Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.     

NHD脱碳工段技改总结

合成氨装置脱碳工段采用NHD脱碳工艺,由于脱碳后的脱碳气中CO2含量偏高,造成H 2损耗较大,为此采用ZUPAC系列双向金属折峰式波纹填料和新型槽盘式液体分布器对脱碳塔进行改造。改造后,脱碳气中CO2体积分数从2.0%降至1.6%,年可增加经济效益1000万元左右。     

均匀沉淀法制备纳米氧化锌和片状氧化锌粉体

以氯化锌、尿素为原料 ,采用均匀沉淀法在一定条件下制备得到纳米级氧化锌粉体。并以TEM、SEM、XRD等测试手段对产物的粉体结构、形貌进行了研究。结果表明 ,在 2 0 0℃下热处理得到的氧化锌粉体结晶性能良好 ;在较大的反应物浓度及反应物浓度比下可以得到较小的晶体粒径 ,平均为 2 0nm ,且分散性好 ;在较小的浓度及较小的浓度比下得到的晶体粒径较大 ,并呈片状生长。阐述了浓度对于粒径大小的影响并得出片状氧化锌微晶生长的最佳条件。     

Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

多无限远目标模拟装置光轴共面测试技术研究

提出一种基于激光准直五棱镜回转扫描和CCD技术的非接触检测方法,通过检测三块立板平面度来实现对多无限远目标模拟装置光轴共面度的高精度非接触测量。给出误差评定方法,同时对仪器精度进行分析,通过实验测得共面度为0.039mm,满足精度要求。     

基于二氨基苯基卟啉的新型聚酰亚胺的合成与表征

卟啉类化合物的结构特征使其在很多领域受到广泛的关注,现在通常在卟啉上做修饰以获得更优的性能。以氨基苯基取代的卟啉化合物作为二胺单体和均苯四甲酸二酐为二酐单体,以苯甲酸为溶剂,通过反应合成粗产品新型的聚酰亚胺材料,用丙酮和氯仿洗涤得到纯产品,并进一步合成了Zn-卟啉聚酰亚胺。采用傅里叶红外吸收光谱、紫外-可见吸收光谱对产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,以及原料与产物的对比分析,初步确定了合成产物的结构。结果表明,聚合产物是以卟啉骨架结构为主要聚合单元的聚酰亚胺类共聚物。     

环氧涂层/镀锌板电极系统腐蚀电化学行为

利用EIS研究环氧型有机涂层的腐蚀电化学行为。在浸泡初期阻抗谱是一个时间常数的单容抗弧,阻抗值基本不变,此时漆膜能够阻止介质渗入。在浸泡中期阻抗值随时间逐渐增大,原因为镀锌钢板表面预处理层的铬酸盐自修复作用以及铬酸盐转化膜溶解物和腐蚀产物沉积堵塞漆膜微孔隙,阻止介质渗入到达镀锌钢板表面,导致阻抗值变大。后期,预处理膜完全溶解破坏,金属基体腐蚀反应加快,阻抗值变小.     

少齿差减速器偏心轴及偏心套加工工艺研究

针对具有较高精度的偏心轴及偏心套加工问题,采用了组合式工艺偏心轴——套,并利用电火花线切割保证偏心精度。     

VP PMIG双向高压稳弧脉冲叠加控制

为了解决变极性脉冲MIG焊（VP PMIG）变换电弧极性时使电弧可靠再引燃问题,逆变弧焊电源给电弧空间输出电压的同时,再给电弧空间叠加高压脉冲.控制电弧变换为正极性时需要加正向高压脉冲,控制电弧变换为负极性时需要加负向高压脉冲.研究了逆变弧焊电源的逆变结构及二次功率逆变电路的控制模式,设计了叠加双向高压稳弧脉冲的电力电路及其控制模式.试验表明,采用设计的变极性控制系统及双向高压稳弧脉冲叠加控制系统焊接铝合金,控制系统运行稳定,满足了焊接可靠再引燃电弧的需要,稳弧效果良好.     

基于行为金融理论的非理性投机泡沫模型

为了从投资者非理性的角度揭示资产泡沫的生成机理,为股市泡沫监管提供更有效的工具,本文在基于行为金融理论的价值函数基础上,对噪音投资者模型进行改进,从利空和利多两个方面考查投资者行为因素的影响,从而构造出新的非理性投资泡沫模型,并利用我国股市数据对模型进行实证研究.结果证明,该模型更切合事实的非理性投机泡沫的发展过程.