20 1, Fundamental 1.6 ELECTROCHEMICAL CELLS Electrochemical cells (see Chapter 2) are divided into two sub-types, galvanic and elec- trolytic. Galvanic cells ate those whose reactions are spontaneous (AG < 0) when the electrodes are connected via a conductor (i.e., a copper wire), while an electrolytic cell requires a potential in excess of its OCP to be applied in order to drive an electrochemi- cal process (¢.g., non-spontancous, AG = 0), In order to better describe the composition of an electrochemical cell, a notation system has been devised to represent both the indi- vidual components of the cell and the phases in which they reside, A comma separates components that exist within the same phase in this system, and phase boundaries are rep- resented by a single slash mark. Phase boundaries that possess a potential that is consid- cred to be a negligible component of the overall cell potential (ic, a salt bridge) are depicted with a double slash. The activities or concentrations of all species should also be specified, and the cell is always written from the anode (at left) to the cathode (at right). For example, a copper plating electrolytic cell comprised from copper and platinum elec- twodes immersed in an aqueous solution containing H,SO, and CuSO, (Figure 1.4) would be written as Cu/Cu", 1", SOF Pt (6a) If the cell contained two divided chambers linked by a KCI salt bridge, with the first con- taining the platinum electrode in CuCl, and the second containing the copper electrode in HCI, it would then be written as CH! Cu" Pt 62) Electrolytic processes are used by the pharmaceutical industry (electrochemical synthe- sis) and heavily by the metal-refining industry where they represent the only currently uti- lized means of production of aluminum fzom alumina ore. These industial electrolytic processes, by some estimates, use a significant fraction of the electricity produced world- wide today (5). Power supply cl Cathode co Figure 1.4 An electrolytic electrochemical cell (for colour version: see colour section atthe end of the book). Sur tam bai: www.daihoc.com.vn,1.6 Blectrochemical Cells a Figure 15 A galvanic electoc! the book). jal cell, (for colour version; see colour section atthe end of ‘The schematic depiction of Volta's battery (Section 1.1), which is composed of stacked copper and zine disks separated by paper soaked in an acidic solution (Figure 1.5), could be represented as, olla 10a (Co (1.6.3) ‘This is an example of a primary (non-rechargeable) cell, Other types of important galvanic cells include secondary (rechargeable) cells and fuel cells. I should be noted that when a secondary galvanic cell is being recharged, it becomes an electrolytic cell, because a potential is being applied in order to reverse the direction of the spontaneous electro- chemical reaction, While it may suffice to describe the electrodes of a galvanic cell as simply an anode or cathode, electrodes in electrolytic cells are called on to perform more specialized roles. In ‘order to differentiate the electrodes, they are labeled according to their specific role in the cell: the working electrode (WE), the reference electrode (RE). and the counter electrode (CE), also known as the auxiliary electrode. The use of these labels helps to avoid confu- sion since in some experiments, where the direction of current flow reverses periodically, the WE and CE alternate between acting as anode and cathode. ‘The WE, typically a cathode, is generally where the reaction of interest occurs. Typical WEs (see Chapters 5 and 6) include the noble metals (especially gold and platinum), car- bon (including pyrolytic carbon, glassy carbon, catbon paste, nanotubes, and vapor- deposited diamond), liquid metals (mercury and its amalgams), and semiconductors (indiuim-tin oxide, Si, see Chapter 9). WEs can be chemically modified (see Chapter 8) in ‘order to increase their sensitivities toward specific species (i. become chemical sensors) or to decrease the potential required to drive a particular reaction (i.e. catalysis) Regardless of whether an electrolytic cell is of the two-electrode or three-electrode con- figuration, it must contain a reference electrode, typically classified as an anode. The RE (see Chapter 4) is composed of a system of phases, which retain an essentially constant composition, and therefore provides a stable potential by which the WE potential can be ‘monitored, The phases present in REs undergo reversible redox processes at a very high rate, enabling them to rapidly adjust to changes in the solution’s ionic activity, but leaving them sensitive to the passage of large current densities, For some systems, where there are ‘no major fluctuations of ionic activity, a noble metal electrode (e.g., a platinum wire) may Sur tam bai: www.daihoc.com.vn,2 1, Fundamental be substituted for the reference electrode. In this case, the substitute is referred to as @ quasi-reference electrode. ‘Since REs can be damaged by the presence of large current densities and may lose their ideal non-polarizable behavior, a three-electrode configuration is often used. The third electrode, called the CE/auxiliary electrode, is provided as a current sink to shunt excess curtent away from the RE. The CE is generally chosen to be inert under the reaction con- ditions ((e., a large-area noble metal electrode such as platinum is common), and may be placed in a separate cell joined by a sintered glass frit for experiments where very large currents are generated, 1.7. CELL RESISTANCE; CAPACITANCE; UNCOMPENSATED RESISTANCE Two types of current may flow in an electrochemical cell, faradaic and non-faradaic. All currents that are ereated by the reduction and/or oxidation of chemical species in the cell are termed faradaic currents. Faradaic currents may be described by the following equation: dod — ari , gM anF any where Q [Cl] isthe charge, t [sec] is the time, n is the number of electrons transferred, F is Faraday’s constant, and Nis the number of moles reacted. All other current is deemed non- faradaic in nature, and is directly related to Obm’s law: viv RZ 72) where i [A] is the current, V [V] is the potential, R [Q) is the resistance, and Z [0] is the impedance. While the resistance is applicable when considering Ohm's law in an electri- cal citcuit, the application to an electrochemical cell requires the usage of impedance, which includes elements of resistance and capacitance. In order to describe the effects of resistance and electrode capacitance in electrochemi- cal cells, it is useful to introduce the concept of the ideal polarizable electrode (IPE). The IPE (Figure 1.6) is one that will not pass any charge across the solution/metal interface when the potential across it is changed. The behavior of the IPE then mimics that of @ capacitor in an electrical circuit, with the one difference being that the capacitance of an Figure 1.6 The ideal polarizable electrode in theory (dashed line) and in practice (solid line). Sur tam bai: www.daihoc.com.vn,1.7 Cell Resistance; Capacitance; Uncompensated Resistance 2 IPE will be dependent on the potential placed across it, while for a normal capacitor it will not. In Figure 1.6 the dashed line depicts how close a real electrode can come to behaving as an IPE over a limited potential range. Above and below that range, the real electrode ‘will begin to pass a charge. Therefore within that specific potential range, the real elec- ‘ode will mimic the IPE and behave as a capacitor. The electrode/solution interface itself is thought of as an electrical double layer com- posed of the electrical charge atthe surface of the electrode itself and the charge of the ions disbursed in the solution at a small distance from the electrode surface. This double layer is formed when a potential is applied to the electrode and causes a charging current (non- faradaic current) to pass through the cell. The solution half of the double layer can be ‘thought of as being made up of distinet sub-layers (Figute 1.7). The first layer consists of solvent molecules and specifically adsorbed (desolvated) ions. The locus of the electrical centers of this layer is termed the boundary of the inner Helmholtz plane (IHP) and lies at a distance of 7%, from the electrode surface. The second layer consists of solvated ions. Since these ions arc completely surrounded by solvent molecules, they may approach no closer than 7, and the locus of the electrical charges from these ions is known as the outer Helmholtz plane (OHP). Ions that remain solvated are termed non-specifically adsorbed, ‘and may only approach up to the OHP, The interactions of non-specitically adsorbed ions ‘with the electwode surface only involve long-range electrostatics and are independent of chemical properties, The ionic species in this plane are less compact than the IHP and are disbursed in a three-dimensional region called the diffuse layer, which extends well into the bulk of the solution. During most electrochemical experiments, only the reaction occurring at one electrode, usually the WE, is of interest. In these cases, an IPE is paired with an electrode whose behavior approaches that of an ideal non-polarizable electrode (e.g., an RE). When the potential is measured between the WE (IPE) and the RE, there will be a voltage drop ‘observed that is equivalent to iR,, as given by Ohm's law. 73) Solvated wittin 7 Lome, Figure 1.7 The electrical double layer (adapted from reference (3), with permission). (for colour version: see colour section atthe end of the book). Sur tam bai: www.daihoc.com.vn,4 1. Fundamentals ‘where i [Al is the current passing through the cell and R, [9] isthe solution resistance. For systems where iR, is small (< 1-2 mV) a two-electrode system may be used. If i, is larger, two-electrode cell may still be used, but it will require a smaller current. The usage of an ultramicroelectrode (UME, Chapter 6), with diameter <50 jum, will result in a drastic decrease in current. Currents measured in systems with UMES are typically in the nA=pA (10-%-10" A) range. Therefore, with a UME even non-polar solvents can be utilized without breaking the 2 mV bartier (R, of 2 M&2 and i of 1 nA give 2 mV of potential drop) For cases where if, cannot be kept below 2 mV, a three-electrode cell must be used Usually potentiometric applications employ two-electrode cells, whereas three-clectrode cells improve results for voltammetry and amperometry. The third electrode is a CE and is used as a current sink for the cell (Figure 1.8) Inthe three-electrode cell, the majority of the current passes between the WE and the CE, which lowers the potential drop resulting from ik, measured between the RE and the WE, but does not completely eliminate it. If the cell is pictured as a potentiometer (Figure 1.9), the solution resistance (R,) can be split into two components, termed the compensated resistance (R,) and the uncompensated resistance (R,), one of which (R.) can be eliminated from the measurement based on the positioning of the RE. By positioning the RE as close as possible to the WE, a majority of R, can be eliminated. In some cases (e.g., where an organic solvent is used) the total resis- tivity of the solution cannot be minimized sufficiently through the placement of the RI due to the low conductivity (i.e, higher R,) of the solvent itself. In these cases ultramicro- electrodes are generally required, since their very much smaller area greatly reduces the current, which reduces the overall value of i, ® I|He poy fd i [a 1 Figure 18 Schematic representation of two-electrode (left) and three-electrode (right) electro- chemical cells, (for colour Version: see colour section atthe end ofthe book) nn weeWVWVVWVVWVV0 CE — Rt 2p —— RE Figure 1.9 Schematic representation ofan electrochemical cell as a potentiosta, ‘Suu tim béi: www.daihoc.com.vn