C-13 CP/MAS NMR studies were carried out on trans-1,2-cyclopentanediol, on 4,4-dimethyl-trans-1,2-cyclopentanediol, and on sulfolane at variable temperatures. The spectra showed evidence of three dynamic solid-state processes: hydrogen bond exchange, ring pseudorotation, and whole molecule rotations about local C-2 axes. Fitting of T-1 rho data to calculated values of the C-13-H-1 dipolar interactions allowed differentiation between ring pseudorotations and whole molecule C-2 reorientations. Isotopic H-1/H-2 substitution demonstrated the existence of hydrogen bond exchange processes in the diols. Activation parameters for these processes were derived from both coalescence measurements and the T-1 rho measurements.