Extraction of pertechnetate with tetraphenylphosphonium in the presence of various acids, salts and hydroxides

Solvent extraction of pertechnetate anions from aqueous solutions of some mineral acids (HCl, HNO₃, HClO₄, H₂SO₄), (NaCl, NaNO₃, NaClO₄, K₂CrO₄, NaCO₃), NaOH and NH₄OH by tetraphenylphosphonium chloride in chloroform and nitrobenzene was studied. The results are presented in the form of the dependencies of extraction characteristics of TcO ₄ ⁻ (distribution ratio, percentage of extraction) on the (C₆H₅)₄PCl, H⁺ and competitive anion concentrations. The solvent extraction of sub-and super-stoichiometric ratio of TcO ₄ ⁻ : (C₆H₅)₄P⁺ was performed. The extraction constant values of ion pairs TcO ₄ ⁻ −Cl⁻, TcO ₄ ⁻ −NO ₃ ⁻ , TcO ₄ ⁻ −ClO ₄ ⁻ and of individual anions TcO ₄ ⁻ , Cl⁻, NO ₃ ⁻ , ClO ₄ ⁻ were calculated.     

Synergistic solvent extraction of lanthanides with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one and aliphatic amines: Influence of the ammonium salt ions

Summary The synergistic solvent extraction of Pr, Gd, and Yb with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HP) and tridodecylammonium (TDAHA), trioctylammonium (TOAHA), and dioctylammonium (DOAHA) salts (A ^–=Cl^–, NO ₃ ^– , and ClO ₄ ^– ) in C₆H₆ has been studied. The composition of the extracted species has been determined asAmH⁺[LnP ₄]^– (AmH⁺: ammonium salt cation). The values of the equilibrium constant have been calculated. The influence of the ammonium salt ions on the extraction process is discussed.

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Synergetische Extraktion von Lanthaniden mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on und aliphatischen Aminen: Einfluß der Ammoniumsalzionen

Zusammenfassung Die synergetische Extraktion von Pr, Gd und Yb mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on (HP) und Tridodecylammonium-(TDAHA), Trioctylammonium-(TOAHA) und Dioctylammoniumsalzen (DOAHA) (A ^–=Cl^–, NO ₃ ^– und ClO ₄ ^– ) in C₆H₆ wurde untersucht. Die Zusammensetzung der Extraktionskomplexverbindungen wurde zuAmH⁺[LnP ₄]^– bestimmt; die Gleichgewichtskonstanten wurden berechnet. Der Einfluß der Ionen des Ammoniumsalzes auf die Extraktion wird diskutiert.

     

Koordinationsverbindungen des zweiwertigen Nickels und dreiwertigen Kobalts mit Äthylendiimino-bis-acetylaceton

The preparation of compounds with formula Ni(enac ₂) and [Co(enac ₂)L ₂]X is reported [H₂(enac ₂)=ethylenediimino-bis-acetylacetone, C₁₂H₂₀N₂O₂,L=NH₃,py, -pic, diethylamine;X=Cl^–, ClO _– ⁴ , B(C₆H₅) _– ³ ]. The complexes have been studied by means of magnetic susceptibility measurements, infrared, electronic and NMR spectra and conductivity measurements.     

Kinetic investigation of sulfur(IV) oxidation by peroxo compounds R-OOH in aqueous solution

Summary Normal and rapid-scan stopped-flow spectrophotometry in the range of 260–300 nm was used to study the kinetics of sulfur(IV) oxidation by peroxo compounds R-OOH (such as hydrogen peroxide, R=H; peroxonitrous acid, R=NO; peroxoacetic acid, R=Ac; peroxomonosulfuric acid, R=SO ₃ ^– ) in the pH range 2–6 in buffered aqueous solution at an ionic strength of 0.5 M (NaClO₄) or 1.0 M (R=NO; Na₂SO₄). The kinetics follow a three-term rate law, rate=(k_H[H]+k_HX[HX]+k_p)[HSO ₃ ^– ][ROOH] ([H] = proton activity; HX = buffer acid = chloroacetic acid, formic acid, acetic acid, H₂PO ₄ ^– ). Ionic strength effects (I=0.05–0.5 M) and anion effects (Cl^–, ClO ₄ ^– , SO ₄ ^2– ) were not observed. In addition to proton-catalysis (k_H[H]) and general acid catalysis (k_HX[HX]), the rate constant k_p characterizes, most probably, a water induced reaction channel with k_p=k_HOH[H₂O]. It is found that k_Hf(R) with k_H(mean)=2.1·10⁷ M^–2 s^–1 at 298 K. The rate constant k_HX ranges from 0.85·10⁶ M^–2 s^–1 (HX=ClCH₂–COOH; R=NO; 293 K) to 0.47·10⁴ M^–2 s^–1 (HX=H₂PO ₄ ^– ; R=H; 298 K) and the rate constant k_p covers the range 0.2·M^–1 s^–1 (R=H) to 4.0·10⁴ M^–1 s^–1 (R=NO). LFE relationships can be established for both k_HX, correlating with the pK_a of HX, and k_p, correlating with the pK_a of the peroxo compounds R-OOH. These relationships imply interesting aspects concerning the mechanism of sulfur(IV) oxidation and the possible role of peroxonitrous acid in atmospheric chemistry. A UV-spectrum of the unstable peroxo acid ON-OOH is presented.     

Peculiarities of dissociative ionization of alkylcyclopentadienyl nitrosyl π-complexes of nickel

The decomposition of alkylcyclopentadienyl nitrosyl -complexes of nickel, (C₅H₄R)(NO)Ni (R=H, Et,i-Pr, CH₂Ph), under the action of electron impact has been studied. The nature of the nitrosyl ligand has been shown to be the factor determining the main fragmentation pathway which involves the abstraction of an NO molecule. The effect of the nature of the ligand on the ability of the molecular ion (C₅H₄R)LNi⁺ (L=C₅H₄R, C₅H₅, C₃H₅, NO) to rearrange with hydrogen atom migration from one ligand to another has been considered. The structure of the alkyl group R determines a competing fragmentation pathway involving cleavage of the -C-C bond with respect to the cyclopentadienyl ring in the substituent.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1985–1988, November, 1993.     

Transition metal compounds of the purinic isomer allopurinol. Part 1

Summary The synthesis, spectral and magnetic properties of a series of new compounds of Co^II, Ni^II and Cu^II with the purinic isomer allopurinol (L) are reported. The counterions employed were Cl^–, Br^–, NO ₃ ^– , SO ₄ ^2– , ClO ₄ ^– and MeCO ₂ ^– . The metal:ligand stoichiometries found for the compounds range from 11 to 13. Allopurinol exhibits two classes of coordination behaviour: neutral monodentate (M^II=Co, Ni and Cu; X^–=Cl or Br) and monoanionic bidentate for the compound [CuL(OH)]_n. The latter was obtained when the counterion used in the syntheses was NO ₃ ^– , SO ₄ ^2– , ClO ₄ ^– or MeCO ₂ ^– . The coordination behaviour of theN-pyrazolic ring atoms may relate to the interaction mode of this heterocyclic fragment with the xanthine oxidase metalloenzyme.     

Electron spin resonance and electronic spectral investigation on square planar copper(II) complexes ofN-ethyl- andN-propylimidazole

Summary Electron spin resonance studies have been carried out onN-ethylimidazole andN-propylimidazole 4 : 1 complexes of CuX₂ salts (X = ClO ₄ ^– , NO ₃ ^– , , Br^– or Cl^–) in their polycrystalline and undiluted form at 295 K and 77 K. Cupric ion hyperfine structural resolution is observed for all the complexes at 295 K and the spectra are characteristic of a CuN₄ chromophore with axial symmetry. In complexes involving ClO , Br^– and Cl^– the anions are nonbonding, whereas those with the NO ₃ ^– anion are weakly bonding. The electronic and e.s.r. spectral data have been correlated. The resolution of Cu²⁺ ion hyperfine structure in these complexes is attributed to a decrease in the dipolar interaction and has been observed for the first time since the first resolution reported in 1954 for CuN₄ coordination with square planar symmetry for ,,,-tetraphenylporphyrincopper (CuTPP).     

Antimony(III) Complexes with Quaternary Ammonium Bases: Synthesis, Spectral, and Luminescent Properties

Complexes of antimony(III) halides with quaternary ammonium bases of different composition were synthesized and characterized by elemental and X-ray diffraction analyses and IR and luminescence spectroscopy. For complexes [R"₃R"N]SbHal₄ (Hal = Cl^–, Br^–, R" = R" = CH₃, C₂H₅, C₄H₉), the maximum of the emission band and fluorescence intensity was found to depend on the nature of the halide ion and the alkyl radical length.     

Synthesis and properties of 2,2′-dipyridyl and 4,4′-dipyridyl complexes with thulium salts

Summary New complexes of 2,2-dipyridyl and 4,4-dipyridyl with thulium salts TmX ₃ (whereX=Cl^–, Br^–, NO ₃ ^– , NCS^–, and ClO ₄ ^– ) have been prepared and their solubilities in water at 21 °C were determined. The IR spectra of these compounds are discussed. The conditions of thermal decomposition of the complexes were also studied.

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Synthese und Eigenschaften von 2,2-Dipyridyl- und 4,4-Dipyridylkomplexen mit Thuliumsalzen

Zusammenfassung Es wurden neue 2,2-Dipyridyl- und 4,4-Dipyridyl-Komplexen mit Thuliumsalzen TmX ₃ (X=Cl^–, Br^– No ₃ ^– , NCS^–, ClO ₄ ^– ) dargestellt und ihre Wasserlöslihkeit bei 21 °C bestimmt. Die IR-Spektren werden diskutiert. Das thermische Verhalten der erhaltenen Komplexe wurde untersucht.

     

Crystal structure determination and properties of hydrogen hexacyanododeca-μ-chloro-octahedro-hexatantalate(4−)-Dodecahydrate

Summary The cluster compound H₄[Ta₆Cl₁₂(CN)₆] · 12H₂O was prepared and identified by potentiometric titrations, i.r. and visible spectra and by three-dimensional single-crystal x-ray diffraction methods. Discrete [Ta₆Cl₁₂(CN)₆]^4– ions contain a linear Ta–CN unit with Ta–C=2.21(4) and C–N=1.16(5) Å, respectively. Each nitrogen atom is hydrogen bonded [2.63(12)Å] to two oxygen atoms.     

Potentiometric behaviour of a perchlorate-selective polyvinyl chloride matrix membrane electrode using tris-bathophenanthroline ferrous perchlorate

Summary A perchlorate ion-selective electrode using tris-bathophenanthroline ferrous salt in a polyvinylchloride matrix was investigated. The electrode was tested in terms of the measuring range, average slope, resistance, asymmetric potential, reproducibility, stability and of the selectivity for ClO ₄ ^– ion over BF ₄ ^– , I^–, NO ₃ ^– , NO ₂ ^– , Br^–, BrO ₃ ^– , Cl^–, and SO ₄ ^2– ions. Molar solubilities of potassium perchlorate, tris-2,2-bipyridine ferrous perchlorate, tris-1,10-phenanthroline ferrous perchlorate and tris-5,6-dimethyl-1,10-phenanthroline ferrous perchlorate were calculated from the direct potentiometric perchlorate determinations.

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Potentiometrisches Verhalten einer perchloratselektiven Membranelektrode unter Verwendung von Tris-bathophenanthrolineisen(II)-perchlorat in PVC-Matrix

Zusammenfassung Die Elektrode wurde in bezug auf folgende Größen getestet: Meßbereich, durchschnittliche Steilheit, Widerstand, asymmetrisches Potential, Reproduzierbarkeit, Stabilität, Selektivität für Perchlorat gegenüber BF ₄ ^– , J^–, NO ₃ ^– , NO ₂ ^– , Br^–, BrO ₃ ^– , Cl^–, SO ₄ ^2– . Die molaren Löslichkeiten von Kaliumperchlorat, Tris-1,10-phenanthrolin-eisen(II)-perchlorat, Tris-5,6-dimethyl-1,10-phenanthrolin-eisen(II)-perchlorat und Tris-2,2-bipyridyl-eisen(II)-perchlorat wurden aus direkten potentiometrischen Perchloratbestimmungen berechnet.

     

The outersphere complex of EuCl2+ in a mixed system of methanol and water of 1.0M (H, Na) (Cl, ClO4)

The stability constans, ₁, of each monochloride complex of Eu(III) have been determined in the methanol and water mixed system with 1.0 mol·dm^–3 ionic strength using a solvent extraction technique. The values of ₁ increase with an increase in the mole fraction of methanol (X _S ) in the mixed solvent system when 0X _S 0.40. The, distance of Eu³⁺–Cl^– in the mixed solvent system was calculated using the Born-type equation and the Gibbs' free energy derived from ₁. Calculation of the Eu³⁺–Cl^– distance and the preferential solvation, of Eu³⁺ by water proposed the variation of the outersphere complex of EuCl²⁺ as follows: (1) [Eu(H₂O)₉]³⁺Cl^–, [Eu(H₂O)₈]³⁺Cl^– and [Eu(H₂O)₇(CH₃OH)³⁺Cl^– inX _S0.014, (2) [Eu(H₂O)₈]^3–Cl^– and [Eu(H₂O)₇(CH₃OH)]³⁺Cl^– in 0.014<X _S <0.25 and (3) [Eu(H₂O)₇(CH₃OH)]^3–Cl^– and [Eu(H₂O)₆(CH₃OH)[₂ ³⁺Cl^– in 0.25<X _S 0.40.     

Abtrennung und gas-chromatographische Bestimmung von Fluoridspuren

Zusammenfassung Spuren an Fluorid können aus wäßrigen Lösungen mit (C₂H₅)₃SiCl in m-Xylol oder mit (C₆H₅)₄SbOH in CH₂Cl₂ ausgeschüttelt werden. Von verschiedenen untersuchten Mitfällungsreaktionen erwies sich die Adsorption an Hydroxylapatit als am günstigsten.Durch Gas-Chromatographie mit Flammenionisationsdetektor können noch 0,05 g F^–/ml m-Xylol als (C₂H₅)₃SiF bestimmt werden. Wegen der normalerweise auftretenden schwankenden Blindwerte von etwa 0,5–1,5 g F^– lassen sich jedoch Mengen von weniger als ca. 3 g F^– in der Regel nicht mehr bestimmen.

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Separation and gas-chromatographic determination of traces of fluoride

Traces of fluoride can be separated from aqueous solution by extraction with (C₂H₅)₃SiCl in m-xylene or with (C₆H₆)₄SbOH in CH₂Cl₂. Furthermore, several coprecipitation reactions were tested; adsorption on hydroxyl apatite is most suitable.Determination of 0.05 g F^–/ml can be performed by gas chromatography of (C₂H₅)₃SiF in m-xylene using flame ionisation detectors; but variable blanks of 0.5–1.5 g F^– normally prevent the determination of less than ca. 3 g F^–.

     

Molecular state of hydrochloric acid in its tributyl phosphate extracts

Using IR spectroscopy we have shown that at digerent equilibrium concentrations of HCl in aqueous phases, its tributyl phosphate @acts contain: 1) at C_Hcl ^a < 2.3 M, micelle-like associates H₅O₂ ⁺(H₂O)_n–2(TBP)_mCl^–·(H₂0·TBP)₂ (n 26 and m 13), the structure of micelles is discussed 2) at 2.3 M < C_HCl ^a < 5.6 M, dimer associates [H₅O₂ ⁺(H₂O)₂Cl^–(H₂O·TBP)₂]₂; 3) at 5.6 M < C_HCl ^a < 8.5 M, H-bonded molecular fragments H₅O₂ ⁺(TBP)_2/3Cl^–(A); and 4) at C_HCl ^a > 8.5 M, considerable amounts of the H₃O⁺ tisolvate start to form in molecular fragments H₃O⁺(TBP)_1/3Cl ^–(B) H-bonded with the nearest neighbors. At C_Hcl ^a > 5.6 M, almost no free TBP molecules occur in the extracts and a structured liquid forms from the A fragments; and at C_Hcl ^a > 8.5 M, from the B fragments.Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturmoi Khimii, Vol. 34, No. 5, pp. 72–79, September–October, 1993.Translated by K. Shaposhnikova     

Structural Dynamics of Isomorphic Substitution in N,N′-Diallylbenzimidazolium Copper Halide π-Complexes [C7H5N2(C3H5)2]+[Cu2Cl3?xBrx]? (x=0, 1.60, 2.33, 3)

Two new -complexes of copper(I) halides with the 1,3-diallylbenzimidazolium cation, [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl_1.40Br_1.60]^– and [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Br₃]^–, have been synthesized and structurally defined (space group P2 ₁/c for both; a = 22.094(6), b = 9.272(8), c = 9.22(1) , = 118.26(4)° and a = 22.267(5), b = 9.311(3), c = 9.263(2) , = 117.51(2)°). The mutual effects of chlorine–bromine substitution and the efficiency of -interactions are discussed based on XRD data for these two compounds and for the compounds [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl₃]^– and [C₇H₅N₂(C₃H₅)₂]⁺[Cu₂Cl_0.67Br_2.33]^– studied previously.     

Preparation,spectroscopic and structural analysis of uranium-arabinose complexes

The reaction betweenL-arabinose and hydrated uranyl salts has been investigated in aqueous solution and the solid complexes of the type UO₂(L-arabinose)X ₂ · 2 H₂O, whereX=Cl^–, Br^–, and NO ₃ ^– , have been isolated and characterized. Due to the marked similarities with those of the structurally known Ca(L-arabinose)X ₂ · 4 H₂O and Mg(L-arabinose)X ₂ · 4 H₂O (X=Cl^– or Br^–) compounds, the UO ₂ ²⁺ ion binds obviously to twoL-arabinose moieties, through O1, O5 of the first and O3, O4 of the second molecule resulting into a six-coordinated geometry around the uranium ion with no direct U-X (X=Cl^–, Br^– or NO ₃ ^– ) interaction. The intermolecular hydrogen bonding network of the freeL-arabinose is rearranged upon uranium interaction. The -anomer configuration is predominant in the freeL-arabinose, whereas the -anomer conformation is preferred in the uranium complexes.

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Darstellung, spektroskopische und Strukturanalyse von Uran-Arabinose Komplexen

Zusammenfassung Es wurde die Reaktion zwischenL-Arabinose und hydratisierten Uranylsalzen in wäßriger Lösung untersucht und kristalline Komplexe des Typs UO₂(L-Arabinose)X ₂ · 2 H₂O mitX=Cl^–, Br^– und NO ₃ ^– isoliert und charakterisiert. Wie aus markanten Ähnlichkeiten der Komplexe mit den bekannten Verbindungen Ca(L-Arabinose)X ₂ · 4 H₂O und Mg(L-Arabinose)X ₂ · 4 H₂O (X=Cl^– oder Br^–) abzuleiten ist, bindet das UO ₂ ²⁺ -Ion mit zweiL-Arabinose Einheiten, wobei sich durch die O1,O5-Koordination des ersten und die O3,O4-Koordination des zweiten Moleküls eine sechs-koordinierte Geometrie um das Uranylion [ohne direkte U-X (X=Cl^–, Br^– oder NO ₃ ^– ) Wechselwirkung] ausbildet. Die intermolekularen Wasserstoffbrücken zeigen nach der Wechselwirkung mit dem Uranylion eine Umgruppierung. In der freienL-Arabinose ist das -Anomere vorherrschend, in den Urankomplexen hingegen das -Anomere.

     

Coordination chemistry of poly(1-pyrazolyl)alkanes Part V: Preparation and characterization of cobalt(II) complexes with bis(1-pyrazolyl)methane and bis(3-methylpyrazolyl)propane

Summary Bis(1-pyrazolyl)methane, H₂Cbpz, and bis(3-methylpyrazolyl)propane, Me₂Cbmpz, react with cobalt(II) salts to give the solid complexes: [Co(H₂Cbpz)₂X₂] ·2H₂O (X=Cl^–, Br^–, I^–, NO ₃ ^– or ClO ₄ ^– ) and [Co(Me₂-Cbmpz)X₂] (X=Cl^–, Br^–, or I^–), which were isolated and characterised by elemental analysis, i.r. and electronic spectra and conductance measurements. From spectral data, octahedral and tetrahedral structures have been proposed for the H₂Cbpz and Me₂Cbmpz complexes respectively. The molar conductance of the complexes indicates that they are non-ionic.     

Extraction of gallium with tetraphenylarsonium chloride

Summary Gallium is completely extracted with tetraphenylarsonium chloride from hydrochloric acid medium. The extraction behavior was studied by determining gallium with complexometric titration using gallocyanine indicator, spectrophotometrically with rhodamine B, and also with gallium-72 tracer. Complete extraction is observed from 2.5M hydrochloric acid; the extractable species is GaCl₄ ^–, (C₆H₅)₄As⁺. In the presence of lithium chloride (total chloride ion concentration 2.5M) complete extraction occurs at hydrochloric acid concentrations 0.25M. The following ions do not interfere: aluminum, thallium, zinc, cadmium, mercury, cobalt, nickel, permanganate, molybdate, tungstate, tin, phosphate and fluoride.

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Zusammenfassung Gallium läßt sich aus salzsaurem Medium vollständig mit Tetraphenyl-arsoniumchlorid extrahieren. Das Extraktionsverhalten wurde durch Bestimmung des Galliums komplexometrisch mit Gallocyanin als Indikator, spektrophotometrisch mit Rhodamin B und radiometrisch mit⁷²Ga untersucht. Vollständige Extraktion erhält man, wenn die Salzsäure mindestens 2,5-m ist, wobei (C₆H₅)₄As[GaCl₄] extrahiert wird. In Gegenwart von Lithiumchlorid genügt eine geringere Salzsäurekonzentration, wenn [Cl^–]2,5. Folgende Ionen stören nicht: Al³⁺, Th⁺, Zn²⁺, Cd²⁺, Hg²⁺, Co²⁺, Ni²⁺, MnO₄ ^–, MoO₄ ^2–, WO₄ ^2–, Sn²⁺, PO₄ ^3– und F^–.

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This work was partially supported by the U. S. Atomic Energy Commission, Contract No. At (30-1)-3417.