Carbonates, basic behavior

These reduction products may dissolve in the bulk solution or may precipitate to produce surface films. (However, this depends strongly on the type of cation in the solution.) An important issue that relates to the basic behavior of carbons in nonaqueous systems is their use as insertion anodes in high energy density, rechargeable batteries [82], This subject is an extensive one and includes surface and material science consideration of carbonaceous material, and thus is beyond the scope of this chapter. However, some aspects of insertion carbon... 

The mechanism describing the basic behavior of the edge pyrone groups in the graphitic basal planes of the carbon black is depicted below it derives from the... 

Much less clear is the nature of basic sites on the surface of carbons. It is well known for a long time that carbons can adsorb acids. Hydrochloric acid is usually taken for the determination of acid-binding sites, and a preferred concentration is 0.05N [37, 38], analogous to the titration of acidic functions with NaOH. In particular, such carbons show basic behavior, which have been outgassed at high temperatures, e.g., 800-1100°C, and cooled to ambient temperature in a high vacuum or under an inert gas. Thus, many freshly produced carbon materials, such as activated carbons or carbon blacks, show basic reaction. 

Concerning the surface science of carbons, up to now, very little attention has been paid to the inorganic matter usually found in carbon materials, and to its contribution on the acidic/basic behavior of the carbon [68, 349]. 

Recently, Menendez [78] reviewed the use of calorimetric techniques to assess the chemical properties of carbons (e.g., the nature of surface groups, hydrophobic/ hydrophilic character, acidic/basic behavior). Here we summarize the key issues. 

The IR spectra of these samples have been studied, as well as the interaction with CO and CO2, this latter with the purpose of obtaining evidence of any possible basic behavior. Carbon dioxide can indeed react with possibly occurring basic oxygen species to yield carbonates with characteristic IR features. No carbonate species was observed. Instead, a molecular interaction with cations, reversible at room temperature, was found, which was monitored both by IR and microcalorimetry. Besides showing the absence of basicity, interaction with carbon dioxide allowed to titrate the exposed M+ cations, thus showing that only a fraction of cations are accessible. A dramatic decrease in the differential heats of adsorption, not accompanied by a concomitant shift in IR bands of the adsorbed species, indicated that interaction with CO2 implies some extraction of cations from the surface, to which corresponds an endothermic step. 

The percolation threshold, cpc, is the fiUer loading level at which the polymer first becomes conductive, which is generally considered to be a value of about 10 S/cm. Comprehensive experimental and theoretical treatments describe and predict the shape of the percolation curve and the basic behaviors of composites as a function of both conductive filler and the host polymer characteristics (36-38). A very important concept is that the porous nature of the conductive carbon powders significantly affect its volume filling behavior. The typical inclusive stractural measurement for conductive carbon powder porosity is dibutyl phthalate absorption (DBF) according to ASTM 2314. The higher the DBF, the greater the volume of internal pores, which vary in size and shape. The crystalhnity of the polymer also reduces the percolation threshold, because conductive carbons do not reside in the crystalhtes but instead concentrate in the amorphous phase. Eq. (2) describes the percolation curve (39). 

Many solids have foreign atoms or molecular groupings on their surfaces that are so tightly held that they do not really enter into adsorption-desorption equilibrium and so can be regarded as part of the surface structure. The partial surface oxidation of carbon blacks has been mentioned as having an important influence on their adsorptive behavior (Section X-3A) depending on conditions, the oxidized surface may be acidic or basic (see Ref. 61), and the surface pattern of the carbon rings may be affected [62]. As one other example, the chemical nature of the acidic sites of silica-alumina catalysts has been a subject of much discussion. The main question has been whether the sites represented Brpnsted (proton donor) or Lewis (electron-acceptor) acids. Hall... 

Acid-Base Behavior. The relative acidity-basicity of the filler, generally determined by measuring the pH value of a slurry of a specific mass of filler in 100 mL of deionized water, can influence the behavior of a filler in some systems. For example, the curing behavior of some elastomers is sensitive to the pH value of carbon black. 

Many factors affect the mechanisms and kinetics of sorption and transport processes. For instance, differences in the chemical stmcture and properties, ie, ionizahility, solubiUty in water, vapor pressure, and polarity, between pesticides affect their behavior in the environment through effects on sorption and transport processes. Differences in soil properties, ie, pH and percentage of organic carbon and clay contents, and soil conditions, ie, moisture content and landscape position climatic conditions, ie, temperature, precipitation, and radiation and cultural practices, ie, crop and tillage, can all modify the behavior of the pesticide in soils. Persistence of a pesticide in soil is a consequence of a complex interaction of processes. Because the persistence of a pesticide can govern its availabiUty and efficacy for pest control, as weU as its potential for adverse environmental impacts, knowledge of the basic processes is necessary if the benefits of the pesticide ate to be maximized. 

Most compounds in which carbon is the key element are classified as organic. Common examples of organic compounds include degreasing solvents, lubricants, and heating and motor fuels. This subsection highlights some of the more common characteristics of organics as they relate to hazards. Various relevant classes of organics are presented in terms of chemical behavior and physical properties. In order to facilitate the discussion to follow, a few basic definitions will be presented first. 

It is noteworthy that only in the case of dehydroquinolizidine derivatives does monomethylation produce the N-alkylated product. The formation of dialkylated products can be explained by a disproportionation reaction of the monoalkylated immonium salt caused by either the basicity of the starting enamine or some base added to the reaction mixture (most often potassium carbonate) and subsequent alkylation of the monoalkylated enamine. Reinecke and Kray 113) try to explain the different behavior of zJ -dehydroquinolizidine and zJ -dehydroquinolizidine derivatives by the difference in energies of N- and C-alkylation transition states because of the presence of I strain. 

On both experimental and theoretical grounds there is little doubt of the importance of polarizability as a major factor in determining the commonly encountered, though variable, high RS /RO ratios. Were thermodynamic carbon affinities mainly responsible for the usual reactivity order RS > RO, the peculiar behavior of chloroquinolines would be very difficult to understand. There is some indication, however, that carbon affinities roughly parallel basicities (hydrogen affinities), In the latter case, lower RS /RO ratios could be explained in terms of the intermediate complex mechanism, ... 

Nucleophilicity roughly parallels basicity when comparing nucleophiles that have the same reacting atom. For example, OH- is both more basic and more nucleophilic than acetate ion, CH3CO2-, which in turn is more basic and more nucleophilic than H20. Since "nucleophilicity" is usually taken as the affinity of a Lewis base for a carbon atom in the Sfj2 reaction and "basicity" is the affinity of a base for a proton, it s easy to see why there might be a correlation between the two kinds of behavior. 

Sneen et al. formulated an intermediate-mechanism theory. The formulation is in fact very broad and applies not only to borderline behavior but to all nucleophilic substitutions at a saturated carbon. According to Sneen, all SnI and Sn2 reactions can be accommodated by one basic mechanism (the ion-pair mechanism). The substrate first ionizes to an intermediate ion pair that is then converted to products ... 

Before dealing with reinforcement of elastomers we have to introduce the basic molecular features of mbber elasticity. Then, we introduce—step-by-step—additional components into the model which consider the influence of reinforcing disordered solid fillers like carbon black or silica within a rabbery matrix. At this point, we will pay special attention to the incorporation of several additional kinds of complex interactions which then come into play polymer-filler and filler-filler interactions. We demonstrate how a model of reinforced elastomers in its present state allows a thorough description of the large-strain materials behavior of reinforced mbbers in several fields of technical applications. In this way we present a thoroughgoing line from molecular mechanisms to industrial applications of reinforced elastomers. 

Whether for a class demonstration, a practical joke, or perhaps a clandestine activity, disappearing ink is a fascinating substance. What is the secret to its action One formulation of disappearing ink contains a common acid-base indicator, that is, a substance that by its color shows the acid or basic nature of a solution. One acid-base indicator that shifts from a colorless hue under acidic conditions to a deep blue color in alkaline solutions is thymolphthalein. If the indicator starts off in a basic solution, perhaps containing sodium hydroxide, the typical blue color of an ink is perceived. How does the ink color disappear This behavior is dependent upon the contact of the ink with air. Over time, carbon dioxide in the air combines with the sodium hydroxide in the ink solution to form a less basic substance, sodium carbonate. The carbon dioxide also combines with water in the ink to form carbonic acid. The indicator solution responds to the production of acid and returns to its colorless acid form. A white residue (sodium carbonate) remains as the ink dries. 

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