The decomposition of 1,3,5-trioxane at very high temperatures

Irdam, Erwin; Kiefer, J. H.

doi:10.1016/0009-2614(90)87139-i

Cited by 27 publications

(31 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This mechanism for 1,3,5-trioxane decomposition was confirmed in a laser schelieren study by Irdam and Kiefer 14 and later by Aldridge et al 12 and Hochgreb and Dryer…”

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Cosupporting

confidence: 55%

“…5. As can be seen, our data fill up the void spaces in the mid-temperature range and encompass both the Irdam and Kiefer 14 and…”

supporting

confidence: 60%

“…This conclusion was later supported by the shock tube study of Irdam and Kiefer 14 who observed the dissociation of trioxane over 950 to 1270 K and 138 to 362 Torr using laser schlieren technique. Their computed density gradient profiles, in accordance with reaction…”

mentioning

confidence: 77%

“…[1][2][3] Its importance in combustion led to a number of high temperature kinetic studies for its pyrolytic dissociation [3][4][5][6] and bimolecular reactions. 1,[7][8][9][10] A substantial number of earlier studies 5,7,9,[11][12][13][14][15][16] consisted of utilizing 1,3,5-trioxane (C 3 H 6 O 3 ) as a clean thermolytic source of formaldehyde to avoid the problem of formaldehyde polymerization. These studies assumed reaction (1)…”

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Comentioning

confidence: 99%

“…They also reported RRKM rates and falloff based on the selected molecular parameters that were most consistent with 4 the experimental data. 11,14,15 Almost a year later, Aldridge et al 12 studied reaction (1) in a static reactor over the temperature range of 523 -603 K and pressures of 25 -800 Torr. In addition to the experimental work, they performed RRKM calculations using the data from BAC-MP4 quantum chemical method.…”

mentioning

confidence: 99%

See 4 more Smart Citations

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Alquaity

Giri

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775 -1082 K and pressures near 900 Torr using a fast response time-of-flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly and it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration time-histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the fall off behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all the species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies of the stationary points were calculated using coupled-cluster with

show abstract

“…This mechanism for 1,3,5-trioxane decomposition was confirmed in a laser schelieren study by Irdam and Kiefer 14 and later by Aldridge et al 12 and Hochgreb and Dryer…”

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Cosupporting

confidence: 55%

“…5. As can be seen, our data fill up the void spaces in the mid-temperature range and encompass both the Irdam and Kiefer 14 and…”

supporting

confidence: 60%

mentioning

confidence: 77%

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Comentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Alquaity

Giri

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

Direct measurements of the reaction OH + CH₂O → HCO + H₂O at high temperatures

Vasudevan

Davidson

Hanson

2004

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The reaction of hydroxyl [OH] radicals with formaldehyde [CH 2 O] was studied at temperatures ranging from 934 K to 1670 K behind reflected shock waves at an average total pressure of 1.6 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide [(CH 3 ) 3 CO OH], while 1,3,5-trioxane [(CH 2 O) 3 ] was used in the preshock mixtures to generate reproducible levels of CH 2 O. OH concentration time-histories were inferred from laser absorption using the well-characterized R 1 (5) line of the OH A-X (0, 0) band near 306.7 nm. Detailed error analyses, taking into account both experimental and mechanism-induced contributions, yielded uncertainty estimates of ±25% at 1595 K and ±15% at 1229 K for the rate of the reaction between CH 2 O and OH. These uncertainties are substantially lower than the factor of two uncertainty currently used for this reaction at high temperatures. The rate constants were fit with the recent low-temperature measurements of Sivakumaran et al. (Phys Chem Chem Phys 2003,5,4821-4827) to the three-parameter form shown below; this fit reconciles experimental data on the title reaction at low, intermediate, and high temperatures (200-1670 K).The reaction of OH with CH 2 O was also studied using quantum chemical methods at the CCSD(T) level of theory using the 6-311++G(d,p) basis set. The transition state for the H-atom metathesis reaction was located, and reaction rate coefficients were calculated. Reasonable agreement with the experimental measurements was obtained.

show abstract

Shock tube study of 1,3,5‐triazine dissociation and relaxation and relaxation of pyrazine

Kiefer

2010

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The three-body dissociation of 1,3,5-triazine (s-triazine, s-C 3 H 3 N 3 → 3HCN) has been observed in incident shock waves with the laser-schlieren technique. The experiments use 5% triazine/Kr and cover 1630-2350 K for 100-600 Torr. These experiments show dissociation rates with strong falloff and a slight but fully expected pressure dependence. The dissociation is without secondary reaction save for a possible, but rather unlikely, contribution from the isomerization HCN → HNC. Electronic structure calculations of the transitionstate properties (G3B3, HL1, E o = 84.6 kcal/mol) are used to construct a Rice-RamspergerKassel-Marcus (RRKM) model whose fit to the rate measurements suggests a E down of 1200 cm −1 . However, a seemingly better fit is achieved using the barrier of 81 kcal/mol proposed by Dyakov et al. (J. Phys. Chem. A 2007, 111, 9591-9599). With this barrier k ∞ (s −1 ) = 5.3 × 10 16 exp(−86.6(kcal/mol)/RT), and the fit now accepts the more routine E down = 126(T /298) 0.9 . It seems the dissociation most likely occurs by a direct, one-step, "triple" dissociation to 3HCN, although the present experiments cannot rule out a multistep process. Vibrational relaxation of the triazine was also examined in 5% and 20% mixtures with Kr over 770-1500 K for pressures between 6 and 14 Torr. Relaxation is very fast, with a slight inverse temperature dependence, P τ rising from 100 to 200 ns-atm over the full temperature range. Integrated gradients are in good accord with calculated total changes in density, indicating a single exponential relaxation. A separate investigation of relaxation in the related molecule pyrazine (500-1300 K, in 1% and 5% in Kr, between 13 and 66 Torr) is included. Again relaxation is rapid, but here the temperature dependence seems more normal, the relaxation times decreasing slightly with temperature. C

show abstract

The decomposition of 1,3,5-trioxane at very high temperatures

Cited by 27 publications

References 10 publications

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Direct measurements of the reaction OH + CH₂O → HCO + H₂O at high temperatures

Shock tube study of 1,3,5‐triazine dissociation and relaxation and relaxation of pyrazine

Contact Info

Product

Resources

About

The decomposition of 1,3,5-trioxane at very high temperatures

Cited by 27 publications

References 10 publications

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Direct measurements of the reaction OH + CH2O → HCO + H2O at high temperatures

Shock tube study of 1,3,5‐triazine dissociation and relaxation and relaxation of pyrazine

Contact Info

Product

Resources

About

Direct measurements of the reaction OH + CH₂O → HCO + H₂O at high temperatures