Chem 101 Lab Manual

Department of Chemistry
2012 FIRST YEAR CHEMISTRY LABORATORY MANUAL

Daniel Southam Director of First Year Studies, Department of Chemistry
In case of an emergency dial 5 from any fixed-line phone on campus. All other phones use 08 9266 4444 or 1300 00 4444.
Write the name and contact information for your demonstrator and supervising demonstrator in the space below. This should be your first contact if a problem arrises in the laboratory. My demonstrator Name Email The experiments in this laboratory manual may not be performed in the order in which they are found or in a numeric sequence. Please refer to your unit outline for the correct sequence and ensure you bring the full laboratory manual to every laboratory session. My supervising demonstrator
STOP
This laboratory manual has been revised and updated with the kind assistance of your demonstrators, technicians and lecturers.
No part of this manual may be reproduced without the written permission of the Department of Chemistry COMMONWEALTH OF AUSTRALIA Copyright Regulation 1969 WARNING This material has been copied and communicated to you by or on behalf of Curtin University of Technology pursuant to Part VA of the Copyright Act 1968 ( the Act). The material in this communication may be subject to copyright under the Act. Any further copying or communication of this material by you may be the subject of copyright or performers' protection under the Act. Do not remove this notice
TABLE OF CONTENTS
Introduction Safety Care and use of balances A guide to uncertainties in volumetric analysis Advancing Science by Enhancing Learning in the Laboratory (ASELL) Part 1: Principles of chemistry and chemical measurement
Experiment 1.1: Introduction to the laboratory Chemical puzzles Experiment 1.2: Determination of acetic acid in vinegar Experiment 1.3: Standardisation of hydrochloric acid with borax Experiment 1.4: Standardisation of hydrochloric acid with a standard solution of sodium carbonate Experiment 1.5: An introduction to organic chemistry
5 7 11 12 16 17
19 33 45 53 61
Part 2: Chemistry of the elements

Experiment 2.1: Identication of common ions in solution Experiment 2.2: Simulation of extraction of gold from its ores Experiment 2.3: Coordination chemistry Synthesis of metal acac complexes Experiment 2.4: Hard soft acid base theory
75
77 89 99 115
Part 3: Synthesis, isolation & purication

Experiment 3.1: Identication of components in a mixture by chromatography Experiment 3.2: Purication of benzoic acid by recrystallisation Experiment 3.3: Preparation and reactions of cyclohexene Experiment 3.4: Preparation of 4-nitroacetanilide Experiment 3.5: Carboxylic acids and their derivatives using mind maps to link concepts Experiment 3.6: Alcohols and phenols
137
139 151 163 173 181 193
Part 4: Chemical and physical changes

Experiment 4.1: Intermolecular forces Solubility in liquids Experiment 4.2: Designing and making buffer solutions Experiment 4.3: Kinetics of the iodine clock reaction Experiment 4.4: Exploring Hess law using calorimetry
203
205 217 225 243
Part 5: Techniques in quantitative analysis

Experiment 5.1: Atomic Absorption Spectrometry Experiment 5.2: Determination of vanillin in imitation vanilla essence Experiment 5.3: Gas Chromatography Experiment 5.4: Analysis of vegetable oils Experiment 5.5: Determination of iron in cereals Experiment 5.6: Analysis of vitamin C
261
263 275 287 301 313 329
Preface
This page is left intentionally blank.
Preface
INTRODUCTION
Assessment and attendance
In addition to gaining at least 50% of the total marks, to gain a pass in this unit you must complete at least 80% of the available experiments and gain at least 50% of the total laboratory marks. Students who are absent from the laboratory due to illness, University business or participation in the Elite Athletes Program may be granted an exemption from an experiment at the discretion of the Unit Coordinator or the Head of the Department of Chemistry. If you were absent from the laboratory due to one of the aforementioned reasons, you should complete an Absence from the Laboratory form available from FLECS- Blackboard and attach the requisite documentary evidence. If approved, exemptions do not count toward the total number of laboratories for this pass requirement or the total laboratory mark. All requests for exemption must be received within ten working days of the missed laboratory. In many exercises, there are pre-laboratory questions to be answered prior to attending the laboratory class. These pre-laboratory questions must be handed in prior to the commencement of the pre-laboratory presentation. Pre-laboratory questions are an important part of the laboratory program to such an extent that two marks will be deducted from any exercise where they have not been attempted. All calculations are to be shown in full. In some experiments, students will be assessed on their accuracy, so pay particular attention to your technique.
Laboratory notes and pre-laboratory presentations

Before you commence an experiment, you should be fully aware of the hazards associated with the reagents and equipment you are about to use. To assist you with this, you must read and understand the procedures in this laboratory manual before entering the laboratory. This manual has notices throughout that highlight some important information, for example the safety requirements for a procedure you are about to perform.
The procedure you are about to perform contains a hazard. Safety is your responsibility. Take care!
Hazards are highlighted in the pre-laboratory presentation given by your demonstrator at the commencement of the laboratory. If you are not present at this presentation, you can put yourself and your fellow students at risk of injury. If you arrive after the pre-laboratory presentation, your demonstrator has the right to bar your entry to the laboratory, you will not be able to perform the experiment and you risk receiving zero for the missed experiment.
STOP
The experiments in this laboratory manual may not be performed in the order in which they are found or in a numeric sequence. Please refer to your unit outline for the correct sequence and ensure you bring the full laboratory manual to every laboratory session.
Preface
Equipment
To work in the laboratories, you must have the following items and be wearing them at all times in the laboratory. Laboratory coat Safety glasses Fully enclosed at-soled shoes covering the forefoot, toe and heel. Thongs, sandals, ballet slippers, ugg boots or similar are not acceptable.
Students who are not correctly attired will not be permitted entry to the laboratory and risk getting zero for the experiment. Forgetting these items does not warrant an excuse to gain an exemption under any circumstances. Laboratory coat and safety glasses only are available for hire at your cost from the technical staff. Students without correct footwear will not be permitted into the laboratory and will not necessarily be able to attend another session. The following items are recommended, particularly for students progressing to second year chemistry: Spatula, preferably metal Permanent marker, for marking of glassware
Contacts
Dr Daniel Southam Director of First Year Studies Ms Alicia Harrison Student Support Officer 08 9266 7265 firstyearchem@curtin.edu.au Reception, Level 2, Building 500
Telephone: Email: Location:
Preface
SAFETY
An important part of the laboratory experience is learning to work safely. Safety is everyones responsibility while in the laboratory. Even if youre not working with chemicals other people may be, so be aware at all times and follow some simple rules to avoid injury or causing injury to others. At the beginning of each experiment, you will see some important notices in the laboratory manual about safety. Failure to follow these and the instructions of staff may put you or other people at risk of injury. Students who fail to follow instructions will be asked to leave the laboratory and may face disciplinary action. The laboratory manual contains three important types of notices that must be read and understood before you commence any procedure in the laboratory:
A warning about specific hazards in this laboratory will be mentioned in these notices. This will occur both at the commencement of the laboratory and throughout the procedure. Many injuries can be avoided by following the verbal and written instructions from your demonstrator and in the laboratory procedure. If youre not sure, please ask staff for clarification.
PPE
All staff and students must wear the minimum Personal Protective Equipment (PPE) at all times whilst in the laboratory: safety glasses, a laboratory coat and fully enclosed shoes covering the forefoot, toe and heel. Additional or specialised PPE may be required when handling some equipment and chemicals.
STOP
Stop notices are used to draw your attention to a particular procedure which must be carefully followed to ensure your experiment works well and marks are not lost.
Preface
11 simple rules for safety in laboratories
!
1. 2.
The primary rule for safety in an undergraduate laboratory is to follow the instructions of all staff at all times. Demonstrators in the laboratory can be identified by their yellow safety vests. Other technical staff will be introduced to you in the first lab. It is a requirement that you follow their instructions without exception. Always act responsibly. Horseplay, running, unauthorised experiments etc. are strictly forbidden. Appropriate clothing must always be worn. This includes as a minimum: Safety glasses with colourless transparent lenses. Personnel wearing contact lenses must inform the laboratory supervisor as special precautions may be required. Neither sunglasses nor common prescription glasses are acceptable. A laboratory coat of a type that fastens up the front and comes to above the knee. Fully enclosed water-resistant shoes covering the forefoot, toe and heel completely. Thongs, sandals, ballet slippers, ugg boots or similar are not acceptable. Disposable gloves are available and must be worn as required. Ask your demonstrator to ensure the appropriate gloves are being used. Long hair should be tied up, regardless of gender. Any person wearing a headscarf or hijab should take extra care to ensure it is tucked into the laboratory coat.
3. 4. 5.
No food or drink is to be handled or consumed in a laboratory. Do not smoke in any place on campus. All buildings and grounds are smoke free. Never undertake any work unless the hazards of the operation are known and the safety precautions adopted. Students will be made aware of the risks during the pre-laboratory presentation at the beginning of the laboratory session. The instructions given by any member of staff regarding safety must be obeyed without question. You may be barred from the laboratory if you miss the pre-laboratory presentation at the discretion of the demonstrator.
6. 7. 8. 9. 10.
Always use protective devices appropriate to the type of operation being carried out, giving consideration to personnel operating in your vicinity. Regard all substances as hazardous unless there is denite information to the contrary. Report all accidents and spills, no matter how trivial, to your demonstrator. Ensure all spills are cleaned up immediately. Immediately wash skin areas which come into contact with chemicals, irrespective of concentration, and report this to your supervisor. Always use a fume hood when working with highly toxic, volatile or odourous substances. You will be given instructions by your demonstrator about the use of certain chemicals in the fume hood. Please ensure they are followed at all times. Dispose of specialised wastes (e.g. broken glassware) in containers reserved for the particular type of waste.
11.
Chemical Hazards
1. All chemicals should be handled with care. The following are particularly hazardous:
8
Preface
Concentrated acids, e.g. sulfuric, nitric; concentrated alkalis, e.g. sodium hydroxide, aqueous ammonia; hydrofluoric acid, chlorine, bromine, phenols, benzene, sodium or potassium metal, hydrogen sulfide gas. In case of spillage or splashing: (a) (b) (c) (d) 2. 3. on skin - wash off immediately under the nearest tap. on clothing - remove clothing and rinse thoroughly in water. on floor or bench - dilute with water and mop up with paper towels or mop. in eye - wash immediately with the eye irrigators situated at eye wash station.
Organic solvents, if in continual contact with skin, can cause skin diseases such as dermatitis. All experiments likely to generate toxic, flammable or irritating gases must be carried out in a fumehood. You will be instructed by your demonstrator in the pre-laboratory presentation which steps in the procedure require a fumehood. Particular care should be exercised in disposing of waste or spilt chemicals and reaction residues. This should be done on the advice of your demonstrator. Rubbish, waste filter paper, used paper towels etc must not be thrown into sinks or yellow sharp waste bins but placed in the green general waste bins with black liner provided. All sharp and/or contaminated wastes, such as broken glassware, must be placed in the yellow sharp waste bins.
4. 5. 6.
For a more complete list of chemicals with their first aid treatment, consult the Safety Data Sheets (SDS) available from ChemAlert at the PC located in the level 4 corridor.
Fire hazards
1. 2. Every student should learn from the demonstrator where to find the fire blanket, and fire extinguisher, nearest their place of work. Clothing catching fire causes the most distressing laboratory accidents. Since the victim's chances of recovery rapidly diminish with the extent of skin surface burned, immediate and correct action is essential. When clothing catches fire, throw the person to the floor and roll to smother the flames quickly. If a fire blanket or a laboratory coat is very handy, it may be used. If near a shower, roll the person under and then turn on the water, but never let them stand even if you have to be forceful. This procedure prevents injury to the respiratory passages and eyes by the flames, which would naturally rise and envelop the head. Never use an extinguisher of any type on a person. The soda-acid extinguisher may damage the eyes, whilst the carbon dioxide type may cause severe frostbite. 3. Flammable liquids should never be handled near an open flame, including when used in fumehoods. Never distil solvents such as alcohol, ether, petrol, etc. over or near an open flame. Volatile vapours will travel many metres to an open flame and ignite, thus setting the liquid in the container alight. Students are advised to tie up long hair since loose flowing hair may be a serious fire hazard in a chemical laboratory. Similarly, a headscarf or hijab may pose an extra risk, so extra care should be taken by tucking it into your laboratory coat.
4.
Preface
Handling glassware
The most common laboratory accidents arise from the careless handling of glassware. The following rules must be observed: 1. Ensure there are no jagged or chipped edges. Do not use glassware that is broken, chipped or damaged. Report any damaged glassware to your demonstrator or a technician. Before inserting glass tubing into corks, rubber tubing, or stoppers, make sure that the hole is large enough and moisten the tubing or stopper. Hold the stopper, etc., between thumb and forefinger, not in the palm of the hand. Grasp the glass tubing close to the end that is to fit into the stopper and push the tubing with an even pressure. Glycerine may be used as a lubricant instead of water. Never use force to remove rubber or corks from glass tubing. If necessary, cut the rubber or cork away from the glass. Do not try to force an oversize stopper into a flask.
2.
3. 4.
Approximate concentrations of some laboratory reagents

1. Concentrated Reagents (in fumehoods) Name Hydrochloric Acid Nitric Acid Sulfuric Acid Glacial Acetic Acid Aqueous Ammonia Sodium Hydroxide 2. Formula HCl HNO3 H2SO4 CH3COOH NH3 NaOH Molarity 10.2 16 18 17.4 14 9 % w/w 32 70 95 99.5 28 36 S.G. 1.16 1.42 1.84 1.04 0.89
Dilute Aqueous Reagents (on benches) Name Hydrochloric Acid Nitric Acid Sulfuric Acid Aqueous Ammonia Sodium Hydroxide Molarity 3 3 3 3 3
Preface
10
CARE AND USE OF BALANCES

The balances in our laboratories are expensive and fragile apparatus. Extra care must be taken when using them and the following rules are to be observed. 1. 2. 3. 4. Report any fault in balance operation to the laboratory technician. Do not try to rectify faults yourself. The glass doors at the sides of the balance case must be closed during weighing since drafts will upset the measurement. Before weighing, ensure that the pan is clean and dry and examine the object you are weighing to see that it is not wet or dirty on the outside. Take your laboratory notebook and record all weighings immediately. Do not rely on your memory or on scraps of paper. Check that the weight has been written correctly. It may save you hours repeating the experiment. Chemicals must not be weighed directly on the balance pan. Always use a suitable container such as a weighing bottle (see below) or crucible. Both weights, not merely the weight of substance, must be recorded. Anything spilt in the balance must be brushed out immediately. The bench on which the balance sits must also be kept free of spilt chemicals. Warm or hot objects must not be weighed. Convection currents in the air within the balance will cause errors. These are known as buoyancy errors. Objects placed on the balance pan are subject to the upthrust of the air that their volume displaces. A stoppered vessel will weigh less in the laboratory than in a vacuum. Corrections for buoyancy should be applied to substances of low density such as water. Further errors may be caused by samples that evaporate or absorb moisture.
5.
6.
7.
Steps involved in weighing

1. Whenever possible a weighing bottle should be used. If the quantity of solid to be weighed exceeds the capacity of the weighing bottle, a 50 mL or 100 mL beaker should be used - never use a watchglass. Remove the weighing bottle from the balance - never weigh any materials directly into a container on the balance. Weigh out approximately the required weight of the substance into a clean weighing bottle and record the total weight. Transfer the contents of the weighing bottle to a beaker, crucible, etc. Re-weigh the weighing bottle containing any remnants of the substance that did not come out in the transfer stage in 3 above and record the weight. By subtraction, the weight of substance transferred can be accurately determined.
2.
3. 4.
This method of weighing is known as weighing by difference. You should use this technique at all times in these experiments.
Preface
11
A GUIDE TO UNCERTAINTIES IN VOLUMETRIC ANALYSIS

When the result of a determination is presented, some indication should be given of the limits of accuracy. The first indication of the accuracy of a result is the way the relevant figure is written. For example, the Avogadro constant, NA, is written as 6.023 1023 mol1. This indicates that the value is known to at least four significant figures, i.e. the fourth figure, the 3, has some meaning. The table below lists ten separate readings that illustrates this uncertainty in measurement. No. 1 2 3 4 NA 6.025671 1023 6.021902 1023 6.024008 1023 6.022319 1023 No. 5 6 7 8 NA 6.023912 1023 6.023006 1023 6.020978 1023 6.022702 1023 No. 9 10 NA 6.024181 1023 6.023409 1023
These figures average 6.0232088 1023, yet they certainly would not justify writing NA as 6.0232088 1023. The results give the number as somewhere between 6.021 1023 and 6.026 1023, and the average should be written as 6.023 1023. As the 3 is uncertain, writing the 2088 part of the figure would imply accuracy not actually achieved. If a measurement is repeated many times, statistical methods may be used to determine the uncertainty of the result. Usually a determination is made only once or in duplicate, and other methods are needed to estimate accuracy. These methods are based on a consideration of the uncertainty in each measurement involved in the determination, and an estimation of their effect on the accuracy of the final figure. There are two broad classes of uncertainty - systematic uncertainty and random uncertainty. Systematic uncertainty will always act in the one direction. Examples are uncertainties in weighing hygroscopic (water absorbing) samples (always positive) or in weighing volatile samples (always negative). It is often possible to cope with these uncertainties by one of two methods: 1. 2. They can be minimised by improvements in technique, e.g. weighing more rapidly, etc. They can be allowed for by correction factors. In a titration of acid into base a little acid is required to change the colour of the indicator - apart from that required to neutralise the base. By titrating acid into distilled water plus indicator an estimate of this indicator or blank uncertainty can be made and subtracted from all titration figures. This technique cannot always be applied, e.g. the weighing uncertainty for hygroscopic samples will vary according to size and surface area of sample, time taken in weighing, humidity, room temperature, etc.
Random uncertainty can act in any direction. It is brought about by uncontrolled variables. For example, a pipette may deliver up to 0.02 mL too much or too little - even if care is taken.
Preface
12
In this laboratory manual the following random uncertainties should be allowed for:
Weighing
0.001 g on a 3-decimal place balance.
Pipette
0.05 mL for a 20 mL pipette. For more accurate work, the manufacturer's uncertainty can be determined by calibrating the pipette, leaving a random delivery uncertainty of 0.02 mL for a 20 mL pipette.
Burette
0.05 mL for each reading.
Volumetric asks
Assume an overall uncertainty of 0.2mL per 100mL capacity. An uncalibrated 250mL volumetric flask would give an uncertainty of 0.50 mL. The relative uncertainty is always 0.2%.
Steps for Calculating Uncertainty

Rule 1 Rule 2 When two figures are added or subtracted, the absolute uncertainty in the answer is the sum of the individual absolute uncertainties. When two figures are multiplied or divided, the relative (%) uncertainty in the answer is the sum of the individual relative (%) uncertainties.
For a simple titrimetric analysis: 1. Identify sources of uncertainty, which include any piece of apparatus that you are relying on a value to calculate from. Each apparatus has an inherent uncertainty in its reading or tolerance. This includes volumetric glassware like pipettes and volumetric flasks, balances or analytical instrumentation. For example, for apparatus used in these laboratories: Balance 0.001g per reading for 3-decimal place balance, giving total uncertainty of 0.002 g for each mass (when using weigh by difference, each number has uncertainty) 0.05 mL for a 20 mL pipette 0.05mL for each reading, giving total uncertainty of 0.10mL per titre 0.2 mL per 100 mL capacity; relative uncertainty always 0.2%
Pipette Burette Volumetric Flask 2.
Calculate the value of each uncertainty as a percentage
where
The uncertainty value is the value The measured value is the mass, titre, volume, etc
Preface
13
This describes the relative uncertainty associated with each measurement as a percentage. Only relative uncertainties can be combined to calculate the total uncertainty associated with each part of an experiment, since units are eliminated. 3. 4. Calculate total percentage uncertainty for the experiment by adding up the relative uncertainty for each source Calculate the absolute uncertainty on the final answer for the experiment Absolute uncertainty = % uncertainty calculated answer Quote as calculated answer absolute uncertainty with units e.g. 1. 2. 0.100 0.001 M 0.223 0.003 g L1
Example
Sodium hydroxide solution was standardised by titration of a 10.02 mL sample (from a calibrated pipette) with 0.102 0.002 M hydrochloric acid. The titration readings were: Final reading Initial reading Volume delivered (Titre) 45.20 mL 0.05 mL 34.30 mL 0.05 mL 10.90 mL
From Rule 1, uncertainty in titre due to reading uncertainty is: 0.05 mL + 0.05 mL = 0.10 mL The molarity of the NaOH solution is given by: From Rule 2, the relative (%) uncertainty in 0.1109 M is the sum of the relative uncertainties in 0.102, 10.90 and 10.02. This can be set out as follows: Uncertainty (mL) Molarity Burette (mL) Pipette (mL) 0.102 10.90 10.02 0.002 0.10 0.02 Relative Uncertainty (%) 2.0 0.9 0.2 3.1 3.1% of 0.1109 M = 0.0034 M
The answer should be expressed only to the first uncertain figure, in this case the third decimal place. The uncertainty should be rounded off to one significant figure and however many decimal places this produces, determines the number of decimal places in the answer. In this case, 0.111 0.003 M
Preface
14
Notes on uncertainties
Determinations are usually based on duplicates. In general it is satisfactory to calculate the uncertainty in one of the duplicates and apply this to the mean result. If the two results differ by more than twice the calculated uncertainty, they are not close enough and another determination should be carried out. The uncertainties expressed are based only on predictable random uncertainties. Uncertainties due to careless work are not accounted for, nor are systematic uncertainties. Variable systematic uncertainties may appear as too divergent in the duplicates. Constant systematic uncertainties are obscured. The above rules are a simplified treatment and tend to exaggerate those uncertainties that are due to predictable random causes.
Preface
15
ADVANCING SCIENCE BY ENHANCING LEARNING IN THE LABORATORY (ASELL)

Why?
Laboratory activities have long been seen as important components of a science course. They can be a popular component of these courses and can stimulate and motivate students to learn more about science. Indeed, most educators agree that the laboratory experience consistently ranks highly as a contributing factor toward students interest and attitudes to their science courses. Consequently, good laboratory programs should play a major role in influencing student attitudes, learning and performance. In fact the laboratory program can define a student's experience in the sciences, and if done poorly, can be a major contributing factor in causing students to disengage from the subject area. The challenge remains to provide students with laboratory programs that are relevant, engaging and offer effective learning outcomes.
How?
Curtin University is an active participant in the ASELL research project, with Prof. Mark Buntine (Head of Chemistry) a co-director of this national project and several other members of staff in the School of Science heavily involved. Over the course of this year we will ask you to complete surveys on the experiments you have undertaken and then the program as a whole. Your participation is voluntary and the surveys are anonymous. Nonetheless, you will be asked to identify the experiment you are evaluating and/or the unit in which you are enrolled. Neither whether you choose to respond to the survey, nor any feedback you provide, will have any influence whatsoever on your progress, results or grades in this unit. Returning the survey will constitute consent for its use for research purposes. The confidentiality of the information you provide will be safeguarded subject to any legal requirements. The results from this research will be used to improve undergraduate laboratory programs across Australia, and may be published in both refereed and non-refereed journals. If you are willing to participate in this project, please complete the survey after completing the experiment, and return it to the nominated location indicated by your laboratory supervisor. Please do not hesitate to speak to your laboratory supervisor during the experiment if you have any questions about this study. Thank you for your cooperation.
Who?
For questions regarding the ASELL project at Curtin, please contact: Dr Daniel Southam, Project Coordinator Telephone: (08) 9266 7265, Facsimile: (08) 9266 2300, Email firstyearchem@curtin.edu.au
Curtin University administers human ethics concerns relating to data collection under the auspices of ASELL. Any person with concerns or complaints about the conduct of this research study at Curtin can contact the Secretary of the Human Research Ethics Committee (phone: 9266 2784 or hrec@curtin.edu.au or in writing C/- Office of Research and Development, Curtin University, GPO Box U1987, Perth WA 6845) quoting the following project number: SMEC-50-10.
Preface 16
PART 1: PRINCIPLES OF CHEMISTRY AND CHEMICAL MEASUREMENT
17
18
EXPERIMENT 1.1: INTRODUCTION TO THE LABORATORY CHEMICAL PUZZLES

Safety
!
PPE
The chemical hazards in this laboratory a minimal. Your demonstrator will illustrate the procedural hazards during the pre-laboratory briefing. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Introduction
As is always the case in the conduct of science, today's tasks are as much about thinking as about doing. You will be given some problems that have a chemical basis. For each problem, there is more than one "correct" solution: indeed there are many valid solutions. Supervisors and demonstrators do not have the answers. There are no recipes. There is no specification of apparatus. We will be looking for: (a) (b) (c) (d) (e) (f) originality of approach validity of logic awareness of assumptions underlying the method used ability to communicate thought processes use of different approaches to the same problem reproducibility of your experiment (i.e. did you attempt it more than once)
There are two purposes to this "laboratory exercise": 1. 2. The problems are inherently interesting. Enrollment in this unit suggests that you want to develop some of the skills of scientists. Scientists are students - students of nature, to be sure, but like students, dependent for their success on the taking of notes. In even the most routine of scientific research, scientists must preserve external records of their work. Most externalise far more than just data: they might include making records of their hypotheses and predictions, "What if ...?" statements, notes from research literature, bright ideas (or wild speculations), plan, attempts to make sense of unexpected observations, and so on.
Your demonstrator will give you five tasks. During the laboratory session, you should do a minimum of at least two of the tasks in-depth. At least one of these should be task 3. The choice is yours. There is no pre-laboratory exercise for this experiment.
Experiment 1.1: An introduction to the laboratory
19
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. recognise the various glassware and apparatus available in the Chemistry laboratory, form an aim or hypothesis, test it with an experiment, discuss the results obtained and draw a conclusion, write a brief scientic report using appropriate language. work as a team to achieve complex tasks, communicate within a team.
Report writing
Each of the four scenarios must be written as a short mini lab report. There are four headings which are common to most scientific reports. You should write all scientific reports in third person past-tense. Your demonstrator will assist you in developing this skill by showing some examples. The relative length of the space provided will guide you about how much you write.
Aim
What does your experiment hope to achieve? Write two or three sentences using scientific language that describes your experimental aim. This explains to the reader (your demonstrator) what you hoped to achieve.
Experimental Procedure
Write the experimental procedure exactly as you perform the experiment. This section should be written with enough detail such that any other skilled person could perform the same experiment and achieve the same results.
Results and Discussion

This section should state your results, or a summary of your results, such as in tables and graphs. Discuss the meaning of the results in the context of the aims of the experiment and state their relevance to the findings of the experiment. Presentation of results without discussion will result in significantly lower marks. As a guide, when you present a result always think what does it mean? and try to communicate this meaning to the reader. This is where your demonstrator will be looking for a description of your individual logical thinking and marking you accordingly.
Conclusion
Your conclusion should be brief sentence or two answering the stated aim. Include a brief summary of any relevant results. While you will work in teams, its important to put the report in your own language. If you copy the words from a report submitted by another student this is called plagiarism.
STOP
Plagiarism is taking the ideas or words of someone else and representing them as your own. It is often considered easier just to copy rather than to put the ideas into your own words. However, students who copy or who are copied from are considered to have plagiarised this work and all parties will be reported to the University and may face disciplinary action. See the Academic Integrity website for more details: http://academicintegrity.curtin.edu.au/
20
Name
Student ID
Results and discussion

This will be hard work! There are many "correct" answers. The session is as much about thinking and communicating as it is about doing, but all the tasks require experimentation. You should discuss your thoughts, plans and ideas (written up in your laboratory report, of course) with your demonstrator. Problem 1: You are given a piece of sponge.
Task: What percentage of the volume of the sponge is air space?
Aim
21
Conclusion
22
Problem 2:
You are part of an emergency team that must decide whether the Eskimo settlement will be flooded if the icebergs melt.
Task: For a given mass of ice, m, and volume of water, V, with surface area, A, what will be the change of water level, h, when the ice melts?
Aim
23
Conclusion
24
Problem 3:
You must find the most accurate and precise measure of volume
Task: Using the apparatus available in the laboratory, you must find the piece of equipment that most accurately dispenses 20.00 mL of water the most often using the weight dispensed as the measure of accuracy.
Aim
25
Conclusion
26
Problem 4:
You are provided with some anti-acid tablets.
Task: Find the volume of gas released when one tablet dissolves in water.
Aim
27
Conclusion
28
Problem 5:
You are given five colourless solutions labelled A, B, C, D and E. One is a 0.5 M hydrochloric acid solution, one is a 0.5 M sodium hydroxide solution, one is a 0.5 M sodium carbonate solution, one is a phenolphthalein solution and one is water.
Task: Using only the above reagents, identify the five solutions.
Aim
29

The table below will help you with framing your results (and perhaps your experimental)! A B C D E
Conclusion
30
Departure Checklist
STOP
You must complete this checklist before you leave the laboratory. Your demonstrator will initial where indicated when the report is received and will check you have performed each of these tasks.
A two mark deduction from the total mark for this experiment will apply if the checklist is not complete and your demonstrator has not initialed your report. Tick each task as you complete it and ensure your demonstrator has initialed it before you leave the laboratory. Reports without your demonstrators initials will not be marked. My work area is clean and tidy I have cleaned and returned all glassware to the lockers I have wiped down all common areas, such as fumehoods and sinks I have returned all the reagents used I have attached the pre-laboratory questions to my result sheets only. Demonstrators initials
Assessment
Your demonstrator will assess your performance in this laboratory according to this assessment key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability. Criteria Originality of approach, statement of aims provided Validity of logic, experimental procedure stated and valid Communication of the logic underlying the method used, discussion of results Ability to communicate the experiment through writing of a logically structured report Awareness of reproducibility, experiment was repeated and results were comparable Poor 0 0 0 0 0 0.5 0.5 0.5 0.5 0.5 Good 1 1 1 1 1 Excellent 1.5 1.5 1.5 1.5 1.5 2 2 2 2 2
Total (out of 10)
31
32
EXPERIMENT 1.2: DETERMINATION OF ACETIC ACID IN VINEGAR

Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. manipulate volumetric glassware to achieve an accurate and reproducible volumetric analysis, standardise from a hydrochloric acid solution of known concentration a provided sodium hydroxide solution of unknown concentration and calculate its concentration, using this standardised sodium hydroxide solution determine the concentration of acetic acid in a provided sample of vinegar,
Principles of volumetric analysis

1. The aim of quantitative analysis is to determine the quantity of a particular species in a given sample. Analysis that depends on measurement of volume is called volumetric analysis. This analysis is carried out by matching a known quantity of a reactant A (the standard) against an unknown quantity of a reactant B (the unknown). For this purpose a solution of one reactant is added progressively to a solution of the other. This process is called titration. Only certain chemical reactions are suitable as a basis for matching reactants in a titration. There are several requirements. (a) (b) (c) (d) (e) 2. There must be some means of knowing when the matching quantity of one reactant has been added to the other. The point where the quantities are matched is called the equivalence point. The reaction must be free from side-reactions so it can be represented by a single equation. The reaction rate should be fast so that the equivalence point can be accurately detected. The reaction must go essentially to completion, i.e. the equilibrium constant for the reaction must be large.
The reactions used in volumetric analysis are of three types. (a) Those dependent on the combination of ions, as in acid-base titrations and precipitation titrations.
33
Experiment 1.2: Determination of acetic acid in vinegar
(b) (c) 3.
Those dependent on electron transfer (oxidation-reduction reactions). Those dependent on complex formation.
The technique of volumetric analysis involves the understanding and mastering of the following equipment. (a) (b) (c) (d) The pipette - used in the delivery of accurately known aliquots (volumes) of solution. The burette - used in the technique of titration to dispense and accurately measure the volume of titrant. The balance - weighing of objects on both top-loading and analytical balances. The volumetric flask - used in the preparation of standard solutions of accurately known concentrations.
Each of these techniques will be covered in extensive detail so that students can familiarise themselves with the mastery required in the collection of accurate analytical data.
Using a pipette correctly

The pipette is used to deliver a known volume, but will only do so if used as follows: (a) (b) (c) (d) Clean the pipette by washing thoroughly with detergent and tap water. Allow the pipette to drain, wash thoroughly with tap water and finally rinse with deionised water. Rinse the pipette two or three times with a small amount of the liquid, tilting to ensure that the whole inner surface is rinsed. Insert the pipette into the a pipette filler with a slight pressure. This assures a secure fit. Never insert the pipette more than 1 cm into the pump.
!
(e) (f) (g)
Be careful inserting a pipette into a pipette filler. Always grasp the pipette at wide top, never at or below the bulb, and never apply too much force. One of the most common laboratory injuries is from a pipette filler being inserted with too much force causing cuts or even penetration into hands or arms as a result. Draw up the liquid until it is above the graduation mark. Wipe away any adhering liquid from the outside of the lower stem with a cloth or paper towel. Allow the liquid to drip out slowly until the bottom of the meniscus just reaches the graduation mark. The pipette must be held vertically with the mark at eye level. The meniscus is the rounded top surface of the solution caused by adhesion of the solution to the walls of narrow glass tubes. The base of the meniscus is where all volumetric glassware should be read from.
STOP
(h) (i) (j) (k)
Remove any drop adhering to the tip by touching against a glass surface, not by wiping. Allow the liquid to run into the receiving vessel with the tip of the pipette touching the wall of the vessel. Do not allow the tip to be immersed in the liquid. When the continuous discharge has ceased, hold the jet in contact with the side of the vessel for 15 seconds (draining time). The liquid remaining in the jet at the end of the drainage time must not be removed either by blowing or any other means. Pipettes are calibrated to exclude any remaining solution.
34
(l)
All pipette volumes should be recorded in one decimal place as 10.0, 20.0, 50.0 mL.
The specifications for pipettes in common use are: Capacity (mL) Tolerance ( mL) (Class B) Delivery Time (secs) (Classes A and B) 10.0 0.04 15-25 20.0 0.05 15-30 50.0 0.08 25-40
How to read a burette accurately

It is important that you learn how to read a burette accurately. A well-trained titrator can read a burette to 0.01 mL. In this unit we expect you to be able to read the burette to 0.05 mL and report all volumes accurately. The figure at the right illustrates how this is done by positioning the baseline of the meniscus using the volume marks on the burette. A burette has volume marks at 0.10 mL increments. To read it accurately we look at the meniscus being on or close to the line (.00 mL) or about half way (.05 mL). Note how we still report the 0 when the meniscus is on the line as this digit is significant (e.g. 3.10 mL, 3.40 mL etc). You must write this number down and include the significant figures in the calculations.
3.10 mL 3.25 mL 3.40 mL 3.55 mL 3.70 mL 3.80 mL
When reporting the volumes, ensure that you include the value of the number immediately above your meniscus and count down the number of tenth markings, as illustrated above. You must bring your eye level with the meniscus to read this accurately. To do this when looking at the burette marking you should see one continuous line through the glass wall of the burette. If you see two lines you are not at eye level. You will read the burette twice; before your titration for the initial reading which should never be at 0.00 so you have marking above the meniscus to accurately judge its position and then immediately after your titration. Always record the volume of the burette to two decimal places.
Acid-base titrations
A titration is performed by reacting a standard solution with an unknown solution. Either the standard solution, or the solution containing the unknown, is pipetted into a conical flask. The other solution is then added progressively from a burette. Up to the equivalence point the solution contains an excess of one reactant; after the equivalence point it contains an excess of the other reactant. Some means of observing this changeover must be available. In acid-base titrations, the change in colour of an indicator may be used as evidence of the changeover. The observable point in the titration is called the end point. The end point must be as close as possible to the equivalence point; to achieve this the indicator must be carefully selected.
Experiment 1.2: Determination of acetic acid in vinegar 35
Steps involved in a simple acid-base titration procedure: e.g. Sodium hydroxide (NaOH) versus hydrochloric acid (HCl)
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Clean and rinse with deionised water two 250 mL beakers and three 250 mL conical flasks into which samples will be placed. Rinse one beaker with a small amount of the HCl solution to be taken and label accordingly. Pour the required amount of HCl into the beaker. Rinse the other beaker with a small amount of the NaOH solution to be taken and label accordingly. Pour the required amount of NaOH into the beaker. Rinse the pipette with the HCl. Fill the pipette with the HCl and deliver the 20.0 mL into the previously washed flask from (1). Add 2 or 3 drops of the appropriate indicator to the HCl. Do not add more than the specified amount. Repeat steps (7) and (8) for two or more further conical flasks as required. Clean and rinse a burette. Check for free running of the tap. With a ground glass tap ensure there is no excess grease. Rinse the burette with the NaOH solution. Mount the burette on a retort stand using a burette clamp and adjust the height of the burette such that the tip height is below the mouth of the 250 mL conical flask. Fill the burette with NaOH using a small plastic funnel. Close the tap before filling and remove funnel before commencing the titration. Run a few mL of NaOH out the tap of the burette to force the air out of the tip. Touch the tip of the burette against a wall of the waste beaker to remove any excess NaOH. Place a piece of white paper beneath the conical flask. This will assist you in detecting indicator colour changes. Record the initial volume to two decimal places. Holding the burette tap in your left hand and swirling the conical flask with your right hand titrate the HCl until the first colour change is noted. Ensure all splashings, etc. are washed down into the bulk solution. Record the final volume to two decimal places. Carry out a blank titration if necessary. Repeat this procedure until titration readings agree to within the tolerance required for the particular titration.
17. 18.
36
Part 1: Standardisation of an approximate 0.1 M sodium hydroxide solution

Titrations require the concentration of at least one component to be accurately known. The process of obtaining the concentration is called standardisation, and in part 1 we will standardise an approximate 0.1 M solution of sodium hydroxide (NaOH) using a known concentration of hydrochloric acid (HCl) that will be around 0.1 M (the accurate concentration will be provided by your demonstrator). These two will react together such that every 1 mole of HCl will react with 1 mole of NaOH in the following reaction: NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) Sodium hydroxide is not a good standard reagent because it will react slowly over time with carbon dioxide in the air to produce sodium carbonate, and therefore must be regularly standardised.
Procedure
Pipette three 20.0 mL aliquots of the HCl solution into three clean conical flasks, and add 2 3 drops of methyl red to each. Titrate the first solution to obtain a rough volume of titrant required and then carry out consecutive titrations until your results are within 0.10 mL of each other. Leave the burette with the NaOH solution for Part 2.
STOP
Read the burette to 0.05 mL. If youre not sure how, ask your demonstrator!
Part 2: Determination of acetic acid in vinegar

Now we have a standardised sodium hydroxide, we can use this to determine the concentration of acetic acid in vinegar. Acetic acid is our analyte in our sample of vinegar and it will react with sodium hydroxide in a 1:1 reaction as we saw in part 1. CH3COOH (aq) + NaOH (aq) H2O (l) + NaCl (aq)
Procedure
STOP
Your sample of commercial vinegar has been diluted 7 times. Make sure you include this when calculating the final concentration in the original vinegar.
Pipette three 20.0 mL aliquots of the vinegar solution into three clean conical flasks and add 2 drops of phenolphthalein indicator to each. Titrate these solutions with the standardised sodium hydroxide solution from Part 1. The end point is shown when the indicator changes from colourless to pink. Express your result as moles of acetic acid per litre the commercial vinegar to one decimal place. Clean your burette thoroughly after use.
37
This page is left intentionally blank
38
Name
Student ID
Pre-laboratory questions: Acid-base titrations

1. Why should the pipette be rinsed with NaOH (and the burette with HCl) prior to their use in dispensing these solutions?
2.
Can the NaOH solution be blown out of the pipette to reduce the time for the transfer? Briefly explain.
3.
Why should a constant, minimum amount of indicator be used in titrations?
39
4.
Calculate what volume of 0.100 M NaOH would you expect to deliver from the burette to standardise 20.00 mL of 0.102 M HCl?
5.
Assume that you will be carrying out four titrations using 20.0 mL of 0.1 M HCl. Approximately what volume of NaOH should you require?
Submit this sheet to your demonstrator when you enter the laboratory at the start of the session.
Experiment 1.2: Determination of acetic acid in vinegar 40
Name
Student ID
Part 1: Standardisation of approximately 0.1 M NaOH

Concentration of provided HCl (see the carboy in the laboratory and write this value down here)

Titrations
Burette Readings (mL) Final Initial Titre Rough Titration
mol L1
Accurate Titrations Place an asterisk next to your concordant results
Mean titre volume of your concordant results Determine the accurate concentration of NaOH, showing all working clearly. If required, determine the error in this value using the procedure given in the preface of your laboratory manual. You may attach additional sheets if necessary.
mL
Concentration of NaOH (to three decimal places)

mol L1
41
Part 2: Determination of acetic acid in vinegar

Concentration of NaOH (from part 1)

Titrations
Burette Readings (mL) Final Initial Titre Rough Titration
mol L1
Accurate Titrations Place an asterisk next to your concordant results
Mean titre volume of your concordant results
mL
Determine the concentration of acetic acid in the undilute vinegar in moles per litre, showing your working clearly. If required, determine the error in this value using the procedure given in the preface of your laboratory manual. You may attach additional sheets if necessary.
Concentration of acetic acid in undiluted commercial vinegar (to three decimal places) taking into account that the sample provided was diluted before analysis.

mol L1
42
Departure Checklist
STOP
Assessment
Your demonstrator will assess your performance in this laboratory according to this assessment key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability.
Criteria Pre-laboratory questions were...
0 Not attempted 0.5 Poorly attempted 1 Mostly incorrect 1.5 Mostly correct 0 No 2 Complete and mostly correct 0 No 2 Complete and mostly correct 2 All correct 1 Yes 3 Complete and fully correct 1 Yes 3 Complete and fully correct
Part 1: Concordant titre values with appropriate number of significant figures were provided Part 1: Calculations from the concordant results were...
0 Not attempted 0.5 Incomplete or partially attempted 1 Complete but incorrect
Part 2: Concordant titre values with appropriate number of significant figures were provided Part 2: Calculations from the concordant results were...
0 Not attempted 0.5 Incomplete or partially attempted 1 Complete but incorrect
Total (out of 10)
43
44
EXPERIMENT 1.3: STANDARDISATION OF HYDROCHLORIC ACID WITH BORAX

Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. recognise a primary standard, use a solid to standardise an unknown concentration of a solution and, master skills in weighing by difference, analytical transfer of solids and titration.
Aim
To utilise a standard solution of known concentration to determine the unknown concentration of a hydrochloric acid solution.
Introduction
As we discovered in experiment 1.2, it is necessary to standardise sodium hydroxide regularly due to constant reaction with atmospheric carbon dioxide reducing the concentration of hydroxide present in solution. To do this in experiment 1.2 we used a standardised hydrochloric acid solution. But how was the hydrochloric acid standardised? In this experiment we will standardise a solution of approximately 0.1 M hydrochloric acid. Solutions are standardised against substances known as primary standards, which should have the following desirable properties. 1. 2. Be readily preserved in a pure state and easy to dry. Must not be hygroscopic or efflorescent, i.e. must not alter in weight during weighing or vary in composition due to reaction with atmospheric gases, such as moisture or carbon dioxide. Have a high molecular weight so that weighing uncertainties are minimised. Be readily soluble under the conditions being employed. Must react stoichiometrically with the substance being standardised.
3. 4. 5.
Certain solutions when standardised may be used as standards themselves. These are known as secondary standards, e.g. HCl. In this experiment we will use borax or sodium tetraborate decahydrate, Na2B4O710H2O, as our primary standard. This will react with an acid, such as hydrochloric acid, according to the following reaction. Na2B4O7 (aq) + 2HCl (aq) + 5H2O (l) 4H3BO3 (aq) + 2NaCl (aq)
Therefore, the reaction between the tetraborate ion and hydrochloric acid has a molar ratio of 1:2 respectively.
Experiment 1.3: Standardisation of hydrochloric acid with borax
45
Procedure
Accurately weigh three samples of the required weight of borax directly into three clean 250 mL conical flasks using the following procedure. 1. 2. Place a clean dry weighing bottle onto a tared (zeroed) balance. Never tare (zero) the balance with the empty container on the pan. Remove the weighing bottle and weigh out approximately the required amount of the primary standard. Never weigh reagents into a container while it is still on the balance. Record the mass of the weighing bottle plus borax. Transfer the contents of the weighing bottle to a clean 250 mL conical flask, ensuring that you do not lose any of the borax. Re-weigh the weighing bottle containing any residue of the substance that did not come out in the transfer stage in 3 above and record the weight. By subtraction, the weight of substance transferred can be accurately determined. Ensure you clean the weighing bottle before your next measurement.
3. 4.
Dissolve the borax in about 100mL of deionised water. It is not necessary to know accurately the volume of water as we know the mass present in the flask and from this can determine the number of moles of the tetraborate ion present. Add three drops of methyl red indicator and titrate against the approximately 0.1 M solution of hydrochloric acid. Repeat the titration twice more. As it is unlikely that you will get exactly the same mass of borax three times, a quick check for concordance of your results is to divide the titre volume by the mass of borax present. Your results should be 0.10 mL g1. Calculate the concentration of hydrochloric acid accurately for each of the three borax titrations, not forgetting that for every one mole of tetraborate present two moles of hydrochloric acid will react. In this procedure we will also begin to examine the uncertainty associated with volumetric analysis. When calculating your concentration of hydrochloric acid, also calculate the uncertainty in this measurement by considering the tolerances of the volumetric glassware and balances used.
STOP
See pages 13 15 of this lab manual for a simple method for calculation of uncertainties.
46
Name
Student ID
Pre-laboratory questions: Standardisation of hydrochloric acid with borax

1. Calculate the weight of borax required to give a titre of 20.00 mL with 0.1 M HCl. Borax is sodium tetraborate decahydrate (Na2B4O710H2O) and we will use the analytical reagent (AR) grade, which we can assume is 99.9% pure. This will be the mass you will require to give a reasonable titre value in this experiment.
2.
Is it necessary to accurately measure the 100 mL of deionised water used to dissolve the borax? Briefly explain.
47
48
Name
Student ID
Results: Standardisation of hydrochloric acid with borax

Weighings (g) Wt weighing bottle + borax Wt weighing bottle Wt borax Burette Readings (mL) Final Initial Titre Quick check for concordance, if the ratios are close then we have accurate titre values Ratio 1 2 3 1 2 3 1 2 3
Calculate the concentration of HCl, including uncertainties, in three titrations

Titration 1
49
Titration 2
Titration 3
Concentration of HCl Titration 1 Titration 2 Titration 3 Average concentration M M M M
50
Departure Checklist
Assessment
Your demonstrator will assess your performance in this laboratory according to the assessment key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability.
Criteria 0 Pre-laboratory questions were... Concordant titre values with values given to 1 mL per gram of borax... Concentration of HCl calculate correctly, including uncertainty... Accuracy of calculated HCl concentration compared to expected value...
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
No
1
Sometimes
2
Always
0
No
1
Partially
2
Completely
0
20%
1
15%
2
10%
3
5%
4
2%
Total (out of 10)
51
52
EXPERIMENT 1.4: STANDARDISATION OF HYDROCHLORIC ACID WITH A STANDARD SOLUTION OF SODIUM CARBONATE
Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. weigh accurately by difference, transfer a solid quantitatively, prepare a solution of known concentration and, use this solution titrimetrically to quantify the unknown concentration of an solution.
Aim
To utilise a standard solution of known concentration to determine the unknown concentration of a hydrochloric acid solution.
Introduction
A solution of a primary standard can be used in exactly the same way it was used experiment 1.3. A solution of the primary standard may be preferable to using the solid directly if this solid is likely to change over time due to atmospheric moisture. To prepare a standard solution we must know the accurate mass of our primary standard, which is then dissolved in deionised water and transferred to a volumetric flask and made to the volume. To make a solution accurately we must use a volumetric flask. This piece of glassware has an accurately known volume and typically they are found in sizes from 1.000 mL up to 10.0 L. Today we will use a 250.0 mL flask with a tolerance of 0.5 mL. By transferring a solution containing a known mass of a primary standard (and therefore a known number of moles) we can make the flask to volume and it will have an accurately known concentration. To make the flask to volume we must fill it carefully to the mark with our solvent, usually deionised water. To do this fill with a wash bottle until the solvent is at the base of the neck then add your solvent dropwise with a pasteur pipette (not a
Experiment 1.4: Standardisation of hydrochloric acid with a standard solution of sodium carbonate 53
volumetric pipette) until the base of the meniscus is at the etched volume mark. You cannot remove solvent if you go over the mark accidentally, so be careful at this step, otherwise you must start again.
Procedure
In pairs prepare 250.0 mL of an approximately 1 0.05 M solution of sodium carbonate using the following procedure. 1. 2. Place a clean dry weighing bottle onto a tared (zeroed) balance. Never tare (zero) the balance with the empty container on the pan. Remove the weighing bottle and weigh out approximately the required amount of the primary standard. Never weigh reagents into a container while it is still on the balance. Record the mass of the weighing bottle plus sodium carbonate. Transfer the contents of the weighing bottle to a clean 250 mL beaker, ensuring that you do not lose any of the sodium carbonate. Re-weigh the weighing bottle containing any residue of the substance that did not come out in the transfer stage in 3 above and record the weight. By subtraction, the weight of substance transferred can be accurately determined. Dissolve the solid in 50 mL of deionised water. Transfer the solution from the beaker to a clean 250.0 mL volumetric flask using a small filter funnel to facilitate transfer. Wash the beaker thoroughly with deionised water and transfer the washings to the volumetric flask. Wash the filter funnel with a little deionised water and then remove from the volumetric flask. Using deionised water make up the solution in the flask until the bottom of the meniscus is level with the graduation mark, as illustrated in figure. Finally stopper the flask firmly and shake thoroughly, inverting several times to aid mixing.
3. 4.
5. 6. 7. 8. 9.
Individually transfer approximately 100 mL of the sodium carbonate solution into a clean and dry beaker and pipette three 20.0 mL aliquots of the standard sodium carbonate solution into clean conical flasks. Dilute each to about 60 mL with water 2. Add three drops of methyl orange-indigo carmine indicator and titrate with the hydrochloric acid until the indicator turns grey. The end point has been overstepped if a magenta colour develops. Sodium carbonate will react with an acid, such as hydrochloric acid, according to the following reaction. Na2CO3 (aq) + 2HCl (aq) 2NaCl (aq) + CO2 (g) + H2O (l)
Therefore, the reaction between the carbonate ion and hydrochloric acid has a molar ratio of 1:2 respectively.
STOP
See the preface of this lab manual for a simple method for calculation of uncertainties.
You are unlikely to get exactly the correct mass to obtain exactly 0.0500 M sodium carbonate solution, but it will still be accurately known, typically within three signicant gures. It doesnt matter whether you have 0.0512 M or 0.0474 M, so long as you use your accurately known concentration in your calculations. It is not necessary to note how much deionised water you add, as the only source of sodium carbonate should be from the standard solution. 54
Experiment 1.4: Standardisation of hydrochloric acid with a standard solution of sodium carbonate
Name
Student ID
Pre-laboratory questions: Standardisation of hydrochloric acid with a standard solution of sodium carbonate
1. Calculate the weight of anhydrous AR sodium carbonate (Na2CO3) required to make 250.0 mL of 0.0500 M solution. This will be the mass you will require to give a reasonable titre value in this experiment.
2.
Why should all solid be dissolved before transfer of the solution from the 250 mL beaker to the volumetric flask?
3.
Why is it necessary to shake the volumetric flask thoroughly after the solution has been made up to the mark?
55
56
Name
Student ID
Results: Standardisation of hydrochloric acid with a standard solution of sodium carbonate

Part 1: Preparation of a standard 0.05 M solution of sodium carbonate
Weighings (g) Wt weighing bottle + Na2CO3 Wt weighing bottle Wt Na2CO3
Calculate the concentration of anhydrous sodium carbonate including uncertainties
Concentration of sodium carbonate
M
57
Part 2: Titration of sodium carbonate against hydrochloric acid

Burette Readings (mL) Final Initial Titre Mean titre volume mL Rough Titration Accurate Titrations
Calculate the concentration of HCl including uncertainties

Recall that every one mole of sodium carbonate reacts with two moles of hydrochloric acid.
Concentration of hydrochloric acid
M
58
Departure Checklist
Assessment
Criteria 0 Pre-laboratory questions were... Concentration of Na2CO3 calculated correctly, including uncertainty... Concordant titre values with values given to 0.05 mL... Concentration of HCl calculated correctly, including uncertainty... Accuracy of calculated HCl concentration compared to expected value...
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
No
1
Partially
2
Completely
0
No
1
Sometimes
2
Always
0
No
1
Partially
2
Completely
0
20%
0.5
15%
1
10%
1.5
5%
2
2%
Total (out of 10)
59
60
EXPERIMENT 1.5: AN INTRODUCTION TO ORGANIC CHEMISTRY

Safety
!
PPE
Many of the substances used in this experiment are flammable. Please use them in the fumehood and ensure there are no sources of ignition. Sodium must be kept out of contact with water. It is also highly corrosive. Do not let it come into contact with your skin. Dispose of excess sodium by reacting it completely in ethanol and pouring the solution into the waste beaker in the fumehood. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment. This includes when using molecular models.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. visualise the three-dimensional structure of some simple hydrocarbons using a molecular model kit, represent the three-dimensional structure using conventional two-dimensional notation and, observe some characteristic reactions of four common functional groups.
Aim
To observe representations of the three-dimensional structures of some simple hydrocarbons using a molecular modeling kit. To explore the characteristic reactions of some common organic functional groups.
Introduction
Organic Chemistry is the study of hydrocarbons and their derivatives. Hydrocarbons are compounds made up of carbon and hydrogen. Hydrocarbons can be saturated and unsaturated. Derivatives can contain elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, phosphorus and the halogens (group 17 elements). Here are some examples of names of alkanes and cycloalkanes. Look carefully at these so that you can work out how the different styles of representing these molecules are used, and how to translate from one style to another.
Experiment 1.5: An introduction to organic chemistry
61
Name methane ethane propane butane pentane hexane
Condensed formula CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 or CH3(CH2)2CH3 CH3CH2CH2CH2CH3 or CH3(CH2)3CH3 CH3CH2CH2CH2CH2CH3 or CH3(CH2)4CH3
Structural formula CH4 CH3CH3 CH3CH2CH3 or CH3CH2CH2CH3 or CH3CH2CH2CH2CH3 or CH3CH2CH2CH2CH2CH3 or
cyclohexane
C6H12 or
The molecules obviously do not exist in two dimensions as represented on the two-dimensional paper. Nor are most molecules locked into a single fixed shape. There is free rotation about many covalent bonds and of the molecules listed above, only one has a single shape. The C atom is always tetravalent (it forms four covalent bonds with neighbouring atoms). Bearing in mind the constant covalence of C and the importance of atomic sequence, examine the next set of examples. Notice that although 1,1-dichloroethane is represented in six different forms (more are possible), you should recognise that each represents the same molecule.
1,1-dichloroethane
or
or
or
or Cl2CHCH3 or CH3CHCl2
Part 1: Molecular models

In the first part of the experiment today, we will use molecular models to represent the structure of organic molecules. An appreciation of the three-dimensional arrangement of atoms in molecules is important in order to rationalise and understand many of the physical and chemical properties of organic compounds. In this exercise you are asked to: (i) (ii) (iii) construct models of a number of simple molecules draw a reasonable three-dimensional representation of the resulting structures answer some questions regarding these structures
The FlexibleStereoChemistry model kit utilises lengths of plastic tubing to represent chemical bonds. While this is useful for many purposes, the models do not give a good indication of the effective size of atoms or groups of atoms. Space-filling models are required for that purpose.
Experiment 1.5: An introduction to organic chemistry 62
Part 2: What is organic chemistry? An exploration of functional groups

A functional group is the component of an organic molecule that gives it its characteristic reactivity or function. This experiment involves some of the fundamental reactions of the common functional groups. It also includes the formation, on test tube scale, of crystalline derivatives characteristic of a particular functional group. Students are expected to regard every test as an investigation and through this develop an awareness of the correlation between structure and reactivity. Write equations for every reaction. The functional groups we will examine in this experiment have the following general formulae, where R is any hydrocarbon chain or ring. Name General Formula Example methanol CH3OH Alcohols and phenols phenol
OH
OH
O
Aldehydes
propanal O
C R O H
H3C C H2
C H
propanone O
Ketones
C R R'
H3C
C CH3
STOP
The procedure for todays experiment is included with your report sheet.
63
64
Name
Student ID
Pre-laboratory questions: An introduction to organic chemistry

Draw structural formulas or unambiguous condensed structural formulas for each of the following: (a) octane
(b)
decane
(c)
cyclobutane
(d)
cyclopentane
(e)
methylcyclobutane
(f)
1,1-dimethylcyclobutane
(g)
2-bromo-1-chlorobutane
(h)
1-bromo-2-chlorocyclobutane (two isomers)
65
Complete the following table for some of the reagents you will be using today. Common name Structure IUPAC name
methyl alcohol
ethyl alcohol
n-butyl alcohol
sec-butyl alcohol
tert-butyl alcohol
formaldehyde
benzaldehyde
acetone
acetaldehyde
cyclohexanone
66
Name
Student ID
Part 1: Procedure and results
STOP
Before you commence Part 1, read Part 2 thoroughly. You do not need to complete this experiment in sequence. Make sure to manage your time effectively.
Construct a model of methane, CH4, by clicking together two pieces of black tubing to create a tetrahedral carbon atom. Place a white ball on each "bond" to represent H atoms. Note the equivalence of all four bonds, i.e. of all four hydrogen atoms. 1. What is the HCH bond angle in methane? Draw a diagram representing this structure.
Make a model of ethane, CH3CH3. Note that rotation about the CC bond can lead to an infinite number of arrangements of the six hydrogen atoms, i.e. an infinite number of conformations. 2. What is the HCH bond angle in ethane? Draw a diagram representing this structure.
Make a model of ethylene (ethene), CH2=CH2, using two trigonal carbon atoms (grey). Note that the double bond prevents rotation about the axis joining the two bonded atoms. 3. What is the HCH bond angle in ethylene? Draw a diagram representing this structure.
67
4.
You cant make a model of acetylene, CHCH, as there is no triple bond in the set. Assuming a linear molecule draw a diagram representing the structure of acetylene.
5.
Make a model of both isomers of 1,2-dichloroethylene (ClCH=CHCl). Draw them and identify which is cis and which is trans.
6.
Make a model of 1,2-dichloroethane and draw it. Are there cis / trans isomers possible? Explain.
7.
Draw the structure of 1,2-dichloroacetylene. Are there cis / trans isomers possible?
68
8.
Construct a model of cyclobutane. Note that the four carbon atoms are constrained to be essentially coplanar. Cyclopropane, the smallest cycloalkane, is highly strained and it is difficult to construct with the present model kit without causing damage to the plastic tubing. Draw a diagram representing the structure of cyclobutane. Is free rotation around the C C bonds possible?
9.
Make models of the five possible isomeric dimethylcyclobutanes. Draw the structures of the these and name them.
10.
Attach four different coloured balls to a tetrahedral carbon atom (to represent, say, CHFClBr) to generate structure A. Place this structure on the bench and construct structure B that is the mirror image of A. Are structures A and B the same, i.e. are they superimposable? Draw each structure.
If they are superimposable, then they are identical. If they are not superimposable, then they are isomers known as enantiomers. Enantiomers belong to the class of isomers known as stereoisomers and give rise to a special sort of isomerism known as optical isomerism. Stereoisomers have the same atom connectivity but have a different arrangement in space. Your hands exhibit the same phenomenon, where your hands are mirror images but they are not the same.
69
Part 2: Procedure and results

Reactions of alcohols and phenols
Reaction with sodium
!
1.
Sodium must be kept out of contact with water. It is also highly corrosive. Do not let it come into contact with your skin. Dispose of excess sodium by reacting it completely in ethanol and pouring the solution into the waste beaker in the fumehood.
Place a small piece (rice grain size) of clean sodium in 0.5-1 mL of an alcohol in a test tube. What is the gas evolved? How would you test for it?
When the sodium is completely reacted divide the solution into two. Allow one portion to evaporate on a watch glass. 2. What is the residue?
Test the second portion with 2-3 drops of Universal Indicator. Colour observed pH 3. What are the equations for the reactions above?
70
Reaction with iron(III) chloride To 0.5 mL of ethanol add 2-3 drops of iron(III) chloride solution. Repeat the experiment using 0.5 mL of 2% phenol solution. Note any colour change.
4.
What do you conclude from these experiments?
Oxidation of alcohols Compare the action of an oxidant, potassium dichromate, on n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Place three test tubes side by side, each containing five drops of one of the alcohols. To each add 2 drops of acidified potassium dichromate solution and shake. Record your observations. Alcohol n-butyl alcohol Observations
sec-butyl alcohol
tert-butyl alcohol 5. How does the structure of the alcohol affect its ability to be oxidised?
71
Reactions of aldehydes and ketones

Silver mirror test Rinse a large test tube with 1 mL of 3 M sodium hydroxide. Place 2 mL of silver nitrate solution. Add 3 M ammonia solution drop by drop until the precipitate first formed just redissolves. To 0.5 mL of this solution in a small test tube, add 1 drop of each reagent from the table. Record in the table what you observe at room temperature and on warming in hot water. Reagent Observations
formaldehyde
benzaldehyde
acetone
Fehling's Solution Prepare a stock of Fehlings solution in a large test tube as follows. To 2 mL of Solution A, containing copper sulfate, add solution B, containing potassium sodium tartrate and sodium hydroxide, until the blue precipitate formed just dissolves to obtain a clear dark blue solution. To 1 mL of this prepared solution in a small test tube, add 3 drops of each reagent from the table. Record in the table what you observe at room temperature and on warming in hot water. Reagent Observations
formaldehyde
acetaldehyde
acetone
72
Schiffs reagent To 0.5 mL of Schiff's Reagent (aqueous rosaniline hydrochloride decolourised with sulfur dioxide) add 3 drops of formaldehyde and observe the colour immediately produced. Repeat the test with acetone, benzaldehyde and cyclohexanone. Reagent Observations
formaldehyde
acetone
benzaldehyde
cyclohexanone
Condensation with 2,4-dinitrophenylhydrazine (Brady's Reagent) To 0.5 mL of Brady's Reagent A in a test tube add 2-3 drops of acetone. Warm the test tube gently and allow to cool. If necessary, scratch the inside of the test tube with a glass rod to promote crystallisation. Repeat the test with acetaldehyde, and, using Reagent B, cyclohexanone and benzaldehyde. Reagent Observations
acetone
cyclohexanone
acetaldehyde
benzaldehyde
73
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions were... Part 1: Correct structures and diagrams were provided Part 2: Detailed observations were... Part 2: Correct reactions of selected observed reactions were provided... In-laboratory questions were... Poor 0
Not attempted
Good 0.5
Poorly attempted
Excellent 1.5
Mostly correct
1
Mostly incorrect
2
All correct
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
Not provided
0.5
Very poor
1
Adequate
1.5
Good
2
Excellent
0
Not provided
0.5
Rarely
0.5
Sometimes
1.5
Often
2
Always
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
74
PART 2: CHEMISTRY OF THE ELEMENTS
75
76
EXPERIMENT 2.1: IDENTIFICATION OF COMMON IONS IN SOLUTION

Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. give accurate and detailed observations, draw logical and relevant inferences, relate the theory to experimental observations, balance chemical reactions.
Introduction
When a chemical reaction occurs, substances called reactants are transformed into different substances called products that may have different appearances and different properties. Often you can follow these changes with your own eyes. Learning the skill of making accurate observations is absolutely essential for a scientist. You are going to observe a number of chemical reactions in this laboratory experiment. You must write down your observations, try to draw conclusions based on your observations, figure out what chemical change took place, and express this change in the form of a balanced chemical equation. In this experiment you need to concentrate on writing the correct chemical formulae for all the reactants and products in each reaction. When you write an equation, make sure also that the correct physical state of each substance is designated (g for gas, l for liquid, s for solid, or aq for aqueous species). You must also check each chemical equation to confirm that it is balanced (i.e. it obeys the Law of Conservation of Mass). Common polyatomic ions are detailed in the following table. You should remember the common atomic ions formed. For example, the halogens (F, Cl, Br, I) form halide ions of charge 1 (F, Cl, Br, I), hydrogen forms a H+ cation, and Group 1 metals form +1 cations.
Experiment 2.1: Identication of common ions in solution
77
Name Ammonium Acetate Bicarbonate (hydrogen carbonate) Bisulfate (hydrogen sulfate) Bisulfite (hydrogen sulfite) Carbonate Chlorate Chlorite Chromate Cyanide Dichromate Dihydrogen phosphate
Formula Name NH4

+
Formula HPO42 OH ClO NO3 NO2 C2O42 ClO4 MnO4 O22 SO42 SO32 PO43 S2O32
Hydrogen phosphate Hypochlorite Nitrate Nitrite Oxalate Perchlorate Permanganate Peroxide Sulfate Sulfite Phosphate Thiosulfate
CH3COO Hydroxide HCO3 HSO4 HSO3 CO32 ClO3 ClO2 CrO42 CN Cr2O72 H2PO4
In this experiment, students will determine the solubility rules for cations and anions by carrying out a series of chemical reactions and observing the changes that take place. A number of solubility rules have been devised to allow the prediction of which ionic compounds are insoluble and would form a precipitate for a given reaction. In exchange reactions, two ionic compounds are reacted together in aqueous solution, and the resulting products reflect an exchange of the anions and cations. If one or both of the products is insoluble in water, a solid (precipitate) is formed. AB (aq) + CD (aq) AD (s or aq) + CB (s or aq) For example, the reaction of silver nitrate and sodium chloride is written as, AgNO3 (aq) + NaCl (aq) AgCl (s) + NaNO3 (aq)
78
Procedure
All ionic solutions are available in dropper bottles, at 0.1 M concentration. You will be provided a copy of the observation grid and a transparency sheet to place over the top. The data grid includes sodium salts across the top horizontal row (labelled 1-8) and a series of nitrate salts in the vertical column (labelled A-H). Carefully add the reagents dropwise onto the transparency sheet To each horizontal row (A through H) add 2 to 3 drops of the following reagents: A. B. C. D. E. F. G. H. To Row A add 0.1 M silver nitrate, AgNO3. To Row B add 0.1 M barium nitrate, Ba(NO3)2. To Row C add 0.1 M calcium nitrate, Ca(NO3)2. To Row D add 0.1 M copper(II) nitrate, Cu(NO3)2. To Row E add 0.1 M zinc nitrate, Zn(NO3)2. To Row F add 0.1 M lead(II) nitrate, Pb(NO3)2. To Row G add 0.1 M potassium nitrate, KNO3. To Row H add 0.1 M iron(III) nitrate, Fe(NO3)3.
To the vertical column (1 through 8) add add 2 to 3 drops of the following reagents: 1. 2. 3. 4. 5. 6. 7. 8. To Column 1 add 0.1 M sodium carbonate, Na2CO3 To Column 2 add 0.1 M sodium chloride, NaCl. To Column 3 add 0.1 M sodium hydroxide, NaOH. To Column 4 add 0.1 M sodium sulfate, Na2SO4. To Column 5 add 0.1 M sodium phosphate, Na3PO4. To Column 6 add 0.1 M sodium oxalate, Na2C2O4. To Column 7 add 0.1 M sodium iodide, NaI. To Column 8 add 0.1 M sodium thiosulfate, Na2S2O3.
Observe carefully (observations should be made and recorded as solutions are combined) to determine which combinations of solutions produced precipitates. In your data table, record each combination of ions that showed the formation of a precipitate. Record the color, texture, and other observations for each.
STOP
Rinse your plastic sheet in the washup sink using plenty of water. Make sure you wipe the plastic sheet and your bench clean before beginning to answer any questions.
79
80
Name
Column 1 Na2CO3
A3 A4 A5 A6 A7 A8
Column 2 NaCl
Column 3 NaOH
Column 4 Na2SO4
Column 5 Na3PO4
Column 6 Na2C2O4
Column 7 NaI
Column 8 Na2S2O3
A1
A2
Observations
Row A AgNO3
B3 B4 B5 B6 B7 B8
B1
B2
Row B Ba(NO3)2
C3 C4 C5 C6 C7 C8
C1
C2
Row C Ca(NO3)2
D3 D4 D5 D6 D7 D8
Experiment 2.1: Identication of common ions in solution E3 E4 E5 E6 E7 E8 F3 F4 F5 F6 F7 F8 Student ID G3 G4 G5 G6 G7 G8 H3 H4 H5 H6 H7 H8
D1
D2
Row D Cu(NO3)2
E1
E2
Row E Zn(NO3)2
F1
F2
Row F Pb(NO3)2
G1
G2
Row G KNO3
H1
H2
Row H Fe(NO3)3
81
Balancing equations
Where a chemical reaction was observed for a particular anion, write at least one example of a balanced chemical equation for the reaction with the corresponding cation. Include all physical states (s, l, aq or g) in the chemical equations. 1. Column 1: carbonates
2.
Column 2: chlorides
3.
Column 3: hydroxides
4.
Column 4: sulphates
82
Balancing equations continued...

Where a chemical reaction was observed for a particular anion, write at least one example of a balanced chemical equation for the reaction with the corresponding cation. Include all physical states (s, l, aq or g) in the chemical equations. 5. Column 5: phosphates
6.
Column 6: oxalates
7.
Column 7: iodides
8.
Column 8: thiosulfates
83
Inferences
An inference is where you can make an assessment of the results or observations and draw a conclusion based on your scientific knowledge. Using the following questions as a prompt, draw some inferences from your observations. 1. The anion solutions (Columns 1-8) were all sodium salts. What can you conclude about the general solubility of sodium salts?
2.
All of the cation solutions (Rows A-H) are nitrates. What can you conclude about the general solubility of nitrates?
3.
Which cation(s) formed precipitates with nearly all (7 out of 8) the anions?
4.
It is concluded that all chlorides are soluble except silver chloride. How do your results compare with this expectation?
5.
What can you generalise about the solubilities carbonates, chlorides, sulphates and iodides?
84
6.
Repeat the analysis of the data to create a generalized rule (5 or more similar outcomes out of 8) for the solubility of each of the metallic cations: (a) Row F: lead(II), Pb2+
(b)
Row C: calcium, Ca2+
(c)
Row D: copper(II), Cu2+
(d)
Row E: zinc, Zn2+
Questions
1. The anion solutions (Columns 1-8) were all sodium salts. Could potassium salts be substituted for the sodium salts? Explain your answer.
85
2.
How might these solubility rules be used by an environmental chemist interested in the removal of iron to purify water for drinking? (Hint: think precipitation).
3.
An old box of chemicals is found in the chemistry store. There are two brown bottles of solutions. Unfortunately, the labels have come off the bottles, although they are still in the same box. The labels are for solutions of barium nitrate and sodium nitrate. Describe how you could use your solubility rules to identify the contents of each bottle.
86
4.
Use the chemical species in the following table and the solubility rules you have just determined to answer these questions. Ag+ K+ (a) S O2 Ca2+ Pb2+ NO3 C2O42 SO42 Cl
Which are cations?
(b)
Which are not ions?
(c)
Which will precipitate with 0.1 M lead(II) ions?
(d)
Which will precipitate with 0.1 M potassium ions?
(e)
Which will not precipitate with 0.1 M silver ions?
(f)
Which will precipitate with 0.1 M sulfate ions?
(g)
Which will precipitate with 0.1 M nitrate ions?
(h)
Which will precipitate with 0.1 M calcium ions?
(i)
Which will precipitate with 0.1 M chloride ions?
87
Departure Checklist
A two mark deduction from the total mark for this experiment will apply if the checklist is not complete and your demonstrator has not initialed your report. My work area is clean and tidy I have cleaned and returned all glassware to the lockers I have wiped down all common areas, such as fumehoods and sinks I have returned all the reagents used I have attached the pre-laboratory questions to my result sheets only. Demonstrators initials
Assessment
Your demonstrator will assess your performance in this laboratory according to the assessment key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability. Criteria Accuracy and detail of observations: the observations all match the expectations and are provided with sufficient detail Balanced chemical equations: a correctly balanced chemical equation is given for each reaction observed Inferences are logical and correct: correct inferences are drawn based on the observations provided Answers to questions are correct: a logical and thoughtful answer is given for each question posed Poor 0 0.5 Good 1 1.5 Excellent 2
0.5
1.5
0.5
1.5
Total (out of 10)
88
EXPERIMENT 2.2: SIMULATION OF EXTRACTION OF GOLD FROM ITS ORES

Safety
!
PPE
Care should be exercised when handling the ethylenediamine solution and hydrogen peroxide solution. Avoid contact with the skin. You will be asked to wear gloves when handling ethylenediamine and hydrogen peroxide solutions. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. observe a coordination reaction that permits extraction of a metal from unwanted material, write detailed experimental observations and draw logical theoretical inferences, relate a laboratory-scale experiment to an industrial process.
Aim
To reinforce the importance to chemistry, industry and life of the reactions of coordination compounds.
Introduction
In metallurgy there is a generalised procedure for obtaining many metals from their ores: 1. 2. 3. Add a reagent which takes the metal or metal compound from its mineral form into solution. Separate the gangue (rest of the material) from the desired component. Reduce the desired component from its soluble form back to the free and pure metal.
Where heat is used and the solution is a solid, this is called pyrometallurgy, where an aqueous solution is used this is called hydrometallurgy. The extraction of gold from gold ore (gold metal and gangue) is a good example. The following flow chart represents the separation of gold from gangue during the extraction of gold from its ores. There are two chemical steps in the process: 1. The first step involves the dissolution and hence oxidation of the gold metal. Air can be bubbled into water in contact with gold for a long period of time, but the gold would not be oxidised. However, in the presence of cyanide ions, gold is oxidised to a water-soluble complex ion. The driving force for the reaction is the formation of the very stable complex ion, [Au(CN)2]. Complex ions and compounds are formed by the coordination of ions or molecules having an unshared pair of electrons to a metal cation.
89
Experiment 2.2: Simulation of extraction of gold from its ores
Other examples of complex ions and compounds are: 1. 2. 3. 4. 2. the [Cu(NH3)4]2+ ion the [Fe(CN)6]3 ion chlorophyll, the green pigment found in plants that allows photosynthesis haemoglobin, the metalloprotein responsible for oxygen transport in mammals
The second chemical step involves the reduction of the [Au(CN)2] ions by the more reactive zinc, according to the following equation: Zn(s) + 2 [Au(CN)2](aq) [Zn(CN)2](aq) + 2 Au(s)
Ore Au + gangue
Crusher
Powdered ore Au + gangue
Sodium cyanide NaCN
Chemical Reactor 4 Au + 8 NaCN + O2 + 2 H2O 4 Na[Au(CN)2] + 4 NaOH
Oxygen O2
Residue Gangue
Filtration
Solution [Au(CN)2]
Product Au (s)
Reduction
Zn
The extraction of gold is not a suitable laboratory experiment because gold is very expensive and cyanide solutions are very poisonous. Instead, the process will be illustrated by separating copper from a simulated copper ore (~1% mixture of copper in clean sand) using a 5% aqueous solution of ethylenediamine and oxygen to dissolve the copper according to the following equation: 2 Cu(s) + 2 H2O(l) + O2(g) + 4 en(aq) 2 [Cu(en)2]2+(aq) + 4 OH(aq) and zinc to reduce the bis(ethylenediamine)copper(II) ions: [Cu(en)2]2+(aq) + Zn(s) [Zn(en)2]2+(aq) + Cu(s)
H2N H2C
NH2 CH2
ethyelenediamine, en
90
Since the reaction is very slow when the air above the flask is the source of oxygen, hydrogen peroxide will be used as the oxidant. Hydrogen peroxide reacts according to the following equation. 2 H2O2(l) 2 H2O(l) + O2(g)
Important
An essential part of this laboratory is noting down your observations (what you see) and your inferences (what you think is happening, chemically) for this laboratory. At each step in the procedure note down what you observe, such as colours of solutions and significant events, such as gases or heat evolved. Where a significant event has occurred, note down your inference including the relevant chemical equation.
Procedure
Caution: Care should be exercised when handling the ethylenediamine solution and hydrogen peroxide solution. Avoid contact with the skin. Weigh about 5 g of the simulated ore into a 100 mL conical flask, and add about 20 mL of a 5% aqueous solution of ethylenediamine. With continuous swirling, add successive portions of about 0.5 mL of 3% (10 volume) hydrogen peroxide solution. Allow bubbling to subside between additions. Add a total of 20 mL of the hydrogen peroxide solution. Swirl for another 5 minutes. The bubbling is due to evolution of oxygen produced by decomposition of hydrogen peroxide. Decant the slurry into a beaker and wash the residue several times with a small volume of water. Add a pea-sized sample of powdered zinc and stir the solution. Wait until the solution is colourless (more zinc may need to be added). Decant the solution. Wash the residue and decant the liquid at least twice. The black residue is a mixture of copper metal and surplus (unreacted) zinc. Remove the zinc by adding about 4 mL of 3 M sulfuric acid solution.
91
92
Name
Student ID
Pre-laboratory questions: Simulation of extraction of gold from its ores

1. Given that for a chemical reaction to occur its products must be stable, consider the following two reactions: I. II. 4 Au(s) + 2 H2O(l) + O2(g) 4 Au+(aq) + 4 OH(aq) 4 Au(s) + 8 CN (aq) + 2 H2O(l) + O2(g) 4 [Au(CN)2](aq) + 4 OH(aq)
Reaction I does not occur readily, while reaction II does. What does this say about the relative stability of Au+ versus [Au(CN)2]?
2.
What species is reduced when the gold is oxidised to form [Au(CN)2]?
93
3.
Coordination compounds, like [Au(CN)2], are often found in nature. Every coordination complex contains an electron deficient metal centre and several electron rich donor atoms surrounding it. For each of the following naturally occurring coordination compounds give the metal centre and the donor atom molecular structure immediately about this metal centre: a) chlorophyll a
b)
haemaglobin
4.
Do you notice any chemical structural similarities between the metallic sites in both haemaglobin and chlorophyll a? Explain.
Experiment 2.2: Simulation of extraction of gold from its ores 94
Name
Student ID
Observations and inferences

You can include diagrams, chemical equations and written observations and inferences. Discuss these with your partner, but write them up in your own words.
STOP
Plagiarism is taking the ideas or words of someone else and representing them as your own. It is often considered easier just to copy rather than to put the ideas into your own words. However, students who copy or who are copied from are considered to have plagiarised this work and all parties will be reported to the University and may face disciplinary action. See the Academic Integrity website for more details: http://academicintegrity.curtin.edu.au
95
Questions
1. What observations may be seen to indicate that rapid dissolution of copper occurs during the first step?
2.
During this process describe the evidence you observed for: a) the presence of [Cu(en)2]2+ ions?
b)
the dissolution of zinc?
96
3.
During the addition of the 3 M sulfuric acid: a) Name the colourless gas evolved. Write a balanced chemical equation for the reaction.
b)
How can you tell when the zinc is completely removed?
c)
Does the residual sludge look like copper? Explain this.
d)
Devise two tests to demonstrate that the residue is copper.
97
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... 0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Observations - detail: The observations were...
0
Not provided
0.5
Poorly detailed
1
Partially detailed
1.5
Mostly detailed
2
Fully detailed
Observations - accuracy: The observations were...
0
Not provided
0.5
Not accurate
1
Fully accurate
Inferences - detail: The inferences were...
0
Not provided
0.5
Partially detailed
1
Fully detailed
Inferences - logic: The inferences were...
0
Not provided
0.5
Not logical
1
Partially logical
1.5
Mostly logical
2
All logical
0 In-laboratory questions were...

Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
98
EXPERIMENT 2.3: COORDINATION CHEMISTRY SYNTHESIS OF METAL ACAC COMPLEXES

Safety
!
PPE
Acetylacetone is toxic and has a foul odour. Handle in the fume hood.
You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. synthesise and isolate a coordination compound, purify some products by recrystallisation, observe the colours of coordination compounds with different metal centres but identical ligands, predict the chemical and electronic structures about each metal centre through observation and measurement.
Aim
To synthesise three coordination compounds with a common bidentate ligand (acetylacetonate, acac) and different metal centres (Mn3+, Fe3+ and Cu2+).
Introduction 3
A characteristic property of transition metals is their ability to form a large number of stable coordination compounds. These are often coloured, and are made up of the transition metal ion with one or more attached ligands. A ligand is a molecule or anion that has donor atoms containing a lone pair of electrons that can donate this electron density to the electron deficient metal centre to form a bond. The number of bonds formed in this way is known as the coordination number of the metal ion, and this can be any number greater than 2, with 4- and 6-coordinate complexes being the most common for d-transition metals. The physical properties of metal complexes are often related to the coordination number and the spatial arrangement of the ligands or geometry. The majority of 4- and 6-coordinate transition metal complexes have one of the following structures.
This experiment was adapted from First Year Experiment 3.10 undertaken at Queensland University of Technology. 99
Experiment 2.3: Coordination chemistry - synthesis of metal acac complexes
L L L M L L L L L octahedral M L L L
L L L tetrahedral M
square planar
Figure 2.3.1: The three most common coordination geometries encountered in transition metal complexes
Stereoisomers are defined as isomers that have the same connectivity (exactly the same set of atoms connected together with exactly the same set of bonds), but with different spatial arrangements of atoms. Geometric isomers or diastereomers cannot be interconverted without breaking a chemical bond. In an octahedral or square planar geometry the most common pair of geometric isomers encountered are cis and trans. Additionally for octahedral geometries facial (fac-) and meridional (mer-) isomers may also be encountered. cistwo particular atoms or groups of atoms are adjacent to each other two atoms or groups of atoms are on opposite sides facthree particular atoms or groups of atoms are found on the faces of the octahedron three particular atoms or groups of atoms are found on the meridians of the octahedron
trans-
mer-
Referring to Figure 2.3.1, cis-trans isomerism can occur for both octahedral and square planar geometries, but not tetrahedral. The cis and trans isomers generally have quite different colours, melting points, dipole moments and chemical reactivities. For example, the square-planar diamminedichloroplatinum(II) complexes (Figure 2.3.2) are examples of cis-trans isomers that show markedly different properties. While the cis form (cisplatin) is very important because of its ability to act as an antitumour agent, the trans form is highly toxic, and has no antitumour properties.
Cl Cl cischloro ligands at 90 to each other Pt NH3 NH3 H3N Cl transchloro ligands at 180 to each other Pt Cl NH3
Figure 2.3.2: Chemical structures of cis- and trans-diamminedichloroplatinum(II)
Enantiomers are stereoisomers that are nonsuperimposable mirror images. Objects or molecules that are not superimposable on their mirror image are said to be chiral, and chiral compounds have the property of rotating the plane of polarisation of plane-polarised light; they are described as optically active. Objects that can be superimposed on their mirror image are described as achiral, and are not optically active. Illustrated below are the structures of two enantiomers of the complex tris(acetylacetonate)iron (III) [Fe(acac)3] (Figure 2.3.3) that you will make in todays experiment. They are mirror images of each other and cannot be superimposed. A pair of enantiomers always rotate plane-polarised light by the same amount, but in opposite directions. Thus, in an equimolar mixture of the two enantiomers, the net rotation is zero. Such a mixture is called a racemic mixture.
100
O O O O Fe O O O O
O Fe O O O
O O O O Fe O O
Figure 2.3.3: The two enantiomers of the chiral complex [Fe(acac)3]. Acetylacetonate (acac) is a bidentate ligand with two oxygen donor atoms and is represented by the two Os joined with an arc. The mirror plane lies between the two isomers, perpendicular to the plane of the page. You can see that the arcs representing the carbon chain linking the two oxygens in acac prohibits us from reattaining the original mirror-image structure.
Unlike cis-trans isomers, a pair of enantiomers has identical physical and chemical properties, (eg melting point, boiling point, chemical reactivity), except when they are interacting with another chiral molecule. Note that the ligand in Figure 2.3.3 coordinates to the central Fe(III) ion via both of its oxygen atoms. Such a ligand is described as bidentate (whereas a ligand that forms only one bond is monodentate). Bidentate ligands are also called chelates. The chelating ligand in Figure 2.3.3 will be used in this experiment and is the acetylacetonate anion ("acac"). This is formed from acetylacetone (2,4-pentanedione) by removal of an H+ ion, called deprotonation. The anion can be represented by resonance structures as shown in Figure 23.4, or as a simple arc joining the two oxygen donor atoms, as illustrated in Figure 23.3.
O H+ O
Deprotonation
Figure 2.3.4. Deprotonation of acetylacetone to form the acac anion. Resonance stabilisation of the formal charge then permits both oxygen donor atoms to coordinate to the metal centre
When bound to a metal, the negative charge is delocalised over the two oxygen atoms and the central carbon atom, and the bonding within the ligand is represented with a curved line as shown in Figure 2.3.4. One consequence of the delocalisation is that the 6 membered chelate ring formed from a metal and an acac ligand is planar.
101
Procedure
Acetylacetone is toxic and has a foul odour. Handle in the fume hood.
Work in pairs to produce the three complexes. Part 1: bis(acetylacetonato)copper(II), [Cu(acac)2]

1. 2. 3. 4. 5. 6. 7. Dissolve 0.50 g of Cu(NO3)2.2H2O in 20 mL H2O in a 50 mL conical ask. While stirring, add 2 mL acetylacetone. Stir for about 5 minutes. Write down your observations. If no solid forms, stir with a glass rod until your product crystallises. Collect the product by vacuum ltering through a small Buchner funnel. Rinse any solid adhering to the ask into the funnel with water. Rinse the product with a small amount of ethanol and suck air through the crystals for several minutes. Weigh the product. Show it to your demonstrator and obtain initials on your report sheet.
Part 2: tris(acetylacetonato)iron(III), [Fe(acac)3]

1. 2. 3. 4. 5. Dissolve 0.60 g of Fe(NO3)3.9H2O in 10 mL of water in a 50 mL conical ask. Add 2 mL acetylacetone and start stirring. Write down your observations. Carefully add 0.8 g of NaHCO3 dissolved in 15 mL water in dropwise with stirring. CAUTION! Write down your observations. After addition is complete, stir for a further 10 minutes, then lter off the solid product. Rinse the product with a minimal amount of ethanol (this product is very soluble so if you use too much ethanol you will dissolve your product) and pull air through the crystals for several minutes. Weigh your crude product using the top pan balance and record the crude yield. Recrystallise your product in the following manner: Put the solid into a small conical ask. Add 3 mL of water and warm on a steam bath. Add ethanol dropwise with swirling, until the hot sample just dissolves (approximately 5 mL). Cool in an ice bath and vacuum lter your puried product. Remember that an ice bath must contain water. Weigh the recrystallised product. Show it to your demonstrator and obtain initials on your report sheet.
6.
7. 8.
102
Part 3: tris(acetylacetonato)manganese(III), [Mn(acac)3]

1. 2. 3. Dissolve 0.50 g of MnCl2.4H2O in 20 mL of water in a 50 mL ask, add 1.5 g hydrated sodium acetate, Na(CH3COO).3H2O and stir to dissolve. Add 2 mL of acetylacetone with continued stirring. Write down your observations in the Results sheet. Carefully add a solution of 0.1 g KMnO4 dissolved in 10 mL water. NOTE: This solution is intensely coloured and it can be difcult to see if it is dissolved. Ensure that ALL permanganate is transferred to your reaction ask, but do not add additional water or rinse any residual solid. Write down your observations. In a separate 50 mL conical ask, dissolve another 1.5 g Na(CH3COO).3H2O in 15 mL of water. Add this to the solution from step 3. Heat the mixture on a boiling water bath for around 10 minutes, then cool in an ice bath. Filter off the solid product, rinse the product with a small amount of ethanol and pull air through the crystals on the lter paper for several minutes. Weigh the product. Show it to your demonstrator and obtain initials on your report sheet.
4. 5. 6. 7. 8.
When working out the limiting reagents youll need to know the density of acetylacetone, which is 0.98 g mL-1.
103
104
Name
Student ID
Pre-laboratory questions: Metal acac complexes

1. Complete the following table. Complex Structure and name Metal centre oxidation state, d-electron conguration and coordination geometry Oxidation state = [Cu(acac)2] d e config = geometry = Oxidation state = [Fe(acac)3] d e config = geometry = Oxidation state = [Mn(acac)3] d e config = geometry = Oxidation state = trans-[Co(en)2Cl2]+ d e config = geometry = Oxidation state = trans-[Co(en)2Cl(OH2)]2+ d e config = geometry =
105
2.
Based on the procedure provided, calculate the theoretical yields for: (a) Part 1: the reaction between acac and Cu(NO3)22H2O to form [Cu(acac)2]
(b)
Part 2: the reaction between acac and Fe(NO3)39H2O to form [Fe(acac)3]
(c)
Part 3: the reaction between acac and MnCl24H2O to form [Mn(acac)3]
106
Name
Student ID
Results: Metal acac complexes

Yields
Weighings (g) Wt weighing bottle + complex Wt weighing bottle Wt complex [Cu(acac)2] [Fe(acac)3] [Mn(acac)3]
Part 1: Preparation of bis(acetylacetonato)copper(II), [Cu(acac)2]

What did you observe during this reaction?
Calculate the percentage yield for your product.
107
Part 2: Preparation of tris(acetylacetonato)iron(III), [Fe(acac)3]

108
Part 2: Preparation of tris(acetylacetonato)manganese(III), [Mn(acac)3]

109
Questions
1. Consider the observed colour of the three complexes. Which has the strongest absorption of light (ie, which is the darkest)?
2.
Your demonstrator will have a sample of [Ni(ox)2], a complex structurally similar to [Cu(acac)2]. Compare this to your sample of [Cu(acac)2]. Which is darker in colour?
3.
Consider the two four coordinate complexes you have observed: [Ni(ox)2] and [Cu(acac)2]. What geometries are possible for these complexes.
4.
A darker colour is often typical of an allowed electron transition, which is only possible for a tetrahedral complex, while a paler colour is often typical of a forbidden electron transition, which is indicative of a square planar geometry. Based on your observations and this understanding, assign a coordination geometry to each of [Ni(acac)2] and [Cu(acac)2] and sketch a line diagram.
110
5.
Based on your answers above, is [Cu(acac)2] chiral? Explain your reasoning.
6.
Are [Fe(acac)3] and [Mn(acac)3] chiral? Would you expect samples of your iron and manganese complexes to rotate plane polarised light? Explain your reasoning and draw any enantiomers that may be formed.
111
7.
Examine the UV-visible spectra for the three complexes you made today, which are given below.
max [Fe(acac)3] = 431 nm
[Fe(acac)3] [Mn(acac)3] [Cu(acac)2]
max [Mn(acac)3] > 400 nm
max [Cu(acac)2] = 640 nm
Explain the relationship between the max for each compound and the colour that it appears.
112
Departure Checklist
A two mark deduction from the total mark for this experiment will apply if the checklist is not complete and your demonstrator has not initialed your report. My work area is clean and tidy I have cleaned and returned all glassware to the lockers I have wiped down all common areas, such as fumehoods and sinks I have returned all the reagents used I have attached the pre-laboratory questions to my result sheets only. Samples were presented to my demonstrator before disposal. Do not dispose until your demonstrator has sighted the samples. Demonstrators initials
Assessment
Criteria Pre-laboratory questions were... Poor
0 Not attempted 0 No sample presented 0 Not provided 0 Not attempted 0.5 Poorly attempted 0.5 Poorly attempted
Good
1 Mostly incorrect 1 Below expected yield and quality 1 Not sufficient 1 Mostly incorrect 2 Mostly correct 1.5 Mostly correct
Excellent
2 All correct 3 Above expected yield and quality 2 Sufficient 3 All correct
Quantity: The sample presented to the demonstrator was of sufficient yield and purity.
Observations: The observations recorded were...
In-laboratory questions were...
Total (out of 10)
113
This page left intentionally blank.
114
EXPERIMENT 2.4: HARD SOFT ACID BASE THEORY

Safety
!
PPE
Concentrated acids and bases are corrosive and cause severe burns on contact with your skin. Thioacetamide generates hydrogen sulfide, a toxic gas, on contact with acids. You should use all concentrated acids and bases and thioacetamide in the fumehood and wear appropriate gloves. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. 5. relate polarisation to electron donor acid-base properties. distinguish between hard and soft acids and bases based on observed reactivity. relate hard or soft behaviour to predominant bond types. determine the likely reactivity for some simple molecules. identify cations based on their reactivity.
Aim
To utilise some simple experimentation to categorise metal cations based on their reactivity. With some knowledge about their electronic characteristics, to explain how these categories occur and to utilise them to identify an unknown cation.
References
Blackman et al, Chemistry, 1st edition (2007), Wiley, Supplement 1 available on Blackboard.
Introduction
Acidic and basic properties are a fundamental component of much of chemistry. Many molecules have acid or base character. Likewise, many reactions can be described in terms of their acid-base chemistry. The Lewis theory can be based on the concept of polarisation and anions and cations can be classified as as acids and bases. By distinguishing the extent of polarisation a new Hard Soft Acid Base theory can be developed to describe some reactivity phenomena, such as formation of minerals and solubility of simple salts. For example, a cation can be categorised into one of five groups based on some simple sequential steps. These groups are not the same periodic table groups, but are based on their reactivity. This gives very useful insights into the chemistry of the cations that allows us to predict the reactivity involving these ions and also the physical properties of minerals formed from them.
Experiment 2.4: Hard Soft Acid Base Theory
115
For example, a group 1 cation in solution will form a precipitate on addition of hydrochloric acid, while the remaining groups will not. This can be represented by the following reaction:
Similarly, a group 2 cation will form a precipitate on addition of acidic H2S. In acidic solution the sulfide ion concentration is minimised through the following equilibrium:
The sulfide ion will be produced in situ by hydrolysis of thioacetamide, CH3CSNH2. The reduction of sulfide ion concentration allows only the most insoluble group 2 cations to precipitate as their sulfide salts, which can be represented by the following reaction:
A basic solution allows the formation of a greater concentration of sulfide ions. However, it will also precipitate out some very insoluble hydroxides (group 3A). Their precipitation can be controlled by using aqueous ammonia with addition of ammonium chloride, this minimises the hydroxide ion concentration:
The group 3A cation can then precipitate as a hydroxide before the remainder of group 3 (called group 3B) can precipitate. The precipitation of group 3A cations can be represented by the following reaction:
Group 3B will precipitate as sulfides in the absence of ammonium chloride. The reaction will be the same as group 2. Finally the group 4 will precipitate as a carbonate in the presence of ammonium carbonate. This process to categorise the compounds can be illustrated by the flow chart overleaf. If performed correctly, this process can also be used to separate a mixture of metal cations in solution. Because we do not have time to categorise cations from groups 3B, 4 and 5, these are included below.
About this experiment

This experiment is designed to be an investigative laboratory, leading into the topics covered in lectures on periodic properties of the elements. This experiment will be conducted over a two week period during which students will be expected to complete the activities and experiments.
116
Mixture of metal cations
Insoluble
Addition of HCl
Soluble
Group 1 Insoluble Addition of acidic H2S Soluble
Group 2 Insoluble with NH4OH Group 3A Addition of basic H2S without NH4OH Soluble
Group 3B Mn2+ Fe2+ Co2+ Ni2+
Insoluble
Addition of (NH4)2CO3
Soluble
Group 4 Ca2+ Sr2+ Ba2+

Figure 2.4.1: Diagram outlining the procedure to categorise some metal cations.
Group 5 Na+ K+ Li+
Notes on technique and general procedure

Cleanliness
All apparatus should be thoroughly washed using detergent and test tube brush and then thoroughly rinsed with deionised water prior to use. Any contamination of apparatus, even in quite small amounts, will produce spurious results.
Addition of reagents
Use a clean pasteur pipette for all transfer operations involving solutions. When adding reagents, it is important to follow as precisely as possible the instructions regarding the number of drops to be added and the concentration of reagent. After adding reagent, make sure that the solution is homogeneous by stirring or shaking well.
Use of centrifuge
Be gentle. The centrifuges are fragile and can be easily broken. Always balance a tube by a second tube containing an equal volume of water. Should any liquid be spilled in the cups, they must be washed and dried immediately. After centrifuging, the supernatant liquid may be
Experiment 2.4: Hard Soft Acid Base Theory 117
removed by means of a pasteur pipette and the remaining precipitate washed by half-filling the tube with deionised water, stirring the precipitate, centrifuging, and removing the wash liquid with the pipette.
Heating solutions
Small volumes (less than 1.5 mL) can be boiled gently over a small flame. Larger volumes tend to spurt from a semi-micro test tube, and hence are best evaporated in a larger test tube. Heating solutions for prolonged periods at a temperature just below the boiling point can be achieved by immersing the solution in a water bath.
Use of thioacetamide
Thioacetamide, CH3CSNH2, is used as the source of sulfide ions for the precipitation of the acid sulfides of Group 2. Thioacetamide slowly hydrolyses in water to produce H2S, HS and S2 ions. When you intend to carry out such a precipitation, set up a 250 mL beaker for a boiling water bath at the beginning of the laboratory class. Add one or two anti-bumping granules to the bath and maintain on a rolling boil. All heating with thioacetamide must be carried out under your fumehood.
Procedure
STOP
Experimental Part 1 should be completed in pairs during the first lab session. Experimental Part 2 should be completed individually during the second lab session.
Part 1: Categorisation of cations

You will be provided with a solution containing one of the following metal ions: aluminium(III), Al3+ bismuth(III), Bi3+ cadmium(II), Cd2+ chromium(III), Cr3+ copper(II), Cu2+ iron(III), Fe3+ lead(II), Pb2+ mercury(I), Hg22+ silver(I), Ag+
An individual stock solution of each of the above cations will be provided. Using the procedure below assign each of the provided cations with a category (group 1, group 2 or group 3A) based on its reactivity.
STOP
Notes
Cross contamination of solutions can lead to erroneous results. Please ensure that you only use the pipettes provided with a single solution. Let your demonstrator know if you inadvertently contaminate a solution.
Wherever a group precipitate is obtained it is essential to verify that excess precipitant has been added. A group reagent will separate its particular group only from those that follow it and not those that precede it. Hence one group must be completely precipitated before precipitation of the next group can be attempted.
118
Step 1 In a micro test tube add 0.1 mL of 3 M hydrochloric acid to 1 mL of ice cold stock solution. Some cations will give a rapid precipitation, others may require scratching of the walls with a glass pasteur pipette to induce crystallisation. If no precipitation, proceed to step 2 with the same solution. Test the solution for complete precipitation by adding a drop of 3 M hydrochloric acid.
The cation is from Group 1. Confirm the assignment by repeating this step on fresh stock solution. Note the colour of the precipitate.
Step 2 Add a few drops of 0.125 M thioacetamide solution and heat in a water bath to completely precipitate any group 2 sulfides. If no precipitation, proceed to step 3 with the same solution. Test the solution for complete precipitation by adding a few more drops of 0.125 M thioacetamide solution.
The cation is from Group 2. Confirm the assignment by repeating steps 1 and 2 on fresh stock solution. Note the colour of the precipitate.
Step 3 Transfer the solution to a 20 mm diameter boiling tube and heat rapidly in the fumehood until half the volume is reached. Take care not to boil it completely away. Add one drop of 14 M nitric acid and continue boiling until the volume is about 1 mL. Add 0.25 mL of 5 M ammonium chloride and then 3 M ammonia solution until the solution is alkaline (test with red litmus until a blue colour is reached).
The cation is from Group 3A. Confirm the assignment by repeating from step one on fresh stock solution. Note the colour of the precipitate.
Part 2: Identication of a cation

Your demonstrator will provide you with a solution that may contain up to two of the cations above from Group 1, 2 or 3A. Your task is to identify the cations group. Your demonstrator will confirm your assignment and provide you with a procedure to separately identify the cation from its group.
STOP
The centrifuges are the most time limiting step in these procedures. Take care and follow your demonstrators instructions at each stage. Ensure you have made progress on your activity as additional time to complete it will not be provided.
119
Step 1 In a micro test tube add 0.1 mL of 3 M hydrochloric acid to 1 mL of ice cold stock solution. Some cations will give a rapid precipitation, others may require scratching of the walls with a glass rod to induce crystallisation. If no precipitation, proceed to step 2 with the same solution. If precipitation is present, centrifuge and decant the solution. Test the solution for complete precipitation by adding a second drop of 3 M hydrochloric acid and centrifuge if necessary. Proceed to step 2 with the same solution.
The cation is from Group 1. Keep the precipitate to perform a confirmatory test to identify the specific cations present from this group. See your demonstrator for this procedure.
Step 2 Add a few drops of 0.125 M thioacetamide solution and heat in a water bath to completely precipitate any group 2 sulfides. If no precipitation, proceed to step 3 with the same solution. If precipitation is present, centrifuge and decant the solution. Test the solution for complete precipitation by adding a few more drops of 0.125 M thioacetamide solution and centrifuge if necessary. Proceed to step 3 with the same solution.
The cation is from Group 2. Keep the precipitate to perform a confirmatory test to identify the specific cations present from this group. See your demonstrator for this procedure.
Step 3 Transfer the solution to a 20 mm diameter boiling tube and heat rapidly in the fumehood until half the volume is reached. Take care not to boil it completely away. Add one drop of 14 M nitric acid and continue boiling until the volume is about 1 mL. Add 0.25 mL of 5 M ammonium chloride and then 3 M ammonia solution until the solution is alkaline (test with red litmus until a blue colour is reached).
The cation is from Group 3A. Keep the precipitate to perform a confirmatory test to identify the specific cations present from this group. See your demonstrator for this procedure.
The procedure to separate the cations into groups is the same as Part 1, but note that it is essential you follow this procedure correctly. Where a positive is made ensure all precipitate is removed from the solution before proceeding to the next step. Failure to do so will result in false positives as any group 1 cations will give a positive test for group 2 and group 1 and 2 cations will give a positive for group 3A and so on.
Name
Student ID
Pre-laboratory activity
STOP
This pre-laboratory activity should be completed and submitted to your demonstrator at the end of the first laboratory session.
Model 1: Two denitions of acids and bases

Theory Brnsted-Lowry definition Lewis definition Acid An acid is a substance that donates a proton, H+, to another species. An acid is an electron-pair acceptor. Base A base is a substance that accepts a proton, H+, from another species. A base is an electron-pair donor.
Examples:
Reaction Lewis or Brnsted-Lowry Acid or Base?
Critical Thinking Questions

1. Write your answers to the following questions on the table in Model 1: a) b) c) Classify each reaction as a Brnsted-Lowry or Lewis Acid or Base. Identify the acidic and basic species in each of the forward reactions. Identify the acidic and basic species in each of the reverse reactions.
121
2.
Correlate the terms electron rich and electron decient with: a) a Brnsted-Lowry acid.
b)
a Brnsted-Lowry base.
3.
Correlate the terms electrophile and nucleophile with: a) a Lewis acid.
b)
a Lewis base.
Model 2: Polarisability and polarising power

Polarisability () is the degree to which an electron cloud is deformed in an applied magnetic field. As an ion gets bigger and the charge gets increasingly negative it becomes easier to polarise. Polarising power is the inverse and refers to the ability of an ion to distort the electron cloud of an adjacent atom. Polarising Power increases as the ion gets smaller and formal charge gets larger
2 +
3 +
Idealised ion pair Predominantly ionic character
Mutually polarised ion pair Some ionic and covalent character
Polarisation sufcient to form a covalent bond Predominantly covalent character
122

4. Explaining your answer briey, which of an anion or cation in each of the pairs in Model 2 will act as the: a) Lewis acid?
b)
Lewis base?
5.
Consider example 1 in Model 2 of an idealised ion pair: a) What is the extent of polarisability of the ions?
b)
What is the extent of polarising power of the ions?
6.
Consider example 2 in Model 2 of an mutually polarised ion pair: a) What is the extent of polarisability of the ions?
b)
What is the extent of polarising power of the ions?
c)
How does the size of the ions correlate with the idealised ionic pair illustrated by dashed lines?
123
7.
Explaining your answer briey identify which example has the highest level of covalency? How does this relate to the size of the idealised ionic pair illustrated by the dashed line?
8.
Would size of an atom increase or decrease polarisability? Explain your answer.
124
Name
Student ID
Results: Part 1
Complete the following table. Cation aluminium(III), Al3+ bismuth(III), Bi3+ cadmium(II), Cd2+ chromium(III), Cr3+ copper(II), Cu2+ iron(III), Fe3+ lead(II), Pb2+ mercury(I), Hg22+ silver(I), Ag+ Group Observations
Questions
Did you notice any ions that were difficult to precipitate?
Were there any observations that may be useful in identifying an ion?
125
In-laboratory activity
STOP
This in-laboratory activity may be completed while you proceed with the experimental section. It must be submitted at the end of the second laboratory session.
Model 3: Hard and soft acids and bases

Acid High polarising power due to: Small size Hard Small size Base Low polarisability due to:
Large difference in electronegativity be- Large difference in electronegativity between donor and acceptor atoms tween donor and acceptor atoms High positive charge at acceptor site Few or no d electrons Low polarising power due to: Large size High negative charge at acceptor site Absence of empty orbitals suitable for bonding High polarisability due to: Large size
Soft
Small difference in electronegativity be- Small difference in electronegativity between donor and acceptor atoms tween donor and acceptor atoms Low positive charge at acceptor site Often have large number of d electrons Low negative charge at acceptor site Presence of empty orbitals suitable for bonding

9. Explain how the following changes to atomic or ionic properties inuence polarisability: a) increasing radius.
b)
decreasing charge.
126
10.
Explain how the following changes to atomic or ionic properties inuence polarising power: a) decreasing radius.
b)
increasing charge.
11.
Using your answers to previous CTQs explain why charge density (Z/r) is a useful measure of polarising power and polarisability and hence hard soft acid base character.
127
12.
Which combination of a hard or soft acid and base will give a compound with: a) predominantly ionic character?
b)
predominantly covalent character?
c)
some ionic and some covalent character?
13.
Explaining your answer, classify each of the examples given in Model 2 as a hard-hard, hard-soft or soft-soft combination. a) Example 1
b)
Example 2
c)
Example 3
128
Departure Checklist
Assessment
Criteria Pre-laboratory: The pre-laboratory activity was... Part 1: Categorisation of the known cations was... Part 1: Model 2 critical thinking questions were... Part 1: Model 3 critical thinking questions were... Poor
0 Not attempted 0 Not attempted 0 Not attempted 0 Not attempted 0.5 Poorly attempted 1 Poorly attempted 0.5 Poorly attempted 0.5 Poorly attempted
Good
1 Mostly incorrect 2 Mostly incorrect 1 Mostly incorrect 1 Mostly incorrect 1.5 Mostly correct 3 Mostly correct 1.5 Mostly correct 1.5 Mostly correct
Excellent
2 All correct 4 All correct 2 All correct 2 All correct
Subtotal for part 1 (out of 10)
129
130
Name
Student ID
Results: Part 2
My unknown sample:
Observations
Group identication
Cation identication within group
The cations present in my sample were: ...........................................................................................

Model 4: Hard, borderline and soft acids and bases and periodicity
Hard acids H+ Li+ Na+ K+ Be2+ Mg2+ Ca2+, Sr2+ Al3+ Cr3+ Mn2+ Fe3+ Co3+ Any ion with formal charge of 4+ or higher Hard bases F- ClH2O OH- O2ROH RO- R2O CH3COONO3- ClO4CO32- SO42- PO43NH3 RNH2 N2H4 Borderline BrBorderline Soft acids
Fe2+ Co2+ Ni2+ Cu2+ Zn2+ Rh3+ Ir3+ Ru3+ Os2+
Cu+ Ag+ Au+ Cd2+ Hg22+ Hg2+, Pd2+ Pt2+ Pt4+ Br2 I2 Metals with zero oxidation state Soft bases HI- S2H2S HS RSH RS- R2S SCN- CN- RNC CO S2O32R3P (RO)3P R3AsC2H4 C6H6
NO2- N3SO32C6H5NH2 C5H5N

14. Using your experimental results from part 1 place the group number of each cation in its location on the periodic table below. Where a cation with different oxidation states is categorised into different groups, include both groups and their oxidation states. You should also include group 3B and 4 cations provided in Figure 2.4.1. Group 5 has been completed for you.
Grp 5
Li
Grp 5
Na K
Grp 5
132
15.
What do you notice about the positioning of the groups on the periodic table?
16.
Explain how you generalise about the chemistry of a metal cation based on its position on the periodic table.
17.
Explaining your reasoning, classify the three counter-ions you have encountered as either a hard or soft base: a) chloride ion (Cl)
b)
sulde ion (S2)
c)
hydroxide ion (OH)
133
18.
Classify each of the insoluble precipitates observed as a hard-hard, hard-soft or soft-soft combination. a) Group 1
b)
Group 2
c)
Group 3A
19.
Classify each of the insoluble precipitates observed as a predominantly covalent in character or predominantly ionic in character. Explain your reasoning in each case. a) Group 1
b)
Group 2
c)
Group 3A
134
20.
In general, what type of interaction (hard-hard, hard-soft or soft-soft) is likely to form a precipitate?
21.
Explain why sodium, potassium and hydrogen ions can rarely form a precipitate.
22.
Explain why silver(I), lead(II) and mercury(I) ions form a precipitate with moderately hard base such as chloride while the remaining ions do not.
135
Departure Checklist
Assessment
Part 2: Identification of the unknowns was... Observations: The observations recorded were... Part 2: Model 4 critical thinking questions were...
0 Not attempted 0 Not provided 0 Not attempted 1 Poorly attempted 2 One correct 1 Not sufficient 2 Mostly incorrect 3 Mostly correct 4 Both correct 2 Sufficient 4 All correct
Subtotal for part 2 (out of 10)
136
PART 3: SYNTHESIS, ISOLATION & PURIFICATION
137
138
EXPERIMENT 3.1: IDENTIFICATION OF COMPONENTS IN A MIXTURE BY CHROMATOGRAPHY

Safety
!
PPE
m-cresol (1 %) is harmful in contact with skin and if swallowed, and irritating to skin and eyes. Toluene is highly flammable, and harmful by inhalation. Keep away from sources of ignition. Avoid contact with eyes. You should wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. 5. construct a chromatogram and observe a chromatographic separation, relate molecular properties and resulting intermolecular forces of eluent, stationary phase and analyte to resulting separation order and efciency, calculate experimental retention factors (Rf), identify components of a mixture from their Rf values and compare separation efciencies of paper and thin-layer chromatography.
Introduction
Chromatography is a technique used in chemistry to separate a mixture of compounds for identification and analysis. It exploits the concept of varying solubility to achieve this separation of components in solutions, either in the gas or liquid phases. There are two phases present, a mobile phase and a stationary phase, and the movement of the mobile phase or eluent across the stationary phase achieves separation or elutes the compound of interest. Components that are more soluble in the stationary phase will move slower through the process than components that are more soluble in the mobile phase. We are going to use two types of chromatography to separate a mixture into its components, and a range of standards identify the components.
Part 1: Identication of food dyes by paper chromatography

Paper chromatography is an example of partition chromatography. In this type of chromatography, a porous solid (such as cellulose in filter paper) acts as a support for water which forms a thin layer and acts as a stationary liquid phase. The mobile liquid phase carries the mixture of components to be separated over the stationary phase. Separation occurs due to differences in the solubility between the two phases, that is partitioning of the components between the stationary and the mobile liquid phases. A very small concentrated spot of the solution containing a substance or mixture of substances is placed on the baseline (origin) drawn near one end of a sheet of chromatographic paper
Experiment 3.1: Identication of components in a mixture by chromatography 139
(chromatogram). Pure reference solutions are also spotted on the paper for visual comparison. The chromatogram is developed by placing the lower edge of the chromatogram in the selected solvent system (eluent, developing solvent or mobile phase); capillary action causes the solvent to flow up the paper at a uniform rate, resulting in the solvent front gradually moving up the paper. When the solvent front reaches a spot, the components of the spot will begin to migrate upward with the mobile phase. Each component will have a characteristic affinity for the paper and for the solvent; since each component of a mixture will have its own characteristic affinities, each component will travel up the paper at its own characteristic rate. The chromatogram is removed from the mobile phase when the solvent front is a couple of centimetres from the top of the paper. The chromatogram will now contain a vertical array of spots arranged according to their rates of ascent. The position of each spot on a chromatogram can be described in terms of its retention factor, Rf value:
In a given chromatographic system the movement of any substance relative to the solvent front is constant and characteristic of that substance. If an effective separation of all components is not achieved in a particular solvent system, a different solvent system may be chosen which gives a bigger difference in the Rf values of the components and thus permits a positive identification. This form of partition chromatography will be used to identify food colouring dyes. The Australia New Zealand Food Standards Code allows only certain colouring substances, considered to have no harmful effects on health, to be added to foodstuffs. Aqueous solutions of food colouring substances are sold for household use and, by regulation, must be labelled to show the permitted dyes present. The chemical structures, along with corresponding food additive code numbers and Colour Index (CI) numbers, of some commonly used food colouring dyes are given below.
Allura Red AC (CI 16035; Additive Code 129)
Amaranth (CI 16185; Additive Code 123)
Brilliant Blue FCF (CI 42090; Additive Code 133)
(also known as indigotine) Indigo Carmine (CI 73015; Additive Code 132)
Experiment 3.1: Identication of components in a mixture by chromatography
140
Sunset Yellow FCF (CI 15985; Additive Code 110)
Tartrazine (CI 19140; Additive Code 102)
Paper chromatography will be used to identify the dye components in three different commercial colouring dyes.
Procedure
3. 4. 5. Draw a pencil base line 2.5 cm from the narrow edge of piece of large chromatography paper. Mark nine places at even intervals to spot known and unknown substances. Spot and label six of the marked places with the following standard dyes. These standard dyes will be used to identify the unknown components in the commercial dyes. Name Sunset yellow Brilliant blue Tartrazine Amaranth Ponceau 4R Carmoisine 6. Colour Index Number 15985 42090 19140 16185 16225 14720 Code Number 110 133 102 123 124 122
Spot and label any three of the following six commercial dyes, with at least one of them commercial dye 6. Record the commercial dyes you have used on your report sheet. Commercial Dye 1 Commercial Dye 2 Commercial Dye 3 Commercial Dye 4 Commercial Dye 5 Commercial Dye 6 Queen Blue Queen Green Queen Yellow Queen Pillar Box Red Queen Rose Pink Queen Black
7. 8.
Set up a developing tank. Add enough 2 w/v% sodium citrate: 5 v/v% conc. aqueous NH3 mixture (eluting solvent) so that the bottom of the tank is covered. Roll the paper chromatogram and fasten with a paper clip, then carefully stand the paper in the developing tank, ensuring that each sample spot is just above the liquid surface. Cover the tank. Allow the chromatogram to develop for 30 40 minutes (or until the solvent front is about 2 cm from the top of the paper). Immediately mark the solvent front and, after drying, calculate the Rf values of the dyes.
141
9.
10.
Present these data in a table and identify the constituents of the commercial colouring dyes. Include the chromatogram with your report.
Part 2: Identication of phenols by thin layer chromatography

Thin layer chromatography (TLC) is similar to one-dimensional paper chromatography. However TLC utilises a thin layer of suitable adsorbent as the stationary phase. The relative magnitudes of adsorption and partition forces differ to those in paper chromatography. The thin layer consists of a finely divided adsorbent (silica or alumina) mixed with a suitable binder like gypsum (plaster of Paris, CaSO4.2H2O). It is prepared by mixing the adsorbent and binder with water to produce a slurry. This slurry is spread on the inert support, usually a sheet of glass or aluminum, smoothed to give an even thin surface and finally dried. TLC has several advantages over paper chromatography: (a) (b) (c) (d) The time for satisfactory separation is short. The spots remain compact. Extremely small quantities can be used. Strongly corrosive locating agents, e.g. H2SO4 can be used on silica and alumina without deleterious effect. The thin layer is easily scraped away for recovery, by elution, of the spot. Different adsorbents can be used.
Figure 3.1.1: Typical thin layer chromatography setup. (from Christian, G.D. Analytical Chemistry, 6th Edition, 2004, John Wiley)
(e) (f)
TLC is a very powerful separative process for small quantities of mixtures.
Procedure
The reference phenols chosen in this experiment are m-cresol, o-nitrophenol, m-nitrophenol and resorcinol.
m-cresol
o-nitrophenol m-nitrophenol
resorcinol
A 1 % ethanolic solution of each phenol is used for spotting the plate. The unknowns, labelled A, B, C and D, are mixtures, each containing at least two of the above phenols.
!
1. 2. 3.
m-cresol (1 %) is harmful in contact with skin and if swallowed, and irritating to skin and eyes. Draw a pencil base line on a 10 cm x 7 cm silica gel coated sheet from the base. Mark six places at even intervals. Spot and label four of the following phenols and two of the unknown phenols.
142
!
4. 5. 6. 7.
Toluene is highly flammable, and harmful by inhalation. Keep away from sources of ignition. Avoid contact with eyes. Do not dispose of down the sink; place in designated residue bottle. Examine the sheet under ultraviolet light and mark the positions of all phenols using a pencil. Calculate the Rf values of each known phenol and those in the mixtures, tabulating all results. Draw a full-scale diagram of the chromatogram, positioning the spot locations precisely. Include this diagram in your report. Identify the phenols in the unknowns using the Rf values.
143
144
Name
Student ID
Pre-laboratory questions: Paper and thin layer chromatography

1. In your own words, describe the mechanisms of the separation processes that occur in paper chromatography.
2.
List the advantages of TLC over paper chromatography.
3.
If the solvent front moves 8.0 cm and a component in a sample being analysed moves 3.2 cm from the baseline, what is the Rf value for this component?
145
146
Name
Student ID
Results: Paper chromatography

Dye Sunset yellow Brilliant blue Tartrazine Amaranth Ponceau 4R Carmoisine Rf Value(s) Dye Commercial Dye Commercial Dye Commercial Dye Rf Value(s)
Using the Rf values above, identify the constituent(s) in your chosen three commercial dyes. Dye Commercial Dye Commercial Dye Commercial Dye Constituent(s)
Questions
1. Why must the spot applied to the chromatogram be above the level of the developing solvent?
2.
Which dye has: i) the highest Rf value; and ii) the lowest Rf value?
3.
Would the Rf values be the same if the chromatogram was re-run using a different solvent?
147
Results: Thin layer chomatography

Phenol resorcinol m-cresol m-nitrophenol o-nitrophenol Unknown Unknown Identify the phenols present in the unknown based on their Rf values. Phenol(s) Unknown Unknown Draw a full scale diagram of your TLC plate - do not attach the plate itself with your report. Rf value(s)
Question
4. Explain, in terms of structure and intermolecular forces, why o-nitrophenol has a much higher Rf value than the other phenols.
148
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Part 1: The measured Rf values of the standard dyes were... Part 1: The quality of the paper chromatogram was... Part 1: The components of the commercial dyes were... Part 2: The quality of the thin-layer chromatogram was... Part 2: The identity of phenols in the mixture were... 0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
Not attempted
0.5
Outside range
1
Within range
0
Poor
0.5
Good
1
Excellent
0
Not identified
1
Partially correct
2
Fully correct
0
Poor
0.5
Good
1
Excellent
0
Not identified
1
Partially correct
2
Fully correct
0
Not attempted
0.5
Incorrect
1
Correct
Total (out of 10)
149
150
EXPERIMENT 3.2: PURIFICATION OF BENZOIC ACID BY RECRYSTALLISATION

Safety
!
PPE
All organic solvents used in this experiment should be regarded as toxic and flammable. You should use all organic solvents in the fumehood and wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. 5. utilise owcharts to visualise an experimental procedure, identify potential solvents for recrystallisation using variations in solubility of the desired product purify a compound by recrystallisation using variations in solubility, use various ltration techniques (gravity and vacuum ltration) to separate phases, use melting point to examine a compounds purity and potentially its identity.
Aim
In todays experiment we are going to purify a crude sample of benzoic acid using recrystallisation. We are then going to use melting point determination to determine the identity of an unknown.
Introduction
Purification of a solid is usually carried out by crystallisation from a solution in water or an organic solvent. The solubility of most solids in liquids increases with increasing temperature. Consequently, a hot, saturated solution will deposit crystals of the solute on cooling. This process is called crystallisation and the solute is said to crystallise. The choice of the most suitable solvent requires care. The substance to be purified should be readily soluble at the boiling point of the solvent and only very sparingly soluble at room temperature or a little below. Frequently it is necessary to use a mixture of solvents, a common one being ethanol-water.
Experiment 3.2: Purication of benzoic acid by recrystallisation
151
Use of Organic Solvents

When an organic liquid is used for crystallisation, or in a reaction at elevated temperatures, the apparatus usually employed is termed a reflux apparatus. The vapour of the boiling liquid is condensed in a reflux condenser (an ordinary condenser used vertically) and drops back into the flask. This allows heating at the boiling point of the solvent without losing any of the solvent.
STOP
Part 1 - Crystallisation of crude benzoic acid should be performed individually. Part 2 - Melting point determination may be undertaken in groups of four.
Part 1: Crystallisation of crude benzoic acid

The 'crude' benzoic acid used is a mixture of benzoic acid with a soluble impurity and an insoluble impurity.
Procedure
Place 2 3 granules of impure benzoic acid in 1 mL of solvent in a small test tube to determine which of the solvents: toluene, ethanol, hexane, or water is the most suitable for purification by crystallisation. Remember that the main requirement is the substance should dissolve in the hot solvent and crystallise on cooling. Record your observations and indicate the most suitable solvent, considering both solubility and safety aspects in your decision-making process. Confirm your decision with your demonstrator. Weigh out 1 g of impure benzoic acid and place it in a 100 mL conical flask. Purify it by crystallisation using the following procedure: 1. Dissolving the impure compound in the solvent to produce a solution that is saturated with respect to the major component at or near the boiling point of the solvent (about 50 mL). Removing any insoluble impurities by ltration. It is usually necessary to take some precautions to ensure that the solution does not cool and deposit crystals during this process. The simplest method of avoiding this difculty is by using a lter funnel from which the stem has been cut together with a 'uted' lter paper to encourage rapid ltering (see overleaf). It is necessary to warm the funnel as well. This is best done by placing the funnel and lter paper above the ask containing the crude sample and allowing the hot vapours, from the boiling solvent, to warm them. Allowing the ltrate to cool and crystallisation to occur. If time is pressing, the ask can be cooled under the tap or in ice. Impurities that are more soluble than the substance to be puried remain in solution after the desired compound has crystallised. Separating the crystals by suction ltration and washing them to remove any adhering 'mother liquid' (the solution remaining after crystallisation has occurred). This is carried out using a Hirsch or Buchner funnel and a vacuum pump (see the glossary overleaf).
2.
3.
4.
The recrystallised substance may then be dried by drawing air through the sample while it is in the Hirsch funnel, by pressing between filter papers or in a vacuum desiccator or 'drying pistol' (see Furniss et al.4, Section 2.20). It is usually desirable to obtain the final product having crystals as large as possible (to aid rapid filtration and drying). This is best achieved by slow cooling of the hot solution under normal atmospheric conditions. An enhanced yield results from a final cooling in an ice-bath, but this should be done only after the solution has cooled to room temperature. Dry the sample by suction on the Hirsch funnel until your sample is dry.
4
Furniss, B.S., Hannaford, A.J., Smith, P.W.G. and Tatchell, A.R. (1989) "Vogels Textbook of Practical Organic Chemistry" 5th ed., Longman Scientic and Technical, Harlow 152
STOP
Ensure that you provide your sample to your demonstrator to view and mark before discarding the sample. 50% of the marks come from the demonstrators observations of your final product.
Assessment
You will be assessed both on the quantity of the recrystallised product and far more importantly its purity. You must obtain its melting point using the technique described in Part 2.
Filtration glossary
A 'fluted' filter paper is obtained by taking an ordinary filter paper and folding it in halves and then in quarters in the normal way. Instead of opening the paper to fit the funnel at this stage, the folded sections are folded in halves again by doubling them inwards towards the centre fold. Each of the sections obtained in this way is then folded in halves again, the first fold being outwards and then the rest arranged so that the edge of the paper eventually presents a zigzag appearance.
Fold outwards
It is then opened and when fitted into the funnel only folded edges Fold inwards come in contact with the glass, except for two flat sides. These are then creased inward so only folded edges are in contact with the glass. In this way the maximum filtering area is obtained with a paper of given size, and filtration is as rapid as possible. Bchner and Hirsch funnels are porcelain or glass funnels with a perforated disc to support the filter paper in vacuum filtration. The Bchner type has a cylindrical shape, while Hirsch funnels are conical like ordinary glass filter funnels. In use they are fitted into the neck of a filter flask, the side arm of which is connected to the vacuum pump and the whole apparatus clamped in place with a retort stand and clamp as illustrated. A filter paper cut accurately to fit over the porcelain disc is then put in place, moistened with a little of the solvent to be used in the filtration and sucked down tightly by turning on the pump. The suspension of solid is now poured onto the filter and the liquid drains rapidly away from the solid. Any residual solid in the flask should be washed out using some of the filtrate (the liquid in the filtration flask). The solid should be washed with a little of the cold solvent used. This is done by disconnecting the pump, pouring a little solvent onto the solid, reconnecting the pump, and allowing it to suck the liquid through until the solid is as dry as possible. Finally, the solid should be firmly pressed down with a spatula to allow any further liquid to drain away. The main value of Bchner and Hirsch funnels is in recovering a fairly large amount of solid from a suspension as in recrystallisation. When a little solid impurity has to be removed from a large volume of liquid, it is usually better to use a fluted filter paper.
Hirsch funnel and vacuum ask
153
Flowcharts
The procedure given above can also be represented by a simple flowchart. In organic chemistry it is common for procedures to be represented this way, making it clear to follow, particularly when there are multiple similar steps. Flowcharts do not need to be so detailed as you become more familiar with the techniques. For an experienced organic chemist, this procedure can be simplified to recrystallise with [solvent].
Step 1: Add crude mixture to conical ask
Step 2: Add minimum amount of boiling solvent to dissolve most of mixture
Step 4: Discard insoluble impurities
Step 3: While hot, lter the solution through a stemless funnel tted with a uted lter paper Step 7: Keep residue, dry between two pieces of lter paper on a pre-weighed watchglass. Determine yield and melting point. Step 5: Keep the ltrate and cool to room temperature then in an ice bath to promote crystallisation
vacuum
Step 6: Filter by vacuum through a Hirsch funnel tted with two lter papers. Wash the crystals with a little cold solvent. Allow air to draw through to dry puried benzoic acid.
Step 8: Discard ltrate. Clean all glassware and work area

In future experiments, you will be expected to construct a similar flowchart as part of your prelaboratory preparation.
154
Part 2: Melting point determination

The melting point of an organic compound is of considerable value as a criterion of purity and also in characterisation and identification. When reporting a melting point, this is given as a range, from the first signs of melting until the sample is fully molten. A wide melting point range usually indicates impurity, while a sharp melting point, unchanged by further purification (e.g. crystallisation) indicates purity. You will be using an Electrothermal melting point apparatus. A procedure is available with the instrument and your demonstrator will explain its use. A picture is shown above. Melting points may be used to identify a compound. An unknown sample of either benzamide, maleic acid or urea is provided. By mixing the unknown sample with some of the pure sample, the identity of the unknown can be found, remembering that a pure compound will have a narrow melting point range close to its reported value. The accepted melting points from the literature of the three possible candidates is given in the notes.
Procedure
Part 2 should be performed in groups of four to save time. Firstly, determine the melting point of your purified benzoic acid. The apparatus can take multiple samples simultaneously, so ensure that you are determining the melting point of your sample. For comparison, also record the melting points of your other group members. Using the mixed melting point test, identify the unknown compound that is one of the above by mixing a small amount of the unknown with each of the three samples and determining, based on the impact on magnitude of range of melting point, the identity of the unknown.
STOP
Turn the melting point apparatus off immediately after use to ensure there is sufficient time for it to cool before the next use.
155
156
Name
Student ID
Pre-laboratory questions: Purication by recrystallisation

1. Study the ow sheet shown in the introduction and answer the following questions: a) how many ltrations are used in this experiment and name each step?
b)
how, and at what step, are the insoluble impurities removed?
c)
how, and at what step, are the soluble impurities removed?
157
2.
In choosing a suitable solvent for the purication of an organic solid by crystallisation, what essential features must be looked for?
3.
Fred obtained a very small amount of benzoic acid from his recrystallisation experiment. Suggest possible reasons for his low yield, and suggest ways he could maximise his yield next time!
Experiment 3.2: Purication of benzoic acid by recrystallisation 158
Name
Student ID
Results: Crystallisation of crude benzoic acid

Record your observations for the preliminary tests in the following table: Solvent Toluene Solubility in Cold Solubility in Hot Crystals on Cooling
Ethanol
Hexane
Water
Questions
1. Which solvents are suitable for recrystallisation of benzoic acid? Explain your answer.
2.
Which solvent is preferred and why?
STOP
Check with your demonstrator before you proceed with your recrystallisation. You may have more than one option.
159
3.
Weight of crude benzoic acid ...................................... g Weight of pure benzoic acid ...................................... g % Recovery ..................................... % What is the principal advantage of using a uted lter paper?
4.
It is important to wash the crystals after they have been collected. What type of impurities are being removed?
5.
In pre-lab question 3, you were asked to comment on why Fred obtained a very low yield after recrystallisation. Considering the experiment youve just completed, comment on any additional reasons Freds yield was so low and ways to avoid it next time.
Results: Melting points

Record the melting point range for each of the samples and mixed samples below: Melting Point Range (C) Benzamide Maleic Acid Urea 127 130 C 131 - 139 C 133 - 135 C Mixed Melting Point Range (C) Unknown + Benzamide Unknown + Maleic Acid Unknown + Urea
160
6.
Based on your mixed melting point, what is the identity of the unknown? Explain your answer.
Record the melting point range and observations about colour and dryness for your pure benzoic acid sample and those for each member of your group. Make sure you include their names. Group Members Your sample Name: ......................................... Name: ......................................... Name: ......................................... 7. Compare your melting point of the puried sample to the accepted melting point of benzoic acid of 122 C 5. Comment on the purity of your sample. Melting Point Range Colour C Grey, off-white or white Dryness
Dry, slightly wet or wet
8.
Compare the melting point of your sample to that of your group members. Suggest reasons why you may get less than the theoretical melting point of benzoic acid.
CRC Handbook of Chemistry and Physics, p 3-42 161
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions: Correct and logical answers to questions posed. Part 1: The benzoic acid was sufficiently dried. Poor 0 0
Very wet
Good 0.5 0.5

Wet
Excellent 1.5 1.5

Mostly dry
1 1
Slightly wet
2 2
Dry
Part 1: There was sufficient yield of purified benzoic acid present. Part 1: The colour of the benzoic acid sample indicated a high purity Part 1: Answers to questions were logical and correct Part 2: Melting points were correct and answers to questions were related to the observations from the experiment.
0
Very poor
0.5
Fair
1
Good
0
Grey
1
Offwhite
2
White
0 0
Very poor
0.5 0.5
Poor
1 1.5
Good
1
Fair
2
Very Good
Total (out of 10)
162
EXPERIMENT 3.3: PREPARATION AND REACTIONS OF CYCLOHEXENE

Safety
!
PPE
Cyclohexene is a flammable liquid. Phosphoric acid is corrosive.
All procedures in this experiment must be conducted in the fumehood. You should avoid naked flames in the vicinity of cyclohexene and wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. carry out an elimination reaction to form an alkene and identify the alkene functional group through some chemical tests, assemble, use and disassemble Quick-Fit glassware, perform a distillation to safely distill a ammable liquid, use a separating funnel to achieve purication and separation of immiscible liquids.
Aim
To prepare cyclohexene from cyclohexanol, and to carry out several tests on the product to illustrate reactions which are characteristic of alkenes.
Introduction
The elimination reaction that is the basis of this experiment can be expressed as:
H3PO4 heat
OH
H2O
The cyclohexanol and phosphoric acid are placed in the distillation flask (which acts also as a reaction vessel), and when the mixture is heated, the vapour consists mainly of the component with the lowest boiling point. Chemical Cyclohexanol Cyclohexene Phosphoric acid Water
Experiment 3.3 Preparation and reactions of cyclohexene
Boiling Point (C) 161 83 213 (with decomposition) 100

163
You can see from these values that cyclohexene is most volatile, although a little water vaporises as well. In practice, it is impossible to effect complete conversion in this experiment: some cyclohexanol decomposes in other ways, some cyclohexene remains in the reaction vessel, some cyclohexene remains in the condenser and receiving vessel, and some vaporises into the atmosphere and is lost. When you obtain your pure cyclohexene, you measure its volume and using its density (0.8110 g cm3) calculate the mass obtained. Expressed as a fraction of the theoretical yield, this gives you the percentage yield. You will also try some reactions on the cyclohexene you have prepared and compare these reactions with those of cyclohexane, the saturated analogue. To refresh your memory, some reactions of alkanes and alkenes are given below.
CH3 H3C + Br2 no immediate reaction (without UV light)
Br CH3 H3C + Br2 CH3 H3C Br

CH3 H3C + MnO4no reaction
OH CH3 H3C CH3 + H3C OH diol (major)
O O CH3 + H3C O diketone (minor) acid (minor) OH
MnO4-
H3C
This last equation is not balanced, but organic equations are often expressed in this way. The important thing is to be able to follow what happens to the organic molecule. When the last reaction is carried out under mild conditions (e.g. dilute acidified MnO4 and room temperature), the product of the reaction is mainly the diol (di-alcohol).
164
Procedure
STOP
Before commencing the experiment, carefully read the following safety issues and practical points. There is a very real risk from odour and fire in this experiment. You must always follow the advice of your demonstrator.
Prepare the reaction mixture

Into a 100 mL pear-shaped flask, add 20 mL (19 g) of cyclohexanol (directly from the dispenser) and 10 mL of phosphoric (orthophosphoric) acid (directly from the dispenser) and mix well.
Caution: mixing cyclohexanol with phosphoric acid will produce a significant amount of heat. Add them together slowly, with swirling.
Add two or three boiling chips to aid boiling before commencing assembly of your distillation apparatus.
Assembling the distillation apparatus

Assemble your distillation apparatus as shown in the diagram. Poor assembly of the apparatus is the greatest factor in the fire risk. Particular problem areas are the joints between the reaction flask and the stillhead, and the stillhead and the condenser. Ice/water slurries cool more efciently than ice alone. Efcient cooling of the distillate reduces both the re hazard and the odour problems in the laboratory.
Clamp here
Clamp here
Ice/water Reaction mixture and boiling chips Water out
Make sure that you clamp the Water in apparatus in the positions shown and note that the bulb of the thermometer must sit at the junction of the distillation head. Do not clamp the equipment tightly. You want the clamp held tightly enough to prevent it dropping, but not too tight to restrict rotation. The condenser should just rest on the clamp with the fixed arm under the condensor.
Before you turn on your Bunsen burner you must get your demonstrators permission. The greatest risk to fire is due to incorrectly assembled glassware. Cyclohexene is a flammable liquid! Ensure the vapours are properly condensed and do not allow vapour or distillate to be near your flame or your neighbour's flame!
Performing the reaction

Heat the flask gently, using a low blue flame applied directly to the reaction vessel and keeping the flame in constant motion. By slowly waving the Bunsen around the base of the flask, adjust
Experiment 3.3 Preparation and reactions of cyclohexene 165
the heat so that cyclohexene and water slowly distill over. The temperature of the vapour passing into the condenser should not rise above 105C. The distillate is collected in a 100 mL conical flask that is cooled in an ice-water bath. Continue slow distillation until about 10mL of residue (mainly phosphoric acid) remains.
Purifying the product

To the distillate, add 10% sodium carbonate solution (2-3 mL) until the aqueous layer is basic, and transfer the mixture to a small separating funnel (see illustration). You can test for pH using red litmus (it will turn blue when basic). Run off the aqueous layer, and transfer the crude cyclohexene to a dry 100 mL conical flask. Add a small quantity (two spatula tips) of anhydrous calcium chloride, and allow the flask to stand, with occasional swirling, for 10-15 minutes.
Which one is the aqueous layer? Which one is the cyclohexene layer? An easy way to tell is to note the volume of each and add a small amount of water and note which one increases!
Wash the residue from your reaction into the residue container in the fumehood, not in the open laboratory. Filter the cyclohexene into a dry measuring cylinder through a small plug of cotton wool in a filter funnel.
Clean-up
STOP
Its at clean-up that most of the odours in the lab are generated. Make sure you keep all contaminated glassware and waste in the fumehood until the cyclohexene is removed from them. Your demonstrators will deduct marks if odours are detected!
All glassware should be rinsed with acetone prior to washing and the acetone residue placed in the residue container in the fumehood. When you have finished filtering, throw the cotton wool into the solid residue container in the ventilated cupboard, not into the laboratory bins. Determine the weight of cyclohexene using your volume and its density and calculate the percentage yield of cyclohexene.
STOP
Do not dispose of your product until your demonstrator has witnessed your product and recorded a mark on your result sheet.
Present your sample (in the measuring cylinder whilst in the fumehood) to your supervisor.
Reactions of cyclohexene
Perform the following reactions on both your cyclohexene produced above and on a sample of cyclohexane provided. In all reactions make sure you compare results between the two to compare the reactions of an alkene to its saturated analogue. To 5 drops of the cyclohexene in a small test tube add an equal volume of 0.02 M potassium permanganate solution drop by drop and shake well. Add 2 drops of a solution of bromine in dichloromethane (supplied) to 5 drops of cyclohexene in a small test tube, and shake well. Repeat these two tests using the sample of cyclohexane.
166
Name
Student ID
Pre-laboratory questions: Preparation and reactions of cyclohexene

1. Calculate the molecular weight of cyclohexanol and cyclohexene.
2.
How many moles of cyclohexanol are there in 19 g of cyclohexanol?
3.
What weight of cyclohexene would be obtained if all the cyclohexanol were converted into cyclohexene? This mass is termed the theoretical yield.
167
4.
Complete the procedural flow chart for the preparation of cyclohexene up to the purification stage by writing each of the steps in the boxes provided.
Step 2 Step 1
2 Pear-shaped ask
This procedure must be performed in a fumehood
Step 3
3 Distillation apparatus
Step 4
Step 7 Upper layer
5 7 Conical ask
Step 6 Lower layer Step 5
Separating funnel
Submit this sheet to your demonstrator when you enter the laboratory at the start of the session. They will return it after the pre-lab so you may use it during the experiment.
Name
Student ID
Results
Questions: Reaction
1. What is the function of boiling chips?
2.
What is the purpose of distillation of cyclohexene and water from the reaction mixture?
3.
Why distill slowly?
4.
Why have the collection ask in an ice-water bath?
169
Questions: Purication
In the separation of product cyclohexene from water: 5. Why was Na2CO3 solution added?
6.
What is the lower layer?
7.
What is the purpose of the anhydrous CaCl2?
Using the expected 100% conversion of cyclohexanol calculated in the pre-lab, calculate the final yield from the mass of product as a percentage.
170
Reactions of cyclohexene
8. To 5 drops of the cyclohexene in a small test tube add 0.02 M potassium permanganate solution drop by drop and shake well. Compare this to your observations of this process with cyclohexane. Explain your observations (what you see) for both your prepared cyclohexene and the sample of cyclohexane.
9.
Write a chemical equation describing any reaction observed in Question 8 above.
10.
Add 2 drops of a solution of bromine in dichloromethane (supplied) to 5 drops of cyclohexene in a small test tube, and shake well. Compare this to your observations of this process with cyclohexane. Explain your observations (what you see) for both your prepared cyclohexene and the sample of cyclohexane.
11.
Write a chemical equation describing any reaction observed in Question 10 above.
171
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions: Correct and logical answers to questions posed. Preparation: The yield of the product was... Poor 0 0
Very poor
Good 0.5 0.5

Poor
Excellent 1.5 1.5

Very good
1 1
Good
2 2
Excellent
Purification: The colour of the product was...
0
Deeply coloured
0.5
Lightly coloured
1
Colourless
Purification: The product clarity and dryness was... Preparation and purification: Answers to questions posed were logical and correct. Reactions: Observations and inferences were correct and logical. Equations were provided for all reactions observed.
0
Water droplets
0.5
Very cloudy
1
Cloudy
1.5
Slightly cloudy
2
Very clear
0
None
0.5
Some
1
All
0.5
1.5
Total (out of 10)

EXPERIMENT 3.4: PREPARATION OF 4-NITROACETANILIDE

Safety
!
PPE
This experiment uses concentrated acids, which are corrosive and may cause burns if they come into contact with your skin. You will be asked to wear gloves when handling the concentrated acids and during clean up of the reaction mixture. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. 5. prepare a detailed procedural owchart from a written experiment, safely handle concentrated acids to prepare a nitrating mixture, utilise recrystallisation to purify a product, calculate crude and pure yields for a reaction and apply the mechanism for electrophilic aromatic substitution to explain the formation of this product.
Aim
To prepare 4-nitroacetanilide from acetanilide by electrophilic aromatic substitution.
Introduction
The nitro group (NO2) is a very important functional group in aromatic chemistry, since it is readily introduced into an aromatic ring. It can be reduced to the amino group (NH2), and diazotization of a primary amine yields a diazonium salt, from which a range of compounds, including dyes, can be prepared. This experiment is an example of an electrophilic aromatic substitution (EAS) in which the electrophile is the NO2+ ion.
NHCOCH3 + HNO3 H2SO4 NHCOCH3 + H2O
NO2 acetanilide 4-nitroacetanilide
The nitrating mixture is generated through reaction of nitric acid (HNO3) and sulfuric acid (H2SO4) to form the electrophile NO2+.
Experiment 3.4 Preparation of 4-nitroacetanilide 173
Procedure
Concentrated acids, such as nitric, sulfuric and glacial acetic acid, are highly corrosive and all contact with skin and clothing must be avoided. Drops of acid spilt on the bench are a common cause of acid burns; therefore ensure that any spillage is cleaned up immediately. Ask your demonstrator for advice/assistance.
Prepare the nitrating mixture

Prepare a nitrating mixture by cautiously adding 1 mL of concentrated nitric acid to 3 mL of cold concentrated sulfuric acid directly from the dispensers into a small, dry flask. Cool the mixture in an ice bath for later use. Leave this to one side while you prepare the acetanilide for reaction.
Prepare the reaction mixture

In a dry 100 mL conical flask, dissolve 1.6 g of acetanilide in 3 mL of glacial acetic acid (directly from the dispenser) by warming gently. Cool the acetanilide solution in an ice bath, and then add slowly, with swirling, 3 mL of concentrated sulfuric acid. Cool the acetanilide solution in an ice bath, remove the flask from the bath, and add the nitrating mixture, 3 or 4 drops at a time, from a dry Pasteur pipette. Mix the viscous mixture thoroughly during the addition, and keep the temperature below 30 C by cooling in the ice bath. After all the nitrating mixture has been added, allow the mixture to stand at room temperature for 15minutes. Pour the mixture slowly with stirring into a 250 mL beaker containing 50 mL of ice cold water and a handful of crushed ice.
Separation and purication of the product

Collect the product by suction filtration on the Hirsch funnel, and wash the filter cake with about 5mL of water. Recrystallize this crude product using ethanol. Follow the procedures in Experiment 3.2 for recrystallisation of benzoic acid. Determine the melting point of your sample using the procedure given in Experiment 3.2.
STOP
Do not dispose of your product until your demonstrator has witnessed your product and recorded a mark on your result sheet.
Show your sample to your demonstrator for assessment. Once a mark is recorded on your report sheet, you may dispose of the sample in the yellow hazardous waste bins.
Experiment 3.4 Preparation of 4-nitroacetanilide
174
Name
Student ID
Pre-laboratory questions: Preparation of 4-nitroacetanilide

1. Calculate the molecular weight of acetanilide and 4-nitroacetanilide.
2.
How many moles of acetanilide are there in 1.6 g of acetanilide?
3.
How many moles of 4-nitroacetanilide would be obtained if all the acetanilide were converted into 4-nitroacetanilide? This amount is termed the theoretical yield. The percentage yield is determined by dividing the moles of product obtained by the moles of theoretical yield and multiplying by 100.
4.
From a reference source, such as the CRC Handbook of Chemistry and Physics, find the theoretical melting points of acetanilide and 4-nitroacetanilide. Cite this reference6 .
You may use any referencing style. Information on how to cite references is available here: http://libguides.library.curtin.edu.au/content.php?pid=141214 175
5.
Using the examples given in Experiments 3.2 and 3.3 construct your own flowchart for this experiment. This should be sufficiently detailed and contain all the relevant procedural steps for this experiment. Your demonstrator must view and approve this flowchart before you will be permitted to commence this experiment. If it is incomplete or incorrect, you will be given time at the start of the lab to finish it.
STOP
176
Name
Student ID
Results: Preparation of 4-nitroacetanilide

Questions
1. The reaction to form 4-nitroacetanilide is an electrophilic aromatic substitution. Identify the following components of this reaction. a) the entering group (this must be an electrophile)
b)
the leaving group (this is the species that is lost, also an electrophile)
c)
the solvents present in the reaction mixture
2.
Consider your answers to Question 1. In the reaction mixture, what is the function of the: a) sulfuric acid in the nitrating mixture
b)
acetic acid, and
c)
added sulfuric acid?
177
3.
The amide group (NHOCCH3) attached to the aromatic ring causes a directive effect, stabilising and activating electrophilic substitution at the ortho- (2-) and para (4-) positions on the ring. a) Why is the product 3-nitroacetanilide never observed in this reaction?
b)
Why would the minor product 2-nitroacetanilide not be observed under these conditions?
4.
Based on your answers to Question 3, why is the temperature kept below 30 C?
5.
Why is the mixture: a) left 15 minutes at room temperature,
b)
poured into ice-water?
178
6.
Using the expected 100% conversion of acetanilide calculated in the pre-lab, calculate the final pure and crude yields from the mass of product as a percentage.
7.
Determine the melting point of your product and comment on its value with reference to the literature value determined in the pre-lab.
179
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions were... Poor 0
Not attempted
Good 0.5
Partially attempted
Excellent 1
All correct
Flowchart: The flowchart prepared was... Quantity: The pure yield was... Quality - dryness: The product was...
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Very wet
0.5
Damp
1
Dry
Quality - colour: The product was...
0
Not observed
0.5
Deeply coloured
1
Brown
1.5
Yellow
2
Pale cream

Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
180
EXPERIMENT 3.5: CARBOXYLIC ACIDS AND THEIR DERIVATIVES USING MIND MAPS TO LINK CONCEPTS
Safety
!
PPE
Concentrated sulfuric acid is corrosive. Methyl salicylate has a strong odour and you should ensure that the concentration of the vapour in the laboratory is kept to a minimum. All procedures in this experiment must be conducted in the fumehood. You should wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. prepare a detailed procedural owchart from a written experiment, carry out a nucleophilic acyl substitution reaction to form an ester, distinguish between a carboxylic acid and its derivatives through some chemical tests and, construct a mind map of related and interlinked concepts in chemistry.
Aim
To prepare an ester by the reaction of a carboxylic acid with an alcohol and to examine some of the characteristic reactions of carboxylic acids and derivatives. Using these results a mind map linking these and other related concepts will be constructed.
Introduction
Carboxylic acids and their derivatives have the general formula:
where Y may be oxygen, nitrogen, halogen or sulfur atoms contained in attached groups. The four common carboxylic acid derivatives are the acid halides, acid anhydrides, esters and amides. In this exercise you will be given three unlabelled compounds (a carboxylic acid, an ester and an amide) and asked to determine which is which by using simple chemical tests.
Carboxylic acid
Acid halide (X = F, Cl, Br, I)
Acid anhydride
Ester
Amide
181
Experiment 3.5 Carboxylic acids and their derivatives using mind maps to link concepts
To refresh your memory some reactions of these compounds are listed below. Acidity Carboxylic acids are acidic and are readily soluble in basic solutions.
RCOOH RCOO- + H+ RCOOH + NaHCO3 RCOO-Na+ + H2O + CO2

Acid halides and anhydrides are not acidic themselves, but react with water to form acidic solutions. Esters and amides are neutral and do not normally react with water.
RCOX + H2O RCOOH + HX (RCO)2O + H2O 2RCOOH

Nucleophilic Acyl Substitution Most of the chemistry of carboxylic acids and their derivatives can be described as nucleophilic acyl substitution (NAS). A general equation is given below.
Particular examples of NAS are described below. Ester Formation Esters can be formed by the reaction of alcohols with carboxylic acids, acid chlorides or anhydrides.
RCOOH + ROH RCOOR + H2O RCOCl + ROH RCOOR + HCl (RCO)2O + ROH RCOOR + RCOOH
Ester Hydrolysis Esters are readily hydrolysed under basic conditions to give alcohols and the carboxylic acid salt.
RCOOR + NaOH RCOO-Na+ + ROH

The hydrolysis can also be achieved under acid conditions but it does not go so well. Amide Formation Amides can be formed by the reaction of ammonia, primary or secondary amines with acid chlorides or anhydrides.
RCOCl + 2NH3 RCONH2 + NH4+ + Cl(RCO)2O + 2NH3 RCONH2 + NH4+ + RCOORCOCl + 2RNH2 RCONHR + RNH3+ + ClAmides are not readily prepared from carboxylic acids. Amide Hydrolysis Amides can be hydrolysed under acidic or basic conditions. Under acidic conditions, the carboxylic acid and the ammonium salt are obtained, while under basic conditions, the carboxylate salt and the amine (or ammonia) are obtained.
RCONH2 + H+ + H2O RCOOH + NH4+ RCONH2 + OH- RCOO- + NH3

Base hydrolysis of primary amides produces ammonia that can be readily detected by odour or with litmus paper. This reaction has commonly been used for the identification of amides.
Experiment 3.5 Carboxylic acids and their derivatives using mind maps to link concepts 182
Reduction Reactions Esters can be reduced to give primary alcohols, and amides to give amines. These are usually reduced with lithium aluminium hydride (LiAlH4).
RCOOR
RCH2OH + ROH
RCONH2
RCH2NH2
The reduction of carboxylic acids, acid halides and anhydrides can also be achieved with LiAlH4. These also give primary alcohols.
Procedure
Preparation of methyl salicylate
STOP
The yield of ester can be increased substantially by using a longer reflux time. Methyl salicylate has a strong odour and you should ensure that the concentration of the vapour in the laboratory is kept to a minimum.
The reaction to prepare methyl salicylate is shown below:

O C OH + CH3OH H2SO4 O C OCH3 + H2O
OH salicylic acid
OH methyl salicylate (Oil of Wintergreen)
Into a dry, 100 mL pear-shaped flask, add approx. 5 g of salicylic acid and 35 mL of methanol. Carefully add 5 mL of concentrated sulfuric acid with swirling.
Caution: This process is quite exothermic and may cause the methanol to boil.
Add a few anti-bumping granules and set up the apparatus for reflux as illustrated.
183
There is no need to grease the joint in this experiment; the grease will contaminate your product. Reflux the mixture using a water bath for 1.5-2 hours. Keep an eye on the water flow through your reflux condensor or it may boil dry! During this reflux period carry out Part 2 below Identification of Unknown Compounds and commence work on the concept mapping exercise. Cool the flask, then pour the mixture into a separating funnel containing 50 mL of cold water. Shake the mixture and run out (and retain) the organic layer. Discard the aqueous layer and return the organic extract to a separating funnel with 10 mL of 10% sodium hydrogen carbonate solution. The washing process involves shaking the organic extract with an aqueous solution and separating the organic layer from the aqueous layer.
Caution: A lot of carbon dioxide may be released when adding the sodium hydrogen carbonate so avoid a pressure build-up in the separating funnel! Your demonstrator will show you how to do this correctly. The glassware may explode if not handled correctly.
Separate the organic extract from the aqueous layer and dry it with a little calcium chloride (approximately two spatula tips). Allow the mixture to stand for about 5 minutes, or until the liquid is no longer turbid. Filter the ester through a small filter funnel containing a small plug of cotton wool into a clean, dry measuring cylinder. Record your yield (and % yield) of methyl salicylate and show to your demonstrator for assessment. Density of methyl salicylate = 1.174 g cm3.
Identication of unknown compounds

You are provided with three sample bottles labelled A, B and C containing white solids. One contains an acid, another an amide and the third an ester, though not necessarily in that order. Without being told which ones, use some simple chemical tests to identify the contents of the three bottles. The structure of the three compounds are below.
184
Concept Maps
Concept maps are diagrams that can assist in understanding the degree of interconnectedness between the concepts that are relevant to a given topic. The value in creating concept maps lies in the fact that the creator may need to recognise which concepts are relevant as well as which are directly related. Furthermore, the process of creating a map encourages rigorous reflection upon the nature of the relationship between concepts. Different people working independently will rarely produce similarly arranged concept maps. The maps will often indicate the different perceptions that their creators have of the topic under investigation. For any given topic, there is no uniquely correct concept map. A completed concept map (either provided to students or created by students) can be an excellent summary of a particular topic.
Example
Students were asked to construct a concept map showing the relationship between the concepts; nucleophile, Lewis base, SN reaction, backside attack, solvolysis, SN1 reaction, leaving group, SN2 reaction, inversion of configuration, nucleophilic substitution reaction, nucleophilic displacement reaction and any others that are appropriate. Below is a possible solution of a completed concept map relating these concepts.
185
Your Task
In the laboratory, you will be given a partial concept map relating to the functional groups: alcohols, aldehydes, alkyl halides, amides, amines, carboxylic acids, esters, ethers and ketones. Complete the map by indicating how the groups are related, and how they can be interconverted. You may wish to extend the map by including other functional groups. Bring your lecture notes and/or textbook.
Experiment 3.5 Carboxylic acids and their derivatives using mind maps to link concepts 186
Name
Student ID
Pre-laboratory questions: Carboxylic acids

1. Explain why the preparation of methyl salicylate will not proceed if dilute sulfuric acid is used instead of concentrated sulfuric acid.
2.
In this experiment, 0.034 moles of salicylic acid were reacted with 0.864 moles of methanol. This is a mole ratio of approximately 1:24. However, the stoichiometry of the reaction suggests that a mole ratio of 1:1 is all that is required. Why do you think such a large excess of methanol was used?
3.
In this experiment, you will carry out tests to identify three unknown compounds. What functional groups are present in each of the possible unknown compounds?
187
4.
Using the examples given in Experiments 3.2 and 3.3 construct your own flowchart for this experiment. This should be sufficiently detailed and contain all the relevant procedural steps for this experiment. Your demonstrator must view and approve this flowchart before you will be permitted to commence this experiment. If it is incomplete or incorrect you will be given time at the start of the lab to finish it.
STOP
188
Name
Student ID
Results: Questions
Part 1: Preparation of methyl salicylate
1. What is the function of the sulfuric acid?
2.
Which is the organic layer? How could you tell if you are unsure?
3.
What is the function of the sodium hydrogen carbonate solution?
Calculate the yield of your compound:
189
Part 2: Identication of unknown compounds

4. What tests did you perform and what were your observations and conclusions?
5.
Using the results of the test you performed, what is the contents of each of the sample bottles?
STOP
Attach your concept map to your lab report for this experiment.
190
Departure Checklist
A two mark deduction from the total mark for this experiment will apply if the checklist is not complete and your demonstrator has not initialed your report. My work area is clean and tidy I have cleaned and returned all glassware to the lockers I have wiped down all common areas, such as fumehoods and sinks I have returned all the reagents used Attach your pre-laboratory questions to your result sheets and mind map only, with your name and student ID where indicated. Demonstrators initials
Assessment
Your demonstrator will assess your performance in this laboratory according to the assessment key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability. Criteria
Pre-laboratory questions were... Flowchart: The flowchart prepared was... Quantity: The pure yield was... Quality: The product was...
Poor
0
Not attempted
Good
0.5
Partially attempted
Excellent
1
All correct
0
Very poor
0.5
Good
1
Excellent
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Very wet
0.5
Damp
1
Dry
Quality: The product was...
0
Deeply coloured
0.5
Slightly coloured
1
Colourless
Concept map: The product was...
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct

Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
191
192
EXPERIMENT 3.6: ALCOHOLS AND PHENOLS

Safety
!
PPE
The oxidation of benzyl alcohol is very vigorous so it is essential that the alcohol be added dropwise. All procedures in this experiment must be conducted in the fumehood. You should wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. prepare a detailed procedural owchart from a written experiment, construct a reux apparatus safely, utilise recrystallisation to purify a product and calculate crude and pure yields for a reaction.
Aim
To prepare benzoic acid from benzyl alcohol, recrystallise this product and determine melting point to assess its purity.
Introduction
The reaction that is the basis of this experiment can be expressed:
1. KMnO4/NaOH CH2OH COOH 2. H2SO4
benzyl alcohol
benzoic acid
To refresh your memory, some reactions of alcohols are listed below. 1. Reaction with Active Metals Alcohols react with Li, Na, K and other active metals to form metal alkoxides, which are stronger bases than NaOH and KOH. ROH + Na RO-Na+ + H2 2. Formation of Haloalkanes Alcohols, when treated with HCl, HBr or HI give the corresponding haloalkane. CH3CH2CH2CH2OH + HBr CH3CH2CH2CH2Br + H2O Haloalkanes can also be prepared by the treatment of alcohols with phosphorus or sulfur based reagents, e.g. PCl3, PCl5, PBr3, SOCl2.
Experiment 3.6: Alcohols and phenols 193
3ROH + PX3 3RX + H3PO3 ROH + SOCl2 RCl + HCl + SO2 3. Dehydration of Alcohols Under acidic conditions, alcohols may be dehydrated (elimination of water). Typical conditions involve the use of either concentrated sulfuric acid or phosphoric acid and heat. CH3CH2CH(OH)CH3 CH3CH=CHCH3 + CH3CH2CH=CH2 4. major product
Formation of Esters Alcohols will react with carboxylic acids (with an acid catalyst) to form esters. Esters can also be formed by the reaction of alcohols with acid chlorides or acid anhydrides. ROH + RCOOH ROCOR + H2O ROH + RCOCl ROCOR + HCl ROH + (RCO)2O ROCOR + RCOOH
5.
Oxidation of Alcohols Primary and secondary alcohols are oxidised by a variety of reagents including potassium permanganate, sodium or potassium dichromate, pyridinium dichromate (PDC) and pyridinium chlorochromate (PCC). PDC and PCC are usually used for the controlled oxidation of primary alcohols to aldehydes.
6.
The chemistry of phenols is similar to that of alcohols in many ways. Phenols will react with active metals to form phenoxide ions that are weaker bases than hydroxide ions. Phenols will form esters in the same way as alcohols. Phenols can be oxidised to form quinones.
Phenols do not usually undergo reaction with HCl, PCl3 or SOCl2, nor can they be dehydrated.
Experiment 3.6: Alcohols and phenols
194
Procedure
Place 2 g of potassium permanganate, 5 mL of 3 M of sodium hydroxide and a few anti-bumping stones into a 100 mL pearshaped flask and add approximately 25 mL of water. After adding the reagents, grease the joint and then set up the apparatus for reflux as shown at right. Clamp loosely
Figure 3.6.1: The reux apparatus is set up as shown. Before commencing your reux, please ensure your demonstrator has observed your apparatus.
Water out
The clamps must be fitted as shown, with the lower clamp holding the apparatus together and the upper clamp loosely tightened to stop the condenser moving during reaction.
Clamp rmly
Water in
Pear-shaped ask
Water bath Bunsen burner, with tripod and gauze
STOP
Glass joints must be greased with Vaseline when strongly alkaline solutions are being used (for neutral or acidic solutions, grease is not necessary).
Heat the flask so that the reaction mixture is boiling gently and continuously. Too vigorous heating or stop-start boiling may cause problems, e.g. vigorous bumping so that the contents of the flask splash up the condenser. Slowly add by Pasteur pipette drop by drop 1 mL (1.04 g) of benzyl alcohol using a dropper (see Safety Issues (a) and (b)). The addition should take about 5-10 minutes (slower addition offers no advantage).
The oxidation of benzyl alcohol is very vigorous so it is essential that the alcohol be added dropwise. This is best done using a Pasteur pipette dropping the alcohol down the inside of the condenser. The tip of the pipette should be as low as possible down the condenser.
Rinse the residual benzyl alcohol down the condenser with a few millilitres of water and allow the reaction to continue until the reaction appears complete (10-15 minutes).
195
Cool the reaction mixture in an ice bath and filter off the manganese dioxide using a Hirsch funnel. Wet the paper with a little water first to make sure it is seated properly in the funnel. Wash the manganese dioxide on the filter paper with two 3 mL portions of water to remove adsorbed sodium benzoate.
Care is needed as too much metabisulfite and acid may produce high levels of SO2.
Transfer the filtrate to a 100 mLconical flask and add enough sodium metabisulfite (one spatula at a time) so that the solution becomes clear and colourless. It may be necessary to add a few millilitres of dilute sulfuric acid. Caution: SO2 may be produced.
STOP
Glassware stained with manganese dioxide must be cleaned with a dilute solution of sodium metabisulfite.
Then acidify the solution with dilute sulfuric acid until a large amount of white solid is precipitated. Avoid using too much acid as the extra solvent will dissolve some of the product. Collect the benzoic acid by vacuum filtration and recrystallise it from water. About 60-80 mL is usually required, but it is better to start with <50 mL and add more as needed. Refilter the recrystallised product and allow air to draw through the product until dry. Transfer the product to a clean and dry preweighed watch glass and record its mass. If time permits, determine the melting point of the dried product and calculate the percentage yield.
STOP
Show your dried sample of benzoic acid to your demonstrator for assessment before discarding.
196
Name
Student ID
Pre-laboratory questions: Alcohols and phenols

1. The common names of some reactants that will be used in this laboratory exercise are listed below. Write the structure of each compound and give the correct IUPAC name. Common Name Structure IUPAC Name Molecular weight
Benzyl alcohol
Benzoic acid
2.
Explaining your answer briey, what appearance do you expect the reaction mixture to have at i) the beginning, and
ii)
the completion of the reaction?
197
3.
Using the examples given in Experiments 3.2 and 3.3 construct your own owchart for this experiment. This should be sufciently detailed and contain all the relevant procedural steps for this experiment. Your demonstrator must view and approve this flowchart before you will be permitted to commence this experiment. If it is incomplete or incorrect, you will be given time at the start of the lab to finish it.
STOP
198
Name
Student ID
Results: Alcohols and phenols

Questions
1. What is the purpose of the reflux condenser?
2.
Why is the benzyl alcohol added slowly?
3.
How could you easily tell when the reaction is complete? Hint: Look at the condensing vapour.
199
4.
Including chemical equations as part of your answer, what is the purpose of the addition of: a) sodium metabisulfite?
b)
sulfuric acid?
Yield and purity

1. With the assistance of your demonstrator, calculate the expected 100% conversion of benzyl alcohol to benzoic acid using your quantities of starting reagents.
200
2.
Determine the mass of your puried and dry product. Mass of container Mass of container + your sample Mass of your sample (by difference) g g g
3.
Using the 100% conversion value calculated above determine your yield (mass obtained) as a percentage of this conversion value.
Yield 4.
Determine the melting point of your product and comment on its value with reference to the literature value provided in Experiment 3.2.
201
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions were... Poor 0
Not attempted
Good 0.5
Partially attempted
Excellent 1
All correct
Flowchart: The flowchart prepared was... Quantity: The pure yield was... Quality - dryness: The product was...
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Very wet
0.5
Damp
1
Dry
Quality - colour: The product was...
0
Not observed
0.5
Brown
1
Cream or yellow
1.5
White fine powder
2
White crystals

Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
202
PART 4: CHEMICAL AND PHYSICAL CHANGES
203
204
EXPERIMENT 4.1: INTERMOLECULAR FORCES SOLUBILITY IN LIQUIDS

Safety
!
PPE
Methanol, ethanol, 1-propanol, hexane and toluene are all flammable.
All procedures in this experiment must be conducted in the fumehood. You should wear appropriate gloves if requested. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. relate the structure of a molecule to the likely intermolecular forces it will undergo, observe variations in solubility of compounds as a function of their intermolecular forces, draw some general rules about solubility based on structure and intermolecular forces.
Introduction
The physical properties of pure molecular substances (such as melting point, heat of fusion, boiling point, heat of vaporisation, specific heat, viscosity and surface tension) depend on the strengths of intermolecular forces. The strengths of intermolecular forces are also important factors that govern whether or not one molecular substance dissolves in another. If two molecular substances dissolve, then each of the following processes occurs. (a) (b) (c) Solute molecules are separated from each other. Solute-solute attractions resist this. Solvent molecules are separated from each other. Solvent-solvent attractions resist this. Solute and solvent molecules mix with each other. Solute-solvent attractions assist this.
Whether or not two molecular substances dissolve in each other can be accounted for as follows. (a) (b) There is a natural tendency for molecules of different substances to mix amongst each other. Molecular substances will dissolve in each other if: (i) (ii) both solute-solute attractions and solvent-solvent attractions are weak so that there is little resistance to the tendency to mix. the solute-solvent attractions are sufficiently strong to overcome the resistance to mixing due to solute-solute and solvent-solvent attractions. Otherwise, the substances will not dissolve in each other.
Experiment 4.1: Intermolecular forces - solubility in liquids
205
Forces between uncharged species (neutral molecules) are called van der Waals Forces. They range from hydrogen bonding, to dipole/dipole interaction, dispersion, or London dispersion, forces. 1. 2. 3. The forces of hydrogen bonding are significant with NH, OH and FH groups. The forces of dipole/dipole interaction are the forces that will cause the + part of one molecule to be attracted to the part of a neighbouring molecule. Dispersion forces (or London dispersion forces) are present in all substances. They are the forces that attract non-polar molecules to each other.
The aim of this experiment is to test a number of pairs of substances for mutual solubility, and to explain your observations in terms of intermolecular interactions. To make these explanations you will need to examine the structure of each molecule investigated and its polarity.
Procedure
Methanol, ethanol, 1-propanol, hexane and toluene are all flammable. Do not light any Bunsen burners while using them at the open bench. The organic solvents used in this experiment should not be poured into the sink. Discard these solvents and solutions of these solvents in the waste solvents bottle.
Part 1: Solubilities of molecular substances in molecular liquids

In this experiment we shall attempt to find out which molecular substances dissolve in one another and seek explanations for our observations. Our investigations will include: (i) (ii) (iii) (iv) (v) hexane, C6H14, CH3(CH2)4CH3. toluene, C6H5CH3. methanol, CH3OH. glycerol, HOCH2CHOHCH2OH. water, H2O. Before you begin ensure that all test tubes are clean and dry by rinsing first with 0.5 mL of ethanol and allowing them to dry. If the test tubes are wet or contaminated will you get erroneous results.
STOP
With a dropper pipette, put about 1 mL of hexane into a clean, dry, small (7 cm) test tube. Add about 1 mL of toluene. Shake the test tube. In the appropriate place in the table, record whether or not toluene is soluble in hexane. In a similar way, test the solubility of toluene in each of the following. (i) (ii) (iii) methanol, CH3OH. glycerol, HOCH2CHOHCH2OH. water, H2O.
Record your observations in the table. Using 1 mL of each liquid and the small test tubes, test the solubilities of the liquids in each other. Shake each test tube thoroughly by inverting it. Record your observations in the table. To your test tube containing 1 mL of water and 1 mL of hexane add about five drops of methyl orange, shake the test tube vigorously and record your observations.
Experiment 4.1: Intermolecular forces - solubility in liquids 206
Part 2: Polar and non-polar parts of molecules

In part 1 we saw that methanol dissolves in water but not in hexane. Do all alcohols behave similarly? We shall see that the solubility of an alcohol depends on the number of OH groups in its molecules, as well as on the structure of the rest of the molecule. In this experiment we will test the solubilities of the following alcohols in water and in hexane and seek explanations for our observations. (i) (ii) (iii) (iv) (v) (vi) (vii) methanol ethanol 1-propanol 1-butanol 1-pentanol ethylene glycol (ethane-1,2-diol) glycerol
Put 1 mL of hexane into each of seven, dry, 7 cm test tubes. Use about 1 mL of each alcohol to test its solubility in hexane. Repeat the procedure for water.
207
208
Name
Student ID
Pre-laboratory questions: Intermolecular forces solubility in liquids

1. Draw the structures of the following compounds: a) hexane
b)
toluene
c)
water
d)
methanol
e)
ethanol
f)
1-propanol
g)
1-butanol
h)
1-pentanol
i)
ethylene glycol (1,2-ethanediol)
j)
glycerol
209
2.
Which of the compounds in question 1 contain a dipole moment? Explain your answer and include a diagram. (Hint: look for differences in electronegativities)
3.
Which of the compounds in question 1 do not contain a dipole moment? Explain your answer and include a diagram.
4.
Compounds that contain a dipole moment are said to be polar. Based on this observation, which of the two main solvents is polar and which is non-polar? Explain your answer briefly. a) hexane
b)
water
210
Name
Student ID
Results: Intermolecular forces solubility in liquids

Part 1: Solubilities of molecular substances in molecular liquids
Complete the following table with your observations. In the final row state whether each is polar or non-polar (based on the results) hexane hexane toluene methanol glycerol water polar/ non-polar soluble soluble soluble soluble soluble toluene methanol glycerol water
Questions
1. By inspection of your results, make generalisations and note any exceptions found about the solubilities of: (i) non-polar substances in non-polar substances.
(ii)
polar substances in polar substances.
(iii)
non-polar substances in polar substances.
211
2.
In terms of the relative strengths of the different intermolecular forces in terms of solvent and solute interactions, make some generalisations about the solubilities of: (i) non-polar substances in non-polar substances.
(ii)
polar substances in polar substances.
(iii)
non-polar substances in polar substances.
3.
When you added 1 mL of hexane to 1 mL of water, which substance was the upper layer? Which substance is denser?
4.
When you added methyl orange to the water/hexane mixture, which layer did the methyl orange end up in? Is methyl orange polar or non-polar?
212
Part 2: Polar and non-polar parts of molecules

Complete the following table with your observations. Alcohol methanol ethanol 1-propanol 1-butanol 1-pentanol ethylene glycol glycerol Solubility in water Solubility in hexane
Questions
5. Describe the trends in the solubilities of methanol, ethanol, 1-propanol, 1-butanol and 1pentanol: (i) in water.
(ii)
in hexane.
6.
Compare the structures of molecules of methanol, ethanol, 1-propanol, 1-butanol and 1pentanol with respect to: (i) the number of hydroxyl groups in their molecules.
(ii)
the size of the hydrocarbon portion of their molecules.
213
7.
How do the solubilities in water of alcohols with one hydroxyl group in their molecules depend on the size of the hydrocarbon portion of their molecules?
8.
Account for your conclusion in Q7, using arguments based on intermolecular forces, particularly hydrogen bonds.
9.
Compare the solubilities of ethanol and ethylene glycol in hexane.
10.
Compare the structures of molecules of ethanol and ethylene glycol with respect to: (i) the number of hydroxyl groups in their molecules.
(ii)
the size of the hydrocarbon portion of their molecules.
214
11.
Ethanol is soluble in water. Do you expect ethylene glycol to be soluble in water? Why?
12.
How do the solubilities in hexane of alcohols with two carbon atoms in their molecules depend on the number of hydroxyl groups in their molecules?
13.
Explain why 1-propanol is soluble in hexane, but glycerol is not.
14.
Trends in solubilities are also seen for substances other than alcohols. For example, the larger the hydrocarbon part of aldehydes, ketones, acids and amines, the less soluble they are in water. Explain why acetic acid is soluble in water, but decanoic acid, CH3(CH2)8COOH, is not.
215
Departure Checklist
Assessment
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0 Part 1: Student observations were...

not given
1
partially detailed & correct
2
fully detailed & correct
Part 1: Answers to questions were...
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0 Part 2: Student observations were...

not given
1
partially detailed & correct
2
fully detailed & correct
Part 2: Answers to questions were...
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
216
EXPERIMENT 4.2: DESIGNING AND MAKING BUFFER SOLUTIONS

Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. 5. calculate pH of a buffer solution using the Henderson-Hasselbalch equation, construct a buffer by addition of a weak acid and weak base to a solution, construct a buffer by addition of a weak base to a solution and adjusting by addition of a xed amount of a strong acid or vice-versa, observe the impact of addition of strong acids and bases to a buffer and relate to its buffer capacity, measure the pH of solutions using a pH probe, relate calculated values to observed values and rationalise the difference due to analyte activity.
Aim7
To construct a buffer solution at a particular pH by two different mechanisms and measure the impact of addition of small amounts of strong acid or base.
Introduction
Buffers are an enormously important phenomenon in chemistry. They are commonly found in many biological and industrial systems. A buffer is a solution that resists rapid and uncontrolled changes in pH. In the body blood is buffered by the carbonic acid (H2CO3/HCO3) buffer system which keeps blood pH at 7.40 0.05. The buffer maintains function in a process called homeostasis. Failure to maintain blood pH can lead to serious disease or even death. A buffer is a solution containing a weak acid and its conjugate base, which is also weak. When both species are found in water they form an equilibrium, for example between the hydrogen carbonate ion (HCO3) and the carbonate ion (CO32). Because this is an acid dissociation the equilibrium is governed by the acid dissociation constant (Ka) of the weakly acidic hydrogen carbonate ion
This experiment has been adapted from a rst year experiment undertaken at The University of Western Australia. 217
Experiment 4.2: Designing and making buffer solutions
When a strong acid (H3O+) is added to this solution it contains both a weak acid (HCO3) and a weak base (CO32). The strong acid reacts completely with the weak base and forms the weak acid, for example:
When a strong base (OH) is added to a buffer solution it reacts completely with the weak acid and forms the weak base, for example:
Therefore, as long as there is sufficient buffer components (weak acid and weak base) present in the solution, the pH can be maintained nearly constant. This capacity for change is called the buffer capacity and can be measured by titrating the buffer solution with a strong acid or base. At every stage, where there are still buffer components present, the pH of the buffer can be determined using the Henderson-Hasselbalch equation:
pH = pKa + log [CO2 ] 3 (aq) [HCO(aq) ] 3
When there are no more buffer components present then pH will rapidly change. The addition of strong acids or bases will be in excess and will dominate the pH seeing a rapid decrease or increase respectively. There are three methods through which we can make a buffer and estimate its pH. 1. Dissolve the weak acid and weak base into the same solution. Here the pH can be determined directly by applying the Henderson-Hasselbalch equation directly given the concentrations of the acid and base in the nal solution and Ka (and pKa) of the weak acid. Dissolve the weak base into solution and partially neutralise with a strong acid (such as hydrochloric acid). Here we assume the strong acid will react with the weak base completely and produce the same number of moles of the weak acid (as per the reaction given on page 1). We can then estimate the pH using the Henderson-Hasselbalch equation as for Method 1. Dissolve the weak acid into solution and partially neutralise with a strong base (such as sodium hydroxide). Here we assume the strong base will react with the weak acid completely and we can then estimate the pH using the Henderson-Hasselbalch equation as for Method 1 and 2. This exercise will involve as much thinking as doing. You should discuss your approach as a group and with your demonstrator, if necessary.
2.
3.
STOP
The procedure is provided on your report sheet.
218
Name
Student ID
Pre-laboratory questions: Designing and making buffer solutions

1. 0.10 mol of solid sodium hydrogen carbonate and 0.20 mol of solid sodium carbonate are dissolved in the same beaker of water, transferred to a volumetric ask and made to 250.0 mL. The Ka for HCO3 is 4.7 x 1011. a) What is the pH of the resulting buffer?
b)
What is the pH of solution after 20.00 mL of 0.050 mol L1 hydrochloric acid solution is added to the original solution?
c)
What is the pH of the resulting buffer after 0.040 g of solid sodium hydroxide is added to the original solution?
219
2.
Plan how you would make 100.0 mL of a buffer solution with a pH of 10.80 to be made using only sodium carbonate, sodium hydrogen carbonate and water. You should specify the amounts of sodium carbonate and sodium hydrogen carbonate that you would use. Show all calculations clearly to your demonstrator before you proceed to step 2.
STOP
Remember that reagents are expensive. Do not use more than you think is necessary.
220
Name
Student ID
Results
Part 1: Making a buffer solution from a weak acid and its conjugate base
1. Based on your answer to pre-lab question 2, record the masses of sodium carbonate and sodium hydrogen carbonate you dissolved and made up to 100.0 mL volume with deionised water. Adjust your calculation for pH using your actual masses. sodium carbonate (Na2CO3) Mass of container Mass of container + compound Mass of compound (by difference) g g g sodium hydrogen carbonate (NaHCO3) g g g
2.
What was the measured pH of your buffer?
Measured pH = .....................................
Experiment 4.2: Designing and making buffer solutions 221
3.
Calculate how much the pH of 100 mL of your buffer solution would change if 5.00 mL of 0.20 mol L1 hydrochloric acid solution were added to it.
4.
Add 5.00 mL of 0.20 mol L1 hydrochloric acid solution to your buffer and measure its pH.
Measured pH = .....................................
?
5.
A pH measures the activity (effective concentration) rather than the actual concentration. Activities are usually much less than 100% of the concentration value, for this system around 70%, therefore you can expect a lower than anticipated pH. Is the change in pH consistent with your prediction? Explain your answer.
222
Part 2: Making a buffer solution from a weak base and partial neutralisation with hydrochloric acid.
1. Your demonstrator will give you a target pH. Write this down on your report sheet.
Target pH = ..................................... 2. Accurately weigh out between 1.9 and 2.1 g of sodium carbonate and based on this mass calculate how much 0.20 mol L1 hydrochloric acid solution as is required to get your target pH. Show all supporting calculations clearly.
3.
Dissolve your mass of sodium carbonate in a little water. Add to it as much 0.20 mol L1 hydrochloric acid solution as is required to get your target pH and check to ensure you have the correct value. Take your solution to your demonstrator for testing. Explain how you might make the same buffer solution using 2.00 g of sodium hydrogen carbonate and 0.20 mol L1 sodium hydroxide solution.
4.
223
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Part 1: The experimental plan to produce the buffer was... Part 1: The measured pH of the buffer was... Part 2: The experimental plan to produce the buffer was... Part 2: The demonstrators pH of my buffer was... 0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
Not provided
0.5
Incorrect
1
Correct
0
Outside range
1
Within range
0
Not provided
1
Incorrect or invalid
2
Correct and valid
0
Not measured
0.5
> 10% of expected
1
10% of expected
2
5% of expected
3
2% of expected
0
Not attempted
0.5
Mostly incorrect
1
Mostly correct
Total (out of 10)
224
EXPERIMENT 4.3: KINETICS OF THE IODINE CLOCK REACTION

Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. inspect how concentration effects rate of reaction and relate to an order of reaction with respect to that reagent, determine a rate law experimentally and compare to a theoretical mechanism, observe the inuence of temperature change and catalysts on the rate of reaction and, calculate the activation energy for this process.
Aim8
To examine the effect of concentration changes on the rate of the iodine clock reaction and determine an experimental rate law. Using this experimentally determined rate law two proposed mechanisms can be inspected and confirmed or denied. Similarly, the impact of temperature and catalysis will also be assessed.
Background
Why should the rate of a reaction be important? Indeed, what is the rate of a chemical reaction? To answer the last question first. The rate of a chemical reaction is a measure of how fast products are being formed by that chemical reaction. Conversely, it is also a measure of how fast reactants are being consumed. This will be discussed in more detail later on. The rates of chemical reactions are of great importance in industrial and biological processes. The economic viability of many industrial processes is largely effected by the rate at which the products can be formed. Of more vital importance, in the true sense of the word, every chemical reaction taking place in your body is occurring at a rate carefully controlled by the most complex of catalystsenzymes. Life would be impossible without the rates of countless, complicated chemical processes being controlled with exceptional precision by exquisitely formed enzyme catalysts. The thermodynamic favourability of a process (ie the work needed to complete that process or the energy released by that process) can be determined by applying the Laws of Thermodynamics and simply measuring the initial and final energy of the system. This tells us nothing about the rate at which the process can occur. Indeed, many highly favourable processes will not proceed at a measurable rate until something triggers or catalyses them.
8
This experiment was partially adapted from First Year Experiment 6 from The University of Adelaide. 225
Experiment 4.3: Kinetics of the iodine clock reaction
For example: a litre of petrol will burn vigourously in air to produce a great deal of energy. However, no obvious reaction will be observed until the vapour above the petrol is ignited9. In this exercise the kinetics of the iodide-peroxodisulfate reaction will be studied. This is known as the Iodine Clock Reaction. The effect of concentration of reactants, and of temperature on the rate of reaction will be considered. Reaction kinetics is the study of the rate and mechanism of chemical reactions. Our understanding of chemistry is greatly increased by studying the details of chemical processes.
Mechanisms
The equation for the overall reaction may be written:
When we write such an equation we are making a statement about the starting materials and the end products of the reaction. A chemical equation does not imply that the process takes place in one step. To state that this is the reaction mechanism is to imply that the three reactant molecules will collide absolutely simultaneously,with the correct orientation and sufficient energy, and then instantly be converted to products. This is extremely unlikely. When studying reaction kinetics an attempt is made to describe a chemical reaction as a series of single steps or elementary steps. The elementary steps must satisfy two requirements: 1. 2. The sum of the elementary steps in a mechanism must give the overall balanced equation for the reaction. The rate determining step (RDS), which is the slowest step in the sequence of steps leading to product formation, should predict the same rate law as is determined experimentally.
If it is possible to write a series of chemical equations that describe each of the elementary steps in a chemical process then that series of steps is a reaction mechanism. Thus, the sequence of steps in the study of a reaction mechanism are: measuring the rate of reaction through experimentation formulating the rate law based on the results postulating a reasonable mechanism based on the rate law
In the experiment you will do today, you will measure the rate of the reaction of the oxidation of iodide ions (I) with peroxodisulfate (S2O82) ions under various conditions and use your results to formulate an experimentally determined rate law. Several possible hypothetical mechanisms for the reaction being studied and the rate law or rate expression which can be derived from them will be provided. Your experimental rate law will either support or contradict the mechanisms provided. The mechanism which supports your experimentally derived rate law will be the likely mechanism for the reaction. For example, one of the proposed mechanisms for the oxidation of iodide ions with peroxodisulfate ions is:
Dont try this at home! 226
These two equations are elementary steps in the overall chemical reaction. They state that two iodide anions collide to form an intermediate di-iodide species which lasts long enough to react, at some time later with one molecule of peroxodisulfate to form the final products. This is much more plausible than a simultaneous and instantaneous reaction, however it is only one of several possible mechanisms which you will consider.
Rate determining step and rate law

As already stated it is often the case that one of the elementary steps in a reaction mechanism is much slower than the rest. If this is so, the overall reaction rate is equal to the rate of this slowest step and this step is called the rate determining step (RDS). Some reactants may be not be involved in the RDS. Consider the hypothetical mechanism for the oxidation of iodide ions with peroxodisulfate ions above. The first step is the rate determining step so the rate of the reaction can be determined from the first step alone:
This is the rate law or rate expression for the reaction where k is the rate constant. If this rate law is the same as the experimentally determined rate law formulated from your experimental results, the mechanism is the likely one for the reaction. If the rate law contradicts your results, other mechanisms must be considered.
Rate laws and elementary steps

Once the mechanism of a reaction is determined, the observed rate of the reaction may be rationalised and, if necessary, the reaction conditions can be adjusted to control the rate of the process. While it is not possible generally to predict the rate of a chemical reaction from the equation that describes it, it is possible to do so for an elementary step in a reaction mechanism. For two atoms, ions or molecules to react they must first collide. The rate of the reaction is therefore proportional to the rate of collision for any given temperature. The rate of collision is proportional to the concentration of the species involved in the elementary step. The rate of an elementary step is proportional to the concentration of reactants involved in that step. Consider three simple examples of elementary steps: Example 1 Example 2 Example 3
First order process overall First order process with respect to A
Second order process overall First order process with respect to C First order process with respect to D
Second order process overall Second order process with respect to F
The order with respect to a reagent can only be determined by experiment, which then allows us to postulate a proposed mechanism of elementary steps which matches these findings.
Experiment 4.3: Kinetics of the iodine clock reaction 227
The order of an overall reaction or with respect to an individual reactant can not be determined from the reaction stoichiometry.
The iodine clock

In determining the rate of the reaction the rate of change of concentration of reactants or products at any time "t" must be known. For this reaction it is convenient to study the rate of formation of iodine (I2) since this product is coloured and also gives an even stronger deep blue colour when an indicator is present. In this case well use a synthetic indicator, but the naturally occurring polysaccharide starch may also be used. However, since the colour of the iodine in solution builds up gradually, it would be difficult to compare accurately the rate of production of iodine for one kinetic run with that of another. The problem may be overcome by adding, to the reacting system, a standard amount of a material that would react with the iodine formed and so delay the formation of any iodine colour until all the added material had reacted. The time elapsing before the first trace of iodine colour in the reacting system would be the time required (t) for a standard amount of iodine to be formed. From this the initial rate of change of concentration of iodine may be determined. The reagent used here is sodium thiosulfate. The thiosulfate ions (S2O32) are oxidised by iodine according to the reaction,
Thus, according to this equation, if 10 mL of a 0.1 g L1 Na2S2O3.5H2O solution is added to the iodide-peroxodisulfate reacting system, the S2O32 would react with 2.02 106 moles of I2. This represents the amount of I2 formed before an iodine colouration appears. The easiest way to visualise this experiment is through the following diagram:
00:00 88:88
+
Peroxodisulfate Iodide Iodine
+
Sulfate
Is there any thiosulfate present? Yes +

Tetrathionate Iodide Iodine
+ No
Iodine Starch
+
Thiosulfate
25:45 88:88
228
1. 2.
In all reaction mixtures there is a xed and constant concentration of thiosulfate. A known concentration of peroxodisulfate is added to a known concentration of iodide and the stop watch is started. The reaction between these proceeds and iodine and sulfate is formed. If there is thiosulfate present it will react with the iodine reducing it to iodide, which is consumed in the original reaction. This cycle will continue until all of the thiosulfate is consumed. Once the thiosulfate is consumed it will react with the starch and form a blue complex. The stopwatch is stopped and time recorded. This time represents the time (t) required to consume a xed concentration of iodide. The experiment is repeated at different concentrations of iodide or peroxodisulfate or a different temperature. In all cases the same concentration of thiosulfate is always used.
3. 4. 5.
6.
Calculations
Part 1: Effect of concentration: determination of order
The rate law for the overall reaction can be given by:
The time measured for the blue colour is dependent on the fixed concentration of thiosulfate present and a fixed change in iodine concentration produced. Therefore [I2] is constant and:
The aim of the first two experiments is to determine x and y. From the first experiment, where the iodide concentration is held constant you will have plotted t1 versus [S2O82]. From this graph the value of x may be determined, i.e. the order of reaction with respect to the peroxodisulfate concentration. The graph will either: 1. 2. 3. be independent of [S2O82] (does not vary with [S2O82]), i.e. zero order, x = 0. vary directly as [S2O82] (the graph will be linear), i.e. rst order, x = 1. vary as a higher order of [S2O82] (the graph will be parabolic), x > 1.
To confirm the order as second or third order, plot t1 against [S2O82]2 or [S2O82]3. A straightline plot is the necessary evidence for assigning a value to x. From the second experiment with the data provided, where the peroxodisulfate concentration is held constant you will have plotted t1 versus [I] and you can determine y using the same mechanism described above. Knowing the values of x and y, the rate constant, k, may be calculated from the equation:
229
You can calculate k using data from any experiment and it should be the same for all experiments conducted at that concentration and temperature.
Part 2: Effect of temperature: determination of activation energy

Using the rate expression you derived above, the rate constant k can be determined at each of the four temperatures studied (on ice, at room temperature, 30 and 40 C). The Arrhenius equation relates temperature and the rate constant:
This can be rearranged into a linear form:
where:
k T Ea A R
= rate constant = temperature (in K) = activation energy (in J) = frequency factor = ideal gas constant = 8.314 J K1 mol1
Based on the rate expression, if concentrations of all reagents are held constant between the different temperature experiments then: and A plot of ln t versus T1 will give a straight line, with the slope +Ea/R. From your data calculate the value of the activation energy (Ea) in kJ.
Procedure
When performing kinetics experiments it is important to change just one variable at a time to determine the impact to the rate of reaction with respect to that variable. In this experiment we will examine two variables: the influence of concentration of each of the two reactants and then the temperature of reaction.
Part 1: Varying concentration
STOP
1.
There are six experiments given in the table below. You should work in pairs to complete at least three of the six experiments and collaborate with another pair who will do the other three experiments.
Using a measuring cylinder add the required volume from the table below of potassium iodide along with the given mass of iodine indicator 10 (which is a solid) to a clean and dry 100 mL conical ask. Label this ask 1. Using a pipette add the required volume from the table below of thiosulfate solution to ask 1 and swirl to dissolve and mix the reagents.
2.
10
For the indicator 0.2 g equals about half of a spatula full, which is sufcient. There is no need to accurately weigh this mass. 230
3.
Into a second clean and dry 100 mL conical ask using a measuring cylinder add the required volume from the table below of peroxodisulfate solution and water. Label this ask 2. This will give the nal concentration of peroxodisulfate given in the last row. Quickly add the contents of ask 1 to ask 2 and start a stopwatch. Mix the reagents by swirling once only and carefully observe the reaction. Halt the stopwatch when the rst appearance of a blue colour is seen. Note this time down for this experiment: t. Repeat for another two experiments, noting down which of these you performed on your report sheet, and obtain the missing data from another group. Note their full names down in the space provided on your report sheet. Construct graphs of t1 versus the concentration of peroxodisulfate for each of the reactions performed where iodide concentration is held constant. Repeat step 6 for the varying concentrations of iodide when concentration of peroxodisulfate is held constant. There is no need to perform these experiments the data is already provided in the table.
4.
5.
6.
STOP
7.
Using the linearity of the graphs constructed in Part 1 determine the orders of reaction with respect to peroxodisulfate and iodide and therefore the overall reaction order and rate law for this experiment. Using this rate law calculate the rate constant, k, for two different experiments and compare the values. Reagent iodide (0.125 M) 1 thiosulfate (0.1 g indicator peroxodisulfate (0.025 M) 2 water [peroxodisulfate] mol L1 L1) Experiment 1 20 mL 10.00 mL 0.2 g 20 mL 0 mL 0.025 2 20 mL 10.00 mL 0.2 g 10 mL 10 mL 0.0125 3 20 mL 10.00 mL 0.2 g 8 mL 12 mL 0.01 4 20 mL 10.00 mL 0.2 g 6 mL 14 mL 0.0075 5 20 mL 10.00 mL 0.2 g 4 mL 16 mL 0.005 6 20 mL 10.00 mL 0.2 g 2 mL 18 mL 0.0025
Flask
Part 2: Effect of temperature and catalysis
STOP
There are five experiments given in the table below. You should work in pairs to complete at least two of the first four experiments and collaborate with another pair who will do the other two experiments. All groups should perform experiment 5.
In this experiment the effect of temperature on the rate of the reaction between iodide ion and peroxodisulfate ion is studied. The effect of concentration on this reaction rate has already been studied above. The concentrations will be held constant in this experiment, and the temperature will be varied. The effect of a catalyst on the reaction will also be studied. 1. Using a measuring cylinder add the required volume from the table below of potassium iodide along with the given mass of iodine indicator 11 (which is a solid) to a clean and dry 100 mL conical ask. Label this ask 1. Using a pipette add the required volume from the table below of thiosulfate solution to ask 1 and swirl to dissolve and mix the reagents.
2.
11
For the indicator 0.2 g equals about half of a spatula full, which is sufcient. There is no need to accurately weigh this mass. 231
3.
Into a second clean and dry 100 mL conical ask using a measuring cylinder add the required volume from the table below of peroxodisulfate solution and water. Label this ask 2. This will give the nal concentration of peroxodisulfate given in the last row. You will need to perform each experiment at a xed and known temperature: 4.1. For Experiment 1 place the two asks into a large beaker of tap water. This will maintain the temperature during the reaction. Record the temperature of each of the two asks and wait until they are constant. Note this temperature down and keeping the asks in the water bath proceed to step 5. 4.2. For Experiment 2 place the two asks into a large beaker of ice and water. This will maintain the temperature during the reaction. Record the temperature of each of the two asks and wait until they are constant. Note this temperature down and keeping the asks in the water bath proceed to step 5. 4.3. For Experiment 3 place the two asks into the water bath set at 30 C. This will maintain the temperature during the reaction. Record the temperature of each of the two asks and wait until they are constant. Note this temperature down and keeping the asks in the water bath proceed to step 5. 4.4. For Experiment 4 place the two asks into the water bath set at 40 C. This will maintain the temperature during the reaction. Record the temperature of each of the two asks and wait until they are constant. Note this temperature down and keeping the asks in the water bath proceed to step 5. 4.5. For Experiment 5 repeat the process for Experiment 1, just with the addition of the copper/iron sulfate catalyst.
4.
5.
Quickly add the contents of ask 1 to ask 2 and start a stopwatch. Mix the reagents by swirling once only and carefully observe the reaction. Halt the stopwatch when the rst appearance of a blue colour is seen. Note this time down for this experiment: t. Repeat for another experiment, noting down which of these you performed on your report sheet, and obtain the missing data from another group. Note their names down in the space provided on your report sheet. Construct graphs of ln t1 versus the inverse temperature T1 for each of Experiments 1 4. Determine the slope from the line of best fit for the curve constructed in step 7 and determine the activation energy (Ea) for this reaction. Comment on the effect of a catalyst on the rate of reaction based on your results for Experiments 1 and 5. Reagent iodide (0.125 M) 1 thiosulfate (0.1 g L1) indicator peroxodisulfate (0.025 M) 2 water [peroxodisulfate] mol L1 FeSO4CuSO4 solution Conditions Experiment 1 20 mL 10.00 mL 0.2 g 10 mL 10 mL 0.0125 None Room temp 2 20 mL 10.00 mL 0.2 g 10 mL 10 mL 0.0125 None On ice 3 20 mL 10.00 mL 0.2 g 10 mL 10 mL 0.0125 None 30 C 4 20 mL 10.00 mL 0.2 g 6 mL 14 mL 0.0075 None 40 C 5 20 mL 10.00 mL 0.2 g 4 mL 16 mL 0.005 Four drops Catalyst room temp
232
6.
7. 8. 9.
Flask
Name
Student ID
Pre-laboratory questions: Kinetics of the iodine clock reaction

1. 20 mL of 0.125 M potassium iodide solution is mixed with 10 mL of 0.1 g L1 sodium thiosulfate solution and 0.2 g of solid iodine indicator is added. To this solution is added 20 mL of 0.025 M peroxodisulfate solution. After 46 seconds a blue colour appears, indicating that sufficient I2 has been formed from the reaction between KI and peroxodisulfate to consume all the thiosulfate present. The final temperature is 18 C. a) What is the initial concentration of iodide in the reaction mixture?
b)
What is the initial concentration of peroxodisulfate in the reaction mixture?
c)
What is the number of moles of thiosulfate consumed after 46 seconds of the reaction?
Question 1 continued overleaf...

Question 1 continued... d) What is the number of moles of iodine formed after 46 seconds of the reaction?
e)
What is the change in concentration of iodine (I2) formed after 46 seconds of the reaction?
f)
Assuming the reaction is first order in both reactants (x = y = 1) use the rate expression below to calculate the rate constant, k.
234
2.
The time taken for the blue colour to appear following the mixture of 20 mL of 0.125 M potassium iodide solution, 20 mL of 0.025 M potassium peroxodisulfate solution, 10 mL of 0.1 g L1 sodium thiosulfate solution and 0.2 g of indicator is measured as a function of temperature. To determine the activation energy of the reaction the logarithm of rate constant is plotted against the reciprocal of the Kelvin temperature and a straight line drawn through the points. The co-ordinates of two points on the line are: 1. 2. T1 = 3.39 x 103 K; T1 = 3.60 x 103 K; ln t = 3.82 ln t = 5.09
Using this data, determine the slope of the graph between these two points and find the activation energy for this reaction under these conditions.
235
3.
Prepare a flow chart12 of the procedure indicating the practical steps used to determine the time taken in the iodine clock reaction.
12
Flowcharting are covered in Part 3 of this laboratory manual. If youre not sure how to complete this owchart, see your demonstrator the week before the experiment commences. 236
Name
Student ID
Part 1: Effect of concentration

The name of my partner: ................................................................................................................. The names of the group we shared results with: ................................................................................................................... Experiment
Mark the experiments you conducted with an asterisk (*).
Concentration / mol L1 Iodide [I] Initial solution 0.125 0.125 0.125 0.125 0.125 0.125 Reaction mixture Peroxodisulfate [S2O82] Initial solution 0.0250 0.0125 0.0100 0.0075 0.0050 0.0025 Reaction mixture
Time t / s t1 / s1
1 2 3 4 5 6
Construct a graph of inverse change in time versus concentration of peroxodisulfate.
t1 / s1
[K2S2O8]mixture / mol L1
Concentration / mol L1 Experiment Iodide [I] Initial solution 0.125 0.100 0.063 0.050 0.025 Reaction mixture Peroxodisulfate [S2O82] Initial solution 0.0250 0.0250 0.0250 0.0250 0.0250 Reaction mixture
Time t / s 46 58 92 116 230 t1 / s1
1 2 3 4 5
Construct a graph of inverse change in time versus concentration of iodide.
t1 / s1
[KI]mixture / mol L1 Rate law

Visually inspect the two graphs in Part 1. Which is linear, which is not? Based on these observations, determine the orders with respect to the two reagents.
The order of the reaction, with respect to S2O82 (x) is: .................................................................. The order of the reaction, with respect to I (y) is: .........................................................................
What units with the rate constant, k, have in this case? (Hint: the overall units of rate are mol L1 s1 where time is measured in seconds)
Showing your calculations clearly and using any two of the results from the experiments above, derive the value of k in each case under these conditions using your experiment rate law. Include any units! Reaction conditions [I] / M [S2O82] / M t / s [I] / M k Varying peroxodisulfate Varying iodide
239
Results: Effect of temperature

The name of my partner: ................................................................................................................. The names of the group we shared results with: ................................................................................................................... Experiment
Mark the experiments you conducted with an asterisk (*).
Time t / s
Temperature T / K
1/Temp T1 / K1
ln t / s
1 2 3 4 5 Construct a graph of natural log of change in time versus inverse temperature in Kelvins.
ln t
T1 / x 103 K1
240
Compare Experiments 1 and 5. What impact did the addition of a catalyst have on this reaction?
Construct a line of best fit and determine the slope of this line
From this slope, determine the value of the activation energy (in kJ).
241
Departure Checklist
Assessment
Not attempted
0.5
Partially attempted
1
All correct
Flowchart: The flowchart prepared was... All parts: All graphs were complete, neat, detailed and fully labelled Part 1: Correct order, with working, wrt S2O8
2
0
Poor
0.5
Good
1
Excellent
0
None
0.5
Poorly presented
1
Few were complete
1.5
Mostly complete
2
All complete
0
No
1
Yes
0 Part 1: Correct order, with working, wrt I

No
1
Yes
Part 1: Rate constant value within accepted range (less one mark if units are absent) Part 2: Activation energy value within accepted range
0
35%
0.5
25%
1
20%
1.5
15%
2
10%
0
15%
0.5
10%
1
5%
Total (out of 10)
242
EXPERIMENT 4.4: EXPLORING HESS LAW USING CALORIMETRY

Safety
!
PPE
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. measure heat using simple adiabatic calorimetry, calculate the enthalpy of a process using calorimetry, apply Hess Law to determine an unknown enthalpy and, construct and manipulate graphical data.
Aim13
To use calorimetry to determine the enthalpy of neutralisation for ammonia by hydrochloric acid and the enthalpy of solution for ammonium chloride. Through application of Hess Law the enthalpy of formation of ammonium chloride can be calculated.
Introduction
Thermodynamics is the study of energy changes and transfer. Thermodynamics allows us to measure, calculate and predict the amount of energy released or consumed in, and therefore work done by or on, a process. When this process is a chemical reaction this is called thermochemistry. For example, these processes may be the combustion of fuel to drive your car or the amount of energy generated by solar panels.
Heat
Heat in thermodynamics has a very specific definition: If energy flows between two bodies, or between a system and its surroundings, due solely to their temperature difference then that energy is heat. In most cases the terms energy or thermal energy can replace heat with no loss of meaning. Any process that gives off heat is called an exothermic process. If chemical energy is converted to thermal energy during a chemical reaction then that process is described as exothermic. If thermal energy is converted to chemical energy during a chemical reaction (that
13
This experiment has been adapted from First Year Experiment 2 - Thermochemistry undertaken at The University of Adelaide. 243
Experiment 4.4: Exploring Hess Law using calorimetry
is, heat has to be supplied to the system by the surroundings) then that process is described as endothermic. If the process occurs at constant pressure (isobaric) it can be shown that the heat change (qreaction) is equivalent to the enthalpy change (Hreaction). Heat changes are not measured directly but by the effect the heat has on the temperature of the substances involved. To do this we will use calorimetry to measure the temperature changes and given the heat capacity of the substances determine the heat produced or consumed
Heat and Calorimetry

First, we need to determine the heat capacity, (C units of Joules per Kelvin, J K1), of the calorimeter and the mass and specific heat, (CS units of Joules per Kelvin per gram, J K1 g1), of any substances involved. Heap capacity is the amount of heat energy required to change the temperature of the substance (per unit mass or per device or system) by 1K or 1C. This step allows us to calibrate the calorimeter. Once this is done the heat required to raise the temperature of the inside of the calorimeter can be calculated (its heat capacity). The calorimeters that you will use are a pair of well insulated coffee cups (see Figure 4.4.1 at right) that minimise the loss of heat to the surroundings and you can assume that there will be neglible heat conduction from the system during the experiments that you perform. The calorimeter cannot be sealed to maintain it at a constant atmospheric pressure, however a lid is used to minimise heat loss. In this case the system comprises the chemical reaction, the contents of the calorimeter (mostly water) and the calorimeter itself. If the system is adiabatic (ie no heat is lost to the surroundings) then first law of thermodynamics states that energy cannot be lost or gained, so the energy of the system must remain constant at 0.
qsystem = qreaction + qcontents + qcalorimeter = 0

As we wish to know the heat generated by the chemical reaction, we can rearrange this formula to determine qreaction.
qreaction = (qcontents + qcalorimeter)

The contents have a variable mass (depending on how much solution you add to the calorimeter), so we can determine the heat absorbed by or from the contents using this equation:
Figure 4.4.1: A simple coffee cup calorimeter allows adiabatic measurement of the heat generated or consumed in a chemical reaction (Blackman et al, Chemistry, g 8.9)
qcontents = m CS T
where:
m = mass of contents (in g) CS = specific heat of contents (in J K1 g1) T = change in temperature of contents (in K)
Assume that the contents are mostly water, so we can use its specific heat: CS (water) = 4.18 J K1 g1
244
However, we need to know the mass of our contents, which we can find from its density. The density of water can vary with temperature, however well assume all reactions will start at room temperature.
STOP
Your demonstrator will measure the room temperature for you and give you the value of density of water for today. As a guide, the density of water at 1 atmosphere and 21 C is 0.998 g mL1.
The calorimeter has a fixed mass, so we can determine the heat absorbed by or from the contents using this equation:
qcalorimeter = C T
where:
C = heat capacity of calorimeter (in J K1) T = change in temperature of contents (in K)
So combined, we can determine the heat of the reaction using this equation: qreaction = [(m CS T) + (C T)] Given that the calorimeter is at a constant pressure, the heat of reaction can be used to determine the molar enthalpy of reaction if the number of moles of reactant are known.
where:
nreactant = number of moles of reactant (in mol) Hreaction = enthalpy of reaction (in J mol1 or kJ mol1)
Temperature (T) / K
No calorimeter is perfectly adiabatic. Consequently, measuring the temperature change associated with the heat of a reaction is complicated by a temperature variation caused by heat energy leaking into or out of the vessel.
32 30 28 26 24
Tafter = 30.3 C
To correct for this effect, 22 temperature readings are recorded for several minutes before and 20 Tbefore = 19.2 C after a reaction is initiated and a graph of the data constructed. 18 The curves on either side of the 0 1.5 3 4.5 6 7.5 9 10.5 12 13.5 15 time of mixing are extrapolated Time (t) / min and the change of temperature at the instant of mixing determined. In the example at the right for an exothermic reaction (one where heat is given off and a temperature increase is recorded) the time of mixing is 3.0 min and the change in temperature (in C and K) is measured as 11.1 K. Firstly, we need to determine the heat capacity of the calorimeter by using a reaction with a known heat, then using the calibrated calorimeter perform two experiments to determine the enthalpy of neutralisation and enthalpy of solution of ammonium chloride.
= 11.1 C = 11.1 K
245
Part 1: Calibrate the calorimeter

The heat of neutralisation (Hneutralisation) of an acid by a base is the heat evolved when one mole of water is formed from the acid-base reaction. In this experiment, the enthalpy change due to the neutralisation of hydrochloric acid by sodium hydroxide will be utilised to determine the heat capacity of our calorimeter. Under adiabatic conditions the enthalpy of neutralisation will equal the heat of neutralisation (qneutralisation).
Procedure
1. Ensure your calorimeter is clean and dry. Do not use any organic solvent to dry your calorimeter. Using solvents, such as acetone, will rapidly dissolve the polystyrene coffee cup.
STOP
2. 3.
Using the appropriate measuring cylinder, add 100 mL of 2.0 mol L1 hydrochloric acid solution to the calorimeter and a magnetic stirrer bar. Stir the solution by placing on a hotplate stirrer (do not turn on the heat) and record its temperature at thirty second intervals on your report sheet until you are sure that it is constant. This will typically take approximately two to three minutes. Using the appropriate measuring cylinder, quickly add 100 mL of a slightly greater than14 2.0 mol L1 sodium hydroxide solution to the calorimeter. For our purposes, you may assume that the temperature of the acid is the same as that of the sodium hydroxide. Note down the time of mixing. Place the lid on the container and commence stirring. Record the temperature at thirty second intervals until the maximum temperature is reached and the contents of the calorimeter begin to cool. Do not stir with or allow the magnetic stirrer bar to come into contact with the themometer while stirring. To do so may break the thermometer.
4.
5.
STOP
6. 7.
Construct a plot of temperature versus time, noting the time of mixing and determine the change in temperature. Your plot should be constructed in pencil to allow erasure of errors. The enthalpy of neutralisation for hydrochloric acid is 57.9 kJ mol1. Based on the concentration , volume and hence number of moles of hydrochloric acid, predict the heat given off by this reaction (qreaction). Using this value, determine the heat capacity (C) of the calorimeter using the equations given on page 248.
8.
14
The sodium hydroxide is slightly in excess to ensure complete neutralisation of the hydrochloric acid. 246
Part 2: Determination of enthalpy of neutralisation of an aqueous ammonia solution

As in Part 1, well use an acid-base reaction to determine the enthalpy of neutralisation, this time for ammonia. A similar procedure to part 1 will be used, but this time the heat of reaction (and hence enthalpy of neutralisation) is unknown. 1. 2. 3. Make sure you are using the same calorimeter set up as in Part 1. Ensure your calorimeter is clean and dry. Using the appropriate measuring cylinder, add 125 mL of 0.4 mol L1 ammonia solution to the calorimeter and a magnetic stirrer bar. Stir the solution by placing on a hotplate stirrer (do not turn on the heat) and record its temperature at thirty second intervals on your report sheet until you are sure that it is constant. Using the appropriate measuring cylinder, quickly add 25 mL of a 2.0 mol L1 hydrochloric acid solution to the calorimeter. For our purposes, you may assume that the temperature of the acid is the same as that of the ammonia solution. Note down the time of mixing. Place the lid on the container and commence stirring using the magnetic stirrer. Record the temperature at thirty second intervals until the maximum temperature is reached and the contents of the calorimeter begin to cool. Construct a plot of temperature versus time, noting the time of mixing and determine the change in temperature. Determine the heat of neutralisation using the equations on page 248. Based on the number of moles of ammonia present, determine the enthalpy of neutralisation (in kJ mol1) for this reaction.
4.
5.
6. 7. 8.
247
Part 3: Determination of enthalpy of solution of ammonium chloride

In this step we will measure the heat of solution in exactly the same way we measured heats of neutralisation in Parts 1 and 2. The enthalpy of solution is the amount of energy released or consumed when a solid is dissolved into solution. 1. 2. 3. 4. 5. Make sure you are using the same calorimeter set up as in Part 1. Ensure your calorimeter is clean and dry. Weigh by difference15 around 2.700 g of ammonium chloride into a small beaker noting the accurate weight to three decimal places. Using the appropriate measuring cylinder, add 150 mL of deionised water to the calorimeter. Stir the solution and record its temperature at thirty second intervals on your report sheet until you are sure that it is constant. Empty the contents of the small beaker into the calorimeter and replace the lid. You will need to reweigh the beaker for any residue and adjust your recorded weight after the temperature measurements have been taken. Place the lid on the container and commence stirring using only the stirring rod provided. Record the temperature at thirty second intervals until the maximum temperature is reached and the contents of the calorimeter begin to cool. Construct a plot of temperature versus time, noting the time of mixing and determine the change in temperature. Your plot should be constructed in pencil to allow erasure of errors. Determine the heat of solution using the equations on pages 248 and 249. Based on the mass and hence number of moles of ammonium chloride present, determine the enthalpy of solution (in kJ mol1) for this process.
6.
7. 8. 9.
15
Weighing by difference: you should record the weight of the empty and clean beaker, then removing the beaker off the balance, add around 2.700 g of the solid ammonium chloride and record the mass of beaker + solid. At step 5 you will need to weight the beaker + residue to determine the accurate mass added to the calorimeter. It doesnt need to be exactly 2.700 g, just within 0.1 g of this gure. See the notes given in the preface of your lab manual for details on care and use of balances. 248
Part 4: Application of Hess Law to determine enthalpy of formation of ammonium chloride

Hess Law states that when a reaction occurs the change is the same regardless of whether the process occurs in one step or a series of steps. This is called a state function. In this experiment we will use some theoretical values and our experimentally derived values to calculate the enthalpy of formation of ammonium chloride from its components. The diagram below illustrates this process of applying Hess Law to this problem. The enthalpies of neutralisation and solution are known. The enthalpies of formation for ammonia and hydrochloric acid solutions are given below.
Calculate the enthalpy of formation (reaction 2) for ammonium chloride from the data determined in Parts 2 (neutralisation, reaction 4) and 3 (solution, reaction 3) and the theoretical values (reaction 1) given above.
249
Gibbs free energy and spontaneity

As with heat, the word spontaneous has a particular meaning. In the field of thermodynamics a spontaneous process is one that lowers the free energy of the system. Such a process is thermodynamically favourable but will only occur if a suitable pathway exists. A process may be spontaneous and yet proceed almost infinitely slowly. Therefore, both thermodynamics and kinetics can govern the likelihood of a reaction measurably occurring. Gibbs free energy (G) is a thermodynamic function that can be used to predict if a process is spontaneous at constant temperature and pressure, i.e. a function is spontaneous if G < 0. A spontaneous process releases energy and can be used to do work. Conversely, a nonspontaneous process requires work to be done to cause it to happen. Were not going to fully explore Gibbs free energy here, however it can be given that for a reaction at constant temperature and pressure:
Greaction = Hreaction T Sreaction

where:
Greaction Hreaction T Sreaction
= = = =
change in Gibbs free energy change in enthalpy temperature of reaction change in entropy
Entropy and spontaneity

Entropy is a direct measure of the randomness or disorder of a system. The second law of thermodynamics tells us that to be spontaneous a reaction must lead to an increase in the entropy of the universe. The above equation says that for a process carried out at temperature T, if the changes in enthalpy and entropy of the system are such that the right hand side of the equation is less than zero, the process must be spontaneous. In order to predict the sign of G, we need to know both H and S. A negative H (an exothermic reaction) and a positive S (a reaction that results in an increase in disorder of the system) tend to make G negative, although a process with a positive H may still be spontaneous if the TS term is large and positive (remember the minus sign!
250
Name
Student ID
Pre-laboratory questions: Exploring Hess Law using calorimetry

1. Write an equation describing the reaction between an aqueous solution of ammonia and hydrochloric acid. Indicate the acid/base conjugate pairs.
2.
The enthalpy of solution of potassium chloride (KCl) is +17.2 kJ mol1. a) Calculate how much heat would be generated if 0.745 g is added to 300 mL of water contained in a calorimeter described in this experiment.
b)
What temperature increase would be recorded in this calorimeter given its heat capacity is 100 J K1? Assume the contents are mostly water.
c)
Is this process exothermic or endothermic? Explain your answer.
251
3.
Consider the following illustration of a bomb calorimeter and answer the following questions.
(a)
What is the purpose of the stirrer?
(b)
Why is it important that the tank is heavily insulated?
(c)
Does the volume of the reaction chamber change during the reaction?
(d)
Why is the bomb surrounded by water and not air?
252
Name
Student ID
Results
Part 1: Calibrate the calorimeter
Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 Temp (C) Time (min) 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 Temp (C) Time (min) 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 Temp (C)
Temperature (T) / C
Time (t) / min
253
Calculate the heat capacity of the calorimeter:
Part 2: Determination of enthalpy of neutralisation of an aqueous ammonia solution

Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 Temp (C) Time (min) 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 Temp (C) Time (min) 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5
254
Temp (C)
Temperature (T) / C
Time (t) / min

Calculate the enthalpy of neutralisation:
255
Part 3: Determination of enthalpy of solution of ammonium chloride

Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 Temp (C) Time (min) 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 Temp (C) Time (min) 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 Temp (C)
Temperature (T) / C
Time (t) / min
256
Calculate the enthalpy of solution:
Part 4: Determination of enthalpy of formation of ammonium chloride

Part 2 Part 3
Hneutralisation Hsolution
Calculate the enthalpy of formation:
257
Questions
1. In each of Parts 13, which process was exothermic and which was endothermic? Explain your answer.
2.
In each of the processes observed in Parts 13 did energy ow from the calorimeter to its contents or vice versa? Explain your answer.
3.
In Part 2 you examined a spontaneous process that was exothermic. In Part 3 you examined a spontaneous process that was endothermic. What does this tell you about a spontaneous process?
258
2.2 2.3
Calculate the energy energy absorbed calorimeter alone, qcalorimeter. Refer .to Laboratory Manual, 2.2 Calculate the absorbed by the by the calorimeter alone, qcalorimeter Refer to Laboratory Manual, Page 23. 23. Page Calculate the energy energy absorbed contents of the calorimeter, qcontents. You may assumeassume that the 2.3 Calculate the absorbed by the by the contents of the calorimeter, qcontents. You may that the specific heat and densitydensitysolution equals that of that of pure Refer to Laboratory Manual, Page 2 specific heat and of the of the solution equals pure water. water. Refer to Laboratory Manual, Page 2 3. 3. Calculate the total thermal energy,energy, q , of the,reaction. q 2.4 Calculate the ). (Hreaction total thermal reaction reaction of the reaction. Calculate the thermal energy energy per mole of reactants. energy energy released or absorbed? per mole of reactants. Is this Is this released or absorbed? 2.5 Calculate the thermal
2.4 2.5
4.
You have considered spontaneous reactions with positive and negative enthalpy changes
Is that has warmedpredict the spontaneity of a been converted from chemical energy in to the calorimeter and contents has process given the The thermal energyit possiblehas warmed the calorimeter and contents has been converted enthalpy change of that The thermal energy that from chemical energy in process alone? the reactants. the reactants.
2.6 2.7 Was Was the reaction exothermic or endothermic? reaction exothermic or endothermic? 2.6 theIf not, what does determine spontaneity and thus what other factors must also be considered? (Use an equation to of neutralisation ( Hneutralisation) of NH What value do you do you for the for theenthalpysupport your answer.) H 2.7 What value obtain obtain molar molar enthalpy of neutralisation ( neutralisation)3(aq) with with of NH3(aq) HCl(aq). Be sureBe sure tothe correct correct units complycomply with sign conventions. Thiswill vary vary HCl(aq). to quote quote the units and to and to with sign conventions. This value value will with the concentration of the reactants. When quoting your Hneutralisation you should should state the with the concentration of the reactants. When quoting your Hneutralisation you state the concentration at which it was determined. concentration at which it was determined. Calculate the energy energy required to decrease the temperaturecontents of the calorimeter by the by the 2.9 Calculate the required to decrease the temperature of the of the contents of the calorimeter observed T(qcontents). You may assumeassume that the specific heat and densityammonium chloride observed T(qcontents). You may that the specific heat and density of the of the ammonium chloride solution is the same as pureas pure (Remember, mcontents = the total mass of everything you have have solution is the same water. water. (Remember, mcontents = the total mass of everything you added to yourto your flask.) added flask.) Calculate the energy energy transfer for the calorimeter(qcalorimeter). 2.10 Calculate the transfer for the calorimeter alone alone (qcalorimeter). Did Did flow from the calorimeter to its contents or vice versa? 2.11 energy energy flow from the calorimeter to its contents or vice versa? Calculate the enthalpy changechangeone mole of ammonium chloride, NH4Cl(s), is dissolved in water. water. 2.12 Calculate the enthalpy when when one mole of ammonium chloride, NH4Cl(s), is dissolved in RecordRecord the concentrationresulting solution as this will effect the value obtained. the concentration of the of the resulting solution as this will effect the value obtained. In One you examined a spontaneous process that was exothermic. In Part Two you examined a 2.13 PartIn Part One you examined a spontaneous process that was exothermic. In Part Two you examined a spontaneous processprocess that was endothermic.does this tellthis tell youaabout a spontaneous process? spontaneous that was endothermic. What What does you about spontaneous process? You You have considered spontaneous reactions with positive and negative enthalpy changes ( H 2.14 have considered spontaneous reactions with positive and negative enthalpy changes ( Hreaction). ). Is it possible to predict predict the spontaneity of a processthe enthalpy changechange processprocess reactionIf If Is it possible to the spontaneity of a process given given the enthalpy of that of that alone? alone? not, what does determine spontaneity and thus what other factors factors must also be considered? (Use an not, what does determine spontaneity and thus what other must also be considered? (Use an equation to supportsupport your answer.) 5. equation to the following experiment. A beaker containing 1000 black beads and 1000 white Consider your answer.) beads is mixed. The beads are identical except for their colour. Consider the following thought experiment. A beaker beaker containing 1000beads and 1000 white white 2.15 Consider the following thought experiment. A containing 1000 black black beads and 1000
2.9
2.10 2.11 2.12 2.13 2.14
2.15
mixingMixing mixing
The potential energy of the beads on the left is identical to those on the right and thus the change in enthalpy left the mixing those on Explain in thus theof entropy how this mixing The potential energy energybeads on the for theidentical tois zero. the right and terms thus the change in enthalpy for is left is The potential of the can be spontaneous. identical to those on the right and change in enthalpy for process of the beads on the mixing is zero. Explain in terms of entropy how this mixing process can be spontaneous.
the mixing is zero. Explain in terms of entropy how this mixing process can be spontaneous.
beads is mixed. mixed. Theare identical except except for their colour. beads is The beads beads are identical for their colour.
EXPERIMENT 29 29 EXPERIMENT
259
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Part 1: Measured heat capacity of the calorimeter compared to expected value was... Part 2: Measured enthalpy of neutralisation compared to expected value was... Part 3: Measured enthalpy of solution compared to expected value was... Part 4: Calculated enthalpy of formation compared to expected value was... All parts: All graphs were complete, neat, detailed and fully labelled In-laboratory questions were... 0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0
Not attempted
0.5
Outside range
1
Within range
0
Not attempted
0.5
Outside range
1
Within range
0
Not attempted
0.5
Outside range
1
Within range
0
Not attempted
0.5
Outside range
1
Within range
0
None
0.5
Poorly presented
1
Few were complete
1.5
Mostly complete
2
All complete
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
Total (out of 10)
260
PART 5: TECHNIQUES IN QUANTITATIVE ANALYSIS
261
262
EXPERIMENT 5.1: ATOMIC ABSORPTION SPECTROMETRY

Safety
!
PPE
Follow the instructions provided with each AAS very carefully. Flame-AAS uses an explosive mixture of air and acetylene to achieve atomic absorption and emission. At all times take care and follow the directions of your demonstrator. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. observe atomic emission and the characteristic colours they impart to the ame, relate absorption to concentration through Beers law to obtain a calibration curve, quantify the concentration of an analyte in a real sample by interpolation of a calibration curve and, compare results between groups to ascertain accuracy and precision of a series of analyses.
Aim
To utilise atomic absorption spectrometry to quantify the concentration of metals in drinking water and Diet Pepsi. To compare the technique for four different analytes. Observe the correct operation of common instrumentation.
Introduction
Spectrometry is an analytical technique that depends on the absorption of electromagnetic radiation by a chemical species in a sample. The basic system involves: source of radiation sample detection of transmitted radiation If a substance absorbs visible radiation, then the substance must itself be coloured. For example, a solution of copper is blue because it absorbs the complementary colour, yellow, from white light. white light Cu2+ solution yellow light absorbed blue light transmitted
Visible spectrometry is particularly useful for the determination of low concentrations (parts per million) of anions or cations in solution. Atomic absorption spectrometry is typically used for analysis of free metal atoms in the gas phase produced by volatilising a solution containing the metal ions. For all solutions, one part per million (ppm) is usually defined as 1 mg of substance dissolved in 1 L of solvent (that is, mg/L).
Absorption versus emission

When an atom absorbs a photon (h1), the energy of the atom increases. The energy absorbed from the visible region of the spectrum by a chemical species (M) causes the excitation of outer
Experiment 5.1: Atomic absorption spectrometry 263
valence electrons, which are promoted to an excited state (M*). The excited species are usually unstable, and quickly revert to a ground state (through the emission of a photon, h2). The frequency absorbed (1) may not be the same as the frequency emitted (2): M + h1 M* M + h2 This permits two modes of detection in analytical spectrometry: absorption (h1) or emission (h2) of a characteristic wavelength of light by the sample. In atomic spectroscopy under the conditions we will examine, absorption is more frequently encountered as it offers greater sensitivity and thus lower detection limits.
Atomic Absorption Spectrometers

A modern spectrometer has the following components, which will be highlighted by your demonstrator. Hollow cathode lamp: Emits discrete wavelengths that are characteristic of the element under analysis (the analyte). Use the recommended lamp current. Nebuliser and spray chamber: Converts the sample solution into a mist of very fine droplets that are mixed with oxidant (usually air, sometimes nitrous oxide) and fuel (acetylene). Flame: Generates gaseous atoms of the analyte that can selectively absorb radiation emitted from the hollow cathode lamp. Slit/monochromator: Isolates a chosen wavelength (resonance line) to be used for the analysis. Detector/amplifier: Produces the readout signal.
(a)
(b)
Schematic diagram of (a) an atomic absorption spectrometer and (b) nebuliser and burner system. 16
16
Skoog, D.A., et al. Fundamentals of analytical chemistry, 8th Edition, 2004, Thomson Brooks/Cole: California. (suggested pages 858 - 867) 264
Experiment 5.1: Atomic absorption spectrometry
Beers Law
Most quantitative measurements are carried out by comparison of a blank with the sample solution. The amount of monochromatic radiation absorbed by a sample is described by the Beer-Bouguer-Lambert Law, commonly known as Beers Law.
The molar absorptivity coefficient (or the molar extinction coefficient in some early texts), is related to the intensity of absorption which is proportional to the number of electrons excited. The value of is characteristic of the absorbing molecule or ion in a given solvent at a given wavelength. Values of range from about 500 (weakly absorbing) to 20,000 (strongly absorbing). Under ideal circumstances a linear plot of A vs c is obtained, provided: a) b) c) d) the incident radiation is monochromatic from a stable light source. the absorbing species act independently of each other - solution must be dilute, usually 102 107 M, giving absorbances in the range 0.05-1.00. absorption occurs in a volume of uniform cross-section (the cells must be a matched pair, correctly positioned in the beam). the temperature of standards and reference should be the same.
Deviations from the Beers law occur if any of the above conditions are not met. In practice it is always necessary to prepare a calibration curve of A against known concentrations of absorbing species. This is called the working curve. Determinations should be carried out so that all unknowns fall within the range of the working curve, with the concentration of the unknown interpolated from the working curve. Even if the calibration line deviates from ideal behaviour, accurate analytical determination can be made providing identical experimental conditions are used. For accurate work, the %T should be between 90% and 10% (absorbance 0.05 1.0), but the most accurate measurements will be at 50% transmittance (absorbance 0.3). Sample dilution may be necessary in some instances to achieve this condition. True deviations from the Beers law only occur when the concentration of absorbing species is very high. Apparent deviations occur as a result of instrumental or chemical effects.
Instrumental effects:
The use of non-monochromatic radiation, as for example in filter photometers, produces negative deviations.
References
Skoog, D.A., et al. Fundamentals of Analytical Chemistry, 8th Edition, 2004, Thomson Brooks/ Cole: California. (Chapter 24)
265
Demonstration 1: Flame colours

Some metal cations exhibit characteristic colours in a flame. This property is enhanced when the solution is introduced into the flame through a nebulizer. The visible colour is due to atomic emission. It is mainly evident for Group I and Group II metals. Your demonstrator will perform the following experiment. Note down the visible colour observed (if any) and relate this to the metal identity and its position in the periodic table. Note that for zinc and the majority of other metals, whilst it is possible to produce a cloud of atoms in the flame, there is insufficient energy to cause measurable atomic emission. This is the main reason for the widespread use of atomic absorption.
Demonstration 2: Analysis of copper in brass by AAS
STOP
1.
If time permits your demonstrator will perform the following tasks. Watch carefully and take notes, as you will have to perform similar analyses for your own samples in the following experiment.
(Set up the instrument on the copper resonance line (324.7 nm) using the recommended lamp current and spectral band pass (slit width). Click Optimize; this will drive the monochromator to 324.7 nm, and ne tune the wavelength peak. Ensure that hollow cathode lamp is correctly aligned for maximum transmission. Light the ame and adjust the acetylene ow to produce a lean ame. Zero the instrument using deionised water. Click Optimize Signal and then spray the 8 mg L-1 copper standard and adjust the burner position to give maximum absorbance. Re-zero the instrument. Measure the absorbances of the standard copper solutions and the unknown. The AAS software can be used to plot a non-linear calibration curve; use this calibration curve to determine the concentration of the unknown.
2.
3. 4.
Exercise: Determination of metal ions in tap water and Diet Pepsi

A suite of four metals, sodium, potassium, calcium, and magnesium and will be analysed by flame atomic absorption spectrometry. Calibration curves will be constructed for each element using standards of appropriate concentration and the unknowns determined from their measured absorbances.
Follow the instructions provided with each AAS very carefully. Flame-AAS uses an explosive mixture of air and acetylene to achieve atomic absorption and emission. At all times take care and follow the directions of your demonstrator.
Note the wavelengths, slit widths and approximate working ranges to be used Element Ca Mg K Na Wavelength (nm) 422.7 202.6 769.9 589.6 Slit width (nm) 0.5 1.0 1.0 0.2 Working range (mg L1) 1 10 1 20 16 0.1 2.0
266
Name
Student ID
Pre-laboratory questions: AAS

1. The typical results for the analysis of the metals of interest in the two samples are given below: Sample Tap Water Diet Pepsi Typical concentration / mg L1 Na 50 60 K 5 22 Ca 30 3.0 Mg 5 2.5
Using these results determine any dilution that will be necessary to place these concentrations within the working range of standards suggested in the procedure. These working ranges are given on your answer sheet. Calculate this as a dilution factor. For example, if the concentration is ten times too concentrated, the dilution factor required will be ten fold. We will use an autodiluter to get the concentrations within the working range before analysis.
267
2.
What is the purpose of the hollow cathode lamp used in atomic absorption spectrometry?
3.
Arethe absorbance peaks ofmetals observed in flame AAS wide or narrow? Explaining your answer briefly, how does this comparewith those observed in molecular spectroscopyof solutions?
4.
Visible atomic emission can be seen when the Group I and some Group II elements are aspirated into an air/acetyleneflame. However for most transition metals no atomic emission occurs at such temperatures. Suggest a reason.
Experiment 5.1: Atomic absorption spectrometry 268
Name
Student ID
Results: AAS
Demonstration 1: Flame colours
Complete the following table with your observations. Element Li Na K Cs Zn Flame Colour Element Mg Ca Sr Ba Al Flame Colour
Demonstration 2: Determination of copper by AAS

Complete the following table with your observations. Concentration of Cu (mg L-1) 1.0 2.0 4.0 6.0 8.0 Unknown Result: Unknown Concentration = mg L-1 Absorbance
269
Exercise: Determination of metal ions in tap water and Diet Pepsi

Sodium
Wavelength: 589.6 nm Slit: 0.2 nm Approx. Working Range: 0.12.0 mg L1 Absorbance
[Na] / mg L-1 Cal Blank = 0.00 Standard 1 = Standard 2 = Standard 3 = Standard 4 = Tap water Diet Pepsi Tap water Dilute concentration / mg L-1 Dilution factor Sample concentration / mg L-1
Diet Pepsi
Potassium
Wavelength: 769.9 nm Slit: 1.0 nm Approx. Working Range: 1.06.0 mg L1 Absorbance
[K] / mg L-1 Cal Blank = 0.00 Standard 1 = Standard 2 = Standard 3 = Standard 4 = Tap water Diet Pepsi Tap water Dilute concentration / mg L-1 Dilution factor Sample concentration / mg L-1
Diet Pepsi
270
Calcium
Wavelength: 422.7 nm Slit: 0.5 nm Approx. Working Range: 1.010 mg L1 Absorbance
[Ca] / mg L-1 Cal Blank = 0.00 Standard 1 = Standard 2 = Standard 3 = Standard 4 = Tap water Diet Pepsi Tap water Dilute concentration / mg L-1 Dilution factor Sample concentration / mg L-1
Diet Pepsi
Magnesium
Wavelength: 202.6 nm Slit: 1.0 nm Approx. Working Range: 1.020 mg L1 Absorbance
[Mg] / mg L-1 Cal Blank = 0.00 Standard 1 = Standard 2 = Standard 3 = Standard 4 = Tap water Diet Pepsi Tap water Dilute concentration / mg L-1 Dilution factor Sample concentration / mg L-1
Diet Pepsi
271
Comparison of results
Put your results in the table and compare them with the class averages. Analyte Na K Ca Mg 1. Comment on your accuracy and precision as it compares to the class average. Do you notice any anomalies? Tap water / mg L-1 Your result Average Diet Pepsi / mg L-1 Your result Average
2.
Explain how it is that the technique of AAS can determine the concentration of a particular analyte even in the presence of a complex mixture of other elements.
3.
Suggest two ways you could analyse for sodium in both samples without dilution. HINT: You may refer to the AAS Cookbook available in the lab.
272
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Demonstrations 1 and 2: The observations were fully detailed and correct. Exercise: The determination of sodium, potassium, calcium and magnesium was... Poor
0 Not attempted 0 Strongly disagree 0 Not attempted 0 Not provided 0 Not attempted 0.5 Poorly attempted 0.5 Poorly attempted 0.5 Disagree
Good
1 Mostly incorrect 1 Neutral 1 outside expected range 0.5 Provided without discussion 1 Mostly incorrect 1 Provided but poorly discussed 1.5 Mostly correct 1.5 Mostly correct 1.5 Agree
Excellent
2 All correct 2 Strongly agree 2 within expected range 2 Provided and discussed 2 All correct
Exercise: The comparison of the class results was...
Total (out of 10)
273
274
EXPERIMENT 5.2: DETERMINATION OF VANILLIN IN IMITATION VANILLA ESSENCE

Safety
!
PPE
Dichloromethane is toxic and a suspected carcinogen. Avoid any inhalation or contact with skin and eyes You must wear appropriate gloves when handling dichloromethane. All preparative steps must be undertaken in the fumehood. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. perform a quantitative extraction of an analyte (vanillin) from a sample (vanilla essence), prepare a range of standards and apply Beers law to construct a calibration curve, quantify the concentration of an analyte in a real sample by interpolation of a calibration curve and, determine extraction efciency of vanillin using the same process.
Aim
To determine the concentration of the active ingredient vanillin in an imitation vanilla essence by UV-Visible spectrometry.
Introduction
Vanillin is the common name for 4-hydroxy-3-methoxybenzaldehyde, and is readily recognised by its aroma and taste due to extensive use in food as a flavouring agent. Genuine vanilla essence was originally extracted from the beans of the vanillin plant using ethanol as solvent, but most vanillin today is derived from lignin, a waste product from paper pulp manufacture. Use of vanillin in the synthesis of a number of important drugs now surpasses its use as a flavouring agent. The method of analysis involves the following steps: 1. 2. 3. Extraction of the vanillin from the other components of the essence using an organic solvent, dichloromethane. Back extraction of the vanillin as its sodium salt into the aqueous phase using dilute sodium hydroxide solution. Determination of the concentration of vanillin in the aqueous extract by UV-Visible spectrometry.
Spectrometry is an analytical technique that depends on the absorption of electromagnetic radiation by a chemical species in a sample. The basic system involves:
Experiment 5.2: Determination of vanillin in imitation vanilla essence 275
source of radiation sample detection of transmitted radiation If a substance absorbs visible radiation, then the substance must itself be coloured. For example, a solution of copper is blue because it absorbs the complementary colour, yellow, from white light. white light Cu2+ solution yellow light absorbed blue light transmitted
Visible spectrometry is particularly useful for the determination of low concentrations (parts per million) of coloured species in solution. For all solutions, one part per million (ppm) is usually defined as 1 mg of substance dissolved in 1 L of solvent (that is, mg/L).
Absorption of Radiation
When a molecule absorbs a photon (h1), the energy of the molecule increases. The energy absorbed from the visible region of the spectrum by a chemical species (M) causes the excitation of outer valence electrons, which are promoted to an excited state (M*). The excited species are usually unstable, and quickly revert to a ground state (through the emission of a photon, h2). The frequency absorbed (1) may not be the same as the frequency emitted (2): M + h1 M* M + h2 The energy absorbed is directly proportional to the concentration of absorbing species and hence can be used for quantitative analysis through the application of Beers Law. The energy can also be plotted as a graph of energy absorbed (absorbance) vs wavelength, called an absorption spectrum.
Each peak corresponds to the absorption of energy of a particular wavelength corresponding to one of the electronic transitions. The wavelength of maximum absorbance is max. Since a spectrum is characteristic of an absorbing species, it can be used for identification purposes (that is, qualitative analysis). Unfortunately in the visible region usually only one broad band is evident and hence visible spectrometry is mainly used for quantitative purposes.
UV-Visible Spectrometers
The spectrophotometer is the instrument used to quantitatively measure transmitted radiation. The principal components of the instrument are:
Radiation Source
Monochromator (wavelength filter)
P0
Sample Holder
Detector
Recorder
Experiment 5.2: Determination of vanillin in imitation vanilla essence
276
Radiation Source
Visible Range: Tungsten Filament Lamp: a cheap, stable source of visible light emitting over the range 330 2500 nm. At 3000K, these lamps are only 12% efcient in the visible range, emitting mostly IR radiation. Tungsten-Halogen Lamp (Quartz-Iodine Lamp): compact W lament in a quartz bulb lled with halogen gas. These lamps have a high-energy output between 300 - 400 nm, and a long operational life. Ultra-Violet Range: Deuterium Lamp: a tube with quartz windows and a pair of arcing electrodes lled with D2 gas. These lamps give satisfactory performance below 330 nm, and are continuous around 180 nm. Intensity Control: The radiation intensity varies with wavelength, and so a slit or shutter control is required which maintains the incident light at constant intensity. A stabilised power supply is required as uctuations in power supply may also cause changes in incident radiation.
Monochromator (or wavelength lter)

The purpose of monochromators (or wavelength filters) is to reduce the broad band of polychromatic radiation of the radiation source to a narrow band. This can be achieved by: i) lters - absorb a wide range of incident radiation white light ii) filter transmits about 50 nm band
monochromators - have a narrow band pass, usually 1 nm. These can be prisms, diffraction gratings or holographic devices.
Sample Holder
The material from which the sample holder is made needs to be transparent, i.e. have no absorption in the test frequency range. For the visible region, glass or plastic cells are used. Polymethyl methacrylate (PMMA, acrylic) cells can be used down to 280 nm, but silica cells are essential in the UV range below 280 nm. Sample holders need to be clean, especially on the transparent faces through which the incident light passes. When several cells are used for sequential measurements, they require similar light transmitting properties, i.e. matched cells.
Detector and Recorder

The incident energy causes some change in property that generates a proportionate signal that is received by the recorder. Requirements: (i) (ii) (iii) (iv) High sensitivity. Short response time. Long term stability. Gives a signal that can be easily amplified.
The most common detectors are photomultipliers and phototubes.
277
Beers Law
Most quantitative measurements are carried out by comparison of a blank with the sample solution. The amount of monochromatic radiation absorbed by a sample is described by the Beer-Bouguer-Lambert Law, commonly known as Beers Law.
Reflection losses at interfaces
Absorption of radiation (P: power of incident radiation, P0: power of emergent radiation) Source: Skoog, D.A., et al. Fundamentals of analytical chemistry, 8th Edition, 2004, Thomson Brooks/ Cole: California. The power of the transmitted radiation from the blank, taken as 100% transmission and denoted P0, represents the power of the incident radiation minus any intensity loss due to light scattering, reflection or absorption by solvent. This intensity loss is assumed to be identical for both blank and sample.
Incident beam
Emergent beam
Scattering losses in solution
When the incident radiation passes through a solution of absorbing species (at c: concentration, and b: pathlength), there is a decrease in power dP0, resulting in the emergent (transmitted) radiant power, denoted as P. The fraction of radiant energy transmitted was found to decay exponentially with pathlength: Equation (1) where k is a constant, T is transmittance (the fraction of radiant energy transmitted), and b is pathlength. It was later determined that transmittance was also similarly dependent on the concentration of the absorbing species present, c: Equation (2) where k is a new constant. Beers law is derived from the combination of both Equation (1) and Equation (2), and reflects the dependence of transmittance on both the pathlength and concentration:
Beers Law
The molar absorptivity coefficient (or the molar extinction coefficient in some early texts), , is related to the intensity of absorption which is proportional to the number of electrons excited. The value of is characteristic of the absorbing molecule or ion in a given solvent at a given wavelength. Values of range from about 500 (weakly absorbing) to 20,000 (strongly absorbing). Under ideal circumstances, a linear plot of A vs c is obtained, provided: a) b) the incident radiation is monochromatic from a stable light source. the absorbing species act independently of each other - solution must be dilute, usually 102 107 M, giving absorbances in the range 0.05-1.00.
278
c) d)
absorption occurs in a volume of uniform cross-section (the cells must be a matched pair, correctly positioned in the beam). the temperature of standards and reference should be the same.
Deviations from the Beers law occur if any of the above conditions are not met. In practice it is always necessary to prepare a calibration curve of A against known concentrations of absorbing species. This is called the working curve. Determinations should be carried out so that all unknowns fall within the range of the working curve, with the concentration of the unknown interpolated from the working curve. Even if the calibration line deviates from ideal behaviour, accurate analytical determination can be made providing identical experimental conditions are used. For accurate work, the %T should be between 90% and 10% (absorbance 0.05 1.0), but the most accurate measurements will be at 50% transmittance (absorbance 0.3). Sample dilution may be necessary in some instances to achieve this condition. True deviations from the Beers law only occur when the concentration of absorbing species is very high. Apparent deviations occur as a result of instrumental or chemical effects.
Instrumental effects:
The use of non-monochromatic radiation, as for example in filter photometers, produces negative deviations.
Chemical effects:
The shape of a Beer plot may sometimes change with changes in concentration of species in solution.
orange
yellow max = 370 nm
max = 350 nm
As the Cr2O72 solution is diluted, the equilibrium moves to the right, and the solution measured is the result of a mixture of Cr2O72 and CrO42 ions. Since Cr2O72 < CrO42, dilution results in only a slight decrease in A. Several other factors cause incorrect absorbance values, and some of these will be investigated in the laboratory program.
References
1. 2. 3. Skoog, D.A., et al. Fundamentals of analytical chemistry, 8th Edition, 2004, Thomson Brooks/Cole: California. (suggested pages 911 914) Ainscough, E.W. and Brodie, A.M., 1990, Journal of Chemical Education, 67, 1070. Budavari, S. et al. (ed.), The Merck Index, 12th Edition, 1996, Merck & Co. Inc.: New Jersey.
279
Procedure
Part 1: Sample preparation in pairs
Dichloromethane is harmful (limited evidence of a carcinogenic effect). Do not breathe vapour; avoid contact with skin and eye. Place all used dichloromethane in the residue bottle; do not pour it down the sink!
The diluted vanillin solution provided has been prepared from imitation vanilla essence by dilution 100 times with deionised water. Pipette 10 mL of diluted essence into a 100 mL separating funnel containing approximately 20 mL of dichloromethane (SG = 1.33). Shake well for about 2 minutes, releasing excess pressure as necessary, and then allow the two phases to separate. Carefully drain off the organic phase and repeat the extraction procedure with another 20 mL portion of dichloromethane. Combine the organic extracts that now contain most of the vanillin. Transfer the organic extracts into the 100 mL separating funnel. Add 40 mL of 0.1 M sodium hydroxide solution and shake well for two minutes. Transfer the aqueous extract into a 250 mL volumetric flask and make up to volume with 0.1 M sodium hydroxide solution.
Part 2: Preparing standards in groups of 4 to 6

Using 50 mL volumetric flasks, prepare a series of standards having concentrations of 5, 4, 3, 2 and 1 mg L1 of vanillin in 0.1 M sodium hydroxide solution by suitable dilution of the 50 mg L1 standard provided.
Part 3: Measuring absorbance in groups of 4 to 6

Following the procedure accompanying the instrument and using the 5 mg L1 vanillin standard and water as the blank, scan over the range 300 400 nm and find the wavelength of maximum absorbance (max) in this region. Measure the absorbances at max of the standards and the extract in 1 cm Kartell 1939 PMMA plastic cuvettes using ultra-violet spectrometry with water as the blank at the chosen analytical wavelength and following the instructions with the instrument. An additional vanilla essence extract is provided as a reference solution for this analysis, representing 100% extraction efficiency. Measure its absorbance at max and calculate the percentage recovery for your extract, based on the reference standard. Using Excel, construct a calibration curve by plotting concentration on the x axis and absorbance values for each of the standards on the y axis. By finding the line of best fit (using Ordinary Least Squares regression) and obtaining the linear equation describing this line you can interpolate from the absorbance and determine the concentration of vanillin in the extract. NB: Dont forget to include the dilution factor in your calculation for final concentration.
STOP
You may wish to bring your laptop to find your calibration curve. Alternatively, a limited number of computers will be provided in the student common room (500.4105/4106) to perform your calibration.
Comment on the result and discuss possible sources of uncertainty.
280
Name
Student ID
Pre-laboratory questions: Vanillin

1. Draw the structure of vanillin.
2.
Give the reaction of vanillin with sodium hydroxide solution.
3.
If you add water and dichloromethane to a separating funnel, two phases will form. Would you expect water to be the upper or lower phase? HINT: consider their relative densities.
4.
Explaining your answer, predict, by considering the relative intermolecular forces, which phase of a separation each of the following species would prefer: i) molecular vanillin.
ii)
vanillin as its sodium salt.
281
5.
Prepare a flow chart17 of the procedure indicating the preparative and analytical steps. For each separation, indicate where your analyte, vanillin, will be found and ensure you retain the correct fractions. Remember that vanillin may be present in the molecular or ionic forms.
17
Flowcharting is covered in Part 3 of the manual. If youre not sure how to complete this owchart, see your demonstrator the week before the experiment commences. 282
Name
Student ID
Results: Vanillin
Why do you add an additional 20 mL of dichloromethane?
Would you use a pipette or measuring cylinder to add the sodium hydroxide? Explain your answer.
What dilution scheme do you propose to prepare the required standard solutions from the stock standard?
283
From your spectrum max = ..................................... nm [Vanillin] / mg L-1 1.00 2.00 3.00 4.00 5.00 Your vanillia essence extract Solution for 100% extraction efficiency What dilution factor was applied to achieve your final vanilla essence extract? Consider both the initial dilutions made to the sample you obtained and the initial and final volumes of this sample. Absorbance
What is the equation (in the form Absorbance = slope x concentration + y-intercept) from your line of best fit?
Calculate from the above data the concentration in your final extract, the concentration in the original vanilla essence and the extraction efficiency (as a percentage of the 100% efficient sample) of this process. Ensure you include appropriate units of concentration.
[Vanillin]extract
= . ..........................................mg L-1
[Vanillin]essence
= ...........................................mg L-1
Extraction efficiency
= ...........................................%
284
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Flowchart: The flowchart prepared was... Construction of a calibration curve: The calibration curve was... Poor 0
Not attempted
Good 0.5
Partially attempted
Excellent 1
All correct
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0 Not included 0 Not attempted
0.5 Non-linear with no equation 0.5 Within 10% of the accepted value
1 Non-linear with equation 1 Within 5% of the accepted value 0.5 Outside the accepted value
1.5 Linear with some points removed 1.5 Within 2% of the accepted value
2 Linear and fully correct 2 Within 1% of the accepted value 1 Within the accepted value
Determination of vanillin: The determination of vanillin in the sample was...
Determination of extraction efficiency: The comparison to the extraction efficiency was...
0 Not attempted 0 Not attempted 0.5 Poorly attempted
1 Mostly incorrect
1.5 Mostly correct
2 All correct
Total (out of 10)
285
286
EXPERIMENT 5.3: GAS CHROMATOGRAPHY

Safety notes
!
PPE
In addition to the normal obligations to safety in laboratories, the Gas Chromatography Laboratory has some specific hazards. At all times follow the direction of your demonstrators and always ask if youre unsure of a procedure to operate an apparatus. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
There are a number of common sense safety considerations to keep in mind at all times in using the HP 5890 GC: Hydrogen (H2) is ammable, and explosive when conned in an enclosed volume, e.g. the column oven. The oven, inlet and detector zones may be hot enough to cause burns. Connected hardware may also be sufciently hot enough to cause burns. The syringe is sharp and care must be exercised when using in a crowded laboratory. Compressed gases are used via central supply taps and gas cylinders within the laboratory. Do not operate any pressure equipment if you have not been instructed on its use. Hexane is a highly ammable solvent that is commonly used within the GC laboratory. Refer to MSDS for more detailed information prior to using. The HP 5890 GCs use 250 volt A.C. mains power; report any electrical faults to the area technician or Laboratory Manager. The HP 5890 GCs are sensitive and expensive scientic instruments and are only to be operated as instructed by your laboratory supervisor and according to the instructions within this laboratory manual.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. observe a gas chromatograph and interpret the results it produces, perform a correct injection to ensure optimum separation and, utilise the technique to identify and quantify components in a mixture.
Aim
Understand the operation of common gas chromatographs and become familiar with correct injection technique. Utilise the technique to identify a compound in a mixture and quantitatively determine its concentration.
Experiment 5.3: Gas Chromatography
287
Introduction
Gas chromatography achieves separation of analytes by passing a mixture through a column that contains a stationary phase, usually an immobilised liquid or silica compound. A small volume (microlitres) of a solution of analytes is injected into the system and the solution is immediately volatilised by the injector oven. The analytes must be able to be volatilised easily and not be degraded by heat. The analyte gas is then passed into the carrier gas, which must be chemically inert, and the varying interactions between the analyte and stationary phase achieve separation of the analytes. The presence of an analyte is determined using a detector, which in this experiment is a flame ionisation detector or FID. With gas chromatography it is necessary that users become familiar with the day-to-day procedure for setting up an instrument and gaining practice in overcoming any problems that may be encountered. The simple task of igniting the flame in a FID can become a nightmare if gas flow rates are incorrectly set. Poor operating parameters and/or poor injection techniques can hinder the quality of results during routine analysis. Early GC technology used packed columns that allowed high carrier gas ows into the detector, i.e.30 mL/min of nitrogen. The detector also required hydrogen gas as the fuel at a ow rate of 30mL/min and air at a rate of 300 mL/min, giving a total gas ow of 360 mL/min. If this total gas ow was not achieved, the detector may have been difcult to light and in the event of successful ignition, detector responses may be noisy and insensitive. More recent GC technology utilises capillary columns, where the carrier gas ow rate is between 0.7 and 3.5 mL/min. The hydrogen, ame gas, and airow rates are still maintained at 30 and 300 mL/min. With these ow rates, there is a short fall in the total gas ow to the detector. It is necessary to use a make-up gas i.e.nitrogen at 30mL/min to make up the difference.
General Procedures for Setting Up 5890 Gas Chromatograph

GC head pressure gauge shows pressure (if it reading 0, then get the demonstrator). Oven is on and at the set temperature (press [OVEN TEMP] to display). FID is lit (you will observe condensation on a spanner when held over the detector)
Setting up and using the eDAQ software

1. 2. 3. 4. If eDAQ is not already running, double click on the eDAQ icon. Click on the Run Table icon (icon second from bottom). Select the appropriate method le for the exercise from the list, and then click Open. The Save As: PowerChrom window appears; you need to enter a new le name. Select the last le on the list and increment the number by one Eg: HP100076 is the last on the list, becomes HP100077 Click on the save button, the computer is now ready and waiting for the GC to start Inject your sample into to the GC and press [START] on the GC When the run is nished, click the OK button (top right hand corner) Select Windows on the menu bar; then Run Info. Enter your name(s) and sample details in the run info comments section. To print your trace and report select File from the menu bar, then Print
5. 6. 7. 8.
288
Exercise 1: Injection technique

Aim
On completion of this exercise you will be able to: 1. 2. 3. 4. Use the eDAQ software. Check the GC head pressure and the ame ionization detector (FID). Inject samples repeatably into a GC system. Understand the relative problems associated with injection techniques.
Introduction
In gas chromatography, several factors contribute to errors in quantitative analysis. One of these is operator skill in the introduction of samples. To be able to obtain the best precision for quantitative analysis, that is reproducible quantitative data, one must have a proper injection technique. The following steps should yield good results. 1. 2. 3. 4. 5. 6. 7. 8. Rinse the syringe with solvent, completely lling and expelling syringe several times. Wipe excess solvent from the syringe needle. Draw in 1 L of air. Ensure that the end of the plunger is aligned with the 1 L mark. Draw in 0.5 L of sample. This is achieved by drawing the plunger and aligning it with the 1.5L mark. This ensures the required injection volume is achieved, i.e. 0.5 L. Wipe excess sample from the needle. Draw in air until the sample/solvent is entirely within the syringe barrel. The sample is ready for injection as shown below. With the syringe in a vertical position, push the needle into the injector and inject the sample in a continuous, rapid manner. Do not use heavy force, as this will damage the syringe. Remember to clean the syringe with solvent after use to prevent ceasing of the plunger and cross contamination.
This method results in the syringe lled as shown in the diagram below.
Figure 5.3.1: Properly lled syringe for split or splitless injection.
Solvent following the sample (about 0.7 L) helps to wash components from the syringe and needle bore. For split sampling, with high gas velocity through the inlet, injection must be made in a continuous, rapid manner. Any lack of smooth motion may cause multiple injections and hence extra peaks. Note: Retention times can depend upon amount injected; so total sample volume should be kept constant.
289
Procedure
1. As described above, setup eDAQ on the computer and use Injection Technique as the method le. Record the detector, injector and column temperature from the instrument. Inject the rst sample press [START] on the GC. Wait for the analyte to elute before injecting the next replicate. Continue until you have three analyte peaks of equal height. Following is an example of the expected resultant chromatogram. Click on the [STOP] button located in the top right of the computer screen. From the eDAQ menu bar, select Data then Analyse Runs. Select Windows on the menu bar; then Run Info. Enter your name(s) and sample details in the run info comments section. Select File from the menu bar, then Print. Use the data in the eDAQ report to complete the laboratory report sheet for this exercise.
2.
3.
4. 5. 6.
Exercise 2: Identication of cineole in eucalyptus oil using temperature programming

Aim
On completion of this exercise, you will be able to: 1. 2. 3. 4. 5. Understand the limitations of low and high temperature isothermal runs for samples with components covering a wide range of boiling points. Set up a temperature program for the separation of a complex mixture. Recognise the distinct advantages of temperature programming in GC analysis. Identify compounds by using analyte additions. Understand the relative advantages and limitations of using the spiking technique.
Introduction to temperature programming

One of the key elements in the efficient separation of components on a GC column is the degree of partitioning of these components between the liquid stationery phase and the gaseous mobile phase. The partition coefficient of a compound in a mixture is strongly influenced by its vapour pressure, which in turn is directly related to column temperature. For example, the increase in vapour pressure from a 30 C rise in column temperature will approximately halve the partition coefficient, and thus double the rate of migration of a component through the column. Clearly, the most immediate effect of an increase in column temperature is a reduction in analysis time, often a very important factor to be considered when the sample contains components having a wide range of boiling points.
290
A further consideration is the influence of column temperature on resolution, the ability of the system to separate components, which have similar retention times, on a given column. A temperature increase will reduce differences between the partition coefficients of components and decrease the separation efficiency of the column. Conversely, a reduction in column temperature will improve the resolution of components, which may well co-elute at higher temperatures. When analysing a complex sample using an isothermal run, it is often found that no single column temperature can produce an entirely satisfactory chromatogram. A low temperature isothermal run, whilst probably adequately separating the components has some limitations. 1. 2. 3. It may require a very long analysis time to elute all components. Those with long retention times will usually elute as poorly shaped peaks, being both flat and broad or irregular in profile. The operator is often unsure whether all the high boiling components have been eluted from the column.
A high temperature isothermal run does not suffer from the above problems, but will most often produce a poorly resolved chromatogram having the low boiling components co-eluting at a very short retention time. A temperature-programmed run is therefore the best option: 1. It can start at a sufciently low temperature to ensure that all low boiling components are efciently separated. A short isothermal interval at this temperature can also be used for enhanced separation of these components. The rate of increase in column temperature can be adjusted to produce satisfactory resolution, sharp peaks and reduced analysis time as required. The column temperature can be held at the maximum selected until all high boiling components are eluted.
2. 3.
The main limitation to the use of temperature programming is the choice of a suitable liquid stationary phase. Many phases produce a background signal at higher temperatures due to the stationary phase bleeding from the column, and this may become excessive at high temperatures, with increasing signal to noise also apparent.
Introduction to standard additions and spiking

The eucalyptus tree is indigenous to Australia. The genus contains about 300 species with differing quantities of essential oils. People are often fooled into thinking that a plant oil extract has only one constituent. That is not the case. The oils may be roughly divided into three classes of commercial importance. 1. 2. 3. The medicinal oils. The industrial oils, containing terpenes, which are used for otation purposes in mining operations. The aromatic oils, which are characterised by their aroma.
The essential oil of eucalyptus is obtained by the steam distillation of fresh leaves. It is a colourless or straw-coloured fluid with a characteristic odour and taste. Cineole may be the predominate constituent, depending on species. Other components present include large amounts of terpene, cymene and limonene. To determine the presence and quantity of cineole, the technique of standard addition or spiking is employed. The sample is first analysed by GC. The sample is then enriched with a
Experiment 5.3: Gas Chromatography 291
known quantity of analyte, in this case cineole. The additional signal produced by the addition of standard increases the area of the original signal. As an example of this, one of the peaks shown on the chromatogram of eucalyptus oil in Figure 5.3.2 is believed to be cineole. By adding (enriching or spiking) a small volume of pure cineole to the eucalyptus oil, an increase in peak size (height and area) can be observed when inspecting the resultant chromatogram (Figure 5.3.3) and comparing it to the original unspiked sample, Figure 5.3.2. This allows the identification of cineole as a component of eucalyptus oil. This is however not conclusive when GC-FID is used alone. Techniques such as gas chromatography-mass spectrometry can confirm the result. The original concentration can be calculated either mathematically or graphically. Increasing the number of additions produces a straight-line calibration. The x-axis intercept value (made positive) represents the original concentration. A typical calibration graph is shown in Figure C. It is necessary to normalise the areas or height before carrying out any calculation. This is achieved by selecting a reference compound appearing in the chromatogram and adjusting the area of this peak such that it is the same for each chromatogram. The areas (or height) ratio should be calculated using the reference compound.
Figure 5.3.2
Figure 5.3.3
292
Example: The area of the largest peak (say, just before 7 mins, not the solvent) in Figure 5.3.2 is 8000. The area of the cineole peak is 800. The ratio is therefore 0.1. Therefore the ratio can be used to plot the calibration curve for the standard addition. From the plot, cineole content = 9%.
Procedure
The following solutions are provided: (a) (b) (c) (d) Eucalyptus oil diluted with hexane sample Cineole diluted with hexane standard Eucalyptus oil spiked with 10% cineole Eucalyptus oil spiked with 20% cineole
Preset instrument details: 1. 2. 3. 4. 5. 6. 7. Instrument: Column: Hewlett Packard 5890 GC 50 m BP-5, 0.2 mm ID 240 C 290 C 60:1
Injector temperature: Detector temperature: Split ratio:
Locate and check the GC head pressure gauge to ensure that there is carrier gas ow. Head pressure should be approximately 20 psi. Set the following isothermal parameters using the GCs keypad: GC PARAMETER Initial temperature: Final temperature: Rate: Initial time: Final time: KEY IN ON GC KEYPAD [INIT TEMP] [1] [0] [0] [ENTER] [FINAL TEMP] [1] [0] [0] [ENTER] [RATE] [1] [5] [ENTER] [INIT TIME] [0] [ENTER] [FINAL TIME] [1] [2] [.] [5] [ENTER]
100C 100C 15C/min 0.00 12.50
Conrm the FID is lit by observing the signal [SIG 1] or by checking for condensation. Switch on the GC oven by pressing [OVEN TEMP] [ON], allow the GC to reach the set point temperature. On the computer, set up the eDAQ software selecting Cineole as the method le (See page 2; Setting up and using eDAQ). Inject 0.5 L of the eucalyptus oil diluted in hexane sample following the procedure for lling a syringe. REMEMBER: Press START on the GC as you inject. Collect 12.5 minutes of data, then print the trace after entering the relevant information in the run info comments section. Examine the chromatogram for resolution, shape of peaks and analysis time.
293
8. 9. 10. 11. 12.
Now set the following temperature-program conditions on the GC using the GCs keypad: GC PARAMETER Initial temperature: Final temperature: Rate: Initial time: Final time: KEY IN ON GC KEYPAD [INIT TEMP] [1] [0] [0] [ENTER] [FINAL TEMP] [2] [4] [0] [ENTER] [RATE] [1] [5] [ENTER] [INIT TIME] [0] [ENTER] [FINAL TIME] [3] [ENTER]
100C 240C 15C/min 0 min 3 min
Inject the eucalyptus oil and run the temperature-program using the above GC conditions. REMEMBER: Press START on the GC as you inject. Finally set the following isothermal conditions and repeat the injection. GC PARAMETER Initial temperature: Final temperature: Rate: Initial time: Final time: KEY IN ON GC KEYPAD [INIT TEMP] [2] [4] [0] [ENTER] [FINAL TEMP] [2] [4] [0] [ENTER] [RATE] [1] [5] [ENTER] [INIT TIME] [0] [ENTER] [FINAL TIME] [1] [2] [.] [5] [ENTER]
240C 240C 15C/min 0 min 12.5 min
Once you have tried all three conditions, choose the best condition (or program) and analyse the cineole diluted with hexane standard and determine the retention time. Now analyse the two eucalyptus oil samples spiked with 10% and 20% cineole.
294
Name
Student ID
Pre-laboratory questions: GC
1. Before using the GC you must check the following;
1.
The GC ......................... ......................... gauge shows pressure.
2.
The .............................. is on and at the set temperature.
3. 2.
The FID is lit (you will observe .......................................... on a spanner when held over the detector).
After rinsing the syringe with solvent and wiping excess from the needle, you draw up
3.
................... L of ..................., followed by ................... L of sample. Circle which temperature option is best for separating a complex mixture such as in eucalyptus oil? (a) (b) (c) Low temperature isothermal run. High temperature isothermal run. Temperature program run.
4.
What advantages are there in using the best temperature option as selected in Q3?
Experiment 5.3: Gas Chromatography 295
296
Name
Student ID
Results: Exercise 1
1. Obtain the peak heights from the eDAQ integration report and copy them into the table below then calculate: (a) (b) average height relative error Peak Time - tR(min) Height - HNorm Area - ANorm
Average % RSD If the relative error exceeds 3%, and if time permits, repeat the exercise. 2. 3. Repeat the calculation using peak area instead of heights and compare the two results. How do the RSD values compare?
Post laboratory questions

Suggest three reasons why you may not achieve repeatable injections.
1: 2: 3:
297
Results: Exercise 2
1. Record the retention time for cineole from the programmed run for the pure sample and use this to identify and label the cineole peak on the eucalyptus oil and spiked eucalyptus oil chromatograms. Complete the table below showing the retention time - tR(min) and peak areas - ANorm for cineole and a nearby reference peak in each chromatogram.
Cineole Peak Cineole Peak Reference Time Area Peak Time Reference Peak Area Ratio Cineole/ Reference
2.
Sample Pure cineole Eucalyptus oil Eucalyptus oil spiked with 10% Cineole Eucalyptus oil spiked with 20% Cineole
3.
Construct a calibration curve as described in the introduction and determine the original cineole concentration in the sample (the unspiked sample).
% Cineole in Eucalyptus Oil =......................................
298
4.
Discuss the advantages of temperature programming when analysing a complex mixture.
5.
Does the spiking technique prove conclusively the identity of an unknown peak? Explain your answer. How might this be achieved?
STOP
Make sure all chromatograms are attached to your report.
299
Departure Checklist
Assessment
Criteria Pre-laboratory questions were... Poor
0 Not attempted 0 Not included 0 Not attempted 0 Not included 0 Not attempted 0.5 Poorly attempted 0.5 Very poor or incomplete 0.5 Poorly attempted 0.5 Very poor or incomplete 0.5 Poorly attempted
Good
1 Mostly incorrect 1 Poor, but complete 1 Mostly incorrect 1 Poor, but complete 1 Mostly incorrect 1.5 Mostly correct 1.5 Acceptable 1.5 Mostly correct 1.5 Acceptable
Excellent
2 All correct 2 Very good 2 All correct 2 Very good
Exercise 1: The results were... Exercise 1: The in-laboratory questions were...
Exercise 2: The results were...
Exercise 2: The in-laboratory questions were...
1.5 Mostly correct
2 All correct
Total (out of 10)
300
EXPERIMENT 5.4: ANALYSIS OF VEGETABLE OILS

Safety notes
!
PPE
The 9 M sodium hydroxide solution is corrosive. Avoid contact with skin. Dichloromethane is toxic and a suspected carcinogen. Avoid any inhalation or contact with skin and eyes You must wear appropriate gloves when handling dichloromethane. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. identify and categorise lipids, utilise industry-standard techniques for the investigation of vegetable oils, relate the observations from these industry-standard techniques to the chemistry of triglycerides specically and lipids more generally, appreciate the importance of lipids in biology.
Aim
To analyse the organic components of vegetable oils using a series of laboratory techniques, to observe some chemical reactions to illustrate their functional groups and to identify the source of an unknown vegetable oil from these tests.
Introduction
Lipids are an important class of biological molecules and comprise the waxy, greasy or oily water insoluble components of most plants and animals. They can be simple lipids, such as the organic classes of compounds alcohols or carboxylic acids. They may also be more complex. The diagram below illustrates how lipids can categorised.
Lipids
Saponifiable
Non-saponifiable
Simple
Complex
Waxes
Triglycerides
Phosphoglycerides
Sphingolipids
Steroids
Prostaglandins
Figure 5.4.1: The major types of lipids (Seager and Slabaugh, Organic and Biochemistry, 7th edn (2011), f 8.3) Experiment 5.4: Analysis of vegetable oils 301
In this experiment we will analyse the chemistry of some common vegetable oils by utilising some of the typical reactions of the triglycerides found in these vegetable oils. Animal fats and vegetable oils are a complex mixture of compounds mostly of a class called triglycerides. A triglyceride is a tri-ester formed between glycerol (a tri-alcohol) and a fatty acid, such as in the reaction represented below between glycerol and three molecules of the saturated fatty acid stearic acid.
O H2C OH HO C O C O C (CH2)16CH3 H2C O O C O C O C (CH2)16CH3
HC
OH + HO
(CH2)16CH3
HC
(CH2)16CH3
+ 3H2O
H2C
OH
HO
(CH2)16CH3
H2C
(CH2)16CH3
glycerol 1 molecule
stearic acid 1 molecule
glyceryl tristearate 1 molecule a saturated triglyceride
In general, a triglyceride may be represented by the glyceride back bone and the long chain of the fatty acid represented by the general group R, such as in the diagram below.
O H2C O C O C O C R H2C O O C O C O C (CH2)7 C H C H (CH2)7CH3
oleate
HC
R'
HC
(CH2)14CH3 palmitate H2 C
H2C
R''
H2C
(CH2)6
C H
C H
(CH2)4CH3
2
linoleate
general representation of a trigylceride
an example of a triglyceride with three different fatty acid chains
Most naturally occurring fats and oils contain mixed triglycerides, where acid groups R, R', and R" may be the same or, more likely, they may be different. The example above has three different fatty acids (oleic, palmitic and linoleic acids) contributing to the formation of the triglyceride. The fatty acid chains can be fully saturated (all single CC bonds, eg palmitate), monounsaturated (one double bond, eg oleate) or polyunsaturated (two or more double bonds, eg linoleate). In all cases, the typical reaction of this class of lipids is between the triglyceride and a strong base (such as sodium or potassium hydroxide) to form glycerol and the salt of the fatty acids. These salts are known as soaps and the reaction is called saponification. Saponification of glyceryl tristearate forms, shown below, glycerol and sodium stearate, a common component in many soaps and beauty products.
Experiment 5.4: Analysis of vegetable oils
302
O H2C O C O C O C (CH2)16CH3 H2C OH O (CH2)16CH3
HC
+ 3NaOH
HC
OH
+ 3 Na
(CH2)16CH3
H2C
(CH2)16CH3
H2C
OH
Some commonly found fatty acids are given below: Saturated: C16 C18 Palmitic Stearic CH3(CH2)14CO2H CH3(CH2)16CO2H
Unsaturated: C18
Oleic Linoleic
CH3(CH2)7CH=CH(CH2)7CO2H CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2H
Acids with more than one double bond in their structure are variously described as polyolefinic, polyethanoid, or polyunsaturated and are said to be beneficial in our diet, especially towards the lowering of blood cholesterol levels. In this experiment, we will explore the typical chemistry of a range of commercial vegetable oils and compare the various techniques used in industry to characterise the compounds. Natural oils are of a highly heterogeneous nature. Their analysis and quality assurance demands the use of a number of parameters such as limits on acid value, saponification value, iodine value, acetyl value where applicable (castor oil), non-saponifiable matter, and physical constants such as weight per mL, refractive index, and optical rotation (castor oil). To guard against deliberate adulteration of the oil, there may also be tests for sesame, cottonseed and other oils. The sample you are given will be one of those listed below. Carry out all tests on the same oil and draw conclusions from your work. The accepted values for each of the tests is given below, though these may vary with the condition or age of the oil. Oil Sesame Olive Safower Sunower Coconut Canola Saponication Value 188-193 187-196 188-194 188-194 255-258 170-177 Iodine Value 103-122 79-90 140-150 125-136 8-9.5 97-105 Acid Value 0.4-2.0 0.2-2.8 1.0-9.9 0.6 1-6 <2 Refractive Index n (25) 1.471-1.474 1.466-1.468 1.472-1.475 1.472-1.474 1.450-1.453 1.472-1.475 n (40) 1.465-1.467 1.460-1.464 1.469-1.469 1.466-1.468 1.448-1.450 1.465-1.466
STOP
This experiment does not have a pre-lab. Please use this time to work carefully to understand how to calculate each of the values from the tests that are used to identify the oils. This will make it much easier to understand the calculations and greatly decrease the time spent in the laboratory. As usual, your demonstrator will be on hand to assist.
303
Procedure
STOP
This experiment runs over two weeks. Please perform Tests 1 (saponification value) and 2 (refractive index) in the first week and Tests 3 (iodine value) and 4 (acid value) in the second week on the same vegetable oil.
Test 1: Saponication value

The saponification value is the number of mg of KOH required to neutralise the fatty acids resulting from the complete hydrolysis of 1 g of the oil. Prepare an alcoholic sodium hydroxide solution approximately 0.7 M by diluting 5 mL of 9 M sodium hydroxide solution to 60 mL with alcohol. Mix very thoroughly. Note When refluxing alcoholic alkali solution using ground-glass joint equipment it is essential to carefully grease the joint between the flask and the condenser before refluxing. During the heating, frequently rotate the condenser to avoid the joint seizing.
STOP

Carry out a blank determination using the same quantity of reagents, but no oil. Accurately weigh about 1.5 mL of the oil (from the burette) into an accurately weighed 100 mL pear-shaped flask, pipette in 20 mL of the alcoholic NaOH solution, add a few boiling stones and reflux gently for 1hour on a water bath. Dilute with about 15 mL of water, add 3 drops of phenolphthalein indicator, and titrate the excess alkali with standard HCl solution (approx. 0.5 M). Calculate the saponification value.
Test 2: Refractive index

Determine the refractive index by using the Abb refractometer, expressing the value to four decimal places. Your demonstrator will explain its use and assist you in obtaining a value. Note the temperature at the time of measurement.
STOP
Complete the remaining experiments in the following lab session.
Test 3: Iodine value

The iodine value of an oil is defined as the number of grams of iodine reacted with 100 g of sample, i.e. it is a measure of unsaturation in the substance. It is the most useful value in identifying the oil, so pay particular attention to your technique. As iodine itself reacts too slowly, iodine monochloride is used which ideally reacts
In order for this reaction to be quantitative, it is performed in the dark to avoid the occurrence of undesirable side reactions.
304
Carry out a blank determination using the same quantity of reagents, but no oil. Accurately weigh about 0.13 g (3 drops) of the oil (from the burette) into a dry, screw-top bottle. Add 10 mL of dichloromethane and dissolve the oil. Pipette in 20 mL of the iodine monochloride solution, screw on the lid previously moistened inside with potassium iodide solution, and allow to stand in the dark for 30 minutes. Add 15 mL of 10% KI solution and 100 mL of water. Shake well and titrate with 0.1 M sodium thiosulfate solution using a starch indicator added near the end of the titration. After titration pour the aqueous layer into the sink and the organic layer into the waste organic bottle provided in the fumehood. Calculate the iodine value using the assumptions below. Your demonstrators will be able to assist with this step. For accurate results no more than half the available halogen should be absorbed.
Adding KI/H2O,
Thus, ICl I2 The reaction remains neutral because:
Test 4: Acid value

The acid value of an oil is defined as the number of mg of KOH required to neutralise the free acids in 1 g of the oil. Accurately weigh about 5.5 mL (5 g) of the oil (from the burette) into an accurately weighed 100mL conical flask and add 25 mL of the neutralised ethanol/ether solvent mixture provided (contains phenolphthalein indicator). If necessary, warm in a hot water bath (using hot water obtained from the tap) to completely dissolve the oil Fill the burette only to 30 mL mark as the titre volume required is too small. Titrate the solution with 0.0200 M sodium hydroxide solution, shaking constantly until a pink colour persists for fifteen seconds. After titration pour the aqueous layer into the sink and the organic layer into the waste organic bottle provided in the fumehood. Calculate the acid value.
305
306
Name
Student ID
Results and discussion (Part 1)

Unknown Oil Number: .......................
Test 1: Saponication value

Results: Weighings (g) Wt container + oil Wt container empty Wt oil
Molarity of HCl:
............................ M
Calculations:
Saponification value:
................................
Test 2: Refractive index

Refractive Index: ................................
Temperature at time of measurement:

........................... C
307
Departure Checklist (Part 1)
STOP
Assessment
Your demonstrator will assess your performance in this laboratory according to this marking key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability. Criteria Test 1: Determination of the saponification value using appropriate techniques and calculations. Test 2: Determination of the refractive index. ** Correct identification of the oil, with appropriate reasoning.
**
Poor 0 1
Good 2 3
Excellent 4
0.5
1.5
Your identification of the oil in part 2 will be added to your part 1 mark.
Total (out of 10)
Your marks for identification of the oil will be added to your part 1 mark and recorded for the first laboratory session (out of 10).
308
Name
Student ID
Results and discussion (Part 2)

Unknown Oil Number: .......................
Test 3: Iodine value

Molarity of sodium thiosulfate: Burette Readings (mL) Final Initial Titre
............................ M Sample Blank
Calculations:
Iodine value:
................................
309
Test 4: Acid value

Molarity of NaOH:
............................ M Sample
Burette Readings (mL) Final Initial Titre
Calculations:
Acid value:
................................
310
Discussion
Summarise your results below and compare to the table in the introduction to assist in your identification of your unknown oil. Oil Number Saponication Value Refractive Index Iodine Value Acid Value Which test gives the most useful result to identify the oil?
Which tests are used to confirm your determination based on the test identified above?
Are there any tests that are not discriminatory, that is, useful, in identifying the oil?
Based on these observations, what is the identity of the oil?
311
STOP
Assessment
Your demonstrator will assess your performance in this laboratory according to this marking key below. Up to 20% of the mark associated with this lab can come from your demonstrators perspective on your laboratory conduct, including cleanliness and general capability. Criteria Test 3: Determination of the iodine value using appropriate techniques and calculations. Test 4: Determination of the acid value using appropriate techniques and calculations. Poor 0 1.5 Good 3 4.5 Excellent 6
Total (out of 10) Your marks for identification of the oil will be added to your part 1 mark and recorded for the first laboratory session (out of 10).
312
EXPERIMENT 5.5: DETERMINATION OF IRON IN CEREALS

Safety
!
PPE
This experiment uses concentrated acids, which are corrosive and may cause burns if they come into contact with your skin. Potassium persulfate is an oxidising agent and harmful. Contact with combustible material may cause a fire. You will be asked to wear gloves when handling the concentrated acids and during clean up. If you spill any solution suspected to contain concentrated acids, you must wear gloves before cleaning up the spill. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. 4. appreciate techniques for preparation of a real sample for analysis, understand the importance of minimising contamination in the laboratory to permit accuracy and precision, prepare a range of standards and apply Beers law to construct a calibration curve and, quantify the concentration of an analyte in a sample by interpolation of a calibration curve.
Aim
To determine the amount of iron in a breakfast cereal and relate the determined value to that stated by the manufacturer. To investigate techniques used to quantify elements in food, such as iron, and relate the importance of trace elements to human nutrition.
STOP
This is a two week investigation. In week 1, please bring along a sample of around 10g of a breakfast cereal. Note down from the nutritional information on the packet the amount of iron reported.
Introduction
Iron is an important trace element required for human nutrition and is found in all cells in the human body. Iron deciency is the most commonly found nutritional deciency and can lead to the chronic condition anemia. Iron from cereals is a minor but important source of iron in our diets. In this experiment, we will develop a method and an appropriate range of standards to analyse for iron in a sample of breakfast cereal. When a thiocyanate (SCN-) solution is added to an Fe(III) solution, coloured complexes form which are in equilibrium with each other. The formation of the complexes is represented in the following reaction scheme:
Experiment 5.5: Determination of iron in cereals
313
[Fe(OH2)6]3+ + SCN- [Fe(OH2)5(SCN)]2+ + SCN- [Fe(OH2)4(SCN)2]+ + SCN-
[Fe(OH2)5(SCN)]2+ [Fe(OH2)4(SCN)2]+ [Fe (OH2)3(SCN)3]
[Fe(SCN)6]3
As the concentration of SCN- increases for a fixed concentration of iron, the equilibrium shifts further to the right. The terminal species is the 6-coordinate [Fe(SCN)6]3-. Although all of these thiocyanato complexes are red, they differ from one another in two important ways. For each species: (a) (b) The wavelength of maximum intensity (max) value varies slightly. The intensity of absorption () is different, with the fully complexed species having the greatest .
Hence for accurate analytical purposes, it is necessary to be certain that the 6-coordinate species is being measured and therefore that a sufficiently high concentration of SCN- is maintained in all solutions. When solutions of iron(III) and thiocyanate ions are mixed, the colour intensity will vary for some time after mixing. This is explained by the following reaction:

[Fe(SCN)6]3- + e- Fe(III) red
[Fe(SCN)6]4 Fe(II) colourless
A redox equilibrium is set up promoted by trace amounts of reducing species in the solution. Since the Fe(II) complex is colourless, the absorbance value decreases with time. To carry out accurate analytical work, we therefore need to add an oxidising agent such as potassium persulfate (K2S2O8) in all solutions to force this equilibrium to the left.
STOP
See Experiment 5.2: Determination of vanillin in vanilla essence for a complete description of UV-Visible Spectrometry.
Determination of very low concentrations of iron requires that all glassware must be free from iron contamination. All glassware must be cleaned to the required degree because iron can be adsorbed from solution onto the surface of glass. A suitable cleaning agent such as dilute nitric acid (3M) can be used to remove iron contamination.
314
Part 1
STOP
This section should be completed in week 1 and the week 1 pre-laboratory and result forms should be handed to your demonstrator for assessment.
Sample preparation
In preparation for the analysis of your cereal in Part 2, consult with your demonstrator for how much cereal you should accurately weigh into a porcelain dish. This will be between 1 and 3 g of the cereal. With the assistance of your demonstrator, place the porcelain dish into the furnace and heat to 550 C for at least 1 hour to ash your sample. While your sample is ashing begin determining an appropriate range of standards for use in Part 2. One of the techniques available for the removal of unwanted organic material is ashing. This involves heating the sample in a muffle furnace under oxidising conditions to about 550C. The organic matter is combusted and inorganic materials, i.e. metal oxides, are left as an ash. Sometimes, if combustion is not complete, a small amount of carbon residue remains.
Both nitric acid and hydrochloric acid are corrosive and can cause severe burns. Take care when handling these reagents and wear gloves.
After the cereal has been ashed, transfer the ash into a 100 mL conical flask and add 2 mL of concentrated HNO3 and 2 mL of concentrated HCl from the dispenser and allow to stand for 5 minutes. Add 5 mL of water in small portions with swirling and boil gently for 10-15 minutes. It may be necessary to add 3M HCl from time to time to prevent the solution boiling dry. Dilute with about 10 mL of water and carefully decant into a clean and dry sample bottle. Wash the residue, and transfer the wash solution to the sample bottle. Limit the volume of extract plus washings to no more than 25 mL. Label your sample with your name, student ID and mass of sample originally weighed and place in the storage cupboard indicated by your demonstrator.
Determining an appropriate range of standards

In order to determine the concentration of an unknown, it is necessary to prepare a calibration curve of absorbance vs concentration under standardised conditions. Some of the necessary experimental conditions for the determination of Fe(III) are recorded in the following table:
Potassium persulfate is an oxidising agent and harmful. Contact with combustible material may cause a fire.
Prepare a solution in a 50.0 mL volumetric flask containing as follows: SCN- concentration 30 mL of 0.5 M KSCN (to give 0.3 M) Acid used and concentration 3.3 mL of 3 M HNO3 (to give 0.2 M) Oxidant concentration 5 mL of 0.2 M K2S2O8 ( to give 0.02 M) Analyte (Fe3+) concentration 5 mL of 30 mg L1 Fe3+ solution (to give 0.15 mg L1)
315
Make the volumetric flask up to the mark with deionised water. Mix well and leave for 15 minutes to equilibrate. Also prepare a blank solution in a 50.0 mL volumetric flask containing all of the reagents except the analyte. For spectrometry, it can be shown that the most accurate results are obtained using solutions with transmission readings between 20% and 80%. Therefore the last parameter that needs to be decided is the iron(III) concentrations that give transmittance readings in that range. Percentage transmittance (%T) is related to absorbance through the following relationship:
Low concentrations can be expressed as parts per million (mg L-1 or ppm); for this work, this simply involves dividing the quantity of Fe(III) taken by the total volume of solution in litres: e.g. = 3 mg L-1 (3 ppm) The values for your range of standards can be calculated from the absorbance value obtained for the previous solution. That is, if all the transmittance values in the table on the following page are converted to absorbances, the quantity of iron(III) required in each solution can be calculated from the known value of A, its concentration (c, 0.15 mg iron(III) in 50 mL = 3 ppm) and the molar absorptivity () of the solution according to Beers law:
Part 2: Analysis for iron by the thiocyanate method

When performing spectrophotometric measurements, it is necessary to prepare a blank solution; in this case, the blank solution should contain all the chemical species used except the iron. The blank is used as a zero absorbance solution, against which the iron solutions are measured. Prepare your standards by pipetting the volumes of the 30 mg L1 iron(III) standard you determined in Part 1 into six 50.0 mL volumetric flasks. To each flask, add the volumes indicated of each of the three reagents (30 mL of 0.5 M KSCN, 3.3 mL of 3 M HNO3 and 5 mL of K2S2O8), make to the mark with deionised water, mix well and allow to equilibrate. Also prepare a reagent blank which contains all reagents except the iron(III) standard. Take your sample from Part 1 and decant with a minimum of rinsing into a 100 mL volumetric flask. Add 60 mL of 0.5 M KSCN and 5 mL K2S2O8 and allow to equilibrate. After 15 minutes equilibration, measure the absorbance of your reagent blank, your standards in order of increasing concentration and your sample. Plot a graph of absorbance (y) versus concentration (x) of your reagent blank and standards using Excel. Obtain a line of best fit and determine the equation describing this line and its Pearsons correlation coefficient (R2). Using the equation describing the calibration, calculate the concentration of your sample (x) using its measured absorbance (y).
STOP
You may wish to bring your laptop to find your calibration curve. Alternatively, a limited number of computers will be provided in the student common room (500.4105/4106) to perform your calibration.
Comment on the result and discuss possible sources of uncertainty.
316
Name
Student ID
Pre-laboratory questions: Determination of iron in cereals (Part 1)

1. Give the name of the breakfast cereal you chose and the reported typical concentration of iron (in mg per 100 g).
2. 3.
Complete the following scheme for the progressive reaction between the hexaaquairon(III) ion and thiocyanate. [Fe(OH2)6]3+ + SCN- [Fe(OH2)5(SCN)]2+ + SCN- [Fe(OH2)4(SCN)2]+ + SCN- [Fe(SCN)6]3

[Fe(OH2)5(SCN)]2+ [Fe(OH2)4(SCN)2]+ [Fe (OH2)3(SCN)3]
Explain why the concentration of thiocyanate is kept high and what impact this would have on the equilibria described in Question 2 above.
317
4.
Prepare a flow chart18 of the procedure indicating the preparative and analytical steps in this experiment.
18
Flowcharting is covered in Part 3 of this manual. If youre not sure how to complete this owchart, see your demonstrator the week before the experiment commences. 318
Name
Student ID
Results: Determination of iron in cereals (Part 1)

Sample preparation
1. Give the mass of your sample you weighed out. Mass of container Mass of container + your sample Mass of your sample (by difference) g g g
Determining an appropriate range of standards

2. Recorded absorbance across the region 470 490 nm for the 3 ppm iron(III) standard solution: max Measured absorbance Calculated molar absorptivity 3. nm AU L mg1(Fe3+) cm1
Calculate the absorbances, concentrations of iron(III) and therefore volumes of the 30 mg L1 iron(III) standard solution required to make your appropriate range of standards. Blank Std. 1 Std. 2 Std. 3 Std. 4 Std. 5 Std. 6
% Transmittance
20
30
40
50
60
80
Calculated Absorbance
[Fe3+] required (mg L1)
Quantity Fe3+ required in 50 mL (mg) Volume Fe3+ standard solution required (mL)
319
4.
Is it possible to measure the volumes you calculated in question 3 above using standard volumetric pipettes (1.00, 2.00, 5.00, 10.0, 20.0 mL etc)? If not, comment on the pipettes you could use to construct a similar range of standards.
320
STOP
Assessment
Not attempted
0.5
Partially attempted
1
All correct
Flowchart: The flowchart prepared was... The molar absorptivity of the iron(III) complex was... The calculation for the appropriate range of standards was... The answer to question 4 was...
0
Very poor
0.5
Poor
1
Good
1.5
Very good
2
Excellent
0
Not calculated
0.5
Incorrect
1
Correct
0
Not attempted
1
Poorly attempted
2
Mostly incorrect
3
Mostly correct
4
All correct
0
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
Fully correct
Total (out of 10)
321
322
Name
Student ID
Pre-laboratory questions: Determination of iron in cereals (Part 2)

1. Citing your source fully 19, what is the recommended intake of iron per day for: (a) adult human males?
(b)
adult human females?
(c)
children?
2.
Why is iron necessary to the metabolism of mammals?
19
We recommend you use the Vancouver method for referencing. Details are on the library website. 323
324
Name
Student ID
Results: Determination of iron in cereals (Part 2)

1. Calculate the concentrations of iron(III) in your standards and measure their absorbances at max. Blank Volume Fe3+ standard solution pipetted (mL) Volume 0.5 M KSCN (mL) 0 Std. 1 Std. 2 Std. 3 Std. 4 Std. 5 Std. 6
30
30
30
30
30
30
30
Volume 3 M HNO3 (mL) Volume 0.02 M K2S2O8 (mL) Concentration of Fe3+ in final solutions (mg L1) Recorded absorbance (AU)
3.3
3.3
3.3
3.3
3.3
3.3
3.3
Measured absorbance of sample 2. What is the equation (in the form y = slope concentration + y-intercept) and Pearsons correlation coefcient (R2) from your line of best t?
AU
325
3.
Using the equation describing the calibration, calculate the concentration of iron in the solution and therefore the concentration in the original sample weighed in Part 1 (in mg 100 g1).
Concentration of iron in solution (mg L1)

Concentration of iron in sample (mg 100 g1)
mg L1 mg 100 g1
4.
What is the expected quantity of iron per 100 g of cereal as specied by the manufacturer? How do your results compare with this value? Offer possible explanations for any variations that may be observed.
326
Departure Checklist
STOP
Assessment
Criteria Pre-laboratory questions were...
0 Not attempted 0 Not included 0 Not attempted 0.5 Poorly attempted 1 Non-linear with no equation 0.5 Within 10% of the accepted value 0.5 Poorly discussed 1 Mostly incorrect 2 Non-linear with equation 1 Within 5% of the accepted value 1.5 Mostly correct 3 Linear with some points removed 1.5 Within 2% of the accepted value 2 All correct 4 Linear and fully correct 2 Within 1% of the accepted value
Construction of a calibration curve: The calibration curve was...
Determination of iron: The determination of iron in the sample was...
Comparison to manufacturers stated value was...
0 Not discussed
1 Logically discussed with some detail
2 Logically discussed with full detail
Total (out of 10)
327
This page left intentionally blank
328
EXPERIMENT 5.6: ANALYSIS OF VITAMIN C

Safety
!
PPE
The chemical hazards in this laboratory are minimal. Your demonstrator will illustrate the procedural hazards during the pre-laboratory briefing. You must wear safety glasses, a laboratory coat and fully enclosed shoes covering your forefoot, toe and heel at all times whilst in the laboratory during this experiment.
Learning Outcomes
On successful completion of this experiment, students will be able to: 1. 2. 3. perform an iodometric titration and utilise its complex stoichiometry to determine concentration, standardise a solution using potassium iodate as a primary standard and, determine ascorbic acid in a powdered sample.
Aim
To standardise sodium thiosulfate using potassium iodate and using the standard solution of sodium thiosulfate determine the concentration of vitamin C (ascorbic acid) in a powdered sample.
Introduction
The oxidation-reduction reaction of iodate with excess iodide in acid solution is used to generate an excess of iodine that oxidises the ascorbic acid in the sample. The reaction is fast and stoichiometric.
The excess iodine is titrated with standard sodium thiosulfate solution using solid iodine indicator. Iodine is a useful oxidising agent in analytical chemistry. It reacts according to the half equation: I2 + 2e 2I If a strong oxidising agent is treated in acid solution with a large excess of iodide ion, the latter acts as a reducing agent and the oxidant will be quantitatively reduced. In such cases, an equivalent amount of iodine is liberated, and is then titrated with a standard solution of a reducing agent, usually sodium thiosulfate. This technique is known as Iodometry. Sodium thiosulfate reacts according to the half equation,
Experiment 5.6: Analysis of vitamin C 329
2S2O32 S4O62 + 2e Therefore, the overall reaction between iodine and sodium thiosulfate is: 2S2O32 + I2 2I + S4O62 Iodine in solution has an intense yellow to brown colour. As the thiosulfate solution is added, the colour changes to pale yellow and finally to colourless. This end point is difficult to detect accurately and a more satisfactory method uses starch that forms an intensely blue coloured complex with iodine. Similar intense colourations are formed using solid iodine indicators available commercially.
Standardisation of thiosulfate
Before we commence our analysis, we must first standardise the titrant, which is a solution of approximately 0.05 M sodium thiosulfate (Na2S2O3). The primary standard used in this exercise is AR potassium iodate (KIO3), which liberates a definite amount of iodine from an excess of acidified potassium iodide according to the reactions: IO3 + 6H+ + 5e I2 + 3H2O 2I I2 + 2e IO3 + 6H+ + 5I 3I2 + 3H2O 1 mole of IO3 produces 3 moles of I2 that reacts with 6 moles of sodium thiosulfate. Thus a 0.0083 M KIO3 solution is required to standardise an approximately 0.05 M Na2S2O3 solution.
Procedure
Standardisation of an approximately 0.05 M solution of sodium thiosulfate
Accurately weigh out the required amount of KIO3 calculated in your pre-lab, dissolve in deionised water and make up to 250mL in a volumetric flask. Pipette 20 mL portions of the KIO3 solution into clean conical flasks, add an excess of potassium iodide (about 0.5 g) and 5 mL of 3 M sulfuric acid. Titrate the liberated iodine with the sodium thiosulfate solution until a pale yellow colour is reached. Add half a spatula of solid iodine indicator and continue to titrate until the colour changes from blue to colourless. Record your titre value and repeat until a concordant triplicate result is obtained.
Determination of vitamin C in a powdered sample

Record in the results section which of the powders A, B or C you used. Suspend an accurately weighed sample of approximately 0.25 g in 100 mL of deionised water in a 250 mL conical flask. Warm the flask for approximately 15 minutes. Repeat this process twice more so you have three separate flasks each containing a known amount of your sample. The resulting solutions will be cloudy due to the presence of inert substances and must be titrated within 2 hours or significant decomposition will occur.
Experiment 5.6: Analysis of vitamin C
330
To one sample, add 5 mL of 3 M H2SO4, 1 g of KI and pipette in 40 mL of the standard KIO3 prepared above and immediately titrate the excess iodine with the standardised sodium thiosulfate solution from above. Add half a spatula of solid iodine indicator when you have a pale yellow coloured solution and continue titrating until the blue solution turns colourless. Repeat on your two other sample flasks starting at the addition of H2SO4, KI and KIO3, immediately titrating the resulting solutions. Calculate the % by weight of ascorbic acid in the powder.
331
332
Name
Student ID
Pre-laboratory questions: Analysis of vitamin C

1. Calculate the weight of potassium iodate (KIO3) required to make 250 mL of 0.0083 M solution.
2.
Iodine and sodium thiosulfate cannot be used as a primary standards. Why?
3.
Why must the solid iodine indicator be added only when the iodine solution attains a pale yellow colour?
333
5.
Prepare a flow chart20 of the procedure indicating the preparative and analytical steps. For each separation, indicate where your analyte, vanillin, will be found and ensure you retain the correct fractions. Remember that vanillin may be present in the molecular or ionic forms.
20
Flowcharting is covered in Part 3 of the manual. If youre not sure how to complete this owchart, see your demonstrator the week before the experiment commences. 334
Name
Student ID
Results: Analysis of vitamin C

Standardisation of an approximately 0.05 M solution of sodium thiosulfate
Mass of container Mass of container + KIO3 Mass of KIO3 (by difference) 1. g g g
Caclulate the exact molarity of your 250.0 mL solution of KIO3 using the mass you weighed above.
Concentration of potassium iodate, [KIO3]
335
Burette Readings (mL) Final Initial Titre
Rough Titration
Accurate Titrations
Mean titre volume Indicate which results are concordant with an asterisk (*). 2.
mL
Calculate the concentration of sodium thiosulfate, recalling that is approximately 0.05 M.
Concentration of sodium thiosulfate, [Na2S2O3]

M
336
Determination of vitamin C in a powdered sample

Your sample powder (A, B or C)
Flask 1 Mass of container Mass of container + sample Mass of sample (by difference) Burette Readings (mL) Final Initial Titre 3. g g g Flask 1
Flask 2 g g g Flask 2
Flask 3 g g g Flask 3
Calculate the number of moles of ascorbic acid in each flask.
337
4.
Calculate the mass of ascorbic acid in each ask.
5.
Calculate the percentage of ascorbic acid based on the mass of sample weighed into each ask. Average this value to obtain the concentration (as w/w%) of ascorbic acid in the original powder sample.
[ascorbic acid]
w/w%
338
Departure Checklist
STOP
Assessment
Criteria 0 Pre-laboratory questions were...
Not attempted
0.5
Poorly attempted
1
Mostly incorrect
1.5
Mostly correct
2
All correct
0 Concentration of Na2S2O3 calculated correctly... Concordant titre values with values given to 0.05 mL... Concentration of ascorbic acid was calculated correctly... Accuracy of calculated ascorbic acid concentration compared to expected value...
No
1
Partially
2
Completely
0
No
2
Yes
0
No
1
Partially
2
Completely
0
20%
0.5
15%
1
10%
1.5
5%
2
2%
Total (out of 10)
339
This page left intentionally blank
340

Chem 101 Lab Manual

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chem 101 Lab Manual

Uploaded by

Copyright:

Available Formats

Department of Chemistry

2012 FIRST YEAR CHEMISTRY LABORATORY MANUAL

Part 2: Chemistry of the elements

Part 3: Synthesis, isolation & purication

Part 4: Chemical and physical changes

Part 5: Techniques in quantitative analysis

This page is left intentionally blank.

Laboratory notes and pre-laboratory presentations

Telephone: Email: Location:

11 simple rules for safety in laboratories

Approximate concentrations of some laboratory reagents

CARE AND USE OF BALANCES

Steps involved in weighing

A GUIDE TO UNCERTAINTIES IN VOLUMETRIC ANALYSIS

Steps for Calculating Uncertainty

Pipette Burette Volumetric Flask 2.

Calculate the value of each uncertainty as a percentage

ADVANCING SCIENCE BY ENHANCING LEARNING IN THE LABORATORY (ASELL)

PART 1: PRINCIPLES OF CHEMISTRY AND CHEMICAL MEASUREMENT

This page is left intentionally blank.

EXPERIMENT 1.1: INTRODUCTION TO THE LABORATORY CHEMICAL PUZZLES

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

Results and discussion

Task: What percentage of the volume of the sponge is air space?

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

You are provided with some anti-acid tablets.

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

Experiment 1.1: An introduction to the laboratory

Results and Discussion

Experiment 1.1: An introduction to the laboratory

Total (out of 10)

Experiment 1.1: An introduction to the laboratory

This page is left intentionally blank.

Experiment 1.1: An introduction to the laboratory

EXPERIMENT 1.2: DETERMINATION OF ACETIC ACID IN VINEGAR

Principles of volumetric analysis

Experiment 1.2: Determination of acetic acid in vinegar

Using a pipette correctly

Experiment 1.2: Determination of acetic acid in vinegar

How to read a burette accurately

3.10 mL 3.25 mL 3.40 mL 3.55 mL 3.70 mL 3.80 mL

Experiment 1.2: Determination of acetic acid in vinegar

Part 1: Standardisation of an approximate 0.1 M sodium hydroxide solution

Part 2: Determination of acetic acid in vinegar

Experiment 1.2: Determination of acetic acid in vinegar

This page is left intentionally blank

Experiment 1.2: Determination of acetic acid in vinegar

Pre-laboratory questions: Acid-base titrations

Why should a constant, minimum amount of indicator be used in titrations?

Experiment 1.2: Determination of acetic acid in vinegar

Part 1: Standardisation of approximately 0.1 M NaOH