Electrochemical Techniques

CHEM 269
Course Content
 This course is designed to introduce the basics (thermodynamics
and kinetics) and applications (experimental techniques) of
electrochemistry to students in varied fields, including analytical,
physical and materials chemistry. The major course content will
include
 Part I Fundamentals
 Overview of electrode processes (Ch. 1)
 Potentials and thermodynamics (Ch. 2)
 Electron transfer kinetics (Ch. 3)
 Mass transfer: convection, migration and diffusion (Ch. 4)
 Double-layer structures and surface adsorption (Ch. 13)
 Part II Techniques and Applications
 Potential step techniques (Ch. 5): chronoamperometry
 Potential sweep methods (Ch. 6): linear sweep, cyclic voltammetry
 Controlled current microelectrode (Ch. 8): chronopotentiometry
 Hydrodynamic techniques (Ch. 9): RDE, RRE, RRDE
 Impedance based techniques (Ch. 10): electrochemical impedance
spectroscopy, AC voltammetry

 Grade: 1 mid-term (30%); 1 final (50%); homework (20%)

Chronoamperometry (CA)
Chronoamperometry
E
i i iLIM,c
E4
E3
E1 E2 E4
E3
t E2 t E
0 0 t
Sampled-current
voltammetry
Co Co
Co* Co*
–
E t

x x
Current-Potential Characteristics
 Large-amplitude potential step
Totally mass-transfer controlled
Electrode surface concentration ~ zero
Current is independent of potential
 Small-amplitude potential changes
i =iof
RT CO
 Reversible electrode processes E  Eo  ln
nF C R
 Totally irreversible ET (Tafel region)
 
nF
EE 
o'
1 
nF
E  E o'

i  nFAk CO 0, t e
o RT  C R 0, t e
RT 
 
 
Electrode Reactions

Osurf O’surf O’bulk

electrode Oads
electron mass
chemical
transfer transfer
Rads
Rsurf R’surf R’bulk

Double layer

Mass-transfer control
Kinetic control
Mass Transfer Issues
In a one-dimension system,

C j ( x ) z jF  ( x)
J j ( x)   D j  D jC j  C j v( x)
x RT x
In a three-dimension system,

    z jF    
J j ( r )   D j C j ( r )  D j C j  ( r )  C j v ( r )
RT

diffusion migration convection

diffusion migration convection

current current current
 Potential Step under Diffusion Control

Planar electrode: O + ne  R
CO(x,0) = CO*
Fick’s Law CO ( x, t )  2CO ( x, t )
 DO CO(0,t) = 0
t x 2
LimCO(x,t) = CO*
Laplacian transformation x∞

s
 *  x
L{F (t )}   e  st F (t )dt C
CO ( x , s )   A( s )e
O DO
0 s
CO (0, s)  0

CO*  
s


x
CO ( x , s )  1 e
DO

s  
 
 Cottrell Equation
i(t )  CO ( x, t ) 
  J O (0, t )  DO  
nFA  x  x 0

i (s)  CO ( x, s ) 
  DO  
nFA  x  x 0 CO(0,t) = 0
1
*
i ( s) DO * nFADO2 CO
 CO Reverse LT i(t )  1 1
nFA s  t 2 2

 Frederick Gardner Cottrell (1877 - 1948) was born in Oakland, California. He received a B.S. in
chemistry from the University of California at Berkeley in 1896 and a Ph.D. from the University of
Leipzig in 1902.
 Although best known to electrochemists for the "Cottrell equation" his primary source of fame was as
the inventor of electrostatic precipitators for removal of suspended particles from gases. These devices
are still widely used for abatement of pollution by smoke from power plants and dust from cement kilns
and other industrial sources.
 Cottrell played a part in the development of a process for the separation of helium from natural gas. He
was also instrumental in establishing the synthetic ammonia industry in the United States during
attempts to perfect a process for formation of nitric oxide at high temperatures.
Depletion Layer Thickness
Do *
i  nFA Co
 o (t )
30 mm 1s

 O (t )  DOt DO t = 1 mm at t = 1 ms

30 nm 1 ms

Co
Co*

x
Concentration Profile

C  
s
* 

x
CO ( x , s )  1 e
O DO

s  
 
    x 
* x 
CO ( x, t )  CO 1  erfc   C erf 
* 
 2 D t  O 2 D t 
  o   o 

In mathematics, the error function (also called the Gauss error function) is a
special function (non-elementary) which occurs in probability, statistics, materials
science, and partial differential equations. It is defined as:
Sampled Current Voltammetry
 Linear diffusion at a planar electrode
 Reversible electrode reaction
Stepped to an arbitrary potential

E  Eo 
RT CO (0, t )
ln
nF C R (0, t )

CO (0, t )
C R (0, t )
 
 exp nf E  E o 

CO ( x, t )  2CO ( x, t ) C R ( x, t )  2 C R ( x, t )
 DO  DR
t x 2 t x 2
CO(x,0) = CO* CR(x,0) = CR* = 0
LimCO(x,t) = CO* LimCR(x,t) = CR* = 0
x∞ x∞
Flux Balance

s

CO* x
CO ( x , s )   A( s )e
DO

CO ( x, t ) C R ( x, t ) s
DO [ ] x  0  DR [ ]x  0  0
x x s
 x
C R ( x, s )  B ( s )e
DR
Incoming flux Outgoing flux

s s
 A( s)  B( s)  0
DO DR s
 x
C R ( x, s )  A( s )e
DR

DR
B( s)   A( s )  A( s )
DO
I-E at any Potential

CO (0, t )
C R (0, t )
 
 exp nf E  E o 
CO (0, s )

C R (0, s ) 1
*
nFADO2 CO
i(t ) 
1   
1 1
CO*  t 2 2
 A( s)  A( s)
s  
s 
x
CO*  e DR 
CO ( x , s )  1  
s
 1   
CO*
 
A(s)   s
1    C ( x, t ) 
i  nFADO  O 
CO*  
s
x  x  x 0
C R ( x, s ) 
DR
e
s
1  
Shape of I-E Curve
At very negative potentials,   0, and i(t)  id
y
1
*
nFADO2 CO id Slope  n
i(t )  1 1 
 2 t 2 1    1   
E1/2 E
RT  DR  RT  id  i(t ) 
EE  o'
ln  ln  
nF  DO  nF  i(t ) 

E1/2 Wave-shape analysis

CA Reverse Technique
1
E *
nFADO2 CO
i f (t ) 
Ef
1   
1 1
 2t 2

Ei
Er * 
1

nFADO2 CO  1 1  1 1
t
t  ir (t )      
0 
1
2  1   ' 1   "  t  t (1   )t 
1
2

 
 '  exp nf E f  E o   
 "  exp nf Er  E o 
1
*
nFADO2 CO  1 1 
 ir (t )     when ’ =0 and ” =∞
 t t
1
 2 t

 ir tf tf  ir t
  tr – tf = t  1 1
if tr  t tr if tr
Semi-Infinite Spherical Diffusion

CO (r , t )   2CO (r , t ) 2 CO (r , t ) 

 DO   
t  r 2 r r 
1
* 1 1
i (t )  nFADO2 CO  1 1  
  2 t 2 ro 
CO(r,0) = CO*
boundary
CO(r0,t) = 0
conditions
LimCO(r,t) = CO*
r∞

 1
1 1 *
nFADO2 CO
1

i (t )  nFADO CO  1 1  
2 *
i(t ) 
  2 t 2 ro 
1 1
 t 2 2

Cottrell equation
Ultramicroelectrode
 Radius < 25 mm, smaller than the diffusion layer
 Response to a large amplitude potential step
1
* 1 1
i (t )  nFADO CO 
2
1 1
 
 t 2 2 ro 

First term: short time (effect of double-layer charging

Second term: steady state

*
nFADO CO
iss   4nFDO ro CO
*
ro
 i
1
* 1 1
i (t )  nFADO CO 
2
1 1
 
 t 2 2 ro 
spherical
1
*
electrode
nFADO2 CO
i(t )  1 1
planar iss
 2t 2 electrode
t
Amperometric glucose sensor based on platinum–iridium
nanomaterials
Peter Holt-Hindle, Samantha Nigro, Matt Asmussen and Aicheng Chen
Electrochemistry Communications, 10 (2008) 1438-1441

 This communication reports on a novel amperometric glucose sensor based on

nanoporous Pt–Ir catalysts. Pt–Ir nanostructures with different contents of iridium
were directly grown on Ti substrates using a one-step facile hydrothermal method
and were characterized using scanning electron microscopy and energy dispersive
X-ray spectroscopy. Our electrochemical study has shown that the nanoporous Pt–
Ir(38%) electrode exhibits very strong and sensitive amperometric responses to
glucose even in the presence of a high concentration of Cl− and other common
interfering species such as ascorbic acid, acetamidophenol and uric acid, promising
for nonenzymatic glucose detection.
(a) S0: Pt–Ir(0%), (b) S1: Pt–Ir(22%), (c) S2: Pt–Ir(38%). (d) EDX
spectra of samples S0 and S2. Insert: the enlarged portion of the
EDX spectrum of samples S0 and S2 between 9.0 and 12.0 keV.

(a) Chronoamperometric responses of S0, S1, S2 and

S3 measured at 0.1 V in 0.1 M PBS (pH 7.4) +0.15 M
NaCl with successive additions of 1 mM glucose (0–
20 mM). (b) The corresponding calibration plots.
Interference Study

Pt–Ir(38%)

Pt–Ir(0%)

 Chronoamperometric curves of S0 and S2 recorded in 0.1 M PBS

+0.15 M NaCl with successive additions of 0.2 mM UA, 0.1 mM AP,
0.1 mM AA and 1 mM Glucose at 60 second intervals under the
applied electrode potential 0.1 V.
Electroanalysis 1997, 9, 619.
Microelectrode Voltammetry

Fig. 1 Plot showing cyclic

voltammograms recorded for a
series of 25 mm Pt microelectrodes
recorded at 2 mV/s in a solution
containing 10 mM K3[Fe(CN)6] in
Sr(NO3)2 at 25 mm under
anaerobic conditions. The insert in
the figure shows a SEM image of
the 93 mC HI-ePt modified
microelectrode recorded after the
experiments were performed. The
scale bar on the SEM represents
10 mm.

Electrochemical reduction of oxygen on mesoporous platinum microelectrodes

Chronocoulometry (CC)
1
*
nFADO2 CO
i(t )  1 1
Cottrell Equation (at large potential steps)
 t 2 2

1 Surface adsorbed species nFAG*

* 2
nFADO CO 1
Q(t )  1
t 2  QDL  Q ADS
 2
Q
Double-layer charging

intercept
t1/2
Reverse CC
1
*
nFADO2 CO  t 1 2  t  t  12 
Qd (t  t )  1
 2  

So the net charge removed in the reverse step is 

1
*
nFADO2 CO t 12  t 12  t  t  12 
Qr (t  t )  Q(t )  Qd (t  t )  1
 2  

Q t<t t1/2

t>t

Potential Sweep Techniques

C
O

R
x
Nernstian Processes
 O + ne  R CO (0, t )
C R (0, t )
 nF
 f (t )  exp
 RT
 

Ei  vt  E o'   S t 

 E(t) = Ei - vt nFv
S (t )  e t  
RT

CO ( x, t )  2CO ( x, t )
 DO
t x 2

Laplacian transformation

s
 x
CO* DO
CO ( x, s )   A( s)e
s
 i(t )  C ( x, t ) 
  J O (0, t )  DO  O 
nFA  x  x 0

1 t  12
 CO   i (t )(t  t ) dt
*
CO (0, t )
nFA DO 0

i (t )
f (t ) 
nFA

1 t  12
 CO   f (t )(t  t ) dt
*
CO (0, t )
DO 0

1 t  12
C R (0, t )   f (t )(t  t ) dt
DR 0
CO (0, t )
C R (0, t )
 nF
 f (t )  exp
 RT
 
Ei  vt  E o'   S t 



t *
 12 CO
 f (t )(t  t ) dt 
 12  12
0 S (t )(DR )  (DO )

DO

DR

1
t  12 nFA(DO ) CO *2
 i (t )(t  t ) dt 
0 S (t )  1
 Let z = t so that t = z/
 At t = 0, z = 0, and at t = t, z = t
t  12 t z  12 dz
 f (t )(t  t ) dt   g ( z )(t  )
0 0  

t  12  12 CO*
DO
 g ( z )(t  z )  dz 
0 1  s (t )

t  12 1
  ( z )(t  z ) dz 
0 1  s (t )

g ( z) i(t )
 ( z)  
*
CO DO *
nFACO DO

nFv
i  nFACO
*
DO  (t )  
RT
Numerical Simulations
Linear Sweep / Cyclic Voltammetry
Key Features For Reversible Reactions

i  v1/2 for linear diffusion

Peak current at 1/2(st) = 0.4463,
thus iP = (2.69  105)n3/2ADO1/2CO*v1/2
Peak potentials E 1/2
EP = E1/2 – 1.109(RT/nF) EP/2

EP/2 = E1/2 + 1.09(RT/nF)

|EP – EP/2|= 2.20(RT/nF)
E1/2 = |EP,a + EP,c|/2
Totally Irreversible Reactions
O + ne  R

 CO x, t  
 k f CO 0, t 
i
 DO  
nFA   x  x 0

E  Ei  vt


nF

E  E o'  
nF
 
Ei  E o ' 
nF
vt
kf k e o RT k e
o RT e RT  k f ,i ebt

i  nFACO
*
DO b  (bt )
1
 F 
DO v     (bt )
1 2
i *
nFACO 2
 RT 
Key Features
At 1/2(bt) = 0.4958,
1 1 1
iP  (2.99  10 )
5 2 * 2 2
nACO DO v

iP  0.277nFACO
 F
k exp
* o
 RT

E P  E o' 

 
Peak potential
|EP – EP/2|= 1.857(RT/nF)
  12  1 
RT  D   Fv  2 
EP  E  0.780  ln  o   ln 
o' O
 
n F   k   RT  
   
Reversible vs Irreversible Reactions
Cyclic Voltammetry
 Current reflects the combined
contributions from Faradaic
processes and double-layer
charging
 For chemically reversible
reactions, iP,a = iP,c
(independent of v)
 Peak splitting
DEP = |EP,a – EP,c|=2.3RT/nF
DEP = 59/n mV at 298 K, or
at steady state, 58/n mV.
Reversible vs Kinetically Slow Reactions

DEp = constant
DEp decreases with increasing k
DEp increases with increasing sweep rate
 Bispicolinate Copper (II)

The separation between them, DEp, exceeds

the Nernstian requirement of 59 mV
expected for a reversible one-electron
process. This value increases from DEp =
0.11V at 0.05 V/s to 0.33 V at 5 V/s
indicating a kinetic inhibition of the electron
transfer process
Cyclic voltammogram of [Cu(pic)2].2H2O in DMF solution
 Multistep Reactions

+1/0
0/-1
-1/-2

A low band gap conjugated metallopolymer

with nickel bis(dithiolene) crosslinks

Christopher L. Kean and Peter G. Pickup*

Chem. Commun., 2001.

Fig. 1 Cyclic voltammetry (100 mV s 1) of: (a) 1 in

CH2Cl2 containing 0.1 M Bu4NPF6; (b) a poly-1
coated Pt electrode in acetonitrile containing 0.1 M
Et4NClO4.
Multistep Reactions

Identify peak positions

Identify peak pairing
Deconvolution of
overlapped
voltammetric peaks (A) Cyclic voltammogram at 0.05 V s−1 of a
GCE modified with KxFey[Ir(CN)6]z in 50 mM
KCl/HCl. (B) Cyclic voltammogram after the
GCE was immersed in Cu2+ for 120 minutes
Voltammetric Responses of Adsorbed
Species
 Only adsorbed O and R are
electroactive (Nernstian reaction)
GO (t ) GR (t ) GO (t ) O GO CO (0, t ) bOCO (0, t ) bO
 
*
i  nF o' 
      exp  RT E  E 
t t nFA GR (t )  R G* CR (0, t ) bRCR (0, t ) bR
R
 

bO
bR
 nF
exp 
 RT
 
E  E o' 
 G*

GO (t ) 
1
bO
bR
exp 
 nF
 RT
EE  
o' 

O


2 2 G *  bO  exp  nF ( E  E o ' )
n F vA    RT 
GO (t )  n 2 F 2  O
iP  vAGO* i   nFA 
 RT 
 bR   
4 RT t    bO
2
   nF o'  
1   b  exp  ( E  E ) 
  R   RT 
Key Features

iP  v (slope defines G*)

iP  G*
Qads = nFAG* (peak area)
EP = Eo’
Reversible reaction, peak
width at half maximum
RT 90 .6
DE P , 1  3.53  mV
2 nF n
Physical Chemistry Chemical Physics DOI: 10.1039/b101561n

A ligand substitution reaction of oxo-centred triruthenium complexes assembled as monolayers

on gold electrodes

Akira Sato , Masaaki Abe* , Tomohiko Inomata , Toshihiro Kondo , Shen Ye , Kohei Uosaki* and Yoichi
Sasaki*

G* = 1.8  10-10 mol/cm2

Cyclic voltammograms for monolayers of 1 assembled on

the polycrystalline Au electrode in 0.1 M HClO4 aqueous
solution at 20oC in the electrode potential region between -
0.25 and + 0.85 V/s. Ag/AgCl. A platinum wire is used for
the counter electrode. Scan rate = 50, 100, 200 and 400
mV/s. Inset: A linear correlation of current intensities of the
anodic and cathodic waves (ipa and ipc, respectively) with
the scan rate.
 PcFe

PcFe
Wave-Shape Analysis

Question
- Reaction proceeds with a
simultaneous two-electron
transfer or two successive one-
electron reductions?
Controlled Current Techniques

Galvanostat

t
t
Classification
Constant-current chronopotentiometry
Programmed current chronopotentiometry
I E

t t

Cyclic chronopotentiometry
E

t1 t2
t
General Theory
O  ne  R
CO x, t   2 CO  x , t 
CO(x,0) = CO*, CR(x,0) = 0
 DO CO(∞,t) = CO*, CR(∞,t) = 0
t x 2  C x, t   it 
DO  O 
C R x, t   2 C R  x, t 

 x  x 0 nFA
 DR
t x 2
s  C x, s   i s 
 x DO  O  
CO* DO  x  x 0 nFA
CO ( x, s )   A( s)e
s
s
 x
CO* i(s) DO
CO ( x, s )   1 1
e
s nFADO2 s 2

s
 x
i( s) DR
C R ( x, s )  1 1
e
nFADR2 s 2
Sand Equation
s
 x
CO* i DO
CO ( x, s )   1 3
e
s nFADO s 2 2

i  D t  x 2   x 
CO ( x, t )  CO
*
 2 O exp    xerfc 
nFADO      2 D t 
  4 DO t   O 

1
2it 2
CO (0, t )  CO
*
 1 1
nFAD  2 2
O

1 1
nFAD 
1 2
it
2
2

*
 O Sand equation
CO 2

1  *
it  nF  A DOt CO
2 
Potential-Time Transient
1
2it 2
Reversible Reactions CO (0, t )  CO
*
 1 1
nFAD  2 2
RT CO (0, t ) O
EE  o'
ln 1
nF C R (0, t ) 2it 2
C R (0, t )  1 1
nFAD  2 2
R

1 1 1 1 1
RT  DR 2
RT t  t
2 2 RT t  t 2 2
E  E o'  ln    ln 1
 Et  ln 1
nF  DO  nF t2 4 nF t2
y
Slope  n

x
Totally Irreversible Reactions
O  ne  R

 nF E  E o'
i  nFAk CO (0, t ) exp 
o  
 RT 
 
1
CO 0, t 
1
t 2it
2 2
 1   CO (0, t )  CO
*
 1 1
*
CO t  nFAD  2 2
O

RT  nFACO k  RT   t  2 
 * o  1

EE 
o'
ln  ln 1    
nF   
i  nF   t  
Quasi-Reversible Reactions
 1
  1

 t  2
 t  
 exp(1   )nf 
2
i  2i  exp(nf )  1  2i
 1   
io  nFACO*
 DO    nFAC*  R 
D
   R 

Small 

 1   
RT  2t 2  1 1  1
  i     
nF  nFA 12 1 1
 C * D 2 C * D 2  io 
  O O R R 

Double-Layer Effect


idl   AC dl
t

Most significant at the beginning or at the

end of the charging step
if = i - idl
Reverse Technique

t1 t2
t

For a reversible reactions, t2 = t1/3, i.e.,

maximum 1/3 of the R produced in the
forward step will be re-oxidized into O.
Anal. Chem. 1969, 41, 1806
Hydrodynamic Methods
Hydrodynamic Techniques
 Advantages
A steady state is attained rather quickly
Double-layer charging does not enter the measurements
Rate of mass transfer » rate of diffusion alone
Dual electrodes can be used to provide the same kind of
information that reverse techniques achieve
C j ( x ) z jF  ( x)
J j ( x)   D j  D jC j  C j v( x)
x RT x

diffusion migration convection

Theoretical Treatments

Convection maintains the concentrations

of all species uniform and equal to the bulk
values beyond a certain distance from the
electrode surface, 
Within this layer (0 < x < ), no solution
movement occurs, and mass transfer is
purely diffusion.
Convective Diffusion Equation
    z jF    
J j ( r )   D j C j ( r )  D j C j  ( r )  C j v ( r )
RT

C j    
   J j  D j  C j  v  C j
2
t

For a one-dimensional system,

C j  2C j C j
 Dj  vy
t x 2 y
y
Velocity Profile
 For an incompressible fluid, continuity equation dictates that
the local volume dilation rate is zero 

 v  0
 Navier-Stokes equation
 Named after Claude-Louis Navier and George Gabriel
Stokes, describe the motion of viscous fluid substances
such as liquids and gases.
 The equation arises from applying Newton's second law to
fluid motion, together with the assumption that the fluid
stress is the sum of a diffusing viscous term (proportional
to the gradient of velocity), plus a pressure term.
  
dv 2
ds  P   s  v  f
dt
Pressure Stress Body
gradient tensor force
 Claude-Louis Navier (10 February Sir George Gabriel Stokes, 1st Baronet FRS (13
1785 in Dijon – 21 August 1836 in August 1819–1 February 1903), was a mathematician
Paris) was a French engineer and and physicist, who at Cambridge made important
physicist who specialized in contributions to fluid dynamics (including the Navier–
mechanics. Stokes equations), optics, and mathematical physics
(including Stokes' theorem). He was secretary, then
president, of the Royal Society.

The Navier-Stokes equation is one of the most useful sets of equations

because they describe the physics of a large number of phenomena of academic
and economic interest. They may be used to model weather, ocean currents,
water flow in a pipe, flow around an airfoil (wing), and motion of stars inside a
galaxy. As such, these equations in both full and simplified forms, are used in the
design of aircraft and cars, the study of blood flow, the design of power stations,
the analysis of the effects of pollution, etc. Coupled with Maxwell's equations they
can be used to model and study magnetohydrodynamics.
Rotating Disk Electrode (RDE)
 
dv 1  2 f 
  P  v v 
dt ds ds y=0
r
At steady-state Kinematic
 viscosity vy
dv vr
0
dt
Uo
2 b 3 y
vr  rF ( )  r (a     ...)
2 3
a = 0.51023
a 3
v  rG ( )  r (1  b    ...) b = 0.6159
3  = (/v)1/2y
 4
   2 H ( )    2 (a 2   3 
1 1 1 b
vy  ...)
3 6
Velocity Profiles
At the electrode surface (y  0 or   0)
vy = 0.513/21/2y2 at y = 0, vy = 0 = vr, i.e., at
the electrode surface, no
vr = 0.513/21/2ry convection, only diffusion

At bulk solution (y  ∞) vy

vr = 0
Uo
v = 0
y
vy = Uo = 0.88447(v)1/2 vr r2

r2 > r1
r1
y
Hydrodynamic Boundary Layer

At  = (/v)1/2y = 3.6, vy = 0.8Uo, the

corresponding distance yh = 3.6(v/)1/2
defined as the hydrodynamic boundary
layer thickness ()
For water, v = 0.01 cm2/s,
 at  = 100 s-1, yh = 36 nm
 at  = 10-4 s-1, yh = 36 mm
Convective-Diffusion Equation
C
   J  D 2C  v  C
At steady state, dC/dt = 0 t

CO v CO CO   2CO  2CO 1 CO 1  2CO 

vr   vy  DO     
r r  y  y 2
r 2 r r r  
2 2

At y = 0, CO = 0

limCO = CO*
y∞
CO  2 CO
CO is not a function of , i.e., 
0
 2

1
*   3
 CO  CO  0.17 
    
 y  y 0 0.8934  D   2 2 
3 1

 O 
Levich Equation
 CO 
i  nFADO  
 y  y 0
2
 16 1
il ,c  0.62 nFAD O 3

* 2
CO

DO
il ,c  *
nFAmO CO  nFA *
CO
O
1 1
 12
 O  1.61 DO 3 6

Diffusion layer thickness

Current-Potential Relationship

i  0.62 nFADO
2
3
 16
*
CO 
 C O ( y  0) 
1
2

 CO ( y  0)   C R ( y  0) 
i  il ,c 1   and i  il ,a 1  
* *
 CO   CR 

i
RT  il ,c  i 
E  E1  ln
2 nF  i  il ,a 
E
Kinetic Effects
*
 i   i 
i  nFAk f ( E )CO ( y  0)  nFAk f ( E )CO 1 
 iK 1  
 
il ,c   il ,c 
  
1 1 1
  Levich-Koutecky Equation
i i K il ,c

il,c  1/2

il,c

independent of 

1/2
Consideration In Experimental
Applications of RDE
 Rotating rate must be sufficient large to
maintain a small diffusion layer at the
electrode surface, e.g.,  > 10 s-1 (for water 
= 0.01 cm2/s and disk radius r1 = 0.1 cm)
 Potential scan rate must be small compared to
 so that a steady state can be achieved,
typically  20 mV/s
 Upper limit of  is governed by the onset of
turbulent flow, generally  < 2  105 /r12
 Flat electrode surface
 Electrode aligned to the center of the rotating rod
Rotating Ring-Disk Electrode (RRDE)
 The difference between a rotating ring-disk
electrode (RRDE) and a rotating disk
electrode (RDE) is the addition of a second
working electrode in the form of a ring
around the central disk of the first working
electrode. The two electrodes are separated
by a non-conductive barrier and connected
to the potentiostat through different leads.
 To operate such an electrode it is necessary
to use a bipotentiostat.
Rotating Ring-Disk Electrode (RRDE)

The disk current (RDE) is unaffected by

the presence of the ring electrode (current
or potential)
In the case where the disk is open, the
electrode behaves as a rotating ring
electrode (RRE)
When a potential is applied to the disk
electrode, the ring current varies (RRDE)
Rotating Ring Electrode (RRE)
 Disk radius r1, inner radius r2, outer
radius r3,so the ring area A   (r32  r22 )
   16
2 2 1
il , R  0.62 nF r23  r23 DO *

3 3
CO 2

 CO ( y  0)  r1
i  il , R 1  
*
 CO 
r2
 In two independent measurements by
r3
RDE and RRE
2
iR  r33 r 3  3

  2 
2
 3
iD  r3 r3 
 1 1 
Collection Experiments
 Disk electrode (iD): O + ne  R
Disk potential is being scanned
 Ring electrode (iR): R  O + ne
Ring potential is held at a positive enough position to
ensure that CR(y=0)  0
 Collection efficiency N = iR/iD

  1  F    1      3 1  F   1     
2
N  1 F    
2
3

 1

3
1  
3    2 13  1  1
3

F ( )  ln   
3
arctan 
4  1    2  3  4

 
3
r 
   2   1
 r1 
Collection Experiment
i
iD
At r1 = 0.187 cm, r2 = 0.200
cm and r3 = 0.332 cm, ED

iR
N = 0.555, i.e., 55.5% of the
product generated at the
disk may be recovered by
the ring electrode
 Shielding Experiments
Disk electrode (iD): O + ne  R
Disk potential is held at a constant position
Ring electrode (iR): O + ne  R
Ring potential is being scanned
iR iD = 0

2 Shielding factor
iRo ,l   iD,l3
iR,l
iR = NiD,l
ER
Ni D  iRo ,l 1 
 23 
Collection Shielding iR,l  iRo ,l  N 
Experiment Experiment  
Collection Experiment

disk
N = 0.22,
cf. theoretical value 0.25

ring
Electrochemical Impedance Spectroscopy
 Ohm's law defines resistance in
terms of the ratio between voltage
E and current I, I = E/R. While this
is a well known relationship, its use
is limited to only one circuit
element -- the ideal resistor.
 An ideal resistor has several
simplifying properties:
 It follows Ohm's Law at all current and
voltage levels.
 It's resistance value is independent of
frequency.
 AC current and voltage signals though
a resistor are in phase with each other.
Inductor (coil)
 The light bulb is a resistor. The wire
in the coil has much lower
resistance (it's just wire), so what
you would expect when you turn on
the switch is for the bulb to glow
very dimly. Most of the current
should follow the low-resistance
path through the loop.
 What happens instead is that when
you close the switch, the bulb burns
brightly and then gets dimmer.
When you open the switch, the bulb
burns very brightly and then quickly
goes out.
 Example: viscous/viscoelastic thin
films
Electrochemical Impedance
 The real world contains circuit elements that exhibit much more
complex behavior (inductors and capacitors, for instance). These
elements force us to abandon the simple concept of resistance. In
its place we use impedance, which is a more general circuit
parameter. Like resistance, impedance is a measure of the ability of
a circuit to resist the flow of electrical current.
 Electrochemical impedance is usually measured by applying an AC
potential to an electrochemical cell and measuring the current
through the cell. Suppose that we apply a sinusoidal potential
excitation. The response to this potential is an AC current signal,
containing the excitation frequency and it's harmonics. This current
signal can be analyzed as a sum of sinusoidal functions (a Fourier
series).
e(t )  E sin(t )
Phase shift
i (t )  I sin(t   )
Phase Shift

For a pure resistor, i = e/R = (E/R)sin(t),

so  = 0
For a pure capacitor, q = Ce, so i = dq/dt
=CEcos(t) = CEsin(t+/2) , i.e.,  =
/2
RC Circuits (series)

e = eR + eC = i(R  j/C) = iZ
Z = R  j/C
|Z|=[R2+1/(C)2]1/2
tan( = 1/CR
R


Z
Impedance Plots

log|Z|

log

 Zim
/2
increasing 

log Zre
R
Bode plots Nyquist plots
RC Circuits (parallel)
e e e 1  1 1
i    e  jC    j C
Z R ZC R  Z R
R 2
R C
Z  j
1  RC 
2
1  RC 2 tan     RC 

Bode plots Nyquist plot

 Equivalent Circuit for an Electrochemical Cell

Rs: solution resistance

Cdl: double-layer capacitance
Rct: Charge-transfer resistance
ZW: Warburg resistance (diffusion)
idl

if+idl

if
Kinetic Parameters from EIS
RS CS
Faradaic branch

  

1  O  R 
2nFA  DO DR  
RS  Rct 
O 
E 
CO (0, t ) 1
CS 
E  
Mass R 
C R (0, t )
transfer
terms
Kinetic Evaluation
O  ne  R Butler-
Volmer
RT  CO (0, t ) C (0, t ) i  equation
   R  
F  CO *
CR* io 

RT 1 RT
Rct  RS 
C S
 Rct 
Fio
 io  k o
Fio
 

RT  1

1 
O 
RT 2 F 2 A  CO
*
DO C R* DR 
*
FCO
at io  ∞ (Rct  0)
RT  2
R   Rct  Zf 


FCR*  Mass-transfer
 = /4 controlled
Randle’s Circuit

Rct 

Z re  R 
C dl 
2
2   
2
 1  C dl   Rct  
  

 Cdl  1
2
   

C dl  Rct   
   
Z im 
Cdl 
2
2   
2
 1  C dl   Rct  
  
Low-Frequency Domain
0

Z re  R  Rct  Slope = 1

  = /4
Z im  2 C dl 
2


Z im  Z re  R  Rct  2 2Cdl
intercept
High-Frequency Domain

Warburg term becomes insignificant, i.e.,

the ET reaction is under kinetic control
The equivalent circuit becomes C dl
Rct R
Z re  R 
1  2 2 2
C dl Rct

Cdl Rct2 Rct

Z im 
1   2Cdl
2 2
Rct

Rct
2 2
 R  R  2
 Z re  R  ct   Z im   ct 
2
 2   2 
Experimental Procedure
Structural details of electrochemical Cell
Impedance spectra
Design an equivalent circuit
Curve fitting for kinetic parameters
mercaptoacetic acid
(MAA) HSCH2COOH

mercaptopropionic
acid (MPA)
HSCH2CH2COOH

mercaptoundecanoic
acid (MUA)
HS(CH2)10COOH

mercaptobenzoic
acid (MBA)
HSC6H4COOH
 Cdl
R

Rct

Fig. 4 Normalized capacity of Au

coated electrodes, (A) DTT, (B) TG
as a function of metal ion
concentration

Fig. 2 Nyquist plots obtained with an Au polycrystalline electrode at –0.40 V vs. Hg/HgSO4 in electrolyte solution
containing 0.1 M NaNO3, and various concentrations of Sr(NO3)2. (A) Au coated with 1-thioglycerol (TG); (B) Au
electrode coated with 1,4-dithiothreitol (DTT).
Electrochemical Impedance Spectroscopy
Pseudo-Inductor Components
The quartz crystal microbalance: a tool for probing
viscous/viscoelastic properties of thin films
Tenan, M. A., Braz. J. Phys. vol.28 n.4, 405-412. 1998

 The QCM consists basically of

an AT-cut piezoelectric quartz
crystal disc with metallic
electrode films deposited on its
faces. One face is exposed to
the active medium. A driver
circuit applies an ac signal to
the electrodes, causing the
crystal to oscillate in a shear
mode, at a given resonance
frequency.
 Measured resonance
frequency shifts, Df, are
converted into mass changes
by the well-known Sauerbrey
equation.
EQCM
 The resonant mechanical
oscillations are basically fixed
by the crystal thickness,
whereas the damping depends
on the characteristics of the
mounting and the surrounding
medium.
 The use of the QCM in a liquid
medium together with
electrochemical techniques
increased enormously the
possibilities of this tool; and
hence electrochemical quartz
crystal microbalance, EQCM.