Bisulfate acid constant

Here the values of a are the activities of the designated ions in solution, and and are the equiHbrium constants for the dissociation reactions. is infinity because dissociation to hydrogen and bisulfate ions is essentially complete. The best value for is probably 0.0102 (17). Thus sulfuric acid contains a mixture of hydrogen, bisulfate, and sulfate ions where the ratios of these ions vary with concentration and temperature. 

To verify the integrity of the extraction system in the presence of bisulfate, an experiment was run in which the TTA stoichiometry was determined at constant acidity and two different concentrations of HSOIJ. At 0.015 M HSOiJ, the Pu(IV)-TTA stoichiometry was 3.79 (+ 0.25) while at 0.07 M HSOiJ, the stoichiometry was 3.84 (+ 0.33). Both values are in agreement with observed stoichiometries in the absence of HSOi . 

N-nitro amines, RNHN02, decompose to alcohols and nitrous oxide in strong acid media. Rate constants obtained for R = methyl in sulfuric acid222 224 are illustrated as excess acidity plots in Fig. 12.119 This shows multiple curvature, but analysis according to equation (59) shows that one water molecule is involved in the reaction up to about 80 wt% H2S04, and one bisulfate ion above this point, see Fig. 13. The proposed mechanism is shown in Scheme 2. 19... 

We have found that HCrOr" in dilute solutions will undergo condensation with hydrogen phosphate, bisulfate, and even hydrochloric acid in water to form these mixed anhydrides like CrSCb-2. We have been able to measure equilibrium constants, and I wondered if this wouldn t prove fruitful in studying such reactions as the oxidation of sulfite with chromate. Sulfite is oxidized to a mixture of dithionate and sulfate. 

The discussion in the previous sections concerning solvated species indicates that a complete knowledge of the chemical reactions that take place in a system is not necessary in order to apply thermodynamics to that system, provided that the assumptions made are applied consistently. The application of thermodynamics to sulfuric acid in aqueous solution affords another illustration of this fact. We choose the reference state of sulfuric acid to be the infinitely dilute solution. However, because we know that sulfuric acid is dissociated in aqueous solution, we must express the chemical potential in terms of the dissociation products rather than the component (Sect. 8.15). Either we can assume that the only solute species present are hydrogen ion and sulfate ion (we choose to designate the acid species as hydrogen rather than hydronium ion), or we can take into account the weak character of the bisulfate ion and assume that the species are hydrogen ion, bisulfate ion, and sulfate ion. With the first assumption, the effect of the weakness of the bisulfate ion is contained in the mean activity coefficient of the sulfuric acid, whereas with the second assumption, the ionization constant of the bisulfate ion is involved indirectly. 

There are four reactions that deal explicitly with the H+ ion (Table 3.3) one is the dissociation constant for water (Kw), two are the first and second dissociation constants of carbonic acid (K and K2), and the fourth deals with the dissociation of the bisulfate (HSOJ) ion (iFbisuifate)-... 

FIGURE 20.5 Illustration of the all the evaporation and condensation rate constants the are required for multi-component nucleation of sulfuric acid (H2SO4) and water (H2O) including the relevant products of sulfuric acid dissociation bisulfate (HSO ), sulfate (SO ), and hydronium (H3O+). 

Differences in the speciation of other ions at the surface can be noted. Using an analysis similar to that above for metal ions, one finds that adsorbed anions are less acidic than in bulk solution. For example, it was shown in Figure 6 that protolysis of adsorbed sulfate ions becomes significant in the pH range 4-5, whereas in solution bisulfate is formed at much more acidic conditions (pH 2). Complexes formed by supporting electrolyte, e.g. Na" ,. with oxide surface sites have greater stability constants (logK 0.5-1.7) than observed for complex formation with oxyanions in solution (log K 0.0) (J.). ... 

Dissociation constants and reaction enthalpy data for the stable and most important metastable sulfur species are summarized in Table 12.4. The log K values in Table 12.4 indicate the pH at which the acid and conjugate base have equal concentrations. Bisulfate (HSO4) is a relatively strong acid. 

Molar ratio (MR) between sulfuric acid and sodium sulfate at constant sodium sulfate concentration. The second dissociation constant of sulfuric acid is rather low, in the range of 0.01. Consequently, in a solution containing both sulfuric acid and sodium sulfate at MR < 1, substantially all the sulfuric acid reacts with the stoichiometric amount of sodium sulfate to give sodium bisulfate (buffer action). Hence, the actual concentration of free protons (H ) is directly proportional to the actual concentration of sodium bisulfate and inversely proportional to that of the unreacted sodium. sulfate. This type of dependence indicates that the actual concentration of free protons should increase quickly when MR exceeds a certain critical value (ca. 0.5). At higher MR values the current transported by the protons becomes significant at the expense of that transported by the sodium ions, and the cathodic efficiency shows a sharp decrease. 

The decarboxylation of 2-substituted pyridinecarboxylic acids was studied in ethylene glycol at constant pressure and in sulfuric acid and in ammonium bisulfate. The reactions obeyed apparent first order kinetics. The determined parameters of activation are given in Table X-1. The data were again... 

A site in Pennsylvania receives a total annual deposition of 2.688 g/m of sulfate from fertilizer and acid rain. The ratio by mass of ammonium sulfate to ammonium bisulfate to sulfuric acid in the deposited material is 3.0/5.5/1.0. (a) How much acid, expressed as kg of sulfuric acid, is deposited over an area of 10. km 7 (b) How many pounds of CaC03 are needed to neutralize this acid (c) If 10. km is the area of an unpolluted lake 3 m deep and there is no loss of acid, what pH would the lake s water have at the end of the year (Assume constant volume and negligible runoff from the surrounding land.)... 

Depending on the mole ratio of reactants used, the polyacetals have either both terminal vinyl groups, both terminal hydroxyl groups, or one vinyl ether and one hydroxyl group. The reaction can be run at -10° to 20°C using acid salts of strong acids, e,g, alkali metal bisulfate or a-haloethers. Organic acids with dissociation constants of 10 to 10 are used if a reaction temperature of 20°-180°C is desired. 

The bisulfate (or hydrogen sulfate) anion, HS04, is a weak acid.The equilibrium constant for the aqueous acid reaction... 

Fig. 1. Low iodide, unstable, and high iodide steady states on composition line. Combined reactant feed stream concentrations [lOg lQ = 1.00 X 10-3 M, [HgAsOglo = 5.00 x 10-3 M, [I ]o = 4.41 X 10-5 m (indicated by vertical dashed line). Acidity maintained constant with sulfate/bisulfate buffer at pH = 2.122 ([H+] = 7.55 X 10-3 M). Reciprocal residence time ko = 8.20 X 10 3 s-1. Temperature 25.0 + 0.2°C. From Ref. [1].

We see that at this concentration the first ionization is practically complete, but that the second is only about 1 % complete. Most of the sulfuric acid placed in this solution is in the form of HSO4 (bisulfate) ion. In this example we computed the ionization constants from Table A.8 (see Problem 13.1). Most handbooks list the ionization constants directly, saving us this minor effort (see Problem 13.3 (b)). 

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