5:6-Benzoquinaldinic acid as an analytical reagent: Determination of titanium

The reagent 5 :6 -benzoquinaldisic acid precipitates titanium(lV) completely from solution at and above pH 3.0 in the presence of rare earths. Coprecipitation of magnesium and the alkaline earths is easily prevented by the addition of ammonium chloride. Separation from iron(III), thorium or zirconium can be carried out in the presence of complexone III. magnesium sulphate being used as a demasking agent. Separation from aluminium is not possible. The titanium precipitate is not of definite composition and so it is ignited to the oxide before weighing.     

5:6-Benzoquinaldinic acid as a colorimetric reagent

5:6-Benzoquinaldinic acid, like α-picolinic acid, has been utilised as a colorimetric reagent for iron (ous). Transmittancy measurements with the Lumetron 402 EF having a cell of capacity 16 ml and thickness 20 mm show that iron from 0.4 to 20 p.p.m. may be estimated, while that with Klett-Summerson photoelectric colorimeter, iron from 5 to 50 p.p.m. may be determined in a tube cell of capacity 15 ml and diam. 12 mm. The optimum range with the minimum error is from 2.4 to 14 p.p.m. The effect of diverse ions, reagent, reducing agent, cyanide and other physical conditions as temperature, time, etc. on the colour system has been investigated.     

Diphenic acid as an analytical reagent

Summary Diphenic acid behaves as a selective reagent for the estimation of thorium in presence of phosphate, arsenate, molybdate, alkaline, earths, copper, cadmium, lead, bismuth, tin, aluminium, chromium, nickel, cobalt, zinc, manganese, magnesium and palladium. Thorium can be successfully separated from the cerite earths by the reagent from solutions having thoria: earth oxide ratio 126 by single precipitation and by double precipitation when the above ratio is 144. The reagent can separate thorium from solutions having ThO₂U₃O₈ ratio upto 180 by double precipitation. The metal can also be recovered from monazite sands.Thanks are expressed hereby to Dr. A. K. Ghosal, Principal, Darjeeling Government College and Dr. A. K. Mukherjee of Indian Association for the Cultivation of Science, Calcutta, for their kind encouragement and to the Government of India, Ministry of Natural Resources and Scientific Research for a gift of Indian Monazite for analysis.     

Salicylhydroxamic acid as an analytical reagent

Summary Salicylhydroxamic acid has been used as a colorimetric reagent for the estimation of uranium, vanadium, molybdenum and iron. It permits the direct estimation of vanadium in presence of molybdenum and uranium, though iron interferes, while the estimation of uranium or molybdenum is not possible in presence of each other or of vanadium. The vanadium complex can be removed from solution by extraction with ethyl acetate and estimated colorimetrically between p_H 0.8 to 3.5. This permits its determination in steels after removal of iron. Sensitivity: U 0.1 g, V 0.017 g, Mo 0.015 g, Fe 0.0125 g.     

Diphenic acid as an analytical reagent

Summary Diphenic acid can separate thorium completely from moderate amounts of ferrous iron and titanium in almost neutral solutions. As the reagent forms quantitative precipitates with ferric iron and zirconium, workable methods for their separation from thorium and their co-determinations in a mixture with the help of this reagent have also been developed. The reagent can separate thorium from zirconium by precipitating the latter below p_h2, and the same from iron(ic) can be accomplished by the use of ascorbic acid as a masking agent. Ferric iron can be precipitated from solution containing ascorbic acid, by the ammonium salt of the reagent. A convenient process for the estimation and separation of zirconium, thorium, iron(ic) and titanium, when present in a mixture, has also been described, which involves the proper control ofph and the use of ascorbic acid as a complexing agent for ferric iron.My sincere thanks are due to Dr. A.K. Mukherjee of the Indian Association for the Cultivation of Science, Calcutta for his valuable suggestions and to Dr. A. K. Ghosal, Principal, Darjeeling Government College for providing laboratory facilities.     

Use of o-cresotic acid as a reagent for the estimation of thorium and zirconium

Summary Thorium as well as zirconium are quantitatively precipitated by o-cresotic acid at pH 3.7 and above. The precipitate in both the cases can be ignited and weighed as oxide. In the case of thorium, the precipitate can also be weighed directly as ThC₈H₁₄O₈ after drying at 105–110 C. But the same is not possible in the case of zirconium as the precipitate is a basic salt of variable composition.     

Haematein as a reagent for thorium, zirconium and uranium

Summary Haematein gives violet colored complexes with thorium and uranium and an orange colored complex with zirconium of the stoichiometric ratios 16, 13, and 11 respectively of the metal and the reagent (Job's method). The reagent and the complexes of thorium, uranium and zirconium show absorption maxima at 520–540 m, 520–540 m 500–520 m respectively. In observations at 540 m in 60 percent aqueous acetone 0.05 mg of thoria (a 12 fold excess of cerite earths has no influence), 0.029 mg U₃O₈ and 0.025 mg of zirconia may be determined. The spectral characteristics of the complexes indicate a similarity in character in spite of differences in stoichiometric composition.     

Acenaphthenequinonedioxime as an analytical reagent: Determination of nickel in mixtures

Summary The titled reagent (ANDO) has been used as a reagent for gravimetric determination of nickel and for its separation from common cations and anions. Nickel (II) precipitates quantitatively by ANDO within the pH range 6.8–8.4. After drying the precipitate at 110°, its composition corresponds to the formula Ni(C₁₂H₇O₂N₂)₂. Many commonly associated ions, except Fe(III), Co(II) and Cu(II), do not interfere. Solvent-extraction techniques have been utilized to separate Cu(II) and Co (II) from the binary mixture. For masking Fe(III) excess citrate ion has been used. Elemental analysis confirms 12 metal-ligand ratio. The complex is approximately diamagnetic ( _eff=0.95 B. M.) and gives typical d-d spectral bands as generally observed in square planar complexes involving d⁸ electronic configuration. Electronic spectra of the metal chelate in pyridine are discussed and results of thermo gravimetric analysis are also presented. I. R. and far I. R. spectral analysis indicate the involvement of strong hydrogen bridges and metal-nitrogen bond.

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Acenaphthenchinondioxim als analytisches Reagens: Bestimmung von Nickel in Gemischen

Zusammenfassung Acenaphthenchinondioxim (ANDO) wurde für die gravimetrische Bestimmung von Nickel und für dessen Trennung von üblichen Kationen und Anionen verwendet. Ni(II) wird mit diesem Reagens quantitativ ausgefällt innerhalb des pH-Bereiches 6,8–8,4. Getrocknet bei 110° entspricht der Niederschlag der Zusammensetzung Ni(C₁₃H₇O₂N₂)₂. Viele üblicherweise anwesende Ionen, ausgenommen Fe(III), Co(II) und Cu(II), stören nicht. Die beiden letztgenannten lassen sich durch Extraktionen abtrennen, Fe(III) wird mit Citrat maskiert. Das Metall-Ligand-Verhältnis beträgt 12. Die Komplexverbindung ist nahezu diamagnetisch ( _eff=0,95 B. M.) und gibt typische d-d-Spektralbanden, wie sie üblicherweise von planar-quadratischen Komplexen mit d⁸-Elektronenkonfiguration gezeigt werden. Die Elektronenspektren des Metallchelates in Pyridin wurden diskutiert und die Ergebnisse der thermogravimetrischen Untersuchung angeführt. IR- und ferne IR-Analyse weisen auf die Anwesenheit starker Wasserstoffbrücken und auf eine Metall-Stickstoff-Bindung hin.

     

Thiodiglycolic acid as a reagent for zirconium

Thiodiglycolic acid is shown to be a suitable precipitating reagent for zirconium. The analysis is completed by igniting the precipitate and weighing the ZrO₂. Several metal ions do not interfere. Interference due to cerium(IV) is avoided by reducing it initially to cerium(III). Estimation of zirconium can be carried out in presence of thorium. The composition of the Complex is slightly variable but corresponds to zirconyl thiodiglycolate: O =

     

Bismuthiol as an analytical reagent

Summary Lead can be determined from its Bismuthiol II complex volumetrically by dissolving it in an excess of EDTA at a p_H of about 10 and titrating the excess of the EDTA against a magnesium or lead solution. In the same way silver can be determined by dissolving the complex in an excess of cyanide and back titrating the excess against a standard silver nitrate with iodide as the indicator. The results of the former are fairly accurate while those due to latter are highly satisfactory with silver less than 20 mg. With higher amounts of silver, however, the results are within +2%.Part VIII see Z. analyt. Chem. 156, 103 (1957).     

Nicotinamidoxime as an analytical reagent

Summary Cobalt(II) gives a deep blue colour with nicotinamidoxime in alkaline aqueous-ethylalcoholic medium which has been used with advantage for the spectrophotometric determination of this metal. The optimum p_H for the development of colour is 9.8–11.3 in aqueous-alcoholic (40% v./v.) medium in presence of a large excess of the reagent, at 15–40°C. The colour intensity is measured at 580 m,. Sensitivity is 0.01 g cobalt per cm², while visual identification limit is 0.5 g cobalt per ml (12·10⁶). Beer's law is obeyed in the range of 0.2–20 ppm of the metal, with an optimum range of 2–16 ppm. The colour is stable for about half an hour in the p_N range of 9.8–11.3 and at least one hour in the range of 10.5 to 11.0. On account of the high p_N and alcoholic medium used, most of the cations and anions interfere and, hence, must be removed.Part I: See Z. anal. Chem. 168, 326 (1959).     

Bis-salicylaldehyde-ethylenediamine as an analytical reagent

Summary The compound bis-salicylaldehyde-ethylenediamine was prepared by the condensation of salicylaldehyde with ethylenediamine. It was crystalline and quite stable. The solution of the compound in caustic alkali was used for the analytical reactions of various ions. Ions of Cu²⁺, Ni²⁺, Bi³⁺, Zn²⁺, Hg²⁺, Sb³⁺, Sn²⁺ and Ce⁴⁺ formed precipitates, while those of As³⁺ and Pd²⁺ gave slight turbidity and Fe²⁺, Pe³⁺, Co²⁺ gave colour reactions. Rest of the ions did not respond towards the reagent. The sensitivity of the reactions for Cu²⁺, Ni²⁺, Fe²⁺, Fe³⁺, Ce⁴⁺, Co²⁺ and Sb³⁺ was high and their quantitative determinations are possible.

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Zusammenfassung Die Verbindung Bis-salicylaldehyd-äthylendiamin wurde durch Kondensation von Salicylaldehyd mit Äthylendiamin dargestellt. Sie ist kristallin und durchaus stabil. Die ätzalkalische Läsung dieser Verbindung wird zu analytischen Reaktionen mit verschiedenen Ionen benutzt. Die Ionen Cu²⁺, Ni²⁺, Bi³⁺, Zn²⁺, Hg²⁺, Sb³⁺, Sn²⁺ und Ce⁴⁺ ergeben Niederschläge, As³⁺ und Pd²⁺ geben eine geringe Trübung und Fe²⁺, Fe³⁺ sowie Co²⁺ liefern Farbreaktionen. Die übrigen Ionen sprechen auf das Reagens nicht an. Die Empfindlichkeit der Reaktionen mit Cu²⁺, Ni²⁺, Fe²⁺, Fe³⁺, Ce⁴⁺, Co²⁺ und Sb³⁺ ist groß und eine quantitative Bestimmung dieser Ionen ist möglich.

     

Nicotinamidoxime as an analytical reagent

Summary Alkaline solutions of nicotinamidoxime containing traces of nickel(II) give a deep blue color on treatment with iodine. At a p_H of 10.5–11.5 in presence of an excess of the amidoxime the color develops almost instantaneously and is stable for at least 24 hrs. The system adheres to Beer's law in the range of 0.3–10 ppm of nickel, and the optimum range for measurement (1 cm cell) is 3–10 ppm of the metal. The color reaction is highly sensitive (spectrophotometric: 0.014 g Ni cm^–2 at 575 nm identification limit: 0.5 g Ni ml^–1; 12 · 10⁶).All the common anions are without any effect excepting CN^– and EDTA which interfere seriously. Interference of Pb²⁺, Bi³⁺, Al³⁺, Ti⁴⁺, Zr⁴⁺ and Th⁴⁺ can be masked by excess tartrate; while in the presence of Cu²⁺, Co²⁺, Zn²⁺, Mn²⁺ and Fe³⁺, the Ni²⁺ is first separated by the anion exchange method of Kraus and Moore ³ and then determined as usual.From the results of polarographic investigations it has been concluded that in alkaline medium nicotinamidoxime is first oxidized possibly to an azo type of compound which interacts with nickel(II) forming the deep blue color.Part II: K. K. Tripathi and D. Banarjea: Z. analyt. Chem. 168, 407 (1959).     

Bis-salicylaldehyde-ethylenediamine as an analytical reagent

Summary Copper has been determined gravimetrically as its bis-salicylaldehyde-ethylenediamine complex of the composition C₁₆H₁₄O₂N₂ · Cu, dried at 100–120° C. The complex is completely precipitated in theph range of 10.5–13.5, adjusted with ammonia or caustic alkali. It is stable in presence of excess ammonia, 0.1 N alkali, ammonium salts and complexing agents as tartrate, citrate, sodium-thiosulphate, fluoride, thiourea, triethanolamine and EDTA. In presence of tartrate and ammonia the ions of alkali metals, alkaline earths, Ag⁺, Tl⁺, Tl³⁺, Pb²⁺, Cd²⁺, Co²⁺, Mn²⁺, Pd²⁺, Al³⁺, Cr³⁺, La³⁺, Ce³⁺, Au³⁺, Pt⁴⁺, Ti⁴⁺, Zr⁴⁺, Th⁴⁺, UO₂ ²⁺ and anions as VO₃ ^–, MoO₄ ^2–, WO₄ ^2–, CrO₄ ^2–, PO₄ ^3–, AsO₄ ^3– do not interfere. Ni²⁺ and Hg²⁺ are masked by tartrate, EDTA and ammonia; As³⁺, Sb³⁺ and Sn²⁺ are separated using fluoride as the complexing agent; at an alkalinity of 0.1 N caustic alkali in presence of tartrate As³⁺, Sb³⁺, Sn²⁺, Bi³⁺, Zn²⁺ and Fe³⁺ are separated. Fe³⁺ can also be separated using triethanolamine as the masking agent at aph of about 13.0. Copper can be separated from almost all the ions, thus affording a highly selective method for the determination of copper.

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Zusammenfassung Es wird eine gravimetrische Methode zur Bestimmung von Kupfer beschrieben, die auf der Bildung des Bis-salicylaldehyd-äthylendiaminkomplexes beruht. Dieser hat die Zusammensetzung C₁₆H₁₄O₂N₂ · Cu. Die Fällung wird imph-Bereich 10,5–13,5 (mit Ammoniak oder Alkalilauge eingestellt) vorgenommen und der Niederschlag bei 100°–120° C getrocknet. Der Komplex ist beständig in Gegenwart von überschüssigem Ammoniak, 0,1 n Alkali, Ammoniumsalzen sowie Tartrat, Citrat, Natriumthiosulfat, Fluorid, Thioharnstoff, Triäthanolamin und ÄDTA. In Gegenwart von Tartrat und Ammoniak stören nicht: Alkalien, Erdalkalien, Ag⁺, Tl⁺, Tl³⁺, Pb²⁺, Cd²⁺, Co²⁺, Mn²⁺, Pd²⁺, Al³⁺, Cr³⁺, La³⁺, Ce³⁺, Au³⁺, Pt⁴⁺, Ti⁴⁺, Zr⁴⁺, Th⁴⁺, UO₂ ²⁺ sowie VO₃ ^–, MoO₄ ^2–, WO₄ ^2–, CrO₄ ^2–, PO₄ ^3– und AsO₄ ³⁺. Ni²⁺ und Hg²⁺ können mit Tartrat, ÄDTA und Ammoniak maskiert werden, As³⁺, Sb³⁺ und Sn²⁺ mit Fluorid. In 0,1 n ätzalkalischer Lösung in Gegenwart von Tartrat können As³⁺, Sb³⁺, Sn²⁺, Bi³⁺, Zn²⁺ und Fe³⁺ abgetrennt werden. Fe³⁺ kann ebenfalls mit Triäthanolamin beiph 13,0 maskiert werden. Das beschriebene Verfahren erlaubt somit eine Abtrennung des Kupfers von fast allen anderen Ionen.

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Part I: Singh, B. R., and S. Kumar: Z. analyt. Chem. 185, 211 (1962).     

Isonitrosoacetanilide as an analytical reagent

In a continuation of earlier work on the reactivity of various isonitrosoacetarylides, the simplest of the series, isonitrosoacetanilide was examined. In acidic medium, this reagent gives a specific reaction with palladium (dilution limit 1:400,000), and in ammoniacal medium a very sensitive reaction with cobalt (dilution limit 1:1,000,000). The composition of the complexes involved was established as R₂Pd and R₃Co₂. The effect of substitution on the reactivity is discussed.     

Nicotinamidoxime as an analytical reagent

Summary Uranium (VI) has been found to give a yellow colour with nicotinamidoxime in alkaline medium which is highly satisfactory for the spectrophotometric estimation of the metal. The optimumph for development of the colour is 10.9–11.5 in presence of a large excess of the reagent, at 10–40C. The colour intensity is measured at 400 m. Sensitivity is 0.045 g uranium per cm², with a visual identification limit of 5 g uranium per ml. Beer's law is obeyed in the range of 5–40 ppm of the metal with an optimum range of 8–40 ppm. The colour is stable for at least one hour. All the common anions are without effect, excepting however, phosphate, carbonate, and cyanide which are tolerated only in traces. Use of tartrate or EDTA helps to mask effectively all the interfering cations excepting copper, iron and vanadium.     

2-Mercapto-benzimidazole as an analytical reagent

Summary Palladium is quantitatively precipitated at aPH 5.0 to 10.1 by 2-mercapto-benzimidazole and the complex, Pd(C₇H₅N₂S)₂, which is found to be diamagnetic, is stable up to a temperature of 447 C. In presence of EDTA and tartrate or citrate and at aPH between 6 and 8, it is separated from alkalis, alkaline earths, Mg, Fe³⁺, Cr, Th, Zr, Ti, UO₂ ²⁺, Be, Ce³⁺, Ce⁴⁺, rare earths, Zn, Mn, Ni, Co, Pb, Bi, As, Sb³⁺, Sn⁴⁺, Tl⁺, Cu²⁺, Cd, Ir⁴⁺, Rh³⁺, Ru³⁺, Os⁴⁺, CrO₄ ^2–, MoO₄ ^2–, WO₄ ^2–, VO₃ ^–, PO₄ ^3– and AsO₄ ^3–. Pb, Ag and Hg²⁺ are kept in solution by potassium iodide while a small amount of Au³⁺ by thiosulphate. The palladium complex is either weighed after drying at 110 C or dissolved in a cyanide solution and determined volumetrically by back titrating the excess cyanide with a standard silver nitrate solution.     

Bismuthiol II as an analytical reagent

Summary Bismuthiol II reacts with trivalent arsenic and antimony to form complexes of compositions As(C₈H₅N₂S₃)₃ and Sb(C₈H₅N₂S₃)₃ respectively, while with stannous the reaction is not stoichiometric. The ions of arsenic and antimony can be estimated, from an acid solution, 0.1 N in hydrochloric or sulphuric acid, with the ammonium or the sodium chloride as the coagulant. The complexes have low melting points and they are soluble in organic solvents.Part XI see Z. analyt. Chem. 161, 257 (1958).     

Bismuthiol II as an analytical reagent

Summary Lead was estimated as Bismuthiol II complex of composition (C₈H₅N₂S₃)₂Pb by precipitating it from its chloride or nitrate solution in presence of a mineral acid, acetic acid, tartrate or cyanide. The estimation is quantitative up to a maximumph of about 6.5. The lead-Bismuthiol II complex is stable up to about 311° C and the conversion factor is 0.315. The method affords a complete separation of lead from alkalis and alkaline earths, Be²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Co²⁺, Ni²⁺, Fe²⁺, Fe³⁺, Cr³⁺, Al³⁺, rare earths, Ti⁴⁺, Zr⁴⁺, Th⁴⁺, UO₂ ²⁺, Pd²⁺, As³⁺, Sb³⁺, Cl^–, SO₄ ^2–, PO₄ ^3–, AsO₄ ^3–, MoO₄ ^2– and WO₄ ^2–. Among the sulphide group members Ag⁺, Au³⁺, Hg⁺, Hg²⁺, Tl⁺, Tl³⁺, Cd²⁺ and platinum metals, except Pd²⁺, interfere while oxidising agents decompose the excess reagent. Bi³⁺, Cu²⁺ and Sn²⁺, do not interfere up to a maximum limit of 30 mg, 50 mg, and 250 mg respectively.Part I: see Z. analyt. Chem. 154, 262 (1957).