Thermodynamic properties of 1,3,3,-trimethylcyclopropene

Kosova, D.A.; Pimenova, S.M.; Lukyanova, V.A.; Druzhinina, A.I.

Авторы: Kosova D.A., Pimenova S.M., Lukyanova V.A., Druzhinina A.I.
Сборник: XVI International Conference on Thermal Analysis and Calorimetry in Russia (RTAC-2020). July 6th, 2020, Moscow, Russia. Book of Abstracts
Тезисы
Год издания: 2020
Место издания: “Pero” Publisher Moscow
Первая страница: 113
Последняя страница: 113
Аннотация: At present, cyclopropene and its derivatives cause increasing interest of researchers. The ringstress energy of these compounds is significantly higher compared to other cycloolefins. Electronunsaturation of the cycle is a cause low stability of these compounds and their increased tendencyto various transformations. Because of this, they are widely used in organic synthesis.This work is devoted to the experimental determination of thermodynamic properties 1,3,3-trimethylcyclopropene. The sample of 1,3,3-trimethylcyclopropene (C6H10(liq)) was synthesizedin the laboratory of organic synthesis of Chemical Department of Lomonosov Moscow StateUniversity by decomposing to sylhydrozone of mesityl oxide with sodium methylate in diglyme.It was purified by multiple distillation (column 80 theor. plates) and preparative chromatography(Table). The energy of combustion of liquid 1,3,3-trimethylcyclopropene was determined in static-bombisoperibolic calorimeter at T = 298.15 K. The temperature rise was measured with a copperresistance thermometer using a bridge circuit. The temperature measurement sensitivity was5·10-5 K. The combustion products were analyzed for carbon dioxide by the Rossini method [1]and the absence of CO was controlled by indicator tubes. The results of the CO2 analysis are shownin the Table. The content of HNO3 in the solution was determined by titration of washing watersby ~0.1 mol∙dm-3 of NaOH (aq). The formation enthalpy of liquid 1,3,3-trimethylcyclopropenewas calculated using experimental data.The saturated vapor pressures were determined by the comparative ebulliometry in the temperaturerange 295–310 K [2]. Experimental data are approximated by a linear equation:Ln (p/Pa) = A + B/T(K), where A = 22.37±0.07, B = –3439±20 (r2 = 0.9999).The normal boiling temperature, Tn.boil = 317.04±0.01 K, and the enthalpy of vaporization,ΔvHоm(298.15 K) = 27.7±0.4 kJ·mol-1, were estimated based on p-T-data.The enthalpy of vaporization at T = 298.15 K was also measured using the calorimetric method[3], ΔvHоm(298.15 K) = 27.63±0.19 kJ·mol-1. The coincidence within the error range of the valuesobtained by the two methods indicates the reliability of the found value of the vaporizationenthalpy.The density at T = 293.15 K was determined by pycnometric method, ρ = 0.6898±0.0006 g∙сm-3.The formation enthalpy of the compound in gas states was obtained using measured experimentaldata.Acknowledgements investigation was performed in the framework of Program “ChemicalThermodynamics” (AAAA-A16-116061750195-2). The authors acknowledge partial supportfrom M.V. Lomonosov Moscow State University Program of Development.
Добавил в систему: Калинюк (Косова) Дарья Александровна

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