A New Formulation of the Lindemann Mechanism of Unimolecular Reactions

A new formulation of the Lindemann mechanism of unimolecular reactions in gaseous phase is presented, without the use of steady state hypothesis. It is hereby shown that the nature of applicability of steady state hypothesis in the regime of high reactant gas pressure is different from that in the regime of low gas pressure. In the former case it is an equilibrium approximation, while in the latter case it is a highly reactive intermediate approximation in no connection with a steady state. Furthermore for the latter case it is shown that in the classical formulation of Lindemann mecbRnism the use of steady state hypothesis is an ad hoc assumption. A highly reactive intermediate in the sense that its concentration is very small during the whole course of reaction is a necessary condition for the applicability of very reactive intermediate approximation. When the two distinctive nature of the applicability of steady state hypothesis is mlxed-up, wrong or useless conclusion may be arrived at. The only possible case of realizing a true steady state in a complex reaction is pointed out.     

取向非晶态聚对苯二甲酸乙二酯(PET)膜的结晶

采用小角和广角X-散射法比较了未拉和热拉PET膜在结晶性能方面的差别,热拉试样在分子链段的小尺度范围内基本上是无规取向,而在分子链的大尺度范围内却是高度取向的。研究结果表明:热拉PET膜的结晶诱导期较短,长周期发展得较快,结晶后小角X-线散射表现出明显的各向异性,在热处理过程中先出现显著的热收缩,随后又表现出结晶伸长现象,这些都和未拉试样有明显的差别。     

聚丙烯分子量分布的一种简易流变性质表征法

<正> 分子量分布是聚丙烯的一个重要参数,它对纺丝过程中的织构形成、卷绕丝的不均匀性和牵伸性能都有很大的影响,但是它的表征和测量却不容易。目前最常见的方法是用凝胶透过色谱法(GPC)测量试样的分子量分布曲线,并用其重均与数均分子量之比(D=(?)_w/(?)_n)作为分子量分布宽窄的表征量。可是聚丙烯的高温GPC测定需要昂贵的设备和细致的实验技巧,由于难于精确测量高分子量尾端的含量等实验技术上的原因,     

聚N-乙烯基丁内酰胺的分子量测定

聚N-乙烯基丁内酰胺的特性粘数-分子量关系,已有许多作者研究过,如表1.但是从一个试样25°±0.02时在水溶液中测得的[η]=19.9毫升/克,用表1中式(3),(4),(5),(6)计算所得分别是(3.19,2.17,4.27,3.08)×10~4,有相当的分歧,作为血浆填充剂的应用,分子量值有重要的意义,因此对这样一种试样进行了超速离心沉降和扩散的研究。     

真空浇铸聚苯乙烯薄膜的拉伸力学行为

高分子溶液的浓度从极稀到极浓的转变过程是高分子链从单链体系转变成相互穿透的多链体系的分子凝聚过程 .在极稀溶液中高分子链以无规线团状态孤立地存在于溶剂介质中 ;在良溶剂中是溶涨的无规线团 ,可以设想溶液浓度逐渐增大时 ,有一高分子线团开始相互接触的所谓接触浓度 ;随着浓度进一步增加高分子线团之间就发生交叠而相互穿透 ,这时溶液就转变成物理交联结构的浓溶液 .分子链的互穿程度会随浓度的继续增加而增加 .如果能用一些特殊的实验方法将高分子在不同浓度的溶液中的凝聚状态尽量全部或部分的保留到高分子固体中 ,则所得到的具有…     

聚甲基丙烯酸甲酯混合溶剂体系Ⅲ.——在苯-庚烷中的偶极矩

带有极性侧基的高分子链,其偶极矩的计算与末端距的计算极为相似。高分子链的均方末端距值受链段间的远程相互作用和链段与溶剂分子间的相互作用(溶剂化)影响甚大,因     

VOLT-AMPERE CHARACTERISTICS OF CIS-POLY(PHENYL ACETYLENE)

The volt-ampere (Ⅰ-Ⅴ) characteristics of the c/s-poly (phenyl acetylene) (PPA) of cis-transoidal structure has been studied in the temperature range of 253-288K. An ITO/ PPA/ Au sandwich configuration was used for the measurements. Under an applied field of less than 10~5V/ cm it showed ohmic behavior, while the space charge limited current (SCLC) was observed at applied fields above 5×10~5V/ cm. In the ohmic region a conductivity of 1.37×10~(-16)S/ cm was obtained at room temperature with an activation energy of 0.5eV. These data indicate that the conduction is not intrinsic one but is the result of thermal release of trapped carriers. In fact the data in the SCLC region treated according to the theory for a single Gaussian distribution of traps gave a mean trap energy of 0.48 eV with a half-width of 0.4 eV and a total density of trapping states of 5×10~(16)/cm~3.     

低苯乙烯含量的丁二烯-苯乙烯共聚物的激基缔合物荧光研究

本文报导一种低苯乙烯含量(5％,Wt.)的丁二烯-苯乙烯共聚物,经~1H NMR证明其分子链上不存在相邻苯乙烯单元。荧光光谱结果表明,它在良溶剂(二氯乙烷)的稀溶液状态下只呈现单分子荧光。从良溶剂-θ溶剂(二氯乙烷-甲醇体系)及稀溶液-浓溶液-固体之荧光光谱的变化,证明形成了链内非近邻生色团之间和链间生色团之间的激基缔合物(Excimer)。从固体与θ溶剂的激基缔合物荧光的比较,还可区分链内非近邻和链间苯环形成激基缔合物对荧光强度的贡献。这一结果对阐明高分子链内非近邻和链间激基缔合作用提供了新的证据,并有助于了解高聚物本体中相互穿透、相互缠结的无规线团的形态。     

有机固体中载流子陷阱的表征

有机固体包括有机分子晶体、非晶态有机固体、有机高聚物等.在有机固体中保持单个分子的特性,如吸收光谱;分子间的范德瓦耳斯相互作用能比较小,即使是单晶体,也容易产生结构欠序和杂质、晶界等缺陷.这些缺陷使电子价带与导带间的禁区中出现局域能级,导带的载流子(电子)或价带的载流子(空穴)会被局域于这些杂质或缺陷的附近,出现电荷存储现象,影响稳态和瞬态电导下的载流子输运,导致暗导的非欧姆性、载流子迁移率的下降、光导衰减时间大于光激发载流子的寿命等.多年来,这些一直被固体的电导和光导研究者所重视[1-6],并称这些局域能级为陷阱.…     

聚酰胺6的红外光谱

根据对聚酰胺类高聚物红外光谱的类比和对聚酰胺6试样进行氘化和碘处理后红外光谱的改变,以及根据对拉伸过的聚酰胺6薄膜试样的偏振红外光谱的观察,我们对聚酰胺6红外光谱中400cm^-1—1400cm^-1之间的主要吸收带,作了如下解释:1370cm^-1吸收带为ν_(cщN);1265cm^-1和1205cm^-1吸收带为δ_N-H+ν_(cщN)(酰胺Ⅲ);1170cm^-1吸收带为ν_(cN);730cm^-1吸收带为γ_(CH2)[当(CH₂)_n的n≥4时];690cm^-1吸收带为δ_N-H(面外);580cm^-1吸收带亦为δ_N-H(面外)。