Heat Capacities and Enthalpies of Normal Alkanes in an Ideal Gas State

Abstract

The reference literature contains data on the ideal gas-phase heat capacities and enthalpies of substances obtained experimentally. In this brief report, the highly accurate and simple unified analytical dependences of the heat capacity and enthalpy of normal alkanes larger than propane in the ideal gas state on temperature and the number of carbon atoms in a molecule are derived based on the analysis of the structure of chemical groups in the molecules and on the reference values of heat capacity and enthalpy for any two selected normal alkanes at one temperature. The dependences include a single set of coefficients for all normal alkanes and can be applied even to normal alkanes with the number of carbon atoms larger than 20, for which there is no data available. The dependences are thoroughly checked against two different sets of experimental data and two different sets of computational data obtained by low- and high-level theoretical methods: PM6 and G4. The error in calculating the heat capacity and enthalpy in the temperature range 300–1500 K is about 0.1% or less, which is comparable with the error of reference experimental data. Due to the generality of these dependences, one can treat the arising deviations as the indication of possible errors in the sets of reference data used for analysis. Such dependences are useful for estimating the heat capacities and enthalpies of vapors of large n-alkanes with scarce or lacking data. In addition, they can be readily used in computational fluid dynamics applications and provide the accurate interpolation/extrapolation of the tabulated experimental data without using semi-empirical methods of chemical thermodynamics and high-order polynomials.

Keywords

• normal alkanes
• heat capacity
• enthalpy
• ideal gas state
• analytical dependences