Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

Sonolysis of chlorobenzene in Fenton-type aqueous systems

The influence of ultrasounds (200 kHz frequency) on the decomposition of chlorobenzene (CB) in a water solution (around 100 ppm concentration) containing iron or palladium sulfates was investigated. The intermediates of the sonolysis were identified, thus allowing a deeper insight into the degradation mechanism. It was established that CB degradation starts by pyrolysis inside the cavitation bubbles. The initial sonolysis product is benzene, formed in a reaction occurring outside the cavitation from phenyl radicals and the hydrogen atoms sonolytically generated from the water. Polyphenols as products of the CB sonochemical degradation are reported for the first time. The palladium salt was found to be a useful and sensitive indicator for differentiating the sites and mechanisms of the product formation. An alternative mechanism for the CB sonolysis is advanced, explaining the formation of phenols, polyphenols, chlorophenols and benzene.     

Sonolysis of an aqueous mixture of trichloroethylene and chlorobenzene

The effect of the initial concentration on the ultrasonic degradation of two volatile organic compounds trichloroethylene (TCE) and chlorobenzene (CB) was investigated. At higher concentrations, slower sonolysis rates were obtained due to the lowering of the average specific heat ratio gamma of the gas inside the cavitation bubbles. Furthermore, the effect of different concentrations of CB on the sonolysis of 3.34 mM TCE and the effect of different concentrations of TCE on the sonolysis of 3.44 mM CB was examined. The presence of CB lowered the sonolysis rate of TCE, while the sonolysis rate of CB did not decrease by TCE addition. An even higher sonolysis rate was obtained for 3.44 mM CB in the presence of 0.84 mM TCE than without TCE. The explanation for the different effects of both volatile organics on each other's sonolysis rate is thought to be the difference in reaction rate of TCE and CB with the radicals formed during sonolysis. The effect of TCE on the sonolysis rate of CB by lowering the gamma value is compensated by an increased indirect degradation of CB by radicals formed out of TCE. The decreased thermal degradation and the increased indirect radical degradation of CB in the presence of TCE is demonstrated by determining the kinetics of the degradation products styrene and dichlorobenzene.     

Sonolysis of aqueous 4-nitrophenol at low and high pH

The sonolysis of 4-nitrophenol in argon-saturated aqueous solution has been studied at 321 kHz. In order to evaluate separately the effect of OH radicals that are formed in the cavitational bubble and part of which react in the aqueous phase with this substrate, radiolytic studies in N2O-saturated solutions were carried out for comparison. A detailed product study of the sonolysis of 4-nitrophenol solutions shows that at pH 10, where 4-nitrophenol is deprotonated (pKa = 7.1), its sonolytic degradation is fully accounted for by OH-radical-induced reactions in the aqueous phase. At this pH, the sonolytic yield of H2O2 resulting from OH radical recombination in the solution, measured as a function of the 4-nitrophenol concentration, is reduced in line with the scavenging capacity of the 4-nitrophenolate. In contrast, at pH 4 the formation of H2O2 is already fully suppressed when the solution is 7 x 10(-4) mol dm-3 in 4-nitrophenol, and oxidative-pyrolytic degradation predominates, as exemplified by the large yields of CO and CO2 which are accompanied by a large H2 yield. The basis of this difference in behavior is a hydrophobic enrichment of 4-nitrophenol (which is undissociated at pH 4) at the interface of the cavitational bubble by a factor of about 80. The pH dependence of the yields of the pyrolytic products reflects the hydrolytic equilibrium concentration of 4-nitrophenol. The paper also demonstrates that the complexity of this sonochemical system precludes its use a gauge to determine the temperature in the interior of the cavitational bubble.     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

The mechanism of sonophotocatalytic degradation of methyl orange and its products in aqueous solutions

In this study, it was found that a hybrid technique, sonophotocatalysis, is able to degrade a parent organic pollutant (methyl orange) as well as its by-products. The analysis of products formed during the whole degradation has demonstrated that the pH or the selection of oxidation process (sonolysis/photocatalysis/sonophotocatalysis) is able to control the degradation pathway. It was shown in the by-products analysis that the solution pH can alter the amount of each product generated during the sonophotocatalytic degradation. It was revealed that the different degradation rates of methyl orange and its products result from the solution pH and the nature of the organic products. Furthermore, a comparison of the data obtained from the oxidation processes on the degradation of the reaction intermediates identified the advantages of the combined system. It is concluded that sonophotocatalysis is capable of yielding a more complete and faster mineralization of organic pollutants than the individual processes. However, as in the degradation of the parent compound, the overall mineralization is lower than an additive effect (negative synergistic effect).     

Sonochemical degradation of azo dyes in aqueous solution: a new heterogeneous kinetics model taking into account the local concentration of OH radicals and azo dyes

The sonochemical decolorization and decomposition of azo dyes, such as C. I. Reactive Red 22 and methyl orange, were performed from the viewpoints of wastewater treatment and to determine the reaction kinetics. A low concentration of the azo dye solution was irradiated with a 200 kHz and 1.25 W/cm2 ultrasound in a homogeneous aqueous solution. The azo dye solutions were readily decolorized by the irradiation. The sonochemical decolorization was also depressed by the addition of the t-butyl alcohol radical scavenger. These results indicated that azo dye molecules were mainly decomposed by OH radicals formed from the water sonolysis. In this paper, we propose a new kinetics model taking into account the heterogeneous reaction kinetics similar to a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. The proposed kinetics model is based on the local reaction site at the interface region of the cavitation bubbles, where azo dye molecules are quickly decomposed because an extremely high concentration of OH radicals exists in this region. To confirm the proposed kinetics model, the effects of the initial concentration of azo dyes, irradiated atmosphere and pH on the decomposition rates were investigated. The obtained results were in good agreement with the proposed kinetics model.     

Effect of pH on the ultrasonic degradation of ionic aromatic compounds in aqueous solution

The sonolysis of 4-nitrophenol (4-NP) and aniline in O2-saturated aqueous solutions was performed at 610 kHz with ultrasonic power of 25 W and aqueous temperature of 15 +/- 1 degrees C. The initial rate of degradation of both 4-NP and aniline in sonolysis of aqueous media follows pseudo-first-order reaction kinetics. Investigation of the H2O2 generation rate in phosphate buffer media (0.01 M) over the range of pH 2-9 revealed a maximum yield at pH approximately 3.2. The pH, which results in modification of the physical properties (including charge) of molecules with ionisable functional groups, plays an important role in the sonochemical degradation of chemical contaminants. For hydrophilic substrates, the neutral species more easily diffuse to and accumulate at the hydrophobic interface of liquid-gas bubbles in comparison with their corresponding ionic forms. As a consequence, the degradation rate of 4-NP under ultrasonic irradiation decreases with increasing pH. In contrast, the disappearance rate of aniline exhibits a maximum under alkaline conditions due to the high solubility of the ionic anilinium ion and the (potentially) preferential movement of the uncharged form to the interface. Additionally, the rate of reaction of the uncharged aniline molecule (which dominates at pH > 4.6) with hydroxyl radicals is reported to be about three times as fast as the rate of reaction of the cationic anilinium species.     

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.     

Aquasonolysis of selected cyclic C(6)H(x) hydrocarbons

Aquasonolysis rates and products of selected cyclic C(6)H(x) hydrocarbons, benzene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclohexene, cyclohexane, and methylcyclopentane have been investigated. The sonolysis of selected compounds in aqueous solution follows first-order kinetics, and the aquasonolysis rate correlated well with the water solubility. The degradation rate decreased with the increase of initial concentration. The effect of initial concentration on the degradation of cyclohexene was more significant than that of benzene. The transfer process of organic solutes between cavitation bubbles and the bulk liquid affects the rates and products of their aquasonolysis.     

The kinetics and mechanism of ultrasonic degradation of p-nitrophenol in aqueous solution with CCl4 enhancement

The ultrasonic degradation of p-nitrophenol (p-NP) in aqueous solution with CCl₄ enhancement was studied. The effects of operating parameters such as CCl₄ dosage, ultrasonic power, media temperature, the initial concentration of p-NP and initial pH value of the aqueous solution on the degradation of p-NP were investigated, and the enhancement mechanism of CCl₄ for p-NP sonolysis was also discussed. The results showed that the sonochemical degradation of p-NP was obviously enhanced by adding CCl₄. It attributed to the increase OH radicals concentration in the presence of CCl₄ as a hydrogen atom scavenger, and the formation of some oxidizing agents such as free chlorine and chlorine-containing radicals. The degradation of p-NP follows a pseudo-first-order kinetics. The degradation rate of p-NP increased with decreasing the temperature, the initial pH value of the solution and decreasing the initial concentration of p-NP. It was also found that p-NP can be mineralized in this process.     

Sonochemical degradation of martius yellow dye in aqueous solution

The sonolytic degradation of the textile dye martius yellow, also known as either naphthol yellow or acid orange 24, was studied at various initial concentrations in water. The degradation of the dye followed first-order kinetics under the conditions examined. Based on gas chromatographic results and sonoluminescence measurements of sonicated aqueous solutions of the dye, it is concluded that pyrolysis does not play a significant role in its degradation. The chromatographic identification of hydroxy added species indicates that an OH radical induced reaction is the main degradation pathway of the dye. Considering the non-volatility and surface activity of the dye, the degradation of the dye most probably takes place at the bubble/solution interface. The quantitative and qualitative formation of the degradation intermediates and final products were monitored using HPLC and ESMS. The analytical results suggest that the sonolytic degradation of the dye proceeds via hydroxylation of the aryl ring and also by C-N bond cleavage of the chromophoric ring, either through OH radical attack or through another unidentified process. The identification of various intermediates and end products also imply that the degradation of martius yellow proceeds through multiple reaction pathways. Total organic carbon (TOC) analyses of the dye solutions at various times following sonication revealed that sonolysis was effective in the initial degradation of the parent dye but very slow in achieving mineralization. The slow rate of mineralization is likely to be due to the inability of many of the intermediate products such as, the carboxylic acids, to accumulate at the bubble (air/water) interface and undergo decomposition due to their high water solubility (low surface activity).     

Sonolysis of fluoro-, chloro-, bromo- and iodobenzene: a comparative study

The sonolysis at 520 kHz of the four monohalogenated benzenes, fluoro- (FB), chloro- (CB), bromo- (BB) and iodobenzene (IB) at different initial concentrations, 0.5, 1 and 2 mM, was studied. The sonolysis rate of all four compounds depends on the initial concentration. During sonolysis of FB, CB, BB and IB analogous apolar organic degradation products were determined, indicating that all four monohalogenated benzenes degrade following a similar degradation mechanism. The relative yield of the different degradation products was different, as was shown for the degradation product benzene. A previously developed kinetic model was applied to the sonolysis of the monohalogenated benzenes and a good correlation between experimental and simulated concentration versus time profiles was obtained for all four compounds. By comparing the influence of the different monohalogenated benzenes on their own sonolysis rate, it could be deduced that the proportionality between their concentration in the cavitation bubbles and their concentration in the bulk solution depends on their aqueous diffusion coefficient rather than on their Henry's law coefficient.     

Oxygen-induced concurrent ultrasonic degradation of volatile and non-volatile aromatic compounds

Acoustic cavitation, induced by ultrasound, can be used to eliminate organic pollutants from water. This type of ultrasonic treatment of polluted water can be grouped with those generally referred to as advanced oxidative processes since it involves hydroxyl radicals. In this case these highly active species are generated from the dissociation of water and oxygen dissociation caused by cavitation bubble collapse. The cavitation induced degradation rates of organic compounds in water are mainly linked to their vapor pressure and solubility and here we will further explore these links by examining the degradation of a mixture of two materials with different physical properties, chlorobenzene and 4-chlorophenol. The results obtained when a dilute solution of a mixture of these compounds saturated with argon is subjected to sonication at 300 kHz, parallels previous observations achieved in an aerated aqueous medium at 500 kHz. The two compounds exhibit sequential degradation with the more volatile chlorobenzene entering the cavitation bubble and being destroyed first. The 4-chlorophenol degradation occurs subsequently only when the chlorobenzene has been completely destroyed. The two compounds exhibit different behavior when sonicated in water saturated with oxygen. Under these conditions the two compounds are degraded simultaneously, a remarkable result for which two explanations can be proposed, both of which are based on the formation of additional OH radical species: The ability to produce conditions for the simultaneous elimination of two organic compounds by the use of oxygen is of great importance in the developing field of ultrasonic water treatment.     

Sonochemical reaction of selected cyclic C6Hx hydrocarbons in organic solvents

The rates and products of the sonochemical reactions of benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, and cyclohexane in selected organic solvents have been investigated. The sonochemical reactions of these educts in the investigated organic solvents follow first-order kinetics. Generally, they are sonicated more rapidly in polar than in non-polar solvent; higher volatility of the solute results in faster sonolysis in the organic solvents. However, the sonication of cyclohexane in n-decane and the sonication of benzene in n-propanol are exceptional cases. Since cyclohexane exhibits a much higher lipophilicity and benzene a much higher hydrophilicity than other educts, it might be more difficult to transfer either educt from the bulk liquid into the cavitation bubbles. In tetrachloroethylene, the reactivity of the tested educts with in situ generated chlorine as well as chlorine-containing radical intermediates can accelerate the rate of sonochemical reactions under the employed conditions. In n-propanol and n-decane, the pyrolysis during the collapse of the cavitation bubbles is the only reaction pathway of sonolysis. In tetrachloroethylene, the pyrolysis during the collapse of the cavitation bubbles and the free radical reaction in the bulk liquid may occur simultaneously. Except for the products generated from sonolysis, products formed from chlorine transformations (substitution or addition reactions) are detected. Benzene is hardly decomposed in tetrachloroethylene. However, when FeCl3 is added into the reaction system, benzene is sonoconverted rapidly, and the product chlorobenzene was detected. In organic solvents, the sonoreaction rates and the sonoproducts are dependent on the physicochemical properties of the solvents used, as well as the volatility, the polarity and the reactivity of educts.     

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.     

Sonolytic hydrolysis of peptides in aqueous solution upon addition of catechol

The sonolytic hydrolysis of peptides with addition of phenolic reagents to aqueous solutions is described. Sonolysis of an aqueous solution of peptides to which catechol (o-dihydroxybenzene) had been added resulted in hydrolytic products reflecting the amino acid sequence without any side reactions, while sonolysis without any additives resulted in oxidation analytes and degradation products caused by side reactions. Although the use of additives such as resorcinol (m-dihydroxybenzene), hydroquinone (p-dihydroxybenzene) and phenol was also effective in producing sequence related products, several degradation products were produced by side reactions. A characteristic of the sonolysis of peptides is that the N-terminal side of proline, Xxx-Pro, is more susceptible than other amino acid residues to the process. This characteristic of sonolysis is superior to that of acid hydrolysis in which cleavage at the C-terminal side of proline, Pro-Xxx is difficult, and where dehydration products result due to side reactions.     

Enhanced sonochemical degradation of azure B dye by the electroFenton process

The degradation of azure B dye (C₁₅H₁₆ClN₃S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H₂O₂ at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe²⁺, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton > Fenton > sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes.     

Sonophotocatalytic degradation of methyl orange by nano-sized Ag/TiO2 particles in aqueous solutions

Sonophotocatalytic behaviour of methyl orange (MeO) in aqueous solution illuminated by light generated by a xenon lamp was investigated. For all three kinds of photocatalysts: Degussa P25 (75% anatase, 25% rutile, with a surface area of 55.07 m(2)/g), Yili TiO(2) (mainly anatase, with a surface area of 10.45 m(2)/g) and Ag/TiO(2) (silver loaded on Yili TiO(2)), the degradation followed pseudo-first order kinetics. The results showed a synergistic effect between sonolysis and photocatalysis. Some parameters affecting the sonophotocatalytic degradation of MeO with nanoparticles Ag/TiO(2) were determined. The results indicated that the degradation ratio of MeO increased with the increase of ultrasonic power. An optimum 60 mg/L of Ag/TiO(2) added to relatively low concentrations of MeO was proved to have the most effective degradation efficiency. The study on the effects of hydroxyl radical (*OH) scavengers (i.e. mannitol and dimethyl sulfoxide) on the MeO degradation indicated that *OH radicals played an important role during MeO degradation, which enhanced MeO to be completely decomposed.