LECTURE 5

DETERMINATION OF RATE EQUATIONS FROM

THE EXPERIMENTAL DATA
 INTERPRETATION OF BATCH REACTOR DATA
Overall objective: Determining the rate law parameters and obtaining the rate equation
for a specific reaction
Specific objectives:
 getting the experimental data for a specific reaction
 analyzing the experimental data
 determining the rate law parameters (α&k)
 obtaining the rate law (rate equation)(e.g. -rA=kCAα)
 Batch reactors are used primarily to determine rate law parameters for homogeneous
reactions
 In batch reactor experiments, concentration, pressure, and/or volume are usually
measured and recorded at different times during the course of the reaction

 Usually achieved by measuring concentration as function of time

 Using data analysis methods to determine the reaction order, α and specific reaction
rate constant, k
 Five different methods of analyzing the data collected are used:

 The integral method

 The differential method

 The method of half-lives

 Method of initial rates

 Linear and non-linear regression (Least-squares method)

 For batch systems, the usual procedure is to collect concentration vs time data.
 1. Integral Method of Analysis
 Uses a trial and error procedure to determine the reaction order.
 Steps followed during integral method of data analysis are;
 Combine the rate law and material balance equation

 Guess the reaction order

 Integrate the differential equation

 Plot the integrated equation

 If the plot 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 C A versus t for zero order, lnCA
versus t for 1st order, 1/CA versus t for 2nd order reactions.
 CONT….
 For the reaction A P carried outin a constant-volume batch reactor, the mole
balance is
Step 1: Combine rate law and material balance equations

Step2: Guess the order: Guessing zero order( =0)

Step3: Integrating the differential equation

 Integrating with CA = CA0at t = 0 and CA=CA at t= t, we have

CA = CA0 −kt
Step4: Plot concentration versus time
 If the plot of concentration as a function of time is linear, our guessed order is correct
 The slope of the linear line is (-k) and its intercept is CA0
Step4: If the plot doesn’t fit linear, guess another order of reaction(1st or 2nd order)
 CONT…
Step1: Guess first order
 Combined rate law and material balance equation.

dC A
  kC A
dt
Step2: Integrating the deferential equation
 With the limit CA= CA0 at t= 0 and CA=CA at t=t, gives

Step3: Plot the natural logarithm of concentration versus time

 If the plot of concentration as a function of time is linear, our guessed order is correct
 The slope of a plot ln(CA0/CA) as a function of time is k, a plot of ln (CA/CA0) as a function
of time is (-k) and a plot of lnCA as a function of time is (-k)
Step4: If the plot doesn’t fit linear, guess another order of reaction ( 2ndorder)
 CONT…
Step1: Guess second order
 Combined the rate law and material balance equation.
dC A 2
   kC A
dt
Step2: Integrating the deferential equation
 Integrating with CA = CA0 initially, and CA= CA finally, yields

Step3: Plot the reciprocal of concentration versus time

 If the plot is linear, our guessed order is correct
 The slope of a plot 1/CA as a function of time is k

Step4: If the plot doesn’t fit linear, guess another order of reaction
 But the three commonly known orders are zero, 1st and 2nd
CONT….
CONT….
CONT…
Example 1: 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)
A B C

t(s) 0 1000 2000 3000 4000

PA (pa) 10.9 7.63 5.32 3.71 2.59

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

Initial point: at t = t0 , PA = PA0

Final point: at t = t, PA = PA = -kPt After integration
 CONT…
t(s)
t(s) 00 1000
1000 2000
2000 3000
3000 4000
4000
P
PAA/P
/PA0
A0
11 0.69768
0.69768 0.48675
0.48675 0.33892
0.33892 0.23669
0.23669
ln(P
ln(PAA/P
/PA0 )
A0)
00 -0.360
-0.360 -0.720
-0.720 -1.082
-1.082 -1.441
-1.441

 Plot versus t

 If the plot is straight line, our guess is correct

 The plot is straight, confirming a first-order reaction, and

its slope is −4 × 10−4.

 Therefore, kP = 4× 10−4 s−1.

 2. Differential method of analysis
Steps
i) Combining the rate law and mole balance equation
dC A 
  kC A
dt

ii) Taking the natural logarithm of both sides

 dC A 
ln     ln k   ln C A
 dt 
iii) Plotting ln(-dCA/dt) versus ln CA gives reaction
order(α) as the slope and the rate constant (k) as the
intercept.
 CONT…
 To obtain the derivative -dCA/dt, we must differentiate the concentration-time data

 Three methods to determine the derivative -dCA/dt from data:-

 Graphical differentiation

 Numerical differentiation formulas

 Differentiation of a polynomial fit to the data

 CONT…
i) Graphical Method
(a) Equal-area differentiation method
Steps:
1. Record concentration(CA) versus time data from an experiment
2. Generate (– ΔCA / Δt) versus Δt data
3. Plot graph of (– ΔCA / Δt) versus Δt
4. Obtain (- dCA /dt ) using equal - area differentiation
CONT…
(b) Slope calculation of tangent lines to smooth curve
Steps:
1. Record CA versus t data from an experiment
2. Plot the CA versus t a smooth curve.
3. Plot different tangent lines to a smooth curve
4. Determine the slope of tangent lines. These slopes are equivalent to -dCA/dt = -rA
5. Taking natural logarithm of -dCA/dt and CA
6. Draw ln(-dCA/dt) vs ln CA, then the slope and intercept of the best line gives α and k.
CONT…
ii) 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
Time (min) t0 t1 t2 t3 t4 t5
Concentration(mol/dm3) CA0 CA1 CA2 CA3 CA4 CA5
iii) Polynomial Fit
steps:
 Conduct an experiment and record concentration-time data
 Plot the polynomial graph of concentration-time data and choose the order of the
polynomial.

 Differentiate Equation with respect to time:

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

Example 2: 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
HCl that then precipitates as pyridine hydrochloride thereby making the reaction
irreversible. O
𝖨𝖨
(C6H5)3CCl + CH3OH (C6H5)3 CCH3 + HCl
A B C D
Time(min) 0 50 100 150 200 250 300

Concentration of A(mol/dm3)*103 50 38 30.6 25.6 22.2 19.5 17.4

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 wrt methanol was
found to be first order. Determine the specific reaction rate constant.
Part (1) Find reaction order wrt 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

i. Graphical Method
ii. Finite Difference Method
iii. Polynomial Method
Using the Polymath software package to express concentration as a function
of time
 CONT…
 Example 3: Reactant A decomposes in a batch reactor
A Products
Determine the order of the reaction
 3. Method of Initial Rate
 The method of initial rates could be used to determine the reaction order and specific
rate constant for the reaction more than one reactant involved.
 A serious of experiment is carried out at different initial concentrations, C AO,and the initial
rate of reaction, r0 , is determined from each run.

 Keeping the initial concentration of species B constant and varying initial concentration of
species A
ln (r0 ) = lnk +ln CA0

 The plot of ln (r0 ) versus ln CA0 will give a reaction order

 Keeping the initial concentration of species A constant and varying initial concentration of
species B
ln (r0 ) = lnk + ln CB0

 The plot of ln (r0 ) versus ln CB0 will give a reaction order

CONT…
 CONT…
 This rate law signifies that the
reaction is second-order in [I],
first-order in [Ar], and third-order
overall. The intercept corresponds
to k = 9 × 109 mol−2 dm6 s−1.
4. Method of Half-life
 By determining half-life of a reaction as a function of the initial concentration, the
reaction order and specific reaction rate can be determined.

 If two reactants involved in the chemical reaction, the experimenter will use the
method excess in conjunction with the method of half-lives to arrange the rate law
in the form -rA= kCAα

 For the irreversible reaction A Products

CONT…
 Integrating with the initial condition CA = CA0 when t = 0 we find that

1  1 1 
t   1  
K   1  C A C A0 
 1

 Substituting t = t1/2 when CA= 1/2CA0

2 1  1  1 
t1/ 2   
K   1  C A0 
 1

 Taking the natural log of both sides

2 1  1
ln t1/ 2  ln  1   ln C A0
K   1
CONT…
 Slope of the plot of ln t1/2 as a function of InCA0, is equal
to 1 minus the reaction order [i.e.. slope = (I – α)]
 5. Least Square Method
 There are three techniques in use for the least-square method: Linearized,
Non-Linearized and Weighted Least-Squares.
 Least-square method is effectively used for the reaction more than one reactant
involved
 It gives the order of the reaction with respect to all the components at once.
 It is not possible to use the method of excess.

i) Linear Regression
 Letus consider the reaction,
A + B ⎯⎯→ P
 Rate expression
 Cont.
 Taking the natural log both side

 Which is a general form of

where
 If there is N experimental runs carried out, for the jth run, the equation

(eqn 1)
 For N runs, it will be 1,2 -------------- N.
summation of eqn 1 for all runs
summation of product of eqn1 and X1j
summation of product of eqn1 and X2j
 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 using Matrix
 Cont.
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.

Cont.
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.
 Cont.
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 calculated values of concentration, rate reaction or reaction time
 END!!!
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