Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine-Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO2 in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO3- is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO2 is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO2 and O-2 in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O-2, Cu(II) and HSO3-. This suggests a first-order termination of the free radicals of bisulfite ions.

Co-2-Ions In A Low-Pressure Glow-Discharge Of Carbon-Dioxide

$CO_2^{-}$ ions have been detected in the gas phase and measured by a mass spectrometer with a flight time of 30 µs in the positive column of carbondioxide glow discharge.

The carbon dioxide hydration activity of the sulfonamide-resistant carbonic anhydrase from the liver of male rat: pH independence of the steady-state kinetics

The steady-state kinetic constants for the catalysis of CO2 hydration by the sulfonamide-resistant and testosterone-induced carbonic anhydrase from the liver of the male rat has been determined by stopped-flow spectrophotometry. The turnover number was 2.6 ± 0.6 × 103 s− at 25 °C, and was invariant with pH ranging from 6.2 to 8.2 within experimental error. The Km at 25 °C was 5 ± 1 mImage , and was also pH independent. These data are in quantitative agreement with earlier findings of pH-independent CO2 hydration activity for the mammalian skeletal muscle carbonic anhydrase isozyme III. The turnover numbers for higher-activity isozymes I and II are strongly pH dependent in this pH range. Thus, the kinetic status of the male rat liver enzyme is that of carbonic anhydrase III. This finding is consistent with preliminary structural and immunologic data from other laboratories.

Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0)

Increasing concentrations of atmospheric CO2 decrease stomatal conductance of plants and thus suppress canopy transpiration. The climate response to this CO2-physiological forcing is investigated using the Community Atmosphere Model version 3.1 coupled to Community Land Model version 3.0. In response to the physiological effect of doubling CO2, simulations show a decrease in canopy transpiration of 8%, a mean warming of 0.1K over the land surface, and negligible changes in the hydrological cycle. These climate responses are much smaller than what were found in previous modeling studies. This is largely a result of unrealistic partitioning of evapotranspiration in our model control simulation with a greatly underestimated contribution from canopy transpiration and overestimated contributions from canopy and soil evaporation. This study highlights the importance of a realistic simulation of the hydrological cycle, especially the individual components of evapotranspiration, in reducing the uncertainty in our estimation of climatic response to CO2-physiological forcing. Citation: Cao, L., G. Bala, K. Caldeira, R. Nemani, and G.Ban-Weiss (2009), Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0).

Insoluble anode of porous lead dioxide for electrosynthesis: preparation and characterization

Preparation of a novel type of titanium-substrate lead dioxide anode with enhanced electrocatalytic activity for electrosynthesis is described. It has been demonstrated that in the presence of a suitable surfactant in the coating solution, an adherent and mainly tetragonal form of lead dioxide is deposited on a platinized titanium surface such that the solution side of the coating is porous while the substrate side is compact. By an analysis of anodic charging curves and steady-state Tafel plots with such porous electrodes in contact with sodium sulphate solution, it has been proved that the electrochemically active area of these anodes is higher by more than an order of magnitude when compared to the area of conventional titanium-substrate lead dioxide anodes. The electrocatalytic activity is also thereby enhanced to a significant degree.

Kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on lead dioxide electrodes

The kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on titanium-substrate lead dioxide electrodes have been investigated experimentally and theoretically. It has been demonstrated that the ionic strength of the solution has a marked effect on the rate of perchlorate formation, whereas the pH of the solution does not influence the reaction rate. Experimental data have also been obtained on the dependence of the reaction rate on the concentration of chlorate ion in the solution at constant ionic strength. With these data, diagnostic kinetic criteria have been deduced and compared with corresponding quantities predicted for various possible mechanisms including double layer effects on electrode kinetics. It has thus been shown that the most probable mechanisms for anodic chlorate oxidation on lead dioxide anodes involve the discharge of a water molecule in a one-electron transfer step to give an adsorbed hydroxyl radical as the rate-determining step for the overall reaction.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

A model for doped-oxide-source diffusion with a chemical reaction at the silicon-silicon dioxide interface

A mathematical model for doped-oxide-source diffusion is proposed. In this model the concept of segregation of impurity at the silicon-silicon dioxide is used and also a constant of “rate limitation” is introduced through a chemical reaction at the interface.

Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate

Thermal decomposition of powdered ammonium perchlorate, catalysed by manganese dioxide (MnO2), has been studied in the low concentration ranges of the catalyst. MnO2 sensitises the thermal decomposition of ammonium perchlorate. The activation energy estimations of catalysed ammonium perchlorate show that the value is about 30 kcal/mol throughout the low and the high temperature regions whereas uncatalysed ammonium perchlorate gives two activation energies, 20 kcal/mol in the low temperature region (280-320°C) and 60 kcal/mol in the higher temperature region (350-390°C). This behaviour has been explained on the basis of an electron transfer process. The effectiveness of MnO2 in the thermal decomposition further increases on pre-heating the sample at 50°C for two weeks; manganese ions enter the ammonium perchlorate lattice during the process of pre-heating.

Solubilities of palmitic and stearic fatty acids in supercritical carbon dioxide

The solubilities of two fatty acids, namely hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) in supercritical carbon dioxide (SCCO2), were determined at T = (328 and 338) K from 12.8 MPa to 22.6 MPa. Three models, namely a thermodynamic model based on the Peng-Robinson equation of state with Kwak and Mansoori mixing rules, a model based on dilute solution theory proposed by Mendez-Santiago and Teja and a new reformulated Chrastil equation model, were used to correlate the solubilities. In all the models, the correlation constants are temperature independent. All the models successfully correlated the experimental results for the solubilities of hexadecanoic acid within 3%.

Abatement of fluoride from water using manganese dioxide-coated activated alumina

Batch adsorption of fluoride onto manganese dioxide-coated activated alumina (MCAA) has been studied. Adsorption experiments were carried out at various pH (3–9), time interval (0–6 h), adsorbent dose (1–16 g/l), initial fluoride concentration (1–25 mg/l) and in the presence of different anions. Adsorption isotherms have been modeled using Freundlich, Langmuir and Dubinin–Raduskevich isotherms and adsorption followed Langmuir isotherm model. Kinetic studies revealed that the adsorption followed second-order rate kinetics. MCAA could remove fluoride effectively (up to 0.2 mg/l) at pH 7 in 3 h with 8 g/l adsorbent dose when 10 mg/l of fluoride was present in 50 ml of water. In the presence of other anions, the adsorption of fluoride was retared. The mechanism of fluoride uptake by MCAA is due to physical adsorption as well as through intraparticle diffusion which was confirmed by kinetics, Dubinin–Raduskevich isotherm, zeta-potential measurements and mapping studies of energy-dispersive analysis of X-ray.

Solubility of n-(4-Ethoxyphenyl)ethanamide in Supercritical Carbon Dioxide

The solubility of a drug, n-(4-ethoxyphenyl)ethanamide (phenacetin), in supercritical carbon dioxide was determined by a Saturation method at (308, 318, and 328) K from (9 to 19) MPa. The Solubilities in mole fraction of n-(4-ethoxyphenyl)ethanamide in supercritical carbon dioxide were in the range of 1.29.10(-5) to 2.88.10(-5), 1.13.10(-5) to 3.65.10(-5), and 0.91.10(-5) to 4.28.10(-5) at (308, 3 18, and 328) K, respectively. The solubility data were correlated with the Peng-Robinson equation of state models and the Mendez-Santiago and Teja model.

New empirical expressions to correlate solubilities of solids in supercritical carbon dioxide

Supercritical processes are gaining importance in the last few years in the food, environmental and pharmaceutical product processing. The design of any supercritical process needs accurate experimental data on solubilities of solids in the supercritical fluids (SCFs). The empirical equations are quite successful in correlating the solubilities of solid compounds in SCF both in the presence and absence of cosolvents. In this work, existing solvate complex models are discussed and a new set of empirical equations is proposed. These equations correlate the solubilities of solids in supercritical carbon dioxide (both in the presence and absence of cosolvents) as a function of temperature, density of supercritical carbon dioxide and the mole fraction of cosolvent. The accuracy of the proposed models was evaluated by correlating 15 binary and 18 ternary systems. The proposed models provided the best overall correlations. (C) 2009 Elsevier BA/. All rights reserved.

Effect of Chain Length of Alcohol on the Lipase-Catalyzed Esterification of Propionic Acid in Supercritical Carbon Dioxide

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.