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Practical Organic Chemistry (I)

Experiment Findings · October 2017

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Practical Organic
Chemistry (I)

Dr. Pr. Nejib Hussein MEKNI

2011-2015
Preface Dr. Pr. Nejib

Preface

This workbook is intended first and foremost for the students of the second year chemistry

bachelor. The first aim of this practical work is to introduce the student to practical organic

chemistry and to familiarize them with the material (glasswares, balance, heater, stirrer …). In the

other hand to remember them the general cautions in the chemistry organic laboratory and its

particularities, using essentially flammable organic substances.

This workbook is divided into four major parts:

The first part is a general introduction to practical organic chemistry and the simple list of

organic experiment material.

The second part contains the experimental purification and separation of organic compounds

technics. (crystallization and sublimation, distillation and liquid-liquid extraction)

The third part is conserved to the chemical identification tests of different families of organic

compounds, based on their functional groups. (Hydrocarbons, Ketones, aldehyde, alcohols,

phenols, carboxylic acids and salts, amines, amides, imides, urea, anilides amino acids,

carbohydrates), followed by the an application to identification of unknown organic

compounds.

In the last part the students practice the synthesis and the purification of aspirin as an

application and a revision of the major parts previously studied.

 List of Topics

Topic Page

P1 List of Organic Experiment Material 1

P2 Crystallization & Sublimation 6

P3 Distillation 8

P4 Liquid-Liquid Extraction 12

P5 Identification of Hydrocarbons 13

P6 Identification of Ketones and Aldehyde 16

P7 Identification of Alcohols and Phenols 19

P8 Identification and reactions of Carboxylic Acids and Salts 23

Identification and reactions of Amines, Amides, Imides, Urea, Anilides and

P9 28
Amino Acids

P10 Identification Test of Carbohydrates and their Classification 30

P11 Identification of Unknown Organic Compounds 32

P12 Synthesis and Purification of Aspirin 39

Lecture 1: List of Organic Experiment Material Dr. Nejib

List of Organic Experiment Material

I. Objectives:

To know the name of organic experiment material and its use.

II. Material

Simple distillation head Bend head Multiple adapter

receiver adapter with

Adapter receiver adapter
Vacuum Connection

1
Lecture 1: List of Organic Experiment Material Dr. Nejib

Round Bottom quikfit Flask Round Bottom quickfit Flask Flat-bottomed

bottomed quickfit flask

Three Necks round Bottom Two Necks round Bottom

Funnel
quickfit flask quickfit flask

Erlenmeyer flask (Conical flask)

2
Lecture 1: List of Organic Experiment Material Dr. Nejib

Buchner Funnel Büchner flask Beaker

Separating funnel Fractionation column Thermometer quickfit

3
Lecture 1: List of Organic Experiment Material Dr. Nejib

Condenser Dropping funnel Chromatographic Column

Stirrer and Hot plate laboratory stand pole

4
Lecture 1: List of Organic Experiment Material Dr. Nejib

Report

Complete the following spaces by the corresponding names.

5
Lecture 2: Crystallization & Sublimation Dr. Nejib

Crystallization & Sublimation

I. Objectives:

The practical realization of Crystallization & Sublimation.

II. Material and Products

Apparatus: Beaker Funnel, Heater, Buchner funnel.

III. Background

1. Necessity of purification

Organic compounds are isolated from either natural sources or reaction synthetic

mixtures. In natural mixtures, the target is generally constitute a low percentage

proportion. In synthetic mixture, the target may be the major product, but not pure. The

reactional mixture contains alwys impurities.

In order to obtain pure organic substances, mixtures are purified by physical technics.

according to their nature, espacialy physical state and polarity. This purification my

follow one or more purification steps and methods.

2. Crystallization

Crystallization is the most common

method for purification of solid organic

compounds.

Impurities and organic compound have

different solubilities in a given solvent.

The organic compound should be

insoluble or sparingly soluble in the

solvent at room temperature but readily

soluble in hot conditions.

The impurities should be insoluble in the solvent even in hot conditions.

The organic compound should not react with the solvent.

6
Lecture 2: Crystallization & Sublimation Dr. Nejib

3. Sublimation

Sublimation is the direct physical transformation from of a substance from solid state to

gasous one. (Example: Naphthalene, benzoic acid and camphor).

The reverse transformation is possible it is called deposition. It is observed by when

cooling the vapors, yielding pure solid crystals called sublimate.

Scheme: Sublumation-Deposition apartus.

VI. Experimental

1. Realize the crystallization of 2 g of benzoic acid using water as solvent.

2. Realize the sublimation of 1 g of naphthalene.

3. Describe briefly how to choose the best crystallization solvant.

7
Lecture 3: Distillation Dr. Nejib

Distillation

I. Objectives
To study the different distillation techniques.

II. Material and Products

Apparatus: Hot plate, a quick fit round-bottom flask, condenser, Erlenmeyer, funnel,
thermometer, distillation head, fractionation column, receiver adapter.

Chemicals : Acetone, water.

III. Background

Distillation is a physical method for separation and purification of liquids based on their
different boiling points.

Scheme 1

8
Lecture 3: Distillation Dr. Nejib

Distillations have different application fields. It is used for example to separate petroleum
into its derivatives Water is distilled to remove impurities, such as salt from seawater.

i) Simple Distillation

It is a process used to separate a pure liquid from a solid-liquid solution. Example pure
water from soft drinks, sea-water, etc

Difference in boiling points of compounds is more than 40ºC. e.g. chloroform (b. p. 61 0C)
and aniline (b. p. 184 0C).

A liquid boils and turns into vapor at its boiling point.

When the vapor is condensed, the (pure) liquid is obtained again.

Scheme 2

(ii) Fractional distillation

This process is used to separate miscible liquids having different boiling points.

Liquid with lower boiling point are obtained first e.g. Ethanol (78 0C) first, then water (100
0C).

9
Lecture 3: Distillation Dr. Nejib

Scheme 3

10
Lecture 3: Distillation Dr. Nejib

(iii) Vacuum distillation

This method is used for organic compounds, which decompose at or below their boiling
points. e.g. Glycerol.

(iv) Steam distillation

Used for organic compounds which are immiscible with water and are steam volatile. e.g.
Aniline.

11
Lecture 4: Liquid-Liquid Extraction Dr. Nejib

Liquid-Liquid Extraction

I. Objectives

Practice the experimental liquid-liquid separation, to extract an organic product.

II. Material and Products
Apparatus: separating funnel, conical flask, funnel.
Chemicals: Organic solvants (diethylic ether, chloroform or dichloromethane) organic
substance.
III. Background
What is a liquid-liquid extraction?
It is a method of separating of a substance from a liquid solution by
mixing it with an organic solvent or the reverse.
How to have an effective liquid-liquid extraction?
* The added solvent must be more volatile than the desired
component.
* It must also specifically dissolve the desired component.
* The component must have a greater tendency to dissolve in the
added solvent than in the solution.
* The added solvent must be immiscible with the solution.
* The added solvent and the solution must be of different densities.
* If possible, the added solvent must not be toxic.
VI. Experimental
1- Prepare a tea solution.
2- Place the prepared tea solution in the separating funnel then add
an organic solvent (chloroform or Ether).
3- Mix and stir, evacuate the gas.
4- Place the separating funnel on the support to repose.
Separating funnel
5- Wait until you observe clearly the separation of the two phases.
6- Place each phase in an Erlenmeyer.
7- Evaporate the organic solvent.
8- Weight the solid product
9- Calculate the mass percent of the tea extracted in this organic phase.

12
Lecture 5: Identification of Hydrocarbons Dr. Nejib

Identification of Hydrocarbons

I. Objectives:

The practical identification of hydrocarbons.

II. Material and Products

Apparatus: 6 test tube with a support, pipettes and small-size beakers.

Chemicals: (Toluene, Hexane, Cyclohexene, Unknown hydrocarbons A, B and C),

Petroleum ether, bromine solution, KMnO4 solution and H2SO4.

III. Background

The total number of known organic compounds is about one million. The simplest of them
are those containing only carbon and hydrogen atoms called hydrocarbons.

Hydrocarbons constitute four general families (alkane, alkene, alkyne and aromatic
hydrocarbons) to distinguish between them some simple test should be realized.

VI. Experimental

A. Physical Properties

1. Water solubility:

On six test tubes indicate the name of the hydrocarbon to be tested, then place about 1 mL
in each tube.

Add dropwise about 0.5 mL of water into each tube.

Is the obtained mixture homogenous or heterogeneous?

Which substance is on the top and which one is on the bottom?

Mix the content of each tube, then observe. What happens when it allowed to settle?

Conclude about the density of the hydrocarbons relatively to the water?

Take notes and save the solutions for the next part.

2. Solubility in Petroleum ether:

On six test tubes indicate the name of the hydrocarbon to be tested, then place about 1 mL
in each tube.

Add dropwise about 0.5 mL of ligroin (non polar solvent) into each test tube.

Is the mixture homogenous? If not which layer is on the top?

13
Lecture 5: Identification of Hydrocarbons Dr. Nejib

Mix the contents and observe if there is any appearance change of the contents.

Compare the obtained results to those of the previous part.

Observe and make a conclusion about the hydrocarbons densities.

B. Chemical Properties

1. Reaction with bromine.

Bromine reacts with alkene and alkyne (unsaturated) compounds.

On six test tubes indicate the name of the hydrocarbon to be tested, then place about 1 mL
in each tube.

Add dropwise about 0.5 mL of a bromine solution.

Does the yellow color of the brome persists or disappears.

Conclude for each substance. Does it saturated or not?

2. Reaction with KMnO4 :

On six clean and dry test tubes indicate the name of the hydrocarbon to be tested, then
place about 1 mL in each tube.

Carefully add 1% aqueous KMnO4 (dropwise) solution; Shake to mix the solutions after
each drop. Do not exceed 10 drops.

Give a conclusion.

3. Reaction with concentrated H2SO4

The appearance of a color, the formation of a homogeneous mixture or the evolution of

heat indicates that a chemical reaction occurred.

On six clean and dry test tubes indicate the name of the hydrocarbon to be tested, then
place about 1 mL in each tube.

Place the tubes in an ice bath.

Wear gloves and carefully add 3 drops of cold, concentrated sulfuric acid in each tube.

What happens in each tube?

Give a conclusion.

4. Unknowns:

Compare the observations of the unknowns to those of the known hydrocarbons and
identify the unknown compounds.

Complete the following report sheet.

14
Lecture 5: Identification of Hydrocarbons Dr. Nejib

Report

Physical properties
Solubility: Does the compound dissolves in water?
Conclude about the hydrocarbons polarity.
Density: Does hydrocarbons float on water or sink?
For ligroin, conclude about the relative densities?

Water Petroleum ether

Hydrocarbon Solubility Density Solubility Density
Hexane

Cyclohexene
Toluene

Compound A

Compound B

Compound C

Chemical properties

Hydrocarbon Bromine Test KMnO4 Test H2SO4 Test

Hexane

Cyclohexene

Toluene

Compound A

Compound B
Compound C
From the above results give the hydrocarbon family name of each compound

Compound A is _____________________________

Compound B is ______________________________

Compound C is ______________________________

15
Lecture 6: Identification of Ketones and Aldehyde Dr. Nejib

Identification of Ketones and Aldehyde

I. Objectives

Experiment with some aldehydes and ketones to understand some of their chemical
properties and use these knowledge to distinguish characterize carbonyl compounds.

Apparatus: six test tube rack, Test tube holder, heater, Becker (500 mL), pipettes, small
size beakers.

Chemicals: 0.10 M AgNO3 solution, 2,4-Dinitrophenylhydrazine(DNP), propan-2-ol,

Benzaldehyde, 10 % NaOH solution, butan-2-ol, butan-2-one, 2 % NH4OH, methanol, Methyl
isobutyl Ketone, cyclohexanone, I/KI (Iodoform test), Propanone, Propaldehyde, 6 M NaOH
solution, Jones’ reagent and unknowns.

II. Experimental

Part I. Reaction with nitrogen compounds (DNP)

Into each one three labeled test tubes, place respectively 3 drops of benzaldehyde,
methyl ethyl ketone, and your unknown and add 8 mL of methanol into each one. Then, add
dropwise 2 mL of DNP reagent to each tube (20 drops = 1 mL).

If the DNP product does not precipitate immediately, place the solution in a hot water
bath for 5 minutes, to ensure complete reaction. Then, place the solution in an ice bath. If the
product is still too soluble, add dropwise cold water to the solution (do not exceed 10 mL of
water).

Part II. Chromic Acid Oxidation Test (Jones’ Reagent)

In a test tube place 3 drops of butan-2-one and add under agitating, 4 drops of chromic
acid solution. Let stand for 10 minutes. Record any color change and how long time it takes to
occur.

Curry out the simultaneously test for propaldehyde, acetone, and the unknown.

Part III. Tollens’ Silver Mirror Test for Aldehydes

Perform this test (place 3 drops) on propaldehyde, benzaldehyde, butan-2-one and

the unknown.

16
Lecture 6: Identification of Ketones and Aldehyde Dr. Nejib
In a clean test tube place one drop of 10 % NaOH and 1 mL of 0.1 M AgNO3, then add
dropwise 2 % NH4OH until just dissolving the Ag2O precipitate. Be careful do not add an
excess of NH4OH.

To the above test tube, add two drops of the carbonyl compound to be tested, mix and
allow the tube to stand for 10 minutes. If no reaction occurs within this time, place the tube in
a water bath (40 0C). The formation of a silver mirror or a black precipitate of finely divided
silver is a signe of a positive test.

Part IV. Iodoform Test for Methyl Ketones

In a small test tube, place 3 drops of an unknown liquid, 2.0 mL of water and 1 mL of 10
% NaOH aqueous solution. Add dropwise an iodine/potassium iodide solution (I/KI) under
agitation and look for a light yellow precipitate of iodoform (CHI3) appearance. This indicates
a positive test for a methylated ketones. Note your results.

Identify the unknown substance which will be either an aldehyde or ketone.

17
Lecture 6: Identification of Ketones and Aldehyde Dr. Nejib
Report

Part I. Reaction with (DNP)

a) Benzaldehyde:
b) Butan-2-one:
c) Unknown :
Part II. Chromic Acid Oxidation Test (Jones’ Reagent)
a) Propanal:
b) Propanone (Acetone):
c) Butan-2-one:
d) Unknown :
Part III. Tollens’ Silver Mirror Test for Aldehydes
a) Propanal:
b) Benzaldehyde:
c) Butan-2-one:
d) Unknown :
Part IV. Iodoform test for Methyl Ketones
a) Butan-2-one:
b) Unknown :

Give a conclusion describing the common and the different aldehyde and ketone
characterization tests.

18
Lecture 7: Identification of Alcohols and Phenols Dr. Nejib

Identification of Alcohols and Phenols

I. Objectives

To use the chemical characterization

characteri tests to identify and distinguish phenols and the three classes
of alcohols.

II. Background

Alcohols and Phenols contain the -OH functional group. In a phenol, the -OH
OH group is connected to a
carbon on a benzene ring where as in alcohols, the -OH
OH group is connected to a sp3 hybridized carbon
atom.

There are three classes of alcohols, 10, 20 and 30 depending

nding on the number of carbon atoms,
atoms linked
to the carbon bearing the -OH
OH group.
group

Examples:

Phenols are more acidic than alcohols. Alcohols as well as phenols find a variety of industrial,
pharmaceutical, and even household applications. Derivatives of alcohols and phenols are found in
medicines, alcohols are used as common industrial solvents etc …

Ferric Chloride test: Alcohols are readily differentiated from phenols using this test.
test Addition of
oneor two drops of ferric chloride solution to a sample of phenol will produce a distinct violet/purple
violet/purp
coloration but, alcohols
lcohols do not produce such deep coloration.
coloration

Lucas Test: A solution of zinc chloride in concentrated hydrochloric acid is called the Lucas
Reagent. Tertiary alcohols react almost instantaneously with Lucas Test to give water insoluble
insolu alkyl
chlorides as products.
ZnCl
R—OH
R + HCl 2
 R—Cl+ H2O

Secondary alcohols will form cloudy products upon standing while primary alcohols need to be
heated with the reagents before the reaction can occur. This qualitative test can be used to identify a
primary alcohol from secondary and tertiary alcohols.

Chromic Acid Test: Potassium dichromate, K2Cr2O7 in aqueous acid and Jones Reagent (CrO
( 3 in

acetone and sulfuric acid) are two common oxidizing agents. In both these reagents, Cr is present as
Cr(VI) which is red orange in color. However after the oxidation reaction, Cr (VI) gets reduced to

19
Lecture 7: Identification of Alcohols and Phenols Dr. Nejib

Cr(III) which is dark green in color. Both primary as well as secondary alcohols are oxidized using
these reagents, producing a green Cr(III) precipitate. Tertiary alcohols are not oxidized with these
reagents.

Pre-laboratory

Consider the structures of the various alcohols and phenols

phenols shown and complete the report sheet
by noting the expected outcome of the indicated reactions.

III. Experimental

Ferric Chloride Test:

1. Place into separate clean and dry test tubes,

tubes 5 drops of each sample to be tested.

2. Add to each tube 2 drops of ferric chloride solution. Note the coloration before and after the
addition of the reagent. Record your observations.Lucus
observations. Test:

1. Obtain the six unknown compounds.

2. Label 7 clean dry test tubes with the unknown numbers.

3. Add 5 drops off each sample to the appropriate test tube.

4. Add 1 mL of Lucas reagent.

5. Mix by tapping the tube with a finger. If there is no cloudiness mix by stoppering and gently shaking
the test tubes. Look for cloudiness that may detected during this time. Note your observations. If there
is no cloudiness after 10 minutes at room temperature, warm the test tubes in a water bath (60 0C) for
15 minutes.

6. At the conclusion of this test, rinse the contents of the test tube down the drain with
wit plenty of tap
water. Do not remove safety glasses until the rinsing is complete.

Chromic Acid Test: Bordwell--Wellman Test

1. Place into separate clean and dry test tubes,

tubes 5 drops of each sample to be tested.

2. Add into
to each test tube 10 drops of reagent grade acetone and 2 drops of the chromic acid reagent.

3. Place the tubes in a water bath maintained at 50 0C. Note the coloration before and after heating.
Record your observations.

20
Lecture 7: Identification of Alcohols and Phenols Dr. Nejib

Report

Pre-Laboratory

Compound Ferric Chloride Lucas Test (Fast, Medium, Jones Reagent

(Positive or Slow and No Reaction) (Green for expected reaction
Negative) and NR for no reaction)
A
B
C
D
E
F
G
H
I
J
K

Data Table

Lucas Test Chromic Acid Test

Ferric
Results Results (Green for PhenolorAlcohol
Unknown Chloride Test
expected reaction Category Boiling Point
Number (Positive or (Fast, Medium,
Negative) Slow and No and NR for no (10, 20, 30,)
Reaction) reaction)

21
Lecture 7: Identification of Alcohols and Phenols Dr. Nejib

Report

1. Is it necessary to perform the Lucas Test in order to determine the unknowns? Explain.

2. Compare the boiling points of the compounds with three simplycarbons bonded to four carbons
bonded.

Give a general statement of the effect of chain length on boiling point.

Explain why this trend makes sense using your knowledge of London Dispersion Forces.

3. Compare your predicted boiling point for alcohols with the hydroxyl groups on the end as opposed
to in the middle of compound.

Give a general statement of the effect of the chain branching on boiling point.

What must happen to the London Dispersion Forces as branching increases?

4. The boiling points of aliphatic isomer of phenol range from 120- 1580C.

Give a general statement of the effect of the cyclical shape of hydrocarbons on their boiling points.

Based on your data, are London Dispersion forces greater in a cyclic compound or an aliphatic
compound?

Identification of unknowns

Each unknown is one of the alcohols in the chart below. First, use the name of the alcohol to sketch
the structural formula. Next, determine from the structural formula if the alcohol is a primary,
secondary, or tertiary alcohol. Finally, use the boiling point, Lucas test & Chromic Acid test data from
your unknowns to determine the identities of the unknowns.

Alcohol boiling point structural formula alcohol category Unknown number

Butan-1-ol 1180C

Butan-2-ol 1000C

2-methylpropan-2-ol
(tert-butyl alcohol) 830C

3-methylbutan-l-ol
(isoamyl alcohol or 1300C
isopentyl alcohol)
Propan-1-ol 980C

Propan-2-ol 820C

Phenol 1810C

22
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib

Identification and reactions of carboxylic acids and salts

I. Objectives:

The identification and reactivity of carboxylic acids and their salts.

II. Chemicals: Litmus paper, sodium hydroxide NaOH, sodium bicarbonate NaHCO3,
sodium carbonate Na2CO3, soda lime, methnol, (H2SO4, HCl gas or ZnCl2) ferric chloride
FeCl3 or calcium chloride CaCl2. AgNO3 HgCl2, KMnO4, Acids and acid salts.

III. Background

Organic acids contain the carboxylic group COOH. They are in general weaker than
mineral acids, thus, they are displaced from their salts through the addition of HCl, HNO3
and H2SO4.

It also divided into a) aliphatic and b) aromatic acids. Aromatic acids being usually
soluble in water and are precipitated from their salt solution on addition of mineral acids,
e. g. HCl.

VI. General reactions:

1. Their aqueous solutions are acidic to litmus paper.

2. They dissolve in sodium carbonate solution with the evolution of carbon dioxide,
distinction from the phenols, they also dissolved readily in sodium hydroxide solution.

3. The carboxylic group can be eliminated as CO2 when the acid or its salt is heated with
soda lime.

4. They give ester when treated with alcohol in presence of dehydrating agent (e. g.
H2SO4, HCl gas, ZnCl2).

5. They give characteristic color or precipitate when their neutral solutions are treated
with ferric chloride or calcium chloride.

23
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib

V. Experimental

1- Acidity test:

When the free acid is treated with a solution of sodium bicarbonate NaHCO3, carbon
dioxide (CO2) is observed with effervescence.

2- Dilute sulfuric acid:

When added to a formate and heated, formic acid is liberated and can be detected by its
odor.

3- Conc. Sulphuric acid

When the salt is heated with conc. H2SO4, CO2 evolves which burns with a blue flame.

4- Ferric chloride

With 1-2 drops of FeCl3 are added to the neutral solution, a red color is produced which
change into a brown precipitate on heating.

5- Ammonium AgNO3

When 2-3 drops of ammoniacal AgNO3 solution are added to the neutral solution, a
white precipitate of Ag is formed rapidly and reduced to metallic silver on heating
(black precipitate or mirror).

6- HgCl2

When 2-3 drops of HgCl2 solution added to the neutral solution, a white precipitate of
Hg2Cl2, which is reduced further to Hg on heating with excess formate. When NH4OH is
added to the white precipitate, it turns grey.

7- KMnO4

When a few drops of Na2CO3 were added to the solution followed by few drops of
KMnO4, the color is destroyed.

8- Ester formation

Two parts of ethanol are mixed with on part of concentrated H2SO4, then, the carboxylic
acid is added. Heat in a water bath for 10 minutes and then pour into a beaker containing
Na2CO3, where the pleasant odor of ester is detected.

24
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib

Report

1- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4 solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

2- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4
solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

25
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib

3- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4
solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

4- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4
solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

26
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib

5- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4
solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

6- Acid name and structure

Chemical properties

Experiment Observation Inference

Acidity test
Effect of dil. H2SO4 solution
Effect of conc. H2SO4
solution
Ferric chloride
Ammonium AgNO3
HgCl2
KMnO4
Ester formation

27
Lecture 9: Identification and reactions of amines, amides, imides, urea, anilides and amino acids Dr. Nejib

Identification and reactions of amines, amides, imides, urea, anilides

and amino acids


Objectives

The experimental identification and reactivity of amines, amides, imides, urea, anilides and
amino acids.

II. Chemicals: 10 % Copper sulfate solution, Benzenesulfonyl chloride, 10% NaOH, 10%
HCl, distillated water, amines, amides, imides, urea, anilides and amino acids

III. Background

Primary aromatic amines are used as a starting material for the manufacture of azo dyes. They
react with nitric acid to form the corresponding diazonium salt. These later can undergo
coupling reactions to produce azo compounds, which are highly colored, widely used in dyes
industries and drugs.

Diphenhydramine: Antihistamine, benadryl.

Chlorpheniramine: Antihistamine helps to relief allergic disorders due to cold, itchy skin, hay
fever, insect bites and stings.

Acetaminophen: Paracetamol (p-acetaminophenol), is an analgesic that relieves pains such as

headaches. It is less corrosive to the stomach, used as an alternative to aspirin.

Chlorpromazine: Tranquillizer drug, that acts without inducing sleep, anxiety reliever,
excitement, restlessness or even mental disorder.

VI. Experimental

a) Copper ion test

Procedure:

In a small test tube place 8 drops of 10 % Copper Sulfate aqueous solution, then add a drop
of the unknown compound (or few crystals from a solid).

The appearance of a blue-green color or a precipitate, is a positive test indication of the

presence of amine functional group.

28
Lecture 9: Identification and reactions of amines, amides, imides, urea, anilides and amino acids Dr. Nejib

b) Hinsberg test

Procedure:

In 25 mL Erlenmeyer flask, place 0.1 mL (~2 drops) of the unknown (0.1 g of a solid), then
add Benzenesulfonyl chloride (0.2 mL, 4 drops). Stir for 1 minute, then add 5 mL of 10 %
NaOH(aq). Stir vigorously the reaction mixture for 5 minutes or longer, until the oily
sulfonyl chloride has reacted. Test the reaction mixture with litmus paper to insure that
the medium is alkaline.

Place the reaction contents in a hot water bath for few minutes, then cool it to room
temperature and note whether or not a residue (oil) or a precipitate appears in the
medium.

If there is no observed residue or precipitate, treat the mixture with 10 % HCl(aq) solution.
The appearance of a precipitate upon acidification of the mixture is an indication that the
unknown is a primary amine.

Separate the obtained residue or a precipitate from the medium, and test it its solubility in
a 10 % HCl(aq) solution. If it is insoluble in 10 % HCl(aq) solution, the unknown compound is
a secondary amine, if it is soluble, the unknown is a tertiary amine.

Distinction between aliphatic and aromatic primary amines.

The aromatic amine reacts with nitrous acid, to produce the diazonium salt, which can be
detected by the formation of a red dye with alkaline phenol solution.

Ar-NH2 + HONO → Ar-N+≡N

Ar-N+≡N + C6H5OH → HO-C6H4-N=N-Ar (red dye)

29
Lecture 10: Identification Test of Carbohydrates and their Classification Dr. Nejib

Identification Test of Carbohydrates and their Classification

I. Objectives

The classification and the identification of carbohydrates.

II. Chemicals

-naphthol, concentrated sulphuric acid, Fehling solution, dilute HCl, sodium hydroxide
solution, phenyl hydrazine hydrochloride, sodium acetate, acetic acid, resorcinol,
concentrated HCl, oxy-sugars, ferric chloride.

III. Background

Definition

Carbohydrates are aldehydic or ketonic polyols (CnH2nOn). Examples: glucose, sucrose,

maltose etc ...

Carbohydrates are the most abundant constituents of the plants (starch and cellulose).
They are produced by the photosynthesis chemical reactions by which plant synthesizes
various chemical subsequent constituents. In the animals they are usually present in
polysaccharides form (glycogen), produced by metabolic processes like glycogenesis.

Carbohydrates classification:

Carbohydrates are classified into two groups: Sugars and Polysaccharides.

1-Sugars called also saccharides, are water soluble and make sweet solution, such
products contain an unbroken chain of carbon atom. They are divided into three classes
(Monosaccharide, Disaccharide and Oligosaccharide).

Monosaccharide the simplest sugar unit, that it cannot be hydrolyzed. They are highly
soluble in the water and are most sweet (glucose, galactose, mannose and fructose).

Disaccharides are water soluble, sugars, yielding two monosaccharides by hydrolysis,

sweeter than monosaccharide and present abundantly in plants (sucrose).

Oligosaccharides are the carbohydrates that containing three to ten monosaccharides,

linked through oxygen atoms.

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Lecture 10: Identification Test of Carbohydrates and their Classification Dr. Nejib

2- Polysaccharides are substances that constituted from a large number of

monosaccharides linked through oxygen atoms. They are also hydrolysable by enzymes
and reagents, yielding monosaccharide as final product. For this reason they are classified
as hexose called hexosan, glucosan, fructosan etc…

VI. Experimental

A- Molisch test: To a carbohydrate aqueous solution containing -naphthol, concentrated

sulphuric acid is added along the wall of test tube. The appearance of purple ring on the
junction of the two liquids, indicates the presence of carbohydrates.

B- Fehling solution test: The sugar is heated in a dilute HCl solution, then the mixture is
neutralized by a sodium hydroxide solution. Add 1 to 2 drops of Fehling solution, to the
mixture, a red precipitate of CuO is observed.

C- Osazone test (lactose test): Sugar is heated with acetic acid, sodium acetate and phenyl
hydrazine hydrochloride solution, Osazone yellow crystals are observe.

D- Resorcinol test (ketoses test): To a sugar aqueous solution some resorcinol crystals
are added, the mixture is heated with an equal volume of concentrated HCl. Pink color
appears.

E- Test for pentose: A sugar aqueous solution is heated with an equal volume of
concentrated HCl. A red color is formed indicating the formation of Phloro glucinol.

F- Kaller-kiliani test for de oxy sugars: A deoxy sugar is dissolved in acetic acid
containing trace of ferric chloride. Concentrated sulphuric acid is added and a reddish
brown color is formed which turns on blue later.

31
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

Identification of Unknown Organic Compounds

Introduction

Fully identification characterization and of unknown or new synthesized compounds is an

important and necessary part of organic chemists work. Although, it is often possible to
elucidate the compound structure based on its spectroscopic data (IR, NMR, MS). Typically
many other information are important for the compound characterization, such as: elemental
analysis, physical properties (solubility, color, odor, melting point, boiling point, confirmatory
tests, etc ...).

In this experiment, we will carry out several qualitative tests that allow us to identify
functional groups. So, we will apply what that we have learned previously when
characterizing unknown organic compounds functional group and their solubilities. We will
examine carboxylic acids, alcohols, amines, alkanes, alkenes, and alkyl halides functional
groups.

Solubility and functional group tests

Each functional group has a particular set of chemical properties that allow to its
identification. Some of these properties can be demonstrated by observing solubility, while
others can be seen through chemical reactions, showing precipitate formation, color changes,
temperature variation or other visible effects.

1. Solubility tests

The solubility in water, dilute basic or dilute acid aqueous solutions of an organic
compound, can provide useful information indicating the absence or the presence of certain
functional groups. The following chart (Figure 1) shows the solubility sequence tests along
with the appropriate conclusions.

Solubility in water: Except for low molecular-weight (fewer than five carbon atoms) oxygen
and nitrogen-containing compounds, most organic compounds are not soluble in water.

 Carboxylic acids containing less than five carbon atoms are soluble in water and form
acidic solutions (red litmus paper test).

 Amines containing less than five carbons are also soluble in water and give basic
solutions (bleu litmus paper test).

32
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

 Alcohols, aldehydes and ketones, containing fewer than five carbon atoms are soluble in
water and give neutral solutions.

Solubility in NaOH solution: Solubility in 6 M NaOH solution is a positive identification test

for acids. A carboxylic acid that is insoluble in pure water, but soluble in sodium hydroxide
aqueous solution, yields the corresponding sodium acid salt.

Solubility in HCl solution: Solubility in 6 M HCl solution is a positive identification test for
amines. Amines, that are insoluble in pure water, but soluble in hydrochloric acid aqueous
solution, produce the corresponding ammonium chloride salt.

Figure 1: The solubility test Flowchart.

2. Silver Nitrate test for Alkyl Halides and Carboxylic Acids

Silver nitrate reacts with an alkyl halide in ethanol, yielding a white or yellow silver halide
precipitate that is insoluble in nitric acid. This reaction quite often proceeds slowly, and
occasionally slight heat is necessary.

33
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

RX + AgNO3 RONO2 + AgX(s)

Carboxylic acids form insoluble precipitate silver salts, that dissolve in nitric acid solution,
whereas the silver halides do not.

3. Beilstein test for Halides

It is the simplest method to detect the presence of halogens, but it cannot distinguish
among chlorine, bromine, and iodine. The production of a volatile copper halide when an
organic halide is heated with copper oxide is a positive result for Beilstein test. The copper
halide imparts a blue-green color to the flame.

4. Lucas test for Alcohols

Lucas reagent is prepared from zinc chloride and hydrochloric acid mixture, its action it
allows to detect the presence of an alcohol by its transformation into an alkyl chloride,
insoluble in the solution.
ZnCl2
ROH + HCl RCl + H2O

At room temperature, tertiary, benzylic, and allylic alcohols react instantaneously.

Secondary alcohols react slowly, whereas primary alcohols do not react, therefore, it is seen
simply to dissolve.

5. Chromic Acid test for Alcohols

Chromium test consists in a reduction of orange chromium(IV), into green chromium(III),

by oxidizing of alcohol. Primary alcohols are directly oxidized into the corresponding
carboxylic acids. Secondary alcohols are oxidized into ketones. But, tertiary alcohols are not
oxidized.

Contrary to the Lucas test, chromic test can be used with all kinds of alcohols, regardless of
their solubility, molecular weight and structures. Hence, this reaction can be used to
determine the class of an alcohol.

34
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

6. Bromination test for Alkenes

Bromine immediately adds on the carbon-carbon alkene double bond, yielding a

dibromoalkane. When adding some drops of a red solution of bromine in CH2Cl2 to a colorless
alkene, the red bromine color disappears quickly, from its reaction with the alkene. (Scheme):

7. Potassium Permanganate test for Alkenes

This test is positive for alkenes but not for aromatic compounds. It consists in the
conversion of the alkenes into the corresponding diol from the reduction of purple ion MnO4-
into a brown precipitate of MnO2.

Other easily oxidized compounds such as aldehydes, some alcohols, phenols, and aromatic
amines, give also a positive test.

35
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

Report

A. Characterization of Known Compounds

Describe the positive tests and indicate the experimental conditions and observations such
as precipitate formation, color change, reaction time, heating needs, shaking or stirring.

1. Solubility tests

Indicate the solution nature for the water soluble organic compounds (acid, neutral, or
basic).

2. Silver Nitrate test

1-bromobutane:
Other compounds:
What happened when HNO3 was added to each precipitate?

3. Beilstein test

Unknown:
Benzoic acid

4. Lucas test

Butan-1-ol:
Butan-2-ol:
t-butanol:

5. Chromic Acid test

Butan-1-ol:
Butan-2-ol:
t-butanol:

6. Bromination test

Cyclohexane:
Cyclohexene:

7. Permanganate test

Cyclohexene:
Toluene:

36
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

B. Characterization of Unknown Compounds

Unknown numbers: (a) ____________ (b) ____________

Test Observations Conclusions

(a) (a)
Solubility in water
(b) (b)
Solubility in 6M NaOH (a) (a)
solution (if needed) (b) (b)
Solubility in 6M HCl solution (a) (a)
(if needed) (b) (b)
Silver nitrate test (a) (a)
(b) (b)
Beilstein test (a) (a)
(b) (b)
Lucas test (a) (a)
(b) (b)
Chromic Acid test (a) (a)
(b) (b)
Bromination test (a) (a)
(b) (b)
Permanganate test (a) (a)
(b) (b)
Indicate the functional group of the unknown:
(a) Unknown number ______: __________________________
(b) Unknown number ______: __________________________
From its solubility in water, is the unknown of low molecular weight?
(Answer yes, no, or test was indecisive.)
(a) Unknown number ______: __________________________
(b) Unknown number ______: __________________________
3. What is the functional group of an organic compound containing less than five carbon
atoms, and dissolves in water to form a slightly acidic solution?
Draw an equation that represents the reaction.

4. What is the functional group of an organic compound containing less than five carbon
atoms that dissolves in water to form a slightly basic solution?
Draw an equation that represents the reaction.

37
Lecture 11: Identification of Unknown Organic Compounds Dr. Nejib

5. What is the functional group of an organic compound that contains more than five
carbon atoms and insoluble in water but readily dissolves in aqueous basic solution?
Draw an equation to represent this reaction.

6. Draw the reaction between cyclohexene and bromine in CCl4. Indicate the reaction
type.

7. What is the reaction type that occurs between an alkyl halide and alcoholic silver
nitrate?

Do you think that the class of the alkyl halide that affects the reaction rate? Justify?

38
Lecture 12: Synthesis and Purification of Aspirin Dr. Nejib

Synthesis and Purification of Aspirin

I. Objectives

The synthesis and purification of acetyl salicylic acid (aspirin).

II. Material

Erlenmeyer, hotplate, stir bar, spatula, salicylic acid, acetic anhydride, sulfuric acid.

III. Background

Aspirin is one of the oldest drugs, it was discovered by Bayer in 1893. Actually it is one of
the most consumed drugs.

Aspirin is biological active, it is used as an Analgesic (painkiller), Anti-inflammatory

(inhibition of the synthesis of prostaglandins), Antipyretic (fever reducer). But it have
some side effects such as bleeding and gastric irritation.

Reaction

Acid Water Acetic acid Benzoic acid Formic acid Sulfuric acid

pKa 14.0 4.75 4.19 3.75 1

IV. Experimental

In a 50 mL Erlenmeyer flask place 2 g of salicylic acid (solid), 5.0 mL acetic anhydride

(liquid) and 5 drops of H2SO4 (catalytic amount). Heat the mixture for 10 min at 500C, than
cool down to room temperature and add water (crystallization solvent).

Realize the crystallization of the obtained product. Filter the crystals. Measure the melting
point (Mp = 135 0C).

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 Lecture 12: Synthesis and Purification of Aspirin Dr. Nejib

Report

1. Rewrite the reaction scheme.

2. Calculate the molar mass of the salicylic acid.

3. Calculate the number of moles of the salicylic acid.

4. Calculate the molar mass of the acetic anhydride.

5. Calculate the number of moles of acetic anhydride.

6. Compare the number of moles of the salicylic acid and the acetic anhydride.

7. Calculate the molar mass of the acetyl salicylic acid.

8. Calculate the mass of the expected acetyl salicylic acid.

9. The experimental mass of the acetyl salicylic acid is 1.9 g. Calculate the % Yield =
nexp/nth.

40

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