Thermodynamics (CHE 330)

Winter 2016
HW #12
Due: Friday, April 15 by the start of class
Guidelines:
1. On the first page, in the upper right hand corner, write:
Your Name
Your Discussion Section Number and GSI Name
Problem Set and Due Date (format the date using the ISO 8601 convention
ofYYYY-MM-DD, e.g., 1776-07-04 for the 4thof July, 1776)
Students you have studied with while working on this assignment
2. Use 8.5 11 inch paper with straight edges (not paper torn from a spiral bound
notebook). You are welcome to format your solutions digitally; however, this is not
mandatory.
3. Number all pages (e.g., 1/5, 2/5, etc.), put your name on each page, and staple the pages
together do not paper clip or fold the corners.
4. Use a ruler (or computer application) when making sketches and drawings.
5. Please be neat and write legibly. If your work is illegible, the graders are instructed to
assume that it is incorrect.
Problem 1

The Clean Air Act was last amended in 1990, which requires EPA (Environmental Protection
Agency) to set National Ambient Air Quality Standards (NAAQS) for pollutants such as nitric oxide
(NO) that are considered harmful to public health and the environment. As an environmental
engineer at a power plant, you are asked to reduce NO from the exhaust. You propose the
following gas phase selective non-catalytic reduction (de-NOx) reaction to dispose of nitric oxide:
4NO + 4NH 3 + O2 4N2 + 6H 2 O
where ammonia is the product of urea hydrolysis. The equation of state for these components is
PV
given as = 1+ BP , where BNO = 68 108 , BNH3 = 7.4 108 , BO2 = 1.2 10 8 , and,
RT
BN2 = 1.1108 Pa 1 .

If the reaction takes place at 327C and 101.3 kPa, solve the following to support your proposal:

( )
a. Show that = exp BP for pure components under the proposed reaction conditions.
Hint: you need to set a reference state for the pressure.

b. Calculate H2O at the proposed reaction conditions.

c. What is the chemical equilibrium constant at this temperature? Hint: you should use the
tables in Appendix A.II and A.IV for the molar heat capacities, enthalpy, and Gibbs energies
of formation.

d. You set up a pilot plant to demonstrate the feasibility of the proposal. The feed to the
reactor contains 9 mol% O2, 36 mol% NO, and 55 mol% NH3. The operating pressure of
the reactor is 101.3 kPa. Evaluate the equilibrium percent conversion of NO.
(Assumptions: you may approximate the fugacity coefficients in the mixture by their pure
species fugacity coefficients, and you may work with assumption of 4 moles of NO, 6 moles
NH3, and 1 mole of O2 at initial condition.)

e. If a higher conversion is desired to meet NAAQS, should you increase or decrease the
operating pressure? Why? Also, should you increase or decrease the operating temperature?
Why?

f. If you were to add some gaseous inert material in the feed stream, would the equilibrium
conversions increase or decrease? Why? What if, instead of the inert gas, you added some
superheated steam? Why?
Problem 2

Internal combustion engines are used to burn hydrocarbon fuels, but this often results in
simultaneous NOX formation. NOX gases are undesired because they react in the atmosphere to
produce acid rain and smog. Catalytic convertors are used to capture these gases in the exhaust of
automobiles. You are doing research to understand this process. The formation of nitrogen dioxide
follows this reaction:
N2 ( g ) + 2O2 ( g ) 2NO2 ( g )
Assume that the reaction mixture behaves as an ideal gas with a molar heat capacity of
C P* = a + bT + cT 2 + dT 3 + eT -2 J/mol for the relevant temperature range. Assume no other
equilibrium reactions occur simultaneously.

Species a b 103 c 107 d 109 e 105

N2 (g) 0 0 27.318 6.23 -9.50 - -
O2 (g) 0 0 28.167 6.30 -7.50 - -
NO (g) 86.58 kJ/mol 90.25 kJ/mol 27.034 9.87 -32.2 0.365 -22.9
NO2 (g) 51.3 kJ/mol 33.2 kJ/mol 22.929 57.11 -351.9 7.866 -

a. Calculate , , and Ka at 298.15 K and 1 atm.

b. Calculate Ka at 1200 K and 150 bar.

c. Starting with 2 moles of nitrogen and 4 moles of oxygen, the reaction is conducted at 1200
K and 150 bar. Calculate the molar compositions at equilibrium.

d. After equilibrium is attained at 1200 K and 150 bar, you increase the temperature to 1500 K.
Would you expect to increase the mole fraction of nitrogen dioxide by doing so? Why or
why not?

e. After equilibrium is attained at 1200 K and 150 bar, a reactor malfunction causes the
pressure to drop to 10 bar. What happens to the mole fraction of nitrogen dioxide when
equilibrium is re-established at 10 bar? Explain.

f. Your colleague encourages you to introduce 2 moles of argon into the reactor after reaching
equilibrium while keeping temperature and pressure constant at 1200 K and 150 bar. If you
take your colleagues advice, what would happen to the conversion to nitrogen dioxide?
Justify briefly.

g. If you were instead investigating the production of nitric oxide, NO, in our reactor at 1200
K and 150 bar, what would be the effect of adding 2 moles of argon on the equilibrium
conversion to NO?
Problem 3

You would like to assess the feasibility of producing hydrogen for energy storage using the following
reaction mechanism. Water reacts with graphite to form carbon monoxide and hydrogen (1), and
the carbon monoxide formed reacts with water to form more hydrogen gas and carbon dioxide via
the water-gas shift reaction (2). Determine the equilibrium composition when pure water vapor is
passed over a hot carbon bed maintained at:

a. 1 bar and 500 K; and

b. 1 bar and 2000 K.

c. At which of the above temperatures would you run the reaction at in order to maximize the
amount of hydrogen produced?

(1) C (s) + H 2O ( g ) CO ( g ) + H 2 ( g )

(2) CO ( g ) + H 2O ( g ) CO2 ( g ) + H 2 ( g )
Use the following reaction data and assume that graphite is in excess:

Reaction (500 K, kJ mol ) ( 2000 K, kJ mol )

1 64.4 -136.3
2 -25.1 0.7