A kinetic study of the effect of ultrasound power on the sonohydrolysis of tetraethyl orthosilicate

A kinetic study of the ultrasound-stimulated and acid-catalyzed sonohydrolysis of tetraethyl orthosilicate (TEOS) in solventless TEOS–water heterogeneous mixtures was carried out by means of a calorimetric method as a function of the ultrasound power. The hydrolysis reaction starts in acidulated heterogeneous water–TEOS mixtures after an induction period under ultrasonic stimulation. The ultrasound power seems to play a role on the dynamical coupling of the system originating a continuum upward shifting of the base line during the induction period of sonication. The rate in which the base line is upward shifted diminishes with the power. The best coupling between the ultrasound and the reactant heterogeneous mixtures for this experimental setup was found to occur at 50 W, for which the gelation time was found to be a minimum. The kinetics of the heterogeneous TEOS sonohydrolysis was studied on the basis of a dissolution and reaction modeling. The heterogeneous reaction pathway as deduced from the kinetic study was drawn in a ternary diagram as a function of the ultrasound power.     

A dissolution and reaction modeling for hydrolysis of TEOS in heterogeneous TEOS-water-HCl mixtures under ultrasound stimulation

A simplified dissolution and reaction modeling was employed to study the hydrolysis of heterogeneous tetraethoxysilane (TEOS)-water-HCl mixtures under ultrasound stimulation. The nominal pH was changed from 0.8 to 2.0. The acid specific hydrolysis rate constant was determined as k = 6.1 mol-1 1 min-1 [H+]-1 at 39 degrees C, in good agreement with the literature. Along the heterogeneous step of the reaction, the ultrasound maintains an additional quantity of water under a virtual state of dissolution besides the water dissolved due to the homogenizing effect of the alcohol produced in the reaction. The forced virtually dissolved water is probably represented by water at the TEOS-water interface during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TEOS phase, while hydrolysis has not started yet, was evaluated as about 290 A. The HCl concentration accordingly increases the hydrolysis rate constant but its fundamental role on the immiscibility gap of the TEOS-water-ethanol system has not been unequivocally established.     

Adsorption kinetics of 4-chlorophenol onto granular activated carbon in the presence of high frequency ultrasound

This work describes the results of investigations carried out to examine the adsorption kinetics of 4-chlorophenol (4-CP) from aqueous solution containing tert-butyl alcohol (10%, v/v) onto granular activated carbon (GAC) in the presence of ultrasound of different high frequencies (516, 800 and 1660 kHz) and acoustic powers (15.2, 21.5, 31.1 and 38.3 W). The main objective of this study is to describe the mechanism of ultrasound-assisted adsorption rather than the enhancement of adsorption capacity. Sonochemical degradation of 4-CP was studied in the absence and presence of tert-butyl alcohol. The sonolysis of 4-CP is effectively inhibited by the addition of tert-butyl alcohol (10%, v/v) and very little 4-CP degradation occurs, indicating that little or no pyrolysis of the compound occurs. Without addition of tert-butyl alcohol, after 300 min and at 1660 kHz, the removal of 4-CP in the presence of ultrasound for an acoustic power of 38.3 W was nearly total (99%), but in the conventional method only 60% was eliminated. In this case, the removal of 4-CP by GAC in the ultrasound-assisted technique is due to both adsorption and ultrasonic degradation, but the removal by simple stirring is only due to adsorption, which makes a direct comparison unacceptable. In order to distinguish sonochemical degradation and adsorption of 4-CP onto GAC and to make an exact and practical comparison of the adsorption in the absence and presence of ultrasound, kinetic adsorption experiments were conducted using aqueous solution containing 10% (v/v) tert-butyl alcohol. The obtained results show that both adsorption rate and adsorbed amount were significantly enhanced and improved in the presence of ultrasound for all the studied frequencies and powers. The enhancement of adsorption is favored by increasing ultrasonic power. Adsorption kinetic data were modeled using the liquid-film mass transfer equation and intraparticle diffusion model. The values of the intraparticle diffusion coefficient obtained in the presence of ultrasound are greater than that obtained in the absence of ultrasound. In the initial period of adsorption, where external mass transfer is assumed to predominate, liquid-film mass transfer coefficients significantly increased by the assistance of ultrasound. These results indicate that ultrasound enhances the mass transport in the pores as well as across the boundary layer. This effect increased with increasing ultrasonic power for the three studied frequencies. The average order for the studied ultrasonic waves according to the initial adsorption rate, the intraparticle diffusion coefficient and the liquid-film mass transfer coefficient is 516 kHz>800 kHz>1660 kHz.     

Phase-transfer catalysis and ultrasonic waves II: saponification of vegetable oil.

Saponification of oils which is a commercially important heterogeneous reaction, can be speeded up by the application of ultrasound in the presence of phase-transfer catalyst (PTC). This paper focuses on the ability of ultrasound to cause efficient mixing of this liquid-liquid heterogeneous reaction. Castor oil was taken as a model oil and the kinetic of the reaction was followed by the extent of saponification. The hydrolysis of castor oil was carried out with different PTC such as cetyl trimethyl ammonium bromide (CTAB), benzyl triethyl ammonium chloride (BTAC) and tetrabutyl ammonium bromide (TBAB) in aqueous alkaline solution. As hydroxyl anion moves very slowly from aqueous to oil phase, the presence of a PTC is of prime importance. For this purpose, cationic surfactants are selected. The sonication of biphasic system were performed by 20 kHz (simple horn and cup horn) and 900 kHz. It was found that CTAB was better than the two others and this could be related to the molecular structure of the PTCs. The effect of temperature was also studied on the saponification process. By increasing the temperature, the yield was also increased and this could be explained by intermolecular forces, interfacial tension and mass transfer. Saponification of three different vegetable oils shows that the almond oil is saponified easier than the two others and this could be related to their properties such as surface tension, viscosity and density.     

Ultrasound-assisted adsorption of copper(II) ions on hazelnut shell activated carbon

The present study was aimed to removal of Cu(II) ions from aqueous solution by ultrasound-assisted adsorption onto the granular activated carbon obtained from hazelnut shells. The attention was focused on modeling the equilibrium and kinetics of Cu(II) adsorption onto the granular activated carbon. The granular activated carbon was prepared from ground dried hazelnut shells by simultaneous carbonization and activation by water steam at 950 °C for 2 h. Adsorption isotherm data were better fitted by the Langmuir model than the Freundlich model in both the absence and the presence of ultrasound. The maximum adsorption capacity of the adsorbent for Cu(II), calculated from the Langmuir isotherms, in the presence of ultrasound (3.77 mmol/g) is greater than that in the absence of ultrasound (3.14 mmol/g). The adsorption process in the absence and the presence of ultrasound obeyed to the pseudo second-order kinetics. The removal of Cu(II) ions was higher in the presence of ultrasound than in its absence, but ultrasound reduced the rate constant. The intraparticular diffusion model indicated that adsorption of Cu(II) ions on the granular activated carbon was diffusion controlled as well as that ultrasound promoted intraparticular diffusion.     

The effect of ultrasound upon the oxidation of thiosulphate on stainless steel and platinum electrodes

Ultrasound was found to increase the oxidation peak current and hence the decomposition rate of thiosulphate 50-fold compared to silent conditions. The effects of the ultrasonic frequency (20 and 38 kHz) and power upon the electrochemical oxidation of thiosulphate in aqueous KCl (1 mol dm-3) at stationary stainless steel and platinum electrodes were studied chronoamperometrically and potentiostatically (at various scan rates). No sigmoidal-shaped voltammograms were observed for the redox couple S4O6(2-)/S2O3(2-) in the presence of ultrasound. However, application of ultrasound to this redox couple provided an increase in the oxidation peak current at the frequencies employed, the magnitude of which varied with concentration, scan rate and ultrasonic power. Under sonication at 20 and 38 kHz, the oxidation peak potential shifted anodically with increasing ultrasonic power. This anodic shift in potential may be due to the formation of hydroxyl radicals, changes in electrode surface composition and complex adsorption phenomena. The large increase in oxidation peak currents and the rates of decomposition of thiosulphate, in the presence of ultrasound, are explained in terms of enhanced mass transfer at the electrode due to cavitation and acoustic streaming together with microstreaming coupled with adsorption phenomena. It is also shown that changes in macroscopic temperature throughout the experiment are insufficient to cause the observed enhanced diffusion.     

Reaction kinetics of the Pt, O2(g)|c-ZrO2 system: precursor-mediated adsorption

A micro kinetic model of the Pt, O₂(g)|c-zirconia electrode/electrolyte system was developed in state space form (model M3). The oxygen adsorption/desorption process was modeled as a precursor-mediated surface reaction. The surface diffusion of atomic oxygen and the electrochemical reduction of atomic oxygen near the three-phase boundary (tpb) were considered. It was shown that the simulated charge-transfer behavior of M3 is significantly different from models with ordinary Langmuir kinetics (model M2). The electrochemical rate constant was estimated from selected experimental data as k₁₀=(6.05±0.25)·10⁶ m³/(mol·s). From experimental results it was concluded that only one adsorbed oxygen species is relevant for the dynamic behavior. In porous Pt electrodes binary gas phase diffusion of oxygen in O₂/N₂ gas mixtures becomes relevant at oxygen partial pressures below 10⁻³ atm. The general procedure for state and parameter estimation can be well adopted for the investigation of further reaction mechanisms.     

Sonoelectrochemical recovery of silver from photographic processing solutions

This paper describes the effect of ultrasound upon the electrochemical recovery of silver from photographic processing solutions using a newly designed electrochemical cell--SonoEcoCell. Rates of deposition of silver (obtained potentiostatically) were studied in the model 'fix' solutions (dilute aqueous Na2S2O3/NaHSO3 at a stainless steel cylinder electrode in both the absence and the presence of ultrasound. Under silent conditions, the magnitude of the cathodic potential is a major factor in the removal of silver. Under 20 kHz sonication, the rate of deposition of silver increases with increasing ultrasonic intensity. The cathode efficiency is also enhanced under insonation. The position of the ultrasonic probe with respect to the rotating cylinder electrode (RCE) was studied. It was found that for a 'face-on' geometry (probe parallel to the electrode) led to higher rate constants compared with a 'side-on' geometry (probe perpendicular to the electrode). The effect of coupling an RCE with ultrasound upon these rate constants employing the two geometry was also investigated. It was found that, employing either the face-on or the side-on geometry alone, improved rate constants were obtained below approximately 1500 and 2000 rpm, respectively.     

Effects of ultrasound on both electrolytic and electroless nickel depositions

The effects of ultrasound on both electrolytic and electroless nickel depositions were investigated by polarization and a.c. impedance methods. The ultrasound accelerated the charge transfer process at the metal-electrolyte interface in the electrodeposition and the mass transport process in the electroless deposition. In the electrodeposition with Watts bath, the crystal orientations of deposited film largely changed in the presence of ultrasound. The imposition of ultrasound gave rise to decreasing cathodic overpotential and increasing exchange current density, and these effects depended upon the ultrasonic frequency. The values of exchange current density estimated from a.c. impedance were dependent upon the measured electrode potentials. In the electroless deposition with citrate bath, the deposition rates increased in the presence of ultrasound. There were two kinds of Ni(2+)-citrate complex which were reduced at -0.7 V and -1.1 V. The electroless deposition process was controlled by the Ni(2+)-citrate complex that was reduced at -0.7 V. This reduction rate was diffusion controlled and largely increased in the presence of ultrasound. The effects of ultrasonic frequency on both electrodeposition and electroless deposition increased in order of no irradiation < 100 kHz < 28 kHz < or = 45 kHz.     

Enhanced electrocatalytic oxidation of hydroxylamine on Pt/polypyrrole composite modified glassy carbon electrode

A sensitive hydroxylamine sensor is developed by electrodeposition of Pt nanoparticles on pre-synthesized polypyrrole nanoparticles modified glassy carbon electrode. The modified electrode presents distinctly electrocatalytic activity toward hydroxylamine oxidation. The kinetic parameters such as the overall numbers of electrons involved in hydroxylamine oxidation, the electron transfer coefficient, standard heterogeneous rate constant, and diffusion coefficient are evaluated. The current response increases linearly with increasing hydroxylamine concentrations and exhibits two wide linear ranges of 5.0?×?10^?7–1.1?×?10^?3 and 1.1?×?10^?3–18.8?×?10^?3 M with a detection limit of 0.08 μM (s/n?=?3). The proposed electrode presents excellent operational and storage ability for determining hydroxylamine. Moreover, the sensor shows good sensitivity, selectivity, and reproducibility properties.     

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.     

Ultrasonic frequency effects on the removal of Microcystis aeruginosa

Algae bloom in source water causes high chemical consumption and deteriorates water quality in waterworks. This paper studied the ultrasonic removal of Microcystis aeruginosa. The results showed that algae cells could be effectively removed by sonication and gas vesicle collapse was the main mechanism. The ultrasonic algae removal followed the first order reaction with a rate constant of 0.023 min(-1) (80 W, 80 kHz). Higher ultrasound frequency benefited algae removal; the algae removal rate constant was 0.114 min(-1) at 1320 kHz and 0.0224 min(-1) at 20 kHz (80 W). Higher ultrasound power also accelerated algae removal; the algae removal rate constant was 0.023 min(-1) at 80 W and 0.007 min(-1) at 32 W (80 kHz). However, high ultrasound power and long irradiation caused microcystins to increase. 80 W, 80 kHz sonication for 5 min increased the extracellular microcystins concentration from 0.87 microg/L to 3.11 microg/L. Sound frequency had little impact on the microcystins release. The chlorophyll a concentration initially decreased and then stabilized after 5 min of sonication.     

玻碳电极上ABTS的电化学行为

通过循环伏安法和旋转圆盘电极装置研究了2,2′-偶氮-双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐(ABTS),ABTS^2-和ABTS^·-氧化还原对在pH=4.4的磷酸缓冲溶液中和玻碳电极上的电化学和传质行为. 由不同转速下记录的i-E曲线, 得到在磷酸缓冲溶液的电极反应速率常数和传递系数以及ABTS^2-的扩散系数分别为4.6×10^-3 cm/s、0.28和4.4×10^-6 cm^{2相似文献}   

Liquid-phase adsorption and desorption of phenol onto activated carbons with ultrasound

The effect of 48-kHz ultrasound on the adsorption and desorption of phenol from aqueous solutions onto coconut shell-based granular activated carbons was studied at 25 degrees C. Experiments were performed at different carbon particle sizes (1.15, 2.5, 4.0 mm), initial phenol concentrations (1.06-10.6 mol/m3), and ultrasonic powers (46-133 W). Regardless of the absence and presence of ultrasound, the adsorption isotherms were well obeyed by the Langmuir equation. When ultrasound was applied in the whole adsorption process, the adsorption capacity decreased but the Langmuir constant increased with increasing ultrasonic power. According to the analysis of kinetic data by the Elovich equation, it was shown that the initial rate of adsorption was enhanced after sonication and the number of sites available for adsorption was reduced. The effect of ultrasonic intensity on the initial rate and final amount of desorption of phenol from the loaded carbons using 0.1 mol/dm3 of NaOH were also evaluated and compared.     

Effect of ultrasound on desorption kinetics of phenol from polymeric resin

This work mainly involves the study of desorption kinetics of phenol from polymeric resins under the influence of an ultrasound field. A new phase equilibrium-kinetics model (PEKM), for estimation of diffusion coefficient was proposed, kinetic experiments of phenol desorption on NKA-II resin in the presence and the absence of ultrasound were separately conducted, and diffusion coefficients of phenol within an adsorbent particle were estimated by means of proposed PEKM. Results showed that the use of ultrasound could enhance the diffusion of phenol within the resin. The diffusion coefficient of phenol in the resin in an ultrasonic field increased by an order of magnitude in comparison with the diffusion coefficient in the absence of ultrasound. The more intense the ultrasonic field the larger was the diffusion coefficient.     

Bistable kinetics of simple reactions on solid surfaces: lateral interactions, chemical waves, and the equistability criterion

In heterogeneous reactions, the rate constants of desorption, diffusion and elementary reaction steps are usually strongly dependent on reactant coverages due to adsorbate-adsorbate lateral interactions. We analyze the effect of this factor on the bistable regime of the reaction kinetics. As an example, we consider CO oxidation on Pt(111). The equistability lines in the bistable region for this reaction are calculated by analyzing propagation of chemical waves and taking into account the coverage dependence of the CO diffusion coefficient. The results of simulations are compared with the available experimental data. We show that it is possible to obtain the relationship between various kinetic parameters, for example, between CO and oxygen sticking probabilities, by studying special features of the bistable kinetics.     

Ultrasound-assisted removal of malachite green from aqueous solution by dead pine needles

The dead needles of Aleppo pine (Pinus halepensis) were tested as a possible sorbent for the removal of malachite green from aqueous solutions in the absence and presence of ultrasound. Batch process was employed for sorption kinetic and equilibrium studies. Sorption experiments indicated that the sorption capacity was dependent of operating variables. Both the rate and the amount of malachite green sorption are markedly increased in the presence of the ultrasonic field. The dye removal with the assistance of ultrasound was enhanced with the increase of sorbate initial concentration and temperature, and with the decrease of sorbent dosage and ionic strength. The combination of stirring and ultrasound leads to an improvement of the removal of dye. The sorption kinetics was controlled by the intraparticle diffusion. The intraparticle diffusion coefficient increased 1.7 times in the presence of ultrasound and up to 3.6 times in the combined process. The sorption capacity, estimated according to the Freundlich model, indicates that ultrasound enhanced the sorption properties of the sorbent. The effect of ultrasound on the improvement of dye sorption is due to a variety of physical and mechanical effects as well as to thermal properties. The combination of ultrasound and stirring for the sorption process was shown to be of interest for the treatment of wastewaters contaminated with malachite green.     

Ultrasound irradiation promoted efficient solvent-free lipase-catalyzed production of mono- and diacylglycerols from olive oil

This work reports the enzymatic production of mono- and diacylglycerols under the influence of ultrasound irradiation, in a solvent-free system, with and without the presence of surfactants at a constant temperature of 65°C, glycerol to oil molar ratio of 2:1 and a commercial immobilized lipase (Novozym 435) as catalyst. For this purpose, two operation modes were adopted: the use of a sonotrode (ultrasonic probe), without agitation, varying reaction time, irradiation amplitude (25-45% of the total power) and type of surfactant, and a mechanically stirred reactor (600 rpm) under ultrasound irradiation in a water bath, testing different surfactants. Results show that very satisfactory MAG and DAG yields, above 50 wt.%, can be obtained without the use of surfactant, at mild irradiation power supply (～130 W), with no important enzyme activity losses verified, in a relatively short reaction time (2h), and low enzyme content (7.5 wt.%). Also, reaction kinetic results show that contents of MAG+DAG as high as ～65 wt.% can be achieved at longer times (6h), indicating a promising route for producing MAG and DAG using ultrasound irradiation.     

Ultrasound assisted arylation of benzyl alcohol with 4-nitrochlorobenzene under a new multi-site phase-transfer catalyst in solid–liquid condition

The ultrasound assisted preparation of 1-(benzyloxy)-4-nitrobenzene from the reaction of 4-chloronitrobenzene (CNB) and benzyl alcohol was carried out successfully using potassium hydroxide and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., 1,3,5-triethyl-1,3,5-trihexyl-1,3,5-triazinane-1,3,5-triium trichloride in a solid–liquid reaction condition (SL-MPTC). The advantage of using SL-MPTC is to avoid a serious hydration of potassium salt of benzyl alcohol in the reaction between 4-chloronitrobenzene (CNB) and benzyl alcohol. The reaction is greatly enhanced in the solid–liquid system, catalyzed by multi-site quaternary ammonium salt (MPTC) and ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction greatly enhanced with ultrasound irradiation than without ultrasound. The reaction mechanism is proposed and verified by examining the experimental evidence. A kinetic model is proposed in which a pseudo first-order rate law is sufficient to describe the results, such as the effects of agitation speed, ultrasound, different phase transfer catalysts and the effect of organic solvents, the amount of newly prepared MPTC, the effect of temperature, the amount of water, the concentration of 4-chloronitrobenzene (CNB) and potassium hydroxide concentrations. The apparent rate constant (k_app) were investigated in detail. Rational explanations to account for the phenomena on the results were made.     

The effect of ultrasonic vibrations on heterogeneous catalysis

The effect of ultrasonic vibrations on vapour phase decomposition of cumene to benzene and propylene, was investigated employing a silica-alumina cracking catalyst. Ate temperatures and flow rates where external bulk diffusion controlled the rate of reaction, the application of ultrasound increased the mass transfer coefficient up to 40%. When surface reaction and internal pore diffusion controlled the speed of the reaction, the combined catalyst effectiveness factor — surface reaction rate constant was increased up to 160%.