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<p>This is the first study of the light emission during the sonolysis of liquid ammonia and of solutions of cerium and silver salts in this solvent at –70°C. A Ce<sup>3+</sup> luminescence band with a maximum at 400 nm in the moving singlebubble sonoluminescence spectrum generated by ultrasound in a solution of 5·10<sup>–4</sup> M Ce(SO<sub>4</sub>)<sub>2</sub> in ammonia was discovered. This band was found in addition to the bubble luminescence continuum usual for liquids (240–800 nm in ammonia). The quenching of this band in the presence of AgNO<sub>3</sub> in ammonia solution indicates that electron acceptor Ag<sup>+</sup> ions suppress the probable sonochemiluminescence reaction Ce<sup>4+</sup> + <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10812_2025_1874_Article_IEq1.gif" Format="GIF" Height="19" Rendition="HTML" Resolution="72" Type="Linedraw" Width="21" /> </InlineMediaObject> <EquationSource Format="TEX">\({e}_{s}^{-}\)</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mi>e</mi> <mrow> <mi>s</mi> </mrow> <mo>-</mo> </msubsup> </math></EquationSource> </InlineEquation> → η(Ce<sup>3+</sup>)<sup>*</sup> + (1 − η) Ce<sup>3+</sup>, (Ce<sup>3+</sup>)<sup>*</sup> → Ce<sup>3+</sup> + hν responsible for the detected Ce<sup>3+</sup> glow. The concentration of Ce4+ in the solution is diminished when it is reduced in this reaction and the sonoluminescence intensity of the Ce<sup>3+</sup> band also decreases during the sonolysis but then reaches a constant level a few minutes after its onset. This behavior is attributed to the attainment of a dynamic equilibrium between the rates of cerium ion reduction and oxidation: Ce<sup>4+</sup> → Ce<sup>3+</sup> and Ce<sup>3+</sup> → Ce<sup>4+</sup>, respectively. The one-electron oxidizing agent in the latter reaction is presumably the NH<sub>2</sub> radical, which is another primary product of ammonia sonolysis, in addition to a solvated electron (<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10812_2025_1874_Article_IEq2.gif" Format="GIF" Height="19" Rendition="HTML" Resolution="72" Type="Linedraw" Width="21" /> </InlineMediaObject> <EquationSource Format="TEX">\({e}_{s}^{-}\)</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mi>e</mi> <mrow> <mi>s</mi> </mrow> <mo>-</mo> </msubsup> </math></EquationSource> </InlineEquation>). The formation of Ce<sup>3+</sup> cations during the sonolysis of a Ce(SO<sub>4</sub>)<sub>2</sub> solution was confirmed by the detection of Ce<sup>3+</sup> photoluminescence. The excitation yield in the sonochemiluminescence reaction η = 2·10<sup>–6</sup>.</p>

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Electron-Stimulated Sonochemiluminescence of Ce3+ Ions in Liquid Ammonia

  • 期刊论文

  • 发表日期：

    2025年2月26日

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  • B. M. Gareev,
  • A. M. Abdrakhmanov,
  • L. R. Yakshembetova,
  • G. L. Sharipov

摘要

This is the first study of the light emission during the sonolysis of liquid ammonia and of solutions of cerium and silver salts in this solvent at –70°C. A Ce3+ luminescence band with a maximum at 400 nm in the moving singlebubble sonoluminescence spectrum generated by ultrasound in a solution of 5·10–4 M Ce(SO4)2 in ammonia was discovered. This band was found in addition to the bubble luminescence continuum usual for liquids (240–800 nm in ammonia). The quenching of this band in the presence of AgNO3 in ammonia solution indicates that electron acceptor Ag+ ions suppress the probable sonochemiluminescence reaction Ce4+ + \({e}_{s}^{-}\) e s - → η(Ce3+)* + (1 − η) Ce3+, (Ce3+)* → Ce3+ + hν responsible for the detected Ce3+ glow. The concentration of Ce4+ in the solution is diminished when it is reduced in this reaction and the sonoluminescence intensity of the Ce3+ band also decreases during the sonolysis but then reaches a constant level a few minutes after its onset. This behavior is attributed to the attainment of a dynamic equilibrium between the rates of cerium ion reduction and oxidation: Ce4+ → Ce3+ and Ce3+ → Ce4+, respectively. The one-electron oxidizing agent in the latter reaction is presumably the NH2 radical, which is another primary product of ammonia sonolysis, in addition to a solvated electron ( \({e}_{s}^{-}\) e s - ). The formation of Ce3+ cations during the sonolysis of a Ce(SO4)2 solution was confirmed by the detection of Ce3+ photoluminescence. The excitation yield in the sonochemiluminescence reaction η = 2·10–6.