Distribution coefficient in adsorption

Distribution coefficient in adsorption chromatography with adsorbents of unknown surface area ... 

Leckie [14] emphasized the advantage of chemical speciation over overall distribution coefficients in adsorption modeling. On the other hand, in many theoreticar studies of adsorption even the speciation in solution is neglected and only the total concentration of dissolved species is taken into account. One probable reason of paying no attention to well-known experimental facts is that some authors use adsorption equations borrowed from gas adsorption, and obviously these equations are not suitable to deal with multiple solution species involving the adsorbate. 

Distribution Coejjicient D. The amount of a component in a specified amount of stationary phase, or in an amount of stationary phase of specified surface area, divided by the analytical concentration in the mobile phase. The distribution coefficient in adsorption chromatography with adsorbents of unknown surface area is expressed as... 

The distribution coefficient in adsorption chromatography with well-characterized adsorbent of known surface area is expressed as... 

Type I isotherms result where there is essentially no affinity for the surface by the two molecules. Depending upon the distribution coefficient, the adsorption isotherms for ideal binary solutions can be shown in Figure 9.12. Here the distribution coefficient, K, as defined in equation 9.42 determines the shape of these isotherms. 

Li (1981) has proposed that the distribution coefficients reflect adsorption-desorption reactions at the surface of mineral grains. To emphasize this point, Li plotted a slightly different distribution coefficient (log Cop/Q , where Qp and Cs are the concentrations in oceanic pelagic clay sediments and seawater respectively vs the first hydrolysis constants of the metals or the dissociation constant of the oxyanion acids. The argument is that those elements that hydrolyze the strongest will adsorb the... 

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... 

The upper curve shows the adsorption isotherm that normally occurs in liquid chromatography separations where the concentration of solute in the system is very low. The isotherm is linear and thus the distribution coefficient is constant at all concentrations of solute in either phase. It follows that as the peak velocity is inversely related to the distribution coefficient, all solute concentrations travel at the same velocity through the column and the peak is symmetrical. 

In case when the notion of inhomogeneous surface is introduced it is assumed that all surface can be represented by areas characterized by various adsorption heats Qi or, in a more general case, by various inverse adsorption coefficients 6,- = boi exp -Qi/kT. Introducing the distribution function of adsorption heats or inverse adsorption coefficients one obtains the following expression for a surface occupation degree... 

The distribution coefficient assumes that adsorption is linear (i.e., the amount of adsorption is directly proportional to the concentration of the compound in solution) and is actually a special case of the Langmuir and Freundlich isotherms, which are nonlinear.31 32... 

This equation is widely used to describe adsorption in soil and near-surface aquatic environments. Another widely used linear coefficient is the organic-carbon partition coefficient Koc, which is equal to the distribution coefficient divided by the percentage of organic carbon present in the system as proposed by Flamaker and Thompson.131... 

Major problems are associated with using the linear distribution coefficient for describing adsorption-desorption reactions in groundwater systems. Some of these problems include the... 

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). 

Model Studies. In model studies of adsorption, one deals with simple, well-defined systems, where usually a single well-characterized solid phase is used and the composition of the ionic medium is known, so that reactions competing with the adsorption may be predicted. It is not a trivial problem to compare the results from such model studies with those from field studies, or to use model results for the interpretation of field data. In field studies, a complex mixture of solid phases and dissolved components, whose composition is only poorly known, has to be considered competitive reactions of major ions and trace metal ions for adsorption may take place, and the speciation of the trace metal ions is often poorly understood. In order to relate field studies to model studies, distribution coefficients of elements between the dissolved and solid phases are useful. These distribution coefficients are of the following form ... 

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. 

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