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Kinetics and mechanisms of oxidations by metal ions. Part VI. Oxidation of α-hydroxy acids by cerium(IV) in aqueous nitric acid

 

作者: Narain Datt,   Ratan R. Nagori,   Raj N. Mehrotra,  

 

期刊: Canadian Journal of Chemistry  (NRC Available online 1986)
卷期: Volume 64, issue 1  

页码: 19-23

 

ISSN:0008-4042

 

年代: 1986

 

DOI:10.1139/v86-005

 

出版商: NRC Research Press

 

数据来源: NRC

 

摘要:

The kinetics of oxidation of glycolic, malic, tartaric, and citric acids by cerium(IV) ammonium nitrate were investigated in 0.006 mol dm−3nitric acid. The reaction was catalysed by H+in the range 0.006–0.016 mol dm−3at constant(0.02 mol dm−3). The pseudo first-order rate constantkobswas independent of [CeIII] (0.0004–0.002 mol dm−3). The proposed mechanism is based on the assumption that the formation of the precursor Ce(IV) – α-hydroxy acid complex precedes its rate controlling disproportionation, which is assisted by a proton, possibly due to the formation of the activated state [H+—CeIV– HA]≠(where CeIVis the reactive cerium(IV) species and HA is the α-hydroxy acid). The free radical R1R2ĊOH produced in the rate controlling step further reacts with a number of Ce(IV) molecules in the fast step to yield the final oxidation product. The activation parameters for the rate controlling step could be evaluated only in the oxidation of tartaric acid

 

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