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  • 1 Kyushu University Department of Chemistry, Faculty of Science Fukuoka Japan 812-8581 Hakozaki, Higashi-ku Fukuoka Japan 812-8581 Hakozaki, Higashi-ku
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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 CoClnn(2–n)+ (n=1–4) complexes are formed in the mixtures of NMF mole fraction xNMF=0.05 and 0.25, and the CoCl+, CoCl3 and CoCl42– complexes in the mixture of xNMF=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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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
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Founder Akadémiai Kiadó
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Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
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CH-6330 Cham, Switzerland Gewerbestrasse 11.
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ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)