.),
Prof. Lalita S. Kumar
Gargi College, University of Delhi
New Delhi Prof. Kamalika Banerjee
Dr. Sangeeta Pandita

Department of Chemistry
Zakir Husain Delhi College
University of Delhi, Delhi
Block Preparation Team

Prof. Kamalika Banerjee (Units 1 and 2)
School of Sciences, IGNOU
Prof. Bharat Inder Fozdar (Experiments 7, 8, 9 and 10 )

School of Sciences, IGNOU
Course Coordinator: Prof. Kamalika Banerjee

Production
Mr. Rajiv Girdher Mr. Hemant Kumar
AR (P), MPDD, IGNOU SO(P), MPDD, IGNOU
Acknowledgements: Sh. Sarabjeet Singh and Sh. Deepak Kumar for word processing and Sh.
Sarabjeet Singh for CRC preparation.
Unit 1 has been adapted from Experiment 4 of CHE-12L chemistry course, portions of Unit 2 of
CHE-07L and Unit 18 of AEC-01 has been utilised in the writing of the four experiments of Unit 2. The
utilisation of some content of Chemistry Lab III course (BCHCL 136) for developing Part B is gratefully
acknowledged.
March, 2022
 Indira Gandhi National Open University, 2022
ISBN:
All rights reserved. No part of this work may be reproduced in any form, by mimeograph or any other means,
without permission in writing from Indira Gandhi National Open University.
Further information on Indira Gandhi National Open University courses may be obtained from the University’s
office at Maidan Garhi, New Delhi-110 068 or IGNOU website www.ignou.ac.in.
Printed and published on behalf of Indira Gandhi National Open University, New Delhi by the Registrar, MPDD,
IGNOU.
Printed at:
CHEMISTRY LAB: Organometallics, Bioinorganic
Chemistry, Polynuclear Hydrocarbons and UV, IR
spectroscopy
Welcome to the sixth Semester laboratory course in chemistry. This manual gives the
procedural details of various experiments you are required to perform in the course of this lab
work. Appropriate conceptual basis has also been laid for each experiment to make this
manual complete in itself.
This Laboratory manual has two sections. Section A deals with experiments in inorganic
chemistry and Section B with experiments in organic chemistry. There are six experiments
in the Section A. First unit has two experiments based on paper chromatography. Thereafter
the second unit, the first three experiments provide procedural detail for preparation and the
purification of three inorganic compounds.. In the last experiment you will also compare the
conductance of these prepared complexes with M/1000 solution of NaCl, MgCl2 and LiCl3. ,
respectively.
Part B mainly deals with qualitative organic analysis. We shall study the experiment
procedures for the qualitative classification tests and preparation of derivatives for organic
compounds having commonly encountered functional groups such as phenolic, carbonyl,
carboxylic, amino, and nitro.
All the experiments of this course are to be performed in about six days.
Expected Learning Outcomes
After studying this course and performing the given experiments, you will be able to:
 understand theoretical principle of chromatography and separate and identify cations of
analytical group I and II with the help of paper chromatography;
 prepare and purify complexes and compare their conductances with those of standard
solutions;
 describe the steps involved in the identification organic compounds by classical
qualitative organic analysis;
 describe functional group tests and methods of the preparation of derivatives;
 identify the unknown organic compounds; and
 maintain laboratory records for the experiments performed during this course;
Study Guide
The general pattern of discussion of experiments in this course is similar to that of 1st , 2nd ,
3rd and 4th semesters Chemistry Labs. In this lab course, you would be doing ten
experiments. In this course, the performance of the experiments, recording the data,
calculations and expression of result are to be done as in earlier chemistry lab course. The
maintenance of Laboratory note book may be done as per the detail guidelines given for
each Section. Some general guidelines for the maintaining Laboratory note book are given
on next page. Remember that each experiment is going to be evaluated. Hence, read the
Lab manual before going the laboratory for performing the experiments. This will help you in
doing experiment in a proper way.
We want you to share the thrill of learning by doing. There is no better way to learn.
So, Best of Luck.

Laboratory Notebook
It is essential to keep a proper record of the work that has been done. The record should
reflect all the observations at various stages of the experiment. The observations prove
helpful in correct interpretation of an experimental result.
While preparing a laboratory note book, the following important points may be kept in mind.
 A bound note book should be used for laboratory record. You may use a laboratory
record note book in which one side has ruled pages and other side is unruled.
 All entries must be made in ink. If you commit a mistake, it should be crossed and
correct entry should be made.
 The first few pages in the note book should be left for making a list of contents.
 Graphs drawn should be attached to the laboratory note book.
 The laboratory note book is a complete record of all operations. Date, time, the number
and the title of each experiment must be entered regularly.
 Record all observations and data in the note book at the time they are obtained. Never
use scraps of paper for noting particulars like masses of substances weighed, melting
points etc. They might get lost or mixed up.
 The record should be clearly written and well organised. On reading it, one should be
able to understand what has been done.
 It may not be necessary to copy out the exact procedure, since this is given in your
laboratory manual.
 The detailed calculations are to be shown.
 Results and conclusions drawn should be summarised for each experiment and
explanation provided, if the results vary from those expected.
Certain marks have been allotted for maintaining a good laboratory note book too.
IMPORTANT
 Attendance is compulsory in the Laboratory Course work held generally
at the Study Centre.
 The Laboratory Course is worth 2 credits to be completed over 7 days
duration:
 6 days of the Guided Laboratory work
 1 day of the Unguided Laboratory work
 To successfully complete the laboratory course you will have to pass (at
least 35% marks) in the Guided and Unguided components separately.
Unit 1 Paper Chromatographic Separation and Identification of Metal Ions
UNIT 1
PAPER CHROMATOGRAPHIC
SEPARATION AND
IDENTIFICATION OF METAL
IONS
Structure
1.1 Introduction Requirements
Expected Learning Outcomes Procedure
1.2 Theory of Chromatography Observations and Calculations
Definition and Classification Result and Discussion
Principle 1.5 Experiment 2: Separation and

Identification of Cations of
The Concept of Rf Value
Analytical Group II
1.3 Paper Chromatographic
Requirements
Separation of Metal Ions
Procedure
1.4 Experiment 1: Separation and
Identification of Cations of Observations and Calculations
Analytical Group I
Result and Discussion
1.1 INTRODUCTION
In this BCHEL-148 laboratory course, first two experiments are based on
paper chromatography. Here we shall first discuss the basic theory of
chromatography with some fundamental concepts. After that you will be
introduced to the actual experiments in which you will perform paper
chromatography of metal ions (Experiments 1 and 2).

After studying this unit and performing the given experiments you should be
able to:
 define and classify chromatography;

5
BCHEL 148 Organometallics, Bioinorganic Chemistry,
Polynuclear Hydrocarbons and UV, IR Spectroscopy: Lab
 understand theoretical principle of chromatography;
 calculate the Rf values; and
 separate and identify cations of analytical group I and II.
1.2 THEORY OF CHROMATOGRAPHY

1.2.1 Definition and Classification
Chromatography is referred to any of a diverse group of techniques that effect
a separation through a distribution of sample between two immiscible phases.
One phase is stationary whereas the second is mobile which percolates
through the first phase. The stationary phase may be a solid or a liquid while
the mobile phase may be a liquid or a gas.
There are various ways to classify chromatography. On the basis of physical

state of mobile phase the chromatography is classified into two broad groups.
 Liquid chromatography in which mobile phase used is in the form of a

liquid.
 Gas chromatography in which mobile phase used is a gas.
1.2.2 Principle
Chromatography is essentially a separation process which affects a separation
by distributing the sample into two phases. One phase is stationary and
second is mobile and flows through the stationary phase. During the process
of movement of mobile phase, small differences in adsorption-desorption or
partitioning or ion-exchange behaviour of each component of a mixture are
multiplied many fold and these parameters distinguish between the different
solutes. The ability of chromatography to separate two solutes depends on the
selectivity of the process and the degree to which the system can distinguish
between the two solutes. The magnitude of the distribution is determined by
the physico chemical nature of the solute and that of the mobile and stationary
phases, beside various physical interaction (such as: hydrogen bonding,
dipole moment etc.) of the solute with stationary-and mobile phases.
Some common steps used in different chromatographic techniques are:

application of the sample onto a stationary phase, percolating a mobile phase
over the stationary phase, obtaining the separation of components, collection
of the different components for qualitative or quantitative purposes. Therefore,
the principle of chromatography can be understood by taking a one kind of
chromatography. For this purpose, let us consider a simple example of
separation by column chromatography. This can be applied to other methods
as well.
Let us suppose that we wish to separate a mixture of two (say coloured)

components A and B. A small amount of the sample solution is introduced at
the top of the column which is packed with suitable adsorbent (stationary
phase). First a narrowband is formed at the top of the column. The developer
6 (mobile phase) is now poured into the column and is allowed to flow through
the column. The two important steps are: (i) formation of the initial zone (ii)
development of the initial zone and allowing the components to appear as
separate zones. As soon as the solution comes in contact with the stationary
phase (column material or adsorbent) and the mobile phase the following
reversible reaction occurs:
Solute in the Stationary phase ⇌ solute in the mobile phase
For which the equilibrium concentration are related as
C Cs
K   1/ K m or K … (1.1)
Cs Cm
where, K' = 1/K and K' is equilibrium constant.
K is called as the distribution coefficient, Cs is the concentration of the solute in

the stationary phase and Cm that in mobile phase.
For two solutes A and B there is competition of A and B (i) for the stationary
phase and (ii) for the mobile phase.
If the stationary phase takes B more likely than A, the value of KA will be less
than KB. Thus when the developer leaves the narrow band it is richer in A than
B. The developer flowing downwards now comes in contact with fresh
stationary phase and the solutes A and B face the new competition and when
the mobile phase leaves this part of the stationary phase, each time it
becomes richer and richer in A. Small differences in the interactions of A and
B with stationary and mobile phases become exaggerated as the developer
proceeds down the column, soon after the well separated bands of A and B
are obtained.
If the development further proceeds (elution analysis) the components A and B

of the mixture are elute out of the column. Solute A which has smaller K
emerges first followed by B which has a larger K The two fractions may be
quantitatively analysed for A and B respectively.
1.2.3 The Concept of Rf Value

Rf value of a solute is the ratio of the rate of movement of the solute peak to
the rate of movement of the eluting solvent.
distance to leading edge of spot
However, one can not readily detect the position of the solvent front or of the Rf 
distance to solvent front
solute on the column chromatography. These are better measured now in
terms of retention volume or retention time.
6
A Rf   0.50
12
In paper chromatography Rf value is constantly quoted as a characteristic of 10
B Rf   0.83
the solute. It describes the migration of solute relative to that of developer and 12
is given by
Measuring Rf values in
distance moved by the centre of the solute zone paper chromatography
Rf 
distance moved by the solvent front
With this background, now we will take up experiment based on different types
paper chromatography. 7
1.3 PAPER CHROMATOGRAPHIC SEPARATION

OF METAL IONS
Paper chromatography (PC) is a simple technique to separate complex
mixtures of metal ions, amino acids, sugars, dyes and drugs. A very small
amount of sample is required for the analysis. PC has become a popular
technique for the separation of metal cations. In this experiment, the use of PC
will be illustrated to separate a mixture of cations of group I and group II.
1.3.1 Principle
In paper chromatography of cations, the principles of partition, adsorption and
ion exchange may be exploited, out of these the most important is partition the
involves the distribution of a solute between a mobile liquid phase and a gel (a
kind of water cellulose complex) as the stationary phase. The different
components of the sample are distributed across the paper depending on their
partition coefficients.
Attempts have been to employ paper chromatography for the systematic

qualitative analysis of metal cations. However, it is not possible to separate all
the cations simultaneously and therefore, the separation of a group of cations
can be handled. Most frequent of these is the preliminary separation into the
current analytical groups, each of which is then subjected to a separate
chromatographic analysis. In the Experiments (1 and 2) you will learn the use
of paper chromatography for the separation of cations of analytical group I and
group II, respectively.
1.4 EXPERIMENT 1: SEPARATION AND

IDENTIFICATION OF CATIONS OF
ANALYTICAL GROUP I
This experiment of an easy ascending paper chromatographic technique is
rapid and requires no special apparatus or reagents. A very simple procedure
for this separation has been employed with the use of only distilled water as
the developer. However, other developers can also be utilised depending on
the availability of the reagents and precautions in their use [e.g. butanol -1 +
pyridine + water (15:1:9)]. In this experiment you will perform the separation of
cations of group I.
1.4.1 Requirements
Apparatus Chemical
Boiling tubes or chromatographic jar 5 Potassium chromate
Measuring cylinder 1 Lead nitrate
Pipette 1 Silver nitrate
Spotting capillaries 5 Mercurous nitrate
Small test tubes 5 Nitric acid
Whatman No. 1 filter paper
8
Solution provided
1) Unknown solution: It can be prepared by dissolving any one or two

nitrate of analytical group in water.
2) Detector: 0.25 M aqueous solution of potassium chromate K2Cr2O4 is Application of the

prepared by dissolving 24.25 g K2CrO4 in distilled water in 250 cm3 sample on the paper
volumetric flask. should be on a small
area. Larger spots
1.4.2 Procedure lead to poorer
separations.
Proceed according to the following steps: Please indicate the
name of test sample
1. Preparation of solutions on the top of the
paper strip.
i) Prepare 1 cm3 aqueous solutions of (i) lead nitrate (ii) silver nitrate (iii)
The paper in the
mercurous nitrate by dissolving about .1g crystals in a small test tube.
boiling tube or in the
Add few drops of HNO3 to prevent hydrolysis. For the preparation of jar should be
mixture of cations, add few drops of each cation solutions in a test tube. vertically changed
and it should not
ii) Developer: Distilled water. touch the sides of the
tube.
2. Cut whatman No. 1 filter paper strips of the required size: 15 cm x 2 cm
to fit usual boiling tube or 15 cm x 3 cm for chromatographic jar. The spot of the solute
(at the point of
3. On each strip draw a line at about 1 cm of the one and put a dot in the application) should
centre of line. This end will be the bottom of the strip and development always be above the
will take place from this end. level of the developer
otherwise the solute
4. Apply the solutions of Pb2+, Ag+ and Hg 22 separately on 3 strips with the will mix with the
developer and error
help of a fine capillary. Use a fresh capillary for each solution. The
will be resulted.
teacher is supposed to demonstrate the technique of application of the
solution. Ensure that the spot
gets dried before
5. On the 4th paper strip apply the mixture of the three cations. placing the paper in
the boiling tube.
6. Apply the unknown solution (e.g., containing any one or two on the 5th
paper strip. Do not allow the
paper to come in
7. Place 5 dry boiling tubes vertically in a stand. contact with
impurities.
8. Add distilled water, with the help of a pipette, to each of the boiling tubes
so that the height of the developer (distilled water) in each of the boiling
tubes is less than 1 cm. The sides of the boiling tube must be dry as far
as possible.
9. Suspend the spotted and dried paper strips in the respective boiling
tubes containing distilled water with the upper end pinned to the cork
and the lower end touching the developer. Care is taken to see that this
is done gently and the strip is vertical. The spot should always be above
the developer level.
10. Allow the developer to rise along the paper and wait till the developer
(solvent front) reaches near the upper end of the paper. 9
Apparatus for paper

chromatography
11. Remove the paper from the boiling tube and mark the solvent front with
the help of a pencil.
12. Get it dried to evaporate the developer.
13. Take potassium chromate solution in a pettri dish (or a watch glass) and
dip the dried paper in the detector.
An alternate method for developing paper chromatogram by making paper

cylinder. Beaker can be covered by aluminum foil.
14. Encircle the coloured zones with pencil and mark the centre of the zone.
15. Calculate the Rf values.
16. Compare the Rf values of individual cations with that of their Rf values in
known mixture and in unknown.
10 17. Identify the cations present in the unknown on the basis of Rf values.
1.4.3 Observations and Calculations

Observe the coloured spots of different cations. Pb2+ will appear as yellow;
Ag+ as orange-red and Hg 22 as orange zones. Measure the distance of the
centre of each solute zone from the point of application. Call this distance ds.
Measure the distance between the solvent front and the starting line and call
this distance as dm. Calculate the Rf value of each solute by the relation:
distance travelled by the centre of the solute zone d s

Rf  
distance travelled by the solvent front dm
Record your data in the following way:
Observation Table
PC of Metal Ions of Group I
Sample ds dm Rf = ds/dm Remark

+
Ag
Hg22 
2+
Pb
Mixture
Unknown
1. Rf resembles with………
1.4.4 Result and Discussion

Metal ions present in the unknown sample are: .
1…………
2…………
The metal ions of analytical group I move along the paper in distilled water at
different rates. On dipping in detector K2CrO4 solution the coloured
precipitates of the chromates of lead, mercurous and silver appear as yellow,
orange and orange-red zones on the paper. Sometimes, when the coloured
spot of Hg22  is not intense, the paper is exposed to ammonia vapours: the
mercurous compound gives black spot. Lead migrates with the fastest rate
and appears at the upper most area on the paper. Mercurous follows the lead.
Silver migrates with the slowest rate and appears below the mercury zone.
1.5 EXPERIMENT 2: SEPARATION AND

IDENTIFICATION OF CATION OF
ANALYTICAL GROUP II
In this experiment you will perform the separation of bismuth (III), copper (II),
cadmium (II), lead (II) and mercury (II) using paper chromatography. This 11
separation is achieved by 1-butanol saturated with 3M HCI as developer.

However, another simple developer containing ethanol + water + 1M HCI
(18:1:1) can also be used to separate Pb2+ , Cu2+, Cd2+ (excluding Hg2+ from
Group II).
1.5.1 Requirements
Apparatus Chemical
Boiling tubes 5 1-Butanol
Measuring cylinder 1 3M HCl
Pipette 1 bismuth chloride
Cupric chloride Lead chloride
Spotting capillaries 7 Mercuric chloride
Small test tubes 7
Pettridish
Whatman No. 1 filter paper sheets
Solution provided
1. Unknown Solution: It can be prepared by dissolving any one or two

chlorides of analytical group II in water.
2. Preparation of Detector 1: H2S water. It is prepared by passing H2S gas

in water and add a few drops of ammonia to it. Keep it in a covered
container.
3. Preparation of Detector 2: Dithizone. Prepare a conc. solution of

dithizone in chloroform or carbon tetrachloride.
1.5.2 Procedure
Proceed according to the following steps.
1. i) Preparation of Solution:
Sample Preparation: prepare 1 cm3 concentrated aqueous solutions

of (i) bismuth chloride (ii) cadmium chloride (iii) cupric chloride
(iv) lead chloride and (v) mercuric chloride. Add 1-2 drops of
hydrochloric acid to prevent hydrolysis. For the preparation of the
mixture of their cations, add few drops of each cation solutions in a
test tube.
ii) Preparation of Developer: Developer (1-butanol saturated with 3M

HCl): Prepare this developer by taking equal volumes of 1-butanol
and 3M hydrochloric acid in a separatory funnel. Shake well and allow
to stand to separate the layers clearly. Reject the lower aqueous layer
12 and use the upper (organic) layer as the developer.
2. Cut whatman No. 1 filter strips of about 15  2 cm to be placed in usual

boiling tubes (or chromatographic jars).
3. On each strip draw a line with pencil at about 1 cm of one end and mark a
point in the centre of line. This point is the point of application of the
solute/sample solution.
4. Apply the test solution to the point of application with the help of a fine
capillary. Apply bismuth, cadmium, copper, lead and mercury solutions
separately on 5 strips. Use a fresh capillary for each solution.
5. Apply the mixture solution and unknown solution separately on other

strips. Application of solution can be repeated twice or thrice if the
solutions are dilute.
6. Take the clean and dry boiling tube and place (10-15 cm3 of) the
developer in each of these boiling tube.
7. Suspend the spotted and dried paper strips in the respective boiling tubes
containing distilled water with the upper end pinned to the cork and the
lower end touching the developer. Care is taken to see that this is done
gently and the strip is vertical. The spot should always be above the
developer level.
8. Allow the developer to rise along the paper and wait till the developer
(solvent), reaches near the upper end of the paper.
9. Remove the paper strip and mark the solvent front with the help of a
pencil.
10. Leave the paper for some time to get it dried.
11. Hold the paper in an atmosphere of H2S gas until the zones of metallic
sulphides are seen. An alternative way is to use H2S water in which the
paper is dipped to locate the zones. Another alternative method is use
dithizone for detecting the zones of metal ions. Spray the paper (or dip in)
with a concentrated solution of dithizone in chloroform.
12. Encircle the coloured zones and mark the centrer of each zone. Calculate
the Rf values of individual cations with that of their Rf values in mixture to
identify the cations in the mixture and unknown sample solution.
1.5.3 Observations and Calculations

Observe the colour of the spots of various cations of group II. With H2S
bismuth (III) will appear as dark brown: cadmium (II) as yellow: copper (II) as
chocolate brown: lead (II) as black and mercury (II) as black zones.
Measure the distance travelled by the centre of the solute zone (ds) and the
distance travelled by the solvent front (dm) on the paper chromatogram.
ds
Calculate the Rf values of each solute by the relation. R f  .
dm
Record your data in the following way: 13

Observation Table
PC Separation of Pb2+, Cu2+, Cd2+, Bi3+ and Hg2+
Sample cation ds dm Rf = ds/dm Remark
Hg2
Cd 2
Bi 3 
2+
Pb
Cu 2 
Mixture
Unknown
1.5.4 Result and Discussion

Metal ions present in the unknown sample are:
1. …………
2. …………
The rate of migration of group II metal ions inn butanol saturated with 3M HCI
appears in the order Hg 2   Cd 2   Bi 3   Pb 2   Cu 2  .
When H2S is used as detector the coloured zones of metallic sulphides are
seen: HgS black, CdS yellow, Bi2S3 dark brown, PbS black and CuS
Chocolate brown.
When dithizone is used as detector, coloured complexes of metal ions are

formed with dithizone. Dithizone is the commercial name of diphenyl-1-
thiocarbazone (see formula in below).
Metal ion + Dithizone  coloured complex
Colours of the complexes of metal ions are: mercury-pink, cadmium- purple,

bismuth-purple and copper brown. Lead is not clearly detected for which
rhodizonic acid may be used.
S
NH NH C NH NH
Diphenylthiocarbazone
(dithizone)
14
Unit 2 Inorganic Preparations and Measurement of Their Conductivities
UNIT 2
INORGANIC PREPARATIONS
AND MEASUREMENT OF THEIR
CONDUCTIVITIES
Structure
2.1 Introduction 2.5 Experiment 5: Preparation of
Expected Learning Outcomes Potassium Trioxalatoferrate (III)
Trihydrate
2.2 Conductance and
Principle
Conductometry
Requirements
2.3 Experiment 3: Preparation of
Tetraamminecarbonatocobalt Procedure
(III) nitrate Observations
Principle Calculations
Requirements Result
Procedure 2.6 Experiment 6: Comparison of
Observations the conductance of the
complexes (prepared by
Calculations Experiments 3 to 5) with
Result M/1000 solution of NaCl, MgCl2
2.4 Experiment 4: Preparation of and LiCl3
Tetraamminecopper(II) Sulphate Principle
Monohydrate Requirements
Principle Procedure
Requirements Observations
Procedure Calculations
Observations Result
Calculations
2.7 Summary
Result
2.8 Answers
2.1 INTRODUCTION
In Unit 1, we discussed the use of paper chromatography to separate a
mixture of cations of group I and group II. In this unit, we will discuss the 15
preparation and the purification of three inorganic compounds. You will have
to prepare and purify these compounds during the laboratory practicals of this
course. You will also compare the conductance of these prepared complexes
with M/1000 solution of NaCl, MgCl2 and LiCl3.

After studying this unit, you should be able to:
 prepare and purify tetraamminecarbonatocobalt (III) nitrate,

tetraamminecopper(II) sulphate and potassium trioxalatoferrate(III)
trihydrate;
 perform various laboratory operations involved in these preparations;
 calculate percentage yield of these compounds;
 explain the principles involved in the preparation of these compounds;
 measure the conductance of these compounds; and
 compare their conductance with that of M/1000 solution of NaCl, MgCl2

and LiCl3.
2.2 CONDUCTANCE AND CONDUCTOMETRY

Some Basic Concepts of Conductance
The ease of flow of electric current through a body is called its conductance. In
metallic conductors it is caused by the movement of electrons, while in
electrolytic, solutions it is caused by applied electrical field. The electrolytic
conductance, G; of a medium is equal to the reciprocal of its electrical
resistance R in ohms:
1
G … (2.1)
R
The flow of current through an electrolytic solution is due to the charge

carried-out by - ions and causes electrolytic conduction. We thus expect
movement of ions in aqueous’ solutions of electrolytes and also in molten
electrolytes.
Specific Conductance
Since a solution is a three dimensional conductor, the ‘exact resistance will

depend on the spacing (l ) and area (A) of the electrodes.
16
The resistance of a solution is proportional, to the distance between the

electrodes and inversely proportional to the electrode surface area. If two
electrodes having a cross sectional area of A m2 and separated by l m are
dipped in a solution of some electrolyte, the resistance (R) of the solution
present between the two electrodes is:
R  l
1
R 
A
l
and R   … (2.2)
A
were  (Rho) is proportionality constant and is called as specific resistance Conductivity

or resistivity. increases with:
Reciprocal of specific resistance is known as specific conductance or (i) Concentration of

conductivity designated by  (kappa): the solution and
(ii) Speed of the
1
 … (2.3) ions concerned.

Hence Eq. (2.2) can be written as

1 1
R 
 A
1 l
  … (2.4)
R A
The ratio (1/A) is known as cell constant, Kcell and (1/R) = G (from Eq. 2.1).
Now we can summarise as,   1/   (1/ R ) ( l / A )  G K cell … (2.5)
Conductivity = observed conductance  cell constant
Since the resistance is expressed in ohm,  (omega) the reciprocal ohm (1)
was earlier used as the unit for conductance. However, in SI system, the unit
for conductance is ‘Siemens’ and, given the symbol ‘S’. Hence, the unit for
conductivity will be S m1 (1S = 11) or S cm1. It may be remembered that
S m1 = 1/100 S cm1. However specific conductance is customarily reported
in smaller units as milli Siemens per meter (mS m1) and micro Siemens per
cm (S cm1).
Molar Conductivity
In order to compare quantitatively the conductivities of electrolytes, a quantity

called molar conductivity is frequently used. The molar conductivity, m,
(capital lambda) is the conductivity per unit molar concentration of dissolved
electrolyte. It is related to conductivity,  by the relation:

Λm  … (2.6)
c
where c is the concentration in mol m3. The molar conductivity is usually

expressed in S m2 mol1 or S cm2 mol1. It may be remembered that
S m2 mol1 = 10,000 S cm2 mol1. 17
It is to be remembered that c in Eq. 2.6 is to be expressed in mol m3 unit.
If the concentration is given in terms of molarity (mol dm3), then the
following conversion is to be carried out
c (mol m 3 )  Molarity  1000 … (2.7)
Earlier equivalent conductivity (eq), which is given by the following

expression, was in use
1000  
Λeq  … (2.8)
c
where c is the concentration expressed in terms of normality of the solution.

However, IUPAC recommends the use of molar conductivity only.
For example, consider equimolar solutions of sodium chloride and magnesium

chloride. The concentration of chloride ions in the solution of magnesium
chloride is double the concentration of chloride ions in the solution of sodium
chloride. The amount of charge carried by one magnesium ion is double the
amount of charge carried by sodium ion. Molar conductivity will therefore
change with the number of ions produced per mole of solute.
Thus, the number of ions in ionic salts relate to molar conductivity m, as
shown below.
Table 2.1: Molar Conductivity Values of Some Ionic salts
Number of ions m (S cm2 mol1)

2 118-131
3 235-275
4 408-435
5 ~560
In conductometry we examine the transport of electricity in solution and

application of this phenomenon to chemical analysis. The principle advantage
of this technique is its simplicity and relatively good sensitivity. The behaviour
of electrolytic solutions, determining the purity of water, acid-base,
precipitation, determination of ionization constants, solubilities and complex
formation, all these can be studied with the help of conductometry.
Now we will see how conductance is measured.
Measurement of Conductance
Principle of Wheatstone Bridge is used to measure the conductance of

solution. Therefore, before taking up the measurement of conductance of
solution, let us study the principle of Wheatstone Bridge.
The Wheatstone Bridge Principle
A Wheatstone bridge (Fig. 2.1) is employed to measure the resistance of

an electronic conductor. It works on the principle of obtaining balance between
two arms with the help of a balance indicator (e.g. a galvanometer) at the
18 condition of potential being equal.
Let Rx be an unknown resistor, R1 and R2 two standard resistors, R3 an

adjustable resistor and G a galvanometer. The bridge is connected to a source
of power S, a battery, and a tapping key K is placed in the path to control the
connections.
i1 i2
R1 R2
S
B D
G K
_
i1
R3 i2 RX
Fig. 2.1: A DC Wheatstone Bridge circuit.
To measure the resistance Rx, the tapping key K is held down momentarily
and the bridge is balanced by adjusting R3 to get no deflection in
galvanometer under these conditions.
In the bridge the total current is divided into two paths: i1 through R1 and R3,
and i2 through R2 and Rx. Under the balancing conditions, the potential at
points B and D must be the same, i.e. the ohmic voltage drop through the
resistors Rl; and R2 must be the same. Hence, the potential at B (EB) must be
equal to potential at D (ED).
EB  ED … (2.9)
or i l R l  i 2 R2 … (2.10)
Similarly i l R3  i 2 R x … (2.11)
Dividing Eq. (2.10) by Eq. (2.11) we get,

R1 R 2

R3 R x
R2 R3
and Rx  … (2.12)
R1
Thus, we can calculate Rx as R1, R2 and R3 are all known. Conductance G,

being the reciprocal of resistance will be,
R1
G … (2.13)
R2R3
Alternatively, the conductometric cell can be incorporated into operational

amplifier control circuit, as shown in. Fig. 2.2. The amplifier balances the
potential of two inputs. The current from the input potential, Ei, is balanced by
the current from amplifier output which passes through a feedback resistor
(Rf). The output potential, E0 is in terms of resistance:
 Rf 
E 0  E i  
 Rx  1
where Rx is the resistance of conductometric cell. 19

With respect to the solution conductance, G, above equation becomes
E 0  E i ( R f G  1)
Rf
_
D
E0
+
Rx
Ei
Fig.2.2: An operational amplifier control circuit for conductometric

measurement. Rx is the solution resistance and Rf is the feedback
resistance.
Measurement of Conductance of a Solution

The Principle of the Wheatstone bridge can be used to measure the
conductance of solutions. However, the following considerations must also be
kept in mind:
(i) since a direct current would polarize the electrodes in the conductivity
cell by electrolyzing the solution to avoid polarization an alternating
current (ac) source of power must be used in place of a dc Source
(battery) usually ac voltages of 3-6 volts with frequency of 50 Hz or 1000
Hz used across points A and C of Fig. 2.3.
(ii) A suitable conductivity cell (with electrodes dipped in the solution) is

located between points C and D. Thus Rx represents the resistance of
the conductivity cell.
(iii) Since, the cell also acts like a small capacitor (Cx), and to balance its
capacitive resistance a variable capacitor, CB, must be inserted into the
bridge.
A
R1 R2
ac
B BI D
Conductivity cell
R3
RX
CB
CX
C
Fig. 2.3: A conductivity bridge circuit.
(iv) The balance indictor (BI) may be an ac galvanometer, but some other
devices are also be used:
 An earphone can act as a balance indicator if the frequency of the

ac source is in audio-range.
 A magic eye, which gives a green fluorescence as a result of

electrons striking a phosphor coating inside the glass tube, is used
20 in several commercial instruments.
 For much precise conductance measurements a cathode ray

oscilloscope is used as the balance indicator.
(v) Conductance (G = 1/Rx) can be read directly on commercially available

instruments as a panel mounted meter. Now several digital instruments
are also available, such instruments give the conductance directly as the
numerical value.
SAQ 1
At 298 K, the resistance of 2.00  102 M KCl is 195.96  and that of 2.50 
103 M K2SO4 is 775.19 . The conductivity () of 2.00  102 M KCI at 298 K
is 0.2768 S m1. Calculate molar conductivity of K2SO4 solution.
2.3 EXPERIMENT 3: PREPARATION OF

TETRAAMMINECARBONATOCOBALT(III)
NITRATE
In this experiment you will learn how to prepare tetraamminecarbonatocobalt
(III) nitrate.
2.3.1 Principle
Cobalt(III) forms kinetically inert coordination complexes. In comparison with
other transition metals they have slower ligand exchange. The slow reactivity
of this octahedral complex has made the chemists to further investigate it in
great detail. In this experiment, we will prepare the coordination compound of
cobalt, i.e. [ Co(NH3 ) 4 CO 3 ] NO 3 with the help of ligand substitution reaction.
Cobalt nitrate [Co(NO3)2] is deliquescent and therefore tends to absorb water
vapours from atmosphere and forms Co(NO3)2 . 6H2O. Since Co(II) complexes
react very rapidly by ligand exchange, therefore in the first step following
reaction takes place:
Co(OH2 )26  4NH3 (aq )  CO23  Co(NH3 ) 4 CO3  6H2 O
The intermediate tetraamminecarbonato cobalt(II) when formed, is oxidized by

+
addition of hydrogen peroxide (H2O2) to form [Co(NH3)4CO3] .
[Co(NH3 ) 4 CO 3 ]  { oxidation}  [ Co(NH3 ) 4 CO 3 ] 

by H2O2
Reaction involved:
Co(NO3 ) 2  NH3 (aq)  (NH4 ) 2 CO 3  H2 O 2  [ Co(NH3 ) 4 CO 3 ] NO 3  NH 4NO 3  H2 O
This sort of intermediate which has a carbonato ligand is a useful in the

synthesis of coordination complex. The carbonate ion is easily removed by the
additional of HCl and the carbonate forms carbon dioxide. The carbonate ion
is a bidentate ligand and leaves two open coordination sites. Water molecules
or chloride ions may occupy the open coordination sites. Water is not a strong

ligand and addition of ions such as X , NH3 or NO2 leads to the replacement of
these coordinated water molecules. 21
2.3.2 Requirements
Chemical Apparatus
Cobalt nitrate Beakers 150 cm3 2 No.

hexahydrate
Bunsen burner 1 No.
Ammonia
Evaporating dish 1 No.
Ammonium carbonate
Funnel glass 1 No.
Hydrogen peroxide
Funnel stand 1 No.
Distilled water
Glass rod 1 No.
Measuring cylinder 1 No.
Porous plate 1 No.
Tripod stand 1 No.
Watch glass 1 No.
Wire gauze 1 No.
Filter paper Few circles
2.3.3 Procedure
Weigh 10.0 g ammonium carbonate. Transfer to a 150 cm3 beaker. Dissolve in
25 cm3 distilled water and add 25 cm3 of concentrated aqueous ammonia. To
this, add around 4 g of cobalt nitrate (in 10 cm3 water) with continuous stirring.
After that add 3 cm3 of 30% hydrogen peroxide with stirring. Heat the solution
and reduce the volume to about 30 cm3 . During the evaporation, add 1.25 g
of ammonium carbonate slowly. Filter the solution while hot if it is not fully
dissolved. Cool the dark purple coloured solution (or filtrate) in ice bath and
then allow the red precipitate of [Co(NH3)4CO3] NO3 to settle. Filter the red
crystalline product by washing with cold distilled water. Dry the crystals by
pressing them gently between pads of filter papers. Allow to dry on a porous
plate. Weigh the crystals and record the yield. Calculate the percentage yield.
Structure
The tetraamminecarbonato cobalt(III) nitrate complex is having octahedral

geometry in which carbonate ligand is acting as a bidentate ligand.
+
Fig. 2.4: Structure of [Co(NH3)4CO3] ion.
22
2.3.4 Observations
Weight of cobalt nitrate taken = g
Weight of tetraamminecarbonatocobalt(III) nitrate = g

The reactant that is
(experimental yield)
completely consumed
in a chemical reaction
2.3.6 Calculation of Percent Yield
is called limiting
reagent.
Your objective should be to prepare as high a yield of
tetraamminecarbonatocobalt(III) nitrate as possible. To measure the efficiency
of the procedure, you should calculate the percent yield, where
exeperimental yield
Percent yield   100%
theoretical yield
The theoretical yield is the calculated maximum amount of product which

might be obtained under ideal conditions from the starting materials. In an
experiment, the theoretical yield is seldom, if ever, reached.
2.3.7 Result
The percent yield of tetraamminecarbonatocobalt(III) nitrate = %

TETRAAMMINECOPPER(II) SULPHATE
MONOHYDRATE
In this experiment you will synthesise a complex compound,
tetraamminecopper(II) sulphate monohydrate, [Cu(NH3 )4 ] SO 4 . H2O .
2.4.1 Principle
When aqueous ammonia is added to a solution containing copper(II) sulphate,

a pale blue precipitate of basic copper(II) sulphate is first formed. This
dissolves in excess of aqueous ammonia solution giving a deep blue solution
containing the complex ion, tetraamminecopper(II). Addition of ethanol to this
solution results in precipitation of a deep blue coloured complex,
tetraamminecopper(II) sulphate monohydrate:
2Cu2  (aq )  SO24 (aq )  2NH3 (aq )  2H2O (l)  Cu(OH)2 . CuSO 4 (s )  2NH 4(aq )
Cu(OH)2 . CuSO 4 (s )  8NH3 (aq )  [Cu(NH3 )4 ]2  (aq )  2OH (aq )  SO24 (aq )
[Cu(NH3 )4 ]2 (aq) SO 24 (aq )   [Cu(NH3 )4 ] SO 4 . H2O(s )

ethanol
The names and gram molecular weights of important compounds involved in this
experiment are listed below:
23
Name Formula Gram Formula Weight

g/mole
Copper(II) sulphate CuSO4.5H2O 249.5
Ammonia NH3 17
Tetraamminecopper(II) [Cu(NH3)4]SO4 . H2O 245.74

sulphate monohydrate
2.4.2 Requirements
Chemical Apparatus
Copper(II) sulphate Beakers 250 cm3 1 No.
Ammonia(aq), Sp. gr. 0.88 (15 M) Bunsen burner 1 No.
Ethanol Buchner funnel 1 No.
Distilled water Filtration apparatus 1 No.
Glass rod 1 No.
Measuring cylinder 1 No.
Tripod stand 1 No.
Watch glass 1 No.
Water bath 1 No.
2.4.3 Procedure
Weigh out 2.0 g copper(II) sulphate and powder it. Add powdered crystals to a
250 cm3 beaker. Prepare ammonia solution by adding 10 cm3 ammonia (aq) to
5 cm3 distilled water. Slowly add ammonia solution to the powder with stirring
until all the copper(II) sulphate dissolves resulting in a deep blue solution. Add
1-2 cm3 of ammonia solution in excess. Add ethanol dropwise and with stirring
till a deep blue precipitate is formed. Heat the beaker on a water bath at 60°C,
stir and wait till the blue precipitate just dissolves. Cover the beaker with a
watch glass and set aside to crystallise. Beautiful dark blue needle like
crystals separate after 1 hour. Filter off the crystals using a Buchner funnel
and wash with 2-3 cm3 ethanol at the pump. Allow the air to pass for 5
minutes. Transfer the product to a watch glass and dry in a desiccator. Store
the crystals in a weighed weighing bottle.
Weigh the dry crystals. Calculate the percent yield.
2.4.4 Observations
Weight of copper(II) sulphate taken = g
Weight of tetraamminecopper(II) = g
24 sulphate monohydrate (experimental yield)
2.4.5 Calculations
g of CuSO 4 . 5H2 O taken
No. of moles of copper(II) sulphate 
gram molecular weight
2.0
 moles
249.5
No. of moles of complex formed = No. of moles of copper(II) sulphate taken

2.0
 moles
249.5
Theoretical yield in gram = No. of moles  gram molecular weight

2.0
  245.74  1.97 g
249.5
Explained yield
Theoretical yield
2.4.6 Result
The percent yield of the tetraamminecopper(II) sulphate monohyderate = %
2.4.7 Structure of the Complex
Tetraamminecopper(II) sulphate is an example of a complex, in which

copper(II) ion is bound to four unindentate ammonia molecules. The
coordination number of copper(II) is 4. The complex has a square planar
structure (Fig. 2.5) and possesses one unpaired electron.
2+
Fig. 2.5: Structure of [Cu(NH3)4] ion.
This can be explained on the basis of dsp2 hybridisation of Cu2+ ion, which you
might have studied in Units 4 and 5 of the BCHCT 137 course.

POTASSIUM TRIOXALATOFERRATE(III)
TRIHYDRATE
In this experiment, you will synthesis the complex compound potassium
trioxalatoferrate(III) trihydrate.
2.5.1 Principle
The synthesis of potassium trioxalatoferrate(III) is achieved in two steps. The
first step consists in the preparation of the yellow iron (II) oxalate from
ammonium iron(II) sulphate by reaction with oxalic acid in the presence of
dilute sulphuric acid. 25
The second step involves the oxidation of iron(II) oxalate with H2O2 in the
presence of excess oxalate ions when emerald green crystals of potassium
trioxalatoferrate(III) are obtained.
Step 1
H O  ,Heat
Fe(NH4 )2 (SO4 )2 (aq )  H2C2O 4 (aq ) 3 
 FeC2O 4 . 2H2O(s )  (NH4 )2 SO4 (aq )  H2SO4 (aq )
Step 2
Heat
2FeC2O4 . 2H2O(s)  H2C2O4 (aq )  H2O2 (aq )  3K 2C2O4 (aq )   2K 3 [Fe(C2O4 )3 ]. 3H2O(s )
The names and gram formula weights of important compounds involved in this
experiment are listed below:
Name Formula Gram Formula Weight

g/mole
Ammonium iron(II) sulphate Fe(NH4)2(SO4)2 . 6H2O 392.13
Oxalic acid H2C2O4 . 2H2O 126.07
Potassium oxalate K2C2O4 . H2O 184.25
Hydrogen peroxide H2O2 34.02
Potassium trioxalatoferrate(III) K3[Fe(C2O4)3 . 3H2O 491.25
2.5.2 Requirements
Chemical Apparatus
Ammonium iron(II) sulphate Beakers 250 cm3 1 No.

Oxalic acid Beaker 100 cm3 1 No.
Potassium oxalate Buchner funnel 1 No.
Dilute sulphuric acid (5 M) Bunsen burner 1 No.
Hydrogen peroxide (3%) Desiccators 1 No.
Acetone Filtration apparatus 1 No.
Ethanol Glass rod 1 No.
Distilled water Measuring cylinder 1 No.
Tripod stand 1 No.
Watch glass 1 No.
Water bath 1 No.
Wire gauze 1 No.
2.5.3 Procedure
Step 1: Preparation of FeC2O4. 2H2O
Weigh 5.0 g ammonium iron(II) sulphate and transfer to a 250 cm3 beaker.
26 Add 15-20 cm3 distilled water and 1 cm3 dil. H2SO4. Stir to dissolve.
Add 10% oxalic acid (25 cm3) solution to the above iron(II) solution and heat to
boiling with continuous stirring. [Caution: Do not leave it unattended as this
solution is susceptible to spillover and there can be bumping once the
solid starts separating]. Add more oxalic acid, if necessary to get the
maximum yield of the yellow iron(II) oxalate, FeC2O4.2H2O.
Allow the yellow product to settle. Carefully decant the hot supernatant liquid
and repeatedly wash the precipitate with hot water. Retain the solid in the
beaker for the next step.
Step 2: Synthesis of K3[Fe(C2O4)3].3H2O
Add a warm solution of potassium oxalate (5.0 g in 15 cm3 distilled water) to

the iron(II) oxalate precipitate in the beaker. Suspend a thermometer in the
solution. Take 3% H2O2 (20 cm3) in a measuring cylinder. Stir the solution and
add hydrogen peroxide very slowly a few drops at a time with the help of a
dropper so as to maintain the temperature around 40C. In all 20 cm3 of 3%
H2O2 is added. The addition may take up to 30 minutes.
Heat to boiling. Add 10% H2C2O4 solution, first 4-5 cm3 in one lot and later
dropwise until the precipitate just dissolves. In all about 10 cm3 solution will be
required. Keep the solution boiling till a green colour is obtained. Heat for
another 5 minutes. Filter the solution in a 100 cm3 beaker and allow to cool to
room temperature in a dark cupboard since the product is photosensitive. Add
10 cm3 ethanol to the beaker and redissolve any crystals formed by gentle
warming on a water bath and put the solution in a dark cupboard to crystallise.
Cover with a watch glass. Slower evaporation encourages the development of
larger and purer crystals.
Filter the crystals on a Buchner funnel by suction. Wash with ethanol-water

(1: 1) mixture and finally with acetone. Dry in a desiccator over calcium
chloride. Weigh the crystals and record the yield.
2.5.4 Observations
i) Weight of ammonium iron(II) sulphate taken = g
ii) Weight of oxalic acid taken =g
iii) Weight of potassium oxalate taken =g
iv) Weight of complex formed =g
(Experimental yield)
2.5.5 Calculation of Percent Yield

g of Fe(NH4 ) 2 (SO 4 ) 2 . 6H2 O
No. of moles of Fe(NH4 ) 2 (SO 4 ) 2 . 6H2 O 
gram molecular weight
5.0
  0.013 mole
392.13
No. of moles of K3[Fe(C2O4)3 . 3H2O formed = 0.013 mole
Theoretical yield in gram = No. of moles  gram molecular weight
= 0.013  491.25 = 6.40 g 27

Explained yield
Theoretical yield
Explained yield
  100%
6.40
2.5.6 Result
Percent yield of potassium trioxalatoferrate(III) trihydrate = %
2.5.7 Alternate Procedure for the Synthesis of

Potassium Trioxalatoferrate(II) Trihydrate
There are two more procedures, which are straight forward, less time
consuming and involve more cost efficient method of synthesis. These require
the use of iron(III) nitrate or chloride instead of ammonium iron(II) sulphate.
Procedure A: Use iron(III) nitrate
Requirements
Chemical Apparatus
Potassium oxalate, K2C2O4 . H2O Beakers 150 cm3 2 No.
Iron(III) nitrate, Fe(NO3)3 . 9H2O Buchner funnel 1 No.
Distilled water Desiccators 1 No.
Ethanol Filtration apparatus 1 No.
Acetone Glass rod 1 No.
Ice Watch glass 1 No.
Water bath 1 No.
H / H O
Fe(NO 3 ) . 9H 2 O  3K 2 C 2 O 4 . H 2 O  2
 K 3 [Fe(C 2 O 4 ) 3 ] . 3H 2 O  3KNO 3
Prepare a solution of iron(III) nitrate (4.0 g in 20 cm3 distilled water) in a 150

cm3 beaker. Add this solution slowly to a stirred hot solution of potassium
oxalate (containing 6.0 g of the salt in 40 cm3 of distilled water) taken in
another 150 cm3 beaker. A clear green coloured solution is obtained. Heat for
2-3 minutes more.
Cool in an ice bath. Filter the crystals using a Buchner funnel. Wash with ice
cold water, followed by ethanol and acetone.
The emerald green product may be redissolved in warm water (15-20 cm3)
and reprecipitated by cooling in ice bath at 0°C. Collect the crystals by
filtration. Wash with ethanol-water (1: 1) mixture and finally with acetone.
Dry in a desiccator in a dark cupboard. Weigh the crystals and calculate the
28 percent yield.
Procedure A: Use iron(III) chloride
Requirements
Chemical Apparatus
Iron(III) chloride (anhydrous) Beakers 150 cm3 1 No.
Potassium oxalate K2C2O4. H2O Buchner funnel 1 No.
Distilled water Desiccators 1 No.
Ethanol Filtration apparatus 1 No.
Acetone Glass rod 1 No.
Ice Watch glass 1 No.
Water bath 1 No.
FeCl3 (aq )  3K 2C 2O 4 .H2 O  K 3 [Fe(C2 O 4 )3 ]. 3H2 O(aq )  3KCl(aq )
Take 6.0 g of potassium oxalate in a 150 cm3 beaker. Add 20-25 cm3 of
distilled water. Heat using a wire gauze to get a clear solution. Add 1.6 g
iron(III) chloride in small lots to hot solution of K2C2O4. Heat again till a green
coloured solution is obtained.
Cool the solution in ice bath at 0C. Keep at this temperature until
crystallisation is complete. Filter the crystals using a Buchner funnel. Collect
the product after washing with ethanol and acetone. Recrystallise the complex
as in procedure A. Dry the complex in a desiccator in a dark cupboard. Weigh
the complex and calculate the percent yield.
2.5.8 Structure
Potassium trioxalatoferrate(III) is an example of a complex compound, in
which iron(III) is chelated to three bidentate oxalate groups forming six bonds.
Coordination number of iron is six. It is octahedrally surrounded by six oxygen
atoms, two each from each oxalate group as shown in Fig. 2.6.
O 3
O O
C O O
O O C
Fe
O O C
O O
C
O C
O
3
Fig. 2.6: Structure of [Fe(C2O4)3] ion. 29
2.6 EXPERIMENT 6: COMPARISON OF THE

CONDUCTANCE OF THE COMPLEXES
(PREPARED BY EXPERIMENTS 3 TO 5) WITH
M/1000 SOLUTION OF NaCl, MgCl2 AND LiCl3
In this experiment you will compare the conductance of the complexes
(prepared by Experiments 3 to 5) with M/1000 solution of NaCl, MgCl2 and
LiCl3.
2.6.1 Principle
The high sensitivity of the conductometric measurements makes it an
important analytical tool for environmental analysis and certain other
applications. A continuous or spot check measurement of conductance is
employed, usually, with a dip electrode cell and meter. In certain cases
continuous recording of conductance is also employed.
Since conductance depends on ionic concentrations, the purity of steam

distillate, demineralized water, and the ionic contents of raw water can be
checked with measuring conductance directly. Metal industries, electroplating
baths and rinse baths are monitored by conductance methods.
Perhaps the most common application of direct condutometry has been for
estimating the purity of distilled water. Kohlrausch with a painstaking work
after 42 successive distillations of water in vacuum obtained a conductivity
water with | specific conductance,  = 4.3  108 S cm1 at 18°C. Traces of an
ionic impurity will increase the conductance appreciably. Ordinary distilled
water in equilibrium with the carbon dioxide of the air has a conductivity of
about 7.0  107 S cm1. The sea water has much higher value of conductivity
and the conductometric measurements are widely used to check the salinity of
water in oceanography.
Measuring conductance of soil helps in finding the moisture content of soils at

various places with portable instruments. All soils contain varying amount of
water soluble salts upto 0.1% or even more. These salts are usually present
as sulphate, chloride, carbonate or bicarbonate of sodium, potassium, calcium
and magnesium and contribute to the conductance of the soil. The soil may be
classed as saline and non-saline depending on the nature and quantity of the
salts present. Conductivity of a saturated extract with water of saline soil at
25°C has conductivity greater than 4 mS cm1.
Conductivity of coordination compounds (or complex) gives the degree to

which a given coordination compound (or complex) can conduct electricity.
They are different for different compounds. Based on the values of their
conductivities, the compounds may be classified as electrolytes and non-
electrolytes. You have learnt about Werner’s theory of coordination
compounds in your previous courses (BCHCT 137, unit 4). This theory may
be supported from the conductivity data and help in determining the structure
of a compound. Werner introduced primary and secondary valence to support
his postulates. (Recapitulate the terms ligands, coordination number,
30 coordination compounds)
2.6.2 Requirements
Chemical Apparatus
M/1000 solution of NaCl Beakers 250 cm3 1 No.
M/1000 solution of MgCl2 Beaker 100 cm3 4 No.
M/1000 solution of LiCl3 Measuring cylinder 1 No.
Distilled water Conductivity meter 1 No.
2.6.3 Procedure
Let us now discuss the experimental measurement of conductance.
Conductance is reciprocal of resistance and the resistance of a cell can be
measured by placing it in an arm of a Wheatstone bridge. The inverse of the
resistance gives the conductance and can be directly read on a conductivity
measuring instrument, known as “Conductometer”.
A typical conductometer consists of an ac source, a Wheatstone bridge circuit,

a null detector or direct reading display and a conductivity cell. .
To avoid the effects or polarization, i.e. the change is composition of the

measuring cell, alternating current (ac) is used. The instrument has an
arrangement to convert the supply of 50 Hz to higher frequency, say 1000 Hz.
For measuring low conductance solutions, the lower frequency is preferable
and for high conductive solutions higher frequencies are preferably used.
Several inexpensive conductometers are commercially available. The

instruments come as a line-operated unit with and without digital readout. For
spot checking on a process stream or tank, a dip-type of conductivity cell is
used. For titration work conductivity cells of varied designs are available. In
some titrations on open beaker with fixed electrodes is sufficient. However, for
fairly dilute solutions an open beaker would not be satisfactory because
atmospheric CO2 may alter the conductance.
Fig. 2.7 gives the view of a typical conductometer, which can be operated as
with oven instructions.
Read
.4 .8 1.2 Cal.
0 1.6
2.0 Sensitivity
mS range
selector
Conductometer
Fig.2.7: Conductometer.
1. Plug the instrument to an ac supply.
2. Put the frequency selector switch to required frequency (say 1000 Hz). 31
3. Set the mode selector on CAL and set the range selector on the desired
setting e.g., 2, 20 or 200. These figures refer to the full scale meter value
in milli Siemens (mS). With the help of sensitivity knob keep the pointer
roughly midway between the lowest and highest sensitivity say at 1
position.
4. Connect the conductivity cell electrodes to the appropriate terminals of

the instrument. Clean the conductivity cell with distilled water
(Conductivity water).
5. Take the standard KCl solution (say 0.1M) in a clean beaker. Introduce a
stirring rod (to be used for magnetic stirring) in the solution and put the
solution beaker on a magnetic stirrer plate.
6. Insert the conductivity cell in the solution. Ensure that the platinum plate
electrodes are completely immersed in the solution and they do not
touch the stirring rod or the sides or the bottom of the beaker.
7. Switch on the instrument and allow it to warm up for 2-5 minutes.
8. Measure the conductance, Gs, of the standard KCl solution by putting

meter switch to READ position.
9. Remove the KCI solution from the beaker; wash the conductivity cell
properly with distilled water. Take the unknown solution in the beaker
and measure its conductance, Gu, in the manner as for standard KCI
solution.
10. Calculate the cell constant, from the conductance and conductivity
values of the standard,
Conductivity (sepcific conductance)

K cell 
Observed conductance of the standard
S
 cm 1
GS
11. Calculate the conductivity (specific conductance) of the unknown

solution = cell constant  observed conductance
 u   cell . Gu
12. For titration work, the value of cell constant, Kcell is not required to
be calculated, since the cell constant will remain unchanged during the
course of any given titration.
Notes:
When the range selector is switched to a new position, it is essential to check

the calibration again. Set the meter again to read one with the sensitivity
control, if any deviation is observed.
The conductivity cell, when not in use, should be kept in distilled water to
32 prevent drying the platinum electrodes.
In case of fouling the conductivity cell electrode plates, clean them by keeping
in dilute K2Cr2O7 containing H2SO4 solution (i.e. dilute chromic acid) for 24
hours and then washing with running water followed by rinsing with distilled
water.
Prepare 0.001 M solutions of (a) Tetraamminecarbonatocobalt (III) nitrate, (b)

tetraamminecopper(II) sulphate monohydrate and (c) potassium
trioxalatoferrate(III) trihydrate complex in 100.00 ml volumetric flask. Measure
the electrical conductivity  of freshly prepared (a)
Tetraamminecarbonatocobalt (III) nitrate, (b) tetraamminecopper(II) sulphate
monohydrate and (c) potassium trioxalatoferrate(III) trihydrate complex.
Calculate the molar conductivity, and relate to the number of ions, in order to
conclude the formula of complex. Compare values with that of 0.001 M
solution of NaCl, MgCl2 and LiCl3. Be sure to rinse the cell with distilled water
before and after use.
Precautions
 Rinse the cell with distilled water before and after use.
 Stirring is required constantly to prevent bumping.
2.6.4 Observations
Observation Table I
Molar Conductivity Values
Sl. Sample Conductance, Conductivity, Molar Conductivity,

No. Siemen (S)  (S cm1) m (S cm2 mol1)
1. NaCl (0.001 M)
2. MgCl2 (0.001 M)
3. LiCl3(0.001 M)
4. [Co(NH3)4CO3] NO3(0.001M)
5. Cu(NH3)4SO4 . H2O (0.001 M)
6. K3[Fe(C2O4)3] . 3H2O (0.001 M)
Result:
1. The molar conductivity of tetraamminecarbonatocobalt(II) nitrate is found

to be ...... and is comparable with molar conductivity value of M/1000
solution of…...
2. The molar conductivity of tetraamminecopper(II) sulphate is found to be

...... and is comparable with molar conductivity value of M/1000 solution of
......
3. The molar conductivity of potassium trioxalatoferrate(II) trihydrate is found

to be ...... and is comparable with molar conductivity value of M/1000
solution of …… 33
2.7 SUMMARY
In this unit we discussed the preparation of the following three inorganic
compounds:
1. Tetraamminecarbonatocobalt(III) nitrate
2. Tetraamminecopper(II) sulphate
3. Potassium trioxalatoferrate(III) trihydrate
We also described the calculation of percentage yield of the prepared

complexes. At the end we have compared the conductance of these prepared
complexes with M/1000 solution of NaCl, MgCl2 and LiCl3.
2.8 ANSWERS
Self Assessment Questions
1. From Eq. 2.5 for KCI solution:
Kcell =   R
= 0.2768 S m-1 x 195.96 
= 54.24 m-1.
Conductivity of K2SO4 solution can be given by,
K cell 54.24 m 1
 
R 775.19 
= 0.06997 S m-1.
concentration of K2SO4 in mol m-3 unit:
c = 1000 x 2.50 x 10-3 mol m-3
= 2.50 mol m-3
Molar conductivity of K2SO4 can be calculated using Eq. 2.6

 0.06997
Λm   S m 2 mol 1
c 2.50
= 0.028 S m2 mol-1
34
Experiment 7 Systematic Qualitative Analysis of Carboxylic
Acids and Phenols and Preparation of their Derivatives
EXPERIMENT 7
SYSTEMATIC QUALITATIVE
ANALYSIS OF CARBOXYLIC
ACIDS AND PHENOLS AND
PREPARATION OF THEIR
DERIVATIVES
Structure
7.1 Introduction Procedure
Expected Learning Outcomes Observations and Results
7.2 Functional Group 7.4 Experiment 7b: Identification
Identification of Phenols and Preparation of
their Derivative
7.3 Experiment 7a: Identification
of Carboxylic Acids and Functional Group Tests
Preparation of their Preparation of Characteristic
Derivatives Derivatives
Solubility Test Requirement
Functional Group Test of Procedure
Carboxylic Acids
Observation and Result
Characteristic Derivatives
7.5 Answers
Requirements
7.1 INTRODUCTION
Organic compounds are classified into different classes based on the
presence of functional groups. In the previous course, BCHCL-134 you have
studied elementary analysis of organic compounds, e.g., physical examination,
elemental analysis and determination of physical constants etc. In this
Experiment and Experiments 9 and 10, you will learn some basic concepts of
functional group analysis and perform qualitative tests for identification of
some important functional groups. Along with this, you will also prepare their
derivatives. 35
Both carboxylic acids and phenols are acidic in nature. Phenols are
less acidic than carboxylic acids and do not react with NaHCO3 to form
water-soluble salts. As a result, phenols are insoluble in 5% NaCHO3 but most
of phenols are soluble in 5% NaOH. In this experiment, our focus will be on
qualitative tests used in identification of carboxylic acids and phenols. For the
confirmation of the presence of these functional groups, we will also prepare
some derivative of carboxylic acid and phenols.

After performing the experiment given, you should be able to:
 explain the meaning of functional group of an organic compound;
 identify the carboxylic acids by sodium bicarbonate test;
 identify the phenol by ferric chloride test and Liebermann’s test;
 prepare characteristic derivatives of carboxylic acids; and
 prepare characteristic derivatives of phenols.
7.2 FUNCTIONAL GROUP IDENTIFICATION

Organic compounds are classified into different classes based on the
presence of functional groups. You can recall from your theory course that the
functional groups are the sites of chemical reactions. The identification of
functional groups depends on their specific features of structure and reactivity.
Somehow identification of functional group depends basically on the correct

determination of the elements, which you have studies in BCHCL-134 Course.
It is rare for an unknown compound to possess just one functional group. You
must always be aware of the possibility that more than one functional group
may be present. However, here we will examine only monofunctional
compounds. Some common classes of monofunctional organic compounds
are listed in Table 7.1
Table 7.1: Common monofunctional organic compounds
Sr. No. Functional Group Class Nature
H
1. C Aldehydes Neutral
O
2. Ketones Neutral
C O
36
O
3. R C OH Carboxylic acids Acidic
4. OH Phenols Weakly acidic
5. –NO2 Nitro compounds Neutral
6. –CONH2 Amides Neutral
NH 2 Amines Neutral
7.
For the identification of the functional group, we generally follow the following
steps;
1. Physical examination
2. Elemental analysis
3. Solubility test
4. Identification of functional groups using chemical tests
5. Preparation of derivatives
In your earlier course (BCHCL 134), we have covered steps 1 and 2. In this
experiment and in next two experiments (Experiments 9 and 10), our focus will
be on the remaining three steps. Our classical scheme for identification of
functional group involves performing a number of chemical tests on a
substance, each of which is specific for a type of functional group. After
confirming the presence of the functional group in an organic compound, we
prepare crystalline derivative to identify the actual compound by comparison of
melting point with literature value of the compound. The ideal derivative should
be able to be simply and quickly prepared with good yield. It should also be
easily purified and identified. These should also have sharp and definite
melting points preferably between 50oC and 250oC. In this work, you are
advised not to jump to premature conclusions about the identity of the
compound. Always prepare one derivative and check that its properties agree
with those expected values before leaping into the preparation of the second
confirmatory derivative. The methods for preparing derivatives for different
functional groups will be discussed in this experiment and also in Experiments
9-11. 37
SAQ 1
Identify the functional group present in the following compounds.
i) R
C O
R'
C OH
ii)
O
iii) R C OH
H
iv) C
O
So far in this experiment, we have discussed different steps that are evolved
to establish the identity of the unknown compound. Now, we will apply them in
identification of carboxylic acids and phenols.
7.3 EXPERIMENT 7a: IDENTIFICATION OF

CARBOXYLIC ACIDS AND PREPARATION OF
THEIR DERIVATIVES
Before going in detail of chemical tests used for the identification of carboxylic
acids and phenols, we would like to discuss solubility test as it plays an
important role in the identification of the carboxylic acid functional groups.
7.3.1 Solubility Test

Solubility test of an organic compound in water, dilute acid or dilute base can
provide useful, but not definitive, information about the presence or absence of
certain functional groups.
Procedure for Solubility Tests
The solubility tests are done at room temperature. Take 100 mg of a solid
(finely crushed) or 0.2 cm3 liquid and 3.0 cm3 of solvent in small test tubes.
The mixture should be shaken vigorously. It is recommended that the solubility
tests to be done in the order presented below:
Solubility in Water
Weight 100 mg of the finely crushed solid or measure 0.2 cm3 of liquid with the
help of graduated pipette or burette and treat it with successive 1.0 cm3 portion
of distilled water; shake vigorously after each addition until 3.0 cm3 have been
added. If the compound does not dissolved completely in 3.0 cm3 of water, it
may be regarded as insoluble in water.
Now test the contents of the test tube with pH paper. This test can be done by
taking one drop of solution with the help of glass rod and touching it with pH
38 paper.
The solubility of the compound in distilled water suggests that the compound is
a low molecular weight organic compound having 4-5 carbon atoms, which
contain a polar group such as
- OH, -COOH, - NH2, C=O
If higher molecular weight compound soluble in water, it must be

polyfunctional, for example carbohydrates. On the other hand, alkanes,
alkenes, alkynes and alkyl halides are water-insoluble.
If the organic compound is water soluble and gives a positive acidic test with
pH paper, it is likely to be a low molecular weight carboxylic acid such as
acetic acid. If compound gives positive basic test with pH paper, the
compound is a low molecular weight organic base such as diethylamine. A
neutral solution suggests the presence of a neutral polar compound such as
ethanol or acetone.
Solubility in 5% Sodium Hydroxide
If the compound is insoluble in distilled water, it should be similarly tested for

solubility in 5% aqueous sodium hydroxide solution. This solubility indicates
the presence of a carboxylic acid, sulphonic acid, or phenol. Because they are
converted into their water – soluble sodium salts.
NaOH  +
Carboxylic acids: RCOOH RCOO Na
water water
insoluble soluble
NaOH soluble organic compound should then be tested for solubility in the
weaker base, 5% NaHCO3 solution, which may permit distinction between
carboxylic and phenolic functional groups.
Solubility in 5% Sodium hydrogencarbonate (Sodium bicarbonate)

Solution
Similar to the procedure adopted for the solubility of water, the solubility of the Highly acidic phenols
are soluble in 5%
compound is checked with 5% aqueous solution of sodium
sodium bicarbonate.
hydrogencarbonate. If it is soluble, the presence of a carboxylic acid group
may be tentatively concluded, owing to the formation of the water-soluble
sodium salt. Phenols are insoluble in sodium hydrogencarbonate.
NaHCO3  +
Carboxylic acids: RCOOH RCOO Na
insoluble soluble
Solubility in 5% Hydrochloric Acid
The solubility in 5% aqueous hydrochloric acid is evidence for an amino

compound or a heteroaromatic base.
RNH 2 HCl + 
RNH 3 Cl
insoluble soluble
Any unknown insoluble in all the reagents so far should also be checked for
solubility in concentrated sulphuric acid. 39
Solubility in Concentrated Sulphuric Acid
Take 3 cm3 of concentrated sulphuric acid with the help of graduated pipette in
a dry test tube and add 100 mg of solid or 0.2 cm3 of liquid. The solubility of
organic compound in sulphuric acid indicates the presence of oxygenated and
unsaturated aliphatic compound.
R2C CR2 + H2SO4 R2C CR2
H OSO3H
+ 
R2C O + H2SO4 R2C O HSO 4
H or
+ 
ROR + H2SO4 R-O-R HSO4
H
The general solubility behaviour of common classes of organic compound is

shown schematically in Fig. 7.1.
Sample
Insoluble Soluble
H2O
Mono functional compounds

with less than 5 carbons,
ionic compounds, carbohydrates
5% NaOH
Insoluble Soluble
Insoluble
Carboxylic acids and
Soluble 5% NaHCO3 phenols
5% HCl
Soluble
Carboxylic acids, some

Aliphatic amines, Insoluble highly acidic phenols
Insoluble aromatic amines
Phenols
Soluble
Conc. H2SO4
Insoluble
Oxygen containing
compounds, alkenes, alkynes
Alkanes, haloalkanes
Fig.7.1: Solubility behaviour or common classes of organic compounds.
7.3.2 Functional Group Test for Carboxylic Acids

Carboxylic acids are represented by general formula RCOOH. The –COOH
group is known as carboxylic group. The presence of carboxylic group in the
40 compound is ascertained by following test:
Sodium Bicarbonate Test
One of the best tests for the carboxylic group is solubility in basic solution.
Carboxylic acids liberate carbon dioxide from sodium bicarbonate.
RCOOH + NaHCO3 RCOONa + H2O + CO2
Take 0.2 g of the unknown compound in a test tube and add 1 cm3 of 5%
aqueous sodium bicarbonate. Vigorous evolution of carbon dioxide with
effervescence indicates the presence of carboxylic group.
7.3.3 Characteristic Derivatives

Common derivatives prepared for identification of carboxylic acids are:
amides, anilides and p-toluidides. Amides, anilides and p-toludides are
prepared from the corresponding acid chloride by treatment with ammonia,
aniline or p-toluidine, respectively. It is considered that the method for the
preparation of anilides and p-toluidides has advantage over amide. This is
because amides are more soluble in water and as a result are harder to
isolate. The acid chloride is prepared from the acid or its salt, and thionyl
chloride.
RCOOH + SOCl2 RCOCl + SO2 + HCl

Thionyl chloride Acid chloride
Be very careful white
or adding conc. NH4OH,
the reaction is quite
RCOONa + SOCl2 RCOCl + SO2 + NaCl vigorous.
Thionyl chloride Acid chloride
Acid chloride can be used to make the amide, amilides or p-toluidides.

Therefore, let us first study the method for preparation of acid chloride. Then,
we will learn the method for preparation derivative of carboxylic acids.
Preparation of Acid Chloride
Take the sample of carboxylic acid (1 g), thionyl chloride (2 cm3) and
dimethylformamide (DMF) (5 drops) in a small round bottom flask. Attach a
reflux condenser and reflux for about 30 minutes. Precipitate of acid chloride
will appear at the bottom of the flask. This mixture, containing acid chloride,
can be used to prepare amide, anilide or p-toludide derivative as described
below:
Procedure for Preparing Derivatives
Common derivatives use for identification of carboxylic acids are Amides,

p-Toluidides and Anilides Derivatives. Let us discuss the method of
preparation for these derivatives individually.
i) Amide Derivative
To about 2 gm of the above mixture, containing acid chloride, and add 15 cm3
of ice-cold conc. NH4OH. A vigorous reaction takes place. Filter off the solid
formed as the result of the reaction. Recrystallise it from water or aqueous
ethanol. The reaction involved in this process is: 41
RCOCl + NH4OH cold RCONH2
ii) p-Toluidides and Anilides Derivatives
Take about 2 g of the crude acid chloride in a 100 cm3 conical flask and
dissolved it in 5 cm3 of acetone. To this add 1 g p-toluidine (dissolved in
acetone). Shake the mixture for few minutes and ad 50 cm3 of NaOH to the
flask. Filter off the solid p-toluidide which formed during the reaction. Wash the
p-toluidide with water and recrystallised from ethanol. The reaction involved in
this process is:
+ -
RCOCI + 2 NH2 RCONH + NH 3Cl
If you want to prepare anilide, use aniline in place of p-toluidine and you will
get anilides.
After drying the derivative, determine its M.P and compare it with theoretical
value.
SAQ 2
Fill in the blanks.
i) Carboxylic acids liberate ....................from sodium bicarbonate.
ii) Reaction of acid chloride with ammonia yields ........................
iii) Reaction of carboxylic acid with .......................yields anilides.
SAQ3
Complete the following reactions
i) RCOOH + NaHCO3 ........... + ........... + ..........
ii) RCOOH+ SOCl2 ........... + ........... + ..........
iii) RCOCl + NH4OH ............
7.3.4 Requirements
S. No. Apparatus S. No. Chemicals
1. Beakers 2 1. NaOH
2. Conical flask 1 2. Acetone
3. Droppers 1 3. Carboxylic acid
4. M.P. apparatus 1 4. Ethanol
5. Reflux condenser 1 5. conc. H2SO4
6. Round bottom flask 1 6. HCl
7. Test tubes 1 7. conc. NH4OH
8. Thermometers 3 8. p-Toluidine
9. Water bath 1 9. Pyridine
10. Sodium bicarbonate
42
10 pH paper 1 11. Thionyl chloride

12. 2,4-Dimethylformamide
(DMF)
13. 2-3 Samples of Carboxylic
acid
7.3.5 Procedure
1. Collect sample(s) of carboxylic acid from your counsellor and carry out
physical examination of the sample as discussed in BCHCL 134
course.
2. Carry out solubility test as discussed in Sec. 7.3.1. If your compound is

soluble in water, check the pH of solution using pH paper.
3. Carry out functional group test (class determination test) as discussed

in Sec. 7.3.2.
4. Prepare at least one derivative using procedure discussed in 7.3.3
5. Dry the prepared derivative and take the m.p. of both derivative and
sample if it is solid. Predict the actual compound by comparison of
melting point of sample and its derivative with literature values. Use
appendix A for this purpose.
7.3.6 Observations and Result

1. Physical Examination
a) Physical state :
b) Colour :
c) Odour :
d) Ignition test :
Comment: This suggests that the unknown ‘A’ is either aromatic or aliphatic
compound
2. Elemental Analysis: Not necessary at this point
3. Solubility test
H2O 5% NaOH 5% NaHCO3 5% HCI Conc. H2SO4 Expected Class
4. Test with pH paper :
5. Melting point/Boiling point observed :
5. Class determination :
Sodium bicarbonate Test
6. Preparation of derivatives 43
(a) Derivative chosen:
M.P. observed
(b) Derivative chosen
M.P. observed
7. Examination of literature
Possible M.P. in Derivative(s)/ M.P. of M.P. of

Compound Literature M.P. in Sample Derivative(s)
Literature
8. The unknown compound is ……….
9 The structure of this compound is………………
7.4 EXPERIMENT 7b: IDENTIFICATION OF

PHENOLS AND PREPARATION OF THEIR
DERIVATIVES
The aromatic compounds in which hydroxyl (OH) group is directly attached to
benzene ring are called phenols. Phenols are mildly acidic. These require
careful handling, especially in laboratories, because these can cause chemical
burns. There are few laboratories tests which confirm the presence phenolic
group in organic compounds.
In this section, we shall study the method for carrying out functional group test
of phenols and preparation of their characteristic derivatives.
7.4.1 Functional Group Test

There are following three main functional group tests for identification of
phenols.
i) Ferric Chloride Test
ii) Liebermann’s Test
iii) Ceric Ammonium Nitrate Test
Following apparatus and chemicals are required for these test;
i) Ferric Chloride Test
Most phenols react with ferric chloride and give colour. Some phenols, that do
not give colour in aqueous or alcoholic solution, but they do so in chloroform
especially after addition of a drop of pyridine. Some phenols do not give colour
at all. So a negative test must not be taken as significant without supporting
44 further information.
Procedure
Dissolve 0.5 g of the unknown compound in 1-2 cm3 of water (or a mixture of
water and 95% ethanol if the compound is not water soluble ) and add a few
drops of very dilute (1%) ferric chloride solution. Wide range of colours given
below, show the presence of phenolic -OH.
Compound Colour
Phenol, o-Cresol Violet
p-Cresol, quinol Blue
m-Cresol, 1-Naphthol(alcoholic) Blue-violet
Resorcinol --
1- Naphthol Pink
2- Naphthol (alcoholic) Green
Following compounds do not respond with ferric chloride test,
i) Picric acid
ii) Naphtholsulphonic acid
The reaction involved in this test is,

-3
+
6 OH + FeCl 3 3H +
Fe O + 3 HCI
6
OH
There are mainly to functional group tests for identification of phenols which
Enols (R'C = CHR')
are given below: also give a wide range
of colour with FeCl3.
The phenol complexes
are probably
Phenols in which para position is free, give positive Liebermann’s test,
coordination compounds
although few exception are noted. For example, p- substituted phenols and in which iron is
nitrophenols do not respond to Liebermann’s test. Dihydroxyphenols, except hexavalent.
resorcinol, do not give satisfactory result with this test. 6 Ar –OH + FeCl3 →
- + -
[ArO)6)Fe] + 6H +3Cl
Procedure
Take few crystals of sodium nitrite and compound (0.5 g) in a dry test tube.
Heat the mixture gently for about 30 seconds, allow it to cool and add 0.5 cm3
of conc. sulphuric acid. On shaking the contents a deep green or blue colour
develops. Dilute the content with water, the colour changes to red. Now add
excess of dilute sodium hydroxide solution, the green or blue again reappears.
Colour formation is observed due to the production of salt of indophenols.
The reactions of the test are:

+
NaNO 2 H
HNO 2 HO.NO
Nitrus acid 45
HO HO.NO
HO NO O NOH
p - nitrosophenol monoxime of quinone
H2SO4
O N OH + H OH O N OH
Condensation
indophenol
O4
H 2S
+ - - +
OH N OH HSO 4 O N O Na
green blue
Ceric ammonium nitrate can also be used as a qualitative test for phenols.
You carry out the test at room temperature because hot solutions of the
reagent oxidise many of organic compounds.
Procedure
Prepare the solution of the unknown compound (0.2 g or 1 cm3) in water, (or
dioxane for water insoluble compounds) add few drops of ceric ammonium
nitrate. A red colour is obtained. This indicates the presence of primary,
secondary and tertiary alcohols. Alcohols replace nitrate ions in complex
cerate anions, resulting in a change from a yellow to red solution.
The preliminary reaction for phenol/alcohols is,

HNO3
2 ROH + (NH4)2Ce(NO3)6 2 NH4NO3 + [(ROH)2Ce(NO3)4]
Ceric ammonium Red Complex
Nitrate
7.4.2 Preparation of Characteristic Derivatives

Some common derivatives which are used to identify the phenols are:
i) 3,5- Dinitrobenzoate Derivatives
ii) 1-Naphthyl Urethane Derivative
Let us discuss each of them separately
i) 3,5- Dinitrobenzoate Derivatives
The reaction between 3,5-dinitrobenzoyl chloride and alcohol gives the

corresponding ester (3,5-dinitrobenzoate). 3.5,-Dinitrobenzoate esters
are suitable derivatives for both alcohols and phenols. The reaction
involved in this preparation is as under:
NO2
O NO2
O
ROH + Cl C Pyridine
ROC + HCI
NO2
NO2
46 3,5-Dinitrobenzoyl chloride 3,5-dinitrobenzoate

Procedure
Dissolve the alcohol (2 cm3) in dry pyridine (5 cm3) and add 3,5-
dinitrobenzoyl chloride (1.2 g) in a 100 cm3 round-bottomed flask. Reflux
the reaction mixture for about 30 minutes and pour it into 40 cm3 of
hydrochloride acid. Separate the solid or oily product and stir with 15 cm3
sodium carbonate solution (1M) to remove any 3,5-dinitrobenzoic acid
formed. Filter the solid and recrystallised from petroleum (60-80o C),
ethanol or aqueous ethanol.
ii) 1-Naphthyl Urethane Derivative
This derivative is also suitable for both alcohols and phenols. When aryl
substituted isocyanate, ArN=O, react with alcohols, it gives a urethane.
R R
O
ROH + N=C=O
NH C OR
Aryl isocyanate Urethane
A major side reaction is that of water with isocynate. To avoid the side
reaction, take precautions to ensure that the alcohol is anhydrous.
Procedure
Place the phenol (0.5 g), dry pyridine (1 cm3) and 1-naphthylurea (0.5 cm3)
in a dry test tube. Shake the mixture for few minutes. If no precipitate
forms, warm gently on a water bath for 5 minutes and then cool the mixture
in ice. Filter off the solid product. Recrystallise the crude derivative from
petroleum ether (40-60oC). (Remove 1-naphthylurea by filtration which is
insoluble in petroleum).
SAQ 4
Which of the following would give colour with FeCl3?
i) p-Cresol
ii) Phenol
iii) Resorcinol
iv) 2-Napthol (alcoholic)
SAQ 5
Which one of the following compounds does not show colour with FeCl3
i) Picric acid
ii) o-cresol
iii) Quinol
iv) 2-Napthol (alcoholic)
47
SAQ 6
Give the three main functional group tests for identification of phenols.
7.4.3 Requirements
S. No. Apparatus S. No. Chemicals
1. Beakers 2 1. conc. NH4OH

2. Conical flask 2. pH Paper
3. Droppers 1 3. Carboxylic acid
4. Ethanol
4. M.P. Apparatus 1 5. Pyridine
5. Reflux 1 6. Acetone
condenser
6. Round bottom 1 7. Sodium nitrite
flask
7. Test tubes 3 8. 3,5-Dinitrobenzoyl chloride
8. Thermometers 1 9. Ceric ammonium nitrate
9. Water bath 1 10. H2SO4
11. HCI
12. NaOH
13. Ferric chloride
14. Sodium carbonate
15. petroleum ether (40-60oC)
16. 1-naphthylurea
17. Samples of Phenols
7.4.4 Procedure
1. Collect sample(s) of phenol from your counsellor and carry out physical
examination of the sample as discussed in BCHCL-134 course.
2. Carry out solubility test as discussed in Sec. 7.3.1. Check the pH of

water solution using pH paper.
3. Carry out class determination test as discussed in Sec. 7.4.1.
5. Dry the prepared derivative and take the m.p. of both the derivative
and sample if your sample is solid. Predict the actual compound by
comparison of melting point of sample and its derivative with literature
values.
48

a) Physical state :
b) Colour :
c) Odour :
d) Ignition test :
Comment: This suggests that the unknown ‘A’ is aromatic/aliphatic

compound.
2. Elemental Analysis: Not necessary at this point.
3. Solubility test
4. Test with pH paper :
5. Melting point/Boiling point observed :
5. Class determination
Ferric Chloride Test
Liebermann’s Test
Ceric Ammonium Nitrate Test
(a) Derivative chosen
M.P. observed
M.P. in literature
(b) Derivative chosen
M.P. observed
M.P. in literature
Possible compound.......... M.P....... Derivatives
8. The unknown compound is ………..
9. The structure of this compound is........... 49

7.5 ANSWERS
1. i) Ketones
ii) Alcohols
iii) Carboxylic Acids
iv) Aldehydes
2. i) Carbon dioxide
ii) Amide
iii) Aniline
3. i) RCOONa + H2O + CO2
ii) RCOCl+SO2+HCl
iii) RCONH2
4. All four
5. i)
6. i) Ferric Chloride Test
50
Experiment 8 Systematic Qualitative Analysis of Aldehydes and
Ketones and Preparation of their Derivatives
EXPERIMENT 8
ANALYSIS OF ALDEHYDES AND
KETONES AND PREPARATION
OF THEIR DERIVATIVES
Structure
8.1 Introduction Procedure
Expected Learning Outcomes Observation and Result
8.2 Aldehydes and Ketones 8.3 Answers
Functional Group Tests
Preparation of Characteristic
Derivatives
Requirement
8.1 INTRODUCTION
In the last experiment, we have learnt some basic concepts of functional group
chemistry and performed qualitative tests for identification of carboxylic acids
and phenols and methods of preparation of their derivatives. In this
experiment, you will carry out tests for the identification of aldehydes and
ketones using Brady’s test, Tollen’s test, Schiff test and Iodoform test. You will
also perform tests to differentiate these two categories of compounds. Once
your functional group has been determined, you will prepare a derivative of
your compound to established actual identity of your given sample.

After performing the experiment, you should be able to:
 identify the aldehydes and ketones by Brady’s test, Tollen’s test and
Schiff test.
 prepare characteristics derivatives of aldehydes and ketones. 51

8.2 EXPERIMENT 8: IDENTIFICATION OF

ALDEHYDES AND KETONES AND
PREPARATION OF THEIR DERIVATIVES
Both aldehydes and ketones have carbonyl group (>C=O). You have studied
the reactions of carbonyl group in organic chemistry course (BCHCT-133). In
this experiment you will perform the tests for detecting aldehydes and ketones.
In the last section, you will learn the methods of preparation of derivatives of
aldehydes and ketones.

There are four main following functional group tests for identification of
aldehyde and ketones. They are:
i) Brady’s Test
ii) Tollen’s Test
iii) Schiff Test
iv) Iodoform Test
Let us discuss each of these separately.
i) Brady’s Test
2,4-Dinitrophenylhydrazine (2,4-DNP) is known as Brady’s reagent. It is a red-orange

solid, usually supplied wet to reduce the risk of explosion. The structure of
2,4-Dinitrophenylhydrazine is given below.
NO 2
H2NNH NO 2
2,4-Dinitrophenylhydrazine derivatives offer a convenient way of separating the

components of a mixture of aldehydes and ketones.
The carbonyl compounds (aldehydes/ketones) react with 2,4-

dinitrophenylhydrazine (DNP) and give crystalline 2,4-dinitrophenylhydrazone
product having orange/ yellow/ red colour. The reaction involved in the Brady’s
test in given:
NO 2 NO 2
R R
C O+ H2NNH NO 2 C NNH NO 2 + H2O
R' R'
2,4 - Dinitrophenyl - hydrazone

(Yellow/Orange/Red)
This test is carried out as given below:
Procedure
Take 0.5 g of the unknown compound in a test tube and dissolve it in few
52 drops of water or ethanol. Add 1 cm3 of Brady’s reagent. Heat he reaction
mixture on water bath for few minutes and then cool it in ice. The appearance
of yellow/orange/red crystalline precipitate indicates the presence of
aldehydes or ketones.
The colour of the precipitate gives some idea of the type of carbonyl
compounds.
Colour of Precipitate Compound
Yellow Saturated carbonyl compounds
Orange α, β-Unsaturated carbonyl compounds
Red Aromatic carbonyl compounds
SAQ 1
Write the structural formula of 2,4-Dinitrophenylhydrazine.
ii) Tollen’s Test
If Brady’s test is positive, than aldehydes and ketones are differentiate through
Tollen’s test. A positive Tollen’s test indicated by the or sometimes precipitation
of elemental silver, often producing a characteristic "silver mirror" on the inner
surface of the reaction vessel.
Tollens' reagent is used to determine the presence of aldehydes in organic

compounds. The reagent consists of a solution of silver nitrate, ammonia and
sodium hydroxide (to maintain a basic pH of the reagent solution). It was
named after its discoverer, the German chemist Bernhard Tollens. A positive
Tollens test indicates the presence of an aldehyde. Normally, ketones do not
give Tollen’s test but there are few exceptions, for example acetophenone and
cyclohexanone. Some easily oxidisable compounds (e.g., certain phenols, 2-
naphthol; and amines) also give positive Tollen’s test but these compounds do
not give positive test with DNP.
Silver ammonium ion [Ag(NH3)2]+ is present in Tollen’s reagent. In this test,

aldehyde is oxidised to carboxylic acid and silver ion reduced to free silver.
Procedure
Place the unknown compound (2 drops of liquid or 0.05 g of solid) and add 1
cm3 of freshly prepared Tollen’s reagent in a clean test tube. Shake the test
tube and place it in the stand for about 10 minutes. If black precipitate or silver
mirror on the wall of test tube is not appeared, warm the test tube for few
minutes on a water bath. Formation of black precipitate of silver or silver mirror
indicates the presence of aldehydic group.
The reaction can be given as:
RCHO + 2 Ag(NH 3)2OH 2 Ag + RCOONH 4 + 3 NH 3 + H2O

Tollen's reagent Silver mirror
Colorless or Black ppt
53
SAQ 2
Name the chemist who discovered the Tollens Test.
iii) Schiff’s Test
Another method for distinguishing between aldehyde and ketone is Schiff Test.
Aldehydes give positive Schiff’s test whereas ketones do not react with Schiff’s
reagent. In this test, an aldehyde reacts with Schiff’s reagent to form a
characteristic magenta colour. Some aromatic aldehydes (e.g., vanillin), give a
negative result with the Schiff’s reagent. Methyl ketones (CH3CO-) may restore
the colour of Schiff’s reagent very slowly. Your test tube should be free from
alkali and the salts of weak acids because these also redden the Schiff’s
reagent like an aldehyde. The reaction sequence of this is:
H 2N
C NH 2 -
Cl + 3 H2SO 3
H 2N
HSO 2NH
+ -
C NH 3 Cl + H2O
SO3H
HSO 2NH
Schiff's reagent (colourless)
2 RCHO
-H 2SO 3
OH
RCHSO 2NH
+ -
C NH 2 Cl
RCHSO 2NH
OH
Perform this test as given below:
Procedure
Take 2 cm3 of unknown compound or 2 cm3 of aqueous or alcoholic solution of

the unknown compound in a test tube. Then add 2 cm3 of Schiff’s reagent in
the test tube and shake it for 2 minutes. Do not warm or heat the Schiff’s
reagent because pink colour develops on heating even in the absence of
aldehyde. The appearance of wine-red or purple colour indicates the presence
54 of an aldehyde group.
SAQ 3
What are the compounds involved in the preparation of Schiff ‘s reagent?
iv) Iodoform Test
Iodoform test is useful for the identification of methyl ketones (CH3COR) and
secondary methyl carbinols CH3CH(OH)R. Since this test is positive for
CH3CH(OH)- groups, it is advised that you should perform iodoform test after
confirming the presence of carbonyl group. Ethanol, acetaldehyde (ethanol),
CH2ICO- also gives positive iodoform test. The test is negative for acetic acid
and some other similar compounds.
Reaction involved in the test is given by,
I2, NaOH
CH3COR RCO2Na + CH 3l
H2O
Pale yellow ppt
Carry out the test as given below:
Procedure
Dissolve 0.5 cm3 of the unknown liquid or 0.2 g of the solid in water (3 cm3) or
aqueous dioxane (2 cm3 water + 2 cm3 dioxane) in a boiling tube. Add iodine-
potassium iodide solution (1 cm3) and then few drops of 3 M sodium hydroxide
solution with shaking until the brown colouration vanishes. A positive test is
indicated by immediate formation of pale yellow precipitate of iodomethane
(iodoform), melting point. 1190 C, without heating.
SAQ 4
Write the reaction involved in the Iodoform test.
SAQ 5
Which of the following compounds will give a positive haloform test?
a) C6H5COCH3; b) CH3COOH; c) CH3CHO;
d) CH2ICOR; e) CH3COCH2COOR
8.2.2 Preparation Characteristic Derivatives

For the preparation of derivatives, carbonyl group of aldehydes and ketones
are converted into another groups such as > C = NNHR, oximes, etc. Some
important derivatives which help in the identification of aldehyde and ketones
are:
i) 2,4-Dinitropheylhydrazone
55
ii) Semicarbazone
iii) Oximes
Methods for the preparation of some common derivatives are given below this
section.
Procedure
Dissolve 0.5 g of the unknown carbonyl compound in a small volume of

ethanol and add 2-3 cm3 of the 2,4-dinotrophenylhydrazine reagent. Heat the
mixture on water bath for 15-20 minutes, if no solid separates immediately,
cool it and if a precipitate still does not form, add water dropwise until
precipitate forms. Filter off the resulting solid, wash it with aqueous methanol
(equal volumes of water) and methanol and recrystallise the solid from ethanol
or ethyl acetate. Take the melting point. Reaction involve in the process is
given below:
NO 2 NO 2
R R
C O+ H2NNH NO 2 C NNH NO 2 + H2O
R' R'
2,4-Dinitrophenylhydrazone
(Yellow/Orange/Red)
ii) Semicarbazone
Procedure
Dissolve the semicarbozide hydrochloride (0.5 g) and sodium acetate (0.8 g)

in 5 cm3 of water in a test tube and then add the carbonyl compound (0.5 g).
Add minimum amount of ethanol dropwise to get a clear solution if the solution
is not clear. Heat the mixture for 10-20 minutes on a water bath, cool in the ice
and filter. Recrystallisese the product from ethanol, aqueous ethanol, water or
benzene.
R R
C O + H2NNHCONH 2 C NNHCONH 2 + H2O
R' R'
Semicarbazone
iii) Oximes
This is used for higher molecular weight aldehydes and ketones.
Procedure
Place a mixture of 0.5 g of carbonyl compound, 0.5 g of hydroxylamine

hydrochloride, 3 cm3 of pyridine and 3 cm3 of absolute ethanol in a small round
bottom flask. Fit reflux condenser to the round bottom flask and reflux the
mixture for 2 hours on water bath. Evaporate the recrystallised the residue
from ethanol or aqueous ethanol. The reaction involved in the preparation of
56 oxime is given below:
R R
C O + H2NOH.HCI Pyridine C NOH + H 2O + HCI
R' R'
Hydroxyl amine Oxime
hydrochloride
SAQ 6
What are the main derivatives used to for identification of aldehyde an
ketones?
SAQ 7
Write the chemical formula of the following compounds.
ii) Semicarbazone
iii) Oximes
8.2.3 Requirements
S. No. Apparatus Qty. S. No. Chemicals
1 Beakers 2 1 Alcohol
2 Boiling tube 1 2 2,4-Dinitrophenylhydrazine

(2,4-DNP)
3 Conical flask 1 3 Dioxane
4 Droppers 1 4 Ethanol
5 M.P. Apparatus 1 5 Hydroxylamine hydrochloride
6 Reflux condenser 1 6 Iodine- potassium iodide

solution
7 Round bottom 1 7 Methanol

flask
8 Test tubes 3 8 Pyridine
9 Thermometers 1 9 Schiff ’s reagent
10 Water bath 1 10 Semicarbazide hydrochloride
11 Sodium acetate
12 Tollen’s reagent
13 Samples of aldehydes and

ketones
57
Solution Provided
Brady’s reagent: Dissolve 1 g of DNP in 5 cm3 concentrated sulphuric acid.
Add this solution slowly with shaking and cooling to a mixture of water (7 cm3)
and ethanol (25 cm3). Filter it to remove any suspended solid and store as a
stock solution.
Tollen’s reagent:
Solution A: Dissolve silver nitrate (2.5) g in distilled water (40 cm3).
Solution B: Dissolve potassium hydroxide (3 g) in distilled water (40 cm3).
Mix equal volumes of solutions A and B. A white precipitate (Ag2O) is

obtained. Now add concentrated ammonia solution (30%) drop by drop until
the mixture is almost clear.
Ag2O + 4NH3 + H2O 2[Ag(NH3)2]+OH-

Tollen’s reagent Schiff ‘s reagent
should be prepared
immediately before Dissolve p- rosaniline hydrochloride (0.2 g) in saturated solution (20 cm3) of
the experiment sulphur dioxide in water. Shake and allow it to stand for few hours until
because on long
standing it becomes colourless or pale yellow. Dilute with water (180 cm3) and separate
decomposes to yield the clear solution by filtration.
a potentially explosive
solid, silver nitride Iodine-potassium iodide reagent: It is prepared by adding 50 g of potassium
iodide and 25 g of iodine to distilled water (200 mL). A clear solution is
(Ag3N).
obtained after stirring. Deep brown colour of the solution is due to the
formation of triodide anion (I3).
Schiff’s reagent tends H2O

to acquire colour on Kl + l 2 Kl3
storage. Therefore, it
is necessary to use 8.2.4 Procedure
only colourless Schiff
s reagent. 1. Collect sample(s) of aldehyde and ketone from your counsellor and carry
Keep the Schiff’s out physical examination of the sample as discussed in BCHCL 134
reagent in a well course.
stopped bottle in
dark. 2. Carry out solubility test as discussed in Sec. 8.3.1. If your compound is
3. Carry out functional group test (class determination test) as discussed in

Sec. 8.2.1.

a) Physical state :
58 b) Colour :
c) Odour :
d) Ignition test :

compound.
2. Elemental Analysis: Not necessary at this point.
3. Solubility test
4. Test with pH paper:
5. Melting point/Boiling point observed:
5. Class determination:
Brady’s Test
Tollen’s Test
Schiff Test
Iodoform Test
a) Derivative chosen
M.P. observed
M.P. reported in literature
b) Derivative chosen
M.P. observed
Possible compound..........M.P.......Derivatives
9. The structure of this compound is
8.3 ANSWERS
1. NO 2
H2NNH NO 2
59
2. A German chemist Bernhard Tollens discovered. Tollens test
3. p- rosaniline hydrochloride, ii. sulphur dioxide, iii. water
4. I2, NaOH
CH3COR RCO2Na + CH 3l
H2O
5. a, c and d
6. i) 2,4-Dinitropheylhydrazone
ii) Semicarbazone
iii) Oximes
7. i) NO 2
R
C NNH NO 2
R'
2,4-Dinitrophenyl-hydrazone
R
ii)
C NHCONH 2
R'
Semicarbazone
iii) R
C NHCONH 2
R'
Semicarbazone
60
Experiment 9 Systematic Qualitative Analysis of Amide, Nitro and
Amino Compounds and Preparation of their Derivatives
EXPERIMENT 9
ANALYSIS OF AMIDES, NITRO
AND AMINO COMPOUNDS
AND PREPARATION OF THEIR
DERIVATIVES
Structure
9.1 Introduction Requirement
Expected Learning Outcomes Procedure
9.2 Experiment 9A: Identification of Observation and Result
Amines
9.4 Experiment 9C: Identification
Functional Group Tests of Amides
Preparation of Characteristic Functional Group Tests
Derivatives
Requirement Derivatives
Procedure Requirement
Observation and Result Procedure
9.3 Experiment 9B: Iidentification Observation and Result
of Nitro Compounds
9.7 Answers
Functional Group Tests
Derivatives
9.1 INTRODUCTION
Use caution in
In the last experiment we have discussed the qualitative analysis of aldehydes handling amines.
and ketones. In this experiment we shell test the functional group of Many are toxic.
compounds having i) carbon, hydrogen and nitrogen atoms (amines) and ii)
carbon, nitrogen and oxygen atoms (nitro compounds and amids).
First we will learn how to identify amines by i) Hinsberg test ii) Nitrous acid test
iii) Diazotisation and iv) Cablyamin test. In the next section we will discussed 61
the methods of identification of nitro compounds by i) ferrous hydroxide test

and ii) by reduction process.
In the last section we will learn how to identify the amide by i) ammonia
evaluation test and ii) hydroxamic acid test. We will also learn the method for
preparation of derivatives of these compounds.

After performing the experiment given, you should be able to:
 identify the amines by Hinsberg , nitrous acid, diazotisation and

Cablyamin tests;
 prepare characteristic derivative of amines by Scotten-Baumann

method;
 identify the nitro compounds by ferrous hydroxide test and by reduction

process;
 prepare characteristic derivatives of nitro compounds by reduction to

amine;
 identify the amide by ammonia evaluation test and hydroxamic acid test;
and
 prepare characteristic derivatives of amides by hydrolysis.
9.2 EXPERIMENT- 9a: IDENTIFICATION OF

AMINES AND PREPARATION OF THEIR
DERIVATIVES
Compounds that contain a basic nitrogen atom with a lone pair are called
amines. The substituent -NH2 is called an amino group. They are
formally derivatives of ammonia, wherein one or more hydrogen atoms have
been replaced by a substituent such as an alkyl or aryl groups (these may
respectively be called alkylamines and arylamines). Amines in which both alkyl
and aryl of substituents are attached to one nitrogen atom may be called
alkylarylamines.
Amines can be classified according to the nature and number of substituents

on nitrogen. There are three types of amines i.e. Primary (1°) amines,
Secondary (2°) amines and Tertiary (3°) amines
 Primary (1°) amines: In primary amines one of three hydrogen atoms in

ammonia is replaced by an alkyl or aromatic group.
 Secondary (2°) amines: In secondary amines nitrogen atom has one

hydrogen atoms and two organic substituents (alkyl, aryl or both) .
 Tertiary (3°) amines: In tertiary amines, nitrogen has three organic

substituents (alkyl, aryl or both) without any hydrogen atom.
62
SAQ 1
Classify the following as Primary (1°) amines, Secondary (2°) amines and
Tertiary (3°) amines.
ɺɺ H
a) RN ɺɺ
b) R3N ɺɺ H
c) R 2N
2

In this section we shall study about the test used for the characterisation of
amines. The amines can be mainly identified by (i) Hinsberg Test (ii) Nitrous
Acid Test (iii) Diazotisation and Coupling and (iv) Cabylamine test (Positive for
primary amines).
i) Hinsberg Test
Primary, secondary and tertiary amines can be identifed by Hinsberg test.

These three amines can be distinguished by this test. The reaction between
primary or secondary amines and benzensulfonyl chloride gives the
corresponding substituted benzenesulfonamide. The reaction is carried out in
excess base. Sulfonamides, of primary and secondary amines, are
Do you allow
distinguishable because sulphonamides from primary amine have acidic
benzenesulphonyl
amino hydrogen, which make the product soluble in alkali. On the other hand, chloride to come in
the benenesulfonamide secondary amines bear no acidic aminmo hydrogen contact with skin. Use
and they are insoluble in both acid and base. Tertiary amines lack the caution in handling
necessary acidic hydrogen for formation of benzenesulfonyl derivatives. amines. Many of
these are toxic.
Thus, with few exceptions, primary amines react with benzensulfonyl chloride
to provide homogeneous reaction mixtures and secondary amines react to
yield heterogeneous reaction mixture.
.. KOH ..
SO2Cl + RNH 2 SO2NHR + KCI + H 2O
Primary
amine
Benzenesulphonyl
deravative
excess excess
HCI KOH
.. +
SO2NR
.. K + H2O
excess
.. KOH ..
SO2Cl + R2NH KOH
SO2NR 2 No reaction
Secondary
amine
Benzenesulphonyl
deravative
63
Procedure
In a test tube take 3-4 drops (or 0.1 g) of the unknown compound, 0.2 g of
benzenesulfonyl chloride 1 cm3 of methanol and 5 cm3 of 10% sodium
hydroxide. Heat the mixture for few minutes. Just below its boiling point, till
order of benzenesulfonyl chloride is gone. Then cool the reaction mixture in
ice. On cooling, if no precipitate appears than the substance is probably a
tertiary amine. If precipitate appears, the amine is either primary or
secondary.
If a precipitate is present, filter it, wash it with 2 cm3 of water and transfer it to a
test tube. Add 2 cm3 of 5% sodium hydroxide solution and warn the reaction
mixture to 50° C and shake it well. If the precipitate dissolves, the amine is
primary. If the precipitate does not dissolve it indicates a secondary amine.
ii) Nitrous Acid Test
The nitrous test is useful to differentiate between primary aliphatic, primary

aromatic, secondary and tertiary amines.
Primary amines react with nitrous acid to yield diazonium ion. The aliphatic
amines yield unstable diazonium ion which decomposes to give nitrogen gas
and alcohol. On the other hand aromatic amines give stable diazonium salt
(stable in solution at 0°C).
Aq. NaNO2 H2O

RNH2 [RN = NCl] ROH + N2 + HCl
HCl
Diazonium salt
Procedure
Take 0.5 g of the compound in a test tube and dissolve it in 2 cm3 2 M

hydrochloride acid (Note: few weakly basic amines require conc. Hydrochloric
acid). Cool it to 5°C in ice and add 4 or 5 drops of 5% aqueous sodium nitrite.
Note which of the following is observed:
i) There is effervescence (nitrogen gas is evolved) and clear solution is

obtained. This shows the presence of primary aliphatic amine or amide
(RCONH2).
ii) No effervescence and formation of a clear solution indicates the

presence of primary aromatic amine or tertiary amine.
iii) Formation of dark brown solution indicates the presence of tertiary

aromatic amine.
NR 2 KOH NR 2
O=N
HCI
4- Nitroscompound
Brown colour
iv) No effervescence but the formation of cloudy solution or emulsion

(generally yellow) indicates the presence of secondary amine.
64
NaNO2
R 2N R2NN O
HCl
N-Nitrosamine
iii) Diazotisation and Coupling
The diazo group is an organic moiety consisting of two nitrogen atoms (azo) at
the terminal position. The general structural formula is R2C=N+=N–.They are
called diazo compounds or diazoalkanes. The process of conversion of
primary aromatic amines into its diazonium salt is called diazotization or
Destroy the
diazotation. Diazonium salts are important synthetic intermediates that can isocyanide by adding
undergo coupling reactions to form azo dyes. Reaction between primary excess of
aromatic amine and nitrous acid give a diazo compound. This reaction is hydrochloric acid and
known as diazotization. It was first given by Peter Griess. Diazonium salt is throw it outside.
used at very low temperature because of the fact that at the
Anilides
higher temperature they are unstable. Secondary and tertiary amines do give
(C6H5NHCOR) also
this test. Secondary amine has only have one hydrogen atom on the nitrogen give positive
and hence they cannot complete the diazotization reaction and gives yellow carbylamines test.
oily nitrosamine products. Tertiary amines do not have any hydrogen atom on
nitrogen; simply undergo an acid–base reaction with nitrous acid giving soluble
salts. Many diazonium salts are highly explosive and decompose violently on
heating. One must be very careful while using them.
Procedure
If nitrous acid test gives a clear solution, then to this solution add 5% 2-napthol
dissolved in sodium hydroxide (2M) and note which of the following is
observed:
a) Formation of bright red to dark brown precipitate indicates the presence of

primary aromatic amine.
b) If no colour appears (ignore white to yellow precipitate) and test (ii) (a) is
positive then perform carbylamines test for primary amines.
iv) Cabylamine test: Positive for primary amines
The carbylamine reaction is used for the identification of primary amines. This
is also known as Saytzeff's isocyanide test. In this reaction, the analyte is
heated with alcoholic potassium hydroxide and chloroform. Formation
of isocyanide (carbylamine) indicates the presence of a primary amine, the
presence of an amine being indicated by the characteristic foul smell of an
isocyanide. Secondary and tertiary amines do not give carbylamine test, since
they have more than one alkyl group which hinders the approach of
-NH2 group. The carbylamines reaction, also known as Hoffman’s isocyanide
test
RNH2 + 3 KOH +CHCl3 R C N + 3 H 2O + 3 KCl
Carbylamide
(isocynaide)
Procedure
Place a small quantity of organic compound, alcoholic KOH (caustic potash)
solution (1 cm3) and chloroform (few drops) in a test tube. Shake the contents 65
of tube and heat gently. A bad smell of isocyanide indicates the presence of a
primary amine.
SAQ 2
Fill in the following blanks.
a) The reaction between primary and benzensulfonyl chloride gives

……………
b) Nitrous Acid test is useful to differentiate between ……, …….. and

………. amines.
c) Primary amine on reaction with alcoholic caustic potash in presence of

chloroform gives ………..
d) ) Cabylamine test gives positive ………. for amines
The most common derivatives of primary and secondary amines are benzoate
and toluene -4- sulphonate. Acetyl derivative is also quite common. However,
tertiary amines do not undergo same reactions. Solid derivatives suitable for
characterisation of tertiary amines are the picrate and methiodes.
Experimental procedures for the preparation of these derivatives are given
below:
Procedure
i) Benzoate and Toluene-4 sulphonate (Scotten-Baumann Method)
Place the compound (0.5 g), 2 M sodium hydroxide (10 cm3) and
benzoylchloride (1 cm3) in a boiling tube. If the mixture is not
homogenous, add sufficient amount acetone. Shake the contents
vigorously until a solid is obtained. Sometimes few drops of water is
added in order to get the precipitate. Filter off the precipitate, wash with
cold water and recrystallise from alcohol.
If you want to prepare toluene -4- sulphonate, use toluene -4- sulphonyl
in place of benzoylchloride.
Aq. NaOH
RNH2 + C6H5COCl RNHCOC6H5 HCl
Aq. NaOH
R2NH + C 6H5COCl R2NCOC6H5 HCl
R2NH + CH 3C6H4SO2Cl R2N . SO 2C6H4 CH3 + HCl
RNH2 + CH3C6G4SO2Cl RHNSO 2C6H4 CH3 + HCl
ii) Acetyl Derivative
Primary and secondary amines are best acetylated with acetic

66 anhydride.
RRNH + (CH3CO)2O RRNCOCH3
CH3COO
R = alkyl, aryl or H
Procedure
Place amine (0.5 g), acetic acid (1 cm3) and acetic anhydride (1 cm3) in
a conical flask. Heat the reaction mixture for about 20 minutes, cool and
pour the contents into ice-water. Filter the solid and crystallise from
water or aqueous ethanol.
Some ortho substituted derivatives of aromatic amines are difficult to

derivatise because of satiric hindrance. Such derivatives can be
prepared by adding a few drops of concentrated sulphuric acid, which
acts as a catalyst, and by use of an excess of acetic anhydride.
iii) Picrates
Procedure
Dissolve the amine (0.5 g) in ethanol (10 cm3) and add saturated
ethanolic solution of picric acid (5 cm3). Heat the reaction mixture on
water bath for 3 minutes and allow it to cool. Filter the solid product and
recrystallize from ethanol.
-
OH O
NO 2 NO 2 NO 2 NO 2
+
R 3N + R3NH
NO 2 NO 2
iv) Methiodides
Procedure
Gently Warm a mixture of the amine (0.5 g) with methyliodide (0.5 g
cm3) on a water bath for several minutes. Then cool it in an ice and
recrystallise the product from ethanol or methanol or ethyl acetate.
R 3 + CH 3Cl R 3NCH 3l
SAQ3
Complete the following reactions;
Aq. NaOH
a) RNH2 + C6H5COCl
CH3COOH
b) RRNH + (CH3CO)2O
c) R3 + CH3Cl
67
SAQ 4
Tick the correct answer from the following choices given below:
a) Carbylamine test is responded by:
i) CH3CH2NH2
ii) CH3NHC2H5
iii) (CH3)3N
iv) (C6H5)2NH
b) Nitrosoamines are formed by
i) Primary amine
ii) secondary amine
iii) tertiary amine
iv) none of above
9.2.3 Requirements
1 Beakers 1 1 HCl
2 Boiling tube 1 2 KOH
3 Burner 1 3 NaOH
4 Conical flask 1 4 Acetic acid
5 Droppers 1 5 Acetic anhydride
6 M.P. Apparatus 1 6 Aqueous sodium nitrite
7 Reflux condenser 1 7 Benzenesulfonyl chloride
8 Round bottom flask 1 8 Benzoylchloride
9 Test tubes 3 9 Chloroform
10 Thermometers 1 10 Ethanol
11 Water bath 1 11 Ethyl acetate
12 ice
13 Methanol
14 Methyliodide
15 2-Napthol
16 Picric acid
17 Toluene -4- sulphonyl
18 Samples of amines
68
9.2.4 Procedure
1. Collect sample(s) of amine from your counsellor and carry out physical
examination and also elemental test of the sample as discussed in
BCHCL 134 course.


Sec. 9.2.1.

a) Physical state :
b) Colour :
c) Odour :
d) Ignition test :

compound.
2. Elemental Analysis: Nitrogen test:
3. Solubility test

(i) Hinsberg Test
(ii) Nitrous Acid Test
(iii) Diazotisation and Coupling and
(iv) Cabylamine test
M.P. observed
69
M.P. observed
9.3 EXPEMENT 9b: IDENTIFICATION OF NITRO

COMPOUNDS AND PREPARATION OF THEIR
DERIVATIVES
Organic compounds having –NO2 as a functional group are known as nitro
compounds. They may be aliphatic (R-NO2) or aromatic (Ar-NO2) compounds.
Both aliphatic and aromatic compounds are oxidising agents.

The most common functional group tests for nitro compound sare
i) Ferrous hydroxide test and
ii) Reduction to amines and Dye Test
i) Ferrous Hydroxide Test
Organic compounds that are oxidizing agents will oxidize ferrous hydroxide
(blue) to ferric hydroxide (brown). The most common oxidizing agents are
nitro compounds. Practically this test is given by all nitro-compounds in
about one minute. During the reaction Fe (II) is oxidised to Fe (III) in the
presence of nitro compounds. The reaction involved is:
++
Fe + OH Fe(OH)2
Fe(OH)2
R(Ar)NO 2 R(Ar)NH 2 + Fe(OH)3
Nitro compound (Brown ppt)
Ferric hydroxide
Procedure
A slight darkening or
To a freshly prepared solution of 2 cm3 of 5% aqueous ferrous ammonium
greenish colouration sulphate, add 2 drops of sulphuric acid (1 M), 1 cm3 of ethanolic sodium
of the blue precipitate potassium hydroxide (2 M) and unknown compound (2 drops of liquid or 0.5 g
should not be of solid). Warm the solution with continuous shaking on a water bath for few
considered a positive minutes. The positive test is indicated by blue precipitate turning rust brown
test. within a minute. Prepare a similar mixture without unknown compound (Blank
test). There will be no change in initially, formed blue precipitate in the blank
70 test.
ii) Reduction to Amines and Dye Test
Nitro compounds can identify by reduction of nitro group. The reaction

involved is:
NO 2 NH 2
Sn/HCI + 2 H2O
+ 6H
-
O
NH 2 + -
N NCI
OH N=N
NaNO 2
HCI
NaOH
red to brown precipitate

Procedure
Take about 0.5 g of the unknown compound and 3 cm3 of 7 M hydrochloride

acid in a boiling tube. Add 1 g of stannous chloride to it and warm with
continuous shaking for 15 minutes. Filter the mixture, cool it in ice (5°C) and
add 5% aqueous sodium nitrite (5-6 drops). To this add 2 cm3 of 5% solution
of 2-napthol in 2 M sodium hydroxide and note which of the following happens:
i) A red to brown precipitate forms which indicates the presence of

aromatic nitro compounds.
ii) No coloured precipitate formation which indicates the presence of

aliphatic nitro compounds. (Ignore white to yellow precipitate).

Preparation of derivatives of nitro compounds depends on the type of nitro
compounds detected. Nitro compounds are reduced to amines and derivatized
as primary amines. This method can be utilized for both alilphatic and aromatic
nitro compounds.
Reduction of Nitro compounds to Primary Amines
Preparation of derivatives of nitro compounds depends on the type of nitro

compounds. Nitro compounds are reduced to amines and derivatised as
primary amines. This method can be utilised for both aliphatic and aromatic
nitro compounds. Nitro compounds can be converted to primary amines by the
following method.
Procedure
Place the nitro compound (1 g) and concentrated hydrochloric acid

(10 cm3) into a small round bottom flask and add ethanol (2 cm3) and tin (3 g).
Cool the reaction mixture until initial reaction subsides and then heat under
reflux for 25 minutes. Decant the supernatant liquid, cool it and basify with
40% sodium hydroxide with stirring and cooling in ice (use excess of 40% 71
Sodium hydroxide to dissolve tin (II) hydroxide formed). Extract the alkaline
mixture with diethyl ether and, dry on anhydrous sodium sulphate, filter and
then evaporate ether. Crystallize the solid from aqueous ethanol.
Sn/HCl
RNO2 RNH2
SAQ 5
Fill up the blanks:
Fe, HCI
a) CH3CH2CH2NO 2
Sn, HCI NaNO 2

b) NO 2
Sn/HCl
c) RNO2
9.3.3 Requirements
1. Test tubes 3 1. NaOH
2. Droppers 1 1. H2SO4
3. Water bath 1 2. HCl
4. Thermometers 1 3. Sodium nitrite
5. Beakers 2 4. Ethanol
6. M.P. Apparatus 1 5. Diethyl ether
7. Round bottom flask 1 6. Phenolphthalein
8. Reflux condenser 1 7. Ferrous ammonium

sulphate
9. Conical flask 8. Sodium potassium

hydroxide
10. Burner 1 9. Stannous chloride
11. Boiling tube 1 10. Tin
12. Erlenmeyer flask. 11. Samples of nitro

compound
9.3.4 Procedure
1. Collect sample(s) of nitro compound from your counsellor and carry out
physical examination and also elemental test of the sample as discussed
72 in BCHCL 134 course.

Sec. 9.3.1.

a) Physical state :
b) Colour :
c) Odour :
d) Ignition test :

compound.
3. Solubility test
(i) Ferrous hydroxide test and
(ii) Reduction to amines and Dye Test.
M.P. observed
M.P. observed
M.P. reported in literature 73

9.4 EXPERIMENT 9c: IDENTIFICATION OF

AMIDES AND PREPARATION OF THEIR
DERIVATIVES
Amides are represented by the general formula RCONH2. The qualitative test
generally used for amides are ammonia evolution test and hydroxamic acid
test.

There are two main functional group tests for identification of amides.
i) Ammonia Evolution Test and
ii) Hydroxamic Acid Test.
i) Ammonia Evolution Test
Amides are hydrolysed with aqueous sodium hydroxide to carboxylic acid salt
and ammonia. The evolution of ammonia is indicative of amide.
This test fails if hydrogen at the nitrogen atom is replaced by an alkyl or aryl
group, then amines are produced.
Aq. NaOH
RCONH2 RCOONa + NH3
Procedure
Heat about 0.2 g of the compound with 2 cm3 of 2 M aqueous sodium
hydroxide. Evolution of ammonia indicates the presence of an amide group.
Detect the evolution of ammonia by its smell and/or by its action on moist red
litmus paper (red  blue).
ii) Hydroxamic Acid Test
Amides, give a coloured solution on treatment with hydroxylamine and ferric

chloride.
O O O
+ NH2OH FeCl 3
R C NH 2 R C NHOH R C Fe + 3HCl
N O
Procedure
Take 2-3 drop or 0.02 g of sample compound in a boiling tube and add 0.2 g of
solid hydroxylamine hydrochloride and 5 cm3 10% NaOH solution. Heat the
mixture on a boiling water bath. Cool and acidify the reaction mixture with
74 dilute hydrochloric acid and add 2-3 drops of 5% aqueous ferric chloride.
Purple or deep red colour due to formation of ferric complex of hydroxamic
acid indicates the presence of amide.
Primary amide (RCONH2) on hydrolysis furnishes carboxylic acid. Carboxylic

acid is identified to characterize the amide.
NaOH H3O
RCONH2 RCOONa + NH3 RCOOH
i) Hydrolysis of Amide-Isolation of Acid
Place the unknown compound (0.5 g) and 2 M aqueous sodium hydroxide (10
cm3) into a conical flask and heat the reaction mixture on water bath for about
30 minutes. The reaction mixture is cooled and acidified with dilute sulphuric
acid. The precipitated acid is filtered, washed with water and recrystallize from
water or ethanol. If on acidification no precipitate is formed, use if for the
preparation of acid derivatives.
ii) Picrate Derivatives
Some amides from picrates. Prepare picrate derivatives as described under

9.3.2 (iii).
SAQ 6
Fill in the blanks:
a) Benzamide upon hydrolysis with alkali followed by acidification

furnished ………………… and ……………………
b) Ethanoic acid on reaction with ammonia afforded ………………….
9.4.3 Requirements
1. Test tubes 3 1. Ethanol
2. Droppers 1 2. Sulphuric acid
3. Water bath 1 3. Sodium hydroxide
4. Thermometers 1 4. Potassium hydroxide
5. Beakers 2 5. Ferric chloride
6. M.P. Apparatus 1 6. Hydroxylamine

hydrochloride
7. Round bottom 1 7. Hydrochloric acid

flask
8. Reflux condenser 1 8.
75
9. Conical flask 9.
10. Burner 1 10.
11. Boiling tube 1 11.
12. Erlenmeyer flask. 12.
9.4.4 Procedure
1. Collect sample(s) of nitro compound from your counsellor and carry out
physical examination and also elemental test of the sample as discussed
in BCHCL 134 course.


Sec. 9.3.1.

a) Physical state :
b) Colour :
c) Odour :
d) Ignition test :

compound.
3. Solubility test
H2O 5% NaOH 5% NaHCO3 5% HCI Conc. Expected Class

H2SO4
i) Ammonia Evolution Test
76 ii) Hydroxamic Acid Test

M.P. observed
M.P. observed
9.4 ANSWERS
1. a) primary amine, b) tertiary amine, c) secondary amine
2. a) benzenesulfonamide, b) primary, secondary, tertiary

c) isocyanide d) primary
3. a) RNHCOC6H5+HCl
b) RRNCOCH3
c) R3NCH3l
4. a) i b) ii
5. a) CH3CH2CH2NH2
NH 2 + -
b) N NCI
c) RNH2
6. a) benzoic acid; ammonia
b) ethanamide
77
UNIT 10
IDENTIFICATION OF
UNKNOWN ORGANIC
SAMPLES
Structure
10.1 Introduction 10.4 Reporting Results for
Qualitative Analysis of
Expected Learning Outcomes Unknown Organic
10.2 Requirements Compounds
10.3 Procedure 10.5 APPENDIX
10.1 INTRODUCTION
After having good practice with the known functional group compound collect
few samples (at least six samples) for the identification of unknown
compounds from the category of functional group discussed in this course.

After performing the given experiments you should be able to:
 describe functional group tests and methods of the preparation of

derivatives of a unknown sample;
 identify the unknown organic compounds
10.2 REQUIREMENTS
1. The requirements for unknown organic samples will be remain same
as for earlier experiments which you have conducted for known organic
sample.
2. Six unknown organic samples
10.3 PROCEDURE
78 Follow the steps given below:
Unit 10 Identification of Unknown Organic Samples
a) Physical State
b) Colour
c) Odour
d) Ignition test
2. Physical constants
Melting point/Boiling point
3. Element detection
(N,S, halogen)
4. Solubility test
5. Functional Group test
Prepare suitable derivatives of the proposed compound and compare

the melting point with the literature report.
Compare the information obtained so far (1-6) with the literature report.
8. Write correct name and structure of the compound
Various experimental steps may be recorded in systematic way for the

identification of compound. This may be illustrated by taking the example of 2-
Napthol.
10.4 REPORTING RESULTS FOR QUALITATIVE

ANALYSIS OF UNKNOWN ORGANIC
COMPOUNDS
Here we will discuss some important points one should keep in mind while
reporting results in a laboratory note book for qualitative analysis of organic
compounds.
Each experiment should start on a fresh page, which should contain a title and
experiment number at the top. A sample note book format for qualitative
experiment is given here. Identification of 2-naphthol ( β -naphthol) is taken as
our example.
Experiment No. ‘A' Identification of an Unknown Organic Compound
a) Physical state.....................Solid
b) Colour.................................white 79
c) Odour..................................Faint phenol-like odor
d) Ignition test .........................luminous, sooty flame, no residue
Comments: This suggest that the compound ‘A’ aromatic compound.
2. Physical Constants
Melting point observed .........................122-124°C
3. Elemental Analysis
N,S,Cl,Br, I...............................................None
4. i) Solubility test
H2O Aq. NaOH Aq.NaHCO3 HCl Conc.H2SO4 Expected class
Soluble Slightly soluble - - Aromatic

phenols
No bubbles
5. Reaction to pH paper .................................not visible colour change
6. Functional Group Test
i) With alcoholic FeCl3..........................................Green solution.
Comment: The above tests indicated the presence of phenolic

compound
7. Preparation of Derivatives
a) Derivatives chosen ........................... 3,5-Benzoate
M.P. Observed ................................. 208-210°C
M.P. reported .................................... 210°C
b) Derivative chosen ..............................1-Naphthylurethane
M.P. observed .................................. 156-158°C
M.P. in literature ............................... 157°C
M.P. of Derivatives
Possible compound M.P 3,5-benzoate 1-Naphthylurethane
2-Naphthol M.P. M.P.
123°C 210°C 157°C
80 Comment: The above data correspond to 2-naphthol

9. Result: The unknown compound is 2-naphthol. The structure of this
compound is
OH
10.5 APPENDIX: Tables for B.P./M.P. of

Organic Compounds and their
Derivatives
Aldehyde and their derivatives
Compound Formula B.P./ B.P./ M.P. of Derivatives (°C)

M.P.* 2,4-Dinitrophenyl Semicabazone Oxime
(°C) hydrazone
Formaldehyle HCHO -21 166 169 with decomposition
Acetaldyhyde CH3CHO 20 168 169 47
Propionaldyhyde CH3CH2CHO 49 150 89 40
Benzaldehyle 179* 236 222 35

CHO
OH
Salicyladehyde 196* 252 Decomposed 231 63
CHO
Ketones and their Derivatives
Compound Formula B.P./ M.P. of Derivatives (°C)

M.P.* 2,4-Dinitrophenyl Semicarbazone Oxime
(°C)
hydrazone
Acetone CH3COCH3 56 128 190 59
Ethylmethyl CH3COC2H5 80 115 145

ketone
Acetophenone 202 240 199 60

COCH 3
O
Benzophenone 48* 239 165 143
C
81
Phenols and their Derivatives

M.P.*
3,5- 1-Naphthyl
(°C)
Dinitrobenzoate urethane
OH
Phenol 182 146 133
o-Cresol 191 138 142

OH
m-Cresol 202 165 128
CH3
OH
p-Cresol 201 189 146
CH3
OH
Resorcinol 118* 201 206
OH Disubstituted
OH
Hydroquinon 171* 317 247
or Quinol
OH
OH
Pyrogallol 132* 205
OH
OH
OH
1-Naphthol 95* 217 152
O
2-Naphthol 123* 210 157
OH
o-Nitrophenol 45* 155 113
NO2
82
Carboxylic Acids and Their Derivatives
M.P.*
(°C) Amide Anilide p-toluidide
Formic acid HCOOH 101 --- 50 53
Acetic acid CH3COOH 118 82 114 147
Propenoic acid CH3CH2COOH 140 85 105 141
Undecanoic CH3(CH2)9COOH 26* 123 99 125

acid
Oxalic acid COOH 101* 419d 254 268

.2H 2O
(Dihydrate) COOH
Citric acid CH 2COOH 100* 210 192 189

(Hydrated) C(OH)COOH
CH 2COOH
Tartaric acid 169* 196d 246d --

CH(OH)COOH
CH(OH)COOH
Succinic acid CH 2COOH 189* 260 230 255

CH 2COOH
Benzoic acid 121* 130 160 158

COOH
OH
Salicyclic acid 158* 139 135
COOH
COOH
Phthalic acid 210* 200 253 201
COOH
83
Ester and Amides
Compound Formula B.P./ Amide Formula M.P.
M.P.*
(°C)
Methyl CH3COOH3 57 Acetamide CH3CONH2 82

acetate Urea
NH2CONH2
Ethyl CH3COOC2H5 77 N-Methylurea CH3NHCONH2 132

acetate
Diethyl COOC 2H5 N,N-Dimethyl CH3NHCONHCH3 102

Oxalate urea
COOC 2H5
Methyl COOCH 3 186 Benzamide 182

CONH 2
Oxalate
COOCH 3
OH
Methyl 54* Salicylamide 129
COOCH 3
benzoate
CONH 2
OH CO
Methyl 199 Phthalimide 139
salicylate NH
COOCH 3
CO
OH
Phenyl 224 235
salicylate COO 42*
Primary and Secondary Amines and Their Derivatives

M.P.*
Benzoate Picrate Toluen Acet-
(°C)
e-4- amide
sulpho
nate
Primary Amines
1-Aminopropane CH3CH2CH2NH2 49 84 135 52 ....
Aniline 181 163 ... 103 114
NH 2
o-Toluidine NH2 200 144 213 110 112

CH3
84
m-Toluidine NH2 203 125 200 114 66
CH3
o-Anisidine 225 60 200 127 88

NH 2 OCH 3
o-Phenetidine NH2 229 104 ... 164 79

NH2
NH 2
p-Toluidine 45* 158 181 118 154
CH 3
NH 2
1- 50* 161 163 157 160
Aminonaphthalene
NH2
2- 113* 162 195 133 134
Aminonaphthalene
Secondary Amines
Diethylamine (C2H5)NH 56 42 155 60 ...
N-Methylaniline 193 63 145 95 ....
NHCH 3
Diphenylamine 54* 180 182 142 ....

NH
Tertiary Amines and Their Derivatives

Compound Formula B.P./ B.P./ M.P. of Derivatives (°C)
(°C)
Picrate Methiodides
Trimethylamine (CH3)3N 33 216 230
Triethylamine (C2H5)3N 89 173 ...
N,N- CH2N(CH3)2 184 93 179
Dimethylbenzyl
amine
N,N- N(CH3)2 193 164 228

Dimethylaniline
N,N-Diemthyl-o- CH 3 185 122 210

toluidine N(CH3)2
85
Nitro Compounds
Compound Formula B.P./M.P. (oC)

1-Nitropropane CH3CH2CH2NO2 131
Nitrobenzene 211
NO 2
CH3
o-Nitrotoluene 222
NO 2
p-Nitrotoluene 54
H3C NO 2
NO 2
m-Dinitrobenzene 90
NO 2
NO 2
Nitronaphthalene 61
o-Nitrophenol NO2 45
OH
Amides
Compound Formula B.P./M.P. (oC)
Acetamide CH3CH2CH2NO2 82
Palmitamide CH3(CH2)14CONH2 106
Benzamide 129
CONH 2
M-Methylurea CH3NHCONH2 102
Urea NH2CONH2 132
CO
Phthalimide 238
NH
CO
86

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BCHEL-148

Indira Gandhi National

Experiment 8: Systematic Qualitative Analysis of Aldehydes and

Experiment 9: Systematic Qualitative Analysis of Amides, Nitro and

Experiment 10: Identification of Unknown Organic Samples 78

Dr Pritam Mukhopadhyay , School of Sciences,

Dr. Sangeeta Pandita

Block Preparation Team

Prof. Bharat Inder Fozdar (Experiments 7, 8, 9 and 10 )

Course Coordinator: Prof. Kamalika Banerjee

So, Best of Luck.

 Graphs drawn should be attached to the laboratory note book.

 The detailed calculations are to be shown.

Expected Learning Outcomes Procedure

1.2 Theory of Chromatography Observations and Calculations

Definition and Classification Result and Discussion

Principle 1.5 Experiment 2: Separation and

Expected Learning Outcomes

 define and classify chromatography;

 understand theoretical principle of chromatography;

 calculate the Rf values; and

 separate and identify cations of analytical group I and II.

1.2 THEORY OF CHROMATOGRAPHY

There are various ways to classify chromatography. On the basis of physical

 Liquid chromatography in which mobile phase used is in the form of a

 Gas chromatography in which mobile phase used is a gas.

Some common steps used in different chromatographic techniques are:

Let us suppose that we wish to separate a mixture of two (say coloured)

Solute in the Stationary phase ⇌ solute in the mobile phase

For which the equilibrium concentration are related as

where, K' = 1/K and K' is equilibrium constant.

K is called as the distribution coefficient, Cs is the concentration of the solute in

If the development further proceeds (elution analysis) the components A and B

1.2.3 The Concept of Rf Value

1.3 PAPER CHROMATOGRAPHIC SEPARATION

Attempts have been to employ paper chromatography for the systematic

1.4 EXPERIMENT 1: SEPARATION AND

1) Unknown solution: It can be prepared by dissolving any one or two

2) Detector: 0.25 M aqueous solution of potassium chromate K2Cr2O4 is Application of the

Apparatus for paper

12. Get it dried to evaporate the developer.

An alternate method for developing paper chromatogram by making paper

15. Calculate the Rf values.

1.4.3 Observations and Calculations

distance travelled by the centre of the solute zone d s

Record your data in the following way:

Sample ds dm Rf = ds/dm Remark

1.4.4 Result and Discussion

1.5 EXPERIMENT 2: SEPARATION AND

separation is achieved by 1-butanol saturated with 3M HCI as developer.

Boiling tubes 5 1-Butanol

Measuring cylinder 1 3M HCl

Pipette 1 bismuth chloride

Cupric chloride Lead chloride

Spotting capillaries 7 Mercuric chloride

Small test tubes 7

Whatman No. 1 filter paper sheets

1. Unknown Solution: It can be prepared by dissolving any one or two

2. Preparation of Detector 1: H2S water. It is prepared by passing H2S gas