Abstract
Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R4N]+ with commonly used anion hydroxide [OH]- were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R4N]+[OH]- are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH3) 4N]+[OH]- (TMAH), tetraethyl ammonium hydroxide [(C2H5)4N]+[OH]- (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N] +[OH]- (TPAH) and tetrabutyl ammonium hydroxide [(C 4H9)4N]+[OH]- (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (VE), the deviation in isentropic compressibility (Δκs) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.
| Original language | English |
|---|---|
| Pages (from-to) | 4561-4574 |
| Number of pages | 14 |
| Journal | Journal of Physical Chemistry B |
| Volume | 116 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - Apr 19 2012 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry
Cite this
Influence of alkyl chain length and temperature on thermophysical properties of ammonium-based ionic liquids with molecular solvent. / Kavitha, T.; Attri, Pankaj; Venkatesu, Pannuru; Devi, R. S.Rama; Hofman, T.
In: Journal of Physical Chemistry B, Vol. 116, No. 15, 19.04.2012, p. 4561-4574.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Influence of alkyl chain length and temperature on thermophysical properties of ammonium-based ionic liquids with molecular solvent
AU - Kavitha, T.
AU - Attri, Pankaj
AU - Venkatesu, Pannuru
AU - Devi, R. S.Rama
AU - Hofman, T.
PY - 2012/4/19
Y1 - 2012/4/19
N2 - Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R4N]+ with commonly used anion hydroxide [OH]- were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R4N]+[OH]- are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH3) 4N]+[OH]- (TMAH), tetraethyl ammonium hydroxide [(C2H5)4N]+[OH]- (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N] +[OH]- (TPAH) and tetrabutyl ammonium hydroxide [(C 4H9)4N]+[OH]- (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (VE), the deviation in isentropic compressibility (Δκs) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.
AB - Mixing of ionic liquids (ILs) with molecular solvent can expand the range of structural properties and the scope of molecular interactions between the molecules of the solvents. Exploiting of these phenomena essentially require a basic fundamental understanding of mixing behavior of ILs with molecular solvents. In this context, a series of protic ILs possessing tetra-alkyl ammonium cation [R4N]+ with commonly used anion hydroxide [OH]- were synthesized and characterized by temperature dependent thermophysical properties. The ILs [R4N]+[OH]- are varying only in the length of alkyl chain (R is methyl, ethyl, propyl, or butyl) of tetra-alkyl ammonium on the cationic part. The ILs used for the present study included tetramethyl ammonium hydroxide [(CH3) 4N]+[OH]- (TMAH), tetraethyl ammonium hydroxide [(C2H5)4N]+[OH]- (TEAH), tetrapropyl ammonium hydroxide [(C3H7)4N] +[OH]- (TPAH) and tetrabutyl ammonium hydroxide [(C 4H9)4N]+[OH]- (TBAH). The alkyl chain length effect has been analyzed by precise measurements such as densities (ρ), ultrasonic sound velocity (u), and viscosity (η) of these ILs with polar solvent, N-methyl-2-pyrrolidone (NMP), over the full composition range as a function of temperature. The excess molar volume (VE), the deviation in isentropic compressibility (Δκs) and deviation in viscosity (Δη) were predicted using these properties as a function of the concentration of ILs. Redlich-Kister polynomial was used to correlate the results. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions, and hydrogen bonding between ILs and NMP molecules. Later, the hydrogen bonding features between ILs and NMP were also analyzed using a molecular modeling program with the help of HyperChem 7.
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U2 - 10.1021/jp3015386
DO - 10.1021/jp3015386
M3 - Article
C2 - 22443087
AN - SCOPUS:84859940327
VL - 116
SP - 4561
EP - 4574
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 15
ER -