Fundamentals of

Electrochemistry
It’s shocking!
Electroanalytical Chemistry: group of analytical methods
based upon electrical properties of analytes when part of
an electrochemical cell

Potentiometry involves the measurement of

potential for quantitative analysis.

Electrolytic electrochemical phenomena involve

the application of a potential or current to drive a
chemical phenomenon, resulting in some
measurable signal which may be used in an
analytical determination
If you think about it!......

• The majority of chemical reactions can be classified

as one of two kind of major reaction types.

• Acid/Base Reactions: proton transfer

• Oxidation/Reduction (Redox) Reactions : electron

transfer
 Basic Concepts
Redox reactions involve a species which is
oxidized and another that is reduced.

Fe 3  V 2  Fe 2  V 3

In the above, Fe3+ is reduced to Fe2+ .

It is the oxidizing agent.

Since DG<0 for this reaction we can say that

V3+ wants the extra electron less than Fe3+.

V 3  Fe 3
 2 2 Galvanic Cell
Cd  2Ag
 An Aside
Why won’t this cell work?

Ag+ will go to left

electrode and ask for
e from Cd(s) directly.
Will this cell work?
How badly do the electrons want to flow?

q
 I  E/R
sec

I = current in amps
R = resistance in ohms
E = potential difference
q = n x F in Volts

Coulombs  Moles 
Coulomb
DG  -nFE
Moles
 Voltaic Cells
Electrochemical cells that use an oxidation-
reduction reaction to generate an electric current
are known as galvanic or voltaic cells.
Voltaic Cells
 The voltaic cell consist of the two reactions.
Zn(s)  Zn 2  2e  oxidation

+ 2H  2e -
 H (g)
2
reduction
2H   Zn(s)  Zn 2  H 2 (g)
Or equivalently we can write the reactions as follows
2H   2e-  H 2 (g)
Zn 2  2e  Zn(s)

2H   Zn(s)  Zn 2  H 2 (g)
We can only measure E for the full reaction.
We would like to calculate E for the half reactions.
Before doing this, we must recognize the E depends on
concentrations.
Voltaic Cells

 Zn 2   1
H  1
 H2 ( g )  1
Since reactants and products are in their standard states, we
call the E for this cell the standard reduction potential (Eo).
Here Eo = .76V.

2 
Zn(s)  Zn  2e
+ 2H   2e-  H 2 (g)

2H   Zn(s)  Zn 2  H 2 (g)
We arbitrarily define the potential for, one half reaction, the
second reaction above to be exactly 0V when reactants and
products are in their standard states.

Since Eo for the cell is the sum of Eo’s for the two half reactions
we see that Eo for the first half reaction is .76V.
Oxidizing Power
Increases
Voltaic Cells

 Zn 2   1
H  1
 H2 ( g )  1
 Zn(s)  Zn 2  2e 

+ 2H  2e  H 2 (g)
-

 2
2H  Zn(s)  Zn  H 2 (g)

This voltaic cell on the previous slide is fully described

with
the following notation
Zn(s) | Zn 2 (aq, Α  1) || H  (aq, Α  1) | H 2 (g, Α  1) | Pt(s)

Zn(s) | Zn 2 (aq, Α  1) || S.H.E.

 Line Notation For Voltaic Cells

Voltaic cells can be described by a line notation based on the

following conventions.
Single vertical line indicates change in state or phase.
Within a half-cell, the reactants are listed before the
products.
Activities of aqueous solns are written in parentheses after
the symbol for the ion or molecule.
A double vertical line indicates a junction between half-
cells.
The line notation for the anode (oxidation) is written before
the line notation for the cathode (reduction).
Electrons flow from the anode to the cathode in a voltaic cell.
(They flow from the electrode at which they are given off to the
electrode at which they are consumed.) Reading from left to
right, this line notation therefore corresponds to the direction in
which electrons flow.

Zn | Zn2+(1.0 M) || Cu2+(1.0 M) | Cu
anode cathode
(oxidation) (reduction)
 The Nernst Equation
The Nernst equation relates the potential of a cell in its
standard state to that of a cell not in its standard state.
.
Zn 2  2e   Zn(s) 2Zn 2 
 4e  2 Zn(s)
We know from Le Chatelier’s principle that increasing the
concentration of Zn2+ should drive the reaction to the right. In
other words it should decrease the potential of the half cell.
The Nernst equation allows us to calculate this increase for
the above half reaction as

RT  Zn(s) RT 
2

EE  o
ln EE  lno Zn(s)

2F  Zn 2 4F  2
Zn 2
 
The Nernst Eq. for the reaction bB  ne  cC is

RT  c
EE  o
ln C

nF  b
B

At 25oC this equation

simplifies to

.05916V  c
EE  o
log C

n  b
B
 The Nernst Equation For Complete Cell
E  E  E
Here E+ and E- are the potentials of the half
cells connected to the positive and negative
terminals of potentiometer respectively. Let’s
consider an example.
 Voltaic Cells
- +
 Zn 2   1
H  1
 H2 ( g )  1

Taken from http://chemed.chem.purdue.edu/genchem

 E  E  E
E+ and E- are potentials of half cells connected to positive and
negative terminals of potentiometer respectively
2H   2e-  H 2 (g)
Zn 2  2e  Zn(s)
 2
2H  Zn(s)  Zn  H 2 (g)

 .05916V H2 ( g )   .05916V  Zn(s) 

E   log  -  - .76  log 
 2  2   2  
 H 
  Zn 2

.05916  H 2 ( g )  Zn 2
E  .76  log
2  2H 
 Calculating Equilibrium Constants
Ce4  Fe2  Ce3  Fe3
made up of the following two half reactions

Ce4  e   Ce3 Eo=1.700V

3  2
Fe  e  Fe Eo=0.767V

Since Eo is greater for cerium this reaction will be the reduction

reaction. The standard potential for the galvanic cell would be

E  E - E  1.700 - (0.767)
o o

o

 Calculating Equilibrium Constants
Continued
Ce4  Fe2  Ce3  Fe3
In a galvanic cell we would have
3 3
RT [Fe ][Ce ]
E  E  - E-  E  - E  -
0 0
ln
nF [Fe 2 ][Ce 4 ]
At equilibrium E=0 and
3 3
RT [Fe ][Ce ]
E - E 
o o
ln 2 4
 .05916  log K at 25o
C
F [Fe ][Ce ]
K  1016

 DG o
E o - E o  This connection to free
nF energy is important
 Calculating Equilibrium Constants for
Nonredox Reactions
FeCO3 ( s)  Fe2  CO32-
This is a Ksp problem. Not a redox problem. Nonetheless we
can use electrochemistry to calculate Ksp by considering

FeCO3 ( s)  2e  Fe(s)  CO 2-
3 E  0.756V
o


Fe 2  2e   Fe(s) E o  0.44V

E -E 
o

o

.059
2
 2
log [Fe ][CO 3 ] 
2-

.059
2
log K sp
2- .316  2.316/ .059 11
 log K sp Ksp  10  10
.059
(at 25oC)
 Electrochemistry Skills
• Understand how voltaic cells work.
• Be able to calculate standard reduction potentials for
voltaic cells, given the chemical reactions.
• Be able to describe a voltaic cell using the line notation
and visa versa. Know which way electrons flow and
where the anode and cathode are.
• Know how to work with the Nernst Eq. to include
concentration dependencies and calculate equilibirum
constants