Degradation of Isoprene in the Presence of Sulphoxy Radical Anions     

Krzysztof J. Rudzinski 《Journal of Atmospheric Chemistry》2004,48(2):191-216

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.  相似文献   

Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds     

W. Pasiuk-Bronikowska  T. Bronikowski  M. Ulejczyk 《Journal of Atmospheric Chemistry》2003,44(1):97-111

To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO₃.1/2 H₂O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe₂(SO₄)₃ or CoSO₄, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)10⁸ M^–1s^–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.  相似文献   

硝酸根对颗粒状铁降解三氯乙烯的影响(英文)     

Qiong LU　 Lai GUI　 Robert W.GILLHAM 《地学前缘》2005,12(Z1):176-183

为研究硝酸根对颗粒状铁降解三氯乙烯的影响,进行了柱实验和相应的反应铁腐蚀电位测定。在硝酸根离子存在条件下,铁的腐蚀电位相应升高,系统条件也因之发生变化,导致钝性的铁氧化物在铁表面生成。因而,三氯乙烯和硝酸根离子降解速率明显减小, 并且降解速率减小的程度与硝酸根离子的浓度成比例。当污染液流过反应柱时,硝酸根离子与铁反应, 被还原为氨根离子。该反应造成硝酸根离子的浓度梯度,使钝化区在柱中上移,从而影响了三氯乙烯的降解曲线。与三氯乙烯单独与铁反应相比,当含4 7 mg/L硝酸根的三氯乙烯溶液流经反应柱170 孔隙体积后,降解50% 三氯乙烯所需的时间(t50) 从小于4 h增加到大于10 h;而当三氯乙烯溶液中加入100 mg/L硝酸根离子,仅17 孔隙体积溶液流经反应柱后,三氯乙烯降解t50就已大于14 h。研究结果表明,由于硝酸根离子对铁的腐蚀电位和铁表面氧化膜的不利作用,在处理靶污染物为高浓度硝酸根离子和三氯乙烯共同污染的地下水时,铁渗透反应隔栅不是最佳选择。如果靶污染物中硝酸根离子浓度比较低,则在设计铁隔栅时应考虑到硝酸根离子造成的不利因素,相应增加铁墙的厚度,从而确保三氯乙烯的降解效果。  相似文献   

Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?     

Jae-Young Yu 《Aquatic Geochemistry》1996,2(1):81-105

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.  相似文献   

Effect of Agents on Hydrate Formation and Low-Temperature Rheology of Polyalcohol Drilling Fluid     

蒋国盛  宁伏龙  张凌  涂运中 《中国地质大学学报(英文版)》2011,(5)

In order to ensure safe drilling in deep water and marine gas hydrate bearing sediments,the needed characteristics of drilling fluid system were analyzed.Moreover,the effect of different agents on hydrate formation and the low-temperature rheology of designed polyalcohol drilling fluid were tested,respectively.The results show that clay can promote gas hydrate growth,while modified starch and polyalcohol can inhibit hydrate formation to some extent,and PVP K90 has a good performance on hydrate inhibition.Th...  相似文献   

低土相高密度钻井液体系的配方研制     

梁文利  刘杰  吴易成 《海洋地质译丛》2011,(3):81-88

针对高密度钻井液体系普遍存在的黏度偏大、流变性难以调控、经常出现井下复杂情况等问题,通过对聚合物包被剂、膨润土含量、润滑剂、抑制剂的优选,确定了低土相高密度钻井液体系的最佳配方,开发了一套低土相高密度钻井液体系。室内研究结果表明,该钻井液体系具有良好的抗钻屑、NaCl和石膏的污染能力和良好的抑制封堵能力,岩屑滚动回收率达到93．7％,能够满足高温高压、严重造浆、高渗透率以及微裂缝发育等复杂地层的钻井技术要求。  相似文献   

中原老区井壁稳定技术应用          下载免费PDF全文

秦献民  赵润琦  路艳 《探矿工程》2012,39(2):28-30

造成井壁失稳的原因是多方面的,主要影响可归结为力学因素、化学因素和工程技术因素。通过对2010年施工的钻井数据进行分析,对中原油田老区井壁稳定技术进行了研究。根据施工中遇到的问题,采取的措施,提出了对油田老区井壁稳定技术的一些想法,利于提高油田老区钻井的速度和质量。  相似文献   

有机溶剂来源污染物对中国鲎N-乙酰-β-D-氨基葡萄糖苷酶的影响     

林建城  吴建洪  林娟娟 《中国海洋大学学报(自然科学版)》2021,(6):42-49

N-乙酰-β-D-氨基葡萄糖苷酶(EC3.2.1.52,NAGase)是几丁质酶系的主要组成分之一,节肢动物周期性脱皮生理和生长发育与NAGase密切相关。为了探讨有机溶剂对中国鲎(Tachypleus tridentatus)NAGase的影响,从中国鲎内脏分离提取了NAGase,研究甲醇、乙醇、正丙醇、正丁醇、乙二醇、丙三醇、甲醛和丙酮等8种有机溶剂对中国鲎NAGase的影响;利用酶抑制作用动力学方法,研究丙酮对NAGase的抑制机理和抑制作用类型。结果表明:甲醇对中国鲎NAGase有激活作用,乙醇、正丙醇、正丁醇、甲醛和丙酮对该酶均有不同程度的抑制作用;乙二醇和丙三醇对NAGase表现为低浓度下呈激活现象,随浓度增大则转为对酶的抑制作用;丙酮对中国鲎NAGase的抑制有剂量效应关系,0.1 mol/L丙酮可使酶活力丧失49.53%;丙酮对中国鲎NAGase的抑制作用是个可逆过程;动力学研究显示,该酶抑制作用类型属于混合型。丙酮对游离酶(E)的抑制常数KI和对酶-底物络合物(ES)的抑制常数KIS分别为0.117和0.608 mol/L,KI相似文献   

Kinetic Modeling for Simultaneous Biodegradation of Phenol and Formaldehyde at Inhibitory Concentrations by Ralstonia eutropha          下载免费PDF全文

Alireza Habibi  Shahin Sharifi 《洁净——土壤、空气、水》2016,44(9):1113-1122

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三元复合驱采油污水阻垢缓蚀剂电化学分析     

张国成  谢欣 《东北石油大学学报》2012,(3):96-99,109,11

研制适用于三元复合驱采油污水工况条件下的MPM固体缓蚀阻垢剂,分析三元复合驱采油污水中MPM的电化学特性.结果表明:随着温度增加,20#钢在采油污水的腐蚀速率呈增加趋势,极化曲线显示钝化区表面材料在表面高温下处于钝化状态,产生的钝化膜能够降低腐蚀速度.在阻垢缓蚀剂质量浓度相同的情况下,不同温度的电化学阻抗谱在高频区出现容抗弧,显示优良的缓蚀性能.不同质量浓度MPM极化曲线表明,缓蚀率随MPM质量浓度的增加而增大,MPM极值质量浓度为80mg/L.污水体系中的Ca2+、Cl-对缓蚀率产生影响.MPM适用于高质量浓度Ca2+的三元复合驱采油污水处理.  相似文献