Abstract
In this study, the standard molar Gibbs energy of formation of Y2Ru2O7(s) and Y3RuO7(s) was determined using calcia-stabilized zirconia (CSZ) as an electrolyte and air as a reference electrode. The cells can be represented by: (−)Pt/{Y2O3(s) + Y2Ru2O7(s) + Ru(s)}//CSZ//O2(p(O2) = 21.21 kPa)/Pt(+), (−)Pt/{Y3RuO7(s) + Y2Ru2O7(s) + Y2O3(s)}//CSZ//O2(p(O2) = 21.21kPa)/Pt(+). The electromotive force was measured in the temperature range from 981 to 1155 K and 932 to 1186 K, respectively. The standard molar Gibbs energy of formation of Y2Ru2O7(s) and Y3RuO7(s) from elements in their standard state was calculated by the least squares regression analysis of the data obtained in the present study and can be given, respectively, by: {ΔfG(Y2Ru2O7, s)/(kJmol−1) ± 2.22} = − 2554.1 + 0.625 ⋅ (T/K) and {ΔfG(Y3RuO7, s)/(kJmol−1) ± 2.45} = − 3249.5 + 0.635 ⋅ (T/K). The standard molar heat capacity Cop,m(T) of Y2Ru2O7(s) was measured using a heat flux–type differential scanning calorimeter (DSC) in the temperature range, from 307 to 780 K. The heat capacity was fitted into a mathematical expression and can be represented by: Cp, m(Y2Ru2O7, s, T)(JK−1mol−1) = 256.1 + 5.88 ∙ 10−2T(K) − 34.75 ∙ 105/T2(K). (307 ≤ T (K) ≤ 780). The heat capacity of Y2Ru2O7(s) was used along with the data obtained from the electrochemical cell to determine its decomposition temperature and stability in air and to calculate other thermodynamic parameters.
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References
Wiss F, Raju NP, Wills AS, Greedan JE (2000) Structure and magnetism in Pr3RuO7. Int J Inorg Mater 2:53–59
Greedan JE (2001) Geometrically frustrated magnetic materials. J Mater Chem 11:37–53
Cao G, McCall S, Crow JE, Guertin RP (1997) Magnetic ordering and enhanced electronic heat capacity in insulating. Phys Rev Lett 78:1751–1754
Rard JA (1985) Chemistry and thermodynamics of ruthenium and some of its inorganic compounds and aqueous species. Chem Rev 85:1–39
Cava RJ (2004) Schizophrenic electrons in ruthenium-based oxides. Dalton Trans 10:2979–2987
Greedan JE, Sato M, Ali N, Datars WR (1987) Electrical resistivity of pyrochlore compounds R2Mo2O7 (R = Nd, Sm, Gd, Tb, Y). J Solid State Chem 68:300–306
Nishimine H, Wakeshima M, Hinatsu Y (2005) Structures, magnetic and thermal properties of Ln3MoO7 (Ln=La, Pr, Nd,Sm,Eu). J Solid State Chem 178:1221–1229
van Berkel FPF, Ijdo DJW (1986) The orthorhombic fluorite related compounds Ln3RuO7 Ln=Nd, Sm and Eu. Mater Res Bull 21:1103–1106
Rossell HJ (1979) Fluorite-related phases Ln3MO7, Ln = rare earth, Y or Sc, M = Nb, Sb, or Ta. J Solid State Chem 27:115–122
Harada D, Hinatsu Y (2002) Magnetic and calorimetric studies on one dimensional Ln3RuO7(Ln=Pr,Gd). J Solid State Chem 164:163–168
Harada D, Hinatsu Y (2001) A study of the magnetic and thermal properties of Ln3RuO7 (Ln=Sm,Eu). J Solid State Chem 158:245–253
Lam R, Wiss F, Greedan JE (2002) Magnetic properties of the fluorite related La3MoO7 phases M=Ru and Os. J Solid State Chem 167:182–187
Cruickshank KM, Glasser FP (1994) Rare earth platinum group mixed metal oxide systems. J Alloys Comp 210:177–184
Kobayashi H, Kanno R, Kawamoto Y, Kamiyama T, Izumi F, Sleight AW (1995) Synthesis, crystal structure, and electrical properties of the pyrochlores Pb2-x LnxRu2O7-y(Ln = Nd, Gd). J Solid State Chem 114:15–23
Blacklock K, White HW, Gurmen E (1980) Specific heats of the pyrochlore compounds Y2Mo2O7 and Y2Ru2O7. J Chem Phys 73:19661969
Taira N, Wakeshima M, Hinatsu Y (1999) Magnetic properties of ruthenium pyrochlores Y2Ru2O7 and Lu2Ru2O7. J Solid State Chem 144:216–219
Lee YS, Lee JS, Kim KW, Noh TW, Yu J, Takeda Y, Kanno R (2001) Optical investigation of A(2)Ru(2)O(7) (A = Y, Tl, and Bi): temperature dependent selfdoping effects. Physica C 364:632–635
Parrondo J, Morgan G, Capuano C, Ayersb KE, Raman V (2015) Pyrochlore electrocatalysts for efficient alkaline water electrolysis. J Mater Chem A 3:10819–10827
Park J, Park M, Nam G, Kim MG, Cho J (2017) Unveiling the Catalytic Origin of Nanocrystalline Yttrium Ruthenate Pyrochlore as a Bifunctional Electrocatalyst for Zn-Air Batteries. Nano Lett 17:3974–3981
Kim J, Shih PC, Tsao KC, Pan YT, Yin X, Sun CJ, Yang H (2017) High-performance pyrochlore-type yttrium ruthenate electrocatalyst for oxygen evolution reaction in acidic media. J Am Chem Soc 139:12076–12083
Shin JM, Park JJ, Shin SW, Kim KY (2005) Effectiveness of yttria filters for the removal of volatile ruthenium at high temperatures. Key Eng Mater 277:470–474
Kleykamp H (1988) The chemical state of fission products in oxide fuels at different stages of the nuclear fuel cycle. Nucl Tech 80:412–422
Kanno R, Takeda Y, Yamamoto T, Kawamoto Y, Yamamoto O (1993) Crystal structure and electrical properties of the pyrochlore ruthenate Bi2-xYxRu2O7. J Solid State Chem 102:106–114
Banerjee A, Singh Z, Venugopal V (2009) Heat capacity and Gibbs energy of formation of the ternary oxide CdRh2O4(s). J Solid State Ionics 180:1337–1341
Pratt JN (1990) Applications of solid electrolytes in thermodynamic studies of materials: a review. Metall Trans A 21:1223–1250
Banerjee A, Singh Z (2009) System Zn–Rh–O: Heat capacity and Gibbs free energy of formation using differential scanning calorimeter and electrochemical cell. J Solid State Electrochem 13:1201–1207
Sabbah R, Xu-wu AX, Chickos JS, Planas Leitao ML, Roux MV, Torres LA (1999) Reference materials for calorimetry and differential thermal analysis. Thermochim Acta 331:93–204
Hohne GWH, Hemminger WF, Flammershein HJ (2003) Differential scanning calorimetry, 2nd edn. Springer, Berlin
ASTD, Ver. 2.0, G. V. Belov, B. G. Trusov, 1983-1995, Moscow
Chase MW, Jr. JANAF Thermochemical Tables, Fourth edn., J Phys Chem, (monograph no. 91995)
Kubachewski O, Alcock CB, Spencer PJ (1993) Materials Thermochemistry, 6th. edn. Pergamon, Oxford
Leitner J, Vonka P, Sedmidubsky D, Svoboda P (2010) Application of Neumann-Kopp rule for the estimation of heat capacity of mixed oxides. Thermochim Acta 487:7–13
Grimvall G (1999) Thermophysical properties of materials, Elsevier, 367-368
Kmeic R, Swinkowska Z, Gurgul J, Rams M, Zarzycki A, Tomala K (2006) Investigation of the magnetic properties of Y2Ru2O7 by 99Ru Mössbauer spectroscopy. Phys Rev B 74:104425–104429
Taira N, Wakeshima M, Hinatsu Y (2000) Specific heat and ac susceptibility studies on ruthenium pyrochlores R2Ru2O7 (R = Rare Earths). J Solid State Chem 152:441–446
Graves K, Kirby KB, Rardin R (1991) FREED Version 2.1
Cordfunke EHP, Konings RJM (1988) The enthalpy of formation of ruthenium dioxide. Thermochim Acta 129:63–69
Acknowledgements
The authors wish to thank Dr. Meera Keskar, from FCD, BARC, for the XRD analysis. The authors are thankful to Dr. S. Kannan Head, Fuel Chemistry Division, and Dr. P. K. Pujari, Associate Director, R C, and I Group BARC, Mumbai, for their constant support and encouragement.
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Banerjee, A. Determination of thermodynamic properties of the ternary oxides in the Y-Ru-O system by electromotive force measurements and differential scanning calorimetric measurements. J Solid State Electrochem 23, 1749–1755 (2019). https://doi.org/10.1007/s10008-019-04268-8
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DOI: https://doi.org/10.1007/s10008-019-04268-8