Cobalt(II) chloro complexation in N-methylformamide-N, N-dimethylformamide mixtures: TTTTitration calorimetry and spectrophotometry

K. Fujii, Y. Matsumoto, Y. Kaieda, D. Kobayashi, Y. Umebayashi, S. Ishiguro

研究成果: ジャーナルへの寄稿学術誌査読

3 被引用数 (Scopus)

抄録

Cobalt(II) chloro complexation has been studied by titration calorimetry and spectrophotometry in solvent mixtures of N-methylformamide (NMF) and N,N-dimethylformamide (DMF). It revealed that a series of mononuclear CoCln n (2-n)+ (n=1-4) complexes are formed in the mixtures of NMF mole fraction x NMF=0.05 and 0.25, and the CoCl+, CoCl3 - and CoCl4 2- complexes in the mixture of x NMF=0.5, and their formation constants, enthalpies and entropies were obtained. As compared with DMF, the complexation is markedly suppressed in the mixtures, as well as in NMF. The decreasing formation constant of CoCl+ with the NMF content is mainly ascribed to the decreasing formation entropy. DMF is aprotic and thus less-structured, whereas NMF is protic to form hydrogen- bonded clusters. In DMF-NMF mixtures, solvent clusters in neat NMF are ruptured to yield new clusters involving DMF, the structure of which depends on the solvent composition. The entropy of formation of CoCl + will be discussed in relation to the liquid structure of DMF, NMF and their mixtures.

本文言語英語
ページ(範囲)567-573
ページ数7
ジャーナルJournal of Thermal Analysis and Calorimetry
85
3
DOI
出版ステータス出版済み - 9月 2006

!!!All Science Journal Classification (ASJC) codes

  • 凝縮系物理学
  • 材料化学
  • ポリマーおよびプラスチック
  • 歯科学(全般)
  • 物理化学および理論化学

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