Mercury-solution Interface Research Articles

A preliminary investigation of ionic adsorption at the mercury—hexamethyl phosphoric triamide interface

A reference electrode is described that is reversible and reproducible in hexamethyl phosphoric triamide; it was used to study the adsorption of 1 : 1 electrolytes at the mercury—solution interface. The differential capacity curves show features similar to those found for water and the degree of specific adsorption of the anions follows the same sequence: PF − 6 < BF − 4, ClO − 4 < Br −. There appears to be no specific adsorption of the alkali metal cations at negative charge values whereas the tetraalkyl ammonium ions are strongly adsorbed.

ChemInform Abstract: A STUDY OF THE INTERFACIAL BEHAVIOR OF SEVERAL ALKALOIDS AT A MERCURY‐SOLUTION INTERFACE

Chemischer InformationsdienstVolume 13, Issue 13 Article ChemInform Abstract: A STUDY OF THE INTERFACIAL BEHAVIOR OF SEVERAL ALKALOIDS AT A MERCURY-SOLUTION INTERFACE E. TRONEL-PEYROZ, E. TRONEL-PEYROZSearch for more papers by this authorD. SCHUHMANN, D. SCHUHMANNSearch for more papers by this authorM. JUBAULT, M. JUBAULTSearch for more papers by this author E. TRONEL-PEYROZ, E. TRONEL-PEYROZSearch for more papers by this authorD. SCHUHMANN, D. SCHUHMANNSearch for more papers by this authorM. JUBAULT, M. JUBAULTSearch for more papers by this author First published: March 30, 1982 https://doi.org/10.1002/chin.198213079AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume13, Issue13March 30, 1982 RelatedInformation

ChemInform Abstract: Interfacial Behaviour of N1‐Substituted Sulfanilamides at the Mercury‐Solution Interface. Adsorption of N1‐2‐Pyrimidinyl and N1‐2(4,6‐Dimethyl)pyrimidinyl Derivatives(I) and Structural Parameters (Adsorptionserscheinungen an der Hg‐Tropfelektrode).

Chemischer InformationsdienstVolume 13, Issue 13 Article ChemInform Abstract: Interfacial Behaviour of N1-Substituted Sulfanilamides at the Mercury-Solution Interface. Adsorption of N1-2-Pyrimidinyl and N1-2(4,6-Dimethyl)pyrimidinyl Derivatives(I) and Structural Parameters (Adsorptionserscheinungen an der Hg-Tropfelektrode). G. BATTISTUZZI GAVIOLI, G. BATTISTUZZI GAVIOLISearch for more papers by this authorG. GRANDI, G. GRANDISearch for more papers by this authorL. BENEDETTI, L. BENEDETTISearch for more papers by this authorR. ANDREOLI, R. ANDREOLISearch for more papers by this authorR. BATTINI, R. BATTINISearch for more papers by this author G. BATTISTUZZI GAVIOLI, G. BATTISTUZZI GAVIOLISearch for more papers by this authorG. GRANDI, G. GRANDISearch for more papers by this authorL. BENEDETTI, L. BENEDETTISearch for more papers by this authorR. ANDREOLI, R. ANDREOLISearch for more papers by this authorR. BATTINI, R. BATTINISearch for more papers by this author First published: March 30, 1982 https://doi.org/10.1002/chin.198213077Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue13March 30, 1982 RelatedInformation

Adsorption of poly- DL-alanine at the mercury-solution interface

The adsorption of poly- DL-alanine (mean molecular weight 3900) at the mercury-solution interface was studied by means of differential capacity and surface tension measurements. The poly- DL-alanine adsorbed in the potential region between 0.0 and −1.6V( sce). At the potentials of −0.15 and −1.1 V the maximum surface concentration Γ m , and the surface area occupied by one molecule, S, were derived from the diffusion-controlled adsorption behavior with the assumption of the diffusion coefficient. The values of S at −1.1V in 0.1 N sulfuric acid, 0.1N sodium sulfate and 0.1N sodium hydroxide were 348, 282 and 274Å 2/molecule, respectively, and the values at −0.5V became somewhat larger than the above values. The above S values derived from the differential capacity measurement were supported from those derived from the surface tension measurement by means of the Lippmann adsorption equation. The adsorbed conformation at the mercury-solution interface was discussed from those S values.

On virtual interactions of adsorbed molecules and ions: Sucrose and chloride in the ternary system water + sucrose + NaCl at the mercury-solution interface

The mutual effects of chloride on sucrose adsorption and vice versa were studied at the mercury—water interface by measuring the interfacial tension with a computer-controlled maximum bubble pressure instrument. Measurements were made at constant salt activity and varying sucrose activity, as well as at fixed sucrose activity and changing salt activity. No strong effects of adsorbed chloride on simultaneously adsorbed sucrose, or vice versa, were found. Some pitfalls in the interpretation of isotherm parameters in terms of physical reality have been emphasized.

Interfacial behaviour of N1-substituted sulfanilamides at the mercury-solution interface Adsorption of N1-2-pyrimidinyl and N1-2(4,6-dimethyl) pyrimidinyl derivatives and structural parameters

Interfacial behaviour of N1-substituted sulfanilamides at the mercury-solution interface Adsorption of N1-2-pyrimidinyl and N1-2(4,6-dimethyl) pyrimidinyl derivatives and structural parameters

Interfacial behaviour of N 1-substituted sulfanilamides at the mercury-solution interface : Adsorption of N 1-2-pyrimidinyl and N 1-2(4,6-dimethyl) pyrimidinyl derivatives and structural parameters

The adsorption of two N 1-sulfanilamide derivatives, N 1-2-pyrimidinyl and N 1-2(4,6-dimethyl)pyrimidinyl, was studied by a differential capacitance method at pH=12 at the dropping mercury electrode. The area occupied by each molecule of these compounds, adsorbed at the mercury-electrolyte solution interface, corresponds well to the area expected for a molecule adsorbed flat on the electrode with its pNH 2Ø-S moiety. This is confirmed by the correlation between the adsorption free energy (at constant potential) and the polarographic “substituent constant” which reflects the effect of N 1-substitution on the electronic structure on the pNH 2Ø-S moiety. Finally, the good linear correlation between Δ G ads 0 values and the activity parameters related to the biological activity of sulfanilamides suggests the presence of an adsorption step in the mechanism of action able to account for the different bacteriostatic potencies of the compounds.

A study of the interfacial behaviour of several alkaloids at a mercury-solution interface

The results obtained for the measurement of the differential capacity of the interface between mercury and an aqueous buffer solution of acetic acid containing different alkaloids are reported. The properties of the capacity peak, as well as polarographic and electrocapillary results reported elsewhere, indicate the existence of a qualitative relation between the adsorption of the alkaloid and its catalytic influence on the reduction of hydrogen ions as a result of the chemisorption of an intermediate product. The impedance for such a model has been calculated and found to be in agreemen with the experimental values. In the case of strychnine, several parameters characteristics of this model have been evaluated and in particular the value of the fraction of the charge transferred during the chemisorption which is equal to 0.5. The correlation between the results given here and those obtained previously for asymmetric syntheses induced by adsorbed alkaloids is discussed.

The adsorption of strychnine at a mercury—solution interface

The adsorption of strychnine in an aqueous acetate buffer has been studied in order to explain the optimum conditions of an electrochemical asymmetric synthesis in which it is used as inductor. In dilute solutions ( m < 10 −4) the adsorption is a slow kinetic process while at more concentrated values ( m > 10 −4) it is affected by an association in solution. This explains the fact that the optimum conditions for the synthesis are known to correspond to a concentration 10 −4 M in strychnine. Further more while it is not adsorbed at very positive charges, this molecule saturates the surface of the electrode for negative charges between −2 and −7 μCcm −2 ie between −500 and −900 mV (Calomel electrode KCl 0.1 M). At still more negative charges (−1300 mV) hydrogen is catalytically discharged.

The adsorption of choline halides at a mercury—solution interface

The adsorption of choline halides at a mercury—solution interface

The adsorption of choline halides at a mercury-solution interface

The cationic and anionic adsorption from solutions of choline halides at different concentrations and electrode charge have been studied. The results are compared with those of quaternary ammonium halide solutions and qualitatively explained by considering the hydrophobic interactions.

On the kinetics of adsorption and desorption of perchlorate ions in the presence of 3-methyl-isoquinoline at the mercury—aqueous solution interface

Coadsorption of perchlorate ions and 3-methyl-isoquinoline molecules at the mercury—aqueous solution interface results in the formation of a condensed film. The process of ClO − 4 incorporation (or removal) is very slow. Characteristic relaxation times (about 10 −2 s) are several orders of magnitude larger than values typical of ion adsorption at a mercury—solution interface which is free from organic surfactant. The relationships between the rate of the process, the electrode potential and the amount of adsorbed ClO − 4 ions are determined and discussed. The results indicate that the rate of the overall process is controlled by a slow adsorption (or desorption) step whose kinetics are consonant with an isotherm of the Temkin type.

A study of the interfacial behaviour of several alkaloids at a mercury-solution interface

A study of the interfacial behaviour of several alkaloids at a mercury-solution interface

Progress in interfacial chemistry in relation to colloid stability

This paper describes a number of developments in the domain of imterfacial (electro—)chemistry that have repercussions on the understanding of colloid stability. Under conditions of coagulation, the double layers are almost entirely non—diffuse. Information on such double layers is obtainable with the mercury-solution interface and much attention is paid to the translation of this information to systems with which, as a matter of routine, stability studies are done. The silver iodide system is very suitable and as a special example the congruence issue of electrosorption is discussed. Insoluble oxides offer a number of specific problems that require separate treatment. Furthermore, attention is paid to lyotro— pic sequences, to structural contributions to stability and to the dynamics of interaction.

Adsorption isotherms for thiourea at the mercury-solution interface

Double layer parameters for the adsorption of thiourea on mercury were obtained at constant charge and at constant potential on the electrode. In both cases the adsorption isotherm was found to be congruent on the electrical variable. The virial adsorption isotherm is quite adequate to describe the adsorption of thiourea but a different virial coefficient is needed in each case. The study of this simultaneous congruence led to the conclusion that when the adsorption of neutral molecules is considered in terms of the two electrical variables a much more convenient picture of the behaviour of the interface is obtained.

A study of superficial associations at a mercury electrode in the case of tetrabutylammonium halide solutions

The influence of the nature of the anion on the adsorption of the tetrabutylammonium cation from halide solutions at a mercury—solution interface has been studied. A series of measurements of the interfacial tension for such solutions also containing a non-adsorbable cation, have led to the evaluation of the adsorption of both the tetraalkylammonium cation and of the halide anion. The variation of global surface excesses of entropy and concentration with temperature have also been determined. The results obtained can be explained by the formation, at the surface of the electrode, of both paired and non-paired ions, the latter neutralizing the charge on the electrode. The role of hydrophobic forces whose importance has been recognized in the adsorption of neutral substances is stressed in the case of surfaceactive cations.

The behaviour of allyl thiourea at a mercury-solution interface as an example of adsorption in several states with partial electron transfer

The superficial excesses determined from electrode charge measurements have been studied at constant potential or charge. The usual tests suggest a change in the orientation of the adsorbed molecule. It is shown theoretically that the Frumkin isotherm still offers an useful approximation when two adsorbed states are considered. In this case, two at least of the three adjustable parameters, the apparent adsorption energy, and the apparent molecular area, change with the electrical variable, being function of the adsorption energies for both states and also of the corresponding molecular areas. Consistent results are obtained from the consideration of isotherms using this approximation and from examination of the apparent adsorption valency.

The behaviour of allyl thiourea at a mercury-solution interface as an example of adsorption in several states with partial electron transfer

The superficial excesses determined from electrode charge measurements have been studied at constant potential or charge. The usual tests suggest a change in the orientation of the adsorbed molecule. It is shown theoretically that the Frumkin isotherm still offers an useful approximation when two adsorbed states are considered. In this case, two at least of the three adjustable parameters, the apparent adsorption energy, and the apparent molecular area, change with the electrical variable, being function of the adsorption energies for both states and also of the corresponding molecular areas. Consistent results are obtained from the consideration of isotherms using this approximation and from examination of the apparent adsorption valency.

Electrochemical behaviour of mono- and oligonucleotides and the corresponding nucleosides Part VI. Comparative voltammetric study on the adsorption of 1-β-D-arabinofuranosylcytosine and 1-β-D-ribofuranosylcytosine at charged interfaces

Cytostatic actions of 1-β-D-arabinofuranosylcytosine have been reported. Therefore a systematic comparative study was undertaken on the adsorption and association of 1-β-D-arabinofuranosylcytosine (ara-C) and 1-β-ribofuranosylcytosine (r-C) in acid and neutral solution at the mercury-solution interface constituting a model for charged biological interfaces in the living cell with respect to the biophysicochemical behaviour of the studied nucleosides. The adsorption was followed by out-of-phase a.c. voltammetry and by single sweep voltammetry at the hanging mercury drop electrode (HMDE). Characteristic properties and adsorption parameters of the dilute and compact adsorption layers of ara-C and r-C were evaluated from the obtained double step Frumkin isotherm and from the potential dependence of adsorption. While the properties in the dilute layer are rather similar for both, ara-C and r-C, the compact layer of ara-C is more dense indicating a substantial influence of the different steric arrangement in the sugar moiety of both otherwise similar nucleosides. The importance of the obtained results for the biochemical behaviour at natural charged surfaces is discussed.

Electrochemical behaviour of mono-and oligonucleotides and the corresponding nucleosides: Part VI. Comparative voltammetric study on the adsorption of 1-β-D-arabinofuranosylcytosine and 1-β-D-ribofuranosylcytosine at charged interfaces

Cytostatic actions of 1-β-D-arabinofuranosylcytosine have been reported. Therefore a systematic comparative study was undertaken on the adsorption and association of 1-β-D-arabinofuranosylcytosine (ara-C) and 1-β-ribofuranosylcytosine (r-C) in acid and neutral solution at the mercury-solution interface constituting a model for charged biological interfaces in the living cell with respect to the biophysicochemical behaviour of the studied nucleosides. The adsorption was followed by out-of-phase a.c. voltammetry and by single sweep voltammetry at the hanging mercury drop electrode (HMDE). Characteristic properties and adsorption parameters of the dilute and compact adsorption layers of ara-C and r-C were evaluated from the obtained double step Frumkin isotherm and from the potential dependence of adsorption. While the properties in the dilute layer are rather similar for both, ara-C and r-C, the compact layer of ara-C is more dense indicating a substantial influence of the different steric arrangement in the sugar moiety of both otherwise similar nucleosides. The importance of the obtained results for the biochemical behaviour at natural charged surfaces is discussed.