Determination of thiuram disulphides and analysis of thiuram disulphide-dithiocarbamate mixtures

Potassium trithiocarbonate is used as reluctant for the titrimetric determination of thiuram disulphides in dimethylformamide-water media. The method is based on reductive cleavage of the disulphide linkage to yield the corresponding dithiocarbamates. In visual titrations, the end-point is marked by appearance of a yellow colour with the first drop of reagent added in excess. The method is simple, accurate, reliable and of wide applicability. It has been successfully extended to the analysis, in the same sample solution, of thiuram disulphide-dithiocarbamate mixtures.     

Titrimetric determination of hydrogen peroxide in alkaline solution

Direct titration of hydrogen peroxide in alkaline bromide media has been accomplished with sodium hypochlorite. The relative standard deviation is 0.2%. A photometric end-point is recommended for the determination of 0.10-1.0 mequiv of peroxide. Larger samples are evaluated by use of Bordeaux Red as visual indicator. The hypochlorite procedure compares favourably with iodometry and permanganate in the analysis of commercial peroxides.     

Nitron as a titrant in potentiometric determination of nitrate

A volumetric method of nitrate determination has been developed, using nitron as a titrant and detecting the end-point potentiometrically with a membrane electrode sensitive to nitrate. To get a better insight into the characteristics of the system, the acid dissociation constant of nitron was evaluated spectrophotometrically (pK(a) = 10.34). The solubility product of nitron nitrate was found to be 1.78 +/- 0.03 x 10(-6) (20 degrees , 0.05M K(2)SO(4)). The optimal nitrate concentration for titration is about 0.01M and this method may be successfully applied for determination of nitrate nitrogen in fertilizer samples.     

Spectrophotometric determination of some dithiocarbamates

A procedure has been developed for the determination of six dithiocarbamates [sodium dimethyldithiocarbamate (dibam), sodium diethyldithiocarbamate (NaDDC), tetramethylthiuram disulphide (thiram), zinc dimethyldithiocarbamate (ziram), sodium N-methylpiperazinecarbodithioate and potassium morpholine-4-carbodithioate] in microgram quantities by converting them into selenium dithiocarbamate complexes, which are then extracted into chloroform and measured at 430 nm against a reagent blank. The method is sensitive and can be used for the determination of dithiocarbamates in commercial samples and synthetic mixtures.     

Some aspects of the determination of water by the karl fisher method

Conditions for eliminating systematic errors and minimizing random errors in the determination of water in methanol and α-alumina using Karl Fisher reagent with visual end-point detection are studied. The concentration dependence of the relative standard deviation of the determination of water by the Karl Fisher method is found to be linear in RSD-1/c coordinates. To exclude the effect of moisture contained in the titration flask, it is suggested to bind water with a titrant in the presence of a small amount of methanol. The methanol effect (that is, the dependence of the titration results on the water: methanol ratio and the total amount of the titrated water-methanol mixture) is shown to be eliminated in the presence of the products of water interaction with Karl Fisher reagent that form on the water binding stage. It is found that the use of a background dye, methylene blue, eliminates significant systematic errors in the determination of water by the Karl Fisher method, particularly, at low concentrations. It is noted that the visual detection of the titration end-point has some advantages over the automated electrometric versions of the method; in particular, it is characterized by a better reproducibility of the determination of low concentrations of water.     

Oxidation with permanganate in presence of fluoride: Determination of hypophosphite

A rapid method is described for the determination of hypophosphite by oxidation with permanganate in acid medium in the presence of fluoride to prevent formation of insoluble oxides of manganese. The optimum conditions for visual and potentiometric end-point detection are given. Hypophosphite is oxidized to H(2)PO(-)(3). Under optimum conditions the titrations are fast and exhibit a reasonable potential change at the end-point. The method demonstrates the feasibility of determining amounts of H(2)PO(-)(2) corresponding to 0.08-7 mg of phosphorus.     

Stability-indicating methods for the determination of disopyramide phosphate

Four methods were developed for the determination of intact disopyramide phosphate in the presence of its degradation product. In the first and second methods, third-derivative spectrophotometry and first derivative of the ratio spectra were used. For the third-derivative spectrophotometric method, the peak amplitude was measured at 272 nm, while for the derivative ratio spectrophotometric method, disopyramide phosphate was determined by measuring the peak amplitude at 248 and 273 nm. Both methods were used for the determination of disopyramide phosphate in the concentration range 12.5-87.5 microg/mL, with corresponding mean recovery 100.8 +/- 0.7% for the first method and 99.9 +/- 0.7% and 99.6 +/- 0.7% for the second method at 248 and 273 nm, respectively. In the third method, an ion selective electrode (ISE) was fabricated using phosphotungstic acid as an anionic exchanger, PVC as the polymer matrix, and dibutylsebacate as a plasticizer. The ISE was used for the determination of disopyramide phosphate in pure powder form in the concentration range 10(-2)-10(-5) M. The slope was found to be 58.5 (mV/decade), and the average recovery was 99.9 +/- 1.6%. The fourth method depended on the quantitative densitometric determination of the drug in concentration range of 0.25-2.5 microg/spot using silica gel 60 F245 plates and ethyl acetate-chloroform-ammonium hydroxide (85 + 10 + 5, v/v/v) as the mobile phase, with corresponding mean accuracy of 100.3 +/- 1.1%. The 4 proposed methods were found to be specific for disopyramide phosphate in presence of up to 80% of its degradation product for the spectrophotometric methods, 90% of its degradation for the densitometric method, and 40% for the ISE method. The 4 proposed procedures were successfully applied for the determination of disopyramide phosphate in Norpace capsules. Statistical comparison between the results obtained by these methods and the official method of the drug was done, and no significant differences were found.     

Spectrophotometric determination of iron(III) dimethyldithiocarbamate (ferbam)

A spectrophotometric method was developed for the determination of ferbam (iron(III) dimethyldithiocarbamate) by converting it into an iron-phenanthroline complex, which was then absorbed on microcystalline naphthalene in the presence of tetraphenylborate, and the absorbance was measured at 515 nm against a reagent blank. The molar absorptivity of the complex was 1.2 x 10(4)l mol(-1)cm(-1). Ten replicate analyses of a sample solution containing 150 mug of ferbam gave a relative standard deviation of 0.84%. Beer's law was obeyed over the concentration range 22.4-372.9 mug of ferbam. The effects of various factors such as reagent concentration and naphthalene, shaking time and diverse ions were studied in detail. The method is sensitive and selective and can be applied to the direct determination of ferbam in commercial samples and in mixtures containing various other dithiocarbamates (e.g. ziram, zineb and maneb) in foodstuffs.     

Simple instrument for titrimetry without visual indicators. gasometric titrations: Cerimetry,chlorometry, nitrate,nitrite, hydroxide and carbonate determination

It was shown in previous papers, that many titrimetric problems can be solved by observing the pressure change of a closed system above the solution titrated at the equivalence point. This principle was made the basis of a gasometric titration method in which the end-point is found graphically. The titrant is added to the sample solution in measured increments at fixed intervals of time and the corresponding gas pressure or volume of the system is recorded and then plotted against the volume of added titrant. Half a dozen readings are sufficient to establish the end-point of a titration, which is found at the intersection of two straight lines. This graphical method was applied to cerimetry and chlorometry, as well as to some other analytical reactions (determination of nitrite, nitrate, hydroxide and carbonate) already described in previous papers on the gas pressure end-point technique. The results are comparable in precision and accuracy to the values obtained by the conventional visual end-point titrations. A gasometric titration takes about 10 minutes. The presence of other substances in the sample capable of reacting with the titrant does not necessarily cause interference.     

Amperometric determination of organic isothiocyanates

An amperometric titration method is described for the determination of 1-5 mg of organic isothiocyanates, based on their quantitative reaction with n-butylamine in dimethylfonnamide to form N,N-disubstituted thioureas which are then titrated amperometrically in aqueous ammonia-ammonium nitrate buffer with silver nitrate (dropping mercury electrode at -0.56V). The end-point corresponds to a silver:thiourea ratio of 2:1, with precipitation of silver sulphide. The method is simple, accurate, widely applicable, and gives reproducible results.     

Amperometric determination of thioacetamide with copper(I)

A method is given for the amperometric determination of thioacetamide (TAA) based on the reaction of TAA with copper(I) in ammoniacal solution. The reduction current due to the copper(I) is used to determine the end-point. The determination is carried out at constant temperature (25°), pH 8.0-9.8 (ammonia-urotropine buffer), and at constant potential (−0.6 V vs. S.C.E.), with a dropping mercury electrode as cathode and a saturated calomel electrode as anode. The solution is deaerated by a stream of electrolytically generated hydrogen. The titrations are carried out simply and rapidly and the results are fairly reproducible. The error is generally 1.0% for amounts of TAA ranging from 0.07 to 1.8 mg.     

Chemically modified carbon paste electrode for iodide determination on the basis of cetyltrimethylammonium iodide ion-pair.

A new carbon paste electrode (CPE) for the determination of iodide ion based on a cetyltrimethylammonium iodide (CTMAI) ion pair as an electroactive material is described. The electrode shows a linear response for iodide ion over the concentration range of 4 x 10(-5) M to 1 x 10(-1) M with a lower detection limit of 4 x 10(-5) M at 25 degrees C. The electrode has a Nemstian slope of -55.0 +/- 0.4 mV/decade and a fast potential response of 45 s, which is almost constant over a pH range of 5.0 - 9.0. Selectivity coefficient data of the CTMAI-CPE for some common ions show negligible interference, and the electrode has high selectivity towards the iodide ion. An average recovery of 101.83% with a relative standard deviation of 1.53% has been achieved for the determination of iodide in Flaxedil (gallamine triethiodide) ampoules, a muscle relaxant drug. The electrode has been examined for the determination of iodide in saline water; the results were found to compare favorably with those obtained using Metrohm iodide ISE. The electrode has been utilized as an end-point indicator electrode for the determination of Hg(II) and phenylmercury(I) in their aqueous solutions using potentiometric titration with a potassium iodide standard solution.     

Potentiometric determination of potassium ferricyanide

A rapid and accurate electrometric method for the determination of potassium ferricyanide solutions has been investigated. It consists in titrating ferricyanide solutions potentiometrically against standard AgNO₃, using a silver indicator electrode in conjunction with a saturated calomel electrode connected by a KNO₃ bridge. Either of the reagents may be used as the titrant. A marked change in e.m.f is observed at thc end-point corresponding to the formation and precipitation of Ag³[Fe(CN)₆]. The curves have a regular form, a pronounced maximum in dE/dV occurs at the end-point and the results are very accurate and reproducible. The reaction, though simple, affords a quantitative method for the determination of ferricyanide or silver. The effect of neutral salts and ethanol on the accuracy of the end-point has been studied.     

Extraction spectrophotometric determination of maneb with 1-(2'-pyridylazo)-2-naphthol (PAN)

A rapid, sensitive, simple and selective spectrophotometric method has been developed for the determination of micro-quantities of maneb (manganese ethylenebisdithiocarbamate) after extraction of the manganese-PAN complex in isobutyl methyl ketone (MIBK). The complex absorbs strongly at 550 nm. Beer's law is obeyed over the concentration range 0.37-3.75 microg/ml. The molar absorptivity was found to be 4.1 x 10(4) l. mole(-1) . cm(-1). The developed method has been applied to the determination of maneb in commercial formulations, synthetic mixtures, grain and in the presence of various other dithiocarbamates.     

Analytical applications of copper(II) and copper(I) in acetonitrile: potentiometric and spectrophotometric determination of dithiocarbamates

The use of copper(II) perchlorate and tetra-acetonitrilocopper(I) perchlorate (in acetonitrile) for the potentiometric and spectrophotometric determination of dithiocarbamates in acetonitrile medium is described. The proposed methods are simple, accurate and reliable and show promise of wide applicability. They are recommended for routine determination of dithiocarbamates. Their advantages over the carbon disulphide evolution method, commonly employed for the determination of these compounds, are discussed.     

Spectrofluorimetric determination of acetaminophen with N-bromosuccinimide

A simple, sensitive, and selective method for determination of acetaminophen based on its oxidation using N-bromosuccinimide (NBS) to produce a highly fluorescent product. Optimization of reaction variables was carried out concerning NBS concentration, pH, temperature, reaction time, and stability time. Under optimal analytical conditions, the fluorescent intensity was measured at lambda emission. 442 nm (excitation at lambda 330 nm). The linearity range is 120-800 ng/mL with lower detection limit of 33.6 ng/mL acetaminophen. The method was applied successfully to the determination of the compound in pharmaceutical preparations, with average recovery of 100.3 +/- 2%. The method was also applied successfully to the determination of the drug in spiked plasma samples, with an average recovery of 101.2 +/- 1%. Interference effects of some compounds, present in combination with acetaminophen, were studied and the tolerance limits of these compounds were determined.     

Amperometry with two polarisable electrodes-XI Determination of bismuth by EDTA titration

Optimum conditions have been found for a highly selective determination of bismuth via EDTA titration with biamperometric indication of the end-point. The influence of the applied potential, pH and stirring on the accuracy and selectivity of the determination has been studied. In a medium of 0.4M nitric acid only high concentrations of iron(III) and copper(II) interfere with the determination of bismuth. Zirconium, thallium(III) and indium interfere even in small concentrations. The average error of the determination of 5-100 mg of bismuth (when titrated with 0.05M EDTA solution) is +/-0-1 % rel. and for the determination of 0.5-10 mg it is +/-0.3% rel. (0.005M EDTA). The method has been verified by the analysis of a Wood's metal of known composition.     

Stability-indicating methods for determination of tiapride in pure form, pharmaceutical preparation, and human plasma

Four different stability-indicating procedures are described for determination of tiapride in pure form, dosage form, and human plasma. Second derivative (D2), first derivative of ratio spectra (1DD), spectrofluorimetric, and high-performance column liquid chromatographic (LC) methods are proposed for determination of tiapride in presence of its acid-induced degradation products, namely 2-methoxy-5-(methylsulfonyl) benzoic acid and 2-diethylaminoethylamine. These approaches were successfully applied to quantify tiapride using the information included in the absorption, excitation, and emission spectra of the appropriate solutions. In the D2 method, Beer's law was obeyed in the concentration range of 1.5-9 microg/mL with a mean recovery of 99.94 +/- 1.38% at 253.4 nm using absolute ethanol as a solvent. In 1DD, which is based on the simultaneous use of the first derivative of ratio spectra and measurement at 245 nm in absolute ethanolic solution, Beer's law was obeyed over a concentration range of 1.5-9 microg/mL with mean recovery 99.64 +/- 1.08%. The spectrofluorimetric method is based on the determination of tiapride native fluorescence at 339 nm emission wavelength and 230 nm excitation wavelength using water-methanol (8 + 2, v/v). The calibration curve was linear over the range of 0.2-3 microg/mL with mean recovery of 99.66 +/- 1.46%. This method was also applied for determination of tiapride in human plasma. A reversed-phase LC method performed at ambient temperature was validated for determination of tiapride using methanol-deionized water-triethylamine (107 + 93 + 0.16, v/v/v) as the mobile phase. Sulpiride was used as an internal standard at a flow rate of 1 mL/min with ultraviolet detection at 214 nm. A linear relation was obtained over a concentration range of 2-30 microg/mL with mean recovery of 99.66 +/- 0.9%. Results were statistically analyzed and compared with those obtained by applying the reference method. They proved both accuracy and precision.     

Chemically modified carbon paste electrode for the potentiometric determination of dicylomine hydrochloride in batch and in FIA conditions.

A carbon-paste electrode for dicyclomine hydrochloride (DcCl) was prepared and fully characterized in terms of composition, life span, usable pH range and temperature. The electrode was applied to the potentiometric determination of dicylominium ion in its pure state and in pharmaceutical preparations in batch and flow injection conditions and in biological fluids using standard additions method. The electrode is based on a mixture of two ion-exchangers, namely, dicyclominium-phosphomolybdate and dicylominium-tetraphenylborate, dissolved in dioctyl phthalate as pasting liquid. The modified electrode showed a near-Nernstian slope of 58 +/- 2 mV over the concentration range of 1.2 x 10(-5)-1.6 x 10(-2) M with an average recovery of 97-102% and a RSD of 0.090-1.00. The electrode exhibits good selectivity for DcCl with respect to a large number of inorganic cations, sugars, amino acids and organic substances of biological fluids. Potentiometric titrations of DcCl with several titrants have been monitored using this modified carbon paste electrode as an end-point indicator electrode.     

Determination of some dithiocarbamates by catalytic thermometric titration

The determination of dithiocarbamates by catalytic thermometric titration is described. The dithiocarbamates can be determined in the range 0.5-20 mumole with relative errors of about 5%.