Apparent Henry coefficient

The equilibrium (4.207) only describes the physical dissolved gas species (Fig. 4.7) without considering the subsequent protolysis equilibrium as discussed for the example of CO2 absorption in Chapter 2.S.3.2. In Eq. (2.117), we introduced an apparent Henry coefficient, where the dissolved matter comprises the anhydride (for example CO2 or SO2) and the acid (H2CO3, H2SO3). The acid can dissociate according to Eq. (4.174) and thereby increases the total solubility of gas A, as described by the effective Henry coefficient Hgf/. 

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. 

The calculation is illustrated in Table 1.5.5 for pentachlorophenol. The experimental aqueous solubility is 14.0 g/m3 at a pH of 5.1. The environmental pH is 7. Higher environmental pH increases the extent of dissociation, thus increasing the Z value in water, increasing the apparent solubility, decreasing the apparent KqW and Henry s law constant and the air-water partition coefficient, and decreasing the soil-water partition coefficient. 

It is apparent from Table II that variations in the experimental rate constants (k) are essentially controlled by the Henry s law constant, in agreement with the two-film theory prediction. A plot of kys. H for the five pesticides gave an intercept of 5.4 x 10 hr, a slope of 6.9 x 10 mol/(hr atm m" ), and a correlation coefficient of 0.969. Thus, it seems that Henry s law values could be used to predict relative volatilization rates of the pesticides, and an absolute volatilization rate for one pesticide can be calculated if the volatilization rate is known for another and Henry s law constants are known for both ... 

The several early efforts to use Kow or the Henrys law constant H as descriptors for the influence of physical-chemical properties on KPA (Bacci and Gaggi, 1987 Travis and Hatte-mer-Frey, 1988 Reischl et al., 1989) were based on very limited data sets. As mentioned above, at the end of the 1980s an apparent consensus emeged that the quotient of K, )W and Kaw (or Koa) was a more suitable descriptor for partitioning into the lipid-like compartments. The first and simplist model assumed that there were one or several lipid-like compartments whose partition coefficients were all equal to Kow/Kaw (Schramm et al., 1987 Paterson and Mackay, 1989 Paterson et al., 1991b). Equation (1) then becomes... 

The primary variable that determines whether the controlling resistance is in the liquid or gas film is the H or Henry constant. As shown in Figure 5.15, and as is apparent from equation 39, for small values of H the water phase film controls the transfer, and for high values of H the transfer is controlled by the air phase film. Gas transfer conditions that are liquid film controlled sometimes are expressed in terms of thickness, Zw, of the water film. As indicated by equation 38, this can be done from a measured value of (or K,o,) and the diffusion coefficient of the substance Zw decreases with the extent of turbulence (current velocity, wind speed, etc.). Typical values for are in the range of micrometers for seawater, a few hundred micrometers in lakes and up to 1 nun in small wind-sheltered water bodies (Brezonik, 1994). 

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