Cl-initiated photo-oxidation reaction of methyl propionate was investigated experimentally using relative rate method. Gas chromatography/mass spectrometry (GC-MS) and GC/infrared spectroscopy (GC-IR) were used as analytical tools to follow the concentrations of reactants and products during reaction. The gas-phase kinetics of methyl propionate with Cl atoms was measured over the temperature range of 263–363 K at 760 Torr in N2 atmosphere using C2H6 and C2H4 as reference compounds. The temperature-dependent rate coefficient for the reaction of methyl propionate with Cl atom was obtained as k(T) = [(3.25 ± 1.23) × 10−16] T2 exp [− (33 ± 4) / T] cm3 molecule−1 s−1. Theoretical calculations were also performed at CCSD(T)/cc-pVDZ//B3LYP/6-31G(d,p) level of theory, and the rate coefficients for H abstraction reactions were evaluated using canonical variational transition state theory (CVT/SCT) with interpolated single point energy (ISPE) method over the temperature range of 200–400 K. The rate coefficients over the studied temperature range yielded the Arrhenius expression k(T) = (7.22 × 10−16) T1.5 exp (466 / T) cm3 molecule−1 s−1. The reaction mechanism based on product analysis, thermochemistry, branching ratios, atmospheric implications, degradation pathways, and cumulative lifetime of methyl propionate is also presented in this manuscript.
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Andersen VF, Berhanu TA, Nilsson EJ, Jorgensen S, Nielsen OJ, Wallington TJ, Johnson MS (2011) Atmospheric chemistry of two biodiesel model compounds: methyl propionate and ethyl acetate. J Phys Chem A115:8906–8919
Atkinson R, Baulch DL, Cox RA, Crowley JN, Hampson RF, Kerr JA, Rossi MJ, Troe J(2001) Summary of evaluated kinetic and photochemical data for atmospheric chemistry, Web Version
Atkinson R (2000) Atmospheric chemistry of VOCs and NOx. Atmos Environ 34:2063–2101
Balaganesh M, Dash MR, Rajakumar B (2014) Experimental and computational investigation on the gas phase reaction of ethyl Formate with cl atoms. J Phys Chem A118:5272–5278
Bendtz K (2007) EU-25 - oilseeds and products: biofuels situation in the European Union 2005, GAIN report. USDA and Foreign Agricultural Service, Washington DC
Berg M, Müller SR, Mühlemann J, Wiedmer A, Schwarzenbach RP (2000) Concentrations and mass fluxes of chloroacetic acids and trifluoroacetic acid in rain and natural waters in Switzerland. Environ Sci Technol 14:2675–2683
Billaud F, Dominguez V, Broutin P, Busson C (1995) Production of hydrocarbons by pyrolysis of methyl esters from rapeseed oil. J Am Oil Chem Soc 72:1149–1154
Cavalli F, Barnes I, Becker KH, Wallington TJ (2000) Atmospheric oxidation mechanism of methyl propionate. J Phys Chem A104:11310–11317
Chang CT, Liu TH, Jeng FT (2004) Atmospheric concentrations of the Cl atom, ClO radical and HO radical in the coastal marine boundary layer. Environ Res 94:67–74
Chemseddine A, Boehm HP (1990) A study of the primary step in the photochemical degradation of acetic acid and chloroacetic acids on a TiO2 photocatalyst. J Mol Catal 60:295–311
Coquet S, Ariya PA (2000) Kinetics of the gas-phase reactions of Cl atom with selected C2–C5 unsaturated hydrocarbons at 283< T< 323 K. Int J Chem Kinet 32:478–484
Cometto PM, Daele V, Idir M, Lane SI, Mellouki A (2009) Reaction rate coefficients of OH radicals and Cl atoms with ethyl propanoate, n-propyl propanoate, methyl 2-methylpropanoate, and ethyl n-butanoate. J Phys Chem A113:10745–10752
Dash MR, Rajakumar B (2014) Reaction kinetics of cl atoms with limonene: an experimental and theoretical study. Atmos Environ 99:183–195
Dash MR, Rajakumar B (2015) Experimental and computational investigation on the gas phase reaction of p-cymene with Cl atoms. J Phys Chem A 119:559–570
European Biodiesel Board (2010). http://www.ebb-eu.org/stats.php
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2010) Gaussian 09, revision B.01. Gaussian, Inc., Wallingford
Garrett BC, Truhlar DG, Grev RS, Magnuson AW (1980) Improved treatment of threshold contributions in Variational transition-state theory. J Phys Chem A 84:1730–1748
Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154–2161
Hertz HS, Hites RA, Biemann K (1971) Identification of mass spectra by computer-searching a file of known spectra. J Anal Chem 43:681–691
Hoare DE, Kamil M (1970) The combustion of ethyl acetate, methyl propionate, and i-propyl acetate. Combust Flame 15:61–70
Notario A, Le Bras G, Mellouki A (1998) Absolute rate constants for the reactions of Cl atoms with a series of esters. J Phys Chem A102:3112–3117
Page M, McIver JW Jr (1988) On evaluating the reaction path Hamiltonian. J Chem Phys 88:922–935
Prinn RG, Weiss RF, Miller BR, Huang J, Alyea FN, Cunnold DM, Fraser PJ, Hartley DE, Simmonds PG (1995) Atmospheric trends and lifetime of CH3CCl3 and global OH concentrations. Science 269:187–192
Pszenny AP, Keene WC, Jacob DJ, Fan S, Maben JR, Zetwo MP, Springer-Young M, Galloway JN (1993) Evidence of inorganic chlorine gases other than hydrogen chloride in marine surface air. Geophys Res Lett 20:699–702
Singh HB, Thakur AN, Chen YE, Kanakidou M (1996) Tetrachloroethylene as an indicator of low Cl atom in the troposphere. Geophys Res Lett 23:1529–1532
Spicer CW, Chapman EG, Finlayson-pitts BJ, Plastridge RA, Hubbe JM, Fast JD, Berkowitz CM (1998) Unexpectedly high concentrations of molecular chlorine in coastal air. Nature 394:353–356
Srinivasulu G, Rajakumar B (2015) Gas phase kinetics of 2,2,2-trifluoroethylbutyrate with the Cl atom: an experimental and theoretical study. J Phys Chem A119:9294–9306
Stutz J, Ezell MJ, Finlayson-Pitts BJ (1998) Inverse kinetic isotope effect in the reaction of atomic chlorine with C2H4 and C2D4. J Phys Chem A 102:8510–8519
Tanaka PL, Oldfield S, Neece JD, Mullins CB, Allen DT (2000) Anthropogenic sources of chlorine and ozone formation in urban atmospheres. Environ Sci Technol 34:4470–4473
Thornton JA, Kercher JP, Riedel TP, Wagner NL, Cozic J, Holloway JS, Dube WP, Wolfe GM, Quinn PK, Middlebrook AM, Alexander B, Brown SS (2010) A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry. Nature 464:271–274
Truhlar DG, Kupperman A (1971) Exact tunneling calculations. J Am Chem Soc 93:1840–1851
Wingenter OW, Blake DR, Blake NJ, Sive BC, Rowland FS, Atlas E, Flocke FJ (1999) Tropospheric hydroxyl and atomic chlorine concentrations, and mixing time scales determined from hydrocarbon and halocarbon measurements made over Southern Ocean. J Geophys Res 104:21819–21828
Worldwatch Institute Biofuels for transport. London: Earthscan: Oxford (2007)
Authors wish to acknowledge Professor D.G. Truhlar for providing the GAUSSRATE 2009A as well as POLYRATE 2008 programs. The authors acknowledge Mr. V. Ravichandran and HPCE for supercomputing facility. BR acknowledges the Department of Science and Technology, Government of India for the financial support.
Responsible editor: Gerhard Lammel
Electronic supplementary material
Vibrational frequencies and structural parameters of reactants, transition states, and products obtained at the B3LYP/6-31G (d, p) level of theory. The details of the products of Cl initiated oxidation of methyl propionate. Variational plots of TS2, TS3, TS4, and TS5. IRC plots for the transition states. Mass spectrum, chromatograms and IR spectrum of each product obtained for the reaction of Methyl propionate with Cl atom.
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Balan, R.C., Balla, R. Cl-initiated photo-oxidation reactions of methyl propionate in atmospheric condition. Environ Sci Pollut Res 25, 20999–21010 (2018). https://doi.org/10.1007/s11356-018-2062-7
- Methyl propionate
- Atmospheric oxidants
- Rate coefficients
- Cumulative lifetimes
- Product analysis and relative rate method