Solvent structural effects on proton dissociation

Journal Article · Wed Feb 14 04:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00160a010· OSTI ID:7069782

Krishnan, R; Fillingim, T G; Lee, J; Robinson, G W ^[1]

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1. Texas Tech Univ., Lubbock (USA)

Lifetime and quantum yield measurements are performed on the excited states of 1-naphthol-2-sulfonic acid potassium salt and its associated anion in aqueous solutions. In comparison to 1-naphthol, the intramolecular hydrogen bonding in the sulfonate derivative sterically reduces the extramolecular proton dissociation k{sub dis} and recombination k{sub rec} rates. Despite the large differences between excited state rates in 1-naphthol-2-sulfonic acid and those in 1- and 2-naphthol, proton dissociation in all these molecules is controlled by reorientational motions of the adjacent water and requires a common (H{sub 2}O){sub 4{plus minus}1} cluster as the proton acceptor. It is indeed found that k{sub dis}{sup {minus}1} and k{sub rec}{sup {minus}1} at different temperatures are scaled to the Debye orientation time {tau}{sub D}. These findings further support the Robinson-Lee-Moore hydration model for endothermically produced protons in aqueous environments.

• OSTI ID: 7069782
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:4; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALKALI METAL COMPLEXES
AQUEOUS SOLUTIONS
AROMATICS
CALCULATION METHODS
CHARGED-PARTICLE TRANSPORT
COMPLEXES
DATA ANALYSIS
DISPERSIONS
ENERGY LEVELS
EXCITED STATES
HYDROXY COMPOUNDS
LIFETIME
MEASURING INSTRUMENTS
MEASURING METHODS
MIXTURES
NAPHTHOLS
ORGANIC COMPOUNDS
PHENOLS
POTASSIUM COMPLEXES
PROTON TRANSPORT
RADIATION TRANSPORT
SOLUTIONS
SOLVENT PROPERTIES