Name: activating molecules, ions, and solid particles with acoustic cavitation
Uploaded: 2014-04-11T21:30:00
Description: Watch this Scientific Journal Video about Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation at JoVE.com

The authors would like to acknowledge the French ANR (grant ANR-10-BLAN-0810 NEQSON) and CEA/DEN/Marcoule.

1. Measurement&#160;of Uranium Sonoluminescence
The thermostated cylindrical sonoreactor is mounted on top of a high-frequency transducer providing 203 or 607 kHz ultrasound. Ultrasonic irradiation with low frequency ultrasound of 20 kHz is performed with a 1-cm2 titanium horn placed reproducibly on top of the reactor. The emission spectra are recorded in the range 230&#8211;800 nm using a spectrometer coupled to a liquid-nitrogen cooled CCD camera. Hydrogen in the outlet gas is measu...

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The most critical parameters for successful observation of sonoluminescence and sonochemistry are: 1) rigorous control of the saturating gas and the bulk temperature during sonication, 2) careful selection of ultrasonic frequency, 3) using an optimal composition of sonicated solution to prevent quenching.
The kinetics of the sonochemical reactions as well as the intensity of sonoluminescence is very sensitive to the temperature of solution submitted to ultrasound: in contrast to the kinetics o...

The use of power ultrasound in numerous industrial and research areas, such as the cleaning of solid surfaces, degassing of liquids, material sciences, environmental remediation, and medicine, has received much attention during the last decade 1. The ultrasonic treatment increases the conversion, improves the yield, and initiates the reactions in homogeneous solutions as well as in heterogeneous systems. It is generally accepted that the physical and chemical effects of ultrasonic vibrations in liquids arise from acoustic cavitation or, in other words, to the implosive collapse of microbubbles in fluids irradiated with power ultrasound 2. Violent implosion of the cavitation bubble generates transient extreme conditions in the gas phase of the bubble, which are responsible for the formation of chemically active species and sonoluminescence. Nevertheless, debate still continues over the origin of such extreme conditions. Spectroscopic analysis of the sonoluminescence helps to better understand the processes occurring during the bubble collapse. In water, saturated with noble gases, the sonoluminescence spectra are composed from OH(A2&#931;+-X2&#928;i), OH(C2S+-A2S+) bands and a broad continuum ranging from UV to NIR part of the emission spectra 3. Spectroscopic analysis of OH(A2&#931;+-X2&#928;i) emission bands revealed formation of nonequilibrium plasma during sonolysis of water 4, 5. At low ultrasonic frequency, weakly excited plasma with Brau vibrational distribution is formed. By contrast, at high-frequency ultrasound, the plasma inside collapsing bubbles exhibits Treanor behavior typical for strong vibrational excitation. The vibronic temperatures (Tv, Te) increase with ultrasonic frequency indicating more drastic intrabubble conditions at high-frequency ultrasound.
In principal, each cavitation bubble can be considered as a plasma chemical microreactor providing highly energetic processes at almost room temperature of the bulk solution. The photons and the "hot" particles produced inside the bubble enable to excite the non-volatile species in solutions thus increasing their chemical reactivity. For example, the mechanism of ultrabright sonoluminescence of uranyl ions in acidic solutions is influenced by uranium concentration: photons absorption/re-emission in diluted solutions, and excitation via collisions with "hot" particles contributes at higher uranyl concentration 6. Chemical species produced by cavitation bubbles can be used for the synthesis of metallic nanoparticles without any templates or capping agents. In pure water sparged with argon, the sonochemical reduction of Pt(IV) occurs by hydrogen issued from sonochemical water molecules splitting yielding monodispersed nanoparticles of metallic platinum 7. Sonochemical reduction is accelerated manifold in the presence of formic acid or Ar/CO gas mixture.
Many previous studies have shown the advantages of ultrasound to activate the surface of divided solids due to the mechanical effects in addition to chemical activation 8,9. Small solid particles that are much less in size than the cavitation bubbles do not perturb the symmetry of collapse. However, when a cavitation event occurs near big aggregates or near extended surface the bubble implodes asymmetrically, forming a supersonic microjet leading to the cluster disaggregating and to the solid surface erosion. Ultrasonic treatment of plutonium dioxide in pure water sparged with argon causes formation of stable nanocolloids of plutonium(IV) due to both physical and chemical effects 10.

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">20 kHz Ultrasound Generator</td>
			<td style="width:71px;">Sonics Vibracell</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">Multifrequency Generator AG 1006</td>
			<td style="width:71px;">T&#38;C Power&#160; Conversion</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Cryostat RE210&#160;</td>
			<td style="width:71px;">Lauda</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Spectrometer SP 2356i</td>
			<td style="width:71px;">Roper Scientific</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">CCD camera SPEC10-100BR cooled with liquid nitrogen</td>
			<td style="width:71px;">Roper Scientific</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Quadrupole mass-spectrometer PROLAB 300</td>
			<td style="width:71px;">Thermoscientific</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Centrifuge Sigma 1-14</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">H2PtCl6 6H2O</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ar; Ar/CO gases</td>
			<td style="width:71px;">Air Liquid</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Uranium and Plutonium compounds</td>
			<td style="width:71px;"></td>
			<td style="width:119px;"></td>
			<td>Prepared in the laboratories of Marcoule Research Center</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Perchloric acid</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Phosphoric acid</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Formic acid</td>
			<td style="width:71px;">Sigma-Aldrich</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
	</tbody>
</table>

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 cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species and to the emission of light, named sonoluminescence. In this manuscript, we describe the techniques allowing study of extreme intrabubble conditions and chemical reactivity of acoustic cavitation in solutions. The analysis of sonoluminescence spectra of water sparged with noble gases provides evidence for nonequilibrium plasma formation. The photons and the "hot" particles generated by cavitation bubbles enable to excite the non-volatile species in solutions increasing their chemical reactivity. For example the mechanism of ultrabright sonoluminescence of uranyl ions in acidic solutions varies with uranium concentration: sonophotoluminescence dominates in diluted solutions, and collisional excitation contributes at higher uranium concentration. Secondary sonochemical products may arise from chemically active species that are formed inside the bubble, but then diffuse into the liquid phase and react with solution precursors to form a variety of products. For instance, the sonochemical reduction of Pt(IV) in pure water provides an innovative synthetic route for monodispersed nanoparticles of metallic platinum without any templates or capping agents. Many studies reveal the advantages of ultrasound to activate the divided solids. In general, the mechanical effects of ultrasound strongly contribute in heterogeneous systems in addition to chemical effects. In particular, the sonolysis of PuO2 powder in pure water yields stable colloids of plutonium due to both effects.

Uranyl ion sonoluminescence is extremely weak in HClO4 solutions: though typical light absorption by UO22+ ions is observed below 500 nm, emission lines from excited (UO22+)* (centered at 512 nm and 537 nm) are hardly seen (Figure 1). The SL of UO22+ is quenched. This quenching can be attributed to reduction of the excited uranyl ion by a coordinated water molecule 11-13:
(...

Watch this Scientific Journal Video about Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation at JoVE.com

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

Acoustic cavitation in liquids submitted to power ultrasound creates transient extreme conditions inside the collapsing bubbles, which are the origin of unusual chemical reactivity and light emission, known as sonoluminescence. In the presence of noble gases, nonequilibrium plasma is formed. The "hot" particles and the photons generated by collapsing bubbles are able to excite species in solution.

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

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