The Reaction of Nitric Oxide With Phosphine and Several Difluorophosphine Molecules

Odom, J. D.; Zozulin, A. J.

doi:10.1080/03086648108078254

Cited by 7 publications

(11 citation statements)

References 15 publications

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“…The research discussed herein suggests that when products that are outgassing NO into the headspace are stored in semipermeable containers, they are prone to promote the formation of both oxyacids of phosphorus as well as the yellow polyhydric phosphorus polymer (21). This reaction involves PH 3 interaction with NO and/or nitrogen dioxide (NO 2 ) (immediately formed from the oxidation of NO on contact with air).…”

Section: Resultsmentioning

confidence: 98%

Residue Formations of Phosphorus Hydride Polymers and Phosphorus Oxyacids during Phosphine Gas Fumigations of Stored Products

Flora

Byers

Plunkett

et al. 2005

J. Agric. Food Chem.

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With the extent of international usage and the critical role phosphine gas (PH3) plays in commercial pest control, identification of the residual components deposited during fumigation is mandatory. It has been postulated that these infrequent residues are primarily composed of phosphoric acid or reduced forms of phosphoric acid [hypophosphorous acid (H3PO2) and phosphorous acid (H3PO3)], due to the oxidative degradation of phosphine. Using environmental scanning electron microscopy, gas phase Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy, the structural elucidation and formation mechanism of the yellow amorphous polyhydric phosphorus polymers (P(x)H(y)) that occur in addition to the lower oxyacids of phosphorus in residues deposited during PH3 fumigations of select tobacco commodities are explored. This research determined that nitric oxide gas (or nitrogen dioxide) initiates residue formation of phosphorus hydride polymers and phosphorus oxyacids during PH3 fumigations of stored products.

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Section: Resultsmentioning

confidence: 98%

Residue Formations of Phosphorus Hydride Polymers and Phosphorus Oxyacids during Phosphine Gas Fumigations of Stored Products

Flora

Byers

Plunkett

et al. 2005

J. Agric. Food Chem.

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“…In previous studies the NO monomer was thought to react with phosphine in a consecutive manner. 14,16 These conclusions are in stark contrast with recent kinetics and theoretical studies that have suggested that the nitric oxide dimer (NO) 2 is a more effective oxidant than NO. 6,14,15 In this work we use highly correlated ab initio electronic structure calculations in order to shed some light on the mechanism for the reaction between NO and PH 3 .…”

Section: Introductionmentioning

confidence: 67%

“…Interestingly, similar to the case of the black/red phosphorus, the solid material is rather stable in air and water and insoluble in most solvents, including water, acetone, and chloromethanes (CH 2 Cl 2 and CHCl 3 ). 16,17 Initial studies reported in the literature indicated that the yellow material was mainly "phosphorus" containing H 3 PO 3 and H 3 PO 4 . 16 A more recent study based on X-ray fluorescence (XRF) measurements has not found considerable amounts of oxygen or nitrogen on the solid material surface.…”

Section: Introductionmentioning

confidence: 99%

“…16,17 Initial studies reported in the literature indicated that the yellow material was mainly "phosphorus" containing H 3 PO 3 and H 3 PO 4 . 16 A more recent study based on X-ray fluorescence (XRF) measurements has not found considerable amounts of oxygen or nitrogen on the solid material surface. 17 As discussed in detail later in this article measurements performed in the present study combining thermogravimetric analysis and mass spectrometry (TGA-MS) indicate that a large amount of reduced phosphorus in the form of PH 3 and P 4 (as much as 80 wt % in mass of phosphorus) is released from the solid material when the temperature is increased to 873 K in a helium atmosphere.…”

Section: Introductionmentioning

confidence: 99%

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Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism

et al. 2008

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A yellow solid material [P(x)H(y)] has been obtained in the reaction of phosphine (PH(3)) and nitric oxide (NO) at room temperature and characterized by thermogravimetric analysis mass spectrometry (TGA-MS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In this work using complete basis set (CBS-QB3) methods a plausible mechanism has been investigated for phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab initio method suggest (a) instead of the monomer the nitric oxide dimer acts as an initial oxidant, (b) the resulting phosphine oxides (H(3)P=O <--> H(3)P(+)O(-)) in the gas phase draw each other via strong dipolar interactions between the P-O groups, and (c) consequently an autocatalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations a series of cluster models was computed to simulate polymerization.

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“…The potential oxidation processes of PH 3 have been studied in the lab and are listed as follows (Fritz et al 1982;Odom and Zozulin 1981;Withnall and Andrews 1988):…”

Section: Radiationmentioning

confidence: 99%

Phosphine in the Lower Atmosphere of Qingdao—A Coastal Site of the Yellow Sea (China)

Zhang

et al. 2009

Water Air Soil Pollut

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Gaseous phosphine (PH 3 ) in the inshore atmosphere was observed from October 2005 to August 2006 at a coastal site of the Yellow Sea in China. The concentration of PH 3 ranged from 0.01 to 14.86 ng m −3 with an average of 1.14 ng m −3 . The concentration showed a diurnal variation in PH 3 with the peak occurring at morning and the lowest point at noon. An obvious seasonal variation of atmospheric PH 3 was found, with the PH 3 levels in the summer higher than those in the winter. The PH 3 levels in the atmosphere were apparently affected by temperature, radiation, sources, and other meteorological factors. The data indicate that PH 3 can be transported between the terrestrial and inshore atmosphere of Qingdao and the Yellow Sea or the East China Sea in both directions. The study increases evidence that PH 3 participates within the global biogeochemical phosphorus cycle in P transport from land and inshore waters to the sea where commonly P is scarce and where PH 3 inflow could be of important.

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The Reaction of Nitric Oxide With Phosphine and Several Difluorophosphine Molecules

Cited by 7 publications

References 15 publications

Residue Formations of Phosphorus Hydride Polymers and Phosphorus Oxyacids during Phosphine Gas Fumigations of Stored Products

Residue Formations of Phosphorus Hydride Polymers and Phosphorus Oxyacids during Phosphine Gas Fumigations of Stored Products

Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism

Phosphine in the Lower Atmosphere of Qingdao—A Coastal Site of the Yellow Sea (China)

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