The Origin of Isotope Effects in Sonoluminescence Spectra of Heavy and Light Water

Ndiaye, Abdoul Aziz; Pflieger, Rachel; Siboulet, Bertrand; Nikitenko, Sergey I.

doi:10.1002/anie.201208891

Cited by 20 publications

(16 citation statements)

References 22 publications

(34 reference statements)

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“…The formation of nonequilibrium plasma inside the cavitation bubble is in strong correlation with the isotope effects in MBSL spectra of heavy and light water observed recently by Ndiaye et al [46]. Despite a very small variation in physicochemical properties of H 2 O and D 2 O, their MBSL …”

Section: Sonoluminescence As a Probe Of Intrabubble Conditionssupporting

confidence: 74%

“…Moreover, the MBSL spectra of water exhibit much stronger OH(C 2 Σ + -A 2 Σ + ) emission bands in the presence of Xe compared to those in Ar [46]. In terms of nonequilibrium plasma model, the higher vibronic temperatures in Xe are the result of lower ionization potential of Xe compared to Ar (12.13 eV for Xe, 15.76 eV for Ar).…”

Section: Sonoluminescence As a Probe Of Intrabubble Conditionsmentioning

confidence: 95%

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Plasma Formation during Acoustic Cavitation: Toward a New Paradigm for Sonochemistry

Nikitenko

2014

Advances in Physical Chemistry

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The most recent spectroscopic studies of single bubble (SBSL) and multibubble (MBSL) sonoluminescence reveal that the origin of extreme intrabubble conditions is related to nonequilibrium plasma formed inside the collapsing bubbles. Analysis of the relative populations of OH(A 2 Σ + ) vibrational states observed during MBSL in water saturated with noble gases shows that in the presence of argon at low ultrasonic frequency weakly excited plasma is formed. At high-frequency ultrasound the plasma inside the collapsing bubbles exhibits Treanor behavior typical for strong vibrational excitation. Plasma formation during SBSL was observed in concentrated H 2 SO 4 preequilibrated with Ar. The light emission spectra exhibit the lines from excited Ar atoms and ionized oxygen O 2 + . Formation of O 2 + species is inconsistent with any thermal process. Furthermore, the SBSL spectra in H 2 SO 4 show emission lines from Xe + , Kr + , and Ar + in full agreement with plasma hypothesis. The photons and the "hot" particles generated by cavitation bubbles enable the excitation of nonvolatile species in solutions increasing their chemical reactivity. 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.

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Section: Sonoluminescence As a Probe Of Intrabubble Conditionssupporting

confidence: 74%

Section: Sonoluminescence As a Probe Of Intrabubble Conditionsmentioning

confidence: 95%

Plasma Formation during Acoustic Cavitation: Toward a New Paradigm for Sonochemistry

Nikitenko

2014

Advances in Physical Chemistry

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“…4). Moreover, the vibrational population distribution of OH(A 2 R + ) state exhibits strong excitation in Xe, even at low ultrasonic frequency [53]. Fig.…”

Section: Spectroscopic Analysis Of Oh Radical Mbslmentioning

confidence: 87%

“…The vibrational temperature of OH(A 2 R + ) radicals calculated for 20 kHz ultrasound in Xe is almost twice (9570 K) that in Ar [53]. In terms of plasma model the higher vibronic temperatures in Xe are the result of the lower ionization potential of Xe compared to Ar (12.13 eV for Xe, 15.76 eV for Ar).…”

Section: Spectroscopic Analysis Of Oh Radical Mbslmentioning

confidence: 89%

Toward a new paradigm for sonochemistry: Short review on nonequilibrium plasma observations by means of MBSL spectroscopy in aqueous solutions

Nikitenko

Pflieger

2017

Ultrasonics Sonochemistry

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This review summarizes recent studies of multibubble sonoluminescence (MBSL) in aqueous media in order to highlight new insights into the origin of the sonochemical activity. The observation of OH(CΣ-AΣ) emission band and a spectroscopic analysis of OH(AΣ-XΠ) emission band in MBSL of water pre-equilibrated with noble gases revealed the formation of a nonequilibrium plasma inside the collapsing bubble (T>T>T, where T is an electron temperature, T is a vibrational temperature and T is a rotational (gas) temperature). The T and T estimated using OH(AΣ-XΠ) emission band increase with ultrasonic frequency. In Xe the T of OH(AΣ) state is much higher than in Ar most probably due to the lower ionization potential of Xe. The MBSL of C Swan band (dΠ-aΠ) measured in aqueous tert-butanol (t-BuOH) solutions correlates with the data obtained for OH(AΣ-XΠ) emission band. Analysis of the gaseous products of t-BuOH sonolysis revealed a significant sonochemical activity even at high t-BuOH concentration when MBSL is totally quenched, indicating that drastic intrabubble conditions (plasma) are not necessarily accompanied by sonoluminescence. The nonequilibrium plasma model of cavitation allows to explain the reverse carbon isotope effect observed during the sonolysis of water in the presence of Ar/CO gas mixture.

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“…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(A 4,5 . At low ultrasonic frequency, weakly excited plasma with Brau vibrational distribution is formed.…”

Section: Introductionmentioning

confidence: 99%

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

Pflieger

Chave

Virot

et al. 2014

JoVE

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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 PuO 2 powder in pure water yields stable colloids of plutonium due to both effects. Video LinkThe video component of this article can be found at

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The Origin of Isotope Effects in Sonoluminescence Spectra of Heavy and Light Water

Abstract: 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.

Cited by 20 publications

References 22 publications

Plasma Formation during Acoustic Cavitation: Toward a New Paradigm for Sonochemistry

Plasma Formation during Acoustic Cavitation: Toward a New Paradigm for Sonochemistry

Toward a new paradigm for sonochemistry: Short review on nonequilibrium plasma observations by means of MBSL spectroscopy in aqueous solutions

Activating Molecules, Ions, and Solid Particles with Acoustic Cavitation

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