1 2 3

Lecture 1 on Electrochemistry
Electrode potential, kinetics of
electron transfer, water splitting,
blood glucose sensors

Key Idea:
The use of an external power source
allows us to control the direction and the
rate of electron transfer at electrodes.

majda@berkeley.edu Chem 105, UC Berkeley, Spring 2017

 1
Electrochemical systems are not homogeneou
O + e- => R
O could be anthracen or Fe3+, for example

Electrode Diffusion Layer Bulk

1 to 50 m in thickness untouched by interfa
Excess charge on surface
Depletion of O near surface

Chem 105, UC Berkeley, Spring 2017

 Chem 105, UC Berkeley, Spring 2017
Electrolysis: what potential must be applied
to pass a certain current?

Rsolution

l = Ecath Eanode iRsolution kinetic overpotenti

Chem 105, UC Berkeley, Spring 2017
 2
Electrolysis:
We can control electron energy: Eappl

Electrode potential is expression of electron energy!

Chem 105, UC Berkeley, Spring 2017

 Electrolytic Production of Aluminum:
Hfo (Al203) = -1676 kJ/mol; Eo = -1.68 V; Tmelting(Al2O3) = 2050
Invention of
Hall, Hrault (1886): electrolysis of alumina/cryolite melt at 950 C
Melt contains: Al3+, Na+, O2-, AlF63-

Al2O3
Na3AlF6

Ecath -1.5 V: Al3+ + 3e- -> Al (l) Eanode +1.0 V: C + 2O2- - 4 e- -> CO2

Eappl = 1.5 1.0 1 -4 V; Rsolution(950 oC) 2; I 5 x 105 A !!

Chem 105, UC Berkeley, Spring 2017
 Production of Aluminum ?
Hfo (Al203) = -1676 kJ/mol; Eo = -1.68 V; Tmelting(Al2O3) = 2050

uminum apex of the Washington Memorial: 18

Chem 105, UC Berkeley, Spring 2017

Charles Martin Hall 1863 - 1914

Chem 105, UC Berkeley, Spring 2017

 2
ctrode potential is expression of electron ener
s not quantized; it can be adjusted continuou
()E, Electron energy Consider anthracene, An:

e_
E 0 (An/ An ) 1.5V vs. SHE
LUMO

At this potential neither reduction of An to An*- nor oxidation to An*+ is pos

e_ E 0 (An / An) 1.5V vs. SHE

HOMO

Chem 105, UC Berkeley, Spring 2017

 3
Current is proportional to
the electrochemical reaction rate

Rate of electrochemical reactions, v [mol s-1 cm-2]

1 dN mol Q 1 dQ
v cm 2s ; N th u s : v
A dt nF nF A dt

since dQ/dt = i then i =nFAv

Rate is proportional to concentration: v = kC*

Thus: i =nFAkC*

Chem 105, UC Berkeley, Spring 2017

What are the rate limiting steps?

1. Electron transfer

2. Mass transport

Chem 105, UC Berkeley, Spring 2017

Rate Constant of Chemical Reactions
R P

G*f

Reactants Gb*

Grxn
0

Products

G*f /RT
kf Ae
Chem 105, UC Berkeley, Spring 2017
 Ox + e- R
G = -nFE

(-)E Reduction Reduction Reduction

Oxidatio Oxidation Oxidatio

n n

G* G*0 G*0 G*0

G*

-nF
E 0
+nF
Ox + e- R Ox + e- R Ox + e- R

nF

EE 0
kRed k e 0 RT

of electron transfer increases exponentially with pot

Chem 105, UC Berkeley, Spring 2017
 Ox + e- R 4

nF
EE 0
kkin k e 0 RT

nF
EE 0
i nFAkC * i nFAk C * e
0 RT ilim nFAkmtC *
Chem 105, UC Berkeley, Spring 2017
 Kinetic Overpotential

nF
EE 0
kkin k e
0 RT

iR
i nFAkkinC *
Overpotential

Eo (-)E
To reduce overpotential, we develop catalysts.
Chem 105, UC Berkeley, Spring 2017
Electrochemical energy storage
and conversion

Chem 105, UC Berkeley, Spring 2017

 Water Splitting

athode: 2H2O + 2e- => H2 + 2OH-

E o
cell= - 1.23 V
node: 2H2O 4e- => O2 + 4H+

In reality Ecell -2. V

Due to high overpotential of O2 evolution
Chem 105, UC Berkeley, Spring 2017
 Kinetic Overpotential

nF
EE 0
kkin k e
0 RT

iR
i nFAkkinC *
Overpotential

Eo (-)E
To reduce overpotential, we develop catalysts.
Chem 105, UC Berkeley, Spring 2017
Amperometric Sensors
Clark oxygen electrode
O2 + 4H+ + 4e- 2H2O

ilim nFAkmtC *

i/ A

[O2]/M

Chem 105, UC Berkeley, Spring 2017

Amperometric Glucose Sensors

Chem 105, UC Berkeley, Spring 2017

Amperometric Glucose Sensors

glucose
oxidase

Chem 105, UC Berkeley, Spring 2017

Amperometric Glucose Sensors

ilim nFAkmtCglucose
*

ferrocene/ferrocenium mediator
Chem 105, UC Berkeley, Spring 2017
THE END

Chem 105, UC Berkeley, Spring 2017