Acid-base interactions measurement surface properties

A study of the interaction of Lewis acids and bases (or electron acceptors and donors) in surface dynamics has led to new insight into interactions with various solid surfaces [26,64,99,100,104,110,130-142], as well as interactions at interfaces between two different substances. It is noted that the acid-base interactions of Lewis, including the orientational properties of charge transfer forces of Mulliken [143], occur between specific (or polar) groups in substances. These interactions are quite dependent on the Stockmayer degree of polarity, <5, [126] as measured by dipole moment in Eq. (58). Furthermore, it can be found that a concept of acids attract bases may be substituted... 

As discussed above, there have been few systematic studies in which the acid or basic strength of materials relevant to catalysis has been correlated on a quantitative scale. The utility of microcalorimetric measurements of the heats of adsorption of various molecules is evident. These measurements can be used to determine the acid or basic strength of surfaces and establish their effect on the catalytic behavior of the materials. If we desire to control these acid-base properties to tailor and improve catalysts for existing processes and to design improved catalysts for new catalytic processes, a quantitative scale of the acid-base interactions is required. Appropriate correlations, perhaps involving electronegativity scales, would allow the prediction of the acid-base strength of the surface sites which can then be related to the catalytic activity of those sites. Additional research in this area is required. 

Inverse gas chromatography at infinite dilution appears to be a powerful tool for studying the surface properties of carbon fibres and polymer matrices. The use of alkane probes and acid/base probes allows the characterization of the surfaces in terms of their London dispersive component of surface energy and their acid/base or acceptor/donor characteristics. A strong correlation was obtained between fibre-matrix adhesion, measured by a destructive fragmentation technique, and the level of acid base interactions calculated from the chromatographic analysis. 

It is shown in [4] that the presence of two types of centres possessing the discriminate reductive-oxidation and acid-base properties and participating in transformation processes of an alcohol molecule is an essential requirement to achieve high sensor response values when alcohol detection is mentioned. Alcohol detection is considered as a multi-step process involving both red-ox and acid-base interactions. Oxide phases within composites differ by oxygen-oxide surface bonding energy which can be the relative measure of oxide activity in oxidation reactions. The reactivity of... 

Inverse gas chromatography involves the sorption of a known probe molecule (adsorbate, vapour) and an unknown adsorbent stationary phase (solid sample). IGC may be experimentally configured for finite or infinite dilution concentrations of the adsorbate. The latter method is excellent for the determination of thermodynamic properties such as surface energies and Lewis acid-base parameters. Measurements in this range are extremely sensitive due to the low concentration regime where the highest energy sites of the surface interact with the probe molecules. 

As noted in the preceding section, IGC is an excellent tool for measurements of surface properties and of acid base interaction potentials of macromolecular solids (2,10,16). In this section the importance of acid-base interactions relative to the adhesion of PUs is considered in greater detail. IGC has been applied to a series of PU adhesives and to selected polymer substrates, allowing quantitative measurements to be made of the acid/base (electron donor-acceptor) interaction parameters applicable to the surfaces of these materials. Acid base pair-interaction parameters for substrate/PU combinations have been calculated. The bond characteristics of polymer/PU combinations have been measured, in part by conventional lap-shear procedures and in part, by the more recent constrained blister detachment method [11, 12]. Possible relationships between bond properties and acid base interactions have been considered, and a comparison of the two adhesion tests has been made. 

A tentative model has been proposed to relate the interfacial shear strength at the fibre-matrix interface, measured by a fragmentation test on single fibre composites, to the level of adhesion between both materials. This last quantity has been estimated from the surface properties of both the fibre and the matrix and was defined as the sum of dispersive and acid-base interactions. This new model clearly indicates that the micromechanical properties of a composites are mainly determined by the level of physical interactions established at the fibre-matrix interface and, in particular, by electron acceptor-donor interactions. Moreover, to a first approximation, our model is able to explain the stress transfer phenomenon through interfacial layers, such as crystalline interphases in semi-crystalline matrices and interphases of reduced mobility in elastomeric matrices. An estimation of the elastic moduli of these interphases can also be proposed. Furthermore, recent work [21] has shown that the level of interfacial adhesion plays a major role on the final performances (tensile, transverse and compressive strengths and strains) of unidirectional carbon fibre-PEEK composites. 

Carbon dioxide fulfills some of the relevant criteria and contradicts others. Evidently, although C02 exhibits acidic properties, the adsorbed amounts cannot be taken as a measure of surface basicity strong chemisorption of C02 occurs through interaction with acid-base pair sites preferentially. Thus, specific poisoning of basic sites by C02 chemisorption is not possible. Furthermore, a... 

In order to try to clarify the different types of mechanism involving either redox cycles and/or acid-base properties, a study of the surface chemistry of single, doped and mixed oxides is of much interest. The calorimetric technique, by allowing heat transfer measurements, can provide very informative data on the thermodynamics of solid-gas interactions and for the study of the surface and reactivity of these metal oxides. 

Formic acid is a popular molecule for probing the catalytic properties of metal oxides [23-28], The selectivity of its decomposition has frequently been used as a measure of the acid-base properties of oxides. This is a tempting generalization to make oxides that produce dehydration products (H2O and CO) are described as acidic oxides, while their basic counterparts produce dehydrogenation products (H2 + CO2). It has been shown that in many cases the product selectivity is better connected to the surface redox behavior of the oxide [29], Thus, more reducible surfaces produce higher yields of CO2, Consequently, particular attention has been paid in surface science studies to the interaction between adsorbed formate ions (the primary reaction intermediate) and surface metal cations, as well as to the participation of lattice oxygen anions in the surface reaction mechanism,... 

The acid-base properties of DOM are of intrinsic interest because acidic functional groups contribute to the acid-base balance of natural waters, affect complexation and transport of dissolved metals, and interact with mineral surfaces. The concentrations of carboxyl and phenolic functional groups are among the most widely measured and reported properties of DOM. Methodologically, there are two basic approaches for measuring acidic group content—indirect titrations and direct titrations (Perdue et al., 1980 Perdue, 1985 Ritchie and Perdue, 2003). 

Attempts have been made of correlating the oxide acid-base properties, as determined by calorimetric techniques, and the corresponding catalytic activity and selectivity for the decomposition of propan-2-ol [126] and 4-methylpentan-2-ol [125]. As discussed in ref [127], however, this sort of correlations, in addition to the limitations inherent to the cleaning procedure applied in the calorimetric measurements, has a second difficulty under reaction conditions, the interaction of alcohols with the surface of rare earth sesquioxides leads to the formation of carboxilate and carbonate species which certainly will modify the acid-base properties of the actual catalytic surface. 

This book presents coverage of the dynamics, preparation, application and physico-chemical properties of polymer solutions and colloids. It also covers the adsorption characteristics at and the adhesion properties of polymer surfaces. It is written by 23 contemporary experts within their field. Main headings include Structural ordering in polymer solutions Influence of surface Structure on polymer surface behaviour Advances in preparations and appUcations of polymeric microspheres Latex particle heterogeneity origins, detection, and consequences Electrokinetic behaviour of polymer colloids Interaction of polymer latices with other inorganic colloids Thermodynamic and kinetic aspects of bridging flocculation Metal complexation in polymer systems Adsorption of quaternary ammonium compounds art polymer surfaces Adsorption onto polytetrafluoroethylene from aqueous solutions Adsorption from polymer mixtures at the interface with solids Polymer adsorption at oxide surface Preparation of oxide-coated cellulose fibre The evaluation of acid-base properties of polymer surfaces by wettability measurements. Each chapter is well referenced. 

Where y is the contribution of dispersive forces and y is the contribution of specific interaction forces such as H-bonding, dipole-dipole, acid-base, etc. The IGC method was successfully applied in recent years to determine the surface properties of divided solids 45,46), From gas chromatographic measurements, Vg is determined by using equation (1). Vg relates to the equilibrium constant K between the adsorbed solute and the polymer surface as follows ... 

The liquid-solid interactions of physical (essentially van der Waals) and chemical (essentially acid-base) type can quench or put out some surface sites, so modifying their reactivity towards reagents. Therefore, in order to understand and predict the catalytic ability of given surfaces in different liquids, it is very important to measure the effective surface properties, besides the knowledge of the intrinsic properties. 

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