Gas-phase organic reactions at low pressures

2010 ◽  
Vol 105 (9) ◽  
pp. 245-253 ◽  
Author(s):  
Nico M. M. Nibbering
Author(s):  
M. A. Gallis ◽  
J. R. Torczynski ◽  
D. J. Rader ◽  
B. L. Bainbridge

Noncontinuum gas-phase heat transfer in two microscale geometries is investigated using two computational methods. The motivation is microscale thermal actuation produced by heating-induced expansion of a near-substrate microbeam in air. The first geometry involves a 1-μm microgap filled with gas and bounded by parallel solid slabs. The second geometry involves a heated I-shaped microbeam 2 μm from the adjacent substrate, with gas in between. Two computational methods are applied. The Navier-Stokes slip-jump (NSSJ) method uses continuum heat transfer in the gas, with temperature jumps at boundaries to treat noncontinuum effects. The Direct Simulation Monte Carlo (DSMC) method uses computational molecules to simulate noncontinuum gas behavior accurately. For the microgap, the heat-flux values from both methods are in good agreement for all pressures and accommodation coefficients. For the microbeam, there is comparably good agreement except for cases with low pressures and near-unity accommodation coefficients. The causes of this discrepancy are discussed.


Hydrogen peroxide has been obtained in appreciable concentrations when a flame of hydrogen and oxygen burning at pressures of 3 to 4 cm. mercury was directed against a surface cooled to —180° C ( c . 5 to 10%), and when an oxy-hydrogen mixture was exploded by the action of a spark, in glass or aluminium vessels c . 2 x 15 cm., cooled in liquid air, the products were shown to contain up to 30% hydrogen peroxide ( w / v ), depending on the conditions. The conditions controlling the formation of hydrogen peroxide in such explosions have been investigated more fully than was done by previous authors. It was found that as the overall gas pressure was decreased the yield of peroxide passed through a maximum value. The effects were also investigated of varying the dimensions of the vessels, the gas composition, the external temperature, and other factors. A series of experiments was carried out in order to ascertain whether the hydrogen peroxide was formed in the gas phase or only on the walls. In these experiments, the ultra-violet absorption spectrum of the explosion region was studied. It was found that a considerable quantity of hydrogen peroxide was present in the gas phase, even when the walls of the reaction tube were not cooled. The results are discussed in the light of modern views regarding the combination of hydrogen and oxygen. It would appear that the peroxide is formed by two mechanisms; one of these consists of recombination of hydroxyl radicals on the cold walls, the other involves the formation of an excited HO 2 radical, and its subsequent reaction with a hydrogen molecule to give a hydrogen atom and a molecule of excited hydrogen peroxide, which then decomposes unless it is stabilized and frozen on the walls. No other explanation has been found to account for all the observed facts, and at the same time not to contradict established mechanisms for the hydrogen oxygen reaction.


2013 ◽  
Vol 353 ◽  
pp. 1-6 ◽  
Author(s):  
Charles M. Nichols ◽  
Zhibo Yang ◽  
Veronica M. Bierbaum

1987 ◽  
Vol 101 ◽  
Author(s):  
D.W. Squire ◽  
C.S. Dulcey ◽  
M.C. Lin

ABSTRACTLaser ionization mass spectrometry has been used to study the deposition of gallium from trimethylgallium with and without AsH3. The apparent Arrhenius activation energy for the production of gas-phase methyl radicals from trimethylgallium is measured to be 28 ± 2 kcal/mol in the presence of AsH3, about the same value as measured in the absence of AsH3. At a substrate temperature of 1150 K where gallium desorption is substantial, addition of AsH3 is found to increase methyl radical yield but drastically decrease gallium atom desorption. A mechanism is presented to describe the deposition of GaAs at low pressures under single gas-surface collision conditions.


2021 ◽  
Author(s):  
Thomas Mikal-Evans ◽  
David Sing ◽  
Joanna Barstow ◽  
Tiffany Kataria ◽  
Jayesh Goyal ◽  
...  

Abstract The temperature profile of a planetary atmosphere is a key diagnostic of radiative and dynamical processes governing the absorption, redistribution, and emission of energy. Observations have revealed dayside stratospheres that either cool [1,2] or warm [3,4] with altitude for a small number of gas giant exoplanets, while others are consistent with constant temperatures [5,6,7,8]. Here we report spectroscopic phase curve measurements for the gas giant WASP-121b,[9] which constrain stratospheric temperatures throughout the diurnal cycle. Variations measured for a water vapor spectral feature reveal a temperature profile that transitions from warming with altitude on the dayside hemisphere to cooling with altitude on the nightside hemisphere. The data are well explained by models assuming chemical equilibrium, with water molecules thermally dissociating at low pressures on the dayside and recombining on the nightside [10,11]. Nightside temperatures are low enough for perovskite (CaTiO3) to condense, which could deplete titanium from the gas phase [12,13] and explain recent non-detections at the day-night terminator [14,15,16,17]. Nightside temperatures are also low enough for refractory species, such as magnesium, iron, and vanadium, to condense. Detections [16,17,18,19] of these metals at the day-night terminator suggest, however, that if they do form nightside clouds, cold trapping is not as effective at removing them from the upper atmosphere. Note: Numbered references have been entered into the "Manuscript Comment" box.


2021 ◽  
pp. 1-14
Author(s):  
Parisa Gholamirad ◽  
Morteza Rouhani

A computational study about the effect of BX3 (X = H, F, Cl and Br) interaction in C–H acidity enhancement of some aldehyde, ketone and imine molecules is performed by B3LYP/6- 311++G(d,p) method in gas phase. The boron derivatives of model molecules show more acidity in comparison with their pure forms. This acidity improvement is attributed to the effective interaction of the C = O/C = N group with the B atom of BX3. The acidity enhancement is according to the BBr3 >  BCl3 >  BF3 >  BH3 order which shows that boron compounds with electron withdrawing groups and especially BBr3 can be used as an effective and promising C–H activator in various organic reactions.


Author(s):  
H. E. Audier ◽  
J. Fossey ◽  
D. Leblanc ◽  
P. Mourgues ◽  
V. Troude

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