Simultaneous kinetic spectrophotometric determination of cyanide and thiocyanate using the partial least squares (PLS) regression

The partial least squares (PLS-1) calibration model based on spectrophotometric measurement, for the simultaneous determination of CN⁻ and SCN⁻ ions is described. The method is based on the difference in the rate of the reaction between CN⁻ and SCN⁻ ions with chloramine-T in a pH 4.0 buffer solution and at 30 °C. The produced cyanogen chloride (CNCl) reacts with pyridine and the product condenses with barbituric acid and forms a final colored product. The absorption kinetic profiles of the solutions were monitored by measuring absorbance at 578 nm in the time range 20-180 s after initiation of the reaction with 2 s intervals. The experimental calibration matrix for partial least squares (PLS-1) calibration was designed with 31 samples. The cross-validation method was used for selecting the number of factors. The results showed that simultaneous determination could be performed in the range 10.0-900.0 and 50.0-1200.0 ng mL⁻¹ for CN⁻ and SCN⁻ ions, respectively. The proposed method was successfully applied to the simultaneous determination of cyanide and thiocyanate in water samples.     

Determination of cyanide and thiocyanate by a spectrophotometric flow-injection method

A rapid spectrophotometric flow-injection method is described for the determination of cyanide and thiocyanate. The method involves a two-step procedure in which the total concentration of both species is first determined (using sodium isonicotinate/sodium barbiturate reagents), after which the cyanide is complexed with nickel(II) and thiocyanate is quantified separately; the cyanide concentration is calculated by difference. Various parameters such as pH, temperature and nickel concentration were optimized. The method is applied to synthetic sample solutions and the results are compared with those obtained by the ASTM distillation method. The limits of detection for cyanide and thiocyanate are 0.05 and 0.08 μg ml^?1, respectively, with a sample throughput rate of 10 h^?1.     

Indirect spectrophotometric determination of cyanide

A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator.     

The effect of barbituric acid concentration in the spectrophotometric determination of cyanide and thiocyanate by the pyridine-barbituric acid method

Summary The König reaction forms the basis of many analytical methods including those for the determination of chlorine, nicotinic acid, thiocyanate and cyanide. The colorimetric methods have, however, been plagued with various problems such as the use of hazardous, often carcinogenic compounds, and the instability of the final color formed as well as of the color reagent itself.Using a mixture of pyridine, hydrochloric acid and barbituric acid as the color reagent, the present study shows the effect of barbituric acid concentration on the intensity and stability of the color complex. The problems associated with the use of barbituric acid can be attributed mainly to the high concentration used by previous workers. A color reagent containing about 0.1% (w/v) barbituric acid shows marked improvements in color intensity and stability as well as reagent stability.     

Simultaneous determination of cyanide and thiocyanate in plasma by chemical ionization gas chromatography mass-spectrometry (CI-GC-MS)

An analytical method utilizing chemical ionization gas chromatography-mass spectrometry was developed for the simultaneous determination of cyanide and thiocyanate in plasma. Sample preparation for this analysis required essentially one-step by combining the reaction of cyanide and thiocyanate with pentafluorobenzyl bromide and simultaneous extraction of the product into ethyl acetate facilitated by a phase-transfer catalyst, tetrabutylammonium sulfate. The limits of detection for cyanide and thiocyanate were 1?μM and 50?nM, respectively. The linear dynamic range was from 10?μM to 20?mM for cyanide and from 500?nM to 200?μM for thiocyanate with correlation coefficients higher than 0.999 for both cyanide and thiocyanate. The precision, as measured by %RSD, was below 9?%, and the accuracy was within 15?% of the nominal concentration for all quality control standards analyzed. The gross recoveries of cyanide and thiocyanate from plasma were over 90?%. Using this method, the toxicokinetic behavior of cyanide and thiocyanate in swine plasma was assessed following cyanide exposure.     

Simultaneous determinationof cyanide and thiocyanate by the pyridine/barbituric acid method after diffusion through a microporous membrane

A flow-injection system for the simultaneous determinationof cyanide and thiocyanate is described. A microporous tubular PTFE membrane module with an outer casing was constructed and included inthe system. Cyanide and thiocyanate diffuse thourgh the membrane wall from the phosphoric acid donor stream to a phosphate or carbonate buffer acceptor stream. Percentage transference of cyanide and thiocyanate were 68% and 59%, respectively, at pH 6.0. At pH 8.1, the percentage transference of cyanide was only 19%. The transferred cyanide and thiocyanate are determined by a pyridine/barbituric acid method. Thiocyanate reacts slowly with chloramine-T at pH 8.1, so that cyanide can be determined without interference from thiocyanate. Total cyanide and thiocyanate are determined at pH 6.0. The detection limits (S/N = 3) are 0.3 μM cyanide and 0.2 μM thiocyanate at pH 6.0, and 5 μM cyanide at pH 8.1. A mechanism for the transference thourgh the membrane is discussed. Bromine interferes with the determination of cyanide and thiocyanate at both pH 6.0 and 8.1. Hexacyanoferrate(II) and hexacyanoferrate(III) interfere at pH 8.1, but not at pH 6.0. Cyanate, oxaloacetate, oxalate, tartrate, albumin, globulin and lysozyme do not interfere.     

Kinetic spectrophotometric determination of nanogram amounts of cyanide

A sensitive kinetic method for determination of nanogram amounts of cyanide is reported. It is based on the measurement of the induction period imposed by cyanide on the copper(II)-catalysed oxidation of 3-hydroxybenzaldehyde azine (3-OHBAA) by potassium peroxydisulphate. Kinetic data are recorded spectrophotometrically at 465 nm, the maximum absorption wavelength of the oxidation product of 3-OHBAA. From the kinetic study and other experimental tests it may be concluded that the cyanide ion undergoes copper(II)-catalysed oxidation during the induction period. The calibration plot is linear in the range 150-600 ng/ml cyanide and the detection limit is 50 ng/ml. The precision of the method, expressed as the relative standard deviation, is 3.2% for 350 ng/ml cyanide. Good recoveries are obtained in applying the method to analysis for cyanide in water samples.     

Effects of γ-radiation on spectrophotometric determination of uranium as thiocyanate

The effects of γ-radiation on the spectrophotometric determination of uranium as the thiocyanate complex in water and acetone-water solutions have been studied. When tin(II) chloride is present, the absorbance of uranium thiocyanate in aqueous solution decreases with increasing radiation dose until the appcarance of radiolytic elemental sulfur causes an apparent increase. In the absence of tin(II) chloride, the turbidity caused by radiolytic sulfur causes an increase in absorbance over the whole dose range studied. In acetone-water solution, similar but much more severe effects occur. Observations of radiation effects of some of the individual reagents used in the spectrophotometric determinations are included, as well as indications of the errors caused by specific radiation doses.     

Speciation analysis of chromium by separation on a 5-palmitoyl oxine-functionalized XAD-2 resin and spectrophotometric determination with diphenylcarbazide

The method developed in this work for the separation and preconcentration of Cr(III) is based on its retention by an Amberlite XAD-2 copolymer resin functionalized with 5-palmitoyl-8-hydroxyquinoline (oxine), abbreviated XAD-POx, with the ligand covalently bound to the copolymer. Cr(III) sorption was quantitative within the pH range 4.5–7.0 and Cr(VI) was not retained. The Cr(III) held by the resin column was eluted with a hot solution of H₂O₂ in pH9.0 aqueous NH₃–NH₄Cl buffer, and Cr oxidized to CrO₄^2– was rejected by the chelating cation-exchanger column. Any Cr(VI) originally present with Cr(III) could be reduced with an acidic solution of H₂O₂, and retained by the column yielding total Cr results, Cr(VI) being determined from the difference. The resin showed a maximal preconcentration factor of 60 for Cr(III), the LOD and LOQ being 9.3 and 30.1 nmol L^–1, respectively. The developed preconcentration-speciation analysis was finished with a diphenylcarbazide (DPC) spectrophotometric procedure suitable for conventional laboratories. The resin showed excellent salt tolerance, enabling Cr analysis in seawater, and was stable over extended use. All the interferents of this procedure that normally occur in an electroplating effluent, a blended coal CRM, and a standard steel sample could be removed by the recommended procedure, by use of partial and total selectivity at the adsorption and desorption stages, respectively, enabling preconcentration and colorimetric determination of chromium in various complex matrices.     

Direct spectrophotometric determination of thiocyanate in serum and urine with a continuous-flow analyzer

A spectrophotometric method for the rapid measurement of thiocyanate in serum and urine without separation from interfering substances is described. Thiocyanate reacts immediately with chloramine-T in presence of iron(III) chloride catalyst to give cyanogen chloride, which reacts with a mixture of γ-picoline (4-methylpyridine) and barbituric acid to form a soluble violet—blue product, which is measured at 605 nm. Other components of physiological fluids react more slowly and do not interfere if the reaction time of the chlorinating step is kept very short. The proposed procedure is compared with a highly selective method, based on the oxidation of thiocyanate to cyanide, and good agreement was obtained for both serum and urine. The method is readily adapted to a continuous-flow procedure with a Technicon AutoAnalyzer.     

Indirect spectrophotometric determination of trace cyanide with cationic porphyrins

Three highly sensitive methods for the determination of cyanide have been developed, based on the fact that the complexation of silver ions with three cationic porphyrins, 5,10,15,20-tetrakis-(1-methyl-2-pyridinio)porphine [T(2-MPy)P], 5,10,15,20-tetrakis(1-methyl-3-pyridinio)porphine [T(3-MPy)P] and 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphine [T(4-MPy)P], in alkaline media is inhibited by cyanide and the decrease in absorbance of the silver(II) complex is proportional to the cyanide concentration. Sensitivities of the procedures developed are 0.133, 0.126 and 0.234 ng/cm(2), respectively for an absorbance of 0.001. Cadmium(II), copper(II), mercury(II), zinc(II), iodide and sulfide interfere with the cyanide determination. One of the proposed methods was applied to the determination of cyanide in waste-water samples, with satisfactory results.     

Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

Simultaneous spectrophotometric determination of tetravalent and hexavalent selenium

Two rapid, accurate and reproducible methods are reported for the simultaneous spectrophotometric determination of tetravalent and hexavalent selenium in the presence of each other. Both procedures involve the sequential complexation and solvent extraction of the selenium(IV)-diethyldithiocarbamate complex by chloroform in the presence of perchlorate ions followed by reduction of hexavalent selenium in the remaining aqueous phase to tetravalent selenium by 25% hydrobromic acid and its subsequent determination after complexation with 3,3′-diaminobenzidine or sodium diethyldithiocarbamate.     

葡聚糖凝胶分离富集催化动力学光度法测定痕量铜(Ⅱ)

研究了在邻苯二甲酸氢钾 盐酸介质中 ,在抗坏血酸 (VC)存在下铜 (Ⅱ )催化溴酸钾氧化偶氮氯膦 mA的褪色反应及其动力学条件 ,该法测定铜 (Ⅱ )的范围为 0～ 2 5 μg/2 5mL ,检出限为 3 1 2× 1 0 - 1 1 g/mL ,采用葡聚糖凝胶 (DG)分离富集 ,使方法的选择性得到了大大的提高 ,已用于多种样品中痕量铜的测定     

Analytical applications of ternary complexes-V Indirect spectrophotometric determination of cyanide

An indirect spectrophotometric method is proposed for the determination of cyanide down to 0.2 ppm. It is based on the fact that cyanide prevents the formation of the strongly absorbing ternary complex between silver(I), 1,10-phenanthroline and Bromopyrogallol Red in nearly neutral aqueous solution. Among 17 cations examined, only mercury(II) could not be tolerated. Zinc, cadmium and cobalt interfered only when present in large amounts. A 1000-fold molar excess (over cyanide) of 14 anions can also be tolerated. Bromide, iodide and thiocyanate interference is overcome by addition of lead nitrate, ammonium sulphate and barium nitrate, followed by centrifugation.     

Flow injection spectrophotometric determination of cyanide by the phenolphthalin method

The phenolphthalin method for the determination of cyanide has been modified and adapted to a continuous flow system based on the flow injection principle. Aqueous cyanide samples are injected into a carrier stream (0.001 M NaOH), which is then merged with the combined reagent stream of phenolphthalin and carbonate buffer (pH 10.3), and the mixture is passed through an on-line cupric sulfide packed column. The resulting phenolphthalein (the oxidized form of phenolphthalin) is measured in a flow-through spectrophotometer at 552 nm, to determine the cyanide content. The chemical factors and flow injection analysis (FIA) variables influencing the system are discussed. The calibration graph is linear from 0.6 to 4.3 ppm cyanide. At a sampling rate of about 70 samples h(-1) with 50 mul sample injections, precision was about 1% relative S.D.     

Solvent extraction flow-injection manifold for the simultaneous spectrophotometric determination of free cyanide and thiocyanate ions based upon on-line masking of cyanides by formaldehyde

This study reports a sensitive solvent extraction flow-injection (FI) method for the simultaneous spectrophotometric determination of free cyanide and thiocyanate in human saliva and pralidoxime solutions. Cyanide and thiocyanate form colored (λ_max=540 nm) ternary complexes with copper and 2,2′-dipyridyl-2-quinolylhydrazone (DPQH) that are extractable into chloroform. The determination of thiocyanates in the presence of cyanides is accomplished after on-line masking of the latter with formaldehyde through a binary inlet static mixer (BISM). Total thiocyanates and cyanides are determined in a second run, without the use of the masking agent. The proposed method allows the determination of the analytes in the range of 0-4 mg l⁻¹ thiocyanates and 0-3 mg l⁻¹ cyanides, with the 3σ detection limits being 0.007 and 0.004 mg l⁻¹, respectively. The precision of the method (s_r<1.0% at 1 mg l⁻¹ CN⁻ or SCN⁻, n=12 in both cases) and the sampling rates were quite satisfactory (60 injections per hour). The method was applied to the analysis of human saliva and pralidoxime solutions and gave recoveries in the range of 98.0-102.2% for both analytes whereas the mean relative error was e_r=1.7%.     

Improved spectrophotometric determination of cyanide with organic disulfides using dimethylformamide

The rate of reaction of cyanide ion with the dissulfide 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB) is increased considerably with N,N-Dimethylformamide present. The time required for the spectrophotometric determination of cyanide using this procedure is decreased from 2 hours to 30 minutes or less.     

Microencapsulation of styrene with melamine-formaldehyde resin

Melamine-formaldehyde (MF) resin-walled microcapsules containing styrene were prepared by in situ polymerization in an oil-in-water emulsion. In response to the characteristics of styrene (i.e., high volatility, non-polarity, low molecular weight, and low viscosity), the synthesis method was improved by optimizing the reaction conditions accordingly. It was found that utilization of macromolecular emulsifier of lower molecular weight, moderate dispersion rate, and higher feeding weight ratio of core/shell monomers is critical for the fast formation of capsules’ wall. The highest loading of styrene in the resultant microcapsules can be about 60%, and mean diameter of the capsules fell in the range of 20∼71 μm, which can be adjusted by changing processing parameters. It is believed that the present work provides a feasible approach to encapsulate monomers for manufacturing polyester based self-healing composites.