Molecular emissions in sonoluminescence spectra of water sonicated under Ar-based gas mixtures.

Sonoluminescence (SL) spectroscopy is one of the very few ways to study the plasma formed in solutions submitted to ultrasound. Unfortunately, up to now only very limited emission bands were reported in SL spectra of aqueous solutions, moreover broad and badly resolved. It is shown here that by adding some N2 and/or CO2 in Ar, new molecular emissions (CN, N2 and CO) can be observed and that for some of them rovibronic temperatures can be derived. The paramount importance of Stark broadening in these emissions is underlined, together with the need for data on Stark parameters for molecular emissions.

Multibubble Sonochemistry and Sonoluminescence at 100 kHz: The Missing Link between Low- and High-Frequency Ultrasound.

Ultrasonic frequency is one of the most important parameters that decides the characteristics of acoustic cavitation. Low- (16-50 kHz) and high- (≥200 kHz) frequency ultrasounds present opposite physical and chemical behaviors and have been extensively studied, yet frequencies in between are poorly characterized. In this study, acoustic cavitation at the intermediate ultrasonic frequency of 100 kHz is compared with that at 20 kHz and at 362 kHz by different experimental investigations: sonochemical yield (H2O2), images of sonochemiluminescence and sonoluminescence, as well as sonoluminescence spectra in aqueous media saturated with Ar or Ar/(20 vol %)O2. The chemical activity (H2O2 yield) of cavitation bubbles at 100 kHz presents a transitional behavior between low and high frequencies. The active cavitation zone distributes in the whole sonicated volume, similarly to high-frequency ultrasound and much further than at 20 kHz. The spectral shape of 100 kHz spectra is similar to that at 20 kHz. On the contrary, 100 kHz ultrasound provides the dissociation of O2 and N2 molecules inside the bubble, which is more typical for high-frequency ultrasound. This faculty is explained by the more extreme conditions reached at collapse compared with 20 kHz. Rovibronic temperatures of OH (A2Σ+) excited radicals derived from spectroscopic simulations confirm this interpretation.

Potential applications of sonochemistry in spent nuclear fuel reprocessing: a short review.

The industrial treatment of spent nuclear fuel is based upon a hydrometallurgical process in nitric acid medium. In order to minimize the volume of radioactive waste it seems interesting to generate the reactive species in situ in such solutions using ultrasonic irradiation without addition of salt-forming reagents. This review summarizes for the first time the versatile sonochemical processes with uranium, neptunium and plutonium in homogeneous nitric acid solutions and heterogeneous systems. The dissolution of refractory solids, ultrasonically driven liquid-liquid extraction and the sonochemical degradation of the volatile products of organic solvent radiolysis issued from PUREX process are considered. Also the guidelines for required further work to ensure successful application of the studied processes at industrial scale are discussed.

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes.

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.

Influence of gamma irradiation on hydrophobic room-temperature ionic liquids [BuMeIm]PF6 and [BuMeIm](CF3SO2)2N.

Stability of neat hydrophobic Room-Temperature Ionic Liquids (RTIL) [BuMeIm]X, where [BuMeIm]+ is 1-butyl-3-methylimidazolium and X- is PF6-, and (CF3SO2)2N-, was studied under gamma radiolysis (137Cs) in an argon atmosphere and in air. It was found that the density, surface tension, and refraction index of RTILs are unchanged even by an absorbed dose of approximately 600 kGy. Studied RTILs exhibit considerable darkening when subjected to gamma irradiation. The light absorbance of ionic liquids increases linearly with the irradiation dose. Water has no influence on radiolytic darkening. A comparative study of [BuMeIm]X and [Bu4N][Tf2N] leads to the conclusion that the formation of colored products is related to gamma radiolysis of the [BuMeIm]+ cation. The radiolytic darkening kinetics of RTILs is influenced by the anions as follows: Cl- < (CF3SO2)2N- < PF6-. Electrospray ionization mass spectrometry and NMR analysis reveal the presence of nonvolatile radiolysis products at concentrations below 1 mol% for an absorbed dose exceeding 1200 kGy. Initial step of BuMeIm+ cation radiolysis is the loss of the Bu* group, the H* atom from the 2 position on the imidazolium ring, and the H* atom from the butyl chain. Radiolysis of ionic liquid anions yields F* and CF3* from PF6- and [Tf2N]-, respectively. Recombinations of these primary products of radiolysis lead to various polymeric and acidic species.

Spectroscopic and electrochemical studies of U(IV)-hexachloro complexes in hydrophobic room-temperature ionic liquids [BuMeIm][Tf2N] and [MeBu3N][Tf2N].

The behavior of U(IV) octahedral complexes [cation]2[UCl6], where the [cation]+ is [BuMeIm]+ and [MeBu3N]+, is studied using UV/visible spectroscopy, cyclic staircase voltammetry, and rotating disk electrode voltammetry in hydrophobic room-temperature ionic liquids (RTILs) [BuMeIm][Tf2N] and [MeBu3N][Tf2N], where BuMeIm+ and MeBu3N+ are 1-butyl-3-methylimidazolium and tri-n-butylmethylammonium cations, respectively, and Tf2N- is the bis(trifluoromethylsulfonyl)imide anion. The absorption spectra of [cation]2[UCl6] complexes in the RTIL solutions are similar to the diffuse solid-state reflectance spectra of the corresponding solid species, indicating that the octahedral complex UCl6(2-) is the predominant chemical form of U(IV) in Tf2N--based hydrophobic ionic liquids. Hexachloro complexes of U(IV) are stable to hydrolysis in the studied RTILs. Voltammograms of UCl(6)2- at the glassy carbon electrode in both RTILs and at the potential range of -2.5 to +1.0 V versus Ag/Ag(I) reveal the following electrochemical couples: UCl6-/UCl6(2-) (quasi-reversible system), UCl(6)2-/UCl6(3-) (quasi-reversible system), and UCl(6)2-/UCl6(Tf2N)x-3+x (irreversible reduction). The voltammetric half-wave potential, Ep/2, of the U(V)/U(IV) couple in [BuMeIm][Tf2N] is positively shifted by 80 mV compared with that in [MeBu3N][Tf2N]. The positive shift in the Ep/2 value for the quasi-reversible U(IV)/U(III) couple is much greater (250 mV) in [BuMeIm][Tf2N]. Presumably, the potential shift is due to the specific interaction of BuMeIm+ with the uranium-hexachloro complex in ionic liquid. Scanning the negative potential to -3.5 V in [MeBu3N][Tf2N] solutions of UCl6(2-) reveals the presence of an irreversible cathodic process at the peak potential equal to -3.12 V (at 100 mV/s and 60 degrees C), which could be attributed to the reduction of U(III) to U(0).

Scavenging of OH(*) radicals produced from H(2)O sonolysis with nitrate ions.

The scavenging of OH(?) radicals formed during H(2)O sonolysis with nitrate-ions was studied in HNO(3)/NaNO(3) mixture at the constant NO(3)(-) ions concentration ([HNO(3)]+[NaNO(3)])=1 M in Ar atmosphere. Small amounts of N(2)H(5)NO(3) was added to solutions to avoid HNO(2) accumulation due to HNO(3) sonolysis. It was shown that the increase of [H(+)] causes the increase of H(2)O(2) formation rate (W(H(2)O(2)). (W(H(2)O(2)) values reach the plateau at [HNO(3)] approximately 1 M. The (W(H(2)O(2)) ratio in solution with [H(+)]=1 M and pure water was found to be equal to 2.4+/-0.4. It was assumed that (W(H(2)O(2)) increase in nitric acid medium is related to the changing of H(2)O(2) formation mechanism. In pure water H(2)O(2) is formed due to the OH(*) radicals recombination. In HNO(3)+NaNO(3) mixture the mechanism of H(2)O(2) formation consists in conversion of OH(*) radicals to NO(3)(*) radicals followed by NO(3)(*) radicals hydrolysis. Results obtained show that OH(*) radicals recombination mainly occurs in the liquid phase surrounding the cavitating bubble.

Sonolysis of metal beta-diketonates in alkanes.

The kinetics of metal beta-diketonates sonolysis was studied in hexadecane solutions using a UV/VIS spectrophotometric technique. The following complexes were prepared and studied: Cu(HFAA)(2), Cu(DPM)(2), Fe(ACAC)(3), Ni(DPM)(2), Er(DPM)(3), Nd(DPM)(3), Th(DPM)(4), UO(2)(BTFA)(2).TOPO, and Np(HFAA)(4), where HHFAA is hexafluoroacetylacetone, HDPM is dipivaloylmethane, HACAC is acetylacetone, HBTFA is benzoyltrifluoroacetone, and TOPO is trioctylphosphine oxide. Sonolysis was performed under the following conditions: ultrasonic frequency 22 kHz, intensity of ultrasound 3-5 Wcm(-2), temperature 70-92 degrees C, Ar atmosphere. The kinetic behavior of the studied complexes are interpreted using a two-site model of the sonochemical processes. In the case of metal beta-diketonates with high vapor pressure the sonochemical reactions tend to occur in the gaseous phase of the cavitating bubbles. The sonolysis of less volatile complexes first occur in the liquid reaction zone surrounding the bubbles. Sonication of the studied complexes results in the formation of X-ray amorphous products consisted of a mixture of metal beta-diketonates partial degradation products. Heating of as-prepared sonication products in air yields nanocrystalline oxides of corresponding metals.

Sonochemical polymerization of diphenylmethane.

Sonolysis of diphenylmethane (DPhM) has been studied under the effect of 20 kHz ultrasound (absorbed acoustic power 0.45 W/ml, surface area of sonotrode 1 cm(2), volume of sonicated solution 100 ml) under argon at 60 degrees C. The solid product of the sonolysis was characterized by elemental analysis, FTIR, 13C MAS NMR, TGA/DSC, XRD and TEM techniques. It was found that the sonolysis of DPhM causes formation of the polymer with the composition similar to crosslinked polystyrene. Assumed mechanism of DPhM sonolysis consists of DPhM molecules dissociation inside the cavitating bubble. Secondary radical scavenging and radical recombination processes yields the sonopolymer in the liquid phase. The breakdown of the aromatic ring during DPhM sonolysis confirms that a very high temperature established in the cavitating bubble.

Volatile metal beta-diketonates--new precursors for the sonochemical synthesis of nanosized materials--sonolysis of thorium(IV) beta-diketonates.

Ultrasonic irradiation (22 kHz, Ar atmosphere) of Th(IV) beta-diketonates Th(HFAA)4 and Th(DBM)4, where HFAA and DBM are hexafluoroacetylacetone and dibenzoylmethane respectively, causes them to decompose in hexadecane solutions, forming solid thorium compounds. The first-order rate constants for Th(IV) beta-diketonate degradation were found to be (9.3 +/- 0.8) x 10(-3) for Th(HFAA)4 and (3.8 +/- 0.4) x 10(-3) min-1 for Th(DBM)4, (T = 92 degrees C, I = 3 W cm-2). The rate of the sonochemical reaction increased with the rising beta-diketonate volatility and decreased with the rising hydrocarbon solvent vapor pressure. Solid sonication products consisted of a mixture of thorium carbide ThC2 and Th(IV) beta-diketonate partial degradation products. The average ThC2 particle size was estimated to be about 2 nm. ThC2 formation was attributed to the high-temperature reaction occurring within the cavitating bubble. The thorium beta-diketonate partial degradation products formed in the liquid reaction zones surrounding the cavitating bubbles.

Isotope effect in hydrogen peroxide formation during H2O and D2O sonication.

The kinetics of hydrogen peroxide formation have been studied during H2O and D2O sonication in the presence of argon and oxygen (f = 22 kHz, I = 3.0 W cm-2, Pac = 0.52 W ml-1, V = 20 ml, T = 20 degrees C). It was found that the sonochemical reaction rate W has a zero order with respect to hydrogen peroxide (H2O, D2O or DHO2) concentration. In argon atmosphere the kinetic isotope effect was found to be equal to alpha = WH2O/WD2O = 2.2 +/- 0.3. The alpha value decreases in H2O-D2O mixtures with increasing H2O concentration. In oxygen atmosphere the isotope effect is not observed (alpha = 1.05 +/- 0.10). It is assumed that the revealed isotope effect is related to the mechanism of water sonolysis including the H2O-Ar* and D2O-Ar* energy transition, where Ar* is an argon atom in an excited state, in nonequilibrium plasma generated by the shock-wave.

Kinetics of nitrous acid formation in nitric acid solutions under the effect of power ultrasound.

Sonochemical nitrous acid formation was investigated in 0.1-4.0 mol dm(-3) aqueous nitric acid solutions under the effect of power ultrasound with 20 kHz frequency. HNO2 steady-state concentration was obtained under long-time sonication; the excess HNO2 formed is decomposed and evoluted from the solution as NO and NO2 gases. The HNO2 steady-state concentration and the HNO2 initial formation rate depend linearly on the HNO3 concentration and acoustic intensity (1.8-3.5 W cm(-2)) and decrease with rising temperature in the range 21-50 degrees C. The HNO2 formation rate depends on the type of saturating gas as follows: Ar > N2 > He > air. NO and O2 are the major gaseous products of HNO3 sonication. The NO2 accumulation of in the gas phase is observed only when the decomposition of HNO2 formed becomes noticeable. The gaseous products formation rates depend on the HNO3 concentration, acoustic intensity and the type of saturating gas. The mechanism of HNO2 sonochemical formation is assumed to be the thermal decomposition of HNO3 in the gaseous vicinity of collapsing bubbles or in the overheated liquid reaction zone surrounding the cavitational bubbles.