CHEM 110 LABORATORY ASSIGNMENT 3

PART I: THE HYDROLYSIS OF AN ESTER

PART II: SPECTROSCOPIC STRUCTURE DETERMINATION

BEFORE COMING TO THE LAB: Read through the assignment carefully and
complete the “110 Pre-Lab Ester Hydrolysis” on Canvas. Completion of the pre-lab module
contributes towards your final lab grade.

1. INTRODUCTION
In Part I of this experiment you will hydrolyse an ester and separate and recrystallise the product.
In Part II you will complete a spectroscopy problem.

The grading criteria for this laboratory are outlined on page 7.

PART I
2. ESTER HYDROLYSIS
Esters are derivatives of carboxylic acids, in
which the -OH group is replaced by -OR¢.

These and other carboxylic acid derivatives react with nucleophilic species (NuH or Nu-) to give
products in which a leaving group, X, is substituted by Nu.
The reactivity towards substitution varies with the
nature of X.
Acid derivatives can be converted to a less reactive
derivative by reaction with the appropriate
nucleophile.

The reaction you will carry out today is an

example of a reaction of an ester with the
nucleophile (OH-), a reaction which gives the
acid as product. The reaction is carried out in
aqueous solution with heating and is called
hydrolysis. The initial benzoate anion product
is then converted to benzoic acid by
acidification with mineral acid.

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 CHEM 110 Laboratory Assignment 3 [2020] 2
3. TECHNIQUES
3.1 Reflux
Although some reactions can be carried out at room temperature, product formation is often slow
and some reaction mixtures must be heated for a period of time to ensure a good yield. A reaction
mixture can be kept at constant elevated temperature using a technique known as reflux.
To reflux a reaction mixture it is boiled in a flask, which is attached directly to an upright water-
cooled condenser. As the vapours come into contact with the inside (see diagram page 3) of the
water-cooled condenser, they condense and drip back into the reaction mixture. Boiling can thus
be continued for a long period without loss of volume.
3.2 Vacuum filtration
Solid products are often collected by vacuum filtration. The
apparatus used is a heavy walled flask with a side arm (Büchner filter paper

flask) fitted with a plastic or porcelain funnel with a perforated flat clamp here rubber disk

bed (Büchner funnel). heavy-walled

To assemble the apparatus, first clamp the flask to the clamp stand. tubing to
vacuum outlet .
Next, using heavy walled tubing connect the side arm to a vacuum
source, before the funnel is placed through the rubber adaptor which
fits over the neck of the flask. A piece of filter paper is placed in the bed of the funnel and should
cover all holes and be moistened with water (or the solvent being used) before the vacuum is turned
on and the slurry containing solid is poured in.
3.3 Recrystallisation
Solids are often purified by recrystallisation from a solvent in which the solid has a high
solubility at high temperature and a low solubility at room temperature. To recrystalise a solid it
must first be dissolved in the minimum amount of heated solvent. Less soluble impurities can be
filtered off at this point. If the solvent has been chosen correctly the solubility of the solid
decreases as the solution cools and the solid crystalises out.
3.4 Calculating %yield
Chemists need to monitor the success of their reactions. One measurement used is %yield – the
yield obtained in the reaction compared to the theoretical maximum yield.
First, the number of moles of starting material is calculated from the mass
used. The number of moles of product can then be determined, using the 𝑚𝑎𝑠𝑠
𝑚𝑜𝑙 =
mole ratios in the balanced equation for the reaction. In this lab, one mole 𝑚𝑤
of methyl benzoate is converted into one mole of benzoic acid, so the ratio
is 1:1.
Now that the number of moles of product is known, this can be converted to a mass using the
equation above. This mass is the theoretical yield – i.e. the maximum possible yield.
The %yield is then given by: -./-012-3456 81-69
%𝑦𝑖𝑒𝑙𝑑 = 4:-;0-41<56 81-69 × 100

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 CHEM 110 Laboratory Assignment 3 [2020] 3
4. SAFETY INFORMATION
We are required under the Health and Safety in Employment Act, 1992, to make available safety
information concerning chemicals used in any experiment. You must read this information before
beginning the experiment.
Precautions: Safety glasses, a laboratory coat and appropriate footwear must be worn at all times.
Spillage: Avoid skin contact in all cases. If any chemical is accidentally splashed into your eyes,
call for help and use the eye-wash spray immediately. If you spill a chemical on your
skin or clothes, rinse the affected area with plenty of water and notify a staff member
immediately. If a water-insoluble chemical (eg. many organic compounds) is spilled in
the work area, shut off all ignition sources, adsorb the spill onto sand and transfer the
sand to a vented area; protective gloves must be used.
Disposal: Except where indicated otherwise, aqueous solutions of water-soluble chemicals can be
disposed of by rinsing them down the sink with plenty of water.
Water-immiscible chemicals (solid or liquid) must be placed in the appropriate
RESIDUES container in the fume hood.

Potassium hydroxide KOH 10% solution Methyl benzoate C6H5CO2CH3

Description: Colourless solution. Description: Colourless liquid.
Risk: Causes burns. Seek immediate Risk: Flammable. Eye irritant.
assistance if contact with skin or eyes.

WHEN YOU HAVE READ THIS SECTION ON SAFETY, AND ARE SURE YOU UNDERSTAND THE
INFORMATION, SIGN IN THE BOX AT THE TOP OF THE REPORT SHEETS (PAGE 7).

5. EXPERIMENT [WORK INDIVIDUALLY]

5.1 The hydrolysis of methyl benzoate
5.1.1 Reaction procedure
1. Position the hot plate unit, which is shared between a pair of students, adjacent to a clamp
stand such that one student can clamp their apparatus to this clamp stand, whilst the other
student can use the clamp stand of the hot plate unit.
2. From the appropriate automatic dispensers, dispense:
0.5 mL (0.55 g) of methyl benzoate and 7 mL of 10% w/v (10 g of KOH
per 100 mL of water as solvent) potassium hydroxide solution directly
into your Quickfit flask. Quickfit
3. Place 3 or 4 antibumping granules into your Quickfit flask. flask
Stand the Quickfit flask in a 100 mL beaker.
4. Smear a very thin film of lubricant around the ground glass joint of the water out
condenser, which fits into the flask.
5. Clamp your condenser to the clamp stand and attach the Quickfit flask clamp here
with a plastic clip. (Your apparatus should look like the diagram shown
to the right.) water in
6. Position your apparatus in a heating block. clip here
7. Your condensers will be connected in series. First, with the short hose
provided, connect the two condensers from the water out on one
condenser to the water in on the other condenser. Use a long hose to ....
..
connect the ‘water in’ on the first condenser with the PCWF tap. Attach
the final hose to the ‘water out’ on the second condenser but do not attach this to the PCWR
tap. This will be done by your supervisor after bleeding the lines.
YOUR SUPERVISOR WILL CHECK YOUR APPARATUS AND TURN ON THE WATER.
[THIS MUST BE DONE BEFORE PROCEEDING TO STEP 8.]

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 CHEM 110 Laboratory Assignment 3 [2020] 4
8. With the water flowing through the condensers turn on the hot plate to maximum heat.
9. When the mixture in the flask boils, allow it to reflux for at least 15 minutes. Record your
experimental observations on page 9.
The completion of hydrolysis will be apparent by the disappearance of the insoluble ester
globules in the reaction mixture. The products of hydrolysis, methanol and potassium
benzoate, are themselves water soluble. Please note: the lubricant used in step 4 is not water
soluble and, if too much was used, it may drip into your reaction mixture during reflux.
10. Raise the reflux apparatus out of the heating block and allow the reaction mixture to cool.
11. Reduce the hot plate setting from maximum heat to ~200°C, which is appropriate for the
recrystallisation step of your product.
YOUR SUPERVISOR WILL DISCONNECT YOUR CONDENSERS FROM THE
RECIRCULATING WATER TO AVOID FLOODS.

5.1.2 Isolation of benzoic acid

When your reaction mixture has cooled, carefully remove the clip connecting the flask and
condenser and decant the solution from the anti-bumping granules into a clean 100 mL beaker.
Cool the beaker in an ice-water bath for a few minutes. Collect 10 mL of 1 mol L-1 sulfuric acid
from the automatic dispenser and add it to the solution in the beaker, whilst it is cooling in the ice
bath. The solid, which precipitates, is benzoic acid. Collect the solid by vacuum filtration. (See
page 2.) Wash the solid with one 5 mL portion of cold water, and suck dry for a few minutes.
5.1.3 Recrystallisation of benzoic acid
Transfer the benzoic acid to a 50 mL conical flask using a solid(s) addition funnel.
Remove the addition funnel and add 20 mL of water. Stand a boiling stick in the solid(s) addition
flask and then place the flask on the hot plate between the heating blocks. Bring funnel
the contents of the flask to the boil, stirring occasionally with the boiling stick to
encourage dissolution. If all the solid has not dissolved to give a clear solution add more water in
small portions (~5 mL at a time) and heat again.

Once the benzoic acid has dissolved take the flask off the hot plate, remove the boiling stick and
leave the solution to stand undisturbed whilst cooling to room temperature.

RECORD THE VOLUME OF WATER USED IN THE RECRYSTALLISATION ON P9 AND ASK YOU SUPERVISOR
TO ASSESS YOUR RECRYSTALLISATION.

Collect the recrystallised benzoic acid by vacuum filtration.

5.1.3 Calculation of % Yield

Collect a plastic petri dish from the window-bench and take it to the balance. Zero the balance.
Then place the petri dish on the balance, and record its mass to 0.001 g on page 7. Take the petri
dish back to your desk and transfer your product to the petri dish. Return to the balance, and zero
the balance again. Place the petri dish on the balance, and record its mass to 0.001 g on page 9.
*ASSESS YOUR PRODUCT (RECORDING YOUR DECISION ON PAGE 6) BY
COMPARISON WITH THE SAMPLES ON THE SIDE BENCH, BEFORE GIVING
YOUR PRODUCT TO YOUR SUPERVISOR FOR ASSESSMENT.*
Calculate the %yield for this experiment.

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 CHEM 110 Laboratory Assignment 3 [2020] 5
PART II
You may begin PART II while completing your experimental work. However:
AFTER COMPLETION OF EXPERIMENTAL WORK (including
recrystallisation)
1. SWITCH OFF THE HOT PLATE.
2. ALL QUICKFIT APPARATUS MUST BE THOROUGHLY CLEANED.

6. INTERPRETATION OF SPECTRA
Spectral data specific to the problem in this lab will be supplied by your supervisor. A
spectroscopic data sheet is supplied on p6. For help with spectral interpretation you should read
below and consult your spectroscopy lecture shell.

It is important to carry out spectral interpretation in a systematic way.

Remember:
a) Calculate the DBEs (total number of rings and/or p bonds) associated with the molecular
formula. Four or more DBEs, in this assignment, can be taken as indicating the presence of a
phenyl (C6H5-) substituent. The phenyl accounts for four DBEs (one ring and three p bonds)
and any over and above four are associated with the functional group. Decide which
functional groups could be present, on the basis of molecular formula and the total number of
DBEs and establish which functional group is present by consideration of the appropriate
spectra.
b) Subtraction of the atoms accounted for from the molecular formula should then allow
formulation of the potential constitutional isomers, which can be distinguished by
consideration of the NMR spectra.
c) The number of signals in the proton decoupled 13C NMR spectrum allows one to differentiate
between compounds which have different numbers of non-equivalent environments for
carbon.
d) The 1H NMR spectrum allows one to determine:
The number of non-equivalent environments for hydrogen.
The number of hydrogens in a particular environment.
The number of hydrogens vicinal (neighbouring) to those giving rise to the absorption signal.
The chemical shift (d) value for a particular absorption signal gives information as to the
specific environment of these hydrogens.

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 CHEM 110 Laboratory Assignment 3 [2020] 6

CHEM 110 SPECTROSCOPY DATA SHEET

TABLE 1
IMPORTANT INFRARED ABSORPTION REGIONS
(STRETCHING FREQUENCIES)
Bond Present n (cm-1)
O-H (alcohol, phenol) 3700 – 3200
(carboxylic acid) 3600 – 2500 (broad)
N-H 3500 – 3100
C-H 3100 – 2800
C=O 1850 – 1600
C=C (aliphatic) 1680 – 1600
(aromatic) 1620 – 1550
C-O 1250 – 1050 (less definitive)
TABLE 2
1
H NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (1H NMR)
Approximate Chemical Shifts (d) of Hydrogens in Organic Compounds
Hydrogens (H) in various d
chemical environments (ppm downfield from TMS)
(CH3)4Si (TMS) 0
R2CHCR 1.0 (approx.)

R2CHCZ* 1.0 - 2.0

Hydrogens bonded
to sp3 carbon R2CHC=C 1.6 - 1.9

R2CHC=O 2.0 - 2.5

R2CHAr 2.5 - 3.5

R2CHX** 2.0 - 3.7
R2CHO- 3.3 - 4.5

HC=C 4.5 - 7.0

Hydrogens bonded 6.5 - 8.0
H-Ar
to sp2 carbon
HCR 9.5 - 10.0
O
HOR 3.0 - 6.0 (variable)
Hydrogen bonded HOCR 10.5 - 12.0
to oxygen
O

Notes: **X = Cl, Br, I or the N of an amine

*Z = O, C=O, or X (as defined above)
R = H or alkyl group

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 CHEM 110 Laboratory Assignment 3 [2020] 7
TIME MANGAGEMENT PLAN

To complete this lab on time, you need to work effectively. Here is a suggested time management
plan for the lab, but you may wish to develop your own.

1. Welcome and group introduction (15-20 min)

2. Experimental work

- Set up ester hydrolysis. You must wait for a supervisor before you turn on your
experiment and this can take some time.
- If you find yourself waiting for a supervisor, start the spectroscopy exercise.
- While waiting for your reaction to reach completion (20-25 min), work on the
spectroscopy exercise.

- Remove reaction from the heating block. While this is cooling:

o collect all equipment required for step 5.2.1 (including ice bath).
- Complete step 5.2.1. While the product is drying:
o Collect all equipment required for recrystallisation.

- Set up recrystallisation. While this is cooling:

o Work on spectroscopy exercise.

- Filter product. While this is drying:

o Pre-weight petri dish and record relevant data.
o Calculate Theoretical yield of product.
- Transfer, weigh and assess dried product.
- Calculate %yield.
- Clean up all glassware

- Complete any remaining elements of the spectroscopy exercise.

Please remember: cleaning up and handing in on time is one element of the marking rubric
for this lab.

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 CHEM 110 Laboratory Assignment 3 [2020] 8
REPORT SHEETS

Name:________________________________ Stream#:______ Gp:____ Bench#:_______

Supervisor:________________________

I have read and understood the safety

information for this assignment. Signed:_________________________

SUPERVISOR USE ONLY

0 (not achieved) 0.5 (progress) 1 (mastery)

Overall Report Quality More than 2 questions Major errors or 1-2 All questions answered.
unanswered/incomplete missed questions. Minor errors only.
Follow a procedure to
make a compound in D yield or below C yield A to B yield
good yield
Use recrystallisation to Poor Average and Dry Excellent
make a compound of OR OR AND
high quality Average and Wet Excellent and Wet Dry
Record experimental No observations Limited or unclear Clear and concise
observations recorded recording of recording of
observations observations
Minor errors in %yield calculated
Weigh a compound and Significant errors or calculation correctly. Calculation in
calculate %yield incomplete calculation AND/OR agreement with
not consistent with ‘quantity’ assessment.
‘quantity assessment
Use standard All structures drawn
notation(s) to draw Significant errors in Minor errors in using standard chemical
chemical structures structure drawing. structure drawing. notations except were
otherwise specified.
Use spectroscopic data Major issues/errors in Minor errors in Structure correctly
to determine the structure identification. structure identification identified and soundly
structure of a OR and/or major justified, with only
compound No justification provided errors/omissions in minor omissions in
justification. justification.

Issues

Safety non-compliance Incomplete tidy-up Late submission

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 CHEM 110 Laboratory Assignment 3 [2020] 9

PART I: THE HYDROLYSIS OF AN ESTER

7. BENZOIC ACID PREPARATION

Apparatus assessment:
Supervisor’s comments:
OK Minor problems Major problems ___________________
Supervisor’s signature

Experimental Observations: (During reflux and isolation of product.)

Recrystallisation (information and supervisor assessment):

Volume of water used in recrystallisation = ________ mL

Product assessment: STUDENT SUPERVISOR

Quantity:
[Based on samples A B C D A B C D
available for comparison.]
Excellent / Average / Poor Excellent / Average / Poor
Quality:
Dry / Wet Dry / Wet
Supervisor’s signature:

___________________________
7.1 Experimental Data and Calculations:
Note: m.w. benzoic acid = 122.12 and m.w. methyl benzoate = 136.15

Mass of petri dish _______________ Mass of petri dish + product _______________

Experimental Yield ______________

Theoretical Yield. ________________

%Yield: __________________

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 CHEM 110 Laboratory Assignment 3 [2020] 10

PART II:
8. PROBLEM
Compound A has the molecular formula C10H12O2. Calculate the DBEs (rings and/or p bonds)
associated with the molecular formula for A.

Assuming the presence of a phenyl group and a single functional group, name the
two functional groups which could be present?
_________________ or _________________

The IR spectrum for compound A shows a strong signal at 1780 cm-1 and a peak 3000 cm-1
corresponding to C-H stretching. There are no other peaks in the 1700-3700 cm-1 region of the IR
spectrum. Based this information, the functional group present in compound A is:
Justify your choice.
____________________

Looking at the aromatic region of the 1H NMR spectrum for compound A, there is/are:

__________ signal(s) and a total of __________ hydrogens on the phenyl ring.

This indicates the presence of a

mono-substituted / 1,2-disubsituted / 1,3-disubstituted / 1,4-disubstituted aromatic ring

(circle as appropriate)

Complete the tabulated 1H NMR data for compound A using the spectrum provided.

Signal Signal Signal: lines

Position Area observed

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 CHEM 110 Laboratory Assignment 3 [2020] 11
Determine the structure of Compound A and show how this fits with the 1H NMR data given.

How many signals would you expect in the 1H decoupled 13C NMR spectrum for compound A?
Justify your choice by appropriate labelling of your structure.

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