Graduate School ETD Form 9

(Revised 12/07)

PURDUE UNIVERSITY
GRADUATE SCHOOL
Thesis/Dissertation Acceptance

This is to certify that the thesis/dissertation prepared

By John Leo Grutsch, Jr.

Entitled AN INVESTIGATION OF STUDENT UNDERSTANDING IN THE

UNDERGRADUATE ORGANIC CHEMISTRY LABORATORY

For the degree of Doctor of Philosophy

Is approved by the final examining committee:

George M. Bodner
Chair
Marcy H. Towns

Mark A. Lipton

Mingji Dai

To the best of my knowledge and as understood by the student in the Research Integrity and
Copyright Disclaimer (Graduate School Form 20), this thesis/dissertation adheres to the provisions of
Purdue Universitys Policy on Integrity in Research and the use of copyrighted material.

George M. Bodner
Approved by Major Professor(s): ____________________________________
____________________________________

Approved by: R. E. Wild 7/24/2014

Head of the Graduate Program Date
AN INVESTIGATION OF STUDENT UNDERSTANDING IN THE
UNDERGRADUATE ORGANIC CHEMISTRY LABORATORY

A Dissertation

Submitted to the Faculty

of

Purdue University

by

John Leo Grutsch, Jr.

In Partial Fulfillment of the

Requirements of the Degree

of

Doctor of Philosophy

August 2014

Purdue University

West Lafayette, Indiana

 UMI Number: 3669234

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 ii

To my father Dr. John L. Grutsch, Sr.

In the summer that I was baptized,

My father held me to his side,
As they put me to the water,
He said how on that day I cried.
We were prisoners of love, a love in chains,
He was standin in the door, I was standin in the rain,
With the same hot blood burning in our veins,
Adam raised a Cain (heh)
Adam raised a Cain (heh)
Adam raised a Cain (heh)
Adam raised a Cain (heh)
(Springsteen, 1978)
 iii

ACKNOWLEDGMENTS

First and foremost I must give thanks and praise to the three persons of the Holy

Trinity; God the Father, Jesus Christ his only begotten son, and the Holy Spirit. For it is

only through the grace and mercy of the most high God that I live and breathe. Without

him I can do nothing. As the psalmist wrote so many centuries ago: The Lord is my

strength and my shield: my heart trusts in him and I am helped (Psalm 28:7).

I will also ever be grateful the many friends who offered help and assistance

during my time as a graduate student at Purdue University. Many more than who could

be mentioned here. However, there are a few persons whose support has been so

essential that they must be acknowledged. I must thank my advisor and friend Dr.

George Bodner. Dr. Bodner, I will always be grateful for your support in allowing me to

pursue a research project that perhaps only has meaning to me, but answered questions

that I needed to answer for myself. Thank you for your patience in watching me make so

many mistakes, falling flat on my face, and encouraging me to get back up and continue.

I must also thank the director of the undergraduate teaching laboratories Mr. Kurt Keyes

for allowing me to be the laboratory coordinator for the upper division organic chemistry

laboratory courses. Kurt thank you for allowing me to assume full responsibility for the

upper-division organic chemistry laboratory courses, if it was not for your confidence in

me, this research project and dissertation would not have been possible. I must also
 iv

thank my parents John and Theresa Grutsch. Mom and Dad, thank you for your support

during the darkest moments of the project when it seemed too big and insurmountable. I

also must thank the students who took the time to participate in numerous interviews and

had the courage to share their thoughts, ideas, feelings, and experiences. I will forever be

grateful for the insights you provided. I also thank Elizabeth Hewitt for her help in

formatting this dissertation, Ms. Debbie Packer for making sure I was always properly

registered each semester, Dr. Robert Wild for allowing me teach both organic and general

chemistry courses at Purdue University, and Ms. Amy Jines for her support and kindness

during the first few years of graduate school.

 v

TABLE OF CONTENTS

Page

LIST OF TABLES ............................................................................................................. xi

LIST OF SCHEMES........................................................................................................ xiii

ABSTRACT ..................................................................................................................... xiv

CHAPTER ONE INTRODUCTION ..................................................................................1

1.1. Pedagogical Effectiveness of the Organic Chemistry

Teaching Laboratory ...............................................................................................1

CHAPTER TWO LITERATURE REVEIW ......................................................................4

2.1 Introduction ..............................................................................................................4

2.2. Styles of Laboratory Instruction .............................................................................4
2.2.1. Expository Style of Laboratory Instruction....................................................6
2.2.2. Guided Inquiry or Discovery Style of Laboratory Instruction.......................8
2.2.3. Open Inquiry Style of Laboratory Instruction .............................................11
2.2.4. Problem or Project based Styles of Laboratory Instruction ........................13
2.3 Conclusion .............................................................................................................17

CHAPTER THREE METHODOLOGY ..........................................................................18

3.1 Introduction ............................................................................................................18

3.2 Research Paradigm.................................................................................................18
3.2.1 Quantitative Methodological Paradigms......................................................19
3.2.2 Qualitative Methodological Paradigms ........................................................20
3.2.2.1 Guiding Research Question ..............................................................22
3.2.2.1.1 Categories of Research Questions .....................................23
3.2.2.1.2 Guiding of Research Question ...........................................24
3.2.2.2 Theoretical Paradigm .......................................................................24
3.2.2.2.1 Positivism ...........................................................................25
3.2.2.2.2 Post Positivism ...................................................................26
3.2.2.2.3 Constructivism ...................................................................27
3.2.2.2.4 Conceptual Change Research ............................................30
 vi

Page

3.2.3 Mixed Methodological Paradigms ................................................................31

3.3 Sampling Technique ..............................................................................................33
3.3.1 Research Sample ...........................................................................................34
3.3.2 Interview Participants...................................................................................36
3.3.2.1 Buffy ..................................................................................................36
3.3.2.2 Jody ...................................................................................................37
3.4 Data Collection ......................................................................................................39
3.4.1 Methods of Data Collection ..........................................................................39
3.4.2 Use of Open Ended Questions ......................................................................40
3.5 Data Analysis .........................................................................................................41
3.5.1 Inductive Approach to Data Analysis ...........................................................41
3.5.2 Thematic Content Analysis ...........................................................................42
3.6 Validity ..................................................................................................................43
3.6.1 Transactional Validity ..................................................................................43
3.8 Conclusion .............................................................................................................44

CHAPTER FOUR THE RESEARCH SETTING ............................................................45

4.1 Introduction ............................................................................................................45

4.2 Description of the Second Semester Organic Chemistry Laboratory Course....... 46
4.3 Description of Classroom Environment.................................................................47
4.4 Experiments Investigated .......................................................................................48
4.4.1 Williamson Synthesis of Ethers, Preparation of
Methyl p-Ethylphenyl Ether ..........................................................................49
4.4.2 Diels-Alder Reaction: Preparation of 4-Cyclohexene-cis-1,2-
dicarboxylic Acid Anhydride..........................................................................52

CHAPTER FIVE STUDENT RESPONSES TO PRELABORATORY

QUIZ QUESTIONS ............................................................................59

5.1 Introduction ............................................................................................................59

5.2 The Williamson Synthesis of Methyl p-Ethylphenyl Ether ...................................60
5.2.1 Student Understanding of the Mechanism of the Williamson
Synthesis of Methyl p-Ethylphenyl Ether ......................................................63
5.2.1.1 Methyl or Primary Alkyl Halide .......................................................63
5.2.1.2 Backside Attack .................................................................................65
5.2.1.2.1 Backside Attack Without Mechanistic
Arguments .........................................................................66
5.2.1.2.2 Substitution .......................................................................67
5.2.1.2.3 Formation of Iodide ...........................................................68
5.2.1.3 Nucleophilic Attack Releases Iodine.................................................69
5.2.1.4 One Step Reaction .............................................................................70
5.2.1.5 Substitution .......................................................................................71
 vii

Page

5.2.1.6 SN2 Without Discussion.....................................................................72

5.2.1.7 Intermediates.....................................................................................72
5.2.2 Student Understanding of the Purpose of the 25% Sodium
Hydroxide Solution .......................................................................................73
5.2.2.1 Deprotonation ...................................................................................74
5.2.2.1.1 4-Ethylphenol ......................................................................75
5.2.2.1.2 Phenol .................................................................................76
5.2.2.1.3Unspecified ..........................................................................77
5.2.2.2 To Produce a Basic Environment .....................................................77
5.2.2.3 Creation of a Nucleophile .................................................................79
5.2.2.4 Catalyst .............................................................................................80
5.2.2.5 Phase Transfer Catalyst....................................................................81
5.2.2.6 Creates Water and Na+ .....................................................................82
5.2.3 Student Understanding of the Purpose of Tetrabutylammonium
Bromide .........................................................................................................83
5.2.3.1 Phase Transfer Catalyst....................................................................84
5.2.3.1.1 Transfers Phenoxide ...........................................................85
5.2.3.1.2 Transports Halide ...............................................................86
5.2.3.1.3 Brings Down Salt ................................................................87
5.2.3.2 Moves Between Phases .....................................................................87
5.2.3.2.1 4-Ethylphenol ......................................................................88
5.2.3.2.2 Carries Product Across Boundary ......................................89
5.2.3.2.3 Transfer Na+ and I- .............................................................89
5.2.3.3 Catalyst .............................................................................................90
5.2.3.4 Environment ......................................................................................91
5.2.3.5 Miscellaneous ...................................................................................92
5.2.4 Student Understanding of the Purpose of the 5% Sodium Hydroxide
Solution .........................................................................................................93
5.2.4.1 Reacts with Reagents ........................................................................96
5.2.4.2 Deprotonate ......................................................................................97
5.2.4.3 Remove Impurities ............................................................................98
5.2.4.3.1 Remove Acid Molecules .....................................................99
5.2.4.3.2 Remove Ions .....................................................................100
5.2.4.3.3 Remove Unspecified Impurities .......................................101
5.2.4.4 Purify...............................................................................................102
5.2.4.5 Removes Aqueous Layer .................................................................103
5.2.4.6 Separate Layers ..............................................................................104
5.2.5 Student Understanding of the Purpose of the Water Wash
of the Combined Diethyl Ether Extracts .....................................................105
5.2.5.1 Removes Traces of Sodium Hydroxide ...........................................106
5.2.5.2 Removes Ions ..................................................................................108
5.2.5.3 Removes Impurities and Contaminates...........................................110
5.2.5.4 Removes Water................................................................................111
 viii

Page

5.2.5.5 Miscellaneous ...................................................................................113

5.3 Diels-Alder Synthesis of 4-Cyclohexene-1,2-Dicarboxylic Acid
Anhydride ............................................................................................................114
5.3.1 Student Understanding of the Purpose of 3-Sulfolene ................................116
5.3.1.1 1,3-Butadiene is a Gas ....................................................................117
5.3.1.1.1 3-Sulfolene is Easier to Handle .......................................117
5.3.1.1.2 1,3-Butadiene is a Gas that is Difficult
to Handle/Measure...........................................................118
5.3.1.1.3 3-Sulfolene is a Source of 1,3-Butadiene .........................119
5.3.1.1.4 3-Sulfolene is Used Instead of 1,3-Butadiene ..................120
5.3.1.1.5 Miscellaneous ..................................................................121
5.3.1.2 3-Sulfolene is More Stable ..............................................................122
5.3.1.3 Miscellaneous .................................................................................122
5.3.2 Student Understanding of How Sulfur Dioxide Produced
is Handled ...................................................................................................125
5.3.2.1 Use of Fume Hood ..........................................................................127
5.3.2.2 Use of Fume Hood and Drying Tube ..............................................127
5.3.2.2.1 Drying Tube with Calcium Chloride.................................128
5.3.2.2.2 Drying Tube Packed with Absorbent ................................129
5.3.2.2.3 Drying Tube ......................................................................130
5.3.2.3 Experimental Apparatus .................................................................130
5.3.2.3.1 Column ..............................................................................131
5.3.2.3.2 Condenser .........................................................................132
5.3.2.4 Tube to Trap SO2 ............................................................................132
5.3.2.5 Miscellaneous .................................................................................133
5.3.3 Student Understanding of the Use of Xylenes a Solvent .............................135
5.3.3.1 Dissolves Reactants ........................................................................137
5.3.3.1.1 High Boiling Point ............................................................138
5.3.3.1.2 Does not Interact with Reactants ......................................138
5.3.3.1.3 Stable at Reaction Temperatures ......................................139
5.3.3.1.4 Dissolves Reactants ..........................................................140
5.3.3.1.5 Xylenes Boils Off ...............................................................140
5.3.3.2 Non-Reactive ...................................................................................141
5.3.3.2.1 Wont React.......................................................................141
5.3.3.2.2 Ease of Isolating Product..................................................143
5.3.3.2.3 Keeps Butadiene in Solution .............................................143
5.3.3.3 Presence of Double Bonds ..............................................................144
5.3.3.4 Miscellaneous .................................................................................145
5.3.4 Student Understanding of the Need for Anhydrous
Conditions ...................................................................................................149
5.3.4.1 Reaction ..........................................................................................150
5.3.4.1.1 Maleic Anhydride .............................................................151
5.3.4.1.2 Product.............................................................................152
 ix

Page

5.3.4.1.3 Reactants ..........................................................................153

5.3.4.1.4 Xylenes .............................................................................153
5.3.4.1.5 Side Reactions ..................................................................155
5.3.4.2 Miscellaneous .................................................................................156
5.3.5 Student Understanding of Methods to Dry Xylenes ....................................158
5.3.5.1 Distillation ......................................................................................160
5.3.5.1.1 Distillation Only...............................................................160
5.3.5.1.2 Molecular Filter ...............................................................161
5.3.5.1.3 Drying Agent ....................................................................162
5.3.5.2 Drying Agent ...................................................................................162
5.3.5.3 Oven ................................................................................................163
5.3.5.4 Desiccator .......................................................................................164
5.3.6 Student Understanding of the Nature of Petroleum
Ether............................................................................................................165
5.3.6.1 Mixture of Hydrocarbons ................................................................167
5.3.6.2 Mixture of Alkanes ..........................................................................168
5.3.6.3 Ether................................................................................................169
5.3.6.4 Solvent .............................................................................................169
5.3.6.4.1 Product Not Soluble at Cold
Temperatures ...................................................................170
5.3.6.4.2 Wash Solvent .....................................................................170
5.3.6.4.3 Organic Solvent ................................................................171
5.3.6.4.4 Volatile Solvent .................................................................171
5.3.6.4.5 Recrystalization Solvent ....................................................172
5.3.7 Student Understanding of the Purpose of Petroleum
Ether............................................................................................................173
5.3.7.1 Products not Soluble at Cold Temperatures ...................................174
5.3.7.2 Product not Soluble but Impurities Are Soluble .............................174
5.3.7.3 Washes Away Impurities .................................................................175
5.3.7.4 Recrystalization Solvent ..................................................................177
5.3.7.5 Miscellaneous .................................................................................178

CHAPTER SIX STUDENT INTERVIEWS ..................................................................180

6.1 Student Responses to Pre-laboratory Quiz Questions .........................................180

6.1.1 Purpose of the 5% Sodium Hydroxide Solution in the Williamson
Synthesis of Methyl p-Ethylphenyl Ether ....................................................181
6.1.2 Use of Xylenes as Solvent in the Diels-Alder Synthesis of
4-Cylcohexene-cis-1,2-Dicarboxylic Acid Anhydride .................................182
6.1.3 Need for Anhydrous Conditions in the Diels-Alder Synthesis
of 4-Cyclohexene-cis-1,2-Dicarboxylic Acid Anhydride .............................184
6.2 Student Perception of the Lack of Learning in the Organic
Chemistry Teaching Laboratory ..........................................................................185
 x

Page

6.3 Student Experiences of the Organic Chemistry Teaching

Laboratory ............................................................................................................190
6.4 Student Perception of the Teaching Assistants ....................................................193
6.5 Student Perception of the Relationship between Lecture
and the Laboratory ...............................................................................................197
6.6 Student Perception of the Course .........................................................................199

CHAPTER SEVEN CONCLUSIONS ...........................................................................201

7.1 Introduction ..........................................................................................................201

7.2 Characteristics of Student Responses ..................................................................201
7.3 Student Perception of the Lack of Learning ........................................................204
7.4 Assertions............................................................................................................205

BIBLIOGRAPHY ............................................................................................................211

APPENDICES

Appendix A Guided Inquiry Experiments by Technique of

Characterization ...................................................................................221
Appendix B Student Responses to Pre-Laboratory Quiz
Questions..............................................................................................223
Appendix C Pre-Laboratory Quizzes ........................................................................249
Appendix D Williamson Synthesis of Methyl p-Ethylphenyl
Ether .....................................................................................................256
Appendix E Diels-Alder Synthesis of 4-Cyclohexene-cis-1,2-
Dicarboxylic Acid Anhydride ..............................................................261
Appendix F IRB Application ...................................................................................270

VITA ................................................................................................................................277

PUBLICATION ...............................................................................................................278
 xi

LIST OF TABLES

Tables Page

2.1 Styles of Laboratory Instruction ....................................................................................5

3.1 Categories of Guiding Research Questions .................................................................23

3.2 Theoretical Paradigms .................................................................................................25

3.3 Forms of Constructivism..............................................................................................30

Appendix Tables

2.1 Synthetic and Preparative Guided Inquiry Laboratory Activities

by Technique of Characterization ..............................................................................221

5.1.Student Mechanistic Classification of the Williamson Synthesis of

Methyl p-Ethylphenyl Ether ......................................................................................223

5.2 Student Understanding of the Purpose of the 25% Sodium

Hydroxide Solution ....................................................................................................226

5.3 Student Understanding of the Purpose of Tetrabutylammonium

Bromide Forms of Constructivism.............................................................................228

5.4 Student Understanding of the Purpose of the Wash of the Combined Diethyl
Ether Extracts with a 5% Sodium Hydroxide Solution .............................................230

5.5 Student Understanding of the Water Wash of the Combined Diethyl

Ether Extracts Forms of Constructivism ....................................................................232

5.6 Student Mechanistic Understanding of the use of Sulfolene .....................................234

5.7 Student Understanding of how the Sulfur Dioxide Produced in the

Reaction is Handled ...................................................................................................237

5.8 Student Mechanistic Understanding of the use of Xylenes as Solvent ......................239

 xii

Appendix Tables Page

5.9 Student Mechanistic Understanding of the need for Anhydrous

Conditions ..................................................................................................................242

5.10 Student Mechanistic Understanding of how to dry Xylenes ...................................244

5.11 Student Understanding of the Nature of Petroleum Ether .......................................245

5.12 Student Understanding of the use of Petroleum Ether .............................................246

 xiii

LIST OF SCHEMES

Scheme Page

4.1 Phase Transfer Catalysis Cycle ....................................................................................52

4.2 Electron Flow in Diels Alder Reaction ........................................................................54

4.3 Stereoselectivity of the Diels Alder Reaction ..............................................................54

4.4 Stereochemical Consequences of Orientation of Reactants.........................................55

4.5 Diels-Alder Reaction of 1,3-Butadiene with Maleic Anhydride .................................56

5.1 Williamson Synthesis of Methyl p-Ethylphenyl Ether ................................................60

5.2 Mechanism of the Williamson Synthesis of Methyl p-Ethylphenyl Ether ..................62

5.3 Resonance Stabilization of the Phenoxide Ion.............................................................62

5.4 Role of the 25% Sodium Hydroxide Solution .............................................................74

5.5 Diels-Alder Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic

Anhydride .................................................................................................................115

5.6 Thermal Decomposition of 3-Sulfolene.....................................................................116

 xiv

ABSTRACT

Grutsch, John Leo., Jr. PhD. Purdue University, August, 2014. An Investigation of
Student Understanding in the Undergraduate Organic Chemistry Teaching Laboratory.
Major Professor: George M. Bodner.

Laboratory activities in organic chemistry involve a mixture of sophisticated logic

and empirical observation that requires the integration of mechanistic thought, laboratory

technique, and problem-solving skills. In an effort to understand how students develop

the thought processes and problem-solving skills necessary for laboratory work in

organic chemistry, student understanding of how the interaction between a reaction

system (reactants or starting material(s), reagent(s), and/or solvent), experimental

variables (pH, temperature, concentrations, etc), provides a result of interest (yield,

selectivity, purity, etc.) for an experiment performed in the organic chemistry laboratory

was investigated through the collection of responses to questions posed on pre-laboratory

quizzes followed by in-depth interviews during which student volunteers discussed their

responses along with their experiences in the laboratory. The conceptual change theory of

learning which assumes new conceptions are understood, judged, acquired, or rejected in

a conceptual context was used as a theoretical paradigm to examine students responses to

questions posed on pre-laboratory quizzes and transcripts of the interviews with student

volunteers. Students were found to not have developed a mechanistic understanding of

 xv

how the interaction between a reaction system (reactants or starting material(s),

reagent(s), and/or solvent), experimental variables (pH, temperature, concentrations, etc),

provides a result of interest (yield, selectivity, purity, etc.) for an experiment performed

in the organic chemistry laboratory. However, students prior exposure to and

understanding of chemical concepts was found to simultaneously assist and hinder in

their development of a partial mechanistic understanding of how a reaction system

(reactants or starting material(s), reagent(s), and/or solvent), experimental variables (pH,

temperature, concentrations, etc), interact to provide a result of interest (yield, selectivity,

purity, etc.). Even though students were able to develop a partial mechanistic

understanding, they still did not understand the rationale behind chemical or physical

manipulation performed in the organic chemistry laboratory or how either may be applied

to other experiments. Therefore, experiments performed in the organic chemistry

laboratory became activities in which students gave little thought to what they were doing

resulting in little meaningful learning, unsafe practices, and an unpleasant experience that

demotivated students. To address this deficiency, instructors need to create an

environment where students are allowed to develop an understanding of the role of

reagents and reaction conditions in an experiment in order to acquire the knowledge and

skills that permits them to develop a deep mechanistic understanding of how organic

chemistry reactions are implemented in the organic chemistry laboratory.

 1

CHAPTER ONE

INTRODUCTION

1.1 Pedagogical Effectiveness of the Undergraduate Organic

Chemistry Teaching Laboratory

Since the time of Liebig (1903-1873), laboratory instruction has held a distinctive

and central role in chemistry education (Brock, 1997). In chemistry, laboratory

instruction involves a mixture of sophisticated logic and empirical observation that

develops basic skills in problem solving. Although laboratory instruction has the

potential to enhance the development of scientific concepts held by students through the

encouragement of inquiry, intellectual development, problem solving, and manipulative

skills, research has shown it rarely obtains its full potential (Hofstein & Lunetta, 1982).

Unfortunately, the chemistry teaching laboratory has too often been found to be an

environment where little meaningful learning takes place. It is also ineffectual in the

promotion of conceptual change (Gunstone & Champange, 1990), provides an unrealistic

portrayal of scientific experimentation (Merritt, Schneider, & Darlington, 1993), and does

not promote thinking among students (Raths, Wassermann, Jonas, & Rothstein, 1986).

Consequently, many educators have come to question the pedagogical value of traditional

methods of laboratory instruction that give little consideration of how to plan an

investigation or interpret experimental results (Merrit et al., 1993) and only facilitate the
 2

development of lower-order cognitive skills such as rote learning and algorithmic

problem solving (Bloom, Engelhart, Furst, Hill, & Krathwohl, 1956).

In recent years, considerable attention has focused on the pedagogical

effectiveness of the undergraduate organic chemistry laboratory. Although the organic

chemistry laboratory has long been a fundamental and vital part of the organic chemistry

curriculum, educators have come to question instructional methods that emphasize the

proper handling of chemicals, important laboratory techniques, how to follow

experimental procedures, the preparation of representative compounds, demonstration of

reactions covered in lecture, and that require students to reproduce previously published

data (Mohrig, 2004). Concern about methods of instruction that present students with a

cookbook of foolproof recipes that do not encourage thinking or learning was expressed

by Wade (1979) as follows:

Students can successfully complete the coursewithout acquiring a

fundamental understanding of the rationale behind any given manipulation
or how it might be applied in another situationsince they must simply
follow instructions to achieve the proper result (p. 825).

Almost ten years later concern about traditional methods of instruction where students are

only required to blindly follow procedures with little thought about what they are doing

was reiterated by (Pickering, 1988):

Organic labs have degenerated into cookingthere is some sort of

cosmic futility in most organic labs. Make a white powder, prove it
is what you expect, donate it to chemical waste, again, again, and
again (p. 144).
 3

Today, debate continues over the educational value of traditional methods of instruction

that reduce the organic chemistry laboratory to a rote exercise designed to consume

minimal resources whether these be time, space, equipment, or personnel (Lagowski,

1990).

To address questions of how to best engage students, many colleges and

universities have begun to incorporate laboratory activities in nontraditional styles of

instruction such as guided inquiry (discovery), open inquiry, and problem or project

based experiments ((Deters, 2005; Leonard, 1989; Ruttledge, 1998; Shiland, 1999;

Wilson, 1987) into the chemistry laboratory curriculum. Laboratory activities in

nontraditional styles of laboratory instruction are believed to promote the development of

critical thinking skills (DeBoer, 1991; Gunstone & Champange, 1990; Merritt et al.,

1993; Raths et al., 1986), reasoning skills (Merritt et al., 1993; Tamir, 1977), literature

searching (Ruttledge, 1998), reading comprehension (Gunstone & Champange, 1990),

and teamwork (Merritt et al., 1993). Laboratory activities in nontraditional styles of

instruction are also believed to promote the development of higher-order cognitive skills

such as analysis, synthesis, and evaluation (Bloom et al., 1956).

 4

CHAPTER TWO

LITERATURE REVIEW

2.1 Introduction

The constructivist theory of knowledge asserts that knowledge cannot be directly

transferred from one individual to another (Bodner, 1986).. Rather, the learner actively

constructs knowledge through his or her interaction with the environment. Within this

theory of knowledge, the environment is operationally defined as those external

influences with which the learner interacts during the learning process (White & Tisher,

1986). Hence the constructivist theory of knowledge implies that when the education of

an individual is considered, the nature of the environment is just as important as the

characteristics of the learner. Consequently, modification of the environment or the

external influences that interact with the learner could potentially lead to different

learning outcomes. In the organic chemistry laboratory, the learning environment may be

most readily modified through the use of different styles of laboratory instruction

2.2 Styles of Laboratory Instruction

Four distinct styles of laboratory instruction have been identified: expository,

guided inquiry or discovery, open inquiry, and problem or project based (Domin, 1999b).

Each of the four styles of laboratory instruction may be differentiated from one another
 5

by three descriptors: outcome, approach, and procedure (Table 2.1). Each of the three

descriptors exists as a dichotomy. For example, the outcome of a laboratory activity may

be predetermined or undetermined, its approach may be either deductive or inductive, and

the procedure may be either provided by the instructor or student generated.

Table 2.1.Styles of Laboratory Instruction

Style Procedure Approach Outcome

Expository Given Deductive Predetermined

Guided inquiry Given Inductive Predetermined
Open inquiry Student Generated Inductive Undetermined
Problem-based Student Generated Deductive Undetermined

Whether the outcome of a laboratory activity is predetermined or undetermined

depends primarily on the style of laboratory instruction. Activities in the expository and

guided inquiry or discovery styles of laboratory instruction typically have predetermined

outcomes. In the expository style of laboratory instruction, the outcome of a laboratory

activity is known to both the student and instructor whereas the outcomes of laboratory

activities in the guided inquiry or discovery style of laboratory instruction have outcomes

known only to the instructor. In contrast, laboratory activities in the open inquiry and

problem or project styles of laboratory instruction usually have undetermined outcomes

that are known neither to the instructor nor student.

Laboratory activities may employ either a deductive or inductive approach

depending upon the style of laboratory instruction. Laboratory activities in the

 6

expository and problem or project based styles of laboratory instruction typically employ

a deductive approach where students are required to apply a general principle in order to

understand a specific phenomenon. In contrast, laboratory activities in the guided inquiry

or discovery and open inquiry styles of laboratory instruction typically utilize an

inductive approach where students are required to derive a general principle through

observation of a particular phenomenon.

The procedure for a laboratory activity may be either provided to the student

through an external source such as a laboratory manual or textbook, or developed by the

students themselves. Laboratory activities in the expository and guided inquiry or

discovery styles of laboratory instruction typically provide students with a prewritten

procedure. However, the procedure provided in expository and guided inquiry or

discovery styles of laboratory instruction have very different styles of content.

Laboratory activities in both the open inquiry and problem-based styles of laboratory

instruction typically require students to create and develop their own procedures.

2.2.1 Expository Style of Laboratory Instruction

Because the expository style of laboratory instruction (also known as the

verification style) has been the traditional style of instruction in the organic chemistry

teaching laboratory, it has also been the most criticized. In the expository style of

laboratory instruction, the instructor identifies the topic of investigation, provides

connections to previous work, and directs the activities of students. Students read and

implement instructions that are written in a laboratory textbook, manual, or are provided
 7

by their instructor (Tamir, 1977). In either case, students follow unambiguous

procedures that are carefully prepared so a predetermined outcome known to both the

instructor and students is obtained.

The dominate characteristic of activities in the expository style of laboratory

instruction is their cookbook nature in which students are provided with little or no

instruction on how the experiment was planned or how results are interpreted and

assigned meaning. As noted by Tobin (1987) students are usually required to follow a

recipe in order to arrive at a predetermined conclusion. Data and results obtained by

students are used only for comparison to expected results. As noted by Pickering (1987)

never are the students forced to reconcile results or are confronted with a challenge to

what is naively predictable. As a result, activities in the expository style of laboratory

instruction have been criticized for not emphasizing thinking skills (Raths et al., 1986),

not being effectual for conceptual change (Gunstone & Champange, 1990), and providing

an unrealistic portrayal of scientific experimentation (Merritt et al., 1993).

Because the intellectual decision making that characterizes laboratory research is

already performed for the student, the cognitive demand of laboratory activities in the

expository style of laboratory instruction tends to be low not allowing for the

development of students scientific thinking skills (Tobin, 1987). Laboratory activities in

the expository style of instruction, however, are believed to develop students

observational skills, their ability to use laboratory equipment, their manual dexterity, and

the accuracy and precision of chemical measurements (Montes & Sanabria-Rios, 2010).

When engaged in activities in the expository style of instruction, students spend

the majority of their time assessing whether the correct results are being obtained rather
 8

than thinking about how to organize and plan the experiment (Stewart, 1988). Students

also do not spend enough time thinking about the scientific principles being applied in the

experiment. Consequently, the deep processing that allows the learner to integrate new

experiences with prior knowledge is precluded. Therefore, students do not establish a

context for why the experiment is being performed that determines the relevance of the

experiment to the student (Novak & Gowin, 1984). As a result, the experience is not

integrated with previous knowledge and little if any meaningful learning takes place.

Furthermore, laboratory activities in the expository style of laboratory instruction

typically stress lower-order cognitive skills such as rote learning and algorithmic problem

solving rather than requiring student to operate at higher cognitive levels (Domin, 1999a)

Despite both its benefits and its limitations, the expository style of laboratory

instruction has been extensively used in the organic chemistry laboratory. The

widespread use of the expository style of instruction has allowed laboratory activities for

the organic chemistry teaching laboratory to evolve so that: a large number of students

may perform the experiment simultaneously, involvement of the instructor is kept to a

minimum, costs are minimized, and completion of the entire procedure maybe

accomplished in a two to three hour time span (Lagowski, 1990).

2.2.2 Guided Inquiry or Discovery Style of Laboratory Instruction

The guided inquiry style of laboratory instruction, also known as the discovery

style of laboratory instruction, originated from the British science educator Henry

Armstrong who employed a heuristic method to teach chemistry in which students had to

define their own questions for investigation (DeBoer, 1991; Hodson, 1996). By limiting
 9

guidance and not providing a laboratory manual, Armstrong placed students in the role of

discoverer. Several decades later, the guided inquiry or discovery style of instruction

provided the foundation for the education reform movement of the 1960s. Bruner

(1961) believed the guided inquiry style of laboratory instruction was a necessary

condition for learning the variety of techniques of problem solving. Schwab (1962)

argued in favor of the guided inquiry or discovery style of laboratory instruction by

suggesting the traditional laboratory manual be replaced by permissive and open

materials which point to areas in which problems can be found.

Laboratory activities in the guided inquiry or discovery style of instruction also

have predetermined outcomes. Unlike the expository style of laboratory instruction,

however, the outcomes are only known by the instructor and not the students. In the

guided inquiry or discovery style of laboratory instruction, the instructor leads students as

they discover the desired outcome through directions and procedures that inform them of

what they are to do. In contrast to the expository style of laboratory instruction in which

a deductive approach is employed, the guided inquiry or discovery style of laboratory

instruction employs an inductive approach whereby, through the study of a specific

example of a phenomenon, students develop an understanding of the principles that cause

it.

Those who support the guided inquiry or discovery style of laboratory instruction

underscore the benefits of learning by direct interaction (National Academies Press,

2000). By requiring students to find out for ones self, the guided inquiry or discovery

style of laboratory instruction personalizes the experience and makes the information

obtained by students more meaningful and therefore more accessible to memory

 10

(Hodson, 1996). By requiring students to both define and solve a problem, the guided

inquiry style of laboratory instruction more closely resembles scientific methodology

(Ricci & Ditzler, 1991).

In the organic chemistry laboratory, experiments in the guided inquiry or

discovery style of laboratory instruction most commonly feature synthetic or preparative

procedures where students deduce the identity of a product, determine the regioselectivity

and/or stereoselectivity of an organic reaction, or deduce the mechanism of a reaction

based upon data obtained in the laboratory (see Appendix A, Table 2.2). Such

experiments typically require students to utilize a variety of characterization techniques

to generate data to support their conclusions.

The guided inquiry or discovery style of laboratory instruction present several

advantages over other styles of laboratory instruction used in the organic chemistry

teaching laboratory. Guided-inquiry or discovery-based laboratory activities are easy to

design and implement. Traditional verification laboratory experiments are readily

converted to guided-inquiry or discovery-based experiments through the elimination of

experimental outcome information from student laboratory manuals or handouts.

Guided-inquiry or discovery-based laboratory activities discourage the cookbook

approach because they require students to think about the results of the experiment.

However, because guided inquiry or discovery based laboratory activities provide explicit

instructions, they do not require students to think about the procedure used in the

experiment.
 11

2.2.3 Open-Inquiry Style of Laboratory Instruction

In contrast to both the expository and guided inquiry or discovery styles of

laboratory instruction, laboratory activities in the open-inquiry style of instruction have

outcomes that are not predetermined and unknown to both the instructor and the student.

Like the guided inquiry or discovery style of laboratory instruction, the open inquiry style

of laboratory instruction utilizes an inductive approach that requires students to derive a

general principle through the observation of a particular phenomenon. However, the

open inquiry style of laboratory instruction provides the student with less direction and

places more responsibility on the student for evaluation of procedural options than either

the expository and the guided inquiry or discovery styles of laboratory instruction.

Consequently, the open inquiry style of laboratory instruction encourages students to find

their own problems to solve, define the purpose of an investigation, connect the

investigation with prior work, suggest an outcome, determine a suitable procedure, and

perform the investigation. As a result, the open inquiry style of laboratory instruction is

believed to promote greater student involvement by giving the student ownership of the

investigation. In this way, laboratory activities in the open inquiry style of instruction are

believed to improve student attitudes toward science education.

Although laboratory activities in the open inquiry style of instruction provide

students with the opportunity to participate in authentic investigative processes,

laboratory activities in the open inquiry style of instruction are still not examples of

scientific inquiry with students in the role of novice scientists (Kyle, 1980). Scientific

inquiry is a pursuit of novel, broad, or applied principles where a specific outcome is not
 12

anticipated (Ausubel, 1961). In contrast, laboratory activities in the open inquiry style of

instruction involve the learning of fundamental concepts and principles in which a

specific outcome is anticipated (Hodson, 1996).

A movement towards open-inquiry-based instruction flourished in the education

reform movement of the 1960s but eventually failed to achieve its expected goals of

increased student understanding of scientific concepts, experience in the performance of

scientific investigations, and enhancement of various inquiry skills such as the creation of

a hypotheses, planning of experiments, making observations, recording measurements,

and formulating conclusions (Rubin & Tamir, 1988). Kohlberg and Gilligan suggested

that this approach failed was because the inquiry activities that were employed assumed

formal operational thought rather than attempting to develop it (Kohlberg & Gilligan,

1971). Linn (1977) claimed that inquiry activities placed too much of a burden on the

working memory of the learner who faced new subject matter concepts, unfamiliar

laboratory equipment, and new problem solving task. Analysis of content by Herron

(1971), Tamir and Lunetta (1978), and Lunetta and Tamir (1978) suggested that activities

were employed in a manner that did not provide students with opportunities to perform

and cultivate inquiry skills such as defining a research problem, formulating a

hypotheses, planning an experiment, and identification of limitations. Other problems

identified include emphasizing the scientific process to the detriment of content and

wrongly associating unguided student inquiry with scientific inquiry (Hegarty-Hazel,

1990).

Although activities in the open inquiry style of instruction have been successfully

implemented in the general chemistry teaching laboratory, activities in the open inquiry
 13

style of laboratory instruction are rarely employed in the organic chemistry teaching

laboratory and only a few examples appear in the literature (Amsterdamsky, 1998;

Browne & Blackburn, 1999; Neeland, 1999; Stoub, 2004). This disparity is attributed to

the fact that organic chemistry laboratory procedures and techniques are typically more

complex than those used in the general chemistry laboratory. In addition, to design

procedures to be used in the organic chemistry laboratory requires a level of experience

undergraduate students have not yet obtained.

2.2.4 Problem or Project Based Style of Laboratory Instruction

Although the popularity of problem or project based learning has increased during

the past couple of decades, it is not a new style of laboratory instruction. At the

beginning of the twentieth century Smith and Hall (1902) used a method of laboratory

instruction where students were encouraged to apply their understanding of a concept to

answer questions that they had previously not been taught answers to. The style of

laboratory instruction Smith and Hall (1902) used represents an approach to laboratory

instruction in which the instructor posed a question or problem to students, provided

needed materials, and guided students to a solution of the problem based upon their

conceptual understanding. It wasnt until the education reform movement of the 1950s

and 1960s however, that the problem-based style of laboratory instruction became

popular. Young (1968) implemented an approach to laboratory instruction where a

laboratory manual was not used in order to encourage independent thinking among

students through the emphasis of the creation of a testable hypothesis over the generation

of correct experimental result. Battino (1960) used a style of laboratory instruction in

 14

which students generated experimental designs through participation in prelaboratory

discussion. Similarly, Cheronis (1962) had students apply facts and principles they had

previously learned to new situations in which they were required to create and execute

experiments they created stating that:

It is unrealistic to expect a beginner before orientation and understanding

of principles to perform a so-called research or problem solving
project (p. 105).

In the problem or project based style of laboratory instruction students apply their

understanding of a concept to developing a method to obtain a solution to a problem. In

so doing, students must be able to think about what they are doing and why. As a result,

the problem becomes the instrument for both investigation and learning (Stepien,

Gallagher, & Workman, 1993). Problems provided to students are typically both

conceptually simple and open-entry in that they have an unambiguous goal with several

different paths that may provide a solution (Wright, 1996). The problem statement

provided to students also commonly lacks critical information. Consequently students

are required to redefine the problem statement in addition to developing a procedure that

will provide an answer.

Despite its increase in popularity, the problem or project based style of laboratory

instruction has received criticism. Similar to both the open inquiry and guided inquiry or

discovery styles of laboratory instruction, the problem or project based style of laboratory

instruction requires more time and puts greater demand on both the instructor and student

than the expository style of laboratory instruction (Domin, 1999a). The problem or
 15

project based style of laboratory instruction also requires students to have prior

knowledge of and experience with the concepts and principles of interest before

execution of the experiment with conceptual understanding measured by successful

completion of the problem or project based activity. In addition, although most college

and university science courses emphasize that students be successful problem solvers,

Stepien points out most problem-solving programs present students with sterile

heuristics that are commonly considered more important than the problems the

heuristic is meant to help solve (Stepien et al., 1993).

Activities in the problem or project based style of laboratory instruction are not

utilized in the organic chemistry laboratory as often as activities in the guided inquiry or

discovery style of laboratory instruction. However, activities in the problem or project

based styles of laboratory instruction are more prevalent than activities in the open

inquiry style of laboratory instruction. When implemented in the organic chemistry

teaching laboratory, activities in the problem or project based style of instruction often

require students to work on research like projects over several weeks to solve new

synthetic problems through the modification and adaptation of existing procedures. In

this way, laboratory activities in the problem or project based style of instruction often

require students to conduct research by carrying out experiments that have not been tried

previously. Unlike the guided inquiry or discovery style of laboratory instruction that

have experimental outcomes known by the instructor but not the student. Because

laboratory activities in the problem based style of laboratory instruction have outcomes

(for example will the experiment succeed or not) that are unknown to both the instructor

and the student, students are required to think about both the procedure and outcome.
 16

Use of the problem or project based style of instruction in the organic chemistry

teaching laboratory typically consists of either open-ended laboratory activities where

students are free to choose any precursor or target molecule that is of interest to them and

plan a multistep synthetic route involving the molecule of their choice (Chisholm, 1975;

Davis, Hargrove, & Hugdahl, 1999; Dobrev, 1996; Graham, Schaller, Johnson, &

Klassen, 2002; Ruttledge, 1998) or a research question assigned by the instructor that

consists of a synthetic route, target molecule, or functional group transformation that may

or may not be based upon the instructors area of research (Adrian & Hull, 2001;

Callahan, Marshall, Rothchild, & Rosmarion, 2001; DeLannoy, Mann, Maycock, &

Davidson, 1999; Gallet, 1998; Hull, 2001; Vyvyan, Pavia, Lampman, & Kriz, 2002).

Laboratory activities in the problem or project based style of laboratory

instruction have many disadvantages. In addition to being more time consuming,

experiments in the problem based style of laboratory instruction are expensive to put into

practice (Fife, 1968), result in student frustration when not successful (Davis et al., 1999;

Letcher, 1980; Silberma.R & McConnel.J, 1968), and require expensive resources such

as electronic databases and instrumentation that may not always be available (Horowitz,

2007). Student procedures also need to be screened for safety issues before being

implemented in the organic chemistry teaching laboratory. Consequently, activities in

the problem based style of laboratory instruction are not often utilized in the organic

chemistry teaching laboratory even though many educators recognize their advantages.
 17

2.3 Conclusion

Although new laboratory activities for use in the organic chemistry teaching

laboratory along with their alleged pedagogical benefits continue to be published, few

formal quantitative or qualitative investigations of student understanding in the organic

chemistry teaching laboratory have been reported that present empirical data generated

from controlled studies nor state how assessment was made other than student self-

reports. Consequently this research study sought to investigate what students understand

about the reactions they perform in the organic chemistry teaching laboratory. Through

investigation of what students understand about the reactions they perform in the organic

chemistry teaching laboratory, I hoped insights might be gained into the principles of

how and by what processes students acquire the knowledge and skills that allow them to

develop an understanding of how organic chemistry reactions are implemented in the

laboratory.
 18

CHAPTER THREE

METHODOLOGY

3.1 Introduction

For a research study to provide results that are valid and trustworthy, a rigorous

methodology needs to be employed that states and explains the process by which data,

results, and evidence is collected, organized, and analyzed. A rigorous research method

will have three clearly defined elements: a research paradigm, a sampling technique, and

a method of data collection and analysis (Bodner & Orgill, 2007). If an inappropriate

methodology or if an appropriate methodology is used poorly, the results of a study could

be misleading.

3.2 Research Paradigm

Three major research paradigms or perspectives based upon a set of assumptions,

concepts and values held by the investigator are commonly used for research in the social

and behavioral sciences. Through the first half of the twentieth century, quantitative

research, or research that relies primarily on the collection of quantitative data, was the

predominate research paradigm used in scholarly inquiry. In the 1980s, qualitative

research, or research that relies on the collection of qualitative data, became popular as an

alternative to the quantitative paradigm. Recently, mixed research that involves the
 19

mixing of the characteristics of both quantitative and qualitative research has gained

acceptance as a paradigm for scholarly inquiry (Harwell, 2011).

3.2.1 Quantitative Methodological Paradigms

Quantitative methodological paradigms allow the investigator to measure the

reaction of a large number of individuals to a limited set of questions (Patton, 2002).

Quantitative methodological paradigms therefore facilitate the comparison and

accumulation of statistical data that provide for the creation of broad and generalizable

conclusions. Some prefer quantitative research because it is based on cold, hard, and

objective data. However, validity in quantitative research depends on the careful

construction of an instrument to ensure that it measures that which it is intended to

measure and that it is administered in a standardized manner consistent with prescribed

procedures.

There are two major types of quantitative research studies: experimental and

nonexperimental (Creswell, 2012). The purpose of experimental research is to study

cause and affect relationships and is characterized by the active manipulation of an

independent or causal variable that is presumed to cause changes to occur in a dependent

or outcome variable. The strongest experimental research designs utilize the technique of

random assignment to create equivalent groups to minimize extraneous or confounding

variables that destroy the integrity of the research study because they may compete with

the independent variable in determination of the outcome.

In contrast to experimental research, nonexperimental research does not involve

the manipulation of an independent variable nor the random assignment of participants to

 20

groups. Consequently, if a relationship between two variables is found in a

nonexperimental research study, a cause and effect relationship cannot be assumed

because there are too many alternative explanations for the relationship. There are two

distinct types of nonexperimental research studies: causal-comparative and correlational

research studies. In a causal-comparative research study, a relationship between an

independent categorical variable made up of different types or categories of phenomenon

and a dependent quantitative variable that varies in degree or amount of a phenomenon

are examined. In a correlational research study the relationship between an independent

quantitative variable and a dependent quantitative variable is examined.

Quantitative methods have several disadvantages. Quantitative research methods

tend to focus on the average student and may produce erroneous conclusions if a change

benefits some students but not others (Bodner & Orgill, 2007). In addition, quantitative

research focus on things that may be measured quantitatively and are often influenced by

numerous confounding qualitative variables that make it difficult to derive the effect one

is looking for. Furthermore, although results from large samples may be statistically

significant, they may not be important. Conversely, quantitative studies of small samples

may not have statistical significance, but that does not mean that an effect is not present.

3.2.2 Qualitative Methodological Paradigms

Qualitative methods of inquiry have increased in popularity in the social and

behavioral sciences because they allow investigators to gain an in-depth understanding of

human behavior and the reasons that govern such behavior (Denzin & Lincoln, 2005)

Qualitative methods of research investigate the why and how of decision making not just
 21

the what, where, and when through the gathering of data in the form of words obtained

from in-depth, open-ended interviews or think aloud problem solving sessions; artifacts

generated during the interview process that consist of drawings, equations, calculations,

or ideas written by the participant; and field notes. In this way, qualitative research

methods produce detailed information about a smaller group of individuals but provide

greater depth of understanding. However, because responses are often variable in

content, not systematic, nor standardized, analysis is often difficult producing

conclusions that are propositions or assertion rather than broad generalizable claims.

Qualitative research methods are more participatory and activist orientated rather

than other passive observer/research methods (Savin-Baden & Major, 2013). In

educational research, the investigator departs from assumptions of objectivity no longer

viewing the student as a lone, passive, learner. Investigators also relinquish their reliance

on simple correlational models and one-time measurements of achievement afforded by

standardized tests. Instead, the researcher may be thought of as a participant-observer

who practices self-reflexivity viewing the learner as both an individual and as a social

learner in a complex classroom environment; and toward collecting thick, ethnographic

descriptions that recognize the theory-ladenness of observation (Lesh & Kelly, 2000).

Because qualitative research methods are more participatory and activist orientated,

validity in qualitative research depends upon the skill, competence, and rigor of the

investigator conducting the fieldwork.

Within the field of science education, systematic research is influenced by several

features such as the presence of numerous disciplinary perspectives, the diversity of

individuals involved (students, teachers, and administrators), the inconsistency of

 22

instruction, curriculum, and authority across educational settings, and the different

learning styles and abilities of students from diverse backgrounds (Hatch, 2002). These

characteristics impact both the nature of research and the conceptions held by

participants. Consequently, a qualitative methodology will be used to attempt to bring

these features together through the incorporation of theories with research data.

Two fundamental elements of a qualitative research study are a set of guiding

research questions that the study will attempt to answer and a theoretical paradigm upon

which the study may be constructed (Bodner, 2004). Usually the first element to be

developed in the design of a qualitative research study is the drafting of a set of guiding

research questions.

3.2.2.1 Guiding Research Question

The fundamental purpose of a set of guiding research questions is to state the

questions the researcher wishes to find answers too (Bodner, 2004). A set of guiding

research questions provides the research study with direction, limits the scope of the

investigation and provides focus, provides an instrument for evaluation of progress and

completion of research, provides an initial structure for data analysis, and ties together all

elements of design. The set of research questions must be answerable within the

theoretical paradigm used in the investigation, open-ended, few in number, and stated in

straight forward language. Close-ended questions are more suited for quantitative

studies, having too many questions leads to data collection that is fragmented, and the use

of complex language may cause confusion and misinterpretation.

 23

3.2.2.1.1 Categories of Research Questions

In qualitative research, a set of research questions may be thought of as belonging

to one of four primary categories: exploratory, explanatory, descriptive, and

emancipatory (Table 3.1) depending on the purpose of the questions (Creswell, 2007).

Guiding research questions in each of the four categories share the common

characteristics of being evolving and non directional. Qualitative research questions state

the purpose of the investigation in specific terms and commonly begin with words such

as what or how instead of why and are written in the language of the theoretical

paradigm used in the investigation.

Table 3.1 Categories of Guiding Research Questions

Category Purpose of Question

Exploratory To investigate a phenomenon

Explanatory To elucidate patterns associated with a phenomenon

Descriptive To depict, portray, or illustrate a phenomenon

Emancipatory To undertake social action in regards to a phenomenon

A researcher usually has one overarching central question the study addresses that

may be divided into several sub questions. The overarching central question reflects the

intent of the study but it restricts its scope. Sub questions may be thought of as either

issue sub questions or procedural sub questions. Issue sub-questions break down the

central research question into subtopics of concern to be investigated. Procedural sub

questions communicate the steps to be taken by the research approach.

 24

3.2.2.1.2 Guiding Research Question

In this research study, the overarching central question of investigation was: What

do students understand about how the interaction between a reaction system (reactants or

starting material(s), reagent(s), and/or solvent), experimental variables (pH, temperature,

concentrations, etc), produces a result of interest (yield, selectivity, purity, etc.) in an

experiment conducted in the organic chemistry teaching laboratory?

3.2.2.2 Theoretical Paradigm

Within the discipline of qualitative inquiry, various theoretical paradigms exist

that serve several functions (Denzin & Lincoln, 2005). Primarily, a theoretical paradigm

provides the assumptions that guide the research. The theoretical paradigm assists the

researcher in the selection of appropriate questions for investigation. It also helps the

researcher choose methods of data collection appropriate for a study. Each theoretical

paradigm has limitations that affect its suitability for a particular research study.

Consequently, some theoretical perspectives are more appropriate for certain

investigations than others. A researcher doesnt necessarily have to accept all of the

assumptions of a particular perspective; however, those assumptions that are applicable to

an investigation must be specified (Bodner & Orgill, 2007). Table 3.2 summarizes

theoretical paradigms relevant to the investigation of student understanding in the organic

chemistry laboratory.
 25

Table 3.2 Theoretical Paradigms

Issue
Theoretical
Paradigm
Ontology Epistemology Methodology

Positivist Objective reality There is one Discourse structured

exists that may be knowable truth or & transparent -
found reality reflects reality

Post Positivist Objective reality Truth consists of Discourse is

only imperfectly nonfalsified constitutive of reality
apprehensible hypotheses

Constructivist Reality is subjective Many truths exist Discourse is dialogic

and constructed and creates reality

Conceptual Reality is based on Conceptions are Discourse is dialogic

Change experiences and understood, judged, and promotes change
perceptions, culture, acquired, or rejected at the core of a
and language in a conceptual system of concepts
context

3.2.2.2.1 Positivism

Historically, scientific research has been dominated by a positivist paradigm that

assumes the infallibility of scientific knowledge to describe a knowable external reality

(Denzin & Lincoln, 1994). In a positivist paradigm, knowledge is assumed to consist of

verified hypotheses that may be thought of as established facts or laws. Consequently the

purpose or aim of inquiry in a positivist paradigm is that of explanation to enable the

prediction and control of phenomena whether physical or human. Knowledge is believed

to accumulate through a process of accretion where each probable fact adds to a growing

edifice of knowledge that allows generalizations to be made with confidence to a

population or setting. Facts are gained through methods that allow careful measurement,
 26

manipulation, and control that are dominated by a deductive model constructed upon

empirically verified propositional hypotheses. Experiments, quasiexperiments,

correlation studies, and surveys are used along with sophisticated sampling and statistical

techniques. Quality of inquiry is determined by internal validity (correspondence of

findings with reality), external validity (generalizability), reliability (in terms of stability),

and objectivity (researcher neither influences nor is influenced by subject). Values are

thought of as confounding variables to an objective reality and specifically excluded.

Ethics are considered to be extrinsic to the inquiry process and monitored by external

mechanisms such as internal review boards and codes of professional conduct. The voice

of the researcher is that of the disinterested scientist who informs others who

independently use the information.

Activities performed by students in the organic chemistry teaching laboratory are

built upon substantive technical theory, techniques of procedural manipulation, along

with qualitative and quantitative methods of characterization that are assumed to define a

knowable external reality. However, the positivists paradigm upon which activities in

the organic chemistry teaching laboratory are based is not compatible with qualitative

methods of research.

3.2.2.2.2 Post Positivism

Post positivism also accepts that an external reality exists. However, the

postpositive paradigm acknowledges that because of the limitations of human intellectual

processes, this external reality can only be imperfectly apprehended (Hatch, 2002).

Consequently, in a post-positivist paradigm, knowledge is assumed to consist of

 27

nonfalsified hypotheses that are probably true rather than verified facts or laws. Like

investigators following a positivist investigators paradigm, post positivist researchers

seek to maintain an objective position in relation to the phenomena of study. However,

because post positivist researchers see themselves as data collection instruments,

disciplined and rigorous research techniques are followed to ensure empirical data drives

findings and not the researchers impressions. Qualitative inquiry within a postpositive

paradigm is performed in natural settings to collect situational information to help

discover the meanings and purposes participants ascribe to their actions.

3.2.2.2.3 Constructivism

As a theoretical paradigm for qualitative inquiry, the principle assumption of

constructivism is that the world created by human perception may be different from the

physical, natural world (Guba and Lincoln, 1990). Human beings have the ability to

interpret and construct their own unique perception of reality. Therefore, the world

created by human perception is not an objective representation of physical reality, but is

constructed and shaped by cultural and linguistic constraints (Patton, 2002).

Consequently, Humans do not have access to a singular, stable, and fully knowledgeable

external reality. All of our understandings are contextually embedded and necessarily

limited (Neimeyer, 1993). Although the worlds created by human perception are a

subjective representation of reality, it is important to remember that constructivism as a

theoretically paradigm is concerned only with how individuals construct knowledge

about reality, not with reality itself (Shadish, 1995). Because of these considerations

truth is not believed to arise from an interaction with an objective realisty, but is a result
 28

of consensus amongst those who construct what is considered truth (Guba and Lincoln,

1989).

Although Socrates was the first to propose the idea that knowledge is constructed

by the learner (Nolan, 1997), the use of constructivism as a theoretic paradigm for

research in education is generally thought to have originated from the pioneering work of

Piaget on the cognitive development of children (Fosnot & Perry, 2005). From his

research Piaget proposed that: (1) learning occurs in stages; (2) knowledge is organized

into cognitive structures; (3) learning occurs through the dynamic interaction of an

individual and the environment; (4) knowledge is continually constructed and

reconstructed based upon prior and novel experiences (Brooks & Brooks, 1993). Piaget

also asserted that learning occurs through the interaction of learners with their

environment by which knowledge is continuously constructed and reconstructed through

the processes of assimilation and accommodation. Assimilation occurs when new

knowledge is incorporated into an individuals existing cognitive structures. In contrast,

accommodation occurs when new knowledge does not fit into an individuals existing

cognitive structure. In this case, an individual may either ignore the lack of fit and

preserve the original cognitive structure, make each cognitive structure hold for separate,

specific cases, or construct a new encompassing cognitive structure that explains and

resolves the contradictions.

In contrast to Piagets emphasis on the stages of learning, Vygotsky asserted that

language and social interactions had a large impact on what and how a learner

constructed knowledge (Vygotsky, 1986). Vygotsky hypothesized that the learner was

cognitively limited to a zone of proximal development that was bounded on one side by
 29

skills and knowledge that the learner already possessed and on the other by skills and

knowledge that the learner had to obtain with outside help. An experience that only

requires the skills or knowledge the learner already possesses demands little cognitive

effort from the individual whereas an experience that requires skills or knowledge the

learner lacks may be beyond the cognitive ability learner.

Constructivism was first used as a theoretical paradigm for research in science

education by Tobin and coworkers who investigated the teaching methods of an

exemplary high school science teacher through the lens of radical constructivism

proposed by von Glasersfled (Tobin, et. al, 1988). As a theoretical paradigm for

research in science education, constructivism provides a way of thinking about how

individuals interact with the world around them and how they make sense of that world.

Constructivism assumes that a person does not discover preexisting knowledge. Rather,

individuals actively construct knowledge by inventing concepts and models to make

sense of their experiences and continually test and modify these constructions in the light

of new experiences (Bodner, 2006).

A number of different forms of constructivism for use as a theoretical paradigm in

education research exist, each with a different emphasis on individual verses social

learning and objectivist verses relativist perspectives on the nature of science. Several of

the most common forms are presented in Table 3.3 along with the name of the person

with whom the form is associated (Geelan, 1997).

 30

Table 3.3 Forms of Constructivism

Form Description Proponent

Personal Knowledge is individual and adaptive Kelly (1955)

Constructivism Rather than objective and exists within
the cognizing individual

Radical Knowledge is actively constructed within Von Glaserfeld

Constructivism the individuals mind for the purpose of (1989, 1993)
enhancing survival by making experience
meaningful.

Social Emphasizes the social effects of the desire Solomon (1987)

Constructivism for consensus and peer approval in the Gergen (1995)
modification of scientific ideas.

Critical Suggests the processes of teaching and Taylor (1994)

Constructivism learning are socially constructed and
socially developed repressed myths may
lead to failure of constructivism in the
classroom

Contextual Recognizes culture as a central force in the Cobern (1993)

Constructivism development and organization of student
ideas

3.2.2.2.4 Conceptual Change Research

The central claim of the conceptual change view of learning asserts that new

conceptions are understood, judged, acquired, or rejected by a learner in a conceptual

context (Posner et al., 1982). Learning is considered to be a process of inquiry where the

learner relates what they encounter to existing conceptual structures deeply rooted in their

experiences and perceptions, cultural values and ideas, and language factors.

Consequently new conceptions are not merely added to existing conceptions, but interact

with them sometimes requiring alteration of one or both. However, because the learners
 31

pre-instructional understandings are sufficient to interpret and guide they may

significantly hinder learning in the context of the science classroom. Therefore views

that emphasize conceptual change assume students ability to learn and what students

learn depend on the conceptions they bring to the experience. Thus, learning and

understanding may only be appreciated by explaining how these conceptual resources

function for the learner.

Conceptual change research focuses on two important questions postulated by the

conceptual change view of learning: how do learners incorporate new conceptions into

current cognitive structures and how do learners replace conceptions that have become

dysfunctional with new conceptions (Strike, 1992). However, conceptual change

research does not focus on the insurmountable task of altering all of the possible

misconceptions that could be held by learners. Rather, conceptual change researchers

focus their efforts on conceptions that are at the core of a system of concepts analogous

to Piagets (1952) accommodation that involves the replacement or reorganization of

central concepts or Kuhns (1970) paradigm shift that involves the replacement of

concepts that are organizing in nature.

3.2.3 Mixed Methodological Paradigms

One difficult with the distinction between quantitative and qualitative research

paradigms is that it exemplifies an either or dichotomy. Research is either quantitative or

qualitative. However, quantitative and qualitative research paradigms are the ideal ends

of a continuum along which actual research may take place. There are several kinds of
 32

both quantitative and qualitative research that may be combined to afford a mixed

method paradigm.

Mixed method approaches to scholarly inquiry employ characteristics of both

quantitative and qualitative research paradigms (Tashakkori and Teddlie, 2003). Two

major types of mixed methods research may be distinguished: mixed method versus

mixed model research. In mixed method research the researcher uses the qualitative

research paradigm for one phase of a research study and the quantitative research

paradigm for another phase of the study. Mixed method research may be compared to

conducting two mini-studies within one overall research study. Mixed model research

uses both qualitative and quantitative research approaches within the same stage of a

study or across two stages of the research process.

Supporters of mixed method approaches to research claim quantitative and

qualitative research methods, procedures, and paradigm characteristics may be combined

in a way that the resulting mixture has complementary strengths and non overlapping

weaknesses (Harwell, 2011). In addition, if the different approaches used to examine the

same phenomenon provide the same result, corroboration occurs that gives stronger

evidence for a result. Other reasons for conducting a mixed research study include to

expand a set of results, complement on set of results with another, or to discover a result

that may have been missed if only a qualitative or quantitative method had been

employed.
 33

3.3 Sampling Technique

Whether a quantitative, qualitative, or mixed methods research paradigm is used

in an inquiry, the sampling technique employed must be consistent with the aims and

assumptions inherent in the research paradigm used (Patton, 2002). A quantitative

paradigm is typically used to achieve a wide breadth of understanding. Therefore,

quantitative sampling techniques emphasizing the generalizability of results that are

representative of the population from which a sample is taken are typically employed. In

contrast, a qualitative paradigm is typically used to achieve depth of understanding.

Consequently, qualitative sampling techniques emphasizing saturation that provide a

comprehensive understanding through sampling until no new information is acquired are

typically employed (Miles, 1994).

Each research paradigm has different standards for determining the number of

participants required to reach the goals of the inquiry. Quantitative research paradigms

use established statistical methods to determine the number of participants required to

avoid the incorrect rejection of a true hypothesis and the failure to reject a false null

hypothesis. Qualitative research paradigms use precedents for determining the number of

participants based upon the methodological approach (three to six participants

interviewed multiple times for a phenomenological study verses 20-30 participants

interviewed once or twice in a grounded theory study), as well as the level of detail, and

level of homogeneity (Guest et al. 2006: Morse and Niehaus, 2009; Padgett, 2008).

In contrast to probabilistic or random sampling used in quantitative research to

guarantee the generalizability of results by minimizing bias in sample selection and the

potential influence of known and unknown confounders, purposeful sampling is

 34

frequently used in qualitative research to identify and select the most information rich

cases for the most efficient use of limited resources (Patton, 2002). Purposeful sampling

involves the recruitment of individuals or groups of individuals that are especially

knowledgeable about or experienced with a particular phenomenon and able to provide

the greatest insights (Creswell, 2011). Other important criteria for the identification and

selection of information rich cases include availability and willingness to participate, and

the ability to communicate in an articulated, expressive, and reflective manner (Bernard,

20002; Spradley, 1979).

3.3.1 Research Sample

The sample used in this research study consisted of all twenty one students

enrolled in a second semester organic chemistry laboratory course offered by the

Department of Chemistry of a large Midwestern research university for students enrolled

in the Universitys College of Engineering who were pursuing an undergraduate degree

in chemical engineering. Information about the students background was obtained

through a questionnaire administered the first day of class. Nineteen of the 21

participants declared chemical engineering as their academic major, while two of the

participants declared chemistry as their academic major. Thirteen of the participants

indicated their semester classification as sophomores, three as juniors, and five as seniors.

Twelve of the participants indicated they had professional experience as part of their

involvement in the professional practice program in the school of engineering. Two of

the participants stated they had prior work experience in a research laboratory. Twenty

of the participants had previously completed their first semester of the two semester
 35

organic chemistry lecture and laboratory course sequence offered by the Universitys

Department of Chemistry for students enrolled in the Universitys College of Engineering

who were pursuing an undergraduate degree in chemical engineering. One of the

participants had completed their first-semester organic chemistry lecture and laboratory

courses at a University other than the University where the investigation was conducted.

The questionnaire revealed students enrolled in the course had a diverse

background in general chemistry. Five of the participants indicated they had completed a

two-semester general chemistry course sequence offered by the Universitys Department

of Chemistry for students enrolled in the Universitys College of Engineering. Seven of

the participants indicated they had completed a two-semester general chemistry course

sequence required of students who declared science or engineering as their academic

majors and were not enrolled in the two-semester general chemistry sequence offered by

the Department of Chemistry for students enrolled in the Universitys College of

Engineering. Two of the participants indicated they had completed a one-semester

general chemistry course open to students who had been admitted to the honors program

in science or engineering, or a score of at least 70% on the general chemistry test out

exam. Four of the participants indicated they had completed general chemistry but did

not specify what courses they completed; one participant indicated they had completed

general chemistry at another university; and two participants did not respond to the

question.
 36

3.3.2 Interview Participants

Although all of the 21 students who were enrolled in the second semester organic

chemistry laboratory course during the summer of 2011 participated in the research

study, only two of the students enrolled in the course volunteered to participate in weekly

interviews with the researcher in addition to their participation in other aspects of the

study. Both students were chemical engineering majors who participated in the

professional practice program in the College of Engineering and had gained industrial

experience as chemical engineers prior to enrolling in the second semester organic

chemistry laboratory course.

3.3.2.1 Buffy

Buffy was a chemical engineering student in the professional practice program in

the College of Engineering at the university where the investigation was conducted. She

had just completed her third year of study and was to begin her fourth year in the fall

semester. In our interviews, Buffy indicated she had completed the two-semester general

chemistry course sequence intended for students enrolled in the Universitys College of

Engineering her Freshman year. She also indicated she had completed the first semester

of the two organic chemistry lecture and laboratory courses intended for students enrolled

in the Universitys College of Engineering who were pursuing an undergraduate degree

in chemical engineering the previous fall semester.

Originally from the Chicago suburbs, Buffy had taken honors chemistry her

freshman year of high school and advanced placement chemistry her junior year of high

school. Buffy became interested in chemical engineering because she liked chemistry in
 37

high school and believed engineering pays well. During alternate semesters when not

attending classes at the university where the study was conducted, Buffy is employed by

a leading manufacturer of printing inks and pigments as a Project Engineer. Buffy stated

that where she works, chemical reactions were not performed, just the mixing of

materials where I work we dont do reactions, its just mixing. Although Buffy stated

she did some pilot plant work her first term at the company, she had been involved in the

construction of plant additions the past two terms.

My second and third term Iwe have a big team project where
all of us are involved in building two separate plant additions so
Ive been ordering piping instruments and doing a lot of project
management work and working in automation for the plant. I
have been all over the place in terms of building plants.

3.3.2.2 Jody

Jody was also a chemical engineering student in the professional practice program

in the College of Engineering at the University where the investigation was conducted.

He had just completed his second year of study and was to begin his third year in the fall.

Originally from Normal Illinois, Jody had taken honors chemistry his sophomore year of

high school and advanced placement chemistry his junior year of high school. Because

Jody scored a five on the AP chemistry exam, he received credit for the two-semester

general chemistry course sequence intended for students enrolled in the Universitys

College of Engineering. Consequently he elected to enroll in the one-semester general

chemistry course open to students who had been admitted to the honors program in

science or engineering the fall semester of his freshman year. Jody then enrolled in the
 38

first semester of the two organic chemistry lecture and laboratory courses intended for

students enrolled in the Universitys College of Engineering who were pursuing an

undergraduate degree in chemical engineering the fall semester of his second year. In our

interviews Jody discussed how having semesters in which he did not take chemistry in

between semesters he was enrolled in chemistry courses impacted his learning.

Its kind of been disjointedwhich is always interestingyou come

back and you (think) what was thatbut that will happen later on
too. (laughs)

When asked how he became interested in chemical engineering, Jody stated he knew he

wanted to do something that involved mathematics. He looked at actuarial science and

mechanical engineering but decided upon chemical engineering because he had really

enjoyed his previous chemistry classes.

During alternate semesters when Jody was not attending classes at Purdue

University he was employed by a provider of specialty chemicals for the transportation,

industrial, and consumer markets. In our interviews Jody indicated that his first term at

the corporation where he was employed focused on operations during which time he

learned about the various reactors, how to put a nitrogen purge on them, and how

everything worked. In his most recent term, Jody worked as a project engineer on

capital process improvement projects such as updating control systems and

instrumentation. Jody seemed to be especially proud to have been responsible for the

design and implementation of a special seal system for agitators on the plants main
 39

reactors. In his interviews Jody stated he hoped to become involved in process research

and development activities in the companys pilot plant in the future.

3.4 Data Collection

This investigation followed the research tradition of probing students conceptions

(also referred to as preconceptions, prior conceptions, and misconceptions) as a necessary

starting point for the design of effective instruction (Driver, Guesne, & Tiberghien, 1985;

Driver, Leach, Miller, & Scott, 1996; Libarkin & Kurdziel, 2002). This line of research

was extended in this study, to examining students experiences in the organic chemistry

laboratory rather than just their understanding of science concepts. In this sense, the

investigation probes student understanding of how organic chemistry reactions are

actually implemented in the laboratory as opposed to simply probing their understanding

of organic chemistry.

3.4.1 Methods of Data Collection

Two methods of data collection were used in this investigation. The first method

consisted of obtaining the responses provided by all twenty one students enrolled in the

course to questions posed on pre-lab quizzes given at the beginning of each laboratory

period in which a new experiment was begun. Each quiz consisted of four to six

questions and was administered in the natural setting of the organic chemistry laboratory

with the teaching assistants and researcher present. Students were given approximately

ten to fifteen minutes to complete the quiz. The quizzes were administered to the entire

class to gather the range of conceptions held by individual members of the class. To gain
 40

deeper insights into student understanding of activities performed in the organic

chemistry teaching laboratory, weekly semi-structured interviews were conducted with

volunteer participants during which time students responses to quizzes were discussed

along with participants experiences implementing the various reactions in the laboratory.

Interviews were conducted in the researchers office and lasted between 30 and 60

minutes. Interviews were transcribed verbatim by the researcher.

3.4.2 Use of Open Ended Questions

Open-ended questions were used in both the pre-laboratory quizzes and during the

interviews because the researcher did not want to prejudge or constrain the nature of the

understandings and misunderstandings that could emerge from the study. Because the

researcher also did not want to be bound to pre-established constructs of pre-designed

and structured questions that could potentially preclude context rich phenomena

emerging from the data, an inductive approach was used and questions were not pilot

tested (Miles, 1994). The questions asked were general enough so as not to be leading in

order that key themes could emerge naturalistically from the data rather than forcing the

data into a predetermined structure.

To keep in the research tradition of probing students prior or alternative

conceptions (Driver et al., 1985) broad open-ended questions were intentionally used to

allow whatever was in the forefront of students thoughts to emerge in their own words.

Although the use of broad open-ended questions has the potential to reveal concepts held

by students, the technique is limited in that students may not completely or fully disclose

their conceptions. Consequently, the reader should bear in mind that the presence of a
 41

conception in a students response indicates students are conscious of the conception,

however absence of the conception does not necessarily indicated students were not

conscious of the conception.

3.5 Data Analysis

As a systematic search for meaning, data analysis represents a method by which

qualitative data may be processed in order that what has been learned may be

communicated to others (Hatch, 2002). Data analysis consists of the organization of

information so that the investigator is able to see patterns, themes, relationships, develop

explanations, and make interpretations, and generate theories. Often, data analysis

involves synthesis, evaluation, interpretation, categorization, hypothesizing, comparison,

and pattern finding. Making sense of qualitative data requires mind work where the

investigator engages their own intelligence, creativity, and reflexivity to provide meaning

to the data. Data analysis may be thought of as asking questions of the data. The types

of questions asked are related to the set of paradigmatic assumptions of the study with

different paradigms leading to different analysis strategies.

3.5.1 Inductive Approach to Data Analysis

An inductive approach to data analysis that involved a search of the data for

connections among specific elements for patterns of meaning to generate understanding

and allow general statements to be made was used in this study (Bryman & Burgess,

1994: Dey, 1993; Potter, 1996). The use of an inductive approach to data analysis is

compatible with many types of qualitative data analysis especially ground theory (Strauss
 42

& Corbin, 1998) and consistent with general patterns of qualitative analysis discussed by

other authors (Miles & Huberman, 1994, Pope et al., 2000, Punch, 1998). Inductive

analysis begins by the inspection of particularities within the data followed by the

discovery of relationships across individual observations and ending with the

establishment of relationships expressed as general explanatory assertions. In this way

particular pieces of evidence are pulled together into a meaningful whole. This allows

research findings to emerge from frequent, dominant, or significant themes present in the

raw data without the constraints imposed by structured methodologies.

3.5.2 Thematic Content Analysis

Thematic content analysis was used to examine student responses to the open

ended questions posed on pre-laboratory quizzes and in the interviews (Chi, 1997;

Libarkin & Kurdziel, 2002; Miles & Huberman, 1994). In thematic content analysis,

themes are extracted from the text of participant responses rather than assumed without

reference to experimental data. Themes that emerge naturally from the data are linked or

reorganized to develop a dominate structure. In this investigation, the researcher

examined the keywords and phrases that students used discuss what they understand

about the reactions performed in the organic chemistry teaching laboratory. Responses

provided by students that discussed the same mechanistic concepts were grouped together

under a core theme. Student responses were then evaluated in terms of the levels of

mechanistic understanding demonstrated.

 43

3.6 Validity

Traditionally, validity in qualitative research has meant establishing the extent to

which researchers assertions about knowledge are consistent with reality (or participants

construct of reality). Two different approaches to the question of validity have emerged

within qualitative research literature; transactional validity and transformational validity

(Cho & Trent, 2006). Transactional validity may be thought of as an interactive process

between the investigator, the subject, and data with the purpose of obtaining a high level

of accuracy and agreement through the re-examination of facts, feelings, experiences, and

beliefs amassed and interpreted. In contrast, transformational validity in qualitative

research may be defined as an emancipative and progressive method that leads toward

social change through the research process itself.

3.6.1 Transactional Validity

Transactional approached to validity assume that credibility may be increased

through the use of certain techniques, methods, and/or strategies during inquiry.

Consequently, validity consists of methods and techniques by which misunderstandings

may be corrected. Two techniques crucial for establishing credibility in transactional

approaches are triangulation and member checking (Cho & Trent, 2006). Triangulation

involves trying to verify facts through the use of multiple data sources to generate

evidence in support of key claims. In this investigation triangulation was achieved

through the use of pre-laboratory quizzes, observation of laboratory experiences, and the

collection of documents such as laboratory notebooks and spectral data. Member

checking consists of the reassurance of the credibility of the constructions provided by

 44

participants. This is accomplished through the play back of collected data to

participants to check for perceived accuracy. In this investigation member checking was

accomplished through participant interviews in which participants responses to pre-

laboratory quizzes, observed laboratory experiences and documents were reviewed and

discussed.

3.8 Conclusion

To gain an in-depth understanding of how students create meaning of their

experiences performing experiments in the organic chemistry teaching laboratory, a

qualitative study was performed through the collection of responses provided by students

to open ended questions on pre-laboratory quizzes. Responses provided by students and

their experiences executing the experiments were further explored during semi-structured

interviews. Thematic content analysis was used to extract key words and phrases that

demonstrated the level of understanding by the student.. Through the use of this

methodology, I hoped to gain insight into how students develop their conceptual

understanding of how reactions are executed in the organic chemistry teaching

laboratory.
 45

CHAPTER FOUR

THE RESEARCH SETTING

4.1 Introduction

Qualitative research focuses on the interpretation of phenomena in its natural

setting to make sense of the meaning individuals bring to those settings (Denzin and

Lincoln, 1994). It attempts to understand the unique interactions that occur in a

particular situation (Patton, 2002). The purpose of this understanding is not to predict

what may occur, but rather to understand in depth the characteristics of the situation and

the meaning brought by participants. Consequently, qualitative research studies

phenomena in its natural settings in an effort to discover its meanings to those who are

being researched rather than that of the researcher (Pope and Mays, 1995). Because the

goal of this research study was to investigate students understanding of how the

interaction between a reaction system (reactants or starting material(s), reagent(s), and/or

solvent), experimental variables (pH, temperature, concentrations, etc), provides a result

of interest (yield, selectivity, purity, etc.) in an experiment performed in the organic

chemistry laboratory, the investigation was conducted in the natural setting of the second

semester of the two organic chemistry laboratory course intended for students enrolled in

the Universitys College of Engineering who were pursuing an undergraduate degree in

chemical engineering at a large Midwestern research university

 46

4.2 Description of the Second Semester Organic

Chemistry Laboratory Course

The Universitys course catalogue describes the second-semester organic

chemistry laboratory course as a continuation of the first-semester organic chemistry

laboratory course such that experiments are designed to illustrate principles discussed in

the corresponding organic chemistry lecture course. The course catalogue lists six

learning objectives for the course that presume students will be able to: (1) use theory to

understand and predict experimental observations; (2) demonstrate and understanding of

the physical properties and a molecular understanding of chemical reactivity and

materials; (3) document scientific information and experimental data and write scientific

reports, with graphical presentation of data; (4) plan and perform chemical

transformations; (5) recognize and use chemical instrumentation and spectroscopy; and

(6) identify and handle hazardous materials.

When the second-semester organic chemistry laboratory course is offered during

the summer, students are required to toil in the laboratory twice a week for eight weeks

so that the an equivalent amount of material is covered as when the course is offered

during the Fall or Spring semesters. Each laboratory session was two hours and fifty

minutes in length. Students performed eight experiments over the course of the semester.

Five of the eight experiments were in the traditional expository style of laboratory

instruction and included: the Williamson synthesis of ethers, preparation of methyl p-

ethylphenyl ether; photochemical isomerization of an alkene, cis-1,2-dibenzoylethylene;

Diels Alder reaction, preparation of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride;

microscale Suzuki cross coupling of phenylboronic acid with 4-iodophenol in aqueous

 47

media; and evaluation of L-proline as a catalyst for an asymmetric aldol reaction. Two of

the eight experiments were in the guided inquiry or discovery style of laboratory

instruction: proton exchange and integral evaluation; and Friedel Crafts acylation of 2-

chlorotoluene and subsequent haloform reaction. One of the eight experiments was in the

project or problem-based style of laboratory instruction: synthesis of substituted

chalcones. Students were given a comprehensive final exam at the end of the semester

Each laboratory session was led by two teaching assistants who were graduate

students in the Department of Chemistry of Purdue University. Both teaching assistants

were engaged in research within the organic chemistry division. The graduate teaching

assistants were responsible for providing a ten- to fifteen- minute pre-laboratory lecture

and guiding the day to day activities of undergraduate students. The teaching assistants

also graded all pre-laboratory quizzes and final laboratory reports. Undergraduate

students worked in pairs with the same partner throughout the semester. Students

decided among themselves in regards to the distribution of work.

4.3 Description of Classroom Environment

The classroom environment consisted of a room with six rows of laboratory

benches that could accommodate four students each, for a maximum capacity of 24

students. Each student was provided with a microscale glassware kit to use in the

execution of laboratory activities. Instrumentation available included four analytical

balances, eight Meltemp devices to determine melting point and boiling point data, and

two attenuated total reflectance infrared spectrometers. A 300 MHz Varian nuclear

magnetic resonance spectrometer maintained by the Universitys Interdepartmental NMR

 48

facility was made available for the collection of both 1H and 13C NMR spectra. Various

print sources of information were available to students within the classroom such as a

Merck Index and Aldrich catalogue along with electronic media through the department

of chemistry library webpage.

4.4 Experiments Investigated

Students understanding of how the interaction between a reaction system

(reactants or starting material(s), reagent(s), and/or solvent), experimental variables (pH,

temperature, concentrations, etc), provides a result of interest (yield, selectivity, purity,

etc.) in an experiment was investigated for four of the experiments performed during the

summer 2011 session of the second semester organic chemistry laboratory course: the

Williamson synthesis of ethers; preparation of methyl p-ethylphenyl ether; the Diels-

Alder preparation of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride; the Friedel-

Crafts acylation of 2-chlorotoluene and subsequent Haloform reaction to prepare 2-

chloro-3-methyl benzoic acid; and the evaluation of L-proline as a catalyst for an

asymmetric aldol reaction to prepare a chiral -hydroxycarbonyl and subsequent Mosher

analysis to quantify the enantiomer enrichment of the product.

Only the results obtained for the experiments in the traditional expository style of

laboratory instruction; the Williamson synthesis of methyl p-ethylphenyl ether and the

Diels-Alder preparation of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride will be

discussed in depth. Results obtained from the experiments in the guided inquiry style of

laboratory; the Friedel-Crafts acylation of 2-chlorotoluene and subsequent Haloform

reaction to prepare 2-chloro-3-methyl benzoic acid and the experiments in the project-
 49

based style of laboratory instruction, the evaluation of L-proline as a catalyst for an

asymmetric aldol reaction to prepare a chiral -hydroxycarbonyl and subsequent Mosher

analysis to quantify the enantiomer enrichment of the product, an experiment in the

project based style of laboratory instruction, will be discussed elsewhere.

The four experiments performed that were not part of this research included:

NMR training/proton exchange/integral evaluation; photochemical isomerization of an

alkene, cis-1,2-dibenzoylethylene; Microscale Suzuki Cross-Coupling of phenylboronic

acid and 4-iodophenol in aqueous media, and the synthesis of substituted chalcones. The

NMR training/proton exchange/integral evaluation experiment consisted of a classic

alcohol-exchange experiment that demonstrated changes in chemical shift, spin-spin

coupling, and integration of protons on heteroatoms along with the relationship between

spin-spin dynamics and NMR integration and was outside the scope of this research

study. The photochemical isomerization of an alkene, cis-1,2-dibenzoylethylene and the

microscale Suzuki Cross-Coupling of phenylboronic acid and 4-iodophenol in aqueous

media, while instructive experiments, presented little opportunity to investigate students

mechanistic understanding of reagents and reactants. Consequently, neither experiment

was included in this study.

4.4.1 Williamson Synthesis of Ethers

Preparation of Methyl p-Ethylphenyl Ether

The Williamson synthesis of methyl p-ethylphenyl ether experiment allowed

students to explore conditions under which alkyl aryl ethers are prepared by the

Williamson synthesis of ethers. As the simplest and most widely used method for the
 50

preparation of both symmetrical and asymmetrical ethers, the Williamson synthesis

involves an SN2 reaction between a nucleophilic alkoxide (-or aroxide-) ion and an

electrophilic alkyl halide. The alkoxide (-or aroxide-) may be either primary, secondary,

or tertiary. In contrast, the alkyl halide is most often primary. Because alkoxide ions

may also act as bases, base-catalyzed E2 elimination of the alkyl halide often competes

with the Williamson synthesis of ethers. Whether substitution or elimination

predominates depends on the nature of the leaving group as well as the reaction

conditions (particularly temperature and solvent). When an aroxide ion is used,

alkylation of the ring also competes with ether synthesis. This is due to the fact that

aroxides are ambident nucleophiles that have two reactive sites.

To explore the Williamson synthesis of ethers students were assigned the

preparation of methyl p-ethylphenyl ether by the reaction of 4-ethylphenol with methyl

iodide in a 25% sodium hydroxide solution as described in the laboratory textbook for the

course (Forbes, Mayo, & Pike, 2011). Written in the expository style of laboratory

instruction, the experiment included a mechanistic discussion of the Williamson synthesis

of ethers as well as a detailed procedure. A deductive approach was employed where

students were required to perform the reaction and prove the correct product was

obtained by comparison of characterization data obtained on the material they

synthesized with that provided in the course textbook.

The synthesis of methyl p-ethylphenyl ether was accomplished by first combining

4-ethyl phenol with a 25% sodium hydroxide solution and stirring the mixture at room

temperature until dissolution occurred. Dissolution provided a visual indication that all

of the water-insoluble 4-ethylphenol had been deprotonated by the 25% sodium

 51

hydroxide solution transforming it into the water-soluble sodium 4-ethylphenoxde salt.

Tetrabutylammonium bromide is then added followed by methyl iodide. The mixture

was then heated to 65C for one hour before being cooled to room temperature. Diethyl

ether was then added to create a two phase mixture. After separation of the aqueous and

organic layers, the diethyl ether layer was washed sequentially with a 5% NaOH solution

followed by water. The crude product was purified by chromatography on silica gel.

Performed under phase transfer conditions, the reaction involved both an organic

and aqueous phase. The alkyl halide used in the reaction, methyl iodide, acted as the

organic phase along with the product methyl p-ethylphenyl ether. Initiation of the

reaction occurred by deprotonation of 4-ethylphenol by the 25% sodium hydroxide

solution to give the 4-ethylphenoxide ion that was carried from the aqueous phase across

the phase boundary into the organic phase as the tetrabutylammonium 4-ethylphenoxide

ion pair by reaction with the phase transfer catalyst tetrabutylammonium bromide. Once

in the organic phase, reaction occurs by the classic SN2 process of backside attack of the

phenoxide ion on methyl iodide. Both the product methyl p-ethylphenyl ether and the

corresponding halide salt of the phase transfer catalyst tetrabutylammonium iodide were

produced. The halide salt of the catalyst then returned to the aqueous phase where the

halide ion is exchanged for another phenoxide ion and the process repeats itself. The

catalyst is able to cross the barrier between the aqueous and organic phases because its

four butyl groups allow for solubility of the ion pair in the organic phase while the

charged ionic center of the ion pair provide solubility in the aqueous phase (scheme 4.1).

Once reaction was complete, the crude product was extracted from the reaction

mixture with diethyl ether. Because diethyl ether will also extract any unreacted 4-
 52

ethylphenol and methyl iodide, the diethyl ether layer is washed with a 5% sodium

hydroxide solution to convert any 4-ethyl phenol and methyl iodide into their water

soluble phenoxide and methoxide salts and separate them from the ether product. A

subsequent wash with water is performed to remove any traces of sodium hydroxide and

other water soluble impurities from the product ether.

-
CH3CH2 O CH3 I CH3CH2 O CH3

-
(C4H9)4N+ (C4H9)4N+ I

Organic Phase

Aqueous Phase

- -
CH3CH2 O CH3CH2 O H (C4H9)4N+ I

-
(C4H9)4N+ Br - Na+ OH

Scheme 4.1 Catalytic Phase Transfer Cycle

4.4.2 Diels-Alder Reaction:

Preparation of 4-Cyclohexene-cis-1, 2-dicarboxylic Acid Anhydride

Commonly used for the preparation of six-membered carbocyclic rings, the Diels-

Alder reaction is one of the most important synthetic reactions in organic chemistry. Its

utility derives from the fact that in one step, two new carbon-carbon bonds are formed

and up to four stereocenters may be produced. The Diels-Alder reaction is an example of

a [4 + 2] cycloaddition between a conjugated 1,3-diene that contributes four carbons and

an alkene (the dienophile) that contributes two carbons to form a six member ring that is
 53

part of a cyclic compound (the adduct) produced in the reaction. When an alkyne is used

instead of an alkene, the Diels-Alder reaction yields a 1,4-cyclohexadiene. The Diels-

Alder reaction allows for the preparation of a large number of different compounds by

varying the nature of the diene and dienophile. Because the rate of the Diels-Alder

reaction is increased if the alkene or alkyne dienophile bears electron withdrawing

groups, -unsaturated esters, ketones, nitriles, and are frequently used as dienophiles.

Unsubstituted alkenes such as ethylene are poor dienophiles and react with butadiene

only at elevated pressures and temperatures.

The Diels-Alder reaction is a reversible equilibrium reaction that is usually not

very exothermic. Often, the reactants are dissolved in a solvent and heated. However,

the equilibrium constant (Keq) is temperature dependent, decreasing as temperature

increases, and may become very small at the elevated temperatures required for

unactivated dienophiles to proceed at a reasonable rate. Although increasing temperature

increases the rate of the reaction, it will reduce the amount of obtainable product.

Consequently, the Diels-Alder reaction is usually run at the lowest possible temperature.

The Diels-Alder reaction is a concerted one step thermal cycloaddition where a

ring is formed. Three bonds in the reactants break simultaneously as one new bond

forms along with two new carbon-carbon single bonds (scheme 4.2). Because the

electrons flow is in a cyclic manner, the Diels-Alder reaction is considered to be a

pericyclic reaction. To yield a cyclic product with a cis carbon-carbon double bond

required by the six-member ring, the diene must be in an s-cis conformation about the

single bond. Consequently, cyclic dienes usually react more rapidly than acyclic dienes.
 54

H
H R R

H R R
H

Scheme 4.2. Electron Flow in Diels-Alder Reaction

The reaction is also highly stereospecific with the stereochemistry of the dienophile

retained in the product. If two groups are cis on the dienophile then they will be cis in the

product. It they are trans on the dienophile, they will be trans in the product (scheme

4.3). Consequently, addition is suprafacial-suprafacial with both new carbon-carbon

single bonds formed on the same face of the diene and dienophile.

O O
H
OCH3 OCH3
+
OCH3 OCH3
H
O O

Carbomethoxy groups cis Carbomethoxy groups cis

O O
H
H3CO OCH3
+
OCH3 OCH3
H
O O

Carbomethoxy groups trans Carbomethoxy groups trans

Scheme 4.3. Stereoselectivity of the Diels-Alder Reaction

 55

A further stereochemical consequence arises from the relative orientation of the

reactants in Diels-Alder reactions. The reaction of cyclopentadiene with maleic anhydride

illustrates that there are two possible ways in which the reactants may interact that lead to

the formation of two possible products, the endo and exo stereoisomers (scheme 4.4).

Typically the endo isomer predominates as a result of secondary orbital overlap between

the diene and dienophile. However, the ratio of endo to exo product may vary depending

on steric and electronic factors and reaction conditions

O O
H
O + H O
+ O
HO O
O H O

Exo Adduct Endo Adduct

Scheme 4.4. Stereochemical Consequence of Orientation of Reactants

In the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride, a six-membered carbocyclic ring is prepared by reaction of a conjugated diene

with an alkene. This was accomplished by treatment of 1,3-butadiene with maleic

anhydride to yield the corresponding Diels-Alder adduct 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride (reaction scheme 2). 1,3-butadiene was generated in situ by

the thermal decomposition 3-sulfolene via a retro-cycloaddition (scheme 4.5).

 56

Generation of s-cis-1,3-butadiene

O heat O
S + S
O O
3-Sulfolene s-cis -1,3-Butadiene

Reaction of s-cis-1,3-butadiene with maleic anhydride

O H O
H
heat
+ O O
H
O H O

Maleic Diels-Alder Product

Anhydride 4-cyclohexene-cis-1,2-
dicarbocyclic anhydride

Scheme 4.5. Diels-Alder Reaction of 1,3-Butadiene with Maleic Anhydride

The Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic anhydride

experiment provided to students in their course textbook was written in the expository

style of laboratory instruction and included a mechanistic discussion of the reaction as

well as a detailed experimental procedure. A deductive approach was employed where

students were required to perform the reaction and prove the correct product was

obtained by comparison of characterization data obtained on the material they

synthesized with that provided in the course textbook.

 57

The synthesis of 4-cyclohexene-cis-1,2-dicarboxylic anhydride was accomplished

by combining xylenes, maleic anhydride, and 3-sulfolene in a conical vial equipped with

an air condenser capped with a drying tube filled with calcium chloride. The reaction

mixture was then gently heated to reflux for 20 minutes taking care not to overheat the

reaction mixture. After the reflux period was complete, the reaction mixture was allowed

to cool to ambient temperature. Toluene was then added followed by the dropwise

addition of petroleum ether until a slight cloudiness was observed. The solution was then

reheated until it became clear and then cooled in an ice bath. The crystalline product was

collected by vacuum filtration and washed with cold petroleum ether. Characterization of

the product obtained by students included melting point determination, and both infrared

and nuclear magnetic spectroscopy.

Although maleic anhydride and 1,3-butadiene readily condense to give endo-cis-

4-cyclohexene-1,2-dicarboxylic anhydride, it is not convenient to use 1,3-butadiene as a

reagent because it is a gas at room temperature making it difficult to handle and measure.

Consequently, 3-sulfolene is used as the source of 1,3-butadiene. The primary

advantages of using 3-sulfolene as a source of 1,3-butadiene include its high stability at

room temperature and its rapid and complete decomposition to sulfur dioxide and pure

1,3-butadiene upon moderate heating (110-130C). Other advantages of using 3-

sulfolene include it is relatively inexpensive, odorless, nonflammable, and practically

nontoxic.

The reaction is performed in xylenes because not only is xylenes is an excellent

solvent for both reactants and the product, but also controls the reaction rate so that 25 to

30 minutes at its reflux temperature of 137-140C is sufficient for complete

 58

decomposition of 3-sulfolene. Because both the starting material maleic anhydride and

the product endo-cis-4-cyclohexene-1,2-dicarboxylic anhydride are vulnerable to

hydrolysis, it is important to perform the reaction under anhydrous conditions.

Consequently the xylenes must be anhydrous and a calcium chloride drying tube used to

prevent moisture from entering the reaction apparatus. After the reflux period is

complete, the product is isolated by the addition of toluene followed by the dropwise

addition of petroleum ether until cloudiness develops. The mixture is reheated until all

solid material dissolves and allowed to cool. The crystalline product is then collected by

vacuum filtration and rinsed with petroleum ether.

 59

CHAPTER FIVE

STUDENT RESPONSES TO PRE-LABORATORY QUIZ QUESTIONS

5.1 Introduction

Throughout the summer 2011 session of the second semester organic chemistry

laboratory course, pre-laboratory quizzes were given to students at the beginning of each

laboratory session in which a new experiment was begun. The use of prelaboratory

quizzes was initiated by a previous instructor who believed the quizzes would motivate

students to study the material provided in both the laboratory manual and course textbook

about the experiment prior to coming the laboratory. Having studied the material in the

laboratory manual and course textbook, students would arrive at the laboratory with a

thorough understanding of the experiment to be performed. Consequently students would

be enabled to work efficiently and safely in the laboratory creating an environment where

learning would be maximized.

In this chapter, students responses to the questions posed on the pre-laboratory

quizzes will be presented and discussed in terms of the mechanistic themes discussed by

students in their responses. The mechanistic arguments provided by the students in their

responses is assumed to reveal the depth of mechanistic understanding held by the

students
 60

5.2 The Williamson Synthesis of Methyl p-Ethylphenyl Ether

The authors of the course textbook began their discussion of the Williamson

synthesis of methyl p-ethylphenyl ether with the following statement of the purpose of

the experiment: to demonstrate conditions under which alkyl aryl ethers are prepared

and the use of phase transfer catalysis (Mayo, Pike, & Trumper, 2000). The reader was

then instructed to review the techniques for solvent and liquid-liquid extraction presented

in an earlier chapter of the course textbook. A one-step reaction scheme that did not

include arrow pushing formalism illustrating the reaction of p-cresol with propyl iodide

to afford proyl p-toyl ether and sodium iodide is then presented. However, a reaction

scheme for the reaction of 4-ethylphenol with methyl iodide to give methyl p-ethylphenyl

ether and sodium iodide was not presented until immediately prior to the experimental

procedure for synthesis of methyl p-ethylphenyl ether (scheme 5.1).

NaOH
CH3CH2 OH + CH3I CH3CH2 OCH3 + Na+,I-
(C4H9)4N+,Br-

4-Ethylphenol Methyl Iodide Methyl p-ethylphenyl ether

Scheme 5.1. Williamson Synthesis of Methyl p-Ethylphenyl Ether

A brief discussion of the reaction conditions used in the Williamson synthesis of

ethers experiment was then presented. In the first paragraph of the discussion, the

authors instruct the reader that alkyl aryl ethers are generally prepared by use of the

Williamson synthesis of ethers an SN2 reaction specifically between a phenoxide ion

(ArO-) nucleophile and an alkyl halide (Mayo, Pike, & Trumper, 2000). The authors
 61

further note that the Williamson synthesis of ethers is often used for the synthesis of

symmetrical and unsymmetrical ethers where at least one of the carbon atoms is primary

or methyl and thus amenable to an SN2 reaction . In addition, the authors stated that

elimination (E2) is generally observed if secondary or tertiary halides are used, since

phenoxide ions are also bases.

A one-paragraph discussion of the phase transfer catalysis conditions used in the

experiment that did not include an illustration of the catalytic cycle was then provided. In

their discussion, the authors of the course textbook stated that the phase transfer catalyst

carries a phenoxide ion across the aqueous-organic phase barrier from the aqueous layer

to the organic layer where reaction occurs producing the ether product and halide salt of

the phase transfer catalyst. The authors then stated that the halide salt of the phase

transfer catalyst migrates to the aqueous phase where the halide ion is replaced by

another phenoxide ion and the process repeats.

After the phase transfer conditions are discussed, the authors stated that the

mechanism of the Williamson synthesis of ethers is a classic SN2 process and involves a

backside nucleophilic attack of the phenoxide ion on the alkyl halide (Mayo, Pike, &

Trumper, 2000). The authors then show a two-step reaction scheme that illustrates the

deprotonation of p-cresol by sodium hydroxide to give p-methylphenoxide, a sodium

cation, and water followed by the backside attack of propyl iodide by sodium p-methyl-

phenoxide to afford propyl methylphenyl ether and sodium iodide (scheme 5.2).
 62

-
CH3 OH + NaOH CH3 O Na+ + H2O

H
-
CH3 O Na+ + CH3CH2 C I CH3 O CH2CH2CH3 + Na+ I-
H

Scheme 5.2. Mechanism of the Williamson Synthesis of

Methyl p-Ethylphenyl Ether

Lastly, the authors provided a brief comparison of the acidity of phenols with

simple alcohols. In their comparison, the authors stated that phenols (pKa 10) are more

acidic than simple alcohols (pKa 16) due to resonance delocalization of the resulting

negative charge on oxygen throughout the aromatic system. An illustration of the

delocalization of the charge on phenoxide was then shown. The authors do not provide

additional mechanistic details with respect to either the preparation of propyl p-toyl ether

or the preparation of methyl p-ethylphenyl ether (scheme 5.3).

O O O O

Phenoxide ion

Scheme 5.3 Resonance Stabilization of the Phenoxide Ion

 63

5.2.1 Students Understanding of the Mechanism of the Williamson Synthesis

of Methyl-p-Ethylphenyl Ether

To investigate students mechanistic understanding of the Williamson synthesis of

methyl p-ethylphenyl ether, students were asked to classify the reaction with respect to its

mechanistic pathway and justify their response. All of the students correctly responded

that the Williamson synthesis of methyl p-ethylphenyl ether proceeds by a SN2

mechanism. However, students defended their response with a variety of mechanistic

arguments. Consequently, responses provided by students were organized into one of

seven themes: (1) methyl or primary alkyl halide, (2) backside attack, (3) displacement of

iodine, (4) one step reaction, (5) substitution, (6) SN2 with no discussion, and (7)

intermediates based upon the mechanistic arguments provided by the student (see

Appendix B, Table 5.1).

5.2.1.1 Methyl or Primary Alkyl Halide

The first subtheme of methyl or primary alkyl halide was found in the responses

of two students who demonstrated a mechanistic understanding of how the reaction

conditions utilized in the experiment determined the mechanistic pathway followed by

the Williamson synthesis of methyl p-ethylphenyl ether. These students defended their

response that the Williamson synthesis of methyl p-ethylphenyl ether occurs by an SN2

mechanism based upon the statement made by the authors of the course textbook that the

Williamson synthesis of ethers is often used for the synthesis of symmetrical and

unsymmetrical ethers where at least one of the carbon atoms is primary or methyl and

thus amenable to an SN2 reaction (Mayo, Pike, & Trumper, 2000). For example one of
 64

the two students responded it is a SN2 reaction since it is a primary carbon on the methyl

iodide or other haloalkane that is being attacked. The other of the two students

responded it is an SN2 reaction if the carbon is methyl or primary. By responding in

this manner, these two students demonstrated understanding that the Williamson

synthesis of methyl p-ethylphenyl ether proceeds by an SN2 mechanism because methyl

iodide was employed as the alkyl halide electrophile in the experiment. The use of

methyl iodide restricts the Williamson synthesis of methyl p-ethylphenyl ether to a SN2

mechanistic pathway due to the instability of the methyl cation that would form if the

reaction proceeded by an SN1 pathway.

These two students were further able to demonstrate a mechanistic understanding

of how the reaction conditions utilized in the experiment determined the mechanistic

pathway followed by the Williamson synthesis of methyl p-ethylphenyl ether by using

the statement made by the authors of the course textbook that elimination (E2) is

generally observed if secondary or tertiary halides are used, since phenoxide ions are also

bases (Mayo, Pike, & Trumper, 2000). For example one of the two students also

responded if it was a secondary or tertiary carbon then it would most likely be an E2

reaction since phenoxide is a base. Similarly, the other of the two students responded it

is an E2 reaction if the carbon is secondary or tertiary. By responding in this manner,

these two students demonstrated their understanding that the use of methyl iodide as the

alkyl halide electrophile prevents the reaction from proceeding by an elimination

mechanistic pathway due to the absence of a hydrogen beta to the carbon atom bearing

iodide
 65

Because the responses provided by these two students demonstrated they

understood how the use of methyl iodide as the electrophile in the Williamson synthesis

of methyl p-ethylphenyl ether restricted the reaction to a SN2 mechanistic pathway, the

answers provided by these two students were considered to represent a mechanistic

understanding with no mechanistically incorrect statements.

5.2.1.2 Backside Attack

The second subtheme of backside attack was found in the responses of six

students who demonstrated an understanding of how reactions that occur by a SN2

mechanistic pathway proceed but not how the reaction conditions utilized in the

experiment determined the mechanistic pathway in the Williamson synthesis of methyl p-

ethylphenyl ether. In their responses, each of the six students defended their response the

Williamson synthesis of methyl p-ethylphenyl ether occurs by an SN2 mechanism

because of backside attack. These six students based their responses upon the argument

provided by the authors of the course textbook that the Williamson synthesis of ethers is

a classic SN2 process and involves a backside nucleophilic attack of the phenoxide anion

on the alkyl halide (Mayo, Pike, & Trumper, 2000) and the reaction scheme that shows

backside attack of propyl iodide by sodium p-methylphenoxide with arrow pushing

formalism. However, the hypothesis that a reaction proceeds by an SN2 mechanism due

to backside attack is supported experimentally by the observation that the rate of reaction

decreases with branching at both the and carbon atoms of the electrophile with

tertiary alkyl halides favoring -elimination instead of substitution. Because the

Williamson synthesis of methyl p-ethylphenyl ether is a preparative experiment, the

 66

effect of branching at both the and carbon atoms of the electrophile was not

investigated. The hypothesis of backside attack is also supported experimentally by the

observation that inversion of stereochemistry is observed when the carbon atom attacked

by the nucleophile is chiral. However, the conditions used in the experiment were not

chiral. Consequently the hypothesis of backside attack was not evident or demonstrated

in the Williamson synthesis of methyl p-ethylphenyl ether.

Two of the six students who defended their response that the Williamson

synthesis of methyl p-ethylphenyl proceeds by an SN2 mechanistic pathway because it

occurs by backside attack did not provide additional mechanistic arguments. However,

four of the six students who proposed the same answer defended their response that the

reaction occurs by backside attack by the inclusion of additional mechanistic arguments

in their response. Consequently the subtheme of backside attack was further organized in

to the three sub subthemes: (1) backside attack without further discussion, (2)

substitution, and (3) loss of iodine based upon the additional mechanistic arguments

provided by the students in their response.

5.2.1.2.1 Backside Attack without Mechanistic Arguments

The first sub-subtheme of backside attack was found in the responses of two

students who defended their response that the Williamson synthesis of methyl-p-

ethylphenol ether proceeds by a SN2 mechanism by stating it involves backside attack but

did not provide additional mechanistic arguments. For example, the first of the two

students simply responded backside attack while the second of the two students

responded SN2 because it takes place with a backside nucleophilic attack. Although the
 67

Williamson synthesis of methyl p-ethylphenyl ether does proceed with backside attack,

neither student discussed how backside attack was demonstrated in the experiment or the

chemical species involved. Consequently, the responses provided by these two students

were considered to represent a partial mechanistic understanding without mechanistically

incorrect arguments.

5.2.1.2.2 Substitution

The second sub-subtheme of substitution was found in the responses of three

students who further defended their response that the Williamson synthesis of methyl p-

ethyl phenyl ether precedes by a SN2 mechanistic pathway because it occurs by backside

attack with the mechanistic argument of substitution. Two of the three students correctly

responded that a SN2 mechanism involves substitution without including mechanistically

incorrect statements. For example, one of the two students responded SN2 substitution

reaction mechanism. It involves backside attack of a methyl group. The other of the

two students responded Williamson ether synthesis is a SN2 reaction i.e. bimolecular

nucleophilic substitution since the alkoxide attacks the back end of the alkyl halide.

Although both of these two students recognized that an SN2 mechanistic pathway, is by

definition a substitution reaction, neither noted that substitution was demonstrated

experimentally by substitution of 4-ethylphenol for the iodine of methyl iodide.

Consequently the responses of these two students were considered to represent a partial

mechanistic understanding with no mechanistically incorrect statements.

The response of the remaining of the three students demonstrated this student did

not have a clear understanding of the stereo-chemical consequences of backside attack

 68

with substitution. Although this students response of SN2 because the oxygen of the 4-

ethylphenol back attacks the methyl iodide and the 4-ethylphenol is substituted for where

the iodide was demonstrates that they understood what chemical entities were involved

in the substitution, their response precludes the inversion of stereochemistry.

Consequently the response provided by this student was considered to represent a partial

mechanistic understanding with incorrect mechanistic statements.

5.2.1.2.3 Formation of Iodine

The third sub-subtheme of formation of iodine was found in the response of one

student who defended their response that the Williamson synthesis of methyl p-

ethylphenyl ether proceeds through a SN2 mechanism with backside attack because of the

formation of the product and iodine. This students response of the phenoxide ion

attacks the methyl iodide from the backside. This causes the iodine to form an ion and

the product to form is based upon both the argument provided by the authors of the

course textbook that the Williamson synthesis of ethers is a classic SN2 process and

involves a backside nucleophilic attack of the phenoxide anion on the alkyl halide and

the reaction scheme that shows the reaction of sodium p-methylphenoxide with propyl

iodide to give propyl p-methylphenyl ether and sodium iodide. However, it is the use of

methyl iodide as the electrophile that causes the reaction to follow an SN2 mechanistic

pathway not the formation of an iodine ion and product. Consequently the response

provided by this student was considered to represent a partial mechanistic understanding

with no mechanistically incorrect statements.

 69

5.2.1.3 Nucleophilic Attack Releases Iodine

The third subtheme of nucleophilic attack releases iodine was found in the

responses of two students who also demonstrated an understanding of how reactions that

occur by a SN2 mechanistic pathway proceed but not how the reaction conditions utilized

in the experiment determined the mechanistic pathway followed in the Williamson

synthesis of methyl p-ethylphenyl ether. In their responses, both of the two students

defended their response that the Williamson synthesis of methyl p-ethylphenyl ether

occurs by an SN2 mechanism because nucleophilic attack releases iodine. The students

based their responses upon the argument provided by the authors of the course textbook

that the Williamson synthesis of ethers is a classic SN2 process and involves a backside

nucleophilic attack of the phenoxide anion on the alkyl halide and a reaction scheme that

shows backside attack of propyl iodide by sodium p-methylphenoxide. For example, one

of the two students responded the electron from the O attacks the carbon releasing the

iodine. The other of the two students provided more detail by responding the 4-

ethylphenol ion acts as a nucleophile and attacks the methyl iodide. The iodine is a

good leaving group which allows the reaction to take place. Although the phenoxide ion

does act as a nucleophile in the Williamson synthesis of methyl p-ethylphenyl ether, it is

the fact that methyl iodide is used as the electrophile that determines the mechanistic

pathway followed in the reaction. Consequently the responses provided by the two

students were considered to represent a partial mechanistic understanding with no

mechanistically incorrect statements.

 70

5.2.1.4 One-Step Reaction

The fourth subtheme of one-step reaction was found in the responses of one

student who also demonstrated an understanding of how reactions that occur by a SN2

mechanistic pathway proceed but not how the reaction conditions utilized in the

experiment determined the mechanistic pathway followed in the Williamson synthesis of

methyl p-ethylphenyl ether. This student defended their response the Williamson

synthesis of methyl p-ethylphenyl ether occurs by an SN2 mechanism with mechanistic

arguments that were not discussed by the authors of the course textbook nor

demonstrated in the experiment. In their response, the student stated that the Williamson

synthesis of methyl p-ethylphenyl ether is a SN2 reaction. Simultaneous reactions (one

step). One primary product is formed from two reactants. By responding in this

manner, the student demonstrated not understanding that the mechanistic pathway

followed in the reaction is determined by the use of methyl iodide as the electrophile.

The student also demonstrated not understanding experimental evidence supporting the

hypothesis a reaction occurs in a one-step concerted manner is provided by kinetic

studies that show the rate of the reaction depends on both the concentration of the

nucleophile and electrophile. As a preparative laboratory activity, the Williamson

synthesis of methyl p-ethylphenyl did not investigate how the rate of the reaction changes

with concentration of the reactants and reagents. Consequently the hypothesis of

simultaneous one-step reaction was not evident or demonstrated in the Williamson

synthesis of methyl p-ethylphenyl ether. Because the response provided by the student

did not contain misconceptions, the response provided by this student was considered to

represent a partial mechanistic understanding with no misconceptions.

 71

5.2.1.5 Substitution

The fifth subtheme of substitution was found in the responses of four students

who defended their response that the Williamson synthesis of methyl p-ethylphenyl ether

precedes by an SN2 mechanistic pathway because it involves substitution. For example,

one of the four students defended their response that the Williamson synthesis of methyl

p-ethylphenyl ether synthesis proceeds by an SN2 mechanism because it is a substitution

reaction. However, the student did not discuss that substitution is demonstrated in the

Williamson synthesis of methyl p-ethylphenyl ether by the substitution of 4-

ethylphenoxide for the iodide of methyl iodide. Because the response provided by this

student did not include erroneous mechanistic concepts, their response was considered to

represent a partial mechanistic understanding with no incorrect mechanistic statements.

Although two of the four students discussed the substitution in greater detail than

the first student, neither of them correctly identified the atoms that were involved in the

substitution. In their responses, these students did not discuss that the iodine of methyl

iodide is replaced by 4-ethylphenol in the reaction. For example, one of the two students

erroneously responded the reaction is an SN2 substitution reaction because a proton is

removed to make way for a methyl group. In a similar manner the other of the two

students erroneously responded the Williamson synthesis of methyl p-ethylphenyl ether

was a SN2 reaction. The NaOH is substituted in the reaction.

The remaining of the four students erroneously stated The reaction is an SN2

reaction. This can be seen because the OH group is attached to a tertiary carbon and the

iodide is attached to a methyl carbon allowing for nucleophilic attack for substitution

incorrectly referring to the sp2 hybridized carbon bearing the hydroxyl group as tertiary.
 72

Because the responses provided by these students included incorrect mechanistic

concepts, their responses were considered to represent a partial mechanistic

understanding with incorrect mechanistic arguments.

5.2.1.6 SN2 Without Discussion

The sixth subtheme of SN2 with no discussion was found in the responses of two

students who demonstrated a lack of a mechanistic understanding of the Williamson

synthesis of methyl p-ethylphenyl. In their responses, these two students noted that the

Williamson synthesis of methyl p-ethylphenyl ether proceeds through a SN2 mechanistic

pathway but did not provide further information. By responding in this manner, neither

student demonstrated that they understood how the reaction conditions determined the

mechanism of the reaction. Instead, these two students were simply repeating the

comments provided by the author of the course textbook that the Williamson synthesis of

ethers proceeds by an SN2 mechanistic pathway. However, because the responses

provided by these two students did not include misconceptions their answers were

considered to represent a lack of a mechanistic understanding with no explicitly stated

incorrect mechanistic statements.

5.2.1.7 Intermediates

The seventh subtheme of intermediates was found in the response of one student

who not only demonstrated a partial mechanistic understanding of how the reaction

conditions determine the mechanism that the Williamson synthesis of methyl p-

ethylphenol ether follows but also demonstrated that they did not understand how an SN2
 73

mechanism proceeds. In their response, the student noted that the Williamson synthesis

of methyl p-ethylphenyl ether proceeds by an SN2 mechanism because intermediates were

formed in the reaction. However, reactions that proceed by a SN2 mechanistic pathway

occur in a one-step concerted manner without the formation of intermediates. Because

the responses provided by this student included misconceptions, their response was

considered to represent a partial mechanistic understanding with erroneous mechanistic

arguments.

5.2.2 Student Understanding of the Purpose of the

25% Sodium Hydroxide Solution

In their discussion of the Williamson synthesis of methyl p-ethylphenyl ether, the

authors of the course textbook do not discuss the purpose of the 25% sodium hydroxide

solution. Rather, the authors show two chemical equations shown in Scheme 5.4. The

first equation is a balanced chemical equation for the reaction of 4-methyl phenol with

sodium hydroxide yielding sodium 4-methylphenoxide and water that does not utilize the

arrow pushing formalism. The second is a balanced chemical equation for the reaction of

sodium 4-methylphenoxide with propyl iodide to yield propyl p-methylphenyl ether and

sodium iodide that includes arrow pushing formulism indicating backside attack of

propyl iodide by sodium 4-methyl phenoxide. In their discussion of the chemical

equations, the authors refer to sodium 4-methylphenoxide as the phenoxide anion.

 74

-
CH3 OH + NaOH CH3 O Na+ + H2O

H
-
CH3 O Na+ + CH3CH2 C I CH3 O CH2CH2CH3 + Na+ I-
H

Scheme 5.4 Role of the 25% Sodium Hydroxide Solution

To investigate students mechanistic understanding of reagents and reaction

conditions in the Williamson synthesis of methyl p-ethylphenyl ether, students were

asked to discuss the purpose of the 25% sodium hydroxide solution in the experimental

procedure. In their responses, students discussed the purpose of the 25% sodium

hydroxide solution using a variety of mechanistic arguments. Consequently, responses

provided by the students were able to be organized into six themes: (1) deprotonation, (2)

to produce a basic environment, (3) creation of a nucleophile, (4) catalyst, (5) phase

transfer catalyst, and (6) produces water and Na+ salts based upon the purpose of the 25%

sodium hydroxide solution provided by the student in their discussion (see Appendix B,

Table 5.2)

5.2.2.1 Deprotonation

The first theme of deprotonation was found in the responses of seven students

who demonstrated either a mechanistic or partial mechanistic understanding of the

purpose of the 25% sodium hydroxide solution in the Williamson synthesis of methyl p-

ethylphenyl ether. In their responses, these students noted that the purpose of the 25%
 75

sodium hydroxide solution was to deprotonate. However, responses provided by these

students differed with respect to what species the student believed was deprotonated.

Consequently the responses of these seven students were able to be further divided into

three subthemes: (1) 4-ethylphenol, (2) phenol, and (3) unspecified based upon what

species the student indicated was deprotonated by the 25% sodium hydroxide solution.

5.2.2.1.1 4-Ethylphenol

The first subtheme of 4-ethylphenol consists of the responses of four students who

demonstrated a mechanistic understanding of the purpose of the 25% sodium hydroxide

solution in the Williamson synthesis of methyl p-ethylphenyl ether. In their responses,

each of these four students correctly noted that the purpose of the 25% sodium hydroxide

solution was to deprotonate 4-ethylphenol. Two of the four students discussed the 25%

sodium hydroxide solution in greater mechanistic detail than that provided by the authors

of the laboratory course textbook. In their responses, these students demonstrated an

understanding that sodium hydroxide dissociates into Na+ and OH- and that it is the OH-

ion that deprotonates 4-ethylphenol. One of these two students also stated that the

deprotonation of 4-ethylphenol is the first step in the mechanism while the other student

stated the hydrogen is removed from 4-ethylphenol so that it may react with the methyl

iodide. Because the responses provided by these two students demonstrated that they

held a mechanistic understanding of the purpose of the 25% sodium hydroxide solution

and did not exhibit any explicit misconceptions, their answers were considered to

represent a mechanistic understanding with no incorrect mechanistic statements.

 76

One of the four students also discussed the purpose of the 25% sodium hydroxide

solution in greater mechanistic detail than that provided by the authors of the course

textbook. This students response demonstrated an understanding of the role of sodium

hydroxide as a source of the hydroxide anion and that deprotonation of 4-ethylphenol

would leave a formal negative charge on the oxygen allowing it to participate in the

subsequent SN2 reaction. However, the student also incorrectly stated the OH- group

will attach to the H+ in the 4-ethylphenols and leave as H2O suggesting the student

confused deprotonation with the acid catalyzed dehydration of an alcohol. Consequently

the response of this student was considered to represent a mechanistic understanding with

incorrect mechanistic statements.

The response of the remaining of the four students that it removes the H from

OH group on the 4-ethylphenol demonstrates this student understood the purpose of the

25% sodium hydroxide solution was to deprotonate 4-ethylphenol. However, the student

did not note that the purpose of the deprotonation of 4-ethylphenol was to create a

nucleophilic phenoxide anion that would attack methyl iodide. Nevertheless the response

provided by this student did not include mechanistically incorrect statements.

Consequently their response was considered to represent a mechanistic understanding

with no incorrect mechanistic statements.

5.2.2.1.2 Phenol

The second subtheme of phenol was found in the responses of two students who

demonstrated an understanding that the purpose of the 25% sodium hydroxide solution

was to deprotonate. However, these students used the terminology provided in the course
 77

textbook to describe the species deprotonated as phenol instead of 4-ethylphenol. One of

the two students also correctly stated deprotonation would create a phenoxide anion that

will allow the reaction to proceed. Because the responses provided by these students

demonstrated that they understood the purpose of the 25% sodium hydroxide solution

was to deprotonate 4-ethylphenyl and did not include misconceptions, their responses

were considered to represent a mechanistic understanding with no incorrect mechanistic

statements.

5.2.2.1.3 Unspecified

The third subtheme of unspecified was found in the response of one student who

demonstrated a partial mechanistic understanding of the purpose of the 25% sodium

hydroxide solution. In their response, the student demonstrated understanding that the

purpose of the 25% sodium hydroxide solution was to deprotonate 4-ethylphenol by

stating The nucleophilic NaOH is used to strip off the hydrogen to make room for the

methyl group becoming Na+ and H2O. However, the student incorrectly stated that

sodium hydroxide acts as a nucleophile instead of a Brnsted base. In addition, the

student did not discuss the purpose of the deprotonation of 4-ethylphenol. Because the

student confused the concepts of nucleophile and base, their response was considered to

represent a partial mechanistic understanding with incorrect mechanistic statements.

5.2.2.2 To Produce a Basic Environment

The second theme of to produce a basic environment was found in the responses

of two students who demonstrated a partial mechanistic understanding of the purpose of

 78

the 25% sodium hydroxide solution in the Williamson synthesis of methyl p-ethylphenyl

ether. In their responses both of these students noted the 25% sodium hydroxide solution

produces a basic environment. However, in their responses neither of these students

correctly discussed how the 25% sodium hydroxide functions in the Williamson synthesis

of methyl p-ethylphenyl ether.

For example, one of the two students simply responded to provide basic

conditions for the experiment. Although the 25% sodium hydroxide does provide a

basic environment, the student did not note that the 25% sodium hydroxide solution is

used as a base to deprotonate 4-ethylphenol to create the nucleophilic phenoxide anion.

Consequently the response provided by this student was considered to represent a partial

mechanistic understanding with no incorrect mechanistic arguments.

In contrast, the response of the other of the two students included erroneous

statements in regards to the purpose of the 25% sodium hydroxide solution that suggest

the student combined the use of the 25% sodium hydroxide solution as a base to

deprotonate 4-ethylphenol to produce the nucleophilic phenoxide ion with the acid

catalyzed dehydration of alcohols. In their response the student erroneously stated the

25% sodium hydroxide solution produces a basic environment so the hydroxyl group

can leave the 4-ethylphenol and then can the 4-ethylphenol continue the reaction.

Consequently the response of this student was considered to represent a partial

mechanistic understanding with incorrect mechanistic statements.

 79

5.2.2.3 Creation of a Nucleophile

The third theme of creation of a nucleophile was found in the responses of two

students who also demonstrated a partial mechanistic understanding of the purpose of the

25% sodium hydroxide solution in the Williamson synthesis of methyl p-ethylphenyl

ether. In their responses these students indicated that the 25% sodium hydroxide solution

produced a species that was capable of nucleophilic attack on methyl iodide. One of the

two students stated that the sodium hydroxide creates a negative charge on the 4-

ethylphenol in order for it to be able to do a backside attach on methyl iodide in order to

the iodide to come off easily to form Na+I-. Although the 25% sodium hydroxide

deprotonates 4-ethylphenol to create 4-ethylphenoxide, it does not assist in the removal

of iodide from sodium iodide. Because the response provided by this student included

incorrect mechanistic conceptions, the response of this student was considered to

represent a partial mechanistic understanding with incorrect mechanistic arguments.

The response provided by the other of the two students demonstrated that they

understood the 25% sodium hydroxide solution was involved in the creation of a

nucleophilic oxygen that attacks methyl iodide. However, in this students answer of

provides OH for reaction (hydrolysis) so the O would have available electrons to bond

to the methyl group the student demonstrated they held misconceptions by incorrectly

refering to the process as hydrolysis. Consequently the response provided by this student

was considered to represent a partial mechanistic understanding with misconceptions.

 80

5.2.2.4 Catalyst

The fourth theme of catalyst was found in the responses of three students who

demonstrated a lack of a mechanistic understanding of the purpose of the 25% sodium

hydroxide solution in the Williamson synthesis of methyl p-ethylphenyl ether. In their

responses, these three students erroneously assumed the 25% sodium hydroxide solution

was a catalyst. However, each of the responses provided by the students differed with

respect to whether additional statements were included as well as in the nature of the

comments they made. For example, one of the three students simply replied that the 25%

sodium hydroxide solution was a catalyst. However, the 25% sodium hydroxide solution

is present as a stoichiometric base and is consumed in the Williamson synthesis of methyl

p-ethylphenyl ether as it deprotonates 4-ethylphenol producing sodium 4-ethylphenoxide

and water. Consequently, the response provided by this student was considered to

represent a lack of a mechanistic understanding with no incorrect mechanistic arguments.

The response of another of the three students of It is a catalyst to the reaction. It

reacts the OH with the H from the reactant to remove the H demonstrates this student

understood the purpose of the 25% sodium hydroxide solution was to act as a base and

deprotonate one of the reactants. However, the student did not specify which reactant

would be deprotonated. The students response also demonstrates that this student

incorrectly thought of the 25% sodium hydroxide solution as a catalyst. Consequently

the response provided by this student was considered to represent a lack of a mechanistic

understanding with no incorrect mechanistic arguments.

The remaining of the three students argued that the NaOH is used to help remove

the iodide form the methyl iodide. Basically the NaOH is used to catalyze the reaction
 81

and help it perform best. This answer suggests that the student did not understand the

role of the 25% sodium hydroxide solution as a stiochiometric base in the Williamson

synthesis of methyl 4-ethylphenyl ether. Instead, the response provided by this student

consisted almost entirely of incorrect mechanistic conceptions such as the NaOH helps

remove iodide from methyl iodide and that it functions as a catalyst that enhances the

Williamson synthesis of methyl p-ethyylphenyl ether. Consequently, the response

provided by this student was considered to represent a lack of a mechanistic

understanding with incorrect mechanistic statements.

5.2.2.5 Phase Transfer Catalyst

The fifth theme of phase transfer catalyst was found in of the responses of two

students who demonstrated a lack of a mechanistic understanding of the role of the 25%

sodium hydroxide solution in the Williamson synthesis of methyl p-ethylphenyl ether. In

their responses, these students erroneously assumed that the 25% sodium hydroxide

solution functions as a phase transfer catalyst. For example, one of the two students

responded it is a phase transfer catalyst and will bring the phenol ion across the phase

barrier. Although this student correctly understood how the phase transfer catalyst

tetrabutylammonium bromide functions in the Williamson synthesis of methyl p-

ethylphenyl, they incorrectly responded that the 25% sodium hydroxide solution

functions as the phase transfer catalyst instead of as a base. Consequently the response

of this student was considered to represent a lack of a mechanistic understanding of the

role of the 25% sodium hydroxide solution with no misconceptions.

 82

The other of the two students responded after the reaction has occurred the salt

goes back to the aqueous phase and is replaced by a new phenoxide so the process

repeats. Although this student also demonstrated an understanding of how the phase

transfer catalyst tetrabutylammonium bromide functions in the Williamson synthesis of

methyl p-ethylphenyl ether, this student also erroneously responded the 25% sodium

hydroxide solution functioned as the phase transfer catalyst instead of a base.

Consequenlty, the response of this student was considered to represent a lack of a

mechanistic unnderstanding of the purpose of the 25% sodium hydroxide solution with

no incorrect mechanistic statments.

5.2.2.6 Creates Water and Na+

The sixth theme of creates water and Na+ salts was found in the response of one

student who also demonstrated a lack of a mechanistic understanding of the purpose of

the 25% sodium hydroxide solution by stating that the hydroxide uses a proton to create

water and the Na becomes a salt ion. Although the hydroxide ion does gain a proton to

afford water and sodium iodide is produced as a byproduct, the purpose of the 25%

sodium hydroxide solution in the Williamson synthesis of methyl p-ethylphenyl ether is

to deprotonate 4-ethylphenol to give the 4-ethylphenoxide nucleophile that attack methyl

iodide. However, because the response provided by the student did not contain incorrect

mechanistic statements, their response was considered to represent a lack of a

mechanistic understanding with no incorrect mechanistic statements.

 83

5.2.3. Student Understanding of the Purpose

of Tetrabutylammonium Bromide

In the discussion section of the Williamson synthesis of ethers experiments, the

authors of the textbook provide the reader with a brief one-paragraph explanation of the

phase transfer catalyst conditions under which both reactions, the preparation of propyl p-

toyl ether and the preparation of methyl p-ethylphenyl ether, are performed. Because

only one discussion is provided for both the preparation of propyl p-toyl ether and the

preparation of methyl p-ethylphenyl ether experiments, the phase transfer catalysis cycle

is discussed in general terms.

The authors of the textbook describe the reaction system as comprised of two

phases; an aqueous phase and an organic phase. The organic phase was found in of the

alkyl halide methyl iodide which also serves as the solvent for the reaction and the ether

product. The authors instruct the reader that the phase transfer catalyst carries the

phenoxide ion from the aqueous phase to the organic phase where reaction occurs and

the ether product is formed. After reaction is complete, the halide salt of the phase

transfer catalyst then moves to the aqueous phase where a new phenoxide ion replaces the

iodide ion and the cycle repeats. An illustration of the catalytic phase transfer cycle is

not provided.

The phase transfer catalyst used in the experiment is described in the discussion

section of the textbook as having four large organic butyl groups that provide solubility in

the organic phase and an ionic core that provides solubility in the aqueous phase.

However, the exact phase transfer catalyst used in the experiment is not fully revealed

until the procedure section where the reader is instructed to add 15mg of
 84

tetrabutylammonium bromide (Bu4N+Br-) to the reaction mixture. No further information

about the phase transfer catalyst is provided by the authors of the course textbook in the

experiment. Instead, the authors refer the reader to an earlier experiment in the

laboratory textbook, alkene preparation by the Wittig reaction, where aliquot 336 is used

as the phase transfer catalyst in a Horner-Wadsworth-Emmons reaction.

To further investigate students mechanistic understanding of the reaction system

used in the Williamson synthesis of methyl p-ethylphenyl ether, students were asked to

discuss the purpose of tetrabutylammonium bromide in the experiment. Students

provided a variety of responses that revealed they held a range of mechanistic

understandings with respect to the purpose of tetrabutylammonium bromide.

Consequently, student responses were organized into one of five themes: (1) phase

transfer catalyst, (2) move between phases, (3) catalyst, environment, and (4)

miscellaneous based upon the purpose students gave in their responses for the purpose of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether

(see Appendix B, Table 5.3)

5.2.3.1 Phase Transfer Catalyst

The first theme of phase transfer catalyst was found in of the responses of five

students who demonstrated a partial mechanistic understanding of the purpose of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether.

In their responses, each of the five students answered tetrabutylammonium bromide

functions as a phase transfer catalyst. However, the responses provided by the five

students were different with respect to the chemical species the student answered was
 85

transported between the aqueous and organic phases. Consequently, the first theme was

able to be further divided into three subthemes: (1) transfers phenoxide, (2) transports

halide, and (3) brings down salt based upon what the student answered was being

transported between phases.

5.2.3.1.1 Transfers Phenoxide

The first subtheme of transfers phenoxide was found in of the responses of three

students who demonstrated a partial mechanistic understanding of the role of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether.

In their responses, each of the students identified tetrabutylammonium bromide as a

phase transfer catalyst and argued that its purpose was to transport the phenoxide anion

from the aqueous phase to the organic phase. Two of the three students also

demonstrated understanding that the tetrabutylammonium bromide transported 4-

ethylphenoxide from the aquesous phase to the organic phase is so it may react. For

example, one of the two students responded the tetrabutyl ammonium bromide is a

phase transfer catalyst and brings the phenoxide ion into the organic phase from the

aqueous phase so it may react. Similarly, the other of the two students responded It is

used as a phase transfer catalyst. It transports the phenoxide from the aqueous layer to

the organic layer where the reaction takes place. In contrast to the previous two

students, the response provided by the remaining of the three students of It is a phase

transfer catalyst. It transfers the phenoxide from the aqueous phase to the organic phase

does not discuss of the reason for the transfer of the phenoxide ion from the aqueous

phase to the organic phase.

 86

Although each of the three students demonstrated understanding

tetrabutylammonium bromide is used as a phase transfer catalyst to transport the

phenoxide anion from the aqueous phase to the organic phase, none of the three students

demonstrated understanding the phase transfer catalyst also transports the iodide ion

displaced from methyl iodide by 4-ethylphenoxide from the organic phase to the aqueous

phase as the halide salt. Nevertheless, because the responses provided by these three

students did not include incorrect mechanistic statements, the students responses were

considered to represent a partial mechanistic understanding with no incorrect mechanistic

statements.

5.2.3.1.2 Transports Halide

The second subtheme of transports halide was found in of the response of one

student who demonstrated a partial mechanistic understanding of the role of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether.

In their response, tetrabutylammonium bromide is the phase transfer catalyst

transporting the halide through the barrier this student recalled the statement made by

the authors of the course textbook that after reaction is complete, the halide salt of the

phase transfer catalyst then moves to the aqueous phase. However, the student failed to

discuss the phase transfer catalyst transports 4-ethylphenoxide from the aquesous phase

to the organic phase where reaction with methyl iodide occurs. Nonetheless, because the

response provided by this student did not include erroneous mechanistic statements, their

response was considered to represent a partial mechanistic understanding with no

incorrect mechanistic statements.

 87

5.2.3.2.1.3 Brings Down Salt

The third subtheme of brings down salt also was found in of the response of one

student who demonstrated a partial mechanistic understanding of the purpose of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether.

In their response, this student answered This acts as the phase transfer catalyst. It brings

down the salt to the organic phase to allow it to react. The response provided by this

student suggests they understood tetrabutylammonium bromide functions as a phase

transfer catalyst by transporting ions to the organic phase where reaction occurs.

However, the student did not specify the ions transported as either 4-ethylphenoxide or

iodide. In addition, the students response suggests they incorrectly thought the organic

layer was the bottom layer of the two phase system. Consequently, the response provided

by this student was considered to represent a partial mechanistic understanding with

incorrect mechanistic arguments.

5.2.3.2. Moves Between Phases

The second theme of moves between phases was found in of the responses of four

students who demonstrated a partial mechanistic understanding of the role of tetrabutyl-

ammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether.

However, in their responses none of the four students identified tetrabutylammonium

bromide as the phase transfer catalyst. In addition, the responses provided by each

student differed with respect to the chemical species tetrabutylammonium bromide

transported across the phase barrier. Consequently, the second theme of moves between

phases was divided into three subthemes: (1) moves 4-ethylphenol, (2) carries product
 88

across phase boundary, and (3) transfers Na+ and I- based upon the species students stated

was transferred between phases in their responses.

5.2.3.2.1 4-Ethylphenol

The first subtheme of 4-ethylphenol was found in the responses of two students

who demonstrated a partial mechanistic understanding of the purpose of

tetrabutylammonium bromide. In their responses, these two students replied

tetrabutylammonium bromide moves 4-ethylphenol instead of 4-ethylphenoxide across

the phase barrier. For example one of the two students responded the

tetrabutylammonium bromide helps move the 4-ethylphenol from the aqueous to the

organic phase to help it mix while the other of the two students responded Stabilizes

the 4-ethylphenol ion so it can pass through the phase barrier and complete the reaction.

Consequently, it is not clear if these two students understood it was the

tetrabutylammonium phenoxide ion pair that is transported.

The lack of a clear mechanistic understanding is further evident from the

additional comments provided by these two students in their responses. For example, one

of the two students responded the purpose of moving 4-ethyl phenol from the aqueous

phase to the organic phase was so it could mix instead of react. The other of the two

students erroneously responded that tetrabutylammonium bromide stabilized the 4-

ethylphenol ion in addition to allowing it to pass through the phase barrier and

complete the reaction. Consequently, the responses provided by these two students were

considered to represent a partial mechanistic understanding with incorrect mechanistic

statements.
 89

5.2.3.2.2 Carries Product Across Phase Boundary.

The second subtheme of carries product across phase boundary was found in the

response of one student who demonstrated a partial mechanistic understanding that

tetrabutylammonium bromide functions as a phase transfer catalyst in the Williamson

synthesis of methyl p-ethylphenyl ether. In their response, the student correctely

answered tetrabutylammonium bromide acts as a way to move from the aqueous to the

organic phase. However, the student erroneous answered tetrabutylammonium bromide

carries the product across the phase boundary. Because the response provided by this

student included misconceptions, their response was considered to represent a partial

mechanistic understanding with incorrect mechanistic statements.

5.2.3.2.3 Transfer Na+ and I-

The third subtheme of transfers Na+ and I- was found in the response of one

student who demonstrated a partial mechanistic understanding tetrabutylammonium

bromide functions as a phase transfer catalyst in the Williamson synthesis of methyl p-

ethylphenyl ether. In their response, this student answered tetrabutylammonium bromide

transfers Na+ and I- ions between phases. Although the phase transfer catalyst

transports the iodide ion produced in the reaction from the organic phase to the aqueous

phase, the sodium cation is not transported across the phase barrier but remains in the

orginal aqueous layer. Consequenlty the response provided by this student was

considered to represent a partial mechanistic understanding with incorrect mechanistic

statements.
 90

5.2.3.3 Catalyst

The third theme catalyst was found in the responses of three students who

demonstrated a lack of a mechanistic understanding of the role of tetrabutylammonium

bromide in the Williamson synthesis of methyl p-ethylphenyl ether. In their responses,

each of these three students replied tetrabutylammonium bromide is a catalyst. However,

none of the three students demonstrated understanding how tetrabutylammonium

bromide acts as a catalyst. For example, two of the three students responded that

tetrabutylammonium bromide is catalyst without further discussion. For example one of

the two students responded catalyst while the other of the two students responded it

is a catalyst. In their responses, neither of these two students demonstrated

understanding tetrabutylammonium bromide functions as a phase transfer catalyst that

transports 4-ethylphenoxide from the aqueous layer across the phase boundary into the

organic layer. Nor did either of the students demonstrated understanding

tetrabutylammonium bromide also transports the iodide ion displaced from methyl iodide

from the organic layer to the aqueous phase. However, because the responses provided

by these two students did not include incorrect mechanistic arguments, their responses

were considered to represent a lack of a mechanistic understanding with no

mechanistically incorrect statements.

In contrast to the previous two students, one of the three students erroneously

responded It is a catalyst used to create the intermediate ions which are easier to

transfer". Although tetrabutylammonium bromide transfers the 4-ethylphenoxide and

iodide ions between phases, it does not create either ion. Consequently the response
 91

provided by this student was considered to represent a lack of a mechanistic

understanding with incorrect mechanistic arguments.

5.2.3.4 Environment

The fourth theme of environment was found in the responses of two students who

demonstrated a lack of a mechanistic understanding of the purpose of tetrabutyl

ammonium bromide. These two students responded tetrabutyl ammonium bromide

creates an environment favorable for the Williamson synthesis of ethers. For example,

the response of one of the two students of it makes a better environment for the SN2

reaction reflects the statement made by the authors of the course textbook in the

discussion section of the experiment that the conditions under which these reactions

(Williamson synthesis of ethers) are conducted lend themselves to the use of phase-

transfer catalysis. Although the response provided by the student did not include

misconceptions, the student did not demonstrate understanding the purpose of

tetrabutylammonium bromide as a phase transfer catalyst was to transport 4-

ethylphenoxide from the aqueous layer across the phase boundary into the organic layer

and the iodide ion displaced from methyl iodide from the organic layer to the aqueous

phase. Consequently, the response provided by this student was considered to represent a

lack of a mechanistic understanding with no mechanistically incorrect statements.

The response provided by the other of the two students of to provide an ionic

environment for the iodine ions to be contained in demonstrates that not only did this

student not understand tetrabutylammonium bromide functions as a phase transfer

catalyst by transporting 4-ethylphenoxide from the aqueous layer across the phase
 92

boundary into the organic layer and the iodide ion displaced from methyl iodide from the

organic layer to the aqueous phase, but that this student also erroreously thought

tetrabutylammonium bromide would essentially trap and hold the iodide ions displaced

from methyl iodide in the reaction. Consequently the response provided by this student

was considered to represent a lack of a mechanistic understanding with incorrect

mechanistic assertions.

5.2.3.5 Miscellaneous

The fifth theme of miscellaneous includes the responses of three students whose

answers could not be placed into any of the previous themes and were unrelated to each

other. The responses provided by these students demonstrated they held a lack of a

mechanistic understanding of the role of tetrabutylammonium bromide in the Williamson

synthesis of ethers. For example, one of the three students erroneously responded

tetrabutylammonium bromide was the original organic layer of the solution. However,

methyl iodide is the original organic layer of the reaction mixture. Consequently, the

response provided by this student was considered to represent a lack of mechanistic

understanding with incorrect mechanistic statements. The response provided by another

of the three students of provide a negative ion for bonding to help separate methyl

iodide suggests this student did not understand the tetrabutylammonium ion is a cation

and is not involved in the separation of methyl iodide. Consequently, the response

provided by this student was also considered to represent a lack of a mechanistic

understanding with incorrect mechanistic statements. Lastly, the response provided by

the remaining of the three students of so that bromide would break up from the methyl
 93

and for the carbocation and then bind to the 4-ethylphenol was found to be comprised of

misconceptions. Consequenlty, the response of this student was considered to represent a

lack of a mechanistic understanding with incorrect mechanistic statements.

5.2.4 Student Understanding of the Purpose of

the 5% Sodium Hydroxide Solution

Once reaction is complete, the crude methyl p-ethylphenyl ether product is

isolated from the reaction mixture by extraction of the reaction mixture with two one

milliliter portions of diethyl ether. Because diethyl ether will also extract excess methyl

iodide and unreacted 4-ethylphenol from the reaction mixture as well, the combined

diethyl ether extracts are washed with a 5% sodium hydroxide solution. The 5% sodium

hydroxide solution converts excess methyl iodide and unreacted 4-ethylphenol that may

have been extracted along with the desired product by the diethyl ether into their

corresponding water soluble sodium methoxide and sodium phenoxide salts by ensuring

basic conditions maintained. The water soluble sodium methoxide and sodium phenoxide

salts migrate to the aqueous 5% sodium hydroxide solution and are removed upon

separation of the organic diethyl ether phase from the aqueous 5% sodium hydroxide

phase.

Although the experimental procedure for the Williamson synthesis of methyl p-

ethylphenyl ether given in the course textbook provides students with a step by step

procedure for the isolation of the crude methyl p-ethylphenyl ether product from the

reaction mixture, the authors of the course textbook do not provide a discussion of how

the solvent extraction procedure used in the experiment results in the isolation of the
 94

product. Instead, the authors refer the reader to the technique section of the course

textbook that provides a general discussion of microscale liquid-liquid extraction.

In their discussion of microscale liquid-liquid extraction in the technique section

of the course textbook, the authors list the following four criteria for choosing a solvent

for the extraction and isolation of a component from a solution: the extraction solvent

must be immiscible with the solution solvent, the distribution coefficient for the

component being extracted must be favored by the extraction solvent, the extraction

solvent must be readily separated from the desired component after extraction, and the

organic extraction solvent should not be reactive chemically with any component in the

aqueous mixture being extracted. The authors of the textbook also discuss; how to

choose an appropriate vessel for an extraction, alternative methods of mixing the two

immiscible solutions, and how to separate the two phases after mixing. The authors also

provide a practical example by discussing the microscale separation of benzanilide from

an acid solution by extraction with dichloromethane. In the example the authors provide

detailed instruction of how the two immiscible solutions are mixed followed by detailed

instructions of the use of a disposable Pasteur pipet for the separation of a mixture of

diethyl ether and water and the separation of the dichloromethane and aqueous phases.

Although the authors of the course text discuss criteria for the selection of an

appropriate solvent for microscale liquid-liquid extraction, selection of an appropriate

vessel for extraction, and, provide an example, the authors of the course textbook do not

discuss how these criteria may be applied to the Williamson synthesis of methyl p-

ethylphenyl ether. The authors of the course textbook also do not refer the reader to

earlier pages in the course textbook where the solubility of organic compounds in various
 95

solvents is discussed along with the partition or distribution coefficient of a substance

partially soluble in each of two immiscible solvents is discussed. Neither do the authors

refer the reader to later pages in the textbook where the affect of pH on the distribution

coefficient of organic acids on bases and how changes in pH may be used to assist in the

separation of organic acid and bases by extraction methods are discussed.

To investigate students mechanistic understanding of the role of reagents in the

isolation of the product methyl p-ethylphenyl ether from the reaction mixture, students

were first asked: What is the purpose of washing the combined diethyl ether extracts with

a 5% sodium hydroxide solution? Because the authors of the course textbook do not

specifically discuss how the solvent extraction conditions used in the Williamson

synthesis of methyl p-ethylphenyl ether result in the isolation of the crude methyl p-

ethylphenyl ether product, it is not surprising that when asked what is the purpose of the

5% sodium hydroxide wash of the combined diethyl ether extracts of the reaction

mixture, none of the students were able to provide a response that was both complete and

correct. However, responses provided by students revealed they held a wide range of

understandings in regards to the purpose of the 5% sodium hydroxide solution wash of

the combined diethyl ether extracts. Consequently, student answers were organized into

six themes: (1) react with reagents, (2) deprotonate, (3) remove impurities, (4) removes

aqueous layer, (5) separate, and (6) purify based upon the discussion provided in their

response (see Appendix B, Table 5.4).

 96

5.2.4.1. React with Reagents

The first theme of react with reagents was found in the response of one student

who demonstrated a partial mechanistic understanding of the purpose of the 5% sodium

hydroxide wash of the combined diethyl ether extracts. This students response of The

purpose of washing the diethyl ether layer with NaOH is to ensure all R-OHs and R-I

have been reacted with as well as bringing down all polar groups to aqueous levels

demonstrates the student understood unreacted 4-ethylphenol and excess methyl iodide

may have been extracted along with the product methyl p-ethylphenyl ether into the

diethyl ether. However, the student did not explain what they meant by reacted with.

Consequently it is not clear from their response if the student understood the 5% sodium

hydroxide solution would convert unreacted 4-ethylphenol and excess methyl iodide into

their corresponding water soluble sodium 4-ethylphenoxide and sodium methoxide salts.

The second part of their response of bringing down all polar groups to aqueous levels

suggests the student understood the 5% sodium hydroxide solution would assist in the

removal of polar impurities that may be present. Because the response provided by the

student did not contain mechanistically incorrect statements, their answer was considered

to represent a partial mechanistic understanding with no mechanistically incorrect

statement.

5.2.4.2 Deprotonate

The second theme of deprotonate was found in the responses of four students who

demonstrated a range of mechanistic understanding with respect to the purpose of the

wash of the combined diethyl ether extracts with a 5% sodium hydroxide solution. Each
 97

of the four students stated the purpose of 5% sodium hydroxide solution was to

deprotonate. However, the response provided by each of the four students was different

with respect to the chemical species the student stated would be deprotonated by the 5%

sodium hydroxide solution and with regards to the purpose of the deprotonation. For

example, the one of the four students correctly responded The diethyl ether was washed

because it could still have some 4-ethylphenol in it. The NaOH would deprotonate the 4-

ethylphenol. However the student did not discuss that the sodium hydroxide would also

convert any methyl iodide that may be also be present into sodium methoxide. Instead,

the student erroneously responded the resulting 4-ethylphenoxide would then react with

any remaining methyl iodide to make more product via a SN2 reaction. Consequently,

the response provided by this student was considered to represent a partial mechanistic

understanding with misconceptions.

Another of the four students who responded the purpose of the wash of the

combined diethyl ether extracts with a 5% sodium hydroxide solution was to deprotonate

also correctly stated the sodium hydroxide would remove any hydrogens on the

phenols. However, like the previous student, this student also did not discuss that the

sodium hydroxide would react with any methyl iodide that may be also be present. In

addition, the student also erroneously responded the deprotonation was to make sure that

the reaction has been carried out to completion. Consequently the response of this

student was also considered to represent a partial mechanistic understanding with

mechanistically incorrect statements.

Another of the four students who responded the purpose of the wash of the

combined diethyl ether extract with a 5% sodium hydroxide solution was to deprotonate
 98

correctly realized the ether layer still might have reactant. However, the student also

inaccurately responded the wash of OH will help finish anything that didnt take off

the H+. Consequently, the response provided by the this student was considered to

represent a partial mechanistic understanding with mechanistically incorrect statements.

Lastly, the response provided by the remaining of the four students of to remove

Hs from the compound (will make H2O) suggests this student based their response

upon their previous experience with using sodium hydroxide as a base to deprotonate

acidic species resulting in the formation of water. However, the student did not

demonstrate a mechanistic understanding the purpose of the wash of the combined

diethyl ether extracts with a 5% sodium hydroxide solution was to convert a remaining 4-

ethylphenol and methyl iodide to their water soluble sodium salts. Although the student

did not demonstrate a mechanistic understanding of the purpose of the 5% sodium

hydroxide solution, their response did not include misconceptions. Consequently, the

response of this student was considered to represent a lack of a mechanistic

understanding with no mechanistically incorrect statements.

5.2.4.3 Remove Impurities

The third theme of remove impurities was found in the responses of eight students

who demonstrated they held a partial mechanistic understanding of the purpose of

washing the combined diethyl ether extracts with a 5% sodium hydroxide solution. Each

of these eight students responded the 5% sodium hydroxide solution removes impurities

from the methyl p-ethylphenyl ether product. However, the response provided by the

students differed with respect to the impurity the student stated would be removed by the
 99

5% sodium hydroxide solution. Consequently the third theme of removes impurities was

further divided into four subthemes: (1) removes acidic components, (2) remove ions, (3)

removes aqueous layer, and (4) unspecified impurities.

5.2.4.3.1 Remove Acid Molecules

The first subtheme of removes acid molecules was found in the responses of two

students who demonstrated a lack of a mechanistic understanding of the purpose of

washing the combined ether extracts with a 5% sodium hydroxide solution. In their

responses, each of these two students answered the wash of the combined diethyl ether

layers with a 5% sodium hydroxide solution would remove acidic components instead of

unreacted 4-ethylphenol and methyl iodide. For example, one of the two students

erroneously responded the NaOH will pull out any slightly acid molecules in our diethyl

solution into the aqueous phase. We are then able to pipet it out to purify our solution.

Although the student did not demonstrate understanding the wash of the combined

diethyl ethers with the 5% sodium hydroxide wash would convert 4-ethylphenol and

methyl iodide to their corresponding water soluble sodium salts, the student demonstrated

understanding the impurities would be transferred to the aqueous layer and removed by

pipeting the aqueous phase away from the combined diethyl ether extracts.

Consequently, the response provided by this student was considered to represent a lack of

a mechanistic understanding with no mechanistically incorrect statements.

The other of the two students erroneously responded this reacts any acid

byproducts with the base so they can be removed with the rest of the aqueous layer.

Although this student also demonstrated not understanding that the wash of the combined
 100

diethyl ether extracts with a 5% sodium hydroxide solution would convert any remaining

4-ethylphenol and methyl iodide to their water soluble sodium salts, this student also

demonstrated understanding the impurities would be transferred to and removed with the

aqueous phase. Consequently, the response provided by this student was also considered

to represent a lack of a mechanistic understanding with no mechanistically incorrect

statements.

5.2.4.3.2 Remove Ions

The second subtheme of removes ions was found in the responses of three

students who also demonstrated a lack of a mechanistic understanding of the purpose of

washing the combined ether extracts with a 5% sodium hydroxide solution. In their

responses, each of the three students answered the wash of the combined diethyl ether

layers with a 5% sodium hydroxide solution would remove ions instead of responding it

would convert any residual 4-ethylphenol and methyl iodide into their water soluble salts.

In addition, the responses provided by each of the three students also contained

mechanistically incorrect statements. For example, one of the three students responded

the wash of the combined diethyl ether extracts with a 5% sodium hydroxide solution was

to remove any salt ions from the reaction. However, the reaction between 4-

ethyphenoxide and methyl iodide was complete prior to this step in the procedure.

Consequently the response provided by this student was considered to represent a lack of

a mechanistic understanding with mechanistically incorrect statements.

Another of the three students responded the NaOH solution will pull any

remaining ions away from the organic layer while the product dissolved in it. Although
 101

the student recognized the 5% sodium hydroxide solution would remove ions from the

organic phase, they did not demonstrate understanding the purpose of the 5% sodium

hydroxide wash was to convert any remaining 4-ethyphenol and methyl iodide to their

water soluble salts. In addition, the student also erroneously responded: and ensure that

the reaction was complete. However, the reaction between 4-ethylphenoxide and

methyl iodide is complete prior to this step. Consequently the response of this student

was considered to represent a lack of a mechanistic understanding with mechanistically

incorrect statements.

Lastly, the remaining of the three students erroneously answered washing with

NaOH pulls out any remaining methyl ions by bonding with OH in NaOH. However,

methyl cations are not formed in the synthesis of methyl p-ethylphenyl ether due to their

relative instability. In addition, the reaction follows a SN2 mechanistic pathway with the

hydroxide anion displacing iodide from methyl iodide in a one step concerted mechanism

by backside attack. Consequently, the response provided by this student was considered

to represent a lack of a mechanistic understanding with mechanistically incorrect

statements.

5.2.4.3.3 Removes Unspecified Impurities

The third subtheme of removes unspecified impurities was found in the responses

of two students who demonstrated a lack of a mechanistic understanding of the purpose

of washing the combined diethyl ether extracts the 5% sodium hydroxide solution. In

their responses, these two students stated the 5% sodium hydroxide wash removes

impurities from the diethyl ether layer. For example, one of the two students responded
 102

the 5% sodium hydroxide solution removes impurities from the diethyl ether layer by

adding a polar solvent. However, the student did not demonstrate understanding the 5%

sodium hydroxide solution would convert remaining 4-ethylphenoxide and sodium iodide

to there corresponding water soluble salts. In addition, the student referred to the 5%

sodium hydroxide solution as a polar solvent rather than an aqueous solution of an

inorganic base. Consequently, the response provided by this student was considered to

represent a lack of a mechanistic understanding with incorrect mechanistic statements.

In a similar manner, the response of the other of the two student of washing the

diethyl ether layer with 5% NaOH helps to isolate and purify the product demonstrates

this student understood the wash of the combined diethyl ether extracts removes

impurities. However, like the first student, this student also did not demonstrate

understanding the 5% sodium hydroxide solution would convert and excess 4-

ethylphenol and sodium iodide to their corresponding water soluble sodium salts. In

addition, this student also erroneously stated it is not as polar. Consequently, the

response provided by this student was also considered to represent a lack of a mechanistic

understanding with incorrect mechanistic statements.

5.2.4.4 Purify

The fourth theme of purify was found in the responses of two students who

demonstrated a lack of a mechanistic understanding of the purpose of the wash of the

combined diethyl ether extracts with a 5% sodium hydroxide solution. In their responses,

these two students erroneously responded the purpose of the wash of the combined

diethyl ether extracts with a 5% sodium hydroxide solution was performed to help purify
 103

either the combined diethyl ether extracts or the product. For example, one of the two

students answered to help purify the diethyl ether further while the other of the two

students answered to separate organic chemicals chemical from other solutions. By

responding in this manner, both students failed to demonstrate a mechanistic

understanding that the purpose of the wash of the combined diethyl ether extracts with a

5% sodium hydroxide solution was to convert residual 4-ethylphenol and methyl iodide

that may have been extracted along with product into their corresponding water soluble

sodium salts. In addition, the students response suggests they did not understand the

product would be purified in a subsequently column chromatography step.

Consequently, the responses provided by these two students were considered to represent

a lack of a mechanistic understanding with incorrect mechanistic statements.

5.2.4.5 Removes Aqueous Layer

The fifth theme of removes aqueous layer was found in the responses of two

students who demonstrated a lack of a mechanistic understanding of the purpose of

washing the combined diethyl ether extracts with a 5% sodium hydroxide solution.

These two students incorrectly answered the combined diethyl ether extracts were

washed with a 5% sodium hydroxide solution to ensure all of the aqueous phase was

removed. For example, one of the two students responded the NaOH allows for more

separation to get the last bit of aqueous layer out whereas the other of the two students

responded the washing was to ensure that none of the aqueous layer was in the diethyl

ether vial. These students likely confused the washing the combined diethyl ether

extracts with a 5% sodium hydroxide solution with the technique of washing an organic
 104

phase with a brine (saturated sodium chloride) solution to remove residual water.

Because the students not only demonstrated not understanding the combined diethyl ether

extracts were washed with a 5% sodium hydroxide solution to remove excess 4-

ethylphenol and methyl iodide by converting them to their corresponding sodium salts

but also demonstrated they erroneously believed the 5% sodium hydroxide solution

would help remove water from the combined diethyl ether extracts, the responses

provided by these students were considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.2.4.6 Separate Layers

The sixth theme of separate layers was found in the response of one student who

demonstrated a lack of a mechanistic understanding of the purpose of washing the

combined diethyl ether extracts with a 5% sodium hydroxide solution. This student

incorrectly answered the combined diethyl ether extracts were washed with a 5% sodium

hydroxide solution to separate the two phases organic solvent layer and aqueous solvent

layer efficiently. The separate those two layers exactly. This student likely confused

washing the combined diethyl ether extracts with a 5% sodium hydroxide solution with

the technique of adding of a saturated solution of sodium chloride (brine) to help separate

an aqueous phase from an organic phase during a workup procedure or break up an

emulsion. Because the student not only demonstrated not understanding the combined

diethyl ether extracts were washed with a 5% sodium hydroxide solution to remove

excess 4-ethylphenol and methyl iodide by converting them to their corresponding

sodium salts but also demonstrated erroneously believed the 5% sodium hydroxide
 105

solution would help separate the organic and aqueous phases, the response provided by

this student was considered to represent a lack of a mechanistic understanding with

misconceptions.

5.2.5 Student Understanding of the Purpose of the Water Wash

Of the Combined Diethyl Ether Extracts

After the combined diethyl ether extracts were washed with the 5% sodium

hydroxide solution and the aqueous phase removed, the ether extracts are washed with

water to remove any traces of the 5% sodium hydroxide solution that may remain. As

was the case for the 5% sodium hydroxide wash of the combined diethyl ether extracts,

the authors of the course textbook do not discuss the purpose of the water wash of the

combined diethyl ether extracts. Consequently, when asked to discuss the purpose of the

water wash of the combined diethyl ether extracts, it is not surprising most students were

unable to provide a complete and correct response. However, most of the students

demonstrated a general understanding the purpose of the water wash was to assist in the

purification of the product of the reaction. Even so, student responses were different with

respect to how the water washes purified the reaction product. Consequently, student

responses were organized into one of five themes: (1) to remove traces of sodium

hydroxide, (2) remove ions, (3) remove impurities/contaminates, (4) remove water, and

(5) miscellaneous responses (see Appendix B, Table 5.5).

 106

5.2.5.1 Removes Traces of Sodium Hydroxide

The first theme -to remove traces of sodium hydroxide- was found in the

responses of five students who demonstrated a mechanistic understanding that the

purpose of the water wash of the combined diethyl ether extracts was to remove traces of

the 5% sodium hydroxide solution used in the previous step. For example, one of the five

students correctly responded the purpose of the water wash of the combined diethyl ether

extracts was to remove leftover NaOH from the wash previous. Because the answer

provided by this student did not include misconceptions, their response was considered to

represent a mechanistic understanding with no mechanistically incorrect statements.

Although the remaining four of the five students also demonstrated a mechanistic

understanding that the purpose of the water wash of the combined diethyl ether extracts

was to remove any sodium hydroxide that remained from the previous wash of the

combined diethyl ether extracts with 5% sodium hydroxide solution, the responses

provided by these four students also contained various misconceptions. For example, one

of the four students erroneously responded the water wash of the combined diethyl ether

extracts was performed to wash away the remaining traces of 5% NaOH and diethyl

ether. Although the purpose of the water wash was to remove any residual sodium

hydroxide, it was not performed to remove diethyl ether. The student likely incorporated

their understanding diethyl ether and water are miscible to derive their response.

Consequently this students response was considered to represent a mechanistic

understanding with incorrect mechanistic statements.

Another of the four students responded the water was to ensure that none of the

aqueous layer or any of the NaOH was left in the diethyl ether vial. Although this
 107

student correctly responded the water wash of the combined diethyl ether extracts was

performed to remove any sodium hydroxide that may remained, the student also

incorrectly responded the water wash would also remove the aqueous layer. In forming

their response, the student likely confused the purpose of the final water wash of the

combined diethyl ether extracts with that of washing an organic phase with a brine

(saturated sodium chloride) solution to remove residual water. Consequently, the

response provided by this student was considered to represent a mechanistic

understanding with incorrect mechanistic statements.

Another of the four students erroneously responded the water wash would

remove any remaining NaOH and other impurities present in the ether layer. Although

the water wash of the combined diethyl ether extracts was performed to remove sodium

hydroxide, impurities other than residual NaOH are removed by a subsequent column

chromatography step. Consequently, the response provided by this student was also

considered to represent a mechanistic understanding with mechanistically incorrect

statements.

Lastly, the remaining of the four students responded the purpose of the water

wash is to grab any reminant or unreacted NaOH from the diethyl ether layer to make

sure it is pure. Although this student also demonstrated understanding the purpose of

the water wash of the combined diethyl ether extracts was to remove residual sodium

hydroxide, this student also incorrectly responded the purpose of the water wash was to

purify the combined diethyl ether extracts. The combined diethyl ether extracts are

purified in a subsequent column chromatography step. Consequently, the response

 108

provided by this student was also considered to represent a mechanistic understanding

with mechanistically incorrect statements.

5.2.5.2. Removes Ions

The second theme of removes ions was found in the responses of four students

who demonstrated either a mechanistic or a partial mechanistic understanding of the role

of the water wash in the Williamson synthesis of methyl p-ethylphenyl ether. In their

responses, these four students responded the purpose of the water wash of the combined

diethyl ether extracts was to remove undesired ions. For example, one of the four

students responded that the purpose of the water wash of the combined diethyl ether

extracts with water was to pull away any ions like the NaOH wash but is also supposed

to pull away any remaining Na+ and OH- ions. The response provided by this student

demonstrated they held a mechanistic understanding the purpose of the water wash of the

combined diethyl ether extracts was to remove any sodium and hydroxide ions remaining

from the previous wash with a 5% sodium hydroxide solution. However, in their

response, the student appears confused with respect to the nature of sodium hydroxide

and the sources of sodium hydroxide in the experiment. Consequently, the response

provided by this student was considered to represent a mechanistic understanding with

mechanistically incorrect statements.

The response provided by another of the four students of the water will pull out

any ionic salts formed to the aqueous phase demonstrates this student understood the

water wash of the combined diethyl ether extracts would dissolve and remove inorganic

salts that may be present. However, the student did not demonstrate understanding the
 109

primary role of the water wash was to remove residual sodium hydroxide leftover from

the previous wash of the combined diethyl ether extracts with a 5% sodium hydroxide

solution. Because the response provided by this student did not include misconceptions,

their response was considered to represent a partial mechanistic understanding with no

mechanistically incorrect statements.

Another of the four students reponded to help remove any impurities from the

diethyl ether phase such as Na+ and I- ions. The response provided by this student

demonstrates this student also understood the water wash of the combined diethyl ether

extracts would dissolve and remove inorganic ions that may be present. However,

similar to the previous student, this student also did not demonstrate understanding the

primary role of the water wash was to remove residual sodium hydroxide leftover from

the previous wash of the combined diethyl ether extracts with a 5% sodium hydroxide

solution. In addition, this student also erroneously responded the purpose of the water

wash of the combined diethyl ether extracts was to remove any impurities. Since

impurities are removed by column chromatography in a subsequent step, the response of

this student was considered to represent a partial mechanistic understanding with

misconceptions.

Lastly, the response provided by one of the four students of this helps to remove

ions demonstrates this student also thought the purpose of the water wash of the

combined diethyl ether extracts was to remove any water soluble ions that may be

present. However, similar to the previous two students, this student also did not

demonstrate understanding that the primary role of the water wash was to remove

residual sodium hydroxide left over from the previous wash of the combined diethyl ether
 110

extracts with a 5% sodium hydroxide solution. In addition, this student also incorrectly

stated the combined diethyl ether layers were washed with water so that the final

product is as pure as possible. The product is in the organic phase and everything not

wanted in the aqueous phase. Although the product is in the organic phase, the organic

phase is subsequently concentrated under a flow of nitrogen and purified by column

chromatography in a subsequent step. Consequently, the response provided by this

student was considered to represent a partial mechanistic understanding with incorrectly

incorrect statements.

5.2.5.3 Removes Impurities or Contaminates

The third theme of removes impurities or contaminates was found in the

responses of two students whose answers consisted of the broad and generalizable

statement that the purpose of the water wash of the combined diethyl ether extracts was

to remove impurities or contaminates. For example, the response provided by one of the

two students of the washing with water is also used to remove impurities so that the

product can be isolated after extraction. The water is polar, so it can attract certain polar

molecules which arent supposed to be with the product did not demonstrate the student

understood that the purpose of the wash of the combined diethyl ether extracts with water

was to remove traces of the 5% sodium hydroxide solution used in the previous step.

However, the response provided by this student did not contain misconceptions.

Consequently, the response provided by this student was considered to represent a lack of

a mechanistic understanding with no mechanistically incorrect statements.

 111

The response provide by the other of the two students of to remove some not

useful parts such as contamination. To help to activate the synthesis reaction well also

did not demonstrate an understanding that the purpose of the water wash of the combined

diethyl ether extracts as to remove remnants of the 5% sodium hydroxide solution used in

the previous step. In addition, the student also erroneously stated that the water wash of

the combined diethyl ether extracts would activate the reaction. Consequently the

response provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.2.5.4 Removes Water

The fourth theme of removes water was found in the responses of four students

who demonstrated a lack of a mechanistic understanding of the role of the water wash of

the combined diethyl ether extracts. These students erroneously stated the purpose of the

water washes was to remove any water that may be present in the diethyl ether extracts.

The responses provided by these four students suggest that they confused the water wash

of the combined diethyl ether layers with the washing of an organic phase with brine to

remove water, a procedure that they had performed in previous experiments. For

example, one of the four students simply replied the purpose of the water wash of the

combined diethyl ether extracts was to get any remaining aqueous layer. In their

response, the student failed to demonstrate a mechanistic understanding the purpose of

the water wash of the combined diethyl ether extracts was to remove remnants of the 5%

sodium hydroxide solution used in the previous step. Because the response provided by

this student did not include misconceptions, the response provided by this student was
 112

considered to represent a lack of a mechanistic understanding with no mechanistically

incorrect statements.

In contrast, the other three students provided additional mechanistic arguments in

their responses. For example, the response provided by one of the three students of

collect water made from mechanism into one layer. Water hydrogen bonds with itself

demonstrates the student understood water is produced in the reaction mechanism and

that water is capable of hydrogen bonding to itself. However, the student response did

not demonstrate they understood the purpose of the water wash of the combined diethyl

ether extracts was to remove residue of the 5% sodium hydroxide solution used in the

previous step. Because the response provided by this student did not include

misconceptions, their answer was considered to represent a lack of a mechanistic

understanding with no mechanistically incorrect statements.

The response of another of the three students of to bond the newly formed H2O

molecules through hydrogen bonding to allow for removal of the newly produced H2O

demonstrates this student also understood water is produced in the reaction mechanism

and that water is capable of hydrogen bonding to itself. However, as with the previous

student, this students response does not demonstrate they understood the purpose of the

water wash of the combined diethyl ether extracts was to remove residue of the 5%

sodium hydroxide solution used in the previous step. Even though the response provided

by this student did not demonstrate a mechanistic understanding of the purpose of the

water wash of the combined diethyl ether extracts, the response provided by this student

did not include misconceptions. Consequently the response provided by this student was
 113

considered to represent a lack of a mechanistic understanding with no mechanistically

incorrect statements.

The response provided by the remaining of the three students of H2O is the

leaving group so wash with water to get rid of any water. Has to do with the H bonding

and polarity of washes demonstrates the student not only did not have a mechanistic

understanding that the purpose of the water wash of the combined diethyl ether extracts

was to remove traces of the 5% sodium hydroxide solution used in the previous step, but

also that the student held misconceptions For example, the student inappropriately

incorporated the concept of protonation of an hydroxyl group to convert it to an oxonium

ion that will leave as water into their response in stating that water was a leaving group.

In addition, the student also inappropriately incorporated the concepts of hydrogen

bonding and solvent polarity into their response. Consequently, the response provided by

this student was considered to represent a lack of a mechanistic understanding with

misconceptions.

5.2.5.5 Miscellaneous

The fifth theme of miscellaneous was found in the responses of two students who

demonstrated a lack of a mechanistic understanding of the purpose of the water wash of

the combined diethyl ether extracts. For example, one of the two students responded the

purpose of the water wash of the combined diethyl ether extracts was to purify the

organic product. By responding in this manner, the student did not demonstrate

understanding the purpose of the water wash of the combined diethyl ether extracts was

to remove traces of the 5% sodium hydroxide solution used in the previous step. In
 114

addition, the student failed to note that the product is purified by column chromatography

in a subsequent step. However, because the response of this student did not contain

misconceptions, their response was considered to represent a lack of a mechanistic

understanding with no mechanistically incorrect statements.

The response provided by the other of the two students of washing with water

ensures that all organic compounds have been dissolved so collecting through drying can

occur does not demonstrate this student understood the purpose of the water wash of the

combined diethyl ether extracts was to remove traces of the 5% sodium hydroxide

solution used in the previous step. In addition, the response provided by this student was

found to be comprised primarily of misconceptions. Consequently, the response

provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.3 Diels-Alder Synthesis of 4-Cylcohexene-cis-1,2-Dicarboxylic Acid Anhydride

The authors of the course textbook begin their discussion of the Diels-Alder

synthesis of 4-cyclohexene-cis-1,2-dicarboxylic anhydride with the statement that the

purpose of the experiment is to demonstrate the use of the Diels-Alder reaction in the

preparation of six-membered carbocyclic rings. The statement is immediately followed

by a two step reaction scheme that includes curved arrow formalism illustrating the

thermal decomposition of 3-sulfolene to yield s-cis-1,3-butadiene and sulfur dioxide

followed by addition of s-cis-1,3-butadiene to maleic anhydride to afford 4-cyclohexene-

cis-1,2-dicarboxylic anhydride (scheme 5.5).

 115

O heat O
S + S
O O
3-Sulfolene s-cis -1,3-Butadiene

O H O
H
heat
O O
H
O H O

Maleic Diels-Alder Product

Anhydride 4-cyclohexene-cis-1,2-
dicarboxylic anhydride

Scheme 5.5 Diels-Alder synthesis of 4-cyclcohexene-cis-1,2-dicarboxylic anhydride.

The authors of the course textbook then present a brief biography of Otto Paul

Hermann Diels that highlights the discovery and publication of the Diels-Alder

cycloaddition in 1928. After the biography of Otto Paul Hermann Diels, the authors of

the course textbook provide a brief mechanistic discussion of the Diels-Alder reaction as

a concerted [4 + 2] thermal cycloaddition between a conjugated 1,3-diene and alkene. In

their discussion of the Diels-Alder cycloaddition, the authors of the course textbook

delineate three characteristics of the reaction: the reaction is faster if the dienophile bears

electron withdrawing groups, the diene must be in the s-cis conformation, and that the

reaction is highly stereospecific in terms of both cis/trans and endo/exo isomerism. A

detailed stepwise experimental procedure is then provided followed by an in-depth

discussion of the characterization of the 4-cyclohexene-cis-1,2-dicarboxylic anhydride

product by infrared spectroscopy including a description of the expected absorption

bands.
 116

5.3.1 Student Understanding of the Purpose of 3-Sulfolene

In the discussion section of the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-

dicarboxylic acid anhydride, the authors of the course textbook explain that because 1,3-

butadiene is a gas at room temperature (boiling point of -5C) it is difficult to handle and

measure. Consequently, the 1,3-butadiene used in the experiment is generated in-situ

from the thermal decomposition of 3-sulfolene, a solid at room temperature that is easily

handled. The authors of the course textbook describe the thermal decomposition 3-

sulfolene at moderate temperature to produce 1,3-butadiene and sulfur dioxide as an

example of a retro-Diels Alder reaction. A reaction scheme used previously that

illustrates the thermal decomposition of 3-sulfolene to yield s-cis-1,3-butadiene and

sulfur dioxide with curved arrow formalism is then shown (scheme 5.7).

O heat O
S + S
O O
3-Sulfolene s-cis -1,3-Butadiene

Scheme 5.6 Thermal decomposition of 3-Sulfolene

To investigate students mechanistic understanding of reagents and reaction

conditions used in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride, student were first asked why 3-sulfolene was used in the experiment rather

than 1,3-butadiene. Students provided a variety of responses that demonstrated they held

a wide range of understanding of why 3-sulfolene was used instead of 1,3-butadiene in

the experiment. Consequently the responses provided by students were organized into
 117

three themes: (1) 1,3-butadiene is a gas, (2) 3-sulfolene is more stable, and (3)

miscellaneous responses based upon the reasons students provided in their answers as to

why 3-sulfolene was used instead of 1,3-butadiene in the experiment (see Appendix B,

Table 5.7).

5.3.1.1 1,3-Butadiene is a Gas

The first theme of 1,3-butadiene is a gas was found in the responses of eleven

students who responded 3-sulfolene is used in the Diels-Alder synthesis of 4-

cylcohexene-cis-1,2-dicarboxylic acid anhydride because 1,3-butadiene is a gas.

However, these eleven students defended their response 1,3-butadiene is a gas with a

variety of mechanistic arguments. Consequently, the responses provided by these eleven

students were further organized into one of five subthemes: (1) 3-sulfolene is easier to

handle, (2) 1,3-butadiene is a gas that is difficult to handle/measure, (3) 3-sulfolene is a

source of 1,3-butadiene, (4) 3-sulfolene used instead of 1,3-butadiene, and (5)

miscellaneous based upon the mechanistic arguments presented by the student in their

answer. The different mechanistic arguments provided by students revealed they held a

range of mechanistic understandings as to why 3-sulfolene was used instead of 1,3-

butadiene in the experiment.

5.3.1.1.1 3-Sulfolene is Easier to Handle

The first subtheme of 3-sulfolene is easier to handle was found in the responses of

two students who demonstrated a mechanistic understanding of why 3-sulfolene is used

instead of 1,3-butadiene in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-

 118

dicarboxylic acid anhydride. In their responses, these two students discussed the

following three mechanistic arguments of why 3-sulfolene is used instead of 1,3-

butadiene: (1) 1,3-butadiene is a gas, (2) 3-sulfolene is easier to handle, and (3) 1,3-

butadiene can be easily obtained from 3-sulfolene. For example one of the two students

responded 1,3-butadiene is gaseous at room temperature and 3-sulfolene is easier to

handle and 1,3-butadiene can be easily made from it while the other of the two students

responded 3-sulfolene is a solid and can be easily produce 1,3-butadiene when we need

to. 1,3-buatdiene is a gas so it can be hard to use on its own. Basically it is easier to

handle 3-sulfolene than 1,3-butadiene. Because these two students were able to discuss

all three mechanistic arguments in their answers without incorporating misconceptions,

the responses provided by these two students were considered to represent a mechanistic

understanding with no mechanistically incorrect statements.

5.3.1.1.2 1,3-Butadiene is a Gas that is Difficult to Handle/Measure

The second subtheme of 1,3-butadiene is a gas that is difficult to handle/measure

was found in the responses of three students who demonstrated a partial mechanistic

understanding of why 3-sulfolene is used in the Diels-Alder synthesis of 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride instead of 1,3-butadiene. In their responses, each of

the three students stated because 1,3-butadiene is a gas, it is difficult to handle or

measure. However, none of these three students discussed 1,3-butadiene may be readily

obtained from 3-sulfolene or that 3-sulfolene is easier to handle than 1,3-butadiene

because it is a solid at room temperature. For example, one of the three students

responded 1,3-Butadiene is a gas at room temperature which makes it difficult to

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measure and mess with. Another of the three students responded 1,3-Butadiene is in a

gaseous state and difficult to measure. Lastly, the remaining of the three students

responded 1,3-butadiene is a gas at room temperature so it would be hard to handle.

Although the responses provided by these three students did not discuss all of the

mechanistic reasons why 3-sulfolene is used instead of 1,3-butadiene in the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride, there was no evidence of

misconceptions in their responses. Consequently, the responses provided by these three

students were considered to represent a partial mechanistic understanding without the

inclusion of mechanistically incorrect statements.

5.3.1.1.3 3-Sulfolene is a Source of 1,3-Butadiene

The third subtheme of 3-sulfolene is a source of 1,3-butadiene was found in the

responses of two students who also demonstrated a partial mechanistic understanding of

why 3-sulfolene is used in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride instead of 1,3-butadiene. In their responses, both of the two

students answered 3-sulfolene is used as a source of 1,3-butadiene in the experiment

because 3-sulfolene is a gas. However, neither of the two students discussed that being a

gas makes 1,3-butadiene difficult to handle and measure nor did either student discuss 3-

sulfolene is easier to handle and measure than 1,3-butadiene because it is a solid at room

temperature. For example, one of the two students responded 1,3-butadiene is a gas at

room temperature so starting with 3-sulfolene will give us 1,3-butadiene that can react

quickly to give us our product while the other of the two students responded 1,3-

butadiene is a gas and is difficult to control. 3-Sulfolene produces this gas in our reaction
 120

vial. So 3-sulfolene gives us a way to produce the needed reagent. Although the

responses provided by these two students did not discuss all of the mechanistic reasons

why 3-sulfolene is used instead of 1,3-butadiene in the Diels-Alder synthesis of 4-

cylcohexene-cis-1,2-dicarboxylic acid anhydride, there was no evidence of

misconceptions. Consequently, the responses provided by these two students were also

considered to represent a partial mechanistic understanding with no mechanistically

incorrect statements.

5.3.1.1.4 3-Sulfolene is Used Instead of 1.3-Butadiene

The fourth subtheme of 3-sulfolene is used instead of 1,3-butadiene was found in

the responses of two students who responded 3-Sulfolene is used instead of 1,3-butadiene

because 1,3-butadiene is a gas at room temperature. For example, one of the two students

responded because 1,3-butadiene is a gas under room temperature. So 3-sulfolene is

used instead while the other of the two students responded because 1,3-butadiene is a

gas at room temperature. So using 3-sulfolene and heat you can avoid it being a gas.

However, neither of the two students discussed that being a gas makes 1,3-butadiene

difficult to handle and measure or that 1,3-butadiene may be readily obtained from 3-

sulfolene. Nor did either student state that as a solid, 3-sulfolene is easier to handle and

measure. Although the responses provided by these two students do not discuss all of the

mechanistic reasons why 3-sulfolene is used instead of 1,3-butadiene in the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride, neither of the responses

included misconceptions. Consequently, the responses provided by these two students

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were considered to represent a partial mechanistic understanding with no mechanistically

incorrect statements.

5.3.1.1.5 Miscellaneous

The fifth subtheme of miscellaneous was found in the responses of two students

who also demonstrated a partial mechanistic understanding of why 3-sulfolene is used in

the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride instead of

1,3-butadiene. In their responses, both of the two students correctly responded 1,3-

butadiene is a gas. For example one of the students responded 1,3-butadiene is a gas at

room temperature. Similarly the other student responded 1,3-butadieneis a gas

However, neither of the two students provided additional mechanistically correct

arguments of why 3-sulfolene is used instead of 1,3-butadiene in their experiment, such

as being a gas makes 1,3-butadiene difficult to handle and measure, 1,3-butadiene may be

readily obtained from 3-sulfolene, and 3-sulfolene is easier to handle and measure

because it is a solid at room temperature. Although neither of the two students included

all of the mechanistic arguments for why 3-sulfolene is used instead of 1,3-butadiene in

the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride, both of

the two students did include mechanistically incorrect statements in their responses. For

example, one of the two students erroneously included so instead we make it and keep it

trapped whereas the other of the two students erroneously added 1,3-butadiene is

usually found in the trans formby synthesizing it from 3-sulfolene we get the correct

conformation. Consequently the responses of these two students were considered to

represent a partial mechanistic understanding with mechanistically incorrect statements.

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5.3.1.2 3-Sulfolene is More Stable

The second theme of 3-sulfolene is more stable was found in the responses of two

students whose answers demonstrated a lack of a mechanistic understanding of why 3-

sulfolene is used rather than 1,3-butadiene in the Diels-Alder synthesis of 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride. In their responses, both of the two students

erroneously responded 3-sulfolene is used instead of 1,3-butadiene because 3-sulfolene is

more stable than 1,3-butadiene. For example, one of the two students responded 3-

sulfolene is more stable than 1,3-butadiene. The other of the two students responded

because 3-sulfolene is more stable and not flammable. Although neither student

provided mechanistically incorrect arguments for why 3-sulfolene is used instead of 1,3-

butadiene in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride, one of the two students correctly added 3-sulfolene is not flammable.

However, because neither student provided a correct mechanistic argument for why 3-

sulfolene is used instead of 1,3-butadiene in the Diels-Alder synthesis of 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride, the responses provided by these two students were

considered to represent a lack of a mechanistic understanding with mechanistically

incorrect statements.

5.3.1.3 Miscellaneous

The third theme of miscellaneous was found in responses of five students that

could not be placed into one of the previous themes and were unrelated to each other.

The responses provided by the five students demonstrated they held a range of

mechanistic understanding of why 3-sulfolene was used instead of 1,3-butadiene in the

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Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride. For

example, the response provided by one of the five students of 1,3-butadiene has a very

low boiling point which makes it hard to handle. 3-Sulfolene can be turned into 1,3-

butadiene and is easier to handle demonstrated they possessed a mechanistic

understanding of why 3-sulfolene is used instead of 1,3-butadiene. Because this student

was able to provide three mechanistically correct arguments as to why 3-sulfolene is used

instead of 1,3-butadiene in the experiment without the inclusion of misconceptions, the

response provided by this student was considered to represent a mechanistic

understanding with no mechanistically incorrect statements.

The response provided by another of the five students of It is easier to control its

decomposition through controlling the temperature demonstrated this student did not

have a mechanistic understanding of why 3-sulfolene was used instead of 1,3-butadiene

in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid. Although the

rate of decomposition of 3-sulfolene to 1,3-butadiene is readily controlled by changes in

temperature, it is not the reason 3-sulfolene is used instead of 1,3-butadiene. 3-Sulfolene

is used instead of 1,3-butadiene because 1,3-butadiene is a gas, 3-sulfolene is easier to

handle, and 1,3-butadiene can be easily obtained from 3-sulfolene upon heating.

Although the responses provided by this student did not demonstrate they had a

mechanistic understanding of why 3-sulfolene is used instead of 1,3-butadiene, thier

response did not include misconceptions. Consequenlty, the response provided by this

student was considered to represent a lack of a mechanistic understanding without

mechanistically incorrect statements.

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The response provided by another of the five students of because we can keep 3-

sulfolene at room temperature and then heat it when we want it to react. Raw 1,3

butadiene may react with other things in the solution before we are ready to begin the

reaction demonstrates this student held a partial mechanistic understanding of why 3-

sulfolene is used in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride instead of 1,3-butadiene. Although this students response suggests they

understood 3-sulfolene is used instead of 1,3-butadiene because it is easier to handle and

that 1,3-butadiene may be readily obtained from 3-sulfolene upon heating, it also

contained misconceptions. For example, the student erroneously stated that raw 1,3-

butadiene may react with other things in solution before we are ready to begin the

reaction. Because the response provided by this student contained misconceptions, their

answer was considered to represent a partial mechanistic understanding with

mechanistically incorrect statements.

The response provided by another of the five students of because 3-sulfolene has

SO2 group. This group will easily leave more than other groups making it easier for us to

end up with the 1,3-butadiene. Also, 1,3-butadiene isnt found isolated in nature

demonstrates this student did not have a mechanistic understanding of why 3-sulfolene

was used instead of 1,3-butadiene in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-

dicarboxylic acid anhydride. In their response, this student did not discuss that 3-

sulfolene is used instead of 3-sulfolene because being a gas makes 1,3-butadiene difficult

to handle and measure nor did the student discuss 3-sulfolene is easier to handle and

measure than 1,3-butadiene because it is a solid at room temperature. Instead, the

response provided by this student consisted primarily of misconceptions such as 1,3-

 125

butadiene is not found in nature. Consequently, the response provided by this student

was considered to represent a lack of a mechanistic understanding with misconceptions.

Lastly, the response provided by the remaining of the five students of because of

its special structure, electrons are leaving and reforming elsewhere and the moderate

temperature is a good environment condition for 3-sulfolene to decompose rather than

1,3-butadiene demonstrated this student also did not have a mechanistic understanding

of why 3-sulfolene was used rather than 1,3-butadiene in the Diels-Alder synthesis of 4-

cylcohexene-cis-1,2-dicarboxylic acid anhydride. Instead, response provided by this

student reflects the cyclic flow of electrons as three bonds in the reactants break

simultaneously to form one new bond forms along with two new carbon-carbon single

bonds in the pericyclic mechanistic pathway. In addition, the student erroneously stated

that 3-sulfolene would decompose under mild temperatures when relatively high

temperatures are required. Consequently, the response provided by this student was

considered to represent a lack of a mechanistic understanding with mechanistically

incorrect statements.

5.3.2 Student Understanding of How Sulfur Dioxide Produced is Handled

Organic reactions performed in the laboratory frequently release poisonous or

irritating gases as byproducts such as hydrogen chloride, ammonia, and sulfur dioxide.

When poisonous or irritating gases are produced in an organic reaction, the experiment is

usually performed in a hood to limit exposure to hazardous or toxic fumes. A gas trap

may also be used to prevent the gases produced from being released into the laboratory

environment. If the gas produced is insoluble in water, collection may be easily

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accomplished by the displacement of water from a collection tube. If the gas produced is

water soluble, the gas evolved may be directed from the reaction vessel to a container of

water or other aqueous solution wherein it dissolves. For example, for acidic gases such

as hydrochloric acid a dilute solution of sodium or ammonium hydroxide may be used

whereas for basic gases such as ammonia or low molecular weight amines a dilute

hydrochloric or sulfuric acid solution are commonly used.

The authors of the course textbook provide little instruction on how the sulfur

dioxide produced in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride should be handled. In the procedural section of the experiment the authors of

the laboratory course textbook warn sulfur dioxide is evolved in the process and

adequate ventilation should be provided. The authors of the course textbook also advise

that in large laboratory sections it is recommended that the evolved SO2 be trapped.

However, the authors do not specify how the sulfur dioxide should be trapped. Instead,

the authors refer the reader to the appropriate pages of the course textbook where

techniques for the collection and control of gases that are insoluble in water and gases

that are soluble in water are discussed.

To investigate students mechanistic understanding of the experimental variables

utilized in the Diels Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride, students were asked how the sulfur dioxide produced in the decomposition of

3-sulfolene should be trapped. Students provided a variety of responses that were

organized into one of five themes: (1) use of a fume hood; (2) use of fume hood and

drying tube; (3) experimental apparatus; (4) tube to trap SO2; and (5) miscellaneous
 127

depending upon how the student answered the sulfur dioxide produced in the reaction

should be handled (see Appendix B, Table 5.8).

5.3.2.1 Use of Fume Hood

The first theme of use of a fume hood was found in the responses of two students

who demonstrated a mechanistic understanding of how the sulfur dioxide generated from

the decomposition of 3-sulfolene in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride was to be actually handled in the laboratory. These two

students responded the sulfur dioxide produced in the experiment should be vented by the

use of a fume hood. For example, one of the two students responded it can be captured

using a fume hood. In a similar manner the other of the two students responded it can

be trapped after evolution by using a vent hood. Because the answers provided by these

two students demonstrated they understood the actual technique used to handle the sulfur

dioxide gas produced by the decomposition of 3-sulfolene without the inclusion of

misconceptions, the responses provided by these two students were considered to

represent a mechanistic understanding without mechanistically incorrect statements.

5.3.2.2 Use of Fume Hood and Drying Tube

The second theme of use of a fume hood and drying tube was found in the

responses of five students who also demonstrated a mechanistic understanding of how the

sulfur dioxide generated by the decomposition of 3-sulfolene in the Diels-Alder synthesis

of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride was to be handled. In their

responses, these five students correctly answered the sulfur dioxide generated was to be
 128

vented by the use of a fumehood. However, each of the five students also erroneously

stated the sulfur dioxide gas produced could also be trapped by the use of a drying tube.

By responding in this manner, these students demonstrated they did not have a

mechanistic understanding that the use of drying tube in the Diels-Alder synthesis of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride was to keep atmospheric moisture out of

the experimental apparatus. In addition, the responses provided by these five students

differed with respect to the identity of the material the drying tube contained.

Consequently, the responses provided by these five students were further divided into the

three subthemes: (1) drying tube with calcium chloride, (2) drying tube packed with

absorbent, and (3) drying tube.

5.3.2.2.1 Drying Tube with Calcium Chloride

The first subtheme of drying tube with calcium chloride was found in the

responses of two students who demonstrated a mechanistic understanding that the sulfur

dioxide gas produced by the decomposition of 3-sulfolene in the Diels-Alder synthesis of

4-cyclohexene-cis-1,2-dicarboxylic acid anhydride would be vented through the use of a

fume hood. However, both of the two students also erroneously stated that a drying tube

filled with calcium chloride could also be used to capture the sulfur dioxide. For

example, one of the two students responded a lab fume hood can be used to control the

gas from going into the rest of the lab. The calcium drying tube might go after this gas.

Similarly, the other of the two students answered this could be accomplished by hood or

using the drying tube (Craig tube) used with calcium chloride. Because the responses

provided by these two students demonstrated they understood the sulfur dioxide gas
 129

generated in the reaction would be captured by the use of a fume hood but also

erroneously stated the sulfur dioxide gas could also be captured by the use of drying tube

filled with calcium chloride, their answers were considered to represent a mechanistic

understanding with mechanistically incorrect statements.

5.3.2.2.2 Drying Tube Packed with Absorbent

The second subtheme of drying tube with absorbent was found in the responses of

two students who demonstrated a mechanistic understanding that the sulfur dioxide gas

produced by the decomposition of 3-sulfolene in the Diels-Alder synthesis of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride would be vented through the use of a

fume hood. However, both of the two students also erroneously stated that a drying tube

filled with an absorbent could also be used to capture the sulfur dioxide. For example,

one of the two students responded To trap it, a packed vent will be on the reaction vial

to absorb. Also, should be done in a hood. Similarily the other of the two students

answered Sulfur dioxide istrapped with a drying column packed with material to

absorb it as well as under a bench hood. Although the responses provided by both of the

two students demonstrated they understood the sulfur dioxide gas generated by the

decomposition of 3-sulfolene would be vented by the use of a fume hood, their responses

also erroneously stated that the sulfur dioxide gas evolved would also be captured by the

use of drying tube filled with an absorbent. Consequently, their answers were considered

to represent a mechanistic understanding with mechanistically incorrect statements.

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5.3.2.2.3 Drying Tube

The third subtheme of drying tube was found in the response of one student who

responded we will perform the experiment under the hood and use a drying tube to help

collect the gas. Although the students response demonstrated a mechanistic

understanding that the sulfur dioxide gas produced by the decomposition of 3-sulfolene in

the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride would be

vented through the use of a fume hood, this student also erroneous answered a drying

tube would be used to capture the sulfur dioxide. However, in contrast to the responses

observed by students in the first two subthemes, this student did not specify what, if

anything, the drying tube was to be packed with. Because the answer provided by this

student correctly stated the sulfur dioxide gas produced by the decomposition of 3-

sulfolene would be vented by the use of a fume hood but also erroneously stated a drying

tube could be used to capture the sulfur dioxide, the response provided by this student

was considered to represent a mechanistic understanding with mechanistically incorrect

statements.

5.3.2.3 Experimental Apparatus

The third theme of experimental apparatus was found in the responses of four

students who responded the sulfur dioxide gas produced by the decomposition of 3-

sulfolene in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride would be trapped by the reflux condenser capped with a drying tube.

However, the responses provided by the students were different with respect to whether

they referred to the reflex condense as either a column or condenser. Consequently, the
 131

responses provided by the four students were divided in to the subthemes of either (1)

column or (2) condenser depending upon whether the student referred to the reflux

condenser as a distillation column or condenser.

5.3.2.3.1 Column

The first subtheme of column was found in the responses of two students who

referred to the reflex condenser as a column. For example, one of the two students

responded this will be done with the distillation column and filter (calcium chloride) on

top while the other of the two students responded this is accomplished using a column

and drying tube on the reaction vial. In their responses, neither of the two students

demonstrated understanding the sulfur dioxide produced by the decomposition of 3-

sulfolene would be prevented from being released into the laboratory by being exhausted

through a vent hood. In addition, neither of the two students demonstrated understanding

the purpose of the reflux condenser was to condense the xylene vapors produced by

heating the reaction mixture to reflux and return them to the reaction vessel. Also,

neither of the two students demonstrated understanding the purpose of the drying tube

packed with calcium chloride was to keep atmospheric moisture out of the experimental

apparatus. Consequently, the responses provided by these two students were considered

to represent a lack of a mechanistic understanding with mechanistically incorrect

statements.
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5.3.2.3.2 Condenser

The second subtheme of condenser was found in the responses of two students

who referred to the reflex column as a condenser. For example, one of the two students

responded you trap the sulfur dioxide using an air condenser with a calcium drying tube.

This is connected to the vial while the other of the two students responded

accomplished by using a drying tube set to a condenser to keep it out of the air. As

with the prior two students, neither of these two students demonstrated understanding the

sulfur dioxide produced by the decomposition of 3-sulfolene would be prevented from

being released into the laboratory by being exhausted through a vent hood. Nor did either

of the two students demonstrate understanding the purpose of the reflux condenser was to

condense the xylene vapors produced by heating the reaction mixture to reflux and return

them to the reaction vessel. Also, neither of the two students demonstrated understanding

the purpose of the drying tube packed with calcium chloride was to keep atmospheric

moisture out of the experimental apparatus. Consequently, the responses provided by

these two students were also considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.3.2.4 Tube to Trap SO2

The fourth theme of tube to trap SO2 was found in the responses of two students

who answered the sulfur dioxide produced by the decomposition of 3-sulfolene in the

Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride should be

handled by trapping it in a tube. For example, one of the two students responded we can

use a tube attached to our vial with a material in it that will trap the SO2 while the other
 133

of the two students responded it is important to trapthis is done using a tube above the

vial with a trap in it that will hold the SO2. However, neither of the two students

demonstrated understanding the sulfur dioxide produced by the decomposition of 3-

sulfolene would be prevented from being released into the laboratory by being exhausted

through a vent hood. Nor did either of the two students demonstrate understanding the

purpose of the reflux condenser was to condense the xylene vapors produced by heating

the reaction mixture to reflux and return them to the reaction vessel. Also, neither of the

two students demonstrated understanding the purpose of the drying tube packed with

calcium chloride was to keep atmospheric moisture out of the reaction. Consequently,

the responses provided by these two students were considered to represent a lack of a

mechanistic understanding with mechanistically incorrect statements.

5.3.2.5 Miscellaneous

The fifth theme of miscellaneous was found in responses provided by four

students that could not be placed into any of the previous themes and were unrelated to

each other. In their responses, these four students demonstrated a range of mechanistic

misunderstanding of how the sulfur dioxide produced by the decomposition of 3-

sulfolene in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride should be handled. For example, one of the four students answered the sulfur

dioxide should be handled by using either a tube system to trap it under water in a vial

or release it to the hood. Because the response provided by this student consisted of two

mechanistically valid techniques of how to handle the sulfur dioxide produced by the

decomposition of 3-sulfolene without the inclusion of misconceptions, it was considered

 134

to represent a mechanistic understanding with no mechanistically incorrect statements.

However, the student did not specify the sulfur dioxide produced by the decomposition of

3-sulfolene in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride demonstrated understanding the sulfur dioxide produced by the decomposition

of 3-sulfolene would be prevented from being released into the laboratory by being

exhausted through a vent hood.

Another of the four students responded sulfur dioxidecan be trapped by

controlling the exhaust path by running the reaction in a closed vessel. Although

controlling the exhaust path is the primary method of dealing with toxic gasses produced

by organic reactions, the student did not demonstrate understanding the sulfur dioxide

produced by the decomposition of 3-sulfolene would be prevented from being released

into the laboratory by being exhausted through a vent hood. In addition, the student also

erroneously responded the reaction would be run in a closed vessel. Consequently, the

response provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

The response provided by another of the four students of it can be trapped by

using a drying tube or it could be condensed and collected demonstrates this student did

not understand the sulfur dioxide produced by the decomposition of 3-sulfolene in the

Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride would be

prevented from being released into the laboratory by being exhausted through a vent

hood. In addition, the response provided by this student also demonstrates they did not

understand the purpose of the drying tube packed with calcium chloride was to keep

atmospheric moisture out of the reaction. The student also erroneously responded that
 135

the sulfur dioxide would be trapped, condensed, and collected. Consequently, the

responses provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

The response provided by the remaining of the four students of just collect it in a

tube and dissolve it in a solvent represents a combination of statements provided by the

authors of the course textbook with respect to how toxic gases produced by organic

reactions should be handled. However, the student did not demonstrate understanding the

sulfur dioxide produced by the decomposition of 3-sulfolene in the Diels-Alder synthesis

of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride would be prevented from being

released into the laboratory by being exhausted through a vent hood. Consequently, the

response provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.3.3 Student Understanding of the use of Xylenes as Solvent

In the discussion section of the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-

dicarboxylic acid anhydride experiment, the authors of the course textbook note that the

Diels-Alder reaction is reversible with an equilibrium constant (Keq) given by the

expression:

Keq = e-G/RT

Examination of the expression reveals the equilibrium constant (Keq) is proportional to

temperature. As the temperature at which the reaction is performed increases the

 136

equilibrium constant (Keq) decreases and may become quite small at high temperatures.

Consequently, the Diels-Alder reaction is usually performed at the lowest possible

temperature.

The lowest temperature to perform the Diels-Alder synthesis of 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride experiment is determined by the decomposition of 3-

sulfolene to give 1,3-butadiene and sulfur dioxide. A minimum temperature of 135 C is

required for the decomposition of 3-sulfolene to occur at a rate that allows completion of

the experiment to be completed within the two and a half hour time limit of the laboratory

period. In the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid

anhydride experiment, the technique of reflux is used to mix the reactants and reagents at

a stable maximum temperature. Xylenes is used as the reflux solvent because its boiling

point of 138C - 140C is high enough that 25-30 minutes at its reflux temperature is

sufficient for complete decomposition of 3-sulfolene at a rate that allows students to

complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride

within the two and a half hour laboratory period.

The authors of the laboratory course textbook do not discuss the use of xylenes as

a solvent in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride experiment until the procedure section of the experiment. When the authors

of the course textbook do discuss the use of xylenes in the procedure section of the

experiment, it is only in terms that it should be anhydrous to prevent the hydrolysis of

maleic anhydride. For example the authors of the laboratory course textbook state:
 137

The maleic anhydride should be finely ground and protected from

moisture to prevent hydrolysis to the corresponding acid. A mixture
of xylenes in the boiling-point range 137-140C will suffice. Use
freshly distilled solvent or dry it over molecular sieves before use.

To investigate students mechanistic understanding of the reaction conditions

utilized in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride, students were asked what are the characteristics of xylenes that make it a

suitable solvent. Responses provided by the students demonstrated they held a variety of

partially correct and incorrect mechanistic understandings of the characteristics of

xylenes that makes it a suitable solvent for the Diels-Alder synthesis of 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride. Consequently, the responses provided by students

were organized into four themes: (1) dissolves reactants, (2) nonreactive, (3) presence of

double bonds, and (4) miscellaneous (see Appendix B, Table 5.9).

5.3.3.1 Dissolves Reactants

The first theme of dissolves reactants was found in the answers of five students

whose answers were based upon various physical properties of xylene. In particular,

each of the five students responded the characteristic of xylene that makes it a good

solvent for the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride is its ability to dissolve the reactants and reagents used in the experiment. Four

of the five students also discussed other characteristics of xylenes in addition to its ability

to dissolve the reactants and reagents in their responses. Consequently, the first theme of

dissolves reactants was further divided into five subthemes: (1) dissolves reactants, (2)
 138

high boiling point, (3) ease of removing xylenes, (4) does not interact with reactants, and

(5) stable at reaction temperature based upon the characteristics of xylenes discussed by

the student in thier response.

5.3.3.1.1 High Boiling Point

The first subtheme of high boiling point was found in the response of one student

who answered it has a relatively high boiling point so the solution can be heated

properly. Xylenes can also dissolve all reagents without interfering in the reaction.

Although the students response lists two desirable characteristics of a solvent, dissolve

reagents and is not reactive and also revealed the student understood the reaction mixture

was to be heated, it did not demonstrate the student understood xylenes is used as the

reflux solvent because its boiling point of 138C-140C is high enough that 25-30

minutes at its reflux temperature is sufficient for complete decomposition of 3-sulfolene

allowing students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-

dicarboxylic acid anhydride within the two and a half hour laboratory period.

Consequently the students response was considered to represent a partial mechanistic

understanding with no mechanistically incorrect statements.

5.3.3.1.2. Does not Interact with Reactants

The second subtheme of does not interact with reactants was found in the

response of one student who answered xylenes are a good solvent for the reactants and it

will not react with or ionize them either. Although the characteristics discussed by the

student in their response are desirable characteristics of a solvent for an organic reaction
 139

such as it will not react with reactants, it does not demonstrate the student understood

xylenes is used as the reflux solvent because its boiling point of 138C - 140C is high

enough that 25-30 minutes at its reflux temperature is sufficient for complete

decomposition of 3-sulfolene at a rate that allows students to complete the Diels-Alder

synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half

hour laboratory period. Consequently, the response of this student was also considered to

represent a partial mechanistic understanding with no mechanistically incorrect

statements.

5.3.3.1.3 Stable at Reaction Temperatures.

The third subtheme of stable at reaction temperatures was found in the response

of one student who answered xylenes is a suitable solvent because of the solubility of all

reagents in the solvent at the reaction temperatures. This student also added xylenes is

also stable at the reaction temperatures so it will not breakdown and react with the

products or reactants. Although the characteristics discussed by the student in their

response such as dissolves reagents and is stable at the reaction temperature are desirable

characteristics of a solvent for an organic reaction, it does not demonstrate the student

understood xylenes is used as the reflux solvent because its boiling point of 138C-140C

is high enough that 25-30 minutes at its reflux temperature is sufficient for complete

decomposition of 3-sulfolene at a rate that allows students to complete the Diels-Alder

synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half

hour laboratory period. Consequently, the response of this student was considered to
 140

represent a partial mechanistic understanding with no mechanistically incorrect

statements.

5.3.3.1.4 Dissolves Reactants

The fourth subtheme of dissolves reactants was found in the response of one

student who answered its a good solvent because the reactants are easy to be solved in

this solvent. Although the ability to solubilize the reactants and reagents is a desirable

characteristic of a solvent, the student does not demonstrate they understood xylenes is

used as the reflux solvent because its boiling point of 138C - 140C is high enough that

25-30 minutes at its reflux temperature is sufficient for complete decomposition of 3-

sulfolene at a rate that allows students to complete the Diels-Alder synthesis of 4-

cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half hour

laboratory period. Consequently, the response of this student was also considered to

represent a partial mechanistic understanding with no mechanistically incorrect

statements.

5.3.3.1.5 Xylene Boils Off

The fifth subtheme of xylenes boils off was found in the response of one student

who answered xylenes is a suitable solvent because our reactants are both soluble in

xylene. Although the ability to dissolve reactants is a desirable characteristic of a

solvent, the student did not demonstrate understanding xylenes is used as the solvent

because its boiling point of 138C-140C is high enough that 25-30 minutes at its reflux

temperature is sufficient for complete decomposition of 3-sulfolene at a rate that allows

 141

students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid

anhydride within the two and a half hour laboratory period. In addition, the student also

erroneously stated both (reactants) have a significantly higher boiling point than xylene,

so xylene is able to boil off letting the reaction take place and concentrate the product.

Because the later statement made by the student is mechanistically incorrect, the response

provided by the student was considered to represent a partial mechanistic understanding

with mechanistically incorrect statements.

5.3.3.2 Non-Reactive

The second theme of non-reactive was found in the responses of four students

whose answers were primarily based upon the chemical properties of xylene. In

particular, each of the four students responded the characteristic of xylene that makes it a

good solvent for the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride is that it is nonreactive and will not react with or as one of the reactants or

reagents. However, each of the students discussed other characteristics of xylenes in

addition to it being nonreactive in their responses. Consequently, the second theme of

nonreactive was further divided into three subthemes: (1) wont react, (2) ease of

isolating product, and (3) keeps butadiene in solution based upon the characteristics

discussed by the student in their response.

5.3.3.2.1 Wont React

The first subtheme of wont react was found in the responses of two students who

answered xylenes is a suitable solvent for the Diels-Alder synthesis of 4-cylcohexene-cis-

 142

1,2-dicarboxylic acid anhydride because it will not react. However, the responses

provided by these two students were different in terms of what xylenes would not react

with and whether or not their answers included misconceptions.

For example, one of the two students responded It does not react with the

reagents. All the xylenes have similar boiling points. Although the not reacting with

the reagents is a desirable characteristic of a solvent and the isomers of xylenes do have

similar boiling points, the student did not demonstrate understanding xylenes is used as

the solvent because its boiling point of 138C-140C is high enough that 25-30 minutes

at its reflux temperature is sufficient for complete decomposition of 3-sulfolene at a rate

that allows students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-

dicarboxylic acid anhydride within the two and a half hour laboratory period.

Consequently, the response of this student was also considered to represent a partial

mechanistic understanding with no mechanistically incorrect statements.

In contrast to the previous student, the response provided by the other of the two

students of wont react as a Diels-Alder reagent. Some isomers are polar included

misconceptions. Although the not reacting as a Diels-Alder is a desirable characteristic,

the student did not demonstrate understanding xylenes is used as the solvent because its

boiling point of 138C-140C is high enough that 25-30 minutes at its reflux temperature

is sufficient for complete decomposition of 3-sulfolene at a rate that allows students to

complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride

within the two and a half hour laboratory period. In addition, the student also erroneous

responded some of the isomers of xylenes are polar. Consequently, the response
 143

provided by this student was considered to represent a partial mechanistic understanding

with mechanistically incorrect statements.

5.3.3.2.2 Ease of Isolating Product.

The second subtheme of ease of isolating product was found in the response of

one student who in addition to answering xylenes are unlikely to react with the

reactants also stated xylenes have a complete cyclic hydrocarbons and xylenes are

soluble in petroleum ether, making it easier to isolate the product. Although the student

correctly responded xylenes is unlikely to react with the reactants, is a cyclic

hydrocarbon, and is miscible with petroleum ether that is used later in experiment as an

anti-solvent to cause the 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride product to

precipitate, xylenes itself does not assist in the isolation of the product anhydride. In

addition, the students response does not demonstrate the student understood xylenes is

used as the solvent because its boiling point of 138C-140C is high enough that 25-30

minutes at its reflux temperature is sufficient for complete decomposition of 3-sulfolene

at a rate that allows students to complete the Diels-Alder synthesis of 4-cyclohexene cis-

1,2-dicarboxylic acid anhydride within the two and a half hour laboratory period.

Consequently the response provided by this student was considered to represent a partial

mechanistic understanding with mechanistically incorrect statements.

5.3.3.2.3 Keeps Butadiene in Solution

The third subtheme of keeps butadiene in solution was found in the response of

one student who in addition to answering xylenes is relatively unreactive with our
 144

reagents and products also stated xylenes will be able to keep the butadiene in solution

once it is separated from the sulfur dioxide group. Although being unreactive with

reagents and products is a desirable property for a solvent, xylenes is used as the solvent

because its boiling point of 138C-140C is high enough that 25-30 minutes at its reflux

temperature is sufficient for complete decomposition of 3-sulfolene at a rate that allows

students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid

anhydride within the two and a half hour laboratory period. In addition, xylenes is not

used to solvate the 1,3-butadiene produced by the decomposition of 3-sulfolene and hold

it in solution. Consequently the response provided by this student was considered to

represent a partial mechanistic understanding with mechanistically incorrect statements.

5.3.3.3 Presence of Double Bonds

The third theme of presence of double bonds was found in the answers of two

students whose answers were primarily based upon the structural properties of xylene. In

their responses, both students answered it was the structural similarities between xylenes

and the starting materials and products, in particular the presence of double bonds, that

makes xylenes a good solvent for the reaction. For example, one of the two students

responded xylenes contains the benzene ring which structurally close to 3-sulfolene and

maleic anhydride so it makes it a better solvent. Presence of double bonds in xylene. In

a similar manner the other of the two students responded the double bond help make it a

suitable solvent. These two students were likely recalling the axiom that like dissolves

like. However, neither student demonstrated understanding xylenes is used as the

solvent because its boiling point of 138C-140C is high enough that 25-30 minutes at its
 145

reflux temperature is sufficient for complete decomposition of 3-sulfolene at a rate that

allows students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-

dicarboxylic acid anhydride within the two and a half hour laboratory period.

Because the response of the first of the two students did not include

misconceptions, it was considered to represent a lack of a mechanistic understanding with

no mechanistically incorrect statements. However, because the second of the two

students erroneously added the methyl groups are electron donating which helps with

the reaction the response of this student was considered to represent a lack of a

mechanistic understanding with mechanistically incorrect statements.

5.3.3.4 Miscellaneous

The fourth theme of miscellaneous was found in responses provided by seven

students that could not be placed into any of the previous themes and were unrelated to

each other. In their responses, these seven students provide a variety of characteristics

they thought made xylenes a good solvent for the reaction that demonstrated a range of

mechanistic understanding of why xylenes is a suitable solvent for the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride.

For example, one of the seven students responded xylenes is a nonpolar aprotic

solvent and because of that it is a good solvent for the maleic anhydride and 3-sulfolene.

Although xylenes is a nonpolar aprotic solvent, it is not the reason xylenes is used as a

solvent for the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride. Xylenes is used as the solvent because its boiling point of 138C-140C is

high enough that 25-30 minutes at its reflux temperature is sufficient for complete
 146

decomposition of 3-sulfolene at a rate that allows students to complete the Diels-Alder

synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half

hour laboratory period. Consequently the response provided by this student was

considered to represent a partial mechanistic understanding without mechanistically

incorrect statements.

Another of the seven students responded it can be mixed together to change the

range of its boiling point. We will use a mixture that has a boiling point of 137-140C

Although the student correctly responded xylenes is used as the solvent because its

boiling point is 137-140C, the student did not demonstrate understanding a solvent with

a boiling point of approximately 135C is required to allow the decomposition of 3-

sulfolene to give 1,3-butadiene and sulfur dioxide. In addition, the student erroneously

thought that like petroleum ether, xylenes is available is available in different grades with

different boiling points. Consequently, the response of this student was considered to

represent a partial mechanistic understanding with mechanistically incorrect statements.

Another of the seven students responded xylenes can have many resonance

forms so they will have high electron density and help to dissolve the compounds using

the many different electron locations. This will help the quick electron transfer between

3-sulfolene and maleic anhydride which will result in the product. The students

response demonstrates they did not understand xylenes is used as the solvent because its

boiling point of 137-140C allows the decomposition of 3-sulfolene to give 1,3-butadiene

and sulfur dioxide at a rate that allows students to complete the Diels-Alder synthesis of

4-cyclohexene-cis-1,2-dicarboxylic acid anhydride within the two-and-a-half hour

laboratory period. Instead, their response appears to be a collection of various

 147

mechanistic concepts that were erroneously applied. For example, although it is possible

to draw various resonance forms, the resonance forms do not contribute to its ability to

dissolve compounds. Also, the resonance forms of xylenes do not contribute to the [4+2]

cycloaddition reaction. Consequently, the response provided by the student was

considered to represent a lack of a mechanistic understanding with mechanistically

incorrect statements.

The response provided by another of the seven students of xylenes can be used

as catalyst to help the reaction is going well. With the small amount of activation energy,

xylenes help to get the Diels-Alder product (because we will use as lowest as possible

temperature to prevent the loss of product) demonstrates this student understood the

Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride should be

done at the lowest possible temperature to prevent loss of product. However the

students response included several misconceptions. For example, the student

erroneously answered xylenes may be used as a catalyst to lower the activation energy

and help obtain product. In addition, the student does not discuss that xylenes is used as

the solvent is because its boiling point of 137-140C allows the decomposition of 3-

sulfolene to give 1,3-butadiene and sulfur dioxide at a rate that allows students to

complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid anhydride

within the two and a half hour laboratory period. Consequently, the response provided by

this student was considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

The response of another of the seven students of It is in a locked arrangement

and will not react with anything. It will not react with the sulfur dioxide. It also has a
 148

high boiling point so it will not evaporate that fast was found to include several

mechanistic concepts although are not incorrect, they are not the reason xylenes is used

as a solvent. For example, as an aromatic cyclic hydrocarbon, xylene is rigid and

nonreactive and does not participate in the reaction. In addition, xylenes also has a

relatively high boiling point and is not very volatile. However, the students response

does not demonstrate an understanding xylenes is used as the solvent because its boiling

point of 137-140C allows the decomposition of 3-sulfolene to give 1,3-butadiene and

sulfur dioxide at a rate that allows students to complete the Diels-Alder synthesis of 4-

cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half hour

laboratory period. Consequently, this students response was considered to represent a

lack of mechanistic understanding with no mechanistically incorrect statements.

The response provided by another of the seven students of good for

recrystallization. The product is soluble at high temperatures but not at cold

demonstrates this student erroneously thought xylenes was used because it is a good

solvent for recrystallization. Although the student discusses characteristics of a good

recrystallization solvent in their response, xylenes is used as a solvent for the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride because its boiling point

of 137-140C allows the decomposition of 3-sulfolene to give 1,3-butadiene and sulfur

dioxide at a rate that allows students to complete the Diels-Alder synthesis of 4-

cyclohexene cis-1,2-dicarboxylic acid anhydride within the two and a half hour

laboratory period. Although the student did not demonstrate understanding why xylenes

are used as a recrystallization solvent, their answer did not include misconceptions.
 149

Consequently the response provided by this student was considered to represent a lack of

a mechanistic understanding with no mechanistically incorrect statements.

The response provided by the last of the seven students of the methyl groups (of

xylenes) create a polarity to help remove SO2, allowing the two reagents to react and

form product revealed this student held misconceptions with respect to the structural

features of xylenes and how xylenes interacts with the reactants, reagents, and reaction

system. Although the methyl groups present on xylenes may be considered electron

donating, they do not create polarity, help remove SO2, nor do they allow the reactants to

react and form product. In addition, the student did not demonstrate understanding

xylenes was used as a solvent because its boiling point of 137-140C allows the

decomposition of 3-sulfolene to give 1,3-butadiene and sulfur dioxide at a rate that allows

students to complete the Diels-Alder synthesis of 4-cyclohexene cis-1,2-dicarboxylic acid

anhydride within the two and a half hour laboratory period. Consequently, the response

provided by this student was considered to represent a lack of mechanistic understanding

with mechanistically incorrect statements.

5.3.4 Student Understanding of the Need for Anhydrous Conditions

As discussed previously, the authors of the laboratory course textbook do not

discuss the use of xylenes as a solvent in discussion section of the Diels-Alder synthesis

of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride experiment. It is not until the

procedure section of the experiment that the authors of the course textbook discuss

xylenes and when they do, it is only in terms that it should be anhydrous to prevent the
 150

hydrolysis of maleic anhydride to its corresponding acid. For example, the authors of the

laboratory course textbook state:

The maleic anhydride should be finely ground and protected from

moisture to prevent hydrolysis to the corresponding aciduse freshly
distilled solvent or dry it over molecular sieves before use.

To prevent hydrolysis of maleic anhydride and the product 4-cylcohexene-cis-1,2-

dicarboxylic acid anhydride to their corresponding acids, the Diels-Alder synthesis of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride is performed under anhydrous

conditions. One of the ways anhydrous conditions are maintained in the experiment is

through the use of anhydrous xylenes. To further investigate students mechanistic

understanding of the reaction system utilized in the Diels Alder synthesis of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride, students were asked why it was

necessary for the xylenes to be anhydrous. Students provided a variety of responses that

demonstrated they held a wide range of mechanistic understandings of why anhydrous

xylenes is used in the experiment. However, student responses were able to be organized

into the two main themes of (1) reactions and (2) miscellaneous responses based upon the

mechanistic arguments provided by the student as to why the xylenes used in the

experiment needed to be anhydrous (see Appendix B, Table 5.10).

5.3.4.1 Reaction

The first theme of reaction was found in the responses of fourteen students who

demonstrated a range of mechanistic understanding of why it is necessary for the xylenes

 151

used in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride

be anhydrous. In their responses, each of the fourteen students answered water would

react if it was present. However, the responses provided by the students differed with

respect to what species the water would react with. Consequently, the theme of reaction

was further divided into the five subthemes of: (1) maleic anhydride, (2) product, (3)

reactants, (4) xylenes, and (5) reactions depending upon what the student indicated water

would react with in their response.

5.3.4.1.1 Maleic Anhydride

The first subtheme of maleic anhydride was found in the responses of three

students who answered it is necessary for the xylenes used in the Diels-Alder synthesis of

4-cylcohexene-cis-1,2-dicarboxylic acid anhydride to be anhydrous because maleic

anhydride will react with water. For example, one of the three students responded if it

has H2O in it, the H2O would react with the maleic anhydride which is undesirable.

Another of the three students answered maleic anhydride is very sensitive to moisture.

In a similar manner, the remaining of the three students responded if it is wet the H2O

will react with maleic anhydride and compromise it. In their responses these three

students echoed the statement made by the authors of the course textbook in the

procedure section of the experiment that:

the maleic anhydride should be protected from moisture to prevent

hydrolysis to the corresponding acidUse freshly distilled solvent or
dry it over molecular sieves before use.
 152

However, not one of the three students discussed that the 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride product is also susceptible to hydrolysis. Although the

responses provided by these three students only discussed that maleic anhydride is

sensitive to water, the answers provided by these three students did not include

misconceptions. Consequently the responses provided by these three students were

considered to represent a partial mechanistic understanding without mechanistically

incorrect statements.

5.3.4.1.2. Product

The second subtheme of product was found in the response of one student who

answered it must be dry because any H2O in the reaction will react with the desired

product giving us an unwanted product acid instead of the anhydride acid. Although not

discussed by the authors of the course textbook in the discussion or procedure section of

the experiment, this student recognized similar to maleic anhydride, the 4-cylcohexene-

cis-1,2-dicarboxylic acid anhydride product is also susceptible to hydrolysis. The student

also recognized hydrolysis of the 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride

product would result in the undesired corresponding acid byproduct. Although this

student demonstrated having a mechanistic understanding that water would hydrolyze the

product anhydride to its corresponding acid, the student did not discuss that maleic

anhydride was also susceptible to hydrolysis. However the response provided by the

student did not include misconceptions. Consequently, the response provided by this

student was considered to represent a mechanistic understanding without mechanistically

incorrect statements.
 153

5.3.4.1.3. Reactants

The third subtheme of reactants was found in the response of one student who

answered any H2O in the xylenes may react with the reactants (i.e. protonate oxygens).

In their response, the student did not specify the identity of the compounds water would

react with but only used the broad and generalizable term of reactant. In addition the

student demonstrated not understanding how water would interact with the reactants by

erroneously answering water would protonate oxygens. However, the reaction is not

performed under acidic conditions required for the protonation of oxygen atoms to occur.

Consequently, the response provided by this student was considered to represent a partial

mechanistic understanding with mechanistically incorrect statements.

5.3.4.1.4 Xylenes

The fourth subtheme of xylenes was found in the response of six students who

erroneously believed xylenes would react with any moisture that is present. For example,

two of the six students incorrectly responded xylenes would react with any moisture that

may be present. One of the two students erroneous responded xylenes can react with the

moisture while the second of the six students responded because if it has water in it, it

will react. In their responses, neither of the two students demonstrated understanding

any moisture present would react with maleic anhydride to give the unwanted carboxylic

acid byproducts. In addition, both the two student erroneously stated water would react

with xylenes. Consequently the responses provided by these two students were

considered to represent a lack of a mechanistic understanding with mechanistically

incorrect statements.
 154

Another two of the six students erroneously responded that if water was present,

hydrolysis of xylenes would occur. For example, one of the two students stated if they

are wet, it will react as if with an acid and hydrolysis will occur while the other of the

two students responded so it doesnt go through hydrolysis with moisture (destroy

double bonds). These two students likely based their responses upon their

understanding of the acid catalyzed hydrolysis of alkenes, a reaction learned in the first

semester of organic chemistry. However, as an aromatic compound, xylenes does not

undergo acid catalyzed hydrolysis. In addition, neither students demonstrated

understanding the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride is performed under anhydrous conditions to prevent the hydrolysis of maleic

anhydride and the product anhydride. Consequently, the response provided by these two

students were considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

The remaining two students erroneously responded xylenes would react with any

moisture present rendering it useless. For example, one of the two students responded

water would react with the double bonds and make the xylenes useless while the other

of the two students answered because it reacts with the moisture in air, so it needs to be

kept dry. If it is wet it doesnt work. The responses provided by these two students

were likely based upon their experiences with moisture sensitive reactants and reagents

they had used in previous experiments such as the Grignard reagent with will be

quenched upon contact with water. However, as an aromatic compound, xylenes does

not undergo acid catalyzed hydrolysis. In addition, neither students demonstrated

understanding the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

 155

anhydride is performed under anhydrous conditions to prevent the hydrolysis of maleic

anhydride and the product anhydride. Consequently, the response provided by these two

students were considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

5.3.4.1.5 Side Reactions

The fifth subtheme of side reactions was found in the responses of three students

who responded water will cause side reactions. Two of the students simply responded

water would cause side reactions without much further explanation. For example, one of

the three students responded water will cause reactions other than the desired one.

Another of the three students provided more detail by responding because excess water

will cause side reactions and lower yield. Although the responses provided by each of

the two students demonstrated they understood anhydrous conditions were required to

prevent side reactions, neither of the two students demonstrated understanding that if

water is present in the reaction system it would hydrolyze both the starting material

maleic anhydride and the 4-cyclohexene-cis-1,2-dicarboyxlic anhydride product.

Although the responses provided by these students did not demonstrate they had a

mechanistic understanding of why xylenes needed to be dry, the responses provided by

these two students did not include misconceptions. Consequently the answers provided

by these two students were considered to represent a partial mechanistic understanding

without mechanistically incorrect statements.

In contrast to the previous two students, the response provided by the remaining

of the three students of if it has some moisture on the xylene it will cause other reaction
 156

with corresponding acid included misconceptions in addition to answering water would

cause other reactions. Similar to the first two students, the response provided by this

student was also likely based upon their experience with water sensitive reagents in the

laboratory. However, it is not clear what the student meant by responding with

corresponding acid. Because the students response did not demonstrate they understood

that if water is present in the reaction system it would hydrolyze both the starting material

maleic anhydride and the 4-cyclohexene-cis-1,2-dicarboyxlic anhydride product, the

answers provided by this student was considered to represent a partial mechanistic

understanding with mechanistically incorrect statements.

5.3.4.2 Miscellaneous

The second theme of miscellaneous was found in the responses of four students

that could not be placed into the previous theme and were unrelated to each other. In

their responses, these four students provided a variety of arguments that demonstrated a

range of mechanistic understanding for why they believed the Diels-Alder synthesis of 4-

cylcohexene-cis-1,2-dicarboxylic acid anhydride needed to be performed under

anhydrous conditions.

One of the four students responded wet xylenes would mean H2O would be all

through the solvent and they could get in the way for the reaction. Although the student

demonstrated understanding water would impede the reaction, the student did not

specifically demonstrate understanding water would react both with maleic anhydride and

the product anhydride to produce unwanted acidic by products. Because the students
 157

response did not include misconceptions, their answer was considered to represent a lack

of a mechanistic understanding with mechanistically incorrect statements.

Another of the four students response of the chemical properties of xylenes may

change it its a liquid. It has to be dry to mix with 3-sulfolene demonstrates this student

held many misconceptions in addition to not understanding that any water present would

react with maleic anhydride and the product anhydride to produce carboxylic acid

byproducts. For example, the students response suggests they believed xylenes was a

solid instead of a liquid and that it would mix with 3-sulfolene instead of dissolving it. In

addition, the student erroneous thought that changing state from a solid to a liquid would

change the chemical properties of xylenes. Because the response provided by the student

did not demonstrate an understanding that any moisture present would potentially

hydrolyze maleic anhydride and the product anhydride but instead consisted of

miconceptions, the students response was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

Another of the four students responded you dont want water to cause the

reactants to turn into ions. Although the response provided by this student demonstrated

they understood the reactants could reaction with water, it does not specifically

demonstrate understanding water would convert both maleic anhydride and the the

anhydride product into unwanted acid byproducts. In their response, the student was

likely recalling their understanding that water dissolves ionic compounds by solvation of

the corresponding cations and anions. Consequently, the response provided by this

student was considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

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The remaining of the four students of it is a fine powder so if any moisture gets

in it, it will clump suggests that this student erroneously thought xylenes was a solid. In

formulating their response, this student likely confused xylenes with drying agent such as

either magnesium sulfate or sodium sulfate they had used in prior experiments to remove

water from an organic phase. This is supported by the statements such as it is a fine

powder and if any moisture gets in it, it will clump. Although these statements would

be true of the drying agents listed above, it is not true of xylenes. Consequently, this

students response was considered to represent a lack of a mechanistic understanding

with mechanistically incorrect statements.

5.3.5 Student Understanding of Methods to Dry Xylenes

Although organic solvents are generally immiscible with aqueous solutions, some

are able to dissolve significant amounts of water due to their polarity. For example,

diethyl ether dissolves approximately seven percent of its weight in water while

tetrahydrofuran is completely miscible with water. Consequently, water must be

removed from organic solvents that are used in reactions where water sensitive reagents

and reactants are employed. Traditionally, anhydrous solvents for use in the organic

synthesis laboratoratory are prepared by a distillation process that removes the solvent

from an active metal such as sodium or metal hydride. However due to the risk of fires

or explosions in the laboratory when this method is used, alternative methods and

desiccants are also used. For example, Grubbs developed a convenient method of

generating anhydrous solvents by passing bulk solvent through cartridges of highly

activated alumina as the desiccant. Other drying agents used to dry organic solvents
 159

include those that react with water chemically such as phosphorus pentoxide (P2O5),

calcium hydride (CaH2), and sulfuric acid (H2SO4). Drying agents that sequester water

such as molecular sieves are also commonly utilized. Molecular sieves are composed of

alkali aluminum silicates [Na12(Al12Si12O48)] with specific pore sizes that only permit

water to penetrate) and are useful with essentially any solvent.

The authors of the course textbook do not provide a discussion of the various

techniques used to prepare anhydrous organic solvent for use in synthetic organic

reactions that are moisture sensitive. However, the authors of the course textbook do

provide a discussion of drying agents for use in solvent extraction techniques. In their

discussion the authors of the course textbook state organic extracts separated from

aqueous phases usually contain traces of water...organic extracts must therefore be dried

to remove any residual water before the solvent is evaporated or further purification is

performed. The authors of the course textbook then discuss how anhydrous inorganic

salts such as sodium sulfate (Na2SO4), magnesium sulfate (MgSO4), and calcium chloride

(CaCl2) remove water from an organic extract by absorbing water to form insoluble

hydrates that may be removed by filtration or decanting. A table listing the properties of

common drying agents such as sodium sulfate, magnesium sulfate, calcium sulfate,

calcium chloride, silica gel, and molecular sieves is then provided followed by a brief

discussion of each of the drying agents.

To investigate students mechanistic understanding of how water is removed from

organic solvents that are used in reactions that require anhydrous conditions, students

were asked how xylenes could be dried. Nonpolar aromatic hydrocarbons such as

benzene, toluene, and xylenes are typically pre-dried by placing them over calcium
 160

chloride. Water is further removed by fractional distillation with rejection of the first 5-

10% of the wet forerun. However, in their responses, students provided a variety of

answers that demonstrated they held a wide range of understanding with respect to how

traces of water could be removed from xylene. Consequently, responses provided by

students were organized into one of the four themes of (1) distillation, (2) drying agent,

(3) oven, and (4) desiccators depending the technique discussed by the student in their

response (see Appendix B, Table 5.11).

5.3.5.1 Distillation

The first theme of distillation was found in the responses of five students who

responded xylenes could be dried by the use of technique of distillation. Although none

of the three students specified the technique used as fractional distillation, the responses

provided by these five students could be differentiated with respect to whether or not the

student also responded xylenes could also be dried by the use of a drying agent and what

drying agent the student suggested should be used. Consequently, student responses were

again organized into the three subthemes of: (1) distillation only, (2) molecular filter, and

(3) drying agent depending upon what the student stated how xylenes could be dried.

5.3.5.1.1 Distillation Only

The first subtheme of distillation only was found in the responses of three

students who answered xylenes could be dried by distillation. Although each of the

students demonstrated understanding xylenes could be dried by distillation, none of the

three students discussed the process used would actually be fractional distillation with
 161

rejection of five to ten percent of forerun. In addition, none of the three students

discussed pre-drying xylenes with calcium chloride prior to distillation in their answers.

For example, one of the three students responded I would distill it in the presence of N2

so that it would be less likely to catch on fire but still separate the H2O and xylenes.

Because the authors of the course textbook do not discuss the technique of distillation as

a method to dry solvents, this student likely based their response upon experiences

participating in undergraduate research. In contrast to the first student, another of the

three students simply responded xylenes can be dried through distillation while the

remaining of the three students responded dry by distilling the solvent. Although these

three students did not demonstrate a complete understanding of the distillation process

used to dry xylenes, their response did not contain misconceptions. Consequently, the

responses provided by these three students were considered to represent an partial

mechanistic understanding with no mechanistically incorrect statements.

5.3.5.1.2 Molecular Filter

The second subtheme of molecular filter was found in the response of one student

who answered the xylene can be dried by distillation or a molecular filter. Similar to

the previous three students, this student also failed to discuss that the distillation process

used would actually be fractional distillation with rejection of five to ten percent of

forerun or that xylenes would be pre-dried with the use of a drying agent such as calcium

chloride prior to distillation. However, the student did correctly discuss xylenes could

also be dried by placing it over molecular sieves Although this student did not

demonstrate a complete understanding of the distillation process used to dry xylenes,

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their response did not contain misconceptions. Consequently the answer provided by this

student was also considered to represent a partial mechanistic understanding with no

mechanistically incorrect statements.

5.3.5.1.3 Drying Agent

The third subtheme of drying agent was found in the response of one student who

answered to dry xylene you need to either distill it or add a drying agent to soak up the

water. Similar to the previous four students, this student also failed to discuss the

distillation process used would actually be fractional distillation with rejection of five to

ten percent of forerun or that xylenes would be pre-dried with the use of a drying agent

such as calcium chloride prior to distillation. However, the student did correctly discuss

xylenes could also be dried by placing it over a drying agent to absorb water. Although

this student also did not demonstrate a complete understanding of the distillation process

used to dry xylenes, their response did not contain misconceptions. Consequently the

answer provided by this student was also considered to represent a partial mechanistic

understanding with no mechanistically incorrect statements.

5.3.5.2 Drying Agent

The second theme of drying agent was found in the responses of three students

who responded xylenes could be dried by the use of a drying agent. However, the drying

agents discussed by the students were those used for the removal of residual water from

organic phases generated from an aqueous workup of a reaction mixture rather than from

solvents. For example, one of the three students responded xylenes will be dried using
 163

a drying agent such as anhydrous sodium sulfate. In a similar manner, another of the

three students responded you dry xylenes by using the calcium drying agent. The

remaining of the three students responded it is possible to dry it using a powdered

drying agent then filtering it out or distillation. In formulating their responses, these

three students based their response upon their experience using either anhydrous sodium

or magnesium sulfate to dry an organic phase once it had been separated from an aqueous

phase during the workup of a reaction mixture. However, not one of the three students

discussed the use of fractional distillation with rejection of five to ten percent of forerun

preceded by pre-drying with the use of a drying agent such as calcium chloride before

distillation. Even so, none of the three students included misconceptions in their

responses. They simply inappropriately applied a correct mechanistic concept or

technique in answering the question. Consequently, the responses provided by these

three students were considered to represent a lack of a mechanistic understanding without

the inclusion of mechanistic incorrect statements.

5.3.5.3 Oven

The third theme of oven was found in the responses of three students who

erroneously responded xylenes could be dried by placing it in an oven (1 Corinthians

13:11 New King James Version). For example, one of the three students responded to

dry xylenes, xylenes should be put in the oven for 5 10 minutes. Another of the three

students provided a little more depth in their response by answering xylenes could be

dried by placing it in the oven and evaporating all the water. Likewise the remaining

of the three students answered xylenes is dried by heating in an oven and cooled in a
 164

desiccators to protect from atmospheric moisture. These three students based their

responses primarily on their previous experiences drying laboratory glassware in the

vacuum oven present in the back of the laboratory followed by cooling in a desiccator

immediately prior to use in moisture sensitive reactions such as the Grignard reaction.

However, the students responses demonstrate they did not understand organic solvents

such as xylenes are commonly dried by fractional distillation with rejection of five to ten

percent of forerun preceded by pre-drying with the use of a drying agent such as calcium

chloride. Furthermore, the responses provided by the students also reveal these three

students did not understand xylenes is an organic liquid with a lower vapor pressure than

water. Consequently, upon heating in an oven, xylenes would evaporate before water.

Because the responses provided by these three students included misconceptions, their

answers were considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

5.3.5.4 Desiccator

The fourth theme of desiccator was found in the responses of two students who

erroneously responded xylenes could be dried by using a desiccator. For example, one of

the two students answered put the flask in a flask and put it metal desiccators for 5-10

minutes. Likewise the other of the two students answered you can dry xylenes using a

desiccator. Similar to the previous three students, these two students based their

responses primarily on their previous experiences drying laboratory glassware in the

vacuum oven present in the back of the laboratory followed by cooling in a desiccator

immediately prior to use in moisture sensitive reactions such as the Grignard reaction.
 165

However, the students responses demonstrate they did not understand organic solvents

such as xylenes are commonly dried by fractional distillation with rejection of five to ten

percent of forerun preceded by pre-drying with the use of a drying agent such as calcium

chloride. Furthermore, the students responses also reveal these two students did not

understand xylenes is an organic liquid with a lower boiling point and vapor pressure

than water. Consequently, xylenes can not by dried by placing it in a desiccator.

Because the responses provided by these two students included misconceptions, their

answers were considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

5.3.6 Student Understanding of the Nature of Petroleum Ether

After the reflux period is complete, the reaction mixture is allowed to cool to

room temperature. Once at room temperature, the product is isolated from the reaction

mixture by the addition of toluene followed by the drop wise addition of petroleum ether.

Toluene is added to further dilute the reaction mixture in order to keep impurities such as

residual 3-sulfolene and maleic anhydride in solution. Petroleum ether, a mixture of

non-polar hydrocarbons, is added as an anti-solvent to precipitate the endo-cis-4-

cyclohexene-1,2-dicarboxylic anhydride product. However, neither in the discussion or

procedure sections of the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic

acid anhydride experiment do the authors of the course textbook provide an explanation

of how the addition of toluene and petroleum ether isolates the product anhydride from

the reaction mixture. Instead, the authors simply provide student with the following

procedure:
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Add 0.5 mL of toluene to the cooled solution, and then add petroleum
ether (60-80C) dropwise until a slight cloudiness persists. Roughly
0.25-0.35mL of petroleum ether will be needed. Reheat the solution
until it becomes clear and then cool it in an ice bath. During the
recrystallization step, the sides of the vial may have to be scratched
with a glass rod to induce crystallization. Collect the crystalline
product by vacuum filtration and wash the filter cake on the Hirsch
funnel with 0.5 mL of cold petroleum ether (60-80C). Do not wash
with an excess of the petroleum ether or a loss of product will result.

Although the nature of petroleum ether is not discussed by the authors of the

course textbook in either the discussion or procedure sections, one of the teaching

assistants did explain the nature of petroleum ether to the entire class immediately prior

to the pre-laboratory quiz upon being asked by one of the students. In their explanation,

the teaching assistant told students petroleum ether is not an actual ether but rather a

mixture of hydrocarbons that is available in different grades with different boiling point

ranges of 30 to 40C, 60 to 80C, and up to 120C. The teaching assistant also explained

to the students that what the authors of the course textbook are saying in the procedure

section is that petroleum ether with a boiling point range of 60 - 80C should be added

drop wise to the reaction mixture at room temperature until it becomes cloudy. After

cloudiness develops, the reaction mixture should then be heated to redissolve any solid

precipitate.

To investigate students understanding of reactants and reagents used in the

isolation of the Diels-Alder adduct 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride

product from the reaction mixture, students were first asked what is petroleum ether.

Students provided a variety of responses that demonstrated a wide range of

 167

understandings as to what petroleum ether is. Consequently, student responses were

organized into the four themes of: (1) a mixture of hydrocarbons, (2) a mixture of

alkanes, (3) ether, and (4) solvent depending upon the students discussion as to what

petroleum ether is (see Appendix B, Table 5.12).

5.3.6.1 Mixture of Hydrocarbons

The first theme of a mixture of hydrocarbon was found in the responses of two

students who demonstrated a mechanistic understanding of what petroleum ether is. In

their responses, these two students correctly answered petroleum ether is a mixture of

hydrocarbons. For example, one of the two students responded petroleum ether is a

mixture of organic compounds such as hydrocarbons like benzin. By responding in this

manner the student demonstrated having a deeper understanding of what petroleum ether

is than the information the teaching assistant had just discussed with the class

immediately prior to the pre-laboratory quiz or what (if any) is provided by the authors of

the course textbook discusses. Therefore, the response given by the student demonstrates

they had knowledge in regards to the chemical nature of petroleum ether prior to coming

to the laboratory. Because the response provided by this did not include misconceptions.

it was considered to represent a mechanistic understanding with no mechanistically

incorrect statements.

In contrast to the previous student, the other of the two students responded a

mixture of hydrocarbons not an actual ether. Although the students response is

mechanistically correct, their answer simply reflecting what the teaching had said

moments before. Therefore the response provided by this student did not demonstrate
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having an understanding of what petroleum ether is beyond what the teaching assistant

had explained immediately prior to the pre-laboratory quiz. However, the answer

provided by this student was mechanistically correct and did not include misconceptions.

Consequently the response provided by this student was considered to represent a

mechanistic understanding with no mechanistically incorrect statements.

5.3.6.2 Mixture of Alkanes

The second theme of a mixture of alkanes was found in the responses of two

students who also demonstrated an accurate understanding of the nature of petroleum

ether. In their responses, these two students stated petroleum ether was a mixture of

alkanes. For example, one of the two students simply responded it is a mixture of

alkanes. By responding in this manner, this student did not demonstrate an

understanding of the nature of petroleum ether beyond what the teaching assistant

discussed immediately prior to the quiz. However, the response provided by the other of

the two students of a mixture of alkanes obtained from distillation of crude oil

demonstrated a greater understanding of what petroleum is beyond that which was

discussed by the teaching assistant immediately prior to the pre-laboratory quiz. Because

responses provided by these two students were mechanistically correct and did not

include misconceptions, their answers were considered to represent a mechanistic

understanding with no mechanistically incorrect statements.

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5.3.6.3 Ether

The third theme of ether was found in the responses of four students who

answered petroleum ether is an ether even though the teaching assistant had immediately

prior to the pre-laboratory quiz had explained to the class that petroleum ether is not an

actual ether. For example, one of the four students answered petroleum ether is one of

the species of the ethers. Another of the four students responded dioctyl ether while

another of the four students responded petroleum ether is raw ether. The remaining of

the four student responded petroleum ether was ether R-C-O-R erroneously using an

abbreviation that suggested it was a ketone. Because the answers provided by these four

students demonstrated they did not have an understanding of the nature of petroleum

ether. Rather their responses consisted almost entirely of misconceptions. Consequently,

their responses were considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

5.3.6.4 Solvent

The fourth theme of solvent was found in responses of six students who identified

what petroleum ether was in terms of its function rather than its chemical composition.

In their responses, each of the six students answered petroleum ether was a solvent.

However, in their responses the five students defined how petroleum ether functions as a

solvent differently. Consequently the theme of solvent was divided into five subthemes:

(1) product not soluble at cold temperatures, (2) wash solvent, (3) organic solvent, (4)

volatile solvent, and (5) recrystallization solvent depending on how the student described

petroleum ether functioned as a solvent.

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5.3.6.4.1 Product Not Soluble at Cold Temperatures

The first subtheme of product not soluble at cold temperatures was found in the

response of one student who demonstrated a mechanistic understanding of how

petroleum ether assists in the isolation of the 4-cyclcohexene-cis-1,2-dicarboxylic acid

anhydride from the reaction mixture but not of the nature of petroleum ether. In their

response the student answered petroleum ether is a solvent that our product is not very

soluble in at cold temperatures. Although the response provided by the student correctly

discusses how petroleum ether is used in the Diels-Alder synthesis of 4-cyclcohexene-

cis-1,2-dicarboxylic acid anhydride, it does not answer the question of what is petroleum

ether. Consequently, the response provided by the student was considered to represent a

lack of a mechanistic understanding with no mechanistically incorrect statements.

5.3.6.4.2 Wash Solvent

The second subtheme of wash solvent was found in the response of one student

who also demonstrated a mechanistic understanding of how petroleum ether assists in the

isolation of the 4-cyclcohexene-cis-1,2-dicarboxylic acid anhydride from the reaction

mixture but not of the nature of petroleum. In their response, the student answered

petroleum ether is the solvent we will wash our product with. Although petroleum

ether is used as a wash solvent to rinse the solid product after it is collected by vacuum

filtration, its primary function is that of an anti-solvent to precipitate the product from the

diluted reaction mixture. Although the response provided by the student correctly

discusses one of the ways petroleum ether is used in the Diels-Alder synthesis of 4-

cyclcohexene-cis-1,2-dicarboxylic acid anhydride, it does not answer the question of

 171

what is petroleum ether. Consequently, the response provided by the student was

considered to represent a lack of a mechanistic understanding with no mechanistically

incorrect statements.

5.3.6.4.3 Organic Solvent

The third subtheme of organic solvent was found in the response of one student

who simply answered petroleum ether is an organic solvent. Although petroleum ether is

an organic solvent, the students did not demonstrate understanding petroleum ether is a

mixture of low molecular weight hydrocarbons that is available in different grades with

different boiling point ranges. Nor did the student demonstrate understanding petroleum

ether is primarily used as an anti-solvent in the Diels-Alder synthesis of 4-cyclcohexene-

cis-1,2-dicarboxylic acid anhydride. Consequently the response provided by this student

was considered to represent a lack of a mechanistic understanding with no

mechanistically incorrect statements.

5.3.6.4.4 Volatile Solvent.

The fourth subtheme of volatile solvent was found in the response of one student

who answered petroleum ether is a fairly volatile solvent. In their response, the student

was likely recalling what they had previously learned that a desirable characteristic of

solvents used in the isolation of products is that it should be volatile so to easily

evaporate from the product. However, although the grades of petroleum ether with low

boiling point ranges would be considered fairly volatile, grades of petroleum ether with

high boiling point ranges of up to 120C would not be very volatile. The student also did
 172

not demonstrate understanding petroleum ether is a mixture of hydrocarbons available in

different grades with different boiling points. Nor did the student demonstrate

understanding petroleum ether is used as an anti-solvent in the Diels-Alder synthesis of

4-cyclcohexene-cis-1,2-dicarboxylic acid anhydride. Consequently the response

provided by this student was considered to represent a lack of a mechanistic

understanding with mechanistically incorrect statements.

5.3.6.4.5 Recrystalization Solvent.

The fifth subtheme of recrystallization was found in the responses of two students

who answered what petroleum ether is in terms of the characteristics that make a solvent

a good solvent for recrystallization. Both of the two students discussed that petroleum

ether was a good solvent because the product was soluble in hot petroleum ether but

insoluble in cold petroleum ether. For example, one of the two students responded it is a

solvent in which our product is soluble in at high temperatures and insoluble at low

temperatures whereas the other of the two students responded a very volatile organic

solvent that the product is not soluble in at cold temperatures yet it is at higher

temperature. Although the responses provided by these two students correctly defined

petroleum ether in terms of a recrystallization solvent, the students did not answer the

question of what s petroleum ether. In addition, petroleum ether is used as an anti-

solvent rather than a recrystallization solvent. Consequently, the responses provided by

these two students were considered to represent a lack of a mechanistic understanding

with no mechanistically incorrect statements.

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5.3.7 Student Understanding of the Purpose of Petroleum Ether

Petroleum ether assists in the isolation of the 4-cyclohexene-cis-1,2-dicarboxylic

acid anhydride product from the reaction mixture by functioning as an anti-solvent. As a

mixture of hydrocarbons, petroleum ether possesses two characteristics that allows it to

function as an anti-solvent in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride. First, petroleum ether is miscible with the xylenes/toluene

solvent system present at the end of the experiment. Second, the anhydride product

produced in the Diels-Alder synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid

anhydride has limited solubility in petroleum ether at low temperatures. Consequently,

the slow addition of petroleum ether to the reaction mixture at reduced temperatures

causes the anhydride product to precipitate from solution. In this way petroleum ether

assists in the isolation of the 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride product

from the reaction mixture.

To further investigate students understanding of the role of reactants and reagents

in the Diels-Alder synthesis of the 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride,

students were asked how petroleum ether assists in the isolation of the anhydride product

from the reaction mixture. The responses obtained revealed students held a wide range of

understandings of how petroleum ether assists in the isolation of the product.

Consequently, student responses were able to be organized into the five themes of: (1)

product not soluble (precipitates) at cold temperatures, (2) product not soluble but

impurities are, (3) washes away impurities, (4) recrystallization solvent, and (5)

miscellaneous depending upon how the student discussed petroleum ether assisted in the
 174

isolation of the 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride product from the

reaction mixture. (see Appendix B, Table 5.14)

5.3.7.1 Product not Soluble at Cold Temperatures

The first theme of product not soluble (precipitates) at cold temperatures was

found in the responses of two students whose answers discussed the purpose of petroleum

ether in terms of being an anti-solvent in that the product is not soluble in cold petroleum

ether. For example, one of the two students responded the product will precipitate out at

low temperatures in a solution of petroleum ether while the other of the two students

responded petroleum ether is a solvent that our product is not very soluble in at cold

temperatures. The responses provided by these two students demonstrated an accurate

understanding that petroleum ether helps isolate the 4-cylcohexene-cis-1,2-dicarboxylic

acid anhydride product from the reaction mixture by functioning as an anti-solvent.

Because both of the students demonstrated an accurate mechanistic understanding of how

petroleum ether assists in the isolation of the anhydride product from the reaction mixture

without the inclusion of misconceptions, the responses provided by these two students

were considered to represent a mechanistic understanding with no mechanistically

incorrect statements.

5.3.7.2 Product not Soluble but Impurities Are Soluble

The second theme of product not soluble but impurities are was found in the

responses of three students who demonstrated a partial mechanistic understanding of how

petroleum ether assists in the isolation of the 4-cyclohexene-cis-1,2-dicarboxylic acid

 175

anhydride product from the reaction mixture. In their responses, each of the three

students demonstrated understanding petroleum ether functions as an anti-solvent by

answering the product of the reaction is not soluble in petroleum ether. For example, one

of the three students responded the product is not soluble in cold petroleum ether so

anything that solubilized was not part of the product while another of the three students

responded it will not dissolve the product but will dissolve other impurities, it is used to

purify the product. Likewise, the remaining of the three students responded it isolates

the product because the product is insoluble in it but organic impurities are not.

Although petroleum ether does function as an anti-solvent in the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride, the product is not

completely insoluble in petroleum ether. The authors of the course textbook

acknowledge this by cautioning students do not wash with an excess of the petroleum

ether, or a loss of product will result. In addition, each of the three students erroneously

stated the impurities are soluble in petroleum ether. However, the impurities present

including unreacted 3-sulfolene and maleic anhydride are dissolved by the addition of

toluene to the reaction mixture prior to the addition of petroleum ether. Consequently,

the responses provided by these three students were considered to represent a partial

mechanistic understanding with mechanistically incorrect statements.

5.3.7.3 Washes away Impurities

The third theme of washes away impurities was found in the responses of five

students who demonstrated a partial mechanistic understanding of how petroleum ether

assists in the isolation of the product anhydride in the Diels-Alder synthesis of 4-

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cyclcohexene-cis-1,2-dicarboxylica acid anhydride. In their responses, each of the

students answered petroleum ether assists in the isolation of the product anhydride from

the reaction mixture by functioning as a wash solvent. Although the product obtained by

vacuum filtration at the end of the experiment is washed by petroleum ether, the primary

role of petroleum ether as an anti-solvent to precipitate the product anhydride from the

reaction mixture. However, not one of the responses provided by the five students

discussed petroleum functions as an anti-solvent. For example, the responses provided

by two of the five students of it washes off any impurities and other organic (unwanted)

compounds and it can help isolate the products by washing out the organic substances

to help get the product do not contain misconceptions, they do not discuss petroleum

ethers use as an anti-solvent. Consequently, the answers provided by these two students

were considered to represent a partial mechanistic understanding with no mechanistically

incorrect statements.

In contrast to the previous two students, each of the three remaining students

stated that the 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride product was not soluble

in petroleum ether in addition to discussing petroleum ether washes away impurities. For

example, one of the three students responded the product is not soluble in cold

petroleum ether, but it will wash away contaminants from the product while another of

the three students responded it helps isolate by washing away any organics we dont

want when we wash the filter cake with cold petroleum ether. It has to be cold because

solubility is proportional to temperature (solubility decreases as temperature decreases).

Wont wash away any crystals already made.

 177

Similarily, the remaining of the five students responded petroleum ether is used

to wash the product with. Our product should not be soluble in it so the petroleum ether

washes away any unwanted material or impurities. However, as previously discussed,

the anhydride product is not totally insoluble in petroleum ether. Consequently, the

responses provided by these three students were considered to represent a partial

mechanistic understanding with mechanistically incorrect statements.

5.3.7.4 Recrystalization Solvent

The fourth theme of recrystallization solvent was found in the responses of four

students whose responses discussed petroleum ether in terms of being a recrystallization

solvent in the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride. In their responses, each of the four students answered the anhydride product

is soluble in petroleum ether at higher temperatures (warm or hot) but not in chilled

petroleum ether at lower temperatures. For example, one of the four students responded

it is used because the product is soluble in warm ether but not in chilled ether while the

another of the four students responded the product is soluble in hot petroleum ether but

not in cold ether. By dissolving and recystallizing we can trap waste organic in the

ether. Similarly another of the four students responded the product is not soluble in at

cold temperatures yet it is at higher temperatures. This property can help in isolating the

product while the remaining of the four students stated our product is soluble in at high

temperatures and insoluble at low temperatures. Although the students accurately

discussed how a recyrstallization solvent purifies a compound, the students did not

demonstrate understanding petroleum ether functions as an anti-solvent in the

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xylenes/toluene/petroleum ether solvent system. Consequently, the responses provided by

these four students were considered to represent a lack of a mechanistic understanding

without mechanistically incorrect statements.

5.3.7.5. Miscellaneous

The fifth theme of miscellaneous was found in the responses of four students who

responses demonstrated a variety of mechanistic conceptions with respect to how

petroleum ether assists in the isolation of the product 4-cylcohexene-cis-1,2-dicarboxylic

acid anhydride from the reaction mixture. For example, one of the four students

erroneously responded it can be used as a solvent to dissolve the unwanted products of

the reaction and leave the desired product. However, as discussed previously, the

xylenes/toluene solvent system dissolves the impurities while petroleum ether acts as an

anti-solvent to precipitate the product anhydride. Consequently the response provided by

this student was considered to represent a lack of a mechanistic understanding with

mechanistically incorrect statements.

Another of the four students erroneously responded petroleum ether is helpful to

isolate the polar product by stripping any organic solvent or unwanted compounds still

present. However, residual organic solvent is allowed to evaporate from the product

while the xylenes/toluene solvent pair carries away impurities. By responding in this

manner, this student did not demonstrate understanding petroleum ether use as an anti-

solvent to cause precipitation of the product anhydride. Consequently the response

provided by this student was considered to represent a lack of mechanistic understanding

with mechanistically incorrect statements.

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The response provided by another of the four students of petroleum ether helps

to form the cyclic form of product well. It removes the impurities of the product.

Petroleum ether is one of the species on the ether and used to wash the product during the

process of filtration was found in several unrelated concepts and many misconceptions.

For example, petroleum ether is not involved in the Diels-Alder 4+2 cycloaddition steps

of the reaction mechanism. In addition, petroleum ether does not remove impurities from

the product, rather it functions as an anti-solvent. Also, petroleum is not an ether but a

mixture of hydrocarbons. However, the student did correctly discuss its use to wash the

product a collection by vacuum filtration. Even so, because the response provided by this

student consisted primarily of misconception, their response was considered to represent

a lack of a mechanistic understanding with mechanistically incorrect statements.

The response provided by the remaining student of petroleum ether helps

isolating the product by reacting with the alkene or alkyne to form the product also

consisted of misconceptions. Similar to the previous student, this student also

erroneously stated petroleum ether would help in the 4+2 cycloaddition step of the

reaction mechanism. In addition, the response provided by this student did not

demonstrate they understood petroleum ether acts as an anti-solvent in the Diels-Alder

synthesis of 4-cylcohexene-cis-1,2-dicarboxylic acid anhydride. Because the response

provided by this student did not demonstrate they understood petroleum ether is used as

an anti-solvent but rather consisted of misconceptions, their response was considered to

represent a lack of a mechanistic understanding with mechanistically incorrect

statements.
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CHAPTER SIX
STUDENT INTEVIEWS

6.1 Student Responses to Pre-laboratory Quiz Questions

As part of the pre-lab assignment, students were required to provide a step-wise

mechanism for each reaction they perform. The course instructor believed that having

students write a step-wise mechanism provided a theoretical basis for each reaction and

helped students understand the experimental methodology. Unfortunately, simply having

students write a step-wise reaction mechanism does not mean students necessarily

develop an in-depth mechanistic understanding of the experimental procedure. Evidence

of this can be found by noting that students often provided a generalized reaction

mechanism, similar to that presented in textbooks used for the organic chemistry lecture

course that failed to address how the reaction system (reactants or starting materials,

reagents and solvents), and the experimental variables ( pH, temperature, concentration,

etc), interact to produce a result (yield, selectivity, purity, etc). As a result, students

rarely know the purpose of the various reagents used in the reaction, workup, and

isolation steps, nor the reasons for the various operations they perform. Consequently,

the act of providing a step-wise mechanism became an exercise in the use of arrow

pushing formalism rather than the development of a deep mechanistic understanding of

reactions performed in the organic chemistry laboratory. Because of the absence of a

deep mechanistic understanding of the reaction, students often did not understand what
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they are doing in the organic chemistry laboratory and feel as though they are not

learning.

6.1.1 Purpose of the 5% Sodium Hydroxide Solution in the

Williamson Synthesis of Methyl p-Ethyphenyl Ether

Buffys response to the first question of quiz three provides an illustration of the

consequences of a students lack of a mechanistic understanding of the workup and

isolation step of the Williamson synthesis of ethers. The question asks: What is the

purpose of washing the diethyl ether extracts of the reaction mixture with a 5% NaOH

solution? In her interview, Buffy said she actually didnt know the purpose of the 5%

NaOH washes because it was not discussed in the laboratory manual. Consequently she

made her best guess as to the purpose of the 5% NaOH washes.

I made something up. You know, I took an educated guess. Obviously

I just didnt write down whatever, but I felt like I should have known,
but I was never, it was never in the prelab. I was never asked a question
about that, and we hadnt done the final, I mean the final report is due
tomorrow. I never looked at that even when I wrote the final report this
was not in it at all.

To create her answer, Buffy took what she understood about the reaction to construct her

response that the 5% NaOH solution reacts with residual 4-ethyl phenol to make the

corresponding phenoxide ion that would subsequently react with residual methyl iodide

to make more product.

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Jody also noted that the laboratory manual did not discuss the purpose of washing

the diethyl ether extracts with a 5% NaOH solution nor the subsequent washing with

water. Consequently he argued that the 5% NaOH solution reacts any acid byproducts

with the base so that they can be removed with the rest of the aqueous layer and that the

subsequent water wash helps to remove any ions so that the final product is pure as

possible. The product is in the organic phase and everything not wanted is in the aqueous

phase which both represent guesses.

I guess that wasnt uhmit wasnt in the lab manualand you know
I was like you know, uhm it wasnt in here so you know so I just
guessed basically. Just an educated guess.

Because the information was not discussed in the laboratory manual, Buffy and Jody

made up their answers to the questions on quiz three based on what they understood

about organic chemistry and the reaction.

6.1.2 Use of Xylenes as Solvent for the Diels-Alder Synthesis of

4-Cylcohexene-cis-1,2-dicarboxylic Acid Anhydride

Students lack of an understanding of the mechanistic reasoning behind the choice

of a solvent for an organic reaction was seen in their responses to the first question of

quiz four that asked: What are the characteristics of xylenes that make it a good solvent

for the Diels Alder reaction as performed in the laboratory? Xylene was used as a solvent

in this experiment because its boiling point of 137-140C provides a reaction temperature

just high enough for the thermal decomposition of 3-sulfone to s-cis-1,3-butadiene and
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sulfur dioxide within 25 to 30 minutes to prevent excessively shifting the equilibrium

constant (Keq) of the reaction toward starting materials. Not having an understanding of

the mechanistic reasoning behind why xylene were used as a solvent for the Diels-Alder

reaction Jody answered the question by noting that xylenes are a non-polar aprotic

solvent, an answer based on what he had learned in the first-semester lecture organic

chemistry lecture course.

I knew that well Im pretty sure xylene is a nonpolar aprotic solvent

right? Yea, I knew, that was the only fact I knew about it, uhm, so I
missed, I guess they wanted more characteristic than that (laughs).
Why would it be a good solvent because it was a non-polar aprotic but
I didnt really remember any of that from orgo one.

Some of the students answered the question that asks what characteristics of

xylenes make it a suitable solvent for the Diels Alder reaction as if they were choosing a

solvent for recrystallization, discussing criteria such: (1) as the product being soluble in

hot solvent but insoluble in cold solvent, (2) impurities are soluble in the solvent, and (3)

xylenes have a boiling point at least 10C lower than the melting point of the solute. In

my interviews with Buffy, I discovered that a possible explanation for the responses

provided by students to this question is that the one of the post-laboratory questions for

the final laboratory report for a previous experiment that students handed in to the

graduate teaching assistant just prior to the quiz that asked students to list the

characteristics of a good recrystallization solvent.

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John: One of the things I noticed is that first question when they were
asked about the characteristics of xylenes as a solvent, a lot of
students seemed to give answers that if you were choosing that
as a recrystallization solvent instead of like the reaction solvent.

Buffy: I didnt know the answer to that one (laughs). But uhm, yea the
recrystallization solvent was a question on the (previous) final
lab report.

John: Ahhh, ok on the (previous) final report. So thats why people were
thinking about that.

Buffy: Uh huh.

6.1.3 Need for Anhydrous Conditions in the Diels-Alder Synthesis of

4-Cylcohexene-cis-1,2-Dicarboxylic Acid Anhydride

Anhydrous conditions are necessary in the Diels Alder reaction to prevent

hydrolysis of maleic anhydride, the dieneophile used in the reaction. To investigate

students mechanistic understanding of why anhydrous conditions are necessary, the

second question on the fourth quiz asks why the xylenes used as the solvent in the Diels

Alder reaction must be dry. Responses provided by students revealed significant

confusion as to why anhydrous conditions are necessary. Like many students, Buffy was

confused about why the xylenes needed to be dry. Buffy thought the presence of water

would result in the hydrolysis of the xylenes instead of maleic anhydride.

Isnt it because it (xylenes) would go through hydrolysis if it came

into contact with (water)
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To maintain anhydrous conditions and prevent moisture from entering the experimental

apparatus, the reflux condenser used in the reaction was capped with a drying tube filled

with a desiccant: calcium chloride. Students lack of a mechanistic understanding of how

anhydrous conditions are maintained was indirectly revealed through their responses to

question 3(b) of the fourth quiz that asked why it is important to trap the sulfur dioxide

produced in the reaction and how would this be accomplished. In their responses, many

students incorrectly stated that the sulfur dioxide produced in the reaction would be

trapped by the drying tube filled with calcium chloride that was used to prevent moisture

in the air from entering the reaction apparatus.

6.2 Student Perception of a Lack of Learning in the

Organic Chemistry Teaching Laboratory

In the 2010 fall semester, when Buffy was enrolled in the first semester of a two-

semester organic chemistry laboratory course intended for students who majors were

chemical engineering; she had told me she did not like the organic chemistry teaching

laboratory. Consequently, during our first interview I took the opportunity to ask her

why she didnt like this course.

I just feel like Im not learning anything all the time. When Im
actually in lab, Im not always sure why am I doing this. I feel
like we were never told whats expected of us for outside of lab.
Just do the pre-lab, come in, and we are going to give you a quiz.
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In our interview Buffy discussed how she never feels prepared for the lab.

Although she studies the material about the experiment in both the laboratory manual and

the course textbook she still feels like she never knows what to expect.

I always feel unprepared when I walk in for the quiz even though
I sit there, I take notes on the prelab stuff and uhI highlight and
Ill reread it and reread it and reread it and hthe first semester I would
get like two out of ten on some quizzes and ten out of ten on others
and I never changed how I studied.so I never understood. Im
like oh my God what do I need to know for this quiz. I have no idea
what to expect. So I always feel like when I walk into lab I dont
know what to expect.

Buffy stated that one of her biggest frustrations with the organic chemistry laboratory

course is that the students are provided little guidance about what is important to know

and understand.

Buffy: So my thing is ok I can understand we are supposed to do a

little bit of homework outside of class beyond the lab reports
but we have no guidance to know what that is.

John: Whats important and whats not important

Buffy: Yea, yea. so I just I never never do anything besides the

pre-labs and the lab reports. I mean Ill go online and search
for stuff to answer the lab questions but Ive never gone
online and looked up why do I wash this or whats an
equivalent.
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In our interview Buffy continued to discuss her frustration that she wasnt being taught

what she needed to know to be successful in the laboratory.

I think the information on the quizzes you are testing us on is,

things that we, that should know based on the point of were in
organic chemistry, most of us are Chemical Engineers and this
is information that we need to know. But, were never learning it.

Buffy continued to express her sense of frustration about her feeling that she was not

learning organic chemistry.

The lab manual doesnt teach us, the TAs dont teach us, you dont
learn it in lecture. We, theres never ever a time when we see it
Its not even in the prereadings. I mean if it was in our lab manual
or if we had like an hour of lab lecture a week that might do
something, or once a month even.

Buffy stated that they were not being taught the reasons why various operations were

being performed in the laboratory and that what the course needed was something like a

weekly one hour lecture where student are taught the reasons why they were doing things

in the lab.

There should be something that tells us why we are doing things

cause I have no idea and weve washed stuff in organic one and
I didnt know how it was working or why so.

Because she didnt have a mechanistic understanding of the experiment and why she is

adding various reagents and performing various operations, Buffy felt like she was
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simply following a procedure. Consequenlty the experiments became a cookbook

exercise.

Buffy: Yea sometimes I feel like with lab you go in, and you get it
done, you leave, write your lab report.

John: Yea, like you said before you just fell like you are following a
procedure without really understanding whats going on.

Buffy: Right

In our interviews Buffy discussed how her initial experiences with infrared spectroscopy

in the organic chemistry laboratory is just one of many possible examples of how she

does a procedure or technique without understanding it.

I personally think that in (the first semester organic chemistry

course) we shouldnt be doing IR because I did not know what I was
looking at. I had no idea what it was, so I just kind of made
stuff up. I didnt know. So I feel like for if we are going to continue
to do IR, it should be explained the first time you use it. At least some
sort of theory

Because she dids not have a mechanistic understanding of the experiments she performed

in the organic chemistry laboratory course, Buffy felt that she was just going through the

motions in the lab.

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As far as understanding everything, yea we really need to be knowing

these basics before we do the lab or else. I feel like lab is just going
through the motions, Im not really learning anything that I can apply
to the real world. The only thing that forces me to learn more is the
quizzes. And if it wasnt for the quizzes I mean I would just go into
lab and do it and do the final lab report and usually you can find the
answers to the questions for the final online. So youre still even then
not learning as much.

In our interviews Buffy discussed with me that she does believe that it is important to

have a mechanistic understanding of the reactions and techniques used in the organic

chemistry teaching laboratory for her future career.

I think its important to understand for industry if you go into things

that have reactions so what kind of solvent would you use for this
when would you add this and to be able to understand that important
and if were not understanding that in basic labs then theres no
hope (laughs).

Because she believed that it is important for students to develop a mechanistic

understanding , Buffy suggested that students should be required to discuss the role of

reactants and reagents and why they perform various operations.

It should also be either a requirement to do that in your prelab like

maybe every couple of steps like say why you did certain things or
it should be a prelab questions because otherwise we are never going
to learn it because you know most of us I know ninety nine percent of
the people in lab this summer are chemical engineers and we have
other things to do so were not going to just look it up unless were
asked to, to be honest.
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6.3 Student Experiences in the Organic Chemistry Teaching Laboratory

At the end of the first day of the Diels Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride, the course instructor told me students had experienced

trouble with the experiment. Upon investigation I determined the primary difficult

students had in the execution of the Diels Alder synthesis was over-heating the reaction

mixture. Students looked at an illustration in the textbook used in the class which shows

a thermometer in the sand bath. The word thermometer was written in the illustration

along with 200C. The authors intended it to indicate a 200C thermometer was being

used. However, student misunderstood and instead of simply heating to the boiling point

of xylenes (139C) they tried to heat the reaction mixture to 200C. Buffy discussed the

problem of misunderstanding the temperature the reaction mixture should be heated too

by students.

Yesterday wasnt really that great of a day for anybodya lot of

people overheated their reaction when we were heating up for
twenty minutesso they burnt it

Buffy then discussed her reaction and the fact that the teaching assistant instructed her to

heat her reaction mixture for an additional 20 minutes because the thermometer in the

sand bath was only at 100C even though her reaction mixture was boiling indicating the

reaction mixture was at the correct temperature.

Uhm, and mine, I dont know, I didnt overheat itI kept it under 150
but the problem was that nobody knew what temperature we were
supposed to be at, cause it didnt say...and the teaching assistant didnt
 191

tell us until after half the class burned it, soI heated mine for 20
minutes but I think it was at 100 and he goes oh no youre supposed to
be between 130 and 140, so I said are you serious? And he said yea
you have to heat for another 20 minutes.

Buffy worried about the extra time she was required to heat her reaction mixture because

the textbook indicated students should be careful not to overheat the reaction mixture

because it would shift the equilibrium back towards starting material. In addition, Buffy

also observed the presence of a white solid in her reaction mixture when it was heated a

second time.

So I dont know what happened but we got some crystals but I think,
I dont know, there is, when we were heating it a second time, there
is a lot of white solid in it, and so we continued I.it heating at like
80.and I raised it to like 70 and swirled it around and eventually
the white solid went away, but then it came back pretty quickSo
there is white solid and crystals so I dont know if our characterization
is going to turn out that great.

I asked Buffy if she knew why people overheated the reaction mixture.

Like if they did it on purpose or.I think uhm the rumor in the lab
the teaching assistantI know the teaching assistant had said
something to me oh you have to use to use this thermometer because
it goes up to 200 degrees Celsius and I think people took that as
your reaction or you need to get it up to 200C so thats what some
people did. But I think they misinterpreted it. The teaching assistant
never actually said your sand bath needs to be thislike it was never
explicitly said so people heard a number and they thought that what
it needed to be.
 192

The students misunderstood that the thermometer in the sand bath was to simply measure

the temperature of the sand bath. Buffy seemed to recognize that the temperature of the

sand bath was not necessarily the temperature of the reaction mixture in the reaction

vessel.

John: And the temperature of your sand bath will not necessarily.

Buffy: Reflect whats the temperature in there yea

The sand bath simply had to be hot enough to get the xylenes to its boiling point, it did

not have to be at a specific temperature. However students overheated the sand bath and

reaction mixture even though they knew the textbook cautioned against it.

Yea because everybody was saying it did say not to overheat so people
remembered thatbut overheated it.

Buffy discussed how this was an example of confusion between what is written in the

textbook, the laboratory manual, what the students are doing in the laboratory and what

the teaching assistant is telling the students to do.

So a lot of times uhm they dont know what were supposed be, what
characterization were supposed to do that day verse the next day
because we do two day labs everytime and I dont know the teaching
assistant was confused about it one day. I said no this is what it says
exactly in the book like in our manuals and he said oh ok you know so.
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6.4 Student Perception of the Teaching Assistants

The teaching assistant has a central role with the instruction of students and the

direction of their daily activities in the teaching laboratory. Although the graduate

teaching assistants are occasionally a fourth- or fifth-year graduate student, they are more

likely to be a first- or second-year graduate student and sometimes are not even a member

of an organic chemistry research group. Most importantly though, teaching assistants are

not provided with training in regards to individual experiments and are not asked to

perform the experiments prior to working with the undergraduate students in the teaching

laboratory. Consequently, the graduate teaching assistants are often ill-prepared to assist

the students. In our interviews Buffy described how this often adds to student frustration

in the organic chemistry teaching laboratory.

Thats another thing I feel about lab, the teaching assistants

never seem to know the answers to our questions. And Im not
saying that they are stupid, but I feel like theres like a missing link
somewhere in the system. I mean sometimes the teaching assistants
dont even know if were supposed to do certain characterization tests.
So, I mean yesterday I asked my lab partner after labI said Oh, did
you do the solubility test she said nono one else is doing it so I
didnt. And I said ok (laughs).

Buffy discusses an instance where the teaching assistant told her that they had never

performed the experiment. Consequently the teaching assistant was unable to provide her

guidance.
 194

Which is exactly what happened yesterday Iyou know the teaching

assistant said hows it going" I said I dont know how does it look
and they said uh it looks Ok theyre like Ive never done this
experiment before. So they literally said I dont know what its
supposed to look like. When I showed him the white solid he goes
I have no idea.

During our interviews Buffy discussed how the drying of an organic layer over MgSO4 is

an example of a technique that she does not feel comfortable with because the

explanation provided by the teaching assistant to just look for the snow globe effect

didnt provide her with an understanding of how MgSO4 removes water from the organic

layer.

Ok, the drying of the organic layer over MgS04. I dont think Ive ever
done that before. I didnt understand what was going on when we did
it. I didnt you knowour teaching assistant said look for the snow
globe effect and once you see that youre good to goand were like
okay it looks like this. Theres a snow globe in there so I guess were
alright but we had no idea. You know what I mean? So, things like
this part needs to be explained more of what youre doing and why.
So we kept swirling and she goes it looks like snow globe were done
and I was but like I dont know is theres something more, it needed,
change color, I dont know.

However, as an example of a useful laboratory skill that should be taught to everybody in

the organic chemistry teaching laboratory, Buffy discussed how she and her lab partner

often experienced difficulty distinguishing between the aqueous and organic layers and

how the teaching assistant helped them distinguish between the two layers.
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It was even very difficult distinguishing which layer is which. In

every lab, every lab that we have two layers we all have difficulty
figuring out which is the organic layer and which is the aqueous layer.
The teaching assistant does not announce it but he came and helped
me and my lab partner and he said just add water, where does it go?
Thats your aqueous layer. He showed us that because we were like
really confused, we didnt really know what we had in this beaker
anymore. He said well just add water and then you can reseparate it.

Buffy stated she thought what the teaching assistant told her about how to distinguish

between the organic and aqueous layers was very helpful and thought that kind of

practical knowledge should be taught to everyone.

So that was really useful, I feel like thats some practical knowledge
that we should all know.

Because of her experiences with teaching assistants in the laboratory, Buffy suggested the

teaching assistants should be provided with a reference sheet that instructs them what to

have the student do under various circumstances.

Like I feel like there should be a.a list of common things that
happenthat could happen while the students are doing the lab
and what you should do if it happens so if you get a white solid
around this step because it commonly happened then you should
do this. Or if this is what it could beyou know...this is how you
figure out what it could be if you want to make the students do
more work, you know so I justthere should be something to...
if the TAs havent done the lab that they could at least reference.
 196

Buffy also stated she that she felt the teaching assistants should have experience with the

reactions so they are better able to guide students.

I hope that in the future the TAs are more experienced with the
experiments we are doing so that when something happens that I
didnt expect they can maybe say this is what it could be because
this and this is what you should do.

During our interviews I also asked Buffy if she found it helpful when the graduate

teaching assistance goes over the mechanism of the reaction with students.

Yea, I mean I already had the mechanism but I didnt.I think its
helpful that they do that because now all of it..not every lab do I
get the correct mechanism when I try and figure it out or try and look
it up. So I think its helpful when they go over whats happening so
that when you do it your like ok this is happening right now so I
really need to make sure I get it all stirred up.

I also asked Jody if he found it helpful when the graduate teaching assistance goes over

the mechanism of the reaction in the pre-laboratory lecture with students.

I remember last week uhmthe teaching assistant spend a lot of time

on stuff we already knewhe spent a lot of time on like SN2 reaction,
and so its like well were already pretty familiar with that from last
semester so I think it would help if they were more familiar with what
we knew and what we didnt know. Like the teaching assistants were
surprised that we didnt know anything about NMR and they didnt
really tell us very much about it you know. We were really trying to get
some answers out of them because we didnt know what it was. We
didnt even know what NMR stood for. So, that was difficult. And
 197

then they spent you know half an hour on a SN2 reaction and its like
well we already spent time on that so its the, its the you know we
already know this but we dont know this but they dont know that
we dont know any of it you know so.

6.5 Student Perception of the Relationship Between Lecture and the Laboratory

In our interviews, Jody brought up another common problem with the organic

chemistry laboratory course: Students are routinely to it perform reactions that have not

been discussed in the lecture course. I asked Jody if he felt this made working in the

organic laboratory more difficult.

Yea, it makes it harder to understand whats going on

I asked Jody if he thought that doing the Williamson synthesis of ethers in the organic

chemistry teaching laboratory before it was covered in lecture was helpful or if he

thought it would have been better to learn about it in lecture first before he did the

laboratory experiment

Just because of the way grading works I would prefer to have it in

lecturethan to have it in lab because if I have it in lecture first
then Im not graded on it until I have the test but if I have it in lab
they are just going to say you know were performing Williamson
ether synthesis and its an SN2 reaction. But in lecture you know
were going to spend, you know half an hour on that or something.
I can read it in the book and I can see itIll see it ten times before
Ill have to actually write a lab report about it or something like that.
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Jody discussed how he appreciated our interviews because I would take the time to go

over the experiments in detail with him.

Its enlightening for me, so, you know, I mean, things like today, they
dont explain it. Talking through it is really helpful. Soput, put it
somewhere, where we can find it. A lot of this stuff, you know, I can
spend hours on the internet looking at journals or just googling stuff
and Ill find one article that is, you know, like the Moscher approach.
Like I found one, one thing that was close but, it didnt have any of
the same reagents in it. So, everything had a different use than what
we were dealing with so it didnt really help with anything I was
trying find.

I asked Buffy if she thought there was a connection between the material being covered

in the lecture course and the experiments being performed in the laboratory and if the two

courses complimented each other.

Yea, or else I wouldnt have been able to do this. I feel this is doing
a lot, organic two lab is matching up with lecture better than organic
lab one did.

I then asked Buffy if she thought the lecture helped her understand the laboratory better

or if the laboratory experiences help her understand the lecture

In this case I think the lecture helped me understand the lab more for
the Friedel-Crafts. But going back to the first lab, the lab (NMR)
helped me understand the lecture more but had we learned it in lecture
first I think it would have been the other way around.
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6.6 Student Perception of Course

During my interviews with students in which their responses to questions posed

on the pre-laboratory quizzes were discussed, students often talked about the organic

chemistry laboratory course as a whole. Comments provided by students in their

discussions of the course provided much insight into what they liked and found helpful

and what they disliked and found frustrating during the semester. In this section, I will

present and discuss vignettes from my interviews with students that exemplify what

students liked and found helpful and what students disliked and found frustrating in the

course. During our interviews, I asked Buffy about how she felt about the course overall

Well, its definitely an improvement from 263working with the

(lecture) class and figuring out when to do labs is a good, a really
good way to do it. Cause it helps. It was a lot of work for a one
credit hour class though I have to say. And a lot of people are really
upset about it. Two credit hours would be nice. I feel like 263 is
good for one, but if you kept the amount of work we had to do the
same for 264 and then like with the quizzes and all that, then, and the
presentations and the paper and the final exam, I think it should be
worth two. I take some one-credit hour classes and this was like a
lot of work. Cause you have prelabs and final lab reports, a paper
and then lab eight in general, trying to do that on your own, a
presentation and a final exam.

In our last interview, I asked Buffy in what ways could the organic chemistry laboratory

course be improved.

The lab manual in general needs to be tossed. (laughs)

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I then asked Buffy what she didnt like about the lab manual? Her reply indicated that it

did not explain what was going on in the experiments nor provide her with a mechanistic

understanding of the experiments she wished she had.

Its just like what we always talk about. It does not explain concepts its just do it
and then were going to ask you these quiz questions that you should know the
answers to, but you dont. Because the lab manual sucks. So, I would definitely
improve the lab manual and I would, like, I would look into adding a credit hour
because then you could then justify it with adding a lecture, a lab lecture.
Because, I think it would really be helpful for people going into research.

In addition to getting rid of the laboratory manual, Buffy suggested that the quizzes

should be eliminated and the questions used as a prelab assignment instead.

Because that forces people to get up and get it right instead of oops
got two out of twenty on the quiz. That sucks, its like curved. You
know.
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CHAPTER SEVEN

CONCLUSIONS

7.1 Introduction

The constructivist theory of knowledge suggests that learners do not simply

mirror and reflect what they read (von Glaserfeld, 1989). Rather, learners construct their

own understanding by searching for meaning and attempting to find regularity and order

in their experiences even in the absence of full or complete information. Unlike

traditional educational perspectives that placed the responsibility of learning on the

instructor who teaches a passive and receptive learner, constructivism emphasizes the

importance of understanding that the learner is actively involved in the learning process.

Learning is a reconstruction rather than a transmission of knowledge where individual

learner constructs mental models that allow them to understand the world (Sabelli, 2008).

7.2 Characteristics of Student Responses

When instruction was explicitly given students were observed to construct

understanding of how the interaction between a reaction system and experimental

variable provides a result of interest for an experiment performed in the organic

chemistry laboratory through the synthesis of mechanistic concepts from three principle

sources: mechanistic concepts provided by either the laboratory course textbook or the
 202

graduate teaching assistant, mechanistic concepts they had been exposed to elsewhere,

and their experiences with techniques and procedures used in the organic chemistry

laboratory. Even in the absence of explicit instruction, students were observed to

construct understanding of how the interaction between a reaction system and

experimental variable provides a result of interest for an experiment performed in the

organic chemistry laboratory through the synthesis of mechanistic concepts from only

two of the principle sources list above: mechanistic concepts they had been exposed to

elsewhere, and their experiences with techniques and procedures used in the organic

chemistry laboratory. The extent to which a student was able to synthesize concepts from

these sources into a response that directly answered the question posed on a pre-

laboratory quiz, that was mechanistically correct, and was sufficiently complete

determined whether the response provided by the student demonstrated a mechanistic

understanding, partial mechanistic understanding, or a lack of a mechanistic

understanding.

Students who demonstrated a mechanistic understanding that was essentially

correct were able to incorporate one or more correct mechanistic concepts from the

sources listed above into a response that directly answered the question posed on the pre-

laboratory quiz that was mechanistically correct, and sufficiently complete. Often, these

students demonstrated a greater depth of mechanistic understanding than that provided by

the textbook or graduate teaching assistant by including mechanistic concepts not

provided by either source. Even though the responses provided by these students

demonstrated a mechanistic understanding, their answers would occasion include

mechanistically incorrect statements.

 203

Students who provided responses that demonstrated a partial mechanistic

understanding gave answers that, although mechanistically correct, often did not directly

answer the question posed on the pre-laboratory quiz or were not sufficiently complete.

Responses provided by these students typically consisted of only one principle

mechanistic concept that was often stated in broad and generalizable terms. These

students did not demonstrate a greater depth of mechanistic understanding than that

provided by the textbook or graduate teaching assistant and also occasionally included

mechanistically incorrect statements in their responses.

A third catgory consisted of responses from students that demonstrated a lack of a

mechanistic understanding and therefore gave answers that consisted of one or more

mechanistic concepts that did not correctly answer the questions posed on the pre-

laboratory quizzes. The concepts provided by these students were often specific and

mechanistically correct in themselves, but were not appropriate as responses to the

question asked on the pre-laboratory quiz. By responding in this manner, these students

demonstrated not understanding the concepts about which the question asked and the

concepts they provided in their response. As was observed in the responses of the

previous two groups of students, these students also occasionally included

mechanistically incorrect statements in their responses.

 204

7.3 Student Perceptions of the Lack of Learning

Comments made by students during the interviews suggested that they did not feel

they were learning in the organic chemistry laboratory course. This perception may be

attributed to several factors. First, students felt as if they were not provided with

guidance in regards to what is important to know and understand. Students therefore felt

unprepared for the laboratory and reported not knowing what to expect even though they

put a lot of time and effort into studying the material provided in the laboratory textbook

and laboratory manual.

Another reason students felt as though they were not learning anything in the

organic chemistry laboratory may be understood by noting that the students felt they were

not being taught the reasons why various reactants and reagents are used in the

experiments or why various operations were performed. Consequently the students failed

to develop a mechanistic understanding of the reactions they perform in the laboratory.

Because they did not understand what they are doing in the organic chemistry laboratory

or why they were doing it, the students felt that they simply had to follow a recipe in a

cookbook manner without any understanding of why.

Interestingly, students expressed a desire for a greater understanding of the

experiments they performed and suggested that a one-hour lecture be provided where

students could be taught the reasons why they were doing things in the laboratory.

Students also discussed frustration with the graduate teaching assistants lack of

experience with the experiments performed in the laboratory. Because of the teaching

assistants lack of experience with the experiments, they were often unable to effectively

guide students in the laboratory and often unable to answer students questions.
 205

7.4 Assertions

Assertion One: The mechanistic discussions of the Williamson synthesis of methyl p-

ethylphenyl ether and the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-dicarboxylic

acid anhydride experiments provided in the course textbook were not sufficient to allow

most of the students to develop a mechanistic understand how the interactions between

the reaction systems and experimental variables provided a result of interest in the

organic chemistry laboratory.

For example, the discussion in regards to the Williamson synthesis of methyl p-

ethylphenyl ether in the course textbook does not explain how the reaction system or

experimental variables used specifically determines the mechanistic pathway followed in

the experiment. Instead, the textbook discusses the mechanism of the reaction as a

classic SN2 process that involves backside nucleophilic attack of the phenoxide anion on

the alkyl halide and where at least one of the carbons on the resulting ether product is

primary or methyl. Consequently, only two of the students demonstrated an

understanding that it was the use of methyl iodide as the alkyl halide that necessitated

that the reaction follows an SN2 mechanistic pathway. Most of the students provided

mechanistic arguments in their responses that were a consequence of the reaction

following a SN2 pathway such as backside attack, substitution, one step concerted

reaction, and release of iodide.

Similarly, the mechanistic discussion provided for the Diels-Alder synthesis of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride only describes the reaction in general

terms that do not specifically address how the reaction system and experimental variables

used in the experiment interact to provide a result of interest. For example, the course
 206

textbook discusses the Diels-Alder reaction as a [4+2] thermal cycloaddition between a

conjugated 1,3-diene and alkene where: The diene must be in the s-cis conformation, the

equilibrium constant of the reaction is dependent on temperature, the reaction is highly

stereospecific with the orientation of the groups on the dieneophile retained in the

product, and that the endo adduct is generally preferred over the exo adduct.

Consequently, when asked why xylenes were used as a solvent for the reaction, none of

the students demonstrated an understanding that xylenes was used as a solvent because its

boiling point is high enough so that the rate of the reaction is fast enough to be completed

within twenty- to thirty-minutes allowing students to complete the experiment in the two-

and-a- half hour laboratory period.

Assertion Two: When explicit instruction was provided, students tended to provide

responses that demonstrated either a partial mechanistic understanding or a lack of a

mechanistic understanding of how interactions between the reaction system and

experimental variables provided a result of interest in the organic chemistry laboratory.

For example, most of the discussion in regards to the Williamson synthesis of

methyl p-ethylphenyl ether in the course textbook consisted of a description of the phase

transfer catalysis conditions and the role of the phase transfer catalyst. In their

discussion, the authors of the course textbook explained that the phase transfer catalyst

carries the phenoxide ion from the aqueous phase to the organic phase as an ion pair.

After reaction occurs, the iodide displaced from methyl iodide is transported to the

aqueous phase as the halide salt. However, when asked to discuss the role of

tetrabutylammonium bromide in the Williamson synthesis of methyl p-ethylphenyl ether,

 207

none of the students provided a response that demonstrated a complete mechanistic

understanding. Most of the students demonstrated a partial mechanistic understanding by

responding it carried the phenoxide ion from the aqueous phase to the organic phase but

also believed it carried the iodide from the organic to the aqueous phase. The students

also frequently reported that the phase transfer catalyst carries the phenol instead of the

phenoxide ion suggesting they did not understand the phase transfer catalyst carries 4-

ethylphenoxide as an ion pair from the aqueous to the organic phase.

In the discussion section of the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride, the authors of the course textbook state that the diene used

in the reaction, 1,3-butadiene, is a gas at room temperature which makes it difficult to

handle and measure. Consequently, 3-sulfolene, a solid at room temperature that is easier

to handle and measure, is used instead because it decomposes at moderate temperature to

give 1,3-butadiene. However, when asked why 3-sulfolene was used in the experiment

rather than 1,3-butadiene, only three of the students responses demonstrated a

mechanistic understanding. Most of the students provided a response that only discussed

one of the concepts presented in the textbook such as 1,3-butadiene is gas at room

temperature, 1,3-butadiene is difficult to handle or measure, or 3-sulfolene may be used

as a source of 1,3-butadiene.

Assertion Three: In the absence of instruction, students may use mechanistic concepts

they had learned elsewhere or through their experiences with techniques and procedures

in the organic chemistry laboratory from prior experiences to provide a response that

demonstrated mechanistic understanding of the experiment

 208

For example, the purpose of the 25% sodium hydroxide solution in the

Williamson synthesis of methyl p-ethylphenyl ether was not explained in the discussion

section of the experiment in the course textbook. However, six students provided a

response that demonstrated a mechanistic understanding of the role of the 25% sodium

hydroxide solution in the experiment. These students based their responses upon their

knowledge of and experiences with using sodium hydroxide to answer the 25% sodium

hydroxide solution is used as a base to correctly respond that it is used to deprotonate 4-

ethylphenol.

Assertion four: In the absence of explicit instruction, students often use mechanistic

concepts they had learned elsewhere or through their experiences with techniques and

procedures in the organic chemistry laboratory to provide a response that demonstrated

an incorrect mechanistic understanding of the experiment

Although the textbook provides students with a step by step procedure for the

isolation of the crude product in the Williamson synthesis of methyl p-ethylphenyl ether,

the authors did not explain how the steps assist in the isolation of the desired product.

For example, the students were not told that the wash of the combined diethyl ether

extracts with a 5% sodium hydroxide solution was used to convert excess methyl iodide

into its water soluble sodium methoxide salt. Consequently, when asked to discuss the

purpose of the wash of the combined diethyl ether extracts with a 5% sodium hydroxide

solution, students were unable to provide mechanistically correct responses. However,

some students based their responses upon mechanistic concepts that they had learned

elsewhere or through their experiences with techniques and procedures in the organic
 209

chemistry laboratory. For example, six of the students based their responses upon their

understanding of the use of sodium hydroxide as a source of a basic hydroxide anion by

responding that it would either deprotonate or react with acidic species. These six

students based their responses upon their understanding and use of sodium hydroxide as a

base rather than a source of nucleophilic hydroxide. In a similar manner, two of the

students responded that the 5% sodium hydroxide would remove any water that may be

present. Another one of the students responded the 5% sodium hydroxide solution helped

in the separation of the organic and aqueous phases. These three students incorrectly

based their responses upon their experiences with the use of a saturated brine solution to

remove traces of water from an organic phase and help in the separation of layers..

Assertion five: Students used mechanistic concepts based upon their experiences with

techniques and procedures in the organic chemistry laboratory to provide a responses to

questions asked on the prelaboratory quizzes instead of the mechanistic concepts

presented in the course textbook.

In the discussion section of the Diels-Alder synthesis of 4-cyclohexene-cis-1,2-

dicarboxylic acid anhydride, the authors of the course textbook state that malic anhydride

should be protected from moisture to prevent hydrolysis. Consequently, freshly distilled

xylene should be used. However, when asked how the xylenes used in the experiment

should be dried, several students provided responses that were based upon their

experiences in the organic chemistry laboratory rather than concepts presented in the

course textbook, Several students, for example, responded that xylenes should be dried

using drying agents such as magnesium or sodium sulfate, both of which are commonly
 210

used to dry an organic phase during the isolation of product steps of an experiment.

Other students responded that xylenes could be dried by placing it in an oven followed by

cooling in a desiccator. These students based their answers upon their experiences drying

glassware prior to its use in moisture sensitive reactions.

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APPENDICES
 221

Appendix A

Guided Inquiry Experiment by Technique of Characterization

Table A2.2.Synthetic and Preparative Guided Inquiry Laboratory Activities

by Technique of Characterization

Technique References

Melting Point Determination Adrian & Hull, 2001; Holden & Crouch, 2001;
McGowens & Silversmith, 1998; Pickering, 1990a,
1990b; Silversmith, 1991; Todd, 1992; Todd &
Pickering, 1988.

Infrared Spectroscopy Duarte, Nielsen, & Dragojlovic, 2004; Pelter,

Macudzinski, & Passarelli, 2000.

Infrared Spectroscopy and Silversmith, 1991

Melting Point Determination

Nuclear Magnetic Cooley & Williams, 1997; D. R. Crouch, Holden, &

Resonance Spectroscopy Weaver, 1998; R. D. Crouch & Holden, 2002; R. D.
Crouch, Holden, & Romany, 2004; R. D. Crouch &
Nelson, 1995; Gingrich & Pickering, 1991; McElveen,
Gavardinas, Stamberger, & Mohan, 1999; Saba,
Ciaccio, Espinal, & Aman, 2007; Wachter-Jurcsak &
Reddin, 2001.

Melting Point Determination J. A. Ciaccio, 1995; J. A. Ciaccio et al., 2001; J. A.

and Nuclear Magnetic Ciaccio, Volpi, & Clarke, 1996; Jarret, New, Hurley, &
Resonance Spectroscopy Gillooly, 2001; Sgariglia, Schopp, Gavardinas, &
Mohan, 2000; Shadwick & Mohan, 1999; Silversmith,
1998.

Infrared and Nuclear Breton, 1999; Centko & Mohan, 2001; James A.
Magnetic Resonance Ciaccio, Guevara, Alam, & D'Agrosa, 2010; Cooley,
Spectroscopy 1991; D. R. Crouch et al., 1998
 222

Table A2.2. continued

Technique References
Gas Chromatography and Gail Horowitz, 2009; Latimer, 2003; Pearsall et al.,
Nuclear Magnetic 1995; Cabay, Ettlie, Tuite, Welday, & Mohan, 2001;
Spectroscopy Cawley & Lindner, 1997; Pienta, Crawford, & Kropp,
1993.
Gas Chromatography/Mass Jarret & McMaster, 1994; Jarret, New, & Patraitis,
Spectrometry 1995; John J. Nash, Leininger, & Keyes, 2008; M.
Novak & Heinrich, 1993; M. Novak, Heinrich, Martin,
Green, & Lytle, 1993; Padias & Baron, 1998.

Infrared Spectroscopy, Bendorf & McDonald, 2003; Cook & Kreeger, 2000;
Nuclear Magnetic Krishnamurty, Jain, & Samby, 2000; McDonald, 2000;
Spectroscopy, Mass Moroz, Pellino, & Field, 2003; Mosher, Kelly, &
Spectrometry Mosher, 1996

Molecular Modeling and Poon, Bodolosky, & Norris, 1999.

Melting Point Determination

Molecular Modeling, (Graham, Skoglund, Schaller, Muldoon, & Klassen,

Infrared Spectroscopy, and 2000; Klassen, Graham, & Muldoon, 1999)
Gas Chromatography

Molecular Modeling and Hull, 2001b

Nuclear Magnetic
Spectroscopy
 223

Appendix B

Student Responses to Pre-Laboratory Quiz Questions

Table B5.1 Student Mechanistic Classification of the Williamson Synthesis

of Methyl p-Ethylphenyl Ether

Theme Student Statement Code

SN2
Methyl or It is a SN2 reaction since it is a primary Mu/nm
primary alkyl carbon on the methyl iodide or other
halide haloalkane that is being attacked. If it
was a secondary or tertiary carbon then it
would most likely be an E2 reaction since
phenoxide is a base.
It is an SN2 reaction if the carbon is Mu/nm
methyl or primary. It is an E2 reaction if
the carbon is secondary or tertiary. We
will use SN2 for this lab.

Backside attack
backside attack Backside attack. Pmu/nm
SN2 because it takes place with a backside Pmu/nm
nucleophilic attack.

substitution SN2 substitution reaction mechanism. It Pmu/nm

involves backside attack of a methyl group.
Williamson ether synthesis is a SN2 Pmu/nm
reaction ie. bimolecular nucleophilic
substitution since the alkoxide attacks the
back end of the alkyl-halide
 224

Table B5.1, continued

Theme Student Statement Code

SN2 because the oxygen of the 4-ethyl Pmu/wm
phenol back attacks the methyl iodide and
the 4-ethylphenol is substituted for
where the iodide was.

formation of It is an SN2 reaction. The phenoxide ion Pmu/nm

iodine attacks the methyl iodide from the
backside. This causes the iodine to form
an ion and the product to form.

Nucleophilic SN2 The electron from the O attacks the Pmu/nm

attack releases carbon releasing the iodine.
iodine SN2 The 4-ethylphenol ion acts as a Pmu/nm
nucleophile and attacks the methyl iodide.
The iodine is a good leaving group which
allows the reaction to take place.

One step SN2 reaction. Simultaneous reactions (one Pmu/nm

reaction step). One primary product is formed from
two reactants

Substitution Substitution reaction Pmu/nm

The reaction is an SN2 substitution reaction Pmu/wm
because a proton is removed to make way
for a methyl group.
It was a SN2 reaction. The NaOH is Pmu/wm
substituted in the reaction
The reaction is an SN2 reaction. This can Pmu/wm
be seen because the OH group is attached
to a tertiary carbon and the iodide is
attached to a methyl carbon allowing for
nucleophilic attack for substitution.
 225

Table B5.1, continued

Theme Student Statement Code

SN2 with no SN2 Lmu/nm
discussion SN2 Lmu/nm

Intermediates SN2 reaction because there are Pmu/wm

intermediates and substitutions
 226

Table B5.2 Student Understanding of the Purpose of the

25% Sodium Hydroxide Solution

Theme Student Statement Code

Deprotonation
4-ethylphenol NaOH is actually Na+ OH- and the OH- ...Mu/nm
removes the hydrogen from 4-ethylphenol
in the first step of the mechanism.
The NaOH dissociates into Na+ OH- and Mu/nm
the OH-pulls the hydrogen off of the 4-
ethylphenol so that it may react with the
methyl iodide.
NaOH provides the OH- group to attach to Mu/wm
the H+ in the 4-ethylphenol and leave as
H2O. This leaves the negative charge on
the oxygen to do SN2.
It removes the H from the OH group Mu/nm
on the 4-ethylphenol

phenol It is used to remove the H from the phenol Mu/nm

to create a phenoxide ion that will allow
the reaction to proceed.
The hydroxide in NaOH acts as a base to Mu/nm
remove a proton from the phenol OH.

unspecified The nucleophilic NaOH is used to strip off Pmu/wm

the hydrogen to make room for the methyl
group becoming Na+ and H2O.

To produce basic To provide basic conditions for the Pmu/nm

environment. experiment.
Provides a basic environment so the Pmu/wm
hydroxyl group can leave the 4-ethyl
phenol and then can the 4-ethylphenol
continue the reaction.
 227

Table B5.2, continued

Theme Student Statement Code

Creation of a NaOH is used in order to create a negative ...Pmu/wm

nucleophile charge on the 4-ethylphenol in order for
it to be able to do a backside attach
methyl idodide and in order for iodide to
come off easily to form Na+, I- .
To provide OH for reaction (hydrolysis) ...Pmu/wm
so the O would have available electrons
to bond to the methyl group.

Catalyst Catalyst Lmu/nm

It is a catalyst to the reaction. It reacts the Lmu/nm
OH with the H from the reactant to remove
the H.
The NaOH is used to help remove the Lmu/wm
iodide from the methyl iodide. Basically
the NaOH is used to catalyze the reaction
and help it perform best.

Phase transfer It is a phase transfer catalyst and will Lmu/nm

catalyst bring the phenol ions across the phase
barrier
After the reaction has occurred the salt Lmu/nm
goes back to the aqueous phase and is
replaced by a new phenoxide so the
process repeats

Creates water and The hydroxide uses a proton to create Lmu/nm

Na+ salts waterand the Na becomes a salt ion
 228

Table B5.3 Student Understanding of the Purpose of Tetrabutylammonium Bromide

Theme Student Statement Code

Phase Transfer
Catalyst
transfers The tetrabutylammonium bromide is a Pmu/nm
phenoxide phase transfer catalyst and brings the
phenoxide ion into the organic phase from
the aqueous phase so it may react.
It is used as a phase transfer catalyst. It Pmu/nm
transports the phenoxide from the aqueous
layer to the organic layer where the
reaction takes place.
It is a phase transfer catalyst. It transfers Pmu/nm
the phenoxide from the aqeuous phase to
the organic phase.

transports halide Tetrabutylammonium bromide is the Pmu/nm

phase transfer catalyst transporting the
halide through the barrier.

brings down salt. This acts as the phase transfer catalyst. Pmu/wm
It brings down the salt to the organic phase
to allow it to react.

Move between
Phases
moves 4-ethyl The tetrabutylammonium bromide helps Pmu/wm
phenol move the 4-ethylphenol from the aqeuous
to the organic phase to help it mix.
Stabilizes the 4-ethylphenol ion so it can Pmu/wm
pass through the phase barrier and
complete the reaction.

carries product The tetrabutylammonium bromide acts Pmu/wm

across phase as a way to move from the aqueuos to the
boundary. organic phase by carrying the product
 229

Table B5.3, continued

Theme Student Statement Code

Transfers Na+ Transfers Na+. and I- ions between phases. Pmu/wm
and I-.

Catalyst Catalyst Lmu/nm

It is a catalyst. Lmu/nm
It is a catalyst used to create the Lmu/wm
intermediate ions which are easier to
transfer.

Environment It makes a better environment for the SN2 Lmu/wm

reaction
To provide an ionic environment for the Lmu/wm
iodine ions to be contained in.

Miscellaneous To provide a negative ion for bonding to Pmu/wm

help separate methyl iodide.
The original organic layer of the solution. Lmu/nm
So that bromide would break up from the Lmu/wm
methyl and form the carbocation and then
bind to the 4-ethylphenol.
 230

Table B5.4 Student Understanding of the 5% Sodium Hydroxide Wash

of the Combined Diethyl Ether Extracts

Theme Student Statement Code

React with The purpose of washing the diethyl ether Pmu/nm

reagents layer with NaOH is to ensure all R-OHs
and R-I have been reacted with as well as
bringing down all polar groups to aqueous
levels.

Deprotonate The diethyl ether was washed because it Pmu/wm

could still have some 4-ethylphenol in it.
The NaOH would deprotonate the 4-
ethylphenol. The resulting 4-ethyl
phenoxide would then react with any
remaining methyl iodide to make more
product via a SN2 reaction.
To make sure that the reaction has been Pmu/wm
carried out to completion by helping
remove any hydrogens on the phenols.
The ether layer still might have reactant. Pmu/wm
The wash of OH- will help finish anything
that didnt take off the H+
To remove Hs from the compound (will Lmu/nm
make H2O).

Remove impurities
remove acid The NaOH will pull out any slightly acid ...Lmu/nm
molecules. molecules in our diethyl solution into the
aqueous phase. We are then able to pipet it
out to purify our solution.
This reacts any acid byproducts with the Lmu/nm
base so that they can be removed with the
 231

Table B5.4, continued

Theme Student Statement Code

remove ions To remove any salt ions from the reaction Lmu/wm
The NaOH solution is to pull any remaining Lmu/wm
ions away from the organic layer while the
product dissolved in it and ensure that the
reaction was complete.
Washing with NaOH pulls out any Lmu/wm
remaining methyl ions by bonding with
the OH in NaOH.

removes Removes impurities from the diethyl ether Lmu/wm

unspecified layer by adding a polar solvent.
impurities Washing the diethyl ether layer with 5% Lmu/wm
NaOH helps to isolate and purify the
product. It is helping to remove
impurities. It is not as polar.

Purify To help purify the diethyl ether further. Lmu/wm

To separate organic chemicals from other Lmu/wm
solutions. Purify the organic product.

Remove aqueous The NaOH allows for more separation to Lmu/wm

Layer get the last bit of aqueous layer out.
The washing was to ensure that none of the Lmu/wm
aqueous layer was in the diethyl ether vial.

Separate layers To separate the two phases organic solvent Lmu/wm

layer and aqueous solvent layer efficiently.
To separate those two layers exactly.
 232

Table B5.5 Student Understanding of the Water Wash

of the Combined Diethyl Ether Extracts

Theme Student Statement Code

To remove traces To remove leftover NaOH from the wash Mu/nm
of NaOH previous.
To wash away the remaining traces of 5% Mu/wm
NaOH and diethyl ether.
The water was to ensure that none of the Mu/wm
aqueous layer or any of the NaOH was left
in the diethyl ether vial.
Remove any remaining NaOH and other Mu/wm
impurities present in the ether layer.
The purpose of the wash of water is to grab Mu/wm
any reminant or unreacted NaOH from the
diethyl ether layer to make sure it is pure.

Remove ions To pull away any ions like the NaOH Mu/wm
wash, but it is also supposed to pull away
any remaining Na+ and OH- ions.
The water will pull out any ionic salts Pmu/nm
formed to the aqueous phase.
To help remove any impurities from the Pmu/wm
diethyl ether phase such as Na+ and I-
ions.
This helps to remove any ions so that the Pmu/wm
final product is as pure as possible. The
product is in the organic phase and
everything not wanted is in the aqueous
phase.

Remove impurities The washing with water is also used to Lmu/nm

or contaminates remove impurities so that the product can
be isolated after extraction. The water is
polar, so it can attract certain polar
molecules which arent supposed to be
with the product.
 233

Table B5.5, continued

Theme Student Statement Code

To remove some not useful part such as Lmu/wm
contamination. To help to activate the
synthesis reaction well.

Remove water To get any remaining aqueous layer. Lmu/nm

Collect water made from mechanism into Lmu/nm
one layer. Water hydrogen bonds with
itself.
To bond the newly formed H2O molecules Lmu/nm
through hydrogen bonding to allow for
removal of the newly produced H2O.
H2O is the leaving group so wash with Lmu/nm
water to get rid of any water. Has to do
with the H bonding and polarity of washes.

Miscellaneous To purify the organic product Lmu/wm

Washing with water ensures that all Lmu/wm
organic components have been dissolved
so collecting through drying can occur.
 234

Table B5.6. Student Mechanistic Understanding of the use of 3-Sulfolene

Theme Student Statement Code

1,3-Butadiene is a
gas
3-Sulfolene is 1,3-Butadiene is gaseous at room Mu/nm
easier to handle temperature and 3-sulfolene is easier to
handle and 1,3-butadiene can be easily
made from it.
3-Sulfolene is a solid and can easily Mu/nm
produce 1,3-butadiene when we need to.
1,3-butadiene is a gas so it can be hard to
use on its own. Basically it is easier to
handle 3-sulfolene than 1,3-butadiene.

1,3-Butadiene is 1,3-Butadiene is a gas at room Pmu/nm

a gas that is temperature which makes it difficult
difficult to handle to measure and mess with.
and measure 1,3-Butadiene is in a gaseous state and Pmu/nm
difficult to measure.
1,3-Butadiene is a gas at room Pmu/nm
temperature so it would be hard to handle.

3-Sulfolene is a 1,3-Butadiene is a gas at room temperature Pmu/nm

source of so starting with 3-sulfolene will give us
1,3-butadiene 1,3-butadiene that can react quickly to give
us our product.
1,3-Butadiene is a gas and is difficult to Pmu/nm
control. 3-Sulfolene produces this gas in
our reaction vial. So 3-sulfolene gives us a
way to produce the needed reagent.
 235

Table B5.6, continued

Theme Student Statement Code

3-Sulfolene used Because 1,3-butadiene is a gas under the Pmu/nm
instead of room temperature. So 3-sulfolene is used
1,3-butadiene instead.
Because 1,3-butadiene is a gas at room Pmu/nm
temperature. So using 3-sulfolene and
heat you can avoid it being a gas.
.
Miscellaneous 1,3-Butadiene is a gas at room temperature Pmu/wm
so instead we make it and keep it trapped.
1,3-Butadiene is usually found in the trans Pmu/wm
form and is a gas by synthesizing it from
3-sulfolene we get the correct
conformation and can use solid reagents.

3-Sulfolene is more 3-Sulfolene is more stable than 1,3- Lmu/wm

stable. butadiene.
Because 3-Sulfolene is more stable and Lmu/wm
not flammable.

Miscellaneous 1,3-Butadiene has a very low boiling Mu/nm

. point which makes it hard to handle.
3-Sulfolene can be turned into 1,3-
butadiene and is easier to handle.

It is easier to control its decomposition Lmu/nm

through controlling the temperature.

Because we can keep 3-sulfolene at room Lmu/wm

temperature and then heat it when we
want it to react. Raw 1,3-butadiene may
react with other things in the solution
before we are ready to begin the reaction.
 236

Table B5.6, continued

Theme Student Statement Code

Because 3-Sulfolene has SO2 group. This Lmu/wm
group will easily leave more than other
groups making it easier for us to end up
with the 1,3-butadiene. Also, 1,3-
butadiene isnt found isolated in nature.

Because of its special structure, electrons Lmu/wm

are leaving and reforming elsewhere and
the moderate termperature is a good
environment condition for 3-sulfolene to
decompose rather than 1,3-butadiene.
 237

Table B5.7. Student Understanding of how the Sulfur Dioxide Produced

in the Reaction is Handled.

Theme Student Statement Code

Use of a fume hood It can be captured using a fume hood Mu/nm
It can be trapped after evolution by using Mu/nm
a vent hood.

Use of a fume hood

and drying tube
drying tube with A lab fume hood can be used to control Mu/wm
calcium chloride The gas from going into the rest of the lab.
The calcium drying tube might go after
this gas.
This could be accomplished by hood or Mu/wm
using the drying tube (craig tube) used
with calcium chloride.

drying tube To trap it, a packed vent will be on the Mu/wm

packed with reaction vial to absorb. Also, should be
absorbent done in a hood.
Sulfur dioxideis trapped with a drying Mu/wm
column packed with material to absorb it
as well as under a bench hood.

drying tube We will perform the experiment under the Mu/wm

hood and use a drying tube to help collect
the gas.

Experimental
apparatus
column This will be done with the distillation Lmu/wm
column and filter (calcium chloride) on top
This is accomplished using a column and Lmu/wm
drying tube on the reaction vial.
 238

Table B5.7, Continued.

Theme Student Statement Code

condenser You trap the sulfur dioxide using an air Lmu/wm
condenser with a calcium drying tube.
This is connected to the vial.
Accomplished by using a drying tube set Lmu/wm
To a condenser to keep it out of the air.

Tube to trap SO2 We can use a tube attached to our vial with Lmu/wm
a material in it that will trap the SO2.
It is important to trapthis is done using a Lmu/wm
tube above the vial with a trap in it that
will hold the SO2.

Miscellaneous We can use a tube system to trap it under Mu/wm

water in a vial or release it to the hood.
Sulfur dioxidecan be trapped by Lmu/wm
controlling the exhaust path by running the
reaction in a closed vessel.
It can be trapped by using a drying tube or Lmu/wm
it could be condensed and collected.
Just collect it in a tube and dissolve it in a Lmu/wm
solvent.
 239

Table B5.8. Student Mechanistic Understanding of the use

of Xylenes as Solvent

Theme Student Statement Code

Dissolves reactants
high boiling point It has a relatively high boiling point so the Pmu/nm
. solution can be heated properly. Xylenes
can also dissolve all reagents without
interfering in the reaction.

does not interact Xylenes are a good solvent for the Pmu/nm
with reactants Reactants and it will not react with or
ionize them either.

stable at reaction Xylenes is a suitable solvent because of Pmu/nm

temperatures The solubility of all the reagents in the
Solvent at the reaction temperatures.
Xylenes is also stable at the reaction
temperatures so it will not break down
and react with the products or reactants.

dissolves Its a good solvent because the reactants Pmu/nm

reactants are easy to be solved in this solvent

boil off xylenes Xylenes is a suitable solvent because our Pmu/wm

reactants are both soluble in xylene and
both have a significantly higher boiling
point than xylene so xylene is able to boil
off letting the reaction take place and
concentrate the product.

Non Reactive
wont react It does not react with the reagents. All Pmu/nm
the xylenes have similar boiling points.
Wont react as a Diels-Alder reagent. Pmu/wm
Some isomers are polar
 240

Table B5.8, continued

Theme Student Statement Code

ease of isolating Xylenes have complete cyclic Pmu/wm
product hydrocarbons and are unlikely to react
with the reactants. Also xylenes are
. soluble in petroleum ether, making it
easier to isolate the product.

keeps butadiene in It is relatively unreactive with our reagents Pmu/wm

solution and product and will be able to keep the
butadiene in solution once it is separated
from the sulfur dioxide group.

Presence of double Xylenes contains the benzene ring which is Lmu/nm

Bonds structurally close to 3-sulfolene and maleic
anhydride so it makes it a better solvent.
Presence of double bonds in xylene.
The double bonds help make it a suitable Lmu/wm
solvent. The methyl groups are electron
donating which helps with the reaction.

Miscellaneous Nonpolar aprotic solvent and because of Pmu/wm

. that it is a good solvent for the maleic
anhydride and 3-sulfolene.

It can be mixed together to change the Pmu/wm

Range of its boiling point. We will use a
Mixture that has a boiling point of 137-
140C.

Xylenes can have many resonance forms Lmu/wm

so they will have high electon density and
help to dissolve the compounds using the
many different electron locations. This
will help the quick electron transfer
between 3-sulfolene and maleic anhydride
which will result in the product
 241

Table B5.8, continued

Theme Student Statement Code

Xylenes can be used as catalyst to help the Lmu/wm
reaction is going well. With the small
amount of activation energy, xylenes help
to get the Diels Alder product (because we
will use as lowest as possible temperature
to prevent the loss of product).
.
It is in a locked arrangement and will not Lmu/nm
react with anything. It will not react with
the sulfur dioxide. It also has a high
boiling point so it will not evaporate that
fast.
.
Good for recrystallization. The product is Lmu/nm
soluble at high temperatures but not at
cold.
.
The methyl groups create a polarity to help Lmu/wm
remove SO2, allowing the two reagents to
react and form the product.
 242

Table B5.9. Student Mechanistic Understanding of the Need for Anhydrous Conditions

Theme Student Statement Code

Reaction
maleic anhydride If it has H2O it, the H2O would react with Pmu/nm
the malice anhydride which is undesirable.
Maleic anhydride is very sensitive to Pmu/nm
moisture.
If it is wet the H2O will react with maleic Pmu/nm
anhydride and compromise it.

product It must be dry because any H2O in the Pmu/nm

reaction will react with the desired product
giving us an unwanted product acid instead
of the anhydride acid.

reactants Any H2O in the xylene may react with the Pmu/wm
reactants (ie protonate oxygens).

xylenes So it doesnt go through hydrolysis with Lmu/wm

the moisture (destroy double bonds).
Xylenes can react with the moisture. Lmu/wm
Water would react with the double bonds Lmu/wm
and make the xylene useless.
Because it reacts with the moisture in air, Lmu/wm
so it needs to be kept dry. If it is wet it
doesnt work.
If they are wet, it will react as if with an Lmu/wm
acid and hydrolysis will occur.
Because if it has water in it, it will react. Lmu/wm

side reactions Because water will cause reactions other Pmu/nm

than the desired one.
Because excess water will cause side Pmu/nm
reactions and lower yield.
 243

Table B5.9, continued

Theme Student Statement Code

If it has some moisture on the xylene Pmu/nm
it will cause other reaction with
corresponding acid.

Miscellaneous Wet xylenes would mean H2O would be Lmu/wm

Responses all through the solvent and they could get
in the way for the reaction.

The chemical properties may change if Lmu/wm

its a liquid. It has to be dry to mix with 3-
sulfolene.

You dont want water to cause the Lmu/wm

reactants to turn into ions.
.
It is a fine powder so if any moisture gets Lmu/wm
in it, it will clump.
 244

Table B5.10. Student Mechanistic Understanding of How to Dry Xylenes

Theme Student Statement Code

Distillation
distillation I would distill it in the presence of N2 so Pmu/nm
that it would be less likely to catch on fire
but still separate the H2O and xylenes.
Xylenes can be dried through distillation Pmu/nm
Dry by distilling the solvent Pmu/nm

molecular filter The xylene can be dried by distillation or a Pmu/nm

molecular filter.

drying agent To dry xylene you need to either distill it Pmu/nm

or add a drying agent to soak up the water.

Drying agent Xylenes will be dried using a drying agent Pmu/nm

such as anhydrous sodium sulfate.
You dry xylenes by using the calcium Pmu/nm
drying agent.
It is possible to dry it using a powdered Pmu/wm
drying agent then filtering it out or
distillation.

Oven By placing it in the oven and evaporating Lmu/wm

all the water it can be dried.
To dry xylenes, xylene should be put in the Lmu/wm
oven for 5 10 minutes.
Xylenes is dried by heating in an oven Lmu/wm
(and cooled in a dessicator to protect from
atmospheric moisture).

Desiccator Put the flask in a flask and put in Lmu/wm

metal dessicator for 5 - 10 minutes
You can dry xylenes using a desiccator Lmu/wm
 245

Table B5.11 Student Mechanistic Understanding of the Nature

of Petroleum Ether

Theme Student Statement Code

A mixture of Petroleum ether is a mixture of organic Mu/nm
hydrocarbons compounds such as hydrocarbons like
benzin.
A mixture of hydrocarbons not an actual Mu/nm
ether.

A mixture of It is a mixture of alkanes. Mu/nm

alkanes A mixture of alkanes obtained from Mu/nm
distillation of crude oil.
.
Ether Petroleum ether is one of the species of Lmu/wm
the ethers
Dioctyl ether Lmu/wm
It is raw ether Lmu/wm
Ether R-C-O-R Lmu/wm

Solvent
product not Petroleum ether is a solvent that our Lmu/nm
soluble at cold product is not very soluble in at cold
temperatures temperatures

wash solvent Petroleum ether is the solvent we will Lmu/nm

wash our product with.

organic solvent It is an organic solvent Lmu/nm

volatile solvent Petroleum ether is a fairly volatile solvent Lmu/wm

recrystallization It is a solvent in which our product is Lmu/nm

solvent soluble in at high temperatures and
insoluble at low temperatures. A very Lmu/wm
volatile organic solvent that the product
is not soluble in at cold temperatures yet
it is at higher temperature.
 246

Table B5.12. Student Understanding of Purpose of Petroleum Ether.

Theme Student Statement Code

Product not soluble The product will precipitate out at low Mu/nm
(precipitates) at cold temperatures in a solution of petroleum
temperatures ether
Petroleum ether is a solvent that our Mu/nm
product is not very soluble in at cold
temperature.

Product not soluble The product is not soluble in cold Pmu/wm

but impurities are petroleum ether so anything that
solubilizes was not part of the product.
It will not dissolve the product but will Pmu/wm
dissolve other impurities, it is used to
purify the product.
It isolates the product because the product Pmu/wm
is insoluble in it but organic impurities are
not.

Washes away It washes off any impurities and other Pmu/nm

impurities organic (unwanted) compounds.
It can help isolate the products by washing Pmu/nm
out the organic substances to help get the
product.
The product is not soluble in cold Pmu/wm
petroleum ether, but it will wash away
contaminants from the product.
It helps isolate by washing away any Pmu/wm
organics we dont want when we wash the
filter cake with cold petroleum ether. It
has to be cold because solubility is
proportional to temperature (solubility
decreases as temperature decreases).
Wont wash away any crystals already
made.
 247

Table B5.12, continued

Theme Student Statement Code

Petroleum ether is used to wash the Pmu/wm
product with. Our product should not be
soluble in it so the petroleum ether washes
away any unwanted material or impurities

Recrystallization It is used because the product is soluble in Lmu/nm

solvent warm ether but not in chilled ether.
The product is soluble in hot petroleum Lmu/wm
ether but not in cold ether. By dissolving
and recrystallizing we can trap waste
organic in the ether.
The product is not soluble in at cold Lmu/nm
temperatures yet it is at higher
temperatures. This property can help in
isolating the product.
Our product is soluble in at high Lmu/nm
temperatures and insoluble at low
temperatures.

Miscellaneous It can be used as a solvent to dissolve the Lmu/wm

responses unwanted products of the reaction and
leave the desired product.

Petroleum ether is helpful to isolate the Lmu/wm

polar product by stripping any organic
solvent or unwanted compounds still
present.

Petroleum ether helps to form the cyclic Lmu/wm

form of product well. It removes the
impurities of the product. Petroleum ether
is one of the species on the ether and used
to wash the product during the process of
filtration.
 248

Table B5.12, continued

Theme Student Statement Code

Petroleum ether helps isolating the product Lmu/wm
by reacting with the alkene or alkyne to
form the product.
 249

Appendix C

Prelaboratory Quizzes

Chemistry 264 Quiz #2

Williamson Synthesis of Ethers

Name:_____________________________ Date:____________

1. A student performed the experiment you will begin today (Williamson

synthesis of ethers) using 200mg of 4-ethylphenol (122.17g/mole), 120L of
methyl iodide (141.94g/mole), 24mg of tetrabutylammonium bromide
(322.38g/mole), and 347L of a 25% NaOH solution.

NaOH
CH3CH2 OH + CH3 I CH3CH2 O CH3 + Na+,I-
(C4H9)4N+Br-

a. How many mmoles of 4-ethylphenol were used? (2 pts)

1mmole
200mg x = 1.64mmole
122.17mg

b. How many mmoles of methyl iodide were used? (2 pts)

1mL 2.28g 1000mg 1mmole

120 L x x x x = 1.93mmole
1000 L mL 1g 141.94mg

c. How many equivalents of methyl iodide were used? (2 pts)

1.93mmole
= 1.18equivalents
1.64mmole

d. What is the theoretical yield of methyl p-ethylphenyl ether

 250

(136.09g/mole). (3 pts)

136.19mg
1.64mmole x = 223mg
1mmole

e. The student obtained 200mg of product methyl p-ethylphenyl ether.

What was the percent yield? (2 pts)

200mg
x 100 = 89.7%
223mg

2. What is the role of NaOH in the experiment? (3 pts)

4-Ethylphenol (a weak nucleophile) is converted to a phenoxide ion

(a stronger nucleophile) by deprotonation with NaOH.

3. What is the role of tetrabutylammonium bromide in the experiment? (3 pts)

Tetrabutyl ammonium bromide is the phase-transfer catalyst that

carries the phenoxide ion, as an ion-pair, from the aqueous phase, across
the phase boundary into the organic phase, where it reacts with methyl
iodide.

4. What type of reaction is the Williamson Ether Synthesis? Justify your answer.
(3 pts)

The Williamson Ether Synthesis is an SN2 reaction between a

strong nucleophile (phenoxide ion) and a primary alkyl halide (methyl
iodide)
 251

Chemistry 264 Quiz #3

Williamson Synthesis of Ethers and

Photochemical Isomerization of an Alkene

Name:_____________________________ Date:____________

1. A student performed a Williamson synthesis of ethers using the same procedure

as you executed last Thursday using 1.64 mmoles of 4- ethylphenol and 1.93
mmole of methyl iodide.

NaOH
CH3CH2 OH + CH3 I CH3CH2 O CH3 + Na+,I-
(C4H9)4N+Br-

After stirring the reaction mixture at 110oC for approximately 60 minutes,

the student allowed the reaction mixture to cool to ambient temperature
before adding diethyl ether creating a two phase mixture. After separation
of the aqueous and diethyl ether layers, the diethyl ether layer was
washed sequently with a 5% NaOH solution followed by water.

a. What is the purpose of washing the diethyl ether layer with a 5% NaOH
solution? (4 pts.)

The diethyl ether layer contains both the desired ether product and excess
methyl iodide. The 5% NaOH solution converts the excess unreacted
methyl iodide to sodium methoxide which is soluble in the aqueous NaOH
solution and easily removed from the ether product.

b. What is the purpose of the subsequent washing with water. (4 pts.)

The water wash removes any remaining water soluble impurities

from the product ether,
 252

2. In the Photochemical Isomerization of an Alkene experiment that you will start

today, you will separate the cis and trans isomers of 1,2-dibenzoylethylene by
crystallization. Why are cis-1,2-dibenzoylethylene and trans-1,2-
dibenzoylethylene amenable to separation by crystallization? (4 pts)

cis-1,2-dibenzoylethylene and trans-1,2-dibenzoylethylene are

diastereomers (isomers that differ only in the arrangement of atoms in space).
Diastereomers have different physical properties such as melting points,
boiling points, dipole moments, densities, and solubilities as well as different
spectroscopic properties. Consequently, diastereomers are amenable to
separation by crystallization.

3. If a solute you wish to purify by recrystallization is soluble in a particular

solvent when it is cold, is it necessary to test the solubility of the solute in
the same solvent when it is hot? Explain your answer. (4 pts)

To achieve high recoveries, the compound to be recrystallized

should be very soluble in the hot solvent but nearly insoluble in the cold
solvent. Because the solute is soluble in cold solvent, a high recovery is
not possible. Consequently, the solvent is not suitable for recrystallization
of the solute and the solubility of the solute in the same solvent when hot
need not be determined.

4. What is the purpose of using activated carbon in a recrystallization procedure.

(4 pts)

The activated carbon will absorb minor amounts of colored impurities.

 253

Chemistry 265 Quiz #4

Diels Alder Reaction

Name:_____________________________ Date:____________

O H O
O Xylenes
S + O O
O heat
O H O
3-Sulfone
Maleic Anhydride

1. In the Diels-Alder reaction of 3-Sulfone and Maleic Anhydride that you will
perform in lab today, xylenes (a mixture of dimethylbenzene structural
isomers) will be used as the solvent. What characteristics of xylenes make it
a suitable solvent for todays experiment?

(a) Xylenes boiling point range of 137-140oC will allow for the use of
temperatures that will provide the thermal decomposition of 3-sulfone to s-
cis-1,3-butadiene and sulfur dioxide and increase the rate of the thermal
cycloaddition of 1,3-butadiene with maleic anhydride and the thermal
decomposition of 3-sulfone to s-cis-1,3-butadiene and sulfur dioxide without
reducing the equilibrium constant (Keq) significantly and thus reduce the
amount of product formed by overheating. (3 pts)

(b) The pi bonds of xylenes help solubilize 3-sulfone, maleic anhydride,

and the product through pi-stacking interactions. (3 pts)

2. Why is it important that the xylenes used as solvent in today experiment

be dry? How would one go about drying xylene?

(a) The maleic anhydride used in todays experiment needs to be

protected from moisture to prevent hydrolysis to the corresponding
acid. (3 pts)
 254

(b) Xylenes my be dried by either distillation or placing it over molecular

sieves. (3 pts)

3. 3-Sulfone decomposes at a moderate temperature to yield sulfur dioxide

and 1,3-butadiene (the actual diene used in this experiment).

O O
S + S
O O

(a) Why is 3-sulfone used instead of 1,3-butadiene?

1,3-butadiene is a gas at room temperature (bp = -5oC) which

makes it a difficult reagent to measure and handle in the
laboratory. (2 pts)

3-sulfone is a solid reagent that is easily handled. (2 pts)

(b) The decomposition of 3-sulfone to form 1,3-butadiene generates one

mole of sulfur dioxide gas per mole of 3-sulfone. Why is it important
to trap the sulfur dioxide produced and how would this be
accomplished?

Furthur oxidation of sulfur dioxide with O2 and H2O produces

H2SO4 and contributes to acid rain. (2pts)

Numerous organic reactions lead to the formation of gaseous

products. If the gas is insoluble in water, collection is easily
accomplished by displacing water from a collection tube. If the gas
is water soluble, the evolved gas is directed from the reaction
vessel to a container of water or other aqueous solution, wherein it
dissolves (reacts). (2 pts)

4. (Bonus) What is petroleum ether and how does it help isolate the product?

Petroleum ether is a mixture of alkanes (pentane, hexanes, and

heptane) and is used primarily as a nonpolar solvent. It is
 255

miscellible with both exylenes and toluene and helps isolate the
product by making the solvent system less polar and disrupting pi
interactions inducing the product to crystallize out of solution.
(3 pts)
 256

Appendix D

Williamson Synthesis of Methyl p-Ethylphenyl Ether

257
258
259
260
 261

Appendix E

Diels-Alder Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic

Acid Anhydride
262
263
264
265
266
267
268
269
 270

Appendix F

IRB Approval Form

Revised 11/08 RESEARCH EXEMPTION REQUEST Ref. # _______

(Category 1)
Purdue University
Institutional Review Board
Exemption under Title 45 CFR 46.101

(b)(1) exempts research conducted in established or commonly accepted

educational settings, involving normal educational practices, such as
(i) research on regular and special education instructional
strategies, or
(ii) research on the effectiveness of or the comparison among
instructional techniques, curricula, or classroom management
methods.

PLEASE BE AWARE that you cannot begin the project until you have received
notification that the exemption has been granted.

1. Project Title:
Student understanding of experiments performed in the Undergraduate Organic
Chemistry Teaching Laboratory

2. Anticipated Funding Source:

3. Principal Investigator [ See Policy on Eligibility to serve as a Principal Investigator

for Research Involving Human Subjects]:
Dr. George Bodner, Arthur Kelly Distinguished Professor, Department of Chemistry,
WTHR 216, 765-494-5313, gmbodner@purdue.edu
Name, Title, Department, Building, Phone, Fax, E-mail address

4. Co-Investigators and key personnel [See Education Policy for Conducting Human
Subjects Research]:
John Grutsch, Graduate Student, Department of Chemistry, WTHR 216, 765-494-
5312, jgrutsch@purdue.edu
Name, Title, Department, Building, Phone, Fax, E-mail address

5. Consultants [See Education Policy for Conducting Human Subjects Research]:

 271

Name, Title, Department, Building, Phone, Fax, E-mail address

6. Anticipated Duration of Study: Please indicate when this project will end. Estimate
how long it will take to transcribe audio and/or video tapes if used, and when they will be
destroyed.
Project END Anticipated project completion date is 06/2012. All audio tapes will
Date: be transcribed within three months of initial recording and
maintained in a locked office in WHTR 216 for the duration of the
project and then maintained indefinitely in a secure location by
researcher. Video tapes will not be transcribed but maintained in a
locked office in WHTR 216 for the duration of the project and then
maintained indefinitely in a secure location by researcher.

Participant Population

7. Expected Age Range

Check all that apply:
0-7
8-17
X 18-64
65 and older

8. Describe location of subjects during research data collection

Check all that apply:
X Purdue University, specify campus: West Lafayette
Elementary/Secondary Schools, specify:
Community Center, specify:
Other University Campus, specify:
Subjects Home, specify:
International Location, specify:
Other location, specify:

Research procedures or recruitment conducted off-campus within a school, business, or

other setting must have permission from an appropriate authority associated with that site.
I have attached letters of permission from the appropriate authority allowing the research
to occur at the proposed setting(s).
In the case of research conducted in educational settings (i.e. primary and secondary
schools, institutions of higher education, etc.), please note that you should check with
each school district you will work with to determine if separate school IRB approval or
 272

district approval is required.

Summary of Activities

(use lay language, do not cut and paste from or refer to grant or abstract)

9. Briefly state your research question.

What do undergraduate students and their graduate teaching assistants understand
about the experiments performed in the organic chemistry teaching laboratory course?

10. Will the activity/activities occur during class time or outside of class time?
X During Class Time
X Outside of Class Time
11. What research activity/activities will take place? Can Subjects
(check all that apply, then check if subjects can choose not to Choose Not to
participate) Participate?

YES NO

Implementation of a novel educational method

Describe how it differs from the standard method:

YES NO

Testing
Describe how often and when:
No more than ten pre-lab quizzes will be administered during any
academic semester. Prelab quizzes will be administered prior to the
beginning of a new experiment.
PLEASE BE AWARE that if you do not already have access to any of the
above information, you may only obtain it after the custodian of the
records de-identifies the data.

YES NO
 273

Review and collection of student grades and standardized test scores

Describe what scores or grades will be collected:

PLEASE BE AWARE that if you do not already have access to any of the
above information, you may only obtain it after the custodian of the
records de-identifies the data.
YES NO

X Will you be observing and recording data on teacher or student? X

1. Indicate teacher or student below:

X On Teacher
X On Student

2. How will the data be recorded?

X Written Notes
X Audio
X Video
Photographs
YES NO

X Review of student coursework X

Describe what course work will be reviewed and how identity will be
protected:
Coursework reviewed will consist of pre-lab assignments and quizzes,
in-lab reports, and final laboratory reports prepared by undergraduate
students enrolled in the course. Participants will be provided a
pseudonym and only the PI and co-investigator will know the identity of
the participant.
PLEASE BE AWARE that if you do not already have access to any of the
above information, you may only obtain it after the custodian of the
records de-identifies the data.
YES NO

X Use of questionnaires, interview questions, etc. If applicable, include a copy. X

Describe procedures to be followed:
Subjects will participate in no more than 10 face to face interviews with
co-investigator during any academic semester. Each interview will last no
more than 60 minutes. See attached copy of interview questions
 274

YES NO

X Other. X
Describe:
Pre-lab lecture given by graduate teaching assistant will be videotaped
by co-investigator. Co-investigator will make in-class observations of
interactions of graduate teaching assistant with undergraduate
participants. Co-investigator will also make in-class observations of
undergraduate participants as they set-up and complete experiments.
All observations will be recorded by co-investigator in a field notebook.

Attach all surveys, instruments, interview questions, focus group questions, etc.

12. Will the activity occur regardless of whether you are conducting research or not?
X YES
NO

13. Describe what non-participants will do during the research (activities and supervision):
It is important that the study design not penalize students who will not be participating if not all
students will be participating.
Non-participants will complete assigned experiments during class time without
interference from researcher or participants. Observations of participants will be
made in a manner so as not to hinder non-participants. Interviews of participants will
occur outside of class time.

Compensation

14. Will you give subjects gifts, payments, compensation, reimbursement, services, or extra
credit?
YES
X NO
Note: If extra credit will be offered for participation in the research activity, an alternative
activity must be provided to non-participating students for a comparable amount of credit.
If yes, please explain:

Recruitment
 275

15. How will potential subjects be identified for recruitment? (i.e. how will you select the
schools, teachers, and students for recruitment)
Subjects will be identified for recruitment from course rosters for the summer 2011,
fall 2011, and spring 2012 semesters of the undergraduate organic chemistry
laboratory courses CHM 26300, CHM 26400, CHM 26500, CHM 26600, CHM
26700, and CHM 26800. Subjects will include both undergraduate students enrolled
in the courses and graduate teaching assistants.

16. Describe your relationship with the population you wish to study. (i.e. are you the
teacher, principal, a graduate assistant, a fellow student, or clarify if you have not had prior
contact with this group, etc.)
PI is not the course instructor and has not had prior contact with the group. However, the
co-investigator has been the course supervisor for the undergraduate organic chemistry
teaching laboratory courses CHM 26300, CHM 26400, CHM 26500, CHM 26600,
CHM 26700, and CHM 26800 for the past two academic years and may be the course
supervisor in the future.

17. Describe with whom (i.e. graduate student) and how (i.e. in a classroom setting, by mail,
e-mail, etc.) you will make initial contact with the subjects.
Subjects will be students engaged in the undergraduate organic chemistry laboratory
courses CHM 26300, CHM 26400, CHM 26500, CHM 26600, CHM 26700, and CHM
26800. Subjects will include both undergraduate students enrolled in the courses and
graduate teaching assistants. Subjects will be informed of study at the beginning of
the first class period and instructed to contact co-investigator via email if they have
any questions about the research study or wish to volunteer and participate in the
project
Attach a copy of any and all recruitment materials to be used (i.e. advertisements, bulletin
board notices, e-mails, letters, phone scripts, or URLs).

Confidentiality

18. Will the data be collected anonymously (without identifiers)?

YES. Skip to end of document.
X NO. Describe the identifiers to be collected:
Data will be collected by use of questionnaires, face-to-face interviews, and field
observations of participants by co-investigator

19. Describe provisions that will be taken to maintain confidentiality of data (i.e. surveys,
audio, video, etc.):
All data (responses to quiz questions, audio and video tapes, interview transcripts,
field notebook, and all artifacts) will be maintained in a locked office in WHTR 216
 276

for the duration of the project and then maintained indefinitely in a secure location by
researcher. All subjects will be provided a pseudonym and only the PI and co-
investigator will know the identity of the participant.

20. Estimate how long it will take to transcribe audio and/or video tapes and when they will
be destroyed.
Audio tapes will be transcribed within three months of initial recording and maintained
indefinitely by co-investigator in a secure location. Video tapes will not be transcribed
and maintained indefinitely by co-investigator in a secure location.

21. Will the PI be able to identify subjects (i.e. identifiers, code keys, etc.)?
X YES
NO

22. Will identifiable data be made available to anyone other than the PI?
X YES
NO
If yes, explain who and why they will have access to the identifiable data:
Co-investigator will conduct face to face interviews with participants and transcribe all
interview data. Co- investigator will video tape pre-lab lecture given by graduate
teaching assistant. Co-investigator will also make field observations of participants.

As Principal Investigator of this study, I assure the IRB that the following statements are
true: I have read the Human Subjects "Research Exemption Request Guidelines. The
information provided on this form is correct. I will seek and obtain prior written approval
from the IRB for any substantive modification in the protocol, including changes in
procedures, research team members, funding agencies, etc. I will not begin my research until
I have received written notification of final IRB exemption. I will comply with all IRB
requests to report on the status of the study. I will maintain records of this research
according to IRB guidelines.

_________________________________________
Principal Investigator Signature Date

Submit the original request to: Institutional Review Board (IRB), Ernest C. Young Hall
10th Floor, Room 1032
VITA
 277

VITA

John L. Grutsch, Jr was born and raised in Fort Wayne Indiana. He completed a

Bachelor of Science in Chemistry from Purdue University (Fort Wayne campus) in 1993.

Upon completion of his Bachelor of Science in Chemistry, John began working as an

Associate Organic Chemist in the Chemical Process Research and Development Division

of Eli Lilly and Company in Indianapolis Indiana where he participated in the

development of synthetic routes for the preparation of potential drug candidates co-

authoring several papers and one patient. During this time he also completed a Master of

Science in Chemistry from Purdue University (Indianapolis campus) in 2000 and was

promoted to the position of Organic Chemist. In 2005, John began to teach the evening

Organic Laboratory section at Purdue University (Indianapolis campus) and in 2007 left

Eli Lilly and Company to pursue a Ph.D in Chemistry under the direction of Dr. George

M. Bodner where he investigated student understanding in the organic chemistry teaching

laboratory. While pursuing his Ph.D. John taught both general and organic chemistry

courses and also was the course supervisor for the organic chemistry teaching

laboratories. Upon graduation John hopes to continue both teaching of chemistry and

investigating student understanding across the chemistry curriculum.

PUBLICATION
 278

To be submitted for publication.

Student Understanding of the Williamson Synthesis of

Methyl p-Ethylphenyl Ether

John L. Grutsch, Jr., * George M. Bodner

*, Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, United

States

ABSTRACT
Laboratory activities in organic chemistry involve a mixture of sophisticated logic and
empirical observation that requires the integration of mechanistic thought, laboratory
technique, and problem-solving skills. In an effort to understand how students develop
the thought processes and problem-solving skills necessary for laboratory work in
organic chemistry, student understanding of how the interaction between a reaction
system (reactants or starting material(s), reagent(s), and/or solvent), experimental
variables (pH, temperature, concentrations, etc), produce a result of interest (yield,
selectivity, purity, etc.) in the Williamson Synthesis of Methyl p-Ethylphenyl Ether was
was investigated through the collection of responses to questions posed on pre-
laboratory quizzes followed by in-depth interviews during which student volunteers
discussed their responses along with their experiences in the laboratory. Students were
found to have little understanding of the rationale behind the chemical and physical
manipulations performed in the experiment. Consequently the experiment became an
activity in which students gave little thought about what they were doing which lead to
little meaningful learning, unsafe practices, and an unpleasant experience that
demotivated students.

ABSTRACT GRAPHIC

NaOH
CH3CH2 OH + CH3I CH3CH2 OCH3 + Na+,I-
(C4H9)4N+,Br-

4-Ethylphenol Methyl Iodide Methyl p-ethylphenyl ether

KEYWORDS
Second-Year Undergraduate , Chemical Education Research, Organic Chemistry Teaching
Laboratory, and Synthesis.

INTRODUCTION
Since the time of Liebig, laboratory instruction has held a distinctive and central
role in science education.1 In chemistry, laboratory instruction involves a mixture of
sophisticated logic and empirical observation that develops basic skills in problem
 279

solving. Although laboratory instruction has the potential to enhance the development
of scientific concepts held by students through the encouragement of inquiry,
intellectual development, problem solving, and manipulative skills, research has shown
it rarely obtains its full potential.2 Unfortunately, the chemistry teaching laboratory has
too often been found to be an environment where little meaningful learning takes place,
is ineffectual in the promotion of conceptual change3, provides an unrealistic portrayal
of scientific experimentation4, and does not promote thinking among students5.
Consequently, many educators have come to question the pedagogical value of
traditional methods of laboratory instruction that give little consideration of how to plan
an investigation or interpret experimental results3 and only facilitate the development of
lower-order cognitive skills such as rote learning and algorithmic problem solving.5
In recent years, considerable attention has focused on the pedagogical
effectiveness of the undergraduate organic chemistry teaching laboratory in addition to
the general chemistry laboratory. Although the organic chemistry teaching laboratory
has long been a fundamental and vital part of the organic chemistry curriculum,
educators have come to question instructional methods that emphasize the proper
handling of chemicals, important laboratory techniques, how to follow experimental
procedures, the preparation of representative compounds, demonstrate reactions
covered in lecture, and require students to reproduce previously published data.6
Concern about methods of instruction that present students with a cookbook of
foolproof recipes that do not encourage thinking or learning was expressed by Wade7
as follows:

Students can successfully complete the coursewithout acquiring a

fundamental understanding of the rationale behind any given manipulation
or how it might be applied in another situationsince they must simply
follow instructions to achieve the proper result.

Concern about traditional methods of instruction where students are only required to
blindly follow procedures with little thought about what they are doing was reiterated by
Pickering.8

Organic labs have degenerated into cookingthere is some sort of cosmic

futility in most organic labs. Make a white powder, prove it is what you
expect, donate it to chemical waste, again, again, and again (p. 144).
Today, debate continues over the educational value of traditional methods of
instruction that reduce the organic chemistry teaching laboratory to a rote exercise
designed to consume minimal resources whether these be time, space, equipment, or
personnel.9 To address questions of how to best engage students, many colleges and
 280

universities have begun to incorporate laboratory activities in nontraditional styles of

instruction such as guided inquiry (discovery), open inquiry, and problem or project
based experiments into the chemistry laboratory curriculum.10,11,12,13, 14 Laboratory
activities in nontraditional styles of laboratory instruction are believed to promote the
development of critical thinking skills15,3,4,5, reasoning skills4,16, literature searching12,
reading comprehension3, and teamwork4. In addition, laboratory activities in
nontraditional styles of instruction are also believed to promote the development of
higher-order cognitive skills such as analysis, synthesis, and evaluation.6
Although new laboratory activities for use in the organic chemistry teaching laboratory
along with their alleged pedagogical benefits continue to be published, few formal quantitative or
qualitative investigations of student understanding in the organic chemistry teaching laboratory
have been reported that present empirical data generated from controlled studies nor state how
assessment was made other than student self-reports. Consequently this research study sought
to investigate what students understand about the reactions they perform in the organic
chemistry teaching laboratory. Through investigation of what students understand about the
reactions they perform in the organic chemistry teaching laboratory, the authors hope insights
may be gained into the principles of how and by what processes students acquire the knowledge
and skills that allow them to develop an understanding of how organic chemistry reactions are
implemented in the laboratory. To this end, our guiding research question was:

What do students understand about how the interaction between a reaction

system (reactants or starting material(s), reagent(s), and/or solvent), experimental
variables (pH, temperature, concentrations, etc), produce a result of interest (yield,
selectivity, purity, etc.) in an experiment conducted in the organic chemistry teaching
laboratory?

THEORETICAL FRAMEWORK
Within the discipline of scholarly qualitative inquiry, various theoretical paradigms exist
that serve several functions.17 Primarily, a theoretical paradigm provides the assumptions that
guide the research. The theoretical paradigm assists the researcher in the selection of
appropriate questions for investigation. It also helps the researcher choose methods of data
collection appropriate for a study. Each theoretical paradigm has limitations that affect its
suitability for a particular research study. Consequently, some theoretical perspectives are more
appropriate for some investigations than others. A researcher doesnt necessarily have to accept
all of the assumptions of a particular perspective; however, those assumptions that are applicable
to an investigation must be specified.18 Table 1 summarizes the major theoretical paradigms
important to this research study.
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Table 1 Theoretical Paradigms

Issue
Theoretical
Paradigm
Ontology Epistemology Methodology

Positivist Objective reality exists There is one knowable Discourse structured

that may be found truth or reality & transparent -reflects
reality

Post Positivist Objective reality only Truth was found in Discourse is

imperfectly nonfalsified hypotheses constitutive of reality
apprehensible

Constructivist Reality is subjective Many truths exist Discourse is dialogic

and constructed and creates reality

Conceptual Reality is based on Conceptions are Discourse is dialogic

Change experiences and understood, judged, and promotes change
perceptions, culture, acquired, or rejected in at the core of a
and language a conceptual context system of concepts

Posititivism
Historically, scientific research has been dominated by a positivist paradigm that

assumes the infallibility of scientific knowledge to describe a knowable external reality.19 In a

positivist paradigm, knowledge is assumed to consist of verified hypotheses that may be thought

of as established facts or laws. Consequently the purpose or aim of inquiry in a positivist

paradigm is that of explanation to enable the prediction and control of phenomena whether

physical or human. Knowledge is believed to accumulate through a process of accretion where

each probable fact adds to a growing edifice of knowledge that allows generalizations to be made

with confidence to a population or setting. Facts are gained through methods that allow careful

measurement, manipulation, and control that are dominated by a deductive model constructed

upon empirically verified propositional hypotheses. Experiments, quasiexperiments, correlation

studies, and surveys are used along with sophisticated sampling and statistical techniques.

Quality of inquiry is determined by internal validity (correspondence of findings with reality),

external validity (generalizability), reliability (in terms of stability), and objectivity (researcher

neither influences nor is influenced by subject). Values are thought of as confounding variables

to an objective reality and specifically excluded. Ethics are considered to be extrinsic to the
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inquiry process and monitored by external mechanisms such as internal review boards and codes

of professional conduct. The voice of the researcher is that of the disinterested scientist who

informs others who independently use the information. Activities performed by students in the

organic chemistry teaching laboratory are built upon substantive technical theory, techniques of

procedural manipulation, along with qualitative and quantitative methods of characterization that

are assumed to define a knowable external reality. However, the positivists paradigm upon

which activities in the organic chemistry teaching laboratory are based is not compatible with

qualitative methods of research.

Post-Posititivism
Post positivism also accepts that an external reality exists. However, the postpositive

paradigm acknowledges that because of the limitations of human intellectual processes, this

external reality can only be imperfectly apprehended.20 Consequently, in a post positivist

paradigm, knowledge is assumed to consist of nonfalsified hypotheses that are probably true

rather than verified facts or laws. Like investigators following a positivist investigators paradigm,

post positivist researchers seek to maintain an objective position in relation to the phenomena of

study. However, because post positivist researchers see themselves as data collection

instruments, disciplined and rigorous research techniques are followed to ensure empirical data

drives findings and not the researchers impressions. Qualitative inquiry within a postpositive

paradigm is performed in natural settings to collect situational information to help discover the

meanings and purposes participants ascribe to their actions.

Constructivism
As a theoretical paradigm for scholarly qualitative inquiry, the principle assumption of

constructivism is that the world created by human perception may be different from the physical,

natural world.21 Human beings have the ability to interpret and construct their own unique

perception of reality. Therefore, the world created by human perception is not an objective

representation of physical reality, but is constructed and shaped by cultural and linguistic

constraints.22 Consequently, Humans do not have access to a singular, stable, and fully

knowledgeable external reality. All of our understandings are contextually embedded and

necessarily limited.23 Although the worlds created by human perception are a subject

representation of reality, it is important to remember that constructivism as a theoretically

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paradigm is concerned only with how individuals construction knowledge about reality, not with

the construction of reality itself.24 Because of these considerations, truth is believed to not arise

from an interaction with an objective reality, but is a result consensus amongst those who

construct what is considered truth.25

Although Socrates was the first to propose the idea that knowledge is constructed by the

learner26, the use of constructivism as a theoretic paradigm for research in education is generally

thought to have originated from the pioneering work of Piaget on the cognitive development of

children.27 From his research Piaget proposed that: learning occurs in stages; knowledge is

organized into cognitive structures; learning occurs through the dynamic interaction of an

individual and the environment; and that knowledge is continually constructed and reconstructed

based upon prior and novel experiences.28 Piaget also asserted that learning occurs through the

interaction of the learner with their environment by which knowledge is continuously constructed

and reconstructed through the processes of assimilation and accommodation. Assimilation

occurs when new knowledge is incorporated into an individuals existing cognitive structures. In

contrast, accommodation occurs when new knowledge does not fit into an individuals existing

cognitive structure. In this case, an individual may either ignore the contradictions and preserve

the original cognitive structure, make each cognitive structure hold for separate, specific cases, or

construct a new encompassing cognitive structure that explains and resolves the contradictions.

In contrast to Piagets emphasis on the stages of learning, Vygotsky asserted that

language and social interactions had a large impact on what and how a learner constructed

knowledge.29 Vygotsky hypothesized that the learner was cognitively limited to a zone of proximal

development that was bounded on one side by skills and knowledge that the learner already

possessed and on the other by skills and knowledge that the learner had to obtain with outside

help. An experience that only requires the skills or knowledge the learner already possesses

demands little cognitive effort from the individual whereas an experience that requires skills or

knowledge the learner lacks may be beyond the cognitive ability learner.

Constructivism was first used as a theoretical paradigm for research in science education

by Tobin and coworkers who investigated the teaching methods of an exemplary high school

science teacher through the lens of radical constructivism proposed by von Glasersfled.30 As a
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theoretical paradigm for research in science education, constructivism provides a way of thinking

about how individuals interact with the world around them and how they make sense of that

world. Constructivism assumes that a person does not discover preexisting knowledge. Rather,

individuals actively construct knowledge by inventing concepts and models to make sense of

their experiences and continually test and modify these constructions in the light of new

experiences.18

Conceptual Change Research

The central claim of the conceptual change view of learning asserts that new conceptions

are understood, judged, acquired, or rejected by a learner in a conceptual context.31 Learning is

considered to be a process of inquiry where the learner relates what they encounter to existing

conceptual structures deeply rooted in their experiences and perceptions, cultural values and

ideas, and language factors. Consequently new conceptions are not merely added to existing

conceptions, but interact with them sometimes requiring alteration of one or both. However,

because the learners pre-instructional understandings are sufficient to interpret and guide

they may significantly hinder learning in the context of the science classroom. Therefore views

that emphasize conceptual change assume students ability to learn and what students learn

depend on the conceptions they bring to the experience. Thus, learning and understanding may

only be appreciated by explaining how these conceptual resources function for the learner.

Conceptual change research focuses on two important questions postulated by the

conceptual change view of learning: how do learners incorporate new conceptions into current

cognitive structures and how do learners replace conceptions that have become dysfunctional

with new conceptions.32 However, conceptual change research does not focus on the

insurmountable task of altering all of the possible misconceptions that could be held by learners.

Rather, conceptual change researchers focus their efforts on conceptions that are at the core of

a system of concepts analogous to Piagets33 accommodation that involves the replacement or

reorganization of central concepts or Kuhns34 paradigm shift that involves the replacement of

concepts that are organizing in nature.

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METHODS
Reseach Setting
Qualitative research focuses on the interpretation of phenomena in its natural setting to

make sense of the meaning individuals bring to those settings.19 It attempts to understand the

unique interactions that occur in a particular situation.22 The purpose of this understanding is

not to predict what may occur, but rather to understand in depth the characteristics of the

situation and the meaning brought by participants. Consequently, qualitative research studies

phenomena in its natural settings in an effort to discover its meanings to those who are being

researched rather than that of the researcher.35 Therefore, to investigate students understanding

of how the interaction between a reaction system (reactants or starting material(s), reagent(s),

and/or solvent), experimental variables (pH, temperature, concentrations, etc), produce a result

of interest (yield, selectivity, purity, etc.) in an experiment performed in the undergraduate

organic chemistry teaching laboratory, this research study was conducted in the natural setting

of a undergraduate organic chemistry laboratory course of a large midwest research university.

To gain insight into student understanding investigate students understanding of how

the interaction between a reaction system (reactants or starting material(s), reagent(s), and/or

solvent), experimental variables (pH, temperature, concentrations, etc), produce a result of

interest (yield, selectivity, purity, etc.), the second semester of a two-semester organic chemistry

laboratory course sequence was investigated. The universitys catalogue describes the course as

a continuation of the first semester organic chemistry laboratory course in that experiments are

designed to illustrate principles discussed in the corresponding lecture course. Six learning

objectives are enumerated that presume students will be able to: (1) use theory to understand

and predict experimental observations; (2) demonstrate and understanding of the physical

properties and a molecular understanding of chemical reactivity and materials; (3) document

scientific information and experimental data and write scientific reports, with graphical

presentation of data; (4) plan and perform chemical transformations; (5) recognize and use

chemical instrumentation and spectroscopy; and (6) identify and handle hazardous materials.

The Summer 2011 Semester of Chemistry 264 was an accelerated eight week semester

that met twice per week for eight weeks. Each laboratory session was two hours and fifty

minutes in length. Eight experiments were performed throughout the semester. Five of the eight
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experiments were in the traditional expository style of laboratory instruction and included: the

Williamson synthesis of ethers, preparation of methyl p-ethylphenyl ether; photochemical

isomerization of an alkene, cis-1,2-dibenzoylethylene; Diels Alder reaction, preparation of 4-

cyclohexene-cis-1,2-dicarboxylic acid anhydride; microscale Suzuki cross coupling of

phenylboronic acid with 4-iodophenol in aqueous media; and evaluation of L-proline as a catalyst

for an asymmetric aldol reaction. Two of the eight experiments were in the guided inquiry or

discovery style of laboratory instruction: proton exchange and integral evaluation; and Friedel

Crafts acylation of 2-chlorotoluene and subsequent haloform reaction. One of the eight

experiments was in the project or problem-based style of laboratory instruction: synthesis of

substituted chalcones. Students were given a comphrensive final exam at the end of the

semester

Each laboratory session was lead by two teaching assistants who were graduate students

in the Department of Chemistry of Purdue University. Both teaching assistants were engaged in

research within the organic chemistry division. The graduate teaching assistants were

responsible for providing a ten- to fifteen- minute pre-laboratory lecture and guiding the day to

day activities of undergraduate students. The teaching assistants also graded all pre-laboratory

quizzes and final laboratory reports. Undergraduate students worked in pairs with the same

partner throughout the semester. Students decided among themselves in regards to the

distribution of work.

Description of Classroom Environment

The classroom environment consisted of a room with six rows of laboratory benches that

could accommodate four students each, for a maximum capacity of 24 students. Each student

was provided with a microscale glassware kit to use in the execution of laboratory activities.

Instrumentation available included four analytical balances, eight meltemps to obtain melting

point and boiling point data, and two ATR infrared spectrometers. A 300 MHz Varian nuclear

magnetic resonance spectrometer maintained by the Purdue Interdepartmental NMR facility was

made available for the collection of both 1H and 13C NMR spectra. Various print sources of

information were available to students within the classroom such as a Merck Index and Aldrich

catalogue along with electronic media through the department of chemistry library webpage.
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Experiments Investigated
Students understanding of how the interaction between a reaction system (reactants or

starting material(s), reagent(s), and/or solvent), experimental variables (pH, temperature,

concentrations, etc), produce a result of interest (yield, selectivity, purity, etc.) in an experiment

was investigated for four of the experiments performed during the Summer 2011 Semester of

Chemistry 264 was investigated: the Williamson synthesis of ethers; preparation of methyl p-

ethylphenyl ether; the Diels-Alder preparation of 4-cyclohexene-cis-1,2-dicarboxylic acid

anhydride; the Friedel-Crafts acylation of 2-chlorotoluene and subsequent Haloform reaction to

prepare 2-chloro-3-methyl benzoic acid; and the evaluation of L-proline as a catalyst for an

asymmetric aldol reaction to prepare a chiral -hydroxycarbonyl and subsequent Mosher analysis

to quantify the enantiomer enrichment of the product.

Only the results obtained for the experiments in the traditional expository style of

laboratory instruction, the Williamson synthesis of ethers; preparation of methyl p-ethylphenyl

ether and the Diels-Alder preparation of 4-cyclohexene-cis-1,2-dicarboxylic acid anhydride will be

presented an discussed in depth in this paper. Results obtained from the experiments in the

guided inquiry style of laboratory; the Friedel-Crafts acylation of 2-chlorotoluene and subsequent

Haloform reaction to prepare 2-chloro-3-methyl benzoic acid and the experiments in the project

based style of laboratory instruction, the evaluation of L-proline as a catalyst for an asymmetric

aldol reaction to prepare a chiral -hydroxycarbonyl and subsequent Mosher analysis to quantify

the enantiomer enrichment of the product, an experiment in the project based style of laboratory

instruction, will be discussed in another paper.

Participants
The sample used in this research study consisted of the students enrolled in the Summer

2011 Semester of Chemistry 264. Information about Students background was obtained through

a questionnaire administered the first day of class. In total, 21 engineering and science students

participated in the investigation. Nineteen of the 21 participants declared chemical engineering

as their academic major, while two of the participants declared chemistry as their academic

major. Thirteen of the participants indicated their semester classification as sophomores, three

as juniors, and five as seniors. Twelve of the participants indicated they had professional

experience as part of their involvement in the professional practice program in the school of
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engineering. Two of the participants stated they had prior work experience in a research

laboratory. Twenty of the participants had previously completed the first semester of the organic

lecture course Chemistry 261 and laboratory course Chemistry 263 at the Purdue University

campus in West Lafayette. One of the participants had completed their first-semester organic

chemistry lecture and laboratory course at Indiana University-Purdue University Indianapolis.

The students had a diverse background in general chemistry. Five of the participants

indicated they had completed the two-semester Chemistry 123/124 general chemistry course

sequence intended for students enrolled in the school of engineering. Seven of the participants

indicated they had completed the two semester Chemistry 115/116 general chemistry sequence

required of science and engineering majors not enrolled in Chemistry 123/124. Two of the

participants indicated they had completed Chemistry 136, a one semester general chemistry

honors course for students advanced placement chemistry credit, admission to the honors

program in science or engineering, or a score of at least 70% on the Chemistry 115 test out exam.

Four of the participants indicated they had completed general chemistry but did not specify what

courses they completed; one participant indicated they had completed general chemistry at

another university while two participants did not respond to the question

Although all of the 21 students enrolled in Chemistry 264 participated in the research

study, two students participated in weekly interviews with the researcher in addition to their

participation in other aspects of the study. Both students were chemical engineering majors who

participated in the co-operative work study program and had gained industrial experience as

chemical engineer prior to enrolling in Chemistry 264. Participation in the weekly interviews

allowed the researcher to gain a more in-depth and detailed understanding of the background

Buffy was a chemical engineering student in the engineering co-operative education program at

Purdue University. She had just completed her third year of study and was to begin her fourth

year in the fall semester. In our interviews, Buffy indicated while at Purdue she had completed

the two-semester general chemistry course sequence of Chemistry 123/124 and the first semester

of the two-semester organic chemistry lecture and laboratory sequence Chemistry 261 and

Chemistry 263. Originally from the Chicago suburbs, Buffy had taken honors chemistry her

freshman year of high school and advanced placement chemistry her junior year of high school.
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Buffy became interested in chemical engineering because she liked chemistry in high school and

believed engineering pays well. Buffy was employed by Sun Chemical as a Project Engineer

during alternate semesters when not at Purdue University. Buffy stated that where she worked,

chemical reactions were not performed, just the mixing of materials. Although Buffy stated she

did some pilot plant work her first term at Sun Chemical, she had been involved in the

construction of plant additions the past two terms.

Jody was also a chemical engineering student in the engineering co-operative education

program at Purdue University. He had just completed his second year and was to begin his third

year in the fall. Originally from Normal Illinois, Jody had taken honors chemistry his sophomore

year of high school and advanced placement chemistry his junior year of high school. Because

Jody scored a five on the AP chemistry exam, he received credit for Chemistry 115. Consequently

he elected to take Chemistry 136 the fall semester of his freshman year at Purdue. Jody then

enrolled in the first semester of the two-semester organic chemistry lecture and laboratory

sequence of Chemistry 261 and 263 the fall semester of his second year. In our interviews Jody

discussed how having semesters in which he did not take chemistry in between semesters he was

enrolled in chemistry courses impacted his learning.

When asked how he became interested in chemical engineering, Jody stated he knew he

wanted to do something that involved mathematics. He looked at actuarial science and

mechanical engineering but decided upon chemical engineering because he had really enjoyed his

chemistry classes. During alternate semesters when Jody was not attending classes at Purdue

University he was employed by Lubrizol at their Cleveland Ohio plant. In his interviews Jody

indicated his first term at Lubrizol focused on operations during which time he learned about the

various reactors, how to put a nitrogen purge on them, and how everything worked. In his most

recent term, Jody worked as a project engineer on capital process improvement projects such as

updating control systems and instrumentation. Jody seemed to be especially proud to have been

responsible for the design and implementation of special seal systems for agitators on the plants

main reactors. In his interviews Jody stated he hoped to become involved in process research

and development activities in the companys pilot plant in the future.

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Data Collection
This investigation followed the research tradition of probing students conceptions (also

referred to as preconceptions, prior conceptions, and misconceptions) as a necessary starting

point for the design of effective instruction (Driver, Guesne, & Tiberghien, 1985; Driver, Leach,

Miller, & Scott, 1996; Libarkin & Kurdziel, 2002). However, this line of research was extended to

examine students experiences in the organic chemistry teaching laboratory rather than just their

understanding of a science concept. In this sense, this investigation probes student

understanding of how organic chemistry reactions are implemented in the laboratory as opposed

to simply probing their understanding of organic chemistry.

Two methods of data collection were used in this investigation. The first method

consisted of obtaining student responses to pre laboratory quizzes given to the entire class at the

beginning of each laboratory session in which a new experiment was begun. Each quiz consisted

of four to six questions and was administered in the natural setting of the teaching laboratory

with the teaching assistants and researcher present. Students were given approximately ten to

fifteen minutes to complete the quiz. The quizzes were administered to the entire class to gather

the range of conceptions held by individual members of the class. To gain deeper insights into

student understanding of activities performed in the organic chemistry teaching laboratory,

weekly semi-structured interviews were conducted with volunteer participants during which time

students responses to quizzes were discussed along with participants experiences implementing

the various reactions in the laboratory. Interviews were conducted in the researchers office and

lasted between 30 and 60 minutes. Interviews were transcribed verbatum by the researcher.

Open ended questions were used in both the pre-laboratory quizzes and during the

interviews because the researcher did not want to prejudge or constrain the nature of the

understandings and misunderstandings that could emerge from the study. Because the

researcher also did not want to be bound to pre-established constructs of pre-designed and

structured questions that could potentially preclude context rich phenomena emerging from the

data, an inductive approach was used and questions not pilot tested (Miles, 1994).

Consequently, questions asked of students were general enough so as not to be leading in order

that key themes could emerge naturalistically from the data rather than forcing the data into a

predetermined structure.
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To keep in the research tradition of probing students prior or alternative conceptions

(Driver et al., 1985) broad open-ended questions were intentionally used to allow whatever was in

the forefront of students thoughts to emerge in their own words. Although the use of broad open

ended questions has the potential to reveal concepts held by students, the technique is limited in

that students may not completely or fully disclose their conceptions. Consequently, the reader

should bear in mind that the presence of a conception in a students response indicates students

are conscious of the conception, however absence of the conception does not necessarily

indicated students were not conscious of the conception.

Data Analysis
As a systematic search for meaning, data analysis represents a method by which

qualitative data may be processed in order that what has been learned may be communicated to

others (Hatch, 2002). Data analysis was found in the organization of information so that the

investigator is able to see patterns, themes, relationships, develop explanations, and make

interpretations, and generate theories. Often, data analysis involves synthesis, evaluation,

interpretation, categorization, hypothesizing, comparison, and pattern finding. Making sense of

qualitative data requires mind work where the investigator engages their own intelligence,

creativity, and reflexivity to provide meaning to the data. Data analysis may be thought of as

asking questions of the data. The types of questions asked are related to the set of paradigmatic

assumptions of the study with different paradigms leading to different analysis strategies.

An inductive approach to data analysis that involved a search of the data for connections

among specific elements for patterns of meaning to generate understanding and allow general

statements to be made was used in this study (Bryman & Burgess, 1994: Dey, 1993; Potter,

1996). The use of an inductive approach to data analysis is compatible with many types of

qualitative data analysis especially ground theory (Strauss & Corbin, 1998) and consistent with

general patterns of qualitative analysis discussed by other authors (Miles & Huberman, 1994,

Pope et al., 2000, Punch, 1998). Inductive analysis begins by the inspection of particularities

within the data followed by the discovery of relationships across individual observations and

ending with the establishment of relationships expressed as general explanatory assertions. In

this way particular pieces of evidence are pulled together into a meaningful whole. This allows
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research findings to emerge from frequent, dominant, or significant themes present in the raw

data without the constraints imposed by structured methodologies.

Thematic content analysis was used to examine student responses to the open ended

questions posed on pre-laboratory quizzes and in the interviews. In thematic content analysis,

themes are extracted from the text of participant responses rather than assumed without

reference to experimental data (Chi, 1997; Libarkin & Kurdziel, 2002; Miles & Huberman, 1994).

Themes that emerge naturally from the data are linked or reorganized to develop a dominate

structure. In this investigation, the researchers examined the keywords and phrases that

students used discuss what they understand about the reactions performed in the organic

chemistry teaching laboratory. Responses provided by students that discussed the same

mechanistic concepts were grouped together under a core theme. Student responses were then

evaluated in terms of the levels of mechanistic understanding demonstrated.

Validity
Traditionally, validity in qualitative research has meant establishing the extent to which

researchers assertions about knowledge are consistent with reality (or participants construct of

reality). Two different approaches to the question of validity have emerged recently within

qualitative research literature; transactional validity and transformational validity (Cho & Trent,

2006). Transactional validity in qualitative research may be thought of as an interactive process

between the investigator, the subject, and data with the purpose of obtaining a high level of

accuracy and agreement through the re-examination of facts, feelings, experiences, and beliefs

amassed and interpreted. In contrast, transformational validity in qualitative research may be

defined as an emancipative and progressive method that leads toward social change through the

research process itself

Transactional approached to validity assume that credibility may be increased through

the use of certain techniques, methods, and/or strategies during inquiry. Consequently, validity

was found in methods and techniques by which misunderstandings may be corrected. Two

techniques crucial for establishing credibility in transactional approaches are triangulation and

member checking. Triangulation is the verificiation of facts through the use of multiple data

sources to generate evidence in support of key claims. In this investigation triangulation was

achieved through the use of pre-laboratory quizzes, observation of laboratory experiences, and the
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collection of documents such as laboratory notebooks and spectral data. Member checking was

found in the reassurance of the credibility of the constructions provided by participants. This is

accomplished through the play back of collected data to participants to check for perceived

accuracy. In this investigation member checking was accomplished through participant

interviews in which participants responses to pre-laboratory quizzes, observed laboratory

experiences and documents were reviewed and discussed.

RESULTS
To investigate students mechanistic understanding of the Williamson synthesis of methyl

p-ethylphenyl ether, students were asked to classify the reaction with respect to its mechanistic

pathway and justify their response. All of the students correctly responded the Williamson

synthesis of methyl p-ethylphenyl ether proceeds by a SN2 mechanism. However, students

defended their response with a variety of mechanistic arguments. Consequently, responses

provided by students were organized into one of eight sub-themes of methyl or primary alkyl

halide, backside attack, displacement of iodine, one step reaction, substitution, SN2 with no

discussion, and intermediates based upon the mechanistic arguments provided by the student.

The subtheme of methyl or primary alkyl halide was found in the responses of two

students who demonstrated a mechanistic understanding of how the reaction conditions utilized

in the experiment determined the mechanistic pathway followed in the Williamson synthesis of

methyl p-ethylphenyl ether. Both of the two students responded the Williamson synthesis of

methyl p-ethylphenyl ether proceeds by a SN2 mechanistic pathway due to the use of methyl

iodide as the electrophile. These two students based their response upon the statements made by

the authors of the course textbook that the Williamson synthesis of ethers is often used for the

synthesis of symmetrical and unsymmetrical ethers where at least one of the carbon atoms is

primary or methyl and thus amenable to an SN2 reaction and that elimination (E2) is generally

observed if secondary or tertiary halides are used, since phenoxide ions are also bases. In their

responses, these two students demonstrated understanding the use of methyl iodide as the alkyl

halide electrophile restricts the Williamson synthesis of methyl p-ethylphenyl ether to a SN2

mechanistic pathway due to the instability of the methyl cation that would result if an SN1

mechanistic pathway was followed. The use of methyl iodide as the alkyl halide electrophile also
 294

prevents the Williamson synthesis of methyl p-ethylphenyl ether an elimination mechanistic

pathway due to the lack of a hydrogen beta to the carbon atom bearing iodide.

The subthemes of backside attack and nucleophilic attack releases iodine consist of the

responses of eight students who demonstrated an understanding of how reactions that occur by a

SN2 mechanistic pathway proceed but not how the reaction conditions utilized in the experiment

determined the mechanistic pathway followed in the Williamson synthesis of methyl p-

ethylphenyl ether. Six of the eight students responded the Williamson synthesis of methyl p-

ethylphenyl ether proceeds by an SN2 mechanism because of it occurs by backside attack while

two of the eight students responded the Williamson synthesis of methyl p-ethylphenyl ether

proceeds by an SN2 mechanism because of nucleophilic attack releases iodide. These eight

students based their responses upon the statement provided by the authors of the course

textbook that the Williamson synthesis of ethers is a classic SN2 process and involves a backside

nucleophilic attack of the phenoxide anion on the alkyl halide and the reaction scheme that

shows the reaction of sodium p-methylphenoxide with propyl iodide to produce propyl p-

methylphenyl ether and sodium iodide that includes arrow pushing formalism. However,

backside attack is a consequence of the reaction following an SN2 mechanistic pathway rather

than what causes the Williamson synthesis of methyl p-ethylphenyl ether to follow an SN2

mechanistic pathway. In addition, none of the six students demonstrated understanding the

hypothesis reactions that proceed by an SN2 mechanism occur with backside attack is supported

experimentally by the observation that the rate of reaction decreases with branching at both the

and carbon atoms of the electrophile with tertiary alkyl halides favoring -elimination instead of

substitution and that inversion of stereochemistry is observed when the carbon atom attacked by

the nucleophile is chiral,

The subtheme of substitution was found in the responses of four students who also

demonstrated an understanding of how reactions that occur by a SN2 mechanistic pathway

proceed but not how the reaction conditions utilized in the experiment determined the

mechanistic pathway followed in the Williamson synthesis of methyl p-ethylphenyl ether. Each of

the four students responsed the Williamson synthesis of methyl p-ethylphenyl ether occurs by an

SN2 mechanism because of substitution without inclusion of the mechanistic concept of backside

attack. These four students based their responses upon the statement provided by the authors of
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the course textbook that the Williamson synthesis of ethers is a classic SN2 process, their prior

understanding that a SN2 mechanism involves substutition, and the reaction scheme that shows

the reaction of sodium p-methylphenoxide with propyl iodide to produce propyl p-methylphenyl

ether and sodium iodide that includes arrow pushing formalism. However, substitution is a

consequence of the reaction following an SN2 mechanistic pathway rather than what causes the

Williamson synthesis of methyl p-ethylphenyl ether to follow an SN2 mechanistic pathway. In

addition, none of the four students provided a mechanistically incorrect discussion of how

substitution is demonstrated in the Williamson synthesis of methyl p-ethylphenyl ether.

The subtheme of SN2 with no discussion was found in the responses of two students who

demonstrated a lack of a mechanistic understanding of the Williamson synthesis of methyl p-

ethylphenyl ether. In their responses, these two students answered the Williamson synthesis of

methyl p-ethylphenyl ether proceeds through a SN2 mechanistic pathway but did not provide

further discussion. Although both students based their response upon the statement made by

the authors of the course textbook that the Williamson synthesis of methyl p-ethylphenyl ether

is a classic SN2 process neither student demonstrated they understood how the reaction

conditions determined the mechanism of the reaction. Instead, these two students were simply

repeating the comments provided by the author of the course textbook that the Williamson

synthesis of ethers proceeds by an SN2 mechanistic pathway.

The subtheme of intermediates was found in the response of one student who also

demonstrated a lack of a understanding of how the reaction conditions utilized in the experiment

determined the mechanistic pathway followed in the Williamson synthesis of methyl p-

ethylphenyl ether. In their response, the student answered the Williamson synthesis of methyl p-

ethylphenyl ether proceeds through a SN2 mechanistic because of intermediates and

substitutions. The student based their response upon the statement provided by the authors of

the course textbook that the Williamson synthesis of ethers is a classic SN2 process, their prior

understanding that a SN2 mechanism involves substutition, and the reaction scheme that shows

the reaction of sodium p-methylphenoxide with propyl iodide to produce propyl p-methylphenyl

ether and sodium iodide that includes arrow pushing formalism. Although the student correctly

stated the Williamson synthesis of methyl p-ethylphenyl ether proceeds by an SN2 mechanistic

pathway including substitutions, the student did not demonstrate understanding how the
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reaction conditions determined the mechanistic pathway. In addition, reactions that proceed by a

SN2 mechanistic pathway occur in a one step concerted manner without the formation of

intermediates.

The subtheme of one-step reaction was found in the response of one student who also

demonstrated an understanding of how reactions that occur by a SN2 mechanistic pathway

proceed but not how the reaction conditions utilized in the experiment determine the mechanistic

pathway followed in the Williamson synthesis of methyl p-ethylphenyl ether. This students

response of the Williamson synthesis of methyl p-ethylphenyl ether proceeds by an SN2

mechanistic pathway because it occurs in a one step concerted manner. Because the authors of

the course textbook do not the Williamson synthesis of methyl p-ethylphenyl ether as a one step

concerted reaction, this students response is based upon thier prior understanding that reactions

that proceed by a SN2 mechanism occur in a one step concerted manner. However, experimental

evidence that shows reactions that follow a SN2 mechanistic pathway occur in a one-step

concerted manner is provided by kinetic studies that show the rate of the reaction depends on the

concentration of both the nucleophile and electrophile, neither or which is evident or

demonstrated in the Williamson synthesis of methyl p-ethylphenyl ether.

CONCLUSIONS
The constructivists theory of knowledge asserts learners do not simply mirror and reflect

what they read (Von Glaserfeld, 1989). Rather, learners construct their own understanding by

searching for meaning and attempting to find regularity and order in their experiences even in the

absence of full or complete information. Unlike prior educational perspectives that placed the

responsibility of learning on the instructor who teaches a passive and receptive learner,

constructivism emphasizes the importance of the learner being actively involved in the learning

process. Learning is a reconstruction rather than a transmission of knowledge where individual

learner constructs mental models that allow them to understand the world (Sabelli, 2008).

Students develop their mechanistic understanding in regards to how the interaction

between a reaction system (reactants or starting material(s), reagent(s), and/or solvent),

experimental variables (pH, temperature, concentrations, etc), produces a result of interest (yield,
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selectivity, purity, etc.) in an experiment conducted in the organic chemistry teaching laboratory

through the synthesis of concepts obtained from several sources including the laboratory course

textbook, their understanding of chemical concepts they learned previously and brought forward

with them to the organic chemistry teaching laboratory understanding, and their experiences in

the organic chemistry teaching laboratory. Very rarely were students able to synthesize concepts

from the various sources of information and their experiences to provide a response to a question

posed on the prelaboratory quizzes that demonstrated a mechanistic understanding by being

mechanistically correct, concise, and directly answered the question. More often students

provided a response that demonstrated either a partial mechanistic understanding or a lack of a

mechanistic understanding. Responses that demonstrated a partial mechanistic understanding

typically consisted of broad and generalizable chemical concepts that were not concise and did

not directly answer the questions. Responses that demonstrated a lack of a mechanistic

understanding typically consisted of either correct chemical concepts that were inappropriately

used to answer the question posed on the pre-laboratory quiz or of chemical concepts that were

not correct. Whether the response provided by the student demonstrated a mechanistic

understanding, partial mechanistic understanding, or a lack of a mechanistic understanding,

responses provided by students could also include statements that were not mechanistically

correct.

Providing instruction does not means students will develop a mechanistic understanding

of how the interaction between a reaction system (reactants or starting material(s), reagent(s),

and/or solvent), experimental variables (pH, temperature, concentrations, etc), produces a result

of interest (yield, selectivity, purity, etc.) in an experiment conducted in the organic chemistry

teaching laboratory. For example, the authors of the course textbook devoted most of the

discussion section of the Williamson Synthesis of methyl p-ethylphenyl ether experiment to an

explanation of the phase transfer catalysis conditions used in the experiment. However, none of

the students provided a response that demonstrated a mechanistic understanding that the

purpose of tetrabutylammonium bromide was to transfer the 4-ethylphenoxide ion from the

aqueous layer to the organic layer and the iodide ion displaced from methyl iodide from the

organic layer to the aqueous. Instead most students provided a response that only demonstrated
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they understood tetrabutylammonium bromide moved species between phases or move between

phases but were unable to correctly specify the identity of the species transported.

When the authors of the course textbook did not provide instruction in the discussion

section of an experiment in the laboratory course textbook, students based their responses upon

concepts they had previously learned and brought forward with them to the organic chemistry

teaching laboratory. The concepts brought forth by students both enhanced and interfered with

the students ability to develop a mechanistically correct understanding of how the interaction

between a reaction system (reactants or starting material(s), reagent(s), and/or solvent),

experimental variables (pH, temperature, concentrations, etc), produces a result of interest (yield,

selectivity, purity, etc.) in an experiment conducted in the organic chemistry teaching laboratory.

For example, in the discussion section of the Williamson Synthesis of Methyl p-Ethylphenyl Ether

experiment, the authors of the laboratory course textbook do not discuss that the purpose of the

25% sodium hydroxide solution is to deprotonate 4-ethylphenol. However, students were draw

upon the knowledge of and experiences of using sodium hydroxide as a base to answer its

purpose was to deprotonate with several students stating it would deprotonate 4-ethylphenol.

Consequently, in this instance students prior understanding and experience with using sodium

hydroxide provided the background necessary to understand the use of the 25% sodium

hydroxide solution as a base to deprotonate 4-ethylphenol.

In contrast, students understanding and experience of using sodium hydroxide as a base

interfered with their understanding of the purpose of washing the combined diethyl ether extracts

with a 5% sodium hydroxide solution. Similar to the 25% sodium hydroxide solution, the authors

of the course textbook do not discuss that the primary purpose of washing the combined diethyl

ether extracts with a 5% sodium hydroxide solution is to convert any methyl iodide, that was

used in excess in the reaction mixture to drive the equilibrium forward, that may have been

extracted along with the desired ether product into the water soluble sodium methoxide salt.

However most the students replied the purpose of the 5% sodium hydroxide salt was to either

deprotonate 4-ethylphenol or react with acidic species that may be present. In addition, students

also confused the use of the 5% sodium hydroxide solution with the use of a saturated brine

solution to remove water or help separate the aqueous and organic layers, a procedure they had

previously performed many times in the organic chemistry teaching laboratory.

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ASSOCIATED CONTENT
Supporting Information [required for the manuscript types Laboratory Experiment and Activity]
Add a brief description here.

AUTHOR INFORMATION
John L. Grutsch, Jr.
*E-mail: jgrutsch@purdue.edu

ACKNOWLEDGMENT
The authors are grateful to the students who shared their pre-laboratory quizzes
with us, allowed us to observe them in the laboratory, and record our conversations
with them about the pre-laboratory quizzes and their experiences about the
undergraduate organic chemistry teaching laboratory. The authors also thank the
director of the undergraduate teaching laboratories at the participating University for
allowing us access to student participants before, during, and after each laboratory
session.

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