THE RADIOLYSIS OF ETHANOL: IV. DEUTERATED ETHANOLS IN THE LIQUID AND GAS PHASES

1965 ◽  
Vol 43 (5) ◽  
pp. 1484-1492 ◽  
Author(s):  
J. J. J. Myron ◽  
G. R. Freeman

The value of G(–ethanol) in the vapor phase is nearly double that in the liquid phase. Part of the difference appears to be due to the recombination of radicals in liquid cages. Ethanol molecules, on the average, break into smaller fragments in the gas than in the liquid phase radiolysis. The isotopic compositions of the hydrogen produced from various deuterated ethanols are consistent with the suggestion that the reaction[Formula: see text]occurs to a significant extent in the liquid but not in the gas phase. This reaction probably involves the shift of a hydrogen atom along a hydrogen bond. The reaction[Formula: see text]does not occur to an appreciable extent in the liquid phase. In the liquid phase the relative contributions of the three different groups in the ethanol molecule to hydrogen production are in the order [Formula: see text] A similar trend occurs in the gas, although the contributions of the three groups are more nearly equal in this phase. Isotope effects, in the range kH/kD = 2.2–3.9 per bond, occur in the methane formation mechanism. The isotope effects are somewhat smaller in the liquid than in the vapor phase and somewhat smaller in the inhibited than in the uninhibited systems. A comparison of product distributions in the liquid and gas radiolyses of several compounds by γ-rays and by α-particles indicates that L.E.T. effects can also occur in the gas phase.

1982 ◽  
Vol 53 (5) ◽  
pp. 1116-1124 ◽  
Author(s):  
R. P. Cole ◽  
P. C. Sukanek ◽  
J. B. Wittenberg ◽  
B. A. Wittenberg

The effect of myoglobin on oxygen consumption and ATP production by isolated rat skeletal muscle mitochondria was studied under steady-state conditions of oxygen supply. A method is presented for the determination of steady-state oxygen consumption in the presence of oxygen-binding proteins. Oxygen consumed in suspensions of mitochondria was replenished continuously by transfer from a flowing gas phase. Liquid-phase oxygen pressure was measured with an oxygen electrode; the gas-phase oxygen concentration was held constant at a series of fixed values. Oxygen consumption was determined from the characteristic response time of the system and the difference in the steady-state gas- and liquid-phase oxygen concentrations. ATP production was determined from the generation of glucose 6-phosphate in the presence of hexokinase. During steady-state mitochondrial oxygen consumption, the oxygen pressure in the liquid phase is enhanced when myoglobin is present. Functional myoglobin present in the solution had no effect on the relation of mitochondrial respiration and ATP production to liquid-phase oxygen pressure. Myoglobin functions in this system to enhance the flux of oxygen into the myoglobin-containing phase. Myoglobin may function in a similar fashion in muscle by increasing oxygen flux into myocytes.


1965 ◽  
Vol 43 (6) ◽  
pp. 1714-1719 ◽  
Author(s):  
David L. Bunbury

The reaction of benzene and nitrogen dioxide to produce nitrobenzene has been studied in the liquid and gas phases, in the dark, and with irradiation by light of 439 mμ and of 366 mμ. The concentration of NO2 in the liquid was varied from 0.08 to 1.6 moles/1 and in the gas from 0.0035 to 0.053 moles/1. No nitrobenzene was produced under any conditions in the liquid phase. Nitrobenzene is produced in the gas phase at high NO2 concentrations with irradiation by 366 mμ light. The quantum yield is 0.2. At 439 mμ the quantum yield is not more than 0.02. There is a very small dark reaction. As the concentration of NO2 in the gas is reduced the yield of nitrobenzene falls off very rapidly and is zero at the lowest concentration used, both in dark and light.


2003 ◽  
Vol 3 (5) ◽  
pp. 1509-1522 ◽  
Author(s):  
K. Sellegri ◽  
P. Laj ◽  
A. Marinoni ◽  
R. Dupuy ◽  
M. Legrand ◽  
...  

Abstract. Chemical reactions of dissolved gases in the liquid phase play a key role in atmospheric processes both in the formation of secondary atmospheric compounds and their wet removal rate but also in the regulation of the oxidizing capacity of the troposphere. The behavior of gaseous species and their chemical transformation in clouds are difficult to observe experimentally given the complex nature of clouds. During a winter field campaign at the summit of the Puy de Dôme (central France, 1465 m a.s.l), we have deployed an experimental set-up to provide a quantification of phase partitioning of both organic (CH3COOH, HCOOH, H2C2O4) and inorganic (NH3, HNO3, SO2, HCl) species in clouds. We found that nitric and hydrochloric acids can be considered close to Henry's law equilibrium, within analytical uncertainty and instrumental errors. On another hand, for NH3 and carboxylic acids, dissolution of material from the gas phase is kinetically limited and never reaches the equilibrium predicted by thermodynamics, resulting in significant sub-saturation of the liquid phase. On the contrary, SIV is supersaturated in the liquid phase, in addition to the presence of significant aerosol-derived SVI transferred through nucleation scavenging. Upon droplet evaporation, a significant part of most species, including SIV, tends to efficiently return back into the gas phase. Overall, gas contribution to the droplet solute concentration ranges from at least 48.5 to 98% depending on the chemical species. This is particularly important considering that aerosol scavenging efficiencies are often calculated assuming a negligible gas-phase contribution to the solute concentration. Our study emphasizes the need to account for the in-cloud interaction between particles and gases to provide an adequate modeling of multiphase chemistry systems and its impact on the atmospheric aerosol and gas phases.


1977 ◽  
Vol 30 (11) ◽  
pp. 2371 ◽  
Author(s):  
DV Fenby

Equilibrium constants for a number of water-alcohol deuterium exchange reactions in the gas phase are calculated from harmonic frequencies of CH3OH, CH3OD, CD3OH and CD3OD obtained from recent infrared studies. These are combined with vapour-pressure isotope effects to give equilibrium constants for the same reactions in the liquid phase. Calculated equilibrium constants agree well with most published experimental values.


2018 ◽  
Vol 240 ◽  
pp. 01034
Author(s):  
Zdzisław Salamonowicz ◽  
Radosław Makowski

During gas-phase release from the tank containing liquefied gas, the phenomenon of boiling, heat transfer from moist air to the tank, heat exchange between shell, liquid, and vapor, and mass loss can be observed. The aim of this paper is modelling the thermal response of the tank containing liquefied gas during jet emission of the vapor phase. The model takes into account heat exchange between air, tank’s shell, liquid phase, vapor phase and mass balance. The proposed model predicts: pressure inside the tank, tank’s shell temperature in part with liquid and vapor, the temperature of the liquid phase and vapor phase, and mass loss from the tank. The results of the theoretical model were compared with experimental results. An experiment based on the typical home container for LPG, containing 10 kg of propane (27 dm3 volume) was conducted. In general, the proposed model predicts well the changes in measured parameters temperatures and pressure - during vapor phase emission from a tank containing liquefied gas.


OENO One ◽  
2006 ◽  
Vol 40 (1) ◽  
pp. 35 ◽  
Author(s):  
Jean-Claude Vidal ◽  
Michel Moutounet

<p style="text-align: justify;">The assaying of oxygen in the headspace of a bottle combined with that of dissolved oxygen in the wine makes it possible to obtain the total oxygen per bottle. The first analyses performed at bottling show that 0.38 to 3.58 mg oxygen per bottle is trapped in the headspace. Operating conditions account for these substantial variations. Monitoring the oxygen contents in the liquid and gas phases of three batches of wine over a period of several months and the analysis of old bottles show that the headspace functions as an oxygen reserve for the wine, that is to say that as the wine uses oxygen, there is passage of the gas from the headspace to the wine. This is related to a movement towards a balance between the two phases as the partial pressure of oxygen in the gas phase is always greater than that of the liquid phase. Finally, this gas exchange kinetics within the bottle outweighs the kinetics of penetration of the bottle by oxygen in the external atmosphere, at least while the total oxygen trapped at bottling has not been used up.</p>


2017 ◽  
Author(s):  
Robson de Farias

<p>In the present work, a computational study is performed in order to clarify the possible magnetic nature of gold. For such purpose, gas phase Au<sub>2</sub> (zero charge) is modelled, in order to calculate its gas phase formation enthalpy. The calculated values were compared with the experimental value obtained by means of Knudsen effusion mass spectrometric studies [5]. Based on the obtained formation enthalpy values for Au<sub>2</sub>, the compound with two unpaired electrons is the most probable one. The calculated ionization energy of modelled Au<sub>2</sub> with two unpaired electrons is 8.94 eV and with zero unpaired electrons, 11.42 eV. The difference (11.42-8.94 = 2.48 eV = 239.29 kJmol<sup>-1</sup>), is in very good agreement with the experimental value of 226.2 ± 0.5 kJmol<sup>-1</sup> to the Au-Au bond<sup>7</sup>. So, as expected, in the specie with none unpaired electrons, the two 6s<sup>1</sup> (one of each gold atom) are paired, forming a chemical bond with bond order 1. On the other hand, in Au<sub>2</sub> with two unpaired electrons, the s-d hybridization prevails, because the relativistic contributions. A molecular orbital energy diagram for gas phase Au<sub>2</sub> is proposed, explaining its paramagnetism (and, by extension, the paramagnetism of gold clusters and nanoparticles).</p>


1991 ◽  
Vol 24 (7) ◽  
pp. 277-284 ◽  
Author(s):  
E. Gomólka ◽  
B. Gomólka

Whenever possible, neutralization of alkaline wastewater should involve low-cost acid. It is conventional to make use of carbonic acid produced via the reaction of carbon dioxide (contained in flue gases) with water according to the following equation: Carbon dioxide content in the flue gas stream varies from 10% to 15%. The flue gas stream may either be passed to the wastewater contained in the recarbonizers, or. enter the scrubbers (which are continually sprayed with wastewater) from the bottom in oountercurrent. The reactors, in which recarbonation occurs, have the ability to expand the contact surface between gaseous and liquid phase. This can be achieved by gas phase dispersion in the liquid phase (bubbling), by liquid phase dispersion in the gas phase (spraying), or by bubbling and spraying, and mixing. These concurrent operations are carried out during motion of the disk aerator (which is a patent claim). The authors describe the functioning of the disk aerator, the composition of the wastewater produced during wet gasification of carbide, the chemistry of recarbonation and decarbonation, and the concept of applying the disk aerator so as to make the wastewater fit for reuse (after suitable neutralization) as feeding water in acetylene generators.


1999 ◽  
Vol 39 (4) ◽  
pp. 85-92 ◽  
Author(s):  
J. Behrendt

A mathematical model for nitrification in an aerated fixed bed reactor has been developed. This model is based on material balances in the bulk liquid, gas phase and in the biofilm area. The fixed bed is divided into a number of cells according to the reduced remixing behaviour. A fixed bed cell consists of 4 compartments: the support, the gas phase, the bulk liquid phase and the stagnant volume containing the biofilm. In the stagnant volume the biological transmutation of the ammonia is located. The transport phenomena are modelled with mass transfer formulations so that the balances could be formulated as an initial value problem. The results of the simulation and experiments are compared.


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