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CHEM 4700
CHAPTER 2
ELECTRODE REACTIONS
&
INTERFACIAL PROPERTIES
CYCLIC VOLTAMMETRY
- Solution is unstirred
Provides information on
- the thermodynamics of redox processes
- the kinetics of heterogeneous electron transfer reactions
- the kinetics of coupled reactions
CYCLIC VOLTAMMETRY
Characteristic Parameters
- Anodic peak current (ipa)
- Cathodic peak current (ipc)
- Anodic peak potential (Epa)
- Cathodic peak potential (Epc)
CYCLIC VOLTAMMETRY
Reversible Systems
i p 2.69 x 105 n 3/2ACD1/2 1/2
n = number of electrons
A = electrode area (cm2)
C = concentration (mol/cm3)
D = diffusion coefficient (cm2/s)
= potential scan rate (V/s)
CYCLIC VOLTAMMETRY
Reversible Systems
ip is proportional to C
ip is proportional to 1/2
2
CYCLIC VOLTAMMETRY
Reversible Systems
0.059
E p E pa E pc V
n
Reversible Systems
RT k o
a
n F
1/2
Ep E
o
0.78 ln 1/2 ln
n a F D RT
2.99 x 10 nn
1/2
ip 5
a ACD1/2 1/2
CYCLIC VOLTAMMETRY
Irreversible Systems
= transfer coefficient
na = number of electrons involved in a charge transfer step
ko = standard heterogeneous rate constant (cm/s)
For = 0.5
ip,reversible/ip,irreversible = 1.27
- That is irreversible peak current is ~ 80% of reversible ip
CYCLIC VOLTAMMETRY
Quasi-reversible Systems
Applications
E
- Only redox step
O + ne- R
CYCLIC VOLTAMMETRY
Applications
EC
- Redox step followed by chemical step
O + ne- R + A Z
EC
- Redox step followed by chemical step
O + ne- R + A Z
Examples
- Ligand exchange reactions as in iron porphyrin complexes
- Oxidation of chlorpromazine to produce a radical cation and
subsequent reaction with water to produce sulfoxide
CYCLIC VOLTAMMETRY
Applications
EC
- Catalytic regeneration of O during a chemical step
O + ne- R + A O
Example
- Oxidation of dopamine in the presence of ascorbic acid
CYCLIC VOLTAMMETRY
Applications
CE
- Slow chemical reaction precedes the electron transfer step
Z O + ne- R
ECE
- Chemical step interposed between redox steps
O1 + ne- R1 O2 + ne- R2
Symmetric CV
Ep = 0
Applications
Symmetric CV
- Peak current is directly proportional to surface coverage ()
and scan rate ()
n 2 F 2 A
ip
4RT
Holds for relatively
- slow scan rates
- slow electron transfer
- no intermolecular attractions within the adsorbed layer
CYCLIC VOLTAMMETRY
Applications
Symmetric CV
Q (area under peak) current
Ep,1/2
Q nFA
volts
CYCLIC VOLTAMMETRY
Applications
Symmetric CV
Q
Q nFA or
nFA
CYCLIC VOLTAMMETRY
Applications
3. Quantitative Determination
Examples
Indium tin oxide (ITO), platinum, gold, silver, nickel
deposited on optically transparent glass or quartz substrate
SPECTROELECTROCHEMISTRY
-2.5 1000
Epc
Io
Current (Milliamps)
-1.5 800
ipc
-0.5 600
Intensity
0.5 400 I
ipa
1.5 200
Epa
2.5 0
0.8 0.6 0.4 0.2 0 -0.2 -0.4 0 100 200 300 400 500 600
Examples of Species
Ru(bpy)32+
Nitro compounds
Polycyclic hydrocarbons
Luminol
SCANNING PROBE MICROSCOPY
Examples
- Scanning Tunneling Microscopy (STM)
- Atomic Force Microscopy (AFM)
- Scanning Electrochemical Microscopy (SECM)
SCANNING TUNNELING MICROSCOPY (STM)
- Very sharp atomic tip moves over the sample surface with a
ceramic piezoelectric translator
- The probe has a sharp tip made from silicon or silicon nitride
attached to a force-sensitive cantilever
Used to investigate
- Ionic flux through the skin or membranes
2mnf o2
f
A
n = overtone number
fo = base resonant frequency of the crystal (prior to mass change)
A = area (cm2)
= shear modulus of quartz (2.95 x 1011 gcm-1s-1)
= density of quartz (2.65 g/cm3)
ELECTROCHEMICAL QUARTZ CRYSTAL
MICROBALANCE (EQCM)
Impedance
- Complex resistance encountered when a current flows
through a circuit made of combinations of
resistors, capacitors, or inductors
IMPEDANCE SPECTROSCOPY
Consists of
- a semicircle portion at high frequencies
(corresponds to the electron-transfer-limited process)
and