Search PubMedSearch

PubMed · 8368534

Improved data-processing method for atomic absorption spectroscopy with electrothermal atomization.

Abstract

A new approach is described for processing transient data from electrothermal atomizers used in atomic absorption spectroscopy. The transient responses are first integrated and then a pseudo-first-order model is fit to the time-dependent integrals in order to predict the response that would be measured if the atomization process were monitored to completion. The principal advantage expected and observed for the new approach is its ability to reduce effects of variables such as atomization temperature. For all elements studied (Cr, Mn, K, Yb, Fe), the new predictive approach is shown to be virtually independent of temperature in the range from 2200 to 2600 degrees C. The predictive approach exhibited lower temperature coefficients than either the peak-height or peak-area options for all elements examined. For the more volatile elements (Mn, K, Yb, Fe), the improvement ratio at 2400 degrees C of the predictive approach relative to the others ranged from 1.4 to 8.2. For chromium at 2400 degrees C, the temperature coefficient of the predictive method was approximately 10- and 30-fold lower than those for the peak-area and peak-height options, respectively.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

C Hsiech, H L Pardue. 1993-07-15. Improved data-processing method for atomic absorption spectroscopy with electrothermal atomization.. https://doi.org/10.1021/ac00062a003

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

Background-subtraction of fast-scan cyclic staircase voltammetry at protein-modified carbon-fiber electrodes.

Background-subtraction techniques were applied to the voltammetry of nicotinamide adenine dinucleotide (NADH) at protein-modified carbon-fiber microelectrodes. The background currents at carbon-fiber electrodes were stable and voltammetric scans immediately before or after the analyte were effectively used for background subtraction. Digital step-potential waveforms were used to excite these carbon-fiber electrodes, where the resulting voltammetric analysis assessed the optimal switching and initial potentials and the electrochemical response time was determined. The initial potential was 0.0 V and the switching potential 1.1 V (versus Ag/AgCl) and the response time was approximately 300 ms. Some sensitivity to NADH was lost and voltammetric prescans were required at protein-modified electrodes to obtain a stable baseline. Current versus time was assessed by the average current of the faradaic region from each voltammogram and by differential current; the average current minus the current from a non-faradaic potential range. Differential current assessments discriminated against artifacts caused by pH (as high as 1.0 pH unit) and ionic strength flux (100 mM). These background-subtraction techniques allowed the faradaic information to be obtained quickly and conveniently while maximizing sensitivity and maintaining selectivity.

Electrochemistry

Electrochemical studies of S-nitrosothiols.

S-nitrosothiols (RSNO), such as SNAP, GSNO, and Glc-SNAP-1 exhibited a single, totally irreversible, diffusion controlled reduction peak at potentials of -0.97 V, -0.98 V and -0.91 V, respectively, vs. Ag/AgCl (3 M NaCl) reference electrode. This corresponded to the nitric oxide (NO) release from the S-nitrosothiols. A possible mechanism is proposed for the reduction process.

Electrochemistry

Spectroscopic and electrochemical evaluation of a perfluorosulfonated ionomer and its gel as preconcentrating media for [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane.

The interaction of [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane, a nonradioactive analogue of a heart imaging agent, with Nafion gel, which is Nafion plasticized with tri-n-butyl phosphate, has been evaluated spectroscopically and electrochemically. Thin-layer spectroelectrochemistry on the rhenium compound yields a linear Nernst plot with an n value of 0.99 and E degree' of 0.049 V vs Ag/AgCl. The electrochemistry is consistent with a reversible one-electron transfer between the mono- and dicationic forms of the complex. The UV-visible spectrum of electrogenerated [ReII(DMPE)3]2+ is identical to that obtained by air oxidation of [ReI(DMPE)3]+. Thin, free-standing films of Nafion gel and Nafion that were sufficiently clear to record visible spectra were cast. Spectroscopic measurement of the partitioning of [ReI-(DMPE)3]+ from aqueous solution into these films shows a more rapid uptake of the complex by the Nafion gel. Preconcentration factors into Nafion gel and Nafion were 350 and 50, respectively, after 4 h of soaking. Cyclic voltammetry of 1.0 x 10(-4)-1.0 x 10(-7) M (ReI(DMPE)3]+ in 0.15 M supporting electrolyte aqueous solution at bare gold and spectroscopic graphite electrodes suggests that the complex adsorbs to these electrodes. By comparison, the well-defined cyclic voltammograms at Nafion gel-modified electrodes exhibit diffusion-controlled behavior. The formal reduction potential at Nafion gel-modified electrodes is shifted positively compared to bare electrodes. A current enhancement of approximately 4 was observed at Nafion gel-modified spectroscopic graphite over a bare electrode. A calibration plot of peak current for differential pulse voltammetry vs concentration at Nafion gel-modified spectroscopic graphite was linear in the 10(-7)-10(-5) M concentration range, with a detectable signal down into the 10(-9) M range.

Electrochemistry