Titration method surface area

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

Another key contribution of the Schwarz group was the recognition of the dramatic influence of oxide surfaces on bulk solution pH. In a landmark 1989 paper, Noh and Schwarz [7] demonstrated the method of mass titration, in which successive additions of oxide cause stepwise shifts in solution pH. This procedure is illustrated in Figure 6.7 [7], As indicated in Figure 6.1, the protonation-deprotonation chemistry of the surface hydroxyl groups is coupled to the liquid-phase pH. In mass titration, as the mass (or more appropriately, the surface area) of oxide in solution increases, the solution pH is brought to the PZC of the oxide, at which point no driving force for proton transfer exists... 

Another way of investigating structure is through the classical method on metals of varying catalyst particle size. The key to this method is to measure active catalyst surface areas in order to determine changes in turnover rates with ensemble size. In recent years several chemisorption techniques have been developed to titrate surface metal centers on oxides (25). In this volume Rao and Narashimha and Reddy report on the use of oxygen chemisorption to characterize supported vanadium oxide. 

The detailed synthesis procedure and textural properties (surface area, Sggy in m2 g-1 pore volume, V in ml g"1 and main pore diameter, d in nm), determined by nitrogen adsorption from 8.E.T. method have been published elsewhere (refs. 13-18) and are summarized in Table 1, where the surface acidity and basicity of supports are also collected. These values were determined by a spectro-photometric method described elsewhere (ref. 19), that allows titration of the amount (in tunol g 1) of irreversibly adsorbed benzoic acid (BA, pKa> 4.19), pyridine (PY, pka= 5.25) or 2,6-diterbutyl-4-methylpyridine (DTMPY, pKa 7.5) employed as titrant agents of basic and acid sites, respectively. Furthermore, the apparent rate constant values of different supports in the gas-phase skeletal isomerization of cyclohexene (CHSI), in Mmol atm"1 g"1 s-1, at 673 K, are also collected in Table 1, because these values are another way of measuring the stronger acid sites of supports (ref. 19). 

The major advantage of protein adsorption studies on high surface area materials is that changes of some extensive properties which accompany the process of adsorption are large enough to be directly measured heat of adsorption through microcalorimetry 141), uptake or release of small ions by a combination of electrokinetic methods and titration 142), thickness of adsorbed layer or an increase of the volume fraction of solid phase by a hydrodynamic method like viscometry 143). Chromatographiclike analysis can also be applied to protein adsorption 144). 

In most applications we want to know the charge density of dispersed systems. To determine the surface charge of dispersed particles, titration methods can be used. Before we can do a quantitative titration experiment we need to know the specific surface area, that is the total... 

This unique micro structure can be described as an intermediate stage between a supported catalyst and a bulk metallic sponge or skeletal Raney-type catalyst. It enables a reasonably high dispersion of Cu and exposure of many Cu-ZnO interfaces at a high total Cu content. The specific Cu surface area (SACu) of methanol catalysts can be determined by reactive N20 titration [59, 60], which causes surface oxidation of the Cu particles and allows calculation of SAcu from the amount of evolved N2. The SACu of state-of-the-art methanol synthesis catalysts measured by this method... 

Selective chemisorption methods have been used with success for the determination of metal surface area and particle size in supported catalysts, and for titration of acid sites on silica-alumina and zeolite catalysts. The chemisorption methods are sometimes neglected in the quest for a more physical description of the catalyst surface, possibly with the penalty of missing an important and quantitative piece of information about the catalyst surface. 

Il e degree of adsorption saturation and the area occupied by an emulsifier molecule in the satiuated adsorption layer on the surface of latex particles were determined by means of the adsorption titration method (16). Sizes of latex particles were determined... 

Hydroxyl-Zr bentonite catalyst for esterification was prepared. Effects of the preparation conditions (calcination temperature, calcination time and ageing time) on interlayer distance, specific surface area and surface total acidity of catalyst have been studied. XRD, BET method and potentiometric titration were respectively used to detennine interlayer distance, specific surface area and surface total acidity of catalyst. Scanning Electron Microscopy was performed to observe the images of samples. 

Surfaces of disperse materials are less well defined than that of mercury. Problems are Incurred with heterogeneity, non-zero solubility, non-inertness on titration, the presence of impurities remaining after the preparation, etc. Some uncertainty as to the specific surface area Ag also presents itself even if a reproducible value is determined when using an established method such as BET (Nj) gas adsorption some reservation remains about its physical meaning do Ions adsorbing from solution "see" the same surface as Nj molecules adsorbing from the gas phase at subzero temperatures on evacuated samples Because of... 

Phenol and the three dihydroxybenzenes (20, 42, 66) in water were determined by LLE with a hydrophilic solvent followed by amperometric titration. LOD was in the ppm range . A dual electrode in a FIA system has been used as detector for total phenols in wastewater. The upstream coulometric electrode has a large surface area and is used to eliminate compounds that cause interference and the second one is an amperometric electrode for oxidative detection of all phenols. Optimal results were found working with a phosphate buffer at pH 6.8, at potentials of +0.35 V and +0.78 V for the coulometric and amperometric electrodes, respectively. A high sample throughput of 60 per hour can be attained with RSD of 0.1-4%. This method is more reliable than the colorimetric method . The concentration of fenobucarb (142) in drinking water was determined after a short alkaline hydrolysis, and oxidation of the resulting 2-s-butylphenol with a GCE at 750 mV, pH 3.5 LOD was 3.6 x 1Q- M, RSD 3.74% for 1 x IQ- M (n = 11, p = 0.05)37 . 

A carbon black sample is treated with excess of iodine. The excess iodine is then titrated with a sodium thiosulfate solution. The result is expressed as adsorbed iodine per unit of mass of the sample. The iodine number depends on amount of volatiles, surface porosity, and extractables. The iodine number correlates with the nitrogen specific surface area. It is a simple method used to evaluate the quality of carbon black. 

A chromatographic method to determine the Gq of materials with low surface area was proposed in [694], Gq was calculated from the diffuse front of a breakthrough curve. Measurements at pH = 7 are not possible in this method, since the solution is unbuffered and it is difficult to obtain a solution of well-defined pH. As is classical potentiometric titration, the charging curves usually require a correction for an acid or base associated with solid particles. 

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