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Oxidation States of Vanadium Lab Report

The experiment investigated the oxidation state of vanadium in silicate glasses using resonant inelastic X-ray scattering (RIXS). RIXS planes were collected for glasses synthesized under different oxygen fugacities to contain varying amounts of V2+, V3+, V4+, and V5+. The RIXS planes showed continuous variation with no distinct features corresponding to individual oxidation states. Attempts to model the spectra as distributions of species were complicated by uncertainty in the number of components for each valence state and broadening with decreasing valence state.

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301 views2 pages

Oxidation States of Vanadium Lab Report

The experiment investigated the oxidation state of vanadium in silicate glasses using resonant inelastic X-ray scattering (RIXS). RIXS planes were collected for glasses synthesized under different oxygen fugacities to contain varying amounts of V2+, V3+, V4+, and V5+. The RIXS planes showed continuous variation with no distinct features corresponding to individual oxidation states. Attempts to model the spectra as distributions of species were complicated by uncertainty in the number of components for each valence state and broadening with decreasing valence state.

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ahmedali
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Experiment title: Experiment

The oxidation state of vanadium in geological melts number:


EC-650

Beamline: Date of experiment: Date of report:


ID26 from: 07/04/2010 to: 13/04/2010 28/02/2011

Shifts: Local contact(s): Received at ESRF:


18 Janine Grattage

Names and affiliations of applicants (* indicates experimentalists):


Dr Andrew Berry, Imperial College London
Professor Hugh O'Neill, Australian National University
Dr Guilherme Malmann, Australian National University

Report:

Vanadium can occur as V2+, V3+, V4+ and V5+ and the transition from V2+ to V5+ covers the entire spectrum of
redox conditions observed in high-temperature geological and cosmochemical materials. As a result, the
oxidation state of V (either determined directly or inferred from its relative abundance in coexisting crystals
and melt) can be used as an indicator of the redox conditions under which a material formed. Redox
conditions are important as they are indicative of geological settings and processes, and can provide insight
into how the Earth has evolved with time

To investigate the redox chemistry of V we prepared a series of silicate glasses that are synthetic analogues
of geological melts (such as basalts) over a range of oxygen fugacities (fO2). The oxidation state of V in
these samples is expected to vary systematically from entirely V5+ to entirely V2+. The glasses contain 0.4
wt% V, are ~5 mm in size, and were presented as polished surfaces in epoxy resin.

In previous work, V K-edge XANES spectra were recorded at the APS for over 60 samples. The 1s→3d pre-
edge appears to be the spectral feature that is most sensitive to changes in oxidation state and has been used
to determine the average V valence. However, it has not been possible to distinguish between, for example,
V4+ and a mixture of V3+ and V5+. This severely limits our ability to understand the redox behaviour of V in
melts and to test models inferring valence state from partitioning behaviour (i.e. abundance in coexisting
phases). In the present experiment 1s2p RIXS and Kβ spectra were recorded for a subset of these samples.
The hope was that these sensitive probes of orbital structure would yield spectral features that were
diagnostic of each oxidation state (as appears to be the case in some V L-edge spectra). In the K-edge
spectra it is not possible to determine the abundance of four different species from the behaviour of a single
peak; additional features in the RIXS place could potentially solve this problem.
RIXS planes were recorded for V2+, V3+, V4+ and V5+ standards and approximately 30 glass samples. The
beamline functioned exceedingly well and was ideal for the proposed experiment. The samples studied
covered the full range of V redox states, two different compositions, and included some additional glasses for
which the V oxidation states had been (tentatively) determined by a combination of chemical titrations and
optical absorption spectroscopy. Representative RIXS planes are shown in the Figure.

Figure: V 1s2p RIXS contour plots for glasses that were equilibrated as melts under (from left to right) progressively more reduced
conditions. The sample represented by the plot on the left should predominantly contain V5+, that in the centre a mixture of V4+
and V3+, and that on the right mainly V2+.

The 1s2p RIXS planes for glasses in which the V oxidation state varies systematically from V5+ to V2+ show
differences, however, these are continuous. Distinct features do not appear or disappear as could occur for
the appearance and disappearance of different V oxidation states. Profiles through the planes give a single
lineshape that varies in intensity and energy. Attempts to model the profiles as a distribution of species is
complicated by the uncertainty of the number of components that may be expected for each V valence state
in poorly defined coordination environments. Further, due to a systematic broadening and decrease in
intensity with decreasing valence state the error associated with any attempt at quantifying V2+ (and possibly
V3+) will be significant. We should stress that methods for modelling RIXS are complex and still under
development. We are currently attempting a type of principal component analysis using software that is
normally used for modelling landforms such as mountain ranges.

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