Identification of Aggregation Processes in Hexamethylenetetramine Aqueous Solutions: A Comprehensive Raman and Acoustic Spectroscopic Study Combined with Density Functional Theory Calculations

Stefanos Tsigoias; Michael G Papanikolaou; Themistoklis A Kabanos; Angelos G Kalampounias

doi:10.3390/molecules28237838

Identification of Aggregation Processes in Hexamethylenetetramine Aqueous Solutions: A Comprehensive Raman and Acoustic Spectroscopic Study Combined with Density Functional Theory Calculations

Molecules. 2023 Nov 29;28(23):7838. doi: 10.3390/molecules28237838.

Authors

Stefanos Tsigoias¹, Michael G Papanikolaou², Themistoklis A Kabanos², Angelos G Kalampounias^{1

3}

Affiliations

¹ Physical Chemistry Laboratory, Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece.
² Section of Inorganic and analytical Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece.
³ Institute of Materials Science and Computing, University Research Center of Ioannina (URCI), 45110 Ioannina, Greece.

Abstract

Raman scattering has been employed to study in detail the concentration dependence of the vibrational modes for hexamethylenetetramine (HMTA) aqueous solutions. The formation of protonated and/or aggregated species has been clarified by comparing the experimental with the theoretically predicted vibrational spectra by means of quantum mechanical calculations. The analysis has shown that the vibrational modes of the solutions arise from a contribution of the vibrational modes of the HMTA self-aggregates and hetero-aggregates of HMTA with water molecules that are formed in the low- and intermediate-concentration regions, respectively. The protonation of HMTA is ruled out due to the large differences between the experimental and the theoretically calculated spectra of the protonated molecules of HTMA in the fingerprint region. In the low-concentration solutions, the hetero-aggregation reaction of HMTA with water is the dominant mechanism, while at higher concentrations, a self-aggregation mechanism occurs. Ultrasonic absorption and velocity measurements were carried out for hexamethylenetetramine aqueous solutions. The acoustic spectra reveal the presence of only one single Debye-type relaxation process that is assigned to the aggregation mechanism of HMTA. The sound absorption data follow two different dependencies on the HMTA mole fraction. The crossover 0.018 mole fraction signifies two separate regions with distinct structural characteristics. The relaxation mechanism observed in dilute solutions was attributed to hetero-association of HMTA with water molecules, while at higher concentrations, the observed relaxation process was assigned to the self-association reaction of HMTA molecules. This structural transformation is also reflected in several physicochemical properties of the system, including the kinematic viscosity, the mass density, the sound speed and the adiabatic compressibility of the HMTA aqueous solutions. The combination of vibrational and acoustic spectroscopies with molecular orbital calculations allowed us to disentangle the underlying processes and to elucidate the observed relaxation mechanism in the HMTA aqueous solutions.

Keywords: Raman; aggregation mechanism; hexamethylenetetramine; molecular orbital calculations; ultrasonic relaxation spectroscopy.

Grants and funding

This research received no external funding.