Solochrome violet R.S. as a new colorimetric reagent

Summary Solochrome violet R.S. has proved to be a sensitive colorimetric reagent for the microdetermination of vanadium in the limits of 0.05 to 6 ppm with a sensitive filter photometer or a spectrophotometer, at 580 nm. A large number of cations up to 100 fold the vanadium amount do not interfere with its determination. The present work comprises a comparative study on the behaviour of solochrome violet and Fast Grey, based upon the great similarity in the molecular structure of the two dyes and the influence of the orthonitrophenolic group in the molecule of Fast Grey.Part I: See Z. analyt. Chem. 178, 184 (1960).     

Applications involving oxidation with KBrO3: Potentiometric determination of some inorganic white and yellow pigments

Rapid potentiometric methods were given for determination of some sulfide and chromate pigments in pure as well as adulterated samples. The methods are based on oxidation of S^2? or Cr³⁺ with known excess of KBrOs³ to the corresponding (S ↓) or Cr^6?. Oxidation of trivalent chromium proceeds only toward completion in presence of a catalyst such as Co²⁺. Sulfide oxidation needs gradual liberation of H₂S—which can be achieved by dropwise additions of the acid—together with the presence of excessive amount of water, in order to obtain accurate results excess oxidant was subsequently reduced with SO₂ to produce Br^? that can be titrated against Hg(I). The potential breaks are quite sharp for accurate determination of the equivalent points.     

Selective separation of uranium using trimethylammonium acetosalycoylhydrazone modified Duolite C20 resin</p> </p>

Summary Duolite C20 resin modified with trimethylammonium acetosalycoylhydrazone has been developed, for the selective separation and/or preconcentration of uranium. The modified resin was characterized by elemental analysis and infrared spectra. Batch and column modes were applied. The newly designed resin quantitatively sorbs uranium ion at pH 3 when the flow rate equals to 2 ml ^. min ^-1 . The sorption capacity was 0.750 mmol ^. g^-1 for uranium ion, whereas its preconcentration factor was 200. The lower limit of detection was 5 ng ^. ml^-1 and its desorption was effective with 5 ml of 3 mol ^. l^-1 HCl or HNO₃ prior to detection spectrophotometry. The modified resin was highly ion-selective in nature even in the presence of large concentrations of electrolyte or organic media, with a preconcentrating ability for uranium ion. The modified resin was tested on its utility with synthetic, real and certified ore samples, showed RSD values of <2% reflecting the accuracy and reproducibility of the newly modified resin.</p> </p>     

Characterization of the photoisomers from cis- and trans-chlordanes, trans-nonachlor and heptachlor epoxide

Irradiation of acetone solutions of trans-chlordane (4a) and trans-nonachlor (4b) with UV light produces new half-cage photoisomers (5a or 6a and 5b or 6b, respectively) with bridging that differs from that of the photoisomers (2 and 8a) obtained from cis-chlordane (1b) and heptachlor epoxide (7). A new photoisomer (10) obtained from heptachlor epoxide is transformed into photoisomer 8a on further irradiation. Detailed PMR and ¹³C-NMR studies establish the structures of the new photoisomers and permit a decision between alternative formulations for the structures of the half-cage photoisomers of heptachlor epoxide and cis-chlordane,     

Solochrome Black P.V. as a new reagent in chelatometry

Summary The acid-base properties of Solochrome Black P.V. have been studied with the object of applying it as a metallochromic or as a chromophoric indicator. The pK values of 4.1, 7.0 and 11 corresponding to the three steps of ionisation of the free acid were evaluated by aid of the relation between log (acid)/(salt) and p_H values obtained during the course of the potentiometric titration of the free acid with a free base together with the E-p_H relation. The molecular ratio of the magnesium-dye chelate and its mode of chelation are given.

---

Zusammenfassung Die Eigenschaften des Farbstoffs Solochrome Black P.V. werden im Hinblick auf seine Verwendung als Metalloder Farbindicator untersucht. Entsprechend den drei Dissoziationsstufen der freien Säure werden pK-Werte von 4,1, 7,0 und 11 gefunden. Diese werden mit Hilfe der Beziehungen zwischen log [Säure]/[Salz] und p_H sowie zwischen E und p_H ausgewertet. Bildung und Zusammensetzung des Mg-Farbstoffchelats werden näher untersucht.

     

Applications,involving the iodide ion: VIII. Direct and indirect determination of mercury(I) and analysis of mixtures. Analysis of chromium(VI)-chromium (III) mixtures. Determination of hypochlorite

Mercury(I), down to 3 ppm, has been accurately determined by direct titration with iodide or by back-titrating excess of iodide with mercury (II) using silver amalgam as the indicator electrode. The direct method and additional volumetric ones were applied to the rapid analysis of various mixtures involving mercury(I) with fair accuracy and precision. Analysis of Cr(VI)-Cr(III) mixtures involved potentiometric back-titration of excess iodide and of excess EDTA separately with mercury(II). Back-titration of excess iodide was successfully applied to the determination of hypochlorite.     

Back titration with mercuric nitrate in alkaline medium

Summary A rapid, reliable and accurate method for the determination of trivalent chromium, based on back titrating excess EDTA solutions in the presence of chromium versenate, with mercuric nitrate in alkaline media is given. By its aid amounts of chromium in the order of 50 micro- to 15 milligrams can be determined with fair accuracy. The method is applied for analysis of binary mixtures of chromium with thorium, copper(II), bismuth or mercury(II).     

Stereocontrolled synthesis and determination of the c-24 and 25 stereochemistry of glaucasterol

(24S,25S)- and (24R,25R)-24,26-Cyclocholesta-5,22E-dien-3β-ols (1a and 1b) were synthesized stereoselectively. Their ₁H NMR comparison with natural glaucasterol (1) allowed to conclude that 1 possesses 24S,25S stereochemistry.     

Substituent effects on the stability of copper(II) chelates with some Neville Winter's azo dyes

The effect of substituents on the stability of the complexes formed by reaction of Neville Winter's acid para-substituted azo dyes (p-chloro, methoxy, nitro, and sulfonic) is studied. Log K values for the complexes were determined spectrophotometrically. The p-methoxy and p-chloro chelates exhibited maximum and minimum stabilities, respectively, the methoxy group being electron repelling and chlorine electron withdrawing. Calculations applying Hammett and linear free energy equations indicate that copper in these chelates acts as a π-electron accepter and that such chelates exhibit coplanarity.