The strong cooperativity of dioxygen binding by dicobalt (II) diporphyrin compounds in nonaqueous solution at room temperature

Thermodynamic data were determined for the reversible binding of O₂ to two compounds of dicobalt(II) di(meso-tetra-phenyl)porphyrin derivatives with different lengths of diamidoaliphatic bridge (abbreviated to Co₂PP₈ and Co₂PP₄) in N,N-dimethylformamide at room temperature. The partial pressure of dioxygen necessary for half-oxygenation (P _1/2) and hill coefficient (n) at 298 K were determined as follows:P _1/2=54.2 kPa,n=2.0 for Co₂PP₈ andP _1/2=6.8 kPa,n=1.8 for Co₂PP₄, respectively. The rate equations of reversible oxygen binding by Co₂PP₈ were determined and the reaction path was proposed. The results of ther-modynamic and kinetic studies indicate that there exists strong cooperative effect during oxygenation of the compounds. The ESR observation reveals that the dioxygen complexes formed in the solutions are of superoxo (Co-O ₂ ⁻ ) type. Supported by the Research Foundation of the State Education Commission of China Zhou Xiaohai: born in 1962, Ph.D. Associate professor     

溶剂－油，溶剂－蜡汽液平衡的连续热力学研究

应用连续热力学方法，对实验测定的甲乙酮－蜡、苯－蜡、甲苯－蜡、丙酮－调合油、甲乙酮－调合油、苯－调合油、甲苯－调合油７个系统在常压下的汽液平衡数据进行了关联。将连续组分的密度分布函数Ｆ（Ｉ）分别用Γ函数和样条函数，并假定连续组分（油或蜡）间的相互作用参数、离散组分（溶剂）与连续组分之间的相互作用参数为常数，取得了满意的结果。并将该法与虚拟组分法进行比较，结果表明，连续热力学方法具有计算准确度高，计算效率高的优点，是一种值得推荐的好方法。     

QSL炼铅过程的热力学分析

根据已提出的直接炼铅过程的计算机模型，分析了ＱＳＬ炼铅法在工业上得不到弃渣而失败的根本原因，同时对精矿成分、熔炼温度、重油量和风量等操作条件进行了模拟，发现提高温度不能得到弃渣，而还原性的气氛却可极大地降低炉渣中铅含量，从而提出降低渣含铅的具体改进措施与方案，为在实际生产中解决这一问题提供可靠的依据．     

熵的相对标准法问题研究

根据热力学第三定律和统计热力学，运用“相对标准法”对单质和化合物的熵的相对标准进行了讨论，并指出熵与焓的相对标准状态不同，应该统一起来，以满足热力学函数定义式；G＝H－TS。     

Entropy budget of the earth, atmosphere and ocean system

The energy budget in the system of the earth, atmosphere and ocean conforms to the first law of thermodynamics, namely the law of conservation of energy, and it is balanced when the system is in a steady-state condition. However, the entropy budget following the second law of thermodynamics is unbalanced. In this paper, we deduce the expressions of entropy flux and re-estimate the earth, atmosphere and ocean annual mean entropy budget with the updated climatologically global mean energy budget and the climatologically air-sea flux data. The calculated results show that the earth system obtains a net influx of negative entropy (-1179.3 mWm-2K-1) from its surroundings, and the atmosphere and the ocean systems obtain a net input of negative entropy at about -537.4 mWm-2K-1 and -555.6 mWm-2K-1, respectively. Calculations of the entropy budget can provide some guidance for further understanding the spatial-temporal change of the local entropy flux, and the entropy production resulting from all kinds of irreversible processes inside these systems.     

新型螯合纤维的制备及其动力学和热力学性质

目的研究自制聚丙烯腈螯合纤维用于Cu(Ⅱ)离子的吸附,考察pH值对Cu(Ⅱ)离子吸附性能的影响。方法以聚丙烯腈丝为原料,经醇解、肼解及胺肟化反应来制备多配位螯合纤维,并用于对铜的吸附,对吸附动力学和热力学进行了理论分析。结果制备了一种多配位的螯合纤维,用红外和扫描电镜对螯合纤维进行了表征。该多配位螯合纤维在pH为4时,对Cu(Ⅱ)离子的饱和吸附量为137.5 mg/g,且具有较好的吸附行为,随着温度升高吸附速率加快,同一温度下,浓度增大吸附速率减小。结论Freundlich吸附等温式能较好地描述该化学吸附过程。     

CO2热力学性质的量子化学计算

采用MP2,QCISD和密度泛函B3LYP方法,在6-311g**和6-311+g**水平上优化和计算了CO2和O2平衡几何结构、能量和谐性振动频率,导出了在标准条件(T=298.15 K,p=1.013×105Pa)下的熵、热焓和热容,并由此计算得到了CO2的标准生成焓和标准生成自由焓.结果显示,B3LYP/6-311G**方法计算得到的CO2和O2的平衡几何结构、能量、谐性振动频率、熵和热容与实验值符合最好;而MP2/6-311G**方法计算得到的CO2标准生成焓和标准生成自由焓与实验值符合最好.     

吡啶改性凹凸棒废渣对亚甲基蓝废水的吸附

过氧化二苯甲酰为引发剂,以吡啶为单体改性凹凸棒废渣处理亚甲基蓝废水,研究吸附剂对亚甲基蓝的吸附机理以及动力学和热力学吸附性质.在实验范围内,废渣对亚甲基蓝的吸附可以用Langmuir吸附等温线描述,吸附过程符合准二级动力学方程.计算结果△G0＜0,△H0＜0,△S0＜0,说明此吸附是一个自发、放热、熵减的过程.     

Characterization of Cu（Ⅱ） Ion Adsorption Behavior of the Polyacrylic Acid-Polyvinylidene Fluoride Blended Polymer

A blended polymer adsorbent prepared using acrylic acid and polyvinylidene fluoride was used to remove copper from aqueous solutions. The polymer was prepared using thermally induced polymerization and phase inversion. The blended polymer was characterized by X-ray diffraction analysis （XRD）, environ- mental scanning electron microscopy （ESEM）, X-ray photoelectron spectroscopy （XPS）, and N2 adsorption/desorption experiments. The sorption data was fit to linearized adsorption isotherms of the Langmuir, Freundlich, and Dubinin-Radushkevich （D-R） isotherms models. The batch sorption kinetics was evaluated using pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetic reaction models. △H0 is greater than 0, AGo is lower than 0, and △S0 is greater than 0, which shows that the adsorption of Cu （Ⅱ） by the blended polymer is a spontaneous, endothermic process. The adsorption isotherm fits better to the Freundlich isotherm model and the pseudo-second-order kinetics model gives a better fit to the batch sorption kinetics. The adsorption mechanism is assumed to be ion exchange between the cupric ion and the carboxylic acid functional group of the blended polymer.     

LiF-NaF-KF体系的相图计算

基于CALPHAD技术首先评估了LiF-NaF和LiF-KF两个二元熔盐体系,液相和端际固溶体Halite相均采用RedlichKister多项式置换熔体模型描述,模型参数的优化选取实验相平衡数据和热化学数据以及本文根据第一性原理预测的数据.结合文献中已报道的NaF-KF体系的热力学参数,用Muggianu模型扩展至LiF-NaF-KF三元体系,根据三元共晶点的实验数据调整三元交互参数.最终的相图计算结果与绝大部分实验数据和第一原理计算数据吻合较好,由此获得了一套自洽且可靠的热力学参数,其能够准确描述LiF-NaF-KF体系的相平衡与热力学性质.