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In this study, we determined the enthalpies of vaporisation for a suitable set of molecular and ionic liquids using modern techniques for vapour pressure measurements, such as the quartz crystal microbalance, thermogravimetric analysis (TGA), and gas chromatographic methods. This enabled us to measure reasonable vapour pressures, avoiding the problem of the decomposition of the ionic liquids at high temperatures. The enthalpies of vaporisation could be further analysed by applying the well-known "group contribution" methods for molecular liquids and the "centerpiece" method for ionic liquids. This combined approach allowed for the dissection of the enthalpies of vaporisation into different types of molecular interaction, including hydrogen bonding and the dispersion interaction in the liquid phase, without knowing the existing species in both the liquid and gas phases.
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We show that the carboxyl-functionalized ionic liquid 1-(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC-CH2 -py][NTf2 ] exhibits three types of hydrogen bonding: the expected single hydrogen bonds between cation and anion, and, surprisingly, single and double hydrogen bonds between the cations, despite the repulsive Coulomb forces between the ions of like charge. Combining X-ray crystallography, differential scanning calorimetry, IR spectroscopy, thermodynamic methods and DFT calculations allows the analysis and characterization of all types of hydrogen bonding present in the solid, liquid and gaseous states of the ionic liquid (IL). We find doubly hydrogen bonded cationic dimers (c+ =c+ ) in the crystalline phase. With increasing temperature, this binding motif opens in the liquid and is replaced by (c+ -c+ -a- species, with a remaining single cationic hydrogen bond and an additional hydrogen bond between cation and anion. We provide clear evidence that the IL evaporates as hydrogen-bonded ion pairs (c+ -a- ) into the gas phase. The measured transition enthalpies allow the noncovalent interactions to be dissected and the hydrogen bond strength between ions of like charge to be determined.
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Volatile metal ß-diketonates are of interest from both practical and theoretical perspectives (manufacturing of film materials, catalysis, and the nature of metal-ligand bonding). Knowledge of their reliable thermochemical properties is essential for effective applications. However, there is an unacceptable scattering of the available data on the enthalpies of formation. In this work, we proposed "in vitro" and "in vivo" diagnostic tools to verify the available enthalpies of formation in both the crystalline and gaseous states for metal tris-ß-diketonates. The "in vitro" procedure involved high-level quantum-chemical calculations and was applied to define a consistent data set on the enthalpies of formation for iron(III) ß-diketonates. This data set has provided the basis for "in vivo" structure-property-based diagnostics to evaluate the robustness of the thermochemical data for ß-diketonate tris-complexes with metals other than iron.
Asunto(s)
Compuestos Férricos , Metales , Hierro , Ligandos , Compuestos Orgánicos , TermodinámicaRESUMEN
Ionic liquids (ILs) are recognized as an environmentally friendly alternative to replacing volatile molecular solvents. Knowledge of vaporization thermodynamics is crucial for practical applications. The vaporization thermodynamics of five ionic liquids containing a pyridinium cation and the [NTf2] anion were studied using a quartz crystal microbalance. Vapor pressure-temperature dependences were used to derive the enthalpies of vaporization of these ionic liquids. Vaporization enthalpies of the pyridinium-based ionic liquids available in the literature were collected and uniformly adjusted to the reference temperature T = 298.15 K. The consistent sets of evaluated vaporization enthalpies were used to develop the "centerpiece"-based group-additivity method for predicting enthalpies of vaporization of ionic compounds. The general transferability of the contributions to the enthalpy of vaporization from the molecular liquids to the ionic liquids was established. A small, but not negligible correction term was supposed to reconcile the estimated results with the experiment. The corrected "centerpiece" approach was recommended to predict the vaporization enthalpies of ILs.
Asunto(s)
Líquidos Iónicos , Líquidos Iónicos/química , Temperatura , Termodinámica , Presión de Vapor , VolatilizaciónRESUMEN
The paradigm of supramolecular chemistry relies on the delicate balance of noncovalent forces. Here we present a systematic approach for controlling the structural versatility of halide salts by the nature of hydrogen bonding interactions. We synthesized halide salts with hydroxy-functionalized pyridinium cations [HOCn Py]+ (n=2, 3, 4) and chloride, bromide and iodide anions, which are typically used as precursor material for synthesizing ionic liquids by anion metathesis reaction. The X-ray structures of these omnium halides show two types of hydrogen bonding: 'intra-ionic' H-bonds, wherein the anion interacts with the hydroxy group and the positively charged ring at the same cation, and 'inter-ionic' H-bonds, wherein the anion also interacts with the hydroxy group and the ring system but of different cations. We show that hydrogen bonding is controllable by the length of the hydroxyalkyl chain and the interaction strength of the anion. Some molten halide salts exhibit a third type of hydrogen bonding. IR spectra reveal elusive H-bonds between the OH groups of cations, showing interaction between ions of like charge. They are formed despite the repulsive interaction between the like-charged ions and compete with the favored cation-anion H-bonds. All types of H-bonding are analyzed by quantum chemical methods and the natural bond orbital approach, emphasizing the importance of charge transfer in these interactions. For simple omnium salts, we evidenced three distinct types of hydrogen bonds: Three in one!
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Ionic liquids are described by a delicate balance of Coulomb interaction, hydrogen bonding and dispersion forces. Dissecting the different types of interactions from thermodynamic properties is still a challenge. Here, we show that comparison of vaporization enthalpies of tetra-alkyl-ammonium ionic liquids with bis(trifluoromethylsulfonyl)imide [NTf2]- anions and the related molecular liquids, trialkylamines, allows for determining dispersion interactions in the gas phase ion-pairs. For this purpose, we measured vapor pressures and vaporization enthalpies of these ionic and molecular liquids by using a quartz-crystal microbalance. For supporting these data, we determined the vaporization enthalpies additionally from experimental activity coefficients at infinite dilution. Characteristic alkyl chain length dependences of the vaporization enthalpies have been established and were used for quantifying the dispersion forces in the gas phase species. The dissected dispersion contributions suggest that the alkyl chains do not show star-like topologies but embrace the anion maximizing the dispersion interactions. For the longest alkyl chains with eight carbon atoms, the dispersion interaction is as strong as two and a half hydrogen bonds. The proportion of dispersion in the gas phase species depending on the number of methylene groups in the ammonium cations is strongly supported by quantum chemical calculations.
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Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), vastly depends on the quality of the pure-component parameters. The pure-component parameters for low-volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture-independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure-IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor-pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10-5 â Pa even at elevated temperatures. In this work, such vapor-pressure data of a series of 1-ethyl-3-methyl-imidazolium-based [C2 mim]-ILs with various IL-anions (e. g. tetrafluoroborate [BF4 ]- , hexafluorophosphate [PF6 ]- , bis(trifluoromethylsulfonyl)imide [NTf2 ]- ) were experimentally determined and subsequently used for PC-SAFT parameter estimation. The so-determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid-density data only for the molecular PC-SAFT and the ion-based electrolyte PC-SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure-component vapor-pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion-specific parametrization in the long term.
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Combustion calorimetry is the predominant method for determination of enthalpies of formation for organic compounds. Both initial and final states of the calorimeter deviate significantly from the standard conditions. Correction of the obtained results to the standard state must be applied as accurately as possible to determine the combustion energy with an acceptable uncertainty, which is typically a few hundredths of a percent. The correction procedures in their current form were introduced in 1956 with simplifications to allow application in a pre-computer era. In this work, the procedures have been updated with respect to both the equations and reference values. The most reliable data sources are identified, and the updated algorithm is presented in the form of a Web-based tool available through the NIST TRC Web site.
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A series of nine different known ionic liquids or low melting salts was synthesised and purified. They are composed of the [NTf2 ]- (bis(trifluoromethane)sulfonimide), [OTf]- (trifluoro-methane-sulfonate), or [B(CN)4 ]- (tetracyanidoborate) anion and [Ph4 P]+ (tetraphenylphosphonium), [Ph3 BzP]+ (triphenylbenzyl phosphonium), [n Bu4 P]+ (tetra-n butylphosphonium), [n BuPh3 P]+ (tri-phenyl-n butylphosphonium), [n Bu4 N]+ (tetra-n butylammonium), or the [PPN]+ (bis(triphenylphosphine)iminium) cation. Precise vapour pressure data and enthalpies of vaporisation were measured using the Quartz Crystal Microbalance (QCM) method and evaluated. Structure-property relations are established using the obtained data as well as literature known data of ILs with alkyl-substituted imidazolium cations. It turns out that ILs with the tetracyanidoborate anion have even higher values of the enthalpy of vaporisation than those with the common [NTf2 ]- or [OTf]- anion and therefore are even less volatile.
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S-alkyltetrahydrothiophenium, [Cn THT]+ bis(trifluorosulfonyl)imide, [NTf2 ]- room temperature ionic liquids (ILs) and tetraphenylborate, [BPh4 ]- salts with alkyl chain lengths from C4 to C10 have been prepared. The ILs and salts were characterized and their purity verified by 1 H- and 13 C-nuclear magnetic resonance, elemental analysis, ion chromatography, Karl-Fischer titration, single crystal X-ray diffraction as well as thermogravimetric analysis. The experimentally determined density and viscosity decrease with increasing temperature. The experimental solubility of the [Cn THT][NTf2 ]-ILs in water (75 to 2.2â mg/L for C4 to C10 ) was modelled with very good agreement by Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT), based on the extremely low vapor pressures for the [Cn THT][NTf2 ]-ILs measured in this work (4.15 to 0.037 â 10-7 ×psat for C4 to C10 ). PC-SAFT is able to predict and correlate different thermodynamic properties by estimating the Helmholtz residual energy.
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We provide comprehensive understanding of "like-likes-like" charge attraction in hydroxy-functionalized ionic liquids (ILs) by means of infrared spectroscopy (IR), quantum chemistry and differential scanning calorimetry (DSC). We show that hydrogen bonding between cation and cation (c-c) is possible despite the repulsive forces between ions of like charge. Already at room temperature, the (c-c) hydrogen bonds can compete with the regular Coulomb-enhanced hydrogen bonds between cation and anion (c-a). For a large set of well-selected ILs, we show that "like-charge attraction" between the OH-functionalized cations is controllable by the polarizability of the cation, the interaction strength of the anion and the length of the hydroxyalkyl chain. In particular, we clarify whether tethering the OH group away from the positive charge center of the cationic ring with longer hydroxyalkyl chains compensates for unfavourable cation/anion combinations with respect to (c-c) cluster formation. For that purpose, we synthesized and characterized twelve ionic liquids including the differently polarizable cations, 1-(n-hydroxyalkyl)-1-methylpiperidinium [HOCnMPip]+ and 1-(n-hydroxyalkyl)-pyridinium [HOCnPy]+, as well as the weakly and strongly interacting anions, bis(trifluoromethanesulfonyl)imide [NTf2]- and methanesulfonate [OMs]-, respectively. On top, we varied the hydroxyalkyl chain length (HOCn) (n = 2-5). We systematically show how these three molecular ion parameters affect like-charge attraction. The use of polarizable cations, weakly interacting anions, and long alkyl chain tethers results in (c-c) clustering already at room temperature. Kinetic trapping is not a prerequisite for the existence of (c-c) cluster species in ILs. Moreover, we demonstrate that micro structuring affects macroscopic behavior of this type of ILs. We observed that substantial (c-c) interaction prevents ILs from crystallizing. Instead, these ILs supercool and finally form a glass.
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The state-of-the-art unit operation for separation and purification of amino acids is still crystallization, which requires solubility data and melting properties of pure compounds. Since measuring solubility is time-consuming, prediction tools are desired. Further, melting properties are not yet available due to decomposition of amino acids upon slow heating. In this work, melting properties of twenty amino acids (except Met) were measured by Fast Scanning Calorimetry (FSC) with heating rates up to 20 000 K s-1. PC-SAFT was used to predict interactions in amino acid + water systems. Additionally, solubility, pH, and PXRD was measured. By combining FSC and PC-SAFT, the solubility of 15 amino acids was successfully predicted in a wide temperature range in good agreement with the experimental data. Thus, this work provides melting properties of amino acids for the first time and highlights the usefulness of such data to predict material properties such as aqueous solubility of amino acids.
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Heat capacities of the antiviral drug rimantadine hydrochloride in the crystalline state were measured by adiabatic calorimetry and differential scanning calorimetry in the temperature range from (7 to 453) K. A broad low-enthalpy solid-state phase anomaly was detected between (170 and 250) K. Thermodynamic functions for crystalline rimantadine hydrochloride were derived. Decomposition of the studied compound was probed by the Knudsen effusion method and thermogravimetry with the support of quantum chemical calculations. The enthalpy of decomposition of rimantadine hydrochloride into the corresponding amine and hydrogen chloride was estimated from those data. The thermodynamic functions of the corresponding amine in the ideal gaseous state, including enthalpy of formation, were obtained using statistical thermodynamics with the necessary molecular parameters computed using quantum chemical methods. The enthalpy of formation of crystalline rimantadine hydrochloride was estimated.
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We present deuteron quadrupole coupling constants (DQCC) for hydroxyl-functionalized ionic liquids (ILs) in the crystalline or glassy states characterizing two types of hydrogen bonding: The regular Coulomb-enhanced hydrogen bonds between cation and anion (c-a), and the unusual hydrogen bonds between cation and cation (c-c), which are present despite repulsive Coulomb forces. We measure these sensitive probes of hydrogen bonding by means of solid-state NMR spectroscopy. The DQCCs of (c-a) ion pairs and (c-c) H-bonds are compared to those of salt bridges in supramolecular complexes and those present in molecular liquids. At low temperatures, the (c-c) species successfully compete with the (c-a) ion pairs and dominate the cluster populations. Equilibrium constants obtained from molecular-dynamics (MD) simulations show van't Hoff behavior with small transition enthalpies between the differently H-bonded species. We show that cationic-cluster formation prevents these ILs from crystallizing. With cooling, the (c-c) hydrogen bonds persist, resulting in supercooling and glass formation.
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The enthalpy of vaporization is mainly the amount of the energy needed for transferring quantities from the liquid into the gas phase. It simply describes the energy required to overcome the interaction energy between quantities if those evaporate as monomers as is the case for molecular liquids. The situation for ionic liquids (ILs) is more complex. We do not know the delicate composition of different types of interaction, neither for the liquid nor for the gas phase. Additionally, we have to consider that ILs evaporate as ion pairs which carry substantial interaction energy of all kind into the vapor phase. In this study, we measured the vaporization enthalpies of well-selected hydroxyl-functionalized and non-hydroxyfunctionalized ILs. In particular, we focussed on the case of hydroxyl-functionalized ILs providing possible hydrogen bonding between cation and anion in the liquid as well as in the gas phase. With infrared spectroscopy, we showed that all the hydroxyl groups are involved in hydrogen bonding in the liquid state of the ILs. However, molecular dynamics simulations showed that the evaporating ion pairs also include this hydrogen bond. A detailed analysis of the potential energies for all IL constituents showed that the hydrogen bond hinders favourable interaction between the polarizable ring of the cations and the anions leading to higher vaporization enthalpies for the hydroxyl-functionalized ILs.
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The quantification of hydrogen bonding and dispersion energies from vaporization enthalpies is a great challenge. Dissecting interaction energies is particularly difficult for ionic liquids (ILs), for which the composition of the different types of interactions is known neither for the liquid nor for the gas phase. In this study, we demonstrate the existence of ion pairs in the gas phase and dissect the interaction energies exclusively from measured vaporization enthalpies of different alkylated protic ILs (PILs) and aprotic ILs (AILs) and the molecular analogues of their cations. We demonstrate that the evaporated ion pairs are characterized by H-bond-enhanced Coulomb interaction. The overall interaction energy for the ILs in the bulk phase is composed of Coulomb interaction (76â kJ mol-1 ), hydrogen bonding (38â kJ mol-1 ), and minor dispersion interaction (10â kJ mol-1 ). Thus, hydrogen bonding prominently contributes to the overall interaction energy of PILs, which is reflected in the properties of this class of liquids.
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Melting properties (melting temperature, melting enthalpy and heat capacity difference between liquid and solid phase) of biomolecules are indispensable for natural and engineering sciences. The direct determination of these melting properties by using conventional calorimeters for biological compounds is often not possible due to decomposition during slow heating. In the current study this drawback is overcome by using fast scanning calorimetry (FSC) to directly measure the melting properties of five dipeptides (glycyl-glycine, glycyl-l-alanine, l-alanyl-glycine, l-alanyl-l-alanine and cyclo(l-alanyl-glycine)). The experimental melting properties were used as inputs into a thermodynamic solid-liquid equilibrium relation to predict solubility of the dipeptides in water. The required activity coefficients were predicted with PC-SAFT using solubility-independent model parameters. PC-SAFT predicted different solubility profiles (solubility vs. temperature) of isomers. The predictions were validated by new experimental solubility data, and the crystal structure of the dipeptides in saturated solution was verified by X-ray diffraction. The different water solubility profiles of isomers (glycyl-l-alanine and l-alanyl-glycine) were found to be caused by the big difference in the melting enthalpy of the two dipeptides. To conclude, combining the PC-SAFT and FSC methods allows for accurate prediction of dipeptide solubility in water in a wide temperature range without the need to fit any model parameters to experimental solubility data.
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In this review, results of the studies of thermodynamic properties of organic substances conducted at the Chemistry Department of the Belarusian State University (Minsk, Belarus) over a period of more than 50 years are summarized. Emphasis is made on precise measurements (both calorimetry and equilibria) and prediction methods, including group-contribution, quantum chemical, and statistical mechanical, for a broad range of thermodynamic properties of various classes of chemical substances. The principal purposes of these studies were to establish relationships between thermodynamic properties of organic substances and their molecular structure, develop methods of extrapolation and prediction of the properties of substances lacking experimental data, and provide thermodynamic background for innovative energy- and resource-saving technologies.
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Three selenoether-functionalized ionic liquids (ILs) of N-[(phenylseleno)methylene]pyridinium (1), N-(methyl)- (2) and N-(butyl)-N'-[(phenylseleno)methylene]imidazolium (3) with bis(trifluoromethanesulfonyl)imide anions ([NTf2]) were prepared from pyridine, N-methylimidazole and N-butylimidazole with in situ obtained phenylselenomethyl chloride, followed by ion exchange to give the desired compounds. The crystal structures of the bromide and tetraphenylborate salts of the above cations (1-Br, 2-BPh4 and 3-BPh4) confirm the formation of the desired cations and indicate a multitude of different supramolecular interactions besides the dominating Coulomb interactions between the cations and anions. The vaporization enthalpies of the synthesized [NTf2]-containing ILs were determined by means of a quartz-crystal microbalance method (QCM) and their densities were measured with an oscillating U-tube. These thermodynamic data have been used to develop a method for assessment of miscibility of conventional solvents in the selenium-containing ILs by using Hildebrandt solubility parameters, as well as for modeling with the electrolyte perturbed-chain statistical associating fluid theory (ePC-SAFT) method. Furthermore, structure-property relations between selenoether-functionalized and similarly shaped corresponding aryl-substituted imidazolium- and pyridinium-based ILs were analyzed and showed that the contribution of the selenium moiety to the enthalpy of vaporization of an IL is equal to the contribution of a methylene (CH2) group. An incremental approach to predict vaporization enthalpies of ILs by a group contribution method has been developed. The reaction of these ILs with zinc acetate dihydrate under microwave irradiation led to ZnSe nanoparticles of an average diameter between 4 and 10 nm, depending on the reaction conditions.
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Structure-property analyses of thermodynamic properties in chemical families of R-substituted benzamides, R-substituted benzoic acids, as well as R-substituted benzenes have been performed. The general linear interrelations for the vaporization enthalpies and the gas-phase enthalpies of formation between the chemical families under study have been established. These linear correlations provide a simple method for prediction of thermodynamic properties for benzenes with various combination of R-group substituents on the benzene ring. In addition, the robust structure-property correlations revealed in this study can serve for the establishment of the internal consistency of experimental results available for each chemical series.