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

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)567-573
Number of pages7
JournalJournal of Thermal Analysis and Calorimetry
Volume85
Issue number3
DOIs
Publication statusPublished - Sep 1 2006

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methylformamide
Dimethylformamide
Spectrophotometry
Calorimetry
spectrophotometry
Cobalt
Complexation
cobalt
heat measurement
entropy
Entropy
titration
enthalpy

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Cobalt(II) chloro complexation in N-methylformamide-N, N-dimethylformamide mixtures : TTTTitration calorimetry and spectrophotometry. / Fujii, K.; Matsumoto, Y.; Kaieda, Y.; Kobayashi, D.; Umebayashi, Y.; Ishiguro, S.

In: Journal of Thermal Analysis and Calorimetry, Vol. 85, No. 3, 01.09.2006, p. 567-573.

Research output: Contribution to journalArticle

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AU - Kaieda, Y.

AU - Kobayashi, D.

AU - Umebayashi, Y.

AU - Ishiguro, S.

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AB - 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.

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