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And Raos 2012
And Raos 2012
And Raos 2012
www.rsc.org/cerp PERSPECTIVE
Green chemistry teaching in higher education: a review of effective
practicesw
John Andraos*a and Andrew P. Dicks*b
Received 13th September 2011, Accepted 12th January 2012
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
DOI: 10.1039/c1rp90065j
This account reviews published green chemistry teaching resources in print and online literature and
our experiences in teaching the subject to undergraduate students. Effective practices in lecture and
laboratory are highlighted and ongoing challenges are addressed, including areas in cutting edge green
chemistry research that impact its teaching in the undergraduate curriculum. In particular, the
influence of green chemistry on the overall teaching of organic chemistry is discussed.
This journal is c The Royal Society of Chemistry 2012 Chem. Educ. Res. Pract., 2012, 13, 69–79 69
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70 Chem. Educ. Res. Pract., 2012, 13, 69–79 This journal is c The Royal Society of Chemistry 2012
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There are additional issues with how the subject of organic course, or to try and add greener modules to existing courses
chemistry is presented in some introductory textbooks. The across the curriculum? The pedagogical literature has shown
following is an outline of some important concerns: that either approach can be successful, but that there are
textbooks are often organized according to functional obvious ‘‘pros and cons’’ (Andraos, 2012(a)).
groups, not patterns of reactivity Launching a new offering with ‘‘green’’ in the title will
chemical transformations are rarely (if ever) balanced capture undergraduate interest given the current publicized
there are few citations to the original literature, so issues of sustainability and global environmental stewardship
students are forced to believe what the author says without (Marteel-Parrish, 2007). Ideas and concepts can be thoroughly
checking for themselves the validity of the claims made discussed and placed within the context of ‘‘real-world’’ case
examples are often not taken from the original literature, studies from the current chemical literature, leading to development
especially when discussing fundamental concepts such as of more advanced problems and assignments. Considering the
molecular structure and bonding extra time a dedicated course affords, students more clearly
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
there is a disconnect between concepts introduced and the appreciate that for problems posed in this field there is no single
originator(s) of the idea, and the circumstances around which ‘‘correct green answer’’, but rather there are a range of options that
the idea arose (the mechanics of how research is done is not need to be evaluated according to some criteria, and then a decision
shown to the student) is made as to which ‘‘answer’’ is best. A multivariate green exercise
there is an overwhelming emphasis on individual examples has recently been published where students consider nine life-cycle
(memorization) rather than on pattern recognition (understanding). assessment metrics in the context of an organic transformation
From a green chemistry perspective, there are also some (e.g. benzene to aniline) (Mercer et al., 2012). The instructor selects
textbook ‘‘myths’’ that impact the impressions students have several literature methods for each transformation with the student
about organic synthesis. These are listed below: goal of selecting the greenest route. In a similar vein at the
the terms ‘‘side product’’ and ‘‘by-product’’ are synonymous University of Porto, Portugal, students search for the greenest
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convergent synthesis plans are always more material- metal-acetylacetonate synthesis experiment commonly included in
efficient than linear plans the teaching laboratory literature, and attempt to improve its
short synthesis plans are always more material-efficient greenness (Ribeiro and Machado, 2011). This idea of considering
than long plans multiple solutions and making decisions is typically a tremendous
the amount of catalyst used in a reaction (catalyst loading) departure from their previous chemistry learning experiences.
is much smaller than the substrate on which it acts. There is also a shift in how an instructor is to evaluate student
4. Curricular issues assignments based on this paradigm.
Integration of a green chemistry course is preferable with
Perhaps surprisingly, there are still relatively few undergraduate other non-science related courses in areas of business, ethics,
green chemistry courses in Canada that are available for students law and regulatory affairs, that have relevance in team-driven
to take (Andraos, 2012(a)). There are significantly more offerings in research strategies of the chemical industry. Conversely, a new
the United States, with one model published in JCE (Marteel- course is time-consuming to prepare and may not find room
Parrish, 2007), and another taught at Monash University, Australia within an already-crowded curriculum, especially if it is
(Raston and Scott, 2001). Such courses are invariably considered proposed as an elective. There will likely be a significant
electives, and are not mandatory to fulfill the requirements of an learning curve for the instructor(s) involved in delivering the
undergraduate chemistry major program. A common misconcep- course. Significant resistance may arise from research faculty
tion within academia is that green chemistry is a ‘‘soft’’ and who object to precious resources being spent in such a manner.
descriptive subject, with only rudimentary numerical analysis In comparison, the ‘‘greening’’ of existing courses has the
required (Amato, 1993). Quantitative reasoning is usually not advantage of being less time-consuming in terms of implemen-
considered a necessary skill in synthetic organic chemistry courses tation. Fewer resources are required in terms of administrative
at any undergraduate level. In fact, the essential skill of balancing costs. Students benefit from potentially seeing green principles
chemical equations is often not carried forward into organic from a variety of different perspectives in both lecture and
courses from first year general courses, yet this is compulsory laboratory venues, and new textbooks are unnecessary. However,
for the proper itemization and quantification of waste material green approaches will likely have to replace some more traditional
produced in chemical reactions. Toxicology, hazard analysis, content (which may be unpalatable), and material cannot be
safety, and waste minimization strategies are subjects not routinely covered at the same level of detail compared with a stand-alone
included in the core curriculum for the chemistry major degree. course. This strategy requires ‘‘buy-in’’ from a number of faculty
Finally, green chemistry is often mistaken as being synonymous members and instructors within a department, and ongoing close
with environmental chemistry amongst students and sometimes coordination between them.
even research faculty.
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Presidential Green Chemistry Challenge Awards (Cann, 1999; discovery that green chemistry is all about decision making—by
Marteel-Parrish, 2007). These annual recognitions are in five its very nature, it is often an indefinite and ambiguous field. The
categories: the Greener Synthetic Pathways Award, the Greener final decision is a choice based on weighing favourable and
Reaction Conditions Award, the Designing Greener Chemicals unfavourable factors until an acceptable compromise is achieved,
Award, the Small Business Award and the Academic Award although the main goal is reaching certainty when a truly ‘‘green’’
(www.epa.gov/gcc/pubs/pgcc/award_categories.html). The project optimized plan is established (Mercer et al., 2012). The quest for
details of many awardees are suitable for inclusion in under- ‘‘greening’’ reactions is an iterative process that is never fully
graduate curricula, Table 2 lists three examples from the five 2011 reached. There is always room for improvement as new reactions
winners. Other instructive real-world organic teaching examples and methodologies are constantly being discovered. Important
have been described (Cann and Dickneider, 2004). Finding target molecules (such as the ones analyzed in the assignment
current green literature written at an appropriate level for instruc- described here) are always revisited for trying out new synthetic
tors and students at different academic levels to digest is straight- strategies. A corollary key concept is that the evaluation of
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
forward. Excellent journals include, but are not limited to Organic ‘‘greenness’’ is a relative comparison and not an absolute one.
Process Research and Development, ChemSusChem, Green This leads to the realization that if there is only one documented
Chemistry and Chemical & Engineering News (Table 2). Several synthesis plan available for a given target molecule then its
articles in Green Chemistry specifically deal with undergraduate ‘‘greenness’’ ranking cannot be determined formally, although
teaching methodologies (Matlack, 1999; Lennon et al., 2002; it may have some green attributes according to the Twelve
Tavener et al., 2003; Grant et al., 2004; Grant et al., 2005). Principles.
Many web-based green chemistry materials have additionally
been designed and published during the last decade. Table 3 4. Laboratory resources
illustrates a selected number of these to highlight the variety of
features available. There are on-line repositories of successful It is clear from peer-reviewed materials that a meaningful way
to teach and learn green chemistry is in a laboratory setting.
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72 Chem. Educ. Res. Pract., 2012, 13, 69–79 This journal is c The Royal Society of Chemistry 2012
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The Ecoscale EcoSynth, Oostende, Belgium post-synthesis tool to evaluate ‘‘greenness’’ of an organic
reaction (Van Aken et al., 2006)
Educating the Next Generation: Green and American Chemical Society on-line green chemical education conference; seven
Sustainable Chemistry Committee on Computers in academic papers presented during April–June 2010
Chemical Education
inorganic chemistry (Huheey, 1996). A search of the recent organic reactions, having often heard the opposite during
pedagogical literature identifies a number of appropriate lecture classes. After learning about ‘‘traditional’’ textbook
experiments in ‘‘non-organic’’ areas (Table 4), illustrating reaction solvents such as dichloromethane and acetonitrile,
the cross-curricular impact of green chemistry. More work they embrace performing reactions under solventless condi-
is needed in these venues to develop a comprehensive suite tions. A novel green laboratory teaching approach has been
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of practical resources that facilitates implementation within adopted where data generation and interpretation leads to
larger and smaller courses. The journal Green Chemistry has development of a principle statement (Teixeira et al., 2010).
additionally published educational efforts from a laboratory Students are guided to devise a more sustainable solvent
perspective (Warner et al., 2001; Houri and Wehbe, 2003; system for Grignard reactivity based upon their own acquired
McKenzie et al., 2004). data and that provided to them. A one-term, integrated
Direct application of the founding Twelve Principles in a project for the undergraduate organic laboratory involves
practical environment is now so straightforward that it makes synthesis of Nylon 6,6 from cyclohexanol (Dintzner et al.,
little sense for educators to avoid ‘‘greening’’ their experi- 2012). The product of one reaction is used as a starting
ments. Most contemporary students have a heightened sense material for the following one in an effort to minimize waste,
of environmental responsibility, and consider it important to and students are exposed to several other green principles in
be taught about modern approaches towards laboratory sus- the context of a familiar target compound.
tainability (Kitchens et al., 2006). They are, for example, A third-year undergraduate catalytic chemistry course
initially surprised that water is an excellent solvent for many (‘‘Organic Synthesis Techniques’’) has been designed at the
Field/sub-
discipline Experiment description Ref.
Introductory/ Colligative properties of fatty acids McCarthy and Gordon-Wylie, 2005; Iacobucci
General et al., 2006
Stoichiometry: composition of a sodium carbonate/sodium bicarbonate mixture Cacciatore and Sevian, 2006
Nanoparticle synthesis using a plant leaf extract Richardson et al., 2006
Solubility, equilibrium, and periodicity concepts surrounding Group II Cacciatore et al., 2008
hydroxides
Calculating the formula of copper(II) chloride dihydrate Klingshirn et al., 2008
Superconductor synthesis: the Meissner effect She and Liu, 2008
Analytical Spectrophotometric measurement of creatinine in urine Correia et al., 2004
Measurement of mercury in cow and goat milk by atomic fluorescence Armenta and de la Guardia, 2011
Electrochemical cell for cyclic voltammetry Olson and Buhlmann, 2010
Biological Purification of Escherichia coli DNA using laundry detergent Sims et al., 2010
Environmental Extraction of metal contaminants from environmental samples with micelles Giokas et al., 2003
Inorganic Preparation of tetraamido-N Cu(III) and Co(III) complexes Uffelman et al., 2004(a), 2004(b)
Cation qualitative analysis via spot tests Sidhwani and Chowdhury, 2008
Synthesis of Group II metal oxalate hydrates Canal, 2009
Metalloporphyrins as oxidation catalysts Clark et al., 2012
Solvent-free synthesis of Cu(II) phthalocyanine Sharma et al., 2011
Materials Alkanethiol monolayer formation on gold films McKenzie et al., 2004
Physical Synthesis and analysis of quantum dot nanocrystals Boatman et al., 2005
Properties of biodiesel: heat of combustion, density and cloudpoint Akers et al., 2006
Energy content and viscosity of biofuels Wagner et al., 2010
Density measurements using a Galilean thermometer Priest et al., 2011
This journal is c The Royal Society of Chemistry 2012 Chem. Educ. Res. Pract., 2012, 13, 69–79 73
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University of Toronto where green chemistry is a thread the experiment?’’; (ii) ‘‘what was not green?’’; (iii) ‘‘how could the
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
running through both lecture and laboratory components experiment be made greener?’’. It is certainly the case that ‘‘all
(Dicks and Batey, 2012). A number of novel pedagogical that glitters is not green’’ in the chemical research literature—a
experiments featuring catalysis are incorporated and listed in point elaborated on in the ‘‘inaccurate assertions of ‘‘greenness’’’’
Table 5, along with additional green aspects of each reaction. section concluding this article.
For each system, students undertake metric analysis (calcu-
lation of experimental atom economies and waste production). 6. Retooling introductory general and organic courses
This becomes especially instructive when ‘‘traditional’’ and In order to facilitate the introduction of either a new green
‘‘modern’’ approaches towards the same Biginelli reaction chemistry course or separate units into a number of different
are employed (Aktoudianakis et al., 2009). The traditional offerings, some important curricular issues should be
Biginelli reaction involves heating an aromatic aldehyde, ethyl addressed. Firstly, it is ideal if the instructor charged with
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acetoacetate and urea with mineral acid catalyst in ethanol designing and implementing a green course is the same one
solvent for 90 min to form a dihydropyrimidone. In compari- who teaches at least one introductory prerequisite course.
son, the modern solventless method utilizes ZnCl2 as the A need exists to integrate important principles into first-year
catalyst, reducing the heating time to 20 min. This addresses general chemistry courses, particularly dealing with stoichio-
two of the Twelve Principles: ‘‘use of auxiliary substances metry discussions. An attempt to achieve this in the context of
should be made unnecessary wherever possible’’ and ‘‘energy some introductory exercises has been published (Song et al.,
requirements of chemical processes should be recognized and 2004). Also, both lectures and laboratories associated with
should be minimized’’ (Anastas and Warner, 1998). Each such courses are ideal for discussing the principles of process
student performs both procedures within one laboratory atom economy and E-factor. Secondly, there are specific items
session so that quantitative comparison between the reactions in introductory organic chemistry courses (typically taught in
is straightforward. second-year) that require revision and/or amendment. These
The impact of being trained to critically evaluate transfor- include the following major points:
mations from a green perspective is apparent towards the end how to consistently balance chemical equations, indicating
of Organic Synthesis Techniques. Each class member is the presence of all organic and inorganic products
assigned an individualized target compound to synthesize in how to clearly represent organic molecules on paper/using
two laboratory periods from a given starting material. They chemical drawing software, keeping the same structural aspect
are encouraged to generally employ green chemistry principles, throughout a synthetic pathway
adopting catalytic measures where possible. Students are respon- how to locate the starting materials of a chemical synthesis
sible for all aspects of planning and synthesis execution in the desired product structure
and routinely incorporate a number of sustainable strategies making it known to students from the outset the complete
(e.g. using solvents derived from biomass and greener reagents, classification of organic reaction types: substitutions, rearrange-
solvent-free reactivity, reactions under mild conditions) (Dicks ments, redox reactions, additions (includes couplings, multi-compo-
and Batey, 2012). nent reactions, cyclizations, condensations), and eliminations
how to identify nucleophilic/electrophilic sites in any kind
5. Different ‘‘shades of green’’ of chemical structure
The term ‘‘shades of green’’ has been applied to describe the how to identify BrØnsted-type and Lewis-type acidic/basic
variable environmental friendliness of different reaction solvents sites in any kind of chemical structure
(Clark and Tavener, 2007). This is instructive terminology to establishing connections between correctly balancing an
share with undergraduates, who are much more familiar (and equation, pinpointing starting materials in the target product
comfortable) with a ‘‘correct’’ answer to a chemical problem. It structure and constructing a reasonable curved arrow mechanism
should be emphasized that applying green chemistry principles to for every new reaction taught.
a system is a comparative exercise and not an absolute one, and
that it is not ‘‘all or nothing’’ (Kerr and Brown, 2009; Bennett,
Payoffs of green chemistry thinking
2010). An asymptotic approach has been outlined where students
consider the following three questions after performing any There are major advantages afforded to undergraduates by
laboratory work (Goodwin, 2004): (i) ‘‘what was green about inclusion of green principles into their educational experience.
74 Chem. Educ. Res. Pract., 2012, 13, 69–79 This journal is c The Royal Society of Chemistry 2012
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As most materials have been developed for organic courses, trends. As mentioned earlier, there are many false claims of
three important skills typically acquired from them are ‘‘greenness’’ in the chemical literature. Often an argument is
outlined below with specific examples. made on the basis of only one of the Twelve Principles. This
Deeper analysis and richer discussion of synthesis perfor- represents a narrow view rather than a multivariate global
mances by comparative analysis. In a third-year undergraduate approach which considers all material and energy consump-
Industrial and Green Chemistry course, students analyze multiple tion, and the environmental impact of any waste produced. An
synthesis plans towards three synthetic targets: ibuprofen, prava- example here is the oft-quoted declaration of a ‘‘solventless’’
doline and a dihydrodiazepine (Andraos, 2012(a)). Each synthesis reaction. In the vast majority of cases, this only applies to no
plan is taken from the primary chemical literature. Each example reaction solvent being used—it does not include or take into
illustrates the ubiquitous problem that, for most of the time, no account any solvents used in product work-up or purification
one plan has all the ‘‘right’’ fully optimized characteristics in every operations (Dicks, 2009(a)). A ‘‘dry-laboratory’’ teaching
category. By exposing students to such well-documented real- approach has been reported where students focus on the
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
world scenarios they begin to appreciate the difficulties involved in impact of auxiliary substances such as extraction solvents
reaction optimization. They become able to directly link that and separation agents as sources of waste after a solvent-free
the endeavours of optimization and ‘‘greening’’ are one and the organic transformation (Van Arnum, 2005).
same – a point emphasized by Laird’s editorial (Laird, 2012). They In a similar fashion, just because a reaction is run in water or
also discover that because chemistry is an experimental science in an ionic liquid does not make it inevitably ‘‘green’’, and simply
governed by compromise, optimization inevitably involves prioriti- because a reaction begins with a biofeedstock does not make it
zation of variables. They additionally learn that metrics are automatically ‘‘sustainable’’. Interestingly, the journal Green
important tools to verify claims of greenness made in the literature Chemistry has revised its editorial policy on accepting papers
and to proofread experimental procedures. for publication on the subject of ionic liquids precisely because of
Critical evaluation of merits and bottlenecks in synthesis false advertisements of ionic liquids as ‘‘green solvents’’ (Welton,
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plans, consequently offering creative solutions that can address the 2011). Multi-component reactions (MCRs) and ‘‘one-pot’’
shortcomings. In the same course, students undertake innovative reactions are not necessarily ‘‘green’’—even though they gener-
problem set questions covering various aspects of synthesis ally proceed with high atom economy, they may require toxic
optimization. These include reaction network analysis, cost ana- reagents/solvents or chromatographic separation of products.
lysis, energy input analysis, comparison of linear, convergent, and A similar situation exists for reactions performed under catalytic
divergent strategies, green metrics analysis for material efficiency conditions. The tetrapropylammonium perruthenate (TPAP)
and probability analysis based on target thresholds for reaction catalysis of primary alcohol oxidation to an aldehyde has been
‘‘greenness’’. They suggest multiple synthesis plans for a single undertaken and analyzed by undergraduates within the context
target molecule given various constraints simulating real-world of the Twelve Principles (Koroluk et al., 2011). Student laboratory
situations, including availability of source starting materials and reports reflect the understanding that simply because a reaction
threshold limits on atom economies for reactions and the overall employs a catalyst, it is not automatically a perfectly green
proposed synthesis plans (Andraos, 2012(a)). process. A recent statistical survey of over 1400 such reactions
Increased memory retention of fundamental concepts published up to 2010 as part of a larger evaluation of a synthesis
learned, particularly if real-world industrial chemistry examples database showed that 54% of them would satisfy simultaneously
are discussed. A nice illustrative example is the three industrial the basic criteria of kernel reaction mass efficiencies (excluding all
syntheses of beta-carotene, a food colourant, which highlights the solvents and auxiliary materials) exceeding 60% and reaction
discovery and application of three fundamental organic reactions yields exceeding 80% (Andraos, 2011(b)). These kinds of reality
that students learn about in introductory organic chemistry checks compel educators to ensure that students learn to adopt a
courses: the Wittig reaction (BASF synthesis) (Nuerrenbach balanced modus operandi when assessing ‘‘greenness’’.
et al., 1977), the hydrogenation of alkynes to cis-olefins using
2. Attention to experimental detail
Lindlar’s catalyst (Hoffmann-LaRoche synthesis) (Isler et al.,
1947; Inhoffen et al., 1950; Isler et al., 1956; Surmatis and Ofner, The itemization of experimental procedural details needs to
1961), and the McMurry coupling of ketones to olefins (McMurry dramatically improve in journal articles and patents, if any
and Fleming, 1974). Telling students the background story behind reliable estimates of waste production analysis are to be made.
the discovery of these reactions not only helps them remember the There is often casual reporting of quantities of materials used
reactions, but also illustrates the circumstances, motivation, and in work-up and purification procedures (e.g. volumes of all
mechanics of how real research is done in an industrial setting. extraction solvents, volumes of chromatographic packing
materials, volumes of elution solvents, masses of drying
agents, masses of gaseous reagents). Reaction yields may not
Conclusions—areas for improvement in teaching and be quoted or may be incorrectly calculated. The frequency of
research revealing reaction performance in patents is lower than in
journal articles, which impacts on the metrics evaluation of
1. Inaccurate assertions of ‘‘greenness’’
good industrial examples taken from the patent literature to
A symbiotic relationship exists between research and teaching illustrate green chemistry ideas. Evaluation of plans and
aspects of any academic discipline. The next generation of reactions should include the synthesis of ionic liquid solvents
researchers ‘‘learn their trade’’ in the undergraduate classroom and specialized catalysts or ligands, as these are routinely
and modern teaching practices are shaped by current research omitted from the main synthesis evaluation. Often the structure
This journal is c The Royal Society of Chemistry 2012 Chem. Educ. Res. Pract., 2012, 13, 69–79 75
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of a specialized catalyst involves a more complicated synthesis and is also the medium of choice for work-up washes, it is not
than the target product that the catalyst is designed to help universally included in cost calculations of input materials in a
generate. This lack of detail severely hampers the decision- synthesis plan. Research into increasing its use as a reaction
making process between the relative ‘‘greenness’’ of two or more solvent for a wide variety of organic reactions is gaining
synthetic routes. Biocatalytic transformations are generally traction in the undergraduate laboratory curriculum (Dicks,
poorly documented in terms of the needs of a chemist to evaluate 2009(b); Sauer, 2012). Widespread success in these and associated
reaction performance. Reaction yields are often reported as fields may lead to a re-writing of undergraduate textbooks as a
molar yields with respect to the substrate of interest, which paradigm shift evolves (Tucker, 2010). The emerging field of
may or may not be the limiting reagent. Stoichiometrically continuous flow reactors to carry out reactions instead of tradi-
balanced equations may not be possible to write down for such tional round-bottomed flasks promises to revolutionize the scope
reactions since the chemistries of the transformations may not be of reaction possibilities including control of thermodynamic and
fully known. kinetic products by changing flow rates of reagents (Ley and
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