Chemical potential electrolytes

Aqueous electrolyte chemical potentials are described on the moial scale. To nlustrate the additional issues that enter into the thermodynamic interpretation of individual ion activity coefficients and chemical potentials and the relation of these to actual electrolyte experimental measurement, we briefly review the properties of the system NaCl(aq), that is, NaCl dissolved in water. [For a detailed discussion, see. e.g., Denbigh, 1971 Hamed and Owen, 1959 Klotz, 1964 Robinson and Stokes, 1959). 

Once electroneutrality applies, it is no longer necessary to describe the system in terms of electrochemical potential, and the only quantities experimentally available then become the electrolytes chemical potentials. On the other hand, if one wishes to describe media that demonstrate a deviation from electroneutrality, for instance interfacial zones in electrochemistry, then the concept of electrochemical potential becomes a very useful tool... 

We conclude this section by discussing an expression for the excess chemical potential in temrs of the pair correlation fimction and a parameter X, which couples the interactions of one particle with the rest. The idea of a coupling parameter was mtrodiiced by Onsager [20] and Kirkwood [Hj. The choice of X depends on the system considered. In an electrolyte solution it could be the charge, but in general it is some variable that characterizes the pair potential. The potential energy of the system... 

This is Kirkwood s expression for the chemical potential. To use it, one needs the pair correlation fimction as a fimction of the coupling parameter A as well as its spatial dependence. For instance, if A is the charge on a selected ion in an electrolyte, the excess chemical potential follows from a theory that provides the dependence of g(i 2, A) on the charge and the distance r 2- This method of calculating the chemical potential is known as the Gimtelburg charging process, after Guntelburg who applied it to electrolytes. 

The electrochemical potential, )T, of a species is a function of the electrical state as well as temperature, pressure, and composition is the absolute activity, which can be broken down into three parts as shown. Eor an electrolyte. A, which dissociates into cations and v anions, the chemical potential of the electrolyte can be expressed by... 

In contrast chemical and electrolytic polishing enables a smooth level surface to be produced without any residual stress being developed in the surface because the surface is removed by dissolution at relatively low chemical potential and at relatively low rates is such a way that metallic surface asperities are preferentially removed. For this to be most effective the solution properties must be optimised and the pretreatment must leave an essentially bare metal surface for attack by the electrolyte. 

The electrolyte is sandwiched between two electrodes which have different but precisely known chemical potentials for the electroactive species. Since no overall current is allowed to pass the external electric circuit (i.e., =0), integration of Eq. 

Chemically active plastics such as the polyelectrolytes have been used to make artificial muscle materials. This is an unusual type of mechanical power device that creates motion by the lengthening and shortening of fibers made from a chemically active plastic by changing the composition of the surrounding liquid medium, either directly or by the use of electrolytic chemical action. Obviously this form of mechanical power generation is no competitor to thermal energy sources, but it is potentially valuable in detector equipment that would be sensitive to the changing... 

For a strong electrolyte such as HC1 we assume that all of the electrolyte is dissociated to form the ionic species. In this case, it is appropriate to consider the chemical potential of the HC1 as the sum of the chemical potentials of the dissociated species. That isdd... 

In concentrated NaOH solutions, however, the deviations of the experimental data from the Parsons-Zobel plot are quite noticeable.72 These deviations can be used290 to find the derivative of the chemical potential of a single ion with respect to both the concentration of the given ion and the concentration of the ion of opposite sign. However, in concentrated electrolyte solutions, the deviations of the Parsons-Zobel plot can be caused by other effects,126 279"284 e.g., interferences between the solvent structure and the Debye length. Thus various effects may compensate each other for distances of molecular dimensions, and the Parsons-Zobel plot can appear more straight than it could be for an ideally flat interface. 

No. Because that would imply we know how to split, at least conceptually, the electrochemical potential, jl, of electrons (which is the same in the metal and in the electrolyte at their contact) into the chemical potential of electrons, p, and the electrical potential of electrons, (p, in the metal and in the electrolyte. 

In equilibrium dialysis of a solution of a polyanion (valence Zp negative) with molar concentration Cp against a solution of imi-imivalent electrolyte CA (C = cation, A = anion) with molar concentration Cqa it was shown that the requirement for equal chemical potentials of the salt in the polyanion (a) and diffusate ()) phases results in the following relation... 

For diffusion in liquid electrolytes such as molten salts, two forces acting on an ion of interest should be taken into account the gradient of the chemical potential and the charge neutrality. Thus the electrochemical potential rather than the chemical potential should be the driving force for diffusion. 

The general way in which a Galvani potential is established is similar in all cases, but special features are observed at the metal-electrolyte interface. The transition of charged species (electrons or ions) across the interface is possible only in connection with an electrode reaction in which other species may also be involved. Therefore, equilibrium for the particles crossing the interface [Eq. (2.5)] can also be written as an equilibrium for the overall reaction involving all other reaction components. In this case the chemical potentials of aU reaction components appear in Eq. (2.6) (for further details, see Chapter 3). 

Like its chemical potential, the activity of an individnal ion cannot be determined from experimental data. For this reason the parameters of electrolyte activity % and mean ionic activity are nsed, which are defined as follows ... 

It is typical that in Eq. (3.23) for the EMF, all terms containing the chemical potential of electrons in the electrodes cancel in pairs, since they are contained in the expressions for the Galvani potentials, both at the interface with the electrolyte and at the interface with the other electrode. This is due to the fact that the overall current-producing reaction comprises the transfer of electrons across the interface between two metals in addition to the electrode reactions. 

Electrode potentials (as well as values of the EMF of galvanic cells) depend on the composition of the electrolyte and other phases of variable composition. The electrode potential corresponds to the Galvani potential of the electrode-electrolyte interface, up to a constant term f =(Po + const. Introducing the concendation dependence of the chemical potential p into Eq. (3.21), we find that... 

Nucleation Consider an idealized spherical nucleus of a gas with the radius on the surface of an electrode immersed in an electrolyte solution. Because of the small size of the nucleus, the chemical potential, of the gas in it will be higher than that ( To) in a sufficiently large phase volume of the same gas. Let us calculate this quantity. 

The activity coefficient of the solvent remains close to unity up to quite high electrolyte concentrations e.g. the activity coefficient for water in an aqueous solution of 2 m KC1 at 25°C equals y0x = 1.004, while the value for potassium chloride in this solution is y tX = 0.614, indicating a quite large deviation from the ideal behaviour. Thus, the activity coefficient of the solvent is not a suitable characteristic of the real behaviour of solutions of electrolytes. If the deviation from ideal behaviour is to be expressed in terms of quantities connected with the solvent, then the osmotic coefficient is employed. The osmotic pressure of the system is denoted as jz and the hypothetical osmotic pressure of a solution with the same composition that would behave ideally as jt. The equations for the osmotic pressures jt and jt are obtained from the equilibrium condition of the pure solvent and of the solution. Under equilibrium conditions the chemical potential of the pure solvent, which is equal to the standard chemical potential at the pressure p, is equal to the chemical potential of the solvent in the solution under the osmotic pressure jt,... 

A great many electrolytes have only limited solubility, which can be very low. If a solid electrolyte is added to a pure solvent in an amount greater than corresponds to its solubility, a heterogeneous system is formed in which equilibrium is established between the electrolyte ions in solution and in the solid phase. At constant temperature, this equilibrium can be described by the thermodynamic condition for equality of the chemical potentials of ions in the liquid and solid phases (under these conditions, cations and anions enter and leave the solid phase simultaneously, fulfilling the electroneutrality condition). In the liquid phase, the chemical potential of the ion is a function of its activity, while it is constant in the solid phase. If the formula unit of the electrolyte considered consists of v+ cations and v anions, then... 

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