Comments

It is important to point out once again that explanations (rationalizations) of isotope effects which employ arguments invoking hyperconjugation and/or steric effects are completely equivalent to the standard interpretation of KIE s in terms of isotope independent force constant differences, reactant to transition state. In turn, these force constant differences describe isotope dependent vibrational frequencies and frequency differences which are not the same in reactant and transition states. The vibrational frequencies determine the partition functions and partition function ratios in the two states and thus define KIE. The entire process occurs on an isotope independent potential energy surface. This is not to claim that the 

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Each year the capital allowance is a fixed percentage of the unrecovered value of the asset at the end of the previous year. The same comments about when the allowance can start apply. 

The same general comments hold as for Unit 3. Figure 7 provides an example of the AE monitoring data collected from 19.06.97 to 16.07.97, in terms of the main plant parameters vs time (fig. 7a), as well as of the AE RMS values (fig. 7b). 

Several practical results will be presented and commented. [ Ac uisiiion )... 

To determine time dependent behaviours of the specimen up to 25 measurements in series with different time delays are possible. To prevent mistakes in application many help comments appear when inputs are necessary or differences between the calibration and the measurement are detected. All calibration conditions, a description for the specimen and results can be printed or saved by the hard disk. To reduce the input expenditure, the last configuration is made to current values when the program is stopped ore leave. 

Redaction of the draft was finished during the meeting of September 1997, and it has been sent for two-month enquiry in December 1997. The ad hoc group is now expecting the comments drawn by this enquiry to proceed to the revision of the document and to get it ready for six-month enquiry. 

The authors are grateful to Dr J M Farley of Mitsui Babcock Energy Limited for useful comments. 

Plot the scaling behavior for the surface tension of polystyrene solutions using Eq. III-64, for N = 1,000 and T from zero to Tc- Now plot the behavior for T = 0.87 for N = 100-1000. Comment on the influence of polymers on surface tension. 

About this time Miss Pockelsf [3] showed how films could be confined by means of barriers thus she found little change in the surface tension of fatty-acid films until they were confined to an area corresponding to about 20 per molecule (the Pockels point). In 1899, Rayleigh [5] commented that a reasonable interpretation of the Pockels point was that at this area the molecules of the surface material were just touching each other. The picture of a surface film... 

As a general comment, it is fortunate for the study of monolayers that dissolving processes are generally slow enough to permit the relatively unperturbed study of equilib-... 

Calculate 7wh for the cyclohexane-water interface using the Good-Fowkes approach. Repeat the calculation using Eq. IV-13. Compare both results with the experimental value and comment. 

It was commented that surface viscosities seem to correspond to anomalously high bulk liquid viscosities. Discuss whether the same comment applies to surface diffusion coefficients. 

Using Eqs. VI-30-VI-32 and data from the General References or handbooks, plot the retarded Hamaker constant for quartz interacting through water and through n-decane. Comment on the relative importance of the zero frequency contribution and that from the vuv peak. 

Calculate the heat of immersion of talc in water around 2S°C. Comment on the value. 

An adsorbed film obeys a modified Amagat equation of state, t(t = qkT (see Eq. ni-107). Show that this corresponds to a Freundlich adsorption isotherm (Eq. XI-12) and comment on the situation. 

Irreversible adsorption discussed in Section XI-3 poses a paradox. Consider, for example, curve 1 of Fig. XI-8, and for a particular system let the equilibrium concentration be 0.025 g/lOO cm, corresponding to a coverage, 6 of about 0.5. If the adsorption is irreversible, no desorption would occur on a small dilution on the other hand, more adsorption would occur if the concentration were increased. If adsorption is possible but not desorption, why does the adsorption stop at 6 = 0.5 instead of continuing up to 0 = 1 Comment on this paradox and on possible explanations. 

This description is traditional, and some further comment is in order. The flat region of the type I isotherm has never been observed up to pressures approaching this type typically is observed in chemisorption, at pressures far below P. Types II and III approach the line asymptotically experimentally, such behavior is observed for adsorption on powdered samples, and the approach toward infinite film thickness is actually due to interparticle condensation [36] (see Section X-6B), although such behavior is expected even for adsorption on a flat surface if bulk liquid adsorbate wets the adsorbent. Types FV and V specifically refer to porous solids. There is a need to recognize at least the two additional isotherm types shown in Fig. XVII-8. These are two simple types possible for adsorption on a flat surface for the case where bulk liquid adsorbate rests on the adsorbent with a finite contact angle [37, 38]. 

Brunauer (see Refs. 136-138) defended these defects as deliberate approximations needed to obtain a practical two-constant equation. The assumption of a constant heat of adsorption in the first layer represents a balance between the effects of surface heterogeneity and of lateral interaction, and the assumption of a constant instead of a decreasing heat of adsorption for the succeeding layers balances the overestimate of the entropy of adsorption. These comments do help to explain why the model works as well as it does. However, since these approximations are inherent in the treatment, one can see why the BET model does not lend itself readily to any detailed insight into the real physical nature of multilayers. In summary, the BET equation will undoubtedly maintain its usefulness in surface area determinations, and it does provide some physical information about the nature of the adsorbed film, but only at the level of approximation inherent in the model. Mainly, the c value provides an estimate of the first layer heat of adsorption, averaged over the region of fit. 

On the other hand, as applied to the submonolayer region, the same comment can be made as for the localized model. That is, the two-dimensional non-ideal-gas equation of state is a perfectly acceptable concept, but one that, in practice, is remarkably difficult to distinguish from the localized adsorption picture. If there can be even a small amount of surface heterogeneity the distinction becomes virtually impossible (see Section XVll-14). Even the cases of phase change are susceptible to explanation on either basis. 

Rate effects may not be chemical kinetic ones. Benson and co-worker [84], in a study of the rate of adsorption of water on lyophilized proteins, comment that the empirical rates of adsorption were very markedly complicated by the fact that the samples were appreciably heated by the heat evolved on adsorption. In fact, it appeared that the actual adsorption rates were very fast and that the time dependence of the adsorbate pressure above the adsorbent was simply due to the time variation of the temperature of the sample as it cooled after the initial heating when adsorbate was first introduced. 

When plotted according to the linear form of the BET equation, data for the adsorption of N2 on Graphon at 77 K give an intercept of 0.004 and a slope of 1.7 (both in cubic centimeters STP per gram). Calculate E assuming a molecular area of 16 for N2. Calculate also the heat of adsorption for the first layer (the heat of condensation of N2 is 1.3 kcal/mol). Would your answer for Vm be much different if the intercept were taken to be zero (and the slope the same) Comment briefly on the practical significance of your conclusion. 

Make a plot of Eq. XVII-69 as 6 versus P, and, for comparison, one of a Langmuir adsorption isotherm of same limiting or Henry s law slope. Comment on the comparison. 

Plot the data of Problem II according to Eq. XVII-76 and according to Eq. XVII-79. Comment. 

Referring to Fig. XVII-17, use handbook data to calculate the vapor pressure of O2 ordinary liquid at the melting point of the 6 phase. Comment on the result. Locate the 2D S-L-V triple point. 

Use the data of Problem XVII-11 to obtain an MP plot, as in Fig. XVII-30. Comment on the result. 

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