吸附剂性能和操作参数对液相色谱流出峰不对称性的影响

色谱流出峰的拖尾现象普遍存在于制备和大型色谱分离过程中,它直接影响分离的产率和回收率．本文提出采用色谱流出峰形的不对称偏差度来表征色谱流出峰的拖尾程度;并基于液相制备色谱分离过程FAD－SMT模型及吸附速率理论,通过计算机模拟,定量分析了吸附剂性能和操作参数对色谱流出峰形不对称性的影响。结果表明：不仅是吸附剂的热力学和动力学性能（包括吸附相平衡关系、液固两相间的传质阻力）;而且柱的设计和吸附剂的装填状况（包括轴向扩散系数）,以及色谱分离的操作条件（进料时间、浓度和流速等）都直接影响色谱流出峰形的不对称性。随着吸附相平衡等温线的非线性程度增大,或者总传质系数的减小,色谱流出峰形的不对称偏差度明显增大;吸附剂吸附容量的减小也将引起色谱流出峰形的不对称偏差度的增加;色谱流出峰形的不对称偏差度与进科体积、浓度和流体线速,以及轴向扩散系数的增大成正比。     

液相制备吸附色谱流出峰对称性的若干影响因素

在色谱分离连续性方程和质量传递速率方程基础上,对色谱分离过程进行计算机模拟,定量分析了分离体系的热力学、动力学参数和操作条件对色谱流出峰形对称性的影响。结果表明,吸附相平衡关系、液固两相间的传质阻力及进料体积、进料浓度和流体线速等都将直接影响色谱流出峰形的对称性。流出峰形的不对称程度随着吸附等温线的非线性程度、液固两相间的传质阻力、流体线速、进料体积、进料浓度的增大而增大;在线性条件下,随着吸附剂吸附容量的减小而增大。     

液相色谱技术测定葡萄糖果糖在Ca型吸附剂上相平衡常数和总传质系数

]考虑轴向扩散的影响,导出液相色谱技术测定吸附相平衡常数和总数传质系数参数估值模型,测定葡萄糖果糖吸附相平衡常数和总传质系数,研究流速、温度对这些参数的影响。获得理论计算与色谱分离实验流出曲线相吻合结果。     

大型液相色谱分离甘露醇和山梨醇的热力学及动力学参数辨识

本文研究了液相色谱分离过程的吸附平衡常数、传质系数参数的估值模型，用色谱技术和以惰性物示踪的扰动应答实验技术测定甘露醇和山梨醇在钙型吸附剂上的吸附相平衡常数和总传质系数以及床层中的轴向扩展系数，结果表明：吸附平衡常数和吸附剂的选择性随温度的升高而下降；液固相间的总传质系数随温度的升高而增大；轴向扩散系数随流速的增大而增大，参数灵敏度分析的结果表明，相平衡关系，尤其是吸附选择性，对色谱分离的影响有较     

吸附剂性能和操作参数对流相色谱流出峰不对称性的影响

色谱流出峰的拖展现象普遍存在于制备和大型色谱分离过程中,它直接影响分离的产率和回收率。本文提出采用色谱流出峰形的不对称偏差度来表征色谱流出峰的拖尾程度,并基于液相色制备色谱分离过程ＦＡＤ－ＳＭＴ模型及吸附速率计算机模拟,定量分析了吸附剂性能和操作参数对色谱流出峰形不对称性的影响。     

连续环状色谱分离木糖—山梨糖混合溶液的研究──轴向扩散系数和总传质系数的辨识

本文提出了连续环状色谱分离过程的参数辨识方法，包括其轴向扩散系数的辨识模型，以惰性物ＣａＣｌ２作示踪剂，００１×７树脂为填料，采用扰动－应答法技术在环状色谱床中测定轴向扩散系数。考虑轴向扩散的作用，建立了线性吸附平衡体系的相平衡常数及总传质系数的辨识模型，并对木糖──山梨糖体系，采用扰动－应答技术测定相平衡常数及总传质系数。考察了操作因素对轴向扩散系数与总传质系数的影响规律。结果表明，流速增加，轴向扩散系数加大，环状色谱床中的流动明显地偏离理想活塞流；流速增加，总传质系数也相应增大。     

基于随机行走扩散模型的气相色谱分离模拟

利用粒子在受限空间内随机行走的扩散理论,构建了气相色谱毛细管柱分离的仿真模型,系统地考察了各模拟参数对粒子在色谱柱内的碰撞情况和峰宽的影响。模拟结果表明随机速度和时间步长的增加以及载气流速的降低均会加剧粒子碰撞和色谱峰展宽,而相互作用虽与碰撞行为无关,但峰宽会随着相互作用的增加而显著增大。模拟结果证实了该模型与色谱基本理论的一致性。     

胰岛素反相制备色谱的方法开发

以胰岛素反相制备色谱方法的开发和优化为目标,通过考察色谱保留参数、峰展宽及样品流出曲线的浓度分布等色谱参数,对流动相梯度、色谱填料、载样量等色谱条件进行了优化,并建立了胰岛素制备色谱峰参数的描述方法。结果表明,所建立的方法可快速筛选出最适于胰岛素分离的色谱条件(包括流动相梯度及分离填料),即流动相中的强洗脱溶剂(有机相)需采取缓梯度窄区间的变化条件,筛选出的分离填料需具备峰向两侧展宽且展宽程度较小、样品最高浓度居中分布的特点。将方法用于实际胰岛素粗品的纯化制备,获得了杂质去除效果好、胰岛素纯度高的产品。该法为胰岛素反相色谱纯化制备方法的快速建立提供了指导,具有较强的实用价值,同时为发展大分子化合物的制备色谱方法提供了参考。     

HPLC柱效对检测水中磺胺二甲基嘧啶色谱条件的影响

研究色谱柱的柱效降低后对高效液相色谱测定水中磺胺二甲基嘧啶色谱条件的影响。比较了新旧色谱柱的分离效果、色谱峰的对称性和峰面积,结果表明,旧色谱柱的柱效降低,对目标物的分离效果变差,目标物的吸收峰面积变小,峰形不对称。对色谱条件进行了优化试验,结果表明,对流动相水相添加0.125%的冰乙酸调节p H值为4.5后色谱峰的峰形对称性和分离效果得到改善。     

用非极性固定相分离不同极性化合物时色谱峰峰形的EMG参数及计算机拟合

对用非极性固定相分离不同极性的化合物时色谱峰的峰形与保留值的关系进行了研究使用非极性固定相分离不同极性的化合物时,不同极性化合物的色谱峰的EMG参数σ、τ与组分的保留值不存在线性关系：建立了使用非极性固定相分离极性化合物时色谱峰峰形的计算机模拟方法该法作为《开放式气相色谱仿真软件》中的模拟方法之一,效果较好。     

相转移催化剂对催化柴油氧化脱硫作用的数学模型

经过顺序氧化反应动力学方程、相转移催化剂强化作用数学模型方程和萃取相平衡方程的推导,确定了催化柴油氧化萃取脱硫数学模型方程。研究表明,呈指数函数形式的相转移催化剂作用数学模型具有较高的计算精度。通过模型参数估值确定了氧化速率常数的频率因子和活化能、相平衡常数、相转移催化剂作用模型参数,建立了脱硫率数学模型。模型预测显示,柴油脱硫率随着氧化时间延长呈先提高后降低的趋势;氧化时间较短时,柴油脱硫率随相转移催化剂用量提高而增大,但氧化时间较长时的情况相反;柴油脱硫率随着氧化溶液体积分数增大或萃取剂与油比增大均呈提高的趋势。     

Investigation on critical aggregation concentration of carbosiloxane dendrimer in dilute solution probed by rhodamine B

We propose a novel method for probing aggregation of dendrimers by investigating the isomerization equilibrium between pink zwitterionic form (Z-form) and colorless lactonic form (L-form) of rhodamine B (RhB) molecules in dilute solution. Investigation using carbosiloxane dendrimers (CSiO-D) with different generations as the model dendrimer molecules showed that the equilibrium constant of isomerization of RhB increased dramatically at the critical aggregation concentration (CAC) of dendrimers. The redox potential differences between isomers of RhB indicated that aggregation of CSiO-D accelerated the isomerization of RhB and stabilized the L-form of RhB. The data on Gibbs energy and electrolytic conductivity provided further evidence for confirming the CAC of dendrimers in dilute solution and showed good agreement with our other experimental results. The proposed method is effective in estimating the CAC of dendrimers in dilute solution.     

Removal of 2,4-Dichloro phenoxy acetic acid pesticide by solvent sublation: Experimental and theoretical studies

The removal of the pesticide 2, 4 D from water using solvent sublation process was investigated in this paper. A lab scale unit was set up and various experimental runs were carried out to study the efficiency of the removal process. The experimental findings show that the method is very effective (>90% removal) in removing traces (ppb level) of the pesticide which is not easily removable by simple air stripping. In addition a mathematical model was developed to describe the experimental findings. Some parameters of the model were measured or calculated while others such as the aqueous mass transfer coefficient and the solute partition coefficient were adjusted to fit the experimental data. The calibration of the model was carried out using the experimental results of change in gas flow rate (the easiest parameter to vary). A numerical sensitivity analysis was carried out using the calibrated model to study the effect of various parameters such as the bubble radius, aqueous phase drag-up by air, column radius and ratio of organic to aqueous volume phases.     

Electrolyte effect on adsorption and the phase transition from microstructures to nanostructures in ionic/ionic surfactants mixture

The effect of salt concentration on intermicellar interactions and aggregate structures of anionic and cationic-rich mixtures of CTAB (cetyltrimethylammonium bromide) and SDS (sodium dodecyl sulfate) were investigated with conductometry, surface tension, zeta potential, cyclic voltammetry measurements and by determining the surfactant NMR self-diffusion coefficients. The critical aggregate concentration (CAC), surface excess (Γ(max)), and mean molecular surface area (A(min)) were determined from plots of the surface tension (γ) as a function of the log of total surfactant concentration. The electrochemical behavior of cationic-anionic (catanionic) mixed surfactant and self-assembled surfactant monomers at Pt wire electrode were studied by cyclic voltammetry (CV). A variation in the peak current versus the total concentration of surfactant allow us to evaluate the CAC and related parameters from regular solution theory along with the diffusion coefficient of the electroactive species. It was observed that, for both the planar air/aqueous interface and micellar systems, the nonideality decreased as the amount of electrolyte in the aqueous medium was increased. Finally, we investigated the variations of electrostatic, transfer and steric free energy in phase transition between mixed micelle and vesicle in the presence of electrolyte using the presented model by our groups.     

顺丁烯二酸酐与邻苯二甲酸二甲酯二元体系在4.00, 8.00和12.00 kPa下的等压气液平衡

采用沸点仪测定了顺丁烯二酸酐和邻苯二甲酸二甲酯二元体系在4.00, 8.00和12.00 kPa下的等压气液平衡数据以及纯DMP组分饱和蒸气压数据, 将实验数据回归得到了纯DMP在417~525 K范围内的Antoine方程. 根据实验平衡温度、 压力和组成数据进一步回归得到NRTL方程参数, 推算出平衡气液相组成, 并利用UNIFAC方程对实验数据进行了预测, 其结果与沸点仪测定结果及NRTL拟合的结果基本相符.     

金属溶剂萃取的热力学研究(Ⅶ)——2-乙基己基膦酸单(2-乙基己基)酯-硫酸钻-硫酸铜体系

本文提出了具有相同电荷的同号离子间作用力相等的假定, 简化了Pitzer的电解质溶液活度系数计算公式, 用此公式, 计算了H_2SO_4-CoSO_4-CuSO_4水相体系各单个离子活度系数以及水的渗透系数。本文还应用由作者提出的工作参考态法, 应用改进的Scatchard-Hildebrand模型计算了EHEHPA-CoSO_4-CuSO_4萃取体系中有机相各组分的活度系数以及萃取反应热力学平衡常数.     

A theoretical plate model accounting for slow kinetics in chromatographic elution

The chromatographic elution has been studied from different perspectives. However, in spite of the simplicity and evident deficiencies of the plate model proposed by Martin and Synge, it has served as a basis for the characterization of columns up-to-date. This approach envisions the chromatographic column as an arbitrary number of theoretical plates, each of them consisting of identical repeating portions of mobile phase and stationary phase. Solutes partition between both phases, reaching the equilibrium. Mobile phase transference between the theoretical plates is assumed to be infinitesimally stepwise (or continuous), giving rise to the mixing of the solutions in adjacent plates. This yields an additional peak broadening, which is added to the dispersion associated to the equilibrium conditions. It is commonly assumed that when the solute concentration is sufficiently small, chromatographic elution is carried out under linear conditions, which is the case in almost all analytical applications. When the solute concentration increases above a value where the stationary phase approximates saturation (i.e. becomes overloaded), non-linear elution is obtained. In addition to overloading, another source of non-linearity can be a slow mass transfer. An extended Martin and Synge model is here proposed to include slow mass-transfer kinetics (with respect to flow rate) between the mobile phase and stationary phase. We show that there is a linear relationship between the variance and the ratio of the kinetic constants for the mass transfer in the flow direction (τ) and the mass transfer between the mobile phase and stationary phase (ν), which has been called the kinetic ratio (κ=τ/ν). The proposed model was validated with data obtained according to an approach that simulates the solute migration through the theoretical plates. An experimental approach to measure the deviation from the equilibrium conditions using the experimental peak variances and retention times at several flow rates is also proposed.     

Application of Surface Diffusion Model to the Adsorption of Dyes on Bagasse Pith

A homogeneous solid phase diffusion model (HSDM) has been developed using a computer to predict the performance of a batch adsorber. The computer program utilises a semi-analytical solution for a two resistance model based on external mass transfer and homogeneous solid phase diffusion. The model has been successfully applied to four adsorption systems, namely, the adsorption of AB25, AR114, BB69 and BR22 onto pith. The method produces excellent correlations between experimental and theoretical concentration decay curves in batch adsorbers. The model developed presents a solution using a single solid diffusion coefficient and a single external mass transfer coefficient which are sufficient to characterise the system within a range of initial dye concentration, 25–300 mg · dm3 and solid/liquid ratios (w/v) 0.25–2.     

Studies on transport mechanism of Cr(VI) extraction from an acidic solution using liquid surfactant membranes

A mathematical model for analysing the extraction of Cr(VI) from aqueous acidic solution by emulsion liquid membrane using Aliquat 336 as extractant and NaOH as stripping agent has been presented. The existing models developed so far do not account for the existence of different forms of Cr(VI) ions in the aqueous phase depending on pH conditions. Accordingly, in the present model, reaction equilibrium has been considered instead of distribution coefficient to represent realistically the transport mechanism for this type of system through liquid surfactant membrane. Unlike other models, liquid–liquid equilibrium of sodium hydroxide-chloride of Aliquat 336 has also been considered. The carrier thus exists in the membrane phase in hydroxide and chloride forms and extraction of hexavalent chromium from the external phase proceeds by the two carriers. The validity of the model has been checked from comparison of the simulated curves and experimental data using chemical reaction equilibrium constant and D_eff/R² as fitting parameters.     

Electronic factor in electron self-exchange reaction of hydrated redox ion pairs from thermodynamic data

An accurate scheme for determining the electronic factor of the electron self-exchange reaction in solution is presented in this paper. The used various activation parameters and slopes of potential energy surfaces are obtained in terms of an improved activation model and the accurate potential function determined from the vibrational spectroscopic and thermodynamic data. The coupling matrix elements are determined using numerical integral method over the perturbed double-zeta Slater-type state functions. Theoretical results of electronic factor in this work are found in close agreement with those extracted from experimental rate constant data and to be less than unity. Results indicate that outer-sphere electron transfer reactions in solution involving hydrated transition metal ions are nonadiabatic in nature.