New Mechanistic Aspects of the Fenton Reaction

被引:101
作者
Rachmilovich-Calis, Sandra [1 ]
Masarwa, Alexandra [1 ]
Meyerstein, Naomi [2 ]
Meyerstein, Dan [1 ,3 ]
van Eldik, Rudi [4 ]
机构
[1] Ben Gurion Univ Negev, Dept Chem, Beer Sheva, Israel
[2] Ben Gurion Univ Negev, Fac Hlth Sci, Dept Physiol, Beer Sheva, Israel
[3] Ariel Univ, Dept Biol Chem, Ctr Samaria, Ariel, Israel
[4] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany
关键词
activation parameters; Fenton reaction; kinetics; mechanism; oxidation; TRANSITION-METAL-COMPLEXES; AERATED AQUEOUS-SOLUTIONS; HYDROGEN-PEROXIDE; OXIDATION; ACTIVATION; CHEMISTRY; ION; DECOMPOSITION; RADICALS; DIOXYGEN;
D O I
10.1002/chem.200802572
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The kinetics of the Fenton reaction was studied in detail. A second reaction step in the presence of excess H2O2 is attributed to formation of the complex Fe-III(-O2H)(aq). Therefore, the reaction of Fe(H2O)(6)(2+) with Fe-III(-O2H)(aq) in the presence of Fe-II to form Fe-aq(III) (k = (7.7 +/- 1.5) x 10(5) M-1 S-1) may contribute to the overall Fenton reaction, and could account for some of the debate in the literature concerning its detailed mechanism. If this is correct for LFeIII(-O2H)(aq) also, then it might be of significant biological importance. The activation parameters Delta H double dagger, Delta S double dagger, and Delta V double dagger for the Fenton reaction were measured under various experimental conditions, and are used in the mechanistic interpretation.
引用
收藏
页码:8303 / 8309
页数:7
相关论文
共 58 条
[1]   REACTIONS OF LOW VALENT TRANSITION-METAL COMPLEXES WITH HYDROGEN-PEROXIDE - ARE THEY FENTON-LIKE OR NOT .3. THE CASE OF FE(II)(N(CH2CO2)3)(H2O)2- [J].
BAMNOLKER, H ;
COHEN, H ;
MEYERSTEIN, D .
FREE RADICAL RESEARCH COMMUNICATIONS, 1991, 15 (04) :231-241
[2]   REACTIONS OF FERROUS AND FERRIC IONS WITH HYDROGEN PEROXIDE .1. THE FERROUS ION REACTION [J].
BARB, WG ;
BAXENDALE, JH ;
GEORGE, P ;
HARGRAVE, KR .
TRANSACTIONS OF THE FARADAY SOCIETY, 1951, 47 (05) :462-500
[3]   THE MECHANISM AND KINETICS OF THE INITIATION OF POLYMERISATION BY SYSTEMS CONTAINING HYDROGEN PEROXIDE [J].
BAXENDALE, JH ;
EVANS, MG ;
PARK, GS .
TRANSACTIONS OF THE FARADAY SOCIETY, 1946, 42 (3-4) :155-169
[4]  
Bolzan J.A., 1963, Electrochimica Acta, V8, P375, DOI DOI 10.1016/0013-4686(63)80066-3
[5]   Ferryl ion, a compound of tetravalent iron [J].
Bray, WC ;
Gorin, MH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1932, 54 :2124-2125
[6]  
Buda F, 2001, CHEM-EUR J, V7, P2775, DOI 10.1002/1521-3765(20010702)7:13<2775::AID-CHEM2775>3.0.CO
[7]  
2-6
[8]   O2 evolution in the Fenton reaction [J].
Buda, F ;
Ensing, B ;
Gribnau, MCM ;
Baerends, EJ .
CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (14) :3436-3444
[9]  
CHIU D, 1989, SEMIN HEMATOL, V26, P257
[10]  
CLERICI MG, 1993, STUD SURF SCI CATAL, V78, P21