二氧化氯在炼油循环水中的杀菌除泥作用

采用强氧化剂二氧化氯对炼油循环水进行杀菌灭藻、除垢和减缓腐蚀现场试验研究 ,且对试验结果进行了分析 .结果表明 :稳定性二氧化氯可有效控制炼油循环水中微生物量 ,加药量约 1mg/L ,2 4h后杀菌率达 10 0 % ;同时减少粘泥在热交换设备上的形成 ,有效除去污垢 ,使缓蚀剂发挥作用 ,腐蚀速率明显减小 (小于 0 .1mm /a) ,循环水浊度小于 10mg/L ;加药量小于 1mg/L时其对有机磷水稳定剂的影响小 .     

Homogeneous chemiluminescence system in neutral and near neutral aqueous solution with ClO2 as oxidant and its analytical application

Using ClO₂ as chemiluminescence (CL) oxidant, a novel homogeneous CL system in neutral and near neutral aqueous solution is proposed in this paper. ClO₂ could oxidize sulfite in pH 5.0–8.5 acetate buffer to produce CL emission, and pipemidic acid could sensitize the CL system. The ClO₂–SO₃²⁻–pipemidic acid reaction was used as a model CL system and explored the possibility of highly active and eco-friendly ClO₂ being used as CL oxidant in neutral and near neutral aqueous solution. Combined with flow-injection analysis, the proposed CL system was applied to the automated dissolution testing of pipemidic acid tablet. Compared with the common strong acidic or strong basic CL system, this proposed CL owns its advantages.     

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO− coupling system

On the basis of the structures and properties of the ClO/ClO^? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C₁), 20.54 (EC2: C₂, ²B), 20.69 (EC3: C₁), 20.70 (EC4: C_s, ²A′), and 20.69 (EC.5: C_2h, ²B_u) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

CH_3O与CIO双自由基反应机理的量子化学研究

在QCISD(T)/6-311+G(d,p)//B3LYP/6-311+G(3df,3pd)水平上,对CH3O与ClO双自由基反应进行了理论研究.结果表明,该反应共有三个反应通道,产物分别为HOCI+CH2O,CH2O2+HCl和CH3Cl+O2(1△).不论从动力学角度,还是从热力学角度看,形成产物HOCl+CH2O的通道均是最有利的,因此为主要反应通道,这与实验观察到的结果是一致的.     

稀土钬及铒钇丙氨酸配合物的量热与热分析研究

合成了两种固态稀土丙氨酸配合物[Ho2(Ala)4(H2O)8]Cl6和[ErY(Ala)4(H2O)8](ClO4)6 (Ala为丙氨酸),用量热和热分析方法研究了这两种配合物的热力学性质.用全自动高精密绝热量热计测定了在78～377 K温区内的低温热容.对于[Ho2(Ala)4(H2O)8]Cl6,在214～255 K温区内发现一固-固相变,其相变温度为235.09 K.对于[ErY(Ala)4(H2O)8](ClO4)6,在99～121 K温区内也发现一固-固相变,其相变温度为115.78 K. [Ho2(Ala)4(H2O)8]Cl6固-固相变焓为3.02 kJ• mol－1,相变熵为12.83 J•K－1•mol－1； [ErY(Ala)4(H2O)8](ClO4)6 固-固相变焓为1.96 kJ•mol－1,相变熵为16.90 J•K－1•mol－1.同时,用TG技术在40～800 ℃温区研究了两配合物的热稳定性.由TG/DTG曲线分析可知, [Ho2(Ala)4(H2O)8]Cl6从80 ℃到479 ℃热分解分两步完成, [ErY(Ala)4(H2O)8](ClO4)6从120 ℃到430 ℃热分解分三步完成.     

Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2（L-Glu）2（H2O）6]（ClO4）4·6H2O（s）

A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.     

银纳米微粒荧光猝灭法测定水中痕量ClO2

在pH 9.1的NH4Cl-NH3·H2O缓冲溶液中,银纳米微粒在470 nm处产生一个荧光峰;它能被ClO2氧化导致体系的荧光发生猝灭.ClO2浓度在0.001 1～0.185μg·mL-1范围内与荧光猝灭强度成良好的线性关系,检测限为0.004 7μg·mL-1 ClO2.据此建立了测定ClO2的荧光分析新方法,用于饮用水中ClO2的测定,结果满意.     

Synthesis and thermodynamic properties of a metal-organic framework: [LaCu6(μ-OH)3(Gly)6im6](ClO4)6

A metal-organic complex, which has the potential property of absorbing gases, [LaCu₆(μ-OH)₃(Gly)₆im₆](ClO₄)₆ was synthesized through the self-assembly of La³⁺, Cu²⁺, glycine (Gly) and imidazole (Im) in aqueous solution and characterized by IR, element analysis and powder XRD. The molar heat capacity, C_p,m, was measured from T = 80 to 390 K with an automated adiabatic calorimeter. The thermodynamic functions [H_T − H_298.15] and [S_T − S_298.15] were derived from the heat capacity data with temperature interval of 5 K. The thermal stability of the complex was investigated by differential scanning calorimetry (DSC).     

Reactions Between Humic Acid Solutions and Excessive ClO2 or Cl2

Reactions between humic acid solutions and excessive ClO2 or Cl2 have been investigated. Under various experimental conditions, the removal efficiency of TOC, UV254 and A140 from humic acid solutions were examined. The relationship between the removal efficiency and the consumption of ClO2 or Cl2 was discussed. The results showed that the maximum demand of ClO2 was 2.19 mg/mg TOC for the humic acid solution under the experimental conditions, and that of Cl2 was 1.88 mg/mg TOC. The variation tendency of ClO2 consumption was similar to that of Cl2. TOC of humic acid solutions decreased 15.2% and 15.6% after the reaction with ClO2 or Cl2 respectively. Under the experimental conditions, 21.4% of unsaturated bonds and 52.8% of humic acid color were removed by ClO2 in 168 h. As for Cl2, removal efficiency of unsaturated bonds and humic acid color were 16.8% and 41.7% respectively. Larger molecules from humic acid were oxidized to smaller molecules by ClO2 and Cl2. Higher oxidation potential of ClO2 than that of Cl2 was also indicated by variation of UV254/A410 ratios. The similar tendency, that exhibited faster variation in the initial 24 h, existed for all the research factors.     

H~ 和SO_4~(2-)离子对PbO_2电极上ClO_4~-阳极形成过程的影响

用分解极化曲线法研究了Ｈ＋和ＳＯ２－４离子对ＰｂＯ２电极上Ｏ２和ＣｌＯ－４阳极形成过程的影响．分解得到的稳态极化曲线φ～ｌｇｉＣｌＯ－４和φ～ｌｇｉＯ２上均有一电位突跃;在２５℃下前一突跃发生在１．９～２．０Ｖ;后一突跃发生在２．０５～２．１５Ｖ左右．两者在突跃区前后的Ｔａｆｅｌ斜率均接近于２．３０３ＲＴ／βＦ（其中β约为０．５１～０．５４）．在突跃前当［Ｈ＋］减小时,使ＣｌＯ－４形成或氧的析出过程均加速,同时使开始发生电位突跃的电流密度（ｃ．ｄ．）向高ｃ．ｄ．方向推移．在高氯酸溶液中当［Ｈ＋］增加时,对Ｏ２析出过程几乎没有影响,但对突跃后的ＣｌＯ－４阳极形成具有加速作用．ＳＯ２－４对ＣｌＯ－４形成和Ｏ２的析出均有阻滞作用,但对前者的阻滞作用要大于对后者的阻滞作用,因而使ＣｌＯ－４的电流效率下降