Electrode second order

Sometimes a metal electrode may be directly responsible to the concentration of an anion which either gives rise to a complex or a precipitate with the respective cations of the metal. Therefore, they are termed as second-order electrodes as they respond to an ion not directly involved in the electron transfer process. The silver-silver chloride electrode, as already described in Section 16.3.1.1.3, is a typical example of a second-order electrode. In this particular instance, the coated Ag wire when dipped in a solution, sufficient AgCl dissolves to saturate the layer of solution just in contact with the respective electrode surface. Thus, the Ag+ ion concentration in the said layer of solution may be determined by the status of the solubility product (Kvfa equilibrium ... 

An insoluble salt electrode (also called a second-order electrode) consists of a metal covered by a porous layer of its insoluble salt. The whole assembly is immersed in asolution containing a corresponding anion. For example, a silver-silver chloride electrode is denoted Ag(s) AgCl(s) CH the electrode potential is a combination of the equation analogous to Eq. (7), and the solubility product of a sparingly soluble salt, Vs(AgCl) = fl(Ag+). fl(CH), is shown in Eq. (14) ... 

The difficulty that can arise with the cells comprising the first- and second-order electrodes noted above is whether oxidized and reduced species of more than one redox couple are present in solution so that they can contribute to the overall equilibrium potential that is thus a mixed potential. Such a measurement can have low selectivity in some real situations. This can be overcome by measuring the difference of potential across a membrane composed from a material that can selectively participate at ionic exchange equilibria. 

The role of the traditional internal reference electrode is adopted in CWEs by a redox couple at the support/polymer interface (e.g., the potential of a Pt-based CWE is dependent on the concentration of oxygen) or by a second-order electrode formed on this interface (in the case of Ag or Cu substrates). Reliable, response is obtained in the concentration range 10 to 10" M and lifetimes of over 6 months have been achieved. Frequent recalibration is necessary since the potential drift is typically 5 mV/day. 

The measurement of a from the experimental slope of the Tafel equation may help to decide between rate-determining steps in an electrode process. Thus in the reduction water to evolve H2 gas, if the slow step is the reaction of with the metal M to form surface hydrogen atoms, M—H, a is expected to be about If, on the other hand, the slow step is the surface combination of two hydrogen atoms to form H2, a second-order process, then a should be 2 (see Ref. 150). 

Table 26 shows some steps in the chronological sequence of compilations, which are evidently related to improvements in the preparation and control of electrode surfaces. In second order, the control of the cleanliness of the electrolyte solution has to be taken into consideration since its effect becomes more and more remarkable with solid surfaces. A transfer of emphasis can in fact be recognized from Hg (late 1800s) to sp-metals, to sd-metals, to single-crystal faces, to d-metals, although a sharp chronological separation cannot be made. 

This is an example of a reversible reaction the standard electrode potential of the 2PS/PSSP + 2c couple is zero at pH 7. The oxidation kinetics are simple second-order and the presence of a radical intermediate (presumably PS-) was detected. Reaction occurs in the pH range 5 to 13 with a maximum rate at pH 6.2, and the activation energy above 22 °C is zero. The ionic strength dependence of 2 afforded a value for z Zg of 9 from the Bronsted relation... 

For adsorbates on a metal surface, an SFG spectmm is a combination of resonant molecular transitions plus a nonresonant background from the metal. (There may also be a contribution from the water-CaF2 interface that can be factored out by following electrode potential effects see below.) The SFG signal intensities are proportional to the square of the second-order nonlinear susceptibility [Shen, 1984] ... 

A semi-empirical, second-order response lag is used. This consists of a first-order lag equation representing the diffusion of oxygen through the liquid film on the surface of the electrode membrane... 

Such electrodes are described as Class II or second order. ... 

An alternative electrochemical method has recently been used to obtain the standard potentials of a series of 31 PhO /PhO- redox couples (13). This method uses conventional cyclic voltammetry, and it is based on the CV s obtained on alkaline solutions of the phenols. The observed CV s are completely irreversible and simply show a wave corresponding to the one-electron oxidation of PhO-. The irreversibility is due to the rapid homogeneous decay of the PhO radicals produced, such that no reverse wave can be detected. It is well known that PhO radicals decay with second-order kinetics and rate constants close to the diffusion-controlled limit. If the mechanism of the electrochemical oxidation of PhO- consists of diffusion-limited transfer of the electron from PhO- to the electrode and the second-order decay of the PhO radicals, the following equation describes the scan-rate dependence of the peak potential ... 

More complicated reactions that combine competition between first- and second-order reactions with ECE-DISP processes are treated in detail in Section 6.2.8. The results of these theoretical treatments are used to analyze the mechanism of carbon dioxide reduction (Section 2.5.4) and the question of Fl-atom transfer vs. electron + proton transfer (Section 2.5.5). A treatment very similar to the latter case has also been used to treat the preparative-scale results in electrochemically triggered SrnI substitution reactions (Section 2.5.6). From this large range of treated reaction schemes and experimental illustrations, one may address with little adaptation any type of reaction scheme that associates electrode electron transfers and homogeneous reactions. 

Figure 4.12 A solid-state electrode showing a second-order response. The electrode shown in Figure 4.11 can be modified by the incorporation of silver chloride into the membrane to enable the activity of chloride ions in a sample to be measured. A surface reaction between the test chloride ions and the membrane silver ions alters the activity of the latter, resulting in a change in the potential difference across the membrane.

Most electrode reactions of interest to the organic electrochemist involve chemical reaction steps. These are often assumed to occur in a homogeneous solution, that is, not at the electrode surface itself. They are described by the usual chemical kinetic equations, for example, first- or second-order reactions and may be reversible (chemical reversibility) or irreversible. 

Using a different convention, a simple metal in contact with its cations is also commonly termed an electrode of the first kind, or a class I or first-order electrode, while an electrode covered with an insoluble salt, e.g. AgCI I Ag for determining u(Cr), is termed an electrode of the second kind, or a class II or second-order electrtxle. In this latter convention, inert electrodes fur following redox reactions (cf. Chapter. 4) are somewhat confusingly termed redox electrodes. 

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 order to determine the net current flowing, i, as a function of q (and in some cases time) it is generally necessary to work with three or four electrode cells where the electrode of interest (the working electrode) carries current into the cell and a second electrode (the auxiliary or subsidiary electrode) carries the current out of the cell. The third electrode is the reference electrode although in cases where one of the phases is not a metal a second reference electrode is required (four electrode cell). 

Reactions (2.205) and (2.206) are called second-order cathodic stripping reactions [134]. If the reacting ligand has a tendency to adsorb on the electrode snrface, the following mechanisms are encountered [136,137] ... 

Here, cp = (E —E ) is a dimensionless potential and rs = 1 cm is an auxiliary constant. Recall that in units of cm s is heterogeneous standard rate constant typical for all electrode processes of dissolved redox couples (Sect. 2.2 to 2.4), whereas the standard rate constant ur in units of s is typical for surface electrode processes (Sect. 2.5). This results from the inherent nature of reaction (2.204) in which the reactant HgL(g) is present only immobilized on the electrode surface, whereas the product is dissolved in the solution. For these reasons the cathodic stripping reaction (2.204) is considered as an intermediate form between the electrode reaction of a dissolved redox couple and the genuine surface electrode reaction [135]. The same holds true for the cathodic stripping reaction of a second order (2.205). Using the standard rate constant in units of cms , the kinetic equation for reaction (2.205) has the following form ... 

The second-order reaction with adsorption of the ligand (2.210) signifies the most complex cathodic stripping mechanism, which combines the voltammetric features of the reactions (2.205) and (2.208) [137]. For the electrochemically reversible case, the effect of the ligand concentration and its adsorption strength is identical as for reaction (2.205) and (2.208), respectively. A representative theoretical voltammo-gram of a quasireversible electrode reaction is shown in Fig. 2.86d. The dimensionless response is controlled by the electrode kinetic parameter m, the adsorption... 

SWV has been applied to study electrode reactions of miscellaneous species capable to form insoluble salts with the mercury electrode such as iodide [141,142], dimethoate pesticide [143], sulphide [133,144], arsenic [145,146], cysteine [134, 147,148], glutathione [149], ferron (7-iodo-8-hydroxyquinolin-5-sulphonic acid) [150], 6-propyl-2-thiouracil (PTU) [136], 5-fluorouracil (FU) [151], 5-azauracil (AU) [138], 2-thiouracil (TU) [138], xanthine and xanthosine [152], and seleninm (IV) [153]. Verification of the theory has been performed by experiments at a mercury electrode with sulphide ions [133] and TU [138] for the simple first-order reaction, cystine [134] and AU [138] for the second-order reaction, FU for the first-order reaction with adsorption of the ligand [151], and PTU for the second-order reaction with adsorption of the ligand [137]. Figure 2.90 shows typical cathodic stripping voltammograms of TU and PTU on a mercuiy electrode. The order of the... 

This reaction scheme involves the second-order homogeneous disproportionation of NO2. It was stated that the rate of the latter process is independent of the electrode material, the supporting electrolyte, the presence of oxygen, and the pH of the solution. 

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