Surface Concentration Effects

As already noted (p. 30) effects of surface concentrations are really effects of adsorption, since it is the adsorption properties of the components of the electrolyte solution that influence the structure of the inner Helmholtz layer. 

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In many cases, however, well-designed catalysts provide intrinsically different reaction paths, and the specific nature of the catalyst surface can be quite important. This is clearly the case with unimolecular reactions for which the surface concentration effect is not applicable. 

When surface-enhanced Raman spectroscopy (SERS) was discovered in 1974 by Eleischman, Hendra, and McQuillan, it was initially attributed to a surface concentration effect rather than to a surface enhancement effect [8]. The foundations of the... 

In order to study the influence of different parameters on the reaction, specially the role of the support on the intrinsic activity and selectivity of heterogenized catalysts, as well as, the surface concentration effect and the geometrical constraints, three different silanes with a wide range of steric bulkiness, phenyldimethylsilane, diphenylsilane and triethylsilane have been used. 

Instead of pursuing so general a method of treatment, the subject of capillary chemical effects has been studied experimentally, by investigations of Gibbs expression for the surface concentration effects due to surface tension Gibbs foe at) showed as a thermodynamical necessity that IF A DISSOLVED SUBSTANCE HAD THE PROPERTY OF LOWERING THE SURFACE TENSION OF THE SOLUTION (SAY, AT THE LIQUID AIR SURFACE), THE SUBSTANCE WOULD EXIST AT A HIGHER CONCENTRATION IN THE SURFACE LAYER THAN IN THE BULK OF THE SOLUTION... 

It was pointed out that a bimolecular reaction can be accelerated by a catalyst just from a concentration effect. As an illustrative calculation, assume that A and B react in the gas phase with 1 1 stoichiometry and according to a bimolecular rate law, with the second-order rate constant k equal to 10 1 mol" see" at 0°C. Now, assuming that an equimolar mixture of the gases is condensed to a liquid film on a catalyst surface and the rate constant in the condensed liquid solution is taken to be the same as for the gas phase reaction, calculate the ratio of half times for reaction in the gas phase and on the catalyst surface at 0°C. Assume further that the density of the liquid phase is 1000 times that of the gas phase. 

Since capillary tubing is involved in osmotic experiments, there are several points pertaining to this feature that should be noted. First, tubes that are carefully matched in diameter should be used so that no correction for surface tension effects need be considered. Next it should be appreciated that an equilibrium osmotic pressure can develop in a capillary tube with a minimum flow of solvent, and therefore the measured value of II applies to the solution as prepared. The pressure, of course, is independent of the cross-sectional area of the liquid column, but if too much solvent transfer were involved, then the effects of dilution would also have to be considered. Now let us examine the practical units that are used to express the concentration of solutions in these experiments. 

In a foam where the films ate iaterconnected the related time-dependent Marangoni effect is mote relevant. A similar restoring force to expansion results because of transient decreases ia surface concentration (iacteases ia surface tension) caused by the finite rate of surfactant adsorption at the surface. 

From known properties of solution, at measured or calculated concentration. Effective AT if a surface condenser. 

A numerical solution of this equation for a constant surface concentration (infinite fluid volume) is given by Garg and Ruthven [Chem. Eng. ScL, 27, 417 (1972)]. The solution depends on the value of A. = n i — n )/ n — n ). Because of the effect of adsorbate concentration on the effective diffusivity, for large concentration steps adsorption is faster than desorption, while for small concentration steps, when D, can be taken to he essentially constant, adsorption and desorption curves are mirror images of each other as predicted by Eq. (16-96) see Ruthven, gen. refs., p. 175. 

Stress concentration. Stress concentration refers to physical discontinuities in a metal surface, which effectively increase the nominal stress at the discontinuity (Fig. 9.7). Stress-concentrating discontinuities can arise from three sources ... 

An effect which is frequently encountered in oxide catalysts is that of promoters on the activity. An example of this is the small addition of lidrium oxide, Li20 which promotes, or increases, the catalytic activity of dre alkaline earth oxide BaO. Although little is known about the exact role of lithium on the surface structure of BaO, it would seem plausible that this effect is due to the introduction of more oxygen vacancies on the surface. This effect is well known in the chemistry of solid oxides. For example, the addition of lithium oxide to nickel oxide, in which a solid solution is formed, causes an increase in the concentration of dre major point defect which is the Ni + ion. Since the valency of dre cation in dre alkaline earth oxides can only take the value two the incorporation of lithium oxide in solid solution can only lead to oxygen vacaircy formation. Schematic equations for the two processes are... 

Surface SHG [4.307] produces frequency-doubled radiation from a single pulsed laser beam. Intensity, polarization dependence, and rotational anisotropy of the SHG provide information about the surface concentration and orientation of adsorbed molecules and on the symmetry of surface structures. SHG has been successfully used for analysis of adsorption kinetics and ordering effects at surfaces and interfaces, reconstruction of solid surfaces and other surface phase transitions, and potential-induced phenomena at electrode surfaces. For example, orientation measurements were used to probe the intermolecular structure at air-methanol, air-water, and alkane-water interfaces and within mono- and multilayer molecular films. Time-resolved investigations have revealed the orientational dynamics at liquid-liquid, liquid-solid, liquid-air, and air-solid interfaces [4.307]. 

Irritants Have a corrosive or a vesicant (blistering) effect on moist or mucous surfaces. Concentration may be more important than duration of exposure. Animals and man react similarly. ... 

This is an oversimplified treatment of the concentration effect that can occur on a thin layer plate when using mixed solvents. Nevertheless, despite the complex nature of the surface that is considered, the treatment is sufficiently representative to disclose that a concentration effect does, indeed, take place. The concentration effect arises from the frontal analysis of the mobile phase which not only provides unique and complex modes of solute interaction and, thus, enhanced selectivity, but also causes the solutes to be concentrated as they pass along the TLC plate. This concentration process will oppose the dilution that results from band dispersion and thus, provides greater sensitivity to the spots close to the solvent front. This concealed concentration process, often not recognized, is another property of TLC development that helps make it so practical and generally useful and often provides unexpected sensitivities. 

You may be surprised, but fouling is not always detrimental. The term dynamic membrane describes deposits that benefit the separation process by reducing the membrane s effective MWCO Molecular Weight cut-off) so that a solute of interest is better retained. Concentration polarization refers to the reversible build-up of solutes near the membrane surface. Concentration polarization can lead to irreversible fouling by altering interactions between the solvent, solutes and membrane. 

We have developed a theory that allows to determine the effective cluster interactions for surfaces of disordered alloys. It is based on the selfconsistent electronic structure of surfaces and includes the charge redistribution at the metal/vacuum interface. It can yield effective cluster interactions for any concentration profile and permits to determine the surface concentration profile from first principles in a selfconsistent manner, by... 

Random and structured packings are susceptible to surface fouling due to process conditions and/or the presence of oxygen as may be related to bacterial growth. Some systems will precipitate solids or crystals from solution usually due to the temperature and concentration effects. Bravo [135] discusses air-water stripping and illus-... 

A very similar effect of the surface concentration on the conformation of adsorbed macromolecules was observed by Cohen Stuart et al. [25] who studied the diffusion of the polystyrene latex particles in aqueous solutions of PEO by photon-correlation spectroscopy. The thickness of the hydrodynamic layer 8 (nm) calculated from the loss of the particle diffusivity was low at low coverage but showed a steep increase as the adsorbed amount exceeded a certain threshold. Concretely, 8 increased from 40 to 170 nm when the surface concentration of PEO rose from 1.0 to 1.5 mg/m2. This character of the dependence is consistent with the calculations made by the authors [25] according to the theory developed by Scheutjens and Fleer [10,12] which predicts a similar variation of the hydrodynamic layer thickness of adsorbed polymer with coverage. The dominant contribution to this thickness comes from long tails which extend far into the solution. 

It is necessary to note the limitation of the approach to the study of the polymerization mechanism, based on a formal comparison of the catalytic activity with the average oxidation degree of transition metal ions in the catalyst. The change of the activity induced by some factor (the catalyst composition, the method of catalyst treatment, etc.) was often assumed to be determined only by the change of the number of active centers. Meanwhile, the activity (A) of the heterogeneous polymerization catalyst depends not only on the surface concentration of the propagation centers (N), but also on the specific activity of one center (propagation rate constant, Kp) and on the effective catalyst surface (Sen) as well ... 

Here KP is the propagation rate constant, catalyst effective surface, C the monomer concentration near the catalyst surface, and Na the surface concentration of propagation centers. 

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