Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 183−189.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
V.I. Men’shikov, I.Yu. Voronova, O.A. Proidakova, S.F. Malysheva, N.I. Ivanova, N.A. Belogorlova, N.K. Gusarova, B.A. Troﬁ mov, 2009,
published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 2, pp. 189−195.
AND INDUSTRIAL INORGANIC CHEMISTRY
Preconcentration of Gold, Silver, Palladium, Platinum,
and Ruthenium with Organophosphorus Extractants
V. I. Men’shikov, I. Yu. Voronova, O. A. Proidakova, S. F. Malysheva, N. I. Ivanova,
N. A. Belogorlova, N. K. Gusarova, and B. A. Troﬁ mov
Vinogradov Institute of Geochemistry, Russian Academy of Sciences, Siberian Branch, Irkutsk, Russia
Favorskii Irkutsk Institute of Chemistry, Irkutsk, Russia
Received August 1, 2008
Abstract—Extraction of noble metals in acid media with new tertiary phosphines and phosphine chalcogenides
was examined. Tristyrylphosphine, tristyrylphosphine sulfide tris(2-phenylethyl)phosphine oxide, tris-
(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)[2-(propylthio)ethyl]phosphine oxide, bis(2-phenylethyl)-
[2-(butylthio)ethyl]phosphine oxide, and tris[2-(butylthio)ethyl]phosphine oxide were used as extractants. The
suitability of the extractants for determination of Au, Ag, and Pd in rock and ore samples was elucidated.
The content of noble metals in nature objects
is typically low, and their determination requires
preconcentration and separation from matrix elements.
For these purposes, liquid-liquid extraction is promising
[1–4]. The use of organic solvents and extractants opens
better prospects for preconcentration of noble metals
when determined in various matrices, since, along with
preconcentration, this allows separating them from other
elements, thereby signiﬁ cantly weakening the inﬂ uence
of the sample composition and increasing the sensitivity
of determination. These factors are of deciding import-
ance in determining low concentrations of noble metals
in mineral raw materials and some process products
[5, 6]. In this context, despite a wide spectrum of
existing extractants [1, 2, 4], the development and
implementation of new high-performance extractants
for selective separation and preconcentration of noble
metals, including those occurring in real geological
matrices, remains topical.
At the present time, noble metals are preconcentrated
mostly with petroleum sulﬁ des (Au and Ag) or alkylanilines
(Au, Pt, Pd, Ru, Rh, Os, Ir). Of special interest are
organophosphorus compounds because of their high
selectivity and stability of the resulting complexes [1,
2, 4, 7–10]. For example, tributyl phosphate [2, 4, 7, 8]
and di(2-ethylhexyl)dithiophosphoric acid (DEHDTPA)
are used for preconcentration and subsequent recovery of
noble metals, and triphenylphosphine, for determination
of gold  and silver [12, 13]. Platinum group metals
are extensively preconcentrated with DEHDTPA 
and triphenylphosphine [12–14]; α-aminophosphonates
are used for analyzing platinum and palladium ,
and alkylenediphosphine dioxide is used for gold
. There are published data on spectrophotometric
determination of gold  and silver  with the
use of organophosphorus extractants, specifically,
trioctylphosphine oxide, hexamethyltriamidophosphate
, arylphosphinic acids, esters of phosphoric acid and
thiophosphoric acids, trialkyl phosphates and their thio
analogs . To increase the number of extractable metals,
organophosphorus extractants are used in combinations.
For example, DEHDTPA is mixed with alkylanilines to
include silver into the group of extractable metals .
A broad spectrum of existing extractants, on the one hand,
allows choosing the best one by practical analysts, and,
on the other hand, the latter are faced with the dilemma
of giving preference to one of them.
Here, we undertook a search for and development
of high-performance organophosphorus extractants for
noble metals, suitable for analytical applications. The
subjects of our examinations were readily available
tertiary phosphines and phosphine chalcogenides, for
which there exist convenient methods of synthesis from
elemental phosphorus [20–22].