Reactivity of Zn<sup>+</sup><sub>aq</sub> in high-temperature water radiolysis

Lisovskaya, Alexandra; Markad, Uddhav S.; Carmichael, Ian; Bartels, David M.

doi:10.1039/d2cp02434a

Cited by 2 publications

(3 citation statements)

References 47 publications

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“…Recently we deduced that nominally ultrapure Zn(ClO 4 ) 2 salts (99.99% metals basis) contained some nonmetallic impurity that reacts very quickly with e − aq and the ZnCl 2 and ZnSO 4 salts also gave reproducibly lower rate constants for e − aq reaction with Zn 2+ near room temperature. 20 We can only surmise that a similar problem with the nickel perchlorate salt might explain the discrepancy between our present measurements and the earlier report of Kanjana et al 8 As of this writing, we have not been able to identify the postulated impurity.…”

Section: Pulse Radiolysis Experimentalcontrasting

confidence: 96%

“…A possible reason could be an impurity that competes with the Ni 2+ ion in the reaction with e – aq , resulting in a lower value for the extinction coefficient. We observed a similar behavior of an impurity in perchlorate salt when we reported the extinction coefficient for Zn + formed in various salts in our previous paper …”

Section: Resultssupporting

confidence: 75%

“…We observed a similar behavior of an impurity in perchlorate salt when we reported the extinction coefficient for Zn + formed in various salts in our previous paper. 20 We studied the effect of pH on absorption of monovalent Ni + ion formed after pulse radiolysis of 0.5 mM Ni(ClO 4 ) 2 solution saturated with argon (see Figure S1 in Supporting Information). It is established that the maximum absorption is observed in a neutral medium, and with a shift toward an acidic medium, the signal decreases.…”

Section: Pulse Radiolysis Experimentalmentioning

confidence: 99%

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Reactions of Nickel Ions in Water Radiolysis up to 300 °C

2023

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Radiation chemistry of hydrated metal ions plays a significant role in the field of nuclear energy, especially regarding water radiolysis in coolant water in nuclear reactors. This work reports new experimental data on the reactivity of Ni2+/+ species under critical conditions of temperature and pressure. The reaction rates of hydrated nickel ions with water radiolysis products (e– aq, •OH, H, and H2O2) have been investigated for a 25–300 °C temperature range and 200 bar pressure using electron pulse radiolysis/transient absorption. Extensive experiments with the Ni2+/+ species in various salts and pH up to 300 °C were performed. Kinetic decay traces of short-lived monovalent nickel ions were fitted to extract the rate constants versus temperature up to 300 °C. A blue shift of the absorption spectrum of the monovalent nickel ion with increasing temperature was demonstrated, which may indicate a change in the average coordination number. The Arrhenius parameters for the reactions of Ni2+ with e– aq and Ni+ with •OH, H, and H2O2 were obtained. All measured rate constants increased with temperature and followed Arrhenius behavior.