ABSTRACT
Colloidal suspensions of EuCl2, EuBr2, and EuSO4 nanoparticles (<50â nm) in dodecane and EuSO4 in 70% H2SO4 were synthesized. Moving single-bubble sonoluminescence (m-SBSL) spectra were obtained for a bubble performing radial oscillations in these suspensions and translational motions at the antinode of a standing ultrasonic wave with a frequency of about 27â kHz. In these spectra (at a spectral resolution of 10â nm), the sono-excited luminescence bands of the Eu2+ ion were detected for the first time, coinciding in the shape and position of the maxima (404, 413, and 377â nm for EuCl2, EuBr2, and EuSO4, respectively) with the bands of Eu2+ located in a crystalline environment in the photoluminescence spectra of nanoparticles of europium salts in suspensions. The detected sonoluminescence of Eu2+ arises due to the injection of nanoparticles into a bubble deformed during motion and excitation of a lanthanide ion at the periphery of the bubble volume during collisions of nanoparticles with charged particles, mainly electrons, coming from a hot nonequilibrium plasma, which periodically arises during bubble compression. Evidence for the excitation of the europium ion in the bubble is the absence of its luminescence bands in the SBSL spectra of the translationally immobile bubble, in which nanoparticles are unlikely to enter. The nanoparticles that enter the bubble also undergo decomposition in the plasma into fragments, in particular, with the formation of Eu, Eu+ in the excited state. The atomic lines of these fragments were recorded for the first time in the m-SBSL spectrum with a resolution of 1â nm for a suspension of EuSO4 nanoparticles in 70% H2SO4. The resulting m-SBSL spectra will add to the library of characteristic spectra of objects of sonoluminescent spectroscopic analysis and will make it possible to identify and determine the content of Eu or Eu2+ in these objects.
ABSTRACT
This is a brief research review on the new method of development for element luminescence determination, namely, sonoluminescent spectroscopy. The advantages and disadvantages of the technique of multibubble sonoluminescence (MBSL) in solutions used to apply this method are discussed. It has been shown that the use of a new technique moving single-bubble sonoluminescence (m-SBSL) in colloidal suspensions of nanoparticles (<50 nm) containing the elements analyzed seems preferable for this purpose. This makes it possible to determine elements not only at lower concentrations than when using MBSL in solutions but also to find elements that are unavailable for determination through previous techniques. Thus, this new technique expands the range of elements that can be determined using sonoluminescent spectroscopy. The article provides a detailed description of the standard procedure for the preparation and recording of m-SBSL in colloidal suspensions, as well as examples of characteristic spectra of some elements obtained and recorded for the first time according to this new technique (Al, K, Mn, Cd, Pt, Ni, and Ti), including those not previously found using the MBSL in solutions (Al, Cd, Pt, Ni, and Ti). An example of the analytical line at 396 nm in the Al spectrum obtained through this new technique on the basis of an AlCl3 initial aqueous solution, the region of the linear dependence of the intensity on the AlCl3 concentration was registered, and the lower limit of the spectroscopic determination of the Al content in this solution was estimated as 8.3·10-3 M. Using the analysis of the obtained Cd spectrum as an example, we carried out a spectroscopic measurement of the electronic temperature achieved at m-SBSL in bubble plasma at the moment of greatest compression of a bubble with light emission during its acoustic oscillations in dodecane, Te = 7900 ± 500 K.
ABSTRACT
The moving single-bubble sonoluminescence of Ce3+ in water and ethylene glycol solutions of CeCl3 and (NH4)2Ce(NO3)6 was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10-4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce4+ reduction by a solvated (or hydrated in water) electron: Ce4+ + es (eaq) â *Ce3+. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl3 solutions, the Ce4+ ion is formed at the oxidation of Ce3+ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br- (acceptor of OH) and H+ ions (acceptor of eaq). In water and ethylene glycol solutions of (NH4)2Ce(NO3)6, the sonochemiluminescence also quenched by the H+ ion. The sonochemiluminescence in CeCl3 solutions is registered at [Ce3+] ≥ 10-5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10-2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce3+ in solutions with [Ce3+] ≥ 10-4 M. If the cerium concentration is more than 10-2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce3+ ions penetrating into the moving bubble.
