Ecm. Chen et al., Modified kinetic model of the electron-capture detector - Molecular electron affinities and electron collection modes, J CHROMAT A, 827(1), 1998, pp. 91-104
The kinetic model for electron-capture detection (ECD) has recently been ex
panded to include excited states. Multiple electron affinities for C6F6, an
thracene and tetracene have been reported in the literature. The temperatur
e dependence of the ECD response is calculated using these values and the e
xpanded two state model. Activation energies and pre-exponential terms for
kinetic rate constants are determined. The pre-exponential terms for therma
l electron attachment are compared with the maximum value calculated from t
he DeBroglie wavelength of the electron and the probability for stabilizati
on. Temperature data from different methods of electron collection are comp
ared. A general procedure for the determination of electron affinities from
ECD data is presented. The following ECD electron affinities are reported:
C6Cl6, 1.17+/-0.02 and 0.71+/-0.01; C6F5Cl, 0.96+/-0.03 and 0.82+/-0.02; C
6F5NO2, 1.52+/-0.02; C6H5NO2, 1.00+/-0.01 and m-hydroxyacetophenone, 0.74+/
-0.02 (all values in electron volts, eV). (C) 1998 Published by Elsevier Sc
ience B.V. All rights reserved.