Analysis of the aqueous solubility of trialkyl phosphates, dialkyl alkylphosphonates, dialkylphosphites and alkyl dialkylphosphinates

Abstract

Linear free energy relationship (LFER) analysis based on the molar intrinsic volume (Vx), McGowan hydrophile‒lipophile balance (HLB) and cumulative Kabachnik constants (Σσϕ) of considered solutes has been performed for the solubility of trialkyl phosphates, dialkyl alkylphosphonates, dialkyl phosphites and alkyl dialkylphosphonates in pure water (called also as their aqueous solubility). The descriptors mentioned above are known for all considered solutes and are strongly correlated with their aqueous solubility. From the correlation found for trialkyl phosphates, dialkyl alkylphosphonates and dialkyl phosphites it follows that the mean contribution of each methylene group in their structure (Δlog Sw) is a constant for these homologous series and equal to − 0.41. It means that within of homologous series the aqueous solubility of succeeding solutes decreases regularly. The established increment has been further used as a tool for the preliminary selection of solutes whose aqueous solubility at 25 °C is in agreement with this condition. The adequate model (further denoted as AR model) based on the accessible data of temperature effects upon the aqueous solubility of tributyl phosphate, dibutyl butylphosphonate and butyl dibutylphosphinate has been formulated and then tested with positive results for the other solutes whose solubility is known at a selected constant temperature, e.g. at 25 °C. It should noticed, however, that in this case there are some serious restrictions. First, the interpretation and formulation of conclusions for the solutes which aqueous solubility is known at one selected temperature (e.g. 25 °C) or if it has been determined at a few temperatures only, should be made with care. Second, the obtained results with AR model cannot be used for prediction of temperature effects upon the aqueous solubility of such solutes. Simultaneously, the results obtained with AR model have been compared with those following from the modified Abraham model. Such comparison has been possible due to a significant progress in the different application of Abraham model for several organophosphorus derivatives as monobasic dialkyl- and diarylphosphoric acids, dialkyl- and diphenylphosphinic acids, trialkyl- and triaryl phosphates, dimethyl methylphosphonate, dialkylphosphites and some of trialkyl- and triarylphosphine oxides, respectively.