Pyrolysis of 3-carene: Experiment, Theory and Modeling
Article
First Online:
Received:
Revised:
Accepted:
- 181 Downloads
Abstract
Thermal decomposition studies of 3-carene, a bio-fuel, have been carried out behind the reflected shock wave in a single pulse shock tube for temperature ranging from 920 K to 1220 K. The observed products in thermal decomposition of 3-carene are acetylene, allene, butadiene, isoprene, cyclopentadiene, hexatriene, benzene, toluene and p-xylene. The overall rate constant for 3-carene decomposition was found to be
Ab-initio theoretical calculations were carried out to find the minimum energy pathway that could explain the formation of the observed products in the thermal decomposition experiments. These calculations were carried out at B3LYP/6-311 + G(d,p) and G3 level of theories. A kinetic mechanism explaining the observed products in the thermal decomposition experiments has been derived. It is concluded that the linear hydrocarbons are the primary products in the pyrolysis of 3-carene.
$$ \mathrm {k/s}^{-1}=10^{(9.95\,\pm \,0.54)}\; \exp (-40.88 \pm 2.71 \, \mathrm {kcal mol}^{\mathrm {-1}}/\text {RT}) . $$
Graphical Abstract
A detailed study on the pyrolysis of 3-carene showed that linear molecules were the primary products from its decomposition process. It has also been found that the C3 ring opening process was the initiation step both in 3-carene and C10H15 radical, formed by the H-dissociation/abstraction from 3-carene.
Keywords
Shock Tube Monoterpene Thermal Decomposition IsopreneNotes
Acknowledgements
We acknowledge funding from the following organizations: IISc-ISRO Space Technology Cell, Defence Research Development Organization, Defence Research Development Laboratory and Aeronautics Research and Development Board.
Supplementary material
References
- 1.Granata S, Faravelli T and Ranzi E 2003 Combust. Flame 132 533Google Scholar
- 2.Van D B and Anderson S L 2006 Energy Fuels 20 1886Google Scholar
- 3.Nakra S, Green R J and Anderson S L 2006 Combust. Flame 144 662Google Scholar
- 4.Chenoweth K, van Duin A C, Dasgupta S and Goddard I. W A 2009 J. Phys. Chem. A 113 1740Google Scholar
- 5.Davidson D F, Horning D C, Oehlschlaeger M A and Hanson R K 2001 In Proceedings of the 37th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, Salt Lake City, UT, July 8-11, 2001, AIAA 01–3707Google Scholar
- 6.Simonsen J L 1920 J. Chem. Soc., Trans. 117 570Google Scholar
- 7.Simonsen J L 1922 J. Chem. Soc., Trans. 121 2292Google Scholar
- 8.Simonsen J L and GopalaRau M 1923 J. Chem. Soc., Trans. 123 549Google Scholar
- 9.Saei D S S, Khalighi-Sigaroodi F, Pirali-Kheirabadi K, Saei-Dehkordi S S, Alimardani-Naghani F and Fallah A A 2014 J. Food Safety 34 87Google Scholar
- 10.Salem M Z M, Ali H M and Basalah M O 2014 BioResources 9 7454Google Scholar
- 11.Kulkarni S G, Bagalkote V S, Patil S S, Kumar U P and Kumar V A 2009 Propellants Explos. Pyrotech. 34 520Google Scholar
- 12.Sharath N, Reddy K P J, Barhai P K and Arunan E 2015 Curr. Sci. 108 2083Google Scholar
- 13.Cocker W, Hanna D P and Shannon P V R 1968 J. Chem. Soc. (C) 489Google Scholar
- 14.Feltham E J, Almond M J, Marston G, Ly V P and Wiltshire K S 2005 Spectrochim. Acta A 56 2605Google Scholar
- 15.Plemenkov V V, Rul S V, Kuzmina L G, Kataeva O N and Litvinov I A 1997 J. Mol. Struct. 412 239Google Scholar
- 16.Luo D, Pierce J A, Malkina I L and Carter W P 1996 Int. J. Chem. Kinet. 28 1Google Scholar
- 17.Tkachev A V and Denisov A Y 1991 Mendeleev Commun. 1 98Google Scholar
- 18.Paulson S E, Orlando J J, Tyndall G S and Calvert J G 1995 Int. J. Chem. Kinet. 27 997Google Scholar
- 19.Bakhvalov O V, Bagryanskaya I Y, Gatilov Y V, Korchagina D V and Barkhash V A 2002 Russian J. Org. Chem. 38 507Google Scholar
- 20.Oro J, Han J and Zlatkis A 1967 Anal. Chem. 39 27Google Scholar
- 21.Badger G M, Donnelly J K and Spotswood T M 1966 Aust. J. Chem. 19 1023Google Scholar
- 22.Weber K H and Zhang J 2007 J. Phys. Chem. A 111 11487Google Scholar
- 23.Nagaboopathy M, Vijayanand C, Hegde G, Reddy K P J and Arunan E 2008 Curr. Sci. 95 78Google Scholar
- 24.Rajakumar B, Reddy K P J and Arunan E 2002 J. Phys. Chem. A 106 8366Google Scholar
- 25.Rajakumar B, Reddy K P J and Arunan E 2003 J. Phys. Chem. A 107 9782Google Scholar
- 26.Sharath N, Reddy K P J and Arunan E 2014 J. Phys. Chem. A 118 5927Google Scholar
- 27.Frisch M J et al. 2009 (Wallingford CT: Gaussian Inc.)Google Scholar
- 28.CHEMKIN-PRO 15101 2010 (San Diego: Reaction Design)Google Scholar
- 29.Curtiss L A, Raghavachari K, Redfern P C, Rassolov V and Pople J A 1998 J. Chem. Phys. 109 7764Google Scholar
- 30.Alexiou A and Williams A 1996 Combust. Flame 104 51Google Scholar
- 31.Sivaramakrishnan R, Tranter R S and Brezinsky K 2006 J. Phys. Chem. A 110 9388Google Scholar
- 32.Gudiyella S, Malewicki T, Comandini A and Brezinsky K 2011 Combust. Flame 158 687Google Scholar
- 33.Wang D, Violi A, Kim D H and Mullholland J A 2006 J. Phys. Chem. A 110 4719Google Scholar
- 34.Harding L B, Klippenstein S J and Georgievskii Y 2007 J. Phys. Chem. A 111 3789Google Scholar
- 35.Westmoreland P R, Dean A M, Howard J B and Longwell J P 1989 J. Phys. Chem. 93 8171Google Scholar
Copyright information
© Indian Academy of Sciences 2015