Journal of Physical Chemistry p. 7142 - 7146 (1994)
Update date:2022-08-11
Topics:
Holroyd, Richard A.
Schwarz, Harold A.
Stradowska, Elizabeth
Ninomiya, Shiro
Itoh, Kengo
Nishikawa, Masaru
The rate constants for attachment of excess electrons to 1,3-butadiene (ka) and detachment from the butadiene anoin (kd) in n-hexane are reported.The equilibrium constant, Keq = ka/kd, increases rapidly with pressure and decreases as the temperature increases.At -7 deg C attachment is observed at 1 bar.At high pressures the attachment rate is diffusion controlled.The activation energy for detachment is about 21 kcal/mol; detachment is facilitated by the large entropy of activation.The reaction volumes for attachment range from -181 cm3/mol at 400 bar to -122 cm3/mol at 1500 bar and are largely attributed to the electrostriction volume of the butadiene anion (Δ<*>el).Values of Δ<*>el) calculated by a model, which includes a glassy shell of solvent molecules around the ion, are in agreement with experimental reaction volumes.The analysis indicates the partial molar volume of the electron in hexane is small and probably negative.It is shown that the entropies of reaction are closely related to the partial molar volumes of reaction.
View MoreTianjin SPHINX SCIENTIFIC LAB.
Contact:+86-022-66211289
Address:Tianda high-tech Park. No.80,the 4th Avenue
Shanghai Dynamic Industrial Co.,Ltd.
website:http://www.shdynamic.com
Contact:86-021 3392 6680
Address:Room 805 Information Tower, No.1403 Minsheng Road, Pudong New Area, Shanghai 200135, P. R. China
Contact:+44 (0)161 367 9441
Address:
Xi'an Tizan Tech & Industry Co., Ltd.
Contact:86-18629066522
Address:C3009 TANG FENG INTERNATIONAL PLAZA, NO.18 FENGHUI NAN ROAD, XI'AN HIGH TECH ZONE, 710075 CHINA.
FOSHAN NANHAI ZHONGNAN PHARMACEUTICAL FACTORY
Contact:0086-0757-85609331
Address:XIAHENGTIAN INDUSTRIAL ZONE,SHAYONG VILLAGE,LISHUI TOWN
Doi:10.1055/s-0040-1707117
(2020)Doi:10.1021/op500109v
(2014)Doi:10.1021/ja0710858
(2007)Doi:10.1021/jo01257a022
(1969)Doi:10.1021/acscatal.8b02610
(2018)Doi:10.1021/ja208544g
(2012)