Gas chromatograph calibration of gas mixtures using a versatile precision volumetric apparatus

A compact, volumetric apparatus was developed for accurate automated preparation of standard gas and gas-liquid mixtures for gas chromatograph detector calibration, with accuracies comparable to those from gravimetric or Coriolis flow methods. The method developed by the principal author is not an adaptation or extension of any other apparatus or technology, and measurements involve only stepper motor steps, temperature, and pressure ratios. Mixture preparation is accomplished via the displacement of gas between chambers in a highly uniform cylinder, separated by a movable piston. Piston movement, with piston end rods of exactly equal diameter, ensures that there is no change in interior volume, and the volume of gas displaced from the bottom into the top compartment is exactly proportional to the piston travel measured to within 10 μm. The apparatus, operation, and previously unpublished measurements on common refinery gas mixtures over large concentration ranges are described in detail. These confirmed the accuracy and versatility of the apparatus and also the principle of no pressure change during mixture preparation, from sensitive pressure measurements. Conservative expanded uncertainties in prepared mixture mole fraction ranged from 0.001 to 0.002 over extended composition ranges. Absolute average deviations for the detector response factor for the mixtures ranged from 0.001 to 0.002. An exact new mathematical solution procedure permits the use of impure "pure" gases without loss of accuracy and can be applied to other procedures for standard gas mixture preparation. An exact expression is listed for determining "pure" gas purity.