Spectrokinetic Study of the Reaction System of 2NO2_N2O4 with Some Fluorinated Derivatives of Ethanol and Propanols Between 293-358 K in the Gas Phase

• Autorzy: Wójcik-Pastuszka D. , Golonka I. , Ratajczak E.
• Języki publikacji: EN

Abstrakty

EN

The gas phase kinetics of the reversible reactions between nitrogen tetroxide and some fluorinated alcohols in the reaction system 2NO2_N2O4 (1, 2) N2O4+ ROH--RONO + + HNO3 (3, 4) have been studied by UV-Vis spectrophotometry to follow the NO2 decay. The products - RONO (R = CH2FCH2, CHF2CH2, CF3CH2, CHF2CF2CH2, CF3CF2CH2, CF3CHCF3) - were identified by their UV spectra and the values of the maxima UV absorption cross sections were determined in the range 320-400 nm. The rate constants for the forward reaction are 10-19k3 av /cm3molec-1s-1 9.7š1.5; 2.5š0.4; 1.8š0.3; 23š3.5, 2.3š0.3, 0.2š0.03 and for the reverse reaction 10-19k4 av /cm3molec-1s-1 4.6š0.7; 5.5š0.8; 4.9š0.7; 9.1š1.4; 7.7š1.2; 23š3.5 at 298 K for the reaction with 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-pentafluoro- 1-propanol and 1,1,1,3,3,3-hexafluoro-2-propanol, respectively, were derived by the computer simulation of monitored NO2 decay profiles. The temperature dependence of the bimolecular rate constants k3 and k4 were studied in the temperature range 293-358 K and the activation energy for the forward E3 and for the reverse E4 reaction were derived. From the observed temperature dependence of the equilibrium constants K3,4 , expressed in terms of the van't Hoff equation, the thermochemical parameters for all reactions studied were estimated.

Słowa kluczowe

EN

nitrogen dioxide; dinitrogen tetroxide; fluorinated alcohols

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2006
• Tom: Vol. 80, nr 9
• Strony: 1559--1574
• Opis fizyczny: Bibliogr. 34 poz., rys.

Twórcy

autor

Wójcik-Pastuszka D.

autor

Golonka I.

autor

Ratajczak E.

• Department of Physical Chemistry, Wroclaw Medical University, Pl. Nankiera 1, 50-140 Wroclaw, Poland

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