Chapter 6 Potential Sweep Methods

Linear Sweep Voltammetry Perturbation signal: E(t) Ei + t = scan rate = V/s

Ei

Ef

Time Ep

Ox + e- Red ip Co

Ep/2 ip 0

Macroelectrodes: max. 1000 mV/s Microelectrodes: max. 106 V/s

E (vs. ref)

Chapter 6 Potential Sweep Techniques

Eo Ep i Ep/2 ip 0 CR E (vs. ref) Distance (x) (-) C Co

Potential reached vicinity of Eo and current begins to flow. As potential grows more negative surface concentraion of Ox must drop hence the flux and current increase. Steep C/x! As potential moves past Eo, the surface concentration drops to nearly zero and mass transport of Ox reaches a maximum rate. Current then declines as a depletion effect sets in.

Chapter 6 Potential Sweep Techniques

Eo Ep i Ep/2 ip 0 i Ep/2 ip 0 (-) E1/2 Ep

E (vs. ref)

E (vs. ref)

(-)

Nernstian (Reversible) System Co(0,t)/CR(0,t) = (t) = exp [nF/RT(Ei+t Eo) ip = (2.69x105)n3/2ADo1/2Co*1/2

Chapter 6 Potential Sweep Techniques

Equations for reduction half reaction! E1/2 Ep i Ep/2 ip 0

Ep - E1/2 = 1.109 RT/nF = 28.5 mV at 25 oC Ep/2 = E1/2 + 1.109RT/nF = E1/2 + 28.0/n mV at 25 oC

E (vs. ref)

(-)

E1/2 = Eo + (RT/nF)ln (DR/Do)1/2 Ep Ep/2 = 2.20 RT/nF = 56.5/n mV at 25oC

Ep ()

ip = (1/2)

{id = (t-1/2)}

ip/1/2Co* = current function = constant (can be used to estimate n)

Chapter 6 Potential Sweep Techniques

Totally Irreversible Systems
Eo

Ox + e- Red kf, kb, ko and have more of an effect on shape. Hence they can be evaluated!

i Larger driving potential E ( vs. ref)

Ep = () 30/n for each tenfold inc. in ip = (1/2)

(-)

ip = (2.99. x 105) (n)1/2ACo*Do1/21/2

Plot ln ip vs. Ep-Eo at different Slope -F/RT Yinter ko

Ep = Eo RT/nF[0.780 + ln(Do1/2/ko) + ln (F/RT)1/2 Ep Ep/2 = 1.86RT/nF = 47.7/n mV at 25 oC

Chapter 6 Potential Sweep Techniques

Quasireversible Reactions
Ox + e- Red Increasing scan rate tends to shift a reduction peak more negative and an oxidation peak more positive. Shape depends on ko, and ! Parameter = ko/(D0(1-)Dr)1/2
Low , big effect on red wave

Remember: the perturbation signal is a time dependent potential sweep. Where the wave shows up on the potential axis (time!) depends on the time dependence of the electrode reaction (reaction kinetics).

iR effects also shift peak positions in a manner similar to that of kinetic effects! Must correct for this.

Chapter 6 Potential Sweep Techniques

Effect of Double Layer Charging Current
ich = ACdl (A)
Faradaic current must always be measured from baseline of the charging current. ich/if = Cdl/(2.69x105)n3/2D1/2C* The background/faradaic current ratio increases with scan rate. This means reduced S/B ratios with increased scan rate! Remember that Etrue = Eappl - iRu Increased scan rates mean increased current and more iR effect!

Chapter 6 Potential Sweep Techniques

Effect of Potential Sweep Rate on Wave Shape
Transition from peak shape to steady state depends on and ro. Large (short time) and conventional ro planar diffusion or peaks shape. Small (long time) and small ro non-planar diffusion or steady state.

For << RTD/nFro2 steady state i-E curve observed.

Chapter 6 Potential Sweep Techniques

Cyclic Voltammetry
Reversal technique Useful for determining ko, concentrations of analyte and studying electrode reaction mechanisms (generate a product at the electrode surface on the forward sweep and probe its fate on the rev. sweep
EpOX Current Density (A/cm2)

E2 Potential (V)

i=0

E1 Time (sec)

EpRED E1 Potential (V) E2

Chapter 6 Potential Sweep Techniques

Important Diagnostics
EpOX Current Density (A/cm2)

i=0

Epox and Epred Ep = Epox Epred ipox and ipred ipox/ipred ratio Qpox and Qpred Ep/2

EpRED E1 Potential (V) E2

Remember: the perturbation signal is a time dependent potential sweep. Where the wave shows up on the potential axis (time!) depends on the time dependence of the electrode reaction (reaction kinetics).

Chapter 6 - Potential Sweep Techniques

Reversible or Nernstian Kinetics
EpOX Current Density (A/cm2)

Ep = Epox Epred = 60/n mV Ep () ipox/ ipred = 1 i=0 ipox and ipred = (1/2) Qpox/Qpred = 1 Ep - Ep/2 = 2.20 RT/nF = 56.5/n mV
E2

EpRED E1 Potential (V)

ip = (2.69 x 105) n3/2AD1/2C*1/2

Chapter 6 Potential Sweep Techniques

Slope = (2.69 x 105) n3/2AD1/2C*

ip (corr) (A) 0 0

1/2 (V/s)

Linearity indicates: Semi-infinite linear diffusion controls the reaction rate. Electrochemical reversibility or irreversibility. Non-complicated redox reaction (can be reflective of this).

ip = (2.69 x 105) n3/2AD1/2C*1/2

Chapter 6 Potential Sweep Techniques

Technique is extremely useful for studying electrode reaction mechanisms!
ket kch Red Ox + e- X (chemical rxn. prod)
EpOX Current Density (A/cm2)

ipox/ipred i=0

Rate of change reflective of kch

1
EpRED E1 Potential (V) E2

(V/s)

Chapter 6 Potential Sweep Techniques

A

20

n = 1, = 0.5 T = 25 oC

Method for estimating ko in quasireversible systems! 0.2 > ko > 10-5 cm/s

Kinetic Parameter

15

10

(Do/Dr)/2ko (Do) Ep values are nearly independent of 0.3 < < 0.7.

60

80

100

120

140

Peak Potential Separation

Nicholson method links kinetic parameter, , to ko