Experiment No.

02

Objective:

To synthesize acetic acid in the laboratory via oxidation of ethanol.

Apparatus:

i. Bolt head flask
ii. Reflux water condenser
iii. Dropping funnel
iv. Knee tube
v. Measuring cylinder
vi. Funnel and beaker

Chemicals used:

i. Sulfuric acid
ii. Ethanol
iii. Sodium dichromate
iv. Distilled water

Principle:

Acetic acid is the carboxylic acid and can be formed by following the oxidation of an alcohol
(i.e. ethanol). Oxidation of ethanol results in the formation of respective aldehyde (i.e.
acetaldehyde) which again undergoes oxidation to give the desired acetic acid.

Theory:

Porcelain - is a ceramic material made by heating materials. It is good heat absorber.
Carboxylic acids – These are the class of organic compounds contains --COOH as a functional
group. It can be viewed as the carbonyl group –C=O is attached with the hydroxyl group –OH.
They are actually the oxidize product of aldehydes. The simplest carboxylic acid is formic acid.
The most commonly used is acetic acid (or ethanoic acid) i.e. CH3COOH.

Acetic acid - chemically ―ethanoic acid” is the commonly used carboxylic acid. It is simply two
small functional groups, an acetyl group (CH3−C(=O)−) and a hydroxyl group, linked (AcOH);
it can also be viewed as a methyl group and a carboxyl group linked. Although it is classified as
a weak acid, concentrated acetic acid is corrosive and can attack the skin. It is an
important chemical reagent.

Glacial acetic acid - is a name for water-free (anhydrous) acetic acid. The name comes from the
ice-like crystals that form slightly below room temperature at 16.6 °C (61.9 °F) (the presence of
0.1% water lowers its melting point by 0.2 °C).

Oxidation - is the loss of electrons or an increase in oxidation state by a molecule, atom, or ion.
It may be defined as the process involving the addition of oxygen or the removal of hydrogen
from a molecule during the chemical process/reaction.

Oxidation of alcohols – alcohols on oxidation gives carbonyl compounds (i.e.
aldehydes/ketones) which on further oxidation yields carboxylic acids.

i.e.

Alcohols Aldehydes/ Carboxylic
Ketones acids

However, the outcome of oxidation reactions of alcohols depends on the substituents on the
carbonyl carbon. In order for each oxidation step to occur, there must be H on the carbonyl
carbon.

Primary alcohols on oxidation yield aldehydes which on further oxidation gives carboxylic
acids. i.e.
Secondary alcohols on oxidation yield ketones which do not further oxidized as there is no more
H present on carbonyl carbon which displaced out to give an acid. i.e.

No Reaction

Tertiary alcohols should not be oxidized as there is no H available to be displaced out. i.e.

No Reaction

Tertiary alcohol

Oxidants / oxidizing agents – these are the species that can remove electrons from another
species or providers of oxygen or acceptor of hydrogen. These are actually those species that
itself reduces but oxidizes others. There are many oxidants used to make sure the oxidation of
alcohols which are:
We take an example of dichromate salts where oxidation state of Cr changes from +6 to +3:

The electron-half-equation for this reaction is

Mechanism for oxidation of alcohols:
Reactions & mechanism for acetic acid synthesis:
Properties of Acetic acid:

Chemical formula CH3COOH or (C2H4O2)

Molar mass 60.05 g.mol-1

Appearance colorless liquid

Odor pungent/vinegar like

Solubility in water miscible

Acidity (pKa) 4.76

Boiling point 1180C

Liquid acetic acid is a hydrophilic (polar) protic solvent, similar to ethanol and water. It
dissolves not only polar compounds such as inorganic salts and sugars, but also non-polar
compounds such as oils and elements such as sulfur and iodine. It readily mixes with other polar
and non-polar solvents such as water, chloroform, and hexane.

Applications:

i. Acetic acid is used as coagulant in the manufacture of rubber.
ii. It is used in the manufacture of various dye stuffs and perfumes.
iii. It is used in the manufacture of rayon fiber.
iv. It is used as a solvent.
v. 5% solution of acetic acid is used as vinegar which is used in pickling of vegetables and
other foods.
vi. Dilute acetic acid is used in physical therapy.
vii. It is used in the formation of esters and other industrial chemicals.

Condensers:

A condenser is an apparatus or item of equipment used to condense (change the physical state of)
a substance from its gaseous to its liquid state. In the laboratory, condensers are generally used in
procedures done with organic liquids brought into gaseous state through heating with or without
lowering the pressure (applying vacuum)—though applications in inorganic and other chemistry
areas exist. It involves the phenomenon of heat transfer that is heat from the vapors is transferred
to the cooling fluid (may be air or liquid).

Condensers are of many types varying with the type of cooling fluid used and thus varying in
their applications.

i. Air cooled condensers
ii. Fluid cooled condensers

Air cooled condensers - The simplest sort of condenser consists of a single tube wherein the
heat of the vapor is conducted to the glass wall, which is only cooled by air; such air
condensers are often used for condensation of high boiling liquids (i.e., for distillations at high
temperatures).

For example:

Vigreux column – contains finger like indentations. It is a type of air condenser where
a glass blower has modified the simple tube to include an abundance of downward-
pointing indentations, thus dramatically increasing the surface area per unit length of the
condenser. A Vigreux column is a glass distillation column used from fractional
distillation. The inside of the column contains many rows of downward facing 'spikes'
that condenses the distilling vapor as it passes through the column. This column is
designed to face upwards so that the condensate falls back into the heated flask. The
repeated vaporization and condensation processes that occurs as the condensate passes up
the column allows for a more accurate distillation.

Fluid cooled condensers – use fluid as a cooling or condensing medium.

Two types:

i. Graham type condensers: The water flows around a tube (whether straight or coiled)
that contains the vapor/condensed liquid. This type of condensers clog (or flood) more
easily since they have a more restricted path for the liquid to return to the pot.
Graham type condensers include:
Liebig condenser - a most basic circulating fluid-cooled
design consisted of an inner, straight tube surrounded by
an outer straight tube, with the outer tube having ports
for fluid inflow and outflow. It is easy to construct and
inexpensive. It is simple, but has low cooling capacity
and can be fairly easily clogged as the condensed liquid
flows back into the flask and blocks the vapor that is
trying to escape.

Allihn condensers – also called bulb condenser or
simply reflux condenser. This condenser consists of a
long glass tube with a water jacket. A series of bulbs on
the tube increases the surface area upon which the vapor
constituents may condense. This design is improved as it
have a wider bore at the bottom and condensing the
liquid on the "bubbles" where it can run down the sides
and avoid blocking the vapor. It is ideally suited for
laboratory-scale refluxing.

Graham condenser - has a coolant-jacketed spiral coil
running the length of the condenser serving as the
vapor/condensate path. The condensation tube is coiled
which provides more surface area for cooling but also
tends to send the condensed liquid right into the path of
the vapor trying to move up. It is particularly prone to
flooding.

ii. Coil condensers: have high capacity for cooling with fewer problems from flooding
since the vapor condenses on the coils and drips back from the little prominence at
the bottom of the coils into the center of the pot. The vapor has an easy time getting
past the drops falling into the pot.
Dimroth condensers - It has an internal double spiral through
which coolant flows such that the coolant inlet and outlet are both
at the top. The vapors travel through the jacket from bottom to
top. Dimroth condensers are more effective than conventional coil
condensers. They are often found in rotary evaporators.

Friedrichs condensers - a spiraled finger condenser, consists of a
large, spiraled internal cold finger-type capillary tube disposed
within a wide cylindrical housing. Coolant flows through the
internal cold finger; accordingly, vapors rising up through the
housing must pass along the spiraled path. This is used with
rotovaps where you are taking a lot of solvent off quickly, but not
with an ordinary reflux apparatus. This would be over-kill for a
simple reflux reaction situation.

Reflux: is the process of boiling reactants while continually cooling the vapor returning it back
to the flask as a liquid. It is used to heat a mixture for extended periods and at certain
temperatures. A condenser is attached to the boiling flask, and cooling water is circulated to
condense escaping vapors.

If you are refluxing a mixture, as you might in organic synthesis to increase the speed of the
reaction by doing it at a higher temperature (i.e., the boiling point of the solvent), then any of the
condensers that worked well enough to avoid the loss of solvent and avoid "flooding" would
work equally well.

Procedure:

i. Take the bolt head flask and make sure that the unglazed porcelain is present in it.
ii. Then place in 5 ml of water in the flask and then add 3.3 ml of H2SO4 and shake it
slowly.
iii. Then add 3.5 g of porcelain crushed sodium dichromate in it. The dichromate rapidly
dissolves in it due to which solution becomes hot.
iv. Now take the dropping funnel and add 1.5 ml of ethanol and 6 ml of water in it.
v. Attach funnel to the flask and add mixture drop wise into the flask. The color of mixture
turns from orange to green due to the oxidation of dichromate.
vi. After the completion of addition and the reaction has subsided; attach the condenser in
the middle neck of the flask while other two necks should be closed with a stopper.
vii. Heat the mixture for 15 minutes in the water bath.
viii. After heating detached the condenser and reverse it and attach it again using a knee tube
for direct distillation.
ix. Slowly heat the mixture and collect 5 – 8 ml of distillate in the beaker.
x. The obtained distillate is acetic acid.

Precautions:

i. Make sure that porcelain should be placed in the bolt head flask.
ii. Ensure the use of wire gauze during heating.
iii. The flow of the tapped water through the condenser should be counter current and the top
of the condenser should remain open.
iv. Safety wears should be used while handling acids.

Observations & calculations:

Weight of sodium dichromate = 3.5 g

Ethanol used = 1.5 ml

Acetic acid (distillate) collected = 7.6 ml
Results:
Acetic acid was prepared in the laboratory and the volume collected is 7.6 ml.