A group contribution model for determining the sublimation enthalpy of organic compounds at the standard reference temperature of 298K

Abstract

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Abstract  The sublimation enthalpy provides a measure of molecular interactions in the solid phase. Practical applications involving sublimation enthalpies include the estimation of the crystal lattice energy of molecular crystals, estimation of the enthalpy of solvation of crystalline organic compounds, and prediction of the environmental fate and vapor pressures of solid compounds. Recently an extensive compilation of phase change enthalpies, including sublimation enthalpies of pure organic and organometallic compounds, was published [1]. This collection of sublimation enthalpies for 1269 compounds at the standard temperature of 298.15 K was used in this study for the development of a predictive model. The compounds in the collection are composed of carbon, hydrogen, nitrogen, oxygen, phosphorous, sulfur, fluorine, chlorine, bromine, and iodine. This paper presents a reliable group contribution model for the estimation of the sublimation enthalpies of organic compounds. The group contribution model developed is able to predict the standard molar enthalpies of sublimation to within an average absolute relative deviation of 6.4%, which is of sufficient accuracy for many practical applications.

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

“…A number of computational approaches to E latt assessment are reported in the literature. They mostly concern single-component crystals and two-component crystals without an intermolecular proton transfer (cocrystals), and they use either careful quantum chemical modeling [6,[79][80][81][82] or semi-empirical schemes [23,24,[83][84][85][86]. Molecular salts present new challenges for those developing theoretical approaches describing the lattice energy E latt .…”

Calculation of Abraham model L-descriptor and standard molar enthalpies of vaporization and sublimation for C9 - C26 mono-alkyl alkanes and polymethyl alkanes

“…The key is to find a fragmentation method that results in a general predictive expression for a wide range of chemical compounds or mixtures. Published functional group contribution and atom group additivity methods provide reasonably accurate predictions of enthalpies of combustion, 22 enthalpies of formation, [22][23][24] standard molar enthalpies of vaporization 25.26 and sublimation, 25,27 solidliquid total phase entropies, 28,29 surface tensions, 25 isobaric molar heat capacities of liquid and solid organic and organometallic compounds. [30][31][32][33] Mathematical expressions for mixtures are more complex and include the mixture compositions as well as terms describing interactions between functional groups on neighboring molecules, [34][35][36][37][38] The method that we have been promoting in recent years for predicting thermodynamic properties is based on the Abraham solvation parameter model [39][40][41][42][43] which was originally developed to describe solute transfer between two phases.…”

Accurate or Fast Prediction of Solid-State Formation Enthalpies Using Standard Sublimation Enthalpies Derived From Geometrical Fragments

“…The first one is a QSPR based on so-called HYBOT descriptors, 26 and the second one is a group contribution (GC) method. 30 The former requires a proprietary software package whose details are not fully disclosed in the literature, whereas the latter exhibits other issues, as detailed below. In this context, the best demonstrated performance is currently obtained within the above-mentioned GIPF approach.…”