The Determination of Organic Compounds by Ther Oxidation with Permanganate

Abstract

The possibility of applying the graphical logarithmic ¹ extrapolation method of Siggia and co-workers to the analysis of mixtures of two organic subatences based on their redox reaction with permanganate has been verified. For this task, the oxidation of a mixture of formic and tartaric acids with pemanganate ir? a buffered medium was chosen.     

Chemiluminescence method with potassium permanganate for the determination of organic pollutants in seawater.

A chemiluminescence method with potassium permanganate was developed for use as an indicator of organic pollutants in fresh water. This method could be applied to the determination of organic pollutants in seawater as well. However, the flow chemiluminescence method suffered from the interference of chloride ions at the same concentration of seawater because of the production of manganese dioxide in the oxidation of chloride ions with permanganate. The conditions (concentrations of potassium permanganate and sulfuric acid and sample volume, i.e. flow injection method) were chosen to minimize the interference of chloride ions. The chemiluminescence method shows a good correlation with the chemical oxygen demand method on fresh water added artificial sea salt and seawater samples. Natural seawater was analyzed by the chemiluminescence method. The results obtained were compared with those obtained by chemical oxygen demand under the alkaline condition and total organic carbon methods. The chemiluminescence method has higher sensitivity and reproducibility than the conventional chemical oxygen demand and total organic carbon methods.     

Chemiluminescence of Potassium Permanganate–Glyoxal–Sulfur Contained Compound System

Abstract

Sulfur contained compound (SCC) had different abilities in term of increasing the intensity of chemiluminescence of potassium permanganate with glyoxal. In a flow system, including methimazole, captopril, cimetidine, methionine, chloropromazine hydrochloride, chlorprothixene and propacil, enhanced intensity was detected, therefore the CL of potassium permanganate–glyoxal–SCC system was studied. Under the optimized experimental conditions, low detection limit and large calibration ranges for Sulfur contained compound were obtained. The proposed method allowed 90 injections h^?1 with excellent repeatability and precision. The method was successfully applied to the determination of six SCC in commercial pharmaceutical formulations with recoveries in the range of 97.24–102.2%. The method was validated through the pharmacopoeia reference method. The possible chemiluminescence reaction mechanism of potassium permanganate–glyoxal–SCC was discussed briefly.     

Factorial design and response surface optimization of spectrophotometric sequential injection analysis of olanzapine formulations

A new spectrophotometric sequential injection analysis (SIA) method for the assay of olanzapine in pharmaceutical formulations was optimized by the factorial design and the response surface approaches. The method was based on the oxidation of olanzapine by an excess amount of permanganate in sulfuric acid media. The reduction of permanganate was spectrophotometrically detected at 570 nm. The 2³ full factorial design was adopted for the optimization of permanganate concentration, sulfuric acid concentration and flow rate. The method was validated based on the IUPAC guidelines. Real pharmaceutical samples were subjected to the proposed SIA method and the results were in satisfactory agreement with those obtained by a previous spectrophotometric method. The full-automation of SIA empowered the proposed method with high repeatability (RSD 1.74%, n = 7) and intermediate-precision (RSD 2.53%, n = 5). Additionally, both automation and miniaturization offered high sampling frequency (26 samples/h). Furthermore, the employment of chemometric optimization enhanced sensitivity of the method with limits of detection and quantification of 1.07 and 3.57 mg/L, respectively. Comparing with previous olanzapine assay methods, which employing conventional analytical techniques, the new SIA method is inexpensive in terms of instrumentation, consumption of reagents and samples as well as effort and manpower. The SIA method is also safer for handling solutions and for the environment.     

Vapor-Liquid Equilibrators To Aid In Making Measurements To Determine Solvent Adducts On Metal Chelates

Abstract

Two vapor-liquid equilibrators to saturate water with organic solvent without forming two liquid phases were developed, thus permitting a more accurate determination of organic adducts to metal chelates. An equation was developed to show that vapor pressure measurements could be used as an alternative method for determining the number of organic adducts on a metal chelate in the aqueous phase.     

Synthesis of quaternary ammonium tribromides: a novel green approach

Abstract

Potassium permanganate (KMnO₄) oxidizes quaternary ammonium bromides to the corresponding tribromides conveniently and effectively. The procedure adopted is environmentally friendly as it is solvent-free. High purity, excellent yield, shorter reaction time and mild reaction conditions are some of the advantages of this synthetic protocol. The efficacy of quaternary ammonium tribromides, especially benzyltrimethylammonium tribromide, is also studied for bromination of some organic substrates.     

Studies on Mercury Pollution: Microdetermination of Mercury in Biological Materials by Cold Vapour Atomic Absorption Spectrometry

Abstract

A simple, rapid, precise and accurate method for the determination of mercury in biological material is described. Biological samples were digested with nitric acid and acidified potassium permanganate and determined by cold vapour analyser. The proposed method was successfully employed for the determination of mercury in samples of fish, hair and blood.     

Organic interferences and their elimination in the 2,4-xylenol spectrophotometric method for nitrate

The 2,4-xylenol spectrophotometric method for nitrate involves formation of 6-nitro-2,4-xylenol, which is steam-distilled into an ammonia—water—isopropanol mixture. The yellow color of the ammonium salt of 6-nitro-2,4-xylenol is measured at 455 nm. A detailed study of the possible interferences from 123 representative organic compounds is described; 61 compounds interfered (when present in amounts of 0.1 g in the original sample). The interfering compounds can be classified according to their mode of interference: (1) compounds that are readily nitrated or oxidized by nitrate in the sulfuric acid medium used cause low results; (2) compounds containing the ONO₂ group that hydrolyze to nitrate cause high results; (3) compounds that steam-distil to produce colored solutions; (4) compounds that steam-distil to produce turbid solutions; (5) compounds that hydrolyze, either in water or sulfuric acid solution, to produce inorganic ions or compounds (e.g. Cl^-, S^2-, and H₂O₂) that repress the color development. Three procedures are described for the elimination of the interferences: (1) oxidation of the organic compound with permanganate, reduction of the excess of permanganate with hydrogen peroxide, and destruction of the peroxide by boiling in the presence of Fe(III) catalyst (this is unsuitable for organic compounds containing nitrogen, as there is invariably some oxidation to nitrate); (2) extraction of interfering organic compounds with methyl isobutyl ketone; (3) precipitation—adsorption method involving treatment with zinc sulfate and sufficient sodium hydroxide to precipitate most of the zinc as zinc hydroxide, addition of 3 g of activated carbon, digestion at 55–65°C for 20 min. cooling, dilution, and filtration. Method (3) is applicable to all organic compounds tested except formaldehyde. The amount of organic compound used to test the methods was normally 0.25 g in the solution being treated.     

光催化氧化法测定地表水化学需氧量的研究

用溶胶-凝胶法在石英管上制备了纳米TiO₂膜, 并采用光催化氧化法建立了一种测定地表水化学需氧量(COD)的新方法. 以Ce(IV)作为纳米TiO₂光生电子的接受体, 从而减少了纳米TiO₂光生电子和光生空穴的复合, 提高纳米TiO₂的光催化氧化能力. 以测定Ce(IV)的紫外吸收为手段探讨了光催化氧化测定COD的机理, 考察了测定COD的最佳反应条件. 实验结果表明, 该方法条件温和, 不会造成二次污染, 能够实现地表水等低COD值水样的快速准确测定. 在该实验所选择的条件下, 可准确地测定1.0～12 mg?L^－1之间的COD值, 检测限为0.4 mg?L^－1.     

Determination of Surfactants Using Ion Pair Extraction of Near-infrared Laser Dyes

Abstract

Ionic surfactants and near-infrared laser dyes formed complexes which were extracted into organic solvents as ion pairs. Surfactants were determined spectrophotometrically by measuring the near-infrared absorbance and fluorescence of the ion pair in the organic solvent. Several of the commercially available near infrared dyes have been found suitable for surfactant determination in water using this technique. The excess near-infrared dye coextracted into the organic solvent was determined by blank extractions. The calibration curves were linear within two orders of magnitude of surfactant concentrations. Non-linear calibration curves are obtained for wider concentration range of surfactants. This method using the recently developed near-infrared laser diode intracavity technique was applied to the determination of SDS in water. Lower detection limits and ease of operation are the major advantages of using this new laser diode technique. The extraction efficiency of different solvent systems was evaluated.     

The determination of total mercury in biological tissues by a modified potassium permanganate procedure.

A simple cold-tube atomic absorption method with a silver-mercury amalgam trap and potassium permanganate as oxidizing agent is described for the determination of total mercury in tissue homogenates. Results are presented for animals fed inorganic (HgCl₂) and organic (CH₃HgOH) mercury orally at a level of 1 mg Hg kg^?1. Data are presented which compare potassium permanganate oxidation of tissue homogenates with whole tissue analysed by cold-tube atomic absorption after digestion with acid, or by neutron activation. For kidney tissue there is good agreement between all three methods for animals fed inorganic and organic mercury. For liver, however, homogenization produced an average loss of about 50 % of the mercury in rats fed mercury(II) chloride. Factors such as adsorption of mercury on sample container walls, bacterial action on the tissue and inadvertent introduction of reducing agents which could reduce the mercury to its elemental state, are not significant. Despite the loss of mercury in the liver by homogenization, rank ordering of mercury values for potassium permanganate—homogenate versus direct neutron activation analyses was essentially the same.     

Isolation and Determination of Volatile Organic Compounds from Water by Dynamic Purge-and-Trap Technique Coupled with Capillary Gas Chromatography

The preconcentration technique of purge-and-trap has been investigated in the present work for quantitative adsorption of volatile organic pollutants purged from water samples. A dynamic purging device with variable volume size has been constructed and tested to purge different concentrations of organic compounds. With Tenax GR as the adsorbent, a dynamic purge-and-trap technique was developed combining on-column preconcentration procedures using ambient trapping/thermal desorption/cryogenic focusing/back-flash injection prior to separation and determination using capillary gas chromatography. Various aromatic compounds in water were determined, giving linear working ranges over five orders of magnitude from 0.02 to 5000 µg/L. The analytical procedures were optimized under the assistance of ultrasonication with results validated for the determination of organic contaminants in underground water and tap water, giving over 93% recoveries and a detection limit of 0.01 µg/L, two orders of magnitude lower than those obtained using commercial available instruments with on-line configuration to minimize cross-contamination. The technique provides a potential automated method for in situ monitoring of volatile organic compounds in water.     

Determination of Volatile Halogenated Compounds in Tap and Surface Waters from the Gdańsk District

Abstract

The present method is based on preconcentration of organic contaminants on XAD-4 as sorbent, thermal desorption, mineralization and coulometric argentometric titration for the final determination of halides. The results were calculated as the total parameter VOX (volatile organic halogen) expressed as chlorine. The method has been used for the VOX determination in tap water, Vistula river water and Baltic Sea water. Sampling of the Baltic Sea water has been carried out during the research cruise of the r/v ‘Oceania’. The relatively high anthropogenic pollution of the river Vistula (c _vox = 11–45 μg Cl/cd³), Gulf of Gdańsk (c _vox = 0.6–4.5 μg Cl/dm³) and the Pomerania Bay (c _vox = 2 μg Cl/dm³) has been determined. The VOX concentration in the tap water varied between 13 and 56 μg/dm³; that is, this water is seriously polluted by volatile organic halogen compounds.     

Determination of Sulfur in Trace Amounts

Abstract

An absolute method for the determination of trace amounts of sulfur in water and organic matrices is described. The method involves decomposition of organic samples in an oxygen bomb or oxidation of water samples with hydrogen peroxide. The resultant sulfates are reduced and distilled as hydrogen sulfide by the action of stannous phosphate in anhydrous phosphoric acid. The evolved hydrogen sulfide is absorbed in zinc acetate solution, converted to methylene blue and measured spectrophotometrically at 665 mm. The range is from 2 to 40 μg of sulfur using 1 cm cells.     

The Permanganate Ion in Alkaline Solutions as a Reagent for CS2N− 3Analytical Determination - A Potentiometric Method

Abstract

The oxidation of the 1, 2, 3, 4-thiatriazol-5-thiolate ion CS₂ N^? ₃by, permanganate ions in an alkaline medium was investigated. The pseudo-halide undergoes a quantitative seventeen-electron change reaction yielding sulphate, nitrogen and carbon dioxide as final products. Despite the similar chemical behavior exhibited by thiocyanate and CS₂N^? ₃ ions the experimental data strongly suggested that the oxidation reactions of the pseudo-halides dealt with in this study do not follow the same mechanism. On the basis of this reaction an oxidative analytical method was developed for the CS₂N^? ₃. The pseudo-halide is oxidized by an excess of permanganate ions. The remaining oxidant is titrated with standardized thalium (I) or hexacyanoferrate (II) solutions. Considerable improvements over former procedures were achieved employing two polarized platinum electrodes to detect the end point, by potentiometry. The method proposed here is simple, precise, accurate, rapid and allows the determination of pseudo-halide concentrations down to 1 × 10^?3 M.     

False Detection of Cyanide Ion in Photographic Processing Waste Solutions Using Standardized Reference Methods

Abstract

Although cyanide compounds are not incorporated in photographic processing solutions, false detection of cyanide ion is often encountered during the determination of total cyanide by various standardized methods such as ISO, ANSI and JIS. Various organic compounds and nitrogen compounds in the processing solutions were examined because of this false detection. The results suggest that hydrogen cyanide is formed by a reaction between these compounds during the distillation process for the separation of total cyanide, even though ISO, ANSI and JIS were used. The results support the following three mechanisms of cyanide formation involved in the process: (1) Hydroxylammonium salts reacts with another ingredient, formaldehyde, to form formaldoxime, which then decomposes to HCN. (2) Hydroxylammonium is oxidized by air to form nitrite ion, which subsequently reacts with organic compounds such as aminocarboxylic acids and aromatic amines (the colour-developing agent) to form HCN. (3) Potassium permanganate oxidizes aromatic amines to form HCN.     

SYNTHESIS OF SOME NEW 3-BENZYL-2-ARYLIMINO-4-THIAZOLIDINONE-1,1-DIOXIDES

Abstract

Twenty new 3-benzyl-2-arylimino-4-thiazolidinone-1,1-dioxides (2) were synthesized by oxidising 3-benzyl-2-arylimino-4-thiazolidinones (1) with potassium permanganate in glacial acetic acid. The homogeneity and purity was confirmed by TLC and some of the dioxides were screened for their insecticidal, acaricidal and herbicidal activities.     

Enzymic Formation of β-D-Fructofuranosides from Sucrose: Activity and Selectivity of Inventase in Mixtures of Water and Alcohol

Abstract

Invertase-catalysed alcoholysis of sucrose in water - primary alcohol mixtures containing up to 70% organic solvent shows 5-40% alkyl β-D-fructofuranoside formation. No formation of fructosides was observed under anhydrous conditions. The kinetics of the competing reactions of water and primary alcohol as fructosyl acceptors with sucrose as fructosyl donor were studied in order to establish the scope and limitations of the method. On a molar basis, water was a relatively unreactive acceptor. 6-Kestose formation due to sucrose itself as a fructosyl acceptor was suppressed by the presence of aliphatic alcohols. The results have been explained by assuming an nonspecific non-polar binding site to be present in the enzyme cavity near the specific polar binding site for the β-D-fructofuranosyl group of the substrate.     

PHOTOLYSIS OF PHENACYL ESTERS IN A TWO-PHASE SYSTEM

ABSTRACT

Phenacyl esters are useful photoremovable protecting groups for carboxylic acids in organic synthesis and biochemistry. In this work, simple one-pot arrangements of the phenacyl and 2,5-dimethylphenacyl ester photolysis are proposed. The reactions were performed in both the benzene/water two-phase system and in water. Cetyltrimethylammonium bromide was found to increase substantially the efficiency of the deprotection as well as the purity of the products by lowering the interfacial tension between the phases. Utilizing water as a medium significantly reduced the necessity to use environmentally malign organic solvents. The overall yields varied from 72 to 98% depending on the reaction conditions.     

Critical comparison of two standard digestion procedures for the determination of total mercury in natural water samples by cold vapour atomic absorption spectrometry

Two pretreatment procedures for total mercury determinations in natural water samples were compared. The first, the Swedish Standard method (DP1), involves digestion of water in the presence of concentrated nitric acid at 120°C and under pressure for 30 min. In the West German Standard method (DP2), small volumes of nitric and sulphuric acids, permanganate and peroxodisulphate are added to the sample, and digestion proceeded at 50°C in an ultrasonic bath. Mercury was determined after both digestion procedures using a modified cold vapour atomic absorption spectrometric method, in which mercury generated on addition of a reducing agent is collected and subsequently atomized in a platinum-lined graphite furnace. The efficacy of the two digestion procedures was tested using various standard organic mercury compounds and it was found that only DP2 provided quantitative recoveries. Purification of the reagents required by DP2 was achieved using a mercury-selective ion-exchange resin, Chelite S, resulting in blank levels below 1.5 ng Hg l^?1. Both methods were applied to the determination of total mercury in an unpolluted marsh water sample, giving 2.0 ng Hg l^?1 (DP1) and 2.7 ng Hg l^?1 (DP2). The West German Standard digestion procedure (DP2) is recommended for the determination of total mercury in natural water samples.