Pb-207 and Sn-119 Solid-State NMR and Relativistic Density Functional Theory Studies of the Historic Pigment Lead-Tin Yellow Type I and Its Reactivity in Oil Paintings


Catalano J., Murphy A., Yao Y., Alkan F. , Zurnbulyadis N., Centeno S. A. , ...More

JOURNAL OF PHYSICAL CHEMISTRY A, vol.118, no.36, pp.7952-7958, 2014 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 118 Issue: 36
  • Publication Date: 2014
  • Doi Number: 10.1021/jp505908j
  • Title of Journal : JOURNAL OF PHYSICAL CHEMISTRY A
  • Page Numbers: pp.7952-7958

Abstract

Lead soaps (lead carboxylates) have been detected in traditional oil paintings in layers containing the pigment leadtin yellow type I (LTY-I). LTY-I has been used by artists from at least the second quarter of the 15th century until the first half of the 18th century. Soap formation can lead to protrusions in paint layers and increased transparency, causing the paint support to become visible. We have characterized LTY-I by Sn-119 and Pb-207 solid-state NMR (ssNMR) spectroscopy. Using a combination of NMR techniques and DFT molecular cluster calculations, we identify the individual species in LTY-I and determine their Sn-119 and Pb-207 chemical-shift tensors. The presence of starting materials from the synthesis, minium, and tin(IV) oxide was also verified. Knowledge of the chemical-shift tensor components and the impurities in LTY-I is important for examining the chemistry of degradation processes and soap formation. We demonstrate that ssNMR can be used to detect reaction between Pb2SnO4 and added palmitic acid in a model paint sample containing LTY-I.