Explanations

In this Dictionary 1 have aimed to provide an explanation of the terms used in the various branches of chemistry, together with brief accounts of important substances and chemical operations. The Dictionary is intended for use in schools, colleges and universities from the first study of chemistry up to about second year at university or college. We have necessarily had to be selective rather than comprehensive but most chemicals met with at this level should be included. 

The recovery factors for oil reservoirs mentioned in the previous section varied from 5 to 70 percent, depending on the drive meohanism. The explanation as to why the other 95 to 30 percent remains in the reservoir is not only due to the abandonment necessitated by lack of reservoir pressure or high water cuts, but also to the displacement of oil in the reservoir. 

It Is important to know how much each well produces or injects in order to identify productivity or injectivity changes in the wells, the cause of which may then be investigated. Also, for reservoir management purposes (Section 14.0) it is necessary to understand the distribution of volumes of fluids produced from and injected into the field. This data is input to the reservoir simulation model, and is used to check whether the actual performance agrees with the prediction, and to update the historical data in the model. Where actual and predicted results do not agree, an explanation is sought, and may lead to an adjustment of the model (e.g. re-defining pressure boundaries, or volumes of fluid in place). 

We used the concept of sound velocity dispersion for explanation of the shift of pulse energy spectrum maximum, transmitted through the medium, and correlation of the shift value with function of medium heterogeneity. This approach gives the possibility of mathematical simulation of the influence of both medium parameters and ultrasonic field parameters on the nature of acoustic waves propagation in a given medium. 

Two features in relation to the essential requirements merit further explanation, the so-called recognised third party organisations and the European approvals for materials. 

The combined result of two such determinations yielded a leak size figure of 8.8% of the feed flow (with a relative standard deviation of less than 5%). This figure could sufficiently explain the product quality problems experienced, whose alternative explanation in turn was catalyst poisoning. 

Here, r is positive and there is thus an increased vapor pressure. In the case of water, P/ is about 1.001 if r is 10" cm, 1.011 if r is 10" cm, and 1.114 if r is 10 cm or 100 A. The effect has been verified experimentally for several liquids [20], down to radii of the order of 0.1 m, and indirect measurements have verified the Kelvin equation for R values down to about 30 A [19]. The phenomenon provides a ready explanation for the ability of vapors to supersaturate. The formation of a new liquid phase begins with small clusters that may grow or aggregate into droplets. In the absence of dust or other foreign surfaces, there will be an activation energy for the formation of these small clusters corresponding to the increased free energy due to the curvature of the surface (see Section IX-2). 

Theoretical models of the film viscosity lead to values about 10 times smaller than those often observed [113, 114]. It may be that the experimental phenomenology is not that supposed in derivations such as those of Eqs. rV-20 and IV-22. Alternatively, it may be that virtually all of the measured surface viscosity is developed in the substrate through its interactions with the film (note Fig. IV-3). Recent hydrodynamic calculations of shape transitions in lipid domains by Stone and McConnell indicate that the transition rate depends only on the subphase viscosity [115]. Brownian motion of lipid monolayer domains also follow a fluid mechanical model wherein the mobility is independent of film viscosity but depends on the viscosity of the subphase [116]. This contrasts with the supposition that there is little coupling between the monolayer and the subphase [117] complete explanation of the film viscosity remains unresolved. 

The visible crystals that develop during a crystallization procedure are built up as a result of growth either on nuclei of the material itself or surfaces of foreign material serving the same purpose. Neglecting for the moment the matter of impurities, nucleation theory provides an explanation for certain qualitative observations in the case of solutions. 

There are numerous references in the literature to irreversible adsorption from solution. Irreversible adsorption is defined as the lack of desotption from an adsoibed layer equilibrated with pure solvent. Often there is no evidence of strong surface-adsorbate bond formation, either in terms of the chemistry of the system or from direct calorimetric measurements of the heat of adsorption. It is also typical that if a better solvent is used, or a strongly competitive adsorbate, then desorption is rapid and complete. Adsorption irreversibility occurs quite frequently in polymers [4] and proteins [121-123] but has also been observed in small molecules and surfactants [124-128]. Each of these cases has a different explanation and discussion. 

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. 

The basic law of friction has been known for some time. Amontons was, in fact, preceded by Leonardo da Vinci, whose notebook illustrates with sketches that the coefficient of friction is independent of the apparent area of contact (see Refs. 2 and 3). It is only relatively recently, however, that the probably correct explanation has become generally accepted. 

The coefficient of friction between two unlubricated solids is generally in the range of 0.5-1.0, and it has therefore been a matter of considerable interest that very low values, around 0.03, pertain to objects sliding on ice or snow. The first explanation, proposed by Reynolds in 1901, was that the local pressure caused melting, so that a thin film of water was present. Qualitatively, this explanation is supported by the observation that the coefficient of friction rises rapidly as the remperarure falls, especially below about -10°C, if the sliding speed is small. Moreover, there is little doubt that formation of a water film is actually involved [3,4]. 

An alternative explanation that has been advanced is that at the lower temperatures... 

Another indication of the probable incorrectness of the pressure melting explanation is that the variation of the coefficient of friction with temperature for ice is much the same for other solids, such as solid krypton and carbon dioxide [16] and benzophenone and nitrobenzene [4]. In these cases the density of the solid is greater than that of the liquid, so the drop in as the melting point is approached cannot be due to pressure melting. 

While pressure melting may be important for snow and ice near 0°C, it is possible that even here an alternative explanation will prove important. Ice is a substance of unusual structural complexity, and it has been speculated that a liquidlike surface layer is present near the melting point [17,18] if this is correct, the low /t values observed at low sliding speeds near 0°C may be due to a peculiarity of the surface nature of ice rather than to pressure melting. 

Hardy s explanation that the small coefficients of friction observed under boundary lubrication conditions were due to the reduction in the force fields between the surfaces as a result of adsorbed films is undoubtedly correct in a general way. The explanation leaves much to be desired, however, and it is of interest to consider more detailed proposals as to the mechanism of boundary lubrication. 

The traditional, essentially phenomenological modeling of boundary lubrication should retain its value. It seems clear, however, that newer results such as those discussed here will lead to spectacular modification of explanations at the molecular level. Note, incidentally, that the tenor of recent results was anticipated in much earlier work using the blow-off method for estimating the viscosity of thin films [68]. 

Fuerstenau and Healy [100] and to Gaudin and Fuerstenau [101] that some type of near phase transition can occur in the adsorbed film of surfactant. They proposed, in fact, that surface micelle formation set in, reminiscent of Langmuir s explanation of intermediate type film on liquid substrates (Section IV-6). 

After reviewing various earlier explanations for an adsorption maximum, Trogus, Schechter, and Wade [244] proposed perhaps the most satisfactory one so far (see also Ref. 243). Qualitatively, an adsorption maximum can occur if the surfactant consists of at least two species (which can be closely related) what is necessary is that species 2 (say) preferentially forms micelles (has a lower CMC) relative to species 1 and also adsorbs more strongly. The adsorbed state may also consist of aggregates or hemi-micelles, and even for a pure component the situation can be complex (see Section XI-6 for recent AFM evidence of surface micelle formation and [246] for polymeric surface micelles). Similar adsorption maxima found in adsorption of nonionic surfactants can be attributed to polydispersity in the surfactant chain lengths [247], Surface-active impuri-... 

One may rationalize emulsion type in terms of interfacial tensions. Bancroft [20] and later Clowes [21] proposed that the interfacial film of emulsion-stabilizing surfactant be regarded as duplex in nature, so that an inner and an outer interfacial tension could be discussed. On this basis, the type of emulsion formed (W/O vs. O/W) should be such that the inner surface is the one of higher surface tension. Thus sodium and other alkali metal soaps tend to stabilize O/W emulsions, and the explanation would be that, being more water- than oil-soluble, the film-water interfacial tension should be lower than the film-oil one. Conversely, with the relatively more oil-soluble metal soaps, the reverse should be true, and they should stabilize W/O emulsions, as in fact they do. An alternative statement, known as Bancroft s rule, is that the external phase will be that in which the emulsifying agent is the more soluble [20]. A related approach is discussed in Section XIV-5. 

The importance of steric factors in the formation of penetration complexes is made evident by the observation that although sodium cetyl sulfate plus cetyl alcohol gives an excellent emulsion, the use of oleyl alcohol instead of cetyl alcohol leads to very poor emulsions. As illustrated in Fig. XIV-3, the explanation may lie in the difficulty in accommodating the kinked oleyl alcohol chain in the film. 

Make a numerical estimate, with an explanation of the assumptions involved, of the specific surface area that would be found by (a) a rate of dissolving study, (b) Harkins and Jura, who find that at the adsorption of water vapor is 6.5 cm STP/g (and then proceed with a heat of immersion measurement), and (c) a measurement of the permeability to liquid flow through a compacted plug of the powder. 

The polarization model suggests strongly that orientational effects should be present in multilayers. As seen in Section X-6, such perturbations are essential to the explanation of contact angle phenomena. 

Fig. XVn-16. Infrared absorption spectra of H2 physisorbed on NaCl(lOO) at 30 K. See text for explanations. (From Ref. 96. Reprinted with permission from American Institute of Physics, copyright 1993.)...

The accepted explanation for the minimum is that it represents the point of complete coverage of the surface by a monolayer according to Eq. XVII-37, Sconfig should go to minus infinity at this point, but in real systems an onset of multilayer adsorption occurs, and this provides a countering positive contribution. Some further discussion of the behavior of adsorption entropies in the case of heterogeneous adsorbents is given in Section XVII-14. 

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. 

It is not surprising, in view of the material of the preceding section, that the heat of chemisorption often varies from the degree of surface coverage. It is convenient to consider two types of explanation (actual systems involving some combination of the two). First, the surface may be heterogeneous, so that a site energy distribution is involved (Section XVII-14). As an example, the variation of the calorimetric differential heat of adsorption of H2 on ZnO is shown in Fig. 

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