Adsorption, coefficient

Settling and rainout are important mechanisms of contaminant transfer from the atmospheric media to both surface soils and surface waters. Rates of contaminant transfer caused by these mechanisms are difficult to assess qualitatively however, they increase with increasing soil adsorption coefficients, solubility (for particulate contaminants or those adsorbed to particles), particle size, and precipitation frequency. 

The first terms in (99) and (100) say that adsorption can take place either on the remaining sites of the reconstructed surface or on those surface sites that are neither reconstructed nor occupied. The first term in (101) allows for reconstruction from the unreconstructed area, 1 — 9, but also says that this reconstruction may be hindered or helped if there is an adsorbate on the unreconstructed surface. A similar interpretation holds for the last term in (101) describing the lifting of the reconstruction. For the adsorption coefficients Wy, Ws, etc., one writes expressions analogous to (47). 

Simultaneously with the decrease of the number of variables, the number of the parameters to be determined also decreases the remaining parameters are, of course, only relative values of, in our case, the rate constants and adsorption coefficients... 

A further procedure will be described only for m-xylene, for which we obtained the following values of the constants fci = 173.7, fc2 = 84.2 mole hr-1 kg-1 atm-1 K — 20.6, Ko = 25.8 atm-1. The conclusions drawn from the study of consecutive hydrodemethylation were similar for all the three xylenes studied (100). The influencing of individual reactions by products and by the intermediate product was determined experimentally, by measuring their effect on the reaction of m-xylene and toluene. The adsorption coefficients, which express this effect, are listed in Table III. 

Values of Adsorption Coefficients Kj (atm 1) of Products Obtained in the Study of Demethylation of m-Xylene and Toluene... 

In contrast to consecutive reactions, with parallel competitive reactions it is possible to measure not only the initial rate of isolated reactions, but also the initial rate of reactions in a coupled system. This makes it possible to obtain not only the form of the rate equations and the values of the adsorption coefficients, but also the values of the rate constants in two independent ways. For this reason, the study of mutual influencing of the reactions of this type is centered on the analysis of initial rate data of the single and coupled reactions, rather than on the confrontation of data on single reactions with intergal curves, as is usual with consecutive reactions. 

The values of the rate constants and adsorption coefficients obtained by the study of isolated reactions agreed well with those obtained by the study of parallel reactions (Table V). The three values of the adsorption coefficient of each acid were obtained independently. In addition to one value from the study of isolated reactions, two additional values were determined by the study of the parallel system one from the kinetics of the consumption of the given acid by reaction (Vila) or (Vllb), and one from the kinetics of reaction (Vile). 

Values of Rate Constants ki (mole hr lkg l) and Adsorption Coefficients Kj (otm l) Obtained in the Study of Ketonization... 

Dimension of constants k1 is (mole X 102 hr-Ikg-Iatm-2) and of adsorption coefficients K, is (atm-1)-b From the study of competitive system (Villa). 

The above mentioned studies were in most cases performed with the aim of obtaining relative reactivities or relative adsorption coefficients from competitive data, sometimes also from the combination of these with the data obtained for single reactions. In our investigation of reesterification (97,98), however, a separate analysis of rate data on several reactions provided us with absolute values of rate constants and adsorption coefficients (Table VI). This enabled us to compare the relative reactivities evaluated by means of separately obtained constants with the relative reactivities measured by the method of competitive reactions. The latter were obtained both from integral data by means of the known relation... 

We have further attempted to suggest a procedure which would make use of the advantages of the method of competitive reactions, i.e. its simplicity and little time demand, and at the same time would yield separately the absolute values of rate constants and adsorption coefficients also for reactions with a more complicated kinetics. Using the values of relative reactivities S from the method of competitive reactions, the adsorption coefficients, for example, of the alcohols (Kb) in the reesterification reaction described by Eq. (26) can be evaluated from the relation... 

Comparison of the Absolute Values of Adsorption Coefficients (atm 1) Obtained by Two Methods in Reesterification Reactions... 

From the results of other authors should be mentioned the observation of a similar effect, e.g. in the oxidation of olefins on nickel oxide (118), where the retardation of the reaction of 1-butene by cis-2-butene was greater than the effect of 1-butene on the reaction of m-2-butene the ratio of the adsorption coefficients Kcia h/Kwas 1.45. In a study on hydrogenation over C03O4 it was reported (109) that the reactivities of ethylene and propylene were nearly the same (1.17 in favor of propylene), when measured separately, whereas the ratio of adsorption coefficients was 8.4 in favor of ethylene. This led in the competitive arrangement to preferential hydrogenation of ethylene. A similar phenomenon occurs in the catalytic reduction of nitric oxide and sulfur dioxide by carbon monoxide (120a). 

From the results of this kinetic study and from the values of the adsorption coefficients listed in Table IX, it can be judged that both reactions of crotonaldehyde as well as the reaction of butyraldehyde proceed on identical sites of the catalytic surface. The hydrogenation of crotyl alcohol and its isomerization, which follow different kinetics, most likely proceed on other sites of the surface. From the form of the integral experimental dependences in Fig. 9 it may be assumed, for similar reasons as in the hy-drodemethylation of xylenes (p. 31) or in the hydrogenation of phenol, that the adsorption or desorption of the reaction components are most likely faster processes than surface reactions. 

Values of Constants ki (mole hr lkff ialm Jl) and of Adsorption Coefficients K j (atm-1) in Parallel-Consecutive Hydrogenation of Crotonaldehyde... 

It is noteworthy that even a separate treatment of the initial data on branched reactions (1) and (2) (hydrogenation of crotonaldehyde to butyr-aldehyde and to crotyl alcohol) results in practically the same values of the adsorption coefficient of crotonaldehyde (17 and 19 atm-1)- This indicates that the adsorbed form of crotonaldehyde is the same in both reactions. From the kinetic viewpoint it means that the ratio of the initial rates of both branched reactions of crotonaldehyde is constant, as follows from Eq. (31) simplified for the initial rate, and that the selectivity of the formation of butyraldehyde and crotyl alcohol is therefore independent of the initial partial pressure of crotonaldehyde. This may be the consequence of a very similar chemical nature of both reaction branches. 

The values of the adsorption coefficient of hydrogen for both reactions were practically identical (1.9 and 2.1 atm-1). Here, the selectivity of the branched reactions depends on the partial pressure of methylcyclopentane. This difference may be accounted for by assuming that either the cleavage of the C—C bond of methylcyclopentane in the (3-position and in the 7-position with respect to the methyl group does not take place on the same sites of the surface of platinum (or on the sites of the same activity), or that the mechanism of hydrogenolysis is more complex than that ex-... 

A similar difference in the adsorption coefficients of the starting reactant of branched reactions was also found in the parallel dehydration and dehydrogenation of isopropyl alcohol on some oxide catalyst (123) here, of course, the chemical nature of both branches is clearly different. It is of interest, however, to note that for the series of catalysts with varying... 

Ratios of Rate Constants and of Adsorption Coefficients in Parallel Dehydrogenation (1) and Dehydration (2) of Isopropyl Alcohol on Some Oxide Catalysts (123)... 

In the cases under study the behavior of each of the compounds present could be expressed by a single value of the adsorption coefficient in all the reactions occurring on the given catalyst. This indicates that this coefficient has a more general meaning, since it is able to characterize a certain substance in different reacting systems [cf. (97) J. It is reasonable to... 

The relative reactivities obtained by the method of competitive reactions corresponded to the values of the separately obtained rate and adsorption constants. The reactivities obtained by the competitive method differ, of course, from the ratio of the rates of the separately studied single reactions this difference increases with the difference in the values of the adsorption coefficients of competing substances. 

Ki adsorption coefficient in the monomolecular isomerization of crotyl alcohol... 

Adsorption Coefficient (K c)—The ratio of the amount of a chemical adsorbed per unit weight of organic carbon in the soil or sediment to the concentration of the chemical in solution at equilibrium. 

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