1.

Mole Balances
o The Rate of Reaction, -rA
o The General Mole Balance Equation
o Continuous Flow Reactors
- CSTR (Continuous-Stirred Tank Reactor)
- PFR (Tubular Reactor)
- PBR (Packed-Bed Reactor)
o Industrial Reactors
0. Chemical Identity

o Reaction
- When a chemical species has lost its chemical
identity
o Identity of a chemical species
- The kind, number, and configuration of that species’
atoms
• decomposition CH3CH3 → H2 + CH2=CH2
• combination N2 + O2 → 2NO
• isomerization C2H5CH=CH2 → CH2=C(CH3)2

2/21/2011 2011 Spring 2

1. Reaction Rate I (p.2)
o Reaction Rate
- The rate at which a species looses its chemical
identity per unit volume
A→B
rA = the rate of formation of species A per unit
volume
-rA = the rate of a disappearance of species A per unit
volume
rB = the rate of formation of species B per unit
volume
☞ For a catalytic reaction, we refer to -rA', which is the
rate of disappearance of species A on a per mass
of catalyst basis

2/21/2011 2011 Spring 3

1. Reaction Rate II
o Reaction Rate [Example]
A→B
- If B is being created at a rate of 0.2 moles per liter
per second, ie, the rate of formation of B is,
rB = 0.2 mole/l/s
then A is disappearing at the same rate:
-rA = 0.2 mole/l/s
the rate of formation of A is
rA = -0.2 mole/l/s

2/21/2011 2011 Spring 4

1. Reaction Rate III
o Is sodium hydroxide reacting?
- Reaction rate definition, rA = dCA/dt
• only holds for constant volume batch system
carried out to obtain chemical reaction rate data
- Sodium hydroxide and ethyl acetate are
continuously fed to a rapidly stirred tank in which
they react to form sodium acetate and ethanol:
NaOH + CH3COOC2H5 → CH3COONa + C2H5OH

2/21/2011 2011 Spring 5

1. Reaction Rate IV
o Consider species j
- rj is the rate of formation of species j per unit volume
[e.g. mol/dm3*s]
- rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)
- rj is independent of the type of reaction system
(batch, plug flow, etc.)
- rj is an algebraic equation, not a differential equation
o Examples of other rate laws
k1C A
 rA   rA  k  rA  k1C A
1 k 2C A

2/21/2011 2011 Spring 6

1. Reaction Rate V
o Self test
- The convention for rates of reaction
A + 2B → 3C
in which the rate of disappearance of A is 5 moles of
A per dm3 per second at the start of the reaction.
- At the start of the reaction
(a) What is -rA?
(b) What is the rate of formation of B?
(c) What is the rate of formation of C?
(d) What is the rate of disappearance of C?
(e) What is the rate of formation of A, rA?
(f) What is -rB?
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2. General Mole Balance Equation (p.8) I
o In a given boundary system
- FA0= Entering molar flow rate of A (mol/time)
FA= Exiting molar flow rate of A (mol/time)
GA= Rate of generation(formation) of A (mol/time)
V = Volume (vol e.g. m3)
rA= rate of generation(formation) of A (mole/time•vol)
NA= number of moles of A inside the system Volume
V (mols)

2/21/2011 2011 Spring 8

2. General Mole Balance Equation II
o Self Test
1. The rate law
(a) is a differential equation T F
(b) relates reaction rate and concentration of
reacting species T F
(c) is a function of temperature; T F
2. The rate of formation of species A is per unit volume
(a) rA T F
(b) -rA T F
(c) the rate of generation of species A per unit
volume T F
(d) r'A T F
(e) none of the above T F
2/21/2011 2011 Spring 9
2. General Mole Balance Equation III
3. At a particular time t, the rate of formation of B in
the reaction, rB, is 10 mole/dm3*min. Which of the
following are true? A → B
a. The rate of disappearance of B is -10 moles/dm3*min.
b. The rate of formation of A is -10 mole/dm3*min.
c. The rate of disappearance of A is 10 moles/dm3*min.
d. rA = -10 moles/dm3*min
e. -rA = 10 moles/dm3*min
f. -rB = -10 moles/dm3*min
g. Some of the above
h. All of the above
i. None of the above
j. A will disappear faster if a magician is present
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3. Batch Reactors I
o Batch Reactors
- Used for a small-scale operation,
• testing a new process not fully developed
• manufacturing expensive products
• processes difficult to convert to
continuous operation
- Advantages
• high conversion
- Disadvantages
• high labor cost per batch
• variability of product quality
• difficulty of large-scale production
2/21/2011 2011 Spring 11
3. Batch Reactors II
dN j
Fj 0  Fj   rj dV 
V
o Reaction rate
dt
- Neither inflow not outflow
V dN A
 rA dV 
dt
- Rxn rate is uniform throughout the reactor volume
dN A
 rAV
dt
- For isomerization of species A
A→B

2/21/2011 2011 Spring 12

3. Batch Reactors III
o Reaction time
- Time t1 to change NA0 → NA1, (Generally NA0 > NA1)
dN A
 rAV
dt
- Rearranging dN A
dt 
rAV
- Integrating

dN A

N A0
t1 
N A1  rAV

2/21/2011 2011 Spring 13

4. Continuous Flow Reactors I
o Continuous-Stirred tank Reactor 1
- CSTR, vat, or Backmix reactor
- Primarily for liquid phase reactions
- Operated at steady state (perfectly mixed)
• T, Cj, rj inside CSTR is uniform
☜ residence-time distribution study for
highly non-ideal mixing system

2/21/2011 2011 Spring 14

4. Continuous Flow Reactors II
o Continuous-Stirred tank Reactor 2
- General mole balance dN j
Fj 0  Fj   rj dV 
V

dt
- Operated at st-st
dN A
0
V

dt  rA dV  VrA

- Design equation for CSTR

V dN A FA0  F A
FA0  FA   rA dV  or V 
dt  rA

- With volumetric flow rate v, FA = CA • v

2/21/2011 2011 Spring 15
4. Continuous Flow Reactors III
o Tubular Reactor 1
- A cylindrical pipe normally operated at st-st
- Used most often for gas-phase rxn
- Reactants are continually consumed as they flow
down the length of the reactor
- Plug flow along pipe

2/21/2011 2011 Spring 16

4. Continuous Flow Reactors IV
o Tubular Reactor 2
- General mole balance dN j
Fj 0  Fj   rj dV 
V

dt
- Operated at st-st
dN A
0
dt
V
- Design equation for PFR
FA0  FA   rA dV  0
- Differential w.r.t V dFA
0  rA
dFA dV
- Or  rA
dV
2/21/2011 2011 Spring 17
4. Continuous Flow Reactors V
o Tubular Reactor 3
- Rearranging and integrating between
V = 0, FA = FA0
V = V1, FA = FA1
dFA FA 0 dF
V1   
FA1
A
FA 0 r FA1  r
A A

2/21/2011 2011 Spring 18

4. Continuous Flow Reactors VI
o Pack-Bed Reactor 1
- Involving fluid-solid heterogeneous rxns
• the rxn takes place on the surface of the catalysts
• rxn rat is based on mass of solid catalyst W (rather
than on volume V
-r’A = mol A reacted/s • g cat.

2/21/2011 2011 Spring 19

4. Continuous Flow Reactors VII
o Pack-Bed Reactor 2
- General mole balance dN j
Fj 0  Fj   rj dV 
V

dt
- Operated at st-st
dN A
0
dt
V
- Design equation for PBR FA0  FA   rA' dW  0
dFA
- Differential w.r.t W 0  rA'
dW
dFA
- Or  rA'
dW
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4. Continuous Flow Reactors VIII
o Pack-Bed Reactor 3
- Rearranging and integrating between
W = 0, FA = FA0
W = W1, FA = FA1

FA1dFA FA 0 dF
W1    FA1  r ' A
A
FA 0 r ' A

2/21/2011 2011 Spring 21

5. Industrial Reactors I
o Liquid-Phase Reactions 1
- Semibatch reactors
• T control by regulation of
feed rate
• minimizing side rxns to
maintain conc of one of the
reactants
• 2-phase rxns where gas
bubbled out

2/21/2011 2011 Spring 22

5. Industrial Reactors II
o Liquid-Phase Reactions 2
- CSTRs
• intense agitation required
• stand alone or in series
• relatively good T control
• the smallest conversion ⇒ large size necessary

2/21/2011 2011 Spring 23

5. Industrial Reactors III
o Gas-Phase Reactions 1
- PFRs
• easy to maintain (no moving parts)
• the highest conversion
• difficult T control ⇒
hot spot if exothermic rxn

2/21/2011 2011 Spring 24

5. Industrial Reactors IV
o Gas-Phase Reactions 2
- PBRs
• basically the same to PFRs with solid catalyst
particles
• the catalyst is troublesome to replace
• channeling of the gas flow ⇒ dead zone

2/21/2011 2011 Spring 25

5. Industrial Reactors V
o Gas-Phase Reactions 3
- Fluidized-Bed Reactors
• analogous to CSTR – well mixed, even T
distribution
• approximately modeled as a CSTR [for exact
design, it need customizing]
• often high cost of reactor and
catalyst regeneration

2/21/2011 2011 Spring 26