Adjustable parameters

For each binary combination in a multicomponent mixture, there are two adjustable parameters, t 2 21 turn,... 

Two generally accepted models for the vapor phase were discussed in Chapter 3 and one particular model for the liquid phase (UNIQUAC) was discussed in Chapter 4. Unfortunately, these, and all other presently available models, are only approximate when used to calculate equilibrium properties of dense fluid mixtures. Therefore, any such model must contain a number of adjustable parameters, which can only be obtained from experimental measurements. The predictions of the model may be sensitive to the values selected for model parameters, and the data available may contain significant measurement errors. Thus, it is of major importance that serious consideration be given to the proper treatment of experimental measurements for mixtures to obtain the most appropriate values for parameters in models such as UNIQUAC. 

While many methods for parameter estimation have been proposed, experience has shown some to be more effective than others. Since most phenomenological models are nonlinear in their adjustable parameters, the best estimates of these parameters can be obtained from a formalized method which properly treats the statistical behavior of the errors associated with all experimental observations. For reliable process-design calculations, we require not only estimates of the parameters but also a measure of the errors in the parameters and an indication of the accuracy of the data. 

Substitution of Equations (2) and (3) into the equilibrium relations dictated by Equation (2-l)[Pg.99]

If the parameters were to become increasingly correlated, the confidence ellipses would approach a 45 line and it would become impossible to determine a unique set of parameters. As discussed by Fabrics and Renon (1975), strong correlation is common for nearly ideal solutions whenever the two adjustable parameters represent energy differences. 

An apparent systematic error may be due to an erroneous value of one or both of the pure-component vapor pressures as discussed by several authors (Van Ness et al., 1973 Fabries and Renon, 1975 Abbott and Van Ness, 1977). In some cases, highly inaccurate estimates of binary parameters may occur. Fabries and Renon recommend that when no pure-component vapor-pressure data are given, or if the given values appear to be of doubtful validity, then the unknown vapor pressure should be included as one of the adjustable parameters. If, after making these corrections, the residuals again display a nonrandom pattern, then it is likely that there is systematic error present in the measurements. ... 

In many process-design calculations it is not necessary to fit the data to within the experimental uncertainty. Here, economics dictates that a minimum number of adjustable parameters be fitted to scarce data with the best accuracy possible. This compromise between "goodness of fit" and number of parameters requires some method of discriminating between models. One way is to compare the uncertainties in the calculated parameters. An alternative method consists of examination of the residuals for trends and excessive errors when plotted versus other system variables (Draper and Smith, 1966). A more useful quantity for comparison is obtained from the sum of the weighted squared residuals given by Equation (1). 

This sum, when divided by the number of data points minus the number of degrees of freedom, approximates the overall variance of errors. It is a measure of the overall fit of the equation to the data. Thus, two different models with the same number of adjustable parameters yield different values for this variance when fit to the same data with the same estimated standard errors in the measured variables. Similarly, the same model, fit to different sets of data, yields different values for the overall variance. The differences in these variances are the basis for many standard statistical tests for model and data comparison. Such statistical tests are discussed in detail by Crow et al. (1960) and Brownlee (1965). 

Subroutine VPLQK. VPLQK calculates K factors (K = for given values of pressure, temperature, liquid and vapor compositions, and the adjustable parameters. The K factors are calculated from the following relation (Prausnitz, 1969) ... 

The are essentially adjustable parameters and, clearly, unless some of the parameters in A2.4.70 are fixed by physical argument, then calculations using this model will show an improved fit for purely algebraic reasons. In principle, the radii can be fixed by using tables of ionic radii calculations of this type, in which just the A are adjustable, have been carried out by Friedman and co-workers using the HNC approach [12]. Further rermements were also discussed by Friedman [F3], who pointed out that an additional temi is required to account for the fact that each ion is actually m a cavity of low dielectric constant, e, compared to that of the bulk solvent, e. A real difficulty discussed by Friedman is that of making the potential continuous, since the discontinuous potentials above may lead to artefacts. Friedman [F3] addressed this issue and derived... 

Figure C3.5.6 compares the result of this ansatz to the numerical result from the Wiener-Kliintchine theorem. They agree well and the ansatz exliibits the expected exponential energy-gap law (VER rate decreases exponentially with Q). The ansatz was used to detennine the VER rate with no quantum correction Q= 1), with the Bader-Beme hannonic correction [61] and with a correction based [83, M] on Egelstaff s method [62]. The Egelstaff corrected results were within a factor of five of experiment, whereas other corrections were off by orders of magnitude. This calculation represents the present state of the art in computing VER rates in such difficult systems, inasmuch as the authors used only a model potential and no adjustable parameters. However the ansatz procedure is clearly not extendible to polyatomic molecules or to diatomic molecules in polyatomic solvents.

Additionally to and a third adjustable parameter a was introduced. For a-values between 14 and 15, a form very similar to the Lennard-Jones [12-6] potential can be obtained. The Buckingham type of potential has the disadvantage that it becomes attractive for very short interatomic distances. A Morse potential may also be used to model van der Waals interactions in a PEF, assuming that an adapted parameter set is available. 

Breindl et. al. published a model based on semi-empirical quantum mechanical descriptors and back-propagation neural networks [14]. The training data set consisted of 1085 compounds, and 36 descriptors were derived from AMI and PM3 calculations describing electronic and spatial effects. The best results with a standard deviation of 0.41 were obtained with the AMl-based descriptors and a net architecture 16-25-1, corresponding to 451 adjustable parameters and a ratio of 2.17 to the number of input data. For a test data set a standard deviation of 0.53 was reported, which is quite close to the training model. 

C oniparing ihc corc-core repulsion ol lhe above two ec nations with those in the MNDO method, it can be seen that the only dil -ference is in the last term. The extra terms in the AMI core-core repulsion deline spherical Ciaiissian Tun ctioii s — the a. h, and c are adjustable parameters. AMI has between two and I onr Gaussian full ctiori s per atom, ... 

Proposed flux models for porous media invariably contain adjustable parameters whose values must be determined from suitably designed flow or diffusion measurements, and further measurements may be made to test the relative success of different models. This may involve extensive programs of experimentation, and the planning and interpretation of such work forms the topic of Chapter 10, However, there is in addition a relatively small number of experiments of historic importance which establish certain general features of flow and diffusion in porous media. These provide criteria which must be satisfied by any proposed flux model and are therefore of central importance in Che subject. They may be grouped into three classes. 

Equations (8.21) still contain too many adjustable parameters to be of much value for predictive purposes, and Feng and Stewart propose three simpler special cases which may be of practical value. 

Since the void fraction distribution is independently measurable, the only remaining adjustable parameters are the A, so when surface diffusion is negligible equations (8.23) provide a completely predictive flux model. Unfortunately the assumption that (a) is independent of a is unlikely to be realistic, since the proportion of dead end pores will usually increase rapidly with decreasing pore radius. 

In Gunn and King s work only part of the experimental data is available as a check on the form of the dusty gas flux relations the remainder is absorbed in determining the values of the three adjustable parameters K, and In an interesting parallel investigation, Remick and... 

The Lennard-Jones 12-6 potential contains just two adjustable parameters the collision diameter a (the separation for which the energy is zero) and the well depth s. These parameters are graphically illustrated in Figure 4.34. The Lennard-Jones equation may also be expressed in terms of the separation at which the energy passes through a minimum, (also written f ). At this separation, the first derivative of the energy with respect to the internuclear distance is zero (i.e. dvjdr = 0), from which it can easily be shown that v = 2 / cr. We can thus also write the Lennard-Jones 12-6 potential function as follows ... 

The size of the move at each iteration is governed by the maximum displacement, Sr ax This is an adjustable parameter whose value is usually chosen so that approximately 50/i of the trial moves are accepted. If the maximum displacement is too small then mam moves will be accepted hut the states will be very similar and the phase space will onb he explored very slowly. Too large a value of Sr,, x and many trial moves will be rejectee because they lead to unfavourable overlaps. The maximum displacement can be adjuster automatically while the program is running to achieve the desired acceptance ratio bi keeping a running score of the proportion of moves that are accepted. Every so often thi maximum displacement is then scaled by a few percent if too many moves have beei accepted then the maximum displacement is increased too few and is reduced. 

The Hiickel constant k has been inserted here as one more adjustable parameter. Note that the integrated form of equation (126) is exact. 

At moderate ionic strengths a considerable improvement is effected by subtracting a term bl from the Debye-Hiickel expression b is an adjustable parameter which is 0.2 for water at 25°C. Table 8.4 gives the values of the ionic activity coefficients (for Zi from 1 to 6) with d taken to be 4.6A. 

The terms Po, Pa, Pt, Pat, Paa, and Pt,t, are adjustable parameters whose values are determined by using linear regression to fit the data to the equation. Such equations are empirical models of the response surface because they have no basis in a theoretical understanding of the relationship between the response and its factors. An empirical model may provide an excellent description of the response surface over a wide range of factor levels. It is more common, however, to find that an empirical model only applies to the range of factor levels for which data have been collected. 

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