Synthesis and kinetics of decomposition of some novel S-nitrosothiols

1999 ◽  
Vol 77 (5-6) ◽  
pp. 550-556 ◽  
Author(s):  
Andrew P Munro ◽  
D Lyn H. Williams
Keyword(s):  
Nitric Oxide ◽  
Room Temperature ◽  
Alternative Pathway ◽  
Copper Catalysis ◽  
Induction Periods ◽  
Kinetics Of Decomposition ◽  
Initial Generation ◽  
Kinetics Of ◽  
Reaction Schemes

TheS-nitrosothiols 2-acetamido-2-deoxy-S-nitroso-1-thio-β-D-glucopyranose 3,4,6-triacetate (GPSNO) and S-nitroso-N-carbamyl-D,L-penicillamine (SNCP) were synthesized by S-nitrosation of the corresponding thiols, isolated, and fully characterized. The nitrosothiol (TGSNO) from 1-thioglycerol was obtained as a red gelatinous liquid, which decomposed rapidly at room temperature and so was not characterized. The kinetics of decomposition of GPSNO showed that there is a surprisingly large thermal pathway overlaid with a Cu2+/RS- catalyzed reaction. The results strongly suggest that the product disulfide complexes Cu2+ (for which there is some spectral evidence), leading to incomplete conversion by that route. Ascorbate also acts as a Cu2+ reductant. Another S-nitroso sugar, S-nitroso-1-thio-β-D-glucose (SNTG), behaved very similarly from solutions generated and used in situ. The decomposition of TGSNO shows induction periods suggesting that slow initial generation of Cu+ (the true catalyst) is taking place. There appears to be also a significant alternative pathway (analogous to that found for GPSNO), where the rate appears to be independent of [Cu2+], but very unusually this pathway is effectively halted by addition of EDTA either at the start of the reaction or at a later time. Reaction schemes are put forward to account for these unusual reaction characteristics.Key words: S-nitrosothiols, nitric oxide, ascorbate, copper catalysis.

In situ high temperature X-ray diffraction study of the kinetics of phase separation in the uranium-plutonium mixed oxide (U0.55Pu0.45)O2-x

2014 ◽  
Vol 1645 ◽  
Author(s):  
Romain VAUCHY ◽  
Renaud.C. BELIN ◽  
Anne-Charlotte ROBISSON ◽  
Fiqiri HODAJ
Keyword(s):  
Phase Separation ◽  
Room Temperature ◽  
Mixed Oxides ◽  
Oxygen Stoichiometry ◽  
X Ray Diffraction ◽  
Fundamental Interest ◽  
X Ray ◽  
Uranium Plutonium ◽  
Kinetics Of

ABSTRACTUranium-plutonium mixed oxides incorporating high amounts of plutonium are considered for future nuclear reactors. For plutonium content higher than 20%, a phase separation occurs, depending on the temperature and on the oxygen stoichiometry. This phase separation phenomenon is still not precisely described, especially at high plutonium content. Here, using an original in situ fast X-ray diffraction device dedicated to radioactive materials, we evidenced a phase separation occurring during rapid cooling from 1773 K to room temperature at the rate of 0.05 and 2 K per second for a (U0.55Pu0.45)O2-x compound under a reducing atmosphere. The results show that the cooling rate does not impact the lattice parameters of the obtained phases at room temperature but their fraction. In addition to their obvious fundamental interest, these results are of utmost importance in the prospect of using uranium-plutonium mixed oxides with high plutonium content as nuclear fuels.

THE INFRARED SPECTRUM AND THERMAL DECOMPOSITION OF HYDRAZINE PERCHLORATE HEMIHYDRATE

1966 ◽  
Vol 44 (20) ◽  
pp. 2435-2443 ◽  
Author(s):  
P. W. M. Jacobs ◽  
A. Russell-Jones
Keyword(s):  
Infrared Spectrum ◽  
Reaction Mechanisms ◽  
Low Temperatures ◽  
Room Temperature ◽  
Kcal Mole ◽  
Absorption Bands ◽  
Kinetics Of Decomposition ◽  
Salt Melts ◽  
Chemical Equation ◽  
Kinetics Of

The infrared spectrum of hydrazine perchlorate hemihydrate (HPH) has been determined and an assignment of the absorption bands made. Invacuo, HPH will partially dehydrate even at room temperature; when heated the remainder of the half-mole of water is lost at 61 °C. The dehydrated salt melts at 138 °C and decomposition ensues. The kinetics of decomposition may be followed in the temperature range 180–280 °C. The activation energy is 36.3 kcal/mole. At low temperatures the decomposition is represented by the chemical equation[Formula: see text]but when the temperature is high enough the rate of decomposition of the ammonium perchlorate formed becomes appreciable also. Possible reaction mechanisms are discussed.

Kinetics of Decomposition of Nitric Oxide

1953 ◽  
Vol 21 (4) ◽  
pp. 751-751 ◽  
Author(s):  
Frederick Kaufman ◽  
John R. Kelso
Keyword(s):  
Nitric Oxide ◽  
Kinetics Of Decomposition ◽  
Kinetics Of

Hydrogen-Induced Phase Separation of Palladium-Rhodium Alloys Using an Environmental Cell TEM

1997 ◽  
Vol 3 (S2) ◽  
pp. 591-592
Author(s):  
D.F. Teter ◽  
R.D. Field ◽  
D.J. Thoma
Keyword(s):  
Phase Separation ◽  
Hydrogen Absorption ◽  
Melt Spinning ◽  
Room Temperature ◽  
Annealing Treatment ◽  
Miscibility Gap ◽  
Environmental Cell ◽  
Cold Rolled ◽  
Kinetics Of

The palladium-rhodium system has been extensively studied for its hydrogen absorption characteristics. However, the phase diagram of the palladium-rhodium system has not been conclusively determined below 800 K. Shield and Williams have experimentally determined the incoherent miscibility gap in Pd-Rh alloys using electrical resistivity studies, however the coherent miscibility gap and spinodal have not been determined. Recently work by Noh and Flanagan has suggested that hydrogen enhances metal atom mobility and may increase the kinetics of phase separation in Pd-Rh alloys. Field and Thoma found that hydrogen causes a Pd-10%Rh alloy to decompose during an in situhydrogen charging experiment in an environmental cell TEM. According to the calculations by Gonis et al. of the miscibility gap for the palladium-rhodium system, the Pd-10%Rh alloy may be within the chemical spinodal at room temperature.In this work, two palladium-rhodium compositions were investigated. The first was a Pd-10 at.% Rh alloy produced by melt-spinning, and the second was a Pd-30at.%Rh alloy which had been arc-melted and cold rolled followed by an annealing treatment to homogenize the material. TEM specimens were prepared by punching 3 mm disks from the material.

Kinetics Of The Growth Of Copper Clusters On The Alumina (0001) Surface : Influence Of Surface Structure

1998 ◽  
Vol 524 ◽  
Author(s):  
M. Gautier-Soyek ◽  
S. Gota ◽  
L. Douillard ◽  
P. Le Fevre ◽  
H. Magnan ◽  
...  
Keyword(s):  
Surface Structure ◽  
Room Temperature ◽  
Deposition Time ◽  
Cluster Radius ◽  
Copper Clusters ◽  
The Mean ◽  
Reconstructed Surface ◽  
Kinetics Of ◽  
Diffusion Properties

ABSTRACTThe kinetics of the growth of copper clusters on the alumina (0001) surface was studied as a function of surface structure, using EXAFS at the Cu K edge. Equivalent Cu coverages ranging from 0.5 to 4 equivalent monolayers were deposited in situ, at room temperature, on alumina (0001) surfaces exhibiting the (1×1) or the reconstructed structure. The evolution of mean cluster size with deposition time was followed from the mean Cu coordination number in the clusters deduced from the EXAFS data. The increase of the mean cluster radius with deposition time is characteristic of a coalescence mechanism on both surfaces. The growth is quicker on the reconstructed surface, likely due to different surface diffusion properties of both surfaces.

Temperature Dependence of Nanoscale Friction Investigated with Thermal AFM Probes

2009 ◽  
Vol 1226 ◽  
Author(s):  
Christian Greiner ◽  
Jonathan R. Felts ◽  
Zhenting Dai ◽  
William P. King ◽  
Robert W. Carpick
Keyword(s):  
Room Temperature ◽  
Capillary Condensation ◽  
Constant Load ◽  
Native Oxide ◽  
Silicon Substrates ◽  
Ambient Atmosphere ◽  
Ambient Conditions ◽  
Nanoscale Friction ◽  
Kinetics Of

AbstractMeasurements of nanoscale friction between silicon AFM tips featuring an in-situ solid state heater and silicon substrates (both with native oxide) were performed. The temperature of the heater was varied between room temperature and approximately 650 °C. For these temperatures and the silicon substrate, the temperatures at the point of contact are estimated to range from room temperature to approximately 120±20 °C. Experiments were carried out in ambient atmosphere (˜30% relative humidity) and under dry nitrogen. Tests under constant load revealed that in the presence of ambient, friction increased with heater temperature whereas it did not change in dry nitrogen. For experiments carried out for different tip velocities (40 to 7800 nm/s), friction decreased with velocity in ambient and did not change in dry nitrogen. Both trends can be explained by thermally-assisted formation of capillary bridges between tip and substrate and the kinetics of capillary condensation under ambient conditions.

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