title: Carbonic acid: from polyamorphism to polymorphism.
abstract: Layers of glassy methanolic (aqueous) solutions of KHCO3 and HCl were deposited sequentially at 78 K on a CsI window, and their reaction on heating in vacuo in steps from 78 to 230 K was followed by Fourier transform infrared (FTIR) spectroscopy. After removal of solvent and excess HCl, IR spectra revealed formation of two distinct states of amorphous carbonic acid (H2CO3), depending on whether KHCO3 and HCl had been dissolved in methanol or in water, and of their phase transition to either crystalline alpha- or beta-H2CO3. The main spectral features in the IR spectra of alpha- and beta-H2CO3 are observable already in those of the two amorphous H2CO3 forms. This indicates that H-bond connectivity or conformational state in the two crystalline phases is on the whole already developed in the two amorphous forms. The amorphous nature of the precursors to the two crystalline polymorphs is confirmed using powder X-ray diffraction. These diffractograms also show that alpha- and beta-amorphous H2CO3 are two distinct structural states. The variety of structural motifs found within a few kJ/mol in a computational search for possible crystal structures provides a plausible rationalization for (a) the observation of more than one amorphous form and (b) the retention of the motif observed in the amorphous form in the corresponding crystalline form. The polyamorphism inferred for carbonic acid from our FTIR spectroscopic and powder X-ray diffraction studies is special since two different crystalline states are linked to two distinct amorphous states. We surmise that the two amorphous states of H2CO3 are connected by a first-order-like phase transition.
authors.affiliation: Institute of General, Inorganic, and Theoretical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria.
authors.forename: Katrin
authors.initials: K
authors.lastname: Winkel
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Hage
authors.forename: Thomas
authors.initials: T
authors.lastname: Loerting
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Price
authors.forename: Erwin
authors.initials: E
authors.lastname: Mayer
mesh_terms: D001639:Bicarbonates / Q000737:chemistry; D002255:Carbonic Acid / Q000737:chemistry*; D006851:Hydrochloric Acid / Q000737:chemistry; D006860:Hydrogen Bonding; D044367:Phase Transition; D017680:Potassium Compounds / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013696:Temperature
chemical_list: D001639:Bicarbonates; D017680:Potassium Compounds; D012997:Solvents; D002255:Carbonic Acid; C026329:potassium bicarbonate; D006851:Hydrochloric Acid