Making a liquid Pure!

– Distillation

Synopsis

Background
Distillation is the main method used for purifying liquid compounds and is therefore one of the basic crafts of
chemistry. Distillation can take a variety of forms, increasing in sophistication from the simple distillation at
atmospheric pressure used in this Experiment, through fractional distillation, to fractional distillation under
reduced pressure.

You will commence development of your distillation skills in this Experiment, where the essential elements of
simple distillation (i.e. assembling the apparatus, monitoring and controlling the distillation) are illustrated by
purification of ethyl acetate.

* Applications of simple distillation

If the impurities in the liquid are non-volatile, the liquid can be purified by simple (direct)
distillation. The impure liquid is boiled and the vapour, which consists only of the pure
compound, is condensed and collected. The impurities, which might be non-volatile solids
dissolved in the liquid or non-volatile miscible with the liquid, are left behind in the distillation
flask.

If, however, the impurities are themselves volatile liquids, it is usually necessary to use a
“fractional distillation” in which the volatile components of the mixture are separated.

During the distillation, the temperature at which the vapour condenses is measured. If this
temperature remains constant while the majority of the liquid boils off, it is taken as the
boiling point of the liquid (at atmospheric pressure).

Sometimes direct distillation is useful for separating two liquids with widely differing boiling
points (b.p.). For example, in the preparation of aniline, diethyl ether (b.p. 35 oC) is distilled
from aniline (b.p. 184 oC) at low temperature. The separation will not be perfect, but the
direct distillation achieves bulk separation and purification can be completed by distillation of
aniline itself.

* Boiling point
The b.p. of a liquid is an important parameter for characterising the liquid and it is sometimes
useful for identifying an ‘unknown’. It is normally determined during distillation (see above).

A pure liquid (which does not decompose on boiling) will have a sharp b.p. (1 or 2 oC range).
However, because b.p. is sensitive to barometric pressure, there may be variation over
several degrees in experimental and literature values of b.p. for a particular compound.

Unlike melting points for solids, sharp boiling points are not necessarily good indications of
high purity in liquids because a sharp b.p. may be caused by constant boiling mixture of two
or more liquids (see Ref. 1 for further details).

* Choice of apparatus
(a) Size
The size of apparatus chosen must be compatible with the volume of liquid to
be distilled. The distillation flask should be large enough to ensure that when
the liquid boils it does not bubble over into the condenser. If this happens,
your “distillation” will be quick, but the impurities are also carried over! On the
other hand, the distillation flask and the rest of the apparatus should not be so
large that the available vapour from the boiling liquid barely fills the apparatus.
In this case the large, cool apparatus will tend to condense the vapour before
it reaches the condenser and what little does reach the condenser will provide
only a small volume of distillate.

Aim to start with the distillation flask about one half to two thirds full.

(b) Condenser
 A water condenser is most frequently used (as in this Experiment), but for
liquids boiling above about 150 oC an air-cooled condenser is preferred (see
Ref 2).

(c) Heating
Several methods are available:
1. Bunsen burner. This method has all the attendant dangers of a naked flame
in close proximity to organic vapours. Use of a Bunsen burner is not
recommended except in skilled hands for special circumstances.
2. Electric heating mantle. Though convenient and free from “naked flame
dangers”, there is a risk of overheating because there is no means of
monitoring the mantle temperature, For this reason, DISTILLATIONS
USING HEATING MANTLES MUST BE CONTINOUSLY ATTENDED. (A
mantle is used in this Experiment).
3. Water bath. Generally to be avoided because the water condenses all over
distillation apparatus, creating a mess and risking contamination of the
distillate. However, warm water (not directly heated, e.g. from the tap) is
recommended for distillation of diethyl ether (b.p. 35 oC).
4. Oil bath on a hot plate. Undoubtedly the best method because of the ease
of monitoring and controlling the rate of heating. Disadvantages are the
danger posed by hot oil (spills, or accidental addition of water to very hot
oil!) and fumes which often arise from reused oil when it gets very hot.

Recording
The work should be carried out on your own. You must of course, keep your Laboratory Notebook Record
up to date throughout the Experiment, and it should be maintained strictly according to the guidelines
provided at the start of the module. You are also reminded that your Laboratory Notebook Record should
contain a detailed record of all your procedures and observations, including those obtained from video
material. However, on the basis that “a picture is worth a thousands words”, you are not expected to write a
detailed description of either the distillation apparatus or how you built it! Instead, you should provide a
detailed, cross-sectional diagram of the apparatus, introduced with words such as “The apparatus was
assembled as shown in the diagram”.

Once the apparatus has been constructed, the distillation will take about 30-45 minutes, so there will be
ample time to repeat the distillation if “things go wrong”. Each separate distillation which you carry out
should be recorded, in detail, in a table in your Laboratory Notebook Record.

Assessment
The quality and volume of your distilled product will be assessed by your Tutor when you present your
sample (in a measuring cylinder) for inspection during the practical class.

The top copy of your Laboratory Notebook Record should be submitted for assessment at the end of the
laboratory session.

An important part of the assessment for this Experiment will depend on the quality of your record for each
individual distillation.

Preparation

The instructions for this Experiment, which are given under “Procedure” are purposely rather brief. They are
given on the assumption that you have gained knowledge about how to set up the distillation apparatus and
carry out a distillation of atmospheric pressure from the video clip provided. It would be very tedious for you
to have to read through instructions which covered all the detailed procedures required to carry out a
distillation – it is far better for you to see the techniques demonstrated (you would be wise to make some
notes about the techniques as you watch the video).
Watching this video clip is absolutely essential before coming to the laboratory to start the Experiment.
You will not know how to carry out the Experiment unless you have done this (because the detailed method
is not given in the instructions for this Experiment!). Given the importance of this, you will understand when
your Tutors ask you to stop work and watch a section of the video if they judge from your performance that
you have not prepared sufficiently for this Experiment.

You should prepare yourself to carry out the following tasks:

 * Assemble the distillation apparatus in such a way that all recommended safety features are
implemented.
* Charge the distillation flask with the impure sample, taking appropriate safety precautions.
* Carry out the distillation carefully and with patience, while monitoring progress and recording
your monitoring in a suitable table.
* Change receiver flasks at points in the distillation which ensure that your purified sample
contains only liquid which has boiled in the narrow temperature range which you will be
reporting as the b.p. of your sample.
* Use the correct procedure for “closing down” the distillation.

You can support your preparation, and find answers to part of the Pre-lab Assignment, in the following
references:

1. Practical Organic Chemistry, F.G. Mann and B.C. Saunders, 4th Ed., Longmans, 1960; brief
discussion of b.p.’s as a criterion of purity, p. 6-7; determination of b.p., including single distillation,
p.7.-9.

2. Vogel’s Textbook of Practical Organic Chemistry, revised by B.S. Furniss et.al., 4th Ed., Longmans,
1978; details of distillation at atmospheric pressure, p.141-143; survey of heating methods for
distillation and reaction mixtures, p.44-50.

3. Handbook of Chemistry and Physics, R.C. Weast, Ed., 64th Edition, CRC Press, 1983/84; THE “first
choice” reference book for chemical and physical data! Any of the editions (i.e. not only the 64 th!) will
provide most of the data routinely required for well known compounds. Taking the trouble to find
your way round this tome will be a sound investment.

Health and Safety

Electrical equipment
Before issuing the heating mantle, the technical staff will have made a quick visual check of plugs and cables
according to the procedure in Section 7 of the Departmental Safety Code of Practice. Since this apparatus
will be used by many different people in different parts of the laboratory, you should also carry out a visual
check on the plug and cable. If there is any sign of damage or wear, do not use the mantle, but report the
problem immediately to one of the technical staff.

Charging the distillation flask with sample

The heating mantle MUST be removed from under the distillation flask before pouring the sample into the
flask.

Water condenser
Plastic tubing which carries water to and from the condenser MUST be wired (or tied) in place.

During the distillation

Once heating has commenced, a distillation MUST NOT be left unattended.

Nearing the end of a distillation

The distillation MUST NOT be continued beyond the point where 5 cm3 of sample remains in the flask.

Control of Substances Hazardous to Health (COSHH) Regulations

Some of the risks involved in this Experiment arise from the use of a hazardous substance (i.e. the sample to
be purified). In compliance with the COSHH Regulations, the risks are assessed as follows:

Substances to be Quantity Exposure limit* Hazards Waste disposal

used / mg m-3
 ethyl acetate <100 cm3 1460 highly non-chlorinated
flammable organic waste

* long term exposure limit (8 h reference period)

Control measures to be used: Safety spectacles and laboratory coat must be worn.

Provided that the Safety Code of Practice and the experimental instructions are followed, and that the above
control measures are applied, the risk to health and safety from the use of these substances and equipment
is minimal.

Procedure

Briefly discuss the COSHH risk assessment with your Tutor, who will ascertain that you have read, and
understand, the assessment.

A sample of ethyl acetate containing a non-volatile impurity will be issued to you from the stores.

Note, in your Laboratory Notebook Record (under “Results”), the literature value for the b.p. of ethyl acetate
which you obtained as part of the Pre-lab assignment. Remember to give the reference for the source of this
information in exactly the style used for the references in the instructions for this Experiment. This is the
internationally accepted convention for writing down references to the chemical literature, and you will want
to adopt this at an early stage in your training. (Since you will not be able to reproduce “italic” in your
handwriting, the convention is to underline words which you intend to be italic).

Set up “Quickfit” apparatus for distillation of ethyl acetate (40 cm 3) using a 100 cm3 round-bottomed
distillation flask and an electric heating mantle. Add a few “antibumping” granules to the cold liquid before
starting distillation. (Remember to include a detailed cross-sectional drawing of your apparatus in your
Laboratory Notebook Record).

Distil the ethyl acetate using gentle heating and a distillation rate of 1-2 drop s -1. Monitor the time,
temperature, distillation rate and other features of the distillation, using a table to record your observations.

WARNING: DO NOT DISTIL THE LAST 5 cm3 OF LIQUID.

Using a measuring cylinder, determine the volume of the discarded “fractions” of distillate. Also record the
volume and b.p. of the pure distillate. Present the pure distillate in a measuring cylinder to your Tutor who
will confirm the volume and endorse your Laboratory Notebook records accordingly.