Kinetic Rate Law Research Articles

Kinetics of UV Irradiation Induced Chain Scission and Cross-Linking of Coumarin-Containing Polyester Ultrathin Films

Photoresponsive thin films are commonly encountered as high performance coatings as well as critical component, photoresists, for microelectronics manufacture. Despite intensive investigations into the dynamics of thin glassy polymer films, studies involving reactions of thin films have typically been limited by difficulties in decoupling segregation of reacting components or catalysts due to the interfaces. Here, thin films of coumarin polyesters overcome this limitation where the polyester undergoes predominately cross-linking upon irradiation at 350 nm, while chain scission occurs with exposure to 254 nm light. Spectroscopic ellipsometry is utilized to track these reactions as a function of exposure time to elucidate the associated reaction kinetics for films as thin as 15 nm. The cross-linking appears to follow a second order kinetic rate law, while oxidation of the coumarin that accompanies the chain scission and enables this reaction to be tracked spectroscopically appears to be a first order reaction in coumarin concentration. Because of the asymmetry in the coumarin diol monomer and the associated differences in local structure that result during formation of the polyester, two populations of coumarin are required to fit the reaction kinetics; 10–20% of the coumarin is significantly more reactive, but these groups appear to undergo chain scission/oxidation at both wavelengths. These reaction rate constants are nearly independent (within 1 order of magnitude) of film thickness down to 15 nm. There is maximum rate at a finite thickness for the 254 nm exposure, which we attribute to constructive interference of the UV radiation within the polymer film, rather than typical confinement effects; no thickness dependence in reaction rates is observed for the 350 nm exposure. The utilization of a single polymer with two distinct reactions enables unambiguous investigation of thickness effects on reactions.

Uranium Reduction by Shewanella oneidensis MR-1 as a Function of NaHCO3 Concentration: Surface Complexation Control of Reduction Kinetics

It is crucial to determine the controls on the kinetics of U(VI) bioreduction in order to understand and model the fate and mobility of U in groundwater systems and also to enhance the effectiveness of U bioremediation strategies. In this study, we measured the rate of U(VI) reduction by Shewanella oneidensis strain MR-1 as function of NaHCO3 concentration. The experiments demonstrate that increasing concentrations of NaHCO3 in the system lead to slower U(VI) reduction kinetics. The NaHCO3 concentration also strongly affects the speciation of U(VI) on the bacterial cell envelope. We used a thermodynamic surface complexation modeling approach to determine the speciation and concentration of U(VI) adsorbed onto the bacteria as a function of the NaHCO3 concentration in the experimental systems. We observed a strong positive correlation between the measured U(VI) reduction rates and the calculated total concentration of U(VI) surface complexes formed on the bacterial cell envelope. This positive correlation indicates that the speciation and concentration of U(VI) adsorbed on the bacterial cell envelope control the kinetics of U(VI) bioreduction under the experimental conditions. The results of this study serve as a basis for developing speciation-based kinetic rate laws for enzymatic reduction of U(VI) by bacteria.

Hydrophobicity and kinetic inspection of hydroxide ion attack on some chromen-2-one laser dyes in binary aqueous–methanol and aqueous–acetone mixtures: Initial state-transition state analysis

In the present study, reactivity base-catalyzed hydrolysis of 7-dimethylamino-4-methyl-2H-chromen-2-one (DMAC) and 7-diethylamino-4-methyl-2H-chromen-2-one (DEAC) in binary aqueous–methanol and aqueous–acetone mixtures was examined at 298K. Kinetic results, rate laws and reaction mechanisms were established. Moreover, the change in the activation energy barrier of the investigated compounds from water to water–methanol and water–acetone mixtures was estimated from the kinetic data. Base-catalyzed hydrolysis of (DMAC) and (DEAC) in aqueous–methanol and aqueous–acetone mixtures follows a rate law with kobs=k2[OH]. The decrease in the rate constants of (DMAC) and (DEAC) as the proportion of methanol and acetone is due to the destabilization of OH− ion. The solubilities of the studied compounds, DMAC and DEAC in water–methanol and water–acetone mixtures were established and their transfer chemical potentials were calculated. Solvent effect on reactivity trends of the investigated compounds has been analyzed into initial and transition state components by using the transfer chemical potentials of the reactants and the kinetic data of the studied compounds. The decrease in the observed rate constant values (kobs) of the base hydrolysis of DMAC and DEAC with increasing of methanol% or acetone% is dominated by the initial state (IS).

Kinetic modeling of laboratory CO2‐exposure experiments performed on whole rock reservoir samples

AbstractMineralogical and geochemical observations from laboratory CO2‐exposure experiments on reservoir rocks are compared with predictions from geochemical modeling that was performed using PHREEQC software. The Pitzer‐based Eq 3/6 thermodynamic database, provided by Quintessa Ltd., was applied. For kinetic modeling, a Lasaga‐type rate equation was implemented and different models were parameterized taking kinetic rate law parameters from literature. Based on previous modeling studies a modified inverse modeling approach is presented here. This comprises several different Fe‐proxies and improved statistical ranking preferences that were implemented in particular to better match modeled and measured concentrations of dissolved K+, Fe2+ and Al3+. Compared to the previous approach, the presented modeling results are in good (better) agreement with experimental data. Systematic discrepancies between modeling and observation still occur regarding K‐bearing mineral phases and corresponding K+ brine concentrations. Despite missing correlation between K+ and Cl− concentrations, potential reasons for these discrepancies may be increased K+ brine concentrations during the experiments due to dissolution of K‐rich salt(s), such as sylvite. Much better matches were generated for dissolved Fe2+ concentrations. Goethite mainly controls the chemical behavior of dissolved Fe2+ in kinetic simulations. Based on both the available equilibrium and kinetic modeling results, the ultimate fate of dissolved Al3+ and the analysis of Al‐bearing mineral phases potentially controlling dissolved Al3+ brine concentrations cannot be conclusively determined. The overall best ranked kinetic model comprises anhydrite, dolomite, goethite, K‐feldspar and kaolinite. Despite minor inconsistencies dissolved Fe2+, Al3+ and Si4+ were in particular much better reproduced by the best ranked kinetic models.

Chemical Sequence and Kinetics of Alkali–Silica Reaction Part II. A Thermodynamic Model

This manuscript describes development of a thermodynamic model for the chemical sequence of the alkali–silica reaction (ASR) process in the model, closed reactive system consisting of mixture of reactive silica mineral, calcium hydroxide, and alkali hydroxide solution. The focus of the first part of the study is on formulating the kinetic rate law for silica dissolution as a function of several factors, including pH, temperature, concentration of alkalis in solution, and type of the reactive silica mineral. This kinetic rate law was then incorporated into the commercial modeling software (Geochemist's Workbench®) in an attempt to simulate the chemical sequence of the ASR process. Once the proper input data and parameters were selected, the model generated reasonably accurate predictions of the distribution of species in the reacting system and captured distinct features of experimental data. In addition, this model suggested that the thermodynamic equilibrium condition among reactant (reactive silica mineral), products, and ionic species in the solution resulted in the threshold value of alkali concentration needed for the ASR to take place. Though the application of the proposed model is currently limited to the closed ASR system, the model may offer the possibility of the establishment of the unified theory which can bridge the gap between fundamental (chemical) mechanisms of ASR and the mechanical responses of concrete by providing the kinetic basis for the evolution of ASR process.

Quantification Of Pyrrhotiye O2 Consumption By Using Pyrite Oxidation Kinetic Data

ABSTRACTExperiments on the dissolution kinetics of natural pyrrhotite (FeS1-x-) and pyrite (FeS2) under imposed redox conditions to evaluate the oxygen uptake capacity of both minerals were carried out at 25°C and 1 bar. Experimental data indicate that in both cases, Fe(II) released from dissolution of these Fe-bearing sulphides is kinetically oxidized to Fe(III) to precipitate as Fe(III)-oxyhydroxides. While the system is pH controlled by the extent of the sulphide oxidation, Eh is controlled by the redox pair Fe2+/Fe(III)-oxyhydroxides. Pyrrhotite dissolution is faster than that of pyrite but generates less acidity. Consequently, the achieved redox value is more reducing. Experimental data show that the oxidation rates of both minerals (in mol·g-1·s-1) are equivalent under the studied conditions. This fact gives a new opportunity to quantify the reductive buffering capacity of pyrrhotite, for which no kinetic rate law has been still established.

Use of Experimental Designs to Establish a Kinetic Law for a Gas Phase Photocatalytic Process

Abstract The photocatalytic degradation of three common indoor VOCs – acetone, toluene and heptane – is investigated in a dynamic photocatalytic oxidation loop using Box–Behnken designs of experiments. Thanks to the experimental results and the establishment of a kinetic rate law based on a simplified mechanism, a predictive model for the VOC degradation involving independent factors is developed. The parameters under investigation are initial concentration, light intensity and air velocity through the photocatalytic medium. The obtained model fits properly the experimental curves in the range of concentration, light intensity and air flow studied.

Interaction between dipeptide (glycyl-phenylalanine) and ninhydrin: Role of CTAB and gemini (16-s-16, s = 4, 5, 6) surfactant micelles

The kinetics of interaction of dipeptide glycylphenylalanine (Gly-Phe) with ninhydrin have been studied by following the reaction spectrophotometrically at 70°C and a particular pH 5.0 in the absence and presence of conventional cetyltrimethylammonium bromide (CTAB) and gemini (alkanediyl-α,ω-bis(dimethylhexadecylammonium bromide)) surfactants. The rate shows first- and fractional-order dependence on [Gly-Phe] and [ninhydrin], respectively. The surfactants were found to catalyse the reaction. Furthermore, whereas the typical rate constant (kΨ) increase and leveling-off regions are observed with geminis, just like as seen with conventional surfactants, the former produced a third region of increasing kΨ at higher concentrations. A kinetic rate law consistent with experimental results has been derived on the basis of the proposed mechanism.

New types of experimental data shape the use of enzyme kinetics for dynamic network modeling

Since the publication of Leonor Michaelis and Maude Menten's paper on the reaction kinetics of the enzyme invertase in 1913, molecular biology has evolved tremendously. New measurement techniques allow in vivo characterization of the whole genome, proteome or transcriptome of cells, whereas the classical enzyme essay only allows determination of the two Michaelis-Menten parameters V and K(m). Nevertheless, Michaelis-Menten kinetics are still commonly used, not only in the in vitro context of enzyme characterization but also as a rate law for enzymatic reactions in larger biochemical reaction networks. In this review, we give an overview of the historical development of kinetic rate laws originating from Michaelis-Menten kinetics over the past 100 years. Furthermore, we briefly summarize the experimental techniques used for the characterization of enzymes, and discuss web resources that systematically store kinetic parameters and related information. Finally, describe the novel opportunities that arise from using these data in dynamic mathematical modeling. In this framework, traditional in vitro approaches may be combined with modern genome-scale measurements to foster thorough understanding of the underlying complex mechanisms.

Heteroleptic Alkyl and Amide Iminoanilide Alkaline Earth and Divalent Rare Earth Complexes for the Catalysis of Hydrophosphination and (Cyclo)Hydroamination Reactions

[{N^N}M(X)(thf)n] alkyl (X=CH(SiMe3)2) and amide (X=N(SiMe3)2) complexes of alkaline earths (M=Ca, Sr, Ba) and divalent rare earths (Yb(II) and Eu(II) ) bearing an iminoanilide ligand ({N^N}(-)) are presented. Remarkably, these complexes proved to be kinetically stable in solution. X-ray diffraction studies allowed us to establish size-structure trends. Except for one case of oxidation with [{N^N}Yb(II){N(SiMe3)2}(thf)], all these complexes are stable under the catalytic conditions and constitute effective precatalysts for the cyclohydroamination of terminal aminoalkenes and the intermolecular hydroamination and intermolecular hydrophosphination of activated alkenes. Metals with equal sizes across alkaline earth and rare earth families display almost identical apparent catalytic activity and selectivity. Hydrocarbyl complexes are much better catalyst precursors than their amido analogues. In the case of cyclohydroamination, the apparent activity decreases with metal size: Ca>Sr>Ba, and the kinetic rate law agrees with R(CHA) =k[precatalyst](1)[aminoalkene](1). The intermolecular hydroamination and hydrophosphination of styrene are anti-Markovnikov regiospecific. In both cases, the apparent activity increases with the ionic radius (Ca<Sr<Ba) but the rate laws are different, and obey R(HA) =k[styrene](1)[amine](1)[precatalyst](1) and R(HP) =k[styrene](1)[HPPh2 ](0)[precatalyst](1), respectively. Mechanisms compatible with the rate laws and kinetic isotopic effects are proposed. [{N^N}Ba{N(SiMe3)2}(thf)2] (3) and [{N^N}Ba{CH(SiMe3)2}(thf)2] (10) are the first efficient Ba-based precatalysts for intermolecular hydroamination and hydrophosphination, and display activity values that are above those reported so far. The potential of the precatalysts for C-N and C-P bond formation is detailed and a rare cyclohydroamination-intermolecular hydroamination "domino" sequence is presented.

Reactivity of sandstone and siltstone samples from the Ketzin pilot CO2 storage site-Laboratory experiments and reactive geochemical modeling

To evaluate mineralogical-geochemical changes within the reservoir of the Ketzin pilot CO2 storage site in Brandenburg, Germany, two sets of laboratory experiments on sandstone and siltstone samples from the Stuttgart Formation have been performed. Samples were exposed to synthetic brine and pure CO2 at experimental conditions and run durations of 5.5 MPa/40 °C/40 months for sandstone and 7.5 MPa/40 °C/6 months for siltstone samples, respectively. Mineralogical changes in both sets of experiments are generally minor making it difficult to differentiate natural variability of the whole rock samples from CO2-induced alterations. Results of sandstone experiments suggest dissolution of the anorthite component of plagioclase, anhydrite, K-feldspar, analcime, hematite and chlorite + biotite. Dissolution of the anorthite component of plagioclase, anhydrite and K-feldspars is also observed in siltstone experiments. In an inverse modeling approach, an extensive set of equilibrium simulations was set up in order to reproduce the experimental observations of the sandstone experiments. Simulations generally show fairly good matches with the experimental observations. Best matches with measured brine data are obtained from mineral combinations of albite, analcime, anhydrite, dolomite, hematite, illite, and kaolinite. The major discrepancies during equilibrium modeling, however, are reactions involving Fe2+ and Al3+. The best matching subsets of the equilibrium models were finally run including kinetic rate laws. These simulations reveal that experimentally determined brine data was well matched, but reactions involving K+ and Fe2+ are not fully covered. The modeling results identified key primary minerals as well as key chemical processes, but also showed that the models are not capable of covering all possible contingencies.

Kinetics of Mn2O3–Mn3O4 and Mn3O4–MnO Redox Reactions Performed under Concentrated Thermal Radiative Flux

Manganese oxide based on the thermochemical cycle for splitting water is considered using concentrated solar energy. The high-temperature endothermic step is the thermal reduction of Mn2O3, which proceeds at above 1835 K via two sequential chemical reactions from Mn2O3 to Mn3O4 and then to MnO. The kinetic mechanisms of both reactions are investigated by a solar-driven thermogravimeter, with reactants directly exposed to high-flux thermal irradiation. With this arrangement, the overall kinetic rate laws are derived under similar heat- and mass-transfer characteristics existing in highly concentrating solar systems, such as solar towers or parabolic dishes. The experimental results suggest a nth-order rate for the conversion of Mn2O3 to Mn3O4 and a diffusion-controlled regime for the conversion of Mn3O4 to MnO. Activation energies for both reduction steps are determined and compared to previous reported data.

Comparison of the kinetic rate law parameters for the dissolution of natural and synthetic autunite in the presence of aqueous bicarbonate ions

This research evaluated the effect of aqueous hydrogen carbonate solutions on the uranium rate of release from natural Ca-autunite and quantified the process kinetic rate law for a better prediction of the stability of autunite-group minerals. Testing was accomplished via a single-pass flow-through (SPFT) apparatus using buffered aqueous bicarbonate solutions (0.0005 to 0.003M) at temperatures of 23–90°C and pH values of 7–11. The release rate of uranium from Ca-autunite was directly correlated to increasing concentrations of hydrogen carbonate solutions and showed strong pH dependency. Ca-autunite kinetic rate law parameters were compared to the values obtained for synthetic Na-autunite. The power law coefficient and intrinsic rate constant were higher at pH9–11 for Ca-autunite than for Na-autunite. The lower stability of Ca-autunite was attributed to the high Ca-autunite surface cracking, fractures and basal plane cleavages as compared to Na-autunite and the combined effect of the formation of aqueous uranyl–carbonate and calcium uranyl carbonate species as a driving force for uranium(VI) detachment and the formation of secondary Ca–P hydroxyapatite and uranyl phosphate mineral phases as a driving force for phosphate and calcium detachment controlling the net release of elements.

The stubborn roots of metabolic cycles.

Efforts to catalogue the structure of metabolic networks have generated highly detailed, genome-scale atlases of biochemical reactions in the cell. Unfortunately, these atlases fall short of capturing the kinetic details of metabolic reactions, instead offering only topological information from which to make predictions. As a result, studies frequently consider the extent to which the topological structure of a metabolic network determines its dynamic behaviour, irrespective of kinetic details. Here, we study a class of metabolic networks known as non-autocatalytic metabolic cycles, and analytically prove an open conjecture regarding the stability of their steady states. Importantly, our results are invariant to the choice of kinetic parameters, rate laws, equilibrium fluxes and metabolite concentrations. Unexpectedly, our proof exposes an elementary but apparently open problem of locating the roots of a sum of two polynomials S = P + Q, when the roots of the summand polynomials P and Q are known. We derive two new results named the Stubborn Roots Theorems, which provide sufficient conditions under which the roots of S remain qualitatively identical to the roots of P. Our study illustrates how complementary feedback, from classical fields such as dynamical systems to biology and vice versa, can expose fundamental and potentially overlooked questions.

The formation of iron hydroxide coatings in an Emscher Marl: inverse reactive transport modeling of reactive surface area

The possible effects of iron oxide coatings on the reactive surface area of calcite in column experiments have been studied and then modeled numerically. A column with six compartments separated by teflon filters was packed with Emscher Marl (essentially calcite). The marl was initially mixed with corundum as an internal standard. Hydrochloric acid with pH 3 was percolated through the column for a given period, after which the mineralogical changes were quantified by X-ray diffraction ex-situ. Then, the column compartments were re-filled and again percolated with HCl. This procedure was repeated five times. The losses and gains of calcite in the column compartments provided the data basis for modeling the entire experiment with the reactive transport code TOUGHREACT using a kinetic rate law. The experimental results showed that during the first period, loss of calcite in the first compartment is about 50 % less than that determined from the theoretical analysis. This showed the entrance of acid into the higher compartments through preferential flow paths (wormholes) which was observed at the boundary between sample and cell wall. This pattern could also be verified by the relatively high Peclet and low Damkohler numbers, showing a strongly advection-dominant system. Apart from calcite dissolution, structural Fe2+ released from calcite oxidized and formed iron hydroxide (FeOOH) coatings along preferential fluid pathways. Despite specific assumptions such as using pure calcite in the model, a comparison between modeling results and lab observations is instructive. The simulated calcite change patterns in the most compartments are consistent with the experiments. Some discrepancies are noted in the last compartment, which may bring the attention to a need for model improvements.

Surface chemistry controlled diameter-modulated semiconductor nanowire superstructures

The authors demonstrate that semiconductor nanowire diameter can be rationally controlled as a function of axial position during vapor–liquid–solid synthesis. Such nanoscale structural tuning is achieved with a “molecular resist,” specifically tetramethyltin, that adsorbs on the nanowire sidewall and restricts radial deposition without destabilizing the growth front. The temporal modulation of tetramethyltin delivery during Ge nanowire growth yields user-programmable diameter-modulated superstructures with sub-100 nm periodicities. The authors also investigate the effect of Sn accumulation in the growth catalyst and propose a second-order kinetic rate law that accurately predicts changes to nanowire axial growth rate.

Mechanistic analysis of multi-omics datasets to generate kinetic parameters for constraint-based metabolic models

BackgroundConstraint-based modeling uses mass balances, flux capacity, and reaction directionality constraints to predict fluxes through metabolism. Although transcriptional regulation and thermodynamic constraints have been integrated into constraint-based modeling, kinetic rate laws have not been extensively used.ResultsIn this study, an in vivo kinetic parameter estimation problem was formulated and solved using multi-omic data sets for Escherichia coli. To narrow the confidence intervals for kinetic parameters, a series of kinetic model simplifications were made, resulting in fewer kinetic parameters than the full kinetic model. These new parameter values are able to account for flux and concentration data from 20 different experimental conditions used in our training dataset. Concentration estimates from the simplified kinetic model were within one standard deviation for 92.7% of the 790 experimental measurements in the training set. Gibbs free energy changes of reaction were calculated to identify reactions that were often operating close to or far from equilibrium. In addition, enzymes whose activities were positively or negatively influenced by metabolite concentrations were also identified. The kinetic model was then used to calculate the maximum and minimum possible flux values for individual reactions from independent metabolite and enzyme concentration data that were not used to estimate parameter values. Incorporating these kinetically-derived flux limits into the constraint-based metabolic model improved predictions for uptake and secretion rates and intracellular fluxes in constraint-based models of central metabolism.ConclusionsThis study has produced a method for in vivo kinetic parameter estimation and identified strategies and outcomes of kinetic model simplification. We also have illustrated how kinetic constraints can be used to improve constraint-based model predictions for intracellular fluxes and biomass yield and identify potential metabolic limitations through the integrated analysis of multi-omics datasets.

Local CFD kinetic model of cadmium vaporization during fluid bed incineration of municipal solid waste

The emissions of heavy metals during incineration of Municipal Solid Waste (MSW) are a major issue to health and the environment. It is then necessary to well quantify these emissions in order to accomplish an adequate control and prevent the heavy metals from leaving the stacks. In this study the kinetic behavior of Cadmium during Fluidized Bed Incineration (FBI) of artificial MSW pellets, for bed temperatures ranging from 923 to 1073K, was modeled. FLUENT 12.1.4 was used as the modeling framework for the simulations and implemented together with a complete set of user-defined functions (UDFs). The CFD model combines the combustion of a single solid waste particle with heavy metal (HM) vaporization from the burning particle, and it takes also into account both pyrolysis and volatiles’ combustion. A kinetic rate law for the Cd release, derived from the CFD thermal analysis of the combusting particle, is proposed. The simulation results are compared with experimental data obtained in a lab-scale fluidized bed incinerator reported in literature, and with the predicted values from a particulate non-isothermal model, formerly developed by the authors. The comparison shows that the proposed CFD model represents very well the evolution of the HM release for the considered range of bed temperature.

Kinetics and Mechanism of Electron-Transfer Reactions: Oxidation of Butanone and Cyclohexanone by Thallium (III) in Acid Perchlorate Medium- An Appraisal of Keto Form Reactivity

The kinetics of oxidation of ketones by thallium (III) has been studied in acid perchlorate medium. The reaction does not indicate enolization to be the rate controlling step in the reaction mechanism. The kinetic rate law (1) has been observed. -d[TlIII] / dt= k1Kh [Tl(III)Ketone] / ([H+] + Kh) Where Kh is the hydrolysis constant of the oxidant. A plausible reaction mechanism is suggested conforming to the rate law (1). Activation parameters were evaluated.

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

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.