Thermodynamic functions of bismuth perrhenate doped by neodymium and indium

Thermodynamic functions of bismuth perrhenate doped by neodymium and indium

J. Chem. Thermodynamics 101 (2016) 31–34 Contents lists available at ScienceDirect J. Chem. Thermodynamics journal homepage: www.elsevier.com/locate...

583KB Sizes 1 Downloads 14 Views

J. Chem. Thermodynamics 101 (2016) 31–34

Contents lists available at ScienceDirect

J. Chem. Thermodynamics journal homepage: www.elsevier.com/locate/jct

Thermodynamic functions of bismuth perrhenate doped by neodymium and indium N.I. Matskevich a,⇑, Th. Wolf b a b

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia Karlsruhe Institute of Technology, Institute of Solid State Physics, Karlsruhe D-76344, Germany

a r t i c l e

i n f o

Article history: Received 25 January 2016 Received in revised form 10 May 2016 Accepted 14 May 2016 Available online 17 May 2016 Keywords: Bismuth oxide Rare earth compounds Heat capacity

a b s t r a c t For the first time the heat capacities of phase Bi12.5Nd1.4In0.1ReO24.5 have been measured in the temperature range of 175–550 K. Differential scanning calorimetry has been used for measurements. The temperature dependence of heat capacity is well described by a polynomial Cop,m (T) = 542.62 + 1.5107 T – 1.0402  10 3 T2 – 2.7875  106/T2. On the basis of smoothed heat capacities the enthalpy and entropy increments were calculated (T = 175–550 K). Ó 2016 Elsevier Ltd.

1. Introduction At present all over the world the search for promising materials to be used in devices operating at high temperatures, in particular in fuel cells, oxygen ceramic generators etc. is carried out intensively. Mixed oxides on the basis of rare-earth elements are promising materials for these purposes [1–10]. The d-form of Bi2O3 possesses one of the highest ionic conductivities, 1 S cm 1 at 1023 K, which is 2 orders of magnitude larger than the value of Y-stabilized zirconia. The disadvantage of d-bismuth oxide is its very narrow stability range, only 1000–1100 K. A lot of scientific papers were devoted to the problem of stabilizing bismuth oxide to room temperature. In first experiments to stabilize d-Bi2O3 using rare earth elements a satisfactory solution was not found. Substitution of VI group elements like sulfur, tungsten, and others led to a steep decrease of the ionic conductivity. About 10 years ago new compounds with the general formula Bi12.5Ln1.5ReO24.5 (Ln – lanthanides) were synthesized [11–15]. Measurements of the conductivity showed that the compounds were well-conductive and their conductivity was comparable with bismuth compounds doped by vanadium and copper. Bismuth compounds doped by neodymium and lanthanum possessed the highest conductivity. To learn more about the perspectives of these materials further detailed studies are necessary. At the same time it was shown in papers [16–18] that adding indium to mixed oxides leads to an increasing stability of the ⇑ Corresponding author. E-mail address: [email protected] (N.I. Matskevich). http://dx.doi.org/10.1016/j.jct.2016.05.009 0021-9614/Ó 2016 Elsevier Ltd.

compounds. Therefore we synthesized new compounds with the general formula Bi12.5Nd1.4In0.1ReO24.5. In this paper we present for the first time heat capacities of bismuth perrhenate doped by neodymium and indium (Bi12.4Nd1.4In0.1ReO24.5). Heat capacities were measured by differential scanning calorimetry in the temperature range of 175– 550 K. In future we plan to measure thermodynamic functions for compounds Bi12.5(Ln,In)1.5ReO24.5 with different lanthanides to construct dependence ‘‘thermodynamic property-structural property”. Knowledge of these relationships is very important to understand the nature of properties change [19]. 2. Experimental part We prepared Bi12.5Nd1.4In0.1ReO24.5 phase by solid state reaction. The initial reagents for synthesis were: Bi2O3, NH4ReO4, Nd2O3, In2O3. Detailed information about precursors is presented in Table 1. Nd2O3 and In2O3 were treated before synthesis at high temperatures up to constant weight. Starting reagents were mixed in an agate mortar and ground for about several hours with several intermediate reground in a planetary mill. Then the mixture was pressed and heated in air at temperature higher than 900 K. The procedures of reground and heating were repeated until Bi12.5Nd1.4In0.1ReO24.5 became a phase pure ceramic. The phase purity was analyzed with X-ray diffractometer (STADI-P, Stoe diffractometer, Germany, Cu Ka radiation). XRD pattern is presented in Fig. 1. X-ray diffraction indicated that the sample was single phase and that d-Bi2O3 structure had been stabilized to room temperature. Using the FullProf program we determined

32

N.I. Matskevich, Th. Wolf / J. Chem. Thermodynamics 101 (2016) 31–34

Table 1 Purity of initial compounds for synthesis.

Table 2 Results of chemical analysis of Bi12.5Nd1.4In0.1ReO24.5.

Compounds

Content of compounds (%) and method

Production company

Bi2O3

99.999%, Spectrophotometric method 99.9%, Spectrophotometric method 99.99%, Spectrophotometric method >99%, Fluorescence analysis

ABCR, Karlsruhe

Nd2O3 In2O3 NH4ReO4

Reacton, Johnson Matthey Company Reacton, Johnson Matthey Company Alfa Aesar, Johnson Matthey Company

the lattice parameters and space group. Space group was Fm-3m (cubic structure). We determined the lattice parameter for Bi12.5Nd1.4In0.1ReO24.5 as a = 0.56116 (16) nm. Sample Bi12.5Nd1.4In0.1ReO24.5 was characterized by chemical analysis as well. For the analysis of Bi, Nd, In a spectrophotometric method was used. The ARL ADVANT’XP sequential X-ray Fluorescence Spectrometer was used to analyze Re content. The oxygen content was determined by reducing melting method. Detailed information is presented in Table 2. According to the results of the analysis, the sample Bi12.5Nd1.4In0.1ReO24.5 was found to be single phase with an accuracy of about 0.1%. Differential scanning calorimetry was used to measure heat capacities of Bi12.5Nd1.4In0.1ReO24.5 in the temperature range of 175–550 K. We used calorimeter of Netzsch DSC 204 F1 Phoenix. DSC measurements of the sample and standard of Al2O3 were performed by the heat flow measurement method at a constant heating rate of 6 K min 1 in an aluminum crucible in an Ar flow of 25 ml min 1. The sample mass for Bi12.5Nd1.4In0.1ReO24.5 was 24.62 mg (molar mass is 3403.8653 g mol 1). The mass of Al2O3 was 24.78 mg. The baseline signal obtained by heating 2 empty crucibles was subtracted from the experimental results of samples. Al2O3 was used as standard to calculate heat capacity. Temperature scale graduation was performed by determination of the melting points of standard samples (C6H12, Hg, KNO3, In, Sn, Bi, Pb, Cd, Zn, CsCl).

Compounds

Content of elements (experimental data (%)) and methods of analysis

Content of elements (calculated data (%))

Impurities and method of analysis

Bi12.5Nd1.4In0.1ReO24.5

Bi, 76.68 ± 0.07; Nd, 5.99 ± 0.05; In, 0.31 ± 0.03; Re, 5.49 ± 0.04; O, 11.48 ± 0.05

Bi, 76.74; Nd, 5.93; In, 0.34; Re, 5.47; O, 11.52

Ho, Dy, Eu, Yb, La, Tm, Er, Pr, Sm, Ce, Te, Ca, Mg, Mn, Pb, Ag are presented at the level 10 3– 10 4 at.%

Bi, Nd, In – spectrophotometric method; Re – Xray fluorescence analysis; O – reducing melting method

Mass spectrometry method

Here the expanded uncertainty with 0.95 level of confidence is provided.

3. Results and discussion We measured 169 experimental points for heat capacities of Bi12.5Nd1.4In0.1ReO24.5 in the temperature range of 175–550 K (Table 3). The measurements of heat capacity showed that the curve of the heat capacity is smooth (Fig. 2) in the temperature interval. The relative standard uncertainty for the heat capacities ur(Cp,m) = 0.015. To calculate the smoothed values of heat capacities as well as the increment enthalpy and entropy we approximated our experimental data on the heat capacity by different polynomials. As it was shown our data can be well described by a polynomial Cop,m(T) = 542.62 + 1.5107 T – 1.0402  10 3 T2 – 2.7875  106/T2 (sum of squares of discrepancy is 1094.1). Preliminary the data were approximated by polynomials: (1) Cop,m(T) = 360.55 + 2.2328 T – 1.7996  10 3 T2 (sum of squares of discrepancy is 1938.7);

Fig. 1. Experimental and calculated patterns for Bi12.5Nd1.4In0.1ReO24.5.

33

N.I. Matskevich, Th. Wolf / J. Chem. Thermodynamics 101 (2016) 31–34 Table 3 Experimental values of heat capacity for Bi12.5Nd1.4In0.1ReO24.5 (molar mass is 3403.8653 g mol T/K 174.30 176.51 178.73 180.95 183.16 185.38 187.60 189.83 192.05 194.27 196.49 198.72 200.95 203.17 205.39 207.60 209.81 212.03 214.26 216.49 218.71 220.94 223.17 225.40 227.63 229.86 232.09 234.32 236.55

Cp,m(T)/ J mol 1 K 678.7 684.2 689.6 694.8 700.1 705.2 710.0 714.6 719.7 725.4 730.7 735.1 738.9 742.4 746.0 749.4 752.4 755.2 757.9 760.4 762.7 765.4 769.0 773.6 779.0 784.7 789.2 791.8 792.8

T/K 1

238.78 241.01 243.24 245.48 247.71 249.94 252.17 254.41 256.64 258.87 261.11 263.34 265.57 267.81 270.04 272.27 274.50 276.74 278.97 281.21 283.44 285.67 287.91 290.14 292.38 294.61 296.85 299.08 301.32

Cp,m(T)/ J mol 1 K 793.8 796.3 800.3 805.0 809.6 813.7 817.1 820.2 823.0 825.5 827.9 830.9 834.6 837.9 839.3 839.1 837.7 835.8 837.1 843.4 850.3 853.0 853.0 853.0 854.0 855.9 859.0 862.7 865.6

T/K 1

303.57 305.81 308.05 310.29 312.52 314.76 317.00 319.24 321.48 323.71 325.95 328.19 330.43 332.67 334.91 337.16 339.40 341.63 343.87 346.12 348.36 350.60 352.84 355.08 357.32 359.56 361.80 364.04 366.29

Cp,m(T)/ J mol 1 K

T/K 1

868.6 873.1 877.8 880.7 882.8 885.4 888.6 892.3 896.1 899.7 902.8 905.5 908.0 910.5 912.9 915.4 917.6 919.6 921.2 922.0 922.2 922.0 922.2 923.3 924.7 926.2 927.7 929.3 931.0

368.53 370.77 373.01 375.25 377.49 379.74 381.98 384.22 386.47 388.71 390.95 393.20 395.44 397.68 399.93 402.17 404.41 406.65 408.90 411.14 413.38 415.63 417.87 420.11 422.36 424.60 426.85 429.09 431.33

1

) at pressure p = 0.1 MPa (u(p) = 0.05 p). Cp,m(T)/ J mol 1 K 932.7 934.7 937.0 939.1 940.9 942.6 944.6 946.4 948.3 950.5 953.4 957.2 961.6 965.9 969.5 971.9 973.0 973.3 973.5 974.2 975.3 976.8 978.5 980.0 981.8 983.9 985.9 987.1 987.6

T/K 1

433.58 435.82 438.07 440.31 442.55 444.80 447.04 449.28 451.53 453.77 456.01 458.26 460.50 462.75 464.99 467.24 469.48 471.73 473.97 476.22 478.46 480.71 482.95 485.20 487.44 489.69 491.93 494.17 496.42

Cp,m(T)/ J mol 1 K 988.1 989.2 990.8 992.7 994.5 995.7 996.1 996.7 998.1 1000.1 1002.2 1004.2 1006.0 1007.9 1009.5 1010.6 1011.5 1012.6 1013.9 1015.1 1016.0 1016.8 1017.9 1018.9 1019.5 1019.5 1019.5 1020.0 1021.0

T/K 1

498.66 500.91 503.15 505.40 507.64 509.88 512.13 514.38 516.62 518.87 521.11 523.36 525.60 527.85 530.09 532.34 534.58 536.83 539.08 541.32 543.57 545.81 548.06 550.30

Cp,m(T)/ J mol 1 K

1

1022.4 1023.8 1025.4 1027.1 1028.8 1030.4 1031.7 1032.9 1033.9 1034.6 1035.3 1036.1 1037.1 1038.8 1041.2 1043.6 1045.0 1045.7 1046.5 1047.2 1047.9 1049.0 1050.3 1051.4

Standard uncertainty for temperature u(T) = 0.01 K; relative standard uncertainty for the heat capacities ur(Cp,m) = 0.015.

Fig. 2. Experimental and smoothed values of heat capacities of Bi12.5Nd1.4In0.1ReO24.5.

(2) Cop,m(T) = 248.06 + 3.2857 T – 4.8714  10 3 T2 + 2.8233  10 6 T3 J mol 1 K 1 (sum of squares of discrepancy is 1287.0); (3) Cop,m(T) = 774.19 + 0.55507 T – 6.0616  106/T2 (sum of squares of discrepancy is 2452.8). As was shown a polynomial A + B T + C T2 + D/T2 describes the obtained experimental data with the greatest accuracy. The scatter of heat capacity experimental data against approximating curve did not exceed 1%.

We used programs of Bank Data on Properties of Electronic Technique Materials [20] to calculate thermodynamic functions for Bi12.5Nd1.4In0.1ReO24.5. Using these programs on the basis of the heat capacity smoothed values the entropy and enthalpy increments [H(T) H(298.15 K) and S(T) S(298.15 K)] were calculated. Results are given in Table 4. The heat capacity under standard conditions was calculated as 869.2 J K 1mol 1 and within 2% agreement with the heat capacity estimated as the sum of binary

34

N.I. Matskevich, Th. Wolf / J. Chem. Thermodynamics 101 (2016) 31–34

Table 4 Smoothed values of heat capacities, enthalpy and entropy for Bi12.5Nd1.4In0.1ReO24.5 (molar mass 3403.8653 g mol 1). T/K

Cop,m/J mol

1

K

1

Hom(T) Hom (298.15)/ J mol

1

Som(T) Som (298.15)/J K

175.0 180.0 185.0 190.0 195.0 200.0 205.0 210.0 215.0 220.0 225.0 230.0 235.0 240.0 245.0 250.0 255.0 260.0 265.0 270.0 275.0 280.0 285.0 290.0 295.0 300.0 305.0 310.0 315.0 320.0 325.0 330.0 335.0 340.0 345.0 350.0 355.0 360.0

685.1 697.2 705.2 714.9 724.3 733.5 742.3 750.8 759.0 767.0 774.8 782.4 789.7 796.9 803.9 810.7 817.3 823.8 830.2 836.4 842.5 848.5 854.4 860.1 865.7 871.2 876.7 882.0 887.2 892.3 897.3 902.3 907.1 911.9 916.6 921.2 925.7 930.2

96,943 93,484 89,978 86,429 82,830 79,186 75,496 71,764 67,989 64,174 60,319 56,426 52,496 48,529 44,527 40,491 36,421 32,318 28,182 24,016 19,818 15,591 11,333 7047 2733 1610 5980 10,376 14,799 19,248 23,722 28,221 32,745 37,293 41,864 46,458 51,076 55,715

415.1 395.6 376.4 357.5 338.8 320.3 302.1 284.1 266.4 248.8 231.5 214.4 197.5 180.8 164.3 148.0 131.8 115.9 100.2 84.58 69.18 53.94 38.87 23.96 9.214 5.383 19.83 34.13 48.28 62.29 76.17 89.90 103.51 117.0 130.3 143.6 156.7 169.6

365.0 370.0 375.0 380.0 385.0 390.0 395.0 400.0 405.0 410.0 415.0 420.0 425.0 430.0 435.0 440.0 445.0 450.0 455.0 460.0 465.0 470.0 475.0 480.0 485.0 490.0 495.0 500.0 505.0 510.0 515.0 520.0 525.0 530.0

934.5 938.8 943.0 947.2 951.3 955.3 959.2 963.1 966.9 970.6 974.2 977.8 981.4 984.8 988.2 991.6 994.8 998.0 1001 1004 1007 1010 1013 1016 1019 1022 1024 1027 1029 1032 1034 1037 1039 1041

60,377 65,061 69,765 74,491 79,237 84,003 88,789 93,595 98,420 103,264 108,126 113,006 117,904 122,819 127,752 132,701 137,667 142,650 147,648 152,661 157,690 162,734 167,793 172,866 177,953 183,054 188,168 193,295 198,436 203,589 208,754 213,931 219,120 224,320

182.5 195.2 207.9 220.4 232.8 245.1 257.3 269.4 281.4 293.2 305.0 316.7 328.3 339.8 351.2 362.5 373.8 384.9 395.9 406.9 417.8 428.6 439.3 449.9 460.4 470.9 481.3 491.6 501.8 512.0 522.0 532.0 542.0 551.8

1

mol

1

Table 4 (continued) T/K 535.0 540.0 545.0 550.0

Cop,m/J mol

1

1043 1046 1048 1050

K

1

Hom(T) Hom (298.15)/ J mol 229,532 234,754 239,987 245,230

1

Som(T) Som (298.15)/J K

1

mol

1

561.6 571.3 581.0 590.6

Relative standard uncertainty for Cop,m, Hom(T) – Hom (298.15), Som(T) ur = 0.015.

Som (298.15) is

oxides heat capacities which equal to 874.7 J K 1mol 1. We estimated entropy for standard conditions as sum of binary oxides entropies: 1156.0 J K 1mol 1 (T = 298.15 K). The entropies and heat capacities of binary oxides were taken from Ref. [21]. 4. Conclusions For the first time we measured the heat capacities of Bi12.5Nd1.4In0.1ReO24.5 in the temperature range of 175–550 K. Differential-scanning calorimetry was used for measurements. We obtained smoothed data for heat capacities approximating experimental heat capacities by polynomial A + B T + C T2 + D/T2. On the basis of smoothed heat capacities we calculated entropy and enthalpy increments in the temperature range of 175–550 K. Acknowledgements This work is supported by Karlsruhe Institute of Technology (2015, Germany), Russian Fund of Basic Research (Project 13-08-00169) and Government Task for the Nikolaev Institute of Inorganic Chemistry. References [1] T.E. Crumpton, J.F.W. Mosselmans, C. Greaves, J. Mater. Chem. 15 (2005) 164– 167. [2] A. Zahariev, N. Kaloyanov, V. Parvanova, C. Girginov, Thermochim. Acta 594 (2014) e11–e15. [3] M.A. Pogosova, D.I. Provotorov, A.A. Eliseev, M. Jansen, P.E. Kazin, Dyes Pigments 113 (2015) 96–101. [4] J.C. Boivin, Int. J. Inorg. Mater. 3 (2001) 1261–1266. [5] D.A. Medvedev, J.G. Lyagaeva, E.V. Gorbova, A.K. Demin, P. Tsiakaras, Progress Mater., Science 75 (2016) 38–79. [6] N.I. Matskevich, M.V. Chuprova, R. Punn, C. Greaves, Thermochim. Acta 459 (2007) 125–126. [7] A.N. Bryzgalova, N.I. Matskevich, C. Greaves, C.H. Hervoches, Thermochim. Acta 513 (2011) 124–127. [8] D.S. Khaerudini, G. Guan, P. Zhang, X. Hao, A. Abudula, Rev. Chem. Eng. 30 (2014) 539–551. [9] M. Drache, P. Roussel, J.P. Wignacourt, Chem. Rev. 107 (2007) 80–96. [10] M. Colmont, M. Drache, P. Roussel, J. Power Sources 195 (2010) 7207–7212. [11] R. Punn, A.M. Feteira, D.C. Sinclair, C. Greaves, J. Am. Chem. Soc. 128 (2006) 15386–15387. [12] C.H. Hervoches, C. Greaves, J. Mater. Chem. 20 (2010) 6759–6763. [13] N.I. Matskevich, Th. Wolf, C. Greaves, P. Adelmann, I.V. Vyazovkin, M.Yu. Matskevich, J. Chem. Thermodyn. 91 (2015) 234–239. [14] N.I. Matskevich, A.N. Bryzgalova, T. Wolf, P. Adelmann, D. Ernst, T.I. Chupakhina, J. Chem. Thermodyn. 53 (2012) 23–26. [15] N.I. Matskevich, T. Wolf, J. Alloys Compd. 538 (2012) 45–47. [16] N.I. Matskevich, Th. Wolf, J. Chem. Thermodyn. 42 (2010) 225–228. [17] N.I. Matskevich, M.Yu. Matskevich, Th. Wolf, A.N. Bryzgalova, T.I. Chupakhina, O.I. Ahyfrieva, J. Alloys Compd. 577 (2013) 148–151. [18] N.I. Matskevich, Th. Wolf, P. Adelmann, A.N. Semerikova, O.I. Anyfrieva, Thermochim. Acta 615 (2015) 68–71. [19] L.M. Sprunger, J. Gibbs, A. Proctor, W.E. Acree Jr., M.H. Abraham, Y. Meng, C. Yao, J.L. Anderson, Ind. Eng. Chem. Res. 48 (2009) 4145–4154. [20] Yu.F. Minenkov, N.I. Matskevich, Yu.G. Stenin, P.P. Samoilov, Thermochim. Acta 278 (1996) 1–8. [21] V.P. Glushko, Termicheskie Konstanty Veshchestv (Thermal Constants of Substances), VINITI, Moscow, 1965–1982. pp. 1–10.

JCT 16-67