T [K] 134.0 128.7 125.0 121.2 117.2 114.2 112.1 109.9 108.3 106.6 106.0 Ge Me Ge Me Me.

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Presentation transcript:

T [K] 134.0 128.7 125.0 121.2 117.2 114.2 112.1 109.9 108.3 106.6 106.0 Ge Me Ge Me Me

DG# eq (eq->#; see below) G ax Ge Me Ge Me parameter value unit R 8.315 J K-1 mol-1 <T> 114 K K(eq->ax) 0.7761989 - %a(e) (low field; eq) 56.3 %b(a) (high field: ax) 43.7 DG(eq->ax) 240.14962 J mol-1 0.2401496 kJ mol-1 0.0573958 kcal mol-1 conversion factor 0.239 kcal/kJ kB 1.381E-23 J K-1 h 6.626E-34 J s DG# eq (eq->#; see below) G ax Ge Me Ge Me

DH# = 3.92 kcal mol-1; DS# = +0.0089 kcal mol-1K-1 / +8.9 cal mol-1K-1 Me analysis: k(sum) kcal mol-1 Tc k(eq->ax) k(ax->eq) sum check DG#(eq->#) 105.9773245 242.972 313.028 556 4.82933172 106.5521349 4.85667094 108.2509773 310.707 400.293 711 4.88460717 109.9131943 396.796 511.204 908 4.90951832 112.0763123 534.014 687.986 1222 4.94432954 114.1832764 721.05 928.95 1650 4.97336667 117.2489699 1215.297 1565.703 2781 4.99143154 121.1835424 1966.5 2533.5 4500 5.05097828 124.9742516 3801.9 4898.1 8700 5.05289649 128.6521286 6205.4 7994.6 14200 5.08375727 134.0182064 15251.3 19648.7 34900 5.06718596 DG# (eq->#) 4.967643082 +/- 0.075228675 Average: DG# = DH# -TDS# => DH# = 3.92 kcal mol-1; DS# = +0.0089 kcal mol-1K-1 / +8.9 cal mol-1K-1 Tcorr

Analysis results: K (eq -> ax): + 0.78 DG(eq ->ax): + 0.057 kcal /mol (for T = 114 K) Average DG# (eq->#): 5.0 +/- 0.1 kcal/mol (4.97 +/- 0.08 kcal/mol) for temperature range 106 – 134 K

Exp. Calc. Dd/ppm T(K) keq,ax(s-1 ) 125 117 114 112 110 107 3800 1200 720 530 400 240 Dd/ppm