CHEM2711 Spectroscopy and Data Analysis
Lab 3: Synthesis and Characterisation of an Ester
Objective: Synthesise an ester from a carboxylic acid and an alcohol. Characterise the ester
product, obtaining evidence for its structure and purity using 1H NMR spectroscopy, IR
spectroscopy and Gas Chromatography – Mass spectrometry (GC-MS).
Background: Esters are common functional groups found in natural products, synthetic
polymers, pharmaceuticals and many other fine chemicals. A classic method for preparing an
ester is the acid-catalysed condensation of a carboxylic and an alcohol:
O O
H+
R OH + HO R* + H 2O
R OR*
carboxylic acid alcohol ester
The mechanism of the reaction is outlined below. Briefly, a strong acid (sulfuric acid in this lab)
protonates the carboxylic acid and the alcohol attacks the carbonyl as a nucleophile. The strong
acid can then protonate one of the OH groups on the resulting intermediate, converting it into a
water leaving group. The carbonyl is reformed and water is expelled as a byproduct. The proton
is regenerated as the ester product is formed. The proton can then re-enter the catalytic cycle.
H
O O OH H+
H+
R OH
R OH R OH
O R*
HO R*
H+
+ H
O OH H
O R O
R OR* H
+ O
R OR*
R*
H 2O
To drive the equilibrium to the product ester, heat can be applied so that the water generated can
be removed by distillation. Alternatively, a chemical reagent that traps water can be added to the
reaction, such as sulfuric acid or molecular sieves. In the workup, the acid catalyst is neutralised
with base.
Prelab activities (to be included in final report too):
1. Select a carboxylic acid and alcohol from the table of reagents on the next page. These will
be the reagents you use in your synthesis.
2. Draw the structure of your carboxylic acid and alcohol, and the expected product ester.
3. For the expected product ester, what is its expected boiling point? What is its expected
density? (See data table provided in FLO).
4. Calculate the mass and/or volume of your reagents required for the reaction of 0.15 mol
carboxylic acid and 0.12 mol alcohol. What is the limiting reagent under these conditions?
5. Predict what will be in the product mixture at the end of the reaction. Explain the purpose of
the workup procedure and how the ester product will be purified in this workup.
6. Identify the risks associated with the following reagents and techniques:
a. What risks are associated with handling the carboxylic acid and alcohol you will use
in your reaction?
b. What risks are associated with the sulfuric acid catalyst?
c. In the extractive workup in which an aqueous solution of bicarbonate is used to
neutralise the reaction, what reactions occur? Is there any risk associated with this
process?
Reagents available for this lab activity and relevant properties
Compound CAS No. Molar Mass Density Boiling point
Sulfuric acid 7664-93-9 98.08 g/mol 1.84 g/mL 290 ºC
Acetic acid 64-19-7 60.0 g/mol 1.05 g/mL 118 ºC
Propanoic acid 79-09-4 74.1 g/mol 0.99 g/mL 141 ºC
Butanoic acid 107-92-6 88.1 g/mol 0.96 g/mL 164 ºC
1-Propanol 71-23-8 60.1 g/mol 0.80 g/mL 98 ºC
3-Methyl-1-butanol 123-51-3 88.1 g/mol 0.81 g/mL 131 ºC
1-butanol 71-36-3 74.1 g/mol 0.81 g/mL 118 ºC
Experimental protocol:
To a 100 mL round bottom flask add the carboxylic acid (0.15 mol) and the alcohol (0.12 mol).
Carefully swirl the flask to mix. Next, add a few boiling chips, followed by 1.0 mL of sulfuric acid.
Equip the flask with a condenser and heat the reaction to reflux using a heating mantle. Heat the
reaction at reflux for 30 minutes. After this time, remove the flask from the heating mantle and
cool to room temperature. Then, transfer the reaction mixture to 100 mL separatory funnel and
then wash with 20 mL of deionised water. Separate the aqueous (bottom) and organic layers
(top). Collect the organic layer in a 100 mL beaker and then slowly add 10 mL of a saturated
solution of sodium bicarbonate (CO2 gas may be generated). Stir with a glass rod until no gas is
generated, then add an additional 10 mL of the saturated sodium bicarbonate solution. Stir with
a glass rod until no gas is released. Check the pH of the mixture with pH paper. Add more of the
sodium bicarbonate solution until the mixture is basic (pH >7). Return the mixture to the
separatory funnel, shake carefully (vent to release pressure), and separate the aqueous (bottom)
and organic layers (top). Collect the organic fraction in clean Erlenmeyer flask and then add a
drying agent (MgSO4 or Na2SO4) to remove water. Enough drying reagent should be added so
that the excess is free flowing (~1-2 g). Remove the drying agent by gravity or vacuum filtration
to obtain the crude ester product for characterisation.
Characterisation:
Demonstrators will assist you in both sample preparation and running the instruments. Please
don’t hesitate to ask for their assistance if you have questions.
1
H NMR: Add 20-50 mg of your product to a test tube or glass vial and dissolve it in 0.7 mL
deuterated chloroform (CDCl3). Transfer this solution to a clean NMR tube, cap the tube, and
label your sample with a tag or piece of paper. Submit your sample to the demonstrator, who will
acquire the 1H NMR spectrum of your product and provide you with a printout of the spectrum.
GC-MS: Obtain a GC-MS trace of your product with the assistance of a demonstrator. You will
analyse both the chromatogram and the mass spectrum in your report.
IR: Obtain an IR spectrum for both of your starting materials and the product. Add a drop of the
neat compound to the NaCl disc and sandwich between a second NaCl disk to spread the
compound evenly across the disc. Acquire an IR spectrum (transmittance mode) of the thin film.
Wash the disc with ethanol (wash bottle) and wipe with a Kimwipe between each sample.
Lab report guidelines:
Your lab report should contain the following information:
Introduction: short description of the purpose of the experiment and some general information on
esters, including the ester you synthesised. A brief description on the analytical characterisation
should also be addressed in the introduction.
Experimental Protocols: provide a concise and detailed procedure for the specific experiment you
did. This should be written with sufficient detail that the reader could repeat your experiment. Also
provide information about the protocols you used in the analysis, including sample preparation
and information about any relevant settings, instrument type, or method used in the analysis. For
NMR, this should include the solvent and the frequency of operation (600 MHz). For GC-MS,
information about the sample injection, method, and ionisation should be specified.
Results and discussion: Present your results and discuss the outcome of your synthesis and the
evidence you obtained to support your description of the outcome. This should include a
description of the synthesis, your observations and the results for the reaction and workup. The
IR spectra for the starting materials and product should be presented and discussed, clearly
pointing out and explaining key peaks in the spectrum and what functional groups and modes of
vibration to which they correspond. The 1H NMR spectra should be presented, fully assigned, and
discussed (chemical shift, integration and multiplicity should all be analysed). The GC trace and
MS spectrum should be presented and discussed. Please comment on the purity, retention time,
and rationalise the observed peaks in the mass spectrum. Clearly present your argument for the
identity and purity of the sample.
Conclusion: Provide a conclusion describing the outcome of the synthesis, including evidence for
the identity and purity of the product. Describe how you would revise the protocol or design
another follow-up experiment if the outcome was not one that was expected.
