Dielectric polarization and polarizability of 1-pentanol+n-octane mixtures from static dielectric constant and refractive index data at 0,25 and 45°C

Static dielectric constants and refractive indices of 1-pentanol+n-octane mixtures were measured in the temperature range between 0 and 45°C. Data discussed in terms of Kirkwood correlation factor and Lorentz-Lorenz molar refractivity give information on the short range intermolecular interactions between the components. The role played by the nonpolar n-octane in the destruction of 1-pentanol oligomers is also pointed out.     

Adsorption of Carbon Dioxide on Chemically Modified High Surface Area Carbon-Based Adsorbents at High Temperature

The adsorption capacity of carbon dioxide on high surface area carbon-based adsorbents before and after chemical modification at 28°C and 300°C have been studied. The high adsorption capacity adsorbents for carbon dioxide at high temperature have been developed by introducing MgO and S–CaO–MgO on carbon-based adsorbents. Their adsorption capacities for carbon dioxide were 0.28 and 0.22 m mol/g at 300°C, 1 Bar, respectively.     

Hydrogel microspheres III. Temperature-dependent adsorption of proteins on poly-N-isopropylacrylamide hydrogel microspheres

Precipitation polymerization of N-isopropylacrylamide (NIPAM) with methylenebisacrylamide (MBAAm) in water at 70°C gave thermosensitive hydrogel microspheres. The adsorbability of proteins on the poly-NIPAM microspheres was found to depend on temperature. Below the lower critical solution temperature (LCST) of poly-NIPAM in an aqueous medium, that is, around 32°C, the microspheres hold a large amount of water inside and their surface is hydrophilic enough to suppress the adsorption of proteins. On the contrary, above 32°C, the micropheres deswell and their surface becomes hydrophobic and, consequently, susceptible to adsorption of a large amount of proteins. Proteins once adsorbed on the microspheres at a high temperature could be desorbed more or less by lowering the temperature to below 32°C. The extent of desorption at low temperatures was found to depend on the incubation time for adsorption at high temperatures.     

Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer

Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents.     

Acid and redox properties of mixed oxides prepared by calcination of chromate-containing layered double hydroxides

Layered double hydroxides (LDHs) with Mg and Al in the layers and carbonate, nitrate or chloride in the interlayer, or with Zn and Al in the layers and chloride in the interlayer, have been prepared by coprecipitation, and have been used as precursors to prepare chromate-containing LDHs. All these systems, as well as those obtained upon their calcination up to 800 °C, have been characterised by powder X-ray diffraction, FT-IR and vis-UV spectroscopies, temperature-programmed reduction (TPR), nitrogen adsorption at −196 °C for surface texture and porosity assessment, and FT-IR monitoring of pyridine adsorption for surface acidity determination. The results obtained show that the crystallinity of the chromate-containing LDH depends on the precursor used. The layered structure of the Mg, Al systems is stabilised up to 400 °C upon incorporation of chromate; however, the Zn,Al-chromate samples collapse between 200 and 300 °C, with simultaneous formation of ZnO. Calcination of the samples above 400 °C gives rise to a reduction of Cr(VI) to Cr(III), as concluded from vis-UV spectroscopic studies. The TPR profiles show that chromate in ZnAl hydrotalcite is more easily reduced than that incorporated in the magnesium ones. Moderately strong surface Lewis acid sites exist in all samples calcined below 500 °C.     

Molecular association ofn-alcohols in nonpolar solvents. excess volumes and viscosities ofn-pentanol+n-octane mixtures at 0, 5, 25, 35 and 45°C

Densities and viscosities of n-pentanol +n-octane mixtures in the temperature range 0 to 45°C are reported. The data are discussed in terms of molar excess volumes, molar excess fluidities and molar excess activation energies of viscous flow in order to obtain structural information of the mixtures. It is shown that the structural modifications of n-pentanol and n-octane upon mixing, significantly contribute to the parameters governing the viscous flow and the volume of the mixtures.     

Kinetic Parameters of the Dissolution of Gold in Thiourea Solutions

The temperature dependence of the rate constants for the dissolution of gold in thiourea solutions was determined. The activation energies calculated suggest that the rate of gold dissolution is diffusion-controlled at 5-22 °C but is kinetically-controlled at 25-60 °C (E _a = 42.83 kJ/mol). Auger spectroscopy was used to study the composition of the surface adsorption layers and a mechanism for the passivation of the reactive surface during the gold dissolution process was proposed.     

Cooperativity in the adsorption of cellulose ethers and fibrinogen at liquid-solid interfaces

The possibility of reducing fibrinogen adsorption to solid surfaces by competitive adsorption of cellulose ethers (EHEC, HEC) was investigated. The surface concentration of fibrinogen adsorbed onto hydrophilic and hydrophobic (methylized) glass was measured with an enzyme-linked immunosorbent assay. The immunoassay was calibrated by ellipsometry, using the initial mass transport limitation of adsorption for calculations of the maximum amount of adsorbed protein.At a hydrophobic surface, the presence of cellulose polymers caused a decrease of the adsorption of fibrinogen. The hydrophobic EHEC (cloud point 35°C) was most efficient and abolished surface-adsorption of the protein.At a hydrophilic surface, positive cooperativity was seen between fibrinogen and cellulose polymers. The hydrophilic HEC (cloud point >100°C) gave the most prominent effect.The results indicate that the affinity between a water soluble polymer or protein and a solid surface is not the only factor determining surface adsorption. The finding that there may be both positive and negative cooperativity in the adsorption of polymers shows the importance of polymer compatibility in layers of adsorbed polymers.     

Modification of the Quartz Surface by the Adsorption of a Cationic Polyelectrolyte

A capillary electrokinetics method is applied to measure the electrokinetic potential of the surface of quartz capillaries during the continuous flow of the aqueous solutions of a cationic polyelectrolyte (PE). At a low polymer concentration (10^–5 g/l), the adsorption is determined mainly by the electrostatic forces and its kinetics, by the conformational rearrangement of adsorbed macromolecules. As the concentration of PE increases, the charge of quartz surface reverses; and further adsorption is due to the forces of hydrophobic and molecular attraction between macromolecules. The adsorption energy is estimated for this case. The charge reversal of the surface is associated with the presence of adsorption sites of two different types. At a low concentration of PE, the adsorption takes place on negatively charged sites of quartz surface. At higher concentrations of PE, after the neutralization of the surface, the adsorbed PE molecules become new adsorption sites, and the adsorption acquires two-layer character. After adsorption, the quartz surface is hydrophobized: the contact angle measured by the bubble method is close to 33°–34°.     

Entropy of transfer of n-nitroalkanes from n-octane to water at 25°C

Entropy of transfer of nitromethane, nitroethane, 1-nitrobutane, 1-nitropentane, and 1-nitrohexane from n-octane to water at 25°C is calculated using an electrostatic model. The calculations indicate that the electrostatic transfer entropy depends primarily on the dipole moment and the size of the-C–NO₂ group, showing a trend which is similar to that previously found for the transfer free energy of the same process.     

Temperature and pH dual-responsive coatings of oligoperoxide-graft-poly(N-isopropylacrylamide): Wettability, morphology, and protein adsorption

Poly(N-isopropylacrylamide) (PNIPAM) coatings attached to glass with novel approach involving polymerization from oligoperoxide grafted to surface with (3-aminopropyl)triethoxysilane exhibit not only temperature- but also pH-dependence of wettability and protein adsorption. Wettability and composition of coatings, fabricated with different polymerization times, were determined using contact angle measurements and Time Of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS), respectively. Thermal response of wettability, measured between 20 and 40 °C, was prominent at pH 9 and 7 and diminished or absent at pH 5 and 3. This indicates a transition between hydrated loose coils and hydrophobic collapsed chains that is blocked at low pH. Higher surface roughness and dramatically increased adsorption of model protein (lentil lectin labeled with fluorescein isothiocyanate) were observed with AFM and fluorescence microscopy to occur in hydrophobic phases (at pH 3, for pH varied at constant temperature of 22 °C and at ∼33 °C, for temperature varied at constant pH 9). Protein adsorption response to pH was confirmed by TOF-SIMS and Principal Component Analysis.     

Role of Microporosity of Activated Carbons on Their Adsorption Abilities for Phenols and Dyes

The amounts of adsorption of two commercial dyes, phenol, and 4-chlorophenol from water on activated carbons were measured at 30°C. The carbons were prepared from cane (bagasse) piths and were activated by steam. The activation temperature and time were in the ranges of 750–840°C and 2 h, respectively. It was shown that the isotherm data of all four solutes could be well fitted by the Langmuir equation under the conditions studied. The adsorption capacities of the solutes were correlated with the microporosity properties of the activated carbons including micropore volume and external surface area. Finally, the adsorption characteristics of the present carbons was compared with those prepared from various agricultural wastes.     

Micellization and surface activity ofn-alkyldimethylaminopropanesulfonates in aqueous solutions

Surface tension experiments were performed on severaln-alkyldimethylaminopropanesulfonate aqueous solutions at 15°, 25°, and 35°C. The critical micellar concentrations have been obtained and the surface properties calculated. The enthalpic and entropic contributions to either micellization and adsorption processes have been discussed. The observed properties have been related to the zwitterionic character of these surfactants.     

Electrochemical Sensors for Sulfur- and Lead-Containing Gases: Effect of Nonstoichiometry of Measuring Electrodes

In accordance with the fact that the region of homogeneity of lead sulfide is two-sided, i.e. it includes compositions with both sulfur excess and lead excess relative to the stoichiometric composition, it is shown that a sensor with a Pb_{1 ±} S measuring electrode (ME) may be used for analyzing both sulfur- and lead-containing media. The general principle of operation of electrochemical sensor Me, Pb/PbCl₂–CaCl₂/Pb_{1 ±} S, is based on measuring EMF of an electrochemical circuit with a lead-conducting electrolyte at a specified sulfur vapor pressure above the reference electrode. At a fixed temperature, the cell's EMF is uniquely defined by the sulfur content on ME. The studies are done in the temperature interval 285 to 300°C where characteristics of the solid electrolyte used are optimum; its upper boundary is limited by mp of the lead reference electrode (327°). The interval of determinable concentrations of sulfur- and lead-containing gases is 10^–1 to 10^–9 vol %. If analysis is performed in a dynamic mode (in a carrier gas flow), the limiting stage is the adsorption of gas molecules on the ME surface and the sensor sensitivity increases after modifying the surface by various techniques and also due to the ME composition altering only in a surface layer. The sensor's working characteristics are affected mostly by the degree of deviation of the ME material from stoichiometry.     

Sorption of hypoiodous acid on activated carbon

In spite of good adsorption characteristics of activated carbon for molecular iodine, from water solution, problems arising due to complexity of chemistry of iodine and hydrolysis as well as influences of other relevant factors in water solutions which easily change the equilibrium concentrations toward domination of species with lower absorbability. Sorption of hypoiodus acid as predominant chemical form of iodine in neutral and weak alkaline solution within the range of micro concentrations has been studied in great details. In the experiments sorption of hypoiodous acid from water solutions on activated carbon with surface area of 1000 m²/g, under static and dynamic conditions, has been performed. Isotherms on various temperatures (25°C, 50°C, 70°C) has been obtained. Parameters of the sorption are determined and mechanism of adsorption of hypoiodous acid molecules on activated carbon has been discussed.     

Prediction of Ternary Liquid Adsorption on Solids from Binary Data

The adsorption behavior of the ternary n-hexane/n-octane/n-tetradecane mixture and the binary n-hexane/n-octane, n-octane/n-tetradecane, n-hexane/n-tetradecane mixtures on the well-characterized TA 95 activated carbon has been studied. Measured binary data at 25 degrees C are used to predict the ternary data which are compared with measured ones. With the measured binary data at 15 degrees C, a prediction of ternary data is proposed without ternary experimental support. To predict ternary data from the binary ones, a thermodynamical model combining the methods of Myers and Price and Danner is used. Copyright 2000 Academic Press.     

PMo or PW heteropoly acids supported on MCM-41 silica nanoparticles: Characterisation and FT-IR study of the adsorption of 2-butanol

Mesoporous silica, prepared in basic conditions, has been loaded (20% weight) with 12-molybdophosphoric (PMo) or 12-tungstophosphoric (PW) acid and calcined at different temperatures ranging between 250 and 550 °C. The samples have been characterised by N₂ adsorption-desorption at −196 °C, transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), UV-visible diffuse reflectance, Raman spectroscopy and temperature programmed reduction (TPR). The acidity and catalytic activity have been, respectively, examined by monitoring the adsorption of pyridine and 2-butanol by FT-IR spectroscopy. The results indicate that PW and PMo acids are highly dispersed on mesoporous silica MCM-41 spherical nanoparticles. While PMo retains its Keggin structure up to 550 °C, PW decomposes at this temperature into crystalline WO₃ and phosphorous oxides. In both cases, the morphology, hexagonal symmetry and long-range order observed for the support are preserved with calcination up to 450 °C. The Brönsted-type acid sites found in all samples, whose surface concentration decreases as the calcination temperature increases, are responsible for the selective formation of cis-butene detected upon adsorption of 2-butanol. The sample containing PW calcined at 450 °C also shows selectivity to methyl ethyl ketone.     

The Mechanism of Selective NO<Subscript>x</Subscript> Reduction by Hydrocarbons in Excess Oxygen on Oxide Catalysts: III. Adsorption Properties of the Commercial STK Catalyst

According to X-ray diffraction data, the STK catalyst is a mixture of Fe₂O₃ and Cr₂O₃. The temperature-programmed reduction spectrum exhibited two reduction peaks: one, with T _max = 250°C, corresponds to the reduction process Cr₂O₃ → CrO and the other, with T _max = 360°C, corresponds to the reduction Fe₂O₃ → Fe₃O₄. The results of thermal desorption measurements suggest that the individual adsorption of oxygen on the surface of the STK catalyst is low; in this case (according to IR-spectroscopic data), an atomic form is the main species. Surface nitrite-nitrate complexes are formed upon the adsorption of NO. Nitrite and nitrate complexes desorbed at maximum rates at 105 and 160°C, respectively. Unlike the NTK-10-1 catalyst, the NO species, which desorbed at high temperatures (250–400°C), was absent from the surface of STK. Propane adsorbed at room temperature to form surface compounds containing an acetate group. The interaction of propane with the surface of the STK catalyst at reaction temperatures resulted in strong surface reduction.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 550–558.Original Russian Text Copyright © 2005 by Tret’yakov, Burdeinaya, Zakorchevnaya, Matyshak, Korchak.     

Static and Kinetic Studies on the Adsorption Behavior of Sulfadiazene

To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10^–3 mol cm^–3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl^–, SO^2– ₄ and PO^3– ₄ (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.     

Effect of the Sulfate Sulfur Content and the Preparation Procedure on the Catalytic Properties of Sulfated Zirconium Oxide

The effects of the composition and the procedure of preparing sulfated zirconium oxides on their catalytic properties in the reactions of 1-butene isomerization to 2-butenes and isobutanol dehydration were studied. The activity was found to depend on the nature of parent zirconium oxide, the sulfate sulfur content, and the temperature of calcination. Catalysts prepared from a crystalline oxide exhibited the highest activity. Their activity depends on the sulfate sulfur content. The calcination of catalysts at temperatures higher than 400°C resulted in a detectable loss of sulfate. The activity of sulfated oxides prepared from an amorphous oxide was noticeably lower; it depended only slightly on the temperature of calcination and sulfate sulfur content. The catalytic behavior of the sulfated oxide in both of the reactions is indicative of the absence of superstrong proton sites. Based on the results, assumptions on the nature of formed surface compounds were made.