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.     

利用ADCP回波强度估算河流悬移质含沙量的应用研究

通过简要介绍利用声学多普勒水流剖面仪(ADCP)回波强度估算悬移质含沙量的基本原理,结合梧州水文站的应用实例,利用ADCP的回波强度数据和现场采集的水样含沙量建立相关关系,根据相关关系由回波强度反演估算的水体悬移质含沙量验证了利用ADCP的回波强度估算悬移质含沙量的可行性。应用于梧州水文站的实践表明,左河道推算的系统误差为-0.1%,右河道推算的系统误差为1.5%。这种方法具有不扰动流场、测量剖面同步性较好、数据空间分辨率较高的优点,与传统的取样过滤称量法相比,计算效率显著提高。     

森林植被改善对鄱阳湖流域径流和输沙过程的影响

以河流基流为切入点,研究流域植被调节径流、水土保持等微观作用影响大中型河流湖泊径流过程和水沙过程宏观效应的机理。鄱阳湖流域60年来天然降水没有发生趋势性变化。流域森林覆盖率由34.73%上升到63.00%,植被质量改善,赣江等入湖河流基流增加83 m~3/s,河流输沙量减少。2000年以后和2000年以前相比较,枯水期降水径流系数增大,年流量过程平坦化,一定程度上减小洪灾风险,有利于水资源利用和生态环境保护。2001年以后进入鄱阳湖泥沙平均每年减少1 007×10~4t;出湖泥沙增加314×10~4t。因此,鄱阳湖入江水道由淤积转变为冲刷,但出湖流量过程没有趋势性变化。     

Selective gas transport in miscible PPO-PS blends

The permeation rates of He, CO₂ and CH₄ though miscible blends of polystyrene and poly(phenylene oxide) at 35°C are reported as a function of pressure. Sorption isotherms for CO₂ and CH₄ are also presented. By using ratios of the permeabilities of the pure gases the separation factors for the gas pairs He---CH₄ and CO₂---CH₄ can be estimated. For both pairs the estimated separation factor goes through a prominent maximum, thus indicating that these blends are more permselective than expected from the behaviour of polystyrene and poly(phenylene oxide). This stems from mobility considerations rather than solubility effects and a qualitative free volume argument is proposed as an explanation. The sorption and transport data have been interpreted and correlated using the dual sorption-mobility models developed previously for glassy polymers. Since the commercial polystyrene used contained a small amount of mineral oil to improve flow behaviour, the effect of this additive on polystyrene properties was explored in some detail.     

Influence of silicon on the growth of barrier-type anodic films on titanium

Amorphous anodic titania, stabilised by incorporation of silicon species, is shown to grow to high voltages on sputter-deposited, single-phase Ti-Si alloys during anodizing at a constant current density in ammonium pentaborate electrolyte. The films comprise two main layers, with silicon species confined to the inner layers. An amorphous-to-crystalline transition occurs at ∼60 V on the Ti-6 at.% Si alloy, while the transition is suppressed to voltages above 140 V on alloys with 12 and 26 at.% silicon. The crystalline oxide, nucleated at a depth of ∼40% of the film thickness, is associated with the presence of a precursor of crystalline oxide in the pre-existing air-formed oxide. The modified structure of the air-formed oxide due to increased incorporation of silicon species suppresses the amorphous-to-crystalline transition until the onset of dielectric breakdown. The transport numbers of cations and anions during growth of the anodic oxides are independent of the concentration of silicon species in the inner layer, despite the marked change in the field strength.     

EFFECTS OF ASYMMETRIC TEMPERATURE PROFILES ON THERMAL CONVECTION DURING PHYSICAL VAPOR TRANSPORT OF Hg2Cl2

Asymmetric horizontal thermal profiles can change the flow field structure in the physical vapor transport (PVT)of Hg₂Cl₂. It is found that for the ratios of horizontal to vertical thermal Rayleigh numbers Ra_H/Ra ≥ 1·5, the convetive flow structure changes from multicellular to unicellular for the base parametric state of Ra = 2·79 × 10⁴, Pr = 0·91, Le=l·01. Pe = 4·60, Ar= 0·2 and C_r = 1·01. The unicellular flow structure obtained by increasing ∇*_H(Ra_H) is not likely to support the conjecture of the presence of unicellular convective mode in the laser Doppler velocimetry (LDV) experiments for PVT process of Hg₂Cl₂ (Kim el al., 1996). When the six parameters of Ra, Pr, Le, Pe, Ar and C_r are fixed, the dimensional maximum magnitude of the velocity vector |U|_max is proportional to √∇T*_H.     

An analytical framework for integrated maritime terminal scheduling problems with time windows

Container transport, an integral part of intercontinental trade, has steadily increased over the past few decades. The productivity of such a system, in part, hinges on the efficient allocation of terminal resources such that the container transit time is minimized. This study provides an analytical framework, which entails efficient scheduling of quay and yard cranes, to minimize the time spent by containers at a terminal. A mixed-integer programming model is developed to capture the two-stage multi-processor characteristic of the problem, where each crane has specific time window availability. A genetic algorithm equipped with a novel decoding procedure is developed. The mixed-integer model is tested on a number of problem instances of varying sizes to gain managerial insights.     

Separation of kinetics and mass-transfer in a batch alkoxylation reaction

The quantitative aspects of the role of interfacial mass-transfer and reaction kinetics in ethoxylation of lauryl alcohol were examined in a batch recirculation reactor. The liquid droplets falling through a gas column were obtained by utilizing a recirculation loop and a set of spray nozzles. The CO₂/NaOH reaction was employed to characterize the interfacial area. The alkoxylation reaction was studied at temperatures between 124°C and 171°C, at catalyst levels between 0.09 and 0.50 weight percent and at ethylene oxide partial pressures between 68 kPa and 204 kPa. A model was developed which permits the prediction of reactor performance at various operating conditions. The mass-transfer during free fall dominates the interfacial mass-transfer and the contributions during the drop formation and coalescence stages are small. The rate of ethylene oxide (EO) addition to lauryl alcohol was constant during the batch run, indicating similar activity for the unreacted lauryl alcohol and the lauryl alcohol ethoxylated to varying extents. The rate of ethoxylation is first-order in both catalyst and ethylene oxide concentrations. The liquid-phase reaction kinetics and interfacial mass-transfer occur in series, with kinetics dominating the overall ethoxylation rate. As expected, an increasing role of mass transfer is observed at higher temperatures, and/or higher catalyst concentrations where the kinetic rate becomes significantly high. The intrinsic activation energy for the ethoxylation of lauryl alcohol is 55.2 kJ/mole.     

Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004