Redox Processes in the Organic Phase during Cobalt Extraction with the bis(2,4,4-trimethylpentyl)dithiophosphinic Acid and Trioctyl Phosphine Oxide Mixtures
Abstract
The redox processes taking place in the organic phase during cobalt extraction with the mixtures of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HR, CYANEX 301) and trioctyl phosphine oxide (TOPO, CYANEX 921) have been studied. It was shown that CoR2 stabilization by the phosphine oxide prevents cobalt oxidation with air oxygen as well as with the disulfide of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (R–R). The introduction of TOPO into the extract containing Co(III) dithiophosphinate results in an increase in the rate of cobalt reduction to Co(II). Analysis of the interphase cobalt distribution as well as of the IR and electronic absorption spectra of the extracts showed that cobalt forms a pentacoordinated tetragonal-pyramidal high-spin complex with the dithiophosphinate ions and TOPO with a tetragonal-pyramidal geometry. The base of the pyramid is made up of sulfur atoms while an oxygen atom is on the top. The composition of the complex was found to be CoR2·TOPO. Examples of the possible use of the CYANEX 301 and trialkyl phosphine oxide (TAPO, CYANEX 923) mixtures in cobalt extraction technology are given.
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Some researchers have found metal to oxidize by air during solvent extractions.
“Some researchers have found metal to oxidize by air during solvent extractions [54,55].”
From Review on the Comparison of the Chemical Reactivity of Cyanex 272, Cyanex 301 and Cyanex 302 for Their Application to Metal Separation from Acid Media (2020) · cites this paper as [55]
The resulting Co(III) complex is kinetically very inert, leading to difficulty in stripping.
“The resulting Co(III) complex is kinetically very inert, leading to the di culty in stripping.”
From Review on the Comparison of the Chemical Reactivity of Cyanex 272, Cyanex 301 and Cyanex 302 for Their Application to Metal Separation from Acid Media (2020) · cites this paper as [55]
Back reaction, reduction in Co(III) to Co(II) under normal conditions, is very slow due to inertness of cobalt(III) complexes.
“The back reaction, namely the reduction in Co(III) to Co(II) under normal conditions, is very slow due to the inertness of the cobalt(III) complexes [55].”
From Review on the Comparison of the Chemical Reactivity of Cyanex 272, Cyanex 301 and Cyanex 302 for Their Application to Metal Separation from Acid Media (2020) · cites this paper as [55]
Co(II) is possibly oxidized to Co(III) by air in the organic phase.
“They suggested that Co(II) is possibly oxidized to Co(III) by air in the organic phase.”
From Review on the Comparison of the Chemical Reactivity of Cyanex 272, Cyanex 301 and Cyanex 302 for Their Application to Metal Separation from Acid Media (2020) · cites this paper as [55]
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- Authors
- Grigorieva, N. A., & Fleitlikh, I. Y.
- Affiliations
- Institute of Chemistry and Chemical Technology (RU)
- Corresponding author
- Grigorieva, N. A.
- ORCID
- Grigorieva, N. A.
- Venue
- Solvent Extraction and Ion Exchange
- Publisher
- Informa UK Limited
- Published
- 2015-01-21
- Volume
- 33
- Issue
- 3
- Pages
- 278-294
- ISSN
- 0736-6299 (ISSN-L)
- 1532-2262
- OpenAlex
- W2001017492
- Cited by
- 7
- References
- 24
- Citations by year
- 2026: 1 · 2025: 1 · 2023: 2 · 2020: 1 · 2017: 2
- FWCI
- 0.78
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Solvent Extraction and Ion Exchange (publishedVersion)
- Topics
- Physical Sciences › Engineering › Mechanical Engineering › Extraction and Separation Processes
- Physical Sciences › Chemistry › Inorganic Chemistry › Radioactive element chemistry and processing
- Physical Sciences › Chemistry › Analytical Chemistry › Analytical chemistry methods development
- Keywords
- cobalt extraction, redox reactions, Cyanex 301, trioctylphosphine oxide, topos, TRPO, Cyanex 923, cobalt oxidation, cobalt reduction, mixed extractant systems
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