Bronsted acidity constant

Like other Bronsted-Lowry acids discussed in Section 2.7, carboxylic acids dissociate slightly in dilute aqueous solution to give H30+ and the corresponding carboxylate anions, RC02. The extent of dissociation is given by an acidity constant, Ka. 

This study was extended by Satchell517, who investigated the effect of stannic chloride with various Bronsted acids on the rate of tritiation of toluene (excess) at 25 °C. Using tritium-hydrogen chloride the data in Table 153 were obtained, and whereas the first-order rate coefficients were closely proportional to the stannic chloride concentration, they were relatively independent of the total concentration of hydrogen chloride at a constant tritium chloride concentration, the small rate... 

What Are the Key Ideas Bronsted acids are proton donors Bronsted bases are proton acceptors. The composition of a solution of an acid or base immediately adjusts to satisfy the values of the equilibrium constants for all the proton transfer reactions taking place. 

This equation corresponds to today s general convention of expressing base strength also be means of pKa, where K is considered in the sense of the Bronsted acid-base theory as a protolysis constant of the following protolytic reactions for acids ... 

The authors studied, as they call it, "acid-base equilibria in glacial acetic acid however, as they worked at various ratios of indicator-base concentration to HX or B concentration, we are in fact concerned with titration data. In this connection one should realize also that in solvents with low e the apparent strength of a Bronsted acid varies with the reference base used, and vice versa. Nevertheless, in HOAc the ionization constant predominates to such an extent that overall the picture of ionization vs. dissociation remains similar irrespective of the choice of reference see the data for I and B (Py) already given, and also those for HX, which the authors obtained at 25° C with I = p-naphthol-benzein (PNB) and /f B < 0.0042, i.e., for hydrochloric acid K C1 = 1.3 102, jjrfflci 3 9. IQ-6 an jjHC1 2.8 10 9 and for p-toluenesulphonic acid Kfm° = 3 7.102( K ms 4 0.10-6) Kmt = 7 3.10-9... 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

Apparent site-specific bimolecular rate constant, obtained by relating the kB app iimol-gcat."1 s"1) to the concentration of Bronsted acid sites (pmol-gc., 1). 

The duality of cracking mechanisms is summarized in Fig. 5, where RH paraffin feed, R -C=C = olefinic product, Kq = equilibrium constant of olefin chemisorption. Free Bronsted acid sites HZ interact directly with the paraffin feed by protonation, producing monomolecular cracking. When the acid sites are covered with adsorbed olefins to form... 

The relative sizes of the Hammett p and Bronsted a constants will determine the relative rate of 5-nitrosalicylamide. If intramolecular base catalysis applies, then 5-nitrosalicylamide should hydrolyse more rapidly, since the nitro group will increase the susceptibility of the amide bond to attack by hydroxide ion and increase the efficiency of the phenolic hydroxyl as a general acid catalyst. The value of Jtobs at the plateau region was found to be 18 times smaller for the 5-nitrosalicylamide than for salicylamide a mechanism of intramolecular general base catalysis is, therefore, the preferred mechanism. 

We can consider decarboxylation reactions in terms that are analogous to those in proton transfer reactions the reactivity of the carbanion in carboxylation reactions is analogous to internal return observed in proton transfer reactions from Bronsted acids. Kresge61 estimated that the rate constant for protonation of the acetylide anion, a localized carbanion (P A 21), is the same as the diffusional limit (1010 M s1). However, achieving this rate is highly dependent on the extent of localization of the carbanion. Jordan62 has shown that intermediates in thiazolium derivatives are also likely to be localized carbanions, which implies that protonation of these intermediates could occur at rates approaching those of other localized carbanions. 

The equilibrium constants for numerous reactions of the general type described by equation 34, where AH is a Bronsted acid and X is a halogen, are available from a series of investigations which utilized high ion source-pressure and FT-ICR mass spectrometers. 

Positive ions are often regarded as Lewis acids. However, many of these, particularly polyvalent ions, are strongly hydrated in solution and thus become ordinary Bronsted acids (of the same type as Co(NH3)q+). Thus salts of tripositive iron yield a hydrate, expressed noncommittally as Fe(H20)l+ whose dissociation constant in water has been found to be about the same as that of H3PO4 ... 

This representation is over-simplified, each of the ions being further solvated in each acid. Autoprotolysis constants have been reported as 3 x 10 13 mol2 kg-2 (0°C) for HF[6], 3.8 x 10 8 (25°C) for HS03F[7] and 7.9 x 1(T7 (25°C) for CF3S03H[8]. Protonic media are made more acidic by addition of an entity which increases the proton concentration. Superacids are themselves so very weakly basic that very few, if any, compounds can act as Bronsted acids to donate protons to the solvent directly. Lewis acids combine with X- to shift the autoprotolysis equilibria to increase the proton concentration. Superacids are rendered basic by direct addition of the X species, the base of the system, (e.g. from an alkali metal compound MX) or by addition of compounds which accept protons from the medium, increasing the concentration of the base X. ... 

The ionisation constants of many acidic organic compounds determined in water [110a] and in twelve of the most popular dipolar non-HBD solvents [110b] have been compiled, as have the methods of determination [111] and prediction [112] of p.Ka values. Particular attention has been paid to C—H acidic compounds [113]. Whereas the ionisation constants of Bronsted acids and bases for aqueous solutions are well known, the corresponding pAa values for nonaqueous solutions are comparatively scarce. 

Sections 3.3.1 and 4.2.1 dealt with Bronsted acid/base equilibria in which the solvent itself is involved in the chemical reaction as either an acid or a base. This Section describes some examples of solvent effects on proton-transfer (PT) reactions in which the solvent does not intervene directly as a reaction partner. New interest in the investigation of such acid/base equilibria in non-aqueous solvents has been generated by the pioneering work of Barrow et al. [164]. He studied the acid/base reactions between carboxylic acids and amines in tetra- and trichloromethane. A more recent compilation of Bronsted acid/base equilibrium constants, determined in up to twelve dipolar aprotic solvents, demonstrates the appreciable solvent influence on acid ionization constants [264]. For example, the p.Ka value of benzoic acid varies from 4.2 in water, 11.0 in dimethyl sulfoxide, 12.3 in A,A-dimethylformamide, up to 20.7 in acetonitrile, that is by about 16 powers of ten [264]. 

Constant K is identical with the ionization or dissociation constant in the classical sense, also known as the acidity constant for Bronsted acids or the basicity constant for Bronsted bases. 

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