Complex formation and fluorescence : Part II The use of 8-hydroxyquinoline-5-sulfonic acid as an indicator

The use of fluorescent 8-hydroxyquinoline-5-sulfonic acid complexes in titrations was examined. The disappearance of the fluorescence of these metal complexes, upon titration with a stronger, nonfluorescing complexing agent can be used to indicate endpoints in both complexometric titrations and acid-base titrations.     

Complex formation and Fluorescence : Complexes of 8-hydroxyquinoline-5-sulfonic acid

The fluorescence of solutions of cation complexes with 8-hydroxyquinoline-5-sulfonic acid has been studied. The complexes formed with transition elements do not fluoresce. The additivity of the fluorescence at certain pH values has been used to indicate new generally applicable analytical method for mixtures of cations which have similar reactions. The method is especially applicable to small or very dilute samples.     

Benzohydroxamic acid as a reductometric titrant: Determination of thorium

Milligram quantities of thorium can be accurately determined by precipitating it as oxalate, dissolving the precipitate in 11 sulphuric acid and oxidizing the liberated oxalic acid with a known excess of standard permanganate solution above 60 °C in sulphuric acid medium, and finally estimating the excess permanganate by titrating with a standard solution of benzohydroxamic acid either visually or potentiometrically. 10 mg quantities of thorium has been estimated with an error not exceeding 0.12%. The coefficient of variation for 10 estimations is found to be 0.06% and 0.12% for potentiometric and visual methods, resp.     

Fluorosulphuric acid as a titrant in alcoholic solvents

Fluorosulphuric acid gives highly conducting solutions in alcohols and alcoholic mixtures. Solutions in methanol or in ethylene glycol -methanol give the best results for the direct titration of organic bases, although other alcohols are also satisfactory. Potontioimetric and visual methods of end-point detection are suitable.     

Trifluoromethyl sulphonic acid as a titrant in glacial acetic acid systems

Trifluoromethyl sulphonic acid in glacial acetic acid has been compared with perchloric acid in glacial acetic acid as a titrant in a limited number of cases. It does not appear that the reagent is likely to compete seriously with perchloric acid in non-aqueous titrimetry. Although comparable to perchloric acid in acid strength in acetic acid as well as in instrument response, it is unlikely that the considerably higher cost can be justified on the grounds of freedom from precipitate formation alone and no other advantageous feature has been observed which could justify this.

Abstract

Trifluoromethylsulfonsäure in Eisessig wurde mit Perchlorsäure in Eisessig als Titrationsmittel verglichen. Es scheint nicht wahrscheinlich, dass das Reagens ernsthaft mit Perchlorsäure als Titrationmittel in nichtwässrigem Medium konkurrieren kann. Das Reagens ist zwar mit Perchlorsäure vergleichbar, soweit es die Stärke (in Essigsäure) und das Ansprechen des Instrumentes betrifft; es ist aber unwahrscheinlich, dass sich die beträchtlich höheren Kosten lediglich wegen Nichtauftretens von Niederschlägen rechtfertigen lassen. Dies ist der einzige auffindbare Vorteil.     

Use of sodium citrate as a new titrant for the microdetermination of sulfanilic acid

Sulfanilic acid was determined in microquantities with a new titrant, i.e., sodium citrate solution using bromocresol purple as indicator. Estimation were carried out in the range of 0.096–0.574 mg with a maximum error of ±0.004 mg.     

Benzohydroxamic acid as a reductometric titrant determination of manganese in ores and alloys

Benzohydroxamic acid has been employed as a reductometric titrant for the determination of manganese in various ores and alloys. The determination is based on the fact that benzohydroxamic acid reduces Mn(VII) quantitatively to Mn(II) in 1.5N sulphuric acid.     

Benzohydroxamic acid as a reductometric titrant: Determination of manganese, chromium and vanadium in steels

A method has been developed for the rapid determination of manganese and chromium by direct stepwise reductometric titration with benzohydroxamic acid, and of vanadium by titration with ascorbic acid (with benzohydroxamic acid as indicator) in the same aliquot. The method is free from the interference of common alloying elements present in steels. Some BCS steel samples have been analysed with good precision and accuracy.     

8-Quinolinol-5-sulfonic acid-loaded resin as a preconcentrating agent in the neutron activation analysis of the chalcophile elements (author's transl)]

A chelating agent-loaded resin consisting of 8-quinolinol-5-sulfonic acid and an anion-exchange resin (HOx-resin) was prepared in order to concentrate trace chalcophile elements in natural water samples selectively before neutron activation analysis. The exchange capacity of the Diaion SA No. 100 for the reagent (1.8 meq . g-1 resin) corresponds approximately to that for chloride ion (1.83 meq . g-1 resin), indicating that 8-quinolinol-5-sulfonic acid is adsorbed quantitatively on the exchange site of the resin through the sulfonate anion in the reagent. The basic conditions for the adsorption of the metal ions on the resin were investigated by employing the column method. The nitrate concentration and the pH of the sample solution affect the adsorption behavior of metal ions. Several solutions containing metal ions with varying pH or varying nitrate concentration were applied to the resin column (35 mm x 7 mm phi) with a flow rate of 2.0 cm3 . min-1. As a result, the optimum conditions for the quantitative adsorption of copper(II), zinc(II), cadmium(II), cobalt(II), nickel(II) and manganese(II) were as follows: NO3- less than 0.01 mol . dm-3 pH greater than 4.6. Furthermore, the feasibility of the above conditions as well as quantitative adsorption of the chalcophile elements was confirmed through the neutron activation analysis of the synthesized metal solutions.     

Complex formation of gallium(III) with 8-hydroxy-7-iodoquinoline-5-sulphonic acid (ferron)

The complex formation of gallium(III) with 8-hydroxy-7-iodoquinoline-5-sulphonic acid (ferron) (L) was studied by potentiometry; and the dissociation constants of the ligand were redetermined. A new computer program made it possible to make allowance for a considerable number of equilibria. In the pH range 2–10, the main species were as follows (the logarithm of the absolute stability constants at 25.0 ±0.1° for ionic strength 0.1 M are given in parentheses): GaHL (11.3), GaL (14.7), Ga(OH)₂L (32.3), GaL₂ (23.9), GaOHL₂ (31.0) and GaL₃ (29.6). For 1:1, 1:2 and 1:3 mixtures of metal with ferron, the mole fractions of the various complexes as a function of pH were calculated; the effect of pH on the conditional constants of the species GaL, GaL₂ and GaL₃ was also established.     

OH⋅⋅⋅N and CH⋅⋅⋅O Hydrogen Bonds Control Hydration of Pivotal Tropane Alkaloids: Tropinone⋅⋅⋅H2O Complex

The effect of monohydration in equatorial/axial isomerism of the common motif of tropane alkaloids is investigated in a supersonic expansion by using Fourier‐transform microwave spectroscopy. The rotational spectrum reveals the equatorial isomer as the dominant species in the tropinone???H₂O complex. The monohydrated complex is stabilized primarily by a moderate O?H???N hydrogen bond. In addition, two C?H???O weak hydrogen bonds also support this structure, blocking the water molecule and avoiding any molecular dynamics in the complex. The water molecule acts as proton donor and chooses the ternary amine group over the carbonyl group as a proton acceptor. The experimental work is supported by theoretical calculations; the accuracy of the B3LYP, M06‐2X, and MP2 methods is also discussed.     

Crystal Structure of the p-cumylcalix[8]arene-dimethylsulfoxide 1:5 Complex

p-cumylcalix[8]arene crystallizes with 5 DMSO molecules in the tetragonalspace group P4. The parameters have values: a = b = 17.443(3), c = 9.829(2) Å. Refinement based on 2454 observed reflections led to afinal R value of 0.073. Four dimethylsulfoxide molecules are connected by hydrogenbonds to the calixarene. The macrocycle shows an alternate conformation around the 4 axis. In the network, another DMSO in disordered manner is a foundbetween the calixarenes.     

Enhancement and quenching of fluorescence of metal chelates of 8-hydroxyquinoline-5-sulfonic acid

Fluorescence enhancement of 8-hydroxyquinoline-5-sulfonic acid complexes of Mg, Ca, Sr, Ba, Al, Zn and Cd were studied in micellar and hydroorganic solvents. Al is extraordinarily amenable to both types of fluorescence enhancement, an order of magnitude to two order of magnitude enhancement of fluorescence intensity has been observed with aqueous hexadecyltrimethylammonium chloride (HTAC) and certain mixed aqueous-organic solvents. Fe(III) appears to be an unusually powerful fluorescence quencher in these systems — the effect is noticeable in low micromolar concentrations and is greatly amplified by cationic surfactants such as HTAC.     

5-Naphthylazo-8-hydroxyquinoline (5NA8HQ) as a novel corrosion inhibitor for mild steel in hydrochloric acid solution

In this study, 5-naphthylazo-8-hydroxyquinoline (5NA8HQ) was synthesized, characterized, and tested as a corrosion inhibitor for mild steel in 1 M HCl solution in the temperature range 20 to 50 °C. Weight-loss and potentiodynamic polarization measurements were used to analyse the corrosion behaviour of the metal in the absence and presence of different concentrations of the inhibitor. Analyses of surface film and inhibited solutions by FT-IR and UV–visible spectroscopy enabled us to clarify aspects of the inhibition mechanism. Further examination using X-ray diffraction confirmed the action of 5NA8HQ as an effective inhibitor of corrosion of mild steel in acidic media. The results obtained showed that this compound was a good inhibitor of corrosion. The inhibition is of mixed anodic–cathodic nature with predominance of anodic character. The Langmuir isotherm was found to accurately describe the adsorption behaviour of 5NA8HQ. Spectrophotometric analysis showed the formation of a layer at the surface of the corroded sample; this was interpreted as formation of complexes between 5NA8HQ and metal cations present in the steel structure.     

Aqueous phenylacetic acid as a low-dose fluorescence dosimeter

Total fluorescence of aqueous phenylacetic acid system at neutral pH has been evaluated as low-dose -ray chemical dosimeter, using the fluorescence accessory of a UV-Vis spectrophotometer. The useful working range of the system is from 4 to 70 Gy. The postirradiation stability of the dosimeter response has been studied at different pH's, storage temperatures and light conditions. The post-irradiation stability of the dosimeter decreases with an increase in storage temperature. The stability is not affected in diffuse sunlight but it is very unstable in direct sunlight.     

Complex formation of alkaline-earth cations with crown ethers and cryptands in methanol solutions

The complexation of alkaline-earth cations by different crown ethers, azacrown ethers, and cryptands has been studied in methanol solutions by means of calorimetric and potentiometric titrations. The smallest monocyclic ligands examined form 21 complexes (ratio of ligand to cation) with cations which are too large to fit into the ligand cavity. With the smallest cryptand, only Sr²⁺ and Ba²⁺ ions are able to form exclusive complexes. In the case of the reaction of cryptand (211) with Ca²⁺, a separate estimation of stability constants for the formation of exclusive and inclusive complexes was possible for the first time. Higher values for stability constants are found for the reaction of alkaline-earth cations with cryptands compared to the reaction with alkali ions. This increase is only caused by favorable entropic contributions.