New knowledge on the temperature-entropy saturation boundary slope of working fluids

The slope of temperature-entropy saturation boundary of working fluids has a significant effect on the thermodynamic performance of cycle processes. However, for the working fluids used in cycles, few studies have been conducted to analyze the saturated slope from the molecular structure and mixture composition. Thus, in this contribution, an analytical expression on the slope of saturated curve is obtained based on the highly accurate Helmholtz energy equation. 14 pure working fluids and three typical binary mixtures are employed to analyze the influence of molecular groups and mixture compositions on the saturated slope, according to the correlated parameters of Helmholtz energy equation. Based on the calculated results, a preliminary trend is demonstrated that with an increase of the number of molecular groups, the positive liquid slope of pure fluids increases and the vapor slope appears positive sign in a narrow temperature range. Particularly, for the binary mixtures, the liquid slope is generally located between the corresponding pure fluids', while the vapor slope can be infinity by mixing dry and wet fluids ingeniously. It can be proved through the analysis of mixtures' saturated slope that three types of vapor slope could be obtained by regulating the mixture composition. - Highlights: • The saturated slope is derived from the Helmholtz function for working fluids. • The effect of molecular structure on the saturated slope is analyzed. • The variation of saturated slope with the mixture composition is investigated.