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CO2/O2 Exchange in Magnesium-Water Clusters Mg+(H2O) n.


ABSTRACT: Hydrated singly charged metal ions doped with carbon dioxide, Mg2+(CO2)-(H2O) n, in the gas phase are valuable model systems for the electrochemical activation of CO2. Here, we study these systems by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry combined with ab initio calculations. We show that the exchange reaction of CO2 with O2 proceeds fast with bare Mg+(CO2), with a rate coefficient kabs?=?1.2 × 10-10?cm3?s-1, while hydrated species exhibit a lower rate in the range of kabs = (1.2-2.4) × 10-11?cm3?s-1 for this strongly exothermic reaction. Water makes the exchange reaction more exothermic but, at the same time, considerably slower. The results are rationalized with a need for proper orientation of the reactants in the hydrated system, with formation of a Mg2+(CO4)-(H2O) n intermediate while the activation energy is negligible. According to our nanocalorimetric analysis, the exchange reaction of the hydrated ion is exothermic by -1.7 ± 0.5?eV, in agreement with quantum chemical calculations.

SUBMITTER: Barwa E 

PROVIDER: S-EPMC6331139 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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CO<sub>2</sub>/O<sub>2</sub> Exchange in Magnesium-Water Clusters Mg<sup>+</sup>(H<sub>2</sub>O) <sub>n</sub>.

Barwa Erik E   Ončák Milan M   Pascher Tobias F TF   Taxer Thomas T   van der Linde Christian C   Beyer Martin K MK  

The journal of physical chemistry. A 20181219 1


Hydrated singly charged metal ions doped with carbon dioxide, Mg<sup>2+</sup>(CO<sub>2</sub>)<sup>-</sup>(H<sub>2</sub>O) <sub>n</sub>, in the gas phase are valuable model systems for the electrochemical activation of CO<sub>2</sub>. Here, we study these systems by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry combined with ab initio calculations. We show that the exchange reaction of CO<sub>2</sub> with O<sub>2</sub> proceeds fast with bare Mg<sup>+</sup>(CO<sub>2</sub>),  ...[more]

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