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1.
The generation of hydroxyl (OH) radicals was investigated during ultrasonic irradiation and in the presence of TiO(2). The effect of TiO(2) on an ultrasonic system's oxidation power was evaluated by examining the oxidation of salicylic acid. The generation of the salicylic acid derivatives, 2,3-dihydroxybenzoic acid (DHBA) and 2,5-DHBA, was measured by high-performance liquid chromatography coupled with electrochemical detection under different experimental conditions. The presence of TiO(2) enhanced the generation of DHBA during ultrasonic irradiation, thus indicating a higher oxidation power in the ultrasonic system. Al(2)O(3) also increased the generation of DHBA during irradiation; however, the effect of TiO(2) was found to be higher than that of Al(2)O(3). The addition of OH radical scavengers such as dimethylsulfoxide (DMSO), methanol and mannitol significantly suppressed the production of DHBA, and DMSO was found to have the highest suppressive effect among all scavengers. The effects of dissolved gases on the generation of OH radicals were further studied, and their power was found to be in the order Xe > Ar > O(2) > N(2). The degassing of the irradiation solution completely suppressed the generation of OH radicals. These results indicate that the presence of TiO(2) accelerates the generation of OH radicals during ultrasonic irradiation, and that the process may be mediated through the induction of cavitation bubbles in irradiating solutions.  相似文献   

2.
Hydrodynamic cavitation (HC) has been extensively investigated for effluent treatment applications. Performance of HC devices or processes is often reported in terms of degradation of organic pollutants rather than quantification of hydroxyl (OH) radicals. In this study, generation of OH radicals in vortex based cavitation device using coumarin dosimetry was quantified. Coumarin was used as the chemical probe with an initial concentration of 100 µM (15 ppm). Generation of OH radicals was quantified by analysing generated single hydroxylated products. The influence of operating parameters such as pH and type of acid used to adjust pH, dissolved oxygen, and inlet and outlet pressures was investigated. Acidic pH was found to be more conducive for generating OH radicals and therefore subsequent experiments were performed at pH of 3. Sulphuric acid was found to be more than three times effective than hydrochloric acid in generating OH radicals. Effect of initial levels of dissolved oxygen was found to influence OH radical generation. Performance of vortex based cavitation device was then compared with other commonly used cavitation devices based on orifice and venturi. The vortex based cavitation device was found to outperform the orifice and venturi based devices in terms of initial per-pass factor. Influence of device scale (nominal flow rate through the device) on performance was then evaluated. The results presented for these devices unambiguously quantifies their cavitational performance. The presented results will be useful for evaluating computational models and stimulate further development of predictive computational models in this challenging area.  相似文献   

3.
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.  相似文献   

4.
P Riesz  T Kondo  C M Krishna 《Ultrasonics》1990,28(5):295-303
Recent spin trapping studies of the free radical intermediates generated by the sonolysis of aqueous solutions are reviewed. Studies of rare gas saturated solutions of volatile solutes (e.g., methanol and ethanol) and of non-volatile solutes (acetate, amino acids, sugars, pyrimidines, nucleotides and surfactants) are consistent with the theory of three reaction zones in aqueous sonochemistry. The very high temperatures and pressures induced by acoustic cavitation in collapsing gas bubbles in aqueous solutions lead to the thermal dissociation of water vapour into hydrogen atoms and hydroxyl radicals. Reactions take place in the gas phase (pyrolysis reactions), in the region of the gas-liquid interface, and in the bulk of the solution at ambient temperature (similar to radiation chemistry reactions). By use of the rare gases with different thermal conductivities, the contributions of individual reaction steps with widely different energies of activation can be evaluated.  相似文献   

5.
Recently it has been shown that long chain (C5-C8) n-alkyl glucopyranosides completely inhibit ultrasound-induced cytolysis [J.Z. Sostaric, N. Miyoshi, P. Riesz, W.G. DeGraff, and J.B. Mitchell, Free Radical Biol. Med., 39 (2005) 1539]. This protective effect has possible applications in HIFU (high intensity focused ultrasound) for tumor treatment, and in ultrasound assisted drug delivery and gene therapy. n-Alkyl glucopyranosides with hexyl (5mM), heptyl (3mM), octyl (2mM) n-alkyl chains protected 100% of HL-60 cells in vitro from 1.057 MHz ultrasound-induced cytolysis under a range of conditions that resulted in 35-100% cytolysis in the absence of glucopyranosides. However the hydrophilic methyl-beta-d-glucopyranoside did not protect cells. The surface active n-alkyl glucopyranosides accumulate at the gas-liquid interface of cavitation bubbles. The OH radicals and H atoms formed in collapsing cavitation bubbles react by H-atom abstraction from either the n-alkyl chain or the glucose moiety of the n-alkyl glucopyranosides. Owing to the high concentration of the long chain surfactants at the gas-liquid interface of cavitation bubbles, the initially formed carbon radicals on the alkyl chains are transferred to the glucose moieties to yield radicals which react with oxygen leading to the formation of hydrogen peroxide. In this work, we find that the sonochemically produced hydrogen peroxide yields from oxygen-saturated solutions of long chain (hexyl, octyl) n-alkyl glucopyranosides at 614 kHz and 1.057 MHz ultrasound increase with increasing n-alkyl glucopyranoside concentration but are independent of concentration for methyl-beta-D-glucopyranoside. These results are consistent with the previously proposed mechanism of sonoprotection [J.Z. Sostaric, N. Miyoshi, P. Riesz, W.G. DeGraff, and J.B. Mitchell, Free Radical Biol. Med., 39 (2005) 1539]. This sequence of events prevents sonodynamic cell killing by initiation of lipid peroxidation chain reactions in cellular membranes by peroxyl and/or alkoxyl radicals [V. Misik, P. Riesz, Ann. N.Y. Acad. Sci., 899 (2000) 335].  相似文献   

6.
OH*自由基是火焰中主要的激发态自由基之一,它所产生的化学发光可用于描述火焰的结构、拉伸率、氧燃当量比和热释放速率等特征信息,因此被广泛应用于火焰燃烧状态的在线诊断。以甲烷/氧气层流同轴射流扩散火焰作为研究对象,采用GRI-Mech 3.0机理结合OH*自由基生成和淬灭反应进行数值计算,对OH*自由基的二维分布特性进行研究,分析不同区域内OH*自由基的生成路径,并探讨不同氧燃当量比例和不同喷嘴出口尺寸对OH*自由基强度和分布特性的影响。模拟结果与实验研究基本吻合,表明计算模型能够准确描述火焰中OH*自由基的二维分布。结果表明:在甲烷/氧气层流同轴射流扩散火焰中,OH*自由基存在两种不同形态的分布区域,分别由反应CH+O2=OH*+CO和H+O+M=OH*+M生成;随着氧燃当量比提高,OH*自由基的分布区域逐渐向火焰下游扩张,根据其分布形态的变化可以对火焰燃烧状况进行判断;如果OH*自由基仅分布于火焰的上游区域且呈断开形态,则说明火焰处于贫氧燃烧状态。如果OH*分布呈环状形态,则说明火焰处于富氧燃烧状态;相同氧气流量条件下,缩小喷嘴出口的环隙尺寸有助于加强燃料和氧气的化学反应程度,从而使火焰中OH*自由基的摩尔分数显著提高,增强OH*化学发光的辐射强度,提高火焰光谱诊断的准确性。  相似文献   

7.
Single bubble cavitation offers an unique opportunity to evaluate the effect of bubble activity in promoting chemical reactions. In this paper we study the isomerization reaction of maleic acid into fumaric acid using an aqueous solution of maleic acid saturated with CH2Br2. The Br* radicals are generated at the bubble surface and a whitish thread forms. For comparison, the same reaction was conducted in a sonochemical bath. A possible scheme of the reactions activated at bubble surface after the decomposition of organic brominated substances is proposed.  相似文献   

8.
Hydroxyl free radicals produced in Fricke solution exposed to 80 kV X-rays or 23 kHz ultrasound (intensity 3 W cm−2) or 20 kHz ultrasound (intensity 18.9 W cm−2) or 3.5 MHz clinical ultrasound (intensity 1.47 W cm−2), as estimated from the Fricke dosimetric data, exhibited a linear dose-response relationship. The dosimeter was found to be effective in the concentration range 1.0–8.0 mM of FeSO4 solution. The hydroxyl radicals produced in Fricke solution were inhibited by the OH radical scavengers dimethyl sulfoxide (200 mM), -histidine (10 mM) and sodium benzoate (10 mM) in a manner proportional to the rate constants of their reaction with the OH radicals. The power threshold for OH radical formation, which is presumably the threshold for cavity formation, was estimated for 23 kHz ultrasound by this dosimeter as 1.28 W cm−2 for a 4 cm3 sample volume.  相似文献   

9.
In this investigation, an attempt has been made to establish the physical mechanism of sonochemical synthesis of zinc ferrite with concurrent analysis of experimental results and simulations of cavitation bubble dynamics. Experiments have been conducted with mechanical stirring as well as under ultrasound irradiation with variation of pH and the static pressure of the reaction medium. Results of this study reveal that physical effects produced by transient cavitation bubbles play a crucial role in the chemical synthesis. Generation of high amplitude shock waves by transient cavitation bubbles manifest their effect through in situ micro-calcination of metal oxide particles (which are generated through thermal hydrolysis of metal acetates) due to energetic collisions between them. Micro-calcination of oxide particles can also occur in the thin liquid shell surrounding bubble interface, which gets heated up during transient collapse of bubbles. The sonochemical effect of production of OH radicals and H2O2, in itself, is not able to yield ferrite. Moreover, as the in situ micro-calcination involves very small number of particles or even individual particles (as in intra-particle collisions), the agglomeration between resulting ferrite particles is negligible (as compared to external calcination in convention route), leading to ferrite particles of smaller size (6 nm).  相似文献   

10.
The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.  相似文献   

11.
Ultrasonically initiated emulsion polymerization of styrene was carried out in the presence of aliphatic alcohols, e.g. methanol, ethanol, n-pronanol and n-butanol, as volatile hydroxyl radical scavengers. With the addition of methanol, the polymerization rate of styrene increased, while the molecular weight and the average particle size of the produced polystyrene decreased because more radicals were produced in the presence of methanol. This is true also for the other polymerization system using other aliphatic alcohols, such as ethanol, n-pronanol and n-butanol, suggesting that the alcohols enter into cavitation bubbles and further react with hydroxyl radicals (*OH) from the sonolysis of water to produce hydroxyalkyl radicals, so as to reduce the recombination of *H and *OH radicals, therefore more radicals will be present in the systems for initiating polymerization. Obviously, it is an effective way to enhance ultrasonically initiated emulsion polymerization rate of styrene by adding volatile hydroxyl radical scavenger.  相似文献   

12.
This study investigates the sonolytic degradation mechanism of non-volatile organic compounds and reaction sites for its degradation using various tools that allow OH* to be monitored, such as: the spin-trapping method of OH* detection using non-volatile nitrone trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the hydrogen peroxide analytical methods and the p-chlorobenzoic acid (pCBA)-probe method. These methods can successfully monitor OH* produced during sonochemical processes, and identify the major reaction sites involving OH* of the three proposed reaction zones--within the cavity, in the bulk solution, and at the gas-liquid interfacial (shell) region. The patterns of hydrogen peroxide accumulation under the various conditions suggest that peroxides pre-form at the interfacial region, but the self-scavenging reaction by hydrogen peroxide simultaneously takes place in the same region. The simultaneously measured peroxide concentration, in the absence and presence of DMPO, and that of the DMPO-OH adduct indicated the peroxide production and DMPO-OH adduct formation reaction occur at the shell region. The sonolytic destruction efficiency of ultrasound coupled with Fe(II) has been also investigated. The coupled Fe(II)/ultrasound process was found to enhance the OH* production rate by 70% compared to the ultrasound process alone due to the reaction of Fe(II) with sonochemically produced hydrogen peroxide (Fenton's reaction). This accelerated reaction was also found to occur at the shell region rather than in the bulk solution. The enhancement effect of Fe(II)/ultrasound was also examined using pCBA as a probe. 2.8-fold and 3.6-fold increases of the pCBA degradation rate were observed at Fe(II) concentrations of 10 and 20 microM, respectively.  相似文献   

13.
羟自由基与水杨酸反应机理的初探   总被引:2,自引:0,他引:2  
探讨羟自由基与水杨酸的反应动力学过程。水杨酸与Fenton反应产生的的羟自由基反应,采用紫外-可见分光光度法(UV)和质谱法(MS),考察反应物的浓度、反应时间、反应温度、溶剂pH值等对反应产物的浓度以及反应速率的影响。水杨酸与.OH反应生成的紫色产物在波长530nm处有最大UV吸收峰,但仅于pH=4.51的缓冲溶液和水中有吸收峰;且该产物的吸光度值,随着反应物浓度的增加而增加;随反应时间的延长而减少;随着反应温度的升高而减少。反应速率t=5s达到最大值,其后随着反应时间的延长而逐渐降低,1min时达到平衡。通过MS分析,可得到质荷比(m/Z)=153,248,249,288,289,304,328,329,344,345的离子峰。推测羟自由基与水杨酸反应的中间产物是紫色的大分子自由基,而最终产物为二羟基苯甲酸,该反应可能是加成反应和聚合反应同时进行。  相似文献   

14.
The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the advanced Fenton process--AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 min of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules.  相似文献   

15.
The gas-phase basicities (GBs), gas-phase proton affinities (PAs) and ionization potentials (IPs) of all six isomers of dihydroxybenzoic acid have been calculated using density functional theory at the B3LYP/6-311++G(2df,p)//B3LYP/6-31+G** level. A detailed conformational analysis of each isomer was performed, and the calculated thermodynamic properties were Boltzmann averaged over all conformations. Respectively, the GBs and the gas-phase PAs vary from 803.8 and 832.5?kJ?mol?1 for the least basic species (3,5-DHB) to 830.1 and 861.4?kJ?mol?1 for the most basic isomer (2,4-DHB). The reported GBs and gas-phase PAs of 2,3-DHB and 2,4-DHB, are in excellent agreement with previous experimental measurements. Agreement for the 2,5-DHB and 3,4-DHB isomers are not as good, but still close to or within the experimental error estimates. The calculated values for the GB and gas-phase PA of 2,6-DHB and especially 3,5-DHB are significantly outside the experimental error brackets. Repeating these calculations on the lowest energy conformation of each isomer at the MP2/6-311++G(2df,p)//MP2/6-31+G** level yielded significantly worse results. Our results indicate that protonation in all isomers takes place on the carboxylic sites. The vertical IPs vary from 8.14 eV for 2,5-DHB to 8.56 eV for 2,4-DHB.  相似文献   

16.
采用三组单色仪探测系统,测量了甲基环己烷在高温反射激波作用下瞬态燃烧反应过程中三种激发态自由基OH*,CH*和C*2的特征光辐射,得到了激发态自由基时间历程和光辐射相对强度随温度的变化规律。反射激波温度1 200~1 700 K,激波压力1.5 atm,甲基环己烷摩尔分数0.1%,当量比1.0。在点火燃烧初始阶段三种自由基几乎同时产生,自由基持续时间随着温度的升高而变短。相同温度下CH*和OH*自由基持续时间大于C*2自由基,在1 400 K以下C*2自由基发光消失。OH*和CH*自由基发光强度在T<1 400 K时对温度变化不敏感,而在T>1 400 K时CH*自由基峰值随温度快速增长,C*2和OH*峰值随温度增大比较平缓。将实验结果和化学反应机理模拟结果进行了对比,实验获得的OH*自由基时间历程在低温时和机理预测结果吻合较好,但在高温时有一定差异。CH*自由基时间历程在高温与机理结果吻合较好,在低温时机理预测结果CH*自由基持续时间要长于实验结果。实验测得的结果为含激发态物种化学反应动力学机理的验证和优化提供了依据。  相似文献   

17.
多相脉冲放电体系中羟基自由基的光谱诊断   总被引:1,自引:0,他引:1  
采用多针-板电极形式的气液混合脉冲放电系统,在其中加入玻璃珠负载的TiO2膜光催化剂形成了一个气-液-固多相脉冲放电体系,研究中利用脉冲放电过程中产生的紫外光效应诱导其中的TiO2的光催化作用,通过对放电体系中羟基自由基(·OH)的光谱诊断考察TiO2光催化作用与脉冲流光放电的协同作用效果。结果表明,本脉冲放电体系中产生的·OH在306 nm(A2Σ+→X2Π跃迁)、309 nm(A2Σ+(ν′=0)→X2Π(ν″=0)跃迁)和313 nm(A2Σ+(ν′=1)→X2Π(ν″=1)跃迁)处均产生发射光谱,其中313 nm处的·OH的光谱强度最强;脉冲放电协同TiO2光催化作用系统中·OH的发射光谱强度较单独的脉冲放电体系强,同时,条件实验(不同鼓气种类和水溶液初始pH值)的研究结果表明用氩气作为鼓气源时,多相反应体系中313 nm处·OH的发射光谱强度比以空气和氧气作为鼓气源时的强度高,酸性溶液中313 nm处·OH的发射光谱强度比中性和碱性溶液中高。  相似文献   

18.
Experiments on the removal of organic matters and ammonia nitrogen from landfill leachate by ultrasound irradiation were carried out. The effects of COD reduction and ammonia removal of power input, initial concentration, initial pH and aeration were studied. It was found that the sonolysis of organic matters proceeds via reaction with ()OH radicals; a thermal reaction also occurs with a small contribution. The rise of COD at some intervals could be explained by the complexity of organic pollutant sonolysis in landfill leachate. Ultrasonic irradiation was shown to be an effective method for the removal of ammonia nitrogen from landfill leachate. After 180 min ultrasound irradiation, up to 96% ammonia nitrogen removal efficiency can be obtained. It was found that the mechanism of ammonia nitrogen removal by ultrasound irradiation is largely that the free ammonia molecules in leachate enter into the cavitation bubbles and transform into nitrogen molecules and hydrogen molecules via pyrolysis under instant high temperature and high pressure in the cavitation bubbles.  相似文献   

19.
火焰的辐射光谱可为燃烧诊断提供诸多信息,因此目前对简单的气态火焰自由基辐射特性已进行了大量研究,而关于非均相火焰的辐射光谱特性研究则相对较少。采用改进的热氧喷嘴技术在敞开空间下直接点燃水煤浆,并利用光纤光谱仪和紫外成像系统,着重对甲烷和水煤浆火焰的辐射光谱及OH*的二维分布特性进行研究。结果表明:与甲烷火焰的光谱辐射相比,水煤浆火焰不仅存在OH*,CH*和C2*特征辐射,还产生了Na*,Li*,K*和H*的发射谱线,并出现了连续的黑体辐射,这些光谱辐射特征可作为水煤浆气化或燃烧的标志,也可作为水煤浆是否点燃的判据;通入水煤浆后,OH*强度明显下降,而CH*和C2*强度增大。对比甲烷火焰OH*二维分布,水煤浆火焰OH*峰值强度明显下降,化学反应区域面积显著减小;沿着火焰传播方向,甲烷和水煤浆火焰轴向的OH*强度均呈先增大后减小的趋势;甲烷火焰径向的OH*在反应核心区出现了双峰形态分布,而水煤浆火焰OH*径向始终呈单峰分布。随着氧碳当量比增大,水煤浆火焰OH*的存在范围扩大,说明氧气的增加促进了OH*的产生;随水煤浆流量提高,OH*的反应核心区域缩小,峰值强度明显下降,CH*,C2*,Na*,Li*,K*和H*的强度显著增强,连续的黑体辐射强度也明显增大,这些辐射光谱的变化可用于表征操作负荷的变化。  相似文献   

20.
Cavitation results in conditions of turbulence and liquid circulation in the reactor which can aid in eliminating mass transfer resistances. The present work illustrates the use of cavitation for intensification of biodiesel synthesis (esterification) reaction, which is mass transfer limited reaction considering the immiscible nature of the reactants, i.e., fatty acids and alcohol. Esterification of fatty acid (FA) odour cut (C(8)-C(10)) with methanol in the presence of concentrated H(2)SO(4) as a catalyst has been studied in hydrodynamic cavitation reactor as well as in the sonochemical reactor. The different reaction operating parameters such as molar ratio of acid to alcohol, catalyst quantity have been optimized under acoustic as well as hydrodynamic cavitating conditions in addition to the optimization of the geometry of the orifice plate in the case of hydrodynamic cavitation reactors. Few experiments have also been carried out with other acid (lower and higher)/methanol combination viz. caprylic acid and capric acids with methanol with an aim of investigating the efficacy of cavitation for giving the desired yields and also to quantify the degree of process intensification that can be achieved using the same. It has been observed that ambient operating conditions of temperature and pressure and reaction times of <3h, for all the different combinations of acid (lower and higher)/methanol studied in the present work, was sufficient for giving >90% conversion (mol%). This clearly establishes the efficacy of cavitation as an excellent way to achieve process intensification of the biodiesel synthesis process.  相似文献   

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