Reactions of HCl and D2O with molten alkali carbonates.

TY - JOUR

T1 - Reactions of HCl and D2O with molten alkali carbonates.

AU - Krebs, Thomas

AU - Nathanson, Gilbert M

PY - 2011

Y1 - 2011

N2 - The acidic oxide SO? and protic acid HCl are among the gases released in the combustion of coal and the incineration of municipal waste. They are typically removed by wet or dry scrubbing involving calcium carbonate or calcium hydroxide. The molten alkali carbonate eutectic provides a liquid-state alternative that readily absorbs SO? and HCl and does not become covered with a passivating layer. Gas-liquid scattering experiments utilizing the eutectic mixture (44 mol % Li?CO?, 31 mol % Na?CO?, 25 mol % K?CO?) reveal that the reaction probability for HCl(g) + CO?²? ? CO?(g) + OH? + Cl? is 0.31 ± 0.02 at 683 K and rises to 0.39 at 783 K. Gaseous CO? is formed within 10?? s or less, implying that the reaction takes place in a liquid depth of less than 1000 Å. When the melt is exposed to D?O, the analogous reaction D?O(g) + CO?²? ? CO?(g) + 2OD? occurs too slowly to measure and no water uptake is observed. Together with previous studies of SO?(g) + CO?²? ? CO?(g) + SO?²?, these results demonstrate that molten carbonates efficiently remove both gaseous HCl and SO? while reacting at most weakly with water vapor. The experiments further highlight the remarkable ability of hot CO?²? ions to behave as a base in reactions with protic and Lewis acids.

AB - The acidic oxide SO? and protic acid HCl are among the gases released in the combustion of coal and the incineration of municipal waste. They are typically removed by wet or dry scrubbing involving calcium carbonate or calcium hydroxide. The molten alkali carbonate eutectic provides a liquid-state alternative that readily absorbs SO? and HCl and does not become covered with a passivating layer. Gas-liquid scattering experiments utilizing the eutectic mixture (44 mol % Li?CO?, 31 mol % Na?CO?, 25 mol % K?CO?) reveal that the reaction probability for HCl(g) + CO?²? ? CO?(g) + OH? + Cl? is 0.31 ± 0.02 at 683 K and rises to 0.39 at 783 K. Gaseous CO? is formed within 10?? s or less, implying that the reaction takes place in a liquid depth of less than 1000 Å. When the melt is exposed to D?O, the analogous reaction D?O(g) + CO?²? ? CO?(g) + 2OD? occurs too slowly to measure and no water uptake is observed. Together with previous studies of SO?(g) + CO?²? ? CO?(g) + SO?²?, these results demonstrate that molten carbonates efficiently remove both gaseous HCl and SO? while reacting at most weakly with water vapor. The experiments further highlight the remarkable ability of hot CO?²? ions to behave as a base in reactions with protic and Lewis acids.

M3 - SCORING: Journal article

VL - 115

SP - 482

EP - 489

JO - J PHYS CHEM A

JF - J PHYS CHEM A

SN - 1089-5639

IS - 4

M1 - 4

ER -