Vladimir N. Emel'yanenko

Pyrrolidinium-Based Ionic Liquids. 1-Butyl-1-methyl Pyrrolidinium Dicyanoamide: Thermochemical Measurement, Mass Spectrometry, and ab Initio Calculations

The standard molar enthalpy of formation of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide has been determined at 298 K by means of combustion calorimetry, while the enthalpy of vaporization and the mass spectrum of the vapor (ion pairs) have been determined by temperature-programmed desorption and line of sight mass spectrometry. Ab initio calculations for 1-butyl-1-methylpyrrolidinium dicyanamide have been performed using the G3MP2 and CBS-QB3 theory, and the results from homodesmic reactions are in excellent agreement with the experiments.

Ionic Liquids. Combination of Combustion Calorimetry with High-Level Quantum Chemical Calculations for Deriving Vaporization Enthalpies

In this work, the molar enthalpies of formation of the ionic liquids [C2MIM][NO3] and [C4MIM][NO3] were measured by means of combustion calorimetry. The molar enthalpy of fusion of [C2MIM][NO3] was measured using differential scanning calorimetry. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. We have used a combination of traditional combustion calorimetry with modern high-level ab initio calculations in order to obtain the molar enthalpies of vaporization of a series of the ionic liquids under study.

Thermodynamic analysis of strain in the five-membered oxygen and nitrogen heterocyclic compounds.

Cyclopentane is conventionally strained. Replacement of a carbon atom by a heteroatom obviously impacts angular strain in the five-membered ring compounds. Changes of strains in the five-membered cycles are also caused by a double bond or atttached benzene rings. We studied the thermochemical properties of Indane, 2,3-dihydrobenzofuran, indoline, N-methyl-indoline, carbazole, and N-ethyl-carbazole to obtain a better quantitative understanding of the energetics associated with these compounds containing five-membered ring units. We used combustion calorimetry, transpiration method, and high-level first-principles calculations to derive gaseous enthalpies of formation of the five-membered heterocyclic compounds. Our new values together with the selected values for parent heterocyclic compounds, available from the literature, were used for calculation of the strain energies H(S) of five-membered C-, N-, and O-containing cycles. Quantitative analysis of the resulting stabilization or destabilization of a molecule due to interaction of benzene rings with the heteroatom has been performed.

Imidazolium-based ionic liquids. 1-methyl imidazolium nitrate: thermochemical measurements and ab initio calculations.

In this work data of the molar enthalpies of formation of the ionic liquid 1-methylimidazolium nitrate [H-MIM][NO3] was measured by means of combustion calorimetry. The molar enthalpy of fusion of [H-MIM][NO3] was measured using DSC. Experiments to vaporize the ionic liquid into vacuum or nitrogen stream in order to obtain vaporization enthalpy have been performed. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. The combination of traditional combustion calorimertry with modern high-level ab initio calculations allow the determination of the molar enthalpy of vaporization of the ionic liquid under study. The ab initio calculations indicate that [H-MIM][NO3] is most probably separated into the neutral species methyl-imidazole and HNO3 in the gaseous phase at conditions of the vaporization experiments.

Structure–Property Relationships in Ionic Liquids: A Study of the Anion Dependence in Vaporization Enthalpies of Imidazolium‐Based Ionic Liquids

Vaporization enthalpies for a series of ionic liquids (ILs) with the common cation 1-ethyl-3-methylimidazolium [C(2)mim] and different counter anions are determined using a quartz crystal microbalance method. Dependences of vaporization enthalpies on physicochemical parameters specific for cation and anion interactions are revealed. A linear relation between enthalpies of vaporization and the intermolecular vibrational frequencies is observed and suggested for calculation of unknown ILs. A simple group-contribution method is developed for prediction of vaporization enthalpies of alkyl imidazolium-based ILs.

Vaporization Enthalpies of Imidazolium Based Ionic Liquids: Dependence on Alkyl Chain Length

Vaporization enthalpies of a series of ten 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (ILs) [C(n) mim][NTf(2) ] with alkyl chain lengths of n=2, 3, 4, 6, 8, 10, 12, 14, 16, and 18 are determined by using a recently developed quartz crystal microbalance method. Due to the high sensitivity of the microbalance vapor studies can be extended to temperatures 60-100 K lower than those available with other methods. The results reveal a remarkably linear dependence of the vaporization enthalpies on the chain length at the reference temperature of 298 K.

Volatile times for the very first ionic liquid: understanding the vapor pressures and enthalpies of vaporization of ethylammonium nitrate.

A hundred years ago, Paul Walden studied ethyl ammonium nitrate (EAN), which became the first widely known ionic liquid. Although EAN has been investigated extensively, some important issues still have not been addressed; they are now tackled in this communication. By combining experimental thermogravimetric analysis with time of flight mass spectrometry (TGA-ToF-MS) and transpiration method with theoretical methods, we clarify the volatilisation of EAN from ambient to elevated temperatures. It was observed that up to 419 K, EAN evaporates as contact-ion pairs leading to very low vapour pressures of a few Pascal. Starting from 419 K, the decomposition to nitric acid and ethylamine becomes more thermodynamically favourable than proton transfer. This finding was supported by DFT calculations, which provide the free energies of all possible gas-phase species, and show that neutral molecules dominate over ion pairs above 500 K, an observation that is in nearly prefect agreement with the experimental boiling point of 513 K. This result is crucial for the ongoing practical applications of protic ionic liquids such as electrolytes for batteries and fuel cells because, in contrast to high-boiling conventional solvents, EAN exhibits no significant vapour pressure below 419 K and this property fulfils the requirements for the thermal behaviour of safe electrolytes. Overall, EAN shows the same barely measurable vapour pressures as typical aprotic ionic liquids at temperatures only 70 K lower.

Temperature-dependent prediction of the liquid entropy of ionic liquids.

Modeling of the temperature-dependent liquid entropy of ionic liquids (ILs) with great accuracy using COSMO-RS is demonstrated. The minimum structures of eight IL ion pairs are investigated and the entropy, calculated from ion pairs, is found to differ on average only 2% from the available experimental values (119 data points). For calculations with single ions, the average error amounts to 2.6% and stronger-coordinating ions tend to give higher deviations. Additionally, the first parameterization of the standard liquid entropy for ILs is presented in the context of traditional volume-based thermodynamics (S(l)(0)=1.585 kJ mol(-1) K(-1) nm(-3)·r(m)(3)+14.09 J mol(-1) K(-1)), which sheds light on the statistical treatment of ionic interactions. The findings provide the first direct access to accurate predictions of liquid entropies of ILs, which are tedious and time-consuming to measure.

Dispersion and Hydrogen Bonding Rule: Why the Vaporization Enthalpies of Aprotic Ionic Liquids Are Significantly Larger than those of Protic Ionic liquids.

It is well known that gas-phase experiments and computational methods point to the dominance of dispersion forces in the molecular association of hydrocarbons. Estimates or even quantification of these weak forces are complicated due to solvent effects in solution. The dissection of interaction energies and quantification of dispersion interactions is particularly challenging for polar systems such as ionic liquids (ILs) which are characterized by a subtle balance between Coulomb interactions, hydrogen bonding, and dispersion forces. Here, we have used vaporization enthalpies, far-infrared spectroscopy, and dispersion-corrected calculations to dissect the interaction energies between cations and anions in aprotic (AILs), and protic (PILs) ionic liquids. It was found that the higher total interaction energy in PILs results from the strong and directional hydrogen bonds between cation and anion, whereas the larger vaporization enthalpies of AILs clearly arise from increasing dispersion forces between ion pairs.

Benchmark Thermochemistry for Biologically Relevant Adenine and Cytosine. A Combined Experimental and Theoretical Study.

The thermochemical properties available in the literature for adenine and cytosine are in disarray. A new condensed phase standard (p° = 0.1 MPa) molar enthalpy of formation at T = 298.15 K was measured by using combustion calorimetry. New molar enthalpies of sublimation were derived from the temperature dependence of vapor pressure measured by transpiration and by the quarz-crystal microbalance technique. The heat capacities of crystalline adenine and cytosine were measured by temperature-modulated DSC. Thermodynamic data on adenine and cytosine available in the literature were collected, evaluated, and combined with our experimental results. Thus, the evaluated collection of data together with the new experimental results reported here has helped to resolve contradictions in the available enthalpies of formation. A set of reliable thermochemical data is recommended for adenine and cytosine for further thermochemical calculations. Quantum-chemical calculations of the gas phase molar enthalpies of formation of adenine and cytosine have been performed by using the G4 method and results were in excellent agreement with the recommended experimental data. The standard molar entropies of formation and the standard molar Gibbs functions of formation in crystal and gas state have been calculated. Experimental vapor-pressure data measured in this work were used to estimate pure-component PC-SAFT parameters. This allowed modeling solubility of adenine and cytosine in water over the temperature interval 278-310 K.