C33J – ELECTROCHEMISTRY

Electrochemistry is concerned with:

- thermodynamics and kinetics of (homogeneous and

heterogeneous) redox processes

- structure of electrified interfaces

- ion transport

Applications to the living and nonliving world

- bio-electrochemistry, electrophysiology, biosensors,

biomimetics (modified electrodes)

- energy technology (batteries, fuel cells)

- metallurgy (metal purification), electroplating

- corrosion prevention and control

- electrocatalysis, organic synthesis

- analytical and environmental chemistry (detection of trace

amounts of metals)

- semiconductor devices
 ELEMENTS OF ELECTROSTATICS

v v
F −F -
+

r
v qq
Coulomb’s Law: F = 1 2 2 rˆ
4πε 0 r
v
E
2
v v
Field E (r ) = force acting on
1
unit of +ve charge (1 Coulomb)
v
q at position r

v
Potential φ ( r ) = - (work done by field in carrying 1 C from ∞
v
to r )

v v
r r
E = - ∫ (| E | cosθ ) dr (independent of path!)
∞
θ
v dφ
dr φ decreases in the direction of E = − v
dr
v
Potential difference φ ( 2) − φ (1) is uniquely determined by r1
v
and r2 in a given electrostatic field (unit: Volt ; 1 V = 1 J/C)
CONDUCTING MEDIA

Metals (electronic), electrolyte solutions (ionic)

+
+
+
φ uniform inside a conductor
v (if current I = 0)
+ E=0 + Net charge accumulates at the
+
+ surface

Define potential difference E between two conductors

Metal/metal contact potential : E = φZn − φ Fe > 0

- +
Fe - + Zn
- +
v
E
Metal/electrolyte solution

qM qS = - qM (surface charge density)

- + E = φ M − φ S (< 0) : metal/solution
- (double layer) potential difference
+ +
-
φ -
+
- + φS
- +
+
-
φM
d
 GALVANIC CELLS
V: Voltmeter (“∞” resistance)
Pt V Pt (1) Cell without liquid junction (LJ)
M1 M2
E = φ Pt 2 − φ Pt1
= (φ Pt 2 − φ M 2 ) + (φ M 2 − φ S )
+ (φ S − φ M 1 ) + (φ M 1 − φ Pt1 )

cell EMF (open circuit potential: I = 0)

V (2) Cell with liquid junction
Pt Pt

Salt bridge serves to:

(i) prevent mixing of reactants
M1 M2 (ii) provide a conducting path-
way between half-cell
solutions
(iii) eliminate contact potential
between solutions (LJ
LJ’s salt bridge potentials cancel)
(KNO3 or KCl, sat’d)

E = φ Pt 2 − φ Pt1 > 0 : M2 = cathode (+), M1 = anode (-)

In a cell at finite current: electrons in external circuit move from
anode to cathode
In solution(s): Anions migrate towards the Anode,
-
e Cations towards the Cathode
- +
+
-
I
EXAMPLES
Pt V Pt
(1) _
_+
H2

_
Ag/AgCl

HCl(aq)

Hydrogen electrode

1
L: H+ + e- H (g)
2 2
R: AgCl(s) + e- Ag(s) + Cl-

Balanced half-reactions (same number of e- ’s)

Net cell reaction:

1
AgCl(s) + H (g)
2 2
Ag(s) + H+ + Cl-

Cell notation:

Pt(H2) | HCl(aq) | AgCl | Ag | Pt

– +
Spontaneous reaction:
Cathode: Reduction
Anode: Oxidation
 e-
(2)
_ + _ +

Zn Cu

ZnSO4(aq, 0.1M) CuSO4(aq, 0.1M)

Zn | ZnSO4(aq, 0.1M) | | CuSO4(aq, 0.1M) | Cu

Anode: Zn Zn2+ + 2e- electrodissolution

Cathode: Cu2+ + 2e- Cu electrodeposition

Cell rxn: Cu2+ + Zn Cu + Zn2+

(spontaneous)

Cu

Zn

“electroless plating”

CuSO4(aq)
 THERMODYNAMICS OF GALVANIC CELLS
dQ
_
E +
E = cell EMF if I = 0
(reversible charge
đq transfer)
?
cell = closed
system

surroundings (T, p)

First Law : dU = đq + đw

Second Law : đq ≤ TdS = : reversible change (I = 0)

< : irreversible change

đw = - pdV + EdQ : net work done on cell by surroundings

hydrostatic work = – pdV (only significant if gases are
involved)
electrical work = EdQ (E = terminal voltage)

∴ dU ≤ TdS − pdV + EdQ

T, p constant: d (U + pV − TS )T , p ≤ EdQ

dQ = - nF coulombs, the charge on n moles of e-’s

(∆ r G )T , p ≤ − nFE or: E ≤ −( ∆ r G )T , p / nF

Gibbs energy of net cell reaction

Spontaneous cell reaction: ( ∆ r G )T , p < 0 ⇒ E = φc − φa > 0

Cathode: nAA + ne- n BB

Anode: n CC nDD + ne-

Cell rxn: nAA + nCC n BB + n D D

(∆ r G )T , p = nB µ B + nD µ D − n A µ A − nC µ C < 0

µ X = µ θX + RT ln a X : chemical potential ( = partial molar

Gibbs energy) of X

µ θX (T , p ) = standard chem. pot. (activity aX = 1)

Solutes: aX = yXcX (yX = activity coefficient , cX = molarity,

ideal solution : aX = cX)
Solvent: aS ≅ 1
Gases: aX = pX / atm (partial pressure of X)
Solids: aX = 1

θ  aBnB aDn D 
∴ (∆ r G )T , p = ( ∆ r G )T , p + RT ln n n 

 a A aC 
A C

θ θ θ θ θ
defining ( ∆ r G )T , p = nB µ B + nD µ D − n A µ A − nC µ C
Standard Gibbs energy of the cell reaction

Open circuit potential (EMF) E = −( ∆ r G )T , p / nF

 RT  a An A aCnC
θ 
∴ E=E + ln n n 
 Nernst equation
nF  aBB aDD 

Eθ = −( ∆ r Gθ )T , p / nF : Standard cell potential

Chemical equilibrium: ( ∆ r G )T , p = 0 ⇒ E = 0 (cell is “dead”)

RT  aBn B aDn D
θ 
0=E − ln n n 

nF  a AA aCC eq

=K equilibrium constant

∴ K = exp(nFEθ / RT )

If T = 298 K, it is customary to use the following conversion

from “ln” to “log”

RT
ln x = 0.06 log x (in volts)
F
 STANDARD REDOX POTENTIALS

Consider the cell:

SHE | | Ox, Red | Pt

SHE = Standard Hydrogen Electrode (reference electrode)

(a(H+) = 1, p(H2) = 1 atm, T = 298 K)

Half reaction: Ox + ne- Red

n
Cell rxn: Ox + H2 Red + n H+
2

θ 0.06  aO 
Cell EMF : E = E (Ox/Red) + log 
n  aR 

Standard Redox Potential (Volts vs. SHE) of Ox/Red couple

( Eθ (H+/H2) = 0 by definition)

⇒ Electrochemical series (T = 298 K)

EXAMPLE

Zn | ZnSO4 | | CuSO4 | Cu

Eθ(Cu2+/0) = +0.34 V vs SHE

Eθ(Zn2+/0) = -0.76 V vs SHE

Eθ(cell) = +0.34 – (- 0.76) = 1.10 V

 APPLICATIONS

(i) Calculation of Eθ for a composite half-reaction

Eθ / mV vs SHE

(1) Fe3+(aq) + e- Fe2+(aq) + 771

(2) Fe2+(aq) + 2e- Fe(s) - 440
(3) Fe3+(aq) + 3e- Fe(s) ?

θ θ
Thermodynamic cycle ( ∆ r G = − nFE ) :

3+ - - FE(1)θ
Fe + 3e Fe2+ + 2e-

-3FE(3)θ - 2FE(2)θ

Fe

θ θ θ θ E(θ1) + 2 E(θ2)
− 3FE(3) = − FE(1) − 2 FE( 2) or E(3) =
3
3+/0
E (Fe
θ
) = (771 – 2 × 440)/3 = - 36 mV vs SHE

(ii) Equilibrium constant for the disproportionation reaction

3 Fe2+(aq) 2 Fe3+(aq) + Fe(s) ( = (2) – 2 × (1))

∆ r Gθ = ∆ r G(θ2) − 2∆ r G(θ1) = 2 F ( E(θ1) − E(θ2) )

= +233.7 kJ mol-1
K = exp(− ∆ r Gθ / RT ) = 10 - 41 , no disproportionation
 OTHER THERMODYNAMIC RELATIONSHIPS
ASSOCIATED WITH REDOX REACTIONS

Reversible change of state of cell: dU = TdS – pdV + EdQ

Gibbs energy of cell: G = U + pV – TS

dG = dU + pdV + Vdp – TdS – SdT

= Vdp – SdT + EdQ

Apply this relationship to a cell before and after transfer of n

moles of electrons between reactants (so that charge |Q| = nF
is passed around the circuit), then subtract.
The result is

d∆ r G = ∆ rVdp − ∆ r SdT − Ed (nF )

with ( ∆ r G )T , p = − nFE
Thus,

 ∂∆ G   ∂E 
∆ r S = − r  or ∆ r S = nF  
 ∂T  p  ∂T  p

Entropy of cell reaction

Similarly, for the enthalpy (heat) of cell reaction (T, p constant):

> 0 : endothermic
qrxn = ∆ r H = ∆ rU + p∆ rV = ∆ r G + T∆ r S
< 0 : exothermic
  ∂E  
∴ ∆ r H = − nF  E − T    Gibbs-Helmholtz equation
  ∂T  p 
 ACTIVITY COEFFICIENTS OF STRONG
ELECTROLYTES
(DEBYE-HÜCKEL THEORY)

Chemical potential of ion type i:

µi = µiθ + RT ln ai = µiθ + RT ln ci + RT ln yi

= µ iideal = µ iexcess

no interactions with
other ions in solution

µi = Gi = reversible (non-pV) work of inserting 1 mol of

ions i into solution

µiideal = reversible work of inserting 1 mol discharged

ions i into solution
w(discharge) <0 w(recharge) >0
+
+ + +
+ + + +
+

µiideal - -
+
- -
-
- +- - +
-
- - -

µiexcess = RT ln yi = w(discharge) + w(recharge) < 0

Dilute electrolyte solutions:

− log yi = Azi2 I single-ion activity coefficient yi

A = 0.509 M-1/2 (T = 298 K)

I = 12 ∑ c j z 2j ionic strength
j
(sum over all ionic species j present in solution)

yi is not accessible to measurement because ions are necessarily

added to solution in the form of neutral compounds (salts),

Cνz++ Aνz−− < 0 such that ν + z+ + ν − z− = 0 (e.g., Na2CO3)

µ salt = ν + µ + + ν − µ − = µ salt
ideal
(
+ RT ln yν+ + yν− − )
≡ yν± + +ν −
y± : mean activity coefficient of the salt

ν + log y+ + ν − log y−
− log y± = −
ν + +ν −

ν + z+2 + ν − z−2
=A I = − Az+ z− I
ν + +ν −

∴ − log y± = A | z+ z− | I Debye-Hückel limiting law

(I < 0.01 M)
Generalisation:

A | z+ z− | I
− log y± = (I < 0.1 M)
1+ I
Extended Debye-Hückel equation

log y±
0
1:1 (NaCl)

2:1 (MgCl2)

2:2 (MgSO4)

I / M 1/ 2

APPLICATION : DETERMINATION OF Eθ AND y±

Pt(H2, 1 atm) | HCl(aq, c M) | AgCl | Ag

AgCl(s) + 1/2 H2(g) Ag(s) + H+ + Cl- Eθ(AgCl/Ag)

E = Eθ − 0.06 log(aH + aCl − ) = Eθ − 0.06 log( y±2c 2 )

= Eθ + 0.12 × 0.509 c − 0.12 log c

E + 0.12 log c = Eθ + 0.06 c

(E + 0.12logc)/V limiting slope = 0.06

0.222

√(c/M)

Measurement of y± (HCl) at arbitrary c :

log y±(HCl) = 8.33(0.222 – E) – log c

Definition: Formal standard potential Eθ’ of a redox couple

Ox/Red in a given medium

0.06  yO [O] 
E = Eθ (O / R ) + log 
n  R
y [ R ] 
0.06  yO  0.06  [O ] 
= Eθ (O / R ) + log  + log 
n  R
y n  [ R ] 

≡ E θ ' (O / R )
APPLICATIONS OF EMF MEASUREMENTS

(1) Solubility product of a sparingly soluble salt

Ag | AgCl(sat’d), KCl | | AgNO3 | Ag

E = ER – EL

R: AgR+ + e- Ag +0.80

L: Ag AgL+ + e- +0.80 (i)

Ag + Cl- -
AgCl + e +0.22 (ii)

Cell rxn:
AgR+ AgL+ (i)

AgR+ + Cl- AgCl (ii)

 a ( Ag R+ ) 
E = 0.06 log + 
 (i)
 a ( Ag L ) 
(
E = 0.58 + 0.06 log a ( Ag R+ )a (Cl − ) ) (ii)

0 = 0.58 + 0.06 log(a ( Ag +

L ) a (Cl
−
))

= Ksp(AgCl) = y±2 [AgL+][Cl-]

Ksp(AgCl) = 10 - 0.58/0.06 ≅ 10 – 10
+ 1.02√I
Solubility: s = [AgL ] = 10 Ksp(AgCl)/[Cl-]

I = [KCl] = [Cl-] “Common-ion effect”

(2) Potentiometric titration
KMnO4(aq)
V
H2

pH buffer
Mn2+
H+ Fe2+, Fe3+

MnO4- +8H+ + 5e- Mn2+ + 4 H2O +1.51

5 Fe2+ 5 Fe3+ + 5e- +0.77
titration rxn:
5 Fe2+ + MnO4- + 8H+ 5 Fe3+ + Mn2+ + 4 H2O

Initially, 5N moles of Fe2+ present

Before equivalence point (y < N moles of MnO4- added):

E = Eθ’(Fe3+/2+) + 0.06log((Fe3+)/(Fe2+))
 y 
= 0.77 + 0.06log  
 N − y

At equivalence point (N moles of MnO4- added):

(Fe3+) = 5x, (Mn2+) = x, (Fe2+) = 5(N – x), (MnO4-) = N – x
 x 
Eequiv = Eθ’(Fe3+/Fe2+) + 0.06log   (i)
 N − x
0.06  N − x  0.06
Eequiv = Eθ’(MnO4-/Mn2+) + log  − 8× pH
5  x  5
(pH = - log a(H+)) (ii)
 (i)+5×(ii):

6 Eequiv = Eθ’(Fe3+/2+) + 5 Eθ’(MnO4-/Mn2+) – 8×0.06pH

Eequiv = 1.39 – 0.08pH

Beyond equivalence point (y > N):

0.06
E = Eθ’(MnO4-/Mn2+) + log ((MnO4-)a(H+)8/(Mn2+))
5
 y−N
= 1.51 + 0.012log   − 0.096pH
 N 

E / V vs SHE

1.51 – 0.096pH

1.39 – 0.08pH

0.77

# moles MnO4-
added (y)
0 N/2 N 2N
 MEMBRANE EQUILIBRIUM :
ELECTROCHEMICAL POTENTIALS

2e- V

Zn Cu

Zn2+ Cu2+
SO42-

ZnSO4(aq) CuSO4(aq)
Membrane selectively permeable to water and SO42-

Cu2+ + 2e- Cu
Zn Zn2+ + 2e-
2-
SO4 (R) SO42-(L)

Cu2+ + Zn + SO42-(R) Cu + Zn2+ + SO42-(L)

θ
(∆ r G )T , p = µCu + µ Zn 2 + + µ SO 2 − ( L) − µCu 2 + − µ θZn − µ SO 2 − ( R )
4 4

 a 2 + a 2 − ( L) 
θ θ θ θ
+ RT ln 
Zn SO4
= µCu + µ Zn 2 + − µ Zn − µCu 2 +
 a 2 + a 2 − ( R) 
 Cu SO4 
= (∆ r Gθ )T , p

E = φCu − φZn = −( ∆ r G )T , p / 2 F
 RT  aCu 2 +  RT  aSO 2 − ( R ) 
E=E + θ
ln + ln 4

2 F  aZn 2 +  2 F  a 2 − ( L) 
  SO4 

= (φCu − φ RS ) − (φZn − φ LS ) = φ RS − φ LS
EMF measured with membrane potential
salt bridge i.s.o.
membrane
⇒ φ LS < φ RS
µ θSO 2 − + RT ln aSO 2 − ( L) − 2 Fφ LS
4 4
θ
= µ SO 2 − + RT ln aSO 2 − ( R ) − 2 Fφ RS - +r
4 4
or - +E
- +
µ SO 2 − ( L) = µ SO 2 − ( R )
4 4

defining aSO 2 − ( L) < aSO 2 − ( R )

4 4

µ = µ + zFφ electrochemical potential

(condition of material equilibrium
for ions: µ must be uniform)
Dilute solutions:

µ θ + RT ln c1 + zFφ1 = µ θ + RT ln c2 + zFφ2

e = F/NA elementary charge

k = R/NA Boltzmann constant

c2
= exp(− ze(φ2 − φ1 ) / kT ) Boltzmann distribution
c1
 Applications:

(1) Ion-selective electrodes

Example: K+-selective (micro-)electrode

0.5 M KCl

valinomycin/diphenyl ether Ag/AgCl electrode

Ag | AgCl | internal solution external solution | AgCl | Ag

0.5M KCl [K+]

Valinomycin is a cyclic peptide that selectively binds K+ and

transports the ions across the membrane

Equilibrium condition:

RT ln[ K + ] + Fφext = RT ln(0.5) + Fφ int

RT
E = φext − φ int = const. − 2.303 log[ K + ]
F
used to determine [K+] in soils, sea water, blood plasma, etc.
(2) pH measurement: Glass electrode

Ag/AgCl electrode

0.1 M HCl

glass membrane

dry glass
external internal
(test) Na+ solution
solution

hydrated zones
(ion exchange equilibria)

RT
E = 2.303 (pH – 7)
F

(1 < pH < 12)

(3) Gas sensing electrodes

Example: CO2 sensing electrodes

reference
electrode A

reference
electrode B

glass electrode

test solution
(0.01 M NaHCO3)

membrane

CO2(g) CO2(aq)

CO2(aq) + H2O H2CO3(aq)

H2O + H2CO3(aq) H3O+ + HCO3-(aq)

excess
+
[ H 3O ][ HCO3− ]
K= ⇒ pCO2 ∝ [ H 3O + ]
pCO2

RT
E = φ B − φ A = const. − 2.303 log pCO2
F
 ION TRANSPORT IN ELECTROLYTE SOLUTIONS
_ e-
+
I
r
E r r
+ - Fvisc Fel
+ + v+ +
+ - -
_
+ v- - vi
r r
( Fel = zi eE , Fvisc ∝ vi )
Average drift velocity of (hydrated) ions of type i = vi
r
vi ∝| E |

ionic flux = # moles ions (of type i) crossing unit area in unit
time
-2 -1 +
Ji / mol cm s
+
+
J i = ci vi
+
+
Empirical relationship:
vi
r
J i = ciui | E | migration flux

ui / cm2 s-1 V-1 = ionic mobility

Electrical current density j /Amp cm-2 = F ∑ | zi | J i = ∑ ji
i i

partial current density

r
j =κ | E | Ohm’s law
 κ / Ω-1cm-1 = F ∑ | zi | ui ci conductivity
i

λi =| zi | Fui ionic conductivity

Define:

ji λc u±
ti = = i i e.g., NaCl : t± =
j ∑ λk ck u+ + u −
k
( t+ + t− = 1)
transport number of ionic species i

Strong electrolyte: Cν + Aν − , total conc. = c

c+ = ν+c , c- = ν-c

ν ± λ±
t± =
ν + λ+ + ν − λ−

κ
Define: Λ m = molar conductivity
c

Λ m = F (ν + z+u+ + ν − | z− | u− ) = ν + λ+ + ν −λ−

Effect of ion-ion interactions at finite ionic strength (I):

Λ m = Λ0m − K I Kohlrausch’s law

0 0 0
( Λ m = ν + λ+ + ν − λ− = limiting molar conductivity)
 MEASUREMENT OF TRANSPORT NUMBERS

(1) Potentiometric method

Concentration cell with liquid junction:

1 mol e- V

Ag/AgCl t- mol Cl- Ag/AgCl

t+ mol Na+
cL cR

NaCl(aq)

Membrane is permeable to both Na+ and Cl-

⇒ steady state liquid junction potential (no equilibrium!)

ELJ = φ Rsol − φ Lsol

= − ∆GLJ / F
where
∆GLJ = t+ ( µ +( R ) − µ +( L ) ) + t− ( µ −( L ) − µ −( R ) )
c 
= (t+ − t− ) RT ln R 
 cL 
Recall that t− = 1 − t+

RT  cL 
∴ ELJ = (2t+ − 1) ln 
F  cR 
liquid junction (diffusion) potential
The measured cell potential E is the sum of ELJ and the resultant
of the two metal/solution contact potentials, i.e. the “Nernstian”
potential, ENernst, that would be measured by the voltmeter if the
liquid junction were to be replaced by a salt bridge (which is
normally used to eliminate ELJ).

Half reactions:

AgCl + e- Ag + Cl-(R)

Ag + Cl-(L) AgCl + e-

Cell reaction: Cl-(L) Cl-(R)

RT  cL 
E Nernst = ln 
F  cR 

Thus,
RT  cL 
E = 2t+ ln  ⇒ t±
F  cR 

We saw earlier that, for a strong 1:1 electrolyte,

λ± Fu±
t± = = ⇒ u± = t ± Λ m / F
λ+ + λ− Λm
(2) Moving Boundary method

I
cathode

t + ∆t - M+X-(aq)
X
δ leading solution
t M+ (low density)

X- N+X-(aq)
N+ indicator solution
(high density)
A
anode
I
t(N+) and t(X-) known , t(M+) unknown

u(N+) < u(M+) (drift velocity vi = −ui dφ / dx )

charge carried by M+ ions across area A during time ∆t =

tM + I∆t = FAδ [MX ]

∴ tM + = Fv[ MX ] / j (j = I/A current density;

v = δ/∆t speed of boundary)
φ
indicator solution leading solution
sharp boundary
N+ constant speed M+ constant speed
M+ accelerated N+ slowed down
distance along tube
 ELECTRODE PROCESSES

- kf
electrode solution Half reaction: Ox + ne Red
Ox kb
e.g., Fe3+ + e- Fe2+
ne-
r s
r = k f [O ]surf , r = kb [ R]surf
Red
Rate constants kf,b are functions of E:
kf increases, kb decreases if E is made
more negative (“e- concentration” on
electrode surface increases), and vice
versa
Sign convention:

Ox + ne- Red net oxidation: anodic current, I > 0

Ox + ne- Red net reduction: cathodic current, I < 0

Slow e- transfer : “irreversible rxn” (I activation-controlled)

Fast e- transfer : “reversible rxn” (I diffusion-controlled)

In practice, one always adds excess inert (“supporting”)

electrolyte, typically NaClO4 (~ 1 M) to increase conductivity,
suppress electric fields inside solution and hence reduce the
migration flux of Ox and Red in bulk solution.
( t Na + + tClO − ≅ 1 , tO , R ~ 0)
4

At electrode surface, Ox and Red are consumed or generated

concentration gradients if e- transfer relatively fast
diffusion transport of Ox/Red towards or away from
electrode
E.g., net oxidation (I > 0)

conc.

[O]surf
Jdiff,O
[R]bulk

[O]bulk
Jdiff,R
[R]surf

0 δ distance from electrode

(diffusion layer
thickness ~ 0.1 mm)

[O]surf − [O ]bulk
Diffusion fluxes: J diff ,O = DO
δ
[ R]bulk − [ R]surf
J diff , R = DR
δ
2 -1
D / cm s : diffusion coefficient

Faradaic current density (steady state):

jF = nFJ diff ,O = − nFJ diff , R

Reversible (= fast) e- transfer: local equilibrium at surface.

RT  [O ]surf
θ


“local” Nernst equation (I ≠ 0) : E = E '+ ln
nF  [ R ]surf 

RT  [O ]bulk 
“global” equilibrium (I = 0) : Eequil = Eθ '+ ln 
nF  [ R]bulk 
 Concentration polarisation. Polarography

RT  [O]surf [ R ]bulk 
Overvoltage η = E − Eequil = ln
nF  [O]bulk [ R ]surf 
(η > 0 in this example)

Current/voltage characteristic of reversible redox couple

jF

jlim,a

Red Ox + ne-

(jlim,a + jlim,c)/2

Eequil E1/2 E/V vs SHE

-
Ox + ne Red
jlim,c polarogram

η << 0 : [O]surf ~ 0 , cathodic limiting current density :

[O]bulk
jlim,c = − nFDO
δ
η >> 0 : [R]surf ~ 0 , anodic limiting current density :
[ R]bulk
jlim,a = + nFDR
δ
E1/2 : half-wave potential

( E1/2 ≅ Eθ’ )
 3-electrode cell configuration:

potentiostat
Hg

RE (SCE)
N2

sat’d KCl(aq) Hg2Cl2

WE (DME)
(~ 4.2M)
Ox/Red
+ 1M NaClO4 Hg
A
CE (Hg pool)

WE = working (or indicator) electrode

(DME: dropping mercury electrode)
CE = counter (or auxiliary) electrode
RE = reference electrode
(SCE: saturated calomel electrode)

Prior to measurement, cell solution purged with N2 (~ 1 hr) to

remove dissolved O2

Current flows between WE and CE, potentiostat controls E of

WE w.r.t. RE: Eliminates contribution of Ohmic potential drop
inside solution to E.
Area of WE << area of CE, so that WE acts as a bottleneck for
current flow current/voltage characteristic of cell is
essentially identical to that of WE
Advantages of using DME:
- simple spherical geometry
- smooth, clean surface produced every ~ 4 sec
- high reproducibility of results
- broad potential window (ca. -2 to +0.5 V vs SCE) available
for observing oxidation/reduction currents (high overvoltage
for H2 evolution)
Disadvantage: toxicity

Example:
Test solution containing Zn2+ and Cd2+ ions
Sampled-dc polarogram:

- I / mA

Zn2+ + 2e- Zn(Hg)

Cd2+ + 2e- Cd(Hg)

0.64 1.00 - E / V vs SCE

(M(Hg) = amalgam)

− I lim,c = 2 FAD[ M 2 + ]bulk / δ (A = electrode area)