Determination of the Degradation Compounds Formed by the Oxidation of Thiophosphinic Acids and Phosphine Sulfides with Nitric Acid
Abstract
The degradation process that takes place at room temperature when bis(2,4,4-trimethylpentyl)monothiophosphinic acid (R2P(S)OH), bis(2,4,4-trimethylpentyl)dithiophosphinic acid (R2P(S)SH) and tris(2,4,4-trimethylpentyl)phosphine sulfide (R3PS) are in contact with 5 M HNO3 has been studied by FT-Infrared, FT-Raman spectroscopy and by gas chromatography with mass spectrometry detection (GC-MS). An exposure period of ten days of the rough reagents to 5 M HNO3 causes complete oxidation of the compounds. This process mainly leads to the formation of nitrogen dioxide, elemental sulfur and the oxo-analogues of the reagents. For dilute solutions of the reagents it was observed that after 15 min of contact with phase-shaking, R2P(S)OH and R3PS are completely oxidized to yield R2P(O)OH and R3PO, respectively, whereas for R2P(S)SH, the oxidation process is less severe, because the dithioacid is still present in the oxidized mixture, the oxidation products being R2P(S)OH and R2P(O)OH.
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Cyanex 302 and tris (2,4,4-trimethylpentyl) phosphine sulfide are completely oxidized to Cyanex 272 and tris (2,4,4-trimethylpentyl) phosphine oxide.
“Cyanex 302 and tris (2,4,4-trimethylpentyl) phosphine sulfide are completely oxidized to Cyanex 272 and tris (2,4,4-trimethylpentyl) phosphine oxide.”
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 [60]
The decomposition of Cyanex 301 results in the formation of Cyanex 302 as an intermediate product which is finally oxidized to Cyanex 272.
“The decomposition of Cyanex 301 results in the formation of Cyanex 302 as an intermediate product which is finally oxidized to Cyanex 272 [60].”
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 [60]
The formation of a yellow solid (sulfur) at the interface and the evolution of a brown gas (NO2) through the organic phase are evidence of the degradation of Cyanex 301/302 after contact with 5 M HNO3 for ten days.
“Besides the frequent change in the characteristic functional groups on IR spectra data, the formation of a yellow solid (sulfur) at the interface and the evolution of a brown gas (NO2) through the organic phase are evidence of the degradation of Cyanex 301 / 302 after contact with 5 M HNO3 for ten days [60].”
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 [60]
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- Authors
- Menoyo, B., Elizalde, M. P., & Almela, A.
- Affiliations
- University of the Basque Country (ES)
- Venue
- Analytical Sciences
- Published
- 2002-07
- Volume
- 18
- Issue
- 7
- Pages
- 799-804
- ISSN
- 0910-6340 (ISSN-L)
- 1348-2246
- OpenAlex
- W1976137167
- Cited by
- 38
- References
- 15
- Citations by year
- 2026: 1 · 2022: 1 · 2021: 2 · 2020: 3 · 2018: 2 · 2017: 4 · 2016: 1 · 2015: 2 · 2013: 5 · 2012: 6
- FWCI
- 0.74
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Analytical Sciences (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organophosphorus compounds synthesis
- Physical Sciences › Chemistry › Analytical Chemistry › Analytical chemistry methods development
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Keywords
- phosphine sulfides, dithiophosphinic acids, nitric acid oxidation, degradation products, nitrogen dioxide, elemental sulfur, room-temperature oxidation
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