The e.p.r. spectra of polycrystalline RDX, and its single crystals, when irradiated with γ-radiation and 254 nm light at 77–298 K, indicate that ˙NO2 may be a primary photochemical product of RDX. Mass spectral analyses of the gaseous products suggested that N2 and NO may also be primary photolysis products of RDX. The identity of these products was consistent with the theoretically predicted bond cleavage patterns of the axial and equatorial nitramine groups of RDX and HMX. A combination of theory and experiment thus permitted the tentative assignment of the primary photochemical steps for polycrystalline RDX.
{"title":"Chemistry of aliphatic unconjugated nitramines. Part 5.—Primary photochemical processes in polycrystalline RDX","authors":"J. Stals, A. Buchanan, C. G. Barraclough","doi":"10.1039/TF9716701749","DOIUrl":"https://doi.org/10.1039/TF9716701749","url":null,"abstract":"The e.p.r. spectra of polycrystalline RDX, and its single crystals, when irradiated with γ-radiation and 254 nm light at 77–298 K, indicate that ˙NO2 may be a primary photochemical product of RDX. Mass spectral analyses of the gaseous products suggested that N2 and NO may also be primary photolysis products of RDX. The identity of these products was consistent with the theoretically predicted bond cleavage patterns of the axial and equatorial nitramine groups of RDX and HMX. A combination of theory and experiment thus permitted the tentative assignment of the primary photochemical steps for polycrystalline RDX.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1749-1755"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701749","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57622076","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}
Bond moment constants calculated from infra-red band intensities are compared with theoretical estimates calculated by the CNDO (complete neglect of differential overlap) method taking the dipole moment contribution of hybird orbitals into account. Support is obtained for the suggestion by Steele and Wheatley that a rehybridization moment contributes to the intensity of certain bond-bending vibrations. The theoretical model developed is illustrated by calculations on the out-of-plane bending vibration of benzene and on the bending vibration of hydrogen cyanide.
{"title":"Origin and role of rehybridization moments in determining infra-red intensities","authors":"G. Jalsovszky, W. J. Orville-Thomas","doi":"10.1039/TF9716701894","DOIUrl":"https://doi.org/10.1039/TF9716701894","url":null,"abstract":"Bond moment constants calculated from infra-red band intensities are compared with theoretical estimates calculated by the CNDO (complete neglect of differential overlap) method taking the dipole moment contribution of hybird orbitals into account. Support is obtained for the suggestion by Steele and Wheatley that a rehybridization moment contributes to the intensity of certain bond-bending vibrations. The theoretical model developed is illustrated by calculations on the out-of-plane bending vibration of benzene and on the bending vibration of hydrogen cyanide.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1894-1903"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701894","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57624005","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}
Free energy, enthalpy and entropy variations associated with solution and hydration processes have been determined for the following compounds: tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,3-dioxolan and 1,4-dioxan. Negative ΔSh and ΔHh values result from the transfer of the above-mentioned ethers from the gaseous state to dilute aqueous solutions. Their absolute values, however, are markedly smaller for the diethers than for monoethers, this being particularly so for ΔSh values. Comparisons are made between the thermodynamic behaviour in aqueous solutions of cyclic ethers and amines and the analogue, open-chain derivatives. On the basis of views currently held on water structure, hypotheses are suggested to explain effects associated with (i) changing from open to cyclic systems, (ii) lengthening of the chain and methyl substitution, and (iii) the presence, in cyclic systems, of several hydrophilic centres.
{"title":"Thermodynamic study on aqueous dilute solutions of organic compounds. Part 2.—Cyclic ethers","authors":"S. Cabani, G. Conti, L. Lepori","doi":"10.1039/TF9716701943","DOIUrl":"https://doi.org/10.1039/TF9716701943","url":null,"abstract":"Free energy, enthalpy and entropy variations associated with solution and hydration processes have been determined for the following compounds: tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,3-dioxolan and 1,4-dioxan. Negative ΔSh and ΔHh values result from the transfer of the above-mentioned ethers from the gaseous state to dilute aqueous solutions. Their absolute values, however, are markedly smaller for the diethers than for monoethers, this being particularly so for ΔSh values. Comparisons are made between the thermodynamic behaviour in aqueous solutions of cyclic ethers and amines and the analogue, open-chain derivatives. On the basis of views currently held on water structure, hypotheses are suggested to explain effects associated with (i) changing from open to cyclic systems, (ii) lengthening of the chain and methyl substitution, and (iii) the presence, in cyclic systems, of several hydrophilic centres.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"1943-1950"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716701943","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57624530","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}
A simple analytical expression using three parameters is presented which describes the variation of Nκ with x for a ring-disc electrode to an accuracy of about 2 % in the range x > 1. Values of the three parameters are tabulated for electrodes of common radius ratios. The parameters can also be used to describe transient behaviour at the ring-disc electrode.
{"title":"Ring disc electrodes. Part 14.—Kinetic and transient parameters","authors":"W. Albery, J. S. Drury, M. Hitchman","doi":"10.1039/TF9716702162","DOIUrl":"https://doi.org/10.1039/TF9716702162","url":null,"abstract":"A simple analytical expression using three parameters is presented which describes the variation of Nκ with x for a ring-disc electrode to an accuracy of about 2 % in the range x > 1. Values of the three parameters are tabulated for electrodes of common radius ratios. The parameters can also be used to describe transient behaviour at the ring-disc electrode.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2162-2166"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702162","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57625751","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}
Electron-diffraction intensity data have been collected for gaseous sulphur dioxide (250 K) and rioxide (300 K) at camera lengths of 50 and 25 cm. Least squares refinement led to the following ra distances, root-mean-square amplitudes of vibration, and estimated standard deviations; for SO2, rS–O= 1.431 ± 0.002 A, rO‥O= 2.460±0.012 A, uS–O= 0.041±0.003 A, and uO‥O= 0.053±0.012 A, for SO3, rS–O= 1.418±0.003 A, rO‥O= 2.457±0.009 A, uS–O= 0.048±0.005 A and uO‥O= 0.067±0.010 A. The corresponding value for the angle in the dioxide is 118.5±1.0°, whilst the trioxide is planar within experimental error. For both molecules, spectroscopic estimates of the vibrational amplitudes have been made from force-constant data, and for SO2 these are in satisfactory agreement with the diffraction results. For SO3, however, agreement is poorer and this may indicate the presence of a small amount of S3O9 trimer in the diffracting vapour. Mean-square parallel and perpendicular amplitudes of vibration and centrifugal distortion corrections have also been calculated for both molecules and the electron-diffraction ra parameters converted to equilibrium (re), and zero-point-average (r°α), values. For SO2, these structures differ insignificantly from corresponding microwave re and rz estimates.
在相机长度为50和25厘米处，收集了气态二氧化硫(250 K)和氧化物(300 K)的电子衍射强度数据。最小二乘细化得到以下ra距离、振动的均方根振幅和估计的标准差;对于SO2, rS-O = 1.431±0.002 A, rO…n = 2.460±0.012 A, uS-O = 0.041±0.003 A，和uO…n = 0.053±0.012 A，对于SO3, rS-O = 1.418±0.003 A, rO…n = 2.457±0.009 A, uS-O = 0.048±0.005 A和uO…n = 0.067±0.010 A。在实验误差范围内，二氧化二氮的角度对应值为118.5±1.0°，而三氧化二氮为平面。对于这两种分子，振动振幅的光谱估计已经从力常数数据中得到，对于SO2，这与衍射结果是令人满意的。然而，对于SO3，一致性较差，这可能表明在衍射蒸汽中存在少量的S3O9三聚体。还计算了分子的均方平行和垂直振动振幅和离心畸变校正，并将电子衍射参数转换为平衡(re)和零点平均(r°α)值。对于SO2，这些结构与相应的微波re和rz估计值差别不大。
{"title":"Electron-diffraction investigations of gaseous sulphur dioxide and trioxide","authors":"A. Clark, B. Beagley","doi":"10.1039/TF9716702216","DOIUrl":"https://doi.org/10.1039/TF9716702216","url":null,"abstract":"Electron-diffraction intensity data have been collected for gaseous sulphur dioxide (250 K) and rioxide (300 K) at camera lengths of 50 and 25 cm. Least squares refinement led to the following ra distances, root-mean-square amplitudes of vibration, and estimated standard deviations; for SO2, rS–O= 1.431 ± 0.002 A, rO‥O= 2.460±0.012 A, uS–O= 0.041±0.003 A, and uO‥O= 0.053±0.012 A, for SO3, rS–O= 1.418±0.003 A, rO‥O= 2.457±0.009 A, uS–O= 0.048±0.005 A and uO‥O= 0.067±0.010 A. The corresponding value for the angle in the dioxide is 118.5±1.0°, whilst the trioxide is planar within experimental error. For both molecules, spectroscopic estimates of the vibrational amplitudes have been made from force-constant data, and for SO2 these are in satisfactory agreement with the diffraction results. For SO3, however, agreement is poorer and this may indicate the presence of a small amount of S3O9 trimer in the diffracting vapour. Mean-square parallel and perpendicular amplitudes of vibration and centrifugal distortion corrections have also been calculated for both molecules and the electron-diffraction ra parameters converted to equilibrium (re), and zero-point-average (r°α), values. For SO2, these structures differ insignificantly from corresponding microwave re and rz estimates.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2216-2224"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702216","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57626408","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}
The permittivity and loss of solutions of tri(n-butyl)ammonium picrate and iodide in various polar solvents have been measured at a number of frequencies between 0.2 and 3.0 GHz. The relative static permittivities of the pure solvents used range from 3.37 to 20.7 at 25°C. For all the solutions investigated, the observed dispersion of permittivity is adequately described by a single relaxation time, which for a given solvent depends on the concentration as well as the nature of the solute. Apparent dipole moments evaluated from the dispersion amplitude by means of Bottcher's theory, on the assumption that the dipole occupies a spherical cavity, are 12.3±0.4 D and 11.2±0.6 D for the picrate and iodide respectively. These values indicate that the relaxing dipole is an ion pair. Dielectric relaxation times corrected for internal field effects by different relations are compared with those calculated from the partial molar volume of the solute and the viscosity of the solvent by means of the Debye-Stokes equation. Density data for solutions of the two salts in 1,2-dichloroethane are included and from these data, partial molar volumes of the salts have been evaluated.
{"title":"Dielectric relaxation in non aqueous solutions. Part 2.—Solutions of tri(n-butyl)ammonium picrate and iodide in polar solvents","authors":"E. Cavell, P. Knight, M. A. Sheikh","doi":"10.1039/TF9716702225","DOIUrl":"https://doi.org/10.1039/TF9716702225","url":null,"abstract":"The permittivity and loss of solutions of tri(n-butyl)ammonium picrate and iodide in various polar solvents have been measured at a number of frequencies between 0.2 and 3.0 GHz. The relative static permittivities of the pure solvents used range from 3.37 to 20.7 at 25°C. For all the solutions investigated, the observed dispersion of permittivity is adequately described by a single relaxation time, which for a given solvent depends on the concentration as well as the nature of the solute. Apparent dipole moments evaluated from the dispersion amplitude by means of Bottcher's theory, on the assumption that the dipole occupies a spherical cavity, are 12.3±0.4 D and 11.2±0.6 D for the picrate and iodide respectively. These values indicate that the relaxing dipole is an ion pair. Dielectric relaxation times corrected for internal field effects by different relations are compared with those calculated from the partial molar volume of the solute and the viscosity of the solvent by means of the Debye-Stokes equation. Density data for solutions of the two salts in 1,2-dichloroethane are included and from these data, partial molar volumes of the salts have been evaluated.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2225-2233"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702225","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57626500","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}
Pentachloroethyl 1,1,2,2-tetrachloroethyl and 1,1,2-trichloroethyl radicals were produced by the reactions of radiolytically generated cyclohexyl radicals with pentachloroethane and sym-tetrachloroethane. The kinetics of the following reactions were studied: c-C6H11+ C2Cl5H →c-C6H11Cl + C2Cl4H (2), c-C6H11+ C2Cl5H →c-C6H12+ C2Cl5(3), C2Cl4H + c-C6H12→C2Cl4H2+ c-C6H11(4), C2Cl4H →C2Cl3H + Cl (5), c-C6H11+ C2Cl4H2→c-C6H11Cl + C2Cl3H2(11), c-C6H11+ C2Cl4H2→c-C6H12+ C2Cl4H (12), C2Cl3H2+ c-C6H12→C2Cl3H3+ c-C6H11(13), C2Cl3H2→C2Cl2H2+ Cl. (14). The following rate expressions were obtained: log10(k2/k3)= 1.40±0.15 –(660±230)/4.576T; log10(k11/k12)= 1.07±0.06 –(3780±120)/4.576T: log10(k5/k4)(mol l.–1)= 5.63±0.07 –(8100±100)/4.576T; log10(k14/k13)(mol l.–1)= 5.91±0.21 –(6900±400)/4.576T. R the gas constant was taken to be 1.9872 cal K–1mol–1 and subsequent activation energies expressed in cal mol–1(1 cal = 4.1855 J).
{"title":"Radiation-induced dechlorination of pentachloroethane and sym-tetrachloroethane. Reactions of 1,1,2,2-tetrachloroethyl and 1,2,2-trichloroethyl radicals","authors":"M. Katz, A. Horowitz, L. Rajbenbach","doi":"10.1039/TF9716702354","DOIUrl":"https://doi.org/10.1039/TF9716702354","url":null,"abstract":"Pentachloroethyl 1,1,2,2-tetrachloroethyl and 1,1,2-trichloroethyl radicals were produced by the reactions of radiolytically generated cyclohexyl radicals with pentachloroethane and sym-tetrachloroethane. The kinetics of the following reactions were studied: c-C6H11+ C2Cl5H →c-C6H11Cl + C2Cl4H (2), c-C6H11+ C2Cl5H →c-C6H12+ C2Cl5(3), C2Cl4H + c-C6H12→C2Cl4H2+ c-C6H11(4), C2Cl4H →C2Cl3H + Cl (5), c-C6H11+ C2Cl4H2→c-C6H11Cl + C2Cl3H2(11), c-C6H11+ C2Cl4H2→c-C6H12+ C2Cl4H (12), C2Cl3H2+ c-C6H12→C2Cl3H3+ c-C6H11(13), C2Cl3H2→C2Cl2H2+ Cl. (14). The following rate expressions were obtained: log10(k2/k3)= 1.40±0.15 –(660±230)/4.576T; log10(k11/k12)= 1.07±0.06 –(3780±120)/4.576T: log10(k5/k4)(mol l.–1)= 5.63±0.07 –(8100±100)/4.576T; log10(k14/k13)(mol l.–1)= 5.91±0.21 –(6900±400)/4.576T. R the gas constant was taken to be 1.9872 cal K–1mol–1 and subsequent activation energies expressed in cal mol–1(1 cal = 4.1855 J).","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2354-2364"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702354","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57627845","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}
Absorption spectra of GeBr and SnBr have been photographed during the flash photolysis of GeBr4 and SnBr4. The spectrum of GeBr consists of the B2Σ–X2Π system between 280 and 320 nm and numerous new bands below 250 nm. The bands have been analyzed into several systems, the most prominent of which have the following parameters. State C: Te= 41 046 cm–1(relative to X2Π½). ωe= 359 cm–1, ωexe= 3 cm–1, A= 110 cm–1. State E: Te= 44 805 cm–1, ωe= 366 cm–1, ωexe= 5 cm–1, A∼0. State G: Te= 47 544 cm–1, ωe= 358 cm–1, ωexe= 1.5 cm–1. The spectrum of SnBr contains bands of the B2Σ—X2Π systems and a number of new band systems below 250 nm, the analyses of which are discussed.
{"title":"Ultra-violet absorption spectra of germanium monobromide and tin monobromide","authors":"G. Oldershaw, K. Robinson","doi":"10.1039/TF9716702499","DOIUrl":"https://doi.org/10.1039/TF9716702499","url":null,"abstract":"Absorption spectra of GeBr and SnBr have been photographed during the flash photolysis of GeBr4 and SnBr4. The spectrum of GeBr consists of the B2Σ–X2Π system between 280 and 320 nm and numerous new bands below 250 nm. The bands have been analyzed into several systems, the most prominent of which have the following parameters. State C: Te= 41 046 cm–1(relative to X2Π½). ωe= 359 cm–1, ωexe= 3 cm–1, A= 110 cm–1. State E: Te= 44 805 cm–1, ωe= 366 cm–1, ωexe= 5 cm–1, A∼0. State G: Te= 47 544 cm–1, ωe= 358 cm–1, ωexe= 1.5 cm–1. The spectrum of SnBr contains bands of the B2Σ—X2Π systems and a number of new band systems below 250 nm, the analyses of which are discussed.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2499-2504"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702499","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628167","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}
Apparent molar volumes of KCl in formamide in the concentration range 0.005–1.0 M at 25°C have been measured using a magnetically-operated dilatometer. The Debye-Huckel appa rent molar volume limiting slope for 1-1 electrolytes in formamide at 25°C has been calculated to be 1.104 ml mol– l.½ This value is satisfactorily approached experimentally with KCl in very dilute formamide solutions.
在25℃下，用磁操作膨胀计测量了浓度范围为0.005-1.0 M的甲酰胺中KCl的表观摩尔体积。在25°C时甲酰胺中1-1电解质的Debye-Huckel表观摩尔体积极限斜率计算为1.104 ml mol -1。这个值在实验中用KCl在非常稀的甲酰胺溶液中令人满意地接近。
{"title":"Apparent molar volumes of electrolytes. Part 4.—KCl in formamide at 25°C","authors":"L. Dunn","doi":"10.1039/TF9716702525","DOIUrl":"https://doi.org/10.1039/TF9716702525","url":null,"abstract":"Apparent molar volumes of KCl in formamide in the concentration range 0.005–1.0 M at 25°C have been measured using a magnetically-operated dilatometer. The Debye-Huckel appa rent molar volume limiting slope for 1-1 electrolytes in formamide at 25°C has been calculated to be 1.104 ml mol– l.½ This value is satisfactorily approached experimentally with KCl in very dilute formamide solutions.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2525-2527"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702525","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628461","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}
A Pt,H2—AgCl,Ag e.m.f. cell is described whereby accurate measurements may be obtained from additions of stock solutions. Measurements with HCl + H2SO4 mixtures are used to evaluate the dissociation constant of the HSO–4 ion at 25°C. A method of extrapolation is described which aims at reducing uncertainties due to the ion size parameter. Some previous measurements with e.m.f. cells are also re-examined.
{"title":"E.m.f. studies of electrolytic dissociation. Part 11.—The bisulphate ion at 25°C","authors":"C. E. Evans, C. Monk","doi":"10.1039/TF9716702652","DOIUrl":"https://doi.org/10.1039/TF9716702652","url":null,"abstract":"A Pt,H2—AgCl,Ag e.m.f. cell is described whereby accurate measurements may be obtained from additions of stock solutions. Measurements with HCl + H2SO4 mixtures are used to evaluate the dissociation constant of the HSO–4 ion at 25°C. A method of extrapolation is described which aims at reducing uncertainties due to the ion size parameter. Some previous measurements with e.m.f. cells are also re-examined.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2652-2658"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702652","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628919","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}
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