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by Kenneth S. Suslick
Ultrasound can produce temperatures as high as those on the surface of the Sun and
pressures as great as those at the bottom of the ocean. In some cases, it can also
increase chemical reactivities by nearly a millionfold.
Ultrasound is simply sound pitched above human hearing. It has found many uses in many
areas. At home, we use ultrasound for dog whistles, burglar alarms, and jewelry cleaners. In
hospitals, doctors use ultrasound to remove kidney stones without surgery, to treat cartilage
injuries (such as "tennis elbow"), and to image fetal development during pregnancy. In
industry, ultrasound is important for emulsifying cosmetics and foods, welding plastics, cutting
alloys, and large-scale cleaning. None of these applications, however, take advantage of the
effects that ultrasound can have on chemical reactivity.
The chemical applications of ultrasound, "sonochemistry", has become an exciting new field
of research during the past decade. The history of sonochemistry, however, begins in the late
1800s. During field tests of the first high-speed torpedo boats in 1894, Sir John I. Thornycroft
and Sydney W. Barnaby discovered severe vibrations from and rapid erosion of the ship's
propeller. They observed the formation of large bubbles (or cavities) formed on the spinning
propeller and postulated that the formation and collapse of these bubbles were the source of
their problems. By increasing the propeller size and reducing its rate of rotation, they could
minimize this difficulty of "cavitation". As ship speeds increased, however, this became a
serious concern and the Royal Navy commissioned Lord Rayleigh to investigate. He
confirmed that the effects were due to the enormous turbulence, heat, and pressure produced
when cavitation bubbles imploded on the propeller surface. In the same work, he explained
that cavitation was also the origin of teakettle noise!
This phenomenon of cavitation occurs in liquids not only during turbulent flow but also under
high-intensity ultrasonic irradiation. It is responsible for both propeller erosion and for the
chemical consequences of ultrasound. Alfred L. Loomis noticed the first chemical effects of
ultrasound in 1927, but the field of sonochemistry lay fallow for nearly 60 years. The
renaissance of sonochemistry occurred in the 1980's, soon after the advent of inexpensive
and reliable laboratory generators of high-intensity ultrasound.
Scientists now know that the chemical effects of ultrasound are diverse and include
substantial improvements in both stoichiometric and catalytic chemical reactions. In some
cases, ultrasonic irradiation can increase reactivities by nearly a millionfold. The chemical
effects of ultrasound fall into three areas: homogeneous sonochemistry of liquids,
heterogeneous sonochemistry of liquid-liquid or liquid-solid systems, and sonocatalysis
(which overlaps the first two). Because cavitation can take place only in liquids, chemical
reactions do not generally occur during the ultrasonic irradiation of solids or solid-gas
systems.
Figure 1. Chemistry: the interaction of energy and matter. The three axes represent duration
of the interaction, pressure, and energy per molecule. The labeled islands represent the
nature of the interaction of energy and matter in various different kinds of chemistry.
Sound is nothing more than waves of compression and expansion passing through gases,
liquids or solids. We can sense these waves directly through our ears if they have frequencies
from about Hertz to 16 kHz (the Hertz unit is cycles of compression or expansion per second;
kiloHertz, abbreviated kHz, is thousands of cycles per second). These frequencies are similar
to low frequency radio waves, but sound is intrinsically different from radio or other
electromagnetic radiation. For example, electromagnetic radiation (radio waves, infrared,
visible light, ultraviolet, x-rays, gamma rays) can pass through a vacuum without difficulty; on
the other hand, sound cannot because the compression and expansion waves of sound must
be contained in some form of matter.
High intensity sound and ultrasound are generally produced in a similar fashion: electric
energy is used to cause the motion of a solid surface, such as a speaker coil or a
piezoelectric ceramic. Piezoelectric materials expand and contract when an electric field is
applied. For ultrasound a high frequency alternating electric current is applied to a
piezoelectric attached to the wall of a metal container (as in an ultrasonic cleaning bath of the
kind used, for example, by jewelers) (Figure 2).
Figure 2. Diagram shows a typical sonochemical apparatus. Ultrasound can easily be
introduced into a chemical reaction in which there is good control of temperature and ambient
atmosphere. The titanium rod shown immersed in the reaction liquid is driven into vibration by
a piezoelectric, which vibrates when subjected to an alternating current electric field. The
usual piezoelectric cerramic is PZT, a lead zirconate titanate material.
Ultrasound has frequencies pitched above human hearing (above roughly 16 kHz). Scientists
can make narrow beams of "silent" ultrasound far more intense than the roar of a jet engine,
but completely unheard by our ears. Ultrasound has wavelengths between succession
compression waves measuring roughly 10 cm to 10-3 centimeters. These are not comparable
to molecular dimensions. Because of this mismatch, the chemical effects of ultrasound cannot
result from a direct interaction of sound with molecular species.
Nonetheless, the ultrasonic irradiation of liquids does produce a plethora of high energy
chemical reactions. This occurs because ultrasound causes other physical phenomena in
liquids that create the conditions necessary to drive chemical reactions. The most important of
these is cavitation: the formation, growth, and implosive collapse of bubbles in a liquid. The
dynamics of cavity growth and collapse are strikingly dependent on the local environment.
Cavity collapse in a homogeneous liquid is very different from cavitation near a liquid-solid
interface, which will be considered later.
As ultrasound passes through a liquid, the expansion cycles exert negative pressure on the
liquid, pulling the molecules away from one another. If the ultrasound is sufficiently intense,
the expansion cycle can create cavities in the liquid. This will occur when the negative
pressure exceeds the local tensile strength of the liquid, which varies according to the type
and purity of liquid. (Tensile strength is the maximum stress that a material can withstand
from a stretching load without tearing.) Normally, cavitation is a nucleated process; that is, it
occurs at pre-existing weak points in the liquid, such as gas-filled crevices in suspended
particulate matter or transient microbubbles from prior cavitation events. Most liquids are
sufficiently contaminated by small particles that cavitation can be readily initiated at moderate
negative pressures.
Once formed, small gas bubbles irradiated with ultrasound will absorb energy from the sound
waves and grow. Cavity growth depends on the intensity of the sound. At high intensities, a
small cavity may grow rapidly through inertial effects. If cavity expansion is sufficiently rapid
during the expansion half of a single cycle, it will not have time to recompress during the
compression half of the acoustic cycle.
At lower acoustic intensities cavity growth can also occur by a slower process called rectified
diffusion (Figure 3). Under these conditions a cavity will oscillate in size over many expansion
and compression cycles. During such oscillations the amount of gas or vapor that diffuses in
or out of the cavity depends on the surface area, which is slightly larger during expansion
than during compression. Cavity growth during each expansion is, therefore, slightly larger
than shrinkage during the compression. Thus, over many acoustic cycles, the cavity will grow.
The growing cavity can eventually reach a critical size where it can efficiently absorb energy
from the ultrasonic irradiation. Called the resonant size, this critical size depends on the liquid
and the frequency of sound; at 20 kHz, for example, it is roughly 170 micrometers. At this
point the cavity can grow rapidly during a single cycle of sound.
Figure 3. Liquids irradiated with ultrasound can produce bubbles. These bubbles oscillate,
growing a little more during the expansion phase of the sound wave than they shrink during
the compression phase. Under the proper conditions these bubbles can undergo a violent
collapse, which generates very high pressures and temperatures. This process is called
cavitation.
Once the cavity has overgrown, either at high or low sonic intensities, it can no longer absorb
energy as efficiently. Without the energy input the cavity can no longer sustain itself. The
surrounding liquid rushes in, and the cavity implodes. It is the implosion of the cavity that
creates an unusual environment for chemical reactions.
Compression of a gas generates heat. On a macroscopic scale, one can feel this when
pumping a bicycle tire; the mechanical energy of pumping is converted into heat as the tire is
pressurized. The compression of cavities when they implode in irradiated liquids is so rapid
than little heat can escape from the cavity during collapse. The surrounding liquid, however, is
still cold and will quickly quench the heated cavity. Thus, one generates a short-lived,
localized hot spot in an otherwise cold liquid. Such a hot spot is the source of homogeneous
sonochemistry; it has a temperature of roughly 5000° C (9,000° F), a pressure of about 1000
atmospheres, a lifetime considerably less than a microsecond, and heating and cooling rates
above 10 billion° C per second. For a rough comparison, these are, respectively, the
temperature of the surface of the sun, the pressure at the bottom of the ocean, the lifetime of
a lightning strike, and a million times faster cooling that a red hot iron rod plunged into water!
Thus, cavitation serves as a means of concentrating the diffuse energy of sound into a
chemically useful form. Alternative mechanisms involving electrical microdischarge have been
proposed (most recently by M.A. Margulis of the Russian Institute for Organic Synthesis), but
they do not appear fully consistent with observed data.
When a liquid is subjected to ultrasound, not only does chemistry occur, but light is also
produced (Figure 4). Such "sonoluminescence" provides an alternate measure of the
temperature of the high-energy species produced during cavitation. High-resolution
sonoluminescence spectra were recently reported and analyzed by E.B. Flint and Suslick.
From a comparison of synthetic to observed spectra, the effective cavitation temperature of
the emitting species is 5,100 K. The agreement between this spectroscopic determination of
the cavitation temperature and that made by comparative rate thermometry of sonochemical
reactions is surprisingly close.
Figure 4. High intensity ultrasound creates localized hot spots in liquids through the process
of cavitation. Local heating produces excited states of molecules that emit light, just as they
do in a flame. The image shown is such sonoluminescence seen from a vibrating titanium rod
(about 0.4 inch) in diameter. False color is used to enhance contrast. The temperature
created in cavitation hot-spots, determined from the spectrum of this emission, is ~5000 K.
When cavitation occurs in a liquid near a solid surface, the dynamics of cavity collapse
changes dramatically. In pure liquids, the cavity remains spherical during collapse because its
surroundings are uniform. Close to a solid boundary, however, cavity collapse is very
asymmetric and generates high-speed jets of liquid (Figure 5). The potential energy of the
expanded bubble is converted into kinetic energy of a liquid jet that moves through the
bubble's interior and penetrates the opposite bubble wall. Werner Lauterborn at the
Technische Hochschule in Darmstadt, Germany, observed liquid jets driving into the surface
with velocities of roughly 400 kilometers/hour (Figure 6). These jets hit the surface with
tremendous force. This process can cause severe damage at the point of impact and can
produce newly exposed, highly reactive surfaces; it has great importance for understanding
the corrosion and erosion of metals observed in propellers, turbines, and pumps where
cavitation is a continual technological problem.
Figure 5. A bubble in a liquid irradiated with ultrasound implodes near a solid surface. The
presence of the solid causes the implosion to be asymmetrical, forming a high-speed jet of
liquid that impacts the surface. The cavity is spherical at first, but as it collapses the jet
develops opposite the solid surface and moves towards it. (L.A. Crum)
Figure 6. High-speed microcimemagraphic sequence of laser-induced cavitation near a solid
surface shows the formation of a microjet impact with a velocity of approximately 400
kilometers (250 miles) per hour. (W. Lauterborn)
Distortions of bubble collapse depend on a surface several times larger than the resonant
size of the bubble. The presence of fine powders, therefore, does not induce jet formation. In
the case of liquid-powder slurries, the shock waves created by homogeneous cavitation can
create high-velocity interparticle collisions. The turbulent flow and shock waves produced by
intense ultrasound can drive metal particles together at sufficiently high speeds to cause
effective melting at the point of collision (Figure 7). Such interparticle collisions are capable of
inducing striking changes in surface texture, composition, and reactivity, as discussed later.
S. J. Doktycz and K. S. Suslick used metal powders to estimate the effective maximum
temperatures and speeds reached during interparticle collisions (Figure 8). When chromium,
molybdenum, and tungsten powders of a few micrometers in size are irradiated in decane at
20 kHz and 50 watts per square centimeter, one observes agglomeration and welding of
particles for the first two metals but not for the third. On the basis of the melting points of
these metals, the effective transient temperature reached at the point of impact during
interparticle collisions is roughly 3000° C. On the basis of the volume of the melted region of
impact, the amount of energy generated during collision was determined. From this, the
velocity of impact is estimated to be roughly 1800 kilometers per hour, which is half the speed
of sound in liquids. It should be noted that the conditions reached during interparticle
collisions are not directly related to the temperatures reached during cavitational collapse of
bubbles.
Figure 7. Scanning electron micrograph reveals zinc powder after ultrasonic irradiation. The
neck formation from localized melting or plastic deformation was caused by high-velocity
collisions of the zinc particles.
Figure 8. Scanning electron micrographs reveal slurries of metal powders both before and
after ultrasonic irradiation. Chromium has a melting point of 1857° C (3,374.6° F), and its
particles both agglomerate and are deformed; molybdenum melts at 2617° C (4,742.6° F), and
its particles are slightly agglomerated but not smoothed or deformed; tungsten melts at 3410°
C (6,170° F) and is unaffected.
High-intensity ultrasonic probes (10 to 500 watts per square centimeter) are the most reliable
and effective sources for laboratory-scale sonochemistry. A typical laboratory apparatus
permits easy control over ambient temperature and atmosphere (Figure 2). Lower acoustic
intensities can often be used in liquid-solid heterogeneous systems because of the reduced
liquid tensile strength at the liquid-solid interface. For such reactions a common ultrasonic
cleaning bath will often be adequate. The low intensity available in these devices ( about one
watt per square centimeter) can, however, prove to be a limitation. On the other hand,
ultrasonic cleaning baths are easily accessible, comparatively inexpensive, and usable on
moderately large scales. Finally, for large-scale irradiations, flow reactors with high ultrasonic
intensities are commercially available in modular units as powerful as 20 kilowatts.
The chemical effect of ultrasound on aqueous solutions have been studied for many years.
The primary products are molecular hydrogen (H2) and hydrogen peroxide (H2O2). Other high-
energy intermediates may include HO2 (superoxide), H• (atomic hydrogen), OH• (hydroxyl),
and e-(aq) (solvated electrons). Peter Riesz and collaborators at the National Institutes of
Health used electron paramagnetic resonance with chemical spin-traps to demonstrate
definitively the generation of H• and OH• . The extensive recent work in Arne Henglein's
laboratory at the Hahn-Meitner Institute involving aqueous sonochemistry of dissolved gases
has established analogies to combustion processes. As one would expect, the sonolysis of
water, which produces both strong reductants and oxidants, is capable of causing secondary
oxidation and reduction reactions, as often observed by Margulis and coworkers.
In contrast, the ultrasonic irradiation of organic liquids has been little studied. Suslick and co-
workers established that, as long as the total vapor pressure is low enough to allow effective
bubble collapse, almost all organic liquids will generate free radicals (uncharged, reactive
intermediates possessing an unpaired electron) when they undergo ultrasonic irradiation. The
sonolysis of simple hydrocarbons creates the same kinds of products associated with very
high temperature pyrolysis. Most of these products - H2, CH4 (methane), and the smaller 1-
alkenes, derive from a well-understood radical chain mechanism. Relatively large amounts of
acetylene (C2H2) are also produced, which is explained by the stability of this gas at very high
temperatures.
The sonochemistry of solutes dissolved in organic liquids also remains largely unexplored,
though that of metal carbonyl compounds is an exception. In 1981, P. F. Schubert, J. W.
Goodale and Suslick reported the first sonochemistry of discrete organometallic complexes
and demonstrated the effects of ultrasound on metal carbonyls. Detailed studies of these
systems led to important understandings of the nature of sonochemistry. Unusual reactivity
patterns have been observed during ultrasonic irradiation, including novel metal cluster
formation and the initiation of homogeneous catalysis at low ambient temperature, with rate
enhancements greater than 100,000-fold.
The effects of ultrasound on polymers (giant molecules formed by the coupling of small
molecules-monomers) have been thoroughly studied over the past 30 years. The controlled
cleavage of polymers in solutions irradiated with ultrasound has been examined in detail.
Polymer degradation produces chains of smaller lengths with relatively uniform molecular
weight distributions, with cleavage occurring primarily in the center of the polymer chain.
Several mechanisms have been proposed for this sonochemical cleavage, which is usually
described as a mechanical breakage of the chains induced by shock waves or solvent flow
created by cavitation during the ultrasonic irradiation of liquids.
This polymer fragmentation has been used by G. J. Price at the University of Bath to
synthesize block copolymers of various sorts. Block copolymers are long chain polymers with
two different, but linked, parts. As an analogy, imagine a train made up in front by passenger
cars and in back by freight cars. In this fashion, block copolymers can do double-duty in their
properties. Peter Kruus at Carleton University, Ottawa, reported the use of ultrasound to
initiate polymerization in solutions of various monomers.
One recent example is the use of high intensity ultrasound to make aqueous suspensions of
long-lived proteinaceous microspheres filled with air or with water-insoluble liquids for medical
applications (Figure 9). By itself, emulsification is insufficient to produce these long-lived
microspheres; chemical reactions requiring oxygen are critical in forming them. Specifically,
the sonolysis of water produces hydrogen atoms that react with oxygen to produce
superoxide. Suslick and M. W. Grinstaff demonstrated that the proteinaceous microspheres
are held together by disulfide bonds between protein cysteine residues and that superoxide is
the cross-linking agent.
Figure 9. Protein microspheres filled with the oily hydrocarbon dodecane were formed by the
ultrasonic irradiation of albumin solutions. Such microspheres may prove useful for drug
delivery and medical diagnostic imaging.
A few years after the discovery of sonochemical reactions, H. Frenzel and H. Schultes in
1934 first observed sonoluminescence from water. As with sonochemistry, sonoluminescence
derives from acoustic cavitation. Although sonoluminescence from aqueous solutions has
been studied in some detail, only recently has significant work been reported on
sonoluminescence from non-aqueous liquids containing no water. In both cases, the emission
of light comes from the high temperature formation of reactive chemical species in electronic
excited states. The emitted light from these excited states provides a spectroscopic probe of
the cavitation event.
High resolution sonoluminescence spectra from hydrocarbons and silicone oil were recently
analyzed by Flint and Suslick. The observed emission comes from excited state diatomic
carbon which are the same transitions responsible for the blue color of a hydrocarbon flame
(from the kitchen stove, for example). The details of this emission depend on the temperature
of the emitted C2 and can be accurately modeled with synthetic spectra as a function of
presumed temperature. From a comparison of synthetic to observed spectra, the average
effective temperature of the excited state of C2 is about 5,100 K, as mentioned above.
Considerably less work has been done on the activation of less reactive metals. This goal
continues to attract major efforts in both synthetic organometallic chemistry and
heterogeneous catalysis. Ultrasound can be used at room temperature and pressure to
promote heterogeneous reactions that normally occur only under extreme conditions of
hundreds of atmospheres and hundreds of degrees. For example, R. E. Johnson and Suslick
found good results with the use of ultrasound to drive some of the most difficult reactions
known for transition metals: the attack of carbon monoxide on the very unreactive early
transition metals such as vanadium, tantalum, molybdenum and tungsten.
Sonocatalysis
Catalytic reactions are of enormous importance in both laboratory and industrial applications.
Catalysts increase the rates of chemical reactions without being consumed themselves; they
are generally divided into two types. If the catalyst is a molecular or ionic species dissolved in
a liquid, then the system is "homogeneous"; if the catalyst is a solid, with the reactants either
in a percolating liquid or gas, then it is "heterogeneous." In both cases, it is often a difficult
problem either to activate the catalyst or to keep it active.
Using ultrasound offers some hope of activating less reactive, but also less costly, metals.
Some early investigations of the effects of ultrasound on heterogeneous catalysis can be
found in the Soviet literature. In this early work, increases in turnover rates were usually
observed upon ultrasonic irradiation, but were rarely more than 10-fold. In the case of modest
rate increases, it appears likely that the cause is increased effective surface area; this is
especially important in the case of catalysts supported on brittle solids.
A Sound Future
In addition, ultrasound is well suited to industrial applications. Since the reaction liquid itself
carries the sound, there is no barrier to its use with large volumes. In fact, ultrasound is
already heavily used industrially for the physical processing of liquids, such as emulsification,
solvent degassing, solid dispersion, and sol formation. It is also extremely important in solids
processing, including cutting, welding, cleaning, and precipitation.
The extension of ultrasound to the chemical processing of liquids is underway. The future
uses of ultrasound to drive chemical reactions will be diverse. It is becoming a common tool in
nearly any case where a liquid and a solid must react. In the synthesis of pharmaceuticals, for
example, ultrasound may permit improved yields and facilitate reactions run on larger scale.
In the development and use of catalysts, ultrasound also has potential applications. Its ability
to create highly reactive surfaces and thereby increase their catalytic activity has only just
now been established. Ultrasound can produce materials with unusual properties. The
extraordinary temperatures and pressures reached during cavitational collapse, combined
with the exceptionally high rates of cooling, may allow researchers to synthesize novel solid
phases difficult to prepare in other ways. One may be optimistic that the unusual reactivities
caused by ultrasound will find important industrial application in the years to come.
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