A comparison between multibubble sonoluminescence intensity and the temperature within cavitation bubbles

Cavitation bubble temperatures have been measured using a methyl radical recombination method and compared with the changes in the sonoluminescence intensity in aqueous ethanol solutions over a range of concentrations. Whereas the sonoluminescence intensity was decreased by more than 90% at low ethanol concentrations (<0.1 M), the measured bubble temperatures seem to be unaffected at this level of additive. The cavitation bubble temperatures were noticeably decreased at substantially higher ethanol concentrations (0.5 M). It has been concluded that the methyl radical recombination method does not report on the true sonoluminescence temperatures. However, it does report on the average bubble temperatures at which sonochemical reactions occur.     

An electron diffusion model of the space-time distribution of radicals in a multibubble cavitation field

Conditions under which electric discharges can arise in cavitation bubbles pulsating in a multibubble cavitation field are considered. Possible electric discharge types are discussed. It is shown that, in an electric breakdown in a cavitation bubble, the probability of the formation of a streamer (all the more, a leader) or corona discharge is negligibly small. It was found that, in a cavitation bubble, the development of an electron avalanche is most probable. The basic parameters of an elementary electron avalanche are estimated.     

Correlation between hydrocarbon distribution and water-hydrocarbon ratio in Fischer-Tropsch synthesis

In order to shorten the evaluation cycle of cobalt catalyst before the optimized catalyst is fixed on, a mathematical method is proposed to calculate weight percentage of C5+ hydrocarbons. Based on the carbide polymerization mechanism and the main hydrocarbons being linear alkanes and α-olefins, the correlation between hydrocarbon distribution and the molecular mass ratio of water to hydrocarbons is discussed. The result shows the ratio was within the range of 1.125-1.286 and the lower the ratio, the more gaseous hydrocarbons were obtained. Moreover, a linear equation between the weight percentage of C5+ hydrocarbons and the weight ratio of C5+ hydrocarbons to the total water is established. These results are validated by corresponding experiments. The weight percentage of C5+ hydrocarbons could be immediately calculated by this linear equation without detailed gas chromatography (GC) analysis of them.     

Electrostatic attraction between a hydrophilic solid and a bubble

The contact between fine hydrophilic α-Al(2)O(3) particles and nitrogen bubbles was studied as a function of solution composition in single bubble capture experiments, where the bubble collection efficiency was measured. The surface charges of both bubble and particle were controlled by varying the electrolyte concentration and pH of the solution. In all experiments the bubbles were negatively charged while the α-Al(2)O(3) particles were either negatively (above pH of the isoelectric point, pH(IEP)) or positively (below pH(IEP)) charged. The collection efficiency was found to be strongly influenced by the surface charge of the particles. The maximum collection efficiency occurred when the bubble and particle were oppositely charged (at low pH values) and at low salt concentration, i.e. when a long range attractive electrostatic interaction is present. In the case where both bubble and particle were of the same charge, the collection efficiency was near to zero within experimental error and was not influenced by either salt concentration or pH. This is the first experimental proof of the concept of 'contactless flotation', first proposed by Derjaguin and Dukhin in 1960, with far reaching implications from minerals processing to biology.     

Acoustic multibubble cavitation in water: A new aspect of the effect of a rare gas atmosphere on bubble temperature and its relevance to sonochemistry

Acoustic cavitation generates transient microbubbles with extremely high temperatures and high pressures, which can provide unique reaction routes. The maximum bubble temperature attained is widely known to be dependent on the polytropic index and thermal conductivity of the dissolved gas. Here, we show for the first time experimental evidence that the bubble temperature induced by a high frequency ultrasound is almost the same among different rare gases and the chemical efficiency is in proportion to the gas solubility of rare gases, which would be closely related to the number of active bubbles.     

A comparison between photon counting histogram and fluorescence intensity distribution analysis

Photon counting histogram (PCH) and fluorescence intensity distribution analysis (FIDA) are two methods that were developed independently but reported almost simultaneously. Both of them have been successfully applied to fluorescence fluctuation spectroscopy (FFS). Though publications have indicated that they are theoretically equivalent, they are still commonly considered as different methods, especially in their ways to treat the point spread functions (PSFs). In this paper, the two methods are examined in detail for a direct comparison. After a direct proof of the theoretical equivalence, the authors further point out that PCH and FIDA are completely equivalent in the way of modeling PSFs; that is, any modeling approach developed from one of them can always be applied to the other. It is also demonstrated that simplified FIDA and PCH formulas in the form of power series can be applied for fast and precise numerical calculations. The two methods are also compared for their merits in the calculation efficiency.     

Correlation between the rates of a catalytic reaction and the charge distribution in an intermediate complex

Theoretical and Experimental Chemistry -     

加温加压条件下气液固三相鼓泡塔体积传质系数的测定

气液固三相鼓泡塔反应器被广泛地应用于化工、石油化工、煤化工、化工冶金、环境工程等领域,如石油馏分的加氢、煤的脱硫与脱氮、对二甲苯氧化、费托合成、甲醇合成、二甲醚合成以及含有机物废水的湿式氧化等工业过程[1.2].     

Transient complex oscillations in a closed chemical system with coupled autocatalysis

In this study, hydroquinone was introduced to the classic Belousov-Zhabotinsky (BZ) reaction to build up coupled autocatalytic feedbacks. Various complex dynamical behaviors including successive period-adding bifurcations, irregular oscillations, and frequency modulations were observed in the coupled reaction system. Not only the complexity of oscillations but also the time period during which complex oscillations persist were found to depend greatly on the initial concentration of hydroquinone, which was expected to manifest the coupling strength in the studied system. Dependence of the observed transient complex oscillations on concentrations of ferroin, sulfuric acid, bromate, and malonic acid was also characterized systematically. Numerical simulations with a modified BZ model via incorporating reactions involving hydroquinone and products of hydroquinone qualitatively reproduced the influence of hydroquinone seen in experiments.     

Correlation between phosphorescence lifetimes and ratios of steady state phosphorescence to fluorescence intensity for biacetyl in various solvents

The phosphorescence of biacetyl in fluid solutions is quenched not only by oxygen but also by impurities resulting from the distillation procedure and from the freeze-pump-thaw degassing technique. A linear correlation between the measured phosphorescence lifetimes and the ratios of the phosphorescence to the fluorescence intensities is established; the slope affords reliable calculations of the biacetyl triplet lifetimes from steady state measurements and additionally the determination of the rate constant k_p of radiative triplet deactivation. This constant is dependent on the solvent, whereas the fluorescence constant k_F is not.     

Generalized Rabi oscillations in a three-level metastable system under periodic and quasiperiodic perturbations

The quantum dynamics of prototypical three-level metastable system under external perturbations, both time-independent and time-dependent, are studied numerically as well as analytically. The regular Rabi oscillations generated in the system under a monochromatic perturbation are shown to develop additional features when the system has a metastable state. The autocorrelation function of ψ(t) reveals nondecaying, almost quasiperiodic, behavior in such systems. The Rabi oscillations turn more complex when a bichromatic perturbation with two incommensurate frequencies is allowed to interact with the three-level system, irrespective of the presence or absence of a metastable state. A rapid decay in the autocorrelation function of the wavefunction [ψ(t)] is observed in such cases. © 1996 Wiley & Sons, Inc.     

Three-phase contact line profile between a large air bubble and a flat solid surface

The spreading of the three-phase contact (TPC) line after rupture of the thin film between a large air bubble and a flat solid surface was experimentally studied by means of a CCD high-speed video technique. The present study shows that the TPC line profile is noncircular for a deformed bubble.     

Dilution reinitiated oscillations in the Bray-Liebhafsky system

The resumption of oscillatory trains in the non-oscillatory region subsequent to completion of the last oscillation, as a phenomenon interesting for the stability of any reaction which can reach the oscillatory state in principle, is analyzed here for the case of the Bray-Liebhafsky reaction. It is shown that this effect is affected by temperature, acidity, initial concentration of hydrogen peroxide and quantity of added water.

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浆态床反应器中相含率及粒径分布的研究

以空气－水－石英砂体系为对象，研究了费托合成浆态床反应器中表观气速、平均淤浆浓度、床层轴向位置等因素对气含率、固体浓度轴向分布和粒径分布的影响，并通过实验得出了气含率与操作变量之间的关联式。     

Correlation effects in a few-particle one-dimensional Coulomb-interacting system

Summary A model of the one-dimensional Coulomb-interacting few-particle system is studied in detail. The model is similar to a many-electron system which in a zero-order approximation of the non-interacting particles has only singly occupied one-electron levels. Such model cancels the divergencies in the Coulomb and exchange interaction energies found regularly for a conventional one-dimensional system which is built up of the doubly occupied one-electron levels and is submitted to the Coulomb perturbation. In the present case, the correlated wave functions for the system can be obtained from the Slater determinants constructed for the sets of the one-electron levels and combined according to the rules given by the standard perturbation theory. The calculations allow us to discuss the correlation influence and the effect of the size of the model on: (i) the excitation energies including the criterion corresponding to the metal-insulator transition (the Mott transition), (ii) the distribution of the correlated charge along the model, (iii) the average velocity of a two-particle system being in different states, and (iv) the dipole moments and transition probabilities. In the last case, the lifetime of the uncorrelated and correlated excited states obtained in the situation of the allowed one-photon transitions can be compared with the lifetime obtained for a similar system in the case when the one-photon transitions are forbidden and two-photon transitions should be taken into account. No data other than the length of the model and the fundamental constants of nature enter the calculations.     

Study of spatial correlations in a supercooled molecular system

Spatial heterogeneities have been investigated in a supercooled system composed of diatomic molecules with an associated dipole moment by using the molecular dynamics simulation technique. Pair distribution functions of molecules with different mobilities have been evaluated, and it has been found that molecules belonging to the same dynamic domain are spatially correlated. Molecules with extremely large mobilities form larger clusters than those resulting from random statistics. These clusters are stringlike shaped. The mean cluster size displays a maximum at times between the ballistic and the diffusive regime, approximately at the end of the beta-relaxation zone. The value of this maximum increases upon cooling the system. An analogous profile has been observed for the characteristic cluster length when plotted against time. Agreement with Adam-Gibbs predictions has been encountered when considering these clusters as the basic dynamic units of the theory. For the extremely slow molecules, a cluster distribution has also been encountered. These clusters are smaller than the ones composed by fast molecules; they do not have a quasilinear geometry and no maximum is observed for their mean cluster size.     

Interaction between a stationary mercury electrode and a hydrogen bubble in an aqueous sodium dodecyl sulphate solution

The stability and rupture of thin liquid films formed from an aqueous solution of Na₂SO₄ (0.05 mol dm⁻³) in the presence of 5 × 10⁻⁵ mol dm⁻³ sodium dodecyl sulphate between a stationary mercury electrode and a hydrogen bubble has been investigated as a function of electrode potential. The electrostatic component of disjoining pressure has been calculated using the results of capacity measurement for the mercury-solution interface. Special attention has been paid to films formed on positively charged mercury surfaces. In this case, despite the positive electrode polarization, the outer Helmholtz plane potential is found to be negative due to the high surface activity of the dodecyl sulphate anion. The van der Waals component of disjoining pressure has been calculated on the basis of a double sheath model of the two interacting surfaces, taking into consideration the orientation of the adsorbed surfactant layers at the interfaces. Calculations of the total disjoining pressure can explain film stability at negative mercury potentials, but do not explain film rupture when the polarization of the mercury is positive. The existence of a hydrophobic attractive interaction is postulated in the latter case.