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A cubic formalism for linking dilute and concentrated regions of ternary and
multicomponent solutions

Article  in  Mineral Processing and Extractive Metallurgy IMM Transactions section C · March 2012
DOI: 10.1179/1743285511Y.0000000026

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 A cubic formalism for linking dilute and
concentrated regions of ternary and
multicomponent solutions
K. T. Jacob*, B. Konar and G. N. K. Iyengar
A cubic formalism is proposed for representation of thermodynamic properties of ternary and
higher order systems that connect data on interaction parameters for solutes in metallic
solvents with available thermodynamic data on binary systems. Since most metallic alloys
have asymmetric excess Gibbs energies of mixing, a cubic expression in mole fraction is the
minimum requirement for representation of binary data. Subregular solution model provides
such a minimum framework. To link seamlessly with binary data, activity coefficients of solutes
in metallic solvents have to be represented by third-order interaction parameter formalism.
Although this requires values for a large number of interaction parameters, it is shown that
these parameters are interrelated and many parameters can be obtained from data on the
constituent binaries; only a limited number have to determined by measurement on ternary
systems. For example, for a ternary 1–2–3 rich in component 1, 18 interaction parameters are
required for defining the activity coefficients of both solutes 2 and 3 when third-order
formalism is used. However, when interaction parameter formalism is made consistent with
the Gibbs–Duhem relation, 11 separate relations are obtained between interaction
parameters, reducing the number of independent parameters to seven. Six of these
parameters can be obtained from the properties of the constituent binaries and only one
parameter need to be determined from measurements in the ternary system. The number of
independent parameters required becomes explicit when the excess Gibbs energy of mixing
of the ternary system is represented by a subregular type model with an additional ternary
parameter. Relations between coefficients of the subregular model and interaction
parameters are derived. Thus, the use of the cubic formalism does not necessarily require
additional measurements. The advantage is better representation of data at higher
concentrations compared to the quadratic formalism of Darken or the unified interaction
parameter formalism, which are essentially identical.
Keywords: Multicomponent solutions, Thermodynamics, Activity, Activity coefficient, Interaction parameters, Analytical representation

Introduction evaluated. Using these interaction parameters, activity

A large amount of data on interactions between two
solutes in liquid metallic solvents have been measured
over three decades starting from 1960s to assist
physiochemical analysis of refining and deoxidation
processes for ferrous and non-ferrous metals and alloys.
Most of these data are reported as Wagner (1962) first-
order interaction parameters, although in a few cases
second- and third-order parameters have also been
Department of Materials Engineering, Indian Institute of Science,
Bangalore 560012, India
*Corresponding author, email katob@materials.iisc.ernet.in
coefficient of a solute in multicomponent dilute solu-
tions can be estimated. Measurements of interaction
parameters in several metallic solvents have been
assessed and tabulated (Sigworth and Elliot, 1974a, b;
Sigworth et al., 1976, 1977). A theoretical approach for
calculating interaction parameters has been proposed
based on the pseudopotential formalism and free energy
of the hard sphere system (Ueno, 1988). At the pre-
sent time, the theoretical predictions are qualitative.
Unfortunately the interaction parameter formalism in its
simplest forms is thermodynamically inconsistent and
some methods for removing this inconsistency have been
discussed in the literature (Lupis and Elliot, 1966;
Darken, 1967; Schuhmann Jr, 1985; Pelton and Bale,

ß 2012 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 22 January 2010; accepted 11 August 2011 Mineral Processing and Extractive
48 DOI 10.1179/1743285511Y.0000000026 Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 1
 Jacob et al. A cubic formalism for temary and muliticomponent solutions

1986, 1990; Srikanth and Jacob, 1988, 1989a; Nagamori,    

L ln c2 L ln c2
1989). Analysis of thermodynamic measurements in ln c2 ~ ln c02 zX2 zX3 z
dilute solutions is constrained by the formalism selected LX2 X1 ?1 LX3 X1 ?1
for the representation of data. ! !
2 2
1 L ln c 2 1 L ln c 2
In parallel with this development, phase diagrams and X22 zX32 z
thermodynamic properties of a large number of binary 2 LX22 2 LX32
X1 ?1 X1 ?1
and some ternary alloys have been measured to assist ! !
alloy development, understand phase transformations, L2 ln c2 1 L 3
ln c 2
X2 X3 zX23 z
and provide a rationale for the development of thermal LX2 LX3 6 LX23
X1 ?1 X1 ?1
and thermomechanical processes. With the advent of ! !
computer coupling of phase diagrams and thermody- 1 L3 ln c2 2 1 L3 ln c2
namics, a large body of information has been integrated X2 X3 z X2 X32 z
2 LX22 LX3 2 LX2 LX32
and compiled across the full range of composition. X1 ?1 X1 ?1
!  n 
Based on this database, properties of multicomponent 3
3 1 L ln c2 1 n L ln c2
systems can be generated, thus reducing the amount of X3 z . . . z ½X2 z
6 LX33 n! LX2n X1 ?1
experimentation required for the development of com- X1 ?1
plex alloys for a variety of applications. It would be  
n! Ln ln c2
useful if the information available in chemical metal- X n{m X3m z
(n{m)!m! LX2n{m LX3m X1 ?1 2
lurgy on interactions between solutes in liquid metallic
 n 
solvents can be coupled with information on full range n L ln c2
of alloy compositions available in data banks. The X3 
LX3n X1 ?1 (1)
purpose of this article is to show that a cubic formalism
for dilute solutes in metallic solvents is the minimum
requirement for achieving integration with thermody- where components 2, 3 are the solutes and component 1
namic data for the full range of binary and ternary is the solvent. The infinite Maclaurin series expansion is
alloys. exact (Lupis and Elliot, 1966). The coefficients of the
Maclaurin series expansion are termed as free-energy
interaction parameters. Current limitations on experi-
Requirement for cubic formalism mental accuracy make it difficult to measure interac-
Since most alloy systems exhibit asymmetric behaviour tion parameters beyond the third-order. To justify a
with respect to composition, the simplest model that can truncation, the remainder term arising out of the
be used with reasonable generality for a binary system is truncation should be less than the estimated experi-
the subregular model of Hardy (1953). The representa- mental error. The truncated expressions are inexact
tion of partial thermodynamic properties of a compo- (Srikanth and Jacob, 1988). The first-order free-energy
nent in the subregular model requires terms involving interaction
  parameters
 defined
 by Wagner (1962) are
L ln c2 L ln c2
the cube of composition. Binary subregular solutions e22 ~ 3
LX2 X ?1 , e2 ~ LX3 X ?1 . The self-interaction
can be combined to form higher order systems, with or 1 1

parameter e22 represents the effect of concentration of

without ternary parameters. The need for higher order
terms is dictated by the nature of the system and the solute 2 on its own activity coefficient. The parameter
accuracy of data. can be obtained from binary thermodynamics of system
Any treatment of dilute solutions must include at least 1–2. The parameter e32 represents the effect of concen-
the cubic terms if they have to be incorporated into a tration of solute 3 on the activity coefficient of solute 2.
larger framework extending across a larger composition To derive a value for this parameter, measurements are
range. With the advent of concentrated alloys for required on the ternary system 1–2–3, where compo-
corrosion and erosion resistance in high temperature nents 2 and 3 are in the dilute domain.
technology, the study of solute interactions in multi- The second-order free-energy interaction coefficients
component systems to higher solute compositions has defined by Lupis and Elliot (1966) are
become necessary. A cubic formalism would fulfil this ! !
requirement. Before developing the cubic formalism, a 2 1 L2 ln c2 3 1 L2 ln c2
r2 ~ , r2 ~ ,
short review of the interaction parameter formalism and 2 LX22 2 LX32
X1 ?1 X1 ?1
methods of making it thermodynamically consistent, !
and Darken’s quadratic formalism (Darken, 1967a, b) 23 L2 ln c2
will be presented to provide historical continuity and r2 ~
LX2 LX3
X1 ?1
outline the evolution of the subject.
where r22 represents the second-order self-interaction
Interaction parameter formalism parameter obtained from measurements on the binary
Wagner (1962) suggested the interaction parameter system 1–2. The parameter r32 , representing the second-
formalism based on Maclaurin (Taylor) series expansion order effect of component 3 on activity coefficient of
for the activity coefficient of a solute expanded at the component 2, is obtained from measurements in ternary
composition corresponding to the pure solvent. The system 1–2–3. The parameter r23 2 , which represents the
formalism has been cast in a more general framework combined effect of components 2 and 3 on activity
and extended by Lupis (1983). The series expansion for coefficient of 2, is again obtained from measurements on
the activity coefficient of solute 2 in a ternary system 1– the 1–2–3 system, with components 2 and 3 in dilute
2–3 can be written as range.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 1 49
Jacob et al. A cubic formalism for temary and muliticomponent solutions

The third-order free-energy interaction coefficients are The second-order interaction parameter formalism is
! ! also used in the literature for the representation of
2 1 L3 ln c2 3 1 L3 ln c2 activity coefficient or excess partial free energies in the
h2 ~ , h2 ~ ,
6 LX23 6 LX33 multicomponent solutions. The second-order interaction
X1 ?1 X1 ?1
! ! parameter formalism as introduced by Lupis (1983) is
223 1 L3 ln c2 233 1 L3 ln c2 given by
h2 ~ , h2 ~
2 LX22 LX3 2 LX2 LX32 X
m
X1 ?1 X1 ?1
ln ci ~ ln c0i z eji Xj z
where h22
represents the third-order self-interaction j~2

parameter obtained from measurements on the binary X

m XX
m{1 m
system 1–2. The third-order parameters h32 , h2232 and h233
2
rji Xj2 z rjk
i Xj Xk z . . . (7)
have to determined by measurements on ternary alloys j~2 j~2 kwj

rich in component 1. Thus for a ternary system 1–2–3 rich
in component 1, there are nine interaction parameters
defining the activity coefficient of each solute (2, 3). Thus,
18 interaction parameters are required to describe the
system if third-order terms are included.
The Maxwell’s relation
   
L LG L LG
~ (2)
Lni Lnj Lnj Lni
can be used to provide a link between interaction
parameters. A universally valid relation, often referred
to as the reciprocal relation (Lupis, 1983) between first-
order parameters obtained from Maxwell’s relation,
valid irrespective of the nature of truncation, is
where i, j and k indicate solutes, 1 denotes the solvent in
system of mz1 components and r denotes the second-
order free-energy interaction parameter. The second-
order formalism can be used at higher concentrations.
However, it does not satisfy the condition for exactness
(Maxwell’s relation) (Srikanth and Jacob, 1988). Thus,
the formalism is inexact except at infinite dilution of the
solute. Only path dependant integrals can be applied to
solve for the activity coefficient of the solvent, when the
activity coefficient of the solutes is defined by Maclaurin
series expansion truncated to the second-order terms.
Special relationships between the interaction parameters
(Srikanth and Jacob, 1988, 1989a), are required to
ensure consistency with the Gibbs–Duhem equation

eji ~eij (3) eii ~{2rii (i~2 . . . m),

Lupis and Elliot (1966) have derived other general
recurrence relations between interaction parameters of
the Maclaurin infinite series expansion using the Gibbs–
Duhem relation. The recurrence relations between solute
interaction parameters in the second-order representa-
tion for a solution with mz1 components are
riji zeji ~2rij zeii
rjk j ki k ij i
i zek ~rj zei ~rk zej
for all values of i, j, k from 2 to m where i?j?k.
The Wagner (1962) first-order interaction parameter
formalism has been extensively used to compute activity
coefficients of solutes in multicomponent solutions;
for example, oxygen in steels. For a multicomponent
solution, the activity coefficient of the solute i can be
written as
X
m (for example, e22 and e33 ) can be obtained from binary
ln ci ~ ln coi z eji Xj
j~2
where Xj (j52 … m) are the mole fraction of the solutes.
The advantage of the first-order interaction parameter
formalism is its simplicity and availability of an
extensive range of first-order parameters. The reciprocal
relationship between first-order interaction parameters
reduces the number of independent parameters that have
to be obtained from experiment. At higher concentrations
of solutes, higher order interaction coefficients are re-
quired. It is also realised now that the first-order
representation is thermodynamically inconsistent at finite
solute concentrations (Lupis and Elliot, 1966; Darken,
1967; Schuhmann Jr, 1985; Pelton and Bale, 1986, 1990;
Srikanth and Jacob, 1988) and its continued use is
unjustified except for rough estimates.
eji ~{riji (i, j~2 . . . m, i=j),
rjk jk
i ~rq (i, j, k, q~2 . . . m and j=k),
rji ~rjq (i, j, q~2 . . . m) (8)
Special relations are not equivalent to the recurrence
relations proposed by Lupis (1983) (equations (4) and
(4)
(5)), though they satisfy them. The special relations give
more information than the recurrence relations. As a
(5) matter of consequence on imposing these relations, the
condition for exactness is restored. In a ternary system
1–2–3 rich in component 1, five interaction parameters
are required for each solute in the second-order
formulation. For both solutes together, 10 interaction
parameters are needed. Since seven special relations
between interaction parameters are required to make the
formalism consistent with Gibbs–Duhem relation, only
three independent parameters are needed, of which two
(6) data on 1–2 and 1–3 systems. Only one parameter (for
example, e32 ) needs to be obtained accurately by mea-
surement on the ternary system.
Darken (1967b) showed in the terminal regions of
many binary systems, extending in many cases up to
y30 at-% of the solute, the solvent obeys regular
solution type behaviour (ln c1 ~g12 X22 ). The activity
coefficient of the solute in the terminal region is then
given by ln (c2 =co2 )~g12 ({2X2 zX22 ). This quadratic
formalism of Darken (1967b) is different from the
regular solution model since ln co2 is not generally equal
to the g12. Darken has shown that the extension of this
the formalism to ternary systems provides a thermo-
dynamically consistent and adequate framework for
representation of data for relatively concentrated so-
lutions. Srikanth and Jacob (1989b) have extended

50 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 1
 Jacob et al. A cubic formalism for temary and muliticomponent solutions

Darken’s quadratic formalism to multicomponent sys- Among the three components of the ternary, let
tems. The corresponding expressions (Srikanth and component 1 be the solvent and 2, 3 the solutes. The
Jacob, 1989b; Srikanth et al., 1989) for the activity partial Gibbs free-energy of solvent 1 can be expressed
coefficients for a solution with mz1 components, where as
solvent is denoted as 1 and i, j, k … m are the solutes, are E
given as G 1 ~G E z(1{X1 )(LG E =LX1 )X2 =X3 (12)
m X
X X
m Equations (11) and (12) are combined to obtain an
ln c1 ~ (g1j zg1k {gjk )Xj Xk z g1j Xj2 (9) E
jvk j~2
equation for G 1 in terms of aij, bij, at, X1, X2 and X3.
E
X
m G 1 ~f½a12 X1 X2 z(1{X1 )a12 (L(X1 X2 )=LX1 )z
ln ci ~ log c0i {2g1i Xi { (g1i zg1j {gij )Xj z
j~2
½a23 X2 X3 z(1{X1 )a23 (L(X2 X3 )=LX1 )z
j=i
½a31 X1 X3 z(1{X1 )a31 (L(X1 X3 )=LX1 )z
X
m X X
m
(g1j zg1k {gjk )Xj Xk z g1j Xj2 (10) ½b12 X1 X2 (X1{X2 )z(1{X1 )b12 (L(X1 X2 (X1 {X2 ))=LX1 )z
jvk j~2
½b23 X2 X3 (X2{X3 )z(1{X1 )b23 (L(X2 X3 (X2{X3 ))=LX1 )z
where the constants g1j and g1k are obtained from the ½b31 X1 X3 (X3{X1 )z(1{X1 )b31 (L(X1 X3 (X3{X1 ))=LX1 )z
corresponding binary systems 1–j and 1–k. The constant
gij is obtained from ternary 1–i–j solution rich in solvent ½at X1 X2 X3 z(1{X1 )at (L(X1 X2 X3 )=LX1 )g (13)
1. The quadratic formalism is identical to the second-
order interaction parameter formalism with the special Simplifying
relations (Srikanth and Jacob, 1988). Pelton and Bale
(1986, 1990) have proposed a ‘unified interaction E dX1 dX2
parameter formalism’ which on careful examination is G 1 ~f½a12 X1 X2 z(1{X1 )(a12 X2 za12 X1 )z
dX1 dX1
found to be identical to Darken’s quadratic formalism,
and the truncated Maclaurin series expansion including dX2 dX3
½a23 X2 X3 z(1{X1 )(a23 X3 za23 X2 )z
terms up to second-order along with the special relations dX1 dX1
suggested by Srikanth and Jacob (1989b) which makes dX1 dX3
the formalism thermodynamically consistent. ½a31 X1 X3 z(1{X1 )(a31 X3 za31 X2 )z
dX1 dX1
The asymmetrical nature of experimental data for
integral thermodynamic excess properties of most binary ½b12 X1 X2 (X1 {X2 )z(1{X1 )b12
systems makes it difficult to integrate them with the dX2 dX2
quadratic formalism (Darken, 1967b; Srikanth and (2X1 X2 zX12 {X22 {2X1 X2 )z
dX1 dX1
Jacob, 1989b) or by the second-order interaction
parameter formalism with special relations (Srikanth ½b23 X2 X3 (X2 {X3 )z(1{X1 )b23
and Jacob, 1988). The quadratic formalism is restricted dX2 dX3 2
to the terminal regions, whereas the cubic formalism can ( (2X2 X3 {X32 )z (X {2X2 X3 ))z
express the thermodynamic properties of solutions to dX1 dX1 2
more extended regions. ½b31 X1 X3 (X3 {X1 )z(1{X1 )b31
dX3 dX3
Cubic formalism for ternary systems (X32 z2X1 X3
dX1
{2X1 X3 {X12
dX1
)z
The basic equation for the excess Gibbs free-energy of
½at X1 X2 X3 zat (1{X1 )
mixing of a ternary system can be written as
dX1 dX2 dX3
X
3 X
3 (X2 X3 zX1 X3 zX1 X2 )g (14)
GtE~ aij Xi Xjz bij Xi Xj (Xi{Xj )zat Xi Xj Xk (11) dX1 dX1 dX1
i=j=k i=j=k

In order to further simplify equation (14), differentials

where aij, bij are subregular solution parameters of i–j of X2 and X3 with respect to solvent composition X1
binary (Hardy, 1953) and at is a parameter characteristic need to be evaluated. For convenience, let (X2/X3)5r.
of the ternary. The subregular solution parameters can Since the sum of mole fractions is unity, X1zX2zX351,
be obtained from the thermodynamic data for the binary X1zX3(1zr)51. Expression for dX3/dX1 and dX2/dX1
system GbE ~Xi Xj faij zbij (Xi {Xj )g. It is advantageous can be obtained as
to start with an expression for the integral property since
the partials derived there from will obviously satisfy the dX3 {1 {1 {X3 {X3
~ ~ ~ ~ (15)
Gibbs–Duhem equation and Maxwell’s relation. For a dX1 1zr 1z(X2 =X3 ) X3 zX2 1{X1
ternary system, there are seven parameters in equa-
tion (7), of which six come from the binaries and only Similarly
one from the ternary. dX2 {X2
The partial excess Gibbs energy of component i can be ~ (16)
dX1 1{X1
obtained from equation (11)
Substituting equations (15) and (16) in equation (14),
E
G i ~G E z(1{Xi )(LG E =LXi )Xj =Xk one obtains

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 1 51
Jacob et al. A cubic formalism for temary and muliticomponent solutions

E
G 1 ~fa12 X22 za31 X32 z(a12 za31 {a23 )X2 X3 z RTlnc3 ~½a31 X12 za23 X22 z(a31 za23 {a12 )X1 X2 z

b12 ½X1 X2 (X1 {X2 )z2X1 X2 {X22 {3X12 X2 z3X1 X22 z b31 ½{X12 z2X1 X3 {2X1 X32 z2X12 X3 z

b23 ½X2 X3 (X2 {X3 ){3X22 X3 z3X2 X32 z b12 ½2X1 X22 {2X12 X2 z

b31 ½X1 X3 (X3 {X1 ){2X1 X3 z3X12 X3 zX32 {3X1 X32 z b23 ½X22 {2X2 X3 {2X22 X3 z2X2 X32 z
at ½X1 X2 X3 zX2 X3 {3X1 X2 X3 g (17) at X1 X2 ½1{2X3  (21)

The activity coefficient of solutes 2 expressed in terms of

Equation (17) can be rewritten in terms of activity
coefficient as
RTlnc1 ~½a12 X22 za31 X32 z(a12 za31 {a23 )X2 X3 z
b12 ½{X22 z2X1 X2 {2X12 X2 z2X1 X22 z
b23 ½2X2 X32 {2X22 X3 z
b31 ½X32 {2X1 X3 z2X12 X3 {2X1 X32 z
at X2 X3 ½1{2X1 
composition variables X2 and X3 becomes
RTlnc2 ~½(a12 zb12 )zX2 ({2a12 {6b12 )z
X3 (a23 {a31 {a12 {2b12 z2b31 zat )z
X22 (a12 z9b12 )zX32 (a31 zb12 {b23 {6b31 {at )z
X2 X3 (a12 za31 {a23 z8b12 z2b23 {4b31 {3at )z
X23 ({4b12 )zX33 (4b31 )zX22 X3 ({6b12{2b23z2b31z2at )z
(18)
X2 X32 ({2b12 z2b23 z6b31 z2at ) (22)

The activity coefficient of solvent 1 in terms of two

composition variables of components 2 and 3 can be
written as
RTlnc1 ~½X22 (a12 z3b12 )zX32 (a31 {3b31 )z
X2 X3 (a12 za31 {a23 z2b12 {2b31 {at )z
X23 ({4b12 )zX33 (4b31 )z
X22 X3 ({6b12 {2b23 z2b31 z2at )z
X2 X32 ({2b12 z2b23 z6b31 z2at )
As X2,X3R0, c1R1, equation (19) is consistent with
Raoult’s law for the solvent. Similarly, the activity
coefficient for the components 2 and 3 can be written as
RTlnc2 ~½a12 X12 za23 X32 z(a12 za23 {a31 )X1 X3 z
When X2, X3R0, the activity coefficient of component 2
is represented as c02 and from equation (22), its value is
defined by RT ln c02 ~(a12 zb12 ). Equation (22) is written
such that the first-, second- and third-order free-energy
interaction parameters can be readily identified by
comparison with the corresponding expression for the
activity coefficient in the third-order interaction para-
meter formalism
RTlnc2 ~RTlnc02 zRT½e22 X2 ze32 X3 zr22 X22 zr32 X32 z
(19)
2 3 3 3 223 2 233
r23 2
2 X2 X3 zh2 X2 zh2 X3 zh2 X2 X3 zh2 X2 X3  (23)
where e represents the first-order interaction parameters,
r the second-order interaction parameters and h the
third-order interaction parameters. For example, the
first-order interaction parameters (Wagner, 1962) are

b23 ½{2X22 X3 z2X2 X32 z2X2 X3 {X32 z RTe22 ~({2a12 {6b12 ) and

b31 ½2X12 X3 {2X1 X32 z RTe32 ~(a23 {a31 {a12 {2b12 z2b31 zat )

b12 ½X12 {2X1 X2 {2X12 X2 z2X1 X22 z The expressions for all the interaction parameters in
terms of the coefficients of the cubic formalism are
at X1 X3 ½1{2X2  (20) summarised in Table 1.

Table 1 Expressions for interaction parameters of solutes 2 and 3 in solvent 1 in terms of parameter of cubic
formalism*

Coefficient in the expression Coefficient in the expression for

Composition term for component 2 (equation (23)) IP(2) component 3 (equation (25)) IP(3)

X2 (22a1226b12) RT e22 (a232a312a1222b12z2b31zat) RT e23

X3 (a232a312a1222b12z2b31zat) RT e32 (22a31z6b31) RT e33
X22 (a12z9b12) RT r22 (a12z6b12zb232b312at) RT r23
X32 (a31zb122b2326b312at) RT r32 (a3129b31) RT r33
X2X35X3X2 (a12za312a23z8b12z2b2324b3123at) RT r23
2
(a12za312a23z4b1222b2328b3123at) RT r32
3
X23 (24b12) RT h22 (24b12) RT h23
X33 (4b31) RT h32 (4b31) RT h33
X22 X3 (26b1222b23z2b31z2at) RT h223
2
(26b1222b23z2b31z2at) RT h322
3
X2 X32 (22b12z2b23z6b31z2at) RT h233
2
(22b12z2b23z6b31z2at) RT h332
3

*IP(2)5interaction parameter for component 2; IP(3)5interaction parameter for component 3.

52 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 1

Following an identical procedure, the activity coeffi-
cient of component 3 in terms of composition variables
X2 and X3 is given by
RTlnc3 ~½(a31 {b31 )z
X2 (a23 {a12 {a31 {2b12 z2b31 zat )z
X3 ({2a31 z6b31 )zX22 (a12 z6b12 zb23 {b31 {at )z
X32 (a31 {9b31 )z
X2 X3 (a12 za31 {a23 z4b12 {2b23 {8b31 {3at )z
X23 ({4b12 )zX33 (4b31 )zX22 X3 ({6b12{2b23 z2b31z2at )z
X2 X32 ({2b12 z2b23 z6b31 z2at )
When X2, X3R 0, activity coefficient of component 3 is
represented asc03 ; RTlnc03 ~(a31 {b31 ). By comparison
with the corresponding expression for the activity
coefficient in the third-order interaction parameter
formalism
RTln c3 ~RT ln c03 zRT½e23 X2 ze33 X3 zr23 X22 zr33 X32 z
r32 2 3 3 3 322 2 332 2 (Pelton and Bale, 1990), which are essentially identical.
3 X2 X3 zh3 X2 zh3 X3 zh3 X2 X3 zh3 X2 X3 
the first-, second- and third-order free-energy interaction
parameters for component 3 can be readily identified.
Expressions for all the interaction parameters in terms
of the coefficients of the cubic formalism are listed in
Table 1.
From an inspection of the corresponding terms, it is
seen that the reciprocal relation between first-order
interaction parameters is satisfied e32 ~(a23 {a31 {a12 {
2b12 z2b31 zat )=RT~e23 . The recurrence relations
between first- and second-order interaction parameters
suggested by Lupis (1983) are also satisfied. For example
r23 3 2 2
2 ze2 ~2r3 ze2 ~(6b12 z2b23 {2b31 {2at )=RT
r32 2 3 3
3 ze3 ~2r2 ze3 ~(2b12 {2b23 {6b31 {2at )=RT
Other recurrence relations involving third-order inter-
action parameters obtained from the general relation
proposed by Lupis (1983) and simplified by Srikanth
and Jacob (1988)
3h32 {h332 3 3 2 223 2 2 from the three binaries. Only one parameter needs to be
3 ~2r2 {2r3 , 3h3 {h2 ~2r3 {2r2
are also satisfied. Further, additional special relations
between interaction parameters suggested by Srikanth
and Jacob (1989a) are also satisfied
h22 ~h23 , h32 ~h33 , h223 322 233 332
2 ~h3 , h2 ~h3 ,
e22 z2r22 z3h22 ~e33 z2r33 z3h33 ~
223 332
e32 zr23 2 32
2 zh2 ~e3 zr3 zh3 ~0
The 10 relations listed above along with the universally
valid reciprocal relation between first-order interaction
parameters reduces the number of independent para-
meters required to describe the behaviour of two solutes
in the third-order formalism from 18 to 7, of which six
(e22 , r22 , h22 and e33 , r33 , h33 ) can be obtained from the con-
stituent binary systems and only one parameter has to be
determined from careful measurements in the ternary.
Expressions for lnc1 , lnc2 , lnc3 and GtE given by equa-
tions (21), (22), (24) and (11) respectively, when
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Jacob et al. A cubic formalism for temary and muliticomponent solutions
substituted satisfy the relation RT½X 1 lnc1 zX 2 lnc2 z
X 3 lnc3 ~GtE , thus providing additional confirmation of
the correctness of the derived equations.
Discussion
The cubic formalism developed in this article provides
expressions for the activity coefficients of solutes in
metallic solvents which are analogous to the more
familiar Maclaurin (Taylor) series expansion truncated
to third-order. Although the third-order interaction
parameter formalism looks formidable with 18 interac-
tion parameters to describe the behaviour of two solutes
in a ternary system, they can all be related to the seven
(24) coefficients of the cubic formalism, six of which are
directly obtained from data on the three constituent
binary systems and only one parameter needs to be
established by measurements on ternary alloys. Thus,
the cubic formalism does not add any extra burden of
measurement. The main advantage is better representa-
tion of data over a more extended composition range
compared to either the quadratic formalism of Darken
(1967b) or the unified interaction parameter formalism
(25)
The cubic formalism provides a thermodynamically
consistent representation of both solute and solvent
properties. It integrates seamlessly data available in the
literature on activity coefficients of solutes in metallic
solvents with data on binary alloys. It provides a marked
improvement over Darken’s quadratic formalism.
In the traditional approach to the study of solute
interactions in ternary and higher order systems, the
activity coefficient of a solute is measured as a function
of composition of all other solutes. Depending on the
accuracy of data obtained and composition range of
solutes covered, the first- and second-order, and in some
rare cases third-order interaction coefficients can be
evaluated. Only the self-interaction parameters (six for a
ternary system in the third-order formalism) come from
binary data; all others (twelve) are to be derived from
measurements on ternary alloys if special relations
between interaction parameters (Srikanth and Jacob,
1988) are not invoked. This is a formidable experimental
task. If the cubic formalism is adopted, there are only
seven coefficients to be evaluated, six of which come
measured in the ternary, which is relatively easy. All the
interaction parameters up to third-order can be derived
from the seven coefficients. The approach in this new
formalism is to rely more on binary parameters available
in the literature and use interrelations between solute
interaction parameters to reduce the burden of measure-
ments on ternary alloys.
The validity of the cubic formalism for representa-
tion of data on selected ternary systems will be
presented in a separate communication. It is concei-
vable that even the subregular format with cubic terms
may not be adequate to represent some binaries. More
complex polynomial expressions for excess Gibbs
energy of mixing may be necessary. The consequences
of more complex expressions for Gibbs energy on the
relations between interaction parameters will explored
separately if required. Experimental data on the va-
riation of activity coefficient of solutes with composi-
tion in metallic solutes can be reanalysed using the
cubic formalism and available binary data to generate
2012 VOL 121 NO 1 53
Jacob et al. A cubic formalism for temary and muliticomponent solutions
coefficients or interaction parameters, which can repre-
sent the data more accurately over more extended
ranges of composition.
The cubic formalism can be readily extended to
multicomponent systems. For a system of n components,
the number of constituent binaries is given by n!/
{(n22)!2!}, and the number of constituent ternaries by
n!/{(n23)!3!}. Each binary requires two coefficients and
each ternary requires one coefficient. Hence, the total
number of coefficients required to describe all the activity
coefficients in the system can be easily assessed. For
example for a quaternary system, 16 coefficients are
needed, 12 coefficients that can be obtained from the six
binaries and four ternary parameters that can be assessed
from each constituent ternary. If the activity coefficients
have to be expressed as a function of temperature, each
free energy coefficient or interaction parameter has to be
decomposed into an enthalpy and entropy term. Hence
twice the number of coefficients will be needed to express
the activity coefficients as a function of temperature.
Acknowledgements
The authors wish to record the support of Indian
National Academy of Engineering (INAE), New Delhi,
for grant of INAE Distinguished Professorship to K. T.
Jacob and Summer Research Fellowship to Bikram
Konar at the Indian Institute of Science.
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