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Nejib Mekni
Faculty of Science of Tunis, University of Tunis Al Manar, Tunisia
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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
The first part is a general introduction to practical organic chemistry and the simple list of
The second part contains the experimental purification and separation of organic compounds
The third part is conserved to the chemical identification tests of different families of organic
phenols, carboxylic acids and salts, amines, amides, imides, urea, anilides amino acids,
compounds.
In the last part the students practice the synthesis and the purification of aspirin as an
Topic Page
P3 Distillation 8
P4 Liquid-Liquid Extraction 12
P5 Identification of Hydrocarbons 13
I. Objectives:
II. Material
1
Lecture 1: List of Organic Experiment Material Dr. Nejib
2
Lecture 1: List of Organic Experiment Material Dr. Nejib
3
Lecture 1: List of Organic Experiment Material Dr. Nejib
4
Lecture 1: List of Organic Experiment Material Dr. Nejib
Report
5
Lecture 2: Crystallization & Sublimation Dr. Nejib
I. Objectives:
III. Background
1. Necessity of purification
Organic compounds are isolated from either natural sources or reaction synthetic
proportion. In synthetic mixture, the target may be the major product, but not pure. The
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
2. Crystallization
compounds.
6
Lecture 2: Crystallization & Sublimation Dr. Nejib
3. Sublimation
Sublimation is the direct physical transformation from of a substance from solid state to
VI. Experimental
7
Lecture 3: Distillation Dr. Nejib
Distillation
I. Objectives
To study the different distillation techniques.
Apparatus: Hot plate, a quick fit round-bottom flask, condenser, Erlenmeyer, funnel,
thermometer, distillation head, fractionation column, receiver adapter.
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).
Scheme 2
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
This method is used for organic compounds, which decompose at or below their boiling
points. e.g. Glycerol.
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
12
Lecture 5: Identification of Hydrocarbons Dr. Nejib
Identification of Hydrocarbons
I. Objectives:
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.
Mix the content of each tube, then observe. What happens when it allowed to settle?
Take notes and save the solutions for the next part.
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.
13
Lecture 5: Identification of Hydrocarbons Dr. Nejib
Mix the contents and observe if there is any appearance change of the contents.
B. Chemical Properties
On six 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.
On six clean and dry test tubes indicate the name of the hydrocarbon to be tested, then
place about 1 mL in each tube.
Wear gloves and carefully add 3 drops of cold, concentrated sulfuric acid in each tube.
4. Unknowns:
Compare the observations of the unknowns to those of the known hydrocarbons and
identify the unknown compounds.
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?
Cyclohexene
Toluene
Compound A
Compound B
Compound C
Chemical properties
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
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.
II. Experimental
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).
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.
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.
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.
17
Lecture 6: Identification of Ketones and Aldehyde Dr. Nejib
Report
Give a conclusion describing the common and the different aldehyde and ketone
characterization tests.
18
Lecture 7: Identification of Alcohols and Phenols Dr. Nejib
I. Objectives
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.
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
III. Experimental
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:
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.
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
Data Table
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.
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.
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.
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
I. Objectives:
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.
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.
When added to a formate and heated, formic acid is liberated and can be detected by its
odor.
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
Chemical properties
Chemical properties
25
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib
Chemical properties
Chemical properties
26
Lecture 8: Identification and reactions of carboxylic acids and salts Dr. Nejib
Chemical properties
Chemical properties
27
Lecture 9: Identification and reactions of amines, amides, imides, urea, anilides and amino acids Dr. Nejib
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.
Chlorpheniramine: Antihistamine helps to relief allergic disorders due to cold, itchy skin, hay
fever, insect bites and stings.
Chlorpromazine: Tranquillizer drug, that acts without inducing sleep, anxiety reliever,
excitement, restlessness or even mental disorder.
VI. Experimental
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).
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.
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.
29
Lecture 10: Identification Test of Carbohydrates and their Classification Dr. Nejib
I. Objectives
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 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:
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).
30
Lecture 10: Identification Test of Carbohydrates and their Classification Dr. Nejib
VI. Experimental
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
Introduction
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.
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 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.
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
Carboxylic acids form insoluble precipitate silver salts, that dissolve in nitric acid solution,
whereas the silver halides do not.
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.
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
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
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
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).
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:
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
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
I. Objectives
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.
Reaction
Acid Water Acetic acid Benzoic acid Formic acid Sulfuric acid
IV. Experimental
Realize the crystallization of the obtained product. Filter the crystals. Measure the melting
point (Mp = 135 0C).
39
Lecture 12: Synthesis and Purification of Aspirin Dr. Nejib
Report
6. Compare the number of moles of the salicylic acid and the acetic anhydride.
9. The experimental mass of the acetyl salicylic acid is 1.9 g. Calculate the % Yield =
nexp/nth.
40