Understanding the hydration process of salts: the impact of a nucleation barrier

Leyla Sögütoglu, M. Steiger, Jelle Houben, D. Biemans, Hartmut R. Fischer, Pim Donkers, Henk Huinink (Corresponding author), Olaf Adan

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Abstract

The solid-state hydration of salts has gained particular interest within the frame of thermochemical energy storage. In this work, the water vapor pressure–temperature (p–T) phase diagram of the following thermochemical salts was constructed by combining equilibrium and nonequilibrium hydration experiments: CuCl2, K2CO3, MgCl2·4H2O, and LiCl. The hydration of CuCl2 and K2CO3 involves a metastable zone of ca. 10 K, and the induction times preceding hydration are well-described by classical homogeneous nucleation theory. It is further shown for K2CO3 (metastable) and MgCl2·4H2O (not metastable) through solubility calculations that the phase transition is not mediated by bulk dissolution. We conclude that the hydration proceeds as a solid–solid phase transition, mobilized by a wetting layer, where the mobility of the wetting layer increases with increasing vapor pressure. In view of heat storage application, the finding of metastability in thermochemical salts reveals the impact of nucleation and growth processes on the thermochemical performance and demonstrates that practical aspects like the output temperature of a thermochemical salt are defined by its metastable zone width (MZW) rather than its equilibrium phase diagram. Manipulation of the MZW by e.g. prenucleation or heterogeneous nucleation is a potential way to raise the output temperature and power on material level in thermochemical applications.
Original languageEnglish
Pages (from-to)2279-2288
Number of pages10
JournalCrystal Growth and Design
Volume19
Issue number4
DOIs
Publication statusPublished - 3 Apr 2019

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Hydration
hydration
Nucleation
Salts
nucleation
salts
phase diagrams
wetting
Phase diagrams
Wetting
Phase transitions
heat storage
Heat storage
output
Steam
energy storage
Vapor pressure
metastable state
Energy storage
Water vapor

Cite this

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title = "Understanding the hydration process of salts: the impact of a nucleation barrier",
abstract = "The solid-state hydration of salts has gained particular interest within the frame of thermochemical energy storage. In this work, the water vapor pressure–temperature (p–T) phase diagram of the following thermochemical salts was constructed by combining equilibrium and nonequilibrium hydration experiments: CuCl2, K2CO3, MgCl2·4H2O, and LiCl. The hydration of CuCl2 and K2CO3 involves a metastable zone of ca. 10 K, and the induction times preceding hydration are well-described by classical homogeneous nucleation theory. It is further shown for K2CO3 (metastable) and MgCl2·4H2O (not metastable) through solubility calculations that the phase transition is not mediated by bulk dissolution. We conclude that the hydration proceeds as a solid–solid phase transition, mobilized by a wetting layer, where the mobility of the wetting layer increases with increasing vapor pressure. In view of heat storage application, the finding of metastability in thermochemical salts reveals the impact of nucleation and growth processes on the thermochemical performance and demonstrates that practical aspects like the output temperature of a thermochemical salt are defined by its metastable zone width (MZW) rather than its equilibrium phase diagram. Manipulation of the MZW by e.g. prenucleation or heterogeneous nucleation is a potential way to raise the output temperature and power on material level in thermochemical applications.",
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Understanding the hydration process of salts : the impact of a nucleation barrier. / Sögütoglu, Leyla; Steiger, M.; Houben, Jelle; Biemans, D.; Fischer, Hartmut R.; Donkers, Pim; Huinink, Henk (Corresponding author); Adan, Olaf.

In: Crystal Growth and Design, Vol. 19, No. 4, 03.04.2019, p. 2279-2288.

Research output: Contribution to journalArticleAcademicpeer-review

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T2 - the impact of a nucleation barrier

AU - Sögütoglu, Leyla

AU - Steiger, M.

AU - Houben, Jelle

AU - Biemans, D.

AU - Fischer, Hartmut R.

AU - Donkers, Pim

AU - Huinink, Henk

AU - Adan, Olaf

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