Skip to main content

New thermodynamic data for CoTiO3, NiTiO3 and CoCO3 based on low-temperature calorimetric measurements

Abstract

The low-temperature heat capacities of nickel titanate (NiTiO3), cobalt titanate (CoTiO3), and cobalt carbonate (CoCO3) were measured between 2 and 300 K, and thermochemical functions were derived from the results. Our new data show previously unknown low-temperature lambda-shaped heat capacity anomalies peaking at 37 K for CoTiO3 and 26 K for NiTiO3. From our data we calculate standard molar entropies (298.15 K) for NiTiO3 of 90.9 ± 0.7 J mol-1 K-1 and for CoTiO3 of 94.4 ± 0.8 J mol-1 K-1. For CoCO3, we find only a small broad heat capacity anomaly, peaking at about 31 K. From our data, we suggest a new standard entropy (298.15 K) for CoCO3 of 88.9 ± 0.7 J mol-1 K-1.

Background

Nickel titanate (NiTiO3) and cobalt titanate (CoTiO3) belong to an important group of ilmenite-type transition metal bearing phases with a number of interesting magnetic and electric properties [15]. They are also important for technical applications due to their catalytic properties [68]. CoCO3 is a phase with interesting magnetic properties, which has not been studied in detail [912]. Structures, phase relations and physical properties of these phases are well documented [5, 9, 1321], there is, however, a lack of low-temperature calorimetric data and associated third-law entropies. Other transition metal bearing oxide phases have recently been shown to exhibit large, hitherto unknown low-temperature heat capacity anomalies [2231] and the aim of this paper is to investigate low-temperature heat capacities for NiTiO3, CoTiO3, and CoCO3. To our knowledge, for NiTiO3, CoTiO3, there are no reported low-temperature CP data published in the literature, and the only data for CoCO3 date back to the 1960s.

Experimental

Samples

Heat capacity measurements were performed on synthetic polycrystalline NiTiO3, CoTiO3, and CoCO3 samples. The NiTiO3 and CoTiO3 sample used in our study were synthesized from equimolar mixtures of CoO (Merck, 99.999% purity), NiO (Merck, 99.999% purity) and TiO2 (Merck, 99.99% purity). The TiO2 powder was previously fired at 1,000°C for 12 h to release any absorbed water or hydroxide. The oxides were mixed under acetone in an agate mortar and pestle for 15 min and subsequently pressed into several high density pellets of 3 mm diameter. CoCO3 was purchased from Alfa Aesar (99.5% purity, metals based). X-ray diffraction indicated CoCO3 only, with cell parameters of a = 4.662 ± 0.002 and c = 14.955 ± 0.005 Å. The NiTiO3 and CoTiO3 pellets were placed in a vertical drop furnace in a small, hand-crafted basket made of platinum wire, were fired in air at 1,150°C for 24 h, then slowly cooled to 1,000°C for 24 h, and further cooled to 900°C and held for another 24 h. The samples were then rapidly drop-quenched in distilled water and dried at 110°C for 1 h. X-ray diffraction indicated CoTiO3 and NiTiO3 only, no impurities or other unreacted oxides were detected. Our synthetic CoTiO3 had cell parameters of a = 5.029 ± 0.004 and c = 13.79 ± 0.02 Å and the NiTiO3 sample had cell parameters of a = 5.061 ± 0.006 and c = 13.91 ± 0.08 Å which compares well with previous results [1].

Low-temperature calorimetry

The heat capacities were measured with a commercially available low temperature Quantum Design Physical Properties Measurement System (PPMS) at the University of Münster. The heat capacities were measured using the heat pulse method, measuring the response of the calorimeter to a heat pulse, which is evaluated as a function of time [32]. The accuracy of the method has been tested by several groups [33, 34] who found that the PPMS is capable of reproducing heat capacities of reference materials to better than 1% at T > 100 K and around 3-5% at T < 100 K. We have performed further tests using the Münster PPMS, coming to the identical conclusions. Our measurements on synthetic Al2O3 (NIST SRM-720, [35]) are depicted in Figure 1. The data show that we reproduce the heat capacity of SRM-720 to better than 1% (with an average of 0.4%) at temperatures higher than 90 K, and around 4% at T < 90 K. Overall, the standard entropy of NIST SRM-720 corundum was reproduced with our calorimeter within 0.8%, a value which is used to estimate the overall uncertainty of our calculated standard entropy values.

Figure 1
figure1

Comparison of published heat capacities of NIST SRM-720 (Ditmars et al. 1982) with PPMS measurements done at Münster University.

For the actual measurements, the sample pellets were fixed onto a pre-calibrated sample holder using Apiezon N-Grease. To compensate for the heat capacity and anomalies caused by the grease [36], addenda measurements were first performed without the sample. These heat capacity values were then subtracted from the sample measurement. Heat capacities were measured from below 5 to 303 K in increments that varied between 0.5 and 20 K at the highest temperatures (Figure 1; Tables 1, 2 and 3).

Table 1 Experimental Molar Heat Capacities for NiTiO3
Table 2 Experimental Molar Heat Capacities for CoTiO3
Table 3 Experimental Molar Heat Capacities for CoCO3

Results and Discussion

The experimental values for the low-temperature heat capacity of NiTiO3, CoTiO3 and CoCO3 are compiled in Tables 1, 2 and 3.

Figures 2, 3, and 4 depict the heat capacity of NiTiO3, CoTiO3 and CoCO3 as a function of temperature. The data for NiTiO3 and CoTiO3 were recorded in two scans, the first one ranging from about 1.5 to about 60 K, the other scan continuously up to room temperature. Figures 2 and 3 show excellent agreement between the two separate measurements. The data for CoCO3 were collected in only one scan, as only a broad low-temperature anomaly was found (Figure 4).

Figure 2
figure2

Low-temperature heat capacity data for NiTiO 3 . The insert shows results from two scans done at low temperatures.

Figure 3
figure3

Low-temperature heat capacity data for CoTiO 3 . The insert shows results from two scans done at low temperatures.

Figure 4
figure4

Low-temperature heat capacity data for CoCO 3 .

The standard entropies at 298.15 K (S298) were calculated from the CP data (using a T3 extrapolation to 0 K) and resulted in S298 = 90.9 ± 0.7 J mol-1 K-1 for NiTiO3, 94.4 ± 0.8 J mol-1 K-1 for CoTiO3 and 88.9 ± 0.7 J mol-1 K-1 for CoCO3 (Tables 4, 5 and 6). Our data for S298 are compared to previous results in Table 7. For CoCO3, our new data agree very well with more than 40 year old data [37]. However, our measured entropies do not agree well with estimated values [38], probably due to the fact that low temperature heat capacity anomalies occur in NiTiO3 and CoTiO3.

Table 4 Thermodynamic properties at selected temperatures for NiTiO3
Table 5 Thermodynamic properties at selected temperatures for CoTiO3
Table 6 Thermodynamic properties at selected temperatures for CoCO3
Table 7 Comparison of our data with previous results

Our data for NiTiO3 show that a lambda-shaped low-temperature heat capacity anomaly occurs at around 26 K (Figure 2), coinciding with the antiferromagnetic transition [15, 16, 39]. In a similar fashion, CoTiO3 exhibits a low-temperature heat capacity anomaly peaking at 37 K, which is in excellent agreement with the old structural and magnetic data [18, 40]. In contrast, CoCO3 shows only a broad anomaly peaking at around 31 K (Figure 4), which may be caused by the transition to an antiferromagnetic state [9, 11, 12]. Our data agree well with a recent study [11] which found that the weak antiferromagnets (Co, Ni)CO3 exhibit magnetic ordering temperatures of well below 40 K. Whilst our data indicate a transition temperature of 31 K, the older magnetic susceptibility data [10] gave a transition temperature of 18 K. The reason for the discrepancy is unknown.

Conclusions

We present new low-temperature calorimetric data for the ilmenite-type oxides NiTiO3 and CoTiO3, and for the weak antiferromagnet CoCO3. Our data show that all three phases show low-temperature heat capacity anomalies peaking between 20 and 40 K. The calorimetric data are used to calculate standard molar entropies (298.15 K), which are, due to the low-temperature anomalies, significantly higher than those previously anticipated.

References

  1. 1.

    Baraton MI, Busca G, Prieto MC, Ricchiardi G, Escribano VS: On the vibrational-spectra and structure of FeCrO3 and of the ilmenite-type compounds CoTiO3 and NiTiO3. J Solid State Chem. 1994, 112: 9-14. 10.1006/jssc.1994.1256.

    CAS  Article  Google Scholar 

  2. 2.

    Chao TS, Ku WM, Lin HC, Landheer D, Wang YY, Mori Y: CoTiO3 high-kappa, dielectrics on HSG for DRAM applications. IEEE Trans Electr Dev. 2004, 51: 2200-2204. 10.1109/TED.2004.839880.

    CAS  Article  Google Scholar 

  3. 3.

    Chuang SH, Hsieh ML, Wu SC, Lin HC, Chao TS, Hou TH: Fabrication and Characterization of high-K dielectric nickel titanate thin films using a modified sol-gel method. J Am Ceram Soc. 2011, 94: 251-255.

    Article  Google Scholar 

  4. 4.

    Kang YM, Kim KT, Kim JH, Kim HS, Lee PS, Lee JY, Liu HK, Dou SX: Electrochemical properties of Co3O4, Ni-Co3O4 mixture and Ni-Co3O4 composite as anode materials for Li ion secondary batteries. J Power Sources. 2004, 133: 252-259. 10.1016/j.jpowsour.2004.02.012.

    CAS  Article  Google Scholar 

  5. 5.

    Lerch M, Laqua W: Contributions to the properties of titanates with ilmenite structure 2. Study on the thermodynamics and the electrical-conductivity of NiTiO3 and other phases with ilmenite structure. Z Anorg Allg Chem. 1992, 610: 57-63. 10.1002/zaac.19926100110.

    CAS  Article  Google Scholar 

  6. 6.

    Arvanitidis I, Kapilashrami A, Du SC, Seetharaman S: Intrinsic reduction kinetics of cobalt- and nickel-titanates by hydrogen. J Mater Res. 2000, 15: 338-346. 10.1557/JMR.2000.0053.

    CAS  Article  Google Scholar 

  7. 7.

    Brik Y, Kacimi M, Ziyad M, Bozon-Verduraz F: Titania-supported cobalt and cobalt-phosphorus catalysts: Characterization and performances in ethane oxidative dehydrogenation. J Catal. 2001, 202: 118-128. 10.1006/jcat.2001.3262.

    CAS  Article  Google Scholar 

  8. 8.

    Voss A, Borgmann D, Wedler G: Characterization of alumina, silica, and titania supported cobalt catalysts. J Catal. 2002, 212: 10-21. 10.1006/jcat.2002.3739.

    CAS  Article  Google Scholar 

  9. 9.

    Alikhanov RA: Antiferromagnetism of CoCO3. Soviet Physics JETP-USSR. 1961, 12: 1029-1030.

    Google Scholar 

  10. 10.

    Borovik-Romanov AS, Ozhogin VI: Weak ferromagnetism in an antiferromagnetic CoCO3 single crystal. Soviet Physics JETP-USSR. 1961, 12: 18-24.

    Google Scholar 

  11. 11.

    Meshcheryakov VF: Crystal field and magnetization of canted antiferromagnet CoCO3. J Exp Theor Phys. 2007, 105: 998-1010. 10.1134/S106377610711012X.

    CAS  Article  Google Scholar 

  12. 12.

    Ozhogin VI: The Antiferromagnets CoCO3, CoF2, and FeCO3 in strong fields. Soviet Physics JETP-USSR. 1964, 18: 1156-1157.

    Google Scholar 

  13. 13.

    Birnbaum H, Scott RK: X-ray diffraction studies of the system-Zn2TiO4 NiTiO3. J Am Chem Soc. 1950, 72: 1398-1399.

    CAS  Article  Google Scholar 

  14. 14.

    Ishikawa Y, Sawada S: The study on substances having the ilmenite structure 1. Physical properties of synthesized FeTiO3 and NiTiO3 ceramics. J Phys Soc Jpn. 1956, 11: 496-501. 10.1143/JPSJ.11.496.

    CAS  Article  Google Scholar 

  15. 15.

    Shirane G, Pickart SJ, Ishikawa Y: Neutron diffraction study of antiferromagnetic MnTiO3 and NiTiO3. J Phys Soc Jpn. 1959, 14: 1352-1360. 10.1143/JPSJ.14.1352.

    CAS  Article  Google Scholar 

  16. 16.

    Heller GS, Stickler JJ, Kern S, Wold A: Antiferromagnetism in NiTiO3. J Appl Phys. 1963, 34: 1033-1035. 10.1063/1.1729357.

    CAS  Article  Google Scholar 

  17. 17.

    Kaczer J: Hexagonal anisotropy and magnetization curves of antiferromagnetic CoCO3. Soviet Physics JETP-USSR. 1963, 16: 1443-1448.

    Google Scholar 

  18. 18.

    Newnham RE, Santoro RP, Fang JH: Crystal structure and magnetic properties of CoTiO3. Acta Crystallogr. 1964, 17: 240-245. 10.1107/S0365110X64000615.

    CAS  Article  Google Scholar 

  19. 19.

    Rudashevskii EG: Antiferromagnetic resonance in CoCO3. Soviet Physics JETP-USSR. 1964, 19: 96-97.

    Google Scholar 

  20. 20.

    Lerch M, Boysen H, Neder R, Frey F, Laqua W: Neutron-scattering investigation of the high-temperature phase-transition in NiTiO3. J Phys Chem Solids. 1992, 53: 1153-1156. 10.1016/0022-3697(92)90032-9.

    CAS  Article  Google Scholar 

  21. 21.

    Busca G, Ramis G, Amores JMG, Escribano VS, Piaggio P: FT Raman and FTIR studies of titanias and metatitanate powders. J Chem Soc-Faraday Trans. 1994, 90: 3181-3190. 10.1039/ft9949003181.

    CAS  Article  Google Scholar 

  22. 22.

    Klemme S, Ahrens M: Low-temperature heat capacity of magnesioferrite (MgFe2O4). Phys Chem Miner. 2005, 32: 374-378. 10.1007/s00269-005-0003-8.

    CAS  Article  Google Scholar 

  23. 23.

    Klemme S, Neill HSO, Schnelle W, Gmelin E: The heat capacity of MgCr2O4, FeCr2O4, and Cr2O3 at low temperatures and derived thermodynamic properties. Am Mineral. 2000, 85: 1686-1693.

    CAS  Article  Google Scholar 

  24. 24.

    Klemme S, van Miltenburg JC: Thermodynamic properties of nickel chromite (NiCr2O4) based on adiabatic calorimetry at low temperatures. Phys Chem Miner. 2002, 29: 663-667. 10.1007/s00269-002-0280-4.

    CAS  Article  Google Scholar 

  25. 25.

    Klemme S, Van Miltenburg JC: Thermodynamic properties of hercynite (FeAl2O4) based on adiabatic calorimetry at low temperatures. Am Mineral. 2003, 88: 68-72.

    CAS  Article  Google Scholar 

  26. 26.

    Klemme S, Van Miltenburg JC: The entropy of zinc chromite (ZnCr2O4). Mineral Mag. 2004, 68: 515-522. 10.1180/0026461046830202.

    CAS  Article  Google Scholar 

  27. 27.

    Klemme S, van Miltenburg JC: The heat capacities and thermodynamic properties of NiAl2O4 and CoAl2O4 measured by adiabatic calorimetry from T = (4 to 400) K. J Chem Thermod. 2009, 41: 842-848. 10.1016/j.jct.2009.01.014.

    CAS  Article  Google Scholar 

  28. 28.

    Manon MRF, Dachs E, Essene EJ: Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks. Contr Mineral Petrol. 2008, 156: 709-720. 10.1007/s00410-008-0311-3.

    CAS  Article  Google Scholar 

  29. 29.

    Dachs E, Geiger CA, Withers AC, Essene EJ: A calorimetric investigation of spessartine: Vibrational and magnetic heat capacity. Geochim Cosmochim Acta. 2009, 73: 3393-3409. 10.1016/j.gca.2009.03.011.

    CAS  Article  Google Scholar 

  30. 30.

    Klemme S, van Miltenburg JC, Javorsky P, Wastin F: Thermodynamic properties of uvarovite garnet (Ca3Cr2Si3O12). Am Mineral. 2005, 90: 663-666. 10.2138/am.2005.1812.

    CAS  Article  Google Scholar 

  31. 31.

    OrtegaSanMartin L, Williams AJ, Gordon CD, Klemme S, Attfield JP: Low temperature neutron diffraction study of MgCr2O4 spinel. J Physics: Condens Matter. 2008, 20: 104238-10.1088/0953-8984/20/10/104238.

    Google Scholar 

  32. 32.

    Hwang JS, Lin KJ, Tien C: Measurement of heat capacity by fitting the whole temperature response of a heat-pulse calorimeter. Rev Sci Instr. 1997, 68: 94-101. 10.1063/1.1147722.

    CAS  Article  Google Scholar 

  33. 33.

    Dachs E, Bertoldi C: Precision and accuracy of the heat-pulse calorimetric technique: low-temperature heat capacities of milligram-sized synthetic mineral samples. Eur J Mineral. 2005, 17: 251-259. 10.1127/0935-1221/2005/0017-0251.

    CAS  Article  Google Scholar 

  34. 34.

    Lashley JC, Hundley MF, Migliori A, Sarrao JL, Pagliuso PG, Darling TW, Jaime M, Cooley JC, Hults WL, Morales L, et al: Critical examination of heat capacity measurements made on a Quantum Design physical property measurement system. Cryogenics. 2003, 43: 369-378. 10.1016/S0011-2275(03)00092-4.

    CAS  Article  Google Scholar 

  35. 35.

    Ditmars DA, Ishihara S, Chang SS, Bernstein G, West ED: Enthalpy and heat-capacity standard reference material: synthetic sapphire (alpha-Al2O3) from 10 to 2250 K. J Res Nat Bur Stand (USA). 1982, 87: 159-163.

    CAS  Article  Google Scholar 

  36. 36.

    Schnelle W, Engelhardt J, Gmelin E: Specific heat capacity of Apiezon N high vacuum grease and of Duran borosilicate glass. Cryogenics. 1999, 39: 271-275. 10.1016/S0011-2275(99)00035-1.

    CAS  Article  Google Scholar 

  37. 37.

    Kostryukov VN, Kalinkina IN: Heat capacity and entropy for manganese, iron, cobalt, and nickel carbonates at low temperatures. Russ J Phys Chem. 1964, 38: 780-781.

    CAS  Google Scholar 

  38. 38.

    Kubaschewski O: The thermodynamic properties of double oxides. High Temp High Pressure. 1972, 4: 1-12.

    CAS  Google Scholar 

  39. 39.

    Ishikawa Y: Magnetic properties of NiTiO3-Fe2O3 solid solution series. J Phys Soc Jpn. 1957, 12: 1165-1165. 10.1143/JPSJ.12.1165.

    CAS  Article  Google Scholar 

  40. 40.

    Ishikawa Y, Akimoto S: Magnetic property and crystal chemistry of ilmenite (MeTiO3) and hematite (alpha-Fe2O3) system 2. Magnetic property. J Phys Soc Jpn. 1958, 13: 1298-1310. 10.1143/JPSJ.13.1298.

    CAS  Article  Google Scholar 

Download references

Acknowledgements and Funding

We are indebted to V. Rapelius and A. Breit for their help with sample synthesis and characterization. Furthermore, our thanks go to two anonymous reviewers for their helpful and constructive reviews.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Stephan Klemme.

Additional information

Competing interests

The authors declare that they have no competing interests.

Authors' contributions

SK drafted the manuscript, synthesized the samples, and performed the data analysis. ME and WH carried out the calorimetric measurements and participated in the design of the experiments and helped to draft the manuscript. RP, AR, CHW participated in the experimental design and coordination and helped to draft the manuscript. All authors read and approved the final manuscript.

Authors’ original submitted files for images

Rights and permissions

Open Access This article is distributed under the terms of the Creative Commons Attribution 2.0 International License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Reprints and Permissions

About this article

Cite this article

Klemme, S., Hermes, W., Eul, M. et al. New thermodynamic data for CoTiO3, NiTiO3 and CoCO3 based on low-temperature calorimetric measurements. Chemistry Central Journal 5, 54 (2011). https://doi.org/10.1186/1752-153X-5-54

Download citation

Keywords

  • Heat Capacity
  • CoCO3
  • Standard Entropy
  • Physical Property Measurement System
  • NiTiO3