Electroanalytical Measurements of Oxide Ions in Molten CaCl 2 on W electrode
Open accessAbstract
The electrochemical interaction of oxide ions with tungsten electrodes in molten calcium chloride (CaCl 2 ) was analyzed by combining electroanalytical techniques with X-ray photoelectron spectroscopy. During a cyclic voltammetry (CV) scan, the oxide ions appear to interact with the tungsten working electrode via a multi-step oxidation and reduction process. The overall redox peaks behave reversibly up to 750 mV s −1 . This electrochemical process enables the oxide ion concentration to be correlated to CV oxidation peaks. The resulting correlation agrees well (8.8% difference) with back titration measurements and can be used to monitor oxide content in the salt in real-time during CaCl 2 based pryoprocesses.
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Cites
Thermochemical data of pure substances
(1993) · Choice Reviews Online · doi:10.5860/choice.31-0632 · Cited by 4,495 · see citing works
Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride
Chen, G. Z., Fray, D. J., & Farthing, T. W. (2000) · Nature · doi:10.1038/35030069 · Cited by 1,537 · see citing works
A new concept for producing Ti sponge: Calciothermic reduction
Ono, K., & Suzuki, R. O. (2002) · JOM · doi:10.1007/bf02701078 · Cited by 309 · see citing works
Electrochemical Reduction of UO[sub 2] in Molten CaCl[sub 2] or LiCl
Sakamura, Y., Kurata, M., & Inoue, T. (2006) · Journal of The Electrochemical Society · doi:10.1149/1.2160430 · Cited by 195 · see citing works
DC Voltammetry of Electro-deoxidation of Solid Oxides
Abdelkader, A. M., Kilby, K. T., Cox, A., & Fray, D. J. (2013) · Chemical Reviews · doi:10.1021/cr200305x · Cited by 191 · see citing works
CaCl2-rich region of the CaCl2-CaF2-CaO system
Wenz, D. A., Johnson, I., & Wolson, R. D. (1969) · Journal of Chemical & Engineering Data · doi:10.1021/je60041a027 · Cited by 170 · see citing works
Electrochemical behaviour of dysprosium in the eutectic LiCl–KCl at W and Al electrodes
Castrillejo, Y., Bermejo, M. R., Barrado, A. I., et al. (2004) · Electrochimica Acta · doi:10.1016/j.electacta.2004.09.013 · Cited by 163 · see citing works
Electrochemical deoxidation of titanium
Okabe, T. H., Nakamura, M., Oishi, T., et al. (1993) · Metallurgical Transactions B · doi:10.1007/bf02666427 · Cited by 147 · see citing works
769. The thermal dissociation of calcium hydroxide
Halstead, P. E., & Moore, A. E. (1957) · Journal of the Chemical Society (Resumed) · doi:10.1039/jr9570003873 · Cited by 130 · see citing works
Molenda, M., Stengler, J., Linder, M., et al. (2013) · Thermochimica Acta · doi:10.1016/j.tca.2013.03.020 · Cited by 130 · see citing works
Voltammetric Studies of the Oxygen-Titanium Binary System in Molten Calcium Chloride
Chen, G. Z., & Fray, D. J. (2002) · Journal of The Electrochemical Society · doi:10.1149/1.1513985 · Cited by 129 · see citing works
The electrochemistry of gadolinium in the eutectic LiCl–KCl on W and Al electrodes
Bermejo, M. R., Gómez, J., Medina, J., et al. (2006) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2005.12.031 · Cited by 125 · see citing works
Voltammetry of Titanium Dioxide in Molten Calcium Chloride at 900°C
Dring, K., Dashwood, R. J., & Inman, D. (2005) · Journal of The Electrochemical Society · doi:10.1149/1.1860515 · Cited by 108 · see citing works
Direct electrochemical conversion of metal oxides to metal by molten salt electrolysis: a review
Mohandas, K. S. (2013) · Mineral Processing and Extractive Metallurgy Transactions of the Institutions of Mining and Metallurgy Section C · doi:10.1179/0371955313z.00000000069 · Cited by 108 · see citing works
Electrochemical behaviour of erbium in the eutectic LiCl–KCl at W and Al electrodes
Castrillejo, Y., Bermejo, M. R., Barrado, E., et al. (2005) · Electrochimica Acta · doi:10.1016/j.electacta.2005.07.004 · Cited by 107 · see citing works
Capture and electrochemical conversion of CO 2 to ultrathin graphite sheets in CaCl 2 -based melts
Hu, L., Song, Y., Ge, J., Zhu, J., & Jiao, S. (2015) · Journal of Materials Chemistry A · doi:10.1039/c5ta05127d · Cited by 94 · see citing works
Semidifferential electroanalysis
Goto, M., & Ishii, D. (1975) · Journal of Electroanalytical Chemistry · doi:10.1016/s0022-0728(75)80237-3 · Cited by 87 · see citing works
Wang, S., Zhang, F., Liu, X., & Zhang, L. (2008) · Thermochimica Acta · doi:10.1016/j.tca.2008.02.007 · Cited by 86 · see citing works
CO2 gas decomposition to carbon by electro-reduction in molten salts
Otake, K., Kinoshita, H., Kikuchi, T., et al. (2013) · Electrochimica Acta · doi:10.1016/j.electacta.2013.02.076 · Cited by 86 · see citing works
Electrochemistry of terbium in the eutectic LiCl–KCl
Bermejo, M. R., Gómez, J., Martínez, A. M., et al. (2008) · Electrochimica Acta · doi:10.1016/j.electacta.2008.02.058 · Cited by 84 · see citing works
Electrochemical studies on the redox behaviour of zirconium in molten LiCl–KCl eutectic
Ghosh, S., Vandarkuzhali, S. A. A., Venkatesh, P., et al. (2008) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2008.12.011 · Cited by 81 · see citing works
Peak shapes in semidifferential electroanalysis
Dalrymple-Alford, P., Goto, M., & Oldham, K. B. (1977) · Analytical Chemistry · doi:10.1021/ac50017a025 · Cited by 72 · see citing works
Direct electrochemical production of Ti–10W alloys from mixed oxide preform precursors
Dring, K., Bhagat, R., Jackson, M., Dashwood, R. J., & Inman, D. (2006) · Journal of Alloys and Compounds · doi:10.1016/j.jallcom.2005.10.029 · Cited by 68 · see citing works
The Production of Ti–Mo Alloys from Mixed Oxide Precursors via the FFC Cambridge Process
Bhagat, R., Jackson, M., Inman, D., & Dashwood, R. J. (2008) · Journal of The Electrochemical Society · doi:10.1149/1.2904454 · Cited by 67 · see citing works
Role of CaCl2 in the reduction of PuO2
Perry, G. S., & MacDonald, L. G. (1985) · Journal of Nuclear Materials · doi:10.1016/0022-3115(85)90312-5 · Cited by 66 · see citing works
Application of Voltammetry for Quantitative Analysis of Actinides in Molten Salts
Tylka, M. M., Willit, J. L., Prakash, J., et al. (2015) · Journal of The Electrochemical Society · doi:10.1149/2.0281512jes · Cited by 58 · see citing works
Method Development for Quantitative Analysis of Actinides in Molten Salts
Tylka, M. M., Willit, J. L., Prakash, J., et al. (2015) · Journal of The Electrochemical Society · doi:10.1149/2.0401509jes · Cited by 55 · see citing works
On the use of electrochemical techniques to monitor free oxide content in molten fluoride media
Massot, L., Cassayre, L., Chamelot, P., et al. (2007) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2007.04.005 · Cited by 55 · see citing works
Electrochemical Reduction of Tungsten Compounds to Produce Tungsten Powder
Erdoğan, M., & Karakaya, İ. (2010) · Metallurgical and Materials Transactions B · doi:10.1007/s11663-010-9374-4 · Cited by 48 · see citing works
Characterization of Nernstian square-wave voltammograms
Aoki, K., Maeda, K., & Osteryoung, J. G. (1989) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(89)87065-2 · Cited by 46 · see citing works
Electrochemical reduction of cerium oxide into metal
Claux, B., Serp, J., & Fouletier, J. (2010) · Electrochimica Acta · doi:10.1016/j.electacta.2010.12.040 · Cited by 46 · see citing works
Production of Ti–W Alloys from Mixed Oxide Precursors via the FFC Cambridge Process
Bhagat, R., Jackson, M., Inman, D., et al. (2008) · Journal of The Electrochemical Society · doi:10.1149/1.2999340 · Cited by 44 · see citing works
Packter, A., & Roy, B. N. (1971) · Kristall und Technik · doi:10.1002/crat.19710060106 · Cited by 37 · see citing works
Bagri, P., & Simpson, M. F. (2016) · Journal of Nuclear Materials · doi:10.1016/j.jnucmat.2016.10.006 · Cited by 36 · see citing works
Self-citationElectrochemical synthesis and characterization of a NdCo5 permanent magnet
Abdelkader, A. M., Hyslop, D. J. S., Cox, A., & Fray, D. J. (2010) · Journal of Materials Chemistry · doi:10.1039/c0jm00096e · Cited by 35 · see citing works
Hydrolysis of fused calcium chloride at high temperature
Kondo, H., Asaki, Z., & Kondo, Y. (1978) · Metallurgical Transactions B · doi:10.1007/bf02654424 · Cited by 32 · see citing works
Cai, Z.-F., Zhang, Z.-M., Guo, Z., & Tang, H. (2012) · International Journal of Minerals Metallurgy and Materials · doi:10.1007/s12613-012-0586-2 · Cited by 28 · see citing works
Production of Fine Tungsten Powder by Electrolytic Reduction of Solid CaWO4in Molten Salt
Tang, D., Xiao, W., Yin, H., Tian, L., & Wang, D. (2012) · Journal of The Electrochemical Society · doi:10.1149/2.113206jes · Cited by 26 · see citing works
Neumann, B. H., Kröger, C., & Jüttner, H. (1935) · Zeitschrift für Elektrochemie und angewandte physikalische Chemie · doi:10.1002/bbpc.19350411005 · Cited by 25 · see citing works
Rappleye, D., Jeong, S.-M., & Simpson, M. F. (2016) · Journal of The Electrochemical Society · doi:10.1149/2.1011609jes · Cited by 23 · see citing works
Self-citationReview of major plutonium pyrochemical technology
Moser, W. S., & NAVRATIL, J. D. (1984) · Journal of the Less Common Metals · doi:10.1016/0022-5088(84)90062-6 · Cited by 20 · see citing works
Wang, X., & Chunfa, L. (2011) · International Journal of Refractory Metals and Hard Materials · doi:10.1016/j.ijrmhm.2011.11.004 · Cited by 19 · see citing works
Faulkner, E., Monreal, M. J., Jackson, M., et al. (2020) · Journal of Radioanalytical and Nuclear Chemistry · doi:10.1007/s10967-020-07413-0 · Cited by 19 · see citing works
Thermodynamic calculation and reference electrode calibration for high temperature molten salts
Zhang, W., Pulham, C. R., Mount, A., Brockie, N. L., & Lewin, R. G. (2008) · Energy Materials · doi:10.1179/174892408x394254 · Cited by 18 · see citing works
On the Electrochemical Reduction Mechanism of CaWO4 to W Powder
Erdoğan, M., & Karakaya, İ. (2012) · Metallurgical and Materials Transactions B · doi:10.1007/s11663-012-9689-4 · Cited by 15 · see citing works
Direct reduction of vanadium oxide in molten CaCl2
Suzuki, R. O., & Ishikawa, H. (2008) · Mineral Processing and Extractive Metallurgy Transactions of the Institutions of Mining and Metallurgy Section C · doi:10.1179/174328508x290894 · Cited by 11 · see citing works
Fused salt processing of impure plutonium dioxide to high-purity plutonium metal
Mullins, L. J., Christensen, D. C., & Babcock, B. R. (1982) · doi:10.2172/5200358 · Cited by 10 · see citing works
Mechanisms of electroreduction and electroplating of VI-A group metal coatings from ionic melts
Малышев, В. В. (2009) · Protection of Metals and Physical Chemistry of Surfaces · doi:10.1134/s2070205109040017 · Cited by 10 · see citing works
Rappleye, D., Jeong, S., Gonzalez, M. A., et al. (2015) · Journal of the Nuclear Fuel Cycle and Waste Technology(JNFCWT) · doi:10.7733/jnfcwt.2015.13.s.29 · Cited by 5 · see citing works
Self-citationZhang, C., Rappleye, D., & Simpson, M. F. (2017) · Journal of The Electrochemical Society · doi:10.1149/2.0321708jes · Cited by 5 · see citing works
Self-citationSolubility of Calcium in CaCl2-CaO
Shaw, S., & Watson, R. (2008) · ECS Meeting Abstracts · doi:10.1149/ma2008-02/49/2999 · Cited by 3 · see citing works
Electrolytic Reduction of Cerium Oxide
Rodríguez, D., Monreal, M. J., Jackson, M., et al. (2018) · ECS Meeting Abstracts · doi:10.1149/ma2018-01/15/1139 · Cited by 2 · see citing works
Electrolytic Oxide Reduction of Plutonium Oxide Surrogates
Los Alamos National Lab. (LANL), L. A., Jackson, J., USDOE, et al. (2018) · doi:10.2172/1475332 · Cited by 2 · see citing works
Flagged first, then by citations
Research works printed but not linked: 3
- [4]4. D. A. Wenz, I. Johnson, and R. D. Wolson, "CaCl 2 -rich region of the CaCl 2 -CaF 2 -CaO system." J. Chem. Eng. Data, 14, 250 (1969).
- [5]5. G. S. Perry and L. G. Macdonald, "Role of CaCl 2 in the reduction of PuO 2 ." J. Nucl. Mater., 130, 234 (1985).
- [39]39. M. W. Chase, (1998), JANAF Thermochemical Tables, NIST Standard Reference Database 13, NIST-JANAF Thermochemical Tables, 10.18434/T42S31. · DOI
Cited by
Sorted by citations
A review and analysis of extraction methods for aluminum and oxygen from Lunar Regolith
Ortega, J. N., Rupp, B., & Han, F. D. (2026) · Space and Planetary Resources · doi:10.1007/s44461-026-00010-1 · Cited by 1 · see citing works
- Authors
- Zhang, C., Rappleye, D., Nelson, A., Simpson, S., & Simpson, M.
- Affiliations
- Lawrence Livermore National Laboratory (US)
- University of Utah (US)
- Corresponding author
- Zhang, Chao
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 2021-09-01
- Volume
- 168
- Issue
- 9
- Pages
- 097502
- ISSN
- 0013-4651 (ISSN-L)
- 1945-7111
- OpenAlex
- W3196233938
- Semantic Scholar
- c08d058ddbb6741a36328279aabd3bc1cb8bb82c
- Cited by
- 33
- References
- 53
- Citations by year
- 2026: 6 · 2025: 8 · 2024: 8 · 2023: 5 · 2022: 4 · 2021: 2
- FWCI
- 2.10
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Licence
- Locations
- Journal of The Electrochemical Society (publishedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- Lawrence Livermore National Laboratory (DE-AC52-07NA27344)
- Topics
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Molten salt chemistry and electrochemical processes
- Physical Sciences › Engineering › Mechanical Engineering › Metallurgical Processes and Thermodynamics
- Physical Sciences › Chemistry › Electrochemistry › Electrochemical Analysis and Applications
- Keywords
- oxide ions, molten calcium chloride, tungsten electrode, electrochemical redox, cyclic voltammetry, real-time monitoring, pyroprocessing, molten salt electrolysis, X-ray photoelectron spectroscopy
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review