List of changes in the manuscript No JSEL-D-13-00395
TITLE
“Thermodynamics of oxygen CaMnO3–δ” was changed to “Thermodynamics of oxygen in CaMnO3–δ”
ABSTRACT
The sentence
“The experimental data for equilibrium oxygen content were used in order to obtain variations of partial
thermodynamic functions of oxygen with changes of oxygen stoichiometry in calcium manganite CaMnO 3–δ”
was changed to “The experimental data for equilibrium oxygen content were used in order to extract
increments of partial molar thermodynamic functions of oxygen with changes of oxygen stoichiometry in
calcium manganite CaMnO3–δ.”
PAGE 2
The sentence
“In particular, the calculated entropy for reaction (1) in the orthorhombic phase occurs in good coincidence
with the experimentally observed oxidation entropy of orthorhombic CаMnO2.5 to CаMnO3 [19].” was
changed to “In particular, the calculated entropy for reaction 1 in the cubic phase occurs in good coincidence
with the observed oxidation entropy of CаMnO2.5 to CаMnO3 at 950 °С [19].”
PAGE 3
The sentence
“Therefore, the absolute values of H O and S O larger in the orthorhombic than in the cubic phase can be
interpreted as reflecting respective differences of H O and S O in the structural modifications of CaMnO3–
[18].” was changed to “Therefore, the absolute values of H O and S O larger in the orthorhombic than in the
cubic phase can be interpreted as reflecting respective differences of H and S in the structural
modifications of CaMnO3–, Table 1 [18].”
The sentence
“…where symbols μ° designate δ independent parts of chemical potentials of respective defect species while
S(conf) is the configuration entropy that can be calculated as” was changed to “…where symbols μ° designate
δ independent parts of chemical potentials of respective defects. Following [21] we assume that interaction
energies between the species entering reactions (1) and (2) are included in μ ’s. The configuration entropy
S(conf) can be calculated as”
PAGE 5
The sentence
“The thermodynamic parameters H Ox , SOx and H D , SD and equilibrium constants KOx and KD for reactions
(1) and (2) are taken from [18] in order to calculate changes in concentration of manganese species with δ and,
consequently, their derivatives with respect to δ.” was changed to “The values of H Ox , SOx and H D , SD in
Table 1 are used for calculations of H O and S O .The concentration values n, g and p for differently charged
manganese
CaMn 3n Mn 4g Mn 5p O3
p
Mn3+,
species
Here D =
and
Mn5+,
respectively,
and
oxygen
non-stoichiometry
in
are found from (10) – (12) as
  2 K D  4 K D  D
4KD  1
Mn4+
,
n = p +2δ,
g =1 – n – p
(23)
KD  4 2 KD   2 and KD is the equilibrium constant for reaction 2, which depends on temperatures as
KD  exp(SD / R)exp(HD / RT ) ,
(24)”
PAGE 6
Conclusions section
“Conclusions
The chemical potential of oxygen in CаMnO3– relative to the standard state is calculated from the experimental
pO2 – Т –  diagram. The partial molar enthalpy H O and entropy S O of oxygen is obtained from the linear
plots of O ( , T ) versus temperature. The partial thermodynamic functions of oxygen in CаMnO3– are found to
depend on nonstoichiometry and crystalline structure. The interrelation of partial molar thermodynamic
functions of oxygen with defect formation parameters is found based on thermodynamic analysis of defect
equilibrium in CаMnO3–. The good coincidence of experimental and calculated values for partial molar
thermodynamic functions demonstrates applicability of the ideal solution approximation for description of
electron defects and oxygen vacancies in CаMnO3–. It is found that the concentration of Mn3+ cations
significantly depends on solid – gas phase oxygen exchange and intrinsic reaction of thermal excitation of Mn4+
cations. As a result, the partial molar enthalpy and entropy of oxygen in CаMnO3– both occur to strongly
depend on nonstoichiometry.”
PAGE 8
Figure Captions
“Fig. 1. Plots of 1/2RTln pO2 vs. temperature at different  ‘s in СаMnO3–δ with orthorhombic (a) and cubic (b)
structure. O – orthorhombic phase, C – cubic phase.
Fig. 2. Plots of partial molar enthalpy H O vs. oxygen content (3–δ) in СаMnO3–δ. Dots – experimental values
(uncertainty ± 3 kJ/mol), solid lines – results of calculations with the help of Eq.(21) at T=const. O –
orthorhombic phase, C – cubic phase.
Fig. 3. Plots of partial molar entropy S O vs. oxygen content (3–δ) in СаMnO3–δ. Dots – experimental values
(uncertainty ± 2 kJ/molK), solid lines – results of calculations with the help of Eq.(22) at T=const. O –
orthorhombic phase, C – cubic phase.
Fig. 4. Isothermal plots of n /  vs. oxygen content (3–δ) in СаMnO3–δ as calculated with the help of Eq.(13).
O – orthorhombic phase, C – cubic phase.
Fig. 5. Isothermal plots of sO (conf ) vs. oxygen content (3–δ) in СаMnO3–δ as calculated with the help of
Eq.(15). O – orthorhombic phase, C – cubic phase.” was changed to
“Fig. 1. Plots of 1/2RTln pO2 vs. temperature at different  ‘s in СаMnO3–δ with orthorhombic (a) and cubic (b)
structure.
Fig. 2. Plots of partial molar enthalpy H O vs. oxygen content (3–δ) in orthorhombic and cubic СаMnO3–δ.
Dots show experimental values (uncertainty ± 3 kJmol–1), solid lines show results of calculations with the help
of Eq.(21) at T=const. The empty squares show data [16].
Fig. 3. Plots of partial molar entropy S O vs. oxygen content (3–δ) in orthorhombic and cubic СаMnO3–δ. Dots
show experimental values (uncertainty ± 2 Jmol–1K–1), solid lines show results of calculations with the help of
Eq.(22) at T=const. The empty squares show data [16].
Fig. 4. Isothermal plots of n /  vs. oxygen content (3–δ) in orthorhombic and cubic СаMnO3–δ as calculated
with the help of Eq.(13).
Fig. 5. Isothermal plots of sO (conf ) vs. oxygen content (3–δ) in orthorhombic and cubic СаMnO3–δ as calculated
with the help of Eq.(15).”