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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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700801
A. H. Taylor, R. Pearce, S. Brummer
{"title":"Effect of adsorbed layers on the anodic oxidation of simple organic compounds. Part 2.—Role of adsorbed HCOOH species","authors":"A. H. Taylor, R. Pearce, S. Brummer","doi":"10.1039/TF9716700801","DOIUrl":"https://doi.org/10.1039/TF9716700801","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"801-808"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700801","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57616080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 18
Laser Raman spectra of adsorbed species 吸附物质的激光拉曼光谱
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700828
P. Hendra, E. J. Loader
{"title":"Laser Raman spectra of adsorbed species","authors":"P. Hendra, E. J. Loader","doi":"10.1039/TF9716700828","DOIUrl":"https://doi.org/10.1039/TF9716700828","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"828-840"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700828","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57616608","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700877
Y. Moro-oka, M. Otsuka, A. Ozaki
{"title":"Interaction of olefins with cobalt oxide using the competitive reaction method","authors":"Y. Moro-oka, M. Otsuka, A. Ozaki","doi":"10.1039/TF9716700877","DOIUrl":"https://doi.org/10.1039/TF9716700877","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"877-883"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700877","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57616998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700990
Graham Williams, M. Cook
{"title":"An application of group theory and the dipole moment correlation function to the dielectric relaxation in site models","authors":"Graham Williams, M. Cook","doi":"10.1039/TF9716700990","DOIUrl":"https://doi.org/10.1039/TF9716700990","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"175 1","pages":"990-998"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700990","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57617218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 36
Thermodynamics of rubber elasticity at constant volume 橡胶定容弹性热力学
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701278
G. Allen, M. Kirkham, J. Padget, C. Price
{"title":"Thermodynamics of rubber elasticity at constant volume","authors":"G. Allen, M. Kirkham, J. Padget, C. Price","doi":"10.1039/TF9716701278","DOIUrl":"https://doi.org/10.1039/TF9716701278","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1278-1292"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701278","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57618354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701336
F. V. D. Touw, M. Mandel
{"title":"Plane-parallel condenser with variable electrode spacing for determination of electric permittivity of highly conducting liquids below 1 MHz. Part 1.—Theoretical considerations","authors":"F. V. D. Touw, M. Mandel","doi":"10.1039/TF9716701336","DOIUrl":"https://doi.org/10.1039/TF9716701336","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1336-1342"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701336","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57618750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 24
Mercury-sensitized luminescence of some aliphatic amines 某些脂肪胺的汞致敏发光
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701360
R. Newman, C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips
{"title":"Mercury-sensitized luminescence of some aliphatic amines","authors":"R. Newman, C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips","doi":"10.1039/TF9716701360","DOIUrl":"https://doi.org/10.1039/TF9716701360","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1360-1364"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701360","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57619364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701467
Peter M. Fichte, T. Flanagan
{"title":"Kinetics of dehydration of single crystals of copper formate tetrahydrate","authors":"Peter M. Fichte, T. Flanagan","doi":"10.1039/TF9716701467","DOIUrl":"https://doi.org/10.1039/TF9716701467","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1467-1479"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701467","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57620221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701605
C. P. Hicks, C. L. Young
{"title":"Critical temperatures of mixtures of quasi-spherical molecules. Alicyclic hydrocarbons + benzene, + hexafluorobenzene and + perfluorocyclohexane","authors":"C. P. Hicks, C. L. Young","doi":"10.1039/TF9716701605","DOIUrl":"https://doi.org/10.1039/TF9716701605","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1605-1611"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701605","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57620758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701612
J. Goates, J. Ott, Elizabeth Delawarde
{"title":"Solid-liquid phase equilibria in the potassium + rubidium and the rubidium + caesium alloy systems","authors":"J. Goates, J. Ott, Elizabeth Delawarde","doi":"10.1039/TF9716701612","DOIUrl":"https://doi.org/10.1039/TF9716701612","url":null,"abstract":"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.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1612-1616"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701612","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57620825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 10
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