MSE 2010, 2160, and 2170

Homework #1
Due 9-1-10

Read chapter 16. Work problems 2, 3, 4, 5, and 16 from Chapter 16 in the textbook
(Note that some problems are not the same in the hardbound copy so use the problems as
given in the paperback edition (file is added under homework helps). In addition, work
the following problems from previous tests (Note that there is a handout on
thermodynamics under “lecture notes” that can be downloaded that will aid you on the
problems shown below).

1. Commercial hydrogen is produced by a steam reforming reaction combined with a

water-shift reaction to give the overall reaction, as shown below.
CH4 + H2O  CO + 3H2 Reforming reaction
CO + H2O  CO2 + H2 Water-shift reaction
CH4 + 2H2O  CO2 + 4H2 Overall reaction

The following free-energy data are valid at the reaction temperature.

Reaction Gof1000K (J/mole)
C + 2H2  CH4 19,572
H2 + 0.5O2  H2O -192,713
C + 0.5O2  CO -200,261
C + O2  CO2 -395,810
o
a) Calculate G f (in kJ/mole) at 727C for the overall reaction.
b) Give the numerical value of the equilibrium constant for the overall reaction at
1000K.
c) The total pressure is the sum of the partial pressures (P=PCH4+PH2O+PCO+PCO2
+PH2). Given that PCH4=8.93x10-3 atm., PCO=1.43x10-1 atm., and PCO2=5.14x10-2 atm.,
calculate what percent of the overall volume of gas is H2 under equilibrium conditions at
atmospheric pressure.

2. High-purity zinc is produced by an electrochemical process called electrowinning

where Zn is plated out on an aluminum electrode by applying a voltage to drive the
reaction in a direction opposite to what it would go without the external driving force.
The overall reaction is given by ZnSO4 + H2O  Zn + H2SO4 + 0.5O2, where the oxygen
is evolved such that it has a partial pressure of 1 atmosphere. Assume that the zinc
sulfate, water and sulfuric acid all have unit activity (i.e., K=1).
a) What is G, at room temperature, for the reaction if Go298K for ZnSO4 is –871.5
kJ/mol, Go298K for water is –237.1 kJ/mol, and Go298K for sulfuric acid is –689.9
kJ/mol?
b) The two half-cell electrowinning reactions are: Zn2+ + 2e-  Zn Vo= -0.763V and
0.5O2 + 2H+ + 2e-  H2O Vo= 1.229V
If zinc is the cathode, what minimum voltage must be applied to the electrochemical cell
to produce metallic zinc at 60C if the concentration of Zn2+ is 1M and the concentration
of H+ is 1.75M?
c) Why is this reaction is carried out commercially at 60C rather than 25C?

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3. Sodium hydroxide and chlorine gas are made commercially in an electrochemical
“chlor-alkali” cell that uses a polymeric membrane which allows sodium ion transfer
through the membrane. Chlorine gas is produced in the anode compartment and
hydrogen gas evolves in the cathode compartment (the polymer membrane does not allow
the chlorine and hydrogen gases to mix). Aqueous ionic solutions make up both cell
compartments. The NaCl concentration in the anode compartment is 35 wt. % and the
NaOH concentration in the cathode compartment is 40 wt. %. The sodium chloride and
sodium hydroxide solutions have densities of 1.25 g/cc and 1.39 g/cc, respectively, at
350K. The two half-cell reactions are given as:
2Cl-  Cl2 + 2e- (anode)
2H2O + 2e-  H2 + 2OH- (cathode)
2Cl- +2H2O  Cl2 + H2 + 2OH- (net reaction)
Since two Na+ are on both sides of the reaction, the net reaction can also be written as
2NaCl +2H2O  Cl2 + H2 + 2NaOH (overall reaction)
The cell operates at 350K, with Go (kJ/mol) values at this temperature of -379.246
(NaCl), -229.059 (H2O), and -371.620 (NaOH).
a) Calculate Vo at this temperature for the overall reaction.
b) Calculate V for the net reaction if the partial pressure of H2 and Cl2 are each one
atmosphere (Hint: Vo for the net reaction is the same as for the overall reaction).
c) Why is a cell voltage of 3.2 V used to produce NaOH and Cl2 by this process?

4. Aluminum is produced electrochemically in a Hall cell, with both graphite cathodes

and anodes. The overall cell reaction involves the reduction of aluminum oxide to
aluminum metal and oxygen. The reaction occurs in molten cryolite (Na3AlF6) by
dissolving alumina (Al2O3) in an ionically conductive liquid such that Al is produced at
the cathode and oxygen evolves at the anode. Assume that the activity of molten
aluminum is 1 and that the activity of alumina dissolved in the cryolite is 0.1. The
overall cell reaction is simply Al2O3 -> 2Al + 1.5O2. The reaction occurs slightly above
1000oC by supplying a voltage to drive the reaction, which is thermodynamically
unfavorable. Use the free energy data given below, and the knowledge that six electrons
are involved in the electrochemical reactions to answer the questions below:
Compound Gof1300K (kJ/mol)
Al2O3 -1,262.044
CO2 -396.079
a) Calculate the voltage necessary to drive the reaction forward if the partial pressure of
oxygen at the anode of the Hall cell is 1 atmosphere and the anode is inert (i.e., anode
does not react with oxygen).
b) In reality, the graphite anode is not really inert and the overall reaction is given by:
Al2O3 + 1.5C  2Al +1.5CO2. What voltage is required to make Al with a consumable
graphite anode if PCO2 =0.13 atmosphere at the anode?
c) The actual electrode reactions are:
2Al2OF62- + 4F-  4AlF4- + O2 + 4e- Reaction 1
AlF4- + 3e-  Al + 4F- Reaction 2
Identify the cathodic reaction (Reaction 1 or Reaction 2) and give the reason for your
answer.

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5. Use the following free energy data for the reaction C + 2H2  CH4 to answer the
questions below: Temperature (K) Gof (kJ/mol)
298 -50.7
800 -2.1
1300 52.7
Carbon and hydrogen react readily to form methane at low temperatures, but not at high
temperatures. Your boss is worried about having flowing hydrogen in his graphite
furnace at 1000oC because he knows that carbon and hydrogen react to form methane,
which would consume the heating element in the furnace. The furnace is used with gas
flowing at atmospheric pressure.
a) Calculate what the partial pressure of hydrogen must be in order for hydrogen to react
with the graphite heating element at 1027oC, assuming that H2 and CH4 are the only gases
flowing through the furnace.
b) Should your boss be worried about consuming his graphite furnace by flowing H2
through his furnace at 1000oC? Why?

6. One limitation of cemented carbides (WC-Co cutting tools) is their poor oxidation
resistance. Use the Gibb’s free energy values given below to answer the following
questions:
a) Write a balanced equation describing the oxidation of tungsten carbide (WC).
b) What is Gof for this reaction at 1300K?
c) Calculate the value of the equilibrium constant at 1300K.
d) If tungsten carbide were put inside a non-reactive vessel initially filled with O2 and
heated in such a manner as to limit further gases from entering the chamber, which was
then heated to 1300K with a bleed-off valve to allow a total pressure of 1 atmosphere to
be maintained, what would be the equilibrium partial pressure of oxygen in the vessel at
1300K?
e) What prevents tungsten carbide from being oxidized in air at room temperature?

Compound Phase Gof1300K (kJ/mol)

WC Solid -35.1
WO3 Solid -513.4
CO Gas -226.5

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7. Right out of school you accept a job with the environmentally friendly company Clean
Air, Inc. designing diesel engines. They want you to design a hotter engine since your
boss thinks that increasing the combustion temperature in the engine from 1000K to
1500K will decrease the amount of NO formed (NO is harmful environmentally since it
is metastable in the atmosphere and can be transformed to NO2 and other toxic
compounds). You go to the literature and find out that the combustion reaction is
N2 + O2 —> 2NO
where both reactants and products are gases. Go for NO at 1000K is 77.7 kJ/mol and is
71.4 kJ/mol at 1500K. The partial pressure of nitrogen gas is 0.69 and that of molecular
oxygen is 0.06 in the combustion gas (there is also 17 % CO and 8 % H2O in the
combustion gas which do not enter into the calculation). Calculate the equilibrium
concentration of NO at both temperatures. Is your boss right?

8. SiC can be formed by the carbothermal reduction of SiO2 where the reactants are silica
(SiO2) and carbon (C) while the products of the reaction are silicon carbide and carbon
monoxide. Write a balanced equation for the reaction. Use the thermodynamic data
below to determine the equilibrium partial pressure of CO at 1800K:

Compound Form Go1800K (kJ/mol)

SiO2 solid -590.4
SiC solid -55.8
CO gas -269.2

9. Alkaline batteries operate in a potassium hydroxide liquid electrolyte which allows

current to flow at room temperature. The two half-cell reactions, written as reduction
reactions, are given below along with their standard potentials in the alkaline solution.

Zn(OH)2 + 2e- → Zn + 2OH- Vo = -1.25 V

2MnO2 + 2H2O + 2e- → 2 MnO(OH) + 2OH- Vo = 0.30 V

a) What material is the anode in an AA battery?

b) What is the valence of the cathode cation after reduction?
c) Write the overall reaction for the battery.
d) Calculate the value of Go (in kJ/mol) for the overall reaction.
e) Calculate the value of the equilibrium constant at room temperature.
f) Calculate Go for MnO(OH) formation at room temperature. (Hint: Assume that
Zn(OH)2 decomposes to ZnO and H2O without changing the voltage (Vo) of the overall
reaction).

Compound Go298K (kJ/mol)

MnO2 -465.138
H2O -237.141
ZnO -320.476