activating-molecules-ions-and-solid-particles-with-acoustic-cavitation

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

The chemical and physical effects of ultrasound arise not from a direct interaction of molecules with sound waves, but rather from the acoustic ...

UMR 5257 CEA-CNRS-UM2-ENSCM

Sonoluminescence from OH(C2Σ+) and OH(A2Σ+) radicals in water: evidence for plasma formation during multibubble cavitation.

The autocatalytic sonochemical reaction of Fe(CO)(5) decomposition in [BuMeIm][Tf(2)N] provides iron nanoparticles in higher yields than in tetralin. Such a difference is explained by the higher decomposition of the intermediate Fe(3)(CO)(12) according to the two-sites model of the sonochemical reactions and the specific properties of the ionic liquid.

Autocatalytic sonolysis of iron pentacarbonyl in room temperature ionic liquid [BuMeIm][Tf2N].

Spectroscopic studies of single-bubble sonoluminescence (SBSL) in water and aqueous sodium chloride solutions with a defined concentration of argon were performed as a function of the driving acoustic pressure. The broad-band continuum ranging from 200 to 700 nm is characterized by fits using Planck's law of blackbody radiation. The obtained blackbody temperatures are in the range of 10(4) K and are revealed to be independent of the presence of a salt and the acoustic pressure, whereas the SL intensity increases by a factor of more than 10 within the studied acoustic pressure range. The different trends followed by SL intensity and blackbody temperatures question the blackbody model. In solutions with 70 mbar of argon, line emissions of OH(•) radicals and Na* are observed. The shape of the OH(•) radical emission spectrum is very similar to that in MBSL spectra, indicating the strong similarity of intrabubble conditions. An increase of the acoustic pressure causes the continuum to overlap the lines until they become indistinguishable. The emission line of Na* in NaCl is observed only at high NaCl concentrations. When sodium dodecylsulfate is used a pronounced Na* line is already observed in a 1 mM solution thanks to enrichment of sodium ions at the interface. The results presented in this work reveal the strong similarity of SBSL and MBSL under certain experimental conditions.

Line emission of sodium and hydroxyl radicals in single-bubble sonoluminescence.

Sonoluminescence of uranyl ions in aqueous solutions.

The sonoluminescence (SL) spectra of OH(A(2)Σ(+)) excited state produced during the sonolysis of water sparged with argon were measured and analyzed at various ultrasonic frequencies (20, 204, 362, 609, and 1057 kHz) in order to determine the intrabubble conditions created by multibubble cavitation. The relative populations of the OH(A(2)Σ(+)) v' = 1-4 vibrational states as well as the vibronic temperatures (T(v), T(e)) have been calculated after deconvolution of the SL spectra. The results of this study provide evidence for nonequilibrium plasma formation during sonolysis of water in the presence of argon. At low ultrasonic frequency (20 kHz), a weakly excited plasma with Brau vibrational distribution is formed (T(e) ~ 0.7 eV and T(v) ~ 5000 K). By contrast, at high-frequency ultrasound, the plasma inside the collapsing bubbles exhibits Treanor behavior typical for strong vibrational excitation. The T(e) and T(v) values increase with ultrasonic frequency, reaching T(e) ~ 1 eV and T(v) ~ 9800 K at 1057 kHz.

Nonequilibrium vibrational excitation of OH radicals generated during multibubble cavitation in water.

Sonochemiluminescence from a single cavitation bubble in water.

Bubble and peak: The isotope effects in the sonoluminescence spectra of light and heavy water under ultrasound indicate the formation of a non-equilibrium plasma inside the collapsing cavitation bubbles. The picture demonstrates the active cavitation zones in water at 204 kHz.

The origin of isotope effects in sonoluminescence spectra of heavy and light water.

This article focuses on the possibility of exciting some lanthanides (Ce(3+), Tb(3+), Gd(3+), and Eu(3+)) by ultrasound in aqueous solutions. Depending on the lanthanide ions and on the acoustic cavitation conditions (single-bubble or multibubble systems), the excitation mechanism is shown to be photoexcitation (e.g., for Ce(3+)) or collision-induced excitation (e.g., for Tb(3+)). The sonoluminescence of Tb(3+) is studied in detail at various ultrasonic frequencies, allowing quantification of the amount of quenching. The latter is much stronger in sonoluminescence than in photoluminescence due to the particular properties of acoustic cavitation. Complexation with citrate ions enhances manifold sonoluminescence of lanthanides due to reduction of intra- and inner-molecular quenching.

Luminescence of trivalent lanthanide ions excited by single-bubble and multibubble cavitations.

Sonoluminescence spectra collected from 0.1 to 3.0M aqueous solutions of formic acid sparged with argon show the OH(A(2)Σ(+)-X(2)Πi) and C2(d(3)Πg → a(3)Πu) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C2 Swan band. It is concluded that C2 emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C2 band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis.

The sonoluminescence spectra from acoustic cavitation in aqueous NaCl solutions are systematically studied in a large range of ultrasonic frequencies under variation of electrical power and argon sparging. At the same time, bubble dynamics are analysed by high-speed imaging. Sodium line and continuum emission are evaluated for acoustic driving at 34.5, 90, 150, 365, and 945kHz in the same reactor vessel. The results show that the ratio of sodium line to continuum emission can be shifted by the experimental parameters: an increase in the argon flow increases the ratio, while an increase in power leads to a decrease. At 945kHz, the sodium line is drastically reduced, while the continuum stays at elevated level. Bubble observations reveal a remarkable effect of argon in terms of bubble distribution and stability: larger bubbles of non-spherical shapes form and eject small daughter bubbles which in turn populate the whole liquid. As a consequence, the bubble interactions (splitting, merging) appear enhanced which supports a link between non-spherical bubble dynamics and sodium line emission.

Rachel Pflieger

Marcoule Institute for Separative Chemistry

UMR 5257 CEA-CNRS-UM2-ENSCM

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

Rachel Pflieger

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Marcoule Institute for Separative Chemistry

UMR 5257 CEA-CNRS-UM2-ENSCM

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

Marcoule Institute for Separative Chemistry