Hydrolysis of Ethylene Oxide Derivatives in Deuterium Oxide-Water Mixtures1

1956 ◽  
Vol 78 (23) ◽  
pp. 6008-6013 ◽  
Author(s):  
J. G. Pritchard ◽  
F. A. Long
Keyword(s):  
Ethylene Oxide ◽  
Deuterium Oxide ◽  
Hydrolysis Of

Preparation of Organized Mesoporous Silica from Sodium Metasilicate Solutions in Alkaline Medium Using Nonionic Surfactants

2003 ◽  
Vol 68 (10) ◽  
pp. 2019-2031 ◽  
Author(s):  
Markéta Zukalová ◽  
Jiří Rathouský ◽  
Arnošt Zukal
Keyword(s):  
Mesoporous Silica ◽  
Ethylene Oxide ◽  
Sodium Metasilicate ◽  
Spherical Particles ◽  
Structure Directing Agent ◽  
Inorganic Species ◽  
Poly Ethylene Oxide ◽  
Acidic Conditions ◽  
Poly Ethylene ◽  
Hydrolysis Of

A new procedure has been developed, which is based on homogeneous precipitation of organized mesoporous silica from an aqueous solution of sodium metasilicate and a nonionic poly(ethylene oxide) surfactant serving as a structure-directing agent. The decrease in pH, which induces the polycondensation of silica, is achieved by hydrolysis of ethyl acetate. Owing to the complexation of Na+ cations by poly(ethylene oxide) segments, assembling of the mesostructure appears to occur under electrostatic control by the S0Na+I- pathway, where S0 and I- are surfactant and inorganic species, respectively. As the complexation of Na+ cations causes extended conformation of poly(ethylene oxide) segments, the pore size and pore volume of organized mesoporous silica increase in comparison with materials prepared under neutral or acidic conditions. The assembling of particles can be fully separated from their solidification, which results in the formation of highly regular spherical particles of mesoporous silica.

THE CHEMISTRY OF ETHYLENE OXIDE: V. THE REACTION OF ETHYLENE OXIDE WITH HALIDE IONS IN NEUTRAL AND ACID SOLUTION

1952 ◽  
Vol 30 (3) ◽  
pp. 169-176 ◽  
Author(s):  
A. M. Eastham ◽  
G. A. Latremouille
Keyword(s):  
Aqueous Solution ◽  
Ethylene Oxide ◽  
Acid Solution ◽  
Activation Energies ◽  
Hydrogen Halide ◽  
Halide Ions ◽  
Neutral Aqueous Solution ◽  
Rate Of Hydrolysis ◽  
Acid Catalyzed ◽  
Hydrolysis Of

The rates of reaction of halide ions with ethylene oxide in neutral aqueous solution and the rate of hydrolysis of ethylene oxide in acid solution have been measured and the activation energies determined. From these data and from the ratio of glycol to chlorohydrin formed when ethylene oxide reacts with excess aqueous hydrogen halide, the rates of the acid-catalyzed addition of halide ions to ethylene oxide at 25 °C. have been estimated.

scholarly journals Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere

2020 ◽  
Vol 117 (52) ◽  
pp. 33011-33016
Author(s):  
Krystal T. Vasquez ◽  
John D. Crounse ◽  
Benjamin C. Schulze ◽  
Kelvin H. Bates ◽  
Alexander P. Teng ◽  
...  
Keyword(s):  
Transport Model ◽  
Deuterium Oxide ◽  
Ambient Air ◽  
Water Volume ◽  
Isomer Ratio ◽  
Atmospheric Measurements ◽  
Laboratory Findings ◽  
Loss Process ◽  
Isomer Distribution ◽  
Hydrolysis Of

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry’s law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions.

Aqueous Nonelectrolyte Solutions. Part IX. Enthalpies of Mixing of Water and Deuterium Oxide with Ethylene Oxide

1971 ◽  
Vol 49 (11) ◽  
pp. 1830-1840 ◽  
Author(s):  
D. N. Glew ◽  
Harry Watts
Keyword(s):  
Hydrogen Bonding ◽  
Ethylene Oxide ◽  
Composition Range ◽  
Deuterium Oxide ◽  
Enthalpy Of Mixing ◽  
Water Systems ◽  
Oxide System ◽  
Water Proton ◽  
Oxide Systems ◽  
Enthalpies Of Mixing

Calorimetric enthalpies of mixing have been measured over the whole composition range for the water – ethylene oxide system at 10.75 and 20.00 °C and for the deuterium oxide – ethylene oxide system at 13.45 and 20.00 °C. Less extensive measurements have been made for dilute ethylene oxide solutions in water at 0.6 °C and in deuterium oxide at 4.1 and 7.3 °C. The experimental S-shaped, enthalpy of mixing – composition curves are interpreted in terms of solution hydrogen bonding changes, with particular reference to the hydrogen bonding of water. At low ethylene oxide mole fractions the deuterium oxide systems are more exothermal and at high ethylene oxide mole fractions more endothermal than the corresponding water systems. A good correlation is found between the enthalpy of mixing and the water proton magnetic resonance chemical shift for solutions with greater than 0.55 mol fraction of ethylene oxide.

The Hydrolysis of Disubstituted Alkyl Phosphorochloridates and N,N,N′,N′-Tetra-stibstituted Phosphorodiamidic Chlorides in Water and Deuterium Oxide: Heat Capacity of Activation and Kinetic Solvent Isotope Effects

1973 ◽  
Vol 51 (4) ◽  
pp. 597-603 ◽  
Author(s):  
E. C. F. Ko ◽  
R. E. Robertson
Keyword(s):  
Heat Capacity ◽  
Thermodynamic Parameters ◽  
Alkyl Group ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Potential Relationship ◽  
Mechanism Of Reaction ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The pseudo-thermodynamic parameters, ΔH≠, ΔS≠, and ΔCp≠ and the kinetic solvent isotope effects have been determined for the three alkyl-phosphorochloridates, where the alkyl group is ethylisopropyl and n-propyl; for tetra-methyl and tetra-ethyl phosphorodiamidic chlorides; the di-n-propyl and di-isopropyl analog, the di(isopropylmethylcarbinyl)phosphorochloridate and the tetra-ethylthiophosphorodiamidic chloride. These compounds have a potential relationship to compounds used as insecticides and as polymers. The mechanism of reaction is discussed on the basis of these data.

Solvent isotope effects in the oxidation of dipeptides by aqueous chlorine

1999 ◽  
Vol 77 (5-6) ◽  
pp. 997-1004 ◽  
Author(s):  
X L Armesto ◽  
M Canle L. ◽  
V García ◽  
J A Santaballa
Keyword(s):  
Isotope Effect ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Second Step ◽  
Solvent Isotope Effect ◽  
General Base ◽  
Peptide Oxidation ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

A kinetic study of the mechanism of oxidation of Ala-Gly and Pro-Gly by aqueous chlorine has been carried out. Among other experimental facts, the deuterium solvent isotope effects were used to clarify the mechanisms involved. In a first stage, N-chlorination takes place, and then the (N-Cl)-dipeptide decomposes through two possible mechanisms, depending on the acidity of the medium. The initial chlorination step shows a small isotope effect. In alkaline medium, two consecutive processes take place: first, the general base-catalyzed formation of an azomethine (β ca. 0.27), which has an inverse deuterium solvent isotope effect (kOH-/kOD- ~ 0.8). In a second step, the hydrolysis of the azomethine intermediate takes place, which is also general base-catalyzed, without deuterium solvent isotope effect, the corresponding uncatalyzed process having a normal deuterium solvent isotope effect (kH2O/kD2O ~ 2). In acid medium, the (N-Cl)-dipeptide undergoes disproportionation to a (N,N)-di-Cl-dipeptide, the very fast decomposition of the latter in deuterium oxide preventing a reliable estimation of the solvent isotope effect.Key words: chlorination, deuterium isotope effects, fractionation factors, peptide oxidation, water treatment.

Sign in / Sign up

Export Citation Format

Share Document