Radiolysis of Ethyl Iodide in the Liquid Phase

1963 ◽  
Vol 2 (2) ◽  
Author(s):  
Ralph N. Schindler

SummaryTheEthane formation in pure irradiated ethyl iodide occurs to only 50% by reactions under steady state conditions. The residual ethane results from diffusion controlled reactions in spurs. "Hot" processes are found to be of minor importance. Ethylene and butane production occurs in the spurs exclusively. The upper limit for ethylene formation via unimolecular elimination is estimated to G < 0.9.

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.


Processes ◽  
2020 ◽  
Vol 8 (3) ◽  
pp. 261 ◽  
Author(s):  
Alberto Boretti

Dual fuel engines using diesel and fuels that are gaseous at normal conditions are receiving increasing attention. They permit to achieve the same (or better) than diesel power density and efficiency, steady-state, and substantially similar transient performances. They also permit to deliver better than diesel engine-out emissions for CO2, as well as particulate matter, unburned hydrocarbons, and nitrous oxides. The adoption of injection in the liquid phase permits to further improve the power density as well as the fuel conversion efficiency. Here, a model is developed to study a high-pressure, 1600 bar, liquid phase injector for liquefied natural gas (LNG) in a high compression ratio, high boost engine. The engine features two direct injectors per cylinder, one for the diesel and one for the LNG. The engine also uses mechanically assisted turbocharging (super-turbocharging) to improve the steady-state and transient performances of the engine, decoupling the power supply at the turbine from the power demand at the compressor. Results of steady-state simulations show the ability of the engine to deliver top fuel conversion efficiency, above 48%, and high efficiencies, above 40% over the most part of the engine load and speed range. The novelty of this work is the opportunity to use very high pressure (1600 bar) LNG injection in a dual fuel diesel-LNG engine. It is shown that this high pressure permits to increase the flow rate per unit area; thus, permitting smaller and lighter injectors, of faster actuation, for enhanced injector-shaping capabilities. Without fully exploring the many opportunities to shape the heat release rate curve, simulations suggest two-point improvements in fuel conversion efficiency by increasing the injection pressure.


2016 ◽  
Vol 20 (12) ◽  
pp. 4867-4879 ◽  
Author(s):  
Roger Moussa ◽  
Jean-Paul Lhomme

Abstract. The Budyko functions relate the evaporation ratio E ∕ P (E is evaporation and P precipitation) to the aridity index Φ  =  Ep ∕ P (Ep is potential evaporation) and are valid on long timescales under steady-state conditions. A new physically based formulation (noted as Moussa–Lhomme, ML) is proposed to extend the Budyko framework under non-steady-state conditions taking into account the change in terrestrial water storage ΔS. The variation in storage amount ΔS is taken as negative when withdrawn from the area at stake and used for evaporation and positive otherwise, when removed from the precipitation and stored in the area. The ML formulation introduces a dimensionless parameter HE  =  −ΔS ∕ Ep and can be applied with any Budyko function. It represents a generic framework, easy to use at various time steps (year, season or month), with the only data required being Ep, P and ΔS. For the particular case where the Fu–Zhang equation is used, the ML formulation with ΔS  ≤  0 is similar to the analytical solution of Greve et al. (2016) in the standard Budyko space (Ep ∕ P, E ∕ P), a simple relationship existing between their respective parameters. The ML formulation is extended to the space [Ep ∕ (P − ΔS), E ∕ (P − ΔS)] and compared to the formulations of Chen et al. (2013) and Du et al. (2016). The ML (or Greve et al., 2016) feasible domain has a similar upper limit to that of Chen et al. (2013) and Du et al. (2016), but its lower boundary is different. Moreover, the domain of variation of Ep ∕ (P − ΔS) differs: for ΔS  ≤  0, it is bounded by an upper limit 1 ∕ HE in the ML formulation, while it is only bounded by a lower limit in Chen et al.'s (2013) and Du et al.'s (2016) formulations. The ML formulation can also be conducted using the dimensionless parameter HP = −ΔS ∕ P instead of HE, which yields another form of the equations.


2001 ◽  
Vol 4 (06) ◽  
pp. 477-482 ◽  
Author(s):  
Kewen Li ◽  
Roland N. Horne

Summary Significant mass transfer between the steam and water phases makes it difficult to measure steam/water capillary pressure using routine methods. Because of the difficulties, few experimental data are available. A formula was derived on the basis of the Kelvin equation to calculate steam/water capillary pressure. The water-phase temperatures and pressures measured with a steady-state flow method were used to perform the calculations. The preliminary results of both drainage and imbibition steam/water capillary pressure were obtained. It was confirmed that the lowering of vapor pressure was small, but the capillary pressure was significant for the system studied. This experimental observation is consistent with thermodynamic analysis. Introduction It has often been assumed in steam numerical simulators that steam/water flow in porous media can be represented as gas (air or nitrogen)/water flow. In recent years, attention has been paid to the measurements of steam/water relative permeability.1–6 Horne et al.2 found that there were significant differences between nitrogen/water and steam/water relative permeabilities. Accordingly, there may also be significant differences between nitrogen/water and steam/water capillary pressures. To compare the two, reliable experimental data for steam/water capillary pressure are required. However, there have been few direct measurements of steam/water capillary pressure from steam/water flow experiments. Less attention has been paid to the measurements of steam/water capillary pressure, even though capillary pressure is of equal significance to relative permeability and plays an important role in controlling fluid distributions and recoveries in petroleum and geothermal reservoirs. Tsypkin and Calore7 developed a mathematical model of steam/water phase transition. They found that steam/water capillary pressure could play a stabilizing role for the vaporization front, causing a sharp zone to develop. Urmeneta et al.8 also studied the role of capillary forces in fractured reservoirs and found that capillary pressure tended to keep the vapor phase in the fracture and the liquid phase in the matrix. Using the adsorption data of Horne et al.9 for rock samples from The Geysers geothermal field, Sta. Maria and Pingol10 inferred the values of steam/water capillary pressure. They found that the steam/water capillary pressure ranged from 0 to 86,000 psi. Persoff and Hulen11 also inferred the capillary pressure from adsorption data of The Geysers rock samples and found that the steam/water capillary pressure ranged from 0 to approximately 28,000 psi. The graywacke core samples used by Persoff and Hulen11 were similar to those used by Sta. Maria and Pingol.10 The porosity was approximately 2%, and the permeability was in the nanodarcy (nd) range. The adsorption/desorption tests that have been used to infer steam/water capillary pressure are static processes in which there is no steam/water flow. In actual petroleum and geothermal reservoirs, however, capillary pressure plays an important role while steam and water flow simultaneously through the rocks. Hence, the process governing an adsorption test may not represent the mechanisms under actual fluid-flow conditions in those reservoirs. The steam/water capillary pressures from adsorption data may or may not be the same as those measured with a dynamic method in which steam and water are flowing. Very strict sealing requirements must be achieved for long periods of time during the adsorption tests, which is very difficult, especially at high temperatures. These disadvantages may be overcome by using a steady-state flow method. The main purpose of this paper was to develop a method to calculate steam/water capillary pressure using data from the experiments of steady-state steam/water flow. An X-ray computerized tomography (CT) technique was used to measure the water saturation and its distribution in the core sample. The effect of temperature on CT values used to calculate the water saturations was studied experimentally. Method Capillary Pressure. Using the Kelvin equation, steam/water capillary pressure can be calculated from the experimental data of liquid-phase pressure, temperature, and related parameters. The procedure is described in this section. The relative pressure (pv/p0) is used to characterize the capillary condensation on curved surfaces. Kelvin established the relationship between the relative pressure and the curvature of the interface, along with other properties of the fluid and the substrate. In a circular capillary tube with a radius of r, the relative pressure can be calculated using the Kelvin equation as follows:Equation 1 where p0=the vapor pressure when the vapor/liquid interface is flat; pv=the vapor pressure in a capillary tube of radius r when the vapor/liquid interface is curved; s=the interfacial tension and ?=the contact angle measured through the liquid phase; R=the gas constant; T=the absolute temperature; Mw=the molecular weight of liquid; and ?w=the density of liquid. The Kelvin equation assumes that (1) all adsorption is caused only by capillary condensation, (2) adsorbate density is equal to bulk liquid density, and (3) the validity is unimpaired at low values of r. The capillary pressure, Pc, in a circular capillary tube is also determined by the interface curvature and fluid and substrate properties and can be calculated asEquation 2 Combining Eqs. 1 and 2,Equation 3 Capillary pressure is defined as the pressure difference between the nonwetting and the wetting phases and is expressed as follows:Equation 4


Fractals ◽  
1995 ◽  
Vol 03 (02) ◽  
pp. 251-267 ◽  
Author(s):  
T. GREGORY DEWEY

The effect of time-dependent diffusional rate constants on chemically-controlled reactions in solution is considered. A general mechanism is examined that consists of a two step process. First the reactants diffuse together to form an “encounter complex.” This is followed by the collapse of the complex to the final product. The first step is diffusion controlled and the second step is chemically controlled. For reactions in restricted geometries or on fractals the rate constants associated with the diffusive process will scale with time as t−h where h is a constant between 0 and 1. The chemical processes are assumed to have time-independent rate constants. For reactions in which the encounter complex achieves a steady state, the differential equations governing the time course of the reaction can be solved exactly. At short times, the concentration of the reactants decays exponentially, reflecting the time constant of the chemical processes. At longer times, the decreasing diffusive rate constants result in the process being diffusion controlled. A stretched exponential of the form, exp{−kt1−h}, is observed. Approximate solutions for the pre-steady state behavior of the system are also determined using a Liouville transformation and corresponding asymptotic expansions. The short time regime shows power law decays of reactants. These decays will depend both on the dimensionality of the system as well as on the value of the rate constants associated with individual steps in the mechanism. Conditions can exist where a transformation to logarithmic oscillations will occur. Using this theoretical foundation a model is developed to analyze the kinetics of hydrogen isotope exchange kinetics in proteins. The exchange reaction is assume to occur in the boundary volume of the protein. Using the predicted fractal dimension of this boundary volume, scaling exponents are calculated and used as an unadjusted parameter. Highly accurate fits to the experimental data are achieved and activation energies are obtained that reflect the energetics of isotope exchange. This approach allows chemical kinetic behavior to be predicted from X-ray structure information.


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