Enthalpies of adsorption

As with enthalpies of adsorption, the entropies tend to approach the entropy of condensation as P approaches in further support of the conclusion that the nature of the adsorbate is approaching that of the liquid state. 

Flere is the volume of gas required to saturate the monolayer, V the total volume of gas adsorbed, P the sample pressure, P the saturation vapour pressure and C a constant related to the enthalpy of adsorption. The resulting shape of the isothemi is shown plotted in figure Bl.26.6 for C = 500. A plot of P/V(P - Pq) against P/Pq should give a straight line having a slope (C - )/y C and an intercept The BET surface area is... 

Similarly, one may define the molar integral enthalpy of adsorption, SJt as... 

Similarly, the differential molar enthalpy of adsorption, Ji is defined as... 

J is alternatively called "derivative enthalpy of adsorption", and "derivative entropy of adsorption". ... 

Now A. the diflerential molar enthalpy of adsorption, is often termed the isosteric enthalpy of adsorption (or alternatively the isosteric heat of adsorption) and is given the opposite sign. Thus... 

Fig. 2.11 Curves of the differential enthalpy of adsorption of nitrogen against surface coverage 0 (= for samples of Sterling carbon black heated at the following temperatures (a) 1500°C (fc) 1700°C (c) 2200 C (d) 2700°C. The curve for 2000°C was similar to (c). but with a lower peak. The calorimetric temperature was 77-5, 77-7, 77-4, 77-4 K in (a), (fc), (c) and (d) respectively.

Fig. 2.12 Plot of the calorimetric difTeFential enthalpy of adsorption A h) against amount adsorbed (n), for (u) n-pentane, (f)) /i-hexane, (c) n-heptane, d) n-octane, all adsorbed on graphitized car n black. The point corresponding to n = is marked on each curve. (Courtesy Kiselev.)...

The lower pressure sub-region is characterized by a considerable enhancement of the interaction potential (Chapter 1) and therefore of the enthalpy of adsorption consequently the pore becomes completely full at very low relative pressure (sometimes 0 01 or less), so that the isotherm rises steeply from the origin. This behaviour is observed with molecular sieve zeolites, the enhancement of the adsorption energy and the steepness of the isotherm being dependent on the nature of the adsorbent-adsorbate interaction and the polarizability of the adsorbate. -... 

In the higher pressure sub-region, which may be extended to relative pressure up to 01 to 0-2, the enhancement of the interaction energy and of the enthalpy of adsorption is relatively small, and the increased adsorption is now the result of a cooperative effect. The nature of this secondary process may be appreciated from the simplified model of a slit in Fig. 4.33. Once a monolayer has been formed on the walls, then if molecules (1) and (2) happen to condense opposite one another, the probability that (3) will condense is increased. The increased residence time of (1), (2) and (3) will promote the condensation of (4) and of still further molecules. Because of the cooperative nature of the mechanism, the separate stages occur in such rapid succession that in effect they constitute a single process. The model is necessarily very crude and the details for any particular pore will depend on the pore geometry. 

As already shown in Figures 2.6, 2.15, 2.22 and 5.26 very often it is found that the binding energy, Ebj, or enthalpy of adsorption, AHj, is related linearly to the change in work function [Pg.300]

Although we do not wish to imply that equation (6.20) is a general fundamental equation, we are also not aware of any published exceptions to the physical meaning it conveys, i.e. that the enthalpy of adsorption and thus, according to any isotherm, the coverage of an electron acceptor/donor adsorbate decreases/ increases with increasing work function O and thus decreasing Fermi level EF. 

The term free enthalpy of adsorption is synonymonsly used for free energy of adsorption and Gibbs energy of adsorption. 

Obviously AGad depends on the strength of the solvent-surfaee and the adsorbate-surfaee interaction in addition S-S-, A-A- and S-A-interactions contribute. Various simplifications are possible [74Tra]. As a further complication the electrical field being always present (except at at the electrode/solution-interface has to be considered. Consequently the free enthalpy of adsorption can be split into a chemical part and an electrical part ... 

Proper definition of the reference state is essential for the compatibility of values of the free enthalpy of adsorption results in values of obtained by various authors and with different methods [87Jas,... 

Table 4.1. Free enthalpies of adsorption of ions and organie moleeules at metal eleetrodes.

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