Thermoanalysis of Binary Condensed Eutectic Phases Evincing Molecular Interactions
Thermoanalysis of Binary Condensed Eutectic Phases Evincing Molecular Interactions
DOI 10.1007/s10973-011-1673-8
Arun K. Sharma
Received: 17 February 2011 / Accepted: 17 May 2011 / Published online: 3 June 2011
Ó Akadémiai Kiadó, Budapest, Hungary 2011
123
448 B. L. Sharma et al.
This study aims to three aspects, which are to: dimensions. The experimental Pyrex tubes were sealed
(a) ascertain the behaviour of a binary metallic eutectic under vacuum to prevent the evaporation of the tubes’-
system in comparison to its transparent analogs; (b) obtain content, and the homogeneity of the mixtures was attained
quantitative idea of molecular interactions; and (c) com- by heat–chill method. The diagrams of state for binary
bine this approach with standard equations to predict naphthalene–o-nitrophenol, a-naphthol–naphthalene, diphe-
alternate procedure of binary phase diagram. nylamine–a-naphthol, benzil–diphenyl and acenaphthene–
antimonytrichloride eutectic systems were studied by
determining solidus–liquidus temperatures over their
Experimental details respective entire mole fraction composition range with
thaw–melt technique, whereas the melting and liquidus
Materials and their purification temperatures of Cd–Bi eutectic system were likewise,
obtained by thermal analysis.
Homogeneous materials, diphenylamine (Reanal, AR); o-
nitrophenol (Himedia, AR); benzil (Thomas Baker, AR); a-
naphthol (E. Merck, AR); antimonytrichloride (Himedia, Results
AR); and diphenyl (Himedia, AR), were used as supplied,
whilst naphthalene (Aldrich, AR) and acenaphthene (Alpha The experimental data comprising of melting temperatures,
Aesar) were, respectively, purified by sublimation method heat flows and enthalpies of fusion of the constituent
and repeated crystallization from ethyl acetate (AR). The materials are provided in Table 1. Tables 2, 3 and 4,
melting temperatures of the aforementioned materials respectively, record the solidus–liquidus equilibrium data
determined by thaw–melt technique are found on the order of binary naphthalene–o-nitrophenol, a-naphthol–naphtha-
comparable to the literature values [23, 24]. The metals, lene and diphenylamine–a-naphthol eutectic systems.
bismuth (Merck, AR), and cadmium (Merck, AR), were Likewise, the solidus–liquidus equilibrium curves drawn in
also used as such, and their melting temperatures obtained Figs. 1, 2, and 3, respectively, represent the phase equi-
by thermal analysis are found approaching the literature librium data of binary benzil–diphenyl, acenaphthene–an-
attributions [23, 24]. The enthalpies of fusion of the timonytrichloride and cadmium–bismuth eutectic systems.
homogeneous materials were vouched at their respective
melting temperatures by thermal analysis, which are in
good agreement with the reported values [23, 24]. Theory
123
Thermoanalysis of binary condensed eutectic phases 449
Table 2 Solidus–liquidus equilibrium data for naphthalene (1)–o- Table 4 Solidus–liquidus equilibrium data for diphenylamine (1)–a–
nitrophenol (2) eutectic system naphthol (2) eutectic system
Mole fraction Solidus Liquidus Ideal Mole fraction of Solidus Liquidus Ideal
of component (1) temperature temperature temperature component (1) temperature temperature temperature
Ts/°C Tm/°C Tid/°C Ts/°C Tm/°C Tid/°C
Table 3 Solidus–liquidus equilibrium data for a-naphthol (1)–naph- temperatures of the binary naphthalene–o-nitrophenol,
thalene (2) eutectic system a-naphthol–naphthalene and diphenylamine–a-naphthol
Mole fraction Solidus Liquidus Ideal eutectic systems calculated by Eq. 1 putting c‘i = 1 are
of component (1) temperature temperature temperature recorded in Tables 2, 3 and 4, whilst those of binary ben-
Ts/°C Tm/°C Tid/°C zil–diphenyl, acenaphthene–antimonytrichloride and cad-
0.0000 80.50 mium–bismuth eutectic systems are likewise obtained and
0.1002 61.50 74.50 73.50 plotted by dotted lines in Figs. 1, 2, and 3.
0.2003 61.50 68.50 68.50
0.3003 61.50 64.00 62.00
0.3950 (e*) 61.50 (Te) 61.50 61.50
0.4002 61.50 62.00 59.50
0.5001 61.50 67.50 65.50
0.6003 61.50 72.50 72.00 370
0.7004 61.50 78.50 78.50
0.8005 61.50 84.50 84.00
350
0.9003 61.50 90.00 90.00
II I
Temperature/K
1.0000 95.00
330
deviation from its ideal regions was ascertained by com- III
e*, Te
puting the activity coefficients of the eutectic phases,
i (= 1, 2) depending on their richness in the pre- or post- 310
binary mixtures vis–a-vis eutectic mixture, at respective
liquidus temperature, T by the following equation [13, 25]:
290
Df Hi0 1 1
lnx‘i c‘i ¼ 0 ð1Þ
R T Ti
where superscript ‘ refers to the condensed phase, whilst 270
x‘i ; c‘i , Df Hi0 and Ti0 , respectively, are the mole fraction, 0.0 0.2 0.4 0.6 0.8 1.0
activity coefficient, enthalpy of fusion and melting tem- Mole fraction of benzil
perature of eutectic phase, i (= 1, 2); T represents liquidus
Fig. 1 Diagram of state for benzil–diphenyl system. I Liquidus
temperature of the phase mixture at mole fraction temperatures curve; II Ideal temperatures curve; III Solidus temper-
composition, x‘i ; and R is the gas constant. Ideal liquidus atures; e* eutectic composition Te eutectic temperature
123
450 B. L. Sharma et al.
600
380
580
560
360 540
520
Temperature/K
Temperature/K
500
340
480 I
II
I 460
II 440
320
III
420 x x x x x
IIIx x x
e*, Te
e*, Te
400
0.0 0.2 0.4 0.6 0.8 1.0
300 e*
0 0.2 0.4 0.6 0.8 1.0 Mole fraction of cadmium
Mole fraction of acenaphthene
Fig. 3 Diagram of state of cadmium–bismuth system. I Liquidus
Fig. 2 Diagram of state for acenaphthene–antimonytrichloride sys- temperatures curve; II Ideal temperatures curve; III Solidus temper-
tem Liquidus temperatures curve. I Liquidus temperatures curve; II ature; e* eutectic composition; Te eutectic temperature
Ideal temperatures curve; III Solidus temperatures; e* eutectic
composition; Te eutectic temperature
their respective temperature and composition from Eq. 1
The experimental and theoretical solidus–liquidus and thereby, inserted in Eqs. 2 and 3 [12, 26]:
equilibrium curves in each system evidentially do not
coincide with each other confirming its deviation from RTlnc‘1 ¼ Aðx‘2 Þ þ Bðx‘2 Þ2 þ Cðx‘2 Þ3 ð2Þ
ideality and the occurrence of molecular interactions RTlnc‘2 ¼ A0 ðx‘1 Þ þ B0 ðx‘1 Þ2 þ C 0 ðx‘1 Þ3 ð3Þ
between condensed phases as well. With a view to achieve
physical understanding and the quantitative idea of The constants A; B; C; A0 ; B0 and C0 evaluated with the
molecular interactions, the activity coefficients of the application of least-squares method are provided in
eutectic phases either side of a solidus–liquidus equilib- Table 5. The application of Gibbs–Duhem transformation
rium curve of each system are computed as a function of would determine ln c‘1 and ln c‘2 for each experimental
123
Thermoanalysis of binary condensed eutectic phases 451
composition comprising of mole fractions x‘1 and x‘2 , with lEi ¼ RTlnc‘i ð9Þ
liquidus temperature T of the same branch of the curve.
olnc‘
This implies that the corresponding equations for Eqs. 2 The values of ½ oT i P (i = 1, 2) for any binary system
and 3 at the same temperature could readily be obtained in can be determined from the slopes of the liquidus lines
the following forms: obtained by plotting the activity coefficients ln c‘1 and ln c‘2
of the eutectic phases in variable compositional mixtures
3 0
RTlnc1 ¼ ðA 2B Þx1 A lnx1 þ B C ðx‘1 Þ2
‘ 0 0 ‘ 0 ‘ 0
against their liquidus temperatures T, for that system. The
2
0 ‘ 3 0 0 C0 slopes for each system determined in this manner were
þ C ðx1 Þ þ B A þ ð4Þ utilized in computing the excess functions, viz., GE, SE, HE
2
and lEi (i = 1, 2) by Eqs. 6, 7, 8 and 9 which are recorded
3
RTlnc‘2 ¼ ðA 2BÞx‘2 Alnx‘2 þ B C ðx‘2 Þ2 in Tables 6, 7, 8, 9, 10 and 11. The obtained excess
2
functions for the binary benzil–diphenyl, acenaphthene–
‘ 3 C
þ Cðx2 Þ þ B A þ ð5Þ antimonytrichloride and cadmium–bismuth eutectic
2
systems are also represented in Figs. 4, 5, and 6, with a
The physical significance of the transformation is that
definite purpose to reveal qualitative variation aspects of
Eqs. 4 and 5 can, respectively, predict quantitative values
the excess functions over the entire mole fraction
of ln c‘1 and ln c‘2 as functions of x‘1 and x‘2 for any com-
composition range in general and at the eutectic
position at the same liquidus temperature, T. The computed
composition in particular (Table 5).
activity coefficient data for the eutectic phases in various
binary mixtures of the systems at respective liquidus tem-
peratures are recorded in Tables 6, 7, 8, 9, 10 and 11. The
Discussion
activity coefficient data can further facile the process of
reckoning the excess functions, viz., GE, SE and HE of pre-,
The eutectic compositions (e*) and eutectic temperatures (Te)
post-, and eutectic compositions along with the excess
of binary naphthalene–o-nitrophenol, a-naphthol–naphtha-
chemical potentials of the eutectic members, lEi (i = 1, 2)
lene, diphenylamine–a-naphthol and benzil–diphenyl, ace-
at the same liquidus temperature, T in all the systems at
naphthene–antimonytrichloride and cadmium–bismuth
constant pressure using the following relations [9, 13]:
systems manipulated from their respective diagrams of state
GE ¼ RT½x‘1 lnc‘1 þ x‘2 lnc‘2 ð6Þ and later experimentally verified are given numerically in
Tables 2, 3 and 4 and theoretically indicated in Figs. 1, 2,
olnc‘1 olnc‘2
SE ¼ R x‘1 lnc‘1 þ x‘2 lnc‘2 þ Tx‘1 þ Tx‘2 and 3. The perusal of both quantitative (Tables 6, 7, 8, 9, 10
oT oT
and 11) and qualitative (Figs. 4, 5 and 6) analyses explores
ð7Þ that the excess free energy of mixing, GE would decrease
gradually either side of solidus–liquidus equilibrium curves
olnc‘1 olnc‘2
H E ¼ RT 2 x‘1 þx‘2 ð8Þ (Figs. 1, 2, 3, 4, 5 and 6) and furnish minima at the eutectic
oT P oT P
compositions. Evidentially, the variation of GE over the
entire mole fraction composition range of each experimental
Table 6 Activity coefficient and excess thermodynamic functions for the binary system naphthalene(1)–o-nitrophenol (2)
Mole fraction Liquidus lnc1 lnc2 Excess Gibb’s Excess HE/ Chemical potential Chemical potential
of component temperature/ free energy GE/ entropy SE/ J mol-1 of component (1) of component (2)
(1) K kJ mol-1 J mol-1 K-1 lE1 /J mol-1 lE2 /J mol-1
123
452 B. L. Sharma et al.
Table 7 Activity coefficient and excess thermodynamic functions for the binary system a-naphthol (1)-naphthalene (2)
Mole fraction Liquidus lnc1 lnc2 Excess Gibb’s Excess HE/ Chemical potential Chemical potential
of component temperature/ free energy GE/ entropy SE/ J mol-1 of component (1) of component (2)
(1) K kJ mol-1 J mol-1 K-1 lE1 /J mol-1 lE2 /J mol-1
Table 8 Activity coefficient and excess thermodynamic functions for the binary system diphenylamine (1)–a-naphthol (2)
Mole fraction Liquidus lnc1 lnc2 Excess Gibb’s Excess H E/ Chemical potential Chemical potential
of component temperature/ free energy GE/ entropy SE/ KJ mol-1 of component (1) of component (2)
(1) K kJ mol-1 J mol-1 K-1 lE1 /J mol-1 lE2 /J mol-1
Table 9 Activity coefficient and excess thermodynamic functions for the binary system benzil (1)–diphenyl (2)
Mole fraction Liquidus lnc1 lnc2 Excess Gibb’s Excess HE/ Chemical potential Chemical potential
of component temperature/ free energy GE/ entropy SE/ J mol-1 of component (1) of component (2)
(1) K kJ mol-1 J mol-1 K-1 lE1 /J mol-1 lE2 /J mol-1
123
Thermoanalysis of binary condensed eutectic phases 453
Table 10 Activity coefficient and excess thermodynamic functions for the binary system acenaphthene (1)–antimonytrichloride (2)
Mole Liquidus lnc1 lnc2 Excess Gibb’s free Excess entropy HE/ Chemical Chemical
fraction of temperature/ energy SE 9 10-1/ J mol-1 potential of potential of
component K GE 9 10-2/ J mol-1 K-1 component (1) lE1 / component (2) lE2 /
(1) kJ mol-1 J mol-1 J mol-1
Table 11 Activity coefficient and excess thermodynamic functions for the binary system cadmium (1)–bismuth (2)
Mole fraction Liquidus lnc1 lnc2 Excess Gibb’s Excess HE/ Chemical potential Chemical potential
of component temperature/ free energy GE/ entropy SE/ J mol-1 of component (1) lE1 / of component (2) lE2 /
(1) K kJ mol-1 J mol-1 K-1 J mol-1 J mol-1
system is consistent with the miscibility criteria of sponta- being the Boltzmann constant and weight of configuration
neity [27], because the mixing of the eutectic phases of any which is estimated the most probable one at the eutectic
binary system would progress only if every infinitesimal composition.). It may be pertinent to mention here that the
change in the composition of that system is accompanied by number of distinct arrangements of phase molecules in any
a decrease in free energy. Obviously, the miscibility argu- compositional configuration do determine the weight of that
ments favour the cause of most negative value of Gibbs free configuration, and the most probable compositional config-
energy, GE at the eutectic composition. On the contrary, the uration is characterized by optimum value of w. The excess
excess entropy of mixing, SE would acquire maxima at the chemical potentials, lEi (i = 1, 2), of the eutectic phases
eutectic compositions of the experimental systems which numerically signify the equilibrium stages in the condensed
should be there because of its obedience to the miscibility states of the experimental binary systems. Likewise, the
criteria. The explanation of the maximum value of SE, at the excess enthalpy of mixing, HE, offers supporting evidence to
eutectic composition, lies in the concept that the most strengthen the observations of GE and SE for the experimental
probable configuration of the eutectic phase molecules in the binary systems to be far from being ideal, since HE is found
condensed state, occurs at this very composition (e*) and nontrivial for the systems. Further, the Tables 6, 7, 8, 9, 10
temperature (Te) owing to the co-existence of three phases and 11 record positive and negative magnitudes of HE which
(two solidus and one liquidus) in equilibrium. Further, the are, respectively, consistent with the positive and negative
minimum and maximum values of GE and SE, respectively, at deviations from the ideal regions of the systems. Besides, the
the eutectic compositions, implicitly, predict that the exper- higher value of HE for the eutectic composition in each
imental binary systems follow the criteria of spontaneity and system conforms to the most stable composition in the entire
Planck hypothesis, S = klnw (where k and w, respectively, mole fraction compositional range at all liquidus
123
454 B. L. Sharma et al.
1.8
E
SE
.
S 5.0
1.5
4.5 .
4.0
1.2
E
.
H
E 3.5 .H
0.9 3.0
.
HE/J mol–1
2.5
0.6 2.0
.
0.3
1.5
.
1.0 . .
0.5 .. . .
.. 0.2.. 0.3.. .0.4
0.0 e* e*
0.1 0.3 0.5 0.7 0.9 1.0 0.0
0.1 0.5 0.6 0.7 0.8 0.9 1.0
–1.5
–0.2
–3.0
GE/kJ mol–1
–0.4 –4.5
–6.0
.
–0.6 E
G E x 10–2/kJ mol–1 –7.5
G
–0.8
–9.0 .
–10.5
Mole fraction of benzil
. .
–12.0
–13.5
Fig. 4 Excess thermodynamics functions GE, SE and HE for benzil–
–15.0
.
diphenyl system. e* eutectic composition GE
–16.5
Mole fraction of acenaphthene
temperatures covered by solidus–liquidus phase equilibrium Fig. 5 Excess thermodynamics functions GE, SE and HE for
curve. The computational procedure of the excess functions acenaphthene–antimonytrichloride system. e* eutectic composition
from enthalpies of fusion data of the eutectic phases confirms
their reliability and authenticity in predicting the non-ideal x‘i c‘i Df Hi0 1 1
ln ¼ ð11Þ
nature of liquidus solutions of the binary systems, since the xsi csi R T Ti0
excess functions express their obedience to miscibility cri-
teria and Planck formulation, thus provide quantitative idea where x‘i ; c‘i ; Df Hi0 and Ti0 are already defined for the
of the molecular interactions. eutectic phase i (= 1, 2) with mole fraction xsi and activity
Moreover, the Guggenheim lattice theory [28] would coefficient csi in the solidus phase in equilibrium with the
evidentially offer supporting evidence to the occurrence of liquidus phase at temperature T. The excess functions GE
molecular interactions in terms of excess thermodynamic and SE calculated by Eqs. 6 and 7 for the eutectic
functions. The theory speaks that the activity coefficients of compositions of the binary systems are not found in
the eutectic members can be computed from the following agreement with their values obtained by Eqs. 12 and 13,
equation [9, 13, 21, 28]: which are an extraction of Eq. 11 presuming the nature of
eutectic mixture to be regular:
RTlnc‘i ¼ Að1 x‘i Þ þ Bð1 x‘i Þ2 ð10Þ
Tm T10 0
0 T m T2
The activity coefficient data accomplished by Eq. 10 GE ¼ ðx‘1 Þm Df H10 þ ðx ‘
Þ D H
2 m f 2
T10 T20
inferred that the experimental systems are not regular.
ð12Þ
Imagine an equilibrium composition of a binary system
which shows complete miscibility in solidus–liquidus Tm T10 0 Tm T2
0
SE ¼ ðx‘1 Þm Df H10 þ ðx ‘
Þ D H
2 m f 2
regular solution at liquidus temperature, T at which Tm T10 Tm T20
applicability of the lattice theory is represented by Eq. 11: ð13Þ
123
Thermoanalysis of binary condensed eutectic phases 455
SE/J mol–1 K–1 the phase molecules that occur in the regular eutectic melt
E
S predominating the weight of phase molecules configuration
2.8
in the non-ideal eutectic melt. This implies that molecular
2.4 interactions exhibit the ability to uphold the inequality
2.0 E wreg [ wreal, where wreg and wreal, respectively, represent
H
the number of distinct arrangements of phase molecules in
1.6 the regular and non-ideal eutectic melts. The conformity of
HE/J mol–1
1.2 all the experimental binary eutectic systems with the cri-
teria of miscibility and Planck formulation explicitly
0.8 evinces the reliability of thermodynamic analysis and
0.4 thereby, the computational procedure of excess functions
e*
using lone enthalpy of fusion data of the constituent phases.
0 Besides, the negative and positive numerical signs of
0.1 0.3 0.5 0.7 0.9 1.0
–0.3 the excess functions, viz., GE is negative, and SE and
HE are positive, for the eutectic compositions of binary
–0.6
GE/kJ mol–1
123
456 B. L. Sharma et al.
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