Lab Manual for Organic Chemistry: A Short Course

514 Pages·2011·5.815 MB·English

by  T.K. Vinod, Leslie E. Craine

Laboratory Manual

Organic Chemistry
A Short Course

THIRTEENTH EDITION

David J. Hart
The Ohio State University

Leslie E. Craine
Central Connecticut State University

Harold Hart
Michigan State University, Professor Emeritus

T. K. Vinod
Western Illinois University

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Contents

Preface(cid:2) (cid:2)v

Introduction: To the Student(cid:2) (cid:2)viii

1. Melting Point Determination: Purity and Identity of Crystalline
Organic Compounds(cid:2) (cid:2)1

2. Recrystallization: Purification of Crystalline Organic Compounds(cid:2) (cid:2)11

3. Distillation: Separation and Purification of Organic Liquids(cid:2) (cid:2)23

4. Extraction: A Separation and Isolation Technique(cid:2) (cid:2)33

5. Isolation of Natural Products: Caffeine and Eugenol(cid:2) (cid:2) 47

Chemistry at Home: Spice Essences(cid:2) (cid:2)57

6. Chromatography: Column, Thin-Layer, Gas-Liquid, and Paper(cid:2) (cid:2)59

Chemistry at Home: Food Dyes and Marking Pens(cid:2) (cid:2)77

7. Conformations of Alkanes and Cycloalkanes: An Exercise with Molecular Models and
Computer Modeling(cid:2) (cid:2)79

8. Preparation of Alkenes from Cyclohexanol or 2-Methyl-2-butanol, and Tests for
Unsaturation(cid:2) (cid:2)107

9. Cis-Trans Isomerism in Alkenes: Models and Experiments(cid:2) (cid:2)123

10. Cycloadditions: The Diels-Alder Reaction(cid:2) (cid:2) 133

11. Electrophilic Aromatic Substitution(cid:2) (cid:2)149

12. Stereoisomerism: Principles Illustrated with Molecular
Models, Computer Modeling and Experiments(cid:2) (cid:2)169

13. Alkyl Halides: Structure and Reactivity in Nucleophilic Substitutions(cid:2) (cid:2)199

14. The Hydroxyl Group: Reactions of Alcohols and Phenols(cid:2) (cid:2)215

15. Reactions of Aldehydes and Ketones(cid:2) (cid:2)231

16. Oxidation of Alcohols and Reduction of Ketones(cid:2) (cid:2)253

17. Oxidation of Aldehydes to Carboxylic Acids: A Green Chemistry Experiment(cid:2) (cid:2)265

18. Two Ways to Synthesize a Carboxylic Acid(cid:2) (cid:2)271

iii
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iv Contents

19. Reactions of Carboxylic Acids and Their Derivatives(cid:2) (cid:2)283

Chemistry at Home: Eggshells and Vinegar(cid:2) (cid:2)301

20. Esters: Synthesis and Saponification of Methyl Benzoate(cid:2) (cid:2)303

Chemistry at Home: Saponification Is Making Soap(cid:2) (cid:2)315

21. Synthesis of Aspirin (Acetylsalicylic Acid)(cid:2) (cid:2)319

22. Amines and Diazonium Compounds(cid:2) (cid:2)327

23. Preparation of Sulfanilamide: A Multistep Synthesis(cid:2) (cid:2)341

24. Dyes and Dyeing(cid:2) (cid:2)351

Chemistry at Home: Natures’s Indicators and What They Indicate(cid:2) (cid:2)366

25. Infrared and NMR Spectroscopy(cid:2) (cid:2)369

26. Synthesis of a Heterocycle: 2-Amino-4,6-dimethylpyrimidine(cid:2) (cid:2)379

27. Storage and Release of Light Energy: Benzopinacol and Luminol(cid:2) (cid:2)387

28. Synthetic Polymers(cid:2) (cid:2)395

29. Fats and Oils; Soaps and Detergents(cid:2) (cid:2)409

Chemistry at Home: Soap and Talcum Powder(cid:2) (cid:2)421

30. Reactions of Carbohydrates(cid:2) (cid:2)423

Chemistry at Home: Where’s the Starch?(cid:2) (cid:2) 439

31. Amino Acids and Proteins(cid:2) (cid:2) 441

Chemistry at Home: Enzymes Are Nature’s Catalysts(cid:2) (cid:2)461

Appendix A Some Useful Atomic Weights(cid:2) (cid:2)463

Appendix B Boiling Points and Densities of Some Common Organic Liquids(cid:2) (cid:2)463

Appendix C Concentrations of Common Reagents(cid:2) (cid:2)463

Appendix D Preparation of Special Reagents(cid:2) (cid:2)464

Appendix E Chemicals Required for Each Experiment(cid:2) (cid:2) 465

Appendix F Suggested Equipment for Each Student(cid:2) (cid:2)481

Index(cid:2) (cid:2)483

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Preface

This laboratory manual is designed for a short introductory course in organic chemistry. It is ideal
for a one-semester or a one- or two-quarter course. Most of the experiments can be completed by
a beginner in a single three-hour laboratory period, and some in considerably less time. Many
experiments have multiple parts that can easily be adapted to a two-hour period, if necessary.
The manual consists of thirty-one experiments, offering instructors a wide selection from
which to choose. In addition, those experiments with multiple parts allow instructors flexibility
in choosing experiments particularly suited to their own students, facilities, and schedules. For
further alternatives, nearly half the experiments offer optional microscale procedures. The lab
manual also includes a set of eight experiments under the heading of Chemistry at Home that
students can do outside a laboratory setting.
Among the many features of this manual is the useful combination of varied experiments:
technique experiments; preparative experiments; experiments that illustrate reactions of and tests
for various functional groups; and general-interest, or practical, experiments illustrating
applications of organic chemistry. In this edition we have included an experiment for an eco-
friendly oxidation of aldehydes to carboxylic acids thus introducing students to the concepts of
Green Chemistry. Also in this edition is the inclusion of Pre-Lab Exercises, a set of questions
following each experiment which instructors may utilize and include as part of the required pre-
lab write up or use as pre-lab quizzes to ascertain student preparedness to successfully carry out
the experiment. Immediately following the Pre-Lab exercise of every experiment, report sheets on
perforated paper help students take notes in an orderly manner. Questions at the end of the report
enable students to reinforce what they have learned from the experiment.
For the instructor’s convenience, the appendices include instructions for preparing special
reagents and complete lists of the chemicals required for each experiment and their quantities
per ten students.

Organization

The experiments are organized as follows: The first six illustrate common laboratory techniques.
The next sixteen give the student experience with some important reactions of the common
functional groups. This sequence parallels the order in which these groups are discussed in the
accompanying text (Hart, Organic Chemistry: A Short Course, 13th edition) and approximates the
order in most brief texts. Next comes a simple multistep synthesis, followed by experiments on
practical applications, on spectroscopy, and on biomolecules (or their analogs). Chemistry at Home
experiments are located at the end of experiments to
which they are related.
Unique to this manual are Experiments 7 and 12—which give the student experience in
manipulating molecular models in the context of conformational analysis and stereochemistry,
and subsequently giving them an opportunity to verify what they learned about strain energy and
conformations by having them perform molecular modeling (mechanics) calculations using
commercially available modeling programs. Molecular models are also used in Experiment 9 in
conjunction with experimental sections to highlight the configurational aspects and reactivity
patterns of cis-trans isomers. In Experiment 17 and 18, the student synthesizes the same
compound by three different methods and consequently learns that one’s objectives can be
achieved through more than one approach.
v
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vi Preface

The Thirteenth Edition

The order of experiments in the thirteenth edition follows closely the order in which topics are
introduced in the accompanying text. Experiment 11 (Electrophilic Aromatic Substitution) uses
a discovery format, although it can be carried out in the traditional manner at the instructor’s
discretion. In the discovery format, students make individual contributions to a common data
pool, from which conclusions can be drawn about substituent directing effects (Part A) and
activating effects (Part B). Either Part A or Part B can be carried out within one
3-hour lab period. Experiment 17, describing an eco-friendly protocol for a convenient
oxidation of aldehydes to carboxylic acids, is a new experiment included in this edition.
Experiments 1, 4, 5, 7, 8, 10, 12, 14, 15, and 22 have been revised significantly, including
some changes in existing experiments, some additions, and some deletions.

Microscale A large number of undergraduate teaching laboratories have converted to microscale
Experiments techniques for reasons of laboratory safety, economy of scale, and reduction of waste-
disposal problems. As in the previous four editions, this edition contains both macroscale
and microscale experiments. Microscale procedures are included in Experiments 2, 4, 8-11,
13, 15-21, 23, 26, and 27.
The procedures for the microscale experiments are based on the glassware designed and
developed by Mayo, Pike and Forbes.* Most of these experiment, however, can also be
adapted to the glassware designed for Williamson’s text,** and many can be run in readily
available glassware and do not require a special kit. The microscale experiments that can be
run without special glassware are Experiments 2 Part A, 4, 9 Part B (Sec. 2), 10, 11, 15, 16
Part B, 21, 23, 26, and 27 Part A.

Chemistry A thirteenth edition contains a set of eight experiments that students can do outside the
at Home laboratory. These experiments are located at the end of Experiments 5, 6, 19, 20, 24, 29, 30
and 31. Each one contains a brief introduction, a list of materials needed (all of which are
readily obtained household items), a procedure, some questions for thought, some suggestions
for additional explorations, and some suggested reading materials. No report form is provided
since these experiments are meant to be exploratory and open-ended. The instructor may wish
to assign these experiments, use them as a springboard for other laboratory or classroom
activities, or simply encourage students to try them out.

Safety and As in previous editions, safety is emphasized in this edition. Readily identifiable “Cautions”
Waste Disposal advise students and instructors of potential hazards and precautionary measures. Safer
Instructions heating methods have been substituted for oil baths and Bunsen burners when possible. Safety
and environmental considerations have prompted us to include the suggested waste
disposal directions to the experiment procedures. Students are clearly instructed to dispose of
both organic and aqueous wastes in appropriately labeled waste containers. Under no
circumstance should aqueous waste from experiments be disposed of in the sink flushing it
with large amounts of water. Although chemical experimentation always carries some risk
with it, most of these experiments have been used safely with thousands of students for more
than 30 years. The microscale experiments offer additional safety advantages because they
involve decreased exposure to toxic substances and use smaller quantities of flammable
solvents. With care, common sense, and good judgment, all of these experiments should be
safe, even in the hands of beginners.

*Mayo, D. W., Pike, R. M., and Forbes, D. C., Microscale Organic Laboratory: with Multistep and
Multiscale Syntheses, 5th ed., John Wiley & Sons: Hoboken, 2011.

**Williamson, K. L., and Masters, K. M., Macroscale and Microscale Organic
Experiments, 6th ed., Brooks/Cole, Cengage Learning: Belmont, 2011.
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
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Preface vii

The Chemistry at Home experiments are as safe as any normal activity carried out in the home
and do not, therefore, require special safety instructions. However, students should be reminded to
pay attention to the cautions on the labels of the household products they use and in general to
behave sensibly around kitchen appliances. In two of the experiments, additional cautions are
explicitly given because pf the nature of the household products used.

Safety Note It is assumed throughout this manual that each instructor is thoroughly familiar with ordinary
safety precautions involved with solutions he or she prepares for students. If students, lab
assistants, or untrained personnel are used to prepare these solutions, the instructor is solely
responsible for the safety of the students who use the laboratory manual; even though safety
precautions are featured as required in each experiment, they are not intended as a substitute for
the instructor’s directions and supervision.

Acknowledgments

Reviewers of previous editions of this manual have found that there is a “good representative
selection of well-described experiments that work well when performed by beginners” and that
“in general this manual requires less costly materials and relatively safe procedures and materials
when compared to other lab manuals.” We hope that users of previous editions and new users of
this one will continue to find these virtues in the manual. Suggestions for improvement are
always welcome and should be sent to Dr. T. K. Vinod, Department of Chemistry, One
University Circle, Western Illinois University, Macomb, IL 61455.

DAVID J. HART
THE OHIO STATE UNIVERSITY

LESLIE E.CRAINE
CENTRAL CONNECTICUT STATE UNIVERSITY

HAROLD HART
MICHIGAN STATE UNIVERSITY

DR. T. K. VINOD
WESTERN ILLINOIS UNIVERSITY

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Introduction: To the Student

Aims of Laboratory Work

The experiments in this book illustrate many of the reactions discussed in your text. When you
perform a reaction in the laboratory, it should become more vivid to you and therefore easier to
conceptualize and remember.
Before each set of experiment directions, you will find a brief discussion of the chemistry
that the experiment illustrates. It is important that you read and understand these discussions
before doing the experiment. You may find it helpful to look up the particular reaction in your
text and read about it there, as well. There is not much point in performing an experiment
without really understanding what you are doing.
The primary aim of laboratory work in this course is to illustrate the chemical reactions and
properties of molecules discussed in lecture and to help you learn them. We hope that you will
also find some of the experiments fun to do and that you will be encouraged to try your hand at
some of the new Chemistry at Home experiments as well.

General Laboratory Instructions and Pre-Lab Preparations

Learning experimental chemistry efficiently requires one to arrive at the laboratory prepared. Be
sure to read the experiment directions before your scheduled laboratory period. Familiarize
yourself with the equipment and procedure before you enter the laboratory. If you do not
understand them, or if you have some questions about the chemistry involved in an experiment,
ask your instructor directly for a reliable response.
Many students come to the laboratory ill-prepared to perform the experiment and consider
it perfectly acceptable to carry out their work by following a given experimental procedure as a
recipe to obtain their final desired result or product. Blindly following a procedure (often
asking oneself in the middle of the experiment, what do I add next? or what do I do next?)
invariably results in adding or doing the wrong thing at the wrong time. The ill consequences
of such an approach in the laboratory can result in having to re-do the experiment, not getting
the desired product/result at the end, and, even worse, creating accidents that can potentially
hurt the student and other occupants of the lab.
In order to enhance the learning experience and enjoyment of a laboratory experience,
instructors often require students to complete a detailed pre-lab write-up prior to attending the
laboratory, thus forcing the students to read the theory and practical aspects of the experiment.
Individual instructors vary in their preference for the type of laboratory notebook to be used, but
universally all instructors prefer a bound notebook with entries made in ink. The pre-lab write-
up includes the title of the experiment, purpose, chemical equations in case of preparative
experiments, reagents and amounts used, a detailed procedure, and, finally, answers to any
assigned pre-lab questions.
Following each experiment, you will find a set of questions under the heading of Pre- Lab
Exercise. Your instructor may assign all or some of these questions as part of your pre- lab write-up
or may choose to use these questions as a pre-laboratory quiz to ascertain your preparedness to do
that particular experiment. In any case, by answering these questions, you will able to comprehend
the underlying concepts, both theoretical and practical, of the experiment and will also be able to
assess your preparedness to successfully complete the experiment in the allotted time.
viii
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