In the Classroom

Unified Electroanalytical Chemistry: Application of the Concept of Electrochemical Equilibrium

Robert Q. Thompson* and Norman C. Craig Department of Chemistry, Oberlin College, Oberlin, OH 44074; *robert.q.thompson@oberlin.edu

Recently, through an ACS symposium (1) and an article in Analytical Chemistry (2), the analytical chemistry community has considered the concept of unified chromatographythe blurring of gas, supercritical fluid, and liquid chromatography. Proponents argue that the separation principles in each area of chromatography are essentially the same and it is the different ranges of pressure and temperature under which the experiments are conducted that lead to the artificial distinction and segregation of the topics. In our opinion the same kind of argument holds true for electroanalytical chemistry. Electrochemical cells, static electrochemical techniques (e.g. potentiometry), and dynamic electrochemical techniques (e.g. voltammetry) are usually treated as distinct, stand-alone topics. Yet all these techniques can be linked through simple thermodynamic notions, particularly the concept of electrochemical equilibrium, where in electrochemical systems the tendency for an oxidation reduction reaction to occur is balanced by the tendency of an electrical device to supply electrons. Sanger and Greenbowe have addressed significant student misconceptions in electrochemistry at the level of a first course in college chemistry (3, 4), and at least two authors have

distinguished electrochemical equilibrium from chemical equilibrium (5, 6 ). In this paper, we show that the definitions and equations related to electrochemical equilibrium parallel those of chemical equilibrium. Thus the approach builds on topics from general chemistry and allows students to construct new knowledge from what they already know. Through figures, experiments suitable for classroom demonstration, and a problem from a leading analytical chemistry textbook, we provide pedagogical support for this proposed view of electronalytical chemistry. Our aim in the undergraduate analytical chemistry classroom is to demonstrate convincingly the power and simple beauty of electrochemistry. If the applied voltage is set equal to the electrochemical cell potential, no reaction occurs (electrochemical equilibrium), and potentiometric or thermodynamic measurements can be made. Free energies and even enthalpies and entropies of reaction, if the temperature of the cell is varied, are easily and directly measured. With an applied voltage less positive or more positive than the cell potential, an electrochemical process does occur (electrochemical nonequilibrium). By altering the applied voltage, both the

Table 1. Quantities Used in This Paper

Symbol Stot Sch Ssurr T Hsurr Hch G rG z Definition Total entropy change (of the universe), measured in joules per Kelvin. Entropy change in a chemical system or the chemical part of an electrochemical system, measured in joules per Kelvin. Entropy change in the thermal surroundings, measured in joules per Kelvin. Absolute temperature of the system, measured in Kelvin. Enthalpy change in the thermal surroundings under constant atmospheric pressure, measured in joules. Enthalpy change in a chemical system or the chemical part of an electrochemical system under constant atmospheric pressure, measured in joules. Gibbs energy change for a chemical system or the chemical part of an electrochemical system, measured in joules. Reaction Gibbs energy change for a chemical system or the chemical part of an electrochemical system, measured in joules per mole reaction. Moles of reaction in the chemical system or subsystem; a positive value means that the reaction proceeds left to right in the direction as written; a negative value means that the reaction proceeds right to left, opposite to the direction as written. Free energy equivalent for the electrical part of an electrochemical system, measured in joules. Electromotive force, measured in volts, due to the chemical part of the electrochemical system; a positive value indicates pumping of electrons into the left-hand (L) electrode and out of the right-hand (R) electrode within the chemical subsystem. Voltage, measured in volts, applied by the electrical part of the electrochemical system; a positive value indicates pumping of electrons from the (+) terminal to the ( ) terminal within the electrical subsystem. Number of moles of electrons transferred per mole of reaction; always positive. Time, measured in seconds. Faraday constant (96,485 coulombs per mole of electrons). Charge in coulombs; a positive value means that the electrons flow into the ( ) terminal and out of the (+) terminal of the electrical subsystem. Electrical current, measured in amperes; a positive value means that the electrons flow into the ( ) terminal and out of the (+) terminal of the electrical subsystem.

Uel E

Vel n t F q I

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direction and rate of the electrochemical process can be controlled. Furthermore, reaction rates are calculated directly from the measurement of electrical current. Entropy Changes For this presentation we use concepts from the global formulation of thermodynamics as presented in Entropy Analysis (7 ) and traceable to ideas developed in Bents The Second Law (8). Although it is not necessary to adopt in full this formulation, it is helpful to have as background a few of
Box 1. Entropy Change in Chemistry and Electrochemistry Chemistry Stot = Sch + Ssurr Hsurr + Hch = 0
by the first law, at constant pressure

Electrochemistry Stot = Sch + Ssurr Hch + Hsurr + Uel = 0

by the first law, at constant pressure

Ssurr = Hsurr /T = Hch /T

where the entropy change in the thermal surroundings is expressed first in terms of enthalpy change in the thermal surroundings and then in terms of enthalpy change in the chemical system

where Uel is the change in energy in the electrical subsystem

Ssurr = Hsurr /T = Hch /T Uel /T

Stot = Sch Hch /T G = Hch TSch

at constant temperature and pressure

Stot = Sch Hch /T Uel /T G = Hch TSch

at constant temperature and pressure

Stot = G/T T Stot = G

Stot = G/T Uel /T T Stot = G+ Uel

the fundamental concepts. Table 1 defines the variables and quantities used in the paper. Stot, the total change in entropy, is the universal index of spontaneous change (Stot > 0) and of equilibrium (Stot = 0). It is important to note that Stot can never be less than zero in actual processes, although thermodynamic calculations of theoretical systems may lead to negative values. In such cases, the experimental outcome must be interpreted in a way that leads to a positive Stot. The proper interpretation is essential for understanding chemical and electrochemical systems, and it is mainly in this interpretation that textbook treatments and the new view presented here diverge. Typically, chemical systems have three interacting components: a chemical reaction part (ch), a thermal energy reservoir (thermal surroundings, surr), and a mechanical energy part (atmosphere in the earths gravitational field, wt).1 Contributions to the total entropy change associated with a chemical system are from the first two of these components (see Box 1); no entropy change is associated with the mechanical energy part. The Gibbs energy, G, for a chemical system has several interpretations: (i) as G, the maximum amount of useful work available from a chemical reaction; (ii) the measure of the tendency of the reaction to occur; (iii) the measure of chemical energy. In an electrochemical system, a fourth component, an electrical subsystem (el), is added to the three described above. The electrical subsystem is regarded as interacting directly with the chemical subsystem (ch) only, whereas the chemical subsystem also interacts with its surroundings, the mechanical energy reservoir and the thermal energy reservoir. Uel for the electrical subsystem is not fully parallel to G because the electrical subsystem contributes no intrinsic entropy change and has no spontaneous tendency per se. Uel is, however, like interpretations i and iii above, equivalent to the maximum available work and the measure of electrical energy. Chemical Systems Figure 1 shows the possible outcomes when in a chemical system a reactant converts to a product. A distinction is made between rG, the reaction Gibbs energy in units of joules per mole reaction, and G, the Gibbs energy in units of joules (9). The former is an intensive property that is always taken for the reaction in the direction it is written, whereas the latter is extensive. The two are interconverted through G = z rG, where z ( by IUPAC) is the change in the extent of reaction in units of moles reaction and can be either positive (movement from reactants to products) or negative (movement from products to reactants). This interpretation is a departure from standard practice in which z is regarded as a positive value only but will prove useful when electrochemical systems are discussed. Figure 1b illustrates the chemical equilibrium case. Chemical equilibrium applies when a chemical reaction and its surrounding mechanical energy and thermal energy reservoirs are in mutual equilibrium; Stot = 0 and G = 0. From the kinetics perspective, the net reaction rate is zero or dz/dt = 0 at equilibrium. When the spontaneous chemical reaction is from left to right (Fig. 1a) Stot is positive and G is negative. The net reaction rate is no longer zero; dz/dt > 0. When a chemical reaction is nonspontaneous as written, a negative Stot and positive G are calculated (Fig. 1c). Since this result is a prac929

>0 <0

<0 >0

S tot G

Spontaneous chemical reaction A B

Chemical equilibrium C D

Nonspontaneous chemical reaction E F

rG < 0 z>0
F E

r G = 0 z>0

rG < 0 z >0
E F

reverse reactants and products

rG > 0 z<0

reverse reaction arrow

Figure 1. Possible outcomes for chemical systems when a reactant converts to a product. As related to the Stot and G continua: (a) system is spontaneous as described; (b) system is at equilibrium; (c) system is nonspontaneous as described. Interpretations of the chemical system in c: (d) reaction equation is rewritten in reverse, and system is spontaneous as described; (e) reaction equation is maintained, and system is spontaneous in the reverse direction. The assignment of reactants (left side of equation) and products (right side of equation), not the direction of the reaction arrow, is a factor in the sign of rG. The arrows direction indicates the sign of z.

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tical impossibility, we may interpret the situation in one of two ways. As shown in Figure 1e, we understand that the reaction proceeds in the opposite direction. In this case, rG remains positive (regardless of which way the reaction arrow points) because the reaction is still written with reactant E and product F; the reaction arrow is reversed, indicating a negative z. Together these changes make G negative and Stot positive. Alternatively, we may write the reaction anew with reactants F and products E (see Fig. 1d). Now rG is negative and z is positive, yielding the desired negative G and positive Stot. For chemical reactions alone, these two interpretations are comparably useful. For the electrochemical system in which a chemical reaction occurs in the nonspontaneous chemical sense, only one of the two possible interpretations is desirable. Prior analysis of the simpler chemical system helps clarify the distinction. Classroom Demonstration Practicing the principle that people learn best when confronted with the concrete before the abstract (10), we introduce a classroom demonstration of an electrochemical process before describing the thermodynamic analysis. All one needs to introduce at this point is that the measured current, I, is proportional to chemical reaction rate, and thus electrochemical equilibrium is indicated by I 0. Box 2 describes an electrochemical cell that can be set up for classroom demonstration. The cell consists of a conventional three-electrode system used for electroanalytical chemistry (11)a platinum

working electrode, a silversilver chloride reference electrode, and a platinum auxiliary electrodeand a voltammograph (e.g., Bioanalytical Systems, model CV-27) that controls the voltage between the working and reference electrodes and measures the current between the working and auxiliary electrodes. We will focus on the chemical reaction at the working electrode connected to the (+) terminal of the electrical subsystem as is common practice in analytical electrochemistry. By calculation, using the Nernst equation,2 the potential E is +0.213 V for the cell reaction in Box 2. Measurement of the cell potential when a very large resistance (essentially infinite) is part of the electrical subsystem (by turning the cell mode knob on the CV-27 to the potentiometric mode) gives +0.21 V. The corresponding negative rG (= nFE = 20.3 kJ/mol) clearly indicates the chemical nonequilibrium; a spontaneous reduction is favored at the working electrode. Even so, the overall electrochemical system shows no net change, as evidenced by a nearly zero current (I 0) measured with the instruments integrated ammeter. The very large resistance prevents significant current flow and consequently prevents any significant reaction in the chemical subsystem, even though the chemical subsystem, interacting with the mechanical and thermal reservoirs, is far from chemical equilibrium. This situation is like a chemical reaction system that is thermodynamically spontaneous but kinetically frozen. Electrochemical equilibrium can be established, as evidenced by I 0, when a finite resistance is used and a voltage is applied by the electrical subsystem that exactly matches the potential of the chemical cell. Specifically, when the cell of Box 2 is activated (resistance lowered by turning the cell

Box 2. Demonstration of Electrochemical Equilibrium and Nonequilibrium

Example Cell: ( ) Ag|AgCl, 4 M KCl||Fe(CN)63 (5 10 4 M) , Fe(CN)64 (5 10 4 M) , = 0.10|Pt (+) Reaction in the half-cell connected to the (+) terminal: e + Fe(CN)63 (aq) Fe(CN)64 (aq).
E = E ferrocyanide ferrocyanide 0.05916 V mole e log E Ag/AgCl + E j ferricyanide ferricyanide 1 mole e 0.197 V + 0.010 V = +0.213 V = Vel

E = 0.356 V 0.05916 V log 0.18

Ion activity coefficients, i, are determined using the Davies model. The reference silversilver chloride electrode has a known and constant potential. The junction potential, Ej , is estimated from experiment.

Electrochemical Equilibrium First, the electrical subsystem is set such that the resistance is very large, and, thus, electrochemical equilibrium is enforced, since I 0. The measured voltage, Vel, is equal to E.
Next, the electrical subsystem is set so that the resistance is finite and Vel equals E. Electrochemical equilibrium is enforced, since G + Uel = 0. The current meter reads zero, confirming the equilibrium condition. In both cases, the electrochemical system is operating under conditions of electrochemical equilibrium even though the chemical subsystem itself is not at chemical equilibrium (since G = nFEz 0).

Electrochemical Nonequilibrium Vel is set to +0.05 V, which is < E. I > 0 (measured).

G + Uel < 0 (calculated). Use the Nernst equation to compute aferrocyanide /aferricyanide 100 at the electrode surface. A reduction occurs in the half-cell connected to the (+) terminal of the electrical subsystem in order to increase the ratio of activities from ~0.2 (at electrochemical equilibrium) to ~100.

Vel is set to +0.21 V, which is = E. I 0 (measured). G + Uel = 0 (calculated). aferrocyanide / aferricyanide 0.2 at the electrode surface This shows that electrochemical equilibrium can be re-established simply by changing the applied voltage and that the electrochemical system operates along a continuum. Vel is set to +0.35 V, which is > E. I < 0 (measured). G + Uel > 0 (calculated). Use the Nernst equation to compute aferrocyanide /aferricyanide 0.001 at the electrode surface. An oxidation occurs in the half-cell connected to the (+) terminal of the electrical subsystem in order to decrease the ratio of activities from ~0.2 (at electrochemical equilibrium) to ~0.001.

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mode knob to Cell) and the applied voltage, Vel, is set to +0.21 V (= E ), electrochemical equilibrium is established and the measured current is essentially zero. When a less positive voltage (+0.05 V) than E is applied to the cell described in Box 2, a significant positive current (several microamperes) is measured, and the electrochemical system is at nonequilibrium. In response to the voltage change, the ratio of activities at the surface of the platinum working electrode, calculated using the Nernst equation, increases from ~0.2 to ~100. To achieve this new ratio a reduction must occur at the working electrode; electrons flow out of the (+) terminal of the electrical subsystem and into the working electrode, there to be captured by the ferricyanide ion. Anion and cation movement through the chemical subsystem completes the electrical circuit. Unless the bulk activities of the reactants and products change significantly (i.e., z is assumed to be small), rG remains 20.3 kJ/mol and the effective spontaneity of the chemical subsystem is unchanged from the equilibrium case. It is Vel with respect to E that is altered to activate the electrochemical system. In a similar fashion, the applied voltage can be made more positive (+0.35 V) than the cell potential. Now a negative value appears on the ammeter. In response to the voltage change, the ratio of activities at the surface of the platinum working electrode decreases to ~0.001. To achieve this new ratio an oxidation must occur; electrons flow into the (+) terminal of the electrical subsystem from the working electrode. It is the change in Vel with respect to E that causes the direction of the reaction and the sign of the current to be reversed. Conceptual Framework for Electrochemical Systems How does one explain the changes in the sign and magnitude of the measured current when the applied voltage is varied? Let us develop answers with symbols and with pictures. As described above, the total entropy change, Stot, is the fundamental thermodynamic quantity governing change

in both chemical and electrochemical systems. Secondary quantities are G and {G + Uel}, respectively. Uel = Vel q = Vel (z n F ) G = E (z n F ) {G + Uel} = E (z n F ) + Vel (z n F ) = {Vel E } (z n F ) So, the total entropy change, the measure of the electrochemical systems spontaneity, is related to the difference between the applied voltage, Vel, and the cell potential, E. This opposition between the electrical and chemical subsystems is depicted in Figures 2 and 3. As defined in Figure 2, the electrical subsystem at positive applied voltages (curved arrow) pumps electrons from the (+) terminal and to the ( ) terminal.3 The chemical subsystem with a positive cell potential (curved arrow) pumps electrons from the R electrode and to the L electrode as result of a chemical reaction. Positive current and z > 0 are accompanied by anion flow from R to

>0 <0 0

< 0 S tot > 0 G + U el

Spontaneous electrochemical reaction

Electrochemical equilibrium

Nonspontaneous electrochemical reaction

a
R O + e

+
A + e B

b
R O + e

+
A + e B

c
R O + e

+
B

A + e

d
B A + e

+
O + e R

reverse half-cells and sign of E reverse sign of Vel z > 0; I > 0

Electrical Subsystem with Terminals Marked and +

A positive voltage, Vel, is indicated by a curved arrow from the (+) terminal to the ( ) terminal. The length of the curved arrow indicates the magnitude of local electron pumping (of Vel ). The dashed straight arrow indicates the direction of electron movement. A positive current, I, is indicated by arrows into ( ) and out of (+).

e
R O + e

+
B A + e

reverse reaction arrows reverse flow of negative charge z < 0; I < 0

Chemical Subsystem with Half-Cells L and R

A positive potential, E , is indicated by a curved arrow from R to L. The length of the curved arrow indicates the magnitude of local electron pumping (of E). The dashed, straight arrow indicates the direction of anion movement. A positive z is indicated by an arrow from R to L. In such a case, the reactants at R are reduced and at L are oxidized.

Figure 2. Diagrams and definitions of symbols for the electrical subsystem and chemical subsystem of an electrochemical system. The signs and magnitude of applied voltage Vel, electromotive force E, and the electrical current I are defined in relation to the diagrams.

Figure 3. Possible outcomes for electrochemical systems. As related to the Stot and {G + Uel} continua: (a) system is spontaneous as described; (b) system is at equilibrium; (c) system is nonspontaneous as described. Interpretations of the electrochemical system in c: (d) reaction equation is rewritten in reverse, half-cells are switched, and the signs of Vel and E are reversed; system is spontaneous as described; (e) reaction equation, Vel, and E are maintained; system is spontaneous in the reverse direction. The assignment of reactants (left side of equation) and products (right side of equation), not the direction of the reaction arrow, is a factor in the sign of rG. The arrows direction indicates the sign of z. The components of the chemical subsystems in ae are identical.

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L (dashed straight arrow). When the two subsystems are connected (see Fig. 3) the stronger electron pump wins and determines the direction of current flow. In the case where the chemical subsystem is dominant, the electrochemical system is usually termed a galvanic cell. In contrast, an electrolytic cell is defined as an electrochemical system in which the electrical subsystem is dominant. Electrochemical Equilibrium Electrochemical equilibrium applies when a coupled electrical subsystem and chemical subsystem and its surroundings are in mutual equilibrium: Stot = 0 and {G + Uel} = 0. Note the similarity to the case of a chemical system where equilibrium is indicated by Stot = 0 and G = 0. As depicted in Figure 3b, the tendency to pump negative charge from the R electrode to the L electrode in the chemical subsystem is exactly counterbalanced by the tendency to pump electrons from the (+) terminal into the ( ) terminal of the electrical subsystem. The applied voltage of the electrical system Vel equals E, the quantity related through the Nernst equation to E and the activities of species in the chemical subsystem. In other words, {Vel E } = 0. The definition of chemical equilibrium in kinetics terms is that the net number of moles of reaction per time unit (dz/dt) is zero. For an electrochemical process this translates into a current (I ) of zero (a very small current when measurement is made), since q = nzF z = q/n F dz/dt = 0 = (dq/dt) /n F = I /n F Overall, no net charge or electron movement occurs (no dashed arrows in Fig. 3b). Static electroanalytical techniques are ones that operate under conditions of electrochemical equilibrium. In potentiometry, E is found by measuring Vel (since the two are equal), and then E is used to compute the analyte activity from the Nernst equation for conventional electrochemical cells or the similar NicolskyEisenman equation for ionselective electrodes (12, p 291). All static techniques function at this special point, the zero point along a {G + Uel} continuum (Fig. 3). Electrochemical Nonequilibrium An electrochemical system is no longer at equilibrium when the chemical and electrical energy inputs are unbalanced. An electrochemical process proceeds in the direction as written when Stot is positive, {G + Uel} is negative, and more specifically, {Vel E } is negative. Again, the similarity to chemical systems (Stot > 0, G < 0) is noted. Because the direction of the reaction is forward as written, z, the moles of reaction, is positive, and the measured current is positive. Figure 3a depicts this galvanic cell case and illustrates the dominance (larger curved arrow) of the chemical subsystem; electrical energy is increased at the expense of chemical energy. The net chemical reaction is A + R B + O. Overall, negative charge flows from the R electrode to the L electrode and electrons flow into the ( ) terminal and out of the (+)

terminal of the electrical subsystem. The species A at the R electrode gains electrons through the electrical subsystem; a reduction occurs at this working electrode. When a calculated rG is positive for a chemical system, we understand that the reaction must be spontaneous in the direction opposite to what is written and two reasonable interpretations are possible (Figs. 1d and 1e). In similar fashion, interpretation is needed when {Vel E } is made positive in an electrochemical system and the calculated {G + Uel} is positive and Stot is negative. Figure 3c depicts this electrolytic cell case and illustrates the dominance (larger curved arrow) of the electrical subsystem; chemical energy is increased at the expense of electrical energy. The possible interpretations, depending on which variables are changed, are depicted in Figures 3d and 3e. Since TStot = {Vel E }(znF ) and nF is always positive, to change the sign of Stot either z must change sign or the Vel,E pair must change sign. Changing the signs of Vel and E concurrently is the conventional approach (Fig. 3d) used in analytical textbooks (and even in Entropy Analysis before our own view was transformed!). The chemical reaction is written in reverse, thus reversing the sign of E, and to comply, the sign of Vel is also reversed. The net chemical reaction is B + O A + R. While this interpretation makes Stot positive, it requires a change in sign of the experimental observable Vel even though the electrode connections to the electrical subsystem and the applied voltage dial are untouched in actual practice. Furthermore, the approach always predicts positive current values (since z is always positive), whereas in practice both positive and negative currents are measured. The disjunction between theory and practice makes this standard approach undesirable. Our alternative interpretation (Fig. 3e) is that the more positive applied voltage Vel than cell potential E causes a current to flow in a direction opposite to the current in the galvanic cell case (Fig. 3a). Electrons flow into the (+) electrode and out of the ( ) electrode; anions in the chemical subsystem flow from L to R. Current I and moles of reaction z are negative. Since the reaction is not rewritten, still A + R B + O, and since no electrical settings are altered, E and Vel are unchanged. It is the negative z that makes {G + U el} negative and Stot positive. We understand that species B at the R electrode loses electrons through the electrical system; an oxidation occurs at this working electrode. Dynamic electroanalytical techniques such as voltammetry, coulometry, and amperometry are ones that operate under conditions of electrochemical nonequilibrium, at any nonzero point along a {G + Uel} continuum (Fig. 3). In most of these techniques, current is measured and can be directly related to the analyte concentration, usually owing to control of the reaction rate by diffusion or other slow mass transport of reactants and products to and from the electrode surface. Textbook Problem A common electrochemistry problem found in texts for a first course in analytical chemistry describes an electrochemical cell and asks for its cell potential and the applied potentials for initiating reactions. An example is given below (12, p 465, problem 17-8).

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In the Classroom Consider the following cell, whose resistance is 3.50 ohms: () (0.10 M), (0.10 M), HClO4 (0.050 M), Ce4+ (0.10 M), HClO4|Pt(s) (+) Pt(s) | Fe2+ Fe3+ || Ce3+

a. What applied voltage is required to initiate a reaction in the forward direction and produce a current of 30.0 mA? Suppose that there is no concentration polarization or overpotential. b. What applied voltage is required to initiate a reaction in the reverse direction and produce a current of 30.0 mA? Suppose that there is no concentration polarization or overpotential.

does not match experimental practice. Our approach provides those answers and a straightforward, logical, unified view of electrochemical reactions, building on prior knowledge of chemical reactions and thermodynamics. Conclusions It is important to show as review, by displaying Figure 3 and demonstrating the system described in Box 2, that a small rotation of the applied voltage dial from the electrochemical equilibrium point in the direction of less positive voltage supports the spontaneous chemical reaction as writtenthat is, reduction at the working electrode, accompanied by a positive current that is related to reaction rate and analyte concentration (Fig. 3a). The chemical subsystem is the dominant electron pump, increasing the electron concentration at the ( ) electrode; electrons flow out of the (+) terminal of the electrical subsystem (positive current). Further rotation in the same direction yields increasing current until the reaction rate is limited by mass transport of reactants and products to and from the electrode surface (e.g. voltammetry). This is the realm of dynamic electrochemical techniques. The voltage dial then can be turned back so that the system again returns to electrochemical equilibrium (Fig. 3b). The electron pumps of the chemical and electrical subsystems are exactly in balanceno net current is measured. This is the domain of static electroanalytical techniques, such as potentiometry. Continued rotation of the applied voltage dial in this direction of more positive voltage again activates the electrochemical process, this time supporting the reverse chemical reaction that is, oxidation at the working electrode and a negative current (Fig. 3e). Now the electrical subsystem is the dominant electron pump; electrons flow into the (+) terminal of the electrical subsystem (negative current). Again, dynamic techniques reign. Notes
1. In Entropy Analysis the thermal reservoir is designated with rather than surr and the reactive system is designated with rather than ch. We chose to use the more familiar designations and subscripts here, in the absence of the full treatment. 2. Electrochemical reaction equations are written in the following manner. Half-reactions are written as reductions for each halfcell, with the same number of electrons in each. The half-reaction associated with the electrode connected to the ( ) terminal of the electrical part of the system is subtracted from the half-reaction associated with the electrode connected to the (+) terminal. Cell potentials are calculated in a parallel fashion: E = E(+) E( ). 3. An electrical subsystem as part of an overall electrochemical system may be conceptualized as a large, ideal capacitor, the charges on which can be altered in sign and magnitude. When electrons are added to the ( ) electrode (dashed straight arrows in Fig. 2), then Uel is positive. When electrons flow out of the ( ) electrode, then Uel is negative.

The spontaneous chemical reaction as written is Ce4+ + Fe2+ Ce3+ + Fe3+, and the reduction reaction is at the electrode connected to the (+) terminal. Students can calculate the thermodynamic potential of the cell by writing both half-reactions as reductions, consulting a table of standard reduction potentials, using the Nernst equation for half-cells, and subtracting E( ) from E(+). One gets +0.95 V, with the implicit assumption that the system is at electrochemical equilibrium and I 0. The textbook problem asks for calculation of the voltage required to overcome the cell resistance (3.50 ) and to initiate a reaction in the forward direction. A less positive applied voltage than E is necessary to initiate the current, particularly to overcome the cell resistance to current flow. The calculation is Vel = E IR = +0.95 V (0.030 A)(3.5 ) = +0.84 V An applied voltage of +0.84 V, a voltage less than E, results in a positive, +30-mA current with electrons from the electrical subsystem moving into the electrode connected to the (+) terminal to cause a reduction at that electrode. The authors analysis matches our own. The second part of the textbook problem illustrates the difference in results from using our new approach and the authors conventional approach. The author takes the view that the applied potential necessary to reverse the spontaneous chemical reaction, that is, to cause an oxidation in the half-cell connected to the (+) terminal, is 1.06 V. This comes from the calculation: 0.95 V (0.030 A)(3.5 ) = 1.06 V. Our answer differs in sign and comes from +0.95 V ( 0.030 A) (3.50 ) = +1.06 V; oxidation with 30 mA current begins at +1.06 V, where {Vel E } > 0. The discrepancy arises in the interpretation of a negative calculated Stot. As described above, our response is to maintain the written chemical reaction equation and to set z < 0. Consequently, E remains +0.95 V, and the current is negative. In the standard approach, the response is just the opposite; the sign of z is maintained positive and the sign of {Vel E } is changed to negative. However, an experimental observable is not open to interpretation; the sign of Vel cannot be reversed. The textbook approach also raises logical questions concerning the actual electrochemical experiment. For example, a less positive applied potential (+0.84 V) than E (+0.95 V) accompanies a reduction of Ce4+ in part a of the question. Yet a negative, even less-positive potential ( 1.06 V) supposedly causes an oxidation in part b. What reaction occurs in the chemical subsystem between the two limits of applied potential? At what potential does the reduction stop and oxidation begin? Answers are not forthcoming because the theoretical discussion

Literature Cited
1. Unified Chromatography; Division of Analytical Chemistry symposium; presented at the 216th National Meeting of the American Chemical Society, Boston, MA, Aug 1998; papers 155159, 170174, 180184.

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In the Classroom 2. Chester, T. L. Anal. Chem. 1997, 69, 165A169A. 3. Sanger, M. J.; Greenbowe, T. J. J. Chem. Educ. 1997, 74, 819823. 4. Sanger, M. J.; Greenbowe, T. J. J. Chem. Educ. 1999, 76, 853860. 5. Craig, N. C. J. Chem. Educ. 1986, 63, 8083. 6. Birss, V. I.; Truax, D. R. J. Chem. Educ. 1990, 67, 403409. 7. Craig, N. C. Entropy Analysis: An Introduction to Chemical Thermodynamics, VCH: New York, 1992. 8. Bent, H. A. The Second Law; Oxford University Press: New York, 1965. 9. The distinction between G, an extensive quantity, and rG, an intensive quantity, is subtle but important in discussions of electrochemistry. See DeKock, R. L. J. Chem. Educ. 1996, 73, 955956, and Craig, N.C. J. Chem. Educ. 1987, 64, 668 669. 10. Spencer, J. N. J. Chem. Educ. 1999, 76, 566569. 11. A lucid discussion of three-electrode systems and circuits for control of applied potential and measurement of current in electroanalytical techniques can be found in Kissinger, P. T.; Heineman, W. R. Laboratory Techniques in Electroanalytical Chemistry; Dekker: New York, 1984; Chapter 6. 12. Harris, D. Quantitative Chemical Analysis, 5th ed.; Freeman: New York, 1999; p 391.

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