Surface inhibition effects

To account for surface inhibition effects, an assumption is made that the development rate near the surface of the resist exponentially approaches the bulk development rate, giving a rate as a function of depth r(z) as ... 

Paraffin wax additives are effective in overcoming surface inhibition by forming a monomolecular wax layer at the curing surface. Although effective in excluding oxygen, this waxy layer must be removed for subsequent lamination or bonding processes (see Waxes). 

Effect of HjS, Carbon Oxides, Etc. Hydrogen sulfide in the treat gas has an inhibiting effect on the kinetics of hydrotreating. Being a product of the desulfurization reactions, HjS must diffuse from the catalyst surface into the bulk gas stream. Any HjS present beyond that formed, further slows down the rate of diffusion with a consequent decrease in the amount of desulfurization for a given amount of catalyst. Therefore, additional catalyst would be required. 

It is in this area that most work has been carried out, particularly in relation to corrosion resistance in sulphuric acid solutionsBourelier etal. and Raicheff etal. investigated the inhibitive effect of chloride ions on corrosion in sulphuric acid. The inhibition efficiency was found to depend on the alloy composition, alloy surface and chloride concentration. The more aggressive the environment, the greater the inhibition efficiency. Yagupol skaya etal studied the effect of iodine additions to sulphuric acid on the corrosion resistance of Ni and Ni-Fe alloys. Again there was an inhibitive effect caused by the halide ion. 

In the case of ions, the repulsive interaction can be altered to an attractive interaction if an ion of opposite charge is simultaneously adsorbed. In a solution containing inhibitive anions and cations the adsorption of both ions may be enhanced and the inhibitive efficiency greatly increased compared to solutions of the individual ions. Thus, synergistic inhibitive effects occur in such mixtures of anionic and cationic inhibitors . These synergistic effects are particularly well defined in solutions containing halide ions, I. Br , Cl", with other inhibitors such as quaternary ammonium cations , alkyl benzene pyridinium cations , and various types of amines . It seems likely that co-ordinate-bond interactions also play some part in these synergistic effects, particularly in the interaction of the halide ions with the metal surfaces and with some amines . 

Conversely, an atom in Fig. 6.23 with an affinity level that initially is empty becomes partly occupied upon adsorption. Hence, charge is transferred from the metal to the atom. This sets up a dipole that increases the surface contribution to the work function. This is the case for adsorbed halides, which will be negatively charged at the surface. We will later see that such dipole fields can explain promotion and inhibition effects caused by various adsorbates in catalysis. 

Besides this, the inhibiting effects are dependent on the nature of the Pt surface as has been demonstrated by investigations on single crystals [37, 38] and on polycrystalline material with preferred surface orientation [39],... 

S. Fortier, M. Touaibia, S. Lord-Dufour, J. Galipeau, R. Roy, and B. Annabi, Tetra- and hexavalent mannosides inhibit the pro-apoptotic, antiproliferative and cell surface clustering effects of concanavalin A Impact on MT1-MMP functions in marrow-derived mesenchymal stromal cells, Glycobiology, 18 (2008) 195-204. 

Fischer-Tropsch synthesis can be regarded as a surface polymerization reaction since monomer units are produced from the reagents hydrogen and carbon monoxide in situ on the surface of the catalyst. Hence, a variety of hydrocarbons (mainly n-paraffines) are formed from hydrogen and carbon monoxide by successive addition of C, units to hydrocarbon chains on the catalyst surface (Equation 12.1). Additionally, carbon dioxide (Equation 12.3) and steam (Equations 12.1 and 12.2) are produced C02 affects the reaction just a little, whereas H20 shows a strong inhibiting effect on the reaction rate when iron catalysts are used. 

Micelles have effects on spontaneous reactions which can be related to mechanism and the properties of the micellar surface. Inhibition of bimolecu-lar, micelle-inhibited reactions is also straightforward because micelles keep reactants apart. 

As is well known (Morse and Berner, 1972) even very small concentrations of HPO (and some organic solutes) inhibit nucleation of CaC03, most likely because these adsorbates block essential surface sites on the substrate or on the mineral clusters. Mg2+ is known to inhibit many nucleation processes, especially also the nucleation of Mg bearing minerals. The water exchange rate of Mg2+ is slower than that of many cations, such as Pb2+, Cu2+, Zn2+, Cd2+, Ca2+. The inhibition effect of Mg2+ may be due to its sluggishness to (partial) dehydration. (Mg2+ has among the bivalent ions a very large enthalpy (-AHj,) of hydration.)... 

Alfassi, Z. B., and Benson, S. W., A simple empirical method for the estimation of activation energies in radical molecule metathesis reactions, Int. J. Chem. Kinetics S, 879 (1973). Allara, D. L., and Edelson, D., A computational analysis of a chemical switch mechanism. Catalysis-inhibition effects in a copper surface-catalyzed oxidation, J. Phys. Chem. 81, 2443 (1977). 

The major factors probably responsible for the acceleration effect of additives are (1) the charge density of the electron system of the additive and (2) the exchange of electrons between electrode, 7r-bonded additive molecule, and the complexed metal ions in the solution. Inhibition effect and cathodic passivation are explained in terms of blocking of the catalytic surface, which results in a decrease in the available surface area (45). 

Most transition metals (for Fe, Co and Ni see the following paragraphs) are located on the descending branch of the volcano curve. For these metals, the adsorption of H is strong and 5h close to saturation, making H2 desorption from the surface difficult. For these metals, the inhibiting effect of 5h prevails over the... 

As seen in reaction (6.5.3) photogenerated holes are consumed, making electron-hole separation more effective as needed for efficient water splitting. The evolution of CO2 and O2 from reaction (6.5.6) can promote desorption of oxygen from the photocatalyst surface, inhibiting the formation of H2O through the backward reaction of H2 and O2. The desorbed CO2 dissolves in aqueous suspension, and is then converted to HCOs to complete a cycle. The mechanism is still not fully understood, with the addition of the same amount of different carbonates, see Table 6.2, showing very different results [99]. Moreover, the amount of metal deposited in the host semiconductor is also a critical factor that determines the catalytic efficiency, see Fig. 6.7. 

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