Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K

Abstract

An estimation method developed by S.W. Benson and coworkers, for calculating the thermodynamic properties of organic compounds in the gas phase, has been extended to the liquid and solid phases for hydrocarbon compounds at 298.15 K. The second order approach which includes nearest neighbor interactions has been applied to the condensed phase. A total of 1311 comparisons are made between experimentally determined values and those calculated using additive group values. Of the 559 comparisons given for the enthalpy of formation (ArHO) in the gas, liquid, and solid phases, the average difference (residual), without regard to sign, is 2.6 kJ/mol. The average differences for 390 comparisons for the heat capacity (C p 0) and 352 comparisons for the entropy (SO) in the three phases are 1.9 and 2.3 J/mol•K, respectively. The good agreement between experimental and calculated values shows that the Benson group additivity approach to the estimation of thermodynamic properties of organic compounds is applicable to the liquid and solid phases as well as the gas phase. Appendices provide example calculations of the thermodynamic properties of selected hydrocarbon compounds, total symmetry numbers, and methyl repulsion corrections. Most of the 144 references listed offer an indication of the activity in the development of estimation methods for calculating thermodynamic properties since 1931.

Enthalpies of Sublimation of Organic and Organometallic Compounds. 1910–2001

“…11 A number of group additivity methods have been developed to estimate gas phase heat capacities. [11][12][13] However, group values for some functional groups are not available. This has encouraged the development of other estimation methods.…”

“…In an effort to provide some assistance to the reader in this regard, a brief discussion of one of the few group additivity methods that are available for estimating the heat capacity of solids is included below. 12,19 This is followed by an illustration of how this value can be used in conjunction with Eq. ͑7͒ to provide temperature adjustments.…”

Artificial intelligence and molecular biology

“…Group-Contribution methods [Benson, 1968;Benson et al, 1969;Domalski and Hearing, 1988;Joback and Reid, 1987;Mavrovouniotis et al, 1988;Mavrovouniotis, 1990b;Reid et al, 1977;Reid et al, 1987] have been widely used to estimate numerical values of properties of pure compounds. To estimate a property, one views the compound as composed of functional groups and sums amounts contributed by each group to the overall value of the property.…”

Entropy Prediction of Benzene Derivatives Using Topological Indices

“…Prediction of entropies and enthalpies of organic compounds by using group contribution methods was also published [17][18][19]. Prediction of standard absolute entropy (S 298 K) of gaseous organic and inorganic compounds was reported in [20,21].…”