CHEM1002 Laboratory Manual Semester 1 - 2019 - Final

CHEM1002: Reactivity and Function in Chemistry
Laboratory Manual
Semester 1, 2019
Published: 21 February 2019
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This laboratory manual has been revised and updated with the kind assistance of your demonstrators,
technicians and lecturers.
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Department of Chemistry
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Contents
Introduction ........................................................................................................................................5
Safety .................................................................................................................................................................................... 5
General principles for volumetric analysis ............................................................................................................11
General lab procedures ...............................................................................................................................................12
Assessment .......................................................................................................................................................................24
The laboratory session .................................................................................................................................................29
Purification of benzoic acid by recrystallization ...........................................................................31
Introduction .....................................................................................................................................................................31
Completing your logbook ..........................................................................................................................................32
Procedure..........................................................................................................................................................................34
Glossary .............................................................................................................................................................................38
Assessment .......................................................................................................................................................................41
Pre-laboratory questions ............................................................................................................................................43
Preparation of benzoic acid ............................................................................................................45
Background ......................................................................................................................................................................45
Procedure..........................................................................................................................................................................46
Results ................................................................................................................................................................................48
Assessment .......................................................................................................................................................................49
Preparation and reactions of cyclohexene ....................................................................................53
Background ......................................................................................................................................................................53
Procedure..........................................................................................................................................................................55
Results ................................................................................................................................................................................58
Glossary .............................................................................................................................................................................59
Assessment .......................................................................................................................................................................61
Preparation of 4-nitroacetanilide ...................................................................................................65
Introduction .....................................................................................................................................................................65
Procedure..........................................................................................................................................................................66
Assessment .......................................................................................................................................................................69
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Determination of acetic acid in vinegar .........................................................................................73
Background ......................................................................................................................................................................73
Procedure..........................................................................................................................................................................76
Glossary .............................................................................................................................................................................80
Assessment .......................................................................................................................................................................85
Designing and making buffer solutions ........................................................................................89
Background ......................................................................................................................................................................89
Procedure..........................................................................................................................................................................92
Assessment .......................................................................................................................................................................95
Kinetics of the iodine clock reaction ..............................................................................................99
Background ......................................................................................................................................................................99
Procedure....................................................................................................................................................................... 107
Assessment .................................................................................................................................................................... 121
Pre-laboratory questions ......................................................................................................................................... 123
Extraction of organic compounds: Separation using acid-base properties ............................ 125
Introduction .................................................................................................................................................................. 125
Procedure....................................................................................................................................................................... 130
Assessment .................................................................................................................................................................... 135
Carboxylic acids and their derivatives – using mind maps to link concepts ........................... 139
Introduction .................................................................................................................................................................. 140
Procedure....................................................................................................................................................................... 141
Assessment .................................................................................................................................................................... 147
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Introduction
Welcome to the laboratory manual for Reactivity and Function in Chemistry at

Curtin University. You will be enrolled in CHEM1002.
This laboratory manual is an important resource that will give you instructions on
how to work safely in the laboratory to successfully complete a series of
experiments that are essential in learning chemistry.
Every experiment in this laboratory program has goals in three categories which all
link together to meet the learning outcomes you will gain on successful completion
of this laboratory program. These goals are highlighted with symbols throughout
this laboratory manual and are designed to support you in developing key
competencies identified for each experiment.
• You will develop important practical skills in the correct and safe handling of
hazardous substances and modern scientific apparatus, including
instrumentation.
• The laboratory is a hands-on environment to help you understand key
chemical concepts.
• Being able to communicate scientific principles is vital to success in all areas
of science.
Part 0.1____________________________________________________________________________
Safety
You should read and understand all instructions given in this laboratory
manual before you commence any experiments. If you are unsure or uncertain
of the hazards or risks associated with any procedure, you should ask your
laboratory demonstrator. They can be identified by their yellow safety vests.
An important part of the laboratory experience is learning to work safely. Safety is

everyone’s while in the laboratory. Even if you’re not working with chemicals other
people may be, so be aware at all times and follow some simple rules to avoid
injury or causing injury to others.
Pre-laboratory work
Before you commence each experiment, you should be fully aware of the hazards
associated with the reagents and equipment you are about to use. To assist you
with this, you must read and understand the procedures in this laboratory manual
before entering the laboratory. All experiments have mandatory pre-lab questions
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that you must complete before you come to the lab.
Instructions
Each experiment you undertake has important notices that must be read and
understood before you commence this procedure in the laboratory. Failure to
follow written instructions in the laboratory manual, the verbal and written
instructions of staff, or signs posted around the laboratory, may put you or other
people at risk of injury. Students who fail to follow instructions will be asked to
leave the laboratory and may face disciplinary action. Important notices in this
laboratory manual are clearly identifiable:
Notices that must be read and understood to avoid injury are clearly
signposted in the laboratory manual, like this.
Containers or bottles of hazardous substances are affixed with different diamond-

shaped labels—for example in Figure 1. The dangerous goods diamonds give an
indication, at-a-glance, of the hazards associated with storing and using this
substance. You should become familiar with these symbols.
(a) Flammable liquid (b) Oxidising agent (c) Corrosive substance (d) Toxic substance
Figure 1: Some of the

dangerous goods
Throughout the laboratory there are signs with blue circles that give a mandatory
diamond labels you will
instruction that must be followed by all personnel. These instructions require the
observe on containers
wearing of personal protective equipment or outline an action that must be taken of hazardous
to avoid injury. Figure 2 gives an example of a mandatory instruction that requires substances in our
all personnel to wash their hands. laboratories
Hazards are also highlighted in a pre-laboratory presentation given by your

demonstrator at the commencement of each experiment. If you are not present at
this presentation, you can put yourself and your fellow students at risk of injury. If
you arrive after the pre-laboratory presentation your demonstrator has the
right to bar your entry to the laboratory and you will not be able to perform
the experiment. Due to limited capacity in our laboratories, you will not be
permitted to attend a later laboratory, and make-up laboratory sessions are not
available. Figure 2: A mandatory
instruction to wash
hands
Personal protective equipment, PPE
To work in the laboratories, you must purchase your own personal protective
equipment (PPE), bring them to every laboratory class, and be correctly wearing
them at all times in the laboratory.
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• Laboratory coat of a type that fastens up the front, has long sleeves and
comes to your knee.
• Safety glasses containing colourless transparent lenses. Prescription or
sunglasses are not acceptable, including safety glasses with tinted or
mirrored lenses.
The minimum requirements of dress for entry into the laboratory is a laboratory
coat, safety glasses, and fully enclosed shoes. Footwear must be a well- made, low
heeled, fully enclosed shoe or boot that would limit slipping and protect the feet
from chemical spills and broken glassware. The footwear upper should be made
from synthetic, leather, canvas or a combination to achieve protection from spills
of liquids and must cover your forefoot, toe and heel. Mandatory signs, like those
in Figure 3, are displayed at the entry to laboratories to indicate these PPE must be
worn before entry is permitted.
Figure 3: Mandatory
personal protective
equipment that must
be correctly worn in the
laboratory at all times
Prohibited
No food or drink is to be handled or consumed at any time in the laboratory. This
includes bottled water and chewing gum or sweets. Do not smoke in any place on
campus. All buildings and grounds are smoke free. You will see prohibition signs,
like those in Figure 4.
Figure 4: Certain
actions like handling
food and drink are
prohibited in the
laboratory, in addition
to general prohibitions
against smoking on
campus
Safety equipment
There are a number of apparatus available in the laboratory that are designed to
prevent serious injury after a chemical spill—especially into sensitive organs like
eyes or over a large part of the body. These are indicated by signs such as those in
Figure 5. The location and operation of these equipment will be demonstrated in
your first laboratory class.
If you get any chemicals in your eyes, immediately go to an eyewash station,
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remove any glasses, and hold open your eyes while irrigating the eye thoroughly.
To start the flow of water, pull the eyewash station towards you.
If you get chemicals on your skin, immediately wash skin areas which come into
contact with chemicals, irrespective of concentration, and report this to your
supervisor. Note: For concentrated acids or bases, or particularly harmful chemicals,
you will need to continually rinse the affected area under cool running water for at
least 20 minutes!
Figure 5: Signs
indicating the location
of safety equipment in
the laboratory
Eye wash station Safety shower
Chemical hazards
All chemicals should be handled with care. The following are particularly hazardous:
1. Concentrated acids, e.g. sulfuric, nitric; concentrated alkalis, e.g. sodium

hydroxide, aqueous ammonia; hydrofluoric acid, chlorine, bromine,
phenols, benzene, sodium or potassium metal, hydrogen sulfide gas.
(a) In case of spillage or splashing:
(a) on skin—wash off immediately under the nearest tap and

continue rinsing for at least 20 minutes.
(b) on clothing—remove clothing and rinse thoroughly in water.
(c) on floor or bench—dilute with water and mop up with paper
towels or mop.
(d) in eye—wash immediately with the eyewash station and
continue rinsing for at least 20 minutes.
2. Organic solvents, if in continual contact with skin, can cause skin
diseases such as dermatitis.
3. All experiments likely to generate toxic, flammable or irritating gases
must be carried out in a fumehood. You will be instructed by your
demonstrator in the pre-laboratory presentation which steps in a
procedure require a fumehood.
4. Particular care should be exercised in disposing of waste or spilt
chemicals and reaction residues. This should be done on the advice of
your demonstrator.
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5. Rubbish, waste filter paper, used paper towels etc. must not be thrown
into sinks or yellow sharp waste bins but placed in the green general
waste bins with black liner provided.
6. All sharp and/or contaminated wastes such as broken glassware, used
filter paper, disposable gloves, plastic pipettes etc. must be placed in
the yellow sharp waste bins.
For a more complete list of chemicals with their first aid treatment, consult the
Safety Data Sheets (SDS). SDS for every chemical in use in our laboratories can be
found by accessing the ChemAlert database, which is accessible here:
� https://healthandsafety.curtin.edu.au/hazardous-materials/chemicals.cfm
Fire hazards
1. Every student should learn from the demonstrator where to find the fire
blanket and fire extinguisher nearest their place of work.
2. Clothing catching fire causes the most distressing laboratory accidents.
Since the victim’s chances of recovery rapidly diminish with the extent
of skin surface burned, immediate and correct action is essential.
When clothing catches fire, throw the person to the floor and roll to
smother the flames quickly. If a fire blanket or a laboratory coat is very
handy, it may be used. If near a shower, roll the person under and then
turn on the water, but never let them stand even if you have to be
forceful. Ensuring the person remains on the floor minimises injury to
the respiratory passages and eyes by the flames, which would naturally
rise and envelop the head.
Never use an extinguisher of any type on a person. The soda-acid

extinguisher may damage the eyes, whilst the carbon dioxide type may cause
severe frostbite.
3. Flammable liquids should never be handled near an open flame,

including when used in fumehoods. Never distil solvents such as
alcohol, ether, petrol, etc. over or near an open flame. Volatile vapours
can travel many metres to an open flame and ignite, thus setting the
liquid in the container alight.
4. Students are required to tie up long hair since loose flowing hair may
be a serious fire hazard in a chemical laboratory. Similarly, a headscarf
or hijab may pose an extra risk, so extra care should be taken by tucking
it into your laboratory coat.
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Handling glassware
The most common laboratory accidents arise from the careless handling of
glassware. The following rules must be observed:
1. Ensure there are no jagged or chipped edges. Do not use glassware that
is broken, chipped or damaged. Report any damaged glassware to your
demonstrator or a technician.
2. Before inserting glass tubing into rubber tubing or stoppers, or
volumetric pipettes into fillers, make sure that the hole is large enough.
Hold the stopper between thumb and forefinger, not in the palm of the
hand. Grasp the glass tubing close to the end that is to fit into the
stopper. Hold the pipette close to the point of insertion. Push the tubing
or pipette with an even pressure.
3. Never use force to remove rubber stoppers or tubing from glass tubing.
If necessary, cut the rubber away from the glass.
4. Do not try to force an oversize stopper into a flask, and avoid using
stoppers that are too small and can be pushed through into the flask.
Behaviour
There are some simple rules for behaviour in the laboratory to prevent injury to
yourself or to others.
1. Always act responsibly. Horseplay, running, unauthorised experiments

etc. are strictly forbidden.
2. Never undertake any work unless the hazards of the operation are
known and the safety precautions adopted.
3. Always use protective devices appropriate to the type of operation
being carried out, giving consideration to personnel operating in your
vicinity.
4. Regard all substances as hazardous unless there is definite information
to the contrary.
5. Report all accidents and spills, no matter how trivial, to your
demonstrator. Ensure all spills are cleaned up immediately.
6. Dispose of specialised wastes (e.g. broken glassware, contaminated
disposable items and hazardous chemicals) in containers reserved for
the particular type of waste.
Common laboratory reagents
We keep some common reagents about the laboratory for general use. These fall
into two types.
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1. Concentrated reagents (in fumehoods)
−1 −1 −3
Name Formula Molarity / mol L w/w% / g 100g Density / g cm
Hydrochloric acid HCl 10.2 32 1.16
Nitric acid HNO3 16 70 1.42
Sulfuric acid H2SO4 18 95 1.84
Glacial acetic acid CH3COOH 17.4 99.5 1.04
Ammonia (aqueous solution) NH4OH 14 28 0.89
Sodium hydroxide NaOH 9 36 1.39
2. Dilute reagents (on benches) includes hydrochloric acid (HCl), nitric

acid (HNO3), sulfuric acid (H2SO4), aqueous ammonia solution
−1
(NH4OH) and sodium hydroxide (NaOH). They are all 3 mol L .
Part 0.2__________________________________________________________________________
General principles for volumetric analysis
The aim of quantitative analysis is to determine the quantity of a particular species

in a given sample. Analysis that depends on measurement of volume is called
volumetric analysis. This analysis is carried out by matching a known quantity of a
reactant A (the standard) against an unknown quantity of a reactant B (the
unknown). For this purpose a solution of one reactant is added progressively to a
solution of the other. This process is called titration.
Only certain chemical reactions are suitable as a basis for matching reactants in a
titration. There are several requirements.
• There must be some means of detecting when the stoichiometric equivalent

amount of one reactant has been added to the other. The point where the
quantities are matched is called the equivalence point. The observable
change that can be seen to indicate this is referred to as the end point.
Reagents and reaction conditions used are carefully designed to ensure that
the observable end point closely matches the actual equivalence point.
• The reaction must be free from side-reactions so it can be represented by a
single balanced chemical equation.
• The reaction rate should be fast so that the equivalence point can be
accurately determined.
• The reaction must go essentially to completion, i.e. the equilibrium constant
for the reaction must be large.
Typical reactions used in volumetric analysis include:
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• Those dependent on the combination of ions, such as acid-base and
precipitation reactions.
• Those dependent on electron transfer (oxidation-reduction reactions).
• Those dependent on complex formation.
The technique of volumetric analysis involves understanding and mastering the
following equipment:
• The volumetric pipette - used in the delivery of accurately known aliquots

(volumes) of solution.
• The burette - used in the technique of titration to dispense and accurately
measure the volume of titrant.
• The balance - weighing of objects on both top-loading and analytical
balances.
• The volumetric flask - used in the preparation of standard solutions of
accurately known concentrations.
The reliability of all apparatus used for quantitative measurement depends on the
tolerance margins established by the manufacturer and its correct preparation and
use by you.
Part 0.3 ______________________________________________________________________________
General lab procedures
The following descriptions present the correct procedures for handling the most
commonly used pieces of volumetric glassware and balances in the laboratory. It
also outlines some general procedures for handling tolerances in measurement
when determining the final uncertainties in a calculated value.
Mass using electronic balances
You must use the weighing by difference method when determining accurate
masses of solids. This procedure is as follows:
1. Whenever possible a weighing bottle should be used. If the quantity of solid

to be weighed exceeds the capacity of the weighing bottle a 50 mL or 100
mL beaker should be used—never use a watch glass.
2. Record the mass of the clean empty weighing bottle first—then remove it
from the balance—never add any materials directly into a container whilst
still on the balance. Add approximately the required amount of the
substance into the weighing bottle and then record the total weight.
3. Transfer the contents of the weighing bottle into a beaker, crucible, etc.
4. Re-weigh the weighing bottle as it may contain remnants of the substance
that did not come out in the transfer step in 3 above and record its mass.
By subtraction, the weight of substance transferred can be accurately
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determined. (Mass of substance transferred = total mass of weighing bottle
with contents – final recorded mass of weighing bottle with potential non-
transferred remnants).
The balances in our laboratories are expensive and fragile apparatus. Extra care
must be taken when using them and the following rules are to be observed:
a. Report any fault in balance operation to the demonstrator or

laboratory technician. Do not try to rectify faults yourself and do not
move the balances as this may interfere with their calibration.
b. The glass doors at the sides of the balance case must be closed
during weighing since drafts will upset the measurement.
c. Before weighing, ensure that the pan is clean and dry and examine
the object you are weighing to see that it is not wet or dirty on the
outside.
2. Take your laboratory notebook and record all weighings immediately. Do
not rely on your memory or on scraps of paper. Check that the weight has
been written correctly. It may save you hours of needing to repeat an
experiment!
3. Chemicals must not be weighed directly on the balance pan. Always use a
suitable container such as a weighing bottle (see below) or crucible. Both
weights, not merely the weight of substance, must be recorded. Anything
spilt in the balance must be brushed out immediately. The bench on which
the balance sits must also be kept free of spilt chemicals
4. Warm or hot objects must not be weighed. Convection currents in the air
within the balance will cause errors. These are known as buoyancy errors.
Objects placed on the balance pan are subject to the upthrust of the air that
their volume displaces. A stoppered vessel will weigh less in the laboratory
than in a vacuum. Corrections for buoyancy should be applied to
substances of low density such as water.
5. Further errors may be caused by samples that evaporate or absorb
moisture.
Volumetric flask
A volumetric flask is a calibrated piece of glassware that, when used correctly,

contains an accurately known volume—typically in sizes from 1.00 mL up to
10.0 L. It is most commonly used to make a primary standard solution or to make

dilutions of samples or standards.
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Making a primary standard
A standardised solution is one in which its concentration is accurately known. For

example, to determine the concentration of a solution (unknown) using titrimetric
techniques, a reactant of known concentration (standard) is required. This known
solution can be a previously standardised solution (secondary standard), or it can
be a solution of a primary standard. To be able to be used as a primary standard, a
substance must have the following desirable properties:
• It must not absorb water or react with atmospheric gases, i.e. must not alter
in weight during weighing due to composition variances.
• Have a high molecular weight so that weighing uncertainties are minimised.
• Be readily soluble under the conditions being employed.
• Must react stoichiometrically with the substance being analysed.
To prepare a primary standard solution we must know the accurate mass of our
primary standard using an electronic balance. For the correct care and use of the
electronic balances, please refer to the section above.
The accurately weighed solid can be made into a primary standard solution using
a volumetric flask. The solid must first be dissolved in deionised water before being
quantitatively transferred into the volumetric flask. A quantitative transfer involves Figure 6: Make your
pouring the dissolved solute into the volumetric flask (using a plastic funnel in the solution up to the mark
such that the bottom of
neck of the flask to ensure no spillage), followed by at least 2 rinsings of the beaker
the meniscus is on the
used to dissolve the original solid. Make sure that you do not use too much
mark
solvent—your overall volume cannot exceed the calibration volume specified for
the flask!
After transferring the dissolved solute, the volumetric flask must be carefully filled
to the mark with the solvent. To do this, fill using a deionised water wash-bottle
until the solvent is at the base of the neck then add your solvent dropwise with a
Pasteur pipette until the base of the meniscus is at the etched volume mark, as
illustrated in Figure 6. You cannot remove solvent if you go over the mark
accidentally, so be careful at this step, otherwise you will need to start again!
With the lid in place, and your hand over it so it cannot fall out, the flask is then
inverted and swirled for three repetitions to ensure complete mixing to result in a
homogeneous solution. As the number of moles of solute has been determined,
the concentration of this solution can now be calculated.
Dilution of a sample or standard
Instead of adding a known mass of dissolved solute into the volumetric flask, a
known volume is added using a volumetric pipette. For example, you may need to
dilute a stock solution by a factor of 10. You could use an appropriate volumetric
pipette to transfer 10.00 mL of the stock solution into a 100.0 mL volumetric flask.
Fill the flask with solvent (usually deionised water) and mix well following the same
procedure as outlined above.
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Volumetric pipette
A volumetric pipette will deliver an accurately known volume, but only if used
correctly. It requires a filler to draw the measured solution up into the pipette. One
of the most common laboratory injuries is from a pipette filler being inserted with
too much force causing cuts or even penetration into hands or arms as a result.
Take care when inserting a pipette into a pipette filler. Always grasp the pipette
at its top end, not at or below the bulb, and never apply too much force.
1. Clean the pipette by rinsing thoroughly with deionised water.

2. Insert the pipette into a pipette filler using a slight pressure by grasping at
the end being inserted into the filler.
3. Rinse the pipette with a small amount of the solution to be transferred.
During this step, tilt the pipette to ensure that the whole inner surface is
rinsed.
4. Draw up the liquid until it is above the graduation mark. Take care not to
draw up too much liquid. If you accidentally draw chemical solution up into
the pipette filler, remove the filler and rinse immediately with water. Let
your demonstrator know and leave it to drain on paper towel.
5. Carefully remove the pipette filler and quickly place your forefinger on the
top end of the pipette.
6. Wipe away any adhering liquid from the outside of the lower stem with a
cloth or paper towel.
7. Allow the liquid to drain out slowly until the bottom of the meniscus just
reaches the graduation mark, as illustrated in Figure 7. Hint: slowly rotating
the pipette while resting your forefinger on the top allows more control
during this step than lifting your forefinger. The pipette must be held
vertically with the mark at eye level. Figure 7: Bring the
solution down to the
8. Remove any drop adhering to the tip by touching against a glass surface. mark until the bottom
Do not wipe with an absorbent material such as a paper towel! of the meniscus is on
9. Allow the liquid to run into the receiving vessel with the tip of the pipette the mark
touching the inside wall of the vessel. Do not allow the tip to become
immersed in the liquid.
10. When the continuous discharge has ceased, hold the jet in contact with the
side of the vessel for 15 seconds to ensure a correct draining time. The
liquid remaining in the jet at the end of this drainage time must not be
removed either by blowing or by any other means—the pipettes used in
our laboratories are calibrated to account for this residual solution.
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Burette
The burette is used to deliver a flexible known volume. It is most commonly used
in a titration to deliver a titre—the volume of titrant added to a reaction vessel,
usually a 250 mL conical flask—is determined by subtracting the initial burette
reading from the final burette reading. Steps to prepare and correctly use the
burette are:
1. Clean the burette by washing thoroughly with detergent and tap water;
Rinse thoroughly with tap water and then with deionised water.
2. Using a small plastic funnel, add a small amount of the solution to be
delivered in order to rinse the burette with it. In this step, ensure that the
whole inner surface is rinsed including the tap. You do not need to fill the
burette for this—add a small amount of solution and open the tap briefly
to allow some solution to flow through the tap. Then remove the funnel
and invert the burette to allow the remaining solution to pour out through
the top into a waste beaker–rotate the burette during this stage to ensure
contact of the rinse solution with the inner surface of the burette.
3. Ensure the tap is closed and mount the burette to a retort stand using a
burette clamp, ensuring that it is securely placed and vertical (see Figure 8).
Figure 8: How to set up

and read the volume on
a burette
4. Bring the burette in its stand to the floor and using a small plastic funnel,
approximately fill the burette with solution.
5. Take care to fill the burette safely. Never fill it by lifting a container above
shoulder height, as you may spill hazardous substances into your face.
6. Remove the funnel! The funnel may have some residual solution remaining
in its stem. This can drip at any time during the titration and affect the
results.
7. Pour solution through the tap to fill it as well as the burette column. During
this stage carefully watch the solution as it goes through the tap mechanism
to ensure there are no air bubbles caught up in the tap mechanism. If there
are, keep pouring solution through until they are released.
17
8. Record the initial burette reading at the bottom of the meniscus estimated
to two decimal places as illustrated in Figure 8. Note, it should not be zero
as there is no marking above this to accurately determine this volume.
9. After reaching the end point you should take the final reading the same
way as you took the initial reading. The volume delivered is the difference
between these values and should be reported to two decimal places, where
the final place is a 0 or 5.
Uncertainties in measurement
When the result of a determination is presented, some indication should be given

of the limits of accuracy. If a measurement is repeated many times, statistical
methods may be used to determine the uncertainty of the result. Usually, however,
a determination is made only once or in duplicate or triplicate (due to time
limitations, chemical waste / use considerations, cost evaluations, etc.) and other
methods are needed to estimate accuracy. These methods are based on a
consideration of the uncertainty in each measurement involved in the de-
termination and an estimation of their effect on the accuracy of the final figure.
There are two broad classes of uncertainty—systematic uncertainty and random

uncertainty.
Systematic uncertainty will always act in one direction. Examples are uncertainties
in weighing hygroscopic (water absorbing) samples (always positive) or in weighing
volatile samples (always negative). It is often possible to cope with these
uncertainties by one of two methods:
1. They can be minimised by improvements in technique, e.g. weighing more

rapidly, etc.
2. They can be allowed for by correction factors. E.g. in a titration of acid into
base a little acid is required to change the colour of the indicator, in addition
to that required to neutralise the base. By titrating acid into distilled water
plus indicator an estimate of this indicator or blank uncertainty can be made
and subtracted from all titration figures.
Correction factors cannot always be applied, e.g. the weighing uncertainty for
hygroscopic samples will vary according to size and surface area of sample, time
taken in weighing, humidity, room temperature, etc.
Random uncertainty can act in any direction. It is brought about by uncontrolled

variables. Each apparatus has an inherent absolute uncertainty in its reading, often
cited as a tolerance interval. This includes volumetric glassware like pipettes and
volumetric flasks, balances and analytical instrumentation.
For example, a pipette may deliver up to 0.05 mL too much or too little - even if
care is taken.
18
In this laboratory manual the following random uncertainties, expressed as
measurement tolerances, should be allowed for:
• Weighing: ±0.001 g on a 3-decimal place balance.
• Burette: ±0.05 mL for each reading.
• Pipette: ±0.05 mL for a ±20.00 mL pipette, unless stated as otherwise on

the actual pipette used.
• Volumetric flasks: Assume an absolute uncertainty of ±0.2 mL per 100 mL
capacity, unless stated as otherwise on the actual volumetric flask used.
For example, an uncalibrated 250.0 mL volumetric flask would thus give an absolute
uncertainty of ±0.5 mL.
Calculating overall uncertainty from measurement tolerances
In any experimental procedure, random uncertainties inherent to each piece of

equipment—called tolerances—will all contribute to the final uncertainty of any
quantity determined from the data gathered. An estimate of the final uncertainty
can be determined by applying the following two simple rules:
1. When two figures are added or subtracted, the absolute uncertainty in the
answer is the sum of the individual absolute uncertainties, each expressed
as ± the absolute measure.
2. When two figures are multiplied or divided, the relative % uncertainty in the
answer is the sum of the individual relative % uncertainties.
The absolute uncertainty is the stated tolerance interval; the relative uncertainty is
determined as the absolute uncertainty divided by the measurement value, and is
often expressed as a percentage:
𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑡𝑡𝑡𝑡 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 % 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 = × 100%
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
For a simple titrimetric analysis, the following steps should be followed:
1. Identify sources of uncertainty—these will include any piece of quantitative

apparatus that will be used to gather data that will be included in your
calculations. Quantitative apparatus used in a titrimetric analysis might
include:
• Balance: When using a ’weigh by difference’ approach, this will result in
a total uncertainty of ±0.002 g for each mass weighed (a subtraction
mathematical operation is applied between two readings, each with an
absolute uncertainty of ±0.001 g.
• Volumetric flask: ±0.2 mL per 100 mL, relative % uncertainty of 0.2 %.
• Pipette: ±0.05 mL for a ±20.00 mL pipette.
19
• Burette: ±0.05 mL for each reading, giving total uncertainty of ±0.1 mL per
titre volume (a subtraction operation is applied between two readings,
each with an absolute uncertainty of ±0.05 mL)
2. As the quantity to be determined will involve multiplication and/or division,
only relative uncertainties (in which units are eliminated) can be combined
to calculate the total uncertainty associated with the final value (i.e. ’Rule 2’).
Thus relative % uncertainties will need to be determined for every
measurement.
3. Calculate the total relative percentage uncertainty for the final calculated
value by adding up the relative percentage uncertainties for each source
involved in the analysis.
4. Convert the relative percentage uncertainty into an absolute uncertainty for
the final calculated value for the experiment:
5. absolute uncertainty = (relative % uncertainty)/(100%) × final calculated
value
6. Quote the final answer as the calculated value ± absolute uncertainty, with
correct units. The final absolute uncertainty should contain only one
significant figure, and the number of decimal places cited in the final answer
should match those for the absolute uncertainty.
7. Let’s look at an example. A sodium hydroxide solution was standardised by
titration of a 10.00 mL sample (from a calibrated pipette with tolerance of
0.002 mL) with 0.102 ± 0.002 mol L−1 hydrochloric acid. The average titre
value was 10.87 ± 0.10 mL, and the final concentration was determined to
be 0.1109 mol L−1.
8. Using Rule 2, the relative % uncertainty in the calculated value of 0.1109 mol
L−1 is the sum of the relative % uncertainties each measurement. This can be
set out in tabular form, for example in Table 1.
Measurement Absolute value Absolute uncertainty Relative % uncertainty
Molarity 0.002
0.102 mol L−1 ± 0.002 mol L−1 × 100 = 1.96%
0.102
Average titre 10.87 mL ± 0.1 mL 0.1
× 100 = 0.92%
10.87
Pipette 10.00 mL ± 0.02 mL 0.002
× 100 = 0.20%
10.00
Total relative % uncertainty 3.08 %
Table 1: Tabulation of
relative % uncertainties
for an example titration
The next step is to convert the relative % uncertainty to absolute uncertainty.
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 % 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢
𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 = × 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣
100%
3.08%
= × 0.1109 𝑚𝑚𝑚𝑚𝑚𝑚𝐿𝐿−1
100%
20
The last step is to round the calculated concentration of sodium hydroxide to the
same number of decimal places as the first significant digit of the absolute
uncertainty, i.e.:
0.111 ± 0.003 mol L−1= 0.0034
Notes on uncertainties
Determinations are usually based on duplicates or triplicates. In general it is

satisfactory to calculate the uncertainty in one of the collected data sets and apply
this to the mean result. If the replicated results differ by more than twice the
calculated uncertainty, they are not close enough and further determinations
should be carried out.
The uncertainties expressed are based only on predictable random uncertainties.

Uncertainties due to careless work are not accounted for, nor are systematic
uncertainties. Variable systematic uncertainties may appear as too divergent in
replicated determinations. Constant systematic uncertainties are obscured.
The above rules are a simplified treatment and tend to exaggerate those
uncertainties that are due to predictable random causes.
Acid-base titrations
A titration involves reacting a solution with a known quantity (usually number of

moles from either concentration and volume, or mass and molar mass, with an
unknown solution of known volume but unknown concentration.
One solution is added progressively from a burette to the other solution in a conical
flask until it reaches the point where the two have reacted completely— the
equivalence point. Up to the equivalence point the solution contains an excess of
one reactant; after the equivalence point it contains an excess of the other reactant.
In acid-base titrations, the change in colour of an indicator may be used as

evidence of the changeover. The observable changeover point in the titration is
called the end point. The end point must be as close as possible to the equivalence
point and to achieve this the indicator used must be carefully selected.
At the end point we stop the titration and record two volumes. A fixed volume of
solution in the conical flask—we call this an aliquot; and a variable volume from
the burette—this is called a titre. This is illustrated in Figure 9.
To illustrate the steps in this process we will use sodium hydroxide (NaOH) against
acetic acid (CH3COOH). For this example the NaOH is placed in the burette. In
reality, however, the NaOH solution could be placed in either the burette or it could
be pipetted into the conical flask. This will change the end point colour change
direction, and in some cases the end point may be more difficult to discern.
1. Clean and rinse two beakers and three conical flasks with deionised water.
21
2. Rinse one beaker with a small amount of the acid solution (CH3COOH,
diluted vinegar) and label accordingly. Pour the required amount of acid
solution into the beaker.
3. Rinse the other beaker with a small amount of the base solution (NaOH)
and label accordingly. Pour the required amount of base into the beaker.
4. Rinse a 20.00 mL pipette with the acid solution. Use this pipette to
accurately deliver 20.00 mL aliquots of this solution into each of the
previously rinsed conical flasks.
5. Add 2 or 3 drops of the appropriate indicator to the solution in the conical
flask. Do not add more indicator than needed—indicators are weak acids
and will thus interfere with the results if too much is added as you just need
to add enough to ensure that the colour is clearly discernible.
6. Clean and rinse a burette with the solution you intend to fill it with
(’standard’ NaOH solution). Fill the burette with this solution and record
your initial burette reading. Adjust the height of the burette such that the
tip height is below the mouth of the 250 mL conical flask and place a piece
of white paper beneath the conical flask. This will assist you in detecting
indicator colour changes. Don’t forget to remove the funnel – and ensure
that you record the initial volume to two decimal places.
7. Holding the burette tap in your left hand and swirling the conical flask with
your right hand, add the titrant solution until the first persistent colour
change is noted. Use a deionised water wash-bottle to rinse any splashed Figure 9: Apparatus for
drops from the inside lip of the conical flask down into the bulk solution. a titration, with the
Record the final burette volume to two decimal places and calculate the types of volumes
titre volume delivered (final reading − initial reading). recorded at the end
point
8. Repeat the procedure until you have obtained two or three concordant titre
volumes–that is, three volumes that match within the tolerance required for
the particular titration (often within ±0.1 mL of each other).
Instructions for calibrating the pH meter

Take great care of the electrodes. The glass electrode in particular is very delicate
and easily damaged by careless handling or prolonged exposure to caustic
solutions.
1. Switch instrument on to display pH measurement.
2. Immerse the pH electrode in the pH 7 buffer solution, swirl briefly and wait
3. 20 seconds for thermal equilibrium.
4. Press the "CAL" key. The display should show the temperature
compensated buffer value and the pH symbol should be flashing.
5. Wait until the pH symbol (not the number) stops flashing and press the
"CON" or "CFM" key.
22
6. Remove the electrode and rinse with deionised water before immersing it
into the pH 4 buffer solution. Swirl briefly and wait for thermal equilibrium.
7. The display should show the temperature compensated buffer value and
the pH symbol should be flashing.
8. Wait until the pH symbol stops flashing and press the "CON" or "CFM" key
to confirm the calibration.
9. Rinse the electrodes with deionised water immediately after each use, and
when no longer being used place them back in the conical flask containing
3 mol L−1 KCl solution (do not allow it to become dry).
The instrument is now calibrated and should remain calibrated even after it is
turned off.
UV-Visible spectrometer
When a molecule absorbs a photon (hν1), the energy of the molecule increases.
The energy absorbed from the visible region of the spectrum by a chemical species
(M) causes the excitation of outer valence electrons, which are pro- moted to an
excited state (M*). The excited species are usually unstable, and quickly revert to a
ground state (through the emission of a photon, hν2). The frequency absorbed (ν1)
may not be the same as the frequency emitted (ν2):
M + hν1 M* M + hν2
The energy can also be plotted as a graph of energy absorbed (absorbance) vs

wavelength, called an absorption spectrum, for example Figure 10.
0.3
Figure 10: UV-Vis

Absorbance
spectrum of 0.005 mol L−1

0.2
[Cr(acac)3] in water
recorded at the end point
0.1
0
400 500 600 700 800
Wavelength, λ / nm
Each peak corresponds to the absorption of energy of a particular wavelength

corresponding to one of the electronic transitions. The wavelength of maximum
absorbance is λmax.
Since a spectrum is characteristic of an absorbing species, it can be used for

identification purposes (that is, qualitative analysis). Unfortunately in the visible
23
region usually only one broad band is evident and hence visible spectrometry is
mainly used for quantitative purposes.
The spectrophotometer is the instrument used to quantitatively measure

transmitted radiation. Most quantitative measurements are carried out by
comparison of a blank with the sample solution and at a fixed wavelength
(monochromatic radiation). The amount of monochromatic radiation absorbed by
a sample is then described by the Beer-Bouguer-Lambert Law, commonly known
as Beer’s Law.
A = εbc (3)
The energy absorbed is directly proportional to the concentration of absorbing

species and hence can be used for quantitative analysis, where A is absorbance
(dimensionless), ε is molar absorptivity (L mol−1 cm−1), b is path length (cm) and
c is concentration (mol L−1).
The molar absorptivity coefficient (or the molar extinction coefficient in some early
texts), ε, is related to the intensity of absorption which is proportional to the
number of electrons excited. The value of ε is characteristic of the absorbing
molecule or ion in a given solvent at a given wavelength. Values of ε range from
about 500 L/mol/cm (weakly absorbing) to 20 000 L/mol/cm (strongly absorbing).
Under ideal circumstances, a linear plot of A vs c is obtained, provided:

• the incident radiation is monochromatic from a stable light source.
• the absorbing species act independently of each other—solution must be

dilute, usually 10−2–10−7 mol L−1, giving absorbances in the range 0.05–
1.00.
• absorption occurs in a volume of uniform cross-section (the cells must be
a matched pair, correctly positioned in the beam).
• the temperature of standards and reference should be the same.
Performing a reflux
The majority of reactions are very slow unless heated. For organic reactions it is
not possible to heat a beaker of reagents directly, however, as organic substances
are volatile and evaporate easily. Refluxing allows us to safely heat up a reaction
mixture without loss of reagents, by condensing the vapour from the reaction and
allowing it to fall back into the flask.
To setup for a reflux apparatus we use equipment with ground glass joints— called
Quickfit. We will use a pear-shaped flask and a condenser.
24
When refluxing sodium hydroxide, ground glass joints should be greased
with the minimum amount of petroleum jelly. Caustic solutions can cause
ground glass joints to fuse together.
The reflux apparatus are fitted into the fumehood with two retort clamps— one at
the neck of the flask firmly clamped, and a second loosely clamped to keep the
condenser vertical. This is illustrated in Figure 11.
Figure 11: Reflux

apparatus
Before heat is applied, water is set gently running through the condenser from
bottom to top. When the apparatus is ready and no leaks are detected, leave the
condenser clamped and remove the flask to add your reagents.
Regardless of the reagents added, anti-bumping granules must be added. Anti-
bumping granules (sometimes called boiling chips) are small glass beads or
ceramic chips that help control the bubbling of the boiling mixture and reduce the
risk of breakage of the flask.
If what you are heating is very flammable then a hotplate is the best choice as they
are electrical and have no naked flames. If the operating temperature is below 100
◦C then a water-bath is generally used.
Part 0.4______________________________________________________________________
Assessment
The laboratory program in Reactivity and Function in Chemistry will be assessed in

the following ways:
1. The laboratory journal will assess your performance in completing practical
tasks during the semester through record keeping of what you have done
in the lab. Your demonstrator will assess your logbook and the quality of
your results. You will be assessed on your understanding of chemistry by
completing post-lab reflection questions after each lab.
25
2. You will present a poster to your class during a lab session in the semester.
The mark for this poster will contribute 10% to your final mark. You will be
assigned a poster topic later in the semester. An abstract for your poster
must also be submitted two weeks before your poster presentation via the
Turnitin link on Blackboard. Only one submission per group is required.
Your demonstrator will read it and provide you with feedback.
The schedule of experiments and due dates for related assessment tasks is given
in Table 3.
Laboratory journal
The laboratory program consists of 9 experiments, each of which incorporates a
series of key skills (practical, data manipulation, theoretical) that if successfully
applied will result in the attainment of a specific core competency. The laboratory
is an essential component of the chemistry discipline, hence to pass the Reactivity
and Function in Chemistry unit, you will have to demonstrate a strong commitment
to the Laboratory Journal. The journal consists of three components:
Experimental skills (36 marks)

The practical and data manipulation skills will be evaluated during each laboratory
session and your progress will be noted in your laboratory journal (27marks - 3
marks per lab). Pre-laboratory activities must also be completed prior to your
laboratory session and submitted online via Blackboard (9 marks - 1 mark per lab).
Pre-Laboratory Questions must be submitted via the appropriate link by 11.59 pm of
the day prior to the Laboratory session. Failure to submit the Pre-Lab Questions on
time will result in a mark of 0 for the specific assessment item; late submissions will
no be accepted.
Theoretical understanding (27 marks)

Your theoretical understanding of the experiments will be evaluated by your
answers to post-lab reflection questions (3 marks per lab). The questions are
designed to be completed in a relatively short time commitment, especially if they
are done shortly after the Laboratory session as the collected observations will be
fresh in your mind. Your submission must include your name and student number.
A template is provided on Blackboard. You will answer these questions and submit
a typed document to Turnitin via the link found on Blackboard. You must have
successfully completed the experiments to receive some marks or answer some
questions.
Post Laboratory Questions must be submitted by 11.59 pm on the Tuesday of the
week immediately after the Laboratory Sessions, providing effectively 6 full days to
submit your answers. Failure to submit the Post-Laboratory Questions on time will
result in a mark of 0 for the specific assessment item; late submissions will not be
accepted.
26
Wednesdays: Building 500 Level 4 laboratories

Please check your registration for your laboratory class and session time -
due to strict OH&S regulations students cannot be permitted into a laboratory
Week Begin Date
session for which they are not formally registereda. Punctuality & correct PPE
are also essential for entry into a laboratory. Students are expected to
complete all experiments.
0. 18 Feb Orientation Week
No scheduled experiment (except students registered in Lab 4230):

Laboratory Program Preparation Time.
All students: Visit the labs to know where to come next week! Review safety
information on Blackboard & acquire necessary PPE gear. Download, print
1. 25 Feb and read Laboratory Manual information pages and the first experiment.
Complete online safety induction. You will not be allowed in the laboratory
if you do not complete the safety induction.
Students using elogbooks will be provided with elogbook training. Check

your email closer to the date for details.
2. 4 march Purification of benzoic acid by recrystallisation
3. 11 March Synthesis of benzoic acid
Logbook #1
4. 18 march Preparation and reactions of cyclohexene submit at the end of
lab session
5. 25 March Tuition Free Week
Preparation of 4- nitroacetanilide
6. 1 April
7. 8 April Acid/base titration/titration curve
Logbook #2
8. 15 April Designing and making buffer solutions submit at the end of
lab session
Poster abstract
9. 22 April Tuition Free Week due 24th April, 11.59
pm via Blackboard
10. 29 April Kinetics of the iodine clock reaction
Poster presentation
11. 6 May POSTER presentations
during lab session
12. 13 May Extraction of organic compounds
Logbook #3
13. 20 May Carboxylic acids and their derivatives – using mind maps to link concepts submit at the end of
lab session
14. 27 May No lab
15. 3 June Study Week
16. & 10 & 17

Examinations
17. June
Table 3: Schedule of
experiments and due dates
for related assessment tasks
27
Laboratory logbook (27 marks)
A logbook will be issued to you in your first laboratory session in Week 2 for you
to keep a journal of your laboratory experiences during the semester. Although you
will complete most experiments with a partner, your logbook must be completed
by you as an individual. You may discuss any aspect of the lab with others and help
each other out with understanding any component of the experiment (e.g. purpose,
answers to questions, calculations), but what you record in your logbook must be
in your own words and not copied from others.
In your laboratory logbook you will need to keep a record of your results,
observations, inferences, calculations, discussions, answers to questions (including
pre-lab questions), etc., for each experiment. An example of part of an exercise
written up in a logbook can be found on Blackboard. Guidelines for what to include
in your logbook can also be found in the notes for Experiment 1. If you want further
guidance – ask your demonstrator. You must have successfully completed the
experiment to be able to receive the logbook mark for that experiment.
Your logbook will be marked three times during the semester. The weighting
increases as the semester progresses to recognise your improving competency
with completing your logbook. Table 2 indicates the breakdown of marks. You
must submit your logbook at the end of the lab session to your demonstrator in
the designated logbook marking weeks to have it marked. Failure to submit your
logbook give you a mark of 0 for the experiments that will be marked in that block.
As part of the logbook assessment component, you will need to complete a self-
assessment on your performance in completing your logbook and provide a
reflection on how you could improve.
Task Experiments Weighting Total marks Due date

1 mark each experiment Week 4, at the end
Logbook #1 Experiment 1 & 2, 3 6
3 marks self-assessment of lab session
2 marks each experiment Week 8, at the end
Logbook #2 Experiments 4, 5 & 6 9
3 marks self-assessment of lab session
3 marks each experiment Week 13, at the
Logbook #3 Experiments 7, 8 & 9 12
3 marks self-assessment end of lab session
Table 2: Schedule of due

dates and weighting for
the laboratory logbook.
Summary
Therefore, the combined 9 laboratory sessions will award a maximum of 90 marks,
counting 20% towards the Final Mark for this unit. See the 'Laboratory Journal'
section in the Laboratory manual as well as information posted on Blackboard for
further details about each component and how they will be marked.
28
Posters
A poster and short talk on an experiment or series of experiments undertaken

during the laboratory learning environment will be presented by pairs of students.
Guidelines for preparing your poster and an assessment rubric will be provided on
Blackboard. Poster topics and group allocations will be finalised in Week 7. A group
abstract must be submitted via Blackboard in Week 9. Failure to submit an abstract
will result in a 10% deduction in the group poster presentation mark.
Attendance
We expect you to attend all scheduled laboratory sessions for your chosen class.
The schedule of experiments can be found in Table 3, and your timetable can be
found in OASIS.
If you miss your scheduled laboratory class you will not be able to attend a different
class. We have a restricted capacity in every laboratory, and only students with a
registration can attend a given class.
If you miss a laboratory session you will be able to submit the post-lab questions
without significant impediment. You should prepare and submit it without delay,
and attend your next scheduled laboratory class. However, you will not be able to
obtain any marks for the logbook component or experimental skills component of
the Laboratory Journal assessment, since you have not completed those tasks.
If you have missed an experiment, then you may collaborate with another
student to obtain raw results only to answer the post-lab questions and must
be acknowledged. All other aspects of the assessment task must be your own
work. You must not copy or reproduce any calculations or graphs — this is
collusion. The source of these results must be attributed in the reference list, for
example:
“The results for experiment 1 were obtained from Jane Smith and are used
here with permission”
If you are asked to provide your results to another student you may only give
them raw data (volumes, concentrations of stock solutions, masses etc) and you
have a right to refuse to provide this information. If you provide your results to
another student to use, then you should include the following statement:
“The results for experiment 1 were provided to Kate Jones with my permission”
Assessment extensions
If you miss (or are likely to miss) two or more consecutive laboratory sessions, and
you have an exceptional circumstances beyond your control, you should apply for
an assessment extension.
29
Assessment extensions for laboratories will only be approved if the circumstance is
long term (e.g. more than one week) and beyond your control. Assessment
extensions will not be approved because of isolated or short term circumstances.
You must apply for an assessment extension using the Assessment Extension form
(available from OASIS). It is your responsibility to provide evidence for exceptional
circumstances beyond your control that prevent you from completing experiments
and submitting the associated assessment task.
You will be expected to lodge the completed form and supporting documentation
with the unit coordinator before the assessment task due date.
Please email the completed form and supporting evidence from your Curtin
student email address to mlsstudents@curtin.edu.au.
An application may be accepted up to five working days after the due date of the
assessment task where you are able to provide an acceptable explanation as to why
you were not able to submit the application prior to the assessment date.
The laboratory session
1. Complete Safety Induction on Blackboard to be allowed in the Laboratory.

You must complete the Safety Induction by Tuesday 05/03/2019 at
23.59, or you will be denied access in to the Laboratory. This Induction
is valid for the full semester.
2. Prepare well beforehand by reading all the relevant information in this
Laboratory Manual relative to the session you are going to attend.
3. Download the Pre-Laboratory questions template file from Blackboard,
complete the questions and submit it via the appropriate link. Photos of
mechanisms and flow-charts are accepted and must be inserted into your
document. You have to submit the Pre-Laboratory questions by the end of
the day preceding your laboratory session. The link will disappear at 11.49
pm, and no late submissions will be accepted under any circumstance. If
you have not submitted a copy of your Pre-Laboratory questions, you
will be allowed to view the demonstrator safety briefing but you will not be
able to commence your experiment until your Pre-Laboratory
Questions have been completed, and you will still receive a mark of 0 for
this assessment item.
4. Attend the laboratory session, record all your important data, observations
and inferences in your laboratory logbook. There are also some questions
you must complete during the laboratory session. It is important that you
have access to the Laboratory Manual during each session, whether in
electronic form or printed form. You must bring a printed copy of the
assessment page for your logbook. Make sure you collect all the necessary
data from the Laboratory session; if in doubt, feel free to ask your
demonstrators for advice.
30
5. Download the Post-Laboratory Questions template file from Blackboard
and complete it using the collected data from the previous laboratory
session. The deadline to submit your Post Laboratory Questions is the
Tuesday of the week after the Laboratory Session (e.g. 6 days after the
Laboratory Session). The link will disappear at 11.49 pm, and no late
submissions will be accepted under any circumstance. The completion
of the Post Laboratory Questions should not take more than a couple
of hours; we recommend that you complete them as soon as possible
after the end of the corresponding Laboratory session. When Post-
Lab questions ask for calculations, pictures of handwritten or hand-
drawn pages are not accepted. These must be prepared using
programs such as Word (Equation Editor) and Excel. Equivalent
programs are accepted. Photos of mechanisms and flow-charts are
accepted.
IMPORTANT! Note on submissions to Blackboard: any completed submission
via Turnitin in Blackboard will result in you receiving a submission receipt
via email. If you do not receive a receipt, it means your submission is not
complete. Always keep your submission receipts until the end of the unit.
Leaving the Laboratory neat and tidy, and most importantly safe, is of paramount
important.
Therefore, before leaving the laboratory make sure that:
• The work area is clean and tidy
• All glassware is returned to the lockers
• All used areas, such as bench, fume hoods and sinks are wiped and
clean
• All the reagents used have been returned
IMPORTANT! Failure to comply with these steps will result in you being given
a mark of 0 for the Experimental Skills assessment component of the
Laboratory Journal.
31
Experiment 1 On successful completion of this

experiment you will be able to:
Purification of benzoic acid by  determine which solvent is

appropriate for your sample,
develop filtration skills and
recrystallization determine the purity by measuring
the melting point.
Other goals include:

 Planning an experiment
Safety using flow diagrams. Being able
to identify the key steps in a
procedure and the chemistry
associated with each activity is
critical to successful outcomes.
 Using precise and concise

language. To communicate
All organic solvents used in this experiment should be regarded as toxic and science the language must be
precise and it is also good practice
flammable. You should use all organic solvents in the fumehood and wear to be concise. Answering the pre-
appropriate gloves if requested. laboratory and post-laboratory
questions will provide practice in
You must correctly wear a laboratory coat, safety glasses, and fully enclosed developing this skill.
shoes at all times in the laboratory while conducting this experiment.
Your demonstrator will illustrate the procedural hazards during the pre-
laboratory briefing.
Why?
Recrystallisation is a fundamental technique for the purification of solids and you

will use this technique in subsequent labs. In today’s experiment we are going to
purify a crude sample of benzoic acid using recrystallisation.
Part 1.1_____________________________________________________________________
Introduction
Purification of a solid is usually carried out by crystallisation of a solute from an

appropriate solvent. The solubility of most solids in liquids increases with increasing
temperature. Consequently, a hot, saturated solution will deposit crystals of the
solute on cooling. This process is called crystallisation and the solute is said to
crystallise.
32
The choice of the most suitable solvent requires care. The substance to be purified
should be readily soluble at the boiling point of the solvent and only very sparingly
soluble at room temperature or a little below. The solvent should not react with the
solute, it should not be very toxic and should be readily evaporated from the
crystals. Also, impurities should either be very soluble in the cold solvent, or
insoluble in the hot solvent. Frequently it is necessary to use a mixture of solvents,
a common one being ethanol-water.
Use of Organic Solvents
When an organic liquid is used for crystallisation, or in a reaction at elevated

temperatures, the apparatus usually employed is termed a reflux apparatus. The
vapour of the boiling liquid is condensed in a reflux condenser (an ordinary
condenser used vertically) and drops back into the flask. This allows heating at the
boiling point of the solvent without losing any of the solvent. In this experiment
you will be using water as the solvent. In addition to water having the properties
suitable as a solvent for recrystallisation, water is also cheap, freely available in the
laboratory and non-toxic, making it safe to use in the laboratory.
Part 1.2_____________________________________________________________________
Completing your logbook
In CHEM1002, you will need to complete a laboratory logbook each week for each
experiment you do in the laboratory. Your logbook is your record of all of your
results, observations, calculations, discussions, etc. for CHEM1002. It is an official
document and another person should be able to pick up your logbook and be able
to read it, understand it and to repeat any procedures described. Therefore, your
writing should be neat and tidy, have the correct spelling and be in sentences and
paragraphs.
Many of you may not have experience in do that, so this activity will provide you
with some guidance. An example of part of an exercise written up in a logbook can
be found on the Blackboard. If you want further guidance - ask your demonstrator.
Below are some guidelines for completing your logbook:
1. On the first page of your logbook create a Table of Contents and add to
it each week. This will make it easier to locate specific experiments when
required
2. Each page of your logbook needs to be numbered continuously
throughout logbook and NO pages may be removed.
3. The date on which the experimental work was carried out must be given.
4. You need to write in PEN, but pencil may be used for diagrams and
graphs.
33
5. Pre-laboratory activities must be included (stapled or glued) in your
logbook for each experiment.
6. Unless otherwise stated you should NOT be copying information from
these laboratory notes into your logbook. Write a brief summary of the
experimental aim, and briefly describe the experimental method you used
(past tense!). If you use the same experimental method in a subsequent
experiment you can refer to the experiment in which you originally
described it.
7. Record observations and inferences you make during your experiments,
raw data (in tables where appropriate), work-up of raw data (e.g.
calculations), results and discussion/reflection.
8. Informative titles and sub-titles for each experiment, data set and
accompanying discussion should be given.
9. If you are using an electronic logbook, please ask your demonstrator for
help if you are unsure how to do things on the tablet. Some things listed
above do not apply to you. Guidelines are also provided on Blackboard.
Getting started with your logbook
1. You have just been provided with a logbook. Write your name, lab room
number, lab class time on the front of your logbook in the space provided
2. Each page number of your logbook must be numbered continuously.
3. Starting from page 1, number the first 30 pages of your logbook.
4. On page 1 start a Table of Contents – it can be brief! E.g. your first entry can
be:
• “Expt 1: Equivalence point vs endpoint…….page 2”.
5. The date on which experimental work is carried out must be given.
• Write today’s date on the page 1 for today’s experiment.
• Remember to write the date on all pages of your logbook that you use
today.
6. Informative titles and sub-titles for each experiment, data set and
accompanying discussion should be given.
• Write the title of today’s experiment on page 1.
• Remember to include titles for figures and tables.
7. As records in your logbook, you will be writing down observations and
inferences for each experiment. Observations can be qualitative or quantitative
and are factual descriptions of information gathered in the laboratory using
your five senses. E.g. Bubbles were seen as the reaction proceeded. An
inference is an educated guess or reasonable conclusion drawn from the
34
observation. It is a possible explanation for the observation. E.g. Gas was
produced in the reaction.
Look at the picture on the right and use it to make one observation and
one inference. Write these down in your logbook.
Below are a few statements. Indicate whether these are observations or
inferences.
a) It must have rained because the grass is wet
b) It is 30 degrees today
8. Ask your demonstrator for help if you need clarification of the
difference between observations and inferences (if needed).
Part 1.3 ____________________________________________________________________________
Procedure
When completing an organic chemistry experiment, it is important to recognise

what your starting materials and products are, and even the reaction that is taking
place.
For your log book
1. Draw the structure of your starting material (crude benzoic acid) and
product(s) and write down the molecular weight for each.
In this experiment your starting material (crude benzoic acid) and product (pure
benzoic acid) is the same. This will not be the case for future experiments. So, you
will need to write out the equation. This is required for you to calculate your yields.
See Blackboard for an example.
2. Copy the table below. Don’t forget to include a title for your table.
Wt weighing bottle + impure benzoic acid
Wt “empty” weighing bottle
Wt impure benzoic acid
Weigh out (by difference) 1 g of impure benzoic acid and place it in a 100 mL
conical flask. Then add a few anti-bumping granules.
For your log book
3. Record the mass of your crude benzoic acid under the structure you drew
in Q1.
35
Purify the crude benzoic acid by recrystallisation using the following procedure:
1. Set up a hot plate in the fume-hood.

2. Place a 100 mL conical flask containing ~80 mL of deionized water and
a few boiling chips/anti-bumping granules on the hot-plate to warm.
3. Set up your hot filtration. This is necessary to ensure that your solution
does not cool and deposit crystals during this process.
a. Prepare your fluted filter paper to encourage rapid filtering (see
glossary). Your demonstrator will show you how to do so.
b. It is necessary to warm the funnel as well. This is best done by
placing the funnel and filter paper above the 100 mL conical flask
containing the crude sample and allowing the hot vapours, from
the boiling solvent, to warm them.
4. Dissolve the impure compound in a minimal amount of hot the
solvent (water) to produce a saturated solution at or near the boiling
point of the solvent (about 50 mL).
5. Remove any insoluble impurities by hot filtration using a stemless
funnel with a ‘fluted’ filter paper. The stemless funnel should be
supported in an O-ring mount clamped to the scaffolding in the fume-
hood. This set-up is shown to the right.
6. Allow the filtrate to cool and crystallisation to occur. It is usually
desirable to obtain the final product having crystals as large as possible
(to aid rapid filtration and drying). This is best achieved by slow cooling
of the hot solution under normal atmospheric conditions. If time is
pressing, the flask can be cooled under the tap.
7. A final cooling in an ice-bath will enhance your yield. This should be
done only after the solution has cooled to room temperature.
Impurities that are more soluble than the substance to be purified
remain in solution after the desired compound has crystallised.
8. Separate the crystals by suction filtration and washing them to remove
any adhering 'mother liquid' (the solution remaining after crystallisation
has occurred). This is carried out using a Hirsch or Buchner funnel and
a vacuum pump (see glossary).
9. The recrystallised substance may then be dried by drawing air through
the sample while it is in the Hirsch funnel, by pressing between filter
papers or in a vacuum desiccator or 'drying pistol' (see Furniss et al. 1,
Section 2.20).
10. Dry the sample by suction on the Hirsch funnel until your sample is
dry.
1
Furniss, B.S., Hannaford, A.J., Smith, P.W.G. and Tatchell, A.R. (1989) "Vogel’s Textbook of Practical Organic
Chemistry" 5th ed., Longman Scientific and Technical, Harlow
36
11. When your sample is dry, weigh it and record its accurate mass.
Ensure that you provide your sample to your demonstrator to view and
mark before discarding the sample. You may wish to photograph your
product and apparatus for use in the poster you will present at the end of
semester
For your log book
4. Copy the table below
Wt weighing bottle + pure benzoic acid
Wt “empty” weighing bottle
Wt pure benzoic acid
5. Record your mass of recovered product! Did you remember to note down
observations as well? This is something you should always do… E.g what
is the appearance of our purified compound? How does this compare to
the original crude sample?
6. Determine your % recovery of benzoic acid
𝒎𝒎(𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓)
% 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓 = × 𝟏𝟏𝟏𝟏𝟏𝟏
𝒎𝒎(𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓)
7. What was the principal advantage of using a fluted filter paper for the
hot filtration?
37
Melting point determination
The melting point of an organic compound is of considerable value

as a criterion of purity and also in characterisation and identification.
When reporting a melting point, this is given as a range, from the first
signs of melting until the sample is fully molten.
A wide melting point range usually indicates impurity, while a sharp

melting point, unchanged by further purification (e.g. crystallisation)
indicates purity.
You will be using an Electrothermal melting point apparatus. A

procedure is available with the instrument and your demonstrator will explain its
use. A picture is shown above.
Melting points may be used to identify a compound.
Procedure
Firstly, determine the melting point of your purified benzoic acid. The apparatus
can take multiple samples simultaneously, so ensure that you are determining the
melting point of your sample. For comparison, also record the melting points of
your other group members.
Turn the melting point apparatus off immediately after use to ensure there is
sufficient time for it to cool before the next use.
For your log book
Copy the table below and record the melting point range and observations about
colour and dryness for your pure benzoic acid sample and those for one other
group. Make sure you include their names.
Colour Dryness
Melting Point Range
Group Members Grey, off-white or Dry, slightly wet or
°C
white wet
Your sample
Name: ...........................................................
After completing the experiment and writing in your logbook, check that you have included your pre-
laboratory activity, Feedback/departure checklist page in your logbook before you leave.
38
Glossary
Flowcharts
The procedure given above can also be represented by a simple flowchart. In

organic chemistry it is common for procedures to be represented this way,
making it clear to follow, particularly when there are multiple similar steps.
Flowcharts do not need to be so detailed as you become more familiar with the
techniques. For an experienced organic chemist, this procedure can be
simplified to “recrystallise from [solvent]”.
In future experiments, you will be expected to construct a similar flowchart as

part of your pre-laboratory preparation.
39
Fluted filter paper
A 'fluted' filter paper is obtained by taking an ordinary filter paper and folding
it in halves and then in quarters in the normal way.
Instead of opening the paper to fit the funnel at this stage, the folded sections
are folded in halves again by doubling them inwards towards the centre fold.
Each of the sections obtained in this way is then folded in halves again, the first
fold being outwards and then the rest arranged so that the edge of the paper
eventually presents a zigzag appearance.
Büchner and Hirsch funnels are porcelain or glass funnels with a perforated
disc to support the filter paper in vacuum filtration. The Büchner type has a
cylindrical shape, while Hirsch funnels are conical like ordinary glass filter
funnels. In use they are fitted into the neck of a filter flask, the side arm of which
is connected to the vacuum pump and the whole apparatus clamped in place
with a retort stand and clamp as illustrated.
• A filter paper of an appropriate size is placed on the porcelain disc,

moistened with a little of the solvent to be used in the filtration, and
then sucked down tightly by turning on the pump.
• The suspension of solid is now poured onto the filter and the liquid
drains rapidly away from the solid. Any residual solid in the flask
should be washed out using some of the filtrate (the liquid in the
filtration flask).
• The solid should be washed with a little of the cold solvent used. This
is done by disconnecting the pump, pouring a little solvent onto the
solid, reconnecting the pump, and allowing it to suck the liquid
through until the solid is as dry as possible.
• Finally, the solid should be firmly pressed down with a spatula to allow
any further liquid to drain away.
The main value of Büchner and Hirsch funnels is in recovering a fairly large
amount of solid from a suspension as in recrystallisation. When a little solid
impurity has to be removed from a large volume of liquid, it is usually better to
use a fluted filter paper.
40
This page is left intentionally blank
41
Part 1.4______________________________________________________________________
Assessment
Include this page in your logbook
Your experimental skills will be assessed by your demonstrator during the lab
session. Your theoretical understanding will be assessed by your answers to some
post-lab questions. Your logbook will be assessed according to the schedule on
page 27.
You must ensure you have left your workshop clean, tidy and safe before you leave
the laboratory. Failure to comply will result in you being given a mark of 0.
Experimental Skills
Competent
Criteria Developing (0 marks) Exemplary (1 mark)
(0.5 marks)
The recrystallization was set

No Yes, with guidance Yes, without guidance
up correctly
There was sufficient yield of Fair

Very poor (<30%) Good (>75%)
purified benzoic acid present. (About 50%)
The melting point of the

MP outside range ± MP outside range ±
benzoic acid sample MP within range ± 5oC
15oC 10oC
indicated a high purity
Total Mark
Theoretical Understanding – Post-lab questions
1. Consider the melting point range of your product. How does it compare to the
literature value for benzoic acid, and do you think you were able to recover a
pure sample? If not, what do you think would be the most likely impurity in
your sample?
2. In pre-lab question 5, you were asked to comment on why Fred obtained a very
low yield after recrystallisation. Considering the experiment you’ve just
completed, and the % recovery you achieved, comment on any additional
reasons Fred’s yield was so low and ways he could improve it next time.
3. It was important to rinse the crystals with pure cold solvent after they had been
collected by vacuum filtration. What type of impurities are being removed in
this step?
42
43
Part 1.5______________________________________________________________________
Pre-laboratory questions
These must be completed before your laboratory session and submitted via the
Turnitin link on Blackboard. Make sure you bring a copy to the lab to help you
during the lab session.
Safety
1. Locate a SDS (Safety Data Sheet) for benzoic acid and list three specific
hazards associated with pure benzoic acid and write down what action you
would take to minimise the risk to you and others when handling benzoic
acid in the laboratory. Cite the source you used to get this information.
•
2. Identify two specific safety hazards associated with this experimental

procedure and state what precautions you will take to minimise the risk of
each hazard.
•
Experimental
3. Study the flowchart shown on page 38 and answer the following questions:
a) How many filtrations are used in this experiment? Identify each
filtration step and describe the set-up in each (you may do this
diagrammatically if you wish).
b) How, and at what step, are the insoluble impurities removed?
c) How, and at what step, are the soluble impurities removed?
4. In choosing a suitable solvent for the purification of an organic solid by
recrystallisation, what essential features must be looked for?
5. Fred obtained a very small amount of benzoic acid from his recrystallisation
experiment. Consider the flowchart and information given in the
introduction and suggest three possible reasons for his low yield, as well as
suggestions for how he could maximise his yield next time.
•
6. What is the accepted literature value for the melting point of benzoic
acid? Cite the source you used to get this information (e.g. CRC Handbook of
Chemistry and Physics, chemicals supplier website…, date accessed….).
45

Preparation of benzoic acid  Carry out a synthesis using

reflux and purification by
recrystallisation. You will oxidise
an alcohol under reflux conditions
and then purify the isolated crude
acid by recrystallisation.
Safety
 Oxidation of alcohols and
acid/base properties of
carboxylic acids. This experiment
will demonstrate the oxidation
reactions of alcohols. The isolation
of benzoic acid from the reaction
All organic solvents used in this experiment should be regarded as toxic and mixture will rely on understanding
the acid/base properties of
flammable. You should use all organic solvents in the fumehood and wear carboxylic acids.
appropriate gloves if requested.
 Presentation of results
You must correctly wear a laboratory coat, safety glasses, and fully enclosed through posters and talks. This
shoes at all times in the laboratory while conducting this experiment. experiment may be selected for
inclusion in the poster, so you
should consider photographing
your apparatus and product.
Aim
To prepare benzoic acid from benzyl alcohol, recrystallise this product and
determine melting point to assess its purity.
Part 2.1______________________________________________________________________
Background
The reaction that is the basis of this experiment can be expressed:
a) KMnO4/NaOH
CH2OH
b) H2SO4
COOH
benzyl alcohol benzoic acid

46
Part 2.2______________________________________________________________________
Procedure
1. Place 2 g of potassium permanganate, 5 mL of 3 M of sodium hydroxide

and a few anti-bumping stones into a 100 mL pear-shaped flask and add
approximately 25 mL of water. After adding the reagents, grease the
joint 2 and then set up the apparatus for reflux as shown below.
No stopper - the top stays open
Water out
Clamp loosely
Water in
Clamp firmly Figure 2.1: The reflux

apparatus is set up as
shown. Before
commencing your
reflux, please ensure
your demonstrator has
Heat gently
observed your
2. The clamps must be fitted as shown, with the lower clamp holding the
apparatus together and the upper clamp loosely tightened to stop the
condenser moving during reaction.
Glass joints must be greased with Vaseline when strongly alkaline solutions
are being used (for neutral or acidic solutions, grease is not necessary).
3. Heat the flask so that the reaction mixture is boiling gently and
continuously. Too vigorous heating or stop-start boiling may cause
problems, e.g. vigorous bumping so that the contents of the flask splash
up the condenser. Slowly add by Pasteur pipette drop by drop 1 mL
(1.04 g) of benzyl alcohol using a dropper (see Safety Issues (a) and (b)).
2
Heating under alkaline conditions can cause the Quickfit glass joints to fuse, rendering their separation difficult
and increasing the risk of breakage. The joints must hence be lubricated (e.g. with grease/vaseling/petroleum
jelly).
47
The addition should take about 5-10 minutes (slower addition offers no
advantage).
The oxidation of benzyl alcohol is very vigorous so it is essential that the

alcohol be added dropwise. This is best done using a Pasteur pipette dropping
the alcohol down the inside of the condenser. The tip of the pipette should be as
low as possible down the condenser.
4. Rinse the residual benzyl alcohol down the condenser with a few
millilitres of water and allow the reaction to continue until the reaction
appears complete (10-15 minutes). Cool the reaction mixture in an ice
bath.
5. Filter off the manganese dioxide using a Hirsch funnel. Ensure you wet
the paper with a little water first to make sure it is seated properly in
the funnel. Wash the manganese dioxide on the filter paper with two 3
mL portions of water to remove adsorbed sodium benzoate.
6. Transfer the filtrate to a 100 mL conical flask and add enough sodium
metabisulfite (one spatula at a time) so that the solution becomes clear
and colourless. It may be necessary to add a few millilitres of dilute
sulfuric acid. Caution: SO2 may be produced.
Care is needed as too much metabisulfite and sulfuric acid may produce SO2, a
toxic gas. Ensure that this step (as well as all others!) is carried out in the fumehood.
7. Then acidify the solution with dilute sulfuric acid until a large amount
of white solid is precipitated. Avoid using too much acid as the extra
solvent will dissolve some of the product.
Glassware stained with manganese dioxide must be cleaned with a dilute solution
of sodium metabisulfite.
8. Cool the suspension in ice and then, collect the benzoic acid by vacuum
filtration.
9. Rrecrystallise your crude product from water using the same procedure
you used in Experiment 1: Purification by Recrystallisation. About 60-80
mL is usually required, but it is better to start with <50 mL and add more
as needed. Refilter the recrystallised product and allow air to draw
through the product until dry.
10. Transfer the product to a clean and dry pre-weighed watch glass and
record its mass.
11. If time permits, determine the melting point of the dried product and
calculate the percentage yield.
48
Do not dispose of your product until your demonstrator has witnessed your
product and recorded its quality on the feedback sheet. This experiment may
be selected for inclusion in the poster, so you should consider photographing your
apparatus and product.
Once your demonstrator has recorded his/her feedback, you may dispose of the
sample in the yellow hazardous waste bins.
Part 2.3______________________________________________________________________
Results
For your log book
1. How could you easily tell when the reaction is complete? Hint: Look at the
condensing vapour.
2. Calculate the expected 100% conversion of benzyl alcohol to benzoic acid
using your quantities of starting reagents.
3. Copy the table below and determine the mass of your purified and dry
product
Mass of container g
Mass of container + your sample g
Mass of your sample (by difference) g
4. Using the 100% conversion value calculated above determine your yield
(mass obtained) as a percentage of this conversion value.
5. Determine the melting point of your product and comment on its value with
reference to the literature value.
6. Complete your logbook following the guide on page 32. You will not be
reminded for subsequent experiments.
49
Part 2.4______________________________________________________________________
Assessment
page 27.
Experimental Skills
Criteria Developing (0 marks) Competent (0.5 marks) Exemplary (1 mark)
Set up: The reflux was substantial guidance some guidance with minimal
set up correctly with… required needed guidance
Quality of crude
Moderately coloured Very pale / cream -
product: The colour of Light brown coloured
(brown) white
the crude product was...
White crystals
Quality of purified
obtained but m.p.
product: The colour & Product not purified White crystals & good
either indicates
melting point of the at all melting point range
impurities or wasn’t
purified product was...
done
Total Mark
Theoretical Understanding - Post-lab questions
1. What is the purpose of the reflux condenser?

2. Why is the benzyl alcohol added slowly?
3. What is the purpose of the addition of sulfuric acid? Include chemical
equation(s) as part of your answer. Remember that chemical equations
can include chemical structures.
50
51
Part 2.5______________________________________________________________________
1. In this experiment you will synthesise benzoic acid from benzyl alcohol. Fill
in the following table for the main organic compounds relevant to this
conversion.
Benzyl alcohol Potassium benzoate Benzoic acid
Structure
IUPAC name
CAS number
Molecular weight
Appearance at room
temperature
Boiling or melting point
Solubility in water
(25 °C)
Solubility in water (>75 n/a

°C)
Safety hazards when

handling this substance
2. Benzoic acid can be prepared by oxidation of benzyl alcohol in the presence

of alkaline KMnO4.
a. What colour do you expect the reaction mixture to be at the:
i. start of the reaction?
ii. completion of the reaction?
b. What is the purpose of performing this reaction under reflux

conditions?
52
3. What is the organic product of this oxidation under alkaline conditions, and
what will be its appearance in the reaction mixture?
4. After the reflux is complete, you will cool your reaction mixture and acidify
it. What is the purpose of acidifying the mixture, and what will be the
appearance of the organic product in the cooled reaction mixture after this
step?
5. You will be performing a reflux during this experiment. You have
a) No stopper
performed a distillation before, but a reflux has a different set-up. When
performing a reflux it is important that the equipment is set up correctly
(see adjacent figure). Identify the worst case scenarios if:
b) Bottom =
a) a stopper was incorrectly placed in the top of the condenser tube. water in
top = water out
b) the water hoses were incorrectly placed such that water ran down the
condenser tube rather than being directed upwards?
c) boiling chips were incorrectly not added to the reaction vessel.
c) add boiling chips
6. Using the example given in Experiment 1, construct your own flowchart

for this experiment. This should be sufficiently detailed and contain all
the relevant procedural steps for this experiment. i.e. don’t forget the
steps used to purify your product and test for its purity 3.
Your demonstrator must view and approve this flowchart before you will be
permitted to commence this experiment. If it is incomplete or incorrect, you will
be given time at the start of the lab to finish it.
3
Hint: You will purify your product using recrystallization. You have done this in a previous experiment! You will
need to refer to your previous notes when you conduct this purification.
53

Preparation and reactions of  Use glassware appropriately

to synthesise, isolate, and purify
a product. You will assemble
cyclohexene glassware to safely distil a
flammable liquid and use a
separating funnel to isolate it from
an aqueous solution. Distillation
and separation are fundamental
techniques in organic chemistry
Safety and you will use these techniques
in subsequent labs.
 Synthesise alkenes by
elimination reactions. You will
carry out an elimination reaction
to form an alkene and identify the
alkene functional group through
some chemical tests. In
completing the flow diagram you
Cyclohexene is a flammable liquid. Phosphoric acid is corrosive.
will be able to identify the key
steps in the procedure and the
All procedures in this experiment must be conducted in the fumehood. You
chemistry associated with each
should avoid naked flames in the vicinity of cyclohexene and wear appropriate activity.
gloves if requested.  Use precise and concise
language. You will answer the
You must correctly wear a laboratory coat, safety glasses, and fully enclosed pre-laboratory and laboratory
reflection questions to develop
written communication skills. You
will also use this experiment to
demonstrate your development in
regards to laboratory notebook
skills.
Your demonstrator will illustrate the procedural hazards during the pre- Other goals include:
laboratory briefing.  Presentation of results
through posters and talks. This
experiment may be selected for
Aim
To prepare cyclohexene from cyclohexanol and to carry out several tests on the
product to illustrate reactions which are characteristic of alkenes.
Part 3.1______________________________________________________________________
Background
The elimination reaction that is the basis of this experiment can be expressed as:
54
The cyclohexanol and acid catalyst (phosphoric acid) are placed in the distillation
flask (which acts also as a reaction vessel). As the reaction proceeds and the the
mixture is heated the component with the lowest boiling point should start to
vapourise and enter the condensing tube. Each chemical species in the reaction
mixture, along with their respective boiling points, are shown in Table 3.1.
Chemical Boiling Point (°C) Chemical Boiling Point (°C)

Cyclohexanol 161 Cyclohexene 83
Phosphoric acid 213 (with decomposition) Water 100
Table 3.1: Components

You can see from these values that cyclohexene is most volatile, although a little of the reaction mixture
water vaporises as well. and their boiling points.
In practice, it is impossible to effect complete conversion in this experiment: some

cyclohexanol decomposes in other ways, some cyclohexene remains in the reaction
vessel, some cyclohexene remains in the condenser and receiving vessel, and some
vaporises into the atmosphere and is lost.
When you obtain your pure cyclohexene, you measure its volume and using its
density (0.8110 g cm–3) calculate the mass obtained. Expressed as a fraction of the
theoretical yield, this gives you the percentage yield.
Reactions of cyclohexene
You will also try some reactions on the cyclohexene you have prepared and
compare these reactions with those of cyclohexane, the saturated analogue. To
refresh your memory, some reactions of alkanes and alkenes are given below.
Addition: Saturated alkanes will not react readily with halogens under normal
laboratory conditions. Unsaturated alkenes will readily undergo addition reactions
with halogens. Elemental bromine (Br2) has a distinctive reddish brown colour; the
dibromoalkane product is colourless.
Oxidation: Saturated alkanes will not react with permanganate ions. Unsaturated
alkenes will become oxidised to produce a range of colourless products; this
oxidation is enabled by the reduction of the permanganate ions. In acidic
55
conditions the vivid purple colour of the permangate ions will disappear as they
become reduced to almost colourless manganese(II) ions. Note: If insufficient acid
is added to the reaction solution a dark brown-black MnO2 precipitate may also form.
The following annotated equation represents this reaction.
This last equation is not balanced, but organic equations are often expressed in
this way. The important thing is to be able to follow what happens to the organic
molecule. When the last reaction is carried out under mild conditions (e.g. dilute
acidified MnO4– and room temperature), the product of the reaction is mainly the
diol (di-alcohol).
Part 3.2______________________________________________________________________
Procedure
Before commencing the experiment, carefully read the following safety issues and
practical points. There is a very real risk from odour and fire in this experiment. You
must always follow the advice of your demonstrator.
Prepare the reaction mixture
Into a 100 mL pear-shaped flask, add 20 mL (19 g) of cyclohexanol (directly from

the dispenser) and 10 mL of phosphoric (orthophosphoric) acid (directly from the
dispenser) and mix well.
Caution: mixing cyclohexanol with phosphoric acid will produce a significant

amount of heat. Add them together slowly, with swirling.
Add two or three boiling chips to aid boiling before commencing assembly of your
distillation apparatus.
Assembling the distillation apparatus
Assemble your distillation apparatus as shown in Figure 3.1. Poor assembly of the
apparatus is the greatest factor in the fire risk. Particular problem areas are the
joints between the reaction flask and the stillhead, and the stillhead and the
condenser.
56
Please note the following:
i. Boiling chips must be added to the flask being heated.

ii. The clamp at the neck of this flask is the primary support for the set
up. The clamp around the condenser should not be overtight – it is
used only as a back-up support. Rubber bands can also be used to
provide further support, as shown in the diagram below.
iii. Make sure the bulb of the thermometer is positioned to sit at the
junction of the distillation head.
iv. The water must be directed to flow upwards through the condenser.
Hence the water flow must go in through the bottom arm and out
through the top arm. The water flow rate must not be too high, nor
can it be allowed to drop too low.
v. The receiving vessel must be placed in an ice/water bath (ice/water
slurries cool more efficiently than ice alone) as efficient cooling of
the distillate reduces both the fire hazard and odour problems in
the laboratory.
vi. You must check that all Quickfit joints are correctly sealed.
Clamp lightly here. It is used as a back-up support
Clamp firmly here
Ice bath/slurry
Figure 3.1: Set-up of

distillation
Before you turn on your Bunsen burner you must get your demonstrator’s
permission. The greatest risk to fire is due to incorrectly assembled glassware.
Cyclohexene is a flammable liquid! Ensure the vapours are properly condensed and
do not allow vapour or distillate to be near your flame or your neighbour's flame!
57
Performing the reaction
Heat the flask gently, using a low blue flame applied directly to the reaction vessel
and keeping the flame in constant motion. By slowly waving the Bunsen around
the base of the flask, adjust the heat so that cyclohexene and water slowly distill
over. The temperature of the vapour passing into the condenser should not rise
above 105°C. The distillate is collected in a 100 mL conical flask that is cooled in
an ice-water bath. Continue slow distillation until about 10 mL of residue (mainly
phosphoric acid) remains.
Purifying the product
• To the distillate, add 10% sodium carbonate solution (2-3 mL) until the
aqueous layer is basic. You can test for pH using red litmus (it will turn blue
when basic). Then, transfer the mixture to a small separating funnel (see
Figure 3.2).
• With regular venting (pointing the tap into the fumehood!) mix the
contents well. Mount your separating funnel in the fumehood so it is vertical
and allow the two layers to separate. Don’t forget to remove the lid! Figure 3.2: Diagram of
separating funnel
• Run off the aqueous layer, and transfer the crude cyclohexene to a dry 100
mL conical flask.
Which one is the aqueous layer? Which one is the cyclohexene layer? An easy
way to tell is to note the volume of each and add a small amount of water and note
which one increases!
• Add a small quantity (two spatula tips) of anhydrous calcium chloride, and
allow the flask to stand, with occasional swirling, for 10-15 minutes.
• Wash the residue from your reaction into the residue container in the
fumehood, not in the open laboratory.
• Filter the cyclohexene into a dry measuring cylinder through a small plug
of cotton wool in a filter funnel.
• Present your sample (in the measuring cylinder whilst in the fumehood) to
your demonstrator.
product and recorded a comment on your assessment sheet. You may wish to
photograph your product and apparatus for use in the poster you will present at
the end of semester.
58
Clean-up
• All glassware should be rinsed with acetone prior to washing and the
acetone residue placed in the residue container in the fume-hood.
• When you have finished filtering, throw the cotton wool into the solid
residue container in the ventilated fume-hoods, not into the laboratory
bins.
• Dispose of all organic residue / halogenated waste in the appropriate
waste beakers in the fumehood.
Part 3.3______________________________________________________________________
Results
For your logbook
1. Record the appearance and volume of your product.

2. Determine the weight of cyclohexene using your volume and its density.
3. Using the expected 100% conversion of cyclohexanol calculated in the pre-
lab, calculate the percentage yield of cyclohexene (see glossary if you get
stuck).
Reactions of cyclohexene
Perform the following reactions on both your cyclohexene produced above and
on a sample of cyclohexane provided. In all reactions make sure you compare
results between the two to compare the reactions of an alkene to its saturated
analogue.
For your logbook
4. To 5 drops of the cyclohexene in a micro-test tube add 2-3 drops of 0.02 M

potassium permanganate solution drop by drop and shake well. Repeat the
test with cyclohexane and compare your observations. Explain your
observations (what you see) for both your prepared cyclohexene and the
sample of cyclohexane.
5. Write a chemical equation describing any reaction observed in Question 2
above. What type of reaction is this?
6. Add 2 drops of a solution of bromine in dichloromethane (supplied) to 5
drops of cyclohexene in a micro-test tube, and shake well. Repeat this test
with cyclohexane and compare your observations. Explain your observations
(what you see) for both your prepared cyclohexene and the sample of
cyclohexane.
59
7. Write a chemical equation describing any reaction observed in Question 4
above. What type of reaction is this?
Glossary
A percentage yield calculation will be performed to indicate how much product

you obtained compared to how much product could (theoretically) be obtained
if a) the reaction completely produced only the stated products and b) all
product was able to be recovered. If you have not performed this type of
calculation before you may find the following guide useful.
Guide to Determining the Theoretical Yield:
Calculate the theoretical yield using information known about the reactant
(limiting reagent) and the mole ratio between it and the product as per the
balanced reaction equation:
1. Reactant = cyclohexanol = C6H12O. Its density is given as 0.95 g mL-1 and
you will be using 20 mL. From this information you can determine its mass
(in g), and hence its moles (as n=m/M).
2. Next determine the maximum, or ‘theoretical’, moles of product that could
form using the mole ratio of the balanced chemical reaction.
3. Convert your theoretical yield of product from moles to mass (recall:
m=n×M).
4. Actual Yield: Measure the volume of product you obtained (measuring
cylinder accuracy is OK) and convert this to mass given that the density of
cyclohexene is 0.811 g.mL-1.
5. Percentage Yield: Use the following equation:
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 (𝑔𝑔)

% 𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 = × 100
𝑇𝑇ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 (𝑔𝑔)
60
61
Part 3.4______________________________________________________________________
Assessment
page 27.
Experimental Skills
Quality: The colour of

Moderately coloured Faintly coloured Colourless
the product was...
Very cloudy or water

Quality: The product
droplets clearly Slightly cloudy Very clear
clarity and dryness was...
visible
Reactions: Performed Carried out with at

reactions with least one of the tests Both carried out
Not carried out
cyclohexene and showing predicted successfully
cyclohexane… results
Total Mark
Theoretical Understanding Post-lab questions
1. What is the function of boiling chips?

2. 4.2 Describe how using a distillation set up for this reaction benefits
both the reaction rate as well as product yield?
3. Why distill slowly?
4. Why must the receiving vessel at the end of the condenser tube be
resting in an ice slurry bath for the reaction that you conducted?
5. Why was Na2CO3 solution added? Which layer was the lower layer
(aqueous or organic)?
6. What is the purpose of the anhydrous CaCl2?
62
63
Part 3.5______________________________________________________________________
1. Given that you will be using 20 mL of cyclohexane in this experiment, and the
cyclohexane is the limiting reagent, determine the maximum (theoretical) yield
(in grams) of cyclohexene that you could make. Hint: The densities of both of
these liquids are found in the “Background” section of the experiment. If you get
stuck, refer to the Glossary.
2. Using the following example as a guide, discuss 2 other safety aspects that are
specific to this experiment.
• Boiling chips must be added to reaction flask before distillation. Without
these there is a risk of breaking the glassware while heating. If this happens
the flammable contents can ignite causing a fire in the lab.
3. Construct your own flowchart for the preparation of cyclohexene. This should
be sufficiently detailed and contain all the relevant procedural steps for this
experiment.
Hint: The concept of flowcharts, as well as an example, was given in Experiment 3 –
Purification by Recrystallisation…
65

Preparation of 4-nitroacetanilide  Safely handle of

concentrated acids and
purification of a solid. You will
use safe working practices to
handle hazardous materials in the
synthesis of a compound. The
Safety product will then be recrystallised.
 Plan and complete an
electrophilic substitution
reaction. Using a detailed flow
diagram, you will be able to
identify the key steps in the
procedure and the chemistry
associated with each activity. This
will help you understand the
This experiment uses concentrated acids, which are corrosive and may cause chemistry of EAS discussed in
burns if they come into contact with your skin. You will be asked to wear gloves lectures.
when handling the concentrated acids and during clean-up of the reaction  Use precise and concise
language. Answering the pre-
mixture. laboratory and post- laboratory
You must correctly wear a laboratory coat, safety glasses, and fully enclosed developing written
shoes at all times in the laboratory while conducting this experiment. communication skills.

laboratory briefing. your apparatus and product.
Aim
To prepare 4-nitroacetanilide from acetanilide by electrophilic aromatic

substitution.
Part 4.1_____________________________________________________________________
Introduction
The nitro group (−NO2) is a very important functional group in aromatic

chemistry, since it is readily introduced into an aromatic ring. It can be reduced
to the amino group (−NH2), and diazotization of a primary amine yields a
diazonium salt, from which a range of compounds, including dyes, can be
prepared.
In this experiment you will be making an aromatic nitro compound (4-

nitroacetanilide) by nitration of an aromatic reactant (acetanilide). This experiment
is an example of an electrophilic aromatic substitution (EAS) in which the
66
electrophile is the NO2+ ion. The nitronium ion itself is produced within the nitrating
mixture consisting of a mixture of concentrated nitric acid (HNO3) and sulfuric acid
(H2SO4). The reactions that occur are represented below:
a) Production of electrophile:
HNO3 + H2SO4  NO2+ + HSO4- + H2O
b) Electrophilic Aromatic Substitution:
The nitrating mixture is generated through reaction of nitric acid (HNO3) and
sulfuric acid (H2SO4) to form the electrophile NO2+.
Part 4.2______________________________________________________________________
Procedure
Caution: Concentrated acids, such as nitric, sulfuric and glacial acetic acid, are
highly corrosive and all contact with skin and clothing must be avoided. Wear
gloves when handling these acids. Drops of acid spilt on the bench are a common
cause of acid burns; therefore ensure that any spillage is cleaned up immediately.
Ask your demonstrator for advice/assistance. On mixing these acids, heat and
fuming toxic vapours (NO2) may be released. Handle this mixture in a fumehood.
Prepare the nitrating mixture
Prepare a nitrating mixture by cautiously adding 1 mL of concentrated nitric acid

to 3 mL of cold concentrated sulfuric acid directly from the dispensers into a
small, dry flask. Cool the mixture in an ice bath for later use. Leave this to one
side while you prepare the acetanilide for reaction.
67
Prepare the reaction mixture
In a dry 100 mL conical flask, dissolve 1.6 g of acetanilide in 3 mL of glacial acetic

acid (directly from the dispenser) by warming gently with your hands.
Cool the acetanilide solution in an ice bath, and then add slowly, with swirling,
3 mL of concentrated sulfuric acid.
Cool the acetanilide solution in an ice bath, remove the flask from the bath, and
add the nitrating mixture, 3 or 4 drops at a time, from a dry Pasteur pipette.
If you have not used a glass Pasteur pipette before, seek advice from your
demonstrator for tips on its correct use.
Mix the viscous mixture thoroughly during the addition, and keep the
temperature below 30 °C by cooling in the ice bath.
After all the nitrating mixture has been added, allow the mixture to stand at room
temperature for 15 minutes.
Pour the mixture slowly with stirring into a 250 mL beaker containing 50 mL of
ice cold water and a handful of crushed ice.
Separation and purification of the product
Collect the product by suction filtration on the Hirsch funnel, and wash the filter
cake with about 5 mL of water.
Record the mass of your crude product.
Recrystallize this crude product using ethanol. Follow the procedures in

Experiment 1 for recrystallisation of benzoic acid.
Record the mass of purified product obtained.
Determine the melting point of your sample using the procedure given in
Experiment 1. Record the melting point of purified product.
product and recorded its quality on the assessment sheet. Once your
demonstrator has recorded his/her feedback you may dispose of the sample in the
yellow hazardous waste bins.
68
For your logbook
1. The reaction to form 4-nitroacetanilide is an electrophilic aromatic
substitution (Recall Lecture and Workshop). Identify the following
components of this reaction.
a. the electrophile reacting with the aromatic ring
b. the group that is lost in the reaction
c. the solvents present in the reaction mixture
2. Consider your answers to Question 1. In the reaction mixture, what is the
function of the sulfuric acid in the nitrating mixture?
3. Using the expected 100% conversion of acetanilide calculated in the pre-lab,
calculate the final pure and crude yields from the mass of product as a
percentage.
4. Comment on your melting point value with reference to the literature value
cited in the pre-lab.
69
Part 4.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Conducted safely;
Deemed unsafe. Improvement Gloves were worn
Handling of Gloves not used, or needed; e.g. Gloves only during handling
concentrated acids and gloves were not used appropriately of conc. Acids; were
use of gloves was… removed / disposed but not disposed of disposed of
of appropriately correctly appropriately in
chemical waste bins
Use of Pasteur pipette Very good after some

Deemed unsafe n/a
was... instruction
Quality of purified Brown product

product: The colour, obtained; yield low Pale cream product,
Product not obtained
yield & melting point of &/or m.p. indicates good yield, good
or not purified at all
the purified product impurities or wasn’t melting point range
was... done
Total Mark
1. Using curly arrows, draw the mechanism for:

a. the formation of the electrophile
b. the substitution reaction of the electrophile with acetanilide.
2. Why is the mixture:

a. left 15 minutes at room temperature
b. poured into ice-water
70
3. How did you (or how could you) confirm that your product was 4-
Nitroacetanilide and not some other compound?
71
Part 4.4______________________________________________________________________
These must be completed before your laboratory session. Have them ready to
show to your demonstrator as you enter the lab, and staple or glue them into
your logbook during your laboratory session.
1. The limiting reagent in this experiment is 1.6 g acetanilide. Determine the

theoretical yield of 4-nitroacetanilide, assuming 100% conversion.
2. From a reference source, such as the CRC Handbook of Chemistry and Physics,
find the theoretical melting points of acetanilide and 4-nitroacetanilide. Cite
this reference 41.
3. Summarise the main hazards and safety precautions that you will need to take
in regards to the handling of concentrated acids during this experiment.
4. Construct a flowchart for this experiment. This should be sufficiently detailed
and contain all the relevant procedural steps for this experiment. Also include
in your flowchart the steps for the recrystallisation of your product.
4
You may use any referencing style. Information on how to cite references is available here:
http://libguides.library.curtin.edu.au/content.php?pid=141214
73

Determination of acetic acid in vinegar  Use of volumetric glassware

and pH meter. You will
manipulate volumetric glassware
to achieve an accurate and
reproducible volumetric analysis.
You will also calibrate and use a
Safety pH meter.
 Understand principals of
volumetric analysis and
acid/base chemistry. You will
The chemical hazards in this laboratory a minimal. use a sodium hydroxide solution
of known concentration to
You should use all organic solvents in the fumehood and wear appropriate determine the concentration of
acetic acid in a provided sample
gloves if requested. You must correctly wear a laboratory coat, safety glasses, of vinegar. You will also interpret
and fully enclosed shoes at all times in the laboratory while conducting this a titration curve to determine the
pKa of acetic acid.
experiment.
 Present of data and plot
graphs. Presentation of
concentrations in an appropriate
form and plotting and presenting
graphs (titration curve).
Your demonstrator will illustrate the procedural hazards during the pre- Other goals include:
laboratory briefing.  Presentation of results
Aim your apparatus and product.
To determine the concentration of and acetic acid solution using two methods
– performing volumetric analysis using a standardised sodium hydroxide
solution and using a pH meter to collect data to produce a titration curve
Part 5.1_____________________________________________________________________
Background
Principles of volumetric analysis

The aim of quantitative analysis is to determine the quantity of a particular species
in a given sample. Analysis that depends on measurement of volume is called
volumetric analysis. This analysis is carried out by matching a known quantity of a
reactant A (the standard) against an unknown quantity of a reactant B (the
unknown). For this purpose a solution of one reactant is added progressively to a
solution of the other. This process is called titration.
Only certain chemical reactions are suitable as a basis for matching reactants in a
titration. There are several requirements.
(a) There must be some means of knowing when the matching quantity of one
reactant has been added to the other.
74
(b) The point where the quantities are matched is called the equivalence point.
(c) The reaction must be free from side-reactions so it can be represented by a
single equation.
(d) The reaction rate should be fast so that the equivalence point can be
accurately detected.
(e) The reaction must go essentially to completion, i.e. the equilibrium constant
for the reaction must be large.
The reactions used in volumetric analysis are of three types.
(a) Those dependent on the combination of ions, as in acid-base titrations and

precipitation titrations.
(b) Those dependent on electron transfer (oxidation-reduction reactions).
(c) Those dependent on complex formation.
The technique of volumetric analysis involves the understanding and mastering
of the following equipment.
(a) The pipette - used in the delivery of accurately known aliquots (volumes) of
solution.
(b) The burette - used in the technique of titration to dispense and accurately
measure the volume of titrant.
(c) The balance - weighing of objects on both top-loading and analytical
balances.
(d) The volumetric flask - used in the preparation of standard solutions of
accurately known concentrations.
(e) Each of these techniques will be covered in extensive detail so that students
can familiarise themselves with the mastery required in the collection of
accurate analytical data.
Acid-base titrations
A titration is performed by reacting a standard solution with an unknown solution.

Either the standard solution, or the solution containing the unknown, is pipetted
into a conical flask. The other solution is then added progressively from a burette.
Up to the equivalence point the solution contains an excess of one reactant; after
the equivalence point it contains an excess of the other reactant. Some means of
observing this changeover must be available.
In acid-base titrations, the change in colour of an indicator may be used as

evidence of the changeover. The first point at which the indicator is observed to
undergo a persistent colour change is termed the endpoint of the titration (Part A).
The end point must be as close as possible to the equivalence point; to achieve this
the indicator must be carefully selected.
75
The equivalence point can also be determined using a pH titration curve (Part B)
(see Figure 5.1)
Region 1 Region 2 Region 3 Figure 5.1: A typical titration curve for a
weak acid-strong base titration:
- Region 1: Excess analyte
- Region 2: A narrow range where a very
small amount of additional titrant will
increase the pH significantly. The
equivalence point is located at the point
of inflection. Note that the pH at this
point may not be equal to 7 - it is
dependent on the nature of the salt
produced by the neutralisation reaction.
- Region 3: Excess titrant
Note: the pKa for the acid can be

extrapolated from a titration curve as
shown.
The concentrations of unknown acid and base solutions will be measured by

titration with standardized reagents. The end point will be determined from the
plot of pH versus titre. These titration curves will also be used to determine the
pKa or pKb for the weak acid or base titrated.
It is possible to set up galvanic cells whose voltage depends upon the pH of the
solutions in which they are placed. The most commonly used cell for this purpose
involves the glass electrode and the calomel electrode. The potential developed
across the glass membrane of the glass electrode is a function of the pH of the
solution in which it is placed. A reference electrode, usually calomel, is used in
conjunction with the glass electrode to complete the galvanic cell. The potential
of the reference electrode remains constant during the titration. Hence the
potential of the cell depends only on the pH of the solution in which it is placed.
Combination electrodes are frequently used as a substitute for the separate glass
and calomel electrodes.
A pH meter is used to measure the potential of the galvanic cell. The glass
electrode has a high electrical resistance, of the order 1 to 100 megaohms. The
pH meter is a voltage-measuring device designed for use with cells of high
resistance. It draws very little current and the circuit is designed to give a meter
reading directly proportional to pH.
Take great care of the electrodes - the glass electrode in particular is very delicate.
It is damaged by caustic alkalis. Wash the electrode system immediately after each
titration and allow to stand in a beaker of distilled water.
76
Determining pKa
Acetic acid is a weak acid, the Henderson Hasselbalch equation can be applied:
[conjugate base]
pH = pK a + log10
[conjugate acid]
As shown in Figure 5.1, there is a point along the titration curve where the ratio
is a simple number : ½ titre, where [CH3COOH] =[CH3COO-]
Part 5.2______________________________________________________________________
Procedure
You will be analysing for the concentration of acetic acid (CH3COOH) in a

commercially available vinegar sample. This vinegar sample has been diluted by
a factor of 3.5. Make sure you include this when calculating the final concentration
in the original vinegar.
Titrations require the concentration of at least one component to be accurately

known. This is called the standard solution. In this experiment, we will use a known
concentration of sodium hydroxide (NaOH) that will be around 0.2 M to determine
the concentration of acetic acid in vinegar. Acetic acid is our analyte in our sample
of vinegar and it will react with sodium hydroxide in a 1:1 reaction.
CH3COOH (aq) + NaOH (aq) H2O (l) + NaCH3COO(aq)
Sodium hydroxide is not a good standard reagent because it will react slowly over
time with carbon dioxide in the air to produce sodium carbonate, and therefore
must be regularly standardised. This has been done by the technician just before
the lab.
PART A: Determining the concentration of acetic acid in vinegar using

titration
Refer to the glossary of this experiment and the introduction of the lab manual for
details on how to perform a titration.
1. A range of indicators are available for you to use in this experiment. Using the
information you collected in the pre-lab, select an appropriate indicator from
the available selection. You will need to select an indicator that will change
colour over a pH range that is as close to the equivalence point as possible.
2. Pipette three 20.0 mL aliquots of the vinegar solution into three clean conical
flasks and add 2-3 drops of your chosen indicator to each. Care must be taken
when using a pipette!
3. Titrate these solutions with the standardised sodium hydroxide solution until
the endpoint is achieved (i.e. the first persistent colour change is noted). Some
tips on technique include:
77
• Place a piece of white paper beneath the conical flask. This will assist
you in detecting indicator colour changes.
• Holding the burette tap in your left hand and swirling the conical flask
with your right hand titrate the CH3COOH until the first colour change
is noted. Ensure all splashings, etc. are washed down into the bulk
solution. Record the final volume to two decimal places.
• Titrate the first solution to obtain a rough volume of titrant required.
4. Repeat twice to obtain at least 2 concordant titre volumes (i.e. resultant volumes
within 0.10 mL of each other). Ensure you read the burette to ± 0.05 mL. If
you’re not sure how, ask your demonstrator!
5. Clean your burette thoroughly after use.
For your log book
1. Write down the concentration of NaOH (see the carboy in the laboratory)
2. Copy and complete the table below
Burette Readings Rough Accurate Titrations

(mL) Titration Place an asterisk next to your concordant results
Final
Initial
Titre
Mean titre volume of your concordant results mL
3. Calculate the concentration of acetic acid in the original undiluted vinegar

in (mol L-1) (to three decimal places), showing your working clearly, taking
into account that the sample provided was diluted before analysis.
78
PART B: Determining the concentration of acetic acid in vinegar using a pH
meter
1. You will need to calibrate the pH meter before you commence the titration:
Calibration of the pH meter (HANNA HI8424)
a) Switch instrument on to display pH measurement.

b) Immerse the pH electrode in the pH 7 buffer solution, swirl briefly and wait
c) 20 seconds for thermal equilibrium.
d) Press the "CAL" key. The display should show the temperature
compensated buffer value and the pH symbol should be flashing.
e) Wait until the pH symbol (not the number) stops flashing and press the
"CON" or "CFM" key.
f) Remove the electrode and rinse with deionised water before immersing it
into the pH 4 buffer solution. Swirl briefly and wait for thermal equilibrium.
g) The display should show the temperature compensated buffer value and
the pH symbol should be flashing.
h) Wait until the pH symbol stops flashing and press the "CON" or "CFM" key
to confirm the calibration.
i) Rinse the electrodes with deionised water immediately after each use, and
when no longer being used place them back in the conical flask containing
3 mol L−1 KCl solution (do not allow it to become dry).
The instrument is now calibrated and will remain calibrated even after it is
turned off.
2. Prepare and fill a burette with the standardized NaOH solution . Record the
initial titre volume.
3. Pipette one 20.0 mL aliquots of the pre-diluted vinegar solution into a clean
250 mL beaker, add 100 mL of water, a stirrer bar. Place this beaker onto a
magnetic stirrer and set it to stir at a low - medium pace. Place the probe in the
solution so that it does not obstruct the burette and is not hit by the stirrer.
4. Titrate this solution with the standardised sodium hydroxide solution and
record the titre volumes added along with the measured pH values (directly into
your logbook!) for successive additions of titrant. Allow the pH meter to
stabilize between readings. You will need to record sufficient pH and Vtitre data
points, both before and after the equivalence point, to be able to construct a
titration curve that will show the point of inflection (and thus equivalence point)
clearly. Keep in mind the following tips:
• Save time by adding in larger titrant aliquots at the start and near the
end of your titration
• When close to the equivalence point (within ~5 mL) add smaller and
smaller aliquots of titrant (e.g. 1 mL, 0.5 mL, 0.1 mL…). The equivalence
point will fall within a very narrow range – the more data points you can
79
collect around this range, the better your accuracy will be. Your
equivalence point should occur somewhere between 15 & 30 mL of added
titrant.
• Plot your data points as you go – this will help you see more clearly
when you will need to reduce your titrant volumes as you approach the
equivalence point, and when it is safe to increase the volumes again
after the equivalence point is passed and the point of inflection is
already clearly defined.
5. Remove the electrode from the solution and wash with distilled water.
For your log book
4. Using the following table as a guide, record your raw data for Part B.
Vtitre (mL) pH Vtitre (mL) pH Vtitre (mL) pH

0 +0.5 = 20.5 Larger aliquots at the
start to save time
Example
+5 = 5 etc.
+5 = 10 Note: Your volume increments do not need to Smaller aliquots near
be identical to those shown here. You will equivalence point for
+5 = 15
need to choose your increments as you go – better accuracy
volumes
+2 = 17 keeping in mind that even though you want a

high level of accuracy, you also have a time Larger aliquots at the
+2 = 19
constraint to consider! end to save time
+1 = 20
5. Plot a graph of pH vs volume of NaOH (use graph paper provided on page

80).
6. From your graph, estimate the equivalence point (i.e. the middle of the region
where the pH changes rapidly). Use the titre volume at the equivalence point
to determine the concentration of acetic acid in the original undiluted
vinegar sample (to three decimal places) in moles per litre, showing your
working clearly.
7. Using your graph Determine pKa of acetic acid. How does your
experimentally determined pKa value compare with the literature value of
4.75?
8. Compare the two concentrations from part A and part B. Compare the two
techniques.
80
Glossary
Using a pipette correctly
The pipette is used to deliver a known volume, but will only do so if used as follows:
(a) Clean the pipette by washing thoroughly with detergent and tap water.
(b) Allow the pipette to drain, wash thoroughly with tap water and finally rinse
with deionised water.
(c) Rinse the pipette two or three times with a small amount of the liquid, tilting
to ensure that the whole inner surface is rinsed.
(d) Insert the pipette into the pipette filler with a slight pressure. This assures
a secure fit. Never insert the pipette more than 1 cm into the pump.
Be careful inserting a pipette into a pipette filler. Always grasp the pipette at
wide top, never at or below the bulb, and never apply too much force. One of the
most common laboratory injuries is from a pipette filler being inserted with too
much force causing cuts or even penetration into hands or arms as a result.
(e) Draw up the liquid until it is above the graduation mark.

(f) Wipe away any adhering liquid from the outside of the lower stem with a
cloth or paper towel.
(g) Allow the liquid to drip out slowly until the bottom of the meniscus just
reaches the graduation mark. The pipette must be held vertically with
the mark at eye level.
The meniscus is the rounded top surface of the solution caused by adhesion of the
solution to the walls of narrow glass tubes. The base of the meniscus is where all
volumetric glassware should be read from.
(h) Remove any drop adhering to the tip by touching against a glass surface,
not by wiping.
(i) Allow the liquid to run into the receiving vessel with the tip of the pipette
touching the wall of the vessel. Do not allow the tip to be immersed in the
liquid.
(j) When the continuous discharge has ceased, hold the jet in contact with the
side of the vessel for 15 seconds (draining time).
(k) The liquid remaining in the jet at the end of the drainage time must not be
removed either by blowing or any other means. Pipettes are calibrated to
exclude any remaining solution.
(l) All pipette volumes should be recorded in one decimal place as 10.0, 20.0,
50.0 mL.
81
The specifications for pipettes in common use are:
Capacity (mL) 10.0 20.0 50.0
Tolerance (± mL)(Class B) 0.04 0.05 0.08
Delivery Time (secs)(Classes A and B) 15-25 15-30 25-40
How to read a burette accurately
It is important that you learn how to read a burette accurately. A well-trained

titrator can read a burette to ±0.01 mL. In this unit we expect you to be able to
read the burette to ± 0.05 mL and report all volumes accurately. The figure at the
right illustrates how this is done by positioning the baseline of the meniscus using
the volume marks on the burette. A burette has volume marks at 0.10 mL
increments. To read it accurately we look at the meniscus being on or close to the
line (.00 mL) or about half way (.05 mL). Note how we still report the 0 when the
meniscus is on the line as this digit is significant (e.g. 3.10 mL, 3.40 mL etc). You 3.10 mL
must write this number down and include the significant figures in the calculations. 3 3.25 mL
3.40 mL
3.55 mL
3.70 mL
When reporting the volumes, ensure that you include the value of the number 3.80 mL
immediately above your meniscus and count down the number of tenth markings,
as illustrated above. You must bring your eye level with the meniscus to read this
accurately. To do this when looking at the burette marking you should see one
continuous line through the glass wall of the burette. If you see two lines you are
not at eye level.
You will read the burette twice; before your titration for the initial reading which
should never be at 0.00 so you have marking above the meniscus to accurately
judge its position and then immediately after your titration. Always record the
volume of the burette to two decimal places.
Steps involved in a simple acid-base titration procedure: e.g. Sodium

hydroxide (NaOH) versus acetic acid in a diluted vinegar (CH3COOH)
1. Clean and rinse with deionised water two 250 mL beakers and three 250 mL
conical flasks into which samples will be placed.
2. Rinse one beaker with a small amount of the CH3COOH solution to be taken
and label accordingly.
3. Pour the required amount of CH3COOH into the beaker.
4. Rinse the other beaker with a small amount of the NaOH solution to be
taken and label accordingly.
5. Pour the required amount of NaOH into the beaker.
6. Rinse the pipette with the CH3COOH.
82
7. Fill the pipette with the CH3COOH and deliver the 20.0 mL into the
previously washed 250 mL conical flask from (1).
8. Repeat steps (7) and (8) for two or more further conical flasks as required.
9. Clean and rinse a burette. Check for free running of the tap. With a ground
glass tap ensure there is no excess grease.
10. Rinse the burette with the NaOH solution.
11. Mount the burette on a retort stand using a burette clamp and adjust the
height of the burette such that the tip height is below the mouth of the 250
mL conical flask.
12. Fill the burette with NaOH using a small plastic funnel. Close the tap
before filling and remove funnel before commencing the titration.
13. Run a few mL of NaOH out the tap of the burette to force the air out of the
tip. Touch the tip of the burette against a wall of the waste beaker to
remove any excess NaOH.
14. Record the initial volume to two decimal places.
83
Graph: pH vs volume of NaOH (Vtitre) plot.
84
85
Part 5.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Developing (0 Competent (0.5

Criteria Exemplary (1 mark)
marks) marks)
Part A: Concordant titre values

with appropriate number of No N/A Yes
significant figures were provided
Majority not
All completed
Calculations completed, or n/a
correctly
majority incorrect
Majority not Majority

Part B: Data and calculations for All completed
completed, or completed
the titration curve presented correctly
majority incorrect correctly
Total Marks
1. Was the indicator you chose appropriate? Did your endpoint give a
Vtitre that was consistent with the Vtitre for the equivalence point in
Part A.
a. If so, provide a justification for why you chose your particular
indicator and describe why the endpoint occurred at a pH that fell
within range for its equivalence point.
b. If not, propose what you think might have gone wrong and
suggest a different indicator that you would use if you were able
to repeat the analysis. Provide an explanation for your decision.
2. Compare the two approaches you took in experiment 1: Part A where
you calculated the same concentration by determining the endpoint of
a titration and Part B where you calculated the concentration of acetic
86
acid in vinegar using a graphically determined equivalence point.
Describe at least one advantage and one disadvantage of both
approaches.
3. The concentration of commercial vinegar is usually expressed as %w/v
(i.e. m(CH3COOH) in grams per 100 mL of vinegar). Convert one of
your calculated concentrations for Part A or B into units of %w/v. Was
your experimentally determined concentration consistent with the
manufacturer’s claim (typically between 4 & 8% w/v)?
87
Part 5.4______________________________________________________________________
1. Why should the pipette be rinsed with CH3COOH (and the burette with
NaOH) prior to their use in dispensing these solutions?
2. Why should a constant, minimum amount of indicator be used in

titrations?
3. The choice of indicator used in a specific titration needs to be carefully

selected as different acid-base titrations can have different equivalence
points, and different indicators will undergo colour changes within
different pH ranges. If the indicator chosen does NOT undergo a colour
change within range of the equivalence point for the titration, then an
inaccurate titre volume will be chosen for subsequent calculations and
the final results will be incorrect! Investigate the choice of indicators
that can be used for different types of titrations and complete the table:
Titration Example pH at equivalence point Suitable indicators
Weak acid – Strong CH3COOH/NaOH

base
Strong acid – Weak

base
Strong acid – Strong

base
4. Why is the use of an indictor not suitable for determining the

equivalence point of a weak acid – weak base titration? Refer to the
shape of the titration curve in your answer. How would you determine
the equivalence point?
5. Calculate what volume of 0.100 M NaOH would you expect to deliver
from the burette to standardise 20.0 mL of 0.102 M CH3COOH?
6. Assume that you will be carrying out four titrations using 20.0 mL of 0.1
M CH3COOH. Approximately what volume of 0.100 M NaOH should
you require?
89

Designing and making buffer solutions  Use of volumetric glassware

and pH meter. You will use
volumetric glassware and
balances to prepare buffer
solutions of given pH.
 Understand principals of
Safety acid/base equilibria. You will use
the Henderson-Hasselbalch
equation to calculate the pH of a
buffer solutions and prepare a
The chemical hazards in this laboratory a minimal. buffer of given pH.
 Presentation of data and
You should use all organic solvents in the fumehood and wear appropriate describing procedures.
Presentation of your calculations
gloves if requested. You must correctly wear a laboratory coat, safety glasses,
and explanation of procedures
and fully enclosed shoes at all times in the laboratory while conducting this and results.
experiment.
Aim
To construct a buffer solution of a particular pH by two different methods, and

to measure the impact of addition of small amounts of strong acid or base on
the pH of your prepared buffer system.
This exercise will involve as much thinking as doing. You should discuss your
approach as a group and with your demonstrator, if necessary.
Part 6.1_____________________________________________________________________
Background
Buffer systems
Buffers are an enormously important phenomenon in chemistry. They are

commonly found in many biological and industrial systems. A buffer is a solution
that resists rapid and uncontrolled changes in pH. In the body blood is buffered
by the carbonic acid (H2CO3/HCO3–) buffer system which keeps blood pH at 7.40 ±
0.05. The buffer maintains function in a process called homeostasis. Failure to
maintain blood pH can lead to serious disease or even death.
90
A buffer is a solution containing a weak acid and its conjugate base, which is also
weak. When both species are found in water they form an equilibrium, for example
between the hydrogen carbonate ion (HCO3–) and the carbonate ion (CO32–).
HCO3- (aq) + H2O (l) ⇌ H2CO3 (aq) + OH- (aq) Reaction A

CO3- (aq) + H2O (l) ⇌ HCO3- (aq) + OH- (aq) Reaction B
Addition of strong acid or base to a buffer system
The qualitative effect on the buffer equilibrium by addition of a strong acid or base
can be predicted by applying Le Chatalier’s Principle to Reaction C. To quantify this
effect, however, it is simpler to focus our attention on how the conjugate partners
themselves react with the added strong acid or strong base.
• When a strong acid (H3O+) (e.g. ‘x’ moles) is added to this buffer solution
that contains both a weak acid (HCO3-) and a weak base (CO32–), the strong
acid reacts completely with the weak base and forms the weak acid, for
example:
H3O+ (aq) + CO3- (aq) ⇌ H2O (l) + HCO3- (aq)
As such the moles of weak base in the solution will decrease and the moles
of weak acid will increase by the same, stoichiometrically equivalent,
amount:
nCO3-final = (nCO3-initial – x) & nHCO3-final = (nHCO3-initial + x)

where x = n(added strong acid)
• When a strong base (OH–) (e.g. ‘x’ moles) is added to this buffer solution,
it reacts completely with the weak acid and forms the weak base, for
example:
OH- (aq) + HCO3- (aq) ⇌ H2O (l) + CO3- (aq)
As such the moles of weak acid in the solution will decrease and the moles
of weak base will increase by the same amount:
nHCO3-final = (nHCO3-initial – x) & nCO3-final = (nCO3-initial + x)

where x = n(added strong base)
Note: You can also use an ICE table to complete these calculations
Therefore, as long as there is sufficient buffer components (weak acid and weak
base) present in the solution, the pH can be maintained nearly constant. This
capacity for change is called the buffer capacity and can be measured by titrating
the buffer solution with a strong acid or base.
91
Quantifying pH
Because we are investigating acid/base dissociation, the equilibrium is influenced

by both the respective Ka and Kb values for the conjugate acid/base partners. If we
make our reference point the weak acid the reactant, we can limit our focus towards
the magnitude of Ka when we describe the equilibrium of a buffer system. Thus, for
any given buffer system we can write:
HA (aq) + H2O (l) ⇌ A- (aq) + H3O+ (aq) Reaction C
[𝐴𝐴− ][𝐻𝐻3 𝑂𝑂+ ]

𝐾𝐾𝑎𝑎 =
[𝐻𝐻𝐻𝐻]
When rearranged and put as a logarithmic scale, the Ka expression is converted

into the Henderson-Hasselbalch equation:
[𝐴𝐴− ]
𝐾𝐾𝑎𝑎 = 𝑝𝑝𝐾𝐾𝑎𝑎 + 𝑙𝑙𝑙𝑙𝑙𝑙
[𝐻𝐻𝐻𝐻]
The pH of a buffer solution can be calculated quite simply if we know the

concentrations of both the HA & A- species, along with the pKa value for HA.
At every stage, where there are still buffer components present, the pH of the buffer
can be determined using the Henderson-Hasselbalch equation, for example:
�𝐶𝐶𝐶𝐶3 2− �
𝑝𝑝𝑝𝑝 = 𝑝𝑝𝑝𝑝𝑎𝑎 + 𝑙𝑙𝑙𝑙𝑙𝑙
�𝐻𝐻𝐶𝐶𝐶𝐶3 2− �
�𝐶𝐶𝐶𝐶3 2− �
−log[𝐻𝐻3 𝑂𝑂+ ] = −𝑙𝑙𝑙𝑙𝑙𝑙 𝐾𝐾𝑎𝑎 + 𝑙𝑙𝑙𝑙𝑙𝑙
�𝐻𝐻𝐶𝐶𝐶𝐶3 2− �
When there are no more buffer components present then pH will rapidly change.
The addition of strong acids or bases will be in excess and will dominate the pH
seeing a rapid decrease or increase respectively.
Methods of making a buffer
There are three methods through which we can make a buffer and estimate its pH.
1. Dissolve the weak acid and weak base into the same solution. Here the
pH can be determined directly by applying the Henderson-Hasselbalch
equation directly given the concentrations of the acid and base in the
final solution and Ka (and pKa) of the weak acid.
2. Dissolve the weak base into solution and partially neutralise with a
strong acid (such as hydrochloric acid). Here we assume the strong acid
will react with the weak base completely and produce the same number
of moles of the weak acid (as per the reaction given on page 1). We can
92
then estimate the pH using the Henderson-Hasselbalch equation as for
Method 1.
3. Dissolve the weak acid into solution and partially neutralise with a
strong base (such as sodium hydroxide). Here we assume the strong
base will react with the weak acid completely and we can then estimate
the pH using the Henderson-Hasselbalch equation as for Method 1 and
2.
You will be using a pH meter. A pH meter measures the activity (effective
concentration) rather than the actual concentration. In concentrated solutions,
activities are usually much lower than the concentration value, therefore you can
expect a lower than anticipated pH.
Part 6.2______________________________________________________________________
Procedure
Part A: Making a buffer solution from a weak acid and its conjugate base
1. Using your answers to pre-lab Question 2, weigh out appropriate amounts of

solid sodium carbonate and sodium hydrogencarbonate and dissolve into 100
mL of deionized water to make a buffer solution with a pH of approximately
10.80.
For your logbook
1. Tabulate your data – and make sure you record the masses of Na2CO3 and
NaHCO3 you actually dissolved and made up to 100.0 mL volume with deionised
water.
2. Using the actual masses weighed, calculate the theoretical pH of your buffer
solution.
3. Calibrate a pH meter 5 and measure the pH of your buffer solution.
a. Record your measured pH & discuss how it compares to your calculated
theoretical value.
4. Calculate how much the pH of your 100 mL buffer solution would change if 5 mL
of 0.2 mol L–1 hydrochloric acid solution were added to it.
a. Add 5 mL of 0.2 mol L-1 hydrochloric acid solution to your 100 mL buffer
solution and mix well.
5. Measure (and record) the new pH of your buffer.
a. Is the change in pH consistent with your prediction? If not, suggest some
reasons.
5
If you don’t remember how to do this you will need to revisit the instructions in Experiment 5: Determination of
acetic acid in vinegar
93
Part B: Making a buffer solution from a weak acid and sodium hydroxide.
1. Your demonstrator will give you a target pH – write this into your logbook.
2. Accurately weigh between 1.4 and 1.6 g of sodium hydrogen carbonate and
dissolve in 100 mL of deionized water.
3. Record the accurate mass into your logbook.
4. Based on the mass of sodium hydrogen carbonate you actually weighed,
calculate the volume of 0.2 mol L–1 sodium hydroxide solution required to add to
your sodium hydrogen carbonate solution in order to make it a buffer for your
target pH. Show all supporting calculations clearly.
5. Add the calculated volume of 0.2 mol L–1 sodium hydroxide solution to your
dissolved sodium hydrogen carbonate solution and mix well. Take your solution
to your demonstrator for testing.
6. Compare the measured pH to your target - how close were you? Don’t forget to
note this in your logbook!
94
95
Part 6.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Part A: The measured

Outside range N/A Within range
pH of the buffer was...
Part B: The measured

Outside range N/A Within range
pH of the buffer was...
Calculations: The buffer Very poor, mostly

Good, Mostly correct Excellent, all correct
calculations were... incorrect
Total Mark
1. Making a buffer solution from a weak base and hydrochloric acid:

Describe how you might make the same buffer solution as in Part 2, but
using 2.00 g of sodium carbonate and 0.2 mol L–1 hydrochloric acid solution
instead. Show all supporting calculations clearly.
96
97
Part 6.4______________________________________________________________________
1. 1.047 g of solid sodium hydrogen carbonate (NaHCO3) and 2.473 g of solid

sodium carbonate (Na2CO3) are dissolved in the same beaker of water,
transferred to a volumetric flask and made to 100.0 mL. The Ka for HCO3– is 4.7
x 10–11.
a) Calculate the pH of the resulting buffer.
b) Calculate the theoretical pH of the final solution if 10.00 mL of 0.05
mol L–1 hydrochloric acid solution was added to 50 mL of this buffer
solution.
c) Calculate the pH of the resulting solution if 0.020 g of solid sodium
hydroxide was added to 50 mL of this buffer solution.
2. Plan how you would make ~100.0 mL of a buffer solution with a pH of 10.80
using only sodium carbonate (solid), sodium hydrogen carbonate (solid) and
water, clearly specifying the masses of sodium carbonate and sodium
hydrogen carbonate that you would need to weigh out.
Reagents are expensive! Do not use more than necessary (< 5 g of any one
reagent should suffice). Check your calculation with your demonstrator before
starting your experiment!
99

Kinetics of the iodine clock reaction  Experimentally determine a

rate law. You learn how to
determine the order of reaction
and the activation energy for the
reaction by careful measurement
and observations.
Safety  Understand kinetics and rate
laws. This is an example of how
rate laws and activation energies
are determined and links into the
The chemical hazards in this laboratory a minimal. material discussed in lectures and
workshops.
You should use all organic solvents in the fumehood and wear appropriate  Graphically represent data.
You will use your graphical data
gloves if requested. You must correctly wear a laboratory coat, safety glasses,
to determine the order of reaction
and fully enclosed shoes at all times in the laboratory while conducting this with respect to each reagent and
experiment. the activation energy for the
reaction.

laboratory briefing. should consider photographing
Aim
To examine the effect of concentration changes on the rate of the iodine clock
reaction and determine an experimental rate law. This experimentally
determined rate law will be used to evaluate the plausibility of two proposed
reaction mechanisms.
The impact of temperature and catalysis will also be evaluated, and the value for
the activation energy for the reaction will be deduced graphically.
This exercise will involve as much thinking as doing. You should discuss your
approach as a group and with your demonstrator, if necessary.
Part 7.1_____________________________________________________________________
Background
Kinetics, Rate Laws & Reaction Mechanisms
Why should the rate of a reaction be important? Indeed, what is the rate of a
chemical reaction? To answer the last question first. The rate of a chemical reaction
is a measure of how fast products are being formed by that chemical reaction.
100
Conversely, it is also a measure of how fast reactants are being consumed. This will
be discussed in more detail later on.
The rates of chemical reactions are of great importance in industrial and biological
processes. The economic viability of many industrial processes is largely effected
by the rate at which the products can be formed. Of more vital importance, in the
true sense of the word, every chemical reaction taking place in your body is
occurring at a rate carefully controlled by the most complex of catalysts-enzymes.
Life would be impossible without the rates of countless, complicated chemical
processes being controlled with exceptional precision by exquisitely formed
enzyme catalysts.
The thermodynamic favourability of a process (ie the work needed to complete

that process or the energy released by that process) can be determined by applying
the Laws of Thermodynamics and simply measuring the initial and final energy of
the system. This tells us nothing about the rate at which the process can occur.
Indeed, many highly favourable processes will not proceed at a measurable rate
until something ‘triggers’ or catalyses them. For example: a litre of petrol will burn
vigourously in air to produce a great deal of energy. However, no obvious reaction
will be observed until the vapour above the petrol is ignited.
Kinetics is the study of the rate and mechanism of chemical reactions. From
kinetics experiments we can also derive useful information such as the rate law
(which can be useful in proposing underlying mechanisms for chemical reactions)
and the activation energy, Ea, for a given reaction. Our understanding of chemistry
is greatly increased by studying the details of chemical processes.
In this exercise the kinetics of the iodide-peroxodisulfate reaction will be studied.

This is known as the “Iodine Clock Reaction”. The effect of concentration of
reactants, and of temperature on the rate of reaction will be considered.
Mechanisms
The equation for the overall reaction may be written:
2I-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq) Reaction 1
When we write such an equation we are making a statement about the starting
materials and the products of the reaction. A chemical equation does not imply
that the process takes place in one step. To state that this is the reaction
mechanism is to imply that the three reactant molecules will collide absolutely
simultaneously, with the correct orientation and sufficient energy, and then
instantly be converted to products. This is extremely unlikely.
When studying reaction kinetics an attempt is made to describe a chemical reaction

as a series of single steps or elementary steps. The elementary steps must satisfy
two requirements:
101
1. The sum of the elementary steps in a mechanism must give the overall
balanced equation for the reaction.
2. The rate determining step (RDS), which is the slowest step in the sequence
of steps leading to product formation, should predict the same rate law as is
determined experimentally.
If it is possible to write a series of chemical equations that describe each of the
elementary steps in a chemical process then that series of steps is a reaction
mechanism.
Thus, the sequence of steps in the study of a reaction mechanism are:
postulating a
measuring the rate of formulating the rate
reasonable
reaction through law based on the
mechanism based on
experimentation results
the rate law
In the experiment you will do today, you will measure the rate of the reaction of
the oxidation of iodide ions (I–) with peroxodisulfate (S2O82–) ions under various
conditions and use your results to formulate an experimentally determined rate
law.
Several possible hypothetical mechanisms for the reaction being studied and the
rate law or rate expression which can be derived from them will be provided. Your
experimental rate law will either support or contradict the mechanisms provided.
The mechanism which supports your experimentally derived rate law will be the
likely mechanism for the reaction.
For example, there are two proposed mechanisms:
• Proposed reaction mechanism 1:

A single elementary reaction - simultaneous collision of all 3 reactants to form
products:
2I-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq)
• Proposed reaction mechanism 2:

A two-step process comprising the following elementary steps:
Step 1: I-(aq) + I-(aq)  *[I···I]2-(aq) (slow, RDS)
Step 2: *[I···I]2-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq) (fast)
These two equations are elementary steps in the overall chemical reaction. They
state that two iodide anions collide to form an intermediate di-iodide species which
lasts long enough to react, at some time later with one molecule of peroxodisulfate
to form the final products.
This is much more plausible than a simultaneous and instantaneous reaction,

however it is only one of several possible mechanisms which you will consider.
102
Rate determining step and rate law
As already stated it is often the case that one of the elementary steps in a reaction
mechanism is much slower than the rest. If this is so, the overall reaction rate is
equal to the rate of this slowest step and this step is called the rate determining
step (RDS). Some reactants may be not be involved in the RDS. Only reactants
involved in the RDS will have an impact on the reaction rate.
Consider the hypothetical mechanism for the oxidation of iodide ions with
peroxodisulfate ions above. The first step is the rate determining step so the rate
of the reaction can be determined from the first step alone:
This is the rate law or rate expression for the reaction where k is the rate constant.
If this rate law is the same as the experimentally determined rate law formulated
from your experimental results, the mechanism is the likely one for the reaction. If
the rate law contradicts your results, other mechanisms must be considered.
Rate laws and elementary steps
Which mechanism is more plausible cannot be determined theoretically. A series

of experiments must be performed in order to derive the (experimental) rate law.
This rate law allows us to know the impact of each reactant on the overall rate, and
hence can be used directly to reject or support a proposed reaction mechanism.
The experimental rate law is determined by conducting a series of experiments in

which one reactant’s initial concentration is varied and the impact this has on rate
is determined. The experiment is repeated under identical circumstances, but
varying the initial concentration of each other reactant, one at a time.
Once the rate law has been determined, the observed rate of the reaction may be
rationalised and a plausible mechanism deduced. If necessary, the reaction
conditions can then be adjusted to control the rate of the process.
While it is not possible generally to predict the rate of a chemical reaction from the
equation that describes it, it is possible to do so for an elementary step in a reaction
mechanism.
For two atoms, ions or molecules to react they must first collide. The rate of the
reaction is therefore proportional to the rate of collision for any given temperature.
The rate of collision is proportional to the concentration of the species involved in
the elementary step.
The rate of an elementary step is proportional to the concentration of

reactants involved in that step.
103
Consider three simple examples of elementary steps:
Example 1 Example 2 Example 3
A B C+DE 2F  G
Rate = k[A]1 Rate = k[C]1[D]1 Rate = k[F]2
First order process overall Second order process overall Second order process overall
First order process with respect to

First order process with respect to C Second order process with respect
A First order process with respect to to F
D
The order with respect to a reagent can only be determined by experiment, which
then allows us to postulate a proposed mechanism of elementary steps which
matches these findings. The stoichiometric coefficients of reactants in the
elementary step that governs the rate of a reaction (RDS) matches the order of
those reactants in the experimental rate law.
The order of an overall reaction or with respect to an individual reactant

cannot be determined from the reaction stoichiometry.
Using graphical analysis to determine order of reaction
The rate law for the overall reaction can be given by:
∆[I2 ]
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = = 𝑘𝑘[S2 O8 2− ]𝑥𝑥 [I− ]𝑦𝑦
∆𝑡𝑡
The time measured for the blue colour is dependent on the fixed concentration of
thiosulfate present and a fixed change in iodine concentration produced.
Therefore Δ[I2] is constant and:
∆[I2 ]
∝ 𝑘𝑘[S2 O8 2− ]𝑥𝑥 [I− ]𝑦𝑦
∆𝑡𝑡
The aim of the first two experiments is to determine x and y. This can be done using
graphical analysis of the raw data.
From the first experiment, where the iodide concentration is held constant you will
∆[I2 ]
have plotted versus [S2O82–].
∆𝑡𝑡
From this graph the value of x may be determined, i.e. the order of reaction with
respect to the peroxodisulfate concentration. Table 7.1 shows a summary of the
plots that can be obtained.
104
Table 7.1 6 - Graphically determining the order of reaction with respect to reactant A. Rate
(∆[A]/∆t) is plotted on the vertical (y) axis; [A]initial is plotted on the horizontal (x) axis 7.
Zero order, x = 0 1st order, x = 1 2nd order, x = 2
Rate ∝ [A]0 Rate ∝ [A]1 Rate ∝ [A]2
y = constant (as x0 = 1) y∝x y ∝ x2
The graph will be

independent of [S2O82–] (does The graph will be linear
not vary with [S2O82–])
∆[I2 ]
To confirm the order as second or third order, plot against [S2O82–]2 or [S2O82-]3.
∆𝑡𝑡
A straight-line plot is the necessary evidence for assigning a value to x.
From the second experiment with the data provided, where the peroxodisulfate
∆[I2 ]
concentration is held constant you will have plotted versus [I–] and you can
∆𝑡𝑡
determine y using the same mechanism described above.
Knowing the values of x and y, the rate constant, k, may be calculated from the
equation:
∆[I2 ]
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = = 𝑘𝑘[S2 O8 2− ]𝑥𝑥 [I− ]𝑦𝑦
∆𝑡𝑡
You can calculate k using data from any experiment and it should be the same for
all experiments conducted at that concentration and temperature.
Experimental Determination of Activation Energy
Using the rate expression you derived above, the rate constant k can be determined
at each of the four temperatures studied (on ice, at room temperature, 30 and 40
°C).
The Arrhenius equation relates temperature and the rate constant:

𝐸𝐸𝑎𝑎
𝑘𝑘 = 𝐴𝐴𝑒𝑒 −𝑅𝑅𝑅𝑅
6
Images from https://www.varsitytutors.com/assets/vt-hotmath-legacy/hotmath_help/topics/rate-of-change/image002.gif
7
Note: Integrated Rate Laws offer an even better approach for graphically determining reaction orders. These are not examinable
in this unit, but if interested you can find more information about these in the textbook.
105
This can be rearranged into a linear form:
𝐸𝐸𝑎𝑎 1
ln 𝑘𝑘 = − � � + ln 𝐴𝐴
𝑅𝑅 𝑇𝑇
where:
k = rate constant
Ea = activation energy (in J)
R = ideal gas constant = 8.314 J K–1 mol–1
T = temperature (in K)
A = pre-exponential or frequency factor
A plot of ln k versus T–1 should be linear with a negative slope of -Ea/R and a y-intercept of ln A.
y-intercept: ln A
y-axis: ln k
slope: -Ea/R
x-axis: 1/T or T-1
From your data calculate the value of the activation energy (Ea) in kJ.
The iodine clock
In determining the rate of the reaction the rate of change of concentration of

reactants or products at any time "t" must be known.
For this reaction it is convenient to study the rate of formation of iodine (I2) since
this product is coloured and also gives an even stronger deep blue colour when an
indicator is present. In this case we’ll use a synthetic indicator, but the naturally
occurring polysaccharide starch may also be used.
However, since the colour of the iodine in solution builds up gradually, it would be
difficult to compare accurately the rate of production of iodine for one kinetic run
with that of another.
The problem may be overcome by adding, to the reacting system, a standard

amount of a material that would react with the iodine formed and so delay the
formation of any iodine colour until all the added material had reacted.
The time elapsing before the first trace of iodine colour in the reacting system
would be the time required (Δt) for a standard amount of iodine to be formed.
From this the initial rate of change of concentration of iodine may be determined.
2S2O32-(aq) + I2(aq)  S4O62-(aq) + 2I-(aq)

106
Thus, according to this equation, if 10 mL of a 0.1 g L–1 Na2S2O3.5H2O solution is
added to the iodide-peroxodisulfate reacting system, the S2O32– would react with
2.02 × 10–6 moles of I2.
This represents the amount of I2 formed before an iodine colouration appears.
The following diagram and notes summarises the sequence of reactions for this
experiment:
S2O82-(aq) + 2I-(aq) I2(aq + 2SO42- Reaction 1

Peroxodisulfate + Iodide Iodine + Sulfate
Is there any thiosulfate I2(aq) + (C6H10O5)n(aq)  blue

present?
No Iodine + Starch Indicator
Yes
S4O62-(aq) + 2I-(aq) I2(aq + 2S2O32-(aq)

Reaction 2
Tetrathionate + Iodide Iodine + Thiosulfate
(set amount)
• In all reaction mixtures there is a fixed and constant concentration of

thiosulfate.
• A known concentration of peroxodisulfate is added to a known concentration
of iodide and the stop watch is started. The reaction between these proceeds
and iodine and sulfate is formed.
• If there is thiosulfate present it will react with the iodine reducing it to iodide,
which is consumed in the original reaction.
• This cycle will continue until all of the thiosulfate is consumed.
• Once the thiosulfate is consumed iodine will react with the starch and form a
blue complex. The stopwatch is stopped and time recorded. This time
represents the time (t) required to consume a fixed concentration of iodide.
• The experiment is repeated at different concentrations of iodide or
peroxodisulfate or a different temperature. In all cases the same concentration
of thiosulfate is always used.
107
Part 7.2_____________________________________________________________________
Procedure
When performing kinetics experiments it is important to change just one variable

at a time to determine the impact to the rate of reaction with respect to that
variable. In this experiment we will examine two variables: the influence of
concentration of each of the two reactants and then the temperature of reaction.
Experiment 1 – Varying concentration of peroxodisulfate, S2O82-(aq)
There are six experiments given in the table below. You should work in pairs to
complete at least three of the six experiments and collaborate with another pair
who will do the other three experiments.
For your logbook

1. What are the names of the groups you will share results with? Note
their full names down in your logbook.
a) Using a measuring cylinder add 20 ml of 0.125M potassium iodide along with

0.2g of starch (iodine indicator 8, which is a solid) to a clean and dry 100 mL
conical flask. Label this flask 1.
b) Using a pipette add 10.00 mL of 0.1 g L-1 thiosulfate solution to flask 1 and
swirl to dissolve and mix the reagents.
c) Into a second clean and dry 100 mL conical flask using a measuring cylinder
add the required volume from the table below of peroxodisulfate solution
and water. Label this flask 2.
Experiment
Flask Reagent
1 2 3 4 5 6
iodide (0.125 M) 20 mL 20 mL 20 mL 20 mL 20 mL 20 mL
1 thiosulfate (0.1 g L–1) 10.00 mL 10.00 mL 10.00 mL 10.00 mL 10.00 mL 10.00 mL
indicator 0.2 g 0.2 g 0.2 g 0.2 g 0.2 g 0.2 g
peroxodisulfate
20 mL 10 mL 8 mL 6 mL 4 mL 2 mL
(0.025 M)
2
water 0 mL 10 mL 12 mL 14 mL 16 mL 18 mL
8
For the indicator 0.2 g equals about half of a spatula full, which is sufficient. There is no need to accurately weigh this mass.
108
For your logbook
2. Copy the following table into your logbook (or cut and paste blank table
from page 13 into your logbook) and complete it as you conduct the
experiments.
Experiment Initial Concentration / mol L–1 in overall Time taken to consume

Rate*
Mark the reaction mixture added thiosulfate
experiments you ∆[𝑰𝑰𝟐𝟐 ]
Peroxodisulfate
conducted with an Iodide [I–] Δt (s) ∆𝒕𝒕
[S2O82–] (mol L-1 s–1)
asterisk (*).
*Remember ∆[I2] is set to a fixed amount – so you only need to calculate it once.
d) Quickly add the contents of flask 2 to flask 1 and start a stopwatch. Mix the
reagents by swirling once only and carefully observe the reaction. Halt the
stopwatch when the first appearance of a blue colour is seen. Note this time
down for this experiment: Δt.
e) Repeat for another two experiments, noting down which of these you
performed, and obtain the missing data from another group.
For your logbook
3. Inspect your raw data and predict whether the reaction is 0, 1st or 2nd order
with respect to the reactant that you varied in this series of experiments.
Using the graph paper provided at the end of the laboratory notes, to
construct an appropriate graph (refer to Table 7.1). Staple your graph into
your logbook in the appropriate location.
109
Experiment 2 – Varying concentration of iodide, I-
Experiments (similar to ones that you have just done) were conducted in which
[I-] was varied while [S2O82-] was kept constant. The results are shown below:
Experiment Concentration / mol L–1 Time Rate
Initial concentration (mol L-1) in overall

reaction mixture ∆[𝑰𝑰𝟐𝟐 ]
Δt (s) ∆𝒕𝒕
Peroxodisulfate (mol L-1 s–1)
Iodide [I ]
–
[S2O82–]
1 0.05 0.01 46
2 0.04 0.01 58
3 0.03 0.01 92
4 0.02 0.01 116
5 0.01 0.01 230
*Note: ∆[I2] is set to a fixed amount identical to that used for Experiment 1.
For your logbook

4. (a) Inspect your raw data and predict whether the reaction is 0, 1st or 2nd
order with respect to the reactant that you varied in this series of experiments.
Using the graph paper provided at the end of the laboratory notes, to construct
an appropriate graph (refer to Table 7.1). Staple your graph into your
logbook in the appropriate location.
Determining the overall rate law – combining Experiments 1 & 2
5. (a) Using the linearity of the graphs you plotted for Experiments 1 and
2, determine the order of the reaction with respect to the two reagents,
peroxodisulfate, S2O82– (x), and iodide, I- (y).
(b) Determine the overall reaction order and rate law for this experiment.
Use the following equation to help you.
∆[𝐼𝐼2 ]
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = = 𝑘𝑘[𝑆𝑆2 𝑂𝑂8 2− ]𝑥𝑥 [𝐼𝐼 − ]𝑦𝑦
∆𝑡𝑡
110
6. (a) Use the rate law you derived to calculate the rate constant, k, using
results from two different experiments (Show the data you selected in a table
like the one below). Don’t forget to include the correct units for your rate
constant!
Expt. 1 - Varying peroxodisulfate Expt. 2 - Varying iodide
Experimental data [I–]

used [S2O82–]
Calculated rate Rate

constant k
Part 2: Effect of temperature and catalysis
There are five experiments given in the table on the top of the next page. You
should work in pairs to complete at least two of the first four experiments and
collaborate with another pair who will do the other two experiments. All groups
should perform experiment 5.
In this experiment the effect of temperature on the rate of the reaction between
iodide ion and peroxodisulfate ion is studied. The effect of concentration on this
reaction rate has already been studied above. The concentrations will be held
constant in this experiment, and the temperature will be varied. The effect of a
catalyst on the reaction will also be studied.
a) Using a measuring cylinder add 20 mL of 0.125M potassium iodide along

with ~0.2 g of starch (iodine indicator) 9 (which is a solid) to a clean and dry
100 mL conical flask. Label this flask 1.
b) Using a pipette add 10 mL of 0.1 gL-1 of thiosulfate solution to flask 1 and
swirl to dissolve and mix the reagents.
c) Into a second clean and dry 100 mL conical flask using a measuring cylinder
add 10 mL of 0.025 M peroxodisulfate solution and 10 mL of water. Label
this flask 2. This will give the final concentration of peroxodisulfate given
in the last row.
d) For experiments 1-4, you will need to perform each experiment at a fixed
and known temperature. In each case, allow the flasks to thermally
equilibrate for ~10 minutes before recording the actual temperature of
both flasks. If the temperature is not constant, you may need to wait longer
than 10 minutes. Keep both flasks in the water baths until you are ready for
the next step. Some specific steps for each experiment are are below:
• For Experiment 1 place the two flasks into a large beaker of tap
water.
9
For the indicator 0.2 g equals about half of a spatula full, which is sufficient. There is no need to accurately weigh this mass.
111
• For Experiment 2 place the two flasks into a large beaker of ice and
water.
• For Experiment 3 place the two flasks into the water bath set at
30 °C.
• For Experiment 4 place the two flasks into the water bath set at
40 °C.
e) For Experiment 5 repeat the process for Experiment 1, just with the addition
of the copper/iron sulfate catalyst.
Experiment
Flask Reagent
1 2 3 4 5
iodide (0.125 M) 20 mL 20 mL 20 mL 20 mL 20 mL
1 thiosulfate (0.1 g L–1) 10.00 mL 10.00 mL 10.00 mL 10.00 mL 10.00 mL
indicator 0.2 g 0.2 g 0.2 g 0.2 g 0.2 g
peroxodisulfate (0.025 M) 10 mL 10 mL 10 mL 10 mL 10 mL
water 10 mL 10 mL 10 mL 10 mL 10 mL
2
[peroxodisulfate] mol L–1 0.0125 0.0125 0.0125 0.0125 0.0125
FeSO4CuSO4 solution None None None None Four drops
Catalyst -
Conditions Room temp On ice 30 °C 40 °C
room temp
Note: Do NOT change the settings on the water baths. Also, make sure you record
the actual thermally equilibrated temperature of your solutions, as it may be
different to that stated on the dial.
112
For your logbook
7. Copy the following table into your logbook (or cut and paste blank table from page 13
into your logbook) and complete it and complete it as you conduct each experiment.
Expt. (Mark Time k ln k

∆[𝑰𝑰𝟐𝟐 ]
your Rate*: Temp. Temp. 1/Temp
∆𝒕𝒕 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓 (Note: ln =
group’s (mol L-1 s–1) �= 𝒚𝒚 � logarithm, (°C) T (K) T-1 (K-1)
Δt (s) [𝑰𝑰− ]𝒙𝒙 �𝑺𝑺𝟐𝟐 𝑶𝑶𝟐𝟐−
𝟖𝟖 �
with an *) base e)
5 n/a n/a n/a
f) Quickly add the contents of flask 2 to flask 1 and start a stopwatch. Mix the
reagents by swirling once only and carefully observe the reaction. Halt the
stopwatch when the first appearance of a blue colour is seen. Note this
time down for this experiment: Δt.
g) Repeat for another experiment, noting down which of these you performed
on your report sheet, and obtain the missing data from another group.
8. Construct graphs of ln k Δt versus the inverse temperature T–1 (with
temperature units of Kelvin) for each of Experiments 1 –4 using the graph
paper provided at the end of the laboratory notes then draw a line of best
fit.
113
Tables for Experiment 7
Experiment Concentration / mol L–1 Time Rate
Initial concentration (mol L-1) in overall

reaction mixture ∆[𝑰𝑰𝟐𝟐 ]
Δt (s) ∆𝒕𝒕
Peroxodisulfate (mol L-1 s–1)
Iodide [I ] –
[S2O82–]
1 0.05 0.01 46
2 0.04 0.01 58
3 0.03 0.01 92
4 0.02 0.01 116
5 0.01 0.01 230
Expt. 1 - Varying peroxodisulfate Expt. 2 - Varying iodide
Experimental data [I–]

used [S2O82–]
Calculated rate Rate

constant k
Expt. (Mark Time k ln k

∆[𝑰𝑰𝟐𝟐 ]
your Rate*: Temp. Temp. 1/Temp
∆𝒕𝒕 𝒓𝒓𝒓𝒓𝒓𝒓𝒓𝒓 (Note: ln =
group’s with (mol L-1 s–1) �= 𝒚𝒚 � logarithm, (°C) T (K) T-1 (K-1)
Δt (s) [𝑰𝑰− ]𝒙𝒙 �𝑺𝑺𝟐𝟐 𝑶𝑶𝟐𝟐−
𝟖𝟖 �
an *) base e)
5 n/a n/a n/a

114
115
Part 1: Experiment 1 - Graph of rate versus ___________________________.
116
117
Part 1: Experiment 2 - Graph of rate versus ___________________________
118
119
Part 2: Graph of ln k versus T-1
120
121
Part 7.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Experiments: Ability to
conduct a series of
experiments to Very poor Good Very well
determine the rate of
reaction
Graphs: All graphs were

complete, neat, detailed None Few were complete All complete
and fully labelled
Calculations: Ability to
determine rate law and Very poor, mostly
Good, Mostly correct Excellent, all correct
calculate rate constant incorrect
with correct units.
Total Mark
1. Rate laws can only be determined experimentally. Describe the

experimental methods you used to determine the rate law with respect to
a reactant in Part 1 of this experiment.
2. Determine the slope of the graph you constructed for Part 2. Hence,
calculate the activation energy (Ea) in kJ for this reaction.
3. Comment on the effect of a catalyst on the rate of reaction based on your results for
Experiments 1 and 5 in Part 2.
122
123
Part 7.4______________________________________________________________________
• 20 mL of 0.125 M potassium iodide solution is mixed with 10 mL of 0.1 g L-1

sodium thiosulfate (Na2S2O3.5H2O) solution and ~0.2 g of solid iodine
indicator is added.
• To this solution is added 20 mL of 0.025 M peroxodisulfate solution.
• After 46 seconds a blue colour appears, indicating that sufficient I2 has been
formed from the reaction between KI and peroxodisulfate to consume all
the thiosulfate present. The final temperature is 18 °C.
1. The following prelab questions are designed to guide you through calculations
and processes that will enable you to use experimental data to i) determine the
rate of the reaction, ii) derive the rate law and iii) determine the rate constant,
k. You will do this during the laboratory using your own experimental results.
∆[𝐼𝐼2 ]
Calculated in (f) 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = = 𝑘𝑘[𝑆𝑆2 𝑂𝑂8 2− ]𝑥𝑥 [𝐼𝐼− ]𝑦𝑦
∆𝑡𝑡 Calculated in (a)
Calculated using (c), Calculated in (b)

(d) and (e)
Calculated in (g)
a) What is the initial concentration of iodide in the reaction mixture?
b) What is the initial concentration of peroxodisulfate in the reaction

mixture?
c) What is the number of moles of thiosulfate consumed after 46 seconds

of the reaction?
d) What is the number of moles of iodine formed after 46 seconds of the

reaction?
e) What is the change in concentration of iodine (I2) formed after 46

seconds of the reaction.
f) Hence what is the rate of the reaction (don’t forget to include correct
units)?
2. In your experiment you will determine the order of reaction with respect to
both reactants graphically. For this pre-lab question we will assume the
reaction is first order in both reactants (x = y = 1), so we can use the rate
expression below to calculate the rate constant, k.
124
∆[𝐼𝐼2 ]
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = = 𝑘𝑘[𝑆𝑆2 𝑂𝑂8 2− ]1 [𝐼𝐼 − ]1
∆𝑡𝑡
a) Using your answers to (d), (e) & (f) determine the value for the rate
constant, k, assuming that the reaction is first order with respect to each
reactant. Don’t forget to include the correct units for k.
3. What would the missing plot from Table 7.1 (see Introduction section) look
like? Cite the source you used to obtain this information (e.g. Maths textbook;
CRC Handbook of Chemistry and Physics, chemicals supplier website…, date
accessed….).
4. The time taken for the blue colour to appear following the mixture of 20 mL
of 0.125 M potassium iodide solution, 20 mL of 0.025 M potassium
peroxodisulfate solution, 10 mL of 0.1 g L–1 sodium thiosulfate solution and
0.2 g of indicator is measured as a function of temperature.
To determine the activation energy of the reaction the logarithm of rate

constant is plotted against the reciprocal of the Kelvin temperature and a
straight line drawn through the points. The co-ordinates of two points on
the line are:
1. T–1 = 3.36 x 10–3 K-1; ln k = -9.86
2. T–1 = 2.96 x 10–3 K-1; ln k = -7.13
Using this data, determine the slope of the graph between these two
points and find the activation energy for this reaction under these
conditions.
125

Extraction of organic compounds:  recognise how the common

organic functional groups react
with strong acids and bases,
Separation using acid-base properties  design separation strategies for
organic compounds based on this,
 use a separating funnel safely

Safety  You will develop an appreciation
of the techniques used in organic
and pharmaceutical science to
separate the compounds present
in complex mixtures.
 Using precise and concise

language. To communicate
All organic solvents used in this experiment should be regarded as toxic and science the language must be
flammable. You should use all organic solvents in the fumehood and wear precise and it is also good practice
to be concise. Answering the pre-
appropriate gloves if requested. laboratory and post-laboratory
You must correctly wear a laboratory coat, safety glasses, and fully enclosed developing this skill. This
shoes at all times in the laboratory while conducting this experiment. experiment may be selected for
Your demonstrator will illustrate the procedural hazards during the pre-laboratory
briefing.
Aim
To use the acid/base properties of organic compounds to separate mixtures.
Part 8.1______________________________________________________________________
Introduction
The separation of pure components from a complex mixture is a problem that is

central to practical organic chemistry, and one that cannot usually be solved by
using variations in a single property such as boiling point, or solubility in a single
solvent. However, by taking advantage of the presence of acidic and basic groups,
it is sometimes possible to achieve clean separations of mixtures using a separating
funnel, an organic solvent such as ether or ethyl acetate, and a sequence of
extractions with strong acids and bases. This separation technique uses the
property that charged species are soluble in water (a polar solvent) and neutral or
uncharged species are soluble in organic (non-polar) solvents.
126
To understand this procedure fully, it is necessary to revise some acid/base theory
as it applies in Organic Chemistry.
Acids
A typical acid, HB, can dissociate according to the following equation:
HA A- + H3O+ Reaction 1
The equilibrium constant for this reaction is called the acid dissociation constant
and is given by:
[𝐴𝐴:− ][𝐻𝐻3 𝑂𝑂+ ]
𝐾𝐾𝑎𝑎 =
[𝐴𝐴𝐴𝐴]
The stronger acids have the higher values of Ka. Indeed, for strong acids, Reaction
1 proceeds essentially 100% to the right and thus Ka is very large. The vast majority
of organic acids, however, have Ka values smaller than 10–3 M. This means that the
reverse reaction is actually favoured. We can say that the weaker the acid, the
stronger its conjugate base.
In order to avoid dealing with these small numbers, to use a negative logarithmic
scale and report these values as pKa values instead, where:
pKa = –log10 Ka
The weakest acids have the smallest Ka values and hence have the largest pKa
values. Conversely, the strong acids have high Ka values and small pKa values.
Any organic molecule that contains at least one hydrogen atom can be
considered to be an acid. The vast majority of such compounds have pKa values
greater than 18 and have essentially no tendency to dissociate at all. Their
importance as acids in organic chemistry is because of the reactions that their
conjugate bases (which are very strong bases) undergo. Table 1 gives many
examples of organic “acids” and their conjugate bases.
Potentially, any acid can react with any base in a proton-transfer reaction.
Whether or not any detectable reaction occurs is dependent on the relative
strengths of the acid and base involved.
The hydroxide ion is a strong base and will undergo an acid/base reaction with
any acid that has a pKa less than 14, like the carboxylic acids and phenols. The
reaction can be represented as:
A-H (pKa<14) + OH-  A:- + H2O Reaction 2a
The hydrogencarbonate ion is a weaker base than the hydroxide ion and will
only undergo reaction with relatively strong acids, specifically those that have
pKa values less than 6.35, like the carboxylic acids. The reaction can be
represented as:
A-H (pKa<6.35) + HCO3-  A:- + H2O + CO2 (g) Reaction 2b

127
Table 8.1: Some organic acids

and their conjugate bases
Bases
Any organic compound that contains a lone pair of electrons can be considered
to have basic potential. As represented in the following reactions, bases are
proton acceptors:
B:- + HA ⇌ HB + A:- or B: + HA ⇌ HB+ + A:- Reactions 3a & 3b
Table 2 gives some examples of ‘bases’ and their conjugate acids. Just as the
relative strengths of acids are ranked, it is common practice to tabulate base
strengths as pKb values, or even more commonly as the pKa values of their
conjugate acids. The strongest bases have the smallest pKb values and hence
their conjugate acids have the largest pKa values.
128
Recall: The relationships between Ka/Kb and pKa/pKb for conjugate acid/base
pairs are Ka x Kb = 1 x 10-14 and pKa + pKb = 14 at 25 ºC.
Table 8.2: Some organic acids

and their conjugate bases
Potentially, any base can react with any acid in a proton-transfer reaction.
Whether or not any detectable reaction occurs is dependent on the relative
strengths of the acid and base involved.
When the acid is strong (eg HCl), a reaction will occur with all bases except
those with pKb values greater than 15.74. All the bases listed in Table 2, except
the alcohol and the ether, will react with 2 M hydrochloric acid to yield their
conjugate acids.
129
Similarly, when the acid is water, which is a very weak acid, only the bases that are
stronger than OH- (those with pKb values less than –1.74) will react. When working
with such species in the laboratory, special precautions must be taken to ensure
that dry reaction conditions are maintained, often to the extent of excluding water
vapour in the atmosphere. The bases in Table 2 that are stronger than water, and
hence unstable in the presence of water are CH3CH2O-, NH2- and CH3CH2-
Extraction
The aim of this experiment is to separate a mixture of two aromatic, water-

insoluble compounds using their acid/base properties. The compounds are
an amine and a carboxylic acid, and the separation depends upon the following
properties.
• The aromatic AMINE used is a weak base (pKb ~ 9). The amine can be
protonated by dilute hydrochloric acid (2 M) to form a charged species
that is water soluble.
Ethyl acetate soluble Water soluble
However, amines are often oily compounds that slowly decompose. Hence, for
isolation and storage purposes, they are usually converted to a more stable amide
derivative. To achieve this, the amine is reacted with acetic anhydride in the
presence of an aqueous sodium acetate solution (pKa of acetic acid is 4.76). The
basic properties of sodium acetate ensures that a substantial proportion of the
amine salt is deprotonated, and thus available for acetylation by acetic anhydride.
130
Ethyl p-
acetamidobenzoate
ethyl acetate soluble
The aromatic CARBOXYLIC ACID used is a weak acid (pKa ~ 4) and can be extracted
from ethyl acetate by 2 M NaOH. The carboxylate anion is water soluble and
insoluble in organic solvents.
ethyl acetate soluble water soluble
Part 8.2______________________________________________________________________
Procedure
1. Reread the instructions below on how to use a

separating funnel. Check the tap of your 250 mL
separating funnel to ensure that it does not leak and the
tap moves smoothly. Set up the funnel in a ring holder
attached to the scaffolding in your fumehood (see
photos below). Label two 100 mL conical flasks as
CARBOXYLIC ACID, and AMINE.
131
Holding a separating funnel during shaking
Always point the stem away from

others during venting
2. Prepare your mixture

• Weigh out about 1 g of benzoic acid and about 1 g of ethyl p-
aminobenzoate into a small beaker. Mix your samples together.
3. Dissolve your mixture of compounds in ethyl acetate, transferring the
solution to the separating funnel and using in total about 40 mL of ethyl
acetate.
4. Perform first extraction
• Add 10 mL of 2 M NaOH. Stopper the funnel well, invert (CARE!
do not shake) and immediately open the tap to release
pressure which develops as you shake the ethyl acetate with the
alkaline solution. Close the tap, shake briefly and re-open the
tap to relieve pressure. Repeat this procedure twice and return
the funnel to the stand and remove the stopper.
• When the layers have separated run out the aqueous alkaline
solution (the lower layer) into the flask labelled CARBOXYLIC
ACID. Re-extract the organic layer with 5 mL of NaOH solution
and then 5 mL water adding these extracts to the flask. [Think
about why these extractions are made.] Set aside the
CARBOXYLIC ACID flask.
132
5. Perform second extraction
• Use the same extraction procedure described above.
• Extract the organic layer with 2 M HCl (CARE! Do not use the 10
M HCl.) using 10 mL the first time and 5 mL the second and finally
5 mL water. Collect all the aqueous extracts (lower layers) in the
flask labelled AMINE and set aside this flask also.
6. Conversion to more stable amide derivative
• Take the flask labelled AMINE and add 2 or 3 boiling chips and
warm on a hot plate for a few minutes to boil off any ethyl
acetate dissolved in the aqueous solution.
• Add 5 g of sodium acetate (CH3COONa·3H2O) and then 1.5 mL
of acetic anhydride from the dispenser stored in the fume hood.
(Take your flask to the fume hood and transfer the acetic
anhydride there.)
• Return the flask to your fume hood, mix the contents well and
cool in an ice-bath with swirling. The N-acetyl derivative should
crystallise within 5 minutes.
• After the contents are thoroughly cooled, take the flask back
to your bench, collect the amide product using a Hirsch funnel
(see diagram on page 7-6) and dry at the pump. Label a clean
and dry 100 mL beaker with “AMIDE”, weigh it and transfer your
sample into it once the compound is dry.
7. Regeneration of the carboxylic acid
• While the amide is crystallising add a few boiling chips to the
CARBOXYLIC ACID flask and boil off the dissolved ethyl acetate
using a hotplate.
• Cool the solution and cautiously add 5 mL of 10 M HCl, slowly
with swirling. CARE!
• Cool in ice if necessary and collect the crystals using a Hirsch
funnel. Wash with a little water and dry the crystals at the pump
while you continue the rest of the experiment. Weigh a clean
and dry 100 mL beaker labelled with “CARBOXYLIC ACID” and
transfer your sample into it once the compound is dry.
8. After all your compounds have been checked by your demonstrator,
dispose of them in the appropriately marked containers in the fume hood.
133
For your logbook
1. Copy the table below and determine the mass of your AMINE product
Mass of AMIDE beaker and sample g
Mass of AMIDE beaker g
Mass of ethyl p-acetamidobenzoate g
2. Determine the % Recovery.

3. What is the function of the sodium acetate?
4. Copy the table below and determine the mass of your CARBOXYLIC ACID
product
Mass of CARBOXYLIC ACID beaker g

and sample
Mass of CARBOXYLIC ACID beaker g
Mass of benzoic acid g
5. Determine the % Recovery

6. What is the purpose of adding the hydrochloric acid?
7. Compare your results with the other group’s results and discuss possible
reasons for yields that are quite low (or too high!).
134
135
Part 8.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Extraction: Ability to
correctly use a substantial some guidance with minimal
separating funnel guidance required needed guidance
was…
Carboxylic acid
Yellow-brown Pale/cream White colour/good
product: The
appearance/low coloured/moderate yield of dry product
appearance/%
recovery (<30%) yield (~30–70%) (>70%)
recovery was...
Amide product: The Yellow-brown Pale/cream White colour/good

appearance/% appearance/low coloured/moderate yield of dry product
recovery was... recovery (<30%) yield (~30–70%) (>70%)
Total Mark
1. Construct a flow chart to show how you would separate p-nitrobenzoic acid
and aniline, the structures of which are shown below. (Hint: Both
compounds are soluble in diethyl ether, but neither is soluble in water).
2. For the carboxylic acid extraction, describe:

136
a) the purpose of adding the 10 M hydrochloric acid, and
b) the impact this had on the solubility of the organic compound in
aqueous solution.
3. Provide possible causes for:
a) low yield for either substance, and
b) a recorded yield greater than 100%.
137
Part 8.4______________________________________________________________________
1. Complete the table below regarding substances that used in this

experiment.
Soluble in a) water, Any specific safety hazards
Appearance at
Materials b) ethyl acetate, or when handling this
room temperature
c) both substance in the laboratory
benzoic acid
ethyl p-aminobenzoate
ethyl
p-acetamidobenzoate
sodium acetate
acetic anhydride
ethyl acetate n/a
3 M hydrochloric acid
10 M hydrochloric acid
3 M sodium hydroxide
138
2. A flowchart is a useful way to describe the sequence of operations to
perform in order to extract organic compounds from a mixture. Choosing
appropriate reagents from those listed in Question 1, complete the
following flowchart to describe your plan to extract each compound from
the stated mixture. Inside the boxes of this flowchart include sketches of
relevant chemical species for each step.
Dissolve in _____________
Add ___________________
Organic layer
(top)
Add _______________
Add _______________
Residual
organic
substances
139

Carboxylic acids and their derivatives –  Carry out a synthesis of an

ester using reflux and isolation
of the liquid product. You will
using mind maps to link concepts form an ester and also distinguish
between a carboxylic acid and its
derivatives through some
chemical tests,
 Use mind maps to link
concepts. The construction of a
Safety mind map of the chemistry of the
various functional groups will help
you build links in your mind to
better understand the chemistry.
 Present of results through the
mind map, posters and talks.
This experiment may be selected
Concentrated sulfuric acid is corrosive. Methyl salicylate has a strong odour for inclusion in the poster, so you
and you should ensure that the concentration of the vapour in the laboratory should consider photographing
is kept to a minimum. All procedures in this experiment must be conducted your apparatus and product.
in the fumehood.
You must correctly wear a laboratory coat, safety glasses, and fully enclosed
Aim
1. To prepare and isolate an ester by the reaction of a carboxylic acid with

an alcohol;
2. To examine some characteristic reactions of carboxylic acids and
derivatives;
3. Use the experimental results to start constructing a mind map linking
these and other related concepts.
140
Part 9.1______________________________________________________________________
Introduction
Carboxylic acids and their derivatives have the general formula:
where Y may be oxygen, nitrogen, halogen or sulfur atoms contained in attached

groups. The four common carboxylic acid derivatives are the acid halides, acid
anhydrides, esters and amides. In this exercise you will be given three unlabelled
compounds (a carboxylic acid, an ester and an amide) and asked to determine
which is which by using simple chemical tests.
To refresh your memory some reactions of these compounds are listed below.
Acidity
Carboxylic acids are acidic and are readily soluble in basic solutions.
RCOOH → RCOO- + H+
RCOOH + NaHCO3 → RCOO-Na+ + H2O + CO2
Acid halides and anhydrides are not acidic themselves, but react with water to
form acidic solutions. Esters and amides are neutral and do not normally react
with water.
RCOX + H2O → RCOOH + HX
(RCO)2O + H2O → 2RCOOH
Nucleophilic Acyl Substitution
Most of the chemistry of carboxylic acids and their derivatives can be described
as nucleophilic acyl substitution. A general equation is given below.
141
Particular examples of nucleophilic acyl substitution are described below.
Ester Formation Esters can be formed by the reaction of alcohols with

carboxylic acids, acid chlorides or anhydrides.
RCOOH + R’OH → RCOOR’ + H2O
RCOCl + R’OH → RCOOR’ + HCl
(RCO)2O + R’OH → RCOOR’ + RCOOH
Ester Hydrolysis Esters are readily hydrolysed under basic conditions to give
alcohols and the carboxylic acid salt.
RCOOR’ + NaOH → RCOO-Na+ + R’OH
The hydrolysis can also be achieved under acid conditions but it does not go
so well.
Amide Formation Amides can be formed by the reaction of ammonia, primary

or secondary amines with acid chlorides or anhydrides.
RCOCl + 2NH3 → RCONH2 + NH4+ + Cl-
(RCO)2O + 2NH3 → RCONH2 + NH4+ + RCOO-
RCOCl + 2R’NH2 → RCONHR’ + R’NH3+ + Cl-
Amides are not readily prepared from carboxylic acids.
Amide Hydrolysis A m i d e s can be hydrolysed under acidic or basic conditions.

Under acidic conditions, the carboxylic acid and the ammonium salt are
obtained, while under basic conditions, the carboxylate salt and the amine (or
ammonia) are obtained.
RCONH2 + H+ + H2O → RCOOH + NH4+
RCONH2 + OH- → RCOO- + NH3
Base hydrolysis of primary amides produces ammonia gas that can be readily
detected by odour or with litmus paper. This reaction has commonly been
used for the identification of amides.
Part 9.2______________________________________________________________________
Procedure
The yield of ester can be increased substantially by using a longer reflux time.
Methyl salicylate has a strong odour and you should ensure that the
concentration of the vapour in the laboratory is kept to a minimum.
142
The reaction to prepare methyl salicylate is shown below:
Into a dry, 100 mL pear-shaped flask, add approx. 5 g of salicylic acid and 35
mL of methanol. Carefully add 5 mL of concentrated sulfuric acid with swirling.
Caution. This process is quite exothermic and may cause the methanol to boil.
Add a few anti-bumping granules and set up the apparatus for reflux as
illustrated in Experiment 2.
There is no need to grease the joint in this experiment; the grease will
contaminate your product. Reflux the mixture using a water bath for 1.5-2
hours. Keep an eye on the water flow through your reflux condenser or it may
boil dry!
During this reflux period carry out Part 2 below – Identification of Unknown
Compounds and commence work on the concept mapping exercise.
Cool the flask, then pour the mixture into a separating funnel containing 50 mL
of cold water. Shake the mixture and run out (and retain) the organic layer into
a beaker containing 10 mL of 10% sodium hydrogen carbonate solution. Stir
gently.
Discard the aqueous layer from the separating funnel. Add the organic extract
and sodium hydrogen carbonate solution to a separating and shake gently,
being sure to release the pressure often. The washing process involves gently
shaking the organic extract with an aqueous solution and separating the organic
layer from the aqueous layer.
Caution: A lot of carbon dioxide may be released when adding the sodium
hydrogen carbonate – so avoid a pressure build-up in the separating funnel! Your
demonstrator will show you how to do this correctly. The glassware may explode
if not handled correctly.
Separate the organic extract from the aqueous layer and dry it with a little
calcium chloride (approximately two spatula tips). Allow the mixture to stand
for about 5 minutes, or until the liquid is no longer turbid.
143
Filter the ester through a small filter funnel containing a small plug of cotton
wool into a clean, dry measuring cylinder.
For your logbook
1. Record your yield of methyl salicylate.

2. Calculate the % yield of methyl salicylate given the density of methyl
salicylate = 1.174 g/mL.
product and recorded its quality on the feedback sheet. This experiment may
be selected for inclusion in the poster, so you should consider photographing
Once your demonstrator has recorded his/her feedback, you may dispose of the
sample in the organic residue bottles.
Identification of unknown compounds
You are provided with three sample bottles labelled A, B and C containing white
solids. One contains an acid, another an amide and the third an ester, though
not necessarily in that order.
Without being told which ones, use some simple chemical tests to identify the
contents of the three bottles. The structure of the three compounds are below.
For your logbook
3. Using the results of the test you performed, what is the contents of each of
the sample bottles?
Concept Maps
Concept maps are diagrams that can assist in understanding the degree of
“interconnectedness” between the concepts that are relevant to a given topic.
The value in creating concept maps lies in the fact that the creator may need
to recognise which concepts are relevant as well as which are directly related.
144
Furthermore, the process of creating a map encourages rigorous reflection

upon the nature of the relationship between concepts.
Different people working independently will rarely produce similarly arranged

concept maps. The maps will often indicate the different perceptions that their
creators have of the topic under investigation. For any given topic, there is no
uniquely correct concept map.
A completed concept map (either provided to students or created by students)

can be an excellent summary of a particular topic.
Example
Students were asked to construct a concept map showing the relationship

between the concepts; nucleophile, Lewis base, SN reaction, backside attack,
solvolysis, SN1 reaction, leaving group, SN2 reaction, inversion of configuration,
nucleophilic substitution reaction, nucleophilic displacement reaction and any
others that are appropriate. The next page shows a possible solution of a
completed concept map relating these concepts.
Your Task
In the laboratory, you will be given a partial concept map relating to the
functional groups: alcohols, aldehydes, alkyl halides, amides, amines, carboxylic
acids, esters, ethers and ketones. Complete the map by indicating how the
groups are related, and how they can be interconverted. You may wish to
extend the map by including other functional groups.
Include your concept map to in your logbook.

145
146
147
Part 9.3______________________________________________________________________
Assessment
page 27.
Experimental Skills
Part 1 - Synthesis & Deeply coloured and Slightly coloured or Colourless and good
recovery of ester: yield low yield cloudy and moderate yield
and appearance… (< 20%) yield (20 – 50%) (> 50%)
Part 2 - Reactions: Unsuccessful or not Partially successful (at

Successful with each
Performed reactions to conducted (no least 1 unknown
unknown identified
identify unknowns were... unknowns identified) identified)
Showed some Showed most

Part 3 – Concept Map:
Was not started correctly connected concepts correctly
Concept map...
concepts connected
Total Mark
1. What is the function of the sulfuric acid?

2. Which is the organic layer? How could you tell if you are unsure?
3. What is the function of the sodium hydrogen carbonate solution?
4. In this experiment you conducted tests to identify three unknowns.
Describe two of these tests by completing the table below:
Observation and explanation

Functional group Chemical test/reagent confirming/discounting presence of
functional group
Carboxylic acid
Amide
148
149
Part 9.4______________________________________________________________________
1. Explain why the preparation of methyl salicylate will not proceed if dilute
sulfuric acid is used instead of concentrated sulfuric acid.
2. In this experiment, 5 g of salicylic acid will be reacted with 35 mL of methanol

(density = 0.787 g mL-1).
a) Determine (showing your working out) which reactant is the limiting
reagent and which is present in excess.
b) Your previous calculation should have revealed approximately 0.86

mole of excess reagent compared to approximately 0.04 mole of
limiting reagent. This equates to an actual mole ratio of about 22:1 for
a reaction that has a stoichiometric mole ratio of 1:1. Why do you think
such a large excess of this reagent is used?
3. In this experiment, you will carry out tests to identify three unknown
compounds. In the following table identify the functional groups present in
each of the unknown compounds and state what chemical test(s) you can
perform that will enable you to distinguish them, along with expected
observations.
Observation to confirm / discount

Functional group Chemical test / reagent
presence of functional group
4. Construct your own flowchart for this experiment. This should be sufficiently
detailed and contain all the relevant procedural steps for this experiment.

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CHEM1002: Reactivity and Function in Chemistry

Published: 21 February 2019

Dial 000 call Campus Security

Copyright Regulation 1969

Do not remove this notice

Welcome to the laboratory manual for Reactivity and Function in Chemistry at

An important part of the laboratory experience is learning to work safely. Safety is

Containers or bottles of hazardous substances are affixed with different diamond-

Figure 1: Some of the

Hazards are also highlighted in a pre-laboratory presentation given by your

Eye wash station Safety shower

1. Concentrated acids, e.g. sulfuric, nitric; concentrated alkalis, e.g. sodium

(a) on skin—wash off immediately under the nearest tap and

Never use an extinguisher of any type on a person. The soda-acid

3. Flammable liquids should never be handled near an open flame,

1. Always act responsibly. Horseplay, running, unauthorised experiments

Common laboratory reagents

Hydrochloric acid HCl 10.2 32 1.16

Nitric acid HNO3 16 70 1.42

Sulfuric acid H2SO4 18 95 1.84

Glacial acetic acid CH3COOH 17.4 99.5 1.04

Ammonia (aqueous solution) NH4OH 14 28 0.89

Sodium hydroxide NaOH 9 36 1.39

2. Dilute reagents (on benches) includes hydrochloric acid (HCl), nitric

General principles for volumetric analysis

The aim of quantitative analysis is to determine the quantity of a particular species

• There must be some means of detecting when the stoichiometric equivalent

• The volumetric pipette - used in the delivery of accurately known aliquots

Part 0.3 ______________________________________________________________________________

General lab procedures

Mass using electronic balances

1. Whenever possible a weighing bottle should be used. If the quantity of solid

a. Report any fault in balance operation to the demonstrator or

A volumetric flask is a calibrated piece of glassware that, when used correctly,

10.0 L. It is most commonly used to make a primary standard solution or to make

A standardised solution is one in which its concentration is accurately known. For

• Be readily soluble under the conditions being employed.

• Must react stoichiometrically with the substance being analysed.

Dilution of a sample or standard

1. Clean the pipette by rinsing thoroughly with deionised water.

Figure 8: How to set up

When the result of a determination is presented, some indication should be given

There are two broad classes of uncertainty—systematic uncertainty and random

1. They can be minimised by improvements in technique, e.g. weighing more

Random uncertainty can act in any direction. It is brought about by uncontrolled

• Weighing: ±0.001 g on a 3-decimal place balance.

• Burette: ±0.05 mL for each reading.

• Pipette: ±0.05 mL for a ±20.00 mL pipette, unless stated as otherwise on

Calculating overall uncertainty from measurement tolerances

In any experimental procedure, random uncertainties inherent to each piece of

For a simple titrimetric analysis, the following steps should be followed:

1. Identify sources of uncertainty—these will include any piece of quantitative

0.111 ± 0.003 mol L−1= 0.0034

Determinations are usually based on duplicates or triplicates. In general it is

The uncertainties expressed are based only on predictable random uncertainties.

A titration involves reacting a solution with a known quantity (usually number of

In acid-base titrations, the change in colour of an indicator may be used as

Instructions for calibrating the pH meter