Spectroscopic characterization of chromite from the Moa-Baracoa Ophiolitic Massif, Cuba

Frost, Ray L. & Reddy, B. Jagannadha (2005) Spectroscopic characterization of chromite from the Moa-Baracoa Ophiolitic Massif, Cuba. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61(8), pp. 1721-1728.

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The Cuban chromites with a spinel structure, FeCr 2O4 have been studied using optical absorption and EPR spectroscopy. The spectral features in the electronic spectra are used to map the octahedral and tetrahedral co-ordinated cations. Bands due Cr3+ and Fe3+ ions could be distinguished from UV-VIS spectrum. Chromite spectrum shows two spin allowed bands at 17390 and 23810 cm-1 due to Cr3+ in octahedral field and they are assigned to 4A2g( F) ─> 4T2g(F) and 4A2g( F) ─> 4T1g(F) transitions. This is in conformity with the broad resonance of Cr3+ observed from EPR Spectrum at g = 1.903 and a weak signal at g = 3.861 confirms Fe3+ impurity in the mineral. Bands of Fe3+ ion in the optical spectrum at 13700, 18870 and 28570 cm-1 are attributed to 6A1g(S) ─> 4T1g(G), 6A1g(S) ─> 4T2g(G) and 6A1g(S) ─> 4T2g(P) transitions respectively. Near-IR reflectance spectroscopy has been used effectively to show intense absorption bands caused by electronic spin-allowed dd transitions of Fe2+ in tetrahedral symmetry, in the region 5000-4000 cm-1. The high frequency region (7500-6500 cm-1) is attributed to the overtones of hydroxyl stretching modes. Correlation between Raman spectral features and mineral chemistry are used to interpret the Raman data. The Raman spectrum of chromite shows three bands in the CrO stretching region at 730, 560 and 445 cm-1. The most intense peak at 730 cm-1 is identified as symmetric stretching vibrational mode, A1g(?1) and the other two minor peaks at 560 and 445 cm-1 are assigned to F2g (?4) and Eg (?2) modes respectively. Cation substitution in chromite results various changes both in Raman and IR spectra. In the low-wavenumber region of Raman spectrum a significant band at 250 cm-1with a component at 218 cm-1 is attributed F2g (?3) mode. The minor peaks at 195, 175, 160 cm-1 might be due to Eg and F2g symmetries. Broadening of the peak of A1g mode and shifting of the peak to higher wavenumber observed as a result of increasing the proportion of Al3+O6. The presence of water in the mineral shows bands in the IR spectrum at 3550, 3425, 3295, 1630 and 1455 cm-1. The vibrational spectrum of chromite gives raise to four frequencies at 985, 770, 710 and 650 cm-1. The first tow frequencies ?1 and ?2 are related to the lattice vibrations of octahedral groups. Due to the influence of tetrahedral bivalent cation, vibrational interactions occur between ?3 and ?4 and hence the low frequency bands, ?3 and ?4 correspond to complex vibrations involving both octahedral and tetrahedral cations simultaneously. Cr3+ in Cuban natural chromites has highest CFSE (20868cm-1) when compared to other oxide minerals.

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ID Code: 1273
Item Type: Journal Article
Refereed: Yes
Keywords: Chromite, Electronic spectra, Vibrational spectroscopy, Optical absorption spectrum, EPR, Near, infrared spectroscopy, Raman & IR study, Cr3+, Fe 3+, Fe2+ ions, Octahedral and tetrahedral sites of iron, Jahn, Teller effect, FeCr2O4 vibrational modes, Absorbed water in chromite mineral
DOI: 10.1016/j.saa.2004.07.002
ISSN: 1386-1425
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > INORGANIC CHEMISTRY (030200)
Divisions: Current > QUT Faculties and Divisions > Faculty of Education
Copyright Owner: Copyright 2005 Elsevier
Copyright Statement: Reproduced in accordance with the copyright policy of the publisher.
Deposited On: 06 Oct 2005 00:00
Last Modified: 29 Feb 2012 13:12

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