Influence of Fluorosubstitution on the Heat Capacity of Aliphatic Alcohols
Abstract
In this paper, the principle of corresponding states was used when conducting a comparative analysis of the temperature dependences of the isobaric heat capacity of aliphatic alcohols and their fluorosubstituted analogues. For the heat capacity, both literature experimental data and simulated data, obtained using artificial neural networks, were applied. The isobaric heat capacity for the aliphatic alcohols in the absolute values in a wide temperature range at constant pressure is smaller than that for the corresponding fluorosubstituted analogues. The comparison of the heat capacity data on the aliphatic alcohols and their fluorosubstituted analogues with the heat capacity of water, for which there is a hydrogen bond network, and comparison of the corresponding data with the heat capacity of hydrogen peroxide, where there are hydrogen bonds, but the network is absent, indicates that the change in the physical properties of alcohols upon fluorosubstitution is associated with the hydrogen bond density.
Downloads
References
V.A. Soloshonok, K. Mikami, T. Yamazaki, J.T. Welch, and J.F. Honek, editors, Current Fluoroorganic Chemistry: New Synthetic Directions, Technologies, Materials, and Biological Applications, (American Chemical Society, 2007).
J. Vymětal, L. Bednárová, and J. Vondrášek, “Effect of TFE on the helical content of AK17 and HAL-1 peptides: Theoretical insights into the mechanism of helix stabilization”, The Journal of Physical Chemistry B, 120, 1048-1059 (2016). https://doi.org/10.1021/acs.jpcb.5b11228
A.M. Arnold, P. Dullinger, A. Biswas, C. Jandl, D. Horinek, and T. Gulder, “Enzyme-like polyene cyclizations catalyzed by dynamic, self-assembled, supramolecular fluoro alcohol-amine clusters”, Nature Communications, 14, 813 (2023). https://doi.org/10.1038/s41467-023-36157-0
N. Nakata, R. Okamoto, T. Sumi, K. Koga, T. Morita, and H. Imamura, “Molecular mechanism of the common and opposing cosolvent effects of fluorosubstituted alcohol and urea on a coiled coil protein”, Protein Science, 32, e4763 (2023). https://doi.org/10.1002/pro.4763
V.V. Motov, E.F. Kot, A.V. Shabalkina, S.A. Goncharuk, A.S. Arseniev, M.V. Goncharuk, and K.S. Mineev, “Investigation of lipid/protein interactions in trifluoroethanol-water mixtures proposes the strategy for the refolding of helical transmembrane domains”, Journal of Biomolecular NMR, 77, 15-24 (2023). https://doi.org/10.1007/s10858-022-00408-x
E.L. Godden, R.A. Harris, and T.V. Dunwiddie, “Correlation between molecular volume and effects of n-alcohols on human neuronal nicotinic acetylcholine receptors expressed in Xenopus oocytes”, Journal of Pharmacology and Experimental Therapeutics, 296, 716-722 (2001). https://doi.org/10.1016/s0022-3565(24)38808-1
B. Akitake, R.E. Spelbrink, and S. Sukharev, “2,2,2-Trifluoroethanol changes the transition kinetics and subunit interactions in the small bacterial mechanosensitive channel MscS”, Biophysical Journal, 92, 2771-2784 (2007). https://doi.org/10.1529/biophysj.106.098715
M.I. Lioudyno, M. Broccio, and J.E. Hall, “Effect of synthetic aβ peptide oligomers and fluorosubstituted solvents on Kv1.3 channel properties and membrane conductance”, PLoS One, 7, e35090 (2012). https://doi.org/10.1371/journal.pone.0035090
H. Abdel-Wahab, and J. Bozzelli, “Gaussian M-062x/6-31+g (d,p) calculation of standard enthalpy, entropy and heat capacity of some fluorosubstituted alcohol’s and its radicals at different temperatures”, American Journal of Physical Chemistry, 9, 101 111 (2020). https://doi.org/10.11648/j.ajpc.20200904.13
G.M.C. Silva, J. Justino, P. Morgado, M. Teixeira, L.M.C. Pereira, L.F. Vega, and E.J.M. Filipe, “Detailed surface characterization of highly fluorosubstituted liquid alcohols: Experimental surface tensions, molecular simulations and soft-SAFT theory”, Journal of Molecular Liquids, 300, 112294 (2020). https://doi.org/10.1016/j.molliq.2019.112294
Y.B. Vysotsky, V.S. Bryantsev, F.L. Boldyreva, V.B. Fainerman, and D. Vollhardt, “Quantum chemical semiempirical approach to the structural and thermodynamic characteristics of fluoroalkanols at the air/water interface”, The Journal of Physical Chemistry B, 109, 454-462 (2005). https://doi.org/10.1021/jp048240e
M.P. Krafft, and J.G. Riess, “Chemistry, physical chemistry, and uses of molecular fluorocarbon−hydrocarbon diblocks, triblocks, and related compounds – Unique “apolar” components for self-assembled colloid and interface engineering”, Chemical Reviews, 109, 1714-1792 (2009). http://doi.org/10.1021/cr800260k
A.M. Hetalo, O.V. Khorolskyi, S.A. Stetsenko, S.O. Samoilenko, and O.S. Svechnikova, “Similar behavior of rheological properties and the evaluation of the melting temperatures of fluorosubstituted aliphatic alcohols”, Ukrainian Journal of Physics, 65, 419-427 (2020). https://doi.org/10.15407/ujpe65.5.419
A.M. Hetalo, O.P. Rudenko, O.V. Khorolskyi, S.O. Samoilenko, and L.A. Bulavin, “Temperature dependence of the bulk elasticity modulus of aliphatic alcohols and their fluorosubstituted analogs”, Ukrainian Journal of Physics, 63, 134-137 (2018). https://doi.org/10.15407/ujpe63.2.134
M. Zabransky, M. Bures, and V. Ruzicka Jr., “Types of curves for the temperature dependence of the heat capacity of pure liquids”, Thermochimica Acta, 215, 25-45 (1993). https://doi.org/10.1016/0040-6031(93)80080-T
V. Pogorelov, L. Bulavin, I. Doroshenko, O. Fesjun, and O. Veretennikov, “The structure of liquid alcohols and the temperature dependence of vibrational bandwidth”, Journal of Molecular Structure, 708, 61-65 (2004). https://doi.org/10.1016/j.molstruc.2004.03.003
V.I. Petrenko, M.V. Avdeev, L. Almásy, L.A. Bulavin, V.L. Aksenov, L. Rosta, and V.M. Garamus, “Interaction of mono-carboxylic acids in benzene studied by small-angle neutron scattering”, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 337, 91-95 (2009). https://doi.org/10.1016/j.colsurfa.2008.12.001
I.I. Novikov, “Thermodynamic similarity and prediction of the properties and characteristics of substances and processes”, Journal of Engineering Physics, 53, 1227-1232 (1987). https://doi.org/10.1007/BF00871080
[19] H.W. Xiang, “The Corresponding-States Principle and Its Practice. Thermodynamic, Transport and Surface Properties of Fluids” (Elsevier Science, 2005).
C. Yaws, Thermophysical Properties of Chemicals and Hydrocarbons, (Gulf Professional Publishing, 2014).
M.Z. Southard, and D.W. Green, Perry’s Chemical Engineers’ Handbook, (McGraw-Hill Education, 2019).
P.J. Linstrom, and W.G. Mallard (Eds.), NIST Chemistry WebBook, NIST Standard Reference Database Number 69, (National Institute of Standards and Technology, 2025). https://doi.org/10.18434/T4D303
MiniRefprop Database, (National Institute of Standards and Technology, 2025). https://trc.nist.gov/refprop/MINIREF/MINIREF.HTM
I.H. Bell, J. Wronski, S. Quoilin, and V. Lemort, “Pure and pseudo-pure fluid thermophysical property evaluation and the open-source thermophysical property library CoolProp”, Industrial & Engineering Chemistry Research, 53, 2498-2508 (2014). https://doi.org/10.1021/ie4033999
NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP), (National Institute of Standards and Technology, 2025). https://www.nist.gov/srd/refprop
ThermoData Engine Database, (National Institute of Standards and Technology, 2025). https://trc.nist.gov/tde.html
NIST/TRC Web Thermo Tables (WTT). NIST Standard Reference Subscription Database, (National Institute of Standards and Technology, 2025). https://wtt-pro.nist.gov/wtt-pro/
MOL-Instincts Database, (ChemEssen, 2025). https://www.molinstincts.com/
ChemRTP Database, (ChemEssen, 2025). http://www.chemrtp.com/
M. Zábranský, V. Růžička, V. Majer, “Heat capacities of organic compounds in the liquid state I. C1 to C18 1-alkanols”, Journal of Physical and Chemical Reference Data, 19, 719-762 (1990). https://doi.org/10.1063/1.555860
Pure Property Calculator, (Korea Thermophysical Properties Data Bank, 2025). https://www.mdlkdb.com/calculate/pure
Copyright (c) 2025 Leonid A. Bulavin, Oleksii V. Khorolskyi, Bohdan A. Hetalo, Andrii M. Hetalo, Yevgenii G. Rudnikov
This work is licensed under a Creative Commons Attribution 4.0 International License.
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgment of the work's authorship and initial publication in this journal.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgment of its initial publication in this journal.
- Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access).
