Fundamentals of Electrochemistry

Introduction

1.) Electrical Measurements of Chemical Processes

 Redox Reaction involves transfer of electrons from one species to another.
- Chemicals are separated

 Can monitor redox reaction when electrons flow through an electric current
- Electric current is proportional to rate of reaction
- Cell voltage is proportional to free-energy change

 Batteries produce a direct current by converting chemical energy to electrical

energy.
- Common applications run the gamut from cars to ipods to laptops
 Fundamentals of Electrochemistry
Basic Concepts

1.) A Redox titration is an analytical technique based on the transfer of

electrons between analyte and titrant
 Reduction-oxidation reaction

 A substance is reduced when it gains electrons from another substance

- gain of e- net decrease in charge of species
- Oxidizing agent (oxidant)

 A substance is oxidized when it loses electrons to another substance

- loss of e- net increase in charge of species
- Reducing agent (reductant)

(Reduction)

(Oxidation)

Oxidizing Reducing
Agent Agent
 Fundamentals of Electrochemistry

Basic Concepts

2.) The first two reactions are known as “1/2 cell reactions”
 Include electrons in their equation
3.) The net reaction is known as the total cell reaction
 No free electrons in its equation

½ cell reactions:

Net Reaction:

4.) In order for a redox reaction to occur, both reduction of one compound
and oxidation of another must take place simultaneously
 Total number of electrons is constant
 Fundamentals of Electrochemistry

Basic Concepts

5.) Electric Charge (q)

 Measured in coulombs (C)
 Charge of a single electron is 1.602x10-19C
 Faraday constant (F) – 9.649x104C is the charge of a mole of
electrons

Relation between
charge and moles: q  nF
Coulombs
Coulombs moles
mol e 

6.) Electric current

 Quantity of charge flowing each second
through a circuit
- Ampere: unit of current (C/sec)
 Fundamentals of Electrochemistry

Basic Concepts

7.) Electric Potential (E)

 Measured in volts (V)
 Work (energy) needed when moving an electric
charge from one point to another
- Measure of force pushing on electrons
Higher potential
Relation between
difference
free energy, work G  work  E  q
and voltage:
Joules Volts Coulombs

Higher potential difference requires

more work to lift water (electrons) to
higher trough
 Fundamentals of Electrochemistry

Basic Concepts

7.) Electric Potential (E)

 Combining definition of electrical charge and potential

G  work   E  q q  nF

Relation between free energy

difference and electric potential
difference:
G   nFE

Describes the voltage that can be generated by a chemical reaction

 Fundamentals of Electrochemistry

Basic Concepts

8.) Ohm’s Law

 Current (I) is directly proportional to the potential difference (voltage)
across a circuit and inversely proportional to the resistance (R)
- Ohms () - units of resistance

E
I
R

9.) Power (P)

 Work done per unit time
- Units: joules per second J/sec or watts (W)

q
P E  EI
s
 Fundamentals of Electrochemistry

Galvanic Cells

1.) Galvanic or Voltaic cell

 Spontaneous chemical reaction to generate electricity
- One reagent oxidized the other reduced
- two reagents cannot be in contact
 Electrons flow from reducing agent to oxidizing agent
- Flow through external circuit to go from one reagent to the other

Reduction:
Oxidation:

Net Reaction:

AgCl(s)
Cd(s)isisreduced
Electrons oxidized toto
travel from Ag(s)
Cd
Cd2+
Ag deposited onto
Cd2+ goes
electrode electrode
into and Cl-
Ag solution
electrode
goes into solution
 Fundamentals of Electrochemistry

Galvanic Cells

1.) Galvanic or Voltaic cell

 Example: Calculate the voltage for the following chemical reaction

G = -150kJ/mol of Cd

Solution: n – number of moles of electrons

G
G   nFE  E  
nF

 150  10 3 J
E  0.777 J  0.777V
 4 C 
C
( 2 mol ) 9.649  10 
 mol 
 Fundamentals of Electrochemistry

Galvanic Cells

2.) Cell Potentials vs. G

 Reaction is spontaneous if it does not require external energy
 Fundamentals of Electrochemistry

Galvanic Cells

2.) Cell Potentials vs. G

 Reaction is spontaneous if it does not require external energy

Potential of overall cell = measure of the tendency of this reaction to proceed to

equilibrium
ˆ Larger the potential, the further the reaction is from equilibrium
and the greater the driving force that exists

Similar in concept to balls

sitting at different heights
along a hill
 Fundamentals of Electrochemistry

Galvanic Cells

3.) Electrodes

Anode: electrode Cathode: electrode

where oxidation takes where reduction takes
place place
 Fundamentals of Electrochemistry

Galvanic Cells

4.) Salt Bridge

 Connects & separates two half-cell reactions
 Prevents charge build-up and allows counter-ion migration

Salt Bridge
 Contains electrolytes not
involved in redox reaction.

TwoCd
 K+ (and half-cell
2+ reactions
) moves to cathode with
e through salt bridge (counter
-

balances –charge build-up

 NO3- moves to anode (counter

balances +charge build-up)

 Completes circuit
 Fundamentals of Electrochemistry

Galvanic Cells

5.) Short-Hand Notation

 Representation of Cells: by convention start with anode on left

Phase boundary
Electrode/solution interface

anode Zn|ZnSO4(aZN2+ = 0.0100)||CuSO4(aCu2+ = 0.0100)|Cu cathode

2 liquid junctions
Solution in contact with due to salt bridge Solution in contact with
anode & its concentration cathode & its concentration
 Fundamentals of Electrochemistry

Standard Potentials

1.) Predict voltage observed when two half-cells are connected

 Standard reduction potential (Eo) the measured potential of a half-cell
reduction reaction relative to a standard oxidation reaction
- Potential arbitrary set to 0 for standard electrode
- Potential of cell = Potential of ½ reaction

Ag+ + e-  Ag(s) Eo = +0.799V

 Potentials measured at standard conditions
- All concentrations (or activities) = 1M
- 25oC, 1 atm pressure

Standard Hydrogen Electrode (S.H.E)

Pt(s)|H2(g)(aH = 1)|H+(aq)(aH+ = 1)||

2

Hydrogen gas is bubbled over a Pt electrode

 Fundamentals of Electrochemistry

Standard Potentials

1.) Predict voltage observed when two half-cells are connected

As Eo increases, the more

favorable the reaction and the
more easily the compound is
reduced (better oxidizing
agent).

Reactions always written as

reduction

Appendix H contains a more extensive list

 Fundamentals of Electrochemistry
Standard Potentials

2.) When combining two ½ cell reaction together to get a complete net
reaction, the total cell potential (Ecell) is given by:

E cell  E   E 
Where: E+ = the reduction potential for the ½ cell reaction at the positive electrode
E+ = electrode where reduction occurs (cathode)
E- = the reduction potential for the ½ cell reaction at the negative electrode
E- = electrode where oxidation occurs (anode)

Place values on number line to

Electrons always flow towards determine the potential difference
more positive potential
 Fundamentals of Electrochemistry

Standard Potentials

3.) Example: Calculate Eo, and Go for the following reaction:
 Fundamentals of Electrochemistry

Nernst Equation

1.) Reduction Potential under Non-standard Conditions

 E determined using Nernst Equation
 Concentrations not-equal to 1M

For the given reaction:

aA + ne-  bB Eo

The ½ cell reduction potential is given by:

b
RT A
E  Eo 
Where: E = actual ½ cell reduction potential
ln B Eo = standard ½ cell reduction potential
nF AA a n = number of electrons in reaction
T = temperature (K)
at 25oC R = ideal gas law constant (8.314J/(K-mol)
0.05916 V
o [ B ]b F = Faraday’s constant (9.649x104 C/mol)
EE  log A = activity of A or B
n [ A]a
 Fundamentals of Electrochemistry

Nernst Equation

2.) Example:
 Calculate the cell voltage if the concentration of NaF and KCl were each
0.10 M in the following cell:

Pb(s) | PbF2(s) | F- (aq) || Cl- (aq) | AgCl(s) | Ag(s)

 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is

NOT at Equilibrium
 Concentration in two cells change with current
 Concentration will continue to change until Equilibrium is reached
- E = 0V at equilibrium
- Battery is “dead”
Consider the following ½ cell reactions:
aA + ne-  cC E+ o
dD + ne-  bB E- o
Cell potential in terms of Nernst Equation is:

0.05916 [ C ] c  o 0.05916 [ B ]b 

E cell  E   E   E o  log  E  log
n [ A] a  n [ D ] d 
 
Simplify:
0.05916 [C ]c [ D ]d
E cell  ( E o  E o ) log
n [ A]a [ B ]b
 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

1.) A Galvanic Cell Produces Electricity because the Cell Reaction is

NOT at Equilibrium

Since Eo=E+o- E-o:

o 0.05916 [C ]c [ D ]d
E cell  E  log
n [ A]a [ B ]b

At equilibrium Ecell =0:

Definition of
equilibrium constant

0.05916
Eo  log K at 25oC
n

nE o
0.05916 at 25oC
K  10
 Fundamentals of Electrochemistry

Eo and the Equilibrium Constant

2.) Example:
 Calculate the equilibrium constant (K) for the following reaction:
 Fundamentals of Electrochemistry

Cells as Chemical Probes

1.) Two Types of Equilibrium in Galvanic Cells

 Equilibrium between the two half-cells
 Equilibrium within each half-cell

If a Galvanic Cell has a nonzero voltage then

the net cell reaction is not at equilibrium

Conversely, a chemical reaction within a ½

cell will reach and remain at equilibrium.

For a potential to exist, electrons

must flow from one cell to the
other which requires the reaction
to proceed  not at equilibrium.
 Fundamentals of Electrochemistry

Cells as Chemical Probes

2.) Example:
 If the voltage for the following cell is 0.512V, find Ksp for Cu(IO3)2:

Ni(s)|NiSO4(0.0025M)||KIO3(0.10 M)|Cu(IO3)2(s)|Cu(s)
 Fundamentals of Electrochemistry
Biochemists Use Eo´

1.) Redox Potentials Containing Acids or Bases are pH Dependent

 Standard potential  all concentrations = 1 M
 pH=0 for [H+] = 1M

2.) pH Inside of a Plant or Animal Cell is ~ 7

 Standard potentials at pH =0 not appropriate for biological systems
- Reduction or oxidation strength may be reversed at pH 0 compared to pH 7

Metabolic Pathways
 Fundamentals of Electrochemistry
Biochemists Use Eo´
Eo´ (V)
3.) Formal Potential
 Reduction potential that applies
under a specified set of
conditions

 Formal potential at pH 7 is Eo´

o 0.05916 [C ]c [ D ]d
E cell  E  log
n [ A]a [ B ]b

Need to express concentrations as

function of Ka and [H+].

Cannot use formal concentrations!