Net,excess and absolute adsorption and adsorption of helium

The definitions of absolute, excess and net adsorption in microporous materials are used to identify the correct limits at zero and infinite pressure. Absolute adsorption is shown to be the fundamental thermodynamic property and methods to determine the solid density that includes the micropore volume are discussed. A simple means to define when it is necessary to distinguish between the three definitions at low pressure is presented. To highlight the practical implications of the analysis the case of adsorption of helium is considered in detail and a combination of experiments and molecular simulations is used to clarify how to interpret adsorption measurements for weakly adsorbed components.     

The line adsorption equation: the one-dimensional counterpart of the Gibbs adsorption equation

The thermodynamic development for multiphase contact lines is analogous to that for surfaces or interfaces. However, for one of the most important equations in surface thermodynamics, the Gibbs adsorption equation, the one-dimensional analogue is missing. This paper derives such an analogue, the line adsorption equation. Similarly to the Gibbs adsorption equation, the line adsorption equation is derived from Gibbsian thermodynamics. For a three-phase, three-component contact line system (e.g. an oil lens on the surface of an aqueous solution), the line concentrations (excesses) of two immiscible solvents can be made vanish by appropriately placing the dividing line. Consequently, the line concentration of the solute can be evaluated through the line tension change with the volume concentration of the solute. Such an evaluation provides information about molecular adsorption at the contact line, which is important in physical chemistry of lines, but difficult to obtain by any other means.     

Analysis of Gibbs adsorption equation and thermodynamic relation between Gibbs standard energies of adsorption and micellization through a surface equation of state

The calculation of surface molecular areas through Gibbs adsorption equation has been questioned in some early works on the belief that these areas have been obtained from the apparently constant slope of the surface tension vs. logarithm of concentration curve along the entire region at which surface tension declines rapidly as the concentration increases. This premise leads to consider that Gibbs equation predicts that surface saturation is reached at the beginning of this region. However, through an analysis of the forementioned curve in accordance to Gibbs equation, it can be easily shown that surface saturation is attained at the end of the region. On the other hand, based on a thermodynamic model, it is also shown that the adsorption process, and thus, surface saturation, proceeds before micellization.     

A qualitative approach to adsorption mechanism identification on microporous carbonaceous surfaces

The paper presents results of research on identification of localized and other adsorption mechanisms, on geometrically heterogeneous graphite-like carbonaceous surfaces. It attempts to get an insight into properties of individual adsorptive molecule movement near attractive adsorption sites, arising from adsorbent surface geometrical heterogeneities. In particular, a shape and volume of space occupied by the continuously moving molecule mass center are investigated. To this aim, kinematic equilibrium of the particle moving near a hypothetical microporous carbonaceous adsorbent wall is considered, and then compared with thermodynamic equilibrium. The proposed approach enables to examine effects of certain surface geometry on the shape and volume of space occupied by adsorbed particles, and so to outline temperature conditions for the localized adsorption mechanism predomination. Thus, it provides a cognitive basis to answer the question, what particular mechanism (localized or other—e.g. mobile) should be assumed for a class of adsorption systems in order to select the most appropriate mathematical adsorption model. Hence, it makes it possible for more reliable examination of real porous structures, based on adsorption measurements.     

A new approach to the adsorption kinetics of gas mixtures on heterogeneous surfaces

An attempt is made to develop a general theory for describing the adsorption kinetics of gaseous mixtures on heterogeneous surfaces. This can be made by generalization of the equations obtained for equilibrium adsorption of gas mixtures.

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Restructuring of hydrophobic surfaces created by surfactant adsorption to mica surfaces

Hydrophobic surfaces created by the adsorption of a monolayer of surfactants, such as CTAB or DODAB, to mica display long-range mutual attraction when placed in water. Initially, this attraction was considered to be due to hydrophobic interaction, but more careful measurements using AFM showed that the surfactant monolayer undergoes rearrangements to produce charged patches on the surface; therefore, the nature of the long-range interaction is due to the electrostatic interaction between patches. The monolayer rearrangement depends on the nature of the surfactant and its counterion. To study possible monolayer rearrangements in molecular detail, we performed detailed molecular dynamics computer simulations on systems containing a monolayer of surfactants RN(CH(3))(3)(+)Cl(-) (R indicates a saturated hydrocarbon chain) adsorbed on a mica surface and immersed in water. We observe that when chain R is 18 carbons long the monolayer rearranges into a micelle but it remains a monolayer when the chain contains 24 carbons.     

利用吉布斯吸附等温式探索求解电解质溶液活度的新方法

以吉布斯吸附等温式积分式为基础,数学推证表面势的表达式,并应用表面势的数学表达式探求了一种测算电解质溶液活度系数的新方法.选取KIM计算电解质溶液溶质的活度系数公式为新方法的活度系数经验关系式的具体表达形式,利用实验直接测得的不同浓度下的表面张力数据,采用最优化拟合的方法,求算出活度系数经验关系式中的待定系数,从而可以求得不同浓度下的电解质溶液中的溶质的活度系数和活度.计算结果与KIM文献值对比,活度系数曲线在不同的坐标尺度下有很好的一致性,这使得通过测定电解质溶液表面张力测算其活度成为可能.     

A method for characterizing adsorption of flowing solutes to microfluidic device surfaces

We present a method for characterizing the adsorption of solutes in microfluidic devices that is sensitive to both long-lived and transient adsorption and can be applied to a variety of realistic device materials, designs, fabrication methods, and operational parameters. We have characterized the adsorption of two highly adsorbing molecules (FITC-labeled bovine serum albumin (BSA) and rhodamine B) and compared these results to two low adsorbing species of similar molecular weights (FITC-labeled dextran and fluorescein). We have also validated our method by demonstrating that two well-known non-fouling strategies [deposition of the polyethylene oxide (PEO)-like surface coating created by radio-frequency glow discharge plasma deposition (RF-GDPD) of tetraethylene glycol dimethyl ether (tetraglyme, CH(3)O(CH(2)CH(2)O)(4)CH(3)), and blocking with unlabeled BSA] eliminate the characteristic BSA adsorption behavior observed otherwise.     

Interactions of anionic dyes with silica-aminopropyl 1. A quantitative multivariate analysis of equilibrium adsorption and adsorption Gibbs free energies

In this work silica-aminopropyl (Sil-NH2) was synthesized and employed to evaluate the quantitative roles of temperature, pH, dye concentration, and Hg(II) or anionic surfactant SDB interferents in the adsorptions of blue and red remazol dyes in aqueous medium using four distinct 2(4) factorial designs. The results were analyzed statistically using multiple regressions, Student's t-test, analysis of variance, and F-test. Polynomial modelings were used to define the most important factors affecting dye adsorption. The results indicate that the principal effects of dye concentration and pH, as well as most of the interactions of all factors, are statistically very important in relation to the equilibrium adsorption quantities. However, the adsorption Gibbs free energies are influenced, in general, only by pH, dye concentration, and some binary interactions. Temperature changes do not affect the deltaG values significantly.     

A theoretical revisit to the lowest ionization potentials in metal-metal bonds

The ties that bind: The electrostatic potential of quadruply bonded W(2)(hpp)(4) and its cation support the idea that the very low ionization energies are due to excitations from the metal-metal bonding core. Theoretical MRCI computations based on CASSCF orbitals show that the relativistic effect influences the lowest four ionization energies, leading to distinct IE sequences: IE(δ) < IE(π) < IE(σ) in W(2)(hpp)(4), and IE(δ) < IE(σ) < IE(π) in Mo(2)(hpp)(4).     

Using ferroelectric poling to change adsorption on oxide surfaces

Adsorption has been invoked to explain many phenomena in ferroelectric materials including the unanticipated stability of ultrathin ferroelectric films; however, the intrinsic surface properties of ferroelectric oxides have been largely unexplored. Therefore, the effect of ferroelectric poling on the adsorption/desorption of two polar molecules, acetic acid and 2-propanol, and one nonpolar molecule, dodecane, on LiNbO3(0001) was compared. The two polar molecules were found to adsorb significantly more strongly on the positive surface. Temperature-programmed desorption (TPD) data yielded desorption pre-exponentials of the two polar molecules more than 11 orders of magnitude lower than expected. Ferroelectric materials are also intrinsically pyroelectric, and it is shown that the unusually low desorption pre-exponentials can be explained by temperature dependent heats of adsorption that result from changes in the surface dipole as the samples are heated. This conclusion was supported by dodecane adsorption/desorption, which was independent of polarity with normal desorption pre-exponentials. The differences between the polar and nonpolar molecules indicate that interactions between polar molecules and ferroelectric surfaces are dominated by electrostatics. It is shown that adsorption energy differences between positive and negative surfaces are large enough to switch the polarity of ferroelectric thin films.     

Using a family of dividing surfaces normal to the minimum energy path for quantum instanton rate constants

One of the outstanding issues in the quantum instanton (QI) theory (or any transition-state-type theory) for thermal rate constants of chemical reactions is the choice of an appropriate "dividing surface" (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DSs for use in QI theory, namely, using the family of (hyper) planes normal to the minimum energy path on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an N atom system in three-dimensional space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the collinear H+H(2) reaction) is presented to illustrate the procedure.     

A model for the cooperative adsorption of surfactant mixtures on solid surfaces

Adsorption of surfactant mixtures on solids is of considerable theoretical and practical importance. In this study, cooperative adsorption of surfactant mixtures of nonyl phenol ethoxylated decyl ether (NP-10) and n-dodecyl-beta-D-maltoside (DM) on silica and alumina has been investigated as a function of the distribution of individual surfactants between solution and solid surface. In the mixed adsorption process, DM is identified to be the "active" adsorbing component and NP is the "passive" co-adsorbing one in the process of adsorption on alumina, while their roles are reversed on silica. A modified model has been proposed to quantify the adsorption behavior of surfactant mixtures and to obtain information in terms of aggregation number and standard free energy for surface aggregation. This model is the first model applied to the aggregation of the surfactant mixture at the solid/solution interfaces.     

Antibody adsorption and orientation on hydrophobic surfaces

The orientation of a monoclonal, anti-streptavidin human IgG1 antibody on a model hydrophobic, CH(3)-terminated surface (1-dodecanethiol self-assembled monolayer on gold) was studied by monitoring the mechanical coupling between the adsorbed layer and the surface as well as the binding of molecular probes to the antibodies. In this study, the streptavidin antigen was used as a probe for the Fab portions of the antibody, while bacteria-derived Protein G' was used as a probe for the Fc region. Bovine serum albumin (BSA) acted as a blocking protein. Monolayer coverage occurred around 468 ng/cm(2). Below 100 ng/cm(2), antibodies were found to adsorb flat-on, tightly coupled to the surface and unable to capture their antigen, whereas the Fc region was able to bind Protein G'. At half-monolayer coverage, there was a transition in the mechanism of adsorption to allow for vertically oriented antibodies, as evidenced by the binding of both Protein G' and streptavidin as well as looser mechanical coupling with the surface. Monolayer coverage was characterized by a reduced level in probe binding per antibody and an even less rigid coupling to the surface.     

Protein adsorption to organosiloxane surfaces studied by acoustic wave sensor

Surfaces of the two organosiloxanes, polymercaptopropylmethylsiloxane and octaphenylcyclotetrasiloxane, were prepared on the gold electrodes of thickness-shear mode acoustic wave sensors. Compounds containing the siloxane bond are important in the fabrication of medical implants. The flow-through adsorption of the proteins: human serum albumin, alpha-chymotripsinogen A, cytochrome c, fibrinogen, hemoglobin, immunoglobulin G and apo-transferrin to the two siloxane surfaces and a gold electrode were detected by acoustic network analysis. With the exception of minor wash-off by buffer flow, the adsorption of all proteins to the three surfaces is irreversible. Differences observed for the magnitudes of adsorption for the various cases are ascribed to the role played by molecular interactions at the liquid/solid interface. The results confirm that changes in series resonant frequencies caused by macromolecular adsorption differ significantly from the widely accepted "mass based" model usually employed to characterize the response of this type of acoustic wave device.     

Polyion adsorption onto catanionic surfaces. A Monte Carlo study

The adsorption of a single and negatively charged polyion with varying flexibility onto a surface carrying both negative and positive charges representing a charged membrane surface has been investigated by using a simple model employing Monte Carlo simulations. The polyion was represented by a sequence of negatively charged hard spheres connected with harmonic bonds. The charged surface groups were also represented by charged hard spheres, and they were positioned on a hard surface slightly protruding into the solution. The surface charges were either frozen in a liquidlike structure or laterally mobile. With a large excess of positive surface charges, the classical picture of a strongly adsorbed polyion with an extended and flat configuration emerged. However, adsorption also appeared at a net neutral surface or at a weakly negatively charged surface, and at these conditions the adsorption was stronger with a flexible polyion as compared to a semiflexible one, two features not appearing in simpler models containing homogeneously charged surfaces. The presence of charged surface patches (frozen surface charges) and the ability of polarization of the surface charges (mobile surface charges) are the main reasons for the enhanced adsorption. The stronger adsorption with the flexible chain is caused by its greater ability to spatially correlate with the surface charges.