Temperature dependence of solubility predicted from thermodynamic data measured at a single temperature : application to α, β and γ-glycine

Manson, Andrew and Sefcik, Jan and Lue, Leo (2022) Temperature dependence of solubility predicted from thermodynamic data measured at a single temperature : application to α, β and γ-glycine. Crystal Growth and Design, 22 (3). pp. 1691-1706. ISSN 1528-7483 (https://doi.org/10.1021/acs.cgd.1c01217)

[thumbnail of Manson-etal-CGD-2022-Temperature-dependence-of-solubility-predicted-from-thermodynamic-data]
Preview
 Text. Filename: Manson_etal_CGD_2022_Temperature_dependence_of_solubility_predicted_from_thermodynamic_data.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (3MB)| Preview

Abstract

Understanding of solid-liquid equilibria for polymorphic systems is crucial for rational design and efficient operation of crystallization processes. In this work, we present a framework to determine the temperature dependent solubility based on experimentally accessible thermodynamic data measured at a single temperature. Using this approach, we investigate aqueous solubility of α, β, and γ-glycine, which, despite numerous studies, have considerable quantitative uncertainty, in particular for the most stable (γ) and the least stable (β) solid forms. We benchmark our framework on α-glycine giving predictions in excellent agreement with direct solubility measurements between 273-340 K, using only thermodynamic data measured at the reference temperature (298.15 K). We analyze the sensitivity of solubility predictions with respect to underlying measurement uncertainty, as well as the excess Gibbs free energy models used to derive required thermodynamic quantities before providing solubility predictions for β and γ-glycine between 273-310 and 273-330 K, respectively. Crucially, this approach to predict solubility as a function of temperature does not rely on measurement of solute melting properties which will be particularly useful for compounds that undergo thermal decomposition or polymorph transition prior to melting.

ORCID iDs

Manson, Andrew, Sefcik, Jan ORCID logoORCID: https://orcid.org/0000-0002-7181-5122 and Lue, Leo ORCID logoORCID: https://orcid.org/0000-0002-4826-5337;
CORE (COnnecting REpositories)