Journal of Organometallic Chemistry 690 (2005) 3513–3517

www.elsevier.com/locate/jorganchem

Review

Sonochemistry and sonoluminescence in ionic liquids,

molten salts, and concentrated electrolyte solutions
David J. Flannigan, Stephen D. Hopkins, Kenneth S. Suslick *

Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, IL, United States

Received 8 February 2005; received in revised form 11 April 2005; accepted 12 April 2005
Available online 9 June 2005

Abstract

Ionic liquids have favorable intrinsic properties that make them of interest as solvents for various chemical reactions. The same
properties that make the liquids effective solvents also make them interesting liquids for studies involving sonochemistry, acoustic
cavitation, and sonoluminescence. Recent interest in using ultrasound to accelerate chemical reactions conducted in ionic liquids
necessitates an understanding of the effects of acoustic cavitation on these solvents. Here, we review our previous results on the
effects of cavitation on some room-temperature ionic liquids, including the sonoluminescence spectra of molten salt eutectics and
concentrated aqueous electrolyte solutions. In all cases, regardless of the essentially nonexistent vapor pressure of the solution
atomic and small molecule emitters are observed in the spectra which arise from sonolysis of the ionic liquids.

2005 Elsevier B.V. All rights reserved.

Keywords: Review; Acoustic cavitation; Sonochemistry; Sonoluminescence; Ionic liquids; Molten salts

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3513
2. Sonochemistry and sonoluminescence of room-temperature ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3515
3. Effects of ultrasonic irradiation on molten salt eutectics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3515
4. Single-bubble acoustic cavitation in concentrated aqueous electrolyte solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3516
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3516
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3517
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3517

1. Introduction temperature ionic liquids composed of asymmetric

N,N 0 -dialkylimidazolium cations with a variety of bulky
Ionic liquids are finding widespread use as solvents in anions such as PF6
, BF4
, and BPh4
. These ionic liq-
a variety of applications, including biphasic catalysis, uids are attractive because of their unique intrinsic prop-
liquid–liquid extraction, and organometallic synthesis erties, such as high thermal stability, large liquid range,
[1–3]. Recent research has focused on air-stable, room- and negligible vapor pressure [4]. The uses of ionic liq-
uids as the media for synthetic and catalytic studies
*
Corresponding author. Tel.: +1 2173332794; fax: +1 2173332685. are varied and numerous [5], including the synthesis
E-mail address: [email protected] (K.S. Suslick). and use of transition–metal nanoparticles as recyclable

0022-328X/$ - see front matter
2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.04.024
3514 D.J. Flannigan et al. / Journal of Organometallic Chemistry 690 (2005) 3513–3517

catalysts [6,7]. While the majority of work on room-tem- Sonochemistry and sonoluminescence (SL) are a result
perature ionic liquids has focused on using the solvents of acoustic cavitation: the formation, growth, and implo-
as reaction media, recent research has demonstrated that sive collapse of bubbles in a liquid [12,13]. The rapid col-
organometallic catalysts and compounds can be incor- lapse of such bubbles results in the formation of hot
porated directly into one of the ionic moieties [8–11]. spots with observed temperatures of 5000 K, pressures
For example, Audic et al. [9] synthesized an alkyl imi- of 300 atm, and cooling rates in excess of 1010 K/s [14–
dazolium salt-supported ruthenium catalyst for ring- 16]. The extreme conditions generated inside cavitating
closing olefin metathesis, and Gao et al. [10] reported bubbles are responsible for a variety of chemical and phys-
the first synthesis of room-temperature ionic liquids with ical effects. For example, volatile organometallic precur-
ferrocenylmethyl-substituted cations. It is apparent sors (e.g., Fe(CO)5 and Mo(CO)6) are able to enter the
from the wide-ranging applications that the unique vapor phase inside cavitating bubbles and after sonolysis,
properties of ionic liquids make them suitable for many can produce a variety of nanostructured materials with un-
chemical and physical studies. It is precisely these un- ique morphologies and catalytic activities (Fig. 1) [17,18].
ique properties that make ionic liquids particularly The chemical and physical effects of cavitation are
interesting for use in sonochemical reactions. highly dependent upon the contents of the collapsing
bubble. The choice of solvent for sonochemical reac-
tions is, therefore, critical. To minimize the participation
of the solvent during the reactions and to maximize the
temperatures and pressures reached within cavitating
bubbles, low vapor pressure hydrocarbon solvents have
generally been employed [19,20]. Using these solvents
for sonochemistry, however, is not without some draw-
backs. Significant carbon contamination of the desired
nanostructured materials occurs due to sonolysis of
the solvent. In addition, an upper limit is placed on
the bulk temperatures at which sonochemical reactions
can be effectively run, because the increased temperature
increases the solvent vapor pressure, which arrests the
bubble collapse [21]. Since ionic liquids have essentially
no vapor pressure, they should be ideal as solvents for
sonochemical reactions.
Recently, the ultrasonic acceleration of various chem-
ical reactions has indeed been studied using ionic liquids
as the solvent. Some of these reactions include the syn-
thesis of methanofullerene derivatives [22], the para-
selective nitration of phenols [23], and Suzuki and Heck
cross-couplings [24,25]. There have also been recent re-
ports on the sonochemical preparation of ionic liquids
with 1-alkyl-3-methylimidazolium cations and various
anions (e.g., halides, BF4
, and CF3 SO3
) [26,27]. De-
spite numerous reports of using ultrasound to accelerate
chemical reactions, synthesis of organometallic and so-
lid state species in room-temperature ionic liquids under
ultrasonic irradiation are, however, surprisingly scarce.
In a recent synthesis of [(1-methylimidazole)6FeII](PF6)2
using ultrasound, Jacob et al. [28] reported incorpora-
tion of the ionic liquid anion into the final product. This
result underlines the importance of understanding the
effects of acoustic cavitation on these ionic liquids them-
selves, as well as on related molten salts and concen-
Fig. 1. Organometallic sonochemistry has important and diverse trated electrolyte solutions. Here, we will review the
applications. (a) Schematic representation of the range of materials sonochemistry and sonoluminescence of some room-
prepared by the sonolysis of organometallics [17,18]. (b) TEM of
temperature ionic liquids previously reported by our
amorphous nanocolloid of Fe prepared by the sonolysis of Fe(CO)5
under Ar with oleic acid to trap the nanoparticles (left) and SEM of group. We will also report on SL properties of the mol-
agglomerated nanostructured iron prepared from the sonolysis of ten salt eutectic ZnCl2/NaCl/KCl, as well as those of
Fe(CO)5 under Ar without a surface trapping agent. concentrated aqueous H2SO4 solutions.
 D.J. Flannigan et al. / Journal of Organometallic Chemistry 690 (2005) 3513–3517 3515

2. Sonochemistry and sonoluminescence of room- two-site model of sonochemical reactions: the first site
temperature ionic liquids is the bubbleÕs interior gas-phase, while the second is
an initially liquid phase [31]. The initially liquid phase
Our group has previously examined the effects of corresponds to either the heating of a liquid shell near
acoustic cavitation on a number of room-temperature the gas–liquid bubble interface or to the injection of li-
ionic liquids including butylmethylimidazolium chloride quid droplets by surface waves and bubble translational
(BuMeImCl), butylmethylimidazolium tetrafluorobo- motion into the bubble interior followed by subsequent
rate (BuMeImBF4), butylmethylimidazolium hexaflu- heating of the droplets upon bubble collapse (Fig. 3).
orophosphate (BuMeImPF6), urea ammonium nitrate The temperature of the heated liquid shell or droplets
(UAN), and decylmethylimidazolium tetraphenylborate is thought to be 1900 K; this temperature is much
(DecMeImBPh4) [29]. It was observed that sonication above the temperatures necessary to decompose the io-
led to varying degrees of decomposition of all the ionic nic liquids studied.
liquids studied. Gas chromatography–mass spectrome-
try (GC–MS) analysis of the headgas over each soni-
cated imidazolium ionic liquid indeed confirmed that 3. Effects of ultrasonic irradiation on molten salt eutectics
decomposition was significant, forming various alkyl ha-
lides and imidazole decomposition products. Analysis of To limit the formation of organic decomposition
the headgas during sonication of UAN revealed the products from sonolysis, our group has also explored
presence of NH3 and CO2. Note that in the absence of molten inorganic salt eutectics for use in studies of
ultrasound, no decomposition products were detected acoustic cavitation. Molten salt eutectics, as with
during heating of the ionic liquids even at >150 C. room-temperature ionic liquids, have essentially no va-
Further evidence of the sonochemical decomposition por pressure in addition to lower melting points than
of the ionic liquids was observed in the multibubble the individual components comprising the eutectic.
sonoluminescence (MBSL) spectra. During sonication For example, the eutectic ZnCl2/NaCl/KCl melts at
of BuMeImCl and UAN, light was emitted from clouds 475 K, whereas pure NaCl melts at 1074 K thus making
of cavitating bubbles; this phenomenon has been ob- the salt eutectic experimentally more accessible than the
served and studied with other systems to determine the pure molten salts. Molten salt eutectics also have dis-
temperature and contents of the cavitating bubbles tinct advantages over room-temperature ionic liquids
[14,15,30]. The MBSL spectra of BuMeImCl contained in sonochemical and SL studies; molten salt eutectics
molecular emission from excited states of C2 and CH are optically transparent in the spectral region of inter-
(Fig. 2(a)) while the spectra from UAN were dominated est and will not suffer from the build-up of small carbo-
by CN emission (Fig. 2(b)). Combined with 1H NMR naceous molecules inside the bubble. Importantly, the
data and the previously mentioned GC–MS results, absence of carbon-containing solvent molecules elimi-
the MBSL spectra indicated that not only were the ionic nates the possibility of carbon contamination of the son-
liquids decomposing upon sonication, but the primary olysis products.
sonolysis products of the ionic liquids (which are volatile Initial studies have focused on the 60/20/20 percent by
and therefore easily susceptible to sonochemistry them- weight ZnCl2/NaCl/KCl molten salt eutectic which, as
selves) were being further decomposed. Though the neg- mentioned, melts into a relatively transparent liquid at
ligible vapor pressures of ionic liquids would intuitively 475 K. Analysis of the MBSL spectrum (Fig. 4) indicates
lead one to predict that they would not be susceptible to a broad continuum with an unresolved Na atom emis-
sonochemical degradation, the data clearly indicates sion peak from the 32S1/2 32P3/2 and 32S1/2 32P1/2
otherwise. These observations are consistent with the manifolds. With theoretically no vapor pressure, the

Fig. 2. MBSL spectra of: (a) BuMeImCl and (b) UAN. In both cases, the liquids begin to absorb strongly at 360 nm prohibiting spectral analysis
below this wavelength. The BuMeImCl MBSL spectrum is dominated by C2 emission while the UAN spectrum is dominated by CN emission.
3516 D.J. Flannigan et al. / Journal of Organometallic Chemistry 690 (2005) 3513–3517

volatile liquids for generating and studying SBSL,

including polar aprotic organic liquids [37] and concen-
trated aqueous electrolyte solutions [38]. Similar to
room-temperature ionic liquids and molten salts, con-
centrated aqueous electrolyte solutions have favorable
properties for generating and studying sonochemistry
and SL, including very low vapor pressures and moder-
ate viscosities. Furthermore, the sonolysis products of
the polar aprotic and electrolyte solutions are soluble
Fig. 3. Two-site model of sonochemical reactivity. in the bulk liquid; this is important because sonolysis
products otherwise accumulate in the bubble and sup-
origin of the Na emission again suggests a two-site model press maximum heating during bubble collapse [39].
of sonochemical reactivity. Nonetheless, inorganic eutec- Recently, we discovered that concentrated aque-
tic salt solutions do provide an interesting avenue of ous H2SO4 gives extremely intense SBSL with very
research since there are no organic decomposition prod- informative spectra (Fig. 5) [38]. This is likely due to a
ucts. Future studies could include probing CrCl2/LiCl/ combination of the very low vapor pressure (30 mTorr
KCl eutectic in an attempt to observe Cr atom emission; at 295 K) and increased viscosity (25 cP) of the concen-
the relative intensity of Cr atom emission lines would pro- trated H2SO4 solution relative to pure water. Even at
vide a spectroscopic emission temperature and thus a these low vapor pressures, however, there is still evi-
comparison to cavitation in hydrocarbon liquids [15]. dence of sonolysis of solution vapor in the SBSL spectra
just as is observed in the MBSL spectra of room-temper-
ature ionic liquids and molten salt eutectics. For exam-
4. Single-bubble acoustic cavitation in concentrated ple, when 85% H2SO4 contains a low concentration of
aqueous electrolyte solutions dissolved helium (whose large thermal conductivity low-
ers the temperatures formed during cavitation), emission
A single bubble can be trapped and made to oscillate from SO2 and SO are observed in the SBSL spectra (Fig.
at the velocity node of a liquid-filled resonator by appli- 6). The SO2 and SO likely arise from decomposition of
cation of a standing acoustic wave [32]. Under certain vaporous H2SO4 molecules inside the collapsing bubble
conditions, subnanosecond flashes of light are emitted or from a heated initially liquid shell.
at the point of minimum bubble collapse upon each
and every oscillation (single-bubble sonoluminescence,
SBSL) [33]. This system is ideal for quantifying the phys- 5. Conclusions
ical conditions and identifying the chemical species gen-
erated inside the bubble during cavitation since there is Ionic liquids provide an interesting and unique med-
no interference from other bubbles or from the con- ium for studies of organic, inorganic, and organometal-
tainer walls [34]. Though water has been the liquid of lic syntheses and catalytic reactions. The tunability of
choice for studying SBSL, the spectra are typically de- room-temperature ionic liquids for specific reactions
void of any atomic or molecular emission that could makes them particularly attractive for synthetic studies.
be used to determine conditions during the bubble col-
lapse [35]. SBSL spectra, therefore, are much different
than MBSL spectra which are relatively rich in informa-
tion [36]. Because of this, we have explored other less

Fig. 4. MBSL spectra of 60/20/20 percent by weight ZnCl2/NaCl/KCl Fig. 5. SBSL emission spectra of 85% H2SO4 and water, both regassed
molten salt eutectic. The prominent feature centered at 590 nm is due with Ar. The intensity of the H2SO4 SBSL is 3000· that of pure water
to Na atom emission. SBSL at the same temperature (295 K).
 D.J. Flannigan et al. / Journal of Organometallic Chemistry 690 (2005) 3513–3517 3517

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