Study of the separation of lactose,lactulose and galactose by liquid chromatography using cationic ion-exchange resin columns

Summary A strong acid cation-exchange resin, Dowex AG50W-X8 in potassium, calcium or sodium form, with water as eluent, has been used to separate three sugars (lactose, lactulose and galactose). The linearity of lactulose equilibrium isotherms was verified. Thermodynamic and kinetic parameters were thus determined by the moment method. Evaluation of the parameters revealed in this work can be considered as the first step in scaling up the process towards industrial use. On the other hand, the equilibrium stage model, which takes mass transfer resistance into account, is shown to provide a fair representation of the system’s behaviour.     

Irreversible dissociation of water molecules on the ion-exchange membrane-electrolyte solution interface in electrodialysis

The fluxes of hydrogen ions through the cation-exchange membrane and hydroxyl ions through the anion-exchange membrane in the electrodialysis were measured using the method of selective polarization. The experiments, which were conducted in a wide range of current densities, enabled us to obtain the results of ionic transport different from the literature data and to explain them on the basis of chemical reactions proceeding in the system. It is shown that a decrease in the hydration of ionogenic groups intensifies the ionic fluxes of the medium in the electrodialysis.     

Coadsorption of Cd(II) and oxalate ions at the TiO2/electrolyte solution interface

The study of the adsorptions of cadmium and oxalate ions at the titania/electrolyte interface and the changes of the electrical double layer (edl) structure in this system are presented. The adsorption of cadmium or oxalate ions was calculated from an uptake of their concentration from the solution. The concentration of Cd(II) or oxalate ions in the solution was determined by radiotracer method. For labeling the solution 14C and 115Cd isotopes were used. Coadsorption of Cd(II) and oxalic ions was determined simultaneously. Besides, the main properties of the edl, i.e., surface charge density and zeta potential were determined by potentiometer titration and electrophoresis measurements, respectively. The adsorption of cadmium ions increases with pH increase and shifts with an increase of the initial concentration of Cd(II) ions towards higher pH values. The adsorption process causes an increase of negatively charged sites on anatase and a decrease of the zeta potential with an increase of initial concentration of these ions. The adsorption of oxalate anions at the titania/electrolyte interface proceeds through the exchange with hydroxyl groups. A decrease of pH produces an increase of adsorption of oxalate ions. The processes of anion adsorption lead to increase the number of the positively charged sites at the titania surface. However, specific adsorption of bidenate ligand as oxalate on one surface hydroxyl group may form inner sphere complexes on the metal oxide surface and may overcharge the compact part of the edl. The presence of oxalate ions in the system affects the adsorption of Cd(II) ions on TiO2, increasing the adsorption at low pH range and decreasing the adsorption at high pH range. Using adsorption as a function of pH data, some characteristic parameters of adsorption envelope were calculated.     

Effect of inorganic positive ions on the adsorption of surfactant Triton X-100 at quartz/solution interface

The electrode-separated piezoelectric sensor (ESPS), an improved setup of quartz crystal microbalance (QCM), has been employed to investigate the adsorption behavior of nonionic surfactant Triton X-100 at the hydrophilic quartz-solution interface in mineralized water medium in situ, which contained CaCl2 0.01 mol·L?1, MgCl2 0.01 mol·L?1, NaCl 0.35 mol·L?1. In a large scale of surfactant concentration, the effects of Ca2 , Mg2 and Na on the adsorption isotherm and kinetics are obviously different. In aque-ous solution containing NaCl only, adsorption of Triton X-100 on quartz-solution interface is promoted, both adsorption rate and adsorption amount increase. While in mineralized water medium, multivalent positive ions Ca2 and Mg2 are firmly adsorbed on quartz-solution interface, result in the increasing of adsorption rate and adsorption amount at low concentration of surfactant and the peculiar desorption of surfactant at high concentration of Triton X-100. The results got by solution depletion method are in good agreement with which obtained by ESPS. The "bridge" and "separate" effect of inorganic positive ions on the adsorption and desorption mechanism of Triton X-100 at the quartz- solution interface is discussed with molecular dynamics simulations (MD), flame atomic absorption spectrometry (FAAS) and atomic force microscopy (AFM) methods.     

Diffusion-controlled adsorption kinetics at the air/solution interface

 To describe diffusion-controlled adsorption, the diffusion equation is solved under different initial and boundary conditions by means of a Laplace transformation. By solving this equation, it has been found that the solution, which Ward and Tordai used, is only applicable for x>0; therefore, it is incorrect if the derivation is made at x = 0. Ward and Tordai did not notice this and the first derivation was made at x = 0 in order to get the dynamic surface adsorption, Γ(t). In this paper, an accurate solution, which is applicable for x≥ 0, is given and the expression for Γ(t) is obtained. Furthermore the relationship between the dynamic surface tension and Γ(t) is derived. As an example, the dynamic surface tensions of an aqueous octyl-β-d-glucopyranosid solution were measured by means of the maximum bubble pressure method. By using the derived theory it has been proved that the controlling mechanism of the adsorption process of this surfactant at the long-time-adsorption limits changes as a function of the bulk concentration; only at dilute concentration is it controlled by diffusion. Received: 26 July 1999/Accepted in revised form: 16 September 1999     

Adsorption of methylamine at a polycrystalline gold/solution interface

Adsorptive behaviour of the methylamine molecules has been investigated by measuring changes in the differential capacitance of the double layer at the gold/solution interface by the tensammetric method. The differences in adsorption parameters at Θ < 0.8 and >0.8 have been explained by changes in arrangement of the adsorbate.     

Adsorption of procaine at the mercury/electrolyte solution interface

The adsorption of the local anaesthetic procaine hydrochloride at the mercury/electrolyte interface solution is followed using capacitance measurements. The adsorption is studied at various procaine concentrations, in potassium chloride, potassium bromide or potassium fluoride used as supporting electrolytes, and at various pH values and temperatures. Procaine has basic properties with two acidity constants K. The results indicate the way the procaine molecules orientate at the interface. In all cases studied no hemimicelles or condensed film are observed.     

Adsorption of methylmethacrylate-vinylferrocene copolymers at the solution/solid interface

A series of methylmethacrylate–vinylferrocene random copolymers was synthesized and characterized. Their adsorption from toluene and chloroform was measured onto pyrogenic silicas. The level of adsorption depended on the solvent, the surface area of the adsorbent, and the copolymer composition. Thus, an inverse adsorption-solubility relationship for toluene and chloroform was observed. However, in solvents such as tetrahydrofuran, 2-butanone, and cyclobutanone, which have strong interaction with silica, this trend was not evident. The compositional dependence of the adsorption of these copolymers in toluene and chloroform is similar. Initially, adsorption tends to increase with the vinylferrocene content in the polymer, and at equimolar copolymer compositions the adsorption reaches a maximum which is followed by a decrease in the adsorption values at high vinylferrocene contents. Gel permeation chromatography(GPC) measurements allowed us to conclude that high molecular weight polymer was preferentially adsorbed.     

Effect of deaeration on the adsorption of a mixture of cetyltrimethylammonium bromide and cetyldimethylbenzylammonium chloride at the mercury/electrolyte solution interface

The effect of deaeration on the adsorption of a mixture of cetyltrimethylammonium bromide and cetyldimethylbenzylammonium chloride at the mercury/electrolyte interface solution is studied using capacitance measurements focusing mainly at very low temperatures. Isochronous capacitance vs potential curves reconstructed from capacitance time curves show that the deaeration depends on the type of inert gas used as well as the deaeration process. The deaeration changes mainly the kinetics of the change of the capacitance with time. In cases where a condensed film is formed, the equilibrium capacitance value does not change with deaeration, indicating that the organization of the surfactants at the interface is not connected with the deaeration. The effect is attributed to the removal of dissolved gases from water.     

Competitive adsorption of Ca2+ and Zn(II) ions at monodispersed SiO2/electrolyte solution interface

A study of competitive adsorption of Ca(2+) and Zn(II) ions at the monodispersed SiO(2)/electrolyte solution interface is presented. Influence of ionic strength, pH, and presence of other ions on adsorption of Ca(2+) and Zn(II) in the mentioned system are investigated. zeta potential, surface charge density, adsorption density, pH(50%), and DeltapH(10-90%) parameters for different concentrations of carrying electrolyte and adsorbed ions are also presented. A high concentration of zinc ions shifts the adsorption edge of Ca(2+) ions adsorbed from solutions with a low initial concentration at the SiO(2)/NaClO(4) solution interface to the higher pH values. This effect disappears with a concentration increase of calcium ions. The presence of Ca(2+) ions in the system slightly affects the adsorption of zinc ions on SiO(2), shifting the adsorption edge toward lower pH values and thereby increasing the adsorption slope.     

Interaction between anionic and cationic gemini surfactants at air/water interface and in aqueous bulk solution

The mixture of the anionic O,O′-bis(sodium 2-lauricate)-p-benzenediol (C₁₁pPHCNa) and cationic (oligoona)alkanediyl-α, ω-bis(dimethyldodecylammonium bromide) (C₁₂-2-E_x-C₁₂·2Br) gemini surfactants has been investigated by surface tension and pyrene fluorescence. The results show that the surface tension γ drops faster with total surfactant concentration C_T for α₁ = 0.1 or 0.3 than for α₁ = 0.7 or 0.9, where α₁ is the mole fraction of C₁₁pPHCNa in the bulk solution on a surfactant-only basis. The fast drop in γ for α₁ < 0.5 indicates strong adsorption at the air/water interface owing to the interaction between oppositely charged components, resulting in the formation of the adsorption double layers in the subsurface. The slow descent in γ for α₁ > 0.5 is attributed to the pre-aggregation in the solution before the critical micelle concentration cmc. A possible mechanism is proposed.     

Electrosorption of tert-butanol at the Hg/aqueous NaF solution interface

Electrosorption of tert-butanol (TBUOH) on Hg from aqueous NaF solution has been investigated by means of electrocapillary measurements. The results are analyzed in terms of isotherms at constant potential and constant electrode charge density. The Frumkin isotherm with an attractive interaction parameter is satisfactorily fitted at every potential and electrode charge investigated. The relevant adsorption parameters are also discussed.     

Adsorption of multiple ammonium salts at the air/solution interface

The interfacial behavior of aqueous solutions of newly synthesized bis- and tris-ammonium salts (i.e., bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]alkylamine dichlorides and bis[2-hydroxy-3-(dodecyldimethylammonio)propyl]dialkylammmonium trichlorides, respectively) was analyzed, both experimentally and theoretically. The dynamic and equilibrium surface tension of multiple ammonium salt solutions was measured by using a pendant drop shape analysis method. The determined surface tension isotherms indicated the lack of significant differences in surface activity between bis- and tris-ammonium salts, contrary to the expectations for divalent and trivalent surfactant ions. That effect was explained by assuming the formation of multiple surfactant ion-counterion associates. Taking into account the association process, a good correlation between experimental data and theoretical predictions was obtained by means of the "surface quasi two-dimensional electrolyte" (STDE) model of ionic surfactant adsorption. The degree of association necessary to explain the lack of difference in surface activity between bis- and tris-ammonium salts was in quantitative agreement with the results of measurements of the concentration of free chloride anions in the surfactant solution.     

Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis

We investigated the local atomic and electronic structures of two related systematic sets of ternary uranium oxides, NaUO₃-KUO₃-RbUO₃ and BaUO₃-Ba₂U₂O₇-BaUO₄, by measuring the X-ray absorption near edge structure (XANES). The results are compared with calculations based on a self-consistent real space full multiple scattering analysis. We found a very good agreement between measured and calculated spectra, which indicates that the uranium ions are in a pure U⁵⁺ oxidation state in these compounds. The low energy shoulder observed in the U L₃ edge XANES is an intrinsic feature of the uranium unoccupied 6d electronic states of the U⁵⁺ ions within the studied materials. Specific double shoulder features in the higher energy range of the U L₃ edge XANES can be interpreted as indicative of the pure cubic perovskite structure.     

气-液界面上十六烷基溴化吡啶水溶液动态表面张力的研究

滴体积法测定了十六烷基溴化吡啶溶液的动态表面张力。考察了浓度、温度对动态表面张力的影响。讨论了十六烷基溴化吡啶分子在气／液界面上的吸附动力学,发现吸附遵从扩散-动力学控制机理．从表观扩散系数计算了吸附能垒,分析了吸附能垒存在的原因。     

Polyelectrolyte/surfactant mixtures at the air–solution interface

This review presents some of the recent developments in our understanding of the behaviour of polyelectrolyte/surfactant mixtures at the air–solution interface. The existence of a strong surface polyelectrolyte/surfactant interaction results in a complex pattern of surface adsorption. Recent studies, using a range of surface sensitive techniques, which include ellipsometry, neutron and X-ray reflectivity, surface tension and interfacial rheology, have considerably enhanced the understanding of their surface behaviour, which can be rationalized in terms of the competition between the formation of surface active polymer/surfactant complexes and solution polymer/surfactant micelle complexes.