New Vapor-Pressure Prediction with Improved Thermodynamic Consistency using the Riedel Equation

Abstract

Vapor pressure, heat of vaporization, liquid heat capacity, and ideal-gas heat capacity for pure compounds between the triple point and critical point are important properties for process design and optimization. These thermophysical properties are related to each other through temperature derivatives of thermodynamic relationships stemming from a temperature-dependent vapor-pressure correlation. The Riedel equation has been considered to be an excellent and simple choice among vapor-pressure correlating equations [Velasco et al. J. Chem. Thermodyn. 2008, 40 (5), 789−797] but requires modification of the final coefficient to provide thermodynamic consistency with thermal data [Hogge et al. Fluid Phase Equilib. 2016, 429, 149−165]. New predictive correlations with final coefficients in integer steps from 1 to 6 have been created for compounds with limited or no vaporpressure data, based on the methodology used originally by Riedel [Chem. Ing. Tech. 1954, 26 (2), 83−89]. Liquid heat capacity was predicted using these vapor-pressure correlations, and the best final coefficient values were chosen based on the ability to simultaneously represent vapor pressure and liquid heat capacity. This procedure improves the fit to liquid heat-capacity data by 5−10% (average absolute deviation), while maintaining the fit of vapor-pressure data similar to those of other prediction methods. Additionally, low-temperature vapor-pressure predictions were improved by relying on liquid heat-capacity data.

Liquid Heat Capacity Measurements of the Linear Dicarboxylic Acid Family via Modulated Differential Scanning Calorimetry

“…This method, internally called "the derivative method," has been found to be accurate for many systems if an accurate vapor pressure correlation is used. 10 However, this prediction method often struggles with hydrogen bonding systems because of deficiencies in predicting vapor volume, liquid density, and vapor pressure in associating systems. The last column in Table 4 shows the AAD of predicted values of the liquid heat capacity using the DIPPR-accepted correlations for ideal gas heat capacity, vapor pressure, liquid density, heat of vaporization, and vapor volumes from the Peng−Robinson equation of state.…”

“…In this equation, C p is the liquid heat capacity, C p IG is the ideal gas heat capacity, V P is the vapor pressure, V v is the vapor volume, Δ H vap is the heat of vaporization, and Δ V is the difference between the saturated vapor and liquid volume. This method, internally called “the derivative method,” has been found to be accurate for many systems if an accurate vapor pressure correlation is used . However, this prediction method often struggles with hydrogen bonding systems because of deficiencies in predicting vapor volume, liquid density, and vapor pressure in associating systems.…”