用渗流理论计算高分子溶液中溶剂的自扩散系数

基于微观渗流理论建立了溶剂小分子在高分子溶液中的自扩散模型,并据此模型对不同温度和浓度下的聚苯乙烯(PS)-苯、PS-甲苯、PS-乙苯和PS-四氢呋喃4个体系中小分子的自扩散系数进行了关联,计算出在不同温度下溶剂分子扩散所需的临界浓度。结果表明,在PS玻璃化温度以下,本模型对于温度和浓度具有很好的适用性和关联精度。     

电解质溶液自扩散系数的布朗动力学模拟

采用布朗动力学方法对电解质溶液进行了模拟,在传统布朗动力学的基础上综合考虑了流体力学的影响,并且引入SmartMonteCarlo方法的接受概率,避免了离子不现实的移动和位型重叠,这样不仅可以将模拟过程中的时间步长大幅度提高,而且还可使溶质在相空间的演化过程更接近实际.模拟过程以电解质溶液的原始模型为基础,将溶剂看作连续介质,溶质分子之间的相互作用采用软核加静电的势能函数模型,长程静电力采用Ewald加和的处理方法.模拟得到KCl和NaCl溶液的径向分布函数g+-(r),g++(r)和g--(r),并与文献中HNC计算以及模拟的结果进行比较,使用推广的Green-Kubo公式模拟计算溶液中各种离子的自扩散性质,计算结果与实验数据吻合良好.     

基于扩散势能和自由体积的自扩散系数模型

A new model for self-diffusion coe±cients was proposed based on both the concepts of molecular free volume and activation energy. The unknown parameters of this model were clearly defined and compared with the Chapman-Enskog model. At the same time a new method for calculating activation energy was devised and applied to the new model. In addition, the free volume was defined by implementing the generic van der Waals equation of state, the radial distribution function of which was obtained by using the MorsaliGoharshadi empirical formula. Under the same conditions, the new model was better than the original free volume model.     

用加脉冲梯度场的NMR自旋回波法测量高分子聚合过程中的自扩散系数

通过扩散系数的测量,可以了解高分子聚合反应整个过程的机理,进而控制聚合反应的进程。但能够测量高分子聚合过程中自扩散系数变化的仪器并不多。当前,加脉冲梯度场的自旋回波法被认为是最为有效和实用的方法^[1],此项研究围内尚未报道。     

甘油-水-氯化钠三元溶液中甘油浓度对甘油自扩散系数的影响

利用分子动力学模拟方法研究了浓度对甘油-水-氯化钠三元溶液中甘油自扩散系数的影响. 随着甘油浓度的增大, 甘油的自扩散系数逐渐减小. 氢键分析表明, 甘油自扩散系数的减小来源于其参与的甘油-水氢键数目的减少和甘油-甘油氢键数目的增加.     

溶液中自扩散过程的NMR方法研究

对脉冲梯度场－核磁共振（ＰＦＧ－ＮＭＲ）中测定溶液分子自扩散系数的Ｓｔｉｍｕｌａｔｅｄ ｅｃｈｏ方法进行了改进,把测定自扩散系数的Ｓｔｉｍｕｌａｔｅｄ ｅｃｈｏ脉冲序列与测定自旋－晶格弛豫时间的脉冲序列串接起来,设计了两个新的脉冲序列。     

槲皮素在溶液中的化学交换和自扩散运动

通过对溶于氘代二甲亚砜（DMSO d6）中的槲皮素的自扩散系数和槲皮素羟基质子与溶剂中水质子之间的交换速率常数的NMR测量,研究了交换速率常数与扩散系数随温度和含水量的变化情况.结果表明,化学交换与扩散系数是相互独立的两种运动,活泼质子的化学交换并不需要通过槲皮素分子的扩散而进行.但是活泼质子的表观扩散系数却显著地受化学交换的影响.当以活泼质子为对象时,这种影响需要引起足够的重视.     

醇类液体的热压力系数及内压

本文测定25-85℃温度范围内正戊醇.正已醇.正庚醇和正辛醇的热压力系数,发现这些醇类液体的内压几乎不随温度而变,本文还将修正的vander waals 模型推广到了醇类液体,与非缔合液体一样,它们的排斥体积亦与密度呈线性关系.但是,模型参数之比B/A^2不再是个常数,而是随醇分子中碳原子数的增多而快速地减小, 这个比值可作为合能力的一种量度.     

液体的热压力系数及内压

本文从排斥体积要随密度改变的概念出发,修正了原始的Van der Waals理论,并建立了一个计算液体热压力系数的公式 (P/I)_v=R_(ρm)/(1-A_(ρm) B_(ρ~2m))式中ρm=1/V_m是液体的摩尔密度,A和B都是与分子大小有关的两个特性常数。因此,利用Lennard-Jones位能函数中的参数σ_(LJ)便能预测液体在不同温度下的热压力系数及内压值。     

Self-diffusion coefficients of organic solvents in linear and branched high density polyethylene particles measured by PFG NMR

Pulsed field gradient nuclear magnetic resonance （PFG NMR） has been performed to study the diffusion of organic solvents into semicrystalline polyethylene particles. Self-diffusion coefficients in different domains of the sample can be extracted through a bi- exponential fit to the echo intensity attenuation, which allows the precise determination of the tortuosity of the polyethylene particles. Further exploration comes from the measurements with branched polyethylene particles and it was found that the diffusion in polymer phase contributed significantly to the slow component of the exponential decay curve. 2007 Jing Dai Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Diffusion Coefficients of Imidazolium Based Ionic Liquids in Aqueous Solutions

Diffusion coefficients of the ionic liquids [C₂MIM][EtSO₄], [C₄MIM][OcSO₄], [C₂MIM][NTf₂] and [C₄MIM][NTf₂] in water at high dilution have been measured using the Taylor dispersion technique. Data on the diffusion coefficients have been obtained for each solute at six temperatures between 288 and 313 K. The data have been fitted by the Arrhenius equation and activation energies of diffusion have been determined. Effective radii of the ionic liquid molecules have also been obtained using the Stokes–Einstein relationship.     

A Model of Hydrogen-Bonded Liquids

The orientation defect model can be used for quantitative estimates and for understanding the properties of H-bonded liquids, such as water and alcohol. The defect concentrations can be determined by vibrational spectroscopy, and the applicability of the approximation procedure derives from considering H-bonds as chemical equilibria. Possible extensions of the simple model are critically discussed.     

Review of Mesoscopic Modeling of Liquids in Materials Science

Mesoscopic theories can be used in the field of materials science to derive local average properties of relevance to the engineer such as flux, pressure, average density or composition. In the following density functional theory will be described and applied to different systems of interest and in particular, to materials formed from complex liquids as characterized by atomic structure and the type of interaction between the individual particles. The calculation of the solid to liquid transition will be explained in detail as a prototype for other order disorder transitions. The theory of polymers in solution will be revisited and used to calculate phase separation in mixtures. An extension of the theory to include the orientation of rodlike, long molecules will be applied to liquid crystals. In the presence of an interface, the system properties depend strongly on position in space and can be predicted from parameters obtained in the bulk in a square gradient approximation for sufficiently smooth and small deviations from the uniform distribution. A phase transition is often used to prepare heterogeneous materials by nucleation and growth. It will be shown how the equilibrium theory can be extended to study the dynamics of nonequilibrium phenomena.     

离子液体对锯末中纤维素的溶解及再生研究

探讨了离子液体1-(4-磺酸基丁基)-3-甲基咪唑的硫酸氢盐(IL-1)作为催化剂,金属氯化物作为助催化剂时纤维素的水解,利用离子液体IL-1对杨木锯末中纤维素的直接溶解并再生,考察了温度、碱性溶液的浓度以及溶解时间对溶解率的影响,通过傅里叶红外光谱FT-IR、X-射线衍射仪及热失重对处理前后锯末、再生纤维素的结构、结晶性及热性能进行了研究.结果表明,温度为90℃,NaOH质量分数为6%,溶解时间为2 h时,离子液体对杨木锯末具有最佳的溶解性,溶解率可达45%左右.离子液体主要溶解杨木锯末中的纤维素,且为非衍生化的直接溶解,再生后的纤维素结晶形态由纤维素I变为II,热稳定性能有所降低.     

Coulometry on the Voltammetric Timescale: Microdisk Potential‐Step Chronoamperometry in Aprotic Solvents Reliably Measures the Number of Electrons Transferred in an Electrode Process Simultaneously with the Diffusion Coefficients of the Electroactive Species

Microdisk, single potential‐step chronoamperometry, is applied to a range of organic substrates in the aprotic solvents tetrahydrofuran, propylene carbonate, acetonitrile and the room temperature ionic liquid [C₄dmim][N(Tf)₂]. Fitting of the chronoamperometric transients was achieved using the Shoup and Szabo method [3]. Accurate values for the diffusion coefficients, D, and the number of electron(s) transferred, n, in the electrode process have been simultaneously and consistently obtained. This method is shown to be generally applicable and reliable for the determination of the number of electrons transferred in faradaic processes uncomplicated by relatively slow coupled homogeneous kinetics. Since the experiment is conducted essentially on typical voltammetric timescales it can be commended as a complementary technique for classical coulometry which is only possible on much longer timescales. The chronoamperometric method is therefore likely to be of greater relevance to the interpretation of voltammetric data.     

A Direct NMR Method To Measure Self-Diffusion Coefficients in Liquids by Monitoring Diffusing Molecules through One-Dimensional Imaging

Diffusion processes can be followed directly by recording one-dimensional images of a selected slice at variable intervals after selective inversion of the magnetization. The resulting diffusion coefficients of H₂O and DMSO are consistent with earlier studies at different temperatures, obtained by monitoring the attenuation of NMR signals as a function of the gradient amplitude in gradient echo sequences.