An Anomaly in the Heat Capacity of CoCl_2 ・ 2H_2O at 17.20°K Associated with Antiferromagnetic Ordering

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概要

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• The heat capacities of CoCl_2・2H_2O were measured between 7 and 120°K by a small adiabattc calorimeter in an attempt to find the magnetic transition which was an anticipated below 20°K from the measurements of magnetic susceptibilities of the bydrate. The results of our measurements are depicted in the accompanying figure. A lambdashaped anomaly in the heat capacity, due apparently to a transition between anriferromagnetic and paramagnetic states, occurs below 20°K with the peak at 17.20°K. The results of different series of measurements agreed within experimental error and therefore there was no hysteresis effect. An analysis of the experimental heat capacty curve was made in the light of current theories, though help of the experimental heat capacities of CoCl_2・6H_2O at low temperatures in a semiempirical way. Thus, Wakefield's 〓tatistical-mecbhnical treatment of magnetic or〓〓〓ing was extended so as to include an anisotropy in the exchange interaction, and the theory was used to aid in the separation of the magnetic cotribution to the total heat capacity in the region of the temperature above 20°K. This was accomplished integrals between neighboring Co^<2+> ions from the knowledge of the transition temperature of the dihydrate and of the magnetic heat capacity of the hexahydrate: |J|/k=10.84°K in the direction of the chain of the coordinated Co^<2+> ions and |J'|/k=2,032°K between Co^2÷ions in the neighboring chains. The values of exchange integrals were then found consistent with the experimental heat capacities of the dibydrate below 13°K. The magnitude of |J'|is explicable only by assuming a super-exchange interaction arising from a fairly large overlapping of electron wave functions across the OH・・Cl hydrogen bonds which bridge neighboring chains. The total entropy of the transition is 1.39 cal/deg mole and about 37% of this is aquired in the temperature region above 17.20°K. Details of the experimental determinations and of the analysis of the results will be published shortly.

• 社団法人日本物理学会の論文
• 1964-06-05

著者

• SHINODA Takako

  Department of Microbiology, Meiji College of Pharmacy

• Shinoda Takako

  Department Of Chemistry Faculity Of Science Osaka University

• SEKI Syuzo

  Department of Chemistry, Faculty of Science, University of Osaka

• Seki Syuzo

  Department Of Chemistry Faculity Of Science Osaka University

• CHIHARA Hideaki

  Department of Chemistry, Faculity of Science, Osaka University

• Chihara Hideaki

  Department Of Chemistry Faculity Of Science Osaka University

• Chihara Hideaki

  Department Of Chemistr Faculty Of Science Osaka University

• Seki Syûzô

  Department of Chemistry and Chemical Thermodynamics Laboratory, Faculty of Science, Osaka University

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