Kinetics and mechanism of base-catalyzed hydrolysis of Cu(II)-salicylamide complex

The kinetics of hydrolysis of Cu(II)-salicylamide complex have been studied in sodium hydroxide solution (0.5 to 2.5M). The observed pseudo-first-order rate constants vary according to the empirical equation 1/??_obs = B₁ + B₂/[ōH] up to 2.0 M sodium hydroxide concentration. The mechanism of base-catalyzed hydrolysis has been proposed and it is concluded that the reaction proceeds by the interaction of complex with the nucleophile, forming tetrahedral intermediate which then breaks down to products. The rate equation has been derived. Thermodynamic parameters have also been reported.     

ROMP‐NMP‐ATRP combination for the preparation of 3‐miktoarm star terpolymer via click chemistry

A combination of ring opening metathesis polymerization (ROMP) and click chemistry approach is first time utilized in the preparation of 3‐miktoarm star terpolymer. The bromide end‐functionality of monotelechelic poly(N‐butyl oxanorbornene imide) (PNBONI‐Br) is first transformed to azide and then reacted with polystyrene‐b‐poly(methyl methacrylate) copolymer with alkyne at the junction point (PS‐b‐PMMA‐alkyne) via click chemistry strategy, producing PS‐PMMA‐PNBONI 3‐miktoarm star terpolymer. PNBONI‐Br was prepared by ROMP of N‐butyl oxanorbornene imide (NBONI) 1 in the presence of (Z)‐but‐2‐ene‐1,4‐diyl bis(2‐bromopropanoate) 2 as terminating agent. PS‐b‐PMMA‐alkyne copolymer was prepared successively via nitroxide‐mediated radical polymerization (NMP) of St and atom transfer radical polymerization (ATRP) of MMA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 497–504, 2009     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Comparison of amine-induced cyclization of 6-chloro-1-hexynylphosphonate and isobutyl 7-chlorohept-2-ynoate

The reaction of 6-chloro-1-hexynylphosphonate with primary and secondary amines afforded exclusively 2-aminocyclohexenylphosphonates in 62-85% isolated yields. In contrast, reaction of various amines with isobutyl 7-chlorohept-2-ynoate in acetonitrile at 70 °C gave (E)-sec-butyl 2-(1-alkylpiperidin-2-ylidene)acetates in 65-78% isolated yields. Calculations offer an explanation for the difference in the behavior of the two compounds classes. It is shown that C-C cyclization in the alkyne-phosphonate group occurs via an initial formation of a zwitterionic intermediate, which is stabilized by both an inductive effect of the phosphonate group and a newly formed hydrogen bond. The alkyne-carboxylate group, on the other hand, proceeds via enamine formation as a result of the smaller inductive effect of the carboxylate combined with involvement of an allene-like resonance form. This resonance form both delocalizes the negative charge in the zwitterionic intermediate making it to be less available for attack, and affects the geometry thus preventing formation of the stabilizing hydrogen bond. Hence, the zwitterionic intermediate of the alkyne-carboxylates is less stable leading to formation of an enamine, which is followed by N-C cyclization to give the azaheterocycles.     

A flow pattern map for gas—liquid flow in horizontal pipes

Various flow pattern maps for two-phase gas—liquid flow in horizontal pipes are tested against the 5935 flow pattern observations presently contained in the UC Multiphase Pipe Flow Data Bank.A new flow regime correlation representing an extension of the work done by Govier and Aziz [3] is presented and is shown to be in better agreement with the data than the other correlations tested. A computer program for this correlation is included.It is also shown that there is no significant improvement obtained by including the effects of the physical properties of the fluids using any of the physical property parameters which have been proposed so far.     

Insights into metal borohydride and aluminohydride bonding: X-ray and neutron diffraction structures and a DFT and charge density study of [Na(15-crown-5)][EH(4)] (E = B, Al)

The neutron and X-ray structures of [Na(15-crown-5)][BH(4)] and [Na(15-crown-5)][AlH(4)], respectively, are reported, along with a topological analysis of their DFT-computed charge densities that explores the bonding between the anionic complex hydride [EH(4)](-) (E = B, Al) and the counterion [Na(15-crown-5)](+). In each case, the interaction is weak and mainly electrostatic in nature; however, notable differences are observed in the manner in which [BH(4)](-) and [AlH(4)](-) bind to the metal, which explains their different coordination modes. A range of unconventional E-H···H-C contacts is revealed to play an important role in the overall bonding and crystal packing of both complexes. These interactions can be classified as weak dihydrogen bonds based on the atoms in molecules approach.     

Electron affinities of biscyclopentadienyl and phospholyl uranium(IV) borohydride complexes: Experimental and DFT studies

Electron affinities (EAs) of a series of biscyclopentadienyl and phospholyl uranium(IV) complexes L₂U(BH₄)₂ [L₂ = Cp₂, (tmp)₂, (tBuCp)₂, (Cp*)(tmp) and Cp*₂] related to the U(III)/U(IV) redox system were calculated using relativistic Density Functional Theory (DFT) based methods coupled with the Conductor-like Screening Model for Real Solvents (COSMO-RS) approach. Electrochemical measurements of half-wave potentials in solution (tetrahydrofuran THF) were carried out for all these compounds under the same rigorous conditions. A good correlation (r² = 0.99) is obtained between the calculated EA values, at the ZORA/BP86/TZ2P level, and the half-wave reduction potentials measured by electrochemistry. The investigations bring to light the importance of spin-orbit coupling and solvent effect and the use of a large basis set in order to achieve such a good agreement between theory and experiment. The study confirms the instability of the Cp₂U(BH₄)₂ complex during the reduction process. The influence of the substituted aromatic ligand L₂, namely their electron donating ability, on EA was studied. The role of involved orbitals (singled occupied molecular orbital –SOMO– of anionic species or lowest unoccupied molecular orbital –LUMO– of neutral species) in the redox process was revealed.     

Selective ion exchange separation of uranium from concomitant impurities in uranium materials and subsequent determination of the impurities by ICP-OES

An ion exchange method has been developed for the separation of uranium from trace level metallic impurities prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES) in uranium materials. Selective separation of uranium from trace level metallic impurities consisting Cr, Co, Cu, Fe, Mn, Cd, Gd, Dy, Ni, and Ca was achieved on anion exchange resin Dowex 1 × 8 in sulphate medium. The resin (100–200 mesh, in chloride form) was packed in a small Teflon column (7.8 cm × 0.8 cm I.D.) and brought into sulphate form by passing 0.2 N ammonium sulphate solution. Optimum experimental conditions including pH and concentration of sulphate in the liquid phase were investigated for the effective uptake of uranium by the column. Uranium was selectively retained on the column as anionic complex with sulphate, while impurities were passed through the column. Post column solution was collected and analyzed by ICP-OES for the determination of metallic impurities. Up to 2,500 μg/mL of uranium was retained with >99% efficiency after passing 25 mL sample through the column at pH 3. Percentage recoveries obtained for most of the metallic impurities were >95% with relative standard deviations <5%. The method established was applied for the determination of gadolinium in urania–gadolinia (UO₂–Gd₂O₃) ceramic nuclear fuel and excellent results were achieved. Solvent extraction method using tributylphosphate (TBP) as extractant was also applied for the separation of uranium in urania–gadolinia nuclear fuel samples prior to the determination of gadolinium by ICP-OES. The results obtained with the present method were found very comparable with those of the solvent extraction method.