Apparent acidity

The apparent acid strength of boric acid is increased both by strong electrolytes that modify the stmcture and activity of the solvent water and by reagents that form complexes with B(OH) 4 and/or polyborate anions. More than one mechanism may be operative when salts of metal ions are involved. In the presence of excess calcium chloride the strength of boric acid becomes comparable to that of carboxyUc acids, and such solutions maybe titrated using strong base to a sharp phenolphthalein end point. Normally titrations of boric acid are carried out following addition of mannitol or sorbitol, which form stable chelate complexes with B(OH) 4 in a manner typical of polyhydroxy compounds. EquiUbria of the type ... 

The pK values determined are influenced by the solvent and other conditions of the measurement. The nature of the solvent in which the extent or rate of deprotonation is determined has a significant effect on the apparent acidity of the hydrocarbon. In general. 

VV -values for bromoform and pyrrole, acidic liquids, against poly(vinyl chloride), an acidic polymer, and dimethyl sulfoxide, a predominantly basic liquid, against polyfmethyl methacrylate), a basic polymer, but large values for the acidic liquids against PMMA and the basic liquid against PVC. 2-Iodoethanol, a bifunctional liquid, showed appreciable -values with both polymers. Despite these results in line with expectations, other results based on wettability measurements are not so clear-cut. For example, Vrbanac [94] found significant apparent acid-base interactions of various aromatic liquids against poly(ethylene), presumably a neutral substrate. 

The situation is more interesting when the solution is buffered with a weak acid, say HA. Then, if = (H )[A ]/[HA] is the apparent acid dissociation constant, we have... 

The equilibrium is apparently acid catalysed, for the pure anhydride had no effect unless benzoic acid was present. 

Hogeveen138 measured apparent acidity constants of substituted /i-phenylthio-, /J-phenylsulfinyl- and / -phenylsulfonyl-acrylic acids (cis and trans) in 50% v/v ethanol. The p values for transmission through SCH=CH, SOCH=CH and S02CH=CH were 0.531, 0.389 and 0.320 respectively for the cis acids and 0.652, 0.282 and 0.331 for the trans acids. These results were discussed in considerable detail and compared with those of pertinent related systems. Little importance was attached to the small differences between p values for cis/trans isomers, and the relative transmissions were taken as the mean p values 0.59,0.34 and 0.33. The superior transmission of SCH=CH was attributed to greater polarizability. The values for pKJtrans) — pKJcis) of isomeric acids were also discussed. For the sulfonyl acids this is almost constant at 0.1 unit for the sulfinyl adds there is some variation about a mean value of 0.26 unit, and for the thio adds there is also some variation about a mean value of — 0.15 unit. The differing behavior of the three systems in this respect was explained in terms of hypothetical conformations and electrostatic interactions therein. 

Fig. 6. Apparent Acid Strength of 25% Nd203/Si02-Al203 Increases with Calcination Temperature...

The apparent acidities of zeolite catalysts are characterized by Av0h values induced by adsorption of hexane (Av0h.C6) under the same conditions than those applied during separate catalytic experiments. The Avoh,c6 values for the different zeolite samples shown in fig. 2 were determined as Figure 1. DRIFT spectra measured in the above for the nitrogen probe molecule. vOH region before (solid lines) and after (dashed lines) contacting the samples with N2 at 298 K and 9 bar equilibrium pressure. 

The shift of the acidic OH-band due to the interaction of the Bronsted acid sites with hexane reactant is clearly accompanied by the appearance of the absorption bands in the vCh region (fig. 2). The Av0h, C6 values listed in table 1 suggest that the apparent acidity of the ZSM-5 and mordenite samples is distinctly different (113-116 and 85-94 cm 1 shifts, respectively) and significantly higher than that of the zeolite Y samples (41-52 cm"1). 

Alternatively one could suggest that a micellized sulfuric or sulfonic acid is not strong. For example, apparent acid dissociation constants of weak acids decrease when the acids are bound to anionic micelles (Hartley, 1948), and the rapid hydrolysis of micellized alkyl sulfates at low pH is consistent with... 

The interfacial acidity constant or apparent acidity constant in the membrane phase Kam refers to the relative ratio of acidic and corresponding basic species in the membrane at a given (aqueous) pH-value ... 

Abundant evidence has been gathered to show that pure alumina, prepared either from aluminum isopropoxide or aluminum nitrate and ammonia and calcined at 600-800°, has intrinsic acidic sites. Several physical methods have been used to study the acidity of alumina. Titration with butylamine (33), dioxane (34), and aqueous potassium hydroxide (35) as well as chemisorption of gaseous ammonia (35), trimethylamine (36), or pyridine (37) gave apparent acidity values which approximated those of silica-alumina. On the other hand, the indicator method for testing the acidity of solids as developed by Walling (3S) showed no indication of even weak acids (39, 40). 

The extent of the apparent acid catalysis of the hydrolysis of this ester, like... 

Infrared spectra of glycosaminoglycans in D20 and DC1 were used165 for quantitative evaluation of the uronic acid and acetamido groups in this class of polysaccharide. The results showed that i.r. spectroscopy of compounds in D20 solution provides a simple, quantitative basis for examination of ras(COJ) and amide I bands in heparin and chondroitin 4-sulfate. In DC1, analysis was based on p(C02H) and amide I bands which were well resolved. The apparent acid-dissociation constants of the studied polysaccharides were estimated from the absorbance of p(C02) or p(C02H) bands, or both, at different pH (pD) values. 

With these compounds the presence of the halogen will have been detected in the tests for elements. Most acid halides undergo ready hydrolysis with water to give an acidic solution and the halide ion produced may be detected and confirmed with silver nitrate solution. The characteristic carbonyl adsorption at about 1800 cm -1 in the infrared spectrum will be apparent. Acid chlorides may be converted into esters as a confirmatory test to 1 ml of absolute ethanol in a dry test tube add 1 ml of the acid chloride dropwise (use a dropper pipette keep the mixture cool and note whether any hydrogen chloride gas is evolved). Pour into 2 ml of saturated salt solution and observe the formation of an upper layer of ester note the odour of the ester. Acid chlorides are normally characterised by direct conversion into carboxylic acid derivatives (e.g. substituted amides) or into the carboxylic acid if the latter is a solid (see Section 9.6.16, p. 1265). 

Many water-insoluble drugs are either weak bases or weak acids. There exists an equilibrium of ionized and unionized species for a weak base or a weak acid in an aqueous solution. The pH car affect the equilibrium between ionized and nonionized solute species, and consequently can have an effect on the capacity of micellar solubility. An example of this is the decreased uptake of 4-chlorobenzoic acid by polysorbate 80 micelles observed when the pH is changed from 3 to 4.4 (Collette and Koo, 1975). Another example regarding the effect of SDS micelles orKthefp atenolol, nadolol, midazolam, and nitrazepam is provided by Castro et al. (1998). Apparent acidity constants (p of the drugs were determined potentiometrically or spectrophotometrically in... 

By substituting expressions for the apparent acidity constants the two intrinsic surface acidity constants K J[ K for surface reactions are defined as... 

The exponential term can be thought of as a surface activity coefficient (Dzombak and Morel, 1990) that corrects the apparent acidity constants for surface charge effects. 

The effects of cationic and zwitterionic micelles on the keto-enol tautomerism of 2-phenylacetyl-furan and -thiophene (73, X = O, S) have been studied in aqueous media.285 While the micelles perturb the equilibrium only slightly, the apparent acidity of one or other tautomer is increased, as the micelles have an affinity for the enolate. The systems also show lowered water rates at the minima of their pH-rate profiles, allowing an otherwise undetectable metal ion catalysis to be observed. 

As is shown in Figure 6 (experiments) and Table 4 (Monte-Carlo analysis), a general trend is that Pt catalysts with supports of higher acidity lead to a higher contribution of the a-T)1 (Dl) and di-o-T)2 (D2) intermediates. As the ASA and LTL supports have similar metal particle sizes, this cannot be explained by particle size effects. Apparently, acidic supports enhance... 

In this method, in the equation for surface reaction constants, one can distinguish the part connected with the concentration of the ions in the solution and surface groups, and the part connected with electrostatic interaction. The first one, called apparent acidity quotients may be calculated from the following equation, knowing the concentrations of the relevant ion forms and surface groups. 

It may seem odd that the technique of spectrophotometric titration, so extensively applied to the tyrosyl residues of proteins, has not been used in the study of protein sulfhydryl groups. The only study of this sort known to the author is the determination of the ionization constant of —SH grouj of thiolated gelatin (introduced by reaction with A -acetylhomocysteine thiolactone). By measuring the change in absorptivity as a function of pH at 2380 A, Benesch and Benesch (1958) found the apparent acidity of the thiol groups of the modified gelatin (pK = 9.8) to be nearly the same as that of an appropriate model compound, A -acetylhomocysteine (pK = 10.0). 

Figure 2. Variation of the apparent acidity quotient (pQai) of a-FeOOH as a function of surface charge and concentration of supporting electrolyte, NaCl. Lines are contours for constant electrolyte or constant surface charge. The condition a = C = 0 yields a—FeOOH/NaCl. Balistrieri and Murray (1978).

Histidine participation in catalysis was suggested originally by the pH dependence shown in hydrolyses of simple, neutral substrates such as the methyl ester of an N-benzoyl amino acid. The hydrolysis rate typically increases from nearly zero at pH 5 to a maximum value at pH 8. The rate of change is consistent with that of a catalytic process whose rate-limiting step depends on an ionization with an apparent acid dissociation constant, pKa, close to 7. This is a typical value for the dissociation of a proton from a protonated imidazole group ... 

Dehydration (1, 301-303). Selective dehydration of 2,4-di 2-hydroxy-2-propyl)-cyclohexene-1 (1) to the diene (2) can be achieved by heating thediol in DMSO at 130°. The reaction is apparently acid catalyzed because it is completely inhibited by addition... 

By use of the a value, an apparent acid dissociation constant, pK,pp, is defined as... 

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