Benzoic acid relative acidity

In medicine, the internal uses of benzoic acid are relatively unimportant. Its principal medicinal use is external it is used in dermatology as an antiseptic stimulant and irritant. Combined with salicyLic acid [69-72-7] benzoic acid is employed in the treatment of ringworm of the scalp and other skin diseases (Whitfield s ointment). 

The use of the potassium salt of benzoic acid is relatively new. Concerns regarding sodium intake and its possible relationship to high blood pressure have caused some soft drink manufacturers to switch to potassium benzoate. 

Aromatic carboxyUc acids are produced annually in amounts of several million metric tons. Several aromatic acids occur naturally, eg, benzoic acid (qv), sahcyhc acid (qv), cinnamic acid (qv), and gaUic acids, but those used in commerce are produced synthetically. These acids are generally crystalline sohds with relatively high melting points, attributable to the rigid, planar, aromatic nucleus (see Phthalic acids). 

This method is best suited to the preparation of relatively unhindered esters otherwise some esterification of the benzoic acid may occur at the expense of the acid to be esterified. 

Fig. 40. Flole-burning spectra of thioindigo in benzoic acid crystal at 1.35 K. The scanning laser frequency cu is measured with respect to the burning laser frequency cUb is detuning of the burning laser frequency relative to the center of absorption line.

Because it s much easier to measure the acidity of a substituted benzoic acid than it is to determine the relative reactivity of an aromatic ring toward electrophilic substitution, the correlation between the two effects is useful for predicting reactivity. If we want to know the effect of a certain substituent on electrophilic reactivity, we can simply find the acidity of the corresponding benzoic acid. Worked Example 20.1 gives an example. 

The theory of titrations between weak acids and strong bases is dealt with in Section 10.13, and is usually applicable to both monoprotic and polyprotic acids (Section 10.16). But for determinations carried out in aqueous solutions it is not normally possible to differentiate easily between the end points for the individual carboxylic acid groups in diprotic acids, such as succinic acid, as the dissociation constants are too close together. In these cases the end points for titrations with sodium hydroxide correspond to neutralisation of all the acidic groups. As some organic acids can be obtained in very high states of purity, sufficiently sharp end points can be obtained to justify their use as standards, e.g. benzoic acid and succinic acid (Section 10.28). The titration procedure described in this section can be used to determine the relative molecular mass (R.M.M.) of a pure carboxylic acid (if the number of acidic groups is known) or the purity of an acid of known R.M.M. 

Habid and Malek49 who studied the activity of metal derivatives in the catalyzed esterification of aromatic carboxylic acids with aliphatic glycols found a reaction order of 0.5 relative to the catalyst for Ti(OBu)4, tin(II) oxalate and lead(II) oxide. As we have already mentioned in connection with other examples, it appears that the activation enthalpies of the esterifications carried out in the presence of Ti, Sn and Pb derivatives are very close to those reported by Hartman et al.207,208 for the acid-catalyzed esterification of benzoic and substituted benzoic acids with cyclohexanol. These enthalpies also approach those reported by Matsuzaki and Mitani268 for the esterification of benzoic acids with 1,2-ethanediol in the absence of a catalyst. On the other hand, when activation entropies are considered, a difference exists between the esterification of benzoic acid with 1,2-ethanediol catalyzed by Ti, Sn and Pb derivatives and the non-catalyzed reaction268. Thus, activation enthalpies are nearly the same for metal ion-catalyzed and non-catalyzed reactions whereas the activation entropy of the metal ion-catalyzed reaction is much lower than that of the non-catalyzed reaction. 

De la Mare and Hilton198 measured the rates at 25 °C of bromination of benzene, benzoic acid, phthalic acid, 2-nitrobenzoic acid, trimethylanilinium perchlorate and nitrobenzene by hypobromous acid with sulphuric or perchloric acids as catalysts, in some cases in aqueous dioxan, in an attempt to discover if Br+ or H2OBr+ was the appropriate brominating species since the logarithm of the rates should then follow the acidity functions H0 or HR (J0) respectively. The results, however, were inconclusive and relative rates of bromination were determined (see Table 53). 

With 77 % aqueous acetic acid, the rates were found to be more affected by added perchloric acid than by sodium perchlorate (but only at higher concentrations than those used by Stanley and Shorter207, which accounts for the failure of these workers to observe acid catalysis, but their observation of kinetic orders in hypochlorous acid of less than one remains unaccounted for). The difference in the effect of the added electrolyte increased with concentration, and the rates of the acid-catalysed reaction reached a maximum in ca. 50 % aqueous acetic acid, passed through a minimum at ca. 90 % aqueous acetic acid and rose very rapidly thereafter. The faster chlorination in 50% acid than in water was, therefore, considered consistent with chlorination by AcOHCl+, which is subject to an increasing solvent effect in the direction of less aqueous media (hence the minimum in 90 % acid), and a third factor operates, viz. that in pure acetic acid the bulk source of chlorine ischlorineacetate rather than HOC1 and causes the rapid rise in rate towards the anhydrous medium. The relative rates of the acid-catalysed (acidity > 0.49 M) chlorination of some aromatics in 76 % aqueous acetic acid at 25 °C were found to be toluene, 69 benzene, 1 chlorobenzene, 0.097 benzoic acid, 0.004. Some of these kinetic observations were confirmed in a study of the chlorination of diphenylmethane in the presence of 0.030 M perchloric acid, second-order rate coefficients were obtained at 25 °C as follows209 0.161 (98 vol. % aqueous acetic acid) ca. 0.078 (75 vol. % acid), and, in the latter solvent in the presence of 0.50 M perchloric acid, diphenylmethane was approximately 30 times more reactive than benzene. 

The quantity on the right-hand side of Eq. (10-8) can be written in simplified form. This expression defines the substituent constant rr in terms of the m- and / -substituted benzoic acids, relative to benzoic acid itself. The value of <7 is given by... 

The values of para positions, are thus available from pX measurements of benzoic acids. One cannot so easily extend the correlation to ortho groups, however, because steric effects are superimposed on the electronic effects under study. Table 10-1 presents a list3 of crm and ap values. Note that the groups considered as electron-withdrawing relative to H have positive <7 values, and vice versa. Thus, we have a(p-CF ) — +0.54 and cr(/n-CHi) = —0.069. 

By introducing reasonable values (about 2 for nitrogen, 4 for oxygen) for the electron affinity parameter relative to carbon, 8, and for the induced electron affinity for adjacent atoms (32/8i = Vio), we have shown that the calculated permanent charge distributions for pyridine, toluene, phenyltrimethylammonium ion, nitrobenzene, benzoic acid, benzaldehyde, acetophenone, benzo-nitrile, furan, thiophene, pyrrole, aniline, and phenol can be satisfactorily correlated qualitatively with the observed positions and rates of substitution. For naphthalene and the halogen benzenes this calculation does not lead to results... 

It occasionally happens that a reaction proceeds much faster or much slower than expected on the basis of electrical effects alone. In these cases, it can often be shown that steric effects are influencing the rate. For example, Table 9.2 lists relative rates for the Sn2 ethanolysis of certain alkyl halides (see p. 390). All these compounds are primary bromides the branching is on the second carbon, so that field-effect differences should be small. As Table 9.2 shows, the rate decreases with increasing P branching and reaches a very low value for neopentyl bromide. This reaction is known to involve an attack by the nucleophile from a position opposite to that of the bromine (see p. 390). The great decrease in rate can be attributed to steric hindrance, a sheer physical blockage to the attack of the nucleophile. Another example of steric hindrance is found in 2,6-disubstituted benzoic acids, which are difficult to esterify no matter what the resonance or field effects of the groups in the 2 or the 6 position. Similarly, once 2,6-disubstituted benzoic acids are esterified, the esters are difficult to hydrolyze. 

The ionization of benzoic acids in water at 25° was used by Hammett as the standard reaction for the original qp treatment (2a). This reaction and several analogous reactions, e.g., ionization and ester saponification rates of benzoic acids, cinnamic acids, and phenylpropiolic acids, gives ap correlations of relatively high precision. Taft and Lewis classified such reactions in an A category (2f). Reexamination of these A reactions, as well as additional analogous data which have become available subsequently, provided eight reaction series of data of apparently comparable reliability. In the para position, each of these sets of data meets the necessary condition of a minimal basis set... 

Table 1 Relative Flux (N/N0) for Benzoic Acid Tablets in Sodium Hydroxide Solutions at 25°C...

Fluid loss additives such as solid particles and water-thickening polymers may be added to the drilling mud to reduce fluid loss from the well bore to the formation. Insoluble and partially soluble fluid loss additives include bentonite and other clays, starch from various sources, crushed walnut hulls, lignite treated with caustic or amines, resins of various types, gilsonite, benzoic acid flakes, and carefully sized particles of calcium borate, sodium borate, and mica. Soluble fluid loss additives include carboxymethyl cellulose (CMC), low molecular weight hydroxyethyl cellulose (HEC), carboxy-methYlhydroxyethyl cellulose (CMHEC), and sodium acrylate. A large number of water-soluble vinyl copolymers and terpolymers have been described as fluid loss additives for drilling and completion fluids in the patent literature. However, relatively few appear to be used in field operations. 

This constant characterizes the ionization of a particular substituted benzoic acid in water at 25 °C relative to that of benzoic acid itself. This definition reduces equation 7.4.22 to... 

Kindler [Twi., 450( 1), 1926] has studied the alkaline hydrolysis of the ethyl esters of a number of substituted benzoic acids. The m-nitro compound was found to have a rate constant 63.5 times as fast as the unsubstituted compound. What relative rate constant is predicted for the reaction of p-methoxybenzoate by the Hammett equation The value based on experimental results is 0.214. 

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