Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis

• A ‘reversed column’ GC × GC format was used to separate ten RP-1 fuels.
• Partial least squares (PLS) analysis was used to analyze the GC × GC–TOFMS data.
• Replicate data sets were separately analyzed using leave-one-out cross validation.
• Connections between fuel composition and physical properties were investigated.
• Compounds that appeared most influential for physical properties were identified.

There is an increased need to more fully assess and control the composition of kerosene-based rocket propulsion fuels such as RP-1. In particular, it is critical to make better quantitative connections among the following three attributes: fuel performance (thermal stability, sooting propensity, engine specific impulse, etc.), fuel properties (such as flash point, density, kinematic viscosity, net heat of combustion, and hydrogen content), and the chemical composition of a given fuel, i.e., amounts of specific chemical compounds and compound classes present in a fuel as a result of feedstock blending and/or processing. Recent efforts in predicting fuel chemical and physical behavior through modeling put greater emphasis on attaining detailed and accurate fuel properties and fuel composition information. Often, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is employed to provide chemical composition information. Building on approaches that used GC–MS, but to glean substantially more chemical information from these complex fuels, we recently studied the use of comprehensive two dimensional (2D) gas chromatography combined with time-of-flight mass spectrometry (GC × GC–TOFMS) using a “reversed column” format: RTX-wax column for the first dimension, and a RTX-1 column for the second dimension. In this report, by applying chemometric data analysis, specifically partial least-squares (PLS) regression analysis, we are able to readily model (and correlate) the chemical compositional information provided by use of GC × GC–TOFMS to RP-1 fuel property information such as density, kinematic viscosity, net heat of combustion, and so on. Furthermore, we readily identified compounds that contribute significantly to measured differences in fuel properties based on results from the PLS models. We anticipate this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an improved approach to fuel formulation and specification for advanced engine cycles.