%0 Journal Article %1 Kaiser:2007p3602 %A Kaiser, E. W %A Donahue, C. J %A Pala, I. R %A Wallington, Timothy J %A Hurley, M. D %D 2007 %J Journal of Physical Chemistry A %K Alkenes, Allyl, Cl-Atoms, Mechanisms, No3, Radicals Rotation, Series, %N 7 %P 1286--1299 %R 10.1021/jp067317r %T Kinetics, products, and stereochemistry of the reaction of chlorine atoms with cis- and trans-2-butene in 10-700 torr of N-2 or N-2/O-2 diluent at 297 k %U http://www.google.com/search?client=safari&rls=en-us&q=Kinetics,+products,+and+stereochemistry+of+the+reaction+of+chlorine+atoms+with+cis-+and+trans-2-butene+in+10-700+torr+of+N-2+or+N-2/O-2+diluent+at+297+k&ie=UTF-8&oe=UTF-8 %V 111 %X The reactions of Cl atoms with cis- and trans-2-butene have been studied using FTIR and GC analyses. The rate constant of the reaction was measured using the relative rate technique. Rate constants for the cis and trans isomers are indistinguishable over the pressure range 10-900 Torr of N-2 or air and agree well with previous measurements at 760 Torr. Product yields for the reaction of cis-2-butene with Cl in N-2 at 700 Torr are meso-2,3-dichlorobutane (47%), dl-2,3-dichlorobutane (18%), 3-chloro-1-butene (13%), cis-1-chloro-2-butene (13%), trans-1-chloro-2-butene (2%), and trans-2-butene (8%). The yields of these products depend on the total pressure. For trans-2-butene, the product yields are as follows: meso-2,3-dichlorobutane (48%), dl-2,3-dichlorobutane (17%), 3-chloro-1-butene (12%), cis-1-chloro-2-butene (2%), trans-1-chloro-2-butene (16%), and cis-2-butene (2%). The products are formed via addition, addition-elimination from a chemically activated adduct, and abstraction reactions. These reactions form (1) the stabilized 3-chloro-2-butyl radical, (2) the chemically activated 3-chloro-2-butyl radical, and (3) the methylallyl radical. These radicals subsequently react with Cl-2 to form the products via a proposed chemical mechanism, which is discussed herein. This is the first detailed study of stereochemical effects on the products of a gas-phase Cl+olefin reaction. FTIR spectra (0.25 cm(-1) resolution) of meso- and dl-2,3-dichlorobutane are presented. The relative rate technique was used (at 900 Torr and 297 K) to measure: k(Cl + 3-chloro-1-butene) = (2.1 +/- 0.4) x 10(-10), k(Cl + 1-chloro-2-butene) = (2.2 +/- 0.4) x 10(-10), and k(Cl + 2,3-dichlorobutane) = (1.1 +/- 0.2) x 10(-11) cm(3) molecule(-1) s(-1).

@article{Kaiser:2007p3602, abstract = {The reactions of Cl atoms with cis- and trans-2-butene have been studied using FTIR and GC analyses. The rate constant of the reaction was measured using the relative rate technique. Rate constants for the cis and trans isomers are indistinguishable over the pressure range 10-900 Torr of N-2 or air and agree well with previous measurements at 760 Torr. Product yields for the reaction of cis-2-butene with Cl in N-2 at 700 Torr are meso-2,3-dichlorobutane (47%), dl-2,3-dichlorobutane (18%), 3-chloro-1-butene (13%), cis-1-chloro-2-butene (13%), trans-1-chloro-2-butene (2%), and trans-2-butene (8%). The yields of these products depend on the total pressure. For trans-2-butene, the product yields are as follows: meso-2,3-dichlorobutane (48%), dl-2,3-dichlorobutane (17%), 3-chloro-1-butene (12%), cis-1-chloro-2-butene (2%), trans-1-chloro-2-butene (16%), and cis-2-butene (2%). The products are formed via addition, addition-elimination from a chemically activated adduct, and abstraction reactions. These reactions form (1) the stabilized 3-chloro-2-butyl radical, (2) the chemically activated 3-chloro-2-butyl radical, and (3) the methylallyl radical. These radicals subsequently react with Cl-2 to form the products via a proposed chemical mechanism, which is discussed herein. This is the first detailed study of stereochemical effects on the products of a gas-phase Cl+olefin reaction. FTIR spectra (0.25 cm(-1) resolution) of meso- and dl-2,3-dichlorobutane are presented. The relative rate technique was used (at 900 Torr and 297 K) to measure: k(Cl + 3-chloro-1-butene) = (2.1 +/- 0.4) x 10(-10), k(Cl + 1-chloro-2-butene) = (2.2 +/- 0.4) x 10(-10), and k(Cl + 2,3-dichlorobutane) = (1.1 +/- 0.2) x 10(-11) cm(3) molecule(-1) s(-1).}, added-at = {2010-06-22T19:38:37.000+0200}, affiliation = {Univ Michigan, Dept Nat Sci, Dearborn, MI 48128 USA}, author = {Kaiser, E. W and Donahue, C. J and Pala, I. R and Wallington, Timothy J and Hurley, M. D}, biburl = {https://www.bibsonomy.org/bibtex/2b52ac268f4e509a9bdc098040147a62f/gsmith}, date-added = {2010-05-05 17:07:46 -0400}, date-modified = {2010-05-19 13:33:50 -0400}, doi = {10.1021/jp067317r}, interhash = {33409e35d410281a953c05f2b6deb6a1}, intrahash = {b52ac268f4e509a9bdc098040147a62f}, journal = {Journal of Physical Chemistry A}, keywords = {Alkenes, Allyl, Cl-Atoms, Mechanisms, No3, Radicals Rotation, Series,}, language = {English}, local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Journal%20of%20Physical%20Chemistry%20A/2007/Journal%20of%20Physical%20Chemistry%20A,%20111,%201286-1299%202007.pdf}, month = Jan, number = 7, pages = {1286--1299}, pmid = {000244225000018}, rating = {0}, timestamp = {2010-06-22T19:38:58.000+0200}, title = {Kinetics, products, and stereochemistry of the reaction of chlorine atoms with cis- and trans-2-butene in 10-700 torr of N-2 or N-2/O-2 diluent at 297 k}, uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p3602}, url = {http://www.google.com/search?client=safari&rls=en-us&q=Kinetics,+products,+and+stereochemistry+of+the+reaction+of+chlorine+atoms+with+cis-+and+trans-2-butene+in+10-700+torr+of+N-2+or+N-2/O-2+diluent+at+297+k&ie=UTF-8&oe=UTF-8}, volume = 111, year = 2007 }