Solutions phase boundaries

The exchange of charge carriers in the molecular sphere at the zinc/electrolyte solution phase boundary corresponds to equal anodic and cathodic currents. These compensate each other in the case of equilibrium. 

Various methods have been employed for the determination of E of liquid and solid metals. Besides purely electrochemical ones (e.g. measurement of the differential double layer capacity (see also chapter 4.2)) further techniques have been used for the investigation of the surface tension at the solid/electrolyte solution phase boundary. The employed methods can be grouped into several families based on the meas-... 

Trasatti has calculated the potentials of several organic, solvents from Volta potentials and the partial surface potentials on the mercury solution phase boundaries at the potential of zero charge. ... 

If the corrosive medium is an electrolyte solution, the resulting corrosion reactions are electrochemical. This means that material transport in the form of metal ions and charge exchange in the form of electrons take place at the metal-solution phase boundary because of the conductivity caused in the liquid phase by mobile anions and cations and the electron conductivity of the metals. 

The discussion focuses on two broad aspects of electrical phenomena at interfaces in the first we determine the consequences of the presence of electrical charges at an interface with an electrolyte solution, and in the second we explore the nature of the potential occurring at phase boundaries. Even within these areas, frequent reference will be made to various specialized treatises dealing with such subjects rather than attempting to cover the general literature. One important application, namely, to the treatment of long-range forces between surfaces, is developed in the next chapter. 

Figure A2.4.12 shows the two possibilities that can exist, m which the Galvani potential of the solution, (jig, lies between ( )(I) and ( )(n) and in which it lies below (or, equivalently, above) the Galvani potentials of the metals. It should be emphasized that figure A2.4.12 is highly schematic in reality the potential near the phase boundary in the solution changes initially linearly and then exponentially with distance away from the electrode surface, as we saw above. The other point is that we have assumed that (jig is a constant in the region between the two electrodes. This will only be true provided the two electrodes are iimnersed in the same solution and that no current is passing.

In fact, some care is needed with regard to this type of concentration cell, since the assumption implicit in the derivation of A2.4.126 that the potential in the solution is constant between the two electrodes, caimot be entirely correct. At the phase boundary between the two solutions, which is here a semi-pemieable membrane pemiitting the passage of water molecules but not ions between the two solutions, there will be a potential jump. This so-called liquid-junction potential will increase or decrease the measured EMF of the cell depending on its sign. Potential jumps at liquid-liquid junctions are in general rather small compared to nomial cell voltages, and can be minimized fiirther by suitable experimental modifications to the cell. 

At low currents, the rate of change of die electrode potential with current is associated with the limiting rate of electron transfer across the phase boundary between the electronically conducting electrode and the ionically conducting solution, and is temied the electron transfer overpotential. The electron transfer rate at a given overpotential has been found to depend on the nature of the species participating in the reaction, and the properties of the electrolyte and the electrode itself (such as, for example, the chemical nature of the metal). 

Glassification of Phase Boundaries for Binary Systems. Six classes of binary diagrams have been identified. These are shown schematically in Figure 6. Classifications are typically based on pressure—temperature (P T) projections of mixture critical curves and three-phase equiHbria lines (1,5,22,23). Experimental data are usually obtained by a simple synthetic method in which the pressure and temperature of a homogeneous solution of known concentration are manipulated to precipitate a visually observed phase. 

In the case of solution phase studies, it is clear where we should draw a boundary between the parts of a system that ought to be studied quantum-mechanically and those that can be treated by the techniques of molecular mechanics. 

Once-through boilers may be either sub- or super-critical. Sub-critical boilers are clearly at some potential risk of on-load corrosion owing to the presence of the evaporator zone. Measures aimed at avoiding on-load corrosion include—keeping the overall solute concentration low, keeping the ionic balance matched, and maintaining the waterside oxide suitably thin. With super-critical plant, there is no chance of on-load corrosion whilst it is operating in the super-critical mode, as there is no phase boundary. The risk is present, however, when the plant is run in the sub-critical mode, as all super-critical plant must be at times. 

Ion-selective bulk membranes are the electro-active component of ion-selective electrodes, which sense the activity of certain ions by developing an ion-selective potential difference according to the Nernst equation at their phase boundary with the solution to be measured. The main differences to biological membranes are their thickness and their symmetrical structure. Nevertheless they are used as models for biomembranes. 

At each phase boundary there exists a thermodynamic equilibrium between the membrane surface and the respective adjacent solution. The resulting thermodynamic equilibrium potential can then be treated like a Donnan-potential if interfering ions are excluded from the membrane phase59 6,). This means that the ion distributions and the potential difference across each interface can be expressed in thermodynamic terms. 

This value does not express the actual result since side and/or parallel reactions (e.g., H+ or 02 reduction) are not considered, but it does demonstrate the completeness of the cementation process and the effectiveness of this liquid-liquid extraction. During this extraction no external current flows through the phase boundary Hg (amalgam)/solution thereby establishing a potentiometric condition. The question of the potential difference at the phase boundary can be answered by constructing the experimentally accessible current-voltage curves for the reactions ... 

The presupposition is that parallel electrochemical reactions (i.e., ion or electron transfer) occur across the phase boundary, if the measured ions and interfering ions are both present in the solution. A redox process in which electrons pass the phase boundary is also considered an interfering electrochemical reaction. 

Figure 6. Metal (zinc)/ electrolyte solution (zinc sulfate) phase boundary in the equilibrium state.

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