Surface exchange desorption

For this estimate, values for the surface diffusion coefficient (D) and the surface exchange coefficient (i) in eq 2 were obtained by linearizing Mitterdorfer s rate expressions for surface transport and adsorption/desorption (ref 84) and re-expressing in terms of the driving forces in eq 2. 

Atoms adsorbed on a metal surface exchange electrons with it and, as a result, may be desorbed as either atoms or ions. Only those ions and atoms with enough energy to break the adsorption bond will leave the surface. The strength of this bond is measured by the desorption energy, Ea and ., for atoms and singly... 

The vapor phase synthesis of methacrylic acid from propionic acid and formaldehyde was studied [42]. In particular, the choice of alkali metal cation and loading were evaluated for their effect on the activity and selectivity of silica supported catalysts. Experiments were carried out in 0.5 in. (o.d.) quartz reactors equipped with 0.125 in. thermowells. Alkali metal cations supported on silica are effective base catalysts for the production of methacrylic acid. Silica surfaces exchanged with alkali metal cations are capable of chemisorbing propionic acid yielding surface-bound silyl propionate esters and metal propionate salts. The alkali metal cation influences the temperature at which desorption of the ester occurs (Cs < Na < Li < support). For silica catalysts of equimolar cation loading, activity and selectivity to methacrylic acid show the opposite trend, Cs > K. > Na > Li. Methacrylic acid selectivity reaches a maximum at intermediate cation loadings where interaction of adjacent silyl esters is minimized [42]. 

Process 2, the adsorption of the reactant(s), is often quite rapid for nonporous adsorbents, but not necessarily so it appears to be the rate-limiting step for the water-gas reaction, CO + HjO = CO2 + H2, on Cu(lll) [200]. On the other hand, process 4, the desorption of products, must always be activated at least by Q, the heat of adsorption, and is much more apt to be slow. In fact, because of this expectation, certain seemingly paradoxical situations have arisen. For example, the catalyzed exchange between hydrogen and deuterium on metal surfaces may be quite rapid at temperatures well below room temperature and under circumstances such that the rate of desorption of the product HD appeared to be so slow that the observed reaction should not have been able to occur To be more specific, the originally proposed mechanism, due to Bonhoeffer and Farkas [201], was that of Eq. XVIII-32. That is. 

To specify these transition probabilities we make the further assumption that the residence time of a particle in a given adsorption site is much longer than the time of an individual transition to or from that state, either in exchange with the gas phase in adsorption and desorption or for hopping across the surface in diffusion. In such situtations there will be only one individual transition at any instant of time and the transition probabilities can be summed, one at a time, over all possible processes (adsorption, desorption, diffusion) and over all adsorption sites on the surface. To implement this we first write... 

The chemical properties of oxide surfaces have been studied by several methods, including oxygen exchange. This method has been used to investigate the mechanisms of heterogeneous reactions for which oxides are active catalysts [36]. The dimerization step does not necessarily precede desorption and Malinin and Tolmachev [634], in one of the few reviews of decomposition kinetics of solid metal oxides, use this criterion to distinguish two alternative reaction mechanisms, examples being... 

Inorganic reactions in the soil interstitial waters also influence dissolved P concentrations. These reactions include the dissolution or precipitation of P-containing minerals or the adsorption and desorption of P onto and from mineral surfaces. As discussed above, the inorganic reactivity of phosphate is strongly dependent on pH. In alkaline systems, apatite solubility should limit groundwater phosphate whereas in acidic soils, aluminum phosphates should dominate. Adsorption of phosphate onto mineral surfaces, such as iron or aluminum oxyhydroxides and clays, is favored by low solution pH and may influence soil interstitial water concentrations. Phosphorus will be exchanged between organic materials, soil inter-... 

This study presents kinetic data obtained with a microreactor set-up both at atmospheric pressure and at high pressures up to 50 bar as a function of temperature and of the partial pressures from which power-law expressions and apparent activation energies are derived. An additional microreactor set-up equipped with a calibrated mass spectrometer was used for the isotopic exchange reaction (DER) N2 + N2 = 2 N2 and the transient kinetic experiments. The transient experiments comprised the temperature-programmed desorption (TPD) of N2 and H2. Furthermore, the interaction of N2 with Ru surfaces was monitored by means of temperature-programmed adsorption (TPA) using a dilute mixture of N2 in He. The kinetic data set is intended to serve as basis for a detailed microkinetic analysis of NH3 synthesis kinetics [10] following the concepts by Dumesic et al. [11]. 

---