Kinetics of the reaction of ferrous ions with hydroxyl radicals in the temperature range 25-300 °C.

The kinetics and mechanism of the reaction between OH radicals and ferrous ions in the temperature range 25-300 °C were studied using pulse radiolysis. At temperatures <150 °C the rate of reaction is essentially independent of temperature, while at temperatures >150 °C the activation energy is 45.8 ± 3.0 kJ mol-1. The change in activation energy is attributed to a change in the dominant mechanism from hydrogen atom transfer (HAT) to dissociative ligand interchange. The kinetic isotope effect (KIE) was measured by repeating experiments in heavy water. A value of 2.9 was measured at room temperature where HAT is the dominant mechanism. The KIE decreases to zero at temperatures > 150 °C as ligand interchange becomes dominant and the O-H bond is no longer involved in the reaction.

High-Temperature Reaction Kinetics of the eaq- and HO2• Radicals with Iron(II) Ions in Aqueous Solutions.

Pulsed electron radiolysis was used to determine the chemical reaction kinetics and Arrhenius parameters for iron(II) reactions in aqueous solutions under irradiation. The second-order Fe2+ reactions with the hydrated electron (eaq-) and the perhydroxyl radical (HO2•), arising from water radiolysis, were measured to high temperatures using custom-built flow-through cells with a multichannel optical detection system. The reaction with the HO2• radical was found to proceed via the formation of a metal-ion adduct species, Fe2+-HO2•. The adduct's molar extinction coefficient and its first-order decay rate coefficients are also reported.

Self-radiolysis of tritiated water. 4. The scavenging effect of azide ions (N3 -) on the molecular hydrogen yield in the radiolysis of water by 60Co γ-rays and tritium ß-particles at room temperature.

The effect of the azide ion N3 - on the yield of molecular hydrogen in water irradiated with 60Co γ-rays (∼1 MeV Compton electrons) and tritium ß-electrons (mean electron energy of ∼7.8 keV) at 25 °C is investigated using Monte Carlo track chemistry simulations in conjunction with available experimental data. N3 - is shown to interfere with the formation of H2 through its high reactivity towards hydrogen atoms and, but to a lesser extent, hydrated electrons, the two major radiolytic precursors of the H2 yield in the diffusing radiation tracks. Chemical changes are observed in the H2 scavengeability depending on the particular type of radiation considered. These changes can readily be explained on the basis of differences in the initial spatial distribution of primary radiolytic species (i.e., the structure of the electron tracks). In the "short-track" geometry of the higher "linear energy transfer" (LET) tritium ß-electrons (mean LET ∼5.9 eV nm-1), radicals are formed locally in much higher initial concentration than in the isolated "spurs" of the energetic Compton electrons (LET ∼0.3 eV nm-1) generated by the cobalt-60 γ-rays. As a result, the short-track geometry favors radical-radical reactions involving hydrated electrons and hydrogen atoms, leading to a clear increase in the yield of H2 for tritium ß-electrons compared to 60Co γ-rays. These changes in the scavengeability of H2 in passing from tritium ß-radiolysis to γ-radiolysis are in good agreement with experimental data, lending strong support to the picture of tritium ß-radiolysis mainly driven by the chemical action of short tracks of high local LET. At high N3 - concentrations (>1 M), our H2 yield results for 60Co γ-radiolysis are also consistent with previous Monte Carlo simulations that suggested the necessity of including the capture of the precursors to the hydrated electrons (i.e., the short-lived "dry" electrons prior to hydration) by N3 -. These processes tend to reduce significantly the yields of H2, as is observed experimentally. However, this dry electron scavenging at high azide concentrations is not seen in the higher-LET 3H ß-radiolysis, leading us to conclude that the increased amount of intra-track chemistry intervening at early time under these conditions favors the recombination of these electrons with their parent water cations at the expense of their scavenging by N3 -.

Modeling the radiolysis of supercritical water by fast neutrons: density dependence of the yields of primary species at 400°c.

A reliable understanding of radiolysis processes in supercritical water (SCW)-cooled reactors is crucial to developing chemistry control strategies that minimize the corrosion and degradation of materials. However, directly measuring the chemistry in reactor cores is difficult due to the extreme conditions of high temperature and pressure and mixed neutron and gamma-radiation fields, which are incompatible with normal chemical instrumentation. Thus, chemical models and computer simulations are an important route of investigation for predicting the detailed radiation chemistry of the coolant in a SCW reactor and the consequences for materials. Surprisingly, information on the fast neutron radiolysis of water at high temperatures is limited, and even more so for fast neutron irradiation of SCW. In this work, Monte Carlo simulations were used to predict the G values for the primary species e(-)aq, H(•), H2, (•)OH and H2O2 formed from the radiolysis of pure, deaerated SCW (H2O) by 2 MeV monoenergetic neutrons at 400°C as a function of water density in the range of ∼0.15-0.6 g/cm(3). The 2 MeV neutron was taken as representative of a fast neutron flux in a reactor. For light water, the moderation of these neutrons after knock-on collisions with water molecules generated mostly recoil protons of 1.264, 0.465, 0.171 and 0.063 MeV. Neglecting oxygen ion recoils and assuming that the most significant contribution to the radiolysis came from these first four recoil protons, the fast neutron yields were estimated as the sum of the G values for these protons after appropriate weightings were applied according to their energy. Calculated yields were compared with available experimental data and with data obtained for low-LET radiation. Most interestingly, the reaction of H(•) atoms with water was found to play a critical role in the formation yields of H2 and (•)OH at 400°C. Recent work has underscored the potential importance of this reaction above 200°C, but its rate constant is still controversial.

Long-term γ-radiolysis kinetics of NO3(-) and NO2(-) solutions.

Radiolysis kinetics in NO(3)(-) and NO(2)(-) solutions during γ-irradiation were studied at an absorbed dose rate of 2.1 Gy·s(-1) at room temperature. Air- or argon-saturated nitrate or nitrite solutions at pH 6.0 and 10.6 were irradiated, and the aqueous concentrations of molecular water decomposition products, H(2) and H(2)O(2), and the variation in the concentrations of NO(3)(-) and NO(2)(-) were measured as a function of irradiation time. The experimental data were compared with computer simulations using a comprehensive radiolysis kinetic model to aid in interpretation of the experimental results. The effect of nitrate and nitrite, present at concentrations below 10(-3) M, on water radiolysis processes occurs through reactions with the radical species generated by water radiolysis, (•)e(aq)(-), (•)O(2)(-), and (•)OH. The changes in H(2) and H(2)O(2) concentrations observed in the presence of nitrate and nitrite under a variety of conditions can be explained by a reduction in the radical concentrations. The kinetic analysis shows that the main loss pathway for H(2) is the reaction with (•)OH and the main loss pathways for H(2)O(2) are reactions with (•)e(aq)(-) and (•)OH. Nitrate and nitrite compete for the radicals leading to an increase in the concentrations of H(2) and H(2)O(2). Post-irradiation measurements of H(2), H(2)O(2), NO(2)(-) and NO(3)(-) concentrations can be used to calculate the radical concentrations and provide information on the redox conditions of the irradiated aqueous solutions.