Calculation of the thermodynamic properties at elevated temperatures and pressures of saturated and aromatic high molecular weight solid and liquid hydrocarbons in kerogen, bitumen, petroleum, and other organic matter of biogeochemical interest

Abstract

To supplement the relatively sparse set of calorimetric data available for the multitude of high molecular weight organic compounds of biogeochemical interest, group additivity algorithms have been developed to estimate heat capacity power function coefficients and the standard molal thermodynamic properties at 25°C and 1 bar of high molecular weight compounds in hydrocarbon source rocks and reservoirs, including crystalline and liquid isoprenoids, steroids, tricyclic diterpenoids, hopanoids, and polynuclear aromatic hydrocarbons. A total of ninety-six group contributions for each coefficient and property were generated from the thermodynamic properties of lower molecular weight reference species for which calorimetric data are available in the literature. These group contributions were then used to compute corresponding coefficients and properties for ∼360 representative solid and liquid high molecular weight compounds in kerogen, bitumen, and petroleum for which few or no experimental data are available. The coefficients and properties of these high molecular weight compounds are summarized in tables, together with those of the groups and reference species from which they were generated. The tabulated heat capacity power function coefficients and standard molal thermodynamic properties at 25°C and 1 bar include selected crystalline and liquid regular, irregular and highly branched isoprenoids, tricyclic diterpanes, 17α(H)- and 17β(H)-hopanes, 5α(H),14α(H)-, 5β(H),14α(H)-, 5α(H),14β(H)-, and 5β(H),14β(H)-steranes, double ether- and ester-bonded n-alkanes, and various polynuclear aromatic hydrocarbons, including methylated biphenyls, naphthalenes, phenanthrenes, anthracenes, pyrenes, and chrysenes. However, corresponding coefficients and properties for many more saturated and unsaturated high molecular weight hydrocarbons can be estimated from the equations of state group additivity algorithms. Calculations of this kind permit comprehensive thermodynamic description of the chemical evolution of organic matter with increasing depth in sedimentary basins.