Studies On The Use Of Halide Ion Selective Electordes In Salt Media And The Extension Of The Generalized Standard Addition method To Determine The Concentration Of Halide Ions In Geothermal Brins

Abstract

The effect of chloride on the bromide and iodide solid state precipitate electrodes is studied and selectivity constants calculated. The use of multiple linear regression analysis to determine the initial concentration of halide ions in solutions is studied and the resulting technique is used to determine fluoride, iodide and bromide in a geothermal-geopressured brine.     

Crystal structures of hydrates of simple inorganic salts. III. Water‐rich aluminium halide hydrates: AlCl3·15H2O,AlBr3·15H2O,AlI3·15H2O,AlI3·17H2O and AlBr3·9H2O

Water‐rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low‐temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI₃·15H₂O, half of the Al³⁺ cations are surrounded by two complete hydration spheres, with six H₂O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al³⁺.     

A Fluorescence Quenching Method for the Determination of Iodide Ion with Salicylfluorone and Hydrogen Peroxide

Abstract

A highly sensitive and selective fluorescence quenching method has been developed for rapid determination of iodide ion with salicylfluorone (SAF) as fluorogenic reagent (λ_ex = 495 nm, λ_em = 520 nm) at pH 2.5-3.0. The calibration graph is linear over the range 0.05-300 μg/25 ml. The detection limit is 0.05 μ/25 ml iodide. Other halide ions do not interfere with the determination even when present in large excess. The method is rapid and was successfully applied for the determination of iodide ion in sodium chloride, table salt and low sodium salt.     

Polyelectrolyte behavior and conformation of poly-L-methionine S-methylsulfonium salts in aqueous solution

The influence of the species of counterion on the polyelectrolyte behavior and the conformation of poly-L -methionine S-methylsulfonium salts in aqueous solution was studied by viscometric, electrochemical, and optical measurements. The degree of binding of small counterions to charged polyions increases in the sequence: chloride ? bromide < iodide < thiocyanate. The conformations of chloride and bromide salts are independent of polymer concentration. On the contrary, iodide and thiocyanate salts indicate a conformational transition, probably from a random-coil conformation to an intermolecularly stabilized β-form, with the increase of polymer concentration. The results suggest the existence of a strong specific interaction between counterion and macroion in iodide and thiocyanate salt solutions at high polymer concentration.     

Radioanalytical investigation on rhodium extraction behaviour with tri-N-butylphosphate from iodide solutions

Radioanalytical techniques are used in this work to investigate the extraction behaviour with TBP of rhodium (III) chloride solutions to which a large excess of iodide is added. Extraction yields and distribution coefficients are determined as a function of HClO₄ or H₂SO₄ content in the aqueous phase. Rhodium-stripping from the organic phase with ammonia solutions is also tested.     

Study on the Alkylation and Sulfonylation of 3-Aryl-1-methyl-1,2,4-triazolin-5-ones

The alkylation and sulfonylation of 3-aryl-1-methyl-1,2,4-triazolin-5-ones (1) were studied with various alkyl halides and sulfonyl chlorides. The alkylation of 1 with methyl iodide and ethyl bromide afforded N-alkylated products, however with methyl 2-bromopropionate afforded O-alkylated products predominantly. The sulfonylation by methanesulfonyl chloride afforded a mixture of N-sulfonylated and O-sulfonylated products, while the sulfonylation by p-toluenesulfonyl chloride afforded mainly O-sulfonylated products.     

REACTIONS OF 1,3-OXAZOLIDINE-2-THIONE WITH ZINC(II), CADMIUM(II) AND MERCURY(II) HALIDES

Abstract

The reactivity of 1,3-oxazolidine-2-thione towards II B group metals is considered. Cadmium halides, mercury chloride and bromide react to give coordination compounds, whose stereochemistry is tentatively assigned by their i.r. spectra.

Otherwise zinc halides and mercury iodide induce a ring opening.     

Construction of Suitable Iodide–Selective Electrode Based on Phenyl Mercury (II)(2‐mercaptobezothiozolate) Carrier

Abstract

Highly selective poly(vinyl chloride) (PVC) membrane electrode based on recently synthesized mercury complex i.e., phenyl mercury (II) (2‐mercaptobezothiozolate) (PMMBT) as new carrier for iodide‐selective electrode by incorporating the membrane ingredients on the surface of graphite electrode are reported. The effect of various parameters including the membrane composition, pH, and possible interfering anions were investigated on the response properties of the electrode. The developed sensor exhibited Nernstian responses toward iodide over a wide concentration range of 1×10^?7 to 0.1 M with slopes of 57.6±0.8 mV per decade of iodide concentration and detection limit of 8×10^?8 M, over a wide pH ranges of 2.0–11.5. The sensors have response time of 0.5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrode show good ability to discriminate iodide over several inorganic and organic anions.

The electrode was successfully applied to direct determination of iodide in synthetic mixture, waste water and drinking water, and pharmaceutical samples in addition to applying as indicator electrode in precipitation titration.     

ALKYLATIOIM,ACYLATION, AND ARYLATION PRODUCTS OF 1-CYANO-ISOTHIOCHROMANE

Abstract

1-Cyano-isothiochromane (1a) can be alkylated in position 1, using the carbanion that is formed from sodium amide, sodium hydride, or n-butyllithium. With methyl iodide or ethyl iodide 1c and 1d are formed; with α-halogenated ether or thioether, 1e and 1f; with propargyl bromide, 1h; with bromo acetophenone, li; and with ethyl chloroacetate, 1k. Similarly, acylation with benzoyl chloride leads to 11, and with 2,4-dinitrofluorobenzene to 1m. The alkylation products of 1a can be oxidized with peracids to the sulfones 2 and with LiAlH₄ reduced to 1-aminomethyl-isothiochroman (3): Acid hydrolysis of 1 gave isothiochromane-1-carboxylic acids, 4, whereas when 1 is treated with hydrogen peroxide in alkaline medium the S-dioxide and the S-oxide acid amides, 5 and 6 respectively, are formed.     

A new anion receptor utilising aromatic and aliphatic C…H hydrogen bonds

We have synthesised 2, which bound weakly basic halide ions only with C–H…anion hydrogen bonds. Compound 2 utilised one aromatic C–H hydrogen bond and one benzylic C–H hydrogen bond to bind weakly halide ions such as chloride, bromide and iodide in solution. Ab initio calculations of binding energy values for these anions are in good agreement with experimental data. Although the binding affinities of 2 for these anions were low, 2 could be a unique example of host, which utilised only C–H hydrogen bonds to bind anion.     

Edge Plane Pyrolytic Graphite Electrodes for Halide Detection in Aqueous Solutions

The behavior of chloride, bromide and iodide at edge plane pyrolytic graphite electrodes has been explored in aqueous acid solutions. The voltammetric response in each case has been compared with that of basal plane pyrolytic graphite, glassy carbon and boron‐doped diamond. The electrochemical oxidation of chloride is found to only occur on boron‐doped diamond while the electrochemical reversibility for the oxidation of bromide on edge plane pyrolytic graphite is similar to that seen at glassy carbon whilst being superior to basal plane pyrolytic graphite and boron‐doped diamond. In the case of iodide oxidation, edge plane and basal plane pyrolytic graphite and glassy carbon display similar electrode kinetics but are all superior to boron‐doped diamond. The analytical possibilities were examined using the edge plane pyrolytic graphite electrode for both iodide and bromine where is was found that, based on cyclic voltammetry, detection limits in the order of 10^?6 M are possible.     

Methylation of tin(II) by methyl iodide in porewater

The methylation of tin(II) chloride by methyl iodide in porewater and formation of monomethyltin as the only methyltin product are described. A factorial experiment tested the effects of concentrations of tin(II), methyl iodide, and oxygen on monomethyltin yields. The experiments gave 0.18 to 12.8 % yield. Analysis of variance (ANOVA) calculations showed that all three variables were significant at the 95 % level. Comparison of yields in aqueous 23 g kg^?1 sodium chloride solutions to those in porewater and to those containing fulvic acid, salicylic acid, and EDTA showed that only fulvic acid significantly reduced yields. Reasons for this observation are discussed and the findings in the model system are related to methylation of tin compounds in sediments.     

Electron Capture Gas Chromatography of Nitrazepam in Human Plasma as Methyl Derivative

Abstract

A method for quantitative determination of nitrazepam in human plasma in the range 5 - 100 ng/ml is presented.

Nitrazepam is extracted with benzene from plasma samples of 0.5 ml, methylated with methyl iodide and determined gas chromatographically with an electron capture detector of ⁶³Ni-type.

Acid dissociation constants of nitrazepam are determined and the partition properties studied with benzene, methylene chloride and diethyl ether as organic phases.

The selectivity of the method with respect to the metabolites has been thoroughly studied.     

Oxidation of organic compounds by tervalent manganese compounds: IX. Determination of the titer of hexaquomanganese(III) ion standard solutions in perchloric acid

Optimum conditions have been found for the determination of the titer of 0.005 N solutions of hexaquomanganese(III) ion by potentiometric titration of ferrous chloride. The accuracy and reproducibility of this method were studied. A new method of determining the titer of dilute solutions of hexaquomanganese(III) ion has been proposed, using potassium iodide as a primary standard. The optimum conditions for this titration have been found and its applicability to the determination of the titer of 0.005, 0.001, and 0.0005 N solutions has been verified.     

Comparative effect of N-decyl- and N-phenacylmethylpyridinium bromides in acid corrosion of steel

Comparative analysis of inhibitory effect of N-decyl and N-phenacylmethylpyridinium bromides and their mixtures with potassium chloride, bromide, and iodide, and also with urotropin and paraform was carried out at corrosion of steel 08 KP in 3 M H₂SO₄ solutions.     

Sequential injection system for simultaneous determination of chloride and iodide by a Gran’s plot method

This paper describes an automated set-up based on the sequential injection analysis (SIA) concept with potentiometric detection for the determination of chloride and iodide at low concentrations. The assessment of both ion concentrations is accomplished by titration with silver ions using the Gran’s plot approach. The proposed procedure enables chloride and iodide to be determined simultaneously in the range 6.0×10⁻⁶ to 1.0×10⁻⁴ mol l⁻¹ if a minimum silver concentration in the volumetric solution is chosen (5×10⁻⁵ mol l⁻¹). Conventional titrations based on the first derivative evaluation of the equivalence points applied to the same solutions fail, especially for chloride determinations. Although, a comparison of results obtained for higher analyte concentrations shows that they have similar accuracy and precision.     

Chloride distribution coefficient on strongly basic anion-exchange resin: Dependence on co-ion in alkali fluoride solutions

Summary The dependence of the chloride distribution coefficient on the co-ion of solutions of different alkali fluorides, MF, up to 11M is tested on the strongly basic anion-exchange resin AG1-X10. Under the same experimental conditions the distribution coefficient decreases in the following order for M⁺: Na⁺>K⁺>Rb⁺>Cs⁺. This can be explained by the different co-ion-chloride interactions. The consequence of this interaction for a chromatographic separation of chloride is shown with 5M KF and CsF solutions, used as eluants. Depending on the fluoride concentration, the distribution coefficient passes through a minimum value to increase again at higher electrolyte concentration. The non-exchange electrolyte in the resin phase is responsible for this effect. In addition, the bromide and the iodide distribution coefficients up to 10M KF solutions are determined. One results is that the selectivity coefficient between halide ions increases at higher electrolyte concentrations.     

具有可逆热致变色有机-无机杂化铜化合物的合成及表征

在浓盐酸水溶液中，碘化N，N-二甲基-1，5-二氮杂环[3.2.1]辛烷（[3.2.1-Me₂dabco]I₂）和碘化1-氨基-1，4-二氮杂环[2.2.2]辛烷（[2.2.2-NH₂dabco]I）与氯化铜反应得到2种有机-无机杂化铜化合物[3.2.1-Me₂dabco][CuCl₄]（1）和[2.2.2-NH₂dabco][CuCl₄]（2）。X射线单晶结构衍射证实化合物1和2中的无机阴离子是[CuCl₄]^2-四面体。化合物1和2表现出可逆的热致变色现象，随着温度升高，它们的颜色从黄色变为红色，这应该是由[CuCl₄]^2-四面体的变形引起的。     

Microwave‐Assisted Synthesis of cAMP Phosphodiesterase Inhibitor 8‐Hydroxy‐6,7‐dimethoxy‐3‐hydroxymethylisocoumarin

An efficient microwave‐assisted synthesis of 8‐hydroxy‐6,7‐dimethoxy‐3‐hydroxymethyl isocoumarin (1), a metabolite of Streptomyces mobaraensis and structural relative of reticulol and cytogenin that possesses potent cyclic nucleotide phosphodiesterase inhibitor activity, is described. 3,4,5‐Trimethoxyhomophthalic acid (2) was condensed with acetoxyacetyl chloride under microwave irradiation and the acid hydrolysis of resulting 6,7,8‐trimethoxy‐3‐acetoxymethylisocoumarin (3) afforded the 6,7,8‐trimethoxy‐3‐hydroxymethylisocoumarin (4). Regioselective demethylation of the latter using magnesium iodide in THF yielded the title compound (1).     

Indirect atomic absorption spectrometric determination of mixtures of chloride and iodide by precipitation in an unsegmented flow system

Chloride and iodide are injected into a carrier silver nitrate and the precipitates formed are retained on a stainless-steel filter, so that total chloride and iodide can be determined by the decrease in the atomic absorption signal for silver. The silver chloride precipitate is subsequently dissolved with ammonia and chloride only is determined. Iodide is determined by difference. Mixtures of these anions at μg ml^?1 levels can be determined for chloride/iodide ratios from 7.5:1 to 1:60, with a sampling frequency of ca. 10 h^?1. Applications to the determination of chloride in foodstuffs and wines are described. Up to 10 samples per hour can be handled and 50–100 samples can be run before the filter must be cleaned.