Dissolution of organic solvents from painted surfaces into water

2000 ◽  
Vol 78 (4) ◽  
pp. 464-473 ◽  
Author(s):  
J C Wren ◽  
D J Jobe ◽  
G G Sanipelli ◽  
J M Ball
Keyword(s):  
Organic Compounds ◽  
Organic Solvents ◽  
Nuclear Reactor ◽  
Dissolution Kinetics ◽  
Activation Energies ◽  
Dissolution Mechanism ◽  
Rate Determining Step ◽  
Organic Impurities ◽  
Accident Conditions ◽  
Reactor Accidents

The presence of volatile iodine in containment buildings is one of the major safety concerns in the potential event of nuclear reactor accidents. Organic impurities in containment water, originating from various painted structural surfaces and organic materials, could have a significant impact on iodine volatility following an accident. To determine the source and magnitude of organic impurities and their effects on time-dependent iodine volatility, the dissolution for organic constituents from paints used in reactor buildings has been studied under postulated accident conditions. The studies of the organic dissolution from carbon steel coupons coated with zinc-primed vinyl, epoxy-primed polyurethane or epoxy paints over the temperature range 25-90°C are reported. Relatively large activation energies were measured for the release of the principal organic compounds from painted surfaces, suggesting it is the release of the solvents from the paint matrix rather than their diffusion through the solution that is the rate determining step for the dissolution mechanism. The similarities in the values of activation energies for the dissolution of different organic compounds from the paints suggest the release rate is independent of the nature of the painted surface or the type of organic being released from the surface. These two observations indicate that it may be possible to write a generalized rate expression for the release of organic compounds from painted surfaces in containment following an accident. The possible implications of these results for predicting iodine volatility in containment are also discussed.Key words: dissolution kinetics, organic solvents, painted surfaces, reactor accidents.

Quantification of kinetic rate law parameters of uranium release from sodium autunite as a function of aqueous bicarbonate concentrations

2013 ◽  
Vol 10 (6) ◽  
pp. 475 ◽  
Author(s):  
Ravi Gudavalli ◽  
Yelena Katsenovich ◽  
Dawn Wellman ◽  
Leonel Lagos ◽  
Berrin Tansel
Keyword(s):  
Dissolution Kinetics ◽  
Fold Increase ◽  
Activation Energies ◽  
Complexing Agent ◽  
Dissolution Mechanism ◽  
Rate Law ◽  
Ph Conditions ◽  
Bicarbonate Solutions ◽  
Ph Range ◽  
Relationship Of

Environmental context Uranium is a key contaminant of concern because of its high persistence in the environment and toxicity to organisms. The bicarbonate ion is an important complexing agent for uranyl ions and one of the main variables affecting its dissolution. Results from this investigation provide rate law parameters for the dissolution kinetics of synthetic sodium autunite that can influence uranium mobility in the subsurface. Abstract Hydrogen carbonate (also known as bicarbonate) is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005–0.003M) over the pH range of 6–11 and temperatures of 5–60°C. Consistent with the results of previous investigations, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited a 370-fold increase relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate that the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As the pH increased from 6 to 11, the activation energy values were observed to decrease from 29.94 to 13.07kJmol–1. The calculated activation energies suggest a surface controlled dissolution mechanism.

scholarly journals Hydrogenation of alkynyl substituted aromatics over rhodium/silica

2021 ◽  
Author(s):  
Joseph W. Gregory ◽  
S. David Jackson
Keyword(s):  
Cascade Reactions ◽  
Activation Energies ◽  
Competitive Reaction ◽  
Fresh Catalyst ◽  
Hydrogen Flux ◽  
Rate Determining Step ◽  
Surface Hydrogen ◽  
Alkyne Hydrogenation ◽  
Competitive Hydrogenation ◽  
Styrene Hydrogenation

AbstractThe cascade reactions of phenylacetylene to ethylcyclohexane and 1-phenyl-1-propyne to propylcyclohexane were studied individually, under deuterium and competitively at 343 K and 3 barg pressure over a Rh/silica catalyst. Both systems gave similar activation energies for alkyne hydrogenation (56 ± 4 kJ mol−1 for phenylacetylene and 50 ± 4 kJ mol−1 for 1-phenyl-1-propyne). Over fresh catalyst the order of reactivity was styrene > phenylacetylene ≫ ethylbenzene. Whereas with the cascade hydrogenation starting with phenylacetylene, styrene hydrogenated much slower phenylacetylene even once all the phenylacetylene was hydrogenated. The activity of ethylbenzene was also reduced in the cascade reaction and after styrene hydrogenation. These reductions in rate were likely due to carbon laydown from phenylacetylene and styrene. Similar behavior was observed with the 1-phenyl-1-propyne cascade. Deuterium experiments revealed similar positive KIEs for phenylacetylene (2.6) and 1-phenyl-1-propyne (2.1). Ethylbenzene hydrogenation/deuteration gave a KIE of 1.6 obtained after styrene hydrogenation in contrast to the inverse KIE of 0.4 found with ethylbenzene hydrogenation/deuteration over a fresh catalyst, indicating a change in rate determining step. Competitive hydrogenation between phenylacetylene and styrene reduced the rate of phenylacetylene hydrogenation but increased selectivity to ethylbenzene suggesting a change in the flux of sub-surface hydrogen. In the competitive reaction between 1-phenyl-1-propyne and propylbenzene, the rate of hydrogenation of 1-phenyl-1-propyne was increased and the rate of alkene isomerization was decreased, likely due to an increase in the hydrogen flux for hydrogenation and a decrease in the hydrogen species active in methylstyrene isomerization.

Nuclear Power Plant Fires and Explosions: Part IV — Water Hammer Explosion Mechanisms

2017 ◽  
Author(s):  
Robert A. Leishear
Keyword(s):  
Nuclear Power ◽  
Power Plants ◽  
Nuclear Power Plants ◽  
Nuclear Reactor ◽  
Water Hammer ◽  
Compression Process ◽  
Flammable Gas ◽  
Piping Systems ◽  
Fukushima Daiichi ◽  
Accident Conditions

Water hammers, or fluid transients, compress flammable gasses to their autognition temperatures in piping systems to cause fires or explosions. While this statement may be true for many industrial systems, the focus of this research are reactor coolant water systems (RCW) in nuclear power plants, which generate flammable gasses during normal operations and during accident conditions, such as loss of coolant accidents (LOCA’s) or reactor meltdowns. When combustion occurs, the gas will either burn (deflagrate) or explode, depending on the system geometry and the quantity of the flammable gas and oxygen. If there is sufficient oxygen inside the pipe during the compression process, an explosion can ignite immediately. If there is insufficient oxygen to initiate combustion inside the pipe, the flammable gas can only ignite if released to air, an oxygen rich environment. This presentation considers the fundamentals of gas compression and causes of ignition in nuclear reactor systems. In addition to these ignition mechanisms, specific applications are briefly considered. Those applications include a hydrogen fire following the Three Mile Island meltdown, hydrogen explosions following Fukushima Daiichi explosions, and on-going fires and explosions in U.S nuclear power plants. Novel conclusions are presented here as follows. 1. A hydrogen fire was ignited by water hammer at Three Mile Island. 2. Hydrogen explosions were ignited by water hammer at Fukushima Daiichi. 3. Piping damages in U.S. commercial nuclear reactor systems have occurred since reactors were first built. These damages were not caused by water hammer alone, but were caused by water hammer compression of flammable hydrogen and resultant deflagration or detonation inside of the piping.

The reduction of I2 by H2O2 in aqueous solution

2001 ◽  
Vol 79 (3) ◽  
pp. 304-311 ◽  
Author(s):  
J M Ball ◽  
J B Hnatiw
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Nuclear Reactor ◽  
Ph Dependence ◽  
Radiolysis Product ◽  
Molecular Iodine ◽  
Water Radiolysis ◽  
Reactor Accident ◽  
Rate Law ◽  
Accident Conditions

The reduction of I2 by hydrogen peroxide, a primary water radiolysis product, has been identified as a key reaction that would influence iodine volatility in nuclear reactor accident conditions (1–3). Although there have been a number of studies of the reduction of I2, there exists a great degree of controversy regarding the intermediates involved, the effect of buffers, and the general rate law (1–9). Because the rates and the mechanism of this reaction are important in predicting the pH dependence of iodine behaviour in reactor containment building after a postulated reactor accident, we have undertaken a kinetic study of I2 reduction by H2O2 in aqueous solution over a pH range of 6–9. The experiments were performed using stopped-flow instrumentation and monitoring the decay of I–3 spectrophotometrically. The effects of buffer catalysis have been examined by comparison of kinetic data obtained in sodium barbital (5,5-diethylbarbituric acid), disodium citrate, and disodium hydrogen phosphate buffers. The effect of buffers, combined with the complex acid dependence of the rate law, explains many of the discrepancies reported in earlier literature.Key words: hydrogen peroxide, molecular iodine, kinetics, iodine volatility.

scholarly journals The initial dissolution rates of simulated UK Magnox–ThORP blend nuclear waste glass as a function of pH, temperature and waste loading

2015 ◽  
Vol 79 (6) ◽  
pp. 1529-1542 ◽  
Author(s):  
N. Cassingham ◽  
C.L. Corkhill ◽  
D.J. Backhouse ◽  
R.J. Hand ◽  
J.V. Ryan ◽  
...  
Keyword(s):  
Dissolution Kinetics ◽  
Intrinsic Rate ◽  
Waste Glass ◽  
High Level Waste ◽  
Dissolution Mechanism ◽  
Dissolution Rates ◽  
Forward Rates ◽  
Glass Dissolution ◽  
High Level ◽  
Kinetics Of

AbstractThe first comprehensive assessment of the dissolution kinetics of simulant Magnox–ThORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high-level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.

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