Reactivity of polychlorinated biphenyls in nucleophilic and electrophilic substitutions / Gorbunova Tatyana I.,Subbotina Julia O.,Saloutin Viktor I.,Chupakhin Oleg N. // JOURNAL OF HAZARDOUS MATERIALS. - 2014. - V. 278, l. . - P. 491-499.

ISSN/EISSN:

0304-3894 / 1873-3336

Type:

Article

Abstract:

To explain the chemical reactivity of polychlorinated biphenyls in nucleophilic (S-N) and electrophilic (S-E) substitutions, quantum chemical calculations were carried out at the B3LYP/6-31G(d) level of the Density Functional Theory in gas phase. Carbon atomic charges in biphenyl structure were calculated by the Atoms-in-Molecules method. Chemical hardness and global electrophilicity index parameters were determined for congeners. A comparison of calculated descriptors and experimental data for congener reactivity in the S-N and S-E reactions was made. It is shown that interactions in the S-N mechanism are reactions of the hard acid-hard base type, these are the most effective in case of highly chlorinated substrates. To explain the congener reactivity in the S-E reactions, correct descriptors were not established. The obtained results can be used to carry out chemical transformations of the polychlorinated biphenyls in order to prepare them for microbiological destruction or preservation. (C) 2014 Elsevier B.V. All rights reserved.

Author keywords:

PCBs; Congeners; Nucleophilic substitution; Electrophilic substitution; Descriptors DENSITY-FUNCTIONAL THEORY; CATALYZED DECHLORINATION; AROMATIC-SUBSTITUTION; CHEMICAL-REACTIVITY; GAS-CHROMATOGRAPHY; CONTAMINATED SOIL; REDUCTIVE DECHLORINATION; MOLECULAR-STRUCTURE; HOMO-LUMO; FT-IR

DOI:

10.1016/j.jhazmat.2014.06.035

Web of Science ID:

ISI:000340689100057

Соавторы в МНС:

Другие поля

Поле	Значение
Month	AUG 15
Publisher	ELSEVIER SCIENCE BV
Address	PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS
Language	English
EISSN	1873-3336
Keywords-Plus	DENSITY-FUNCTIONAL THEORY; CATALYZED DECHLORINATION; AROMATIC-SUBSTITUTION; CHEMICAL-REACTIVITY; GAS-CHROMATOGRAPHY; CONTAMINATED SOIL; REDUCTIVE DECHLORINATION; MOLECULAR-STRUCTURE; HOMO-LUMO; FT-IR
Research-Areas	Engineering; Environmental Sciences \& Ecology
Web-of-Science-Categories	Engineering, Environmental; Environmental Sciences
Author-Email	gorbunova@ios.uran.ru
ResearcherID-Numbers	Subbotina, Julia/L-7131-2016
ORCID-Numbers	Subbotina, Julia/0000-0002-2227-0787
Funding-Acknowledgement	Ural Branch of Russian Academy of Sciences {[}12-M-34-2036]
Funding-Text	This research was supported financially by the Ural Branch of Russian Academy of Sciences (project no 12-M-34-2036).
Number-of-Cited-References	58
Usage-Count-Last-180-days	1
Usage-Count-Since-2013	12
Journal-ISO	J. Hazard. Mater.
Doc-Delivery-Number	AN6FA