Improving the accuracy of Kováts’ retention indices in isothermal gas chromatography

Isothermal Kováts’ retention indices are currently reported as whole numbers, and are frequently deduced from a linear least mean squares fitting of the logarithms of adjusted retention times of a number of n-alkanes versus carbon number, following an iterative method that minimises errors. The currently accepted accuracy is about one retention index unit for apolar stationary phases, and lower for polar stationary phases. This paper presents results that show how the accuracy of the retention index may be safely reported to one-tenth of a retention index unit by the use of a non-linear equation, with present day gas chromatographs without electronic flow controllers. Results are presented that prove the correctness of the retention indices found for several substances on one particular capillary column. Hints on the minimum retention times needed to achieve the 0.1 retention index accuracy are mentioned, for retention times recorded in minutes and in seconds. According to results of this paper, two chromatograms, run under the appropriate conditions, are sufficient to obtain the desired accuracy. The method proposed in this paper does not require knowledge of the hold-up time of the chromatogram.