TY - JOUR
T1 - Enthalpy of water adsorption and surface enthalpy of goethite (α-FeOOH) and hematite (α-Fe2O3)
AU - Mazeina, Lena
AU - Navrotsky, Alexandra
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2007/2/20
Y1 - 2007/2/20
N2 - Goethite, α-FeOOH, and hematite, α-Fe2O3, have high affinity for water, especially when particle size is small. To determine the enthalpy of different types of adsorbed water, we performed water adsorption calorimetry on goethite and hematite with surface areas of 60-270 and 2-150 m2/g, respectively, using a new calorimetric technique combining a microcalorimeter and an automated gas dosing system. Several types of strongly bound water can be distinguished on hematite, depending on heating temperature and surface area. These have enthalpies of adsorption relative to liquid water (ΔHads) equal to -67.1 ± 4.9, -48.6 ± 1.8, and -25.5 ± 4.4 kJ/mol. The last value corresponds to water adsorption on very fine grained hematite and is very close to the water adsorption enthalpy for goethite, ΔHads = -19.4 ± 4.2 kJ/mol. Surface enthalpies for anhydrous surfaces of goethite (0.91 ± 0.09 J/m2) and hematite (1.9 ± 0.3 J/m2) determined experimentally are reported for the first time. The significant difference in surface enthalpies of goethite and hematite creates an energy crossover and makes fine-grained hematite metastable relative to goethite.
AB - Goethite, α-FeOOH, and hematite, α-Fe2O3, have high affinity for water, especially when particle size is small. To determine the enthalpy of different types of adsorbed water, we performed water adsorption calorimetry on goethite and hematite with surface areas of 60-270 and 2-150 m2/g, respectively, using a new calorimetric technique combining a microcalorimeter and an automated gas dosing system. Several types of strongly bound water can be distinguished on hematite, depending on heating temperature and surface area. These have enthalpies of adsorption relative to liquid water (ΔHads) equal to -67.1 ± 4.9, -48.6 ± 1.8, and -25.5 ± 4.4 kJ/mol. The last value corresponds to water adsorption on very fine grained hematite and is very close to the water adsorption enthalpy for goethite, ΔHads = -19.4 ± 4.2 kJ/mol. Surface enthalpies for anhydrous surfaces of goethite (0.91 ± 0.09 J/m2) and hematite (1.9 ± 0.3 J/m2) determined experimentally are reported for the first time. The significant difference in surface enthalpies of goethite and hematite creates an energy crossover and makes fine-grained hematite metastable relative to goethite.
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U2 - 10.1021/cm0623817
DO - 10.1021/cm0623817
M3 - Article
AN - SCOPUS:33947137741
VL - 19
SP - 825
EP - 833
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 4
ER -