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MINERALOGIST,
1966
h.r:rnopucrroN
This paper has beenpreparedby Cabri basedon an unpublishedmanuscript by Kracek and Ksanda. Kracek's and Ksanda's experimentalwork
(mostly differential thermal analysis) was performed at the Geophysical
Laboratory of the Carnegie Institution, Washington. Cabri's experimental work (high-temperature r-ray diffraction and optical and f-ray examination of quenchedcharges)was performed at the Department of GeoIogicalSciences,McGill University, Montreal, Canada.Wherever practicable,Kracek's and Ksanda's original text will be indicated by quotation
marks.
This systemis of particular interest to mineralogybecausethe stability
fields of reported minerals may be useful in the interpretation of certain
ore deposits.The compositionof hessite,AgzTe,is undisputed.A mineral
of approximatecompositionAg5-*Te3has been widely known as empressite since1951(Thompson el ol.). However, Honea (1964)confirmedthat
Bradley's (i914) original compositionfor empressitewas AgTe and proI Crown copyright reserved.
1t
Ag-TeSYSTEM
15
posed naming the Ags-,Te3 mineral stuetzite. Stuetzite was the name
given by Shrauf (1878)for a mineral of compositionAg+Te,but this composition was discredited by Thompson et al. (1951). To avoid further
confusion in the use of empressite.chemical compositions will be used for
AgTe and Agr-*Tea.
Pnnvrous Wonr
Previous experimental work in the Ag-Te system indicating only two
binary phaseshas been reviewed by Markham (1960) except for the
following. Kiukkola and Wagner (1957)indicated the presenceof a phase
intermediate between Agr-*Tea and hessite-the "y-phas-and this has
been confirmed (Cabri, 1965a).They showed, by means of solid-state
titrations at 250" and 300o C., that there is evidencefor the existenceof a
third phase.The phaseswere indicated by curves of a plot of the EMF of
a cell Ag/AgI/(Ag, Te) as Ag/Te. The curves were separatedby horizontal lines representing two-phase fields. They designated these phases,
a, y and e corresponding to decreasingAg content. Regarding compositions, they reported (p.386), "At 300" C. the Ag/Te ratio rangesfrom
1.99 to 2.00for the a phase,from 1.88to 1.91for the "y phase,and from
1.63 to 1.66 for the e phase." This would correspondto AgzTe for a,
AgrsTe fory, and Ags-*Teafor e, with x less than 0.11.
Honea (1964) reported that a chemical analysis made on material from
the Empress Josephine mine, Colorado, gave the formula AgTe, thus
substantiating Bradley's (1914) early analysis. He further made c-ray
single crystal and DTA examinations of this material and proposed retaining Bradley's terminology of empressitefor the AgTe phase. He was
unable to synthesize AgTe and found that it decomposed to Agr-*Tea
* T e a b o v e2 1 0 " C .
At room temperature,hessiteis monoclinic (Frueh, 1959),Ags-*Teris
hexagonal (Thompson et al., l95l), and AgTe is orthorhombic (Honea,
1964).
M,q,renrars AND METHoDSor. INVESTTcATToN
Kracek and Ksanda made mixtures of the desired compositions from
silver and tellurium. The silver (999.%fine, as rolled sheet from the U. S.
Mint) was cut into 5-mm squares and heated in air to destrol. surface
sulfide. The tellurium (electrolytic quality) was purified by vacuum
distillation in pyrex glass. The distilled metal had a melting point of
449.8+0.2" C. (Kracek, 1941), which agrees well with Machol and
Westrum (1958). The mixtures were fused in evacuatedp)'rex or clear
silica glasstubes, cooled, then powdered, repeatedly mixed, and annealed
at 300oC. For thermal analysisthe preparedmixtures were sealedunder
1a
Ag-Te SYSTEM
Liquids
lL
(J
a
o
o
ASrT"i*AS
20!5"
o
o
Ag.-rT..n* 7r,
?n+AgrTe,
.o
See Figure
Ie+Agu_*Tea,
Ag.Te,+Ag
60\
Ag,,Te.
RESULTS
Phase reiations in the Ag-Te binarv system are shown in Fig. 1 and 2 as
temperature-composition diagrams. All temperatures are in degrees
Centigrade; compositions are expressed in atomic andf or weight per cent
Ag.
18
r .ry
L-'h
'
'
I
a2a+qo
A^
T^
..t
^v5-xtr5h.
,h
o o
oc
oo
oo
o
o
@
@
7n+ hs,
Te+Agr_rTe.n;
" Agu-J..,*?n
f
a
Te+Agr_rTe.,
Agr-Je.,*
Z
,o
,u/
A9uT".w.ight per cent Ag
/ut
Ag.Te
Frc. 2. Portion of the Ag-Te binary phase diagram in the presence of vapor. Crosses
represent high-temperature camera data, circles represent quenched runs r-rayed with the
Guinier camera, and diamonds are the solid solution limits from Kiukkola and Wagner
(1es7).
the range of 1 to 5 degreesC. per minute. Very few arrestsat the phase
reactionsin the system were actually isothermal. Moreover, becauseof
the low thermai conductivitiesof someof the mixtures and of the glassor
silicacontainersit is inevitable that the observedbeginningsof arrestslay
slightly behind the true beginningsof the phasereactions."
Severalanomalous results were ignored in drawing up Fig. 2 from data
obtained with the Rigaku-Denki high-temperaturediffraction camera.It
was established,for example,that reliabledata could not be obtainedif a
capillary was heated up more than once. Heating the same capillary
Ag-TeSYSTEM
t9
20
P.lttenxs
cl Ag)
d meas.
i_
d meas.
3.57
3.14
3.02
2.63
3.55
311
3.03
2.62
2.57
2.24
2.17
2.25
2.18
z-lJ
m
S
302'C.
275"C
150' C
2.25
218
2.tl
ror'
204
195
1. 8 8
1. 3 5
Jl
tJ
2.O4
195
188
l.Jo
w : weaK
vw: very weaK
m:medium
s: strong.
forms. "At 62.5 at. a/6A,g, (AgrTea),this transition occurs in two well
definedsteps.On heating, the lower step, characteristicof Ag-rich mixtures, has a rounded maximum at about 265" (h); the upper step, characteristic of Te-rich mixtures, has a sharpishpeak at 306o (h). Reversal
on cooling through the upper step beginsjust above 310o,rvith a peak at
about 290o(c); coolingthrough the lower step yields a wave-iikerounded
maximum near 240o (c). The mean temperaturesare: upper step' characteristicof compositionsmore Te-rich than Ag5Tea
, 295+ 10' (m), lower
step, characteristicof compositionsmore Ag-rich than AgsTe:r,252+ l3o
( m ) ; ( N o t e : C a b r i h a s s h o w nt h o s ea s 2 9 5 + 1 0 ' a n d 2 6 5 f 1 5 oi n F i g ' 2 ,
from high-temperaturediffraction data). At 62.83 at.7o Lg, and in more
Ag-TeSYSTEM
21
62.50 to 65.54
(s8.488to 61.655)
122-138"
C.
65.54 to 66.67
(61.655to 62 295)
Note:Ag2Te:66.67 (62.29)
Ag5TeB:62.50
(58.49)
abovewhich it melts to AgrTe prusliquid. The compositionarrangeof the
z-phase at 300ois from 61.38 to 61.75 wt. /6 Ag iccording to Kiukkola
and wagner. The low-to-high poiymorphic inversion, heretofore unreported, occursat about 178o.No detail was obtained for the narrow field
containing both the low and high polymorphs; this field is indicated in
Fig. 2 as dashedline. The evidencefor this transition is given in Table 1
where the high-temperature:u-ravpatterns for the two polymorphs are
compared.
Kracek and Ksanda had difficurty in interpreting their DTA data in
the region between 62.5 and 66.67 at. /6 Ag and below 150o.Their data
are given in Table 2 and can be reinterpretedas folrows based on tr-ra'
diffraction analysis.
( 1 ) 6 2 . 5 0t o 6 5 . 5 4 a t . / 6 A g ( 5 8 . 4 9t o 6 1 . 6 5w t .
% As)
The heating arrest representsthe formation of
7-phase.The cooling
arrest representsthe breakdown of 7 to Ags_*TesfAgzTe. The larger
down to Ags-*Tea*AgzTe.
The existenceof the 7-phasewas confirmedwith the high-temperature
Ag-Te SYSTEM
23
I
I
t,.
rr
o
s
24
at about
data (Fig. 4) indicate the eutectic heat effect decreasing to zero
Agr,Tea."
I AgJe:
I
ilAe'.Tu'
g
0,
o
t
50
Frc. 4' Heat effect at the eutectic e1in cal/g for several compositions'
A g - T eS I ' S T E M
25
26
tures from
66.Oat. /e
66.7at./6
illustrated
proceeded
"
,''
'tt
layers.
Frc. 5. Photomicrograph of 80 at. /, Ag regulus exhibiting separation into two
first heating arrest and the last cooling arrest are typical of this transition, while the secondheating arrest and the first cooling arrest are more
subduedand might representmetastablephenomena'"
Heats of transformalinns."The differential thermal analysis technique has
been used to determine the magnitude of the heat effectsat some transformations with the f ollowing results:
AgzTe (l) : Ag,Te (i') at 67.75 at' /6 Ag,8'5 callg;
Agi-*Te (/z) :7-phase * liquicl at 62'50 at' /6 Ag,2'7 cal/g;
7-phase : AgzTe (d) f tiquid, 2.4 cal/S;
Ag;-*Ter (/z) : 4*r-*t.,
Ag-Te SYSTITM
27
Acr<NowTBoGEMENTS
"Kracek and Ksanda gratefully acknowledgespecimensof silver telIuride minerals lent to Ksanda by the late W. I'. Foshag of the U. S.
National Museum, and the late Professorw. E. Ford of the Department
of Mineralogv of Yale universitl'. T'hey would also like to thank Dr.
Gabrielle Donnav for helpful discussionand other assistanceas well as
the facilitiesprovided by Drs. J. \V. Greig and G. Tunell.',
cabri would like to acknorvledgethe use of the raboratory facilities of
Drs. L. A. Clark, A. J. Frueh, Jr., and G. R. Webber at McGill University, to eachof whom he is indebted for guiclancein severalphasesof the
experimentalwork. He is also thankful to Dr. R. A. Robie, u. S. Geological survey, for sendingthe unpublisheclmanuscript and laboratorv notebooks of the late Dr. F. C. Kracek..
RonnruNcns
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J /-.)9.
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Bneorrv, w. M. (1914) Empressite, a new silver-tellurium mineral from colorado ,{2.
Jour. Sci.38, 163-165.
clnnr, L. J. (1965a) Discussion on "Empressite and Stuetzite redefined,, by R. M. I{onea.
Am. Mineral. 50, 795 801.
(1965b) Phase relations in the Au-Ag-Te system and their mineralogical significance.Dcon. Geol.6O,1569 1606.
cnrcasurcn, M. eNo r. S.lrro (1916) Metallographic investigations of the system: silver
and tellurium. Mern Coll. Sci,.Kyoto Imp. {Jniv.,1,361-369.
Fnurrr, A. L ln., (1959)The structure of hessite,Ag2Te -III: Zeit. Kri,st. ll2, 4+_52.
Hoxn,r, R. M. (1964) Empressite and stuetzite redefin ed.Am Minerat. 49, 325-33g.
Krnn, P. F eno J. L Kurp (1948) Multiple differential thermal analysis. Am. Mineral.
33,387-419.
Krurxola, K. lNo c. wecNrn (1957) Measurements on galvanic cells involving solid
electrolytes. -Iour. filectrochent,.Sac. 104, 379-387.
Konnn, V. (1940) Das binare Legierungssystem Ag:le Naturuiss 27, !-49.
Knecer<, I.. C. (1930) The polymorphism of potassium nitrate lour. phys. Chem., 34,
225-247
(1941) The melting point of tellurium. f oay.Am. Chem.Soc.63, 19g9-1990.
(1946) Phaserelations in the system sulfur-silver and the transitions in silver sulfide
Trans. Am. Geophys. U nion, 27, 36+-31+
Luo, H. L. ANo w. Kr.nlllrxr (1962) Metastable simple cubic structures in gold-tellurium
and silver-tellurium alloys. -Iozr. Chem.phys.36, (7), 1870-1921
Macror, R E. aNo E. F wosrnuu, Jn. (1958) The triple-point temperature of tellurium.
f o u r .P l t y s .C h e m . 6 2 , 3 6 7 .
M.r.nxHeu, N. L. (1960) Synthetic and natural phases in the system A..-Ag-Te. Econ,
Geol 55, 1148-1178,146U1477.
P'ruNr, G. ano E. Qurncrcn (1910) I tellururi d'argento. R. Accad. Lincei. (5), 19, II,
415421.
28