Sulfur Dioxide Oxidation by Zinc and Zinc Oxide Nitrate/Nitrite Complexes in the Gas Phase: An Interplay between Redox‐Active Ligands and Metal

Author:

Salvitti Chiara1ORCID,Bandeira Nuno A. G.2ORCID,Pepi Federico1ORCID,de Petris Giulia1ORCID,Troiani Anna1ORCID

Affiliation:

1. Dipartimento di Chimica e Tecnologie del Farmaco Sapienza Università di Roma P.le Aldo Moro 5 Rome Italy

2. Biosystems and Integrative Sciences Institute (BioISI)- Departamento de Química e Bioquímica Faculdade de Ciências Universidade de Lisboa 8.5.53 - C8 Campo Grande 1749-016 Lisboa Portugal

Abstract

AbstractDifferent oxidative pathways of sulfur dioxide promoted by ZnO(NO3)2, Zn(NO3)2 and Zn(NO2)(NO3) are revealed by a joint investigation by mass spectrometry and theoretical calculations. The reactions are triggered by [Zn2+‐O⋅]+ or by the low‐valence Zn+ through oxygen ion transfer or electron transfer to SO2, respectively. The NOx ligands intervene in the oxidation only when sulfur dioxide is converted to SO3 or SO2, leading to the formation of zinc sulfate and zinc sulfite coordinated to nitrate or nitrite anions. Kinetic analyses show that the reactions are fast and efficient, and theory discloses the elementary steps, namely oxygen ion transfer, oxygen atom transfer and electron transfer, occurring through similar energy landscapes for the three reactive anions.

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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