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Rectangular capillary electrophoresis: Some theoretical considerations

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Summary

A theoretical study of the use of rectangular columns in capillary electrophoresis (CE) is presented. It was done employing some of the most important parameters that normally define the performance of CE separations, i.e. thermal effect, analysis speed, efficiency and sample capacity. Theoretical results from rectangular and cylindrical capillaries are compared in terms of the aforementionated parameters. Also, an estimate of the additional zone broadening that arises from the noninfinite dimension in the y-direction, in which the channel has its largest dimension, is presented.

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Abbreviations

a:

half rectangular column thickness, (m)

b:

half width of rectangular column, (m)

c:

concentration of electrolyte, (mol m−3)

d:

wall thickness of rectangular column, (m)

Dm :

diffusion coefficient, (m2 s−1)

E:

electric field strength, (V m−1)

H:

plate height, (m)

〈H〉:

apparent plate height, (m)

Hd :

plate height related to molecular diffusion, (m)

Hinj :

plate height related to injection, (m)

Ht :

plate height related to Joule heat, (m)

Hct :

plate height into circular column related to Joule heat, (m)

Hrt :

plate height into rectangular column related to Joule heat, (m)

k1 :

thermal conductivity of electrolyte, (W m−1 K−1)

k2 :

thermal conductivity of wall material, (W m−1 K−1)

L:

column length (in this study is equal to separation length), (m)

R1 :

external radius, (m)

R2 :

internal radius, (m)

Scol :

internal cross sectional area of column, (m2)

tm :

analysis time, (s)

TC2 :

temperature of circular column at a distance x (R2≥x≥0) from centre, (K)

Tm :

temperature of rectangular and circular columns at wall exterior, (K)

TR2 :

temperature of rectangular column at a distance x (a≥x≥0) from centre, (K)

ΔT:

difference of temperature between wall exterior and the centre of column, (K)

u:

velocity of eluent, (m s−1)

Δu:

mean velocity excess in column when self-heating present, (m s−1)

Vinj :

injected volume, (m3)

Wv :

power dissipation per unit volume of column, (W m−3)

β:

relative thermal coefficient of the electrophoretic mobility, (dμ/dT)/μ, (K−1)

ϕ:

2b/2a

λ:

molar conductivity, (m2Ω−1mol−1)

μ:

global electrophoretic mobility of solute, (m2 s−1 V−1)

m2s−1V−1 :

electrophoretic band dispersion into circular column related to Joule heat, (m2)

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Cifuentes, A., Poppe, H. Rectangular capillary electrophoresis: Some theoretical considerations. Chromatographia 39, 391–404 (1994). https://doi.org/10.1007/BF02278753

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