Diffusion coefficients of perfluorinated n-alcohols in water and heavy water: experiment and computer simulation

Fluorinated surfactants find nowadays many industrial applications due to their enhanced ability to lower surface tension in aqueous solutions [1]. As a result of their extensive use, emissions of fluorinated surfactants became frequent and, because of their persistent character, have been increasingly found in the environment [2]. Both the development of theoretical models to study the environmental fate of those pollutants and the design of unit operations (e.g. adsorption) used for their removal require the knowledge of some key properties such as the diffusion coefficients in water. n-alcohols with perfluorinated carbon chains can be regarded as the most simple fluorinated surfactants, being suitable to be used as model substances that can make easier the molecular interpretation and the theoretical treatment of fluorinated surfactants in a systematic way. On the other hand, the smallest perfluorinated n-alcohols find applications in many fields, such as the pharmaceutical industry, polymer production and refrigerant technology as components of working fluids. We have recently reported intra-diffusion coefficients of 2,2,2-trifluoroethanol in water for dilute solutions as a function of composition and temperature, obtained both experimentally (NMR spin-echo) and by computer simulation (molecular dynamics) [3]. The results obtained by molecular dynamics closely reproduce the experimental ones, which has encouraged us to attempt predicting the dynamic properties of aqueous solutions of the higher fluorinated alcohols and other fluorinated surfactants. In this work, the intra-diffusion coefficients of 2,2,3,3,3-pentafluoropropan-1-ol, 2,2,3,3,4,4,4-heptafluorobutan-1-ol and 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol in water and heavy water were measured experimentally by NMR spin-echo technique and compared with results obtained from computer simulation (molecular dynamics). The comparison that can be done between experimental and simulation results is used to test the theoretical models for this chemical family of substances and enriches the molecular interpretation of the results, which can be useful to anticipate trends for more complex fluorinated surfactants. [1] Buck, R. C.; Franklin, J.; Berger, U.; Conder, J. M.; Cousins, I. T.; de Voogt, P.; Jensen, A. A.; Kannan, K.; Mabury, S. A.; van Leeuwen, S., Integr. Environ. Assess. Manage 2011, 7, 513−541 [2] D’Hollander, W.; de Voogt, P.; De Coen, W.; Bervoets, L., Rev. Environ. Contam. Toxicol. 2010, 208, 179–215 [3] Pereira, L. A. M.; Martins, L. F. G.; Ascenso, J. R.; Morgado, P.; Prates Ramalho, J. P.; Filipe, E. J. M., submitted to publicatio

Fluorinated surfactants in solution: Diffusion coefficients of fluorinated alcohols in water

Intra-diffusion coefficients of three fluorinated alcohols, 2,2,3,3,3-pentafluoropropan-1-ol (PFP), 2,2,3,3,4,4,4-heptafluorobutan-1-ol (HFB) and 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol (NFP) in water have been measured by the PFG–NMR spin-echo technique as a function of temperature and composition, focusing on the alcohol dilute region. For comparison, intra-diffusion coefficients of 2,2,2- trifluoroethanol (TFE) and HFB have also been measured in heavy water using the same method and conditions. As far as we know, these are the first experimental measurements of this property for these binary systems. Intra-diffusion coefficients for NFP in water and for TFE and HFB in heavy water have also been obtained by molecular dynamics simulation, complementing those for TFE, PFP and HFB reported in a previous work. The agreement between experimental and simulated results for PFP, HFB and NFP in water is reasonable, although presenting higher deviations than for the TFE/water system. From the dependence of the intra-diffusion coefficients on temperature, diffusion activation energies were estimated for all the solutes in water and heavy water

On the mobility of dialkyl adipates by PFGSE NMR, computer simulations and other property measurement methods

Encontro realizado em Alacalá de Henares (Madrid), de 22 a 25 de Setembro de 2014Dialkyl adipates are a class of esters materials used as components of lubricants and plasticizers. Diffusion of plasticizers in polymers is a complex process that is difficult to study [1]. As a contribution to understand this phenomenon, the self-diffusion coefficients of five dialkyl adipates (dimethyl, diethyl, dipropyl, dibuthyl and bis(2-ethylhexyl)) were measured by the PFGSTE method in the temperature range 20 to 60ºC. It was shown that these compounds follow the Stokes-Einstein equation [2]. In effect, the self-diffusion coefficients change linearly with T.η-1(η is the viscosity). The dependence of the activation energies for self-diffusion is discussed in terms of size and branching of the alkyl chains of the adipates. Molecular dynamics (MD) simulations were done for these sytems in order to predict the diffusion coefficients as a function of temperature [3]. Acknolwedgements: This work was supported by the Strategic Projects PEst-OE/QUI/UI0100/2011 and PEst-OE/QUI/ UI0100/2013, both funded by Fundação para a Ciência e a Tecnologia (FCT, Portugal). We thank also FCT for funding the NMR facility through Project RECI/QEQ-QIN/0189/2012. References: [1] Rahman M.; Brazel C. S., Prog. Polym. Sci. 2004, 29, 1223–1248. [2] Price W.S, NMR Studies of Translation Motion, Cambridge University Press, Cambridge, 2009. [3] Pereira, L. A. M.; Martins, L. F. G.; Ascenso, J. R; Morgado, P.; Ramalho, J. P. P.; Filipe, E. J. M., J. Chem. Eng. Data 2014, accepted for publication

Diffusion Coefficients of Fluorinated Surfactants in Water:

Intradiffusion coefficients of 2,2,2-trifluoroethanol in water have been measured by the pulsed field gradient (PFG)-NMR spin−echo technique as a function of temperature and composition on the dilute alcohol region. The measurements extend the range of compositions already studied in the literature and, for the first time, include the study of the temperature dependence. At the same time, intradiffusion coefficients of 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropan-1-ol, and 2,2,3,3,4,4,4-heptafluorobutan-1-ol in water were obtained by computer simulation (molecular dynamics) as a function of composition and temperature. The intradiffusion coefficients of 2,2,2-trifluoroethanol in water obtained by simulation agree with the experimental results, while those of 2,2,3,3,3- pentafluoropropan-1-ol and 2,2,3,3,4,4,4-heptafluorobutan-1-ol are the first estimation of this property for those systems. The molecular dynamics simulations were also used to calculate the intradiffusion coefficients of perfluorooctanesulfonic acid and perfluorooctanoic acid in water at infinite dilution as a function of temperature, which are very difficult to obtain experimentally because of the very low solubility of these substances. From the dependence of the intradiffusion coefficients on temperature, diffusion activation energies were estimated for all the solutes in water

Evaluating the Impact of Nature-Based Solutions: A Handbook for Practitioners

The Handbook aims to provide decision-makers with a comprehensive NBS impact assessment framework, and a robust set of indicators and methodologies to assess impacts of nature-based solutions across 12 societal challenge areas: Climate Resilience; Water Management; Natural and Climate Hazards; Green Space Management; Biodiversity; Air Quality; Place Regeneration; Knowledge and Social Capacity Building for Sustainable Urban Transformation; Participatory Planning and Governance; Social Justice and Social Cohesion; Health and Well-being; New Economic Opportunities and Green Jobs. Indicators have been developed collaboratively by representatives of 17 individual EU-funded NBS projects and collaborating institutions such as the EEA and JRC, as part of the European Taskforce for NBS Impact Assessment, with the four-fold objective of: serving as a reference for relevant EU policies and activities; orient urban practitioners in developing robust impact evaluation frameworks for nature-based solutions at different scales; expand upon the pioneering work of the EKLIPSE framework by providing a comprehensive set of indicators and methodologies; and build the European evidence base regarding NBS impacts. They reflect the state of the art in current scientific research on impacts of nature-based solutions and valid and standardized methods of assessment, as well as the state of play in urban implementation of evaluation frameworks

Synthesis, structural characterisation and metal ion-binding properties of a new p-tert-butyldihomooxacalix[4]crown-6

1,3-Diethoxy-p-tert-butyldihomooxacalix[4]arene-crown-6 (3) was synthesised for the first time. Compound 3 was isolated in a partial cone A conformation in solution at room temperature, as established by NMR measurements (1H, 13C and NOESY). The assignment of both proton and carbon NMR spectra was achieved by a combination of COSY and HSQCTOCSY experiments. The binding affinities of ligand 3 for alkali, alkaline earth, transition and heavy metal cations have been assessed by phase transfer and proton NMR titration experiments. Compound 3 is a reasonable extractant for the alkali cations and also for Ag+, showing preference for Cs+. Ligand 3 forms 1:1 complexes with K+, Ca2+, Ag+ and Pb2+, as determined by proton NMR titrations, which also indicated that these cations should be encapsulated into the cavity defined by the crown ether unit, the ethoxy group and the inverted aryl ring. A new dihomooxacalix[4]crown-6 (3) was synthesised and isolated in a partial cone A conformation in solution at room temperature, as established by NMR (1H, 13C and NOESY). The binding properties of 3 towards alkali, alkaline earth, transition and heavy metal cations have been assessed by phase transfer and proton NMR titration experiments. The results are compared to those obtained with calixcrowns 1 and 2.[image omitted]