Reactors1 16

v ε
XA = − A
N A0
2. Rate Expressions
Before designing a chemical reactor, one must know the reaction(s) rate. Rates of
reaction can be written in intrinsic form or in terms of a specific reactant of interest. An
intensive measure, based on a unit volume of fluid, is normally used for homogeneous
reacting systems. Thus, the general definition of reaction rate can be written as
1  dN 
ri = t  i 

V  dt 
where ri is the number of moles of component i that appear or disappear by reaction per
unit volume and time in kg mol liter -l sec -l, Vt the total volume of reacting fluid in liters,
Ni the number of moles of component i in kg mol, and t the time in seconds. The rates of
formation of products R, S, T,... are related to the rates of disappearance of reactants A,
B,..., by the stoichiometric numbers,
rA r rR r r r
= B = = S = T = i
vA vB vR vS vT vi
With the normal sign convention (positive for products, negative for reactants), a rate is
negative for a reactant (-rA) and positive for a product (rR).
Rates of reactions are functions of the thermodynamic state of the system. For a simple
system, fixing temperature and composition fixes the rest of the thermodynamic
quantities or the state. Thus, the rate can be written in terms of a temperature-dependent
term called the rate constant k (constant at fixed temperature) and a concentration term or
terms Ci.
Example.
− rA = kC A
Rates of reaction vary with changes in temperature or concentration. All reactions are
reversible (i.e., have a forward and a reverse reaction). When the rate of the forward
reaction equals the rate of the reverse reaction, there is no net change in concentrations of
any component, and the system is said to be at thermodynamic equilibrium. This
condition represents a minimum free energy of the system and determines the limits of
conversion. The overall rate of reaction equals zero at equilibrium. A relationship can
be derived between the forward and reverse rate constants and the overall thermodynamic
equilibrium constant. For example, consider the reaction
k1
A + B ←→ R+S
k2
If the forward rate equals k1CACB,and the reverse rate equals k2CRCS, the overall rate of
disappearance of component A is -rA = klCACB - k2CRCS. At equilibrium, -rA ≅ 0,
k1 C C
= R S ≡ Kc
k2 CACB
where Kc is defined as the thermodynamic equilibrium constant based on concentration.

Reactions that have very high values of the equilibrium constant are termed irreversible
since the value of k2 must be very small. Without much loss of accuracy, these equations
can be modeled as dependent only on the forward rate. In this example, if the reaction is
essentially irreversible, -rA = klCACB.
Rate expressions must ultimately come from an analysis of experimental data. We
cannot normally write a rate equation by inspection of the stoichiometric reaction
equation; however, a reaction is termed elementary if the rate expression can be written
by inspection based on the stoichiometric numbers.
Consider the following reversible reaction
k1
A + B ←→ =2R
k2
If this reaction is elementary, the rate expression can be written as
2
− r A = k1C A C B − k 2 C R
In general, an elementary reaction has the form:
− rA = k1C vA A C vB B K − k 2 C vR R C Sv s K
Reactions are classified by their order depending on the sum of the stoichiometric
coefficients of each term.
Examples.
-rA = k zero order

-rA = kCA first-order irreversible
-rA = kC2A second-order irreversible
-rA = k1CA - k2CR first-order reversible
k C
− rA = 1 A complex
1+ k C C
2 A R
0.3 0.7
− rA = kC A C B complex
3. Use of Kinetic Data
To design a chemical reactor the rate expression must be known. Assuming the
reaction is known not to be elementary, we must search for a mechanism that describes
the reaction taking place or use experimental data directly. Mechanisms can be
hypothesized as the sum of a series of elementary reactions with intermediates. Using
methods developed by physical chemists, we can hypothesize whether the proposed
mechanism fits the actual experimental evidence. If no inconsistencies are found, the
hypothesized mechanism is possibly the actual mechanism. However, agreement of the
mechanism with the experimental data does not necessarily mean that the proposed
mechanism is correct, since many mechanisms can be hypothesized to fit such data.
An interpretation of batch or flow reactor data is used to fit an empirical rate
expression. For example, in a simple batch reactor, concentration is measured as a
function of time. Once the experimental data are available, two methods can be used to
fit a rate expression.
The first, called the integral method of data analysis, consists of hypothesizing rate
expressions and then testing the data to see if the hypothesized rate expression fits the
experimental data. These types of graphing approaches are well covered in most
textbooks on kinetics or reactor design.
The differential method of analysis of kinetic data deals directly with the differential
rate of reaction. A mechanism is hypothesized to obtain a rate expression and a
concentration-versus-time plot is made. The equation is smoothed, and the slopes, which
are the rates at each composition, are evaluated. These rates are then plotted versus
concentration; and if we obtain a straight line passing through the origin, the rate
equation is consistent with the data. If not, another equation is tested. Kinetic data can
also be taken in flow reactors and evaluated with the above methods and the reactor
design equation.
4. Temperature Dependence of the Rate Constant
On a microscopic scale, atoms and molecules travel faster and, therefore, have more
collisions as the temperature of a system is increased. Since molecular collisions are the
driving force for chemical reactions, more collisions give a higher rate of reaction. The
kinetic theory of gases suggests an exponential increase in the number of collisions with
a rise in temperature. This model fits an extremely large number of chemical reactions
and is called an Arrhenius temperature dependency, or Arrhenius' law. The general form
of this exponential relationship is
k = k 0 e −E RT

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v ε

where Kc is defined as the thermodynamic equilibrium constant based on concentration.

If this reaction is elementary, the rate expression can be written as

In general, an elementary reaction has the form:

-rA = k zero order

3. Use of Kinetic Data

4. Temperature Dependence of the Rate Constant

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