Organic Chemistry Expt Level 1

@RGANIE CHENATSTRY
IEVEI T
FIRST YEAR ORGANIC PRACTICAL COURSE
AIMS OF THE COURSE
. To illustrate and teach by first hand experience the basic practical

techniques of organic chemistry. Such techniques include those of
handling apparatus and chemicals, purification procedures, and the
use of spectroscopic and chromatographic analytical instruments.
. To complement and supplement lecture course material, especially

mechanistic concepts.
. To develop the student's abiiity to interpret and analyse

observations and data.
o To teach the student to communicate his/her results in a clear and

unambiguous manner.
. To provide a glimpse of the exciting and challenging nature of
organic chemistry.
REPORT WRITING
Except where otherwise stated reports should have the following format and be
written in a hard cover ruled notebook.
Date and title of experiment
Introduction:
A brief background to the theory and general practical procedures

involved in the experiment. Equations and mechanisms should be
inciuded at this point.
NB This section must be written in your own words.
Experimental:
An account of what you did in the experiment (not necessarily the same as
that in the manual). This should be written in impersonal, passive style.
Common abbreviations, such as conc. for concentrated and soln. for
solution, are allowed and quantities of chemicals should be placed in
brackets after their name, eg benzaldehyde (106 g 0.0L mol).
Results:
A11weighings and rough calculations should be recorded, and where

possible results should be presented in tabular form.
A sample of all products should be handed in for assessment, in a

container labelled with your n.une, course and contents.
Conclusion and Exercises:
This section involves the interpretation of results and the .rnswers to any
set questions.
Results:
All weighings and rough calculations should be recorded, and where

possible results should be presented in tabular form.
A sample of all products should be handed in for assessment, in a

container labelled with your name, course and contents.
Conclusion and Exercises:
This section invoives the interpretation of results and the answers to any
set questions.
HAZARD SYMBOLS IN THE CHEMISTRY LABORATORY
All chemicals are hazardous to a greater or lesser extent.

It is probably best to assume that ALL ORGANIC COMPOLINDS ARE
FLAMMABLE. Solvents, in particular, should be kept well clear of bunsen
flames.
Familiarise yourself with the hazard symbols on reagent botties. These symbols
are used within this section to indicate the compounds which require extra care.
Use a fume hood for volatile hazards.
Highty fl ammable substance

Keep away from sources of heat, flames, sparks, etc
Highly
Flammable
Explosive substances
W
Explosive
May explode under certain conditions. Avoid shock, friction,
sparks and heat.
Oxidising substances
W
Oxidising
Can ignite combustible material or worsen existing fires. Keep
away from combustible materials.
Toxic substances
@ Toxic
Very hazardous to health when breathed in, swallowed or in
contact with the skin. Avoid contact with the body and consult
doctor immediately if feeling ill.
a
tr
lrritant
Irritating substances
May have an irritant effect on skin, eyes and respiratory organs.
Do not breath vapour and avoid contact with skin and eyes.
tr
Harmful
Harmful substances
Causes slight damage to body tissue. Do not breath vapour and
avoid contact with skin and eyes. If feeling ill consult a doctor.
Conosive substances
t-s'l Destroy body tissue as well as equipment. Do not breath vapour
lssl
Corrosive
and avoid contact with skin, eyes and clothing.
Specimen Report
Preparation of benyl 2-naphthyl ether
Introduction
Eth:lt lay be formed by interaction of salts of alcohols or phenols with alkyl or

aryl halides.
RONa+R'-X -R-O-R'+NaX
The reaction involves nucleophilic displacement (substitution) of the halogen
atom, as halide ion, by the negatively charged nucleophile.
RO- + X+ R_O_R'
In this experiment, the 2-naphthate ion, prepared by dissolving 2-naphthol in

sodium hydroxide, is the nucleophile, and benzyl chloride is the halide which
can give a carbocation stabilised by delocalisation of the positive charge.
cHz
,"YtcHz+_>
\2
ll |
++ etc
Thus a 519L mechanism may be involved.
An excess of the water soluble sodium 2-naphthate is used so as to convert ajl_the

haiide to the ether. The excess of reagent can then be removed by water washing.
Unreacted halide would be more difficult to remove from the product and
would cause this to appear as an oii.
Method
2-Naphthoi (4.0 g,0.03 mol) was dissolved in sodium hydroxide (12 cm3 of 10%
soln) andbenzyl chloride (1.1 9,0.009 mol) was added. The mixture was heated
under reflux for 30 minutes, cooled and shaken with water (40 cm3;.
The solid product was filtered off, washed with water and crystallised from
ethanol. Recrystallisation gave the pure ether m.p. 100".
Results
t#
Theoretical yield = (since 2-naphthol used in excess)
Actual yield = 1.659 = 81"/o (literature 88%)

m.p. 100.0" (literature Vogel 101.5").
Conclusion
Benzyl,2-naphthyl ether was prepared in 81% yield by reaction of sodium-2-

naphthate and benzyl chloride.
Appendix: CALCULATION OF % YIELD
The theoretical yield for a reaction is the mass of product expected on the basis of
of the stoichiometry of the process.
The actual yield is the mass of product obtained when the reaction is performed.
It will be less than the theoretical yield
because of such factors as unwanted side
reactions, unfavourable equilibrium constant or physical losses occurring during
the work-up of the product.
The % yield expresses the actual yield as a percentage of the theoretical yield. It
provides a convenient guide to the efficiency of a synthesis, usefuI, for example,
when alternative routes to a product are being compared.
%yierd, = #ffix rco%
The overall yield can be calculated for a product obtained from a series of
consecutive reactions. For example if three consecutive reactions have % yields of
u, v and w7o, then
overallyield = ih"#"# x 1,00%
Example 1
n- PhosPhoric
acid / \
-
\-a""
(
cyclohexane
Lott -
cYclohexene
From the equation
l-mol 1 mol product

100 g + 829
-
Lr the laboratory
2s.0g + 9.09 (this is the exprimental yield)
25.0/100 = 0.250 mol 9.0/82 = 0.11 mol

-- 9.0
theoretical yield = 0.250 mol % yield = 2,.,so x 100'/"
= 0.250 x82g
= 43.9"/o
= 20.59
Example 2
From the equation

L mol -+ L mol L mol
L mol
1449 126.5 g
.+ 734 g 36.5 g
In the laboratory
1.65 g
4-o I 1.19
->
.-- 1.65/234rnol
4.0 /1'M mol 1.1./126.5 mol
0.0087(0) mol 0.00705 mol

0.027(8) mot
-
Lr this fiMo-reactant reaction 2-naphthol (0.0278 mol) is present in excess and
reactant'
benzvl chloride (0.00870 mol) is the yield-limiting
theoretical Yield = 0.00870 mol % yield = lf.onx1oo%

= 0.00870 x234g
= 80.9Yo
= 2.049
Example 3
calculate the overall yield'

If each stage of a r.0-stage synthesis has a % yierd, of 90"/o,
r 90 110
overaliYield = lmdl x 100%
= 34.9%
EXPERIMENT :O1
THE PURITY OF ORGANIC CHEMICALS
Introduction
It is important to be able to assess_the purity of compounds in Organic Chemistry.
The complete and unambiguous characterisation of i substut." d1 best be
achieved when its state of purity is high. The correlation of chemical data is only
meaningful when the reactions and properties of ry substances are studied.
The purity of solids and non-volatile liquids may be assessed by thin layer
chromatography (tlc) which is a rapid separation technique; i.e. a pure iubstance
81v9s one spot. The presence of additional minor spots on a tlc plite is indicative
of the ?resence of impurities. Identification of an "unkno*r," io*pound is also
possible by comparing its Rg with that of an authentic standard running on the
same plate.
Pure crystalline organic compounds have sharp characteristic melting points.

The presence of even small amounts of impurity produces a significant
depression in the_melting qoint and a-broadening of the meltin[ tunge. A sharp
melting point is thus a useful index of the purity of a compound und cun
sometimes reveal its identify.
I9t ft1t experiment, you will be aliocated three samples. You are required to
identify which two of the three samples are the samL material.
Objectives
By the end of this experiment you should be able to
(a) select and assemble the correct apparatus to run a tlc on an "unknown"
material;
&) use a melting point apparatus to determine the melting point of a solid;
(c) run a tlc of an "unknowrl" material;

(d) visualise spots on a tlc plate using LIV light or iodine vapour;
(e) measure and record R6 values from a tlc.

Procedure
Make a note of the compound code number now !
See the Teqhniques booklet for more detailed information on tlc's and mpt's.
A: Thin layer chromatography
tr
Harmful
1. Set up a chromatography tank using a dry 150cm9 beaker
containing the eluting solvent (2 or 3 mm deep). Start by
using 1.1.l-trichioroethane as the eluent. Cover with a
watch glass so that the beaker saturates with eluent
vaPour.
2. Using ignition tubes, make up solutions (approx 50 mg in
@Toxic
t cm3) of each of the samples in L,L,L-trichloroethane or
methanol depending on solubility.
J. Using a fine capillary tube (drawn from a melting point

tube in a Bunsen flame), apply a small spot of each of the
sample solutions about L cm from one end of a silica gel
tlc plate. You should be able to load the three samples
onto the same plate but use a new capillary for each
sample. The position of application (the origin) should be
marked lightty at the edges of the plate with a pencil or
spafula.
4. Stand the plate in the tank and replace the lid. The spots
must be above the level of the eluent. When the eluent
front has advanced to within about L cm of the top of the
plate, remove the plate. Quickly mark the eluent front
and allow the eluent to evaporate from the plate.
tr
Harmful
5. If the spots are colourless, they may be visualised in UV
light viewing box
(CAUTION:
DO NOT LOOK DIRECTLY AT LIGHT SOURCD.
The spots appear dark against a green background since

the plates incorporate a fluorescent material. Mark the
centre of each spot. A more permanent record of the spots
can be obtained by spraying the plate with iodine vapour
in the chromatogiuphy f.tti" cupboard
6. Measure the distance moved by the spots and the eluent
from from the origin. Compare the positions of the spots.
7. Repeat using ethyl ethanoate (ethyl acetate) and then
methanol as the eluents.
B: Measurement of melting point
L. Seal one end of a capillary melting point tube in a Bunsen

flame.
(CAUTION:
ENSURE THAT NOBODY /S USING FLAMMABLE
SOLVENTS NEARBY BEFORE LIGHTING THE BUNSEN
FLAME),
2. Powder a small amount of each sample on a watch giass

and introduce the powdered material (2-3 mm) into the
metling point tube. Tap gently to transfer the material
into the sealed end.
3. Place all three tubes alongside a 350" thermometer in a

meiting point apparatus. Adjust the heater controls so
that the temperature rises quickly until each solid melts
and note the temperature. This gives an approximate
melting point. Cool the apparatus until the temperature
is about 20- lower than the lowest melting point and
insert fresh samples. Raise the temperature slowly (2-3-
per minute) and record the accurate melting points.
4. Carefully make L:1 mixtures of the samples, grind them

together; introduce the mixtures into separate melting
point tubes and measure their melting points or melting
ranges.
Reoortine of results
1.. Calculate and tabuiate the R1 values for the compounds in each eluent.
distance moved by samPle sPot from origin

'tt - distance moved by eluent front from origin
-2. Identify the odd one out of the three sampies.

3. What is the effect of increasing polarity of the eluent on Rl value?
4. Tabulate the meiting point data. Does the mp data support the tic
findings? How does the mp of the binary mixtures comPare with the mp
of the constituents?
MANCHESTER METROPOLITAN UNIVERSITY - COSHH ASSESSMENT
FACULTY DEPT/DIVISION/UNIT
Science and Engineering Department of Chemistry
(1) ACTIVITY
DGERIMENT : O 1
THE PURJTY OF ORGANIC CHEMICALS
(2,) REASONS FOR ACTIVITY
To give the students experience in using simple physical techniques to distinguish

between different organic compounds
(3) STATUS OF PERSONS UNDERTAKING ACTIVITY
Undergraduate students qualified to mter the course
(4) HAZARDOUS SUBSTANCES USED AND HAZARD CLASSIFICATION
Sets of unl,nowns
lW / A].,\/P / M,lvfP /43 Treat all the unknown

I(P /87,1,/ff /BZ,NP /83 samples as being
lv[P/CL,l\/tr/C2,1\E/C3 HARMFUL
MP /DI,IW /D2, MP/D3

I\lff /E'1.,1'/E /E2,lW /83 M2-37 / 28; 522-24 / 25-26-28
lvP /FJ.,lvP /FZ,\E /F3
L, 1,1-trichloroethane HARMFUL
F20/22;52-25
Ethyl acetate HIGHLY FLAMMABLE
R11; 516-23-29-33
Methanol TOKC; HIGHLY FLAMMABLE
R11-23/25; 32-7-24
Look up the R and S phrases listed in the Techniques Booklet

EXPERIMENT :O2
PURIFICATION BY RECRYSTALLISATION
Introduction
Recrystallisation is used widely for the purification of organic compounds. Most
compounds are more readily soluble in hot solvent than cold. When a hot
saturated soiution cools, the solute crystallises out leaving minor contaminants
in solution.
In a typical process, the impure material is dissolved in the minimum volume
of boiling soivent. Insolublb materials are removed by filtration and the filtrate
allowed to cool to room temperature. Crystals of the pure material are formed,
coilected by vacuum filtration, washed with ice-cold soivent and dried.
You will recrystallise TWO samples. The solvent for the first will be specified
but you will have to select a solvent for the second sample.
. Obiectives
By the end of this experiment you should be able to:
(a) select and assemble the correct apparatus to recrystallise samples of up to

1og;
(b) select after appropriate tests, a suitable solvent system to recrystallise a

solid sample;
(c) recrystallise a solid sample of up to 10 g:
(d) use vacuum filtration to collect a precipitate;
(e) use appropriate apparatus to dry a solid sample;
(0 calculate yields of recrystallised material.
Procedure
Refer to the laboratory technique booklet available in the stores.

1. Weigh out the sample CR1 (2g) into a 50 cm3
conical flask on a 'two-place' top-pan balance.
@M2
Toxic Highly
Flammable
Add approximately 10cm3 of ethanol. Heat the
mixture to boiling on a steam bath. Add further
small amounts of ethanol until the solid
dissoives.
l--1 3. Allow the flask to cool to room temperuture. If

ttn. l crystals do not form ask advice!
Toxic I ht/t/ |
I\?I
4. Cool 15 cm3 of ethanol on ice.
Highly
Flammable
5. Collect the crystals by vacuum filtration using a

Hirsch funnel and filter tube. Ensure good
adhesion between the pre-weighed filter paper
and funnel by wetting with solvent. Use the
filtrate (mother liquor) to transfer any
remaining solid in the conical flask to the
funnel. Finally wash the crystals with small
amounts of the ice-cold ethanol to remove
residual contaminants.
6. Dry the crystals by continuing to draw air

through the filtration system for a few minutes.
Transfer the crystals to a pre-weighed watch
glass. Cover with a large filter paper and stand
in a warm place (not oven!). Finally weigh the
dry crystals.
tr
Harmful
7. Check the purity of the crystals by tlc and run the
crude starting material alongside. IJser an
eluent of medium polarify (eg 1.1.1-
trichloroethane). An R1 of between 0.2 and 0.8 is
desirable and, to achieve this, it may be necessary
to use another eluent of different polarity. Refer
to the eluent list in the techniques booklet.
8. Measure the melting points of the crude and

pure crystals.
9. Before recrystallising the second sample, a
suitable solvent must be selected from the
following list:
light petroleum 60-80"

Highly
Flammable
l-r
tr
Harmful
methylbenzene (toluene)
tetrachloroethene
ttn.
|vrt
t>iaI
l
I
1,1, 1,-trichloroethane
Highly ethyl ethanoate (eihyl acetate) increasing

Flammable polarity
methanol
Toxic
ethanol
Highly
Flammable
t-; water
ethanoic acid (glacial acetic acid)

l-*?l
Corrosive
Perform small-scale solubility tests in test tubes.

To about 100 mg of solid add about 1cm3 of test
solvent. The 'ideal' solvent for recrystallisation
is one in which the solid is only poorly soluble
in the cold but completely soluble on lhe steam
bath.(use tongs!). Do these tests systematically
and record all your findings. Discuss these #th
the tutor before proceeding.
10. Recrystallise the second sample using the

selected solvent remembering to record the code
number of the sample you use.
Reporting of results
1. Note any problems encountered in the recrystallisations and how they

were overcome.
2. Present your recrystallised samples in sample bags to the tutor.
3. Caiculate the "h recovery for each recrystallisation.

4. Quote the melting point of each purified sample and comment on the
purity of each on the basis of tlc.
(1) ACTIVITY
EXPERIMENT : O2
PURIFICATION BY RECRYSTALLISATION
QI REASONS FOR ACTIVITY
To give the students experiertce in the purification of solid organic compounds and in
purity assessment.
Undergraduate students qualified to enter the course

Un-lcnown samples
CR/1 TOXIC R26/27 /2&33-37 /38;526-28-36/3745

'I<22-36/37/38;526-28
CR/Z HARMFUL
CR/3 HARMFUL R20/27/22-36/38;526-28
CI(/A HARMFUL R20/22-36/37/38;525-28
CR/5 HARMFUL I?C2-36/38;525-28
Ethanol HARMFUL, HIGHLY FLAMMABLE
R1,t-20/2L/22;57-1,6
For other solvents selected for recrystallisation and/or thin layer chromatography; the
officiai hazard ratings and risk and safety phrases are given in the "Practical
Techniques in Organic Chemistry" booklet with which you have been supplied. The
hazard ratings are also given on ALL reagent and solvent bottles in the laboratory.
Note the hazards and take suitable precautions when using them.
If in doubt as to correct usage, consult a member of staff.
Look up the R and S phrases listed in the Techniques Booklet.

EXPERIMENT :O3
PURIFICATION OF LIQUIDS: SIMPLE AND FRACTIONAL DISTILLATION
Introduction
Distillation is the method most commonly used for the separation and
purification of liquids. Here you will attempt to separate cycloheixane (bp 81"C)
from ethylbenzene (bp 135"C). These liquids form an ideal mixture which
conforms to Raoult's Law. The compostion of the distillation fractions obtained
are determined easily from refractiv-e index measurements.
A liquid boils when the vapour pressure becomes equal to atmospheric pressure.
When an ideal liquid mixture boils, the vapour, in equilibrium with it, is
enriched with respect to the lower boiling point component. This is the basis for
separation.
Liquids must have a boiling point difference of at least 60' for effective
separation by simple distillation, otherwise fractional distillation must be used.
With the latter technique, a series of simple distillations takes place
automatically in the fractionating column, each resulting in further enrichment
of the lower bp component.
Obiectives
(a) Use an Abb6 refractormeter to measure the refractive index of liquids;
@) Select and assemble the.correct apparatus for simple and fractional

distillation;
(c) Perform simple and fractional distillations at atmospheric pressure;
Procedure
Refer to the lab techniques booklet available in the stores.
1. Take 5cm3 samples of the following mixtures in

clean and drv test-tubes.
Highly
Flammable % Compostion (v/v) of ethvlbenzene 20 N & 80
Harmful
/cm3
Volume of ethylbenzene 1.0 2.0 3.0 4.0
Volumeof ryclohexane/cm3 4.0 3.0 2.0 1,.0
* Reporting of results
. Draw a gllPh of_refractive index against % composition of ethylbenzene

and use this to determine the composition of each distillation fraction.
2- Draw graphs of mean boiling point against fraction number and. oh

composition against fraction number. Draw the data from both
distillations on one graph.
3. Comment on the separation and purity achieved in each riistillation.
9. Before recrystallising the second sample, a
suitable solvent must be selected from the
following list:
light petroleum 60-80'

Highly
Flammable
EHarmful
methylbenzene (toluene)
tetrachloroethene
1,L,1-trichloroethane
Highly ethyl ethanoate (ethyl acetate) increasing

Flammable polarity
methanol
Toxic
ethanol
tr
water
Highly
Flammable ethanoic acid (glacial acetic acid)
Corrosive
Perform small-scale solubility tests in test tubes.

To about 100 mg of solid add about Lcm3 of test
solvent. The 'ideal' solvent for recrystallisation
is one in which the solid is only poorly soluble
in the cold but completely soluble on the steam
bath. (use tongs!). Do these tests systematically
and record all your findings. Discuss these with
the tutor before proceeding.
10. Recrystallise the secondsample using the

selected solvent remembering to record the code
number of the sample you use.
Reporting of results
r. Note any problems encountered in the recrystallisations and how they

were overcome.
) Present your recrystallised samples in sample bags to the tutor.
J. Caiculate the o/o recovery for each recrystallisation.

A
Quote the melting point of each purified sample and comment on the
purify of each on the basis of tlc.
EXPERIMENT :O4
INFRARED SPECTROSCOPY
Introduction
The classification of organic compounds is usually based on functional groups.
The physical and chemical properties of a compound are related to the functional
group(s) present. Historically, functional group analysis was based on a battery of
simple qualitative 'wet chemical' tests. This has been superceded by
spectroscopic methods (ir, uv and nmr).
Functional groups have characteristic absorptions in the ir spectrum and so

inspection of the ir spectrum of an 'unknown' compound quickly limits the
number of structural possibilities. Another important use of ir spectroscopy is
the identification of 'unknown' compounds by comparing their spectra with
those of known compounds.
Here, you will be introduced to the practical aspects of ir spectroscopy and

produce spectra for two known and two 'unknown' compounds. You will
attempt to identify the main functional group of each 'unknown' by ir
spectroscopy and get confirmation by chemical testing. Possible functionality will
be from the following.
alcohois aldehydes alkenes

amines carboxylic acids esters
ketones phenols
The chemical tests used here are reasonably selective but problems may arise if
your initial deduction from the ir is incorrect.
Obiectives
(a) prepare a nujol mull of solid material;
(b) outiine the mode of operation of an ir spectrometer;

(c) produce acceptable ir spectra of liquids and mulled solids;
(d) identify a compound's main functional group from its ir spectrum;

(e) perform simple functional group tests.
Procedure
1. Read 'OBTAINING AN IR SPECTRUM OF A LIQTIID OR

SOLID' in Appendix I at the end of this schedule.
tr
Harmful
2. The tutor will demonstrate sample preparation and the
operation of the ir spectrometer.
3. Produce spectra for the following samples:
(a) octan 1-o1 (liquid film)

@) benzil (Nujol Mult) r rt | , t r'j
(c) an 'unknown' liquid (liquid film) 4 Y' 7 tr
(d) and 'unknown' solid (Nujoi mutl) 7 L I
/)
4. Interpret as far as possible ir spectra in the form of a table, for
example:
peak position structural assignment comments

/ cm-I
2980 (s) C-H aliphatic stretch alkanic
2750 (w) C-H aldehydic stretch with C=O consistent
with aldehyde
1700 (s) C=O stretch carbonyl
1a50 (m) C-H bend I consistent with

t
1360 (w) C-H bend J aliphatic C-H
Briefly summarise your conclusions, for example:

Compound X is an aliphatic aldehyde
5. Do the classification tests for the appropriate functional group (see

Appendix II). Report your results in tabular form under the
headings: test, observation and inference.
5. If the results of the chemical tests are not consistent

with your ir
deductions then check your data and discuss your findings with
the tutor.
2. Measure their refactive index using an Abb6
refractometer. Include pure cyclohexane and
ethylbenzene in your measurements.
at
J. Lightly grease and, as shown in the techniques booklet,
assemble the apparatus for simpie distillation. This
should be clean and drv and will consist of :
100 cm3 round bottomed flask still head

screw-cap adaptor 360'C thermometer
water-cooled condenser receiver adaptor
electric heating mantle LL identical test tubes
4. Hatse the apparatus checked bu the httor before

oroceedins
Pour 25 cm3 of c]rclohexane and 25 cm3 of

ethvlbenzene into the flask usins a funnel and
add 3 or 4 anti-bump granules.
Highly
Flammable NEI{ER ADD TIIE GRANULES TO HOT
uQtrrD.
Fill one of the test-tubes with 5.0 cm3 of water for use as
a reference tube.
7. Switch on the heater and increase the setting slowly

until distillation begins. Note the temperature when it
becomes steady.
8. Collect approximately 5.0 cm3 fractions using the

reference tube for comparison. The heater control
should be set to give a distillation rate of about 1 drop
per second. As the distillation proceeds the setting will
need to be increased gradually. Note the temperature at
the start of each fraction.
9. Turn off the heating BEFORE the flask becomes dry and
note the temperature at its highest point. The last
fraction will be incomplete because of liquid remaining
in the apparatus.
10. Measure the refractive index of each fraction.
11. Insert a fractionating column into the apparatus and

repeat the above procedure (4-10). Because of 'hold-up'
in the fractioning column, it may only be possible to
collect 9 fractions.
APPENDIX 1
OBTAINING AN IR SPECTRUM OF A LIQI.]ID OR SOLID
Salt plates
-
tr
Harmful
These should be handled by their edges. Th"y should be
cleaned by rinsing in 1.1.l-trichloroethane and dried
carefully on a tissue. Water will dissolve the plates so
materials used with the plates must be dry.
Liouid samoles
Place the clean plates on tissue and apply one drop of the sample to one of the
plates using a clean rod. Place the other plate on top of the first so that a thin film
of sample is formed between the plates. If the spectrum is too intense, separate the
plates, wipe one clean, re-assemble and run the spectrum again. If the sp-ectrum is
too
- weak, then use more sample.
Solid samples
Spectra of solids cannot be obtained directly because of loss of radiation energy due
to scattering. One of the simplest methods of sample preparation is to make a
mull. h:r a mull, the finely divided solid is dispersed in a liquid, transparent to ir
radiation and having a refractive index close to that of the solid.
-
Two liquids commonly used for mulling are Nujol (liquid paraffin - an aliphatic
hydrocarbon) and HCB (hexachiorobutadiene).
Grind about 10 mg of sample using a clean mortar and pestle. Add two drops of
mulling liquid and regrind to give a mull with the consistency of whipped cream!
Transfer the mull to the salt plates to form a sandwich as with liquid samples. If
the spectrum is too weak it may be necessary to prepare another mull containing
more sample.
Runnins a snectrum
Place the plate assembly containing sample in the cell holder of the spectrometer.
Check that the chart and grating mechansim are synchronised at 4000 cm-1, adjust
the transmission to about 70"/o and press the scan button. The most intense peak in
the spectrum should be close to full scale without having a truncated appearance.
tr
Harmful
(b) Mix equal volumes (1 cm3; of Fehlings
Solutions A and B, add the test compound
(0.2 g) then heat by immersion in a steam
bath for 3 minutes). A red precipitate (of
Cu2O) indicates aldehyde.
Alkenes
Dissolve the test compound (0.2 g) rn L,I,1.-
m@1 Toxic
trichloroethane (1 cm3), add one drop of a dilute
solution of bromine in carbon tetrachloride. A
positive result is shown by the rapid loss of the
red colour of the bromine.
,)
Dissolve the test compound (0.2 g) in t-butyl
alcohol (2-methylpropan-2-ol, 1cm3). Add 0.1 M
@ium rermanganate dropwise: a positive
result is the loss of the purple colour.
Amines
1. Amines are soluble in dilute hydrochloric acid.
Dissolve the sample (0.5 g) in 1:1 conc HCl-water
tr@2
Corrosive Toxic
(2 cm3), cool to 0" by adding a piece of ice. Add a
cold solution of sodium nitrite (0.3 g) in water (2
.*3). Keep cold and observe:
t-t (a) steady evolution + 1' alphatic amine
ttn. I
of N2 at OoC
I ta'tz I
IISrtlT'rr I
(b) yellow oily emulsion
Highly (extractable into
Flammable
diethyl ether) + 2o amine
CAUTION:
DISPOSE OF CAREFULLY
Toxic NITRO SA]lIIINES ARE CARCINO GENIC
APPENDIX 2
FUNCTIONAL GROUP TESTS
Alcohols
Htr1 Add a small piece of sodium metal (about the

size of a rice grain) to the dry liquid or a solution
of the solid in dry toluene. Effervescence
indicates an alcohol but may also be caused by
acidic or wet compounds.
CAUTION:
W
Explosive
AVOID CONTACT OF SODIIIM WITH
WATER. DO NOT DISPOSE OF RESIDUES
SII\K. ASK ADWCE ON DISPOSAL.
IN
2. Primary and secondary alcohols are readily

oxidised bv acidified potassium dichromate.
ltal
J{"-rrfri
G ;:Rl
Dissolve @ (1g) in water (L0
.*3). Carefulty add conc. sulphuric acid (1 cm3).
Add the suspected alcohol (5 drops or 50 mg
solid) and mix weil. A positive result is
Corrosive
indicated by changes in temperature, colour and
odour.
Aldehydes and ketones
|--r
)tn. Il
1. Dissolve the test compound (0.1 g) in ethanol (1
ISZI .*3), add ethanolic 2.4-dinitrophenylhvdrazine
Highly
Flammable @l
Toxic
(1 cm3). If an immediate precipitate does not
form, heat to the boil in a steam bath then set
aside to cool. A yellow/red precipitate confirms
aidehyde/ketone.
.-r 2' To distinguish between aldehydes and ketones

l,)l try the following tests which are unfortunately
lNryll'-', not very good (ir is more reliable).
,m"lg' Toxic
(a) Add the compound (0.19), dissolved in a
minimum of ethanol to Schiffs Reagent (1
cm3).An immediate magenta colour
indicates aldehyde.
_ (c) clear soiution, add to a
I frl l=l cold solution of naphth-2-ol
L*l Lu
Corrosive
Harmful !?"'.?il*1ff(5cm3;
irecipitate + 1o aromatic amine
Carbox,vlic Acids
1. Acid reaction of aqueous solution to pH paper.

2. Add the sample (0.5g) to sodium hydrogen
t-s,l carbonate solution (2cm3;. If it is difficult to
lssl
Corrosive
observe the evolution of carbon dioxide add light
petroleum (80-100', 1 cm3).
Esters
f.- - I 1. Add the sample Q.2 s.\ to dilute sodium

| I t ^ t hvdroxide (4 cm3; and hlrdroxyammonium
"ai.
t-] l$.Al A-*id.trhydroxyra'i@sgy.
Gorrosive | ffi I
Toxic
l-;l 2. Boil gently for one minute then cool, just acidify
with dilute hydrochloric acid and add a few
LR]
Corrosive
drops of ferric chloride solution. A positive test
is indicated by a red-purple colour.
Phenols
1. Phenols are soluble in dilute sodium hydroxide

solution but are not strong enough acids to liberate
carbon dioxide from sodium hydrogen carbonate
solution.
Mtr2
_Highly. Harmful
Flammable
Dissolve the sample (0.1 g) in ethanol (0.5 .*3)
and water (0.5 cm3). Add ferric chloride solution
dropwise. Many phenols give red-purple or
gr"et coiours.
Dissolve aniline (0.1 g) in conc. hydrochloric acid
@tr3 Toxic Corrosive

(1 cm3; and water (3 cm3;. Cooi to 0'C by
adding an ice cube
trH
Harmful corrosive
Add sodium nitrite (0.1 g) in water (2 cm3;
dropwise until the yellow colour just fades then
add this cold solution to a solution of the
suspected phenol (0.1 g) in dilute sodium
hvdroxide solution. A positive result is shown
by the formation of arcd/orange azo dye.
-
INFRA-RED CORRELATION TABLES
Hydrocarbons and Oxygen Comporutds
illiiririlliiiiliiiiiiii
iliiiiiiiilliiiiiiiiiiiri
ifillii tt
iiiiT
I ll
ii iii I iiiilil
tl ltll
g,
tt
lt
I
I
tl
ll tl
tl iii tlll
Irl!
liiliriiiiiiiliiiiiiiitii
t,c o
o
o
=
o
ct
E
()o
iiiiiriiriiifiiTiiiiiliii
iiiiiiiiiiiiiliiiliii
C o
o
o c!
tt)
x
o
Eg
o iiiiiiiiiiiiiiiiiiiiiiTi
o
c
o
llL
o
o
sf
fiiiiiiiiriiiiiiiiiiiiiii
iilliiil!i!!iiiiiiiiiiii
(E
C'
o
L
E
o
I o
@
i lilliiiiiiiiriiriiiiii
| | lti; ;; ;l; ; ili;ii;
go
3o
F
tr o iiiiiiiiiiiiiiiiiiTiTllli
o
L
L
o
o
-(E
()
o
€
f
iiiiiiiiiiliiiiiiiiiiiifi
i:;;;;iiliilirrrr
tto o
o
iiiillliiii:iilli
L
G o
C\I
tl
L
Tl
5 tt
tt
o
o
lo
ol
o.9
llllu
I IIIEE C
aE EE 6
o
c
o
'Eo 5E
-gg
E
o 'iIE€
| 40
.Cl 6.= U'
r o S,' S5
(E C) cn
() @U' o o tr
tto 6Ee
o o(D o o (5 o o $
gg
(U(D c E o .c
o lloo(,)
!t l<.Y -Y o c ll <Y<ul
-0)
tr oG
Infrared Correlation Tables N ,S, P and Gl Compounds
1600 1400
?2
..o7
1200
o
tsh
Iln
--il-
:U
uo
-I .I-
-I
oo
on
-I-
BFFl
ttOF
Amine salt RNH
ct -Amino acids
3
E}
oo
fFl
Nitriles (cvanidesF z
Nitro coin'pounds'- l.l
lsocvanatbs
lmin-es
.I
-- ET,
F
Oximes -I FI
vt
Groups
Thiols
Thioketones -
Sulphonic acids -
Sulbhoxides - -
Sulbhones
Sulbhonvl chlorider
-- -il
I--
Sulphonhmides- - J fl-
Phosphorus
Phosphates alipha
aromal
Phosphites aliphat
aroma --
Choro
-I
(1) ACTIVITY
DGERIMENT : O 4
INFRARED SPECTROSCOPY
(21 REASONS FOR ACTIVITY
To give the students experience in detecting functional groups using infrared

spectroscopy with the aid of correlation tables.
Octan-1-ol IRRITANT
Benzil IRRITANT
Nujol Not regulated
1,1,1.-trichloroethane HARMFUL R2O/22;52-25
Unknownsamples
IRlA HARMFUL R20/21/?2;326-29
IR2A IRRITANT R36; 526
IR3A HARMFUL
IR4A IRRITANT
IR5A IRRITANT 523-24/25
IR6A TOXIC R26 / 27 / 28-3340 ; 52v36 / 37 45

EXPERIMENT : O 5
ELECTROPHILIC ADDITION TO ALKENES AND GAS LIQUID

CHROMATOGRAPHY
Introduction
The addition of bromine to an alkene is thought to be a stepwise process and
involve the formation of an ionic intermediate (bromonium ion).
*T"- cH2Br
Br
HCR- CH2 /-\ Br
+ + HCR CHZ
Br- Br *?t'_
x> cH2Br
I
Good evidence for the above mechanism is that other added anions may compete
with bromide in the second step and produce a mixture of products. This mixture
may be analysed using gas liquid chromatography.
Objectives
(a) use a separating funnel to separate and purify reaction products;
(b) use an anhydrous salt to dry a non-aqueous solution;
(c) outline the mode of operation of a gas chromatograph;

(d) perform a separation of compounds by gas chromatography;
(e) determine the composition of a mixture from the gas chromatogram.
Procedure
tr
Corrosive
Two solutions of bromine in acetic acid are available, one
of which contains contains lithium chloride (+ LiCl).
CAUTION:
DISPENSE THESE REAGENTS WITTI EXTREME CARE IN
AEUME HOOD.
1. Pipette, with the aid of a pipette filier, 10 cm3 bromine solution

into a 25 cm3 conical flask.
Add hex-L-ene dropwise from a 'pasteur' pipettee until
the bromine colour disappears. Gently t*iri the flask
during the addition. About 0.5 cm3 of the alkene should
Highly be required.
Flammable
3. Transfer the mixture to a separating funnel containing

water (25 cm3;. Rinse the conicat flask with 20 .*3 oi
diethlzl ether
Highly
Flammable (CAUTION : HIGHLY FLAMMABLE)
and add this to the separating funnel. shake well, then

allow the two layers to separate and run off the lower
acqueous_1uy_"I. Add water (20 cm3; to the funnel, again
shake well, allow to separate and run off the aqueous
washings.
tr
Harmful
4.
5.
wash the ether soiution with 0.1 M sodium thiosulphate
solution (20 cm3; as above.
Finally wash the ether solution with water (10 cm3).
6. Transfer the ether solution to a dry 25 cm3 conical flask

and dry by adding anhydrous magnesium sulphate (ask
advice for how much to add). Filter using a fluted filter
paqgr into_a dry conical flask to remove the drying agent
and keep this stoppered until ready for the glc analysis.
7. Repeat steps 1 - 6 using bromine solution (+LiCl).
& GLC Analvsis
Make a note of the operating conditions:
column packing:(SE-30 or similar non-polar

column)
oven temperature:
injection port temperature:
nitrogen pressure:
air pressure:
hydrogen pressure:
signal attenuation:
chart speed:
9. Inject a 1.0p1 sample from the first preparation, marking
the point of injection. Immediately wash the syringe with
diethyl ether. The first materials coming off the column
are ether and unreacted hex-l-ene. This may be confirmed
later by injecting each of these on their own. The ether
peak will go 'off-scale". If the main product peak goes 'off-
scale' aiso or is too small, the sample must be injected
again using either a different sample volume or a
different attenuation.
10. Inject a sample from the second preparation. This time
there should be two product peaks.
ReDortine of results
1. Write an introduction briefly expiaining the advantages of glc analysis.

Report the operating conditions used for the glc.
2. Determine and tabulate the retention times for the peaks on both
chromatograms. Identify each peak. Name the products formed.
3. Determine the percentage composition of the halogeno compounds

formed in the second preparation (+LiCl) by expressing each peak area as a
percentage of the combined area of both peaks.
NB: Areas are automatically calculated.
4. Explain why a mixture of products arises in the second experiment. What

other possible products could arise? Is there any evidence for them in the
chromatogram?
APPENDIX
GAS LIQUTD CHROMATOGRAPHY
The technique is used to separate and identify the reasonably volatile components
of a mixture. Separation occurs when the components differ in their solubilities in
the stationary phase (a non-volatile liquid) and in the moving phase (the carrier
gas).
The liquid stationary phase (eg a silicone) is coated onto granule-s of an inert solid
(eg silica) and these are packed into a stainless steel column.
The mixture to be separated is introduced onto the top of the column as a gas. The
components travel down the column at different rates and emerge one by one from
the bottom of the column. The time a component spends on the column is known
as the retention time.
Materials emerging from the column are detected by a flame ionisation detector.
The effluent mixes with a hydrogen-air mixture and burns in a flame. Ions
produced on combustion of the material carry a small current between two
electrodes in the flame. This current is amplified and fed to a chart recorder. The
area under the peak produced is proportional to the amount of material detected.
MANCHESTER METROPOLITAN UNIVERSITY . COSHH ASSESSMENT
(1) ACTIVITY
EXPERIMENT :O5
ELECTROPHILIC ADDMON TO ALKENES AND GAS CHROMATOGRAPHY
(2) REASONS FOR ACTIVITY
To give the students experience in carrying out a reaction Fving rise to a mixture of
products and determining the composition of the mixture by glc.
(4) HAZARDOUS STIBSTANCES USED AND HAZARD CLASSIFICATION
Bromine in acetic acid TOXIC, CORROSIVE

R10-23-35; S2-7 / 9 -23-26
Hex-1-ene HIGHLY FLAMMABLE

R1 1-18-36 / 37 / 37 ; 39-16-23-29 -33
Diethyl ether (ether) EXTREMELY FLAMMABLE
RL2-1.4 / 1s-79 -34; 39 -1,6-29 -33
Sodium thiosulphate (0.1M) Not regulated

Magnesium Sulphate Not regulated
Products (in ether) EXTREMELY FLAMMABLE,IRRITANT
R12-1 4 / 15 -19 -34; 39 -L G29 - 33

EXPERIMENT : O6
PREPARATION OF AN ESTE& THE USE OF FITACTIONAL DISTILLATION

AND IR SPECTROSCOPY
Objectives
By the end of this experiment you should be able to
(a) Carry out a fractional distillation,

(b) Appreciate the principle behind fractional distillation,
(c) Prepare and purify a simple ester,
(d) Understand the nature of the esterification reaction,

(e) Use ir spectroscopy to follow the progress of a reaction or separation.
In this experiment ir spectroscopy is used to follow the separation of the products
from an esterification reaction ie
catalyst
RCO2H + R'OH RCO2R' + H2O
acid alcohol ---r' ester
Both reactants contain a hydroxy group (which is readily detected in the ir

spectrum) whereas the product does not. The composition of the reaction mixture
can be rapidly determined at various stages.
The separation of ester from reactants is effected by the technique of FRACTIONAL

DISTILLATION. Using a simple distillation apparatus only poor separation of two
volatile liquids of similar boiling point occurs. If a fractionating cofumn is
incorporated into the apparatus more efficient separations cErn be achieved. A
fractionating column is designed so that a continued series of partial condensations
of the vaPour and partial vaporisations of the distillate is taking place during
distillation and is, thus, simiiar to a number of separate disfillations.
Procedure
Preparation of the Ester
tr
Harmful
1. Into a round-bottomed flask (100 .tt3), place
2-methylpropan-1-ol (38.0 cm3, 30.09), propanoic acid
(30.0 cm3,30.09) and concentrated sulphuric acid (exactly
drops) swirl the flask during addition.
6
tr
Corrosive
2.
3.
Add 3 antibumping granules and heat under reflux for
minutes (using a heating mantle).
During the reflux period record the ir spectra of propanoic

30
acid and 2-methylpopan-L-ol; identify the bands

corresponding to the OH and CO2H groups. (Label the ir
spectra as you run hem - it is all too easy to accumulate
subsequently unidentifiable spectra).
Cool the refluxed mixture to room temperature, transfer

to a separating funnel and wash the mixture successively
with water (2 x 25 cm3), sodium bicarbonate solution (2 x
Harmful Z5 cm3) and again with water (25 m3;. Discard the
aqueous washings.
TAKE CARE uthen washing utith the bicarbonate solution

that the funnel is ztented frequently to reliezte the pressure
of the gas eztolaed.
5. Transfer the organic layer to a small conical flask and dry

by adding some anhydrous magnesium sulphate.
6. Fiiter the drying agent off using a fluted filter paper and
run an ir spectrum of the filtrate.
Ptocedure
Fractional Distiiiation
1. Set up an apparatus for fractional distillation consisting of

a L00 .-3 ,or'rrrd-bottomed flask, fractionating column, 0-
250o thermometer, condenser and receiver.
tr
Harmful
2. Transfer the reaction mixture to the distillation apparatus,
add 3-4 antibumping granules and SLOWLY distil the
mixture using a Bunsen burner.
3. Record the temperature at which the first drop distils and at every
5 cm3 of distillate until the temperature reaches I32'C- Then
replace the receiver with a pre-weighed vessel and continue the
distillation.
4. During the distillation collect in numbered ignition tubes small
samples of the distillate every 5 cm3 corresponding to the
recorded temperatures in (3) above.
5. Record infrared spectra of the starting materials and of the pure
ester. (bpt 130"C)
Results and Conclusions
See the specimen write up as a guide when writing up this report.
1. Record the yield, theoretical yield, and percentage yield of the pure ester.
2. Explain briefly, why in this type of reaction a quantitative yield is never

attained.
3. What is the role of the sulphuric acid in the esterfication reaction?
4. Plot a graph of distillation temperature against volume of distillate

collected. Comment on the shape of the curve and estimate the boiling
points of the alcohol and ester from the graph.
5. Assemble the ir spectra; examine the peak positions and decide whether
the fractionation successfully separated the alcohol and ester.
6. Record the exact positions of the following peaks from your spectra:
-OH stretch acid

C=O stretch acid
OH stretch alcohol
C=O stretch ester
C-O stretch ester
7. Hand in all of the product that boils over 132o for inspection.
Science and Engineering Deparhnent of Chemistry
(1) ACTIVITY
DGERIMENT : O 6
PREPARATION OF AN ESTE& SIMPLE DISTILLATION AND FRACTIONAL

DISTILLATION AND IR SPECTROSCOPT
To give the students experience in the preparation and purification of a liquid and
foliowing the progress of a fractionation using glc.
2-Methylpropan-1-ol HARMFUL, HIGHLY FLAMMABLE

R10-20; 51,6
Propanoic acid CORROSIVE R34; 32-23-26

conc. Sulphuric acid CORROSIVE R35; 52-25-30
2-Methylpropyl propanoate Not registered, treat as HARMFUL
SoLr
Sodium bicarbonate Not regulated
Magnesium sulphate Not regulated

EXPERIMENT : O 7
A CONDENSATION REACTION
Introduction
Compounds containing the -CH2-CO- group will undergo Claisen-Schmidt (Aldol)

condensation reaction with another carbonyl compound in the presence of base. In
this experiment you will carry out such a reaction using two 'unknown' starting
materials. You must determine the structure of these starting materials and of the
product, using the information given and any other data you can find.
Obiectives
By the end of this experiment you should be able to:-
(a) Use the correct apparatus to carry out a Claisen-Schmidt (Aldol) reaction.
(b) Use infra-red spectroscopy to classify the strucfures of unknown

compounds.
(c) Deduce the actual structures of the unknown compounds (A) & (B) using
the information given and hence derive the structure of the product (C)
on the basis of the reaction carried out.
(d) Calculate the theoretical yield of the product from the stoichiometry of the
reaction and hence t}:te o/" yield.
Procedure
Dissolve compound A (5.3 e) and compound B

(1.5 g) in ethanol (50 cm3; in a 250 .*3 quickfit
conical flask.
Highly
|.ll
Flammable
Prepare a solution of dilute sodium hydroxide
EI
Corrosive
3.
(12cm3) in water (40 cm3;.
Add this solution to the alcoholic solution, fit a

stopper and occasionally shake the flask for 10
mins.
A
Allow to stand for with occasional
30 mins
shaking. Run an infra-red spectrum of (A) and
(B) during this time.
5. Filter off the soiid, using vacuum filtration,
drain thoroughly. Suspend the solid in water
Highly and filter again.
Flammable
A Recrvstallise the product C from methanol.
Toxic
7. Collect the pure product by vacuum filtration

and dry the crystals by allowing air to be sucked
through them; check the purity by tlc.
8. Record the yield, melting point and IR data of

the product C.
9. Interpret the IR spectra of A, B and C.
Reoortine of results

1. On the basis of the infra-red spectra and the data given below determine
the strucfure of A and B.
Additional data: RMM of A=106

- $= 58
C=234
2. Deduce the structure of the product (C) and name it according to IUPAC
nomenclature.
3. Calculate the actual, theoretical and percentage yieid of C.
4. Give the mechanism of the reaction.
5. In the compound below, why are oniy cr-hydrogens and not p- and y-
hydrogens etc attacked by the base?
CHsCHzCtbCH2CkIeCH=O
6 v Pct
6. Why is water eliminated at the last stage in this type of reaction?
7. Hand in the whole of your sample C for inspection.

8. Comment on the limitations and scoPe of this type of reaction.
(1) ACTIVITY
EXPERIMENT : 07
A CONDENSATION REACTION
To grve the students experience in synthesising an organic compound and identifying the
reactants and product
Undergraduate studen-.s qualified to enter the course
CompoundA HARMFUL ll22;524

CompoundB HIGHLY FLAMMABLE R11; 59-15-23-33
Ethanol HARMzuL, HIGHLY FLAMMABLE Rll-20/21/22;57-1,6
Sodium hydroxide CORROSIVE R35; 32-26-27-37 /39
Methanol TOXIC. HIGHLY FLAMMABLE Rt0-23/24/24-34-40-43

s2-26-28-36/37-4-51.
ProductC Not registered, treat as HARMFUL

EXPERIMENT :O8
PREPARATION OF 1.,3 - DINTROBENZENE
Introduction
Nitrobenzene can be c_onverted by a mixture of fuming nitric acid and concentrated
sulphuric acid into L,3-dinitrobenzene.
HNO3
----+
H2SOa
Noz
Obiectives
(a) appreciate the practical techniques required to synthesise a sample of 1,3-

dinitrobenzene.
(b) be aware of the hazards and techniques required to handle corrosive
compounds.
(c) check the purify of an organic compound by means of tlc.
(d) correlate the infra-red spectrum of a prepared compound with its known
structure.
Procedure
l- :l 1.. Place fuming nitric acid (11.3 g)in a 100 cm3 round
tEl
Corrosive
bottomed flask and add carefully with shaking
concentrated sulphuric acid (18.a g).
Add 2 or 3 anti-bumping granules and a condenser and

place the apparatus in a fume cupboard.
Add_slowly nitrobenzene (7.5 d in small portions, shaking

the flask to ensure thorough mixing.
Toxic
4. Heat the mixture on a boilins water bath for L5 minutes.

5. Allow the mixture to cool somewhat and pour cautiously with
vigorous stirring into cold water (about 250 cm3).
6. Filter off the solid which separates, and wash thoroughly with
water.
7. Recrystallise the solid from ethanol and air dry the pure crystals.
8. Check the purity of the product by tlc, using a suitable eluent.
ReDortine of results
1. Give a brief account of the mechanism of the nitration of benzene.
2. Why is nitrobenzene less reactive than benzene to electrophilic attack ?
-3. Record the yield, melting point and Rf of the prepared 1,3-
dinitrobenzenee. Calculate the theoretical yield and hence the percentage
yield of l-,3-dinitrobenzene.
4. Record its infra-red spectrum as a nujol mull and interpret it as fully as
you can.
5. Hand in a sample of your L,3-dinitrobenzene for inspection, labelled with

your name and the name of the compound.
6. Comment on the scope and limitations of this type of preparation.

MANCHESTER METROPOLITAN UNIVERSITY, COSHH ASSESSMENT
(1) ACTIVITY
B(PERIMENT: O8
PREPARATION OF 1,3-DINITROBENZENE
(2\ REASONS FOR ACTIVITY
To grve the students experience in the electrophilic substitution of a benzene derivative
Fumingnitricacid CORROSIVE, OXIDISING R8-35' 32-3-78-23-26-27-36

acid CORROSIVE
conc. Sulphuric R35; 32-26-30
Nitrobenzene TOXIC R26/27 /28-33;528-36/3745

R71-20/27/?2;57-1,6

EXPERIMENT :O9
ISOLATION OF EUGENOL BY STEAM DISTILLATION AND
SOLVENT EXTRACTION
Introduction
Many important organic compounds are isolated from natural resources.
Eugenol it tL" principal constituent of oil of cloves and is used extensively in
perfumery. Freshly dried cloves contain 74o/o eugenol, the oil being readi$
isolated by steam distillation. This can be done by passing steam into a heated
flask containing the cloves and collecting the mixture of lteam and organic
co-mPo]rnds which distils out. The oil of cloves forms an azeotrope with water
which boils at a much lower temperature than oil of cloves alone. Oil of cloves
and other similar oils can thus be isolated at a temperature at which little
decomposition occurs.
Eugenol is 4-a11yl-2-methoxyphenol and its isolation from oil of cloves if based on

the ability of phenols to form water soluble alkali salts.
a\
\o
OH
----+
NaOH
O-Na+
OCH1 '-l H'C

I
HrC:69 HrC: g"
Extraction of a solution of the oil with aqueous alkali will therefore separate the
eugenol from the other constituents of the oil.
In this experiment, as dried cloves are now very expensive, an artificial "cloves
mixture" is used. This is made up of eugenol which has been absorbed into
wood shavings. Steam distillation of this mixture will therefore separate it into
a steam volatile fraction (containing the eugenol) and a non steam-volatile
fraction which is rejected. Isolation of eugenol from this mixfure involves the
commonly used techniques of solvent extraction and evaporation.
Obiectives
(a) appreciate the practical techniques required to carry out a steam

distillation;
(b) set up and use a steam distillation apparatus;
(c) carry out an extraction by means of a separating fururel and an appropriate
solvent;
(d) use a rotary film evaporator to isolate a compound from a solution;
(e) test for a phenoi by means of the ferric chloride test.
Procedure
Steam Distillation
1. Set up the steam distillation apparatus as shown in the

techniques booklet, (See the lecturer in charge if you need
help).
E
2. Add the "cloves mixture" to the distillation flask using a
powder funnel. Add about 200 cm3 of hot water and start
the steam distillation. Control the rate of heating so that
lrritant distillation is rapid but the level of water in the steam
distillation flask remains constant.
3. Continue the distillation for 30 minutes. The distillate
consists of a dispersion of oil of cloves and pine oils in
water. Cool to room temperature.
Extraction of Oil of Cloves and Pine Oils from the Steam Distillate
Pour the whole of the distillate into a large separating

funnel (1 litre) (see Techniques sheet) and add 1,1,I-
trichloroethane (25 cm3;. Stopper the flask and shake the
Toxic inverted flask, venting the flask from time to time by
means of the tap (ask the lecturer in charge to show you
how to do this). After completion of the extraction allow
the mixture to settle.
5. Run the lower organic layer (1,L,1.-trichloroethane

solution) into a 250 cm3 conical flask and extract the
aqueous layer that remains in the separating funnel with a
further portion of 1.,1.,7-trichloroethane (25 cm3;. Repeat
the extraction and run the lower organic layer into the
conical flask thus combining the trichlorethane solutions.
Discard the residual aqueous solution.
6. Wash the combined 1,L,L-trichloroethane extracts by
extraction with water (10 cm3; in a separating funnet.
Run the lower organic layer into a conical flask and
discard the aqueous layer in the separating funnel. All the
organic compounds present in the distillate have now
been extracted into 1,L,L-trichloroethane.
Isolation of Eueenol
tr
Corrosive
7. Pour the L,L,1,-trichloroethane solution back into the
separating funnel and add dilute sodium hydroxide
solution (40 cm3;. Shake, allow to settle, then run the
lower organic layer into a conical flask. Run the aqueous
alkaline upper layer into a separate conical flask and keep.
8. Return the organic layer to the separating funnel and

extract with a further portion of dilute sodium hydroxide
solution (20 cm3;. Extract, allow to settle, then discard the
lower organic layer. Combine the upper aqueous layer
with the previously obtained alkaline aqueous solution in
the conical flask. A11 the eugenol has now been extracted
into the sodium hydroxide solution as its sodium salt
whilst the other organic compounds have remained in
the 1,1,1-trichloroethane.
rJ 9. Add dilute hydrochloric acid to the aqueous alkaline

solution in the conical flask until the solution is acid
tRJ
Corrosive
when spotted by means of a glass rod onto a piece of
litmus paper. A white milky suspension of eugenol
should be obtained.
10. Extract the liberated eugenol with L,L,L-trichloroethane (25

.*3) as described in Section 4. Repeat the extraction with
a further portion of 1,'J-,L-trichloroethane (25cm3; and
combine the 1,1,L-trichloroethane extracts in a conical
flask. To dry the L,1,1,-trichloroethane solution add
magnesium sulphate to the solution until a suspension of
magnesium sulphate is apparaent. (See the lecturer in
charge if in doubt).
11. Filter the dried solution through a fluted filter paper and
glass funnel (see the lecturer in charge on how to make a
fluted filter paper) into a weighed dry round bottom flask
(100 cm3;.
12. Remove the 1,1_,1-trichloroethane by means of a rotary
film evaporator (see techniques trootteg until only a
viscous oil remains in the flask. Weigh the flask and
hence deduce the yield of eugenol obtiined. If there was
2g of eugenol in the original "cloves mixture" calculate
the percentage recovery.
13. Check the purity of the eugenol by tlc and also run an
infra-red spectrum of the producf using one drop of the
liquid.
E 74. Transfer the sample of eugenol to a glass sample bottle

and hand in for inspectioi.
lrritant 15. Ferric Chloride Test for Phenols
Eugenol can be shown to be a phenol by its behaviour

with ferric chloride solution. All phenols form complex
ferric salts which are usually coloured.
t--l
tJl Dis^solve 2 drops of your isolated eugenol in ethanol (5
tr
lsflk I .*3) and add 2 drops of ferric chioride solution. Record
your observations. Sometimes the colour is not very
.*Yt -
Harmful
pronounced in ethanol so repeat the test but using 5 cm3
of a 50/50 ethanol/water mixfure instead of ethanol.
t-;r
E]
Corrosive
Repeat the test on the following phenols: phenol, cresol,
catechol, methyl salicylate.
Wash your hands on completion of these tests
Repqrting of Results
see the specimen write up as a guide when writing up this report.

7. Record the yield and percentage yield of eugenol obtained, and its R1
value.
2. Record the colour changes associated with the phenols on the addition of
ferric chloride solution. Give the structure and ruPAC names of the
phenols used.
3. Comment on the scope and limitations of the steam distillation technique.

4. Comment on the results of the ferric chloride test for phenols.
5. There are two immiscible iiquids in a separating funner, one
of which
water. How could you test quickly and safely to"dir.o,o"r whether the is
other liquid was 1-,1,'J.-trichloroethane or ether ?
Interpret the infrared spectrum of the prepared eugenol on the basis

of its
known structure.
Science and Engineering Departrnent of Chemistry
(1) ACTIVITY
P(PERIMENT : O 9
ISOLATION OF EUGEONAT BY STEAM DISTITLATION AND SOLVENT

EXTRACTION
To give the students experience in
Undergraduate studmts qualified to enter the course
Cloves mixture IRRITANT

1,1,1-Trichloroethane HARMFUL R20/22;52-25
dil. Sodium hydroxide CORROSIVE 1135; 32-26-27-37/39
dil. Hydrochloric acid IRRITATANT R36/38;52-25-28

Magnesium sulphate Not regulated
Phenol samples TOXIC, CORROSIVE M5/25-3a; 32-28-4
R-71-20/2L/22;57-16

EXPERIMENT : O 10
PREPARATON OF METHYL ORANGE
Introduction
Aromatic diazonium salts are reasonably stable at OoC and can couple to activated
aromatic {ngs such as phenols and anilines to give highly coloure-d azo
comPounds. In this Experiment the diazonium salt from sulphanilic acid is
coupled to N,N-dimethylaniline to give, upon basification, niethyl orange.
it' fz.*t'anr^\,;""D
cl3c)r\ %n
z\NaNo2 z\ /
V*tV;"'P*
sosH so3H
,ethy,oranin
\ SO3Na*
Obiectives
(a) appreciate the practical techniques required to prepare an azo dye.
(b) understand the need to keep a reaction mixture at low temperature to

prevent decomposition of an intermediate.
(c) be aware of the need to add reagents slowly to a reaction mixture so as to
confrol the rate of reaction and qualif of the product.
Procedure
i. Add finely powdered sulphanilic acid (0.02 mol) to a

solution of anhydrous sodium carbonate (0.01 mol)
in water (25 cm3; contained in a 250 cm3 conical
Harmful flask. Warm the mixture on a steam bath to give a
clear solution. Add a solution of sodium nitrite
(0.025 mol) in water (5 cm3; then cool the mixture
until the temperature is less than 5'C.
lll 2. Add hydrochloric acid (mixfure of conc

hydrochloric acid (4 cm3) water (8 cm3) VERY
lRl
Corrosive
SLOWLY (dropwise) with continuous stirring. Do
not allow the temperature to rise above L0'C. Leave
the solution to stand in an ice-bath for L0 minutes
to ensure complete diazotisation.
l- I 3. Slowly add a solution of dimethylaniline (0.02 mol)
mol
^
| &f/
ffi | l-f
in water (5 cmc)
cm3; and concentrated hydrochloric acid
acic
| | I 5 | tz.*3) to the cold well-stirred diazo solution.
Toxic I i.S |
{.llow the mixture to stand for 5 minutes then add
Conosivd dilute sodium hydroxide soiution SLOWLY WITH
STIRRING. (About 25 cm3 are required to give a
uniform orange colour).
tr
Harmful
4. Warm the mixture to 50oC on a steam bath. When
nearly all the methyl orange has dissolved, add
sodium chloride (59) and stir well until dissolved.
Allow to cool and filter off the product with a
Buchner funnel. Recrystallise the product by
dissolving in the minimum quantity of boiling
water using a Bunsen burner to heat the water, cool
to room temperature and filter off the recrystallised
product.
5. Check the purity of the product by tlc.
5. Dissolve a few crystals of your product in water

(5cm3;. Add dilute hydrochloric acid (2-3 drops)
and observe and record any changes. Comment on
vour observations.
Reoortine of Results
1. Record the yield and R1 of your product and calculate the theoretical and
percentage yields.
2. Hand in a sample of your product, labelled with your name and the name
of the compound.
-
3. Comment on the scope and iimitations of this method for the preparation
of azo dyes.
4. Diazonium coupling to anilines is usually carried out in slightly acidic

conditions, while coupling to phenols takes place most readily under
slightly alkaline conditions.
Explain.
5. Methyl orange might be prepared by another route, using

p-amimodiethylaniline as one of the reagents. What is the route and
comment upon its viability?
(1) ACTIVITY
EXPERIMENT: O1.0
PREPAT(ATION OF METTIYL ORANGE
To give the students experience in the sythesis of an organic compound involving a

diazotisation
Undergraduate studerris qualified to enter the course

(41 HAZARDOUS SUBSTANCES USED AND HAZARD CLASSIFICATION
Suphanilic acid HARMFUL R20/21/?2;S25,-28

Sodium Carbonate IRRITANT R36: 522-26
Sodium nitrite TOXIC, OXIDISING R8-25-31; S44
Hydrochloric acid CORROSIVE Il34-37; 32-26
Dimethylaniline TOXIC 1123/24/25-33;528-37-4
Diazonium solution Not registered, treat as TOXIC
dil. Sodium hydroxide CORROSIVE R35; 32-26-27-37 /39
Sodium chloride Not regulated

Methyl orange TOXIC 522-24/25

EXPERIMENT : O 11
PREPARATION OF ACETANILIDE
Introduction
The reaction between aniline and acetic anhydride is an example of an acylation

reaction. This involves nucleophilic attack by the amino group of aniline on the
carbonyl group of the acid derivative to give an addition intermediate followed
by elimination of ethanoate (acetate) anion.
NH2 NHCOCH3
+ Gr?.ffq2o + + CH3COOH
L/
3
Objectives
By the end of this experiment you should be able to :
(a) Select and assemble the correct apparatus to perform a reaction under
reflux.
(b) Prepare a pure sample of acetanilide.
(c) Correlate the infra-red spectrum of the prepared compound with its
known structure.
(d) Calculate the theoretical yield of product from the stoichiometry of the
reaction.
(e) Calculate the % yield for the reaction.
Procedure
1. Weigh out aniline (5.0g) into a L00 cm3 pear-shaped flask

and fit a reflux condenser.
Toxic 2. Use two clamps to secure the apparatus to a retort stand at

a height to allow the flask to be heated by a micro bunsen.
l- 3' Slowly add a solution of dimethylaniline (0.02 mol)
^l in water (5 cm3; and concentrated hydrochloric acid
roxic E.l
LE] (2 cm31 to the cold well-stirred diazo solution.
jL+ | Allow the mixture to stand for 5 minutes then add
Corrosive dilute sodium hydroxide soiution SLOWLY WITH
ST/RR/NG. (About 25 cm3 are required to give a
uniform orange colour).
tr Harmful
4. Warm the mixture to 50"C on a steam bath. When
nearly all the methyl orange has dissolved, add
sodium chloride (59) and stir well until dissolved.
Allow to cool and filter off the product with a
Buchner funnel. Recrystallise the product by
dissolving in the minimum quantify of boiling
water using a Bunsen burner to heat the water, cool
to room temperature and filter off the recrystallised
product.
5. Check the purity of the product by tlc.
6. Dissolve a few crystals of your product in water

(5cm3;. Add dilute hydrochloric acid (2-3 drops)
and observe and record any changes. Comment on
your observations.
ReDortine of Results

1. Record the yield and Rr of your product and calculate the theoretical and
percentage yields.
2. Hand in a sample of your product, labelled with your name and the name
of the compound.
-
3. Comment on the scope and limitations of this method for the preparation
of. azo dyes.
4. Diazonium coupiing to anilines is usually carried out in slightly acidic

conditions, while coupling to phenols takes place most readily under
slightly alkaline conditions.
Explain.
5. Methyl orange might be prepared by another route, using

p-amimodiethylaniline as one of the reagents. What is the route and
comment upon its viability?
Science and Engineering Departrnent of Chemistry
(1) ACTIVITY
DGERIMENT : O 11
THE PREPARATION OF ACETANITIDE
(2' REASONS FOR ACTIVITY
To grve the students experience in the synthesis of an organic compor.rnd and analysing
the product.
(41 HAZARDOUS STIBSTANCES USED AND HAZARD CLASSIFICATION
Aniline TOXIC R23/24/25-3340;528-36/37-M

Glaciai acetic acid CORROSIVE FLAMMABLE R10-35; 32-23-26
Zincdust FLAMMABLE R10-15; 57/8-43
Ethanoic anhydride CORROSIVE FLAMMABLE R10-34; 526
Acetanilide HARMFUL M0/21/22;526-28
a
EXPERIMENT: O 1"2
MULTISTAGE SYNTHESIS OF AN AZO DYE
Introduction
Many organic compounds cannot be synthesised directly but have to be prepared by
a number of steps. It is important that each step takes space in high yield otherwise
the percentage conversion for the whole slmthesis will be very l<iw. In this case
aminobenzene (aniline) needs to be first converted to the corresponding amide
before nitration. The product is then hydrolysed to give mainly 4-
nitroaminobenzene followed by dtazotisation and coupling to give the required azo
dve.
NH2 NHCO.CH3 NHCO.CH3

(cH2co.)20 HNO3
-----_-+
H2S04
ozN
-.> NO,
r^
I NaOH
1.NaNo2,zHCrl'"
\2
| ,r**a*.^ra"-
ozN
\*
Obiectives
@
(a) Appreciate the practical techniques required to prepare an azo dye.
(b) Be aware of the hazards and the techniques required to handle potentially
dangerous compounds.
(c) carry out colum chromatography of an impure product so as to isolate the

different components.
(d) Correlate the infra red spectrum of a prepared compound with its known
structure.
(e) Use tlc to compare the Rf values obtained of a prepared product with those
of compounds of known structure.
Procedure
HAZARDS
Concentrated acids are used to carry out these reactions: HANDLE THEM WITH
GREAT CARE! Wear glooes. Drench any spillage with water and neutralise
with solid sodium carbonate. An intermediate in the synthesis -is 4-nitroaniline
contaminated usith isomers, these materials are toxic, all contact must be aaoided
- use gloaes and safety spectacles.
:Staee l.:
Preparation of N-ohenvlethanamide (acetanilide)
1. Transfer aminobenzene (aniline) (5 cm3,s.fg)

and glacial acetic acid (5 cnr3,5.2g1to a 100 cm3
Toxic
tr
Corrosive
round-bottomed flask fitted with a water-cooled
condenser. Add a small pinch of zinc dust
(about 0.059) and a few anti-bumping granules.
Add ethanoic anhydride (acetic anhydride) (5
ch3, 5.Ag) cautiously down the condenser, Swirl
the flask to mix the contents then heat the
mixture under reflux using a heating mantle for
30 minutes.
2. Alow the reaction mixture to cool slightly then

decant it in a thin stream into water (100 cm3;
containing one or fwo ice cubes in a 250 cm3
beaker, stirring continuously during the
addition. The small amount of zinc dust that
was added to reduce the coloured impurities in
the aniline should be left in the reaction flask
together with the anti-bumping granules.
3. Filter off the crude product using a Buchner

funnel and flask; wash the solid with cold water
(10 cm3), drain it well in the funnel then
transfer it to a 250 cm3 conical flask.
A
Recrystallise the whole of the crude product
from water, making sure the water bbils and you
obtain a complete solution. Filter the hot
solution through a pre-warrned funnel with a
cotton-wool plug. Do not make the cotton wool
plug too tight, (the recrystallisation technique is
described in experiment 2). Allow the
crystallisation liquors to cool slowly; when cold,
collect the crystals using a Buchner funnel and
flask. Wash with a little ice-cold water, drain
thoroughly then dry on a watch glass in an oven
(not more than 80").
5. Determine the yield and melting temperature of

your purified product. Record the i.r. spectrum
as a Nujol mull, indicate the absorptions due to
NH, CO and ArH on the spectrum. Retain a
small sample of your pure product for
inspection and calculate the percentage yield.
Staee 2:
Nitration of N-phenvlethanamide followed bv hvdrolvsis
tr
Corrosive
1. Place the prepared acetanilide (2.69) in a 100 cm3
pear-shaped flask, add acetic acid (2.0 cm3) using
a pipette fitted with a safety pump. Carefully add
concentrated sulphuric acid (2.0 cm31 to the flask
in the same way. Mix the contents by carefully
rotating the flask; when a complete solution has
been obtained, stand the flask in ice/water.
tr
Corrosive
2. Whilst the solution is cooling, carefully make
up a mixture of concentrated nitric acid (1.2 cm3)
and concentrated sulphuric (2.0 cm3;. Add this
mixture dropwise to the cooled solution in the
flask. Agitate the contents gently by rotating the
flask during the addition and keeping it cold all
the time. When the addition is complete, leave
the flask to stand in the ice/water for 5 minutes
then allow it to warm to room temperature over
15 minutes.
J. Carefully add water (15 cm3; to the acidic

reaction mixture, mix the contents of the flask
thoroughly. Add a few anti-bumping granules
and heat under reflux for 20 minutes.
tr
Corrosive
4. lf the following neutralisation is catied out at
too high a temperature a black tar is formed.
Cool the reaction mixture with an icelwater bath

and add dilute sodium hydroxide slowly until
precipitation is complete (use indicator paper to
check that the pH is higher than 8).
Keep the solution cold at all times.

Filter off the solid product using an appropriate
size of Buchner funnel and flask. Wash the
solid with a little ice cold water (no more than 10
.*3) and drain thoroughly. Dry the product by
pressing between filter papers and standing in a
desiccator overnight, do not use an oven.
Record the yield of the dry product.
Analvsis of the crude product bv tlc
1. Dissolve a small sample of the crude product in
@Toxic
L,L,1-trichloroethane. Spot this solution onto six
tlc plates keeping the spots as small as possible
but still visible, you may find it useful to look at
the instructions and notes you made for
experiment L.
II 2. Run the plates in the following eluents:
trn. l
methanol, ethyl acetate, trichloroethane,
tetrachloroethene, toluene, and 60-80'
@
t\t7I
Highly petroleum ether. Assess which eluent gives the
Flammable best separation, determine the Ri values of the
Toxic
individual components on the plate eluted with
the best eluent and compare these values with
those for authentic samples of 2,3 and 4
nitroanilines run under similar conditions with
the same eluent.
Bulk purification by column chromatography
1. Make up an alumina chromatography column as
@
Toxic
follows: weigh out alumina (40g). Clamp a glass
chromatography column (with built-in tap)
vertically and add about 40 cm3 of 1.,1.,1-
trichloroethane to three-quarters fill the column.
P1ace a clean dry filter funnel in the top of the
column and add the alumina slowly through the
funnel so that it sinks into the trichloroethane.
Add a small quantity of sand to the column so as to
form a thin layer on top of the alumina. Run the
solvent out until the level is iust above the
alumina surface;
Do not allow the surface to run dry.
2. Dissolve about 200-400 mg of the crude product in

the minimum volume of L,'J.,1,-trichloroethane in a
small test tube. LJse a glass rod to crush any lumps
and warm gently on a steam bath. Cool the
solution before carefully pouring onto the top of the
column and furn the tap to allow the eluent to run
out. Keep adding more trichloroethane to the top
of the column to stop it running dry. Collect each
of the coloured bands separately as they elute from
the column and evaporate to drymess using a rotary
evaporator.
3. When the separation is complete allow the column

to run dry then discharge the spent alumina by
inverting the column. Dispose of the spent
alumina by placing it in a plastic bag and put the bag
in the hazardous solids bin.
Spectroscooic analvsis of the product
1.. Record the i.r. spectra of any samples isolated by

chromatography. Compare the spectra with standard
spectra of 2-,3- and 4 nitroanilines: with care you
should be able to identify your products by comparison
of the CH bending region particularly. Confirm your
identification using tlc.
Staee 3:
Preparation of an azo dye
Dissolve 4-nitroaniline (0.599) in a mixture of

water (10 cm3; and concentrated hydrochloric
acid (4 .*3) ir a 50 cm3 beaker. It may be
necessary to warm the mixture to give solution,
but it must be cooled to below SoC afterwards
even if crystals form.
2. Dissolve sodium nitrite (0.4g) in water (4 cm3;

and cool this solution to below 5"C also.
mtrg
Finally dissolve 2-naphthol (0.72g) in dilute
sodium hydroxide (2M, 10 .*3 ) and cool this
solution to below 5oC.
Corrosive
4. To carry out the coupling reaction, the cold

sodium nitrite solution is added dropwise to the
cold nitroaniline suspension swirling after each
addition and keeping the temperature below
5'C. This solution of the diazonium salt is
allowed to stand at or below 5'C for five minutes
before it is added slowly and with stirring to the
naphthol solution. Leave the dye suspension to
stand in the cooling bath for L0 minutes or so
then filter off the dyestuff using a Buchner
funnel and flask. Wash the solid with a little
cold water, then with methanol and finally dry
in air.
Record the yield, percentage yield and ir
spectrum (as a Nujol mull) of the dry dyestuff;
run a tlc using dichloromethane as eluant to see
Toxic how many comPonents are Present.
Reporting of Results
You do not have to write out the experimental procedures given above; any
changes to the above procedures or observations made whilst carrying them out
shouid be reported however. Also if you encountered any unforeseen problems
or hazards, these should be reported. Marks will be given for the following
specific data:
1. Give mechanistic equations for the reactions you have carried out.
Why does the aminobenzene have to be converted to the amide before
nitration?
2. Report the yields, and calculate the theoretical and percentage yields for
each of the materials you have made. Calculate the overall percentage
yield of 4-nitroaniline and the azo dye from aminobenzene.
3. Report the melting point of N-phenylethanamide.
4. Submit samples of all products for inspection.
5. Report the results of the TLC study; what are the advantages or limitations
of column chromatography compared to recrystallisation?
6. Compare the ir spectra of the compounds you have made with standard
spectra and relate the spectra to the structures.
7. Explain the orientation of the azo dye.
8. Mass spectrometry:
Mass spectrometry is a very powerful techniques used to elucidate the
strucfures of organic compounds. In this technique, molecules are
converted into ions in the gas phase by bombardment with electrons for
example. The ions are accelerated then separated by electric and magnetic
fields according to their different masses (strictly mass to charge ratio).
The mass spectrum is thus a sort of histogram showing the populations of
ions of different masses.
Particular functional groups can be recognised in a mass spectrum by the

characteristic fragmentations that take place in the very high energy
conditions of the spectrometer source. For example, figure 1 is the mass
spectrum of 4-nitroaniline; the peak at m/z = 138 corresponds to the
molecular ion (this is the molecule less one electron) and that atm/z = 108
to a fragment ion which arises by loss of moiecule of nitrous oxide from the
138 ion. The ion at m/z = 92 corresponds to the loss of the entire nitro
grouP.
Figure 2 shows the mass spectrum of a co-product formed in the second stage
of this experiment and isolated by column chromatography. Suggest a
structure for this compound.
(1) ACTIVITY
EXPERIMENT: O12
MULTI STAGE OF SYTHESIS OFAN AZO DYE
To give the students experience in multistage syntheses of organic compor:nds and

purification of an intermediate by column chromatography.
Acetanilide HARMFUL 1120/21/22;526-28

Acetic acid CORROSWE, FLAMMABLE
R10-35; 32-23-25
conc. Sulphuricacid CORROSIVE R35; 32-26-30

conc. Nitric acid CORROSIVE, OXIDISING
R8-35; 52-23-26-27-30
dil Hydroxide
Sodium CORROSIVE R35; 32-26-27-37 /39
Nitroanilines TOXIC IU3/24/25-33,528-36/374
Alumina (MFC 200 mesh) Not regulated
4-nitroaniline TOXIC P23/24/25-33,52936/37-44
conc. Hydrochloric acid CORROSIVE F.3/-37,2-26 S
Sodium nitrite TOXIC, OXIDISING R8-25-31; S44

Diazonium salt solution Not registered, treat as TOXIC
2-naphthol HARMFUL tl20/22;524/?5
Dyestuff Not registered, treat as TO)OC

EXPERIMENT : O 13
NITRATION OF N.PHENYLETHANAMIDE (ACETANILIDE) FOLLOWED BY
FINROLYSIS
Introduction
Nitration of acetanilide followed by base-catalysed hydrolysis will give a mixture

of isomers of nitroaniline. The diiferent componenti can be isolat6d by column
chromatography
Obiectives
(a) Be aware of the hazards and the techniques required to handle potentially
(b) Carry out column chromatography of a mixture of product so as to isolate

the different components.
(c) Use tlc to compare Rlvalues obtained of a prepared product with those of
compounds of known structure.
(d) Correlate the infra-red spectra with those of authentic samples and
identify the components of the mixture.
Procedure
Nitration of N-phenylethanamide followed by hydrolysis
EI 1. Place the acetanilide (2.69) in a 100 cm3 pear-
lRl
Corrosive
shaped flask, add acetic acid (2.0 cm3) using a
pipette fitted with a safety pump. Carefully add
concentrated sulphuric acid (2.0 cm3; to the flask
in the same way. Mix the contents by carefully
rotating the flask; when a complete solution has
been obtained, stand the flask in ice/water.
Run the plates in the following eluents:
methanol, ethyl acetate, trichloroethane,
M@2
Flammable
-ffi
tetrachloroethene, toluene, and 60-80'
petroleum ether. Assess which eluent gives the
best separation, determine the Rl values of the
individual components on the plate eluted with
the best eluent and compare these values with
those for authentic samples of 2,3 and 4
nitroanilines run under similar conditions with
the same eluent.
Bulk nurification bv column chromatosraphv
1. Make up an alumina chromatography column
@Toxic
as follows: weigh out alumina ( 0g). Clamp a
glass chromatography column (with built-in tap)
verticaily and add about 40 cm3 of !,L,L-
trichloroethane to three-quarters fil the
column. Place a clean dry filter funnel in the top
of the column and add the alumina slowly
through the funnel so that it sinks into the
trichloroethane. Add a small quantity of sand to
the column so as to form a thin layer on top of
the aiumina. Run the solvent out until the
levei is just above the alumina surface;
Do not allow the surface to run dry.
2. Dissolve about 200-400 mg of the crude product

in the minimum volume of 1.,1.,1.-
trichloroethane in a small test tube. Use a glass
rod to crush any lumps and warm gently on a
steam bath. Cool the solution before carefully
pouring onto the top of the column and turn the
tap to allow the eluent to run out. Keep adding
more trichloroethane to the top of the column
to stop it running dry. Collect each of the
coloured bands separately as they elute from the
column and evaporate to dryrness using a rotary
evaporator.
a
When the separation is complete allow the
column to run dry then discharge the spent
alumina by inverting the column. Dispose of
the spent alumina by placing it in a plastic bag
and put the bag in the hazardous solids bin.
MANCHESTER METROPOLITAN UNIVERSITY - COSHH AS SESSMENT
FACULTY DEPT/DIVISIONruNIT
(1) ACTIVITY
E)(PERIMENT: O13
NTTRATION OF N.PWE (ACETAI{ILIDE) FOLLOWED BY

I{YDROLYSIS
(2, REASONS FOR ACTIVITY
To grve the students experience in multistage syntheses of organic compounds and

purification of an intermediate by crclumn chromatography.
(O HAZARDOUS SUBSTANCES USED AND HAZARD CLASSIFICATION
Acetanilide HARMFUL R20/21/22;522-24/25-2G28

Acetic Anhydride CORROSM,
FLAMMABLE R10-34; S25
conc. Sulphuricacid CORROSM R35; 52-25-30
conc. Nitric acid CORROSM,
OKDISING R35; S2-23-2G27-%
dil Sodium Hydroxide CORROSIVE R35; S2-2G27-37 /39
Nitroanilines TOXIC R23/24/25-33;528-35/37aa
1,1,1-Trichloro ethane HARMFUL R20/22;52-24/25
Methanol TO)OC, HIGHLY
FLAMMABLE Rtt-2l/E; S2-7-1G24
Ethyl acetate HARMFUL Rl7-n/21/22;57-76
Tetrachloroethene HARMFUL R20/2240;52-23-2*36/37
Toluene HARMFUL, HIGHLY
FTAMMABLE R11-20; SLG2V29-33
Petroleum Ether (6G80) I{ARMFUL, HIGHLY
FLAMMABLE R71-20/2740; S9-7G23-29-33
Alumina Not regulated - Treat as harmful

EXPERIMENT : O L4
PREPARATION OF AN AZO DYE
Introduction
The diazonium salt from 4-nitroaminobenzene is coupled to 2-naphthol to give,

upon basification, a highly coloured azo dye.
NH2
1. NaNOz/HCl/0'C
"r-g
Objectives
2. 2-naphthol,/NaOH
(a) Appreciate the practical tecjniques required to prpeare an azo dye.
@) Be aware of the hazards and the techniques required to handle potentially

Procedure
Preparation of an azo dve
tr
Corrosive
1. Dissolve 4-nitroaniline (0.699) in a mixture of
acid (4 .*3) ir a 50 cm3 beaker. It may be
but it must be cooled to below 5oC afterwards
2. Dissoive sodium nitrite (0.4g) in water (4 cm3;

and cool this solution to below 5oC also.
2. Whilst the solution is cooling, carefully make
H
Corrosive
up a mixture of concentrated nitric acid (L.2.*3)
and concentrated sulphuric (2.0 cm3;. Add this
mixture dropwise to the cooled solution in the
flask. Agitate the contents gently by rotating the
flask during the addition and keeping it cold all
the time. \Atrhen the addition is complete, leave
the flask to stand in the ice/water for 5 minutes
then allow it to warm to room temperature over
l-5 minutes.
3. Carefully add water (15 cm3) to the acidic

reaction mixfure, mix the contents of the flask
thoroughly. Add a few anti-bumping granuies
and heat under reflux for 20 minutes.
tr
Corrosive
4. Ifthe following neutralisation is catieil out at
too high a temperature a black tar is farmed.
Cool the reaction mixture with an ice/water bath

and add dilute sodium hydroxide slowly until
precipitation is complete (use indicator paper to
check that the pH is higher than 8).
Keep the solution cold at all times.

Filter off the solid product using an appropriate
size of Buchner funnel and flask. Wash the
solid with a little ice cold water (no more than L0
.*3) and drain thoroughly. Dry the product by
pressing between filter papers and standing in a
desiccator overnight, do not use an oven.
Record the yield of the dry product.
Analvsis of the crude nroduct bv tlc
1,. Dissoive a small sample of the crude product in
@Toxic
L,L,1"-trichloroethane. Spot this solution onto six
tlc plates keeping the spots as smail as possibie
but still visible, you may find it usefui to iook at
the instructions and notes you made for
experiment 1.
r-t
IX I |ll 3. Finaliy dissolve 2-naphthol (0129) in dilute
| | | o€t
*=- | sodium hydroxide (2M, L0 .*3 ) and cool this
ifffii
^ I I solution to below 5'C.
Corrosive

coid nitroaniline suspension swirling after each
soc. This solution of the diazonium salt is
allowed to stand at or below 5"C for five minutes
naphthol solution. Leave the dye suspension to
stand in the cooling bath for 10 minutes or so
in air.
Toxic how many comPonents are Present.
1. See the specimen write-up as a guide when writing up this report.
Z. Give a mechanisitic account of the formation of the azo dye and explain
the position of the couPling.
g. Record the infrared spectrum of the product as a nujol mull and interpret
it as fully as you can.
4. Hand in a sample of your product for inspection.

Spectroscopic analvsis of the product
1. Record the i.r. spectra of any samples isolated by

chromato$aphy. Compare the spectra with standard
spectra of 2-,3- and 4-nitroanilines: with care you
should be able to identify your products by comparison
of the CH bending region particularly. Confirrn your
identification using tlc.
You do not have to write out the experimental procedures given above; any
changes to the above procedures or observations made whilst carrying them out
should be reported however. Also if you encountered any unforeseen problems
or hazards, these should be reported. Marks will be given for the following
specific data:
1. Give mechanistic equations for the reactions you have carried out.
\AIhy does aminobenzene have to be converted to the amide before nitration?
2. Report the yields, and calculate the theoretical and percentage yields for the
crude product.
3. Submit samples of all products for inspection.
4. Report the results of the TLC study; what are the advantages or limitations of
column chromatography compared to recrystallisation?
5. Compare the ir spectra of the compounds you have made with standard
spectra and relate the spectra to the strucfures.
6. Mass spectrometry:
Mass spectrometry is a very powerful techniques used to elucidate the
structures of organic compounds. In this technique, molecules are converted
into ions in the gas phase by bombardment with elecfrons for example. The
ions are accelerated then separated by electric and magnetic fields according to
their different masses (strictly mass to charge ratio). The mass spectrum iJ
thus a sort of histogram showing the populations of ions of different masses.
Particular functional groups can be recognised in a mass spectrum by the

characteristic fragmentations that take place in the very high energy
conditions of the spectrometer source. For example, figure L is the mass
spectrum of 4-nitroaniline; the peak at m/ z = 138 corresponds to the
molecular ion (this is the molecule less one electron) and that atm/z = 108 to
a fragment ion which arises by loss of molecule of nitrous oxide from the 138
ion. The ion at m/z = 92 corresponds to the loss of the entire nitro group.
Figure 2 shows the mass spectrum of a co-product formed in the second stage
of this experiment and isolated by column chromatography. suggest a
structure for this compounc.
FACI,JLTY DEPT/DIVISION/UNIT
Scierrce and Engineering Department of Chemistry
(1) ACTIVITY
D@ERIMENT z OIL
PREPARATION OF AAI AZO DYE
(2) REASONS FOR ACTIVTTY
To grve the shrdents experience in multistage syntheses of organic compounds and

purification of an intermediaE by column chromatography.
(O HAZARDOUS SUBSTANCES USED AND HAZARD CLASSIFICATION
Aniline TOXIC R23/24/2*334048;

s28-%/37-44
Glacial Acetic acid CORROSIVE,
FLAMMABLE R1G35; 32-23-26
Zincdust FLAMMABLE R10-15-17
Acetanilide HARMFUL R20/21/22;522-24/2r2G28
conc. Sulphuric acid CORROSIVE R35; 52-2&30
conc. Nitric acid CORROSIVE,
OKDISING R8-35; S2-23-2G27-96
dil Sodium Hydroxide CORROSIVE k35;52-2G27-37/39
Nitroanilines TOXIC R23/24/25-33,528-%/374
1,1,1-Trichloro ethane HARMFUL R20/22;52-24/E
Methanol TO)(C, HIGHLY
FLAMMABLE Rrr-23/25;52-7-rG24
Ethyl acetate HARMFUL Rn-n/2L/22;57-76
TetracNoroethene HARMFUL R20/224O;52-23-25-36/37
Toluerre HARMFUL, HIGHLY
FLAMMABT^E R11-20; StG25-29-33
Petroleum Ether (@80) HARMFUL, HIGHLY
FLAMMABLE R7L-20/2L40; S9-7G23-29-33
4-nitroaniline TOXIC R23/24/E-33,528-%/374
conc. Hydrochloric acid CORROSM k34-37,2-26 S
Sodium nitrite TO)OC, OXIDISING R8-531; 944
2-naphthol HARMFUL R2O/22;STL/ZS
Azodye product Not registered, Treat as TO)OC
Dichloromethane HARMFUI R2040; SZT24/?h36/37
Look up the R and S ohrases listed in the Techniques Booklet

EXPERIMENT : O 14
PREPARATION OF AN AZODYE
Introduction
The diazonium salt from 4-nitroaminobenzene is coupled to 2-naphthol to give,

upon basification, a highly coloured azo dye.
NH2
1. NaNOz/HCl/0'C
"r-g
Objectives
2. 2-naphthol/NaOH
(a) Appreciate the practical tecjniques required to prpeare an azo dye.
(b) Be aware of the hazards and the techniques required to handle potentially
Procedure
Preparation of an azo dlze
H
Corrosive
L. Dissolve 4-nitroaniline (0.699) in a mixture of
acid (4.tr,3) ir a 50 cm3 beaker. It may be
but it must be cooled to below 5"C afterwards
2. Dissolve sodium nitrite (0.ad in water (4 cm3;

and cool this solution to below 5"C also.
r--l
IX | 3. Finallv dissolve 2-naphthol (0.72g) in dilute
| nL I
| |-lo€t sodium hydroxide (2M, 1.0.*3 ) and cool this
ilarm?ui
- I I solution tb below 5'C.
Corrosive

cold nitroaniline suspension swirling after each
5oC. This solution of the diazonium salt is
allowed to stand at or below SoC for five minutes
naphthol soiution. Leave the dye suspension to
stand in the cooling bath for 10 minutes or so
in air.
Toxic how many components are present.
Reporting of Resuits
1. See the specimen write-up as a guide when writing up this report.
2. Give a mechanisitic account of the formation of the azo dye and explain
the position of the coupling.
3. Record the infrared spectrum of the product as a nujol mull and interpret
it as fully as you can.
4. Hand in a sample of your product for inspection.

MANCHESTER METROPOLITAN UNIVERS ITY - COSHH AS SES SMENT
FACTJLTY DEPT/DIVISIONruNIT
(1) ACTIVITY
E)(PERIMENT : O 14
PREPARATION OF AI{ AZO DYE
(2) REASONS FOR ACTTVTry
To grve the students in multistage syntheses of organic compounds and

purification of an intermediab by column chromatography.
Aniline TOXIC P23/24/2*3340-4{l;

s28-36/374
Glacial Acetic acid CORROSM,
FLAMMABLE R1G35; 52-23-26
Zincdust FLAMMABLE R10-15-17
Acetanilide HARMFUL R20/21/22;522-24/2*2G28
conc. Sulphuric acid CORROSIVE R35; 52-2630
conc. Nitric acid CORROSM,
. OXIDISING R8-35; S2-n-2G27-36
dil Sodium Hydroxide CORROSM R35; S2-2G27-97 /39
Nitroanilines TOXIC P23/24/25-33,SZE-%/37'4
1,1,1-Trichloro ethane HARMFUL R20/22;52-24/E
Methanol TO)OC, HIGHLY
FLAMMABLE Rrr-l3/E; 32-7-1624
Ethyl acetate HARMFUL Rn-2f/21/22r57-16
Tetrachloroethene HARMFUL P20/2240;52-2T2Vj6/37
Toluene HARMFUL, HIGHLY
FL{MIvIABLE R11-20; 51G25-29-33
Petroleum Ether (60401 HARMFUL, HIGHLY
FLAMMABLE RIL-20/2L40; S9-1G23-29-33
4-nitroaniline TOXIC R23/24/E-33,528-X/374
conc. HydrocJrloric acid CORROSM R34-37,2-26 S
Sodium nitrite TO)CC, OXIDISING R8-2F31; Sa4
2-naphthol HARMFUL R20/22;524/E
Amdyeproduct Not registered, Treat as TO)OC
Dichloromethane HARMFUL R20-40;52T24/25-%/37
Look up the R and S ohrases listed in the Techniques Booklet

Organic Chemistry Expt Level 1

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Organic Chemistry Expt Level 1

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@RGANIE CHENATSTRY

AIMS OF THE COURSE

. To illustrate and teach by first hand experience the basic practical

. To complement and supplement lecture course material, especially

. To develop the student's abiiity to interpret and analyse

o To teach the student to communicate his/her results in a clear and

Date and title of experiment

A brief background to the theory and general practical procedures

NB This section must be written in your own words.

A11weighings and rough calculations should be recorded, and where

A sample of all products should be handed in for assessment, in a

Conclusion and Exercises:

All weighings and rough calculations should be recorded, and where

A sample of all products should be handed in for assessment, in a

Conclusion and Exercises:

All chemicals are hazardous to a greater or lesser extent.

Highty fl ammable substance

Eth:lt lay be formed by interaction of salts of alcohols or phenols with alkyl or

In this experiment, the 2-naphthate ion, prepared by dissolving 2-naphthol in

Thus a 519L mechanism may be involved.

An excess of the water soluble sodium 2-naphthate is used so as to convert ajl_the

Actual yield = 1.659 = 81"/o (literature 88%)

Benzyl,2-naphthyl ether was prepared in 81% yield by reaction of sodium-2-

%yierd, = #ffix rco%

overallyield = ih"#"# x 1,00%

From the equation

l-mol 1 mol product

2s.0g + 9.09 (this is the exprimental yield)

25.0/100 = 0.250 mol 9.0/82 = 0.11 mol

From the equation

0.0087(0) mol 0.00705 mol

theoretical Yield = 0.00870 mol % yield = lf.onx1oo%

calculate the overall yield'

Pure crystalline organic compounds have sharp characteristic melting points.

By the end of this experiment you should be able to

(c) run a tlc of an "unknowrl" material;

(e) measure and record R6 values from a tlc.

Make a note of the compound code number now !

A: Thin layer chromatography

2. Using ignition tubes, make up solutions (approx 50 mg in

J. Using a fine capillary tube (drawn from a melting point

The spots appear dark against a green background since

B: Measurement of melting point

L. Seal one end of a capillary melting point tube in a Bunsen

2. Powder a small amount of each sample on a watch giass

3. Place all three tubes alongside a 350" thermometer in a

4. Carefully make L:1 mixtures of the samples, grind them

distance moved by samPle sPot from origin

-2. Identify the odd one out of the three sampies.

THE PURJTY OF ORGANIC CHEMICALS

(2,) REASONS FOR ACTIVITY

To give the students experience in using simple physical techniques to distinguish

(3) STATUS OF PERSONS UNDERTAKING ACTIVITY

Undergraduate students qualified to mter the course

(4) HAZARDOUS SUBSTANCES USED AND HAZARD CLASSIFICATION

lW / A].,\/P / M,lvfP /43 Treat all the unknown

MP /DI,IW /D2, MP/D3

Look up the R and S phrases listed in the Techniques Booklet

By the end of this experiment you should be able to:

(a) select and assemble the correct apparatus to recrystallise samples of up to

(b) select after appropriate tests, a suitable solvent system to recrystallise a

(d) use vacuum filtration to collect a precipitate;

(e) use appropriate apparatus to dry a solid sample;

(0 calculate yields of recrystallised material.