Science

Electrochemistry Skill Builder

The following metal electrodes and salt solutions are available for use in the problems below.
Metal electrodes: Cu, Zn, Ag, Al Half-Reaction E°(V)

Salt Solutions: 0.50 M and 1.0 M solutions of Cu(NO3)2, Cu2+(aq) + 2e− → Cu(s) + 0.34
Zn(NO3)2, AgNO3, Al(NO3)3 Zn2+(aq) + 2 e− →   Zn(s) − 0.76

Ag+(aq) + 1e− → Ag(s) + 0.80

GALVANIC CELLS Al3+(aq) + 3e− → Al(s) − 1.66

1. Using the available materials, design a spontaneous electrochemical cell at standard conditions that will
produce the highest initial voltage.
a. Label the anode and cathode metals
b. Label the anode and cathode solutions
c. Draw arrows through the wire to indicate the direction of electron flow
d. Indicate which ion from the salt bridge will migrate into each chamber
e. Write the balanced half-reactions for each electrode and the overall balanced equation

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f. Circle whether each electrode will increase or decrease in mass
g. Indicate the value of n, the number of electrons/mole rxn, in the balanced equation
h. Calculate E°cell E°cell = (+0.80) + (+1.66) = 2.46 V

A N S W E R
i. Calculate ∆G°

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2. Using the available materials, design a spontaneous electrochemical cell at standard conditions with initial
E°cell of +0.90V.
a. Label the anode and cathode metals
b. Label the anode and cathode solutions
c. Draw arrows through the wire to indicate the direction of electron flow
d. Indicate which ion from the salt bridge will migrate into each chamber
e. Write the balanced half-reactions for each electrode and the overall balanced equation
f. Circle whether each electrode will increase or decrease in mass
g. Indicate the value of n, the number of electrons/mole rxn, in the balanced equation
h. Calculate ∆G°

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3. Design a Voltaic cell in which the addition of solid NaCl to the cathode cell will cause the voltage to
decrease. Label the diagram below and explain why the addition of NaCl(s) reduces the voltage.

The Cl− ion from NaCl will react with the Ag+ ion in the cathode cell to form a precipitate. As the Ag+
precipitates, the cell voltage decreases until finally no Ag+ is available for the reaction.

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4. Write the balanced overall equation for a combination of metals and standard solutions whose anode [ion]

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increases at half the rate that the cathode [ion] decreases as the cell runs. Use the circles below to draw a
particulate view of what is occurring at the surface of each electrode.
2 Ag+(aq) + Zn(s) → Zn2+(aq) + 2 Ag(s)
2 Ag+(aq) + Cu(s) → Cu2+(aq) + 2 Ag(s)
Overall equation:_____________________________________________________

Silver paired with either zinc or copper will have the desired result. Zinc and copper both lose 2e−/mol and
silver gains 1e−/mol. At the cathode, metal ions are gaining electrons to become solid metal. At the anode solid
metal is losing electrons to become metal ions.

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5. Identify all of the combinations of available materials that would produce a spontaneous Galvanic cell
whose Ecell > E°cell. Use the Nernst equation to explain your reasoning.
Anode Cathode
Metal Solution Solution Metal
Zn 0.5M Zn(NO3)2 1.0 M Cu(NO3)2 Cu
Al 0.5 M Al(NO3)3 1.0 M Cu(NO3)2 Cu
Al 0.5 M Al(NO3)3 1.0 M Zn(NO3)2 Zn
Cu 0.5 M 1.0 M AgNO3 Ag
Cu(NO3)2
Zn 0.5M Zn(NO3)2 1.0 M AgNO3 Ag
Al 0.5 M Al(NO3)3 1.0 M AgNO3 Ag
Cu 0.5 M 1.0 M Cu(NO3)2 Cu
Cu(NO3)2
Ag 0.5 M AgNO3 1.0 M AgNO3 Ag

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The Nernst equation allows for calculation of cell voltages at non-standard conditions. In the equation any time
Q<1 the log of Q will be negative, resulting in additional voltage being added to the standard voltage. Q will be
less than 1 when the numerator (product) is smaller than the denominator (reactant). The ion appearing in the
numerator of the Q fraction is the product of the oxidation reaction occurring at the anode. The ions appearing
in the denominator of the Q fraction are the reactants of the reduction reaction occurring at the cathode. In
order to create a Q<1 the [anode] ions must be less than the [cathode] ions after any exponents are applied.
It is also possible to increase voltage by creating a concentration cell using the same metal for both electrodes,
but differing concentrations. Since a concentration cell has the same metal for both electrodes, the standard
E°cell is zero and the only factor contributing to the voltage is that which is created by the Q term in the Nernst
equation. Again, creation of a system where Q<1 will create a positive voltage addition. In a concentration
cell, this necessitates the anode has the lower concentration and the cathode has the greater concentration.

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6. A student tried to design a spontaneous galvanic cell at standard conditions that would produce a standard
cell voltage of 1.10 V. The result is drawn below. Identify all of the problems with this design.
1.10 V

anode metal Zinc Copper cathode metal

0.50 M Al(NO3)3
anode solution 1.0 M Zn(NO 3)2 cathode solution

• The cell solutions much contain the same metal ion as the electrode. If the cathode metal is copper, then
then cathode solution must contain a copper ion.
• There is not a salt bridge. The salt bridge is necessary for the circuit to work. The ions from the salt
bridge migrate to keep the charges balanced and the electrons flowing through the wire.

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• The concentration of the solution in the cathode should be 1.0 M if the cell is at standard conditions.

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ELECTROLYTIC CELLS

Many electrolysis problems can be solved using dimensional analysis or the equation:
I t MM
grams plated =
nF

7. For each of the metals listed, determine how many grams can be plated from a 1.0 M solution of the the
nitrate salt when a current of 1.5 A is applied for 1 hour.

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8. For each metal listed, determine the number of minutes required to plate 1.0 gram of metal with a current
of 2.0 A. What generalization can you draw about the relationship between molar mass and time required?

A N S W E R
Between n and time?

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9. Determine the formula for a Fe(NO3)x salt that was electrolyzed to produce 2.50 g of iron from a current of
1.80 A running for 2 hours.

10. Determine the formula for a metal nitrate that will plate out 3.64 grams of metal M from a concentrated
solution of M(NO3)2 when a current of 2.0 A is run for 30 minutes. Identify metal M.

REFLECTION QUESTIONS

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A. What are some key points to remember when drawing diagrams of Galvanic cells?
Oxidation occurs at the anode (AN OX)

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Reduction occurs at the cathode (RED CAT)
Electrons travel from the anode to the cathode (FAT CAT)
Anions migrate to the anode; cations migrate to the cathode
Standard conditions are 25°C and 1 M solutions

B. What is the purpose of the salt bridge, and what are important characteristics to consider when selecting
the salt bridge contents?
The salt bridge must be present to balance the charge as electrons move through the wires from the anode
to the cathode. The ions in the salt bridge migrate into their respective cells to keep the charges from
building up and bringing the electron flow to a halt. The salt in the salt bridge must be soluble and must
not cause precipitation when migrating into the half cells.
C. What general statement can you write to describe the migration of the cations and anions from the salt
bridge?
Anions migrate to the anode; cations migrate to the cathode

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D. What are standard conditions for electrochemical cells? How can you qualitatively use the Nernst equation
to consider the effect of non-standard concentration conditions on cell potential?
Standard conditions in electrochemical cells call for 1 M solutions. The Nernst equation is useful to adjust
the standard cell voltage by a factor that accounts for the concentration ratio of the ions in the cells when
they are not all 1M. Q is the ratio of [products] to [reactants] raised to the power of their coefficients.
When Q is > 1, the log of Q is positive, and the standard cell voltage is reduced. When Q is < 1, the log of
Q is negative, and the standard cell voltage is increased.

E. For electrolytic cells which variables have a direct relationship with the number of grams plated?
The current, time and molar mass all have a direct relationship with the number of grams plated because
they are in the numerator of the equation

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AP QUESTIONS

2003 B
6. Answer the following questions about electrochemistry.
a. Several different electrochemical cells can be constructed using the materials shown below. Write the
balanced net-ionic equation for the reaction that occurs in the cell that would have the greatest positive
value of E°cell.

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Al(s) → Al3+(aq) + 3e− 1 point for selection of correct two redox
Cu2+(aq) + 2e− → Cu(s) couples
2 Al(s) + 3 Cu2+(aq) → 2 Al3+(aq) + 3 Cu(s) 1 point for correctly balanced net ionic
equation

b. Calculate the standard cell potential, E°cell for the reaction written in part (a).

Al3+(aq) + 3e− → Al(s) E°=−1.66V

Cu2+(aq) + 2e− → Cu(s) E°=+0.34V 1 point for correct E°cell
(Must be consistent with part (a))
E°cell = E°cathode − E°andode = +0.34 V − (−1.66V) = +2.00V

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c. A cell is constructed based on the reaction in part (a) above. Label the metal used for the anode on the
cell shown in the figure below.
The metal is aluminum solid. 1 point for correct metal
(Must be consistent with part (a))

d. Of the compounds NaOH, CuS, and NaNO3, which one is appropriate to use in a salt bridge? Briefly
explain your answer, and for each of the other compounds, include a reason why it is not appropriate.

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NaOH is not appropriate. The anion, OH− would 1 point for correctly indicating
migrate towards the anode. The OH− would react whether each compound is
with the Al3+ ion in solution. appropriate, along with an

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explanation (3 points total)
CuS is not appropriate. It is insoluble in water, so no
ions would be available to migrate to the anode and
cathode compartment to balance the charge.

NaNO3is appropriate. It is soluble in water, and

neither the cation nor the anion will react with the
ions in the anode or cathode compartment.

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2000
7. Answer the following questions that relate to electrochemical reactions.
a. Under standard conditions at 25°C, Zn(s) reacts with Co2+(aq) to produce Co(s).
i. Write the balanced equation for the oxidation half reaction.
Zn(s) → Zn2+(aq) + 2e− 1 point
Note: phase designations not required in part
(i) or part (ii)
ii. Write the balanced net-ionic equation for the overall reaction.
Co2+(aq) + Zn(s) → Co(s) + Zn2+(aq) 1 point

iii. Calculate the standard potential, E° for the overall reaction at 25°C.
0.76 V + (−0.28 V) = 0.48 V 1 point

b. At 25°C, H2O2 decomposes according to the following equation.

2 H2O2(aq) → 2 H2O(l) + O2(g) E° = 0.55V

i. Determine the value of the standard free energy, ∆G° for the reaction at 25°C.

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2 points
∆G° = −nFE° = −2(96,500)(0.55 V) First point earned for n=2 (consistent use of

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n=4 also accepted)
= −1.1x105 J or −1.1x102 kJ
Second point earned for negative sign, correct
number (2 ± 1 sig. figs.), and appropriate
units (kJ or J or kJ/mole or J/mole)

ii. Determine the value of the equilibrium constant, Keq for the reaction at 25°C.
1 point
∆G°=−RTLn(K)
−1.1x105 J = −[8.31 J mol−1 K−1][298 K][ln(K)]
K=2.0x1019 (full credit also for correct use of log K = nE°/0.592)

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iii. The standard reduction potential, E° for the half reaction

O2(g) + 4H+(aq) + 4e− → 2 H2O(l) has a value of 1.23 V. Using this information in addition to the
information given above, determine the value of the standard reduction potential, E°, for the half
reaction below.
O2(g) + 2H+(aq) + 2e− → H2O2(aq)

O2 + 2H2O → 2 H2O −0.55V 2 points

O2 + 4H+ + 4e− → 2H2O2
__________________________________
2O2 + 4H+ + 4e− → 2H2O2
⇒O2 + 2H+ + 2e− → H2O2
required)
1.23 V Two points earned for
correct voltage with
supporting numbers
0.68 V (chemical equations not
necessary)
0.68 V (not
One point earned for
correct chemical equations
with incorrect voltage

c. In an electrolytic cell, Cu(s) is produced by the electrolysis of CuSO4(aq) Calculate the maximum mass
of Cu(s) that can be deposited by a direct current of 100 amperes passed through 5.00 L of 2.00 M

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CuSO4(aq) for a period of 1.00 hour.
2 points

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Two points earned for correct
answer (3±1 sig. figs.)
One point earned for any two of
these steps:
(amp)(sec) ⇒ coulombs
coulombs ⇒ mol e−
mol e− ⇒ mol Cu
mol Cu ⇒ g Cu

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1992
2. An unknown metal M forms a soluble compound, M(NO3)2.
a. A solution of M(NO3)2 is electrolyzed. When a constant current of 2.50 amperes is applied for 35.0
minutes, 3.06 grams of the metal M is deposited. Calculate the molar mass of M and identify the metal.
3 points

1 point for Coulombs

1 pont for moles

1 point for metal

b. The metal identified in (a) is used with zinc to construct a galvanic cell, as shown below. Write the net
ionic equation for the cell reaction and calculate the cell potential, E°.

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K+ Cl-

Metal M Zinc

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1.0 M solution of M(NO 3)2 1.0 M solution of Zn(NO 3)2

Zn → Zn2+ + 2e− 0.76 V 2 points

2e− + Cd2+ → Cd −0.40 V 1 point for correct equations
Zn + Cd2+ → Zn2+ + Cd 0.36 V 1 point for correct voltage

c. Calculate the value of the standard free energy change, ∆G° at 25°C for the reaction in (b).
2 points
1 point for correct equation and
substitution
1 point for correct answer

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d. Calculate the potential, E, for the cell shown in (b) if the initial concentration of ZnSO4 is 0.10-molar,
but the concentration of the M(NO3)2 solution remains unchanged.
2 points
1 point for correct equation and
substitution
1 point for correct answer

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