Review: Degrees of Freedom

 Do you have enough information to solve the problem?

 Does problem have unique solution?

 ndf = nunknowns – nindep. eqs.

 If ndf = 0, problem can be solved, unique solution
 If ndf > 0, more unknowns, underspecified, infinitely many solution
 If ndf < 0, more indep. eqs., overspecified, no solution
Indep. Equations, indep. Species and indep. reactions:

Are these indep.?

No, because

Now consider the reactions

Are these indep.?

No, because
Example:

 N2 and O2 are in same ratio wherever they appear, not indep.

 So, in DoF analysis, only two indep. molecular species instead of 3

 Similarly atomic nitrogen and atomic oxygen in same ratio, and

atomic chlorine and atomic carbon are in same ratio
 So, only two indep. Atomic species
 Balances on Reactive Processes:
Example
Molecular species balance:

▪Each indep. reaction adds a degree of freedom to the system

▪Because of the generation or consumption of species

Atomic species balance:

▪No additional DoF contributed by the reactions

▪Because atomic species can neither be generated nor consumed
in chemical reactions (except nuclear reactions)
Extent of Reaction:
 2
+1
-3
-0
-0
0
Selection of method:
No hard and fast rule, only general guidelines
 Problem:
Methanol is produced by reacting carbon monoxide and hydrogen.

CO + H2 CH3OH

A fresh feed stream containing CO and H2 joins a recycle stream and the combined stream is fed to a reactor.
The reactor outlet stream flows at a rate of 360 mol/min and contains 10.6 wt% H2, 64 wt% CO, and 25.4 wt%
CH3OH. (Notice that those are percentages by mass, not mole percents.) This stream enters a cooler in which
most of the methanol is condensed. The liquid methanol condensate is withdrawn as a product, and the gas
stream leaving the condenser (which contains CO, H2, and 0.5 mole % uncondensed CH3OH vapor) is the
recycle stream that combines with the fresh feed. Convert wt% to mole %, Sketch a properly labeled flow
chart, perform degrees of freedom analysis, determine the production rate of liquid methanol, determine the
molar flow rates of CO and H2 in the fresh feed.