BSCCH 304 PDF

BSCCH- 304
B. Sc. III YEAR

LABORATORY COURSE III
DEPARTMENT OF CHEMISTRY
SCHOOL OF SCIENCES
UTTARAKHAND OPEN UNIVERSITY
LABORATORY COURSES- III BSCCH-304
BSCCH-304
LABORATORY COURCES-III
SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
Phone No. 05946-261122, 261123

Toll free No. 18001804025
Fax No. 05946-264232, E. mail info@uou.ac.in
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UTTARAKHAND OPEN UNIVERSITY Page 1

LABORATORY COURSES-III BSCCH-304
Expert Committee
Prof. B.S.Saraswat Prof. A.K. Pant
Department of Chemistry Department of Chemistry
Indira Gandhi National Open University G.B.Pant Agriculture, University
Maidan Garhi, New Delhi Pantnagar
Prof. A. B. Melkani Prof. Diwan S Rawat

DSB Campus, Delhi University
Kumaun University, Nainital Delhi
Dr. Hemant Kandpal Dr. Charu Pant

Assistant Professor Academic Consultant
School of Health Science Department of Chemistry
Uttarakhand Open University, Haldwani Uttarakhand Open University,
Board of Studies
Prof. A.B. Melkani Prof. G.C. Shah
DSB Campus, Kumaun University SSJ Campus, Kumaun University
Nainital Nainital
Prof. R.D.Kaushik Prof. P.D.Pant

Department of Chemistry Director I/C, School of Sciences
Gurukul Kangri Vishwavidyalaya Uttarakhand Open University
Haridwar Haldwani
Dr. Shalini Singh Dr. Charu Pant

Assistant Professor Academic Consultant
School of Sciences School of Science
Uttarakhand Open University, Haldwani Uttarakhand Open University,
Programme Coordinator
Dr. Shalini Singh

Assistant Professor
Department of Chemistry
Uttarakhand Open University
Haldwani

Unit Written By Unit No.
Dr. Nandan Singh Karki 01

Assistant Professor
LSMGPGC, Pithoragarh
Dr. Manisha Bisht

Assistant Professor 02
LSMGPGC, Pithoragarh
Dr. Tanuja Bisht

Assistant Professor 03
Girls P.G.College, Haldwani
Dr. Pushpa Negi 04 & 05

Assistant Professor
Graphic Era Hill University, Bhimtal
Course Editor
Dr. Geeta Tiwari

Associate Professor
D.S.B. Campus Nainital
Title : Laboratory Courses-III

ISBN No. :
Copyright : Uttarakhand Open University
Edition : 2019

CONTENTS
BLOCK-1 INORGANIC CHEMISTRY

Unit 1: Introduction to lab techniques: Inorganic chemistry 05-30
Unit 2: Synthesis and Analysis 31-46
Unit 3: Gravimetric estimation 47-59
BLOCK-2 ORGANIC CHEMISTRY
Unit 4: Qualitative analysis 60-88

Unit 5: Synthesis of organic compounds (any two) 81-110
BLOCK-3 PHYSICAL CHEMISTRY
Unit 6: Molecular weight determination 111-123

Unit 7: Electrochemistry 124-141

UNIT-1 – INTRODUCTION TO LAB TECHNIQUES:

INORGANIC CHEMISTRY
CONTENTS
1.1 Introduction
1.2 Objectives
1.3 Common lab glasswares and apparatus
1.3.1 Cooling baths
1.3.2 Distillation assembly
1.3.3 Spectrophotometer
1.3.4 Hot-air oven
1.3.5 Weighing balance
1.3.6 Desiccator
1.3.7 Melting point measurement instrument
1.3.8 Commonly used glasswares
1.3.9 Some sophisticated instruments
1.4 Basic techniques and procedures
1.4.1 Titration
1.4.2 Fitration
1.4.3 Calibration of glasswares
1.5 Summary
1.6 Glossary
1.7 Self assessment questions
1.8 References
1.9 Suggested readings
1.10 Terminal questions

1.1 INTRODUCTION
It is essential that the beginner should become familiar with basic laboratory apparatus or
instruments and procedures. Moreover, inculcation of information or understanding to keep the
laboratory clean and put the things back in right place after every laboratory exercise is essential.
Routine habit to wear lab apron and maintaining laboratory note book is also equally important.
Each must have to read or follow laboratory safety guidelines or Material Safety Data Sheet
(MSDS).
Here are some important points to be followed by each student, as such;
• Always wear the laboratory coat, goggles and gloves while working with reagents or
chemicals in the laboratory and make it habit.
• To keep the working benches clean and always use bench-cloth to remove or absorb any
spill of solvent or reagent.
• Always put the reagent bottles back to self or locker immediately after use.
• Maintaining the habit of entering log book prior or after use of each instrument is important.
• Most of the sophisticated instruments are interfaced with computer and operated through
software. Therefore, either the print out of the analysis report should be taken or results
should be noted in the note book and it should be considered in routine practice.
• Some reagents are toxic. So, while using them, always use safety guidelines.
Here in this unit, the basic information about laboratory glasswares, general laboratory
techniques, instruments and procedures are described for the students.
1.2 OBJECTIVES
After completing this unit, the students should;
I. Get familiar with the basic laboratory apparatus and instruments.

II. Learn basic laboratory procedures or methods.
III. Learn laboratory safety procedures or precautions.

IV. Learned how to clean the working benches and after completion of laboratory exercise how
to manage the apparatuses.
1.3 COMMON LAB GLASSWARES AND APPARATUS
1.3.1 Cooling baths
Some chemical reactions required constant temperature to proceed and give better yield,
which we can up to some extent achieved by using ice liquid ammonia or mixture of ethylene
glycol and ethanol in simple beakers. However, few chemical reactions required a more accurate
constant temperature to proceed. The simplest and most commonly used apparatus to achieve
constant temperature is water bath. The simplest model of a water bath is shown in Figure 1.1.
Actually, water bath is laboratory equipment used to keep water at a constant temperature
for incubating samples in a laboratory. Water bath always has electrical circuit with manual
temperature control. The application range of water bath includes reagents warming, substrates
melting as well as used to enable certain chemical reactions to occur at high temperature. Once
the correct temperature is reached, the laboratory water bath turns on and off to maintain a
constant temperature. There are different types of water baths such as; water bath with
circulating system, non-circulating water bath, water bath with shaking system and non shaking
water bath. Circulating water bath required for the reactions those proceed at constant
temperature whereas non-shaking water baths are less accurate in sense of maintaining constant
temperature throughout the water bath. Therefore, the type of water bath required depends on the
type of application or more appropriately how much accurate temperature required to maintain.

Figure 1.1 A simple model of water bath
1.3.2 Distillation assembly
Distillation process is used to separate the two different organic compounds having
different boiling points. In this process, a homogenous mixture of different liquids heated to
convert it into vapour and the liquid which one has lower boiling point converted into vapour
first followed by liquid having higher boiling point. After this, these vapours are condensed into
liquid by passing cold water into distillation assembly. Repeating the process on the collected
liquid to improve the purity of the product is called double distillation. Distillation is used for
many commercial processes, such as the production of gasoline, distilled water, xylene, alcohol,
paraffin, kerosene, and many other liquids. Gas may be liquefied and separated. For example:
nitrogen, oxygen, and argon are distilled from air. Diagrammatic representation of general
distillation assembly is shown in Figure 1.2.

Figure 1.2. General distillation assembly

There are different types of distillation processes or assemblies such as;
1.3.2.1 Simple distillation , 1.3.2.2 Steam distillation, 1.3.2.3 Fractional distillation,

1.3.2.4 vapor distillation
1.3.2.1 Simple distillation
Simple distillation is mainly used to separate liquids having quiet significance difference
in their boiling points especially to separate liquids from solids or non-volatile compounds.
1.3.2.2 Steam distillation
Steam distillation is used to separate heat-sensitive components. Steam is added to the

mixture, causing some of it to vaporize. This vapour is cooled and condensed into two liquid
fractions.
1.3.2.3 Fractional distillation
Fractional distillation is used when the boiling points of the components of a mixture are
close to each other, as determined using Raoult's law. A fractionating column is used to separate
the components in a series of distillations called rectification. In fractional distillation, a mixture
is heated so that vapour rises and enters into the fractionating column. As the vapour cools, it
condenses on the packing material of the column. The heat of rising vapour causes this liquid to

vaporize again, moving it along the column and eventually yielding a higher purity sample of the
more volatile component of the mixture.
1.3.2.4 Vacuum distillation
Vacuum distillation is used to separate components that have high boiling points.
Lowering the pressure of the apparatus also lowers boiling points. Otherwise, the process is
similar to other forms of distillation. Vacuum distillation is particularly useful when the normal
boiling point exceeds the decomposition temperature of a compound.
1.3.3 Spectrophotometer
Spectrophotometer is an optical instrument used in lab for both qualitative and

quantitative analysis. In this instrument, the U.V/visible light is passed through the sample and a
detector is used to confirm the absorbance range. If the wavelength of the absorbing compound is
known, one can do both qualitative and quantitative analysis. Now-a-days, it is very frequently
used as basic laboratories experiments. Spectrophotometer comes in both single and double
beam mode. Double beam is quiet common where there are two cuvette holders; one for
reference and another one for the sample or test solution. Spectrophotometer works on Beer and
Lambert’s law principle where absorbance is directly proportional to the concentration of test
compound. A simple spectrophotometer model is represented in Figure 1.3.
Figure 1.3. General spectrophotometer

1.3.4 Hot-air oven
To sterilize or to dry glasswares, hot air oven is used. It is recommended always to use
clean and dry glasswares in chemistry laboratory. The drying oven is designed on the principle of
recirculation and convection mode of heat transfer, to achieve uniform temperature inside the
oven. Air at high speed is spread inside the oven at set temperature with the help of high
performance centrifugal blower. Hot air after the heat transfer to material is taken to suction of
the blower which is passed over the heater coil to gain fresh heat to continue cycle of
recirculation. Oven is represented in Figure 1.4 a & b.
Figure 1.4. a) Hot air oven picture b) different parts of hot air oven
1.3.5 Weighing balance
Weighing balance in a laboratory is a very important and basic instrument. There are
different types of balances available in market depending upon the sensitivity or range of weight.
However, the most expensive are those which can measure the lowest weight. Now-a-days,

analytical balance in laboratories is very crucial. In analytical balances, the measurement is easy,
fast and accurate compared to two pan balance system. The general representation of balance is
shown in Figure 1.5.
Figure 1.5. Analytical balance
1.3.6 Desiccator
A desiccator is a chamber or box that is used to store the hygroscopic materials. A

traditional desiccator is a glass bowl and lid, each with thick glass rims that permit a seal when
greased (Figure 1.6). Desiccant (a hygroscopic chemical that absorbs water out of the air) is
placed beneath the perforated ceramic disk. If the compound is hygroscopic then it is always
suggested to keep it in desiccator on the disk. Some common desiccants are CaSO4, silica gel,
MgSO4, and P2O5.

Figure 1.6 A classical desiccators
1.3.7 Melting point measurement instrument
Melting point is the physical property that is used in characterization of the solid organic
compound. A pure solid organic compound having the melting point in the small range (less than
1oC) while impurity containing solid organic compound having the melting point in the large
range. So, melting point can also be used to check the purity of an organic compound.
Apparatus used for the measurement of melting point of the solid organic compound
called melting point measurement apparatus. The simple melting point measurement apparatus is
represented in Figure 1.7.
Figure 1.7 Melting point measurement apparatus

1.3.8 Commonly used glasswares

1.3.8.1 Glassware for qualitative use
A. Beakers
I. Beakers are cylindrical in shape and may or may not have a volume mark (Figure 1.8). They
are available in the range from minimum 5-10 mL to 4-5 L. These are used to hold solid and
liquid both. In lab, beakers are used to hold solvents for heating, carrying and storing. Their
graduations are approximate, but very useful when exact volumes are not needed.
Figure 1.8 Beaker

B. Flasks
I. Flasks are designed so that the contents can be swirled without spilling. They are also easily
fitted with stoppers and often have the stopper size written directly on the flask.
II. Erlenmeyer Flask
The most common of all flasks is the Erlenmeyer flask (Figure 1.9). This flask is
having a wide base, narrow neck, and conical form, convenient in laboratory
experimentation for swirling liquids by hand. The flat bottom allows the Erlenmeyer flask to
be directly heated and used in simple reflux (boiling) and condensation procedures.

Figure 1.9 Erlenmeyer flask

III. Florence flask
The florence flask is a hybrid between the round bottom and the Erlenmeyer flask and ranges
from a few hundred milliliters to a few liters in size (Figure 1.10). Florence flasks can have
either a flat bottom or a round bottom. So, applications vary from direct heating to using a
heating mantle. It does not have a ground glass joint, so a stopper is used to seal the
container. The rounded shape is better for applications that involve boiling.
Figure 1.10 Florence flask
C. Test tubes
Test tubes are relatively small cylindrical vessels used to store, heat, and mix chemicals
(Figure 1.11). While the test tube comes in specific sizes, it's typically used in qualitative
observational procedures.

Figure 1.11 Test tube
D. Watch glass
The watch glass is used when a high surface area is needed for a small volume of liquid
(Figure 1.12). This is common for crystallization and evaporation, as well as other qualitative
procedures. Watch glasses can also be used as cover for beakers, but not flasks.
Figure 1.12 Watch glass
E. Crystallization dish
The crystallization dish is a hybrid between a watch glass and the Petri dish (common in
biological procedures) (Figure 1.13). It has a low height-to-width ratio, which means the sides
are very low compared to the width of the vessel. This allows high surface area for evaporation,
but the crystallization dish is more commonly used as a short-term container for liquids in a
variety of bath processes (water, acid, or oil).

Figure 1.13 Crystallization dish
1.3.8.2 Glassware for measuring
A. Graduated cylinder
The graduated cylinder is used to measure a semi-precise volume of liquid (Figure 1.14).
While it is not as precise as volumetric glassware, it is much more accurate and precise than a
beaker or flask (to within 1%). Volumes are measured to the bottom of the meniscus for aqueous
solutions and the top of the meniscus for non-aqueous hydrophobic solutions. Graduated
cylinders are general-use pieces of "To Deliver (TD)" glassware, where the delivery volume is
important. Higher levels of accuracy require volumetric glassware.
100
90
80
70
60
50
40
30
20
10
Figure 1.14 Graduated cylinder
B. Volumetric glassware
I. Volumetric flask

Volumetric flasks are used for making standardized (high precision) solutions, where
precision is known to four significant figures (Figure 1.15). Since volumes are not necessarily
additive, the volumetric flask is used to make solutions of precise volumes. The etched mark on
the neck of the glassware signifies the volume to high precision at the specified temperature. A
solution is prepared by adding enough solvent to dissolve the solute, and then the solute is added
and dissolved. The solution is then diluted to the mark using the solvent. The solution is mixed
throughout the dilution process and sometimes requires being placed in an ice bath in the case of
exothermic dissolution (typically strong acids or bases). Volumetric flasks range in size from 1
mL to 4,000 mL and larger.
Figure 1.15 Volumetric flask
II. Pipettes
Volumetric pipettes are known for high precision, like volumetric flasks, but are used to
dispense liquids, typically in the preparation of solutions in a volumetric flask (Figure 1.16). The
pipette also has an etched mark denoting a precise volume, and the solution is drawn into the
pipette using a pipette bulb, never by mouth.

Figure 1.16 Volumetric pipette

III. Micropipettes
Micropipettes are a specialized class of volumetric pipettes used for very small volumes
from 1 µl to 1,000 µL. The micropipette uses plastic disposable tips, but these can be re-used
under appropriate situations (Figure 1.17). Most micropipettes have an adjustable range of
volumes using separate withdraw and dispense actions on the pipette body. The mechanism for
adjusting, determining volume limits, and ejecting disposable tips varies by manufacturer.
Figure 1.17 Micropipette

IV. Burettes
The burette is an analytical piece of glassware used to dispense variable (but precise)
volumes of liquids (Figure 1.18). Commonly found in analytical chemistry, this burette is used in
a variety of titration experiments.
Figure 1.18 Burette

1.3.8.3 Procedural glassware
A. Round-bottom (Boiling) flasks
Round-bottom flasks, or boiling flasks, are typically found in synthesis experiments,

since the round shape allows for even heating and stirring. The neck typically has a female
ground-glass joint and can be attached to condensers and other pieces of glassware. To prevent
spills, the solution volume should not exceed 50% of the flask volume. Sizes are available from a
range of 50 mL to 20,000 mL.
B. Separatory funnel
While most common to the organic chemistry lab, the separatory funnel is used to
separate liquids of different densities and solubilities (Figure 1.19). The bottom of the separatory
funnel is very narrow and leads to a stopcock, allowing for precise separations of liquids, while
the top is very wide for ease in shaking and mixing.

Figure 1.19 Separatory funnel
C. Filter (Büchner) flask (used for vacuum filtration)
The filter flask looks like an Erlenmeyer flask, but has a hose barb near the top to attach a
vacuum hose (Figure 1.20). The flask typically has thicker walls than an Erlenmeyer due to the
reduced pressure (vacuum) used with the flask. Vacuum (Büchner) funnels fit into the neck of
the flask using a rubber collar or a 1-hole rubber stopper.
Figure 1.20 Büchner funnel
D. Funnels (used for filtering and transferring)
Traditional funnels used for gravity filtration have a wide cone-shaped body, for adding
and filtering solutions, and a long narrow stem, for delivery into a flask (Figure 1.21). Filter

paper is folded into a cone shape, inserted into the funnel, and wetted with a solvent (typically
water). The powder funnel has a wider stem designed for dispensing solids and viscous liquids.
Filter paper is only used in conjunction with the filter funnel.
Figure 1.21 Funnel
E. Ceramics
1. Büchner funnel
The ceramic Büchner funnel fits into the filter (Büchner) flask using a rubber cone or 1-
hole rubber stopper (Figure 1.22). The funnel is typically made of ceramic with pin-sized holes
in the flat bottom. Filter paper is placed on top of the holes and wetted with solvent (water) to
prevent solids from getting under the filter paper.
Figure 1.22 Büchner funnel
2. Crucible
A crucible is made of ceramic and holds small amounts of chemicals during heating at
high temperatures (Figure 1.23). Depending on the specific type, the crucible can withstand

temperatures above 1,000°C and is used in conjunction with a Bunsen burner or furnace.
Common uses include heating a hydrated solid to remove water or combusting a compound to
determine organic content.
Figure 1.23 Crucible
3. Mortar and pestle
While the mortar and pestle originated in chemistry (and alchemy) laboratories, it is more
common in pharmacology, biology, and culinary applications. Made of ceramic or stone,
materials are placed in the bowl-shaped mortar and ground and crushed using the pestle (Figure
1.24).
Figure 1.24 Mortar and pestle

1.3.9 Some sophisticated instruments
Two major categories of methods involving sophisticated instruments are spectroscopic

and chromatographic methods. Spectroscopic methods are based on interaction of
electromagnetic spectra (ranging from U.V-light to X-ray and radio-wave) with material.
Spectroscopic methods are mainly used to characterize the materials. The most important
spectroscopic methods are:
• Atomic Absorption Spectroscopy, Flame Photometry, Atomic Fluorescence Spectroscopy

• Emission Spectroscopy
• Raman Spectroscopy
• Microwave Spectroscopy
• U.V. Absorption Spectrophotometer
• Infrared Spectrophotometry
• Fluorophotometry - Phosphorimetry
• Turbidometry – Nephelometry
• Refractometry - Interferometry
• Raman Spectroscopy
• X-ray: Absorption, Emission, Diffraction
• Nuclear Magnetic Resonance Spectroscopy – Electron Spin Resonance Spectroscopy
• Gamma-ray Spectroscopy – Mossbauer Spectroscopy
Whereas chromatographic methods mainly used to separate the different compounds or

molecules based on their affinity or interaction with stationary and mobile phase.
Chromatographic technique is a modern technique for the separation of individual component
present in the mixture. The chromatographic technique is based on the rate at which the
component of a mixture move through the porous medium (stationary phase) under the influence
of some solvent or gas (mobile phase).
Based on the nature of stationary phase and mobile phase, chromatography can be different types
such as;

1-Partition chromatography, eg; Paper chromatography

2-Adsorption chromatography, eg; Thin layer chromatography (TLC)
3-Ion exchange chromatography, eg; Column chromatography
1.4 BASIC TECHNIQUES AND PROCEDURES
1.4.1 Titration
A titration is a technique where a solution of known concentration is used to determine

the concentration of an unknown solution. Typically, the titrant (the know solution) is added
from a burette to a known quantity of the analyte (the unknown solution) until the reaction is
complete, which is often indicated by a colour change. There are four major classes of titration;
• Acid base titration (HCl v/s NaOH)

• Redox titration (FAS v/s KMnO4)
• Precipitation titration ( NaCl v/s AgNO3)
• Complexometric titration ( EDTA v/s water sample)
1.4.2 Filtration
Filtration is a very basic and routinely applied method in laboratories. This method is
used to sieve the solutions having solid particles such as precipitates and for solutions those are
heat sensitive cannot be separated through distillation process. For the simple precipitate
filtration process, we commonly use Whatman filter papers (usually come in different grades).
However for sophisticated instrument such as HPLC we commonly use 0.2µm filter paper.
1.4.3 Calibration of glasswares
1.4.3.1 Calibration of volumetric flask

For the calibration of volumetric flask, at first the weight of cleaned and dried flask is
accurately determined by using the robust balance. Now air free distilled water is filled in the
flask up to the fixed mark on the neck and determine the weight of water containing flask.
Finally with the help of these two weights volume of volumetric flask is obtained.
1.4.3.2 Calibration of pipettes
Calibration of pipette is carried out by weighing the delivered water from the fixed mark.
For this purpose, at first the pipette is washed and dried then after this air free distilled water is
sucked up to the mark into the pipette. Now determine the weight of water delivered in the
previously weighted flask. From the weight of water calculate the true volume of pipette.
1.5 SUMMARY
This is a basic introductory exercise where general description about common laboratory
apparatuses and instruments is given. A brief account of different types of glasswares and their
applications are provided for beginning students. Different precautions and safety procedures are
also described.
1.6 GLOSSARY
• Beaker – Used to hold and heat liquids. Multipurpose and essential in the lab.
• Bunsen burner – Used for heating and exposing items to flame. They have more uses than a
hot plate but do not replace a hot plate.
• Crucible – Used to heat small quantities to a very high temperature.
• Erlenmeyer flask – Used to heat and store liquids. The bottom is wider than the top so it will
heat quicker because of the greater surface area.
• Evaporating dish – Used to heat and evaporate liquids.
• Funnel – Used to target liquids into any container so they will not be lost or spilled.
• Micro spatula – Used for moving small amounts of solid from place to place.

• Mortar and pestle – Used to crush solids into powder for experiments.
• Pipette – Used for moving small amounts of liquids from place to place.
• Ring stand - Used to hold items being heated. Clamps or rings can be used so that items may
be placed above the lab table for heating by Bunsen burners or other items.
• Stirring rod – Used to stir things. Made of glass they will break easily. They are very useful
in the lab.
• Stopper – These come in many different sizes and are used to seal containers. They can also
have holes in them for thermometers and other probes.
• Test tube holder – Used to hold test tubes when they are hot and untouchable.
• Test tube rack – Used to hold test tubes while reactions happen in them or when they are not
needed.
• Tongs – Used to hold many different thi9ngs such as flasks, crucibles, and evaporating dishes
when they are hot.
• Pipestem triangle – Used to hold crucibles when they are being heated. They usually sit on a
ring stand.
• Watch glass – Used to cover beakers so a reaction can be observed safely.
• Wire gauze – Used to place items on for heating. They usually sit on a ring stand.
1.7 SELF ASSESSMENT QUESTIONS
Q 1. Give the name of burner used in the laboratory and also give the name of gas used in the
burner
Ans: Bunsen burner is used in the laboratory and LPG is used for burning in the Bunsen burner,
which is the mixture of lower alkanes mainly propane and isobutene.
Q 2. Which chemicals are used for cleaning the glass apparatus in the laboratory?
Ans: Mixture of concentrated H2SO4 and HNO3 or chromic acid solution can be used for
cleaning the glass apparatus in the laboratory
Q 3. Which substance is used to prepare the filter paper?
Ans: Cellulose is used to prepare the filter paper.
Q 4. Why we use the chemical balance instead of electronic balance in the laboratory?

Ans: Chemical balance gives the more précised results in compare to the electronic balance due
to which we use the chemical balance instead of electronic balance in the laboratory.
Q 5. Which chemical is used the desiccators?
Ans: Anhydrous CaCl2 is used in the desiccator.
Q 6. Which chemical is used when skin is burnt by acid?
Ans: When skin is burnt by dilute acid then washing with NH4OH can be used but when skin is
burnt by concentrated H2SO4 then washing by BaCl2 solution can be used.
Q 7. Why silica crucible is heated before weighing it during gravimetric experiments?
Ans: Silica crucible having the strong tendency to adsorb the moisture by which its accurate
weight cannot be obtained which cause the non-accuracy in the results during the various
experiments due to this reason silica crucible is heated before weighing it during gravimetric
experiments.
Q 8. Give the name of apparatus used to prepare H2S gas in laboratory and also give the method
to prepare it.
Ans: Kipp,s apparatus is used to prepare the H2S gas in the laboratory and it is prepared by the
reaction of dilute H2SO4 with ferrous sulphide (FeS) according to the following reaction.
FeS +dil. H2SO4 → FeSO4 +H2S ↑
Q 9. What substance is used in making the centre of wire gauge?
Ans: Centre of wire gauge is constructed by the Asbestos.
Q 10. What is the necessary condition for the fractional distillation during the separation of the
two volatile liquids from the mixture
Ans: There should be the difference of boiling points about 40°C for the fractional distillation
during the separation of the two volatile liquids from the mixture.
1.8 REFERENCES
1. R. Sarkar. (2007). General and Inorganic Chemistry Part II, New Central Book Agency (Pt)
Ltd.
2. Satya Prakash, G.D. Tuli, S.K. Basu and R.D. Madan. Advanced Inorganic Chemistry .Vol.
I, S, S. Chand & Com. Ltd.

3. J. E. Huheey, E. A. Keiter and R. L. Keiter (1993). Inorganic Chemistry: Principles of

Structure and Reactivity, 4th ed. Harper-Collins, New York.
4. N. N. Greenwood and A. Earnshaw. (1997). Chemistry of the Elements, 2nd ed.Pergamon.
5. F. A. Cotton and G. W. Wilkinson. (1989). Advanced Inorganic Chemistry, 5th ed. John-
Wiley & Sons.
6. J. E. House. (2009). Inorganic Chemistry, 1st ed. Academic Press.
7. Shriver and Atkins. (2006). Inorganic Chemistry, 4th ed. Oxford Univ. Press.
8. Fred Basolo and Ralph G. Pearson. (1967). Mechanisms of Inorganic Reactions, 2nd ed. John
Wiley and Sons.
9. A. Skoog, D.A. West, F.J. Holler and S.R. Crouch. (1990). Analytical Chemistry, an
Introduction, 7th ed.
10. JoVE Science Education Database. (2019). General Chemistry. Common Lab Glassware and
Uses. JoVE, Cambridge, MA,.
11. Fifield, F. W., & Kealey, D. (2000). Principles and practice of analytical chemistry. Oxford:
Blackwell Science.
12. Douglas A. Skoog, Stanley R. Crouch and F. James Holler. (2007). Principles of
Instrumental Analysis. Belmont, CA.
13. Arikawa Yoshiko. (2001). Basic Education in Analytical Chemistry (pdf). Analytical
Sciences. The Japan Society for Analytical Chemistry. 17 (Supplement): i571–i573.
Retrieved 10 January 2014.
14. Gary D. Christian. (2004). Analytical Chemistry, 6th ed. Wiley, Hoboken, N.J.
15. B.K. Sharma. (2018). Analytical Chemistry, 1st ed. Krishna Prakashan Media (P) Ltd. India.
16. G. R. Chatwal and Madhu Arora. (2015). Pharmaceutical Chemistry, Himalaya Publishing
House, India.
17. A.L. Gupta. (2015). Modern Analytical Chemistry, Pragati Prakashan, India.
18. R.M. Verma. (2015). Analytical Chemistry, CBS Publishers & Distributors, India.
19. S. M. Khopkar. (2007). Analytical Chemistry: Problems and Solutions, New Age
International (P) Limited, India.

1.9 SUGGESTED READINGS
1. Douglas A. Skoog, Stanley R. Crouch and F. James Holler. (2007). Principles of

2. A. I. Vogel and J. Mendham (2000). Vogel's Textbook of Quantitative Chemical Analysis,
6th ed. Harlow, Prentice Hall.
3. R.A. Day and A.L. Underwood. (2006). Quantitative Analysis, 6th ed.Prentice- Hall India.
4. J.N. Miller and J. C. Miller. (2005). Statistics and Chemometrics for Analytical Chemistry,
5th ed. Pearson/Prentice Hall.
5. Willard, Merritt, Dean and Settle. (2004). Instrumental Methods of Analysis, 7th ed. CBS
Publication.
6. Robert L. Grob and Eugene F. Barry. (2004). Modern Practice of Gas Chromatography, 4th
ed. John Wiley & Sons, Inc Pub.
7. C. N. Banwell. (1994). Fundamentals of Molecular Spectroscopy, 4th ed. McGraw-Hill.
8. F. J Holler, S.R Crouch D.M, West and D. A. Skoog. (2014). Fundamentals of Analytical
Chemistry. Fort Worth, Tex Saunders College Pub.
1.10 TERMINAL QUESTIONS
Q 1. Give a brief account about different safety procedure used in chemistry laboratory.
Q 2. Describe the different types of glasswares used in chemistry laboratory and their
applications.
Q 3. Describe the different types of titrations.
Q 4. What are the common chemistry lab instruments? Explain their applications.
Q 5. Describe the general procedure of glassware calibration

UNIT-2 –SYNTHESIS AND ANALYSIS
CONTENTS
2.1 Introduction
2.2 Objectives INTRODUCTION: Sodium Ferrioxalate complex Na3[Fe(C2O4)3]
2.3 Preparation of coordination compounds
2.3.1 Sodium tris (oxalato) ferrate (III) complex; Na3[Fe(C2O4)3]
2.3.2 Nickel dimethylglyoxime
2.3.3 Tetraamine cupric sulphate complex [Cu(NH3)4]SO4.H2O
2.3.4 Cis and trans potassium-dioxalato diaquo chromate (III) K[Cr(C2O4)2(H2O)2].2H2O
2.4 Preparation of double salts
2.4.1 Ferric alum
2.4.2 Chrome alum
2.5 Summary
2.6 Glossary
2.7 Self assessment questions
2.8 References

2.1 INTRODUCTION
Inorganic compounds are generally formed by non-living natural processes or by

laboratory preparation methods as they do not formed from living things. There are two
important classes of inorganic compounds: Double salts and Coordination compounds.
A double salt is a substance that can be prepared by combining two different salts which
crystallize together into a single substance but when dissolved in water, the double salt ionize
into its constituent ions. Alums (isomorphous crystalline solids that are soluble in water) such as
potash alum, chrome alum, ferric alum are the common examples of double salts.
Coordination or complex compounds can be prepared by a large number of transition
metals in which the metal atom is bonded to neutral molecules or to negatively charged species
(ligands). The ligands can donate electrons to the metal atoms to form a ligand-metal coordinate
bond. When dissolved in water, the coordination compounds do not ionize into its constituent
ions. Tetraamine cupric sulphate complex, nickel dimethylglyoxime complex and cis and trans
potassium-dioxalato diaquo chromate complexes are the example of complex compounds.
2.2 OBJECTIVES
After completing this unit, you will understand;

• Basic understanding of inorganic compound synthesis.
• How to synthesize sodium ferrioxalate complex, tetraamine cupric sulphate complex, nickel
dimethyl glyoximate complex and cis and trans potassium-bis (oxalate) diaquo chromate.
• How to prepare double salts such as ferric alum and chrome alum.
2.3 PREPARATION OF COORDINATION COMPOUNDS
2.3.1 Sodium tris (oxalato) ferrate (III) complex; Na3[Fe(C2O4)3]

2.3.1.1 Objective
To prepare sodium tris (oxalato) ferrate (III) complex.
2.3.1.2 Theory
Mixing of FeCl3 and KOH in minimum amount of water forms hydrated ferric oxide
slurry. And when this slurry is added to the hot solution of sodium oxalate, a greenish-brown
solution of Iron (III) oxalate obtained, which on slow evaporation gives greenish crystals of
sodium tris (oxalato) ferrate (III).
FeCl3 +3 NaOH Fe(OH) 3 + 3NaCl
Fe(OH) 3 + 3H 2C2 O 4 + 3NaOH Na3 [Fe(C 2O4 )3 ] + 6H2O
2.3.1.3 Requirements
Apparatus: Electronic weighing machine, beaker 500 mL, beaker 250 mL, Bunsen burner,
desiccator, filtration apparatus, conical flask, funnel, glass rod, pair of tongs, tripod stand, watch
glass, water bath, wire guaze.
Required chemicals: Ferric chloride 2.50 g

Sodium hydroxide 2.75 g
Oxalic acid 3.00 g
2.3.1.4 Procedure
I. Preparation of ferric hydroxide: Separately dissolve 2.5 g of FeCl3 and 1.75 g of sodium
hydroxide in 1-2 mL of water. Now add dodium hydroxide solution to ferric chloride solution to
make brown colour slurry with stirring. This slurry is the precipitate of Fe(OH)3. Filter the

precipitate of ferric hydroxide in Bruckner funnel and wash it with small amount of hot water
2and 3 times.
II. Preparation of sodium tris (oxalato) ferrate (III): Dissolve 3g of oxalic acid in 10-15 mL of
hot water then add 1 g of NaOH. Transfer ferric hydroxide in this hot solution with constant
stirring. Dissolve Fe(OH)3 in hot solution, taking 3 moles of oxalic acid per 1 mole of Fe(OH)3.
This will produce dark greenish-brown solution of iron (III) oxalate. Filter the solution and
concentrate the green filtrate on water bath and obtain green crystal of sodium tris (oxalato)
ferrate (III).
O
O
O O O
O
Fe
Na3 O
OO
O
O
O
Structure of sodium tris (oxalato) ferrate (III)
2.3.1.5. Result
The yield of sodium tris (oxalato) ferrate (III) is …………………….g.
2.3.2 Nickel dimethylglyoxime
2.3.2.1 Objective
To prepare nickel dimethylglyoxime.
desiccator, filtration apparatus, conical flask, funnel, glass rod, pair of tongs, tripod stand, wash
bottle, watch glass, water bath, wire guaze, sintered glass crucible (G-3).

Chemicals required: Nickel ammonium sulphate 9g

1 %alcoholic DMG solution
Ammonical solution
Reagent preparation
Preparation of nickel ammonium sulphate solution: This solution is prepared by dissolving 9

g of nickel ammonium sulphate in distilled water and few mL of dil. hydrochloric acid in 500
mL measuring flask.
Preparation of 1% alcoholic DMG solution-This solution is prepared by dissolving 0.5 g of
HDMG in 50 mL of distilled water.
Preparation of 1꞉1 ammonical solution-This can be prepared by dissolving 25 mL of liquor
ammonia with 25 mL of distilled water.
2.3.2.3 Theory
Nickel dimethylglyoxime [Ni(DMG)2] complex obtained by the reaction of nickel ammonium

sulphate with 1 %alcoholic dimethylglyoxime in ammonical medium,
NiSO4 (NH4)2SO4.6H2O → NiSO4 + (NH4)2SO4 + 6H2O
NiSO4 + 2HDMG +2NH4OH→ [Ni(DMG)2] + (NH4)2SO4 + 2H2O

ppt
2.3.2.4 Procedure
Prepared 1% alcoholic DMG solution is added in prepared nickel ammonium sulphate

solution. Now add ammonia solution slowly with constant stirring until the smell of ammonia
come out, a scarlet red precipitate of DMG is formed. The precipitate is digested on a water bath
for about half an hour. The solution is filtered in a previously washed dried and weighted
sintered glass crucible (G-3). Now dry it at 120°C in an electric oven. This precipitate is cooled
in a desiccator and weighted.

O H
O CH 3
H3 C
C N N C
Ni
N C
C N
H 3C CH3
O
H O
Structure of nickel dimethylglyoxime complex
2.3.2.5 Result
The yield of nickel dimethylglyoxime is ………………………….g.
2.3.3 Tetraamine cupric sulphate complex [Cu(NH3)4]SO4.H2O
2.3.3.1 Objective
To prepare tetraammine cupric sulphate complex
Chemicals:
Copper sulphate 2.5 grams
Liquid ammonia 5 mL
Ethyl alcohol 7.5 mL
Apparatus: Electronic weighing machine, beaker 500 mL, beaker 250 mL, filtration apparatus,
flask conical, funnel, desiccator, glass rod, tongs, tripod stand, watch glass, water bath.

2.3.3.3 Theory
Hydrated tetraammine cupric sulphate is obtained by addition of liquid ammonia in the

solution of copper sulphate followed by the addition of ethyl alcohol in the solution.
CuSO 4+ 4NH3 +H 2O [Cu(NH3) 4]SO4.H 2O
2.3.3.4 Procedure
The four steps involve during the formation of hydrated tetraammine cupric sulphate
complex given as
Step I Firstly dissolve 2.5 g of crystalline CuSO4.5H2O in minimum amount of H2O in 250 mL
beaker. Now add few drop of conc. H2SO4 to clear up the solution if necessary.
Step II Add liquor ammonia to copper sulphate solution from dropping funnel with constant
stirring until the blue precipitate formed is dissolved to give a deep solution.
Step III Now add 20 mL of ethyl alcohol slowly with constant stirring to the deep blue solution.
And allow it to stand to slow evaporation which gives long needle shaped brilliant dark blue-
violet crystal of tetraamine cupric sulphate complex.
Step IV Filter and wash it with ethyl alcohol and dry in a desiccator.
NH3
C u NH 3 SO4 . H2O
H 3N NH 3
Structure of tetraamine cupric sulphate complex

2.3.3.5 Result
The yield of tetraamine cupric sulphate is …………………g.

2.3.4 Cis and trans potassium-dioxalato diaquo chromate (III)

K[Cr(C2O4)2(H2O)2].2H2O
2.3.4.1 Objective
To prepare cis and trans potassium-dioxalato diaquo chromate complex.
Chemicals: Oxalic acid crystal 3g

K2Cr2O7 1g
C2H5OH 20 mL
desiccator, filtration apparatus, conical flask, Funnel, Glass rod, Pair of tongs, Tripod stand,
Watch glass, Water bath, Wire guaze.
2.3.4.3 Theory
Cis and trans potassium dioxalato diaquo chromate (III) ionize in the following fashion:
K[Cr(C2O4)2(H2O)2].2H2O K + + [Cr(C2 O 4 )2 (H 2O )2 ]- + 2H2O
The complex ion obtained from above ionization process exists in the cis and trans
geometrical isomeric forms which can be represented as:

O H O
O H
O O
O OH 2 O O Cr
O
O O
Cr
O OH 2 O O H
O O H
O
O
C is isomer T rans isomer
Structure of cis and trans dioxalato diaquo chromate complex ions
A. Cis potassium dioxalato diaquo chromate (III) complex K [Cr(C2O4)2(H2O)2]2H2O
This isomer is prepared by the reaction of K2Cr2O7 according to the following reaction:
COOH
K 2Cr2O 7 + 7 .2H 2O 2K [ Cr(C 2O4)2(H2O)2] .2H 2O +6CO 2 +13H 2O
COOH
B. Trans potassium dioxalato diaquo chromate (III) complex K[Cr(C2O4)2(H2O)2].2H2O
This isomer is prepared by the reaction of K2Cr2O7 according to the following reaction.
K[Cr(C2O4)2(H2O)2].2H2O K + + [Cr(C2 O 4 )2 (H 2O )2 ]- + 2H2O
2.3.4.4 Procedure
A. Cis potassium dioxalato diaquo chromate (III) complex
Preparation of the cis isomer involves the following steps:

Step I At first, 3g of oxalic acid and 1g of K2Cr2O7 are mixed with each other and grinded to
obtain the powder form.
Step II Take this mixture in the china dish and heat the content in china dish gently on a low
flame by which a vigorous reaction will occur with the evolution of CO2 and water vapour.
Finally the mixture will become deep colored liquid.

Step III Now without cooling the liquid, 20 mL C2H5OH is added over this liquid and triturate
the content by metallic spatula until the solid mass is formed.
Step IV Now warm the content until the product cannot be obtained in the form of granular
crystals. The crystals of cis potassium dioxalato diaquo (III) complex look black in the diffused
day light which are finally weigh.
B. Trans potassium dioxalato diaquo chromate (III) complex
Preparation of the trans isomer involve the following steps:

Step I Take 3g of oxalic acid crystal in a beaker and add small amount of water and heat to
dissolve the oxalic acid crystal in water.
Step II Take 1g of K2Cr2O7 and small amount of water in a boiling tube and heat to dissolve the
K2Cr2O7 in water.
Step III Now introduce the content of boiling tube in the beaker containing oxalic acid solution
and cover the beaker by watch glass.
Step IV Now cool the dark coloured content of beaker and transfer it to a china dish. The content
of china dish is kept in air for 36-48 hours by which volume is reduced to one third of the
original volume.
Step V Now the crystals of trans isomer get deposited and filter by regular filter paper with the
help of funnel which are washed by water and ethyl alcohol and finally weigh the crystals of
trans isomer.
2.3.4.5 Result
A. The yield of cis potassium dioxalato diaquo chromate (III) complex is …………..g.
B. The yield of trans potassium dioxalato diaquo chromate (III) complex is ……….g.

2.4 PREPARATION OF DOUBLE SALTS
2.4.1 Ferric alum
2.4.1.1 Objective
To prepare ferric alum (ferrous ammonium sulphate); FeSO4.(NH4)2SO4.6H2O
Required chemicals: Ferrous sulphate 5g

Ammonium sulphate 2.5 g
Dilute sulphuric acid 1 to 2 mL
Apparatus: Electronic weighing machine, Beaker 500 mL, Beaker 250 mL, water bath, glass
rod etc.
2.4.1.3 Theory
When equimolar quantity of ferrous sulphate FeSO4.7H2O and ammonium sulphate

(NH4)2SO4 are dissolved in water and the solution is evaporater, light blue coloured crystals of
ferrous ammonium sulphate is separate out.
FeSO4.7H2O + (NH4)2SO4 → FeSO4.(NH4)2SO4 .6H2O + H2O
2.4.1.4 Procedure
To prepare the double salt ferrous ammonium sulphate (Mohar salt), at first few drop of
dilute H2SO4 should be added in the ferrous sulphate (to prevent the hydrolysis of ferrous
sulphate) and dissolve it in a 5 mL of water in a beaker. Now dissolve ammonium sulphate in

minimum amount of water (2 to 3 mL) in a test tube. Now the ammonium sulphate solution
should be added in ferrous sulphate solution and solution is boiled to 2 to 3 mL and allowed to
cool, as a result of which crystals of ferrous ammonium sulphate are obtained. These should be
dried in air and weighed.
2.4.1.5 Result
The yield of ferric alum is …………………g.
2.4.2 Chrome alum
2.4.2.1 Objective
To prepare chrome alum; K2SO4.Cr2(SO4)3 .24 H2O
Chemicals: Potassium dichromate (K2Cr2O7) 5g

Ethyl alcohol (C2H5OH) 4 mL
Concentrated H2SO4 4 mL
Apparatus: Electronic weighing machine, beaker 500 mL, beaker 250 mL, water bath, glass rod
etc.
2.4.2.3 Theory
The crystals of chrome alum may be prepared by reducing the acidified solution of
K2Cr2O7. Reduction can be carried out by using the ethyl alcohol or starch solution.
K2Cr2O7 + 4H2SO4 + 3C2H5OH → K2SO4 + Cr2(SO4)3 + 7H2O +3CH3CHO

K2SO4 + Cr2(SO4)3 + 24H2O → K2SO4.Cr2(SO4)3 .24H2O

Chrome alum
2.4.2.4 Procedure
Five gram of K2Cr2O7 should be taken in a 100 mL beaker and 20 mL of water should be
added into it. Now 4 mL of concentrated H2SO4 should be added drop wise with constant
stirring. The content of beaker should be now placed in the water bath and finally 3 to 4 mL of
ethyl alcohol (C2H5OH) is to added drop wise with constant stirring. The content of beaker
should now be placed overnight, when the crystals of chrome alum are prepared. The crystals
should be washed with small amount of water, dried between the fold of filter paper and
weighed.
2.4.2.5 Result
The yield of chrome alum is ………………..g.
2.5 SUMMARY
In this exercise, the synthesis of sodium ferrioxalate, tetraamine cupric sulphate, nickel
dimethyl glyoxime and cis-trans potassium-dioxalato diaquo chromate (III) complexes along
with two double salts namely ferric and chrome alum were explained in a simple way for the
better understanding of beginner students. All these compuonds were synthesized by using
common laboratory apparatus.
2.6 GLOSSARY
Complex: When center metal is surrounded by ligand (molecule or ions) is called complex.
Crystallization: It process is used for the separation of the solid substance from the saturated
solution prepared at high temperature, by cooling it to room temperature.
Triturate: Grind to a fine powder

2.7 SELF ASSESSMENT QUESTIONS
Q 1. Explain why during the formation of cis-potassium dioxalato diaqua chromate (III), gentle
heating is required instead of strong heating ?
Ans: During the formation of cis-potassium dioxalato diaqua chromate (III) gentle heating is
required otherwise the reaction may go out of control and cause explosion.
Q 2. What do you understand by crystallization process ?
Ans: Crystallization process is used for the separation of the solid substance from the saturated
solution prepared at high temperature ,by cooling it to room temperature.
Q 3. What is mother liquor?
Ans: The liquid remaining after the separation of crystal of substance from the saturated solution
is known as mother liquor.
Q 4. What will be the structure of [Cu(NH3)4]SO4 complex?
Ans: According the concept of VBT structure of [Cu(NH3)4]SO4 complex will be tetrahedral.
Q 5. What will be the coordination no of Ni in [Ni(DMG)2] complex compound?
Ans: Coordination no of Ni in [Ni(DMG)2] complex compound will be 4.
Q 6. What is the difference between double salt and complex salt?
Ans: Double salt on dissolving in any solvent retain the test of all the ions of individual
constituent salts while on the other hand complex salt on dissolving in any solvent cannot
retain the test of all the ions of individual constituent salts .
Q 7. Give the IUPAC name of [Cr(C2O4)2(H2O)2] complex ion?
Ans: IUPAC name of [Cr(C2O4)2(H2O)2] complex ion is dioxalato diaqua chromate (III) ion .
Q 8. What will be the magnetic behavior of [Ni(DMG)2] complex compound?
Ans: Due to the absence of unpaired electron at the central metal atom (Ni) in this complex the
magnetic behavior of [Ni(DMG)2] complex compound will be diamagnetic.
Q. 9. Whether the complex K[Cr(C2O4)2(H2O)2].2H2O will behave as a double salt or complex
salt?

Ans: The complex K[Cr(C2O4)2(H2O)2].2H2O will behave as a complex salt because this
complex cannot retain the test of all the ions of constituent salts on dissolving in any
solvent .
Q.10. Why the hot saturated solution should not cooled suddenly?
Ans: When the hot saturated solution are cooled suddenly then small size crystals of the
substance are obtained but on slow cooling large size crystals are obtained due to which the
hot saturated solution are not cooled suddenly .
Q. 11. What do you know about the term seeding?
Ans: Sometime crystals of the substance cannot be prepared on cooling the saturated solution .A
crystal of same substance is placed in the saturated solution which induces crystallization.
This process is known as seeding.
2.8 REFERENCES
1. A. Skoog, D.A. West, F.J. Holler and S.R. (2000). Crouch. Analytical Chemistry, an
Introduction, 7th Edition.
2. Modern Inorganic Synthetic Chemistry. Second Edition (2017), edited by Ruren Xu Yan Xu
Elsevier.
3. L.W. Jolly. (1991). The Synthesis and Characterization of Inorganic Compounds. Waveland
Pr. Inc.
4. P.J. van der Put. (1998). Synthesis of Inorganic Materials. In: The Inorganic Chemistry of
Materials. Springer, Boston, MA.
5. C.N.R. Rao and Kanishka Biswas. (2015). Essentials of Inorganic Materials Synthesis. John
Wiley & Sons, Inc.
6. G. Pass. (1979). Practical Inorganic Chemistry: Preparations, Reactions and Instrumental
Methods (Science Paperbacks). Springer.

• G. Raj. (2016). Advanced Practical Inorganic Chemistry. 16th ed. GOEL publishing house
Meerut, India.
• I.R. Siddiqui, J. Singh, J. Srivastava, L. D. S. Yadav, R.K.P. Singh and J. Singh. (2008).
Advance Practical Chemistry. Pragati Prakashan, Meerut, India.
• R. J. Angelici. (1991). Synthesis and Technique in Inorganic Chemistry. 2nd ed. University
Science Books, U.S.
Q 1. What do you understand by complex?

Q 2. How to synthesis nickel dimethyl glyoxime?
Q 3. How to synthesis tetraamine cupric sulphate complex?
Q 4. Give the synthesis of any cis and trans complexes.

UNIT-3 -GRAVIMETRIC ESTIMATION
CONTENTS
3.1 Introduction
3.2 Objectives
3.3 Gravimetric estimation of copper and nickel in the given solution
3.3.1 Requirements
3.3.2 Theory
3.3.3 Procedure
3.3.4 Observations
3.3.5 Calculations
3.3.6 Results
3.4 Summary
3.5 Glossary
3.6 Self assessment question
3.7 References

3.1 INTRODUCTION
Gravimetric analysis is one of the most accurate and precise analytical methods for
quantitative analysis of analyte. Gravimetric methods are quantitative methods that are based on
measuring the mass of a pure compound to which the analyte is chemically related. In this
method, the solution of pure compound is converted into insoluble form of a compound from
which analyte mass is accurately measured.
There are three most common methods used for gravimetric analysis are:
• Precipitation gravimetry
• Volatilization gravimetry
• Electrogravimetry method
Precipitation gravimetry: As we discussed in previous paragraph, in this method, the analyte of

interest is separated from a solution by precipitation with appropriate reagent followed to
conversion into a compound of known composition that can be weighed.
Volatilization gravimetry: In this method, the interested analyte is separated from other a
sample by converting it into another form of a gaseous compound followed by weight.
Electrogravimetric method: In this method, the analyte of interest is separated by
electrochemical method. The analyte to be separated is deposited on an electrode by electrolysis.
The mass of this product then should be used to calculate the analyte concentration.
In this exercise, we will discuss in detail only about precipitation gravimetric method. In
precipitation gravimetry, the analyte is converted to a sparingly soluble precipitate. This
precipitate is then filtered, washed to be free of impurities, converted to a product of known
composition by suitable heat treatment, and weighed.

3.2 OBJECTIVES
Determination of nickel and copper in a given mixture by precipitative gravimetric

analysis method. In the following exercise, the precipitation of copper (Cu+) and nickel (Ni2+)
from the solution should be done by adding ammonium thiocyanate and dimethyl glyoxime
respectively.
After completing this exercise students should learn;
• The basic understanding of gravimetric analysis.
• Different steps to be followed in the gravimetric analysis.
• How to choose appropriate precipitating agent to avoid contamination of non-essential
analytes.
• Optimization of the precipitation conditions in order to obtain a desirable precipitate.
• Basic calculations related to gravimetric analysis.
3.3 GRAVIMETRIC ESTIMATION OF COPPER AND NICKEL
3.3.1 Requirements
3.3.1.1 Objective
To estimate copper and nickel in the given solution of cupper and nickel ios gravimetrically
3.3.1.2 Apparatus
Electronic weighing machine, beaker 500 mL, beaker 250 mL, Bunsen burner, desiccator,
filtration apparatus, conical flask, funnel, glass rod, pair of tongs, sintered glass crucible (G-3),
sintered glass crucible (G-4), tripod stand, wash bottle, watch glass, water bath, wire guaze.

3.3.1.3 Chemicals
10% Ammonium thiocyanate, aqueous ammonia, copper(II) sulphate, dimethylglyoxime,

ethanol Hydrochloric acid (conc.), nickel(II) sulphate, nitric acid (conc.), ammonium hydrogen
sulphite solution
3.3.2 Theory
During the gravimetric estimation of copper and nickel, copper is estimated first as
cuprous thiocyanate (CuSCN) and in the filtrate, nickel is estimated as nickel dimethylglyoxime
[Ni(DMG)2]. The given solution is first treated with ammonium thiocyanate solution
precipitating cuprous thiocyanate leaving behind nickel in the solution. During precipitation of
cuprous thiocyanate, sulphurous acid is added to reduce Cu(II) to Cu(I).
2Cu2+(aq) + HSO3-(aq) + H2O(l) → 2Cu+(aq) + HSO4-(aq) + 2H+(aq)

2Cu+(aq) + SCN-(aq) → 2CuSCN(s)
2Cu2+(aq) + HSO3-(aq) + 2SCN-(aq) + H2O(l) → 2CuSCN(s) + HSO4-(aq) + 2H+(aq)
After precipitating CuSCN, solution of dimethylglyoxime is added in the filtrate to precipitate

nickel as scarlet red coloured nickel dimethylglyoxime.
Ni2+(aq) + 2H2DMG(aq) → Ni(HDMG)2(s) + 2H+(aq)

Nickel dimethylglyoxime
H
O O
CH3 C N N C CH3
Ni
CH3 C N N C CH3
O O
Nickel dimethylglyoxime

3.3.3 Procedure
Following steps are involved in gravimetric analysis
3.3.3.1 Preparation of the solution
A. Estimation of copper
3.3.3.2 Precipitation
3.3.3.3 Digestion
3.3.3.4 Filtration
3.3.3.5 Washing
3.3.3.6 Drying or igniting
3.3.3.7 Weighing and finally calculation
B Estimation of nickel
3.3.3.9 Digestion
3.3.3.10 Filtration
3.3.3.11 Washing
3.3.3.12 Drying and weighing
3.3.1 Preparation of the solution
a) CuSO4.5H2O solution: 60.0 grams of CuSO4.5H2O is dissolved in 1000 mL distilled water.

b) Nickel ammonium sulphate solution: 40.0 grams of nickel ammonium sulphate is dissolved
in 1000 mL distilled water.
c) 40 mL CuSO4.5H2O and 40 mL of nickel ammonium sulphate solutions are mixed in 250 mL
beaker and make up the volume up to the mark by the addition of distilled water. This
solution is named as solution A.
Now by using the 50 mL of solution “A” (test solution) gravimetric estimation of Cu and Ni can
be done.

B. Estimation of copper
a) Pipette out 50 mL of test solution in a 500 mL beaker. Add into it 2-3 mL dilute HCl and 40-
50 mL of freshly prepared ammonium hydrogen sulphite or sulphurous acid solution and
ensure that smell of SO2 continuously coming out. This solution is diluted by 100 mL of
distilled water.
b) Boil the contents of the beaker gently on a water bath. Remove the flame and add 10%
ammonium thiocyanatesolution (25 mL) in this solution with constant stirring. Keep stirring
the precipitate with a glass rod intermittently.
3.3.3.3Digestion
Now keep the solution along with precipitate in the beaker in water bath for 30 minutes.
This process is called digestion. Digestion involves dissolution of small particles and re-
precipitation on larger ones resulting in particle growth and better precipitate characteristics.
This process is called Ostwald ripening.
3.3.3.4Filtration
Weigh an empty and cleaned sintered glass crucible (G-4) and note it’s mass. Filter the
precipitate through this crucible first by draining off the supernatant liquid and then the
precipitate with minimum quantity of liquid. This procedure of filtration keeps the precipitate
away from clogging the pores of the crucible.
3.3.3.5 Washing
Wash the precipitate with 2-3% NH4SCN solution. Wait and check the filtrate. If any
precipitate appears then filter the precipitate again through the same weighed crucible. Preserve

the filtrate for estimation of nickel. Finally wash the precipitate several times with 20% ethanol
until the precipitate is free from 'SCN-ions.
3.3.3.6 Drying
Now heat the sintered glass crucible at a temperature of 100 - 120°C in a hot air oven for
at least an hour.
3.3.3.7 Weighing and calculation
Cool the crucible in a desiccator and then weigh. Repeat the process of heating, cooling
and weighing till the constant mass of the crucible with precipitate is obtained.
B Estimation of nickel (Ni2+)
3.3.3.8 Evaporation
The filtrate and washing left after the estimation of Cu is placed in an evaporating dish
and evaporate the solution nearly to 80-100 mL on a water bath. Now add 35 mL concentrated
nitric acid and 15 mL concentrated HCl and heat to dryness on a water bath or sand bath in a
fume hood.
To the residue, obtained, add 100 mL of distilled water and dissolve the contents by
shaking. Add 2-3 drops of methyl red indicator and then add 10% aqueous ammonia solution till
smell of ammonia prevails and the colour of the methyl red changes to yellow. Now add 40-50
mL of dimethylglyoxime solution with adequate stirring with a glass rod. Again add ammonia
solution till the colour becomes yellow.

3.3.3.10 Digestion
Digest the precipitates of [Ni(DMG)2] complex on a water bath at least for 30 minutes.
3.3.3.11 Filtration
After digestion, cool the solution for 1 to 2 hours and filter by using previously weighted
sintered crucible (G-3). Drain out the supernatant liquid first and then the precipitate with
minimum quantity of liquid.
3.3.3.12 Washing
Now wash the precipitate 2-3 times with 2-3% dimethylglyoxime solution. If any
precipitate appears in the filtrate, then filter it again through the crucible. Wash the precipitate
with 2-3% aqueous ammonia solution. Finally wash the precipitate with hot water.
3.3.3.13 Weighing
Heat the crucible and precipitate at temperature range 100-120°C in a hot air oven. Cool
the crucible in a desiccator and then weigh it. Repeat heating, cooling and weighing till a
constant mass of the crucible with precipitate is obtained.
3.3.4 Observations
I. Observe the empty mass of sintered crucible (G-4) at least 2-3 times and took the average of
constant readings = w1 g
II. Observe the mass of sintered crucible (G-4) and CuSCN precipitates together 2-3 times and
took the average of constant readings = w2 g

III. Similarly observe the empty mass of sintered crucible (G-3) at least 2-3 times and took
the average of constant readings = w3 g
IV. Again observe the mass of sintered crucible (G-3) and Ni(DMG)2 precipitates together 2-
3 times and took the average of constant readings = w4 g
3.3.5 Calculations
3.3.5.1 Calculations for copper
I. First we should measure the weight of CuSCN as follow
Mass of sintered crucible (G-4) + CuSCN precipitates (w1) - mass of empty sintered crucible (G-
4) (w2) as shown in observation section.
II. Now we should use the stoichiometry for CuSCN formation
Cu CuSCN
(Mol Wt. 63.57 g) (Mol Wt. 121.62 g)
Suppose constant weight of cuprous thiocyanate be x g.

121.62 gram of cuprous thiocyanate contain copper = 63.57g
So, x gram of cuprous thiocyanate will contain copper = g
Since 50 mL of solution contain Cu = g
So 1000 mL of solution will contain Cu = g/L
Concentration of copper = g/L
3.3.5.2 Calculation for nickel
I. First we should measure the weight of Ni(DMG)2 as follow

Mass of (sintered crucible (G-3) + Ni(DMG)2 precipitates) (w4)- (mass of empty sintered
crucible (G-3) (w3) as shown in observation section.
II. Now we should use the stoichiometry for Ni(DMG)2 formation

Suppose the weight of nickel dimethylglyoxime complex = y g
[Ni(DMG)2] Ni
(Mol Wt. 288.91 g) (Mol Wt. 58.69g)
Since, 288.91 gram of [Ni(DMG)2] complex contain nickel =58.69 g
So, y gram of [Ni(DMG)2] will contain nickel = g
Since 50 mL of given solution contain nickel = g
So 1000 ml of given solution will contain nickel = g/L
Concentration of Nickel= g/L
Note: Gravimetric factor = , where n= moles of analyte, m= moles of ppt. compound
based on stochiometry.
3.3.6 Results
Mention the results as:

Concentration of copper in the test solution = g/L
Concentration of Nickel in the test solution = g/L
3.4 SUMMARY
In this exercise, precipitation gravimetric analysis is performed for the determination of

concentration of copper and nickel in a given test solution. For the determination of copper (II)
sulphate in a test solution, copper is precipitated as copper (I) thiocyanate (CuSCN) that is

filtrated and weighed. Similarly, nickel (II) sulphate concentration determined by precipitating
nickel as nickel dimethylglyoxime [Ni(DMG)2] followed by filtration and weighing.
3.5 GLOSSARY
Precipitation: It is a process of particle aggregation to form small nuclei those later combined
together to form large particles or nucleus.
Analyte: It is compound of interest that is determined or analyze in a given sample
Digestion: Digestion involves dissolution of small particles and re-precipitation of larger ones
resulting in particle growth and better precipitate characteristics.
Filtration: It is a physical process used to sieve or separate particles or precipitates from
solution.
Drying: It is also a physical process where solvent is heated up at about 120-150oC in a hot air
oven to remove the moisture or concentrate the solvent.
Desiccator: This is sealable enclosure containing desiccants used for preserving moisture-
sensitive items. A common use of desiccator is to protect chemicals which are hygroscopic or
which react with water from humidity.
Sintered glass crucible: Special glass crucible having specific pore size is used in the laboratory
to contain chemical compounds when heated to extremely high temperatures. Crucibles are
available in several sizes and typically come with a correspondingly-sized lid
Water bath: A water bath is laboratory equipment made from a container filled with heated
water. It is used to incubate samples in water at a constant temperature over a long period of
time.
3.6 SELF ASSESSMENT QUESTION
Q 1.Draw the structure of Ni(DMG)2.

Q2. Describe the process of precipitation.
Q 3. What do you understand by nucleation process in precipitation?
Q 4. Describe the digestion process in precipitation.

Q 5. Describe the threshold concentration of precipitating agent used in precipitation process to

obtained maximum precipitation.
Q 6. Describe the Von-Weimarn ratio in precipitation process.
Q 7. Describe the gravimetric factor
Q 8. Orthophosphate (PO43-) is determined by weighing as ammonium phosphomolybdate,
(NH4)PO4.12MoO3. Calculate the percent P in the sample and the percent P2O5 if 1.1682g
precipitate were obtained from a 0.2711 g sample?
Ans. 7.11 %, 16.30%
Q 9. An ore is analyzed for the manganese content by converting the manganese to Mn3O4 and
weighing it. If a 1.52 g sample yields Mn3O4 weighing 0.126g, what would be the percent Mn
and Mn2O3 in the sample?
Ans. 8.58 % , 5.97 %
Q 10. What is the role of pH in precipitation process?
3.7 REFERENCES
1. A. Skoog, D.A. West, F.J. Holler and S.R. (2000). Crouch. Analytical Chemistry, an
Introduction, 7th Edition.
2. F. W. Fifield and D. Kealey. (2000). Principles and Practice of Analytical Chemistry.
Oxford, Blackwell Science.
3. Douglas A. Skoog, F. James Holler and Stanley R. Crouch. (2007). Principles of
4. Yoshiko Arikawa. (2001). Basic Education in Analytical Chemistry. (pdf). Analytical
Sciences. The Japan Society for Analytical Chemistry. 17 (Supplement): i571–i573.
Retrieved 10 January 2014.
5. Gary D. Christian (2004). Analytical Chemistry, 6th ed. Wiley, Hoboken, N.J.
6. B. K. Sharma. (2018). Analytical Chemistry, 1st ed. Krishna Prakashan Media (P) Ltd. India.
7. G. R. Chatwal and Madhu Arora. (2015). Analytical Chemistry. Himalya Publishing House,
India.
8. A. L. Gupta. (2015). Modern Analytical Chemistry. Pragati Prakashan, India.

9. R.M. Verma. ( 2015). Analytical Chemistry. CBS Publishers & Distributors, India.
10. S. M. Khopkar. (2007). Analytical Chemistry: Problems and Solutions, New Age
International (P) Limited, India.
1. A. I. Vogel and J. Mendham. (2000). Vogel's Textbook of Quantitative Chemical Analysis.

6thed. Harlow, Prentice Hall.
2. J. N. Miller and J. C. Miller. (2005). Statistics and Chemometrics for Analytical Chemistry.
5thed. Pearson/Prentice Hall.
3. Daniel C. Harris. (2002). Quantitative Chemical Analysis. 6th Ed. W. H. Freeman.
Q 1. What do you understand by gravimetric analysis?

Q 2. Briefly describe the precipitation mechanism
Q 3. Describe the precipitation gravimetric method of analysis
Q 4. Write short note on the following
(a) Electrogravimetric method (b) Volatilization gravimetry
Q 5. Describe the relationship between concentration of precipitating agent and precipitates
obtained.

UNIT 4: QUALITATIVE ANALYSIS
CONTENTS
4.1 Introduction
4.2 Objectives
4.3 Systematic identification of organic compound
4.3.1 Physical examination of the compound
4.3.2 Tests for unsaturation (presence of multiple bonds which can be involved in
addition reactions)
4.3.3 Solubility test
4.3.4 Ignition test
4.3.5 Detection of elements
4.3.6 Detection of functional groups
4.3.7 Determination of melting / boiling point of the compound
4.3.8 Confirmatory test for the suspected organic compound and preparation of suitable
derivatives.
4.3.9 Result
4.3.10 Structural formula
4.4 Preparation of some important derivatives
4.5 Separation and systematic identification of compounds present in an organic mixture
4.5.1 Separation of solid-solid mixture on the basis of solubility
4.5.2 Separation of solid-solid mixture on the basis of salt formation

4.1 INTRODUCTION
Separation, identification and structure determination of an unknown substances is an

important aspect of organic chemistry. Different spectroscopic techniques such as Infra-red
spectroscopy (IR), Ultra-Visible (UV) spectroscopy and Nuclear Magnetic Resonance (NMR)
spectroscopy are helpful in elucidation of the structure of organic compounds, but these
spectroscopic techniques must be supplemented with other information such as physical state,
solubility, elements present, melting or boiling point and functional groups about the unknown
compound. Formation of a solid derivative of unknown compound with known melting point
provides final confirmation of structure. This unit is provides the information regarding the
separation and qualitative analysis of unknown organic compounds. Qualitative analysis of
organic compounds involves a study of various chemical characteristics of a given compound
and then a careful correlation of the observed data.
4.2 OBJECTIVES
By studying this unit, the students will be able to understand:

• Qualitative analysis
• Methods of separation of mixture of organic compounds.
• Systematic identification of organic compounds
• Special elements and their identification
4.3 SYSTEMATIC IDENTIFICATION OF ORGANIC COMPOUND
It involves the systematic identification of an unknown organic compound. The

identification of an unknown organic compound includes the following steps-
4.3.12 Tests for unsaturation (presence of multiple bonds which can be involved in addition
reactions)
4.3.13 Solubility test
4.3.14 Ignition test

4.3.15 Detection of elements
4.3.17 Determination of melting / boiling point of the compound
4.3.18 Confirmatory test for the suspected organic compound and preparation of suitable
derivatives.
4.3.19 Result
4.3.20 Structural formula
The following physical characters are helpful in identifying the given organic compound-
(i) Physical state: This physical test indicates the physical state of the compound
(liquid/solid).
(ii) Colour: Each organic compound has a characteristic colour due to the presence of a group
known as chromophore and can be suspected by observing its colour as shown below-
(a) Pale yellow-Nitro compounds, Iodoform
(b) Orange- Ortho Nitroaniline, phenanthroquinone, azo compounds
(c) Red-1,2 Napthaquinone
(iii)Odour: The presence of a characteristics odour is an indication of a particular class of
organic compound.
(a) Pleasant- Esters, ethers, lower aliphatic alcohols, Chloroform
(b) Pungent- Acetic acid, acetyl chloride, acetic anhydride, benzoyl chloride, benzyl
chloride, formic acid and pyridine
(c) Bitter almonds- Nitrobenzene, benzaldehyde
(d) Phenolic-Phenols, naphthols, some derivatives of salicylic acid
(e) Moth balls-Napthalene
(f) Fishy-Amines
(g) Rotten eggs-Sulphur containing compounds

4.3.2 Tests for unsaturation
Positive test of organic compounds for Bromine solution and Baeyer’s reagent (1%
KMnO4, w/v) shows the presence of unsaturated compound
(i) Bromine solution test- Take solution of compound in a test tube and add the bromine
solution dropwise with shaking. Disappearance of reddish brown colour of bromine solution
indicates the presence of unsaturation.
Br
Br Br + C C C C
Br
(ii) Baeyer test- Add Baeyer’s reagent (1%w/v KMnO4) dropwise to a solution of organic
compound prepared in water or ethanol. Shake it continuously and disappearance of purple
colour indicates the presence of unsaturated compound.
4.3.3 Solubility tests

Solubility behaviour of organic compound in H2O, NaOH, NaHCO3 and HCl provides
valuable information for the presence of certain classes of organic compounds. Therefore, careful
observation is important for identification of organic compounds.
The solubility test is performed in a sequential manner which is as follows-
(i) Dissolve 0.5 g organic compound in 2 mL water with shaking.
(ii) If the compound is insoluble in water then observe its solubility in 2M or 5% (w/v) NaOH
solution.
(iii)The compound insoluble in NaOH solution is further checked for its solubility in 1.5M HCl
(iv) An organic compound, insoluble in H2O, NaOH and HCl solution, contains no nitrogen and
again can be tested for its solubility in 2M H2SO4 solution.
Solubility flow chart (Figure 4.1) will give you an idea about the presence of various classes of
organic compounds which thereby will support the identification of given organic compound.

Figure 4.1. Solubility flow chart

4.3.4 Ignition
Take a small amount of compound on metal spatula or water bath ring and burn in a flame, if it
burns
i. With non-sooty flame- Aliphatic compound suspected
ii. With a sooty flame-Aromatic compound suspected
iii. Non ignition- polyhalogenated compound suspected
iv. With charring- Carbohydrate, tartaric acid and its salts, suiphonic acids
v. Violet vapours- Iodoform
4.3.5 Detection of additional (special) elements

Organic compounds are composed of two or more elements. All organic compounds
contain carbon and hydrogen in their basic skeleton but the presence of nitrogen, sulphur and
halogens is determined in certain compounds.
Oxidative or reductive mineralization (ionization) of an unknown organic compound
gives the test for the presence of an additional element using the method of Lassaigne’s. Since

the organic compounds are non-ionic in nature therefore, they are fused with sodium metal for
detection of these elements to convert them into water soluble inorganic compounds. Based on
this fact, the most effective method Lassaigne’s test was developed by J. L. Lassaigne. In this
test, the organic compounds on fusion with alkali metals are first converted into ions i.e. nitrogen
in presence of carbon is converted to cyanide ion (CN-) whereas sulphur and halogen are
converted to sulphide (S--) and halide ions (Cl-) respectively.
4.3.5.1 Fusion with sodium (Lassaigne’s Test)
Place 20-22 mg of the solid or 1 mL of liquid organic sample in an ignition tube. Cut a
small piece of sodium metal, dry it with filter paper so as to remove the adhering liquid that is
kerosene oil and then slide it along the side of the ignition tube to its bottom. Add 5-10 mg of
compound more so that the sodium is now sandwiched between the organic sample. Heat the
ignition tube in a Bunsen flame till sodium melts and then strongly till it becomes red hot. There
is an alternative method of organic compound fusion with sodium. In this method first take dried
sodium piece in a dried ignition tube and slightly heat the ignition tube over a Bunsen burner so
that the sodium piece melt into a shiny liquid. Take a pinch of organic compound with the help
of a spatula into the fusion tube till it becomes red hot. Plunge the red hot ignition tube
immediately into a porcelain dish containing 50 mL distilled water. This breaks the ignition tube.
Plunge two or three ignition tubes into water in the same way. If the ignition tube does not break,
crush the tube with the help of a glass rod. Boil the mixture for 2-3 minutes and then filter. This
filtrate is known as a sodium extract. The filtrate should be clear and alkaline. If it is dark in
colour, it indicates incomplete fusion and so the process should be repeated with fresh ignition
tube. In this process nitrogen is converted into water soluble inorganic cyanide while the
halogens and sulphur formed water soluble halides and sulphide respectively.
Na +C + N →NaCN when nitrogen is present

2Na + X2→ 2 NaX when halogens are present
(X=Cl−, Br−, I−)
2Na + S→ Na2S when sulphur is present
2Na + C + N + S → NaCNS when nitrogen and sulphur both are present

The above sodium extract is alkaline in nature due to the formation of sodium hydroxide.
Na + 2H2O → 2NaOH + H2
4.3.5.2 Test for Nitrogen
• In a test tube, place 1 mL of sodium or Lassaigne’s extract, add 1 mL of freshly prepared

ferrous sulphate solution. A dark green or grey precipitate of ferrous hydroxide is formed.
Heat the tube over a Bunsen burner. Ferrous sulphate reacts with sodium cyanide to form
sodium ferro cyanide. Add a few drops of ferric chloride solution in to the test tube and again
add small amount of conc. HCl to acidify the solution. Appearance of prussian blue colour or
precipitate indicates the presence of nitrogen.
FeSO4 + 2NaOH → Fe(OH)2 + Na2SO4

Ferrous hydroxide
Fe(OH)2+ 2NaCN → Fe(CN)2+ 2NaOH
Ferrous cyanide
Fe(CN)2 + 4NaCN → Na4[Fe(CN)6]
(Final reaction)
FeSO4 + 6NaCN → 2Na4[Fe(CN)6] + Na2SO4
Sodium ferrocyanide
In the presence of hydrochloric acid, ferric chloride reacts with sodium ferrocyanide to
give Prussian blue (blue green) colour of ferric ferro cyanide.
3Na4[Fe(CN)6] + 4FeCl3→ Fe4[Fe(CN)6]3+ 12NaCl

Ferric ferro cyanide
• Acidify 2 mL of sodium extract with glacial acetic acid, add 1-2 drops of freshly prepared
1% solution of benzidine in 50% acetic acid and then stir the solution. Add 1 drop of 1%
CuSO4 solution. A blue coloured solution or precipitate indicates the presence of nitrogen.

4.3.5.3 Test for halogens
In a test tube place 5 mL sodium extract, add dilute HNO3 solution and then boil the
solution to expel H2S or HCN, if present. Add few drops of AgNO3 solution.
(i) White precipitate indicates the presence of chloride in the organic compound.
(ii) Pale yellow precipitate, sparingly soluble but completely soluble in excess of NH4OH, shows
the presence of bromide.
(iii)Yellow precipitate, insoluble in NH4OH, confirms the presence of iodide.
dil HNO3
NaX + AgNO3 → AgX + NaNO3
Silver halide (X=Cl−, Br−, I−)
AgCl + 2NH4OH → [Ag(NH3)2]+ Cl− + 2H2O
White Ammonium Silver aminochloride
Precipitate solution (soluble)
AgBr + 2NH4OH → [Ag(NH3)2]+ Br− + 2H2O
AgI + NH4OH → No reaction
The correct determination of elements in an unknown organic compound gives the idea
of functional group present. Once the functional group present in the organic compound is
known, one is able to find out the name of the probable compound with the help of melting point
or boiling point. After having the idea of functional group, the next procedure is to study some
specific reactions of the compound and then to confirm its name by preparing suitable
derivatives. Test for element carbon, hydrogen and oxygen are not required. This means that if
no other element is present, functional group containing carbon, hydrogen and oxygen are
determined. The test for functional group should be performed in the following sequence-

4.3.6.1 Compounds containing C and H with or without oxygen
(A) Carboxylic acid ( -COOH )
(i) Litmus Test- Take a small amount of given organic compound (0.5 g) and make its solution
with water in a test tube. Dip a blue litmus paper in the solution. If the litmus paper turns red, it
shows the presence of carboxylic group (phenols being acidic in nature also give this test).
(ii) Sodium bicarbonate test- Take 0.5 g of given organic compound in a test tube and 5 mL of
cold 50% aqueous solution of NaHCO3 and shake gently. Effervescence indicates presence of
carboxylic group in the given compound.
(B) Phenols (Phenolic-OH, OH directly attached to an aromatic nucleus)
(i)Take water solution of given organic compound in a test tube and dip the blue litmus paper in
to it. If blue litmus changes to red but no effervescence with NaHCO3 indicates the presence of
phenolic group.
(ii) FeCl3 Test- Take 1 mL of aqueous or alcoholic solution of given organic compound in a test
tube. Add 2-3 drops of neutral or very dilute solution (aqueous) of ferric chloride. A blue, green,
red or violet colour indicates presence of phenolic group (Ar- OH).
(iii) Libermann’s Test- All phenols in which para position is free always gives this test. Take
0.5 g of given organic compound and few crystals of NaNO2 in a dry test tube and heat gently for
a minute. Cool the mixture and add 1 mL of conc. H2SO4 and shake thoroughly. A deep green or
blue colour appears which on further dilution with water turns red. Now add excess of dil. NaOH
to the above red coloured solution which again becomes deep green or blue. It indicates the
presence of phenolic group.
(iv) Phthalein Test-Take 0.5 g of given organic compound and 0.5 g of phthalic anhydride in a
dry test tube, add 1.0 mL of conc. H2SO4 and heat for a minute in Bunsen flame. Cool it and
make it alkaline in with dil. NaOH solution. Pour a few drops of this solution in 20 mL water
taken in a beaker. Following characteristics colours shows the presence of phenolic group-
Pink colour- Phenol, o-Cresol
Blue colour- Catechol, m-Cresol
Fluorescent green - Resorcinol
No colouration- p-Cresol

(C) Carbohydrate
(i) Molisch’s Test- Take 2 mL aqueous solution of given organic compound in a test tube and
add 1 mL of Molisch’s reagent (dissolve 10 g α- naphthol in 100mL alcohol or 10 g β-naphthol
in 100 mL chloroform) and shake well. Now take 2 mL of conc. H2SO4 in a separate test tube
and add it to the tube containing organic compound with Molisch’s reagent from side wall.
Allow to stand for 5 minutes. A reddish violet ring at the junction of two liquids shows the
presence of carbohydrate.
(ii) Reaction with H2SO4- Take 0.5 g of given organic compound in test tube and add 1 mL
conc. H2SO4. An immediate charring and blackening of the solution shows the presence of
carbohydrate.
(D) Aldehydes (-CHO)
(i) Schiff Test- Take 1 mL alcoholic or aqueous solution of given organic compound in a test
tube and add 2 mL of Schiff reagent (Dissolve 1 g p-rosaniline in 50 mL water with gentle
warming. Cool, saturate with SO2 and filter) and shake. A deep red or violet colour shows the
presence of aldehydic group (Never heat during this process).
(ii) Tollen’s Test- Take 2 mL Tollen’s reagent (Take 5 mL AgNO3 solution and add 2-3 drops of
dilute i.e 1% NaOH aqueous solution. A white ppt. is obtained. Now add NH4OH drop by drop
till the ppt. just dissolves. The reagent should be prepared fresh when required) and add 0.5 g of
given organic compound in a boiling test tube. Heat the mixture on water bath. Formation of
silver mirror or blackish precipitate indicates the presence of aldehydic group (reducing sugars
also gives this test).
(iv) Fehling Solution Test-Take a test tube with 1 mL Fehling solution A and further add
1mL Fehling solution B in it until a blue precipitate first formed is redissolved to give a deep
blue solution. Now Add 0.5 g of given organic compound and heat for 2 minutes. Reddish brown
precipitate shows the presence of aldehydic group. This test is also given by reducing sugars.
(Fehling’s solution- consists of two parts, A and B; Solution A: Dissolve 35 g crystalline
CuSO4.5H2O in 500 mL water. Add few drops of conc. H2SO4. Solution B: Dissolve 173 g

sodium potassium-tartarate (Rochelle salt) and 60 g of NaOH in 500 mL water. Equal volume of
A and B are mixed before use.)
(E) Ketones ( CO)
(i) Schiff reagent- No colour

(ii) 2,4 Dinitrophenylhydarzine Test- Take 2 mL of Brady’s reagent in a test tube and add 2-3
drops of given organic compound. Shake it vigorously. Heat and cool the solution. A red, yellow
or orange coloured precipitate indicates the presence of ketonic group. (Brady’s reagent- Mix 4
g 2,4 -dinitrophenyl hydrazine with 8 mL conc. H2SO4. To this solution, add gradually 70 mL
CH3OH with shaking and cooling. Now warm the solution and make up the solution to 100 mL
by adding water).
(F) Esters (R COOR1)
(i) Fruity smell- All the esters have fruity smell.

(ii) Phenolphthalein Test
Take 100 mg of given organic compound in a test tube and add 3 mL of dilute NaOH
solution and 1 mL of phenolphthalein solution. A pink colour is obtained due to the presence of
NaOH which is discharged on heating the solution. Ester is hydrolysed into an acid and alcohol.
The acid neutralizes the NaOH and hence pink colour is disappeared.
NaOH
RCOOR1 + H2O → RCOOH + R1OH
(iii) Hydroxamic acid Test

Take 40 mg of given organic compound and 1 mL of hydroxylamine HCl solution in
ethanol with 0.2 mL, 6M NaOH solution in a boiling test tube. Acidify the above solution with
HCl solution and then cool it. Add 1-2 drops of FeCl3 solution. Appearance of red-violet colour
indicates the presence of ester.
Esters react with hydroxylamine HCl to yield a compound which can make complex with ferric
chloride to give coloured compound.

R-COOR1 + H2NOH → RCONHOH + R1-OH

Hydroxamic acid
3R-CONHOH + FeCl3 → [RCOHNO]3 Fe + 3HCl

Ferric Hydroxamate complex
Red-violet colour
(G) Alcohols ( OH)
(i) Take 2 mL of given organic compound in a dry test tube and add 1 g of anhydrous Na2SO4
and filter. To the filtrate add a small piece of sodium. Effervescence due to the presence of H2
shows the presence of an alcohol.
(ii) Take 1 mL of given organic compound or its aqueous solution in a test tube and add few
drops of ceric ammonium nitrate. A pink colour or red colour shows the presence of an alcohol.
(H) Hydrocarbons
There is no specific group test for hydrocarbons. Hydrocarbons may be either saturated or
unsaturated. Unsaturated hydrocarbons may be aliphatic or aromatic in nature. They are
insoluble in water but soluble in many organic solvents. Since hydrocarbons are non-reactive,
their identification is done on the basis of their results of preliminary tests (like test of
unsaturation, detection of elements), determination of melting point/boiling point, specific test
for particular hydrocarbons and preparation of their derivatives.
4.3.6.2 When nitrogen is present
(A) Amides (-CONH2 )

Take 0.2 g of given organic compound in a test tube and add 1 mL of aq. NaOH and heat,
smell of ammonia shows the presence of an amide.
(B) Primary amines (-NH2 )
(i) Nitrous Acid Test-

Take 0.5 g of given organic compound in a test tube and add 4 mL of dil. HCl in to it and
cool. Now add 10% aq. NaNO2 solution. A brisk effervescence shows the presence of an
aliphatic primary amine.
(ii) Carbylamine Test-
Take 0.5 g of given organic compound in a test tube and add 4 mL of alcoholic solution
of KOH and 2 drops of chloroform (CHCl3) to it. Shake and heat gently. An intolerable offensive
odour of carbylamine shows the presence of primary amine.
(iii) Diazotisation Test- Take 0.2 g or 0.5 mL of given organic compound in a test tube and
dissolve in 2-3 mL of dil. HCl and cool under tap water. Now add 2 mL of 2.5% aqueous
NaNO2 solution, cool again and add 0.5 mL of alkaline β-naphthol solution. An orange-red or a
red dye shows the presence of aromatic primary amine.
(C) Secondary amines (>NH-)
(i) Secondary amines do not give carbylamine test.
(ii) Nitrous Acid Test-
Take 0.2 g or 0.5 mL of given organic compound in a test tube and add 2 mL of dil. HCl
and cool test tube under tape water. Add 2 mL of 2.5% NaNO2 solution. Yellow oily drops are
obtained which shows the presence of secondary amine. This test is given by both aliphatic and
aromatic secondary amines.
(iii) Libermann’s Nitroso Reaction-
Take 0.5 g or 0.5mL of given organic compound in a test tube and add 4 mL of dil. HCl and cool
the test tube under tap water. Now add 2.5% aqueous solution of NaNO2 gradually with
continuous shaking until yellow oil separates at the bottom. Decant off the aqueous layer. Take 2
drops of this oily nitroso compound in a dry test tube, add 0.5 g of phenol and warm gently for a
few seconds. Cool and add 1 mL of conc. H2SO4. A greenish blue colour is obtained which
changes red upon dilution with water. Greenish blue colour reappeared on adding excess of
NaOH solution. This shows the presence of secondary amine.
(D)Tertiary amines ( N:)
(i) Tertiary amines do not give carbylamine test
(ii) Take 0.2 g or 0.5 mL of given organic compound in a test tube and add 4-5 mL of dil. HCl.
Cool the tube under tap water. Now add 2-5 mL of 2.5% aqueous soution of NaNO2 gradually
with shaking and observe:

(a)Production of green or brown coloured salt indicates the presence of aromatic tertiary amine.
(b) No reaction indicates the presence of aliphatic tertiary amine.
(E) Anilides (-NHCOR) (e.g. acetanilide, benzanilide)
All anilides are colourless, odourless crystalline solids. Acetanilides and benzanilides are both
soluble in cold water but acetanilides have the greater solubility in hot water.
(i) 2,4 –Dinitrochlorobenzene Test- Organic compound having anilide group gives intense
colour on a paper soaked with 2,4-dinitrochlorobenzene.
(ii) Tafel’s Test-Take 0.5 g of given organic compound in a test tube and add 3 mL concentrated
H2SO4 and powdered K2Cr2O7 into it. Shake the tube thoroughly. Red or violet colour changes to
green shows the presence of anilide which do not contain any substituent in benzene ring.
(iii) Hydrolysis Test- Take 0.5 g of given organic compound in a boiling test tube and add 5 mL
of dil. HCl. Boil and cool the tube. Now add 2 mL of 2.5% NaNO2 solution, cool again and add
0.5 mL of alkaline β-naphthol solution. An orange –red dye shows the presence of an anilide
(Anilides are hydrolysed on boiling with HCl and thus, liberates primary amino group which
gives the dye-test).
(F) Nitro Compounds (-NO2)
(i) Azo-Dye Test- Take 0.5 g/ 1mL of given organic compound in a boiling test tube, add 3 mL
conc. HCl, 2 mL water and 1 g of solid stannous chloride (or tin granules). Heat the contents on
water bath for few minutes. Filter and cool the filtrate. Now add 2.5% aq. NaNO2 solution drop
by drop to the filtrate to complete the diazotization. Cool again and add 1-2 mL of alkaline β-
naphthol solution. An orange –red or red dye shows the presence of nitro group (The dye is
formed due to liberation of primary amino group by reduction of nitro group) .
Sn, HCl
C6H5NO2 C6H5NH2
(ii)Tollen’s Reagent Test-
Take 0.5 g of given organic compound in a test tube and add 10 mL C2H5OH in to it.
Shake the tube thoroughly and now add 0.5 g NH4Cl and 0.5 g zinc dust with shaking. Heat the
content on a water bath for 5 minutes. Cool the mixture, filter and add 1 mL ammonical silver

nitrate solution (Tollen’s reagent). Formation of silver mirror indicates the presence of nitro
group.
Zn, NH4Cl
C6H5NO2 C6H5NHOH + H2O
Nitrobenzene Phenyl hydroxylamine
C6H5NHOH + 2[Ag(NH3)2] OH C6H5NO + 2Ag + 4NH3 + 2H2O
(Silver mirror)
(ii) Ferrous Hydroxide Test-

Take 0.2 g of given organic compound in a test tube and add 2 mL of 5% Ferrous
ammonium sulphate. Shake test tube content thoroughly. Now add 1 mL of 6N H2SO4 followed
by 2 mL of 2N KOH solution prepared in CH3OH. Formation of red brown precipitate indicates
the presence of nitro group.
R-NO2 + 6Fe(OH)2 + 4H2O 6Fe(OH)3+ R-NH2

Blue green Red brown precipitate
4.3.6.3 When nitrogen and sulphur are present
Thiourea (-NHCSNH-)
(i) Take 0.5 g of given organic compound in a test tube and add 1mL dil. NaOH in to it and
shake the flask thoroughly. Smell of ammonia confirms the presence of thiourea.
(ii) Take 0.5 g of given organic compound in a test tube and add 1 mL dil. NaOH solution, cool
and add lead acetate [Pb(CH3COO)2]. A brown or black colour of precipitate indicates the
presence of thiourea.

4.3.6.4 When halogen is present
(A) Aliphatic halogen compounds (RX)-

Take 0.5 g of given organic compound in a test tube and add 5 mL of alcoholic NaOH
solution in to it and boil the tube content for about 10 minutes. Cool and dilute the solution with
water, add excess of dil. HNO3 and then AgNO3 solution. A precipitate of silver halide is
obtained.
(B) Aromatic halogen compounds (ArX)-
When any one of the halogen atom like chlorine, bromine, iodine is present in aromatic
ring then test depends on the type of the additional functional group.
4.3.7 Determination of melting point of the compound
A thin capillary of about 5 cm in length with uniform bore is sealed at one end by
bringing it near to the flame. The pure, dry and fine powdered compound approximately 2 mg
under identification is filled through open end of the capillary tube by gentle tapping the closed
end. Melting point of unknown compound is determined by placing the capillary tube along with
thermometer either in Kjeldahl’s flask or digital melting point apparatus.
4.3.8 Confirmatory test for the suspected organic compound and preparation
of suitable derivatives
4.3.8.1 Carboxylic acid (R-COOH)
(a) Oxalic acid (COOH)2.2H2O [m.p. 101oC]

1. Oxalic acid is crystalline in nature and colorless in appearance with solubility in cold water.
2. Take aqueous solution of oxalic acid (2 mL) in a test tube and neutralize it with dilute NH4OH
solution. Now add aqueous CaCl2 solution to the tube content; white precipitate, insoluble in
acetic acid but soluble in dilute HCl is obtained. On adding CaCl2 solution, white precipitate
of calcium oxalate (CaC2O4) is formed.

3. Take aqueous solution of the compound and heat it with acidic potassium permanganate
solution. Purple colour of the solution is discharged.
Anilide derivative: M.P. 245°C
(b) Cinnamic acid [M.P. 133°C]
1. Cinnamic acid is crystalline in nature with pale yellow in colour and soluble in hot water.
2. Take a pinch of compound and add it to a solution of potassium permanganate, the pink
colour is discharged and a brown precipitate with bitter almond smell of benzaldehyde is
produced.
3. Add concentrated H2SO4 to the compound, heat gently; a green colouration changing to
brownish red is produced.
4. Take 0.2 g of cinnamic acid and dissolve it in 5 mL Na2CO3 solution. Add bromine water
drop by drop and note the separation of bromostyrene C6H5CH=CHBr as colourless oil,
having pleasant odour.
Amide derivative: M.P. 142°C
4.3.8.2 Phenols (Ar OH)

α-Naphthol [M.P. 94°C]
1. α-Naphthol is dark violet coloured crystal

2. It is insoluble in water.
3. It does not give colour with neutral aqueous ferric chloride but gives white precipitate.

4. Shake a small amount of the compound with a mixture having equal volume of iodine and
potassium iodide (KI) and add excess of NaOH; violet colour appears which rapidly darkens
followed by a precipitate formation.
5. Take 0.2 g of compound in a test tube and 2 mL NaOH solution, a drop of CCl4 and a pinch of
copper powder and warm the contents. Blue colour is formed.
6. It gives green colour with titanic acid and concentrated H2SO4.
2,4 Dibromo-derivative: M.P. 1050C
Benzoate derivative: M.P. 56°C
4.3.8.3 Carbohydrates
α- Glucose [CHO(CHOH)4CH2OH] [M.P. 146°C]
1. Glucose is colourless and powered form soluble in cold water.
2. It reduces Fehling’s solution, Tollen’s reagent and Barfoed’s reagent.
3. Take 2 mL of aqueous solution of compound in a test tube and add 1 g lead acetate
(CH3COO)2Pb, boil and add 5 mL dilute ammonia solution. Continue boiling for 5 minutes.
A rose pink colour confirms the presence of glucose.
4. Take 2 g compound in test tube and add 5 mL dilute NaOH solution, boil the content. The
mixture turns yellow then brown and produces the colour of caramel.
Osazone derivative: M.P. 205°C
Acetate derivative: M.P. 110-111°C
4.3.8.4 Ketones ( CO)

Benzophenone [C6H5COC6H5] [M.P. 48°C]
1. It is colourless crystalline solid with pleasant smell, insoluble in water.
2. Dissolve 2 g of compound in concentrated H2SO4, a yellow solution is obtained.
3. Fusion of the compound with sodium (Na) produces deep blue colour.
4. Take 0.2 g of compound in a test tube, add 1 g naphthalene and heat the content until
completely molten. Add a small piece of sodium metal and heat again. The surface of the
sodium metal becomes green.
5. It does not give iodoform test.
Derivative: 2,4-Dinitrophenylhydrazone: M.P. 238°C

4.3.8.5Hydrocarbons
Napthalene [M.P. 80°C]
1. It is colourless crystalline solid with characteristic odour like naphthalene balls and insoluble
in water.
2. Take 2 g of the compound and dissolve in 5 mL chloroform (CHCl3) and add anhydrous
aluminium chloride (AlCl3). A green colour appears.
Derivative: Picrate, M.P. 70°C
4.3.8.6 Amides (RCONH2)

Urea [NH2CONH2][M.P 132°C]
1. It is white crystalline solid, soluble in water.
2. Take 2 gm of compound and dissolve in 5 mL dilute HCl, cool and add few drops of sodium
nitrite (NaNO2) solution to it. N2 gas is evolved with effervescence.
3. Mix concentrated solution of oxalic acid and urea, white crystals of urea oxalate is formed.
4. Biuret test: Take 2 g of compound in a dry test tube and heat the content. The solid melts and
NH3 is evolved. Cool the tube when a white residue (biuret) is left in it. Dissolve it in 2 mL
water, add a drop of copper sulphate (CuSO4) solution and 2 mL sodium hydroxide (NaOH)
solution when violet colour is produced.
2NH2CONH2
Heat NH CONHCONH + NH
2 2 3
Urea Biuret

4.3.8.7 Primary amines

α-Naphthylamine [M.P. 50°C]
1. It is solid, colourless when freshly crystallized but turns brown on exposure in air.
2. Slightly soluble in hot water.
3. Dissolve 0.5 g of the compound in dil. HCl and add few drops of FeCl3 solution. A blue
precipitate is obtained.
4. It gives carbylamine reaction and dye test positive.
Derivative: Picrate M.P 161°C
4.3.8.8 Anilides (-NHCOR )

Acetanilide [M.P. 114°C]
1. Colourless thin plate like crystals.

2. Acetanilide is sparingly soluble in cold water but has the greater solubility in hot water.
3. Tafel’s Test- Take 0.5 g of compound in a test tube and add 0.3 g of K2Cr2O7 crystals and 3
mL of concentrated H2SO4. Heat the content. Red or violet colour changing to green shows
the presence of anilide which do not contain substituent in the benzene nucleus.
4. Gives carbylamine reaction test.
Derivative: p-Bromoacetanilide, M.P.167°C
p-Nitroacetanilide, M.P. 210°C

4.3.8.9 Nitro Compounds (-NO2)

m-Dinitrobenzene [M.P. 90°C]
1. It is Yellow crystalline solid.

2. It gives red-brown colour on boiling with NaOH.
3. Take 0.5 g of compound in test tube and add 2 mL acetone into it. Now add a drop of NaOH
solution to it. A violet blue colour is produced which changes to violet red on adding acetic
acid.
4. Dissolve 0.5g of compound in dilute NaOH and boil. To this, add a very small amount of
glucose (or tin chloride). Violet colour is produced.
Derivative: m-phenylene diamine, M.P. 63°C
4.3.8.10 Thioureas (H2NCSNH2 )[M.P. 180°C]

1. White crystalline solid soluble in hot water.
2. Take 0.5 g of compound in test tube and add 2 mL dilute NaOH solution. Boil the content,
ammonia gas is evolved.
3. Take 0.2 g of compound in a dry test tube, cool and add few drops of FeCl3 solution. A
blood red colour is produced due to formation of ferric thiocyanate.
4. Take 0.2 g of compound in test tube and dissolve it by adding 2 mL dilute CH3COOH, heat
the content. Now add 2 mL potassium ferrocyanide solution to hot solution. A green colour
changing to blue appears.
5. Add lead acetate solution to the compound dissolved in NaOH solution, black precipitate
appears.

4.3.8.11 Aromatic Halogen Compound (Ar-X)

p-Dichlorobenzene [ M.P.53°C]
Take 1 g of acid in boiling test tube and add 1 mL phosphorus pentachloride in it and
shake the content till the vigorous reaction ceases. Warm the reaction gently and cool it. Now
add 2 mL aniline and shake the reaction mixture vigorously. If necessary, warm and then cool.
Filter off the anilide, wash it with cold water and crystallize from ethanol and dry it.
RCOOH + H2NC6H5 RCONHC6H5 + H2O

Acid Aniline Anilinde
1. It is white crystalline solid with characteristic smell.

2. It does not give white precipitate with AgNO3 solution.
3. It can be readily nitrated.
Derivative: 2,5-Dichloronitrobenzene, M.P. 54°C
4.4 PREPARATION OF SOME IMPORTANT DERIVATIVES
4.4.1 Anilide derivative of carboxylic acids
Take 1 g of acid in boiling test tube and add 1 ml phosphorus pentachloride in it and
shake the content till the vigorous reaction ceases. Warm the reaction gently and cool it. Now
add 2 ml aniline and shake the reaction mixture vigorously. If necessary, warm and then cool.
Filter off the anilide, wash it with cold water and crystallize from ethanol and dry it.

4.4.2 Amide derivative of carboxylic acids
Take 1 g of compound in 100 mL conical flask and add 3 mL of phosphorous

pentachloride. Shake the content till the vigorous reaction ceases. Warm the reaction content
gently for 25-30 minutes and cool it. Now add 10 mL concentrated ammonia solution carefully,
stir with glass rod, cool and filter the produced acid amide. Wash the formed product with cold
water, crystallize from water and dry it.
RCOOH + PCl5 → RCOCl + POCl3 + HCl

Acid Acid Chloride
RCOCl + NH4OH → RCONH2 + HCl + H2O
Amide
4.4.3 Benzoate derivative of phenols
Take 100 mL conical flask, dissolve 1 g α-naphthol in 5 mL acetone and add 2.5 mL
benzoyl chloride to it. Add 10 mL aqueous NaOH gradually with cooling and shaking then
further add 40 mL NaOH solution. Stopper the flask and shake vigorously till the odour of
benzoyl chloride has disappeared. The final solution should be alkaline to the litmus paper. Filter
the product, wash first with dilute HCl, then with cold water and re-crystallize from ethanol or
acetone.
+ C6H5COCl + HCl
Alpha naphthol Alpha naphthyl benzoate

4.4.4 Osazone derivative of carbohydrates
Take 1 g of powdered sugar in a clean and dry test tube. In another test tube, dissolve 1 g
phenylhydrazine hydrochloride and 1.2 g crystalline sodium acetate in 5 mL cold water and add
this solution to tube which contains sugar. Loosely cork the test tube, immersed it in a boiling
water bath with periodical shaking, and note the exact time required for the first appearance of a
turbidity or precipitate of osazone. Cool the solution, filter the precipitate and re-crystallize from
ethanol.
4.4.5 Picrate derivative of naphthalene
Make a concentrated solution of picric acid in acetone. Now take 2 mL of picric acid
solution in a test tube and add 2 mL concentrated solution of naphthalene (concentrated solution
of naphthalene is prepared in acetone). Shake the content thoroughly, warm and allow to stand
for at least 30 minutes. A yellow precipitate of picrate is formed. Wash with water and dry it.
C10H8 + C6H2(NO2)3OH → C10H8C6H2(NO2)3OH

Naphtalene Picric acid Naphthalene picrate
4.5 SEPARATION AND SYSTEMATIC IDENTIFICATION OF

COMPOUNDS PRESENT IN AN ORGANIC MIXTURE
The following steps should be followed by the students for separation and identification
of organic mixture
1. Objective: To separate and identify the organic compounds in the given organic mixture.
2. Separation of organic compounds from a mixture (A&B): The mixture can be separated by
water, NaHCO3 or NaOH
Compound A
(i) Preliminary examinations

(ii) Solubility test

(iii)Ignition test
(iv) Test for unsaturation
(v) Element detection
(vi) Test for functional group
(vii) Melting point determination
(viii) Confirmatory test
(ix) Preparation of derivatives of organic compounds
(x) Structure of compounds
Compound B
(i) Preliminary examinations
(ii) Solubility test
(iii)Ignition test
(iv) Test for unsaturation
(v) Element detection
(vi) Test for functional group
(vii) Melting point determination
(viii) Confirmatory test
(ix) Preparation of derivatives of organic compounds
(x) Structure of compounds
3. Result: The given organic mixture is containing the following compounds:
A: …………………..; B: ………………….
Methods of separation of organic mixture

Organic mixture can be separated by chemical and physical methods. Distillation,
electrophoresis, counter current separation and chromatography are some common physical
methods of separation of organic mixture. Chemical methods of separation may depend upon the
chemical properties (polarity, solubility, acid or basic property) of the constituents of a mixture.
Separation also depends upon the type of mixture (solid-solid, solid-liquid, liquid-liquid).
Separation of a solid-solid mixture can be done on the basis of solubility and salt formation. On
the basis of solubility, the solid-solid mixture can be separated by water separation method while

on the basis of salt formation, NaHCO3 or NaOH separation can be done for a solid-solid
mixture.
4.5.1 Separation of solid-solid mixture on the basis of solubility
4.5.1.1 Water separation
The method is used when one of the components is soluble in water and other is not. The
separation by water can be done by following the Scheme 4.1.
Scheme 4.1: Water separation of an organic binary mixture
4.5.2 Separation of solid-solid mixture on the basis of salt formation
Separation of organic mixture based on salt formation is used when one of the
components is acidic or basic in nature or when both the components are insoluble in water.

4.5.2.1 NaHCO3 separation
NaHCO3 separation is used when one component is acidic and other component is either
basic or neutral or phenolic (Scheme 2).
Scheme 4.2: NaHCO3 separation

4.5.2.2 NaOH separation
NaOH separation is used when one of the components is phenolic and the other either
basic or neutral but not acidic (Scheme 4.3).

Scheme 4.3 NaOH separation
Q 1. What are organic compounds?

Q 2. What is the difference between qualitative and quantitative analysis?
Q 3. Write the steps involved in the systematic identification of an organic compound.
Q 4. Give the name of special elements that may be present in organic compound.
Q 5. How can we test the aliphatic and aromatic nature of an organic compound?
Q 6. What are unsaturated compounds? How can unsaturation be detected in organic
compounds?
Q 7. What is sodium extract? Why one has to prepare sodium extract during systematic
identification of an organic compound?
Q 8. What do you understand by functional group? If nitrogen is present in an organic
compound, what will be the possible functional groups?
Q 10. Differentiate between primary and secondary amine.
Q 11. Which kind of organic mixture can be separated by NaHCO3 solution?

1. O.P. Pandey, D.N. Bajpai and S.Giri. (2010). Practical Chemistry, S. Chand Publisher, New
Delhi.
2. S. Goyal. (2017). Text Book B.Sc Chemistry Practical-II, Krishna Publication, Meerut.

UNIT 5: SYNTHESIS OF ORGANIC COMPOUNDS
CONTENTS
5.1 Introduction
5.2 Objectives
5.3 Acetylation of salicylic acid, aniline and benzoylation of aniline and phenol
5.3.1 Acetylation of salicylic acid
5.3.2 Acetylation of aniline
5.3.3 Benzoylation of aniline
5.3.4 Benzoylation of phenol
5.4 Preparation of idoform
5.4.1 Preparation of Iodoform from acetone
5.4.2 Preparation of idoform from ethanol
5.5 Preparation of benzoic acid
5.5.1 Preparation of benzoic acid from toluene
5.6 Preparation of aniline
5.6.1 Preparation aniline from nitrobenzene
5.7 Preparation of m-nitroaniline
5.7.1 Preparation of m-nitroaniline from m-dinitrobenzene

5.1 INTRODUCTION
Organic synthesis is the process of construction of complex compounds from simpler

ones (feed stock). It plays an important role in chemistry, biochemistry, medicine, agriculture
and other fields. Modern medicine, the dye industry, aromas and cosmetics, vitamins and
nutritional goods, polymers and plastics, energy fuels and high-tech materials are some of its
direct benefits that shaped the world as we know it today. The simplest synthesis of a molecule is
one in which the target molecule can be obtained by submitting a readily available starting
material to a single reaction that converts it to the desired target molecule. However, in most
cases the synthesis is not that straightforward, in order to convert a chosen starting material to
the target molecule, numerous steps that add, change, or remove functional groups, and steps that
build up the carbon atom framework of the target molecule may need to be done. This unit will
enlighten the simplest one or two steps synthesis reactions involved, methodology and careful
characterization of synthesized organic compound.
5.2 OBJECTIVES
By studying this unit, students will be able to understand:

1. How to produce compounds in small scale in laboratory that do not form naturally for
research purpose
2. Theoretical knowledge of reactions involved for synthesis of a particular compound.
3. Detailed procedure, techniques, equipment, feed stock and time engagement for the synthesis
of finished form of compound
4. Characterization of a particular compound by its specific physical properties and its melting
point.
5. The idea about yield of synthesized compound compared with starting material and relative
ratio of feed stock which can be further utilized for up-scaling of synthesis of compound.

5.3 ACETYLATION OF SALICYLIC ACID, ANILINE AND

BENZOYLATION OF ANILINE AND PHENOL
5.3.1 Acetylation of salicylic acid
5.3.1.1 Objective
To prepare acetyl salicylic acid from salicylic acid and acetic anhydride
Salicylic acid, acetic anhydride, conc. H2SO4, ethanol, hot water, ice cold water, conical flask
(100mL.), water bath, glass rod, beaker, glass funnel, filter paper, etc.
5.3.1.3 Theory
Acetylation of salicylic acid with acetic anhydride in the presence of concentrated

sulphuric acid (H2SO4) produces acetylsalicylic acid and a molecule of acetic acid. In this
reaction, sulphuric acid acts as a catalyst which augments the process of detaching the acetate ion
(CH3COO--) from acetic anhydride which thereby gets associated with H+ ion from phenolic
hydroxyl group in salicylic acid and a molecule of acetic acid is eliminated.
conc. H2SO4
+ (CH3CO) + CH3COOH
Salicylic acid Acetic Acetyl salicylic Acetic acid

anhydride acid

Acetyl salicylic acid is commonly known as aspirin and largely used in medicine as an
analgesic (pain killer) and antipyretic (temperature lowering) agent.
5.3.1.4 Procedure
Take 5 g of salicylic acid and 9 g of acetic anhydride in a 100 mL conical flask. Add 3-5
drops of conc. H2SO4 and shake the flask thoroughly. Heat the flask on water bath for 10-15
minutes. Cool the flask at room temperature and then pour the reaction mixture with continuous
stirring into a 200 mL beaker containing 50 mL ice water. Continuous stirring increases the
process of rapid crystallisation. Collect the crude product on funnel with filter paper and wash it
thoroughly with cold water and drain.
5.3.1.5 Recrystallization
Acetyl salicylic acid can be recrystallized using a mixture of equal volume of hot water
and ethanol. Dissolve the obtained crude product in minimum amount of hot water (60oC) and
ethanol and then allow it to cool. Acetyl salicylic acid is obtained as colourless needle within few
hours.
5.3.1.6 Characterization
The crude and recrystallized acetyl salicylic acid can be characterized by determining the
melting point. Melting point of pure salicylic acid is 132-137°C. Melting point closer to this
range shows the formation of desired compound.
5.3.1.7 Result
Acetyl salicylic acid (Aspirin) was synthesized by acetylation of salicylic acid.

Appearance : Colourless crystal
Yield : ...............g

Melting point before recrystallization ........................oC

Melting point after recrystallization ...........................oC
Molecular formula: C9H8O4
5.3.2 Acetylation of aniline
5.3.2.1 Objective
To prepare acetanilide from aniline and acetic anhydride
Round bottom flask (100 mL), reflux condenser, aniline, glacial acetic acid, acetic anhydride, oil
bath, glass rod, beaker (250 mL.), ice cold water, funnel, filter paper, boiling water, animal
charcoal, cotton plug.
5.3.2.3 Theory
Acetylation of aniline involves the reaction between aniline and acetic ahydride in the
presence of glacial acetic acid. In this reaction the hydrogen atom of NH2 group in aniline is
substituted by the acyl group (CH3CO-) of acetic anhydride. The reaction is depicted as
following:
CH3COO
+ (CH3CO)2O + CH3COOH
H
Aniline Acetic anhydride Acetanilide Acetic acid

Acetanilide is medicinally important as it is used as febrifuge (antifebrin)
5.3.2.4 Procedure
Take 5 mL of aniline in a 100 mL round bottom flask fitted with a reflux condenser. Add 5
mL of acetic acid and 5 mL of acetic anhydride in to the flask containing aniline. Heat the
mixture gently under reflux for 15-20 minutes on oil bath and then pour the contents while still
hot with stirring into a 200 mL beaker containing 100 mL ice cold water. Stir the mixture
vigorously to hydrolyse the excess acetic anhydride. After a time, acetanilide has precipitated,
collect it on funnel with filter paper and wash with cold water.
Acetanilide can be recrystallized with hot water. Dissolve the obtained crude product in
minimum amount of hot water (60oC). If the product is excessively coloured add a pinch of
animal charcoal to hot water and then filter hot water containing product through cotton plug and
then allow it to cool. Filter the obtained pure colourless crystals of Acetanilide.
The pure colourless crystals of acetanilide are confirmed by its melting point. Melting
point of pure acetanilide is 114oC. Melting point closer to this point shows the formation of
desired compound.
5.3.2.7 Result
Acetylation of aniline provides acetanilide

Appearance-: Colourless crystal
Yield: ............................g
Melting point before recrystallization: ...........................oC

Melting point after recrystallization: ............................°C

Molecular formula: C8H9NO
5.3.3 Benzoylation of aniline
5.3.3.1 Objective
To prepare benzanilide from aniline.
Aniline, 10%Na OH, benzoyl chloride, cold water, hot alcohol, conical flask, funnel, measuring
cylinder, filter paper.
5.3.3.3 Theory
Benzoylation of aniline involves the insertion of benzoyl (C6H5CO) moiety in the

presence of NaOH to the primary amino group of aniline. In this reaction, benzanilide is
produced. NaOH neutralizes the liberated HCl and also catalyse the reaction. The reaction is as
follows:
NaOH
+ + NaCl + H2O
Aniline Benzoyl Benzanilide

Chloride

Benzanilidesis used as fungicide and acaricide (pesticide that kills ticks and mites).
5.3.3.4 Procedure
Take 2 mL of aniline and 30 mL of 10% NaOH solution in a 250 mL conical flask, then
add 3 mL of benzoyl chloride slowly with vigorous shaking. Cork the flask and shake for further
15-20 minutes or till the odour of benzoyl chloride can no longer be detected. Add 50 mL cold
water and mix well. Collect the crude benzanilide on funnel with filter paper. Wash it again with
cold water.
5.3.3.5 Recrystalization
Benzanilide can be recrystallized from hot alcohol (55-60°C). Dissolve the obtained
crude product in minimum amount of hot alcohol and then filter the pure crystals of benzanilide.
The pure colourless crystals of benzanilide are determined by its melting point. Melting
point of pure benzanilide is 163oC. Melting point closer to this point shows the formation of
desired compound.
5.3.3.7 Result
Benzoylation of aniline provides benzanilide

Appearance: Colourless crystal
Yield: ....................g
Melting point before recrystallization: ......................°C
Melting point after recrystallization:...............................°C
Molecular formula: C13H11NO

5.3.4 Benzoylation of phenol
5.3.4.1 Objective
To prepare phenyl benzoate from phenol and benzoyl chloride.
5.3.4.2 Requirement
Phenol, benzoyl Chloride, NaOH, alcohol, 250 mL conical flask, beaker, volumetric flask,
measuring cylinder, cold water, funnel, filter paper, melting point apparatus, thermometer.
5.3.4.3 Theory
Benzoylation of phenol involves the reaction of phenol with an aromatic acid chloride in
the presence of excess of NaOH at room temperature to form an ester. The reaction is called
Schotten Baumann reaction. If phenol is shaken with benzoyl chloride and excess amount of
NaOH solution, it is benzoylated to give the ester, phenyl benzoate. In this reaction, phenol is
first converted into the ionic compound sodium phenoxide (sodium phenate) by dissolving it in
NaOH solution. The phenoxide ion reacts more rapidly with benzoyl chloride than the original
phenol does, but even so you have to shake it with benzoyl chloride for about 15 minutes. Solid
phenyl benzoate is formed.
NaOH
+ + NaCl + H2O
5.3.4.4 Procedure
Phenol Benzoyl chloride Phenyl benzoate

Take 2.5 gram phenol and dissolve it in 35 mL 10% NaOH in 100 mL beaker. Now add
this phenol solution in to a 100 mL conical flask and then add 5 mL benzoyl chloride to it. Cork
the flask properly and shake the mixture vigorously for 20 minutes or until the pungent smell of
benzoyl chloride has disappeared. Filter off the formed crude product on funnel using filter
paper. Wash it with cold water 2-3 times.
Phenyl benzoate can be recrystallized from alcohol. Dissolved the obtained crude product
in minimum amount of hot alcohol (55-60oC) and then filter the pure crystals of benzoyl
chloride.
The pure colourless needles of benzoyl chloride are determined by its melting point.
Melting point of pure benzoyl chloride is 68-69oC. Melting point closer to this point shows the
formation of desired compound.
5.3.4.7 Result
Benzoylation of phenol provides phenyl benzoate.

Appearance: Colourless needle like crystals
Yield: .................................g
Melting point before recrystallization: °C
Melting point after recrystallization: ...................................°C

5.4 PREPARATION OF IDOFORM
5.4.1 Preparation of Iodoform from acetone
5.4.1.1 Objective
To prepare Iodoform from acetone in the presence of sodium hydroxide
5.4.1.2 Chemicals and equipment required
Ethanol, sodium hydroxide, iodine, distilled water, cold water, round bottom flask, funnel, filter
paper, melting point apparatus, thermometer.
5.4.1 3 Theory
Iodoform is prepared when any α-H containing methyl group (ketone, secondary alcohol
or acetaldehyde) reacts with iodine in the presence of base (NaOH, KOH, Na2CO3). When iodine
reacts with acetone in the presence of NaOH, a pale yellow precipitate of triiodomethane
(iodoform) is produced. The reactions involved in the process are as follows:
CH3COCH3 + 3NaClO + 3KI → CH3COONa + 2NaOH + 3KCl + CHI3
5.4.1.4 Procedure
Take 2 mL acetone and 30 mL of 10% NaOH in a 250 mL conical flask. Add 70 mL of

2N-sodium hypochlorite solution (freshly prepared) in to the reaction mixture and shake it
vigorously. Allow it to stand at room temperature for 2-3 minutes. Filter the yellow precipitate of
iodoform using funnel. Wash it with water twice and crude iodoform is obtained.

Pure iodoform can be recrystallize from alcohol. Take the crude material in a 150 mL
round bottom flask fitted with a reflux water condenser. Add a small quantity of alcohol and heat
to boiling on a water bath and then add more alcohol until all the iodoform is dissolved. Filter the
solution through a filter paper directly into a 100 mL beaker and then cool in ice water. The
iodoform rapidly crystallizes. Filter and dry it.
The pure crystals of iodoform are determined by its melting point. Melting point of
iodoform is 119-120oC. Melting point closer to this point shows the formation of iodoform.
5.4.1.7 Result
Iodination of acetone gives Iodoform

Appearance: Yellow crystals
Yield:..................................g
Melting point before recrystallization:.............................°C
Melting point after recrystallization:..................................°C
Molecular formula: CHI3
5.4.2 Preparation of idoform from ethanol
5.4.2.1 Objective
To prepare Iodoform from ethanol and iodine.

Ethanol, sodium carbonate, iodine, distilled water, cold water, round bottom flask, funnel, filter
paper, melting point apparatus, thermometer.
5.4.2.3 Theory
Iodoform an analogous to chloroform, is also known as triiodomethane and belongs to the

family of organic halogen compounds. Ethanol is the only primary alcohol to give the
triiodomenthane reaction. Many ketones give this reaction but those that do all have a methyl
group on one side of the carbon-oxygen double bond. These are also known as methyl ketones.
Compounds that are easily oxidized to acetaldehyde and secondary alcohols that have the general
formula CH3CHOHR can be oxidized to methyl ketones. Methanol does not give iodoform.
When ethanol reacts with iodine in the presence of base, it first oxidised to ethanal and
then gives iodoform. Reactions involved in the process are given below:
CH3CH2OH + 4I2 + 3Na2CO3 → CHI3 + 5NaI + HCOONa + 3CO2 + 2H2O
Iodoform has antiseptic and disinfectant properties.
5.4.2.4 Procedure
Take 500 mL round bottom flask and add 20 mL water, 20 mL ethanol and 40 gm sodium
carbonate into it. Heat the flask to about 70-80oC on a water bath. To the warm solution, add
small amount of iodine at a time with constant shaking. Add more iodine so that the reaction
product should have a pale yellow colour. Allow the reaction mixture to stand for 5 minutes.
Filter the crude Iodoform and wash it with cold water 2-3 times.

Pure iodoform can be recrystallized from alcohol. Take the crude material in a 100 mL
round bottom flask. Add a small quantity of alcohol and heat to boiling on a water bath and then
add more alcohol until all the iodoform is dissolved. Once the crude iodoform completely
dissolves, allow it to cool in ice cold water. The iodoform rapidly crystallises. Filter the solution
through a filter paper directly into a 100 mL beaker. Wash it with cold water and allow to dry.
The pure crystals of iodoform are determined by its melting point. Melting point of
iodoform is 119-120oC. Melting point closer to this point shows the formation of iodoform.
5.4.2.7 Result
Iodination of ethanol gives Iodoform.

Appearance: Yellow crystals
Yield:.............................g
Melting point before recrystallization:...................................oC
Melting point after recrystallization: ..............................oC
Molecular formula: CHI3
5.5 PREPARATION OF BENZOIC ACID
5.5.1 Preparation of benzoic acid from toluene
5.5.1.1 Objective
To prepare benzoic acid by oxidation of toluene.

Toluene, potassium permanganate, potassium hydroxide (1M), distilled water, Sulphuric acid
(1M).
5.5.1.3 Theory
Benzoic acid is the simplest aromatic carboxylic acid. It is prepared by oxidation of alkyl
benzene i.e toluene with acidic potassium permanganate (KMnO4) in the presence of potassium
hydroxide. Reaction involved in the process is shown as follows:
Toluene Potassium benzoate Benzoic acid
Benzoic acid occurs naturally in many plants. It serves as an intermediate in the

biosynthesis of many secondary metabolites. Salts of benzoic acid are used as food preservatives
and benzoic acid is an important precursor for the industrial synthesis of many other organic
substances.
5.5.1.4 Procedure
Take 10 g KMnO4 in round bottom flask fitted with a reflux condenser and then add 130
mL distilled water. Mix it thoroughly. Now add 20 mL 1M KOH add 10 mL toluene slowly in to
the reaction mixture. Finally reflux condenser should be attached to the flask and system is
heated and refluxed on oil bath. Allow the reaction mixture to reflux for 3-4 hours until oily

toluene disappears. Notice as the reaction proceeds, black coloured MnO2 particles attached on
the wall of flask. Once the reaction is finished, it is allowed to cool down to room temperature.
Filter it on funnel and wash with hot (70°C) distilled water 2-3 times. The filtrate contains
potassium benzoate. Add small amount of conc. sulphuric acid and mix it thoroughly. Check pH
of the reaction mixture with pH paper, which should be in acidic range. Filter and dry crude
benzoic acid.
Benzoic acid is recrystallized with hot water. Take crude benzoic acid in a beaker and
add hot water in to it. Mix thoroughly and allow to cool at 4oC. After 8-10 minutes, colourless
needle shaped crystals obtained. Filter the solution through funnel and dry it.
The pure crystals of benzoic acid can be characterized by its melting point. Melting point of
benoic acid is 122oC. Melting point closer to this point shows the formation of benzoic acid.
5.5.1.7 Result
Oxidation of benzoic acid with KMnO4 gives benzoic acid.

Appearance: Colourless crystals
Yield: .....................................g
Melting point before recrystallization: ................................°C
Melting point after recrystallization: ...............................°C

5.6 PREPARATION OF ANILINE
5.6.1 Preparation aniline from nitrobenzene
5.6.1.1 Objective
To prepare aniline from nitrobenzene by reduction
Sn powder, nitrobenzene, HCl, NaOH, KOH, NaCl, dichloromethane (DCM), round bottom flask,
hot plate, magnetic stirrer, separating funnel, conical flask
5.6.1.3 Theory
Aniline is an organic compound with the molecular formula C6H5NH2 consisting of a

phenyl group attached to an amino group. Aniline is the prototypical aromatic amine. It is used in
the manufacture of precursors to polyurethane and other industrial chemicals. Reduction of
nitrobenzene with Sn in presence of HCl and subsequently with NaOH yields Aniline. Reaction
involved in the reaction is depicted in the following figure.
Sn, HCl
NaOH
Nitro benzene Aniline

5.6.1.4 Procedure
Take 35 g of Sn powder in a round bottom flask. Pour 15 mL nitrobenzene in to the flask

which contains Sn. Connect the flask to the condenser on hot plate and stir with magnetic stirrer.
Add 15 mL of 32% HCl slowly into the flask. With time, color changes to dark brown. If reaction
becomes vigorous, cool it down by cold water. Once the complete HCl is added, the reaction
mixture is heated in water bath for 60 minutes. Now slowly add 60% NaOH to the reaction
mixture in flask. If the reaction mixture becomes too hot, cool it on ice bath. In this process all the
acid will be neutralized by NaOH and aniline will be formed. Mix the formed product thoroughly
and cool it.
5.6.1.5 Distillation and separation of aniline
Set the above flask containing aniline for steam distillation. In distillation process, a
yellow aniline water mixture will come out from the flask as a distillate. Collect initial 100 mL of
clear distillate. Since aniline is soluble in water, add 20 gm NaCl to the 100 mL distillate and
allow to mix it thoroughly and then transfer to a separating funnel. Allow to stand the separating
flask with mixture for 5-10 minutes. A layer of aniline begins to form at the top. Collect the water
layer and aniline layer from the separating funnel in a 100 mL beaker separately.
5.6.1.6 Extraction of aniline
Since aniline is soluble in water so the water layer may contain some amount of aniline.
Therefore remaining aniline from water is extracted by using dichloromethane (DCM). Wash the
aniline containing water sample with DCM. For this purpose, take 25 mL DCM and add to a
beaker which contains aniline-water sample. Stir it with glass rod and transfer to a separating
funnel. Shake it thoroughly and allow to stand for 5-10 minutes. Collect the water layer and
aniline layer in separate beaker. Repeat this process three times with DCM (3X 25 mL DCM).
Pool all the fractions of aniline and extracted solution is then dried using KOH. Store the solution
with KOH for half an hour and then filter on a funnel with filter paper. The filtrate contains DCM
which is removed by simple distillation process.

Set up a simple distillation assembly and discard everything collected below 120°C (boiling point
of DCM is 40oC). Once the DCM has been removed, the collection flask is replaced with new 50
mL collection flask to facilitate the distillation. Collect the fraction between 180-184°C.
The pure liquid aniline can be determined by its boiling point. Boiling point of aniline is
184oC. Boiling point closer to this point shows the formation of aniline.
5.6.1.8 Result
Reduction of nitrobenzene with Sn in acidic medium produces aniline.

Appearance: Yellow colored liquid with fishy odour.
Yield: .......................mL
Boiling point before Extraction : ..............................°C
Boiling point after Extraction: ..........................°C
Molecular formula: C6H6NO2
5.7 PREPARATION OF m-NITROANILINE
5.7.1 Preparation of m-nitroaniline from m-dinitrobenzene
5.7.1.1 Objective
To prepare m-nitroaniline from m-dinitrobenzene through selective hydrogenation

Conical flask, crystallised sodium sulphide, sodium bicarbonate, sodium sulphide, methanol, m-
dinitrobenzene, 250 mL round bottom flask, reflux condenser, water.
5.7.1.3 Theory
Selective hydrogenation of one of the nitro group of m-dinitrobenzene with sodium

sulphide in alkaline medium yields corresponding nitroaniline. In this reaction, first sodium
sulphide gets converted into NaSH and then reacts with m-dinitrobenzene in alkaline medium.
The reaction involved in the process is as follows:
5.7.1.4 Procedure
Take 50 mL water in a conical flask and dissolve 18 g crystallised sodium sulphide

(Na2S.9H2O) in it. Add 6 g of finely powdered sodium bicarbonate (NaHCO3) in sodium
sulphide solution with constant stirring. When the sodium bicarbonate has dissolved completely,
add 50 mL of methanol and cool it below 20oC. Filter the precipitated sodium carbonate on a
funnel with filter paper. Wash the precipitate thrice with 8 mL methanol. Retain the filtrate and
washings, these contain about 3.9 g of NaSH in solution and must be used for the selective
reduction
Now dissolve 7 g of m-dinitrobenzene in 50 mL of hot methanol in a 250 mL round
bottom flask and add with shaking, the previously prepared methanolic solution of sodium
hydrogen sulphide. Attach the round bottom flask with a reflux condenser and boil the mixture for

20 min. Ignore any further sodium carbonate which may precipitate. Allow the reaction mixture
to cool. Fit the condenser for distillation on a water bath and distil off most of the methanol (100-
120 mL). Pour the liquid residue of round bottom flask into 200 mL of cold water with constant
stirring. After 30-40 minutes, yellow crystals of m-nitroaniline appear. Filter the formed crystals
on funnel with filter paper and wash with cold water.
m-Nitroaniline is crystallized with methanol. Take crude m-nitroaniline in a beaker and

add 75% aqueous methanol in to it. Mix thoroughly and allow to cool it to 4°C. After 15-20
minutes, bright yellow crystals obtained. Filter the solution through funnel and dry it.
The pure crystals of m-nitro aniline can be characterized by its melting point. Melting
point of m-nitroaniline is 114°C. Melting point closer to this point shows the formation of m-
nitroaniline.
5.7.1.7 Result
Selective hydrogenation of m-dinitrobenzene yields nitroaniline

Appearance: Colourless crystals
Yield: …………………….g
Melting point before recrystallization: ……………………..°C
Melting point after recrystallization: ………………………..°C
Molecular formula: C6H6N2O2
Q1. Why synthesis of organic compound is important in laboratory?

Q2. Is this possible to synthesize 20 kg organic compound in laboratory?

Q3. What are the basic criteria to characterize a synthesized compound in laboratory?
Q4. What is the formula of acetic anhydride and acetyl salicylic acid?
Q5. What is the use of acetyl salicylic acid?
Q6. What is the role of separating funnel?
Q7. Is this possible to separate out two water miscible liquids by separating funnel?
Q8. What is the formula of iodoform?
Q9. What is the formula of m-nitroaniline?
Q10. What is the molecular formula of benzoic acid?
5.9 SUGGESTED READING
1. O.P.Pandey, D.N. Bajpai and S. Giri. (2010). Practical Chemistry, S. Chand Publisher, New
Delhi.
2. S. Goyal. (2017). Text Book B.Sc Chemistry Practical-II, Krishna Publication, Meerut.
3. Arun Sethi. (2010). Systematic Lab Experiments in Organic Chemistry, New Age Publisher.

UNIT 6: MOLECULAR WEIGHT DETERMINATION
CONTENTS
6.1 Introduction
6.2 Objectives
6.3 Determination of molecular weight of a non-volatile solute by cryoscopy
6.3.1 Rast method
6.3.2 Beckmann’s freezing point method
6.4 Determination of molecular weight and degree of dissociation of a non-volatile solute by
ebullioscopy
6.4.1 Objective
6.4.2 Theory
6.4.3 Procedure
6.4.4 Observations
6.4.5 Calculations
6.4.6 Result
6.4.7 Precautions
6.6 Summary

6.1 INTRODUCTION
Molecular weight measurement is very important as it gives very useful information

about the chemical compounds. The molecular weight is used to deduce possible molecular
formulae. Mass spectrometry offers the most refined method for determination of the molecular
weight of compounds which have vapour pressures higher than 0.1 mm Hg at 350°C. If the
instruments of high resolving power are used then the molecular weight is obtained to an
accuracy of 15 ppm.
In organic synthesis, the characterisation of an organic compound is done by
approximate molecular weight determination. Methods for molecular weight determination of
non-volatile substances include cryoscopic, ebullioscopic, osmotic pressure and lowering of
vapour pressure method. In this unit, we will discuss and study Rast’s camphor method,
Beckmann’s freezing point method and ebullioscopy for determination of molecular weight of
different solutes. Rast’s camphor method is used to determine the molecular weights of
camphor soluble solutes.
6.2 OBJECTIVES
After going through this unit, you will be able to answer the following questions:
• What is molecular weight?
• How can molecular weight of a chemical compound be determined?
• How melting point of a compound can be measured?

6.3 DETERMINATION OF MOLECULAR WEIGHT OF A NON-

VOLATILE SOLUTE BY CRYOSCOPY
6.3.1 Rast method

6.3.1.1 Objective
To determine the molecular weight of a non-volatile solute by Rast method.
6.3.1.2 Theory
The method is useful for determination of molecular weight of solutes which are soluble in
camphor. The advantage of this method is that molal depression constant of camphor is 40°C
(very high) while depression in freezing point is large so that it can be determined by an
ordinary thermometer.
6.3.1.3 Procedure
Take a small clean test tube (e.g. 75 x 10 mm) in a hole bored with a cork and place it on
the pan of a balance. Take weight of the tube (Empty Tube). Now place about 50 mg of the
compound in this test tube of which the molecular weight is to be determined and weigh the
tube (Tube+compound) again. Now add 500-600 mg of pure, resublimed camphor (eg the
micro-analytical reagent) in the tube and weigh again. Keep the Stopper loose and place the
tube in an oil bath previously heated to about 180°C so that the camphor and compounds melt.
Now stir the liquid with a platinum wire. Remember not to heat the liquid for more than 1
minute otherwise camphor will sublime from the solutions. Allow the solution to cool. You will
get a solid mixture. Transfer this solid to a clean watch glass and crush it to make powder. Now
place a small amount of the powder into a thin capillary tube whose one end is closed and is
carefully rounded. Now press the solid down into the closed end with the help of a platinum
wire. You may use another capillary tube of smaller diameter with closed end.

Remember that the level of the solid should not exceed 2 mm. Now determine the melting point
of the mixture using a liquid melting point bath. Use 100-200°C thermometer graduated in 0.1
or 0.2°C, or an electrically- heated apparatus. Remember, good illumination and very careful
control of the rate of heating is essential. The melting point is taken as that temperature at which
the last fragment of solid disappears. Repeat the melting- point determination with a second
sample; if the reading shows much variation then prepare a new mixture as the earlier prepared
mixture was not homogeneous. Now determine the melting point of the original camphor. The
difference in melting points gives the depression of the melting point of camphor caused by the
addition of the compound.
6.3.1.4 Observations
Freezing point of camphor = T1°

Freezing point of mixture of solute and cmphor = T2°
Weight of camphor = W g
Weight of solute dissolved in camphor = w g
6.3.1.5 Calculations
The molecular weight M can then be calculated from the formula:
Where K is the molecular depression constant of camphor (39.7), w is the weight of the
solute dissolved in camphor, W is the weight of the camphor and (T1-T2) is the depression
of the melting point.
6.3.1.6 Result
The molecular weight of the given substance is ..............................

Note: The solute concentration should be above 0.2 M: in dilute solution K increase from 39.7
to about 50.
The Rast camphor method is very simple, but it has some limitations also. One serious
problem is the melting point of camphor which is very high Therefore, the possibility of
decomposition of the compound whose molecular weight is to be determined is very high. As
we know that the solubility of many classes of compound in liquid camphor is very low, so this
difficulty restricts its general applicability. The Table 6.1 below contains few useful alternative
solvents which have high molar freezing point depression constants:
Table 6.1: Solvents for molecular weight determination by depression of freezing points:
Compound Melting Point (°C) Molar depression
constant
Cyclohexanol 24.7 42.5
Camphene 49.0 31.0
Cyclopentadecanone 65.6 21.3
Borylamine 164.0 40.6
Borneol 202.0 35.8
6.3.2 Beckmann’s freezing point method
6.3.2.1 Objective
To determine the molecular weight of a non-volatile solute (urea, glucose etc.) by Beckmann’s
freezing point method.
6.3.2.2 Theory
The depression in freezing point of a liquid produced by dissolving a known weight of

the solute in a known weight of the solvent is related to the molecular weight of the solute by
following equation:

Where kf = Molal depression constant

W = Weight of sample (solute)
m = Molecular weight of solute
M = Molecular weight of solvent
= depression in freezing point
6.3.2.3 Procedure
(i). Set the apparatus as shown in Fig. 6.1. Weigh accurately a 50 mL flask filled with distilled
water. Transfer about 25 to 40 g of water sufficient to cover the bulb of the Beckmann’s
thermometer into a cleaned and dried freezing point tube and weigh the flask again. The
difference of two readings gives the weight of water taken in the tube.
Fig. 6.1. Beckmann’s apparatus
(ii). Weigh accurately 0.2-0.3g of the solute whose molecular weight is to be determined.
(iii). Prepare the freezing mixture by mixing crushed ice and common salt and fill in the beaker.
Shake it from time to time by stirrer to maintain the temperature of the bath at about -4 to -5°C.

(iv). Now immerse the freezing tube carrying the Beckmann’s thermometer and stirrer directly
into the freezing mixture. Stir the water slowly. The temperatures fall rapidly and when solid
being to separate, note the temperature. This is the freezing point of water. Remove the freezing
point tube from the freezing bath and repeat the process two or three times till the concordant
reading are obtained.
(v). Now remove the inner tube and melt the ice. Introduce into it the accurately weighed
sample through the side tube stir well to dissolve the solute and determine the freezing point of
the solution. As above till the concordant reading are obtained. It will be freezing point of the
solution. The difference of these two reading gives depression in freezing point ( .
6.3.2.4 Observation
Weight of the empty flask = w1 g

Weight of the flask + water = w2 g
Weight of the solute = w g
Freezing point of water = T1°C
Freezing point of solvent = T2
Molecular wt. of solvent = M
6.3.2.5 Calculations
Depression in freezing point = (T1 – T2)°C
Weight of water (W) = (w1-w2) g.

Now by substituting the different values in the following formula, the molecular weight of the
solute (m) can be calculated.
6.3.2.6 Result
Molecular weight of the given solute is ……............g.

6.3.2.7 Precautions
(i) The temperature of the freezing bath should not be below more than 3-40C, the freezing point
of the solvent.
(ii) Excessive supper cooling must be avoided.
(iii) The solvent should not form mixed crystal with the solute.
(iv) Stirring should be slow and continuous.
(v) The solution must be dilute.
(vi) The solute must be non-volatile.
6.4 DETERMINATION OF MOLECULAR WEIGHT AND

DEGREE OF DISSOCIATION OF A NON-VOLATILE SOLUTE
BY EBULLIOSCOPY
6.4.1 Objective
To determine the molecular weight and apparent degree of dissociation of an electrolyte (eg.
NaCl) in aqueous solution at different concentrations by Ebullioscopy
6.4.2 Theory
The boiling point of a liquid is that temperature at which it’s vapour pressure become
equal to atmospheric pressure. Since the vapour pressure of a liquid is lowered by the addition
of a non-volatile solute, the boiling point is raised. The elevation in boiling point depends upon
the quantity of the substance added. The molecular weight of the solute is calculated by the
relation:
Where

kv = Molal elevation constant

w = weight of solute
W = weight of solvent
M = Molecular weight of solvent
= Elevation in boiling point
When an electrolyte is dissolved in water, it dissociates into ions. Since the ions behave
as molecule, the total number of molecules in solution exceeds than the normal number of
molecules. The molecular weight (wt.) of the solute can be expressed as:
Thus,
If one gram mole of solute is taken and X be the degree of dissociation then.
NaCl → Na+ + Cl-
1 0 0 before dissociation
(1- ) x x after dissociation
Therefore, No. of particles before dissociation = 1+ 0 + 0 = 1

And No. of particles after dissociation = 1- + + =1+
Hence,
If observed and normal molecular weights of the electrolyte are known, its degree of
dissociation (x) can be calculated.

The apparatus used is shown in Fig 6.1.which consists of a graduated boiling tube whose
middle portion blown into a bulb with a hole in the side. The boiling tube is fitted with a
thermometer (reading up to 0.01°C) and a glass tube having a rose head for uniform heating of
the solution. The boiling tube is surrounded by an outer tube which receives hot vapours from
the inner tube through the hole and prevents the loss of heat by radiation.
Fig. 6.2 Landsberger’s apparatus

6.4.3 Procedure
(i) Set the apparatus as shown in Fig. 6.2. Take about 150 mL of the solvent in a round bottom
flask and about 10 mL in the inner tube and fit in it a rose head tube and a Beckmann
thermometer.
(ii) Now, heat the flask and pass the solvent vapours through the tube into the inner tube. This
will increase the temperature of the solvent which becomes constant at the boiling point of the
solvent. Note this temperature. This is the boiling point of the pure solvent.
(iii) Now stop heating and allow the flask to cool. Introduce an accurately weighed amount (1-
1.5 g) of the solute (NaCl) into inner tube and shake till it dissolves.
(iv) Fit the inner tube and the thermometer in the apparatus and heat the flask again. Allow the
solvent vapours to pass into the inner tube. Note the temperature when it becomes constant. It
is the boiling point of the solvent. The difference of two readings (T1-T2) will be the elevation
in boiling point (∆T). Similarly, repeat the experiment 2 or 3 times by taking different amounts
of the solute.

(v) Note the volume of the solvent on graduated inner tube. Knowing the density of the
solvent, the weight of the solvent (W) can be calculated.
6.4.4 Observations
(i) Boiling point of pure solvent = ……..°C

(ii) Density of the solvent at room temperature = …….°C
S.N. Wt. of the Wt. of the Boiling point Boiling Elevation
solute added solvent of solvent point of boiling point
(T1) solution (∆T = T1 – T2)
(T2)
1 ….. …. …. ….
2 ….. …. …. ….
3 ….. …. …. ….
6.4.5 Calculations
The molecular weight of the solute may be calculated by following formula:
It will be the observed molecular wt. of the solute. Degree of dissociation of NaCl is
calculated by the following relation:
Or
From the above relation, the degree of dissociation (x) can be calculated and expressed
in percentage.

6.4.6 Result
The degree of dissociation of NaCl is …............
6.4.7 Precautions
(i) The solvent used must be pure.

(ii) The heating of the solvent in the inner tube must be uniform.
(iii) The solution should be dilute.
(iv) The solute should be non-volatile.
(i) Which solvent you used in the Rast method and why?
(ii) What are the advantages of Rast’s method?
(iii) The molar masses of what kind of solute can be determined by Rast’s method?
(iv) Which method can be used for finding the molecular weight of a volatile substance?
(v) What are colligative properties?
(vi) Define molal depression constant?
(vii) Rast method is known as micro-method. why?
6.6 SUMMARY
The Rast method for determining molar masses uses camphor as the solvent.
Beckmann’s freezing point method is based on relationship between depression in freezing
point and weight of solute dissolved in weighed solvent. These two methods are based on
cryopscopy. On the other hand, enullioscopy is based on elevation of boiling point which intern
depends upon quantity of the substance added.

1. Brain S. Furniss, Antony J. Hannford, P.W.G. Smith and A. R. Tatchell. (1989). Text Book
of Practical Organic Chemistry. Pearson Education Press.
2. H. Kaur. (2002). Instrumental Methods of Chemical Analysis. Pragati Prakashan, Meerut.
3. S. C. Tripathi and S. P. S Jadon. (2008). Practical Chemistry. Anusandhan Prakashan.
4. Shashi Chawla. (2002). Essentials of Experimental Engineering Chemistry. Dhanpati Rai &
Co (PVT) Ltd.

UNIT 7: ELECTROCHEMISTRY
CONTENTS
7.1 Introduction
7.1.1 Conductometric methods
7.1.2 Specific resistance
7.1.3 Specific conductance
7.2 Objectives
7.3 Conductrometric analysis
7.3.1 Digital conductivity meter
7.3.2 Controls and services of digital conductivity meter
7.4 Determine the strength of the given acid conductometrically
7.4.1 Objective
7.4.2 Theory
7.4.3 Procedure
7.4.3 Observations
7.4.4 Calculations
7.4.5 Result
7.5 Saponification of ethyl acetate
7.5.1 Objective
7.5.2 Theory
7.5.3 Procedure
7.5.4 Observations
7.5.5 Calculations
7.6 Determination of ionization constant of weak acid
7.6.1 Objective
7.6.2 Theory
7.6.3 Procedure
7.6.4 Observation

7.6.5 Calculation
7.6.6 Result
7.1 INTRODUCTION
7.1.1 Conductometric methods
Solutions of electrolytes conduct an electric current by the migration of ions under the
influence of potential gradient. The movement of ions depend on their charge and size, viscosity
of the medium and magnitude of the potential gradient. Like a metallic conductor, the solutions
also obey Ohm’s law which is I = E / R.
For an applied potential E, the current I, that flows between the electrodes immersed in
the electrolyte varies inversely with the resistance of the electrolytic solution. The reciprocal of
resistance (I / R) is termed the conductance (L). It is measured in Ohm-1 or mhos and in SI, the
name Siemen (S) is used. Let us understand some important terminologies being used and their
meaning,
7.1.2 Specific resistance
The resistance R of the conductor of uniform cross section is directly proportional to

length, and inversely proportional to the cross section a.
Thus,

Where ρ is a constant called resistivity or specific resistance. It may be defined as the

resistance in Ohm’s of a specimen of one cm in length and 1 square cm in cross section. It is
the resistance between opposite faces of 1 cm cube of the metal.
= Ohm cm
7.1.3 Specific conductance
The reciprocal of specific resistance is known as the specific conductance (σ). It is the
conductance of one cm cube of the solution of an electrolyte at a specific temperature. Since
conductance, σ is directly proportional to length l and inversely proportional to the cross
sectional area a of the conductor. Hence,
Specific conductance is expressed in ohm-1cm-1 or S/ m.
7.2 OBJECTIVES
This unit will be helpful in:

• Understanding conductometric methods
• Determining the strength of the given acid conductometrically using standard alkali
solution.
7.3 CONDUCTROMETRIC ANALYSIS
The conductometric analysis is performed by using digital conductivity meter. This

instrument is ideal for monitoring salt contents in natural water, treated water, waste water,
drinking water, brine solution, sea water and soluble salts in soil. The use of solid state
Integarated circuit (I.C.) makes the instrument reliable and versatile. The digital conductivity
meter is extremely useful for:

(i) Water quality control in boiler feed water

(ii) Water works departments
(iii) Breweries
(iv) Swimming pools
(v) Agriculture and soil analysis
(vi) Fertilizers to the plants
(vii)Petroleum refineries
(viii)Textile plants, rayon and silk mills etc.
7.3.1 Digital conductivity meter
A conductivity cell dipped in a measuring solution is placed in the inverting input path
of an ‘operation amplifier’ when (ei) voltage of constant amplitude and suitable frequency is
applied to the system, then a given feedback resistance (Rf) the output voltage (e0) is linearly
proportional to the conductance of the solution (Gi). Applying Kirchoff’s current law at the
inverting input path of an ‘operation amplifier’ (Figure 7.1).
Figure 7.1 Schematic presentation of digital conductivity meter

A virtual ground is presumed to be existing that melting input impedance of the
operation amplifier is very high, as a consequence IB = 0
Thus
im = io (1)
from ohm’s law, voltage (e) = current (I) × Resistance (R)

e = IR
Using equation (2) equation (1) becomes:
When Rf and ei are constant

Let Rf ei = K = constant
Therefore,
or
or
With the help of cell constant, the conductivity of the solution under test can be
dtermined. Thus, the output of the amplifier after conditioning is displayed on a digital display
and it indicates directly the conductivity of the solution under test referred at the reference
measurement (25°C).

7.3.2 Controls and services of digital conductivity meter

(1) Front panel control (Figure 7.2)
(a) Cell constant: This control is used to compensate for the cell constant variation.
(b) Digital display: It is a LED digital display that displays the conductivity value of any
aqueous solution.
(c) Range: The range switch is used for setting one of the five ranges of conductivity. The five
ranges are:
200 µs
2 ms
20 ms
200 ms
1000 ms
(d) Temperature: This control is used to compensate for the change in conductivity due to
variation in temperature.
(e) Function switch: When at ‘cheek’ position the conductivity, meter read 1.000. If not, then
adjust with ‘CAL’ control knob provided at rear panel so that the display reads 1.000.
(f) MAN / COND: At this position, the instrument displays the conductivity of the solution
under test with manual temperature compensation.
(g) ATC (Available only in selected models): At this position the instrument displays the
conductivity of the solution under test with Automatic temperature compensation. In this mode,
the temperature probe should be attached to the instrument.
(h) Cell constant: At this position, this instrument displays the cell constant value set by the
user.
Figure 7.2. Front Panel controls of conductivity meter

(2) Back panel controls (Figure 7.3)

(a) Input: For connecting conductivity cell to the conductivity meter, two input banana sockets
are provided at the back panel.
(b) Temperature (available only in selected model): This socket is used for connecting the
temperature probe to the conductivity meter for ATC mode.
(c) Cal: When the function switch is at check position this ‘CAL’ knob is used to adjust 1.000
on the display.
(d) On / Off: This switch is used to switch ‘ON’ the instrument should be switched ‘OFF’
when not in use.
(e) Fuse: 100 mA fuse in used to control the current from the supply to the instrument.
Figure 7.3. Back panel controls of conductivity meter
7.4 DETERMINE THE STRENGTH OF THE GIVEN ACID

CONDUCTOMETRICALLY
7.4.1 Objective
To, determine the strength of the given acid (say HCl) conductometrically using standard alkali
(say NaOH) solution.

7.4.2 Theory
The conductivity cell is made up of Pyrex glass fitted with Platinum (Pt) electrodes. The
electrodes consist of Pt plates sealed into glass tubes which pass through an ebonite cover. The
electrodes are connected to the circuit by means of mercury (Hg) placed in the tubes. The
electrodes are fixed by cementing the tubes to the ebonite cover. The electrodes are coated with
finely divided Pt. the cell is placed in a thermostat. Copper wires re dipped in Hg placed in glass
tubes to make concentrations (Figure 7.4).
Figure 7.4 Determination of conductivity
Thus,
Or
The titration of strong acid (HCl) with a strong base (NaOH) gives the following ionic reaction:
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2O (Freely ionized)
Initially, the conductivity of HCl solution is high due to high concentration of H+ ions.
When NaOH is added, the conductivity of the solution decreases due to the disappearance of H+
ions which combine with OH- ions to form feebly ionised H2O. When all the HCl solution get
neutralised and thereby the neutralization is complete, further addition of NaOH increases
conductivity of the solution due to presence of OH- ions.
When conductance is plotted against the volume of NaOH added, a V-shaped curve will
obtain. The intersect point thus gives the volume of NaOH required to neutralise the given HCl
(Figure 7.5).
7.4.3 Procedure
Pipette out 10 mL of the given HCl solution of N/10 normality in a beaker and dilute it
with distilled water so that the electrodes of the conductivity cell are completely dipped in the
solution. Fill N/10 NaOH solution in the burette. Connect the cell with Wheatstone bridge and
note the conductivity of the HCl solution.
Now add 1 mL of NaOH solution from the burette and note the conductivity. Similarly
note down the reading after addition of 1 mL of NaOH solution. Now plot a graph between
conductance on Y-axis and volume of NaOH used on X-axis. The intersect of the lines gives
volume of NaOH required to neutralize the given HCl.
7.4.3 Observations
(1)Volume of HCl taken = 10 mL.

Observation table
S. No. Volume of NaOH solution Conductivity (mhos)
added (in mL)
1. 0 ….
2. 1 ….
3. 2 ….
4. 3 ….

5. 4 ….
6. 5 ….
7. 6 ….
Figure 7.5 Curve showing conductivity changes in acid and base titration
7.4.4 Calculations
Suppose V mL of standard solution of NaOH is consumed at end point.
HCl NaOH
N1 V1 = N2 V2
N1 × 10 = N2 V2
Therefore,
Normality of HCl = N1 = N2 V2/10
Hence, the strength of HCl = Normality of HCl (N1) × 36.5
7.4.5 Result
The strength of the supplied HCl is …………… g/ L

7.5 SAPONIFICATION OF ETHYL ACETATE
7.5.1 Objective
To study the saponification of ethyl acetate conductometrically.
7.5.2 Theory
This experiment involves a bimolecular reaction for which a second-order constant may
be calculated. A conductometric method is used for this purpose. The rate constant k for
chemical reactions is given by the Arrhenius equation:
Where e = base of natural logarithms

= energy per mole required for activation
R = gas constant
T = absolute temperature
The expression represents the fraction of molecules having an energy equal
to or greater than the energy required for activation.

The rate of a second-order reaction, is proportional to the concentration of each of the two
reacting materials, as expressed in the equation.
Where = number of moles reacting in time t
= initial concentration of one reacting material
= initial concentration of the other
= specific reaction rate

The bimolecular reaction studied in this experiment is the saponification of an ester by

sodium hydroxide.
CH3COOC2H5 + Na+ + OH- CH3COO- + Na+ + C2H5OH
The hydroxyl ion and ethyl acetate are the reacting materials, the sodium ion being
incidental.
A solution containing sodium hydroxide (NaOH) and ethyl acetate (CH3COOC2H5)
undergoes a marked decrease in conductance with time because the highly conducting hydroxyl
ion is replaced by the poorly conducting acetate ion during the reaction.
Accordingly, a conductivity bridge can be used to study the progress of the reaction. An
alternative but more tedious procedure is to withdraw sample from the reaction mixture at
definite intervals, discharge them into excess standard HCl solution, and back-titrate with
standard NaOH.
7.5.3 Procedure
Standard solutions of ethyl acetate and sodium hydroxide having exactly the same
normality are to be prepared. Enough pure ethyl acetate is pipetted into a weighed weighing
bottle containing about 5 mL of water to prepare 250 mL of 0.02M solution (Flask 1). The
bottle is reweighed, the solution transferred quantitatively to a volumetric flask, and distilled
water is added to the mark. The exact normality is calculated.
The same volume of NaOH whose normality is exactly equal to that of the ethyl acetate
is prepared by quantitative dilution of standardized 0.5N stock reagent (Flask 2).
The flasks (Flask 1 and Flask 2) containing these solutions and a 250 mL flask
containing distilled water are clamped in the 25°C thermostat and allowed to come to
temperature equilibrium before use. Record the temperature of the water bath.
A compact bridge utilizing an electron ray tube or “magic eye” as an indicator is
available on the market and can be highly recommended. The Freas-type conductance cell
shown in Figure 7.6.

Figure 7.6 Freas-type conductance cell
The conductance bridge is set up by thermostat, and a cell which has been rinsed with
distilled water is brought to thermostat temperature. Into another 250 mL flask, exactly 25 mL
of ester solution, 25 mL water, and 50 mL NaOH solution should be pipetted. in this order. The
flask is swirled rapidly in the thermostat as the NaOH is introduced, and the stop watch started
after about half has been added. Measure the first conductance reading after 300 seconds and
continuously collect the reading after 300 second intervals for one hour.
For the next run, the proportions of ester and base are reversed, and the experiment is
repeated. Next, equal volumes of the base and ester solutions are mixed, and readings are taken
for about an hour at 25°C. With solution and apparatus transferred to the 35°C thermostat, the
experiment is repeated. It is not necessary to measure a final conductance for these two
experiments.

7.5.4 Observations
Temperature of reaction = _______________________________
Time (Sec) Y (µS) Yo-Y (µS) (Yo-Y)/t (µS/sec)

300 …. ….
600 …. ….
900 …. ….
1200 …. ….
1500 …. ….
1800 …. ….
2100 …. ….
2400 …. ….
2700 …. ….
3000 …. ….
3300 …. ….
3600 …. ….
7.5.5 Calculations
Appropriate plots should be made, and the rate constants should be determined
for each of the experiments performed. The following equation is used where unequal
concentrations of ester and base were present.
To obtain at time t, the quantity (y0 – yt) / (yt - y∞) is multiplied by or b, whichever
was originally present at time t, y0 is the conductance at time 0, and y∞ is the conductance at

completion of the reaction. The conductance at time 0 is obtained by extrapolation of the first
few points on a plot of conductance versus time to zero time. When the concentrations of the
two reactants are the same, the equation is applicable.
It may be rearranged to yield
This is the equation of straight line with and as variables. When is
plotted against the slope of the line is equal to .
From the temperature coefficient of k obtained from the last two experiments, the
energy of activation is calculated.
7.6 DETERMINATION OF IONIZATION CONSTANT OF WEAK

ACID
7.6.1 Objective
To determine the ionisation constant of a weak acid (acetic acid) conductometrically.
7.6.2 Theory
The ionisation of a weak electrolyte (CH3COOH) may be written as below:
Applying law mass action:

…….(1)
Where K is the ionisation constant and [CH3COO–] [H+] and [CH3COOH] are the active
masses of CH3COO-, H+ and unionised CH3COOH respectively.
If 1 mole of the substance is taken and α is the degree of dissociation, v is the total
volume in litters then:
Substituting these values in equation (1):
For weak electrolytes, is very small hence (1- may be taken as unity the equation
(2) becomes:
Where C = concentration in gm mole per litre.
To determine the value of ionisation constant K, the value of is to be determined by
conductivity measurements.
Where = equivalent conductivity at any dilution v (in litre) and = equivalent
conductivity at infinite dilution. = is determined by Kohlraush’s law i.e.
Where and are the ionic conductivities of anion and cation respectively.

7.6.3 Procedure
(i) Prepare exact N/2 acetic acid solution.

(ii) Prepare the solution of different strength like N/10, N/20, N/40 and N/50 by diluting with
conductivity water and measure conductance directly from conductivity meter.
Determination of cell constant: The cell constant is determined by direct measurement of
conductance from conductivity meter.
The specific conductivity of N/10 KCl solution at 25°C is 0.01289.

Thus,
7.6.4 Observation
S. No. Strength of Observed SP. Conductivity = Eq. conductivity

acetic acid Conductivity cell const. × obs.
Conductivity
7.6.5 Calculation
The value of Ionisation constant can be calculated by the following constant (degree of
dissociation) can be calculated by the following relation.

Calculate the value of ionisation constant K for each solution which is constant.
7.6.6 Result
The ionisation constant of acetic acid is ……. .

Note: Standard value of Ionisation constant of acetic acid is 1.75 × 10-5 at 25°C.
Q 1. Explain the following:

(a) Conductivity (b) Specific conductance (c) Cell constant
(d) Equivalent conductivity (e) Molar conductivity.
Q 2. What is the relation between equivalent and molar conductivity?
Q 3. Discuss factors on which conductance of an electrolytic solution depend.
Q 4. Can precipitation titrations be followed by conductance measurements?

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BSCCH- 304

B. Sc. III YEAR

Phone No. 05946-261122, 261123

UTTARAKHAND OPEN UNIVERSITY Page 1

Prof. A. B. Melkani Prof. Diwan S Rawat

Dr. Hemant Kandpal Dr. Charu Pant

Prof. R.D.Kaushik Prof. P.D.Pant

Dr. Shalini Singh Dr. Charu Pant

Dr. Shalini Singh

UTTARAKHAND OPEN UNIVERSITY Page 2

Unit Written By Unit No.

Dr. Nandan Singh Karki 01

Dr. Manisha Bisht

Dr. Tanuja Bisht

Dr. Pushpa Negi 04 & 05

Dr. Geeta Tiwari

Title : Laboratory Courses-III

UTTARAKHAND OPEN UNIVERSITY Page 3

BLOCK-1 INORGANIC CHEMISTRY

BLOCK-2 ORGANIC CHEMISTRY

Unit 4: Qualitative analysis 60-88

BLOCK-3 PHYSICAL CHEMISTRY

Unit 6: Molecular weight determination 111-123

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UNIT-1 – INTRODUCTION TO LAB TECHNIQUES:

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After completing this unit, the students should;

I. Get familiar with the basic laboratory apparatus and instruments.

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1.3 COMMON LAB GLASSWARES AND APPARATUS

1.3.1 Cooling baths

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Figure 1.1 A simple model of water bath

1.3.2 Distillation assembly

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Figure 1.2. General distillation assembly

1.3.2.1 Simple distillation , 1.3.2.2 Steam distillation, 1.3.2.3 Fractional distillation,

1.3.2.1 Simple distillation

1.3.2.2 Steam distillation

Steam distillation is used to separate heat-sensitive components. Steam is added to the

1.3.2.3 Fractional distillation

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1.3.2.4 Vacuum distillation

Spectrophotometer is an optical instrument used in lab for both qualitative and

Figure 1.3. General spectrophotometer

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1.3.4 Hot-air oven

1.3.5 Weighing balance

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Figure 1.5. Analytical balance

A desiccator is a chamber or box that is used to store the hygroscopic materials. A

UTTARAKHAND OPEN UNIVERSITY Page 12

Figure 1.6 A classical desiccators

1.3.7 Melting point measurement instrument

Figure 1.7 Melting point measurement apparatus

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1.3.8 Commonly used glasswares

Figure 1.8 Beaker

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