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J.A. SAWICKI, J.E. DUTRIZAC, J. FRIEDL, F.E. WAGNER, and T.T. CHEN
Copper refinery anode slimes are abundantly produced during the electrolytic refining of copper.
Although the slimes contain significant and economically recoverable amounts of gold and sil-
ver, the chemical state of the gold has not been fully identified. In the present work, the chem-
ical form of gold in a copper anode, in a raw slime, and in slimes treated by different leaching
procedures has been investigated by Mrssbauer spectroscopy with the 77.3 keV y-rays of 197Au.
The Mrssbauer spectrum of the anode is typical of a dilute Au:Cu alloy. The spectrum of the
raw slime consists of two components, namely, a single, rather broad line with an isomer shift
(IS) of about - 0 . 3 m m / s relative to a Pt metal source and a quadrupole doublet with an IS of
+ 1.2 m m / s and a quadrupole splitting of 5.0 mm/s. The single line component can be attrib-
uted to a gold-rich alloy, with an approximate composition of Au60Ag40 or AusoCu20 if it is a
binary alloy, or to a ternary Au-Ag-Cu alloy of appropriate composition. The parameters of the
quadrupole doublet match those of Ag3AuSe2 (fischesserite) or related Ag2_xAuxSe compounds.
In these compounds, the gold atoms are coordinated by two selenium atoms in a linear arrange-
ment, as is typical for Au(I). It was found that the ratio between the concentrations of the
metallic phase and the selenide strongly depends on the leaching conditions. The measurement
of the Lamb-Mrssbauer factor of fischesserite is also reported.
Table I. Compositions of the Anode and Anode Slimes Samples (Weight Percent)
Sample Cu Ag Se Te Ni Pb SiO2 Ba Au Pt Pd
1. Copper anode -99 0.21 0.11 -- 0.13 0.05 -- -- 0.006 -- --
2. Raw anode slimes 13.2 21.2 9.9 1.3 0.4 --20 -- -- 0.51 -- --
3, H2SO4 leached 0.05 21.4 5.9 0.7 0.01 15.2 5.7 0.9 0.99 0.03 0.35
4. HzSO4/NaC1 leached 0.12 24.2 13.0 0.7 0.08 15.6 4.0 0.6 0.82 0.03 0.30
5. H2SO4 leached at 150 ~ 0.05 36.9 13.8 1.3 0.03 11.1 -- -- 4.06 -- --
(--) Not analyzed.
o
spectra of the different slime specimens exhibit two well-
, 9 * ** . . *** ** separated absorption lines. The fight-hand p e a k is al-
9 ~
9 . 9 ..... *o w a y s at virtually the same position, + 3 . 7 2 -+ 0.02
o
o o
o
o ~
o
o
o ~
o
o
m m / s , and has nearly the natural linewidth o f 1.89
_ o
m m / s . The left-hand peak is more intense and broadened
~ o o o
in the spectra o f specimens 2 and 3. This suggests that
it is c o m p o s e d o f the left p e a k o f a quadrupole doublet
attributable to Ag3AuSe2 or a related c o m p o u n d and a
peak due to a g o l d - s i l v e r , g o l d - c o p p e r , or gold-silver-
99.96- #1 9 c o p p e r alloy. The M 6 s s b a u e r spectra o f these samples
o
was therefore d e c o n v o l u t e d a s s u m i n g a s y m m e t r i c a l
q u a d r u p o l e d o u b l e t and a single line, which turned out
100-
to be substantially b r o a d e n e d . F o r the raw anode slime,
this line has an IS o f - 0 . 3 + 0.1 m m / s , a line width
o f 2.9 _+ 0.5 m m / s , and a fractional area o f 27 -+ 3 pct.
The second c o m p o n e n t is a quadrupole doublet with an
99.7- 100
--., 100
.o
?. 92
"~ 99. #3
100'
lO0 . . . . ~ **. r~-"~'-~w-" =
O
o o oo ~
99.
"4~
99.4" #4 t~
o
100
o ~ 9
99
99.6-
o
Velocity (ram/s) :8 6
197
Fig. 3 - - Au M6ssbauer spectra of the copper anode (1), unleached Velocity ( r a m / s )
(raw) anode slime (2), H2SO4 leached slime (3), HzSO4-NaC1 leached
slime (4), and slime I-I2SO4 leached at 150 ~ (5). Fig. 4--197Au MOssbauer spectra of some reference materials: Au-
metal, fischesserite Ag3AuSe2, and 1 pct Au:Cu.
IS QS W RI CA~
Sample (ram/s) (ram/s) (mm/s) (pct) (pct) Identification
1. Copper anode +2.79(10) -- 2.88(44) 100 Au in Cu
2. Raw anode slime +1.22(4) 5.03(6) 2.03(10) 73(3) 88.5 Ag3AuSe2**
-0.30(10) -- 2.94(50) 27(3) 11.5 Au59Ag41or Au76Cu23
3. H2504 leached +1.18(9) 5.13(16) 1.91(14) 44(3) 69.2 Ag3AuSe2**
-0.91(7) -- 2.27(15) 56(3) 30.8 Au86Ag14 or Au92Cu8
4. H2SOa/NaC1 +1.23(2) 5.02(4) 1.99(65) 97(1) 98.6 Ag3AuSe2**
0.46(29) -- 1.99 3(1) 1.4 Au26Ag74 or AussCu42
5. H2SO4 leached at 150 ~ + 1.27(2) 5.14(3) 2.10(4) 100 100 Ag3AuS%**
6. Ag3AuSez synthetic +1.20(1) 4.96(3) 1.94(2) 100 100 References 11, 12, 20
7. Agl.sAu0.2Se +1.28(5) 4.99(5) 2.08(8) 100 100 Reference 19
8. 1 at. pct Au in Cu +2.79(2) -- 2.02(4) 100 100 this work
+2.75 Reference 8
9. 1 at. pct Au in Ag +0.68(1) -- 1.90(4) 100 100 this work
*IS is the isomer shift relative to the source of Au in Pt metal; QS, the electric quadrupole splitting; W, the FWHM line width; RL, the
relative intensity of the respective components in the Mrssbauer spectra; and CAothe relative concentration of gold in the different phases. Figures
in parentheses indicate the uncertainty in the last digit(s) reported.
**Related Ag-Cu-Se selenides are also possible.
IS of +1.22 --- 0.04 m m / s , a QS of 5.03 -+ 0.06 m m / s , Au in Ag3AuSe2 and in metallic gold was measured by
a line width of 2.0 -+ 0.1 m m / s , and a fractional area a reference absorber technique, which implies measuring
of 73-+ 3 p c t . the M6ssbauer spectrum of an absorber consisting of
Within the limits of error, the parameters of the quad- known amounts of Ag3AuSe2 and metallic gold. From
rupole doublet match those of Ag3AuSe2,1~1'1~'2~ the min- the relative line intensities in such a spectrum, the ratio
eral fischesserite t~6'17'~81)or of AgLsAu0.zSe 1~91(Table II). f(Ag3AuS%)/f(Au metal) = 0 . 3 5 ( 1 ) w a s obtained. The
In both compounds, the gold atoms are coordinated by relative amounts of gold in fischesserite and in the gold-
two selenium atoms in a linear arrangement, as is typical silver alloy, CAn, (Table II) were determined, taking the
for Au(I). I5'6'71 However, all (Au,Ag,Cu)2Se-type com- different f factors into account and assuming that the f
pounds containing linearly coordinated Se-Au-Se enti- factor of the alloy phase is the same as that of pure Au.
ties may give very similar Mrssbauer parameters and, Although the above interpretation is generally correct, it
hence, may be nearly indistinguishable by Mrssbauer should be noted that the selenide phase may have a com-
spectroscopy. position somewhat different from that of fischesserite and,
The single line component can be attributed to a gold- accordingly, that a somewhat different f factor may be
rich alloy, whose average composition can be estimated involved.
from the ISs of the Au-Ag and Au-Cu alloys LS~to be near In the raw anode slime, 11.5 pct of the gold is thus
Au6oAg40 or AusoCu20 if it is a binary Au-Ag or Au-Cu present in the form of Au-Ag, Au-Cu, or Au-Ag-Cu al-
alloy. The composition of gold-silver and gold-copper loys, whereas 88.5 pct is chemically bound in Ag3AuSe2
binary alloys can be estimated using an empirical linear or related selenides. The 30.8 pct relative amount of me-
relationship between the content of silver or copper, x, tallic gold in the H2SO4 leached anode slime (sample 3)
in Au~00-xAgx or Au~0o-xCux alloys and the IS of the is nearly three times larger than in the raw anode slime.
Mrssbauer line, I8'91which can be written as x[at. pct Ag]
In this material, the metallic gold contains less Ag or Cu
= 4 4 . ( I S [ r a m / s ] + 1.23) and x[at. pct Cu] =
than in the raw slime. Also, the M6ssbauer line is nar-
2 5 - ( I S [ r a m / s / + 1.23), respectively. The compositions
rower, which means that the distribution of compositions
given in Table II have been derived from these relations
is not as broad as in the raw slime. The H 2 5 0 4 + NaC1
and the observed ISs. Equally, however, the alloy could
leach (sample 4), on the other hand, eliminated the me-
be a ternary solid solution of Au-Ag-Cu. Experimental
tallic fraction almost totally, leaving practically all of the
data for ternary Au-Ag-Cu alloys do not exist, but it ap-
gold in selenide form, possibly fischesserite. The H2SO4
pears reasonable to assume a linear superposition of the
leach at 150 ~ (sample 5) converted all the gold to gold-
influence of Cu and Ag admixtures to gold, at least for
silver selenide, confirming the mineralogical observations.
low Cu and Ag concentrations. A ternary Au-Ag-Cu alloy
of appropriate composition should therefore also yield The fact that more gold occurs in metallic form after
the observed line position. The large linewidth indicates the H 2 S O 4 leach in sample 3 than in the starting material,
that there is a considerable spread in alloy composition, sample 2, suggests that some of the gold bound in the
as reported in the PIXE studies) 3J selenides is liberated when the gold-containing copper
The relative intensities of the individual components selenides are leached. The gold formed in this way con-
in the Mrssbauer spectrum do not represent directly the tains less silver and/or copper than the metallic gold in
relative amounts of gold present in these components, the raw slime. Possibly, silver and/or copper are also
since the recoil-free fractions or L a m b - M r s s b a u e r f fac- leached from the tiny alloy crystallites already present
tors, will be different for gold in different chemical states. in the raw slime, shifting the M6ssbauer spectra toward
In order to account for this, the ratio of the f factors of more negative velocities.