G.K. Sigworth and J.F.

Elliott

The thermodynamics of dilute liquid copper alloys

Abstract. The published data on the thermodynamics of dilute Resume. Les auteurs font la critique des donnees thenno-
liquid copper alloys are reviewed. Selected thermodynamic values dynamiques publiees des alliages liquides de cuivre en region diluee.
have been tabulated for binary and ternary alloys. Des valeurs thermodynamiques selectionnees ant ete classifiees pour
les alliages binaires et les alliages ternaires.

In recent years considerable information on the thermo- ~i is the general composition coordinate and is the ft
dynamic behaviour of elements at dilute concentrations in activity coefficient at infinite dilution. It is to be reco-
liquid copper have been reported in the literature. However, gnized that the actual activity of i at composition ~i = 1 is
this information is widely scattered and presented in a not necessarily equal to 1, since the actual activity
variety of ways. Some of this information has been coefficient, fi, may no longer be equal to one.
compiled by Hultgren and Desai (1) in their survey of the Although data in the literature appear in several forms,
thermodynamic properties of binary systems in which only tw 0 are used in reporting the results of the study here.
copper is one component. One also has the ex tended works They are composition in atom fraction with the pure
on binary phase diagrams (2) by Hansen and Anderko, substance as the refereI~ce and standard states (a, Table I),
Elliott, and Shunk, as phase diagrams intrinsically are and composition in weight per cent with the infinitely dilute
thermodynamic in character. In this contribution the solution as the reference state and the hypothetical 1 per
available data on the behaviour of elements at dilute cent solution as the standard state (d, Table I). By
o
concentrations in liquid copper have been collected and convention, the activity coefficient ai/Xi = 'Yi when Xi + O.
summarized in a coherent and consistent form. In preparing this rnaterial, it has been necessary in many
Three composition coordinates have been used in the instances to change the standard state for the data as
literature reviewed in this work: atom fraction (X), atom reported in the literature. Because the reader may also want
per cent (a/o) and weight per cent (%). Table I shows the to alter the standard state for a set of data, a method for
reference and standard states usually associated with these doing it is presented briefly. It is desired to calculate the
composition coordinates. The associated activity coef- change in standard Gibbs free energy for the reaction in a
ficients and means of designating them in this paper are also solution at constant temperature and one atmosphere
shown in the table. For simplicity, 'Y is the activity pressure.
coefficient where the pure substance is used as the
reference and standard states, and atom fraction is the 2
composition coordinate. The symbol f is reserved for use
when the infinitely dilute solution is the reference state. ~/ and ~t
are the two composition coordinates involved in
The composition coordinate used in each case is shown as the transfer, and .u~'(~/) and .u~"(~t) are the chemical
the argument. It is to be noted that a "hypothetical" potentials for the corresponding standard states. Within the
standard state results when one uses the infinitely dilute solution, the chemical potential is J1i regardless of the
solution as the reference state. Unit activity at the composition coordinate used. Therefore, by the definition
"hypothetical" standard state is obtained by the relation- of activity one may write
ship

o
J1i = J1~' + R T In a/ = J1~" + R T In at 3

ai = fi • ~i = 1; when ~i = 1
where ai
and a~' are the activities of i in the solution in
accordance with Equation 2. Equation 3 can be trans-
formed simply to give for Equation 2
Geoffrey K. Sigworth is a Research Engineer with the Inland Steel
Research Laboratories, East Chicago, Indiana; and a former graduate
student of the Department of Metallurgy and Materials Science, J1~" - J1~' =- RT In at/a/ 4
Massachusetts Institute of Technology. John F. Elliott is a Professor
of Metallurgy at the Massachusetts Institute of Technology, The free energy change associated with a change in standard
Cambridge, Massachusetts, U.S.A. state as given by Equation 4 can be established if for a

CANADIAN METALLURGICAL QUARTERLY Volume 13 Number 3 (1974) 455

Table I. Reference and standard states used in this compilation.

Composition Reference Standard Activity

Coordinate State State Coefficient

(a) atom fraction, Xi

lim. ~ =1 ai = 1, Xi = 1 ~
~ = 'Yi
~~1 ~
lim. _Q:i = 1 ex.
(b) .atom fraction, Xi ai = 1, Xi = 1* -!.- = f.(X)
~~ 0 'Xi ~ 1

a.
(c) atom pet., a/a lim .. ~ = 1 ai = 1, a/oi = 1* _1_ = f. (a/a)
a/o~O a/oi a/oi 1

lim. _~ = 1 a.'
_1_ = f.(%)
(d) wt. pet., % (X.=1,%i=1*
I.,
%i~O %i %i 1

*Hypothetical

Table II. Equations for changing standard states.

Change * Standard Free Energy Change, ~G 0 **

o
(a) i(X, pure i ss) ~ i(X, i.d.) RT In 'Yi

(b) i(X, pure i ss) ~ i(a/o, i.d.) RT In ['Y~ /100]

(c) i(X, pure i ss) ~. i(%, i.d.) RT In 'Y~ -Ml/['lOO -Mil

(d) i(X, i.d.) ~ i(%, i.d.) RT In M1/(lOO-Md

(e) i(a/o, i.d.) ~ i(%, i.d.) RT In [Ml/Md

*ss = standard state; i.d. - infinite dilution (unit concentration is hypothetical standard
state)
**Ml = molecular weight of solvent, Mi = molecular weight of species i

particular solution the activities, or activity coefficients, series expansion of the excess partial molar Gibbs free
based on the two standard states are known. Usually this is energy of mixing of component i, Gr. That is,
true for the infinitely dilute solution. To illustrate, assume
that ~t = wt. pct. and ~/ = Xi in Equation 2. Accordingly, G~ = RT In 'Yi
1
I T,P,XbX 2 ••• Xn
= RT In 'Y.
1
I T,P,Xl ~1
Equation 2 can be re-written
n Oln'Y,.
i (Xi' pure i is std. state) = i (%, hypo 1% i is std. state) + ~ RT __ 1

j=2 cSXj
5

n n a2ln'Yi
using Equation 4. The activity coefficients are 'Yi = ')'~and f~ + j=2
~ k=2 ~ RT axJ.axk k [~] [X ] +0 3
(X ) 6

(%) = 1 in this solution. Mi is the molecular weight of i, and j<k T.P,Xl~l

M1 is the molecular weight of the solvent. The term in the
brackets expresses the ratio of Xi/%i at infinite dilution. The solvent, liquid copper, has been designated as compo-
Formulas for changing standard states that were used in this nent 1 in our n-component system, and the pure substance
compilation are shown in Table II. 1 is used as the reference state. Using the notation of Lupis
and Elliott, (5) Equation 6 becomes.
I nteraction coefficients
There has been general adoption of free energy interaction
coefficients in the literature to describe the behaviour of a
7
solute element over a modest composition range. The
interaction coefficient was introduced by Wagner (3), first
used by Chipman (4), and later extended formally by Lupis
and Elliott (5-10). The coefficients result from the Taylor

CANADIAN METALLURGICAL QUARTERLY

456
Third order terms are usually neglected, since the accura:cy Data
of the available data rarely permit their being calculated The available data on the thermodynamics of liquid copper
with any degree of certainty. alloys are summarized in Tables III, N and V. Tables III
When atom per cent is employed, Equation 6 becomes: and N give selected thermodynamic values for binary
copper-rich alloys. Atomic per cent has not been employed
n •. n •. as a composition coordinate in this tabulation; those
lnfi(a/o)= ~ €~[a/oj]+ ~ p~[a/o.]2
j=2 1 j=2 1 j wishing to do so may use the conversion relationships given
8
n n •. k in Table II. Data for the ternary alloys Cu-i-H, Cu-i-O and
+ ~ ~ p~' [a/o. J [ala k] + 0 (a/o3) Cu-i-S are summarized in Table V. In these tables inter-
j=2 k=2 1 j

j<k action coefficients that have been italicized are experimen-

tally determined values; others have been calculated by
The zeroeth order term in Equa tion 8 vanishes since fi (a/ 0) using Equations 13 to 15. Estimated values are shown in
at a/o = 0 is equal to one. The interaction coefficients in parenthesis. For example, the values for €8:
and p8:are
this coordinate system, €, p, etc., are related directly to based on experiments made at 877°C, and it is necessary to
those found when using mole fraction as a composition extrapolate to the supercooled liquid to determine the
coordinate. That is: coefficients at infinite dilution. The temperature given
indicates the experimental temperature used in the original
9 determina tion of thermodynamic properties. A temperature
range indicates th.at more than one temperature was
employed in the original experiments, and that the values
10
tabulated are valid for that range of temperature. Finally,
and the numbers of references which provide the results
reported in Tables IV and V are italicized. When the
authors have found it necessary to calculate (or recalculate)
p~,k = 10-4 p~,k 11
1 1 interaction coefficients from the data given in a study, an
asterisk follows the corresponding reference number.
When the composition coordinate is weight per cent, Unfortunately, it is not possible to indicate in a
the Taylor series expansion corresponding to Equation 6 is straigh t forward manner the accuracy of values tabulated in
(5): this study. Generally speaking, the error tends to increase
with increased concentration of the solute element. It
n . n. 2
log fi = ~ e~[wt. %j.] + ~ r~ [wt. %j.] would be best, therefore, to consult the original works cited
j=2 1 j=2 1
when second order terms become appreciable at the
12 compositions encountered in a calculation. All references
n n .k
+ ~ ~ r~' [wt. %j] [wt. %k] + 0 (%3) consulted are shown, and the ones used principally in
j=2 k=2 1 determining the tabulated data are italicized.
j<k
The cross product second order terms, pi1k and rii,k,
have not been tabulated in this study. These terms are
The relationships between interaction coefficients on mole generally obscured by the errors inherent in the measure-
fraction and weight per cent scales have been derived by ment of the tabulated interaction coefficients. Even so,
Lupis and Elliott (5). Some of the more useful relationships when the inclusion of these terms is felt to be necessary,
are given below: they often may be calculated from the reciprocal relations
given by Lupis and Elliott (5):

13
€~ = €~ 16
1 J

pl = (::~2 [100 M/r{ + (Mt-Mj)Mjell + 1/2 [M~~M.ir

p~,j
1
+ €~ = 2
1
P~
J
+ €~1 17

14

P~,k + €~ = p~,k + €~ = pi,j + €~ 18

1 J J J k 1
15

and from Equation 15.

Volume 13 Number 3 (1974) 457

Table V. Interaction Coefficients in Ternary Alloys
A. Cuj-H Alloys

Element,j Ei pi eiH e!"I ri TtC) References

H H J H

Ag -0.5 0 0.0006 -0.4 0 1225 50*

AI 6.2 3.4 0.0058 1.4 0 1225 50*
Au -1.9 1.8 0.0003 -0.8 0 1225 50*
Co -3.1 -0.2 0.015 -1.1 0 1150 48,49,57
Cr -1.6 -0.3 0.0092 -0.7 0 1550 57

Fe -2.9 -0.4 -0.015 -1.1 0 1150-1550 48,49, 51, 57

Mn -1.1 -1.9 -0.006 -0.6 -0.0001 1150 48*,49*,51
Ni -5.5 -0.4 -0.026 -1.8 0 1150-1240 48,49,57
P 10. 5. 0.088 2.6 0 1150 48,49,57

Pb 21. -50. 0.031 5.5 0 1100 57

Pt -8. 14. -0.0084 -2.5 0 1225 50*
S 9. 4.3 0.073 2.2 0 1150 48,49
Sb 13. -12. 0.031 3.2 0 1150 48,49

Si 4.8 10. 0.042 1.1 0.0016 1150 48,49,57

Sn 6.0 5.6 0.016 1.4 0 1100-1300 48, 49, 50, 55
Te -6.6 6.1 -0.012 -2.1 0 1150 48,49
Zn 6.8 -0.2 0.029 1.6 0 1150 48,49,57

B. Cu-j-O Alloys

Element Ei pi ei e9 ri TtC) References

0 0 0 J 0

Ag -0.7 0.2 0 -0.025 0 1100-1200 70,85*,10~ 109*,110,111,112,113

Au 8.6 -20. 0.015 0.14 0 1200-1550 84*,112,113
Co -68. 450. -0.32 -1.2 0.023 1200 83,111,114*
Fe -4. 04x1 06 /T (200) -20000/T -70000/T (0.01) 1200-1350 44, 72*,77,79*,83*,111, 114
'+2183 +10.8 +37.7
Ni -36000/r (0) -169/T -621fT (0) 1200-1300 69,71,83,111,112,114,115
+17. +0.079 +0.292
P -700000/T -40. 6230/r -12100/T 0 1150-1300 87,113,116
+385. +3.43 +6.63
Pb -7.4 0 -0.007 -0.14 -0.0001 1100 81
Pt 38. -81. 0.057 0.65 0 1200 111, 112, 113
S -19. (-9.) -0.164 -0.33 (0) 1206 82, 120
Si (-6300) (-3500) (-62) (-110) (0) 1250 122
Sn -4.6 -6. -0.009 -0.09 -0.0001 1100 70, 80,8~ 85*,109,110,115,117*,118

C. Cu-j-SAlloys

Element,j Ei p~ ei e~ ri TtC) References

S S J S

Au 6.7 0 0.012 0.053 0.0001 1115-1200 97*

Co -4.8 5. -0.023 -0.046 0.0003 1300-1500 97*
Fe -25400/r 2.0 -125/T -248fT 0.0002 1300-1500 97*
+8.7 +0.042 +0.08
Ni -29800jT 1.0 -159fT -290fT 0.0001 1300-1500 97*
+13. +0.069 +0.122
Pt 11.5 0 0.019 0.095 0.0001 1200-1500 97*
Si 6.9 0 0.062 0.055 -0.0008 1200 97*

CANADIAN METALLURGICAL QUARTERLY

458
Table III. The solution thermodynamics of elements in liquid copper.

'Y~(a) LlG? (X) (b) LlG? (wt.%)(c) References

0
Element, i 1200 C (cal/g-atom) (cal/g-atom) T tC) Consulted
Ag(l) 3.23 3,900-0.32T 3,900-10.52T 1100-1200 1,11-20
AI(l) 0.0028 -8,630-5.84T -8,630-13.84T 1100 1,14,18,20-26
As(v) (4.8x10-4) (-22,350(1» (-22,350-9.44T(1 » 1000 27,28
Au(l) 0.14 -4,630-0.73T -4,630-12.09T 1175-1325 1,14,18,29-32
Bi(l) 1.25 5,960-3.6T 5,960-15.1 T 1100-1300 1,14,27,33,34
C(gr) 1.4x10s 8,550+17.8T(2) 8,550+12.0T(2 ) 1100-1300 35
Ca(l) 5.1x10-4 -22,200(1) -22,200-8.2T(1) 800-925 36,37
Cd(v) 15.6 -25, 700+22.9T(1 ,3) -25,700+12.7T(1,3) 1,38-41
Cd(1) 0.53 -1,860(1,3) -1,860-10.2T(1,3) 1,38-41
Co(s) 15.4 8,000(4) 8,000-9 .OT(4) 11
Cr(s) 43 11,000(4) 11,000-8.72T(4) 2
Fe(s) 24.1 12,970-2.48T 12,970-11.34T 1460-1580 1,42,43,44
Fe(l) 19.5 9,300-0.41 T 9,300-9.27T 1460-1580 1,42,43,44
Ga(l) 0.034 -10,800+0.61 T -10,800-8.68T 1100-1280 18,45,46
Ge(l) 0.009 -16,000+1.52T -16,000-7.86r 1255-1545 18,45,46,119
1/2H2 (g) 10,400+8.4T 10,400+7.5T 1100-1300 48-57
In(l) 0.41 -9,550+4.71T -9,550-5.58T 700-1000 18,28,58
Mg(v) 0.08 -40,200+22.3T -40,200+15.1 T 650-927 59,60
Mg(l) 0.044 -8,670-0.31 T -8,670-7.53T 650-927 59,60
Mn(l) (0.51) (-1,950)(1) (-1,950-8.83T)( 1) 1244 1,61,62
Mn(s) (0.53) (l,550-2.31T) (l,550-11.14T) 1244 1,61,62
Ni(l) 2.22 2,340(1) 2,340-9. OT(1} 1,11,63-69,71
Ni(s) 2.66 6,550-2.5T 6,550-11.5T 1,11,63-69,71
1/2°2 (g) -20,400+10.8T -20,400+4.43T 1100-1300 1,11,63-73
Pb(1) 5.27 8,620-2.55T 8,620-14.01 T 1000-1300 1,14,27,88-94
Pd(s) (1.3) (800)(1) (800-10.1 T)(1) 1500-1600 95
Pt(s) (0.05) (-10,200+0.87T)(3) (-10,200-10.4 7T)(3) 1,2
1/2S2(g) -28,600+13.79T -28,600+6.03T 1050-1250 82,96-98,120,121
Sb(l) 0.014 -12,500 -12,50Q-10.4T 1000-1200 1,14,27,33,99
Se(v) 0.002 -18,200(1) -18,200-9.58T(1) 1200 88
SiO) 0.006 -15,000(1) -15,000-7.5T(1) 1550 1,100,101,122
SiCs) 0.01 -2,900-7.18T -2,900-14.68T 1550 1,100,101,122
Sn(l) 0.048 -8,900 -8,900-10.4T 1100-1300 1,14,18,30,63,
80,102,103
Te(v) 0.0328 -10,000(1) -10,000-10.5 3T( 1) 1200 88
TI(l) 8.5 6,730-0.31 T 6,730-11. 74T 1000-1300 1,90,93,94
yes) 130 28,100-9.4T(2,5) 28,100-18.1 T(2 ,5) 2
Zn(l) 0.146 -5,640 -5,640-9.17T 1150 1,39,105,106

Notes: (a) For standard state shown in first column. Vapours and gases are at 1 atmosphere pressure.
(b) Change in standard state (a) in Table II.
(c) Change in standard state (c) in Table II.
(1) Regular solution assumed. (2) Calculated from solubility data. (3) Calculated from low temperature data and phase diagram.
(4) Calculated from phase diagram by assuming a regular solution. (5) Henry's law assumed in the solute-rich solid solution.

General remarks References

Informa tion on the behaviour of elements such as (1) R. Hultgren and P.D. Desai. Selected Thermodynamic
Values
and Phase Diagrams for Copper and Some of Its Binary
antimony, bismuth, selenium, and tellurium in copper is Alloys. Monograph Series No.1, Internat. Copper Res.
sparse or non-existent. Also, there is virtually no informa- Assoc., New York, 1971.
tion about the effects of oxygen and sulphur on the (2) (a) M. Hansen and K. Anderko. Constitution of Binary
behaviour of these elements in liquid copper alloys. Thus, it Alloys. 2 nd ed., McGraw-Hill, New York, 1958.
(b) R.P. Elliott. Constitution of Binary Alloys, First Sup-
appears that there is still a considerable need for experi-
plement McGraw-Hill, New York, 1965.
mental work on the thermodynamic properties of liquid (c) F.A. Shunk. Constitution of Binary Alloys, Second
copper alloys. Supplement. McGraw-Hill, New York, 1969.

Volume 13 Number 3 (1974) 459

Table IV. Interaction coefficients in binary liquid copper alloys.

Element, i €~
I
p} e(
I
r~
I
TtC) References

Ag -2.5 1.3 -0.005 0 1150 1*,12,13,16,17*,19*

Al 14. -4. 0.14 -0.003 1100 1 *, 23*, 24, 26
Au 3.7 -1.7 0.008 0 1277 1 *, 29*, 30,32*
Bi -6800/T+ 1.65 3400/T-0.8 -9./T+0.0052 0.0001 1000-1200 1,33*,34
Ca (20.) (-10.) (0.14) (-0.0019) 877 36,37*
Fe -5.7 4.7 -0.029 0.0003 1550 1*,42*

Ga 7. (0) 0.028 (0) 1280 45*., 56

Ge 13.4 0 0.051 0.0001 1255 45*,47*
H (1.0) (0.5) (0) (0) 1123 50*
Mg (9.8) (-4.9) (0.1) (-0.OP3) 927 59*,60*
Mn 6. -8. 0.03 -0.0005 1244 1*, 60*, 61
0 - 24, 000/T+7. 8 0 -414/T+0.122 ·0.004 1100-1300 44,70,71,72,73,74,75,76,77,
78, 79, 80, 81, 82, 83, 84, 85, 86,
87

Pb -2.7 0 -0.0006 0 1200 1*, 89,90*, 91,93*,94*

S -20800/T 0 -179/T-0.004 1.8/T 1050-1250 82, 96*, 97*, 120, 121

Sb (15) (-7.5) (0.04) (0.0001) 1000-1200 33*, 99*
Sn 10. -8. ' 0.025 0 1300-1320 30*, 102, 103
TI -4.8 +3. -0.008 0 1300 1*,93
Zn 4. -2. ,0.017 -:0.0001 1150 39*, 105*

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