Study Material 1 PDF

PRACTICAL
ORGANIC
CHEMISTRY MANUAL
FOR IV SEMESTER
B.Tech CHEMICAL ENGINEERING
By
Dr.V.S.GAYATHRI
Professor and Head
Department Of Chemistry,
SSN College Of Engineering,
SSN Institutions
V.S.Gayathri Page 1 12/14/2019

Contents
Chapter Content Page
SAFETY RULES FOR ORGANIC CHEMISTRY LABORATORY 3
Introduction to techniques involved in practical 5

1 Organic Chemistry
2 Organic Preparations 16
3 Introduction to Qualitative Analysis 29
4 Systematic Analysis of Simple Organic Substances 33
5 Preparation of Derivatives 56
6 Important reaction mechanisms 63
6 Preparation of important reagents 68
Appendix 73
Index 76

SAFETY RULES FOR ORGANIC CHEMISTRY LABORATORY
1. Experiments can only be done during scheduled time only.
2. Organic chemistry lab involves working with chemicals that are

carbon base. Organic chemicals can be one or all of the following:
a. Volatile
b. Flammable
c. Toxic or carcinogenic
d. Respiratory irritants
3. Modes of exposure to organic chemicals are:

• Inhalation
• Absorption through the skin
• Ingestion
4. Absorption through the skin can be minimized by wearing

lab coat and shoes
5. Ingestion: Don’t eat or drink in the lab.
6. Know the health hazard of your reagents. MSDS are available

on-line.
7. Dispose of all solid organic waste into dust bins and liquid
waste into wash basin.
8. Keep flammables away from open flame.
9. Read labels very carefully. Inadvertently mixed chemicals

can cause serious explosion.

10. Excess chemicals are considered waste. DO NOT RETURN
CHEMICALS BACK TO THE REAGENT BOTTLE.
11. Prevent contamination - use droppers in the reagent bottle.
12. Use a clean, dry spatula to get solids out of the reagent
bottle (alternatively you can make you own paper spatula with a
white sheet)
13. Dispose of broken glass using the dust bin.
14. Rinse chemicals off skin for at least 5 minutes with cold water
if it falls on your skin
15. Know the locations of the safety equipment, such as the fire
extinguisher, first aid kit etc.,
16. Report to lab in-charge immediately in case of any

discomfort
17. Follow the instruction given by the lab in charge verbatim to perform
experiments safely and successfully

Chapter 1
Introduction to techniques involved in practical Organic Chemistry
Understanding organic chemistry is impossible without knowledge and

practical skills of preparation, purification, identification and isolation of
organic substances. The laboratory class consists of introduction to
preparation, handling and storage of certain important reagents, Preparation
and purification of a few organic compounds, and the qualitative analysis of
simple organic substances.
This chapter aims to acquaint students with various procedures adopted and
lab ware used for performing preparation, filtration, recrystallisation and
systematic analysis of organic compounds.
To establish the purity and identity of a compound, a simple melting point

determination is very useful.

RECRYSTALLISATION
Recrystallisation is a common method adopted for purifying organic

compounds
Theory of Recrystallization
Fig 1 shows the tightly packed crystal lattice of a pure solid
Fig 2 shows the Disrupted crystal lattice due to the presence of impurities
Fig1 Fig2
Steps in Recrystallization
1. The crude solid is dissolved in hot solvent so as to make a saturated

solution
2. The hot saturated solution is cooled to room temperature, so that crystal

lattice reforms.
3. The solution with the precipitate is placed in an ice bath
4. The solid is then filtered at suction, leaving impurities in solution.
5. The filtered solid is air dried to remove traces of solvent

An Ideal Recrystallization Solvent Should
• Dissolve the entire compound when the solvent is hot (boiling)

• Dissolve none of the compound when the solvent is at room
temperature
• Have different solubilities for the compound and the impurities
• Have a lower boiling point than the melting point of the
compound to be recrystallised
• Be cheap, non-toxic, non-reactive, and non-smelly

Technique of recrystallisation
Required set up :
Pour a small amount of the hot solvent into the flask containing the
solid.

Swirl the flask gently to dissolve the solid.
Place the flask on the hot plate / water bath to keep the solution warm.
When dissolution is complete , allow it to stand for few minutes without

disturbance

After a while, crystals will start appearing in the flask.
At his stage place the conical flask in an ice bath to complete the
crystallization

FILTRATION
The method of isolating solid from liquid (filtrate) using vacuum is called
Suction Filtration
Suction Filtration Apparatus (Buckner Funnel – Flask assembly)
How to filter???
1 – Connect the flask to the suction pump using a rubber tube
2- Place an exact fitting filter paper into the funnel

3- Decant the solution into the funnel
4- Transfer the precipitate into the filter paper, let it dry
Instead of a bucker funnel, a fluted funnel may also be employed

for lesser quantity of precipitate

MELTING POINT
Theory
The melting point of a substance is the temperature at which crystalline

substances change from a solid to a liquid state. During the melting process,
all of the energy added to a substance is consumed as heat of fusion, and
the temperature remains constant.
A pure substance melts at a precisely defined temperature, characteristic

of every crystalline substance. The melting range is determined by
recording the temperature at which a crystal starts melting and the
temperature at which there is no more solid left behind.
An impurity in the compound decreases its melting (freezing) point and

also increases the range at which the compound melts.
Hence a melting point is the quickest and most accessible method for an
organic chemist to confirm the identity of a compound. Additionally, it can
also be used in order to access the purity of a product.
Often organic solids undergo slight change in colour/ shrink/ soften before
actually melting. (Note: The crystals will shrivel up (simmer) before a liquid
drop forms)
Hence temperature is noted when the liquid becomes visible.

DETERMINATION
A capillary tube sealed at one end (also called melting point capillary) and a
melting point apparatus are required.
Step 1
The test sample is packed into the melting point capillary by pressing the
open end gently into a sample. Crystals will stick in the open end of the tube.
Step 2
The solid should fill the tube to a depth of 2-3 mm. Tap the bottom of the
capillary on a hard surface so that the crystals pack down into the bottom of
the tube.

Step 3
Introduce the sample melting tube into the slot provided and switch on the
melting point apparatus
• Do one fast determination to get rough approximation of melting

point
• Cool the sample to temperature at least 30oC less than the
approximate melting point.
• Do next one slower: Go quickly to 10-15 degrees away from melting
point, and then lower the heating range such that the temperature
rises at the rate of 1oC / min.
• Record temperature at which solid first starts to melt ( say for
example 120)
• Record temperature at which all solid is melted ( say 125)
• Report the range: 120-125 oC
PS: The sealed side of capillary tube is placed inside the melting point
determination apparatus and hence it will be VERY HOT DON’T touch
that part of the capillary tube immediately after removal .

Chapter 2
PREPARATION OF META- DINITROBENZENE
Aim
i.To prepare m-dinitrobenzene quantitatively and qualitatively
ii. To purify the m-dinitrobenzene by recrystallisation and find the melting
point
Principle
Type of reaction: Electrophilic substitution reaction
Process :Nitration
Meta-dinitrobenzene is prepared by the nitration of nitrobenzene.
The nitration is effected by fuming HNO3 in presence of concentrated
sulphuric acid.
NO2 NO2
Con. HNO3
Con. H2SO4
NO2
Nitrobenzene m-Dinitrobenzene
(For detailed mechanism refer 3rd Semester ORGANIC CHEMISTRY
class notes)
Chemicals Required
1. Nitrobenzene………………………………..5ml.
2. Fuming HNO3(Sp.gr. 1.5)…………………..6ml.
3.Conc. H2SO4…………………………………7ml.

Procedure
For Preparation (Crude Sample)
6ml of fuming nitric acid is taken in a round bottomed flask and 7ml of
concentrated sulphuric acid is added, a little at a time, cooling the flask
during the addition.
5ml of nitrobenzene is then added in small quantities at a time, to the
nitrating mixture, shaking well after each addition.
The above solution is heated for about 45minutes by immersion in a boiling
water-bath, till a small quantity of the reaction mixture when added to some
quantity of water in a test –tube gives a solid immediately.
The contents of the flask are then poured in a fine stream while still hot,
into 200ml. of cold water contained in a beaker. The mixture is stirred very
vigorously during the addition.
Meta-dinitrobenzene separates as a solid which is filtered at the pump. The
precipitate is washed several times with water and dried . The weight of
the air dry sample is noted.
For Purification by Recrystallisation
A small portion of the crude m - dinitrobenzene is suspended in alcohol and
heated in water bath.
The hot solution is filtered through fluted funnel, into a conical flask.
The flask is left aside without disturbing.
The crystalline substance is filtered at suction pump and air dried.
The melting point of the recrystallised m- dinitro benzene is determined.
Report
Amount of crude meta-dinitrobenzene obtained =…………… .g.
Melting point of recrystallised m-dinitrobenzene = 90 oC

Know your reaction
Nitration is a chemical process by which a nitro group is introduced into an
organic compound. Both aliphatic and aromatic compounds can be nitrated.
Aliphatic nitration often follows free radical mechanism while aromatic
nitration is electrophilic substitution
Most of the nitration reactions are heterogeneous and exothermic (∆H is
often 35kcal/mol). Hence Industrial nitration is carried out in special
anticorrosive nitrators under carefully controlled conditions; the processes
are fully automated. Reaction temperature determines the yield and quality
of the final product.
Nitration reactions are notably used for the production of explosives
(contains more than one nitro group).
Most of the Aromatic nitro compounds are precursors for the synthesis of
dyestuffs, pharmaceuticals, amines, plastics, insecticides etc. They are also
used in for manufacturing rubber, and photographic chemicals.
Aliphatic nitro compounds are used as solvents explosives, rocket
propellants, fumigants and gasoline additives. Many find application in the
rubber, textile, and paint and varnish industries.
The most prominent acute health hazard of the aromatic nitro- compounds is
cyanosis, and the chronic manifestation is anemia.
Nitro paraffins have a depressive effect on the central nervous system and
also cause lesions in the liver and kidneys
Caution
The fat-soluble nitro compounds are very rapidly absorbed through the skin.
So avoid contacting directly.

PREPARATION OF ACETANILIDE
Aim
i.To prepare acetanilide quantitatively and qualitatively
ii. To purify acetanilide by recrystallisation and find the melting point
Principle
Aniline is refluxed with acetic anhydride in presence of fused sodium
acetate when acetanilide is obtained.
Type of reaction: Condensation reaction
Process: Acetylation
Condensation is a complex reaction (involving more than one operation – viz.,
substitution followed by elimination).
It proceeds with the formation small molecules like HCl , MeOH , H2O as by
product (in this reaction water).
In the course of the formation of acetanilide, the lone pair on nitrogen
attacks carbonyl carbon (substitution) then the water is removed from the
intermediate (elimination) giving the final product.
Requirements
1. Freshly distilled aniline…………………..5ml.
2. Acetic anhydride ………………..………6ml
3. Freshly fused sodium acetate……….2g.

Procedure
For Preparation
5ml of aniline, 6ml of acetic anhydride and 2g of fused sodium acetate are
taken in a round bottomed flask. The mouth of the flask is fitted with a long
air condenser and gently refluxed by heating on wire gauze. The heating is
continued for 30 to 45 minutes. The mixture is poured while hot into 100ml.
of cold water contained in a beaker with vigorous stirring. It is cooled and
filtered at the pump. The slightly coloured substance is dissolved in about
150ml. of boiling water, heated with 1g. of animal charcoal and filtered
through a fluted funnel. The filtrate is allowed to cool. The precipitated
acetanilide is filtered, washed with a small quantity of water and dried. The
weight of the crude sample is noted.
For Recrystallisation
A small portion of the crude acetanilide is suspended in alcohol - water
mixture and heated in water bath.
The melting point of the recrystallised acetanilide is determined.
Report:
1. Amount of acetanilide obtained =………………………g.
2. Melting point pure acetanilide = 114.oC

Know your reaction and product
Acetylation /Acylation is a chemical process by which a acetyl (CH3CO) /
acyl (RCO) group is introduced into an organic compound.
Most of the proteins in the human body undergo acetylation. The process of
acetylation is important for several essential chemical reactions in the body
like Protein formation, Drug biotransformation, Regulation of
deoxyribonucleic acid (DNA) etc.
This is an importanct process in synthetic organic chemistry also.
Example: Friedel-Crafts Acylation
Friedel-Crafts acylation process yields products that , used for the
preparation of a variety of pharmaceuticals, agrochemicals, and other
chemical products. It proceeds via electrophilic mechanism.
Important compounds prepared by this reaction : Asprin, Heroin
Acetanilide is an odourless solid chemical which has a leaf or flake-like
appearance. It is also known as N-phenylacetamide, acetanil, or acetanilid,
and Antifebrin (trade name). Acetanilide, was introduced in therapy as early
as 1886 as a fever-reducing drug. Its effectiveness in relieving pain was
discovered soon thereafter, and it was used as an alternative to aspirin for
many years in treating such common complaints as headache, menstrual
cramps, and rheumatism.
Acetanilide is used for the production of 4-acetamidobenzenesulfonyl
chloride, a key intermediate for the manufacture of the sulfa drugs. It is
also a precursor in the synthesis of penicillin and other pharmaceuticals.
Acetanilide causes eye, skin, and respiratory tract irritation. In some causes
allergic skin reactions. Avoid direct contact.

PREPARATION OF BENZOIC ACID FROM ETHYL BENZOATE
Aim
i. To prepare benzoic acid quantitatively and qualitatively
ii. To purify by recrystallisation and find the melting point
Principle
Ethyl benzoate is hydrolysed to sodium salt of benzoic acid by a
solution of sodium hydroxide. Benzoic acid is obtained from sodium benzoate
by acidification.
Type of reaction: Nucleophilic Substitution
Process: Hydrolysis
COOEt COONa
NaOH
COONa COOH
Con.HCl

It is also called soapanification if the reaction is stopped in stage 1 .The
hydroxyl ion attacks the carbonyl carbon and then displaces OEt , resulting
in the formation of soap. Soap on acidification yields the acid.
Requirements
1. Ethyl benzoate…………………………2.5 g
2. Sodium hydroxide……………………..2g.
3. Con. Hydrochloric Acid……………..5-10ml
Procedure
For Preparation
2g of sodium hydroxide is dissolved in about 20ml of water taken in
a round bottomed flask.
2.5 g of ethyl benzoate is added to the above solution. The flask is then
fitted with a Liebig’s condenser and heated over wire gauze for about 45
minutes.
The hydrolysis is complete when no more oily drops are seen in the flask.
The contents are now cooled and transferred completely to a beaker.
Concentrated hydrochloric acid is added with constant stirring till the
solution is distinctly acidic. The precipitated benzoic acid is filtered, washed
and dried. The weight of crude benzoic acid is noted.
A small portion of the crude benzoic acid is suspended in distilled water and
heated till the solution becomes clear.

The melting point of the recrystallised benzoic acid is determined
Report:
1. Weight of crude Benzoic acid =……………………………g.
2. Melting point of recrystallised benzoic acid = 121oC

Hydrolysis is a chemical process in which a molecule of water is added to a
substance. Sometimes this addition causes both substance and water
molecule to split into two parts.
In organic chemistry, acid–base-catalysed hydrolyses are very common.
In living systems, most biochemical reactions (including ATP hydrolysis) take
place during the catalysis of enzymes. The catalytic action of enzymes allows
the hydrolysis of proteins, fats, oils, and carbohydrates.
Hydrolysis of esters is just the reverse of esterification

Benzoic acid is produced commercially by partial oxidation of toluene with
oxygen. The process is catalyzed by cobalt or manganese naphthenates. The
process uses cheap raw materials, proceeds in high yield, and is considered
environmentally green.
Benzoic acid is an important precursor for the synthesis of many other
organic substances. Its salts are used as a food preservative
Benzoic acid is a constituent of Whitfield's ointment which is used for the
treatment of fungal skin diseases such as tinea, ringworm, and athlete's
foot.
As the principal component of benzoin resin, benzoic acid is also a major
ingredient in both tincture of benzoin and Friar's balsam. Such products
have a long history of use as topical antiseptics and inhalant decongestants.
Benzoic acid was used as an expectorant, analgesic, and antiseptic in the
early 20th century.

PREPARATION OF IODOFORM
Aim
i. To prepare iodoform quantitatively and qualitatively
ii. To purify by recrystallisation and find the melting point
Principle
The reaction between a ketone containing a methyl group and iodine in
presence of an alkali yields iodoform.
It is a nucleophilic substitution reaction proceeding in the following two
steps
Step 1
R- C-CH3 + I2 R- C-I3
║ ║
O O
Step 2
R- C-I3 + NaOH RCOONa + CHI3 ↓

║ iodoform
O
Requirements
1. Acetone…………………………......................3.5 ml
2. 10%Sodium Hydroxide solution…………15ml
3. Iodine Solution ……………………………..30ml
Iodine solution is prepared by dissolving 4.2g of iodine in 30ml of 30%
aqueous KI solution.

Procedure
For Preparation
3.5 ml of acetone is added to 15 ml of 10% sodium hydroxide
solution taken in a conical flask. To this 30 ml of iodine solution is added in
drops with constant shaking. If the solution attains a permanent yellow
colour before adding 30 ml, stop adding iodine solution.

O
The conical is heated on a water bath maintained at 70 -80 C till the
iodoform precipitates (for about 20 mins. ). The precipitated iodofrom is
filtred and recrystallised
Note : If the yellow colour of the solution disappears on heating little more
of the iodine solution has to added and continued to heat till the iodoform
precipitates.
A small portion of the crude iodoform is suspended in 1:1 methanol :water
mixture and heated till the solution becomes clear.
The melting point of the recrystallised iodoform acid is determined
Report:
1. Weight of crude Iodoform =……………………………g.
2. Melting point of recrystallised benzoic acid = 119oC

Iodoform is usually made via the haloform reaction, which can be done on any
methyl ketone, and molecular iodine, which forms the triiodo methyl ketone
in situ. The haloform reaction is one of the oldest organic reactions known.
This reaction was traditionally used to determine the presence of a methyl
ketone, or a secondary alcohol oxidizable to a methyl ketone through the
iodoform test.
It was formerly used to produce iodoform, bromoform, and even chloroform
industrially.
Iodoform is occasionally used as a disinfectant. Around the beginning of the
20th century it was used in medicine as a healing and antiseptic dressing for
wounds and sores.
Klara Hitler, Adolf Hitler’s mother died of iodoform poisoning brought on by
her treatment for breast cancer. It is the active ingredient in many ear
powders for dogs and cats, to prevent infection and facilitate removal of ear
hair, along with zinc oxide and propanoic acid.

Chapter 3
Introduction to Qualitative Analysis
Before outlining the general scheme, one or two points of practical

importance should be noted.
(a) Quantities of substance for tests.
For most tests about 0.1 g solid or 0.1 - 0.2 mL (2 - 3 drops) of liquid
material (NOT MORE) should be used.
(b) Quantities of substance to prepare derivatives.
(c) Students are strongly advised against carrying out unnecessary tests,
since not only are they a waste of time and chemicals, but also increase the
possibility of error.
(d) A systematic approach is essential to avoid confusion and error.
(e) 0.1 – 0.5g (or 0.5 - 1 mL) of substance gives the most satisfactory
results for preparation of derivatives. If a practical book instructs to use
larger quantities (3 - 4 g or more), the quantities should be scaled down to 1
g or 1 mL of the unknown substance and corresponding quantities of reagents
should be used.
(f) The students should report only in written format. Oral reporting is
unacceptable.
(g) Till the student arrives at the correct compound, analysis is IN

COMPLETE (partially correct means repeat analysis). The analysis is deemed
to be complete only after the submission of the correct scheme of
analysis.
(h) Without completing Analysis of one substance, next substance will not be
issued

The scheme of Organic qualitative analysis may be divided into the following
five parts
Organic
Analysis
Part 1 Part 2 Part 3 Part 4 Part 5

Preliminary Elemental
Functional
tests analysis Functional Preparation
Group
(Physical Test for Group of derivative
Analysis
State, Sulphur, Analysis
Colour, Nitrogen and
odour , Halogens
Flame test,
Solubility)
Nature Status Nitrogen Nitrogen

Presence Absence
Aliphatic or Saturated or Amines, Acids,
Aromatic Unsaturated Amides, Alcohols,
Nitro and Aldehydes,
Nitroso Ketones,
compounds Carbohydrat
es, Phenols,
Hydrocarbon
s

Solubility Test
Lower acids, alcohols,

amines, carbohydrates
Test Solubility in
etc.
water (if insoluble
continue)
Basic
substanc Weakly
es like
Test Solubility in
acidic and
amines dil.HCl (if insoluble Phenols
continue)
Test Solubility in
dil.NaOH (if
insoluble continue)
Strong
carboxylic acids Test Solubility in
NaHCO3
Continue in the green path
Corresponding inference

COMPOUND CHARACTERISTIC TESTS DERIVATIVE
Acid Na2CO3 or NaHCO3 solution Anilide, / Amide
Amine Nitrous acid. Benzoyl / acetyl /

sulphonamide
derivatives
Lucas' reagent to
distinguish I, II and III
Alcohol alcohols 3,5dinitrobenzoate
Jones reagent / iodoform /

benzoate
Metallic sodium (use dry
liquid and dry tube).
Sodium hydroxide solution
Phenol Ferric chloride solution Benzoate / acetate

/ bromo-derivative
Bromine water
Fehling's solution.
Aldehydes and Tollen's reagent Semicarbazone /

Ketones (ammoniacal AgNO3 2,4-dinitrophenyl-
solution). hydrazone / oxime
Carbohydrates Molisch's test Osazone
P.S. If al the above are absent then, test for hydrocarbon
The derivatives for hydrocarbon : Nitrate / Picrate

Chapter 4
SYSTEMATIC ANALYSIS OF A SIMPLE ORGANIC SUBSTANCE
Experiment Observation Inference
1. Preliminary tests
May be due to the presence

Colourless of Hydrocarbons, Aldehydes,
ketones, acids, etc.
May be due to the presence of
i. Colour and appearance Phenols, aromatic primary,
are noted secondary , tertiary amines
Pale Brown or Black etc. which could have attained
brown or black colour due to
oxidation
(a) Pleasant fruity May be due to the presence of
Esters or certain aromatic
aldehydes or ketones
(b) Kerosene smell May be due to the presence of
ii. Odour is noted Hydrocarbons
(c) Bitter almonds May be due to the presence of
Benzaldehyde
Aliphatic halogen or Aromatic
(d) Pungent compounds with halogen in the
side chain
(e) Carbolic May be due to the presence of
Phenols
(f) No characteristic May be due to the absence of
odour amines, phenols, esters,
hydrocarbons etc.,

iii. Solubility / Miscibility
Solubility in cold water

A little of the substance in Sugars ,Polyhydric phenols,
taken in a test tube and 5- Soluble /miscible in lower aliphatic alcohols,
10 ml of water is added and cold water aldehydes, ketones, acids or
shaken well amines
Solubility in hot water
A little of the substance in May be due to the presence of

taken in a test tube and 5- Soluble /miscible in Aromatic acids/ anhydrides
10 ml of water is added and warm water or Phenolic acids
shaken well then warmed

The above solution is Insoluble / immiscible Aromatic hydrocarbons,
heated to simmering in hot condition phenols, Aldehydes, or
ketones
Dil .HCl
A little of the substance in Soluble May be due to the presence of

taken in a test tube and 5- amines
10 ml of dil.HCl is added
and shaken well
Dil.NaOH
A little of the substance in
taken in a test tube and 5- Soluble May be due to the presence of
10 ml of dil.NaOH is added Phenols and acids
and shaken well

Saturated NaHCO3
Soluble with May be due to the presence of
A little of the substance in effervescence Carboxylic acids
taken in a test tube and 5-
10 ml of saturated
bicarbonate is added and
shaken well
iv. Beilstein Flame test ( Test for halogens)
A piece of copper wire is

shown in non luminous flame (a)Characteristic Green May be due to the presence of
till there is no colour is imparted to Halogens (Cl / Br / I)
characteristic green clour the flame Note : F does answer
in the flame.
The wire is cooled and
dipped in the substance (b) No characteristic
taken in a test tube or in colour is imparted to Absence of halogens
the aqueous solution of the flame
substance (if solid) . It is
then introduced into the
non luminous flame
2. Detection of Elements: Lassaigne’s Sodium fusion Test
a. Preparation of Sodium fusion extract for Solid substance
About 0.1gm of substance is fused with a small pellet of metallic sodium

(after freeing it from kerosene adhering to it by means of a filter paper) in
a clean dry fusion tube.
The mixture is heated first gently and then strongly for 3 – 5 minutes.
When the fusion tube is red hot, it is plunged in about 15 ml. of distilled
water taken in a mortar and crushed with a pestle.

The mixture is stirred, boiled and filtered (when hot) through a fluted
paper. The clear filtrate is called sodium fusion extract.
b. Preparation of Sodium fusion extract for Liquid substance
Sodium is melted and then 1 ml of the given liquid substance is added in

drops. The mixture is heated first gently and then strongly for 3 – 5
minutes. When the fusion tube is red hot, it is plunged in about 15 ml. of
distilled water taken in a mortar and crushed with a pestle.
WARNING:
• When the fusion tube is plunged in water (un reacted)
Residual sodium metal reacts violently with water and burns
• Never through the unused sodium in dust bin –

fire hazard

i. Test For Nitrogen
To one portion of the extract half A blue or green Presence of nitrogen is

its volume of freshly prepared precipitate or confirmed
saturated FeSO4 solution is added colouration is observed
and boiled .To this a few drops of
FeCl3 solution is added, cooled and
acidified with dil HCl
ii. Test For Halogens Presence of Chlorine is
confirmed
(a) White precipitate
The Second portion of the extract soluble in excess of
is acidified with dil.HNO3, boiled ammonium hydroxide
well, cooled and AgNO3 solution is (b) Pale yellow Presence of Bromine is
added precipitate sparingly confirmed
soluble in NH4OH
(c) Yellow precipitate Presence of Iodine is
insoluble in NH4OH confirmed

iii. Test for Sulphur
a) To a third portion of the filtrate Violet colouration Presence of Sulphur is

a few drops of freshly prepared confirmed
sodium nitro prusside solution is
added
b) To a little of the extract add

few drops of lead acetate solution Black Precipitate Presence of Sulphur is
confirmed
iv. Test for compounds containing

both N and S
To a portion of the extract add few Presence of both

drops of dil.HCl. The solution turns red Nitrogen and Sulphur
Shake well and add 2-5 drops of ( blood red colour)
( may be thio urea)
FeCl3
If halogen is present it is essential to find if it is attached to side

chain or nucleus. This is done by a couple of simple tests.
1. A little of the
substance is refluxed (a)Characteristic Halogen is attached to
with excess of 6N precipitate of silver the side chain
NaOH solution in a test- halide is obtained
tube for about 20mins.on
a water bath The
solution is cooled,
acidified with HNO3 and
(b) No precipitate of Halogen is attached to
then AgNO3 solution is
silver halide. the nucleus
added
2. Action of alcoholic
AgNO3 solution. (a)Characteristic Presence of halogen in
precipitate of silver the side chain is
A little of the confirmed
substance about 2ml. the halide
alcoholic AgNO3 solution
is added and warmed
gently for some time. (b) No characteristic Presence of halogen in
precipitate of silver the nucleus is confirmed
halide.
3. Detection of Functional Groups
Functional groups analysis is carried out to identify
a. The Nature of the given substance

b. The Status of the given substance
c. The reactive functional group
a. Tests to identify the nature
i. Ignition Test (a) Burnt with non- May be due to the

smoky flame presence of Aliphatic
compounds
(b) Burnt with a smoky May be due to the
A small quantity of the flame presence of Aromatic
substance is ignited on a compounds
nickel spatula.
(c) Charred mass is May be due to the
obtained. presence of
Carbohydrates and
certain aliphatic acids
ii. Nitration test. Presence of Aliphatic
compound is confirmed
A little of the
substance is treated or
(a) Colourless solution

with conc. HNO3 and Absence of aromatic
conc.H2SO4 (one ml compound
each) in a test tube.
The mixture is heated (b) Yellow solution or Presence of Aromatic

on a boiling water bath precipitate is observed compound is confirmed
for about half an hour,
and then poured into
50ml of water contained
in a beaker.
b. Tests to identify the Status
i. Action of dilute (a) Immediate de May be due to the

KMnO4 ( Bayer’s Test) colourisation or presence of
appearance of a brown Unsaturated
A little of the precipitate compounds
substance in water is
treated with a few (b) Slow Easily oxidisable
drops of dilute KMnO4 decolourisation compounds like acetone,
solution. phenols ,nitro-phenols,
benzaldehydes etc.
ii. Action bromine water (a) Decolourisation Presence of

Unsaturated compound
is confirmed.
A little of the
substance in water is (b) No decolourisation Presence of Saturated
treated with a little compound is confirmed
bromine water
iii. Action of bromine in i. Decolurisation Presence of Saturated

CCl4 with the compound is
liberation of HBr confirmed(evolution of

A little of the j. ( can be tested gas due to substitution
substance is dissolved in by passing the reaction )
about half ml. of CCl4 vapours into a test
In a dry test –tube. tube containing
Bromine in CCl4 is added AgNO3)
drop by drop and
warmed gently
ii. Decolourisation Unsaturated compounds

without the liberation
of HBr (Addition reaction)
iii. Decolurisation with Easily brominatable

the formation of a compounds like phenols,
precipitate aromatic amines etc

Chapter 6
Some reactions involved in the analysis and their mechanisms:
1. Test for unsaturation
Reagents used: Bromine water, Bromine in CCl4 & KMnO4
Nature of reagents: Mild oxidizing
Out come: Decolourisation of the reagent may due to one of the following
type of reaction
Principle: Addition / substitution / oxidation
Reactions:
i. Action of Bromine water / Bromine in CCl4 on
Unsaturated Compound - Addition
Saturated Compound - Substitution
+ HBr
Phenol
under goes substitution
+ 3 HBr

ii. Action of KMnO4
Unsaturated Compound : Addition
+ MnO2
Brown ppt
Some Saturated compounds also under go oxidation but takes some time
Ex: Glucose, aldehydes, phenol, aniline etc., are easily oxidisable
Glucose , aldehyde on oxidation by a mild oxidizing agent forms acid ( CHO

is converted to COOH in case of glucose acid is gluconic acid)
2. Test for elements
In organic compounds the elements commonly occurring along with carbon

and hydrogen, are oxygen, nitrogen, sulphur, chlorine, bromine and iodine.
The detection of these elements depends upon converting them to water-
soluble ionic compounds and the application of specific tests. On fusing with
sodium the covalent bond between C and the element (Cl/Br/I/N/S) breaks
and forms an ionic compound (NaX/NaCN/ Na2S/ NaCNS)
3. Test for amines
Amine Reaction : Action of Nitrous Acid ( in situ formation by the addition

of NaNO2 and HCl)
Primary aliphatic reacts with the evolution of N2

RNH2 + HNO2 ——► ROH + N2 + H2O
Primary aromatic forms a Diazonium salt
ArNH2 + HNO2 ——► ArN=N+
Secondary aliphatic and secondary aromatic amines forms Yellow oily

(nitrosamines)
R2NH + HNO2 -> R2N-NO
Tertiary aliphatic amines: No visible reaction.
Tertiary aromatic Dialkylanilines yield green solid p-nitroso

compounds (if p-position unsubstituted).
_
4. Amides R-CO-NH2
Simple primary amides can be decomposed by boiling with alkali and thereby
evolving ammonia.
CH3-CO-NH2 + NaOH -> CH3-CO2- Na+ + NH3
5. Carboxylic acids - test with cold saturated NaHCO3
R-CO2H + NaHCO3 -> R-CO2- Na+ + CO2 ↑ + H2O
6. Aldehydes and ketones
2,4-Dinitrophenylhydrazine (Borsche’s test) : 2,4-Dinitrophenylhydrazine on

reacting with a carbonyl group (Aldehydes and ketones ) forms a sparingly

soluble yellow or red precipitate (2,4-dinitrophenylhydrazones whose
structure is shown below).
7. Esters : Hydroxamic acid test
Esters react with hydroxylamine in the presence of sodium hydroxide to

form the sodium salt of the corresponding hydroxamic acid.
R-CO-OR' + H2N-OH -> R-CO-NH-OH + R'-OH
On acidification and addition of ferric chloride the magenta-coloured iron

(III) complex of the hydroxamic acid is formed.

Chapter 7
Important Reagents , preparation and use in Organic analysis
Unsaturation
1. Bromine in carbon tetrachloride. ( 2%-3% )

2. Potassium permanganate solution. ( 2% Aqueous )
Saturated hydrocarbons.
1. Fuming sulphuric acid. (20% free SO2)
Halogens
1. Alcoholic silver nitrate solution. (2% in abs. Alcohol)

2. Sodium iodide in acetone. (7.5g. in 50ml. AR acetone)
Aldehydes and ketones
1. 2:4 Dinitrophenylhydrazine.
(Method 1. Suspend 2.0g. of 2:4 dinitrophenylhydrazine in 100ml. of methanol.
Cautiously and slowly add 4.0ml. of conc. Sulphuric acid. Filter if nessary.)
Method 2. Dissolve 0.25g. of the reagent in a mixture of 42ml. conc.HCl and

50ml. of water by warming on a water bath; dilute to 50 ml. with distilled
water.This reagert is more suitable for water soluble aldehydes and ketones
since alcohol is abscent.
Aldehydes
1. Schiffs reagent.(fuchsin aldehyde reagent)

Method (1) Dissolve 0.2g. of pure p-rosaniline hydrochloride in 20ml. freshly
prepared saturated aqueous solution of solphur dioxide. Dilute to 200ml. and

keep in tightly stoppered bottle.
Method (2) Add 2g. of sodium bisulphite to a solution of 0.2g.of p-rosaniline

hydrochloride and 2ml. of conc. HCl in 200ml. of water.
2. Fehlings solution. Solution no. 1. Dissolve 34.64g. of AR copper sulphate

crystals in water containing a few drops of dilute sulphuric acid and dilute to
600ml.)
Solution no. 2. Dissolve 60g. of NaOH and 173g. of sodium potassium tartrate in
water and dilute to 500ml.
Keep the two solutions separately in tightly stoppered bottles and mix exactly
equal volumes immediately before use.
3. Ammoniacal silver nitrate solution.(Tollens reagent)
Solution A. (3g. of silver nitrate in 30ml. of water)
Solution B. (3g. of NaOH in 30ml. of water)
Mix equal volumes of A and B (1ml) and add dilute ammonia solution drop by drop
until the silver oxide is just redissolved. Use this as the reagent.
Esters and anhydrides
1. Hydroxamic acid test.( 5% ferric chloride added in presence of 0.5N

hydroxylamine hydrochloride in 95% ethanol and 6N sodium hydroxide solution.)
2. Saponification; saponification equivalent.(Aqueous sodium hydroxide method

and the diethylene glycol method)
Alcohols
1. Sodium together with reaction 2.

2. Acetyl chloride or benzoyl chloride.
3. Hydrochloric acid / zinc chloride reagent.(Lucas Test - differentiate
between primary, secondary, and tertiary alcohols) Dissolve 68g (0.5mole) of
anhydrous zinc chloride in 52.5g (0.5mole) conc. HCl with cooling to avoid loss of
hydrogen chloride.

Ethers
1. Sodium.(no reaction)
2. Acetyl chloride.(no reaction)
3. Hydriodic acid.- constant boiling point 126-128oC.- fission of ester
Carboxylic acids
1. Sodium bicarbonate and sodium hydroxide solution.(5% solutions Ã¢â‚¬â€œ

soluble)
2. Neutralisation equivalent.
Phenols
1. Sodium bicarbonate and sodium hydroxide solution.(soluble in 5% sodium

hydroxide and insoluble in 5% sodium bicarbonate)
2. Bromine in carbon tetrachloride and bromine water.(substitution reactions)
3. Ferric chloride solution.( yield intense colours-5%solution)
Amines
1. Acetyl, benzoyl, or benzenesulphonyl or pToluebesulphonyl chloride.(for

primary and secondary amines)
2. Nitrous acid.(Prepare in situ - add HCl and 10% cold sodium nitrite solution)
Nitro compounds
1. Zinc and ammonium chloride solution.

2. Tin and hydrochloric acid.
Amides
1. Dilute sodium hydroxide solution.(10% solutions)

2. Dilute sulphuric acid. Boil with 10% solution)

Nitriles
1. Dilute sodium hydroxide solution.(30-40%) boil.

2. Dilute sulphuric acid.(50-70%) boil.
Sulphonic acids
1. Sulphur present.
2. Sodium bicarbonate and sodium hydroxide solution.
3. S-Benzoyl-iso-thiuronium chloride.
4. Neutralisation equivalent.
Sulphonamides
1. Sulphur and nitrogen present.

2. Sodium hydroxide solution.
3. Sulphuric acid, 70-80%.
SPECIFIC GROUP REAGENTS
REAGENTS SPECIFIC TO FUNCTIONAL GROUPS:

Ammoniacal silver nitrate.
Add conc ammonia to bench silver nitrate (0.1M) until the initially
formed ppt. Just disappears.
Bradys/ Borsche’s reagent (2,4 DNPH)

Dissolve 40g of 2, 4 dinitrophenylhydrazine in 80ml conc. Sulphuric
acid. Cool and add 900ml methanol and 100ml water.
Iodine reagent.
Dissolve 20g KI and 10g iodine crystals in 100ml water.
Jones reagent.
Mix 25g of chromium trioxide (chromic anhydride CrO3) with conc.
sulphuric acid to a paste, then dilute with water to 75mls.
Molisch’s reagent.
20% soln. in naphthol. Dissolve 20g of 1-naphthol in 100ml ethanol.

Tollens reagent.
Add sodium hydroxide soln. to silver nitrate soln. to form a ppt. then
add dilute ammonia soln. until ppt. dissolves.

Annexure I
Report Sheet for Analysis of__________________________________
Register Number
Substance number ……………….
Date of issue............................... Date of report…………………………………
Physical characteristics...................... (Solid / Liquid)
Soluble in …………………………………………………………………………
Nature ……………………………………………………………(Aliphatic / Aromatic)
Status is ……………………………………………………..(Saturated /Unsaturated)
Element Presents present are …………………………………………………..
Functional Group(s) identified is / are …………………………………………………
Comment: Repeat / Proceed Signature

Annexure II
Report Sheet for synthesis of_________________________________
Register Number
Date of synthesis: Date of recrystallisation:
Substrate used Product expected
Name
Structure
Mass (in g)
Mol.formula
Molecular
weight
No. of moles
Percentage Yield = no of moles of product X 100 =

no.of moles of substrate
Melting point of recrystallised product (oC) =
Comment: Signature

Annexure III
Scheme for synthesis of_____________________________________
Process:
Type of reaction:
Reaction:
Raw materials used (Name and Mass only)
Solvent used
For washing:
For recrystallisation:

Acetanilide 19 Filtration 11
Action of Bromine 64 Iodoform 26
Action of Metallic Sodium 44 melting point 13
Action of Soda lime 43 meta dinitro benzene 16
Action of Sodium Bicarbonate 43 Molisch Test 45
Action of Sodium Hydroxide 42 Nature of compound 38
Action of Sulphuric Acid 41 Preliminary tests 33
Attachment of Halogen 37 Recrystallisation 6
Bayers reaction 65 Schiffs Test 45
Benzoic acid 22 solubity tests 34
Bielstein Flame Test 35 Status of compound 39
Borsches Test 45 Test for Halogen 36
Confiramatory for Ketones 48,49 Test for Nitrogen 36
Confiramatory for Acid 46 Test for Sulphur 37
Confiramatory for Aldehyde 48,49
Confiramatory for Carbohydrates 50
Confiramatory for Hydrocarbons 52
Confiramatory for Phenol 47,48
Confirmatory for Alcohols 52
Confirmatory for Amides 53
Confirmatory for Amines 54
Confirmatory for Esters 53
Confirmatory for Nitro Compounds 55
Derivatives For Alcohols 61
Derivatives For Aldehydes and 57
Ketones
Derivatives For Amides 63
Derivatives For Amines 62
Derivatives For Carbohydrates 59
Derivatives For Carboxylic Acids 60
Derivatives For Esters 62
Derivatives For Hydrocarbons 56
Derivatives For Phenols 59
Ferric Chloride Test 44

Study Material 1 PDF

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Study Material 1 PDF

Caricato da

Copyright:

Formati disponibili

PRACTICAL

Professor and Head

V.S.Gayathri Page 1 12/14/2019

Chapter Content Page

SAFETY RULES FOR ORGANIC CHEMISTRY LABORATORY 3

Introduction to techniques involved in practical 5

3 Introduction to Qualitative Analysis 29

4 Systematic Analysis of Simple Organic Substances 33

6 Important reaction mechanisms 63

6 Preparation of important reagents 68

V.S.Gayathri Page 2 12/14/2019

1. Experiments can only be done during scheduled time only.

2. Organic chemistry lab involves working with chemicals that are

3. Modes of exposure to organic chemicals are:

4. Absorption through the skin can be minimized by wearing

5. Ingestion: Don’t eat or drink in the lab.

6. Know the health hazard of your reagents. MSDS are available

8. Keep flammables away from open flame.

9. Read labels very carefully. Inadvertently mixed chemicals

V.S.Gayathri Page 3 12/14/2019

13. Dispose of broken glass using the dust bin.

16. Report to lab in-charge immediately in case of any

experiments safely and successfully

V.S.Gayathri Page 4 12/14/2019

Understanding organic chemistry is impossible without knowledge and

To establish the purity and identity of a compound, a simple melting point

V.S.Gayathri Page 5 12/14/2019

Recrystallisation is a common method adopted for purifying organic

Fig 1 shows the tightly packed crystal lattice of a pure solid

1. The crude solid is dissolved in hot solvent so as to make a saturated

2. The hot saturated solution is cooled to room temperature, so that crystal

3. The solution with the precipitate is placed in an ice bath

4. The solid is then filtered at suction, leaving impurities in solution.

5. The filtered solid is air dried to remove traces of solvent

V.S.Gayathri Page 6 12/14/2019

• Dissolve the entire compound when the solvent is hot (boiling)

V.S.Gayathri Page 7 12/14/2019

V.S.Gayathri Page 8 12/14/2019

When dissolution is complete , allow it to stand for few minutes without

V.S.Gayathri Page 9 12/14/2019

V.S.Gayathri Page 10 12/14/2019

Suction Filtration Apparatus (Buckner Funnel – Flask assembly)

1 – Connect the flask to the suction pump using a rubber tube

2- Place an exact fitting filter paper into the funnel

V.S.Gayathri Page 11 12/14/2019

4- Transfer the precipitate into the filter paper, let it dry

Instead of a bucker funnel, a fluted funnel may also be employed

V.S.Gayathri Page 12 12/14/2019

The melting point of a substance is the temperature at which crystalline

A pure substance melts at a precisely defined temperature, characteristic

An impurity in the compound decreases its melting (freezing) point and

Hence temperature is noted when the liquid becomes visible.

V.S.Gayathri Page 13 12/14/2019

V.S.Gayathri Page 14 12/14/2019

• Do one fast determination to get rough approximation of melting

V.S.Gayathri Page 15 12/14/2019

i.To prepare m-dinitrobenzene quantitatively and qualitatively

ii. To purify the m-dinitrobenzene by recrystallisation and find the melting

Type of reaction: Electrophilic substitution reaction

Meta-dinitrobenzene is prepared by the nitration of nitrobenzene.

The nitration is effected by fuming HNO3 in presence of concentrated

(For detailed mechanism refer 3rd Semester ORGANIC CHEMISTRY

2. Fuming HNO3(Sp.gr. 1.5)…………………..6ml.