Oxidation of phosphine and arsine by metal complexes and free and bound oxygen

Dorfman, Ya. A.; Yukht, I. M.; Levina, L. V.; Polimbetova, G. S.; Petrova, Tatiana V.; Emel'yanova, V. S.

doi:10.1070/rc1991v060n06abeh001097

Cited by 14 publications

(10 citation statements)

References 2 publications

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“…Another test with 1 N H2SO4 was conducted with 10 ppm PH3, and after 20 days, there was no obvious loss of PH3 in H2SO4 samples compared to controls. According to our literature review, only very concentrated H2SO4 (concentration in excess of 90 wt %) is expected to remove PH3 from gas (31).…”

Section: Resultsmentioning

confidence: 99%

“…It also seems possible that some of the PH3 was precipitated as a phosphorus solid in the samples. For instance, Dorfman (31) mentioned that silver(I) and mercury(II) in water could remove PH3 by forming phosphide solids.…”

Section: Resultsmentioning

confidence: 99%

“…Mn and Co formed brown precipitates, and Cr formed a light blue precipitate. The oxidation states of chromium and manganese in the stock solution (with HNO3) were +3 and +2, respectively, and it is anticipated that chromium(VI) and manganese(VII) would behave differently because they are widely used in sulfuric acid solution to remove PH3 from gases (31).…”

Section: Resultsmentioning

confidence: 99%

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Phosphates, Phosphites, and Phosphides in Environmental Samples

Morton

Glindemann

Edwards

2003

Environ. Sci. Technol.

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The common assumption that phosphorus occurs exclusively as phosphate in the environment is deserving of increased scrutiny. If a sample contained reduced phosphorus compounds (P in an oxidation state of less than +5), standard methods of phosphorus determination would incorrectly classify the compounds mostly as organic P, although significant fractions were sometimes misclassified as orthophosphates and condensed P. The disappearance of gaseous hydrogen phosphide (PH3) from samples was a function of solution composition, in that certain acids and metals enhanced removal whereas other constituents increased PH3 stability. No previously used extraction method could detect a significant portion of reduced phosphorus in representative samples by measuring PH3 evolution, particularly for highly recalcitrant iron phosphides. Despite analytical limitations, clear evidence was gathered that reduced phosphorus compounds can be leached from cast iron to water and that reduced phosphorus is also present in the scale (rust) that forms on the metal.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Phosphates, Phosphites, and Phosphides in Environmental Samples

Morton

Glindemann

Edwards

2003

Environ. Sci. Technol.

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“…The citations above state that acetylene is passed up a tower down which >95% H2SO4 is sprayed, implying efficient removal (by rapid oxidation of phosphine to phosphoric acid) in 10s of seconds. (Dorfman et al 1991) state that the reaction occurs at negligible rate at concentrations of acid below ~90% acid by weight. Such reaction behavior suggests attack on PH3 by SO3, which is consistent with the electrophilic attack by SO3 on the lone pair on PH3 (PH3 is not significantly ionized in pure sulfuric acid, unlike NH3 which is exclusively present as NH4 + ), and with B3LYP ab initio calculations to 6-311-G level of the energy of the reaction:…”

Section: 1 Phosphine Chemistry In Concentrated Sulfuric Acidmentioning

confidence: 99%

Phosphine on Venus Cannot Be Explained by Conventional Processes

et al. 2021

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The recent candidate detection of ~20 ppb of phosphine in the middle atmosphere of Venus is so unexpected that it requires an exhaustive search for explanations of its origin. Phosphoruscontaining species have not been modelled for Venus' atmosphere before and our work represents the first attempt to model phosphorus species in Venusian atmosphere. We thoroughly explore the potential pathways of formation of phosphine in a Venusian environment, including in the planet's atmosphere, cloud and haze layers, surface, and subsurface. We investigate gas reactions, geochemical reactions, photochemistry, and other non-equilibrium processes. None of these potential phosphine production pathways are sufficient to explain the presence of ppb phosphine levels on Venus. The presence of PH3, therefore, must be the result of a process not previously considered plausible for Venusian conditions. The process could be unknown geochemistry, photochemistry, or even aerial microbial life, given that on Earth phosphine is exclusively associated with anthropogenic and biological sources. The detection of phosphine adds to the complexity of chemical processes in the Venusian environment and motivates in situ follow up sampling missions to Venus.

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“…However, no systematic kinetic data exists for the reaction of phosphine with sulfuric acid, despite the industrial importance of this reaction [11]. Single reaction points were, therefore, identified in five sources [12][13][14][15][16] and matched to Q 10 , m and c values from Equation 2below. This is not ideal, as these are semi-anecdotal reports gathered up to a century ago under a wide range of conditions and illustrates the need for more systematic measurement of some literature values.…”

Section: Literature Search For Datamentioning

confidence: 99%

A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

Bains

Petkowski

Seager

2021

Data

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We describe a dataset of the quantitative reactivity of organic chemicals with concentrated sulfuric acid. As well as being a key industrial chemical, sulfuric acid is of environmental and planetary importance. In the absence of measured reaction kinetics, the reaction rate of a chemical with sulfuric acid can be estimated from the reaction rate of structurally related chemicals. To allow an approximate prediction, we have collected 589 sets of kinetic data on the reaction of organic chemicals with sulfuric acid from 262 literature sources and used a functional group-based approach to build a model of how the functional groups would react in any sulfuric acid concentration from 60–100%, and between −20 °C and 100 °C. The data set provides the original reference data and kinetic measurements, parameters, intermediate computation steps, and a set of first-order rate constants for the functional groups across the range of conditions −20 °C–100 °C and 60–100% sulfuric acid. The dataset will be useful for a range of studies in chemistry and atmospheric sciences where the reaction rate of a chemical with sulfuric acid is needed but has not been measured.

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Oxidation of phosphine and arsine by metal complexes and free and bound oxygen

Cited by 14 publications

References 2 publications

Phosphates, Phosphites, and Phosphides in Environmental Samples

Phosphates, Phosphites, and Phosphides in Environmental Samples

Phosphine on Venus Cannot Be Explained by Conventional Processes

A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

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