Potentiostatic electrolytic measurement

Fig. 22. Pressure composition isotherms of Pd (10 nm) capped YHx (500 nm) determined from potentiostatic electrolytic (A) and QCM ( ) measurements. For comparison the isotherms for bulk Y are also depicted (Griessen et al.,...

While taking these facts into consideration, this section deals with the estimation of Li transport number by the combination of the complex impedance and potentiostatic polarization measurements on the polymer electrolyte sandwiched between two lithium electrodes. As the polymer electrolytes we used three types of amorphous network polymers. The first was the PEO network polymer in which LiC104 was dissolved [91]. The second was the polyelectrolyte-type PEO network polymer, in which Li ions were introduced as counterions of the anion sites fixed to the polymer backbone. The third was the network polymer from PEO-grafted polydimethylsiloxane... 

There is no difference between galvanostatic and potentiostatic polarisation experiments regarding the iR potential drop between the specimen and the tip of the probe used for measuring the electrochemical potential. In either case corrections should be made for accuracy. These could be quite large if the current density is high and/or the conductivity of the electrolyte is low. 

The low conductivity of high-purity water makes it difficult to study electrode processes potentiostatically, since too high an electrical resistance in the circuit can affect the proper functioning of a potentiostat, and it can also introduce large iR errors. The increase in conductivity of water with temperature has been measured and /7 -corrected polarisation data have been obtained in hot water that originally had very low conductivity at room temperature. Other results in high-temperature water are all for tests where the conductivity was deliberately increased through the addition of electrolytes. 

Figure 13. Schematic diagram of the measurement of the ionic conductivity of a conducting polymer membrane as a function of oxidation state (potential), (a) Pt electrodes (b) potentiostat (c) gold minigrid (d) polymer film (e) electrolyte solution (0 dc or ac resistance measurement.133 (Reprinted with permission from J. Am Chem Soc. 104, 6139-6140, 1982. Copyright 1982, American Chemical Society.)...

Spectroelectrochemical Cell Figure 5.4 shows spectroelectrochemical cells used in electrochemical SFG measurements. An Ag/AgCl (saturated NaCl) and a Pt wire were used as a reference electrode and a counter electrode, respectively. The electrolyte solution was deaerated by bubbling high-purity Ar gas (99.999%) for at least 30 min prior to the electrochemical measurements. The electrode potential was controlled with a potentiostat. The electrode potential, current, and SFG signal were recorded by using a personal computer through an AD converter. 

Under potentiostatic conditions, the photocurrent dynamics is not only determined by faradaic elements, but also by double layer relaxation. A simplified equivalent circuit for the liquid-liquid junction under illumination at a constant DC potential is shown in Fig. 18. The difference between this case and the one shown in Fig. 7 arises from the type of perturbation introduced to the interface. For impedance measurements, a modulated potential is superimposed on the DC polarization, which induces periodic responses in connection with the ET reaction as well as transfer of the supporting electrolyte. In principle, periodic light intensity perturbations at constant potential do not affect the transfer behavior of the supporting electrolyte, therefore this element does not contribute to the frequency-dependent photocurrent. As further clarified later, the photoinduced ET... 

Emersion has been shown to result in the retention of the double layer structure i.e, the structure including the outer Helmholtz layer. Thus, the electric double layer is characterised by the electrode potential, the surface charge on the metal and the chemical composition of the double layer itself. Surface resistivity measurements have shown that the surface charge is retained on emersion. In addition, the potential of the emersed electrode, , can be determined in the form of its work function, , since and represent the same quantity the electrochemical potential of the electrons in the metal. Figure 2.116 is from the work of Kotz et al. (1986) and shows the work function of a gold electrode emersed at various potentials from a perchloric acid solution the work function was determined from UVPES measurements. The linear plot, and the unit slope, are clear evidence that the potential drop across the double layer is retained before and after emersion. The chemical composition of the double layer can also be determined, using AES, and is consistent with the expected solvent and electrolyte. In practice, the double layer collapses unless (i) potentiostatic control is maintained up to the instant of emersion and (ii) no faradaic processes, such as 02 reduction, are allowed to occur after emersion. 

In 1980 Bemhardsson et introduced an automated electrochemical method for CPT determination. The specimen is mounted as described in Section IV.2 (ii) using a stream of argon to avoid crevice corrosion and 0.02-5% sodium chloride as electrolyte. The CPT is determined by a potentiostatic test method using an instrument called the Santron CDT 400 for potential control, temperature control, and current measurements. 

V°rev = 1.229V is the standard state reversible potential for the water splitting reaction and Vaoc is the anode potential at open circuit conditions. Term Vmeas-Vaoc arises from the fact that Voc represents the contribution of light towards the minimum voltage needed for water splitting potential (1.229V) and that the potential of the anode measured with respect to the reference electrode Vmeas has contributions from the open circuit potential and the bias potential applied by the potentiostat (i.e. Vmeas= Vapp+Vaoc). The term Vmeas-Vaoc makes relation (3.6.16) independent of the electrolyte pH and the type of reference electrode used. Thus the use of V°rev in relation (3.6.16) instead of VV or V°hz as in the case of relation (3.6.15) is justified. 

Most often, the electrochemical impedance spectroscopy (EIS) measurements are undertaken with a potentiostat, which maintains the electrode at a precisely constant bias potential. A sinusoidal perturbation of 10 mV in a frequency range from 10 to 10 Hz is superimposed on the electrode, and the response is acquired by an impedance analyzer. In the case of semiconductor/electrolyte interfaces, the equivalent circuit fitting the experimental data is modeled as one and sometimes two loops involving a capacitance imaginary term in parallel with a purely ohmic resistance R. 

It is usual in electrochemical measurements to control the potential of the working (or indicator) electrode or the electrolytic current that flows through the cell. A potentiostat is used to control electrode potential and a galvanostat is used to control electrolytic current. Operational amplifiers play important roles in both of these. 

This would be accomplished by immersing the chemically modified electrode, a reference electrode, and an auxiliary electrode into an appropriate electrolyte solution (e.g., 0.1 M NaC104 in acetonitrile). The potential difference between the modified electrode (the working electrode) and the reference would then be adjusted to a value appropriate to drive this reaction, using a commercially available potentiostat, and the resulting anodic current would be measured. 

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