The response of thermionic/nitrogen-phosphorus detection (TID) to a series
of organophosphonate esters has been studied. The response of TID is found
to decrease with the increase in the alkyl chain length of the molecules. A
n attempt has been made to propose the response mechanism of TID for these
compounds. The charge carriers accountable for the response do not necessar
ily arise by combustion of the molecule but by a reaction involving alkali
metal and the compound. This has been supported by thermodynamic parameters
and molecular descriptors. The mechanism of the reaction that appears to b
e bimolecular has been explained by steric effects. The study successfully
explains the observed change in the response of TID with minor changes in s
tructures of the molecules. (C) 2001 Elsevier Science B.V. All rights reser
ved.