Distribution coefficients, estimation

On the basis of data obtained the possibility of substrates distribution and their D-values prediction using the regressions which consider the hydrophobicity and stmcture of amines was investigated. The hydrophobicity of amines was estimated by the distribution coefficient value in the water-octanole system (Ig P). The molecular structure of aromatic amines was characterized by the first-order molecular connectivity indexes ( x)- H was shown the independent and cooperative influence of the Ig P and parameters of amines on their distribution. Evidently, this fact demonstrates the host-guest phenomenon which is inherent to the organized media. The obtained in the research data were used for optimization of the conditions of micellar-extraction preconcentrating of metal ions with amines into the NS-rich phase with the following determination by atomic-absorption method. 

Various amines find application for pH control. The most commonly used are ammonia, morpholine, cyclohexylamine, and, more recently AMP (2-amino-2-methyl-l-propanol). The amount of each needed to produce a given pH depends upon the basicity constant, and values of this are given in Table 17.4. The volatility also influences their utility and their selection for any particular application. Like other substances, amines tend towards equilibrium concentrations in each phase of the steam/water mixture, the equilibrium being temperature dependent. Values of the distribution coefficient, Kp, are also given in Table 17.4. These factors need to be taken into account when estimating the pH attainable at any given point in a circuit so as to provide appropriate protection for each location. 

This equation has been used for estimating migration velocities of radionuclides (e.g. 66). Here Pr is the density of the rock (kg/m3), p the density of water, e the fissure porosity, af the specific surface of fissures in the bedrock (m2/m3) and ap the specific surface of particles used in the Kd determinations (m2/m3). The distribution coefficient Kd represents ar. equilibrium value for the particular rock under the pertinent conditions. 

Multimedia models can describe the distribution of a chemical between environmental compartments in a state of equilibrium. Equilibrium concentrations in different environmental compartments following the release of defined quantities of pollutant may be estimated by using distribution coefficients such as and H s (see Section 3.1). An alternative approach is to use fugacity (f) as a descriptor of chemical quantity (Mackay 1991). Fugacity has been defined as fhe fendency of a chemical to escape from one phase to another, and has the same units as pressure. When a chemical reaches equilibrium in a multimedia system, all phases should have the same fugacity. It is usually linearly related to concentration (C) as follows ... 

MD simulations in expHcit solvents are stiU beyond the scope of the current computational power for screening of a large number of molecules. However, mining powerful quantum chemical parameters to predict log P via this approach remains a challenging task. QikProp [42] is based on a study [3] which used Monte Carlo simulations to calculate 11 parameters, including solute-solvent energies, solute dipole moment, number of solute-solvent interactions at different cutoff values, number of H-bond donors and acceptors (HBDN and HBAQ and some of their variations. These parameters made it possible to estimate a number of free energies of solvation of chemicals in hexadecane, octanol, water as well as octanol-water distribution coefficients. The equation calculated for the octanol-water coefficient is ... 

The limitation of Eq. (2.1) is that measurement of concentrations of solute within different parts of the membrane is very inconvenient. However, since we can estimate (or possibly measure) the distribution coefficients between bulk water and the membrane, log Kj (the pH-dependent apparent partition coefficient), we can convert Eq. (2.1) into a more accessible form... 

Use the following data to estimate the distribution coefficient, KD, and the acid dissociation constant, Ka for trifluoroacetylacetone distributed between water and chloroform ... 

PhC properties most investigated by scientists to date are their water solubility (s, mg/mL), volatility (correlated to the Henry constant H) (pg m atr/pg m wastewater), biodegradability (correlated to pseudo-first-order degradation constant bioi L gSS d ), acid dissociation constant K, distribution and sorption (through the sludge-water distribution coefficient K, expressed in L gSS or the octanol-water partition coefficient Kg ). The main focus has been to find any correlations between these parameters and to determine PhC removal rates during the different treatment steps. Thus, different properties have been quantified for many compounds, and software, such as EPl Suite 4.00 [54], consenting their estimation, is available. 

Fig. 6.4 Calculated, estimated, or apparent salting out constants for various chemicals (a) selected aromatic compounds, (b) selected aliphatic compounds, (c) natural or surrogate hgands, (d) anthropogenic ligands, (e) sediment organic matter (SOM), (f) transition metal complexes, (g) trace metal complexes in the Mersey Estuary. Reprinted with permission from Turner A, Martino M, Le Roux SM (2002) Trace metal distribution coefficients in the Mersey Estuary UK Evidence for salting out of metal complexes. Environ Sci Technol 36 4578-4584. Copyright 2002 American Chemical Society...

These data were measured at or extrapolated to ambient temperature and pH values. The data are discussed in the text. NA = not available. b/ Kq = soil water distribution coefficient (K ) divided by the organic carbon content of the soil, cj Whenever possible, half-life for soil dissipation is derived from the field data half-lives described in the text rather than lab data. As such, it may not represent a true first-order process. Value has been estimated from the equation in ref. 20. e/ Hydrolysis of total residues (aldicarb + sulfoxide + sulfone). pK for p -phthalic acid is 3.5. The chlorine atoms of DCPA should lower the pK to about 2. Conditions optimized for soil metabolism. 

The comparison of the T25 method with the LMS method showed a good correlation between the two methods (correlation coefficient of 0.85 in a log-log plot) for 33 substances identified in the US-EPA IRIS database. The ratios between the lifetime cancer risks calculated by the T25 method and the LMS method were in the range 0.5-2.0 for 30 out of the 33 substances (calculated for the 10 lifetime cancer risk). The distribution of the ratios was plotted and the parameters characterizing this distribution were estimated. The mean and the median were both 1.21, the 5 th and 95 th percentiles were 0.50 and 1.87, respectively, and the minimum and maximum values were 0.45 and 2.31, respectively. For 24 substances, the T25 method gave a higher result than the LMS method, and for the remaining 9 substances a lower result. 

Selected entries from Methods in Enzymology [vol, page(s)j Boundary analysis [baseline correction, 240, 479, 485-486, 492, 501 second moment, 240, 482-483 time derivative, 240, 479, 485-486, 492, 501 transport method, 240, 483-486] computation of sedimentation coefficient distribution functions, 240, 492-497 diffusion effects, correction [differential distribution functions, 240, 500-501 integral distribution functions, 240, 501] weight average sedimentation coefficient estimation, 240, 497, 499-500. 

Separation processes (both liquid-liquid and gas-liquid) are a key element in many industrial processes. For this application, solvent molecules are built from UNIFAC submolecular groups, and the relevant properties of the new molecules such as distribution coefficients and selectivities are estimated. Strategies for the design of solvents for separation processes were initially formulated and later extended to better model the processes of solvent synthesis, solvent evaluation, and solvent screening. A method for solvent design for liquid-liquid extraction has been developed. 

Distribution coefficients for potassium on one clay are summarized in Figure 9. The ideal slope of -1 for log vs log sodium concentration was closely approximated. Values of D were about 1/3 those for cesium on the same clay. A value of K/T [(K )clay(Na+)/(K+)(Na+)ciay] of about 3.75 can be estimated from Figure 9. This agrees satisfactorily with values of about 2.5 reported both by Cast (10) for 0.001 M Na+ and by Shainberg and Kemper (20) for 0.05 Af Na+. 

In all of these cases, the structure of the organic sorbate, the composition of the surface, and the conditions of the vapor or solution exchanging with the solid must be considered. However, it is important to note that with some experience in thinking about the organic chemicals and environmental situation involved, we can usually anticipate which one or two sorption mechanisms will predominate. For example, in Chapter 9 we wrote an expression reflecting several simultaneously active sorption mechanisms, each with their own equilibrium descriptor, to estimate an overall solid-water distribution coefficient for cases of interest (Eq. 9-16) ... 

Estimate the goethite-water distribution coefficients from 10 mM NaCl aqueous solutions of benzoic acid (pKia = 4.1) at 50 nM at pHs 4, 5, and 6 to a synthetic iron oxyhydroxide, goethite, with the following properties (from Evanko and Dzombak, 1998) ... 

By using experimentally obtained data for 1 mM salicylic acid, a plot of reciprocal analytical signal versus reciprocal a, yielded a linear relationship for the pH range 1.65-3.01. This result supported the solvent extraction model. The corresponding estimate of capacity ratio and distribution coefficient using this treatment was 8.5. 

The effect of group (a) (non-polar solvents) was examined in the esterification of benzoic acid with 1-butanol over a Dowex-W X2 catalyst [454]. The solvent affected both the Helfferich distribution coefficients and the esterification rates. Dielectric constants, corresponding to the composition of the pore liquid, were estimated and the kinetic data related to the polar properties of the medium within the catalyst. In Fig. 18 are plotted specific rate coefficients versus the reciprocal value of dielectric constant of the pore liquid. The slope of the correlation is positive as for... 

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