Severity: Warning
Message: file_get_contents(https://...@pubfacts.com&api_key=b8daa3ad693db53b1410957c26c9a51b4908&a=1): Failed to open stream: HTTP request failed! HTTP/1.1 429 Too Many Requests
Filename: helpers/my_audit_helper.php
Line Number: 176
Backtrace:
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 176
Function: file_get_contents
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 250
Function: simplexml_load_file_from_url
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 1034
Function: getPubMedXML
File: /var/www/html/application/helpers/my_audit_helper.php
Line: 3152
Function: GetPubMedArticleOutput_2016
File: /var/www/html/application/controllers/Detail.php
Line: 575
Function: pubMedSearch_Global
File: /var/www/html/application/controllers/Detail.php
Line: 489
Function: pubMedGetRelatedKeyword
File: /var/www/html/index.php
Line: 316
Function: require_once
Despite the promising role of cyclopentanone as a bioderived fuel, thermodynamic and kinetic data are lacking for low temperature oxidation regimes. In this study, calculations at the CBS-QB3 level explore the subsequent reactivity that results from O-addition to 2- and 3-oxo cyclopentyl radicals, including expected reaction classes such as intra-H migration, HO-elimination, cyclic ether formation, and β-scission along with their thermodynamic parameters. Some of the rates are similar to the analogous reactions of cyclopentane, but some other reactions of cyclopentanone are very different. The carbonyl group hinders H-migration from the α' position but promotes HO-elimination. Enol peroxy formation from some hydroperoxy alkyl radicals of cyclopentanone is unexpectedly important, and so is HO-elimination by β-scission. Our calculations also indicated that at engine relevant conditions the α-RO prefers to go back to the reactants 2-oxo cyclopentyl radical and O. Therefore, the reactions resulting from HO-addition to 2-oxo cyclopentyl are also provided. The lowest barrier channel identified on the singlet surface corresponds to an unexpected intra OH-migration path concerted with ring opening. This valuable information will advance the construction of improved kinetic models for the oxidation of cylopentanone.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.jpca.9b05806 | DOI Listing |
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!