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11.
Boris V. L'vov 《Mikrochimica acta》1991,104(1-6):299-308
A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu2O, NiO, PbO and Mg(OH)2 during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis. 相似文献
12.
采用循环伏安法,对SPEPt电极以及SPEAu-Pt电极上还原态CO2的电化学氧化行为研究表明,此类电极的电化学特性与光滑Pt电极一致:CO2在氢原子吸附电位区0~250mV(vs.RHE)处,可与电极上化学吸附的氢反应,生成还原态的CO2,通过线性扫描,还原态CO2即发生一不可逆电化学氧化过程(阳极剥离).在SPEPt系列及SPEAu-Pt系列上CO2的电化学行为表明,当SPEPt系列上Pt的载量为2.5mL的0.01mol·L-1H2PtCl6的Pt时,对还原态CO2的电催化活性最好,当Pt的载量相同时,在SPEAu-Pt上,催化剂对还原态CO2的电化学氧化行为比SPEPt电极更强,这是由于预先沉积的Au对后沉积的Pt有调制作用. 相似文献
13.
Influence of boric acid on the electrochemical deposition of Ni 总被引:1,自引:0,他引:1
M. Šupicová R. Rozik L. Trnková R. Oriňáková M. Gálová 《Journal of Solid State Electrochemistry》2006,10(2):61-68
The electrolytic deposition of Ni onto a paraffin-impregnated graphite electrode from supporting chloride electrolyte (0.5 mol dm−3 NaCl) adjusted to the required pH using dilute HCl is investigated. The effect of electrolyte composition on the Ni electrodeposition
is studied using linear sweep voltammetry in the cathodic region. An elimination voltammetry procedure was applied to evaluate
the polarization curves. The aim of this work was to deduce the mechanism of Ni reduction in the chloride bath as well as
the influence of boric acid on this. Positively-charged NiCl+ ions were found to be the electroactive particles in the Ni reduction mechanism. The strong competition between the NiCl+, Cl− and H+ ions for active sites at the electrode is discussed. Kinetically-controlled adsorption/desorption processes of various species
were also confirmed using elimination voltammetry with a linear scan. The evolution of gaseous hydrogen, catalyzed by the
freshly-deposited Ni, accompanies the electrodeposition process. The presence of boric acid at a sufficiently high concentration
inhibits the deposition of Ni and, at the same time, improves the morphology and brightness, as well as the adhesion of the
deposited Ni.
Elimination voltammetry with a linear scan is an efficient way to evaluate current–potential curves that reflect the electrodeposition
of one-component Ni coatings. By eliminating selected currents, additional interesting and useful information can be obtained
from voltammetric data. 相似文献
14.
Ye Lin Feng Zeng‐Guo Zhao Yu‐Mei Wu Feng Chen Shi Wang Guo‐Qing 《Journal of polymer science. Part A, Polymer chemistry》2006,44(11):3650-3665
A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF3·Et2O as initiator through cationic ring‐opening polymerization. The evidence from 1H and 13C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10?5 S/cm at room temperature and 6.3 × 10?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006 相似文献
15.
Xinyu Huang Roham Solasi Yue Zou Matthew Feshler Kenneth Reifsnider David Condit Sergei Burlatsky Thomas Madden 《Journal of Polymer Science.Polymer Physics》2006,44(16):2346-2357
The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006 相似文献
16.
Chi-So Lee 《中国化学会会志》1987,34(3):207-210
A differential pulse polarographic method for the determination of nitrate ion has been developed. With 0.5 M CaCl2 as supporting electrolyte, NO?3 is reduced to give a peak with E1/2=–1.836 Volt vs. the Ag/AgCl electrode. The differential pulse polarographic peak height is proportional to the nitrate concentration from 20 to 60 ppm. The detection limit for nitrate is 2 ppm in pure aqueous solution. In the determination of 40 ppm nitrate a relative precision (relative standard deviation) of less than 2% was achieved. Nitrite interferes seriously and should be absent if accurate results are required. The method has been applied to the determination of nitrate in Ammonium Uranyl Tricarbonate (AUT) Solution, results obtained by this method are compared to those obtained by ion chromatography. The agreement between the two sets of results suggests that the DPP method can be used with a fair degree of confidence. 相似文献
17.
18.
多电解质溶液中带电胶体粒子的电势分布由球形Poisson-Boltzmann方程(PBE)描述.PBE是一个非线性的微分方程,且难以求得其解析解.本文采用非线性P-B积分方程,计算电势分布的数值解.首先,根据静电场和热力学系统中的物理定理,导出描述电势分布的P-B积分方程(PBIE);其次,用迭代方法求PBIE的数值解.最后,计算了在3-1型电解液中无量纲半径κa分别为0.12和0.22,无量纲表面电势ξ分别为1,2,4,6时球形胶体粒子外部的电势值.为了检验数值解的精度,计算了表面电荷密度,并与Loeb(1961)和Oshima(1995)等人的结果比较,本文结果的相对误差小于1%,优于Oshima的结果. 相似文献
19.
本文续前报在恒定溶液总离子强度I=1.00mol·kg~(-1),改变葡萄糖在混合溶液中的质量百分数x=5%、15%和20%的条件下,应用电动势法测定了无液接界电池(A)和电池(B)的电动势: Pt,H_2(1.013×10~5Pa)|HCl(m),d-Glucose(x),H_2O(1-x)|AgCl-Ag (A) Pt,H_2(1.013×10~5Pa)|HCl(m_A),NaCl(m_B),d-Glucose(x),H_2O(1-x)|AgCl-Ag(B) 其中x代表葡萄糖在水中的质量百分数,m_A和m_B分别是HCl和NaCl在混合溶液中的质量摩浓度。利用电池(A)的电动势数据得到了AgCl-Ag电极在d-Glucose-H_2O混合溶液中的标准电极电势Φ_m~0,讨论了HCl的迁移性质,利用电池(B)的电动势数据,确定了HCl在HCl-NaCl-d-Glucse-H_2O体系中的活度系数γ_A,实验结果表明:在恒定总离子强度下,HCl的活度系数服从Harned规则。HCl的迁移自由能与葡萄糖的质量百分数x成线性关系。计算了HCl 相似文献
20.
综述了近年来利用固体电解质电解池消除NO的研究进展.重点总结了电化学消除NO研究体系、电化学消除NO分解机制、O2-在固体电解质电解池中传导的控速步骤、电极种类和形态对NO分解性能的影响以及直流与交流电作用的差异等几个方面的研究结果.在RuO2—Ag—YSZ—Pd电解池上实现的NO选择性分解是迄今为止的最佳结果,500℃下NO的转化率为31.8%,NO的分解活性是O2的分解活性的13倍.该领域今后研究的主要方向是,进一步提高NO分解相对于共存O2离子化的选择性、降低O2-在阴极界面处的传导阻力和探寻可在更低温度传导O2-的新的固体电解质 相似文献