A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

The mechanisms of CO₂ coupling with the propargylic alcohol using alkali carbonates M₂CO₃ (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs₂CO₃-mediated carboxylative cyclization of the propargylic alcohol with CO₂, and (b) the conversion of the αACC intermediate with Cs₂CO₃ to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO₃ together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO₂ with the propargylic alcohol. Compared to other alkali carbonates M₂CO₃ (M = Li, Na, K), the stronger basicity of Cs₂CO₃ and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Role of FTFSI Anion Asymmetry on Physical Properties of AFTFSI (A=Li,Na and K) Based Electrolytes and Consequences on Supercapacitor Application

This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li⁺, Na⁺ or K⁺) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.     

Studies on basicity of alkali metal catron exchanged β and X zeolites by pyrrole-IR spectroscopy

The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework.     

Desorption behavior of a surfactant in a linear low‐density polyethylene blend at elevated temperatures

The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10^?11 to 6.79 × 10^?11 cm²/s, from 1.10 × 10^?11 to 5.75 × 10^?11 cm²/s, and from 0.58 × 10^?11 to 4.75 × 10^?11 cm²/s, respectively. In addition, the calculated activation energies (E_D) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm^?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm^?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm^?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004     

铁基添加剂增强细水雾灭火性能的实验研究

采用实验模拟的方法,研究了添加氯化亚铁的细水雾在不同添加剂浓度、不同喷头压力下,熄灭不同性质的液体池火的性能。实验结果表明:添加有氯化亚铁的细水雾,其灭火性能发生了显著变化。存在一个最佳的灭火浓度,其对应的灭火时间最短,耗水量最少,灭火效率最高。细水雾喷头的工作压力和燃料的性质也对细水雾的灭火性能有影响:工作压力越大,细水雾的平均灭火时间越短。在相同的实验条件下,细水雾扑灭煤油池火的时间要短于扑灭酒精池火的时间。     

Dislocation unpinning model of acoustic emission from alkali halide crystals

The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constantτ _s for surface annihilation of dislocations and the pinning timeτ _p of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.     

考虑流体湿润性影响的核沸腾RohsenoW修正模型

添加界面活性剂的核沸腾在改变蒸气泡生长特性的同时，主要是强化了对流换热．本文考虑流体湿润性影响，对核沸腾换热沿用最广的对流类比模型－Ｒｏｈｓｅｎｏｗ模型进行了修正．通过对实验数据的检验，表明修正后的模型预示值与实测结果吻合很好．     

Thermal properties of poly(styrene) containing brominated aryl phosphate additives

General purpose poly(styrene) is a large volume commodity polymer widely used in a range of applications. For many of these the presence of an additive to impart some flammability resistance is required. Most commonly, brominated aromatics are used for this purpose. As the polymer undergoes combustion these compounds decompose to generate bromine atoms and/or hydrogen bromide which escape to the gas phase and trap flame propagating radicals. While these species are effective in inhibiting flame propagation they present the opportunity for loss of halogen to the atmosphere. For this reason, the use of these compounds is being limited in some parts of the world. Phosphorus compounds, on the other had, impart a flame retarding influence by promoting char formation at the surface of the burning polymer. This prevents heat feedback to the polymer and consequent pyrolysis to generate fuel fragments. The combination of both bromine and phosphorus present in a single compound might generate a superior flame-retarding additive in that both modes of retardancy might be promoted simultaneously. Should this be the case smaller amounts of additive might be necessary to achieve a satisfactory level of flame retardancy. A series of such additives, brominated aryl phosphates, has been synthesized and fully characterized spectroscopically. Blends of these additives, at various levels, with poly(styrene) have been examined by DSC, TG and in the UL-94 flame test. The flammability of the polymer is dramatically diminished by the presence of the additive.     

Effect of BaBiO3 and Ba0.6K0.4BiO3 additives on the rechargeability of manganese oxide cathodes in alkaline cells

The effect of the incorporation of small amounts (1–5 wt%) of semiconducting BaBiO₃ and metallic Ba_0.6K_0.4BiO₃ additives on the rechargeability of electrolytic manganese dioxide (EMD) cathodes in alkaline cells in the one-electron regime has been investigated. Both the BaBiO₃ and Ba_0.6K_0.4BiO₃ additives lead to better cyclability compared to the previously known binary oxide additive Bi₂O₃. X-ray diffraction patterns recorded before and after 30 cycles as well as cyclic voltammograms recorded after first and 30 cycles reveal that the better cyclability in the presence of BaBiO₃ and Ba_0.6K_0.4BiO₃ additives is due to the suppression of the formation of unwanted, electrochemically inactive birnessite and hausmannite phases and a shifting of the second-electron capacity of Mn to higher potentials.