Triphenylmethane dyes as redox indicators in dichrometry

Summary The use of some triphenylmethane dyes, Erioglaucine A, Eriogreen B, Xylenecyanol FF, Setoglaucine O, Setocyanine Supra, Fast Green FCF, and Night Blue as redox indicators in the dichrometric titration of iron(II), ferrocyanide, uranium(IV), molybdenum(V), and hydroquinone in hydrochloric acid, sulphuric acid and perchloric acid media has been studied. Conditions for the satisfactory titrations employing these indicators have been established.

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Triphenylmethanfarbstoffe als Redoxindicatoren bei Titrationen mit Dichromat

Zusammenfassung Bei der Titration von Eisen(II), Hexacyanoferrat(II), Uran(IV), Molybdän(V) und Hydrochinon mit Dichromat in salz-, schwefeloder perchlorsaurer Lösung wurden folgende Triphenylmethanfarbstoffe als Indicatoren verwendet: Erioglaucin A, Eriogrün B, Xylolcyanol FF, Setoglaucin O, Setocyanin Supra, Echtgrün FCF und Nachtblau. Die entsprechenden Titrationsbedingungen werden mitgeteilt.

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We are grateful to the Council of Scientific & Industrial Research, India, for the award of a Junior Research Fellowship to one of us (V. V. S. E. D.).     

Some triphenylmethane dyes as redox indicators in the titration of antimony(III) with cerium(IV) sulphate

Erioglaucine A, Eriogreen B, Patent Blue and Xylene Cyanol FF work satisfactorily for the titration of Sb(III) with Ce(IV) in 1-2N sulphuric acid medium with iodine as catalyst. In hydrochloric acid medium the colour of the oxidized dye is very evanescent but is very much improved in intensity and stability by the addition of manganese(II) sulphate; no catalyst is needed.     

Sequential titration of iron(II) and vanadium(IV) mixtures with cerium(IV) sulphate, with ferroins as indicators

The titration of vanadium(IV) with cerium(IV) sulphate, with nitroferroin as indicator, is proposed. Unlike ferroin, the indicator does not need a catalyst in this system. By suitable choice of experimental conditions iron(II) can be titrated first to a ferroin end-point and then vanadium(IV) to a nitroferroin end-point.     

Phthalocyanines as oxidation-reduction indicators

Summary Copper phthalocyanine tetrasulphonic acid has been found to work satisfactorily as an inside indicator in the cerimetric titration of hydro-quinone and metol. It has the advantage that the indicator correction in titrations with 0.01 N solutions of ceric sulphate is much less than with the ferroin indicator, amounting to only 0.02 ml for two drops of the indicator solution.Part II: See Z. analyt. Chem. 163, 1 (1958).     

Phthalocyanines as oxidation-reduction indicators

Analytical and Bioanalytical Chemistry -     

Titration of antimony(III) with cerium(IV) sulphate and diphenylamine and its derivatives as reversible indicators

Diphenylamine, barium diphenylamine sulphonate, N-phenylanthranilic acid and 2-nitrodiphenylamine have been investigated as reversible indicators for the titration of antimony(III) with cerium(IV) sulphate in 0.5–2 M sulphuric acid medium. Diphenylamine is the most satisfactory in titrations of antimony(III) in chloride-free solutions, e.g. of potassium antimonyl tartrate. Even low chloride concentrations affect the indicator action of N-phenyl-anthranilic acid or 2-nitrodiphenylamine, but diphenylamine is satisfactory in 1 M hydrochloric acid media. Iodine catalyst is necessary to accelerate the reduction of the oxidized indicator by antimony(III). The indicator colour change is vivid and the colour of the oxidized indicator is stable. Titrations of antimony(III) in mixtures with iron(II) and arsenic(III) are also considered.     

A new spot test for cerium(IV) using triphenylmethane dyes

Summary A new sensitive and selective spot test for cerium(IV) using the triphenylmethane dyes, Erioglaucine A, Eriogreen B, Xylenecyanol FF, Setoglaucine O, and Setocyanine Supra, respectively, is described. The method consists of adding one drop of the dye solution (0.1%) to a drop of cerium(IV) solution, and then treating the mixture with sufficient amount of sulfuric, perchloric, or phosphoric acid to maintain the acidity at 6 to 9M. The colors produced with these dyes are: Erioglaucine A: orange, Eriogreen B: bright red, Xylenecyanol FF: orange yellow, Setoglaucine O: bright orange, and Setocyanine Supra: pink. The identification limit is 1 g in 1.5 ml, and the dilution limit is 11.5 · 10⁶ in all these cases. Many cations and anions do not interfere in the test, whereas reducing agents like Fe(II), Mo(V), U(IV), and hydroquinone, fluoride and EDTA interfere.

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Zusammenfassung Eine neue empfindliche und selektive Tüpfelnachweisreaktion für Cer(IV) mit den Triphenylmethanfarbstoffen Erioglaucin A (I), Eriogrün B (II), Xylolcyanol FF (III), Setoglaucin O (IV) bzw. Setocyanin Supra (V) wurde beschrieben. Man gibt einen Tropfen 0,1%ige Farbstofflösung zu einem Tropfen Cer(IV)-Lösung und behandelt die Mischung mit Schwefelsäure, Perchlorsäure oder Phosphorsäure, um 6 -bis 9-m Acidität zu erreichen. Die mit den genannten Farbstoffen erzielten Farbreaktionen sind: mit I orange, mit II leuchtend rot, mit IV leuchtend orange, mit III orange-gelb, mit V rosa. Die Erfassungsgrenze beträgt 1g/1,5 ml, die Grenzkonzentrationen in jedem Fall 11,5 · 10⁶. Viele Kationen und Anionen stören nicht, aber Reduktionsmittel wie Fe(II), Mo(V), U(IV), Hydrochinon sowie Fluorid und ÄDTA stören.

     

N-substituted phenothiazines as indicators in titrations with chloramine-T

Trifluoperazine dihydrochloride, butaperazine dimaleate, promethazine hydrochloride, diethazine hydrochloride, prochlorperazine maleate and chlorpromazine hydrochloride have been studied as redox indicators in titrations of hydroquinone, metol and ascorbic acid with chloramine-T. The end-points obtained are sharper than with conventional indicators. The molar absorptivities of the oxidized indicators are reported. Simple but accurate methods for the determination of hydroquinone and metol are described.     

Triphenylmethane dyes as fluorescent probes for G-quadruplex recognition

Triphenylmethane (TPM) dyes normally render rather weak fluorescence due to easy vibrational deexcitation. However, when they stack onto the two external G-quartets of a G-quadruplex (especially intramolecular G-quadruplex), such vibrations will be restricted, resulting in greatly enhanced fluorescence intensities. Thus, TPM dyes may be developed as sensitive G-quadruplex fluorescent probes. Here, fluorescence spectra and energy transfer spectra of five TPM dyes in the presence of G-quadruplexes, single- or double-stranded DNAs were compared. The results show that the fluorescence spectra of four TPM dyes can be used to discriminate intramolecular G-quadruplexes from intermolecular G-quadruplexes, single- and double-stranded DNAs. The energy transfer fluorescence spectra and energy transfer fluorescence titration can be used to distinguish G-quadruplexes (including intramolecular and intermolecular G-quadruplexes) from single- and double-stranded DNAs. Positive charges and substituent size in TPM dyes may be two important factors in influencing the binding stability of the dyes and G-quadruplexes.     

Anodic generation of cerium (IV) at glassy carbon in acetic acid and coulometric titrations with the generated reagent

Conditions for electrochemical generation of cerium(IV) at glassy carbon in acetic acid in the presence of alkali-metal acetates and sodium perchlorate, respectively, were investigated. A high current efficiency was achieved in anodic oxidation of cerium(III) in acetate supporting electrolytes. Coulometric titration methods for the determination of reducing substances with the generated oxidant were also developed. The end-points were determined by the biamperometric and bipotentiometric methods. The error of the determinations was less than + 2%.     

Thermal decomposition of cerium(III) perchlorate

Thermal decomposition of Ce(ClO₄)₃ ? 9H₂O and Ce(ClO₄)₃ to give cerium(IV) dioxide in the temperature range 240–460°C was studied by DSC–TGA, X-ray powder diffraction, IR and mass spectroscopy. The thermolysis of these salts was shown to proceed through the stage of formation of intermediate product supposedly cerium oxoperchlorate. The thermal decomposition of cerium(III) perchlorate hydrate at 460°C leads to formation of nanocrystalline cerium dioxide with particle size of 13 nm.     

Photometric titrations with indicators

Various types of photometric titration curves are discussed. If a metal M is titrated conipleximetrically using a metal indicator and the absorbance is plotted vs. the titrant consumed, the inflection point appears at a pM value defined by the equation 3 pM_infl = pM_trans + 2 pM_eqThis expression is valid when M combines in a 1 : 1 ratio with the complexing agent and the indicator and when the indicator concentration is small compared to the total metal concentration.The difference between the pM values at the inflection and equivalence points can be calculated from the equation ΔpM = pM_infl — pM_eq = $\text{1}\text{3}$(pM_trans — pM_eq) = $\text{1}\text{6}$log(C_MK²_MI/K_MY)If the inflection point is taken as the equivalence point, the error arising can be calculated from ΔpM, or more simply, read from a diagram.If transmittance, instead of absorbancc, is plotted as a function of the titrant volume, the inflection point depends on the added amount of indicator. However, at high transmittance values, i.e., at low indicator concentrations, the inflection point of a transmittance curve occurs practically at the same volume of added titrant as the inflection point of an absorbance curve. Rules are given for applying an indicator correction for the amount of metal bound to the indicator at the end-point.The derived equations and discussions can also be applied to acid-base titrations.