The Effects of Solvent and Oxygen Pressure on the Autoxidation of Benzoin Catalysed by Nickel Acetate

1979 ◽  
Vol 32 (2) ◽  
pp. 421 ◽  
Author(s):  
RP Chaplin ◽  
S Vorlow ◽  
MS Wainwright
Keyword(s):  
Free Radical ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Oxygen Pressure ◽  
Second Order ◽  
Nickel Acetate ◽  
Coordination Complex ◽  
First Order ◽  
First Order Kinetics

Kinetic results are reported for the autoxidation of benzoin, catalysed by nickel acetate in methanol and ethanol. The reaction in methanol is first order with respect to benzoin and the catalyst and is independent of the oxygen partial pressure. The reaction is non-free-radical and probably involves a coordination complex between the substrate and the catalyst. In ethanol the reaction is found to obey second-order reversible kinetics with respect to benzoin and first-order kinetics with respect to the catalyst. The oxidation is also at least 10 times faster in ethanol than in methanol at 303 K.

scholarly journals Kinetic Modelling of Biodegradability Data of Commercial Polymers Obtained under Aerobic Composting Conditions

Eng ◽  
2021 ◽  
Vol 2 (1) ◽  
pp. 54-68
Author(s):  
Ilenia Rossetti ◽  
Francesco Conte ◽  
Gianguido Ramis
Keyword(s):  
Kinetic Data ◽  
Kinetic Modelling ◽  
Kinetic Equations ◽  
Second Order ◽  
Aerobic Biodegradation ◽  
First Order ◽  
First Order Kinetics ◽  
Plastic Materials ◽  
Partial Degradation ◽  
Commercial Polymers

Methods to treat kinetic data for the biodegradation of different plastic materials are comparatively discussed. Different samples of commercial formulates were tested for aerobic biodegradation in compost, following the standard ISO14855. Starting from the raw data, the conversion vs. time entries were elaborated using relatively simple kinetic models, such as integrated kinetic equations of zero, first and second order, through the Wilkinson model, or using a Michaelis Menten approach, which was previously reported in the literature. The results were validated against the experimental data and allowed for computation of the time for half degradation of the substrate and, by extrapolation, estimation of the final biodegradation time for all the materials tested. In particular, the Michaelis Menten approach fails in describing all the reported kinetics as well the zeroth- and second-order kinetics. The biodegradation pattern of one sample was described in detail through a simple first-order kinetics. By contrast, other substrates followed a more complex pathway, with rapid partial degradation, subsequently slowing. Therefore, a more conservative kinetic interpolation was needed. The different possible patterns are discussed, with a guide to the application of the most suitable kinetic model.

Examples of the Practical Use of Non-Stoichiometric Compounds

1994 ◽  
Author(s):  
Koji Kosuge
Keyword(s):  
Solid State ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Oxygen Pressure ◽  
Closed System ◽  
Electromotive Force ◽  
Solid Electrolytes ◽  
Coulometric Titration ◽  
Preparation Methods ◽  
Basic Characteristics

In this chapter, we describe four kinds of non-stoichiometric compound, which are or will be in practical use, from the viewpoint of preparation methods or utility. As a first example, the solid electrolyte (ZrO2)0.85(CaO)0.15 is described, which are discussed in Sections 1.4.6–1.4.8 from the viewpoint of basic characteristics. The second example is the magnetic material Mn–Zn ferrite, for which the control of non-stoichiometry and the manufacturing process will be described. Then the metal hydrides or hydrogen absorbing alloys, which are one of the most promising materials for storing and transporting hydrogen in the solid state, are described, mainly focusing on the phase relation. Finally, we describe the relation between the control of composition and the growth of a single crystal of the semiconductive compound GaAs, which is expected to give electronic materials for 1C and LSI etc. Solid electrolytes, which show ionic conductivity in the solid state, are considered to be potential materials for practical use, some are already used as mentioned below. Solid electrolytes have characteristic functions, such as electromotive force, ion selective transmission, and ion omnipresence. Here we describe the practical use of calcia stabilized zirconia (CSZ), (ZrO2)0.85(CaO)0.15, the structure and basic properties of which are discussed in detail in Sections 1.4.5–1.4.8. The most simple practical application of CSZ is for the gauge of oxygen partial pressure, as mentioned in Sections 1.4.7 and 1.4.8. The oxygen partial pressure P2o2 in the closed system as shown in Fig. 3.1 can be measured, taking the air as the standard oxygen pressure P1o2. The electromotive force (EMF) of this concentration cell is expressed as . . . E = (RT/4F)ln(P1o2/ P2o2) . . . This principle is applied in the measurement of oxygen partial pressure in laboratory experiments and of the oxygen activity of slag in refineries. Based on the principle of coulometric titration (see Section 1.4.8), the oxygen partial pressure of a closed system can be kept constant by feedback of the EMF, in the oxygen pressure range 1 to 10−7 atm. By use of this closed system, investigations on redox reactions of metals and also enzyme reactions have been carried out.

Oxidation of Crude Oil in Porous Media

1968 ◽  
Vol 8 (02) ◽  
pp. 137-148 ◽  
Author(s):  
I.S. Bousaid ◽  
H.J. Ramey
Keyword(s):  
Oxygen Partial Pressure ◽  
Crude Oil ◽  
Partial Pressure ◽  
Reaction Kinetics ◽  
Oil Recovery ◽  
Carbon Concentration ◽  
Combustion Process ◽  
Order Reaction ◽  
First Order ◽  
Catalyst Pellets

Abstract Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsolidated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. Introduction The production of crude oil by underground combustion has been studied in the laboratory by many investigators. Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investigators have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on be reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and A accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al., studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. SPEJ P. 137ˆ

Single Crystal Growth of YBa2Cu4O8 and Y2Ba4Cu7O15 Under High Oxygen Pressure

1991 ◽  
Vol 251 ◽  
Author(s):  
T. Miyatake ◽  
T. Takata ◽  
K. Yamaguchi ◽  
K. Takamuku ◽  
N. Koshizuka ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Single Crystal ◽  
Single Crystals ◽  
Oxygen Pressure ◽  
Maximum Size ◽  
Single Crystal Growth ◽  
Mixed Gas ◽  
High Oxygen Pressure

ABSTRACTWe investigate the crystal growth of YBa2Cu4O8 (124) and Y2Ba4Cu7O15 (247) in Al2O3 crucibles at an oxygen partial pressure of 20MPa employing an O2- HIP apparatus in a mixed gas environment of Ar-20%O2. Various melts compositions, rich in Ba and Cu, are explored to optimize crystal growth of 124. Large 124 single crystals up to a size of 1×0.5×0.05mm3 are obtained from compositions with about 65˜67%CuO. 247 single crystals having a maximum size of 3×1.5×0.05mm3 are grown from the same composition of melts. 124 crystals exhibit superconductivity at 75K. 247 crystals show Tc of 20K.

scholarly journals Effect of Oxygen Pressure on the Initial Oxidation Behavior of Cu and Cu-Au Alloys

2011 ◽  
Vol 1318 ◽  
Author(s):  
Langli Luo ◽  
Yihong Kang ◽  
Zhenyu Liu ◽  
Judith C Yang ◽  
Guangwen Zhou
Keyword(s):  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Oxygen Pressure ◽  
Atomic Scale ◽  
Nucleation Theory ◽  
Nucleation Density ◽  
Atmospheric Conditions ◽  
Initial Oxidation ◽  
Effect Of Oxygen ◽  
Pure Cu

ABSTRACTA wide information gap exists between our present atomic-scale knowledge of metal oxidation derived from conventional ultrahigh vacuum (UHV) surface science experiments and the oxidation mechanisms obtained from the growth of bulk oxide thin films under technologically relevant realistic (or near-) atmospheric conditions. To bridge this pressure gap, we present an in-situ transmission electron microscopy (TEM) study of the initial oxidation stage of Cu(100) and Cu-Au(100) surfaces where the oxygen partial pressure varies from 5x10-4 to 150 Torr. For Cu(100), with increasing oxygen partial pressure (pO2), the nucleation density of the oxide islands increases and so does the growth rate of the oxide islands. As the pO2 continues to increase, a transition from epitaxial cube-on-cube Cu2O islands to randomly oriented oxide islands is observed. A kinetic model based on the classic heterogeneous nucleation theory is developed to explain the effect of oxygen partial pressure on the oxide orientation. It is shown that such a transition in the oxide nucleation orientation is related to the effect of oxygen pressure on the nucleation barrier and atom collision rate. The Cu-Au(111) alloy revealed the same oxygen pressure dependency of the oxide nucleation orientation as pure Cu oxidation.

scholarly journals Oxygen supply capacity in animals evolves to meet maximum demand at the current oxygen partial pressure regardless of size or temperature

2019 ◽  
Author(s):  
Brad A. Seibel ◽  
Curtis Deutsch
Keyword(s):  
Metabolic Rate ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Oxygen Pressure ◽  
Thermal Tolerance ◽  
Oxygen Supply ◽  
Cardiovascular Health ◽  
Hypoxia Tolerance ◽  
Aerobic Scope ◽  
Supply Capacity

AbstractPhysiological oxygen supply capacity is associated with athletic performance and cardiovascular health and is thought to cause hypometabolic scaling in diverse species. Environmental oxygen is widely believed to be limiting of metabolic rate and aerobic scope, setting thermal tolerance and body size limits with implications for species diversity and biogeography. Here we derive a quantifiable linkage between maximum and basal metabolic rate and their temperature, size and oxygen dependencies. We show that, regardless of size or temperature, the capacity for oxygen supply precisely matches the maximum evolved demand at the highest persistently available oxygen pressure which, for most species assessed, is the current atmospheric pressure. Any reduction in oxygen partial pressure from current values will result in a decrement in maximum metabolic performance. However, oxygen supply capacity does not constrain thermal tolerance and does not cause hypometabolic scaling. The critical oxygen pressure, typically viewed as an indicator of hypoxia tolerance, instead reflects adaptations for aerobic scope. This simple new relationship redefines many important physiological concepts and alters their ecological interpretation.One sentence summary: Metabolism is not oxygen limited

scholarly journals Stability of carotenoids toward UV-irradiation in hexane solution

2008 ◽  
Vol 73 (1) ◽  
pp. 15-27 ◽  
Author(s):  
Dragan Cvetkovic ◽  
Dejan Markovic
Keyword(s):  
Free Radical ◽  
Uv Irradiation ◽  
First Order ◽  
Chemical Structures ◽  
First Order Kinetics ◽  
Uv C ◽  
Hexane Solution

The stabilities of four selected carotenoids dissolved in hexane, two carotenes and two xanthophylls, toward UV-irradiation of three different ranges (UV-A, UV-B and UV-C) were studied in this work. The carotenoids underwent bleaching via a probable free radical mediated mechanism following first-order kinetics. The bleaching rates were highly dependent on the input of the involved photons and, although not consistently, on the chemical structures of the investigated compounds. For the two xanthophylls, a possible role of oxygen associated with their bleaching cannot be neglected.

The catalysis of the para -hydrogen conversion by the solid free radical αα -diphenyl- β -picryl hydrazyl

1953 ◽  
Vol 220 (1140) ◽  
pp. 77-90 ◽  
Keyword(s):  
Free Radical ◽  
Adsorbed Layer ◽  
Inhomogeneous Magnetic Field ◽  
Langmuir Adsorption ◽  
First Order ◽  
Heterogeneous Catalytic ◽  
Hydrogen Molecules ◽  
First Order Kinetics ◽  
Increasing Temperature ◽  
Kinetics Of

A detailed study of the kinetics of the heterogeneous catalytic ortho - para -hydrogen conversion on the solid free radical αα -diphenyl- β -picryl hydrazyl, shows that this conversion follows the usual first-order kinetics and that the rate is independent of pressure. Examination of the rate at 90, 190 and 290° K indicates that it decreases with increasing temperature. This type of behaviour has been observed for other paramagnetic heterogeneous conversions, and the ‘negative activation energy' has been assumed to indicate that the catalysis takes place in a physically adsorbed layer of hydrogen molecules. Some evidence that this is the true explanation of the phenomenon is shown by the results of studies of the adsorption of hydrogen on the free radical. Experiments carried out at 77 and 90° K indicate that hydrogen is physically adsorbed by the free radical to form a weakly sorbed layer which obeys the Langmuir adsorption isotherm for the case when the surface is only sparsely covered. A theoretical discussion is given for a heterogeneous conversion occurring during the collision of the hydrogen molecule with the catalyst surface both in the absence, and in the presence, of a physically adsorbed layer. It is shown that only the theory based on the latter model is in agreement with experimental results, and so it is concluded that in the present case the catalysis is due to the interaction between the hydrogen molecules in a physically adsorbed layer, and the inhomogeneous magnetic field at the surface of the catalyst, which enables the otherwise forbidden ortho - para transitions to take place.

Crystal growth of YBa2Cu3O7 by the SRL-CP method under low oxygen partial pressure atmosphere

1994 ◽  
Vol 9 (8) ◽  
pp. 1946-1951 ◽  
Author(s):  
M. Nakamura ◽  
Y. Yamada ◽  
Y. Shiohara
Keyword(s):  
Crystal Growth ◽  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Single Crystals ◽  
Oxygen Pressure ◽  
Crystal Surface ◽  
Nitrogen Atmosphere ◽  
Low Oxygen ◽  
Pure Nitrogen ◽  
Rich Liquid

Single crystals of YBa2Cu3O7−x (Y123) were grown by a modified top-seeded crystal pulling method using a BaO-CuO solution with the solid Y2BaCuO5 (Y211) as a solute in an yttria crucible [the so-called solute-rich liquid crystal pulling (SRL-CP) method] under 2% oxygen partial pressure atmosphere [P(O2) = 0.02 atm]. According to the pseudo-binary phase diagrams of Lee and Lee,1 the temperature of Y123 crystal growth was expected to be lower for 0.02 atm oxygen pressure than for 0.21 atm oxygen pressure. The single crystals grown under P(O2) = 0.02 atm and cooled under the same atmosphere after the separation of crystal from a solution had twins near the microcracks on the crystal surface. On the other hand, the single crystals grown under P(O2) = 0.02 atm and cooled under pure nitrogen atmosphere (6N) showed no twin structure. These results indicate that twins did not form during crystal growth but formed due to tetragonal-orthorhombic transition as a consequence of oxygenation at cooling under low oxygen partial pressure.

scholarly journals Application of Intelligent Monitoring of Percutaneous Partial Oxygen Pressure in Evaluating the Evolution of Scar Hyperplasia

2021 ◽  
Vol 2021 ◽  
pp. 1-6
Author(s):  
Wanle Qi ◽  
Mejia Zhuo ◽  
Yan Tian ◽  
Zhuoma Dawa ◽  
Junjie Bao ◽  
...  
Keyword(s):  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Oxygen Pressure ◽  
Hypertrophic Scar ◽  
Normal Skin ◽  
Scar Tissue ◽  
Partial Oxygen Pressure ◽  
Scar Maturation ◽  
Development And Evolution ◽  
Partial Oxygen

The study aimed to investigate the dynamic changes of percutaneous partial oxygen pressure during the development and evolution of a hypertrophic scar. Twenty cases of hypertrophic scar patients at different stages were selected. A percutaneous oxygen monitor was used to measure oxygen partial pressure in the scar and normal skin tissue at 14, 30, 60, and 90 days after surgery. The changes of oxygen partial pressure, tissue structure, HIF-1α, and VEGF expression in the scar tissue were observed, and the correlation was analyzed. In the scar maturation process, with the prolongation of time, the partial oxygen pressure in the tissue increased gradually. The expression intensity of HIF-1α and VEGF decreased gradually, HIF-1α was positively correlated with VEGF (r = 0.98, P < 0.01 ), there was a negative correlation between oxygen partial pressure and HIF-1 α expression (r = −0.92, P < 0.01 ), and it was negatively correlated with VEGF (r = −0.88, P < 0.01 ). TcPO2 measurement can be used to assess scar maturity; HIF-1 α and VEGF may play an essential role in regulating partial oxygen pressure in the scar tissue.

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