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;
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 CA 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
𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘𝐶𝐴𝜶
𝑑𝑡
Step1: Guess the order: Guessing zero order
Combined rate lawand mole balance equations and obtain deferential equation.
𝑑𝐶𝐴
= −𝑘
𝑑𝑡
Step2: Integrating the differential equation
Integrating with CA = CA0at t = 0 and CA=CA at t= t, we have
CA = CA0 −kt
Step3: Plot concentration versus time
If the plot of concentrationas a function oftime 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 mole balance and the rate law equations.
dC A
kCA
dt
Step2: Integrating the deferential equation
With the limit CA= CA0at t= 0 and CA=CA at t=t, gives
𝐶𝐴 𝐶𝐴0
𝑙𝑛 = −𝑘𝑡 , 𝑙𝑛 = 𝑘𝑡 , 𝑙𝑛𝐶𝐴 = 𝑙𝑛𝐶𝐴0 − 𝑘𝑡
𝐶𝐴0 𝐶𝐴
Step3: Plot natural logarithm of concentration versus time
If the plot of concentrationas a function oftime 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 ln CA 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 mole balance and the rate law equations.
dC A
kCA
2
dt
Step2: Integrating the deferential equation
Integrating with CA = CA0initially, and CA=CAfinally, yields
1 1
= + 𝑘𝑡
𝐶𝐴 𝐶𝐴0
Step3: Plot the reciprocal of concentration as a function of time
If the plot is linear, our guessed order is correct
The slope of a plot 1/CAas 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.
−dPA
= k P PA
dt
dPA
= −k P dt
PA
Initial point: at t = t0 , PA = PA0
Final point: at t = t, PA = PA 𝑙𝑛(𝑃𝐴 /𝑃𝐴0 ) = -kPt After integration
CONT…
t(s) 0 1000 2000 3000 4000
PA/PA0 1 0.69768 0.48675 0.33892 0.23669
ln(PA/PA0) 0 -0.360 -0.720 -1.082 -1.441
Plot 𝑙𝑛(𝑃𝐴 /𝑃𝐴0 ) 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 mole balance with the rate law given by
dC A
kCA
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
The three-point differentiation formulas
𝑑𝐶𝐴 −3𝐶𝐴0 + 4𝐶𝐴1 −𝐶𝐴2
Initial point: =
𝑑𝑡 2∆𝑡
𝑑𝐶𝐴 𝐶𝐴(𝑖+1) − 𝐶𝐴(𝑖−1)
Interior point: =
𝑑𝑡 2∆𝑡
𝑑𝐶𝐴 𝐶𝐴3 − 4𝐶𝐴4 + 3𝐶𝐴5
Last point: =
𝑑𝑡 2∆𝑡
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.
𝐶𝐴 = 𝑎0 + 𝑎1 𝑡 + 𝑎2 𝑡 2 + 𝑎3 𝑡 3 + ⋯ + 𝑎𝑛 𝑡 𝑛
Differentiate Equation with respect to time:
𝑑𝐶𝐴
= 𝑎1 + 2𝑎2 𝑡 + 3𝑎3 𝑡 2 + ⋯ + 𝑎𝑛 𝑡 𝑛−1
𝑑𝑡
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, CAO,and the
initial rate of reaction, r0 , is determined from each run.
𝑟0 = 𝑘𝐶𝐴0 𝛼 , 𝑟0 = 𝑘𝐶𝐵0 𝛽
Keeping the initial concentration of species B constant and varying initial concentration
of species A
ln (r0 ) = lnk + αln 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 + βln 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 determininghalf-life of a reaction asa 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 excessin conjunction with the method of half-lives to arrange the rate
lawinthe form -rA= kCAα
For the irreversiblereaction A Product
𝑑𝐶𝐴
− = 𝑘𝐶𝐴𝜶
𝑑𝑡
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 methods 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, especially if it is not possible to use the method of excess.
i) Linear Regression
Let us consider the reaction,
aA+bB⎯⎯→P
Rate expression
Cont.
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 jth - run, the equation
For N runs, it will be 1,2 -------------- N.
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.
Cont.
ii) Non-Linear Regression
Here we search for those parameter values that minimize the sumof 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.
𝑟𝑖𝑐 = 𝑘𝐶 𝑛𝐴𝑖
If we carried out N experiments.
2 𝑁 2
𝑠 (𝑟
𝑖=1 𝑖𝑚 −𝑟𝑖𝑐 )
σ2 = =
𝑁−𝐾 𝑁−𝐾
𝑁
𝑠2 = (𝑟𝑖𝑚 −𝑟𝑖𝑐 )2
𝑖=1
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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