Abstract
In six homologous (RFC(O)O(CH2)mCH3, m=0–5) and six pseudohomologous (CF3-(CF2)nC(O)OR, n=0–5) of saturated, fluorinated carboxylic acid esters the effect of analysis temperature (Ta) in the range 60–160°C on the values of retention indexes (I) and on the differential molar free energy, enthalpy, and entropy of sorption of methylene and difluoromethylene groups when using SE-30 and SKTFT-50Kh as the stationary phase (SP) was studied. For each homolog I decreases linearly as Ta increases, but the values of dI/dTa are different for different homologs and increase as the length of the fluorinated chain increases. The sorption parameters ΔHm (CH2) and ΔSm(CH2) are constant when m > 3 and ΔHn (CF2) and ΔSn(CF2) vary regularly as n varies. The values of ΔHm (CH2) and ΔSm (CH2) exceed those of the corresponding ΔHn (CF2) and ΔSn (CF2) for m=n when adsorbed on both SPs. The thermodynamic sorption parameters of the esters for m=1 and n=1 differ sharply from the corresponding parameters for m > 2 and n > 2.
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