APL 2023 LabManualAndReportBookfinal 2

CHEMISTRY 1
CHE1APL
Laboratory Manual
(Including Lab Report Worksheets)
2023
i
Contents
SECTION A ............................................................................................................. iii

EXPERIMENTS ....................................................................................................iii
1. INTRODUCTION ........................................................................................ iv
1.1 Registration with Allocate+ and Group Numbers ....................................... iv
1.2 Attendance........................................................................................... iv
1.3 Prescribed Items ................................................................................... v
1.4 Compulsory Prelab Online Exercise ........................................................ v
1.5 Pre-Laboratory Instructions ................................................................. vi
1.6 Reporting of Results ............................................................................ vi
1.7 Academic Integrity and Plagiarism ...................................................... vi
1.8 Marks and Marking ..............................................................................vii
1.9 Laboratory Manual Procedures and Notation ......................................vii
1.10 Laboratory Equipment and Cleaning ...................................................vii
1.11 References ......................................................................................... viii
2. SAFETY IN THE CHEMICAL LABORATORY .......................................... viii
2.1 Laboratory Personnel ......................................................................... viii
2.2 Dress Requirements ........................................................................... viii
2.3 Food..................................................................................................... ix
2.4 Information About the Chemicals You Use .......................................... ix
2.5 Risk Minimisation and Laboratory Safety .................................................. xi
2.6 Laboratory Waste ................................................................................ xi
2.7 Emergency Procedures ....................................................................... xi
2.8 Preparation Room................................................................................xii
2.9 Mobile Phones: ....................................................................................xii
3. LABORATORY LAYOUT .......................................................................... xiii
4. Glossary of Common Equipment
5. Calculation of Yields ..................................................................................xix
6. ESTIMATION OF ERRORS ......................................................................xxi
SECTION B: Experiments ...................................................................................... 1
EXPERIMENT 10 ................................................................................................. 1
EXPERIMENT 10: Report Sheet .................................................................... 11
EXPERIMENT 11 ............................................................................................... 17
EXPERIMENT 11: Report Sheet ................................................................... 23
EXPERIMENT 12 ............................................................................................... 29
ii
EXPERIMENT 13 ............................................................................................... 41
EXPERIMENT 14 ............................................................................................... 51
EXPERIMENT 15 ............................................................................................... 63
An Alphabetical List of the Elements and their Atomic Masses .......................... 81
iii
SECTION A
EXPERIMENTS
Number Title
10 Spectrophotometric Determination of the Salicylic Acid

Content in Synthesized Aspirin
11 Acid-Base Indicators
12 Effect of Temperature on Reaction Rate
13 Preparation of Acetate Esters
14 Determination of Calcium and Magnesium -

Complexometric Titrations with EDTA
1
15 H NMR Study of Organic Compounds
iv
1. INTRODUCTION
Chemistry is largely an experimental science and laboratory work constitutes an important

component of the discipline. The laboratory course is designed to help develop chemical skills
and techniques, familiarise you with common chemicals and equipment, to help you learn and
understand chemistry, and to appreciate how chemical information is obtained.
The experiments in this manual involve analytical and consumer chemistry, the preparation of
a coordination compound, and measurements in physical chemistry.
In addition to this manual, which provides the basic instructions for the experiments, references
are given where necessary. The complete list of references is shown in Section 1.11.
While the experiments provide an introduction to some basic techniques and methods in
chemistry, worthwhile results can only be achieved if care is taken when doing experimental
work. It is important to understand all of the techniques involved; there is a correct way to use
a dispenser and a burette, to collect a precipitate quantitatively, to qualitatively analyse an
unknown inorganic compound, or to distil a flammable organic liquid. In case of doubt, consult
one of the demonstrators. It is their job is to assist, so make use of them!
1.1 Registration with Allocate+ and Group Numbers
You are able to choose the day of your lab on ALLOCATE+

(https://mytimetable.latrobe.edu.au/odd/student ), or contact the Laboratory Coordinator
by email (che1apl@latrobe.edu.au).
For the CHE1APL laboratory, students attend the allocated laboratory session for the
semester. An assigned group number will be published for all students on LMS.
Group numbers, together with a detailed timetable, are available on LMS via the La Trobe
University CHE1APL chemistry website Students must check this to see when and where
they do each experiment.
1.2 Attendance
Each student is required to spend 3 hours per week in the laboratory as timetabled. If a class
is missed for a medical or non-medical reason the experiment may be able to be completed
on another day (subject to availability), otherwise a mark of zero will be recorded for that
particular experiment.
If a class is missed on account of illness, your Demonstrator or the First-Year Laboratory

Coordinator (Room 202a, LIMS2 or che1apl@latrobe.edu.au) should be informed as soon as
possible and a medical certificate presented. It is often possible to complete the experiment
on another day, contact Carmel on che1apl@latrobe.edu.au . If this cannot be arranged, an
average mark will be given for ONE missed experiment as calculated from the other marks
received in that semester. Note that this does not count as an “attended” laboratory
session.
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IMPORTANT
If a student enrolled in CHE1APL is absent for more than one laboratory session for
medical or non-medical reasons, the laboratory attendance requirement for that
course will not have been satisfied. Students who fail to meet these requirements will
have their final result withheld (W) until the laboratory component is completed in the
following year. Students must show medical certificates to support absences from the
laboratory classes.
1.3 Prescribed Items
The following compulsory items are required for the CHE1APL laboratory course and must
be brought to each on-campus face-to-face (F2F) laboratory class.
1. One pair of SAFETY GLASSES (regular glasses are not sufficient).
2. STUDENTS MUST have clothing COVERING their legs.

3. One LABORATORY COAT.
4. An electronic CALCULATOR.
5. Laboratory Manual that includes the Report Book

6. Pre-Lab Quiz Receipt
You MUST print this manual (Laboratory Manual) that includes the Laboratory Reports and
bring it to the laboratory session. The Laboratory Reports must be printed to one page per A4
paper and will be submitted at the end of the end of the Lab Class. PRINT each experiment
individually and DO NOT BIND.
1.4 Compulsory Prelab Online Exercise
Students need to undertake suitable preparation before commencing their laboratory session.
This is an important occupational, health and safety (OHS) issue and is standard practice in
industry.
Each student MUST COMPLETE the online Prelab multiple-choice exercise BEFORE their
scheduled laboratory session. Students need to bring a printout (or use smartphone, or
screengrab/photo) of their final Prelab mark as proof that they have completed this task. Any
student failing to do so, WILL NOT BE ALLOWED TO COMMENCE THEIR LABORATORY
SESSION.
IMPORTANT: THE RESPONSIBILITY IS YOURS to show that you have completed the prelab
exercise.
This exercise should take on average 15 minutes. You can attempt the prelab as many times
as you like and for as long as you like. Your score will not be included in your final lab mark.
However, you must have a score shown in your receipt (as described below) that is > 70% to
make your receipt valid. Completing the Prelab will automatically give you four marks out of
twenty towards your report assessment.
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Completing the prelab exercise provides necessary preparation for the lab, which will reduce
the time you need to complete the laboratory session and enable you to achieve the most from
each experiment.
To access the online Prelab:

• Login to LMS
• Select your subject 2023-CHE1APL(BU-2)
• Click on the Laboratory Program tile.
• Complete the H5P video for your timetabled experiment.
• Upon completing the H5P video, complete the appropriate Prelab exercise will be
available (BE CAREFUL, you MUST do the CORRECT Prelab!).
• Click on Start.
• Print screen containing log in name (top right-hand corner), date and your final score
(exactly as shown below).
Note that score shown must be > than 70%.
• REMEMBER to bring your receipt to laboratory session. This receipt allows you into
your laboratory session. You may also use your smart phone showing your completed
Prelab test to indicate a valid receipt.
1.5 Pre-Laboratory Instructions
At the beginning of the laboratory session the demonstrators will give a short introduction to
explain the theory of the experiment to be carried out and also to demonstrate various
laboratory techniques. Students are expected to prepare in advance for each experiment by
reading the relevant theory that is given in the manual and discussed in the references.
1.6 Reporting of Results
For the experiments in CHE1APL you are not required to write detailed laboratory reports. You
must record all observations and results in the Report Book. This must be printed to a size of
one page per A4 paper. The relevant results and report pages for each experiment must be
completed, and handed to the demonstrator at the conclusion of each laboratory session.
YOUR RESPONSIBILITY.
It should be emphasized that an accurate laboratory record is an essential part of good science
and so results must be recorded as they are obtained. It is important that reports are neat,
clear and concise. Marks will be deducted for reports that are not legible. Show ALL working
in any calculations.
1.7 Academic Integrity and Plagiarism
It is your responsibility to always demonstrate academic integrity by submitting your own work;
by not plagiarising, colluding, or cheating.
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https://www.latrobe.edu.au/students/admin/academic-integrity
La Trobe University defines plagiarism as when you:

• use other people's words, ideas, or designs e.g. images
• without acknowledging where they came from
• in order to pass an assessment, get a higher mark or benefit in some other way.
Adapted from the Center for Academic Integrity (2012). Why integrity? Retrieved from
http://www.academicintegrity.org/icai/integrity-1.php
La Trobe University takes plagiarism very seriously. There are serious consequences
for students caught plagiarising work.
1.8 Marks and Marking
Of the total marks for the Chemistry CHE1APL course, 25% are allocated to laboratory work.
The marking schemes vary and depend to some extent on the type of experiments being
carried out. Demonstrators will give further information on how student performance is
assessed. Each experimental report is given a mark out of 20. Marks are available within LMS.
1.9 Laboratory Manual Procedures and Notation
The procedures outlined in this manual conform to consistent notation. Underlined instructions
indicate important aspects of the procedure, for example stir slowly or weigh accurately. Bold
italicized text refers to specific safety instructions, such as do not remove solution from the
fume cupboard.
1.10 Laboratory Equipment and Cleaning
For the CHE1APL laboratory you will be assigned to a bench space for each experiment. The
apparatus is issued in a clean, workable condition and should be checked at the beginning of
each laboratory session. Report any missing or broken items immediately to your demonstrator
or the technician in the Preparation Room. Under no circumstances should you remove
apparatus from another student’s bench.
You are required to keep your bench clean and tidy and, in common with all others in the class,
to assume responsibility for the laboratory as a whole.
At the end of each working period, all apparatus must be carefully cleaned and left in the
appropriate drawer. Draw content lists are provided and you will be required to return your
cleaned equipment to the correct location. The bench and sink should be left clean and any
waste put in the bins provided in the benches. The fume cupboards and balances should
be left in a clean and tidy condition.
Glassware: Detergent is provided in plastic wash bottles and should be used for cleaning
all glassware. If this is ineffective, consult the technician about a special
cleaning mixture.
Reagents: Common reagents, such as acids and alkalis, are provided on the shelves
above each bench. Take care not to contaminate them. Solutions and reagents
will be put out on your benches. A few compounds are kept in the fume
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cupboards. Do not take more solution than you actually require for the
experiment. Do not pour “left overs” back into reagent bottles.
1.11 References
The following texts are referred to in certain experiments:

J.S. Fritz and G.H. Schenk, Quantitative Analytical Chemistry, Allyn and Bacon.
Mahaffy, Bucat, Tasker, Kotz, Treichel, Weaver and McMurray, Chemistry: Human
Activity, Chemical Reactivity.
2. SAFETY IN THE CHEMICAL LABORATORY
Experimental chemistry is a vital part of your chemical training. In the laboratory you will
develop many hands-on skills and consolidate your learning of a range of chemical principles.
In order for this to happen you need to adopt a responsible and mature attitude during your
laboratory classes. Chemicals can be dangerous so it is important that you learn and know
how to handle them safely. The following section explains some of the basic code of safe
laboratory practice.
2.1 Laboratory Personnel
You will have at least one demonstrator in the laboratory with you at any time, together with a
member of the technical staff. These people have a wide knowledge of the chemicals,
equipment and procedures you are using and also appropriate emergency response
procedures. Please consult them if you are in doubt about any procedure or are involved in an
accident. Report all chemical spills and accidents to YOUR DEMONSTRATOR who will inform
other laboratory personnel.
2.2 Dress Requirements
For your safety there are several requirements that must be followed. If you are not suitably
attired, you will be asked to leave the laboratory immediately.
1. SAFETY GLASSES MUST BE WORN AT ALL TIMES (OVER YOUR EYES). Even
if you normally wear prescription glasses you must wear safety glasses. It is
compulsory for students wearing prescription glasses to wear safety
overglasses. Sunglasses are not permitted.
2. Only FOOTWEAR with enclosed, solid uppers are permitted. Students with
thongs, open sandals or slipper type shoes (uncovered uppers) will not be
allowed into the laboratory.
3. LABORATORY COATS protect clothing and person from corrosive chemicals.

Shorts and tops that leave exposed midriffs or shoulders are not permitted.
4. Students with long hair must have it tied back before entering the laboratory.
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2.3 Food
No food, drinks (including water) or chewing gum may be consumed in the laboratory for health
reasons.
Smoking is strictly forbidden in all University buildings and also constitutes a fire hazard in the
laboratory.
2.4 Information About the Chemicals You Use
There are two easy ways to find out about the hazards of a
chemical you are about to use:
(i). Read the label. It should contain the following information:

• Product name
• Dangerous goods warnings (eg. corrosive, poison)
• Chemical name(s) of the contents
• Possible harmful information (risk information)
• How to use the substance safely
(ii). Material Safety Data Sheets (MSDS)

These contain more comprehensive information about the chemicals; including alternative
names, health hazard information, first aid procedures, precautions for safe use, and safe
handling and disposal procedures.
The MSDS for each chemical you use will be held in a folder in the laboratory. Please ask to
see it if you are unsure about what you are handling or would like more information. Many
MSDS are available on the web. You should become familiar with MSDS and what they tell
you.
2.4.1 Health Effects: Hazardous chemicals can adversely affect your health if you expose
yourself to them unwisely. The primary routes of exposure and ways of minimising such
exposure are:
• Respiratory (breathing in gases, vapours and particulate (dust) matter).

Work in fume cupboards when using gases and vapours.
• Contact with intact or broken skin (usually liquids or solids).

Wearing gloves and being careful can minimise this.
Always wipe up spills immediately (if necessary contact a member of staff).
• Ingestion (including accidental ingestion).

Wash your hands frequently and definitely before leaving the laboratory.
In no circumstances pipette by mouth.
2.4.2 Description of Hazard Categories and Rating Scale
The Hazard Category Color system is based on the NFPA system. The Rating Scale system
is based on the J.T. Baker Saf-T-Data © System. There are five categories: Toxicity and
Chronic, Flammability, Reactivity and Contact. In each category there is a Rating Scale, which
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is a number ranging from 0 (for low level of risk) to 4 (for high level of risk).
(i) Health Category (Toxicity and Chronic) refers to the capability of the chemical to cause
personal injury due to inhalation, skin contact, eye contact, or ingestion.
Rating Risk
0 Little to no risk
1 Caution Compound can cause irritation
2 Warning May be harmful if inhaled or absorbed
3 Warning Corrosive or toxic. Avoid skin contact or inhalation.
4 Danger May be fatal on short exposure. Specialized protective equipment required
(ii) Flammability Category refers to the ability of the chemical to create or sustain a fire.
Rating Risk
0 Not combustible
1 Combustible if heated
2 Caution Combustible liquid flash point of 37.8° to 93.4° C
3 Warning Flammable liquid flash point below 37.8° C
4 Danger Flammable gases and materials rapidly vaporized under normal conditions
(iii) Reactivity Category refers to how reactive the chemical is under normal laboratory
conditions.
Rating Risk
0 Very inert substance. Not reactive when mixed with water
1 May react if heated or mixed with water but not violently
2 Caution Unstable or may react violently if mixed with water
3 Warning May be explosive if shocked, heated under pressure or mixed with water
4 Danger Explosive material at room temperature
(iv) Contact Category refers to how dangerous physical contact with the chemical is under
normal laboratory conditions.
Rating Risk
0 No unusual hazard.
1 Compound can cause irritation.
2 Caution May be harmful if inhaled or absorbed
3 Warning Corrosive or toxic. Avoid skin contact or inhalation.
4 Danger May cause severe damage with contact to skin, eyes or mucous membranes
Keep in mind these descriptions are for general conditions and do not cover all possibilities.
For example, water has a health and contact rating of zero. However, one can kill themselves
by drowning, and boiling water or steam can be very dangerous with respect to physical
contact. Similar analogies are possible for every chemical. This just emphasizes that a certain
level of professional understanding and common sense is required when handling chemicals.
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2.5 Risk Minimisation and Laboratory Safety
There are several general principles that relate to the hazard category and rating of chemical.
It should also be noted that for safety reasons, students are not allowed to enter the preparation
room.
• Regard all chemicals as hazardous until you know otherwise. Consult the MSDS. Avoid
unnecessary contact with chemicals. Read the experiment notes before entering the
laboratory. It is a responsibility of the demonstrator to highlight to students the more
hazardous aspects of experiments at the start of each laboratory session.
• Students must not leave experiments unattended.
• As a matter of safety, students should keep their work area tidy, uncluttered and clean.
• Never use force when manipulating glassware. Lubricate glass tubing with water or an
organic solvent when connecting it to rubber tubing.
• Any device that constitutes a fire hazard should not be used within the laboratory, including
cigarette lighters.
2.6 Laboratory Waste
It is vital that laboratory waste is disposed of safely. If in doubt, please consult your
demonstrator.
All broken glass should be placed in the broken glass bins, not in regular paper waste bins.
Sweep up broken glass with a dustpan and brush. Be aware that most minor laboratory injuries
are the result of cleaning up broken glass rather than the initial breakage. Do not use your
hands to collect broken glass.
There are many chemicals that you should not put down the sink. In some experiments
dedicated waste containers will be provided. It is the duty of the demonstrator to let students
know if their liquid waste can be poured down the sink. If the experiment produces a solid
waste, this should not be thrown in the waste-paper bins but should be placed in a dedicated
solid chemical waste container. If you are unsure always discuss with your demonstrator.
Do not take more of a chemical from its original container than the quantity specified in this
manual so as to minimise your chemical waste. Never return excess chemicals to their
original container, as this commonly leads to contamination.
2.7 Emergency Procedures
Demonstrators need to inform students about emergency procedures specific to the first year
laboratory. Students must be made aware of the location of emergency exits, safety showers
and eye wash stations. In the event of an emergency, demonstrators should follow the
instructions of staff members, safety officers and emergency personnel.
2.7.1 First Aid: All accidents must be reported to a member of staff who will contact a first aid
officer. All technical officers are trained first aid officers. Once an injury has been attended to,
you will be asked to sign a University accident/injury form. This form protects you in the event
xii
of any longer term consequences associated with your accident. It also helps us to prevent
similar accidents in the future.
2.7.2 Fire: First of all, do not panic. Most fires can be extinguished by covering them; thus
starving them of oxygen. Fire extinguishers are located in each laboratory with all technical
staff trained in their use (please do not use them yourself). If the fire is serious enough to set
off the fire alarms, please evacuate the building in an orderly manner and assemble in the
appropriate evacuation assembly points.
2.7.3 Evacuation: This may be necessary due to a fire, chemical spill or bomb threat in your
laboratory or elsewhere in the building. If an alarm is sounded please ensure all students and
demonstrators leave the building swiftly through the nearest exit and make your way to the
appropriate assembly point. Follow instructions of the Fire Wardens and Technical Staff. The
nearest Assembly Points are the Visitor Car Park and at the back of the Library.
2.8 Preparation Room

Students are not allowed to enter the preparation room.
2.9 Mobile Phones: Mobile phones should be turned off or to silent while in the laboratory.
If you need to use a mobile phone, first make safe your experiment, inform your demonstrator,
then leave the laboratory to make your call.
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3. LABORATORY LAYOUT
It is important that you are familiar with the safety features of laboratory, including:
• Emergency exits
• Fire extinguishers and fire blankets
• Emergency eye-wash
• Emergency shower
Fume&cupboards&
EXIT&
Student&benches&
Student&benches&
Student&benches&
SINKS&
Project&Rooms&
North&
South&
&306/305&
Student&benches&
Student&benches&
Student&benches&
EXIT& Fume&cupboards&
Preproom&
(No&student&access)&
xiv
4. Glossary of Common Equipment
4.1 Measuring cylinders

Measuring (graduated) cylinders are used to measure the volume of liquids
(and solutions). The graduations on the side of the cylinder indicate the
volume. Typical sizes are 10ml, 50ml, 100ml, 250ml or 1000ml volumes.
Measuring cylinders should either be used dry, or should be rinsed out with
distilled water and twice with 5 ml portions of the solution being used.
4.2 Beakers
Beakers are a general-purpose item of glassware in the chemistry laboratory.
They are used as distillation receiving containers, to hold different layers in
an extraction, as reaction flasks, to heat solvent for crystallizations, as the
crystallization flask, as an ice bath, etc. Beakers must not be used for
titration.
4.3 Watch glass

Watch glasses are small, flat, round pieces of glassware. They are mainly
used to dry and weigh solid compounds and to cover containers such as TLC
developing chambers. Watch glasses come in many sizes.
4.4 Test tubes and Test tube rack

Test tubes are used for holding small amounts of liquids and solids.
Occasionally, reactions are carried out in test tubes. Small test tubes are
called ‘mini’ test tubes. Test tube racks are either wooden, plastic or metal
and are used for holding test tubes.
4.5 Graduated Volumetric Flasks

These flasks are graduated to contain a fixed volume of liquid at a given
temperature (generally 20°C), so care should be taken to ensure that
solutions to be made up to the mark are at room temperature. Flasks
should only be handled by the (narrow) neck.
4.6 Conical or Erlenmeyer Flasks

These should be used for titration work as they can be swirled vigorously
without any loss by splashing. Typical capacity is 250 ml. Beakers must not
be used for titration.
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4.7 Buchner Flask (Vacuum flask)
The vacuum flask looks like a Conical (Erlenmeyer) flask with a short arm
coming out of it. The "arm" is designed to connect the flask to a vacuum
source. When sealed on the top with a stopper or a Buchner funnel, the
vacuum flask will hold a reduced pressure. Note the heavy the walls of this
flask - they are designed to withstand reduced pressure without imploding.
This design feature is the reason for the high cost of this flask. Buchner flasks
are used either for filtering solutions or for removing solvent under reduced
pressure.
4.8 Buchner Funnel

The Buchner funnel is a white porcelein funnel. You need a grey or black
adaptor or a stopper with a hole in it to connect it to a side arm flask. The
Buchner is used exclusively for vacuum filtrations. The adaptor forms a snug
seal so that when reduced pressure is applied to the vacuum flask, liquid
poured into the Buchner is sucked into the flask quickly.
4.9 Hirsch Funnel

The Hirsch funnel is a white porcelain funnel. You need a grey or black
adaptor or a stopper with a hole in it to connect it to a side arm flask.
4.10 Burette
Burettes are used for measuring (dispensing) accurate volumes of solutions,

for example in titrations.
zero mark
Before use, burettes should be rinsed out with distilled water and twice with
5 ml portions of the solution being used. The burette should then be carefully
and gently clamped upright in the stand and allowed to drain before the
stopcock (tap) is closed. Fill the burette to a point just above the zero line.
Turn the stopcock to allow the solution to fill the tip of the burette and the
solution level is in the graduated portion of the tube. Burette tips should be
wiped dry before titration.
The burettes should be read to two decimal places (± 0.01 ml). Make certain Stopcock
that your eye is at the level of the liquid and read the level at the lowest point (tap)
of the meniscus, except for potassium permanganate and iodine solutions,
where you read the level at the top of the meniscus.
After use, the burettes must be rinsed thoroughly with distilled water and
returned to the stand and clamped in an inverted position with the tap open.
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Distillation/reflux glassware
A common experimental set up in organic
chemistry is for distillation or reflux. The
following glassware is used for these
purposes. The glassware is also referred to
as ‘Quickfit’.
Distillation is one of the oldest and still most
common methods for the purification of
liquids. It is used to concentrate dilute
alcoholic beverages and to obtain perfumes
from fruits and flowers. In short, distillation
consists of heating a liquid, separating the
vapours and recondensing them to obtain a
new liquid.
4.11 Round bottom flask
The round bottoms on these flasks allow for uniform heating and/or boiling
of the liquid. They are commonly used in distillation. Always clamp the flask.
Always add boiling chips before heating to avoid super-heating.
4.12 Pear Shaped Flask

Pear-shaped flasks are used in distillation, in particular for semi-micro
distillations. The pear-shape allows rapid distillation down to a small bulk.
4.13 Condenser
A condenser is used to cool hot vapours or liquids. A condenser usually

consists of a large glass tube containing a smaller glass tube running its
entire length, within which the hot fluids pass. The outer glass tube usually
has two hose connections, and a coolant (usually tap water) is passed
through it. The cold water always enters through the bottom fitting, and exits
through the top fitting. Condensers are used for reflux (where the hot solvent
vapours of a liquid being heated are cooled and allowed to drip back) and
distillation (condensing the hot vapours into liquid for collection).
4.14 Distillation head

A distillation head that connects the distillation flask to the condenser. The
distillation head holds a thermometer to allow the temperature of the vapoUrs
to be monitored during the distillation.
4.15 Receiver / Adaptor

A distillation adaptor that connects the condenser to the receiving flask.
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4.16 Boss Head

Used to connect clamps to a retort stand.
4.17 Clamp
Used to clamp glassware. Connected to a retort stand with a boss head.
4.18 Bunsen Burner

Gas burner used for heating. Bunsen burners must never
be left unattended. The heat can be adjusted by changing
the air hole – the blue flame is the hottest. If not heating,
leave the burner with a yellow flame (adjust the air hole).
Mainly used in distillation and reflux. As an alternative,
heating mantles may be used.
4.19 Separatory Funnel

A separating funnel, also known as separation funnel or separatory funnel,
is used in liquid-liquid extractions to separate the components of a mixture
between two immiscible solvent phases of different densities. To use the
funnel, the two phases and the mixture to be separated in solution are added
through the top with the stopcock at the bottom closed. The funnel is then
closed and shaken very strongly to bring the phases into close contact. The
funnel is then inverted and the tap carefully opened to release excess vapour
pressure. The separating funnel is set aside to allow for the complete
separation of the phases. The top and the bottom tap are then opened and
the two phases are released by gravitation.
4.20 Dispensers
These are designed to deliver a fixed quantity of liquid; most of those used
in this course will deliver 20.0 ml. To use a dispenser, the preset amount of
liquid is drawn up into the internal reservoir and then delivered into an
appropriate flask by gently depressing the plunger completely down. Do not
use the full pressure of your palm.
4.13 Balances
Instructions in the use are to be found next to the balances. At the beginning of this course a
demonstration on the use of the balances will be given by your demonstrator. Always consult
a demonstrator if in doubt. The balances are very delicate instruments and must be
handled with care. The following rules should be obeyed at all times:
(a) The floor of the balance, pans, and area around the balance must be kept
scrupulously clean. Use the brush supplied in the balance room.
(b) Samples should be weighed in sample weighing bottles or small beakers. It is
poor technique to use watch glasses or filter papers - except when using the TOP
xviii
LOADING BALANCES. Samples should be added to the weighing bottle OFF the
balance – do not add sample to the balance.
(c) Do not use scraps of paper for recording weighings as these are easily lost.
(d) All analytical data accumulated during an experiment must be recorded directly into
your laboratory notebook.
If a solid material is to be made up as a standard solution, dissolve the accurately weighed

solid in the weighing vessel in some distilled water. Transfer this solution to the volumetric
flask through a short-stemmed funnel. Rinse the weighing vessel with a stream of water from
the wash bottle to remove the last traces of the particles or solution and transfer carefully to
the volumetric flask. Repeat several times. Using a stream from the wash bottle, wash the
funnel and the stem thoroughly into the volumetric flask. Add distilled water to the volumetric
flask until it is about three-quarters full. Swirl to mix. Using a wash bottle, add water to the flask
until the level is about one centimetre below the mark. Using a pasteur pipette or a wash bottle,
add water to the flask until the meniscus is exactly level with the mark. Stopper the flask and
use both hands to invert the flask eight to ten times to thoroughly mix the contents.
If a liquid is to be made up as a standard solution, transfer the liquid to the volumetric flask
using a dispenser. At this point, the procedure is the same as that above for the solid. After
filling to the mark, mix thoroughly as before.
xix
5. Calculation of Yields
5.1 Calculation of Yield When There is No Chemical Change (Reaction)

When there is no chemical reaction occurring, and the product is just extracted from the original
material (such as the extraction of caffeine from tea leaves), the yield is simply the mass of
product expressed as a percentage of the original material.
For example, if we extract 0.01 grams of caffeine from 2.00 grams of tea, the percentage yield
is calculated as:
0.01g 100
% yield = × %
2.00g 1
= 0.05%
If we are purifying a material, such as methylated spirits, to extract the ethanol, and we get 9.0
grams of ethanol from 10.0 grams of methylated spirits, then the percentage yield (or
percentage recovery) is calculated as:
9.0g 100
% yield = × %
10.0g 1
= 90%
5.2 Calculation of Yield in a Chemical Reaction
There are two steps to the calculation of a percentage yield:
1. Calculation of theoretical yield

This is simply a stoichiometry problem. To calculate the theoretical yield in a reaction
requires a balanced chemical reaction, from which you must identify the limiting reagent.
You will need to determine the molecular weight of the reactants and products of interest.
The balanced equation provides the molar ratios, from which a calculation of the number
of moles of reactants enables the theoretical number of moles of products to be
determined.
2. Calculation of percentage yield
The percentage yield is simply ratio of the mass of your actual yield to the theoretical yield.
actual yield 100

% yield = × %
theoretical yield 1
This is best illustrated with an example.

xx
Example. In an experiment, 20.0 grams of sodium bicarbonate (NaHCO3) was decomposed
by heating according to the reaction,
2 NaHCO3 (s) ® Na2CO3 (s) + CO2 (g) + H2O(g)
A student recorded that 9.4 grams of sodium bicarbonate (Na2CO3) was produced.
Firstly, note that the molar ratio of sodium bicarbonate (NaHCO3) to sodium carbonate
(Na2CO3) is 2:1. That is, 2 moles of sodium bicarbonate will produce 1 mole of sodium
carbonate. The molecular weight of NaHCO3 is 23 + 1 + 12 + (3 x 16) = 84 g/mol. The molecular
weight of Na2CO3 is (2 x 23) + 12 + (3 x 16) = 106 g/mol.
Calculate the number of moles of reactant.
n(NaHCO3) = mass / MW
= 20.0 / 84
= 0.238 mol
Since 2 moles of NaHCO3 produces 1 mole of Na2CO3,
n(Na2CO3) = ½ x n(NaHCO3)
= 0.5 x 0.238
= 0.119 mol
Now calculate the expected mass of Na2CO3.
mass(Na2CO3) = n x MW
= 0.119 x 106
= 12.6 g
So if the reaction went to completion, with no experimental errors (spills etc), this reaction
would produce 12.6 grams of sodium carbonate.
Now we can calculate the percentage yield.
actual yield 100

% yield = × %
theoretical yield 1
9.4 100
= × %
12.6 1
= 75% (2 significant figures)
xxi
6. ESTIMATION OF ERRORS
A chemist must establish the probable limits of error that can be placed on a final result. The
calculation of errors can be approached in different ways depending on the nature of the
experiment and the form of the results.
1. In carrying out a quantitative analysis the error estimation involves the calculation of the
highest possible value and the lowest possible value and taking their average. In doing
this the following assumptions are made:
(a) Normally the error associated with any titre is ± 0.05 ml. This represents the accuracy
to which you can read the burette.
(b) The error associated with weighing on the analytical balance is 0.0001 g (0.1 mg)
for a “4-figure” balance and 0.001 g (1 mg) for a “3-figure” balance.
(c) calibration procedures but may be assumed for our purposes to be ± 0.05 ml.
(d) The error associated with the volumetric flask is ± 0.1 ml.
2. The use of Significant figures is an important concept in experimental science. It is

important to remember that when quoting an answer, you must not use more significant
figures than there are in the least accurate data. Retain as many significant figures as
required to give only one uncertain digit. For example, the volume of a 100 ml standard
flask would best be quoted as 100.0 ml, where the volume is considered to be somewhere
between 99.9 and 100.1 ml, i.e. the fourth digit is uncertain. Thus, any calculation based
on a 100 ml standard flask should not be given to more than four significant figures. To
quote an answer to six or seven significant figures (e.g. by taking answers directly from a
calculator) is to imply a much greater degree of accuracy than the experimental procedure
warrants. However, to quote only two figures, in most cases, is to throw away some of the
information that the experiment has provided.
Note: The digit zero is a significant figure except when it is the first figure in the number.
In the numbers 1.2680 and 1.0062 the zeros are significant, but in the number
0.0025 the zeros are not significant figures. Thus, in the first two numbers we have
five significant figures and in the third only two significant figures.
3. When a number of measurements (n) of the same quantity (x) are made in an experiment,
there will usually be some scatter in the values obtained. For example, the enthalpy
change in a reaction may be measured as 55.8, 55.3 and 56.1 kJ mol-1 on three separate
occasions. The average, or mean, of these observations is generally a suitable estimate
of the actual enthalpy change and is given by
where ∑x is the sum of n observations of x.

xxii
In the above example
55.8 + 55.3+ 56.1

x= = 55.7 kJ mol−1
3
Note that there is no point indicating a result to more significant figures than the original
data (in this case the temperature used to derive the enthalpy change was measured to 3-
figure accuracy).
A measure of the confidence which can be placed in this experimental estimate of the
parameter x is conveniently given by the standard deviation, S, where
2
The symbol means “the sum of all values of” ( x – x ) . In the example
2 2 2
S=
(55.8 − 55.7) + (55.3− 55.7) + (56.1− 55.7)
(3-1)
= 0.4 (rounded to the same precision as x )
The value for the enthalpy change in the reaction may then be quoted as 55.7 ± 0.4 kJ/mol.
If the three readings were the same, for example 55.7, 55.7, and 55.7, this would suggest
that the measurement is 55.7 ± 0.05 kJ/mol or better.
a2b
4. In using a simple formula such as x = , the error in x is given by:
c
% error in x = 2 (% error in a) + % error in b + % error in c
For example,
VALUE ERROR % ERROR
a 0.72 ±0.01 1.4

b 1.8 ±0.2 11.1
c 300.5 ±0.5 0.2
0.003105 14.1
(i.e., 2 ´ 1.4 + 11.1 + 0.2 = 14.) Then 14.1% of 0.003105 is 0.000438 and hence, x =
0.0031 ± 0.0004 units.
For a formula x = y + z or x = y – z, the error in x is simply the error in y plus the error in
z. Thus if y = 5.76 ± 0.02 and z = 2.124 ± 0.01 then, x = y + z = 7.90 ± 0.03 and x = y – z
= 3.62 ± 0.03.
xxiii
5. In plotting a straight line of best fit, when theory predicts a direct relationship between the
plotted variables, perhaps the best method is to find the values of the slope and intercept
using the method of least squares. The method is outlined below. Although the method
looks difficult, it is actually very easy to obtain a least squares line of best fit.
If we have available a set of n experimental points for an expected linear relationship, then
the equation of the straight line of best fit may be written as
y = mx + c
where m is the slope (gradient) and c is the intercept on the y axis. That is, c is the value
of y at x = 0. From least squares theory it is found that
, where
and
As before, Sx means the “sum of all n values of x” and Sxy means “the sum of all n values
of x × y ”. The standard deviation in the gradient is given by
where E = yobs – ycalc
Note that E is simply the difference between the observed points, yobs, and those on the
straight line of best fit. An example best illustrates this method. Consider the following
graph of x versus y where the set of points have been obtained by experiment.
x 1.0 2.0 3.0 4.0

y 5.2 3.4 1.1 0.5
xxiv
For the above set of data:
n=4
x = 1.0 + 2.0 + 3.0 + 4.0 = 10.0
y = 5.2 + 3.4 + 1.1 + 0.5 = 10.2
(x)2 = (10.0)2 = 100.0
x2 = 1.02 + 2.02 + 3.02 + 4.02
= 1.0 + 4.0 + 9.0 + 16.0 = 30.0
xy = (1.0 ´ 5.2) + (2.0 ´ 3.4) + (3.0 ´ 1.1) + (4.0 ´ 0.5)
= 5.2 + 6.8 + 3.3 + 2.0 = 17.3
d = (4.0 ´ 30.0) – 100.0 = 120.0 – 100.0 = 20.0
(4.0 × 17.3) – (10.2 × 10.0)

Thus, m= = –1.64
20.0
10.2 – (–1.64 × 10.0)

and c= = 6.65
4
The equation to the straight line of best fit is therefore y = –1.64x + 6.65.
At x = 0, y = 6.65 and at y = 0, x = 4.05 (see graph).
The error associated with the gradient, Sm, may now be calculated:
x 1.0 2.0 3.0 4.0

yobs 5.2 3.4 1.1 0.5
ycalc 5.01 3.37 1.73 0.09
E 0.19 0.03 0.63 0.41
E2 0.036 0.001 0.397 0.168
E2 = 0.036 + 0.001 + 0.397 + 0.168 = 0.60
Thus,
(4 × 0.60)
Sm = = 0.24
(4 – 2) × 20.0
The gradient of the line of best fit is m = –1.64 ± 0.24

SECTION B: Experiments
EXPERIMENT 10
Spectrophotometric Determination of the Salicylic Acid Content
in Synthesized Aspirin
AIMS OF THE EXPERIMENT

The aim of this experiment is to determine the amount of salicylic acid present in an aspirin
sample using UV/VIS spectrophotometry. To develop skills in analytical chemistry.
SKILLS IN FOCUS
• Analytical chemistry using absorption and use of Beer’s Law, A = ecl
• Operation of a UV/VIS Spectrophotometer and the correct use and placement of
cuvettes
• Correct preparation of standard solutions - involving dispensing of solutions into
volumetric flasks and precise diluting to the mark.
• Correct use of a burette
• Generation of absorbance vs. concentration linear plot (calibration curve)
REMEMBER FOR WORKSHOP TESTS

• Stoichiometry / concepts such as mole, concentration dilution calculations etc…
• Complex formation – reaction of a metal ion with an organic ligand (salicylic acid)
RISK ASSESSMENT
Substances Salicylic acid 0.01M in ethanol in 1-5ml volumes, ferric nitrate

2.5% w/v in water in 0.2-2ml volumes, and ethanol (50ml).
Hazards Salicylic acid has a contact rating of 2.

Ferric nitrate has a body contact rating of 2 and a toxicity rating of 2.
Ethanol has a contact and toxicity rating of 2 and a flammability rating of 3.
Protection Read ALL safety warnings, on coded solutions and unknown solids.
Avoid contact with ferric nitrate and salicylic acid.
Safety glasses are required.
Disposable gloves provided.
1
INTRODUCTION
Since its market introduction under the trademark Aspirin® in the year 1899,
acetylsalicylic acid (ASA) has attained a leading position worldwide in the
nonprescription therapy of painful, inflammatory, and feverish states. Aspirin has
proven effective as a general pain reliever, and it is routinely used in a wide range of
pain indications, including headache, body and muscle ache, arthritis, and many more.
Today, Aspirin is also taken daily by millions of people for its antithrombotic effect.
Patients with a prior cardiovascular condition can benefit from the life-saving
preventative properties of acetylsalicylic acid.
acetylsalicylic acid – Aspirin®
By the late 1800s, salicylates had become the standard drug for the treatment of
arthritis. However, salicylates are very harsh and irritating to the stomach. Felix
Hoffman, setting out to create a less-irritating medicine, synthesized acetylsalicylic
acid.
The synthesis acetylsalicylic acid involves esterification of the hydroxyl group of
salicylic acid using either acetic acid or more commonly acetic anhydride in the
presence of a catalyst. The overall reaction is [Scheme 1]:
Scheme 1: Esterification of salicylic acid using acetic anhydride.
Few organic reactions go to completion or give quantitative yields of the intended

product. The crude aspirin that results is often contaminated with free (unreacted)
salicylic acid and requires a number of recrystallization steps to achieve the purity
required for human ingestion.
2
In this experiment, the amount of unreacted salicylic acid in an aspirin sample will be
determined colourimetrically using ferric ions (iron (III), Fe3+). Iron (III) ions reacts with
salicylic acid (due to the strong affinity of Fe(III) ions for the phenol functional group,
) to form a highly coloured, violet compound, called a coordination

complex, according to the following reaction:
A coordination complex is a compound that is characterized by the presence of a

central atom or cation bound to a number of molecules or anions (ligands). The lone
pairs on the ligands form a coordinate bond with the cation. In the above reaction
Fe3+ is the cation in the coordination complex and the water molecules and salicylic
acid are the ligands.
Many d-block (transition metal) compounds are intensely coloured, with the color of
the complex depending on which metals and ligands are present.
A substance appears colored because it absorbs light that corresponds to one or more
of the wavelengths in the visible region of the electromagnetic spectrum (400–700nm)
and transmits or reflects the other wavelengths. A substance only absorbs light of
specific wavelengths because the electronic levels inside molecules are quantized,
meaning that the absorption of radiation (i.e. light) can occur only at values
corresponding to the energies required to promote electrons from one level to others.
The complex formed between Fe3+ ion and salicylic acid is violet (blue-purple) in colour,
which allows its visual detection. The intensity of the observed color is proportional to
the complex’s concentration. This concentration can be determined by
spectrophotometry, where the absorbance of the complex in the visible region is
measured at a wavelength of 540 nm.
3
The Beer–Lambert law states that the amount of light absorbed (A) by a substance
(solute) in a transparent solvent is proportional to the number of absorbing molecules
in the light path. That is, there is a linear relationship between absorbance (A) and
concentration (C) given by,
A = εbC
where:
A = absorbance
ε = molar absorptivity
b = cell (path) length (in cm)
C = sample (absorbent) concentration (in mol/L)
The Beer-Lambert law applies when the concentration of the absorbing species is
present at concentrations below 0.01 M and monochromatic (from Greek for one
colour) or single wavelength light is being used. Under these conditions a linear
relationship exists between the concentration of the species and its absorbance.
Typical of a linear Beer’s law plot
Measuring the absorbance of a range of known molar concentrations at the desired

wavelength enables the construction of a plot of absorbance versus concentration.
Such a plot is called a standard curve or a calibration curve (it should be a straight
line). The molar absorptivity, ε, can be determined from a calibration curve plot as
being the slope (gradient) of the straight line.
4
In this experiment, the amount of salicylic acid present in the aspirin sample will be
determined using spectrophotometry. Salicylic acid does not absorb light in the visible
region of the spectrum, however, the highly coloured, violet complex it forms with Fe3+
does. A spectrophotometer will be used to measure the amount of light absorbed at
540 nm. The intensity of the colour is directly related to the concentration of the
coloured complex.
A calibration curve will be constructed from the net absorbance measurement of the
violet coloured iron(III) complex produced when different salicylic acid concentrations
(including zero concentration) are mixed with ferric nitrate (Fe(NO3)3). The zero
concentration solution is called a blank and consists of a mixture of all the reagents
and solvents used except the salicylic acid. Its absorbance value is subtracted from
every other absorbance value to give the net absorbance due only to the intensity of
the coloured iron (III) complex in the standards and the aspirin sample. The
constructed calibration curve is used to determine the salicylic concentration in a
sample of synthesized aspirin. Further calculation will provide the percentage of
salicylic acid present in the aspirin.
PROCEDURE PART A - Preparation of salicylic acid standards
(i) Supply of Stock Solutions
Near your bench, four work stations have been set up with a 10 mL and 25
mL burette each containing:
0.01 M Salicylic Acid Solution (25 mL burette)
2.5% w/v Ferric Nitrate Solution (10 mL burette)
(ii) Preparation of the salicylic acid standard solutions
(1) Each student is supplied with 7 volumetric flasks in a plastic container.

Students use this container to carry their flasks to the burette stations and
spectrophotometers to avoid any breakage.
(2) A 25 ml burette with the freshly prepared 0.01M salicylic acid solution is
supplied on the bench.
(3) Dispense the appropriate volume of 0.01M salicylic acid solution into each
volumetric flask as indicated in Table 1.
(4) The 2.5% w/v ferric nitrate (Fe(NO3)3) stock solution is provided in the 10 ml
burette. Dispense the appropriate volume of ferric nitrate solution into the
5
volumetric flasks as indicated in Table 1. Note the solution should be violet
in colour after both the salicylic acid and ferric nitrate solutions are
combined.
(5) Using a 10ml measuring cylinder, add 5 ml of ethanol to volumetric flask No.1.
TABLE 1: Standard Solutions Preparation
1 2 3 4 5 6
Standard Number
(Blank)
Salicylic acid (0.01

M) 0 0.5 ml 1 ml 2ml 3 ml 4 ml
Fe(NO3)3 (aq) 2 ml 0.2 ml 0.4 ml 0.8 ml 1.2 ml 1.6 ml
Ethanol 5 ml 0 0 0 0 0
Salicylic acid
concentration
(mol/L)
(6) With a clean pipette, make up to the mark on each volumetric flask with distilled
water.
(7) Stopper each flask well (CHECK THAT THE STOPPER SIZE IS CORRECT
FOR THE GROUND GLASS NECK OF EACH VOLUMETRIC FLASK).
(8) Invert the flask, several times, to obtain a well-mixed, homogeneous solution.
(9) Using n = C x V, calculate the salicylic acid concentration in each of the

volumetric flasks. CHECK YOUR ANSWERS WITH YOUR
DEMONSTRATOR. Use the Calculations page in the Report as a guide
and enter each standard’s concentration in the Table of Results.
PROCEDURE–PART B Preparation of the aspirin solution (make up this

solution at latest possible moment, weigh out the mass early)
(1) Weigh accurately 0.2 g of supplied aspirin onto a pre-weighed weighing jar
and record the weight, in Step 7, on your report sheet.
(2) Use a small funnel to transfer the aspirin into a 50 ml volumetric flask.
6
(3) Rinse the weighing jar and the funnel with 5 ml of ethanol into the volumetric
flask.
(4) Stopper the volumetric flask and gently shake until the aspirin is completely
dissolved- this may take a few minutes. If the aspirin is not completely
dissolved after five minutes, add a further 2 ml of ethanol and continue gentle
shaking until it is dissolved.
(5) Add 2 ml of Fe(NO3)3 to the volumetric flask from the ferric nitrate burette
and swirl to mix.
(6) With a pipette, make up to the mark with distilled water. Stopper and invert the
flask several times to obtain a homogenous mix.
PROCEDURE - PART C Measuring the absorbance of the standard solutions
The VWR UV-1600RC Spectrophotometer will have been switched on before

the lab session and left to warm up.
The demonstrator will explain the use of the spectrophotometer.
(1) Check that the spectrophotometer is set at 540 nm.
(2) Using a plastic disposable pipette, rinse the cell (cuvette) by filling it with
your first standard solution (labelled flask 1, BLANK) and tipping the cell
contents into a 500 ml beaker.
(3) Refill the cell with the same standard solution (flask 1) and wipe the clear
sides of the cell with a tissue.
(4) Place the cell in the spectrophotometer with its clear sides in the direction of
the light path in the cell holder and close the sample compartment. (For
BLANK only, leave this cuvette in cell holder until measurements are
complete).
(5) Zero the instrument by recording (zeroing) the absorbance of the BLANK
(flask 1) in the Table of Results in your report book. Press the zero button on
the spectrophotometer to zero the blank solution.
(6) Repeat steps 2-4 with each standard solution in turn (flasks 2, 3, 4, 5 and 6)
but now do not zero, instead record the absorbances. Clean cell twice with
each new solution and then finally fill 2/3 of the cell before recording
absorbance.
7
(7) After recording the absorbance of your last standard (flask 6), remove the cell
from the spectrophotometer and empty it into the 500 ml beaker. Wash the cell
three (3) times with distilled water from a wash bottle, each time emptying the
cell into the waste beaker.
PROCEDURE – PART D Measuring absorbance of the aspirin solution
(1) Using a clean plastic pipette, rinse the cell by filling it with the aspirin
solution, tipping the cell contents into a 500 ml beaker.
(2) Refill the cell with aspirin solution and wipe the clear sides of the cell with a
tissue.
(3) Place the cell in the spectrophotometer with its clear sides in the direction of
the light path and close the sample compartment.
(4) Record the absorbance of the aspirin sample in the Table of Results in you
report book. (If the net absorbance value of this solution is higher than that of
standard 6, the aspirin sample should be diluted by a factor of 2 using distilled
water (see step 5).
(5) IF you need to dilute your solution, this can be done by placing put 25 ml of
the aspirin solution in a clean 50 ml volumetric flask and filling to the mark with
distilled water. Stopper and mix well. Wash the cell with distilled water three
(3) times. Repeat Steps 1-4 to measure the absorbance of the diluted sample.
(6) Open the sample compartment, remove the cell and wash it three times with
distilled water.
CALCULATIONS:
Determination of salicylic acid concentration in aspirin

(1) Using n = C x V, calculate the salicylic acid concentration in each of the
volumetric flasks. CHECK YOUR ANSWERS WITH YOUR DEMONSTRATOR.
Use the Calculations page in the Report as a guide and enter each
standard’s concentration in the Table of Results.
(2) Use the net absorbance values and salicylic acid concentrations for the
standards from your Table of Results, to construct a calibration curve on the
supplied grid, by plotting net absorbance values on the vertical axis and
concentration on the horizontal axis. Ensure that you use the appropriate scale
to accommodate your data points.
(3) Draw a line of best fit from the origin of the graph to join the data points.
8
(4) Using the net absorbance value for the aspirin sample, determine the
concentration of salicylic acid present in the sample by reading the
corresponding value off your graph. (If you had to dilute the aspirin sample
then the concentration determined from the calibration curve has to be
multiplied by the dilution factor e.g. x2 if the original sample was diluted two
times).
(5) Use n = C x V to determine the number of mole of salicylic acid present in the
50ml aspirin solution.
(6) If the molecular weight of salicylic acid is 138 g mol-1, calculate the number of
gram of salicylic acid present in the 50 ml aspirin solution.
(7) Using the weight of aspirin used to prepare the aspirin solution, calculate the
percentage weight of salicylic acid in the aspirin sample.
CLEANUP:
1. Put on a pair of gloves.

2. Tip the contents of the volumetric flasks into the heavy metal waste container
in the fume cupboard.
3. Rinse flasks with the acid wash dispensers in the fume cupboard
4. Take flasks to sink and wash with detergent and finally with distilled water
5. Ensure that you have wiped down your bench area before you sign the
demonstrator's Sign Out Sheet.
MARKING SCHEME /20

Prelab receipt 4
Calibration Curve
Correctly labelled axes 1
Correctly added data points 1
Line of best-fit 2
Calculations
Standard salicylic acid concentrations 2
Calculation of aspirin sample salicylic acid concentration 3
Calculation of mass of salicylic acid 2
Calculation of % mass of salicylic acid in aspirin 2
Questions (1 mark each) 3
9
Blank Page
10
NAME DATE
Student No: LAB DAY + GROUP ___
EXPERIMENT 10: Report Sheet

/20
SPECTROPHOTOMETRIC DETERMINATION OF SALICYLIC ACID
CONTENT IN SYNTHESISED ASPIRIN.
Prelab receipt (4 marks)
CALCULATIONS
1. Calculate the concentration of salicylic acid in mol/L in each of the standard

solutions and enter each concentration in the Table of Results. (2 marks)
Standard 1: n = CxV = mole in 50 mL
\ C (in 50 mL volumetric flask) = mol/L

=
11
NAME DATE
TABLE of RESULTS
Absorbance of Salicylic Acid Solutions (1 mark)
Aspirin Diluted
Standard 1 sample aspirin
2 3 4 5 6
Number (Blank) sample
Salicylic acid
concentration
(mol/L)
Absorbance 0.00
(540 nm)
2. Prepare a calibration curve for salicylic acid by plotting the net absorbance of the
standards (y axis) against the concentrations (x axis) of the standard salicylic acid
solutions. Ensure that you use the appropriate scale to accommodate your data
points.
3. Draw a line of best fit from the origin of the graph through the remaining data points.
12
NAME DATE
Plot of Absorbance versus Concentration of Salicylic Acid (4 marks)

Absorbance
Concentration (mol/L)
13
NAME DATE
CALCULATIONS
(6 marks)
4. Using the net absorbance value for the aspirin sample, determine the concentration
of salicylic acid in the sample by reading the corresponding value off your graph.
Net Absorbance for Aspirin Sample =
Concentration (read off graph) of Salicylic Acid = mol/L

(in 50 mL sample)
5. Mole of Salicylic Acid in 50 mL Sample, n = CxV = mole
6. Molecular Weight of Salicylic Acid is 138 g/mol
Therefore, gram of Salicylic acid in 50 mL sample g

=
(using n=m/Mw)
7. Weight of Aspirin Sample = g
Therefore,
% Weight of Salicylic Acid in Aspirin Sample = %w/w
14
NAME DATE
QUESTIONS (3 marks)
1. What is the purpose of the blank in this analysis?
2. Since Beer’s Law is A = ε b C, use the net absorbance value for the aspirin
solution and its concentration, to calculate the molar absorptivity ε. What are
its units? In this experiment, the analysis was performed at 540nm. What is an
absorption spectrum and how does it relate to the wavelength used?
3. Aspirin tablets are free of impurities. What technique would be used to remove
salicylic acid from the aspirin?
15
NAME DATE
Blank Page
16
EXPERIMENT 11
Acid- Base Indicators
AIM OF THE EXPERIMENT

The aim of this experiment is to determine endpoints using indicators or using a pH meter.
SKILLS IN FOCUS
• Correct use of a burette
• Determining the best choice of indicator for given acid/base reaction
• Use of a pH meter
• Calibration of a pH meter using standard buffers
• Use of analytical dispensers
• Use of computer to analyze data and presentation of data in graphical form for
interpretation

• Difference between a strong acid/base
• Calculation of pH
• What a buffer solution is and how to determine the pH of a buffer solution
• Ability to predict graphical relationships from mathematical relationships
• Understanding what happens to an acid/base indicator in the titration
• Hendersen-Hasselbalch equation that relates pH to concentrations of acid and its
conjugate base:
RISK ASSESSMENT
Substances: NaOH, HCl, CH3COOH (all 0.1 M), indicators

You are dealing with coded materials.
Hazards: The solutions involved have a maximum body contact rating of 2.
Protection: Read ALL safety warnings on coded solutions and unknown solids.
Disposable plastic gloves are recommended. Safety glasses are
required.
17
THEORY
The pH of the equivalence point in acid-base titrations depends on the relative strengths of the
acid and base. For a strong acid-strong base titration the pH at the equivalence point is 7.0. If
either the acid or the base is weak, the pH at equivalence will not be 7.0 due to hydrolysis of
the salt. If a weak acid is titrated with a strong base, the equivalence point pH will occur on the
alkaline side of neutrality (pH > 7), whereas a strong acid titrated with a weak base will have
an acidic (pH < 7) equivalence point.
An indicator is used in titrations to approximate the equivalence point. Note that the
equivalence point and endpoint are different. The equivalence point occurs when an equal
number of moles of each species are present, whereas the endpoint is the point at which the
observed indicator colour change takes place. A well chosen indicator will change colour very
close to the pH of the equivalence point of the titration - the closer the endpoint is to the
equivalence point, the better the indicator is for that specific titration.
Indicators are substances (generally weak organic acids) that change colour according to the
pH of the solution. Thus, if we know the approximate pH at the equivalence point of a titration
we can select a suitable indicator which will change colour at that pH. An indicator may be
described by the equilibrium reaction,
HIn H+ + In– (1)
where the dissociation constant, Ka(In), is given by
[H + ] [In – ]
K a(In) = (2)
[HIn]
This can be rearranged to give
(3)
so that
(4)
At the endpoint, the concentrations of the two different coloured forms of the indicator (HIn and
In-) will be approximately equal, so that from equation (4), pH = pKa(In). Thus, for a given
titration, the best indicator will be one with a pKa(In) close to the equivalence point pH.
18
The properties of some useful indicators are given in the following table:
Colour
Indicator Acid Alkaline Approximate pKa(In)

(HIn) (In-) pH range
Methyl Violet yellow blue 0.0 - 1.6

Thymol Blue red yellow 1.2 - 2.8 1.7
Methyl Orange red yellow 3.1 - 4.4 3.7
Bromophenol Blue yellow blue 2.9 - 4.6 4.0
Methyl Red red yellow 4.2 - 6.3 5.1
Bromocresol Purple yellow purple 5.2 - 6.8 6.3
Bromothymol Blue yellow blue 6.0 - 7.6 7.0
Phenol Red yellow red 6.8 - 8.4 7.9
Thymol Blue yellow blue 8.0 - 9.6 8.9
Phenolphthalein colourless red 8.3 - 10.0 9.4
A more sensitive method of determining the pH of a solution, and hence of detecting the
equivalence point in an acid-base titration, is based on the fact that the electric potentials of
certain electrodes depend upon the hydrogen ion concentration of the solution in which they
are immersed. The most convenient of these electrodes is the glass electrode. This consists
of a glass tube terminating in a thin-walled glass bulb enclosing a dilute solution of potassium
chloride (KCl) and acetic acid (CH3COOH) in which is immersed a platinum wire coated with
Ag/AgCl. The potential of this electrode, when referred to a standard electrode (usually
saturated calomel or silver/silver chloride) can be directly related to pH. Thus, it is possible to
monitor the pH throughout a given acid-base titration.
PROCEDURE (Do Part B first!)
Solutions of 0.1 M acetic acid (CH3COOH), 0.1 M hydrochloric acid (HCl) and approximately
0.1 M standardised sodium hydroxide (NaOH) are provided.
When reading the burette, use the correct number of significant figures.
Part A. Indicators and Endpoints.
(1) After completing Part B, remove the magnetic stirrer and place a white tile on the stand.
(2) Dispense a 20 ml aliquot of the CH3COOH solution into a clean 250 ml conical flask.
(3) Titrate above (1) with NaOH, using phenolphthalein as the indicator. No more than 4
drops of indicator should be added. Carefully add the NaOH until localized colour
changes indicate the approaching endpoint. Add further NaOH drop-wise until a just-
detectable permanent colour change is observed.
19
(4) Record the volume of the titre. Keep this first titration solution as a reference for
subsequent titrations.
(5) Repeat steps (1-3) until you obtain three concordant titres (± 0.1 ml).
(6) Repeat steps 1-4 using methyl orange as the indicator. It may be necessary to use 5 to
6 drops of indicator to give a convincing colour change.
Part B. The pH Meter and Equivalence Points.
Note: Great care must be exercised when handling the glass-calomel electrode as it is
extremely fragile. Ensure that the electrode is always sitting in water - at no time should
it be allowed to dry out. The pH electrode will need to be calibrated at the start of the
experiment.
Calibration of pH Electrode using Standard Buffers.
1. Remove the pH electrode from distilled water beaker and thoroughly rinse several
times with distilled water.
2. Switch on pH meter.
3. Carefully dry the electrode with a Kimwipe. Place the electrode in the flask labelled Buffer
Solution No 1 pH = 4.0 and gently stirred solution. Wait a few minutes until pH has
become constant and press calibration button and hold it down until the meter said OK
(a few seconds).
4. Repeat rinsing and drying of the electrode and then place pH electrode in flask labelled
Buffer Solution No 2 pH = 9.2. Wait a few minutes until reading has become constant and
then hold calibration button until OK appears.
5. Repeat rinsing and drying of pH electrode and placed it back in the calibration solution
pH = 4.0. The pH reading should be 4.00 ±.02 and after rinsing and drying again the
electrode is readily to use.
NOTE: If the electrode does not read in the range 3.98-4.02 the entire procedure above
must be repeated until it does.
The apparatus consists of a pH meter with a glass-calomel electrode. The electrode may be
left in the titration vessel during the experiment. However, it must be removed immediately the
titration is complete, rinsed thoroughly with distilled water and stored in a flask labelled distilled
water. If the electrode is still reads above 7.0, place the electrode in a flask containing a small
amount of Buffer No 1 (pH = 4). Once the pH reading is below 5 remove electrode, rinsed
again with distilled water. If pH is still not below 7 in the distilled water, repeat procedure (see
demonstrator). The electrode must not be allowed to dry out. The demonstrator will explain
the operation of the pH meter.
20
Determine the Equivalence Point with the pH Meter
(1) The pH meter is used to measure the pH throughout the course of the titration of 0.1 M
acetic acid with 0.1 M NaOH.
(2) Dispense a 20 ml aliquot of the acetic acid solution into a clean 100 mL conical flask
labelled pH titration. Add a stir bar (ask your demonstrator).
(3) Carefully rinse the glass electrode with distilled water and then immerse it in the titration
vessel. Add sufficient distilled water to cover the electrode. Makes sure the stir bar does
not hit the electrode. Why doesn't this addition of water affect the titration results?
(4) Measure the pH of the solution for a series of volumes of added NaOH, carefully stirring
the solution after each addition.
(5) When approaching the equivalence point it is essential that the solution is thoroughly
mixed and that you allow 10 to 15 seconds for the pH reading to stabilize due to the
fluctuating needle. As a guide, NaOH may be added in the following way:
(i). 2 ml additions until 16 ml has been added.

(ii). Two or three additions of 0.5 ml.
(iii). 0.2 ml additions until the pH is approximately 11.
(iv). 2 ml additions until approximately 40 ml of NaOH has been added.
(6) A computer will be used to prepare a graph of pH against volume of NaOH added. Your
demonstrator will explain the operation of the computer program.
(7) Using the pH meter as described above follow the course of the titration of 0.1 M HCl
with 0.1 M NaOH, again plotting the titration curve using the computer.
(8) Clean-up:
a. Ask your demonstrator to collect the stir bar.

b. Make sure that the glass electrode is rinsed and left immersed in distilled water.
c. Burettes need to be rinsed with distilled water, inverted and left with taps open.
d. Place a white tile back in the drawer and place a magnetic stirrer back on the
stand.
e. All liquid waste can be discarded down the sink.
f. Wash all glassware with warm water and detergent and then finally with distilled
water several times.
g. Glassware must be returned to the correct drawers. Sign out with your
demonstrator.
21
GRAPHICAL ANALYSIS
(G1) Identify and mark the equivalence point on each plotted graph. Record the pH and the
volume of NaOH added at the equivalence point.
(G2) On the CH3COOH v NaOH plot, mark the volume of NaOH added at the endpoint of your
titrations with (i) phenolphthalein and (ii) methyl orange in Part A. Record the
corresponding pH at which the indicator changes colour (the endpoint).
(G3) On the HCl curve, mark the point corresponding to the pH determined in step (G2) for
each indicator. Record the volume of NaOH added to achieve this pH.
MARKING SCHEME /20

Prelab Receipt 4
Part A
Concordant titrations 5
Phenolphthalein (±0.1ml = 2.5 marks, ±0.3ml = 1.5 marks, ±0.5ml = 0.5 mark, >1.0 ml = 0 marks)
Methyl orange (±0.2ml = 2.5 marks, ±0.4ml = 2.5 marks, ±0.6ml = 0.5 mark, >1.0 ml = 0 marks)
Part B (only complete one titration)

Plots (2.5 marks each) 5
Including marking equivalence points and indicator endpoints
Graph analysis 3
Questions (1 mark each) 3
22
NAME DATE

/20
Acid-Base Indicators
RESULTS
Part A. Indicators and Endpoints (5 marks)
(i) Phenolphthalein indicator: titration of .......... M CH3COOH (20 mL aliquots)

with .......... M NaOH.
Titration number 1 2 3 4
Burette reading for indicator

just changing colour /mL
Initial burette reading /mL
NaOH titre /mL
A1 Average titre = ....….…...... ± ....….…...... mL
(ii) Methyl Orange indicator: titration of .......... M CH3COOH (20 mL aliquots)

with .......... M NaOH.
Titration number 1 2 3 4
Burette reading for indicator

just changing colour /mL
Initial burette reading /mL
NaOH titre /mL
A2 Average titre = ....….…...... ± ....….…...... mL
23
NAME DATE
Part B. pH Meter and Endpoints (5 marks)
(i) Titration of ........... M CH3COOH (20 mL aliquots) with ........... M NaOH.
Burette Vol. NaOH Burette Vol. NaOH

pH pH
/ mL / mL / mL / mL
24
NAME DATE
(ii) Titration of ............ M HCl (20 mL aliquots) with ............ M NaOH.
Burette Vol. NaOH Burette Vol. NaOH

pH pH
/ mL / mL / mL / mL
25
NAME DATE
GRAPHICAL ANALYSIS (3 marks)
G1. pH meter equivalence points
At equivalence point pH Volume NaOH

added /mL
0.1 M CH3COOH + ……… M

NaOH
0.1 M HCl + ……… M NaOH
G2. For the titration between 0.1M CH3COOH and ..........M NaOH
At endpoint Volume NaOH pH

added /mL (from graph)
(Av. titre from Part A)
A1
Phenolphthalein indicator
A2
Methyl orange indicator
Mark these points on the plot of CH3COOH v NaOH.
G3. From the titration curve for 0.1M HCl with ..........M NaOH
pH at endpoint Volume NaOH

(from G2 added /mL
above) (from graph)
Phenolphthalein indicator
Methyl orange indicator
26
NAME DATE
QUESTIONS (3 marks)
l. Use your titration curve and analysis of results for the reaction between CH3COOH
and NaOH to answer the following:
(a) Which of the two indicators gives the better endpoint? Why?
(b) Could you use methyl violet as the indicator? Explain.
(c) Is the equivalence point at pH 7? Explain.
(d) Use the table of indicators to select the most suitable indicator for the titration,
giving a reason for your choice.
2. Use your titration curve and analysis of results for the reaction between HCl and
NaOH to answer the following:
(a) Which of the two indicators would you expect to give the better endpoint?
Explain why.
27
NAME DATE
(b) Is there a better indicator for the titration? Use the table of indicators and give
a reason for your choice.
(c) Is the equivalence point at pH 7? Explain.
3. Sketch the expected shape of a titration curve for the standardization of 0.1 M
NH3 with 0.1 M HCl, with volume of HCl added on the x-axis and pH on the y-
axis. Indicate the approximate pH at the start and end of the titration. Mark on
your curve the equivalence point and its approximate pH. Suggest a suitable
indicator for this titration, giving a reason for your choice.
28
EXPERIMENT 12
Effect of Temperature on Reaction Rate

The aim of this experiment is to determine the activation energy, Ea, (energy required
by reactants to transform into products) for the reaction of hydrogen peroxide (H2O2)
with iodide ion (I-).
SKILLS IN FOCUS
• Kinetics of a reaction can only be determined experimentally – you will complete an
example of this here.
• Accurately monitor the time it takes to complete a reaction.
• Use of analytical dispensers.
• Use of computer to analyze data and presentation of data in graphical form for
interpretation.
• Use of significant figures.
• Analysis of errors.

• First order kinetics
• The effect of rate given an increase in temperature (always increases rate)
• Ability to predict graphical relationships from mathematical relationships
• Activation Energy, Ea.
• A plot of ln k versus 1/T for any reaction would allow you to determine Ea, from the
gradient (m= -Ea/RT)
RISK ASSESSMENT
Substances: 0.06 M potassium iodide (KI), 0.03M sodium thiosulfate (Na2S2O3),

0.18 M sulfuric acid (H2SO4), 0.15M hydrogen peroxide (H2O2),
starch solution.
You will be dealing with coded materials.
Hazards: H2O2 has a toxicity and reactivity rating of 2 and a body contact rating of 3.
H2SO4 has a toxicity and chronic rating of 3 and a body contact rating of 4.
Disposable plastic gloves are recommended. Safety glasses are required.
Any body contact with chemicals should be washed with water.
29
THEORY
In acid solution, iodide ions are oxidized by hydrogen peroxide (H2O2) according to the
following stoichiometric equation
H2O2 + 2 I- + 2 H3O+ ® 4 H2O + I2 (1)
The rates of reaction at different temperatures can be compared by measuring the time
required for the production of the same pre-arranged quantity of iodine (I2). This is
achieved by adding a constant small amount of Na2S2O3 to each reaction mixture. The
S2O3 ion reacts very rapidly with the free iodine to form the tetrathionate ion,
S4O6 .
A small quantity of starch is also added. Starch forms an intensely coloured, blue
complex with iodine. Thus, when all of the thiosulfate has been used up, free iodine is
available to react with starch and form the blue starch/iodine complex. In this way,
each reaction can be followed to exactly the same stage.
The dependence of the reaction rate constant, k, on the temperature, T, is given by

the Arrhenius equation,
E
k = A exp(- a ) (2)
RT
Here Ea is the activation energy (energy required by reactants to transform into

products) and A the frequency factor (takes into account the number of successful
collisions). Taking the natural logarithm of both sides of Equation 2, we can rearrange
the equation into the form of a straight line (y = mx + c), it may be expressed as
Ea
ln k = - + ln A (3)
RT
where: ln k = y; ln A = constant, c
and 1/T = x (x = variable) and –Ea/R = m
The first-order rate law may be written as
–dc –dc
= kc or = kdt (4)
dt c
where c is the concentration of reactant. At time t = 0 then c = c0 and at time t, c = ct.

Integrating Equation 4, we get
and hence (5)
30
Provided the same original concentration is used and the reaction proceeds to the
same extent, -ln (ct/c0) is a constant and k is proportional to t –1. Substitution into
Equation (3) yields the following relationship
Ea
ln t = + constant (6)
RT
This may be compared to the form of a straight line (y = mx + c), where

a plot of ln t against T–1 will be a straight line with a slope of Ea/R.
In this experiment you will determine time, t, taken for the same reaction:
H2O2 + 2 I- + 2 H3O+ ® 4 H2O + I2
to go to completion at four different temperatures. Since it is the same reaction, you

can assume that Ea will be constant.
By plotting ln t versus 1/T – if you obtain a straight line you will:

§ confirm the relationship (6):
Ea
ln t = + constant
RT
§ confirm that the reaction was first-order (since this expression was originally
derived from the first-order rate law).
§ obtain the activation energy, Ea, for the reaction from the gradient (m = Ea/R)
of the straight line.
PROCEDURE
The following reagents are provided:

0.060 M KI 7% H2SO4 0.15 M H2O2
0.030 M Na2S2O3 1% Starch Solution
(1) Add precisely 90 mL of RO water using your 100 mL measuring cylinder into a
clean dry 250 mL conical flask.
31
(2) Add 15 ml of the potassium iodide solution using the dispenser, into the 250 ml
conical flask.
(3) Add 15 mL of the 7% sulfuric acid, H2SO4, to the conical flask.
(4) Add 1 mL of starch using a plastic 1 mL transfer pipette.
(5) Immerse a thermometer in this mixture. Cool the mixture in an ice-water bath,
stirring the liquid frequently swirling the flask until its temperature is stable
between 0°C and 1°C.
(6) Using a dispenser, add 4.5 ml of sodium thiosulfate (Na2S2O3) to the mixture.
(7) Record the temperature of the reactants before adding the Na2S2O3 and H2O2 to
within 0.1°C.
(8) Finally, transfer to the flask, from a dispenser, 3.0 ml of hydrogen peroxide
(H2O2), noting the time of the addition with the use of a stopwatch (may need help
from a fellow student with the stopwatch).
(9) With continual stirring, maintain the temperature of the reactants by adding ice or
warm water as necessary. The temperature should not change by more than 1°C
over the course of the experiment.
(10) Record the time when the solution turns distinctly blue. Note that reaction times
will vary from only a few minutes at 45°C to approximately 45 minutes at 0°C.
(11) Using the same quantities of reagents, carry out the reaction at slightly below
room temperature (about 15-18°C), 30°C and 45°C, taking care to stabilize the
temperature before adding the sodium thiosulfate and hydrogen peroxide.
(12) Suitable temperature control at the higher values may be achieved by using a
large plastic beaker as a water bath. Hot water from the tap should be sufficient,
with hotter water from the water urns being used to top up as required. The
temperature should be controlled to within 0.5°C and measured to within 0.1°C.
Because of the slow reaction rates at the lower temperatures it is possible to save
considerable time by following two reactions simultaneously.
Cleanup.
a. Return stopwatches and thermometers to demonstrator.
b. Decant waste down the sink.
c. Rinse all glassware in the end sinks with detergent and then with distilled water.
d. Return all glassware to the drawer even though they are wet.
32
CALCULATIONS
(1) Plot a graph of ln t against T-1.
(2) Using the method of least squares (see section 5 of “Estimation of Errors” in this
manual), obtain the line of best fit. It is important that all calculations are recorded
to at least 6 significant figures. Use scientific notation for numbers less than 1.
(3) From the slope and its standard deviation, calculate Ea and its error limits.
(4) A computer can be used to check your calculated values for m, c and Sm.
MARKING SCHEME /20

Prelab receipt 4
Completion of experiment 2
Results and calculations tables 1
Plot 2
Calculation of Ea 3
Calculation of errors 3
Questions 5
Q.1 2
Q.2 1
Q.3 2
33
Blank Page
34
NAME DATE

/20
Effect of Temperature on Reaction Rate
RESULTS (2 marks)
Temperature /°C Time / minutes : seconds
T initial T final T average t initial t final t elapsed
: : :
: : :
: : :
: : :
CALCULATIONS (1 mark)
T /°C T /K 1 t /min : sec t /sec ln t

/K–1
T
:
€ :
35
NAME DATE
Plot of ln(t) against 1/T (2 marks)
8.5
8.0
7.5
7.0
ln t 6.5
6.0
5.5
5.0
4.5
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 0.0037
1/T
36
NAME DATE
Manual Calculation of line of best fit (3 marks)
1
x= K y = ln t xy x2
T
∑x = ∑y = ∑xy = ∑x2 =
n =
(Σx)2 =
d = nΣx2 – (Σx)2 =
(nΣxy – ΣyΣx)
m = Computer m =_________
d
€
(Σy – mΣx)
c = Computer c =__________
n
Ea
m = \ Ea = J mol–1
R
€ Computer Ea = ______kJ mol-1

37
NAME DATE
Calculation of Error in Ea (3 marks)
Equation for line of best fit ( y = mx + c ) :
1
x=
T
yobs = (ln t)obs
€ ycalc = (ln t)calc
E = yobs – ycalc
E2
ΣE2 =
nΣE 2
Sm = =
(n – 2)d
€
Computer error in m =___________
Error in Ea =
Ea = ± J mol-1
= ± kJ mol-1
38
NAME DATE
QUESTIONS (5 marks)
1. Explain how temperature and concentration of reactants/products affects the rate

of reaction. You should consider collision theory (number and rate of collisions)
in your answer.
2. What fraction of the hydrogen peroxide added is reduced by the iodide ion when
the mixture turns blue?
Given: 2S2032- + I2 à S4062- + 2I-
3. Roughly sketch how [I– ] varies with time, both before and after the blue
colouration appears.
39
NAME DATE
Blank Page
40
EXPERIMENT 13
Preparation of Acetate Esters

The aim of this experiment is to synthesize an acetate ester by acid-catalyzed
esterification and then purify the product using a separating funnel and distillation.
SKILLS IN FOCUS
• Refluxing of a reaction
• Careful use of volatile chemicals and exothermic reactions
• Use of separating funnel for extraction
• Assembly and use of distillation glassware for the purification of liquids (exploiting
differences in boiling points (physical property).
• Determination of the yield in a synthetic reaction
• Safe use of chemicals

• Nucleophillic substitution
• Boiling point and when it occurs
• Separation of materials exploiting differences in physical properties (boiling
points, solubility, reactions, etc..)
• The preparation of acetate esters using acetic anhydride and various alcohols
RISK ASSESSMENT
Substances: Approx. 6 g of alcohol (1-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-octanol)

4 drops concentrated sulfuric acid (H2SO4)
6.0 ml acetic anhydride
20 ml saturated sodium chloride (NaCl) solution, 30 ml 10% sodium bicarbonate,
calcium chloride
Hazards: 1-butanol has a contact rating of 3, and a toxicity and flammability rating of 2. 1-
pentanol, 2-pentanol and hexanol have a flammability, toxicity, contact and chronic
rating of 2. 1-octanol has a contact and toxicity rating of 2.
Concentrated sulfuric acid has a contact and chronic rating of 4, a toxicity rating of 3
and a reactivity rating of 2.
Acetic anhydride has a flammability and contact rating of 3 and a toxicity rating of 2.
Calcium chloride has a toxicity and contact rating of 2.
41
RATINGS: 0 = Nil, 1 = Low, 2 = Moderate, 3 = High, 4 = Extreme
Safety glasses are required. Avoid contact with concentrated acid and acetic
anhydride – any spillages or contact should be treated with much cold water.
Disposable gloves are available.
Risk: C2
INTRODUCTION
Esters are a class of compounds widely distributed in nature. The simple esters tend
to have pleasant odours. In many cases, although not exclusively so, the characteristic
flavours and fragrances of fruits and flowers are due to compounds with the ester
functional group. Food and beverage manufacturers are thoroughly familiar with these
esters and often use them as additives to improve the flavour of a dessert or beverage.
Many times, such compounds are not even the main flavour or odour components, as
in the case of the ‘juicy fruit’ principle, isopentenyl acetate. An instant pudding that has
‘rum’ flavour may never have seen its alcoholic namesake – this flavour can be
duplicated by a mixture of ethyl formate, isobutyl propionate along with other minor
components. The natural flavour and odour are not exactly duplicated, but this is not
always necessary.
O
O
O
O
Isopentenyl acetate Isobutyl proionate
Juicy fruit rum
In the laboratory, esters can be made by a number of routes. One method is to react
an acid with an alcohol,
carboxylic acid + alcohol à ester + H2O
The reverse reaction is also possible, in that the ester can be split into the carboxylic
acid and alcohol by adding water (hydrolysis).
ester + H2O à carboxylic acid + alcohol
Example:
CH 3CH 2CH 2COOCH 3 + H 2O → CH 3CH 2CH 2COOH + CH 3OH
methyl butanoate butanoic acid methanol
42
This process enables the nomenclature of esters to be understood more easily. For
example, it should be clear that the methyl butanoate name originates from the
butanoic acid (acid) and methanol (alcohol). The suffix for naming esters is “oate”.
In this experiment, you will carry out the acid-catalysed alcoholysis of acetic anhydride
to prepare one of a variety of possible acetates (the general name for an ester of acetic
acid) – a selection of primary and secondary alcohols is available.
O H+ O OH
+ ROH +
R
O O O O
Alcohol M.W. Densityb.p. of Acetate Ester °C

1-Butanol 74 0.810 126
1-Pentanol 88 0.814 149
1-Hexanol 102 0.814 171
Acetic anhydride can be an eye irritant. This may be exacerbated by its

decomposition to acetic acid by reaction with water. Ensure that you measure
out the required quantity of acetic anhydride into a clean, DRY flask.
The reaction is exothermic (will generate significant heat). The addition of the
acetic anhydride MUST be very slow and the contents MUST be swirled
thoroughly, between each addition of anhydride, to ensure that the reaction has
been completed. If the reaction is not fully completed before reflux is
commenced, the exothermic nature of this experiment will cause to contents of
the flask to erupt out of the top of the condensor under reflux. Before starting
the addition of acetic anhydride, ensure you have checked that each quickfit
apparatus has been set up and clamped properly.
The reaction is too slow at room temperature and the mixture needs to be heated. A
special apparatus setup, as shown in the diagram below (step 4), is required for reflux,
a procedure that allows a solution in a volatile solvent to be boiled without loss of the
solvent.
PROCEDURE
Note: Step 1-10 must be carrying out in the fume cupboard. The reagent tray
must be removed from the fume cupboard before using micro Bunsen burner
(ask demonstrator to do this step). No acetone wash bottle should be left in the
fume cupboard.
(1) Pour 6.5 ml of the selected alcohol into a 50 ml pear-shaped flask.
43
(2) Add 4 drops of conc. sulfuric acid and mix the liquids thoroughly.
(3) Add a few boiling chips to pear-shaped flask and a magnetic stirrer bar (ask
demonstrator).
(4) Set up the apparatus for heating under reflux (as shown below) but do not heat
the flask yet.
OPEN
Coolant
water out
Coolant
water in
Clamp here
Stirrer
Lab
Jack
(5) Turn magnetic stirrer on. Measure out 6 mL of acetic anhydride in a dry
measuring cylinder. Add acetic anhydride (6.0 ml) down the top of the condenser
in 1 ml portions over a period of approximately 10 minutes. The reaction is
exothermic (will generate significant heat). The contents MUST be stirred
thoroughly to ensure that the reaction has been completed. If the reaction
is not fully completed before reflux is commenced, the exothermic nature
of this experiment can be explosive under reflux.
(6) Once addition of acetic anhydride is complete, check the temperature of

the pear-shaped flask. If very hot, wait at least 5 minutes for flask to cool
slightly or wait unit the temperature has reached a maximum heat and then starts
to decrease BEFORE heating with the micro Bunsen burner.
(7) Remove magnetic stirrer bar from flask (see demonstrator). Remove magnetic
stirrer and lab jack.
(8) Heat the flask containing the solution with the micro Bunsen burner so that it
refluxes for 10 minutes.
(9) With the condenser still connected to the flask, cool the solution in the pear-
shaped flask by immersing it in a beaker of ice/water. Leave all glassware
connected; simply hold a beaker of ice/water up and immerse the flask for
approximately 5 minutes.
(10) Dismantle the condenser and pour the cooled solution into a separating funnel.
44
(11) Wash with 20 ml of saturated NaCl, allow layers to separate and run off the
aqueous layer (lower layer) into a 250 ml conical flask (all further aqueous
washings waste will be collected in this flask). GENTLY swirl AND practise the
release of pressure by inverting the separating funnel (stopper in place and
held by the palm of your hand), remove the stopper and carefully opening
the tap then drain the aqueous layer into waste conical.
(12) Next, drain the organic layer into a clean 100 mL conical and add 15 ml of 10%
sodium bicarbonate solution. Washing with bicarbonate produces CO2 gas
so, REMEMBER to FIRST swirl the contents gently in the conical flask after
the addition of the bicarbonate solution until CO2 production has ceased.
Pour the conical flask contents back into the separating funnel in the top
of the separating funnel and allow layers to separate. Carefully opening the
tap drain the aqueous layer into waste conical. Add 15 mL of the 10%
NaHCO3 wash to the separating funnel, again carefully undertaking the swirling
and drain process (collect all aqueous washings waste in the conical flask and
dispose of according to demonstrator’s instructions).
(13) Run the organic layer into a small conical flask and dry with calcium chloride.
(14) Decant the liquid into a 25 ml round-bottomed flask, add a few boiling granules,
and set up for distillation.
(15) Weigh (record weight on report sheet) a clean and dry small conical flask.
(16) Distil the crude product. When the temperature is approx. 5 oC below the quoted
boiling point, replace your collecting flask with your clean pre-weighed small
conical flask and collect the distilled product until the quoted boiling point is
exceeded or JUST BEFORE there is no liquid left in the round-bottomed flask
(leave a small amount!). See Appendix for Distillation/reflux glassware set
up.
(17) Record the weight and boiling point (b.p.) of the purified ester. (check
thermometer temp when distillate is coming off).
(18) Calculate the yield.
45
CLEANUP
• Place all aqueous and organic waste in the suitably labelled bottles in the fume
cupboard, as instructed by your demonstrator.
• Rinse all glassware with acetone into acetone residue bottle in fume cupboard.
• Wash all glassware with detergent and hot water. Rinse glassware with acetone
into acetone waste bottle on sink.
• Leave glassware air dry for a few minutes and replace in YOUR CORRECT
DRAWERS. Sign the “Sign-Off” sheet when your demonstrator is satisfied with
your cleanup.
Sign the “Sign-Off” sheet when your demonstrator is satisfied with your cleanup.
MARKING SCHEME /20

Prelab Receipt 4
Completion of Experiment 2
Boiling point 4 (4 marks b.p. 128-132; 3 marks b.p. <128-124;
1.5 marks b.p. <124)
% Yield Calculations 2 (1 mark each)
Questions (2 marks each) 6
46
NAME DATE

/20
Preparation of Acetate Esters
Completion of Experiment (2 marks)
RESULTS (4 marks)
Alcohol used: ______________
Structural formula of alcohol used: __________________________________
Volume of Alcohol used: _________mL
\Weight of Alcohol used: ________________________g
Weight of Ester product: _________g
Structural formula of Ester product: _________________________________
Boiling Point Range of Ester _____ - _____ °C
How does this compare with the expected value?
CALCULATION OF PERCENTAGE YIELD

(4 marks)
R-OH + (CH3CO)2O ® CH3COOR + CH3CO2H

1 mol 1 mol ® 1 mol
M.W. ______ __
(molecular weight) (chosen alcohol) (acetic anhydride) (ester)
47
NAME DATE
Calculate the no. of mole of alcohol and acetic anhydride used and determine
which of the two reagents is the limiting reactant
Mole of alcohol =_________________________ mol (from weight or volume of

alcohol used)
Density of acetic anhydride = 1.08 g/mL
Weight of acetic anhydride = volume ´ density
=________ ´ ________ = g
Moles of acetic anhydride = mol
Which of the two reagents is the limiting reactant?________________________
Therefore, yield is determined by the initial amount of______________________
actual yield
% Yield of Ester = theoretical yield × 100%
actual yield is the actual weight of ester obtained
theoretical yield is the theoretical weight of ester calculated from the mole of limiting reactant
= ´ 100 %
= %
48
NAME DATE
QUESTIONS (6 marks)
(1) What would be the products from the hydrolysis of your ester?
(2) Esters generally have lower melting or boiling points than do the parent carboxylic
acids. Why is this?
(3) Describe the difference between reflux and distillation.
49
NAME DATE
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50
EXPERIMENT 14
Determination of Calcium and Magnesium Complexometric
Titrations with EDTA
The aim of this experiment is to use volumetric analysis to standardize an EDTA

solution and then use this solution to determine the “hardness” of a water sample.
SKILLS IN FOCUS
• Volumetric analysis using burette
• Obtaining concordant titres
• Stoichiometry

• Definition of a coordination complex and the ability to represent these pictorially
• Understanding of how EDTA binds and solubilizes metal ions.
• Use of EDTA for analysis of metal ions
• Definition of denticity
RISK ASSESSMENT
Substances: 10ml concentrated hydrochloric acid (HCl), EDTA (0.1M), inorganic salts
Hazards: Eriochrome T has a chronic rating of 3 and EDTA and zinc have chronic
ratings of 2.
Conc. HCl has a contact rating of 4.
Disposable plastic gloves are available. Safety glasses are required.
Avoid contact with concentrated HCl.
INTRODUCTION
A coordination complex is a compound that is characterized by the presence of a

central atom or cation bound to a number of molecules or anions (ligands). The lone
pairs on the ligands that are directed towards metal cation are involved in a coordinate
bond with the metal cation.
Ethylenediaminetetraacetic acid (EDTA) is widely used as a complexing agent (ligand)

in titrimetric analysis since it forms complexes with a large variety of metal cations; for
51
example Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+,
Ln3+, (lanthanides) and Th4+.
There are two structural formulae for the neutral EDTA:
The formula for EDTA (I) is preferred to (II), since it has been shown from
measurements of the dissociation constants that two hydrogen atoms are probably
held in the form of zwitterions.
The disodium salt is most widely employed in titrimetric analysis. To avoid the constant
use of the long name the abbreviation, EDTA will be utilised for the disodium salt when
describing its use in titrations.
To simplify the writing of equations, ethylenediaminetetraacetic acid will be assigned

the formula H4Y. The disodium salt is therefore Na2H2Y and affords the complex-
forming ion H2Y2– in aqueous solution. The usefulness of EDTA as a titrant is due to
the presence of lone pairs on the four oxygen and two nitrogen atoms which are all
available to coordinate to a single metal cation in such a way that five-membered rings
are produced [Figure 1]; 1:1-complexes usually form and these are the most important.
Figure 1: The X-ray structure of the coordination complex, CaY(H2O)2.

It shows a deprotonated EDTA ligand that is coordinated to a metal cation (1:1).
Observe the presence of five-membered rings incorporating the metal cation - that
form on the coordination of this ligand to the metal.
52
The reactions with cations, e.g. Mn+, may be written as:
Mn+ + H2Y2– = MYn–4 + 2 H+
which represents:
PART A. STANDARDIZATION OF EDTA USING ZINC METAL

(60-80 minutes)
The EDTA solution is first standardized using a zinc solution, prepared from a known
weight of Analytical Reagent (AR) grade zinc pellets. The reaction is performed in
alkaline solution (pH 10) with the use of a pH buffer.
The indicator ERIOCHROME BLACK T is used in this standardization. This indicator

forms a red complex with zinc ions at pH 10. In the titration, a solution containing zinc
ions and a small quantity of indicator is titrated with EDTA. The zinc ions combine with
EDTA:
H2Y2– + Zn2+ ® ZnY2– + 2 H+
representing:
When all the zinc ions have been reacted, the EDTA displaces the indicator from the
zinc(II)-indicator complex liberating free indicator, which is blue. This is the end-point
reaction.
H2Y2– + ZnIndic ® ZnY2– + HIndic2– + 2 H+

(red) (blue)
53
PROCEDURE
(1) In a weighing jar, weigh out accurately on the analytical balance 0.9 – 1.1 g of
the zinc metal provided. This operation is crucial if accurate results are to be
obtained, so ask your demonstrator to check the weighing procedure with you.
(2) Transfer the metal carefully to a 50 ml conical flask (rinse with RO water
previously!!!). Do the next operation in the fume hood. Using a graduated
dropper provided with the bottle, initially add ~4 ml of concentrated HCl into the
flask to dissolve the metal (if it hasn’t dissolve add another 2 mL acid and then
contact demonstrator).
(3) If the metal has not dissolved when the effervescence ceases, heat in a beaker
of warm water until the metal dissolves completely. Your demonstrator will
instruct you on how to heat it. Don’t heat it for too long just until it dissolves.
(4) Cool the solution and add 15 M NaOH drop-wise and slowly with swirling until a
permanent faint white precipitate forms in the solution after shaking.
(5) Add 5 M HCl drop-wise to neutralize the solution until the zinc hydroxide
(Zn(OH)2) precipitate just dissolves. Add a further 5 drops more of the acid to
acidify the solution.
(6) Transfer the solution carefully to a 250 ml volumetric flask and make up to the
mark with distilled water. Stopper the flask firmly and shake it to ensure a
homogeneous solution.
(7) Calculate the concentration of zinc in the standard solution in mol/L.
(8) Rinse the burette twice with the given EDTA solution and then fill it with the same
solution.
(9) Rinse your 20 mL glass pipette, twice (into the waste beaker) with the zinc
solution.
(10) Deliver exactly 20.00 ml of the standard zinc solution using glass pipette into a
clean (rinsed with distilled water) 250 ml conical flask. Add 70 ml of distilled water
and 10 ml of the buffer solution (pH = 10). Do not remove the buffer solution
from the fume cupboard. Add four (4) drops of the Eriochrome black T indicator
(avoid adding excess indicator, which will cause a diffuse end-point and incorrect
titre values).
(11) Repeat step (10) a further 3 times so that you have four conical flasks of the solution
for repeat titrations.
(12) Titrate with the EDTA solution until the end-point is reached (WINE-RED to PURE
BLUE). Keep the first titrated solution as a reference colour for your next titration.
54
(13) Repeat the titration until three (3) concordant results are obtained. (Titres need
to be concordant, i.e. highest to lowest is within a 0.2 ml range. For example,
these titres of 21.10 ml, 21.24 ml, 21.18 ml are concordant because the volume
range, of highest to lowest is: 21.24 - 21.10 = 0.14 ml. At least 3 concordant titres
should be used to calculate the average.)
PART B. DETERMINATION OF WATER HARDNESS (TOTAL CALCIUM AND

MAGNESIUM CONTENT)
(40-60 minutes)
The hardness of water is an unpleasant characteristic in some industrial and household

uses of water (e.g. in boilers, for washing etc.). However, recently great concern has
developed over the apparent correlation of heart disorders and the consumption of soft
water. Water hardness is an important parameter in freshwater ecosystems. The
hardness of the water is mainly caused by calcium and magnesium salts. Both calcium
and magnesium are involved in many aspects of the body chemistry. Water Hardness
may be classified in terms of the concentration of calcium carbonate (CaCO3) in the
water.
Classification mg/L or ppm

Soft 0-60
Moderately Hard 61-120
Hard 121-180
Very Hard > 180
The total Ca2+ and Mg2+ content of a water sample is determined by titration with
standard EDTA using Eriochrome Black T as indicator. The titration is carried out at
pH10, which permits the Ca-EDTA and Mg-EDTA chelates to be formed
stoichiometrically, and also permits a sharp colour change. The reactions occurring
during the titration are:
H2Y2– + Ca2+ ® CaY2– + 2 H+
H2Y2– + Mg2+ ® MgY2– + 2 H+
When all the free Mg2+ and Ca2+ ions have been consumed, the EDTA displaces the
indicator from its magnesium complex, which is the end-point reaction.
H2Y2– + MgIndic- ® MgY2– + HIndic2– + 2 H+

(red) (blue)
Note that only a very small amount of the Mg2+ is combined with the indicator to give
the red colour. Thus, the number of moles of EDTA used is equal to the total number
of moles of Ca2+ and Mg2+.
55
PROCEDURE
(1) Rinse all glassware 3 times with distilled water.
(2) Dilute the EDTA solution by dispensing 25.0 ml of the given EDTA into a 250 ml
volumetric flask and make up to the mark with distilled water. Ensure that the
resulting solution is mixed thoroughly. Rinse and fill the burette with the diluted
EDTA solution.
(3) Dispense a 20 ml aliquot of the hard water sample into a 250 ml conical flask.
Add 2 ml of buffer solution (pH 10). Do not remove the buffer solution from
the fume cupboard. Add 4 drops of the Eriochrome black T indicator solution.
(4) Repeat step (3) a further 3 times so that you have four conical flasks of the solution for
repeat titrations.
(5) Titrate the water sample with the EDTA solution until the colour changes from
wine-red to pure blue.
NOTE: The colour change is gradual near the end-point and thus within the
vicinity of the end-point the EDTA solution must be added slowly while
swirling the water sample in the flask. Keep the solution from the first
titration as a reference for subsequent titrations.
(6) Repeat the titration until three (3) concordant results are obtained. (Titres
need to be concordant, i.e. highest to lowest is within a 0.1 ml range. For
example, these titres of 21.10 ml, 21.20 ml, 21.15 ml are concordant
because the volume range, of highest to lowest is: 21.20 - 21.10 = 0.10 ml.
At least 3 concordant titres should be used to calculate the average.)
(7) Express the water hardness in mol L–1 of (Ca2+ + Mg2+).
(9) Assuming the water hardness is only due to the presence of Ca2+, express the
water hardness in terms of mg L–1 of CaCO3.
CLEAN UP:
• Place all waste into the heavy metal waste containers in the fume cupboard.
• Take all empty glassware to the sink and wash with warm water and
detergent and finally with distilled water to rinse well several times.
• Put back all glassware into appropriate draw and sign out with your
demonstrator.
56
MARKING SCHEME /20
Prelab receipt 4
Part A
Calculation of Zn concentration 2
Titration reaction 0.5
Concentration of EDTA calc 2
Part B
Concentration of diluted EDTA calc 0.5
Titration reactions 0.5 + 0.5
Concentration of Ca2+ + Mg2+ calc 2
Calculation of water hardness 2
Questions 2
57
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58
NAME DATE

/20
Determination of Calcium and Magnesium -
Complexometric Titrations with EDTA
A. Standardisation of EDTA using zinc metal (7 marks)
Mass of zinc = g.
\No. of moles of zinc in 250 mL = mol
\Conc. of standard zinc solution = mol L-1
Titration of Zinc Solutions using EDTA
Sample No. 1 2 3 4
Final Burette reading
(mL)
Initial Burette reading
(mL)
Final-Initial Titre (mL)
Average of three (3) concordant titres = ______________ mL
Write the equation for reaction between Zn2+ and EDTA (H2Y2-):
No. of moles of Zn2+ in 20 mL = mol
\No. of moles of EDTA in titre = mol
\ Concentration of EDTA = mol L-1
59
NAME DATE
B. Total Calcium and Magnesium Content in Hard Water (9 marks)
Concentration of DILUTED EDTA solution = mol L-1
(Check this concentration with your demonstrator before continuing)
Titration of Hard Water using Diluted EDTA
1 2 3 4
Final Burette reading
(mL)
Initial Burette reading
(mL)
Final-Initial Titre (mL)
Average of three (3) concordant titres = ______________ mL
60
NAME DATE
Write the equation for reaction between Mg2+ and H2Y2- :
Write the equation for reaction between Ca2+ and H2Y2- :
\ No. of moles of diluted EDTA used in titration = mol
\ No. of moles of Ca2+ in the hard water sample = mol
In this experiment, it is assumed that No. of moles of (Ca2+ + Mg2+) = moles

(Ca2+).
\ Concentration of Ca2+ = mol L-1
\ Water Hardness (mg L-1 of CaCO3) = mg L-1

(i.e. calculate the mass of CaCO3)
How would you classify the hardness of this water?
Does this sample require a water softener?
61
NAME DATE
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62
EXPERIMENT 15
1
H NMR Study of Organic Compounds
To introduce to students the technique of nuclear magnetic resonance (NMR). To use

this technique to characterize the structure of simple organic compounds from their 1H
nmr spectra (given their molecular formula).
SKILLS IN FOCUS
• Characterization of organic molecules using 1H and 13C nmr spectra.
• Understanding of concepts such as:
o Nuclear spin
o Chemical shift
o Spin-spin splitting
o Downfield/Upfield shifts
• At the end of Unit 1 (Workshop 1) test you will be expected to predict the number of
different carbon and proton environments in a given molecule
NOTE: An introduction to 1H nmr is required. Make sure you read the introduction
below and look at the Youtube videos in the Prelab quiz. This will help you complete
the exercises in this experiment.
https://www.youtube.com/watch?v=Oj-yxbPz5Ao
https://www.youtube.com/watch?v=ZrVv7VaRjYs
https://www.youtube.com/watch?v=Otq5vrLHHrQ
https://www.youtube.com/watch?v=nAckAxapmc4
There will be a very short quiz at the end worth 3 marks.

There will be four multiple choice questions (based on Prelab questions) and
one question where you will need to draw a simple spectra (including any
expected splitting).
INTRODUCTION
Nuclei with an odd number of protons or neutrons have a permanent magnetic

moment. Nuclear Magnetic Resonance (NMR) is a form of spectroscopy that examines
how the magnetic moments of nuclei interact with magnetic fields (think of the nuclei
63
as being little bar magnets). The sample is placed in a strong magnetic field and its
interaction with electromagnetic radiation in the radiofrequency range is measured.
NMR spectroscopy is one of the most useful spectroscopies in chemistry because it
gives us information on nuclear environment and covalent (bonding) environment to
report on the molecular structure.
Two of the most useful nuclei in chemistry are 1H and 13C they possess an
unpaired proton (1H 1p) and neutron (13C 7n, 6p) respectively and therefore have a
magnetic moment making them nuclear magnetic resonance (nmr) active.
In the absence of an external magnetic field the magnetic nuclei orientate

randomly (Figure 1) and when placed in an external magnetic field (Bo) their magnetic
moment aligns parallel or antiparallel to the external field (like a little bar magnet).
These two orientations do not have the same energy (Figure 2) and are therefore not
exactly equally populated. The parallel orientation, of the nuclei magnetic moment to
the external field, is slightly lower in energy. The nuclei (sample) in the magnetic field
are then excited with a pulse of appropriate radio frequency. The emission of radiation
upon relaxation of the nuclear spins is detected as an FID (free induction decay) and
this is the converted to a frequency spectrum by a process called Fourier Transform
(Figure 3).
Figure 1: a) Randomly orientated nuclear spins in absence of an external magnetic field. b) Nuclear
spins in an external magnetic field, align parallel and antiparallel to the field. Mahaffy
nucleus aligned
against the field
Energy D E = hn
no
applied
field
nucleus aligned
with the field
applied magnetic field (B0)
Figure 2: NMR spectroscopy requires a magnetic field to generate the differences in energy states
that are measured in the experiment. Magnetic moments of nuclei in a magnetic field can either align
with the magnetic field (low energy state) or align against the field (high energy state). The difference
in energy (DE) between states is related to the frequency (n Hz) by Planck’s constant (h). The
frequency is in the radio frequency range (low energy).
64
Fourier
Transform
a) b)
Figure 3: NMR data is acquired as signal decay in time (s) (known as the free induction decay or
FID) and the Fourier transform transforms this data into the frequency (inverse time 1/s or Hz)
spectrum. a) Three FIDs of different compounds and their corresponding b) frequency domain
spectra.
You might expect then that all proton (1H) nuclei absorb energy at the same
frequency to populate the higher energy state. However, all nuclei in molecules are
surrounded by moving electrons. These moving charges set up small local magnetic
fields that alter the magnetic environment of inequivalent nuclei. Therefore, in an
external magnetic field, different nuclei environments will interact with different
electromagnetic radiation frequencies. Chemically equivalent nuclei absorb at the
same frequency. So 1H and 13C nmr provide a means of mapping the carbon-hydrogen
backbone of a molecule. Additional information about the nuclei can be obtained from
the position of the nmr signal on the frequency-axis. Tetramethylsilane (TMS, Figure
4) is added to each experiment and used as a reference. There is only one 1H and 13C
nmr peak in TMS since every proton and carbon is in the same environment. The
chemical shift of the single peak is assigned as zero ( = 0.0) for both 13C and 1H nmr
spectra.
CH3
H3C Si CH3
CH3
Figure 4: Tetramethylsilane (TMS)
H H
H H
A simple nmr example is benzene, C6H6, where every hydrogen and

H
carbon atom are in the same or chemically equivalent environment. Therefore, you
would expect only one peak in both the 1H and 13C nmr spectra (Figure 5) (all 1H nuclei
are related by symmetry operations such as rotation or reflection).
65
Figure 5: a) 1Hnmr spectrum of benzene b) 13Cnmr spectrum of benzene. The horizontal axis is the
chemical shift position and 1H and 13C have different characteristic chemical shift ranges.
In Experiment 4 - Organic Functional Groups (sem 1), you used chemical means
to determine the presence (or absence) of functional groups. In this experiment you
will interpret the 1H nmr spectra of compounds to identify their structure.
Let us consider two examples 1-propanol and 2-propanol (Figure 6). Firstly, we
can predict how many unique 1H nmr peaks you would expect for each molecule (each
number in Figure 6 indicates a unique proton environment). In 1-propanol, carbon 3
has three protons all in the same chemical environment, both protons on carbon 2 are
in the same environment, etc.. The area under these peaks in the spectrum
(integration) reflects the number of protons in each environment and for 1-propanol the
ratio of this integration would be 2:2:3:1 for the protons on carbons 1, 2, 3, 4
respectively. Symmetry plays an important role in determining equivalence. In the
example of 2-propanol there are two carbons that are equivalent (there is a reflection
plane along the C-O bond, Figure 7) and hence the protons on these carbons are
equivalent also. This molecule would be expected to have three peaks in the 1H nmr
spectrum (assuming the –OH proton is observed) due to three different proton
environments.
3
2 OH
4
H2 2
HO 1 C 3 1 CH 1
C CH3 H3C CH3
H2
1-propanol 2-propanol
Figure 6: Structures of 1-propanol and 2-propanol.
66
Figure 7: 2-propanol showing internal mirror plane
Where the peaks occur in the 1H nmr spectrum will depend on the atomic
environment of the particular groups. The position on the frequency axis is called the
chemical shift and given the symbol . Critical to the chemical shift position is how the
electronic environment in the molecule shields the nucleus from the applied magnetic
field. The greater the electron density of the nuclei the more shielded it is expected to
be and the closer to the right of the spectrum it will appear (lower chemical shift).
Conversely, the lower the electron density the more deshielded the protons are and
hence their peaks lie further to the left of the spectrum (higher chemical shift).
Neighbouring functional groups affect the position of the peaks strongly highly
electronegative groups withdraw electron density (deshield) moving the peaks to
higher chemical shift. In summary, the chemical shift (d) of protons are the measures
of their shielding relative to the protons in TMS. Table 1, below, summarizes expected
1
H chemical shifts.
Neighbouring nuclei alter the magnetic environment of nearby nuclei. The

magnetic moment of two nuclei aligned in the same direction will have slightly higher
energy than when the moments of the two nuclei aligns in opposite directions. This
phenomenon is called coupling or spin-spin splitting. Coupling causes NMR peaks to
have fine structure (split). To observe this splitting the nuclei must be connected by a
network of covalent bonds. Splitting patterns of proton resonances gives us information
about covalent connectivity and the number 1H nuclei on neighbouring carbons. The
splitting of 1H resonances is observed if they are connected through bonds (up to three,
H-C-C-H). The nmr peak of a hydrogen with n equivalent 1H on adjacent carbons split
into n+ 1 peaks (the n + 1 rule). An example is 2-propanol (Figure 8), the methyl 1Hs
are three bonds away from the 1H on the next carbon and are therefore split into two
peaks (known as a doublet). Splitting is not observed between equivalent nuclei so the
CH3 protons do not cause the splitting of each other only to the central CH proton.
Conversely, the single proton is next to six identical protons. The peak for this single
proton will be split into a multiplet consisting of seven separate peaks (called a septet)
(n= 6, n+1 = 6+1 = 7). It makes sense that this proton (septet, n = 6, n+1 = 7) has a
67
higher chemical shift since the –CH- is attached to the electronegative oxygen atom,
removing electron density from this group. The only other single proton is likely to be
the -OH proton. Protons attached to an O or N atom are less likely to show splitting
and are often broad peaks due to hydrogen bonding or exchange.
Figure 8: 1Hnmr spectrum of 2-propanol (peaks due to TMS and solvent are not shown).
It is not hard to imagine that the more complicated the molecule the more complex
the 1H nmr spectrum becomes. Overlapping signals can make unambiguous
assignment of splitting patterns difficult.
The purpose of Expt 15 is to gain experience in analyzing and interpreting the 1H

NMR spectra of simple organic molecules. Structural isomers of butanol will be
examined. It is important to recognize that if the compound is analyzed as a solution
there will be associated solvent peaks.
68
Table 1: Expected 1H chemical shifts
http://uhavax.hartford.edu/chemistry/pdb/nmr/nmr_right.html
69
1
PART A. H NMR Spectra of Structural Isomers of Butanol
You will be given four spectra of samples 1, 2, 3 and 4. These are the 1H nmr of
structural isomers of butanol. You will determine which spectrum belongs to which
alcohol.
1. Draw the structures of 1-butanol, 2-butanol, 2-methyl-1-propanol and tert-

butanol.
2. Determine the number of 1H nmr peaks (ignore splitting) that you would
expect for each of the above and predict the simple splitting pattern for each
type of proton.
Note: that some protons adjacent to two different types of protons will
be more complicated and difficult to predict. This is more about
differentiating between spectra.
Data Analysis:
Now, studying the first four spectra given to you:
3. Assign the solvent peak, as appropriate. (CHCl3 (chloroform) is found at

7.24 ppm and for acetone solutions at 2.05 ppm).
4. Using the prediction in 2 (above) and the integration ratios and chemical
shifts, assign each spectrum to the appropriate alcohol. Number the carbons
as shown for example in Figure 6.
5. Assign each of the peaks in the spectra (where possible) by placing the
appropriate protons responsible for each peak (i.e. label the peaks in the
spectra using the carbon label you have indicated in part 4).
Question 1. Briefly justify the assignment of the proton(s) with the highest chemical
shift (the most downfield proton(s)), in each alcohol.
Question 2. Why is/are there peak/s due to solvents?
Question 3. Draw a predicted spectrum of chloroethane (including splitting patterns).
70
PART B. Analysis of Aromatic Spectra
In this exercise we will predict the number of different 1H and 13C nmr peaks expected
for each of the following compounds, by consideration of symmetry.
1. Draw the structures of:
a) 1,2-dichorobenzene b) 1,3-dichorobenzene c) 1,4-dichorobenzene
2. Determine the number of expected proton and carbon environments for each of the
above compounds. Number the carbons on the above structures giving the same
number to equivalent carbons.
3. Consult with your demonstrator to ensure that the answers to 1 and 2 are correct.
Then proceed to 4.
4. Match the above compounds with the following 1H and 13C nmr spectra. Justify your
assignment.
71
72
MARKING SCHEME /20
Prelab receipt 4
Part A
Draw compounds and prediction of the no. of 1H nmr expected peaks 1
Predict expected splitting patterns (not complex patterns) 1
Assignment of spectra to correct alcohol 2 (0.5 – each)
Assignment of peaks to correct protons. 2
Question 1 – good concise answer (full marks) 1
Question 2 – good concise answer (full marks) 1
Question 3 – Draw predicted spectra of ethanol (with splitting) 2
Part B
Prediction of number of different proton environments for
disubstituted benzene compounds (demo look at) 1.5
Identify spectra 1.5
Quiz 3
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74
NAME DATE

/20
1
H NMR Study of Organic Compounds
Test result (3 marks)
Part A.
No. of Expected splitting
Structural Structure expected patterns of 1H nmr
1
Isomers of H nmr peaks
butanol peaks (Total 2 marks)
(Total 1
mark)
1-butanol
2-butanol
2-methyl-1-
propanol
tert-butanol
Staple the 1H nmr spectra handouts of alcohol to the back of this report.
i. Assign each spectrum to the correct alcohol. (2 marks)
ii. Assign the peaks on the spectrum to appropriate protons. (2 marks)
75
NAME DATE
QUESTIONS (4 marks)
Question 1. Briefly justify the assignment of the proton(s) with the highest chemical
shift (the most downfield proton(s)), in each alcohol.
Question 2. Why is/are there peak/s due to solvents?
Question 3. Sketch a predicted spectrum of chloroethane (including splitting patterns).
76
NAME DATE
Part B
Structures of disubstituted benzene No. of expected No. of expected

1 13
compounds H nmr peak/s C nmr peak/s
1,2-dichorobenzene
1,3-dichorobenzene
1,4-dichorobenzene
No. 4: Label the following spectra to the correct aromatic compound, in the
boxes provided. (Make sure you also state whether it is 1H nmr or 13C nmr
spectra.)
77
NAME DATE
78
NAME DATE
79
NAME DATE
80
An Alphabetical List of the Elements and their Atomic Masses
Element Symbol Atomic Mass Element Symbol Atomic Mass
Actinium Ac (227) Mercury Hg 200.59

Aluminium Al 26.98154 Molybdenum Mo 95.94
Americium Am (243) Neodymium Nd 144.24
Antimony Sb 121.75 Neon Ne 20.1797
Argon Ar 39.948 Neptunium Np (237)
Arsenic As 74.92159 Nickel Ni 58.69
Astatine At (210) Niobium Nb 92.90638
Barium Ba 137.327 Nitrogen N 14.00674
Berkelium Bk (247) Nobelium No (259)
Beryllium Be 9.01218 Osmium Os 190.2
Bismuth Bi 208.98037 Oxygen O 15.9994
Boron B 10.811 Palladium Pd 106.42
Bromine Br 79.904 Phosphorus P 30.97376
Cadmium Cd 112.411 Platinum Pt 195.08
Calcium Ca 40.078 Plutonium Pu (244)
Californium Cf (251) Polonium Po (209)
Carbon C 12.011 Potassium K 39.0983
Cerium Ce 140.115 Praseodymium Pr 140.90765
Cesium Cs 132.90543 Promethium Pm (145)
Chlorine Cl 35.4527 Protactinium Pa 231.03588
Chromium Cr 51.9961 Radium Ra (226)
Cobalt Co 58.93320 Radon Rn (222)
Copper Cu 63.546 Rhenium Re 186.207
Curium Cm (247) Rhodium Rh 102.90550
Dysprosium Dy 162.50 Rubidium Rb 85.4678
Einsteinium Es (252) Ruthenium Ru 101.07
Erbium Er 167.26 Samarium Sm 150.36
Europium Eu 151.965 Scandium Sc 44.95591
Fermium Fm (257) Selenium Se 78.96
Fluorine F 18.99840 Silicon Si 28.0855
Francium Fr (223) Silver Ag 107.8682
Gadolinium Gd 157.25 Sodium Na 22.98977
Gallium Ga 69.723 Strontium Sr 87.62
Germanium Ge 72.61 Sulfur S 32.066
Gold Au 196.96654 Tantalum Ta 180.9479
Hafnium Hf 178.49 Technetium Tc (98)
Helium He 4.00260 Tellurium Te 127.60
Holmium Ho 164.93032 Terbium Tb 158.92534
Hydrogen H 1.00794 Thallium Tl 204.3833
Indium In 114.82 Thorium Th 232.0381
Iodine I 126.90447 Thulium Tm 168.93421
Iridium Ir 192.22 Tin Sn 118.710
Iron Fe 55.847 Titanium Ti 47.88
Krypton Kr 83.80 Tungsten W 183.85
Lanthanum La 138.9055 Uranium U 238.0289
Lawrencium Lr (260) Vanadium V 50.9415
Lead Pb 207.2 Xenon Xe 131.29
Lithium Li 6.941 Ytterbium Yb 173.04
Lutetium Lu 174.967 Yttrium Y 88.90585
Magnesium Mg 24.3050 Zinc Zn 65.39
Manganese Mn 54.93805 Zirconium Zr 91.224
Mendelevium Md (258)
Note: (a) Atomic masses are based on atomic mass of 12C = 12.00
(b) Values in brackets refer to the mass number of the most stable or best known
isotope.
81

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CHEMISTRY 1

SECTION A ............................................................................................................. iii

10 Spectrophotometric Determination of the Salicylic Acid

12 Effect of Temperature on Reaction Rate

13 Preparation of Acetate Esters

14 Determination of Calcium and Magnesium -

Chemistry is largely an experimental science and laboratory work constitutes an important

1.1 Registration with Allocate+ and Group Numbers

You are able to choose the day of your lab on ALLOCATE+

If a class is missed on account of illness, your Demonstrator or the First-Year Laboratory

1.3 Prescribed Items

1. One pair of SAFETY GLASSES (regular glasses are not sufficient).

2. STUDENTS MUST have clothing COVERING their legs.

5. Laboratory Manual that includes the Report Book

1.4 Compulsory Prelab Online Exercise

To access the online Prelab:

1.5 Pre-Laboratory Instructions

1.6 Reporting of Results

1.7 Academic Integrity and Plagiarism

La Trobe University defines plagiarism as when you:

1.8 Marks and Marking

1.9 Laboratory Manual Procedures and Notation

1.10 Laboratory Equipment and Cleaning

The following texts are referred to in certain experiments:

2. SAFETY IN THE CHEMICAL LABORATORY

2.1 Laboratory Personnel

2.2 Dress Requirements

3. LABORATORY COATS protect clothing and person from corrosive chemicals.

2.4 Information About the Chemicals You Use

(i). Read the label. It should contain the following information:

(ii). Material Safety Data Sheets (MSDS)

• Respiratory (breathing in gases, vapours and particulate (dust) matter).

• Contact with intact or broken skin (usually liquids or solids).

• Ingestion (including accidental ingestion).

2.4.2 Description of Hazard Categories and Rating Scale

2.5 Risk Minimisation and Laboratory Safety

2.6 Laboratory Waste

2.7 Emergency Procedures

2.8 Preparation Room

4.1 Measuring cylinders

4.3 Watch glass

4.4 Test tubes and Test tube rack

4.5 Graduated Volumetric Flasks

4.6 Conical or Erlenmeyer Flasks

4.8 Buchner Funnel

4.9 Hirsch Funnel

Burettes are used for measuring (dispensing) accurate volumes of solutions,

4.11 Round bottom flask

4.12 Pear Shaped Flask

A condenser is used to cool hot vapours or liquids. A condenser usually

4.14 Distillation head

4.15 Receiver / Adaptor

4.16 Boss Head

Used to clamp glassware. Connected to a retort stand with a boss head.

4.18 Bunsen Burner

4.19 Separatory Funnel

If a solid material is to be made up as a standard solution, dissolve the accurately weighed

5.1 Calculation of Yield When There is No Chemical Change (Reaction)

5.2 Calculation of Yield in a Chemical Reaction

There are two steps to the calculation of a percentage yield:

1. Calculation of theoretical yield

2. Calculation of percentage yield

actual yield 100

This is best illustrated with an example.