Determination of the vapor pressures of select polychlorinated dibenzo-p-dioxins and dibenzofurans at 75-275 °C

Vapor pressures were determined for several polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at 75-275 °C, extending the available literature data to more relevant temperature regions and providing the first experimental data for 2,3,7-trichlorodibenzo-p-dioxin (2,3,7-TriCD). A modification of the effusion technique, based upon controlling the diffusion of the target compound and subsequent high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS) analysis, was proven comparable to other accepted methods for determining the vapor pressures of semi-volatile organic compounds (SVOCs). Vapor pressures for octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) were in excellent agreement with those reported in literature. The application of the current method for the vapor pressure determinations of eight polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) in the extended temperature range (up to 275 °C) is reported. The extension of the vapor pressures to such temperatures, unprecedented for the PCDDs/Fs, is important for vapor-particle partitioning modeling in regions relevant to PCDD/F formation and control. Estimates for the melting temperatures and enthalpies of sublimation and vaporization are also reported, the latter for which no experimentally determined values have been found in the literature. The use of the method to deliver reproducible, trace concentrations (ppt-ppb) of targets was applied to the calibration of the jet-REMPI/TOFMS as an online detector for low chlorinated PCDDs/Fs.     

喷射式气,液反应器在空气—水系统中的传质特性

在对喷射式气、液反应器中复杂的流动行为进行简化和假定的基础上,导得了传质模型,并以空气-水系统进行实验研究。用光电毛细管法测定喷射管内气泡平均直径 d_(32)和比表面积 a,用氮气解吸水中溶解氧的方法获得体积传质系数 k_La,以确定传质模型中的有关参数。实验获得如下结果:α=9.18×10~2β~(0.74)e~(0.372),k_Lα=0.7206β~(0.88)e~(0.492)。其结果与理论分析较接近,可作为喷射式气、液反应器设计参数。     

固态物料超临界CO2萃取过程的传质研究

影响固态物料超临界CO2 萃取过程传质效率的因素很多 ,本文以菊花为原料 ,研究了原料的预处理方式、超临界CO2 流量、固态被萃取物粒径、被萃取物的装填方式等因素对传质效率的影响 ,结果表明 ,降低被萃取物粒径 ,增大超临界CO2 流体的流量 ,改变被萃取物的形状 ,降低原料的自然堆积密度、在塔内采用流体再分布器等措施可以明显提高超临界CO2 流体萃取固态物料的传质效率     

Packed-microtubes model for flowthrough chromatography of protein

A mathematical model for flowthrough (perfusion) chromatography, namely packed-microtubes (PMT) model, has been proposed for a column packed with biporous (BiP) anion exchanger in which the mesopores and flowthrough pores are created with liquid and solid porogens, respectively. The model is established based on the assumption that the BiP particle is made up of packed microtubes. Bovine serum albumin (BSA) is used as a model protein and three kinds of anion exchangers (i.e., mesoporous, macroporous and BiP resins) are used as adsorbents to determine the model parameters and to evaluate the model. Adsorption equilibrium and finite bath experiments are performed to determine the adsorption isotherms and kinetics parameters. Both the bound amounts of the protein on the surface of the mesopores and macropores are experimentally determined and taken into account in the mathematical model. With all the model parameters determined by independent experiments or calculated from available correlations, model simulations are performed and compared with the experimentally determined breakthrough profiles of the BiP column. It is found that the model predictions agree reasonably well with the experimental data obtained under various conditions and the PMT model fit experimental data better than the modified double linear driving force (LLDF) model proposed by Leitão and Rodriogues (1999. Biochemical Engineering Journal 3, 131) in which the adsorbent particle is considered to be made up of packed microparticles. The results indicate that the PMT model is more reasonable for this kind of BiP adsorbent.     

An adaptive neural control scheme for articulatory synthesis of CV sequences

Reproducing the smooth vocal tract trajectories is critical for high quality articulatory speech synthesis. This paper presents an adaptive neural control scheme for such a task using fuzzy logic and neural networks. The control scheme estimates motor commands from trajectories of flesh-points on selected articulators. These motor commands are then used to reproduce the trajectories of the underlying articulators in a 2nd order dynamical system. Initial experiments show that the control scheme is able to manipulate the mass-spring based elastic tract walls in a 2-dimensional articulatory synthesizer and to realize efficient speech motor control. The proposed controller achieves high accuracy during on-line tracking of the lips, the tongue, and the jaw in the simulation of consonant–vowel sequences. It also offers salient features such as generality and adaptability for future developments of control models in articulatory synthesis.     

Use of cascade reduction potential for selective precipitation of Au,Cu, and Pb in hydrochloric acid solution

Optimization of reduction potential for electroseparation was studied for the recovery of gold, copper, and lead from acidic solution. A linear sweep voltammetric method enabled us to determine characteristic reduction potentials for each metal and the kinetics of the metal deposition indicated by current-voltage curves. In order to precipitate the metal species sequentially, reduction potentials were examined for the individual and mixed solutions of Au(III), Cu(II), and Pb(II). The three metals were reasonably well isolated from the mixed solutions such as Cu(II)/ Pb(II) and Au(III)/Cu(II)/Pb(II) in the order of the corresponding reduction potentials, in particular, the mass transfer controlled reduction potentials, obtained from linear sweep voltammetry (LSV) measurement.     

Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

应用质谱扫描测定胸腺肽相对分子质量

目的 精确测定胸腺肽相对分子质量分布。方法 采用质谱扫描法。结果 3批胸腺肽相对分子质量均在2000～4000,无10 000以上的大分子蛋白。结论 本方法灵敏度高,可直观地测定胸腺肽相对分子质量分布状况,为控制胸腺肽质量提供了新的检测方法。     

THE ROLE OF INTERFACIAL PHENOMENA IN A LIQUID-LIQUID REACTION SYSTEM: EXTRACTION OF PROPANOIC ACID BY TRIOCTYLAMINE

The kinetics of extraction of propanoic acid from water to isobulanol by reaction with trioctylamine have been investigated. Mass transfer was modelled by extending the approach used in absorption with chemical reaction, as it is usually done for liquid-liquid reactions. The presence of the amine, however, gave rise to phenomena that cause this method to fail, producing inconsistent results. In order to explain these data, the presence of relevant interfacial phenomena must be supposed.     

Simultaneous measurement of gas hold-up and mass transfer coefficient by tracer dynamic technique in “Emulsair” reactor with an emulsion-venturi distributor

Hydrodynamics and gas-liquid mass transfer have been investigated in an “Emulsair” reactor with cocurrent downflow of gas and liquid. This consists of a cylindrical tank with conical bottom topped by an emulsion-venturi as the gas-liquid distributor in which the gas is self-aspired by action of the kinetic energy of the liquid recirculation. An original tracer dynamic technique using the CO₂-N₂/water system that enables the simultaneous measurement of overall gas hold-up and overall volumetric mass transfer coefficient has been developed and validated using conventional techniques, such as volume expansion for gas hold-up and dynamic oxygenation for mass transfer. It has been shown that gas hold-up and K_La_L can be deduced from the moments of experimental response curves using a CO₂ pulse in the gas feed. Experimental results have proved that hydrodynamics and mass transfer in the Emulsair reactor are strongly influenced by the flow regime in the divergent. Two different regimes have been observed depending on the liquid recirculation flow rate: annular and homogeneous bubbling flows. In both regimes, self-aspired gas flow rate, gas hold-up and K_La_L have been reported to increase with the liquid flow rate. The operation effectiveness, estimated from the gas-to-liquid flow rate ratio, has been shown to pass through a maximum around 0.59 as a function of liquid recirculation. A comparison with the literature proved that this maximum is higher than those observed for other kinds of gas-liquid reactors equipped with a venturi. Correlations for mass transfer estimation have been derived and are in agreement with the literature.