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Anti-sigmoidal Composition Dependence of Glass Transition Temperature and Excess Heat Capacity Across It in a Binary System of Globular Alcohols

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Abstract

Differential scanning calorimetry (DSC) revealed an anti-sigmoidal composition dependence of the glass transition temperature in a binary mixture of dicyclohexylmethanol [\((\hbox {C}_6\hbox {H}_{11})_2\hbox {CHOH}\), DCHM] and tricyclohexylmethanol [\((\hbox {C}_6\hbox {H}_{11})_3\hbox {COH}\), TCHM]. The equimolar mixture, of which state was suggested to be robust by the dependence, was subjected to adiabatic calorimetry. The glass transition occurred around 257 K with a significant enthalpy relaxation. The excess heat capacity beyond the weighted average of heat capacities of neat compounds changes its sign from positive to negative upon the glass transition on cooling. The negative excess implies a denser molecular packing than neat glasses. The excess enthalpy is graphically given relative to \(T=298.15\) K.

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Data Availability

Numerical data of excess heat capacities and integrated excess enthalpy are available on request to a corresponding author.

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Acknowledgements

We dedicate this paper to the memory of the late Professor Jean-Pierre Grolier, a giant in the field of calorimetry and thermal analysis.

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Author notes

  1. Yasuhisa Yamamura and Kazuya Saito have contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8571, Japan

    Yasuhisa Yamamura, Kaoru Nomiya, Mafumi Hishida & Kazuya Saito

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  1. Yasuhisa Yamamura
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  2. Kaoru Nomiya
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  3. Mafumi Hishida
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  4. Kazuya Saito
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YY and KS designed the project, KM mainly performed experiments, all authors participated in discussion, and KS prepared the main manuscript. All authors reviewed the manuscript.

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Correspondence to Yasuhisa Yamamura or Kazuya Saito.

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Yamamura, Y., Nomiya, K., Hishida, M. et al. Anti-sigmoidal Composition Dependence of Glass Transition Temperature and Excess Heat Capacity Across It in a Binary System of Globular Alcohols. J Solution Chem 53, 144–153 (2024). https://doi.org/10.1007/s10953-022-01242-3

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