5.

Methods of analysis of rate data

The chemical engineer needs rate equation for
 designing of reactors
 boosting the performance of a reactor.

Determination of the rate equations can only be found through

experimental data.

This leads to important experiments to be carried on

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 to yield the complete rate equation for some reaction
parameters.
The most difficult part in kinetic is to find the rate law parameters
after having the experimental data.
Raw Data obtained from the batch or flow reactor experiments are analyzed in one
of the following ways:
The differential method;
The integral method ;
The initial rate method;
The half-life method;
The least-square method
For our study and application purposes, we will limit the above
methods analyses in batch reactor systems.
 Differential Methods
 In this method, it requires differentiation of the experimental
data to obtain a rate derived from the experiment.
 Restriction for application for such method is that it should
only be applied for irreversible reactions with a single reactant
Consider the decomposition of the following reactant
A   P
The kinetic expression for such type of reaction is given by
r  r  k C
A A A
dC A 
 k C A
dt
 dC A 
ln   ln k   ln C A
 dt 
Test the fitness of the experimental data using equation directly
without involving integration, to find k and 
 dC A can be determined from concentration versus time data
( )
dt using
graphical,
polynomial,
finite difference/ numerical,
 non-linear least square analysis etc.
In the case of many reactants involved in the reaction, method of
excess can be used.
Example if two reactants involved in the reaction
A + B P
 r  k C C 
A A B
Can be analyzed by applying differential method incorporating isolation
method by assuming the reaction runs excess in B, means concentration of B
remains essentially unchanged during the course of reaction compared to
concentration of A.
r  k ' C 
A A
 k C  and k ' is known as pseudo reaction rate
k ' kCB B ,0
.
constant
ln( rA ) ln k ' ln C A

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 β. In such cases, the rate
equation can be written by
 Procedure to carry out differential method:
• Measure concentration versus time
• Arrange the differential equation in a natural logarithmic
form
e.g  dC A 
ln   ln k  ln C A
 dt 
• Differentiate the CA versus t data either numerically or
graphically.
• Plot the natural logarithmic form of the rate equation

•Observe a straight line graph of ln   dC A  versus ln C

 dt  A
•Obtain the slope of the graph
dC A 
It is to be noted that for the first-order case, ln 
 
 dt 

versus ln C A should yield a straight line with a slope of 1.0.

  dC A 
ln  
 dt 
Slope=order of reaction

ln k

lnC A
 Graphical method
a. Equal-area differentiation
 It is advantageous to use this technique to analyze the data before

planning the next set of experiment

 Involves plotting - ΔCA/ Δt as a function of time and then using

equal- area differentiation to obtain - dCA /dt

b. Slope calculation of tangent lines of smooth curve
1. Plot the CA vs. t data, and then draw a smooth curve to the data.

2. Determine the slope of this curve at suitably selected

concentration values. These slopes dCA/dt = rA are the rates of
reaction at these compositions.
3. Draw ln(dCA/dt) vs ln CA, then the slope and intercept of the
best line gives α and k.
 Example: Reactant A decomposes in a batch reactor
A Products
Determine the order of the reaction
 Polynomial Fit

• To fit the concentration-time data to an nth-order polynomial

• Software packages, polymath, will calculate the best values for the constants a.

• One has only to enter the concentration-time data and choose the order of the p

polynomial. After determining the constants, a,, one has only to differentiate.

• Care must be taken in choosing the order of the polynomial.

 Numerical Method
 Numerical differentiation formulas can be used when the data points in the
independent variable are equally spaced such as t1- t0 = t2 – t1 = Δt

The three-point differentiation formulas

Example: The reaction of triphenyl methyl chloride (trityl) (A) and methanol
(B)
was carried out in a solution of benzene and pyridine at 25°C. Pyridine reacts
with HCI that then precipitates as pyridine hydrochloride thereby making the
reaction irreversible.

The initial concentration of methanol was 0.5 mol/dm3.

Part (I) Determine the reaction order with respect to triphenyl methyl chloride.
Part (2) In a separate set of experiments, the reaction order with respect to
methanol was found to be first order. Determine the specific reaction rate
constant.
Part (1) Find reaction order with respect to trityl.
Step 1 Postulate a rate law.
Step 2 Process your data in terms of the measured variable, which in this
case is CA.
Step 3 Look for simplifications. Because concentration of methanol is 10
times the initial concentration of triphenyl methyl chloride. Its
concentration is essentially constant

1. Graphical Method
Finite Difference Method
Polynomial Method
Using the Polymath software package to express concentration as a function of
time

Substitute the time values to get each the corresponding

rate
Now plot natural logicism of columns 2. 3. and 4 Vs column 5 on log-log paper
and the slope is 2.05 and k” is 0.12 dm3/ mol. min
 Integral Methods
The integral method follows a trial and error approach to find
reaction order
General procedure
 Guess the reaction order
 Integrate the differential equation.
 Plot concentration versus time
 If the plot of the concentration-time data is linear, the order we
guess is correct.
 If the fit is unsatisfactory, another order is guessed and tested

It is important to know how to generate linear plots of functions

of CA versus t for zero order, 1st order, 2nd order reactions.
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.
 For the reaction A P carried out in a constant-volume batch reactor, the
mole balance is

 For a zero-order reaction, rA = -k, and the combined rate law and mole balance is

 Integrating with CA = CA0 at t = 0, we have

CA = CA0 − kt

A plot of the concentration of A as a function of time will be linear with slope (-K).
 If the reaction is first order, integration of the combined mole balance and
the rate law.
With the limit CA = CA0 at t = 0 gives
dC A
 kC A
dt

C A0
ln Kt
CA

 Consequently, we see that the slope of a plot of [In (C A0/CA)] as a function of

time is linear with slope k.
 For a Second order reaction

dC A 2
  kC A
dt

 Integrating with CA = CA0 initially yields

1 1
_ Kt
C A C A0

 For a second order reaction plot of 1/CA as function of time

should be linear with slope K.
 The variation in the partial pressure of azo methane with time was followed at 600 K, with the
results given below. Find the rate constant and the order of the reaction.

CH3N2CH3(g)→CH3CH3(g) + N2(g)

t/s 0 1000 2000 3000 4000

P/pa 10.9 7.63 5.32 3.71 2.59

 Let us guess it’s a first order reaction.

t/s 0 1000 2000 3000 4000

0 -0.360 -0.720 -1.082 -1.441

The plot is straight, confirming a first-order reaction, and its slope is −3.6 × 10 −4. Therefore, k = 3.6 × 10−4 s−1.
 Method of half-lives
The general equation for half-life as defined
2  1  1
t 
k C  1(  1)
1
2 A,0

Taking the natural log of both sides, we get

2  1  1
ln t 1 ln  (1   ) ln C A,0
2 (  1) k

The slope of a plot of ln t 1 as a function of initial

2
concentration ln C A,0 is equal to 1 minus the reaction
order 
 Initial rate methods
In this method,
 A series of experiments is conducted at different initial
concentration
 The initial rate of reaction is determined for each test.
The initial rate can be found by differentiating the data and
extrapolating to zero time. In other words, 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 below
 This rate law signifies that the reaction is second-order in [I],
first-order in [Ar], and third-order overall.
 Least-square methods
There are three techniques in use for the least-square method:
 Linearized,
 Non-Linearized and
Weighted Least-Squares
 The method of least-squares can give the order of the reaction
with respect to all the components at once.
 That is why this method is effectively used, when the rate law
depends on the concentration of more than one species,
frequency factor, activation energy etc.,
 Especially if it is not possible to use the method of excess.
 The Least-Square method requires having a series of
measurements
i) Linear Regression
 Let us consider the reaction,
aA+bB⎯⎯→P
 Rate expression

 Taking the natural log both side

 Which is a general form of

Y = c + aX1 + bX2
where Y= ln(-rA) or ln(-dCA/dt), c =lnk, X1=lnCA, X2=lnCB,
a=α,b=β
 If there is N experimental runs carried out, for the j th - run, the
equation

 For N runs, it will be 1,2 -------------- N.


ii) Non-Linear Regression
 Here we search for those parameter values that minimize the
sum of the squares of the differences between the measured
values and the calculated values for all the data points.
a) Reaction rate(rA) –Concentration data(CA)
 Measured reaction rates, rm and the calculated reaction rates,
rc for all the data points.
i.e. sum of (rm - rc)² to be minimum.
 If we carried out N experiments.
s² N
( ri m  ric )²
 
2

N K i 1 N K

s ²  ( ri m  ric )²

Where N= number of runs.

K= number of parameters to be
determined.
rim= measured reaction rate for run i.
ric= calculated reaction rate for run i.
b) Concentration(CA)- time(t) Data

 Use POLYMATH or MATLAB to find the values of α and k the

would minimize the sum of the squares of the differences
between the measured and the concentration, rate reaction or