Summary Thermal field-flow fractionation separates polymers with high selectivity according to their Soret coefficient,
S
τ, hence, according to their molar mass, and therefore consitutes an efficeint physicochemical tool for the determination of
the Soret coefficient of a given polymer in the carrier liquid from its retention time. However, the polymer concentration
in the sample influences the retention time and, hence, the value of
S
τ derived from it. An experimental study of the influence of sample concentration on retention,
S
τ, and peak shape was performed for the polystyrene-decalin system over a relatively large temperature domain and for various
molar masses.
It is found that the retention time and the value of
S
τ increase with increasing sample concentration, the more so as the cold wall temperature is lower. This appears to be in contradiction
with the general non-equilibrium thermodynamic expression derived for polymer-solvent systems with positive second virial
coefficients, such as the present system over the temperature range investigated. There seems to be a temperature for which
the dependence of
S
τ on sample concentration vanishes. This temperature is about 375 K for the polystyrene-decalin system. As the sample concentration
increases, the peak barycentre and the standard deviation increases. As the peaks are fronting, the skewness is negative and
becomes more negative as the sample concentration increases. The peak skewness appears to be a good indicator of the onset
of sample concentration effects. The threshold concentration, for which these effects begin to become significant, decreases
with increasing molar mass.
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