Automated Colorimetric Method for Total Cyanide in Water and Wastewater

Abstract

An automated benzidine-pyridine method for the analysis of total cyanide is described. Cyanides are converted to cyanogen bromide by the reaction with bromine water. Cyanogen bromide reacts with benzidine in a dilute pyridine medium to form an intense red color directly proportional to the cyanide concentration. Cyanide often is found complexed with metals. Complex iron cyanides such as ferrocyanide or ferricyanide are difficult to decompose, but the conversion is hastened with mercuric chloride and magnesium chloride in a modified Serfass distillation.¹

Hydrogen cyanide is readily formed and absorbed in sodium hydroxide.     

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.     

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.     

Application of hydrocyanic acid vapor generation via focused microwave radiation to the preparation of industrial effluent samples prior to free and total cyanide determinations by spectrophotometric flow injection analysis

A sample preparation procedure for the quantitative determination of free and total cyanides in industrial effluents has been developed that involves hydrocyanic acid vapor generation via focused microwave radiation. Hydrocyanic acid vapor was generated from free cyanides using only 5 min of irradiation time (90 W power) and a purge time of 5 min. The HCN generated was absorbed into an accepting NaOH solution using very simple glassware apparatus that was appropriate for the microwave oven cavity. After that, the cyanide concentration was determined within 90 s using a well-known spectrophotometric flow injection analysis system. Total cyanide analysis required 15 min irradiation time (90 W power), as well as chemical conditions such as the presence of EDTA–acetate buffer solution or ascorbic acid, depending on the effluent to be analyzed (petroleum refinery or electroplating effluents, respectively). The detection limit was 0.018 mg CN l⁻¹ (quantification limit of 0.05 mg CN l⁻¹), and the measured RSD was better than 8% for ten independent analyses of effluent samples (1.4 mg l⁻¹ cyanide). The accuracy of the procedure was assessed via analyte spiking (with free and complex cyanides) and by performing an independent sample analysis based on the standard methodology recommended by the APHA for comparison. The sample preparation procedure takes only 10 min for free and 20 min for total cyanide, making this procedure much faster than traditional methodologies (conventional heating and distillation), which are time-consuming (they require at least 1 h). Samples from oil (sour and stripping tower bottom waters) and electroplating effluents were analyzed successfully.     

An Atomic Absorption Analysis Method for Cyanide

Abstract

An atomic absorption analysis procedure for cyanide has been developed. The procedure is based upon the solubilization of copper(II) from a basic copper carbonate in an alkaline medium. The amount of copper complexed by the cyanide ion is determined by atomic absorption and a calibration curve is constructed concurrently. The stoichiometry of the cyanide-copper complex is 3:1, implying formation of the complex ion Cu(CN)^? ₃, with no formation of CuCN observed at the low concentration of cyanide used. The method is used primarily for analyzing low levels of cyanide; the sensitivity of the method extending down to 2.0 × 10^?5 M CN^?. The most likely interference, iron, is considered. Finally, recovery of cyanide from spiked samples is demonstrated.     

Determination of Free Cyanide in Water by Released Flourescence of a Dissociated Ternary Complex

Abstract

A flourometric procedure for the analysis of free cyanide is described. The method is based on the dissociation of a ternary complex of silver-1, 10-phenanthroline-tetrabromofluorescein by cyanide to produce a fluorescent product. The fluorescence intensity is found to be directly proportional to the cyanide concentration. The method can reliably detect 0.02 μg/mL cyanide.     

Determination of cyanides in electroplating solutions as Ni(CN)42– and analysis by capillary electrophoresis

A CE method was developed for the determination of total (free and weakly bound) cyanide in electroplating solutions based on the use of a cationic surfactant (TTAB) and complexation with Ni(II)-NH₃ solutions to Ni(CN)₄ ^2–. Both direct complexation and cyanide distillation combined with complexation were tested. Under optimized conditions, this method is time-saving compared to standard methods. Total cyanide determined by CE had detection limits (with respect to the initial sample concentration) of 0.5 μg/mL for direct complexation and 50 ng/mL for distillation combined with complexation. Total cyanide and cyanide not amenable by chlorination (CNAC) were determined in real samples from spent electroplating baths.     

Analysis of Cyanide in Blood by Headspace-Isotope-Dilution-GC-MS

Abstract

An uncomplicated, rapid, automated procedure for the analysis of low cyanide concentrations in whole blood is reported. The analysis was performed by headspace gas chromatography and mass spectrometry in the (¹H¹²C¹⁴N) and m/z 29 (¹H¹³C¹⁵N). Carryover from cyanide adsorption onto the surface of the needle was prevented by developing a new method that enabled automated flushing of the needle in between each cyanide analysis. Results were compared of ordinary calibrations and those of isotope dilutions. The total time of analysis was 18 min for a single cyanide analysis.     

Determination of cyanides in electroplating solutions as Ni(CN)42– and analysis by capillary electrophoresis

A CE method was developed for the determination of total (free and weakly bound) cyanide in electroplating solutions based on the use of a cationic surfactant (TTAB) and complexation with Ni(II)-NH₃ solutions to Ni(CN)₄ ^2–. Both direct complexation and cyanide distillation combined with complexation were tested. Under optimized conditions, this method is time-saving compared to standard methods. Total cyanide determined by CE had detection limits (with respect to the initial sample concentration) of 0.5 μg/mL for direct complexation and 50 ng/mL for distillation combined with complexation. Total cyanide and cyanide not amenable by chlorination (CNAC) were determined in real samples from spent electroplating baths. Received: 5 February 1998 / Revised: 26 July 1998 / Accepted: 1 August 1998     

Microdetermination of Cyanide

Abstract

A volumetric procedure is described for the micro-determination of cyanide. Small amounts of cyanide can be estimated even in presence of chloride if it is present in the electrolytic bath. N-Bromosuccinimide (NBS) is used to quantitatively oxidized cyanide to cyanate. The end point is reached when the rose red color of the bordeaux red is changed to distinct yellow. From 1–6 mg. of cyanide were analyzed with an average relative standard deviation of about 0.66%.     

Triphenylphosphine-Mediated Eco-Friendly Synthesis of (Z)-Diisopropyl-2-(Cyano(Aryl)Methylene)Hydrazine-1,1-Dicarboxylates Using Potassium Hexacyanoferrate(II) as a Cyanide Source

Abstract

A triphenylphosphine-mediated synthetic method for (Z)-diisopropyl-2-(cyano (aryl)methylene)hydrazine-1,1-dicarboxylates via one-pot three-component reactions using potassium hexacyanoferrate(II) as a cyanide source was described. This protocol has advantages of no use of strong toxic cyanating agents, high yield, and simple work-up procedure.     

Use of an Aqueous Micellar Medium to Improve the Spectrophotometry Determination of Cyanide Ion with 5,5′-Dithiobis(2-Nitrobenzoic Acid)

Abstract

The spectrophotometric method for the determination of cyanide, which is based on the reaction of cyanide ion with 5,5′-dithiobis(2-nitrobenzoic acid) to displace the corresponding absorbing thiol anion, has been reinvestigated using an aqueous cetyltrimethylammonium bromide micellar reaction medium. The rate of the analytical reaction is increased considerably in the presence of the cationic surfactant. Thus, the time required for the spectrophotometric determination of cyanide ion in the 0.18 – 2.80 μg/ml range using this procedure is decreased from 25 minutes to 1 – 3 minutes.     

Argentometric Determination of Cyanide in the Presence of Dithionite

Abstract

Cyanide can be measured in the presence of dithionite and its decomposition products by the method of Liebig-Deniges after treatment of the sample with excess iodine, followed by sulfite. The iodine oxidizes dithionite, sulfite and thiosulfate to sulfate at pH 10. Any cyanide present in the sample will form iodine cyanide. Sulfite reduces excess iodine to iodide and converts cyanogen iodide to iodide and cyanide. A large amount of iodide in the sample shifts the end point of the titration significantly. An appropriate blank must be carried through the procedure to correct for the excess iodide.     

Spectrophotometric Determination of Phenols and Cyanides After Distillation from Natural Waters

Abstract

Total phenols were determined by molecular spectrophotometry, after distillation, complexation with 4-aminoantipyrine and extraction into chloroform. Cyanides were also determined spectrophotometrically after distillation from the acidified samples, and complexation in moderate acidic solution with barbituric acid. The dynamic ranges were 0 – 100 μg L^?1 for total phenols and 0 – 30 μg L^?1 for cyanides. The above methods were applied in the analysis of river, lake and stream waters collected from Northern Greece. The seasonal and spatial variation of concentrations was evaluated by two-way ANOVA. Background levels (4 – 12 μg L^?1 for total phenols and 0.3 – 3 μg L^?1 for cyanides), were found in almost all surface waters, with some exceptions.     

A New Spectrophotometry Determination of Cyanide by Solvent Extraction as Tris-(1,10-Phenanthroline)-Iron (II)-Thiocymate

Abstract

By shaking aqueous cyanide solution with nitrobenzene contained sulfur, thiocyanate is formed and is extracted into the nitrobenzene as an ion pair of thiocyanate anion and tris-(1,10-phenanthroline)-iron(II) chelate cation. By measuring the color intensity of the organic phase at 516 nm, cyanide is determined spectrophotometrically. A linear calibration curve is obtained up to 4 × 10^?5M of cyanide in the aqueous phase.     

Separation and automatic spectrophotometric determination of low concentrations of cyanide in water

Semi-automatic methods are described for the routine determination of cyanide in water. Membrane diffusion and isothermal distillation are examined for the separation/concentration of cyanide; the isothermal distillation procedure is optimized for routine use. An air-segmented flow analyzer is used to quantify cyanide. Two classical spectrophotometric methods are adapted and compared. The method based on reaction with picric acid is applicable at cyanide concentrations exceeding 1 mg l^?1. A modified Aldridge method is far better for lower concentrations. Combination of isothermal distillation with the automatic version of the Aldridge method is suitable for the determination of cyanide in waters in the concentration range 0.01–10 mg l^?1. Interference by sulphide and sulphite and their removal are described.     

The use of O-Nitrosophenol in the Determination of MI- Croquantities of Zinc

Abstract

A new method for determining microquantities of zinc using o-nitrosophenol as reagent is described. The prepararion of the reagent in the laboratory is also described, because it is not available for sale. The formed complex, after additional pyridine, can be extracted with organic solvent (toluene) and zinc can be determined spectrophotometrically by measuring the absor-bance of the organic layer at 482 nm. The optimum range of concentration was found to be 0.04 μg to 0.8 μg/ml in the final dilution. By masking zinc using cyanide and thiosulphate and selective demasking by the addition of hydrated chloral, Zn can also be determined in the presence of larger amounts of interferences.     

Complex Formation Between Hydroxy Naphthol Blue and First Row Transition Metal Cyanide Complexes

Abstract

It has been found that cyanide complexes of first row transition metal elements exhibit enhanced binding to hydroxy naphthol blue (HNB) relative to the binding of corresponding aquo-ions. HNB forms a 2:1 complex with Fe³⁺ and Cu²⁺ cyanides, and 1:1 complexes with all other transition metal cyanide complexes studied; formation constants have been calculated from the spectrophotometric data in each case. It is possible to use HNB as a spectrophotometric reagent for transition metal cyanide complexes, lower limits of detection being determined for each complex.     

Study of Cyano-Derivatives of Propene as Transfer Agents in Radical Polymerizations

ABSTRACT

A new procedure for determining transfer constants, depending on knowledge of the numbers of initiator fragments in the average molecules of appropriate polymers, has been applied to crotononitrile (1-cyano-1-propene) and allyl cyanide (3-cyano-l-propene) with methyl methacrylate and styrene at 60°C. Allyl cyanide is the more reactive of the two additives, but is less effective than allylbenzene (3-phenyl-1-propene); neither of the cyano-derivatives causes appreciable retardation.     

Determination of Alkylmercury Compounds in Lake Sediments by Steam Distillation-Flameless Atomic Absorption

Abstract

Organic mercury compounds in lake sediments were separated into dialkyl- and monoalkylmercury fractions by steam distillation and subsequently quantified by flameless atomic absorption. The method recovered nearly all CH₃HgCH₃ and CH₃HgCl added to diverse sediments. Parameters influencing the efficacy of the procedure, i.e., Hg concentration, sample size and distillation time, were evaluated.