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

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 nF
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

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 totoAg(s)
travel from CdCd2+
Ag deposited onto
Cd2+ goes
electrode electrode
into and Cl-
Ag solution
electrode
goes into solution
 Fundamentals of Electrochemistry

Galvanic Cells

2.) Cell Potentials

Reaction is spontaneous if it does not require external energy

Reaction Type E Cell Type

Spontaneous + Galvanic
Nonspontaneous - Electrolytic
Equilibrium 0 Dead battery

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

equilibrium
Larger the potential, the further the reaction is from equilibrium
and the greater the driving force that exists
 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 reactions
2+) 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 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 cell reaction together to get a complete net
reaction, the total cell potential (Ecell) is given by:

Ecell E E
Where: E+ = the reduction potential for the cell reaction at the positive electrode
E+ = electrode where reduction occurs (cathode)
E- = the reduction potential for the 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 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 cell reduction potential is given by:

b
RT A Where: E = actual cell reduction potential
E Eo ln B Eo = standard 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)
b
0.05916 V [ B ] F = Faradays constant (9.649x104 C/mol)
E Eo 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 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 n d
[ A] [ 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
at 25oC
K 10 0.05916
 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

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!