In:
Canadian Journal of Chemistry, Canadian Science Publishing, Vol. 49, No. 6 ( 1971-03-15), p. 837-856
Abstract:
A study has been made of the infrared O—H bands for CH 3 OH, DOH, and H 2 O in solution and of their correlation with hydrogen bonding and solvent basicity. Infrared bands for the three fundamentals and the first bending overtone of H 2 O and for the O—H stretching fundamentals of DOH and CH 3 OH have been measured between 30 and −40 °C in a solvent range extending from weakly interacting fluorocarbons to strongly hydrogen-bonding organic amines. The O—H stretching bands for the weakly acidic solutes CH 3 OH, DOH, and H 2 O are mostly Lorentzian in shape and move to lower frequencies with higher extinctions in the more basic solvents. Many correlations are found between the stretching frequencies and band areas, and between the frequencies and solvent basicity. Monofunctional CH 3 OH is found to be a stronger acid and forms stronger hydrogen-bonds with a given base than do the doubly bonded DOH and HOH which show equal dibasic acid strengths.The wide, overlapped, fundamental stretching bands for H 2 O strongly hydrogen-bonded to the tertiary amines and for ice have been partially resolved and unequivocally assigned, showing that there is no cross-over of the ν 3 and ν 1 bands despite the strong hydrogen-bonding.At higher temperatures in solvents containing both hydrophobic and strongly basic groups water was found with the lower C s type symmetry, in which unbonded O—H groups gave sharp bands in the 3680–3650 cm −1 region in addition to the wide hydrogen-bonded bands at lower frequencies.
Type of Medium:
Online Resource
ISSN:
0008-4042
,
1480-3291
Language:
English
Publisher:
Canadian Science Publishing
Publication Date:
1971
detail.hit.zdb_id:
1482256-8
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