122 Rate Laws and Stokhiomatry Chap.

Here C, = N A I V, and C, = & 1 Vo. Substituting Equations (E3-6.2) and

(E3-6.3) into the rate law, we obtain the rate of disappearance of A as a func-
tion of conversion:

2. For a flow system.

Here C, = FAlv and Ca = Fs/u with v = vU ( I t. m. Consequently. we can
and (E3-6.6) ~ntoEquation (B-6.9) 10 oblain
substitute Equations (E3-6.5)

- r , = J - ( X ) for a
flow reactor

As expected, the dependence of reaction rate on conversion for a constant-

volume batch system [i.e., Equation (E3-6.lo)] is different than that fur a Row
system [Equation (E3-6.11)] for gas-phase reactions.
I f we substitute the values for CAO,KC, E, and k = 0.5 min-' in Equation
(E3-6.11). we obtain -rA solely as a function o f X for the flow system.

We can now form our Levenspiel plot.

W e see (I/-r,) goes to infinity as X approaches X,.

I Figure E3-6.1 Levencpiel plot Tor a flow %!\tern.

 5ec. 3.6 Flow Systems 123

(d) CSTR volume. Just for fun let's calcuIate the CSTR reactor voIume nec-
essary to achieve 80% of the equilibrium conversion of 50% {i.e., X = 0.8X,)
X = 0.4 for a feed rate of 3 rnollmin.

1 The CSTR volume necessary to achieve 40% conversion is 1.7 1 m3.

Closure. Having completed this chapter you should l x able to write the
rate law in terns of concentration and the Arrhenius temperature depen-
dence. The next step is to use the stoichiometric table to write the con-
centrations in terms of conversion to finally amve at a relationship
between the rate of reaction and conversion. We have now completed the
fiat three basic building blocks in our algorithm to study isothermal
chemical reactions and reactors.
The CRE Algorithm
mole Balance. Ch 1
.Rate Law. Ch 3
Ch 3
mSto~chiorneiry. S toichiornetry
*Combine. Ch 4
'Evaluate, Ch 4
' E n e ~ yBalance. Ch 8 Rate Law

I Mole Balance 1)
In Chapter 4. we will focus on the curnbine and evaluation building
blocks which will then complete our algorithm for isothermal chemical
reactor design.
 Rate Laws and Stoichiometry Chao.

SUMMARY

PART 1

1. Relative rates of reaction for the generic reaction:

The relative rates of reaction can be written either as

1. Re(rc~criono d r is determined from experimental observation:

The reaction in Equation (S3-3)is a order with respect to species A and

order with respect to species B , whereas the overall order, n. is a + p. Rea
tion order is determined From experimental observation. XF a = I and P =
we would say that the reaction is first order with respect to A, second ord
with respect to B, and overall third order. We say a reaction follows an el
m e n t q sate law if the reaction orders a g m with the stoichiornetric coeA
cients for the reaction as written.
3. The temperature dependence of a specific reaction rate is given by the Arrh
nius equntion,

where A is the frequency factor and E the activation energy.

If we know the specific reaction rate, k, at a temperature, To, and the acl
vation energy, we can find k at any temperature. T,

Similarly from Appendix C, Equation (C-9),if we know the equilibrium co

stant at a temperature, TI. and the heat of reaction, WF can find the equilil
riurn constant at any other temperature
 Chap. 3 Summary

PART 2

4. The sroichiomerric table for the reaction given by Equation 6 3 - 1 ) being car-
ried out in a flow system is

Species Entering Chunge having

A F~ - F~&f FAo(1 - A')

d e b
where 6=

5. In the case of ideal gases, Equations (S3-6) and (S3-7) relate volume and voI-
umetric flow rate to conversion.
Batch constant volume: V= vo (S3-6,

T
Flow systems: Gas:

Liquid: v = u,
For the general reaction given by (S3-11, we have

6 = Change in total number of moles

Mole of A reacted
Definitions of 6 and
and E

Change in totaI number of moles for complete conversion

e=
Total number of moles fed to the reactor
 t26 Rate Laws and Stoichiometry Chap. 3

6. Far pas-phase reactions, we use the definition of concentration (C, = FJu)

along with the stoichiometric table and Equation {S3-7) to write the concen-
tration of A and C in terms of conversion.

Q,irh @, = & - 'c" - 3

F A , CAO ! . ~ n
7. For incompressible liquids. the concentrattons of species A and C i n the reac-
tion gtven by Equatlon rS3-1) can be writ~enas

c, = C,
i ..I
Oc + - X

FZuations (S?- 17 ) and (S3-13) also hold for gas-phase reactions carried out at
constant volume in batch systems
8. I n terms ul' pas-phace molar Row rates, the concentration of species r is

-
Ci = C," Fi -F -To
FT" Po T

CD-ROM MATERIAL
Learning Resuurce
1 . Sun119ran' N o ~ fc~r
s Cliupicr 3
2 We11Mvdtt/e.~
summa^:, Nmes A. Cooking a P o ~ u
The chemical reaclion eng~ncrringis 3ppIred Fa cookin: a polato
k
Starch (c~stalline)-+Starch amorphous
 Chap. 3 CD-ROM Material 127

3. MolecuIar Reaction Engineering

Molecular simulators (Spiman. Ceriuq21 are used to make predictions of
the activation energy. The fundamentals of density fi~nctionalare pre-
sented along with specific examples.

3. Inreracfi1,eCrnrprrrrr Modrrler
A. QUIZ Show I1

Snh~rdPmhler~ir
A. CDP.1-A, Actirnt~nnEnerg! h r a Beetle Pw<hing a Ball of dun^
B CDP1-R, Micrnelccrronic\ Induqrr! and the Sln~chlorne~ricTible
- 'rrtluently Asked Qucstion~J-In Upd;i~eslFAit' I C O \eciion
~
Solved 7rob!ems
 Rate Laws and Stoichiometry Char

Professional Reference ShcIf

R3.1. Coiii~iotiThmy
In h i s section, the fundamentals of collision theory

Schematic of collision cross wclion

are applied to the reaction

A+B+C+D
to arrive at the following rate law

The activation energy, E,, can be estimated from the Pofanyi equation

R3.2. Transition Srclre Theoy

In this section, the nte law and rate Iaw pmmeters are derived for the reacti

using transition state theory. The Figure P3B-1 shows the energy of the ma
ecules along the reaction cmrdinate which measures the progress of the reactic

Figure P3B-I Reaction coordinate for (a) SH2reaction,and (b) generalized reaction. (c) 3-1
energy surhce for generalized reaction.

We will now use statistical and quantum mechanics to evaluate KACto arri
at the equation