Departmental Papers (CBE)

Document Type

Journal Article

Date of this Version

June 2007


The thermodynamic properties of surface ceria were investigated through equilibrium isotherms determined by flow-titration and coulometric-titration measurements on high-surface-area ceria and ceria supported on La-modified alumina (LA). While the surface area of pure ceria was found to be unstable under redox conditions, the extent of reduction at 873 K and a P(O2) of 1.6x10-26 atm increased with surface area. Because ceria/LA samples were stable, equilibrium isotherms were determined between 873 and 973 K on a 30-wt% ceria sample. Oxidation enthalpies on ceria/LA were found to vary with the extent of reduction, ranging from -500 kJ/mol O2 at low extents of reduction to near the bulk value of -760 kJ/mol O2 at higher extents. To determine whether +3 dopants could affect the oxidation enthalpies for ceria, isotherms were measured for Sm+3-doped ceria (SDC) and Y+3-doped ceria. These dopants were found to remove the phase transition observed in pure ceria below 973 K but appeared to have minimal effect on the oxidation enthalpies. Implications of these results for catalytic applications of ceria are discussed.


Postprint version. Published in Surface Science, Volume 601, Issue 12, June 2007, pages 2512-2519.
Publisher URL:


ceria, coulometric titration, thermodynamic properties, surface reduction, oxidation enthalpy



Date Posted: 21 September 2007

This document has been peer reviewed.