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Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited

2004; American Chemical Society; Volume: 108; Issue: 45 Linguagem: Inglês

10.1021/jp047912y

1520-5215

Branko Ruščić, Reinhardt Pinzón, Melita L. Morton, Gregor von Laszevski, Sandra Bittner, Sandeep Nijsure, Kaizar Amin, Michael Minkoff, Albert F. Wagner,

thermodynamics and calorimetric analyses

The concept behind active thermochemical tables (ATcT) is presented. As opposed to traditional sequential thermochemistry, ATcT provides reliable, accurate, and internally consistent thermochemistry by utilizing the thermochemical network (TN) approach. This involves, inter alia, a statistical analysis of thermochemically relevant determinations that define the TN, made possible by redundancies in the TN, such as competing measurements and alternate network pathways that interrelate the various chemical species. The statistical analysis produces a self-consistent TN, from which the optimal thermochemical values are obtained by simultaneous solution in error-weighted space, thus allowing optimal use of all of the knowledge present in the TN. ATcT offers a number of additional features that are not present nor possible in the traditional approach. With ATcT, new knowledge can be painlessly propagated through all affected thermochemical values. ATcT also allows hypothesis testing and evaluation, as well as discovery of weak links in the TN. The latter provides pointers to new experimental or theoretical determinations that will most efficiently improve the underlying thermochemical body of knowledge. The ATcT approach is illustrated by providing improved thermochemistry for several key thermochemical species.