Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound

The kinetics of the pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated with and without ultrasonic irradiation in acetonitrile–water binary mixtures containing 0.008 to 35 wt.% of acetonitrile and the kinetic sonication effects (k_son/k_non) were calculated. Molecular dynamics (MD) simulations of the structure of the solutions were performed with ethyl acetate as the model ester. The ester is preferentially solvated by acetonitrile. The excess of acetonitrile over water in the solvation shell grows fast with an increase in the co-solvent content in the bulk solution. In parallel, the formation of a second solvation shell rich in acetonitrile takes place. Significant kinetic sonication effects for the hydrolysis were explained with facile destruction of the diffuse second solvation shell followed by a rearrangement of the remaining solvent layer under sonication. The rate levelling effect of ultrasound was discussed. In an aqueous-organic binary solvent, independent of the solvent composition, the ultrasonic irradiation evokes changes in the reaction medium which result in an almost identical solvation state of the reagent thus leading to the reaction rate levelling.     

Polymerization of ethyl methacrylate under the influence of ultrasound assisted a new multi-site phase-transfer catalyst system – A kinetic study

The kinetics of multi-site phase-transfer catalyzed free radical polymerisation of ethyl methacrylate (EMA) using potassium peroxy disulphate (PDS) as a water soluble initiator and newly synthesized 1,4-dihexadecylpyrazine-1,4-diium dibromide as multi-site phase-transfer catalyst (MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 55 ± 1 °C under nitrogen atmosphere and ultrasound irradiation conditions. The rate of polymerization increases with an increase in concentrations of EMA, PDS and MPTC. The order with respect to monomer, initiator and MPTC were found to be 1.03, 0.52 and 0.53, respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations and its significance was discussed.     

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 h to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.     

Influence of ultrasound pretreatment on wood physiochemical structure

As an initial step to increase the use of renewable biomass resources, this study was aimed at investigating the effects of ultrasound pretreatment on structural changes of wood. Samples were pretreated by ultrasound with the power of 300 W and frequency of 28 kHz in aqueous soda solution, aqueous acetic acid, or distilled water, then pretreated and control samples were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The results shown that ultrasound pretreatment is indeed effective in modifying the physiochemical structure of eucalyptus wood; the pretreatment decreased the quantity of alkali metals (e.g., potassium, calcium and magnesium) in the resulting material. Compared to the control group, the residual char content of samples pretreated in aqueous soda solution increased by 10.08%–20.12% and the reaction temperature decreased from 361 °C to 341 °C, however, in samples pretreated by ultrasound in acetic solution or distilled water, the residual char content decreased by 12.40%–21.45% and there were no significant differences in reactivity apart from a slightly higher maximum reaction rate. Ultrasound pretreatment increased the samples’ crystallinity up to 35.5% and successfully removed cellulose, hemicellulose, and lignin from the samples; the pretreatment also increased the exposure of the sample to the treatment solutions, broke down sample pits, and generated collapses and microchannels on sample pits, and removed attachments in the samples.     

Ultrasound-assisted butyl acetate synthesis catalyzed by Novozym 435: Enhanced activity and operational stability

The influence of low-frequency ultrasound (40 kHz) in the esterification reaction between acetic acid and butanol for flavor ester synthesis catalyzed by the commercial immobilized lipase B from Candida antarctica (Novozym 435) was evaluated. A central composite design and the response surface methodology were used to analyze the effects of the reaction parameters (temperature, substrate molar ratio, enzyme content and added water) and their response (yields of conversion in 2.5 h of reaction). The reaction was carried out using n-hexane as solvent. The optimal conditions for ultrasound-assisted butyl acetate synthesis were found to be: temperature of 46 °C; substrate molar ratio of 3.6:1 butanol:acetic acid; enzyme content of 7%; added water of 0.25%, conditions that are slightly different from those found using mechanical mixing. Over 94% of conversion was obtained in 2.5 h under these conditions. The optimal acid concentration for the reaction was determined to be 2.0 M, compared to 0.3 M without ultrasound treatment. Enzyme productivity was significantly improved to around 7.5-fold for each batch when comparing ultrasound and standard mechanical agitation. The biocatalyst could be directly reused for 14 reactions cycles keeping around 70% of its original activity, while activity was virtually zeroed in the third cycle using the standard mixing system. Thus, compared to the traditional mechanical agitation, ultrasound technology not only improves the process productivity, but also enhances enzyme recycling and stability in the presence of acetic acid, being a powerful tool to improve biocatalyst performance in this type of reaction.     

Ultrasound irradiation promoted enzymatic alcoholysis for synthesis of monoglyceryl phenolic acids in a solvent-free system

Monoglyceryl phenolic acids (MPAs) were known as the natural hydrophilic antioxidants which could be used in different fields such as food, pharmaceutical, cosmetic etc. A novel enzymatic route of MPAs synthesis by the alcoholysis of phenolic acid ethyl esters with glycerol under ultrasound irradiation in solvent free system was developed. Optimization of reaction parameters shows that a high conversion of above 97.4% can be obtained under the following conditions: phenolic acid ethyl esters to glycerol molar ratio of 1:10, with 6% catalyst (Novozym 435), at 60 °C and 200 rpm, with ultrasound input of 250 W, at 20 kHz frequency. Compared to the conventional stirring method, the activation energy for phenolic acid ethyl esters conversion was decreased from 65.0 kJ/mol to 32.1 kJ/mol under ultrasound promotion; the apparent kinetic constant (V_m/K_m) increased above 1.2-folds; the lipase amount decreased to 50%; the time required for the maximum conversion reduced up to 3-folds without damaging the lipase activity, which is the fastest report for enzymatic synthesis of MPAs.     

Ultrasound assisted polymerization of N-vinyl imidazole under phase-transfer catalysis condition – A kinetic study

The kinetics of phase-transfer catalyzed radical polymerization of N-vinyl imidazole (NVI) using potassium peroxy disulfate (PDS) as water soluble initiator and tetraoctylammonium chloride (TOAC) as PTC has been investigated in ethyl acetate/water two phase system assisted by ultrasound irradiation at constant temperature 60 + 1 °C under nitrogen atmosphere. and. The rate of polymerization increases with an increase in concentrations of NVI, PTC and PDS. The order with respect to [NVI], [PTC], and [PDS] were found to be 1.01, 1.03 and 0.52 respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations followed by a discussion on its significance.     

Improved synthesis of sucrose fatty acid monoesters under ultrasonic irradiation

Sucrose fatty acid esters were synthesized by the transesterification of sucrose with aliphatic esters under ultrasound irradiation in good yield (?73%). The optimum reaction conditions for the transesterification reaction include a molar ratio of sucrose to fatty acid ethyl ester of 2:1 and the use of a 13% mol anhydrous K₂CO₃ catalyst. The optimum reaction temperature was set at 70 °C, the optimum reaction time was 2 h, and the optimum reaction pressure was 11 kPa. The reaction had excellent monoester selectivity. The proportion of monoester (6-monoester + 6′-monoester) in the purified products was up to 92–95% via flash column chromatography over silica gel, the ratios of 6-monoester/6′-monoester are 2.1–2.7, and the sucrose monoesters were identified by HPLC–MS, NMR and IR.     

Synergistic effects of combining ultrasound with the Fenton process in the degradation of Reactive Blue 19

The decoloration of reactive dye C.I. Reactive Blue 19 (RB 19) using combined ultrasound with the Fenton process has been investigated. The effect of varying the concentrations of hydrogen peroxide and iron sulfate, initial pH, ultrasonic power, initial dye concentration and dissolved gas on the decoloration and degradation efficiencies was measured. Calibration of the ultrasound systems was performed using calorimetric measurements and oxidative species monitoring using the Fricke dosimeter and degradations were carried out with a 20 kHz probe type transducer at 2, 4, 6 and 8 W cm⁻² of acoustic intensity at 15, 25, 50 and 75 mg L⁻¹ initial dye concentrations. First order rate kinetics was observed. It was found that while the degradation rate due to ultrasound alone was slow, sonication significantly accelerated the Fenton reaction. While the results were similar to those reported for other dyes, the effects occurred at lower concentrations. The rate and extent of decoloration of RB 19 increased with rising hydrogen peroxide concentration, ultrasonic powers and iron sulfate concentration but decreased with increasing dye concentration. An optimum pH value of pH = 3.5 was found. The rate of decoloration was higher when dissolved oxygen was present as compared with nitrogen and argon confirming the solution phase mechanism of the degradation.     

Influence of ultrasonic condition on phase transfer catalyzed radical polymerization of methyl methacrylate in two phase system – A kinetic study

An ultrasonic condition assisted phase transfer catalyzed radical polymerization of methyl methacrylate was investigated in an ethyl acetate/water two phase system at 60 ± 1 °C and 25 kHz, 300 W under inert atmosphere. The influence of monomer, initiator, catalyst and temperature, volume fraction of aqueous phase on the rate of polymerization was examined in detail. The reaction order was found to be unity for monomer, initiator and catalyst. Generally, the reaction rate was relatively fast in two phase system, when a catalytic amount of phase transfer catalyst was used. The combined approach, use of ultrasonic and PTC condition was significantly enhances the rate of polymerization. An ultrasonic and phase transfer catalyzed radical polymerization of methyl methacrylate has shown about three fold enhancements in the rate compared with silent polymerization of MMA using cetyltrimethylammonium bromide as PTC. The resultant kinetics was evaluated with silent polymerization and an important feature was discussed. The activation energy and other thermodynamic parameters were computed. Based on the obtained results an appropriate radical mechanism has been derived. TGA showed the polymer was stable up to 150 °C. The FT-IR and DSC analysis validates the atactic nature of the obtained polymer. The XRD pattern reveals the amorphous nature of polymer was dominated.     

Kinetics of ultrasound-assisted extraction of antioxidant polyphenols from food by-products: Extraction and energy consumption optimization

Ultrasound-assisted extraction (UAE) of antioxidant polyphenols from chicory grounds was studied in order to propose a suitable valorization of this food industry by-product. The main parameters influencing the extraction process were identified. A new mathematical model for multi-criteria optimization of UAE was proposed. This kinetic model permitted the following and the prediction of the yield of extracted polyphenols, the antioxidant activity of the obtained extracts and the energy consumption during the extraction process in wide ranges of temperature (20–60 °C), ethanol content in the solvent (0–60% (vol.) in ethanol–water mixtures) and ultrasound power (0–100 W). After experimental validation of the model, several simulations at different technological restrictions were performed to illustrate the potentiality of the model to find the optimal conditions for obtaining a given yield within minimal process duration or with minimal energy consumption. The advantage of ultrasound assistance was clearly demonstrated both for the reduction of extraction duration and for the reduction of energy consumption.     

Ultrasound assisted intensification of biodiesel production using enzymatic interesterification

Ultrasound assisted intensification of synthesis of biodiesel from waste cooking oil using methyl acetate and immobilized lipase obtained from Thermomyces lanuginosus (Lipozyme TLIM) as a catalyst has been investigated in the present work. The reaction has also been investigated using the conventional approach based on stirring so as to establish the beneficial effects obtained due to the use of ultrasound. Effect of operating conditions such as reactant molar ratio (oil and methyl acetate), temperature and enzyme loading on the yield of biodiesel has been investigated. Optimum conditions for the conventional approach (without ultrasound) were established as reactant molar ratio of 1:12 (oil:methyl acetate), enzyme loading of 6% (w/v), temperature of 40 °C and reaction time of 24 h and under these conditions, 90.1% biodiesel yield was obtained. The optimum conditions for the ultrasound assisted approach were oil to methyl acetate molar ratio of 1:9, enzyme loading of 3% (w/v), and reaction time of 3 h and the biodiesel yield obtained under these conditions was 96.1%. Use of ultrasound resulted in significant reduction in the reaction time with higher yields and lower requirement of the enzyme loading. The obtained results have clearly established that ultrasound assisted interesterification was a fast and efficient approach for biodiesel production giving significant benefits, which can help in reducing the costs of production. Reusability studies for the enzyme were also performed but it was observed that reuse of the catalyst under the optimum experimental condition resulted in reduced enzyme activity and biodiesel yield.     

First-principles molecular dynamics simulations of uranyl ion interaction at the water/rutile TiO2(110) interface

The effects of temperature and solvation on uranyl ion adsorption at the water/rutile TiO₂(110) interface are investigated by Density Functional Theory (DFT) in both static and Born–Oppenheimer molecular dynamics approaches. According to experimental observations, uranyl ion can form two surface complexes in a pH range from 1.5 to 4.5. Based on these observations, the structures of the complexes at 293 K are first calculated in agreement with vacuum static calculations. Then, an increase in temperature (293 to 425 K) induces the reinforcement of uranyl ion adsorption due to the release of water molecules from the solvation shell of uranyl ion. Finally, temperature can modify the nature of the surface species.     

Comparisons between conventional,ultrasound-assisted and microwave-assisted methods for extraction of anthraquinones from Heterophyllaea pustulata Hook f. (Rubiaceae)

This work reports a comparative study about extraction methods used to obtain anthraquinones (AQs) from stems and leaves of Heterophyllae pustulata Hook (Rubiáceae). One of the conventional procedures used to extract these metabolites from a vegetable matrix is by successive Soxhlet extractions with solvents of increasing polarity: starting with hexane to eliminate chlorophylls and fatty components, following by benzene and finally ethyl acetate. However, this technique shows a low extraction yield of total AQs, and consumes large quantities of solvent and time. Ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) have been investigated as alternative methods to extract these compounds, using the same sequence of solvents. It was found that UAE increases the extraction yield of total AQs and reduces the time and amount of solvent used. Nevertheless, the combination UAE with benzene, plus MAE with ethyl acetate at a constant power of 900 W showed the best results. A higher yield of total AQs was obtained in less time and using the same amount of solvent that UAE. The optimal conditions for this latter procedure were UAE with benzene at 50 °C during 60 min, followed by MAE at 900 W during 15 min using ethyl acetate as extraction solvent.     

Fast,easy ethanolysis of coconut oil for biodiesel production assisted by ultrasonication

Biodiesel is a renewable fuel, consistituting an alternative to petroleum-based diesel fuel. It is non-toxic and biodegradable and has a low emission profile, is better from environmentally sensitive areas. Research study on alternative fuels is essential for increased energy security. Presently, biodiesel is produced mainly is batch reactor. In this process the required energy is given by heating accompanied by mechanical stirring which has several disadvantages because of time consuming high labour cost. Being methanol is a toxic chemical; the objective of this work is to produce coconut oil ethyl ester by using ultrasonic irradiation. The advantages of ethanol are non-toxic domestic all available, having higher carbon atoms which provide higher heat content. The optical conditions for biodiesel production is the molar ratio oil to ethanol 1:6, KOH catalyst 0.75 wt.% of oil and 7 min reaction time. The reaction time reduced 15–40 times comparing to the conventional batch processes and found ?98% biodiesel yield.     

Sonochemical degradation of ethyl paraben in environmental samples: Statistically important parameters determining kinetics,by-products and pathways

The sonochemical degradation of ethyl paraben (EP), a representative of the parabens family, was investigated. Experiments were conducted at constant ultrasound frequency of 20 kHz and liquid bulk temperature of 30 °C in the following range of experimental conditions: EP concentration 250–1250 μg/L, ultrasound (US) density 20–60 W/L, reaction time up to 120 min, initial pH 3–8 and sodium persulfate 0–100 mg/L, either in ultrapure water or secondary treated wastewater.A factorial design methodology was adopted to elucidate the statistically important effects and their interactions and a full empirical model comprising seventeen terms was originally developed. Omitting several terms of lower significance, a reduced model that can reliably simulate the process was finally proposed; this includes EP concentration, reaction time, power density and initial pH, as well as the interactions (EP concentration) × (US density), (EP concentration) × (pH_o) and (EP concentration) × (time).Experiments at an increased EP concentration of 3.5 mg/L were also performed to identify degradation by-products. LC–TOF–MS analysis revealed that EP sonochemical degradation occurs through dealkylation of the ethyl chain to form methyl paraben, while successive hydroxylation of the aromatic ring yields 4-hydroxybenzoic, 2,4-dihydroxybenzoic and 3,4-dihydroxybenzoic acids. By-products are less toxic to bacterium V. fischeri than the parent compound.     

Stability of all-trans-β-carotene under ultrasound treatment in a model system: Effects of different factors,kinetics and newly formed compounds

The effects of factors and kinetics of all-trans-β-carotene degradation under ultrasound treatment in a model system were investigated. The compounds of degradation were also tentatively identified by HPLC-DAD, Raman and FT-IR spectroscopy. The type of solvents and temperature were important factors in determining the degradation reaction. Liquid height, ultrasonic intensity and duty cycle of ultrasound exposure only affected the rate of degradation but did not change the nature of degradation. Degradation rate of β-carotene in dichloromethane was the highest. Degradation rate of β-carotene decreased with increasing of temperature. Degradation kinetics of all-trans-β-carotene under ultrasound fitted first-order reaction at ?5 to 15 °C, and fitted second-order reaction at 25 °C. Degradation products included isomers: 15-cis-β-carotene, di-cis-β-carotene and other compounds with function group of C–O.     

Intensified removal of copper from waste water using activated watermelon based biosorbent in the presence of ultrasound

Copper is one of the most toxic heavy metals having significant effects on the living organisms and hence effective removal of copper from waste water is crucial. The current work investigates the application of activated watermelon shell based biosorbent for the removal of copper from aqueous solution. The effect of activation using calcium hydroxide and citric acid as well as the effect of operating parameters like contact time, adsorbent dosage, temperature, pH, initial concentration and ultrasonic power on the extent of removal has been investigated. Experiments performed in the presence of ultrasound to investigate the degree of intensification as compared to the conventional agitation based treatment revealed that the adsorption rate significantly increases in the presence of ultrasound and also the time required for reaching the equilibrium reduces from 60 min in conventional approach to only 20 min in the presence of ultrasound. The extent of adsorption of Cu(II) on adsorbents was found to increase with an increase in the operating pH till an optimum value of 5. The extent of adsorption also increased with a decrease in the initial concentration and particle size as well as with an increase in ultrasonic power till an optimum. Kinetics and isotherm study revealed that all the experimental data was found to best fit the pseudo second order kinetics and Langmuir adsorption isotherm model respectively. Maximum adsorption capacity was found to be 31.25 mg/g for watermelon treated with calcium hydroxide and 27.027 mg/g for watermelon treated with citric acid. Overall present study established that activated watermelon is an environmentally friendly, low cost and highly efficient biosorbent that can be successfully applied for the removal of copper from aqueous solution with intensification benefits based on the ultrasound assisted approach.     

Ultrasound-assisted dyeing of cellulose acetate

The possibility of reducing the use of auxiliaries in conventional cellulose acetate dyeing with Disperse Red 50 using ultrasound technique was studied as an alternative to the standard procedure. Dyeing of cellulose acetate yarn was carried out by using either mechanical agitation alone, with and without auxiliaries, or coupling mechanical and ultrasound agitation in the bath where the temperature range was maintained between 60 and 80 °C.The best results of dyeing kinetics were obtained with ultrasound coupled with mechanical agitation without auxiliaries (90% of bath exhaustion value at 80 °C). Hence the corresponding half dyeing times, absorption rate constants according to Cegarra–Puente modified equation and ultrasound efficiency were calculated confirming the synergic effect of sonication on the dyeing kinetics. Moreover the apparent activation energies were also evaluated and the positive effect of ultrasound added to mechanical agitation was evidenced by the lower value (48 kJ/mol) in comparison with 112 and 169 kJ/mol for mechanical stirring alone with auxiliaries and without, respectively.Finally, the fastness tests gave good values for samples dyed with ultrasound technique even without auxiliaries. Moreover color measurements on dyed yarns showed that the color yield obtained by ultrasound-assisted dyeing at 80 °C of cellulose acetate without using additional chemicals into the dye bath reached the same value yielded by mechanical agitation, but with remarkably shorter time.     

Esterification of sodium 4-hydroxybenzoate by ultrasound-assisted solid–liquid phase-transfer catalysis using dual-site phase-transfer catalyst

The catalytic esterification of sodium 4-hydroxybenzoate with benzyl bromide by ultrasound-assisted solid–liquid phase-transfer catalysis (U-SLPTC) was investigated using the novel dual-site phase-transfer catalyst 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl dichloride (BTBAMBC), which was synthesized from the reaction of 4,4′-bis(chloromethyl)-1,1′-biphenyl and tributylamine. Without catalyst and in the absence of water, the product yield at 60 °C was only 0.36% in 30 min of reaction even under ultrasound irradiation (28 kHz/300 W) and 250 rpm of stirring speed. When 1 cm³ of water and 0.5 mmol of BTBAMBC were added, the yield increased to 84.3%. The catalytic intermediate 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl di-4-hydroxybenzoate was also synthesized to verify the intrinsic reaction which was mainly conducted in the quasi-aqueous phase locating between solid and organic phases. Pseudo-first-order kinetic equation was used to correlate the overall reaction, and the apparent rate coefficient with ultrasound (28 kHz/300 W) was 0.1057 min⁻¹, with 88% higher than that (0.0563 min⁻¹) without ultrasound. The esterification under ultrasonic irradiation using BTBAMBC by solid–liquid phase-transfer catalysis was developed.