Chapter-4 Determination of Rate Equations from

the Experimental Data

4.1 EXPERIMENTAL STRATEGIES FOR DETERMINING RATE
PARAMETERS

The law of definite proportions for single reaction

rj   jr

  
Mole balance
dC j
r  kC j C C ......
r 
j dt

Rate of reaction / rate equation/ kinetic law /rate law

   
r j   j kC j C  C ......

Rate equation
kinetic law /rate law
can be determine using
experimental results
Means finding: -The order of reaction
-The rate constant
Methods of analyzing experimental data depend on
 the type of reactor used, and,
 in some types, on the way in which it is used.
dC j    Rate equation for
dt
  j kC j C C ...... batch reactor
C  f (t; k{T})
j

dC j   
dt
  j kC j C  C ...... Rate equation for
PFR
C  f (t; k{T})
j
C C
j,0 j  kC  C  C  ...... Rate equation for
t j j   CSTR
C  f (t; k{T})
j
 Looking to the above rate equations
Batch reactor dC j   
dt
  j kC j C  C ......
C  f (t; k{T})
j
Plug flow reactor dC j   
dt
  j kC j C  C  ......
C  f (t; k{T})
CSTR reactor
j
C C
j,0 j  kC  C  C  ......
t j j  
C  f (t; k{T})
j
Experiments to find the rate leads to follow the extent
(progress) of reaction by means of one type of
measurement.
1) to find the concentration dependency of the
substance on time / residence time / at a fixed
temperature for determining the order of the reaction
2) to find the temperature dependency for evaluating
the rate constant at a fixed concentration to yield
the complete rate equation for some reaction
parameters.
 Finding the concentration dependency
 This may be the concentration of one species
”Chemical” method of analysis with
intermittent(broken) sampling
Property dependent on concentration.
“Physical” method with an instrument that could
continuously monitor the chosen characteristic of the
system.
Hence, The above method may be classified into two
categories, namely:
 Chemical and
 Physical analysis
i) Chemical analysis
determine directly the concentration of one of
the reacting substances or products against

time (or more specifically of residence time)

Examples of chemical methods of analysis are
The titration of an acid with a base, or vice versa,
and the precipitation of an ion in an insoluble
compound
Here, the concentration of a species in a liquid sample
removed from a reactor.
 Disadvantage of such methods specially for Batch
reactor is collection of a sample does not stop
further reaction from taking place or the
reaction cannot be turned on and off like a
stopcock. This is not a problem for steady-state
operation of a flow reactor (CSTR or PFR).

Such methods are often suitable for relatively slow

reactions. This is because of the length of time that
may be required for the analysis.
 ii) Physical Analysis
As chemical reaction proceeds in a system, physical
properties of the system change because of the change in
chemical composition.
 the physical change during the course of
reaction that does not require removal
successive samples from the reaction mixture is
continuously measured.
 Theoretically, any property that undergoes
sufficient change may be used to follow the
course of the reaction.
Examples of physical-property changes
(1) Change of pressure in a gas-phase reaction
involving change of total moles of gas in a constant-
volume BR in this case, the total pressure (P) is
measured and must be related to concentration of a
particular species. The instrument used is a pressure
gauge of some type.
(2) Change of volume in a liquid-phase reaction
the density of a reacting system may change very
slightly, and the effect can be translated into a
volume change magnified considerably by means
of a capillary tube mounted on the reactor,

(3) Change of optical rotation in a reacting system involving

optically active isomers (e.g., the inversion of sucrose); the
instrument used is a polarimeter to measure the angle of rotation
of polarized light passing through the system
(4) Change of electrical conductance in a reacting system
involving ionic species
(e.g., the hydrolysis of ethyl acetate); the reaction is carried
out in a conductivity cell in an electrical circuit for
measuring resistance.
(5) Change of refractive index involving use of a refractometer
(for a liquid system) or an interferometer (for a gas system).
(6) Change of color-use of a cell in a spectrophotometer.
(7) Single-ion electrodes for measurement of concentration of
individual species.
(8) Continuous mass measurement for solid reactant, or
absorbent for capture of product(s).
 Advantages of physical methods
 Their measurement rapidity.
 They make it possible to obtain a large number of
experimental data in a given time interval.
As a criteria to implement a physical method is that one has
to know the linear relationship between physical
properties and concentration,
i.e, concentration on the one hand and the electrical

conductivity, optical density, etc.

The experimental measurement can often be performed directly
in reaction vessel itself. The vessel is distinct in two types of
process, namely batch and flow reactors.
 Batch reactor Use for homogeneous reactions
i.e for slow reaction
Experiments
Concentration, pressure, and volume are measured and
recorded at different times during the course of reaction

Differential reactor / Plug flow reactor

Engage also in heterogeneous reactions i.e for fast reaction

Experiments
Product concentration is monitored for different feed condition
Experimental methods for determining rate parameters bases on
 concentration-related parameters in the rate law,

 then on temperature-related parameters.

The objective of experiments is to obtain
a set of point rates on observed rate of formation

r  moles A formed e.g. mol

A unit time s
at various conditions so that best values of the parameters may
be determined.
4.1.1 Concentration-Related Parameters: Order of Reaction

For simplicity, we consider the use of a constant-volume BR to determine the

kinetics of a system represented by reaction, A

Reactant (A) Product

With

 one reactant (A), or

 two reactants (A and B), or
 more (A, B, C, . . .).
Experimental Procedure
In every case, we use the rate with respect to species A,
which is then given by dC
(r )  - A
4.1
A dt
We further assume that Rate of reaction r  kC  C  C 
j 
 the rate law is of the form
rj   jr
 
(r )  kC C C  rate equation/ kinetic
A A B C law /rate law

A  kC  C  C 
dC
dt A B C

 the experiments are conducted at fixed T so that k

is constant
 An experimental procedure is used to
generate values of CA as a function of t,
 The values so generated (experimental data)
may then be treated by

The differential method;

The integral method ;
The initial rate method;
The half-life method and
The least-square method
 It is possible to carry out only one

The differential method experiment to find the order of

 The integral method reaction and the rate constant
with respect to one of the
reactants

Require experiment at many

 The initial rate method
different initial conditions to
 The half-life method
determine order of reaction and
the rate constant
 The least-square method
Used when three or more parameters are involved such as
α, k, E, A etc.
For our study and application purposes, we will limit the above methods
analyses in batch reactor systems
4.2 Differential Methods
In a differential method, a point rate is measured while a small
or “differential” amount of reaction occurs, during which the
relevant reaction parameters (Ci, T, etc.) change very little, and
can be considered constant.

 In this method, it requires differentiation of the experimental

data to obtain rate of reaction

Restriction for application for such method is

that it should only be applied for irreversible
reactions preferably with one reactant.
 Differential Methods using BR
One reactant
Consider the decomposition of the following single reactant
A
 P (B)
The kinetic expression for such type of reaction is given by
r  r   k C
A A A
Differential equation becomes
 k C
dC A
 A
dt

Linearization  dC A 
ln    ln k   ln C A (4.2)
 dt 
we test the fitness of the experimental data using
equation (4.2), to find k and α
 Two reactants
If there were two reactants A and B in reaction (A),
and the rate law were of the form

(r )  kC  C  4.3
A A B
Here we have to obtain k, α, β using the
differentiation procedure
The procedure is similar to that for one reactant, although there is
an additional constant to determine (β).
Linearization of equation (4.3) gives the differential equation

dC
ln( A )  ln k  lnC   lnC
dt A B 4.3.1
Like equation 4.2, this is a linear relation,
 in three-dimensional variation ln(-dCA /dt), - ln(-CA), and
ln(-CB) space.

 It is also linear with respect to the constants lnk,

α, β and hence their values can be obtained by
linear regression from an experiment which
measures CA as a function of t.
 Values of (-rA) can be generated from these as a function of
CA by differentiation, as described above for the case of a
single reactant.
 The concentrations CA and CB are not independent but are
linked by the reaction stoichiometry
C C C C
A A,0  B B,0
 
A B

 Values of CB can thus be calculated from

measured values of CA.
 Alternatively, k, α, and β can be obtained directly
from equation (4.3.1) by nonlinear regression
  in the case of many reactants involved in the reaction,
we can use the so called method of excess

As an example A + B P
 
r A  k C A CB (4.4.1)

analyzed by applying differential method

incorporating isolation method i.e. reaction runs excess in B

i.e concentration of B remains essentially unchanged

during the course of reaction compared to
concentration of A then equation (4.4.1) becomes
  k ' C
dC A
 A
dt
 
k '  kCB  k CB,0 and k ' is known as pseudo reaction
rate constant

 dC A 
ln    ln k ' ln C A
 dt 

.

Here, it is possible to determine k’ and directly.

After determining  we can further process the reaction

with excess of concentration of A to determine 
 dC
Procedure to carry out differential method:  A  k C
dt A
• Measure concentration versus time : data
• Arrange the differential equation in a natural logarithmic form
(Linearization)
 
dC 

ln  A  ln k  lnC
 
Ex 





dt 

A
 
• Differentiate the CA versus t data either numerically or
graphically.
• Plot the natural logarithmic form of the rate equation
ln 
• Observe a straight line graph of dC A 

 dt  versus ln C A
• Obtain the slope of the graph 

It is to be noted that for the first-order case, ln 
dC A 
 versus ln C A
 dt 
should yield a straight line with a slope of 1.0.
ln
dC A 
 
 dt 

Slope=order of reaction

ln k

lnC A
differentiate CA data
 dC A can be determined from Differentiate the CA versus t
( )
dt data using

Graphical and

Numerical methods including

polynomial,

finite difference,

non-linear least square

analysis etc.
Differential Methods using PFR
As in the case of a BR, a PFR can be operated in both a differential
way to obtain kinetics data

Consider steady-state operation for a system reacting according to

A Products
The system is not necessarily of constant density, and to emphasize
this, we write the material balance for calculating (-rA) in the form

dX
(r )  F A (4.5)
A A,0 dV
Depending on the method of analysis for species A, XA may be calculated from
CA, together with the flow rates, FV and FA, by equations
F F F
X  A,0 A C  A
A A F
F V,f
A,0
F F
 F  A A,0
 
A A

By varying CA,0 at the inlet, and/or by varying flow rate, in a series of

experiments, each at steady-state at the same T; one can measure (-rA) as a
function of CA at the given T to obtain values of k and α in the rate law, in the
same manner as described for a BR.
 Differential Methods using CSTR
No need to differentiate CA data
Consider a constant-density reaction with one reactant
A Products
The material balance obtained
C C
(r )  A,0 A  (C C ) F V
A t A,0 A V ,0

The rate law given (r )  k C

A A
One experiment at steady-state generates one point value
of (-rA) for the conditions (CA,0 ,FV,0, T) chosen.
To determine the form of the rate law,
C C
(r )  A,0 A  (C C ) F V
A t A,0 A V ,0
 values of (-rA) as a function of CA may be obtained from a series of
experimental conditions

Experimental conditions are changed by varying either CA,0 or FV,0.

(r )  k C
For a rate law given by A A
 the parameter-estimation procedure is the same as that in the
differential method for a BR in the use of equation 4.2.1
(linearized form of the rate law) to determine k and n.
 Linearization becomes ln( r )  ln k  lnC
A A

The use of a CSTR generates point (-rA) data directly without

the need to differentiate CA data (unlike the differential
method with a BR)
If there is more than one reactant, with a rate law given by


(r )  kC C 
A A B
the procedure to determine (-rA) is similar to that for one
reactant, and the kinetics parameters are obtained by use of
equation 4.3.1, the linearized form of the rate law.
 4.3. Integral methods
 The integral method follows a trial and error
approach to find reaction order
General procedure
generate values of CA as a function of t,
• Guess the reaction order and integrate the mole
balance equation
•Calculate the resulting function for the data and plot
this against function of time.
•If the resulting plot is linear, the reaction order is
probably guessed correctly.
 • If the plot is not linear, guess another order and
repeat the procedure.
The integral method is mostly used for known
order of reaction and
it is best used to evaluate the rate constant at
different temperatures in order to determine the
activation energy.
Integral methods analysis using BR
For a reaction involving a single reactant A with a rate law given
(r )  kC n
A A 4.6
we obtain, using the material balance as
dC
A  kdt
n 4.6.1
C
A
Integration of this between the limits of CA,O at t = 0, and CA at t results in

4.6.2

Equation 4.6.2 implies that a plot of CA1-n versus t is a straight line

with slope and intercept indicated in Figure. Since such a linear
relation is readily identified, this method is commonly used to
determine values of both n and k.
Note, since n is unknown initially, a value must first be
assumed to calculate values of the ordinate.
 As noted in equation 4.6.2, the form given there is not applicable to a first-
order rate law, this is due to that n = 1, equation 4.6.2 becomes indeterminate
(kt = 0/0). In such case, we return to equation 4.6, which then integrates to
dC
- A  kdt 4.7
C
A

which then integrates to C  C ekt 4.7.1

A A,0

or linearization becomes lnC  lnC  kt 4.7.2

A A,0

a linear relation for a first-order reaction is obtained from a plot of ln CA

versus t.
If the rate law involves more than one species, as

(r )  kC  C  C 
A A B C
The rate law with different species
 A B 
 P
A B
 the same general test procedure may be used, but the
integrated result depends on the form of the rate law.
 
The rate law for the above equation becomes r  kC AC B
A B

From the rate law and the material-balance equation, the equation to be
integrated is dC
-  A
  kdt
4.8
C A C B
A B
As we know, CB is not
independent of CA , but is related
to through Stoichiometry, to which
we add the extent of reaction to
emphasize that there is only one
composition variable: CA
 C C C C
A A,0  B B,0  
  V 4.9
A B
Equation 4.9 may then be used to eliminate both CA and
CB from equation 4.8, which becomes
d   k dt
(C  a )(C  b ) a
A,0 B,0
 
Where a A ; b B
V V
Integration by the method of partial fractions become

4.10
Thus, ln CA / CB is a linear function of t, with the intercept and slope
as indicated, for this form of rate law. The slope of this line gives the
value of k, if the other quantities are known.

Integral methods analysis using PFR

It is possible to obtain values of kinetics parameters by means of
such a reactor from the material balance equation rearranged as

V dX
 A
F (-r ) 4.11
A,0 A

If the rate law (for (-rA)) is such that the integral can be evaluated
analytically, then it is only necessary to make measurements (of CA
or XA) at the inlet or out let.
Thus, if the rate law is given by equation 4.6, integration of the right side of equation
4.11 results in an expression of the form
g(XA) / k ,where g(XA) is in terms of the order n, values of which can be assumed
by trial, and k is unknown. The left side of equation 4.11 for a given reactor can be
varied by changing FA,0, and g(XA) is a linear function of V/FA,0 with slope k, if the
correct value of n is used

If the rate law is such that the integral in equation 4.11 cannot be evaluated
analytically, it is necessary to make measurements from samples at several
points along the length of the reactor, and use these in a numerical or graphical
procedure with equation 4.11
 Exercise
If the gas-phase reaction A B +C
is first-order with respect to A, show how the value or the rate
constant k can be obtained from measurements of CA (or XA) at
the inlet and outlet of a PFR and CSTR operated isothermally
at T, and at (essentially) constant P

Solution The rate law is

(r )  kC
A A
V  dX
A
and CA and XA are related by 
F (-r ) 4.11
A,0 A
 F F (1 - X )
C  A  A,0 A
A F F
V,f V,f
If we assume ideal-gas behavior, and that only A is present in
the feed, the dependence is given F F (1  X )
V,f V,0 A

Substitution of the above equations for (-rA) , CA, and FV,f in

equation 4.11 results in

X    
 

V 1 A (1 X ) X 2ln(1 X ) 
A dX   A

A 

F k 0 (1  X ) A k
V,0 A
Thus, for given V, T, and P, if FV,f is varied to
obtain several values of XA at the outlet, the
expression

 X  2ln(1  X )
 
 
 
A
 A 

is a linear function of V/FV,f, with slope k

4.4 Initial rate methods
In this method, initial rate can be found, i.e.
 a series of experiments is conducted at
different initial concentration,
 The initial rate can be found by
differentiating the data and extrapolating
to zero time.
In other words, (say) the initial rates of reaction are
found by plotting the concentration-Vs-time curve and
finding the slopes at t = 0 as shown in Figure

dc
Slope = initial rate = 
dt
C

t
4.5 Method of half-lives
The general equation for half-life as defined

t  2n11
1 k C n1(n 1) (4.12)
2 A,0

This equation lead to the same conclusion that

t C n1  m, cons tant( for all n )

1 A,0
2
This may be used as a test
 to establish the value of n, by trial,
from a series of experiments carried
out to measure t1/2 for different values
of CA,0.
 The value of k can then be calculated
from the value of n obtained, from
equation 4.12.
Taking the natural log of both sides, we get

lnt ln 2n11 (1 n)lnC (4.12.1)

1 (n 1)k A,0
2

The equation can be used in linear form (ln t1/2 versus ln

CA,0) for testing similar to that described in the previous
section.

The slope of a plot of lnt 1 as a function of initial

2
concentration ln C A,0 is equal to 1 minus the reaction
Order n
 lnt 1
2 Slope = 1- n

ln C A,0

Example for a first-order rxn: t1/2 is independent of CA,0. A series of

experiments carried out with different values of CA,0 would thus
all give the same value of t1/2 if the reaction were first-order.
 4.6. Least-square methods
 The method of least-squares can give the order of the
reaction with respect to all the components at once.
 This method is effectively used, when the rate law
depends on
 the concentration of more than one species, if it is
not possible to use the method of excess
 frequency factor,
 activation energy etc.,
  The Least-Square method requires having a series
of measurements
Let us consider the reaction, aA  bB  P

and the rate expression is given by, dC A a b

  r A  kC ACB
dt
Linearization gives

ln(rA )  ln k  a ln C A  b ln CB
Which is a general form of

Y  c  aX1  bX 2 (a)

Where

Y  ln 
dC A 
; c  ln k ; X1  ln C A ; X 2  ln C B
 dt 
If we now carry out N experimental runs, for the
jth run
- the equation can be written as,

Y j  c  a X1, j  b X 2, j
For N runs, it will be 1,2 -------------- N. For which the
equations can be written as,
N N N
 Y j  Nc  a  X1 j  b  X 2 j
j 1 j 1 j 1

N N N 2 N
 X1 j Y j  c  X1 j  a  X1 j  b  X1 j X 2 j
j 1 j 1 j 1 j 1

N N N N 2
 X 2 jY j  c  X 2 j  a  X1 j X 2 j  b  X 2 j
j 1 j 1 j 1 j 1
These equations are three linear with three unknowns, and can be
solved for c, a and b which are rate constants and order of reaction
of A and B.