Electrochemical cells electrical potentials

If a solution forms part of an electrochemical cell, the potential of the cell, the current flowing through it and its resistance are all determined by the chemical composition of the solution. Quantitative and qualitative information can thus be obtained by measuring one or more of these electrical properties under controlled conditions. Direct measurements can be made in which sample solutions are compared with standards alternatively, the changes in an electrical property during the course of a titration can be followed to enable the equivalence point to be detected. Before considering the individual electrochemical techniques, some fundamental aspects of electrochemistry will be summarized in this section. 

Fig. 6-1. Electrochemical cell, electric charge flow in a closed cell circuit, and electron levels of two electrodes in an open cell circuit M = electrode S = electrolyte solution a, = real potential of electrons in electrode, e.Ji -electromotive force.

Each electrode reaction, anode and cathode, or half-cell reaction has an associated energy level or electrical potential (volts) associated with it. Values of the standard equilibrium electrode reduction potentials E° at unit activity and 25°C may be obtained from the literature (de Bethune and Swendeman Loud, Encyclopedia of Electrochemistry, Van Nostrand Reinhold, 1964). The overall electrochemical cell equilibrium potential either can be obtained from AG values or is equal to the cathode half-cell potential minus the anode half-cell potential, as shown above. 

Inside the bulk of the electrolyte, mass transport is mainly because of migration, a mechanism of ionic motion caused by the presence of an applied electric field. In the electrochemical cell the potential drop creates an electric field that is much more intense in the regions near the surface of the electrodes, but is sufficiently intense in the bulk of the electrolyte to promote the migration of the ions to the border of the diffusion layers. 

The Daniell cell is an example of a galvanic cell, in this type of electrochemical cell, electrical work is done by the system. The potential difference, between the two half-cells can be measured (in volts, V) on a voltmeter in the circuit (Figure 7.1) and the value of is related to the change in Gibbs energy for the cell reaction. Equation 7.9 gives this relationship under standard conditions, where is°ceu is the standard cell potential. 

Now that an electrochemical galvanic cell has been described in details, it is convenient at this moment to expand the thermodynamic of electrochemistiy in terms of chemical energy, which in turn, wiU be converted to electrical energy. The subsequent analytical procedure leads to the derivation of the Nemst equation, which is suitable for determining the cell electric potential when ion activities are less than unity as nonstandard conditions. 

Figure 11.2 shows a schematic illustration of an electrochemical cell. The potential difference between the anode and the cathode gives rise to a variation in the electrostatic potential through the ceU. Since the electrolyte is conducting, there is no electrical field there and the potential is constant. The potential variation happens in the so-called dipole layer close to the two electrodes and sets up strong electrical fields there. The field is set up by the electrons in the electrode (or holes for a positive electrode) and the counterions in the electrolyte—the total charge in the surface and in the screening layer in the electrolyte is the same (otherwise, there would be a field in the electrolyte). 

A special example of electrical work occurs when work is done on an electrochemical cell or by such a cell on the surroundings -w in the convention of this article). Themiodynamics applies to such a cell when it is at equilibrium with its surroundings, i.e. when the electrical potential (electromotive force emi) of the cell is... 

Migration is the movement of ions due to a potential gradient. In an electrochemical cell the external electric field at the electrode/solution interface due to the drop in electrical potential between the two phases exerts an electrostatic force on the charged species present in the interfacial region, thus inducing movement of ions to or from the electrode. The magnitude is proportional to the concentration of the ion, the electric field and the ionic mobility. 

This handbook deals only with systems involving metallic materials and electrolytes. Both partners to the reaction are conductors. In corrosion reactions a partial electrochemical step occurs that is influenced by electrical variables. These include the electric current I flowing through the metal/electrolyte phase boundary, and the potential difference A( = 0, - arising at the interface. and represent the electric potentials of the partners to the reaction immediately at the interface. The potential difference A0 is not directly measurable. Therefore, instead the voltage U of the cell Me /metal/electrolyte/reference electrode/Me is measured as the conventional electrode potential of the metal. The connection to the voltmeter is made of the same conductor metal Me. The potential difference - 0 is negligibly small then since A0g = 0b - 0ei ... 

Concentration cell corrosion occurs in an environment in which an electrochemical cell is affected by a difference in concentrations in the aqueous medium. The most common form is crevice corrosion. If an oxygen concentration gradient exists (usually at gaskets and lap joints), crevice corrosion often occurs. Larger concentration gradients cause increased corrosion (due to the larger electrical potentials present). 

The net electrochemical driving force is determined by two factors, the electrical potential difference across the cell membrane and the concentration gradient of the permeant ion across the membrane. Changing either one can change the net driving force. The membrane potential of a cell is defined as the inside potential minus the outside, i.e. the potential difference across the cell membrane. It results from the separation of charge across the cell membrane. 

In this part of Chapter 12, we study electrolysis, the process of driving a reaction in a nonspontaneous direction by using an electric current. First, we see how electrochemical cells are constructed for electrolysis and how to predict the potential needed to bring electrolysis about. Then, we examine the products of electrolysis and see how to predict the amount of products to expect for a given flow ot electric current. 

To visualize how electrochemical cells generate electrical potential differences, consider a zinc electrode dipped into a solution of zinc sulfate. From the macroscopic perspective, nothing happens. At the molecular level, however, some of the zinc atoms of the electrode are oxidized to ions ... 

Electrochemical cells can be constructed using an almost limitless combination of electrodes and solutions, and each combination generates a specific potential. Keeping track of the electrical potentials of all cells under all possible situations would be extremely tedious without a set of standard reference conditions. By definition, the standard electrical potential is the potential developed by a cell In which all chemical species are present under standard thermodynamic conditions. Recall that standard conditions for thermodynamic properties include concentrations of 1 M for solutes in solution and pressures of 1 bar for gases. Chemists use the same standard conditions for electrochemical properties. As in thermodynamics, standard conditions are designated with a superscript °. A standard electrical potential is designated E °. 

In a similar way, electrochemistry may provide an atomic level control over the deposit, using electric potential (rather than temperature) to restrict deposition of elements. A surface electrochemical reaction limited in this manner is merely underpotential deposition (UPD see Sect. 4.3 for a detailed discussion). In ECALE, thin films of chemical compounds are formed, an atomic layer at a time, by using UPD, in a cycle thus, the formation of a binary compound involves the oxidative UPD of one element and the reductive UPD of another. The potential for the former should be negative of that used for the latter in order for the deposit to remain stable while the other component elements are being deposited. Practically, this sequential deposition is implemented by using a dual bath system or a flow cell, so as to alternately expose an electrode surface to different electrolytes. When conditions are well defined, the electrolytic layers are prone to grow two dimensionally rather than three dimensionally. ECALE requires the definition of precise experimental conditions, such as potentials, reactants, concentration, pH, charge-time, which are strictly dependent on the particular compound one wants to form, and the substrate as well. The problems with this technique are that the electrode is required to be rinsed after each UPD deposition, which may result in loss of potential control, deposit reproducibility problems, and waste of time and solution. Automated deposition systems have been developed as an attempt to overcome these problems. 

If as a result of electrochemical processes, electrostatic potential gradients and electric currents can arise in different sections of a cell or whole organism, then conversely, currents or potential gradients applied from outside will produce certain changes in the cells and organisms. It is natural that these changes will depend on the electric field or current parameters. 

Measurement of electrical potential differences requires a complete electrical circuit, i.e., the electrochemical cell. An electrochemical galvanic cell consisting of all conducting phases, and among them at least one interface separating two immiscible electrolyte solutions is called for short a liquid galvanic cell. In contrast, the system composed of con-... 

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