Polychlorinated biphenyls: correlation between experimental data and quantum-chemical simulation

被引：5

作者：

Gorbunova, T. I. ^{[1
]}

Subbotina, Yu O. ^{[2
]}

Saloutin, V. I. ^{[1
]}

Chupakhin, O. N. ^{[1
]}

机构：

[1] Russian Acad Sci, Postovskii Inst Organ Synth, Ural Branch, Ekaterinburg 620990, Russia

[2] Ural Fed Univ, Ekaterinburg, Russia

来源：

RUSSIAN JOURNAL OF GENERAL CHEMISTRY | 2014年 / 84卷 / 03期

基金：

俄罗斯基础研究基金会;

关键词：

REDUCTIVE DECHLORINATION; CONTAMINATED SOILS; METALLIC CALCIUM; PCBS; REACTIVITY; IRON; HYDRODECHLORINATION; BIODEGRADATION; DEGRADATION; REMEDIATION;

D O I：

10.1134/S107036321403013X

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In order to comprehend the data on reactivity of polychlorinated biphenyls of the Sovol mixture in nucleophilic substitution reactions we have performed quantum-chemical simulation using the RB3LYP\6-31G(d) gas phase approximation. Using the "Atoms-in-Molecules" approach, we have computed charges on the biphenyl carbon atoms adjacent to chlorine; furthermore, absolute chemical hardness and global electrophilicity index have been determined for the studied chlorobiphenyls. The calculated descriptors have been correlated with experimentally determined reactivity of the biphenyls in the hard acid-hard base nucleophilic reactions. The higher reactivity of more chlorinated substrates has been confirmed.

引用

页码：486 / 495

页数：10

共 43 条

[1] Enhanced corrosion-based Pd/Mg bimetallic systems for dechlorination of PCBs [J].

Agarwal, Shirish ;

Al-Abed, Souhail R. ;

Dionysiou, Dionysios D. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2007, 41 (10) :3722-3727

[2]

[Anonymous], 2012, Aimall (Version 13.02.26)

[3] Thermal desorption of polychlorobiphenyls from contaminated soils and their hydrodechlorination using Pd- and Rh-supported catalysts [J].

Aresta, M. ;

Dibenedetto, A. ;

Fragale, C. ;

Giannoccaro, P. ;

Pastore, C. ;

Zammiello, D. ;

Ferragina, C. .

CHEMOSPHERE, 2008, 70 (06) :1052-1058

[4]

Bader R. F. W., 1994, ATOMS MOL QUANTUM TH

[5] ANALYSIS OF POLYCHLORINATED-BIPHENYLS (PCB) BY GLASS-CAPILLARY GAS-CHROMATOGRAPHY - COMPOSITION OF TECHNICAL AROCLOR-PCB AND CLOPHEN-PCB MIXTURES [J].

BALLSCHMITER, K ;

ZELL, M .

FRESENIUS ZEITSCHRIFT FUR ANALYTISCHE CHEMIE, 1980, 302 (01) :20-31

[6] On the nature of Parr functions to predict the most reactive sites along organic polar reactions [J].

Chamorro, Eduardo ;

Perez, Patricia ;

Domingo, Luis R. .

CHEMICAL PHYSICS LETTERS, 2013, 582 :141-143

[7] Philicity: A unified treatment of chemical reactivity and selectivity [J].

Chattaraj, PK ;

Maiti, B ;

Sarkar, U .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (25) :4973-4975

[8] Density functional theory study of conformations, barriers to internal rotations and torsional potentials of polychlorinated biphenyls [J].

Dorofeeva, OV ;

Novikov, VP ;

Moiseeva, NF ;

Yungman, VS .

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2003, 637 :137-153

[9] Simultaneous determination of total polychlorinated biphenyl and dichlorodiphenyltrichloroethane (DDT) by dechlorination with Fe/Pd and Mg/Pd bimetallic articles and flame ionization detection gas chromatography [J].

Engelmann, MD ;

Hutcheson, R ;

Henschied, K ;

Neal, R ;

Cheng, IF .

MICROCHEMICAL JOURNAL, 2003, 74 (01) :19-25

[10] Dechlorination kinetics of monochlorobiphenyls by Fe/Pd: Effects of solvent, temperature, and PCB concentration [J].

Fang, Yuanxiang ;

Al-Abed, Souhail R. .

APPLIED CATALYSIS B-ENVIRONMENTAL, 2008, 78 (3-4) :371-380

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