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Frans_M_Everaerts_Isotachophoresis_378342.pdf

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GENERAL EQUATIONS<br />

TABLE 4.2<br />

REDUCED NUMBER OF PARAMETERS, KNOWN PARAMETERS AND EQUATlONS FOR THE<br />

DIFFERENT ZONES IN MOVINGBOUNDARY ELECTROPHORESIS<br />

Zone Parameters and equations<br />

Lea ding Parameters: ifL, PH~, ck, cx,<br />

Known parameters and equations: ck, ci, Ohm’s law, electroneutrality equation<br />

Number of known parameters and equations is equal to the number of parameters<br />

First Parameters: E,, pH,, ci, c$,<br />

Known parameters and equations: Mass balances of B and A,, electroneutrality<br />

equation, Ohm’s law, isotachophoretic condition<br />

Surplus of one equation<br />

Second Parameters: E,, pH,, c fj, ca, I cL2<br />

Known parameters and equations: Mass balances of B, A, and A,, Ohm’s law,<br />

electroneutrality equation<br />

Number of known parameters and equations is equal to the number of parameters<br />

In all other zones, the number of anionic species is increasing. Consequently, the<br />

number of unknown parameters increases, but the number of mass balances also<br />

increases, and the number of unknown parameters and equations and number of<br />

parameters become equal again<br />

Uth Parameters: Eu pHU, cfj, c a t<br />

. . .<br />

Known paramefers and equations.’ Mass balances of B, A,, A,, . . ., AU, Ohm’s law,<br />

electtoneutrality equation<br />

Number of known parameters and equations is equal to the number of parameters<br />

Terminating Parameters: ET pH.,., ck, ci , . . ., ciu<br />

1<br />

Known parameters and e9Uan’onS: cir, . . ., ci, Ohm’s law, electroneutrality<br />

equation<br />

Shortage of one equation<br />

and the pH and the concentration of the counter ions in the terminating zone are<br />

determined by the buffer mass balance of the leading electrolyte zone (the surplus of<br />

one equation). This indicates the problem or calculations with the moving-boundary model.<br />

A surplus of one equation in the first zone determines the pH in the last zone, whereas<br />

the pH in the last zone determines the effective mobilities of the anionic species in that<br />

zone and hence the mass balances of those anionic species which determine the situation<br />

in the first zone. Thus the pH, requires a calculation from the first zone in accordance<br />

with the buffer mass balances, whereas the composition of the first zone is determined<br />

by calculations from the last zone in accordance with the mass balances of the anionic<br />

species.<br />

For nearly all calculations in moving-boundary electrophoresis, simplifications have to<br />

be made in order to avoid this difficulty. A mdel suitable for calculations on strong<br />

electrolytes (for which the mobilities are independent of the pH), neglecting the<br />

53

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