The relaxation of vibrationally excited CS, formed in the flash-initiated reaction: O(3P)+CS2→ SO + CS, has been studied by monitoring the absorption of the A1Π—X1Σ+(2,1) band photoelectrically. Rates of decay were measured in the presence of various added gases, and hence rate constants determined for the de-excitation of CS(ν= 1) by ortho-H2, para-H2, HD, 3He, D2, 4He, N2O, CO2, H2O, D2O, H2S and D2S. The much greater efficiency of N2O compared to CO2 shows clearly how the probability of vibration-vibration energy exchange is enhanced if both species are infra-red active. Vibration-rotation energy transfer may occur with the collision partners which have small moments of inertia. Where appropriate, experimental transition probabilities are compared to those predicted by Sharma's recently published theory.
{"title":"Vibrational relaxation of carbon monosulphide","authors":"C. Morley, Ian W. M. Smith","doi":"10.1039/TF9716702575","DOIUrl":"https://doi.org/10.1039/TF9716702575","url":null,"abstract":"The relaxation of vibrationally excited CS, formed in the flash-initiated reaction: O(3P)+CS2→ SO + CS, has been studied by monitoring the absorption of the A1Π—X1Σ+(2,1) band photoelectrically. Rates of decay were measured in the presence of various added gases, and hence rate constants determined for the de-excitation of CS(ν= 1) by ortho-H2, para-H2, HD, 3He, D2, 4He, N2O, CO2, H2O, D2O, H2S and D2S. The much greater efficiency of N2O compared to CO2 shows clearly how the probability of vibration-vibration energy exchange is enhanced if both species are infra-red active. Vibration-rotation energy transfer may occur with the collision partners which have small moments of inertia. Where appropriate, experimental transition probabilities are compared to those predicted by Sharma's recently published theory.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2575-2585"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702575","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57628967","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 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.
{"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}
Experimental liquid densities of argon + krypton binary mixtures at 115.77 K, of krypton + xenon binary mixtures at 161.36 K, of one argon + xenon binary mixture at 115.77 K and of ethane at both 115.77 and 161.36 K were determined by the pyknometer method. Excess volume and excess Gibbs energy were obtained from the experimental data for argon + krypton and krypton + xenon binaries.
{"title":"Liquid density and excess properties of argon + krypton and krypton + xenon binary liquid mixtures, and liquid density of ethane","authors":"Chen-Hwa Chui, F. Canfield","doi":"10.1039/TF9716702933","DOIUrl":"https://doi.org/10.1039/TF9716702933","url":null,"abstract":"Experimental liquid densities of argon + krypton binary mixtures at 115.77 K, of krypton + xenon binary mixtures at 161.36 K, of one argon + xenon binary mixture at 115.77 K and of ethane at both 115.77 and 161.36 K were determined by the pyknometer method. Excess volume and excess Gibbs energy were obtained from the experimental data for argon + krypton and krypton + xenon binaries.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2933-2940"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702933","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57630966","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 equilibrium constant and standard free energy change for the reactions: 2 ZnS(s)⇌2 Zn(g)+ S2(g)(1), ZnS(s)+ Si(s)⇌Zn(g)+ SiS(g)(2) have been measured around 1000°C by a transportation method. The following free energies were obtained ΔG°= 178 900–92.4 T cal mol–1 1293 K (1b), ΔG°= 101 700–65.7 T cal mol–1 1293 K. (2b) By combination, the free energy change for reaction (3) is obtained: 2Si(s)+ S2(g)= 2 SiS(g)(3), ΔG°= 24 500–39.0 T cal mol–1 Combined with results of other investigators the free energy of formation of SiS2(s, l, g) is estimated.
用输运法测定了2zns (s)+ 2zn (g)+ S2(g)(1)、ZnS(s)+ Si(s) + Zn(g)+ SiS(g)(2)在1000℃左右反应的平衡常数和标准自由能变化。得到了以下自由能ΔG°= 178 900-92.4 T cal mol-1 1293 K (1b)， ΔG°= 101 700-65.7 T cal mol-1 1293 K (2b)，结合其他研究者的结果，得到了反应(3)的自由能变化:2Si(s)+ S2(g)= 2 SiS(g)(3)， ΔG°= 24 500-39.0 T cal mol-1结合其他研究者的结果，估计了SiS2的形成自由能(s, l, g)。
{"title":"Thermodynamics of silicon sulphides and zinc sulphide","authors":"T. Rosenqvist, K. Tungesvik","doi":"10.1039/TF9716702945","DOIUrl":"https://doi.org/10.1039/TF9716702945","url":null,"abstract":"The equilibrium constant and standard free energy change for the reactions: 2 ZnS(s)⇌2 Zn(g)+ S2(g)(1), ZnS(s)+ Si(s)⇌Zn(g)+ SiS(g)(2) have been measured around 1000°C by a transportation method. The following free energies were obtained ΔG°= 178 900–92.4 T cal mol–1 1293 K (1b), ΔG°= 101 700–65.7 T cal mol–1 1293 K. (2b) By combination, the free energy change for reaction (3) is obtained: 2Si(s)+ S2(g)= 2 SiS(g)(3), ΔG°= 24 500–39.0 T cal mol–1 Combined with results of other investigators the free energy of formation of SiS2(s, l, g) is estimated.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"2945-2951"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716702945","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57631091","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}
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.
{"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}
A flame calorimeter, designed to measure the heats of combustion of gaseous chloroalkanes, is described and the following heats of combustion to give products CO2(g) and HCl (600 H2O)(l) at 25°C and 1 atm are reported: ΔH°c(chloromethane, g)=–764.01±0.50 kJ mol–1, ΔH°c(chloromethane, g)=–1413.05±0.59 kJ mol–1, ΔH°c(1-chloropropane, g)=–2072.11±0.79 kJ mol–1, ΔH°c(2-chloropropane, g)=–2059.62±0.79 kJ mol–1. The derived heats of formation agree with those obtained from studies of equilibria involving alkenes, hydrogen chloride and chloroalkanes, but disagree with those obtained by other calorimetric methods. The heats of formation of chloroalkanes are discussed in terms of the Allen bond-energy scheme.
{"title":"Measurements of heats of combustion by flame calorimetry. Part 7.—Chloromethane, chloroethane, 1-chloropropane, 2-chloropropane","authors":"R. Fletcher, G. Pilcher","doi":"10.1039/TF9716703191","DOIUrl":"https://doi.org/10.1039/TF9716703191","url":null,"abstract":"A flame calorimeter, designed to measure the heats of combustion of gaseous chloroalkanes, is described and the following heats of combustion to give products CO2(g) and HCl (600 H2O)(l) at 25°C and 1 atm are reported: ΔH°c(chloromethane, g)=–764.01±0.50 kJ mol–1, ΔH°c(chloromethane, g)=–1413.05±0.59 kJ mol–1, ΔH°c(1-chloropropane, g)=–2072.11±0.79 kJ mol–1, ΔH°c(2-chloropropane, g)=–2059.62±0.79 kJ mol–1. The derived heats of formation agree with those obtained from studies of equilibria involving alkenes, hydrogen chloride and chloroalkanes, but disagree with those obtained by other calorimetric methods. The heats of formation of chloroalkanes are discussed in terms of the Allen bond-energy scheme.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3191-3201"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703191","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57631880","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 adsorption of hydrogen chloride on outgassed, deuterated, and reduced rutile surfaces has been studied by infra-red spectroscopy. Surface Ti4+O2–Ti4+ groups react with hydrogen chloride to form hydroxide ions and chloride ions on adjacent titanium ion sites. The reaction of hydrogen chloride with surface hydroxide ions leads to water coordinately bound to Ti4+ and associated with a chloride ion. Rearrangement to Ti4+Cl– species occurs and leads to the formation of adsorbed water which can react with hydrogen chloride to form H3O+Cl– on the surface. The adsorption of hydrogen chloride leads to surface species which act as Bronsted acid sites in the presence of adsorbed ammonia or pyridine.
{"title":"Infra-red study of hydrogen chloride adsorption on rutile surfaces","authors":"G. D. Parfitt, J. Ramsbotham, C. H. Rochester","doi":"10.1039/TF9716703100","DOIUrl":"https://doi.org/10.1039/TF9716703100","url":null,"abstract":"The adsorption of hydrogen chloride on outgassed, deuterated, and reduced rutile surfaces has been studied by infra-red spectroscopy. Surface Ti4+O2–Ti4+ groups react with hydrogen chloride to form hydroxide ions and chloride ions on adjacent titanium ion sites. The reaction of hydrogen chloride with surface hydroxide ions leads to water coordinately bound to Ti4+ and associated with a chloride ion. Rearrangement to Ti4+Cl– species occurs and leads to the formation of adsorbed water which can react with hydrogen chloride to form H3O+Cl– on the surface. The adsorption of hydrogen chloride leads to surface species which act as Bronsted acid sites in the presence of adsorbed ammonia or pyridine.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3100-3109"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703100","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632006","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 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.
{"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}
The gas-phase radiolysis of C2N2+ argon mixtures has been used as a means of following CN radical reactions with a number of hydrocarbons. Rate constants for the reaction with ethylene, propylene, 1,3-butadiene and benzene approach the collisional limit and reflect the extremely electrophilic nature of CN radicals. Rate constants for hydrogen abstraction from methane and ethane have also been determined and enable comparisons to be made with halogen atom reactions.
{"title":"Reactions of cyanogen radicals with hydrocarbons","authors":"G. Bullock, R. Cooper","doi":"10.1039/TF9716703258","DOIUrl":"https://doi.org/10.1039/TF9716703258","url":null,"abstract":"The gas-phase radiolysis of C2N2+ argon mixtures has been used as a means of following CN radical reactions with a number of hydrocarbons. Rate constants for the reaction with ethylene, propylene, 1,3-butadiene and benzene approach the collisional limit and reflect the extremely electrophilic nature of CN radicals. Rate constants for hydrogen abstraction from methane and ethane have also been determined and enable comparisons to be made with halogen atom reactions.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3258-3264"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703258","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632424","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 specific adsorption of fluoride ion on mercury has been studied at two temperatures. The unusual adsorption isotherm of the fluoride ion has been analyzed in terms of the equilibrium conditions prevailing across the double layer; a Freundlich-type isotherm describes the surface pressure of the adsorbed ionic film. The inner layer capacitance has been analyzed and its various components calculated, and from the variations of the inner layer capacitance at constant amount of adsorbed charge, the inner layer capacitance in the absence of adsorption has been evaluated. The anodic hump in the capacitance of fluoride solutions is due mainly to the adsorption of F– ions, and not to adsorbed solvent reorientation. The adsorption of SiF2–6 does not lead to a large increase in the double-layer capacitance at anodic potentials.
{"title":"Specific adsorption of fluoride ions on mercury and the structure of the mercury/solutions interface","authors":"D. Schiffrin","doi":"10.1039/TF9716703318","DOIUrl":"https://doi.org/10.1039/TF9716703318","url":null,"abstract":"The specific adsorption of fluoride ion on mercury has been studied at two temperatures. The unusual adsorption isotherm of the fluoride ion has been analyzed in terms of the equilibrium conditions prevailing across the double layer; a Freundlich-type isotherm describes the surface pressure of the adsorbed ionic film. The inner layer capacitance has been analyzed and its various components calculated, and from the variations of the inner layer capacitance at constant amount of adsorbed charge, the inner layer capacitance in the absence of adsorption has been evaluated. The anodic hump in the capacitance of fluoride solutions is due mainly to the adsorption of F– ions, and not to adsorbed solvent reorientation. The adsorption of SiF2–6 does not lead to a large increase in the double-layer capacitance at anodic potentials.","PeriodicalId":23290,"journal":{"name":"Transactions of The Faraday Society","volume":"67 1","pages":"3318-3342"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1039/TF9716703318","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"57632712","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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