Thermodynamic Characteristics of
Ethyl-2-cyano-3-(furan-2-yl)-prop-2-enoate Derivatives
Roman Kos, Iryna Sobechko, Yuriy Horak, Valentin Sergeev, Volodymyr Dibrivnyi
Department of Physical and Colloid Chemistry, National University Lviv Polytechnic, Ukraine
Email: romankos.ua@gmail.com
Abstract. Using bomb calorimetry and Knudsen effusion methods the enthalpic characteristics in
condensed state of ethyl-2-cyano-3-(furan-2-yl) prop-2-enoate derivatives were experimentally
determined. The values of the enthalpies of formation in the gas state of investigated esters were
calculated taking into account the values of the enthalpies of sublimation adjusted to 298K. From
obtained thermochemical values we defined new group contributions which can be added to the
Benson’s additive scheme. Using these increments the enthalpies of formation of investigated
compounds in gas state were theoretically calculated and their differences from the experimentally
determined were analyzed.
Keywords: Bomb calorimetry, effusion method, Benson’s scheme
1 Introduction
Heterocyclic compounds are widely distributed in nature [1]. Many of them are particularly important
for living organisms and they serve as a key components of biological processes. Many of drugs are
derived from natural products, but their number is much greater than those synthesized from natural or
synthetic compounds [2]. In particular, furan derivatives are commonly used in the synthesis of
biologically active compounds that exhibit antibacterial, antitumor, and tuberculostatic action [3].
Determination of thermodynamic properties of substances with widespread use will help to optimize the
processes of their synthesis and processing, as well as providing an opportunity to explore the energetic
properties of molecules of this class. Considering these diverse information the need of a greater number
of values of thermochemical parameters for esters of furanacrylic acid becomes evident. Despite this
there are no reported in literature values of the standard molar enthalpies of formation in the crystalline
and gas phase, as well as the standard molar enthalpies of sublimation of investigated compaunds.
The present study provides results of the purification, standard molar energy of combustion, standard
molar enthalpy of sublimation, and standard molar enthalpy of formation in both crystalline and
gaseous states, T = 298.15 K, for the five compounds. The experimental determination of the standard
energies of combustion of the five esters in oxygen at T = 298.15 K was conducted using static-bomb
combustion calorimetry. From the temperature dependence of the vapour pressure using linear form of
the Clausius–Clapeyron equation, the standard molar enthalpies of sublimation, at the average
temperature were derived. Standard molar enthalpies and entropies of sublimation at the temperature of
298.15 K were calculated using estimated values for the heat capacity differences between the gas and
the crystal phases of each compound. From the experimental values of the standard molar enthalpies of
formation in the condensed phase and the values of the standard molar enthalpies of sublimation at T =
298.15 K the standard molar enthalpies of formation in the gaseous phase were calculated for the five
ethyl esters of furanacrylic acid derivatives.
Due to the wide use of thermochemical characteristics of organic compounds, it is important to find
the best theoretical approach for determining these properties, when experimental determination is
impossible. Therefore we compared in this work the experimental data with Benson’s additive scheme [4].
For thermochemical studies we selected number of ethyl esters of furan acrylic acid derivatives:
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Modern Organic Chemistry Research, Vol. 2, No. 2, May 2017
https://dx.doi.org/10.22606/mocr.2017.22006
MOCR Copyright © 2017 Isaac Scientific Publishing