Principles of Polarography

Heyrovský, J.; Kůta, J.

doi:10.1016/b978-0-12-346650-1.50005-9

Cited by 392 publications

(439 citation statements)

References 9 publications

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“…For quasi-labile or non-labile complexes the apparent association rate constant k Ã 0 a can be calculated from the limiting s (i.e.,s * ) using the known expression for the thickness of the pertaining reaction layer, l [16] …”

Section: Dynamic Information Obtained By Sscpmentioning

confidence: 99%

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

Pinheiro

Domingos

Minor

et al. 2006

Journal of Electroanalytical Chemistry

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A lability criterion is developed for dynamic metal binding by colloidal ligands with convective diffusion as the dominant mode of mass transport. Scanned stripping chronopotentiometric measurements of Pb(II) and Cd(II) binding by carboxylated latex core-shell particles were in good agreement with the predicted values. The dynamic features of metal ion binding by these particles illustrate that the conventional approach of assuming a smeared-out homogeneous ligand distribution overestimates the lability of a colloidal ligand system. Due to the nature of the spatial distribution of the binding sites, the change in lability of a metal species with changing ligand concentration depends on whether the ligand concentration is varied via manipulation of the pH (degree of protonation) or via the particle concentration. In the former case the local ligand density varies, whereas in the latter case it is constant. This feature provides a useful diagnostic tool for the presence of geometrically constrained binding sites.

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Section: Dynamic Information Obtained By Sscpmentioning

confidence: 99%

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

Pinheiro

Domingos

Minor

et al. 2006

Journal of Electroanalytical Chemistry

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“…To the contrary, the conventional method, 14 which obtains the formation constant of a complexation reaction in the presence of a large excess of L to M + or M n+ , i.e., Mn…”

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confidence: 99%

Interaction between Monoaza-, Diaza-, or Polyazacrown Ethers and Alkali Metal Ions in Acetonitrile by Polarography

et al. 2000

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Crown-type compounds are of general relevance as synthetic model substances for studying physiological ion-transport processed in biological membranes, for investigating receptor and enzyme interactions as well as for the salt balance and for metabolic processes of living organisms. 1 The complexation between alkali metal ions and macrocyclic polyethers, polyamines or polyetheramines has been extensively studied by means of various methods in many solvent systems. 2,3 The fitness of the cavity size of a macrocyclic compound is an important factor for determining the stability of an alkali metal complex. 4 Solvent effects in the complexation of cryptand [2.2] (1,10-diaza-18-crown-6) with Li + have indicated that the stability of the complex varies inversely with the donicity of the solvent.5 However, little attention may have been paid to the increase in the basicity of coordinating atoms by substitution of the oxygen atoms with NH groups in crown ethers.In the present study, the formation constants of alkali metal complexes with monoaza-, diaza-, and polyazacrown ethers were obtained by means of mainly d.c. polarography; differential pulse polarography on DME and cyclic voltammetry on HMDE were additionally employed.The mercurydissolution processes of the macrocyclic compounds were clarified during the course of examining alkali metal ion complexation. The variation in the formation constants is discussed from the viewpoint of not only cavity size, but also the interaction between the Lewis acids and bases. The main purpose of the present study was to investigate the effects of the number of substitution of the oxygen atoms with NH groups in the crown ethers on the stabilities of the Li + and Na + complexs of 12-crown-4, 15-crown-5, and 18-crown-6.We have developed a new analytical method in d.c. polarography for obtaining the complex formation constant between cations and an anion which induces the mercurydissolution wave on DME. 6 This method was first successfully applied to the Li + -CH3COO-system in acetonitrile. The formation constants of a "reverse coordinated" species, CH3COO -(M + )2 (M + = Li + or Na + ), 6 and later that of (Li + )2Cl -7were obtained. Since then, we have revealed that the Li + ion operates an unexpectedly strong coordination ability in protophobic aprotic solvents. 8,9 Our method was found to be very useful for examining complex formation between alkali metal ions and macrocyclic polyamines (cyclam, tetramethylcyclam) 10,11 as well as acyclic polyamines (ethylenediamine, trien, tetren). 12The complex formation of cryptand[2.2] and its sulfur derivative (ATCO: 1,10-diaza-4,7,13,16-tetrathiacyclooctadecane) with alkali metal or alkaline earth metal ions in acetonitrile has been examined. 13 In principle, "the mercury-dissolution method" utilizes the The complex formation constants between alkali metal ions and monoaza-or diazacrown ethers (L) in acetonitrile have been obtained by the analytical method of d.c. polarography, in which a positive shift in E1/2 of the mercury-dissolution w...

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“…6 The limiting current was independent of the height of the aqueous solution reservoir, indicating that the limiting current is kinetically controlled. 10 The current was proportional to the concentrations of TSDNN (Fig. 2a).…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Study of the SN2 Reaction of 1-p-Toluenesulfonyl-2,4-dinitronaphthalene with Hydroxide Ions at the Nitrobenzene-Water Interface

1998

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The rate of the interfacial nucleophilic reaction of 1-p-toluenesulfonyl-2,4-dinitronaphthalene (TSDNN) with OH -ions at the polarized nitrobenzene (NB)-water (W) interface was studied using a polarographic technique. The TSDNN partitioned into the aqueous phase underwent a displacement of the p-toluenesulfonyl moiety with OH -. The transfer of one of the products, 2,4-dinitronaphthalate (DNN -), from the W phase to the NB phase was monitored as the current across the interface. The rate constant of the reaction of TSDNN with OH -in the aqueous phase was estimated to be 1.03±0.23 dm 3 mol -1 s -1 at 25˚C, which is ten-times higher than the rate constant of the displacement of 2,4-dinitrofluorobenzene with OH -in the aqueous phase, 1.01±0.13×10 -1 dm 3 mol -1 s -1 . The contribution from the reactions in the NB phase and at the interface to the formation of DNN -seems to be negligible, suggesting the absence of an interfacial facilitation of the reaction.

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Principles of Polarography

Cited by 392 publications

References 9 publications

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

Interaction between Monoaza-, Diaza-, or Polyazacrown Ethers and Alkali Metal Ions in Acetonitrile by Polarography

Electrochemical Study of the SN2 Reaction of 1-p-Toluenesulfonyl-2,4-dinitronaphthalene with Hydroxide Ions at the Nitrobenzene-Water Interface

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