Hostname: page-component-78c5997874-g7gxr Total loading time: 0 Render date: 2024-11-10T07:35:29.114Z Has data issue: false hasContentIssue false

Chemical studies on the stabilities of boleite and pseudoboleite

Published online by Cambridge University Press:  05 July 2018

Fawzy A. Abdul-Samad
Affiliation:
Department of Chemistry, University College, Cardiff, CF1 1XL
D. Alun Humphries
Affiliation:
Department of Chemistry, University College, Cardiff, CF1 1XL
John H. Thomas
Affiliation:
Department of Chemistry, University College, Cardiff, CF1 1XL
Peter A. Williams
Affiliation:
Department of Chemistry, University College, Cardiff, CF1 1XL

Synopsis

FREE energies of formation of boleite, Pb26Cu24 Ag9Cl62(OH)47·H2O, and pseudoboleite, Pb5Cu4 Cl10(OH)8·2H2O, have been determined from solution studies at 298.2 K. ΔG°f values for the minerals are −19097.9±4.1 and −3705.4±5.5 kJ mol−1 respectively. These values, together with results of earlier studies (Humphreys et al., 1980) have been used to construct the stability field diagram shown in fig. 1. The boundaries for boleite and pseudoboleite are shown separately. If fields for the two minerals are plotted together, boleite has no thermodynamic stability at the silver ion activity chosen. At higher activities of Ag+(aq) the boleite field is negligible in extent.

The results can, however, be rationalized in terms of kinetics of mineral formation, rather than thermodynamic considerations alone. Since pseudoboleite is never found without boleite upon which it is observed to grow epitaxially (Winchell, 1963), it is clear that boleite must form metastably prior to any pseudoboleite deposition. Accordingly, boleite has a large range of solution compositions, from which it may precipitate. The hatched area of fig. 1 shows this at the Cu2+(aq) and Ag+(aq) activities chosen. The field is terminated at high aCl by the AgCl line, above which silver is precipitated as AgCl(s), chlorargyrite.

It is also evident from the chemical studies that the deposition of several assemblages in the leadcopper-chloride group of minerals is simply related to variations of chloride activity. With decreasing aCl the associations cumengeite + boleite + pseudoboleite, diaboleite + boleite + pseudoboleite, and diaboleite + chloroxiphite are expected in turn. This relationship is apparently borne out by field observations of occurrences of the minerals.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1981

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Alwan, (A. K.) and Williams, (P.A.) 1979. Transition Metal Olas. 4, 128-32CrossRefGoogle Scholar
Anthony, (J. W.), Williams, (S. A.), and Bideaux, (R. A.) 1977. Mineralogy of Arlzona, University of Arizona.Google Scholar
Bideaux, (R. A.) 1980, Mineral. Rec. 11, 155-81.Google Scholar
Humpherys, (D. A.), Thomas, (J. H.), Willams, (P. A.) and Symes, (R. F.) 1980. Mineral. Mag. 43, 901-4.CrossRefGoogle Scholar
Robie, (R. A.) , Hemingway, (B. S.) and Fisher, (J. R.) 1978. U.S.G.S. Bull. 1452.Google Scholar
Roose, (B. C.) 1973. J. Solid State Chem. 6, 8892.Google Scholar
Spencer, (L. J.) and Mountain, (E.D.) 1923. Mineral. Mag., 20, 67-92.Google Scholar
Symes, (R. F.) and Embrey, (P.G.) 1977. Mineral. Rec. 8. 298303.Google Scholar
Wilson, (I. F.) and Rocha, (V.S.) 1955. Prof. Paper U.S.G.S. 273.Google Scholar
Winchell, (R. E.) 1963. Thesis, Ohio State UniversityGoogle Scholar
Winchell, (R. E.) and Rouse, (B.C.) 1974. Mineral. Rec, 5, 280-7.Google Scholar