Synthesis And Structures Of Pb3O2(CH3COO)2 0.5H2O and Pb2O(HCOO)2: Two Corrosion Products Revisited

Abstract

Reactions of carboxylic acids with lead play an important role in the atmospheric corrosion of lead and lead-tin alloys. This is of particular concern for the preservation of lead-based cultural objects, including historic lead-tin alloy organ pipes. Two initial corrosion products, Pb3O2(CH3COO)(2)center dot 0.5H(2)O (1) and Pb2O(HCOO)(2) (2), had been identified through powder diffraction fingerprints in the Powder Diffraction File, but their structures had never been determined. We have crystallized both compounds using hydrothermal solution conditions, and structures were determined using laboratory and synchrotron single-crystal X-ray diffraction data. Compound 1 crystallizes in P (1) over bar, and 2 in Cccm. These compounds may be viewed as inorganic-organic networks containing single and double chains of edge-sharing Pb4O tetrahedra and have structural similarities to inorganic basic lead compounds. Bond valence sum analysis has been applied to the hemidirected lead coordination environments in each compound. Atmospheric exposure experiments contribute to understanding of the potential for conversion of these short-term corrosion products to hydrocerussite, Pb-3(CO3)(2)(OH)(2), previously identified as a long-term corrosion product on lead-rich objects. Each compound was also characterized by elemental analysis, thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), and Raman spectroscopy.

Publisher

American Chemical Society

Publication Date

11-1-2010

Publication Title

Inorganic Chemistry

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://dx.doi.org/10.1021/ic101904j

Keywords

Basic lead carbonates, Acetic acid vapor, Metal-organic framework, Crystal structure, Corrosion and anti-corrosives, X-ray, Inorganic-compounds, Chemistry, Nitrates, Diffraction, Chemistry, inorganic and nuclear

Language

English

Format

text

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