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Nasaba J.C, Lecture Notes On Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Nasaba J.C, Lecture Notes On Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
• Reactor design embodies many different facets and disciplines, the details
of some of which are outside our scope. here, we focus on process design
as opposed to mechanical design of equipment . Other aspects are implicit,
but are not treated explicitly: instrumentation and process control,
economic, and socioeconomic (environmental and safe-operation). Reactor
design is a term we may apply to a new installation or modification;
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued….
• At this stage, type (1) is more apparent than type (2) and we
provide some preliminary discussion of (2) here. Flow
characteristics include relative times taken by elements of fluid
to pass through the reactor (residence-time distribution), and
mixing characteristics for elements of fluid of different ages:
point(s) in the reactor at which mixing takes place, and the level
of segregation at which it takes place (as a molecular dispersion
or on a macroscopic scale). Lack of sufficient information on
one or both of these types is a major impediment to a
completely rational reactor design.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Interpretation of batch reactor data
• A rate equation characterizes the rate of reaction, and its form may
either be suggested by theoretical considerations or simply be the
result of an empirical curve-fitting procedure. In any case, the value
of the constants of the equation can only be found by experiment;
predictive methods are inadequate at present.
• The determination of the rate equation is usually a two-step
procedure; first the concentration dependency is found at fixed
temperature and then the temperature dependence of the rate
constants is found, yielding the complete rate equation.
• Equipment by which empirical information is obtained can be
divided into two types, the batch and flow reactors. The batch
reactor is simply a container to hold the contents while they react.
All that has to be determined is the extent of reaction at various
times, and this can be followed in a number of ways, for example:
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued………..
1. By following the concentration of a given component.
2. By following the change in some physical property of the fluid,
such as the electrical conductivity or refractive index.
3. By following the change in total pressure of a constant-volume
system.
4. By following the change in volume of a constant-pressure
system.
• The experimental batch reactor is usually operated
isothermally and at constant volume because it is easy to
interpret the results of such runs.
• The flow reactor is used primarily in the study of the kinetics
of heterogeneous reactions.
• There are two procedures for analyzing kinetic data, the
integral and the differential methods.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Comparison of differential and integral method
Differential method Integral method
In the differential method of analysis we test In the integral method of analysis we guess a
the fit of the rate expression to the data particular form of rate equation and, after
directly and without any integration. appropriate integration and mathematical
However, since the rate expression is a manipulation, predict that the plot of a certain
differential equation, we must first find concentration function versus time should
(l/V)(dN/dt) from the data before attempting yield a straight line. The data are plotted, and
the fitting procedure. if a reasonably good straight line is obtained,
then the rate equation is said to satisfactorily
fit the data.
The differential method is useful in more The integral method is easy to use and is
complicated situations but requires more recommended when testing specific
accurate or larger amounts of data mechanisms, or relatively simple rate
expressions.
the differential method can be used to develop The differential method is useful in more
or build up a rate equation to fit the data. complicated situations but requires more
accurate or larger amounts of data
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Constant-volume Batch Reactor
• When the constant-volume batch reactor is considered it refers to the
volume of reaction mixture, and not the volume of reactor. Thus, this term
actually means a constant-density reaction system.
• Most liquid-phase reactions as well as all gas-phase reactions occurring in
a constant-volume bomb fall in this class.
• In a constant-volume system the measure of reaction rate of component i
becomes
1 dN i d ( N i / V ) dC i
ri
V dt dt dt
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Analysis of Total Pressure Data Obtained in a Constant-Volume System
• For isothermal gas reactions where the number of moles of material
changes during reaction, let us develop the general expression which
relates the changing total pressure of the system to the changing
concentration or partial pressure of any of the reaction components.
• Let rate equation is
aA bB ....... rR sS ............
• At time t =0 the amount of reactant and product along with inert are NA0,
NB0…….. NR0, NS0. Ninert
• At time t the above amount are (NA0 –ax), (NB0 –bx),……. (NR0 +rx), (NS0
+sx), Ninert
• Let N0 =NA0 +NB0 +…..NR0 +NS0 …………+Ninert
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Conversion
• Suppose that NAo is the initial amount of A in the reactor at time
t = 0, and that NA is the amount present at time t. Then the
conversion of A in the constant volume system is given by
N A0 N A N A /V CA
XA 1 1
N A0 N A0 /V C A0
• or dCA
dX A
C A0
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Integral Method of Analysis of Data
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Overall Order of Irreversible Reactions from the Half-Life
• The half-life of the reaction is defined as the time needed for the
concentration of reactants to drop to one-half the original value.
• Let us consider the decay of reactant A as per following rate equation
dC A
rA
n
kCA
• For n1 dt
1 n 1 n
CA C A0 k (n 1)t
• Therefore half-life is given by
(0.5) 1n 1 1 n
t1/ 2 CA0
• Fractional Life Method k (n 1)
( F )1 n 1 1 n
tF CA0
k (n 1)
• Thus, a plot of log tF versus log CAo, will give the reaction order.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Mechanism of Irreversible Reactions in Parallel
• Consider the simplest case, A decomposing by two competing paths, both
elementary reactions:
A k1
R
A
k2
S
• Thus, the slope of a plot of CR versus Cs gives the ratio k1/k2. Knowing
k1/k2 as well as k1 + k2 gives k1 and k2.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Homogeneous Catalyzed Reactions
• Suppose the reaction rate for a homogeneous catalyzed system is the sum
of rates of both the un-catalyzed and catalyzed reactions,
A
k1
R
A C
k2
R C
• And the corresponding rate equations are
dC A
k 1C A
dt 1
dC A
k 2C AC C
dt 2
dC A
k 1C A k 2 C A C C (k 1 k 2 C C )C A
dt overall
• As concentration of catalyst remains unchanged
CA
ln ( k1 k 2C C )t
C A0
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Autocatalytic Reactions
• A reaction in which one of the products of reaction acts as a catalyst is
called an autocatalytic reaction. The simplest such reaction with rate
equation is
A R R R
dC A
rA kC AC R
dt
• Because the total number of moles of A and R remain unchanged as A is
consumed, we may write that at any time
C R / C R0
ln C A0 C R 0 k t
C A / C A0
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• For an autocatalytic reaction in a batch reactor some product R
must be present if the reaction is to proceed at all.
• Starting with a very small concentration of R, and the rate will
rise as R is formed.
• At the other extreme, when A is just about used up the rate must
drop to zero. This result is that the rate follows a parabola, with
a maximum where the concentrations of A and R are equal.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Irreversible Reactions in Series
• Let us consider consecutive unimolecular first order reactions are in series
and is given by:
A
k1
R
k2
S
• And the rate equations are
dC A
rA k 1C A
dt
dC R
rR k 1C A k 2 C R
dt
dC S
rS k 2C R
dt
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• To find the changing concentration of R, substitute the above expression
form concentration of A from into the differential equation governing the
rate of change of R, and the equation becomes
• The above differential equation will be solved with the help of integrating
factor and the solution becomes
• And
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued….
• Special cases
• Case I: Now if k2 is much larger than k1,
• In other words, the rate is determined by k1 or the first step of the two-step
reaction.
• Case II: If k1 is much larger than k2, then
• which is a first-order reaction governed by k2, the slower step in the two-
step reaction. Thus, in general, for any number of reactions in series it is
the slowest step that has the greatest influence on the overall reaction
rate.
• Case III: The time at which the maximum concentration of R occurs i.e.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• The maximum concentration of R is
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
First-Order Reversible Reactions
• Let us consider reactions for which complete conversion cannot be
assumed. The simplest case is the opposed unimolecular-type reaction
• At equilibrium
• Therefore
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• By combining the above equation the instantaneous conversion may be
written in terms of equilibrium conversion as follows:
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Second-Order Reversible Reactions
• For the bimolecular-type second order reactions
• with the restrictions that CA0 = CB0, and CR0 = CS0 = 0, the integrated rate
equations for A and B are all identical, as follows
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Reactions of Shifting Order
• In searching for a kinetic equation it may be found that the data are well
fitted by one reaction order at high concentrations but by another order at
low concentrations. Let us consider such a reaction as follows:
• Or
• hence
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• The rate form of shifting order reaction and some of its generalizations are
used to represent a number of widely different kinds of reactions.
• For example, in homogeneous systems this form is used for enzyme-
catalyzed reactions where it is suggested by mechanistic studies.
• It is also used to represent the kinetics of surface-catalyzed reactions.
• In mechanistic studies, this form of equation appears whenever the rate-
controlling step of a reaction is viewed to involve the association of
reactant with some quantity that is present in limited but fixed amounts;
for example, the association of reactant with enzyme to form a complex, or
the association of gaseous reactant with an active site on the catalyst
surface.
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Differential Method of Analysis of Data
• The differential method of analysis deals directly with the
differential rate equation to be tested, evaluating all terms in the
equation including the derivative dCi/dt, and testing the goodness of
fit of the equation with experiment. The procedure is as follows.
1. Plot the CA vs. t data, and then by eye carefully draw a smooth curve
to represent the data. This curve most likely will not pass through all
the experimental points.
2. Determine the slope of this curve at suitably selected concentration
values. These slopes dCi/dt = rA are the rates of reaction at these
compositions.
3. Now search for a rate expression to represent this rA vs. CA data,
either by (a) picking and testing a particular rate form, -rA = kf (CA),
(b) testing an nth-order form -rA = k(CA)n : by taking logarithms of
the rate equation
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
Fig: Test for the particular Fig: Test for the n-th order
rate by the differential rate by the differential
method method
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
VARYING-VOLUME BATCH REACTOR
• These reactors are much more complex than the simple constant-volume
batch reactor. Their main use would be in the micro-processing field where
a capillary tube with a movable bead would represent the reactor (see
Fig.). The progress of the reaction is followed by noting the movement of
the bead with time, a much simpler procedure than trying to measure the
composition of the mixture, especially for micro-reactors. Thus,
A varying-volume
batch reactor
• V0 = initial volume of the reactor
• V = the volume at time t.
• This kind of reactor can be used for isothermal constant pressure
operations, of reactions having a single stoichiometry. For such systems
the volume is linearly related to the conversion, or
hence
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• where A is the fractional change in volume of the system between no
conversion and complete conversion of reactant A. Thus
• But with 50% inerts present at the start, two volumes of reactant mixture
yield, on complete conversion, five volumes of product mixture. In this
case
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
Continued…
• The A accounts for both the reaction stoichiometry and the presence of
inerts. Noting that
• Therefore
• Hence and
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics
References
1. H. Scott Fogler, Elements of Chemical Reaction
Engineering, Prentice Hall, 4th edition, 2005.
2. Octave Levenspiel, Chemical Reaction Engineering,
John Wiley & Sons, 3rd edition, 1999.
3. Mark E. Davis, Robert J. Davis, Fundamental of
Chemical Reaction Engineering, McGraw Hill, 1st
edition, 2003.
4. Schmidt. Lanny D. The Engineering of Chemical
Reactions Oxford University Press, Inc., New York, NY
(1998).
Nasaba J.C, Lecture notes on Chemical Reaction Engineering, Chapter I: Chemical Reaction Kinetics