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

BUTLER-VOLMER AND TAFEL EQUATIONS

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

BUTLER-VOLMER AND TAFEL EQUATIONS

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

E/V vs. reference electrode

3.010 -6

I/A

I/A

2.010 -6

1.010 -6

-1.010 -6

-3.010 -6
-0.5

0.0

E/V vs. reference electrode

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

E/V vs. reference electrode

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

E/V vs. reference electrode

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

E/V vs. reference electrode

1.0

-1.010 -5
-1.0

-0.5

0.0

0.5

E/V vs. reference electrode

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

E/V vs. reference electrode

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

E/V vs. reference electrode

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

E/V vs. reference electrode

0.5

-3.010 -07
-0.5

0.0

E/V vs. reference electrode

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