Unit 1

Electrochemical
Energy
Chemistry for Engineers
Objectives:

▪ Define electrochemistry;
▪ Discuss basic concepts in
electrochemistry;
▪ Analyze the process of redox
reactions in electrochemistry; and
▪ Solve some problems involving
electrochemistry.
Electrochemistry
The relationship
between chemical
reactions and
electricity.
•Certain chemical reactions can
create electricity.
•Electricity can make certain
chemical reactions happen that
wouldn’t happen otherwise.
Electrochemistry
The relationship between chemical reactions and
electricity.

Certain chemical reactions can create electricity.

e- wire
A B A e- B
Electrochemistry

Oxidation Reduction
Movement of electrons Reactions
- - - - - - -
e -e -e -e -e -e -e
Electrochemistry
Certain chemical reactions can create electricity.

Image Credit: https://en.wikipedia.org/wiki/Galvanic_cell

Electrochemistry
Electricity can make certain chemical reactions
happen that wouldn’t happen otherwise.
Electrochemistry
Electricity can make certain chemical reactions
happen that wouldn’t happen otherwise.
Electrochemical Cells
An electrochemical cell is a system consisting of
electrodes that dip into an electrolyte in which a
chemical reaction either uses or generates an
electric current.
– A voltaic, or galvanic, cell is an electrochemical cell in which
a spontaneous reaction generates an electric current (+V, rxn
occurs on own).
– An electrolytic cell is an electrochemical cell in which an
electric current drives an otherwise nonspontaneous
reaction (-V, rxn does not occur on own, need outside
source).
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
Electrical Measurements of Chemical Processes
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)
Electrical Measurements of Chemical Processes

The first two reactions are known as “1/2 cell reactions”

Include electrons in their equation
Electrical Measurements of Chemical Processes

The net reaction is known as the total cell reaction

No free electrons in its equation

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
Electrical 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
Electrical Current

Quantity of charge flowing each second

through a circuit
- Ampere: unit of current
Electrical 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

Higher potential difference

requires more work to lift
water (electrons) to higher
trough
Electrical Potential (E)
Combining definition of electrical charge and potential

Describes the voltage that can be generated by a

chemical reaction
Ohm’s Law

Current (I) is directly proportional to the potential

difference (voltage) across a circuit and inversely
proportional to the resistance (R)
- Ohms (Ω) - units of resistance

Power (P)
Work done per unit time
- Units: joules per second J/sec or watts (W)
Sample Problem

How many electrons per

second pass through a cross
section of copper wire
carrying 10-16A?
Sample Problem

A galvanic cell was operated

under almost identically
reversible conditions of 10-16A.
(a) At this current, how long
would it take to deliver 1 mole
electrons? (b) How many
electrons would be delivered by
the cell to a pulsed measuring
circuit in 10ms of operation?
Sample Problem

From the definition of a faraday, calculate

the charge on one electron.
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 travel to
oxidized toAg(s)
from Cd 2+
Cd-
Ag deposited onto
Cd2+ goes
electrode electrode
into and Cl
Ag solution
electrode
goes into solution
Galvanic Cells
1.) Galvanic or Voltaic cell
Example: Calculate the voltage for the following chemical
reaction

ΔG = -150kJ/mol of Cd

Solution: n – number of moles of electrons

Galvanic Cells
Galvanic Cells
Galvanic Cells
Sample Problem
A platinum rod is immersed in an aqueous solution of sodium
iodide containing solid iodine crystals, the salt bridge cell on the
other side has a sodium bromide producing bromine liquid in
the process.
For this cell,
a. Draw a sketch of the cell, labeling the anode, the cathode,
and the direction of the electron flow.
b. Write the half-cell reaction that takes place at the anode and
at the cathode.
c. Write a balanced equation for the cell reaction.
d. Write an abbreviated notation for the cell.
Solution
QUIZ
When chlorine gas is bubbled through an aqueous solution of
NaBr, chloride ions and liquid bromine are the products of the
spontaneous reaction.
For this cell,
a. Draw a sketch of the cell, labeling the anode, the cathode,
and the direction of the electron flow.
b. Write the half-cell reaction that takes place at the anode and
at the cathode.
c. Write a balanced equation for the cell reaction.
d. Write an abbreviated notation for the cell.
Galvanic Cells

2.) Cell Potentials vs. ΔG

Reaction is spontaneous if it does not require external
energy
Galvanic Cells

2.) Cell Potentials vs. ΔG

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
Galvanic Cells

3.) Electrodes
Reaction is spontaneous if it does not require external
energy

Anode: electrode Cathode: electrode

where oxidation takes where reduction takes
place place
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.

Two Cd
▪ 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
Galvanic Cells

5.) Salt Bridge

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
Cell Potential
•The potential difference between the
anode and cathode in a cell (Ecell).
•It is the measure of the driving force of the
redox reactions.
•Cell potential is measured in Volts (V).
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)(aH2 = 1)|H+(aq)(aH+ = 1)||

Hydrogen gas is bubbled over a Pt electrode
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

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

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
Standard Potentials

Determine the Net Cell Potential and the Free energy change.

Using standard potentials,

decide whether at standard
concentrations the reaction
Standard Potentials

Using standard potentials,

decide whether at standard
concentrations the reaction
Sample Problem
3.) Calculate Eo, and ΔGo for the following reaction:
Sample Problem
3.) Calculate Eo, and ΔGo for the following reaction:
Sample Problem
3.) Calculate Eo, and ΔGo for the following reaction:
Thermochemistry and Electrochemistry

∆G = -nFE
If the standard cell potential at 298K is
1.10V for the following reaction
2+ 2+
Zn(s) + Cu (aq) 🡪 Zn (aq) + Cu (s),
then what is the change of Gibbs free
energy change?
Thermochemistry and Electrochemistry
0
∆G = -RTlnK
The equilibrium constant for the
19
reaction below is 1.8 x 10 at 298K.
What is the value of the standard cell
potential for this reaction?
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:

Where: E = actual ½ cell reduction potential

Eo = standard ½ cell reduction potential
n = number of electrons in reaction
T = temperature (K)
at 25oC R = ideal gas law constant (8.314J/(K-mol)
F = Faraday’s constant (9.649x104 C/mol)
A = activity of A or B
Nernst Equation
Nernst Equation
Nernst Equation
Sample Problem
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)

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:

Simplify:
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:

At equilibrium Ecell =0:

Definition of
equilibrium constant

at 25oC

at 25oC
Sample Problem
Calculate the equilibrium constant (K) for the following
reaction:
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.
Sample Problem
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)
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 of Coil in Construction Site

Standard potentials at pH =0 not appropriate for these
processes
- Reduction or oxidation strength may be reversed at pH 0
compared to pH 7
- unintended electrochemical reactions as reinforcement
corrosion and the intended reactions driving
electro-desalination of construction materials.
Use Eo´
Eo´ (V)
Biochemists Use Eo´

3.) Formal Potential

Reduction potential that applies under a specified
set of conditions

Formal potential at pH 7 is Eo´

Need to express concentrations as

function of Ka and [H+].

Cannot use formal concentrations!