King Abdul Aziz University

Faculty of Science
Department of Chemistry

Fundamental Organic Chemistry

Chem. 230 (Lab Manual)

Edited By:
Abeer Nasser Al-romaizan
Hajer Said Al-orfi
Nazeeha Soliman Al-kayal
Under supervision of:
Dr. Nesreen Said Ismail Ahmed

1431 H

1.
Never work alone in the lab.

2. In the lab area do not touch any equipment, chemicals
,or other










materials .
3.
Do not drink or eat food and gum in the lab.
4. Always work in a well-ventilated area.
5. Read carefully instructions of equipment before use .
6.
Keep hands from face, eyes, mouth, and body while using

chemicals or lab equipment and wash your hands with soap and






water after performing all experimentsK
7. Contact lenses may be not being worn in the lab.
8.
Long hair must be tied back, and clothing must be secured





and shoes
must
completely
cover the foot.
9. A lab coat, gloves should be worn during lab
experiments.
10. If a chemical should splash in your eyes or on your skin,










quickly wash with water for at least 20 minutes.

11. All chemicals in the lab are dangerous because of that do not










taste, or smell any chemicals.
12.
Never return unused chemicals to their original container.
13.
Never remove chemicals or other materials from the lab area.
14. Examine glassware before each use and never use cracked or
dirty






glassware.
15. Do not inter hot glassware in cold water.
16.
Do not operate a hot plate by yourself and take care that hair,











clothing, and hands are a safe
distance from the hot plate at all times.

17. Never look into a container that is being heated.

******************************

Toxic substances

Flammable substances

Explosive substances

harmful substances

oxidizing substances

Corrosive substances

First aid in lab

Chemical or causes

neutralizing wash or treatment

Acids

2M ammonium carbonate

Alkalis

M acetic acid

Bromine

2M ammonia

Hydro fluoric acid

As for acids , then hospital treatment

Phenol

Ethanol , then hospital treatment

Phosphorus

0.1 M copper sulphate

Sodium

Ethanol on a cotton wool pad

Poison swallowed

Plenty of water at once if the patient is conscious

Corrosive poisons

Plenty calcium hydroxide(lime water) as soon as

possible
Gassing

In case of gassing acknowledge of artificial respiration

method
May be required ,and the correct person(s)to summon
should

be listed in the emergency procedure

Cuts

The wound is washed well with cold water, inspected,

And any foreign bodies removed. Then an intersected
cream of certrimide is applied and the affected part
protected with a suitable dressing

Severe bleeding

Firm pressure round the wound, a cover with a pad

And firm bandaging

Electrical mishaps

These are usually avoidable by the correct installation

of equipment

Lab Equipment

Test Tube Brushes

Ring stands

Test Tube Holder

Glass Stir Rod

Test Tube

Test Tube Racks

Spatulas

Litmus Paper

Funnel

Dropper

Conical flask

Beaker

Wash Bottle

Cylinder

Buchner funnel

Buchner flask

Mortar & pistil

Separating funnel

Beaker Tongs

Watch Glass

clamp

burette

Filter paper

Pipet

Florence Flask

Rubber Stoppers

Bunsen Burner

Evaporating Dish

SEPARATION TECHNIQUES

Introduction:
Apure substance contains only one kind of molecule; an impure substance
is a mixture of molecules. When the different molecules of a mixture each behave
in a different way under the conditions of some procedures, the procedure can
result in a separation of the different molecules. The theory of each of the
separation procedures described in this section is presented from the point of view
of the different behavior that can be expected from different molecules under the
experimental conditions.
In this part we will discuss the different types of techniques which used for
separation of organic compounds.

Technique 1

Filtration:
Filtration is a technique used for two main purposes. The first is to remove
solid impurities from a liquid or a solution. The second is to collect a solid
product from the solution from which it was precipitated or crystallized. Two
different kinds of filtration are in general use: gravity filtration and vacuum (or
suction) filtration.

Gravity filtration:
Apiece of filter paper and conical glass funnel to support it are all that are
required for gravity filtration see fig. (1). In order to maximize the rate at which
the liquid flows through the filter paper, the paper should be folded as indicated
in the folded paper is then dropped into the funnel.

********************************

Steps of folded filter paper:

Fig. (1): Gravity filtration

Step 1: Fold the paper in half ,then in quarters ,creasing the folds as you proceed.
However, do not crease the very center of paper (the point),which might become
weakened.

Step 2: Open the quarters to a half- sized piece, and then fold the edges in to the
centerfold

Step 3: Open the paper again to a half-sized piece, then accordion-pleat, using the
existing fold lines as guides. (again, do not crease the center of the paper.)

Step 4: crease the folds (except at the point), then open the filter paper and place
it in an appropriately sized funnel.

Vacuum or suction filtration:

Vacuum, or suction, filtration is more
rapid than gravity filtration. In vacuum or
suction filtration, a partial vacuum is created
below the filter, causing the air pressure on the
surface of the liquid to increase the rate of flow
through the filter paper. A typical apparatus is

Fig. (2): Suction filtration

Illustrated in fig. (2) .A circle of filter paper just large enough to cover
the holes in the bottom of the Hirsch or Buchner funnel should be used.

10

Technique 2
Crystallization:
When a solid organic compound is prepared in the laboratory or isolated
from some natural source, such as leaves, it is almost always impure. A simple
technique for the purification of such a solid compound is crystallization. The
compound is first dissolved in a minimum amount of hot solvent. If insoluble
impurities are present, the hot solution is filtered. If the solution is contaminated
with colored impurities, it may be treated with decolorizing charcoal and filtered.

Crystallization is not the same as precipitation. Precipitation is the rapid

formation of solid material, while crystallization is the slow formation of a
crystalline solid. If a hot saturated solution is cooled too quickly, then the
compound may precipitate instead of crystallizing. A precipitated solute may
contain many impurities trapped in the rapidly formed crystal structure. On the
other hand, when a solution is allowed to crystallize slowly, impurities tend to be
excluded from the crystal structure because the molecules in the crystal lattice are
in equilibrium with the molecules in solution.

Solvents for Crystallization:

The ideal solvent for the crystallization of a particular compound is one that:
(1) Does not react with the compound .
(2) Boils at a temperature that is below the compounds melting point .
(3) Dissolves a moderately large amount of the compound on hot .
11

(4) Dissolves only a small amount of compound on cold .

(5) Is moderately volatile so that the final crystals can be dried readily .
(6) Is nontoxic, nonflammable, and inexpensive.

In addition, impurities should be either highly insoluble in the solvent else highly
soluble, so that they remain in solution during the crystallization.

General guidelines for predicting solubilities based upon the structures of

organic compounds do exist. For example, an alcohol, a compound containing the
hydroxyl (-OH) group as its functional group, may be soluble in water because it
can form hydrogen bonds with water molecules. If an alcohols molecules are
largely hydrocarbon, the alcohol may be insoluble in water, but will probably be
soluble in other alcohols, such as ethanol (CH3CH2OH). Carboxylic acids
(compounds containing CO2H groups) and amines (compounds containing NH2,
N H , or N groups) also can form hydrogen bonds and are also generally soluble
in polar solvents such as alcohols.

Compounds that are largely hydrocarbon in structure are not soluble in

polar solvents because C C and C H bonds are not polar. For these
compounds, we would choose a non polar solvent for example, low-boiling
petroleum ether, which is a mixture of alkanes such as pentane, CH3(CH2)3CH3,
and hexane, CH3(CH2)4CH3. Thus, in choosing crystallization solvents, chemists
generally follow the rule of thumb: like dissolves like.

12

solvent

Bp(OC)

water

100

methanol

65

General use

ethanol

78

General use

acetone

56

General use

ethylacetate

77

General use

dichloromethane

40

General use

Diethyl ether

35

General use

Chloroform

61

General use

toluene

111

Aromatic compound

benzene

80

Aromatic compound

69

hydrocarbons

Hexane(petroleum
ether)

Useful for
Salts amides some
carboxylic acids

Table 1: Some common crystallization solvents

Ideally, a compound to be crystallized should be soluble in the hot solvent,

but insoluble in the cold solvent. When a proper solvent cannot be found, a
chemist may use a solvent pair.

13

Steps in Crystallization:
1) Dissolving the compound. The first step in crystallization is dissolving
the compound in a minimum amount of the appropriate hot solvent in an
Erlenmeyer flask. An Erlenmeyer flask is used instead of a beaker or other
container for several reasons. The solution is less likely to splash out and dust is
less likely to get in.
Safety Note:

Toxic solvents should be heated only in a hood.

2) Filtering insoluble impurities. Filtering a hot, saturated solution

inevitably results in cooling and in evaporation of some of the solvent. Therefore,
a premature crystallization of the compound on the filter paper and in the funnel
may be observed. A few precautions can minimize this premature crystallization.
3) Crystallizing the compound. Cover the flask containing the hot, saturated
solution with a watch glass or inverted beaker to prevent solvent evaporation and
dust contamination.
4) Isolation the crystals. Crystals are separated from their mother liquor by
filtration.

Suggested experiments:
Crystallize one of the following compounds from the indicated solvents:
1) benzoic acid from water .
2) Acetanilide from water .

3) Naphthalene from 95% ethanol .

14

Technique 3

Sublimation:
Sublimation is a process whereby a solid is purified by vaporizing and
condensing it without its going through an intermediate liquid state.
Solid compounds that evaporate (that is, pass directly from the solid phase to the
gaseous phase) are rather rare; solid CO2 (dry ice) is a familiar example of such a
compound. Even though both solids and liquids have vapor pressures at any given
temperature, most solids have very low vapor pressures.
Sublimation can be used to purify some solids just as distillation can be
used to purify liquids. In sublimation, nonvolatile solid impurities remain behind
when the sample evaporates, and condensation of the vapor yields the pure solid
compound. Sublimation has the advantages of being fast and clean because no
solvent is used. Unfortunately, most solid compounds have vapor pressures too
low for purification in this fashion. Also, sublimation is successful only if the
impurities have much lower vapor pressures than that of the substance being
purified.

Atmospheric Sublimation:
The atmospheric sublimation apparatus shown can be used only for a solid
with a relatively high vapor pressure. Place the sample in a filter flask equipped
with a water-cooled cold finger or a test tube filled with ice. Warm the flask on a
hot plate or in a water bath, taking care not to melt the solid. Crystal growth on
the test tube (and on the cooler flask sides) soon occurs. Periodically, cool the

15

apparatus, remove the cold finger or test tube carefully, and scrape the sublimed
crystals into a tared container or onto a watch glass. Determine the melting point
of the sample with a sealed capillary fig. (3).

Fig.(3): atmospheric sublimation

Vacuum Sublimation:
For a vacuum sublimation, choose a side-arm test tube to hold the sample,
and then insert a smaller test tube fitted into a neoprene adapter or large-holed
stopper. Place ice in the inner tube, connect the side arm with heavy-walled
rubber tubing to a trap (preferably chilled in an ice bath) and then to the aspirator.
For an illustration of the trap and a discussion of using the aspirator.
Turn on the aspirator and press the test tubes together to obtain a seal.
Then, warm or heat the outer test tube. When the sublimation is complete, allow
the apparatus to cool before breaking the vacuum. Take care in breaking the

16

vacuum and removing the tube so that the sublimed crystals remain on the tube
until they are scraped off. Fig. (4) .

Fig.(4): Vacuum sublimation

Suggested experiments:
1) Perform an atmospheric sublimation of hexachloroethane .
2) Vacuum sublime naphthalene or caffeine.

Problems:
Which of the following compounds could be subjected to sublimation at
atmospheric pressure?
(a) Compound A:vapor pressure at its melting point=770 mmHg
(b) Compound B:vapor pressure at its melting point=400 mmHg
(c) Compound C:vapor pressure at its melting point=10 mmHg

17

Technique 4

Extraction Using a Separatory Funnel:

Extraction is the separation of a substance from one phase by another
phase. The term is usually used to describe removal of a desired compound from
a solid or liquid mixture by a solvent. In a coffee pot, caffeine and other
compounds are extracted from the ground coffee beans by hot water. Vanilla
extract is made by extracting the compound vanillin from vanilla beans.
In the laboratory, several types of extraction techniques have been
developed. The most common of these is liquid-liquid extraction, or simply
extraction. Extraction is often used as one of the steps in isolation a product of
an organic reaction. After an organic reaction has been carried out, the reaction
mixture usually consists of the reaction solvent and inorganic compounds, as well
as organic products and by-products. In most cases, water is added to the reaction
mixture to dissolve the inorganic compounds. The organic compounds are then
separated from the aqueous mixture by extraction with an organic solvent that is
immiscible with water. The organic compounds dissolve in the extraction solvent
while the inorganic impurities remain dissolved in the water.
The most commonly used device to separate the two immiscible solutions
in an extraction procedure is the separatory funnel. Typically the aqueous
mixture to be extracted is poured into the funnel first, and then the appropriate
extraction solvent is added. The mixture is shaken to mix the extraction solvent
and the aqueous mixture, and then is set aside for a minute or two until the
aqueous and organic layers have separated. The stopcock at the bottom of the
18

separatory funnel allows the bottom layer to be drained into a flask and makes
possible the separation of the two layers fig.(5). The result (ideally) is two
separate solutions: an organic solution (organic compounds dissolved in the
organic extraction solvent), and an inorganic solution (inorganic compounds
dissolved in water). Unfortunately, often the water layer still contains some
dissolved organic material. For this reason, the water layer is usually extracted
one or two more times with fresh solvent to remove more of the organic
compound.
After one or more extractions and separations, the combined organic
solutions are usually extracted with small amounts of fresh water to remove traces
of inorganic acids, bases, or salts; treated with a solid drying agent to remove
traces of water; and then filtered to remove the hydrated drying agent. Finally, the
solvent is evaporated or distilled. The organic product can then be purified by a
technique such as crystallization or distillation.

Fig.(5)

19


Distribution Coefficients:
When a compound is shaken in a separatory funnel with two immiscible
solvents, such as water and diethyl ether (CH3CH2OCH2CH3), the compound
distributes itself between the two solvents. Some dissolves in the water and some
in the ether. How much solute dissolves in each phase depends on the solubility
of the solute in each solvent. The ratio of the concentrations of the solute in each
solvent at a particular temperature is a constant called the distribution

coefficient or partition coefficient (K).

Concentration in solvent2
K = --------------------------------Concentration in solvent1
Where solvent1 and solvent2 are immiscible liquids.

Steps in extraction:
1) Preparation of the separatory funnel.
2) Adding the liquids. Be sure the stopcock is closed.
Safety Note:
Never add a volatile solvent to a warm solution. If you are using a
flammable solvent, make sure there are no flames in the vicinity!
3) Mixing the layers.
Insert the stopper and, holding the stopper in place with one hand, pick up the
separatory funnel and invert it. Immediately open the stopcock with your other
hand to vent solvent fumes or carbon dioxide. Swirl the separatory funnel gently
to further drive off solvent vapors or gases.

20

After venting, close the stopcock, gently shake or swirl the mixture in the
inverted funnel, then re-vent the fumes. If excessive pressure build-up is not
observed, the separatory funnel and its contents may be shaken up and down
vigorously in a somewhat circular motion for 2-3 minutes so that the layers are
thoroughly mixed. Vent the stopcock several times during the shaking period.
After completing the shaking, vent the stopcock one last time. Place a large
Erlenmeyer flask under the stem of the separatory funnel in case the stopcock
should develop a leak. Allow the separatory funnel to sit until the layers have
separated.

4)

Separation the layers. Before proceeding, make sure the stopper has

been removed. (It is difficult to drain the lower layer from a stoppered
funnel. Because a vacuum is created in the top portion of the funnel.)

21

5) Cleaning the separatory funnel.

Suggested experiments:
1) Separate a mixture of 2-naphthol and benzoic acid by an ether-bicarbonate
extraction.
2) Separate a mixture of benzoic acid, p-chloroaniline, and naphthalene using
dichloromethane as the organic solvent.

Technique 5
Chromatograph:
Chromatography is a general term that refers to a number of related
techniques used for analyzing, identifying, or separating mixtures of compounds.
All chromatographic techniques have one principle in common liquid or
gaseous solution of the sample, called the mobile phase, is passed (moved)
through an adsorbent, called the stationary phase. The different compounds in
the sample move through the adsorbent at different rates because of physical
differences (such as vapor pressure)and because of different interactions
(adsorptivities, solubilities. etc.)with the stationary phase.

22

1- Column Chromatography
Column chromatography is used to separate mixtures of compounds.
In this technique, a vertical glass column is packed with a polar adsorbent along
with a solvent. The sample is added to the top of the column; then, additional
solvent is passed through the column to wash the components of the sample, one
by one (ideally), down through the adsorbent to the outlet.
The sample on the column is subjected to two opposing forces: the solvent
dissolving it and the adsorbent adsorbing it. The dissolving and the adsorption
constitute an equilibrium process, with some sample molecules being adsorbed
and others leaving the adsorbent to be moved along with the solvent, only to be
re-adsorbed farther down the column. A compound (usually a non polar one) that
is highly soluble in the solvent, but not adsorbed very strongly, moves through
the column relatively rapidly. On the other hand, a compound (usually a more
polar compound) that is more highly attracted to the adsorbent moves through the
column more slowly.
Because of the differences in the rates at which compounds move through
the column of adsorbent, a mixture of compounds is separated into bands .

23

Fig.(6): Column chromatography

(1) The sample has just started to move into column of adsorbent .
(2) and (3) as more solvent is passed through the column, the sample moves down
and begins to separate into its components because of differences in attraction to
the adsorbent and solvent.
(4) The faster-moving compound is eluted into a flask.

Suggested experiments:

1- Separatec a mixture of permanganate and dichromate on silica gel column.

2- Isolate and separate plant pigments from extracts of carrots, tomatoes ,etc.
3- Separate o-and p-nitro anilines.

24

2- Thin-Layer Chromatography(TLC)
Thin-layer chromatography is a variation of column chromatography.
Instead of a column, a strip of glass or plastic is coated on one side with a thin
layer of alumina or silica gel.
In a TLC analysis, about 10 L of a solution of the substance to be tested is
placed (spotted) in a single spot near one end of the plate, using a micro
capillary. The plate is developed by placing it in a jar with a small amount of
solvent. Shows a TLC plate in a developing jar. The solvent rises up the plate by
capillary action, carrying the components of the sample with it. Different
compounds in the sample are carried different distances up the plate because of
variations in their adsorption on the adsorbent coating. If several components are
present in a sample, a column of spots is seen on the developed plate, with the
more polar compounds toward the bottom of the plate and the less polar
compounds toward the top.
As an analytical tool, TLC has a number of advantages: it is simple, quick,
inexpensive, and requires only small amounts of sample. Tlc is generally used as
a qualitative analytical technique, such as checking the purity of a compound or
determining the number of components in a mixture. We can use TLC to follow
the course of a reaction by checking the disappearance of starting material.

25

Fig.(7):Thin-layer Chromatography.

The Rf Value:
The distance that the spot of a particular compound moves up the plate
relative to the distance moved by the solvent front is called the retention factor,
distance traveled by the compound

Rf

= -------------------------------------------distance traveled by the solvent

Equipment for TLC:

TLC sheets and plates. Commercial TLC sheets are coated with silica gel
(SiO2) or alumina (Al2O3). Choose the type that gives the best separation for your
particular mixture.
If commercial TLC sheets are unavailable, plates can be made from
microscope slides and a slurry of 1g aluminum oxide G or silica gel G and 2mL

26

chloroform (CAUTION : toxic). A 2 : 1 mixture by volume of dichloromethane

and methanol (also toxic) may be substituted for the chloroform.
Dip two slides, back-to-back, in the slurry. Allow the excess slurry to drain.
Separate the slides and allow them to dry in a fume hood. Then wipe excess
adsorbent from the backs and edges of the slides. Making satisfactory plates
requires practice; therefore, prepare a number of plates and select the most evenly
coated ones. Microscope slide plates are shorter than commercial sheets;
consequently, the separation of components is not as clean.
Pipets. Commercial 10- L disposable pipets are best for spotting.
If commercial pipets are not available, draw out some soft glass tubing or
melting-point capillary tubes in a flame. The diameter of the pipet should be
about 1/4 of the diameter of a melting-point capillary.
Developing jars. Developing chambers with the proper solvent system may
be prepared in advance and kept in the fume hood. Any tall jar, such as an instant
coffee jar or mason jar, with a lid or screw top, may be used for developing a
TLC plate. The jar should be narrow enough to hold the plate upright inside,
without the danger of its falling over. The lid of the jar should be impervious to
solvent fumes.

Suggested experiments:

1- Analyze a mixture of amino acids.

2- Analyze a mixture of ink.

27

Problems:
1- Calculate the Rf values for the following compounds:
(a) Spot,5 cm; solvent front, 20cm
(b) Spot,3 cm; solvent front,12 cm
(c) Spot,9.8cm;solvent front,12cm

Technique 6
Distillation:
Distillation is a general technique used for removing a solvent, purifying a
liquid or separation the components of a liquid mixture. In distillation, liquid is
vaporized by boiling, then condensed back to a liquid, called the distillate or
condensate, and collected in a separate flask.

Types of distillation:
1-Fractional distillation
Miscible liquids are much more difficult to separate. Mixtures of
miscible liquids can be separated by fractional distillation. It will provide the
boiling points of the liquids are not too close.
If we want to separate a mixture of ethanol and water. The diagram
below is suitable for this process. The fractionating column is packed with glass

28

bead. It provides a large surface area for vaporization and condensation of the
liquid mixture.
Ethanol is more volatile than water, since it has a lower boiling point
(78oC). The vapor rises up the fractionating column when the mixture is heated.
Because ethanol is more volatile, the vapor contains more ethanol. The hot vapor
condenses upon touching the cold glass beads. There is a continues rise of hot
vapor up the fractionating column at the same time. Hot vapor will make the
condensed vapor boils again. It will contain more and more ethanol as the vapor
rises up to the fractionating column.

Fig.(8): Fractional distillation

29

The above process is to be repeated many times before the vapor consists
only pure ethanol. During the process the escaping vapor is measured by a
thermometer of the fractionating column. The temperature will remain steady for
some time and will then rise quickly and become pure ethanol.
When the ethanol has boiled off completely, the escaping vapor will consist of
pure water only.
Generally, for fractional distillation to work best, the difference in boiling points
of liquids in the mixture should be greater than 10C. The separation will not be
complete if it is not.
Fractional distillation is used in industry to separate oxygen and nitrogen from
liquid air. In whisky production it is used to increase ethanol.

2-Vacuum distillation
Vacuum distillation is a method of distillation whereby the pressure
above the liquid mixture to be distilled is reduced to less than its vapor pressure
(usually less than atmospheric pressure) causing evaporation of the most volatile
liquid(s) (those with the lowest boiling points). This distillation method works on
the principle that boiling occurs when the vapor pressure of a liquid exceeds the
ambient pressure. Vacuum distillation is used with or without heating the solution

30

3-Steam distillation
Steam distillation is a special type of distillation (a separation process)
for temperature sensitive materials like natural aromatic compounds.
Many organic compounds tend to decompose at high sustained temperatures.
Separation by normal distillation would then not be an option, so water or steam
is introduced into the distillation apparatus. By adding water or steam, the boiling
points of the compounds are depressed, allowing them to evaporate at lower
temperatures, preferably below the temperatures at which the deterioration of the
material becomes appreciable. If the substances to be distilled are very sensitive
to heat, steam distillation can also be combined with vacuum distillation. After
distillation the vapors are condensed as usual, usually yielding a two-phase
system of water and the organic compounds, allowing for simple separation.

Fig.(9): Steam distillation

31

When a mixture of two practically immiscible liquids is heated while being

agitated to expose the surfaces of both the liquids to the vapor phase, each
constituent independently exerts its own vapor pressure as a function of
temperature as if the other constituent were not present. Consequently, the vapor
pressure of the whole system increases. Boiling begins when the sum of the
partial pressures of the two immiscible liquids just exceeds the atmospheric
pressure (approximately 101 kPa at sea level). In this way, many organic
compounds insoluble in water can be purified at a temperature well below the
point at which decomposition occurs. For example, the boiling point of
bromobenzene is 156 C and the boiling point of water is 100 C, but a mixture of
the two boils at 95 C. Thus, bromobenzene can be easily distilled at a
temperature 61 C below its normal boiling point.
Steam distillation is employed in the manufacture of essential oils, for
instance, perfumes. In this method, steam is passed through the plant material
containing the desired oils. It is also employed in the synthetic procedures of
complex organic compounds. Eucalyptus oil and orange oil are obtained by this
method on the industrial scale.

***********************************************

32

HYDROCARBONS

Compound containing only Carbon and Hydrogen and classified into:

Alkanes R-H
Alkanes are saturated hydrocarbon compounds.
Chemically, alkanes are unreactive compounds because they are
saturated compounds , all the bonds are strong sigma bonds.
The general formula of alkanes is CnH2n+2
Example: Cyclohexane

Test

Observation

Result

The orange color of

It is saturated compound

1-Bromination Test :
In two test tubes put 1ml of
cyclohexane +1ml of bromine
and shake both well.

bromine is not disappears formed via displacement

from the first tube.

Protect one from light and

expose the second to sun light

The color of the second

reaction by the effect of

sunlight (1).

tube disappears.

for 15 min.

Br

+
Cyclohexane

Br2

Bromine

hv

.........(1)

1-Bromocyclohexane

33

2- Potassium Permanganate Test:

In a test tube put 1ml of
cyclohexane + few drops of dilute

The violet color of the

It is saturated

KMnO4 dose not

compound.

acidic KMnO4 with shaking.

changes.

Alkenes R-CH=CH-R
Alkenes are unsaturated hydrocarbon compounds containing double bond .
They are reactive compounds because they contains weak bond .
The general formula of alkenes is CnH2n

Example: Cyclohexene

Preparation of cyclohexene:

Put 3ml of cyclohexanol in dry test tube + 0.5 ml of conc. H2SO4 (2) and
then perform the following tests:
OH
H2SO4 conc.

Cyclohexanol

Cyclohexene

34

H2O

..(2)

Test

Observation

Result

In a test tube put 1ml of

The orange color of

It is unsaturated

cyclohexene + drops of

bromine disappears

compound (3).

1-Bromination Test :

bromine.

immediately.
Br
Br

Br2

...........(3)
1,2-Dibromocyclohexane

2-Potassium Permanganate
Test :
In a test tube put 1ml of
cyclohexene + few drops of
dilute acidic KMnO4 then

The violet color of the

It is unsaturated

KMnO4 disappears

compound (4).

immediately

shake well .
OH
OH
1) 2KMnO4

2) 2H2O
Cyclohexene

MnO2

2 KOH

1,2 - Dihydroxy-cyclohexane

35

...(4)

Alkynes (Acetylenes)
Alkynes are unsaturated hydrocarbon compounds containing triple

bond .
The alkynes are also reactive compounds because they contains

weak bonds .
The general formula of alkynes is CnH2n-2
Example: Acetylenes

CH

HC

Preparation of Acetylene:

Acetylene gas prepared by adding water to calcium carbide CaC2 (5)

Ca

2 H2O
H

Ca(OH)2

..... (5) (5)

Procedure:
Put 0.25 gm from calcium carbide in dry test tube add 1ml of
water and note the evolution of acetylene gas, perform the following
experiments on it:

36

Test

1-Bromination Test :

Observation

Result

The orange color of

It is unsaturated

Pass the acetylene gas on the test the bromine disappears

tube contains bromine.

compound (6).

Immediately.
Br

Br
CH

HC

Br 2

CH

HC
Br

Br 2

HC

Br

CH
Br

Br

(6)
2- Potassium Permanganate
Test :
Pass the acetylene gas on the test
tube contains dilute acidic
KMnO4 with shaking.
3- Pass the acetylene gas on the

The violet color of the

It is unsaturated

KMnO4 disappears

compound.

immediately .
White precipitate

The white precipitate

forms.

is Silver acetylide (7).

test tube contains ammonical

silver nitrate.
HC

CH

2 Ag +

Ag

Ag

Silver acetylide

37

2 H+

(7)

AROMATIC HYDROCARBONS

Examples on Aromatic hydrocarbons:

CH3

Benzene

Toluene

The most characteristic reactions for aromatic hydrocarbons are:

1) Nitration reaction
2) Sulphonation reaction

1-Benzene
Benzene is a colorless liquid , immiscible in water but miscible in all organic
solvent, flammable and burned by heavy smoked yellow flame which indicate
that it rich with carbon .

Test

Observation

Result

1-Nitration Test :
In a test tube put 1ml of
conc.HNO3 acid + 1ml of conc.

Yellow oily layer

The yellow oily layer

H2SO4 acid + 0.5ml of benzene

will be separated

is Nitro benzene (8).

then pour into beaker contains cold

water .

38

NO2
HNO3Conc.

H2SO4 Conc.

H2O

(8)

Nitrobenzene
CH3

2-Toluene
Toluene is a color less liquid , the boiling point is 110C immiscible in water but
miscible in organic solvent behave like benzene on burning .

Test

Observation

Result

1-Nitration Test :
In a test tube put 1ml of

Yellow oily layer will The yellow oily layer is

conc.HNO3 acid + 1ml of conc.

be separated

o-Nitrotoluene

H2SO4 acid + 0.5ml of Toluene

& p-Nitrotoluene (9).

then pour into beaker contains

cold water .

CH3

CH3
HNO3 Conc.

CH3
NO2

.(9)

H2SO4 Conc.

NO2

o-Nitrotoluene

39

p-Nitrotoluene

ALCOHOLS COMPOUNDS
R-OH

Alcohols are compounds contains one or more hydroxyl groups (OH)

Alcohols divided according to the type of carbon atom attached to the
hydroxyl group in the molecule to Primary, Secondary& Tertiary alcohols.

Oxidation test:
It was found that Primary alcohols oxidizing to aldehyde the
Secondary alcohols oxidizing to ketone, but tertiary alcohols not
oxidized according to the following equations.
O

O
[O]

[O]

RCH2OH

Primary alcohol

aldehyde

[O]

Secondary alcohol

R3COH

OH

carboxylic acid

O
R2CHOH

Ketone

[O]
No reaction

Tertiary alcohol

40

1-Methanol

CH3OH

Methyl alcohol is colorless liquid , have characteristic odor , miscible in water ,

toxic , burned by blue flame .

Test

Observation

Result

The orange color

The green color is chromium

of the solution

sulphate Cr2(SO4 )3 which

changes to green.

formed due to the oxidation of

1-Oxidation Reaction:
In a test tube put 1 ml of methanol
+1ml of potassium dichromate
K2Cr2O7 + drops of conc. sulphuric
acid .

methanol to Formaldehyde (10).

O
3H

K2Cr2O7 + 4 H2SO4 + 3 CH3OH

H + K2SO4 + Cr2(SO4)3 + 7 H2O

... (10)
2-Esterification :
In a test tube put 1ml of methanol

Vix (oil of winter

The product is

+ 0.5 gm of salicylic acid + drops

green ) odor

methyl salicylate (11).

of conc. H2SO4 & heat in water

appear.

bath for 3 min. then cool and pour

the content of the test tube into
beaker contains Na2CO3 .
COOH
OH

CH3OH

H2SO4
Conc.

COOCH3
OH

methyl salicylate

41

H2O

(11)

2-Ethanol

CH3CH2OH

Ethyl alcohol is colorless liquid , have characteristic odor , miscible in water ,

toxic , burned by colorless flame .

Test

Observation

Result

In a test tube put 1ml of ethanol

The orange color

The green color is chromium

+1ml of potassium dichromate

of the solution

sulphate Cr2(SO4 )3 which

changes to green.

formed due to the oxidation of

1-Oxidation Reaction:

K2Cr2O7 + drops of conc. sulphuric

acid .

ethanol to acetaldehyde (12 )

O

K2Cr2O7 + 4 H2SO4 + 3 CH3CH2OH

3 CH3

H + K2SO4 + Cr2(SO4)3+ 7H2O

chromium sulphate

(12)

2-Esterification :
In a test tube put 1ml of ethanol
+ 0.5 gm of sodium acetate

Fruity odor appears

The product is

(apple odor) .

Ethyl acetate (13) .

+ drops of conc. H2SO4 & heat in

water bath for 3 min. then cool and
pour the content of the test tube into
beaker contains Na2CO3 solution .

42

CH3COONa + CH3CH2OH

H2SO4 conc.

CH3COOCH2CH3 + NaOH

..(13)

Ethyl acetate

3-Iodoforms Test :
In a test tube put 1ml of ethanol
+ 3ml of iodine solution & heat in

Yellow ppt.

The yellow ppt. is Iodoform

water bath for 3 min. then cool &

formed.

CHI3 (14) .

add NaOH drop wise till the color is

straw yellow a pale yellowish ppt. of
iodoform is produced.
O

O
[O]
CH3CH2OH

CH3

3 I2
- 3 HI

CI3

NaOH
C
Iodal

43

CHI3 + HCOONa
Iodoform

...(14)

CH2

3-Glycerol

OH

CH

OH

CH2

OH

Glycerol is a colorless viscous liquid, melted at 10 C, miscible in water and

alcohol and has a sweet taste.
The most characteristic test for glycerol is the Borax test.

Test

Observation

Result

The color

The disappearance of (ph.ph)

1-Borax Test :
In a test tube add 2 drops of
phenolphthalein (ph.ph) to

disappears and is

color on cold due to the

dilute borax solution then a pink restored on heating. formation of strong acid and
color is produced Add few

by heating this acid

drops of glycerol & shake.

dissociated into boric acid

& glycerol , the pink color
returned (15) .

Na2B4O7

CH2
CH
CH2

OH
OH
OH

Glycerol

7H2O

2 NaOH

4 H3BO3
CH2

CH

CH2

OH

HO
B

OH

HO

Cold
Hot

Boric acid

O
H+

Strong acid
{ Acidic Media } colourless

{ Basic Media } Pink colour

44

H2O

...(15 )

CARBONYL COMPOUND

1-Aldehydes

2-Ketones

Aldehydes are produced by oxidation of primary alcohols,

Ketones produced from oxidation of secondary alcohols.
Examples:

H3C

O
H

Acetaldehyde

H3C

CH3

Acetone

****************************

45

C
Benzaldehyde

1-Formaldehyde

Formaldehyde is a gas and is available as aqueous solution which has a

characteristic pungent odor.

Test

Observation

Result

Yellow precipitate is

The ppt. is hydrazone

formed.

derivative this prove that

2,4-dinitrophenyl hydrazine test:

In a test tube put 1 ml of HCHO
+1ml of 2,4- dinitro phenyl
hydrazine .

formaldehyde contain
carbonyl group (16) .
H

O2N

NHNH2

- H2O

H
O2N

C
H

H2O

NO2

NO2

2,4-dinitrophenyl- hydrazine

NHN

Formaldehyde

Hydrazone derivative

(16)

2-Schiffs Reagent:
In a test tube put 1 ml of HCHO

Magenta color

+ drops of Schiffs reagent.

appears rapidly.

Its Formaldehyde

3-Reduction Reaction
A)- Ammonical AgNO3

A silver mirror is

Due to Oxidation of

In a test tube put 1ml of HCHO

deposited on the inner

HCHO to formic acid

+3 ml of amm. AgNO3 & heat in

wall of the test tube.

& reduction for Ag2O to

water bath for 3 min.

Ag metal (17).

46

O
H

Ag2O

formaldehyde

OH

2Ag

formic acid

....(17)

silver metal

B)- Fehling's solution

In a test tube put 1ml of HCHO

Solution turns green

Due to Oxidation of

+1ml of Fehling solution A +1ml

and after some time

HCHO to formic acid

of Fehling solution B & then heat

a red ppt.

& reduction for CuO to

on water bath for 3 min.

Cu2O (red ppt.) (18)

O
H

O
H

2CuO

formaldehyde

OH

Cu2O

....(18)

formic acid

4-Resorcinol Test :
In a test tube put 1ml of HCHO

Red violet ring is

The aldehyde is

+ drops of resorcinol +1ml of

formed & white ppt.

Formaldehyde.

H2SO4 conc. added down the side

appears over the ring.

of the test tube.

47

O
2-Acetaldehyde

CH3

It is a liquid b.p 21 generally used in aqueous solution which has also

characteristic odor , miscible in water ,alcohol and ether .

Test

Observation

The ppt. is hydrazone

1-2,4-dinitrophenyl hydrazine test :

In a test tube put 1ml of CH3CHO
+1ml of 2,4-dinitro phenyl hydrazine

Result

Yellow precipitate

derivative this prove

is formed.

that acetaldehyde
contain carbonyl group

2-Schiffs Reagent:
In a test tube put 1 ml of CH3CHO

Magenta Violet
color appears

+ drops of Schiffs reagent.

Its Acetaldeyde

rapidly.

3-Reduction Reaction
A)- Ammonical AgNO3

A silver mirror is

Due to Oxidation of

In a test tube put 1ml of CH3CHO

deposited on the

CH3CHO to acetic acid

+ 3 ml of amm. AgNO3 & heat in

inner wall of the

& reduction for Ag2O to

test tube.

Ag metal .

In a test tube put 1ml of CH3CHO

Solution turns

Due to Oxidation of

+1ml of Fehling solution A +1ml of

green and after

CH3CHO to acetic acid

Fehling solution B & then heat on

some time

& reduction for CuO to

water bath for 3 min .

a red ppt.

Cu2O (red ppt.)

water bath for 3 min.

B)- Fehling's solution

48

4-Aldol Condensation
In a test tube put 1ml of CH3CHO

Colloidal Yellow

The precipitate is

ppt. is formed.

2-butenal (19).

+3ml of NaOH then boiling 2 min.

NaOH

2 CH3CHO

CH3CH
CH
2-butenal

CHO

(19)

5-Iodoform Test :
In the test tube put 1ml of CH3CHO

Yellow ppt. is

The Yellow ppt. is

+ 3ml of Iodine &heat on water bath

formed

Iodoform CHI3 (20)

for 3 min. then cool & add drop wise

of NaOH until the iodine color
disappear
O

O
CH3

3 I2
- 3 HI

NaOH

CI3

C H
Iodal

CHI3 + HCOONa

...(20)

Iodoform

6-Sodium nitroprusside Test:

In the test tube put 1ml of CH3CHO

Dark red color

+ 0.5 ml of Sodium nitroprusside then

put drops of NaOH with shaking .

49

Its Acetaldehyde

3-Benzaldehyde

Benzaldehyde is colorless liquid if pure with the odor of bitter almonds

immiscible with water & sinks in it but miscible with alcohol .
Test

Observation

Result

1-2,4-dinitrophenyl hydrazine test:

Dark yellow

The ppt. is hydrazone

In a test tube put 1ml of benzaldehyde

precipitate is

derivative this prove

+1ml of 2,4-dinitro phenyl hydrazine .

formed.

that benzaldehyde
contain carbonyl group

magenta color

2-Schiffs Reagent:
In a test tube put 1 ml of benzaldehyde

appears after some

+ drops of Schiffs reagent.

time and vigorous

Its benzaldehyde

shaking .

3-Reduction Reaction

A silver mirror is

Due to Oxidation of

A ) Ammonical AgNO3

deposited on the

benzaldehyde to

In a test tube put 1ml of benzaldehyde

inner wall of the

benzoic acid

+ 3 ml of amm. AgNO3 & heat in water

test tube by gentle

& reduction for

heating.

Ag2O to Ag metal .

bath for 3 min.

50

B) Fehling's solution

Solution turns

Due to Oxidation of

In a test tube put 1ml of benzaldehyde

green and after

benzaldehyde to

+1ml of Fehling solution A +1ml of

some time

benzoic acid &

Fehling solution B & then heat on water

a red ppt.

reduction for CuO to

bath for 3 min

Cu2O (red ppt.) .

4-Cannizzaro Reaction
In a test tube put 1ml of benzaldehyde

White ppt. is

The white ppt. is

+ 3ml NaOH 30% & heat on water bath

formed

benzoic acid (21).

for 3 min. then add drops of H2O and

drops of HCl Conc.
COONa

CH2OH

O
C

NaOH

+
Sodium benzoate Benzyl alcohol

COOH

NaCl

HCl

+
White ppt.

51

......(21)

O
CH3 C

4-Acetone

CH3

Acetone is colorless liquid with a characteristic odor, inflammable, miscible with

water, alcohol & ether .

Test

Observation

Result

1-2,4-dinitrophenyl hydrazine test:

Yellow precipitate is

The ppt. is hydrazone

formed.

derivative this prove that

In a test tube put 1ml of acetone

+1ml of 2,4-dinitrophenylhydrazine

acetone contain carbonyl

group .

2-Schiffs Reagent:
In a test tube put 1 ml of acetone

magenta color appears

Acetone is ketone not

+ drops of Schiffs reagent.

slowly, need long time

aldehyde .

In the test tube put 1ml of acetone

Yellow ppt. is formed

The Yellow ppt. is

+3ml of Iodine then add drops of

on cold.

Iodoform CHI3 (22) .

3-Iodoform Test :

NaOH immediately.
O
CH3

CH3

3 I2
- 3 HI

NaOH

CH3COC I3

Iodal

C HI3

Iodoform

CH3COONa

(22)

4 - Sodium nitroprusside Test:

In the test tube put 1ml of acetone

Deep Red Solution

+ 0.5 ml of Sodium nitroprusside then

Formed.

Its Acetone
characteristic test for
(- COCH3).

put drops of NaOH with shaking.

52

CARBOXYLIC ACIDS
Liquid organic acids

All acids contains carboxyl group COOH.

Acids divided into two major classes.
Aliphatic acid and aromatic acid. Also can divide into different types
according to number of carboxylic group in the molecules or according to type
or number of another group attached to acid molecules.

Aliphatic acids :
HCOOH
formic acid

COOH

CH3COOH

COOH

Acetic acid

oxalic acid

HO CH COOH
HO CH COOH
Tartaric acid

Aromatic acid:
COOH

COOH
OH

Benzoic acid

Salicylic acid

Neutral Solution of acid::

N.S of acid is the ammonium salt for acid
RCOOH + NH4OH

RCOONH4 + H2O

Some chemical reactions used to identify such acids carried out on its N.S.

53

To Make Neutral Solution N.S.:

Add to the acid aqueous NH3 (NH4OH) till the solution is just alkaline to litmus.
Boil the solution until the evolution of NH3 gas ceases ( this can be ensured by
exposing a red litmus paper to vapor ) .

 General properties for acids :

1. Soluble in sodium hydroxide.
2. Soluble in sodium carbonate or sodium bicarbonate with eff. of CO2 gas.
3. When heated the acids with sodalime CO2 evolved.
COOH
CaO/NaOH
heat

COOH
OH

+ CO2

OH
CaO/NaOH

+ CO2

heat

1. Acids react with alcohol in present of conc. H2SO4 produce ester with specific
odor .

RCOOH

'
ROH

H2SO4

'
RCOOR

'

H2O

2. N.S of acid with ferric chloride solution. Gives specific color for each acid.
3. Acids Solution turns litmus paper to red.

54

1- Formic acids HCOOH

Formic acid is a colorless liquid, immiscible in water, alcohol and ether.
It has a pungent irritating odor. All formate as soluble except those of Ag, Hg, and
some basic salt.

Test

1-Acidity test:
1ml of acid +2ml of NaHCO3

HCOOH + NaHCO3

Observation

Result

CO2 evolves with

Compound is carboxylic

effervescence.

acid (23).

HCOONa

H2O

Sodium formate
2-Ferric chloride test:
1ml of N.S. of acid + few drops

CO2

(23)

Red color turned with

Red color is ferric format

heating into Brown ppt.

(HCOO)3 Fe and brown ppt.

of FeCl3 .

is basic ferric formate

(HCOO) Fe (OH) 2 (24).

3 HCOONH4 + FeCl3
(HCOO)3Fe

(HCOO)3Fe + 3 NH4Cl

2 H2O

(HCOO)Fe(OH)2
basic ferric formate

(24)

3-Mercury chloride test:

White ppt. immediately

White ppt. is Hg2Cl2

1ml of N.S. of acids +1ml

appear &change to gray

& the gray ppt. is

ppt. with boiling .

metallic Hg (25).

HgCl2 & added excess then boil

55

2 HCOOH4 + 2 Hg2Cl2

Hg2Cl2 + CO + CO2 + 2 NH Cl + H O
2
4

Hg2Cl2 + HCOONH4

2 Hg + CO + CO2 + 2 NH4Cl + H2O2

4-Permanganate test:

..(25)

The color of KMnO4

Oxidation for formic acid

will disappear .

(26).

1ml of warm acids + drops of

KMnO4 .

HCOOH

(O)

CO 2 +

H2O
(26)

5-Esterification test:
In dry test tube but 1ml of acids

Pleasant odor is

The odor due to the

+1ml of ethanol +1ml of conc.

detected

formation Ethyl formate

H2SO4 & then heat in water

HCOOC2HS (27)

bath for 3 min., then pour into

beaker contain Na2CO3
solution .

HCOOH + CH3CH2OH

H2SO4

HCOOCH2CH3 + H2O
Ethyl formate

56

(27)

2- Acetic acid

CH3COOH

Acetic acid is a colorless liquid, with a penetrating odor of vinegar , miscible with
H2O, alcohol and ether . Most of its salts soluble with water except those of Ag,
mercurous and basic salts.

Test

1-Acidity test:
1ml of acid + 2ml of NaHCO3.

CH3COOH + NaHCO3

Observation

Result

CO2 evolves with

Acetic acid is carboxylic

effervescence.

acid (28).

CH3COONa + H2O + CO2

Sodium acetate

2-Ferric chloride test :

1ml of N.S. of acid + few drops
of FeCl3.

(28)

Red color

Red color is Ferric acetate

turn with heating

(CH3COO)3 Fe and brown

to brown ppt.

ppt. is basic ferric acetate

(CH3COO) Fe (OH)2 (29)

3 CH3COONH4
(CH3COO)3Fe

FeCl3
2H2O

(CH3COO)3Fe

+ 3NH4Cl

(CH3COO)Fe(OH2)
Basic ferric acetate
(29)

57

White ppt. Change to

Confirmatory test for

1ml of N.S. of acids +1ml of

yellow ppt. with

acetic acid.

HgCl2 & added excess then

boiling.

3-Mercury chloride test

boil .
4-Permanganate test:1ml of warm acid + drops of
KMnO4 .

The color will not

No oxidation for acetic

disappear .

acid occur.

apple odor

This odor characteristic

5-Esterification test:
In dry test tube put 1ml of

for Ethyl acetate

acids +1ml of ethanol

+1ml of conc. H2SO4 & heat

CH3COOC2H5 (30) .

in water bath then pour into

beaker contain Na2CO3
solution .

CH3COOH + CH3CH2OH

H2SO4

CH3COOCH2CH3 + H2O
Ethyl acetate

58

(30)

3-Lactic acid

CH3CH(OH)COOH

Is light yellow color liquid , frozen at 110C miscible with water and
alcohols .
Test

Observation

1-Acidity test:

Result

CO2 evolves with

Lactic acid is from

effervescence.

carboxylic acid .

1ml of acid +2ml of NaHCO3.

CH3 CH COONa + CO 2 + H2O

OH

CH3 CH COOH + NaHCO3

OH

Sodium lactate

(31)

2-Ferric chloride test:

The acid is lactic acid

1ml of N.S. of acid+ few drops No change for FeCl3

color.

of FeCl3.

specific test for lactic acid

3-Iodoform test:
1ml of acid + 3ml of iodine then
add NaOH with shaking

Yellow ppt. is

Yellow ppt. is Iodoform

formed on cold .

CHI3 (32) .

OH
[O]
CH3CHCOOH

CH3CCOOH

O
3I2
-3HI

CI3CCOOH

2NaOH

CHI3

COONa
COONa

Iodoform

(32)
4-Permanganate test:1ml of warm acids + drops of
KMnO4 .

The color of

oxidation for hydroxyl

KMnO4 disappear .

group in lactic acid .

59

Scheme for liquid organics

First: 1ml of unknown + drops of Schiffs reagent

Violet color

- Ve

Unknown is Formaldehyde or Acetaldehyde

Unknown is not aldehyde

 Confirmatory test for Formaldehyde

Go to second step

and Acetaldehyde

Second: 1ml of unknown +1ml of Na2CO3 solution

CO2 evolves with effervescence

- Ve

Unknown is carboxylic acid

Go to the Third step

1ml of N.S. for acid + drops of FeCl3

Red color turn by heating to

- Ve

brown ppt. unknown is formic

Lactic acid

acid or acetic acid

 Confirmatory test for formic
and acetic acid
60

Third: 1ml of unknown + 3ml of iodine then add NaOH gradually by

continuous shaking

- Ve

Yellow ppt. from Idoform

Go to the fourth step

Unknown is Acetone

Forth: 1ml of unknown + 3ml of iodine and heated in water bath for 3min.
then cool and add NaOH gradually by continuous shaking

Yellow ppt. from Idoform

- Ve

unknown is Ethanol

Go to the fifth step

Fifth: 2ml of borax solution + drops of Ph.Ph + 1ml of unknown

Pink color disappears on cold

- Ve

and returned by heating

Go to the sixth step

unknown is Glycerol

61

Sixth:
In dry test tube put 1ml of unknown + 0.5gm of salicylic acid + 2drop of conc.
H2SO4 and heated in water bath for 3 min. then pour the content into beaker
containing Na2CO3 solution.
Vix smell appear ( Methyl salicylate ) unknown is methanol .

Neutral Solution N.S.:

Add to the acid aqueous NH3 ( NH4OH) till the solution is just alkaline to litmus
Boil the solution until the evolution of NH3 gas ceases ( this can be ensured by
exposing a red litmus paper to vapor) .
****************************

Experiment to differentiate between formic and acetic acid :

Test

Formic acid

Acetic acid

1ml of N.S. of acid +1ml

White ppt. immediately

White ppt. change to

of HgCl2 & added excess

appear & change to

yellow ppt. with boiling .

1-Mercury chloride test:

then boil .

gray ppt. with boiling .

2-Permanganate test:
1ml of warm acid + drops

The color disappear.

of KMnO4 .

The color will not

disappear.

62

Experiment to differentiate between formaldehyde and Acetaldehyde :

Test

Formaldehyde

Acetaldehyde

Red violet ring is

- Ve

1-Resorcinol test:
In a test tube put 1ml of HCHO
+ drops of resorcinol +1ml of

formed at the interface

H2SO4 conc. added down the side

(A white ppt. appears

of the test tube.

over the ring ) .

2- nitroprusside sodium test:

In the test tube put 1ml of

- Ve

Dark red color .

aldehyde + 0.5 ml of Sodium

nitroprusside then put drops of
NaOH with shaking .

***************************************

63

AROMATIC ORGANIC ACIDS

1-Benzoic acid C6H5COOH

Benzoic acid is a white crystalline solid undergo sublimation by heating partially
soluble in cold water, freely soluble in hot water and ethanol m.p. is 121 C .

Test

Observation

Result

CO2 evolves with

The compound from

effervescence

carboxylic acid.

1-Acidity test :
0.25gm of acid +1ml of conc.
NaHCO3 solution .
2-Ferric chloride test :

The ppt. is basic ferric

1ml of N.S. + drops of FeCl3 .

buff ppt.

COONH4

benzoate (33) .

COO)Fe(OH)2
+

FeCl3

NH4Cl

(33)

3-Estrification test :
0.25gm of acid +1ml of ethanol

Specific odor

The odor due to Ethyl

+1ml of conc. H2SO4 & heat in water

benzoate (34) .

bath 3 min. then pour into beaker

contain NaHCO3 solution .
COOH
H2SO 4
conc

COOC2H5

+ C2H5OH

Ethyl benzoate

64

H2O

(34)

2-Salicylic acid C6H5(OH)COOH

Salicylic acid is a white crystalline solid undergo sublimation by heating, partially
soluble in cold water, freely soluble in hot water and ethanol m.p. is 159 C .

Test

Observation

Result

CO2 evolves with

The compound from

effervescence

carboxylic acid

1-Acidty test :
0.25gm of acid +1ml of conc.
NaHCO3 solution.
2-Ferric chloride test :

Specific test of

1ml of N.S. + drops of FeCl3 .

Violet color

salicylic acid

Vix odor

The odor due to Methyl

3-Estrification test :
0.25gm of acid +1ml of methanol
+1ml of conc. H2SO4 & heat in
water bath 3 min. then pour into

salicylate ester (35) .

beaker contain Na2CO3 solution

COOH
+

H2SO 4
conc

COOCH3

OH

OH

Methyl salicylat

65

H2O

(35)

DI CARBOXYLIC ACID

COOH

1-Oxalic acid

COOH

Oxalic acid is a colorless crystalline solid freely soluble in water and

alcohol, it undergo pyrolysis without charring up on heating .

Test

Observation

Result

CO2 evolves with

The compound from

effervescence

carboxylic acid.

No change for FeCl3

Oxalic or tartaric or citric

color

acid.

White ppt. on cold

The ppt. is calcium oxalate

1-Acidity test :
0.25gm of acid +1ml of NaHCO3
solution .
2-Ferric chloride test :
1ml of N.S. + drops of FeCl3 .

3-Calcium chloride test :

1ml of N.S. of acid +1ml of CaCl2

specific test for oxalic acid

4-Silver nitrate test:
1ml of N.S. of acids +2ml of silver
nitrate AgNO3 .

White ppt. dissolve

The ppt. is silver oxalate.

in ammonia and
HNO3 acid

5- potassium Permanganate test:

1ml of warm acid + drops of
KMnO4 .

The color of
KMnO4 disappear

66

Oxidation for oxalic acid.

HO

CH

COOH

HO

CH

COOH

2-Tartaric acid

Colorless crystalline solid, freely soluble in water and alcohols. Heating of acid
or its salts, they undergo charring with evolution of burned sugar odor.

Test

Observation

Result

CO2 evolves with

The compound from

effervescence

carboxylic acid

No change for FeCl3

Oxalic or tartaric or

color

citric acid

White ppt. appear after

The ppt. is calcium

scratching the inner wall

tartarate specific test

of the tube

for tartaric acid

White ppt. soluble in

The ppt. is silver

excess of N.S.

tartarate

5- potassium Permanganate test :

The color of KMnO4

Oxidation of

1ml of warm acid + drops of KMnO4

disappear on heating

Tartaric acid

6-Fenton's test:

Green color turns into

1ml of acid + 1drop of dilute solution

intense violet color on

specific test for

of FeSO4 then 1drop of 10% H2O2 .

adding excess NaOH

tartaric acid

1-Acidity test:
0.25gm of acid +1ml of NaHCO3
2-Ferric chloride test:
1ml of N.S. of acid + drops of FeCl3
3-Calcium chloride test:
1ml of N.S. of acid +1ml of CaCl2

4-Silver nitrate test:

1ml of N.S. of acids + 2ml of silver
nitrate AgNO3 .

solution.
7-Potassium dichromate test :

The color change to

specific test for

green .

tartaric acid

1ml of acid +1ml K2Cr2O7 & heat

67

CH2

3-Citric acid

HO

C
CH2

COOH
COOH
COOH

Citric acid is Colorless crystalline solid, freely soluble in water and alcohols. By
heating a heavy vapor with irritating smell evolved and finally undergo charring

Test

Observation

Result

CO2 evolves with

The compound from

effervescence

carboxylic acid

No change for FeCl3

Oxalic or tartaric or

color

citric acid

White ppt. appear

The ppt. is calcium citrate

1-Acidity test :
0.25gm of acid +1ml of NaHCO3
solution .
2-Ferric chloride test:
1ml of N.S. + drops of FeCl3.

3-Calcium chloride test :

1ml of N.S. of acid +1ml of
CaCl2.

after boiling

specific test of citric acid

4-Silver nitrate test :

1ml of N.S. of acids + 2ml of
silver nitrate AgNO3 .
5-Denig's test :

White ppt. dissolve

in ammonia
Color of

2ml of N.S. + 2ml of denig's A

permanganate will

& heating until boiling then add

disappear and heavy

2 drops of deng's B .

The ppt. is silver citrate

white ppt. formed

68

specific test of citric acid

PHENOL
Phenol is aromatic compound contains one or more hydroxyl group (OH)
connected directly to aromatic nucleus.
Phenol classified according to the number of hydroxyl contained group into :
Monohydric phenol
Dihydric phenol
Trihydric phenol

 General properties of phenol:

1- Solubility:
Phenol soluble in sodium hydroxide solution (NaOH) or potassium
hydroxide (KOH) ,phenol differ from acids it doesnt dissolve in basic
carbonate like sodium carbonate Na2CO3 and potassium carbonate
k2CO3.

2- Ferric chloride test:

This test used to identify phenols it gives complex with red, blue, Purple
or green color.

3- Azodye formation test:

Diazonum salt react with phenols in basic medium via substitution
forming compounds, known as AZODYE, most of them used in cloth
dying. Azodyes are colored and they color depend on the kind of
phenol and the aromatic amine which used to form the azo compound.

4- Bromination test:
Phenols react with bromine forming the substituted product
which are mainly solids.

69

OH

1-Phenol
Phenol is a colorless crystals in pure state, which turned to light red when
exposed to air it has characteristic odor. Soluble in water, alcohols, ethers, and
sodium hydroxide. Highly toxic .

Test

Observation

Result

1-Ferric chloride test:

Diluted solution of phenol in alcohol then add Violet color appear
2 drop of FeCl3 .

The compound
from phenols

2-Azo dye formation test:

Take 3 test tube
Tube (1): 1ml of aniline +3.5ml of conc. HCl
Red dye

Tube (2): 1ml of sodium nitrite NaNO2

Dye is Benzene azo

Tube (3): phenol dissolved in excess NaOH.

phenol (36)

Keep the 3 test tubes in ice bath& Put tube

(2) (1) slowly, then add mixture to tube (3).

NH2

NaNO2

HCl

Aniline

NCl

Dyazonium salt

Dyazonium salt

NCl

OH

Phenol

Benzene azo phenol

70

OH

.(36)

3-Chloroform test :
1ml of phenol dissolved in excess 20%
NaOH +1ml of chloroform CHCl3 then heat

-Ve

Compound is

in water bath .

Phenol

4-Phthalein test:
In dry test tube add 0.5gm of phenol

Deep pink color

+ 0.5 gm of phthalic anhydride +2drops of

Specific test for

phenol (37).

conc.H2SO4 , and gently fuse together allow

to cool , and then add 30% NaOH solution in
excess
OH

OH

OH

OH

H 2S O 4 C o n c .

NaO H

F u s io n

O
O
O

P h th a lic a n h yd rid e

P h e n o lp h th a le in in a c id ic m e d iu m

OH

ONa
O

P h e n o lp h th a le in in b a s ic m e d iu m

..(37)

71

OH

2-Resorcinol
OH

Resorcinol is solid ,dissolve in water and alcohol but in soluble in benzene.

Test

Observation

Result

Deep violet color

The compound

appear

from phenols

Red dye

The dye is

1-Ferric chloride test:

Diluted solution of resorcinol in alcohol then
add 2 drop of FeCl3 .
2-Azo dye formation test:
Take 3 test tube
Tube (1): 1ml of aniline + 3.5ml of conc. HCl

Benzene azo

Tube (2): 1ml of sodium nitrite NaNO2

Tube (3): resorcinol dissolved in excess NaOH.

resorcinol

Keep the 3 test tube in ice bath & Put tube

(2)

(1) slowly, then add mixture to tube (3).

3-Chloroform test :
1ml of resorcinol dissolved in excess 20% NaOH

Red fluorescent

+1ml of chloroform CHCl3 then heat in water bath

Compound is
resorcinol

4-Phethalen test:
In dry test tube add 0.5gm of resorcinol

Red fluorescent

Compound is

+ 0.5 gm of phthalic anhydride +2drop of

in the inner &

resorcinol

conc.H2SO4 , and gently fuse together allow to

cool , and then add 30% NaOH solution in excess

72

Green fluorescent
in the wall.

OH

3-
-Naphthol

Solid, insoluble in water, alcohol, ether and sod.hydroxide solution.

Observation

Result

Diluted solution of -naphthol in alcohol then add

Greenish color

The compound

2 drop of FeCl3 .

turns to violet

from phenols

Brownish red

Dye is

ppt.

Benzene azo

Test
1-Ferric chloride test:

2-Azodye formation test:

Take 3 test tube
Tube (1): 1ml of aniline +3.5ml of conc. HCl
Tube (2): 1ml of sodium nitrite NaNO2

-naphthol

Tube (3): -naphthol dissolved in excess NaOH.

Keep the 3 test tube in ice bath& Put tube (2)

(1)

slowly, then add mixture to tube (3) .

3-Chloroform test :
1ml of -naphthol dissolved in excess 20% NaOH
+1ml of chloroform CHCl3 then heat in water bath

Blue color turns

Compound is

to green

-naphthol

4-Phethalein test:
In dry test tube add 0.5gm of -naphthol

Compound is
Green Color

+ 0.5 gm of phthalic anhydride +2drop of

conc.H2SO4, and gently fuse together allow to cool ,
and then add 30% NaOH solution in excess .

73

-naphthol

OH

4--Naphthol

Test

Observation

Result

Diluted solution of -naphthol in alcohol then

Greenish color

The compound

add 2 drop of FeCl3 .

turns to violet

from phenols

1-Ferric chloride test:

2-Azo dye formation test:

Take 3 test tube
Dye is Benzene

Tube (1): 1ml of aniline +3.5ml of conc. HCl

Tube (2): 1ml of sodium nitrite NaNO2

orange dye

azo -naphthol

Blue color turns

Compound is

to green .

-naphthol

Tube (3): -naphthol dissolved in excess NaOH.

Keep the 3 test tube in ice bath & Put tube
(2)

(1) slowly, then add mixture to tube (3) .

3-Chloroform test :
1ml of -naphthol dissolved in excess 20%
NaOH +1ml of chloroform CHCl3 then heat in
water bath .
4-Phethalen test:
In dry test tube add 0.5gm of -naphthol

Compound is
Green Color

+ 0.5 gm of phthalic anhydride +2drop of

conc.H2SO4 , and gently fuse together allow to
cool , and then add 30% NaOH solution in exces

74

-naphthol

Scheme for solid sample

Organic compound
Solid compound:

1- Acids:
Benzoic acid - Salicylic acid - Oxalic acid -Tartaric acid - Citric acid.

2- Sodium salt for acid:

Sodium acetate - Sodium format - Sodium Benzoate - Sodium Salicylate
Sodium Oxalate -Sodium Tartarate - Sodium Citrate.

3- Ammonium salt for acid:

Ammonium acetate - Ammonium format - Ammonium Citrate Ammonium
Salicylate - Ammonium Oxalate - Ammonium Tartarate.

4- Aniline salts:
1-Aniline Hydrochloride

2- Aniline Sulfides

NH2.H2SO4

NH2.HCl

75

First: 0.25 gm of unknown + 1ml of NaOH

No odor of ammonia

odor of ammonia

there is no ammonium salt

we have ammonium salt of acid

Go to second step
1ml of N.S. of salt + drops of FeCl3

-Ve unknown is

Violet color

Puff ppt.

ammonium oxalate

unknown is

unknown is

or tartarate

ammonium salicylate ammonium Benzoate

Red color change

to brown ppt. with
heating unknown is
ammonium format or

or citrate

ammonium acetate
1ml of N.S. of salt +1ml of CaCl2

White ppt. after boiling

White ppt. after scratching the

White ppt. on cold

unknown is ammonium

inner wall of the tube

unknown is

citrate

unknown is ammonium tartarate

ammonium oxalate

76

Second: 0.25 gm of unknown + 1ml of Na2CO3 solution

CO2 evolves with effervescence

No evolution

unknown is carboxylic acid or

we have sodium salt for acid

aniline salts

Go to the Third step

1ml of N.S. of salt + drops of FeCl3

-Ve unknown is

Violet color

Puff ppt.

sodium oxalate or

unknown is

unknown is sodium

tartarate or citrate

sodium salicylate

Benzoate

Red color change to

brown ppt. with
heating unknown is
sodium format or
sodium acetate

1ml of N.S. of salt +1ml of CaCl2

White ppt. after heating

White ppt. after scratching

White ppt. on cold

unknown is sodium

the inner wall of the tube

unknown is

citrate

unknown is sodium tartarate

sodium oxalate

77

Third: test of dye formation

Take 3 test tube
Tube (1): 1ml of aniline + 3.5 of conc. HCl
Tube (2): 1ml of sodium nitrite NaNO2
Tube (3): -naphthol dissolved in NaOH.
Then Put 3 test tube in ice bath & Put tube (2)

(1) slowly, then add

mixture on tube (3)

Red dye formed unknown

No dye formed

is aniline hydrochloride or

Go to the fourth step

aniline sulfides
Forth: 1ml of N.S. of acid + drops of FeCl3

-ve unknown is oxalic

Violet color unknown

Buff ppt. unknown

or tartaric or citric acid

is salicylic acid

is Benzoic acid

1ml of N.S. of acid + 1ml of CaCl2

White ppt. after boiling

White ppt. after scratching

White ppt. on cold

unknown is citric acid

the inner wall of the tube

unknown is Oxalic acid

unknown is Tartaric acid

78

Confirmatory test:
Test

Formic acid or its salt

Acetic acid or its

salt

White ppt. immediately

White ppt. change to yellow by

1ml of N.S. of unknown

change to gray with

boiling

+1ml of HgCl2 and boil.

boiling

1-Mercuric chloride test:

2-Permanganate test:
1ml of warm acid

The color will disappear

The color will not disappear

+ drops of KMnO4 .

Test

Unknown +AgNO3.

Hydrochloride Aniline

Sulfides Aniline

white ppt. from silver

-ve

chloride
white ppt. from silver
Unknown+BaCl2 .

-ve

Notes:
Preparation of N.S. for ammonium and sodium salt :
By dissolve the salt in water only .

79

sulphate