Solid-aqueous interface, adsorption

Adsorption and electrokinetic effects of amino acids, solid-aqueous interface, 311-26 Adsorption density, equilibrium PAA at various pH values, 299f PAA on hematite, 304f SDS with and without polymer, 298f,303f... 

Retention in Porous Media. Anionic surfactants can be lost in porous media in a number of ways adsorption at the solid—liquid interface, adsorption at the gas—liquid interface, precipitation or phase-separation due to incompatibility of the surfactant and the reservoir brine (especially divalent ions), partitioning or solubilization of the surfactant into the oil phase, and emulsification of the aqueous phase (containing surfactant) into the oil. The adsorption of surfactant on reservoir rock has a major effect on foam propagation and is described in detail in Chapter 7 by Mannhardt and Novosad. Fortunately, adsorption in porous media tends to be, in general, less important at elevated temperatures 10, 11). The presence of ionic materials, however, lowers the solubility of the surfactant in the aqueous phase and tends to increase adsorption. The ability of cosurfactants to reduce the adsorption on reservoir materials by lowering the critical micelle concentration (CMC), and thus the monomer concentration, has been demonstrated (72,13). 

Surfactant-polymer interactions in an aqueous solution have been studied by many researchers [132], and the adsorption and surface-induced self-assembly of the surfactant at the solid-aqueous interface have been recently studied [133]. On the other hand, these subjects have been rarely studied for oil solutions. The surfactant-polymer interaction in oil and the surface-induced self-assembly of surfactants at the oil-solid interface are important for further research studies to enhance the polymerization at the interface of the liquid/solid in reversed micellar solutions. 

For a review in this field, see F. Tiberg, J. Brinck, L. Grant, Adsorption and surface-induced self-assembly of surfactants at the solid-aqueous interface, Curr. Opin. Colloid Interf Sd. 2000, 4,411-419. 

In the conditioning process, under suitable alkaline conditions, both ionization of functional groups at the bitumen surface [33, 105] and adsorption of the natural anionic surfactant molecules at the bitumen/ aqueous interface [100,101,104] occur. Descriptions of the experimental techniques, including microelectrophoresis, employed to study the effects are given elsewhere [100,102,104,106]. Figure 14 shows how addition of NaOH in the process increases the concentrations of surfactant in the aqueous phase, which in turn increases the extents of surfactant adsorption at all of the aqueous phase interfaces present in the system gas/ aqueous, bitumen/aqueous, and solid/aqueous. The adsorption increases until monolayer coverage is achieved and thereafter either levels off or continues into multilayer adsorption. 

Adsorption is a physicochemical process whereby ionic and nonionic solutes become concentrated from solution at solid-liquid interfaces.3132 Adsorption and desorption are caused by interactions between and among molecules in solution and those in the structure of solid surfaces. Adsorption is a major mechanism affecting the mobility of heavy metals and toxic organic substances and is thus a major consideration when assessing transport. Because adsorption is usually fully or partly reversible (desorption), only rarely can it be considered a detoxification process for fate-assessment purposes. Although adsorption does not directly affect the toxicity of a substance, the substance may be rendered nontoxic by concurrent transformation processes such as hydrolysis and biodegradation. Many chemical and physical properties of both aqueous and solid phases affect adsorption, and the physical chemistry of the process itself is complex. For example, adsorption of one ion may result in desorption of another ion (known as ion exchange). 

Adsorption of (bio)polymers occurs ubiquitously, and among the biopolymers, proteins are most surface active. Wherever and whenever a protein-containing (aqueous) solution is exposed to a (solid) surface, it results in the spontaneous accumulation of protein molecules at the solid-water interface, thereby altering the characteristics of the sorbent surface and, in most cases, of the protein molecules as well (Malmsten 2003). Therefore, the interaction between proteins and interfaces attracts attention from a wide variety of disciplines, ranging from environmental sciences to food processing and medical sciences. 

Titration calorimetry and cylindrical internal reflection-Fourier transform infrared (CIR-FTIR) spectroscopy are two techniques which have seldom been applied to study reactions at the solid-liquid interface. In this paper, we describe these two techniques and their application to the investigation of salicylate ion adsorption in aqueous goethite (a-FeOOH) suspensions from pH 4 to 7. Evidence suggests that salicylate adsorbs on goethite by forming a chelate structure in which each salicylate ion replaces two hydroxyls attached to a single iron atom at the surface. 

General Observations About x. its Relationship to the Overall Partitioning Coefficient and to the Concept of Surface-Site Heterogeneity. One approach to metal/particle surface interactions which has been developed, historically, in a variety of forms, is a conceptual model that assumes only two conditions for surface sites occupied by an adsorbate or unoccupied. In applying this approach to the solid/aqueous solution interface, the adsorption... 

The mechanism of interaction of amino acids at solid/ aqueous solution interfaces has been investigated through adsorption and electrokinetic measurements. Isotherms for the adsorption of glutamic acid, proline and lysine from aqueous solutions at the surface of rutile are quite different from those on hydroxyapatite. To delineate the role of the electrical double layer in adsorption behavior, electrophoretic mobilities were measured as a function of pH and amino acid concentrations. Mechanisms for interaction of these surfactants with rutile and hydroxyapatite are proposed, taking into consideration the structure of the amino acid ions, solution chemistry and the electrical aspects of adsorption. 

T1he adsorption of metal ions from aqueous solutions is a phenomenon of immediate interest to workers in many diverse disciplines. The incorporation of metals into geological sediments, removal of metal ions from industrial and civic effluent, interference of trace metal ions in analytical and electroanalytical chemistry, ore flotation, metallurgical leaching processes, and the stability of ceramic slips are all processes which are controlled to a large extent by interaction of metal ions with solid-liquid interfaces. 

Recent studies indicate that the adsorption of metal ions is controlled only in part by the concentration of the free (aquo) metal ion of considerable importance is the ability of hydroxo and other complex ions and molecules to adsorb. There have been two apparently divergent approaches to describe the role played by hydroxo metal complexes in adsorption at solid-aqueous electrolyte interfaces. Matijevic et al. (9) have proposed that specific hydrolysis products—e.g., Al8(OH)2o4+ in the A1(III)-H20 system, are responsible for extensive coagulation and charge reversal of hydrophobic colloids. It has also been demonstrated by Matijevic that the free (aquo) species of transition and other metal ions... 

The most general feature of the adsorption behavior of metal ions at solid-aqueous solution interfaces is the abrupt rise in adsorption over a narrow pH range. This has been illustrated, for example, for manganese adsorption on glass (2), cobalt on hydrous ferric oxide (8), manganese on hydrous manganese oxide (12), protactinium on glass (14), and... 

This paper describes a study of the dispersibility of Graphon (graphitized Spheron 6) in aqueous solutions of sodium dodecyl sulfate (SDS) an dodecyl trimethylammonium bromide (DTAB), and its relation to the adsorption behavior of the surfactants at the solid/liquid interface, with a view to determine the controlling process in the dispersibility of these systems. 

This experimental evidence clearly shows the complicated nature of the adsorption isotherm for a detergent at the polar solid-aqueous solution interface. 

In mineral processing, there are numerous systems in which postulates have been made to suggest adsorption of surface active molecules on specific surface sites. Most of the postulates are based on inference from a variety of observations and direct evidence has been lacking. It should now be possible to use Raman spectroscopy to characterize solid/aqueous solution interfaces. 

Polymer Adsorption. A review of the theory and measurement of polymer adsorption points out succinctly the distinquishing features of the behavior of macromolecules at solid - liquid interfaces (118). Polymer adsoiption and desorption kinetics are more complex than those of small molecules, mainly because of the lower diffusion rates of polymer chains in solution and the "rearrangement" of adsorbed chains on a solid surface, characterized by slowly formed, multi-point attachments. The latter point is one which is of special interest in protein adsoiption from aqueous solutions. In the case of proteins, initial adsoiption kinetics may be quite rapid. However, the slow rearrangement step may be much more important in terms of the function of the adsorbed layer in natural processes, such as thrombogenesis or biocorrosion / biofouling caused by cell adhesion. 

For example, in aqueous media, surfactant molecules will migrate to air/water and solid/water interfaces and orientate in such a fashion as to minimise, as much as possible, the contact between their hydrophobic groups and the water. This process is referred to as adsorption and results in a change in the properties at the interface. 

At the beginning, the electric double layer at the solid-aqueous electrolyte solution interface was characterized by the measurements of the electrokinetic potential and stability of dispersed systems. Later, the investigations were supported by potentiometric titration of the suspension, adsorption and calorimetric measurements [2]. Now, much valuable information on the mechanism of the ion adsorption can be obtained by advanced spectroscopic methods (especially infrared ATR and diffuse spectroscopy) [3], Mosbauer spectroscopy [4] and X-ray spectroscopy [5]. Some data concerning the interface potential were obtained with MOSFET [6], and AFM [7]. An enthalpy of the reaction of the metal oxide-solution systems can be obtained by... 

Wadsworth and coworkers (13, 14) have found considerable evidence for surface polarization in double-beam infrared spectroscopy. Not only do new differential peaks due to adsorption appear in the spectrograms but also the bands due entirely to the adsorbent are frequently appreciably shifted by adsorption. This occurred, for example, in calcium fluorite treated with oleic acid, in samples of bentonites taken from aqueous solutions of different pH, and in various minerals treated by flotation collectors. In fact, it is more the rule than the exception that the spectrograms of finely divided solids dispersed in the KI or KBr window exhibit distortion due to adsorption, whether adsorption occurs at the solid-aqueous solution or at the solid-vapor interface. For example, Eyring and Wadsworth (13) found that two (differential) peaks were produced by adsorption on willemite either from the vapor or aqueous solution of hexanethiol. These peaks were due to the influence of adsorption of the hexanethiol on the Si-O bands of the willemite and occurred at about 9.2 and 12.3 microns. 

D.H. Everett, Adsorption at the Solid-Liquid Interface, in Specialist Periodical Report, Colloid Science. The Chemical Society (London), Vol. 1 (1973) 49 (ready access to the literature up to the year of publication non-aqueous systems). 

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