Thermochemistry of Binary Liquid Gold Alloys:

The Systems Au-Ni, Au-Co, Au-Fe, and Au-Mn

LETITIA TOPOR and O.J. KLEPPA

In this paper we report enthalpy of mixing data for the liquid alloys of gold with manganese, iron,
cobalt, and nickel obtained by a Calvet-type calorimeter at 1378 K. The enthalpies of mixing are
compared with Gibbs energies calculated from earlier emf and vapor pressure studies to yield informa-
tion on the excess entropies of mixing. The limiting enthalpies of solution of the liquid transition
metals in liquid gold are compared with values predicted from the semi-empirical model of Miedema
et al. and with earlier data for the same transition metals in liquid copper. The calculated values of
the excess entropy of solution in liquid gold are compared with the corresponding values in liquid
copper near 1400 K. For Ni, Co, and Fe as solutes we observe positive shifts of 5 to 9 J K -~ mol -~
which are attributed to vibrational entropy terms. For Mn there is a strong negative shift of about
35 J K -~ mol -~. This shift probably is due to "complex" or "associate" formation between gold and
manganese atoms.

I. INTRODUCTION A. Procedures and Calibrations

RECENTincreased interest in the theory of alloy formation
has drawn attention to the lack of reliable experimental data
in the area of alloy thermochemistry. This has prompted us
to initiate systematic thermochemical studies of the alloys of
transition metals with the noble metals. So far these studies
have emphasized the alloys of transition metals with liquid
copper; a summary of experimental results for the enthalpies
of solution of the first row transition metals in liquid copper
and a comparison with the semi-empirical predictions of
Miedema et aI. ~ have been published, z
Recently our studies have been extended to the liquid
alloys of gold; in a previous paper we reported new enthalpy
of mixing data for the mixtures of gold with copper and with
silver) In the present communication we report on the alloys
of gold with the first row transition metals Ni, Co, Fe, and
Mn at 1378 K. In this study we have adopted the solid-liquid
calorimetric approach, in which the enthalpies of mixing
refer to the formation of the liquid alloy from liquid
gold + solid Me (Me --- Ni, Co, Fe, Mn). By correcting
these measured enthalpies for the enthalpy of fusion of Me
at 1378 K we find the enthalpies of mixing for the liquid-
liquid process, i.e., liquid gold + undercooled, liquid Me.
in a third paper we will report on the liquid alloys of gold
with the early transition metals Cr, V, Ti, and So. 4
II. EXPERIMENTAL AND MATERIALS
The calorimetric experiments were performed in a Calvet-
type high temperature twin calorimeter which has pre-
viously been operated successfully up to about 1500 K. The
principal features of this equipment have been described
recently. 5 Our experiments were carried out using a fused
silica "liner" assembly and a fused silica calorimetric cell
similar to those used for liquid Au-Cu and Au-Ag alloys. 3
LETITIATOPOR, ResearchAssociate, and O. J. KLEPPA,Professor,
Departments of Chemistryand GeophysicalSciences, are with the James
Franck Institute, University of Chicago, 5640 South Ellis Avenue,
Chicago, IL 60637.
Manuscript submittedDecember t9, 1983.
The silica liner was flushed for about two hours with
purified argon before it was inserted into the calorimeter,
where it was maintained and flushed overnight. The experi-
ments were initiated after a constant background had been
obtained by the electronic integrator. All metal samples
were dropped into the calorimeter cell from room tem-
perature. At the beginning of each series of measurements
the calorimeter was calibrated by two or more drops of pure
gold wire. The calibrations were based on the known en-
thalpy of gold at 1378 K (referred to 298 K) as given by
Hultgren et al. 6 and presented in Table I. We applied a 1 pct
correction to the adopted value in order to allow for the heat
pick-up of the wire during its drop into the calorimeter.
Within a single series of measurements the calibrations gen-
erally were reproducible to -+ 1 pct or better.
In order to obtain the enthatpies of mixing of the binary
alloys we made several consecutive additions of the second
metal to gold. The heat effects of these experiments were
determined and summed so as to yield the enthalpy of mix-
ing for each alloy composition.
B. Materials
The gold used was in the form of 2 mm wire of 99.99 pct
purity purchased from Engelhard. The nickel metal was
5 mm diameter rod of Johnson-Matthey Puratomic quality
(~99.99 pct Ni). This rod was quartered on a jeweller's
saw, and the sections mechanically cleaned by a file. The
cobalt and iron samples also were of Puratomic quality
(-~99.99 pct Me) from Johnson-Matthey. They were in the
Table I. Adopted Enthalpies 6 and Heats of
Fusion of Pure Metals at 1378 K(J mo1-1)
Metal H~, (1378) - H~a~(298) AHfu~
Au 42960
Ni 34905 15100
Co 38508 16200
Fe 41176 12300
Mn 41648 12800

METALLURGICALTRANSACTIONSB VOLUME15B,SEPTEMBER1984--573
form of 2 mm thick foils which prior to use were cut into
rods about 2 m m • 2 mm in cross section.
The manganese sample consisted of vacuum melted mate-
rial of 99.9 pct purity purchased from Atomergic Chemetals
Corp. The metal was broken into small pieces of size suit-
able for calorimetry in a "'diamond" mortar.
III. RESULTS; COMPARISONS
WITH EARLIER DATA
We show in Figure 1 the binary phase diagrams for the
four systems studied. 7 Note that the Au-Ni, Au-Co, and
Au-Fe systems are quite simple and all show extensive solid
solubility of the transition metal in gold; for the Au-Ni
system solid solubility is in fact complete above about
1100 K, but there is a miscibility gap at lower temperatures.
These three binaries have no tendency toward compound
formation or toward the formation of ordered phases. In
contrast to this the Au-Mn system, although exhibiting wide
ranges of solid solubility, presents a number of intermediate
phases. Among these the alloy Au05Mn0.~ gives rise to a
well-defined phase diagram maximum and has a melting
point (1533 K) which rises above those of the two pure
metals Au (1336 K) and Mn (1521 K).
The calorimetric measurements were limited to those
compositions which are liquid at 1378 K. Since all the tran-
sition metals were introduced into the calorimeter from
room temperature, we present in Table I a summary of the
adopted enthalpies relative to 298 K. This table also con-
tains the values which we used for their enthalpies of fusion
at 1378 K in order to calculate the liquid-liquid enthalpies of
mixing from the experimental solid-liquid data.
The heat effects actually observed in the calorimeter,
AHob+, refer to the following reactions:
n ~ ( l , T ) + Anmjs, 298) = (hA, + A n ~ ) ( I , T ) [1]
nA~ represents the total number of moles of gold used in
the calibration experiments (which preceded the mixing
experiments), while Anm~ is the number of moles of the
second metal dropped from room temperature into the mol-
ten gold. Using the enthalpy of the second metal (Table I)
we obtained the molar (solid-liquid) enthalpies of mixing
( A H s-L) from AHoy,.
The thermodynamic properties of the binary alloys of
gold with nickel, cobalt, iron, and manganese have been

1600 9 I ' 1 ' I ' I 1'534 ' I ' I ' I ' I '

1400 _

1200 - ~6.5 3M~ 9 o/; ,~ z~

_ I~'8.5 66.6 ;='~"

68-- b~.L
800
- (Au} -I
%
--.'/3"hi
'?" +f'- .

600 / - - 7-6--9~'- ~'")-~ \ ~615 ~ " +645

L-~ 9 -

400 i
,/
/ I , I l I J 1 ,
Mn

=~
I
.~
~

,,'
,

P+ !t :~
,I I
~ I ,,.
,7

,; ~
-

!;~52o"
'-',
L I
'~

-
-

0 20 40 60 80 I00 0 20 40 60 80 I00
% Au Atomic per cent Iron Fe Mn Atomic per cent Gold Au
1495"

t-- 1400/'
I ff 2 I ' 0 i '0 I' 1';'51

~.9_G3 ~ I ." '+++

,oo01-- _--
+oo y (a-Col

+~176 ~

400L/~R+S ' fORmer,O!

+ I l + I , I
0 20 40 60 80 I00 0 20 40 60 80 I00
Au Atomic per cent Nickel Ni Au Atomic per cent Cobolt Co
Fig. 1--Equilibrium phase diagrams for the systems Au-Ni, Au-Co, Au-Fe, and Au-Mn (from Ref. 7).

574--VOLUME 15B, SEPTEMBER 1984 METALLURGICALTRANSACTIONSB

studied a great deal in the past. Gold-nickel, in particular, 30 * i ' I ' 1 ' i '
has been investigated very extensively both in the solid Series 1 9
and in the liquid state; gold-manganese has been less " ~ o ~ x Series 2 x
well studied than the other alloys. The thermodynamic ~ ~ Series 3 o
properties of the solid alloys have been obtained by the 2o- - - - - - ____ - - _
emf method (Au-Ni,8'9'l~ and Au-Fe, u Au-Mn~2), T
0
by calorimetric measurements (Au-Ni,13,~4,15Au-Co, and E {15.11
Au-Fe16), and very recently also by the isopiestic method,
(Au-Mn~7). The liquid alloys have been studied by CO-CO2
equilibrium measurements (Au-Ni,18Au-Co,19Au-Fe2~ by I0 "+J -]
2~c~P'..~ + ORIANI (1369K)
emf (Au-NiZL22), and by vapor pressure measurements
(Au-Ni, z3, Au-Co, 24, Au-Fe, 25 and Au-Mn26). The only cal- @/- ,,S-L ~ PREDEL(13B3K)
~,,~ Al-lmix
orimetric data have been reported by Oriani and Murphy
(Au-Ni 27) and by Predel and Zehnpfund (Au-Ni/5 Au-Co, /.iP ( , I , I , I I
0 0.2 0.4 0.6 0.8 1.0
and Au-Fe~6). We are not aware of any earlier calorimetric
work on Au-Mn. AU XN i Ni
Our measurements were carried out at 1378 K and were, Fig. 2--Solid-liquid enthalpies of mixing of Au(l) + Ni(s) (Oriani,
as already noted, limited to liquid compositions at this tem- Ref. 27; l~ede]. Ref. 15).
perature (see the phase diagrams in Figure 1). The actual
alloy compositions studied ranged from about XMr ~ 0.05 mixing actually presented refer to the mixing of liquid gold
tOXMr ~ 0.35 for Ni, Co, and Mn in Au and to 0.43 for Fe. with undercooled, liquid Me. Hence, his reported data con-
Our results are presented in Tables II through V. The values tain the inherent uncertainty in the adopted values of the
S-L
of AHmix, which refer to the mixing of liquid gold with solid enthalpy of fusion of Me at the calorimeter temperature.
Me, are shown in the sixth column of these tables and are In order to compare our experimental data with Predel's
plotted graphically against alloy composition in Figures 2 measured values of AH~iCxwe have calculated these quan-
through 5; these figures also show the earlier calorimetric tities from his reported data of ~HCm-~Lxusing the enthalpies
data of Oriani and Murphy 27 for Au-Ni and of Predel and of fusion given in his papers [AHfus = 16.9 kJ mol-l(Ni);
Zehnpfund for Au-Ni, 15 and for Au-Co and Au-Fe. 16 It 13.1 kJ mol-l(Co); 15.98 kJ mol ~(Fe)]. Figures 2 through
should be noted that in Predel's papers the enthalpies of 4 show that the agreement with our results is very good.

Table II. Enthalpies of Mixing for Au (l) + Ni (s) at 1378 K

Series Number nA,,mmol AnN~,mmol ~n,,mmol XN~ A H ~ J/mol

1 22.1374
1.1889 23.3263 0.0509 1312
2.7533 26.0796 0.1511 3850
1.6258 27.7054 0.2009 4892
1.7830 29.4884 0.2493 5992
4.6176 34.1060 0.3509 8221
2 17.7575
1.8762 19.6337 0.0955 2516
2.6052 22.2389 0.2015 4789
3.1020 25.3409 0.2992 7230
3 25.9559
1.3515 27.3074 0.0495 1272
3.2272 30.5346 0.1499 3607
6.5450 37.0796 0.3000 6585

Table III. Enthalpies of Mixing for Au (l) + Co (s) at 1378 K

Series Number hA., m mol Anco, m mol 3~ni, m mol Xco S-L J/mol
AHmix
1 11.5383
0.6168 12.1551 0.0507 2567
0.6694 12.8245 0.1003 4810
1.6115 14.4360 0.2007 8476
2.0438 16.4798 0.2998 11501
1.2592 17.7390 0.3495 12779
2 10.9562
0.9261 11.8823 0.0779 3599
1.0247 12.9070 0.1511 6705
1.7002 14.6072 0.2499 10288
1.7594 16.3666 0.3305 12198

METALLURGICALTRANSACTIONSB VOLUME15B,SEPTEMBER1984--575
 Table IV. Enthaipies of Mixing for Au (1) + Fe (s) at 1378 K

Series Number ?/Au, m mol Anpo, m mol ~nl, m mol XFe S-L J/mol
Anmix
1 16.4872
0.9007 17.3879 0.0518 1490
0.9418 18.3297 0.1005 2785
2.2870 20.6167 0.2003 5256
2.9434 23.5601 0.3002 7418
3.9187 27.4788 0.4000 9345
2 10.5548
0.8066 11.3614 0.0710 2044
1,0688 12.4302 0.1508 4250
1.6330 14.0632 0.2495 6846
2.1711 16.2343 0.3498 8858
2,2784 18.5127 0.4298 10351
3 18.7688
0.9893 19.7581 0.0500 1400
1.7022 21.4603 0.1254 3703
2.8431 24.3034 0.2277 6557
2.5077 26.8111 0.3000 8285
3.2096 30.0207 0.3748 9823
2.8667 32.8874 0.4293 10387

Table V. Enthalpies of Mixing for Au (1) + M n (s) at 1378 K

Series Number nAG AriA.* m mol AnM., m mot Eni, m tool XMn -AHSd~ J/mot
1 10.7246
0,5734 11.2980 0.0507 3783
0.6034 11.9014 0.0988 7196
1.5017 13.4031 0.1998 13374
1.9122 15.3153 0.2997 16266
15,7956
1.2244 1.2876 18.3076 0.0703 5279
2.8952 0.9574 22.1602 0.1013 7725
2.4702 1.7201 26.3505 0.1505 10898
2.7034 4.4143 33.4682 0.2504 15942
2.8177 5.9995 42.2854 0.3400 18740
*In Series 2 we added small amounts of gold along with the manganesein order to obtain an endothermicheat of reaction.

, i ' i I i I I ' I ' I

50 Series I 9 Series 1 9
Series 2 x
30 - - o X , ~~ 0
~x~ S-L-- 0 9 X~x 0 Series 2 x
x,,, a H~i,/Xco 9 ~X 0 Series 3 o

40
\, \
-6 20
E
AI_.IS-L/ y " "~'~o.~
"mix / '"Fe

\
,.-)
T 30 -- \

\ 12.3)
E \
\
IO - ,oi~%s ? S"_L

20 @x.,,.ej x''" AMmixo PREDEL ( 1 3 8 3 K)

.......... --'~ 16.2)
/ , I L I I i I L
0 0.2 0.4 0.6 0.8 1.0
I0 Fe
Au X Fe
- X(~r , S-L PREDEL(1383K)
r ~/ A I"Imix Fig. 4--Solid-liquid entbalpies of mixing of Au(l) + Fe(s) (Predel,
Ref. 16).
~/ , I , I J I J I I
0 0.2 0.4 0.6 0.8 1.0
Au In Figures 2 through 5 we also plot the quantity Anmix/S-L
Xco Co XMe against XMe. The two limiting values of this quantity at
Fig. 3--Solid-liquid enthalpies of mixing of Au(l) + Co(s) (Predel, XMe = 0 and at XMe = 1 are of particular interest. The value
Ref. 16). at XMr = 0 is the partial molar heat of solution of solid Me

576--VOLUME 15B,SEPTEMBER1984 METALLURGICALTRANSACTIONSB

 2o / , I ' I ' I ' 1 ' ' I ' I ' I ' l '
L 12.8) 20 9 Present work
-A-PRATT (v.p. 1535 K )
. . . . . +:c . . . . . . . . .
0 ............... ?~"

-20 /
// - d
///
-40 "'~-J
-40 /
/:

-81
-/-:/
S-L
Hmix/XM.
-60Au,

15-x
'
I
I
Present work
I
I
,
XMn
'
I ~ I
[
1
,

t
Mn

-o PREDEL(col 1383 K]
-81 Series I 9 -§ HULTGREN-from N~G~MORI
Series 2 x
/r (equil. meos. 1473 K
"T- - 10 m

-~,- TOMISKA (v.p. t880 K~

!
-10( , I , I , I ~ I
0.2 0.4
0.6 0.8 1.0
AU XMn Mn
Fig. 5--Solid-liquid enthalpies of mixing of Au(/) + Mn(s).
', e Ol~i I + ] , t , I ,
-r- Au Xfe Fe
in liquid Au at 1378 K; the extrapolated value at XM, = 1 IO~p;ese~, w'ork'o ;RE;EL;cal '138'3Kt
represents the enthalpy of fusion of Me at the temperature of
the calorimeter. By subtracting the latter value from the
former we obtain the limiting partial enthalpy of solution
of undercooled liquid Me in Au at 1378 K, AHM,. The
values of AHf~s at 1378 K which we used to calculate our 01/ , I , I A [ I I i''l
limiting enthalpies of solution were obtained from the en- Au Xco Co
thalpies of fusion at the melting points given by Hultgren, 6 8 " ' l r I ' I ' 1 '--
applying corrections for the heat capacities of the pure solid 9 Present work
"- o PREDEL (col 1383 K)
and liquid metals. These values of AHf,, are given in Table I 6 --+-ORIANI (col 1369K)
and are also shown in parentheses in Figures 2 through 5. -~-TOMISKA ( v p 1820K)
The values allow extrapolation of our experimental curves -o-GRIMSEY (e m f. 1450 K)
into the range of compositions where measurements are 4
not possible. i ] I; m z~x
2 o" A_~e:--~--o--o "% _
Finally, we show in Figure 6 a comparison between our
calculated liquid-liquid enthalpies of mixing and corre-
sponding values given in the earlier literature. We have
-0 0.2 0.4 0.6 0.8 1.0
included in this figure not only the calorimetric values of
AU XN i NJ
Prede115:6 and Oriani, 27 but also some values derived from
earlier equilibrium, vapor pressure, and emf measurements. Fig. 6 - - L i q u i d - l i q u i d entha]pies of mixing for the systems Au-Me
(Au-Mn: Pratt, Ref. 26; Au-Fr Prede], Ref. 16, Tomiska, Ref. 25,
A comparison between AHCmiCxin this figure and the mea- Hu]tgren, Ref. 30; Au-Co: Predel, Ref. 16, Neckel, Ref. 24; Au-Ni:
sured solid-liquid enthalpies plotted in Figures 2 through 5 ~ede|, Ref. 15, Oriani, Ref. 27, Tomiska, Ref. 23, Gfimsey, Ref. 21).
indicates that there is, in fact, considerably better agree-
ment for the actually measured solid-liquid data than for
the liquid-liquid values. This reflects the fact that Predel
adopted different values for the enthalpy of fusion of Ni, IV. DISCUSSION
Co, and Fe at calorimeter temperature.
A. Enthalpies of Mixing
Apart from this, it is of interest to note that there is also
quite good agreement between our liquid-liquid enthalpies It has been recognized for a long time that two empirical
of mixing at 1378 K and the corresponding enthalpy values "factors" are of principal importance in determining the
derived from vapor pressure measurements by Neckel, 24 by thermodynamic properties and phase diagrams of binary
Tomiska, 23'25 and by Spencer. 26 We consider this to be of alloy systems: (i) A "size factor," i . e . , the difference in the
special significance since the vapor pressure measurements atomic size of the two constituents; this difference gives rise
were carried out above the melting points of the transition to p o s i t i v e contributions to the enthalpy of mixing. (ii) An
metals. Hence, the enthalpies do not contain the uncer- "electrochemical" or "electronegativity factor;" this differ-
tainties associated with the adopted values of 2~Hf~. They ence makes a n e g a t i v e contribution. During the past 10 years
do, of course, reflect the very significant uncertainties these ideas have been refined further by Miedema and his
which arise from the possible errors in the temperature de- co-workers ~':8who have developed a semi-empirical scheme
pe=adence of the Gibbs energy. which allows predictions of the enthalpies of mixing for a

METALLURGICAL TRANSACTIONS B VOLUME 15B, SEPTEMBER 1984--577

wide range of alloy systems. In Miedema's approach the
enthalpy of mixing is derived from the difference in two
semi-empirical parameters ~b* and n,,.s
AH ~ -P(A~b*): + Q(An~,';~)2
In this expression the first (attractive) term arises from the
difference in electronegativity between the two metals; this
is measured by the difference in the work function ~b. The
second (repulsive) term arises from the charge density mis-
match between the two metals at the Wigner-Seitz boundary,
Anw,. In order to obtain the correct sign of the enthalpy using
the universal constants P and Q Miedema adjusted the work
function to new values ~b*.
Strictly speaking, Eq. [2] is valid only for alloys of
two transition metals, When one of the two components
is a non-transition metal, an additional attractive term R
is introduced
AH ~ -P(A(h*) z + Q(An,~'3)2 - R
This term is ascribed to a d-p electron hybridization effect
which changes with the number of p-electrons. For the noble
metals copper, silver, and gold, at the very end of their
respective transition series, the term R is small.
We show in Figure 7 a comparison between our experi-
mental values of AHMc(n (Me = Cu, Ni, Co, Fe, Mn) in
liquid gold at 1378 K and the predictions of Miedema et al.
This figure also shows the experimental enthalpies of solu-
tion for the same first row transition metals in liquid copper
taken from recent publications from this laboratory.:
We see from this figure that Miedema's semi-empirical
theory correctly predicts the overall trend of the enthalpies
of solution: a negative value of AHc,, positive values of the
right order of magnitude for Ni, Co, and Fe in gold, and a
negative value for Mn. The largest discrepancy between
prediction and experiment is found for manganese for which
our experimental result, - 9 5 kJ mol -~, is 55 kJ tool ~more
exothermic than the predicted value!
I I [ l
50
/ ~X
I /o,,x
T--
,~ 0 more positive values. This shift is about 5 J K -~ mol -~ for
/ comparable in copper and gold, we believe these shifts in
~' - 5 0 -- [ --
! large measure must be attributed to the vibrational con-
!
C:: / tributions to the entropy.
! The atomic volumes of copper and of the considered
6
,,,-I00
I"1"- - - o - - Present work, Me(4} in Au(,()
<3
9 Miederna, Me[,() in Ao(.()
--• Solo 8 Kteppo, Me (,(l in Cu(,(}
-t50
I I I I
Mo Fe Co Ni
Fig. 7--Limiting partial enthalpies of solution of Me(t) (Me = Cu, Ni.
Co, Fe, Mn) in Au(l) and Cu(/) (Miedema, Ref. 28; Sato and Kleppa,
Refs. 31,32).
578--VOLUME 15B, SEPTEMBER 1984
It is of interest to consider also the difference between the
enthalpies of solution in liquid gold and in liquid copper.
Figure 7 shows that this difference changes in a systematic
[2] manner through the transition series from +7 kJ mol -] for
Ni, to - 6 ld mol -L for Co, - 3 6 kJ mol -~ for Fe, and
- 8 7 kJ mol -) for Mn. This trend presumably in large mea-
sure reflects the increasing importance of the difference in
electronegativity (or workfunction) between copper and
gold as we move from right to left in the transition series.
B. Entropies of Mixing
In our recent work on the solutions of the first row transi-
tion metals in liquid copper we found an extremely inter-
esting systematic trend in the excess entropies of solution?
In large measure this trend could be explained in terms of
the electronic and magnetic contributions to the entropies of
solution. We are now able to explore whether a similar trend
[3] is found for solutions of some of the same transition metals
in liquid gold.
We noted above that the liquid alloys of Ni, Co, Fe, and
Mn with gold have been studied quite extensively by emf
and equilibrium methods. In Figure 8 we have selected for
each of these liquid alloy systems what we believe represents
the most reliable excess Gibbs energy values in order to
calculate the excess entropies of mixing. Unfortunately, the
Gibbs energies and enthalpies generally apply at different
temperatures. This introduces considerable uncertainty in
the calculated excess entropies which we have assigned to
the temperature of the Gibbs energy data.
Figure 8 shows that the partial excess entropies of mixing
in Au-Ni are relatively small and positive, in Au-Co and
Au-Fe somewhat larger and positive, while Au-Mn has
quite large negative values. Note that in all these systems
the excess entropies have the same sign as the enthalpy
of mixing. This is a very common occurrence in liquid
alloy systems.
Special interest is attached to the slopes of AS E as
XMe ~ O, i.e., to the limiting values of the partial excess
entropy of solution, A ~ . Although the entropy data apply
I at somewhat different temperatures (which range from
1450 K for Ni in Au to 1880 K for Fe in Au), we present in
Figure 9 a systematic plot of AS~c in liquid gold along with
corresponding values in liquid copper near 1400 K. We see
that the excess entropies for Ni, Co, and Fe in gold exhibit
the same systematic trend as in copper but are shifted to
Ni, about 9 J K-) mol -] for Co, and about 8 J K -1 mol -~
for Fe. Since the electronic and magnetic factors should be
first row transition metals fall within a relatively narrow
range: Vc, = 7.1 cm3; VNi = 6.6 cm3; Vco = 6.6 cm3;
VFe = 7.1 cm3; VM, ---- 7.4 c m 3. Therefore, it is probable
that in their alloys with copper the vibrational contributions
to the excess entropy are small. The atomic volume of gold,
I
10.2 cm 3, is considerably larger. Hence, it seems very likely
Cu that for the corresponding solutions in liquid gold vibra-
tional entropy terms are going to be quite significant.
Note, however, that solutions of manganese in gold are
qualitatively very different from solutions in copper. This is
METALLURGICAL TRANSACTIONS B
 l ! ! I l
'' I ' I ' I ' I '

~S[(1535 K) / +20
_,o

-20 \x,~Hm,, h378 K)

+I0 I
//ox\
\
~'\
, I , 1 , J , I
Au XMn Mn
9 1 ' l ' 1 ' [ I I I \\ J~"\
gt t %/:,,)
\ --\ - -
- ~r H .i,(1378K )

4- /f/'s K) 14
# w
-I0
<1
0-• /""'-~'O'~K} 0
-20
-2- , , , I , I , I L/ -E
Au XFe Fe T ASMe(, ) in Au(.()
-[
%,, '; '"''' I 9 &S~(z I in Cu{~')
-30 { ASue(s
-E ) in Au(s)
4F/,,
FY / f - - ' - - _ -tz
-40
iI I I l J
Mn Fe Co Ni Cu
Fig. 9--Limiting partial excess entropies of Me(l) in Au (l) and Cu(/),
OIV , I , I , 1 ~ I ' '~0
Au XCo Co
[ ' I ' I ' I ' I '
3p /" the formation of a gold-manganese "complex" or gold-
manganese "associate."
L /x/AHmi,(1378 K )
The problem of "associate" formation in strongly inter-
acting liquid alloy systems has attracted considerable
2| x AGEG' RIMSEY(145K)
0 1.6 attention during the past several years. We refer here, for
example, to the very recent work of Sommer and co-
workers, who have developed a simple formal model which
[ / ~,-gSE(1450K} "\\ 0.8 is used to reproduce quantitatively the concentration de-
(1 pendence of the thermodynamic properties in liquid alloy
0 0.2 0.4 0.6 0.8 1.0v systems. -'9 Most work in this area has emphasized relatively
Au XNi Ni concentrated liquid alloys with large negative enthalpies of
Fig. 8--Enthalpies, excess Gibbs energies, and excess entropies of mix-
mixing. Such systems typically also exhibit negative excess
ing in the liquid alloys Au(l) + Me(l) (Au-Mn: Pratt, Ref. 26, Au-Fe: entropies, which in some cases are large enough to yield
Tomiska, Ref. 25; Au-Co: Neckel, Ref. 24; Au-Ni: Grimsey, Ref. 21). overall integral entropies of mixing which are negative for
wide ranges of composition.
In the model of Sommer all non-configurational con-
reflected both in the large negative enthalpies of solution tributions to the mixing entropy are attributed to the for-
and in the very large negative excess entropies; in fact, mation entropy, ASA#?o f the associate A~j from the two
Figure 9 shows that ASr~,(~) is about 34 J K -l mol -l more pure components A and B. If we attempt to apply Sommer's
negative than the value in liquid copper. model to very dilute solutions of Mn in Au we expect, from
It is of interest to note also that for solutions of solid the appearance of the Au-Mn phase diagram, that the asso-
manganese in solid gold the excess entropies are small and ciate which is formed in the liquid alloys probably should
positive. This is illustrated in Figure 9 in which we include have the stoichiometry AuMn (i.e., i = j = I). We further
an approximate value of ~ e ) taken from the emf study of would equate the observed partial excess entropy of solu-
Eremenko et al. lz If we compare this result with the corre- tion, ASM.,~
-E ~ - 3 5 J K-1 mol -~, with the entropy of for-
sponding value for ASe,( 0 in liquid copper, we find a differ- mation of this associate.
ence of about +5 J K -~ mol-L This difference is roughly There are, however, some difficulties with applying this
comparable to the observed positive shifts for Ni, Co, and model in the present case. Thus, we see from Figure 5 that
Fe on going from copper to gold. the liquid system Au-Mn shows enthalpies of mixing which
It remains to consider briefly the probable physical sig- seem to reflect the characteristic parabolic dependence on
nificance of the very large negative excess entropies of composition which is found in nearly random mixtures.
solution for liquid manganese in liquid gold. We believe While the enthalpies of mixing are fairly strongly negative,
these large negative excess entropies must be attributed to the range of composition studied is somewhat limited and

METALLURGICAL TRANSACTIONS B VOLUME 15B, SEPTEMBER 1984--579

does not allow us to draw any conclusions regarding a spe-
cial stability for the "associate" AuMn. Furthermore, the
excess entropy data in Figure 8 suggest negative excess
entropies in the middle of the liquid system of - 4 to
- 5 J K -l g atom -~, i.e., entropies of formation of the
"associate" AuMn of - 8 to - 10 J K- ~mol- ~rather than the
much more negative partial entropy which we found for
dilute solutions of Mn in Au.
ACKNOWLEDGMENTS
This material is based upon work supported by the
National Science Foundation under Grant CHE-8106980.
It also has benefited from the Central Facilities of the
University of Chicago MRL.
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METALLURGICALTRANSACTIONS B