Kinetics of nitrous acid formation in a two-phase tri-n-butylphosphate-diluent/aqueous nitric acid extraction system under the effect of power ultrasound

The kinetics of nitrous acid formation were investigated in two-phase tri-n-butylphosphate (TBP)-diluent/HNO3 (1.5-6.0 mol l-1) systems, where diluent is n-C16H34, n-C12H26, n-C9H20 and i-C8H18, under the effect of power ultrasound at 20 kHz frequency under Ar atmosphere. The rate of HNO2 sonochemical formation decreases with the rise in diluent vapor pressure. The HNO2 formed is distributed between the aqueous and organic phases due to its extraction with TBP. The kinetics of HNO2 sonochemical formation in the two-phase system exhibits induction periods due to NOx (NO + NO2) gas reactions in the HNO3 medium. This induction period decreases with increasing HNO3 concentration and ultrasound intensity. The HNO2 steady-state concentration was obtained under long-time sonication as the result of HNO2 sonochemical decomposition. HNO2 decomposes faster under sonication in the aqueous phase than in the organic phase.     

Kinetics of hydrazinium nitrate decomposition in nitric acid solutions under the effect of power ultrasound

The effect of ultrasound (f = 20 kHz) on the decomposition of hydrazinium nitrate was investigated in a nitric acid medium. The kinetics of N2H5+ decomposition and initial HN3 formation increase in a linear manner with the HNO3 concentration (from 1 to 6 M) and with the ultrasonic intensity (from 0.5 to 3.1 W cm-2). Both rates were equal to that of HNO2 formation in the absence of N2H5+, indicating that the N2H5+ decomposition mechanism is the same as observed without ultrasound between HNO2 and N2H5+. The variation of the steady-state HN3 concentration with the HNO3 concentration and the ultrasonic intensity suggests the existence of a nonexplosive HN3 thermal decomposition mechanism in the cavitation bubble under the effect of ultrasound. It was also observed at ultrasonic intensities exceeding 3.5 W cm-2 that the decomposition of HN3 led to the accumulation of NH4+ in solution.     

Preliminary results on the effect of power ultrasound on nitrogen oxide and dioxide atmosphere in nitric acid solutions.

The effect of ultrasound (20 kHz, 3 W cm-2) on the kinetics of HNO2 and H2O2 formation was investigated in a 1 M HNO3 medium for NO2-Ar and NO-Ar gas mixtures in various volume fractions (f(NO2) < 1.7 vol% and f(NO) < 1.1 vol%, respectively). The H2O2 formation rate measured in 1 M HNO3 in the presence of N2H5NO3 was observed to be much lower than that of HNO2 without N2H5NO3, and was relatively independent of the NO2 or NO gas volume fractions in the argon atmosphere. The HNO2 formation rate increased under ultrasound, and was higher with NO than with NO2. The induction period observed without ultrasound disappeared when ultrasound was applied. The first step in the sonochemical mechanism of HNO2 formation in the presence of NO2 involves thermal decomposition of NO2 into NO within the cavitation bubble. In the second step of HNO2 formation, NO reacts either with HNO3 in the cavitation bubble, or with NO2 in the cavitation bubble or at the bubble/solution interface.     

Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter

Ultrasonic frequencies of 20 kHz, 382 kHz, 584 kHz, 862 kHz (and 998 kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862 kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862 kHz is around 10% more efficient at generating hydroxyl radicals than the 382 kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42 °C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382 kHz and 862 kHz, though 582 kHz is substantially lower, when the power levels are set at approximately 9 W for all systems. An equivalent power level of 9 W could not be obtained for the 998 kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.     

A vortex mechanism for the formation of two-dimensional domains in cholesteric liquid crystals under the effect of ultrasound

An experimental verification is presented for the new theoretical model of a vortex mechanism that explains the formation of two-dimensional domains in planar layers of cholesteric liquid crystals under the effect of ultrasound in the range of frequencies not exceeding the inverse relaxation time of the orientational order parameter. The limits of applicability of this model are determined.     

A new approach to the decontamination of asbestos-polluted waters by treatment with oxalic acid under power ultrasound

A suspension of chrysotile asbestos fibres in aqueous 0.5M oxalic acid was subjected to power ultrasound with the aim to disrupt and detoxify the mineral by the leaching action of oxalic acid on its structural cations acting simultaneously with a vigorous acoustic cavitation. Sonication was performed in a "cavitating tube", a vertical hollow vibrating cylinder made of titanium, operating at 19.2 kHz and 150 W. Treatment lasted from 2.5 to 21 h. Scanning electron microscopy (SEM) showed that the joint action of the chelating agent and ultrasound (though not of either when applied independently) mostly converted asbestos fibres into micrometric aggregates and nano-sized debris, whose morphology totally differed from asbestos fibres. When treated suspensions were filtered through CA membranes (pore size 0.20 microm), more than half of the asbestos went through the filter because it had either been brought in solution or dispersed in the form of extremely small particles. Most of the structural metal ions were brought into solution (ICP-AES). After the treatment the BET surface area of the recovered solid was tenfold greater than the original. The crystalline fraction of residual solids, though resembling the original sample in XRD, was shown by micro-Raman spectra to be made of antigorite, a polymorph form of serpentine. Furthermore, as the length of these antigorite fibrils lay outside the fibre range rated as a health hazard under worldwide regulations, our procedure can be employed for the decontamination of chrysotile-polluted waters and sediments.     

Kinetics of the consolidation processes in dispersed materials under electric-pulse effect

Electric-pulse pressing (simultaneous action of a high-power current pulse and external pressure) of powder materials has been considered. The processes occurring in a dispersed material under the electric-pulse effect have been analyzed. The experimental data on the kinetics of powder material consolidation under the electric-pulse effect are reported.     

Boiling-up of superheated water and water solutions under ultrasound influence

Boiling-up kinetics of superheated distilled water and sodium chloride solution in a glass cell at atmospheric pressure and low superheating of 15–35 °C has been studied far from the boundary of attainable superheating in the area of heterogeneous nucleation. Temperature dependences of average waiting time of superheated liquids boiling-up have been studied experimentally under natural conditions and in the ultrasonic field Waiting time of boiling-up at these temperatures reaches 1000 s, and average time is 600 s. Empirical distribution functions have been found with the use of the waiting time samples obtained by the method of order statistics. Omega-square goodness-of-fit test has shown that they disagree with exponential distribution describing stationary random process of supercritical embryo generation separating the system to macroscopic phases. Thus, it is shown that this random process is not stationary, consequently, nucleation rate to be depending on time.     

The effect of blood acceleration on the ultrasound power Doppler spectrum

The purpose of the present work was to study the influence of blood acceleration and time window length on the power Doppler spectrum for Gaussian ultrasound beams. The work has been carried out on the basis of continuum model of the ultrasound scattering from inhomogeneities in fluid flow. Correlation function of fluctuations has been considered for uniformly accelerated scatterers, and the resulting power Doppler spectra have been calculated. It is shown that within the initial phase of systole uniformly accelerated slow blood flow in pulmonary artery and aorta tends to make the correlation function about 4.89 and 7.83 times wider, respectively, than the sensitivity function of typical probing system. Given peak flow velocities, the sensitivity function becomes, vice versa, about 4.34 and 3.84 times wider, respectively, then the correlation function. In these limiting cases, the resulting spectra can be considered as Gaussian. The optimal time window duration decreases with increasing acceleration of blood flow and equals to 11.62 and 7.54 ms for pulmonary artery and aorta, respectively. The width of the resulting power Doppler spectrum is shown to be defined mostly by the wave vector of the incident field, the duration of signal and the acceleration of scatterers in the case of low flow velocities. In the opposite case geometrical properties of probing field and the average velocity itself are more essential. In the sense of signal–noise ratio, the optimal duration of time window can be found. Abovementioned results may contribute to the improved techniques of Doppler ultrasound diagnostics of cardiovascular system.     

Destruction of polylactic acid microcapsules under ultrasound irradiation

Hollow microcapsules have been considered for potential applications as drug or gene carriers. This paper describes an investigation into the mechanical properties of microcapsules with a biocompatible polylactic acid (PLA) shell that can be destroyed using ultrasound irradiation. The microcapsules had a radius of 1 to 25 μm and a shell thickness of 100 nm to 3 μm, and their response to ultrasound pulses with a center frequency of 700 kHz to 2 MHz was investigated. It was found that approximately 50% of capsules with a radius of 20 μm were destroyed using pulses with a pressure amplitude of 50 kPa and a frequency of 700 kHz, which is close to the resonance frequency of the capsules.     

Investigations of the inhibition of copper corrosion in nitric acid solutions by ketene dithioacetal derivatives

Ketene dithioacetal derivatives, namely 3-[bis(methylthio)methylene] pentane-2,4-dione (1), 3-(1,3-dithian-2-ylidene) pentane-2,4-dione (2) and 3-(1,3-dithiolan-2-ylidene) pentane-2,4-dione (3) were synthesized and their respective capacity to inhibit copper corrosion in 3 M HNO₃ was investigated by means of weight loss, potentiodynamic polarization, scanning electron microscopy (SEM) and energy dispersive X-ray fluorescence (XRF). The obtained results indicate that the addition of these compounds significantly decreases the corrosion rate. Potentiodynamic polarization studies clearly showed that the inhibition efficiency increases with increasing concentration of the investigated compounds at a fixed temperature, but decreases with increasing temperature. These results on the whole showed that the studied substances are good cathodic inhibitors for copper corrosion in nitric acid medium. SEM and energy dispersive X-ray (EDAX) examination of the copper surface revealed that these compounds prevented copper from corrosion by adsorption on its surface to form a protective film, which acts as a barrier to aggressive agents. The presence of these organic compounds adsorbed on the electrode surface was confirmed by XRF investigations.     

Crystallization of potash alum: effect of power ultrasound.

The influence of power ultrasound on the crystallization of potash alum was investigated. Experiments have been carried out in a batch stirred vessel. It was found that ultrasonic waves decrease the supersaturation limits and modify the morphology of the crystals produced. The average crystal size decreases with an increase of ultrasonic power. To investigate also the action of ultrasound on already existing crystals, crystals produced in silent conditions were suspended in saturated potash alum solution at various ultrasonic powers. The results show that ultrasound has also an abrasive effect on potash alum crystals for high power inputs.     

Ultrasound assisted reduction of graphene oxide to graphene in l-ascorbic acid aqueous solutions: Kinetics and effects of various factors on the rate of graphene formation

The reduction of graphene oxide (GO) to graphene (rGO) was achieved by using 20 kHz ultrasound in l-ascorbic acid (l-AA, reducing agent) aqueous solutions under various experimental conditions. The effects of ultrasound power, ultrasound pulse mode, reaction temperature, pH value and l-AA amount on the rates of rGO formation from GO reduction were investigated. The rates of rGO formation were found to be enhanced under the following conditions: high ultrasound power, long pulse mode, high temperature, high pH value and large amount of l-AA. It was also found that the rGO formation under ultrasound treatment was accelerated in comparison with a conventional mechanical mixing treatment. The pseudo rate and pseudo activation energy (E_a) of rGO formation were determined to discuss the reaction kinetics under both treatment. The E_a value of rGO formation under ultrasound treatment was clearly lower than that obtained under mechanical mixing treatment at the same condition. We proposed that physical effects such as shear forces, microjets and shock waves during acoustic cavitation enhanced the mass transfer and reaction of l-AA with GO to form rGO as well as the change in the surface morphology of GO. In addition, the rates of rGO formation were suggested to be affected by local high temperatures of cavitation bubbles.     

Effects of multi-frequency power ultrasound on the enzymolysis of corn gluten meal: Kinetics and thermodynamics study

The effects of multi-frequency power ultrasound (MPU) pretreatment on the kinetics and thermodynamics of corn gluten meal (CGM) were investigated in this research. The apparent constant (K_M), apparent break-down rate constant (k_A), reaction rate constants (k), energy of activation (E_a), enthalpy of activation (ΔH), entropy of activation (ΔS) and Gibbs free energy of activation (ΔG) were determined by means of the Michaelis–Menten equation, first-order kinetics model, Arrhenius equation and transition state theory, respectively. The results showed that MPU pretreatment can accelerate the enzymolysis of CGM under different enzymolysis conditions, viz. substrate concentration, enzyme concentration, pH, and temperature. Kinetics analysis revealed that MPU pretreatment decreased the K_M value by 26.1% and increased the k_A value by 7.3%, indicating ultrasound pretreatment increased the affinity between enzyme and substrate. In addition, the values of k for ultrasound pretreatment were increased by 84.8%, 41.9%, 28.9%, and 18.8% at the temperature of 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased E_a, ΔH and ΔS by 23.0%, 24.3% and 25.3%, respectively, but ultrasound had little change in ΔG value in the temperature range of 293–323 K. In conclusion, MPU pretreatment could remarkably enhance the enzymolysis of CGM, and this method can be applied to protein proteolysis industry to produce peptides.     

Kinetics of the formation of gas bubbles during polarization of copper and graphite electrodes in electrolytic aqueous solutions

The adsorption and kinetic processes of the formation of gas bubbles passivating the surface during polarization of copper and graphite electrodes in 1% aqueous solution of sulfuric acid have been investigated. Three stages of the process related to the recharging of the double electric layer—adsorption accumulation of the gas escaping from the surface, the critical nucleation of the gas bubbles, and their subsequent growth—have been revealed, distinguished, and quantitatively estimated. It has been shown that potential leveling at the steady-state value specified by the Tafel equation is unambiguously associated with achievement of the limiting surface area screened by the gas bubbles for each particular current density. The surface diffusion constants D _H = (1.5–4.4) × 10⁻⁴ and (0.1–3.8) × 10⁻⁵ cm²/s of hydrogen on copper and graphite, respectively, and D _O = (1.8–4.5) × 10⁻⁷ cm²/s of oxygen on graphite during the motion toward the drain (the gas bubbles) have been calculated.     

Separation of americium and europium from solutions of nitric and perchloric acid using dipicolinic acid diamides

Extraction of nitric acid, perchloric acid, americium, and europium with dialkyldiarylamides of 2,6-pyridinecarboxylic (dipicolinic) acid in polar fluorinated solvents (diluents) was analysed. Among the extractants studied N, N′-diethyl-N, N′-ditolylamide dipicolinate is characterized by the best extraction properties. On passing from nitric to perchloric acid solutions extraction of metals sharply increases. Extraction of americium from nitric acid solutions is significantly greater as compared with europium (separation coefficient reaches 6), whereas extraction of americium and europium from perchloric acid solutions is nearly similar. The effect of diluent on the extraction was analyzed; for different diluents the maximum of extraction from perchloric acid solutions shifts form 3 to 6 M.     

Kinetics of the nanocrystalline structure formation

The kinetics of the nanocrystalline structure formation in the Fe_73.5Cu₁Nb₃Si_22.5?xB_x (x=6. 7. 8. 9 at. %) was followed during the annealing runs interrupted between 300 and 700°C.⁵⁷Fe room temperature Mössbauer spectra were taken and complemented by the electrical resistivity and X-Ray diffraction measurements. It has been found that for the 50 K/min temperature increase the formation of the nanocrystalline phase begins above 450°C reaching a maximum around 500°C and is followed by the second stage of crystallization of the disordered intergranular remainder above ca 600°C accompanied by the changes in the occupation of the iron sites in the crystalline α?Fe?Si phase. Thus gained composition-temperature dependence seems to witness for the inhibiting influence of the substitution of B by Si on the crystallization process.     

The effect of ultrasound on the electrolytic conductivity of aqueous sulphate and nitrate solutions

The electrolytic conductivity of aqueous sulphate and nitrate solutions of various metals such as sodium, magnesium, calcium, etc, have been measured with and without the propagation of ultrasonic waves at 2.4 MHz. The propagation of ultrasound of equal intensities has different effects on different sulphate and nitrate solutions. In all cases a marked increase in the conductivity was observed. The change in electrolytic conductivity showed a gradual fall when recorded in terms of increasing order of atomic weight/number of the metal ions. The trend was repeated at all acoustic pressures used; however, with decreasing acoustic power the dependence of conductivity on atomic weight/number became less apparent. Attempts have been made to interpret this phenomenon on the basis of Debye and other related effects.     

Kinetics and mechanism of nickel ferrite formation under high temperature ultrasonic treatment

The effect of simultaneous ultrasonic and thermal treatment on kinetics and mechanism of nickel ferrite formation was studied. It was established that sonication leads to notable increase of the mean rate of this reaction and decrease of effective activation energy from 190+/-5 to 125+/-7 kJ/mol. XRD data show that ultrasonic treatment significantly affects the microstructure of both initial reagent (Fe(2)O(3)) and reaction product (NiFe(2)O(4)) thus promoting formation of well developed reaction zone. A general model of ferrite formation mechanism under high temperature ultrasonic treatment was proposed.