Thermodynamic properties of calcium-magnesium alloys determined by emf measurements

Jocelyn M. Newhouse; Sophie Poizeau; Hojong Kim; Brian L. Spatocco; Donald R. Sadoway

doi:10.1016/j.electacta.2012.11.063

Thermodynamic properties of calcium-magnesium alloys determined by emf measurements

Jocelyn M. Newhouse
, Sophie Poizeau
, Hojong Kim
, Brian L. Spatocco
, Donald R. Sadoway

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

The thermodynamic properties of calcium-magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi) CaF₂Ca(in Mg) cell over the temperature range 713-1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca-Mg alloys, calcium mole fractions varying from x_Ca = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs-Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 × 10^-4 and 0.94 versus pure calcium. The molecular interaction volume model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca-Mg liquid alloys. Based on this work, Ca-Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte.

Original language	English (US)
Pages (from-to)	293-301
Number of pages	9
Journal	Electrochimica Acta
Volume	91
DOIs	https://doi.org/10.1016/j.electacta.2012.11.063
State	Published - Feb 28 2013

All Science Journal Classification (ASJC) codes

General Chemical Engineering
Electrochemistry

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10.1016/j.electacta.2012.11.063

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@article{9d46ca7ebb564105a963acbd33bbc4f4,

title = "Thermodynamic properties of calcium-magnesium alloys determined by emf measurements",

abstract = "The thermodynamic properties of calcium-magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi) CaF2Ca(in Mg) cell over the temperature range 713-1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca-Mg alloys, calcium mole fractions varying from xCa = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs-Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 × 10-4 and 0.94 versus pure calcium. The molecular interaction volume model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca-Mg liquid alloys. Based on this work, Ca-Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte.",

author = "Newhouse, \{Jocelyn M.\} and Sophie Poizeau and Hojong Kim and Spatocco, \{Brian L.\} and Sadoway, \{Donald R.\}",

note = "Funding Information: The financial support of the US Department of Energy, Advanced Research Projects Agency-Energy (Award No. DE-AR0000047) and TOTAL, S.A. is gratefully acknowledged. The authors would like to thank Dr. Dane Boysen and Rahul Malik for fruitful discussions and their helpful suggestions.",

year = "2013",

month = feb,

day = "28",

doi = "10.1016/j.electacta.2012.11.063",

language = "English (US)",

volume = "91",

pages = "293--301",

journal = "Electrochimica Acta",

issn = "0013-4686",

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T1 - Thermodynamic properties of calcium-magnesium alloys determined by emf measurements

AU - Newhouse, Jocelyn M.

AU - Poizeau, Sophie

AU - Kim, Hojong

AU - Spatocco, Brian L.

AU - Sadoway, Donald R.

N1 - Funding Information: The financial support of the US Department of Energy, Advanced Research Projects Agency-Energy (Award No. DE-AR0000047) and TOTAL, S.A. is gratefully acknowledged. The authors would like to thank Dr. Dane Boysen and Rahul Malik for fruitful discussions and their helpful suggestions.

PY - 2013/2/28

Y1 - 2013/2/28

N2 - The thermodynamic properties of calcium-magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi) CaF2Ca(in Mg) cell over the temperature range 713-1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca-Mg alloys, calcium mole fractions varying from xCa = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs-Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 × 10-4 and 0.94 versus pure calcium. The molecular interaction volume model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca-Mg liquid alloys. Based on this work, Ca-Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte.

AB - The thermodynamic properties of calcium-magnesium alloys were determined by electromotive force (emf) measurements using a Ca(in Bi) CaF2Ca(in Mg) cell over the temperature range 713-1048 K. The activity and partial molar Gibbs free energy of calcium in magnesium were calculated for nine Ca-Mg alloys, calcium mole fractions varying from xCa = 0.01 to 0.80. Thermodynamic properties of magnesium in calcium and the molar Gibbs free energy of mixing were estimated using the Gibbs-Duhem relationship. In the all-liquid region at 1010 K, the activity of calcium in magnesium was found to range between 8.8 × 10-4 and 0.94 versus pure calcium. The molecular interaction volume model (MIVM) was used to model the activity coefficient of Ca and Mg in Ca-Mg liquid alloys. Based on this work, Ca-Mg alloys show promise as the negative electrode of a liquid metal battery in which calcium is the itinerant species: alloying with Mg results in both a decrease in operating temperature and suppression of Ca metal solubility in the molten salt electrolyte.

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UR - https://www.scopus.com/pages/publications/84872685709#tab=citedBy

U2 - 10.1016/j.electacta.2012.11.063

DO - 10.1016/j.electacta.2012.11.063

M3 - Article

AN - SCOPUS:84872685709

SN - 0013-4686

VL - 91

SP - 293

EP - 301

JO - Electrochimica Acta

JF - Electrochimica Acta

ER -

Thermodynamic properties of calcium-magnesium alloys determined by emf measurements

Abstract

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