Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 209–211

www.elsevier.com/locate/calphad

A rigorous proof of the Alkemade theorem

Dmitri V. Malakhov∗
Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada, L8S 4L7

Received 8 July 2004; received in revised form 5 August 2004; accepted 5 August 2004
Available online 21 August 2004

Abstract

The Alkemade theorem avers that if primary crystallization areas of two stoichiometric phases have a common boundary, then along
this boundary temperature is maximal at the point where it is crossed by a straight line connecting the composition points of these phases.
The proof of the theorem presented in this work is rigorous in that sense that it does not invoke a graphical argumentation.
© 2004 Elsevier Ltd. All rights reserved.
Keywords: Alkemade theorem; Adjacent primary phase regions

1. Introduction (or its continuation) corresponds to the maximal temperature

along the intersection of two liquidus surfaces. An
equivalent formulation states that the direction of falling
Let us consider a ternary system. At the liquidus
temperature on the boundary curve is always away from the
temperature, liquid may be in equilibrium with one, two or
Alkemade line.
three solid phases. If it is in equilibrium with one phase, this
Alkemade employed geometrical considerations for
phase is called a primary phase. A locus of compositions
illustrating the validity of the theorem, but the argumentation
for which a given phase is a primary phase is termed a
invoked in [1] cannot be regarded as a rigorous proof.
primary phase region (area) or a region (area) of primary
Although the theorem was formulated more than a century
crystallization. An entire liquidus surface is formed by
ago, a punctilious proof has not been discovered in the
individual smooth liquidus surfaces corresponding to these
literature. The following historical analogy can be perceived.
primary phase areas. If the regions of primary solidification
Schreinemakers, who was studying isothermal isobaric
of two phases α and β are adjacent, then the corresponding
sections of phase diagrams, formulated the rule later named
liquidus surfaces are adjoining. Their intersection is a curve
in his honor [2]. A rigorous thermodynamic proof that on
in the x 2 –x 3 –T space. A projection of this curve on the
isothermal and isoplethal sections extrapolated one-phase
concentration triangle, i.e. on the x 2 –x 3 plane, is named
field boundaries either both fall inside a three-phase field
a boundary curve. Although information on temperature
or both pass into two-phase regions was suggested 73 years
along the intersection of two liquidus surfaces is lost in its
later [3] for ternary systems. Ten more years had passed
projection, the boundary curve has an interesting attribute.
before it was shown that Schreinemakers’ rule remained
Let us assume that α and β are stoichiometric phases. Let
β β valid whatever the number of components [4], i.e. that
us connect two points (x 2α , x 3α ) and (x 2 , x 3 ) representing extrapolated n-phase field boundaries either both fell inside
their compositions with a straight line, which is known as an (n + 2)-phase field or they both extended into (n + 1)-
the Alkemade line. The Alkemade theorem [1] says that a phase regions.
point of intersection of this line with the boundary curve
Elaborating of the analytical proof presented in this
work is believed to be interesting on its own merits. The
∗ Tel.: +1 905 525 9140x24308; fax: +1 905 528 9295. proof is also deemed instructive from the pedagogical
E-mail address: malakhov@mcmaster.ca. viewpoint since the Alkemade theorem is touched on in

0364-5916/$ - see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.calphad.2004.08.002
210 D.V. Malakhov / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 209–211

graduate and sometimes even in undergraduate courses on Expression (9) shows how temperature changes along the
thermodynamics and phase diagrams. intersection of two liquidus surfaces. Let us demonstrate that
at the point of intersection of the Alkemade line with the
boundary curve, the right-hand side of (9) is equal to zero.
2. Proof of the theorem
Firstly, let us realize that for any point (x 2 , x 3 ) belonging to
the Alkemade line the following two conditions are fulfilled:
Let us reiterate that α and β are stoichiometric phases
β
having adjacent primary phase regions. Two respective x 2 − x 2α x 2
liquidus surfaces are defined by the following equations: x 2α − x 2 = (x 3α − x 3 ) β
≡ (x 3α − x 3 ) (10)
x3 − x 3α x 3
F α (x 2 , x 3 , T ) ≡ G + G 2 × (x 2α − x 2 ) β
β β x − x 2α β x 2
+ G 3 × (x 3α − x 3 ) − G α = 0 (1) x 2 − x 2 = (x 3 − x 3 ) 2β ≡ (x 3 − x 3 ) . (11)
β x3 − x 3α x 3
F β (x 2 , x 3 , T ) ≡ G + G 2 × (x 2 − x 2 )
β
β
+ G 3 × (x 3 − x 3 ) − G β =0 (2) If x 3α = x 3 , the relations (10) and (11) are inoperative and
the following expressions have to be used instead:
where x i is the mole fraction of the i -th component in liquid,
G is the molar Gibbs energy of the liquid phase, G ω is x 3α − x 3 = (x 2α − x 2 )x 3 /x 2 (12)
the molar Gibbs energy of the phase ω, ω = α or β, β
x3 − x3 =
β
(x 2 − x 2 )x 3 /x 2 . (13)
G i ≡ ∂ G/∂ x i . The intersection of these liquidus surfaces
is a line, along which the liquid phase L coexists with α and It is immaterial what particular set of equations, (10) and
β. For finding a location of the line, one has to choose an (11) or (12) and (13), is employed in subsequent derivations.
independent variable among x 2 , x 3 and T and then solve the Let us take the partial derivatives of F α and F β in the
system of Eqs. (1) and (2). numerator of (9):
Mathematically, the situation is very close to the case
where equilibrium between two binary solution phases γ F2α = G 22 (x 2α − x 2 ) + G 23 (x 3α − x 3 ) (14)
and δ is calculated via the solution of the following system F3α = G 23 (x 2α − x 2 ) + G 33 (x 3α − x 3 ) (15)
of equations: β β β
F2 = G 22 (x 2 − x 2 ) + G 23 (x 3 − x 3 ) (16)
γ γ γ
F1 (x 2 , x 2δ , T ) ≡ µ1 (x 2 , T ) − µδ1 (x 2δ , T ) =0 (3) β β
F3 = G 23 (x 2 − x 2 ) + G 33 (x 3 − x 3 )
β
(17)
γ γ γ
F2 (x 2 , x 2δ , T ) ≡ µ2 (x 2 , T ) − µδ2 (x 2δ , T ) = 0. (4)
where G i j ≡ ∂ 2 G/∂ x i ∂ x j . Insertion of (14)–(17) into the
Phase boundaries can be determined if one of the variables numerator of (9) yields
γ
x 2 , x 2δ and T is declared an independent variable and
β β β β
the system of Eqs. (3) and (4) is solved. Not only the F2 F3α − F2α F3 = (G 22 (x 2 − x 2 ) + G 23 (x 3 − x 3 ))
phase boundaries but also their slopes can be computed. × (G 23 (x 2α − x 2 ) + G 33 (x 3α − x 3 ))
Let us, for the sake of determinacy, select temperature as
− (G 22(x 2α − x 2 ) + G 23 (x 3α − x 3 ))
the independent variable and differentiate (3) and (4) with
β β
respect to it: × (G 23 (x 2 − x 2 ) + G 33 (x 3 − x 3 )). (18)
γ γ
∂ F1 /∂ T + ∂ F1 /∂ x 2 × dx 2 /dT Substitution of (10) and (11) into (18) results in
+ ∂ F1 /∂ x 2δ × dx 2δ /dT = 0 (5) β β β
F2 F3α − F2α F3 = (x 3 − x 3 )(G 22 x 2 /x 3 + G 23 )
γ γ
∂ F2 /∂ T + ∂ F2 /∂ x 2 × dx 2 /dT × (x 3α − x 3 )(G 23 x 2 /x 3 + G 33 )
+ ∂ F2 /∂ x 2δ × dx 2δ /dT = 0. (6) − (x 3α − x 3 )(G 22 x 2 /x 3 + G 23 )
β
The solution of the system of Eqs. (5) and (6) gives the
γ
× (x 3 − x 3 )(G 23 x 2 /x 3 + G 33 ). (19)
slopes dx 2 /dT and dx 2δ /dT . The same technique is used
here for making the first step towards the proof of the Let us present the right-hand side of (19), which is obviously
Alkemade theorem. Let us use x 2 as the independent variable equal to zero, in the following form:
and differentiate (1) and (2) with respect to it: β β
F2 F3α − F2α F3 = (G 23 x 2 /x 3 + G 33 ) × 0. (20)
F2α+ FTα × dT /dx 2 + F3α × dx 3 /dx 2 = 0 (7)
β β β The molar entropy of the liquid phase, S, and the molar
F2 + FT × dT /dx 2 + F3 × dx 3 /dx 2 = 0 (8) entropies of the stoichiometric phases, S α and S β , appear
where Fiω ≡ ∂ F ω /∂ x i , FTω ≡ ∂ F ω /∂ T . By solving the in the partial derivatives of F α and F β with respect to
system of Eqs. (7) and (8), one obtains temperature in the denominator of (9):

dT
β
F F α − F2α F3
β FTα = −S + G 2T (x 2α − x 2 ) + G 3T (x 3α − x 3 ) + S α (21)
= 2 3β β
. (9) β β β β
dx 2 FTα F3 − FT F3α FT = −S + G 2T (x 2 − x2 ) + G 3T (x 3 − x3) + S (22)
 D.V. Malakhov / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 209–211 211

β
where G iT ≡ ∂ 2 G/∂ x i ∂ T . By using (15), (17), (21) and them, F3α and F3 , are given by (15) and (17). The
(22), the denominator of (9) can be simplified: remaining six derivatives are obtained by differentiating
β β (14)–(17):
FTα F3 − FT F3α = (G 23 x 2 /x 3 + G 33 )(−Sx 3
α
β F22 = G 222(x 2α − x 2 ) − G 22 + G 223 (x 3α − x 3 ) (29)
+ S α (x 3 − x 3 ) − S β (x 3α − x 3 )). (23) α
F23 = G 223(x 2α − x2) + G 233 (x 3α − x 3 ) − G 23 (30)
If (20) and (23) are substituted in (9), the following α
expression is obtained: F33 = G 233(x 2α − x2) + G 333 (x 3α − x 3 ) − G 33 (31)
β β β
dT 0 F22 = G 222(x 2 − x2) − G 22 + G 223 (x 3 − x 3 ) (32)
= β
.
β β β
dx2 x3 (−S + S (x3 − x3 )/x3 − S β (x3α − x3 )/x3 )
α
F23 = G 223(x 2 − x2) + G 233 (x 3 − x 3 ) − G 23 (33)
(24) β β β
F33 = G 233(x 2 − x2) + G 333 (x 3 − x 3 ) − G 33 (34)
Since the molar entropy of liquid is greater than the molar
where G i j k ≡ ∂ 3 G/∂ x i ∂ x j ∂ x k . By making use of (29)–(34)
entropies of the stoichiometric phases α and β, the term in
and (10) and (11), one can reduce the numerator of (28) to a
the parentheses multiplied by x 3 in the denominator of (24)
very compact form:
is always negative. Thus, it has been shown that temperature
has an extremum at the point of intersection of the Alkemade (G 23 x 2 /x 3 + G 33 )x 3 (G 22 + 2G 23 × dx 3 /dx 2
line with the boundary curve. Now, it is necessary to prove + G 33 × (dx 3 /dx 2)2 ). (35)
that it has the maximum in this point.
Let us differentiate (7) remembering that x 2 is the Substitution of (35) and (23) in (28) yields
independent variable: d2 T G 22 + 2G 23 × dx 3/dx 2 + G 33 × (dx 3 /dx 2)2
= β
.
α
F22 α
+ F2T ×
dT
+ FTα ×
d2 T
α
+ F23 ×
dx 3 dx 22 −S + S α (x 3 − x 3 )/x 3 − S β (x 3α − x 3 )/x 3
dx 2 2
dx 2 dx 2 (36)
2

α d x3 α α dT α dx 3 dT It has already been shown that the denominator of (36)
+F3 × + F2T + FT T × + F3T ×
dx 22 dx 2 dx 2 dx 2 is always negative. Since G 23 (dx 3 /dx 2 ) = G 22 and

 G 33 (dx 3 /dx 2 )2 = G 22 , the numerator of (36) is equal to
α α dT α dx 3 dx 3
+ F23 + F3T × + F33 × =0 (25) 4G 22 , which is indeed positive because the Hessian of the
dx 2 dx 2 dx 2
Gibbs energy is positive definite. The inequality d2 T /dx 22
where Fiωj ≡ ∂ 2 F ω /∂ x i ∂ x j , FiT
ω ≡ ∂ 2 F ω /∂ x ∂ T and
i < 0 means that temperature is maximal at the point where
ω 2 ω
FT T ≡ ∂ F /∂ T . Since dT /dx 2 = 0, (25) can be
2 the Alkemade line and the boundary curve cross each other.
drastically simplified: The theorem has thus been proven.
FTα × d2 T /dx 22 + F3α × d2 x 3 /dx 22 = −F22
α α
− 2F23
α Acknowledgements
× dx 3 /dx 2 − F33 × (dx 3 /dx 2)2 . (26)
An expression similar to (26) can be obtained if (8) is Mentioning of the Alkemade theorem in contemporary
differentiated with respect to x 2 : scientific literature is almost never accompanied by a
β β β β reference to the original publication. The author is grateful
FT × d2 T /dx 22 + F3 × d2 x 3 /dx 22 = −F22 − 2F23 to Ms. Shawn Leslie (H.G. Thode Library of Science and
β
× dx 3 /dx 2 − F33 × (dx 3 /dx 2)2 . (27) Engineering, McMaster University) for her help in finding
this paper by tracing cross-references down to the primary
Solution of the system of Eqs. (26) and (27) gives
  source.


2 
d2 T β β dx β dx
= F3α F22 + 2F23
3 3
+ F33
dx 22 dx 2 dx 2 References


 
β α α dx 3 α dx 3 2
− F3 F22 + 2F23 + F33 [1] A.C. van Rijn van Alkemade, Zeitschrift für physikalische Chemie 11
dx 2 dx 2 (1893) 289–327.
[2] F.A.H. Schreinemakers, Die Heterogenen Gleichgewichte Vom
β β
× [FTα F3 − FT F3α ]−1 . (28) Standpunkte Der Phasenlehre, Die Ternären Gleichgewichte, Part 1
“Systeme Mit Nur Einer Flüssigkeit Ohne Mischkristalle Und Ohne
Let us note that the denominator of (28) is identical to the Dampf”, vol. 3, Friedr. Vieweg & Sohn, Braunschweig, 1911.
denominator of (9), which is given by (23). For evaluating [3] M. Hillert, International Metals Review 30 (2) (1985) 45–67.
the numerator of (28), eight derivatives are needed. Two of [4] A.D. Pelton, Journal of Phase Equilibria 16 (6) (1995) 501–503.