A.J. Bard, L.R. Faulkner - Electrochemical methods - Fundamentals and Applications (794273), страница 2
Текст из файла (страница 2)
1.7A.I11.6.2cn^V'V12.3.3, 4.2B.1.47.1.27.3.52.3.3,4.2cm 3V/smol cm" 3 s~lmol cm" 2 s" 1cm/s6.11.3.2,3.11.3.2, 3.21.4.1,9.2mol cm~ 3mol c m " 2mol cm" 3mol cm" 2cm/s3.13.23.13.29.2.1s" 1s-1s" 1s~]xvxviMajor SymbolsSymbol*>mtWj(A,E)wWj*cx>XX\x2YYУzzZ\m^Re7zZjSectionReferencesMeaningUsual Unitsrate of mass transfer to a surfaceprobability density function for species jwidth of a band electrodework term for reactant j in electrontransfercapacitive reactancemole fraction of species jdistance, often from a planar electrodedistance of the IHP from the electrodesurfacedistance of the OHP from the electrodesurfaceadmittanceadmittance vectordistance from an RDE or RRDE(a) impedance(b) dimensionless current parameter insimulationimpedance vectorfaradaic impedanceimaginary part of impedancereal part of impedanceWarburg impedance(a) distance normal to the surface of adisk electrode or along a cylindricalelectrode(b) charge magnitude of each ion in az: z electrolytecharge on species j in signed units ofelectronic chargemol cm s '1eV"cmeV1.4.13.6.35.33.6.2n10.1.213.1.22nonecmcm1.2.3, 13.3.31.2.3, 13.3.3cmrr110.1.210.1.29.3.110.1.2B.1.61ft"cmnnoneftftcm10.1.210.1.310.1.210.1.210.1.35.3none13.3.2none2.3aftftGREEK SYMBOLSSymbolSectionReferencesMeaningUsual Units(a) transfer coefficient(b) absorption coefficient(a) distance factor for extended chargetransfer(b) geometric parameter for an RRDE(c) 1 - a(a) дЕ/дС}(0, t)(b) equilibrium parameter in an adsorptionisotherm for species уsurface excess of species j at equilibriumrelative surface excess of species у withrespect to component rnonecm"1A"13.317.1.23.6.4nonenoneV-cm3/molnone9.4.110.5.210.2.213.5.2mol/cm2mol/cm213.1.213.1.2Major SymbolsSymbolПД8AAxviiSectionReferencesMeaningUsual Unitssurface excess of species j at saturation(a) surface tension(b) dimensionless parameter used to definefrequency (time) regimes in stepexperiments at spherical electrodesactivity coefficient for species уellipsometric parameterl/2r0(s/Do) , used to define diffusionalregimes at a spherical electrode"diffusion" layer thickness for species у atan electrode fed by convective transfer(a) dielectric constant(b) optical-frequency dielectric constant(c) porositycomplex optical-frequency dielectricconstantmolar absorptivity of species уpermittivity of free spacezeta potentialoverpotential, E — Eeqcharge-transfer overpotentialviscosity of fluid уmass-transfer overpotentialmol/cmdyne/cmnone5.4.2, 5.5.2nonenonenone2.1.517.1.25.5.2fractional coverage of an interface byspecies у(a) conductivity of a solution(b) transmission coefficient of a reaction(c) r0kf/Do, used to define kinetic regimesat a spherical electrode(d) double-layer thickness parameter(e) partition coefficient for the primaryreactant in a modified electrode systemelectronic transmission coefficientequivalent conductivity of a solution(a) reorganization energy for electrontransfer(b) £fr1/2(l + £0)/£>o2(c) dimensionless homogeneous kineticparameter, specific to a method andmechanism(d) switching time in CV(e) wavelength of light in vacuoinner component of the reorganizationenergyequivalent ionic conductivity for ion уequivalent ionic conductivity of ion уextrapolated to infinite dilution213.5.21.4.2,9.3.2nonenonenonenone13.3.117.1.211.6.217.1.2M" 1 cm " 1]m"2mVVV1gem' " V = poiseVnones 1/2none17.1.113.3.19.8.11.3.2,3.4.21.3.3, 3.4.69.2.21.3.3, 3.4.65.4.15.8.213.5.2= fl" 1-inonenone3.1.35.5.2cm" 1none13.3.214.4.2none1c m 2 ! ! " 1 equiv "eV3.62.3.33.6nonenone5.5.112.3snmeV6.517.1.23.6.2cm 2 II 1 equiv ]cm 2 fl" 1 equiv" 12.3.32.3.3xviiiMajor SymbolsSymbolКp(E)ФФMeaningUsual UnitsSectionReferencesouter component of the reorganizationenergy(a) reaction layer thickness(b) magnetic permeabilityelectrochemical potential of electrons inphase aelectrochemical potential of species j inphase achemical potential of species у in phase astandard chemical potential of species j inphase a(a) kinematic viscosity(b) frequency of lightstoichiometric coefficient for species у in achemical processnuclear frequency factor(D0/DR)112(a) resistivity(b) roughness factorelectronic density of states(a) nFv/RT(b) (1MFAV2)[/3O/£>O/2 " J3R/£>R2]excess charge density on phase уparameter describing potential dependenceof adsorption energy(a) transition time in chronopotentiometry(b) sampling time in sampled-currentvoltammetry(c) forward step duration in a double-stepexperiment(d) generally, a characteristic time definedby the properties of an experiment(e) in treatments of UMEs, 4Dot/rlstart of potential pulse in pulse voltammetrylongitudinal relaxation time of a solventwork function of a phase(a) electrostatic potential(b) phase angle between two sinusoidalsignals(c) phase angle between / a c and £ a ceV3.6.2cmnonekJ/mol1.5.2, 12.4.217.1.22.2.4, 2.2.5kJ/mol2.2.4kJ/molkJ/mol2.2.42.2.4cm2/s9.2.2none2.1.5s" 1nonefl-cmnonecm 2 eV" 1s" 1C/cm2none3.65.4.14.25.2.33.6.36.2.110.2.31.2,2.213.3.4ss8.2.25.1,7.3(d) film thickness in a modified electrode(a) electrostatic potential differencebetween two points or phases(b) potential drop in the space chargeregion of a semiconductorabsolute electrostatic potential of phase jjunction potential at a liquid-liquid interface5.7.1nonesseVVdegrees,radiansdegrees,radianscmV5.37.33.6.23.6.42.2.110.1.210.1.214.4.22.218.2.2VV2.2.16.8Major SymbolsSymbolФоф2XXU)(bt)x(at)xXfФxixMeaningUsual UnitsSectionReferencesstandard Galvani potential of ion transferfor species j from phase a to phase /3total potential drop across the solution sideof the double layerpotential at the OHP with respect to bulksolution(12/7)1/2£fT1/2/Do/2dimensionless distance of box; in asimulationnormalized current for a totally irreversiblesystem in LSV and CVnormalized current for a reversible system inLSV and CVrate constant for permeation of the primaryreactant into the film at a modifiedelectrode(a) ellipsometric parameter(b) dimensionless rate parameter in CV(a) angular frequency of rotation;2тг X rotation rate(b) angular frequency of a sinusoidaloscillation; 2rrfV6.8mV13.3.2V1.2.3, 13.3.3nonenone7.2.2B.1.5none6.3.1none6.2.1cm/s14.4.2nonenones" 117.1.26.5.29.3s" 110.1.2STANDARD ABBREVIATIONSAbbreviationMeaningADCAESAFMASVBVCBCEanalog-to-digital converterAuger electron spectrometryatomic force microscopyanodic stripping voltammetryButler- Volmerconduction bandhomogeneous chemical process preceding heterogeneouselectron transfer1cyclic voltammetrycapillary zone electrophoresisdigital-to-analog converter(a) dropping mercury electrode(b) 1,2-dimethoxyethaneTV, TV-dimethylformamideDimethylsulfoxidedifferential pulse polarographydifferential pulse voltammetryCVCZEDACDMEDMFDMSODPPDPVSectionReference15.817.3.316.311.83.318.2.212.1.16.1,6.511.6.415.87.1.17.3.47.3.4betters may be subscripted i, q, or r to indicate irreversible, quasi-reversible, or reversible reactions.xxMajor SymbolsAbbreviationMeaningECheterogeneous electron transfer followed by homogeneous1chemical reactioncatalytic regeneration of the electroactive species in a following1homogeneous reactionheterogeneous electron transfer, homogeneous chemical reaction,and heterogeneous electron transfer, in sequenceelectrogenerated chemiluminescenceelectrocapillary maximumstep wise heterogeneous electron transfers to accomplish a2-electron reduction or oxidation of a specieselectrochemical impedance spectroscopyelectromotive forceelectrochemically modulated infrared reflectance spectroscopyelectron spin resonanceelectrochemical scanning tunneling microscopyextended X-ray absorption fine structurefast Fourier transformGouy-Chapman-Sterngalvanostatic double pulsehexagonal close-packedhanging mercury drop electrodehighly oriented pyrolytic graphiteinner Helmholtz planeideal polarized electrodeinfrared reflection absorption spectroscopyinfrared spectroelectrochemistryion-selective electrodeinterface between two immiscible electrolyte solutionsindium-tin oxide thinfilmLangmuir-Blodgettliquid chromatography with electrochemical detectionlow-energy electron diffractionlinear sweep voltammetrymercury film electrodenormal hydrogen electrode = SHEnormal calomel electrode, Hg/Hg2Cl2/KCl (1.0M)normal pulse polarographynormal pulse voltammetryouter Helmholtz planeoptically transparent electrodeoptically transparent thin-layer electrodepulsed amperometric detectionpropylene carbonatepotential difference infrared spectroscopypotential of zero chargequartz crystal microbalanceEC'ECEECLECMЕЕEISemfEMIRSESRESTMEXAFSFFTGCSGDPHCPHMDEHOPGIHPIPEIRRASIR-SECISEITIESITOLBLCECLEEDLSVMFENHENCENPPNPVOHPOTEOTTLEPADPCPDIRSPZCQCM1SectionReference12.1.112.1.112.1.118.113.2.212.1.110.1.12.1.317.2.117.4.116.217.6.1A.613.3.38.613.4.25.2.213.4.21.2.3, 13.3.31.2.117.2.117.2.12.46.818.2.514.2.111.6.417.3.36.111.81.1.17.3.27.3.21.2.3, 13.3.317.1.117.1.111.6.417.2.113.2.217.5Letters may be subscripted /, q, or r to indicate irreversible, quasi-reversible, or reversible reactions.Major SymbolsAbbreviationMeaningQRERDERDSRPPRPVRRDESAMSCESECMSERSSHESHGSMDESNIFTIRSquasi-reference electroderotating disk electroderate-determining stepreverse pulse polarographyreverse pulse voltammetryrotating ring-disk electrodeself-assembled monolayersaturated calomel electrodescanning electrochemical microscopysurface enhanced Raman spectroscopystandard hydrogen electrode = NHEsecond harmonic generationstatic mercury drop electrodesubtractively normalized interfacial Fourier transform infraredspectroscopysolid polymer electrolytesurface plasmon resonancesodium saturated calomel electrode, Hg/Hg2Cl2/NaCl (sat'd)scanning tunneling microscopysquare wave voltammetrytetra-/2-butylammonium fluoboratetetra-ft-butylammonium iodidetetra-w-butylammoniumperchloratetetraethylammonium perchloratetetrahydrofuranultrahigh vacuumultramicroelectrodeunderpotential depositionX-ray photoelectron spectrometryvalence bandSPESPRSSCESTMswvTBABF4TBAITBAPTEAPTHFUHVUMEUPDXPSVBxxiSectionReference2.1.79.33.57.3.47.3.49.4.214.2.21.1.116.417.2.21.1.117.1.57.1.117.2.114.2.617.1.316.27.3.517.35.311.2.117.3.218.2.2CHAPTER1INTRODUCTIONAND OVERVIEWOF ELECTRODEPROCESSES1.1 INTRODUCTIONElectrochemistry is the branch of chemistry concerned with the interrelation of electrical and chemical effects.
A large part of this field deals with the study of chemicalchanges caused by the passage of an electric current and the production of electrical energy by chemical reactions. In fact, the field of electrochemistry encompasses a hugearray of different phenomena (e.g., electrophoresis and corrosion), devices (electrochromic displays, electro analytical sensors, batteries, and fuel cells), and technologies (the electroplating of metals and the large-scale production of aluminum andchlorine).
While the basic principles of electrochemistry discussed in this text apply toall of these, the main emphasis here is on the application of electrochemical methods tothe study of chemical systems.Scientists make electrochemical measurements on chemical systems for a variety ofreasons. They may be interested in obtaining thermodynamic data about a reaction. Theymay want to generate an unstable intermediate such as a radical ion and study its rate ofdecay or its spectroscopic properties.
They may seek to analyze a solution for traceamounts of metal ions or organic species. In these examples, electrochemical methods areemployed as tools in the study of chemical systems in just the way that spectroscopicmethods are frequently applied. There are also investigations in which the electrochemical properties of the systems themselves are of primary interest, for example, in the designof a new power source or for the electrosynthesis of some product.
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