Determination of the degradation compounds formed by the oxidation of thiophosphinic acids and phosphine sulfides with nitric acid

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.