Photochemistry of cerium(IV) ammonium nitrate (CAN) in acetonitrile

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Abstract

Cerium ammonium nitrate (NH4)2CeIV(NO3)6 (CAN) is widely used as a photolytic source of NO3[rad] radicals in acetonitrile. In spite of that, the mechanistic aspects of CAN photochemistry were poorly discussed in the literature. In this work CAN photochemistry in CH3CN was studied using the combination of stationary methods and laser flash photolysis. In accordance with the literature, the inner-sphere electron transfer was found to be the primary photochemical process. The (NH4)2CeIII(NO3)5(CH3CN) complex was found to be the only reaction product formed with the rather high quantum yield (0.6 and 0.4 upon 308 and 355 nm excitation correspondingly). The NO3[rad] radicals decay is mainly caused by the second-order reactions; their rate constants are determined. In addition to the direct release of the NO3[rad] radicals, a part of the light-excited CAN molecules were found to form the radical complex [(NH4)2CeIII(NO3)5…NO3[rad]], which lifetime is ca. 2 μs.

Original languageEnglish
Article number113440
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume418
DOIs
Publication statusPublished - 1 Sep 2021

Keywords

  • NO radical
  • Acetonitrile
  • Cerium ammonium nitrate (CAN)
  • Laser flash photolysis
  • Photochemistry
  • Photoreduction

OECD FOS+WOS

  • 2.04 CHEMICAL ENGINEERING
  • 1.03 PHYSICAL SCIENCES AND ASTRONOMY
  • 1.04 CHEMICAL SCIENCES

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