Transactions of The Faraday Society最新文献_第5页

Vibrational relaxation of carbon monosulphide 单硫化碳的振动弛豫

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702575

C. Morley, Ian W. M. Smith

引用次数: 15

Reactions of group III metalalkyls in the gas phase. Part 3.—Kinetics of the intramolecular elimination of but-1-ene from di-n-alkyl-n-butyl aluminium III族金属烷基在气相中的反应。第3部分。-二烷基正丁基铝分子内消除丁烯的动力学

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702629

K. Egger, A. Cocks

{"title":"Reactions of group III metalalkyls in the gas phase. Part 3.—Kinetics of the intramolecular elimination of but-1-ene from di-n-alkyl-n-butyl aluminium","authors":"K. Egger, A. Cocks","doi":"10.1039/TF9716702629","DOIUrl":"https://doi.org/10.1039/TF9716702629","url":null,"abstract":"The gas phase kinetics and the mechanistics of the unimolecular elimination of but-1-ene from a mixture of methyldi-n-butylaluminium and n-butyldimethylaluminium have been studied in the presence of excess ethylene in the temperature range 401–478 K. The observed rate constants for the apparently homogeneous elimination reaction yield (with standard errors) log k(s–1)=(10.85 ± 0.18)–(27.80±0.36)/θ, where θ equals 4.58 × 10–3T in kcal mol–1[=(10.85 ± 0.18)–(116.3±1.5)/19.15 × 10–3T in kJ mol–1] resulting in a negative intrinsic entropy of activation of 13.0 cal K–1 mol–1[54.4 JK–1 mol–1]. These data when compared with the corresponding activation parameters reported earlier for tri-isobutylaluminium substantiate the concept of a tight polar four-centre cyclic transition state. The apparent stabilizing effect of a methyl group on the positively charged carbon centre in the transition state is only 1.2 kcal mol–1. Available thermodynamic data are used to derive intrinsic ΔH°f-increment values for this class of compounds, resulting in an estimated activation energy for the back reaction, the addition of 1-butene to di-n-alkylaluminium hydride, of ∼5.2 kcal mol–1.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2629-2637"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702629","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57629101","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

Liquid density and excess properties of argon + krypton and krypton + xenon binary liquid mixtures, and liquid density of ethane 氩+氪和氪+氙二元液体混合物的液体密度和过剩性能，以及乙烷的液体密度

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702933

Chen-Hwa Chui, F. Canfield

引用次数: 34

Thermodynamics of silicon sulphides and zinc sulphide 硫化硅和硫化锌的热力学

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702945

T. Rosenqvist, K. Tungesvik

引用次数: 5

Infra-red cryogenic studies. Part 6.—Deuterium chloride in argon and other matrices 红外线低温研究。第6部分。-氩和其他基质中的氯化氘

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703176

J. Davies, H. E. Hallam

{"title":"Infra-red cryogenic studies. Part 6.—Deuterium chloride in argon and other matrices","authors":"J. Davies, H. E. Hallam","doi":"10.1039/TF9716703176","DOIUrl":"https://doi.org/10.1039/TF9716703176","url":null,"abstract":"Infra-red spectra are reported of DCl in a variety of matrices at 20 K. At low DCl concentrations, absorptions due to monomeric DCl are observed. Hindered rotation is observed in three matrices which offer spherically symmetrical substitutional sites (Ar, Kr, SF6) and assignments are made to the vibration-rotation lines including R(2) and P(2). The rotational spacing for DCl decreases less from gas to matrix than for HCl as predicted by a rotational-translational coupling model. Rotation is not observed in matrices offering cylindrical substitutional sites (N2, CO2, CO) or in CH4. Matrix-induced frequency shifts show a similar behaviour to those of HCl. A detailed study has been made of the association of DCl in argon matrices and the two dominant multimer bands that arise are assigned to cyclic dimer and cyclic trimer. Further bands assigned to higher multimers agree well with predictions from an intermolecular resonance interaction model, though detailed study of HCl—DCl mixed multimers in argon shows that this model is only fully successful in dealing with trimers and higher multimers. Spectra of binary mixtures of DCl/X in Ar(X = N2, CO2 and CO) show three groups of induced bands arising from DCl—X, (DCl)2—X and DCl—X—DCl interactions. With N2 and CO2 the interactions are thought to be largely electrostatic but CO has a much stronger effect suggesting a specific hydrogen-bond interaction involving the oxygen atom.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3176-3190"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703176","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57631746","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

Measurements of heats of combustion by flame calorimetry. Part 7.—Chloromethane, chloroethane, 1-chloropropane, 2-chloropropane 用火焰量热法测量燃烧热。第7部分。-氯甲烷，氯乙烷，1-氯丙烷，2-氯丙烷

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703191

R. Fletcher, G. Pilcher

引用次数: 23

Infra-red study of hydrogen chloride adsorption on rutile surfaces 金红石表面氯化氢吸附的红外研究

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703100

G. D. Parfitt, J. Ramsbotham, C. H. Rochester

引用次数: 27

Adsorption of sodium dodecyl sulphate at the silicone fluid/water interface 十二烷基硫酸钠在硅酮液/水界面的吸附

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703127

A. Kanellopoulos, M. Owen

{"title":"Adsorption of sodium dodecyl sulphate at the silicone fluid/water interface","authors":"A. Kanellopoulos, M. Owen","doi":"10.1039/TF9716703127","DOIUrl":"https://doi.org/10.1039/TF9716703127","url":null,"abstract":"The adsorption of sodium dodecyl sulphate (SDS) was studied at silicone fluid/water interfaces at 297 K, as a function of siloxane chain length, surfactant concentration, in the presence of electrolytes and in mixtures with fatty alcohols or silanols. Although the interfacial tensions against water of dimethylpolysiloxanes with 2 to ∼13 siloxane units was constant at around 42.6 mNm–1, the adsorption of SDS at the dimethylpolysiloxane/water interface depended slightly on the number of siloxane units of the fluid, i.e., the limiting surface area per SDS molecule increased from 0.551 nm2 for 3 siloxane units to 0.623 nm2 for ∼13 siloxane units. Similarly, changes were observed for the surface excess (decrease with number of siloxane units) and interfacial tension above the critical micelle concentration (c.m.c)(increase with number of siloxane units) but the c.m.c. did not show any systematic change with the number of siloxane units. In the presence of electrolytes, NaCl and CuCl2, the plot of log (c.m.c.) against log [counter ions] was a straight line with a slope of 0.68. When SDS and fatty alcohols or silanols were simultaneously adsorbed at the silicone fluid/water interface there was no indication from the interfacial tension lowering of the system of molecular interaction between them.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3127-3138"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703127","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632084","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: 42

Reactions of cyanogen radicals with hydrocarbons 氰基与碳氢化合物的反应

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703258

G. Bullock, R. Cooper

引用次数: 8

Specific adsorption of fluoride ions on mercury and the structure of the mercury/solutions interface 氟离子在汞上的特异性吸附及汞/溶液界面的结构

Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703318

D. Schiffrin

引用次数: 79