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High field pulse measurements of the electric anisotropy of polarizability and the electric dipole moment of poly-γ-benzyl-L-glutamate 聚γ-苄基-谷氨酸的电各向异性极化率和电偶极矩的高场脉冲测量
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701630
M. Gregson, G. Jones, M. Davies
{"title":"High field pulse measurements of the electric anisotropy of polarizability and the electric dipole moment of poly-γ-benzyl-L-glutamate","authors":"M. Gregson, G. Jones, M. Davies","doi":"10.1039/TF9716701630","DOIUrl":"https://doi.org/10.1039/TF9716701630","url":null,"abstract":"High electric field pulse measurements have been made on dilute solutions of poly-γ-benzyl-L-glutamate (PBLG) in trans-1,2-dichlorethylene(I) and dioxan(II). One millisecond pulses of field amplitude up to 60 kV/cm have been used and the resulting changes in permittivity measured at 6 MHz. The measurements, which are analogous to Kerr effect birefringence work, yield values of the dipole moment and anisotropy of polarizability for PBLG. The values of the apparent dipole moment are 1930 D for (I) and 1410 D for (II), while the effective molecular anisotropy (α∥–α⊥) is 8.3 × 10–21cm3 for (I) and 10.5 × 10–21 cm3 for (II). Dispersion measurements on solution (I) led to a dipole moment of 1780 D.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1630-1636"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701630","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57621465","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: 19
Shear viscoelastic relaxation of a nitrate melt 硝酸熔体的剪切粘弹性松弛
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716701960
G. Glover, A. J. Matheson
{"title":"Shear viscoelastic relaxation of a nitrate melt","authors":"G. Glover, A. J. Matheson","doi":"10.1039/TF9716701960","DOIUrl":"https://doi.org/10.1039/TF9716701960","url":null,"abstract":"The viscoelastic behaviour of a melt containing 62 mol % KNO3 and 38 mol % Ca(NO3)2 has been studied between 330 and 450 K using shear waves of frequencies 75 and 160 kHz and 5 and 30 MHz. The relaxation mechanism does not change over this range of temperature and frequency. Results may be described by a viscoelastic analogue of the Cole-Davidson expression for dielectric relaxation. This relationship also fits other common forms of viscoelastic behaviour such as that described by Barlow, Erginsav and Lamb.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"41 1","pages":"1960-1970"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701960","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57624246","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: 15
Reactions of atomic carbon C(23PJ) by kinetic absorption spectroscopy in the vacuum ultra-violet 原子碳C(23PJ)在真空紫外线下的动力学吸收光谱研究
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702025
D. Husain, L. Kirsch
{"title":"Reactions of atomic carbon C(23PJ) by kinetic absorption spectroscopy in the vacuum ultra-violet","authors":"D. Husain, L. Kirsch","doi":"10.1039/TF9716702025","DOIUrl":"https://doi.org/10.1039/TF9716702025","url":null,"abstract":"Time-resolved attenuation of the atomic emission transition C(33P°J→23PJ) at 166 nm has been used to study the reactions of C(23PJ). The decay of this atom, following its generation by the vacuum ultra-violet flash photolysis of carbon suboxide, has been monitored directly in the presence of a number of gases. The following rate data for 300 K have been obtained: C(23PJ)+ NO →CN + O, k= 7.3±2.2 × 10–11 cm3 molecule–1 s–1, C(23PJ)+ O2→CO + O, k= 3,3±1.5 × 10–11 cm3 molecule–1 s–1, C(23PJ)+ N2O →CO + N2, k= 2.5±1.6 × 10–11 cm3 molecule–1 s–1, or CN + NO, C(23PJ)+ H2O →CO + H2k⩽3.6 × 10–13 cm3 molecule–1 s–1, or CH2O, C(23PJ)+ CO2→2CO, k≤ 10–14 cm3 molecule–1 s–1, C(23PJ)+ CH4→C2H4, k < 2 × 10–15 cm3 molecule–1 s–1, C(23PJ)+ N2+ M →CN2+ M, k= 3.1±1.5 × 10–33 cm6 molecule–2 s–1(M = Ar), C(23PJ)+ H2+ M →CH2+ M, k= 7.1±2.5 × 10–32 cm6 molecule–2 s–1(M = He), C(23PJ)+ CO + M →C2O + M, k= 6.3±2.7 × 10–32 cm6 molecule–2 s–1(M = He).","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2025-2035"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57624673","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: 96
Anodic oxidation of oxalic acid on gold 草酸在金上的阳极氧化
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702167
J. W. Johnson, S. Mueller, W. James
{"title":"Anodic oxidation of oxalic acid on gold","authors":"J. W. Johnson, S. Mueller, W. James","doi":"10.1039/TF9716702167","DOIUrl":"https://doi.org/10.1039/TF9716702167","url":null,"abstract":"The anodic oxidation of oxalic acid on Au has been studied at 80°C in aqueous media. The reaction rate was measured as a function of potential, oxalic acid concentration, pH, and temperature in H2SO4+ K2SO4+ KOH solutions of unit ionic strength. The oxalic acid was oxidized in acidic media to CO2. A first-order dependence of the rate on both pH and undissociated oxalic acid was found. The first decarboxylation step appears to be rate determining.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2167-2173"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702167","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57626532","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: 20
Thermal isomerization of cyclobutenes. Part 18.—1-Chlorocyclobutene and 1-bromocyclobutene 环丁烯的热异构化。部分18。- 1-氯环丁烯和1-溴环丁烯
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702328
D. Dickens, H. Frey, J. Metcalfe
{"title":"Thermal isomerization of cyclobutenes. Part 18.—1-Chlorocyclobutene and 1-bromocyclobutene","authors":"D. Dickens, H. Frey, J. Metcalfe","doi":"10.1039/TF9716702328","DOIUrl":"https://doi.org/10.1039/TF9716702328","url":null,"abstract":"The thermal isomerization of 1-chlorocyclobutene yielded 2-chlorobuta-1,3-diene quantitatively by a homogeneous first-order reaction. In the temperature range 423–473 K and at pressures of 1 kN m–2 and above, rate constants were determined and yielded the Arrhenius equation, log (k1/s–1)= 13.26±0.03–140 750±270 J mol–1/2.303 RT. At pressures below 150 N m–2 the rate constant decreased with decreasing pressure. The thermal isomerization of 1-bromocyclobutene yielded 2-bromobuta-1,3-diene. This reaction was homogeneous and first order at pressures above 1 kN m–2. In this pressure region, rate constants were determined at 10 temperatures in the range 424–458 K. The rate constants fitted the Arrhenius equation, log (k2/s–1)= 13.53±0.06–141 270±510 J mol–1/2.303 RT. At 446.6 K the rate constant was determined at various pressures in the range 1.26 kN m–2–1.18 N m–2. The “fall-off” curve so obtained was compared with those obtained by the application of the RRKM theory.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2328-2332"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702328","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57627131","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
Heats of ionization of HO2 and OH in aqueous solution 水溶液中HO2和OH的电离热
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702532
J. Baxendale, M. Ward, P. Wardman
{"title":"Heats of ionization of HO2 and OH in aqueous solution","authors":"J. Baxendale, M. Ward, P. Wardman","doi":"10.1039/TF9716702532","DOIUrl":"https://doi.org/10.1039/TF9716702532","url":null,"abstract":"Acid dissociation constants of OH and HO2 were measured over a range of temperature and give heats of ionization of 10 and 0 kcal mol–1 respectively. These values lead to ΔH°f of (O–2)aq and (O–)aq=–8(±2) and 9(±2) kcal mol–1 respectively. Solvation energies of O–2 and O– are estimated to be 94 and 113 kcal mol–1 and the E° of the couples O2/O–2, O/O–, –0.19 and 1.64 V respectively.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2532-2537"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702532","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628540","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: 19
Spectroscopic and thermodynamic study of hexafluorobenzene + aromatic amine complexes 六氟苯+芳香胺配合物的光谱和热力学研究
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702548
D. Armitage, T. G. Beaumont, K. C. Davis, D. Hall, K. W. Morcom
{"title":"Spectroscopic and thermodynamic study of hexafluorobenzene + aromatic amine complexes","authors":"D. Armitage, T. G. Beaumont, K. C. Davis, D. Hall, K. W. Morcom","doi":"10.1039/TF9716702548","DOIUrl":"https://doi.org/10.1039/TF9716702548","url":null,"abstract":"U.-v. spectrophotometric measurements of the association constants and enthalpies of formation for the complexes formed by hexafluorobenzene with N,N-dimethyl aniline (DMA) and N,N-dimethyl toluidine (DMT) are reported. Enthalpies of mixing of hexafluorobenzene with isopropylcyclohexane at 323.15 and 343.15 K are also reported. The spectrophotometric results correlate with the present enthalpy of mixing data taken in conjunction with the enthalpies of mixing for the hexafluorobenzene and amine systems reported previously.1","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2548-2550"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702548","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628862","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
Equilibrium properties of polar gases. Part 2.—The second dielectric virial coefficients of some polar gases 极性气体的平衡性质。第2部分。-某些极性气体的二次介电维利系数
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716702915
A. N. Barnes, L. E. Sutton
{"title":"Equilibrium properties of polar gases. Part 2.—The second dielectric virial coefficients of some polar gases","authors":"A. N. Barnes, L. E. Sutton","doi":"10.1039/TF9716702915","DOIUrl":"https://doi.org/10.1039/TF9716702915","url":null,"abstract":"The second dielectric virial coefficients ℬ for five polar gases CHF3, CHF2Cl, CH3Cl, CH2:CF2 and (CH3)2O were measured at 30, 50 and 70°C. for the gases CF3Cl and CF2Cl2, ℬ was measured at 50°C only. The experimental results were compared with those predicted by the forms of intermolecular potential that have been suggested for polar gases. None of these proves to be entirely satisfactory.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"160 1","pages":"2915-2925"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702915","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57630553","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
Heats of adsorption of organic bases on aerosilogels containing small quantities of aluminium 有机碱在含有少量铝的气凝胶上的吸附热
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703118
S. G. Ash, A. V. Kiselev, B. Kuznetsov
{"title":"Heats of adsorption of organic bases on aerosilogels containing small quantities of aluminium","authors":"S. G. Ash, A. V. Kiselev, B. Kuznetsov","doi":"10.1039/TF9716703118","DOIUrl":"https://doi.org/10.1039/TF9716703118","url":null,"abstract":"Calorimetric heats of adsorption of the organic bases triethylamine and benzene on aerosilogels have been measured. The aerosilogels were prepared from industrial aerosils and dehydroxylated in vacuo at temperatures up to 1150°C. One sample of aerosilogel, which contained 0.4 % by weight of aluminium impurity, produced very active surface sites, which were characterized by a high initial heat of adsorption—about 50 kcal mol–1(209 kJ mol–1) for triethylamine and 20 kcal mol–1(84 kJ mol–1) for benzene. Other samples containing less than 0.02 % aluminium did not show this activity. Aluminium was artificially introduced into a pure sample of aerosilogel using aluminium nitrate solution. The adsorption properties of this sample were similar to those of the aerosilogel prepared from the impure aerosil containing 0.4 % aluminium.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3118-3126"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703118","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632070","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
Molecular acoustics. Part 7.—Ring inversion and internal rotation in some 2-halomethyl-1,3-dioxans 分子的音响。第7部分。-某些2-卤代甲基-1,3-二恶烷的环反转和内旋
Transactions of The Faraday Society Pub Date : 1971-01-01 DOI: 10.1039/TF9716703223
G. Eccleston, B. Walsh, E. Wyn-Jones, H. Morris
{"title":"Molecular acoustics. Part 7.—Ring inversion and internal rotation in some 2-halomethyl-1,3-dioxans","authors":"G. Eccleston, B. Walsh, E. Wyn-Jones, H. Morris","doi":"10.1039/TF9716703223","DOIUrl":"https://doi.org/10.1039/TF9716703223","url":null,"abstract":"A double ultrasonic relaxation has been observed in some 2-halomethyl-1,3-dioxans. Using n.m.r., infra-red and previous knowledge of the ultrasonic relaxation behaviour of simple 1,3-dioxans the two relaxations have been assigned, in turn, to the perturbation of conformational equilibria involving ring inversion and internal rotation. From the temperature dependence of the relaxation times the barriers opposing these conformational changes have been derived.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3223-3229"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703223","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632297","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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