Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301

Kathryn C. Sole; J. Brent Hiskey

doi:10.1016/0304-386X(94)00023-V

Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301

Kathryn C. Sole, J. Brent Hiskey

Mining and Geological Engineering

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

161 Scopus citations

Abstract

The mechanisms of copper(II) solvent extraction by Cyanex 272, Cyanex 302 and Cyanex 301 are discussed. Extraction from sulfate media is strongly dependant upon sulfur substitution in the phosphinic acid and complete extraction of copper by Cyanex 302 and Cyanex 301 occurs below pH 0. Since conventional slope analysis is not possible under these conditions, the complex stoichiometries and geometries are inferred from analysis of the electronic, ³¹P-NMR and FAB-MS spectra of the complexed species. Cu(II) is reduced to Cu(I) on extraction by the sulfur-containing ligands, accompanied by the corresponding oxidation of the extractant. It is shown that copper combines in a 1:1 stoichiometric ratio with these ligands to form multinuclear oligomeric complexes, in which the ligands bridge between metal centers. The enhanced stabilities of the complexes formed with the sulfur-containing ligands are explained in terms of the Hard-Soft Acid-Base concept and pi bonding between the d orbitals of the metal center and the donor atoms.

Original language	English (US)
Pages (from-to)	129-147
Number of pages	19
Journal	Hydrometallurgy
Volume	37
Issue number	2
DOIs	https://doi.org/10.1016/0304-386X(94)00023-V
State	Published - Feb 1995

ASJC Scopus subject areas

Industrial and Manufacturing Engineering
Metals and Alloys
Materials Chemistry

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@article{e31bfa69316044c1b2b30fc21665888e,

title = "Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301",

abstract = "The mechanisms of copper(II) solvent extraction by Cyanex 272, Cyanex 302 and Cyanex 301 are discussed. Extraction from sulfate media is strongly dependant upon sulfur substitution in the phosphinic acid and complete extraction of copper by Cyanex 302 and Cyanex 301 occurs below pH 0. Since conventional slope analysis is not possible under these conditions, the complex stoichiometries and geometries are inferred from analysis of the electronic, 31P-NMR and FAB-MS spectra of the complexed species. Cu(II) is reduced to Cu(I) on extraction by the sulfur-containing ligands, accompanied by the corresponding oxidation of the extractant. It is shown that copper combines in a 1:1 stoichiometric ratio with these ligands to form multinuclear oligomeric complexes, in which the ligands bridge between metal centers. The enhanced stabilities of the complexes formed with the sulfur-containing ligands are explained in terms of the Hard-Soft Acid-Base concept and pi bonding between the d orbitals of the metal center and the donor atoms.",

author = "Sole, {Kathryn C.} and Hiskey, {J. Brent}",

note = "Funding Information: The Cyanex extractants were kindly supplied Cyanamid Canada, Inc. Appreciation for experimental assistance is extended to Dr. K. Christensen ( 31P-NMR), S. Gray (VPO) and Dr. K. Schram and P. Baker (FAB-MS). The suggestions and comments of Dr. H. Freiser are also gratefully acknowledged. This work was partially supported by the Copper Research Center at the University of Arizona under U.S. Defense Logistic Agency, Defense National Stockpile Center, Grant Number DN-004 and by the Foundation for Research Development, South Africa.",

year = "1995",

month = feb,

doi = "10.1016/0304-386X(94)00023-V",

language = "English (US)",

volume = "37",

pages = "129--147",

journal = "Hydrometallurgy",

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publisher = "Elsevier",

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T1 - Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301

AU - Sole, Kathryn C.

AU - Hiskey, J. Brent

N1 - Funding Information: The Cyanex extractants were kindly supplied Cyanamid Canada, Inc. Appreciation for experimental assistance is extended to Dr. K. Christensen ( 31P-NMR), S. Gray (VPO) and Dr. K. Schram and P. Baker (FAB-MS). The suggestions and comments of Dr. H. Freiser are also gratefully acknowledged. This work was partially supported by the Copper Research Center at the University of Arizona under U.S. Defense Logistic Agency, Defense National Stockpile Center, Grant Number DN-004 and by the Foundation for Research Development, South Africa.

PY - 1995/2

Y1 - 1995/2

N2 - The mechanisms of copper(II) solvent extraction by Cyanex 272, Cyanex 302 and Cyanex 301 are discussed. Extraction from sulfate media is strongly dependant upon sulfur substitution in the phosphinic acid and complete extraction of copper by Cyanex 302 and Cyanex 301 occurs below pH 0. Since conventional slope analysis is not possible under these conditions, the complex stoichiometries and geometries are inferred from analysis of the electronic, 31P-NMR and FAB-MS spectra of the complexed species. Cu(II) is reduced to Cu(I) on extraction by the sulfur-containing ligands, accompanied by the corresponding oxidation of the extractant. It is shown that copper combines in a 1:1 stoichiometric ratio with these ligands to form multinuclear oligomeric complexes, in which the ligands bridge between metal centers. The enhanced stabilities of the complexes formed with the sulfur-containing ligands are explained in terms of the Hard-Soft Acid-Base concept and pi bonding between the d orbitals of the metal center and the donor atoms.

AB - The mechanisms of copper(II) solvent extraction by Cyanex 272, Cyanex 302 and Cyanex 301 are discussed. Extraction from sulfate media is strongly dependant upon sulfur substitution in the phosphinic acid and complete extraction of copper by Cyanex 302 and Cyanex 301 occurs below pH 0. Since conventional slope analysis is not possible under these conditions, the complex stoichiometries and geometries are inferred from analysis of the electronic, 31P-NMR and FAB-MS spectra of the complexed species. Cu(II) is reduced to Cu(I) on extraction by the sulfur-containing ligands, accompanied by the corresponding oxidation of the extractant. It is shown that copper combines in a 1:1 stoichiometric ratio with these ligands to form multinuclear oligomeric complexes, in which the ligands bridge between metal centers. The enhanced stabilities of the complexes formed with the sulfur-containing ligands are explained in terms of the Hard-Soft Acid-Base concept and pi bonding between the d orbitals of the metal center and the donor atoms.

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Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301

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