Search Results
Caracterisation par analyse calorimetrique differentielle des complexes entre LiAlH4 et les ethers-couronnes 12-C-4, 15-C-5, dicyclohexano-18-C-6
Comportement thermique des phases solides et de certains de leurs solvates avec le benzène
The thermal behaviour of complexes [Li+-EC](AlH4)− withEC=12-C-4, 15-C-5, DC 18-C-6 (cis-anti-cis andcis-syn-cis isomers) was investigated by Differential Scanning Calorimetry (DSC). These complexes were prepared as solids from benzene solutions. Pure EC and several solvated species [Li+-EC](AlH4)−·nC6H6 (EC=15-C-5, DC 18-C-6syn) were also studied. DSC has revealed various phenomena. Solid-solid transitions were observed before melting for [Li+-EC](AlH4)− withEC=12-C-4 and 15-C-5. They are probably explained by small molecular modifications strongly dependent on the thermal history of the sample. A glass-transition was found for the pure crown-ether DC 18-C-6anti, the complex [Li+-EC](A1H4)− withEC=DC-18-C-6anti and the two solvates mentioned above.
Abstract
The extraction of the trivalent lanthanides Eu, Tm and Yb(Ln) by crown ethers (CE) 12-crown-4 (12C4) and 15-crown-5 (15C5) in chloroform from perchlorate aqueous media of constant ionic strength is investigated. The effect of [H+], [CE] and [ClO
4
–
] on the respective distribution ratio (D) is elucidated. Slope analysis of these results indicated that the extracted species are of the type Ln(OH)
2
+
·ClO
4
–
(CE)2. The extraction constants obtained are in the sequence 15C5>12C4 for the CE's and Eu
Tm<Yb for the elements investigated. Based on the separation factors elucidated, Tm(III) and Yb(III) are separated from Eu(III) with high radiochemical purity; >99.5% by three (or four) successive extraction and strippings.
Abstract
Extraction of microamounts of calcium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of 12-crown-4 (12C4,L) has been investigated. The equilibrium data have been explained assuming that the complexes HL+, HL2 +, CaL2+ and CaL2 2+ are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined.
Abstract
Extraction of microamounts of strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of 12-crown-4 (12C4,L) has been investigated. The equilibrium data have been explained assuming that the complexes HL+, HL2 +, SrL2+ and SrL2 +2- are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined.
Abstract
The extraction of UO 2 2+ , Am3+, and Th4+ by 1-phenyl-3-methyl-4-benzylpyrazolone with crown ethers was studies using 0.1M (NaClO4) aqueous phase and toluene. The crown ethers were 12C4, 15C5, 18C6, DB18C6 and DCH18C6. The synergic equilibrium constant did not show correlation between the cationic radii and the ether cavity size nor did the values follow a simple order of ether basicity. The ether basicity, steric effects, and the number of ether oxygens bound to the cation are the combined factors which seemingly determine the pattern of M(PMBP)n—CE interaction.
Abstract
The production cross sections of L-shell X-ray of some rare earth elements have been measured by collision of 12C4+ and 16O4+ ions of 0.5 to 0.75 MeV/amu. The results were compared with experimental data of other authors and with theoretical predictions gained by the ECPSSR and ECPSSR plus multiple ionization (ECPSSR+MI) models. For atomic parameters (fluorescence yields and probabilities for Coster-Kronig transitions) the role of several databases were studied. The ECPSSR theory underestimates cross sections when compared with experimental results obtained in the present work, but ECPSSR+MI has a better agreement with the experimental data.
The effect of carbonyl carbon atom replacement in acetone molecule (ACN) by sulfur atom (DMSO)
Part III. Effect of base–acid properties of the mixtures of water with acetone or dimethylsulfoxide on the solution enthalpy of cyclic ethers in mixed solvent
Abstract
The enthalpies of solution of cyclic ethers: 1,4-dioxane, 12-crown-4 (12C4), and 18-crown-6 (18C6) in water–acetone mixtures have been measured within the whole mole fraction range at 298.15 K. Based on the obtained data, the effect of base–acid properties of water–acetone mixtures on the solution enthalpy of cyclic ethers in this mixed solvent has been analyzed. The strong dependence of the enthalpy of solution (solvation) of cyclic ethers on basic properties of mixed solvent has been observed. The effects of carbonyl atom replacement in acetone (ACN) molecule by sulfur atom (DMSO molecule) and base–acid properties of mixed solvent on the solvation process of cyclic ethers have been analyzed.
The effect of carbonyl carbon atom replacement in acetone molecule (ACN) by sulfur atom (DMSO)
The preferential solvation of cyclic ethers
Abstract
Enthalpies of solution of 1,4-dioxane, 12-crown-4 ether (12C4), 15-crown-5 ether (15C5) and 18-crown-6 (18C6) have been analyzed from the point of view of preferential solvation of these cyclic ethers (crown ethers) by a molecule of acetone or dimethylsufoxide in the mixtures of water with acetone or dimethylsulfoxide. It has been observed that the carbonyl carbon atom replacement in acetone molecule by sulfur atom brings about completely different behavior of molecules of these solvents in relation to cyclic ethers dissolved in mixed solvents. Crown ethers are preferentially solvated by acetone (ACN) molecules, which is not observed in the case of dimethylsulfoxide (DMSO).
Abstract
The extraction of cesium, strontium and barium by a nitrobenzene solution of dicarbollylcobaltate in the presence of various crown ethers has been investigated and the influence of the substituent of crown to the extraction possibility has been observed. It has been found, that the addition of DB15C5, DB18C6 and DB21C7 (but not DB24C8 and DCH24C8) increases the distribution ratio of Cs by one order of magnitude. The fivemembered crowns are usually more efficient extractants for strontium than DCH18C6, which is widely used for strontium separation. The distribution ratio of strontium DSr decreases in the order 15-crown-5>benzo-15-crown-5>2-hydroxymethyl-15-crown-5>cyclohexyl-15-crown-5 >dibenzo-15-crown-5> nitrobenzo-15-crown-5. The selectivity α(Sr/Ca) decreases in the order 15C5>B15C5>DB15C5>2HM15C5>CH15C5. A selectivity factor α(Sr/Ca)≥1000 can be reached in the presence of 15C5 and B15C5. Six-membered and four-membered crowns extract strontium worse than most of the five-membered crowns. The selectivity factors α(Sr/Ca)≈100 have been reached for six-membered crowns and α(Sr/Ca)<1 has been found for 12C4. The extraction of barium by a nitrobenzene solution of dicarbollylcobaltate in the presence of 15C5 is even more efficient as the extraction of strontium. In that system DSr>104 and DBa>104 have been found for the extraction of Sr and Ba by a 0.01M nitrobenzene solution of dicarbollylcobaltate (cB=0.01 mol/l) from 0.1M HNO3. Maximal values of separation factor α(Ba/Sr) have been found in the system containing DB21C7.
121.08 ∠H6–C2–H7 105.5 H12–C4–Si1–C2 −58
