Abstract
An up to now unknown high “inner time precision” in isocratic gas chromatography (GC) and high pressure column liquid chromatography (HPLC) has been realized using quartz clock driven A/D converters and special statistically evaluating integration software. This millisecond level inner time precision is detectable by two very linear data correlations: a) the log of adjusted retention times (log(t R′)) versus the molecular weight of separated members of homologues and b) the peak width at half height versus correct k-values of the homologues. The inner time precision at the millisecond level is not lost by slight errors (up to seconds) in the starting times of GC or HPLC determinations. The correlation coefficient of the two linear data correlations allows a thorough analysis of instrument quality. The highly linear correlation of peak width and k in a wide range of mobile phase speeds is in disagreement with theoretical models of chromatography. Especially the rule of variance additivity is not valid in isocratic elution chromatography.
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