Electrochemical reaction potential

As a result of these studies on the cathodic and anodic mineral processes, the electrochemical reaction potentials for the main electron-conducting minerals were compiled (Table 2-II). 

Processing of CPC and CLPC data includes determination of the electrochemical reaction potentials that take place on the surface of an ore body. For CPC data this is done directly using the polarisation curves from the ore body for CLPC it is necessary to use additional processing and calculations. Matching these potentials with the corresponding tabulated potentials affords estimation of the mineral composition of the... 

Electrochemical reaction potentials of main ore minerals relative to a saturated calomel electrode (Ryss, 1983)... 

Determination of mineral composition of the ore body requires finding the electrochemical reaction potentials that take place on the ore body surface due to the current that is introduced. Values of the electrochemical reaction potentials correspond to the cross points of lines tangential to the flexure of the polarisation curve and the potential axis (Figs. 2-41 and 2-42). The average mineral composition of an ore body is... 

Fig. 2-52. Cathodic logging polarograms in Pechenga ore field. Kola peninsula, Russia, with lines (arrowed) showing electrochemical reaction potentials for the corresponding ions (reproduced with permission from Putikov, 1993).

Eqs. 5-30 through 5-36 indicate an increase in the cha rge-transfer and dif-fusional components of the Faradaic impedance when applied potentials V is lower than standard electrochemical reaction potential 1. With the appUed potential increase, and and reaches its miiiimiim and stabilizes at a... 

Concentration polarization occurs when a reactant is rapidly consumed at the electrode by the electrochemical reaction so that concentration gradients are established. We learned before that the electrochemical reaction potential changes with partial pressure of the reactants, and this relationship is given by the Nernst equation ... 

Although the applied potential at the working electrode determines if a faradaic current flows, the magnitude of the current is determined by the rate of the resulting oxidation or reduction reaction at the electrode surface. Two factors contribute to the rate of the electrochemical reaction the rate at which the reactants and products are transported to and from the surface of the electrode, and the rate at which electrons pass between the electrode and the reactants and products in solution. 

Activation Processes. To be useful ia battery appHcations reactions must occur at a reasonable rate. The rate or abiUty of battery electrodes to produce current is determiaed by the kinetic processes of electrode operations, not by thermodynamics, which describes the characteristics of reactions at equihbrium when the forward and reverse reaction rates are equal. Electrochemical reaction kinetics (31—35) foUow the same general considerations as those of bulk chemical reactions. Two differences are a potential drop that exists between the electrode and the solution because of the electrical double layer at the electrode iaterface and the reaction that occurs at iaterfaces that are two-dimensional rather than ia the three-dimensional bulk. 

The thermodynamics of electrochemical reactions can be understood by considering the standard electrode potential, the potential of a reaction under standard conditions of temperature and pressure where all reactants and products are at unit activity. Table 1 Hsts a variety of standard electrode potentials. The standard potential is expressed relative to the standard hydrogen reference electrode potential in units of volts. A given reaction tends to proceed in the anodic direction, ie, toward the oxidation reaction, if the potential of the reaction is positive with respect to the standard potential. Conversely, a movement of the potential in the negative direction away from the standard potential encourages a cathodic or reduction reaction. 

The two dashed lines in the upper left hand corner of the Evans diagram represent the electrochemical potential vs electrochemical reaction rate (expressed as current density) for the oxidation and the reduction form of the hydrogen reaction. At point A the two are equal, ie, at equiUbrium, and the potential is therefore the equiUbrium potential, for the specific conditions involved. Note that the reaction kinetics are linear on these axes. The change in potential for each decade of log current density is referred to as the Tafel slope (12). Electrochemical reactions often exhibit this behavior and a common Tafel slope for the analysis of corrosion problems is 100 millivolts per decade of log current (1). A more detailed treatment of Tafel slopes can be found elsewhere (4,13,14). 

In the presence of 6-iodo-l-phenyl-l-hexyne, the current increases in the cathodic (negative potential going) direction because the hexyne catalyticaHy regenerates the nickel(II) complex. The absence of the nickel(I) complex precludes an anodic wave upon reversal of the sweep direction there is nothing to reduce. If the catalytic process were slow enough it would be possible to recover the anodic wave by increasing the sweep rate to a value so fast that the reduced species (the nickel(I) complex) would be reoxidized before it could react with the hexyne. A quantitative treatment of the data, collected at several sweep rates, could then be used to calculate the rate constant for the catalytic reaction at the electrode surface. Such rate constants may be substantially different from those measured in the bulk of the solution. The chemical and electrochemical reactions involved are... 

At open-circuit, the current in the cell is 2ero, and species in adjoining phases are in equilibrium. Eor example, the electrochemical potential of electrons in phases d and P are identical. Furthermore, the two electrochemical reactions are equilibrated. Thus,... 

In general, according to Eq. (2-10), two electrochemical reactions take place in electrolytic corrosion. In the experimental arrangement in Fig. 2-3, it is therefore not the I(U) curve for one reaction that is being determined, but the total current-potential curve of the mixed electrode, E,. Thus, according to Eq. (2-10), the total potential curve involves the superposition of both partial current-potential curves ... 

An electrochemical reaction is said to be polarized or retarded when it is limited by various physical and chemical factors. In other words, the reduction in potential difference in volts due to net current flow between the two electrodes of the corrosion cell is termed polarization. Thus, the corrosion cell is in a state of nonequilibrium due to this polarization. Figure 4-415 is a schematic illustration of a Daniel cell. The potential difference (emf) between zinc and copper electrodes is about one volt. Upon allowing current to flow through the external resistance, the potential difference falls below one volt. As the current is increased, the voltage continues to drop and upon completely short circuiting (R = 0, therefore maximum flow of current) the potential difference falls toward about zero. This phenomenon can be plotted as a polarization diagram shown in Figure 4-416. 

Thus the tendency for an electrochemical reaction at a metal/solution interface to proceed in a given direction may be defined in terms of the relative values of the actual electrode potential E (experimentally determined and expressed with reference to the S.H.E.) and the reversible or equilibrium potential E, (calculated from E and the activities of the species involved in the equilibrium). 

Similarly, all points within a metal, which consists of an ordered rigid lattice of metal cations surrounded by a cloud of free electrons, are electrically neutral. Transport of charge through a metal under the influence of a potential difference is due to the flow of free electrons, i.e. to electronic conduction. The simultaneous transport of electrons through a metal, transport of ions through a solution and the transfer of electrons at the metal/solution interfaces constitute an electrochemical reaction, in which the electrode at which positive current flows from the solution to the electrode is the cathode (e.g. M (aq.) + ze M) and the electrode at which positive flows from it to the solution (e.g. M - M (aq.) -)- ze) is the anode. 

An adsorption isotherm gives the relatiortship between the coverage of an interface With an adsorbed species (the amount adsorbed) and the pressure of gas or concentration of the species in solution in electrochemical reactions the coverage will depend alisO on the potential diHbrcnce at the... 

Some emphasis has been placed inthis Section on the nature of theel trified interface since it is apparent that adsorption at the interface between the metal and solution is a precursor to the electrochemical reactions that constitute corrosion in aqueous solution. The majority of studies of adsorption have been carried out using a mercury electrode (determination of surface tension us. potential, impedance us. potential, etc.) and this has lead to a grater understanding of the nature of the electrihed interface and of the forces that are responsible for adsorption of anions and cations from solution. Unfortunately, it is more difficult to study adsorption on clean solid metal surfaces (e.g. platinum), and the situation is even more complicated when the surface of the metal is filmed with solid oxide. Nevertheless, information obtained with the mercury electrode can be used to provide a qualitative interpretation of adsorption phenomenon in the corrosion of metals, and in order to emphasise the importance of adsorption phenomena some examples are outlined below. 

Exchange Current Density (/ o) the rate of exchange of electrons (expressed as a current per unit area) between the two components of a single electrochemical reaction when the reaction is in equilibrium. The exchange current density flows only at the equilibrium potential. 

Nemst Equation the thermodynamic relationship between the equilibrium potential of an electrochemical reaction and the activities of the species involved in that reaction. 

Potential-pH Equilibrium Diagram (Pourbaix Diagram) diagram of the equilibrium potentials of electrochemical reactions as a function of the pH of the solution. The diagram shows the phases that are thermodynamically stable when a metal reacts with water or an aqueous solution of specified ions. 

Electrical methods of analysis (apart from electrogravimetry referred to above) involve the measurement of current, voltage or resistance in relation to the concentration of a certain species in solution. Techniques which can be included under this general heading are (i) voltammetry (measurement of current at a micro-electrode at a specified voltage) (ii) coulometry (measurement of current and time needed to complete an electrochemical reaction or to generate sufficient material to react completely with a specified reagent) (iii) potentiometry (measurement of the potential of an electrode in equilibrium with an ion to be determined) (iv) conductimetry (measurement of the electrical conductivity of a solution). 

The high potential of the positive electrode, on the other hand, does not allow the use of conducting metals like copper within the positive electrode. Lead can be used instead due to its passive properties caused by a (PbO 2) layer that largely protects the underlying material, but conducts the electronic current and so allows electrochemical reactions at its surface. 

Cyclic voltammetry is the most widely used technique for acquiring qualitative information about electrochemical reactions. The power of cyclic voltammetry results from its ability to rapidly provide considerable information on the thermodynamics of redox processes, on the kinetics of heterogeneous electron-transfer reactions, and on coupled chemical reactions or adsorption processes. Cyclic voltammetry is often the first experiment performed in an electroanalytical study. In particular, it offers a rapid location of redox potentials of the electroactive species, and convenient evaluation of the effect of media upon the redox process. 

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