VAPOR-LIQUID COEXISTENCE AND CRITICAL BEHAVIOR OF IONIC LIQUIDS

ABSTRACT
Ionic Liquids are salts that are liquid near ambient temperatures. Experimental determination of critical points and vapor-liquid coexistence curve is not possible because of thermal stability issues as most Ionic Liquids decompose before reaching the critical point. The paper reports the first vapor-liquid phase diagram and critical point for ionic liquids obtained in silico with an atomistic force field.

IMPORTANCE OF VLE
VLE gives the nature of intermolecular interactions present in the liquid and vapor phases. Useful in developing equations of state and corresponding state theories Knowledge of critical points and VLE are key to achieving fundamental understanding of these complex fluids.

IONIC LIQUID UNDER STUDY

Molecular structure of ionic liquid under study

EXPERIMENTAL PROBLEMS
Conflicting experimental reports of the way in which properties such as vapor pressure and enthalpy of vaporization vary with factors such as size of cation, aggregation of ions etc Most of the experimental uncertainty is due to the pressure being too low and temperature being high which makes measurements extremely difficult to conduct as even trace amount of impurities can cause a large variations in measurements.

SIMULATION STUDIES
Simulation method used here is Gibbs Ensemble Monte Carlo(GEMC). Drawback: Reliance on particle exchanges between vapor and liquid phases to equilibrate the chemical potential but configurational bias Monte Carlo and other enhanced sampling techniques are used to circumvent this problem.

GEMC
Configurational Bias sampling, Parallel computing strategies and enhanced bias sampling specifically designed for ionic systems were used to enhance the efficiency.

COMPUTED VLCC AND CRITICAL POINTS

ANALYZING VLCC
Compared to non-ionic compounds like alkenes, the VLCCs have a high degree of Asymmetry with a very steep vapor branch similar to alkyl halides Effect of a single methylene group o Critical Temperature decreases with increasing alkyl chain, Tc decreases by 65K in going from C2 to C6. For alkanes and Alcohols the Tc increases with increasing alkyl chain. o Critical Density decreases with increasing alkyl chain.

CRITICAL TEMPERATURE, METHYLENE INCREMENT

It is unclear whether Tc will decrease with increasing chain length will hold true after C6. When the chain length becomes very long , it is possible that the columbic screening due to alkyl chain becomes saturated while the van der walls interaction due to increasing chain length continue to increase the cohesive energy, so it is possible that this trend of decreasing critical temperature with chain length might reverse after certain Cn

PRESSURE PLOT

ANALYZING PRESSURE PLOT

Increasing cation alkyl chain length increases the Vapor Pressure, thus lowering the normal Boiling Point. One Plausible explanation is increasing the nonpolar content of the cation weakens the Columbic interaction between ions, resulting in increased volatility Critical pressure can be computed using critical Temperature and subcritical saturation pressure. For ionic Liquids, Pc decreases with increasing alkyl chain length

ANALYZING PRESSURE PLOT

Critical compressibility factor (Zc) ranges from 0.038[C1] to 0.049[C6] Zc smaller than simple fluids suggesting highly nonideal behavior of vapor phase.

TEMPERATURE DEPENDENCE OF ENTHALPY OF VAPORIZATION

TEMPERATURE DEPENDENCE OF ENTHALPY OF VAPORIZATION

At high Temperatures, Hvap decreases with increasing size of cation, while at lower temperatures Hvap increases with increasing size of cation. The Trend reversal maybe due to o Significant aggregation in the vapor phase o Effect of alkyl chain on cohesive energy of condensed phase upon increasing temperature.

TEMPERATURE DEPENDENCE OF ENTHALPY OF VAPORIZATION

Hvap ranges from 68-72 KJ/mole which is twice the value of a H2 bonding liquid like ethanol but lower than energy reqd to dissociate. This suggests that vapor phase exists as ion pairs or large aggregates and not isolated ions.

ASSOCIATION IN VAPOR PHASE

ASSOCIATION OF IONS
Trountons constant for ionic liquids is ~65 J/mol K which is lower than nonpolar(~85 J/mol K) and polar (~105 J/mol K). Associating Liquids like acetic acid also have low Trounton constants Significant aggregation of ions in vapor phase lowers the vapor phase entropy relative to typical fluids where vapor phase consists mainly of isolated molecules.

CLUSTER ANALYSIS
Cluster analysis performed to address the issue of aggregation of ions. 2 ions considered part of cluster if their center of mass of separation <10.5 Angstrom which is determined from ion pair simulation at T=1100 K.

DISTRIBUTION OF CLUSTER SIZES AS A FUNCTION OF TEMPERATURE

TEMPERATURE DEPENDENCE OF IONS IN CLUSTER OF SIZE N(AGG)

AGGREGATION OF IONS
Less than 0.2% of ions are isolated. Single ion pairs account for more than 60% of total clusters. Number of single-ion pairs decreases with increasing temperature. Number of larger clusters increases with temperature. Even though individual ion pairs are dominant species in the vapor phase, substantial fraction of ions is present in larger aggregates. This might be the reason for discrepancies observed between different experimental techniques.

CONCLUSION
VLE of Ionic Liquids differs from conventional molecular liquids by o Shape of VLCC is highly Asymmetrical o Vapor pressure increases as size of cation increases. o Critical density and temperature decreases as size of cation increases. o Trountons constant is smaller than that of conventional fluids, consistent with finding that vapor state consists of significant fraction of aggregated ion pairs.

REFERENCES
Vapor Liquid Coexistence and critical behavior of Ionic liquids via Molecular Simulations, Neeraj Rai and Edward J. Maginn*

THANK YOU