Heterogeneity, constitutional

Molar mass, relative molecular mass, or molecular weight calculated from experimental data without the application of appropriate corrections, such as for finite polymer concentration, association, preferential solvation, compositional heterogeneity, constitutional heterogeneity. 

Constitution heterogeneity (CH) is the variation between individual fragments or particles (for solids) or between individual molecules (for liquids and gases). The constitution of a batch of matter is said to be homogeneous when all the constitutive elements making up the batch are strictly identical with one another with respect to the chemical or physical characteristic of interest (Gy, 1992, p. 49). The batch has a heterogeneous constitution when its units are not strictly identical (Pitard, 1993, p. 58). 

Catalysis in a single fluid phase (liquid, gas or supercritical fluid) is called homogeneous catalysis because the phase in which it occurs is relatively unifonn or homogeneous. The catalyst may be molecular or ionic. Catalysis at an interface (usually a solid surface) is called heterogeneous catalysis, an implication of this tenn is that more than one phase is present in the reactor, and the reactants are usually concentrated in a fluid phase in contact with the catalyst, e.g., a gas in contact with a solid. Most catalysts used in the largest teclmological processes are solids. The tenn catalytic site (or active site) describes the groups on the surface to which reactants bond for catalysis to occur the identities of the catalytic sites are often unknown because most solid surfaces are nonunifonn in stmcture and composition and difficult to characterize well, and the active sites often constitute a small minority of the surface sites. 

Oxide-supported metals constitute one of the most important classes of heterogeneous catalysts, and for this reason they have been investigated by many techniques adsorption isotherms, IR of chemisorbed molecules, electron microscopy, EXAFS, etc. Flowever, the fact that they have been studied by so many methods proves that no one technique is totally satisfactory. 

In the case of coupled heterogeneous catalytic reactions the form of the concentration curves of analytically determined gaseous or liquid components in the course of the reaction strongly depends on the relation between the rates of adsorption-desorption steps and the rates of surface chemical reactions. This is associated with the fact that even in the case of the simplest consecutive or parallel catalytic reaction the elementary steps (adsorption, surface reaction, and desorption) always constitute a system of both consecutive and parallel processes. If the slowest, i.e. ratedetermining steps, are surface reactions of adsorbed compounds, the concentration curves of the compounds in bulk phase will be qualitatively of the same form as the curves typical for noncatalytic consecutive (cf. Fig. 3b) or parallel reactions. However, anomalies in the course of bulk concentration curves may occur if the rate of one or more steps of adsorption-desorption character becomes comparable or even significantly lower then the rates of surface reactions, i.e. when surface and bulk concentration are not in equilibrium. 

The metathesis reaction of alkenes constitutes a major development in the field of hydrocarbon chemistry in recent years. The first examples of the heterogeneously and the homogeneously catalyzed metathesis of linear alkenes have been published by Banks and Bailey (I) and Calderon et al. (2), respectively. By this reaction, linear alkenes are converted with high selectivity into equimolar amounts of two new alkenes, according to ... 

P-Lactamases are enzymes that hydrolyze the P-lactam ring of P-lactamantibiotics (penicillins, cephalosporins, monobactams and carbapenems). They are the most common cause of P-lactam resistance. Most enzymes use a serine residue in the active site that attacks the P-lactam-amid carbonyl group. The covalently formed acylester is then hydrolyzed to reactivate the P-lacta-mase and liberates the inactivated antibiotic. Metallo P-lactamases use Zn(II) bound water for hydrolysis of the P-lactam bond. P-Lactamases constitute a heterogeneous group of enzymes with differences in molecular structures, in substrate preferences and in the genetic localizations of the encoding gene (Table 1). 

Steps 1 through 9 constitute a model for heterogeneous catalysis in a fixed-bed reactor. There are many variations, particularly for Steps 4 through 6. For example, the Eley-Rideal mechanism described in Problem 10.4 envisions an adsorbed molecule reacting directly with a molecule in the gas phase. Other models contemplate a mixture of surface sites that can have different catalytic activity. For example, the platinum and the alumina used for hydrocarbon reforming may catalyze different reactions. Alternative models lead to rate expressions that differ in the details, but the functional forms for the rate expressions are usually similar. 

Aluminas. Aluminas, porous AI2O3, are available in many forms. They constitute the most important carrier material in heterogeneous catalysis. Alumina is amphoteric and, as a con.sequence, soluble in both acidic and basic media. Precipitation can be performed from an acid solution by adding a base or from a basic solution by adding an acid, as schematically represented in Fig. 3.18. If, for example, at a pH of less than about 3 a base is added to an aqueous solution of aluminium sulphate, a precipitate is formed. If this material is filtered, dried and calcined, an amorphous porous AI2O3 is obtained. At other pH values different porous aluminas can be synthesized. 

A solution is a mixture of two or more substances. The substances involved are mixed so intimately (on the atomic scale) that it is not possible to distinguish their individual properties. A solution constitutes a single phase, as distinct from heterogeneous systems which contain several phases. A solution, however, differs from a chemical compound in that its composition is not fixed but can vary over a range. It is customary to designate the major component of a solution as the solvent, and the minor ones as the solutes. A solvent as well as a solute can be a gas, a solid or a liquid. Depending upon the state of the solute and/or the solvent, several types of solutions may exist. 

Structural as well as dynamical studies of membrane proteins, constituting an estimated 30% of all proteins, are very important in view of their crucial biological importance. These membrane proteins are obviously dynamically heterogeneous systems, even though they are structurally homogeneous without any cross-links or aggregation so far discussed. 

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