Effect of the flow rate on the measurement of adsorption data by dynamic frontal analysis

The adsorption data of propyl benzoate were acquired by frontal analysis (FA) on a Symmetry-C18 column, using a mixture of methanol (65%, v/v) and water as the mobile phase, at three different flow rates, 0.5, 1.0 and 2.0 mL/min. The exact flow rates Fv were measured by collecting the mobile phase in volumetric glasses (deltaFv / Fv < or = 0.2%). The extra-column volumes and the column hold-up volume were accurately measured at each flow rate by tracer injections. The detailed effect of the flow rate on the value of the amount adsorbed was investigated. The best isotherm model accounting for the adsorption data was the same BET isotherm model at all three flow rates. Only slight differences (always less than 5%) were found between the three different sets of isotherm parameters (saturation capacity, q(s), equilibrium constant on the adsorbent, b(s) and equilibrium constant on successive layers of propyl benzoate, bL). The reproducibility of the same isotherm parameters measured by the inverse method (IM) is less satisfactory, leading to R.S.D.s of up to 10%. A flow rate increase is systematically accompanied by a slight increase of the amount adsorbed. This phenomenon is consistent with the influence of the pressure on the equilibrium constant of adsorption due to the difference between the partial molar volumes of the solute and the adsorbate. The larger average pressure along the column that is required to achieve a larger flow rate causes a larger amount of solute to be adsorbed on the column at equilibrium. This result comforts the high sensitivity and versatility of the FA method for isotherm determination under any kind of situation.     

Partition of supercritical n-pentane into SE-54 and SE-30 stationary phases in capillary supercritical fluid chromatography

Summary The mass spectrometric tracer pulse (MSTP) chromatography method was used to measure the amount of supercritical n-pentane dissolved or adsorbed into SE-54 and SE-30 capillary columns. Partition data were measured above the critical point of n-pentane at temperatures from 200 ° to 300 °C and pressures between 35.04 and 54.42 atm. The data obtained provide evidence for mobile fluid solubility or adsorption into the stationary phase under the conditions of supercritical fluid chromatography (SFC). At 220 °C, solubility and/or adsorption of supercritical n-pentane decreases by increasing the pressure and reaches a minimum at approximately 45.00 atm. The effect of mobile-fluid pressure on its solubility or adsorption becomes limited at temperatures over 260 °C. This study demonstrates the unique experimental capabilities of the MSTPC method for quantitative measurement of the physico-chemical interaction of the complex multicomponent system encountered in SFC which is not possible by any other technique. An innovative instrumental design for modification of GC/MS systems for SFC, GC/MS operation is also described.

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Verteilung von superkritischem n-Pentan in den stationären Phasen SE-54 und SE-30 bei der Capillar-Chromatographie mit superkritischen fluiden Phasen

     

Adsorption mechanism of polylysine on hydroxyapatite and its effect on dissolution properties of hydroxyapatite

Adsorbed amounts of poly-l-lysine (pLys) and bromide ion on hydroxyapatite (HAp) from aqueous solutions of poly-l-lysine hydrobromide, and amounts of calcium and phosphate ions liberated concurrently from HAp during the adsorption of pLys were determined at 25 degrees . The pLys was adsorbed on HAp by the mechanism of ion-exchange between its amino groups and calcium ions of HAp. The released amount of calcium ion increased, therefore, with the adsorbed amount of pLys. On the other hand, the released amount of phosphate ion first decreased and then increased after attaining a minimum with the equilibrium concentration of pLys. The analysis using an equilibrium dialysis method revealed that the released phosphate ions were mainly in the bound state to the amino groups of pLys remaining in the solution, and that the concentrations of calcium and phosphate ions free from both HAp and pLys were restricted by each other under the law of the solubility product of HAp. The first decrease in the released amount of phosphate ion was concluded to be attributed primarily to the increase in the released amount of calcium ion because pLys remaining in the solution was little in this region. When sodium hydroxide was added to the solution, the adsorbed amount of pLys increased and then slightly decreased with the equilibrium pH of the solution due to the increase or decrease of the electrostatic attractive force between the adsorbate and the adsorbent. However, conformational change in pLys around pH 10 seemed to have little effect on the adsorption.     

Hydrogen capacity of palladium-loaded carbon materials

Several samples of palladium-loaded single-wall carbon nanotubes and palladium-loaded MAXSORB activated carbon were prepared by means of the reaction of the raw carbon support with Pd2(dba)3.CHCl3. When carbon nanotubes were used as the support, the palladium content in the samples reached 13-31 wt % and fine particles of 5-7 nm average size were obtained. In the case of the samples with MAXSORB as the support, the palladium content was higher (30-50 wt %) and the particle size larger (32-42 nm) than in the nanotube samples. At 1 atm and room temperature, the hydrogen capacity of the palladium-loaded samples exceeds 0.1 wt % and is much higher than the capacity of the raw carbon supports (less than 0.01 wt %). The maximum hydrogen capacity at 1 atm and room temperature was found to be 0.5 wt %. A maximum hydrogen capacity of 0.7 wt % was obtained at 90 bar in a palladium-loaded MAXSORB sample, while the capacities for the raw carbon nanotubes and MAXSORB at the same pressure were 0.21 and 0.42 wt %, respectively. At low pressure, it was observed that the H/Pd atomic ratios in the palladium-loaded samples were always higher than in the bulk Pd. The spillover effect is considered as a possible cause of the high H/Pd atomic ratios. On the other hand, the effect of the pressure increase on the spillover was observed to be very low at high pressure and room temperature.     

Removal of arsenious ion by calcined aluminum oxyhydroxide (boehmite)

Aluminum oxyhydroxide (boehmite, BE) shows adsorption ability of arsenious ion. In this study, we calcined BE in the temperature range 200-1150 degrees C, and examined the amount of arsenious ion adsorbed and adsorption mechanism. As a result, the adsorption amount of arsenious ion by BE calcined at 400 degrees C showed the highest value as compared with those by BE calcined at other temperatures. On the other hand, the amounts of arsenious ion adsorbed onto BE showed lower values at 200, 600, and >1000 degrees C than that by BE before calcination. The amount of surface hydroxyl group of calcined BE showed the highest value at the calcination temperature of 400 degrees C. As a result of X-ray analysis, BE showed boehmite structure at less than the calcination temperature of 300 degrees C, while BE was converted to the transitional state of aluminum oxide at more than 400 degrees C. From the result of the amount of arsenious ion adsorbed and FT-IR, it turned out that calcined BE dissociated water molecule when suspended in the water, hydroxyl group was generated on the surface, and the amount of arsenious ion adsorbed was increased because of the ion exchange of these hydroxyl groups with arsenious ions. It was clarified that an adsorbent with high adsorption ability of arsenious ion was obtained by calcination of BE.     

Adsorption behaviors of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> on zeolites JSR and Na<Subscript>n</Subscript>JSR using the GCMC simulations

The adsorption behaviors of CO₂ and CH₄ on new siliceous zeolites JSR and Na_nJSR (n = 2, 8, 16) were simulated using the Grand Canonical Monte Carlo method. The adsorption isotherms of CO₂ became higher with an increase in the Na⁺ number at a low pressure range (<150 kPa), whereas the isotherms showed a crossover with increasing pressure and the adsorption amount became smaller at a high pressure range (>850 kPa). With an increase in Na⁺ number, the pore volume decreased as the pore space was occupied by increasing Na⁺ ions. Additionally, two energy peaks on the interaction energy curves implied that CO₂ was adsorbed on two active sites. On the other hand, the adsorption amount of CH₄ decreased with an increase in the Na⁺ number and only one energy peak was observed. Adsorption isotherms were well fitted with the Langmuir and Freundlich equations up to 1000 kPa and the adsorption affinity of CO₂ on Na₁₆JSR zeolite was highest. The adsorption capacities of CO₂ in the studied zeolites were up to 38 times higher than those of CH₄. Diffusion constants of CO₂ and CH₄ decreased with an increase in the adsorbed amount and Na⁺ number. Considering the adsorbed amount, adsorption selectivity and affinity, zeolites JSR with a low Na⁺ number (JSR and Na₂JSR) is a good candidate for a pressure swing adsorption in the separation of CO₂/CH₄ mixture whereas JSR zeolites with high Na⁺ ratios (Na₁₆JSR and Na₈JSR) may be a better selection for a vacuum swing adsorption.     

Adsorption of gelatin to a polystyrene/water interface as a function of concentration, pH, and ionic strength

The technique of neutron reflection has been used to investigate the adsorption of alpha-enriched gelatin from aqueous solution onto spun polystyrene substrates. Neutron reflection can provide information about the distribution of material perpendicular to an interface as well as total adsorbed amounts. The adsorbed layers were found to have maximum density at the surface, decaying with distance into solution. The adsorbed amount, layer thickness, and density were all seen to increase with solution concentration. Temperature was found to have little effect on adsorption. Thicker, less dense layers were observed at high pH and thinner, denser layers were observed at low pH, but the total adsorbed amount did not change significantly. The presence of sodium chloride had little effect on the adsorbed layers. The results are discussed in the context of other studies and the known amino acid sequence of alpha-gelatin.     

Adsorption of cationic cellulose derivative/anionic surfactant complexes onto solid surfaces. II. Hydrophobized silica surfaces

The effect of the anionic surfactant SDS (sodium dodecyl sulfate) on the adsorption behavior of cationic hydroxyethyl cellulose (Polymer JR-400) and hydrophobically modified cationic cellulose (Quatrisoft LM-200) at hydrophobized silica has been investigated by null ellipsometry and compared with the previous data for adsorption onto hydrophilic silica surfaces. The adsorbed amount of LM-200 is found to be considerably larger than the adsorbed amount of JR-400 at both surfaces. Both polymers had higher affinity toward hydrophobized silica than to silica. The effect of SDS on polymer adsorption was studied under two different conditions: adsorption of polymer/SDS complexes from premixed solutions and addition of SDS to preadsorbed polymer layers. Association of the surfactant to the polymer seems to control the interfacial behavior, which depends on the surfactant concentration. For the JR-400/SDS complex, the adsorbed amount on hydrophobized silica started to increase progressively from much lower SDS concentrations, while the adsorbed amount on silica increased sharply only slightly below the phase separation region. For the LM-200/SDS complex, the adsorbed amounts increased progressively from very low SDS concentrations at both surfaces, and no large difference in the adsorption behavior was observed between two surfaces below the phase separation region. The complex desorbed from the surface at high SDS concentrations above the critical micelle concentration. The reversibility of the adsorption of polymer/SDS complexes upon rinsing was also investigated. When the premixed polymer/SDS solutions at high SDS concentrations (>5 mM) were diluted by adding water, the adsorbed amount increased due to the precipitation of the complex. The effect of the rinsing process on the adsorbed layer was determined by the hydrophobicity of the polymer and the surface.     

Amine functionalised metal organic frameworks (MOFs) as adsorbents for carbon dioxide

Three different porous metal organic framework (MOF) materials have been prepared with and without uncoordinated amine functionalities inside the pores. The materials have been characterized and tested as adsorbents for carbon dioxide. At 298 K the materials adsorb significant amount of carbon dioxide, the amine functionalised adsorbents having the highest CO₂ adsorption capacities, the best adsorbing around 14 wt% CO₂ at 1.0 atm CO₂ pressure. At 25 atm CO₂ pressure, up to 60 wt% CO₂ can be adsorbed. At high pressures the CO₂ uptake is mostly dependent on the available surface area and pore volume of the material in question. For one of the iso-structural MOF pairs the introduction of amine functionality increases the differential adsorption enthalpy (from isosteric method) from 30 to around 50 kJ/mole at low CO₂ pressures, while the adsorption enthalpies reach the same level at increase pressures. The high pressure experimental results indicate that MOF based solid adsorbents can have a potential for use in pressure swing adsorption of carbon dioxide at elevated pressures.     

Pressure effect on positronium reactions in organic solutions

The reaction rate constants of positronium (Ps) atoms with a series of nitrobenzene derivatives and nitromethane in toluene solutions have been determined as a function of external pressure up to 1000 kg cm⁻² (about 1000 atm). The rate constants for relatively weak Ps acceptors such as p-nitroanisole, 1,3-dimethyl-2-nitrobenzene and nitromethane increased considerably with external pressure, while those for relatively strong Ps acceptors like p-dinitrobenzene or nitrobenzene either decreased or changed little with external pressure. Comparison of the experimental results on pressure effects with those on temperature effects revealed that the application of external pressure suppresses the thermal decomposition of Ps complexes which are unstable at room temperature. The effect on a solvent of the Ps reaction was also studied by determining the reactivities of Ps atoms with nitrobenzene in various solvents as a function of external pressure.     

Molecular Dynamics Simulation of Methane Hydrate Decomposition in the Presence of Alcohol Additives

The decomposition process of methane hydrate in pure water and methanol aqueous solution was studied by molecular dynamics simulation. The effects of temperature and pressure on hydrate structure and decomposition rate are discussed. The results show that decreasing pressure and increasing temperature can significantly enhance the decomposition rate of hydrate. After adding a small amount of methanol molecules, bubbles with a diameter of about 2 nm are formed, and the methanol molecules are mainly distributed at the gas-liquid interface, which greatly accelerates the decomposition rate and gas-liquid separation efficiency. The radial distribution function and sequence parameter analysis show that the water molecules of the undecomposed hydrate with ordered ice-like configuration at a temperature of 275 K evolve gradually into a long-range disordered liquid structure in the dynamic relaxation process. It was found that at temperatures above 280 K and pressures between 10 atm and 100 atm, the pressure has no significant effect on hydrate decomposition rate, but when the pressure is reduced to 1 atm, the decomposition rate increases sharply. These findings provided a theoretical insight for the industrial exploitation of hydrates.     

RBM band shift-evidenced dispersion mechanism of single-wall carbon nanotube bundles with NaDDBS

The dispersion process of single-wall carbon nanotube (SWNT) by using sodium dodecylbenzene sulfonate (NaDDBS) was studied by means of surface tension measurements, ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), and transmission electron spectroscopy (TEM). The critical micelle concentration (CMC) and the concentration where the surface tension begins to drop increase by the presence of SWNT. The isotherm of NaDDBS amount adsorbed on SWNT shows the plateau region at 0.2-6 mM and the saturated region above 40 mM. The external surface of SWNT bundle is fully covered with adsorbed NaDDBS at the plateau region, showing that SWNTs can be dispersed with the bundle form. On the other hand, SWNTs are dispersed in individual tubes at the saturated region, where the adsorption amount corresponds to coating of individual tube surfaces with NaDDBS. This dispersion state was confirmed by SEM and TEM observations. The effect of the dispersion state of SWNTs on radial breathing mode in Raman spectrum gave inherent peak shifts, being the in situ evidences on the step-wise dispersion mechanism of the SWNT bundle to the individual tubes.     

Investigation of adsorbed polymer layers by flocculation of oppositely charged sols III. Effect of molecular mass of polymers

The stabilizing effect of water-soluble neutral polymers with different chemical structure and relative molecular mass on AgI sol has been studied. It was shown that the stabilizing effect of the polymers used is independent of the relative molecular mass of the polymer when equal amounts of the adsorbed polymers are compared with each other as stabilizers. The high stabilizing effect of polymers with high relative molecular mass is presumably due to the larger adsorbed amount.Among polyvinyl alcohol, polyvinyl pyrrolidone and methylcellulose, polyvinyl pyrrolidone exhibits the smallest stabilizing layer thickness at equal adsorbed amounts. According to our earlier results this is due to the fact that the polyvinyl pyrrolidone shows the strongest affinity for AgI surfaces, forming short loops or tails.     

Effect of pressure on the luminescence of a series of methoxy phenylacetylene dendrimers neat and in dilute solution in solid poly(tert‐butyl methacrylate)

The effect of pressure up to 60 kbar was measured on the luminescence peak location and efficiency for a series of methoxy phenylacetylene dendrimers (MeO). Dendrimers MeO‐3, MeO‐7, MeO‐15, MeO‐31, MeO‐63, and MeO‐127 were studied as neat polymers. MeO‐3, MeO‐15, MeO‐63, and MeO‐127 were also investigated in dilute solutions in poly(tert‐butyl methacrylate). According to measurements of the dilute solutions, there is a charge‐transfer (CT) state that, for the smaller dendrimers, lies well above the π* state; for the larger dendrimers, it is the emitting state at 1 atm. With increasing pressure, the intramolecular CT state is rapidly stabilized, so that at high pressure the emission is from this state for all dendrimers. For the neat polymers, there is an initial redshift that reverses direction at a pressure that is higher for smaller dendrimers. This reversal is attributed to intermolecular CT. There may be changes in the molecular geometry and/or relative orientation of adjacent dendrimers that tend to stabilize the intermolecular CT in the solid state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2859–2865, 2001     

Headgroup effects of template monolayers on the adsorption behavior and conformation of glucose oxidase adsorbed at air/liquid interfaces

Stearic acid (SA) and octadecylamine (ODA) monolayers at the air/liquid interface were used as template layers to adsorb glucose oxidase (GOx) from aqueous solution. The effect of the template monolayers on the adsorption behavior of GOx was studied in terms of the variation of surface pressure, the evolution of surface morphology observed by BAM and AFM, and the conformation of adsorbed GOx. The results show that the presence of a template monolayer can enhance the adsorption rate of GOx; furthermore, ODA has a higher ability, compared to SA, to adsorb GOx, which is attributed to the electrostatic attractive interaction between ODA and GOx. For adsorption performed on a bare surface or on an SA monolayer, the surface pressure approaches an equilibrium value (ca. 8 mN/m) after 2 to 3 h of adsorption and remains nearly constant in the following adsorption process. For the adsorption on an ODA monolayer, the surface pressure will increase further 1 to 2 h after approaching the first equilibrium pressure, which is termed the second adsorption stage. The measurement of circular dichroism (CD) spectroscopy indicates that the Langmuir-Blodgett films of adsorbed GOx transferred at the first equilibrium state (π = 8 mN/m) have mainly a β-sheet conformation, which is independent of the type of template monolayers. However, the ODA/GOx LB film transferred at the second adsorption stage has mainly an α-helix conformation. It is concluded that the specific interaction between ODA and GOx not only leads to a higher adsorption rate and adsorbed amount of GOx but also induces a conformation change in adsorbed GOx from β-sheet to α-helix. The present results indicate that is possible to control the conformation of adsorbed protein by selecting the appropriate template monolayer.     

BINARY COMPETITIVE AND COOPERATIVE ADSORPTION OF AROMATIC COMPOUNDS ON POLYMERIC RESINS

The adsorption behaviors of 2-naphthalenesulfonic acid and aniline on a conventional macroporous resin Amberlite XAD4 and the other two newly-developed hypercrosslinked resins NDA101 and NDA100 were investigated in a single or binary batch system at 293 K and 313 K,respectively.All the adsorption isotherms of 2-naphthalenesulfonic acid and aniline on the test resins in both systems can fit well with the Langmuir equation,indicating that the adsorption is a favorable process.At the identical equilibrium concentration,the amount of aniline adsorbed on polymeric resins in the single system is higher than that in the binary system because of the competitive adsorption between 2-naphthalenesulfonic acid and aniline on the resin surface.However,the uptake amount of 2-naphthalenesulfonic acid in the binary system is markedly larger than that in the single system,which is presumably due to the cooperative effect arisen from the electrostatic interaction between 2-naphthalenesulfonic acid and aniline adsorbed on the resin surface.The simultaneous adsorption system was proven to be helpful for the selective adsorption toward 2-naphthalenesulfonic acid due to its larger selective index.     

烷烃混合物在Cu-BTC中的吸附与分离

用巨正则系综Monte Carlo (GCMC)和构型导向Monte Carlo (CBMC)相结合的方法模拟了298 K下甲烷-乙烷-丙烷体系以及正丁烷-异丁烷体系在1,3,5-苯三甲酸铜(II) (Cu-BTC)中的吸附行为. 结果表明, Cu-BTC对丙烷以及异丁烷的吸附分离都有较好的选择性. 通过我们发展的“材料剖面成像”方法研究了烷烃混合物在Cu-BTC中不同压力下的吸附位点, 从而进一步分析了烷烃混合物在Cu-BTC中的分离性能. 结果发现, 在吸附过程中主要存在着两种效应, 即能量效应和尺寸效应的竞争. 在甲烷-乙烷-丙烷体系中, 较高压力下, 由于尺寸效应的影响, 丙烷主要吸附在主孔道中, 而对甲烷和乙烷组分, 能量效应占主导地位, 从而导致乙烷主要吸附在四面体孔内, 甲烷则主要吸附在三角形孔窗外. 在正丁烷-异丁烷体系中, 能量效应起主导作用, 从而使异丁烷主要吸附在四面体孔内, 而正丁烷主要吸附在主孔道中.     

Pressure and temperature dependence of hydrophobic hydration: volumetric, compressibility, and thermodynamic signatures

The combined effect of pressure and temperature on hydrophobic hydration of a nonpolar methanelike solute is investigated by extensive simulations in the TIP4P model of water. Using test-particle insertion techniques, free energies of hydration under a range of pressures from 1 to 3000 atm are computed at eight temperatures ranging from 278.15 to 368.15 K. Corresponding enthalpy, entropy, and heat capacity accompanying the hydration process are estimated from the temperature dependence of the free energies. Partial molar and excess volumes calculated using pressure derivatives of the simulated free energies are consistent with those determined by direct volume simulations; but direct volume determination offers more reliable estimates for compressibility. At 298.15 K, partial molar and excess isothermal compressibilities of methane are negative at 1 atm. Partial molar and excess adiabatic (isentropic) compressibilities are estimated to be also negative under the same conditions. But partial molar and excess isothermal compressibilities are positive at high pressures, with a crossover from negative to positive compressibility at approximately 100-1000 atm. This trend is consistent with experiments on aliphatic amino acids and pressure-unfolded states of proteins. For the range of pressures simulated, hydration heat capacity exhibits little pressure dependence, also in apparent agreement with experiment. When pressure is raised at constant room temperature, hydration free energy increases while its entropic component remains essentially constant. Thus, the increasing unfavorability of hydration under raised pressure is seen as largely an enthalpic effect. Ramifications of the findings of the authors for biopolymer conformational transitions are discussed.     

水/硅胶吸附体系的热化学研究

我们用精密自动绝热量热计测定了几种不同吸附水含量的水/硅胶吸附体系在200～320 K温度范围内的热容. 结果表明, 当吸附水含量使表面复盖度(θ)大于1时, 在相应的C_p～T曲线上会出现吸附水的相变峰. 这说明吸附在硅胶表面上的水分子已经形成了聚集态; 而当θ<1时, 由于尚未形成聚集态水, 故没有相变过程出现, 其C_p～T曲线呈光滑状. 这些现象与H_2O/γ-Al_2O_3吸附体系是一致的. 又由于硅胶表面对水分子的吸附力较γ-Al_2O_3的要小, 故在同样的吸附量的C_p～T曲线上, 水/硅胶的峰要比H_2O/γ-Al_2O_3的尖锐, 且蜂温增高的速度要快. 这些都表明, 吸附在硅胶表面上的二维表相水会随吸附量的增加而以较快的趋势接近于体相水. 此外, 由不同含水量的C_p～T曲线外推, 求出了不含吸附水的硅胶在200～300 K范围内的热容.     

Electrochemical oxidation of glucose at Hg adatom-modified Au electrode in alkaline aqueous solution

Electrochemical oxidation of glucose at Hg adatom-modified Au polycrystalline electrode was examined in alkaline aqueous solutions using cyclic voltammetry. Two oxidation current peaks for glucose were observed on Hg adatom-modified Au electrode at almost the same potentials as those observed on a bare Au electrode. The oxidation peak currents were much larger than those on a bare Au electrode in the concentration range from 0.5 to 20 mM. The observed enhancement of the glucose oxidation was considered to be due to the increase in the amount of the adsorbed OH⁻ on the Hg adatom-modified Au electrode. The reaction was catalyzed through the pairing of glucose and the intermediate in the oxidation to the large amount of the adsorbed OH⁻ on the Hg adatom-modified Au electrode.