Electrochemistry

ELECTROCHEMISTRY

▸ Electrochemistry is the branch of chemistry that deals with

electricity-related applications of oxidation-reduction
reactions

▸ These reactions usually take place in an electrochemical

cell.

▸ There are two types of electrochemical cells: Voltaic (also

known as galvanic) and Electrolytic
TERMINOLOGY

❖ Oxidation – A process in which an element attains a more

positive oxidation state
Na(s) —> Na+ + e-

❖ Reduction – A process in which an element attains a more

negative oxidation state
Cl2 + 2e- —> 2Cl-

❑ Oxidizing agent
The substance that is reduced is the oxidizing agent
❑ Reducing agent
The substance that is oxidized is the reducing agent
An old memory device for oxidation and
reduction goes like this…

LEO says GER

Lose Electrons = Oxidation

Gain Electrons = Reduction

OIL RIG
Oxidation is loss; Reduction is gain
● A voltaic cell is an electrochemical cell where a redox
reaction occurs naturally and produces electrical energy

● An electrolytic cell is an
electrochemical cell where a redox
reaction requires electric energy to
occur
So what is the difference between
the cells?
SO WHAT IS THE SAME ABOUT THESE CELLS?

● Both cells have electrodes

▸ An electrode is a conductor in a circuit that
carries electrons

▸ The electrode where reduction occurs is

the CATHODE

▸ The electrode where oxidation occurs is

the ANODE
Synopsis of Assigning Oxidation Numbers
(as a Reminder)
• Elements = 0
• Monatomic ion = charge
• F: –1
• O: –2 (unless peroxide = –1)
• H: +1 (unless a metal hydride = –1)
• The sum of the oxidation numbers equals
the overall charge (0 in a compound).

Electrochemistry

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 Oxidation Numbers
• To keep track of what
loses electrons and
what gains them, we
assign oxidation
numbers.
• If the oxidation number
increases for an
element, that element
is oxidized.
• If the oxidation number
decreases for an
element, that element
is reduced. Electrochemistry

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 Oxidation and Reduction
• A species is oxidized when it loses electrons.
– Zinc loses two electrons, forming the Zn2+ ion.
• A species is reduced when it gains electrons.
– H+ gains an electron, forming H2.
• An oxidizing agent (H+) causes something else to be
oxidized; a reducing agent (Zn) causes something else
to be reduced.

Electrochemistry

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 Half-Reactions

• The oxidation and reduction are written

and balanced separately.
• We will use them to balance a redox
reaction.
• For example, when Sn2+ and Fe3+ react,

Electrochemistry

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 Balancing Redox Equations: The
Half-Reactions Method (a Synopsis)
• Make two half-reactions (oxidation
and reduction).
• Balance atoms other than O and H.
Then, balance O and H using H2O/H+.
• Add electrons to balance charges.
• Multiply by common factor
to make electrons in half-reactions
equal.
• Add the half-reactions.
• Simplify by dividing by common factor
or converting H+ to OH–
if basic.
• Double-check atoms and charges
balance!
Electrochemistry

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 The Half-Reaction Method

• Consider the reaction between MnO4– and C2O42–:

MnO4–(aq) + C2O42–(aq) Mn2+(aq) + CO2(aq)
• Assigning oxidation numbers shows that Mn is reduced
(+7 +2) and C is oxidized (+3 +4).
Electrochemistry

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 Oxidation Half-Reaction

C2O42– CO2

To balance the carbon, we add a coefficient

of 2:

C2O42– 2 CO2

Electrochemistry

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 Oxidation Half-Reaction

C2O42– 2 CO2

The oxygen is now balanced as well.

To balance the charge, we must add
two electrons to the right side:

C2O42– 2 CO2 + 2e–

Electrochemistry

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 Reduction Half-Reaction

MnO4– Mn2+

The manganese is balanced; to balance

the oxygen, we must add four waters to the
right side:

MnO4– Mn2+ + 4 H2O

Electrochemistry

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 Reduction Half-Reaction

MnO4– Mn2+ + 4 H2O

To balance the hydrogen, we add

8H+ to the left side:

8 H+ + MnO4– Mn2+ + 4 H2O

Electrochemistry

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 Reduction Half-Reaction

8 H+ + MnO4– Mn2+ + 4 H2O

To balance the charge, we add 5e– to the

left side:

5e– + 8 H+ + MnO4– Mn2+ + 4 H2O

Electrochemistry

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 Combining the Half-Reactions

Now we combine the two half-reactions

together:

C2O42– 2 CO2 + 2e–

5e– + 8 H+ + MnO4– Mn2+ + 4 H2O

To make the number of electrons equal on

each side, we will multiply the first reaction
by 5 and the second by 2 to give the least
common multiple: Electrochemistry

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 Combining the Half-Reactions

5 C2O42– 10 CO2 + 10e–

10e– + 16 H+ + 2 MnO4– 2 Mn2+ + 8 H2O

When we add these together, we get

10e– + 16 H+ + 2 MnO4– + 5 C2O42–

2 Mn2+ + 8 H2O + 10 CO2 +10e–

Electrochemistry

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 Combining the Half-Reactions
10e– + 16 H+ + 2 MnO4– + 5 C2O42–
2 Mn2+ + 8 H2O + 10 CO2 +10e–

The only thing that appears on both sides is the

electrons. Subtracting them, we are left with

16 H+ + 2 MnO4– + 5 C2O42–
2 Mn2+ + 8 H2O + 10 CO2
(Verify that the equation is balanced by counting atoms
and charges on each side of the equation.) Electrochemistry

© 2018 Pearson Education, Inc.

VOLTAIC CELL
LETS LOOK AT EACH CELL MORE SPECIFICALLY

● Voltaic cells
▸ These cells occur naturally or spontaneously.
▸ Spontaneous redox processes have:
A positive cell potential, E0

A negative free energy change, (-ΔG)

▸ We will look at potentials to determine

when a reaction is spontaneous.
Standard Reduction Potentials in Water at 25 oC

Measured against the

Standard Hydrogen
Electrode
VOLTAIC CELL
Let’s look at the reaction between zinc and copper.

● Zinc and copper are electrodes

● The zinc is in a solution of ZnSO4

● The copper is in a solution of CuSO4

Zn(s) → Zn2+(aq) + 2e-

Cu2+(aq) + 2e- → Cu(s)

The less positive (or more

negative) reduction potential
becomes the oxidation…
Voltaic cell
Zn(s) → Zn2+(aq) + 2e- Oxidation

Cu2+(aq) + 2e- → Cu(s) Reduction

● Let’s identify
● Which reaction is oxidation?
● Which reaction is reduction?
● The anode?
● The cathode?
 Voltaic Cell

e- e- Copper
Zinc
Oxidation Reduction
Anode Cathode
SO42- Salt Bridge
+
l

SO42-
Let’s look a little closer at what is
really happening
Let’s look a little closer at
what is really happening
VOLTAIC CELL

● The following represents the zinc-copper voltaic by the

following shorthand…

Zn(s)│ZnSO4(aq) ║CuSO4(aq)│Cu(s)

ANODE ║ CATHODE

Anode Cathode
| Anode || Cathode
|
material solution solution material
ELECTROLYTIC
CELL
ELECTROLYTIC CELL

● Let’s look at the reaction between iron and

silver.

● Iron and silver are electrodes

● The electrodes are in a solution of Fe(NO3)3
Fe3+(aq) + 3e- → Fe(s)

3Ag(s) → 3Ag+(aq) + 3e-

ELECTROLYTIC CELL

Fe3+(aq) + 3e- → Fe(s) Reduction

3Ag(s) → 3Ag+(aq) + 3e- Oxidation

● Let’s identify
▸ Which reaction is oxidation?
▸ Which reaction is reduction?
▸ The anode?
▸ The cathode?
ELECTROLYTIC CELL

Silver e- Iron
Oxidation e- Reduction
Anode Cathode
+

l
If we wanted to
iron plate something
we could use that
as our electrode

NO3-
Fe3+
LETS LOOK AT EACH CELL MORE SPECIFICALLY

● Electrolytic cells
▸ These cells do not occur naturally or
spontaneously.

▸ Non-spontaneous redox processes have:

A negative cell potential, -E0
A positive free energy change, (+ΔG)

▸ We will look at potentials to determine when a

reaction is spontaneous or not.
TEXT

NO HUMAN RESEARCH CAN BE

CALLED TRUE SCIENCE UNLESS IT CAN
BE MATHEMATICALLY PROVED.

Leonardo da Vinci
YAY!
MATHEMATICS!
 Zn - Cu
Galvanic Cell

From a table
of reduction
potentials:

Zn2+ + 2e-  Zn E = -0.76V

Cu2+ + 2e-  Cu E = +0.34V
Standard Reduction Potentials in Water at 25 oC

Measured against the

Standard Hydrogen
Electrode
 Zn - Cu
Galvanic Cell
The less positive, or
more negative
reduction potential
becomes the
oxidation…
Zn  Zn2+ + 2e- E = +0.76V
Cu2+ + 2e-  Cu E =+0.34V

Zn + Cu2+  Zn2+ + Cu E0 = +1.10 V

 CALCULATING ΔG FOR A CELL
0

ΔG0 = -nFE0
n = moles of electrons in balanced redox equation
F = Faraday constant = 96,485 coulombs/mol e-

Zn + Cu2+  Zn2+ + Cu E0 = + 1.10 V

0 coulombs Joules
ΔG = − (2 mol e )(96 485
−
)(1.10 )
mol e −
Coulomb
0
ΔG = − 212267 Joules = − 212 kJ
 The Nernst Equation
Standard potentials assume a concentration of 1 M.
The Nernst equation allows us to calculate potential
when the two cells are not 1.0 M.

RT 0
E=E − ln(Q)
nF
R = 8.31 J/(mol⋅K)
T = Temperature in K
n = moles of electrons in balanced redox equation

F = Faraday constant = 96,485 coulombs/mol e-

“There’s as many atoms in a single
molecule of your DNA as there are stars
in the typical galaxy. We are, each of us,
a little universe.”

― Neil deGrasse Tyson; Cosmos