RESEARCH FRONT

Full Paper

CSIRO PUBLISHING

Aust. J. Chem. 2009, 62, 236243

www.publish.csiro.au/journals/ajc

Microwave-Assisted Chemistry: a Closer Look

at Heating Efficiency
Richard Hoogenboom,A,B,D Tom F. A. Wilms,A Tina Erdmenger,A,B
and Ulrich S. SchubertA,B,C,D
A Laboratory

of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology,

PO Box 513, 5600 MB Eindhoven, the Netherlands.
B Dutch Polymer Institute (DPI), PO Box 902, 5600 AX Eindhoven, the Netherlands.
C Laboratory of Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena,
Humboldtstrasse 10, D-07743 Jena, Germany.
D Corresponding authors. Email: r.hoogenboom@tue.nl; ulrich.schubert@uni-jena.de

Nowadays, microwave heating has evolved into a common tool for chemists based on its numerous advantages over
conventional conductive heating. Surprisingly, the efficiency of microwave-assisted heating is still rather unexplored. In
this contribution, we report our investigations concerning the heating efficiency of a variety of solvents including polar and
apolar substances. Moreover, the effects of adding salt or passive heating elements on the microwave heating efficiency
will be addressed. Finally, the heating efficiency of demineralized water is discussed at different volumes and with different
microwave power levels in both monomode and multimode microwave synthesizers, demonstrating maximum average
heating efficiencies of 10% for small-scale vessels (5 mL), 20% for medium-scale (50 mL), and 30% for large-scale
microwave heating (400 mL).
Manuscript received: 17 November 2008.
Final version: 16 December 2008.

Introduction
Microwave heating has been used in laboratory applications as an
alternative for conductive heating systems since the 1980s.These
first investigations were highly experimental, using domestic
microwave ovens. Since the beginning of this millennium, a
range of scientific microwave ovens, dedicated and designed
to perform chemical syntheses, is commercially available. The
major advantage of dedicated microwave synthesis equipment
is the real-time monitoring of reaction temperature and pressure, which can be adjusted by controlling the microwave
power. In addition, these reactors are designed to cope with
violent explosions that might occur during runaway exothermic reactions. Nowadays, microwave dielectric heating is an
established method in, e.g. synthetic organic[15] and polymer chemistry[69] as well as bioscience.[10] The popularity of
microwave irradiation for chemistry is based on the observed
higher yields, faster reactions, reduced side-product formation
and even changed selectivity.[11] The occurrence of so-called
non-thermal microwave effects based on selective heating
of more polar substances is still under debate,[12] although
recent studies with careful temperature control tend to disregard
non-thermal microwave effects.[13] Furthermore, microwave
irradiation has been used to develop green synthesis protocols
by the exclusion of organic solvents.[14,15] Based on these advantages of microwave irradiation in chemistry, a variety of reports
discuss scaling up microwave-assisted reactions, of which the
majority of studies focus on continuous-flow reactions because
the limited microwave penetration depth of several centimetres
obstructs the use of large-batch reactors.[1619]

Despite the fact that already several studies have been

reported on scaling up microwave-assisted reactions, only a very
limited number of studies have reported on the efficiency of
microwave heating for chemical transformation to estimate economic viability. As a reference, it should be noted that the use
of microwave irradiation in large-scale (industrial) microwave
ovens has been demonstrated to be more efficient than conventional thermal heating for, e.g. cooking of rice,[20] drying of
cranberries,[21] and waste drying.[22] However, the majority of
such large-scale industrial processes benefit from heating materials with low water content. In other words, with conventional
heating, the entire product has to be heated, whereas microwave
irradiation mainly heats the water present, resulting in lower
power consumption. In contrast, the entire reaction mixtures
should be heated for chemical transformation and, therefore,
these efficiencies reported for drying and cooking processes
are not valid. A recent report by Leadbeater and coworkers
revealed that the synthesis of biodiesel under microwave irradiation could be performed up to four times more energy efficiently
under microwave irradiation compared with thermal heating.[15]
The larger efficiency was achieved by a very fast reaction in a
continuous-flow microwave process, whereas the energy consumption of a microwave batch reaction was similar to the
conventional process. Clark et al. reported that microwave irradiation was more energy efficient than oil bath heating for Suzuki
coupling and FriedelCrafts acylation as well as a Knoevenagel
reaction.[23] The energy efficiency with microwave irradiation
was found to be from 1.5 to 100 times more efficient, which could
be mainly ascribed to the shorter reaction times and higher yields

CSIRO 2009

10.1071/CH08503

0004-9425/09/030236

RESEARCH FRONT

Heating Efficiency in Microwave-Assisted Chemistry

under microwave irradiation. In addition, Kappe and coworkers discussed the energy efficiency for DielsAlder, hydrolysis,
cyclocondensation, and Suzuki reactions using microwave and
oil bath heating as well as a heating mantle.[24] These investigations revealed that the energy efficiency of microwave-assisted
reactions is only superior to conventional heating methods
when the reaction times can be significantly reduced by using
superheated conditions. These previous reports on the energy
efficiency of microwave-assisted chemistry evaluated the efficiency in terms of energy consumed per mole product. However,
basic studies on the heating efficiency of microwave irradiation
are limited. In fact, there is one report concerning microwave
heating of 150 to 1200 mL of water with or without sodium chloride or sucrose in a domestic microwave oven revealing close
to 100% conversion of microwaves to heat.[25] However, the
conversion from electrical energy to microwave has not been
reported. Ondruschka and coworkers reported microwave heating efficiencies from 8% for hexane up to 90% for water and
a variety of alcohols when heating 500 g substance in an open
vessel using a multimode dedicated microwave reactor.[26] However, combining this 90% heating efficiency with the 50 to 65%
efficiency for generating microwaves from electricity results in
overall microwave efficiency below 50%.[27]
Altogether, only very little is known about the efficiency
of converting electricity via microwaves to heat as it is done
in microwave-assisted chemistry. Therefore, the current study
reports on the efficiency of microwave heating of a variety
of common solvents. In addition, the effects of adding salt to
aqueous solutions as well as adding passive heating elements
on the heating efficiency will be discussed. Furthermore, the
heating efficiency for heating water is evaluated for different
volumes using different dedicated microwave reactors including
both monomode and multimode devices.
Background of Microwave Heating
Microwaves are electromagnetic waves in the frequency range
of 0.3 to 300 GHz, which corresponds to wavelengths of 1 m to
1 cm, respectively. This region of the electromagnetic spectrum
lies between the far infrared and radio frequencies. Out of the
several frequency bands that are available for domestic and scientific applications, a frequency of 2.45 GHz is commonly used
for kitchen microwave ovens and industrial microwave reactors.
Radiation of this frequency only affects molecular rotation and
is not strong enough to break chemical bonds. Because equipment is widely available to efficiently generate microwaves at
this frequency, it is a convenient method for heating microwaveabsorbing substances. Microwaves, being of an electromagnetic
nature, consist of time-varying electric and magnetic fields, and
propagate through space at the speed of light. However, the
magnetic part of the electromagnetic waves does not interact
with organic media and, thus, will not participate in microwave
heating for most chemical transformations. The capability of a
compound to convert microwave irradiation to heat is given by
the loss tangent, tan():
tan() =

2 ()
1 ()

in which 1 is the permittivity, 2 is the dielectric loss factor,

and is the frequency. The higher tan() is at 2.45 GHz, the
better the compound will absorb microwaves, resulting in better
heating. Consequently, polar substances are expected to heat up
more efficient than non- or less polar counterparts. In general,

237

the dielectric loss factor of a solvent determines its ability to

absorb microwave energy. The power dissipation by the dielectric material is proportional to this loss factor (2 ). However,
dielectric properties are in general strongly frequency and temperature dependent and, unfortunately, the optimal frequency
for most efficient heating shifts further away from 2.45 GHz on
heating.[28] A recent study reported the effect of using a 5.8 GHz
frequency for microwave-assisted organic synthesis, demonstrating much faster heating compared with using 2.45 GHz.[29]
For further discussion on dielectric heating, the reader is referred
to the excellent reviews of Mingos et al.[27,30]
Besides dielectric heating, ionic species can be heated under
microwave irradiation by an ionic heating mechanism. When an
ionic solution is placed in an electric field, the field causes an
ionic current, which gives rise to joule heating of the solution,
which is proportional to the ionic conductivity (i ) of the material. The ionic conductivity depends on ion concentration and is,
in general, also dependent on temperature and frequency.
In general, ionic heating will occur in combination with
dielectric heating of the surrounding solvent and the total average energy dissipation (P) by a dielectric material in a microwave
field can be given by:
1
1
0 2 ()E02 + i ()E02 ,
2
2
where 0 is the permittivity of a vacuum and E0 is the electric
field amplitude. The second term in this equation represents the
power dissipation due to ionic currents, where i is the ionic
conductivity, which depends in general on ion concentration,
frequency, and temperature.
P=

Results and Discussion

In the present contribution, the total efficiency of heating different solvents will be discussed and the heating efficiency
for heating demineralized water will be compared for various microwave synthesizers. In all experiments, closed reaction
vessels of constant volume were used.
The efficiency () of microwave heating can be defined by
the ratio of the internal energy change of the system (dU ) and
the total input of electric energy (dEin ):
=

dU
.
dEin

As a closed vessel is used, the vessel volume is constant, so

that the change in internal energy with increasing temperature
is given by:
dU = ml cl dT + mg cg dT + vap H dng ,
where ml and mg denote the mass of the liquid and vapour
respectively, cl and cg denote the specific heat of the liquid
and gas phase respectively, vap H is the heat of vapourization
of the liquid, and dng represents the number of moles of liquid that have been vapourized during the temperature change
from T to T + dT. Parameters ml , mg, cl , cg , and vap H may
all depend on temperature and pressure, which is not taken
into account in the current study. However, in the temperature
range from room temperature to 250 C, the working range of the
microwave synthesizers, the last terms are very small compared
with the first, and may thus be neglected (see justification in the
Accessory Publication). Thus, the change in internal energy may
be written as:
dU = ml cl dT .

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R. Hoogenboom et al.

250

678
676

200

674

150

670

T [C]

Pin [W]

672

668

100

666
664
662
660
658

0
0

20

1
2
3

50

1
2
3
40

60

80
t [s]

100

120

140

160

20

40

60

80
t [s]

100

120

140

160

Fig. 1. Input power (left) and temperature profile (right) during 300 W microwave irradiation (Biotage Emrys Liberator) of 5 mL demineralized water
performed in triplicate.

30

dEin = Pin dt,

25

where dt denotes the time interval corresponding to the energy

change. Inserting these equations into the efficiency equation
gives:

20

ml cl dT

=
.
Pin
dt
Thus if the electric input power is known, the overall efficiency of microwave heating may be approximated by taking the
time derivative of the temperature (T) and multiplying this with
ml cl /Pin .
To experimentally determine the microwave heating efficiency, the temperaturetime profile from the microwave synthesizer is taken to calculate dU. In addition, the electrical input
power is measured with a power meter that is inserted in between
the plug of the microwave and the power socket. To compensate
for the power consumption of the microwave operating system, the idle mode power consumption is subtracted from the
measured power consumption.
Small-Scale Microwave Heating Efficiency (15 mL)
The small-scale experiments were performed on a Biotage
Emrys Liberator monomode microwave synthesizer. The idle
mode power consumption was determined to be 135 W, which
will be used in later calculations. Before comparing different volumes and solvents with respect to microwave heating
efficiency, the reproducibility of the experimental set-up was
investigated. Therefore, a microwave vial containing 5 mL demineralized water was heated three times with 300 W microwave
power. The resulting power input as well as temperature profiles
are depicted in Fig. 1, demonstrating rather comparable plots for
the three separate heating experiments. As the set temperature of
250 C was not reached, 300 W microwave irradiation was supplied over the entire time span. To achieve this 300 W microwave
power, 670 W of electrical power (after subtraction of idle mode
power) was required, indicating 45% efficiency for converting
electricity to microwaves. The large decrease in heating rate at a
temperature of 160 to 170 C is due to a rapid decrease of the loss

Efficiency [%]

If the total electric input power to the microwave is given by

Pin , then the total input of energy may be written as

1
2
3

15
10
5
0

20

40

60

80
t [s]

100

120

140

160

Fig. 2. Calculated heating efficiency during 300 W microwave irradiation (Biotage Emrys Liberator) of 5 mL demineralized water performed in
triplicate.

factor of water at high temperatures, which can be ascribed to the

loss of the extended hydrogen bond network in water.[31] The efficiency versus time plot resulting from the electrical power input
and temperature profile is shown in Fig. 2 (a list of specific heat
values used is given in the Experimental section). The heating
efficiency shows an unexpected profile with two distinct peaks
that reach a maximum total efficiency of 25%.The nature of these
peaks is not clear, but might be related to cavity microwave field
tuning, meaning that the controlling software of the microwave
synthesizer optimizes the attenuator for each reaction mixture.
This cavity microwave field tuning is also believed to cause the
observed differences in heating and efficiency profiles. From
the efficiency profiles, the average efficiency over the different
time periods was calculated as summarized in Table 1. Strikingly, the overall efficiency is as low as 5%. Despite the different
temperature profiles for the three consecutive heating runs, the
calculated efficiencies are similar, demonstrating that the experimental set-up provides reliable efficiency data for microwave
heating.

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Heating Efficiency in Microwave-Assisted Chemistry

239

To minimize the error in heating efficiency when comparing

microwave heating of various solvents and volumes, the heating
efficiency was calculated for heating from ambient temperature
up to 100 C to avoid large deviations in the dielectric loss factor.
Furthermore, the full 300 W microwave power was applied for
all solvents up to at least 100 C.
At first, the effect of volume on the heating efficiency was
investigated for demineralized water using conical (A) and
round-bottom (B) microwave vials (Fig. 3; Fig. S1 and Table S1
in the Accessory Publication). There is a distinct difference in
average heating efficiency for the different vials, in which the
conical vials result in lower efficiency even when using the same
volume, which implies that the microwave cavity is not well
optimized for the conical vials. When looking at the larger roundbottom vials, the average efficiency increases from 8 to 10%. A
possible explanation could be the physical shape of the Liberator
cavity, in which only the top part of the vial is irradiated. As a
result, the relative part of the liquid that is irradiated will increase
with increasing volume, resulting in higher heating efficiency.
Based on these previous observations, all subsequent experiments were performed with round-bottom-shaped vials containing 5 mL of solvent. In a next step, the microwave heating
efficiency was investigated for a range of solvents from apolar
to polar as depicted in Fig. 4 (see also Fig. S2 and Table S2).
The difference in heating efficiency for ultra-pure and demineralized water is within the experimental error. Even though
the maximum efficiency (23%) for demineralized water is higher
than for ultra-pure water (17%), the average efficiency differs
only a tenth of a per cent (Table S2). Apparently, the difference
in impurity level is too small to make a significant difference. For
apolar substances having very low dielectric constants, namely
toluene and diethyl ether, the heating process is very inefficient
Table 1. Average heating efficiency for heating 5 mL demineralized
water in the Biotage Emrys Liberator Microwave
Curve

1
2
3

Average efficiency

with average efficiencies of less than 2%. In fact, it might be

speculated that the observed temperature increase is only due to
microwave absorption by the Pyrex glass tubes rather than the
solvents. Surprisingly, substances with very high dielectric constants, such as DMF and 1-butyl-3-methyl imidazolium chloride
(BMIM-Cl) ionic liquid that were heated with 150 W to avoid
thermal runaway showed still rather low average efficiencies
of 12%.
It is generally known that microwave absorption can be
enhanced by the addition of salt to water. However, the effect
of added salt on the heating efficiency has not been addressed
so far. Therefore, we investigated the heating efficiency of
microwave-irradiating aqueous NaCl solutions ranging from
pure water to 5 wt-% NaCl using both 150 and 300 W power
levels, respectively (Fig. 5; Figs S3 and S4 and Table S3).
The average heating efficiency slightly increases with addition of low salt concentrations up to 0.10 wt-% NaCl. When
increasing the concentration of NaCl to 0.60 and 1.80 wt-%, the
average efficiency rises to roughly 17% when using 300 W power
and the efficiency does not significantly change when further

12
10
8
6
4
2
0
Toluene

Diethyl
ether

Maximum efficiency

050 s

50140 s

Overall

11%
12%
11%

2%
2%
2%

4%
5%
4%

Ethanol

Ultra
water

DMF*

Average efficiency [%]

Fig. 4. Average overall efficiency for heating 5 mL of different solvents
up to 100 C in 2.05.0 mL vials with 300 W (*, 150 W). Ultra water is
ultrapure demineralized water; DMF is N,N -dimethylformamide; BMIM-Cl
is 1-butyl-3-methylimidazolium chloride.

21%
24%
23%

10.0
B

8.0
6.0
4.0
A

1 mL

2 mL

2.0
0.0
A

BMIM-Cl*

2 mL

5 mL

Average efficiency [%]

Fig. 3. Left: Picture of the 0.52.0 mL conical (A) and 2.05.0 mL round-bottom (B) microwave vials. Right: Average overall
efficiency for heating different volumes of demineralized water up to 100 C in different vials with 300 W microwave power.

RESEARCH FRONT

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R. Hoogenboom et al.

increasing the concentration to 5.0 wt-%, indicating that, in

terms of heating efficiency, an optimum is reached at 0.60 wt-%.
A similar trend is observed when the microwave power is
decreased to 150 W. However, the maximum overall heating efficiency increases to 22% when changing the microwave power
from 300 to 150 W. This higher efficiency at lower power clearly
indicates that an excess of energy is supplied to the small sample volume and, thus, the excess energy will be relatively smaller
when 150 W is supplied, yielding higher efficiency.
Besides the addition of salt, the use of passive heating elements, such as silicon carbide or graphite, has been introduced
to improve microwave heating of apolar solvents.[12,32,33] The
effect of silicon carbide passive heating elements on the heating efficiency for both polar and apolar solvents is shown in
Fig. 6 (see also Fig. S6 and Table S5). For the de-ionized water
and toluene samples, a microwave power of 300 W was used; the
DMF samples were heated with 150 W to avoid thermal runaway.
The comparison of the average heating efficiency clearly
shows that there was no improvement in efficiency when heating elements were added to the well microwave-absorbing
DMF. However, when adding the elements to the moderately
microwave absorbing water or the poorly microwave absorbing

toluene, a clear increase in heating efficiency was observed for

water and toluene (Fig. 6). This result can be easily rationalized by the fact that all microwave irradiation will be absorbed
by DMF before it reaches the passive heating elements whereas
only a small amount of microwaves are absorbed by toluene and,
thus, a large amount of microwave irradiation will reach the passive heating elements. It is noteworthy to mention that adding
a single heating element did not significantly increase the heating rate or efficiency (see Accessory Publication), which is most
likely due to the position of the heating element at the bottom of
the microwave vial that is not irradiated in the Biotage microwave
reactor.
In conclusion, the very dense monomodal microwave field
supplied to a relatively small sample volume results in low
average heating efficiency (maximum 22% for aqueous NaCl
solutions). Combining this overall heating efficiency with the
observed 45% efficiency of converting electrical energy to
microwaves leads to the conclusion that 49% of the microwave
energy is converted to heat. The use of passive heating elements
was found to only increase the heating efficiency for moderately and poorly microwave absorbing compounds like water
and toluene. The heating efficiency for demineralized water was
found to be higher with added salt compared with the passive
heating elements, indicating that the homogenous distribution
of ionic species results in better microwave absorption than the
heterogeneous heating elements. Improved heating efficiency in
the presence of the elements might be limited by heat transfer
from the element to the liquid via the relative small contact area.

25
20
15

Medium-Scale Microwave Heating Efficiency (2550 mL)

Medium-scale microwave heating of demineralized water was
performed using a CEM Discover single mode microwave synthesizer upgraded with the large vessel capability (80 mL vessel;
max. loading 50 mL). The efficiency of microwave-heating 25
and 50 mL demineralized water was determined at different
microwave power levels, namely 100, 150, 200, 250, and 300 W.
The microwave software was used to record temperature and
pressure curves, whereas the total input power was recorded
manually at 5 s intervals. However, the temperature profile
of the CEM Discover was recorded as integer values, which
would result in a very scattered efficiency plot when integrated.

10
5
0
Water

0.03%

0.10%
150 W

0.60%

1.80%

5.00%

300 W

Fig. 5. Average overall efficiency (%) for heating 5 mL of water with

different wt-% NaCl up to 100 C in 2.05.0 mL vials with 150 or 300 W.

14
12
A

10
8
A

Toluene

Toluene

6
4
2
0
Water
A

Water

DMF*

DMF*

Average efficiency [%]

Fig. 6. Left: Picture of the 2.05.0 mL round-bottom microwave vial without heating elements (A) and with two heating
elements (B). Right: Average overall efficiency for heating different solvents up to 100 C with and without heating elements and
300 W microwave power (*, 150 W).

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Heating Efficiency in Microwave-Assisted Chemistry

241

25

550

20

Electrical power input [W]

500
450

15

400

10

350

300

0
100 W

25 mL
50 mL

250

150 W

200 W
25 mL

250 W

300 W

50 mL

200
100

150

200

250

300

Fig. 8. Average overall efficiency (%) for heating 25 or 50 mL of

demineralized water with different microwave power settings.

Preset microwave power [W]

Fig. 7. Electrical power input versus preset microwave power for the CEM
Discover microwave.

Large-Scale Microwave Heating Efficiency (200400 mL)

The large-scale microwave heating experiments were performed
using the Anton Paar Synthos 3000 multimode microwave synthesizer. These large volumes cannot be fitted into a monomode

Electrical power input [W]

Therefore, 20-point averaging was used to convert the temperature profile to a smooth curve before integrating and calculating
the efficiency.
The electrical power input (i.e. the total power input minus the
idle mode power input of 81 W) is plotted as a function of preset
microwave power in Fig. 7. The conversion of electrical energy
into microwaves is approximately linear in preset power for both
the 25 mL and 50 mL series of experiments, in which it can be
seen that the two series do not overlap. The observed difference
can be explained by the optimization of the microwave field that
is carried out for each heating process, which partly depends on
the sample geometry (i.e. volume). However, the slope of the
electrical power input versus preset microwave power is 1.6 for
both volumes and the conversion from electricity to microwaves
varies from 48% at 100 W to 56% at 300 W. The onset power
value slightly increases from 40 W at 50 mL to 50 W at 25 mL.
The efficiency profiles obtained with the CEM Discover (see
Accessory Publication) are highly dissimilar. Both the curves
for identical volumes and different power levels as well as the
curves for different volumes with identical power levels show
distinctly different shapes. As the only differences between these
experiments should be the microwave power or sample volume,
the most likely reason for this observation is the tuning of the
microwave cavity. The average efficiency values are fairly constant with different microwave power levels although they vary
with volume (Fig. 8; Figs S6 and S7 and Table S5), and higher
efficiencies (1720%) are obtained with 50 mL compared with
25 mL (1416%). Furthermore, the efficiency slightly decreases
with increasing microwave power. The higher heating efficiency
with larger volume and the increasing efficiency with decreasing
microwave power both indicate that the monomode microwave
field is too dense to be completely absorbed by the demineralized water, resulting in significant losses of energy. Of course the
absorbed microwave energy is also closely related to the tan of
the material, which becomes lower with increasing temperature
as discussed previously.

3000
2500
2000
1500
4 50 mL
8 50 mL

1000
500
200

400
600
800
1000
Preset microwave power [W]

1200

Fig. 9. Electrical power input versus preset microwave power for the Anton
Paar Synthos 3000.

35
30
25
20
15
10
5
0
200 W

400 W

600 W

4 50 mL

800 W 1000 W 1200 W

8 50 mL

Fig. 10. Average overall efficiency (%) for heating four or eight parallel vessels containing 50 mL demineralized water with different microwave
power settings.

microwave cavity and, thus, a larger multimode microwave was

used, having two magnetrons with rotors in front to create a
homogeneous microwave field. The heating efficiency was determined for irradiating four or eight parallel vessels containing
50 mL demineralized water, each resulting in 200 or 400 mL

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R. Hoogenboom et al.

Table 2. Liquid phase molar heat capacities, cl , used to calculate the heating efficiency
Substance

Molecular
formula

Demineralized waterA
N,N -Dimethylformamide[33]
Toluene[33]
Ethanol[33]
Diethyl ether[33]
1-n-Butyl-3-methylimidazolium chlorideB

H2 O
C3 H7 NO
C7 H8
C2 H6 O
C4 H10 O
C8 H15 N2 Cl

cl [J mol1 K1 ]
75.3
150.6
157.3
112.3
175.6
322.7

Conditions
293.15 K, 100 kPa

293.15 K

A www.hbcpnetbase.com/

(Handbook of Chemistry and Physics online version: CRC Press LLC) 2006 [accessed
11 November 2008].
B C. P. Fredlake, J. M. Crosthwaite, D. G. Hert, S. N. V. K. Aki, J. F. Brennecke, J. Chem. Eng. Data, 2004, 49, 9.

total volumes, respectively. The temperature profile, recorded

by the immersed temperature sensor and smoothed by 20-point
averaging because only integer values were recorded, and the
electrical input power after subtraction of the idle mode power
(240 W) were used to generate the efficiency profiles (Accessory Publication). The efficiency of converting electrical energy
to microwave irradiation was 46% for both four and eight parallel vessels of 50 mL demineralized water and no onset power
was observed (Fig. 9). The overlap between electrical power
input values for four and eight vessels can be understood by the
fact that there is no microwave field optimization in multimode
microwave synthesizers.
The average heating efficiency obtained for heating four or
eight parallel vessels containing 50 mL demineralized water up
to 100 C is shown in Fig. 10 (see also Figs S8, S9, and Table S6).
The shape of the efficiency profile graphs is rather similar for the
different power levels, although some scatter is observed owing
to inaccuracy in the temperature data (see Accessory Publication). In general, the graphs with eight vessels are stretched
out compared with the four vessels owing to the increasing
heat capacity and thus slower heating. The average efficiency
with four vessels ranges from 23% at 200 W and increases with
increasing power level, yielding a maximal average efficiency
of 30% at 1200 W. The observed average efficiency with eight
vessels is only slightly higher. In fact, 30% overall efficiency in
combination with 46% efficiency of converting electrical energy
to microwaves yields a 65% average efficiency of converting
microwaves to heat.
It is noteworthy to mention that in contrast to small-scale
and medium-scale microwave heating, the average efficiency
increases with increasing microwave power for the large scale
experiment. Therefore, it may be concluded that the less dense
multimode microwave field can be absorbed by the water to a
large extent. However, even though the efficiency increases at
a larger scale, the temperature increase slows down. The slower
temperature rise might suppress some of the observed advantages of microwave heating that are related to side reactions that
occur at intermediate temperatures.

Conclusions
The heating efficiency of various microwave synthesizers could
be successfully determined by integrating the temperature profile in combination with measuring the electrical power input
using a power meter. As expected, small-scale microwave heating experiments revealed that irradiation of dielectric solvents

with a high loss factor is far more efficient than heating nonpolar substances. Heating 5 mL demineralized water yielded an
average efficiency of up to 10%, whereas heating 5 mL toluene
resulted in very low average efficiency, which might even be
ascribed to heating the Pyrex glass rather than the toluene ( of
Pyrex is 4.6 at 1 MHz).34 For highly polar DMF and BMIMCl ionic liquid, the average heating efficiency was only slightly
higher compared with demineralized water. The addition of up
to 0.10 wt-% NaCl to demineralized water slightly increased the
microwave heating efficiency and with at least 0.60 wt-% NaCl,
the average heating efficiency significantly increased up to 22%.
The addition of SiC passive heating elements did not increase the
heating efficiency for very polar substances like DMF, slightly
increased the efficiency for intermediate polar compounds like
water (from 10 to 13%) and significantly increased the heating
efficiency for apolar solvents like toluene (from 1 to 6%). The
limited increase in heating efficiency in the presence of heating
elements might be due to limited heat transfer from the SiC to
the liquid.
The microwave heating efficiency for demineralized water
was found to be rather low (10%) at a small scale (5 mL), somewhat higher (up to 20%) at an intermediate scale (2550 mL),
and the highest (up to 30%) at a large scale (200400 mL). For
the monomode microwave synthesizers, an increase in heating
efficiency was found with decreasing microwave power as well
as with increasing volume, indicating that the dense microwave
field supplies an excess of energy that cannot be absorbed by
the sample. This excess of energy also accounts for the very fast
heating rates commonly observed in monomode microwaves. In
contrast, the heating efficiency of the multimode microwave did
not vary much with changes in volume or microwave power.
In fact, the heating time rather than the heating efficiency was
affected by changing the microwave power or the volume, indicating that no excess of energy is supplied to the larger volume
of water having a larger heat capacity. In addition, the surface
to volume ratio decreases with increasing volume and, thus, the
loss of heat to the surroundings is reduced at larger volumes.
Besides the difference in microwave energy density, the difference in microwave field alignment, i.e. aligned waves in the
monomode microwaves and chaotic non-aligned waves in the
multimode oven, might also influence the heating efficiency. In
the monomode microwaves, not all of the aligned waves might
be focussed on the reaction vessel resulting to a potential loss
of energy while in a multimode oven all waves can interact with
the reaction vessel.
However, mostly owing to the low conversion of electricity to
microwaves (4556%), the efficiency of microwave heating will

RESEARCH FRONT

Heating Efficiency in Microwave-Assisted Chemistry

be always relatively low compared with industrial steam-heating

processes. Therefore, it can be concluded that microwave heating is a rather inefficient process. Nonetheless, in cases where
microwave irradiation provides large advantages with regard to
reaction time, selectivity or yield, microwave synthesis might
be more energy-efficient than conventional conductive heating.
As such, the energy efficiency of microwave-assisted synthesis
procedures should be carefully compared with the conventional
method for each case separately.
Experimental
Solvents were purchased from Biosolve and used as received.
Small-scale heating experiments were performed using an
Emrys Liberator monomode microwave system from Biotage
equipped with an IR-temperature sensor. Medium-scale heating experiments were performed on a Discover monomode
microwave synthesizer from CEM upgraded with the large vessel
accessory. Temperature profiles were recorded with fibre optics.
Large-scale microwave heating was performed on the Synthos
3000 from Anton Paar using the immersion temperature probe.
The total electrical input power was measured by a Voltcraft
Energy-Check 3000 power meter that was inserted between the
wall power socket and the microwave power plug. SiC passive
heating elements were purchased from Anton Paar.
Heating efficiencies were calculated using the liquid phase
molar heat capacities cl listed in Table 2.
Accessory Publication
The Accessory Publication includes efficiency data and
temperature/efficiency curves for all reported experiments
and is available on the journals website.
Acknowledgements
The authors thank the Dutch Polymer Institute (DPI) and the Fonds der
Chemischen Industrie for financial support. CEM is thanked for the grant
that allowed the purchase of the large vessel upgrade.

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