Deuterium Isotope Effect on Glass Transformation Temperatures of Aqueous Inorganic Solutions

Journal Article · Thu Aug 01 04:00:00 EDT 1963 · Journal of Chemical Physics (U.S.)

DOI:https://doi.org/10.1063/1.1734307· OSTI ID:4659325

Shepley, L C; Bestul, A B

Determinations have been made on the effect of deuterium substitution on the glass transformation temperatures (T_g ) evaluated for aqueous solutions of about 15 wt. % HCl and SO₃ by differential thermal-analysis measurements. Complete substitution of D₂O as the solvent shifts T_g from 128.1° to 131.8°K for the HCl solution and from 143.7° to 146.3°K for the SO₃ solution. This shift is linear with extent of D₂O substitution. If it is assumed that the potential-energy barriers to configurational changes in the supercooled liquid are not altered by deuterium substitution, the above shifts can be interpreted as consistent with the proposition that the configurational changes which are immobilized when the solutions are cooled through the glass transformation involve simply the translation of single H₂O or D₂O groups. On the above basis, translational frequencies around 200 cm^—1 observed by Raman spectroscopy in water correspond to potential-energy barriers around 2000 cal/mole. This is in rough agreement with hydrogen-bond energies, which are around 3000 cal/mole. This identification of the barriers with hydrogen bonds provides a reasonable support for assuming the barriers insensitive to deuterium substitution.

• Research Organization: National Bureau of Standards, Washington, D.C.
• Sponsoring Organization: USDOE
• NSA Number: NSA-17-033774
• OSTI ID: 4659325
• Journal Information: Journal of Chemical Physics (U.S.), Journal Name: Journal of Chemical Physics (U.S.) Vol. Vol: 39; ISSN JCPSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

CHEMISTRY
CONFIGURATION
COOLING
DEUTERIUM
GLASS
HEAVY WATER
HYDROCHLORIC ACID
ISOTOPE EFFECTS
LIGHT
RAMAN EFFECT
SCATTERING
SOLUTIONS
SPECTRA
SPECTRAL SHIFT
SPECTROSCOPY
SULFUR OXIDES
TEMPERATURE
WATER