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Effect of adsorbed layers on the anodic oxidation of simple organic compounds. Part 2.—Role of adsorbed HCOOH species 吸附层对简单有机化合物阳极氧化的影响。第2部分。-吸附HCOOH的作用
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700801
A. H. Taylor, R. Pearce, S. Brummer
The anodic oxidation of 0.1 M HCOOH on smooth Pt electrodes in 1 M H2SO4 at 40°C has been examined. An adsorbed material with a high coverage θorganic accumulates on the electrode over a wide potential range. The rate of adsorption is not limited by mass transport. A maximum coverage, θorganic= 0.73, is indicated at +0.30 V, and this falls to zero by 0.65 V (RHE). This material poisons the main HCOOH → CO2 reaction at all potentials. The main oxidation process at ⩽0.45 V (RHE) proceeds via an adsorbed intermediate which has not been isolated on the surface. Electron transfer is the rate-limiting step. At 0.55⩽E⩽0.75 V (RHE), adsorption of the intermediate is rate limiting and this is followed by fast electron transfer. The role of θorganic in inhibiting the main oxidation process is discussed. A possible electroactive solution species is suggested.
研究了0.1 M HCOOH在光滑Pt电极上在1 M H2SO4中在40℃下的阳极氧化。具有高覆盖率θ有机的吸附材料在电极上的电位范围很宽。吸附速率不受质量输运的限制。在+0.30 V时表示最大覆盖θ有机= 0.73,在0.65 V (RHE)时降为零。这种物质在所有电位下都能毒害主要的HCOOH→CO2反应。在< 0.45 V (RHE)时,主要的氧化过程是通过未被吸附在表面的中间体进行的。电子转移是速率限制步骤。在0.55≤E≤0.75 V (RHE)时,中间体的吸附速率受限,随后发生快速电子转移。讨论了θ有机化合物在抑制主要氧化过程中的作用。提出了一种可能的电活性溶液种类。
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引用次数: 18
Laser Raman spectra of adsorbed species 吸附物质的激光拉曼光谱
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700828
P. Hendra, E. J. Loader
Experimental methods for recording laser Raman spectra of molecular species adsorbed on high surface area substrates are described. The origin of the spectra is discussed; they definitely originate from vibrations of the surface adsorbed species. Spectra of a range of adsorbates including halogens, hydrocarbons and halogenated hydrocarbons, nitriles and aldehydes adsorbed on a range of oxide surfaces are discussed. The spectra closely resemble those of the liquid if physical adsorption is involved, but considerable frequency and intensity changes occur if the molecules are chemisorbed. Raman spectroscopy has an advantage over infra-red in this field in that bands due to these adsorbents are not prominent in the spectrum. However, the method lacks sensitivity as yet and is restricted to good Raman scatterers adsorbed on high surface area adsorbents.
描述了记录吸附在高表面积衬底上的分子的激光拉曼光谱的实验方法。讨论了光谱的来源;它们肯定是由表面吸附物质的振动引起的。讨论了一系列吸附物的光谱,包括卤素、碳氢化合物和卤代烃、腈和醛在一系列氧化物表面上的吸附。如果涉及物理吸附,则光谱与液体的光谱非常相似,但如果分子被化学吸附,则会发生相当大的频率和强度变化。拉曼光谱在该领域比红外光谱具有优势,因为这些吸附剂在光谱中不突出。然而,该方法还缺乏灵敏度,并且仅限于吸附在高表面积吸附剂上的良好拉曼散射体。
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引用次数: 35
Interaction of olefins with cobalt oxide using the competitive reaction method 烯烃与氧化钴相互作用的竞争反应方法
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700877
Y. Moro-oka, M. Otsuka, A. Ozaki
The interaction of olefins with cobalt oxide catalyst during their catalytic oxidation was investigated by means of the competitive reaction method. The relative adsorption constants and the rate constants for C4 and C5 olefins were determined. The trend in the adsorption constants for the isomeric olefins was similar to that observed on nickel oxide and on 1,3,5-trinitrobenzene. Increase in the ionization potentials of the olefins resulted in a linear decrease in the logarithms of the adsorption constants. A non-dissociative π-complex having a partial positive charge was estimated for the adsorbed olefin. The role of the adsorbed intermediate in the oxidation reaction is discussed on the basis of the adsorbed state and the rate constants of the isomeric olefins.
采用竞争反应法研究了烯烃与氧化钴催化剂在催化氧化过程中的相互作用。测定了C4和C5烯烃的相对吸附常数和速率常数。对异构体烯烃的吸附常数变化趋势与对氧化镍和1,3,5-三硝基苯的吸附常数变化趋势相似。烯烃电离电位的增加导致吸附常数的对数呈线性下降。估计所吸附的烯烃具有部分正电荷的非解离π配合物。根据同分异构体烯烃的吸附状态和速率常数,讨论了吸附中间体在氧化反应中的作用。
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引用次数: 6
An application of group theory and the dipole moment correlation function to the dielectric relaxation in site models 群理论和偶极矩相关函数在场址模型中介电弛豫的应用
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700990
Graham Williams, M. Cook
The dielectric relaxation of site model systems is evaluated using group theory to solve the basic rate equations and the dipole moment correlation function to predict the dielectrically active relaxation modes and their magnitudes. A number of site models are evaluated and it is considered that this approach is a very useful alternative to earlier methods, and is to be preferred for certain models containing a large number of sites.
利用群理论求解基本速率方程,利用偶极矩相关函数预测介电活性弛豫模式及其大小,对位模型系统的介电弛豫进行了评价。对许多站点模型进行了评估,并认为这种方法是一种非常有用的替代早期方法,并且对于包含大量站点的某些模型是首选的。
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引用次数: 36
Thermodynamics of rubber elasticity at constant volume 橡胶定容弹性热力学
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701278
G. Allen, M. Kirkham, J. Padget, C. Price
Thermoelastic measurements at constant volume are reported for a series of natural rubber samples. The energy component of the stress supported by the network is more or less independent of the network cure at a value of fe/f= 0.12±0.02. The energy component of the stress is independent of whether the measurements are made in the dry or in the swollen state, despite the fact that the dry rubbers have non-Gaussian equations of state and that the swollen rubbers approach Gaussian behaviour. Flory's analysis of rubber elasticity which includes hindered internal rotation in the main polymer chain, is compared with experimental results. To a first approximation it gives the correct order of magnitude for the energy component of stress. Measurements have also been made of the pressure coefficient of stress, from which the dilation coefficient of the rubber has been calculated as a function of strain. Flory's analysis does not appear to predict this coefficient satisfactorily.
报道了一系列天然橡胶样品在等体积下的热弹性测量结果。在fe/f= 0.12±0.02时,网络支撑应力的能量分量与网络固化程度基本无关。应力的能量分量与测量是在干燥状态还是膨胀状态下进行的无关,尽管干燥橡胶具有非高斯状态方程而膨胀橡胶接近高斯行为。Flory的橡胶弹性分析,包括阻碍内旋在主聚合物链,与实验结果进行了比较。近似地说,它给出了应力的能量分量的正确数量级。还测量了应力的压力系数,由此计算出橡胶的膨胀系数作为应变的函数。弗洛里的分析似乎不能令人满意地预测这个系数。
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引用次数: 95
Plane-parallel condenser with variable electrode spacing for determination of electric permittivity of highly conducting liquids below 1 MHz. Part 1.—Theoretical considerations 测定1兆赫以下高导电性液体介电常数的可变电极间距平面平行电容器。第1部分。理论方面的考虑
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701336
F. V. D. Touw, M. Mandel
A method is described for the determination of the relative electric permittivity Iµx of highly conducting liquids below 1 MHz with a measuring cell consisting of a plane-parallel-plate condenser with variable electrode spacing. Both the electrode effects (due to the impedance of the diffuse double layer at the electrodes) and the edge effects (due to the perturbation of the uniform electric field near the edges of the plates) are taken into account in the expressions for the total capacitance and conductance of the cell. Using a series expression of the measured capacitance in negative powers of the spacing between the electrodes, Iµx can be computed from the coefficient of the linear term, if certain conditions are fulfilled. The correction methods for electrode effects only, as proposed previously by Fricke and Curtis or Shaw may lead to erroneous results.
本文描述了一种测定1 MHz以下高导电性液体相对介电常数Iµx的方法,该测量单元由可变电极间距的平面-平行板电容器组成。在电池总电容和电导的表达式中,电极效应(由于电极处扩散双层的阻抗)和边缘效应(由于靠近极板边缘的均匀电场的扰动)都被考虑在内。在满足一定条件的情况下,利用测量电容的电极间距负幂的级数表达式,可以从线性项的系数计算出Iµx。以前由Fricke和Curtis或Shaw提出的仅针对电极效应的校正方法可能导致错误的结果。
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引用次数: 24
Mercury-sensitized luminescence of some aliphatic amines 某些脂肪胺的汞致敏发光
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701360
R. Newman, C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips
Rate constants for quenching of 253.7 nm fluorescence and quantum efficiencies for emission of luminescence during mercury-sensitized photolysis have been measured for methylamine, ethylaminc, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, dimethylamine, diethylamine, trimethylamine and triethylamine. From the variation of luminescent efficiency with the structure of the amine we conclude that the main process competing with luminescence, during the reaction of Hg(3Po) with an amine, is normally the abstraction of an α-hydrogen atom. Strong σ*→n fluorescence was observed during 253.7 nm irradiation of trimethylamine, triethylamine and tri-n-propylamine.
测定了甲基胺、乙胺、正丙胺、异丙胺、正丁胺、异丁胺、叔丁胺、仲丁胺、二甲胺、二乙胺、三甲胺和三乙胺在汞敏化光解过程中253.7 nm荧光猝灭的速率常数和发光的量子效率。从发光效率随胺结构的变化可知,在汞(3Po)与胺反应过程中,与发光竞争的主要过程通常是α-氢原子的抽离。在三甲胺、三乙胺和三正丙胺辐照253.7 nm时,观察到强的σ*→n荧光。
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引用次数: 21
Kinetics of dehydration of single crystals of copper formate tetrahydrate 四水合甲酸铜单晶脱水动力学
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701467
Peter M. Fichte, T. Flanagan
Reproducible kinetic data for the dehydration of individual single crystals of copper formate tetrahydrate have been obtained from –45° to +25°C in vacuo. Although structural studies suggest the presence of two differently coordinated types of water molecule, all of the water molecules behave identically with respect to their kinetics of dehydration. The reactant/product interface penetrates into the crystal at a constant rate in only the two dimensions parallel to the planes (001) which contain the copper and formate ions. A two-dimensional contracting envelope equation describes the α(fraction dehydration) against time curves. The energy of activation, 11.2 ± 0.2 kcal/mol H2O, for penetration of the interface is less than the overall heat of dissociation, 12.5 kcal/mol H2O. The kinetics of dehydration are unaffected by an antiferroelectric transition at –37.7°C. The inhibition of the dehydration process by water vapour has been examined and discussed quantitatively.
在-45°~ +25°C的真空条件下,获得了四水合甲酸铜单晶脱水的可重复动力学数据。尽管结构研究表明存在两种不同的协调类型的水分子,但所有的水分子在脱水动力学方面的行为是相同的。反应物/生成物界面仅在平行于含有铜和甲酸离子的平面(001)的两个维度上以恒定速率渗透到晶体中。二维收缩包络方程描述了α(分数脱水)随时间的变化曲线。穿透界面的活化能为11.2±0.2 kcal/mol H2O,小于总离解热12.5 kcal/mol H2O。脱水动力学不受-37.7℃反铁电跃迁的影响。对水蒸气对脱水过程的抑制作用进行了定量的考察和讨论。
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引用次数: 17
Critical temperatures of mixtures of quasi-spherical molecules. Alicyclic hydrocarbons + benzene, + hexafluorobenzene and + perfluorocyclohexane 准球形分子混合物的临界温度。脂环烃+苯,+六氟苯和+全氟环己烷
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701605
C. P. Hicks, C. L. Young
The critical temperatures Tmc of mixtures of cyclo-alkanes (C5-C8) with benzene, hexafluorobenzene and perfluorocyclohexane have been measured. The results have been compared with the “van der Waals” model proposed by Rowlinson and co-workers. The results are consistent with the unlike interactions between cyclo-alkane + benzene, hexafluorobenzene and perfluorocyclohexane being roughly independent of the cyclo-alkane but becoming increasingly “weak” in the order : benzene, hexafluorobenzene and perfluorocyclohexane. This order is supported by the excess thermodynamic properties of liquid mixtures and second virial coefficients of related mixtures. The unlike interaction energy parameters obtained from the critical temperature data have been compared with those derived from the excess free energy of mixing at equimole fraction. The agreement is fairly good. The possible importance of the lack of balance of non-central forces is briefly discussed.
测定了环烷烃(C5-C8)与苯、六氟苯和全氟环己烷混合物的临界温度Tmc。研究结果与罗林森及其同事提出的“范德华斯”模型进行了比较。结果与环烷烃与苯、六氟苯和全氟环己烷之间的不同相互作用一致,它们大致独立于环烷烃,但在苯、六氟苯和全氟环己烷的顺序上变得越来越“弱”。这种顺序是由液体混合物的超热力学性质和相关混合物的二次维里系数支持的。从临界温度数据得到的不同的相互作用能参数与从等摩尔分数混合的多余自由能得到的相互作用能参数进行了比较。这个协议相当不错。简要讨论了非中心力缺乏平衡的可能重要性。
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引用次数: 8
Solid-liquid phase equilibria in the potassium + rubidium and the rubidium + caesium alloy systems 钾+铷和铷+铯合金体系的固液相平衡
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701612
J. Goates, J. Ott, Elizabeth Delawarde
Thermal methods were used to determine with high precision the solid-liquid phase equilibria diagram for the potassium + rubidium and the rubidium + caesium systems. Both form solid solutions of continuously varying composition with the minima in the liquidus curves occurring at 307.00 K and 0.667 mol fraction rubidium in the K + Rb system and 282.85 K and 0.530 mol fraction caesium in the Rb + Cs system. In the K + Rb system, the liquidus and solidus points are close together, giving a very narrow temperature range for the two phase region. The freezing point minimum in this system, occurring at 0.667 mol fraction Rb, suggests the possible formation of a KRb2 intermetallic compound.
采用热方法高精度地测定了钾+铷和铷+铯体系的固液平衡图。两者都形成了组成连续变化的固溶体,在K + Rb体系中,液相曲线的最小值出现在307.00 K和0.667 mol分数的铷,在Rb + Cs体系中,最小值出现在282.85 K和0.530 mol分数的铯。在K + Rb体系中,液相点和固相点靠得很近,两相区温度范围很窄。该体系的最低凝固点出现在0.667 mol分数Rb,表明可能形成KRb2金属间化合物。
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引用次数: 10
期刊
Transactions of The Faraday Society
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