Summary
It is not commonly appreciated that retention indices are temperature dependent. It is even less common to express this fact in more practical terms by saying that polarity is temperature dependent. Although the meaning of both statements is identical, we believe the second to be particularly relevant, since the majority of practical gas chromatographers tends to handle polarity as an invariable characteristic of a stationary phase.
The variability of polarity with temperature is the major source of inadequate reproducibility of exact finger-printing, this particularly when gc/ms traces have to be compared to those obtained by pure gc. On the other hand, the temperature dependence provides a practical means to optimize the polarity of a given column for a given analysis. Film thickness is an essential parameter in this context because of its influence on column temperature and, therefore, on column polarity.
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Grob, K., Grob, G. Practical aspects of the dependence of polarity on temperature. Chromatographia 17, 481–485 (1983). https://doi.org/10.1007/BF02263269
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DOI: https://doi.org/10.1007/BF02263269