一点法测定特性粘数

特性粘数一般由η_(sp)/C 或 ln η_r/C(η_(sp)是增比粘度,η_r 是相对粘度,C 是浓度)对 C 作图,外推到 C=0而求得。这样每个样品就至少需要测定三个不同浓度下的溶液粘度。在某些情况下,如要快速知道结果,样品很少,不便稀释,实验中途发生意外仅得一个数据等情况时,就感到很不方便。为此,文献中早有一点法测定特性粘数的报导。近年来许多人仍重视该问题的研究。下面将引述几个常用的及一点法表示溶液粘度数据的方程式:η_(sp)/C=[η] k'[η]~2C (1)ln η_r/C=[η]-β[η]~2C (2)[η]=(2(η_(sp)-ln η_r))~(1/2)/C (3)[η]=(η_(sp) r ln η_r)/C(1 r) (4)r=k'/β[η]=(η_(sp) 3 ln η_r)/4C (5)式中,[η]为特性粘数。η_r 为相对粘度。η_(sp)为增比粘度。k'和β在一般情况下是与分子量无关的常数。     

一个适用于Huggins常数K′较大的新的一点法特性粘数方程

本文提出了一个适用于Huggins常数较大(0.472≤K＇≤0.825)的聚合物-溶剂体系的新的一点法特性粘数方程[η]=ηsp/Cη~(1/2).并与其它四个一点法方程分别对19种聚合物的27种聚合物-溶剂体系的192个文献数据进行计算比较,发现本方程所得结果是十分满意的.因此,本方程的建立,扩大了用一点法求算聚合物特性粘数方法中K＇值的范围.     

粘度数据的外推和从一个浓度的溶液粘度计算特性粘数

高分子稀溶液粘度的浓度依賴性,常用式 η_(sp)/[η]+K'[η]~2C (1) 和 1nη/C=[η吁]-β[η]~2C (2)来表示。粘度数据的处理,通常都在同一图紙上,同时以η_(sp)/C和1nη_r/C对C作线性外推,C→0的共同截矩为特性粘数[η],斜率系数应当滿足     

动能改正对赫金斯常数k′的影响

高分子溶液粘度的浓度依賴关系,在很稀的浓度范围內可表达为: (ηsp)/C=[η]+k′[η]~2Ck′卽为赫金斯常数,表征溶液中高分子間、高分子和溶剂分子之間的相互作用,对于柔性結构之綫型高分子在良溶剂內,k′值一般在0.3—0.4之間,如分子鏈有     

极低浓度区高分子溶液异常粘度行为研究进展

极低浓度区高分子溶液粘度的测定涉及到外推法确定高分子溶液特性粘数的实验基础。综述了极低浓度区高分子溶液反常粘度行为的起源，探讨了粘度计毛细管管壁上高分子吸附层、界面效应、高分子溶液或溶剂在毛细管中流动模式的改变、高分子与毛细管管壁界面间相互作用、乌氏粘度计结构限制等对极稀高分子溶液粘度的影响，以及正确测定极低浓度区高分子溶液粘度的实验方法。     

比密粘度和特性粘数的计算及改正

本文导出毛细管粘度计的比密粘度方程: v=η/ρ=At-Bt~(-1)+C 式中-Bt~(-1)和C分别代表动能改正和残液改正。方程在宽的粘度范围内有良好精度。本文提出,准确的特性粘数[η]与忽略任何改正的特性粘数[η]~*之间存在简单的线性关系。例如从以上方程可写出[η]=(1+k_e-k_v)[η]~*+δρ式中k_e=2Bt_o~(-1)/At_0+Bt_0~(-1)+C), k_v=C/(At_0-Bt_0~(-1)+C), δρ=(ρ_1-ρ_0)/(c_1ρ_0), 它们分别是代表动能改正、残液改正和密度改正的常数。利用以上特性粘数改正公式, 可在确保准确性的前提下极大地简化特性粘数的改正计算。     

一组新的高分子溶液粘度与浓度关系函数式

<正> 粘度法是测定高聚物分子的大小与结构最简便、最常用的方法.在用粘度法测定高聚物分子大小与结构时,需求得极限粘数[η].为此,需确立高分子溶液粘度与浓度的关系,文献中有过种种不同的函数式.通常,将ηsp/c、logηsp/c、lnηr/c对c或ηsp/c对ηsp作图外推到c为零或ηsp为零得[η].Heller对各种外推方法进行了详细的研究,可是到目前为止,采用的成对外推公式不多,且有明显的缺陷.     

与《一个新的一点法测定特性粘数方程》一文商榷

<正> 编委: 《高分子通讯》1979年第2期刊登的《一个新的一点法测定特性粘数方程》一文,我觉得该文有一些问题值得提出来,与作者和读者商榷. 一、粘度方程式(1)与(4)中的斜率常数,     

聚苯乙烯-丁酮-正己烷体系稀溶液性质的研究

测定了五个聚苯乙烯级分((?)_η3.2×10~5—2.7×10~6)在丁酮-正己烷体系中的特性粘数,发现高分子量级分的特性粘数-组成曲綫在γ=0.13处出现极大值。简要叙述了自制光电式散射光度计的结构。聚苯乙烯级分在上述混合溶剂体系内光散射测定的结果表明,A_2也在γ=0.13处出现极大。应用溶度参数解释了上述结果。本工作所得聚苯乙烯溶度参数实验值为8.8。 根据在θ-溶剂中A_2=0及Mark-Houwink方程参数α=1/2的条件,从粘度及光散射所测得的聚苯乙烯-丁酮-正己烷体系(30℃)的θ溶剂组成是一致的,γ_θ=0.45。     

一种同时订定高分子凝胶渗透色谱校准参数和K、α常数的新方法

报道一种同时订定高分子凝胶渗透色谱(GPC)校准参数和Mark常数K、α的新方法。待测高分子经粗分级,测得其特性粘数[η]_1和GPC谱图G_1,另取一种已知K_0、α_0值的参考高分子,也经粗分级后测得[η]_(0,1)和G_(0,1),根据普适校准关系,结合Mark方程和由Wesslan分布函数所导出的粘均分子量计算公式,得到联立方程组。通过求解该方程组同时订定了高分子的GPC校准参数和K、α常数。     

Electrostatic interaction between soft particles

Electrostatic interaction between two soft particles (i.e., polyelectrolyte-coated particles) in an electrolyte solution is discussed. An approximate analytic expression for the interaction energy between two dissimilar soft spheres is derived by applying Derjaguin's approximation to the corresponding interaction energy between two parallel dissimilar soft plates for the case where the density of fixed charges within the polyelectrolyte layer is low. The obtained expression covers various limiting cases that include hard sphere/hard sphere interaction, spherical polyelectrolyte/spherical polyelectrolyte interaction, soft sphere/spherical polyelectrolyte interaction, soft sphere/hard sphere interaction, and spherical polyelectrolyte/hard sphere interaction.     

Model chemistry calculations of thiophene dimer interactions: origin of pi-stacking

The intermolecular interaction energies of thiophene dimers have been calculated by using an aromatic intermolecular interaction (AIMI) model (a model chemistry for the evaluation of intermolecular interactions between aromatic molecules). The CCSD(T) interaction energy at the basis set limit has been estimated from the MP2 interaction energy near the basis set limit and the CCSD(T) correction term obtained by using a medium-size basis set. The calculated interaction energies of the parallel and perpendicular thiophene dimers are -1.71 and -3.12 kcal/mol, respectively. The substantial attractive interaction in the thiophene dimer, even where the molecules are well separated, shows that the major source of attraction is not short-range interactions such as charge transfer but rather long-range interactions such as electrostatic and dispersion. The inclusion of electron correlation increases the attraction significantly. The dispersion interaction is found to be the major source of attraction in the thiophene dimer. The calculated total interaction energy of the thiophene dimer is highly orientation dependent. Although electrostatic interaction is substantially weaker than dispersion interaction, it is highly orientation dependent, and therefore electrostatic interaction play an important role in the orientation dependence of the total interaction energy. The large attractive interaction in the perpendicular dimer is the cause of the preference for the herringbone structure in the crystals of nonsubstituted oligothiophenes (alpha-terthienyls), and the steric repulsion between the beta-substituents is the cause of the pi-stacked structure in the crystals of some beta-substituted oligothiophenes.     

过渡金属络合物自旋哈密顿算符的理论分析

利用不可约张量方法讨论了过渡金属络合物自旋哈密顿。在考虑自旋轨作用、电子与其它电子旋轨作用、自旋-自旋偶极作用、Fermi作用和外磁场作用的近似下,得到了由分子参量表示的自旋哈密顿参量。在原子轨道近似下,近似地计算了红宝石的g因子,结果与实验符合得相当好,表明用本法解释过渡金属络合物的ESR谱是成功的。     

Molecular integrals of relativistic effects with gaussian-type orbitals

A mathematical analysis is presented of molecular integrals of relativistic interactions in molecules. The integrals are based on Gaussian-type orbitals and include those arising from variation of electron mass with velocity, one-electron Fermi contact interaction, electron spin-same-orbit interaction, electron spin-nuclear spin interaction, electron spin-spin contact interaction, electron spin-other-orbit interaction, electron spin-spin dipolar interaction and electron orbit-orbit interaction. The integrals are expressed in suitable forms for use in computer. It is also pointed out that the integrals are written essentially in terms of the overlap, nuclear attraction, electron repulsion, or field integrals.     

How does water-nanotube interaction influence water flow through the nanochannel?

Water permeation across various nitrogen-doped double-walled carbon nanotubes (N-DWCNT) has been studied with molecular dynamics simulations to better understand the influence of water-nanopore interaction on the water permeation rate. There exists a threshold interaction energy at around -34.1 kJ/mol. Over the threshold energy, the water flow through N-DWCNT decreases monotonically with the strengthening of the water-nanotube interaction. The effect on the water flow across the channel is found to be negligible when the interaction energy is weaker than the threshold. The water-nanotube interaction energy can be controlled by doping nitrogen atoms into the nanotube walls. Although the van der Waals interaction energy is much stronger than the electrostatic interaction energy, it is less sensitive to the proportion of doped nitrogen atoms. On the other hand, the electrostatic interaction energy weakens after the initial strengthening when the percentage of doped nitrogen atoms increases to ~25%. The doped nitrogen atoms make less influence on the overall electrostatic interaction energy when the proportion is over 25%, due to the repulsions among themselves. Thus, the monotonous strengthening of the van der Waals interaction energy seems to dominate the overall trend of the total interaction energy, whereas the change of the long-range electrostatic interaction energy characterizes the shape of the correlation curve, as the percentage of doped nitrogen atoms increases.     

Origin of attraction and directionality of the pi/pi interaction: model chemistry calculations of benzene dimer interaction.

A model chemistry for the evaluation of intermolecular interaction between aromatic molecules (AIMI Model) has been developed. The CCSD(T) interaction energy at the basis set limit has been estimated from the MP2 interaction energy near the basis set limit and the CCSD(T) correction term obtained by using a medium size basis set. The calculated interaction energies of the parallel, T-shaped,and slipped-parallel benzene dimers are -1.48, -2.46, and -2.48 kcal/mol, respectively. The substantial attractive interaction in benzene dimer, even where the molecules are well separated, shows that the major source of attraction is not short-range interactions such as charge-transfer but long-range interactions such as electrostatic and dispersion. The inclusion of electron correlation increases attraction significantly. The dispersion interaction is found to be the major source of attraction in the benzene dimer. The orientation dependence of the dimer interaction is mainly controlled by long-range interactions. Although electrostatic interaction is considerably weaker than dispersion interaction, it is highly orientation dependent. Dispersion and electrostatic interactions are both important for the directionality of the benzene dimer interaction.     

Intermolecular interaction between hexafluorobenzene and benzene: Ab initio calculations including CCSD(T) level electron correlation correction

The intermolecular interaction energy of hexafluorobenzene-benzene has been calculated with the ARS-E model (a model chemistry for the evaluation of the intermolecular interaction energy between aromatic systems using extrapolation), which was formerly called the AIMI model. The CCSD(T) interaction energy at the basis-set limit has been estimated from the MP2 interaction energy at the basis-set limit and the CCSD(T) correction term obtained using a medium-sized basis set. The slipped-parallel (Cs) complex has the largest (most negative) interaction energy (-5.38 kcal/mol). The sandwich (C6v) complex is slightly less stable (-5.07 kcal/mol). The interaction energies of two T-shaped (C2v) complexes are very small (-1.74 and -0.88 kcal/mol). The calculated interaction energy of the slipped-parallel complex is about twice as large as that of the benzene dimer. The dispersion interaction is found to be the major source of attraction in the complex, although electrostatic interaction also contributes to the attraction. The dispersion interaction increases the relative stability of the slipped-parallel benzene dimer and the hexafluorobenzene-benzene complex compared to T-shaped ones. The electrostatic interaction is repulsive in the slipped-parallel benzene dimer, whereas it stabilizes the slipped-parallel hexafluorobenzene-benzene complex. Both electrostatic and dispersion interactions stabilize the slipped-parallel hexafluorobenzene-benzene complex, which is the cause of the preference of the slipped-parallel orientation and the larger interaction energy of the complex compared to the benzene dimer.     

Theoretical analysis of the hydrogen bond of imidazolium C(2)-H with anions

The intermolecular interaction energies of ion pairs of imidazolium-based ionic liquids were studied by MP2/6-311G level ab initio calculations. Although the hydrogen bond between the C(2) hydrogen atom of an imidazolium cation and anion has been regarded as an important interaction in controlling the structures and physical properties of ionic liquids as in the cases of conventional hydrogen bonds, the calculations show that the nature of the C(2)-H...X interaction is considerably different from that of conventional hydrogen bonds. The interaction energies of the imidazolium cation with neighboring anions in the four crystals of ionic liquids were calculated. The size of the interaction is determined mainly by the distance between the imidazolium ring and anion. The calculated interaction energy is nearly inversely proportional to the distance, which shows that the charge-charge interaction is the dominant interaction in the attraction. The orientation of the anion relative to the C(2)-H bond does not greatly affect the size of the interaction energy. Calculated interaction energy potentials of 1,3-dimethylimidazolium tetrafluoroborate ([dmim][BF(4)]) complexes show that the C(2)-H bond does not prefer to point toward a fluorine atom of the BF(4). This shows that the C(2)-H...X hydrogen bond is not essential for the attraction.     

Experimental and theoretical determination of the accurate CH/π interaction energies in benzene-alkane clusters: correlation between interaction energy and polarizability

The CH/π interaction energies in benzene-alkane model clusters were precisely determined by laser spectroscopy and theoretical calculations. Two-color resonant two-photon ionization spectroscopy was employed to experimentally determine the interaction energies with isomer selectivity. High precision ab initio calculations were also performed to evaluate the CCSD(T) level interaction energies of various isomers at the basis set limit. Binary clusters of benzene with ethane, propane, n-butane, iso-butane, and cyclohexane were studied. The experimental interaction energies were well reproduced by the theoretical evaluations. The magnitude of the interaction energy clearly correlates with the average polarizability of the alkane moiety, demonstrating that the CH/π interaction energy is dominated by the dispersion interaction. On the other hand, the number of C-H groups in contact with the phenyl ring has no relation to the magnitude of the interaction energy, and it indicates that the role of the hydrogen atom in the CH/π interaction is essentially different from that in hydrogen bonds.