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A Raman study on preferential interactions in the formamide/pyridine/pyridazine system and complementary thermodynamic information on the formamide/pyridazine mixture

Authors
Journal
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy
1386-1425
Publisher
Elsevier
Volume
102
Identifiers
DOI: 10.1016/j.saa.2012.10.014
Keywords
  • Raman Spectra
  • Temperature
  • Formamide
  • Pyridine
  • Pyridazine

Abstract

Abstract The formamide (FA)/pyridine (py)/pyridazine (prd) system was investigated by FT-Raman spectroscopy and the results in situ show that FA is preferentially bound to py, as experimentally pointed out by the proton affinity (PA) values of these azabenzenes. Temperature-dependent further investigations for the FA/prd mixture clearly show that the 2:1 FA:prd complex is more stable than the 1:1 FA:py adduct, even though its formation is influenced by the extremely negative entropy of the system, which becomes the spontaneously unfavorable global process. Linear relationships of the complex formation enthalpies (ΔH°) with band shifts (Δν) and dipole moments (μ) of these azabenzenes are observed and are in excellent agreement with our recent studies.

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