a Understanding the Difference between Inner- and Outer-Sphere Mechanisms An Electrochemical Experiment Luz Maria Torres, Adrién F. Gil, Laura Galicia, and Ignacio Gonzalez" Universidad Auténoma Metropoltana—Iztapalapa, Departamento de Quimica, Apartado Postal 55-534. México D.F. México In homogeneous solutions, two mechanisms are recog nized to explain redox reactions for complex molecules: the inner-sphere and outer-sphere mechanisms. In an inner- sphere mechanism, the charge transfer proceeds through a binuclear ligand-bridged complex between the two species involved. In an outer-sphere mechanism, the charge trans- fer is accomplished with the primary coordination spheres remaining intact (1,2). ‘Remember that, in homogeneous redox reactions, both the donor and acceptor are in solution; in this way, the elec- tron-transfer mechanism only involves species in solution. Conversely, in electrochemical reactions, charge transfer is accomplished heterogeneously between an electronic eon- ‘ductor (e.g, @ metal, semiconductor, conducting polymer) ‘and an ioni¢ conductor (a solution containing the electroac- tive species), However, will the nature of the electronic ‘conductor make a difference on the electron-transfer ‘mechanism? ‘Because the nature of the electronic conductor has great {influence in some redox reactions, the con- cepts of outer- and inner-sphere electron- tranafer mechanisms have already been ap- plied to electrochemical reactions. In this 50 ase, mechaniams are referred to the inner land outer Helmholtz plane as follows. “In an innerlayer mechanism, the electron transfer proveeds through a common ligand Shared by the electronic conductor and the lectroactive species. ‘Inan outerlajer mechanism, the electroac- 100 tive species will be located in the outer Helmholtz plane, with its coordination sphere remaining intact during the eleetron- 180 transfer process @), 109 1 pal Even though these concepts are well- Iknovn, there is a lack of electrochemical ex- periments showing the great influence of the type of mechanism on the electrode kinetics. ‘The experiment described hore was de- signed Lo show these differences by eompar- ing the behavior on two different metals (gold and platinum) of two systems: ‘the well-behaved, outertaygr mechanism ‘eouple, [FetCNe)”AF(CN SI «the FeTD/FetTl couple in sufrie acid me- dium, which is known to follow an inner layer mechanism ‘A cyclic voltammetry (CV) experiment (3-5) is used to obtain a preliminary insight of the ‘phenomenon; secondly, the rotating disk vol- fammetry technique (RDE) (6) is used to cal- ‘culate the kinetic parameters Tauthor t whom corespondence should be ad crossed. 808 Journal of Chemical Education Experimental Procedures Reagents Stock solutions of 4 mM KyFe(CN)g prepared in 1 M NaNOs and 4 mM Fea(SOys prepared in 1M HS0q, are used in the CV experiments. In addition, solutions of 4 mM K,Fe(CN)g/4 mM KgFe(CN) prepared in 1M NaNO and 4M Fe{S0,)e/4 mM FeSO, prepared in 1M H_S0, are used in the RDE experiments: All chemicals were reagent- grade and used without prior purification Apparatus ‘The equipment required is a potentiostat with potential sean capability and an XY recorder: A potentiostat PRT 20- 2X and a signal generator (Tacussel GST4) were used. The current versus potential curves were recorded on a Hevwlett Packard 7090A recorder. In addition, a rotating electrode apparatus (Taeussel CTV101T) was used in the E tnv) | MSE wo 0000 iv) MSE Figure 1, Cycle vokammograms for (a) 410°* M KgFe(CNJsin 1M NaNO and (b) 4108 MFex(SOaigin # M H;80,. Electrodes: gold (---) and platinum (—). Scan rete: 20 mvs"Table 1. AE = Epa Epe* aE Gals Pratnum IFerone™ 6 6 Foiil) 425 126 «Mx 103M Feta a 4M NaNO3 and 4 10° Mi Foti 1H ve2omve" Figure 2: Current densiy-overpotential curves of solutions contain- ing (@) 4 x 10°° M [Fe(CN)™ and 4 x 10° M (Fe(ON)I int M NaNO. Sean rato 3 mV"! (o) 4 x 10° Fell and 4 x 10 M fet, Sean sale S mvs « 22800 pm, letodos geld) and platinum () DE experiments. A conventional three-electrode cell is used for both the CV and RDE experiments. The working electrodes were a gold disk and a platinum disk (a glassy carbon disk can also be used), The electrodes used had the same geometric area (0.0314 em”), The reference electrode is @ HyHgS0,/K,S0, (MSE) electrode (Taeussel), and the counterelectrode was'a glassy-carbon rod, Procedure Pretreatment of the electrodes was earried out by polish- ing successively with 0.3- and 0.05-um alumina powder (Brehler) on a Microcloth felt disk (Buehler). Following ‘this, the electrodes were thoroughly rinsed with deionized, distilled water and sonicated in an ultrasonie bath for 10 ‘min, The solution was deoxygenated by bubbling Ny for 10 ‘min. After this, a Ne atmosphere was maintained over the solution during each run. Results and Discussion Cyeic Vottammetry ‘Typical eyctic voltammograms obtained for (Fe(CN)s1 and Fe(II) are shown in Figure 1, For the [Fe(CN)gl?- vole ‘tammograms (Fig. 1a), there is a slight difference in the clectrode potentials betwoen the cyclic voltammograms on gold and platinum electrodes, although the shape of the curves are quite similar, showing no dependence on the electrode material. Meanwhile, in the Fe(IID)-HSO, case Fig. 1b), the shape of the eyclie voltammograms changes, Furthermore, for the gold electrode, the peaks are dis. placed with respect to those obtained on platinum; the re- Auction peak is negatively shifted and the oxidation peak is positively displaced. On 2 more quantitative way, itis known that a fast clec- tron transfer is characterized by a separation between the peak potentials of .059/nV at 25°C (5, 7,8), that is, 8 = Boa Boe 2 283 5-0 ® When we calculate this value for the [Fe(CN)gI* system, ‘we have for both electrodes similar values that correspond. to. reversible system (Table 1). This means that the elec- trode kinetic is indgpenent ofthe electrode material in the case of [Fe(CN)g]"~. Meanwhile, for the Fe(IID-H,S0,, these values are greater than those of the former systerh and different for each electrode; this shows the strong de- pendence of the kinetics of the Fe(III) redox processes on the electrode material used (Table 1) When eathodic peak current (Upc) versus sweep rate 0) carves were plotted, straight lines were obtained: ‘The flux ofthe species is controlled by mass transport (dif. fusion) for both systems, Rotating Disk Electrode Voltammetry In order to obtain quantitative information to show the different behavior of the systems studied with respect to the electrode material, the mass flux to the electrode sur- face was controlled by the use of the RDE technique. Fi ‘ures 2a and 2b show the egrresponding jE curves of sol tions containing [Fe(CN)g)” AFe(CN)g!* gnd Fe(IILVRe(tt) (where jis the current density in mAlem*), In the}-E curves, we can generally distinguish two main regions: At low overpotentials the shape of the curve is given by the electron-transfer kineties and described by the Tafel equation. For the eathodie branch, v(m (Br @ and the suai rch, = {FEY (RE {aes A hih ovrotntls the cectron traf very fs and the charge flus is limited by mass transport to the sur. face of the electrodes, following the Levich equation B= 062R CDE NG o where o is angular velocity of the disk given by @ = 2xN, with N = rps; is the kinematic viscosity, ems (assumed 0.01 for dilute solutions); C” is concentration of eleetroac- tive species, moVem'; jis limiting eurrent density, Alem’, and n is number of exchanged eleetrons. ‘The curves obtained show that it is possible to notice that the behavior observed in the CV experiments is main. tained. The RDE voltammograms for the [Fe(CN)g} AFe(CN)gI* are similar for both gold and platinum elec- trodes; conversely, in the Fe (I1DyFe (11) system (Fig. 2b), a large difference is observed at low overpotentials when the ‘material is changed. At higher overpotentials the limiting current density (j) is the same for each system inde- pendently of the electrode used, This shows that the mass transport of the eleetroactive species to the electrode sur- face is independent of the electrode kinetics. The diffusion coefficients were calculated using the Levich equation; the Jit were obtained from experiments carried out at various, rotation speeds and are reported in Table 2 Kinetic Parameters In order to obtain the kinetic parameters for each sys- tem, we analyzed the overpotential-current density curves Volume 73 Numbers August 1996 809Table 2. Ditfusion Coofficionts Obtained ‘from RDE Voltammetry Curves” Table 3. Kinetic Data Obtained for the Two Systems ‘Studied on Gold and Platinum Electrodes* Dx 10° en’e! Gola Patinum [Fe(CN)el 2.93 317 Fel) 44 467 45.105 MFCR 1 M NEN v= 3 VE" anda x 10° Fl) In IM HS04 v= 5 AVE on geld an petrum isk econ, w = 2500, om of these couples in the kinetically controlled zone. Using the Tafel treatment, we ealeulated the eurrent exchange density (,) and the transfer eoefiient «for the cathodic process. The complementary transfer coefficient, B, was, faleulated independently from the anodic process (Table 5). For the Fe(I}) oxidation reaction, it was not possible to caleulate Because the mechanism is somewhat more com plicated in this region. Transfer Coffciente The transfer coffcientc can be interpreted as the fraction othe ener, imposed by the applied potential, that is used ta change the energy of the free-energy barrier fora eduction reaction; Bis the analogous fraction of energy forthe oxida- tion barrier, In the ease ofa reaetion with a simple reaction mechanism, the complomentary transfer coefficient wil bo tequal to 1a: Consequently the sum of a plus B, ealulated {independents will be unity. On the enatrary, if the reaction follows a more complicated mechanism, the sum of both ‘ansfer coefiients will not equal unity. In the case of the [Fe(CN)gI" Fe(CN)g]* reaction, the o +-flobtained is approximately unity This indicates thatthe potential variation applied to the system is only used for the modifieation ofthe aetivation energy for the anodic and cathodie processes. Consequently, this means that the charge transfer is erried out in one step, which is charac feriatic of an outer sphere mechanism. Ia the ease of the Fe(II) couple, the a yalues obtejned are smaller than those in the (F(CN)g)” AFe(CN)gI* ease; although values for B wore not ealeuiated in this work, Bochmann (Gyhas shown that a+ Bis lower than unity. This fact indi- cates that the electron transfer is carried out ina more complicated way: The variation of potential is not used nly for the activation procosses. It is necessary to use a fraction of the energy celated to the imposed potential in ander ta modify ather processes involved in the heterogene- fons change transfer (eg, adsorption, desorption, modiica- {on of the coordination sphere) ‘The Exchange Current Density ‘The exchange current density (j,) is the rate of electron exchange at equilibrium; here equilibrium means any mo- ‘ment at which the oxidation and reduction events proceed at the same rate. Modification of the , values for the same 810 Journal of Chemical Education Eeciede aD b crn? “FooweP™ | AD ~«Oa08 0378 OT PL «O63t 0363268, Asoo 6 FequntFea | UNF | Oa oe 5 3 ave for ho FO(GNPRHCNT™ oye efor be Exit ye: = 200 cad maspendety tor ha Stele reaction is obtained with changes in the nature of the elec- ‘trode or with changes in the coordination sphere of an in- ner-sphere reaction. When the values of j, calculated for the [Fe(CN)g]* #HFe(CN)g] couple with different electrode are compared, they are very similar (taking into account the experimental error in the kinetic parameters); from this, itis possible to consider that there is no influence of the electrode material on the kinetics of this couple. On the contrary, the j, values obtained in the case of the Fe(IIIvFe(I1) system, are very different for the two elec- trodes used showing that the electrode nature plays an im- portant role in the kinetics of this reactiog. The exchange ‘current density (j.) reported for [Fe(CN)g]” /[Fe(CN)g] is ‘the mean value of the jg values obtained from the anodic and cathodic branches for each electrode. For Fe(IIDVFe(TD), the j is calculated from those obtained from the cathodic branch only. ‘Although in the “time window” (7) of the electrochemical, ‘techniques used in this work, it is not possible to evidence the other steps involved in the charge transfer mechanism for the Fe(II1/Fe(I1) couple, the great influence of the elec- trode material on the kinetics of this couple ean be easily observed. ‘Acknowledgment ‘We thank J. G. Tbafiez for helpful comments. A. F. Gil acknowledges SRE (México), and Luz Maria Torres ac- knowledges CONACYT (México) for their scholarship. ‘Most of this work was supported by CONACYT Grant, 40200-18444, Literature Cited 1, orga a ox Stn Whey Lc, 1978, 2 ee Con Gann Cmi it 25 aa “4. Mati... 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