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ELECTROCHEMICAL KINETICS

19.1 19.2

Introduction................................................................................................................................. Electron Transfer at Metal Electrodes...................................................................................... 19.2.1 19.2.2 19.2.3 19.2.4 19.2.5 19.2.6 Electron Transfer and Reaction Rate.......................................................................... Activation Energy for Electron Transfer.................................................................... The Butler-Volmer Equation...................................................................................... The Tafel Equations.................................................................................................... Mass Transfer Effects................................................................................................. Electrical Double Layer Effects..................................................................................

1 3 3 5 8 13 15 19 20 20 25 29 33 41 41 41 41 43 47 50 57 57 59 63 68

19.3

Redox Electrodes......................................................................................................................... 19.3.1 19.3.2 19.3.3 19.3.4 19.3.5 19.3.6 Multi-step Reactions at Metal Electrodes .................................................................. Adsorbed Intermediates and Electron Transfer.......................................................... The Hydrogen Electrode............................................................................................. The Oxygen Electrode................................................................................................ The Hydrogen Peroxide Electrode.............................................................................. The Chlorine Electrode...............................................................................................

19.4

Mixed Potentials.......................................................................................................................... 19.4.1 19.4.2 19.4.3 19.4.4 Multiple Redox Couples at an Electrode.................................................................... Surface-Controlled Kinetics........................................................................................ Mixed-Control Kinetics.............................................................................................. Transport Controlled Kinetics.....................................................................................

19.5

Electron Transfer at Semiconductor Electrodes...................................................................... 19.5.1 19.5.2 19.5.3 19.5.4 Energy Levels in Electron and Hole Transfer............................................................. Current-Potential Relations......................................................................................... Transport of Charge Carriers in Semiconductors....................................................... Redox Reactions..........................................................................................................

____________________________________________________________________________________________

19.1

Introduction

1

On the basis of the nature of the reactants and products, three main types of electrode processes may be identified: (a) ionic redox reactions, (b) gaseous redox reactions, and (c) phase change reactions. In an ionic redox electrode process (Figure 19.1a), both the reactant and product are water-soluble ionic species, although they have different charges. In gaseous redox reactions (Figure 19.1b), a reactant or a product is a gas. Examples are the oxygen, hydrogen, and the chlorine electrodes. In a typical gaseous redox process, a hydrated ion or a water molecule reacts, through adsorbed intermediates, on the electrode surface; dissolved gas molecules are produced initially, and these subsequently combine to form gas bubbles.

ee- + A2+ A

+ + 2e- + 2A

M M+

+ H 2O

A2 (g)

M(H 2O)+ n

(a)

(b)

(c)

ee - + M+ Mo M M+ + XMX (s)

M Deposit (d) (e)

MX Deposit

Figure 19.1 Types of electrode processes: (a) ionic redox reactions (b) gaseous redox reactions, (c) electrodissolution, (d) electrodeposition, (e) surface film reactions.

2

Phase change electrode processes may involve phase formation or dissolution, as illustrated in Figures 19.1c-e. In the case of electrodissolution (Figure 19.1c), a surface metal ion detaches and enters the aqueous phase as a hydrated ion; the associated electron is donated to the electrode. In electrodeposition (Figure 19.1d), a hydrated metal ion receives electrons from the electrode and the resulting electroneutral metal becomes incorporated into the crystal structure of the metallic deposit. The metal ion released during a dissolution process may combine with an aqueous species to give an insoluble product, i.e., a surface film (Figure 19.1e). In a related process, a previously formed surface film may be made to undergo dissolution. We shall limit the discussion in this Chapter to electron-transfer reactions in which the electrode is inert, i.e., cases where the electrode serves only as a source or sink for electrons, without undergoing any chemical transformation itself. Also, we will not consider here those cases where there is surface deposition. This means that the focus in this Chapter is primarily on ionic redox electrodes and gaseous electrode processes. Dissolution processes are discussed in Chapters 20 and 21 while deposition is treated in Chapters 22 and 23.

3

19.2

Electron Transfer at Metal Electrodes

19.2.1 Electron Transfer and Reaction Rate The potential of an electrode is a measure of the energy of the constituent electrons. As the electrode potential moves in the negative direction, the electrons rise to increasingly high energy levels. At sufficiently negative potentials, the energy levels occupied by the electrons become high enough to permit electron transfer from the electrode to aqueous phase species. Suppose that the working electrode has a potential E relative to a reference electrode. Suppose further, that at this applied potential, the following reaction occurs at the metal electrode surface: kf Az+ + ne- ↔ B kr

(19.1)

That is, electrons from the solid are received by an aqueous species Az+ at the solid/aqueous interface, and the subsequent reaction yields a product B. This electron transfer constitutes current flow. Since the current flow is associated with the Az+/B reaction, it is of interest to establish a quantitative relationship between reaction rate and current. When a current I flows for a time t and results in the consumption of nA moles of a species A, Faraday's law gives

nA = It/nF

(19.2)

where F is the Faraday constant, i.e., 96487 coulombs/g equiv., and n moles of electrons are involved in the reaction of 1 g mol of A; n has units of g equiv./g mol. Let us recall the definition of reaction rate on a unit surface basis (see Equation 15.7),

4

6) For the reaction occurring on a metal electrode surface (Equation 19. Then the net reaction rate is given by rA = (1/S)dnA/dt= -kfCA + krCB (19.e.5) where iA is the current density. rA = (1/S)dnA/dt = I/nFS = i/nF (19. Equation 19. A convention shall be used such that a positive current is said to flow when positive charge flows from electrode to solution.2 can be differentiated with respect to time to give.3) For constant current. let kf and kr respectively be the rate constants for the forward and reverse reactions.1 and 19. defined as i = I/S (19.1). electron generation (anodic 5 ..8) Inspection of Equations 19.6 in Equation 19.8 reveals that the forward reaction (which consumes electrons) contributes a negative current.5 gives i = -nFkf CA + nFkrCB (19.rA = (1/S)dnA/dt (19. i. whereas the reverse reaction (which releases electrons) contributes a positive current.7) Using Equation 19.4) (19.

.o exp [αnF(φ M .reaction) occurs and electrons flow from solution to electrode.e.9b) 6 .e.2 Activation Energy for Electron Transfer The activation energy of a chemical reaction can be taken as a constant at a given temperature.e. In contrast. the forward reaction of Equation 19.9a) kr = kr. This dependence of the rate constants on the potential difference can be expressed quantitatively in terms of an Arrheniustype equation. it would be expected that..1.2. and electrons from the solution to the electrode.1 is associated with a negative current density since it involves the transfer of A z+ (a positively charged species) from the solution to the electrode. 19. its reaction would be affected by the potential difference between the metal electrode (φ M) and the aqueous solution (φ Aq). since Az+ is charged. As the value of (φ M .φ Aq)/RT] (19. Thus.φ Aq = ∆φ ) becomes less positive.o exp[-(1 . the attraction of Az+ to the electrode surface would be enhanced and therefore the rate of the forward reaction would rise (i. it would be harder to reject Az+ from the electrode surface and therefore the reverse reaction would slow down (i. kf would increase). the reverse reaction which transfers a positively charged species to the aqueous phase.. Recalling the electrode reaction described by Equation 19. electrons are consumed (cathodic reaction). kr would decrease). i. the activation energy of an electrochemical reaction is greatly influenced by the electrode potential. gives rise to a positive current. On the other hand.α )nF(φ M . Furthermore.φ Aq): kf = kf. and electrons from the electrode to the solution.φ Aq)/RT] (19. with an activation energy which is proportional to (φ M .

the energy is lowered compared with the E=0 condition. when a negative potential (E<0) is applied. the energy of the electron is lowered (Figure 19. (1 . In contrast.2 Relationship between electrode potential and electron energy.1 are the activation energies ∆G#oc and ∆G#oa respectively. Correponding to the cathodic (forward) and anodic (reverse) reactions of Equation 19. Energy Potential (a) E = 0 (b) E > 0 (c) E < 0 Figure 19.φ Aq).e.φ Aq). we can say that when the electrode potential is zero (E = 0 V). the energy of an electron in the electrode is altered. Referring to Figure 19. as well as the fraction that affects the reverse reaction. It must be noted that the free energy of Az+ increases as it approaches the electrode surface since it becomes necessary to (fully or partially) discard the waters of hydration of this species. the reactants (Az+ + ne-) and the product (B) are associated with free energies which change with distance as shown by the solid curves. i.3.2b) and consequently.2. α is termed the transfer coefficient and gives the fraction of the potential difference that influences the forward reaction. As illustrated in Figure 19. i..where F is the Faraday constant.. the energy of the electron is raised. When a positive potential (E) is imposed on the electrode.e. When a potential is applied to the electrode.α)(φ M . the curve representing the (Az+ + ne-) configuration 7 . with a positive potential (E>0). α(φ M . We can gain some insight into the origin of the α parameter by considering the free energy changes associated with the electron transfer process.

3 further shows that: ∆G#c + αnFE = ∆G#oc + nFE (19. It follows from Figure 19.αnFE (19.10a) Examination of Figure 19. The resulting cathodic and anodic activation energies are ∆G#c and ∆G#a respectively. It can be seen that application of the positive potential E has the consequence of lowering the anodic activation energy by a certain fraction (αnFE) of the overall energy change. as shown by the dashed curve in Figure 19.moves downwards by the amount nFE.3 that ∆G#a = ∆G#oa .10b) Thus ∆G#c = ∆G#oc + (1-α)nFE (19.10c) 8 .3.

11 a.o exp − ∆G# RT f c [ ] ] (19.10 a.o exp −∆G # RT a [ (19. c and 19.E=0 E=E α nFE (1− nFE α) ∆G# oa ∆G# a nFE ∆G# c B Standard Free Energy ∆G# oc Az+ + ne- Reaction Coordinate Figure 19. b.11b) It follows from Equations 19. that 9 .11a) kr = k′r.3 Relationship between electrode potential and the activation energy for electron transfer. We can express the rate constants kf and kr in terms of the following Arrhenius-type equations: kf = k ′ .

12a) kr = k′r.o exp− ∆G# RT) exp αnFE RT] [ oa = k r.kf = k ′ . and therefore (recalling Equations 19.12b. at equilibrium. rA = 0.15) 19.o = k ′ . 19. Equation 19. Also.o exp − ∆G# + (1 − α )nFE RT f oc = k f.oCBexp[αnFE/RT] (19.o exp [− (1 − α )nFE RT ] # = k′f.13a) kr .12b) where # kf . and 19.8. the current density can be expressed as: iA = -nFkf.13b) Based on Equations 19.7 can be rewritten as: rA = -kf.o exp − ∆G oc RT f [ [ ] ] (19.12a and 19.7 and 19. i=0.2.oCAexp[-(1-α)nFE/RT] + kr.o exp − ∆G oc RT exp[− (1− α )nFE RT ] ( [( ) ) ] (19.3 The Butler-Volmer Equation At equilibrium.o = k ′ exp − ∆G # RT r.o exp αnFE RT] [ (19. E = Eeq.14) Also.o exp − (∆G # − αnFE) RT] [ oa = ( k′r.8).12a.oCAexp[-(1-α)nFE/RT] + nFkr. 10 .oCBexp[αnFE/RT] (19. in view of Equations 19.o oa (19.12b.

kf C Ae = k r C Be (19. It follows then from Equations 19. When CAe = CBe. Eθ′ .8). E = Eeq. i = 0 and therefore kfCAe = krCBe.8) Also.17 that kf = k o exp −α (1 − α )nF (E − Eθ ′ )/ RT [ ] (19.17) where ko is termed the standard rate constant. For the special situation where the electrode potential and solution conditions are such that CAe = CBe.1 The Nernst Equation Starting with the expression derived above for the current density associated with the overall electrode reaction (Equation 19.b and 19.12 a.8 that 11 . Equation 19.18a) k r = k o exp αnF (E − E θ ′ )/ RT [ ] (19. at equilibrium. also. show that E eq = E θ′ + (RT nF)ln(CA C B) Solution From Equation 19.b. the corresponding equilibrium potential is termed the formal potential.18a.16 gives: kf = k r = k o (19.18b) EXAMPLE 19. It follows from Equations 19.8 we know that (1) i = −nFkf CA + nFk r CB (19. and 19.16) where CAe and CBe are the corresponding equilibrium concentrations of A and B.

is the cathodic current. [ ) ( αnF ) RT]= CBe k o exp[ (E eq − E θ′ ) RT] (2) (CAe C Be = exp (α + 1 − α)nF Eeq − E [ ( θ′ nF ) RT ]= exp[ (E eq − E θ ′) RT] (3) Rearranging.8 with Equations 19. we get the desired expression: Eeq = Eθ' + (RT/nF)ln(CAe/CBe) Equation 4 represents the Nernst equation for the Az+/B couple.+ i+ (19.21b) 12 .θ′ C Ae k o exp − (1 − α )nF E eq − E Thus.19) Equation 19. and i+ the anodic current: i. (4) Combining Equation 19.20) where i.19 can be rewritten as: i = i.= -nFkoCAexp[-(1-α)nF(E-E ')/RT] θ (19. b gives: i = −nFk o C A exp −(1− α )nF (E − E θ′ ) RT + nFk o C B exp αnF (E − E θ′ ) RT [ ] [ ] (19.21a) and i+ = nFkoCB exp[αnF(E-E ')/RT] θ (19.18a.

e. Equation 19.23a) nFk o CBe = i o exp −αnF E eq − E θ′ RT [ ( ) ] (19.21a and 19. i.24a) From 19. i − = − (C A C Ae )i o exp −(1− α)nF (E − E θ ′ − E eq + E θ′ ) RT] [ = −(CA CAe )i o exp − (1− α )nF (E − E eq ) RT [ ] (19..23a.20 gives: i + = −i − = i o = nFko CBe exp αnF E eq − E θ′ RT = ) ] nFko CAe exp[ (1 − α )nF ( eq − E θ ′ ) RT] − E [ ( (19. io. It follows from Equation 19.23b) From 19. i = 0. i + = (CB C Be )i o exp [αnF (E − E θ′ − E eq + E θ ′ ) RT] = (C B CBe )i o exp αnF (E − E eq ) RT [ ] (19. Thus.24b) 13 . termed the exchange current density.21b and 19.22) That is. the anodic and cathodic currents have the same magnitude. at equilibrium.22 that: nFk o CAe = i o exp (1 − α )nF (E eq − E θ′ ) RT [ ] (19.At equilibrium.23b.

(CA/CAe)exp[-(1-α)nFη/RT]} { [ ( ) ] [ ( ) ] } (19. The above analysis indicates that if the rate of electron transfer is slow. it is necessary to provide an applied potential that is sufficiently greater than the equilibrium potential.24b in Equation 19.25b) Equation 19. then in order to obtain significant reaction rates.24a and 19.Eeq (19. EXAMPLE 19.20. io = nFkoCo Solution Recall the Nernst equation (Ex19.2 Relationship between the exchange current density and the standard rate constant Show that when CAe = CBe = Co. the variation of (i/io) and log (|i|/io) with the overpotential η.1): θ′ E eq = E + (RT nF )ln CAe CBe ( ) 14 (1) .25a) where η is termed the activation overpotential and is given by: n = E .25a is called the Butler-Volmer equation.4a and b illustrate respectively.Using Equations 19. i = i o (CB C Be )exp αnF E − E eq RT − (C A / CAe )exp − (1 − α )nF E − E eq RT = io{(CB/CBe)exp[αnFη/RT] . Figures 19.

α)nF(Eeq .20.nFkf CA (19. i.8 and 19.8 and 19. 15 .26: − nFkf C A = (−C A C Ae )i o exp[− (1 − α )nFη RT] kf = (i o nFC Ae )exp [− (1 − α )nFη RT ] (19.22 can be rewritten as io = nFkoCAe = nFkoCo where the condition CAe = Co has been used.α)] In Equation 3 the condition CAe = CBe has been used.24a and 19. exp nF E eq − E [( θ′ ) RT]= CAe C Be (2) Multiply Equation 2 by exp [-(1-α)]: ′ {exp[ −(1 − α )]} exp[nF( E eq − E θ ) RT ] = (C Ae CBe ) exp[ −(1 − α)] = exp[-(1 .27) Similarly. We know from Equation 19. it follows from Equation 3 that Equation 19.That is.26) Compare 19.22 that io = nFkoCAe exp[-(1 .Eθ')/RT] Therefore. (3) Recall: from 19.20. from 19.= .

28: nFk r C B = (CB CBe )i o exp αnF (E − E eq ) RT [ ] k r = (i o nFCBe )exp αnF (E − E eq ) RT [ ] (19.12b) (19.29) k r = (i o nFC Be )exp [αnFη RT ] Summary kf = k ′ .18a) (19.11b) (19.i+ = nFkr CB (19.2.4 The Tafel Equations If |η| >> (RT/F).12a) (19.o exp [− (1 − α ) nFE RT ] = k o exp −(1− α )nF(E − E θ′ ) RT [ = (i o nFCAe )exp[−(1− α )nFη RT] kr = k′r.27) = k f.24b and 19.11a) (19.o exp[ nFE RT ] α = ko exp αnF (E − E θ ′ ) RT [ = (i o nFC Be )exp [α nFη RT] 19.18b) (19.29) = kr . two simplified relations called the Tafel equations arise: 16 .o exp − ∆G# RT f c [ ] ] (19.o exp −∆G # RT a [ ] ] (19.28) Compare 19.

25a can be neglected. ln |i| = ln {nFCAkf.oexp[-(1 . the second term in Equation 19.30b) (19.4b for large values of |η|. _____________________________________________________________________________ _ 17 .25a can be neglected to give: i = -io exp[-(1 . with the result that: i = io exp[αnFη/RT] or ln i = ln io + αnFη/RT (19.α)nFEeq/RT} . ln i = ln (nFCBkr.30a) That is.31c) The linear relationship between log (|i|/io) and η implied in Equations 19.α)nFη/RT (19.α)nFη/RT (19.o exp[αnFEeq/RT]) + αnFη/RT (19.30b and 19.(a) When η is positive.(1 . the first term in Equation 19.31b can be seen in Figure 19.31a) ln |i| = ln io .(1 .31b) That is.30c) (b) When η is negative.α)nFη/RT] or (19.

5 Mass Transfer Effects It was pointed out in Chapter 17 that the motion of an ion in an aqueous electrolyte solution is controlled by: (a) diffusion caused by a concentration gradient. Soc. Phys.. 573 (1952) ____________________________________________________________________________________________ 19. Z. 54.3 The Fe3+/Fe2+ electrode Gerischer.4 The Ce4+/Ce3+ electrode Vetter . Electrochem. 98. 564. 291 (1950) or 1951? Lewartowicz. 49. 195. 49. 366 (1950) Lewartowicz. Electrochem. Soc. 49. 564 (1952) Vetter and Manecke. 260 (1951) Petrocelli and Paolucci. J. J. 18 . 270 (1950) Lewartowicz. Chim.. Z. Phys. Physik. Z. J..EXAMPLE 19.2. Chim. and (c) a convective or hydrodynamic transport due to bulk fluid motion. 573 (1952) Petrocelli and Paolucci. 196. Chem. Chem. Elektrochem. Phys. 98. (b) migration due to the presence of an electric field. In the absence of migration and convection. Chim. J.. Physik. J. 291 (1950) EXAMPLE 19. the rate of transport is determined by the concentration gradient..

1) Referring to Figure 19.5 Mass transfer in electrode processes Recall the AZ+/B reaction at the electrode surface: kf + ne ↔ B kr − A Z+ (19. A (CA − CAS ) (19.A (s) z+ NA CA A z+ CAS (rA) CBS B(s) Electrode NB Solution CB B δ Figure 19.5 and considering Equation 19.1: Flux of A to the surface: N A = kd.32b) . B (CBS − CB ) Rate of consumption of A by the reaction at the electrode: 19 (19.32a) Flux of B from the surface: NB = k d.

33) From Equation 19.32b.32c) Under steady-state conditions.rA = (1 S)dn A dt = − k f CAS + k r C BS = i nF (19. Equation 19. CAS = CA – (NA/kdA) (19.33. rA = − k f [(NA kdA ) + C A ]+ k r [CB − (NB k dB)] (19.32a. we must have N A = rA = NB = i nF (19.35 into Equation 19.34 and 19.35) Substituting Equations 19. CBS = CB + (NB/kdB) (19.32c. and thus. NA = NB = rA.34) From Equation 19.36) Recalling Equation 19.36 becomes: rA = − (kf k dA )rA − k f C A + k r CB − (k r kdB )rA rA [ + (k f k dA ) + (k r k dB)] = −k f C A + kr C B 1 20 .

39 to substitute for CA and CB respectively. (CB . i.32b) is greatest when CBs « CB..39) Writing rA in terms of current density (Equation 19. any A that reaches the electrode surface is instantaneously consumed by the reduction reaction. What happens when only A is present in solution? Under these conditions. iLa: i La = nFkdBCB (19. It should be noted that both k f and kr are 21 .CAs) ≈ CA.40a) i = [ k f k dA )i LC + (k r k dB)i La ] [ (k f k dA ) + (k r k dB)] ( 1+ (19. any B reaching the electrode surface is immediately oxidized. Equation 19.38 and 19. Under these conditions. iLc.e. CB = 0 → iLa = 0. and using Equations 19.38) Similarly. i.37) It can be seen from Equation 19.40b) CASE 1: Only A is present in solution. and recalling Equation 19. The resulting current density is termed the cathodic limiting current density. In this case. in the case of the anodic reaction.CBS) ≈ CB. the rate of mass transport of B (Equation 19.33: i LC = −nFkdA CA (19.rA = − kf C A + k rC B 1 + (k f k dA ) + (k r k dB ) (19.32a that the rate of mass transport of A is greatest when CAS « CA.37 becomes: (i nF ) = −k f (−i LC nFk dA ) + k r (i La nFk dB ) 1 + (k f k dA ) + (k r kdB ) (19.33). (CA .e.. The resulting current density is termed the anodic limiting current density.

41c becomes: −1 i = 1 nFkf CA (19.38. (i.41b) Recalling Equation 19. Under these circumstances.41d) or i = −nFk f CA (19. it can be seen that as the potential (E) becomes more negative.12a and 19. we get from Equation 19.potential-dependent.e.41a) Rearranging.40b: i = (kf k dA )i LC [ + k f k dA ] 1 = k f i LC [k dA + kf ] (19.12b.nFkdACA).41b becomes −1 i = 1 nFkf CA + 1 nFkdAC A (19. the electrode reaction will be kinetic or transport controlled.41c) Depending on the relative magnitudes of kf and kdA. the potential must be decreased sufficiently to drive the cathodic reaction. Recalling Equations 19. Therefore. and kf » kr. When kdA » kf.41e) 22 . 1 k 1 = dA + i k f i LC i LC (19. iLC = . kf increases while kr decreases. using the constraints iLa = 0. In the absence of B. Equation 19.. kf » kr . Equation 19.

in this case. Here CA = 0 → iLC = 0.42b) Recalling Equation 19.41c simplifies to: −1 i = 1 nFk dAC A (19. Also kr » kf (for reverse of reasons given above for Case 1). Therefore. CASE 2: Only B is present in solution. Equation 19. the reaction is under kinetic control.39 (i.42c) 23 .40b simplifies to: i = (k r kdB )i La [1+ (k r kdB )] = k r i La [k dB + kr ] (19..41g) In this case the reaction is transport controlled.42a) or 1 i = k dB k r i La + 1 i La (19. when kdA « kf. On the other hand. iLa = nFkdBCB).That is.e. Equation 19.41f) or i = −nFk dAC A (19.42b may be rearranged as: 1 i = 1 nFk rC B + 1 nFk dBC B (19. Equation 19.

50a) (19. the hydrogen evolution reaction involves a two-step process of the form: H3O+ +e.6 Electrical Double Layer Effects 19.e.. i = nFkr C B (19. on certain metal surfaces. the reaction is under kinetic control: 1 i = 1 nFk r CB (19.42f) i = nFkdBC B (19.2. Electrochemical reactions are no exception. e.3.42g) 19.42e) On the other hand. for example.1 Multi-step Reactions at Metal Electrodes As discussed in Chapter 16. may involve the following steps: 24 ..g.42d) i.(M) → H (M) + H2O H (M) + H (M) → H2 (19.When kdB » kr. the reaction is under transport control and 1 i = 1 nFk dBCB (19. an overall chemical reaction will typically consist of two or more steps. when kdB « kr. Thus. Cu.50b) The dissolution of a divalent metal ion.3 Redox Electrodes 19.

Cu → Cu+ + eCu+ → Cu2+ + e-

(19.51a) (19.51b)

The Mn4+/Mn3+ redox electrode has the following overall reaction:

Mn3+ = Mn4+ + e-

(19.52a)

The reaction steps are:

2Mn3+ → Mn4+ + Mn2+

(19.52b)

Mn2+ → Mn3+ + e-

(19.52c)

In the case of iodine reduction, the overall reaction is:

I3- + 2e- = 3I-

(19.53a)

The relevant reaction steps are:

I3- ↔ I2 + I(19.53b)

I2 ↔ 2I

(19.53c)

25

I + e- → I-

(19.53d)

Consider a general electrochemical reaction in which 2 electrons are transferred from an electrode to a species A, transforming it to C:

A + 2e- = C

(19.60)

As discussed in Chapter 15, we can derive a rate law for this reaction with the aid of the steadystate assumption or the rapid equilibrium assumption. Suppose this reaction proceeds via the following single-electron transfer steps: Steady-state Assumption

A + e- ↔ (k1, k-1) B

(Step 1)

(19.61)

B + e- ↔ (k2, k-2) C

(Step 2)

(19.62)

Following the procedures developed in Chapter 15, we can write:

rA = -k1CA + k-1CB

(19.67)

rB = k1CA - k-1CB - k2CB + k-2CC

(19.68)

rC = k2CB - k-2CC

(19.69)

26

As found previously in Chapter 15, applying the steady-state approximation to reactive intermediate B (i.e., rB = 0) gives:

CB = (k1CA + k-2CC)/(k-1 + k2)

(19.70)

Inserting Equation 19.70 into Equations 19.67 and 19.69,

rA = (-k1k2CA + k-1k-2CC)/(k-1 + k2)

(19.71)

rC = (k1k2CA - k-1k-2CC)/(k-1 + k2)

(19.72)

Bearing in mind the convention adopted here, i.e., a reaction that releases an electron generates positive current, the net current associated with the overall reaction can be expressed as:

i/F = -k1CA + k-1CB - k2CB + k-2CC Using Equation 19.70 to substitute for CB in Equation 19.73 gives:

(19.73)

i/F = 2(-k1k2CA + k-1k-2CC)/(k-1 + k2)

(19.74)

It can be seen by comparing Equations 19.71 and 19.74 that i/F= 2r A. This is consistent with the fact that the overall reaction involves the transfer of two electrons and that when the steady-state approximation is valid, the rates of the successive steps are equal. Recalling Equations 19.12a and 19.12b, the rate constants can be expressed as:

27

k1 = k1,o exp[-(1-α1)FE/RT] k-1 = k-1,o exp[α1FE/RT] k2 = k2,o exp[-(1-α2)FE/RT] k-2 = k-2,o exp[α2FE/RT]

(19.75) (19.76) (19.77) (19.78)

It is instructive to consider approximate forms of Equations 19.71, 19.72, and 19.74. For example, when k-2 << k1, and k2 << k-1, we get:

CB = k1k2CA/k-1

(19.79)

rA = -k1k2CA/k-1

(19.80)

rC = k1k2CA/k-1

(19.81)

i/F = -2k1k2CA/k-1

(19.82)

Recalling Equations 19.75, 19.76, and 19.77, Equation 19.80 can be rewritten as:

rc = CA • k1, 0 exp[ α 1FE / RT ] • k 2, 0 exp[ α 2 FE / RT ] • k −1,0 exp[(1− α1 )FE / RT ]

= (k1,0 k 2,0 / k−1,0 )CA exp[( α 1 + α 2 + 1− α 1 )FE / RT ]

rc = (k1,0 k2,0 / k−1, 0 )CA exp[(1 + α 2 )FE / RT ]

(19.83a)

= kCA exp[α FE/ RT]

(19.83b)

28

86) The parameter α(=1+α2) is termed an apparent transfer coefficient.0 k 2. Let us now consider the case where the first electron transfer involves a rapid equilibrium: A⇔ B + e− K1 (fast) (19.where k = (k1.85) Accordingly. Rapid Equilibrium Assumption.89 are equal in k1 magnitude: − k1 CA + k−1 + CB = 0 (19.84) α = 1+ α 2 (19. the net current density becomes: i = 2kCA exp[ FE / RT] α (19.91) Also.90) The rapid equilibrium means that the forward and reverse rates of Equation 19. 0 / k −1. 29 .89) B→ C + e− K2 (slow) (19.0 ) (19.

1.91 that CB = (k1 / k−1 )CA (19.95) It can be seen that Equations 19. In fact. applying the conditions k-2<<k2 and k2<<k-1 to Equations 19. Referring to Equation 19. 19.82 respectively. there are many situations where reaction intermediates adsorb on the electron surface. Thus.93.62 is equivalent to replacing Equation 19.92.90.94) Referring to the stoichiometry of the overall reaction (Equation 19. the Butler-Volmer equation was derived on the assumption that the entire metal electrode surface was accessible to the reactants in the aqueous solution.92) It follows from Equation 19.79. production of 1 mole of CA is associated with the generation of two moles of electrons. suppose now that the product B is retained as an adsorbed intermediate on the electrode surface: 30 . Thus: i / F = 2rc = 2k1 k2 CA / k −1 (19. and 19.3. and 19. 19.93) Inserting Equation 19. 19.2 Adsorbed Intermediates and Electron Transfer In the discussion above.rc = k2 CB (19.93 into Equation 19. thereby decreasing the effective surface available for reaction.95 are identical to Equations 19.60).81. rc = (k1 k2 / k−1 )CA (19.62 by the irreversible reaction of Equation 19.94.61 and 19.

α)nFE/RT] + θBkr.oexp[αnFE/RT] (19.oexp[-(1 .θ Be)kf.111a) where θB is the fraction of the electrode surface that is occupied by the adsorbed intermediate B. recalling Equation 19.oexp[-(1 .110) Then recalling Equation 19.α)nFE/RT] + nF[θB/θ Be]θBekr. Similarly.θ B)kf.Az+ + ne.↔ B (ads) (19.14. the corrresponding rate equation can be written as: rA = -CA(1 .oexp[αnFE/RT] (19.oexp[-(1 .112a) = -i.oexp[-(1 .111b) At equilibrium.α )nFEeq/RT] (19.θ B)/(1 .15. Thus. the exchange current density is given by: io = i+ = nFθBekr.oexp[αnFEeq/RT] (19.112b) where θBe is the equilibrium surface coverage of B.= nFCA(1 .α)nFE/RT] + nFθ Bkr.113a) 31 .θ B)kf. we can rewrite Equation 19.111b as: i = -nFCA[(1 . the current density now becomes: i = -nFCA(1 .θBe)](1 .θ Be)kf.oexp[αnFE/RT] (19.

the surface is a composite of Langmuir adsorption sites.113b) = io {[θB/θ Be]exp[αnFη/RT] .θ Be)]exp [-(1 . The standard free energy of adsorption is given by ∆Gads = -RTlnK (19.Eeq)/RT] + io[(1 .θ) = CAKexp[-nFEeq/RT] (19. However.113c) The Langmuir Adsorption Isotherm.114) where K = kf. According to the Temkin treatment.112a and θ/(1 .α)nFη/RT]} (19. heterogeneity of surface sites.115) The Temkin Adsorption Isotherm.Eeq)/RT] (19. 19.o/kr.= -io [θ B/θBe]exp[-(1 .α)nF(E . and surface-dipole effects. The coveragedependent adsorption has a number of origins.[(1 .114 represents a Langmuir adsorption isotherm for the intermediate B. there is experimental evidence indicating that this is not generally the case. each with its own characteristic standard freee energy of adsorption. it follows from Equations 19.θBe)] exp[αnF(E .θ B)/(1 . Equation 19.o.θB)/(1 . It is assumed that the standard free energy of adsorption varies linearly with coverage: 32 . including interactions between adsorbed species.112b that Also. The Langmuir adsorption isotherm is based on the assumption that the free energy of adsorption is independent of the surface coverage.

θ /∂θ = r (19.119) Similarly. it is assumed that the two are related linearly. ∆Gdes.0 + r'θ (19. and r' = -r.e. It follows from Equation 19. i.θ. the magnitude of the free energy of adsorption decreases with coverage.118) where ∆Gdes.0 = -∆Gads.117) Similarly.0. ∂∆G*ads.θ /∂θ = γ∂∆Gdes.θ /∂θ = γ'r' = -(1 . Associated with the coverage-dependence of the free energy of adsorption is a coveragedependence of the activation energy of adsorption (∆G*ads.116) where r is a proportionality constant and ∆Gads. in the case of the free energy of desorption.0 represents the standard free energy of adsorption at zero coverage. Equation 19.θ /∂θ = γ∂∆Gads.θ = ∆Gads. It should be noted that since the free energy of adsorption is a negative quantity.θ = ∆Gdes. In general.0 + rθ (19.γ)r (19. ∂∆G*des.θ = -∆Gads. we can write: ∆Gdes.∆Gads.θ /∂θ = γr (19.116 that ∂∆Gads..116 shows that with r positive.120) where the proportionality constant γ' is related to γ as: 33 . for the activation energy of desorption.θ ).

oexp[-(1-α)nFE/RT]exp[-γrθ/RT] + nFθBkr.0 + γ'r'θ = ∆G*des.122 and 19.119 and 19. It follows from Equations 19.123 respectively to substitute for ∆G*ads.oexp[αnFE/RT]exp[-∆G*des.120 that: ∆G*ads.121) It can be seen from Equation 19.θ B)kf.122) ∆G*des.θ and ∆G*des.γ) (19.γ)rθ (19.125 may be simplified to: 34 .θ in Equation 19. the contributions of the pre-exponential terms in θ are small compared with the corresponding exponential terms.(1 .θ /RT] + nFθBk'r.oexp[αnFE/RT]exp[(1 . Thus.θ B)k'f. we can write the rate equation for the Temkin condition as: i = -nFCA(1 .θ = ∆G*ads.124 gives: i = -nFCA(1 .γ)rθ/RT] (19.0 + γrθ (19.θ/RT] (19.θ = ∆G*des.124) Using Equations 19.121 that γ has the characteristics of a symmetry factor.γ' = (1 .123) Returning now to Equation 19.110.oexp[-(1-α)nFE/RT]exp[-∆G*ads.0 . Equation 19.125) For intermediate coverages.

3 The Hydrogen Electrode In Chapter 10.126) At equilibrium.i = -nFCAkf. They may also represent competing reactions which therefore decrease the efficiency of the reactions of interest. further adsorption becoms less favorable. in oxygen-free solutions metals with 35 . θ increases more rapidly with the Langmuir isotherm compared with the Temkin isotherm. this effect increases with increase in the magnitude of the proportionality constant. This situation can be understood physically by recognizing that as the coverage increases.127 and 19. These reactions frequently serve as the half-reactions for many technologically important electrochemical processes.114) may be reexpressed in logarithmic form as: ln θ − ln (1 .128) Examination of Equations 19.θ) = -nFEeq/RT + ln KCA (19. r.γ)rθ/RT] (19. it was pointed out that water decomposes under reducing conditions to give molecular hydrogen.oexp[αnFE/RT]exp[(1 .126 reduces to: θ = -nFEeq/RTr + (1/r)ln KCA (19. i = 0.127) For purposes of comparison.128 indicates that as CA is increased.oexp[-(1-α)nFE/RT]exp[-γrθ/RT] + nFkr.3. the Langmuir adsorption isotherm (Equation 19. 19. because of the corresponding decrease in |∆Gθ |. and under oxidizing conditions to give molecular oxygen. Thus. and Equation 19.

132) H (ad) + H3O+ + e.130) 2H+ + 2e.→ H2 (19.→ H2 + H2O (19. Pathways for the Hydrogen Evolution Reaction.129) This reaction can be decoupled into its anodic and cathodic half-reactions as: M → M2+ + 2e- (19.standard reduction potentials below that of the standard hydrogen electrode will dissolve.133) and the electrochemical-desorption mechanism: H3O+ + e. Two main mechanisms are accepted for the hydrogen evolution reaction. with evolution of hydrogen: M + 2H+ → M2+ + H2 (19.→ H (ad) + H2O (19. These are the chemical-desorption mechanism: H3O+ + e.131) The cathodic evolution of hydrogen is also of importance in metal deposition systems where it represents a competing reaction to the metal reduction reaction.132) H (ad) + H (ad) → H2 (19.134) 36 .→ H (ad) + H2O (19.

In the chemical-desorption mechanism. the discharge step) is rate-determining: H3O+ + e. For either mechanism. which then desorbs (Equation 19.θ H)exp[-(1 .138) 37 . Let us first consider case (a).134).136) The current density associated with the rate-determining step is given by: i1 = Fk1. additional protons are reduced onto the first layer of adsorbed hydrogen atoms..0[H3O+]exp[-(1 . they react chemically to give a hydrogen molecule. the situation where the first step (i.It can be seen from Equations 19. Atoms from the first and second layers then combine to form hydrogen molecules (Equation 19.e.α)FE/RT] (19..→ H (ad) + H2O k1 (19.0[H3O+](1 .134 that in both cases.137 simplifies to: i1 = Fk1. the two mechanisms differ in what happens next. k-2 (19.e. the first step is the reduction of a hydrated proton to give an adsorbed hydrogen atom.α)FE/RT] (19. In the case of the electrochemical-desorption pathway. However. When two such atoms encounter one another. i. θH → 0 and Equation 19.132-19. The chemical-desorption mechanism. the rate- determining step may be the the first step (case a) or the second step (case b). the adsorbed hydrogen atoms diffuse over the electrode surface.135) H (ad) + H (ad) ↔ H2 k2.133).137) For relatively low surface concentration of adsorbed atomic hydrogen.

0)[H3O+]exp[-FE/RT]} (19.140) H (ad) + H (ad) → H2 k2 (19.. θ H = {k1. and Equation 19.0 + k1. chemical desorption) is ratedetermining.↔ H (ad) + H2O k1.0θHexp[αFE/RT] (19.0/k-1.0.0[H3O+]exp[-FE/RT]} (19. Thus: k1. where the second step (i. we have: H3O+ + e.θ H)exp[-(1 . for case (b).0[H3O+]exp[-FE/RT]}/{k-1.140) is at quasi-equilibrium. the entire two-step reaction involves the transfer of two electrons.142) That is.143 reduces to: θ H = (k1.0[H3O+]exp[-FE/RT] << k-1.e.α)FE/RT] = k-1.139) Alternatively.0[H3O+](1 .141) Here. the net current is given by: i = 2i1 = 2Fk1[H3O+]exp[-(1 .α)F∆ φ /RT] (19. Thus.Now. k-1 (19.144) 38 . k1. the first step (Equation 19.143) For low overpotentials.

148) It can be seen that Equation 19. i. where the electrochemical desorption step is ratedetermining..↔ H (ad) + H2O k1. Thus the same net rate law is obtained (Equation 19. we have: H3O+ + e.The rate equation for the second step (Equation 19. where the first step is ratedetermining.135. On the other hand. for case (b).↔ H2 + H2O k2.150) 39 .144 and 19.141) is given by: i2 = Fk2θ H2 (19.e.149) H (ad) + H3O+ + e.147 is the same as Equation 19.→ H (ad) + H2O k1 (19.→ H2 + H2O k2 (19.145 that the net current is: i = 2i2 = 2Fk2θ H2 = 2Fk2 (k1.146) The electrochemical-desorption mechanism.0/k-1.145) Thus.0)2[H3O+]2exp[-2FE/RT]} (19. k1 (19. it follows from Equations 19. it represents the same situation as that treated above for the chemical-desorption mechanism. the reaction steps can be represented as: H3O+ + e.139). k-2 (19.147) H (ad) + H3O+ + e. For case (a).

144 to represent θ H.α)FE/RT]} (19.5.α) 2 H3O+ R'n order* 1.Here. For the second step.5.0)[H3O+]2exp[-(2 . Table 19. the relevant rate equation is: i2 = Fk2.143 and 19. Hence. we can also use Equations 19.0 2.α) 2.0/k-1.152) The net current is then given by: i = 2i2 = 2Fk2.151 gives: i2 = Fk2.α)FE/RT]} (19. the first step is the same as in case (b) of the chemical desorption pathway.144 and 19.α)FE/RT]} (19.0 (k1.0 ElectrochemicalDischarge (1 .0θ H[H3O+]exp[-(1 .0/k-1.151) Combining Equations 19.0 ____________________________________________________________________________________________ * From (∂lni/∂ln[H3O+])E 40 .0 (k1.153) A summary of kinetic parameters arising from the above reaction mechanisms is presented in Table 19.0)[H3O+]2exp[-(2 .0 desorption Desorption (2 .α) 1. Kinetic parameters for the hydrogen evolution reaction Mechanism Chemical-desorption Rate-limiting step Discharge Desorption αc (1 .

+ H2O + 2e.→ HO2.+ O2 (acid solutions) (acid solutions) (alkaline solutions) (alkaline solutions) (19.155) (19.→ 3OH2HO2.19.→ 2H2O O2 + 2H2O + 4e. These are the four-electron pathway (Equations 19.3.160) (19.4 The Oxygen Electrode Pathways for Oxygen Reduction.→ 2H2O 2H2O2 → 2H2O + O2 HO2.→ H2O2 O2 + H2O + 2e.157) It must be noted that the hydrogen peroxide produced in the two-electron pathway may undergo further reaction: H2O2 + 2H+ + 2e.157): O2 + 4H+ + 4e.158) (19.154) (19.156 and 19.159) (19.→ 2OH.154 and 19.155). and the two-electron pathway (Equations 19.156) (19. Two overall pathways have been identified for oxygen reduction in aqueous solutions.→ 4OHO2 + 2H+ + 2e.+ OH- (acid solutions) (alkaline solutions) (acid solutions) (alkaline solutions) (19.161) 41 .

5 (1986) 42 .g. J. Mol. Co) Oxides: Most transition metal oxides (e. Ni. Yeager. spinels) (Modified from E.g.. NiO. Reaction Pathway Electrode Material Four-electron Platinum group metals Other metals: Ag Oxides: Pyrochlores (e. Hg. lead ruthenate) Two-electron Graphite Metals: Au. 38.. most oxide-covered metals (e..10 Electrode materials and reaction pathways for oxygen reduction.Table 19..g. Catal.

12 Molecular orbital representations of the types of interactions of molecular oxygen with metal atoms.M O Griffiths Model (Side-on) O M M M O O O M O Bridge Model (Cis) (Trans) M O O Pauling Model (End-on) Figure 19. The manner in which molecular oxygen first binds (i. the direct 4-electron process. Oxygen Reduction on Bare Platinum in Acid Solution.e. Molecular orbital representations of the possible modes of attachment are illustrated in Figure 19. On the basis of the pathways noted above. These arrangements should favor the dissociation of O2 and therefore. electrode materials may be classified as indicated in Table 19. The following rate mechanism has been proposed: 43 . adsorbs on) to the metal atoms on the electrode surface determines whether the overall reduction reaction will follow the four-electron or the two electron pathway.10.. The electrochemical reactions of oxygen are influenced by the nature of the metal electrode.12 that with the Griffith and bridge-type interactions. It can be seen from Figure 19.12. both oxygens of O2 form M-O bonds.

163) O (ads) + H+ + e. Thus.166) where ∆G*ads. k-4 (19.θ /RT] + nFθBk'r. while the remaining steps are assumed to be at quasi-equilibrium.α)FE/RT] exp[-∆G*ads.oexp[-(1-α)nFE/RT]exp[-∆G*ads.θ = ∆G*ads. assuming Temkin conditions.122 in Equation 19.oexp[αnFE/RT]exp[-∆G*des.124. in analogy with Equation 19. i = -nFCA(1 .θ/RT] (19.O2 + H+ + e.θ/RT] (19.167) 44 .166 gives: i1 = Fk1[H+]pO2(1 .124) i1 = Fk'1[H+]pO2(1 .θ B)k'f.θ)exp[-(1 .164) OH (ads) + H+ + e.↔ OH (ads) k3.0 + γrθ (19.162) HO2 (ads) + H+ + e.↔ H2O k4.165) The first step (Equation 19. k-3 (19. we can write.162) is taken to be rate-determining.→ HO2 (ads) k1 (19. k-2 (19.θ)exp[-(1 .122) Inserting Equation 19.↔ O (ads) + H2O k2.α)FE/RT] exp[-γrθ/RT] (19.

The steps which follow the rate-determining step are assumed to be in quasi-equilibrium.171) Using Equation 19.170 in Equation 19.167 gives: i1 = Fk1[H+]pO2exp[-(1 .α)FE/RT] exp[(1 .168 reduces to: Fk4[H+]exp[-(1 . Thus.3RT/r)pH -(2.θ)exp[αFE/RT] exp[-γrθ/RT] (19.168) Again.170 gives the surface coverage as: θ = (F/r)∆ φ + (2. Equation 19. Fk4[H+]θ exp[-(1 .169 that exp[-rθ/RT] = K4[H+]exp[-FE/RT] (19.γ)rθ/RT] = Fk-4[H2O]exp[αFE/RT] exp[-γrθ/RT] (19.γ)rθ/RT] = Fk-4[H2O](1 .α + γ)FE/RT] (19.169) It follows from Equation 19.170) Rearranging Equation 19.α)FE/RT] exp[(1 . in the case of the last step.171b) 45 . neglecting the pre-exponential terms in θ.171a) i1 = Fk1K4γ [H+]1+γ pO2exp[-(1 .3RT/r)log K4 (19.α)FE/RT] K4γ [H+]γ exp[-γFE/RT] (19.

173) Combining Equations 5.172) OH (ads) + H+ + e.175a) (19. it can be shown that: i1 = Fk1[H+]3/2pO2exp[-FE/RT] (19. Equation 19. The reaction on iridium has been rationalized in terms of the following mechanism: O2 + 2M ↔ 2MO MO + H+ + e.171a becomes: i1 = k[H+]3/2 pO2exp[-FE/RT] (19.175c) where Step 2 is rate-determining. 46 .→ MOH MOH + H+ + e.171): θ = (RT/r)pH + (F/r)V (19. resulting in a change in the Tafel slope to -2RT/F. 6.174) With increase in the absolute value of the potential.For α ≈ γ ≈ 1/2. k-4 (19. and 7. θ becomes negligibly small and Langmuirian behavior prevails. the relationship between θ and potential is approximately linear (see Equation 19.↔ H2O k4.↔ M + H2O (Step 1) (Step 2) (Step 3) (19.175b) (19.165) Also.

θ)exp[-(1 .Oxygen Reduction on Bare Platinum in Alkaline Solution.176) O2.178) With step one rate-determining and Temkin adsorption for the peroxide intermediate.177) OH (ads) e.180) For α ≈ 0.+ OH (ads) k2.α)FE/RT] exp[-(1 .↔ Ο H- k3.(ads) + H2O ↔ Η O2.→ O2. we get the following rate equation: i1 = Fk1[H+]1/2pO2exp[-FE/RT] (19.179) where f(θ) = F∆ φ /RT . the rate becomes: 47 .α)f(θ)] (19. Accordingly. k-2 (19. we get: i1 = Fk1pO2(1 . k-3 (19.ln[H+] (19. θ → 0 so that surface coverage no longer follows Temkin behavior.(ads) k1 (19.181) When the cathodic potential is relatively high.5. Two pathways have been identified. one of which involves H2O2 intermediate. The mechanism for the H2O2 intermediate pathway is: O2 + e.

i1 = Fk1pO2exp[-(1 . The following mechanism has been proposed by Zurilla et al.182) A comparison of Equations 19.186) O2H (ads) + e. Oxygen Reduction on Iron in Neutral Solution.(ads) k1 (19.↔ O2H- (19.182 indicates a change in the Tafel slope from -RT/F to -2RT/F as the surface coverage changes from Temkin to Langmuirian behavior.181 and 19.α)FE/RT] (19. Oxygen Reduction on Gold in Alkaline Solution.→ O2.185) O2 (ads) + H2O + e.184) The first step is believed to be rate-determining.+ H2O ↔ H2O2 + OH- (19.183) 2O2.188) 48 .↔ O2H (ads) + OH- (19. The following mechanism has been proposed by Zurilla et al: O2 → O2 (ads) k1 (19.187) O2H.+ OH- k2.(ads) + H2O ↔ O2 + HO2. k-2 (19.: O2 + e.

193) On bare iron. (1 .(ads) k1 (19. Equation 19. the first electron transfer was found to be rate-determining: O2 + e. and assuming γ = 1/2.→ O2.α)FE/RT] exp[-∆G*ads. the surface coverage of adsorbed intermediates (O2H (ads)) under Temkin conditions is given by θ = (F/r)E + (2.θ = ∆G*ads.189 and 19.α + γ)FE/RT] (19.192 becomes: i1 = Fk1pO2 [OH-]-1/2exp[-FE/2RT] (19.On oxide-covered iron.190.190) where ∆G*ads.191 in 19.α) = 0.191) Using Equations 19.θ/RT] (19. we can write the following rate equation: i1 = Fk'1pO2 exp[-(1 .183) as the rate-determining step.192) Since the rate-determining step is a chemical rather than an electrochemical reaction.183) 49 .0 + γrθ (19.3RT/r) log[OH-] + const (19.189) Thus with adsorption (Equation 19. i1 = Fk1pO2 [OH-]-1/2exp[-(1 .

197) In the case of acid solutions at low potentials (low current densities).194) OH + OH.+ H2O (19.(slow) (19.200) O + O → O2 (19.→ OH + e- (19.→ O. H2O → OH + H+ + e. ∂log i/∂pH = 0. ∂log i/∂log pO2 = 1.Experimentally it was found that: ∂E/∂log i = -120mV.201) 50 .198) OH + OH. Oxygen Evolution on Platinum in Acid Solution.195) O. The oxygen evolution reaction may be contrasted with the oxygen reduction reaction in that the oxidation reaction occurs on an oxidecoated surface in contrast to the reduction reaction which may involve both oxide and bare surfaces.→ O. OH.196) O + O → O2 (19.+ H2O (19.→ O + e- (19.→ O + e- (19.199) O.

→ O.207a) OH + OH.202) Mz+ + H2O → M(z-1)+ + OH + H+ (slow) (19.→ O. OH. Langmuir.206) Alkaline solutions at low potentials (low current densities) (Conway.→ O + e.→ OH + e- (19.203) OH + OH.6 The Chlorine Electrode 51 .208) O + O → O2 (19.(slow) (19.205) O + O → O2 (19.→ O + e- (19.3.+ H2O (19.+ H2O (19.At higher potentials. mediation by surface metal ions: M(z-1)+ ↔ Mz+ + e- (19.207b) O.3.204) O.209) 19.5 The Hydrogen Peroxide Electrode 19. 1990).

k1 k-1 52 . the metal surface develops two sites. A C + n1eE1 e- B + n2e.9 Multiple electrode reactions and electron flow. however.10. The presence of two different potentials on the same surface represents a non-steady-state situation and in order to achieve a uniform surface potential. electrons will begin to flow through the surface of the metal particle.e.D E2 Figure 19. anodic and cathodic sites at different potentials E1 and E2 respectively. There are many important practical systems. Examples are found in oxidative dissolution and in electroless deposition. These different potentials are a result of the anodic (Equation 19.4.261) and cathodic (reverse direction of Equation 19. Let us consider the surface of a metallic particle immersed in a solution containing the reactants A and B. we have confined our discussion of electrode kinetics to situations where there is only a single overall electron transfer reaction at the electrode. as shown in Figure 19.1 Multiple Redox Couples at an Electrode Up to this point.4 Mixed Potentials 19..262) reactions. The concept of mixed potential is illustrated in Figures 19. where two or more overall electron transfer reactions occur simultaneously at the same electrode. Immediately after contact with the two reactants.19. from the anodic site to the cathodic site.9 and 19.9. i.

.g.e.261) k2 D k -2 (19.10.262) Β + n2e- The current flow reaches a steady-state when the net anodic and net cathodic currents balance each other (i. Em.262) or a reversible potential (i.g. The potential at this stage is termed the mixed potential. e.. due to a single overall electrode reaction. The term rest potential is often used. Equations 19. This term refers to the open circuit potential irrespective of whether the observed potential is a mixed potential (i.261).261 and 19. due to multiple overall electrode reactions. The resulting overall reaction is given by: n2A + n1B = n2C + n1D (19.e.Α Χ + n1e(19. Equation 19.263) 53 . are equal and opposite in sign and therefore the net current is zero)....e. as illustrated for various scenarios in Figure 19. e.

i E1.eq ic ia E2.10 Relationship between the steady-state reaction rate and the mixed potential.eq E i E 1.eq = E1o + (RT/n1F) ln (CC/CA) (19. Figure 19.eq ic E ix m ia E 2.261 and 19.eq ic ia E 2.eq ic ia E2.eq E E ix m (a) A ctivation-controlled oxidation plus activation-controlled reduction (b) A ctivation-controlled oxidation plus m transfer-controlled reduction ass i E 1. Referring to the two redox couples presented above (Equations 19. It follows from Equations 19.261 and 19.265) 19.262).4.eq E ix m E i E 1.eq = E2o + (RT/n2F) ln (CB/CD) (19.eq E ix m E (c) M transfer-controlled oxidation ass plus activation-controlled reduction (d) M transfer-controlled oxidation ass plus m transfer-controlled reduction ass Figure 19.10a is the relevant current vs potential situation.2 Surface-Controlled Kinetics Under conditions where both the overall anodic and the overall cathodic reactions are activation-controlled. the corresponding reaction rates can be expressed as: 54 .262 that the corresponding equilibrium potentials are given by: E1.264) E2.

266a.e. CA = CAs.r1 = dCC/dt = =dCA/dt = i1/n1F = k1CAa = k-1CCc (19. i. 0CA° exp[α1FEm/RT] (19. 19. we can rewrite Equation 19.263 implies that at steady-state. the A/C couple).270a) 55 . and 19.. i1 = -i2 = im = r1n1F = -r2n2F = n1n2Frcat (19.268) Thus..e.267 that i1/n1n2F = -i2/n1n2F = r1/n2 = -r2/n1 = rcat (19.266a as: r1 = i1/n1F = k1CAa = k1. When only the anodic component of the net current is significant for the first redox couple (i.266b.269) where im is the current density at the mixed potential (where E = Em).266a) r2 = dCB/dt = -dCD/dt = i2/n2F = k2CDd = k-2CBb (19. CB = CBs. (1/n2)dCC/dt = -(1/n1)dCB/dt (19.267) It follows then from Equations 19.266b) It is assumed here that stirring is sufficiently high such that both the anodic and cathodic reactions are completely activation controlled. The stoichiometry of Equation 19.

273 that rcat = r1/n2 = ( k1. 2 k −1 .20 k −1 .272) Using Equation 19.270a and 19.266b simplifies to: r2 = i2/n2F = -k-2CBb = -k-2. we can manipulate Equations 19. when only the cathodic current predominates for the second redox couple (i.270b) Recalling Equations 7 and 8.270b to derive an expression for the mixed potential as: α1FEm/RT = -u1 ln(n1k1. 0 n 2.268 and 19. 0CBb exp[-(1 .270a gives: r1 = k 1.271) where u1 = α1/(1 + α1 = α2) (19..275) 56 .e. 0 (n 2 n 1 ) u .273) where u2 = 1 – u1 (19.Similarly. the D/B couple). 0CBb) (19.274) It follows from Equation 19.α2)FEm/RT] (19.271 to substitute for Em in Equation 19. 0CAa/n2k-2. Equation 19. C A 2 C B 1 2 u u au bu (19.20 / n1 1 )C A 2 C B 0 2 u u u u au bu 1 = k cat C A 2 C B au bu 1 (19.

6 23.0 0. Table E19.0 7.0 1.6 According to previous experiments. 2 k −1 . 2277-2282 (1986)).0 10.0 10.0 0.0 10.0 1.9 Effects of reactant concentrations on the initial rates of the gold-sol-catalyzed Feic-Thio reaction Concentration (10-3 mol dm-3) Feic 1.5 14. Solution 57 .35 Thio 10.4 0.8 0.75 Initial Rate (10-9 mol dm-3 s-1) (rexp) 47. Chem.9 34.0 1.where kcat = k1. 1.6 5.3 0.2 1.2 0.5 5.25 Na2SO4 0.3 14.625 0.0 43.6 0. Soc.0 1.+ 1/2S4O62- (1) This reaction was investigated by Freund and Spiro (J.0 K2SO4 0. 0 n 2 2 / n1 1 0 2 EXAMPLE 19.25 0. Show that the results presented in Table E19.6 0.0 1.0 2. the electrochemical reaction order of ferricyanide in the cathodic process is unity and the corresponding order for thiosulfate in the anodic reaction is also unity.+ S2O32.0 7.38 9.0 1.4 20.0 10. Faraday Trans.9 Surface-controlled colloidal gold catalysis of the ferricyanide-thiosulfate reaction u u u u (19.= Fe(CN)64.276) The overall reaction between ferricyanide (Feic) and thiosulfate (Thio) can be written as: Fe(CN)63.0 10.5 39. 82.2 27.75 9.1 19.5 5.1 1.2 46.5 8.9 presents their results. Table E19.8 38. 2.5 1.9 1.9 are consistent with a completely surface-controlled mechanism for the Feic/Thio reaction in the presence of gold sols.0 10.

According to the electrochemical analysis presented in Section 19. the experimental data can be represented by the following rate law: rexp = k(CThio)0.42 (4) Figure E19.2. Therefore. It is seen that a straight line of slope 0. A similar diagram is shown in Figure E19. shows that the experimental data conform to the requirement of Equation 19. Therefore. Equation 2 becomes: rcat = kcat(CThio) u 2 (CFeic) u1 (3) Figure E19. ____________________________________________________________________________________________ 58 .53(CFeic)0. Therefore. referring to Equation 19.275) Thus.53 is obtained by least squares. comparing the overall reaction (Equation 1) and Equation 19. rcat = kcat C A 2 C B 1 au bu (19.275. in this case the slope is 0. and therefore the kinetic results are consistent with a complete surface controlled electrochemical mechanism. we find that u1 + u2 = 0. we note that Feic represents the oxidant (B) and Thio represents the reductant (A).53 + 0.274.42 = 0.9b for ln r exp vs ln CThio.9 Now.9a shows a plot of ln rexp vs ln CFeic.4. we can write: rcat = kcat (CThio) au 2 (CFeic) bu1 (2) We know from the problem statement that the electrochemical reaction order of ferricyanide in the cathodic process is unity and the corresponding order for thiosulfate in the anodic reaction is also unity.95 ~ 1 (5) The fact that the sum of the experimentally based kinetic orders is nearly unity.274.42.

3 Mixed-Control Kinetics If the assumption used above that C = Cs is relaxed.278a that (19.19. CBs = (1 = i2/iLB)CB (19. Recalling the discussion in Section 19. then the bulk and surface concentrations of the reactants and the products can be related with the aid of Fick's first law. for the reactants A and B we have: NA = kdA(CA .278a) NB = r2 = i2/n2F It follows from Equations 19.277a) NB = kdB(CB – CBs) (19.281) 59 .277a and 19.277b and 19278b.4.5.CAs) (19.280) Similarly.2.278b) CAs = (1 – i1/iLA)CA (19.277b) Under steady-state conditions we must have NA = r1 = i1/n1F (19. from Equations 19.279) where iLA is the limiting current density attained when CAs = 0: iLA = n1FkdACA = k′ dA CA (19.

iL → ∞ and. and im = i1 = -i2. at the mixed potential. r1 = i1/n1F = k1CAsa (19.284a and 19. Thus.284a) r2 = i2/n2F = -k-2(1 – i2/iLB)b CBb (19. Therefore.285 becomes 60 .284b that: ln im = u2 ln (n1k1) + au2 ln (1 – im/iLA) + au2 ln CA + u1 ln (n2k-2) + bu1 ln (1-im/iLB) + bu1 ln CB (19. Equation 19.283b) Replacing CAs and CBs with Equations 19.281 gives r1 = i1/n1F = k1(1 – i1/iLA)aCAa (19. thus.where iLB = n2FkdBCB = k′ dBCB (19.285) At infinite stirring speed.282) Referring to Equations 19.270a and 19. it follows from Equations 19.270b. we recognize that we must now use surface concentrations. E – Em.284b) Again.283a) r2 = i2/n2F = -k-2CBsb (19.279 and 19.

0/n2k-2.α2)FEm/RT = ln (CBb/CAa) .ln im.e..16): (1 + α1 . iL → ∞ and Em → Em.ln (n1k1. Equation 19.285 and 19. im << iLA and im << iLB. ∞ + au2/iLA + bu1/iLB (19.291) Reaction at a rotating disc surface. 0) (19.287) For conditions where the mixed current is smaller than the respective limiting currents.289 becomes: (1 + α1 .α2)FEm.289) At infinite stirring speed.15): 1/im = 1/im.286) Combining Equations 19. Recall from Table 18.288) It can also be shown that when im << iLA and im << iLB. ∞ and Equation 19. ∞ + [RT/F(1 + α1 . 0/n2k-2. ∞/RT = ln (CBb/CAa) .ln (n1k1. the mixed potential is given by (see P19. ∞) = au2 ln (1 – im/iLA) + bu1 ln (1 – im/iLB) (19.290 into Equation 19.286 gives: ln (im/im. 0) + (a/iLA – b/iLB)im (19.289 gives the mixed potential as: Em = Em. i.α2)](a/iLA – b/iLB)im (19.3 that the mass transfer coefficient (ki) for a rotating disc is given by: 61 . ∞ = u2 ln (n1k1) + au2 ln CA + u1 ln (n2k-2) + bu1 ln CB (19.290) Substituting Equation 19.287 simplifies to (see P19.

ki = 0. ∞ + [RTn1n2/(1 + α1 . ∞ + (y/x)(1 – rcat/rcat.α2)](a/βA – b/βB)imω -1/2 Alternatively. recalling Equation 19.292) That is. ∞ + [RT/F(1 + α1 . ∞ + n1n2F(au2/βA + bu1/βB)ω -1/2 (19.280 and 19. ∞) = Em.294b) The corresponding mixed potential is obtained from Equations 19.269.297a) (19.62ν-1/6DB2/3)CBω 1/2 = βBω 1/2 Inserting Equations 19.α2)](a/βA – b/βB)rcatω -1/2 It can be shown that (see P19.269.294a) (19. ∞ + (y/x)(1 – im/im. 19.291.296) (19.X): Em = Em.294ª and 19. we can write: 1/rcat = n2/r1 = -n1/r2 = n1n2F/im = 1/rcat. Em = Em.297b) . rcatω -1/2 plot. ∞ + (au2/βA + bu1/βB)ω -1/2 Alternatively. and 19.62ν-1/6DA2/3)CAω 1/2 = βAω 1/2 iLB = n2FkdBCB = n2F(0.62ν-1/6Di2/3ω 1/2 (19. we can write the limiting currents as: iLA= n1FkdACA = n1F(0. ω -1/2 plot and y is the slope of the Em vs. ∞) where x is the slope of the 1/rcat vs.293) Recalling Equations 19. in view of Equation 19.295) (19.294a.(kid/Di) = 0.62(d2ω/ν)1/2(ν/Di)1/3 (19.288 gives: 1/im = 1/im. 62 (19.294b as: Em = Em.298) (19.282.294b into Equation 19.

299) where the subscript (s) denotes surface conditions.eq = Em (19.281. the surface concentrations of the products C and D can be expressed as: CCs = (1 + i1/iLC)CC (19.300b (cf negative signs in Equations 19.19. By using the conditions im = i1 = =i2. 63 .279.281.279 and 19. and Equations 19. Under these conditions.281) reflect the fact that the surface concentrations of C and D are higher than the respective bulk concentrations. the overall reaction will essentially proceed at equilibrium at the solid surface.300a and 19.4 Transport-Controlled Kinetics When the rate of electron transfer is relatively fast while the rate of mass transfer is relatively slow.eq = E2s.279 and 19. Parallel to Equations 19.300b) where iLC = n1FkdCCC = k′ dCCC (19. 19.301b) The positive signs in Equations 10.300a) CDs = (1 + i2/iLD)CD (19.4.301a) iLD = n2FkdDCD = k′ dDCD (19. the following relationship must hold: E1s.

301a.302b) When Equation 19.282.19.302a) E2s.302a is subtracted from Equation 19. 64 .302b.265.280. and 19.300b to relate the surface and bulk concentrations. 19.303 to substitute for f(im) in Equation 19. 19. eq = E1° + (RT/n1F) ln (CC/CA) + (RT/n1F) ln [(1 + im/iLC)/(1 . (C A2 C B1 / C C2 C D1 ) exp[ n1n 2 F(E − E1 ) / RT ] = K / Q − f (i m ) 2 n n n n (19.301b.300a. eq = E2° + (RT/n2F) ln (CB/CD) + (RT/n2F) ln [(1 . while recalling Equations 19.im/iLA)] (19.305) Then from Equations 19. we get upon rearrangement. and 19.306. 19.305. n n g(im) = (k ′ ) n 2 (k ′ ) n 1 C C2 C D1 f(im) dC dD (19. we find: E1s.306) Using Equation 19.303) where f (i m ) = (1 + i m / i LC ) n 2 (1 + i m / i LD ) n 1 /(1 − i m / i LA ) n 2 (1 − i m / i LB ) n 1 (19.im/iLB)/(1 + im/iLD)] (19.304) Let ω define a new function g(im) as: g(im) = (iLC) n 2 (iLD) n 1 f(im) (19.264 and 19.

If the reaction products C and D are absent from the initial reaction mixture. im/iLA << 1.310a) 1/rcat = n1n2F/W + φ n1n22/iLA + φ n12n2/iLB (19. for t → ∞.17) that: 1/im = 1/W + φ n2/iLA + φ n1/iLB (19.311) It can also be shown (see P19.307) Initial Rate.308) Also. im/iLB << 1 (19.n n g (i m ) = (k ′ ) n 2 (k ′ ) n 1 C A2 C B1 exp[ n1n 2 F(E − E1 ) / RT ] dC dD 2 (19.309) Under these conditions it can be shown (see P19.18) that the mixed potential is given by: (F/RT)(n1 + n2)Em = (F/RT)(n1E1° + n2E2°) + ln CB/CA + ln (k′ dD/k′ dC) + ln [(1 – im/iLB)/(1 – im/iLA)] (19. im/iLD >> 1 (19.310b) and n φ n φ W = (k ′ ) n 2 φ (k ′ ) n 1φ C A2 C B1 exp[ n1n 2 φF( E − E1 ) / RT ] dC dD 2 (19.312) 65 . then at the beginning of the reaction the following condition is satisfied: im/iLC >> 1.

0 50 6.43 295 2.10 The platinum-catalyzed hexacyanoferrate(III) plus iodide reaction The reaction between Fe(CN)63.4 265 1. we can write: 66 .+ 1/2I3(1) The kinetics of this reaction was investigated by Freund and Spiro (J. Faraday Trans. Recalling Equation 19. Soc.and I. determine the reaction order for Fe(CN)63.43 294 1. 79. (a) Experiments conducted to examine the effect of the disc stirring rate on the reaction rate gave the following results: Rotation speed (rev min-1) Reaction rate (10-6 mol m-2 s-1) 100 2 200 2.EXAMPLE 19.0 150 10.. Show that these trends are consistent with an electrochemical mechanism of the platinum catalysis.4 244 (d) The experimental results presented above in part (c) also include data on the effects of the reactant concentrations on the mixed potential indicated by the platinum metal.65 500 4. [Feic] (10-3 mol dm-3) [I-] (10-3 mol dm-3) r (10-6 mol m-2 s-1) Emix (mV) 0. Solution (a) Figure E19.0 50 4.10a shows a plot of reaction rate.5 50 2.0 50 4. The overall reaction is: Fe(CN)63.65 2000 9.0 300 10. With the aid of these data.+ 3/2I. assuming (as found in (a) above) a transport-controlled process. stirring rate. r.and for I-.311. 491-504 (1983)). Presented below are experimental data which give the effects of the reactant concentrations on the reaction rate (r).0 50 12.2 307 1.0 30 2.is strongly catalyzed by platinum metal.64 299 5.0 80 6.75 300 3. 1. vs. Rationalize this observation.→ Fe(CN)64.43 1000 6.57 282 1.59 286 1.2 50 1. The potential of the disc was monitored in the course of the reaction and it was found to be independent of the rotation speed.59 307 1.65 (b) (c) Show that these results are consistent with a completely mass transfer-controlled process.27 279 0. the platinum catalyst was used in the form of a rotating disc. Chem.

241b. we can write: k′ k′ dC = k″ dCω 1/2 = k″ dDω 1/2 (4) (5) dD From Equations 2. it is concluded that the experimental data do indeed follow complete mass transfer control. Figure E19.W = (k ′ ) n 2φ (k ′ ) n1φ f dC dD where f = C A2 C B1 exp[ n 1 n 2 φF(E − E 1 ) / RT ] 2 n φ nφ (2) (3) Also. Thus. in view of Equation 19. recall Equation 19.293. iLB. 67 . 4.10a shows such a plot for the data provided. the square root of the disc rotation rate should give a straight line passing through zero.310 gives the mixed current density as: im = βmω 1/2 where i/βm = 1/f′ + φ n2/βA + φ n1/βB (9) (8) It follows from Equation 9 that a plot of im vs.241a. W = f′ω 1/2 where f′ = (k″ dC) n 2 φ (k″ dD) n1φ f Also. and 6 respectively in Equation 19. ω 1/2 should give a straight line. a plot of the reaction rate vs.310) (7) (6) Using Equations 19. and 5.310: 1/im = 1/W + φ n2/iLA + φ n1/iLB (19. and 6 to substitute for i LA. It can be seen from Equation 8 that for a complete mass transport-controlled process. 19.

have different stoichiometric coefficients.263 that 68 .10a (b) The mixed potential that corresponds to total mass transfer control is given by Equation 19. in the case of Equation 11.294a.= 1/2I3. and 19.(feoc). it follows from Equation 19.+ 2e2Fe(CN)63.= Fe(CN)64(11) (12) (10) (c) Comparing Equations 1.(feic). I3.e.e.to be equivalent to a hypothetical species I33-. Based on the overall reaction (Equation 1).= I3. i. and 7 into Equation 19.= I3.+ e. D:Fe(CN)64. Closer comparison of Equations 19. we get: (F/RT)(n1 + n2)Em = (F/RT)(n1E1° + n2E2°) + ln (CB/CA) + ln (k″ dD/k″ dC) + ln [(1 .+ 2Fe(CN)63.+ 2Fe(CN)63.+ 2Fe(CN)64(16) (13) (14) (15) where I33. we must transform Equation 11 into a form in which both the reactant and product have the same stoichiometric coefficient.+ eFe(CN)63. however. Inspection of this equation reveals that it has no dependence on the speed of rotation.= I3.= 2Fe(CN)64I33. and 12 with Figure 19. 19. B:Fe(CN)63.9 and Equations 19. that whereas in the former both A and C have the same value of the stoichiometric coefficient (i.βm/βA)] It follows from Equation 10 that a plot of Em vs. Therefore the experimental observations are consistent with the assumed total mass transfer control. Adopting Equation 15 as our working Equation.+ 2Fe(CN)64It must be noted that Equation 15 is equivalent to: 3I.312.312.263.+ 2e. We proceed by taking 3I. the following half-reactions can be written: 3/2I. ½ and 3/2 respectively. 11. In order to use the equations available in Section 9. Inserting Equations 19. 1). 4. it can be seen that the following correspondence exists: A:I F-.Figure E19.4.in Equation 15 has been replaced with 3I-.261.261 and 11 reveals. Then we can write: I33. C:I3-.and I.βm/βB)/(1 . 3.4 properly..262. w1/2 should have a zero slope..294b. 19.

we can write 1/rcat = (2)(1)F/W + (1/3)(2)(1)2F/iLA + (1/3)(1)(2)2F/iLB = 2F/W + (2/3)F/iLA + (4/3)F/iLB Now. φ = 1/(n1 + n2) = 1/3 (17) It must be noted further. that the 3I-/I33. n2 = 1.+ 2e.n1 = 2.280 and 19. CA = C I 3 − = C I − / 3 3 (26) (25) (24) Using Equation 26 to substitute for CA in Equation 25 and noting that CB corresponds to CFeic. using Equations 19.substitution involves both a stoichiometric and a thermodynamic equivalence.(feic). B:Fe(CN)63. we recognize that the concentrations are related as: C I 3− = C I − / 3 3 (18) The thermodynamic equivalence can be derived by expressing the redox reaction for the I 3-/Icouple in the following two alternative ways: I3.= 3I3 − E1 = E1° + (RT/2F) ln ( C I3 / C I − ) (19) (20) (21) I3.+ 2e.310b) Bearing in mind Equation 17.= I33− E1 = E1° + (RT/2F) ln ( C I3 / C I3− ) (22) 3 It follows from Equations 20 and 22 that: C I3− 3 3 = CI− (23) We now turn to Equation 19. we can write: 69 .282 to substitute for iLA and iLB. we get: 1/rcat = 2F/W + (2/3)F/k′ dACA + (4/3)F/k′ dBCB Referring to the stoichiometric equivalence (Equation 18). In the case of the stoichiometric equivalence. as well as the correspondence A:I33-.310b: 1/rcat = n1n2F/W + φ n1n22/iLA + φ n12n2/iLB (19.

log C Feic for constant CI-. W = (k′ dC)1/3(k′ dD )2/3CA1/3CFeic2/3 exp[2F(E2° .α2)F Similarly.for constant CFeic is shown in Figure E19. The corresponding plot of log q vs. we can write: q = [1/rcat – (4/3)F/k′ dBCFeic] = 2F/f″CI-CFeic2/3 (33) (d) Figure E19.b. CA = C I 3 − 3 − = C I3 (29) Accordingly.a shows a plot of log q vs. Equation 19.5. Referring to Equation 19.289. dA CI.66.311) we can write.in Equation 33. we expect (35) (34) 70 .E1°)/3RT] (30) (31) CI- (32) If the last term on the right hand side is relatively small.302a and 19. we can see that for constant CB.e. dEm/d ln CB = bRT/(1 + α1 .. 0.e.311. i.311 we must use the thermodynamic equivalence (Equation 23).. for constant CA.E1°)/3RT] (28) We note again that CA refers to C I3− . 1/rcat = 2F/f″CI-CFeic2/3 + (4/3)F/k′ dBCFeic + 2F/k′ dA dD )2/3 CI-CFeic2/3 exp[2F(E2° . However. Thus.+ (4/3)F/k′ dBCFeic (27) W = (k ′ ) n 2φ (k ′ ) n1φ C A2 C B1 exp[ n 1n 2 φF(E − E1 ) / RT ] dC dD 2 n φ nφ (19. in Equation 19. The slope of 1. is consistent with the reaction order of 2/3 for CFeic in Equation 33.1/rcat = 2F/W + 2F/k′ Recalling Equation 19. The slope obtained. log CI. and assuming α1 = α2 = 0.311 becomes: W = (k′ dC)1/3(k′ or W = f″CI-CFeic2/3 Combining Equations 27 and 31. now we recognize that the parameter W is 3 related to the thermodynamic treatment of the redox couples (see Equations 19. i. dEm/d ln CA = =aRT/(1 + α1 .α2)F At the temperature of the experiments (5°C).0 is also in consonance with the reaction order of unity for CI.302b).

In order to satisfy the principle of conservation of energy. Figure 19. Then. we have an electron-transfer mechanism (Equation 19.14 that whether the electron or hole transfer pathway predominates depends on the relative positions of the band edges of the semiconductor with respect to the energy levels of the redox couple in the electrolyte.312a) (19.5 19.312b) It can be seen from Figure 19.with a slope of -23.yyb.yya shows a plot of Em vs. depending on whether electron transfer is with the conduction band or the valence band.312a).14.1 Electron Transfer at Semiconductor Electrodes Energy Levels in Electron and Hole Transfer The kinetics of electrochemical reactions at the semiconductor/aqueous interface can be considered in terms of the transfer of carriers (holes or electrons) from energy levels in the solid to those in the aqueous phase. radiationless electron transfer is permissible only if the initial and final locations of the electron are at the same energy level.5. and vice-versa. 71 .312b): A+ + e. Consider that Equation 19. shows a slope of 8. and a hole-transfer mechanism (Equation 19. two different reaction paths are available. 19.2 mV also in agreement with theory (Equation 37). ln I. consistent with theory (Equation 36).99 mV (36) (37) Figure 19. Electron transfer in the valence band can be visualized in terms of the transfer of holes. The corresponding Em vs.2 mV. ln Feic plot. Thus.= B A+ = B + h+ (19.1 now refers to a reaction taking place at the semiconductor/electrolyte interface.0 mV dEm/d ln CB = RT/3F = 7.dEm/d ln CA = -RT/F = -24. as illustrated in Figure 19.

are respectively the proportionality constants for the anodic and cathodic conduction band electron reactions. consideration of all the energy levels will require an integration to be performed. Thus. we can envisage the electrode reaction thus: Az+(aq) + (Occupied State) e.314a) (19.= B SOLID AQUEOUS PHASE Ev VALENCE BAND h+ + A = B + h+ Figure 19. However.kc-°κ(Ec)°CAs°WA(Ec)°ns (19.(s) ↔ B(aq) + (Vacant State) (s) (19.312). only the energy bands in the neighborhood of the band edges Ec and Ev are relevant. in general. Accordingly.14 Electron transfer at a semiconductor electrode. for the conduction band process.313) The rate of electron transfer will be expected to be proportional to the density of empty states on the aqueous species (A+) and the density of occupied energy states at the same energy level in the solid phase.CONDUCTION BAND Ec eA+ + e . It will be recalled (Chapter 9) that the energy states in the semiconductor are spread over a wide range of energies.314b) where kc+ and kc. we can express the rate as: ic = ic+ + ic= kc+°κ(Ec)°CBs°WB(Ec)°Nc . only a few states are occupied in the conduction band while most of the energy states in the valence band are occupied. as far as electron transfer is concerned. Thus. κ(Ec) is the probability that the collision of an aqueous 72 . In the case of the conduction band electron transfer (Equation 19.

73 . and ps is the hole density at the surface.species with the surface will result in electron transfer. Nc is the density of energy states in the conduction band. for a valence band process. the probability of finding the oxidized and the reduced species at an energy state that corresponds to Ec. CAs and CBs are the surface concentrations of the oxidized and reduced aqueous species.315a) (19. and ns is the electron density at the surface. WA(Ec) and WB(Ec) represent respectively.315b) where kv+ and kv.are respectively the proportionality constants for the anodic and cathodic valence band hole reactions.kv-°κ(Ev)°CAs°WA(Ev)°Nv (19. Nv is the density of energy states in the valence band. Similarly. iv = iv+ + iv= kv+°κ(Ev)°CBs°WB(Ev)°ps .

then it follows from Equations 19.316) If the surface concentrations of electrons and holes at equilibrium are denoted by nseq and pseq respectively. there is no net conduction band or valence band electron transfer.319a) (19.318 become: ic = ic..o [1 .o and iv.o = kc+°κ(Ec)°CB°WB(Ec)°Nc = kc-°κ(Ec)°CA°WA(Ec)°nseq iv.o = kv+°κ(Ev)°CB°WB(Ev)°pseq = kv-°κ(Ev)°CA°WA(Ev)°Nv (19.320) (19. When there is no concentration gradient. i.317) (19.5. while ic.319b) (19.e.321) Equations 19.314 .(CAs/CA)] (19.318 take into consideration the fact that at equilibrium the bulk and surface concentrations of the aqueous reactants must be equal.322) 74 . CAs/CA = CBs/CB = 1 Therefore Equations 19.(CAs/CA)(ns/nseq)] iv = iv.317 and 19.19.317 and 19.318) where CA and CB are respectively the bulk aqueous phase concentrations of the oxidized and reduced species.2 is.o [(CBs/CB)(ps/pseq) . Current-Potential Relations At equilibrium.o [CBs/CB .316 that: ic = ic. CAs = CA and CBs = CB. That iv = ic = 0 (19.19.323) (19.o represent respectively the exchange currents for the conduction band and valence band processes and are given by: ic.(ns/nseq)] (19.

iv = iv.329 reveals that for a conduction band electron transfer.331) reveals that in this case the apparent transfer coefficient is unity.∆ φ seq (19.326) (19. the applied potential affects the cathodic current but not the anodic current.327) and ∆ φ seq is the equilibrium value of ∆ φ .o [(ps/pseq) .324) (19. On the other hand. 75 . Here.1)] (19. Further examination of Equation 19. Combination of Equations 19.329) A comparison of the Butler-Volmer equation (Equation 19.325) where nb is the bulk concentration of electrons in the conduction band of the semiconductor.328) (19.1)] Recall Equation 5.21) with Equation 19. It follows that ns/nseq = [nb exp (-e ∆ φ s/kT)]/[nb exp (-e∆ φ seq/kT)] = exp (-ηsce/kT) where ηsc is the overpotential given by ηsc = ∆ φ s . a similar comparison with the expression obtained for hole exchange with the valence band (Equation 19.161. the anodic current is potential-dependent whereas the cathodic current has no potential dependence. ns = nb exp-e ∆ φ s/kT (19.exp (-ηsce/kT)] Also. recall that the bulk and surface hole concentrations are related thus: ps = pb exp e∆ φ s/kT It follows from Equations 19.o [exp (ηsce/kT) .331) (19.330 that: iv = iv.o [1 .330) (19.329 indicates that for electron exchange with the conduction band.327 gives: i = ic.324 and 19. as can be seen from Equation 19.323 and 19. The reverse situation occurs in the case of a valence band electron transfer.331. the apparent transfer coefficient is zero.

16 Current-voltage curves for conduction-band and valence-band electron transfers at the semiconductor/electrolyte interface (after Gerrischer. Sci..= Fe(CN) The cathodic current was found to vary in direct proportion to the surface concentration of electrons and to the ferricyanide concentration.498). 15. p.15 Reduction of oxidizing agents on n-ZnO (a) Ferricyanide ions were reduced at the n-ZnO electrode by applying a cathodic potential: Fe(CN)+ e. _____________________________________________________________________________ _ EXAMPLE 19. 368 (1973)). 119 (1968)..15a presents cathodic currents obtained from the reduction of a number of oneequivalent oxidizing agents at a ZnO electrode. Solution 76 . Rationalize these observations in the light of the above discussion of conduction band electron transfer.329 and 19.. Surface Sci. 9. Surf. Sci.331 respectively. 1970.log i ic iv i v. (see Freund and Morrison.o ic CATHODIC ANODIC η /(kT/e) Figure 19.(see van den Berghe et al. as described by Equations 19. Figure 19. Show that the observed results are consistent with a first-order dependence of the cathodic current on the surface electron density.16 shows a graphical representation of the current-voltage relations for conduction band and valence band charge transfers. Surf.o iv i c.. 363 (1969)) (b) Figure E19. Morrison. 39.

Thus it follows from Equation 3 that ln |i| = ln (k°CA°nseq ) .319b) (2) (19.15a Cathodic currents for one-equivalent oxidizing agents at ZnO. as was observed experimentally.329 becomes: i = -ic. Equation 19. Thus it follows Equations 1 and 2 that i = -k°CA°nseq exp (-ηsce/kT) = -k°CA°ns (3) (4) where Equation 19. Equation 4 shows that the reduction rate is first order in the oxidant concentration and in the surface concentration of electrons. as can be seen from Equation 2 is proportional to C A and nseq .(a) Recall the expression derived above for the current-potential relation for a conduction band electron transfer: i = ic.329) (1) It can be seen from Equation 1 that the rate of the reduction reaction is proportional to the exchange current density.o exp (-ηsce/kT) where ic. Figure E19.ηsce/kT (5) 77 .327 has been used to relate nseq and ns.o = kc-°κ(Ec)°CA°WA(Ec)°nseq = k°CA°nseq (19. which. (b) From Equation 19.exp (-ηsce/kT)] If the cathodic paartial reaction predominates.o [1 .327 we know that ns is exponentially dependent on ηsce/kT.

24. as expected from theory. A.506. ____________________________________________________________________________________________ EXAMPLE 19. p. (see G. Tyagai.16 Reduction of Fe3+ on CdS Show that for the CdS/Fe3+ system a slope of 60 mV/decade is obtained from the experimental data.The curves in Figure 19.15a give slopes of ~60mV/decade. Elecktrokhimiya. Fig. 1. also V. 377 (1965)) _____________________________________________________________________________ _ 78 .

17 for an n-type semiconductor (see Green. they must then be transported to the solid/aqueous interface where the electrochemical reaction takes place. Between the bulk and space charge regions is the diffusion region.3 Transport of Charge Carriers in Semiconductors Where a surface reaction involves the consumption of a minority carrier. A concentration gradient of holes therefore arises outside the space charge region. the diffusion region. the hole concentration must satisfy the following differential equation: Dpd2p/dx2 + rp = 0 (19. the semiconductor electrode can be divided into three regions: the bulk region.17 The diffusion of holes in an n-type semiconductor Recalling Equation 9. p. In order to accomplish this. the rate at which this carrier is transported to the semiconductor electrolyte interface can determine the rate of the overall reaction.19. we must first determine the rate at which holes and electrons are produced in the bulk of the semiconductor. In this case.332) 79 . It is therefore of interest to develop a quantitative description of carrier diffusion in a semiconductor. and the space charge region. under steady-state conditions. it can be stated that. as illustrated in Figure 19. Once the carriers have been produced. characterized by a concentration gradient of holes.5.12a. In the presence of current flow.386). the equilibrium hole and electron distributions are preserved. holes constitute the minority carriers. As a result of the hole-consuming surface reaction. In the bulk region. the hole concentration at the edge of the space charge region (x=x1) will be lower than its equilibrium value. Space Charge Region Bulk Region po Diffusion Region Jp p1 x2 x x1 0 Figure 19.

inside a semiconductor. ln(p/pinitial) = -krecnot (19.krecnop (19. it has been assumed that since for an n-type semiconductor.335) In writing Equation 19. electrons and holes can undergo recombination. p. It follows from Equation 19.334) Let us now consider an n-type semiconductor.335 that.where Dp is the diffusion coefficient of a hole. Then the rate of recombination will be given by: dp/dt = . electrons are the majority carriers.335.336) We can define the lifetime of a minority carrier as the time it takes to decrease the concentration of non-equilibrium holes or electrons to 1/e of its original value.333 represents an elementary reaction.+ h+ = 0 (19. the approximation n=no can be made. Let us suppose that an excess of holes is introduced by some means.337) The lifetime of the minority carrier (tp) can also be viewed as the average time excess minority carriers remain in their excited state after generation (Morrison. This process can be viewed in terms of a homogeneous reaction of the form: e. Therefore.11). substituting (p/pinitial) = 1/e at t = tp in Equation 19. It follows from Equations 19. and r p is the net rate of hole production inside the semiconductor.337 that. tp as: tp = 1/krecno (19.333) The forward reaction represents recombination.krecnp = krec (nopo -np) = krec (ni2 -np) (19.336 gives the lifetime of holes. As noted previously. 80 . while the reverse represents the generation of an electron-hole pair. the corresponding rate equation can be expressed as: r = dp/dt = dn/dt = rgen + rrec = kgen .334 and 19. Assuming that Equation 19.

338) (19. p = po p = p1 (19.343) (19.332 and 19.346b) 81 (19.345) (19.342) The parameter Lp is termed the diffusion length.339) (19.x)/Lp] Therefore.po) = (p1 .341) Applying these boundary conditions to Equation 19.po) exp[(x1 . dp/dx = (p1 .p)/tp = 0 The relevant boundary conditions are: x → ∞. x = x1.340) (19. for x=x1. It follows from Equation 19.339 gives: (p .346a) (19.344) .po)/Lp The hole current at x=x1 is then given by: ip = -eDpdp/dx = -eDp(p1 .p)/tp Combining Equations 19.338.po)/Lp (19.po)/Lp] exp[(x1 . It follows from the definition of the diffusion length that any holes generated in the region between x=(x1+ Lp) and x1 will enter the space charge region without recombining.x)/Lp] where Lp = (Dptp)1/2 (19.343 that dp/dx = [(p1 . we get: Dpd2p/dx2 + (po . It represents the average distance the minority carrier (a hole in this case) diffuses before recombination occurs.rp = dp/dt = (po .

a limiting current (ip. it can be assumed that the holes (or electrons) at the surface are in equilibrium with the holes (or electrons) at the edge of the space charge layer: ps = p1exp(e∆ φ s/kT) ns = n1exp(-e∆ φ s/kT) (19.46b and 19.lim) (19.347 that: ip = -(p1 . the resulting situation can be viewed as a "quasiequilibrium".349.. If the departure from equilibrium is not too drastic.348a) (19.351) (19.When p1 = 0. The surface reaction results in current flow between the bulk regions of the semiconductor and the surface.lim/po or (p1/po) = 1 . Under these conditions. the condition np = ni2 is no longer satisfied. the holes and electrons are not in mutual equilibrium. That is.n2) = (p1 -po) Recalling Equation 19.347) With the aid of Equation 19. ip.348b. we can write: ∆ φ s = (kT/e)ln(ps/p1) = (kT/e)ln[(ps/po)(po/p1)] = (kT/e)ln(ps/po) .lim) is attained.348b) (19. we can obtain a relationship between the surface concentration of holes and the space charge potential in the presence of current flow.350) Also.(kT/e)ln(p1/po) (19.(ip/ip.e. i.352) 82 .349) (19.lim = eDppo/Lp It follows from Equations 19.po)ip. no and po as: (n1 . This current flow results in a departure of the hole and electron distributions from their respective equilibrium values. However. n1 and p1 are related to their equilibrium values. since the region outside the space charge consitutes an electroneutral region.

lim)] We can define a hole-transport overvoltage.353 as: ∆ φ s = (kT/e)ln(ps/po) .ηTp .358.(ip/ip.(kT/e)ln(ps.∆ φ s. the total overvoltage is given by: η = ηs + ηH From 19.354.359) (19.359.eq/po) (19.eq = (kT/e)ln(ps.353) The hole-transport overvoltage can be viewed as the contribution which hole transport makes to the space-charge overvoltage. ηTp.(ip/ip.Combining Equations 19. we get: 83 .ηH + ηTp)/kT] (19.356.eq) = exp[e(η . there is no net current flow and the corresponding space-charge potential is then given by: ∆ φ s.lim)] (19. we can rewrite Equation 19. as ηTp = (kT/e)ln[1 . the space charge overvoltage can be expressed as: ηs = ∆ φ s .eq = (kT/e)ln(ps/po) . with the aid of Equations 19.355 and 19.348b and 19.355) At equilibrium.358) (19.ηTp (19.eq) .357 and 19.354 to substitute for ηTp in Equation 19.ηTp Now.357) Alternatively. Using Equation 19.356) Therefore. using Equation 19.352 gives: ∆ φ s = (kT/e)ln(ps/po) . (ps/ps.eq/po) = (kT/e)ln(ps/ps.(kT/e)ln[1 .354) (19.

L. pp. B. 1967. K. Stokes. New York. U. A. 12. New York. R. New York.(ps/ps. Prentice Hall. pp. Wiley. Englewood Cliffs. NJ. 1959. 118-132. Bockris and S. 14. Theory and Principles of Electrode Processes. Morrison. Electrochemical Methods. Diffusion: Mass Transfer in Fluid Systems. Modern Electrochemistry. 3452. pp. A. NY 1984. O'M.. J. 2. pp. 84 . Prentice Hall. 1991. 2nd ed.(ip/ip. J. Electrochemical Systems. J. New York. Dvorak. D. Henderson. S. Electrochemistry of Metals and Semiconductors.. Faulkner. Kinetics of Electrode Processes. 6. 8. 1970.R. 2nd ed. 1991. Plenum. New York.360) _____________________________________________________________________________ _ FURTHER READING 1. 10. 9a. 1970. Jost. A. 4. 287460. pp.5. New York. Vijh. Principles of Electrochemistry. Koryta. Surface Electrochemistry. M. NJ. Plenum. 9. Bard and L. 7. 463-542. 3. Cussler. 1980. Electrochemical Engineering Principles. Gerischer. 1972. J. Roland Press. 41-48. (429-487?) (488-552).N. J. Vol. New York. Reddy. K. New York. 2nd ed. E. London. 1973. Eyring. 1993. 5. 86-135. Plenum. New York. Marcel Dekker. S. Electrolyte Solutions. J. 284-335. R. Newman. Electrochemical Kinetics. pp.H. 79-113. and W.. Erdey-Gruz. G. 11. Electrochemistry at Semiconductor and Oxidized Metal Electrodes. New York. 13. Englewood Cliffs. Wiley-Interscience.. in Physical Chemistry: An Advanced Treatise. 1965. 1993. T. Academic. 1980. O'M. H. E. Khan. Wiley. Prentice. NY. Academic.4 Redox Reactions (19. eds.eq) = [1 .lim)] exp[e(η-ηH)/kT] 19. and L. J. Robinson and R. Butterworths. Conway.K. H. Cambridge University Press. Kavan. Vetter. New York. Bockris and A. Vol. 2. "Semiconductor Electrochemistry".

Principles. pp. J. J. in Adv. 1973.3. 1993. 4. 79. 85 . SECTION 19. 16. C. 463-542. Etching of III-V Semiconductors.. J.. 9a. Oxford. 2. Marcel Dekker. Chem. Sato. A. Notten. Part 23.. Brett and A. H. 1998. Bard. 79-113. 79. Ferguson. 1. 2. New York. A. P. Eyring. Electrochem. pp. 75.6 1. 3. Kelly. Chem. S. Part 17. Vol. Faraday Trans. Spiro. S. Soc. Electrochemistry of Metals and Semiconductors. Electrochemistry at Semiconductor and Oxidized Metal Electrodes. Spiro. R.. Freund and M. D. G. Bockris and A. H. A. 471-490 (1983). Jost. "Semiconductor Electrode Reactions". Electrochem. J. Gerischer. Eng.5 1. A. and Applications. and W.. M. P. 1991. 4. New York. An Electrochemical Approach. 1980.. 1970. Chem. Miller. H.N. SECTION 19. Part 22. Am. Freund and M. New York. K.K. Plenum. Theory and Experiment”. 3452. 17. "Heterogeneous Catalysis in Solution. 1. Vol. J. E. eds.K. Oxford. P. 2.4 1. NY. O'M. 1. L. L. Soc. Faraday Trans. 3.. New York. van den Meerakker. Vijh. 103. NY. in Physical Chemistry: An Advanced Treatise. ed. Electrochemistry. Kinetics of Oxidation-Reduction Rections Catalyzed by Electron Transfer through the Solid: An Electrochemical Treatment". 1507-1512 (1979). 139-232 (1961). J. Academic.15. “Catalytic Water Reduction at Colloidal Metal ‘Microelectrodes’. Kinetics of a Redox system Showing Complete Mass-transport Control: The Hexacyanoferrate (III) + Iodide Reaction at a Rotatingplatinum-disc Catalyst". Plenum. D. New York. 5336-5341 (1981). M. Faraday Trans. and J. Gerischer. Elsevier. Modern Electrochemistry. J. Elsevier Advance Technology. Oxidation-Reduction Rections Catalyzed by Electron Transfer through the Solid: Theory for Partial and Complete Mass-transport Control". "Semiconductor Electrochemistry". 491-504 (1983). Reddy. pp. Chem. O. 1. 12311264. pp. Methods. "Heterogeneous Catalysis in Solution.. J. and J. H. Soc. "Heterogeneous Catalysis in Solution. Electrochemistry at Metal and Semiconductor Electrodes. N. McLendon. M. Morrison. SECTION 19. M. Soc. New York. P. L. 2. Delahay. U. NY. Spiro. Brett. 1970. Henderson.

Yu. Ya. 1986. Memming. in Comprehensive Treatise of Electrochemistry. Elsevier. 7. O'M. Bockris. NY. New York. Gurevich.529-592. 6. Conway. pp. 86 . S. Semiconductor Photoelectrochemistry. U. Plenum. "Processes at Semiconductor Electrodes". H. 8. E. 1983. 1998. B. 35. J. Acta. Pleskov anf Yu.5. M. R. Sato. Gerischer. 1677-1699. eds. Khan. Electrochemistry at Metal and Semiconductor Electrodes. Electrochim. New York. Vol. Yeager. E. N. Consultants Bureau. and R. White. "The Impact of Semiconductors on the Concepts of Electrochemistry". 7. E. New York.. V.

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