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. Novello Copley'
. .
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~
".,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
596
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.
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.
Figure 1. Binary eutexia. On, O B are the triple points and CA, Cs are
the critical points of A and B, respectively.
597
(Constant P, 2 Po)
Figure 2 .
Iroboris 9ection. mt
Ps, of
Figure 1.
598
+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
Sir SI.
Cornpore
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.
599
Pressore/
kg cm-a
Melting-point/'C
Diph~nylUrethan
amme
-EutecticTE/'C
zx
urethan
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
Figure 7.
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).
~~
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
601
' 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).
".
".
Literature Cited
(1) GUTRRIE,
F.,Phil. Mag., 151, 17, 462 (1884).
(2) GUGGENHEIM,
E . A,, Trans. Faraday Soc., 51, 876 (1955).
(3) BOWDEN,
S. T., "The Phase Rule and Phase Reactions,"
Mctcmillan & Co., Ltd., London, 1938, p. 149.
(4) PRIGOGINE,
I., AND DEFAY,R., "Chemical Thermodynamics," translated by EVERETT,D. H., Longmans, Green &
Co., Ltd., London, 1954, p. 178.
(5) EPSTEIN,P. S., "TextbookoiTherm~dynamic~,"
John Wiley
& Sons, Inc., New York, 1937, p. 196.
(6) ZERNIEE,J., "Chemical Phase Theory," Ae. E. Kluwer,
Deventer, The Netherlands, 1958, p. 76.
(7) PRIGOGINE
A N D DEFAY,op. eit., p. 364.
(8) FINDLAY,
A., CAMPBELL,
A. N., and SMITH, N. O., "The
Phase Rule and its Applioations," Dover Publications,
Inc., New York, 1951, p. 140.
(9) GUTHRIE,F., Phil. Mag., [5],6,105 (1878).
(10) Ibid., 141,49, 1 (1875).
602
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