Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD

Guy A. Crundwell, Brett A. Cowans, Jeffrey A. Hopkins, John B. Grutzner, Bart Kahr

Research output: Contribution to journalArticle

Abstract

Vegard's rule, originally based on powder X-ray diffraction data from BaxPb1-x(NO3)2, is reevaluated through the application of nuclear magnetic resonance (NMR) spectroscopy. Solid state 207Pb NMR and 15N NMR spectra of BaxPb1-x(NO3)2 (0.93>x>0.08) were recorded. The chemical shift dispersions for each magnetic nucleus are remarkable for their sensitivity to the nearest neighbor Pb2+ and Ba2+ distributions. The intensities of the peaks in the 207Pb spectra and their deviations from a simple binomial dependence reveal a non-statistical incorporation of Ba2+ and Pb2+ in the bulk crystals. Complementary analyses were performed by powder X-ray diffraction and with electron spectroscopy for chemical analysis that reveal bulk heterogeneities varying with crystal growth conditions. Vegard's original determination of a linear correlation between lattice constants and composition in BaxPb1-x (NO3)2 is shown to have been a favorable consequence of the low resolution X-ray film methods available in the 1920s, but his additivity relationship is restored locally in the linear correlation of chemical shift with composition of the first metal coordination sphere.

Original languageEnglish (US)
Pages (from-to)327-335
Number of pages9
JournalJournal of Solid State Chemistry
Volume145
Issue number1
DOIs
StatePublished - Jun 1999

Fingerprint

Nuclear magnetic resonance
Chemical shift
X ray powder diffraction
nuclear magnetic resonance
chemical equilibrium
Chemical analysis
X ray films
x rays
Electron spectroscopy
magnetic resonance spectroscopy
Crystallization
chemical analysis
Dispersions
diffraction
Crystal growth
Nuclear magnetic resonance spectroscopy
Lattice constants
electron spectroscopy
crystal growth
Metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Crundwell, G. A., Cowans, B. A., Hopkins, J. A., Grutzner, J. B., & Kahr, B. (1999). Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD. Journal of Solid State Chemistry, 145(1), 327-335. https://doi.org/10.1006/jssc.1999.8288

Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD. / Crundwell, Guy A.; Cowans, Brett A.; Hopkins, Jeffrey A.; Grutzner, John B.; Kahr, Bart.

In: Journal of Solid State Chemistry, Vol. 145, No. 1, 06.1999, p. 327-335.

Research output: Contribution to journalArticle

Crundwell, GA, Cowans, BA, Hopkins, JA, Grutzner, JB & Kahr, B 1999, 'Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD', Journal of Solid State Chemistry, vol. 145, no. 1, pp. 327-335. https://doi.org/10.1006/jssc.1999.8288
Crundwell, Guy A. ; Cowans, Brett A. ; Hopkins, Jeffrey A. ; Grutzner, John B. ; Kahr, Bart. / Vegard's Rule Revisited in BaxPb1-x(NO3)2 by NMR and XRD. In: Journal of Solid State Chemistry. 1999 ; Vol. 145, No. 1. pp. 327-335.
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