title: Partial least squares analysis of rocket propulsion fuel data using diaphragm valve-based comprehensive two-dimensional gas chromatography coupled with flame ionization detection.
abstract: The chemical composition and several physical properties of RP-1 fuels were studied using comprehensive two-dimensional (2D) gas chromatography (GC×GC) coupled with flame ionization detection (FID). A "reversed column" GC×GC configuration was implemented with a RTX-wax column on the first dimension ((1)D), and a RTX-1 as the second dimension ((2)D). Modulation was achieved using a high temperature diaphragm valve mounted directly in the oven. Using leave-one-out cross-validation (LOOCV), the summed GC×GC-FID signal of three compound-class selective 2D regions (alkanes, cycloalkanes, and aromatics) was regressed against previously measured ASTM derived values for these compound classes, yielding root mean square errors of cross validation (RMSECV) of 0.855, 0.734, and 0.530mass%, respectively. For comparison, using partial least squares (PLS) analysis with LOOCV, the GC×GC-FID signal of the entire 2D separations was regressed against the same ASTM values, yielding a linear trend for the three compound classes (alkanes, cycloalkanes, and aromatics), yielding RMSECV values of 1.52, 2.76, and 0.945 mass%, respectively. Additionally, a more detailed PLS analysis was undertaken of the compounds classes (n-alkanes, iso-alkanes, mono-, di-, and tri-cycloalkanes, and aromatics), and of physical properties previously determined by ASTM methods (such as net heat of combustion, hydrogen content, density, kinematic viscosity, sustained boiling temperature and vapor rise temperature). Results from these PLS studies using the relatively simple to use and inexpensive GC×GC-FID instrumental platform are compared to previously reported results using the GC×GC-TOFMS instrumental platform.
authors.affiliation: Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, USA.
authors.forename: Chris E
authors.initials: CE
authors.lastname: Freye
authors.affiliation: Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, USA.
authors.forename: Brian D
authors.initials: BD
authors.lastname: Fitz
authors.affiliation: Air Force Research Laboratory/RQRC, 10 E Saturn Blvd., Edwards AFB, CA 93524, USA.
authors.forename: Matthew C
authors.initials: MC
authors.lastname: Billingsley
authors.affiliation: Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, USA. Electronic address: synovec@chem.washington.edu.
authors.forename: Robert E
authors.initials: RE
authors.lastname: Synovec
keywords: Chemometrics; GC×GC–FID; Gas chromatography; Kerosene; PLS; RP-1