FTIR Reflectance <i>vs.</i> EPR Studies of Structural Iron in Kaolinites

Abstract

Abstract The substitution of Fe 3+ in the kaolinite structure is studied by EPR spectrometry and by FTIR spectrometry on a large set of kaolins from different origins (sedimentary and primary ores, soil kaolins). The IR bands at 3598 and 875 cm −1 , observed in the literature only in the case of disordered kaolins or in Fe-rich environments (synthetic, lateritic), are revealed by high-resolution IR analysis, whatever the origin and the total Fe content of the samples. The EPR bands corresponding to Fe 3+ substituted in sites II of the octahedral sheet increase when the IR absorbance near 3600 cm −1 increases. Two IR absorption bands near 4465 cm −1 and 7025 cm −1 are observed for the first time, both in transmission and diffuse reflectance on all samples. These bands are assigned to the combination of the 3598 and 875 cm −1 bands and to the first harmonic of the band at 3598 cm −1 , respectively. The area of the band at 4465 cm −1 in diffuse reflectance is quantitatively correlated to the abundance of Fe 3+ located in centers II as measured by ESR. This directly confirms the assignment of the two IR bands at 3598 and 875 cm −1 to OH stretching and deformation vibration bands in octahedral FE 3+ environment in the kaolinite structure, respectively. Effects due to the size of particles and to the main kaolins impurities on the near infrared spectra, are also discussed.