Funct. Mater. 2024; 31 (2): 269-275.

doi:https://doi.org/10.15407/fm31.02.269

Metal complex catalysis of initiated oxidation of hydrocarbons and alcohols: features of inhibition

I.A.Opeida2, O.A.Velichko2, Ye.V.Sheludko1, A.V.Pavliuk1, R.B.Sheparovych3, V.E.Sheludko4, M.N.Baran1

1V.P.Kukhar Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 50 Kharkovskoe Shausse, 02160 Kyiv, Ukraine
2L.M.Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, 50 Kharkovskoe Shausse, 02160 Kyiv, Ukraine
3Department of Physical Chemistry of Fossil Fuels of L.M.Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, 3a Naukova Str., 79060 Lviv, Ukraine
4Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanovsky Str., 03142 Kyiv, Ukraine

Abstract: 

Kinetics of initiated oxidation of cumene and benzyl alcohol in the presence of Cu (II) bis-salicylaldiminate complexes containing trifluoromethyl or tetrafluoroethoxy substituents in ligand environments was investigated. The inhibitory properties of the complexes were studied by a gas-volumetric method at T = 343 K and P = 0.09-0.1 MPa. 2,2 I–Azo–bis–isobutyronitrile (АІBN) was used as an initiator. During the oxidation of cumene, all studied Me-complexes exhibit catalytic properties at the concentrations of 1·10-3 – 0.01 mol/lit, accelerating oxidation of cumene. An increase in the oxygen pressure also does not cause the change of the initial oxidation rate. During the oxidation of benzyl alcohol, all the complexes catalytically terminate the oxidation chains. It has been established that when storing the reaction solution without access to air, induction periods are observed on the kinetic curves, increasing with storage time. Theoretical and experimental induction periods and factors of inhibition were determined.

Keywords: 
metal complexes, catalysis, peroxyl radical, hydroperoxides, trifluoromethyl substituent, tetrafluoroethoxy group, induction period, factor inhibition.

Full text in PDF

References: 
. M.Trindade, (ed.), Increased Biodiesel Efficiency: Alternatives for Production, Stabilization, Characterization and Use of Coproduct, Springer (2018). 
https://doi.org/10.1007/978-3-319-73552-8
 
2. V.V.Goncharuk, G.L.Kamalov, G.A.Kovtun et al., Catalysis. Mechanisms of Homogeneous and Heterogeneous Catalysis, Cluster Approaches, Nauk. Dumka, Kiev (2002) [in Russian].
 
3. G.A.Kovtun, V.A.Pluzhnikov, Chemistry of Oxidation Inhibitors of Organic Compounds, Nauk. Dumka, Kiev (1995) [in Russian].
 
4. E.T.Denisov, I.B.Afanas'ev, Oxidation and Antioxidants in Organic Chemistry and Biology, CRC Press, Boca Raton (2005).
https://doi.orgg/10.1201/9781420030853.
 
5. R.R.Hiatt, T.Mill, F. R.Mayo, J.Org. Chem., 33, 1416 (1968). https://doi.org/10.1021/jo01268a022.
https://doi.org/10.1021/jo01268a022
 
6. D.G.Knorre, L.G.Chuchukina, N.M.Emanuel, Zhurn. Phys.

Current number: