196 Journal of Chemical Education

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10.1021/ed8000396 Published on Web 01/12/2010
In the Laboratory
Ionic Liquids and Green Chemistry: A Lab
Experiment
Annegret Stark,* Denise Ott, Dana Kralisch, Guenter Kreisel, and Bernd Ondruschka
Institute for Technical Chemistry and Environmental Chemistry, Friedrich-Schiller University of Jena,
Lessingstrasse 12, 07743 Jena, Germany
*annegret.stark@uni-jena.de
Ionic liquids as solvents have found interest in various
applications (1, 2). Ionic liquids are salts with melting points less
than 100 C and consist of a large organic cation (e.g.,
1,3-dialkylimidazolium) combined with an organic or inorganic
anion (e.g., acetate, chloride, trifluoromethanesulfonate). Because
of this structural variability, which allows for the tuning of the
physicochemical solvent properties, ionic liquids are so-called
designer solvents. In addition, ionic liquids feature a low vapor
pressure and nonflammability, leading to the assumption that
emissions and exposure are reduced. Hence, ionic liquids have
often been uncritically referred to as green or environmentally
benign (e.g., refs 3 and 4). While this may be true in some instances,
generalized statements of this kind are not accurate, especially in
a teaching context. Nowadays, it is widely accepted that no solvent
is a priori green; its greenness strongly depends on its toxicological
properties and on the environmental impact resulting from the
specific application and from the whole life cycle.
To realize more sustainable thinking and an implementation
of sustainability criteria in research, development, and production,
educational strategies have to include green-chemistry principles
and indicators of sustainability. This approach allows students to
judge chemical transformations or the use of chemical compounds,
thus giving additional training for their future professional task. In
this Journal, a number of articles dealing with green-chemistry
concepts andmetrics ineducation as well as laboratory experiments
have been published (e.g., refs 5-14).
In industry, life-cycle assessment (LCA) (15) is carried out
to assess the ecological impact of a process or product. However,
at the research and development level and when carrying out
reactions on a laboratory scale, this approach is too complex and
much of the data required may not be available (e.g., toxicological
data of the products, recycling strategies, etc.). Additionally, LCA
does not take into account the cost of production, which is
presently the prime factor for industry to decide whether to run a
process. Hence, simple ecological and economic metrics for the
assessment of chemical reactions have been developed
1
to deal
with questions of ecological and economic impact at the lab level
and have been applied to ionic liquids (16-18).
1
In the style of
the Web-based NOP (Sustainability in the Organic Chemistry
Laboratory Course) (10-20),
1
the lab experiment presented
herein takes into account the yield, atom economy, energy
efficiency, and E-factor as metrics and integrates a qualitative
assessment of the (eco)toxicity of educts, auxiliaries, and pro-
ducts. Furthermore, the metric reaction mass efficiency is
employed. Besides mass- and reaction-type-based key objectives,
the assessment of the ecological impacts of the starting materials
and products as well as prices of chemicals is advisible to compare
the reactions from a more holistic point of view.
Although ionic liquids have received increasing attention in
both academia and industry, a thorough literature review
1
revealed
that the development of these neoteric solvents is not reflected
appropriately in laboratory experiments (4, 21, 22), although many
of our colleagues cover them in diverse undergraduate lectures.
Experimental Overview
General Considerations
This experiment examines the synthesis of two ionic liquids
via alkylation of 1-methylimidazole by nucleophilic substitution
(Menschutkin reaction) and compares the effect of different
methods of energy input (microwave vs convective heating), the
variationof the alkyl halide reagent, and the variationof the reaction
temperature and time onseveral key indicators of sustainability. The
reactions investigated in the experiment are shown in Scheme 1.
Since both economic and ecological aspects depend on the
reaction scale and the future applications of the ionic liquids are
not known, the holistic from cradle to grave approach of life-
cycle assessment has to be broken down to determine local
optima in the process (cradle to bench). Scheme 2 displays this
approach including provision and reaction on a generalized
example and the key indicators of sustainability investigated.
2
The six quantitative key indicators are the yield, atom economy,
reaction mass efficiency, the E-factor, energy efficiency, and price
of chemicals. The experiments are carried out on a 0.2 mol scale
and standardized to 1 kg.
3
Furthermore, (eco)toxicological data
of starting materials and products are assessed by taking into
account material safety data sheet (MSDS) information and
primary literature data (e.g., references such as 23-27).
edited by
Mary M. Kirchhoff
Educational Division
Washington, DC 20036
Scheme 1. Reaction Parameters in the Synthesis of Ionic Liquids
[C
6
mim]X
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In the Laboratory
The tasks of this lab experiment and the learning goals are
summarized in Table 1. Depending on the organization of the
laboratory course in which this experiment is to be implemented,
one of three modes can be chosen: mode 1 is a conventional lab
experiment; mode 2 is a research project; and mode 3 is a
homework assignment. The requirements and suggested group
sizes for each mode are detailed in Table 2.
1
Experimental Details
The students perform reactions I-V (Scheme 1) as detailed
in the supporting information. In addition to comparing the
common chemical objective, the yield, the energy requirements
of each synthesis and workup, the costs of all chemicals
employed, and toxicological data are compiled. Using the
formulas displayed in Table 3, the students compare the key
indicators.
Hazards
1-Methylimidazole is combustible and causes eye, skin,
digestive, and respiratory tract burns. 1-Bromohexane is com-
bustible and is an eye, skin, and respiratory irritant. 1-Chloro-
hexane is flammable and incompatible with strong oxidizing
agents and strong bases. Diethyl ether is harmful by ingestion,
inhalation, or through skin contact and is highly flammable.
Scheme 2. GeneralizedExample for the Holistic Optimization of aReaction or Product: Use of Key Indicators of Sustainability under Otherwise Constant
Conditions
Table 1. Experimental Tasks and Learning Goals
Experimental Tasks Learning Goals
Literature review and data retrieval Introduction to ionic liquids
Introduction to microwave-assisted chemistry
Compilation of toxicological data, chemical prices, R S codes
Summary of relevant key indicators
Alkylation Reaction yield as function of temperature, time, energy input, and type of alkylating agent
Differences between microwave-assisted and conductively heated reactions in terms of
energy requirement
Chemical analysis (Karl-Fischer titration
and
1
H NMR or HPLC)
Introduction to analytical methods
Discussion of
1
H NMR spectra and HPLC chromatogram (peak assignment, integration)
Determination and deduction of impurities from weighed yield by stoichiometric calculations
Efficiency analysis Introduction to ecological/economic assessment methods
Introduction and calculation of simple green metrics
Optimization potential of reactions in the lab assessed with the help of the metrics
Report writing Writing a scientific essay
Critical analysis of ionic liquids (synthesis, application) and
assessment of reactions with the help of questions and tasks
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In the Laboratory
Discussion
Representative student data are shown in Table 4. Interest-
ingly, the atom economy for reactions I-V is 100% in all cases,
which indicates no formation of byproducts. This metric does
not take into account yields and hence cannot be used to
distinguish the relative greenness of the reactions investigated.
The atom economy serves as a general comparison of organic
reactions or different synthetic strategies. By comparing the
reaction mass efficiencies and E-factors, a more concrete state-
ment about the eco-friendliness of the reactions can be made.
Conditions in reaction III are not favorable as compared to the
other reactions because the amount of waste produced
(unreacted starting material) is much higher than in the other
Table 2. Specifications of the Modes in which the Experiment Can Be Conducted
Mode 1: Lab Experiment Mode 2: Research Project
Mode 3: Homework
Assignment
Group size 2-4 students 1-2 students 1-2 students
Laboratory time 2 4 h 3 8 h 0 h
Homework/report writing Approximately 8 h
per student
Approximately
16 h per student
Approximately
16 h per student
Background information
(ionic liquids,
reaction mechanism,
microwave
assisted synthesis)
Lecture Lecture and/or
literature search
Lecture and literature
search
Data retrieval from literature R S codes toxicological
data market prices
R S codes toxicological
data market prices
R S codes toxicological
data market prices
Experimental data provided Yields, energy requirements,
and analytical data for
reactions III-V
None Yields, energy requirements,
and analytical data for
reactions I-V
Table 3. Quantitative Key Indicators, Formulas, and Units
Key Indicator Formula Unit
Yield
Yield
nproduct
nraw material

raw material

product
100%
%
where is stoichiometric coefficient
Atom economy (28-30)
Atom economy AE
molar mass of the desired product
P
molar mass of the raw materials
100%
%
Reaction mass efficiency (31)
Reaction mass efficiency RME
mass of the desired product
P
mass of chemicals used
kg/kg
E-factor (32-35)
E-factor E
mass of waste
mass of the desired product
kg/kg
Energy efficiency
Energy efficiency
mass of the desired product
energy demand of the synthesis reaction and processing
kg/kJ
Price of chemicals
Cost
prices of the required amounts of chemicals used
mass of the desired product
Currency unit/kg
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In the Laboratory
reactions, resulting in the highest E-factor and lowest reaction
mass efficiency. In general, a higher yield results in higher
reaction mass efficiencies and lower E-factors.
In addition to mass-based statements, energy requirements
must be considered to assess the ecological (and also economic)
performance of processes and products. In this experiment, the
energy demand for the synthesis and workup is measured. In the
conductively heated experiments, the energy efficiency is propor-
tional to the yield (Table 4). However, by contrasting the
conductively heated experiment (I) with the microwave-assisted
experiment (II), the energy efficiency decreases in spite of a
higher yield, which indicates that the former reaction setup is
energetically more favorable. This may be due to either the
peripheral equipment of the microwave apparatus requiring extra
energy or the low energy efficiency of the conversion of electric
energy into microwave radiation energy. To obtain a more
holistic view, the energy required during the entire life cycle of
a product has to be further considered. Therefore, students are
asked to critically comment on questions designed to evoke
thinking in terms of life cycles and cumulative energy demand.
1
An increase in reaction time (I vs V) or temperature (III vs
V) yields a better reaction mass efficiency. Although the energy
demand is higher, a higher yield is beneficial for the overall energy
efficiency. The E-factor is reduced dramatically, since the
amount of waste decreases, while the amount of product
increases.
The energy efficiency increases significantly if the starting
material 1-chlorohexane is replaced with the more reactive
1-bromohexane, and an almost quantitative yield is obtained
within 6 h (III vs IV). Additionally, the price of chemicals is
reduced for IV because a lower total amount of chemicals
is necessary to produce 1 kg of the desired ionic liquid, and
1-bromohexane is the cheaper alkylating agent.
In general, reaction IV seems to be the best alternative
regarding the key objectives reaction mass efficiency, E-factor,
energy efficiency, and price of chemicals. Nevertheless, process
Table 4. Student-Generated Metrics for Assessment of the Ionic Liquid Reaction
Reaction Yield/%
Atom
Economy/%
Reaction Mass
Efficiency/(kg/kg) E-factor/(kg/kg)
Energy
Efficiency/(10
-3
kg/MJ)
Price of
Chemicals/(h/kg)
a
I 47 100 0.29 2.4 5.7 273.5
II 55 100 0.34 1.9 3.5 233.8
III 7 100 0.05 20.9 0.8 1823.3
IV 96 100 0.65 0.5 13.6 90.4
V 80 100 0.50 1.0 8.9 160.4
a
Prices compiled from http://www.sigma-aldrich.com as of June 2008 or http://www.vwr.com (diethyl ether) as of February 2008.
Figure 1. Qualitative assessment of ecological and toxicological effects of the chemicals used in the lab experiment.
200 Journal of Chemical Education
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In the Laboratory
safety and toxicity criteria have to be taken into account.
Therefore, students are asked to research safety data sheets and
the primary literature regarding toxicological and ecological
information of the starting materials, auxiliaries, and products.
The results obtained can be summarized in writing or in the form
of a color scheme (Figure 1).
The assessment in Figure 1 shows that the negative envir-
onmental and health effects of 1-bromohexane are greater than
those of the chloro-substituted analogue, which have to be
balanced against the benefits of the higher reactivity of the
former compound. These results emphasize the need of an
ecological assessment regarding (eco)toxicity criteria. The assess-
ment also indicates that little information concerning ecological
and toxicological effects of the ionic liquids synthesized is
presently available, reflecting the relative novelty of these com-
pounds. It is expected that this situation will change in the near
future.
Besides the efficiency analysis, postlab questions and tasks
can be given to students to consolidate their recently attained
knowledge. The questions should be discussed in the student's
report.
1
Conclusions
This experiment was developed for advanced undergraduate
students to investigate ionic liquids and the ecological assessment
of reactions and chemicals. This is achieved by the combination
of lab experiments that demonstrate the influence of different
methods of energy input (microwaves, convective heating) and
variations in reaction temperature, time, and alkylating agent on
yield; green metrics (atom economy, reaction mass efficiency,
E-factor, energy efficiency); and price of chemicals and
(eco)toxicological data. The comparative discussion of these
aspects enables students to realize that a synthesis method leading
to quantitative yields is not a priori green as other factors (nature
of reactants, energy consumption etc.) have to be assessed in a
more global context as well.
Acknowledgment
We thank Stephan Reich and Claudia Palik for their
contributions in the laboratory. D.O. and A.S. are indebted to
the German Federal Environmental Foundation (DBU) and the
Deutsche Forschungsgemeinschaft (DFG, Priority Programme
Ionic Liquids SPP 1191), respectively, for support.
Notes
1. Refer to the supporting information for further information.
2. A follow-up manuscript will detail the optimization of the
workup process by extraction.
3. Students should be advised that a theoretical scale-up of this
kind is only permissible for similar scales.
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Supporting Information Available
Background information and further reading on ecological and
economic metrics, the Web-based NOP, a summary of the literature on
ecological assessments and educational experiments involving ionic
liquids, Gantt charts detailing the requirements and timetables
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Journal of Chemical Education 201
In the Laboratory
depending on the length of laboratory time, detailed experimental
information (required equipment, glassware, and chemicals), experi-
mental procedures, analytical characterization, tables (S2, protocol of
the energy demands and masses depending on the reaction procedure:
example results; S3, protocol of the metrics atom economy, reaction
mass efficiency, E-factor, and energy efficiency investigated: example
results; S4, determination of the prices of the chemicals used: example
results), postlab questions assisting in the preparation of the research
report, a list of abbreviations, and student handouts. This material is
available via the Internet at http://pubs.acs.org.