Table 5. Equilibrium Coefficients (cm3 molecule–1) for the Formation of •OH···H2O, CH3CH2OH···H2O, and H2O···CH3CH2OH Complexes (Keq1, Keq2, and Keq3, Respectively) and the Concentration Ratio (r•OH···H2O, rEtOH···H2O, rH2O···EtOH in %, EtOH Stands for CH3CH2OH) of the Hydrated Complexes Relative to the Free Hydroxyl Radical or Ethanola,b.
| T (K) | [H2O] | Keq1 | Keq2 | Keq3 | r•OH···H2O | rEtOH···H2O | rH2O···EtOH |
|---|---|---|---|---|---|---|---|
| 216.7 | 1.0 × 1015 | 4.7 × 10–20 | 3.8 × 10–21 | 1.1 × 10–20 | 4.7 × 10–3 | 3.8 × 10–4 | 1.1 × 10–3 |
| 223.3 | 2.1 × 1015 | 3.5 × 10–20 | 3.0 × 10–21 | 8.3 × 10–21 | 7.6 × 10–3 | 6.5 × 10–4 | 1.8 × 10–3 |
| 236.3 | 8.1 × 1015 | 2.1 × 10–20 | 2.0 × 10–21 | 5.0 × 10–21 | 1.7 × 10–2 | 1.7 × 10–3 | 4.0 × 10–3 |
| 249.3 | 2.6 × 1016 | 1.4 × 10–20 | 1.4 × 10–21 | 3.1 × 10–21 | 3.6 × 10–2 | 3.7 × 10–3 | 8.2 × 10–3 |
| 262.2 | 7.4 × 1016 | 9.2 × 10–21 | 1.0 × 10–21 | 2.1 × 10–21 | 6.8 × 10–2 | 7.7 × 10–3 | 1.5 × 10–2 |
| 275.2 | 1.9 × 1017 | 6.4 × 10–21 | 7.8 × 10–22 | 1.4 × 10–21 | 1.2 × 10–1 | 1.5 × 10–2 | 2.7 × 10–2 |
| 288.2 | 4.3 × 1017 | 4.6 × 10–21 | 6.0 × 10–22 | 1.0 × 10–21 | 2.0 × 10–1 | 2.6 × 10–2 | 4.4 × 10–2 |
| 298.2 | 7.8 × 1017 | 3.7 × 10–21 | 5.0 × 10–22 | 8.0 × 10–22 | 2.9 × 10–1 | 3.9 × 10–2 | 6.2 × 10–2 |
| 325.0 | 3.0 × 1018 | 9.9 × 10–21 | 3.2 × 10–21 | 2.4 × 10–22 | 6.5 × 10–1 | 1.0 × 10–1 | 1.4 × 10–1 |
| 425.0 | 8.5 × 1019 | 5.4 × 10–22 | 1.1 × 10–22 | 1.1 × 10–22 | 4.6 | 9.6 × 10–1 | 9.3 × 10–1 |
The concentrations (molecule cm–3) of H2O are calculated at 100% RH.
rOH···H2O = [•OH···H2O]/[•OH] = Keq1[•OH][H2O]/[•OH] = Keq1[H2O], rCH3CH2OH···H2O = [CH3CH2OH···H2O]/[CH3CH2OH] = Keq2[CH3CH2OH][H2O]/[CH3CH2OH] = Keq2[H2O], rH2O···CH3CH2OH = [H2O···CH3CH2OH]/[CH3CH2OH] = Keq3[H2O][CH3CH2OH]/[CH3CH2OH] = Keq3[H2O].