Distribution coefficients range

The rate of sorption of copper to suspended particles was determined for samples collected at the discharge area of a coastal power station (5). Steady-state conditions of sorption were approached within 10 hr after spiking with ionic copper using Cu as a tracer. Distribution coefficients range from 11,000 to 52,000 and k values from 0.2 to 0.8 hr There was some evidence from the data that part of the copper was sorbed in a very short period (less than about 10 min), while the remainder was sorbed onto the particles at an exponential rate over the next 10 hr as steady-state conditions were approached. However, for present purposes, considering sorption on particles as a single compartment, the transfer of copper from labile forms to those sorbed on suspended particles is fairly well represented as a first-order process in which kis approximately equals 0.75 hr ... 

The capacity factors of SN-SiO, for metal ions were determined under a range of different conditions of pH, metal ions concentrations and time of interaction. Preconcentration of Cd ", Pb ", Zn " and CvS were used for their preliminary determination by flame atomic absorption spectroscopy. The optimum pH values for quantitative soi ption ai e 5.8, 6.2, 6.5, 7.0 for Pb, Cu, Cd and Zn, respectively. The sorption ability of SN-SiO, to metal ions decrease in line Pb>Cu> >Zn>Cd. The soi ption capacity of the sorbent is 2.7,7.19,11.12,28.49 mg-g Hor Cd, Zn, Pb, andCu, respectively. The sorbent distribution coefficient calculated from soi ption isotherms was 10 ml-g for studied cations. All these metal ions can be desorbed with 5 ml of O.lmole-k HCl (sorbent recovery average out 96-100%). 

By measuring the retention volume of a solute, the distribution coefficient can be obtained. The distribution coefficient, determined over a range of temperatures, is often used to determine the thermodynamic properties of the system this will be discussed later. From a chromatography point of view, thermodynamic studies are also employed as a diagnostic tool to examine the actual nature of the distribution. The use of thermodynamics for this purpose will be a subject of discussion in the next chapter. It follows that the accurate measurement of (VV) can be extremely... 

Katz et al. also plotted the distribution coefficient of n-pentanol, benzonitrile and vinyl acetate against the concentration of unassociated methanol in the solvent mixture and the results are shown in Figure 32. It is seen that the distribution coefficient of all three solutes is predominantly controlled by the amount of unassociated methanol in the aqueous solvent mixture. In addition, the distribution coefficient increases linearly with the concentration of unassociated methanol for all three solutes over the entire concentration range. The same type of curves for anisole and benzene, shown in Figure 33, however, differ considerably. Although the relationship between distribution coefficient and unassociated methanol concentration is approximately linear up to about 50%v/v of unassociated methanol, over the entire range the... 

In the range of operating temperatures and compositions, the equilibrium relations are monotonic functions of temperature of the MSA. This is typically true. For instance, normally in gas absorption Henry s coefficient monotonically decreases as the temperature of the MSA is lowered while for stripping the gas-liquid distribution coefficient monotonically increases as the temperature of the stripping agent is increased. 

The selectivity of a gel, defined by the incremental increase in distribution coefficient for an incremental decrease in solute size, is related to the width of the pore size distribution of the gel. A narrow pore size distribution will typically have a separation range of one decade in solute size, which corresponds to roughly three decades in protein molecular mass (Hagel, 1988). However, the largest selectivity obtainable is the one where the solute of interest is either totally excluded (which is achieved when the solute size is of the same order as the pore size) or totally included (as for a very small solute) and the impurities differ more than a decade in size from the target solute. In this case, a gel of suitable pore size may be found and the separation carried out as a desalting step. This is very favorable from an operational point of view (see later). 

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... 

Baskaran and Santschi (1993) examined " Th from six shallow Texas estuaries. They found dissolved residence times ranged from 0.08 to 4.9 days and the total residence time ranged from 0.9 and 7.8 days. They found the Th dissolved and total water column residence times were much shorter in the summer. This was attributed to the more energetic particle resuspension rates during the summer sampling. They also observed an inverse relation between distribution coefficients and particle concentrations, implying that kinetic factors control Th distribution. Baskaran et al. (1993) and Baskaran and Santschi (2002) showed that the residence time of colloidal and particulate " Th residence time in the coastal waters are considerably lower (1.4 days) than those in the surface waters in the shelf and open ocean (9.1 days) of the Western Arctic Ocean (Baskaran et al. 2003). Based on the mass concentrations of colloidal and particulate matter, it was concluded that only a small portion of the colloidal " Th actively participates in Arctic Th cycling (Baskaran et al. 2003). 

A comprehensive survey is available in literature on the sorption behavior of elements over a range of hydrochloric acid concentrations. The compiled data show the following (i) a number of elements exhibit no sorption tendency at all (ii) many exhibit a change of behavior with hydrochloric acid concentration and (iii) several cases exhibit high distribution coefficients over at least some part of the concentration range. It can be found out that there is a possibility of separating certain metal combinations not easily obtainable by conventional chemical means. 

Results of adsorption experiments for butylate, alachlor, and metolachlor in Keeton soil at 10, 19, and 30°C were plotted using the Freundlich equation. A summary of the coefficients obtained from the Freundlich equation for these experiments is presented in TABLE IV. Excellent correlation using the Freundlich equation over the concentration ranges studied (four orders of magnitude) is indicated by the r values of 0.99. The n exponent from the Freundlich equation indicates the extent of linearity of the adsorption isotherm in the concentration range studied. If n = 1 then adsorption is constant at all concentrations studied (the adsorption isotherm is linear) and K is equivalent to the distribution coefficient between the soil and water (Kd), which is the ratio of the soil concentration (mole/kg) to the solution concentration (mole/L). A value of n > 1 indicates that as the solution concentration increases the sorption sites become saturated, resulting in a disproportionate amount of chemical being dissolved. Since n is nearly equal to 1 in these studies, the adsorption isotherms are nearly linear and the values for Kd (shown in TABLE IV) correspond closely to K. These Kd values were used to calculate heats of adsorption (AH). 

Indium, cadmium and silver can be extracted into chloroform as their 8-hydroxyquinoline complexes, and the pH1/2 values for these metals are 2.1, 6.3 and 8.8 respectively. Plot a graph of theoretical percent extraction against pH over the range 0 to 9 for each metal. Deduce the pH of incipient extraction (0.01%) and complete extraction (99.99%) for each metal, and comment on the feasibility of separating each from the other assuming that all the distribution coefficients are sufficiently high. 

Data collected with a simple RPLC procedure has been found to be in good agreement with 1-octanol shake-flask partition or distribution coefficients over a 3.5 log range [64], A chemically bonded octadecylsilane support is coated with 1-octanol. With 1-octanol-saturated buffers as mobile phases, a stable baseline (compared to 1-octanol absorbed on silica) is... 

In addition, if the apparent pKa of an ionizable compound lies within the pH operating range of the column support, the apparent pKa usually can be determined simultaneously with logP by measuring the log distribution coefficient at several pH values (Table 15.11). The main advantages of the procedure are that it gives rapid results, requires little material, and can tolerate impurities. 

The distribution coefficients are independent of the concentration of suspended solids in water, which can vary over a wide range they thus give a better picture than the fraction of metal ions in solution. Such distribution coefficients can be predicted on the basis of the equilibrium constants defining the complexation of metals by surfaces and their complexation by solutes (Table 11.1). 

Distribution coefficients based on adsorption equilibria are independent of the total concentrations of metal ions and suspended solids, as long as the metal concentrations are small compared with the concentration of surface groups. Examples of the Kd obtained from calculations for model surfaces are presented in Fig. 11.1. A strong pH dependence of these Kd values is observed. The pH range of natural lake and river waters (7 - 8.5) is in a favorable range for the adsorption of metal ions on hydrous oxides. 

In application of this method to solubility data (8) in the KCl-KBr- O system at 25°C, it is found that equilibrium is in general not attained, though some mid-range compositions may be near equilibrium. As the highly soluble salts are expected to reach equilibrium most easily, considerable caution should be exercised before reaching the conclusion that equilibrium is established in other low-temperature solid solution-aqueous solution systems. It is not appropriate to derive thermodynamic properties of solid solutions from experimental distribution coefficients unless it can be demonstrated that equilibrium has been attained. 

The liquid phase which is absorbed by the synthetic polymer granules (e.g., Sephadex) is mostly available in a wide range as solvent for solute molecules in contact with the gel. It has been observed that the actual distribution of the solute in between the inside and outside of the respective gel granules is nothing but a criterion of the available space. However, the underlying distribution coefficient occurring between the granular and interstitial aqueous phases is found to be independent of three major factors, namely ... 

The review of Martynova (18) covers solubilities of a variety of salts and oxides up to 10 kbar and 700 C and also available steam-water distribution coefficients. That of Lietzke (19) reviews measurements of standard electrode potentials and ionic activity coefficients using Harned cells up to 175-200 C. The review of Mesmer, Sweeton, Hitch and Baes (20) covers a range of protolytic dissociation reactions up to 300°C at SVP. Apart from the work on Fe304 solubility by Sweeton and Baes (23), the only references to hydrolysis and complexing reactions by transition metals above 100 C were to aluminium hydrolysis (20) and nickel hydrolysis (24) both to 150 C. Nikolaeva (24) was one of several at the conference who discussed the problems arising when hydrolysis and complexing occur simultaneously. There appear to be no experimental studies of solution phase redox equilibria above 100°C. 

Both Table XIX and Table XX show that distribution coefficients cover a much larger range for complexes than for the parent ligands, and that variation of ligand substituent can have a very large effect on... 

Soil sorption distribution coefficients (Kd) were determined from centrifuge column tests using kaolinite as the absorbent (Celorie et al, 1989). Values for Kd ranged from 0.010 to 0.054 L/g. 

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