Steady-state current measurements

Most SECM measurements involve steady-state current measurements. This can be a significant advantage in the measurement of kinetics, even for rapid processes, because factors like double-layer charging and adsorption do not contribute to the observed currents. However, one can also carry out transient measurements, recording iT as a function of time. This can be of use in measurements of homogeneous kinetics (Chapter 7) and for systems that are changing with time. It can also be used to determine the diffusion coefficient, D, of a species without knowledge of the solution concentration or number of electrons transferred in the electrode reaction (23). 

Cu2+ at a 25 /Am diameter Pt UME located 1.0 /Am from a copper sulfate pentahydrate (100) face in an area of the crystal with a low dislocation density. The experimental characteristics have been normalized using the steady-state current measured at effectively infinite probe-crystal separation, i(oo) = 1.88 /aA. DCu2+ = 4.56... 

Figure 5. Cuirent-potential curve for GOD-PBT electrode, dqmsition charge 4 mC cnr. Steady-state currents measured using 10 mmol dm glucose solution in 0.1 mol dm phosphate buffer, pH 7.0, at 25°C, flow rate 1 ml min ... 

This section will explore the quantitative behavior of current-potential curves (voltammetry) and steady-state current measurements in flowing solution prior to considering liquid chromatographic assays. A similar examination of quiet solutions is reserved for the section on in vivo measurements. (In this and all subsequent voltammetry discussions, only oxidation reactions are treated, not because reductions are unimportant, but because there are to date few, if any, neurochemical applications.)... 

The samples were characterised under steady state condition. All the electrical properties and the emission spectra were measured at room temperature imder ambient atmosphere. Steady state current measurements on samples were performed using the high voltage Keithley Source Measurement Unit SMU 236. The EL spectra were obtained using the Perkin-Elmer LS50B. 

Sittampalam and Wilson described the preparation and use of an amperometric sensor for glucose. " The sensor is calibrated by measuring the steady-state current when it is immersed in standard solutions of glucose. A typical set of calibration data is shown in the following table. 

A 2.00-mb sample of a solution containing an unknown amount of glucose is diluted to 10 mb in a volumetric flask, and a steady-state current of 23.6 is measured. What is the concentration of glucose in the sample in milligrams per 100 mb ... 

The effect of increasing y is to increase the diffusion coefficient of the solute in phase 2 compared to that in phase 1. For a given value of this means that when a SECMIT measurement is made, the higher the value of y the less significant are depletion effects in phase 2 and the concentrations at the target interface are maintained closer to the initial bulk values. Consequently, as y increases, the chronoamperometric and steady-state currents increase from a lower limit, characteristic of an inert interface, to an upper limit corresponding to rapid interfacial solute transfer, with no depletion of phase 2. 

The interfacial transfer kinetics were then investigated by perturbing the equilibrium, through the depletion of Cu + in the aqueous phase, by reduction to Cu at an UME located in close proximity to the aqueous-organic interface. This process promoted the transfer of Cu into the aqueous phase, via the transport and decomplexation of the cupric ion-oxime complex, resulting in an enhanced steady-state current at the UME. Approach curve measurements of i/i oo) vs. d allowed the kinetics of the transfer process to be determined unambiguously [9,18]. 

In the second category, SECMIT has been used to probe the relative permeability of oxygen between water and DCE or NB, with no supporting electrolyte present in any phase. Under the conditions employed, direct voltammetric measurements in the organic phase would be impractical due to the high solution resistivity (DCE or NB) or limitations of the solvent window available (NB). Figure 24 shows the steady-state current for the... 

According to Eq. (1) the steady-state current across a micro-ITIES is proportional to the bulk concentration of the transferred species. Thus, the micro-ITIES can function as an amperometric ion-selective sensor. Similarly, the peak current in a linear sweep voltam-mogram of ion egress from the micropipette obeys the Randles-Sevcik equation. Both types of measurements can be useful for analysis of small samples [18a]. 

A microhole-based ITIES has been used by Osborne et al. for amperometric determination of ionic species in aqueous solutions [12]. They studied the assisted ammonium transfer with DB1816 at the water-DCE interface. Because the concentration of iono-phore in the organic phase was high, the measured steady-state current was proportional to the concentration of ammonium in the aqueous phase. The time required to reach a steady state was relatively short (e.g., 5 s for an 11/xm hole). A linear relationship was found between the steady-state plateau current and the ammonium concentration over the range 1 to 500/aM. 

In the direct-reading instruments the emf of the cell is led through an (operational) amplifier across a standard high resistor yielding a current that is measured by a milliammeter calibrated to be read in pH units or millovolts. So, while the null-point system provides a truly potentiometric (non-faradaic) measurement where the off-balance adjustment remains limited to an interrupted temporary current draw-off, the direct-reading system represents an amperometric measurement where a continuous steady-state current draw-off takes place as long as the meter is switched on. In fact, the latter is a deflection method as a pointer indicates the pH units or millivolts by its deflection on the meter scale. 

This type of electrode is a particularly powerful analytical tool since by performing steady-state measurements alone, it can measure faster rate constants than any other method. For a second-order reaction, the RRDE can reliably and reproducibly determine rate constants as fast as 10 mol dm ) s, while the maximum first-order rate constant measurable with the RRDE is about 10 s . A further advantage of the RRDE is the way that steady-state currents are measured (see below), whereas other methods of determining such high values ofk require the measurement of transients. 

In general it will be necessary to measure via impedance measurements using a four electrode cell. A schematic diagram of the cell which would be used for such measurements is shown in Fig. 10.15. The expected behaviour will be as described in Eqn (10.3) except that Warburg impedances can arise from either or both phases. An example of an impedance spectrum of the H2O/PVC interface is shown in Fig. 10.16. The application of a constant overpotential will, in general, lead to a slowly decaying current with time due to the concentration changes which occur in both phases, so that steady state current potential measurements will be of limited use. 

Biochemical oxygen demand (BOD) is one of the most widely determined parameters in managing organic pollution. The conventional BOD test includes a 5-day incubation period, so a more expeditious and reproducible method for assessment of this parameter is required. Trichosporon cutaneum, a microorganism formerly used in waste water treatment, has also been employed to construct a BOD biosensor. The dynamic system where the sensor was implemented consisted of a 0.1 M phosphate buffer at pH 7 saturated with dissolved oxygen which was transferred to a flow-cell at a rate of 1 mL/min. When the current reached a steady-state value, a sample was injected into the flow-cell at 0.2 mL/min. The steady-state current was found to be dependent on the BOD of the sample solution. After the sample was flushed from the flow-cell, the current of the microbial sensor gradually returned to its initial level. The response time of microbial sensors depends on the nature of the sample solution concerned. A linear relationship was foimd between the current difference (i.e. that between the initial and final steady-state currents) and the 5-day BOD assay of the standard solution up to 60 mg/L. The minimum measurable BOD was 3 mg/L. The current was reproducible within 6% of the relative error when a BOD of 40 mg/L was used over 10 experiments [128]. 

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