Electrochemistry

Applications of Redox
 Review
 Oxidation reduction reactions involve a
transfer of electrons.
 Lose Electrons - Oxidation; increase in
charge
 Gain Electrons Reduction; decrease in
charge
 Applications
Problem 1
Balance the following equation by the half reaction method.
MnO4-(aq) + Fe2+(aq) -> Mn2+(aq) + Fe3+(aq)
 Connected this way the reaction starts
 Stops immediately because charge builds
up.

H+
Fe+2
MnO4-
 Galvanic Cell
Salt
Bridge
allows
current
to flow

H+
Fe+2
MnO4-
 e- e-
e - e-

Anode Cathode

e- e-
Reducing Oxidizing
Agent Agent
Problem 2
Identify the anode and the cathode of the following redox reaction.
Mg(s) + H+(aq) -> Mg2+(aq) + H2(g)
 Cell Potential
 Oxidizingagent (what gets reduced)
 Reducing agent (what gets oxidized)

 The push or pull (“driving force”) is called

the cell potential Ecell
 Also called the electromotive force (emf)
 Unit is the volt(V)
 1 V= 1 joule/coulomb of charge
 Measured with a voltmeter
 0.76

H2 in

Anode Cathode
H+
Zn+2 SO4-
2 Cl-
1 M ZnSO4 1 M HCl
 Standard Hydrogen Electrode
 This is the reference
all other oxidations
are compared to H2 in
Eº = 0
º indicates standard
states of 25ºC, H+
1 atm, 1 M Cl-
solutions.
1 M HCl
 Cell Potential
 Zn(s) + Cu+2 (aq)  Zn+2(aq) + Cu(s)
 The total cell potential is the sum of the
potential at each electrode.

Eº cell = Eº Zn Zn+2 + Eº Cu+2Cu
 We can look up reduction potentials in a
table.
 One of the reactions must be reversed,
so change it sign.
 Cell Potential
Problem 3
Using the Data from the Appendix in your textbook, calculate the cell
potential (Eocell) for each of the following reactions.
l Cu2+(aq) + 2Ag(s) -> Cu(s) + 2Ag+(aq)
l 2Zn2+(aq) + 4OH-(aq) -> 2Zn(s) + O2(g) + 2H2O(l)

 The higher the reduction potential number the stronger the oxidizing
agent; the lower the reduction potential the stronger the reducing agent
Problem 4
Place the following in order of increasing strength as oxidizing agents.
Fe2+ Ecell=-.4 V; ClO2 Ecell= .94 V; F2 Ecell = 2.87 V; AgCl Ecell = .22 V
Problem 5
Given the following half-cells, decide which is the anode and the
cathode, balance, write the overall cell reaction and calculate
Eocell.
a) Ni2+ + 2e- -> Ni Eo = -0.23 V
O2 + 4H+ + 4e- -> 2H2O Eo=+1.23 V

b) Ce4+ + e- -> Ce3+ Eo= +1.70 V

Sn2+ + 2e- -> Sn E0= -0.14 V
 Line Notation
 solidAqueousAqueoussolid
 Anode on the leftCathode on the right
 Single line different phases.
 Double line porous disk or salt bridge.
 If all the substances on one side are
aqueous, a platinum electrode is
indicated.
Problem 6
Write line notations for each of the following galvanic cells
a) Hg2+ + Cd -> Hg + Cd2+
b) Cu2+ + 2Pu4+ + 4H2O -> Cu + 2PuO2+ + 8H+
 Galvanic Cell
 The reaction always runs
spontaneously in the direction that
produced a positive cell potential.
 Potential, Work and G
 emf = potential (V) = work (J) / Charge(C)
 Faraday constant = 96,485 C/mol e-
AP Exam uses = 96,500 C/mol e-
 ∆G = -nFEo
Problem 7
Calculate the ∆Go for the reaction using Eo.
Zn2+(aq) + Cu(s) <-> Zn(s) + Cu2+(aq)
 Potential, Work and G
 ∆Gº = -nFE º
 if E º > 0, then ∆Gº < 0 spontaneous
 if E º < 0, then ∆Gº > 0 nonspontaneous
Problem 8
Vanadium(V) can be reduced to vanadium (IV) by reaction with a
“Jones reductor,” a Zn-Hg amalgam. The reactions of interest are
VO2+ + 2H+ + e- -> VO2+ + H2O Eo= + 1.00 V
Zn2+ + 2e- -> Zn Eo = -0.76 V
Calculate Eo and ∆Go for the reaction.
 Cell Potential and
Concentration
 Qualitatively - Can predict direction of change
in E from LeChâtelier.
 If the reactants, have a greater concentation, the products will be
favored; increasing Eocell
 If the products, have a greater concentration, the
reactants will be favored, decreasing Eocell
Problem 9
2Al(s) + 3Mn+2(aq)  2Al+3(aq) + 3Mn(s)
Predict if Ecell will be greater or less than Eºcell if
a) [Al+3] = 2.0 M and [Mn+2] = 1.0 M
b) [Al+3] = 1.0 M and [Mn+2] = 3.0M
 The Nernst Equation
 ∆G = ∆Gº +RTln(Q)
 -nFE = -nFEº + RTln(Q)
E = Eº - RTln(Q) nF
 @ 25oC E = Eo - 0.0592 log (Q)
n
 Always have to figure out n by balancing.
Problem 10
Calculate Ecell for a galvanic cell based on the following half reactions
at 25oC
Cd2+ + 2e- -> Cd Eo = - 0.40 V
Pb2+ + 2e- -> Pb Eo = - 0.13 V
[Cd2+] = 0.010 M and [Pb2+] = 0.100 M
(diagram)
Problem 11
Answer the following questions regarding the electrochemical cells
shown above.
a) Write the balanced net-ionic equation for the spontaneous
reaction that occurs as the cell operates, and determine the cell
voltage.
b) In which direction do anions flow in the salt bridge as the cell
operates? Justify your answer.
c) If 10.0 mL of 3.0 molar AgNO3 solution is added to the half-cell
on the right, what will happen to the cell voltage? Explain.
d) If 1.0 gram of solid NaCl is added to each half-cell, what will
happen to the cell voltage. Explain
e) If 20.0 mL of distilled water is added to both half-cells, the cell
voltage decreases. Explain
Problem 12
Answer parts (s) through (e) below, which relate to reactions
involving silver ion, Ag+. The reaction between silver ion and
solid zinc is represented by the following equation.
2Ag+(aq) + Zn(s) -> Zn2+(aq) + 2Ag(s)
a) A 1.50 g sample of Zn is combined with 250. mL of 0.110 M
AgNO3 at 25oC
i) Identify the limiting reactant. Show calculations to support your
answer
l On the basis of the limiting reactant that you identified in part(I),
determine the value of [Zn2+] after the reaction is complete.
Assume that volume change negligible.
b) Determine the value of the standard potential, Eo, for a galvanic
cell based on the reaction between AgNO3(aq) and solid Zn at
25oC.
Another galvanic cell is based on the reaction between Ag+(aq) and
Cu(s), represented by the equation below. At 25oC, the standard
potential, Eo, for the cell is 0.46 V.
2Ag+(aq) + Cu(s) -> Cu2+(aq) + 2Ag(s)
c) Determine the value of the standard free-energy change, ∆Go, for
the reaction between Ag+(aq) and Cu(s) at 25oC.
d) The cell is constructed so that [Cu2+] is 0.045 M and [Ag+] is 0.010
M. Calculate the value of the potential, E, for the cell.
e) Under the conditions specified in part (d), is the reaction in the cell
spontaneous. Justify your answer.
Problem 13
Calculate Ecell for galvanic cell based on the followng half-reactions at
25oC.
FeO42- + 8H+ + 3e- -> Fe3+ + 4H2O EO = 2.20 V
O2 + 4H+ + 4e- -> 2H2O Eo = 1.23 V
[FeO42-] = 2.0 x 10-3; [Fe3+] = 1.0 x 10-3 M; [O2] = 1.0 x 10-5 atm
pH = 5.2
 The Nernst Equation
 As reactions proceed concentrations of
products increase and reactants decrease.
 Reach equilibrium where Q = K and
Ecell = 0
0 = Eº - RTln(K)
nF
Eº = RTln(K)
nF
 Log K = nEo @25oC
0.0592
Problem 14
Calculate the equilibrium constant for the reaction in
3Cu(s) + Cr2O72-(aq) + 14H+(aq) -> 3Cu2+(aq) + 2Cr3+(aq) + 7H2O(l)
Eocell = 0.99V
Problem 15
(Diagram)
Answer the following questions that refer to the galvanic cell shown in the
diagram above.
l Identify the anode of the cell and write the half-reaction that occurs
there.
l Write the net ionic equation for the overall reaction that occurs as the
cell operates and calculate the value of the standard cell potential, Eo.
l Indicate how the value of Ecell would be affected if the concentration of
Ni(NO3)2(aq) was changed form 1.0 M to 0.10 M and the concentration
of Zn(NO3)2 (aq) remained at 1.0 M. Justify your answer
l Specify whether the value of Keq for the cell reaction is less than 1,
greater than 1, or equal to 1. Justify your answer.
 Preventing Corrosion
 Coating to keep out air and water.
 Galvanizing - Putting on a zinc coat
 Has a lower reduction potential, so it is
more. easily oxidized.
 Alloying with metals that form oxide
coats.
 Cathodic Protection - Attaching large
pieces of an active metal like magnesium
that get oxidized instead.
 Electrolysis
 Running a galvanic cell backwards.
 Put a voltage bigger than the potential and
reverse the direction of the redox reaction.
 Used for electroplating.
 Electrolytic cell- uses electrical energy to
produce a chemical change that would
otherwise not occur spontaneously
 Electrolysis - is the process that involves forcing
a current through a cell to produce a chemical
change for which the cell potential is negative
 ampere (amp) (A) = 1 coulomb of charge per
second 1 C/s
Problem 16
How many grams of copper can be reduced by applying a 3.00 A
current for 16.2 min to a solution containing Cu2+ ions?
Problem 17
a) Under standard conditions at 25oC, Zn(s) reacts with Co2+(aq)
to produce Co(s).
i) Write the balanced equation for the oxidation half reaction.
ii) Write the balanced net-ionic equation for the overall reaction.
iii) Calculate the standard potential, Eo, for the overall reaction at
25oC.
b) At 25oC, H2O2 decomposes according to the following equation
2H2O2(aq) -> 2H2O(l) + O2(g) Eo = 0.55 V
i) Determine the value of the standard free energy change, ∆Go, for
the reaction at 25oC.
ii) Determine the value of the equilibrium constant, Keq, for the
reaction at 25oC.
iii) The standard reduction potential, Eo, for the half reaction
O2(g) + 4H+(aq) + 4e- -> 2H2O(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, Eo for the half
reaction below.
O2(g) + 2H+(aq) + 2e- --> H2O2(aq)
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 CuSO4(aq) for a period of 1.00 hour.