Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

25～75℃酸性NaCl溶液中方铅矿的溶解动力学

在25～75℃、pH=0.43～2.45的1mol/LNaCl溶液中进行了方铅矿的溶解动力学实验。发现在远平衡条件下,方铅矿的溶解速率r与氢离子活度犤H+犦呈线性关系,溶解速率方程(速率定律)为:r=k犤H+犦,即对H+而言,溶解反应为一级。其中速率常数k为2.344×10-7mol/m2·s(25℃)、1.380×10-6mol/m2·s(50℃)、7.079×10-6mol/m2·s(75℃)。溶解反应的活化能为43.54kJ/mol,方铅矿的溶解机理为表面化学反应,速率决定步骤为表面配合物的离解。     

MODELING THE FATE AND TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN AN UNSTEADY RIVER-ESTUARINE SYSTEM

1 INTRODUCTION Extensive literature (Brown et al., 1985; Sawhney et al., 1981; Bierman and Swain, 1982; Connolly, 1980; Lopez-Avila and Hites, 1980; O扖onnor, 1988) described lots of sorbed pollutants or toxic substances in bed sediments of rivers, even after the effluent was halted for a long time. This is particularly true for hydrophobic organic compounds that can be sorbed on the particles and accumulated in the river bed sediments (Karickhoff et al., 1979). Pollution events of…     

In situ methods for studying adsorbed phases at the solid/liquid interface: microcalorimetry and ellipsometryLes méthodes d'étude in situ des phases adsorbées : microcalorimétrie et ellipsométrie

The applications of calorimetric and ellipsometric methods to the understanding of adsorption phenomena occurring at the solid–liquid interface are presented with examples in the field of surfactant adsorption. The various experimental approaches are presented and compared, i.e., immersion calorimetry, titration calorimetry and liquid flow calorimetry. It is shown how they can be used to follow, in situ, the building steps of the surfactant adsorbed layer. On the other hand, ellipsometry allows the adsorption isotherm, the adsorption kinetics as well as the thickness of the adsorbed layer to be determined on well-defined flat surfaces. To cite this article: R. Denoyel, C. R. Geoscience 334 (2002) 689–702.     

不同浓度Li2SO4水溶液结构的X射线衍射研究

用θ～ 2θ型粉末衍射仪反射法精确测量了不同浓度的Li2 SO4水溶液的衍射数据 ,通过数据处理给出了溶液的结构函数和径向分布函数 ,由几何结构模型的最小二乘法精修 ,得到了溶液中阳离子和阴离子第一、二水合层的结构参数。     

湍流混合动力学机理研究

在分析传统混合动力学机理基础上,通过宏观混合与微观混合时间量级的对比,提出了湍流条件下,涡流扩散主导宏观混合,分子扩散主导微观混合,而混合过程由宏观混合主导,欧拉数Eu可作为混合效果的控制指标,并通过3种不同容积反应器的混合搅拌试验,进一步证实了该指标的实用性。     

Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

溶液结构的X射线衍射研究──4.用粉末衍射仪精确测定溶液结构的新方法

本文叙述了用θ—2θ型X射线衍射仪精确测定电解质溶液结构的新的实验技术，设计制作了具有恒温功能的超厚液体样品池，并建立了样品池窗口强度的校正方法。建立在Johansson和Yamaguchi工作基础上，发展了液体X射线衍射数据处理和结构参数精细化的计算机程序，获得了非常令人满意的实验结果。由θ－2θ型X射线衍射仪精确测定的径向分布函数与θ－θ型衍射自由表面散射比较，表明DRF分辩率有所提高。