Study of reaction processes by in-line near-infrared spectroscopy in combination with multivariate curve resolution: Esterification of myristic acid with isopropanol

The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra.The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions.     

Theoretical study of some 1,3-substituted (1,3-diketonato)borondifluorides. Potential energy curve relevant to the barrier crossing reaction

Ab initio Hartree-Fock calculations utilising STO-3G, 3-21G^* and 6-31G^* basis sets have been performed on three neutral and highly polar molecules, (diformylmethine)borondifluoride, (acetylacetonato)borondifluoride and (dibenzylmethine) borondifluoride. The calculated and experimental structures are well correlated when using the HF/3-21G^* basis set, except for the structure parameters involving the boron atom. The HF/6-31G^* basis set does not improve the accuracy in structure calculations. The conformational analysis is in agreement with the experimentally observed C_2v symmetrical structures, where the boron atom is tetrahedrally coordinated. The calculations support a one-dimensional ground state barrier crossing reaction for (dibenzylmethine)borondifluoride, where the phenyl torsion is the most likely reaction coordinate. Both HF/6-31G^* calculations and the second-order Møller-Plesset correction with the 3-21G^* basis set suggest an activation energy of the ground state reaction of about 30 kJ mol⁻¹. The ground state barrier crossing reaction kinetics is evaluated by the Kramers theory. The calculated ground state parameters relevant to the barrier crossing reaction are compared with the experimentally observed excited state values.     

水+3-甲基吡啶+溴化钠三元溶液临界跨接现象

采用折射率法在较宽温度范围内研究了溴化钠、3-甲基吡啶和水的临界质量分数分别为0.240、0.192和0.568体系的临界性质, 发现在近临界点临界指数为0.365, 与Fishe重整化值一致. 有效临界指数随着温度逐渐远离临界点, 从0.365下降到0.20左右, 但当排除了“正规项”的影响后, 展现出向平均场理论值0.5单调跨接的行为.     

Etude Experimentale et Modelisation des Equilibres Solide—Liquide du Systeme Binaire H2O—UO2(NO3)2

The binary system H₂O—UO₂(NO₃)₂ was studied by solubility measurements and constant heat flow thermal analysis. Temperature and composition of the eutectic transformation between ice and uranyl nitrate hexahydrate were accurately defined. A new hydrate with 24 molecules of water decomposes at –21°C according to the peritectoid reaction<UO₂(NO₃)₂·24H₂O> <UO₂(NO₃)₂·6H₂O> + 18<H₂O>The quasi-ideal model was applied to the solid—liquid equilibria, using the following reaction hypothesis:((UO ₂ ²⁺ )) + 2((NO ₃ ^– ))+ h((H₂O)) ((UO₂OH⁺aq)) + ((H₃O⁺aq + 2((NO ₃ ^– aq))A complete calculation of the binary system was carried out with a global ionic hydration number h equal to 9 in the aqueous solutions. It allowed to the melting enthalpies of uranyl nitrate hydrates.

This revised version was published online in November 2005 with corrections to the Cover Date.     

Evaluation of the parameters of the Bender equation of state for low acentric factor fluids and carbon dioxide

Volumetric properties of several low acentric factor fluids (Ar, CH₄, C₂H₆, Kr, N₂, Ne, O₂, Xe) as well as CO₂ are modeled using the Bender equation of state. This equation is a linear function of 19 adjustable parameters, which are evaluated from properties data, using a linear numerical procedure. The validity of the EOS is tested by calculating the Joule-Thomson inversion curve. A simple model is in particular used to correlate the inversion properties predicted by the Bender equation, expressed in term of reduced pressure as a function of reduced temperatures ranging from 0.8 to 6. The simple correlation reproduces accurately the used data. We employ data on state behaviour ρ(P,T) of homogeneous fluid phases, vapour-liquid equilibrium, second virial coefficient and the coordinates of the critical point.     

WO3粉在高速层间剪切条件下的颗粒破碎特征

研究了WO3粉和W粉的剪切破碎时间对WO3粉和W粉的沉降曲线、平均粒度、BET比表面及松装密度的影响.用TEM和SEM对剪切破碎前后的粉末进行了直接观察.结果表明:新型剪切破碎机能有效地粉碎微米级WO3等脆性粉末,同时可以破坏超细W粉中的桥接团粒,使W粉和WO3粉的松装密度增加1倍以上,但对比表面积影响不大.     

超细晶粒W-40%Cu合金的烧结和力学性能

以纳米W,Cu粉末为原料,通过测定H2中热压烧结和无压烧结的收缩动力学曲线,研究了纳米W-40%Cu化学混合粉末的致密化过程.对比了纳米W粉与常规Cu粉(-44μm)的机械混合粉和纳米W-Cu化学混合粉的热压烧结致密化过程.测定了烧结合金在300℃和500℃下高温应力一应变曲线.实验结果表明:采用纳米W-40%Cu化学混合粉末在H2中无压烧结时最大收缩速率对应温度为980℃;1 200℃烧结平均晶粒小于2μm,相对密度为97%.纳米W-Cu化学混合粉在H2热压烧结时最大收缩速率对应温度为930℃;1 200℃烧结合金的平均晶粒为0.5 μm,相对密度为98%.纳米W-Cu化学混合粉热压合金高温抗压强度比纳米W与常规Cu粉的热压合金高.     

软土路堤沉降预测方法研究

建立了依据路堤填土期施工期和预压期观测资料计算路堤总瞬时沉降、总固结沉降、地基固结指数的基因反演方法,进而根据这三个反演参数计算最终沉降,并与实际值作比较,二者符合较好.此外,再依据预压期的沉降资料,分别利用三种不同的计算模型反演计算最终沉降,并与实测结果进行比较,进而对沉降计算模型的选取提出建议.     

低速非达西渗流储层产能评价

在低渗透油藏低速非达西渗流模型的基础上，应用具有启动压力影响的不稳定产能评价方法，实现了将地层参数代入相关方程计算产量随时间的变化规律及不稳定IPR曲线，对于工业油层预测了生产时间为180天时油井的极限产量(流压为0．101MPa时的产量)，对这类井的开发投产具有重要的指导意义。     

某滑坡滑带非饱和土强度特性试验研究

借助专门的能够控制吸力的四联式非饱和土直剪仪,对清江水布垭坝区古树包滑坡滑带土的重塑样进行了一系列抗剪强度试验,验证了F red lud提出的非饱和土抗剪强度公式对滑带土的适用性,求出了该滑带非饱和土的强度参数;通过在一定基质吸力条件下量测含水率-固结压力之间的关系,指出土-水特征曲线与固结压力相关的特性。