Definition surface heterogeneity

Since solid acid catalysts are used extensively in chemical industry, particularly in the petroleum field, a reliable method for measuring the acidity of solids would be extremely useful. The main difficulty to start with is that the activity coefficients for solid species are unknown and thus no thermodynamic acidity function can be properly defined. On the other hand, because the solid by definition is heterogeneous, acidic and basic sites can coexist with variable strength. The surface area available for colorimetric determinations may have widely different acidic properties from the bulk material this is especially true for well-structured solids like zeolites. It is also not possible to establish a true acid-base equilibrium. 

For many purposes, including the investigation of surface heterogeneity, the consequences of adsorbing infinitesimal amounts of gas are studied. Then, we obtain the corresponding differential quantities, sometimes also called "derivative" quantities. The required definitions are... 

The Langmuir isotherm is by definition free from interactions between adsorbate molecules (2) and surface heterogeneity (3). It is therefore an ideal model for illustrating the contribution of surface saturation (1) to isotherm nonlinearity. Beginning with the Langmuir isotherm for liquid-solid systems [Eq. (3-5a)], we can define a distribution coefficient K equal to S/iVa , so that ... 

The definition of solubility permits the occurrence of a single solid phase which may be a pure anhydrous compound, a salt hydrate, a non-stoichiometric compound, or a solid mixture (or solid solution, or "mixed crystals"), and may be stable or metastable. As well, any number of solid phases consistent with the requirements of the phase rule may be present. Metastable solid phases are of widespread occurrence, and may appear as polymorphic (or allotropic) forms or crystal solvates whose rate of transition to more stable forms is very slow. Surface heterogeneity may also give rise to metastability, either when one solid precipitates on the surface of auiother, or if the size of the solid particles is sufficiently small that surface effects become important. In either case, the solid is not in stable equilibrium with the solution. See (21) for the modern formulation of the effect of particle size on solubility. The stability of a solid may also be affected by the atmosphere in which the system is equilibrated. 

If all portions of a body have the same specific properties, the body is said to be HOMOGENEOUS if not, it is HETEROGENEOUS. In a sample of matter, any portion that is homogeneous and separated from other parts of the sample by a definite surface or boundary is called a phase. Thus, ice and water are a two-phase system, A layer of oil floating on water is also a two-phase system (oil and water). If the mixture is shaken until the oil is dispersed as droplets in the water, an EMULSION forms, which still consists of two phases (oil and water). 

Apparently, the overlapping of desorption peaks that has its origin in the surface heterogeneity imposes the necessity to resolve the complex TPD curve and to assign particular desorption profiles to the sites of definite strength. Generally, there are two possible methods that can be applied in order to get information concerning the presence and population of particular active sites on the surface of solid material. 

Thus far, Ft has never found a definite position in Ea vs. correlations, more for the uncertainty in the reliability of its pzc than for its work function. On the other hand, Pt is a highly heterogeneous metal and the fact that only polycrystalline surfaces have been used in double-layer studies has not helped remove suspicions. According to Frumkin s data,10,14 the pzc ofpc-Pt is around 0.2 V(SHE) (in acidic solution). If this value is introduced into Fig. 14 (the 0 of pc-Pt is around 5.5 eV),22,65 343,856 865,866 the point of Pt would fall far distant from the line of mercurylike metals and near the line of d-metals. 

The yield of a gas-solid heterogeneous reaction depends not on the total time that molecules spend in the reactor but on the time that they spend on the catalyst surface. The contact time distribution provides a standardized measure of times spent in the absorbed state. A functional definition is provided by the following equation applicable to a first-order, heterogeneous reaction in an isothermal reactor ... 

Attempts to determine how the activity of the catalyst (or the selectivity which is, in a rough approximation, the ratio of reaction rates) depends upon the metal particle size have been undertaken for many decades. In 1962, one of the most important figures in catalysis research, M. Boudart, proposed a definition for structure sensitivity [4,5]. A heterogeneously catalyzed reaction is considered to be structure sensitive if its rate, referred to the number of active sites and, thus, expressed as turnover-frequency (TOF), depends on the particle size of the active component or a specific crystallographic orientation of the exposed catalyst surface. Boudart later expanded this model proposing that structure sensitivity is related to the number of (metal surface) atoms to which a crucial reaction intermediate is bound [6]. 

Let us start with a definition. Semiconductor chemical sensor is an electronic device designed to monitor the content of particles of a certain gas in surrounding medium. The operational principle of this device is based on transformation of the value of adsorption directly into electrical signal. This signal corresponds to amount of particles adsorbed from surrounding medium or deposited on the surface of operational element of the sensor due to heterogeneous diemical reaction. 

A metal cluster can be considered as a polynuclear compound which contains at least one metal-metal bond. A better definition of cluster catalysis is a reaction in which at least one site of the cluster molecule is mechanistically necessary. Theoretically, homogeneous clusters should be capable of multiple-site catalysis. Many heterogeneous catalytic reactions require multiple-site catalysis and for these reasons discrete molecular metal clusters are often proposed as models of metal surfaces in the processes of chemisorption and catalysis. The use of carbonyl clusters as catalysts for hydrogenation reactions has been the subject of a number of papers, an important question actually being whether the cluster itself is the species responsible for the hydrogenation. Often the cluster is recovered from the catalytic reaction, or is the only species spectroscopically observed under catalytic conditions. These data have been taken as evidence for cluster catalysis. 

While CMC is assumed to be an observable and definite value in the case of surfactant monomers, there are frequent reports in the literature of the formation of aggregates or micelle-like associations in solutions of organic solutes so dilute as to preclude apparently the formation of micelles [208, 267-269, 272, 275,278]. Work with different types of commercial surfactants has indicated that molecularly non-homogeneous surfactants do not display the sharp inflection in surface tension associated with CMC in molecularly homogeneous monomers, but rather the onset of aggregation is broad and indistinct [253,267,268]. The lack of well-defined CMCs for non-homogeneous surfactants is speculated to result from the successive micellization of the heterogeneous monomers at different stoichiometric concentrations of the surfactant, which results in a breadth of the monomeric-micelle transition zone. 

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