Kinetics and Mechanism of Oxalic Acid Oxidation by Nitric Acid Catalyzed by Mn(Ⅱ)

doi:10.19894/j.issn.1000-0518.200320

Chinese Journal of Applied Chemistry ›› 2021, Vol. 38 ›› Issue (6): 685-692.DOI: 10.19894/j.issn.1000-0518.200320

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Kinetics and Mechanism of Oxalic Acid Oxidation by Nitric Acid Catalyzed by Mn(Ⅱ)

WANG Yu-Ting, ZHANG Xiao-Teng, LI Xian-Jun, XIA Liang-Shu^*

School of Nuclear Science and Technology, University of South China, Hengyang 421001, China

Received:2020-10-26 Revised:2021-02-05 Published:2021-06-01 Online:2021-08-01

Abstract

Abstract: A kinetic study on the oxidation of oxalic acid by nitric acid using Mn²⁺ as the catalyst was carried out to clarify the reaction mechanism and reaction process, and optimize the process conditions. By investigating the influence of concentrations of oxalic acid and nitric acid on the reaction process, the initial kinetic rate equation of the reaction is obtained: -dc(H₂C₂O₄)/dt=kc^0.7840(H₂C₂O₄)c^0.3192(HNO₃), and the reaction rate constant is k=3.0×10^-3 (mol/L)^-0.1032/min at 393 K. The results show that when the Mn²⁺ concentration is in the range of 0.008~0.020 mol/L, the reaction order of Mn²⁺ is 0.6742 and the increase of concentrations of Mn²⁺ and sodium nitrite promotes the initial consumption rate of oxalic acid. On this basis, the possible reaction mechanism is speculated, and it is believed that Mn²⁺ promotes the production of nitrous acid, and the secondary oxidation and reduction of nitrite and oxalic acid promote the decomposition of oxalic acid.

Key words: Oxalic acid, Manganese(Ⅱ), Nitric acid, Catalytic oxidation, Dynamics

CLC Number:

WANG Yu-Ting, ZHANG Xiao-Teng, LI Xian-Jun, XIA Liang-Shu. Kinetics and Mechanism of Oxalic Acid Oxidation by Nitric Acid Catalyzed by Mn(Ⅱ)[J]. Chinese Journal of Applied Chemistry, 2021, 38(6): 685-692.

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Kinetics and Mechanism of Oxalic Acid Oxidation by Nitric Acid Catalyzed by Mn(Ⅱ)

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