Electrochemistry

BASIC ELECTROCHEMISTRY
THE CHARGE AND CURRENT

Electrochemistry studies the processes which involve charge
The charge is a source of electric field
Element of charge: 1.60210-19 C
The energy change is 1.60210-19 J if we move the charge across the potential
drop of 1V
If we do the same with 1 mol of charges, we obtain
A
+
1V
The current is the change of charge per time
dQ
dt
FARADAYS LAWs (1834)

The chemical power of a current of electricity is in
direct proportion to the absolute quantity of electricity
which passes
Electrochemical Equivalents coincide, and are the
same, with ordinary chemical equivalents
m
Q
M zF
MIt
m
zF
M
m
Idt
t 0
zF
Area under current-time curve (and freqently the currentpotential curve also) is the charge!! This way can be deduced
how much material was transformed.
CONDUCTIVITY
R
l
A
l
()
A
E
R (Ohm law)
I
+
-
Electrolytes: same principle, but

conductivity is preferred
A
G
l
The unit for conductivity is

Siemens, what is the unit
of specific conductivity?
For species KXAY:

Migration velocities can be different
Stokes force is balanced by force induced by electric field
Only the cations distant from the plane by vA or nearer will
cross the plane. In unit field (1V) and unit area will cross the
boundary xcFz cat ucat cations
xcFzcat ucat ycFz anuan
CONDUCTIVITY
V
A
Solutions can have different concentrations:
S m3
2
1
Sm mol
c m mol
This is used for measurements of

dissociation constants:
AB
c (1 -)
c c
c
2 2

c
KD
c 1 1
HOW AND WHERE THE POTENTIAL

DIFFERENCE DEVELOPS
s o lu tio n 1
s o lu tio n 2
Junction potential
(Henderson)
Donnan potential
m e m b ra n e
Potential difference develops where a charge

separation in space occurs
THE NERNST EQUATION

The combination of two basic physical chemistry
equations:
G zFE
and
G RT ln K
All processes in which charge separation occurs go
to equilibrium
but what is K?
DANIEL CELL
Zn | ZnSO4 | | CuSO4 | Cu
Zn+CuSO4 Cu+ZnSO4
Cu ZnSO4
zFEMN RT ln
Zn CuSO4
is it OK?
BACK TO NERNST EQUATION

RT aox
EE
ln
zF ared
0
RT ared
EE
ln
zF
aox
0
aox
2.303RT
EE
log
zF
ared
0
2.303RT
0.059 V
F
(at 25C )
ELECTRODES OF THE FIRST KIND

The term electrode is here used in a sense of a half-cell.
Metal immersed into the solution of its own soluble salt. The potential is
controlled by the concentration of the salt.
EE
0
Me / Me
RT
ln aMe
zF
Zn in ZnCl2, Ag in AgNO3, Cu in CuSO4 etc.
Non-metallic electrodes gas electrodes (hydrogen and chlorine electrode)
THE HYDROGEN ELECTRODE
THE HYDROGEN ELECTRODE
E E 0Hat / H
Pt
Pt
RT
RT
ln KK H p H 2
ln H
F
F
ELECTRODES OF THE SECOND KIND

Argentochloride Ag | AgCl | KCl | |
Calomel Hg | Hg2Cl2 | KCl | |
Mercurysulphate Hg | Hg2SO4 | K2SO4 | |
0
SHE
197 m V 244 m V
640 m V
s a t. H g /H g 2S O
REDOX ELECTRODES
F e 2+
Fe
e-
3+
eFe
Fe
3+
The electrode serves as an electron sink

Redox combo
2+
P t e le c tr o d e
ELECTRODES OF THE THIRD KIND

..just a curiosity
Zn | Zn2C2O4 | CaC2O4 | CaCl2 | |
We can measure the concentration of Ca2+, but

theres a better device to do this
THE ABSOLUTE SCALE OF POTENTIALS

R E D (v a c u u m )
- G
s o lv ( R
IO N
O X (v a c u u m )
- G
ED)
zFE
s o lv ( O
X)
Reference to vacuum
(instead of hydrogen electrode)
ABS
R E D (s o lu tio n )
O X (s o lu tio n )
Thermodynamic cycle for hydrogen
- G
The most commonly accepted

value is 4.42V, but values
around 4.8V are also reported
- G
(v a c u u m )
(v a c u u m )
- G
s o lv
-F E
(s o lu tio n )
d is s /2
0
ABS
1 /2 H
4420 m V
0
Vacuum
IO N
SHE
197 m V 244 m V
640 m V
s a t. H g /H g 2S O
ION SELECTIVE ELECTRODES

Membrane potential reflects the
gradient of activity of the analyte ion in
the inner and outer (sample) solutions.
The trick is to find a membrane material, to

which an analyte is selectively bound. The
membrane must be conductive (a little bit, at
least), but it should not leak
Liquid junction for
reference electrode
(sometimes is high)
Li
Li
H
Si
Li
h y d r a te d H a u g a a r d la y e r s
L i io n s p a r tia lly fr e e
+
400 M
Si
Nikolski eq.
E Eassym
RT
RT
ln a H O X
ln a Na
3
F
F
MEMBRANES FOR ISEs

Glass membranes (H+, for other cations change in the composition of glass
membrane (Al2O3 or B2O3 in glass to enhance binding for ions other than H + (Na+,
Li+, NH4+, K+, Rb+, Cs+ and Ag+)
Crystalline Membranes (single crystal of or homogeneous mixture of ionic
compounds cast under high P, d~10 mm, thickness: 1-2 mm. Conductivity: doping or
nonstechiometry, Ag+ in AgCl or Ag2S, Cu+ in Cu2S. Fluoride electrode: determines
F-, LaF3 crystal doped with EuF2).
Liquid membranes (organic, immiscible liquid held by porous (PVC) membrane
with ion exchange properties or neutral macrocyclic compouds selectively binding
the analyte in their cavities)
POTENTIOMETRY
Cell and voltmeter behaves as a
voltage divider circuit
E(cell)
Ri
RM
E(measured)
R2
E2 E1
R1 R2
R1
E1
Emeasured Ecell
R2
E2
RM
RM Ri
POTENTIOMETRY AND PHYSICAL CHEMISTRY

1. Activity coefficients determination
2. Solubility products determination
3. Ion product of water determination
Pt | H2 | HCl | AgCl |Ag

Ag | AgNO3 | |KNO3 | | KX, AgX | Ag
Pt | H2 | KOH | |KCl | AgCl |Ag
Ionic product of water: 1.00810-14 (25C) good agreement with
conductivity measurement
3-ELECTRODE CELLS AND

POTENTIOSTATS
Polarizable and nonpolarizable
ELECTRODE MATERIALS
Inert metals (Hg, Pt, Au)
Polycrystalline
Monocrystals
Carbon electrodes
Glassy carbon
reticulated
Pyrrolytic graphite
Highly oriented (edge plane, )
Wax impregnated
Carbon paste
Carbon fiber
Diamond (boron doped)
Potential window available for experiments
is determined by destruction of electrode
Semiconductor electrodes (ITO)
material or by decomposition of solvent (or
Modified electrodes
dissolved electrolyte)
ELECTRON TRANSFER PHENOMENON

1-10 nm
The double-layer region is:
Electrode
surface
Solvated
ions
Where the truncation of the metals

Electronic structure is compensated for
in the electrolyte.
1-10 nm in thickness
~1 volt is dropped across this region
Which means fields of order 107-8 V/m
The effect of this enormous field at the electrodeelectrolyte interface is, in a sense, the essence of
electrochemistry. [1]
l
IHL
OHL
[1] Bockris, Fundamentals of Electrodics, 2000
BUTLER-VOLMER AND TAFEL EQUATIONS
ne
ox
re d
E
G
E
#
-
zF E
E
zF E
(E 2)
#
-
(E 1)
#
+
(E 1)
#
+
(E 2)
E 2< E
r e a c tio n c o o r d in a te

i
i0 , = 0 .7
i0 , = 0 .5
Exchange current density

Depends
on
the
species
undergoing redox transformation
and on the electrode material
i0 . = 0 .3
ii
i0 ' < i0 , = 0 .5
In fact, large overpotential for

hydrogen evolution on Hg
surfaces enables us to observe
reductions in aqueous solutions
exp (1 ) nF ( E E ) exp nF ( E E )
0
RT
RT
Also, the development of modern

modified electrodes is based on
finding the modifying layer
which increase the exchange
current density on the electrode
surface

i
lo g (a b s ( i0 ))
i0
i i0
(1 ) zF
zF
( E E ) exp
(EE )
RT
RT
exp
2.303zF
(E E )
RT
log i log i0
MASS TRANSFER
Migration
Convection
Diffusion
We try to avoid migration by the addition excess

supporting electrolyte
TRANSPORT BY DIFFUSION
t1
t2
t3
t= 0
1st Fick Law
j D Cx
C s
x ... d is ta n c e fr o m th e e le c tr o d e
t= 0
ilim
0
x 0
Nernst diffusion layer
c0 cs
i zFD
N
C s
c
i zFD
c0
zFD
N
D E E
D E E
RT cS
ln
zF c0
RT
i
ln 1
zF
ilim
THE COTTRELL EQUATION

t1
t2
t3
t= 0
Cs
t= 0
x ... d is ta n c e fr o m th e e le c tr o d e
c
2c
D 2
t
x
Mathematical solution for boundary conditions of CA

experiment is very complicated, but the result is
simple:
Second Fick law
c0 cs
i zFD
Dt
This is how Nernst layer thickness changes over time
TRANSPORT BY CONVECTION
Rotating disk electrode (RDE)
Rotating ring disk electrode

(RRDE)
c u rre n t ta k e -o ff
r o ta tin g c y lin d e r
s o lu tio n
" ro ta tin g d is k "

A c tiv e a r e a o f
th e e le c tro d e
IL = (0,620)zFAD2/31/21/6c Levich Equation

speed of rotation (rads-1),
kinematic viscosity of the solution (cm2s-1),
kinematic viscosity is the ratio between solution viscosity and its specific weight.
For pure water: = 0,0100 cm2s-1, For 1.0 moldm-3 KNO3 is = 0,00916 cm2s-1
(at 20C).
c concentration of electroactive species (in mol.cm-3, note unusual unit)
D diffsion coefficient (cm2s-1), A electrode area in cm2
POLAROGRAPHY
Halfwave potential
Limiting diffusion current (Ilkovic equation)
CYCLIC VOLTAMMETRY
CV the most important electrochemical method
One or more cycles CV

Half cycle LSV
0 t t r : E Ei vt
t r t 2t r : E Ei v t t r
v the scan rate
REVERSIBLE CYCLIC VOLTAMMOGRAM

Electroactive species attached
to the electrode, both redox
forms stable
F
I FA 0 v
RT
E E0
RT
F
exp
E E0
RT
exp
REVERSIBLE CYCLIC VOLTAMMOGRAM

4.010 -6
fo rw a rd
scan
-2.010 -6
-0.50
Electroactive species in
solution, both stable
2.010 -6
I/A
re ve rs e
scan
IUPAC convention
-0.25
0.00
0.25
E/V vs. reference electrode
Randles-Sevcik equation:
0.50
Peak separation is 59 /z mV
Ipc = Ipa = 2,69.105 A z3/2 D1/2 c v1/2

A in cm2, D in cm2s-1/2, c in molcm-3, v in V/s
QUASI AND IRREVERSIBLE

VOLTAMMOGRAMS
4.010 -6
Black: k=1cmsec-1
Blue: k=0.001
Red: k=0.00001
Black: alpha=0.5
Blue: alpha=0.3
Red: alpha=0.7
-2.010 -6
-0.50
-0.25
0.00
0.25
0.50
3.010 -6
I/A
I/A
2.010 -6
1.010 -6
-1.010 -6
-3.010 -6
-0.5
0.0
0.5
BASIC MECHANISMS IN CV
E, C notation
(E electron transfer,
C coupled chemical reaction)
E, EE, CE, EC, ECcat etc.

Mechanisms can be very complex
even for simple systems
Two electron-two proton system =
square scheme
THE EE MECHANISM
7.010 -6
7.010 -6
E= 400 mV
5.010 -6
3.010 -6
I/A
I/A
3.010 -6
1.010 -6
1.010 -6
-1.010 -6
-1.010 -6
-3.010 -6
-3.010 -6
-5.010 -6
-1.0
-0.5
0.0
0.5
-5.010 -6
-1.0
1.0
0.0
0.5
1.0
1.010 -5
5.010 -6
E= 50mV
E= -100mV
5.010 -6
I/A
3.010 -6
I/A
-0.5
7.010 -6
1.010 -6
-1.010 -6
0
-5.010 -6
-3.010 -6
-5.010 -6
-1.0
E= 200 mV
5.010 -6
-0.5
0.0
0.5
1.0
-1.010 -5
-1.0
-0.5
0.0
0.5
1.0
THE EC MECHANISM
I/A
3.010 -6
O X
R ED
Black: kf=0 cm.s-1

Blue: 0.2
Red: 0.5
Orange: 1
Green: 10
RED
Z
1.010 -6
-1.010 -6
-3.010 -6
-0.5
0.0
0.5
There are many variations of this mechanism:

Reaction with solvent
Dimerization
Radical substrate reaction
EC catalytic etc.
EC catalytic
3.510 -5
I/A
2.510 -5
O X
R ED
R ED + A
O X + Z
1.510 -5
Black : no A
Blue: A (c=1)
Red: A (c=10)
Green: A (c=100)
5.010 -6
-5.010 -6
-0.5
0.0
0.5
THE CE MECHANISM
4.010 -06
1.010 -07
3.010 -06
1.010
-1.410 -14
-06
I/A
I/A
2.010 -06
-2.310 -13
-1.010 -06
-2.010
-2.010 -07
-06
-3.010 -06
-0.5
-1.010 -07
0.0
0.5
-3.010 -07
-0.5
0.0
0.5
MICROELECTRODES
Microelectrode: at least one dimension must be comparable to diffusion layer
thickness (sub m upto ca. 25 m). Produce steady state voltammograms.
Converging diffusional flux
E le c tro d e
M e ta l c o n ta c t
C o n d u c tiv e jo in t
1 1

r
I nFADc 0
E le c tro d e b o d y
F ib e r
A )
In s u la to r
B)
C)
2Dt
Advantages of microelectrodes:
fast mass flux - short response time (e.g. faster CV)
significantly enhanced S/N (IF / IC) ratio
high temporal and spatial resolution
measurements in extremely small environments
measurements in highly resistive media
PULSED TECHNIQUES
TAST POLAROGRAPHY
SAMPLED DC POLAROGRAPHY
NORMAL PULSE VOLTAMMETRY
DIFFERENTIAL PULSE VOLTAMMETRY
SQUARE WAVE VOLTAMMETRY
AC voltammetry
E
tim e

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BASIC ELECTROCHEMISTRY

THE CHARGE AND CURRENT

The current is the change of charge per time

FARADAYS LAWs (1834)

Electrolytes: same principle, but

The unit for conductivity is

For species KXAY:

xcFzcat ucat ycFz anuan

This is used for measurements of

HOW AND WHERE THE POTENTIAL

Potential difference develops where a charge

THE NERNST EQUATION

BACK TO NERNST EQUATION

ELECTRODES OF THE FIRST KIND

Zn in ZnCl2, Ag in AgNO3, Cu in CuSO4 etc.

Non-metallic electrodes gas electrodes (hydrogen and chlorine electrode)

THE HYDROGEN ELECTRODE

THE HYDROGEN ELECTRODE

ELECTRODES OF THE SECOND KIND

The electrode serves as an electron sink

ELECTRODES OF THE THIRD KIND

We can measure the concentration of Ca2+, but

THE ABSOLUTE SCALE OF POTENTIALS

Thermodynamic cycle for hydrogen

The most commonly accepted

ION SELECTIVE ELECTRODES

The trick is to find a membrane material, to

MEMBRANES FOR ISEs

POTENTIOMETRY AND PHYSICAL CHEMISTRY

Pt | H2 | HCl | AgCl |Ag

3-ELECTRODE CELLS AND

Polarizable and nonpolarizable

ELECTRON TRANSFER PHENOMENON

Where the truncation of the metals

Which means fields of order 107-8 V/m

[1] Bockris, Fundamentals of Electrodics, 2000

BUTLER-VOLMER AND TAFEL EQUATIONS

BUTLER-VOLMER AND TAFEL EQUATIONS

Exchange current density

In fact, large overpotential for

Also, the development of modern

BUTLER-VOLMER AND TAFEL EQUATIONS

We try to avoid migration by the addition excess

1st Fick Law

Nernst diffusion layer

THE COTTRELL EQUATION

Mathematical solution for boundary conditions of CA

Second Fick law

This is how Nernst layer thickness changes over time

Rotating ring disk electrode

" ro ta tin g d is k "

IL = (0,620)zFAD2/31/21/6c Levich Equation

One or more cycles CV

REVERSIBLE CYCLIC VOLTAMMOGRAM

REVERSIBLE CYCLIC VOLTAMMOGRAM

E/V vs. reference electrode

Ipc = Ipa = 2,69.105 A z3/2 D1/2 c v1/2

QUASI AND IRREVERSIBLE

E/V vs. reference electrode

E/V vs. reference electrode