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Frans_M_Everaerts_Isotachophoresis_378342.pdf

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THERMOMETRIC RECORDING<br />

T t l<br />

Fig.6.3. Temperature profiles of zone boundaries in isotachophoretic analyses, as derived from<br />

micro-thermocouples. In the direction X, the micro-thermocouple is mounted closer to the centre<br />

of the narrow-bore tube. In the initial phase, the transient response of the thermocouple, mounted<br />

closer to the centre, is more rapid, but the resolution is not improved much. T= Increasing<br />

temperature; t = time.<br />

of the temperature step to be attained is not changed very much; the total mass is<br />

not changed or is changed in the wrong direction.<br />

Calculations show that the sharpness of the temperature step approaches that of the<br />

concentration step if the narrow-bore tube is made of ‘infinite’ thickness [ 171 .<br />

Alist of data for thermometric detection is given in Tables 11.6 and 12.3.<br />

The resolution and stability of thermistors are comparable with those of thermocouples,<br />

but thermistors are not discussed further here because more complicated electronic<br />

circuits are necessary. Optical means of detection have not been tested so far, because<br />

the temperature differences are relatively small and the optics are very expensive,<br />

compared with the thermocouples and thermistors [18] . The information derived from<br />

liquid crystals [19] painted on the wall of the narrow-bore tube is poor and needs<br />

expensive instruments for automatic recording.<br />

6.2.3. Experimental<br />

Thermometric detectors lack high resolution because the heat generated by the electric<br />

current has to diffuse through the wall of the narrow-bore tube. The various heat transi-<br />

tion coefficients influence the final recording of successively migrating narrow zones. As<br />

a general rule, the zone length needed for a full qualitative and quantitative recording<br />

must be about 5 mm, making use of a PTFE (or Pyrex glass) narrow-bore tube with an<br />

outside diameter of 0.7 mm and an inside diameter of 0.45 mm. This value can vary,<br />

depending on the heat production of the adjacent zones, the electric current applied, the<br />

type of solvent used and some other minor factors (e.g., the addition of surfactants to<br />

the electrolytes in order to depress the electroendosmotic flow).<br />

In Fig.6.4, some graphs are shown of actual temperature measurements carried out<br />

with a thin thermocouple mounted on the outside of a narrow-bore tube.<br />

125

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