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Characterization of Cation– Interactions in Aqueous Solution Using Deuterium Nuclear Magnetic Resonance Spectroscopy

^a Department of Civil Engineering, Texas A&M University, College Station, TX 77840
^b Department of Geology and Geophysics, Texas A&M University, College Station, TX 77843
^c Department of Agricultural and Biological Engineering, Clemson University, Clemson, SC 29634-0357
^d Department of Environmental Toxicology and the Clemson Institute of Environmental Toxicology, Clemson University, Pendleton, SC 29670
^e Connecticut Agricultural Experiment Station, 123 Huntington Street, New Haven, CT 06504

View larger version (21K): [in a new window]   Fig. 1. The relaxation of organic solutes in different salt solutions. (a) Spin–lattice relaxation times (T1) for d6–benzene in aqueous solution as a function of salt concentration. Uncertainties in the values were generally less than 2% for a 70% confidence level, and would be approximately the same size as the symbols. (b) Normalized molecular correlation times (c) for d6–benzene in aqueous solution as a function of salt concentration. Uncertainties in the values were generally less than 3% based on the propagated errors of both the measured T1 values and the reported quadrupolar coupling constants. (c) Normalized c values for d2–dichloromethane in aqueous solution as a function of salt concentration.

View larger version (14K): [in a new window]   Fig. 2. Normalized molecular correlation time (c) values for d6–benzene, d2–dichloromethane, and d4–methanol (–CD3 group) in aqueous solution as a function of CsCl concentration.

View larger version (16K): [in a new window]   Fig. 3. Relaxation of d6–benzene in aqueous solution as a function of Ag(I) concentration. (a) Spin–lattice relaxation times (T1). (b) Normalized molecular correlation times (c).

View larger version (12K): [in a new window]   Fig. 4. Spin–lattice relaxation times (T1) of d6–benzene in 0.1 M NaCl aqueous solution as a function of pH.

View larger version (26K): [in a new window]   Fig. 5. Spin–lattice relaxation times (T1) for perdeuterated solutes in 0.1 M methanolic salt solutions: (a) d6–benzene, (b) d8–naphthalene (white bars for peaks and black bars for ß peaks), (c) d12–cyclohexane, and (d) d2–dichloromethane.

View larger version (18K): [in a new window]   Fig. 6. Relative free energies (G) (kcal mol–1) (from Kumpf and Dougherty, 1993) as a function of difference in normalized molecular correlation times (c) between 3 M and water for different cations.