Chemistry 232

Electrochemistry Notes

Electrochemical Cells

Galvanic cells

an electrochemical cell that drives

electrons through an external circuit
spontaneous redox reaction occurring
inside cell.

The Zn/Cu Galvanic Cell

half-reactions
Cu2+ (aq) + 2 e- Cu (s) (cathode, RHS)
Zn2+ (aq) + 2 e- Zn (s) (anode, LHS)

A Schematic Galvanic Cell

e-

Porous Disk
e-

eReducing Agent
Anode

Oxidizing Agent
Cathode

The Zinc/Copper galvanic cell.

e-

Zn(s)

1.10 V

Porous Disk or
Salt Bridge

e-

Cu(s)
e-

ea(Zn2+) = 1.00
Anode

a(Cu2+) = 1.00
Cathode

Cell Reactions
The difference in the RHS and the LHS
reaction
Cu2+ (aq) + Zn (s) Cu (s) + Zn2+ (aq)
For each half reaction, we can write the
reaction quotient as follows
Cu2+ (aq) + 2 e- Cu (s)
Q = 1/ a(Cu2+)
Zn2+ (aq) + 2 e- Zn (s)
Q = 1/ a(Zn2+)
Overall Qcell = a(Zn2+) / a(Cu2+)

Cell Diagrams

A shorthand way of expressing what

takes place in an electrochemical
cell.
For the above electrochemical cell.
Pt Cu (s) Cu2+ (aq) Zn2+ (aq) Zn (s) Pt

Note

phase boundary
salt bridges

liquid junction

Another Example

The cell reaction

H2 (g) + Cu2+ (aq) 2 H+ (aq) + Cu
(s)
Pt H2 (g) H+ (aq) Cu2+ (aq) Cu (s) Pt

Electrochemical cells

a cell that has not reached equilibrium can

do electrical work by driving electrons
through an external wire.

Reversible Electrochemical Cells

In order for us to make measurements

on an electrochemical cell, it must be
operating reversibly.

Place an opposing source of potential in

the external circuit
Cell operates reversibly and at a constant
composition.

we,max = G

The Measurement of Cell

Potentials

Measure the potential of an electrochemical

cell when the cell is at equilibrium, i.e., the
state between the galvanic and the
electrolytic cell.
Counter potential
(load)

ePorous Disk
e-

eReducing Agent

Anode

Oxidizing Agent

Cathode

Derivation of the Nernst Equation

Consider an electrochemical cell that

approaches the equilibrium state by
an infinitesimal amount d

dG J J d rxnG d
J

Reminder

dG
r G J J
J
d

T ,P

The Work in Transporting Charge

The maximum work

dw e ,max rxnG d

For the passage d electrons from the

anode (LHS) to the cathode (RHS)

eN A d F d
F = Faradays constant = e NA = 96485 C/mole

The Cell Potential

The work to transport charge

dw e ,max F d E cell

dw e ,max
rxnG
d

rxnG
- E cell
F

Standard Cell Potentials

From the reaction Gibbs energy

o

r G r G RT ln Qcell F E cell
o

RT ln Qcell
r G
r G

E cell
F
F
F
We define

E cell

r G

The Nernst Equation

E cell

RT
E
ln Qcell
F

E represents the standard cell potential,

the potential of the cell when all cell
components are under standard
conditions.

f (all gases) = 1
a (solutes) = 1
T = 298.15 K
P = 1.00 bar pressure

Cells at Equilibrium

When the electrochemical cell has

reached equilibrium

E cell 0 V Qcell K cell

Kcell = the equilibrium constant for the cell reaction.

RT

FE
E
ln K cell ln K cell
F
RT

Knowing the E value for the cell, we can estimate

the equilibrium constant for the cell reaction.

Equilibrium Constant Calculations

from Cell Potentials

Examine the following cell.

Pt Sn2+ (aq), Sn4+ (aq) Fe3+ (aq) Fe2+ (aq)

Pt

Half-cell reactions.
Sn4+ (aq) + 2 e- Sn2+ (aq) E(Sn4+/Sn2+) = 0.15 V
Fe3+ (aq) + e- Fe2+ (aq)
E (Fe3+/Fe2+) = 0.771 V

Cell Reaction
Sn2+ (aq) + 2 Fe3+ (aq) Sn4+ (aq) + 2 Fe2+ (aq)
Ecell = (0.771 - 0.15 V) = 0.62 V

Standard Reduction Potentials

Standard reduction potentials are

intensive properties.
We cannot measure the potential of
an individual half-cell!
We assign a particular cell as being
our reference cell
Assign values to other electrodes on
that basis.

The Standard Hydrogen Electrode

Eo (H+/H2) half-cell = 0.000 V

e-

f{H2(g)} = 1.00

H2 (g)

a (H+) = 1.00

Pt gauze

A Galvanic Cell With Zinc and the

Standard Hydrogen Electrode.

e-

0.763 V
e-

Porous Disk or
Salt Bridge

Zn(s)

a(Zn2+) = 1.00
Zn2+, SO42-

Anode

a (H+) = 1.00
Source of H+ (e.g.,
HCl (aq), H2SO4 (aq))
Cathode

H2 (g)

Pt gauze

The Cell Equation for the ZincStandard Hydrogen Electrode.

The cell reaction
2 H+ (aq) + Zn (s) H2 (g) + Zn2+ (aq)

Pt Zn (s) Zn2+ (aq),a=1 H+ (aq), a=1 H2 (g), f=1 Pt

When we measure the potential of this cell

Ecell = ERHS - ELHS
but ERHS = E(H+/H2) = 0.000 V
Ecell = E(Zn2+/Zn) = 0.763 V

The Spontaneous Direction of

a Cell Reaction

Examine the magnitude the of the

standard cell potential!

E cell

rxnG o

If the standard cell potential is positive, the

rG is negative!

The Composition Dependence of the

Cell Potential

Nonstandard cell potential (Ecell) will be

a function of the activities of the
species in the cell reaction.

E cell
To

RT
E
ln Qcell
F

calculate Ecell, we must know the cell

reaction and the value of Qcell.

Example

For the following system

Pt H2 (g) H+ (aq) Cu2+ (aq) Cu (s) Pt

Calculate

the value of the cell potential when

the f (H2) = 0.50, a(Cu2+) = 0.20, and a(H+) =
0.40.

Concentration Cells

Electrolyte concentration cell

the electrodes are identical; they simply

differ in the concentration of electrolyte in
the half-cells.

Concentration Cells (II)

Electrode concentration cells

the electrodes themselves have

different compositions. This may be
due to.
Different fugacities of gases involved in
electrode reactions (e.g., The H+ (aq)/H2
(g) electrode).
Different compositions of metal amalgams
in electrode materials.

Applications of Electrochemistry

Measurement of activities and activity

coefficients.

Electrochemical series.

Equilibrium constants and

thermodynamic functions of cell
reactions

Obtaining Standard Cell Potentials

Look at the following cell

Pt H2 (g) HCl (aq) AgCl (s) Ag (s) Pt

E cell E

cell

RT
a H a Cl

ln
F
f (H 2 )

Ecell = E(AgCl/Ag) - E (H+/H2)

= E(AgCl/Ag)

Ecell Values and Activity Coefficients

E cell

In dilute solution, using the DHLL

1
4.606 RT
2.344 RT

log m E ( AgCl Ag )
m 2
F
F

Plot LHS vs. m1/2

Once Ecell is known, we can obtain

experimental estimates of the mean activity
coefficients.

The Calculation of Standard Cell

Potentials
0.236
0.234
0.232
0.230
0.228

y = 0.0582x + 0.2222
R2 = 0.9836

0.226
0.224
0.222
0.220
0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Electrochemical Series

Look at the following series of reactions

Cu2+ (aq) + 2 e- Cu (s)

Zn2+ (aq) + 2 e- Zn (s)

Zn has a thermodynamic tendency to

reduce Cu2+ (aq)
Pb2+ (aq) + 2 e- Pb (s)
Fe2+ (aq) + 2 e- Fe (s)

E(Cu2+/Cu) = 0.337 V
E(Zn2+/Zn) = -0.763 V

E(Pb2+/Pb) = -0.13 V
E(-Fe2+/Fe) = -0.44 V

Fe has a thermodynamic tendency to

reduce Pb2+ (aq)

Thermodynamic Information

Note

FE r G
T ,P

And

FE r G

Entropy Changes

To obtain the entropy change for the

cell reaction

S
rxn S

T
T ,P

rxn S
rxnG
T

T ,P

T ,P

F E

T P

Enthalpy Changes

To obtain the enthalpy change for the cell reaction

H
rxn H

T ,P

T ,P
E
FE FT
T

rxn H FE

S
T

E
FT
T

T ,P

The Liquid Junction Potential

Examine the following electrochemical

cell
Activity difference of the HCl between
compartment 1 and compartment 2
There should be a transport of matter
from one cell compartment to the
other!

A Concentration Cell

e-

0.0592V
e-

Porous Disk or
Salt Bridge

Ag(s)

a(Cl-) = 0.010

Left

a (Cl -) = 0.0010

Right

Ag(s)

The Development of Liquid Junction

Potentials

The cell
compartments
are identical
except for the
activities of
the electrolyte
solutions.

HCl (a2)

HCl (a1)

Ag/AgCl electrode

Note that we
now have the
migration of both
cations and
anions through
the liquid
junction.

H+
Cl-

Ag/AgCl electrode

After a
period of
time

+++++
- - - - -----------

Ag/AgCl electrode

Choose the lower compartment as our

LHS electrode.
Ag AgCl

Cl- (aq) a1 Cl- (aq), a2 AgCl (s) Ag (s)

Note: liquid junction

For

the passage of one mole of charge

through the cell
-F Ecell = GJ

The Cell Reactions

For the LHS and RHS electrodes

AgCl (s) + e- Ag (s) + Cl- (a1) LHS
AgCl (s) + e- Ag (s) + Cl- (a2) RHS

Net change

Cl- (a1) Cl- (a2)

Note that the charge at the interface is

transported by the anions and cations
in the cell reaction!

The Transport Numbers

How is the charge carried at the interface

of the cells?
t+ moles of charge carried by the H+
(cation).
t- moles of charge carried by the Cl(anion).
Passage of one mole of + charge through
the interface

requires the passage of t+ moles of H+ (aq) from

the LHS RHS, and the passage of t- mole of Clcharge from the RHS LHS.

At the boundary
t+ H+(a1) + t- Cl-(a2) t+ H+(a2) + tCl-(a1)
For the entire cell
Cl- (a1) t+ H+(a1) + t- Cl-(a2) Cl- (a2)
t+ H+(a2) +
t- Cl-(a1)
The cell reaction involves the
transport of t+ moles of HCl from the
LHS to the RHs of the cell.

The Gibbs Energy Changes

For the above cell reaction, we can

write the Gibbs energy expressions as
follows

G t (H ) RT ln a (H )2 (Cl ) RT ln a (Cl )2

t (H ) RT ln a (H )1 (Cl ) RT ln a (Cl )1

a (H
t RT ln
a (H

)a (Cl ) 2

)a (Cl ) 1

Cells With Transference

Note a(H+) a (Cl-) = {a (HCl)}2

G 2 t RT

a (HCl ) 2
ln
a (HCl ) 1

Note that the cell potential with

transference, Ewt is determined as follows

E wt

RT a (HCl ) 2
2 t
ln
a (HCl )1
F

Cells without Transference

What if we were able to set up a cell so that

the transport at the interface did not
contribute to the overall G?
The potential of this cell would be the cell
potential without transference, Ewot.
Cl- (a1) Cl- (a2)

G RT
E wot

a (HCl ) 2
ln
a (HCl ) 1

a (HCl ) 2
RT

ln
a (HCl )1
F

The Liquid Junction Potential

The liquid junction potential is the

difference in the cell potentials with
and without transference!

E LJ E wt E wot
E LJ

a (HCl ) 2
RT
1 2 t
ln
a (HCl ) 1
F

L.J. Potentials Depend on

Transport Numbers

What is the following were true?

t+ t- 0.5 ELJ would be very small
and would only make a small
contribution to the overall cell
potential !

L.J. Potentials Depend on

Transport Numbers

ELJ a potential problem any time we

measure the cell potential whose
electrodes have different electrolytes
How does the salt bridge help?

e.g., for species with t+ t- 0.5, the ELJ

values are small and are readily
established!