Photoredox behaviour of the Cr-EDTA complex and its environmental aspects

被引:33
作者
Ciesla, P [1 ]
Karocki, A [1 ]
Stasicka, Z [1 ]
机构
[1] Jagiellonian Univ, Fac Chem, PL-30060 Krakow, Poland
关键词
photoreduction; organic pollutants; electron shuttle mechanism; Cr-III-EDTA; photodegradation;
D O I
10.1016/S1010-6030(03)00418-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Polychromatic radiation from a mercury lamp or light mimicking the sunlight (lambda greater than or equal to 300 nm) is able to initiate an innersphere electron transfer in the [Cr(III)EDTA(OH)](2-) complex, leading to formation of a Cr(II) centre and the EDTA radical. Under defined conditions (pH greater than or equal to 7, O-2 in excess over the Cr(H) concentration) the photoreduction is followed by thermal multi-step electron transfer resulting in the Cr(II) --> Cr(VI) oxidation by molecular oxygen, although EDTA is known to enhance the Cr(VI) reduction. Electron donors, present in the system, enlarge the efficiency of Cr(VI) production. These are also able to take part in the photoinduced electron transfer to CrO42-/HCrO4- in excited states, when pH reaches corresponding level. As Cr(VI) production is accompanied by decrease in pH, and its reduction with an opposite effect, the processes proceed according to an electron shuttle mechanism. Their progress under natural conditions seems attainable, because all conditions needed to the photocatalytic oxidation of organic pollutants by O-2, with oscillatory recovery of the Cr(III) and Cr(VI) species can be provided. (C) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:537 / 544
页数:8
相关论文
共 41 条
[21]   Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range [J].
Metsärinne, S ;
Tuhkanen, T ;
Aksela, R .
CHEMOSPHERE, 2001, 45 (6-7) :949-955
[22]   Absorption spectroscopy in the visible spectral range of trivalent and hexavalent chromium in distilled water and in buffers at different pH values [J].
Mignani, AG ;
Romolini, A .
SPECTROSCOPY LETTERS, 2002, 35 (03) :467-488
[23]   Mechanism of photochemical reduction of chromium(VI) by alcohols and its environmental aspects [J].
Mytych, P ;
Karocki, A ;
Stasicka, Z .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2003, 160 (03) :163-170
[24]  
Mytych P, 2001, INT J PHOTOENERGY, V3
[25]   EQUILIBRIUM AND KINETIC STUDIES OF REACTIONS OF N-SUBSTITUTED ETHYLENEDIAMINE-N,N',N'-TRIACETATOAQUACHROMIUM(III) WITH ACETATE IONS [J].
OGINO, H ;
WATANABE, T ;
TANAKA, N .
INORGANIC CHEMISTRY, 1975, 14 (09) :2093-2097
[26]   Mechanism of oxidation of phenol and 2,6-dimethylphenol in the presence of Cr(phen)33+ excited state:: the role of O2 [J].
Pagliero, D ;
Argüello, GA .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2001, 138 (03) :207-211
[27]  
Palopoli C, 1997, NEW J CHEM, V21, P343
[28]   Ligand field photochemistry of mixed-ligand cyanochromates. Comparative study of [Cr(CN)(5)(OH)](3-) and [Cr(CN)(4)(N-3)(OH)](3-) [J].
Quang, HB ;
Stasicka, Z ;
Mainusch, B ;
Wasgestian, F .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1996, 98 (03) :149-154
[29]  
RICHARD R, 1999, ENV PHOTOCHEMISTRY, P241
[30]   OXIDATION OF ALCOHOLS, ALDEHYDES, AND CARBOXYLATES BY THE AQUACHROMIUM(IV) ION [J].
SCOTT, SL ;
BAKAC, A ;
ESPENSON, JH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (11) :4205-4213