9.

TOPIC: 9.7 GALVANIC (VOLTAIC) AND ELECTROLYTIC CELLS

ENDURING UNDERSTANDING:
ENE-6 Electrical energy can be generated by chemical reactions.
LEARNING OBJECTIVE:
ENE-6.A Explain the relationship between the physical components of an electrochemical cell and the overall
operational principles of the cell.
ESSENTIAL KNOWLEDGE:
ENE-6.A.1 Each component of an electrochemical cell (electrodes, solutions in the half-cells, salt bridge, voltage/current
measuring device) plays a specific role in the overall functioning of the cell. The operational characteristics of
the cell (galvanic vs. electrolytic, direction of electron flow, reactions occurring in each half-cell, change in
electrode mass, evolution of a gas at an electrode, ion flow through the salt bridge) can be described at both
the macroscopic and particulate levels.
ENE-6.A.2 Galvanic, sometimes called voltaic, cells involve a thermodynamically favored reaction, whereas electrolytic
cells involve a thermodynamically unfavored reaction. Visual representations of galvanic and electrolytic cells
are tools of analysis to identify where half-reactions occur and in what direction current flows.
ENE-6.A.3 For all electrochemical cells, oxidation occurs at the anode and reduction occurs at the cathode.
X LABELING AN ELECTRODE AS POSITIVE OR NEGATIVE WILL NOT BE ASSESSED ON THE AP EXAM.
Rationale: Sign conventions vary depending on the type of electrochemical cell, even though oxidation always
occurs at the anode.
EQUATION(S):

NOTES:
Electrical energy can be generated from chemical reactions. In an oxidation-reduction reaction, electrons are
transferred from one species to another. One way to harness this electrical energy is to create an electrochemical
cell. A simple cell is set up as shown in the image below. In each beaker there is a metal (or gas system) and its
corresponding ions in solution (in a standard cell the concentration is 1.0 M at 298 K and 1 atm). This is referred to
as a half cell. They will not react unless two half cells are connected to complete a circuit.

The solids (or gas systems) that are placed into each of the solutions are called electrodes. The electrode where
oxidation occurs is called the anode, because it attracts anions from the salt bridge and the solution. The electrode
where reduction occurs is called the cathode, because it attracts the cations from the salt bridge and in the
solution. The mnemonic that can help you to remember this is red-cat, an-ox. Electrons flow through the wire
from the anode to the cathode. (mnemonic - FAT CAT From Anode To CAThode)
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The salt bridge or porous disc is used to separate the solutions. The ions in the salt bridge will travel through the
solution, agar or glass wool and serves to maintain the neutral charge as the electrons flow from one side to
another through the wire. Without these ions in the salt bridge, the reaction would not occur. A porous disc
between two beakers works similarly without the need for another solution; the ions are able to travel between
the two sides.

To predict which of the potential reactions is thermodynamically favorable, we need to look at a table of standard
reduction potentials. On the AP exam the values will be provided in the problem. You can find a table here. The
table of standard reduction potentials is basically a ranking of different substances; the ones that are the best at
reduction (most likely to be reduced) are at the top, with the substances that are the worst at reduction (least
likely to be reduced) at the bottom. The substances at the bottom would be the best at oxidation. The
electromotive force, or reduction potential, gives the voltage that is generated from that half-reaction.

Let’s compare two substances, silver, Ag/Ag+ and gold, Au/Au3+, by writing their reduction half reactions and
looking up their standard reduction potentials.
Reduction Reaction Reduction Potential
This reaction is better at reduction.
Au3+(aq) + 3e- Au(s) 1.50 V The “winner” stays the way it is written in the table.

Ag+(aq) + e- Ag(s) 0.80 V This reaction is better at oxidation.

The “loser” reaction flips and is written in reverse.

The reduction reaction for the gold ions, Au3+, has a higher reduction potential than the silver ions, Ag+, which
means that the Au3+ ions are better at being reduced than the Ag+ ions. We can use this to predict the
thermodynamically favorable reaction will take place.

Au3+(aq) + 3 Ag(s) Au(s) + 3 Ag+(aq) Will react (thermodynamically favorable)

(includes the favorable reduction reaction)

Au(s) + 3 Ag+(aq) Au3+(aq) + 3 Ag(s) Will not react (thermodynamically unfavorable)

We can also predict the voltage that will be generated when the reaction occurs. When the reaction is “flipped” to
switch the position of the reactants and the products, the sign for the voltage will change. However, when the
reaction is multiplied by a factor, you do not change the voltage. You can think of it as an intensive property
because voltage is the pressure that pushes the electrons (current) through a wire. This means that if the mass of
the electrodes are changed the voltage would not change.
Reaction Reduction Potential
Au3+(aq) + 3e- Au(s) Reduction 1.50 V

3 Ag(s) 3 Ag+(aq) + 3 e- Oxidation - 0.80 V

The thermodynamically favorable reaction:
Au3+(aq) + 3 Ag(s) Au(s) + 3 Ag+(aq)
will generate +0.70 volts (1.50V+(-0.80V)). Cells that are thermodynamically favorable have positive voltages and
are known as Galvanic or Voltaic cells.

Whereas the unfavorable reaction:

Au(s) + 3 Ag+(aq) Au3+(aq) + 3 Ag(s)
will require 0.70 volts (-1.50V+0.80V = -0.70 V) from an external power source in order to proceed. Cells that are
thermodynamically unfavorable have negative voltages, require external power supplies and are known as
Electrolytic cells.
 9.7

I DO:
Given these two reduction half reactions:
Mg2+(aq) + 2 e- Mg(s) E° = -2.37 V
Na+(aq) + e- Na(s) E° = -2.71 V
A) Write the thermodynamically favored balanced overall reaction.
Mg2+(aq) + 2 e- Mg(s)
2 Na(s) 2 Na+(aq) + 2 e-
Mg (aq) + 2 Na(s)
2+ Mg(s) + 2 Na+(aq)
B) Calculate the voltage for this cell
-2.37 + 2.71 = + 0.34 V
C) Write the half reaction that takes place at the anode
2 Na(s) 2 Na+(aq) + 2 e-
D) Write the half reaction that takes place at the cathode
Mg2+(aq) + 2 e- Mg(s)
E) After the reaction has been allowed to take place, what will happen to the anode?
The anode will dissolve in the solution as it forms Na+ ions. It will decrease in mass.
F) After the reaction has been allowed to take place, what will happen to the cathode?
The cathode will increase in size as magnesium metal forms from the ions. It will increase in mass.
WE DO:
Given the reactions:
2H3O+(aq) + 2 e- H2(g) + H2O (l) E° = 0.00 V
Fe2+(aq) + 2 e- Fe(s) E° = -0.45 V
A) Write the thermodynamically favored balanced overall reaction.

B) Calculate the voltage for this cell

C) Write the half reaction that takes place at the anode

D) Write the half reaction that takes place at the cathode

E) After the reaction has been allowed to take place, what will happen to the anode?

F) After the reaction has been allowed to take place, what will happen to the cathode?

YOU DO:
1) The following reduction half reactions were used to create a cell:

flips 3 C A2+ (aq) + 2 e- A(s) E° = 0.55 V

B3+ (aq) + 3 e- B(s) E° = ?
At one electrode, it was observed that solid B was formed.

A) Write the overall reaction that was taking place.

3 Acs 2133Eaa 3AZ caa t2Bcs
B) If the overall cell voltage was 0.95 V, calculate the standard reduction potential for the half reaction
involving B?
X 0.55 0.95 V X 1.5OV
C) What will happen to the electrode in the beaker with the A2+ solution as the reaction progresses?

the Acs will dissolve the mass decreases

D) How many electrons in total were transferred in this reaction?
6
 9.7
2) Consider a cell that is composed of zinc metal in contact with a solution of zinc sulfate, ZnSO4, and
copper metal in a solution of copper (II) sulfate, CuSO4. The zinc is shown in the diagram on the left and
copper is on the right. Answer the following questions, the reduction half reactions are provided.
Reduction Reaction Reduction Potential

fix Zn2+(aq) + 2 e-

Cu2+(aq) + 2e-
Zn(s)

Cu(s)
-0.76 V

0.34 V
e i lov e
bridge
A) Which is the reduction reaction? gut
yakedwdfatea
Heard
Cathode
art 2e Cu anode agng
B) Which is the oxidation reaction? ay Cy
Zn 2nA 2e
C) Write the overall reaction

A t 2n Zn t Ar
D) Calculate the voltage for this cell.

0.34
0.76 It I LOV
E) Label the following on the diagram 21
o Zinc electrode Lncaa Ae caq
o Copper electrode
o Zinc solution
o Copper solution
o Anode
o Cathode
o Salt Bridge (NaNO3)
o Voltage
o Draw an arrow to show the direction that the electrons travel
o Write the ions present in the salt bridge
o Use arrows to indicate the direction that the ions in the salt bridge will travel

F) A student suggests that you could use spectroscopy to measure the amount of the solution that has reacted.
Which solution would you need to use to test this theory?

The cut b c it has a color Cu electrode gets

What visual changes would you expect to see as the reaction progresses? bigger
gets
the Cu solution will get lighter in color mmaGdwdl
3) A cell was created using aluminum metal with an Reduction Reaction Reduction Potential
aluminum nitrate solution and lead with a lead (II)
Al3+(aq) + 3 e- Al (s) -1.66 V
nitrate solution. The salt bridge contained NaCl.
Given the model of the anode, complete a similar model for the Pb2+(aq) + 2e- Pb(s) -0.13 V
cathode. Complete the key.
Anode Anode after reaction Cathode Cathode after reaction
A A A A A A 000
888 o
A A A A A A
A A A A A A
A A
Key= = = = =
A L 00
A
L
At AP A
L
Pb Pba
2At 21131 3Pb2t 3 Pb
 9.7
4) Consider a cell that is composed of tin metal in contact with a solution of tin (II) sulfate, SnSO4, and zinc
metal in a solution of zinc nitrate, Zn(NO3)2. Answer the following questions, the reduction half
reactions are provided.

Reduction Reaction Reduction Potential

Sn2+(aq) + 2 e- Sn(s) -0.14 V
t
Zn2+(aq) + 2e- Zn(s) -0.76 V
0.62V I e
A) Which is the reduction reaction? Anode Saltbridge cathode
Na NG
Sn 2E Sn Zn TE Sn
B) Which is the oxidation reaction?

Zn Zhu tze
C) Write the overall reaction

Sn Ia t2n 2h4m tsn

D) Calculate the voltage for this cell.

0.14 t 0.76 0.62 V y et

E) Label the following on the diagram Zn Sn
o Zinc electrode
o Tin electrode
o Zinc solution
o Tin (II) solution
o Anode
o Cathode
o Salt Bridge (NaNO3)
o Voltage
o Draw an arrow to show the direction that the electrons travel
o Write the ions present in the salt bridge
o Use arrows to indicate the direction that the ions in the salt bridge will travel

F) What will happen to the mass of each electrode as the reaction proceeds?

Zn decreases sin will increase

5) Given the reactions below:
Reduction Reaction Reduction Potential
Ni2+(aq) + 2 e- Ni(s) -0.26 V

Mn2+(aq) + 2e- Mn(s) -1.19 V

No A are
Au3+(aq) + 3e- Au(s) 1.50 V
oxidation
Which combination will have the most thermodynamically favorable reaction with the reduction
reaction: Cu2+(aq) + 2 e- Cu(s) (E° = 0.34 V)? (Cu2+ must be reduced) Support your answer with a
calculation(s).
Thereaction
Cu 2e 0 0.34V 0,60N out't Mn is
Ar
themost thermodynamically
Ni Niu tze 0.26 favorable b c I
the highest
Cua t 2e Ae 0 0.34V o53V has
reduction potential
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