Comparing two tetraalkylammonium ionic liquids. II. Phase transitions.
Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.
Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970 São Paulo, SP, Brazil.
Thamires A
TA
Lima
Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970 São Paulo, SP, Brazil.
Vitor H
VH
Paschoal
Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970 São Paulo, SP, Brazil.
Luiz F O
LF
Faria
Laboratório de Espectroscopia Molecular, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970 São Paulo, SP, Brazil.
Mauro C C
MC
Ribeiro
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.
Fabio F
FF
Ferreira
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil.
Fanny N
FN
Costa
Depto. de Física da Matéria Condensada, Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, 13083-859 Campinas, SP, Brazil.
Carlos
C
Giles