5.

Collection and Analysis of Rate Data

In chapter 4 we showed that once the rate law is known, it can be substituted into appropriate design equation, and through the
use of the appropriate stoichiometric relationships used to size any isothermal reaction system. In this chapter we focus on ways
of obtaining and analyzing reaction rate data to obtain the Rate Law for a specific reaction. We discuss two common types of
reactors for obtaining rate data: The Batch Reactor, which used primarily for homogeneous reactions, and the Differential
Reactor, which is used for solid-fluid reactions.

In batch reactor experiments, concentration, pressure and volume are usually measured and recorded at different times during
the course of the reaction. Data are collected from batch reactor during the unsteady-state operation, whereas the
measurements on the differential reactor are made during steady-state operation. In experiments with a differential reactor, the
product concentration is usually monitored for different feed conditions.

There are two techniques of data acquisition: concentration-time measurements in a batch reactor, and concentration
measurements in a differential reactor. Six different methods of analyzing the data collected are used: the differential method,
the integral method, the method of half-lives, method of initial rates, and linear and non-linear regression (least-squares
analysis). The differential method and integral method are used primarily in analyzing batch reactor data. With this two methods
of analysis, it is possible to carry out only one experiment to find the specific reaction rate and the reaction order with respect to
one of the reactants. The method of half-lives and initial rates require experiments at many different initial conditions to
determine the reaction order and the specific reaction rate.

Objectives:

 Determine the reaction order and specific reaction rate from experimental data
obtained from either batch or flow reactors using graphical and integral methods.
 Describe how to use polynomial fitting and numerical difference formulas to analyze
experimental data to determine the rate law and rate law parameters.

5.1 The Algorithm for Data Analysis

1. Postulate a rate law
A. Power law models for homogeneous reactions
 rA  kC A  rA  kC A C B
B. Langmuir-Hinshelwood models for heterogeneous reactions
kPA kPA PB
 rA   rA 
1  K A PA (1  K A PA  PB ) 2
2. Select reactor type and corresponding mole balances
dC A
 rA 
A. Batch reactor, use mole balance on reactant A dt
B. Differential reactor, use mole balance on product ( A  B)
Fp
 rA   C p 0 / W
W
3. Process your data in terms of measured variables (NA, CA or PA)
If necessary, re-write your mole balances in terms of the measured variable (e.g.,PA).
4. Look for simplifications
 For example, if one of the reactants is in excess, assume its concentration is constant. If the gas-phase
mole fraction of reactant A is small, set   0
5. Batch reactor, calculate  rA as a function of CA to determine reaction order.
A. Differential Analysis

Combine the mole balance and power law model  rA  kC A
dC A  dC A 
  kC A ln    ln(rA )  ln k   ln C A
dt then take natural log:  dt 
dC A

(1) Find dt from CA versus t data by:
a) Graphical method
b) Finite difference method
c) Polynominal
 dC A 
ln   versus ln C A
(2) Plot  dt 
and find reaction order  , which is the slope of the line fit to the data.
(3) Find k.
B. Integral Method
 rA  kC A dC A
  kC A
For the combined mole balance and rate law is dt (5.1
(1) Guess  and integrate equation (5.1). rearrange your eqn. to obtain the appropriate
function of CA, which when plotted as a function of time should be linear. If it is
linear, then the guessed value of  is correct and the slope is the specific reaction
rate, k. if it is not linear, guess again for  .If you guess  =0,1, and 2 and none of
these orders fit the data, proceed to non-linear regression.
(2) Nonlinear regression (Polymath) – integrate eqn. (5.1) to obtain
 1 
1  C A(10 )  C A(1 ) 
t  
k (1   )  for use polymath regression to find &k
6. Differential PBR, calculate A as a function of CA or PA
 r
Fp
 rA   C p 0 / W
A. Calculate W as a function of reactant concentration CA.
kPA
 rA 
B. Choose model e.g., 1  K A PA
C. Use non-linear regression to find the best model and model parameters.
5.2 Batch Reactor Data
Batch reactors are used primarily to determine rate law parameters for homogeneous reactions. This determination is usually
achieved by measuring concentration as a function of time and the using either the differential or integral method of data
analysis to determine reaction order,  , and specific reaction rate, k. If some reaction parameter other than concentration is
monitored, such as pressure, the mole balance must be re-written in terms of measured variable (pressure).
5.2.1 Differential method of Rate Analysis
When reaction is irreversible, it is possible in many cases to determine reaction order and the specific reaction rate constant by
numerically differentiating concentration versus time data. This method is applicable when reaction conditions are such that the
rate is essentially a function of concentration of only one reactant: e.g., if for the decomposition reaction A  products rate law
 rA  kC A the differential method may be used.
However, by utilizing the method of excess, it is also possible to determine the relationship between –rA and the concentration of
the other reactants.
A  B  products  rA  kC A C B  and 
That is, for irreversible reaction with the rate law , where are both unknown,
the reaction could first be run in excess of B so that CB remains essentially unchanged during the course of the reaction and
 rA  k C A ,
where k   kC B  kC B 0 (method of excess)- pseudo-specific reaction rate.
 


, the reaction is carried out in an excess of A, for which the rate law is approximated as  rA  k C B , where

After determining
k   kC A  kC A0 .

both
 and can be determine by using the method of excess, coupled with a differential analysis of data for a batch
reactor. To outline the procedure used in the differential method of analysis, we consider reaction carried out in a constant volume
batch reactor and the concentration recorded as a function of time. By combining the mole balance with rate law we obtain:
dC A  dC A 
  kC A ln    ln(rA )  ln k   ln C A
dt after taking the natural log of both sides  dt 

 dC A 
ln   versus ln C A
plot  dt  to find and k.

 dC A 
 
The slope of a plot is the reaction order. To obtain the derivative  dt  used in the plot, we must differentiate the
concentration-time data either numerically or graphically. However, we are usually given concentration as a function of time from
batch reactor experiments.
time (s) 0 t1 t2 t3
concentration (mol/dm3) CAo CA1 CA2 CA3

5.2.2. Three Ways to Determine (-dCA/dt) from Concentration-Time Data

(Graphical, Numerical and Polynomial)
1. Graphical
 dC A  dC A 
  dt 
Plotting dt as a function of time and then using equal-area differentiation to obtain  .
This method accentuates measurement error!
2. Numerical (Finite Difference)
Numerical differentiation formulas can be used when the data points in the independent variable are
equally spaced, such as t1  t 0  t 2  t 3  t :
Time (min) t0 t1 t2 t3 t4 t5
C CA0 CA1 CA2 CA3 CA4 CA5
(mol/dm )
3

The three-point differentiation formulas

 dC A   3C A0  4C A1  C A 2
  
Initial point:  dt  t0 2t (5.2)
 dC A 
  
1
 
C A(i1)  C A(i1) 
Interior points:  dt  ti 2t (5.3)
 dC A  1
   C A4  C A2 
e.g.,  dt  t 3 2t
 dC A  1
   C A3  4C A4  3C A5 
Last point:  dt  t 5 2t (5.4)
Can be used to calculate dC A / dt .
Equations (5.2) and (5.4) are used for first and last data points respectively, while (5.3) is used for all
intermediate points.
3. Polynomial (using Polymath)
CA = ao + a1t + a2t2 + a3t3 +a4t4

5.2.2 Integral method

To determine the reaction order by the integral method, we guess the reaction order and integrate the differential equation used to
model the batch reactor.
If the order we assume is correct, the appropriate plot (determined from this integration) of the concentration-time data should be
linear. The integral method most often used when reaction order is known and it is desired to evaluate the specific reaction rate
constants at different temperatures to determine the activation energy.
In the integral method of analysis of rate data we are looking for the appropriate function of concentration corresponding to a
particular rate law that is linear with time. We should be familiar with the methods of obtaining these linear plots for reactions of
zero-, first- and second order.

Table5-1-Derivation Equations used to Plot 0, 1st, and 2nd order reactions.

These types of plots are usually used to determine the values k for runs at various temperatures and then used to determine the
activation energy.
Table 5-1
Zero Order First Order Second Order

5.3 Differential Reactors

In a differential reactor the rate of reaction is determine for a specific number of
predetermined initial or entering reactants concentrations. A differential reactor is
normally used to determine the rate of reaction as a function of either concent

ration or partial pressure. It consists of a tube containing a very small amount of

catalyst usually arranged in a form of a thin wafer or disk.
The criterion for a reactor being differential is that the conversion of the reactants in
the bed is extremely small, as is the change in temperature and reactant concentration
through the bed. As a result, the reactants concentration through the reactor essentially
constant, and approximately equal to the inlet concentration. The reaction rate is
considered spatially uniform within the bed.
The differential reactor is relatively easy to construct at low cost. The reactor operates
in an isothermal manner.
The volumetric flow rate through the reactor bed is monitored, as are the entering and
exiting concentrations. If the weight of catalyst, W ,is known, the rate of reaction per
 unit mass of catalyst,  rA , can be calculated. Since the differential reactors is assumed
to be gradientless, the design eqn. will be similar to the CSTR design eqn.
For the reaction A  product at steady-state mole balance on reactant A:
      
 flow rate in 
  flow rate out    rate of generation   rate of accumulation 
      
  
 rate of reaction  
FA0   FAe   
  mass of cat  0
 
 mass of cat  
, where subscript e, refers to the exit of the reactor.
 rA  F  FAe
 rA  A0
Solving for we have W (5.5)
 C  C Ae
 rA  0 A0
In terms of concentration W (5.6) or in terms of conversion or
F X F
 rA  A0 
p

product flow rate: W W (5.7)

The term FA0X gives the rate of formation of the product, Fp, when the stoichiometric
coefficients of A and P are identical.
 (C  C Ae )  0 C p
 rA  0 A0 
For constant volumetric flow rate eqn. (5.6) reduces to: W W
(5.8)
The reaction rate can be determined by measuring the product concentration. By using
very little catalyst and large volumetric flow rates, the (CA0-CAe) can be made very
small. The rate of reaction determined from (5.8) can be obtained as a function of the
reactant concentration in the catalyst bed, CAb.
 rA  rA (C Ab ) C  C Ae
C Ab  A0
where 2 since very little reaction takes place within
the bed , the bed concentration is equal to inlet concentration: C Ab  C A0 , so  rA is a
function of C A0 :  rA  rA (C A0 )
5.4 Laboratory Reactors
The successful design of industrial reactors lies primarily with the reliability of the
experimentally determined parameters used in the scale-up. Consequently, it is
imperative to design equipment and experiments that will generate accurate and
meaningful data. Unfortunately, there is usually no single comprehensive laboratory
reactor that could be used for all types of reactions and catalysts. In this section we
discuss the various types of reactors that can be chosen to obtain the kinetic
parameters for a specific reaction system.
The criteria used to evaluate various types of laboratory reactors are listed in Table 5-
2.

CRITERIA USED TO EVALUATE LABORATORY

REACTORS
1. Ease of sampling and product analysis
2. Degree of isothermality
3. Effectiveness of contact between catalyst and reactant
4. Handling of catalyst decay
5. Reactor cost and ease of construction
5.4.1 Integral (Fixed-Bed) Reactor
One advantage of the integral reactor is its ease of construction (Figure 5-1). On the other hand, while the
channeling or bypassing of some of the catalyst by the reactant stream may not be as fatal to data
interpretation in the case of this reactor as in that of the differential reactor, it may still be a problem. There
is more contact between the reactant and catalyst in the integral reactor than in the differential reactor,
owing to its greater length. Consequently, more product will be formed, and the problems encountered in
the differential reactor in analyzing small or trace amounts of product in the effluent stream are eliminated.
However, if a reaction is highly endothermic or exothermic, significant axial and radial temperature
gradients can result, and this reactor will receive a poor-to-fair rating on its degree of isothermality. If a
reaction follows different reaction paths with different activation energies, different products will be
formed at different temperatures. This makes it difficult to unscramble the data to evaluate the various
reaction rate constants because the reaction mechanism changes with changing temperature along the
length of the reactor.
Figure 5-1 Integral reactor.
If the catalyst decays significantly during the time an experiment is carried out, the reaction rates will be
significantly different at the end of the experiment than at the start of the experiment. In addition, the
reaction may follow different reaction paths as the catalyst decays, so that the selectivity to a particular
product will vary during the course of the experiment. Consequently, it will be difficult to sort out the
various rate law parameters for the different reactions and, as a result, this reactor receives a poor rating in
the catalyst decay category. However, this type of reactor is relatively easy and inexpensive to construct, so
it receives a high rating in the construction category.
5.4.2 Stirred-Batch Reactor
In a stirred-batch reactor the catalyst is dispersed as a slurry, as shown in Text Figure 5-2. Although
this reactor has better contact between the catalyst and fluid than either the differential or integral
reactors, it has a sampling problem. Samples of fluid are usually passed through cyclones or
withdrawn through filters or screens to separate the catalyst and fluid, thereby stopping the reaction.
However, slow quenching of the reaction in the cyclone or plugging of the filter sampling system by
the catalyst particles is a constant concern, thus making the rating in the sampling category only fair.
Since the system is well mixed, its isothermality is good. There is good contact between the catalysts
and reactants, and the contact time is known since the catalyst and reactants are fed at the same time.
However, if the catalyst decays, the activity and selectivity will vary during the course of data
collection.
 Figure 5-2 Stirred-batch reactor.

5.4.3 Stirred Contained-Solids Reactor (SCSR)

Although there are a number of designs for contained-solids reactors, all are essentially equivalent in
terms of performance. A typical design is shown in Text Figure 5-3. In this reactor, catalyst particles
are contained in paddles that rotate at sufficiently high speeds to minimize external mass transfer
effects and, at the same time, keep the fluid contents well mixed. With this type of operation,
isothermal conditions can be maintained and there is good contact between the catalyst and fluid. If
the catalyst particle size is small, difficulties could be encountered containing the particles in the
paddle screens. Consequently, it receives only a fair rating in the ease of construction and cost
category. Although this type of reactor receives a good rating for ease of sampling and analysis of
product composition, like the three previous reactors, it suffers from being unable to generate useful
data when the catalyst being studied decays. As a result, it receives a poor rating in the catalyst decay
category.

Figure 5-3 Stirred contained-solids reactor.

minimizes external mass transfer resistance

5.4.4 Continuous-Stirred Tank Reactor (CSTR)

In this reactor (Figure 5-4), fresh catalyst is fed to the reactor along with the fluid feed and the catalyst
leaves the reactor in the product stream at the same rate that it is fed. As a result, the catalyst in the
reactor is at the same level of catalytic activity at all times. Thus we are not faced with the problem
encountered in the four previous reactors, in which the kinetic parameters evaluated at the beginning of
the experiment will be different than those at the end. However, since there will be a distribution of
time that the catalyst particles have been in the reactor, there will be a distribution of catalytic
activities of the particles in the bed If the mean residence time is large, selectivity disguise could be a
problem. Since the reactor is well-mixed, isothermality and fluid--solid contact categories are rated as
good. However, difficulties can arise in feeding the slurry accurately and, as with the stirred-batch
reactor, it is difficult to quench the reaction products. Consequently, it receives only fair ratings in the
first (sampling) and fifth (construction) categories.
 Fig 5.4 CSTR-one of the best reactors for isothermal operations.

5.4.5 Straight-Through Transport Reactor

Commercially, the transport reactor (Text Figure 5-5) is used widely in the production of gasoline from heavier
petroleum fractions. In addition, it has found use in grain drying operations. In this reactor, either an inert gas or the
reactant itself transports the catalyst through the reactor. With this reactor, any possibility of catalyst decay/selectivity
disguise is virtually eliminated because the catalyst and reactants are fed continuously. For highly endothermic or
exothermic reactions, isothermal operation will be difficult to achieve and it receives a poor-to-fair rating in this
category. At moderate or low gas velocities there may be slip between the catalyst particles and the gas so that the gas-
catalyst contact time will not be known very accurately. Consequently, this reactor receives only a fair-to-good rating
in the gas-catalyst contacting category. This reactor is somewhat easier to construct than the CSTR, but salt or sand
baths may be required to try to maintain isothermal operation, and it therefore receives a fair-to-good rating in the
construction category. Difficulty in separating the catalyst and reactant gas or in thermally quenching the reaction
results in a fair rating in the sampling category.

Figure 5-5 Straight-through transport reactor.

5.4.6 Recirculating Transport Reactor
By recirculating the gas and catalyst through the transport reactor (Figure 5-6), a well-mixed condition can be
achieved provided that the recirculation rate is large with respect to the feed rate. Consequently, isothermal operation
is achieved. Since the reactor is operated at steady state, the kinetic parameters measured at the start of the experiment
will be the same as those measured at the end. However, since fresh catalyst is mixed with decayed catalyst from the
recycle, the product distribution and the kinetic parameters might not be the same as those measured in a straight-
through transport reactor where the gas "sees" only fresh catalyst. The incorporation of a recirculation system adds a
degree of complexity to the construction, which gives it a lower rating in this category as well.

Figure 5-6 Recirculating transport reactor

5.4.7 Summary of Reactor Ratings
The ratings of the various reactors are summarized in Table 5-3
Reactor Sampling and isothermalit Fluid-solid Decaying Ease of construction
analysis y contact catalyst
type
 Differential P-F F-G F P G
Fixed bed G P-F F P G
Stirred batch F G G P G
Stirred- G G F-G P F-G
contained
solids
CSTR F G F-G F-G P-F
Straight- F-G P-F F-G G F-G
through
transport
Recirculating F-G G G F-G P-F
transport
Pulse G F-G P F-G G
From this table note that the CSTR and recirculating transport reactor appear to be the best
choices because they are satisfactory in every category except for construction. However, if the
catalyst under study does not decay, the stirred batch and contained solids reactors appear to be
the best choices. If the system is not limited by internal diffusion in the catalyst pellet, larger
pellets could be used and the stirred-contained solids is the best choice. If the catalyst is non-
decaying and heat effects are negligible, the fixed-bed (integral) reactor would be the top choice,
owing to its ease of construction and operation. However, in practice, usually more than one
reactor type is used in determining the reaction rate law parameters.