Aspects of the thermodynamics of metallic solutions

O.J. Kleppa

To cite this version:

O.J. Kleppa. Aspects of the thermodynamics of metallic solutions. J. Phys. Radium, 1962, 23
(10), pp.763-772. <10.1051/jphysrad:019620023010076300>. <jpa-00236677>

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LE JOURNAL DE

PHYSIQUE

ET LE

TOME

RADIUM

23.

OCTOBRE

1962,

763.

ASPECTS OF THE THERMODYNAMICS OF METALLIC SOLUTIONS

By O. J. KLEPPA,
Institute for the Study of Metals and Department of Chemistry,
The University of Chicago, Chicago 37, Illinois.

Rsum, Un travail rcent sur la thermodynamique des solutions mtalliques a donn des
informations qui ne peuvent tre obtenues partir dune analyse des diffrents diagrammes de
phases seulement. Certains systmes de solutions binaire sont discuts en vue dillustrer linfluence
sur les proprits thermodynamiques dune diffrence de taille, dlectrongativit et la valence
caractristique des deux corps en solution. Une attention particulire sera donne leffet de
valence sur lenthalpie de mlange pour les solutions des mtaux du groupe B et au problme
gnral de lentropie de mlange dans les systmes des solutions mtalliques.
2014

Recent work on the thermodynamics of metallic solutions has produced inforAbstract.

mation which cannot be obtained from an analysis of the various phase diagrams alone. Selected
binary solution systems will be discussed with a view towards illustrating the influence on the
excess thermodynamic properties of a difference in the size, the electronegativity and the characteristic valence of the two solution partners. Particular attention will be given to the effect of
valence on the enthalpy of mixing in terminal solutions of group B metals, and to the general
problem of the excess entropy of mixing in metallic solution systems.
2014

Since the turn of the century a great deal of

information has become available on the thermo-dynamic properties of metallic solutions. This
work originally was stimulated through Gibbs discovery of thelphase rule. Even today the most
extensive body of thermodynamic information on
alloy systems is contained in the literature on phase
equilibria. However, it should be recognized that

all solid state rate processes are exceedingly slow,

compared to the time involved in making the usual
thermodynamic measurements. Therefore, observations made on a given solid solution specimen
may not in fact relate to a state of thermodynamic
equilibrium. Note also that the number of binary
systems with extensive solid solubility is quite restricted.
Some of the complications associated with studies
of solid solutions are eliminated in work on liquid
alloys. In fact, thermodynamic data on liquid
metallic solutions are in certain respects more
extensive and also more reliable than corresponding data on solid solutions. For this reason,
we shall in the present paper consider examples
selected both from solid and from liquid metallic
solution systems. Most of the available information relates to binary alloys involving Group B
metals. We shall restrict our discussion to this
type of system.

GB = HB -TSB.
We shall not hre consider the various experimental techniques used in detailed studies of the

metallic solutions.
During recent decades, impressive strides have
been taken in the statistical mechanics of molecular solutions [3]. However, most of this work
has been based on models which bear very little
resemblance to the metallic state. For example,
a characteristic feature of the important practical
solution theories (i.e. those that lend themselves to
detailed numerical calculations) is the assumption
that the total cohesive energy may be approximated by a summation of pair interactions. It
has become increasingly obvious in recent years
tliat this approach is wholly unsatisfactory for
metallic systems. Nevertheless, among- the sta-

this type of information, valuable as it is, leaves

much to be desired in any detailed discussion of
solution thermodynamics. While the phase diagrams of course reflect the dependence of the total
free energy of the system on composition and on
temperature, they usually do not permit an unambiguous numerical evaluation of the theoretically
interesting excess thermodynamic quantities. In
the present discussion we shall in the main be concerned with the (intgral) excess free energy, GB,
the excess enthalpy, HB, and the excess entropy of
mixing, SB [1]. These quantities are related
through the fundamental thermodynamic relation

thermodynamic properties of metallic solution [2].

Among these the most important are high temperature galvanic cell and vapor pressure methods
for free energy dterminations, and high temperature reaction calorimetry for the mixing enthalpies. The best entropy data usually are obtained
through combination of equilibrium free energy
values with alorimetric enthalpies.
In considering data on metallic solutions reported in th literature, a word of caution is in order.
It is particularly important to keep in mind that

Idealized models for

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphysrad:019620023010076300

764

tistical theories the so-called lattice theories of

solutions merit special comments. These have
contributed substantially toward our understanding of the order-disorder phenomenon, and provide the basis for the usual theoretical estimates of
departures from random mixing in metallic solu-

tions..
In the simplest version of the lattice theory of
solution it is assumed that the total cohesive energy
arises from nearest neighbor interactions or
"
bonds. Each bond has a certain energy, v, the
nature of which is unspecified. This energy is
assumed to be independent of the other bonds
formed by the atoms in question, i.e. it is independent of composition. Under this assumption,
the total internal energy of the alloy A-B is simply

Here nAB,

ngg

and

the numbers of nearest

of fixed energy vAB, vAA and

nBB are

neighbor bonds, each

vBB, respectively.

In statistical calculations based on this model

adopts a latthe frame of reference, with a coordination number z. It is then found that all the
molar excess thermodynamic properties of the considered mixture can be expressed in terms of a

one

single

interaction

parameter

i.e. vAB &#x3E; 1 /2 (VAA + VBB), a larger than random

number of AA and BB bonds in predicted (" clustering "). Similarly, for X 0 one predicts some
preference for the AB configuration at all finite
temperatures (" short range order ").
The theory permits estimates to be made of
these departures from random mixing, and of the
ensuing loss in entropy. For moderate valu"es of
we obtain for this configurational excess entropy

In view of this formula, it is indicated that above

the critical temperature (T &#x3E; /27?) these negative
configurational entropy contributions should be
quite small (- 0. 1 cal/degree/mole or less). Often
they may be neglected compared to other and
much larger thermal contributions (See below).
In recent years attempts have been made to
make calculations of the thermodynamic properties
of metallic solutions on the basis of solid state
theory. So far, these theories have not approached
the solution problems from the more comprehensive point of view of molecular solution theory.
Instead they have focused their attention on some
particular problem which lends itself to theoretical
treatment. The most successful of these theories
is Friedels treatment of the relative valence effect
in terminal solutions [5]. We shall have more to
say about this below.

where No is Avogadros number.

For the purpose of the present brief discussion it
Selected examples of real metallie solutions.
is useful to consider this theory in two approxiIt is well known from the extensivework on binary
mations [4].
a) Inthe" zeroth " approximation it is assumed phase diagrams, particularly by Hume-Rothery
that is sufficiently small (compared to RT) so and his school, that these diagrams reflect the
that the mixing of the two components is essen- working
of at least three important " factors " the
"
size " factor, the " electro-chemical " (or better
tially random. In this (Bragg-Williams) case we
the " chemical affinity " or " electronegativity ")
obtain
factor and the " valence " factor. It is obvious
that these factors are interrelated, and that to consider them separately represents at best a crude
approximation. Nevertheless, it serves as a useful
On general thermodynamic grounds we know starting point in a survey of the properties of real
that for positive values of HE (and of ) this system metallic solutions.
must segregate at low temperatures into an A-rich
These three factors, since they are recognized
and a B-rich phase. In the present approximation readily in the appearance of many phase diagrams,
the critical mixing temperature is 7c = X12R.
are even more strongly reflected in the excess therIn a similar way we arrive at the conclusion that modynamic properties. As might be expected,
for negative values of HE (and X) the equilibrium one usually finds that a diffrence in atomic size
state at low temperature must involve the for- gives rise to positive contributions to H-, FE and SE
mation of an ordered phase AB. Again, in the con- Similarly, a difference in electronegativity gives
sidered approximation, the critical (Curie) point rise to negative contributions. Finally, it is found
for the ordering process is
that a difference in the characteristic valence of the
two solution partners often produces an asymmetry
in the excess thermodynamic functions, i.e. a proof
this
it
is
nounced difference between the solutions of A in B
In
theory
b)
higher approximations
taken into account that for any non-zero value of and those of B in A. We shall illustrate these .
the interaction parameter there will be some general observations by considering some selected
departure from random mixing. For &#x3E; 0, examples of binary solution systems.
-

765

It is

a) SYSTEMS WITHOUT VALENCE EFFECTS. - The

alloys of silver and gold are sometimes uncritically
referred to as " ideal ". Thus this system has a
very simple phase diagram with a complete range
of solid solutions (see fig. 1), the lattice parameter

noteworthy that this system also has a

negative excess entropy of mixing, which amounts
to about 0.3 cal/degree g. atom in the middle of the
system. Although this value is not accurately
known, it certainly is too large to be explained by
departures from random mixing. Therefore, it is
indicated that the excess entropy in this system in
the main must be of thermal, i.e. in this case presumably of vibrational origin. We have, under the
assumption that we can eff ectively " freeze in "
the high temperature random configuration,

Here

Ci represents

the deviation of the heat

capacity from a linear dependence on composition

rule). Note that non-zero values

of C, of course contribute also to HB. However,
these contributions tend to be overshadowed by
the temperature independent terms.
The most significant thermal contributions to
the excess entropy usually arise at temperatures
well below the characteristic temperature of the
alloy. But regrettably, we do not have low-temperature heat capacity data for silver-gold alloys
which permit a check of eqn. (3). On the other
hand, if our identification of the excess entropy as
vibrational is correct, we should be able to turn
the problem around and use the observed excess
entropies to estimate the Debye 6s for the alloys.
For elevated temperatures (T 6) We have on
the Debye model the following simple expression
for the vibrational excess entropy of the alloy

( Kopj-Neumann

Phase diagram and excess

FIG. 1.
for silver-gold alloys (ref. [7]).
-

thermodynamic

data

less than 0.15 % from Vegards rule,

and there is no convincing evidence for phase separation or for the existance of any ordered phase at
low temperatures.
It is well known that the atomic radii of gold
and silver are very similar. Thus the " size
f actor " is very favorable. On the other hand,
these metals have a substantial diffrence in electronegativity (about 0.5 units on Gordys scale [6]).
Thus, chemical reasoning suggests that " ionic "
forms of the type Ag+ Au7- may be of some importance in bonding between these metals. We accordingly anticipate negative departures from ideality.
The phase diagram, given in the upper part of
figure 1, shows a very small liquidus-solidus separation, which points in the same direction.
Detailed thermodynamic measurements, the results
of which have beeri summarized by White, Orr and
Hultgren [7] confirm this, as illustrated in figure 1.
The rather large negative enthalpies of mixing
suggest that this system might be expected to have
an ordered intermetallic phase at low temperature.
So far, this has not been observed.

departs by

Here 0 is the Debye temperature for the alloy

0 -[r0Au + (1-x) OAg]. The observed
and 6E
negative excess entropies for gold-silver accordingly
imply positive departures of 0 from a linear dependence on composition (higher frequencies of vibra=

Fie. 2.

Youngs modulus
system silver-gold (ref. [8]).
-

for solid solutions in the

766

tion). If we adopt values of 0 of 215 and 1800 for

silver and gold, respectively, we estimate from the
entropy data a 6 of 209 for the equi-atomic alloy.
This value is about 6 % larger than the mean of
the values for silver and gold. Our result is consistent with the data on Youngs modulus for this
system reported by Kster and Rauscher [8], and
presented in figure 2. This agreement demonstrates, as was originally suggested by Zener [9], that
data on the elastic constants for metallic solid solutions may be used to advantage in estimating vibrational entropy contributions. Of course this holds
equally well for systems with and without valence
effects.
As a second example of systems without valence
effects let us consider copper-silver, for which the
phase diagram and some other thermodynamic
data are presented in figure 3 [10]. Here the elec-

FIG. 3.
Phase diagram and excess thermodynamic data
for silver-copper alloys (ref. [10]).
-

diffrence is zero on Gordys scale,

while the size factor is fairly large. Thus we
expect and find substantial positive deviations
from ideality, both in the solid and in the liquid
state. Note that the (positive) excess fie energies are significantly larger in the solid than in the
liquid solutions. This behavior is characteristic of
simple alloy systems where there is a large difference in size between the two solution partners.
It

tronegativity

reflects the fact that the size factor is far more critical in the solid than in the liquid state. On the
other hand, when the size difference is small, as in
silver-gold (and in silver-palladium, see below), it
may be found that the solid solutions have lowr
excess free energies of mixing than the corres-

ponding liquid alloys.

Beginning with the

works of Pines [11] and

Lawson [12] several attempts have been made to
calculate excess thermodynamic quantities for
binary solid solutions from elastic theory, i.e. on
the basis of the " misfit " between solvent and
solute atoms. On the whole, there is only fair
agreement between theory and experiment in these
calculations.

Histob) HUME-ROTHERY TYPE SYSTEMS.

rically, the most important systems exhibiting
valence effects are the alloys formed between the
mono-valent metals copper, silver and gold and
many metals of higher valence. Among these systems the simplest ones are those where both solution partners belong to the same row in the periodic
table, such as the alloys of copper with zinc, gallium and germanium and the alloys of silver with
cadmium, indium and tin. In these cases the size
factors are moderate, and there is a relatively
small difference in electronegativity between the
two metals. Thus the setting is right for a display
-

of valence effects.
We give in figure 4 the equilibrium phase diagrams for the alloys of silver with cadmium, indium
and tin. These diagrams may be used to illustrate
the well-known Hume-Rothery rules. However,
we shall restrict the present discussion to thermodynamic information which cannot be derived from
the phase diagrams alone. In particular, we shall
review the data on the enthalpies of mixing, which
are presented in figure 5 [13, 14].
These data
apply for alloys which are stable at 450 OC, at
which temperature cadmium, indium and tin are
all liquid. This circumstance turns out to be a
fortunate one, since it gives an insight into the
thermodynamics of these systems which can not
readily be obtained through study of the solid
phases alone.
The most striking feature of the data in figure 5
is the remarkable difference in the properties of the
terminal solutions in these systems, i.e. between
the solutions of cadmium, indium and tin in silver,
on the one hand, and the solutions of silver in the
liquid multi-valent metals on the other.
From a purely thermodynamic point of view we
may characterize the terminai solutions by two
sets of quantities, namely the liniiting slopes and
the limiting curvatures of the excess thermodynamic
functions. In the special case of the enthalpy of
mixing the limiting slope represents the change in
enthalpy associated with the transfer of a solute

767

FIG. 4.
tems

Phase diagrams in the syssilver-cadmium, silver-indium

-

and silver-tin.

Excess enthalpy data at

FiG. 5.
450 DC for the systems silvercadmium, silver-indium and silvertin (ref. [13], [14]).
-

768

atom from its reference state

(here the pure solid

into
the
solvent.
In general
liquid solute)
pure
this transfer will involve a very drastic change in
the environment of the solute atom. Therefore, it
is obvious that a realistic calculation of this quantity is a very formidable task. This was attempted
by Friedel on th basis of a suitable thermodynamic cycle [5]. However, in this cycle the heat
of solution appears as a diffrence between very
large numbers, and the results are of rather limited
or

value.
More interest is attached to the limiting curvature of the enthalpy of mixing. This quantity is a
measure of the interaction between the solute
atoms in the matrix of the solvent, and was successfully calculated by Friedel [5]. In the present
paper we shall refrain from discussing the fundamental basis for this theory. The most important
conclusion reached is that if the complicating factors of a large diffrence in atomic size and of
strong chemical interaction between solute and
solvent do not overshadow the valence effect, one
might expect the limiting curvature of the enthalpy
of mixing to be determined by the difference in
valence between solvent and solute. Thus, if the
solute is of higher valence than the solvent, there
should be an effective repulsion between the solute
atoms, i.e. a positive curvature. If the situation is
reversed, there should be attraction and a negative
curvature. Furthermore, for diffrent solutes in
the same solvent, it is predicted that there should
be a rough proportionality between valence difference and curvature.
The enthalpy data presented in figure 5 are in
reasonable agreement with these predictions.
Thus we find positive and increasing curvatures for
the solid solution of cadmium, indium and tin in
silver and, what is more remarkable, negative curvatures for silver in liquid indium and tin. The
data for silver in liquid cadmium are somewhat

FIG. 7. - Plot of

HE /x for zinc
(ref. [15]).

and

gallium in copper

uncertain. In this case it is probable that we have

a positive rather than a negative limiting curvature.
In order to attempt a more quantitative check
of the stated predictions we give in figure 6 a suitable graph for the solid solutions of cadmium and
indium in silver. Note that the slope of HE lx
versus x is a measure of the curvature of the
enthalpy of mixing. The figure indicates that the
curvature for indium is about twice that for cadmium. Very recent calorimetric work by Kleppa
and King [15] on the solid solutions of zinc and
gallium in copper shows comparable agreement, as
demonstrated in figure 7. However, it should be
recognized that the data in figures 6 and 7 do not
cover the very dilute range where the theory is
most applicable. Therefore, one should not overemphasize this agreement with theory.
OF GROUP II B METALS. -Many of
B metals fall within a fairly restricted
range with respect to atomic size and electronegativity. Therefore, pursuing the line of reasoning advanced in the present paper, one might
expect that the alloys formed between the divalent
metals zinc, cadmium and mercury, on the one
hand, and metals of higher valence, on the other,
should also display valence correlated solution properties. In this context it is interesting to note
the suggestion made by Raynor [16], that the very

c) ALLLOYS

the

FIG. 6.

Plot of

HEjx for cadmium

(ref. [14]).

and indium in silver

Group

169
low solid sofubilities of multivalent metals in zinc
and. cadmium might be related to certain details of
the band structure of these solvent metals. Apart
from this, there is little evidence in the phase diagrams for the importance of valence effects.

Fic. 8.

Some

excess

It turns out that a detailed analysis of the excess

thermodynamic properties for some of the liquid
alloys of zinc and cadmium is more revealing.
This is illustrated in figure 8, where we present
some of the integral excess thermodynamic quan-

thermodynamic quantities for liquid zinc-cadmium, zinc-indium

tities for the liquid lloys of zinc with cadmium,

indium and tin [17]. The data undoubtedly reflect
both a diffrence in size and a diffrence in valence
between the solution partners. Nevertheless, the
correlation between excess* properties and valence
diffrence is apparent.
A survey of the differential excess quantities for
various solutes in zinc is even more suggestive [181.
For this purpose we give in figure 9 the differential
excess enthalpies of liquid zinc as a solvent for a
wide range of other group B metals. In figure 10
we present a similar graph which shows the differential excess entropies plotted against lectron
concentration. We see that for all the considered,
muttivatent solutes the exeess entropies are posai-

and zinc-tin

(ref. [17]).

tive-and,-except in"the case of bismuth, of comparable magnitude at the same electron concentration. Similarly, the enthalpy data indicate a clear
corrlation between excess enthalpy and valence
difference. However, it should be noted that the
"
valence effect 1) for solutions in liquid zinc (and
cadmium) is opposite in sign to that predicted by
the Friedel theory [18 A).
We have suggested elsewhere [19]7,that the thermodynamic properties in these terminal solutions
may possibly be related to departures from free
electron behavior ni liquid. zinc and cadmium.
There is some support for this in the anomalous
temperature dependenae of th electrical conuctivity ouf thse liquid metals. On the other hand,
.

770

systems would appear to be very simple, and it

might be compared, for example, to silver-gold.
Thus, we estimate from the course of the liquidus
curve that
GE(s)
G(1) for silver-palladium
this

FIG. 9.
Differential excess
rich liquid alloys (ref. [19]).
-

enthalpies

for zincin zinc-

FIG. 11.
Phase diagram and excess thermodynamic data
for silver-palladium alloys (refs. [23], [24]).
-

FiG. 10.
Differential excess entropies for zinc in zincrich liquid alloys (scale on left for Zn-Ag and Zn-In
only. Other curves displaced by multiple of 0.1 cal/deg,
ref. [19]).
-

recent Hall coefficient measurements by Esch

do not seem to support this interpretation.

[20]

ALLOYS INVOLVING TRANSITION METALS

SILVER-PALLADIUM SYSTEM. --At the

THE

Finally, it should be mentioned that the liquid

alloys of mercury with metals of higher valence
show a much more complex pattern of thermodynamic behavior than the corresponding zinc and
cadmium systems [21].
(d)

present time
the bulk of the detailed thermodynamic information on metallic solutions pertains to alloys formed by non-transition metals. Therefore, there
is as yet no basis for any general systematic discussion of the solution properties of transition metal
alloys. On the other hand, reliable thermodynamic data have become available in recent years for
a number of binaries involving transition metals.
In some cases these exhibit features not found in
the examples considered above, as we shall illustrate
the. silver-palladium system.
We present first in the upper part on figure 11
the accepted phase diagram for this system. In
any discussion based only on the phase diagram,

by considering

should be about -150 cal/g; atom in the middle of

the system. The comparable figure for silvergold is about 50 cal/g. atom [22]. On the other
hand, the larger liquidus-solidus separation indi-

a more positive (or less negative) departure

from ideality than in silver-gold.
It was only on the completion of the recent
e. m. f. study by Pratt [23], and the calorimetric
work by Chan, Anderson, Orr and Hultgren [24]
that it became generally recognized that the thermodynamic properties of silver-palladium are
really quite complex. This will be noted from a
brief look at the thermodynamic data given in the
lower part of figure 11. It is particularly noteworthy that silver-palladium has a very large negative excess entropy of mixing, which for equi1.8 cal/degree
atomic alloys amounts to about
g. atom at 1 000 OK. This figure should be compared with the ideal entropy of mixing of + 1.38
cal/degree. Thus we find that at elevated temperatures the formation of an essentially random solid
solution of composition Ago.5Pdo.5 actually is associated with a net reduction in entropy. This somewhat surprising result shows that the unfled dshell in this case gives rise to large thermodynamic
effects which are either absent, or are present only

cates

771
a very limited extent, in the types. of systems
discussed so far. Presumably, these eff ects are of
electronic and magnetic as well as of vibrational

to

origin. To a first approximation it probably is

justified to consider these three effects separately,
and they will of course contribute to all the various
excess thermodynamic properties of the mixture.
However, they are most readily recognized in the
entropy of mixing, and we shall confine our discussion here to this quantity.

Numerical estimates of the vibrational and electronic contributions to the high temperature excess
entropy of silver-palladium alloys can be made
from the helium-range heat capacity data of Hoare
and Yates [25]. Values of 6 and y obtained in
their work are given in figure 12, along with values

--- 0.8 cal/degree g. atom (from elastic constants)

and 20131.2 cal/degree (from heat capacities).
If the electronic heat capacities depend linearly
on the absolute temperature we have for the electronic excess entropies

y
Y-e
[XAg YAg + XPd ypd]. On the
assumption that this applies up to 1. 000 OK, we
estimage Sli for a 50-50 alloy to be about 0.8 cal/
degree g. atom. Actually, available high temperature heat capacity data for pure transition metals

where

indicate that the electronic contributions to the

heat capacity at elevated temperatures probably
are somewhat smaller than yT.
Therefore, this
estimate of S may be high numerically.
Finally, we shall consider very briefly the magnetic contributions to the entropy of mixing. In
gnral such contributions will depend on the
nature of the magnetic properties of the components. In silver-palladium pure silver is diamagnetic, palladium is paramagnetic, and the alloys
are paramagnetic for xpd &#x3E; 0.5 [26].
Clearly the
d-electrons, presumably localized on the palladium
atoms, are spin-paired at high silver contents, with
an ensuing loss in entropy.
This problem has been discussed in a recent
paper by Oriani and Murphy [27]. Adapting an
approach advanced by Weiss and Tauer [28], these
authors assume that in the diamagnetic range the
magnetic contribution to the entropy of mixing
may be represented by - xpd R In (03BCpa + 1).
Here 03BCpd is the effective atomic moment of palladium (1.44 Bohr magnetons). Assuming that the
alloy is fully diamagnetic at xid == 0.4, they
suggests that the magnetic excess entropy in the
paramagnetic range will also vary linearly with
composition (going to zero at pure palladium). In
this manner they arrive at an estimate of about
- 0 . 7 cal/degree g. atom for the magnetic contribution to the excess entropy in Ago.5Pdo.5.
The sum of the quoted vibrational, electronic
and magnetic entropy contributions amounts to
FIG. 12. - 03B8 and y for silver-palladium alloys (refs. [25],
2.3 to --2.7 cal/degree g. atom. lthough
[26]).
this result is numerically somewhat larger than the
of 0 derived from elastic constant measurements experimental value, it is of comparable magnitude.
This work has been supAcknowledgements.
by Hoare, Matthews and Walling [26].
of
Naval Research under
from
these
the
Office
above
we
estimate
of
use
ported
by
(4)
eqn.
By
data the vibrational contribution to the excess contract No. Nori-2121 with the University of
entropy for an equi-atomic alloy to fall between Chicago.
--

REFERENCES

[1] The integral excess thermodynamic quantities are defined through the relations
YE = 0394 Y 2014 0394 Yideal
where 0394 Y is the molar change in the function Y on
mixing. Note that
0394Gideal = RT(x In x + (1 2014 x) In (1
x)).
2014

Here x and

(1 2014 x)

are

the mole fractions of the

two components. Similarly,

for the

entropy of

mixing

0394Sideal = 2014 R(x In x + (1 2014 x) In (1 2014 x)),

i.e. the entropy of random mixing. On the other

hand we have for enthalpy, internal energy, volume

and heat capacity
0.
0394Hideal
0394Eideal = 0394Videal
0394Cp ideal
=

772

[2] Detailed discussions of these methods are presented in

the National Physical Laboratory Symposium No. 9,
The Physical Chemistry of Metallic Solutions and
Intermetallic Compounds. H. M. S. O., London,
1959.

[3] See e.g. PRIGOGINE (I.), The Molecular Theory of

Solutions, North Holland Publishing Company,
Amsterdam, 1957.
[4] An authoritative discussion of the lattice theories of
solution is given in E. A. Guggenheims Mixtures ",
Oxford University Press, Oxford, 1952.
[5] FRIEDEL (J.), Adv. in Physics, 1954, 3, 446.
[6] GORDY (W.) and THOMAS (W. J. O.), J. Chem. Physics,
1956, 24, 439.
[7] WHITE (J. L.), ORR (R. L.) and HULTGREN (R.), Acta
Met., 1957, 5, 747.
[8] KSTER (W.) and RAUSCHER (W.), Z. Meta!lk., 1948,
39, 111.
[9] ZENER (C.), in Thermodynamics in Physical Metallurgy, A. S. M., Cleveland, 1950.
[10] HULTGREN (R.), Private communication.
[11] PINES (B. J.), J. Physics, U. S,B S. R., 1940, 3, 309.
[12] LAWSON (A. W.), J. Chem. Physics, 1947, 15, 831.
[13] KLEPPA (O. J.), Acta Met., 1955, 3, 255.
[14] KLEPPA (O. J.), J. Phys. Chem., 1956, 60, 846.
[15] KLEPPA (O.,J.) and KING (R. C.), To Acta Met (in
"

press).

[16] RAYNOR (G. V.), Progress in Metal Physics, 1949, 1, 1.

LE JOURNAL DE

PHYSIQUE

ET LE

[17] KLEPPA (O. J.), KAPLAN (M.) and THALMAYER (C. E.),
J. Phys. Chem., 1961, 65, 843.

In the dilute range, the differential excess quantities

of the solvent are related in a simple manner to the
curvature of the integral, excess quantity. (See also
ref. [21].)
[18A] Note added in proof. Very recent theoretical work
by Blandin and Deplante reported during this colloquium, represents an improvement on the earlier
Friedel theory, and appears to account for this change
in sign.
[19] KLEPPA (O J.) and THALMAYER (C. E.), J. Phys.

[18]

Chem., 1959, 63, 1953.

(E. G.), Private communication.
(O J.), Acta Met., 1960, 8, 435.
(O. J.), Acta Met., 1960, 8, 804.
PRATT (J. N.) Trans. Faraday Soc. 1960, 56, 975.
CHAN (J. P.), ANDERSON (P. D.), ORR (R. L.) and
HULTGREN (R.), 4th Tech. Report, Mineral Research
Laboratory, Berkeley, Calif.,1959.
[25HOARE (F. E.) and YATES (B.), Proc. Roy. Soc., 1957,
A 240, 42.
[26] HOARE (F. E.), MATTHEWS (J. C.) and WALLING (J. C.),
Proc. Roy. Soc., 1953, A 216, 502.
[27] ORIANI (R. A.) and MURPHY (W. K.j, Acta Met., 1962,

[20]
[21]
[22]
[23]
[24]

WILSON
KLEPPA
KLEPPA

10, 879.

[28] WEISS (R. J.) and TAUER (K. J.), J. Phys.

Solids, 1958, 4, 135.

RADIUM

TOME

23,

OCTOBRE

Chem.

1962,

DIFFUSION STUDIES OF VACANCIES AND IMPURITIES

By
Department
Rsum.

of

Physics,

DAVID

University

LAZARUS, ,
of Illinois,

Urbana, Illinois, U. S. A.

Les dfauts ponctuels dans les mtaux ont dabord t introduits pour expliquer
de diffusion, et le succs des modles est gnralement mesur par le succs dans
la correlation des rsultats des mesures de diffusion. Dans cet article, on passe en revue lutilisation de la diffusion comme instrument dtude des imperfections, et on cherche dfinir les limites
de la validit des modles thoriques la lumire des tudes exprimentales de la variation, en
fonction de la temprature, de la pression et de la masse, de la diffusion dans un ensemble de
mtaux purs et de solutions solides.
2014

les phpomnes

Point defects in metals were first introduced to explain diffusional phenomena,

Abstract.
and the success of the models is generally measured by the success in correlating results of diffusion
measurements. In this paper, the use of diffusion as a tool to study imperfections will be reviewed,
and an attempt made to assess the limits of validity of theoretical models in the light of experimental studies of the temperature, pressure, and mass dependence of diffusion in a variety of
pure metals and solid solutions.
2014

Diffusional phenomena are

1. Introduction.
basic to reactions in metallic systems. Diffusion
limits the rate of phase transformations, solubility,
creep, grain growth, and recrystallization. Diffusion rates dictate whether a material will be
useful in a given environment, as in high temperature reactors, under high flux conditions, or completely useless, as in corrosive atmospheres. Technical interest in the field, therefore, has always been
-

lzigh.
From a purely scientific viewpoint, the most
important problems have been associated with deli-

neating specific mechanisms for diffusion which

permit the observed large flues of matter without
perturbing the essentially perfect lattice structure.
Of the many mechanisms suggested to explain diffusion, the concept of mobile point defects, particularly interstitials and vacancies, has proven most
viable. Since point defects were essentially
invented " to explain diffusion, it is perhaps
appropriate to consider how diffusional measurements have been useful as, a tool for studying
point defects in various systems,.
In homogeneous systems, the diffusion coefficient,