J. Am. Chem. Soc.

1997, 119, 9303-9304 9303

Chemistry Induced by Hydrodynamic Cavitation In a typical run,12a 60 mL of 1.0 M KI in purified water

saturated with carbon tetrachloride was introduced at a constant
Kenneth S. Suslick,* Millan M. Mdleleni, and flow rate into the Microfluidizer with a liquid pressure of 1.24
Jeffrey T. Ries kbar. The reaction solution temperature increased 10 to 12 C
within 90 s and stabilized at the temperatures reported herein.
Department of Chemistry Aliquots (4 mL) of the processed solution were periodically
UniVersity of Illinois at Urbana-Champaign extracted from the reaction system by airtight syringes, analyzed
601 South Goodwin AVenue, Urbana, Illinois 61801 spectrophotometrically, and returned to the reservoir after
analysis. The rate of I3- formation was calculated from the
ReceiVed July 1, 1997
change in absorbance at 353 nm ( ) 26 400 M-1 cm-1)12b as
Cavitation (the formation, growth, and implosive collapse of a function of reaction time. Initial studies conducted with Ar-
gas or vapor-filled bubbles in liquids) can have substantial sparged water gave relatively low rates of I3- production;
chemical and physical effects. While the chemical effects of saturation of the Ar sparged H2O with CCl4 resulted in a 20-
acoustic cavitation (i.e., sonochemistry and sonoluminescence) fold increase in I3- production, as has been typically observed
have been extensively investigated during recent years,1-5 little for ultrasonic cavitation.10 This is attributed to ready formation
is known about the chemical consequences of hydrodynamic of Cl and Cl2 from CCl4 under cavitation conditions.
cavitation created during turbulent flow of liquids. Hydrody- The effect of upstream liquid pressure on the rate of I3-
namic cavitation is observed when large pressure differentials production was investigated over the range 100-1500 bar. The
are generated within a moving liquid and is accompanied by a reaction rate increases linearly with liquid pressure (Figure 1),
number of physical effects, erosion being most notable from a but with a threshold pressure of 150 bar. Below 150 bar of
technological viewpoint.6,7 In contrast, reports of hydrodynami- hydrostatic pressure, no chemical reactions were observed; this
cally induced chemistry or luminescence and direct comparisons probably represents the minimum jet velocity necessary to
to sonochemistry or sonoluminescence have been extremely induce cavitation. The resistance of a turbulent flow to
limited.8,9 cavitation is given by its cavitation number , as defined in eq
In aqueous liquids, acoustic cavitation leads to the formation 1:6
of reactive species such as OH, H, and H2O2. These short-
lived species are capable of effecting secondary oxidation and pd - p v p d
reduction reactions. For example, iodide can be sonochemically
) (1)
pu - pd pu
oxidized to triiodide by OH radicals or H2O2 produced during
cavitation. From aqueous solutions containing chlorocarbons, where pd, pu, and pv are the downstream, upstream, and vapor
Cl and Cl2 are also liberated in high yields and this increases pressures, respectively, and the approximation holds when pu
rates of iodide oxidation.10 The rate of triiodide formation is . pd . pv, as they do under our experimental conditions. An
easily monitored spectrophotometrically. For many years, this increase in upstream pressure should decrease and increase
so-called Weissler reaction has remained the standard dosimeter the number of cavitation events. This in turn should increase
for sonochemical reactions. the rate of I3- formation, if the chemistry is cavitation driven,
The recent advent of commercially available high-pressure consistent with our observations.
jet fluidizers capable of pressure drops as high as 2 kbar and The conditions formed during acoustic cavitation and con-
jet velocities approaching 200 m/s has led to numerous sequently sonochemical rates are known to be affected both by
applications in the physical processing of liquids, for emulsifica- the polytropic ratio of the dissolved gas (i.e., ) Cp/Cv,) and
tion, cell disruption, etc. Chemical consequences of such by the thermal conductivity of the dissolved gas. The former
processing, however, have received little examination. One parameter determines the temperature achieved during bubble
important exception comes from W. R. Moser and co-workers,11 compression, and the latter is responsible for heat dissipation
who have shown that such a device can be utilized to prepare from the collapsing bubble to the surrounding solution. In the
nanostructured catalytic materials. Moser speculated that the present study using Ar/He mixtures, the of the dissolved gas
unusual properties of his catalysts resulted from hydrodynamic was fixed at 1.67, while the thermal conductivity was varied
cavitation within the fluidizer.11 We describe here conclusive from 0.017 to 0.142 W m-1 K-1. As shown in Figure 2, the
experimental evidence for chemical reactions caused by hydro- I3- formation rate decreases exponentially as the thermal
dynamic cavitation within a jet fluidizer. conductivity of the dissolved gas increases. This observation
(1) Suslick, K. S. MRS Bull. 1995, 20, 29 is best explained in terms of the hot-spot model for cavitation
(2) Mason, T. J., Ed. AdVances in Sonochemistry; JAI Press: New York, which suggests that the maximum temperature (Tmax) realized
1990-1994; Vols. 1-3.
(3) Price, G. J., Ed. Current Trends in Sonochemistry; Royal Society of (12) (a) Reagent grade KI and CCl4 were obtained from Aldrich Chemical
Chemistry: Cambridge, U.K., 1992. Co. and used as received. High-purity water was prepared with a Barnstead
(4) Suslick, K. S. Science 1990, 247, 1439. NANOpure. Spectrophotometric measurements were obtained with a Hitachi
(5) Suslick, K. S., Ed. Ultrasound: Its Chemical, Physical, and Biological U3300 UV-vis double-monochromator spectrophotometer. MKS mass flow
Effects; VCH: New York, 1988. controllers 247C were used to adjust the composition of the Ar/He sparge
(6) Knapp, R. T.; Daily, J. W.; Hammitt, F. G. CaVitation; McGraw- gas. Hydrodynamic cavitation studies were performed with an air-driven
Hill: Inc.: New York, 1970. model M-110Y Microfluidizer from Microfluidics International Corp., 30
(7) (a) Young, F. R. CaVitation; McGraw-Hill: Inc.: New York, 1989. Ossipee Rd., Newton, MA 02164. The reaction solutions were exposed only
(b) Brennen, C. E. CaVitation and Bubble Dynamics; Oxford University to stainless steel or glass. The reaction solution was first sparged with high-
Press: Oxford, U.K., 1995. purity argon or Ar/He mixtures and light-proofed to prevent CCl4 photo-
(8) Anbar, M. Science 1968, 161, 1343. decomposition and then injected into the pressurizing reservoir through a
(9) (a) Verbanov, V. S.; Margulis, M. A.; Demin, S. V.; Korneev, Y. self-sealing septum. A portion of the reaction solution was pressurized by
A.; Klimenko, B. N.; Nikitin, Y. B.; Pogodaev, V. I. Russ. J. Phys. Chem. a large pneumatically driven pump into an interaction chamber, where two
1990, 64, 1807. (b) Margulis, M. A.; Korneev, Y. A.; Demin, S. V.; pulsed flows were redirected at each other through jewel orifices with
Verbanov, V. S. Russ. J. Phys. Chem. 1994, 68, 828. velocities of 190 m/s11b controlled by a back-pressure regulator. Cavitation
(10) (a) Weissler, A.; Cooper, N. W.; Snyder, S. J. Am. Chem. Soc. 1950, can occur when there is sufficient turbulence upon liquid jet impact or when
72, 1769. (b) Ibisi, M.; Brown, B. J. Acoust. Soc. Am. 1967, 41, 568. (c) there exists a sufficient pressure drop as the streams pass through the orifices.
Clark, P. R.; Hill, C. R. J. Acoust. Soc. Am. 1970, 47, 649. (d) Chendke, P. High-velocity pumping is also accompanied by bulk heating of the flowing
K.; Fogler, H. S. J. Phys. Chem. 1983, 87, 1362. liquid. The reaction chamber, pump, and plumbing were therefore immersed
(11) (a) Moser, W. R.; Marshik, B. J.; Kingsley, J.; Lemberger, M.; in a thermally equilibrated water bath. The processed stream was returned
Willette, R.; Chan, A.; Sunstrom, J. E.; Boye, A. J. Mater. Res. 1995, 10, to the solution reservoir for recirculation and analysis. (b) Awtrey, A. D.;
2322. (b) Moser, W. R. Personal communication. Connick, R. E. J. Am. Chem. Soc. 1951, 73, 1842.

S0002-7863(97)02171-9 CCC: $14.00 1997 American Chemical Society

9304 J. Am. Chem. Soc., Vol. 119, No. 39, 1997 Communications to the Editor

Figure 1. Dependence of triiodide formation rate on the hydrodynamic

pressure used to induce cavitation. Conditions: 60 mL of 1 M KI Figure 3. Dependence of triiodide formation rate on bulk temperature
solution in CCl4-saturated water was recycled under static Ar atmo- and on solvent vapor pressure during hydrodynamic cavitation. Condi-
sphere at a constant reaction temperature of 12 C. tions: 60 mL of 1 M KI solution in CCl4-saturated water was recycled
under static Ar atmosphere at liquid pressure of 1.24 kbar.
pressure. This same dependence is seen in sonochemical
reactions and is attributed to the increase in polyatomic vapor
inside the bubble before collapse, which decreases and
cushions the collapse of the cavitating bubble.15 While it is
difficult to make direct comparisons of energy efficiency (e.g.,
moles of product per kilowatt hour of electrical energy), acoustic
cavitation provides significantly higher rates for the Weissler
reaction, at least for the specific source of hydrodynamic
cavitation tested here.
In summary, we have demonstrated that the chemical effects
of hydrodynamic cavitation and acoustic cavitation respond
identically to experimental parameters, notably the bulk tem-
perature and the nature of the dissolved gas. In particular, the
rates decrease with increasing solution temperature, due to the
increased solvent vapor pressure inside the bubble; increasing
solvent vapor pressure attenuates the efficacy of cavitational
collapse, the maximum temperature reached during such col-
Figure 2. Dependence of triiodide formation rate on the nature of the lapse, and, consequently, the rates of cavitational reactions. By
dissolved gas during hydrodynamic cavitation. Conditions: 60 mL of reducing the adiabaticity of bubble collapse, the thermal
1 M KI solution in CCl4-saturated water was recycled under static Ar conductivity of the dissolved gas also has a substantial effect
or Ar/He atmosphere at a constant reaction temperature of 12 C and on the maximum temperature achieved inside a cavitating
liquid pressure of 1.24 kbar. bubble; increased thermal conductivity decreased rates of
cavitation reactions.
in a collapsing bubble decreases linearly with increasing thermal Acknowledgment. This work was supported by the National
conductivity of the entrapped gas.13 This inverse relationship Science Foundation (CHE 94-20758) and in part by the DOE. The
of Tmax to the thermal conductivity of dissolved gases should Microfluidizer used in this study was provided on loan from Catalytica,
lead to an exponential decrease in the I3- formation rate Inc., and Microfluidics International Corp. We thank Dr. David L. King
(assuming Arrhenius behavior) with increasing thermal con- and Prof. W. R. Moser for useful discussions.
ductivity, as observed. JA972171I
The influence of bulk solution temperature on the I3-
production rate was investigated to probe the effect of vapor (14) (a) Sehgal, C.; Sutherland, R. G.; Verrall, R. E. J. Phys. Chem.
1980, 84, 525. (b) Didenko, Y. T.; Nastich, D. N.; Pugach, S. P.; Polovinka,
pressure. The I3- production rates decrease sharply with Y. A.; Kvochka, V. I. Ultrasonics 1994, 32, 71.
increasing temperature, as shown in Figure 3. This same (15) (a) Suslick, K. S.; Gawienowski, J. J.; Schubert, P. F.; Wang, H.
behavior has been reported for many previous acoustic cavitation H. Ultrasonics 1984, 22, 33. (b) Suslick, K. S.; Gawienowski, J. J.; Schubert,
P. F.; Wang, H. H. J. Phys. Chem. 1983, 87, 2299.
studies.10b,14,15 Figure 3 also demonstrates that the observed (16) (a) Washington, C.; Davis, S. S. Int. J. Pharm. 1988, 44, 169. (b)
rates decrease exponentially with increasing solvent vapor Lidgate, D. M.; Fu, R. C.; Fleitman, J. S. Biopharm 1989, 2, 28. (c) Lidgate,
D. M.; Trattner, T.; Shulz, R. M.; Maskiewicz, R. Pharm. Res. 1992, 9,
(13) Young, F. R. J. Acoust. Soc. Am. 1976, 60, 100. 860.