Clerici solution

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Clerici's solution
Names
IUPAC name
thallium(1+) 3-carboxylatooxy-3-oxopropanoate
Other names
Thallium(I) malonate/formate
Identifiers
3D model (JSmol)
  • InChI=1S/C4H4O6.2Tl/c5-2(6)1-3(7)10-4(8)9;;/h1H2,(H,5,6)(H,8,9);;/q;2*+1/p-2
    Key: QHRSTSUOSNUUHN-UHFFFAOYSA-L
  • C(C(=O)[O-])C(=O)OC(=O)[O-].[Tl+].[Tl+]
Properties
C4H2O6Tl2
Molar mass 554.82 g/mol
Appearance Colorless to yellow liquid
Density 4.25 g/mL (20 °C)
Fully soluble
Hazards
GHS labelling:
Danger
H301, H311, H315, H318, H331, H410
P261, P270, P280, P301+P310, P302+P352, P310, P332+P313, P403, P405
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Clerici solution is an aqueous solution of equal parts of thallium formate (Tl(HCO2)) and thallium malonate (Tl(C3H3O4)). It is free-flowing and odorless. Its color fades from yellowish to colorless when diluted. At 4.25 g/cm3 at 20 °C (68 °F), saturated Clerici solution is one of the densest aqueous solutions. The solution was invented in 1907 by the Italian chemist Enrico Clerici (1862–1938).[1] Its value in mineralogy and gemology was reported in 1930s. It allows the separation of minerals by density with a traditional flotation method. Its advantages include transparency and an easily controllable density in the range 1–5 g/cm3[2][3][4] as a result of changes in solubility (and therefore density of the saturated solution) with temperature.

Saturated Clerici solution is more dense than spinel, garnet, diamond, and corundum, as well as many other minerals.[3] A saturated Clerici solution at 20 °C (68 °F) can separate densities up to 4.2 g/cm3, while a saturated solution at 90 °C (194 °F) can separate densities up to 5.0 g/cm3.[4] The change in density is due to the increased solubility of the heavy thallium salts at the higher temperature. A range of solution densities between 1.0 and 5.0 g/cm3 can be achieved by diluting with water. The refractive index shows significant, linear and well reproducible variation with the density; it changes from 1.44 for 2 g/cm3 to 1.70 for 4.28 g/cm3. Thus the density can be easily measured by optical techniques.[2]

The color of the Clerici solution changes significantly upon minor dilution. In particular, at room temperature the concentrated solution with the density of 4.25 g/cm3 is amber-yellow. However, a minor dilution with water to the density of 4.0 g/cm3 makes it as colorless as glass or water (absorption threshold 350 nm).[5]

Procedure for determining mineral density using the Clerici solution are available.[2]

Two substantial drawbacks of the Clerici solution are its high toxicity and corrosiveness.[2][3] Today sodium polytungstate has been introduced as a replacement, but its solutions do not reach as high in density as the Clerici solution.

References

  1. ^ Clerici, Enrico (1907). "Preparazione di liquidi per la separazione dei minerali" [Preparation of liquids for the separation of minerals]. Atti della Reale Accademia Nazionale dei Lincei: Memorie della Classe di Scienze Fisiche, Matematiche e Naturale. 5th series (in Italian). 16: 187–195.
  2. ^ a b c d R. H. Jahns (1939). "Clerici solution for the specific gravity determination of small mineral grains" (PDF). American Mineralogist. 24: 116.
  3. ^ a b c Peter G. Read (1999). Gemmology. Butterworth-Heinemann. pp. 63–64. ISBN 0-7506-4411-7.
  4. ^ a b B. A. Wills, T. Napier-Munn (2006). Wills' mineral processing technology: an introduction to the practical aspects of ore treatment and mineral recovery. Butterworth-Heinemann. p. 247. ISBN 0-7506-4450-8.
  5. ^ A. Kusumegi (1982). "Total Absorption Counter and Viewing Shield by The Use of Heavy Liquids". Bull. Inst. Chem. Res., Kyoto Univ. 60 (2): 234. hdl:2433/76969.
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