A Comprehensive Methodology for Development, Parameter Estimation, and Uncertainty Analysis of Group Contribution Based Property Models—An Application to the Heat of Combustion

Abstract

A rigorous methodology is developed that addresses numerical and statistical issues when developing group contribution (GC) based property models such as regression methods, optimization algorithms, performance statistics, outlier treatment, parameter identifiability, and uncertainty of the prediction. The methodology is evaluated through development of a GC method for the prediction of the heat of combustion (ΔHco) for pure components. The results showed that robust regression lead to best performance statistics for parameter estimation. The bootstrap method is found to be a valid alternative to calculate parameter estimation errors when underlying distribution of residuals is unknown. Many parameters (first, second, third order group contributions) are found unidentifiable from the typically available data, with large estimation error bounds and significant correlation. Due to this poor parameter identifiability issues, reporting of the 95% confidence intervals of the predicted property values should be...