气体流动热量计和苯、苯-环己烷气体热容的测量

随着化学热力学理论研究的深入和石化工业的迅速发展,混合物热力学性质的实测数据日显短缺.气体热容的测量一直为人们所重视,先后出现了各种各样的测量方法,其中以流动量热法最突出,发展也较完善.对于混合气体热容的测量,国际上尽管有一些文献报导,但由于没有解决好稳定混合气流的产生问题,测量对象仅为一些沸点相近的二元物系,且测量温度不高,很难推广到多元物系乃至不定组成物系如石油馏分的测量.本文依据Powers等人热量计和Clarke 快速蒸发器的设计原理,从结构上进行了一些改进.并将两者有机地结合起来,建立了一套可在中、低压下测量各种气体热容的金属量热装置.     

Influences of Temperature and Coal Particle Size on the Flash Pyrolysis of Coal in a Fast-entrained Bed

IntroductionCoal is the major primary energy source in China,which accounts for about three quarters of the total en-ergy consumption.Most of coal in China contains a rel-atively high content of volatile substances.The reserveof lignite accounts for about…     

2,5‐Dihydro‐1H‐imidazole‐Based Nitroxides as Prospective Mediators in Living Radical Polymerization

A number of spectroscopic methods were applied to obtain kinetic parameters of reactions modelling the 2,5‐dihydro‐1H‐imidazole 1‐oxide mediated living polymerization of acrylates. The homolysis rate constants of alkoxyamines based on five nitroxides were measured by EPR spectroscopy at different temperatures. The recombination rate constants k_c between the corresponding alkyl radicals and the nitroxides were measured by means of laser flash photolysis. The time‐resolved chemically induced dynamic nuclear polarization (TR‐CIDNP) experiments revealed the negligible contribution of disproportionation in the recombination reaction. In addition, the thermodecomposition of alkoxyamines in the NMR probe showed the absence of intramolecular elimination of hydroxylamines from the corresponding alkoxyamines. Analysis of the kinetic parameters showed that the 2,5‐dihydro‐1H‐imidazole 1‐oxide type radicals are promising mediators for the living polymerization of acrylates and methacrylates.     

Synthesis of helianane, an unusual marine sesquiterpene employing ring-expansion by flash vacuum thermolysis

A total synthesis of the marine sesquiterpene helianane 1 is described involving the thermal rearrangement of the benzoxabicyclo[4.2.0]octenone 4 to generate the dienone 5 incorporating the benzoxocane ring system of 1. This dienone was converted to the key ketone 11, which on interaction with methylmagnesium iodide followed by hydrogenation of the resulting alkene 18 furnished helianane 1.     

A Simple Novel Method for the Analysis of Lubricating Oil Additives by the Use of Sep-Pak Cartridges

In combination with the use of SEP-PAK cartridges and computerized difference infrared spectroscopic technique, a simple novel method for analyzing lubricating oil additives was developed. The present method involves solvent extraction and the use of SEP-PAK C₁₈ for separating polar additives from residual base oil, followed by the use of SEP-PAK Silica for further elution. With the aid of infrared data station, components of the polar additives were identified. The present method is definitely much more rapid and efficient than the conventional column separation method, and the separation efficiency of this simple method is comparable to that of using flash chromatographic technique.     

基于Flash的虚拟物理实验室的设计方法

在Flash中,可以借助组件技术构建功能完备的虚拟仪器,再通过虚拟仪器的有机组合,并辅以复杂计算模式所复现的实验现象以及虚拟现实技术,就能够形成高质量的虚拟实验室,这是利用Flash开发虚拟物理实验室的最有效途径．     

A robust negative flash based on a parameterization of the tie-line field

We propose a novel approach to flash calculation, with particular application to negative flash. The basis of the method is a parameterization of the tie-line field. Rather than solving the Rachford–Rice equation (or any of its variants) we solve directly for the parameters defining the tie line. For an N  -component system, our approach leads to a system of N−2$N-2$quadratic equations, which we solve efficiently using a Newton method. The iterative method is very robust: unlike other negative flash procedures, the solution displays continuous dependence on the overall composition, even in the transition to negative concentrations. We illustrate the properties and behavior of the proposed approach on three-component and four-component systems, and we then generalize the method to systems of N components. From the global triangular structure of the system with constant K-values, it follows that the system of N⁻² quadratic equations can only have two roots. For the important case of three components, the flash calculation is explicit.     

Effects of nano nickel powders addition on flash pyrolysis of poly(ethylene glycol)

Pure PEG and the mixture of PEG and nano nickel powders (PEG/n-Ni) were pyrolyzed at 500 °C for 5 min in N₂ atmosphere. GC/MS and FTIR were employed to detect the volatile products. Some important regularity in the mass spectra of the PEG pyrolysis products was discovered, and 11 series of PEG pyrolysis products were identified. The experimental results show that the nano Ni powders evidently change the relative contents of each products series. The statistical results of the ratio of C-O cleavage to C-C cleavage, as well as the ratio of hydrogenation to dehydrogenation, indicate that nano Ni powders have remarkable effects on the bonds cleavage and free radicals annihilation. The process of hydrogenolysis and hydrogenation were propounded to explain the effects of nano Ni addition on PEG flash pyrolysis.     

Gas chromatography-mass spectrometry analysis of volatile compounds from Houttuynia cordata Thunb after extraction by solid-phase microextraction, flash evaporation and steam distillation

Various sampling techniques including flash evaporation (FE), headspace solid-phase microextraction (HS-SPME) and steam distillation (SD) were compared for the gas chromatography-mass spectrometry of volatile constituents present in Houttuynia cordata Thunb (HCT). 2-Undecanone (22.21%) and houttuynum (7.23%) were predominant components of HCT samples obtained by HS-SPME whereas those levels were 3.95 and 3.60% in the same samples by FE and 25.93 and 6.60% in those by SD, respectively. SPME with polydimethylsiloxane (PDMS) fibre was more selective and particularly efficient for the isolation of biologically active compounds and afforded a higher yield of total compounds than FE and SD. A total of 60 compounds were detected in SPME extracts. While in FE and SD extracts, the detected compounds were 41 and 51, respectively. The total amount of compounds isolated by SPME was much larger than that isolated by FE or SD. Some minor constituents were isolated by SPME, but not by SD and FE. This carries great significance because of the importance of the oil volatiles to clinical therapy. HS-SPME is a powerful tool for determining the volatile constitutes present in the TCMs.     

Sample enrichment in high speed narrow bore capillary gas chromatography

Reduction of the column diameter has proved to be a highly efficient tool to increase the speed of analysis. Unfortunately, the requirements for instrumental design with respect to sample input band width, low dead volume interfacing, and time constants of detection and registration systems are the more critical the smaller the inside diameter. Recently we reported input band widths as low as 1 ms [1] for gaseous samples at ppm concentration levels, without any preconcentration, in a study with narrow bore columns and thermal conductivity detection. In this study a simple versatile micro on-column cold trap/thermodesorption enrichment system for narrow bore columns is introduced and evaluated. The combination of considerable sample enrichment and preservation of the compatibility of the required input band width with column dimensions is critically examined. The process of thermodesorption (reinjection) which is the most critical step, is particularly emphasized. The system consists of a short aluminum coated fused silica or metal capillary with a low mass and a low cost electrical heating. Input band widths down to 1 ms are obtained without extreme demands on electrical power (300 watt). The potential of the system is illustrated with some extremely fast separations.