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Knowing the values of the equilibrium constants corresponding to the reactions N(2)O(4) right harpoon over left harpoon 2NO(2) and N(2)O(4) right harpoon over left harpoon NO(+) + NO(3)(-) in sulpholane, we have undertaken the electrochemical study of N(2)O(4) by means of linear and cyclic voltammetry at the platinum electrode. The N(2)O(4) species undergoes one oxidation step N(2)O(4) right harpoon over left harpoon 2NO(2) right harpoon over left harpoon 2NO(2)(+) + 2e and two reduction steps NO(2) + N(2)O(4) + e(-)right harpoon over left harpoon N(2)O(3) + NO(3)(-) (1st wave), followed by 3N(2)O(4) + 2e(-) right harpoon over left harpoon 2N(2)O(3) + 2NO(3)(-), N(2)O(4) + e(-) right harpoon over left harpoon NO + NO(3)(-), 2N(2)O(3) + e(-) right harpoon over left harpoon 3NO + NO(3)(-) (2nd wave). The redox properties of N(2)O(4) are complicated by trace quantities of water because of the formation of the electroactive species N(2)O(3), HNO(3) and HNO(2) according to N(2)O(4) + H(2)O right harpoon over left harpoon HNO(2) + HNO(3) and N(2)O(4) + HNO(2) right harpoon over left harpoon N(2)O(3) + HNO(3). The standard potentials of the couples concerned have been evaluated and are discussed. sont discutés et évalués.
Boughriet
A
A
Laboratoire de Chimie Analytique et Marine, Université des Sciences et Techniques de Lille, Batiment C(8), 59655 Villeneuve d'Ascq, France.
Wartel
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M
Fischer
J C
JC