The surface phase behavior and micellar properties of two nonionic surfactants, namely, ethylene glycol
mono n-dodecyl ether (EGDE) and ethylene glycol mono n-tetradecyl ether (EGTE), have been investigated
at different temperatures. From the study of film balance and Brewster angle microscopy (BAM), it has been
observed that both of the amphiphiles show a first-order phase transition indicating conspicuous cusp points
in their respective adsorption isotherms. This is further confirmed by the observation of bright 2-D condensed
domains at the solution surfaces just after the appearance of the cusp points in the adsorption isotherms. Each
of the above amphiphiles has a definite temperature above which they cannot show any indicative feature of
phase transition, even with solutions of concentration above the critical micelle concentration (CMC) of the
amphiphiles. These temperatures are found to be 23 and 37 °C for EGDE and EGTE, respectively. The CMC
values of the amphiphiles increase with increasing temperature, showing a maximum value at a definite
temperature (T
max), and then decrease with further increases in temperature, which is just the opposite trend
of the usual behavior of ionic surfactants. Interestingly, T
max values of both of the amphiphiles correspond
well to their respective maximum temperature of the appearance of the phase transition in the adsorbed
monolayers. The standard thermodynamic parameters for micelle formation were calculated to determine the
nature of thermodynamic process involved in micellization. Both enthalpy, ΔH°m, and entropy, ΔS°m, terms
change their sign from negative to positive and increase monotonically with increasing temperature. The
enthalpy term ΔH°m is found to be zero at T
max, which suggests that micellization is entirely an entropy-driven process at this temperature. A linear relation in the ΔH
m° versus ΔS
m° plots is observed with slopes
304 and 296 for EGDE and EGTE, respectively, having dimensions of the Kelvin temperature. Both of the
thermodynamic quantities compensate each other, leading the free energy to be a negative value.
A novel supercritical water flow-reactor was constructed in order to simulate submarine hydrothermal systems. The temperature of fluid inside the reaction tube could be monitored with thermocouples, which was proved to be different from the temperature outside the reaction tube. Oligomers of glycine up to tetraglycine were formed when a 100 mM glycine solution was heated at 200–350 °C for 2 minutes. None of glycine peptides were produced at 400 °C. It was suggested, however, that the formation of glycine condensates at higher temperature, including supercritical conditions of water. The stability of some amino acids under hydrothermal conditions was examined. ω-Amino acids and glutamic acid, which can form intramolecular condensates, showed higher stability than other α-amino acids at higher temperature, including supercritical conditions.
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