2.

In ethanol production by fermentation of corn, hydrolyzed ground corn in a water suspension

containing 50% corn by weight is mixed with sufficient enzyme to produce ethanol by the
approximate reaction C6H12O6→ 2C2H5OH + 2CO2
When the solution reaches 12% ethanol, the yeast dies and the reaction stops.
(a) How many bushels of corn are required to produce 500 tons of pure ethanol per day? Assume
1 bushel of corn weighs 56 lb.

bushel
 CHAPTER FIVE

Methods of analysis of rate data (Determination of Rate Equations from the

Experimental Data)
Monitoring reaction progress
Reaction progress kinetic analysis relies on the ability to accurately monitor the reaction
conversion over time.

The experimental methods used in kinetics classified into two categories, namely chemical and
physical.

(i) In Chemical analysis, it is possible to determine directly the concentration of one of the
reacting substances or products against time (or more specifically of residence time)
(ii) In Physical Analysis, the physical change during the course of reaction is measured.

Some of the physical methods are associated with the measurements of the pressure in gaseous
reaction directly i.e., the measurements of the changes in the volume produced by the reactions.
The other methods are optical methods such as colorimetry, conductometry, mass spectroscopy.
The advantages physical methods, measurement is rapidity.
Raw Data obtained from the batch or flow reactor experiments are analyzed in one of the
following ways:

(i) The differential method;

(ii) The integral method;
(iii) The initial rate method;
(iv) The half-life method;
(v)The least-square method;
5.1 Differential Methods
In the differential method of analysis, we test the fit of the rate expression to the data directly and
without any integration.

these techniques are sometimes categorized as differential (monitoring reaction rate over time)

There is advantage and disadvantage to integral method. The differential method is useful in more
complicated situations but requires more accurate or larger amounts of data.
can be used to develop or build up a rate equation to fit the data.
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 applied for irreversible
reactions with a single reactant.

limit this methods analyses in one of the systems i.e., batch reactor systems.
Consider the decomposition of the following reactant,

A→P
The kinetic expression for such type of reaction is given by
𝑟  𝐴 =− 𝐾 𝐶 𝐴 𝛼  
Now, we test the fitness of the
and the material balance for constant volume is given by experimental data directly without
involving integration, to find k and α.
  𝑑𝐶𝐴
𝑟 𝐴=  − 𝑑 𝐶 𝐴
𝑑𝑡
𝑑𝑡
combining these two equations, we get
 − 𝑑 𝐶 𝐴 can be determined from concentration
𝛼
=𝐾 𝐶 𝐴
𝑑𝑡 versus time data using one of the methods
Taking natural logarithm of both the sides, we get such as graphical, polynomial, finite
  𝑑𝐶𝐴
𝑙𝑛 − (𝑑𝑡 )
=𝑙𝑛   𝑘 + 𝛼   𝑙𝑛 𝐶 𝐴 difference
In the case of many reactants involved in the reaction, we can
where
use the so called method of excess. Let us consider the
following reaction, k′= kCB β
= k CB0 β
and k is known as
A+ B →P pseudo reaction rate constant. Taking

𝑟  𝐴 =− 𝐾 𝐶∞ 𝐴 𝐶 𝛽 𝐵 natural logarithms of both sides we get

where k,∞ and β are unknown.
Such type of reaction can be analyzed by applying differential
method incorporating isolation method. Let us assume that the
reaction runs excess in B in such a manner that the
concentration of B remains essentially unchanged during the
ln(-rA)=ln k′+αln CA
Here, it is possible to determine k and α directly.
After determining α , 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

course of reaction compared to concentration of A then rA  K C  B

It becomes

𝑟  𝐴 =− 𝐾 𝐶• 𝛼 Where, K′′=CαA=′≈KCαA,0
𝐴
The general procedure given in carrying out differential method:

(i) Measure concentration -vs-time

(ii) Arrange the differential equation in a natural logarithmic form.

(iii)Differentiate the CA versus t data either numerically or graphically.

(iv) Plot the natural logarithmic form of the rate equation Observe a straight line graph of ln
-dCA/dt versus ln CA

(v)Obtain the slope of the graph

Figure 5.1 Graphical representation in differential method to find the order of reaction and the rate constant.
5.2 Integral Methods
In the integral method of analysis,

we guess a particular form of rate equation and, after appropriate integration and
mathematical manipulation, predict that the plot of a certain concentration function versus
time should yield a straight line.

The data are plotted, and if a reasonably good straight line is obtained, then the rate
equation is said to satisfactorily fit the data.

The integral method follows a trial and error approach to find reaction order.

integral (monitoring the amount of substrate and/or product over time), simple mathematical
manipulation allows inter conversion of the data obtained.
General procedure followed in the application of this method is:

i. Guess the reaction order and integrate the mole balance equation
ii. 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.
iii. If the plot is not linear, guess another order and repeat the procedure

There is advantage and disadvantage to integral method. The integral method is easy to use and
is recommended when testing specific mechanisms, or relatively simple rate expressions, or
when the data are so scattered that we cannot reliably find the derivatives needed in the
differential method.

The integral method can only test this or that particular mechanism or rate form.
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.

Zero Order, n=0 First Order, n=1 Second Order, n= 2

t t

dC A dC A dC A
 rA =-k  rA =-kCA  rA =-kCA2
dt dt dt
at t=0, CA=CA,0 at t=0, CA=CA0 at t=0, CA=CA0
 CA=CA0-kt C  1 1
 ln  A 0   kt    kt
C A C A0
 CA 
5.3 Initial Rate Methods
o The reactor is operated using different initial concentrations.
o From the initial slope of the concentration vs. time data, the rates corresponding to these
initial concentrations are obtained.
o plotting ln (rate) vs. ln CA0 will give the order and the rate constant, just like in the

differential method
o the big disadvantage of this method is that lot of experiments are required

In this method, a series of experiments is conducted at different initial concentration, and the
initial rate of reaction is determined for each test.

aA product rA,0  k C A ,0
Taking the natural logarithm for both sides,

we obtain ln  rA,0   ln k   lnC A,0

Experiment were performed involving reactants A and B In any well designed experiment,
the following data was collected: there should be a control. varies A
while holding B constant

Experiment Initial rate Initial Initial A good experimenter then reverses

the variables and varies B while
number mol/(L×hr) concentrati concentrati holding A constant
on[A]0 on[B]0 k  reactant   reactant 
m n
rate1

k  reactant   reactant 
m n
rate2
1 0.50×10-2 0.5 0.2
2 0.5×10-2 0.75 0.2 Using trials 1 and 4
3 0.5×10-2 1 0.2
0.50 10 2
k  0.5  0.2
m n
1  1  n=1
 ln    n ln  
4 1×10-2 0.5 0.4 110 2
k  0.5  0.4
m n
2  2
5 1.50×10-2 0.5 0.6
When analyzing a set of data, you should be aware of the following:
 5.4 Method of Half-Life
Another parameter to determine the rate
constant quantitatively by the application of so- o A ’fractional life’ method may easily be

called half- life. The half-life is the time used, performing all calculations and
required for one-half of the reactant to undergo experiments to the time when the
reaction or the time taken for 50% reaction to concentration is something like 10% of
occur (50% conversion). CA 1 the initial concentration.

C A,0 2

o half-life is the time taken for the concentration of a reactant to fall to one-half its original value
o it is just the same half-life when we dealt with radioactivity
half-life of a reaction denoted by
Reaction order Half-life,(t1/2)
For which let us consider the general
reaction. 0 CA0/2k directly to CA0
A P
Where α = α th
- order of the reaction. The rate
1 ln2/k independent of CA0
equation can then be written as,
dC A 1 1
  k AC  A  1
  1
    1 k t
dt CA C A,0 2 1/CA0k inversely to CA0

2 1
t1/2 
   1 ka C A,0 1  3 3/2CA0k inversely to CA0

Taking the natural log of both sides, we get

 1 α th 2  1
 1
ln 2  1
ln t1/2    1    lnC A,0     1 C  1
k 
   1 k
A0
 5.5 Least-Square Methods
Taking the natural log of both sides of the equation, we get
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,
Which is a general form of
frequency factor, activation energy etc., especially if it is
not possible to use the method of excess. The Least- 𝑌  =𝑐+ 𝑎 𝑋 1 +𝑏 𝑋 2
Square method requires having a series of measurements. Where,
Let us consider the reaction,
  𝑑𝐶𝐴
(
𝑌 =𝑙𝑛 −
𝑑𝑡 )
;   𝑐=𝑙𝑛   𝑘 ;   𝑋 1 =𝑙𝑛  𝐶 𝐴 ;   𝑋 2=𝑙𝑛   𝐶 𝐵

𝑎𝐴
  +𝑏𝐵 → 𝑃
If we now carry out N experimental runs, for the jth - run,
and the rate expression is given by,
it can be written as,
  𝑑 𝐶𝐴 𝑎 𝑏
𝑌  𝑗=𝑐+𝑎 𝑋 1 𝑗 +𝑏   𝑋 2 𝑗
− =− 𝑟 𝐴 =𝑘 𝐶 𝐴 𝐶 𝐵
𝑑𝑡
 For N runs, it will be 1,2 -------------- N. For which the equations can be written as,

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.