中国几种典型农田土壤磷素固液相分配规律

土壤养分、污染物的生物有效性与其固液相分配规律密切相关。本研究通过室内模拟试验,设置不同的水、热、肥条件和培养时间序列,采用高速离心法对红壤、黑土、潮土、黑垆土、塿土5种典型土壤的磷素固液相分配规律及其影响因素进行了探讨。结果表明,质地不同土壤磷素固液相分配系数(Kd)值差别很大,整体变化趋势是红壤>黑垆土>塿土>黑土>潮土。不同培养条件下土壤磷素固液相分配系数(Kd)值变化特征表现出随着培养时间延长,土壤磷素Kd值增大,土壤磷素生物有效性逐渐降低。水吸力、浓度与之相反,随着水吸力的增加土壤磷素Kd值变小,随着施入磷素浓度的增加而Kd值降低。在整个温度梯度中,当温度处于20￣25℃左右时,土壤磷素Kd值达到最小值,液相磷素含量相对增多,养分有效性增强。

电荷在液/液界面上的转移反应

针对目前液/液界面电分析化学存在的问题,从三方面研究了电荷在液/液界面上的转移反应.主要结果如下：1将含有氧化还原电对的水相支撑在铂盘电极表面,倒置后插入到有机相中,与参比电极和对电子极构成常规的三电极系统,实现了液/液界面上的电荷转移反应.2应用电化学方法详细探讨了中性载体加速离子在微、纳米管支撑的微、纳米级-水/1,2-二氯乙烷界面上转移反应的机理、热力学和动力学.3研究了手性联萘冠醚与手性酪氨酸在微、纳米管支撑的微、纳米级-水/1,2-二氯乙烷界面上的选择性络合过程的势力学和动力学.研究结果表明R型冠醚易于与D-酪氨酸络合.

微纳米级液/液界面间离子转移反应的研究

液／液界面通常被看作是人工膜和生物膜的简单模型，液界面电分析化学的主要研究对象是界面上的电荷（电子和离子）转移反应以及伴随发生的相关化学反应。本论文简要回顾了液/液界面电分析化学的发展历程，介绍了液/液界面上电分析化学的基本理论。目前，应用扫描电化学显微镜结合微、纳米电极技术研究液/液界面上的电荷转移反应是电分析化学领域的研究热点之一。本文在本实验室以往研究工作的基础上，将扫描电化学显微镜、微、纳米管技术和各种电化学方法相结合，一方面进一步深入研究了在可极化液/液界面上、高驱动力作用下的加速离子转移反应的动力学，另一方面探讨了支持电解质浓度对简单及加速离子在低离子强度溶液相间的转移反应的影响。主要结果如下：1．通过选择适当的研究模型（二苯基18冠6加速Na+、Li+在水1/2-二氯乙烷界面上的转移反应）、实验条件及将三电极系统、纳米管与扫描电化学显微镜相结合，进一步研究了加速离子转移反应的驱动力与异相反应速率常数之间的关系。由实验得到，加速离子转移反应的速率常数匆与反应驱动力直接相关。在低驱动力区，Inkf与驱动力的关系遵循经典的Butier～Voh“方程；高马时力区，反应的动力学逐渐进入Marcus翻转区，即反应的速率常数随驱动力的增加而减小，此与Marcus 理论相一致。本实验是第一次在加速离子转移反应中观察到Marcus翻转现象。2．应用循环伏安法、方波法、计时安培法和微/纳米管技术研究了加速钾离子从水相向高阻抗有泪毛相转移的反应。同时系统讨论了低浓度电解质对水相及有机相TMA~+简单离子转移反应的影响。实验中绷门发现纳米管可被用子有机相无外加支持电解质的加速离子转移反应的研究。而在含少量或不含电解质的两相间的TMA+离子转移反应中，可以清楚的观察到迁移在TMA+转移过程中所起的作用。另外也较详细讨论了简单离子在界面转移的机理。

固液黏着功的Berthelot平均规则的推广及应用

以固液黏着功的Berthelot几何平均规则及其推广为基础的Zisman方程、Fowkes方程和Owens-Wendt方程是固体表面张力测定的基础.对Berthelot几何平均规则进行了进一步的推广,并以此为基础,对Zisman方程中的参数给出了推广的表示式,并对Fowkes方程和Owens-Wendt方程进行了进一步的推广.

Thermal analysis of microstructural evolution of Al2O3 surface modified layers

Solidification behavior and microstructural evolution of surface modified layers in plasma cladding technique are studied via numerical simulations. Both the coupling effect of temperature and solid volume fraction are considered in the proposed thermal analytical model, by which the transient temperature distributions are calculated and the shape of melting pool is determined. Furthermore, we perform microscopic thermal analysis on the nucleation and growth behaviors of ceramic hardening phases and dendrites, as well as the kinetics of related two-phase flow systems. By comparing with experimental observations, the evolution mechanisms of the morphology of Al2O3 ceramic hardening layer are explained. Based on the above results, a relationship among the scanning velocity of plasma stream, dendritic growth rate and the advancing speed of solid/liquid interface is found, and an energy criterion is proposed for predicting the pushing/engulfing transition of ceramic particles by grain growth fronts. (C) 2009 Elsevier B.V. All rights reserved.

Thermodynamic investigation on properties of gasohol

The heat capacities (C-p) of three types of gasohol (which consisted of 20 wt % ethanol and 80 wt % unleaded gasoline 93(#) (system S1), 30 wt % ethanol and 70 wt % unleaded gasoline 931 (system S2), 40 wt % ethanol and 60 wt % unleaded gasoline 930 (system S3), where "93(#)" denotes the octane number) were measured by adiabatic calorimetry in the temperature range of 80320 K. A glass transition was observed at 94.24, 95.15, and 95.44 K for system S1, S2, and S3, respectively. A solid-solid phase transition and solid-liquid phase transition were observed at 135.18 and 151.30 K for system S1, 131.82 and 152.10 K for system S2, and 121.29 and 155.09 K for S3, respectively. The polynomial equations for C, with respect to the thermodynamic temperature (T), and with respect to the content of ethanol (x), were established through the least-squares fitting. The thermodynamic functions and the excess thermodynamic functions of the three samples were derived using these thermodynamic relationships and equations.

Low-temperature heat capacities and derived thermodynamic functions of cyclohexane

The low-temperature heat capacities of cyclohexane were measured in the temperature range from 78 to 350 K by means of an automatic adiabatic calorimeter equipped with a new sample container adapted to measure heat capacities of liquids. The sample container was described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on water. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.3%, while the inaccuracy is within +/-0.4%, compared with the reference data in the whole experimental temperature range. Two kinds of phase transitions were found at 186.065 and 279.684 K corresponding solid-solid and solid-liquid phase transitions, respectively. The entropy and enthalpy of the phase transition, as well as the thermodynamic functions {H-(T)- H-298.15 K} and {S-(T)-S-298.15 K}, were derived from the heat capacity data. The mass fraction purity of cyclohexane sample used in the present calorimetric study was determined to be 99.9965% by fraction melting approach.

Heat capacities and thermodynamic properties of chrysanthemic acid

The heat capacities of chrysanthemic acid in the temperature range from 80 to 400 K were measured with a precise automatic adiabatic calorimeter. The chrysanthemic acid sample was prepared with the purity of 0.9855 mole fraction. A solid-liquid fusion phase transition was observed in the experimental temperature range. The melting point, T-m, enthalpy and entropy of fusion, Delta(fus)H(m), Delta(fus)S(m), were determined to be 390.741 +/- 0.002 K, 14.51 +/- 0.13 kJ mol(-1), 37.13 +/- 0.34 J mol(-1) K-1, respectively. The thermodynamic functions of chrysanthemic acid, H-(T)-H-(298.15), S-(T)-S-(298.15) and G((T))-G((298.15)) were reported with a temperature interval of 5 K. The TG analysis under the heating rate of 10 K min(-1) confirmed that the thermal decomposition of the sample starts at ca. 410 K and terminates at ca. 471 K. The maximum decomposition rate was obtained at 466 K. The purity of the sample was determined by a fractional melting method.

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

Low-temperature heat capacities of the 9-fluorenemethanol (C14H12O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T = 78 K and T = 390 K. The solid-liquid phase transition of the compound has been observed to be T-fus = (376.567 +/- 0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Delta(fus)H(m) = (26.273 +/- 0.013) kJ (.) mol(-1) and Delta(fus)S(m) = (69.770 +/- 0.035) J (.) K-1 (.) mol(-1). The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Delta(c)U(C14H12O, s) = -(7125.56 +/- 4.62) kJ (.) mol(-1) and Delta(c)H(m)degrees(C14H12O, s) = -(7131.76 +/- 4.62) kJ (.) mol(-1), by means of a homemade precision oxygen-bomb combustion calorimeter at T = (298.15 +/- 0.001) K. The standard molar enthalpy of formation of the compound has been derived, Delta(f)H(m)degrees (C14H12O, s) = -(92.36 +/- 0.97) kJ (.) mol(-1), from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle. (C) 2004 Elsevier Ltd. All rights reserved.

Thermodynamic investigation of the azeotropic mixture composed of water and benzene

The molar heat capacity of the azeotropic mixture composed of water and benzene was measured by an adiabatic calorimeter in the temperature range from 80 to 320 K. The phase transitions took place in the temperature range from 265.409 to 275.165 K and 275.165 to 279.399 K. The phase transition temperatures were determined to be 272.945 and 278.339 K, which were corresponding to the solid-liquid phase transitions of water and benzene, respectively. The thermodynamic functions and the excess thermodynamic functions of the mixture relative to standard temperature 298.15 K were derived from the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.

Low-temperature heat capacity and thermodynamic properties of crystalline 2-chloro-5-trichloromethylpyridine

The low-temperature heat capacities of 2-chloro-5-trichloromethylpyridine were measured with a high-precision automated adiabatic calorimeter in the temperature range from 80 K to 345 K. A solid-liquid phase transition was observed from 318.57 K to 327.44 K with peak temperature 324.67 K; the molar enthalpy and entropy of phase transition, DeltaH(m) and DeltaS(m), were determined to be 14.50 +/-0.02 kJ mol(-1) and 44.66 +/- 0.07 kJ K-1 mol(-1), respectively. The thermal stability was investigated through thermogravimetric analysis (TG). The TG and DTG results reveal that 2-chloro-5-trichloromethylpyridine starts to lose mass at 332 K due to evaporation and completely changes into vapour at 483 K under the present experimental conditions.

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

Investigation of facilitated ion-transfer reactions at high driving force by scanning electrochemical Microscopy

The kinetics of facilitated ion-transfer (FIT) reactions at high driving force across the water/1,2-dichloroethane (W/DCE) interface is investigated by scanning electrochemical microscopy (SECM). The transfers of lithium and sodium ions facilitated by dibenzo-18-crown-6 (DB18C6) across the polarized W/DCE interface are chosen as model systems because they have the largest potential range that can be controlled externally. By selecting the appropriate ratios of the reactant concentrations (Kr c(M)+/c(DB18C6)) and using nanopipets as the SECM tips, we obtained a series of rate constants (k(f)) at various driving forces (Delta(O)(W) phi(ML+)(0') - Es, Delta(O)(W) phi(ML+)(0') is the formal potential of facilitated ion transfer and Es is the potential applied externally at the substrate interface) based on a three-electrode system. The FIT rate constants k(f) are found to be dependent upon the driving force. When the driving force is low, the dependence of 1n k(f) on the driving force is linear with a transfer coefficient of about 0.3. It follows the classical Butler-Volmer theory and then reaches a maximum before it decreases again when we further increase the driving forces. This indicates that there exists an inverted region, and these behaviors have been explained by Marcus theory.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.

Studies of effect of phase volume ratio on transfer of ionizable species across the water/1,2-dichloroethane interface by a three-electrode setup

The electrochemical behavior of pyridine distribution at the water/1,2-dichloroethane interface with variable phase volume ratios (r=V-0/V-W) was investigated by cyclic voltammetry. The system was composed of an aqueous droplet supported on a Ag/AgCl disk electrode covered with an organic solution or an organic droplet supported on a Ag/AgTPBCl disk electrode covered with an aqueous solution. In this way, a conventional three-electrode potentiostat can be used to study an ionizable compound transfer process at a liquid/liquid interface with a wide range of phase volume ratios (from 0.0004 to 1 and from 1 to 2500). Using this special cell we designed, only very small volumes of both phase were needed for r equal to unity, which is very useful for the investigation of the distribution of ionizable species at a biphasic system when the available amount of species is limited. The ionic partition diagrams were obtained for different phase volume ratios.