Oxides acid-base properties

Ingo, G.M., Riccucci, C., and Chiozzini, G., Origin of gas porosity in gold-based alloys cast in calcium sulfate-bonded investment and influence of metal oxide acid-base properties on calcium sulfate thermal stabihty, J. Am. Ceram. Soc., 84, 1839, 2001. 

Attempts have been made of correlating the oxide acid-base properties, as determined by calorimetric techniques, and the corresponding catalytic activity and selectivity for the decomposition of propan-2-ol [126] and 4-methylpentan-2-ol [125]. As discussed in ref [127], however, this sort of correlations, in addition to the limitations inherent to the cleaning procedure applied in the calorimetric measurements, has a second difficulty under reaction conditions, the interaction of alcohols with the surface of rare earth sesquioxides leads to the formation of carboxilate and carbonate species which certainly will modify the acid-base properties of the actual catalytic surface. 

Aminopyridines, aminopyridine oxides, and 3-aminoquinoline are obviously diazotized by analogous mechanisms. Kalatzis (1967 b) studied the diazotization of 4-aminopyridine over a very large range of acid concentrations (0.0025-5.0 m HC104). This compound is comparable to 2-aminothiazole in its acid-base properties the heterocyclic nitrogen is easily protonated at pH 10, whereas the amino group is a very weak base (pKa = -6.5). Therefore, the kinetics indicate that the (mono-protonated) 4-aminopyridinium ion reacts with the nitrosyl ion. The... 

Acid-base reactivity is an important property of oxide catalysts, and its control is of interest in surface chemistry as well as being of importance in industrial applications. The exposed cations and anions on oxide surfaces have long been described as acid-base pairs. The polar planes of ZnO showed dissociative adsorption and subsequent decomposition of methanol and formic acid related with their surface acid-base properties[3]. Further examples related to the topic of acid-base properties have been accumulated to date[ 1,4-6]. 

Gas-phase methylation of catechol by methanol was studied on y -AI2O3 modified by the basic elements K, Li, Mg and Ca. Addition of 7.5 at.% Mg to y-AljOa was optimal and increased the 3-methyl catechol selectivity from 0.26 to 0.65. X-ray diffraction experiments showed the diffusion of Li and Mg cations into the y -AI2O3 bulk. This induces a change in the surface species (XPS data) and the surface acid-base properties (TPD experiments). Ca and K addition to y-alumina was ineffective due to formation of basic oxide layers on the sur ce. 

We expected to control the direction of OTM reaction over NiO by sur ce modification, namely making use of the interaction between NiO and other conq>onents to beget a synergistic effect. In this paper, two completely different behaviors of the oxidative transformation of methane were performed over the nickel-based catalysts because of the different modifications by alkali metal oxide and rare earth metal oxide and the different interactions between nickel and supports. Furthermore, the two completely different reactions were related with the acid-base properties of catalysts and the states of nickel present. 

The field of surface-mediated synthesis of metal carbonyl clusters has developed briskly in recent years [4-6], although many organometallic chemists still seem to be unfamiliar with the methods or consider themselves ill-equipped to carry them out. In a typical synthesis, a metal salt or an organometallic precursor is brought from solution or the gas phase onto a high-area porous metal oxide, and then gas-phase reactants are brought in contact with the sample to cause conversion of the surface species into the desired products. In these syntheses, characteristics such as the acid-base properties of the support influence fhe chemisfry, much as a solvenf or coreactant influences fhe chemisfry in a convenfional synfhesis. An advanfage of... 

The acid-base oxides such as aluminas were used as catalysts, adsorbents or catalyst supports and it was interesting to know the surface acid-base properties of these catalysts. 

The aim of this study is to develop model reaction for the characterization of the acidity and basicity of various transition aluminas, the experimental conditions being close to that for catalysis use. Among various model reactions, the transformation of cyclopentanol and cyclohexanone mixture was chosen for this work. Indeed, this reaction was well known for estimating simultaneously the acid-base properties of oxide catalysts [1], Two reactions take place the hydrogen transfer (HT) on basic sites and the alcohol dehydration (DEH) on acid sites. The global reaction scheme is shown in Figure 1. 

Relying on concepts such as hydrolysis, complexation, and acid-base properties, the approach embodied in this advanced mechanism is intriguing and demands further investigation in the context of electroless reactions, perhaps being co-opted into other mechanisms as the experimental conditions and results dictate. A possible drawback to the mechanism of surface incipient hydrous oxide mediators is their suggested low concentration, perhaps as low as 0.1% surface coverage [73], In practical electroless... 

Amphoteric is a chemical term used to describe (mainly) oxides or hydroxides that are able to react both with acids and alkalis. In the present use, it is not related to acid-base properties. 

As discussed in the previous section, metal oxides have both acidic and basic properties. The acid-base properties of metal oxides have led to many interesting catalytic reactions. Catalytic reactions such as H2-D2 exchange, hydrogenation, isomerization, dehydrogenation, dehydrohalo-genation, and benzylation can be considered as examples of acid-base catalysis reactions.31-36 These reactions will be briefly discussed in the following section. The remarkable properties of MgO as a catalyst have been well documented in the literature and we shall discuss some of these unique catalytic properties. 

Describe the acid-base properties of metal oxides. 

Br0nsted-Lowery acids are H+ donors and bases are H+ acceptors. Strong acids dissociate completely in water. Weak acids only partially dissociate, establishing an equilibrium system. Weak acid and base dissociation constants (Ka and Kb) describe these equilibrium systems. Water is amphoteric, acting as both an acid or a base. We describe water s equilibrium by the Kw expression. A pH value is a way of representing a solution s acidity. Some salts and oxides have acid-base properties. A Lewis acid is an electron pair acceptor while a Lewis base is an electron pair donor. 

Compare the solubility of amorphous Fe(OH)3(s), as given in the figure below with the acid base properties of a solid hydrous ferric oxide (cf. Fig. 2.3). Is there a connection between the solubility minimum and the pHpznpc ... 

Di Cosimo et al. investigated the structural requirements and reaction pathways in condensation reactions of alcohols, using Mg/Al mixed oxides obtained by decomposition in N2 at 673 K for 4 h of LDH precursors with a wide range of composition [53], and found that the mechanistic pathway of the condensation reactions is affected not only by the catalyst acid-base properties but also by the chemical nature of the alcohols as well as steric factors. 

Lux-Flood acid-base properties of dissolved oxides. 

It is obvious that the acid-base property of a dissolved oxide may markedly affect the structure of a silicate melt. A dissolved acidic oxide associates the free oxygen, thus displacing reaction 6.4 toward the right, resulting in a marked correlation between the field strength of the dissolved cation and the polymerization constant of the melt. This correlation is shown in the values listed in table 6.2. 

The main usefulness of Eh-pH diagrams consists in the immediacy of qualitative information about the effects of redox and acid-base properties of the system on elemental solubility. Concerning, for instance, cerium, figure 8.20 immediately shows that, within the stability field of water, delimited upward by oxidation boundary curve o and downward by reduction boundary curve r, the element (in the absence of other anionic ligands besides OH groups) is present in solution mainly as trivalent cerium Ce and as soluble tetravalent hydroxide Ce(OH)2. It is also evident that, with increasing pH, cerium precipitates as trivalent hydroxide Ce(OH)3. 

Phenol methylation to 2,6-xylenol has been widely studied for the past few deeades owing to the room for improvisation from the viewpoint of product selectivity. Generally during phenol methylation to 2,6-xylenol, occurs via sequential methylation of phenol to o-cresol to 2,6-xylenol, various reaction parameters mediate the selectivity between the two. For instance, when the reaetants stoichiometry of methanol to phenol molar ratio > 2, and significant residence time of o-cresol may favor 2,6-xylenol selectivity. However, excess methanol is often used, sinee some amount of methanol tend to undergo oxidation into various reformate produets [71] under vapor phase condition. Similarly, reaction temperature, catalyst acid-base property, and space velocity of the reaetant are the parameters that govern the selectivity to 2,6-xylenol. 

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