Abstract
The modification of reorientational correlation times for the various kinds of chemically non-equivalent protons of the ethanol molecule as a result of ionsolvation has been investigated with the help of NMR B′ coefficients. For this purpose, the proton spin-lattice relaxation times of specifically deuterated ethanols, containing only one type of chemically equivalent protons were measured in neat ethanols and their lithium chloride and iodide solutions at a number of concentrations. The measurements were also extended over a wide temperature range below room temperature. Some results of various other chlorides were also included for comparison. The results are discussed in the light of pertinent theories available at present. At 250 K the rotational correlation time of the molecule in pure ethanol is 64 ps and the correlation times of the CH2 and CH3 groups are 8 and 3 ps, respectively. In the solvation sphere of Li+ the correlation times for the molecule and the respective groups are about 4, 7, and 4 times as long. However, the internal reorientation times are found, in some cases, to be virtually zero which we take as an indication that the description of the internal motion by current theories is not satisfactory.
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Ansari, M.S., Hertz, H.G. Effect of ion-solvation on the internal dynamics of the ethanol molecule as studied using NMRB′coefficients. J Solution Chem 13, 877–906 (1984). https://doi.org/10.1007/BF00645334
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DOI: https://doi.org/10.1007/BF00645334