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    HW1

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    The document provides instructions and thermodynamic problems for a homework assignment. It includes: 1) Instructions to read a chapter, work specific textbook problems, and additional practice problems. 2) 9 multi-part thermodynamic chemistry problems involving calculations of Gibbs free energies, equilibrium constants, and equilibrium concentrations/pressures under various conditions. 3) Thermochemical data needed to solve the problems, such as standard Gibbs free energies of formation.

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    HW1

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    The document provides instructions and thermodynamic problems for a homework assignment. It includes: 1) Instructions to read a chapter, work specific textbook problems, and additional practice problems. 2) 9 multi-part thermodynamic chemistry problems involving calculations of Gibbs free energies, equilibrium constants, and equilibrium concentrations/pressures under various conditions. 3) Thermochemical data needed to solve the problems, such as standard Gibbs free energies of formation.

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    The document provides instructions and thermodynamic problems for a homework assignment. It includes: 1) Instructions to read a chapter, work specific textbook problems, and additional practice problems. 2) 9 multi-part thermodynamic chemistry problems involving calculations of Gibbs free energies, equilibrium constants, and equilibrium concentrations/pressures under various conditions. 3) Thermochemical data needed to solve the problems, such as standard Gibbs free energies of formation.

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    Download as PDF, TXT or read online from Scribd
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    157 views4 pages

    HW1

    Uploaded by

    blvckops890
    The document provides instructions and thermodynamic problems for a homework assignment. It includes: 1) Instructions to read a chapter, work specific textbook problems, and additional practice problems. 2) 9 multi-part thermodynamic chemistry problems involving calculations of Gibbs free energies, equilibrium constants, and equilibrium concentrations/pressures under various conditions. 3) Thermochemical data needed to solve the problems, such as standard Gibbs free energies of formation.

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    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?

    1
    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.

    2
    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

    3
    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

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