Defect Energetics and Nonstoichiometry in Lanthanum Magnesium Hexaaluminate

Computer-based atomistic simulation methods are applied to address quantitatively the defect energetics and crystal chemistry of lanthanum magnesium hexaaluminate (LMA). The tetrahedral site preference of Mg in the magnetoplumbite structure is determined by calculating lattice energies for different Mg ion distributions. It is revealed that the intrinsic and extrinsic disorders are much influenced by the distribution of Mg in the structure. Our calculations show that oxygen Frenkel disorder is the dominant defect mode to be expected, even though Schottky disorder may also exist. Several feasible defect processes in nonstoichiometric LMA are determined from the enthalpies of the quasi-chemical reactions for the processes with simple point defect energies. We have also modeled some defect complexes in the mirror plane regions. It is found that the Mg ions positioned in the tetrahedral sites suppress the formation of cation vacancies in the mirror plane, through hindering the relaxation of the 12kAl ions by which the vacancies are stabilized. In Mg-deficient nonstoichiometric LMA, however, it is expected that the defect complex [V_La+V_Al+2(V_Al+Al_i)] will be formed in the interspinel layer. Our calculations also indicate that the O_Ladefect is improbable in LMA not only as a simple point defect but also as a member of a defect complex.     

Melting and vaporization of salts in a U-LiCl-Li2O system

Summary The electrochemical reduction of uranium oxide in the treatment of spent nuclear fuel requires a characterization of the LiCl-Li₂O salt used as a reaction medium. Physical properties, melting and vaporization are important for the application of the salt and thus they have been investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG), respectively. Experimental data suggest LiCl and Li₂O compound formations, leading to a melting point depression of the LiCl and a co-vaporization of the LiCl-Li₂O salt.     

Intermolecular and intramolecular Diels-Alder cycloadditions of 3-ylidenepiperazine-2,5-diones and 5-acyloxy-2(1h)-pyrazinones

The 3-ylidenepiperazine-2,5-diones 16 and 39 and 5-acyloxy-2(1H)-pyrazinones 17 can serve as starting materials for the Diels-Alder reactions of alkenes and alkynes to the piperazine ring, under acidic conditions or in the presence of acetyl chloride, to afford tricyclic piperazine-2,5-diones 19, 20, 23-25, 27, 44, and 45. Intramolecular cycloadditions occur if 3-ylidenepiperazine-2,5-diones 30 and 32 are used as the starting materials. This procedure is a convenient path to bridged bicyclo[2.2.2]diazaoctane ring systems such as 31 and 33, the former being found in biologically active secondary mold metabolites, such as VM55599 (1) or brevianamide A (5), which have been isolated from various fungi. The synthesis of the indole compound 31 provided evidence for the proposed biochemical pathway with a Diels-Alder reaction as key step. Quantum chemical calculations have revealed that piperazinones with a cationic azadiene moiety are the most reactive species in Diels-Alder cycloadditions.