Catarina M S S Neves | Universidade de Aveiro (original) (raw)

Papers by Catarina M S S Neves

The Journal of Physical Chemistry, 2015

This work presents and highlights the differentiation of the physicochemical properties of the [C... more This work presents and highlights the differentiation of the physicochemical properties of the [C 1 Him][NTf 2 ], [C 2 Him][NTf 2 ], [

The Journal of Physical Chemistry, 2012

This work reports on the systematic investigation of the influence of the cation alkyl side-chain... more This work reports on the systematic investigation of the influence of the cation alkyl side-chain length of 1-alkyl-3-methylimidazolium chloride ionic liquids ([C n C 1 im]Cl, with n = 1−14), as well as the substitution of the most acidic hydrogen in the imidazolium core by a methyl group, in the formation of aqueous biphasic systems. Ternary phase diagrams, tie-lines, tieline slopes, tie-line lengths, and critical points for the several systems (ionic liquid + water + K 3 PO 4) were determined and reported at 298 K and atmospheric pressure. It is shown that the increase of the cation alkyl chain length enhances the formation of aqueous biphasic systems if alkyl chain lengths until the hexyl are considered. The results for longer alkyl side chains show, nevertheless, that the phenomenon is more complex than previously admitted and that the capacity of the ionic liquid to self-aggregate also governs its ability to phase separate. The effect of the alkyl side-chain length on the phase-forming ability of the studied systems was quantitatively evaluated based on their salting-out coefficients derived from a Setschenow-type behavior. The aptitude of each ionic liquid for liquid−liquid demixing as a function of the cation alkyl side-chain length clearly follows three different patterns. The results obtained for the trisubstituted cation indicate that the hydrogenbonding interactions between the ionic liquid cation and water are not a relevant issue in the formation of aqueous two-phase systems. In general, for the [C n C 1 im]Cl series, a multifaceted ratio between entropic contributions and the ability of each ionic liquid to self-aggregate in aqueous media control the phase behavior.

De Gruyter eBooks, May 20, 2019

In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-formi... more In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-forming components of aqueous biphasic systems (ABS), which allow the tailoring of polarity differences between the coexisting phases. Although investigations on the IL chemical structure and polymermolecularweight have been carried out, the use of mixtures of polymers can also be seen as a way of tailoring their two-phase formation ability and separation performance, which was not attempted earlier. In this work, we investigate novel ABS composed of cholinium-based ILs and mixtures of polymers, namely polyethylene glycol (PEG) of 400 and 2,000 g·mol-1, at differentmole fractions, as a way of tailoring the formation of ABS and their separation performance. The respective liquid-liquid phase diagrams were determined, and their ability to separate a set of alkaloids (caffeine, theophylline and theobromine) appraised. An increase on the PEG 2000mole fraction favors the formation of ABS. However, this does not follow a monotonous trend, where mole fractions of PEG 400 up to 0.3 do not display significant impact on the two-phase separation capability. Among the studied alkaloids, nicotine preferentially partitions to the IL-rich phase, while the remaining alkaloids majorly partition to the polymer-rich phase. Different selectivity patterns were verified, depending on the cholinium-based IL used and water content at the IL-rich phase. Overall, by using mixtures of polymers it is possible to decrease the viscosity of the coexisting phases and their toxicity impact, without losing their formation and separation capacities, by the addition of PEGs of lower molecular weight.publishe

RSC Advances, 2012

The number of applications involving ionic liquids has dramatically increased in the past few yea... more The number of applications involving ionic liquids has dramatically increased in the past few years, and their production and use in a large scale will inevitably lead to their dispersion into water streams (either by wastewater disposal or accidental leakage). Studies on the removal and recovery of ionic liquids from wastewater streams are therefore of crucial importance, yet particularly scarce. In this work, the use of aluminium salts is proposed to concentrate and remove ionic liquids from aqueous solutions. Two aluminium-based salts (Al 2 (SO 4) 3 and AlK(SO 4) 2 ?12H 2 O) were used to treat various aqueous solutions of ionic liquids containing imidazolium-, pyridinium-and phosphonium-based fluids. The gathered results show the enhanced ability of these salts to remove and recover ionic liquids from aqueous media. The minimum recovery efficiency achieved was 96%, whereas for a large array of systems recoveries of circa 100% of ionic liquid were attained. The residual concentrations of ionic liquids in water range from 0.01 to 6 wt%. The results reported disclose a novel promising technique for the recovery and treatment of aqueous effluents contaminated with ionic liquids by using salts commonly employed in water treatment processes, allowing thus its easy scale-up and adaptation to new processes involving ionic liquids.

Journal of Physical Chemistry B, Oct 24, 2007

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties t... more The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis-(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN) 3 ] < [PF 6 ] < [Tf 2 N] while the hydrophobicity of the cations increases from [C n mim] < [C n mpy] e [C n mpyr] < [C n mpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in... more Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in the past few years as alternatives to some hazardous volatile organic compounds. They are already used by industry, where it was possible to improve different processes by the incorporation of this kind of non-volatile and often liquid solvents. However, even if ionic liquids cannot contribute to air pollution, due to their negligible vapour pressures, they can be dispersed thorough aquatic streams thus contaminating the environment. Therefore, the main goals of this work are to study the mutual solubilities between water and different ionic liquids in order to infer on their environmental impact, and to propose effective methods to remove and, whenever possible, recover ionic liquids from aqueous media. The liquid-liquid phase behaviour of different ionic liquids and water was evaluated in the temperature range between (288.15 and 318.15) K. For higher melting temperature ionic liquids...

Ionic Liquids, 2019

In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-formi... more In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-forming components of aqueous biphasic systems (ABS), which allow the tailoring of polarity differences between the coexisting phases. Although investigations on the IL chemical structure and polymermolecularweight have been carried out, the use of mixtures of polymers can also be seen as a way of tailoring their two-phase formation ability and separation performance, which was not attempted earlier. In this work, we investigate novel ABS composed of cholinium-based ILs and mixtures of polymers, namely polyethylene glycol (PEG) of 400 and 2,000 g·mol-1, at differentmole fractions, as a way of tailoring the formation of ABS and their separation performance. The respective liquid-liquid phase diagrams were determined, and their ability to separate a set of alkaloids (caffeine, theophylline and theobromine) appraised. An increase on the PEG 2000mole fraction favors the formation of ABS. However, this does not follow a monotonous trend, where mole fractions of PEG 400 up to 0.3 do not display significant impact on the two-phase separation capability. Among the studied alkaloids, nicotine preferentially partitions to the IL-rich phase, while the remaining alkaloids majorly partition to the polymer-rich phase. Different selectivity patterns were verified, depending on the cholinium-based IL used and water content at the IL-rich phase. Overall, by using mixtures of polymers it is possible to decrease the viscosity of the coexisting phases and their toxicity impact, without losing their formation and separation capacities, by the addition of PEGs of lower molecular weight.publishe

Frontiers in Chemistry, 2019

no losses on the ABS separation performance. Overall, the obtained results show that the investig... more no losses on the ABS separation performance. Overall, the obtained results show that the investigated ABS are promising platforms to simultaneously separate carbohydrates and antioxidants from real food waste samples, and could be used in further related applications foreseeing industrial food waste valorization.

Thermochimica Acta, 2018

Solid-liquid equilibria (SLE) data for two binary organic mixtures of N-(2-methoxyethyl)-p-nitroa... more Solid-liquid equilibria (SLE) data for two binary organic mixtures of N-(2-methoxyethyl)-p-nitroaniline + Nethyl-4-nitroaniline (S1) and N-(2-ethanol)-p-nitroaniline + N-ethyl-4-nitroaniline (S2) have been measured using differential scanning calorimeter to build the corresponding solid-liquid phase diagrams. The quality of the SLE data has been checked by consistency tests, presenting good quality factors for both systems. Simple eutectic behavior has been observed for these systems with the presence of a solid-solid transition for S2. The SLE data have been correlated by means of Wilson, NRTL, and UNIQUAC equations. The used models calculate the equilibrium temperatures very satisfactorily. The best modeling results were obtained using the Wilson equation with a root mean square deviation between experimental and calculated values for S1 and S2 of 1.15 and 1.99, respectively. The Wilson, NRTL, and UNIQUAC equations have also been used to compute excess thermodynamic functions viz. excess Gibbs energy, enthalpy, and entropy. The obtained results demonstrated a moderate positive deviation to ideality for S1, and a strong positive deviation for S2, unveiling the nature of the interactions between the compounds forming each mixture. In addition, microstructural studies have been carried out by FTIR, XRD and optical microscopy. Weak molecular interactions have been shown for the eutectic compositions. Jackson's roughness parameter was calculated and found to be greater than 2, suggesting the faceted morphology with irregular structures.

Chemical Communications, 2018

Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and ... more Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and fatty acids, were used for the extraction and separation of Cu(ii) from other transition metals in mildly acidic solutions.

Journal of Solution Chemistry, 2018

The order of the salting-in or salting-out inducing ability of ions on the aqueous solubility of ... more The order of the salting-in or salting-out inducing ability of ions on the aqueous solubility of macromolecules in aqueous solutions is known as the Hofmeister series. Taking into account that ionic liquids (ILs) are constituted by ions, they can exert similar effects on the solubility of other ILs in aqueous media. To expand the knowledge of the salting-in/out ability of ILs, experimental studies on the solubility of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) in water and in the presence of other IL/salts, were conducted at 298.15 K and atmospheric pressure. Both the impact of the anion and cation of the IL were evaluated with the following ILs/salts: 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hydrogensulfate, cholinium bis(trifluoromethylsulfonyl) imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and lithium bis(trifluoromethylsulfonyl)imide, over a wide composition range. As happens with common salts, both salting-in and salting-out effects exerted by ILs were observed, with a higher impact exerted by the IL anion on the salting-out phenomenon. These data allow better understanding of the ILs impact when designing liquid-liquid separation processes.

Physical chemistry chemical physics : PCCP, Jan 25, 2015

Due to scarce available experimental data, as well as due to the absence of predictive models, th... more Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg(-1)). At salt molalities higher than 0.2 mol kg(-1), all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.2 mol kg(-1). To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electro...

RSC Advances, 2012

The number of applications involving ionic liquids has dramatically increased in the past few yea... more The number of applications involving ionic liquids has dramatically increased in the past few years, and their production and use in a large scale will inevitably lead to their dispersion into water streams (either by wastewater disposal or accidental leakage). Studies on the removal and recovery of ionic liquids from wastewater streams are therefore of crucial importance, yet particularly scarce. In this work, the use of aluminium salts is proposed to concentrate and remove ionic liquids from aqueous solutions. Two aluminium-based salts (Al 2 (SO 4) 3 and AlK(SO 4) 2 ?12H 2 O) were used to treat various aqueous solutions of ionic liquids containing imidazolium-, pyridinium-and phosphonium-based fluids. The gathered results show the enhanced ability of these salts to remove and recover ionic liquids from aqueous media. The minimum recovery efficiency achieved was 96%, whereas for a large array of systems recoveries of circa 100% of ionic liquid were attained. The residual concentrations of ionic liquids in water range from 0.01 to 6 wt%. The results reported disclose a novel promising technique for the recovery and treatment of aqueous effluents contaminated with ionic liquids by using salts commonly employed in water treatment processes, allowing thus its easy scale-up and adaptation to new processes involving ionic liquids.

Environmental science. Processes & impacts, 2013

The applications and variety of ionic liquids (ILs) have increased during the last few years, and... more The applications and variety of ionic liquids (ILs) have increased during the last few years, and their use at a large scale will require their removal/recovery from wastewater streams. Adsorption on activated carbons (ACs) has been recently proposed for this aim and this work presents a systematic analysis of the influence of the IL chemical structures (cation side chain, head group, anion type and the presence of functional groups) on their adsorption onto commercial AC from water solution. Here, the adsorption of 21 new ILs, which include imidazolium-, pyridinium-, pyrrolidinium-, piperidinium-, phosphonium- and ammonium-based cations and different hydrophobic and hydrophilic anions, has been experimentally measured. This contribution allows an expansion of the range of IL compounds studied in previous works, and permits a better understanding of the influence of the IL structures through the adsorption on AC. In addition, the COSMO-RS method was used to analyze the measured adso...

The Journal of Physical Chemistry B, 2012

This work reports on the systematic investigation of the influence of the cation alkyl side-chain... more This work reports on the systematic investigation of the influence of the cation alkyl side-chain length of 1-alkyl-3-methylimidazolium chloride ionic liquids ([C n C 1 im]Cl, with n = 1−14), as well as the substitution of the most acidic hydrogen in the imidazolium core by a methyl group, in the formation of aqueous biphasic systems. Ternary phase diagrams, tie-lines, tieline slopes, tie-line lengths, and critical points for the several systems (ionic liquid + water + K 3 PO 4) were determined and reported at 298 K and atmospheric pressure. It is shown that the increase of the cation alkyl chain length enhances the formation of aqueous biphasic systems if alkyl chain lengths until the hexyl are considered. The results for longer alkyl side chains show, nevertheless, that the phenomenon is more complex than previously admitted and that the capacity of the ionic liquid to self-aggregate also governs its ability to phase separate. The effect of the alkyl side-chain length on the phase-forming ability of the studied systems was quantitatively evaluated based on their salting-out coefficients derived from a Setschenow-type behavior. The aptitude of each ionic liquid for liquid−liquid demixing as a function of the cation alkyl side-chain length clearly follows three different patterns. The results obtained for the trisubstituted cation indicate that the hydrogenbonding interactions between the ionic liquid cation and water are not a relevant issue in the formation of aqueous two-phase systems. In general, for the [C n C 1 im]Cl series, a multifaceted ratio between entropic contributions and the ability of each ionic liquid to self-aggregate in aqueous media control the phase behavior.

The Journal of Physical Chemistry B, 2013

The Journal of Physical Chemistry B, 2011

The possibility of developing a scale for solubility parameters, with the purpose of predicting t... more The possibility of developing a scale for solubility parameters, with the purpose of predicting the performance and aiding the selection of ILs, was evaluated. For the estimation of solubility parameters, infinite-dilution activity coefficient data were used. The results allowed the identification of a curious behavior for ILs that seem to present more than one solubility parameter, acting as polar molecules in some situations and as nonpolar molecules in others, depending on the medium. This behavior was confirmed by solubility measurements of [C 4 MIM][PF 6 ] in solvent mixtures. In this work, the solubility parameters were also estimated from other properties, namely, viscosities and enthalpies of vaporization, and the relation between the various sets of solubility parameters is discussed. The results obtained suggest that, given the complexity of IL molecules and their liquid phases, a one-dimensional scale for solubility parameters that is able to characterize these fluids is not feasible.

The Journal of Physical Chemistry B, 2007

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties t... more The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis-(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN) 3 ] < [PF 6 ] < [Tf 2 N] while the hydrophobicity of the cations increases from [C n mim] < [C n mpy] e [C n mpyr] < [C n mpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

The Journal of Chemical Thermodynamics, 2011

In this work, the solubility of water in several tetradecyltrihexylphosphonium-based ionic liquid... more In this work, the solubility of water in several tetradecyltrihexylphosphonium-based ionic liquids at 298.15 K, and densities and viscosities of both pure and water-saturated ionic liquids in a broad temperature range were measured. The selected ionic liquids comprise the common tetradecyltrihexylphosphonium cation combined with the following anions: bromide, chloride, bis(trifluoromethylsulfonyl)imide, decanoate, methanesulfonate, dicyanamide and bis(2,4,4-trimethylpentyl)phosphinate. The isobaric thermal expansion coefficients for pure and water-saturated ionic liquids were determined based on the density dependence with temperature. Taking into account that the excess molar volumes of the current hydrophobic water-saturated ionic liquids are negligible, the solubility of water was additionally estimated from the gathered density data and compared with the experimental solubilities obtained. Moreover, the experimental densities were compared with those predicted by the Gardas and Coutinho model while viscosity data were correlated using the Vogel-Tammann-Fulcher method.

Journal of Chemical & Engineering Data, 2011

Among new potential solvents for lignocellulosic materials, ionic liquids (ILs) are attracting co... more Among new potential solvents for lignocellulosic materials, ionic liquids (ILs) are attracting considerable attention. Hence, the knowledge of the thermophysical properties of such fluids is essential for the design of related industrial processes. Therefore, in this work, a set of thermophysical properties, namely, density, viscosity, and refractive index, as a function of temperature, and isobaric thermal expansivity and heat capacities at a constant temperature, were determined for eight ionic liquids with the 1-ethyl-3-methylimidazolium cation combined with the following anions: acetate, methylphosphonate, methanesulfonate, trifluoromethanesulfonate, dicyanamide, thiocyanate, tosylate, and dimethylphosphate. Imidazolium-based ILs were chosen since these are the most studied ionic fluids in biomass dissolution approaches, while a large array of anions was investigated because it was already demonstrated that it is the IL anion that mainly governs the dissolution.

The Journal of Physical Chemistry, 2015

This work presents and highlights the differentiation of the physicochemical properties of the [C... more This work presents and highlights the differentiation of the physicochemical properties of the [C 1 Him][NTf 2 ], [C 2 Him][NTf 2 ], [

The Journal of Physical Chemistry, 2012

This work reports on the systematic investigation of the influence of the cation alkyl side-chain... more This work reports on the systematic investigation of the influence of the cation alkyl side-chain length of 1-alkyl-3-methylimidazolium chloride ionic liquids ([C n C 1 im]Cl, with n = 1−14), as well as the substitution of the most acidic hydrogen in the imidazolium core by a methyl group, in the formation of aqueous biphasic systems. Ternary phase diagrams, tie-lines, tieline slopes, tie-line lengths, and critical points for the several systems (ionic liquid + water + K 3 PO 4) were determined and reported at 298 K and atmospheric pressure. It is shown that the increase of the cation alkyl chain length enhances the formation of aqueous biphasic systems if alkyl chain lengths until the hexyl are considered. The results for longer alkyl side chains show, nevertheless, that the phenomenon is more complex than previously admitted and that the capacity of the ionic liquid to self-aggregate also governs its ability to phase separate. The effect of the alkyl side-chain length on the phase-forming ability of the studied systems was quantitatively evaluated based on their salting-out coefficients derived from a Setschenow-type behavior. The aptitude of each ionic liquid for liquid−liquid demixing as a function of the cation alkyl side-chain length clearly follows three different patterns. The results obtained for the trisubstituted cation indicate that the hydrogenbonding interactions between the ionic liquid cation and water are not a relevant issue in the formation of aqueous two-phase systems. In general, for the [C n C 1 im]Cl series, a multifaceted ratio between entropic contributions and the ability of each ionic liquid to self-aggregate in aqueous media control the phase behavior.

De Gruyter eBooks, May 20, 2019

In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-formi... more In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-forming components of aqueous biphasic systems (ABS), which allow the tailoring of polarity differences between the coexisting phases. Although investigations on the IL chemical structure and polymermolecularweight have been carried out, the use of mixtures of polymers can also be seen as a way of tailoring their two-phase formation ability and separation performance, which was not attempted earlier. In this work, we investigate novel ABS composed of cholinium-based ILs and mixtures of polymers, namely polyethylene glycol (PEG) of 400 and 2,000 g·mol-1, at differentmole fractions, as a way of tailoring the formation of ABS and their separation performance. The respective liquid-liquid phase diagrams were determined, and their ability to separate a set of alkaloids (caffeine, theophylline and theobromine) appraised. An increase on the PEG 2000mole fraction favors the formation of ABS. However, this does not follow a monotonous trend, where mole fractions of PEG 400 up to 0.3 do not display significant impact on the two-phase separation capability. Among the studied alkaloids, nicotine preferentially partitions to the IL-rich phase, while the remaining alkaloids majorly partition to the polymer-rich phase. Different selectivity patterns were verified, depending on the cholinium-based IL used and water content at the IL-rich phase. Overall, by using mixtures of polymers it is possible to decrease the viscosity of the coexisting phases and their toxicity impact, without losing their formation and separation capacities, by the addition of PEGs of lower molecular weight.publishe

RSC Advances, 2012

The number of applications involving ionic liquids has dramatically increased in the past few yea... more The number of applications involving ionic liquids has dramatically increased in the past few years, and their production and use in a large scale will inevitably lead to their dispersion into water streams (either by wastewater disposal or accidental leakage). Studies on the removal and recovery of ionic liquids from wastewater streams are therefore of crucial importance, yet particularly scarce. In this work, the use of aluminium salts is proposed to concentrate and remove ionic liquids from aqueous solutions. Two aluminium-based salts (Al 2 (SO 4) 3 and AlK(SO 4) 2 ?12H 2 O) were used to treat various aqueous solutions of ionic liquids containing imidazolium-, pyridinium-and phosphonium-based fluids. The gathered results show the enhanced ability of these salts to remove and recover ionic liquids from aqueous media. The minimum recovery efficiency achieved was 96%, whereas for a large array of systems recoveries of circa 100% of ionic liquid were attained. The residual concentrations of ionic liquids in water range from 0.01 to 6 wt%. The results reported disclose a novel promising technique for the recovery and treatment of aqueous effluents contaminated with ionic liquids by using salts commonly employed in water treatment processes, allowing thus its easy scale-up and adaptation to new processes involving ionic liquids.

Journal of Physical Chemistry B, Oct 24, 2007

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties t... more The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis-(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN) 3 ] < [PF 6 ] < [Tf 2 N] while the hydrophobicity of the cations increases from [C n mim] < [C n mpy] e [C n mpyr] < [C n mpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in... more Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in the past few years as alternatives to some hazardous volatile organic compounds. They are already used by industry, where it was possible to improve different processes by the incorporation of this kind of non-volatile and often liquid solvents. However, even if ionic liquids cannot contribute to air pollution, due to their negligible vapour pressures, they can be dispersed thorough aquatic streams thus contaminating the environment. Therefore, the main goals of this work are to study the mutual solubilities between water and different ionic liquids in order to infer on their environmental impact, and to propose effective methods to remove and, whenever possible, recover ionic liquids from aqueous media. The liquid-liquid phase behaviour of different ionic liquids and water was evaluated in the temperature range between (288.15 and 318.15) K. For higher melting temperature ionic liquids...

Ionic Liquids, 2019

In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-formi... more In the past years, the relevance of introducing ionic liquids (ILs) has been shown as phase-forming components of aqueous biphasic systems (ABS), which allow the tailoring of polarity differences between the coexisting phases. Although investigations on the IL chemical structure and polymermolecularweight have been carried out, the use of mixtures of polymers can also be seen as a way of tailoring their two-phase formation ability and separation performance, which was not attempted earlier. In this work, we investigate novel ABS composed of cholinium-based ILs and mixtures of polymers, namely polyethylene glycol (PEG) of 400 and 2,000 g·mol-1, at differentmole fractions, as a way of tailoring the formation of ABS and their separation performance. The respective liquid-liquid phase diagrams were determined, and their ability to separate a set of alkaloids (caffeine, theophylline and theobromine) appraised. An increase on the PEG 2000mole fraction favors the formation of ABS. However, this does not follow a monotonous trend, where mole fractions of PEG 400 up to 0.3 do not display significant impact on the two-phase separation capability. Among the studied alkaloids, nicotine preferentially partitions to the IL-rich phase, while the remaining alkaloids majorly partition to the polymer-rich phase. Different selectivity patterns were verified, depending on the cholinium-based IL used and water content at the IL-rich phase. Overall, by using mixtures of polymers it is possible to decrease the viscosity of the coexisting phases and their toxicity impact, without losing their formation and separation capacities, by the addition of PEGs of lower molecular weight.publishe

Frontiers in Chemistry, 2019

no losses on the ABS separation performance. Overall, the obtained results show that the investig... more no losses on the ABS separation performance. Overall, the obtained results show that the investigated ABS are promising platforms to simultaneously separate carbohydrates and antioxidants from real food waste samples, and could be used in further related applications foreseeing industrial food waste valorization.

Thermochimica Acta, 2018

Solid-liquid equilibria (SLE) data for two binary organic mixtures of N-(2-methoxyethyl)-p-nitroa... more Solid-liquid equilibria (SLE) data for two binary organic mixtures of N-(2-methoxyethyl)-p-nitroaniline + Nethyl-4-nitroaniline (S1) and N-(2-ethanol)-p-nitroaniline + N-ethyl-4-nitroaniline (S2) have been measured using differential scanning calorimeter to build the corresponding solid-liquid phase diagrams. The quality of the SLE data has been checked by consistency tests, presenting good quality factors for both systems. Simple eutectic behavior has been observed for these systems with the presence of a solid-solid transition for S2. The SLE data have been correlated by means of Wilson, NRTL, and UNIQUAC equations. The used models calculate the equilibrium temperatures very satisfactorily. The best modeling results were obtained using the Wilson equation with a root mean square deviation between experimental and calculated values for S1 and S2 of 1.15 and 1.99, respectively. The Wilson, NRTL, and UNIQUAC equations have also been used to compute excess thermodynamic functions viz. excess Gibbs energy, enthalpy, and entropy. The obtained results demonstrated a moderate positive deviation to ideality for S1, and a strong positive deviation for S2, unveiling the nature of the interactions between the compounds forming each mixture. In addition, microstructural studies have been carried out by FTIR, XRD and optical microscopy. Weak molecular interactions have been shown for the eutectic compositions. Jackson's roughness parameter was calculated and found to be greater than 2, suggesting the faceted morphology with irregular structures.

Chemical Communications, 2018

Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and ... more Sustainable hydrophobic eutectic solvents, composed of low-priced and biodegradable terpenes and fatty acids, were used for the extraction and separation of Cu(ii) from other transition metals in mildly acidic solutions.

Journal of Solution Chemistry, 2018

The order of the salting-in or salting-out inducing ability of ions on the aqueous solubility of ... more The order of the salting-in or salting-out inducing ability of ions on the aqueous solubility of macromolecules in aqueous solutions is known as the Hofmeister series. Taking into account that ionic liquids (ILs) are constituted by ions, they can exert similar effects on the solubility of other ILs in aqueous media. To expand the knowledge of the salting-in/out ability of ILs, experimental studies on the solubility of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) in water and in the presence of other IL/salts, were conducted at 298.15 K and atmospheric pressure. Both the impact of the anion and cation of the IL were evaluated with the following ILs/salts: 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hydrogensulfate, cholinium bis(trifluoromethylsulfonyl) imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and lithium bis(trifluoromethylsulfonyl)imide, over a wide composition range. As happens with common salts, both salting-in and salting-out effects exerted by ILs were observed, with a higher impact exerted by the IL anion on the salting-out phenomenon. These data allow better understanding of the ILs impact when designing liquid-liquid separation processes.

Physical chemistry chemical physics : PCCP, Jan 25, 2015

Due to scarce available experimental data, as well as due to the absence of predictive models, th... more Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg(-1)). At salt molalities higher than 0.2 mol kg(-1), all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.2 mol kg(-1). To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electro...

RSC Advances, 2012

The number of applications involving ionic liquids has dramatically increased in the past few yea... more The number of applications involving ionic liquids has dramatically increased in the past few years, and their production and use in a large scale will inevitably lead to their dispersion into water streams (either by wastewater disposal or accidental leakage). Studies on the removal and recovery of ionic liquids from wastewater streams are therefore of crucial importance, yet particularly scarce. In this work, the use of aluminium salts is proposed to concentrate and remove ionic liquids from aqueous solutions. Two aluminium-based salts (Al 2 (SO 4) 3 and AlK(SO 4) 2 ?12H 2 O) were used to treat various aqueous solutions of ionic liquids containing imidazolium-, pyridinium-and phosphonium-based fluids. The gathered results show the enhanced ability of these salts to remove and recover ionic liquids from aqueous media. The minimum recovery efficiency achieved was 96%, whereas for a large array of systems recoveries of circa 100% of ionic liquid were attained. The residual concentrations of ionic liquids in water range from 0.01 to 6 wt%. The results reported disclose a novel promising technique for the recovery and treatment of aqueous effluents contaminated with ionic liquids by using salts commonly employed in water treatment processes, allowing thus its easy scale-up and adaptation to new processes involving ionic liquids.

Environmental science. Processes & impacts, 2013

The applications and variety of ionic liquids (ILs) have increased during the last few years, and... more The applications and variety of ionic liquids (ILs) have increased during the last few years, and their use at a large scale will require their removal/recovery from wastewater streams. Adsorption on activated carbons (ACs) has been recently proposed for this aim and this work presents a systematic analysis of the influence of the IL chemical structures (cation side chain, head group, anion type and the presence of functional groups) on their adsorption onto commercial AC from water solution. Here, the adsorption of 21 new ILs, which include imidazolium-, pyridinium-, pyrrolidinium-, piperidinium-, phosphonium- and ammonium-based cations and different hydrophobic and hydrophilic anions, has been experimentally measured. This contribution allows an expansion of the range of IL compounds studied in previous works, and permits a better understanding of the influence of the IL structures through the adsorption on AC. In addition, the COSMO-RS method was used to analyze the measured adso...

The Journal of Physical Chemistry B, 2012

This work reports on the systematic investigation of the influence of the cation alkyl side-chain... more This work reports on the systematic investigation of the influence of the cation alkyl side-chain length of 1-alkyl-3-methylimidazolium chloride ionic liquids ([C n C 1 im]Cl, with n = 1−14), as well as the substitution of the most acidic hydrogen in the imidazolium core by a methyl group, in the formation of aqueous biphasic systems. Ternary phase diagrams, tie-lines, tieline slopes, tie-line lengths, and critical points for the several systems (ionic liquid + water + K 3 PO 4) were determined and reported at 298 K and atmospheric pressure. It is shown that the increase of the cation alkyl chain length enhances the formation of aqueous biphasic systems if alkyl chain lengths until the hexyl are considered. The results for longer alkyl side chains show, nevertheless, that the phenomenon is more complex than previously admitted and that the capacity of the ionic liquid to self-aggregate also governs its ability to phase separate. The effect of the alkyl side-chain length on the phase-forming ability of the studied systems was quantitatively evaluated based on their salting-out coefficients derived from a Setschenow-type behavior. The aptitude of each ionic liquid for liquid−liquid demixing as a function of the cation alkyl side-chain length clearly follows three different patterns. The results obtained for the trisubstituted cation indicate that the hydrogenbonding interactions between the ionic liquid cation and water are not a relevant issue in the formation of aqueous two-phase systems. In general, for the [C n C 1 im]Cl series, a multifaceted ratio between entropic contributions and the ability of each ionic liquid to self-aggregate in aqueous media control the phase behavior.

The Journal of Physical Chemistry B, 2013

The Journal of Physical Chemistry B, 2011

The possibility of developing a scale for solubility parameters, with the purpose of predicting t... more The possibility of developing a scale for solubility parameters, with the purpose of predicting the performance and aiding the selection of ILs, was evaluated. For the estimation of solubility parameters, infinite-dilution activity coefficient data were used. The results allowed the identification of a curious behavior for ILs that seem to present more than one solubility parameter, acting as polar molecules in some situations and as nonpolar molecules in others, depending on the medium. This behavior was confirmed by solubility measurements of [C 4 MIM][PF 6 ] in solvent mixtures. In this work, the solubility parameters were also estimated from other properties, namely, viscosities and enthalpies of vaporization, and the relation between the various sets of solubility parameters is discussed. The results obtained suggest that, given the complexity of IL molecules and their liquid phases, a one-dimensional scale for solubility parameters that is able to characterize these fluids is not feasible.

The Journal of Physical Chemistry B, 2007

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties t... more The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis-(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN) 3 ] < [PF 6 ] < [Tf 2 N] while the hydrophobicity of the cations increases from [C n mim] < [C n mpy] e [C n mpyr] < [C n mpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

The Journal of Chemical Thermodynamics, 2011

In this work, the solubility of water in several tetradecyltrihexylphosphonium-based ionic liquid... more In this work, the solubility of water in several tetradecyltrihexylphosphonium-based ionic liquids at 298.15 K, and densities and viscosities of both pure and water-saturated ionic liquids in a broad temperature range were measured. The selected ionic liquids comprise the common tetradecyltrihexylphosphonium cation combined with the following anions: bromide, chloride, bis(trifluoromethylsulfonyl)imide, decanoate, methanesulfonate, dicyanamide and bis(2,4,4-trimethylpentyl)phosphinate. The isobaric thermal expansion coefficients for pure and water-saturated ionic liquids were determined based on the density dependence with temperature. Taking into account that the excess molar volumes of the current hydrophobic water-saturated ionic liquids are negligible, the solubility of water was additionally estimated from the gathered density data and compared with the experimental solubilities obtained. Moreover, the experimental densities were compared with those predicted by the Gardas and Coutinho model while viscosity data were correlated using the Vogel-Tammann-Fulcher method.

Journal of Chemical & Engineering Data, 2011

Among new potential solvents for lignocellulosic materials, ionic liquids (ILs) are attracting co... more Among new potential solvents for lignocellulosic materials, ionic liquids (ILs) are attracting considerable attention. Hence, the knowledge of the thermophysical properties of such fluids is essential for the design of related industrial processes. Therefore, in this work, a set of thermophysical properties, namely, density, viscosity, and refractive index, as a function of temperature, and isobaric thermal expansivity and heat capacities at a constant temperature, were determined for eight ionic liquids with the 1-ethyl-3-methylimidazolium cation combined with the following anions: acetate, methylphosphonate, methanesulfonate, trifluoromethanesulfonate, dicyanamide, thiocyanate, tosylate, and dimethylphosphate. Imidazolium-based ILs were chosen since these are the most studied ionic fluids in biomass dissolution approaches, while a large array of anions was investigated because it was already demonstrated that it is the IL anion that mainly governs the dissolution.