Experiments for practical organic chemistry I

Experiment 1: Recrystallization
Recrystallization is a purification method used to separate a desired compound from a
mixture of impurities using differences in solubility and temperature. In the
recrystallization technique, the product is dissolved in a hot solvent, then allowed to
cool. While cooling the crystals of the product will reform, producing a purer product.
Recrystallization and crystallization are not the same. Crystallization is the formation of
a new insoluble product by reacting chemicals together. Recrystallization is about
purifying a product. There are no chemical reactions occurring in recrystallization.
Recrystallization is sometimes referred to as fractional recrystallization because crystals
are selectively allowed to reform.
Recrystallization Requirements
One of the key recrystallization requirements is the desired compound must be soluble
in the hot solvent, while being insoluble in cold solvent. A bigger difference in solubility
between the hot and cold solvent will lead to a greater recovery of desired product,
when performing a recrystallization.
The main steps of recrystallization procedure are:

1- Suitable solvent selection

Before carrying out the actual steps of the recrystallization process, you must
determine the suitable solvent for the impure compound (solute) by doing the solubility
tests.
-The compound should have low solubility in a cold solvent and high solubility in a hot
solvent.
- The compound should never react with the solvent.
- The solvent should easily be recovered.
- The solvent should be cheap and easily available.

2- Dissolving the Solute in the Suitable Solvent

The next step after determining the suitable solvent is adding the solvent to a beaker
containing the compound with the impurities. Then, heat the beaker (that is near or at
boiling point) and keep adding the solvent until the solute is dissolved completely.

3- Hot filtration

This step requires if insoluble impurities are present in the mixture.

4. Cooling the Solution

In this step, we will allow the solution to cool slowly, first in the open air, and then allow
it to continue cooling in an ice bath. The slow cooling here is important to obtain purer
crystals that will precipitate at the bottom of the beaker (The slower the cooling rate, the
larger the formed crystals).

Note: The process of “seeding” means the addition of the compound’s pure crystals that
forms a surface for the solute for the recrystallization process.

5- Obtaining the Crystals by Filtration (cold filtration)

The important and desirable part of the mixture is the pure crystals that form at the
bottom of the solution, and so the crystals must be collected and isolated from the
solvent by filtration.
.
6- Allowing the Resulting Crystals to Dry

After rinsing the crystals with a small amount of ice-cold solvent, we will let the crystals
dry by-
1- Leaving them in the aspirator.
2- Transferring them to a glass dish to wait a while longer.

Note: We can test the crystal’s purity by conducting a “melting point determination” test.

Experiment 2: Distillation
Distillation is the process of separating the components of a liquid mixture through
selective evaporation and condensation. The basis of separation is the difference in the
vapor pressures (volatilities) of the respective components.
Distillation is a purification method for liquids, and can separate components of a
mixture if they have significantly different boiling points. In a distillation, a liquid is boiled
in the "distilling flask," then the vapors travel to another section of the apparatus where
they come into contact with a cool surface. The vapors condense on this cool surface,
and the condensed liquid (called the "distillate") drips into a reservoir separated from the
original liquid. In the simplest terms, a distillation involves boiling a liquid, then
condensing the gas and collecting the liquid elsewhere

Distillation refers to the selective boiling and subsequent condensation of a component

in a liquid mixture. It is a separation technique that can be used to either increase the
concentration of a particular component in the mixture or to obtain (almost) pure
components from the mixture. The process of distillation exploits the difference in the
boiling points of the components in the liquid mixture by forcing one of them into a
gaseous state.
It is important to note that distillation is not a chemical reaction but it can be considered
as a physical separation process. An illustration describing the laboratory setup that is
generally used to execute this process is provided below.

Types of Distillation

Some important types of distillation include:

 Simple distillation
 Fractional distillation
 Steam distillation

Simple Distillation

 Simple distillation involves heating the liquid mixture to the boiling point and
immediately condensing the resulting vapors.
 This method is only effective for mixtures wherein the boiling points of the liquids
are considerably different (a minimum difference of 25oC).
 This method is also used to separate a liquid from a mixture of a liquid with
nonvolatile solids.

Fractional Distillation

Fractional distillation is often used to separate mixtures of liquids that have small
differences in boiling points (i,e < 25o c). It involves several vaporization-condensation
steps (which takes place in a fractioning column). This process is also known as
rectification. The apparatus required to perform a fractional distillation on a mixture is
listed below.

 Round-bottom flask or distilling flask

 A source of heat, which can be a fire or a hot bath.
 Receiving flask to collect the condensed vapors
 Fractioning column
 Thermometer to measure the temperature in the distilling flask
 Condenser
 Standard Glassware.
When heated, the liquid mixture is converted into vapors that rise into the fractioning
column. The vapors now cool and condense on the walls of the condenser. The hot
vapors emanating from the distilling flask now heat the condensed vapor, creating new
vapors.

Many such vaporization-condensation cycles take place and the purity of the distillate
improves with every cycle. An illustration depicting a fractional distillation setup is
provided below.
Experiment 3: Chromatography
The term “chromatography” is derived from Greek, chroma meaning, “colour,” and
graphein meaning “to write.” Chromatography is the technique for the separation,
purification, and testing of compounds.

It is a technique for separating the components, or solutes, of a mixture on the basis of

the relative amounts of each solute distributed between a moving fluid stream, called
the mobile phase, and a contiguous stationary phase. The mobile phase may be either
a liquid or a gas, while the stationary phase is either a solid or a liquid.

In this process, we apply the mixture to be separated on a stationary phase (solid or

liquid) and a pure solvent such as water or any gas is allowed to move slowly over the
stationary phase, carrying the components separately as per their solubility in the pure
solvent.

Types of Chromatography

The four main types of chromatography are

1. Adsorption Chromatography

In the process of adsorption chromatography, different compounds are adsorbed on the

adsorbent to different degrees based on the absorptivity of the component. Here also, a
mobile phase is made to move over a stationary phase, thus carrying the components
with higher absorptivity to a lower distance than that with lower absorptivity. The main
types of chromatographic techniques that are used in industries are given as under:
2. Thin Layer Chromatography

In the process of thin-layer chromatography (TLC), the mixture of substances is

separated into its components with the help of a glass plate coated with a very thin layer
of adsorbent, such as silica gel and alumina, as shown in the figure below.

The plate used for this process is known as chrome plate. The solution of the mixture to
be separated is applied as a small spot at a distance of 2 cm above one end of the
plate. The plate is then placed in a closed jar containing a fluid termed as an eluant,
which then rises up the plate carrying different components of the mixture to different
heights.
3. Column Chromatography

Column chromatography is the technique used to separate the components of a mixture

using a column of suitable adsorbent packed in a glass tube, as shown in the figure
below. The mixture is placed on the top of the column, and an appropriate eluant is
made to flow down the column slowly.

Depending upon the degree of adsorption of the components on the wall adsorbent
column, the separation of the components takes place. The component with the highest
absorptivity is retained at the top, while the other flow down to different heights
accordingly.

Column Chromatography

4. Partition chromatography

In this process, a continuous differential partitioning of components of a mixture into a

stationary phase and mobile phase takes place. The example of partition
chromatography can be seen in paper chromatography. In this process,
chromatography paper is used as a stationary phase which is suspended in a mixture of
solvents that act as a mobile phase.

Here, we put a spot at the base of the chromatographic paper with the mixture to be
separated and as the solvent rises up this paper, the components are carried to
different degrees depending upon their retention on the paper. The components are
thus separated at different heights.

Experiment 4: Survey of Functional Group (Chemical Test).

A functional group is defined as an atom or group of atoms within a molecule that has similar
chemical properties whenever it appears in various compounds. Even if other parts of the
molecule are quite different, certain functional groups tend to react in certain ways.

A functional group is a group of atoms in a molecule with distinctive chemical properties,

regardless of the other atoms in the molecule.

 Alkanes C-C

 Alkenes C=C
  Alkynes C≡C

 Phenols Ar-OH

 Alkyl (1o, 2o, 3o) & Aryl Halides R-X

 Alcohols (1o, 2o, 3o) R-OH

 Aldehydes and Ketones C=O

 Caraboxylic acids COOH

 Amines 1, 2, 3 RN

1. Unsaturation Test: ( C=C or C≡C )

Two common types of unsaturated compounds are alkenes and alkynes characterised
by the carbon-carbon double and triple bond, respectively. The two common qualitative
tests for unsaturation are the reactions of the compounds with:

a. Bromine in carbon tetrachloride

Rapid disappearance of the bromine colour to give a colourless solution is a

positive test for unsaturation

b. Oxidation of Alkenes with Potassium permanganate ( Baeyer’s Test)

Manganate(VII) ions are a strong oxidizing agent, and in the first instance oxidize
ethene to ethane-1,2-diol (old name: ethylene glycol).

c. Reaction with concentrated sulfuric acid.

 Alkenes react with sulfuric acid to give alkyl hydrogen sulfates and release heat ( write
the equation).

But since alkanes are saturated hydrocarbons, they are inert and don’t react with the
above very reactive reagents.

2. Phenol Test: ( Ar-OH )

a. Bromine water

Phenols are generally highly reactive towards electrophilic reagents and are readily
brominated by bromine water. e.g.

A white precipitate of the bromophenol may form.

b. Ferric chloride test

Most phenols react with iron (III) chloride, FeCl3, to form coloured complexes. The
colours vary - red, purple, blue or green - depending on various factors, e.g. the
phenolic compound used, the solvent concentration. Since some phenols do not give
colours, a negative test must not be taken as significant without supporting information

The appearance of blue, violet, purple, green, or red-brown colour is a positive test.
3. Alcohol Test: ( R-OH )
i. Alcohols are neutral substances towards litmus

ii. Chromic Acid (Jones Oxidation) test

- Distinguish Primary & Secondary Alcohols from Tertiary Alcohols.

- Chromic Acid (Cr+6) oxidizes Primary and Secondary Alcohols to Carboxylic

Acids and Ketones, respectively.

- Chromium (+6) - orange– is reduced to Chromium (+3) – green.

- Tertiary Alcohols do not react with Chromic Acid.

4. Aldehydes and Ketones Test: ( C=O )

i. 2,4-DinitrophenylhydrazinTest:

2,4-Dinitrophenylhydrazine reacts with carbonyl bond of all ketones and aldehydes to

form orange o red hydrazone precipitate.
Positive test = formation of yellow, orange, or red precipitate

Distinguishing between aldehyde and ketones

Tests for Aldehydes

i. Chromic acid and Tollens’ Test

• Positive chromic acid test: may look brown rather than blue-green ppt, but will be
a change from orange

• Positive Tollens test: formation of silver mirror on side of test tube.

But no reaction with chromic acid and no formation of silver mirror for ketones.

• (Do NOT store test tube: possible explosion!)

- Clean silver mirror with 6M HNO3

5. Carboxylic acid test: ( R-COOH ) or ( Ar-COOH )

i. Reaction with sodium bicarbonate

When carboxylic acid reacts with bicarbonates a salt is formed together with carbon
dioxide and water.

RCOOH + HCO3- → RCOO- + CO2 + H2O

Positive test: Bubbling carbon dioxide or effervescence.

ii. Ester formation

 Ester formation can also be used to test carboxylic acid. This involves reaction of
carboxylic acid with alcohols in the presence of mineral acids as a catalyst.

RCOOH + R’OH → RCOOR’ + H2O

iii. Litmus test

Since carboxylic acids are acidic they turn litmus Red.

6. Amines Test : ( RN or ArN )

i. Hinsberg Test

Primary amine dissolves in base and precipitates from acid are (+) test

Secondary amine precipitates from base and no change from acid is (+) test
Tertiary amine precipitates from base and dissolves in acid is (+) test

Experiment 5: Preparation and properties of Aspirin

Objectives

 Conduct a chemical reaction to produce aspirin.

 Separate the aspirin from the reaction by-products using filtration.

 Analyze the aspirin and estimate its purity.

Aspirin is essentially a medication that people use broadly all over the world. The chemical
name of Aspirin is Acetylsalicylic Acid (ASA). It remains to be one of the oldest and most
used forms of the drug that has common usage as an anti-inflammatory and antipyretic
medication.
Much like other compounds, Acetylsalicylic Acid does not occur naturally in nature. Aspirin
is prepared by chemical synthesis from salicylic acid, through acetylation with acetic
anhydride using sulfuric acid as a catalyst.
Physical Properties

Generally, Acetylsalicylic Acid is colorless to white crystalline solid. It has a smell similar to
that of vinegar. The taste of Aspirin is bitter. Similarly, the density of it is 1.40 g mL-1. The
melting point of Acetylsalicylic Acid is 135 ºC. Thus, if kept in higher temperatures, it will
decompose. Acetylsalicylic Acid is also soluble in water, ethyl ether, ethanol, and
chloroform.

Chemical Properties

Acetylsalicylic Acid is generally known by the ability of it being an anti-inflammatory drug.

The mechanism of action is because it inhibits enzyme cyclooxygenase. Therefore, it
causes suppression of Prostaglandin production (prostaglandins are molecules that are
present in the process of inflammation).

Experiment 6: Preparation and properties of soap

Soaps are the sodium or potassium salts of long chain fatty acids; or Soaps are
carboxylate salts with very long hydrocarbon chains. Soap can be made from the base
hydrolysis of a fat or an oil. This hydrolysis is called saponification.
Saponification is the hydrolysis of an ester of fay acids with NaOH or KOH to give
alcohol(glycerol) and sodium or potassium salt of the acid(soap).
One of the saponification reactions taking triglyceride as an ester and sodium hydroxide
as the base is as follows
Fats, oils, and fatty acids are insoluble in water because their hydrophobic tails are so
long. If a base is used for hydrolysis, the fatty acids produced are deprotonated and are
present as the corresponding carboxylate salts. Because these product carboxylate
salts are charged, they are much more soluble in water than the corresponding
uncharged fatty acids. Since the carboxylate salts also each have a long nonpolar tail,
they are also compatible with nonpolar greases and oils. Soap can emulsify fats and oils
by forming micelles around oil droplets. The soap molecules surround an oil droplet so
that their nonpolar tails are embedded in the oil and their charged “head” groups are on
the exterior of the droplets, facing the water. If the oil droplets are small enough and if
there are enough soap molecules to surround them, the oil droplets become dispersed
in the water and can then easily be washed away.
Soaps are less effective in hard water, which is water that contains a significant
concentration of Mg2+ and Ca2+ ions. These ions form precipitates with soap
molecules, and this precipitate is often seen as a gray line on a bathtub or sink and is
often called “soap scum”. Since soap forms a precipitate with these ions, it means that
many of the soap molecules are no longer present in the solution. Therefore, soap will
form fewer foams in hard water. “Soft water” is water that contains very few or no ions
that precipitate with soap. Soap will therefore be much more effective in soft water than
in hard water.

Detergents
 Detergents are similar to soaps in that they have a charged head group and a long
nonpolar tail group, but they are not prepared from natural fats or oils.
Detergent can be defined as a surfactant or a mixture of surfactants with cleansing
properties when in dilute solutions. There are a large variety of detergents, a common
family being the alkylbenzene sulfonates, which are soap-like compounds that are more
soluble in hard water, because the polar sulfonate (of detergents) is less likely than the
polar carboxylate (of soap) to bind to calcium and other ions found in hard water.

Detergents are useful because they do not form precipitates with magnesium or
calcium ions, which means that they work in both soft and hard water.