Thermodynamic

and

Studies
Ag-Zn

of Liquid

Au-Zn

Systems

By Akira Yazawa* and Alzbeta Gubcova**

In order to clarify

the basic principle

of the Parkes

process, in which precious

metals are extracted

from the crude lead by

the addition of zinc, thermodynamic

studies have been carried out for the liquid Au-Zn and Ag-Zn systems for which thermodynamic data have not been satisfactorily
available.
The electromotive
force was measured using the following type of the
cell:
The error arising from volatilization of zinc was carefully avoided.
The break points on the electromotive
force curves against temperature

suggest that the liquidus

lines for the Au-Zn

system recommended by Hansen are not acceptable, and that higher liquidus temperature may be reasonable.
The activity curves obtained from the electromotive force values show considerably negative deviations from Raoult's
especially in the Au-Zn system, suggesting the large affinity of zinc for gold and silver.
In connection with the present data obtained, the properties of alloys between groups

law,

IB and II have been discussed

terms of the electronegativity,

ionic radius and electron configurations.
It is proved phenomenologically
data may be also interesting from the standpoint of recent stability theories of alloy phases.

that

in

the obtained

To understand the principle of the Parkes process, the results in the present study are combined with the data of the Au-Pb
and Ag-Pb systems, and the free energy of mixing for the ternary Au-Pb-Zn
and Ag-Pb-Zn
systems has been calculated.
Moreover, the removal limit of the precious metals from lead has been explained under the simplified assumptions.
(Received June 8, 1970)

I.

Introduction

In the pyrometallurgical refining of the crude lead,

the Parkes process, in which the precious metals (gold
and silver) are extracted by the addition of zinc, has been
generally used. The process, however, has not yet been
understood quantitatively from the standpoint of thermodynamics because of the lack of reliable fundamental
data. For the liquid binary systems of Pb-Zn, Au-Pb
and Ag-Pb, rather reliable data are available, but there
remain doubtful points for the liquid Au-Zn and AgZn systems although the vapor pressure measurements
were carried out for these systems by Schneider et al.(1)
Because the Gibbs-Duhem integration cannot be done for
the Au-Zn system owing to the lack of experimental
data in the high gold region, the activity of gold was
not given also in the compilation of Hultgren et al.(2)
For the Ag-Zn system, some experimental study was
also done partly by Kleppa et al.(3), but the data of heat
and entropy of mixing are not yet clear.
These systems are also interesting from the standpoint
of recent progress(4)(5) of the alloy theories dealing with
*

Research Institute of Mineral Dressing and Metallurgy,

Tohoku University, Sendai, Japan.
** Research Institute of Mineral Dressing and Metallurgy,
Tohoku University, Sendai, Japan. Present address: Department of Chemical Principles of Metallurgy, Faculty of
Metallurgy, Technical University, Kosice, Czechoslovakia.
(1) A. Schneider and H. Schmid: Elektrochem., 48 (1942), 627.
(2) R. Hultgren, R. L. Orr, D. Anderson and K. K. Kelley:
Selected Values of Thermodynamic Properties of Alloys, (1963),
J. Wiley and Sons.
(3) O. J. Kleppa and C. E. Thalmayer: Phys. Chem., 63 (1959),
1953.
(4) Phase Stability in Metals and Alloys, edited by P. S. Rudman
et al., McGraw-Hill, (1967).
(5) N. Engel: Acta Met., 15 (1966), 557.
Trans.

JIM

phase stability of solid solution between IB noble metals

and IIB metals.
Thus,
the electromotive
force measurements
have
been carried out for the
liquid Au-Zn
and Ag-Zn
systems to clarify their thermodynamic
properties.
II.

Experimental

Procedure

The
experimental
method
and
procedure
were
described already
in a previous paper(6).
The cell for
measuring the electromotive
force was as follows.

In the lower temperature

range, the mixture
KCl was also ueed as a fused electrolyte.

of LiCl and
Although

pure liquid zinc metal was used as a standard electrode,

it was confirmed that the error arising from volatilization
of
zinc
was
negligibly
small.
During
the
measurement
of electromotive
force,
effective
composition changes could be avoided, because the electrodes
were covered with fused electrolytes
to prevent
free
volatilization.
Due to the coexistence with pure zinc
electrode,
the alloy
generally
tend to absorb
some
amount
of zinc, but the increase in zinc content was
always less than 0.5 per cent.
Slight change in composition
was detected by weight difference
before and
after heating.
In the composition range having high gold or silver,
as is suggested from Fig. 1, the measurement
should
be carried out at a higher temperature
where the volatilization of zinc is remarkable.
Thus, in these composition ranges, the alloys having the composition
of AuZn
(6) A. Yazawa and Y. K. Lee: Trans. JIM, 11 (1970), 411.
1970

Vol.11

420

Thermodynamic

Studies of Liquid Au-Zn

and Ag-Zn

Systems

confirm
the liquidus
temperature,
a thermal
analysis
was carried out for the alloys corresponding
to the compositions:
AuZn, and two eutectics
of E1 and E2 in
Fig. 1.
Table 1
shows that
the
thermal
results
obtained here, together with the data of other investigators, are in good agreement
with those estimated from
the
present
electromotive
force
measurement.
The
liquidus line thus obtained is illustrated
in Fig. 1 with
the dashed line, showing rather good agreement
with
those obtained
by Vogel(8) and Kubaschewski(9),
and
hence Hansen's diagram seems to need some corrections.
Table

Fig. 1

Phase diagram of Au-Zn system.

is assumed from this study.

or AgZn

were used as the

reference

Dashed

electrodes

liquidus

It was confirmed
that the electromotive

Experimental

instead

temperatures

in

the

Au-Zn

system()

of

Results

in the preliminary
force was zero when

Melting

line

pure zinc.
III.

experiments
both of the

positive and negative electrodes were pure zinc.

Fig. 2 shows the relationship
between
electromotive
force and temperature
for the Au-Zn system, indicating

In Fig. 3 the electromotive force measured for the

Ag-Zn system is plotted against temperature, showing
a linear relation having a slightly positive temperature
dependence. The liquidus temperatures estimated
from the data in Fig. 3 are in good agreement with
those recommended by Hansen(7).
The electromotive forces of the alloys having less
than 0.5 atomic fraction of zinc were measured in
reference to the AuZn or AgZn alloy. In such cases,
the electromotive force values of the AuZu or AgZn
alloy in reference to the pure zinc electrode were added
to the electromotive force values obtained from experimental measurements, and the resulting values are
illustrated in Figs. 2 and 3.
The activities of zinc, azn, are given by
(1)
where E is the electromotive froce obtained, F is the
Faraday

constant,

and

energy change of zinc.

were calculated by the

Fig. 2

Plots of emf values against

liquid Au-Zn system.

temperatures

GZn

is the

The activities
Gibbs-Duhem

partial

molar

for the

a linear function
of temperature.
As shown in the
figure, when the temperature
is decreasing
gradually
from
homogeneous
liquid
range,
the value
of the
electromotive
force represents
a break
point
at the
liquidus
temperature,
and again shows another
break
point corresponding
to solidus temperature.
In the solid
solution range the linear behavior
was also observed.
Such a line of electromotive
force measurements
suggests
that the liquidus line is located at a considerably
higher
temperature
than that recommended
by Hansen(7).
To
(7) M. Hansen and K. Anderko:
McGraw-Hill, (1958).

Consuauion of Binary Alloys,

Fig. 3

free

of gold or silver
integration.
The

Plots of emf values against temperatures

liquid Ag-Zn system.

for the

(8) R. Vogel: Z. anorg. Chem., 48 (1906), 319.

(9) O. Kubaschewski: Z. phys. Chem.,192 (1943),292.

Akira Yazawa and Alzbeta

activity
and

curves

5 at 750.

thus
Both

obtained
of

the

are

illustrated

systems

show

in Figs.

considerably

negative deviations from Raoult's law, especially the

Au-Zn system, suggesting a large affinity between zinc
and gold. The activity data presented by Hultgren et
al.(2) are also shown in the figures with dashed lines,
indicating the trend similar to the authors' results.
The activity of zinc derived from Kleppa's experiment
for the Ag-Zn system agrees very well with the present
results, although their data were obtained just only in a
high zinc region.
From the knowledge of the heat of fusion(10) of
AuZn and the liquidus line estimated in the present
study, the activity coefficients were derived from
Burylev's equation(11) under the assumption of the
regular solution.
(2)
As will be discussed, the Au-Zn liquid does not obey

Fig. 4

Activity curves in liquid Au-Zn system.

is that suggested by Hultgren et al.(2)

Gubcova

the law of regular solutions, but this equation gives

activity curves in good agreement with the present
experimental results on both terminal regions.
IV.

Discussions

The partial and integral molar quantities were derived

from the experimental data, and the excess integral
quantities are illustrated in Fig. 6. In Table 2, the
heats of mixing of 50/50 liquid between the metals of
group IB and II are tabulated. Although the reliability
of the data is not so high, when the metal of group II,
Me, is fixed, the data of Me-Cu and Me-Ag are comparable but large negative values are always observed in
the Me-Au system. A similar tendency is also observed
in Fig. 7 in which the a function(12) multiplied by RT
is taken as the ordinate.
Such a great affinity found in the Au-Zn system in
comparison with the Ag-Zn or the Cu-Zn system may
be ascribed to the differences in the electronegativities

Dashed line

Fig. 6

Excess quantities
systems

Fig. 5

421

of mixing

in liquid Au-Zn

and Ag-Zn

at 750.

Activity curves in liquid Ag-Zn system. Dashed

lines are those suggested by Hultgren et al.(2)

(10) O. Kubaschewski, E. Ll. Evans and C. B. Alcock: Metallurgical Thermochemistry,4th ed.,Pergamon Press, (1967).
(11) B. P. Burylev: Tsvetnaja Metallurgija, No. 4 (1967), 35.

Fig. 7

Values of RTaZn as a function of composition

liquid Au-Zn, Ag-Zn and Cu-Zn systems.

in

422

Thermodynamic

Studies of Liquid Au-Zn

and Ag-Zn

Systems

Table 2 Heats of mixing of 50/50 liquid alloys between

the metals of IB and II(cal/mol)

(4)
(5)
(6)
From

these

equations,

at

750,

(7)
For Ag-Zn

system,

(8)
(9)
Table

Differences

of electronegativity, X,

and ionic radius, R

(10)
(11)
and

and
in sizes of ionic
radii,
because
the electron
concentration
must be the same for these three systems.
The necessary data are tabulated
in Table 3, and the
great significance
of electronegativity
factor has been
discussed by Hume-Rothery(16)
for the stability
of intermediate
phases
including
IB and II-group
metals.
On the other hand, Zener(17)explained
the stability
of
the

structures

connection
out

that

of

IB

metals

with the difference

the

most

stable

phase

with

II-group

metals

in

in core radii, and pointed

is AuMg,

followed

by

AuZn and AgMg. Such discussions for solid alloy phases

are also quite interesting for the understanding of the
thermodynamic behavior of liquid alloys.
Figs. 6 and 7 show that the Au-Zn and Ag-Zn systems are not considered as regular solutions. The zincrich liquid alloys seem to be subregular behavior(18) as
shown in Fig. 7. In the figure the results for the CuZn liquid alloy obtained by the authors(19) are also
illustrated. Although the behaviors of the solution
rich in gold or silver are not clear, they are assumed to
be regular because the regular behavior is confirmed for
the Cu-Zn liquid rich in copper. Thus, the activity
coefficients are expressed as follows:
For Au-Zn system,
(3)
(12) P. Bolsaitis and L. Skolnik: Trans. Met. Soc. AIME, 242
(1968), 215.
(13) T. Azakami and A. Yazawa: J. Min. Metall. Inst. Japan, 84
(1968),1663.
(14) L. S. Darken and R. W. Gurry: Physical Chemistry of Metals,
McGraw-Hill, (1953).
(15) L. Pauling: The Nature of the Chemical Bond, 3rd ed.,
Cornell Univ. Press, Ithaca, (1960).
(16) W. Hume-Rothery:
Phase Stability in Metals and Alloys,
edited by P. S. Rudman et al., McGraw-Hill, (1967), p. 3.

at 750,

(12)

Although the above equation may be rather a cursory

approximation, it seems to be true that inflection points
are located at around 0.4 mole fraction of zinc in all
these three systems. This result is quite interesting as
viewed in the light of the theory of Engel for copper
alloys(5). He assumed that IB noble metals are transition metals in which d-electrons participate in the bonding, and suggested that metallic copper has a mixture of
the following electron configurations: 25% Cu 1s2 2s2
p6 3s2p6d104s1 and 75%Cu 1s2 2s2p6 3s2p6d8 4s1p2.
Thus, IB noble metals have around 2.5 outer electrons
and 8.5 d-electrons whereby 2.5 outer electrons and 1.5
d-electrons participate in the bonding. Adding the
normal metal such as zinc results in the breakdown of
the d-bonding and at the solubility limit of a solid
solution, i.e. at 38% Zn in the Cu-Zn system, most of
the copper atoms supply only one outer bonding electron
per atom and very few copper, atoms have unfilled dshells. In conclusion, in the alloys of IB noble metals
with zinc, the a solid solution range may be assumed to
be transition metal behavior, and alloys having more
than 0.4 mole fraction of zinc are expected to show
normal metal behavior. Under these assumptions he
could explain various properties of copper alloys successfully. His theory seems also to supply interesting
suggestions for the present results shown in Fig.7.
The fundamental principle of the Parkes process can
be attributed to the difference of affinities of the precious metals for zinc and lead. Accordingly, the ternary
Au-Pb-Zn and Ag-Pb-Zn systems must be taken into
account. Combining the present experimental results
for Au-Zn or Ab Zn with the data for Au-Pb or AgPb given by Hultgren et al.(2), the free energy of mixing for the ternary Au-Pb-Zn or Ag-Pb-Zn system has
been calculated by the method extended by Olson and
Toop(20). The obtained results are shown in Figs. 8 and
(17) C. Zener: ibid, 25.
(18) H. K. Hardy: Acts.Met., 1(1953),203.
(19)A. Yazawa and A. Gubcova: Bull. Research Inst. Mineral
DressingMetall.Tohoku University, 25 (1969),147.
(20) N. T. Olson and G. W.Toop: Trans. Met. Soc. AIME, 236
(1966),590.

Akira

Yazawa and Alzbeta

Gubcova

When
molten

423

(14)
state is established between

the equilibrium
lead

and

the

phase

of

the

Au-Zn

or

Ag-Zn

system, the activity of gold or silver should be equal in

both phases. Thus,
(15)
Hence, theoretical limit of removal for gold in the
Parkes processunder the above assumptions is as follows:
(16)
Under the same condition, the limiting content of silver
in lead is,
(17)
Fig.8

Free

enelgy

under

of mixing

assumption

for

temary

Au-Pb-Zn

of single

liquid

phase

Under the assumed conditions, accordingly, molten lead,

containing 0.00003% Au or 0.011% Ag, may coexist

system

at 750.

with

zinc

crust

consisting

of

the

and

phases

in

which

10 to 20 weight per cent of precious metals may be

contained.
The result obtained in eq. (17) is higher than the limit
obtained in practice. This may be ascribed to the
activity data used. Although the data obtained in the
liquid state are used for solid solutions in the above
calculation, if we can make avail of the data in the
solid state, the lower removal limits may be expected.
Nevertheless, the above calculation may be useful to
understand the process of the Parkes method.
V.

Fig.9

Free

energy

under

of mixing

assumption

of

for

ternary

single

liquid

Ag-Pb-Zn
phase

at

system
750.

9.
In the calculation,
the existence of miscibility
gap
starting from the Pb-Zn
binary system was neglected in
the same way as Hultgren
et al. summarized
the data
for the binary
Pb-Zn
system.
Even so, the larger
affinity of the precious metals for zinc is confirmed
in
comparison with that for lead.
In the practical
Parkes process molten lead coexists
with solid zinc crust which is mainly in the form of the
solid

solution.

ever,

some

remain.
precious

In
amount

the

final

of

the

Accordingly,
metals

equilibrium

the

may

stage

of

limit

between

process,

how-

solution

of

be discussed

relation

the

(Zn)solid

should

removal

of

on the basis

liquid

lead

the

and

of the
solid

solution at the temperature just above the melting point

of lead.
If eqs.(6)
the

activity

and

(11)

are

coefficients

assumed
of

gold

to be

valid

and

silver

at

600K,
in

the

Summary

To elucidate the fundamental principle of Parkes

process, thermodynamic studies have been carried out
for the liquid Au-Zn and Ag-Zn systems for which
thermodynamic data could not be available over the
wide range of compositions. The electromotive force
between the liquid alloy and pure zinc electrodes has
been measured by the ordinary method.
The activity curves obtained from the emf values
show considerably negative deviations from Raoult's
law, especially in the Au-Zn system, suggesting a large
affinity between zinc and precious metals. From the
electromotive force curves against temperature, it was
found that the liquidus lines for the Au-Zn system
recommended by Hansen are not acceptable, and that
higher liquidus temperature may be reasonable. These
thermodynamic properties are discussed from the standpoint of the recent stability theories of alloy phases.
To understand the principle of the Parkes process, the
free energy of mixing for the ternary Au-Pb-Zn and
Ag-Pb-Zn systems has been calculated, using the
present data together with those on the Au-Pb and AgPb systems. Moreover, under the simplified assumptions, the way of derivation for removal limit of precious metals from lead has been explained.

phases containing 3 atomic per cent precious metals,

(13)
On the other hand, from Hultgren's data(2), those in the
infinite dilution in the Au-Pb and Ag-Pb systems are:

Acknowledgment
The authors wish to express their appreciation
to Prof. Dr. Y. K. Lee, Department of Metallurgy,
Chonpuk National University, Korea, for his kind
suggestion on the experimental apparatus.