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George

. Novello Copley'
. .

Liverpool College of Technology


England

Eutexia

A n intimate tmo-phase mixture consisting of 23.6% anhydrous sodium chloride and 76.4% ice
melts, under atmospheric pressure, at -21.1C to give
a liquid solution of salt in water having the same composition as the initial two-phase mixture. Moreover,
a liquid solution of salt in water, of this composition,
freezes at -21.1C under atmospheric pressure to give
a two-phase mixture of ice and solid salt. To these
and related phenomena Frederick Guthrie (1) applied
the term "eutexia." He wrote:
The main argument of the present communication hinges upon
the existence of oompound bodies, whose chief characteristic is
the lowness of their temperature of fusion. This property of the
bodies may be called Eutexia,* the bodies possessing it eutectic
*Used in very much this sense by Aristotle. I should have
preferred the word hypolytic; but I am instructed that, although
sanctioned by its use in chemistry, this employment of ' r 6 is not
strictly admissible" ( 1 ) .
-

p~

bodies or eutecticios (r'rjnrrv). It is a t once apparent that the


cryohydrates are essentially eutectic. I t will, however, perhaps
be better t o make the term more useful by limitingits spplieation.
I shall use it, and should like it to be used by others, for bodies
made up of two or more constituents, which constituents are in
such proportion t o one another as to give the resultant compound
body a minimum temperature of liquefxtion-that is, a lower
temperature of liquefaction than that given by any other proportion. Here, again, the cryohydrates completely satisfy the
definition. But i t will be shown that they constitute only one
term of a series, that their melting or liquefaction is quite continuous with the so-called fusion of mixed metals or salts, and that the
eutectic alloys of metals, many of which have been long imperfectly known, and the eutectic alloys of salts, which I shall describe ($5 207-229), are the perfect homologues of the cryohydrates. Let me, in a word, invite my readers, while looking
upon water as fused ice, t o trace the analogy between the behaviour towards solids of water on the one hand, and some other
f,..d
.-""-

".,h.tanm
""w""u..ub

"- ,ha
"-- -+ha"
""-u.,
An

The majority of
textbooks follow G
~
usage when they say that euteclic means "to melt well"
(.2,) or "easv meltincr" IS).
~ .but, the erroneous o~iuion
has also been expressed that: " . . . eutectic, derived
from the Greek, means "well interwoven" and signifies
that a t this concentration the solid which is formed is
an intimate mixture of crystals" (4). Used as a noun
euteclic means an intimate mixture of two or more kinds
of crystals which exhibits eutexia ( I ) , and to be more
explicit many authors now speak of this as a eulectic
mixture. Euleclic is used very frequently as an adjective, as in eutectic liquid, eutectic composition, eutectic
poinl, eutectic temperature, euteclic transformalion, euteclic horizontal, and eutectic reaction isotherm. Euleclic
line has been given a t least two meanings: (a) a line in
which two liquidus surfaces, each representing a liquid
solution saturated with a solid solution, intersect in a

'Present address: Education Ofiees, 14 Sir Thomas Street,


Liverpool, 1, England.

596

/ Journal of Chemical Education

ternary system (5) and (b) the line showing the variation of point E (Fig. 2) with temperature, pressure, and
composition (6),or as a line a t all points along which
the Gihbs free energy of transfer of the two components
from the solid state to the solution is zero (7).
It has been said (8) that Guthrie regarded eutectics
as definite chemical compounds, but my reading of his
papers does not lead me fully to subscribe to this view.
Guthrie examined a large number of eutectics in
which ice was one of the constitutent solids (9). I n
his original paper "On Salt Solutions and kttached
water" he wrote (lo)
is clear that if ice and the hydrated or anhydrous salt sepsrstetl
out in
not combined, but merelv mixetl
DroDortion
with one another, ihe mass would have a constant solibifyingand melting.point; and this n-ould be below zero t o the same
amount as would be reached on mixing artificially the anhydrous
or hydrated salt with ice in the same proportion. ~~t when
have distinct and unchangeable relation by weight demanded by
the constancy of the solidifying- and melting-point, we have undoubtedly a numerical physical relation as fixed and no less important than the points of fusion or degrees of solubilities. And if,
as I shall show, all the hydrates formed under these conditions
have distinct crystalline forms, w-e have all the conditions of
chemical association; s t least I know of none other. It is an essential element in the existence of these compounds that they
can only exist in the solid state below 0-C. Hence I propose to
callthemforthe present "cryohydrate~."~At the ordinary temperatures they melt in their own water of erystallizat,ion and
appear as ordinary solutions never saturated. And when once
the proportion between the salt and the water in a cryohydrate
has been found, the cryohydrate can he formed in any quantity
by dissolving the salt in water in the required proportion. Such
a solution shows no sign of yielding up ice or anhydrous salt (or
other hydrate) until its temperature, on being lowered, reaches
a. certain temperature peculiar to %he salt (unless under supersaturation); it then solidifies as a whole, mainti~iningthroughout
that constant temperature. Above this temperature (that is, in
the melted state) it is precisely in the same predicament,
~
~
~
~
~
,
~
6s a salt melted in its o m water of crystallization.

Guthrie tabulatedz the formulas of twenty-nine


salts or salt hydrates together with his observations of
the temperatures of solidification and the molecular
ratios between anhydrous salt and water of their
cryohydrates. The latter property of a cryohydrate he
called (11) its aquacalent or water-worth and it is clear
from his table that it is not always an integer. He
also made the following statement (11) about waterworths:
It may he perhaps more than accidental that the numbers of
molecular water-worths show a distinct tendency to he multiples
of 0.5. For my o m part, recognizing the posfiihle range of
analytical error, I for the present distinctly farhear to express any
According to Bowden, S. T. (Ref. (S), p. 222), crvohydrale
means frost water from the Greek. F. Guthrie also introduced
thetermcryogen: "By Cryogen I mean an appliance far obtaining a temperature below 0C. I n this paper it always signifier;a
freezing-mixture." (Phil. Mag., 141, 49, 206 (1875)).

opinion as to whether we are here dealmg with the same physical


force which constitutes a ohemical attraction, and which regulates
the integral ratios of molecular combination as most chemists
appear to understand the term-%= whether it is s. distinct or distinctly conditioned force binding the salt and water together in
quite a new ratio, or a ratio which can only be brought t o the
chemical one by multiplication by constants, a t present arbitrary.

Guthrie also wrote the following words concerning


eutectic alloys and the geological significance of eutexia:
The preconoeived notion that the alloy of minimum temperature
of fusion must have its constituents in simple atomic proportionthat it must be a chemical compound-seems to have misled
previous investigators. Such misconception could ~carcelyhave
arisen if the existence and properties of the cryohydrates had been
known (1s).
We know already, indeed, very many instances in which the
mixture of two bodies has a lower melting-point than either of its
constituents. Whst must happen then, if a mass of molten rock,
such as a silicate, is saturated a t a high temperature with another
silicate? When the mixture cools, the second may separate out
in the solid form, perhaps as quartz, perhaps as feldspar, or what
not. Anon, a t a certain lower temperature, solidification take8
place between the medium and the dissolved rock in d e h i t e
proportion-definite, though perhaps not necessarily in chemical
ratio, but presenting that mineralogical ratio which is so striking,
and which has not hitherto been satisfactorily explained (IS).

I t was also realized quite clearly by Guthrie that


enormous pressure would alter the composition of a
cryohydrate, for he wrote:
Without doubt the cryohydrates would vary in composition if
they were formed at enormous pressures; for the variation
effected by pressure in the freezing-point of water is not likely
to be precisely the same as the variation in the solidifying of a
salt out of a solution (14).

It seems evident that Frederick Guthrie was not insistent in regarding eutectics as solids possessing all the
properties of compounds. It is surprising, therefore,
that errors in the construction of phase diagrams which
originate in the belief that eutectics are compounds
should still persist.

always find that in a binary eutectic-type alloy series


hardness, electrical resistivity, density, and other properties vary smoothly, if not linearly, with composition,
from the value of the property for one pure crystal to
its value for the other (15). Such results show that
the alloy of eutectic composition is in no way to be
regarded as distinct from any other mixture of its two
solid phases under the same conditions.
X-ray crystallography is a means of deciding with
certainty whether a solid is a polyphase mixture, a
solid solution, or a compound (16). The X-ray method
shows beyond doubt that a binary eutectic is a mixture
of two kinds of crystals. Although eutectics are usually
non-stoichiometric they are not Berthollide compouuds,
which are solids containing defect crystal lattices, and
not mixtures of solids. Since eutectics are mixtures,
it is clear that they cannot be regarded as non-stoichiometric compounds.
Thermodynamics of Eutexia

A most important reason for regarding a eutectic as a


mixture of solid phases is that it leads to predictions,
based upon thermodynamical reasoning, which are in
full agreement with the observed equilibrium properties
of eutectic systems as well as showing the analogies
between these systems and other systems treated by
phase theory.
The equilibrium relationships between pressure, temperature, and composition (expressed as a mole fraction)
for a binary eutectic system (components A, B) are
depicted, in diagrammatic form, in Figure 1; A and B
are assumed to be completely immiscible in the solid
state (Sj and completely miscible in the liquid (F)
and gaseous (G) states. I t is possible to have a fourphase equilibrium in this system, comprising solid A
(S,), solid B (S,), a liquid solution of A and B (E.),
and a gaseous solution of A and B (G.). According to

Mixtures and Compounds

The study of eutexia affords a splendid opportunity


for the reconsideration, from a more advanced standpoint, of the student's earlier learning about mixtures
and compounds. There is much evidence that a binary
eutectic is a mixture of two crystalline phases and
neither a one-phase mixture (solid solution) nor a
crystalline compound. The physical and mechanical
properties of a mixture of two crystalline phases would
be expected to be the average of the corresponding
properties of the separate crystals, under the same conditions, weighted according to their proportions in the
mixture. The maximum stability of a mixture of
solids, at constant temperature (T) and pressure (P),
is attained when its Gibbs free energy (F) is a minimum.
Since F = E
P V - TS, F is a minimum when its
energy (E) and volume ( V ) are as small as possible
and its entropy (Sj is as great as possible. Although
the entropy of such a mixture will increase with the
comminution of the solids in it, this state will not
necessarily be the most stable one, for comminution
will also lead to increases in E, and possibly in V , on
account of the effects of the shapes, distribution, and
surface areas of the two kinds of crystals. For these
reasons the simple weighted average result will not he
precisely true in practice. Nevertheless, metallurgists

Figure 1. Binary eutexia. On, O B are the triple points and CA, Cs are
the critical points of A and B, respectively.

Gibbs' phase rule such a system must be nullvariant,


that is, all its intensive properties are naturally determined and none can be arbitrarily assigned. In particular, the temperature (T,), pressure (P.),and the compositions of the liquid (x&) and gaseous (y&)
phases are all naturally fixed for this four-phase equilibVolume 36, Number 12, December 1959

597

(Constant P, 2 Po)

Figure 2 .

Iroboris 9ection. mt

Ps, of

Figure 1.

rium; the line through Go, E. runuing parallel to the


composition axis represents this situation in Figure 1.
For nearly all eutectic systems the pressure Po, which
is the sum of partial pressures of A and B, is extremely
small, whereas the pressures at which eutexia is normally considered are a t least one atmosphere. It is
therefore customary to look upon eutectic equilibria
as condensed systems from which, owing to compression,
the gaseous phase is e ~ c l u d e d . ~The maximum number
of co-existent phases for such a condensed system is
three, namely S,, S,, and a liquid solution (El; and the
variance is unity. The dotted isobaric section of
Figure 1 represeuts such an equilibrium for the constant
pressure, P,, of the isobar by the line through E
parallel to the composition axis. The familiar isobaric
section shown dotted in Figure 1 is reproduced, for
clarity in subsequent discussion, in Figure 2. Since
Pe is normally fixed and equal to the pressure of the
atmosphere, TE (euteclic temperature) and X B (eulectic
~
compositia) are also naturally determined. Point
E is now termed a eutectie point although Guthrie (17)
called it the "point of reflexure."
Three two-phase areas, SAF,SnF, and SASn,are
represented in Fignre 2. To these, as well as to similar
areas on other phase diagrams, the quantitative phase
rule called the tie-line relationship applies and gives
information not given by Gibbs' phase rule. In particular, the tie-line rule applies to all mixtures of SAand Sn
iucluding the mixture of eutectic composition X B ~ .
Because the tie-line relationship concerns only twophase equilibria it does not apply to the eutectic threephase line through TEE,and objection must he made to
any designation of this line as a tie-line (18). The
tie-line rule fails to hold on the eutectic three-phase
line in the sense that if the gross composition of such a
three-phase system at T,, PE is given, it is not possible
to state, without further information, the proportions
For evidence t o the contrary see Petrucci, R. H. (Ref.33).)
See also the disoussion of euteotic fusion later in this article.

598

Journal o f Chemicol Education

of its three phases; the system is an instance of what


Pierre Duhem called an indifferent state (19).
The criterion of constant melting point is neither
necessary nor sufficient to characterize a compound.
That it is not necessary is shown by the fact that compounds not possessing constant melting points are
known: (a) the addition compound formed by benzene
and picric acid melts incongruently (meritectically)
over a range of about 7C ($0); (b) in ternary systems
neither semi-congruently melting nor incongruently
melting compounds satisfy the criterion (21). That it
is not sufficientis shown by the fact that solid solutions
with stationary melting points have this property (22).
Hence the constant melting point of a eutectic neither
proves nor disproves that it is a compound. It remains
of interest to compare the fusion of a binary eutectic
with the fusion of a binary compound. The following
processes, reading from left to right, all occur, at constant temperature and pressure, with increases in
enthalpy and in entropy and represent indifferent
states:
(i) congruent melting: S, = F
(ii) meritectie melting: S, = S2
(iii)eutectic melting:
8, + S2

+F

-F

I n (i), (ii), and (iii) S may represent solid solution instead of pure solid; in this case (i) represents a stationary melting solid solution, (ii) represents peritectic
melting, while (iii) still represents eutectic melting and
indeed, it is this kind of eutectic, involving solid solutions, that is most commonly encountered in practice.
Figure 3, which should be cornparedwith Figure 2, shows
the isobaric condensed phase diagram of a binary eutectic system involving solid solutions (S,, SI). Schemes
(i), (ii), and (iii) also show that eutectic melting is
more akin to meritectic and peritectic melting than t o
congruent melting, in that melting of types (ii) and
(iii) both involve two solid and one liquid phase in a
binary system. On phase diagrams this analogy is

Figure 3. Binary eutectic system with solid rolvtionr


with Figure 2.

Sir SI.

Cornpore

represented by eutectic, meritectic, and peritectic


three-phase lines. These are not the only three-phase
equilibria possible in binary systems: F. N. Rhines (83)
has listed twenty-six types of such equilibria, of which
his type c is depicted on the front isothermal section
of Figure 1, on which a line parallel to the composition
axis represents the equilibrium between solids SA,SB,
and a gas of composition represented by point 7 . An
important type of three-phase equilibrium encountered
in binary alloy systems involves three solid solutions
(81 S2 = S3); because of its close analogy to (iii)
it is said to be eutectoid.
The possible equilibria between two immiscible
solids, A and B, and a liquid solution of A and B, have
been studied in terms of the intensive variables temperature (T), molar Gibbs free energy ( F ) , and mole
fraction (xH) (84). The molar Gibbs free energy of an
ideal solution is

Figure 5.

where F;, F; are the constant molar Gibbs free energies of the pure liquids A and B a t the temperature and
pressure of the solution. Function (1) has the form
shown in Figure 4 and has the property that the tangent
to the curve at X makes intercepts on the A and B
axes (xB = 0 and 1, respectively) equal to FAand FB
(84).
( I ; P constant )

Figure 4.

Gibbs free energie. of solutions of A and B

According to Gibbs' phase rule a binary system


existing in one phase (the liquid solution) has a variance
of three, so that a system represented by X (Fig. 4) is
completely determined, apart from its amount, by the
temperature and pressure of the diagram and by either
the value of XB or F for the solution. If the solution
be in equilibrium with SA,say, then the variance becomes two, and there can be only one point X (Fig. 4)
for which this is possible. This point on the curve is
found by drawing the tangent to the curve from the
point (FAS,XB = O), where FASis the molar Gibbs
free energy of SAat the temperature and pressure of the

Isobaric d i o g r m of F-T-XB relations in o binary eutectic syrtem.

diagram. Let the pressure from hence be assumed to


be fixed and let the temperature T for Figure 4 be considered in relation to the melting points (TAPTB) of A
and B a t this fixed pressure. (i) If T > T,. > TB,
then FAS> F k and FBS> F;, and no tangents can be
drawn from points (FAS,XB = 0) and (FBS, x,, = 1)
to the curve (Fig. 4). In these circumstances the
liquid phase is always unsaturated at all compositions
and is represented by the area above TA in Figure 2.
(ii) Similarly, if TA > T > TB, only one tangent, that
from (FAs,0) can be drawn to the curvc and the solution
is saturated with SA. This situation is rep1,esmted by
an area between parallels to the composition axis
through TAand TBin Figure 2. (iii) If TA> T, > T,
tangents can be drawn from both (FAS,0) and (FgS, 1)
to the curve. This situation is represented by areas
between the lines parallel to the composition axis
through TBand TEin Figure 2. When the two tangeuts
coincide, SAand SHwill be in equilibrium with one
another and this is the interpretation of the eutectic
phenomenon. At temperatures lower than TE the line
joining (FAS,0) and (FsB, 1) lies below the solution
curve, corresponding to the fact that mixtures of SA
and S, are more stable than any systems involving
solutions. This situation is represented, in Figure 2,
by the whole of the area below the eutectic three-phase
line.
Some of the results which have just been discussed
are depicted in Figure 5. Departure of the solution of
A and B from ideality does not materially alter the
foregoing conclusions unless it leads to partial miscibility in the liquid state. Partial miscibility in the
solid state gives rise to Figure 3, the F - x diagram, at
T, and PE,for this case is given in Figure 6 which represents the equilibrium of the eutectic liquid (FE) with
eutectic solid solutions (S,E, S9E).
For the case in which the liquid phase is an ideal
solutior~and the solids A and B are immiscible it is
possible to calculate, with the help of thermodynamics,
values for T, and xBE(85).
Since a binary three-phase system such as a condensed eutectic system is univariant, it follows that
there must exist unique relations between any two of its
intensive properties. The more important of these
Volume 36, Number 12, December 1359

599

nents and on the eutectic temperature and composition


for the system urethan-diphenylamine are given in
the table. This table (27), which illustrates (3) and (4),
shows that although T,,like the melting-point of a pure
solid, is a function of pressure, a eutectic differs from a
compound in that its composition also varies with pressure.
Variation, with Pressure, of Eutectic Temperature and
Composition (27)

Pressore/
kg cm-a

Melting-point/'C
Diph~nylUrethan
amme

-EutecticTE/'C

zx

urethan

Microstructures o f Eutectic Alloys

Figure 6. Gibbr free energies of liquid and solid solutionr or functions


of composition a t the evtectic temperature and pressure.

relations are between (a) the eutectic temperature and


pressure and (b) the eutectic composition and pressure.
Relation (a) has the familiar form of the ClapeyronClausius equation,

which is usually only considered in connection with


univariant two-phase equilibria in unary systems. It
is not difficult to show that relation (a) is (86)

The temperature-composition diagram, a t atmospheric pressure, of the bismuth-cadmium system, is


given in Figure 7. It will be assumed that an alloy of
bismuth and cadmium is cooled quasi-statically, a t
constant gross composition, red = 0.3, from about
350C. The primary solid phase that separates,
starting a t about 250C and continuing until T, =
144C is reached, is bismuth, while a t T , solid bismuth
and solid cadmium separate in the proportions present
in the eutectic liquid (xcg = 0.55). When complete
solidification has occurred, the proportion of primary
solid bismuth to eutectic alloy is given by applying the
tie-line rule to the Bi(S)F two-phase area just above
T,, while the proportion of bismuth to cadmium in
the solid alloy is given by applying the tie-line rule to
the Bi(S) Cd(S) two-phase area just below T,. The
metallurgist is usually more interested in the former
result, which he refers to as the determination of the
proportions of the constitutents, than he is in the latter
result, which is the determination of the proportions

Equations (2) and (3) enable a comparison to be made


between melting, a t constant temperature and pressure,
in the case of (2) a pure solid (pis then the solid phase
and a is the liquid phase) and (ii) a eutectic mixture of
two pure solids. Equation (2) makes it clear that the
transformation concerned is that of one mole of solid
into liquid, whereas equation (3) makes it equally
clear that the corresponding transformation is that of
one mole of a mixture of two solids A and B to give a
liquid solution of the same composition. Thus, although equations (2) and (3) are both ClapeyronClausius equations applying to univariant equilibria,
they refer to physically distinct processes.
Relation (b) can be shown to be (26)

and it can also be shown (26) that the sign of this expression is that of the difference in the final bracket. The
effect of pressure on the melting point,s of t,he compo600

Journal o f Chemical Education

Figure 7.

lraboris evtectic phme diogram of the bismuth-cadmium system.

of the phases. The term constituent is used by metallographers to signify " . . .a characteristic and recognizable structure which can be identified as a unit in microscopic examination of a given material, and which
serves as a structural unit in determining the properties
of that material. A constituent must be carefully
distinguished from a phase or a component of the
alloy (28)." I n eutectic alloy systems the eutectic
constituent is a crystalline structure of eutectic composition. It is often found convenient to draw a dotted
line (ef) from the eutectic point e parallel to the temperature axis in the phase diagram (Fig. 7) to indicate the
composition of the eutectic constituent, but it is quite
erroneous, as is done in some textbooks, to draw this as
a full line in the manner that the solidus Tsi efee"Tcd,
the liquidus TsieTcd,the solvns4e'f', and the solvus eYf"
are drawn in Figure 7. Solidus, liquidus, and solvus
and similar curves on phase diagrams are boundaries
of two-phase areas in binary systems; ef is not such a
line. If it were, it would imply that four phases,
Bi(S), Cd(S), and solid and liquid of eutectic composition could partake in the eutectic equilibrium, so that,
contrary to what is observed, the eutectic temperature
and composition could not be varied by changing the
pressure, for such a system would be nullvariant.
When removal of heat takes place a t T,,the eutectic
liquid is converted into the eutectic constituent by the
simultaneous deposition of the two solids with which it
is in equilibrium. For this reason, the eutectic constituent is often a fine and intimate mixture of two
types of crystals and usually possesses, if an alloy,
great strength aud impact resistance. Nevertheless,
there is not one unique structure that can be regarded as
characteristic of all eutectic constituents. One obvious
reason why this should be so is that the relative proportions of the two solid phases in a eutectic constituent
vary widely; thus, the antimony-lead eutectic has
xpbP = 0.80, whereas the beryllium-silicon eutectic has
xsi' = 0.32. An extreme case is found in the timsilicon system where the eutectic composition is so near
to that of pure tin as to elude identification; in these
circumstances the system is referred to as monote~tic.~
The structures of a variety of binary eutectic constituents as revealed by polishing, etching, and microphotograph~are readily available (39).
X-ray examination of certain eutectics showed that
the particles of the two phases precipitated so that they
were favorably oriented with respect to each other (30).
The interfaces between the particles of the two solids
were arranged so as to give the easiest alignment of the
crystal planes of one phase with those of the other. It
is considered that the solidification of a eutectic alloy is
a process of much greater complexity than that of a
metal (31).
The fine structure of the eutectic constituent usually
observed re~resentsa condition of relativelv
sur" h i ~ h
face energy, but not necessarily, on account of the degree of order of the structure, of relatively high entropy.
In consequence it may be unstable with respect to a mixture of the same composition which has lover surface
energy and a more disordered structure. By keeping a
Thisconvenient termis so used by Rhines. (Ref. (IS), p. 34.)
The term monotectic is also used t o describe a binary threephase reaction in which a liquid phase loses heat t o yield another
liquid phase and a solid phase. (Ref. (la), p. 72).

eutectic alloy just below T, for a long period, growth


of its small crystal grains into larger aggregates occurs
and the typical appearance of the eutectic constituent
is thereby destroyed. Such eutectics are said to be
divorced and can be formed during the freezing of
eutectic alloys if the rate of removal of heat is slow
enough, as well as in the annealing of alloys subsequent
to solidification.
The melting of eutectic alloys is related to their
formation by crystallization; in fact, the first stage of
fusion, and the last stage of freezing, of a eutectic alloy
is always the fusion or freezing, a t t,he eut,ectic temperature, of the eutectic constituent. The mechanism by
which the solids in a eutectic constituent melt to give
the eutectic liquid as soon as the eutectic temperature
is reached has been raised by N. 0. Smith (52) and
discussed further by R. H. Petrucci (33). Professor
Petrucci considers that the process takes place via the
vapor phase, albeit the vapor pressures (or the partial
vapor pressures in air a t one atmosphere pressure)
involved may be extremely low. Yet it will be evident
from the account I have given of the thermodynamics
of eutexia that two solid phases present together in a
mixture should, on being heated a t T, and at some pressure high enough to prevent the appearance of vapor
(if necessary by using a special cylinder and piston),
melt to give eutectic liquid. I think that in this lies
the difficulty which was raised by Smith when he
wrote (33): "Why should an intimate mixture of A
and B begin to melt a t a temperature lover than the
melting point of both pure compounds, even when their
volatility is negligible?"
Anart from
the work cited bv Petrucci i33).
-,
.. I have
been unable to trace any reference to studies of the
mechanism of eutectic fusion, but studies have been
made of the analogous eutect,oid transformation, exemplified by
A~

~~

ferrite

+ cementite = austenite

in the iron-carbon system. The eukctoid transforlwation, S1S2(S3),is univariant, like the eutectic transformation SIX2(F),6under ordinary conditions, since both
involve a binary system of three phases. The inclusion
of either a liquid or a gaseous phase mould make the
eutectoid system nullvariant and this new phase might
be invoked in understanding the mechanism of the
SISz(Ss) transition if Petrucci's lead is followed. Rut
neither of these possibilities seems to have been so used
in the case of iron-carbon eutectoid t~ransformat~ion.
On the other hand, it appears that the interact,ion of a
solid solution of carbon in body-centered cubic iron
(ferrite) with the compound of formula Fe3C (cementite)
to give a solid solution of carbonin face-centered cubic
iron (austenite) is essentially a process of interstitial
diffusion of carbon atoms (34). I t therefore seems to
be a possibility that eutectic fusion is also capable of
interpretation as a diffusion process, interstitial or
otherwise.
Summary

An account has been presented of the reasons why a


binary eutectic must be regarded as a two-phase mix-

' Recently recommended notation for phase transitions


Volume 36, Number 1 2 , December 1 9 5 9

601

ture of solids and not as a Daltonide or Berthollide


compound. At the same time it has been emphasized
that this two-phase eutectic mixture is a structurally
important constituent of many metallic alloys. The
correct representation of these relationships in phase
diagrams has been discussed. It is clear that similar
ideas apply to higher order eutectic system^.^
Acknowledgments

I am grateful for the help I have received in the


preparation of this paper from correspondence with
Professor K. J. Mysels, Professor R. H. Petrucci, Dr. N.
0.Smith, and Dr. A. F. Wells. Raif Copley kindly
drew the diagrams.

' Guthrie (Ref. (I),p. 465) used the terms bi-, tri-, and tetr*
eutectic allovs where the terms binarv. ternarv. and ouaternsrv
eutectic alloy are now used; he also envisaged higher order
eutexia (Ref. (I:, p. 468).

".

".

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602

Journal o f Chemical Educafion

Ibid.. 141 49. 214 (1875)


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