Ion–molecule reactions in vinyl chloride and vinyl bromide

1969 ◽  
Vol 47 (4) ◽  
pp. 647-653 ◽  
Author(s):  
J. A. Herman ◽  
J. J. Myher ◽  
A. G. Harrison
Keyword(s):  
Vinyl Chloride ◽  
Rate Coefficient ◽  
Order Reaction ◽  
Second Order ◽  
Third Order ◽  
Vinyl Bromide ◽  
Ion Molecule Reactions ◽  
Fragment Ions ◽  
Product Distributions ◽  
Energy Formula

The following ion–molecule reactions involving fragment ions in vinyl chloride have been studied and rate constants measured for ions of 2.4 eV exit energy.[Formula: see text]The reaction of the C2H3Cl+ molecule-ion produces C3H4Cl+, C4H5Cl+, and C4H6Cl+ both in a second order and a third order reaction. The apparent rate coefficient for the second order reaction is approximately 1 × 10−11 cm3 molecule−1 s−1 while that for the third order reaction is approximately 1 × 10−25 cm6 molecule−2 s−1. The product distributions from both the second and third order reactions have been determined.In vinyl bromide the C2H3+ ion produces C4H5+, C4H6+, and C2H4Br+ while the C2H3Br+ ion reacts to form C4H6Br+ both in a second order and a third order reaction.

Ion–molecule reactions in vinyl fluoride

1969 ◽  
Vol 47 (6) ◽  
pp. 957-964 ◽  
Author(s):  
J. A. Herman ◽  
A. G. Harrison
Keyword(s):  
Charge Transfer ◽  
Rate Constants ◽  
Order Reaction ◽  
Third Order ◽  
Vinyl Fluoride ◽  
Ion Molecule Reactions ◽  
Fragment Ions ◽  
Consecutive Reactions ◽  
Product Distributions ◽  
The Individual

The ion–molecule reactions in vinyl fluoride have been studied as a function of pressure and electron energy. The C2H2+ and C2HF+ fragment ions react predominantly by charge transfer while C2H3+ produces C2H4F+ and C4H5+. The C2H2F+ fragment forms C2H4F+, CHF2+, C2H3F2+, C4H4F+, and probably C2H3+. The rate constants for the individual reactions have been measured. The C2H3F+ ion reacts to form C3H5+, C3H4F+, C3H3F2+, and C4H5F+ (in minor yield), both by a second order and by a third order reaction. The rate constants and product distributions from the individual reactions have been evaluated. A number of consecutive reactions have been identified and shown to be third order processes.

Termolecular ion–molecule reactions involving C3H5+

1970 ◽  
Vol 48 (22) ◽  
pp. 3549-3553 ◽  
Author(s):  
A. G. Harrison ◽  
A. A. Herod
Keyword(s):  
Kinetic Energy ◽  
Molecular Size ◽  
Order Rate Constant ◽  
Second Order ◽  
Rate Coefficients ◽  
Third Order ◽  
Order Rate ◽  
Ion Molecule Reactions ◽  
Similar Dependence ◽  
Ion Kinetic Energy

The reaction of C3H5+ with C2D4 to produce C5H5D4+ is shown to be second order in C2D4. The rate coefficients are in the range 10−24 to 10−25 cm6 molecule−2 s−1 but decrease markedly with increasing ion kinetic energy. This decrease reflects the effect of the ion kinetic energy on the lifetime of the initial collision complex. Small differences in rate coefficients are observed depending on the source of the C3H5+ ion but these are insufficient to distinguish between possibly different ionic structures. The reaction of C3H5+ with C2H3F forms C5H7+ in a reaction second order in C2H3F. The rate coefficients are also in the range 10−24 to 10−25 cm6 molecule−1 s−1 and show a similar dependence on ion kinetic energy. These high third order rate constants are compared with data for other termolecular reactions and are shown to be consistent with the effect of molecular size on the third order rate constant.

KINETICS AND MECHANISMS OF THE THERMAL DECOMPOSITION OF ACETALDEHYDE: I. THE UNINHIBITED REACTION

1964 ◽  
Vol 42 (8) ◽  
pp. 1851-1860 ◽  
Author(s):  
M. Eusuf ◽  
K. J. Laidler
Keyword(s):  
Order Reaction ◽  
Second Order ◽  
Small Extent ◽  
Kinetic Behavior ◽  
Third Order ◽  
The Third ◽  
Rate Of Reaction ◽  
Ethane Formation ◽  
Kinetics Of ◽  
Initial Process

The kinetics of the uninhibited decomposition of acetaldehyde have been reexamined. The initial rates of the decomposition of pure acetaldehyde show strict three-halves-order dependence at temperatures from 480 to 525 °C, and the activation energy is 47.6 kcal per mole. Foreign gases, which decrease the rate of reaction, cause a significant increase in order. The rate of ethane formation is second order in acetaldehyde, and Trenwith has found the hydrogen formation to be second order in acetaldehyde. The results are shown to be consistent only with a mechanism involving second-order initiation and the third-order reaction 2CH3 + M → C2H6 + M as the terminating step. The rate of the initiation process is increased only to a small extent by the addition of inert foreign gases; it is suggested that the initial process may be CH3CHO + CH3CHO → CH3CHOH + CH3CO, with a subsequent breakdown of CH3CHOH into CH3CHO + H. The mechanism is shown to account for the overall kinetic behavior and for the formation of the minor products.

Bulk Contributions Modulate the Sum-Frequency Generation Spectra of Interfacial Water on Model Sea-Spray Aerosols

2018 ◽  
Author(s):  
Sandeep K. Reddy ◽  
Raphael Thiraux ◽  
Bethany A. Wellen Rudd ◽  
Lu Lin ◽  
Tehseen Adel ◽  
...  
Keyword(s):  
Single Layer ◽  
Sum Frequency Generation ◽  
Second Order ◽  
Interfacial Structure ◽  
Sea Spray ◽  
Third Order ◽  
Systematic Analysis ◽  
Sum Frequency ◽  
Structure Of Water ◽  
Frequency Generation

Vibrational sum-frequency generation (vSFG) spectroscopy is used to determine the molecular structure of water at the interface of palmitic acid monolayers. Both measured and calculated spectra display speci c features due to third-order contributions to the vSFG response which are associated with nite interfacial electric potentials. We demonstrate that theoretical modeling enables to separate the third-order contributions, thus allowing for a systematic analysis of the strictly surface-sensitive, second-order component of the vSFG response. This study provides fundamental, molecular-level insights into the interfacial structure of water in a neutral surfactant system with relevance to single layer bio-membranes and environmentally relevant sea-spray aerosols. These results emphasize the key role that computer simulations can play in interpreting vSFG spectra and revealing microscopic details of water at complex interfaces, which can be difficult to extract from experiments due to the mixing of second-order, surface-sensitive and third-order, bulk-dependent contributions to the vSFG response.

Stability of radical anions derived from substituted 5-nitrofurans investigated by ESR spectroscopy

1985 ◽  
Vol 50 (7) ◽  
pp. 1594-1601 ◽  
Author(s):  
Jiří Klíma ◽  
Larisa Baumane ◽  
Janis Stradinš ◽  
Jiří Volke ◽  
Romualds Gavars
Keyword(s):  
Radical Anion ◽  
High Stability ◽  
Esr Spectroscopy ◽  
Reaction Path ◽  
Order Reaction ◽  
Second Order ◽  
Radical Anions ◽  
Second Order Reaction ◽  
Unpaired Electron Density ◽  
The Stability

It has been found that the decay in dimethylformamide and dimethylformamide-water mixtures of radical anions in five of the investigated 5-nitrofurans is governed by a second-order reaction. Only the decay of the radical anion generated from 5-nitro-2-furfural III may be described by an equation including parallel first- and second-order reactions; this behaviour is evidently caused by the relatively high stability of the corresponding dianion, this being an intermediate in the reaction path. The presence of a larger conjugated system in the substituent in position 2 results in a decrease of the unpaired electron density in the nitro group and, consequently, an increase in the stability of the corresponding radical anions.

Kinetics of the reaction between hexamethylenediisocyanate and 1-pentanol

1983 ◽  
Vol 48 (11) ◽  
pp. 3279-3286
Author(s):  
Slavko Hudeček ◽  
Miloslav Bohdanecký ◽  
Ivana Hudečková ◽  
Pavel Špaček ◽  
Pavel Čefelín
Keyword(s):  
Liquid Chromatography ◽  
Rate Constants ◽  
Reversed Phase ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Reversed Phase Liquid Chromatography ◽  
Consecutive Reactions ◽  
Phase Liquid ◽  
Kinetics Of

The reaction between hexamethylenediisocyanate and 1-pentanol in toluene was studied by means of reversed-phase liquid chromatography. By employing this method, it was possible to determine all components of the reaction mixture including both products, i.e. N-(6-isocyanate hexyl)pentylcarbamate and N,N'-bis(pentyloxycarbonyl)hexamethylenediamine. Relations for the calculation of kinetic constants were derived assuming a competitive consecutive second-order reaction. It was demonstrated that the reaction involved in this case is indeed a second-order reaction, and the rate constants of the first and second consecutive reactions were determined.

Evidence for general base catalysis by protic solvents in a kinetic study of alcoholyses and hydrolyses of 1-(phenoxycarbonyl)pyridinium ions under both solvolytic and non-solvolytic conditions

2009 ◽  
Vol 74 (1) ◽  
pp. 43-55 ◽  
Author(s):  
Dennis N. Kevill ◽  
Byoung-Chun Park ◽  
Jin Burm Kyong
Keyword(s):  
Second Order ◽  
Base Catalysis ◽  
Substitution Reactions ◽  
Third Order ◽  
Methoxy Derivative ◽  
First Order ◽  
General Base ◽  
Protic Solvents ◽  
Kinetics Of ◽  
Pyridinium Ions

The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.

The Asymptotic Second Order Moments of the Estimated Third Order Cumulants of Stationary Processes

1988 ◽  
Author(s):  
Boaz Port ◽  
Benjamin Friedlander
Keyword(s):  
Second Order ◽  
Stationary Processes ◽  
Third Order

scholarly journals An ICR Study of an Association Reaction at Low Pressure

1980 ◽  
Vol 87 ◽  
pp. 305-306
Author(s):  
M.J. Mcewan ◽  
V. G. Anicich ◽  
W.T. Huntress ◽  
P. R. Kemperer ◽  
M. T. Bowers
Keyword(s):  
Pressure Range ◽  
Rate Coefficient ◽  
Low Pressure ◽  
Second Order ◽  
Radiative Association ◽  
Association Reaction

An ICR investigation of the association reactionCH3+ + HCN CH3.HCN+has shown the reaction follows second order kinetics over the pressure range 1 × 10-6 to 3 × 10-4 Torr with a rate coefficient of 2 × 10-10 cm3s-1. These results can be interpreted in terms of a saturated 3-body or radiative association mechanism.

Internal-state nonequilibrium effects for a fast, second-order reaction

1985 ◽  
Vol 89 (1) ◽  
pp. 5-7 ◽  
Author(s):  
Carmay Lim ◽  
Donald G. Truhlar
Keyword(s):  
Internal State ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Nonequilibrium Effects
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