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 CaMnO3–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 DHO and DSO larger in the orthorhombic than in the cubic phase can be interpreted as reflecting respective differences of DHO and DSO in the structural modifications of CaMnO3–

[18].” was changed to “Therefore, the absolute values of DHO and DSO larger in the orthorhombic than in the cubic phase can be interpreted as reflecting respective differences of DH ° and DS° 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 DHOx , DSOx and DHD , DSD 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 DHOx , DSOx and DHD , DSD in

Table 1 are used for calculations of DHO and DSO .The concentration values n, g and p for differently charged

3+ 4+ 5+ 3+ 4 + 5 + manganese species Mn , Mn and Mn , respectively, and oxygen non-stoichiometry in CaMnn Mn g Mn p O3-d are found from (10) – (12) as d+2K - 4 d K - D p = D D , n = p +2δ, g =1 – n – p (23) 4KD - 1

2 2 Here D = KD-4d K D + d and KD is the equilibrium constant for reaction 2, which depends on temperatures as

° ° KD=exp( D S D / R )exp( -D H D / RT ) , (24)” PAGE 6 Conclusions section

“Conclusions

The chemical potential of oxygen in CаMnO3– relative to the standard state is calculated from the experimental

p O2 – Т –  diagram. The partial molar enthalpy DHO and entropy DSO of oxygen is obtained from the linear plots of DmO ( d ,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

3+ electron defects and oxygen vacancies in CаMnO3–. It is found that the concentration of Mn 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

1 p “Fig. 1. Plots of /2RTln O2 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 DHO 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 DSO 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 抖n / d 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

1 p “Fig. 1. Plots of /2RTln O2 vs. temperature at different  ‘s in СаMnO3–δ with orthorhombic (a) and cubic (b) structure.

Fig. 2. Plots of partial molar enthalpy DHO 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 DSO 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 抖n / d 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).”