Engineering Research - Physical Properties of Hydrocarbons and Their Mixtures (T. P. 1060, with discussion)

Knowledge of a large number of the physical properties of the hydrocarbons is needed in the calculations and studies of the production engineer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and temperature,' enthalpy2 and vapor-liquid equilibria13 on the basis of reduced temperatures and pressures, are outstanding examples of this development. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been published by several authors4 and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter propertics are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are