- ELECTROCHEMICALLY INDUCED PROCESSES IN THE FORMATION OF PHOSPHORUS ACID DERIVATIVES. 2. THE ROLE OF POLYMERIZATION PROCESSES IN THE ELECTROSYNTHESIS OF THE ESTERS OF PHOSPHORUS ACIDS FROM WHITE PHOSPHORUS
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The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated.It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop).It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound.It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.Key words: Phosphate esters, white phosphorus, electrosynthesis.
- Romakhin, A. S.,Zaripov, I. M.,Budnikova, Yu. G.,Kargin, Yu. M.,Nikitin, E. V.,et al.
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- Experimental determination and model correlation for the solubilities of trialkyl phosphates in supercritical carbon dioxide
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The solubilities of a series of trialkyl phosphates in supercritical carbon dioxide have been investigated. The solubility measurement was carried out using a dynamic flow method. The measurements were performed at 313, 323 and 333 K and in the pressure range of 10 to 25 MPa. The trialkyl phosphates were found to be highly soluble in supercritical carbon dioxide and the solubilities were in the range of 0.01 to 0.1 mol fraction. The solubility of trialkyl phosphates increases with an increase in pressure at constant temperature. A reverse behavior was observed, wherein the solubilities decreased with increase in temperature in the investigated pressure region. At constant temperature and pressure, the solubilities of the trialkyl phosphates decrease with the alkyl chain length. The solubility data was found to be consistent with the Mendez-Teja model. The solubilities were correlated by the Chrastil model and an association model based on the van Laar activity coefficient model with absolute deviations of less than 10%. A key result is that the model parameters based on the association model varied linearly with the carbon number.
- Pitchaiah,Sivaraman,Lamba, Neha,Madras, Giridhar
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p. 51286 - 51295
(2016/06/09)
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- Absolute viscosity and density of trisubstituted phosphoric esters
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This paper presents measurements on the absolute viscosity (η) and density (ρ) of trisubstituted phosphoric esters which are useful in understanding their flow mechanism necessary for accessing their role as plasticizers. The effect of chain length and branching has been examined on the η and ρ trends. From η data, by using the Vogel-Tammann-Fulchur (VTF) equation, the VTF temperature (To) has been obtained which also represents the ideal glass transition temperature. To is related to the flexibility of the molecules. It is observed that To initially decreases with molecular weight, reaches a minimum, and increases thereafter. The initial decrease in To has been attributed to the enhanced flexibility of the phosphate esters. Reversal of flexibility with relative molar mass beyond 400 is due to the gentle collision of the arms of the trisubstituted phosphoric esters. This has been further corroborated from the molar mass exponent as exhibited in the η-molar mass plot. The isomeric effect on η has also been investigated in tricresyl phosphates, hitherto for the first time. The ortho isomer has highest η among the isomers. The para isomer was found to have lowest To and hence highest flexibility compared to the ortho and meta isomers.
- Kannan,Kishore
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p. 649 - 655
(2007/10/03)
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- Synthesis of Trialkyl Phosphates from White Phosphorus
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A new method was proposed for preparing trialkyl phosphates directly from white phosphorus by its electrolysis in a mixture of acetonitrile, alcohol, and water with tetraethylammonium iodide as supporting electrolyte. To increase the amount of the product synthesized in the unit volume of the electrolyte solution and the productivity of the process, phosphorus and water are added to the electrolyte in portions, which allows synthesis of up to 1 mol of trialkyl phosphate in 1 1 of the electrolyte solution.
- Romakhin,Nikitin
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p. 1023 - 1026
(2007/10/03)
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