Idealized heterogeneous electron transfer: ko Ox + n eRed

e-

eko

Ox counter electrode Red

actual:

e-

Eapplied
P= physisorbed impurity
1- 1

1- 1

Special Features of Electrochemistry

analytical sensitivity (1 pamp = 10-17 moles/second) can make microscopic probes ( < 1 um) wide range of time scales ( ~50 nsec up)
large, tunable driving force direct interconversion of chemical and electrical energy (not a heat engine, not Carnot limited)

1- 2

1- 2

single-cell voltammogram, matching that of noradrenaline

2 um

carbon microelectrodes amperometric response from single adrenal chromaffin cell

Ewing, Strein, Lau, Acc. Chem. Res. 1992, 25, 440

1- 3

1- 3

Special Features of Electrochemistry

analytical sensitivity (1 pamp = 10-17 moles/second) can make microscopic probes ( < 1 um) wide range of time scales ( ~50 nsec up)

large, tunable driving force

(Cl2, Na, F2 production, fast reactions, electrosynthesis)

direct interconversion of chemical and electrical energy

(not a heat engine, not Carnot limited)

1- 4

1- 4

load

e-

(~ 200 amps, 0.5 volt)

(exhaust)

H 2O

recirculated fuel

gas flow channels

heat, ~ 85 oC

air

H2
1- 5

1- 5

polymer electrolyte membrane, catalysis, support, (all of the important stuff)

Fuel cell powered bus, Ballard Power Systems, 1997

1- 6

1- 6

Ballard Fuel Cell + electric motor, 275 hp (205 kW)

1- 7

1- 7

Who cares about electrode kinetics?

electrosynthesis (Al, Mg, NaOH, Cl2, etc) electrochemical energy conversion (fuel cells, batteries, photocells) electroanalysis (glucose, O2, K+, pH, etc.) corrosion (almost everything)
1- 8

$ 40 billion/yr of U.S. GDP

$ 80-200 billion/yr in U.S.A.

1- 8

The Big Issues: 1. Thermodynamics of electrochemical cells (how does an electron affect free energy, etc.?) 2. Kinetics of electron transfer (what happens when an electron is a reagent ?) 3. Mass transport (things have to get to the electrode to react)

1- 9

1- 9

Cu and Pt, both 298 K

Fermi distribution function

Fermi distribution function

-3.0

-3.0

-3.5
V e , m -4.0 u u c a v o t e -4.5 v i t a l e r y g -5.0 r e n E

Cu, Ef= -4.65 V

-3.5
V e , m -4.0 u u c a v o t e -4.5 v i t a l e r y g -5.0 r e n E

Pt, Ef= -5.70 V

-5.5

-5.5

-6.0 -0.1

0.1

0.3

0.5 f(E)

0.7

0.9

1.1

-6.0 -0.1

0.1

0.3

0.5 f(E)

0.7

0.9

1.1

1- 10

1- 10

+ RT ln a K+ + F

K+ activity

aK
K
+

electrostatic potential

in

out

aK
in

+ out

K+ permeable membrane
1- 11

1- 11