Ion–molecule reactions in formic-d acid and methyl formate

1968 ◽  
Vol 46 (12) ◽  
pp. 2141-2146 ◽  
Author(s):  
Howard Pritchard ◽  
J. C. J. Thynne ◽  
A. G. Harrison
Keyword(s):  
Rate Constants ◽  
Methyl Formate ◽  
Ion Molecule Reactions ◽  
Dipole Interactions ◽  
Induced Dipole ◽  
Energy Formula ◽  
Good Agreement

The following ion–molecules reactions have been found to occur in DCOOH for ions produced by bombardment with electrons of 10–15 eV energy (all rate constants in cm3 molecule−1 units).[Formula: see text]In methyl formate the following reactions have been identified and rate constants measured for ions formed by bombardment with electrons of 10–15 eV energy.[Formula: see text]Experiments using DCO2CH3 show that reaction [f] involves transfer of the methyl hydrogen at a rate 1.5 times that of the formyl hydrogen while reaction [g] involves transfer from only the methyl position of CH3OH+. The rate constants for all reactions are considerably higher than predicted on the basis of ion–induced dipole interactions only but are in good agreement with values calculated by including ion–dipole interactions.

scholarly journals Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH5+ and C2H5+

1973 ◽  
Vol 51 (10) ◽  
pp. 1645-1654 ◽  
Author(s):  
A. S. Blair ◽  
A. G. Harrison
Keyword(s):  
Proton Transfer ◽  
Trapped Ions ◽  
Rate Coefficients ◽  
Polar Molecules ◽  
Large Role ◽  
Bimolecular Reactions ◽  
Trapped Ion ◽  
Ion Molecule Reactions ◽  
Dipole Interactions ◽  
Induced Dipole

The ion–molecule reactions in mixtures of methane with the polar molecules dimethyl-d6 ether, ethylene-d4 oxide, acetaldehyde-d4, acetone, and acetonitrile have been studied using the trapped-ion technique. The CH5+ and C2H5+ ions produced by ion–molecule reactions in methane react rapidly (predominantly by proton transfer) with the polar molecules; the rate coefficients range from 1.98 × 10−9 cm3 molecule−1 s−1 (C2H5+ + C2D4O) to 5.26 × 10−9 cm3 molecule−1 s−1 (CH5+ + (CH3)2CO). The rate coefficients are much larger than those predicted from ion – induced dipole interactions only indicating that ion–dipole interactions play a large role in the collision process.Rate coefficients for reaction of CH3+ and CH4+ with the polar molecules also have been measured. Most of these also are larger than predicted from ion – induced dipole interactions indicating in this case as well substantial effects due to ion–dipole interactions.

REACTIONS OF THERMAL ENERGY IONS: II. RATES OF SOME HYDROGEN TRANSFER ION–MOLECULE REACTIONS

1966 ◽  
Vol 44 (12) ◽  
pp. 1351-1359 ◽  
Author(s):  
A. G. Harrison ◽  
A. Ivko ◽  
T. W. Shannon
Keyword(s):  
Field Strength ◽  
Rate Constant ◽  
Thermal Energy ◽  
Rate Constants ◽  
Hydrogen Transfer ◽  
Thermal Reaction ◽  
Dipole Model ◽  
Protonated Molecule ◽  
Ion Molecule Reactions ◽  
Induced Dipole

The rate constants for the ion–molecule reactions forming the protonated molecule in CH3CN, H2, CH4, and CH3OCH3, the equivalent reactions in the deuteriated species, and the reactions forming COD+ in CO–CD4 mixtures have been measured at thermal energies and at 10.5 V/cm repeller field strength. For H2, HD, D2 and the reactions in CO–CD4 mixtures the rate constant for the thermal reaction is approximately 0.3–0.5 that of the 10.5 V/cm rate constant. For all other cases the ratio of rate constants is approximately unity as predicted by the ion-induced dipole model. The absolute values of the rate constants in most cases are considerably lower than predicted by theory.

Reactions of thermal energy ions. VI. Hydrogen-transfer ion–molecule reactions involving polar molecules

1967 ◽  
Vol 45 (24) ◽  
pp. 3107-3117 ◽  
Author(s):  
S. K. Gupta ◽  
E. G. Jones ◽  
A. G. Harrison ◽  
J. J. Myher
Keyword(s):  
Mass Spectrometer ◽  
Thermal Energy ◽  
Pressure Measurement ◽  
Rate Constants ◽  
Hydrogen Transfer ◽  
Collision Theory ◽  
Protonated Molecule ◽  
Ion Molecule Reactions ◽  
Dipole Interactions ◽  
Made In

The rate constants for formation of the protonated molecule by ion–molecule reactions in CH3OH, (CH3)2O, and CH4 have been studied both at thermal energies and at 3.4 eV ion exit energy with a new mass spectrometer described in the present work. The rate constants are found to be approximately a factor of two greater than previously measured and it is concluded that an error in pressure measurement was made in the earlier work. Revised rate constants are presented for a number of systems studied previously. The results are compared with predictions of the collision theory modified in this paper to include the effect of ion-dipole interactions.

Computational Study on the Kinetics and Mechanisms of Unimolecular Reactions of (Z)-(Z)-N-(λ5-phosphanylidene) Formohydrazonic Formic Anhydride: Intramolecular aza-Wittig Reaction in Competition with Mumm Rearrangement

2020 ◽  
Vol 17 (11) ◽  
pp. 884-889
Author(s):  
Somayeh Mirdoraghi ◽  
Hamed Douroudgari ◽  
Farideh Piri ◽  
Morteza Vahedpour
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Wittig Reaction ◽  
Computational Study ◽  
Single Step ◽  
Low Energy ◽  
Coupled Cluster ◽  
Unimolecular Reaction ◽  
Single Step Reaction ◽  
Good Agreement

For (Z)-(Z)-N-(λ5-phosphanylidene) formohydrazonic formic anhydride, Aza-Wittig reaction and Mumm rearrangement are studied using both density functional and coupled cluster theories. For this purpose, two different products starting from one substrate are considered that are competing with each other. The obtained products, P1 and P2, are thermodynamically favorable. The product of the aza-Wittig reaction, P1, is more stable than the product of Mumm rearrangement (P2). For the mentioned products, just one reliable pathway is separately proposed based on unimolecular reaction. Therefore, the rate constants based on RRKM theory in 300-600 K temperature range are calculated. Results show that the P1 generation pathway is a suitable path due to low energy barriers than the path P2. The first path has three steps with three transition states, TS1, TS2, and TS3. The P2 production path is a single-step reaction. In CCSD level, the computed barrier energies are 14.55, 2.196, and 10.67 kcal/mol for Aza-Wittig reaction and 42.41 kcal/mol for Mumm rearrangement in comparison with the corresponding complexes or reactants. For final products, the results of the computational study are in a good agreement with experimental predictions.

An ICR mass spectrometry study of ion/molecule reactions between ethyl chloride and alkylamines

1991 ◽  
Vol 69 (2) ◽  
pp. 363-367
Author(s):  
Guoying Xu ◽  
Jan A. Herman
Keyword(s):  
Mass Spectrometry ◽  
Key Words ◽  
Rate Constant ◽  
Rate Constants ◽  
Ethyl Chloride ◽  
Ion Molecule Reactions ◽  
Mass Spectrometry Study ◽  
Ethyl Cation

Ion/molecule reactions in mixtures of ethyl chloride with C1–C4 alkylamines were studied by ICR mass spectrometry. Ethyl cation transfer to C1–C4 alkylamines proceeds mainly through diethylchloronium ions with rate constants ~3 × 10−10cm3 s−1. In the case of s-butylamine the corresponding rate constant is 0.5 × 10−10 cm3 s−1. Key words: ICR mass spectrometry, ion/molecule reactions, ethylchloride, methylamine, ethylamine, propylamines, butylamines

scholarly journals Probing Protein Shelf Lives from Inverse Mean First Passage Times

2019 ◽  
Author(s):  
Vishal Singh ◽  
Parbati Biswas
Keyword(s):  
Protein Aggregation ◽  
Rate Constants ◽  
Survival Probability ◽  
First Passage Time ◽  
Passage Time ◽  
First Passage ◽  
First Order Kinetics ◽  
The Mean ◽  
Passage Times ◽  
Good Agreement

Protein aggregation is investigated theoretically via protein turnover, misfolding, aggregation and degradation. The Mean First Passage Time (MFPT) of aggregation is evaluated within the framework of Chemical Master Equation (CME) and pseudo first order kinetics with appropriate boundary conditions. The rate constants of aggregation of different proteins are calculated from the inverse MFPT, which show an excellent match with the experimentally reported rate constants and those extracted from the ThT/ThS fluorescence data. Protein aggregation is found to be practically independent of the number of contacts and the critical number of misfolded contacts. The age of appearance of aggregation-related diseases is obtained from the survival probability and the MFPT results, which matches with those reported in the literature. The calculated survival probability is in good agreement with the only available clinical data for Parkinson’s disease.<br>

Mechanism and Structure in the Ion Chemistry of Tetramethyldiphosphine: An Ion Cyclotron Resonance Spectrometric Study

1976 ◽  
Vol 31 (5) ◽  
pp. 414-421 ◽  
Author(s):  
Karl-Peter Wanczek
Keyword(s):  
Mass Spectrum ◽  
Rate Constants ◽  
Cyclotron Resonance ◽  
Double Resonance ◽  
Ion Cyclotron Resonance ◽  
Spectrometric Study ◽  
Ion Chemistry ◽  
Ion Molecule Reactions ◽  
Ion Cyclotron ◽  
Ion Cyclotron Resonance Spectrometry

Abstract The mass spectrum of tetramethyldiphosphine and the ion chemistries of this compound and of its mixtures with phosphine and dimethylphosphine have been investigated by ion cyclotron resonance spectrometry. Numerous ion molecule reactions have been observed. The rate constants of the two most abundant ions formed by the molecular ion, the tetramethyldiphosphonium ion, H(CH3)2P-P(CH3)2+ and the hexamethyltriphosphonium ion, P3(CH3)6+ , are k2.35≦0.1X10-10 cm3 molecule-1 s-1 and k2.40 = 1.5 X10-10 cm3 molecule -1 s -1 respectively. The structures of several ions have been determined with the aid of their ion-molecule reactions. The ions m/e = 79 and 93 are thought to have the structures HP - P(CH3)H+ and HP-P(CH3)2+ . The most probable structures of the ions m/e = 169 and 183 are HP(CH3)2-P(CH3)-P(CH3)2+ and (CH3)2P-P(CH3) - P(CH3)3+ . The protonated molecule undergoes several ion-molecule reactions, which proceed via an intermediate, m/e = 183, [(CH3)6P3+]* which is detected by double resonance experiments.

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

1982 ◽  
Vol 47 (7) ◽  
pp. 1773-1779 ◽  
Author(s):  
T. P. Radhakrishnan ◽  
A. K. Sundaram
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Outer Sphere ◽  
Electrode Reaction ◽  
Transfer Reactions ◽  
Cyclic Voltammetric ◽  
Edta Solution ◽  
Kinetics Of ◽  
Activated Complex ◽  
Good Agreement

The paper is a detailed study of the cyclic voltammetric behaviour of Eu3+ at HMDE in molar solutions of KCl, KBr, KI, KSCN and in 0.1M-EDTA solution with an indigenously built equipment. The computed values of the rate constants at various scan rates show good agreement with those reported by other electrochemical methods. In addition, the results indicate participation of a bridged activated complex in the electron-transfer step, the rate constants showing the trend SCN- > I- > Br- > Cl- usually observed for bridging order of these anions in homogeneous electron-transfer reactions. The results for Eu-EDTA system, however, indicate involvement of an outer sphere activated complex in the electrode reaction.

Reaction of Adsorbed CO with Methanol and Ethanol on Pt Electrode: Estimation of Rate Constants

2020 ◽  
Author(s):  
Keisuke Iida ◽  
Yoshiharu Mukouyama
Keyword(s):  
Rate Constants ◽  
High Performance ◽  
Methyl Formate ◽  
Present Report ◽  
Ethyl Formate ◽  
Infrared Absorption Spectroscopy ◽  
Pt Electrode ◽  
Surface Enhanced ◽  
Langmuir Hinshelwood Mechanism ◽  
Adsorbed Co

It is well accepted that adsorbed CO (COad) on Pt electrode reacts with water (or oxygenated species). We have recently found that COad also reacts with methanol and ethanol to form methyl formate (COad + CH3OH → HCOOCH3) and ethyl formate (COad + C2H5OH → HCOOC2H5), respectively, by using surface-enhanced infrared absorption spectroscopy and high-performance liquid chromatography. In the present report, we estimate the rate constants of the reactions by considering that the reactions proceed via Langmuir-Hinshelwood mechanism. The rate constants are estimated to be in the order of 0.1 s-1.

An ICR Study of Ion-Molecule Reactions in the C2H2/HCN System

1980 ◽  
Vol 87 ◽  
pp. 299-303 ◽  
Author(s):  
M.J. Mcewan ◽  
V. G. Anicich ◽  
W.T. Huntress
Keyword(s):  
Rate Constants ◽  
Interstellar Clouds ◽  
Ion Molecule Reactions

Rate constants obtained by the ICR technique are reported for reaction (1), C2H2+ + HCN and reaction (2) HCN+ + C2H2 such that k1 = 3.6 × 10−10 and k2 = 6.9 × 10−10 cm3 molecule−1 s−1, respectively. Differences between these results and other measurements of reaction (1) are discussed. The relevance of reaction (1) to the formation of HC3N in interstellar clouds is also briefly assessed.

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