10.

37 Chemical and Biological Reaction Engineering, Spring 2007

Prof. William H. Green
Lecture 11: Non-isothermal Reactors, equilibrium limitations, and stability

This lecture covers: Derivation of energy balances for ideal reactors; equilibrium
conversion, adiabatic and non-adiabatic reactor operation.

Non-isothermal Reactors
dN i N streams N rxns

= Fi ,m + Vcv i ,l rl
dt m =1 l =1

stoichiomet
stoichiometric
ric
coefficient

rl - depends on concentration
-T
- catalyst

dU cvtotal dV N streams

+ P cv = H mconc (Tm ) Fmtotal + Q +Ws + (other energy terms)

dx dt m=1

flow work
extensive intensive heat
shaft
do work Ws negative
work
work
expansion
work

If small control volume, pressure constant.

P1 P2 P1 P2

other control
In Vcv1 has a volumes
fixed P

Figure 1. Schematic of a PFR with small control volumes, each with a fixed P.

PFR has many small control volumes, each with its own constant P.

For isothermal Q adjusted to keep T constant

Practical have big cooling bath
or just operate at a particular temperature found after reactor
built
not a good strategy, for design we want to know ahead of
time
before assumed uniform T, actually have hot spots

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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Where is T? In U cv and rl (T ) .
total

dU cvtotal dU cvtotal dT N streams dU cvtotal dN i

= +
dt dT dt i=1 dN i dt

dN i
heat capacity intensive substitute for
of system contribution of dt
each species

dY
Want = F (Y )
dt
Assume ideal mixtures
U cvtotal N iU i (Tcv )

extensive intensive

dU cvtotal
= U i (Tcv )
dN i
If P=Constant (Isobaric)

dH total d (U + PV ) dU dP dV
= = + V +P
dt dt dt Ndt dt
0
total
dU dV
+ P cv
cv

dt 
 dt

total
dH
dt
Assume isobaric, all ideal mixtures, neglecting K.E., P.E., other energies

N species dTcv N streams N species

i p ,i N C = Fi ,m ( H i (Tm ) H i (Tcv ) )
i dt m i
N streams N rxns

H (T
i l
i cv )Vcvi ,l rl (Tcv ) + Q +Ws

i
i ,l H i (Tcv ) H rxn (Tcv )
l
stoichiometric coefficient

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 11

Prof. William H. Green Page 2 of 4

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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 N streams N rxns

H (T
i l
i cv )Vcvi ,l rl (Tcv ) = Vcv rl (Tcv ) H rxn (Tcv )
l l

Assume

Q UA(Ta Tcv ) (conduction)

coolant
heat reactor
transfer
coefficient

area of
contact

W s 0 (As a stirrer, heat negligible)

If designing engines W s 0 .

Now just put into MATLAB and solve

Chapter 8 in Fogler lots of special case equations

be careful of assumptions

Special case: Start up CSTR to a steady state

want to know ultimate T

N streams N species
dTcv
= 0 Fi ,m ( H i (Tm ) H i (Tcv ) ) Vcv rl H rxn +UA(Ta Tcv )
dt m i l

All depend on TCV

When we reach steady state, no more accumulation

FA, in FA, out + rAV = 0 at steady-state

See Fogler: 8.2.3

If just one reaction, one input stream, one output stream, and the system is at
steady-state:

UA(T Ta ) + Fi , input C p , i (T Tin )

XA =
FAo (H rxn )

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 11

Prof. William H. Green Page 3 of 4

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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In this special case, conversion and T linear
1 reaction making heat as product is made.
When H rxn = (-) Exothermic, reactor is hotter than cooling reactor (heat transfer
important)
(+) Endothermic, reactor must be heated so that reaction will run

G (T ) (H rxn )(rA V FAo ) Generation

Fi , in UA
R(T ) = C p, i 1 + (T Tc )
FAo 

Fi, inC p , i


K

Heat removal

K =0 Adiabatic
K = Big Cooling

KTa + Tin
Tc =
1+ K

R(T ) linear with T

G (T ) constant at high T
- not linear with T

Three steady-state solutions

R(T )
cool
a lot H rxn

G (T )

T
Figure 2. Graph of G(T) versus T. Three steady-state points are shown where R(T)
intersects with the heat of reaction.

With multiple steady states must consider stability.

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 11

Prof. William H. Green Page 4 of 4

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
Downloaded on [DD Month YYYY].