Applications of the deferred standard technique in process gas chromatography

Three applications of the deferred standard (DS) technique in on-line gas chromatographic analysis with a rotary injection valve are reported. It is demonstrated how both absolute and relative measurements are affected by several deviations of the experimental conditions, such as atmospheric pressure, sample injection during either flow or stopped-flow conditions and instrumental settings (carrier gas flow-rate, column oven temperature, detector bridge current) of the analytical system. It is shown that the relative DS concept provides an excellent means of improving the reliability of the analytical equipment. Under standard conditions, accurate results were obtained with a relative standard deviation < 1%. Significant deviations in the instrumental settings affected the accuracy of the final analytical results by less than 4%. It is further shown how the DS technique can be applied to obtain early information on maintenance requirements of the system. A diagnostic table is included that relates observed changes with time of the signals, obtained with a thermal conductivity detector, to possible maintenance requirements.