First-principles study of chemical mixtures of CaCl2 and MgCl2 hydrates for optimized seasonal heat storage

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Abstract

Chloride-based salt hydrates form a promising class of thermochemical materials (TCMs), having high storage capacity and fast kinetics. In the charging cycles of these hydrates however hydrolysis might appear along with dehydration. The HCl produced during the hydrolysis degrades and corrodes the storage system. Our GGA-DFT results show that the enthalpy charge during proton formation (an important step in hydrolysis) is much higher for CaCl2·2H2O (33.75 kcal/mol) than for MgCl2·2H2O (19.55 kcal/mol). This is a strong indicator that hydrolysis can be minimized by appropriate chemical mixing of CaCl2 and Mg Cl2 hydrates, which is also confirmed by recent experimental studies. GGA-DFT calculations were performed to obtain and analyze the optimized structures, charge distributions, bonding indicators and harmonic frequencies of various chemical mixtures hydrates and compared them to their elementary salts hydrates. We have further assessed the equilibrium products concentration of dehydration/hydrolysis of the chemical mixtures under a wide range of operating conditions. We observed that chemical mixing leads to an increase of the onset hydrolysis temperature with a maximum value of 79 K, thus increasing the resistance against hydrolysis with respect to the elementary salt hydrates. We also found that the chemical mixing of CaCl2 and MgCl2 hydrates widens the operating dehydration temperature range by a maximum value of 182 K (CaMg2Cl6·2H2O) and lowers the binding enthalpy with respect to the physical mixture by ≈65 kcal/mol for TCM based heat storage systems.

Original languageEnglish
Pages (from-to)20576-20590
Number of pages15
JournalJournal of Physical Chemistry C
Volume121
Issue number38
DOIs
Publication statusPublished - 28 Sep 2017

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heat storage
Magnesium Chloride
Heat storage
Hydrates
hydrates
hydrolysis
Hydrolysis
Dehydration
dehydration
Salts
salts
Discrete Fourier transforms
Enthalpy
enthalpy
Charge distribution
charge distribution
charging
Protons
Chlorides
chlorides

Cite this

@article{175437be0c6b4c4f8d44999861f3bfe1,
title = "First-principles study of chemical mixtures of CaCl2 and MgCl2 hydrates for optimized seasonal heat storage",
abstract = "Chloride-based salt hydrates form a promising class of thermochemical materials (TCMs), having high storage capacity and fast kinetics. In the charging cycles of these hydrates however hydrolysis might appear along with dehydration. The HCl produced during the hydrolysis degrades and corrodes the storage system. Our GGA-DFT results show that the enthalpy charge during proton formation (an important step in hydrolysis) is much higher for CaCl2·2H2O (33.75 kcal/mol) than for MgCl2·2H2O (19.55 kcal/mol). This is a strong indicator that hydrolysis can be minimized by appropriate chemical mixing of CaCl2 and Mg Cl2 hydrates, which is also confirmed by recent experimental studies. GGA-DFT calculations were performed to obtain and analyze the optimized structures, charge distributions, bonding indicators and harmonic frequencies of various chemical mixtures hydrates and compared them to their elementary salts hydrates. We have further assessed the equilibrium products concentration of dehydration/hydrolysis of the chemical mixtures under a wide range of operating conditions. We observed that chemical mixing leads to an increase of the onset hydrolysis temperature with a maximum value of 79 K, thus increasing the resistance against hydrolysis with respect to the elementary salt hydrates. We also found that the chemical mixing of CaCl2 and MgCl2 hydrates widens the operating dehydration temperature range by a maximum value of 182 K (CaMg2Cl6·2H2O) and lowers the binding enthalpy with respect to the physical mixture by ≈65 kcal/mol for TCM based heat storage systems.",
author = "Pathak, {A. D.} and I. Tranca and Nedea, {S. V.} and Zondag, {H. A.} and Rindt, {C. C.M.} and Smeulders, {D. M.J.}",
year = "2017",
month = "9",
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doi = "10.1021/acs.jpcc.7b05245",
language = "English",
volume = "121",
pages = "20576--20590",
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First-principles study of chemical mixtures of CaCl2 and MgCl2 hydrates for optimized seasonal heat storage. / Pathak, A. D.; Tranca, I.; Nedea, S. V.; Zondag, H. A.; Rindt, C. C.M.; Smeulders, D. M.J.

In: Journal of Physical Chemistry C, Vol. 121, No. 38, 28.09.2017, p. 20576-20590.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - First-principles study of chemical mixtures of CaCl2 and MgCl2 hydrates for optimized seasonal heat storage

AU - Pathak, A. D.

AU - Tranca, I.

AU - Nedea, S. V.

AU - Zondag, H. A.

AU - Rindt, C. C.M.

AU - Smeulders, D. M.J.

PY - 2017/9/28

Y1 - 2017/9/28

N2 - Chloride-based salt hydrates form a promising class of thermochemical materials (TCMs), having high storage capacity and fast kinetics. In the charging cycles of these hydrates however hydrolysis might appear along with dehydration. The HCl produced during the hydrolysis degrades and corrodes the storage system. Our GGA-DFT results show that the enthalpy charge during proton formation (an important step in hydrolysis) is much higher for CaCl2·2H2O (33.75 kcal/mol) than for MgCl2·2H2O (19.55 kcal/mol). This is a strong indicator that hydrolysis can be minimized by appropriate chemical mixing of CaCl2 and Mg Cl2 hydrates, which is also confirmed by recent experimental studies. GGA-DFT calculations were performed to obtain and analyze the optimized structures, charge distributions, bonding indicators and harmonic frequencies of various chemical mixtures hydrates and compared them to their elementary salts hydrates. We have further assessed the equilibrium products concentration of dehydration/hydrolysis of the chemical mixtures under a wide range of operating conditions. We observed that chemical mixing leads to an increase of the onset hydrolysis temperature with a maximum value of 79 K, thus increasing the resistance against hydrolysis with respect to the elementary salt hydrates. We also found that the chemical mixing of CaCl2 and MgCl2 hydrates widens the operating dehydration temperature range by a maximum value of 182 K (CaMg2Cl6·2H2O) and lowers the binding enthalpy with respect to the physical mixture by ≈65 kcal/mol for TCM based heat storage systems.

AB - Chloride-based salt hydrates form a promising class of thermochemical materials (TCMs), having high storage capacity and fast kinetics. In the charging cycles of these hydrates however hydrolysis might appear along with dehydration. The HCl produced during the hydrolysis degrades and corrodes the storage system. Our GGA-DFT results show that the enthalpy charge during proton formation (an important step in hydrolysis) is much higher for CaCl2·2H2O (33.75 kcal/mol) than for MgCl2·2H2O (19.55 kcal/mol). This is a strong indicator that hydrolysis can be minimized by appropriate chemical mixing of CaCl2 and Mg Cl2 hydrates, which is also confirmed by recent experimental studies. GGA-DFT calculations were performed to obtain and analyze the optimized structures, charge distributions, bonding indicators and harmonic frequencies of various chemical mixtures hydrates and compared them to their elementary salts hydrates. We have further assessed the equilibrium products concentration of dehydration/hydrolysis of the chemical mixtures under a wide range of operating conditions. We observed that chemical mixing leads to an increase of the onset hydrolysis temperature with a maximum value of 79 K, thus increasing the resistance against hydrolysis with respect to the elementary salt hydrates. We also found that the chemical mixing of CaCl2 and MgCl2 hydrates widens the operating dehydration temperature range by a maximum value of 182 K (CaMg2Cl6·2H2O) and lowers the binding enthalpy with respect to the physical mixture by ≈65 kcal/mol for TCM based heat storage systems.

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U2 - 10.1021/acs.jpcc.7b05245

DO - 10.1021/acs.jpcc.7b05245

M3 - Article

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SP - 20576

EP - 20590

JO - Journal of Physical Chemistry C

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SN - 1932-7455

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