Surface proton affinity

The number of sites titrated by NH3 and pyridine are similar except for sample Al-SBA-15(15) which means a good accessibility of pyridine in the solid pores without any steric hindrance. On the contrary, the integral heats of adsorption are higher when using pyridine due to its higher protonic affinity in gas phase compared to NH3 and the way in which probe molecules bind on the solid surface [6, 7]. 

Attention was paid early on to solution pH, and in particular, to a surface — bulk proton balance. Various models of hydroxyl chemistry have been developed in colloid science literature [21], Perhaps the simplest and most common model assumes a single type of OH group and amphoteric behavior (i.e., one set of Kx and K2 from Figure 6.1). More complicated models invoke multiple OH groups and proton affinity distributions [22]. It will be demonstrated below that the simpler type has worked well for the revised physical adsorption (RPA) model. 

Venema, P. Hiemstra,T. Weidler, P.G. van Riemsdijk,W.A. (1998) Intrinsic proton affinity of reactive surface groups of metal (hy-dr)oxides Application to iron (hydrjoxides. J. Colloid Interface Sci. 198 282-295 Venenna, P. Hiemsta, T. Van Riemsdijk,W.A. 

Even when it can be demonstrated that binding results from proton transfer (adsorption at Brpnsted sites on the surface of the solid), the heat of adsorption is not a measurement of the proton affinity of the site. It is, in fact, a convolution of the proton affinity of the acid site on the solid, the proton affinity of the reference base, and the heat of interaction of the resnlting ion pair. 

The acid sites strength can be determined by measuring the heats of adsorption of basic probe molecules. The basic probes most commonly used are NH3 (pTTa = 9.24, proton affinity in gas-phase = 857.7 kJ/mol) and pyridine (pTTa = 5.19, proton affinity in gas-phase = 922.2 kJ/mol). The center of basicity of these probes is the electron lone pair on the nitrogen. When chemisorbed on a surface possessing acid properties, these probes can interact with acidic protons, electron acceptor sites, and hydrogen from neutral or weakly acidic hydroxyls. 

A catalytic cycle is composed of a series of elementary processes involving either ionic or nonionic intermediates. Formation of covalently bound species in the reaction with surface atoms may be a demanding process. In contrast to this, the formation of ionic species on the surface is a facile process. In fact, the isomerization reaction, the hydrogenation reaction, and the H2-D2 equilibration reaction via ionic intermediates such as alkyl cation, alkylallyl anion, and (H2D)+ or (HD2)+ are structure-nonrequirement type reactions, while these reactions via covalently bound intermediates are catalyzed by specific sites that fulfill the prerequisites for the formation of covalently bound species. Accordingly, the reactions via ionic intermediates are controlled by the thermodynamic activity of the protons on the surface and the proton affinity of the reactant molecules. On the other hand, the reactions via covalently bound intermediates are regulated by the structures of active sites. 

Hopkinson was hired by York to teach theoretical organic chemistry (the Woodward-Hoffmann rules were then a hot topic) and to carry out experimental chemistry. Despite the limited computing capacity at York at the time, he managed to complete some work on the electrophilic addition to alkenes. He is probably best known, however, for his work on proton affinities, destabilized carbocations,234 organosilicon compounds, silyl anions and cations, and more recently, on the calculation of potential energy surfaces and thermodynamic properties. He has had a particularly fruitful collaboration with Diethard Bohme.235... 

The increased reactivity of alkoxysilanes in the reaction with isolated silanol groups can be explained by the higher proton affinity of the oxygen atom of the Si-O-Si group, compared to the Cl-atom in the Si-Cl group. This is evidenced by the observation that the physisorption of an alkoxysilane on a silica surface results in a free hydroxyl band shift of approximately 300 cm 1, whereas the physisorption of a chlorosilane induces a shift of only 100 cm 1.89... 

Mui et al.36 report a comparative experimental - theoretical study of amines on both the Si(001)-(2x 1) and the Ge(001)-(2x 1) surface. Both substrates were modeled by X9H12 (X = Si, Ge) clusters, utilizing DFT at the BLYP/6-31G(d) level of theory. For both, the Si and the Ge substrate, formation of a X-N dative bond (X = Si, Ge) is the initial step of the reaction between the considered amine species and the semiconductor surface. Flowever, while primary and secondary amines display N-H dissociation when attached to Si(001)-(2 x 1), no such trend is observed for the Ge counterpart of this system. This deviating behavior may be understood in terms of the energy barrier that separates the physisorption from the chemisorption minimum, involving the cleavage of an H atom. For dimethylamine adsorption, this quantity turned out to be about 50% higher for the Ge than for the Si surface. The authors relate this characteristic difference between the two substrates to the different proton affinities of Si and Ge. 

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