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Effect of thallous ions on the yields of hydrogen and hydrogen peroxide in radiolyzed aqueous solutions 硫离子对辐射分解水溶液中氢和过氧化氢产率的影响
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702057
M. Faraggi, D. Zehavi, M. Anbar
{"title":"Effect of thallous ions on the yields of hydrogen and hydrogen peroxide in radiolyzed aqueous solutions","authors":"M. Faraggi, D. Zehavi, M. Anbar","doi":"10.1039/TF9716702057","DOIUrl":"https://doi.org/10.1039/TF9716702057","url":null,"abstract":"The radiolysis of Tl2SO4 in neutral and in 0.8 N H2SO4 aqueous solutions in the presence and absence of air was investigated. In the absence of air and with low doses of radiation, a steady-state concentration of H2O2 is observed. In air-saturated solution G(H2O2) decreases with Tl+ concentration. The effect of Tl+ on GH2O2 was measured by two independent methods, following G(H2O2) in aerated solutions and by measuring G(H2O218, 18) formed in H2O18 in the presence of H2O216, 16 as protective additive. In neutral and acid solutions, G(H2)=GH2= 0.42±0.02, which was independent of Tl+ concentration. The relatively high efficiency of Tl+ for scavenging the precursor of H2O2 is discussed and compared with that of other reactants known to diminish GH2O2. The mode of formation of the “molecular” products in the radiolysis of water is discussed in the light of the findings.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2057-2067"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57625610","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: 14
Dilute aqueous solutions of unsymmetrical quaternary ammonium iodides. Part 1.—Viscosity and density measurements 不对称季铵盐的稀水溶液。第1部分。-粘度和密度测量
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702318
B. M. Lowe, H. M. Rendall
{"title":"Dilute aqueous solutions of unsymmetrical quaternary ammonium iodides. Part 1.—Viscosity and density measurements","authors":"B. M. Lowe, H. M. Rendall","doi":"10.1039/TF9716702318","DOIUrl":"https://doi.org/10.1039/TF9716702318","url":null,"abstract":"Viscosity and density measurements at 25°C on solutions of small straight-chain and cyclic quaternary ammonium iodides, and on methyl and ethyl pyridinium iodide are reported. The derived apparent molal volumes ϕ°ν and viscosity B-coefficients Bη change by constant amounts (0.015 dm3 mol–1 and 0.067 dm3 mol–1 respectively) per CH2 group for all except the pyridinium salts, and are related by the equation Bη= 4.6 ϕ°ν–0.54.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2318-2327"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702318","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57627526","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: 29
Effect of matrix rigidity on the reactions of aromatic nitrenes in polymers 基体刚性对聚合物中芳香族亚硝基烯反应的影响
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702389
A. Reiser, L. Leyshon, L. Johnston
{"title":"Effect of matrix rigidity on the reactions of aromatic nitrenes in polymers","authors":"A. Reiser, L. Leyshon, L. Johnston","doi":"10.1039/TF9716702389","DOIUrl":"https://doi.org/10.1039/TF9716702389","url":null,"abstract":"The main products of the photolysis of aromatic azides in matrices of polystyrene, paraffin wax, polyisoprene and some other polymers are primary and secondary amines. The yield of secondary amine in the matrix depends strongly on the rigidity of the polymeric system. Matrix rigidity affects also the reaction kinetics of the nitrene intermediate, lifetimes of photogenerated triplet nitrenes being up to three orders of magnitude longer in rigid matrices than in plasticized materials. From the results of flash photolysis experiments, it is concluded that in the rigid matrix the rate of interaction between a reactive species and the polymer is not controlled by the chemical reactivities of reactant and substrate, but by a steric rearrangement of the polymer chain in the vicinity of the reactive site.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2389-2396"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702389","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57627862","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: 27
Antiferromagnetic interactions in bis(dimethylsulphoxide)copper(II) chloride 双(二甲基亚砜)氯化铜(II)的反铁磁相互作用
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702431
N. T. Watkins, D. Jeter, W. Hatfield, S. M. Horner
{"title":"Antiferromagnetic interactions in bis(dimethylsulphoxide)copper(II) chloride","authors":"N. T. Watkins, D. Jeter, W. Hatfield, S. M. Horner","doi":"10.1039/TF9716702431","DOIUrl":"https://doi.org/10.1039/TF9716702431","url":null,"abstract":"The magnetic susceptibility of bis(dimethylsulphoxide)copper(II) chloride has been measured in the temperature range 4.2–298 K. Antiferromagnetic interactions were observed at very low temperatures. The data are interpreted in terms of electron spin interactions along an infinite chain of copper(II) atoms.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2431-2435"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702431","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628019","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: 11
Phase-shift studies of Hg(3P0) reactions. Part 2.—Complexes of Hg(3P0) with water and alcohols Hg(3P0)反应的相移研究。第2部分。- Hg(3P0)与水和醇的配合物
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702567
C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips
{"title":"Phase-shift studies of Hg(3P0) reactions. Part 2.—Complexes of Hg(3P0) with water and alcohols","authors":"C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips","doi":"10.1039/TF9716702567","DOIUrl":"https://doi.org/10.1039/TF9716702567","url":null,"abstract":"Radiative lifetimes, lower limits for dissociation energies, and rate constants for formation by bimolecular and termolecular reactions, have been determined for the excited complexes of Hg(3P0) with H2O, D2O, and a number of alcohols. The results are discussed in terms of the alternative processes that can occur during reaction of an R—OH molecule with Hg(3P0).","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2567-2574"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702567","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628959","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
Measurement of steric stabilizer barrier thickness in dispersions of poly(methyl methacrylate) in aliphatic hydrocarbon 脂肪族烃中聚甲基丙烯酸甲酯分散体中立体稳定剂阻挡层厚度的测定
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703598
S. J. Barsted, L. J. Nowakowska, I. Wagstaff, D. J. Walbridge
{"title":"Measurement of steric stabilizer barrier thickness in dispersions of poly(methyl methacrylate) in aliphatic hydrocarbon","authors":"S. J. Barsted, L. J. Nowakowska, I. Wagstaff, D. J. Walbridge","doi":"10.1039/TF9716703598","DOIUrl":"https://doi.org/10.1039/TF9716703598","url":null,"abstract":"The thickness of a surface layer of poly(12-hydroxy-stearic acid) stabilizing a dispersion of poly(methylmethacrylate) particles in aliphatic hydrocarbon has been found by a hydrodynamic technique to be 6.2 nm. However, from the point of view of steric stabilization against flocculation, the thickness of a layer of solvated unfractionated polymer may be more closely related to the dimensions of the larger molecular species present. From calculations based upon gel permeation chromatography these molecules could extend at least 15 nm from the particle surface. This prediction is in good agreement with recent determinations of the steric thickness of the layer of solvated polymer.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3598-3603"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703598","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57673395","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: 37
Chlorine abstraction reactions of fluorine. Part 1.—Reaction of fluorine with trichlorofluoromethane 氟的氯萃取反应。第1部分。-氟与三氯氟甲烷的反应
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703038
R. Foon, K. Tait
{"title":"Chlorine abstraction reactions of fluorine. Part 1.—Reaction of fluorine with trichlorofluoromethane","authors":"R. Foon, K. Tait","doi":"10.1039/TF9716703038","DOIUrl":"https://doi.org/10.1039/TF9716703038","url":null,"abstract":"The kinetics and mechanism of the reaction of fluorine with CCl3F have been investigated in a static system over the temperature range 491–598 K. The reaction was at least partly heterogeneous, independent of surface area to volume ratio, independent of diluent and uninhibited by either oxygen or chlorine monofluoride. The rate equation had the form : –d[CCl3F]/dt=k[F2]½[CCl3F]. The rate constants were reproducible using different Pyrex reaction vessels and fitted the Arrhenius equation : log k(l.½ mol–½ s–1)=(6.77 ± 0.10)–(19 250 ± 240)/2.303 RT. A full mechanism is presented which, by using steady-state assumptions, agrees with the experimentally derived rate equation.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3038-3045"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57631430","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: 3
Gas-phase pyrolysis of 1,2-dichloropropane 1,2-二氯丙烷的气相热解
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700080
K. A. Holbrook, J. S. Palmer
{"title":"Gas-phase pyrolysis of 1,2-dichloropropane","authors":"K. A. Holbrook, J. S. Palmer","doi":"10.1039/TF9716700080","DOIUrl":"https://doi.org/10.1039/TF9716700080","url":null,"abstract":"The gas-phase pyrolysis of 1,2-dichloropropane has been studied at temperatures from 393 to 470°C and initial pressures from 0.2 to 26.0 Torr. In a 1-1. silica reaction vessel of low surface/volume ratio, the products are the four monochloropropenes and hydrogen chloride. Above 440°C the product ratios show only a small dependence on temperature and the relative amounts of the various isomers at 457°C are (expressed as percentage of the total chloropropenes), 3-chloropropene 63.6%, cis-1-chloropropene 22.9 %, trans-1-chloropropene 12.7 %, 2-chloropropene 0.8 %. The overall reaction is closely represented by the pressure change which leads to the overall rate-constant log10k(s–1)=(13.78 ±0.21)–(54 760 ±440)/4.576 T. Arrhenius parameters have been derived for each of the chloropropene products from the above expression and the product ratios at various temperatures (extrapolated to zero time). Additions of small amounts of nitric oxide and propene had virtually no effect upon the overall rate. The reaction has also been studied at low temperatures (300–380°C) and in various packed reaction vessels. The product ratios (extrapolated to zero time and corrected for the concurrent homogeneous reaction at the higher temperatures) show increased proportions of 2-chloropropene and cis-1-chloropropene and also formation of propene which can constitute up to 15 mol % of the total organic products. The results are consistent with four parallel unimolecular reactions occurring homogeneously at high temperatures. The heterogeneous reactions are more complicated although similarities are noted with the elimination reactions of other alkyl halides at glass surfaces.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"80-87"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700080","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57612884","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: 9
Identification of oxygen species adsorbed on reduced titanium dioxide 还原二氧化钛吸附氧的种类鉴定
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700506
C. Naccache, P. Mériaudeau, M. Che, A. J. Tench
{"title":"Identification of oxygen species adsorbed on reduced titanium dioxide","authors":"C. Naccache, P. Mériaudeau, M. Che, A. J. Tench","doi":"10.1039/TF9716700506","DOIUrl":"https://doi.org/10.1039/TF9716700506","url":null,"abstract":"The nature of oxygen adsorbed on slightly reduced TiO2 has been investigated using oxygen enriched with 17O2. On anatase, the oxygen adsorbs as O–2 with a hyperfine splitting Axx about g3 of 77 G; no structure could be resolved for Ayy and Azz. On rutile, oxygen adsorbs as O–2 on two sites of different thermal stability; (I) with g1= 2.030, g2= 2.008, g3= 2.004 and Axx= 76 G, and (II) with g1= 2.020, g2= 2.009, g3= 2.003 and Axx= 72 G. The evidence indicates that O–2 exists in a largely ionic form on TiO2 and other oxides. A symmetrical line at g= 2.003 which appears on some anatase samples after oxygen adsorption is attributed to the localization of a conduction electron by the adsorbed oxygen.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"506-512"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700506","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57614834","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: 139
Investigation of lipid + water systems. Part 4.—Proton magnetic resonance in an ordered lyotropic mesophase 脂质+水系统的研究。第4部分。-质子磁共振在一个有序的溶性中间相
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716700890
M. P. Mcdonald, W. Peel
{"title":"Investigation of lipid + water systems. Part 4.—Proton magnetic resonance in an ordered lyotropic mesophase","authors":"M. P. Mcdonald, W. Peel","doi":"10.1039/TF9716700890","DOIUrl":"https://doi.org/10.1039/TF9716700890","url":null,"abstract":"P.m.r. measurements have been made on macroscopically-ordered samples of the smectic mesophase which occurs in the mono-octanoin + water system. The angular dependence of the doublet splittings obtained from both alkyl chain and hydroxyl protons indicate that there is a measurable degree of molecular ordering along a direction perpendicular to the lamellar planes of the mesophase. The degree of ordering of the alkyl chains is similar to that previously observed in magnetically-ordered nematic mesophases. The ordering of the water molecules is much smaller in magnitude and comparable to that previously observed in some hydrated silicates and fibrous materials.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"890-896"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716700890","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57617082","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: 11
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