109-95-5Relevant articles and documents
Kinetic Study of Reactions of C2H5O and C2H5O2 with NO at 298 K and 0.55 - 2 torr
Daele, V.,Ray, A.,Vassalli, I.,Poulet, G.,Bras, G. Le
, p. 1121 - 1134 (1995)
The kinetics of C2H5O and C2H5O2 radicals with NO have been studied at 298 K using the discharge flow technique coupled to laser induced fluorescence (LIF) and mass spectrometry analysis.The temporal profiles of C2H5O were monitored by LIF.The rate constant for C2H5O + NO -> Products (2), measured in the presence of helium, has been found to be pressure dependent: k2 = (1.25 +/- 0.04) x 10-11, (1.66 +/- 0.06) x 10-11, (1.81 +/- 0.06) x 10-11 at P (He) = 0.55, 1 and 2 torr, respectively (units are cm3 molecule-1 s-1).The Lindemann-Hinshelwood analysis of these rate constant data and previous high pressure measurements indicates competition between association and disproportionation channels: C2H5O + NO + M -> C2H5ONO + M (2a), C2H5O + NO -> CH3CHO + HNO (2b).The following calculated average values were obtained for the low and high pressure limits of k2a and for k2b : k02a = (2.6 +/- 1.0) x 10-28 cm6 molecule-2 s-1, kinfinite2a = (3.1 +/- 0.8) x 10-11 cm3 molecule-1 s-1 and k2b ca. 8 x 10-12 cm3 molecule-1 s-1.The present value of k02a, obtained with He as the third body, is significantly lower than the value (2.0 +/- 1.0) x 10-27 cm6 molecule-2 s-1 recommended in air.The rate constant for the reaction C2H5O2 + NO -> C2H5O + NO2 (3) has been measured at 1 torr of He from the simulation of experimental C2H5O profiles.The value obtained for k3 = (8.2 +/- 1.6) x 10-12 cm3 molecule-1 s-1 is in good agreement with previous studies using complementary methods.
-
Ray,Neogi
, p. 1900 (1906)
-
Reaction of alcohol with NO2 on a Cleaned Glass Surface
Maeda, Yasuaki,Fujio, Yoshifumi,Munemori, Makoto
, p. 2127 - 2130 (1986)
Formation of alkyl nitrite from alcohol and NO2 was very fast on a Pyrex glass surface cleaned with chromic acid mixture.The reaction was practically zero order with respect to NO2.The rate constant was (1.7 +/- 0.08)*10E-18 cm3*molecule-1*s-1 for methyl nitrile formation and the apparent activation energy was -53.5 kJ*mol-1.
Flow analysis method for determining the concentration of methanol and ethanol in the gas phase using the nitrite formation reaction
Takenaka,Nguyen,Bandow,Maeda
, p. 5847 - 5851 (2000)
The emission sources of alcohols are significant from plants. The use of alcohol-fueled vehicles has increased. Due to the emission from these alcohol-fueled vehicles, the atmospheric alcohol concentrations are expected to be higher than that in the past from plant emission sources. A flow determination method for low molecular weight alcohols (methanol, ethanol) in the gas phase using the nitrite formation reaction, which was developed from an earlier method using a glass bottle was presented. The ambient air and NO2 (1000 ppm vol) were allowed to continuously flow in glass tube, which had been filled with 10 g of Pyrex glass beads. The flow rates of the ambient air and NO2 were 30 and 20 cc/min, respectively. The gas-phase alkyl nitrites produced by the dark reaction of atmospheric alcohols and NO2 on the Pyrex glass beads were analyzed by GC with an electron capture detector. The alcohol concentrations of the samples were computed using a calibrated conversion factor for each alcohol to its nitrite. The detection limits for the methanol and ethanol were 0.7 and 0.5 ppb vol, respectively. The method indicated significant improvement compared with the other methods for measuring ambient alcohol due to its high sensitivity, no required concentration process, and rather high yields of the alkyl nitrite from alcohol. It can be an automated analysis system for atmospheric alcohol.
Temperature dependence of the near UV absorption spectra and photolysis products of ethyl nitrate
Zhu, Lei,Ding, Chuan-Fan
, p. 177 - 184 (1997)
The UV absorption cross sections for ethyl nitrate were measured as a function of temperature between 265 and 340 nm by using cavity ring-down spectroscopy.Absorption cross sections increased with temperature between 238 and 298 K.The variation with temperature was greater at longer wavelengths.Photodissociation product channels of ethyl nitrate at 308 nm were determined using an excimer laser and a cavity ring-down spectrometer.C2H5O + NO2 were the sole photofragmentation products with a quantum yield of 1.0+/-0.1, independent of temperature.Atmospheric implications are discussed.
-
Krueger,W.E. et al.
, p. 2877 - 2879 (1978)
-
Formation of Organic Mitro-compounds in Flowing H2O2+NO2+N2+Organic Vapour Systems. Part 1.-Surface Initiation Efficiency and Reactions of Ethane
Audley, Gary J.,Baulch, Donald L.,Campbell, Ian M.
, p. 599 - 608 (1984)
When H2O2 vapour is added to an excess of NO2 in a flow system with ethane as the carrier gas in the presence of a boric-acid-coated surface at temperatures in the range 298-363 K, the organic products are niroethane, ethyl nitrate and smaller amounts of ethyl nitrite.On the basis of the initiating steps the total yield of nitro-compounds, extrapolated to =0, provides a direct measure of the H2O2 to OH conversion efficiency in step(1).This is shown to correspond to that indicated by the previously applied indirect method involving measurement of the variation of CO2 yields with the ratio / in H2O2+NO2+CO systems containing diethyl ether (S) as the internal kinetic calibrant.This efficiency does not change significantly throughout the above temperature range.The mechanism of formation of the nitrocompounds involves the following competitive steps: .Arguments are presented that step (8) may proceed by way of partial dissociation of chemically activated C2H5ONO molecules rather than by bimolecular O-abstraction route.A rate constant of k4=(1.3+/-0.2)xE10 dm3mol-1s-1 is obtained for the reaction at ambient temperature for M=C2H6 at a pressure of 40 kPa.
Kinetics of the Reaction between Ethylperoxy Radicals and Nitric Oxide
Maricq, M. Matti,Szente, Joseph J.
, p. 12374 - 12379 (1996)
The kinetic of the C2H5O2 + NO -> C2O5O + NO2 reaction is examined by two real-time techniques.NO consumption and NO2 formation are measured using transient diode laser absorption, whereas ethylperoxy loss and ethylnitrite formation are monitored by time-resolved UV spectrometry.Simultaneous fits of the NO and NO2 concentration versus time profiles yield rate constants consistent with the results of the C2H5O2 and C2H5ONO measurements.The combined data yield a rate constant of k5 = (3.1-1.0+1.5)E-12 e (330+/-11)/T cm3 s-1 over the 220-355 K temperature range.The small negative temperature dependence is consistent with the accepted mechanism of the reaction proceeding through a C2H5O2NO adduct.
Disproportionation to Combination Ratios of Alkoxy Radicals with Nitric Oxide
Morabito, Paul,Heicklen, Julian
, p. 2914 - 2916 (1985)
The disproportionation to combination ratios were measured at 175 deg C for the reactions RO + 15NO -> RO15NO (2a) and RO + 15NO -> RCHO + H15NO (2b), with the following alkoxy radicals: C2H5O, n-C3H7O, n-C4H9O, and i-C4H9O.The alkoxy radical was generated by the termal decomposition of the corresponding alkyl nitrite in the presence of 15NO.The rate of the corresponding isotopically enriched alkyl nitrite was measured by mass spectrometry while the aldehyde rate was determined by gas chromatography.The results obtained for k2b/k2 were 0.22 +/= 0.02, 0.26 +/= 0.03, 0.29 +/= 005, and 033 +/= 0.03, respectively, for C2H5O, n-C3H7O, n-C4H9O, and i-C4H9O.With these values of k2b/k2 we were able to determine the primary quantum yield of the photolysis of the corresponding alkyl nitrites at 366 nm to be, respectively, 0.32 +/= 0.04, 0.44 +/= 0.06, 0.19 +/= 0.04, and 0.19 +/= 0.02.
A New Method for the Synthesis of Nitroethane, Ethyl Nitrite, and Ethyl Nitrate
Audley, Gary J.,Baulch, Donald L.,Campbell, Ian M.
, p. 1053 - 1055 (1982)
When H2O2 vapour and NO2 are mixed in an ethane carrier in a flow system in the presence of a boric acid-coated surface, ethyl nitrate, nitroethane, and some ethyl nitrite are synthesized; a mechanism is advanced in which OH* and C2H5* radicals are the intermediates.
S-alkylation of thiacalixarenes: A long-neglected possibility in the calixarene family
Kundrat, Ondrej,Eigner, Vaclav,Dvorakova, Hana,Lhotak, Pavel
supporting information; scheme or table, p. 4032 - 4035 (2011/09/20)
Despite the high nucleophilicity of sulfur atoms, thiacalixarenes have been alkylated only on oxygen atoms thus far. Using strong alkylating agents (triflates, trialkyloxonium salts), the substitution of the sulfur bridges has been successfully accomplished. The corresponding sulfonium salts of thiacalix[4]arene are formed regio- and stereoselectively as a completely new type of substitution pattern in thiacalixarene chemistry. These compounds possess interesting conformational behavior and could be used as unusual alkylating agents with uncommon selectivity.
