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Phase-shift studies of Hg(3 P 0) reactions. Part 3.?Complexes of Hg(3 P 0) with some primary amines 汞(3p0)反应的相移研究。第3部分。Hg(3p0)与某些伯胺的配合物
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/tf9716703247
C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips
{"title":"Phase-shift studies of Hg(3 P 0) reactions. Part 3.?Complexes of Hg(3 P 0) with some primary amines","authors":"C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips","doi":"10.1039/tf9716703247","DOIUrl":"https://doi.org/10.1039/tf9716703247","url":null,"abstract":"Rate constants for bimolecular and termolecular reactions with Hg(3P0), lifetimes of complexes with Hg(3P0), and lower limits for dissociation energies of complexes with Hg(3P0), have been determined for ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine and tert-butylamine. These results, when supplemented by previous values for the quantum efficiencies of mercury-sensitized luminescence, allow us to assess the relative importance of Hg(3P0) in the sensitized decompositions of amines.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3247"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/tf9716703247","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632545","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
Kinetics of oxidation of α-hydroxyisobutyric acid by aquomanganese (III) ions in aqueous perchlorate media 高氯酸水溶液中水锰离子氧化α-羟基异丁酸的动力学研究
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703297
C. F. Wells, C. Barnes
{"title":"Kinetics of oxidation of α-hydroxyisobutyric acid by aquomanganese (III) ions in aqueous perchlorate media","authors":"C. F. Wells, C. Barnes","doi":"10.1039/TF9716703297","DOIUrl":"https://doi.org/10.1039/TF9716703297","url":null,"abstract":"The kinetics of the oxidation of α-hydroxyisobutyric acid by aquomanganese(III) ions have been investigated in aqueous perchlorate media using conventional and stopped-flow spectrophotometry. The acidity range is more restricted than that used for the oxidation of other organic substrates by MnIIIaq as the MnII added to maintain the ionic strength at µ= 4.00 and to suppress the formation of MnIV has a small effect on the rate at [HClO4]⩽ 1.0 M. The rate-determining step involves the decomposition of an intermediate complex, Mn3+(CH3)2COHCOOHaq, and the overall energy E and entropy ΔS* of activation are compared with E and ΔS* for other organic substrates oxidized by MnIIIaq: the high reactivity of α-hydroxyisobutyric acid arises from the high positive ΔS* derived from chelation. A value is estimated for the protonation constant of α-hydroxyisobutyric acid.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3297-3305"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703297","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632653","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: 2
Specular reflectance and ellipsometric spectroscopy of oriented molecular layers 定向分子层的镜面反射率和椭偏光谱
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703306
M. Dignam, M. Moskovits, R. W. Stobie
{"title":"Specular reflectance and ellipsometric spectroscopy of oriented molecular layers","authors":"M. Dignam, M. Moskovits, R. W. Stobie","doi":"10.1039/TF9716703306","DOIUrl":"https://doi.org/10.1039/TF9716703306","url":null,"abstract":"Assuming an oriented molecular layer to behave optically as a homogeneous, uniaxial medium with its optic axis normal to the interface, such a system is treated theoretically to yield equations relevant to both specular reflectance and ellipsometric spectroscopy. Explicit expressions are derived for the empirical quantities (relating them to the optical constants of the media and other system parameters) which are both reasonably simple and correct to second-order terms in the film thickness. From ellipsometric measurements alone, it is not possible to distinguish between very thin uniaxial and isotropic films. However, data for a very thin non-absorbing uniaxial film on an absorbing substrate (e.g., a metal), if analyzed on the assumption of film isotropy, lead to an apparent absorption index for the film of the magnitude of the absorption index found for semi-conductors. A similar result is predicted for specular reflectance measurements, except that in that case the apparent optical constants of the film depend on the angle of incidence.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3306-3317"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703306","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632695","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: 99
Partial molal enthalpies, excess partial molal heat capacities and structural effects of Bu4NBr and NaBPh4 in aqueous binary solvent mixtures 双溶剂水溶液中丁腈丁烷和NaBPh4的偏摩尔焓、偏摩尔热容及结构效应
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700305
R. K. Mohanty, T. S. Sarma, S. Subramanian, J. C. Ahluwalia
{"title":"Partial molal enthalpies, excess partial molal heat capacities and structural effects of Bu4NBr and NaBPh4 in aqueous binary solvent mixtures","authors":"R. K. Mohanty, T. S. Sarma, S. Subramanian, J. C. Ahluwalia","doi":"10.1039/TF9716700305","DOIUrl":"https://doi.org/10.1039/TF9716700305","url":null,"abstract":"Integral heats of solution of Bu4NBr in aqueous binary solvent mixtures (containing 0.0 to 0.30 mol fraction of consolvent) of t-butanol, acetone, dioxan and ethylene glycol were determined at 15, 25, and 35°C. Integral heats of solution of NaBPh4 in the same aqueous binary solvents containing 20 % by volume (about 0.05 mol fraction) of cosolvent were also determined at 15, 25 and 35°C. Corresponding excess partial molal heat capacities Δtext-decoration:overlineC°p were derived at 20 and 30°C. The partial molal enthalpies Δtext-decoration:overlineH°s of Bu4 NBr increased (sharply in aqueous t-butanol up to 0.06 mol fraction) with the addition of increasing amount of cosolvent to water till the maximum value was attained at 0.1–0.3 mol fraction of cosolvent. The endothermicity maxima Δtext-decoration:overlineH°smax were in the decreasing order of t-butanol > acetone > ethylene glycol > dioxan. text-decoration:overlineH°smax decreased with increasing temperatures in all aqueous binary solvents. text-decoration:overlineC°p results indicate that addition of small amounts of t-butanol and acetone stabilize the water structure, the maximum stabilization occurring around 0.04 mol fraction of acetone and t-butanol. Further addition of t-butanol to 0.06 mol fraction results in complete collapse of the water structure, whereas further addition of acetone results in gradual breakdown of the water structure which continues up to 0.3 mol fraction of acetone. Dioxan and ethylene glycol seem to have net structure breaking influence on the water structure.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"305-315"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700305","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57613871","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
Orthonormal chemical reactions and chemical relaxation. Part 3.—Reactions in solution under various thermodynamic conditions 标准正态化学反应和化学松弛。第3部分。-不同热力学条件下溶液中的反应
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703240
H. Hayman
{"title":"Orthonormal chemical reactions and chemical relaxation. Part 3.—Reactions in solution under various thermodynamic conditions","authors":"H. Hayman","doi":"10.1039/TF9716703240","DOIUrl":"https://doi.org/10.1039/TF9716703240","url":null,"abstract":"The method described previously 2 for obtaining the relaxation times, normal coordinates and normal modes of relaxation of a non-ideal chemical system at constant temperature and pressure is extended to relaxation under adiabatic conditions and/or at constant volume; in each case the normal modes of relaxation are obtained as an orthonormal set satisfying orthonormality conditions similar to those pertaining to constant temperature and pressure. First-order perturbation theory is used for evaluating the various corrections required when the simple dilute-solution theory 1 is used at concentrations which are too high for the theory to be strictly applicable.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3240-3246"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703240","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632408","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: 4
Degrees of association of n-pentyl lithium and n-octyl lithium in benzene 苯中正戊基锂和正辛基锂的缔合度
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700353
D. Margerison, J. D. Pont
{"title":"Degrees of association of n-pentyl lithium and n-octyl lithium in benzene","authors":"D. Margerison, J. D. Pont","doi":"10.1039/TF9716700353","DOIUrl":"https://doi.org/10.1039/TF9716700353","url":null,"abstract":"The degrees of association of n-pentyl lithium and n-octyl lithium in benzene at 30°C have been measured using the method of vapour pressure lowering. The value from n-pentyl lithium is 6.00 ± 0.09 [degrees of freedom (D.F.)]= 13]; the value for n-octyl lithium is 5.953 ± 0.016 (D.F. = 9). It is argued that the two compounds exist predominantly as hexamers in solution.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"353-359"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700353","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57614313","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: 13
Predissociation by the continuum of a bound state without curve crossing. Application to the spectrum of OH 通过无曲线交叉的束缚态连续体预解离。OH光谱的应用
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703395
S. Durmaz, J. Murrell
{"title":"Predissociation by the continuum of a bound state without curve crossing. Application to the spectrum of OH","authors":"S. Durmaz, J. Murrell","doi":"10.1039/TF9716703395","DOIUrl":"https://doi.org/10.1039/TF9716703395","url":null,"abstract":"Calculations of the Franck-Condon overlaps between the bound vibrational levels of the A2∑+ state of OH and the continuum levels of the ground state X2Π suggest that the weak predissociation of the levels ν= 2-5 could be due to a direct predissociation to the ground state and not to the crossing by another excited state. Accurate measurements of the intensity of the emission lines could test this hypothesis.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3395-3398"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703395","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57633361","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
Chemical reactions with accelerated ions. Chemical effects of 32P+-ions implanted in NaCl single crystals 与加速离子的化学反应。32P+离子注入NaCl单晶的化学效应
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703540
T. Andersen, A. Ebbesen
{"title":"Chemical reactions with accelerated ions. Chemical effects of 32P+-ions implanted in NaCl single crystals","authors":"T. Andersen, A. Ebbesen","doi":"10.1039/TF9716703540","DOIUrl":"https://doi.org/10.1039/TF9716703540","url":null,"abstract":"An electromagnetic isotope separator has been used for implantation of 40 keV 32P+ ions in single crystals of sodium chloride. The penetration of the implanted ions and their diffusion during storage at various temperatures have been measured by a new chemical sectioning technique. The chemical distribution of the 32P-ions has been determined after dissolution of the crystals. It reflects the variation in range distribution observed by varying the angle between the incident beam and the (100) plane. Deeply penetrating tails have a high content of the 32P(V)-precursor. A close correlation is established between the 32P(V)-precursor and changes in the range distribution due to diffusion. The chemical distribution depends to some extent on reactions occurring during dissolution. Thermal- and photo-annealing show the existence of two 32P(I)-precursors.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3540-3549"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703540","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57635077","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
Ion-exchange equilibria of synthetic 4A zeolite with Ni2+, Co2+, Cd2+ and Zn2+ ions 合成4A沸石与Ni2+、Co2+、Cd2+和Zn2+离子的离子交换平衡
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700999
I. Gal, O. Janković, S. Malčić, P. Radovanov, M. Todorović
{"title":"Ion-exchange equilibria of synthetic 4A zeolite with Ni2+, Co2+, Cd2+ and Zn2+ ions","authors":"I. Gal, O. Janković, S. Malčić, P. Radovanov, M. Todorović","doi":"10.1039/TF9716700999","DOIUrl":"https://doi.org/10.1039/TF9716700999","url":null,"abstract":"Linde 4A zeolite was converted to Ni, Co, Zn and Cd forms by replacing sodium ions with divalent cations. The replacement was from 82%(Ni) up to 100%(Cd). Chemical, T.G.A., D.T.A. and X-ray analysis of the divalent metal zeolites have been made and data on the composition of the unit cells and the thermal stability of the lattices were obtained. Ni-zeolite is unstable, its crystal lattice being completely destroyed above 70°C, whereas Co-, Zn- and Cd-zeolites are stable up to 750–850°C. The adsorption of water on the latter zeolites is reversible. Ion-exchange isotherms for Co2+, Zn2+ and Cd2+ at three temperatures were obtained and the thermodynamic functions, ΔG°, ΔH° and ΔS°, of the ion-exchange equilibria calculated. The thermodynamic data are discussed with respect to hydration and size of the cations. A possible explanation of the instability of Ni-zeolite is suggested.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"999-1008"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700999","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57617242","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: 48
Ultra-violet spectrum of SiBr SiBr的紫外光谱
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701870
G. Oldershaw, K. Robinson
{"title":"Ultra-violet spectrum of SiBr","authors":"G. Oldershaw, K. Robinson","doi":"10.1039/TF9716701870","DOIUrl":"https://doi.org/10.1039/TF9716701870","url":null,"abstract":"The absorption spectrum of SiBr, observed in the flash photolysis of SiBr4, consists of the B2Σ—X2Π system and a number of new band systems at shorter wavelengths. One of these is shown to be analogous to the C2Π—X2Π systems of SiF and SiCl, and state C has the following parameters : Te= 41 051 cm–1, A= 12 cm–1, ωe= 531 cm–1, ωexe= 2 cm–1. Analyses of the remaining band systems are also discussed.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1870-1874"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701870","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57623826","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
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