Acid-base specification

Many solution reactions are catalyzed by hydrogen or hydroxyl ions and consequently may undergo accelerated decomposition upon the addition of acids or bases. The catalysis of a reaction by hydrogen or hydroxyl ions is known as acid-base specific catalysis. In many cases, in addition to the effect of pH on reaction rate, there may be catalysis by one or more species of the buffer system. This type of catalysis is known as the acid-base general catalysis. Solutions of vitamin were found to be... 

Ahmed AH, Samuel TH, Watt WW. Multiphoton molecular spectroscopy and excited-state dynamics of enhanced green fluorescent protein (EGFP) acid-base specificity. Chem Phys 2001 274 37-55. 

These effects can be illustrated more quantitatively. The drop in the magnitude of the potential of mica with increasing salt is illustrated in Fig. V-7 here yp is reduced in the immobile layer by ion adsorption and specific ion effects are evident. In Fig. V-8, the pH is potential determining and alters the electrophoretic mobility. Carbon blacks are industrially important materials having various acid-base surface impurities depending on their source and heat treatment. 

Until surface contact, the force between molecules is always one of attraction, although this attraction has different origins in different systems. London forces, dipole-dipole attractions, acid-base interactions, and hydrogen bonds are some of the types of attraction we have in mind. In the foregoing list, London forces are universal and also the weakest of the attractions listed. The interactions increase in strength and also in specificity in the order listed. 

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. 

Flame-Retardant Treatments For Wool. Although wool is regarded as a naturally flame-resistant fiber, for certain appHcations, such as use in aircraft, it is necessary to meet more stringent requirements. The Zirpro process, developed for this purpose (122,123), is based on the exhaustion of negatively charged zirconium and titanium complexes on wool fiber under acidic conditions. Specific agents used for this purpose are potassium hexafluoro zirconate [16923-95-8] [16923-95-8] K ZrF, and potassium hexafluoro titanate [16919-27-0], K TiF. Various modifications of this process have been... 

QuaHty control in the production of organic solvent finish removers may be done by gas—Hquid chromatography, which allows the manufacturer to determine the actual ratio of volatile solvent present in the finished product. If the product does not meet specifications, solvents can be added to bring the product to an acceptable composition. A less expensive approach is to use a hydrometer to determine the specific gravity of the product. The specific gravity indicates if the proper blend has been reached. Nonaqueous acid—base titration may be used to determine the amount of acid or alkaline activator present in a remover. 

In choosing a SAM system for surface engineering, there are several options. Silane monolayers on hydroxylated surfaces are an option where transparent or nonconductive systems are needed. However, trichlorosilane compounds are moisture-sensitive and polymeri2e in solution. The resulting polymers contaminate the monolayer surface, which occasionally has to be cleaned mechanically. CarboxyUc acids adsorb on metal oxide, eg, AI2O2, AgO through acid—base interactions. These are not specific therefore, it would be impossible to adsorb a carboxyUc acid selectively in the presence of, for example, a terminal phosphonic acid group. In many studies SAMs of thiolates on Au(lll) are the system of choice. 

The original catalysts for this process were iodide-promoted cobalt catalysts, but high temperatures and high pressures (493 K and 48 MPa) were required to achieve yields of up to 60% (34,35). In contrast, the iodide-promoted, homogeneous rhodium catalyst operates at 448—468 K and pressures of 3 MPa. These conditions dramatically lower the specifications for pressure vessels. Yields of 99% acetic acid based on methanol are readily attained (see Acetic acid Catalysis). 

Thermoplastic polyamides are used in coatings to modify alkyd resins (qv) in thixotropic systems (238) and to plasticize nitroceUulose lacquers (239). DETA-taH oil fatty acid-based polyamides are suggested for use as corrosion inhibitors in alkyd paints (240). Printing inks for fiexo-gravure appHcation on certain paper, film and foil webs rely on EDA- and PDA-based polyamides for their specific performance (241). 

A requirement underlying the validity of Zisman plots is that there be no specific interactions, such as acid-base interactions, between the solid surface and the probe liquids. Such interactions, however, can, in principle, be taken into account by Young s equation, provided the contact angle remains finite. Their... 

W. quantifies the specific, discrete interactions that exist between a wetting liquid and a substrate. These interactions may be Van der Waals, acid-base, or covalent. The reversible work of adhesion is the product of the areal density of these interaction sites (or attachment points) and the energy per attachment point ... 

Fiber Relative strength Specific gravity Normal moisture content (%) Maximum usable temperature ( F) Acid Base Organic solvent Other attribute... 

In this scheme the reversible conversion of A to O is the reaction whose rate is to be studied, whereas the reduction of O to R is the electrode process. Scheme XIV can also represent a pseudo-first-order formation of O. A specific example is the acid-base equilibrium of pyruvic acid, shown in Scheme XV. 

FIGURE 16.11 Specific and general acid-base catalysis of simple reactions in solution may be distinguished by determining the dependence of observed reaction rate constants (/sobs) pH and buffer concentration, (a) In specific acid-base catalysis, or OH concentration affects the reaction rate, is pH-dependent, but buffers (which accept or donate H /OH ) have no effect, (b) In general acid-base catalysis, in which an ionizable buffer may donate or accept a proton in the transition state, is dependent on buffer concentration. 

For exchange of non-labile organic hydrogen atoms, acid-base catalysis (or some other catalytic hydrogen-transfer agent such as palladium or platinum) is required. The method routinely gives tritiated products having a specific activity almost 1000 times that obtained by the Wilzbach method shorter times are required (2-12h) and subsequent purification is easier. 

Poly(L-malate) decomposes spontaneously to L-ma-late by ester hydrolysis [2,4,5]. Hydrolytic degradation of the polymer sodium salt at pH 7.0 and 37°C results in a random cleavage of the polymer, the molecular mass decreasing by 50% after a period of 10 h [2]. The rate of hydrolysis is accelerated in acidic and alkaline solutions. This was first noted by changes in the activity of the polymer to inhibit DNA polymerase a of P. polycephalum [4]. The explanation of this phenomenon was that the degradation was slowest between pH 5-9 (Fig. 2) as would be expected if it were acid/base-catalyzed. In choosing a buffer, one should be aware of specific buffer catalysis. We found that the polymer was more stable in phosphate buffer than in Tris/HCl-buffer. 

Care must be taken here not to confuse acid cleaners with the high-strength, phosphoric acid-based chemical polishes and chemical brighteners, which are used specifically to obtain the surface finish which such materials produce. Also in the category of acid cleaners could be considered the lightweight alkali-metal phosphating cleaner-coater solutions, but a discussion on such materials is best left to specialist publications on metal pretreatment chemicals. 

The general approach illustrated by Example 18.7 is widely used to determine equilibrium constants for solution reactions. The pH meter in particular can be used to determine acid or base equilibrium constants by measuring the pH of solutions containing known concentrations of weak acids or bases. Specific ion electrodes are readily adapted to the determination of solubility product constants. For example, a chloride ion electrode can be used to find [Cl-] in equilibrium with AgCl(s) and a known [Ag+]. From that information, Ksp of AgCl can be calculated. 

In acid-base titrations the end point is generally detected by a pH-sensitive indicator. In the EDTA titration a metal ion-sensitive indicator (abbreviated, to metal indicator or metal-ion indicator) is often employed to detect changes of pM. Such indicators (which contain types of chelate groupings and generally possess resonance systems typical of dyestuffs) form complexes with specific metal ions, which differ in colour from the free indicator and produce a sudden colour change at the equivalence point. The end point of the titration can also be evaluated by other methods including potentiometric, amperometric, and spectrophotometric techniques. 

However, we have to criticize more specifically the paper by Lown et al. (1984), who characterized alkanediazonium ions, as well as (E)- and (Z)-alkanediazoate ions, by 15N NMR spectroscopy. They also report NMR data on the (E)- and (Z)-benzenediazohydroxides as reference compounds, describing the way they obtained these compounds in only three lines. Obviously the authors are not familiar with the work on the complex system of acid-base equilibria which led 30 years earlier to the conclusion that the maximum equilibrium concentration of benzenediazohydroxide is less than 1 % of the stoichiometric concentration in water (see Ch. 5). The method of Lown et al. consists in adding 10% (v/v) water to a mixture of benzenediazonium chloride and KOH in dimethylsulfoxide. In the opinion of the present author it is unlikely that this procedure yields the (Z)- and CE>benzenediazohydroxides. Such a claim needs more detailed experimental evidence. 

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