Acidity constant coefficient, calculations

IF BINARY SYSTEM CONTAINS NO ORGANIC ACIDS. THE SECOND VIRTAL coefficients ARE USED IN A VOLUME EXPLICIT EQUATION OF STATE TO CALCULATE THE FUGACITY COEFFICIENTS. FOR ORGANIC ACIDS FUGACITY COEFFICIENTS ARE PREDICTED FROM THE CHEMICAL THEORY FOR NQN-IOEALITY WITH EQUILIBRIUM CONSTANTS OBTAINED from METASTABLE. BOUND. ANO CHEMICAL CONTRIBUTIONS TO THE SECOND VIRIAL COEFFICIENTS. 

Although these approaches seem to be similar, the former method has several limitations it should be recognized that intrinsic mobility (yu,A ) depends on the ionic strength of the buffer, as shown in Ref. 17. Also, the activity coefficients of the zwitterions could not be calculated via the De-bye-Hiickel equation, and other methods, such as melting point depression, should be used to obtain the activity coefficients of the zwitterions (31). On the other hand, the latter method is directly applicable to the zwitterions to obtain their acidity constants. 

Our final task in this chapter is to demonstrate how partition constants/coefficients can be used to calculate the equilibrium distribution of a compound i in a given multiphase system. As already pointed out earlier, for simplicity, we consider only neutral species. As we will see in Chapter 8, the equilibrium partitioning of ionogenic compounds (i.e., compounds that are or may also be present as charged species, as, for example, acids or bases) is somewhat more complicated to describe. However, the general approach discussed here is the same. 

In the absence of special transport mechanisms (which is not proven, see further in the text), the vacuolar accumulation ratios (VAR) could be predicted from a derivation of the Hendelson-Hasselbach equation using the calculated log/) values. Indeed, for a diacidic base, the log D is a function of the acidity constants (pka) and the partition coefficient (log P) ... 

FIGURE 2-3 Activity coefficients calculated by the limiting Debye-Huckel equation (dotted lines) and those observed experimentally. Left, electrolytes of three charge types in water. Right, hydrochloric acid in water-dioxane mixtures with bulk dielectric constants as indicated. Adapted from Homed and Ow . )... 

The air pollutant sulfur dioxide can be partially removed from stack gases in industrial processes and converted to sulfur trioxide, the acid anhydride of commercially important sulfuric acid. Write the equation for the reaction, using the smallest whole-number coefficients. Calculate the value of the equilibrium constant for this reaction at 25°C, from values of AGf in Appendix K. 

The equilibrium constant for the reaction is equal to the partial pressure of the hydrazoic acid and was calculated by Feitknecht and Sahli to be 4.5 X lO" mm at 25°C [46]. From the distribution coefficient of hydrazoic acid between air and water [48], the concentration of hydrazoic acid in the water is calculated 5.4 X IO " M at 25°C. It is speculated that the Pb(N3)2-H2O reaction does not proceed beyond the basic lead azide because of the high nucleation energy for the formation of lead hydroxide. 

Chemometric methods are very useful allowing for predictions of chemical properties. Quantitative structure activity relationships (QSAR) are used in many modern chemical softwares to give a very decent calculated value for chemical properties such as molar volume, boiling point, acidity constant, or octanol/water partition coefficient [42]. The molecule is seen as an association of fragments, each of which contributing to the overall property [43],... 

A sample contains a weak acid analyte, HA, and a weak acid interferent, HB. The acid dissociation constants and partition coefficients for the weak acids are as follows Ra.HA = 1.0 X 10 Ra HB = 1.0 X f0 , RpjHA D,HB 500. (a) Calculate the extraction efficiency for HA and HB when 50.0 mF of sampk buffered to a pH of 7.0, is extracted with 50.0 mF of the organic solvent, (b) Which phase is enriched in the analyte (c) What are the recoveries for the analyte and interferent in this phase (d) What is the separation factor (e) A quantitative analysis is conducted on the contents of the phase enriched in analyte. What is the expected relative erroi if the selectivity coefficient, Rha.hb> is 0.500 and the initial ratio ofHB/HA was lO.O ... 

In subsequent studies attempting to find a correlation of physicochemical properties and antimicrobial activity, other parameters have been employed, such as Hammett O values, electronic distribution calculated by molecular orbital methods, spectral characteristics, and hydrophobicity constants. No new insight on the role of physiochemical properties of the sulfonamides has resulted. Acid dissociation appears to play a predominant role, since it affects aqueous solubiUty, partition coefficient and transport across membranes, protein binding, tubular secretion, and reabsorption in the kidneys. An exhaustive discussion of these studies has been provided (10). 

Apparent partition coefficient (logZ)) at an ionic strength of / = 0.02M, log P value of the neutral microspecies and the acidic dissociation constant of 5 was calculated (97ANC4143). The distribution coefficient of 5 was determined between 1-octanol and universal buffer in the pH range 3-10 at a... 

Diphenylcarbazide as adsorption indicator, 358 as colorimetric reagent, 687 Diphenylthiocarbazone see Dithizone Direct reading emission spectrometer 775 Dispensers (liquid) 84 Displacement titrations 278 borate ion with a strong acid, 278 carbonate ion with a strong acid, 278 choice of indicators for, 279, 280 Dissociation (ionisation) constant 23, 31 calculations involving, 34 D. of for a complex ion, (v) 602 for an indicator, (s) 718 of polyprotic acids, 33 values for acids and bases in water, (T) 832 true or thermodynamic, 23 Distribution coefficient 162, 195 and per cent extraction, 165 Distribution ratio 162 Dithiol 693, 695, 697 Dithizone 171, 178... 

If the substance shared between two solvents can exist in different molecular states in them, the simple distribution law is no longer valid. The experiments of Berthelot and Jungfleiscli, and the thermodynamic deduction show, however, that the distribution law holds for each molecular state separately. Thus, if benzoic acid is shared between water and benzene, the partition coefficient is not constant for all concentrations, but diminishes with increasing concentration in the aqueous layer. This is a consequence of the existence of the acid in benzene chiefly as double molecules (C6H5COOH)2, and if the amount of unpolymerised acid is calculated by the law of mass action (see Chapter XIII.) it is found to be in a constant ratio to that in the aqueous layer, independently of the concentration (cf. Nernst, Theoretical Chemistry, 2nd Eng. trans., 486 Die Verteilnngssatz, W. Hertz, Ahrens h annulling, Stuttgart, 1909). 

In equation (13.11), the first term corresponds to the catalysed part of the reaction and the remaining terms, which make a relatively small contribution, apply to the uncatalysed part. Kinetic data at constant acidity were in good agreement with the integrated form of the calculated rate expression. The rate coefficients k2,k, k, and the ratio k. jk were evaluated. Almost linear plots of log 2 versus log [ ] were obtained at four temperatures with slopes close to —1.8. This result suggests that the dominant activated complex is that formed by loss of two ions, viz. 

Assuming plug flow of both phases in the trickle bed, a volumetric mass transfer coefficient, kL a, was calculated from the measurements. The same plug flow model was then used to estimate bed depth necessary for 95% S02 removal from the simulated stack gas. Conversion to sulfuric acid was handled in the same way, by calculating an apparent first-order rate constant and then estimating conversion to acid at the bed depth needed for 95% S02 removal. Pressure drop was predicted for this bed depth by multiplying... 

Ketoprofen, a weak-acid drug, with a pKa 4.12 (25°C, 0.01 M ionic strength), was selected to illustrate Eqs. (7.20) and (7.21) in a series of simulation calculations, as shown in Fig. 7.16. The membrane-buffer apparent partition coefficients /(piii were calculated at various pH values, using the measured constants from... 

The terms in Eq. (6) include the gravitational constant, g, the tube radius, R, the fluid viscosity, p, the solute concentration in the donor phase, C0, and the penetration depth, The density difference between the solution and solvent (ps - p0) is critical to the calculation of a. Thus, this method is dependent upon accurate measurement of density values and close temperature control, particularly when C0 represents a dilute solution. This method has been shown to be sensitive to different diffusion coefficients for various ionic species of citrate and phosphate [5], The variability of this method in terms of the coefficient of variation ranged from 19% for glycine to 2.9% for ortho-aminobenzoic acid. 

In the multimedia models used in this series of volumes, an air-water partition coefficient KAW or Henry s law constant (H) is required and is calculated from the ratio of the pure substance vapor pressure and aqueous solubility. This method is widely used for hydrophobic chemicals but is inappropriate for water-miscible chemicals for which no solubility can be measured. Examples are the lower alcohols, acids, amines and ketones. There are reported calculated or pseudo-solubilities that have been derived from QSPR correlations with molecular descriptors for alcohols, aldehydes and amines (by Leahy 1986 Kamlet et al. 1987, 1988 and Nirmalakhandan and Speece 1988a,b). The obvious option is to input the H or KAW directly. If the chemical s activity coefficient y in water is known, then H can be estimated as vwyP[>where vw is the molar volume of water and Pf is the liquid vapor pressure. Since H can be regarded as P[IC[, where Cjs is the solubility, it is apparent that (l/vwy) is a pseudo-solubility. Correlations and measurements of y are available in the physical-chemical literature. For example, if y is 5.0, the pseudo-solubility is 11100 mol/m3 since the molar volume of water vw is 18 x 10-6 m3/mol or 18 cm3/mol. Chemicals with y less than about 20 are usually miscible in water. If the liquid vapor pressure in this case is 1000 Pa, H will be 1000/11100 or 0.090 Pa m3/mol and KAW will be H/RT or 3.6 x 10 5 at 25°C. Alternatively, if H or KAW is known, C[ can be calculated. It is possible to apply existing models to hydrophilic chemicals if this pseudo-solubility is calculated from the activity coefficient or from a known H (i.e., Cjs, P[/H or P[ or KAW RT). This approach is used here. In the fugacity model illustrations all pseudo-solubilities are so designated and should not be regarded as real, experimentally accessible quantities. 

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