This work complements our recent discovery of new phases derived from zirconium perchlorate by addition of hydrogen peroxide. Here, we investigate analogous reactions with hafnium perchlorate, which is found to have modifications of the Clearfield-Vaughan tetramer (CVT). For hafnium perchlorate derivatives, we find distorted versions of CVT by X-ray diffraction and study the reaction solutions by SAXS, Raman spectroscopy, and ESI-MS. Furthermore, we investigate mixed Hf-Zr solution and solid phases and find the latter resemble the zirconium family at low Hf concentrations and the hafnium family at higher hafnium contents.
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http://dx.doi.org/10.1021/acs.inorgchem.0c03128 | DOI Listing |
Inorg Chem
February 2021
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331 United States.
This work complements our recent discovery of new phases derived from zirconium perchlorate by addition of hydrogen peroxide. Here, we investigate analogous reactions with hafnium perchlorate, which is found to have modifications of the Clearfield-Vaughan tetramer (CVT). For hafnium perchlorate derivatives, we find distorted versions of CVT by X-ray diffraction and study the reaction solutions by SAXS, Raman spectroscopy, and ESI-MS.
View Article and Find Full Text PDFInorg Chem
June 2014
Chemical Sciences and Engineering Division, ‡Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States.
The relationship of solution speciation and the structures of corresponding precipitates is examined for an aqueous Hf(4+) sulfate series. High-energy X-ray scattering (HEXS) and Raman spectroscopy data are used to probe atomic correlations in solutions. Hf(4+) in acidic perchlorate solution shows no evidence of a mononuclear metal species but instead has a peak in the pair-distribution function (PDF), generated from the HEXS data, at 3.
View Article and Find Full Text PDFDalton Trans
July 2004
Department of Chemistry, Swedish University of Agricultural Sciences, P.O. Box 7015, SE-750 07 Uppsala, Sweden.
The tetrameric hydrolysis products of zirconium(IV) and hafnium(IV), the zirconyl(IV) and hafnyl(IV) ions, [M(4)(OH)(8)(OH(2))(16)(8+)], often labelled MO(2+).5H(2)O, are in principle the only zirconium(IV) and hafnium(IV) species present in aqueous solution without stabilising ligands and pH larger than zero. These complexes are furthermore kinetically very stable and do not become protonated even after refluxing in concentrated acid for at least a week.
View Article and Find Full Text PDFTalanta
June 1982
Carpenter Technology Corp., Reading, PA 19603, U.S.A.
Data are presented for a refined spectrophotometric procedure for the simultaneous determination of zirconium and hafnium based on the combined effects of hydrogen peroxide, sodium sulphate, and excess of zirconium ion on the hafnium and zirconium complexes with Xylenol Orange in 0.2M perchloric acid. Isolation procedures for the hafnium/zirconium content of complex high-temperature alloys which result in an ionic substrate compatible with the spectrophotometric masking method were devised.
View Article and Find Full Text PDFTalanta
November 1968
Department of Chemistry, University of the Orange Free State, Bloemfontein, South Africa.
The extraction of hafnium(IV) tracer by N-benzoyl-n-phenylhydroxylamine (BPHA) from 1M perchloric acid has been investigated and stability constants have been calculated for the complexes Hf(BPHA)(i)((4-i)+) (i = 1cdots, three dots, centered4). It was found that variation of perchlorate concentration in the range 0.5-2.
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