Electrochemistry

Electrochemistry is a branch of chemistry that

deals with the flow of electric current (the
transfer of electrons) from one chemical
species to another.
 There are two main branches of electrochemistry, both utilizing redox reactions:

1st branch: The generation of electricity through the use of a spontaneous redox chemical reaction.
(SOA
SRA )

Here chemical energy from the redox reaction is converted into electrical energy. This process uses an electrochemical cell (also
called Galvanic Cells or Voltaic Cells).
Examples: batteries for flashlights, car batteries
2nd branch: The use of electricity to drive an
otherwise non-spontaneous redox reaction.

SRA
SOA

This process uses an external power supply for

the construction of an electrolytic cell.
Examples: charging a battery, silver plating a metal, (bronzing baby shoes) electrolysis
of water

Both of these branches of electrochemistry

involve a flow of electrons → redox
reactions.
 20.3: Voltaic Cells
(Electrochemical or Galvanic Cells)

An electrochemical cell is the experimental

apparatus for generating electricity through the use
of a spontaneous redox reaction.

A battery is usually two or more electrochemical

cells connected to each other.
 To Construct an Electrochemical
Cell you need:

1. The chemicals that would cause a spontaneous

redox reaction, in two separate containers.

The chemicals for the oxidation are in one

container and those for the reduction are in
another.

These are referred to as half-cells, each

containing a half-reaction.
 The chemicals involved include:
a) Electrodes connected with a wire.
Electrodes are:

• part of the external circuit that allows for the

electrons to transfer between the two half-cells.
(Electrons always only go through the wire).

•a solid strip of a conductor (any metal or

carbon). If a metal is used, is must be made of
the same substance as the ions found within the
solution (so a chemical reaction is avoided).
• referred to as the anode (where oxidation
occurs) or the cathode (where reduction occurs).

Electrodes: a solid strip of a conductor

Cu Zn Mg Al C
 wire connecting
electrodes

electrodes

2 beakers: half-cells
b) Electrolytes: Each half-cell requires a conducting
solution (part of the internal circuit) which allows ions to
flow. (Examples include: Cu(NO3)2, Al(NO3)3, ZnSO4 ....)
These substances will break apart into ions in solution
(e.g. Cu(NO3)2 becomes Cu2+ and NO3-).

The solution should match the electrode, unless a

carbon rod is used (it is inert). We don’t want a reaction
to occur between an electrode and solution within the
same beaker.

If a Cu(s) electrode is used, then Cu(NO3)2 is the solution.

If a Ag(s) electrode is used, then AgNO3 is the solution.
 + and - ions + and - ions

2 different electrolytes (an ionic conducting solution)

in each beaker. The solution matches the electrode.
Recall: An ionic solution will dissociate into a cation and an ion
in water. (e.g. Cu(NO3)2 → Cu2+ + NO3-)
2. Porous Cup or Salt Bridge:

Only one of these is needed to make an

electrochemical cell.

They each serve to separate the chemicals

involved in the oxidation from those in the
reduction and to allow ions to flow in order to
prevent polarization (a build up of charge)
from occurring.
A salt-bridge is a glass U-tube filled with the solution of an ionic salt
(KNO3, NaCl, KCl....).

The ends are loosely

plugged with cotton
K+ NO3- balls or glass wool to
prevent the solution
from flowing into the
containers while still
allowing the ions
[cations (+ ) and anions
(-)] to move across the
barrier.
Instead of a salt bridge, you could use a porous
cup.

A porous cup is a porcelain container that also

allows the anions and cations to pass through.

In this case, the porous cup is one of the

half-cells.
The porous cup (filled with an
electrolyte) fits right inside the
other half-cell.
Building the Daniell Cell:
Start with a blank electrochemical cell (2-electrodes
(with wire connecting them), 2-beakers, etc.

Reaction is between
Zn and Cu2+, so start Zn
with them, but be
sure to separate
them. Cu2+
NO3-
H2 O
Now add in the other electrode and electrolyte.

The electrode to place in the Cu(NO3)2 solution

would be made of Cu metal.

The electrolyte to go
in the half-cell with
the Zn metal would Cu Zn
be Zn(NO3)2.

Nothing will happen Zn

unless we put in a Cu2+ NO3-
salt bridge (or use a NO3- H2 O
porous cup). H2 O
 The Daniel Cell would look like this:

electrode and K+ NO3- Zn electrode and

Cu
Cu
electrolyte electrolyte
match: Cu and
match: Zn and
Cu(NO3)2
Zn(NO3)2

Cu2+, NO3-, H2O Zn2+, NO3-, H2O

Using a porous cup,
it would look like
this:
Cu Zn

Cu2+, NO3-
Zn2+ NO3-
H 2O
H 2O
What happens:
First: List all the chemical species in both half cells.
Include everything – electrodes and
electrolytes.

Species:
K+ NO3-
Cu Zn
Cu(s), Cu , NO , H2O
2+
3
-

Zn(s), Zn2+

K+
 Second: From the list of
species, determine your SOA
and SRA using your table.

Cu(s), Cu2+, NO3-, H2O, Zn(s), Zn2+, K+

SOA SRA

Reaction is between Cu2+ and Zn (s)

Third: Isolate your SOA and SRA and
write out the two half-reactions
from your table (remembering to
reverse the oxidation).
SRA: Oxidation
(always at the anode):
Zn → Zn2+ + 2e-
SOA: Reduction
(always at the cathode):

Cu2+ + 2e- → Cu
Knowing this information – go to your
diagram and label the two electrodes as
the anode or cathode.
 cathode anode
(where reduction (where oxidation
occurs) K+ NO3- occurs)
Cu Zn
Cu2+ + 2e- → Cu Zn → Zn2+ + 2e-

Cu2+, NO3-, H2O Zn2+ NO3-, H2O

 Fourth: Using the equations, determine the
flow of electrons.

Oxidation is the LOSS of electrons:

Electrons ALWAYS flow through the wire from

anode to cathode.

On your diagram, show the direction of electron

flow, using an arrow. Be sure it’s evident that
this is through the wire.
 e- e-
cathode e- e- anode
(where reduction (where oxidation
occurs) K+ NO3- occurs)
Cu Zn

Cu2+, NO3-, H2O Zn2+ NO3-, H2O

Fifth: Look at the two half-reactions to see what is
happening at each electrode to determine the flow of ions.
Show this movement on your diagram (usually in the salt-
bridge).
The anions move toward Cations flow to the
the anode. cathode.

Cu + 2e- → Cu
2+
Copper ions in solution gain
electrons (are reduced) and
form copper solid.
Zn → Zn2+ + 2e-
Zinc metal loses electrons
(is oxidized) and produce
zinc ions that move into
the solution.
 e- e-
Cathode (+) e- e- Anode (-)

(where (where oxidation

reduction Cu K+ NO3- Zn occurs)
occurs)
Zn → Zn2+ + 2e-
Cu2+ +2e- → Cu e-
e- The Zn bar gets
The Cu bar e- smaller as Zn
gets larger as Cu 2+
Cu2+
Zn2+
Zn2+
Zn2+ atoms turn into
Cu atoms Cu2+, NO3-, H2O Zn2+ NO3-, H2O Zn2+ ions
form on its
surface.
 e- e-
Cathode (+) e-
Anode (-)
e-

As Cu2+ reacts Cu K+ NO3- Zn As Zn loses e-,

anions (NO3-) Zn2+ builds up in
build up in the the beaker.
beaker.
NO3- The positive
This negative Cu2+ Cu2+ Zn2+ Zn2+ charge attracts
charge - Zn the anions (-)
NO3- 2+
NO3- Zn NO
2+
Cu2+ NO3- 3

attracts the from the salt

cations in the bridge.
Cations move to cathode.
salt bridge.
Anions move to anode.
The circuit is complete – the electrons flow in the external circuit
through the wire, but the circuit is completed by the flow of the ions
(cations and anions) in the internal circuit (solutions).
 The flow of ions in the salt bridge allow the continuation of
the flow of electrons.
e- e-
e-
cathode e- anode
(where C K+ NO3
-
Z (where
reduction u n oxidation
occurs) occurs)

NO3- NO3- Zn2+ 2+

Zn 2+
Zn
NO - NO3
-
3 Zn2+ NO3-

Negative electrons won’t flow Electrons wouldn’t want

to a negatively charged to leave a positively
solution, so reaction would charged solution,
stop. Called Polarization. reaction would stop.
Instead of a salt-bridge or porous cup, we could use a porous
barrier:
 The cell notation for this would be:

Zn(s) / Zn(NO3)2(aq) // Cu(NO3)2(aq) / Cu(s)

anode / electrolyte(s) // electrolyte(s) / cathode

half-cell: oxidation // half-cell: reduction

Single lines (/) represent phase boundaries

The double line (//) represents the separation of the
half-cells (e.g. salt bridge or porous cup).
If the electrolytes are not at standard conditions, they are
included in brackets with the phase notation. If no concentration
or pressure is noted, the electrolytes are assumed to be at
standard conditions (1.00 M or 1.00 atm and 298 K).
What would be the cell notation for an electrochemical cell,
under standard conditions, that follows the reaction:
Sn2+ + Mg → Sn + Mg2+

Mg(s) / Mg2+(aq) // Sn2+(aq) / Sn(s)

What would be the cell notation for the following redox

reaction (standard cond.)?
F2(g) + Ni → Ni2+ + 2F-(aq)

Ni(s) / Ni2+(aq) // F-(aq) / F2(g) / Pt(s)

What would be the cell notation for an electrochemical cell,

under standard conditions, that follows the reaction:

Fe2+ + Br2 → Br- + Fe3+

C / Fe2+, Fe3+(aq) // Br2(l) / Br-(aq) / C(s)
One beaker contains 0.15 M Cd(NO3)2 and a Cd
metal electrode. The other beaker contains 0.20 M
AgNO3 and a Ag metal electrode. The net ionic
equation for the reaction is written:

2Ag+(aq)+Cd(s)⇌Cd2+(aq)+2Ag(s)
The Standard hydrogen Half-Cell (SHE):

2H+ + 2e- → H2(g)

This half-cell uses hydrogen gas

bubbled into a hydrochloric acid
solution over a platinum electrode.

The platinum electrode provides a

surface for the reaction and serves
as an electrical conductor for the
external circuit.

This half-reaction has been chosen as a reference point by

which all other half-reactions will be measured. It is called
the standard hydrogen electrode. Under standard
conditions: [H+] = 1.0 M, 25oC, 101.3 kPa, this reaction has
a cell emf (Eo) of zero.
When the standard hydrogen half-cell is used
with any other half-cell (as either a reduction or
an oxidation), the relative voltages can be
determined.
This is how the
values on the
Standard
Reduction
Table were
determined.
Using the table of Reduction Potentials, the cell potential
difference can be determined for any redox reaction.

EMF for a redox reaction (Eo) = Eocathode - Eoanode

(cell potential difference)

Reduction Oxidation

Think RedOx: EoRed - EoOxid

Using the table of Reduction Potentials, the cell potential
difference can be determined for any redox reaction.

EMF for a redox reaction (Eo) = Eocathode - Eoanode

(cell potential difference)

Reduction Oxidation

Think RedOx: EoRed - EoOxid

Using your Table to find Eo:

When you look at your table, all reactions appear from left to
right as reduction half-reactions.

Therefore, when you pick any two reactions, the substance

with the more positive Eo will be reduced.

It acts as the more powerful oxidizing agent.

F2(g) + 2e- ↔ 2F-(aq) +2.87 V more positive,

so F2 will be reduced.

Cl2(g) + 2e- ↔ 2Cl-(aq) +1.36 V will be oxidized,

so flip the equation.
F2(g) + 2e- ↔ 2F-(aq) +2.87 V more positive,
so F2 will be reduced.

Cl2(g) + 2e- ↔ 2Cl-(aq) +1.36 V will be oxidized,

so flip the equation.

Reaction will become: F2 (g) + 2e- ↔ 2F- (aq)

+ 2Cl- (aq) ↔ Cl2 (g) + 2e-

F2 + 2Cl- → 2F- + Cl2

Eo = Eocathode - Eoanode
= +2.87 – (+1.36)
= + 1.51 V
Note – Eo doesn’t change
when equation is reversed.
When balancing the redox reaction, the values
for Eo do not change.

Eo is unaffected by the size of the electrodes

or the amount of solution present.

I2 + 2e- → 2I- Eo = 0.53 V

2I2 + 4e- → 4I- Eo = 0.53 V

E.g. What is the cell potential produced from a
cell made with Ag+ and Zn(s)?

Cathode:
Red: 2[Ag+ + 1e- → Ag] Eo = +0.80 V
(do not multiply by 2)

Anode: Oxid: Zn → Zn2+ + 2e- Eo = -0.76 V

Cell EMF = Eocathode - Eoanode = +0.80 – (-0.76) =

+1.56 V

(reaction is spontaneous, since EMF is positive)

1. Draw an electrochemical cell using the spontaneous reaction
between nickel (Ni(s)) and aluminum ions (Al3+) in Al(NO3)3.
Label the anode and cathode and show the direction of electron
and ion flow. Give your two half-reactions and the overall
balanced redox reaction. Use either a porous cup or a salt
bridge.

Species: Oxidation:

SOA/SRA: Reduction:

Diagram: Redox:
2. Draw an electrochemical cell containing 1.0 M acidified (H+ in solution)
K2Cr2O7 solution with Ni(NO3)2 solution. The electrodes are nickel and
carbon. Use a porous cup.

Species: Oxidation:

SOA and SRA Reduction:

Redox:
Diagram:
20.5: Free Energy and Redox Reactions

Recall: If we look at any redox reaction, the sign of the emf

can tell us whether or not the reaction will be spontaneous.

Eocell = Eo (cathode) – Eo(anode)

If Eocell is: positive – reaction is spontaneous,

negative – reaction is nonspontaneous.

E (nonstandard) vs. Eo (standard)

Since emf (E) can indicate if a reaction is spontaneous,
as can ∆G, there exists a relationship between the two:

∆G = -nFE emf (in J/C or V)

in J/mol

F = faraday’s constant
moles of
electrons (quantity of electrical charge on
transferred one mole of electrons)
In standard states:
1 Faraday = 96 500 C/mol
∆G = -nFE
o o
= 96 500 J / V-mol
Problem:
Calculate the standard free energy change for the following
reaction at 25oC: 2Au(s) +3Ca2+(aq) (1.0 M) → 2Au3+ (1.0M) + 3Ca(s)

Eo = Eocath - Eoanode
2Au(s) → 2Au3+ + 6e- Eo = +1.50 V
3Ca2+(aq) + 6e- → 3Ca(s) Eo = -2.87 V
Eo = -2.87-(+1.50) = -4.37 V
∆Go = -nFEo
∆Go = -(6)(96500J/V)(-4.37 V)
∆Go = 2.5 x 106 J/mol
∆Go = -nFEo And: ∆Go = -RTlnK

Therefore: -nFEo = -RTlnK

Eo = RT lnK
nF

Eo = (8.314 J/K)(298 K) lnK

n(96500 J/V)

Eo = 0.0257 V lnK
n
 Relationships Among ∆Go , K and Eo
∆Go K Eo Reaction under standard
state conditions
negative >1 positive Favours formation of
products.
0 =1 0 Reactions and products
equally favoured
positive <1 negative Favours formation of
reactants
Problem: Calculate the equilibrium constant for the following
reaction at 25oC: Sn(s) + 2Cu2+(aq) ↔ Sn2+(aq) + 2Cu+(aq)

• Using your Standard Reduction Table, calculate Eo

Eo = Eocath - Eoanode Eo = 0.15 V – (-0.14 V)
= 0.29 V
• Plug into equation:

Eo = 0.0257 V lnK 0.29 V = 0.0257 V lnK

n 2

Sn(s) + 2Cu2+(aq) ↔ Sn2+(aq) + 2Cu+(aq) 0.29 V = (0.01285 V) lnK

0 +2
2e- transferred lnK = 22.6
n=2 K = 6.3x109
20.6: Cell EMF Under Nonstandard Conditions

Knowledge of standard Eo is not useful for very long, as the

concentrations of reactants and products change as the cell is
run. Cell emf drops until E = 0 (cell is dead).

At this point the concentrations of the reactants and products

do not change – the cell is at equilibrium.

The cell emf under nonstandard conditions can be

calculated using the Nernst equation.
Derivation of the Nernst equation:

Recall: ∆G = ∆Go + RTlnQ Q = equilibrium expression,

using the concentrations
given.
∆G = -nFE and ∆Go = -nFEo

Therefore: -nFE = -nFEo + RTlnQ

Solving for E: E = Eo – RT lnQ = Eo - 0.0257 lnQ

nF n
Problem: Predict whether the following reaction would
proceed spontaneously as written at 298 K:
Co(s) + Fe2+(aq) → Co2+(aq) + Fe(s) E= Eo - 0.0257 lnQ
n
Given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M
Eo = Eocath - Eoanode
Co(s) → Co2+(aq) + 2e- Eo = -0.28 V Q =[Co2+] = 0.15 = 0.22
Fe2+(aq) + 2e- → + Fe(s) Eo = -0.44 V [Fe2+] 0.68

Eo = -0.44 – (-0.28) = -0.16 V

Plugging it all in: E = -0.16 - 0.0257 ln(0.22)

2

E = -0.14 V E is negative – reaction

is nonspontaneous.
 At what concentrations would the same reaction become
spontaneous? Co + Fe2+ → Co2+ + Fe
(s) (aq) (aq) (s)

E = Eo - 0.0257 lnQ
n

At equilibrium, E = 0 0 = -0.16 - 0.0257 ln[Co2+ ]

2 [Fe2+]

-12.4 = ln[Co2+ ]
[Fe2+] E must be positive
to be spontaneous,
so ratio must be
[Co2+ ] = K = 3.9 x 10-6
smaller than 3.9 x
[Fe2+] 1
10-6 to 1.
Problem: Will the following reaction occur spontaneously at
25oC, given that [Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Cd(s) + Fe2+(aq) → Cd2+(aq) + Fe(s)

E = Eo - 0.0257 lnQ
n

E = (-0.04V) - 0.0257 ln(0.010 )

2 (0.60)

E = 0.01 V Yes - Spontaneous

If gases are involved in the cell reaction, their concentrations
should be expressed in atm. Both gases and aq will go into Q.
Consider the voltaic cell:
Zn(s) + 2H+(aq) (?M) → Zn2+(aq) (1.0 M) + H2 (1.0 atm)
In a certain experiment, the emf (E) of the cell is found to be 0.54 V
at 25oC. Suppose that [Zn2+] = 1.0 M and PH2 = 1.0 atm. Calculate
the molar concentration of H+.

E = Eo - 0.0257 lnQ 0.54 V = 0.76 V - 0.0257 ln [Zn2+]PH2

n n [H+]2

0.54 V = 0.76 V - 0.0257 ln [1.0M](1.0 atm)

2 [H+]2

[H+] = 2.0x10-4 M
Concentration Cells:

Since cell emf depends on concentration, it is possible to

construct a voltaic cell from two half-cells composed of the
same material, but differing in ion concentration.
For example: Cu2+(aq) + 2e- → Cu(s)

If we made a cell using copper sulfate at 0.1 M and 1.0 M

concentrations.

the reduction: Cu2+(aq) + 2e- → Cu(s) will increase with increased

concentration of copper ions.

Reduction will always occur in the

more concentrated half-cell.

Oxidation will always occur in the

more dilute half-cell.
Although Eo = 0 for a concentration cell, the Nernst equation
can be used to determine the actual cell emf.

E = Eo - 0.0257 lnQ
n
anode

E = 0 - 0.0257 ln [ ]dilute
n [ ] conc

cathode
Example:
Calculate cell potential for a concentration cell with two
silver electrodes with concentrations 0.2M and 3.0M.
SOLUTION:
Reaction: Ag1+ +e− →Ag(s)

Cell Notation: Ag(s) | Ag+ (0.20M) || Ag+ (3.0M) | Ag(s)

E = 0 - 0.0257 ln [ ]dilute
n [ ] conc

**Eo= 0 for concentration cells

E = 0 - 0.0257 ln [0.2 ]dilute

E = 0.070 V
n [3.0] conc
20.7: Batteries and Fuel Cells:

Reading Assignment
 20.8: Corrosion
Corrosion is the term usually applied to the deterioration of
metals by an electrochemical process.
E.g.: oxidation of copper
E.g.: Rusting of Iron

E.g.: oxid. of steel

Rust formation: oxidation of Fe metal: Fe → Fe2+ + 2e-

reduction of oxygen dissolved in water:

O2 + 2H2O + 4e- 4OH-
Fe2+ + 2OH- → Fe(OH)2

The hydroxide further reacts with oxygen to give the final

red product: Fe2O3 ∙H2O
 Al

Fe
Zn

Corrosion of zinc.

Aluminum corrodes more easily than iron ,

but the produced aluminum oxide serves
to protect the aluminum metal
underneath.
Ways to prevent
corrosion:

1. Coat the metal

with paint, grease,
enamel, lacquer….

However, once scratched

or pitted, corrosion will
occur under the surface.
 For example, stainless steel is iron and chromium . A layer
of chromium oxide forms a protective later. Choose metals
2. Use alloys. with higher resistance.
Another example –bike frame “chromoly” – chromium –
molybdenum (lighter than normal steel).
3. Cover the metal (plate)
with another metal less
subject to corrosion (a
weaker reducing agent).

For example, you could

plate an object in gold or
silver. Although it would
be expensive, these metals
are weak reducing agents,
so they do not oxidize
easily and would protect
the metal underneath.
4. Coat the metal with
another metal that is
more subject to
corrosion (a strong
reducing agent), so
that the coating acts Coating in Zn is “galvanizing”
as the anode (and
undergoes oxidation).
This is called Cathodic protection (a
sacrificial anode is used). For example,
iron can be covered with zinc,
magnesium or alumimum. The Zn, Mg,
or Al would oxidize first, leaving the iron
underneath intact.
Sacrificial anodes

The installation of
anodes typically last
15 - 25 years.
 The principle of impressed current cathodic protection is
Impressed to connect an external anode to the material to be
current system protected from corrosion and passing an external
electrical DC current to the object, making it the cathode.
20.9: Electrolysis

Electrolysis is the process by which electrical energy is

used to cause an otherwise non-spontaneous redox
reaction to occur.

Electrical energy is converted into chemical energy

(charging a battery, electroplating a metal).

An electrolytic cell is used for electrolysis.

 Like an electrochemical cell, an electrolytic cell
requires electrodes [usually inert – C or platinum
(Pt)] and an electrolyte to maintain the external
circuit.
For electrolysis we also require an external
source of current.

On the power supply the negative end supplies

the electrons and the positive end attracts the
electrons.

+ -

Often drawn this way.

 Both electrodes are found within the same
beaker – there is no salt-bridge or porous cup.

electrolyte
red (+) anode
black (-) cathode
+ -
Electrolysis can involve aqueous (in water) or
molten (melted – no water) electrolytes.
Here’s what happens:
a) electrons flow from the negative terminal of the
battery, making the attached electrode negative.
(cathode)
+ - e-

e-
e-
cathode

e-

e-
e-

+ -
b) the positive terminal draws electrons from the
other metal strip so the electrode becomes
positive. (anode)

+ - e-
e-
e-
anode e- e- cathode

e-

e-
e-

+ -
c) in solution:
- positive ions (cations) move towards the
negative electrode (cathode) and gain
electrons.
+ - e-
e-
e-
anode e-
e- cathode

e-
Reduction
occurs at the
e-
+ e- cathode.
+ + - +
• negative ions (anions) move towards the positive
charge being produced at the other electrode
and lose their electrons.
+ -
e-

anode e- cathode

e-
Oxidation occurs
at the anode. e-
- - e-
- + - -
 Note: The cathode is assigned a negative and
the anode is positive.

+ -
Again – electrons do
not move through
+
anode
e-
e- -
cathode
the solution, instead
it is a flow of ions. e-

Eo will be negative. e-
+ - e-
This is the cell potential that
needs to be supplied.
 To solve an electrolytic cell problem:

Example: Draw the electrolytic cell used for

the electrolysis of a calcium fluoride solution.
Give both half-reactions and label the anode,
cathode, and show the direction of anion,
cation, and electron flow. Describe what will
happen at the anode and cathode.
 Step 1: Draw a generic electrolytic cell.
Remember: 1 beaker, 2-inert electrodes (C or
Pt) and a power supply. Place the substance
in the beaker (include water if it is a solution).
e- e-
calcium fluoride solution
C C
CaF2

Ca2+ F- H2O
Ca2+
F-
H2O
Step 2: List all species present in the beaker:

Species: Ca2+ F- H2O

Step 3: Use your table to identify the SOA

and the SRA.

Species: Ca2+ F- H2O

SOA
SRA
 Step 4: Write out your two half-reactions.
Use these to guide the labelling of the diagram.

Red: 2H2O + 2e- → H2(g) + 2OH-(aq) e- e-

anode cathode

Oxid: 2H2O → O2(g) + 4H+(aq) + 4e-

Ca2+
Note: Oxidation occurs at/around the
F-
anode and reduction occurs at/around H2O
the cathode (ALWAYS).
 In this example:
• hydrogen gas will be produced at the
cathode (will see bubbles)
- e-
Red: 2H2O + 2e- → H2(g) + 2OH (aq)
e-

anode cathode
• oxygen gas will be produced
at the anode (see bubbles)

Oxid: 2H2O→ O2(g)+ 4H+(aq)+ 4e-

 Applications of electrolytic cells:

1. Production of elements:

Most elements occur naturally as compounds,

because they are strong oxidizing agents. To
separate elements such as Mg, Na, and Li
from these compounds, the molten (heated to
liquid) form of a compound is used in the
electrolytic cell.
E.g. electrolysis of molten NaCl (the Downs Cell)

Species: Na+ Cl-

e- e-
Table: SOA SRA
anode cathode
Red: Na + 1e → Na(s)
+ - C C

Cathode gets coated in Na.

Na(s)
Na+ Na
Oxid: 2 Cl → Cl2(g) + 2e
- - Cl2
Cl - Na
Cl 2
(s)

Cl2 (s)

Anode will have bubbles of Cl2

chlorine gas.
Eo = (-2.71) – (+1.36) = - 4.07 V needed!
 2. Refining of metals (Electrorefining, Smelting):

Metals are initially extracted from minerals using heat.

However, by heating metals such as copper, we can
only obtain 99% purity. Any impurities lower the
copper’s electrical conductivity, so that it must be further
refined through electrolysis before it can be used as a
conducting wire.
 e- e-

anode Cu C cathode
Zn
Fe

unrefined impure
metal Reduction:
Cu2+ SOA gains electrons.
Oxidation: Cu2+ + 2e- → Cu
Metals lose electrons. Zn2+
Fe2+
Cu forms on cathode.
3. Electroplating:
Electroplating is the deposition of a thin layer of
metal, whose ions are found in the electrolyte,
on an object at the cathode.

The process improves corrosion resistance (e.g.

metallic chromium on steel bumpers saves
money) and attractiveness (e.g. silver plating
kitchen utensils).
Often the object to be plated is made of a cheap
metal and it is plated with a more expensive
metal.
Electroplating is an electrolytic cell, but with
the following specifications:

1. The object being plated must conduct an

electric current. Nonconductors are coated with
graphite.
2. The object being plated is the CATHODE
(connected to the negative terminal). This
makes the object negatively charged, causing it
to attract the positive metal ions in the solution.

e- e-

anode Oe- cathode

B
e-
J cations (+) gain electrons
Ee-
and forms a solid metal
++ Ce-
on the object (cathode).
+ T
+
 3. A bar of the plating metal is the ANODE
(connected to the positive terminal). This bar
will undergo oxidation and will supply the
metal ions to the solution.
If we want to coat
something in copper, the e- e-
anode is a Cu bar.
Cu → Cu2+ + 2e- anode Oe- cathode
B
e-
J
If we want to coat
Ee-
something in silver, the
+ Ce-
anode is a silver bar. + T
Ag → Ag+ + 1e- + +
 4. The electrolyte contains the metal ion that is
plating the object.

For example, if we are e- e-

coating an object in silver,
than Ag+ must be in anode cathode
solution.

If we are coating an
object in chromium, metal
ions
than Cr3+ is in solution.
Problem: Draw the electrolytic cell capable of plating
an iron fork in silver. Label everything.
Give the equation for the reduction and oxidation.

anode: Ag bar
Fe (cathode)

Ag+ solution:
(AgNO3 or AgSO4) Ag+
NO3-
H2 O

Oxid: Ag → Ag+ + 1e- Red: Ag+ + 1e- → Ag

Problem: Draw the electrolytic cell capable of plating a
Nickelback CD in nickel. Give the reduction and
oxidation half-reactions.
Quantitative Aspects of Electrolysis: Stoichiometric Relationships

Between 1831 and 1834, Michael Faraday

conducted experiments with electrolytic cells.

As a result of the experiments, he observed

that the mass of product formed at an
electrode is proportional to both the amount
of electricity transferred at the electrode and
the molar mass of the substance in question.
The half­-reaction (from your table) relates the
amount of chemical substance consumed or
produced to the number of faradays that the
electric current must supply.

Cu2+ + 2e- → Cu(s)

consumed produced/deposited

number of faradays
 1 mole of electrons = 1 Faraday

Cu2+ + 2e- → Cu(s)

Therefore: 1 mole of copper would require 2 Faraday.

How many Faraday are required to produce 3 moles
of Al(s)? Al3+ + 3e- → Al from your table
(s)

3 mol of e- = 1 mole of Al(s)

3 mol Al 3F
1 mol Al
X = 9 F are required
 In electrolysis, the current (in amperes, A) that flows
through the electrolytic cell in a given period of time
is measured.

The relationship between charge and current is

Q=It

charge = (current) (time) 1 C = 1 A∙s (units)

1 Coulomb = (1 ampere) (1 second)

Experimentally:

1 faraday = 96 500 coulombs of charge (Q)

(and 1 Faraday = 1 mole of electrons)

Linking all these relationships together we can
move between different variables:
mass
moles = mass / molar mass

moles of substance
use ½ reaction knowing
1 mole of e- = 1 faraday
faradays
1 F = 96 500 C

charge in Coulombs
I = Q/t or t = Q/I
current & time
 Ag
Problem 1: How many grams of silver are deposited on the
cathode of an electrolytic cell if an electric current of 3.50 A is
run through a solution of AgNO3 for a period of 15.0 minutes?
(Ag+)
Solution:
Q = It Q = (3.50 A)(15.0 min)(60 s/min) = 3150 C

# F = 3150 C 1F = 0.0326 F
96500 C

Ag+ + 1 e- → Ag 0.0326 F 1 mol Ag = 0.0326 mol

1F

0.0326 mol 107.87 g = 3.52 g

1 mol
Problem 1: How many grams of silver are deposited on the
cathode of an electrolytic cell if an electric current of 3.50 A is
run through a solution of AgNO3 for a period of 15.0 minutes?
You could also solve this in one step:

(3.50 A)(15 min) 60s 1 C 1F 1 mol Ag 107.87 g =

1 min 1 As 96500 C 1F 1 mol

Q = It
Q→F F→mol mol → mass

Unit
conversion
 t=?
Problem 2: How much time would be required to deposit
mass 0.750 g of metallic aluminum on an object if a current of
2.60 A were used? →Al
moles current (I)

0.750 g 1 mol Al 3 F 96500 C 1 A s 1

26.98 g 1 mol Al 1F 1 C 2.60 A

Al3+ + 3e- → Al
t =3095 s
Congratulations
you have finished
(almost)

AP Chemistry.