A new pulsed name photometer detector (PFPD) design is described with
improved performance, Detection limits of 180 fg/s (sulfur), 7 fg/s (p
hosphorus), and 2 pg/s (nitrogen) are demonstrated when 2 rms noise is
considered as the detection limit. The minimum detected amount of sul
fur was further reduced with a sulfur doping method to about 30 fg/s,
The factors affecting the selectivity are analyzed in terms of operati
ng the PFPD as a specific detector without any hydrocarbon interferenc
es, The effect of the pulsed nature of the PFPD on the chromatographic
peak area and height reproducibility is modeled and analyzed, It is s
hown that above 3 Hz, the standard deviation of peak area is 2%, which
is dominated by nondetector effects, The detector temperature effect
was studied and is presented. The difference between light guide and l
ens optics is discussed. The column operation with hydrogen as a carri
er gas is compared to that with helium, and the injection of chlorinat
ed and fluorinated solvents is shown and discussed. New ways of obtain
ing additional information by using the added dimension of time are an
alyzed. It is shown how the simultaneous use of dual gates can provide
unambiguous heteroatom identification, It is also described how a dua
l gate subtraction method results in a considerable enhancement of the
interheteroatom selectivity, especially for phosphorus versus sulfur.
The dual gate approach also provides up to an order of magnitude incr
ease in the measurement dynamic range, Practical utilization of the PF
PD is illustrated with the analysis of real-world samples, including t
hiophene in benzene, pesticides in a broccoli extract, and a sulfur-co
ntaining drug in human serum.