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Frans_M_Everaerts_Isotachophoresis_378342.pdf

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44 MATHEMATICAL MODEL FOR ISOTACHOPHORESIS<br />

B<br />

t t t t t t t ! t<br />

Concentration r-I separation Boundary<br />

boundary boundaries l‘. e. -A I<br />

< r n < .......... ern i rn < rn<br />

AP-l A2 Al A1<br />

Fig.4.3. Zone boundaries formed when an electric current is passed across a zone boundary as shown<br />

in Fig.4.2.<br />

from the mixture, viz., that anionic species with the highest effective mobility of the<br />

anionic species that remain.<br />

The last boundary created is the boundary A,. . . JAl . . . (r- I). The last zone boundary is<br />

the original boundary Al.. .,-/Al . . .r, where an adaptation in concentrations according<br />

to Ohm’s law takes place. This concentration boundary can be considered as stationary<br />

[6]. Two types of boundaries have to be distinguished, viz., the concentration and the<br />

separation boundaries. For the concentration boundary, the number of anionic species<br />

is identical on both sides of the boundary, whereas for the separation boundaries one<br />

particular ionic species is present on one side of the boundary only. In general, rt 1<br />

boundaries will be present if an electric field is passed across the original boundary as<br />

shown in Fig.4.2, considering the separation of anionic species, viz., one concentration<br />

boundary (the original boundary), r-1 separation boundaries and the boundary<br />

between the single electrolyte and the zone containing the anionic species with the<br />

highest effective mobility in the anionic mixture (see Fig.4.3).<br />

The velocity of the boundary A,/A, is equal to the velocity of the anionic species<br />

A, and 4,. The velocities of the separation boundaries are equal to the velocities of the<br />

ionic species with the lowest effective mobilities in those zones (see section 4.2.3).<br />

These anionic species are not present in the preceding zones.<br />

For the derivation of the general equations, the following assumptions are made: the<br />

electric current is constant; the cross-section of the tube is constant; the influence of<br />

diffusion, hydrostatic flow and electroendosmosis is neglected. The activity coefficients<br />

and the influence of the radial temperature differences can be neglected.<br />

Further, only those boundaries that are formed between the original zone boundary<br />

and the anode are considered. The general equations describing electrophoretic processes<br />

are: the equilibrium equations; the electroneutrality equation; the mass balances for all<br />

ionic species; and the modified Ohm’s law. These equations are considered in more detail<br />

in sections 4.2.1-4.2.5.<br />

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