Adsorption of water

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. 

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. 

Wu M-C, Estrada C A, Corneille J S and Goodman D W 1996 Model surface studies of metal oxides adsorption of water and methanol on ultrathin MgO films on Mo(IOO) J. Chem. Phys. 96 3892... 

Fig. 5.13 Adsorption isotherms on graphitized and on ungraphitized charcoal, (a) Adsorption of water vapour (fc) adsorption of nitrogen at — 195°C. The adsorption values are expressed in cm of liquid adsorbate per gram of adsorbent. (Courtesy Kiselev. )...

An outstanding feature of the adsorption of water vapour on silica is its sensitivity to the course and subsequent treatment of the silica sample, in particular the temperature to which it has been heated. Figure 5.15 shows the strong dependence of the isotherm for a particular silica gel on the temperature of its heat treatment the isotherm is progressively lowered as the temperature increases, especially above 400°C, and the shape changes from Type II for the lower temperatures to Type III for 600°C, 800°C and 1000°C. 

The adsorption of water on a fully hydroxylated silica involves hydrogen bonding but is essentially physical in nature and is completely reversible in the low pressure range the isotherm is of Type II on a nonporous sample (Fig. 5.17(a)), and of Type IV, with no low-pressure hysteresis, on a porous sample (Fig. 5.18). 

Fig. 5.17 Adsorption of water vapour at 25°C on samples of nonporous silica (TK 800). (a) The sample had been exposed to nearly saturated water vapour (p/p° = 0-98) before determination of the isotherm, (b) The sample had been outgassed at 1000°C. (Some points omitted for clarity.)...

Fig. 5.19 Adsorption of water vapour on a silica gel which had been heated at 900°C. (The water content, calculated from the loss in weight at 1000°C, was 0-2%.) First run O, adsorption ( ), desorption. Second run , adsorption desorption.

A detailed study of the physical and chemical adsorption of water on three xerogels, ferric oxide, alumina and titania, as well as on silica (cf. p. 272) has been carried out by Morimoto and his co-workers. Each sample was outgassed at 600°C for 4 hours, the water isotherm determined at or near 20°C, and a repeat isotherm measured after an outgassing at 30 C. The procedure was repeated on the same sample after it had been evacuated at a... 

A discussion of the adsorption of water on oxides would be incomplete without some reference to the irreversible effects which are often encountered when samples of oxide, hydroxide or oxide-hydroxide are exposed to the vapour. These effects ( low-temperature ageing ), which manifest themselves in changes in surface area, in pore structure and sometimes in the lattice structure itself, are complex and difficult to reproduce exactly. ... 

H2O/100 kg of adsorbent. At equilibrium and at a given adsorbed water content, the dew point that can be obtained in the treated fluid is a function only of the adsorbent temperature. The slopes of the isosteres indicate that the capacity of molecular sieves is less temperature sensitive than that of siUca gel or activated alumina. In another type of isostere plot, the natural logarithm of the vapor pressure of water in equiUbrium with the desiccant is plotted against the reciprocal of absolute temperature. The slopes of these isosteres are proportional to the isosteric heats of adsorption of water on the desiccant (see... 

XPS was used to determine the surface composition of the anodized aluminum substrate during exposure to warm, moist environments. The information obtained was used to construct surface behavior diagrams that showed that hydration of the surface involved three steps [38]. Step one, which was reversible, consisted of adsorption of water onto the AIPO4 monolayer. The second step, which was rate-controlling, involves dissolution of the phosphate followed by rapid hydration... 

Fig. 20.3 Adsorption of water dipoles, (a) A water dipole showing the positive hydrogen end and negative oxygen end, b) adsorption on metal with large negative excess charge, (c) adsorption on metal with large positive excess charge and (d) adsorption on metal with small negative...

It has been outlined by several authors that the single macromolecule may be irreversibly bound because of the large number of weakly interacting segments. The first papers on the construction of polymer-coated silica adsorbents involved the physical adsorption of water-soluble polymers. Polyethylene oxides [28, 29] and poly-/V-vinylpyrrolidone [30] are examples of the stationary phases of this type. 

Zeolites are naturally occurring hydrous aluminum-sodium silicates in porous granule form. They are capable of exchanging their sodium base for calcium or magnesium and of expelling these alkaline earth metals for sodium by treatment with salt. Thus, they are a type of ion-exchange media. (Some zeolites act as molecular sieves by adsorption of water and polar compounds.)... 

It seems hard to support the above hypothesis on the basis of work function measurements for Hg in the presence of residual gases. Adsorption of water indeed reduces the work function and this is also the case with inert gases. There remains the possibility of surface oxidation by residual oxygen, but the values of Ayr measured with the Hg stream have been shown42,43 to be stable even in the presence of 02 impurities provided the gas flows rapidly, as was the case during the experiments. The same conclusion has been reached recently by measuring the work function of Hg in ambient gas.46... 

Figure 4. Sketch to illustrate the situation believed to exist at a metal surface upon adsorption of water from the gas phase (or at the surface of an emersed electrode). In particular, the layer thickness is so small that the orientation of solvent molecules at the external surface is strongly affected by the orientation at the internal surface.

There are no direct, reliable measurements of 0 based upon adsorption of water from the gas phase. Therefore, 4.25 eV applies to a macroscopic water layer as in the electrochemical configuration. The decrease in 0 upon water adsorption is a general occurrence with metals. The value of A0 observed with Hg is the lowest among those available in the literature.35,36 With reference to Eq. (20), this means that the perturbations of the surfaces of the two phases are small for the Hg/water contact. In other words, the interaction between Hg and water is weak (hydrophobic). 

Figure 27. Gibbs energy of adsorption of water from the bulk of the solution on the given metals as calculated by Afanasyev and Akulova.909 The figures on top of the bars are the values of the interfacial parameter, AX.

Gibbs energy for the adsorption of water and the interfacial parameter, 187 Gokstein and the piezo electric method for the determination of the potential of zero charge, 42 Gold... 

Quantum chemical calculations, 172 Quantum chemical method, calculations of the adsorption of water by, 172 Quantum mechanical calculations for the metal-solution interface (Kripsonsov), 174 and water adsorption, 76 Quartz crystal micro-balance, used for electronically conducting polymer formation, 578... 

In aqueous solution an elevated pressure favors the Kolbe-coupling against non-Kolbe products [37]. A possible explanation is that high pressure aids the formation of a lipophilic medium at the electrode surface that prevents the adsorption of water and thus disfavours the formation of carbenium ions. 

Adsorption of water on salt crystals plays a key role in many atmospheric and environmental processes. Alkah halides in particular play an important role in the first stages of drop growth in clouds. To understand the atomistic details of the wetting and dissolution processes that take place in these crystals, we apphed SPFM to the smdy of the adsorption of water vapor on single crystal surfaces and the role of surface defects, such as steps. 

Step 1 represents adsorption of ammonia and step 2 its activation. The irreversible step 3 is obviously not elementary in nature, but unfortunately much information on the level of elementary steps is not available. Step 4 describes water formation and step 5 is the reoxidation of the site. Step 6 describes the blocking of sites by adsorption of water. The model thus relies on partially oxidized sites and vacancies on an oxide, similarly to the hydrodesulfurization reaction described in Chapter 9. The reactions are summarized in the cyclic scheme of Fig. 10.15. 

The second part of the paper Is devoted to some aspects of the current status of the theory of chemisorption There, in particular, Che adsorption of water and ammonia will be studied and discussed Through the theory a qualitative understanding of the bonding of these molecules to surfaces Is achieved which Is In agreement with Che experimental observations ... 

The main calorimetric studies on adsorption of water and ammonia on TS-1 and silicalite-1 have been reported by Bobs et al. [64,83,84,86], while other contributions came from the Auroux group [92] and Janchen et al. [93]. Cor-ma s group has investigated the interaction of water on zeolite [39]. The most important conclusion from the available literature is that calorimetric data require a very careful analysis, as probe molecules interact both with the silanols of the internal hydroxyl nests (see Sect. 3.8) and with Ti(lV) species. 

Iwasita, T. and Xia, X. (1996) Adsorption of water at Pt(lll) electrode in HCIO4 solutions. The potential of zero charge. 

Water taken up by solid materials is generally classified as water bound by physical forces or water bound by chemical bonds. Physically bound water includes adsorbed water, trapped or liquid-inclusion water, and absorbed water. The physical adsorption of water occurs when water condenses or is held on the surface the surface includes the cracks, crevices, etc. of real materials. Liquid inclusion occurs during the crystallization process when bubbles of water are trapped. 

The potential of relevance for competitive adsorption of water may shift upon alloying Pt. The calculated ratio of water to oxygen binding energies at the UHV... 

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