FACULTY OF SCIENCE
DEPARTMENT OF CHEMISTRY
CHE 212
CHEMISTRY LABORATORY MANUAL
2023/2024 Academic Year
Name: ___________________________________
Reg. Number: _____________________________
Group: ________________
CHE 212: GENERAL CHEMISTRY
CHE 212: GENERAL CHEMISTRY PRACTICAL
ISOLATION AND PURIFICATION OF AN ORGANIC COMPOUND: RECRYSTALLISATION OF
BENZOIC ACID
INTRODUCTION
At the end of this practical, students should be able to crystallise and be able to calculate percent yield of products.
PROCEDURE
You are provided with a sample of benzoic acid, which has had to be swept off the floor after the bottle got broken.
Make sure that your Buchner flask and funnel are clean or else your recrystallised product will be more
contaminated.
1. Weigh 5.00 g of the dirty sample and recrystallise it from water in order to purify it.
Note:
• If too much water is used, the benzoic acid will not crystallise out even after cooling while too little
water will lead to crystallization of the product right at the filter and not in the Buchner flask.
• Use glass stiring rods and not the magnetic followers (bullets) because they have a plastic coating
and it will melt.
• Guard against the melting of the benzoic acid as you raise the temperature of the benzoic acid and
water mixture.
2. Suck your product dry, weigh it and reserve a small sample for melting point determination later.
3. Reweigh your purified sample (this should be your starting material for the second recrystallisation) and further
purify your product by repeating the recrystallisation process.
4. Calculate the % yield in each recrystallisation.
5. Use the same melting point apparatus during the determination of the first and second crystallate.
6. Compare the m.p. for the two samples noting if further crystallisation caused any increase in purity. Explain the
difference in the melting point if any.
REFERENCES
Pasto, D., Johnson, C. and Miller, M. (1992). ExperimentalTechniques in Organic Chemistry, Instructor’s Edition,
Prentice Hall Inc.
Vogel A.I., (1954). Experimental details for recrystallisation. In A Textbook of Practical OrganicChemistry
Including Qualitative Organic Alnalysis, 2nd Edition, London, UK, Longmans, Green and Co. Ltd.
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CHE 212: GENERAL CHEMISTRY PRACTICAL
ESTERIFICATION: SYNTHESIS OF ASPIRIN (ACETYLSALICYLIC ACID)
INTRODUCTION
Salicylic acid, o-hydroxybenzoic acid, can be converted into two important esters, asprin and methyl salicylate. The
conversion of the hydroxy group to an acetate ester gives acetylsalicylic acid, aspirin. Although salicylic acid has an
analgesic effect, it is irritating when taken orally. The acetylester, aspirin, is less irritating and is later hydrolysed to
salicylic acid in the intestinal tract. Aspirin is well established as an analgesic (pain - killer) and an antipyretic
(feverreducing agent). World-wide aspirin is one of the most common OTC and prescription drug. Aspirin is known
to act on the central nervous system to relieve inflammation of tissues and reduce blood pressure. Although aspirin
has a relatively low toxicity level it has some adverse physiological effects that restrict its use. Aspirin inhibits blood
coagulation and can cause stomach, intestinal bleeding and allergic reactions.
For this experiment you will esterify the hydroxy group of salicylic acid using excess acetic anhydride in the
presence of sulphuric acid, to give acetylsalicylic acid (aspirin) according to the following reaction:
O
OCCH3
O
CH3COCCH3
+
C O C OH
O O asprin
O acetic anhydride O
salicylic acid
+
CH3C OH
O
Acetic acid Sulphuric
acid is added to the reactants as a catalyst
MATERIALS
Salicylic acid, Acetic anhydride, sulphuric acid (98%), Filter paper, Funnel, Ice cubes or crushed ice, 100 ml
Erlenmeyer flask, 250 ml filter flask, 3 feet of heavy-walled rubber tubing, suction funnel, and aspirator
PROCEDURE
1. Weigh accurately and record the weight of about 2 grams of salicylic acid in a 125 ml Erlenmeyer flask.
Add 6 ml of acetic anhydride and 3-4 drops of concentrated sulphuric acid. Close/seal the flask with cotton
wool to reduce loss of acetic anhydride.
2. Warm the mixture in a water bath at 60oC for 15 minutes. Remove the flask and add 50 ml of cold water.
Induce the formation of aspirin crystals by scratching the inside of the flask with a glass stirring rod while
holding the flask in an ice-water mixture.
3. Filter the contents of your mixture above using suction and add three 10 ml portions of water to wash the
aspirin. Allow the suction apparatus to air-dry the aspirin for 5 minutes. If available, dry the aspirin in an
oven at 100oC for 5 minutes. (If suction filtration apparatus is not available, filter the using a gravity
filtration technique. Wash the crystals with three 10 ml portions of water and then press the crystals
between paper towels to squeeze out any water. Oven dry at 100 oC for 10 minutes or air dry for 20 minutes.
4. Weigh the product and record the mass as grams of aspirin in your data table in your lab book.
5. Dissolve about half the solid crude product in about 7 cm3 of hot 95% ethanol, and pour the solution into
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about 15 to 18 cm3 of warm water. If any solid separates at this point, warm to dissolve and allow the clear
solution to cool slowly. Beautiful needle-like crystals will separate.
6. Dissolve a few milligrams of the substance in about 1 cm3 of methanol and add 1 drop of aqueous iron(III)
chloride.
7. Acetylsalicylic acid does not have a clearly defined melting point, but instead decomposes at a
characteristic temperature range which varies by about 10 o depending on the rate of heating. Record your
melting (decomposition) point in the form "m.p. = Xo-Yo (degrees)" and submit the crystals in a labelled
sample tube.
8. Run the IR spectrum of your sample of aspirin and obtain copies of the IR spectra of the starting materials.
QUESTIONS
1. Calculate the number of moles of each reactant. Identify the limiting reagent. Calculate your theoretical yield
and actual yield of aspirin. How would your calculated actual yield be affected if your final sample was not
dry?
2. Predict the likely impurities in your product and suggest how you could improve the purity of your product.
Compare the reaction of iron(III) chloride solution with (i) your product (ii) salicylic acid and indicate how this
test assists you in determining the purity of your product. Compare the melting point of your product with that
of pure aspirin and comment on the use of melting point as a criterion of purity.
3. How is aspirin prepared commercially? Is the laboratory preparation similar to the commercial one? If not,
suggest reasons for the differences.
4. Salicylic acid derivatives have been used medicinally for many years. The other important methyl ester of
salicylic acid is known as oil of wintergreen. In this ester the phenol functional group is retained. What is the
structure of this other methyl ester of salicylic acid?
5. Identify the functional groups in these three compounds. What are the IR and 1H n.m.r characteristics of these
groups? Briefly describe the differences you would expect in the following spectra of salicylic acid, aspirin and
the other methyl ester of salicylic acid: i) the IR spectra, and ii) the 1H n.m.r spectra. Suggest the best
spectroscopic method of distinguishing between the compounds.
6. Consult a Physicians’ Desk Reference or Pharmacopoeia and identify four commercial drugs that contain
aspirin. Check under analgesics and antipyretics. List the drugs and any contraindications (adverse
physiological effects). Give the reference for your source.
7. Give the reaction mechanism and explain the role of the sulphuric acid in the preparation of asprin.
REFERENCES
BDH Catalogue, Any introductory organic text.
Physicians’ Desk Reference or Pharmacopoeia
Sollimo, V. J., (1979). Synthesis of Aspirin. In Basic College Chemistry in the Laboratory edited by Sollimo, V. J.,
1st edition, New York, USA, McGraw-Hill Company, pp275-280
The Rubber Book (Physics and Chemistry Hand book) (the latest edition).
Vogel, A.I., (1954). Some physiologically active compounds. In A text-book of Practical Organic Chemistry
including Qualitative Organic Analysis, Second Edition, London, UK, Longman’s, Green and Company Ltd.
Vogel’s Practical Organic Chemistry(several editions)
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CHE 212: GENERAL CHEMISTRY PRACTICAL
BASE CATALYSED ESTERIFICATION: THE PREPARATION OF BIODIESEL
AIM
The objective of this practical is to prepare biodiesel by a base-catalysed transesterification process
LEARNING OBJECTIVES
By the end of this practical students should be able to:
1. Carry out a base catalysed transesterification.
2. Understand the concept of renewable energy.
3. Identify indicators for monitoring the progress of a reaction.
4. Monitor the progress of a reaction using thin layer chromatography.
5. Understand the stages in a typical organic preparation.
6. Understand the importance of knowing the physiochemical characteristics of your desired product and
other unwanted constituents of your final reaction mixture so that you can exploit them to obtain your pure
product.
INTRODUCTION
In this practical you are going to prepare biodiesel by a base-catalysed transesterification process. You will react a
vegetable oil with methanol in the presence of potassium hydroxide as catalyst. Most vegetable oils comprise over
90% triacylglycerols and treatment with methanol in the presence of base results in the formation of methyl esters of
the constituent fatty acids of the oil. Next week you will carry out an acid catalysed direct esterification and you will
compare the two methods.
There are several general methods of preparing esters. For example, esters can be prepared by a direct esterification
process involving reacting an organic acid with an alcohol, in the presence of an acidic or basic catalyst, with overall
reaction as shown below:
CH3CO2H + CH3CH2CH2OH CH3CO2CH2CH2CH3 + H2O
Esters can also be prepared by a transesterification process involving reacting an ester with an alcohol as illustrated
later for biodiesel. Biodiesel consists of a mixture of the monoalkyl esters of long chain fatty acids derived from
renewable lipid sources, usually vegetable oils, and animal fats or recycled cooking oils that are used as a diesel fuel
substitute to run diesel engines. The lipids are converted to biodiesel by a base or acid catalysed transesterification
process in which the animal fat or vegetable oil is reacted with an alcohol, usually methanol and ethanol, in the
presence of a catalyst to yield biodiesel and the byproduct, glycerol as shown below:
Triacyglycerol Biodiesel Glycerol
Although ‘diesel’ is part of biodiesel’s name, there is no petroleum diesel in the fuel. Biodiesel can be used in ‘neat’
form or blended with petroleum diesel for use in diesel engine. The study of biodiesel is relatively new to Malawi
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but the concept of biodiesel dates back to the invention of the diesel engine itself. Rudolf Diesel designed the first
diesel engine in 1895 with the intention of running it on a variety of fuels, including vegetable oils. He used
groundnut oil to demonstrate the diesel engine at the World Exhibition in Paris in 1900. In South Africa, biodiesel
was introduced before World War II to power heavy-duty vehicles. However, use of biodiesel diminished with the
end of hostilities. In the 1980’s, fear of global warming led to increasing biodiesel use in Western Europe and North
America. More recently, environmental and domestic economic concerns have prompted the resurgence of biodiesel
throughout the world. Biodiesel has also attracted the attention of renewable energy alternate lifestyles activists and
even a cursory Internet search reveals a number of biodiesel sites with recipes for producing biodiesel even at home.
The type of oil feedstock commonly used in each region or country varies depends on the relative availability of the
oils. Soybean oil is commonly used in North America but rapeseed oil is used in Europe.
Several research studies on biodiesel have been conducted particularly in Europe and North America. These
investigations have included production process design, emission studies, and engine testing (both on road and
laboratory controlled) as well as economic feasibility studies. Biodiesel has been used in cars, buses, boats and
equipment.
In Malawi, biodiesel research was initiated in the Chemistry and Physics Departments of Chancellor College in 1999
with a study of the preparation and use as biodiesel of methyl esters prepared by the base catalysed reaction of
methanol and the oils of Moringa oleifera, castor, cottonseed, groundnut, rubberseed, soybean and sunflower seeds.
This was later extended to include the inedible oil from the seeds of Jatropha curcas. Biodiesel research in Malawi
was initiated to reduce the country’s heavy dependence on increasingly expensive, imported, environmentally
harmful petroleum products. In 1999, the diesel consumption for Malawi was 130,545,103 liters. Diesel is widely
used in the transportation of people and goods as well as an energy source in industry. Locally produced ethanol is
used as a diluant for petrol in Malawi and this has reduced the imports of petroleum products by 8%. However,
ethanol can not be used as a diluant for diesel for use in an unmodified diesel engine. Biodiesel offers the advantage
that it can beused in an unmodified diesel engine, either as a blend or in its neat form.
The results indicated that the methyl esters of locally available vegetable oils were suitable for biodiesel production.
This was confirmed by engine tests of the biodiesel at Energy Studies Unit of the Faculty of Engineering of
Strathclyde University.
Production of biodiesel is often done using the base catalysed reaction, because the base catalysed reaction is more
economic. The base catalysed reaction utilises low temperature and pressure conditions (150F and 20psi
respectively) and has a high conversion of 98% with a direct conversion to biodiesel with no intermediate steps.
In the process, the oil/animal fat is reacted with an alcohol (methanol or ethanol) in the presence of a catalyst
(sodium hydroxide or potassium hydroxide). The mechanism of the reaction involves nucleophile production by a
reversible, deprotonation of the alcohol by hydroxide to give the alkoxide ion, followed by nucleophilic attack by
the alkoxide on the carbonyl carbon of the triacylgycerol to give a four co-ordinate intermediate that forms the ester.
The reaction is an equilibrium reaction and the alcohol is added in excess to drive the reaction to the right. A
successful transesterification reaction is signified by the separation of the ester and glycerol layers after the reaction
time. The useful glycerol co-product being heavier settles out, carrying most of the dissolved catalyst with it. For a
successful production of biodiesel the catalyst should not contain water.
This preparation is typical of an organic preparation. Before starting the reaction, you should understand the two
stages of this preparation.
Stage 1: The Reaction
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The reactants are mixed in a flask. A catalyst, sodium hydroxide, is added. The procedure for biodiesel preparation
is well documented and the following ratios give excellent results in yields greater than 90%. The volume of
methanol should be 0.225 times the volume of oil and the quantity of potassium hydroxide, in grams is given by
oil/100 where the volume of oil is given in cm3. The mixture is stirred for one hour to allow time for the reaction to
proceed and to obtain a good yield of ester before the next stage. You will use thin layer chromatography to monitor
the progress of your reaction because the Rf’s of the triacylglycerols and the biodiesel are very different.
Stage 2: Separation, Isolation and Drying
The reaction mixture is put in a separating funnel and allowed to settle into an upper non-polar layer (mainly the
nonpolar biodiesel esters with some impurities) and lower polar layer (predominantly the very polar glycerol with
catalyst and very little ester). This is a common procedure in organic preparations. We exploit the physicochemical
characteristics especially the intermolecular forces of the various constituents of our reaction mixture to allow us to
separate our desired product from unwanted starting materials and by-products. Often we have to initiate the
separation by addition of pure water or water containing dissolved salts to force a separation by changing the
physiochemical characteristics of the media. In this case we do not have to force the separation because the heavy
polar glycerol settles out on standing. The glycerol layer is discarded, and the ester layer is shaken with 10 % acetic
acid solution that converts the remaining catalyst into potassium acetate and dissolves it all:
KOH(aq) + CH3CO2H(aq) CH3CO2K (aq) + H2O
The ester is then washed four times with water to remove traces of acetic acid, potassium acetate, glycerol and other
water-soluble impurities.
The ester layer is stored in contact with anhydrous sodium sulphate, which removes the dissolved water by forming
a solid hydrate that can be removed by filtration:
Na2SO4 + 10H2O Na2SO4.10H2O
Study the properties of your ester and other constituents of the reaction mixture at equilibrium that allow you to
utilize this method of separation and isolation.
PROCEDURE
1. Calculate the quantities of reagents required for preparation of biodiesel from 100ml of oil.
2. Dissolve the catalyst in methanol by vigorous stirring in a 250 ml conical flask.
3. Transfer the oil into another 250 ml flask and add the catalyst/methanol mixture to the oil and stir vigorously for
one hour using a magnetic stirrer.
4. After stirring, transfer the mixture into a separating funnel and allow phase separation to occur. Phase separation
is usually completed in about 20 minutes.
5. After settling is complete, separate the lower heavier crude glycerol layer from the upper biodiesel layer.
6. Check if your reaction is complete using thin layer chromatography. Continue working up your sample as
below while waiting for the plate to develop. Consult your demonstrator and technician if the reaction is
incomplete.
7. Wash the ester initially with an equal volume of 10% acetic acid. Avoid emulsions while washing by swirling
gently.
8. Wash the ester four times with an equal volume of de-ionised water. The ester should be clear at this stage.
9. Measure the volume of the wet product.
10. Transfer the ester to a clean dry container and add 5 grams of anhydrous sodium sulphate as a drying agent.
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Leave the ester drying till the next lab session.
11. Measure the volume and mass of your dry product.
QUESTIONS
1. Calculate the number of moles of each reactant. Identify the limiting reagent. Calculate your theoretical yield
(assuming the reaction had gone to completion) and actual yield of ester.
2. What properties of your ester and other constituents of your reaction mixture are exploited in your separation
and isolation procedure?
3. Predict the likely impurities in your product and suggest how you could improve the purity of your product.
Explain why the impurities should be removed from the biodiesel before use as a fuel.
4. Suggest a criterion of purity for the biodiesel.
5. Explain why it is important to ensure that your glassware is dry at the start of the ester preparation.
6. Write the r
7. eaction mechanism and explain the role of the potassium hydroxide.
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