engrd 2190 – lecture 4 - cornell university
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Concept: Process Design – Devising Chemical Reaction Cycles
Context: Producing CH4 from CO2 and thermal energy.(exercise 2.30 – solution is posted)
Defining Questions: Why 2 reaction steps for N2H4 synthesis by green chemistry?
2NH3 + H2O2 N2H4 + 2H2O (Lecture 2)Why 9 steps between landings in Olin Hall stairwalls?
Read Chapter 2, pp. 42-48.
EngrD 2190 – Lecture 4
Homework due Friday 9/10:Problem Redefinition: 2.39, 2.41, and 2.50.
submit all three short answers on a single page.Process Analysis: 2.7.Process Design: 2.25 (A)&(B) only, 2.28.
Read process design guidelines on p. 57.See table of physical data on pp. 86-7.
Submit after lecture or deliver to EngrD 2190 mailboxin the hallway between 130 and 132 Olin Hall. Not to my mailbox.
Work in teams. Submit one solution set per team.
Homework is your chief means of assessing your command of the material.
Do not copy from other sources, such as graded homework and postedSolutions from previous years.
Do not use past solutions to check your answers. Process analysisis part of process Design. You should be developing methods of assessing your designs.
endothermicheat +
How much heat? Reaction temperature?
Thermodynamics: Given 2 chemical states,the relative amounts at equilibrium are determined bythe difference in Gibbs energy and the temperature.
A B energyB
AABrxn GGG
gas constant: PV = nRTR = 8.314 J/(molC)
p.37. 2.4,eqn A ofamount B ofamount :mequilibriuat /rxn RTGe
deductive,verbalstatement
inductive,visualexample
C and O are reduced.Need to couple with a oxidation reaction.
What to oxidize?Metals release energy when oxidized!
Proposal:Couple the reduction of H2O with the oxidation of Fe. Also a
goodreducingagent!
Do the three reactions form a cycle?Is the net sum CO2 + 2H2O CH4 + 2O2?
1. Start with reaction 2; it has the correct stoichiometriccoefficient for CO2.
2. Reaction 2 needs 4H2 Reaction 1 must produce 4H2.
4/3( )
3. Reaction 1 produces 4/3 Fe2O3 Reaction 3 must reduce4/3 Fe2O3
2/3( )
Net sum is CO2 + 2H2O CH4 + 2O2!
Are the reactor temperatures practical?
solid solid + gasReaction favored by high temperature.
% conversion
120 45 99.998200 83 99.999999
3000 76 94.12500 62 6%
too low
FeCl3 (400)
Need a reducing agent less severe than Fe.
(kJ/mol)formationH
0
200
400
600
800
CH4 + 2O2 (set to zero)
CO2 + 2H2O (802)
+802 kJ/mol
Fe (set to zero)
Fe2O3 (824)
1st guess:824 kJ/mol
too large
FeO (272)FeCl2 (342)
2nd guess:82 kJ/mol
New Proposal: Couple the reduction of H2O with the oxidation of FeCl2.
4( )
2( )4( )
CO2 + 2H2O CH4 + 2O2
% conversion
1500 4 99.3200 83 99.99925 38 99.9999
800 72 99.97
practicaltemperatures!
All ~100.%Assume all rxns
go to completion.
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