The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

1981 ◽  
Vol 59 (13) ◽  
pp. 2053-2071 ◽  
Author(s):  
M. H. Charles ◽  
M. Mulenga ◽  
A. Jenard ◽  
H. D. Hurwitz

Differential capacitances are measured as a function of temperature at the ideal polarized Hg electrode in systems of mixed sodium halides at ionic strength J = 10−1 mol kg−1. A quasi-thermodynamic treatment is presented according to which excess entropies of adsorption in the inner layer are determined. The formation entropy of the inner layer and the water and ion molar entropies of adsorption are presented for a range of moderate and small ionic surface coverages.

2000 ◽  
Vol 65 (3) ◽  
pp. 326-342
Author(s):  
María S. Crespo-Pinilla ◽  
Fernando Mata-Pérez ◽  
Rosa M. Villamañán

A study of two prewaves of the Ni(II)-SCN- system was carried out under the experimental conditions when the influence of electroreduction of SCN- is negligible. Kinetics of Ni(II) reduction in thiocyanate media on the dropping mercury electrode was studied by DC Tast Polarography (DCTP) via determination of Koutecký's parameter χ; the influence of different variables was analyzed. The study of prewaves was performed using various polarographic techniques. Values of χ depend on the SCN- concentration, pH, ionic strength (Ψ-effect) and on the nature of the supporting electrolyte. The number of electrons n, the transfer coefficient α, the stoichiometric number ν, ∆H≠, and ∆S≠ were determined (compensation effect). The first prewave has character of a reaction in the solution, the second prewave is a surface process. Main features of both mechanisms are common: catalytic nature, one-electron step discharge and the rate-determining process between species of opposite charges.


1979 ◽  
Vol 103 (3) ◽  
pp. 399-408 ◽  
Author(s):  
Nguyen Huu Cuong ◽  
A. Jenard ◽  
H.D. Hurwitz

1974 ◽  
Vol 51 (2) ◽  
pp. 377-393 ◽  
Author(s):  
Nguyen Huu Cuong ◽  
C.V. D'Alkaine ◽  
A. Jenard ◽  
H.D. Hurwitz

1973 ◽  
Vol 42 (1) ◽  
pp. 77-103 ◽  
Author(s):  
Henri D. Hurwitz ◽  
Carlos V. D'Alkaine

1973 ◽  
Vol 72 (4) ◽  
pp. 714-726 ◽  
Author(s):  
A. Burger ◽  
B. Miller ◽  
C. Sakoloff ◽  
M. B. Vallotton

ABSTRACT An improved method for the determination of serum triiodothyronine (T3) has been developed. After addition of a tracer amount of the hormone, T3 was extracted from 1 ml serum under conditions of pH and ionic strength which favoured T3 extraction (89%) over thyroxine (T4) extraction (58%). Chromatography of the extracted material on Sephadex LH-20 separated T3 completely from residual T4. The T3 eluate was dried, then re-dissolved in 0.5 ml NaOH 0.04 n. To 0.2 ml duplicate aliquots, a standard amount of TBG was added for the competitive protein analysis. After one hour incubation at 4°C, separation of bound from free T3 was achieved on small Sephadex G-25 columns. Overall recovery was 67 ± 10.8% and correction for the loss was made. The solvent blank was 37 ± 27 (sd) ng/100 ml. Accuracy of measurement of known quantities of T3 added to serum was 98.4%. The coefficient of variation within the assay was 6.2% and between the assays it was 11.4%. The limit of detection (0.1 ng) corresponded to a concentration of 25 ng/100 ml. T4 added to serum did not interfere with T3 determination until high non-physiological values were reached. The mean ± sd serum T3 in 54 euthyroid subjects was 153 ± 58 ng/100 ml and in 24 hyperthyroid patients it was 428 ±186 ng/100 ml; 4 out of the 24 hyperthyroid values were within 2 sd of the mean euthyroid group. All the values found in the euthyroid group were well above the limit of detection of the method.


2020 ◽  
Vol 16 (6) ◽  
pp. 722-737
Author(s):  
Cigdem Yengin ◽  
Emrah Kilinc ◽  
Fatma Gulay Der ◽  
Mehmet Can Sezgin ◽  
Ilayda Alcin

Background: Reverse İontophoresis (RI) is one of the promising non-invasive technologies. It relies on the transition of low magnitude current through the skin and thus glucose measurement becomes possible as it is extracted from the surface during this porter current flow. Objective: This paper deals with the development and optimization of an RI determination method for glucose. CE dialysis membrane based artificial skin model was developed and the dependence of RI extraction on various experimental parameters was investigated. Method: Dependence of RI extraction performance on noble electrodes (platinum, silver, palladium, ruthenium, rhodium) was checked with CA, CV and DPV, in a wide pH and ionic strength range. Optimizations on inter-electrode distance, potential type and magnitude, extraction time, gel type, membrane MWCO, usage frequency, pretreatment, artificial body fluids were performed. Results: According to the optimized results, the inter-electrode distance was 7.0 mm and silver was the optimum noble metal. Optimum pH and ionic strength were achieved with 0.05M PBS at pH 7.4. Higher glucose yields were obtained with DPV, while CA and CV achieved almost the same levels. During CA, +0.5V achieved the highest glucose yield and higher potential even caused a decrease. Glucose levels could be monitored for 24 hours. CMC gel was the optimum collection media. Pretreated CE membrane with 12kD MWCO was the artificial skin model. Pretreatment affected the yields while its condition caused no significant difference. Except PBS solution (simulated as artificial plasma), among the various artificial simulated body fluids, intestinal juice formulation (AI) and urine formulation U2 were the optimum extraction media, respectively. Conclusion: In this study, various experimental parameters (pretereatment procedure, type and MWCO values of membranes, inter-electrode distance, electrode material, extraction medium solvents, ionic strength and pH, collection medium gel type, extraction potential type and magnitude, extraction time and etc) were optimized for the non-invasive RI determination of glucose in a CE dialysis membrane-based artificial skin model and various simulated artificial body fluids.


1983 ◽  
Vol 48 (10) ◽  
pp. 2903-2908 ◽  
Author(s):  
Viktor Vrabec ◽  
Oldřich Vrána ◽  
Vladimír Kleinwächter

A method is described for determining total platinum content in urine, blood plasma and tissues of patients or experimental animals receiving cis-dichlorodiamineplatinum(II). The method is based on drying and combustion of the biological material in a muffle furnace. The product of the combustion is dissolved successively in aqua regia, hydrochloric acid and ethylenediamine. The resulting platinum-ethylenediamine complex yields a catalytic current at a dropping mercury electrode allowing to determine platinum by differential pulse polarography. Platinum levels of c. 50-1 000 ng per ml of the biological fluid or per 0.5 g of a tissue can readily be analyzed with a linear calibration.


1981 ◽  
Vol 46 (2) ◽  
pp. 368-376 ◽  
Author(s):  
Josef Veselý

Titration of sulphates with lead perchlorate employing lead ion selective electrode indication was studied using additions of various organic solvents at different pH' and ionic strength values. As the optimum emerged systems with 60-70% 1,4-dioxane, pH' 5.3-5.6. After dehydration with sodium hydroxide, dioxane must be freed from the electrode surface-oxidizing impurities by their reduction with sodium metal and subsequent distillation. The method was applied to determination of sulphates in mountain spring waters. Units of ppm can be determined; the limit of determination, however, depends considerably on the content of dioxane, total salt content in the sample, and speed of the semi-automatic titration. Lead can be determined with EDTA in concentrations down to c(Pb2+) = 5 . 10-6 mol l-1.


1991 ◽  
Vol 56 (7) ◽  
pp. 1434-1445 ◽  
Author(s):  
Jiří Barek ◽  
Ivana Švagrová ◽  
Jiří Zima

Polarographic reduction of the genotoxic N,N’-dinitrosopiperazine was studied and its mechanism was suggested. Optimum conditions were established for the determination of this substance by tast polarography over the concentration region of 1 . 10-3 to 1 . 10-6 mol l-1 and by differential pulse polarography on the conventional dropping mercury electrode or by fast scan differential pulse voltammetry and linear sweep voltammetry on a hanging mercury drop electrode over the concentration region of 1 . 10-3 to 1 . 10-7 mol l-1. Attempts at increasing further the sensitivity via adsorptive accumulation of the analyte on the surface of the hanging mercury drop failed. The methods are applicable to the testing of the chemical efficiency of destruction of the title chemical carcinogen based on its oxidation with potassium permanganate in acid solution.


1996 ◽  
Vol 61 (3) ◽  
pp. 333-341
Author(s):  
Jiří Barek ◽  
Roman Hrnčíř ◽  
Josino C. Moreira ◽  
Jiří Zima

The polarographic behaviour was studied for 6-β-D-glucopyranosyloxy-7-hydroxycoumarin, a natural compound serving as an optical whitening agent. The substance can be quantitated by tast polarography, differential pulse polarography using a conventional dropping mercury electrode, and differential pulse polarography using a static mercury drop electrode over the regions of 20-1 000, 2-1 000, and 0.2-1 000 μmol l-1, respectively. The methods developed for the quantitation of the compound were applied to its direct determination in a raw product.


Sign in / Sign up

Export Citation Format

Share Document