In the foregoing treatment, Cerofolini's method for the estimate of the surface heterogeneity, based on the relation (1), has been analyzed from the standpoint of numerical mathematics. The limited amount of observed data, their experimental error and the properties of regressional procedures led to notable modifications of the original method. The main result is that the series expansion does not give straightforward solution of the problem, tedious iterations are necessary even for simple analytical forms off(U). Serious difficulties are introduced by the consideration of the incipient second-layer coverages, by existence of a number of maxima inf(U) and by existence of homogeneous regions. Deleterious impairment can be caused by differences in coefficients for the expansions of observed data (N, p) and ofθ(p, T, U). As in other methods, there is no possibility to estimate the absolute value of the least adsorption energyU0, only the relative quantitiesq are extracted from a single adsorption isotherm. In spite of the large amount of needed computations, the method does not give any possibility for estimates of the reliability of the calculated distribution. This contrasts with the recently developed method [8], in which the observed data are correlated by the sum (10). By means of this method, continuous and discontinuous distributions can be dealt with equally well and it can be easily tested whether any supposed distribution fits the data within experimental error. When isotherms at several temperatures and/or calorimetric data are at hand, analysis of the thermodynamic properties of different adsorption sites can be performed. The chief difficulty of the method, the solution of a system of non-linear equations, is much less tedious than the treatment analyzed in this paper.
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