Unimolecular Rate Constant and Threshold Energy for the HF Elimination from Chemically Activated CF3CHFCF3

被引：6

作者：

Duncan, Juliana R. ^{[1
]}

Roach, Michael S. ^{[1
]}

Stiles, Brooke Sibila ^{[1
]}

Holmes, Bert E. ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Asheville, NC 28804 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 26期

基金：

美国国家科学基金会;

关键词：

DENSITY-FUNCTIONAL THEORY; AB-INITIO CALCULATIONS; SHOCK-TUBE PYROLYSES; COLLISIONAL DEACTIVATION; 2-H HEPTAFLUOROPROPANE; THERMAL-DECOMPOSITION; HYDROFLUOROCARBONS; MIXTURES; RADICALS; ATOMS;

D O I：

10.1021/jp100195e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Combination of CF3CHF and CF3 radicals at room temperature generated chemically activated CF3CHFCF3 molecules with 95 +/- 3 kcal/mol of internal energy that decompose by loss of HF, initially attached to adjacent carbons, with an experimental unimolecular rate constant of (4.5 +/- 1.1) x 10(2) s(-1). Density functional theory was used to model the unimolecular rate constant for HF elimination, km:, to determine a threshold energy of 75 +/- 2 kcal/mol.

引用

页码：6996 / 7002

页数：7

共 50 条

[41] ION-CYCLOTRON RESONANCE STUDY OF BASE-INDUCED ELIMINATION-REACTIONS OF FLUORINATED ALCOHOLS AND UNIMOLECULAR LOSS OF HF FROM CHEMICALLY ACTIVATED FLUOROALKOXIDE IONS
CLAIR, RL
MCMAHON, TB
[J]. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1980, 33 (01): : 21 - 36
[42] DIRECT MEASUREMENT OF NEAR-THRESHOLD RATE CONSTANTS FOR UNIMOLECULAR DISSOCIATION OF CF3I AFTER IR MULTIPHOTON EXCITATION
ABEL, B
BROUWER, L
HERZOG, B
HIPPLER, H
TROE, J
[J]. CHEMICAL PHYSICS LETTERS, 1986, 127 (06) : 541 - 546
[43] PRIMARY KINETIC ISOTOPE EFFECT FOR THE ELIMINATION OF HCL(DCL) AND HF(DF) FROM CHEMICALLY ACTIVATED CH3CFCL2 AND CD3CFCL2
MCDONIEL, JB
HOLMES, BE
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1994, 207 : 271 - CHED
[44] Unimolecular rate constants and kinetic isotope effects for decomposition of chemically activated CF2BrCF2CH3 and CF2BrCF2CD3:: Evidence for a novel 1,2-FBr interchange.
Lisowski, CE
Heard, GL
Holmes, BE
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2001, 222 : U216 - U216
[45] Reactions of hydroxyl radicals with several hydrofluorocarbons. The temperature dependencies of the rate constants for CHF2CF2CH2F (HFC-245ca), CF3CHFCHF2 (HFC-236ca), CF3CHFCF3 (HFC-277ca), and CF3CH2CH2CF3 (HFC-3561fa)
Zhang, Z.
Padmaja, S.
Rameshwa, D.
Saini, D.
Huie, R.E.
Kurylo, M.J.
[J]. Journal of Physical Chemistry, 1994, 98 (16):
[46] UNIMOLECULAR REACTIONS OF CHEMICALLY ACTIVATED CH3CHFCD3, CH3 CHFCH2CH3, AND (CH3)3CF AT ENERGIES OF 88 AND 110 KCAL MOL
KIM, KC
SETSER, DW
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1972, 164 (AUG-S): : 143 - &
[47] CHEMICALLY ACTIVATED C-14H3CF3 FROM CROSS COMBINATION OF C-14H3 WITH CF3 - INTRODUCTORY EXPERIMENTAL STUDY
PETTIJOHN, RR
MUTCH, GW
ROOT, JW
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (20): : 2077 - 2085
[48] COMPARISON OF ENERGY PARTITIONING FROM 3-CENTERED PROCESSES - BIMOLECULAR TRANSFER AND UNIMOLECULAR ELIMINATION REACTIONS
CHANG, HW
SETSER, DW
PERONA, MJ
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1971, 75 (13): : 2070 - &
[49] CHEMICALLY ACTIVATED (C-14-H-3)CF3 FROM CROSS COMBINATION OF C-14-H-3 WITH CF3 .2. COLLISIONAL ENERGY-TRANSFER TO FLUORINATED ETHANES
PETTIJOHN, RR
MUTCH, GW
ROOT, JW
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (16): : 1747 - 1748
[50] The Unimolecular Reactions of CF3CHF2 Studied by Chemical Activation: Assignment of Rate Constants and Threshold Energies to the 1,2-H Atom Transfer, 1,1-HF and 1,2-HF Elimination Reactions, and the Dependence of Threshold Energies on the Number of F-Atom Substituents in the Fluoroethane Molecules
Smith, Caleb A.
Gillespie, Blanton R.
Heard, George L.
Setser, D. W.
Holmes, Bert E.
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2017, 121 (46): : 8746 - 8756

← 1 2 3 4 5 →