More Accurate Measurement of Return Peak Current in Cyclic Voltammetry Using Diffusional Baseline Fitting.

The difficulty associated with accurately measuring the height of the back peak (Ipb) in cyclic voltammetry (CV) has long plagued electrochemists. Most commonly, Ipb is measured by extrapolating a linear fit from a selected region of a voltammogram after the switching potential (Eλ), but without substantial separation between the peak potential (Ep) and Eλ, this approach always overestimates the background current and so underestimates Ipb. Moreover, experimental conditions can present challenges for this method as an appropriate region for linear fitting is often lacking due to neighboring peaks or solvent electrolysis current. Here, we present a new method for finding the baseline current for the back peak in CV experiments. By examining the CV data as a function of time rather than potential, it is possible to fit a generalized Cottrell or Shoup-Szabo equation to the current decay of the forward peak and extrapolate this function as a baseline for the return peak. This approach was tested by using simulated and experimental data in a variety of conditions, including data demonstrating linear and radial diffusional control. We found that the method allows for more accurate determination of back peak currents, especially when linear fits are complicated by narrow electrochemical windows or radial diffusion. A user-friendly Python program was written to automatically find an appropriate fitting range for this analysis and measure peak currents. We have made this program available to the electrochemical community at large.

A sulphide resistant Ag|AgCl reference electrode for long-term monitoring.

Reference electrodes which demonstrate long-term potential stability are essential for many continuous monitoring applications and are commonly based on Ag|AgCl electrodes; however, these electrodes are susceptible to poisoning from aqueous sulphide species which are commonly present in wastewater and natural groundwater. This work presents a sulphide resistant solid-state reference electrode (SSRE) based on a composite material using suspended KCl electrolyte and sacrificial AgCl in a cross-linked polyvinyl acetate polymer matrix. Sulphidation of the sacrificial AgCl produces a stable Ag2S precipitate and prevents further ingress of the poisoning sulphide species through the composite material. A novel SSRE using this material is compared to a control SSRE without suspended AgCl and a typical liquid filled reference electrode. These three reference electrodes are studied using electrochemical impedance spectroscopy (EIS), and their application is also studied in potentiometric pH sensing and cyclic voltammetry (CV). The long-term sulphide resistance of the two SSREs is also studied with potentiometry, and cross-sections of these electrodes were examined using micro X-ray fluorescence (µXRF). Both SSREs demonstrated higher impedance than the liquid reference electrode but were similar to other SSREs reported in the literature. This impedance did not result a meaningful difference in potentiometric pH sensing or CV experiments done using typical scan rates. The KCl/AgCl SSRE exhibited remarkable sulphide resistance, with all samples demonstrating a stable potential without maintenance after ca. 120 days of continuous immersion in 1 g L-1 Na2S solution, whereas KCl SSRE samples all demonstrated significant drift before this time. µXRF sulphur maps revealed that suspended AgCl prevented sulphide ingress, thus protecting the embedded Ag|AgCl electrode. This work presents a reference electrode that could enable long-term monitoring in challenging sulphide solutions, and also highlights a novel approach for preventing reference electrode poisoning which could be more widely explored.

Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt FeII Spin Crossover Complexes.

A family of halogen-substituted Schiff base iron(II) complexes, [FeII (qsal-X)2 ], (qsal-X=5-X-N-(8-quinolyl)salicylaldimines)) in which X=F (1), Cl (2), Br (3) or I (4) has been investigated in detail. Compound 1 shows a temperature invariant high spin state, whereas the others all show abrupt spin transitions, at or above room temperature, namely, 295 K (X=I) up to 342 K (X=Br), these being some of the highest T1/2 values obtained, to date, for FeII N/O species. We have recently reported subtle symmetry breaking in [FeII (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [FeII (qsal-I)2 ] 4 at low temperature (T(LIESST)=54 °K). The halogen substitution effects on the magnetic properties, as well as the crystal packing of the [FeII (qsal-X)2 ] compounds and theoretical calculations, are discussed in depth, giving important knowledge for the design of new spin crossover materials. In comparison to the well known iron(III) analogues, [FeIII (qsal-X)2 ]+ , the two extra π-π and P4AE interactions found in [FeII (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.

Heteroleptic iron(iii) Schiff base spin crossover complexes: halogen substitution, solvent loss and crystallite size effects.

The influence of the halogen substituent on the qsal moiety of iron(iii) heteroleptic compounds with the formulae [Fe(qsal-X)(thsa)]·nMeCN, where qsal-X- = X-substituted quinolylsalicylaldimine; thsa2- = thiosemicarbazone-salicylaldiminate; X = F; n = 2.5, 1·2.5MeCN and X = Cl 2, Br 3 and I 4, n = 1 (labelled 2·MeCN, 3·MeCN and 4·MeCN, respectively) has been systematically investigated. Magnetic studies on solid samples show incomplete spin crossover in 1-3 which can be related to MeCN solvent loss. Complex 4·MeCN remains fully LS up to 360 K. Single crystals have been examined at variable temperatures for samples possessing different degrees of solvation. Intermolecular C-XH interactions are present for X = F, Cl and Br while a C-Iπ interaction is uniquely observed in 4·MeCN. These preferential interactions result in different supramolecular packings of the various halogen substituted compounds. However, as the LS stability increases from F to I, the ligand field strength is then also suggested to increase from F to I. Consequently, in this family, the electronic structure resulting from halogen variation is believed to influence the magnetic properties more than crystal packing effects. Mössbauer spectra, at variable temperatures, confirm the presence of Fe(iii) and the magnetic properties in these compounds. The effect of different drying methods as well as the crystal/powder effect on the magnetic properties are discussed in the case of 2·MeCN.