298.15K下ccl4在CH3OH—C6H6混合物中的偏摩尔体积

有若干原因促使人们使用混合溶剂,例如对溶解度的技术要求,欲改变溶剂的介电常数,都常常改变溶剂的组成。人们研究溶剂结构及其对溶质性质的影响,则把潜溶剂加入水中就会对溶剂的结构产生影响。关于混合溶剂中各种化学问题的讨论,都必须考虑组份内和组份间的这两种相互作用,体积函数比较直观,有助于对其它偏摩尔数量的理解。近年来,由于商品密度计的开发,对溶液密度的直接测量前进了一步,此种密度计仅需要较小体积的溶液和提供了10~(-6)(克)的准确度。本文采用“高精度读数式液体流动密度计”,测定四氯化碳在甲醇—苯体系中偏摩尔体积。以第三组分在二元混合物中偏摩尔性质变化,探讨三元系中分子间相互作用和机理。     

CH3COSbCl6催化四氢呋喃聚合的研究

ＣＨ_３ＣＯＳｂＣｌ_６催化四氢呋喃聚合的研究栗方星，王红军，马克勤（南开大学化学系，天津，３０００７１）关键词聚四氢呋喃，乙酰基六氯锑酸盐，表观聚合反应速率常数，五氯化锑ＴＨＦ聚合为平衡聚合反应应［１，２］，文献报道［３，４］Ｅｔ３ＯＢＦ４、Ｅｔ３Ｏ...     

Investigation of isothermal and no-isothermal oxidation of SiC powder using an analytic kinetic model

The oxidation of SiC powder has been investigated under non-isothermal and isothermal conditions. X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) were employed to investigate the morphological development during the oxidation. The results show that the major oxidation product was amorphous silica and the oxidation reaction was mainly diffusion-controlled. Based on limited experimental data, an analytic kinetic model, which expresses the oxidation weight gain as a function of time and temperature explicitly, has been used to predict the oxidation behavior of SiC powder. The comparison between experimental results and theoretical calculation shows that this new model works very well. The activation energy of non-isothermal and isothermal oxidation of SiC powder has been derived to be 226.5 kJ/mol and 187.5 kJ/mol, respectively.     

以时温等效方法研究尼龙1010应力松弛行为及使用寿命预测

以尼龙材料的应力松弛行为作为研究对象, 考察初始应变为1.0%, 2.8%和5.1%的尼龙1010样品在温度区间293353 K的松弛曲线, 采用时间-温度等效叠加方法得到了松弛模量主曲线, 计算出叠加过程中的表观活化能、 松弛过程中的活化体积和应力辅助功. 结果表明, 整个松弛过程中的表观活化能和应力辅助功表现出相同的变化趋势, 体现出松弛过程中克服运动单元位垒的过程. 当293323 K区间的松弛曲线叠加时, 随着初始应变的增加, 表观活化能和应力辅助功均逐渐降低, 有助于聚合物内部的运动单元越过能垒发生松弛, 与松弛过程中的应力辅助热活化理论相一致; 当333353 K区间的松弛曲线叠加时, 不同初始应变样品的表观活化能均为260 kJ/mol, 应力辅助功均为60 MPa·nm³, 说明松弛过程中克服运动单元的能垒与应力作用无关. 根据松弛主曲线, 计算出了尼龙1010在1.0%, 2.8%和5.1% 3种形变下, 长时间范围内应力衰减与时间的关系, 为预测实际使用过程中的应力松弛行为提供了依据.     

Abdominal apparent diffusion coefficient measurements: effect of diffusion-weighted image quality and usefulness of anisotropic images

This study aimed to assess the effect of diffusion-weighted image (DWI) quality on abdominal apparent diffusion coefficient (ADC) measurements and the usefulness of anisotropic images. Twenty-six patients (10 men and 16 women; mean, 58.1 years) who underwent DW imaging and were diagnosed not to have any abdominal diseases were analyzed. Single-shot spin-echo echo-planar DW imaging was performed, and one isotropic and three orthogonal anisotropic images were created. ADCs were calculated for liver (four segments), spleen, pancreas (head, body, tail) and renal parenchyma. Image quality for each organ part was scored visually. We estimated the correlation between ADC and image quality and evaluated the feasibility of using anisotropic images. ADCs and image quality were affected by motion probing gradient directions in the liver and pancreas. A significant inverse correlation was found between ADC and image quality. The r values for isotropic images were −.46, −.48, −.70 and −.28 for the liver, spleen, pancreas and renal parenchyma, respectively. Anisotropic images had the best quality and lowest ADC in at least one organ part in 17 patients. DWIs with the best quality among isotropic and anisotropic images should be used in the liver and pancreas.     

强干扰区可控源音频大地电磁勘探处理研究

强干扰区进行地球物理探测,尤其是电磁法勘探时,难以获得可靠的、高质量的原始数据;为取得良好的勘探效果,预处理的重要性更加凸显。通过对原始数据的呈现、分析,提出数据预处理的两套方案,并从理论和实际上证实了方案的可行性。最终结合勘探实例,对比两套数据预处理方案,优选全区视电阻率的方法对原始数据进行预处理,并对其预处理数据反演成图,取得了良好的应用效果。     

Micellar Exchange Kinetics of Quaternary Ammonium Type Gemini Surfactants Monitored by Nuclear Magnetic Resonance

The dynamic NMR (DNMR) method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14(s=2, 3 and 4).The escape rate constant, k^-, was derived based on the simplified equations of DNMR theory, and the apparent activation energy of escape, E_a^-, was obtained based on the Arrhenius equation through temperature variation experiments.Results show that the orders of magnitude of k^- for 14-s-14 and 12-s-12 are respectively 10 and 10³ s^-1, E_a^- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/mol.Furthermore, increases and E_a^- decreases with the spacer length growing.In combination with the micro-polarity measurements, it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the micelles.The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.     

High-pressure densities and derived volumetric properties (excess, apparent, and partial molar volumes) of binary mixtures of {methanol (1) + [BMIM][BF4] (2)}

The density of seven {(0.0087, 0.0433, 0.1302, 0.2626, 0.4988, 0.7501, and 0.9102) mole fraction of [BMIM][BF₄]} binary {methanol (1) + [BMIM][BF₄] (2)} (1-butyl-3-methylimidazolium tetrafluoroborate) mixtures has been measured with a vibrating-tube densimeter. Measurements were performed at temperatures from (298 to 398) K and at pressures up to 40 MPa. The total uncertainties of density, temperature, pressure, and concentration measurements was estimated to be less than 0.15 kg · m⁻³, 15 mK, 5 kPa, and 10⁻⁴, respectively. The uncertainties reported in this paper are expanded uncertainties at the 95% confidence level with a coverage factor of k = 2. The effect of temperature, pressure, and concentration on the density and derived volumetric properties such as excess, apparent, and partial molar volumes was studied. The measured densities were used to develop a Tait-type equation of state for the mixture. The structural properties such as direct and total correlation function integrals and cluster size were calculated using the Krichevskii function concept and the equation of state for the mixture at infinite dilution.     

Enantioseparation of Binaphthol and Its Derivatives on Cellulose Tris(3,5-dimethylphenyl carbamate)

A Chiralcel OD-H column was used for the normal phase enantioseparation of binaphthol and its derivatives. Unexpectedly, binaphthol and its dibromo-substituted analogue could not be enantioseparated fully, whereas its ether and ester derivatives gave complete or partial resolution. Aspects of the chiral recognition are discussed further through calculated thermodynamic parameters.     

Y型分子筛结构破坏的动力学分析(英文)

Y型分子筛是催化裂化(FCC)的速率控制组分.FCC过程中,催化剂在反应器和再生器中往往面临高温水蒸气存在的苛刻环境.因此,分子筛的热稳定性和水热稳定性是催化剂最为关注的性能之一.由于FCC原料中通常含有V、Ni、Na、Fe等不同数量的金属污染物,会对催化剂造成污染及钝化.进料中存在的卟啉类有机复合物持续不断的沉积在催化剂表面,由于含钒的有机金属卟啉化合物在反应中转化形成V_2O_5,V_2O_5在水热条件下形成H_3VO_4组分,在高温水热气氛下加速分子筛骨架结构水解,破坏了Y型分子筛的晶体结构,从而降低了催化剂活性,影响产品选择性.稀土Y型分子筛在FCC中扮演重要的角色,稀土交换分子筛可以提高催化酸性、裂化活性和热与水热稳定性.此外,Na在高温水蒸气条件下也会对分子筛结构造成破坏.一方面,钠能够中和Y型分子筛B酸中心,降低催化裂化活性;另一方面,水热条件下钠的存在会加速破坏Y型分子筛的结构.有关Y型分子筛结构破坏的机理解释较多,然而该过程的动力学研究鲜有报道.反应动力学不能提供一个直接的反应机理,但是任何反应机理的提出必须符合反应动力学的数据.本文采用离子交换法分别制备了一系列不同Na含量USY,不同稀土含量USY,以及含钠和稀土的USY分子筛,通过固相动力学模型考察了上述Y型分子筛水热结构破坏活化能的变化及钒对其活化能的影响.结果表明,Y型分子筛的结构破坏存在三种路径,分别是脱铝、脱硅和La-O键的断裂.钒加速了分子筛骨架水解速率;钒钠具有协同作用,同时存在时对分子筛破坏作用更加显著;NaOH的形成是速率控制步骤;稀土稳定了分子筛的结构,降低了分子筛的水热脱铝速率;钒与定位于分子筛小笼里稀土作用,破坏分子筛的[RE-OH-RE]~(5+)的RE-O键夺取分子筛的骨架氧,导致骨架结构崩塌.由于稀土本身稳定了分子筛的结构,同时钒稀土作用时形成稳定的REVO_4固定了钒的流动性,因此钒对REY结构的影响是几种因素相互叠加和抵消的结果.