scholarly journals The Kiselev isotherm for adsorption at the liquid-solid interface: Solving the mystery of negative equilibrium constants

2021 ◽  
Vol 343 ◽  
pp. 117674
Author(s):  
Khim Hoong Chu
Author(s):  
J.A. Panitz

The first few atomic layers of a solid can form a barrier between its interior and an often hostile environment. Although adsorption at the vacuum-solid interface has been studied in great detail, little is known about adsorption at the liquid-solid interface. Adsorption at a liquid-solid interface is of intrinsic interest, and is of technological importance because it provides a way to coat a surface with monolayer or multilayer structures. A pinhole free monolayer (with a reasonable dielectric constant) could lead to the development of nanoscale capacitors with unique characteristics and lithographic resists that surpass the resolution of their conventional counterparts. Chemically selective adsorption is of particular interest because it can be used to passivate a surface from external modification or change the wear and the lubrication properties of a surface to reflect new and useful properties. Immunochemical adsorption could be used to fabricate novel molecular electronic devices or to construct small, “smart”, unobtrusive sensors with the potential to detect a wide variety of preselected species at the molecular level. These might include a particular carcinogen in the environment, a specific type of explosive, a chemical agent, a virus, or even a tumor in the human body.


1987 ◽  
Vol 48 (3) ◽  
pp. 389-405 ◽  
Author(s):  
P. Nozières ◽  
M. Uwaha

1983 ◽  
Vol 48 (1) ◽  
pp. 52-59 ◽  
Author(s):  
Vlastimil Kubáň ◽  
Miroslav Macka

The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the reactions of formation of the ML and ML2 complexes of both reagents with cadmium(II) ions were determined by graphical analysis and numerical interpretation of the absorbance-pH curves by the modified SQUAD-G program. Optimal conditions were proposed for the spectrophotometric determination of Cd in 10% v/v ethanol medium in the presence of 0.1% w/v Triton X-100 or 1% w/v Brij 35. BrPADAP and ClPADAP are the most sensitive spectrophotometric reagents for the determination of cadmium(II) ions (ε = 1.28-1.44 . 105 mmol-1 cm2 at 560 nm and pH 8.0-9.5) with a high colour contrast in the reaction (Δλmax ~117 nm) and a selectivity similar to that of other N-heterocyclic azodyes (PAR, PAN, etc.).


1982 ◽  
Vol 47 (12) ◽  
pp. 3375-3380 ◽  
Author(s):  
Jaroslav Holeček ◽  
Karel Handlíř ◽  
Milan Nádvorník ◽  
Milan Vlček

Kinetics have been studied of oxidation of (1-hydroxybenzyl)ferrocenes substituted in phenyl ring with bis(triphenylsilyl) chromate in benzene solutions as well as protonation of these alcohols in sulphuric acid medium. Logarithms of the oxidation rate constants (kobs, 20-40 °C) and those of the protonation equilibrium constants (KR+, 25 °C) show linear dependence on the Hammett σ constants, the ρ constant values being -0.86 to -0.40 and -2.50, respectively. These negative values suggest that the both processes are influenced by the same effects and confirm the mechanism proposed earlier for oxidation of alcohols with ferrocenyl substituent by action of bis(triphenylsilyl) chromate in aprotic solvents.


1985 ◽  
Vol 50 (3) ◽  
pp. 581-599 ◽  
Author(s):  
Petr Vaňura ◽  
Emanuel Makrlík

Extraction of microamounts of Sr2+ and Ba2+ (henceforth M2+) from the aqueous solutions of perchloric acid (0.0125-1.02 mol/l) by means of the nitrobenzene solutions of dicarbolide (0.004-0.05 mol/l of H+{Co(C2B9H11)2}-) was studied in the presence of monoglyme (only Ba2+), diglyme, triglyme, and tetraglyme (CH3O-(CH2-CH2O)nCH3, where n = 1, 2, 3, 4). The distribution of glyme betweeen the aqueous and organic phases, the extraction of the protonized glyme molecule HL+ together with the extraction of M2+ ion and of the glyme complex with the M2+ ion, i.e., ML2+ (where L is the molecule of glyme), were found to be the dominating reactions in the systems under study. In the systems with tri- and tetraglymes the extraction of H+ and M2+ ions solvated with two glyme molecules, i.e., the formation of HL2+ and ML22+ species, can probably play a minor role. The values of the respective equilibrium constants, of the stability constants of complexes formed in the organic phase, and the theoretical separation factors αBa/Sr were determined. The effect of the ligand structure on the values of extraction and stability constants in the organic phase is discussed.


1986 ◽  
Vol 51 (3) ◽  
pp. 498-515 ◽  
Author(s):  
Emanuel Makrlík ◽  
Petr Vaňura

Extraction of Eu3+ and Ce3+ microamounts from 0.1-0.4M perchloric acid by the nitrobenzene solution of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (Mr = 200, 300, 400) has been studied. The equilibrium data and the typical maxima on the dependence of the metal distribution ratio on the total analytical concentration of polyethylene glycol in the system can be explained assuming that the species ML3+org, ML3+2org, ML3+3org, MLH2+-1org, and HL+org (where M3+ = Eu3+, Ce3+; L = polyethylene glycol) are extracted into the organic phase. The values of extraction and equilibrium constants in the organic phase were determined and the effect of the polyethylene glycol molecular weight on the equilibrium constants and on the abundances of individual species in the organic phase is discussed. It has been found that the addition of polyethylene glycol to the acid - nitrobezene - dicarbolide system increases the values of the separation factors αCe/Eu.


1982 ◽  
Vol 47 (10) ◽  
pp. 2676-2691 ◽  
Author(s):  
Miroslav Macka ◽  
Vlastimil Kubáň

The optical and acid-base characteristics of BrPADAP and ClPADAP were studied in mixed water-ethanol and water-DMF media and in 10% ethanol medium in the presence of cationic, anionic and nonionic tensides. The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the ML and ML2 complexes with zinc(II) ions were found by graphical analysis and numerical interpretation of the absorbance curves by the modified SQUAD-G program. Optimal conditions were found for the spectrophotometric determination of Zn(II) in the presence of 0.1% Triton X-100 or 1% Brij 35 in alkaline media with pH = 6.5-10. BrPADAP and ClPADAP are the most sensitive reagents (ε = 1.3-1.6 . 105 mmol-1 cm2 at 557 and 560 nm, respectively) for the determination of zinc with high colour contrast of the reaction (Δλ = 104 nm) and selectivity similar to that for the other N-heterocyclic azodyes (PAN, PAR, etc.).


1980 ◽  
Vol 45 (10) ◽  
pp. 2645-2655 ◽  
Author(s):  
Antonín Mikan ◽  
Miloš Bartušek

The reactions of sorbitol, mannitol, adonitol, dulcitol, glucose and glycerol with H3AsO4, H3AsO3, H3BO3 and GeO2 acids in dilute aqueous solutions were studied by potentiometric neutralization titrations. The formation of the following chelates was demonstrated: As(V)L3-, As(III)L(OH)2-, HAs(III)L(OH)2, BL2-, GeL2(OH)- and GeL32- and the equilibrium constants for their formation were found. Conditions for formation of these chelates of organic oligohydroxy compounds are discussed.


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