Ionic hydrogen bond and ion solvation. 8. RS sup minus hor ellipsis HOR bond strengths. Correlation with acidities

Journal Article · Thu Feb 23 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100341a079· OSTI ID:5113207

Sieck, L W; Mautner, M M.N. ^[1]

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1. National Bureau of Standards, Gaithersburg, MD (USA)

The stabilities of RS{sup {minus}}{center dot}HOR association ions have been investigated by pulsed high-pressure mass spectrometry. Equilibrium constants were determined as a function of temperature in order to define the {Delta}H{degree} and {Delta}S{degree} values for solvation. Dissociation energies, {Delta}H{sub D}{degree}, were found to decrease as the difference between the acidities ({Delta}H{degree}{sub acid}) of the two molecular components increased. For C{sub 6}H{sub 5}S{sup {minus}}{center dot}HOR complexes, a linear correlation of the form {Delta}H{sub D}{degree} = 22.1 - 0.20{Delta}{Delta}H{degree}{sub acid} was obtained, while for complexes incorporating HS{sup {minus}} or CH{sub 3}S{sup {minus}} as core ions, the expression was {Delta}H{sub D}{degree} = 19.9 - 0.15{Delta}{Delta}H{degree}{sub acid}, both the kcal/mol. Bonds involving CF{sub 3}CH{sub 2}OH deviated substantially from the correlations, suggesting multiple interactions. The successive hydration of HS{sup {minus}} and CH{sub 3}S{sup {minus}} was also investigated, and the {Delta}H{sub D}{degree} values found for the respective monohydrates, 14.2 and 15.0 kcal/mol, are in excellent agreement with recent ab initio calculations.

• OSTI ID: 5113207
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:4; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
BEAMS
BINDING ENERGY
CHEMICAL BONDS
DATA
DISSOCIATION ENERGY
ELECTRON BEAMS
ENERGY
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
LEPTON BEAMS
MASS SPECTROSCOPY
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PARTICLE BEAMS
PH VALUE
PULSE TECHNIQUES
SOLVATION
SPECTROSCOPY