The thermal decomposition of C2H5I

Kumaran, S. S.; Su, M.‐C.; Lim, K. P.; Michael, J.V.

doi:10.1016/s0082-0784(96)80266-9

Cited by 68 publications

(80 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, reaction (1b), elimination of HI, which is only mildly endothermic (20.6 kcal/mol), makes small contributions to the observed density gradient, whereas the C I fission channel, reaction (1a), dominates the density gradient at t 0 due to the much larger heat of reaction (55.8 kcal/mol). Kumaran et al [8] determined a branching ratio, k 1a /(k 1a + k 1b ) = 0.87, at reaction conditions similar to the current work, which implies that the contribution of the HI elimination channel to the initial density gradient is negligible, thereby allowing accurate determination of k 1a . Although the HI elimination channel has little effect on the observed initial density gradient, its inclusion in the reaction mechanism (Table I) used to simulate the complete density-gradient profile is important as it removes a source of H-atoms.…”

Section: Dissociation Of C 2 H 5 Isupporting

confidence: 75%

“…k 1a was obtained through an iterative procedure where an initial estimate of dρ/dx at [28,34]. b The branching ratio of C-I bond dissociation and HI molecular elimination is temperature independent and k 1 /(k 1 + k 2 ) = 0.87 [8]. c log (A) = 12.3 in [42] and 13.6 in [41].…”

Section: Dissociation Of C 2 H 5 Imentioning

confidence: 99%

“…Consequently, pyrolysis of ethyl iodide efficiently produces ethyl radicals and their subsequent dissociation is used as a source of H-atoms in shocktube experiments [10][11][12][13][14]: Several groups [15][16][17][18] have studied the lowtemperature dissociation of C 2 H 5 I, primarily in flow reactors. At temperatures in excess of 1000 K, the dissociation has been investigated by Kumaran et al [8] and Weber et al [9]. Kumaran et al studied thermal dissociation of ethyl iodide behind reflected shock waves using both H-atom and I-atom atomic resonance absorption spectroscopy (ARAS) under sufficiently dilute conditions to suppress secondary reactions.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

High‐temperature dissociation of ethyl radicals and ethyl iodide

Yang

Tranter

2012

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The decomposition of ethyl iodide and subsequent dissociation of ethyl radicals have been investigated behind incident shock waves in a diaphragmless shock tube by laserschlieren (LS) densitometry (1150-1870 K, 55 ± 2 Torr and 123 ± 3 Torr). The LS density-gradient profiles were simulated assuming that the initial dissociation of C 2 H 5 I proceeded by 87% C I fission and 13% HI elimination. Excellent agreement was found between the simulations and experimental profiles. Rate coefficients for the C I scission reaction were obtained and show strong falloff. Gorin model RRKM (Rice, Ramsperger, Kassel, and Marcus) calculations are in excellent agreement with the experimental data with E 0 = 55.0 kcal/mol, which is in very good agreement with recent thermochemical measurements and evaluations. However, E 0 is approximately 2.7 kcal/mol higher than previous estimates. First-order rate coefficients for dissociation of C 2 H 5 I were determined to be k 55Torr = 8.65 × 10 68 T −16.65 exp(−37,890/T ) s −1 , k 123Torr = 3.01 × 10 69 T −16.68 exp(−38,430/T ) s −1 , k ∞ = 2.52 × 10 19 T −1.01 exp(−28,775/T ) s −1 . Rates of dissociation for ethyl radicals were also obtained, and these are in very good agreement with theoretical predictions (Miller J. A. and Klippenstein S.

show abstract

Section: Dissociation Of C 2 H 5 Isupporting

confidence: 75%

Section: Dissociation Of C 2 H 5 Imentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

High‐temperature dissociation of ethyl radicals and ethyl iodide

Yang

Tranter

2012

Int J of Chemical Kinetics

View full text Add to dashboard Cite

show abstract

“…[ls], CH3Cl [10,11], C3H3Cl [19], CFC13 [16,20], CF2C12 [16,21], CF3Cl [16,22], CF2HCl [13], CF3I [12], CH3I [23], C2H5I [24], C6H5I [25], and CC120 [26]. The methods used are nearly identical in all cases, and for the purposes of discussion, we will illustrate the method with CH3I data -ln(IdIo) (It and Io refer to transmitted and incident I-atom resonance light intensities, respectively), is measured as CH3I decomposes.…”

Section: Resultsmentioning

confidence: 99%

Thermal Decomposition Studies of Halogenated Organic Compounds

Michael¹,

Kumaran²

1998

Combustion Science and Technology

View full text Add to dashboard Cite

“…7. Kumaran et al [44] have previously determined k 31a by monitoring both product H and I atoms behind reflected shock waves over the temperature range of 946-1303 K, and over the density range of (0.82-6.6) × 10 18 molecules cm it is true, the present data can be expected to be larger than their results, because we carried out the experiments at a higher density, 6.0 × 10 18 molecules cm −3 . Furthermore, the present data are in excellent agreement with our colleague's previous data [29], which have been obtained directly by monitoring I atoms behind shock waves in the same density range.…”

Section: Reaction Of Ch 3 Och 3 With Hmentioning

confidence: 99%

Shock‐tube studies on the reactions of dimethyl ether with oxygen and hydrogen atoms

Takahashi¹,

Yamamoto²,

Inomata³

et al. 2006

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The reactions of dimethyl ether (CH 3 OCH 3 , DME) with O( 3 P) and H atoms have been studied at high temperatures by using a shock tube apparatus coupled with atomic resonance absorption spectroscopy (ARAS). The rate coefficients for the reactions CH 3 OCH 3 + O( 3 P) → CH 3 OCH 2 + OH (1) and CH 3 OCH 3 + H → CH 3 OCH 2 + H 2 (2) were experimentally determined from the decay of O( 3 P) and H atoms as:These results show that DME can react with O( 3 P) atoms more easily than with H atoms. By combining these results with the previous lower temperature data, we obtained the following modified Arrhenius expressions applied over the wide temperature range between 300 and 1500 K: Both reactions of DME are faster than those of ethane, because the dissociation energy of the C H bond in DME is smaller. Furthermore, the rate coefficients for reactions (1) and (2) were calculated with the transition-state theory (TST). Structural parameters and vibrational frequencies of the reactants and the transition states required for the TST calculation were obtained from the MP2(full)/6-31G(d) ab initio molecular orbital (MO) calculation. The energy barrier, E ‡ 0 , was adjusted until the TST rate coefficient most closely matched the observed one. The fitting results of E ‡ 0 (1) = 23 kJ mol −1 and E ‡ 0 (2) = 34 kJ mol −1 were in agreement with the G2 energy barriers, within the expected uncertainty, demonstrating that the experimentally determined rate coefficients were theoretically valid. C 2006 Wiley Periodicals, Inc. Int J Chem Kinet

show abstract

The thermal decomposition of C2H5I

Cited by 68 publications

References 27 publications

High‐temperature dissociation of ethyl radicals and ethyl iodide

High‐temperature dissociation of ethyl radicals and ethyl iodide

Thermal Decomposition Studies of Halogenated Organic Compounds

Shock‐tube studies on the reactions of dimethyl ether with oxygen and hydrogen atoms

Contact Info

Product

Resources

About