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
difference
 G  work   E  q
Relation between
free energy, work
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 (W) - 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 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

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  0.777 V
 C  C
( 2 mol ) 9.649  10 4 
 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
 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 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 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:

Ecell  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

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 Where: E = actual ½ cell reduction potential
E  Eo  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)
b
0.05916 V [ B ] F = Faraday’s constant (9.649x104 C/mol)
 E  Eo  log A = activity of A or B
n [ A]a
 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  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

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
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!