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DOI 10.1007/s10853-014-8014-9
Received: 14 October 2013 / Accepted: 2 January 2014 / Published online: 17 January 2014
Springer Science+Business Media New York 2014
Introduction
Ternary oxides LnRhO3 containing lanthanide elements
display interesting magnetic [1, 2], electrochemical [3, 4]
and catalytic [5] properties. Some of the rare earth perovskite oxides (LaRhO3, DyRhO3, GdRhO3 and LuRhO3)
find application as cathode in the photoelectrolysis of water
[3, 4]. Crystal structures of LnRhO3 have also been
investigated by Macquart et al. [6]. Taniguchi et al. [1]
explored the electrical and magnetic properties of LnRhO3
(Ln = rare earth except Ce and Pm). They reported paramagnetic behaviour of LnRhO3 compounds above 5 K.
Magnetic property of these orthorhombic perovskites arises
from the presence of rare earth ions. Six 4d electrons of
Rh3? ion prefer low spin state with no magnetic moment.
Resistivity of all LnRhO3 compounds exhibits semiconductor-like temperature dependence. As the part of organized study of metalrhodiumoxygen systems [719],
thermodynamic properties and phase relations in the system SmRhO were investigated. This is the first study of
phase relations and thermodynamic properties for the system SmRhO. Thermodynamic data for SmRhO3 are
unavailable in the literature.
This article reports measurement of Gibbs energy of
formation of SmRhO3 using solid-state electrochemical
cells in two different temperature ranges. In the temperature range from 875 to 1110 K, C-type Sm2O3 with cubic
structure is in equilibrium with Rh and SmRhO3, whereas
B-type Sm2O3 is present in the temperature range
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11101300 K. Different types of two- and three-dimensional phase diagrams are developed using thermodynamic
data to provide comprehensive coverage.
Experimental
Materials
Sm2O3 powder used in this study is obtained from two
sources. Spectroscopic grade Sm2O3 from Johnson Matthey Rare Earths Products, U.K., consisted mainly of the
cubic phase with small amount of the monoclinic variety.
Sm2O3, *99.9 % pure (Indian Rare Earths Ltd., India),
was mainly monoclinic in the as received condition.
Sm2O3, from both sources, was heated at 1473 K for 1 h in
the vacuum furnace to remove H2O and CO2 and then
cooled to room temperature. The product had monoclinic
structure, C2/m(12), with lattice parameters a =
0.1415 nm, b = 0.3640 nm and c = 0.8828 nm, irrespective of the source. By heating the samarium oxide from
Indian Rare Earths Ltd. at 1073 K for 48 h in the dry
synthetic air, the C-form of Sm2O3, Ia3 (206) with lattice
parameter a = 1.093 nm, was obtained.
Powders of Rh (99.95 %), Sm (99.9 %) and Rh2O3
(99.9 %, metal basis) were obtained from Alfa Aesar.
Rh2O3 was heated at 1273 K under high-purity oxygen gas
for 24 h to obtain phase pure b-Rh2O3 or Rh2O3 (III),
which had orthorhombic structure with lattice parameters
a = 0.5148 nm, b = 0.5438 nm and c = 1.4693 nm. The
intermetallic SmRh was prepared by heating Sm and Rh in
the appropriate ratio at 1473 K for 48 h.
SmRhO3 was prepared by heating in pure oxygen gas a
pelletized mixture of Sm2O3 and Rh2O3 in the stoichiometric ratio first at 1273 K for 96 h and subsequently at
1573 K for 48 h with several intermediate grinding steps.
Oxides powders were ground together in an agate mortar,
XRh
XO
XSm
Sm2O3 ? Rh2O3 ? Rh
0.402
0.403
0.195
Sm2O3 ? SmRhO3 ? Rh
Sm2O3 ? Rh2O3 ? Rh
0.522
0.402
0.076
SmRhO3 ? Rh2O3 ? Rh
Sm ? Rh2O3
0.264
0.401
0.335
SmRh2 ? Rh ? Sm2O3
Sm2O3 ? Rh
0.234
0.351
0.415
Sm ? SmRh ? Sm2O3
0.223
0.297
0.480
Sm5Rh4 ? Sm2O3
Sm ? SmRh ? Sm2O3
0.171
0.296
0.533
Sm ? SmRh ? Sm2O3
0.131
0.301
0.568
Sm ? SmRh ? Sm2O3
0.010
0.305
0.685
Sm (s.s.) ? Sm2O3
Sm2O3 ? Rh2O3
0.106
0.601
0.293
Sm2O3 ? SmRhO3
10
Sm2O3 ? Rh2O3
0.297
0.598
0.105
SmRhO3 ? Rh2O3
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3137
II
Decomposition of Rh2O3 and SmRhO3 determined an oxygen partial pressure over the reference and working electrodes. As the apparatus used in this study was similar to that
used earlier [7, 8], only a brief description is provided here.
Measuring electrodes were prepared by compacting a
mixture of Sm2O3 (C-type in cell I and B-type in cell II),
SmRhO3 and Rh in the molar ratio 1:1.5:1 against the
closed end of the CSZ tube, with Pt13 % Rh wire
embedded in the mixture. The particle size of the powders
used to prepare electrodes was in the range 525 lm. A
bell-shaped Pyrex tube was attached to the top open end of
the CSZ tube using De-Khotinsky cement. The tube was
evacuated through a side arm and sealed under vacuum. An
excess of SmRhO3 was taken because part of it would
decompose to establish oxygen partial pressure in evacuated and sealed enclosure around the measuring electrode
at high temperatures. The reference electrodes were made
by compacting a mixture of Rh and Rh2O3 in the molar
ratio 1:1.5 in a CSZ crucible with an implanted Pt13 %
Rh wire. The crucible was placed inside an outer silica tube
closed at one end. The CSZ tube enclosing the measuring
electrode and the attached bell jar was placed on the reference electrodes. The outer silica tube was also closed
with a Pyrex cover using De-Khotinsky cement. The
chamber containing the reference electrodes was also
evacuated and sealed. The difference in oxygen partial
pressure at the two electrodes at high-temperature was
measured as emf of the cell.
The cell assembled as described above was suspended in
a vertical resistance furnace with the electrodes located in
the even temperature (1 K) zone. The upper part of the
cell with the cement seals was maintained at room temperature during measurement. In order to minimize the
induced emf, a Faraday cage made from stainless steel foil
was placed between the furnace and the cell assembly. The
furnace temperature was controlled to (1) K and was
measured by a Pt/Pt13 %Rh thermocouple, checked
against the melting point of Au. A high-impedance
([1012 X) digital voltmeter with the sensitivity of
(0.01) mV was used to measure the cell potential.
The reversibility of the cell emf was verified by microcoulometric titration in both directions. A small direct
current (*50 lA) was passed through the cell using an
external potential source for *300 s. The open circuit emf
was monitored as a function of time after each titration.
The cell reversibility was confirmed when the emf returned
to the same value after successive titrations in opposite
directions. The emfs were also reproducible on temperature
cycling of the cell.
The electrodes were examined by XRD, SEM and EDS
before and after emf measurement. The phase composition of the electrodes was found to be essentially unchanged during high-temperature measurements. Only minor
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3138
123
Fig. 2 Temperature dependence of the reversible emf of the solidstate electrochemical cells
2
EII 0:26=mV 221:9 0:02407 T=K
The uncertainty limit represents twice to the standard
deviation (2r). The estimated systematic errors associated
with emf and temperature measurements are significantly
smaller than 2r. The reaction taking place at the right-hand
reference electrode of the two cells is
4=3Rh O2 ! 2=3 Rh2 O3
3139
10
11
-1
12
123
3140
1
Dlm
RT ln PO2
O2 128=J mol
349883 197:29 T=K
13
The decomposition temperature of SmRhO3 can be calculated using Eq. (13) at any defined pressure of oxygen. The
decomposition temperature of the ternary oxide in pure
oxygen at standard atmospheric pressure Po = 0.1 M Pa is
1773 (3) K and in air decomposition occurs at 1665
(2) K. Since the computed decomposition temperatures
are well beyond the temperature range of emf measurement,
it would be useful to confirm them by direct measurement.
Thermal analysis of SmRhO3 in air
The results of TGA and DTA analysis of SmRhO3 in air are
displayed in Fig. 3. Heat flow, mass change and temperature
are plotted as a function of time. There is some difference in
the onset temperatures for decomposition indicated in TGA
and DTA. The onset temperature from TGA in Fig. 3 and
differential DTG in Fig. 4 is 1650 (5) K, approximately
15 K below the value calculated from extrapolated thermodynamic data. Although TGA and DTG are generally
more sensitive indicators of decomposition, presence of
oxygen nonstoichiometry in SmRhO3 can bias the results.
More careful study of both cation and anion nonstoichiometry of SmRhO3 is required for resolving the small but
significant differences in data from different techniques.
Temperature-composition phase relations at constant
oxygen partial pressures
Temperature-composition phase diagram for a ternary
system such as SmRhO with a volatile component will
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3141
Fig. 4 Differential
thermogravimetric analysis
(DTG) of SmRhO3 as a function
of temperature in air
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3142
14
15
2
DlRh =J mol1 RT ln XRh XSm
2XRh XSm
3
2XSm XSm XRh 11450
16
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intermetallic phases and Sm2O3. Information on the variation of chemical potential of Sm as a function of composition
is required for the calculation of the oxygen potential corresponding to two- and three-phase equilibria. Proceeding
from the lower end of the diagram, with gradual increase in
oxygen potential pure Sm at unit activity gets oxidized first to
Sm2O3. Thus, the first horizontal line at the bottom of the
oxygen potential diagram represents equilibrium between
Sm, SmRh (l) and Sm2O3. The area between the first and
second horizontal lines signifies two-phase region involving
Sm2O3 and liquid alloy. In two-phase region, oxygen
potential increases with progressive oxidation and consequent decrease in the activity of Sm. The second horizontal
represents three-phase equilibrium between SmRh
(l) ? Sm4Rh ? Sm2O3. In a similar way, with progressive
oxidation of Sm in each intermetallic, a series of two- and
three-phase equilibria are generated. When all the Sm present in SmRh2 is oxidized, then metallic Rh is seen to coexist
with Sm2O3. At significantly higher chemical potential of
oxygen, Rh combines with Sm2O3 and oxygen gas to form
ternary oxide SmRhO3. The oxidation of Rh to Rh2O3 occurs
at an oxygen potential higher than that for the formation of
SmRhO3. Thus, the high oxygen potential region of the
diagram involves the phases Rh, Rh2O3, Sm2O3 and
SmRhO3.
Construction of a three-dimensional (3-D) oxygen
potential-composition diagram with Gibbs triangle representing composition at the base (XY plane) and oxygen
potential along the vertical (Z) axis is possible. However, it
will be cumbersome to read data accurately from such a
diagram. Hence, a two-dimensional (2-D) representation of
chemical potential is preferred. A disadvantage of such
diagrams is that the composition of alloys and oxides with
the same value for metallic fraction, gRh/(gSm ? gRh),
cannot be differentiated since they fall on the same vertical
line. However, as the stability fields of alloys and oxides
are well differentiated along the oxygen potential axis, this
is not generally a major hurdle. Another disadvantage is
that information on the oxygen nonstoichiometry cannot be
provided on the diagram because oxygen is not included in
the modified composition parameter. Nevertheless, oxygen
potential-composition diagram exhibits useful information
regarding the oxygen potential range for the stability of the
various phases. The diagram is complementary to the
conventional Gibbs triangle representation of the phase
relations in the ternary system (Fig. 1), where the composition of each phase can be clearly depicted.
Three-dimensional chemical potential diagram
of the system SmRhO at 1273 K
The isothermal three-dimensional chemical potential diagram for the system SmRhO at 1273 K is presented in
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Conclusions
123
Two-dimensional temperature-composition phase diagrams at different partial pressures of oxygen and oxygen
potential-composition diagrams at 1273 K for the system
SmRhO are computed from experimental data obtained
in this study and auxiliary data from the literature. An
isothermal three-dimensional chemical potential diagram
for the system SmRhO at 1273 K is also presented. The
four types of phase diagrams presented here provide a
comprehensive description of the system. Accurate calorimetric measurements of heat capacity as a function of
temperature and enthalpy of formation can further refine
the thermodynamic data obtained in this study.
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