ABSTRACT
Anin situultrasonic relaxation spectroscopic study is presented in an effort to determine the structural changes and the dynamics involved when norspermidine (NSpd) is dissolved in water. Our aim is to elucidate the mechanism responsible for the observed relaxation mechanism in acoustic spectra and estimate the corresponding thermodynamic parameters and the associated volume change. The experimental spectra of aqueous NSpd solutions revealed a single Debye-type relaxation mechanism attributed to proton-transfer reaction. The concentration and temperature dependence of the acoustic parameters supports this assignment. The activation enthalpy and entropy were estimated equal to ΔH*= 1.79 ± 0.20 kcal mol-1and ΔS*= -18.31 ± 0.73 cal mol-1 K-1, respectively. The concentration and temperature dependence of the sound velocity and absorption in the solutions exhibit characteristic features that are related to alterations in the network rigidity due to variations in hydrogen-bonding interactions at molecular level. The volume change associated to proton-transfer reaction for NSpd has been estimated and compared with the volume change observed for an analogous guanidine, the 1,1,3,3 tetramethyl guanidine. The obtained results are discussed in the framework of an existing theoretical structural model highlighting the strong molecular association in these liquid mixtures leading to complementary information on the structure and dynamics of guanidine amines. A comprehensive model of the whole relaxation processes is presented and discussed in detail.
ABSTRACT
In this work, we report on the structure and dynamics of the 1,1,3,3 tetramethyl guanidine (TMG) aqueous solutions in a wide concentration and temperature range by combining vibrational and ultrasonic spectroscopies. The experimental Raman spectra have been compared with the corresponding spectra obtained by ab initio quantum mechanical and density functional theory electronic structure calculations. This comparison indicated that only a single mechanism occurs when dissolving TMG in water and this is the proton transfer reaction, while the formation of byproducts during hydrolysis of TMG is dubious. This observation is further supported by the concentration dependence of the Raman spectra. The analysis of the ultrasonic relaxation data also revealed that the system exhibits a single relaxation process associated with this proton transfer reaction. It has been also observed that both relaxation amplitude and frequency exhibit a clear monotonous increase with increasing amine concentration in the solutions supporting the concept of the proton transfer reaction. The corresponding activation enthalpy was estimated directly from the temperature dependence of the acoustic data and found equal to ΔH* = 5.56 ± 0.34 kcal/mol, which seems to be reasonable for hydrogen-bond formation. Furthermore, the concentration dependence of the acoustic parameters and kinematic viscosity data has been used as a probe for the molecular association in these solutions. The results have been discussed in relation to the ability or inability of water molecules to form stable clathrates after the addition of amine molecules in the solutions.
ABSTRACT
Vibrational and ultrasonic spectroscopies have been employed to study the composition and polarization dependence of the vibrational and elastic properties of the pseudo-binary mixed fluoride-phosphate glass-forming system xSr(PO3)2-(1-x)(0.62MgF2-0.38AlF3) with x: 0, 0.04, 0.06, 0.1, 0.15, 0.2, 0.3, 0.4, 0.8, 0.9 and 1. Composition-induced alterations in the short-range order have been quantitatively followed by means of Raman and IR spectroscopies. The analysis has shown that the incorporation of the phosphate groups in the fluoride network results in a less interconnected network with suppressed rigidity. The specific amorphous materials have been used as a model system in terms of wide glass-forming ability to elucidate the effect of variation in connectivity between the fluoride and phosphate sub-networks on the Boson peak nature. Emphasis has been given in the low-frequency Raman phenomenology, which in conjunction with the elastic properties allowed us to establish a possible link between the Boson peak and the transverse phonons in these glasses.
