Lawrence Berkeley National Laboratory

The fundamental characteristics of liquid electrode plasma (LEP), a pulsed plasma source for optical emission spectrometry, were investigated. Two distinct phases were observed during the process of pulsed plasma generation, namely bubble generation and active plasma discharge. The ionization efficiency of the LEP, with Mg as a representative analyte, was gauged from the ratio of Mg II 279.553 nm to Mg I 285.213 nm emission and was found to increase from about 5% to 20% in a close-to-linear fashion with the discharge voltage from 800 V to 1200 V. The Mg II/Mg I ratio of the LEP was 2.5 to 3 orders of magnitude less than that typically offered by an inductively coupled plasma (ICP) but was comparable to other solution-based glow discharges. It was found that an off-time interval of more than 150 ms between successive discharge pulses was required to obtain a stable pulse-to-pulse discharge current. Temporally resolved emissions of Mg II 279.6 nm, Mg I 285.2 nm, Fe I 373.5 nm, OH band head at 306 nm, and Hα line at 656.3 nm showed that the background species (OH band and Hα line) reached their maximum emission intensities at around 0.5 ms to 0.7 ms with respect to the onset of the discharge pulse whereas the maximum emissions were observed between 0.7 ms to 0.9 ms for analyte species (Mg and Fe lines). The electron density observed in the present work was in the range from 5.7 × 1015 cm−3 to 8.2 × 1015 cm−3, which was similar to those found in an analytical ICP. The temporal averaged OH rotational temperature was 3300 K, which was comparable to the values of an analytical ICP and solution-based glow discharges. By contrast, the temporally averaged Fe I excitation temperature was around 8900 K, which was even higher than that of an analytical ICP and roughly triple the values obtained by techniques based on glow discharge of liquid samples.