The Design of an Automatic System for the Gravimetric Measurement of Water Sorption

An understanding of the mechanisms by which water molecules are held within a substance or at its surface, either by physical or chemical processes, is of importance in the formulation, preparation and storage of a wide variety of substances. The traditional experimental techniques which have been used to make measurements on samples exposed to specific levels of relative humidity, (e.g. using desiccators containing saturated salt solutions), are slow, laborious, inaccurate, and provide a limited amount of data. This paper describes the conception, operation, and facilities of a new system which by employing recently developed electronic components and transducers, significantly advances the performance capability for moisture sorption analysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Thermal Characteristics,Sorption Isotherms and State Diagrams of the Freeze-Dried Pumpkin-Inulin Powders

Powders based on plant raw materials have low storage stability due to their sorption and thermal properties and generate problems during processing. Therefore, there is a need to find carrier agents to improve their storage life as well as methods to evaluate their properties during storage. Water adsorption isotherms and thermal characteristics of the pumpkin powder with various inulin additions were investigated in order to develop state diagrams. Differential scanning calorimetry (DSC) was used to obtained glass transition lines, freezing curves and maximal-freeze-concentration conditions. The glass transition lines were developed using the Gordon–Taylor model. Freezing data were modeled employing the Clausius–Clapeyron equation and its development–Chen model. The glass transition temperature of anhydrous material (Tgs) and characteristic glass transition temperature of maximum-freeze-concentration (Tg′) increased with growing inulin additions. Sorption isotherms of the powders were determined at 25 °C by the static-gravimetric method and the experimental data was modeled with four different mathematical models. The Peleg model was the most adequate to describe the sorption data of the pumpkin–inulin powders. Guggenheim-Anderson-de Boer (GAB) monolayer capacity decreased with increasing inulin concentration in the sample.     

Water sorption in poly(ammonium sulfopropylbetaines). II. Sorption isotherms

Water sorption by four amorphous acrylic and methacrylic poly(zwitterions) bearing ammonium sulfopropylbetaine side groups () was studied at a constant temperature of 23°C and over a broad range of water activity (0.14-0.90). Whatever the physical state of the hydrated polymer, glassy or viscoelastic, water diffusion is Fickian (average diffusion coefficient D?_s in the range 2-16 × 10^?8 cm² s^?1), and the sorption isotherms may be quantitatively analyzed according to the Guggenheim-Anderson-De Boer amended BET equation for multilayer sorption processes. The number of sitebound water molecules per monomeric unit is in the range 1.5–2.0, and apparently there is no great energy difference between direct site binding and indirect binding in the successive solvation layers. The polymer-water interaction parameter (?0.6 < χ Flory < 0.6) is an increasing function of the water content of the hydrated poly(zwitterions) over the whole composition range (water volume fraction < 0.5), without any clear transition from the glassy to the viscoelastic state. Clustering of water molecules (Zimm-Lundberg theory) is never observed, even at high water content. Because of the charged structure of their dipolar units, the poly(zwitterions) show a water sorption process similar to that of the corresponding poly(electrolytes) of the tetra-alkylammonium sulfonate type. © 1992 John Wiley & Sons, Inc.     

Sorption Isotherms of Aromatic Compounds in Organophilic Polymer Membranes Used in Pervaporation

The sorption isotherms of seven aromatic compounds and some mixtures of them in soft-segment elastomeric polyether-polyamide block-copolymer (PEBA) have been measured at 25 and 50°C using UV-VIS spectroscopic and gas chromatographic analysis. The solubility in PEBA depends significantly on the molecular size of the aromatic compound. Sorption coefficients have been determined. The temperature dependence of the sorption coefficient has been used to determine also the sorption enthalpy of the aromatic compounds from the aqueous solution to the polymer phase. Ternary mixtures consisting of two aromatics in dilute aqueous solution have been investigated in order to study possible synergistic solubility effects. The sorption coefficients can be used for the prediction of the permeation rate across the nonporous PEBA membrane in the so-called pervaporation process. An example is presented.     

溶液间歇结晶动力学模型的新型算法

针对溶液间歇结晶过程, 基于粒数衡算理论和ΔL定律, 借助分段归纳的研究方法, 建立了晶体粒度分布函数各阶矩量的关联式. 利用此关联式, 对文献模型中晶体粒度分布函数的二阶矩量进行替换, 并结合计算机程序设计, 可直接拟合得到结晶体系的成核和生长动力学参数, 从而为结晶动力学模型的求解建立了一种新型算法. 通过对文献报道的硝酸钾水溶液和混二甲苯溶液两组结晶数据的模拟计算, 结果发现, 运用该算法求取的结晶成核和生长动力学参数均与传统的矩量变换法的计算结果相近, 但新建算法无需预知结晶体系的总传热系数.     

Sorption of Water Vapour on Exinite Concentrates

Maceral concentrates of the exinite group, isolated from the hard coals from the Janina and Brzeszcze Mines were studied. Sorption studies in the coal-water vapour system and the concentrates maceral-water vapour system were carried out using the volumetric method (under isothermal-isobaric conditions) at 298 K, at the following relative sorbate pressures: 0.19; 0.34; 0.52; 0.70 and 0.88.The presented sorption isotherms show that the exinites isolated from coals have higher water vapour sorption capacities than the coals from which they were isolated. Their sorption capacity is closely related to the accessibility of their porous structure during the interfacial-volumetric process of water vapour interaction in the coal substance.     

Application of Thermal Analysis for Explaining the Sorption of Benzene and N-Hexane on Silicalite

The origin of kinks (steps) on sorption isotherms was examined for the sorption of benzene and n-hexane on silicalite-1. In both cases sorption revealed the existence of two different binding sites. There was no equilibrium (or a very slow one), between molecules bound at different sites. Sorption energies within particular centres display more or less wide overlapping distributions leading to a single resultant isotherm. Depending on differences in binding energies and degree of overlapping, the resulting isotherms exhibit steps (benzene) or no steps (n-hexane). In fact, the sorption isotherm of benzene being a sum of two elemental isotherms (Ω₁ and Ω₂) of different shapes is characterized by a ‘kink’, in contrast to n-hexane the elemental isotherms of which are of the same shape. This revised version was published online in July 2006 with corrections to the Cover Date.     

Residue Desulfurization: A Kinetic Model Approach

In the refining of petroleum residue, sulfur removal is an important objective to produce low sulfur fuel oil and to obtain a suitable feed for residue catalytic cracking. The increasing severity of sulfur specifications for fuels implies the optimization of heavy residue processes, which in turn requires improving knowledge on reaction mechanism. The goal of this study is to contribute to a better understanding of the reactions in the process desulfurization section and to develop a kinetic model. To carry out this, hydrotreatment pilot tests were performed on demetallized residues. The products were investigated using SEC, ¹³C NMR, liquid chromatography and elemental analyses.     

A Microcalorimetric Study of Water Vapor Sorption on Morphine Sulphate

Water vapor sorption on morphine sulphate was studied in a twin double sorption microcalorimeter at 25°C. The vapor sorption isotherm and the differential heats of sorption were determined simultaneously from dry condition to a water activity of 0.99. Two well resolved hydration steps were obtained on the sorption isotherm at water activities of 0.01 and 0.22 corresponding to the formation of dihydrate and pentahydrate of morphine sulphate. They were accompanied by constant values of the differential heats of sorption: –24 kJ mol^–1(H₂O) for the dihydrate formation and –10 kJ mol^–1(H₂O) for the pentahydrate formation.The calorimetrically obtained sorption isotherms were compared with the results of Karl Fisher titrations of morphine sulphate samples equilibrated at different water activities. The appearance of a liquid phase in the morphine sulphate at high water activities is discussed on the basis of the obtained differential heats of sorption and measured heat capacities of morphine sulphate at different water activities.This revised version was published online in November 2005 with corrections to the Cover Date.     

Sorption of small molecules in various polycarbonates and Kapton-H

Pressure-composition isotherms were determined at 20°C for CO₂ in Kapton and various substituted polycarbonates and for H₂O, Ar, N₂, CH₄, and acetone in bisphenol-A-polycarbonate. The isotherms are described by two parameters an average free energy of sorption and a width of a Gaussian distribution of free sorption energies. Within the framework of a recent model these parameters can be calculated assuming an elastic distortion of the polymer caused by the incorporation of solute atoms in preexisting holes. By comparing experimental values with predictions of the model the experimental width of the free energy distribution is only 30% smaller than the theoretical one. Functional relationships are obeyed between the sorption parameters on the one hand and glass transition temperature, average hole volume, and molecular volume of the solute on the other hand. Deviations occur for larger molecules like acetone and ethylene which are attributed to a viscoelastic distortion of the polymer. Comparing free energies of solution for the rubbery and glassy state of the polymer reveals more negative values for the glassy polymers despite their extra elastic distortion energy. This discrepancy is overcome by taking into account that the occupied volume has to be re-formed in the case of the rubbery or liquid polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 483–494, 1998     

Advances in Modeling Sorption and Diffusion of Moisture in Porous Reactive Materials

Water‐vapor‐uptake experiments were performed on a silica‐filled poly(dimethylsiloxane) (PDMS) network and modeled by using two different approaches. The data was modeled by using established methods and the model parameters were used to predict moisture uptake in a sample. The predictions are reasonably good, but not outstanding; many of the shortcomings of the modeling are discussed. A high‐fidelity modeling approach is derived and used to improve the modeling of moisture uptake and diffusion. Our modeling approach captures the physics and kinetics of diffusion and adsorption/desorption, simultaneously. It predicts uptake better than the established method; more importantly, it is also able to predict outgassing. The material used for these studies is a filled‐PDMS network; physical interpretations concerning the sorption and diffusion of moisture in this network are discussed.     

Sorption of Benzene in CoAlPO4-5 Molecular Sieves

The sorption isotherms of benzene in CoAlPO₄-5 at temperatures of 323–399 K were measured by the gravimetric technique. The sorption capacity and isosteric heat were estimated and interpreted on the basis of the pore topologies of the molecular sieves. The isotherms followed the typical Type-I shape, and could be well fitted with Langmuir and Dubinin-Radushkevich equations. The initial heats of sorption at zero coverage could be well explained by the surface curvature model. The isosteric heats of sorption varied with the coverage, which may suggest a shift of molecular packing manner in the sorbed phase.     

F-T合成校正综合动力学模型

考虑了烯烃、醇与酸的再吸附及其非本征效应(烯烃、醇与酸在催化剂孔道中的扩散作用、物理吸附及溶解度效应)对产物分布的影响,推导了基于详细反应机理的亚甲基插入的烷基机理F-T合成校正综合动力学模型.利用文献数据对动力学模型进行了回归,获得了与文献报道结果相一致的动力学参数.由校正动力学模型计算的烷烃、烯烃、醇与酸产物分布及烯烃比、醇烃比及酸烃比与实验数据较好地吻合.动力学计算结果表明,在铁锰催化剂上,烷烃、烯烃、醇与酸生成的反应是平行竞争反应,烯烃、醇与酸在催化剂表面的再吸附及二次反应导致产物分布偏离了ASF分布.动力学研究还表明,相同碳数的醇与酸产物在催化剂表面上再吸附及二次反应的机会比相同碳数的烯烃大.通过比较相同碳数的烯烃、醇与酸的分子体积及沸点,指出了在铁锰催化剂上,低碳数的烯烃、醇与酸的再吸附及二次反应对产物分布影响的非本征效应中,烯烃、醇与酸的扩散阻力不是主导效应.     

A Thermodynamic Model for Gas Adsorption Isotherms

In this paper based on the principle of solution thermodynamics for gas–solid equilibrium, a relation is developed to express gas adsorption isotherms. An activity coefficient model based on weight fraction of sorbate in the solid phase has been derived that well describes the behavior of various gases on different types of adsorbents. The proposed model has been evaluated and compared with four other models commonly used for gas adsorption isotherms in the literature. For 12 different systems at various isotherms for the temperature range −128 to 100°C and the pressure range 0.02 to 1219 kPa for 689 data points, the proposed model predicts equilibrium pressure with an average deviation of 5.3%, which is about half of the error obtained from other methods. The proposed model clearly outperforms other available methods such as the vacancy solution theory, the ideal adsorption solution model, and other various modified forms of the Langmuir isotherm. Unique features of the proposed model are its simplicity, generality, and accuracy over the entire pressure and temperature ranges.     

Identifying Physical and Chemical Phenomena with Gravimetric Water Sorption Analysis

The technique of gravimetric water sorption was used to identify samples which appear to interact with water as a chemical reagent. These were distinguished from those which take up moisture purely physically. In the latter case water acts as a probe which aids the characterization of the sample surfaces and their hydration states. After identifying the features in the sorption behavior which allow this distinction to be made, we drew the following conclusions: 1. Few if any of the samples investigated interact chemically with water. 2. The demonstration of chemical interaction of a sample with water and other vapors by sorption studies alone is not always straightforward. 3. Chemical interaction of water with samples appears to be relatively rare. The major problems associated with high humidity in the production, storage and handling of samples therefore seem to be due to physical rather than chemical degradation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of Sorption Processes of Selected Pesticides on Soils and Ceramic Porous Cups used For Soil Solution Sampling

Abstract

Soil sorption constants of four organochlorine (lindane, dicofol, chlorfenson and tetradifon) and three organophos-phorus pesticides (dimethoate, fenitrothion and methidathion) were measured using two different soils at six concentrations.

Soil samples were collected at depths of 0-20 cm and around 100 cm from an experimental citrus crop field. Effects of soil properties (organic matter, moisture content, pH and texture) on the sorption processes were also investigated.

Partitioning of pesticides between soil and solution was investigated after batch equilibration, using pesticide concentrations ranging from 10 to 200 μg1^?1. The equilibration time was estimated in 2 h for organochlorine, and 72 h for organophosphorus pesticides. Data fitted to Freundlich types adsorption isotherms.

Analytical determinations were carried out by gas chromatography with ECD and NPD detectors, after liquid-liquid extraction with dichloromethane of the water supernatant.

Moreover, a validation of the use of suction samplers used to collect soil solution samples from the vadose zone, based on a short term study in the laboratory was determined.     

阻抑动力学光度法测定水中微量的银

研究了银阻抑高碘酸钾氧化玫瑰桃红R的褪色反应，建立了阻抑动力学光度法测定痕量银的新方法。找到了最佳试验条件，该方法线性范围为0～2．0μg／mL，应用于水中银的测定，结果满意。     

Calorimetric Studies and Structural Aspects of Ionic Liquids in Designing Sorption Materials for Thermal Energy Storage

The thermal properties of a series of twenty‐four ionic liquids (ILs) have been determined by isothermal titration calorimetry (ITC) with the aim of simulating processes involving water sorption. For eleven water‐free ILs, the molecular structures have been determined by X‐ray crystallography in the solid state, which have been used to derive the molecular volumes of the ionic components of the ILs. Moreover, the structures reveal a high prevalence of hydrogen bonding in these compounds. A relationship between the molecular volumes and the experimentally determined energies of dilution could be established. The highest energies of dilution observed in this series were obtained for the acetate‐based ILs, which underlines their potential as working fluids in sorption‐based thermal energy storage systems.     

Adsorption of Malachite Green by Diatomite: Equilibrium Isotherms and Kinetic Studies

The utilization of diatomite as potential adsorbent to remove malachite green (MG) from aqueous solution was developed. The characterization of the diatomite was evaluated by scanning electron microscope (SEM) and Brurauer Emmerr Teller (BET). The operating variables of pH, diatomite mass, initial MG concentration, and adsorption reaction time were studied. The equilibrium, kinetics, and thermodynamic parameters were investigated as well. It was found that the diatomite was composed of integral and almost circle sieve tray with lots of small pores on it, which afforded the diatomite high specific surface area of 46.09 m² g^?1. The optimum pH and reaction time were 7 and 90 minutes, respectively. The MG removal increased accordingly as the diatomite mass increased. The isotherm results showed that the equilibrium data were fitted to Langmuir model better, indicating the MG adsorption was better characterized by mono-layer. The maximum mono-layer capacity obtained from Langmuir was 23.64 mg g^?1 at 25°C. The kinetic studies indicated that experiment data followed pseudo-second-order model better. It also revealed that intraparticle diffusion was not the only rate-controlling step. The thermodynamic results concluded that the adsorption process was endothermic and more favorable at high temperature. Researches confirmed the applicability of diatomite as an efficient adsorbent and low-cost process to remove hazardous materials.     

非等温反应过程中新的动力学方程

对于非等温过程中的动力学方程，正确的Arrhenius方程的温度积分应该是从T₂到T₁，但是许多动力学方程中的温度积分是从T到0 K，例如Ozawa等方程。我们的研究指出对于某些反应，这些方程中的活化能存在较大的误差，因此我们提出了一个新的动力学方程。凭借等转化率法，应用新的方程可以精确求解线性或非线性加热过程中化学反应的活化能。用新方程对2个经典反应（聚酰胺的热裂解和一水草酸钙的热分解）的研究表明：Ozawa方程的活化能有时是精确的，有时偏差太大。