Analytical applications of the amine-carbon disulphide reaction in acetonitrile

The ease with which carbon disulphide transforms primary and secondary amines in acetonitrile medium into the corresponding monoalkylammonium monoalkyldithiocarbamates and dialkylammonium dialkyldithiocarbamates respectively and the simplicity and reliability of potentiometric and spectrophotometric determination of dithiocarbamates with copper(I) perchlorate in the same medium, provide simple, accurate and reliable methods for the determination of primary and secondary amines and of organic isothiocyanates.     

Ascorbic acid reaction with disulphide compounds: effects and applications

A method was developed for estimation of concentrations of cystine based on the reaction of this oxidised amino acid with ascorbic acid and copper ion. The standard curve which was constructed was used as the basis for investigation of the effects which both cystine and glutathione disulphide, and some disulphide proteins, exerted on the amount of hydrogen peroxide formed in the reaction of ascorbic acid. The hydrogen peroxide product was lowered in the presence of the disulphide compounds. The disulphide compounds also lowered the amount of deoxyribose reacting material formed during the ascorbic acid oxidation. The reaction between ascorbic acid and copper and cystine was used to estimate the amount of the disulphide amino acid in acid digests of proteins.     

Analytical applications of reactors containing immobilized enzymes

The theory for analytical packed-enzyme reactors is discussed and it is shown that a 100% conversion efficiency gives many advantages. This concept has been applied to methods for substrate determinations of urea, amino acids, and glucose. Enzyme reactors have also been used in the effluent from a Chromatographic column to enhance selectivity and sensitivity for cholesterol. Enzyme reactors for the determination of inhibitors, e.g. mercury ions, should be designed differently. A low conversion efficiency gives high sensitivity and a linear response.     

Determination of mixtures containing amines and thioureas

A convenient and accurate method has been described for the analysis, on the same sample solution, of mixture of amines and thioureas. The mixture solution is first analyzed for amines by an acidimetric titration. The titrated solution is acidified with more aqueous acid and then analyzed for thioureas by an oxidimetric titration. The method has been successfully applied to the analysis, also on the same sample solution, of mixtures containing isocyanates and thioureas. A known excess of standard n-butylamine added to the mixture solution in diemthylformamide converts the isocyanates to the corresponding disubstituted ureas. Acidimetric titration of the excess of amine followed by iodatometric titration of thiourea present enable the mixture to be analyzed for both the components. The methods described are reliable and have wide applications.     

The thermodynamic properties of binary mixtures containing carbon disulphide I. Phase diagrams and excess volumes

Phase diagrams and excess volumes at 298.15 K have been measured for the four binary mixtures carbon disulphide+cyclohexane, +n-hexane, +1,5-hexadiene, and +1,5-hexadiyne. The results are discussed qualitatively in the light of recent theoretical calculations of the structure and thermodynamic properties of mixtures containing anisotropic molecules.     

Analytical applications of liquid-liquid phase equilibria: analysis of binary mixtures of chemically similar components

A new, simple and rapid method based on the principle of liquid-liquid phase equilibria has been developed for the analysis of binary mixtures of chemically similar organic compounds. The method does not require elaborate instrumentation and can be used to analyse mixtures of members of homologous series. The application of the method has been illustrated by analysing binary mixtures of n-hexane and n-octane; the maximum uncertainty in this analysis is ~2%.     

Analytical applications of the reaction of thorium with benzenephosphonic acid

Benzenephosphonic acid quantitatively precipitates thorium as Th(C₆H₅PO₃)₂·3H₂O at pH values as low as 0.5. The compound may be dried at 140° to 180° C and weighed, as a gravimetric means of determining thorium. On ignition, Th (C₂H₅PO₃)₂ 3 H₂O undergoes decomposition at 240° to 300° C to form Th(C₆H₅PO₃)₂·2H₂O, at 450° to 650° C to form Th(HPO₄)₂·2H₂O and finally at 800° to 1000° C to form Th(HPO₄)₂. The latter compound is stable to 1200° C.Potentiometrically (pK₁' = 0.91, pK₂' = 6.41) and spectrophotometrically (pK₁' = 0.96, pK₂' = 6.51) determined pK' values are reported. Absorption spectra of C₆H₅PO₃H₂, C₆H₅PO₃H^- and C₆H₅PO₃^-2 are reported. The solubility of Th (C₆H₅PO₃)₂·3H₂O was studied as a function of pH and the average value of the solubility product (K_sp = 4s³) was found to be 3.24·10^-31.     

Analytical applications of the determination of hexacyanoferrate(III) with ascorbic acid : Determination of hydrogen peroxide,peroxydisulphate and their mixtures

Hydrogen peroxide can be determined by reaction with excess of alkaline hexacyanoferrate(III), the excess being titrated with ascorbic acid. Peroxydisulphate is determined by reaction with hexacyanoferrate (II) in acidic medium, the hexacyanoferrate(III) formed being titrated with ascorbic acid. To determine hydrogen peroxide and peroxydisulphate in the presence of each other, two titrations are needed ; the results arc readily calculated.     

Effect of solvent properties on reaction of isocyanates with mercaptans

Generalization of data on the reaction rate of catalyzed process between mercaptans and phenyl isocyanate in various media led to the conclusion that the reaction rate increased due to the specific, especially nucleophilic, solvation. The primary reaction stage is the formation of a complex between the acidic mercaptan and a base, a catalyst (triethylamine) or basic solvent.     

Analytical applications of the o-dianisidine-persulfate reaction: Kinetic determination of silver and cobalt

A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead.     

Determination of carbon disulphide in water

Summary It could be demonstrated that the determination of CS₂ in water and waste water is generally not affected by solids in lower quantities. An alkalization is recommended in the presence of hydrogen sulphide.

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Bestimmung von Schwefelkohlenstoff in Wasser

Zusammenfassung Die Bestimmung von Schwefelkohlenstoff in Wasser und Abwasser wird nachweislich durch geringe Mengen fester Stoffe nicht gestört. In Gegenwart von Schwefelwasserstoff ist Alkalisierung zu empfehlen.

     

Analytical applications of electrochemiluminescence: an overview

The chemical transformations of electrogenerated ion-radicals of a number of complex organic compounds may be accompanied by emission of photons. An electrochemiluminescence (ECL) quantum contains information both on the kinetics of the heterogeneous electrode processes and on the subsequent homogeneous chemical reactions in the solution. Application of ECL to solution analysis provides advantages in comparison to electrochemical methods. Using ECL for electrode surface analysis allows information to be obtained on the rate of an electrochemical process simultaneously at all points of the electrode under analysis in real time, and that is the main difference between this method and the point-by-point testing specific to electrochemical methods. The potential of ECL for analytical chemistry is examined concerning the homogeneous ECL-analysis of solutions and the heterogeneous ECL-analysis of electrode surfaces. Received: 6 April 2000 / Revised: 23 June 2000 / Accepted: 27 June 2000     

Analytical applications of hydroxycoumarins

A review is presented of the analytical potentialities and physico-chemical properties of hydroxycoumarins.     

Analytical applications of quinoxalines

The uses of quinoxalines as analytical reagents are reviewed.     

Analytical applications of bioluminescence

The phenomenon of bioluminescence has, since the time of Sir Robert Boyle, attracted the interest of scientific researchers. The detailed mechanisms of many bioluminescent systems are now well understood and have the potential to form the basis of accurate and sensitive analytical methods.