Showing papers in "Journal of Inorganic and Nuclear Chemistry in 1965"

Abstract: A number of mixed metal oxides with perovskite-like structures are reported. On the sublattice of the smaller cations 1:1 and 1:2 long-range order have been found in the perovskite as well as in the hexagonal barium titanate structure. The Jahn-Teller distortions of these compounds are discussed. Finally the energy terms stabilizing the hexagonal barium titanate structure relative to the perovskite structure are considered. It seems probable that anion polarization and not cation-cation bonding stabilizes the hexagonal barium titanate structure.

Abstract: A description is given of the preparation and properties of a granular form of potassium hexacyanocobalt (II) ferrate (II) that is a highly selective absorbent for cesium ion. The material is suitable for use in a large-scale ion exchange column, and offers the possibility of isolating and concentrating 137 Cs from fission product waste solutions that arise from the processing of nuclear fuels.

Abstract: The dimethylglyoxime complexes of iron (II), iron (III), cobalt (II), cobalt (III), copper (II), nickel (II), palladium (II) and platinum (II) were prepared and their composition was established by elementary analysis (Table 1) The presence of the Me → N = C donor π-bond was proved in the dimethylglyoxime complexes of bivalent metals by infrared spectrophotometry (by the shift of the CN-frequency) It was found that the effect of the donor π bond increases in the order CuII < NiII < CoII < FeII, and NiII < PdII < PtII From the character of the OH bands of the infra-red spectra, conclusions can be drawn about the nature and strength of the hydrogen bridges in the complexes Investigations by ultra-violet spectrophotometry disclosed that in an alkaline solution the absorption band of undissociated dimethylglyoxime (HDMG) splits into two bands The character of the ultraviolet spectrum of the dimethylglyoxime complexes in aqueous solution is quite identical with that of the spectrum of the dimethylglyoximate anion (DMG−)

Abstract: The plutonium-oxygen phase diagram between PuO1·5 and PuO2 and between room temperature and 900° has been studied using a high-temperature X-ray powder-diffraction camera. At temperatures below 300°, α-Pu2O3 and PuO1·98 are in equilibrium; the O/Pu ratio of α-Pu2O3 is 1·515. Above 300°, α-Pu2O3 takes up oxygen and forms a new cubic phase with an O/Pu ratio of 1·61, which is in equilibrium with PuO1·98−x. The measurement of lattice parameters as a function of temperature shows that the eutectoid at PuO1·71, postulated by previous workers, does not exist. For O/Pu ratios 350°, hexagonal Pu2O3 and cubic PuO1·61 are in equilibrium. The upper O/Pu ratio limit of hexagonal Pu2O3 is 1·51, and hexagonal Pu2O3 remains single phase from room temperature to at least 900°. Between PuO1·51 and PuO1·515 at t < 300°, two very narrow phase regions must be present to satisfy the phase rule. The Pu-O phase diagram shows very little similarity with the rare earth oxygen phase diagrams at t < 600°.

Abstract: Well-crystalline complexes of the novel types MCl3(dipy)H2O, M(CH3COO)3(dipy), MCl3(dipy)2, MCl3(dipy)2EtOH and M(CNS)3(dipy)3 are reported and described (M = a lanthanide and dipy = 2,2′-dipyridyl). Further data are presented concerning the complexes M(NO3)3(dipy)2, and all the complexes are compared with the corresponding 1:10-phenanthroline compounds with respect to possible structures and relative stability.

Abstract: The dissociation constants of the DTPA complexes with Am, Cm, Bk, Cf, Es and Fm have been determined by an ion exchange technique, and the values obtained are: Americium 10 −22·92 , Curium 10 −22·99 , Berkelium 10 −22·79 , Californium 10 −22·57 , Einsteinium 10 −22·62 and Fermium 10 −22·70 . A solvent extraction system has been developed to completely separated the transplutonium elements from the lanthanide fission products by extracting the lanthanide elements into an organophosphonate from a carboxylic acid-buffered solution of DTPA. The separation factor between americium and the lanthanide elements is about fifty.

Abstract: The preparation of three types of complexes (1:1, 1:3 and 2:3) by the direct reaction of Cu(I)X (XCl, Br, I) and triphenylphosphine is described. Characteristic absorption bands in the infra-red (KBr region) and ultra-violet absorption frequencies of the 1:3 and 2:3 complexes are reported.

Abstract: Infra-red spectra (900-240 cm−1) of twelve alkali metal uranates are presented. Uranyl stretching vibrations of the monouranates occur between 700 and 800 cm−1, and of the diuranates between 750 and 850 cm−1. The infra-red results are correlated with X-ray diffraction data, and uranyl bond lengths of the compounds have been calculated.

Abstract: The Mossbauer absorption spectra of α-, β-, γ-, and δ-FeOOH have been examined at room temperature and at 77°K. The isomer shift for the four forms has been shown to be in the range characteristics of the Fe3+ ion. The spectra of β- and γ-FeOOH at room temperature show two closely-spaced peaks which indicate a small quadrupole interaction of 2 to 3 Mc/sec. α-, β-, and δ-FeOOH give “six-finger” spectra at 77°K confirming the existence of magnetic interaction in these oxides. Comparison of the temperature variation of the β-FeOOH spectrum with existing susceptibility data suggests that two types of negative exchange interaction occur in this oxide and possibly also in α-FeOOH.

Abstract: An investigation was made on the formation of complexes between the simplest arylhydroxamic acid and the Zr4+, Fe3+ and UO22+ ions. The values were determined of the stability constants of the complexes of zirconium and iron (III) ions with benzohydroxamic acid (using the distribution method), and of the complex between uranyl ion and the same acid (using the pH-potentiometric method). The values of the stability constants thus obtained are the following: β1(Zr) = 2·7 × 1012; β2(Zr) = 1·2 × 1024; β1(Fe) = 1·5 × 1012 β1(UO2) = 5·2 × 108; β2(UO2) = 5·9 × 1016 The very high stability of the zirconium complexes supports the hypothesis recently formulated by other Authors concerning the responsibility of the hydroxamic functions, formed by chemical and radiolitic damage, in the retention of zirconium by solvents used in the reprocessing of irradiated nuclear fuels.

Abstract: Hydrogen ion dependencies and extractant dependencies of M(III) elements represented by Ce 3+ , Eu 3+ , Tm 3+ , Yb 3+ , Y 3+ , Am 3+ and Cm 3+ and of an M(VI) element, UO 2 2+ , into a benzene solution of di n-octyl phosphinic acid, ( n -C 8 H 17 ) 2 PO(OH), H[DOP], from an aqueous acidic chloride medium have been determined radiometrically. The observed stoichiometries are represented as: M A +3 + 2·5(HY) 2 0 ⇌ MY(HY 2 ) 2 0 + 3H A + UO 2 A +2 + 2(HY) 2 0 ⇌ UO 2 (HY 2 ) 2 0 + 2H A + where the subscripts A and O refer, respectively, to the mutually equilibrated aqueous and organic phases and (HY) 2 represents the dimeric form of H[DOP]. Values of K s , defined by the expressions: K s = K [H + ] 3 / F 2.5 , for M(III) K s = K [H + ] 2 / F 2 , for U (VI) where [H + ] is the molar hydrogen ion concentration in the aqueous phase, F is the formal concentration of extractant in the organic phase and K is the observed distribution ratio of the metal are reported for the above elements from an aqueous phase 1·0 M in (NaCl + HCl). Comparison of the K s values of Pm(III), Cm(III) and U(VI) in systems involving di n-octyl phosphinic acid, (n-octyl) 2 PO(OH), H[DOP]; 2-ethyl hexyl 2 ethyl hexyl hydrogen phosphonate, (2-ethyl hexyl 0) (2-ethyl hexyl)PO(OH), HEH[EHP]; and di 2-ethyl phosphoric acid, (20-ethyl hexyl 0) 2 PO(OH), HDEHP, have been made. A plot of log K vs. Z , in a study involving all of the lanthanides (III) except Gd, shows a slight odd-even effect, the even Z elements lying above a straight line which acceptably represents the the odd- Z elements. It is tentatively concluded that in the series: (GO) 2 PO(OH), (GO)(G)PO(OH) if G remains fixed the extraction of U(VI) increases slightly to the right while that of the M(III) elements considered decreased markedly.

Abstract: Far infra-red spectra (650-200 cm−1) have been recorded for a series of complexes in which substituted pyridines are co-ordinated to transition metal halides. The spectra are correlated with the known structures of the complexes.

Abstract: Aniline complexes of manganese (II), cobalt (II), nickel (II), zinc, and cadmium chlorides, bromides, and iodides and of copper (II) chloride and bromide have been prepared. Ultraviolet and visible reflectance spectra and far infrared spectra have been recorded for the solid complexes and the spectra are used to determine the probable co-ordination arrangement about the metal atoms in each complex.

Abstract: Spectrophotometric studies in the visible region have been made on benzene solutions of Cu(chelate)2 [chelate = the hexafluoroacetylacetonate ion (HFacac), the thenoyltrifluroacetonate ion (TTA), the trifluoroacetylacetonate ion (TFacac) and the acetylacetonate ion (acac)] with increasing amounts of 4-methyl-pyridine (4-me-py). All form 1:1 adducts of the type Cu(chelate)2·4-me-py which, with the exception of Cu(acac)2·4-me-py, are very stable. The room-temperature formation constant of this adduct has been determined as approximately 101.mole−1. Again with the exception of Cu(acac)2, they all form 1:2 adducts of the type Cu(chelate)2·(4-me-py)2. Solid complexes have been isolated and analysed. It is suggested that the 1:1 and 1:2 adducts are definite compounds and that, in the latter, the second molecule of base is not simply trapped in the lattice.

Abstract: Extraction of copper (II) with capric acid dissolved in benzene is theoretically treated. The extracted species has the dimeric structure of composition (CuR2HR)2 down to 10−5 M of copper. In the presence of acetate buffer, acetate incorporates in the extracted species and the ultimate composition approaches to (CuRAcHR)2 at acetic acid concentrations higher than about 0·5 M.

Abstract: The complexes [(2-ampy)2 Cu(OR)NO3]2 (2-ampy = 2-aminopyridine; R = Me, Et, Pr″, Amn) together with [(2-ampy)2Cu(OH)X]2 (X = NOstaggered3−, ClO4−1 have sub-normal magnetic moments at room temperature. The preparations of R = Prn and Amn are given and the reaction of copper dinitrate trihydrate and 2-aminopyridine in n-butanol considered. The far infrared spectra of the above complexes, together with those of (2-mepy)2 CuX2 (X = Cl−, NO3−) are reported and the CuO, CuN and CuCl stretching modes are tentatively assigned Cu(bipy)3(ClO4)2, Cu(bipy)2 (ClO4)2 and [(bipy)Cu(OH)X]2 (X = N3−, ClO4−) were also examined to aid the above assignments.

Abstract: Solution and reflectance spectral data at room temperature of some low symmetry complexes with the ligands tartrate, lactate, malate, mandelate, and citrate, reveal three distinct absorption bands in the 11–20 kK region, as opposed to the general observation for all previously reported vanadyl (IV) complexes of only two bands in this region. A fourth band at 24·6 ± 0·2 kK is observed, and further support for its assignment as a charge transfer band is deduced. Tentative assignments of the three optical bands are made and these are in accord with a recent energy level scheme devised to explain additional bands which appear at low temperatures.

Abstract: The total half-lives of 252Cf, 250Cf, 253Cf are 2·646 ± 0·004 years, 13·2 ± 0·5 years and 17·6 ± 0·2 days. The ratios of α-emission to spontaneous fission for 252Cf, 250Cf, 253Es and 244Cm are 31·3 ± 0·2, 1260 ± 40, (1·15 ± 0·03)107 and (7·43 ± 0·01)105. The partial spontaneous fission half-life of 246Cm = (1·66 ± 0·10)107 years. The thermal neutron fission cross sections for 249Cf and 251Cf are 1735 ± 70 barns and 3000 ± 260 barns. A separate determination and a re-evaluation of the data from the MIKE thermonuclear event confirms the 60·5 ± 0· 2 day 254Cf half-life reported by others.

Abstract: Comparative partition data are presented for the solvent extraction of mineral acids, uranium (VI), and some lanthanide elements by dis-(di-n-hexylphosphinyl)-alkanes, [( C 6 H 13 ) 2 P(O)(CH 2 ) n P(O)(C 6 H 13 ) 2 , n=1,2,3,4] , as a function of the aqueous concentration of nitric, hydrochloric, and perchloric acids. Extractions from nitric and hydrochloric acids followed quite similar patterns when comparing partition data from the same acid media among the four compounds. However, large increases were noted in the distribution ratios obtained for extractions from perchloric acid with bidentate ligands having methylene carbon bridge lengths, n ≤ 2. Loading studies, differences in extraction, and visible spectra of the uranium (VI) perchlorate adducts of HDPM ( n = 1) and HDPE ( n = 2) were interpreted as possibly indicating the formation of disolvated complexes containing two chelate rings.

Abstract: By reaction of gaseous chlorine azide with SnCl4, TiCl4 and VOCl3 at 0°C the crystalline, hygroscopic, explosive Azidechlorides SnCl3N3, TiCl3N3 and VOCl3N3 respectively can be obtained in good yields. Infra-red spectra show these compounds to be island-structures with great degree of nonpolar MN3-bondings (M = Sn, Ti symmetry C3v; M = V symmetry Cs). By interaction of solvents TiCl3N3 and VOCl2N3 split off N2 and Cl2 and the well-defined nitride-compounds TiNCl and VON are obtainable.

Abstract: The equations for evaluation of solubility products of uranyl phosphates were derived and the following values for solubility products were determined: [UO 2 2+ ][HPO 4 2− ] = 10 −12·17±0·07 , [UO 2 2+ ] 3 [PO 4 3− ] 2 = 10 −49·7±0·3 , [Na + ][UO 2 2+ ][PO 4 3− ] = 10 −24·21±0·07 , [K + ][UO 2 2+ ][PO 4 3− ] = 10 −25·50±0·1 , [Rb + ][UO 2 2+ ][PO 4 3− ] = 10 −25·72±0·15 , [Cs + ][UO 2 2+ ][PO 4 3− ] = 10 −25·41±0·2 , and [NH 4 + ][UO 2 2+ ][PO 4 3− ] = 10 −26·23±0·2 .

Abstract: Well-crystalline, thermally stable complexes of the types M(CH 3 COO) 3 (phen) and M(NO 3 ) 3 (phen) 2 , where M = all the lanthanides except Pm and phen = 1:10-phenanthroline, have been isolated. Magnetic moments and infra-red spectra are reported and structures are discussed.

Abstract: Crystalline long-chain aliphatic primary, secondary and tertiary amine hydrochlorides ranging from C6 to C12 in the alkyl chain were prepared and their solubilities in various non-polar, water immiscible organic solvents determined at 25°. The solubility parameters of amine hydrochlorides evaluated were used to calculate their activity coefficients in a number of solvents on the assumption that the systems satisfy the requirements of the concept of regular solutions. The deviations of systems from ideal behaviour are discussed in terms of molecular association of the solutes. The information is related to solvent extraction studies involving these solutes.

Abstract: Compounds of formulas Ln(ClO 4 ) 3 ·8DMA (Ln = La, Ce, Pr, Nd; DNA = N,N -dimethylacetamide), Ln(ClO 4 ) 3 ·7DMA (Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er), and Ln(ClO 4 ) 3 ·6DMA (Ln = Tm, Yb, Lu) have been prepared by the reaction of hydrated lanthanide perchlorates with N,N -dimethylacetamide. The visible spectra of some of the compounds, the infra-red spectra, and the X-ray powder patterns have been determined. The compositions of these compounds appear to reflect the increasing spatial constraint produced by decreasing cationic crystal radius as the atomic number of the lanthanide becomes larger.

Abstract: Solid ternary complexes of the type M(TTA)2·TOPO (M = Zn2+ and Cu2+, TTA = thenoyltrifluoroacetone anion and TOPO = tri-n-octyl phosphine oxide) have been prepared and investigated. The phosphorus nuclear magnetic resonance method has been used to determine the equilibrium constant of the reaction Zn(TTA)2 (org.) + TOPO (org.) = Zn(TTA)2·TOPO(org.). This was found to be approximately 10 1/mole in anhydrous carbon tetrachloride medium. It was also shown that in the same medium, the less basic TBEP (tri-n-butoxyethyl phosphate) did not coordinate with Zn(TTA)2 to any measurable extent. In fact, the corresponding ternary complexes M(TTA)2·TBEP could not be isolated. Proton magnetic resonance studies also afford evidence for the reaction: Zn(TTA)2·2H2O + TOPO = Zn(TTA)2·TOPO + 2H2O in carbon tetrachloride medium. It is suggested that the phenomenon of synergism may be due to the enhanced solubility (in the organic phase) of neutral metal chelates caused by adduct formation with ligands such as TOPO.

Abstract: The thermal decomposition of K3[Co(C2O4)3]·3H2O in the solid-state, was studied by thermogravimetry, high temperature reflectance spectroscopy, differential thermal analysis, mass spectrometry, gas evolution analysis, and by magnetic techniques. The stoichiometry of the decomposition reaction was determined and a mechanism is proposed to explain the reaction. The ultraviolet photolysis of the compound, in the solid-state, was also determined. The photolysis and thermal decomposition reactions did not involve exactly the same products.