Negative electrodes hydrogen evolution

Three anodic partial reactions are considered active dissolution of two metals M and M with different kinetics in the absence of their ions in bulk solution and decomposition of water with the evolution of oxygen. The kinetics of the latter process is so slow on most corroding metals that only at very negative potentials can oxygen present in the solution be electroreduced and this eventually becomes limited by mass transport due to the limited solubility of oxygen in water. At even more negative potentials, hydrogen evolution takes place on the electrode surface. The cathodic reduction of some metal ions present on the electrode surface as a consequence of corrosion is also considered in Fig. 13(b). 

Unfortunately, the cathode potential required is usually rather negative, substantial hydrogen evolution occurring as a secondary reaction and suspended particles may clog or foul the electrode. For these reasons, a cheap high-surface area, carbon electrode is a preferred choice, carbon fibre being especially suitable. 

Similar reactions can be written for other metallic additives. At the negative electrode two more reactions can occur. Hydrogen evolution... 

Some battery designs have a one-way valve for pressure rehef and operate on an oxygen cycle. In these systems the oxygen gas formed at the positive electrode is transported to the negative electrode where it reacts to reform water. Hydrogen evolution at the negative electrode is normally suppressed by this reaction. The extent to which this process occurs in these valve regulated lead —acid batteries is called the recombination-efficiency. These processes are reviewed in the Hterature (50—52). 

Hydrogen oxidation according to Eq. (5) is possible above 0 V. If hydrogen evolution occurs at the negative electrode and the H2 evolved reaches the positive electrode, from the thermodynamic situation the reaction that is to be expected is ... 

The surface of the platinum electrode can be studied conveniently in the potential range between 0 and 1.7 V (RHE), where in inert solutions (not containing substances able to be oxidized or reduced), the surface is ideally polarizable. At a more negative potential, cathodic hydrogen evolution starts, whereas at more positive potentials, oxygen is evolved anodicaUy. 

The relation between E and t is S-shaped (curve 2 in Fig. 12.10). In the initial part we see the nonfaradaic charging current. The faradaic process starts when certain values of potential are attained, and a typical potential arrest arises in the curve. When zero reactant concentration is approached, the potential again moves strongly in the negative direction (toward potentials where a new electrode reaction will start, e.g., cathodic hydrogen evolution). It thus becomes possible to determine the transition time fiinj precisely. Knowing this time, we can use Eq. (11.9) to find the reactant s bulk concentration or, when the concentration is known, its diffusion coefficient. 

When such a polyfunctional electrode is polarized, the net current, i, will be given by ii - 4. When the potential is made more negative, the rate of cathodic hydrogen evolution will increase (Fig. 13.2b, point B), and the rate of anodic metal dissolution will decrease (point B ). This effect is known as cathodic protection of the metal. At potentials more negative than the metaTs equilibrium potential, its dissolution ceases completely. When the potential is made more positive, the rate of anodic dissolution will increase (point D). However, at the same time the rate of cathodic hydrogen evolution will decrease (point D ), and the rate of spontaneous metal dissolution (the share of anodic dissolution not associated with the net current but with hydrogen evolution) will also decrease. This phenomenon is known as the difference effect. 

Adsorption of surface-active substances is attended by changes in EDL structure and in the value of the / -potential. Hence, the effects described in Section 14.2 will arise in addition. When surface-active cations [NR] are added to an acidic solution, the / -potential of the mercury electrode will move in the positive direction and cathodic hydrogen evolution at the mercury, according to Eq. (14.16), will slow down (Fig. 14.6, curve 2). When I ions are added, the reaction rate, to the contrary, will increase (curve 3), owing to the negative shift of / -potential. These effects disappear at potentiafs where the ions above become desorbed (at vafues of pofarization of less than 0.6 V in the case of [NR]4 and at values of polarization of over 0.9 V in the case of I ). 

For the cathodic reduction of organic substances, electrodes of two types are used the platinum and the mercury type. Those of the first type (platinum metals, and in alkaline solutions nickel) exfiibit low polarization in hydrogen evolution their potential can be pushed in the negative direction no further than to -0.3 V (RHE). Hydrogen readily adsorbs on these electrodes, which is favorable for reduction... 

Some metals are thermodynamically unstable in aqueous solutions because their equilibrium potential is more negative than the potential of the reversible hydrogen electrode in the same solution. At such electrodes, anodic metal dissolution and cathodic hydrogen evolution can occur as coupled reactions, and their open-circuit potential (OCP) will be more positive than the equilibrium potential (see Section 13.7). 

When the potential of the magnesium electrode is made more positive, the rate of Mg+ ion formation increases, and with it that of reaction (16.5). Therefore, the rate of hydrogen evolution increases instead of falling off, with increasing anodic polarization of the magnesium (see Section 13.7). This phenomenon has become known as the negative difference effect. 

It is recognized, that the overall process consists of the catalysis of reaction 1, an intermediate step being the reduction of water. Reaction 4 can be treated as hydrogen evolution on a compact silver electrode at negative potential. Silver has a small overpotential for evolution Of the two steps of which reaction 4 is composed... 

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